Cambridge International As and A Level Chemistry

Cambridge ENDORSED BY
International AS and A Level !i; f!.~!~!.!?o~o~
Chemistry
Peter Cann and Peter Hughes
ENDORSED BY
& CAMBRIDGE
V International Examinations
Cambridge
International AS and A Level
/.7 EDUCATION
HODDER
AN HACHETTE UK COMPANY
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ISBN978 1444 18 1333
Contents
Int rod ucti on ................................................................................................................... vi
AS Level
Phymalchem1stry
Topic 1 Chemical formulae and moles ......................................................................................................................... 1
Topic 2 The structure of the atom .. ............................ ............................ ............................ ............................ ........... 20
Topi c 3 Chemica l bonding in sim ple molecules ... .................................................... .... ............................................... 44
Topi c 4 Solids, liq uids and gases .... ................ ... .............. .......... ...... .. ..... ................ ... .............. .......... ...... .. ..... ........... 69
Topic 5 Energy changes in chemistry ......................................................................................................................... 97
Topic 6 Acids and bases .......................................................................................................................................... 118
Topic 7 Oxida tion and reduction ............................................................................................................................. 136
Topic& Rates of reactton .............................................................................................................................. l i 4
Topic9 Equilibria ................................................................................................................................................... 172
lnorgamcchem1stry
Topi c 10 Periodi city ..................................................................................................................... 186
Topi c 11 Group 17 .. . ....... 202
Organ1cchem1stry
Topi c 12 Introdu ction to orga nic chemist ry ............................................................................................................. 209
Topic 13 Alka nes .................................................................................................................................................... 234
Topic 14 Alkenes 251
Topi c 15 Halogenoalkanes 267
Topi c 16 Alcohols ................................................................................................................................................... 281
Topic 17 Aldehydes a nd ketones ............................................................................................................................. 294
Topic 18 Carboxylic acids and esters 305
Advanced practical skill s (Paper 3)
Topic 19 Practica l work .. . ............... 316

Contents
A Level
Phys1calchem1stry
Topic 20 Further energy changes...................................................................................................... 329
Topic 21 Quantitative kinetics ............................................................................................ 349
Topic 22 Quantita tive equili bria....................................................................................... 367
Topic 23 Electroc hemistry .. ........ .. ...... .. 381
lnorgamcchem1stry
Topic 24 The 3d block.. . .................................... 397
Orgamc chemistry
Topic 25 Arenes and phenols . .. 41 5

To pic 26 Carboxylic acids - derivatives and further reactions 440
Topic 27 Amines, amides and amino acids 449
To pic 28 Addition and condensation polymers 469
Topic 29 Techniques of analysis . . ...................... 495

To pic 30 Organic synthesis and analysis ............................................................................................. 520
Index . . .............. 540
Student's CD contents
Answers to 'Now try this' questions
Additional work
Interactive tests
Topic summaries
Revisionchecklists
Examination structure
Planning your revision
Examination technique
Glossary of command words
Mathematical background
Chemical data
Glossaries
Acknowledgements
We are grateful for the hdp given by Judy Pom,r in selecting and writing topic-oriented questions, and for the uns1intingly
professional supJX>fl and cooperation given by the Slaff at Hodder Education: Nina Konrad, EmiHe Kenon, Laurice Suess, Anne
TreviJHon and Anne Wanjie.
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Introduction
Cambridge lnternati,mal AS and A l.eu,I Chemistry uses
some of the content from Chemistry for Advanced Level. but 4' :~:': : ; : gr~:,:g~ : 1:t::~~il;!::. ;:::::::ti;fg
has been completely revised by the original authors to cater maneraffectsitsphysicalandchemical properties,and
for those students and teachers in,ulved with the Cambridge influenceshowsubsu.ncesreactchemically.
International Examinations syllabus 9701.
Thelxx>khasbeenfullyendorsedbyCambridge 4' Experiments and eYldcncc - Chemists use evidence
International Examinmions, and is listed as an endor.sed gained from ob.setvations and experiments to build models
textbook for students studying this syllabus . The syllabus andtheoriesofthestructureand reactiviryofmaterials .
contenthasbeenco,.eredcomprehensively,and has been
separated into AS material. which comprises Topics 1- 19, 4' Patterns in chemical beh a,Jour and rcactlons - By
whilst the A Level m:uerial is dealt with in Topics 2o-30 identifyingpanemsinchemicalbehaviourwecanpredict
All the Learning outcomes specified in the syllabus are thepropeni.,.sofsubstancesandhowtheycanbe
included inthelxx>k. AtthesrnnofeachTopicthespecific transformed imo new substances by chemical r.,actions. This
Learning outcome.s relevam to thm Topic are dearly stated. allows us to design new materials of use to sodery.
usingthesame,Nordingasinthesyllabus,sothatstudents
can dearly see the syllabus areas covered by the Topic. 4', Clu..'lllical bonds - The understanding of how chemical
The chan on the following page summarises the syllabus bonds are made and broken by the movement of electrons
coverage in each Topic . allowsustopl'roictpanernsofreactivity.
Throughout each Topic there are worked examples. with
answers,toillustratetheconceptsrecemlyimroduced. These
are followed by a few "Now uy this" questions. allowing
e Energy c hanges - The energy changes that take place
duringchemicalreactionscanbeusedtopredictlxAhthe
students to test themselves. Answers to these questions are extentandtherateofsuchreactions.
on the accompanying Students" CD-ROM.
EachTopicendswithasummaryofthekeyJX>ints This lxx>k has been designed to be acces.sible to all AS
covered. together with a listofkeyreactionswhererelevant. and A Level students. but also attempts to go some way
Finally.severalpast=aminationquestionshavebeen toward.ssatisfyingthecuri01Sityoftheablestudem. and
selected that illustrate how the subject man er of the Topic to answering the que.stions of the inquisitive. Although
has been assessed in the past. Answers to these questions based fim1ly on the AS and A Level syllabus of Cambridge
will be found on the Teachers' CD -ROM. lmemational Examinations, teachers and students wiJJ find
To allow .students and teachers to lornte easily the various the subject maner and style of questions make it suitable
aspectsofthesubjecr.theorderofTopicsisa kigicalone. forseveralcxhersyllabuses . Thesubjectmauerhasbeen
staningwiththeessentialbasicprinciplesofphysicalchemistry .,.xte ded n n e areas wh re an appl"cat on. or a more
and thenimroducingtheapplicationoftho,;eprinciplesfirstly fundamental explanation. is deemed to be appropriate .
to inorganic chemistry and then to organic chemistry. No These extensions are dearly delimited from the main text in
reaching order is implied by this, however. It has been found panels, and can be bypassed on first reading.
thatmixingprinciplesandapplicatiOflswithfactualcoment The majority of students Slatting an AS course in
throughoutthecourseisoftenthebestwaytoachievea chemistry come from a background of ]GCSE Chemistry
deeperandbroaderunderstandingofchemistry. Teachers are orCombinedScience,andtheinitialchaptersstanata
recommendedtoconsuhtheschemesof"urkpublishedby le-velandapacethatissuitedtoall such students.Some
Cambridge International ExaminatiOfls on their website for students come to AS chemistry with the belief that they will
some suggested methods of delivering the subject material. find the mathematics difficult, although th.,. mathematical
A feature of the new 2016 syllabus is the introduction of concepts required for chemistry are simple in principle and
Key con cepts. These are essential ideas. theories. principles few in number. W"e hope to demonstrate that. as long as
or mental tools that help learners to develop a deep theprocessesareunderstood , ratherthanleamedbyro1:e,
understanding of their subject and make links between the the mathematics in lxAh the AS and A Level Topics is well
differenttopics.Althoughteachersarelikelytohavethese within the grasp of those who have gained a grade Cat
inmindatalltim.,.swhentheyareteachingth.,.syllabus,we !GCSE'"'.
have included in the t=t the following icons at points where Siudentsalsosometimesconsiderthatchemistryisa
the Key concepts relate to the t=t. subjectfullof difficulcconcepts . Thisisnoitru.,.. Mostof
Introduction
chcmistiy is based on the very simplest idc-a of e le.:trostatic,i i-,owlMC~ml:lridgeLe.J.rn irigoutcomesarecoveredbytlle30TOpics

- like ch:ugcs n,pd, unlikc charges aurae1 . When the subtle in thi1 boo~
ra mifkation s of 1his 8'"neralisa1ion are 1>1udied d u ring tllo<'
Topk u ,amlngou1t- Topk Lumlngou~
AS and A Le,t'I cou,.,...,., students should =:mtly n,mi nd
1 1.1-1.5 16 17.11
themselves of tllo<' inherent simplicity of 1hts rebtionship.
Chcrnislryisthc=mralsciencc,,atrhecl055ro:ldsof
biology and ilS a560ciatn:l discipli-s Qn the one hand, and 3 3.2.3.3,3.SC), 14. J~ 18 19.1~.b). 19.J
physics on tile- other. Chemisu-y rdit$ on physics for its 4 3.1. 3.4, J .Sa),b), 4.1.
ur>elerscanding o( 1h<- fundamental building blocks cl matter, 4.2, 4.3~.C).d)
andbiologyrelic.sonchemi.slryforan underscandin gof tiK- 5 5.lak),5.2~ 20 2.3g).5.1b),d),S.M
stnictures of living organ isms. and the processes that go on 5.3,5.4,10.lt},g)
insidcthemthatwecalllife.Sm nding atthi scrossroods , the 6 1.5a)-<},7.2a),b) 21 8.1c}-h). 8.2c),8.3e)
chemist lsuniquelypositionedtoundcrscand,and make
7 4.3b),6.1,6.3g) 22 7.2c}-k).7.3
signifiaintcontributionsto, manyimerdisclplln:uyareasof
8 5.2b),8.1~,b).8.2a),b), 23 6.2.6.3,6.4
CtJ <rcnl aOO fu1ure importance. The c hemistry-based sciences
8.3.1)-d)
of biochemistry. genetic engineering, phamucology. and
polymer and matcrfal ~ c c , will all make increasing 24 12.1,12.2.12.3,12.4.
contributions to our physic,,! and material well-being in
thefuture. ChcmlM.Sarealso playing akc,y role in the fight 10 9.1~,9.2,9.J. 25 14.3.15.4,17.2
10.1~).13. 1, 13.2
against indusirial society'.spollurionofo.arenvironmc-nr.
We hopc,youenjoy discovttingthc,.sc,cre15ofchem iS1ry 11 11 .1-11.5 26 17.1~.19.lb)-t)
during rourAS/ A Leve,] course."" 12 1.5b),14.1a),b),d),e), 27 20.1,20.2.20.J
14.2,14.4
Pete rHughe.s 13 15.1,15.3a),b) 28 21.1,21.2.21.3,21.4
14 14.3,15.2 29 22.1,22.2.22 .3,22.4,
lGCSE is the regiSlered trademark of Cambridge
lnte r~tion:i l Exa mi~tions. 15 16.1,16.2 30 231 , 23.2
This page intentionally left blank
AS Level
Physical chemistry
1 Chemical formulae and moles

lnthistopicweintroducechemica/
formulae, and show you how
Learning outcomes
thesecanbeworkedoutusingthe Bytheeodofthistopicyoushouldbeableto
valencies(orcombining~wers)of 1.1a) define and use the terms reliltive atomic, isotopic, molecular and formula rmsses,
atoms and ions. We also introduce basedonthe 11C=le
thechemists'fundamentalcounting 1.2a) definearidusetheteimmoleintermsof theAvogadroconstant
unit, the mole, and show you how 1.4a) defineandusethetermsempirica/andmo/ecu/arfrxmuld
itcanbeusedtoca/culateboth 1.4b) uikukite empirical and mo~ul ar formulae, using rnmbtJstion data or composition
empirical formulae and the amounts
by mass
ofsubstancesthatreact,orare 1.Sa) writeandrnristrlKtbalancedequatioris
formed, during chemical reactions. 1.Sb) perform ca lrnlations, incltJdir,g ll'ie of the moH! concept. invoMng reacting
As )OU read through the topic. study masses(fromformulaeandeql!iltions),volumesof gases(e.g. inthebumingof
the worked examples, and then t,y hydroca rbons),vcltJmesa ndconcentrationsol sollllions,andrelatethenumbefof
the'Nowt,ythis'questionsthat significantligures inyouranswersto tho1egiver1orasked for in the qtJestion
follow them. 1.Sc) deduce stoichiometricrelationshipsTI"omcalrnlations SlKhasthosein 1.Sb)
1.1 Introduction
What is chemistry?
Chemistry is the Sludy of the properties of matter. By matte r . we mean the
substancesthatwecan.see.feel.10uch.tasteandsmell - the.s1uffthatmakesupthe
material world. Passive obsef\'ation forms only a small pan of a chemiSl's interest
in the world . ChemiSls are actively inquisitive sdentiSls. We try to under.stand why
mauer has the properties it does. and how to modify these properties by changing
onesubstanceinroanO!herthroughchemicalreactions.
Chemistry as a modern science began a few hundred years ago, when
chemists started to relate the observations they made about the subsrnnces
they were investigating to theories of the structure of mailer. One of the most
important of these theories was the Atomic Theory . lt is just over 200 years
since John Dalton put forward his idea that all matter was composed of atoms .
His theory stated that :
e theatomsofdifferentelementsweredifferentfromeachother
the atoms of a particular element were identical to each O!her
all a!Oms srnyed the same over time and could be neither created nor destroyed
all maner was made up from a relatively small number of elements (Dalton thought
about SO) combined in various ways.
figure 1.1 John Dalton. who first ~ggested Although Dalton 's theory has had to be modified slightly. it is still a useful starting
lhemo:iernAtomicTheory JX>intforthe.s1udyofchemistry.
PHYSICAL CHEMISTRY
Sincethattimechemistshaveuncoveredandexplainedmanyoftheworld's
mysteries, from working out how elements are formed within stars to discovering
how our genes replicate. On the way they have discovered thousands of new
methods of convening one sub.stance illlo anOl:her. and have made miJHons of new
substances, many of which are of gre:it economic and medical benefit to the human
race (seefigurel.2).
Figure 1.2 Sameexamplesofthel'Cllnomic,

ll\l'dic.ilandagricu!tur.il benefit1ofchemi'itry
Classifying matter - elements, compounds and

mixtures
Chemists classify maner into one of three rntegories.
Elements contain just one son of atom. Alth01Jgh the atoms of a particular element
may differ slightly in mass (see section 2.3). they all have identical chemical
reactions . Examples of elements include hydrogen gas. copper mernl and diamond
ciysrnls (whicha..,-catbon).
Comounds are made up from the atoms of two or more different elements,
bonded together chemically. The ratio of elements within a particular compound is
fixed . and is given by its chemical formula (see page 7). The physical and chemical
properties of a compound are always different from those of the elements that
make it up . Examples of compounds include sodium chloride (containing sodium
and chlorine ions), water (containing hydrogen and oxygen atoms) and penicillin
(containinghydrogen,carbon,nitrogen,oxygenandsulfuratoms).
Chemical formulae and moles I
Mixtures consist of more than one compound or element. mixed but not chemi-
cally combined . The components can be mixed in any proponion. and the proper-
ties of a mixture are often the sum of, or the average of, the propenies of the
individual components . Examples of mixtures include air. sea water and alloys
1.2 Intensive and extensive properties

The propenies of matter may be divided into two groups .
The c xte n.,;ivc propert ies depend on how much matter we are studying. Common
examples are mas.s and volume - a cupful of wa!er has Jes.s mas.s. and Jes.s volume,
than a swimming pool.
The Ol:her g roup are the inten..,;ive propertlc5 , which do nOI: depend on how
much matter we have. Examples include temperature. colour and density. A copper
coinandacopperjugcanbothhavethesameintensivepropetties. although the
jugwillbemanytimesheavier (and larger)thanthecoin.
lne chemical properties of a substance are al.so inte nsiYe . A small or a large Jump of
:sodium wiU =a in the same way with either a cupful or a jugful of water. ln each case ii
willfizz. giveoffste-amandhydrogengas.andproduceanalkalinesolutioninthewater.
The oil-drop experiment

A bowl is filled with clean water and some fine powder, suc h as pollen grains or
flour. is sprinkled over the su1fac e . A small drop of o il is placed on the surface
of the water. as shown in Figure 1.3. The oil spreads out. As it d oes so, it pushes
the powder back. so that there is an approximately circular area clear of powder.
We can measure the volume of one drop by counting how many drops it
takes to fill a micro measuring cylinder. (If we know the oil's density, an easier
method would be to find the mass of. say. 20 drops.) We can calculate the are-a
of the surface film by measuring its diameter. Assuming the volume of oil d oes
not change when the drop spreads out. we can thus find the thickness o f the film.
This cannot be smaller than the length of one oil molecule (though it may be
Figure 1 .3 The ml-drop experiment bigger, if the film is several molecules thick - there is no way of telling) . The
following are typical results:
volume of drop = I.Ox llf"4cml
diameter of oil film = 30cm
radius o f film = 15cm
areaoffilm = 1tr'
= 3.14x 152cm1
= 707cm'
volume = are-a xthickness
volume
so thickness =--;;:;;;-
=l.4 x 10-7 cm ( l.4x10- 9 m)

Distances this small are usually expressed in units of nanometres :
l nanometre (nm) = Ix lo-I' metres ( m)
So the film is 1.4nm thick . Oil molecules cannot be larger than this .
PHYSICAL CHEMISTRY
1.3 The sizes of atoms and molecules

Just as we believe that elements are composed of identical morns, so we also believe
that compounds are made up of many identical units. These units are the smallest
entities that still r<,1ain the chemical propenies of the compound. They a"' called
m o lccu!C'!l or ion s , depending on how the substance is bonded together (see Topics 3
and 4). Mo!C'CU!cs contain two or more atoms bound together. The atoms may be of
the same element (e.g. ozone. OJ, which conrnins three atoms of oxygen) or different
elements (e .g. water, H,O, which contains two atoms of hydrogen and one morn of
oxygen). Io n s are atoms. or groups of atoms, thm carry an electrirnl charge.
Molecules are extremely small - but how small? Sometimes. a simple
experiment. a shon calculation and a little thought can lead to quite an amazing
conclusion. The well-known oil-drop experiment is an =ample. It allows us to
obtain an order--of-magnimde estimate of the size o f a molecu le using evecyday
apparatus(seetheexperimentonpage3).
Because molecules are made up of atoms. this means th.~t atoms must be even
smaller than the oil molecule . We can measure the sizes of atoms by various
techniques . includi ng X-ray ccystallography. A carbon atom is found to have a
diameter of 0.15 nm . That means it takes 6 million carlxm 31oms touching one anOl:her
toreacha lengthofonly Imm!
Flgure1.4 Cokluredscanningtunnelling
electronmicrograpllofcarbonnarmtubes,
rnmpri!il'dofrolled1heet1ofcarbonatoo11
iridMdualatDm1are,;eena1raisedbump-;on
the1urt.Keofthetube1
Standard form
The numbers that chemists deal with can often be very large. or ve ry small . To
Fullyw r1tten-o ut
eq ulv; le nt make these more manageable. and to avoid having to write long lines of zeros
(with the accompanying danger of miscounting them). ,ve often express numbers in
6x1Cl' 600
7. 142x10'
A number in standard form consists of two pans, the first of which is a number
2x10_,, between land 10. and the second is the number JO raised to a positive or negative
3.8521x 10~ power. Some =amples , with their fully written-out equivalents. are given in Table I.I.
If the 10 is raised to a positive power, the superscript tells us how many digits to
the right the decimal point move s. As in the examples in Table I.L we often ne<'d
to wri!e extra zeros to allow this to take place. If the 10 is raised to a neg:11ive
p;:>wer. the superscript number tells us how many digits to the left the decimal poim
moves. Hen, again. we often need to write extra zeros. but this time to the left of the
original number.
Sign ificant figures

In mathematics, numbers are exact quantities . In contrast. the numbers used in
chemistry usually ..,.present physical quantities which a c hemist measures . The
accuracy of the measurement is shown by the number of significant figures to which
thequantityisquO(ed .
If we weigh a small coin on a digital kitchen scale, the machine may tell us that it
has a mass of 4 g. A one-<ledmal-place balance will show its mass as 3.Sg, whereas
on a two-decimal -place balance its mass will be shown as 3 .SOg . We should imerpret
thereadingonthekitchenscaleasmeaningthatthemas.softhe coinliesbetween
3 .S g and 4 .Sg . If it were just a little lighter than 3 .Sg , the scale would have to ld u s
that its mass was J g. If it were a li tt le heavier than 4.Sg, the read-0u t would have
been Sg. The one-decimal-place balance naITOWs the range. telHng us the mass of
the coin is between 3.4Sg and J .SS g . The two-decimal- place balance naITOWs it still
funher. tobetween3.495 g and3.S0S g .
In this way the number of significam figures (I. 2 or 3 in the above examples) tells
ustheaccuracywithwhichthequamityhasbeenmeasured.
The same is true of volumes . Us ing a l()()cml measuring cylinder, we can measure
a vo lume of 2Scml to an accuracy o f O.Scm1, so we would qu{){e the volume
as 2Scml . Using a pipene or burene , however, we can measure volumes to an
accuracy of 0.0Scm 3 and so ""' would qu{){e the same volume as 2S .Ocm3 (that is,
somewherebetween24.95cm 3 and2S .0Scn, 3 ) .
Most chemical balance:s and volumetric equipment will measure quantities to 3 or
4 significant figures. Allowing for the accumulation of errors when values are
calculated us ing se~'eral measured quamities. we tend to quOle values to 2 or 3
significant figures.
lntheexamplesinTable l.1.thenumber6x to"has I significantfigure , andthe
number7.142x1()7 h:is4significantfigures .
1.4 The masses of atoms and molecules

Being so small. a!oms are also very light . Their masses range from l X 10- '"'g to
lxlO- "g. ltisimpossibletoweighthemoutindhidually.bucwernnaccurately
measure their rela th"l' m a s sC'5 , that is. how heavy one atom is compared with another.
The most accurate way of doing this is by using a mas.s spectrometer (see section 2.5)
Orig inally. the atomic mas.ses of all the elements were compared with the mass of
an atom of hydrogen :
massofOflf"atomofE
mas.s of one atom of hydrogen
This is because hydrogen is the lightest element. so the relative atomic masses of all
other elemems are greater than I. which is convenient.
Because of the existence o f isolopes (see section 2.3). and the central importance
of carbon in the masses o f organic compounds, the modern definition uses the
iSOlopecarbon-12. "c. asthestandardofreference :
PHYSICAL CHEMISTRY
The difference between the two defi nitions is small. since a c:ubon-12 atom has
almost exactly 12 time.s the average mass of a hydrogen atom (the actual ratio is
11.91 : I). Rebtive atomic mass is g iven the symOOJ A,. Since it is the ratio of two
masses, it is a dimensionless quantity - it has no units. We shall be l<X>king at
iSOlopes. and rebtive iSOlopic mass, in more detail in Topic 2, where we investigate
thestrucru..,ofmoms .
The masses of a ton1s and sub-atomic panides (see Topic 2) are often expre.ssed in
atomic mass units. An ato m ic mas s unit (amu) is defined as 1/ 12 the mass of one
atomofcarlxm-12.lthasthevalueofl.66o6x l0-"4g.
Although we cannOI use a bboratory balance to weigh out individual moms. we
can use it co weigh out known ratios of morns of various elements, as long as we
know their relative atomic masses . For example, if we know that the relative 3tomic
masses of carbon and magnesium 3re 12.0 and 24 .0 respectively, we can be sure tha!
12.0 g of carbon \\-ill contain the same number of 3toms as 24.0g of magnesium. What
is more, 24.0 g (12 .0 x 2) of carbon will contain !wice the number of atoms as 24.0g of
magnesium. Indeed. we rnn be cenain that any mass of carbon will contain twice
!he number of atoms as the same mass of magnesium. since the mass of each carbon
atom is only half the mass of a magnesium atom .
Similarly. if we know that the relative atomic mass of helium is 4 .0 ( which is
one-third the relative atomic mass of carlxm). we can deduce that identirnl masses
of helium and carbon will always contain three times as many helium atoms as
1.5 The mole

Chemisisdealwith real. measured quantitiesofsubstances. Ratherthancounting
atoms individually. we prefer to count them in units tha! are easily measurable . The
gram is a conveniently sized unit of mass to use for weighing out maner (3 teaspoon
of sugar. for example. weighs 3bout Sg) . The chemist"s unit of amount. the mole>
(symbol nm!). is defined in terms of g rams:
One mo~ of an element is the amount that coo ta ins the same number of atoms as there
arein12.000gofcarbon-12.
Fig u re 1.5 O!\!'-tenthofamoleofeach

oftheelement1aluminium,1u~ur,bromine
andle..d
a Al2.7g b S3.2g(~mo1S.) c 8r8.0g(~moj8r,) d Pb20.7g

The mass of one mole of an element is called its m o la r m ass (symbol M). h is
numerically equal to its relative atomic mass , Ar bu t is given in grams per mole :
relativeatomicmassofcarlxm = 12.0
molar mass of carbon = 12.0gmol- '
relative atomic mass of magnesium = 24 .0

molar mass of magnesium = 24.0 g mol- '
It follows from the above definitiOfl thm there is a dear relationship between the
mass ( m) of a sample of an element and the number of moles (n) it contains :
amountf1nmoles) ~ ~
molar mass
-"'M- ""' {11
Worked example 1
Using the Ar values o ~ 16.0, Mg ~ 24.0, What is the amount (in moles) of carbon in 30g of carbon?
s ~ 32.0,calrnlatetheamountofsubstaflCe Answer
{inmoles)inl'dChofthefollowing Use the valueA,{carbon)~ 12.0towrite its molar ma11, and use equation (1) above
x1mples m = 30g and M = 12.0gmol- 1
1 24.0gofoxygen 30g
2 24 .0golsullur 12.0gmot
3 16.0golmagnesium
=2.Sm ol
As we saw on page S. the actual masses of atoms are very small. We would therefore
=peel the number of atoms in a mole of an element to be very large. This is indeed
the case. One mole of an element contains a staggering 6.022 x 1()23 atoms (six
hundred and two thousand two hundred million million million atoms). This value is
called the Avogadro consta nt , symbol l .
The approximate value of L = 6.0 x 1o'3 mor' is of!en adequa!e. and will be used
The relationship betv,een the number of moles in a sample of an element and the
number of atoms~ L x number of moles
a,
Worked example
CakulatetheamountolsubstaflCe(in How many h'jl'.lmgen atoms are there in 1.5 mol of h'jl'.lrogen atoms?
moles)in
Answer
1 asampleofuranium that contains Useequation{2),andthevalueofLgivenabove
1.0x 1011 atoms L~ 6.0 x 10" 3 mOl 1 and n = l.Smol
2 asampleoffluorinethatcoota im so N~6.0x 1a1 3mot- 1 x 1.smol
Sx 10" 1 atoms = 9.0x 1023
1.6 Atomic symbols and formulae

Each element has a unique ~"J'mbol. Symbols consisi: of either one or two letters . The
firsi: is always a rnpital lener and the secOfld, if presen!. is always a lower-ease lener.
This rule avoids confusions and ambiguities when the symbols are combined to make
the formulae of compounds. For =ample:
the symbol for hydrogen is H

the symbol for helium is He ( n{){ HE or hE)
the symbol forcobal! is Co (n{){ CO - this is the fonnula of caJbon monoxide.
which con!ains two atoms in its molecule, Ofle of carbon and one of oxygen).
PHYSICAL CHEMISTRY
Symbols are combined 10 make up the fonnulae of compounds. If more than ooe atom
of a pankular element is present. its symlx,I is folk,wed by a subscripl gMng the number
of atoms of that ele1nem contained in one formula unit of the compound . For example:
the formula of copper oxide is CuO (Ofle atom of copper combined with one atom
of oxygen)
the formula of water is H 10 (two atoms of hydrogen combined with one morn of
oxygen)
the formula of phosphoric(V) add is H3PO (thr= atoms of hydrogen combined
with one of phosphorus and four of oxygen).
Some1imes. especially when the compound consists of ions rather than molecules
(see Topic 4), g roups of atoms in a formula are kept together by the use of bmcke1s.
If more than one of a particular group is present. the dosing bmckec is followed by a
subscriptgivingthenurnberofgroupspresent. Thispmcticemakestheconnections
between similar comp;:>unds clearer. For =ample:
thefonnubdsodiumnitrnteisNaN03 (ooe,;ocl;umion. Na. combined \\ithonenitrate

ion. N03- . which consists done nitrogen aton1 combined \\ith thi= o:q'gen atoms)
the fonnula of calcium nitrnte is Ca(N0 3) 1 (one calcium ion. Ca', combined with two
nitrate ions).
NO{e that in calcium nitrate, the formula unit consists of one calcium. two nitrogens
and six oxygens. but it is n{){ \\Tim,n as CaN10 6 . This fonnula would not make clear
the connection between Ca(N0 3) 1 and NaNOi . Both compounds are nitrates. and
bcxh undergo similar reactions of the nitrate ions .
The formulae of many ionic compounds can be predicted if the valencies of the
ions are known . (The valency of an ion is the electrical charge on the ion .) Similarly.
the fonnulae of se,..,ml of the simpler covalent (molecular) compounds can be
predicted if the covalencies of the constituent atoms are known . (lbe covalency of
an atom is the number of covalent bonds that the atom can form with adjacent atoms
in a molecule .) Lists of covalendes and ionic valencies, and =amples of how to use
them.are given on pages49and79.
Worked example
How many atoms of e;ich element are pre'il'<ll in one formula unit of each of the following
compounds?
Answer
a Thesubscriptaftertheclosingbracketmu!tipliesallthecontentsolthebfadetbythree
TherearethereforethreeOH(hydroxKle)groops,&Khcontainingoneoxygenandone
How many atorm in total are present in h'jl}rogen atom, making a total of three oxygen atoms and three h'jl}rogen atoms,
ooeformulaunitofe;ichofthefollowing togetherwithonealuminiumatom
compounds? b Here thefe are two ammonium groups, e;ich containir,g one nitrogen atom and lour
h'jl}rogenatoms.andonesulfategroup.conta iningonerulfuratomandlouroxygen
1 NH 4NOi atoms.lntotal,the..efore,thereare:
2 Na1Cr.P 7 two nitrogen atoms
3 KC((SO.i}., eighth~rogenatoms
4 C6H1106 onesulfuratom
5 NaiFe{C10.J1 fouroxygenatoms
1.7 Moles and compounds

Relative molecular mass and relative formula mass
Just as we can weigh out a mole of carbon (12.0g) . so we can weig h out a mole
of a compound such as ethanol (alcohol). We first need to calculate its rclatiYe
m oil..'<.- ula r m ass. M .
To calculate the relative molecular mass (M,) of a compound, we add cogether
the relative a!omic masses (A,) of all the elements present in one molecule o f
the compound (remembering to multiply the A, values by the correct number if
more than one atom of a panicular element is present). So for ethanol, C1H 60.
M, = 2A.(C) + 6A,(H) + A.(O)

= 2x 12.0 + 6x 1.0 + 16.0
= 46.o
Just as with relative atomic mas.s, values of rebtive molecular mas.s are ratios of
masses. and have no units. The molar mass of ethanol is 46.0gmol ' .
For ionic and giant covalent compounds (see Topic 4) , we cannot. strictly, refer
to their relative molecular masses , as they do nOI consist of individual molecules .
For these compounds. we add together the relative atomic masses o f all the
elements present in the simplest (empirical) formula . The result is called the relative
formula mass. but is g iven the same symbol as relative molecular mass. Mr Just as
with molecules, the mass o f one formula unit is called the molar mass , symbol M .
For example. the relative formula mass of sodium chloride, NaCl. is calculated as
M, = A.(Na) + A.(C])
= 23.0 + 35.S
= 58.S
The molar mass of sodium chloride is S8.Sgmol 1.
We can apply equation (I) (page 7) to compounds as well as to elements. Once the
molar mass has been calculated. we can relate the mass o f a sample of a compound
tothenumberofmolesitcontains .
Flgure 1.6 One-tenthofamoleof

eachofthernmpoorrliwater.
potas1ium didiromate(Vl) (K1Cr,o,) and
rnppl'r\ll)'i<Jlfate-5-wate<(C11S0, SH,O)
a H,01 .Sg b K,cr,0,29. 4 g c: CuS04 5H,025.0g
Worked example 1
Calculate the relative molecular mass of g lucose, C 6H1, 0 6
Answer
M,~ 6A~C) + 12A,(H) + 6A,(0)
~ 72.0 + 12.0 + 96.0

=180.0
PHYSICAL CHEMISTRY
Worked example 2
How many moles are there in 609 of glucose?
1 Caku\atethe relativelormu\amassof Answer
e<KhofthefoOowingrnmpourKls.(Use Convert the relative molecular mass ulrulated in Worked example 1 to the molar mass, M,
thelistofA,vallJ.l>S inthedatasectKlll andusetheformu!ainequation(l)
on the CD.}
a irofl{ll)sulfate,H!SO, m = 60g
b calciumhydrngencarbonate, M = 180gmol- 1
Ca(HC01h 609
c ethanokilCid,CiH,Oi n = 1sogmo1-
d ammonium sulfate, (NH,)iSO,
e thecompk!xwiththelormula =0.nmol
Na iFe(CiO,h
2 How many moles of subst.-mce are
thell'ineochofthelollowingsamples?
a 20gofmagnesiumoxide,Mg0
A mole of what?
b 40gofmethane,CH, When dealing with compounds. we need to define dearly what the word 'mole'
c 609ofcalciumcarbonate,CaC01 refers to. A mole of water contains 6 x !()23 molecules of H20. But because each
d 80gofcydopropene,C1H, molecule contains two hydrogen atoms, a mole of H,O molecules will contain two
e 100gofo;odiumdichromate{VJ), moles of hydrogen atoms. that is. 12 x 1o'1 hydrogen atoms. Likewi.se. a mole of
sulfuric acid. H,.S0 4, will contain two moles of hydrogen atoms, one mole of sulfur
l Whatisthem,mofeac:holthe atoms and four moles of oxygen atoms. A mole of calcium chloride. CaCl 2. contains
following samples? twice the number of chloride ions as does a mole of sodium chloride, NaCl.
a 1.Smdesof~msiJfate,MgSO,
Sometimes this also applies to elements. The phrase "one mole of chlorine" is
b 0.333 mole of aluminium dilorkll',
ambiguous. One mole of chlorine molecules contains 6 x 1o'l Cl, units, but it
AICh
contains 12 x 1023 chlorine atoms (2mol of Cl).
1.8 Empirical formulae and molecular

formulae
The empirical formula is the simpJest lomlula that shows the ll!!ative number of atoms of
eacheleme<1tpll!sentinacompound
lf we know the pen::entage composition by mass o f a compound, or the masses of
the various elements thm make it up, we can work out the ratios of atoms.
The steps in the calculation are as follows.
I Divide the percentage (or mass) of each clement by the element"s relative atomic
2 Divideeachofthefiguresobmined instep I bythesmallestofthosefigures

} If the results of the calculations do nOI: approximate to whole numbers. multiply
them all by 2 to obtain whole numbers. (In rare cases we might have to multiply by
}or4toobrninwholenumbers.)
Worked example
Caku!ate the empirical formula of an oxide of iron that conta ins 70% Fe by m;m
Calcu!a tetheempiric.alf0<mulaoleac:hol Answer

the fo llowing compounds. Theoxidecontainsironandoxygenonly,sotheperrentageoloxygenis100
Followingthe:.tepsabove
1 asulfideofrnppercootain ing:0.97gof
copper arid 1.00golsulfur 1 H':~ = 1.25 0:~ = 1.875
2 ahydrocatbonrnnta ining81.8%
1 875
carbonand18.2%hydrogen 2 H':~ ~ 1.00 0: = 1.SO
3 ami~oxideofironandcakium 1.25 1.25
whichcootaim51.9%ironand18.5% 3 Multiplybothnumbersby2:H' = 2,0 = 3.
caki um by mass (the rest being oxyge<i) Thereforetheempiricalformulais Fe 20 3
10
The molecular formub is either the same as, or a simple multiple of. the empirical
formula . For example. the molecule of hydrogen peroxide contains two hydrogen
atoms and two oxygen atoms. Its molecular formula is H,O,. but its empirical
The mo lecula r fo rmulatellsustheactualnumberofatom1of&Khelementpresentin a

moleculeofthecompoor,d
1.9 Equations
Mass is conserved
A chemical equation represents wha! happens during a chemirnl reaction. A key
featur,, of chemical reactions is thm they proceed with no measurable change in mass
m all. Many obvious events can often be see11 taking place - the evolution of heat.
flashesoflight.cha ngesofcolour. noiseandevolutionofgases . But despite these
sometimes drammic signs that a reaction is happening, the sum of the masses o f all
the various products is always found to be equal to the sum of the masses of the
This was one of the first quantitative laws of chemistry, and is known as the Lllw o f
Con sen ' ~tio n o f Mass . It can be illustrated simply but effectively by the following
experiment.
The conservation of mass

Asmallte.s1rubehasalengthofcottonthreadtied round its neck. and is half filled
with lead(]]) nitrate solution . It is carefully lowered into a conical flask containing
potassium iodide solution, taking care not to spill its contents . A bung is placed
intheneckoftheconicalflask,sothatthecottonthreadistrappedbyitsside, as
shown in Figure 1.7. The whole apparatus is then weighed .
The conical flask is now shaken vigorously to mix the contents. A reaction
takes place. and the bright yellow solid lead(IO iodide is formed . On re-weighing
theconicalflaskwithitscontents,themassisfoundtobeidenticaltothe
Flg ure 1.7 During theformabonollead(II)

kxlide,mas1isrnf1Sl'IVed
&:: : : :'"''
mHsb<!for :246.7469
Balanced equations
potassium
:::,1~~~n
ma,safter: 246. 7469
y llow precipitat e
of le ad(II) iodide
The reason why the mass does not change during a chemical reaction is because no
atoms are ever created or destroyed . The number of atoms of each element is the
sameattheendasatthebeginning. Allthat hashappenedisthat theyhavechanged
11
PHYSICAL CHEMISTRY
their chemical environment . ln the example in the experiment above. the change can
be represented in w o rds as:
lead(!]) nitrate + potassium iodide ----) solid lead(]]) + po1assium nitrate

solutio n solution iodide solution
Flgure1.8 Theformatklnoftead(ll)iod ide
There are several steps we muse carry out to conven this won! equation into a
balanced ch e m ica l equatio n .
I Work out and write down the fomrnla of each of the compounds in tum. and
describeitsphysirnlstate usingthecorrectoneofthefollowingfourstatc
~"'}=bols :
(g) = gas (l) = liquid (s) = solid (aq) = aqueous solution (dissolved in water)
lead(]]) nitrate solutiOfl is Pb(NOl):,(aq)

pornssiumiodide solutionisKl(aq)
solid lead(]]) iodide is Pbl,(s)
pornssiurnnitrate solutionisKNO/ aq)
The equation now becomes:
2 The next step is to "balance' U>e" equation. That is, we mmt ensure that we have the
same nurnbe,- of atoms of e-:ich element on the right -hand side as on the left-hand
side .
a Looking at the equation in step I above , we notice that there are two iodine
atoms on the right. in Pbl,. buc only one on the left. in Kl. Also. there are
two nitrate groups on the left. in Pb(NO_i),. but o nly one o n the right. in KN0 3.
b We rnn balance the iodine atoms by having two formula units of Kl on the left.
that is 2KI . (Note that we rnnnot chang e the formula to Kl, - that would not
co1Tectly represent potassium iodide, which always contains equal numbers of
potassium and iodide ions.)
C We can balance the nitrates by having !WO formula units of KN0 3 on the right. that
is 2KN01. This also balances up the potas.sium acorns. which. although originally
the rome on both s ides, became unbalanced when we changed Kl to 2Kl in step b .
The fully balanced equation is now:
1t is clear that we have neither 105! nor gained any atoms. but that they have
swapped partners - the iodine was origi nally combined with potas.sium. but has
ended up being combined with lead ; the nitrate groups have changed their parmer
fromleadtopotas.sium.
12
Worked example
Writethebalancedchemicalequationlorthefollowing redclion-
1 Copythefollowingequatioosand
zincmetal + hydrochlorica.cid----tzincchloridesolutkln + hydrogengas
balance them
Hi(g} + D.!{g)----tHiO(I) Answer
b Ji(s) + Cli(g)----t!CIJ{s) Followingthe:.tepsgivenabove:
c NaOH(aq} t A~OHh{s}----t
1 ZincmetalisZn(s).
NaAIOii!Q) + HiO(I)
HydrochloricacidisHCl(aq)
d H1S{g) + S0i(g)----tS{s) + H10(0
e NHJ(g} + Oi(g)----tNi(g) + HiO{I) Zincchlorideso!utionisZnCli(aq)
Hydrogen gas is Hi(g) (hydrogen, like many non-meta llic eJements, exists in mo~ules
2 Writebalancedsymbolequationsfor
made up of two atoms)
thefollowingr&IC!ion1.
The equatkln now becomes
ao magnesium carbonate----> magnesium
Zn(s) + HCl(aq) ----t Z11Cl1(aq) + H1{9)
oxide + carbondioxide
b lead + silvernitratesoluhon----tlead 2 There are two hydrogen atoms and two chlorine atoms on the right, but only ooe of
eacholtheseontheleft
nitrateso!utioo + si!ver
c sodiumoxkle + wate<----tsodium b We can balance both of them by just one change having two lormu!a units of HCI on
the left
hydroxide solution
d iron{ll)chloride + chlorine(Cb)----> Thefullyba!ancedequationisnow
iron{lll)chlorkle Zn{5)+2HChq}----tZnCl1(aq) + H1(g}
e iroo(lll)sulfate t sod iumhydroxide----t
iron{lll}hydroxide + sodiumsulfate
1.10 Using the mole in mass

calculations
We are now in a position to look 31 how the masses of the individual substances in
a chemical equmion are related. As an example, take the reaction between ma,ble
chips (calcium carbonate) and hydrochloric add:
CaCO,(s) + 2HCl{aq)---t CaC\i{aq) + H 10(1) + C0 1(g)
When this reaction is carried out in an open conical flask on a top-pan balance. the
m:issisob.servedtodecrease. (Notethatthisisnotduetothedestructionofm:itter -
as ,vas mentioned on page 11. the overall number of a1on1s does not change during
a chemical reaction. Rather, ic isduetothefactthmthegaseouscarbondioxide
produced escapes into the air.) We can use the knowledge gained in this topic to
calculate the answer IO the following question:
By how much would the mass decrease if SOg of marble chips were completely
reacted with anexcessofhydrochloricadd?
Weusethefollowingsteps :
1 We can use equation (I ) (page 7) to calculate the number of moles of calcium

carbona!einS,Ogofmarblechips:
M,(CaCOl) = 40.1 + 12.0 + 3X 16.0 = 100.l

so 111 = 100. lgmol'
II =
------'-'--
100.1 gmol- '
= o.somol ofcaco 3
2 From the balanced equalion above. we,..,., that one mole of calcium carbonate
produces one mole of carbon dioxide. Therefore the number of moles of carbon
dioxide produced is the same as the number of moles of calcium carbonate we
stan~'"Cl with. namely 0.50mol of carbon d ioxide.
} Lastly. we can use a rearranged form of equation (I) to calculate what mass of
carbon dioxide this corresponds to.
13
PHYSICAL CHEMISTRY
M,(CO,) = 12.0 + 2
X 16.0 = 44.0
so M = 44.0gmor'
also n = 0.50mol
m = 0.50mol x 44.0gmol- '
= 22.0g
The loss in mass (due to the rnrbon dioxide being evolved) is 22 .0g.
The three steps can be summarised as shown in Figure 1.9.
Flgure 1.9Findingthemassofaproduct
fromthemasso/n,actant,orvice=!i.l I ma .. offir.>treactantorproduct I
ratio from balanced equation
molesofsecondreactantorproduct
I ma"ofw,condreactantorproduct I
Worked example
The highly exothemiic thermit rea ction (5e1:! Figure 1.10) is used to weld together the st~
ra ilsofra ilwaytrads.ltinvo!vesthered uctionofiroo(lll)oxidetoironbyalum inium.
2Al(s)+Fei01(s}-.Al10i(s) + 2Fe(s)
Fi gure 1.10 Theth1.>rmitproc:e,;sfSusedto

weldtogethe1the1teelrall'iofraiM'ayt1ack';
UsethechartinFigure 1.9tocakulatewhatmassofaluminiumisneededtoreact
rnmpletelywith10.0gofiron(lll)oxide
14
Answer
1 M,(Fei01) 5 2x5S.8 + 3x 16.0 111.6 + 48.0~ 1S9.6
so M = 159.6gmoJ-1
numbefofmolesofiron(lll)oxide(n) = S
1 Whatmassofsi!vefwillbeprecipjtated
whenS.OgofcopperarerNctedwith 10.0
anexcessofsi!vefnitratesollllioo? ~ 159.6
~0.0627m~
Cu(s) + 2AgNOJ\aq)
2 From the balanced equation, one mole of iroo(III) oxide reacts with two moles of
----tCu{NO,}.,(aq) + 2Ag(s)
aluminium.therefore
2 What mass of ammonia will be formed number of moles of aluminium (n} = 0.0627 x 2 ~ 0.125mol
when SO.Ogofnitrogenarepas.sed J A,(Al) = 27.0 so M~27.0gmoJ- 1
throughtheHabefprocess?{Assume massofaluminium = nxM
100%conversion.) ~0.125mol x27.0gmoJ-1
Ni(g} + 3Hi(g}----t2NH1(g) ~ 3.38g
1.11 Moles of gases

The nx,lar masses of most compounds are different. The molar volumes of nX>Sl
solid and liquid compounds are also different. But the molar volumes of gases (when
measured at the same temperature and pressure) are all the same. This strange
coincidence results from the fact that most of a gas is in fact empty space - the
molecules take up less than a thousandth of its volume at normal temperatures (see
section 4.IJ). The volume of the molecules is negligible compared with the tO!al volume,
and so any variation in their indi,idual size will not affect the overall volume. At
room temperature (2SC, 298K) and normal pressure (latm. I.OJ x \~Pa):
th e molar voluml'of anygas = 24.0 dmj mo l '
Sowecansaythat:
amountofgas(inmoll.'S) = = = u : ' )
n~__!-'._
24.0
Of volume of gas in dml ~ molar volume x moles of gas
v~24.0 x n
Worked example
What YDlume of h'jdrogen {measured at room temperature and pressure) wi ll be produced
1 WhatYOlumeofcarboodioxide when7.0gofironarereactedwithanexcessofsulfurkacid?
(measured at room temperature and Answer
pressure)will be produced when S.Og Theequationforthereactionisasfollows
ofc.alciumcarbooatearedecomposed fi.,(s) + HiS0 4(aq}----tFeS0 4(aq) + Hi(g)
byheatingiKcOfdingtothefollowing
equatioo? 1 A,(Fe) = 55.8 so M = 55.8gmoJ-1
CaC01 ----tCaO+COi amount {in moles) of iron z ~
2 Su1furdioxideand hydrogensullide _ ---2:2..2...._
gasesredcliKcordingtotheequatkln - ss.sgmor'
2HiS + S0i----t2Hi0 + 3S = 0.125mol
What YDlume of sulfur dioxide will 2 From the balanced equation, one mole of iron produ{es one mole of hydrogen molecules,
beneededtoredclcomplete!y therefore
with 100cm1 ofhydroge<11ullide numberofmoleso1Hi = 0.1 25 mol
(both vciumes measured at room 3 vciume of Hi {in dm3l = molar volume x moles ol Hi
temperature and pressure), and what ~24.0dm1 mcl- 1 x0.125mcl
massofsullurwillbeformed? = 3.0 dm1
15
PHYSICAL CHEMISTRY
1.12 Moles and concentrations

Many chemirnl reactions are carried 01Jt in solu tion . Often it is convenient to dissolve
a reaaant in a solvent in advance, and to use portions as and when needed . A
common example of this is the dilute sulfuric add you find on the shelves in a
bboracory. This has been made up in bulk. at a certain concentration. Solutions are
mos! e:isily measured out by volume. using measuring cylinders, pipettes or bun,nes.
Suppose we need a certain amoum of sulfuric add (that is, a certain number of
moles) for a particular experiment. If we know how many moles of sulfuric add each
lcm1 of solution contains, we can obmin the required number of mole.s by me:isuring
out the correct volume. For example, if our sulfuric add conrnins 0.001 mol of H,.S04
per I cm3, and we need O.OOSmoL we would measur,, out ScmJ of solution .
ln chemistry. the cona,-ntrntions of solutions ar,, nonnally stated in units of molC'S
pl'r c ubic dt,oeimc tre (= moles per litre). The customary abbreviation is moldm- 3.
Occasionallytheolder, andevenshorter, abbreviation !',! is used.
If I dm 3 of a solution coma ins l.Omol of solute, the solution's concentration is
1.0moldm- 3 (or I.OM. veibally described as a one molar solution").
lf more moles are dissolved in the same volume of solution, the solution is a more
concemrated one. Likewise, if the same number of moles is dissolved in a smaller
volume of solution. the solution is also more concentrated. For example. we can
produce a 2.0moldm- 3 solution ( 2.0M. "two molar') by:
either dissolving 2 mol of solute in l dm3 of solution

or dissohing I mol of solute in O.Sdm3 of solution.
amount(inmoie1)
volumeolsolutK)f)(indm')
c~v
or amount (in mo~)3 coocentration x volume {in dm3)
Unlike the mass of a solid, or the volurne d a gas. which are extensive properties of
a.substance(seepage3) ,theconcencrationofasolutionisanintensivepropeity. h
does nOl depend on how much of the solution we have. Properties that depend on the
concentration of a solution ar,, also intensive . For example, the rate of reaction bet,veen
sulfuric add and magnesium ribbon. the colour of aqueous porns.sium manganace(VI[).
the sourness of vinegar and the density of a sugar solution 00 nOl depend on how
much solution we have. bu t only on how much solute is dis.solved in a given volume.
F1g u re1.11 Colou r is relatedto

rnrn:entratkm,anln temrl'epropertythatdoes
ootdependon howmuchmhltionthereis
16
Worked example 1
200cmlofa11Jgarsolutioncontains0.40mololsugar.Whotisthecon=trationofthesolution?
Answer
Usethefirstequationinthe panel on page 16:
Remembef, 1000cm1 ~ 1.0dm1

so 2oocmi ~ o.2odmi
0.40mol
( = ~
3 2.0moldm--l
1 Whatarethernrxentrationsofsolute Worked example 2

inthelollowing'iOlutions?
How many grams of salt, NaCl, need to be dissolved in 0.50dm 3 of solution to make a
2.0mololethanolin7S0cmlof
0.20moldm...i'iOlution?
solution
b 5.3gofsodiumcarbooate,Na1COi, Answer
in2.0dm1 ofsolution Usethesecondequationinthepanelonpage 16
t 40gofethanoicacid, C1H.t01,in nEcxV c~0.20moldm- J
800cmlofsolution
n z 0.20moldm- l x O.Sdml V z O.S0dm1
2 Howffiilnymolesofsoluteareinthe
= 0.10molofNaCI
lollowing'iOlutions?
a O.SOdmlofa 1.Smoldm- 1 'iOlut ion Now use equation (1) (page 7) to convert moles into mass
ofrnlluricacid
b 22cml of a 2.0moldm-1 'iOlution of
-s M,(Ni!C~ : ;~;~~rs S8.SwMd8.Sgmot"1
sod ium hydroxide m ~ 0 .10mol xS8.Sgmol- 1
t 50cm1 ofasolutionrnnta ining20g
=5.85gofsalt ,Ni!CI
ofpotassiumh'iUrogem.arbooate,
KHCOi,perdm1
We sh3ll come across the concentrations of solutions 3gain in Topic 6 . where we look
31thetechniqueoftitrntion.
1.13 Calculations using a combination

of methods
At the he3n of mos! chemistry rnkulations is the babnced chemirnl equmion. This
showsustherntiosinwhichthereae13ntsre3ctto g ivetheproducts.andtherntios
in which the products are formed . This is c3Jled the stoich iome try of the reaaion.
MOISI c3lculations involving re3CTions c3n be broken down into a se1 of three steps (see
Figure 1.12), simibr to those described for m3ss rnkubtions on page 14.
Flgure1.12 Cai::ulatiominYOMngthe
massofsolidA.orvolume ofga,A,
stoichiometryofareactkm orvolume(orconcentration)ofsolutionconta iningA
molesofreactantorproductA
ratiofrombalancedi,quation
mole, ofreactantorproductB
massof,olidB,orvolume ofg asB ,

orvolume(orconcentrtion)ofsolutioncontainingB
17
PHYSICAL CHEMISTRY
Use Figure 1.12 and the Ar values in the data section on the CO to ,mswer the following
questioos
1 What volume of hydrogen gas will begiveo ofl\Mlen 2.3g of sodium metal react
1\ilhwater?
2 The equatioo for the rnm~ete combustion of methane, CH,1, in oxygen is

CH4(g) -t 201(Q)---->CC}.,(g) + 2H10(g}
Calculatethevolurneofoxygeoneededtobum4.0gofmethane
3 What volume of O.SOmoldm- l 5Utluric add, H1S04, is needed to react exact~ with
5.0gofmagr.esium,ar.dwhatvolumeofhydrogenwillbeevolved?
Mg(s) + H1S0 4{aq)----> MgS0 4(aq) t Hz(g)
4 What mass of sulfur will be pieci~tated when an excess of hyd rochloric ilCid is
added to 100cm1 of 0.20moldm- 1 sodium thiosulfate sclutioo?
5 Whatwouldbethecoocentrationofthehydrochlork<Kkiproduc:edifallthe
hydrogenchloridegasfmmthereactioobetweenSOgofpuresulfurkilddarKlan
excess of sodium chloride was collected in watl'f, and the solution made up to a
YOlumeof400cmlwilhwater?
NaQs) + H1S0 40)---+ NaHS04(1) t HCl(g)
Atoms and mo lec:u les aresmallarKll~ht - about 1 x 1o-1lmin Chemkal equations reflect this - when balanced, they cootain
1ize,<1rKl <1bout 1 x 10- 11 g inmas1 the same numbe!'i of atoms of &Kh element oo their left-harKl
Relativeatomicmass and re lativemolecula r mass are andr~ht-handsides
definedintemisofthemassofanatomofcarboo-12 Thelo llm\ingequatioosallowustouk:ulatethenumberof
One mole is the amount of rubstance that has the same molespreseotinasample
number of particles (<1toms, molecules, etc) as there are atoms
in 12.000g ofcarbon-12 . amount {in moles) = mc:;:ss ' n= f
The relative ~ecular mass, M, of a compound is found
by summing the relative atomic masses, A, of all the atoms amount {in moles) volume ~!'3; ~n elm') ' n= 2i:o"
presellt
The emp irical formu la of a compourid is the simplest formula amount = conceotrationof x volume
that shows the relative number of atoms of each element (in moles) solutioo (in moldm---3) {in dm3)
preselllinthecompound ' n ~ exV
The molecularformula tellsustheactualnumberofatomsof
eache~ntpresentinamolec:uleolthecompound.
~;:ior:~) ~~::r{~~:i~~m---3) x volu~! cm')
Chemicalreactionstakep!acewithnochangeinmass.andno n~c x ~
changeinthetotalnumberofatomspresent. 1000
18
Examination practice questions
may....,
Please<;e('thedataSKtionoftheCOforanyA,valuesyou 2 Washingsodaishydratedsodiumcart>onate,
Na,co,.xtt,o.
Astudentwishedtodeterminethevalueofxbycarrying
1 Zincisanessentialtraceelementwhichisneces5aryforthe
outatitration,withthefolloNingresults.
healthy growth of animals and plants. Zinc deficifficy in
5.13g of washing soda crystals were dissolved in water
humanscanbeeasifytreatedbyusingzinc::saltsasdietary
and the solution was made up to 2SOcml in a standard
supplements.
volumetric flask .
a Onesalt'Mlichisusedasadietarysupplementisa
25.0cm 1 of this solution reacted e10ctty with 35.Bcml of
hydrated zinc sulfate, ZnSO..>:HiC), which is a colourless
O. IOOmoldm-1 hydrochloric add and carbon dioxide was
crystajline solid. Crystals of zinc sulfate may be prepared
produced.
ina sch,oojorcollegelaboratorybyreactin,gdilute
a i WriteabalancedequationfO!'thereactionbetween
sulfuric acid with a suitable compound of zinc.
Na,COiandHCI
Give the formulae of two simple compounds of zinc that
ii Calculatetheamount.inmoles,ofHClinthe35.8cm 1
could each react with dilute sulfuricacidtoproduc:ezinc
ofsolutionusedinthetitration
sulf_ate. . (2)
iii Use your answers to i and ii to calculate the amount,
b A simple experiment to determine the value of x in the
in moles, of Na 2COi in the 25.0cm 1 of solution used
formula ZnS0,.xH 20 is to heat it carefully to drive off the
in the titration
water.
iv Useyouranswerto iii tocalculatetheamount,in
ZnSO,.xHp(s)--+ ZnSO.,.(s) + xH 20(g)
moles, of Na 1C01 in the 250cm1 of solution in the
Astudentplacedasampleofthehydratedzincsulfatein
standard volumetric flask .
a weighed boiling tube and reweighed it . He then heated
v Hence calculate the mass of Na 2C01 present in 5.13g
the tube for a short time, cooled ,t and reweighed it
of washing soda crystals. [6]
when cool. This process was repea ted four time5. The
b Useyourcalrulationsin , todeterminethevalueofxin
final A?Sults are stio...m below
Na,co,.xttp. 121
(CambridgelnternarionalAS &A l-1Chemistry9701,
Paper 23 Q2June2012}
3 a Acompounda:r,tanngl'nilg"leSii.xn,5iliconandOllygefl
ispresentrl rod types in ltaf. Asampleofthiscompound
~S.27gwasfOl.rldtohaYethefobNing
i Whywastheboiling1ubeheated,c~and
compaWOnbymass; Mg, 1.82g; Si, 1.05g; 0, 2.40g.
reweighedfourtirnes7
Calculate the empirical formula of the compound. Show
ii Calculate the amount, in moles, of the anhydrous salt
yourwori:ing. [21
produced.
b Pharmacists sell tablets containing magnesium hydfOllide,
iii Calculatetheamourit, in moles,ofw.iterdrivenoff
Mg(OH)i, to combat indigestion. A student carried
by heating .
out an investigation to find the percentage by ma55 of
iv Useyourresultsto ii aod iii tocalculatethevalueofx
Mg(OH)iinanindigestiontablet. Thestudentreactedthe
inZnSO .xHp. [7)
tabletwithdilutehydrochloricacid.
c For many people. an in~ke of approximate ly 1 s mg per
dayofzmcwillbesuff,c,enttopreventdeliciencies. Mg{OHn(s) + 2HCl(aq}-+ M9Cli(aq)+ 2H:O(I)
Zinc ethanoate crystals, (CH 1C0 2)iZn.2H 20, may be used
Thestudentfoundthat32.00cmlof0.500moldm-l
1nth1sway.
HCI was needed to react with the Mg(OH)i in a 500mg
i Whatmassofpurecrystallinezincethanoate
tablet.[19= 1000mg].
(M,=219.4)willneedtobetakentoobtainadose
i Calculatetheamount.inmol.ofHClused. [1]
of 15 mgofzinc7
ii Determine the amount. in mol, of Mg(OH)i present in
ii lfthisdoseistakeninsolutionas5an1 ofaqueous
the tablet [1]
iinc ethanoate, what would be the concentration of
iii Determine the pel'Centage by ma55 of Mg(OH)1 present
thesolutionused7Giveyouranswerinmoldm- 1. [4}
mthetablet. [3]
(Cambridge /nrernariona/ AS & A l ~ Otemilitry9701,
(OCR Chemistry A UnirF321 Q2(pdrt)May2011}
Paper 21 01 No..ember 2012}
19
AS Level
Physical chemistry
2 The structure of the atom

In this topic we introduce the three
sub-atomic particles - the electron,
Learning outcomes
theprotonandtheneutron. We By theeodofthistopicyou shouldbeableto
look at their properties, and how 1.3a) anatysemassspectra in termsofisotopicabundances(part,see al soTopic29),
they a re arranged inside the atom. 1.3b) cakukite the relative atomic mass of an element gtven t he relative abur.dances of
We explain that some elements form its isotopes,oritsmasss.pectrum
isotopes, and desaibe how their relative 2.1a) identify anddescribeprotons,neutronsand electronsint&msof thelrrelat tve
abundancescanbemeasuredusing cha rges ar.drela tivemasses
themass spectrometer.Weoutline 2.1b) deduce thebehavio urof beamsofprotoos,neut romar.defectrons inelectricfields
thetypesofenergyassociated 2.1c) describethedistributi ooofmass andchargewithin an atom
w iththepartic/esinchemistry. 2.1d) deduce t henumbersofprotons,neutrons andelectronspresentinbothatoms ar.d
Against this background, we look ioos givenprotonan dnucleonn umbers andch arge
athow thee/ectrons arearran ged 2.2a) describethecontributionof protons and neutronstoatomicnudeiinte rmsof
aroundthe nuc/eusandhowthis protonnumberand nucleonn umber
a"angement explains the positions 2.2b) distinguishbetween isotopesonthe basisof diff&entnumbersolneut rons pres.ent
ofelements w ithinthePeriodic 2.2c) recog nise arid use the symboli sm ~A fo r isotopes, where is the nucleon number
Tab/e,theirionisationenergies and 1 is theproton number
andthesizesoftheir atoms. 2.3a) describethenumber and relat tve efll'fgiesofthes. p andd0ffiitalsforthe
priricipa l quantumnumbers 1,2and3andalsothe4s and4porbitals
2.3b) describe and sketchtheshapes of s ar.dporbitals
2.3c) statetheelectmnicconligurationof atomsandions giventheprotoonumber and
charge,usingtheconvention 11 2s1 2p6.etc
2.3d) explain andusethe t&mionisiltionenergy,explain the factors influencing the
iooisationenergiesofelemeots,andexplainthe t rer.dsinionisationenergies
aaossa Pl'riodanddown a Groupofthe Period ic Table{seealsoTopiclO)
2.3e) deduce t he electronicconfi gurationsof eleme nts fromSl/ccessive ion isation
energy data
2.3fl int&pretsuuessive ionisiltionene rgydata ofan element in tefmsoftheposition
of thatelementwithinthePeriodicTable
2.1 The discovery of the sub-atomic

particles
Our understanding o f atoms is ve ry muc h a nineteenth- and twentieth-century story.
Altho ugh the Greek philosopher Democritus was the first to coin the te rm "ato m"
(which is derived from the Greek word meaning cannor be cut'), in around 400 IICI!.
his ide a o f maner being composed of small panicles w as dismissed by Aristorle.
Because Aristorle"s reputation was so g reat . Democritus atomic idea was ig nored
for centuries. It was nor until 1808, when John Dalton published his Atomic Theory ,
that the ide a of atoms as being indivisible constitue nts of matter wa s revived . Da lton
suggested that all the ato ms of a g iven element were identical to eac h oiher. but
differed from the aton1s of every oiher element. His moms were the s mallest pans of
an element that could exist . They could nor be broken down or destroyed. and were
themselves without structure.
20
Thestructureoftheatom l
For most of the nineteenth centuiy the ide:i of atoms being indivisible fined in well
with chemists' ide:is of chemical reactions. and was readily accepted. Even today it
is believed that atoms are never destroyed during a chemical reaction , but merely
change their panners. However. in 1897 the physicist J.J . Thomson discovered the first
s ub-a tomic partic le , that is. a panicle smaller than an atom. lt was the electron .
Thomson found thac the electron was much lighter than the lightest atom. and had
aneg ativeelecllicalcharge. Whatis more.hefoundthatundertheconditionsofhis
experiment. acorns of different elements produced identical electron panicles. This
suggested that all atoms contain at least one sub-atomic component in common .
Sinceatomsareelectricallyneutralobjects, iftheycontainnegativelycharged
electronstheymustalsocontainpanicleswithapositivecharge. Animix>nam
experiment carried ouc in 1911 by Ernest Rutherford (a New Zealander). Hans Geiger
(a German) and Ernest Marsden (an Englishman) shov,ed that the !X)Sitive charge in the
atom is concentrated into an incredibly small nuc leus right in the middle of it. They
estimated tillu the diameter of the nucleus could na be g reater than 0.00001 time.s that
of the atom itself. Eventually. Rutherford was able to chip away from this nucleus small
!X)Sitively charged p<1nicles. He showed that these were also identical 10 each <Xher. no
maner which elen,ent they came from. This positive panicle is called the proton. It is
muchheavierthantheelectron.havingne:irlythemassofthehydrogenatom.
Flgure2.1 Eme-;tllulherford(fight)and
HansGl.'igerinthei1laboratoryatManctie1ter
UniversityinabootlW8.Theyare1eenwith
theinstrumentatklntheyusedtodetecta<id
rnunt-partkles.whic:haiethenucleiof
helium.1tom1
It was an<Xher 20 years before the la.st of the thr= sub-atomic panicles. the n e utron .
was discovered . Although its existence was first suspected in 1919. it was n<X until 1932
that James Chadwick eventually pinned it down . As its name suggests. the neutron is
electricaUyneutml.butitisrelativelyheavy.ha,ingaboutthesamemas.sasaprolon.
Scientist.shadthereforctochangctheearlierpictureoftheatom. In a sense the
picture had become mor.,- complicated. showing that atoms had an internal structun,-
and wen,- made up of <Xher. smaller panicles. But l<X>ked al in anaher way it had
become simpler - the 90 or so diffen,-nt cype.s of atoms that are needed to make up
the various elements had been n,-placed by just three sub-atomic panicles. It turns
out thac these. in differenc amounts. make up the atoms of all the different elements .
F1gure2.2Toepictureoflheatominthe
l
early twentieth century
m~<orn.o,om
oftheatomisoccupie d
by the electrons
21
PHYSICAL CHEMISTRY
2.2 The properties of the three

sub-atomic particles
Table 2.l lists some of the propenies of the three sub-atomic particles.
Table2.1 Thepropertiesofthesub-atamk:
partide1.Notethatthem..1sse5inthela1trrm
aregivenrelativetoTJ"themassofanatom eJectricalctlarge/rnulomb-; - 1.6x10- 1' +l.6x10-" 0
ofcarbon-12.Thesemas'>!.'5areoftl.'r1quoted dl arge{relative toth.it ofthe pratoo)
1elativetothema1softhepmtooi111tead,
9.11x101
:e~~~:~~m: ~;: =:~mk
lll'lllrooarebothl
rrm'>lg
rr1aHlam u(1ees.ectkm 1.4) S.48S xlo-'
1.673x10-" 1.67S x10"
Becauseoftheirrelativemassesandcha,ges,thethreepartidesbehavediffcrendyin
an electric field, as shown in Figure 2.3. Neutrons are undeflected, bein g electrica lly
neutral.Protonsareattractcdt0\\11rdsthencgativcpolc. and electrons cowards the
~ \! //~- positive pole. !f !heirinitialvelocitiesarethesame,elcctronsaredef\cctedtoa

grea!erextcntthanprotonsbecausetheyaremuchlightcr.
The picture of the atom assembled from these observations is as follows.
I \!/' Atoms are small, spherical structures with diameters ranging from l x 10-- >om
}x10- 10 m .
to
1 lhe panidcs th.~t contribu !e to the atom"s mass (protons and neutrons) arc contained
=!=
within a , ciy small central nucleus that has a diameter of abou ! l x 10- 1lm.
e lheelectronsoccupytheregion around the nucleus. Theyaretobefound in the space
in.side the atom hut outside the nucleus. which is almost the whole of the atom.
All the atoms of a panirular element contain the same number of proions. This also
i equalsthcnumberofelectronswithinthoseatoms.
be;imofpartide,s The atoms of all elements =cept hydrogen also contain neutrons. These are in the
Flgure2.3Thebehaviourofprotons. nucleus along with the protons. Almost the only effect they have o n the propenics
rieutrnnsandelectrominanelectri::field oftheatomistoincre:iseitsmass.
2.3 Isotopes
A! the same time as Rutherford and his !earn were finding out about the structure of
the nucleus. it was discovered that some elements contained atoms that have different
masses,bu t idcnticalchcmicalpropenics.
These atoms were given the name i!!OIOJX'S , since they occupy the same (iso)
place (lopos) in the Pcricxlic Table. The first isotopes to be discovered were those
o f the unstable radioactive clement thorium . (Thorium is clement number 90 in the
Pericxlic Table .) In 1913, hmvcvcr. Thomson ,;\,11S a ble to show that a sample of neon
obtained from liqu id air contained atoms with a relative atomic mass of 22 as well
as !hose with the usual relative a!omic mass of 20. These heavier neon acorns were
stable, unlike the thoriu m iSOl:opcs. Many Olhcr elements contain isotopes. some of
which are listed inTable2.2 .
Table2.2Therelativeabundanceof Mass relative to hydrogen

some isotopes
magnl.'5ium-24
magnl.'5ium-2S
The isotopesolanelementdifferintheir
magnl.'5ium- 26
compositklnin onlyonerespect - although
theyallcontainthesamenumbersol Mostofthcna!urallyoccurringiS01:opesarestable.but somc,Hkcthoscofuranium
electrons,mdprotons,theyhavedifferent and also many a nificially made ones. are u nstable and emit radiation. These are called
numbers of neutrons rndklactivtisotopes.
22
2.4 Extending atomic symbols to include

isotopes
For most chemical purposes. the atomic symbols imrcxluced in Topic I are 3dequ31e.
If, however, we wish to refer to a particular isowpe of an element. we need to specify
its mass numDCr, which is the number of prowru; and neutrons in the nucleus . \1k
write this as a superscript before the atomic symbol. We often add the prown number
asasubscriptbeforethesymbol.Soforcarbon:
'ic is the symbol for carbon-12, which is the most common iSO{ope, containing
6 protons and 6 neutroru;.withamassnumberof\2
'!c is the symbol for carbon-14, which contains 6 protoru; and 8 neutrons , with a
mass number of 14.
The proton number (atomic number) of an atom is the number of protom in its
nudeus. The mass number of an atom is t he sum of the numbers of protons and
Worked example
How many prntons and neutrons are there in each of the fol lowi ng atoms?
1 1
!0 b Mu
How many protons, 0ectrons and Answe r

neut ronsaretherein eachofthe Thesubsc:riptgivestheprotonnumber,thatis, thenumberof protoos.Soforoxygen,
following atoms? numberof protom =8.a ndforuranium,numberof prntons =92
Subtracting t he proton number from the mass number gives the number of neutrons
, ~{ Na Sofofoxygen,numberofneutrons ~ 18 - 8 = 10,and!Ofura nium.numberof
2 1~)! neutrnns = 23S - 92 ~ 143
2.5 The mass spectrometer

The masses and the relative abundances of individual isotopes are easily measured in
a ma ss SJ)('Ctromctc r . This is a machine in which atoms that have b,e.,n ionised by
thelossofelectronsareaccelemtedto3 high velocity. and theirtmjectories (paths)
are then deflected from a straight line by passing them through a magnetic field . A
mag neticfieldhasasi milarbending e ffect o n moving charged paniclesastheelectric
fieldinHgure2 .J (see page 22).
Flgure2.4 Schematkdiagramofama1s
lpl'(ttometl.'I"
Figure 2.5 A modl.'l"n mao;s spectromeW 4 magnetic fie ld
he avil!f partid .,,

pa rtklesof interm<'diatema,s
lighter particles
tovacuumpump
l3
PHYSICAL CHEMISTRY
F"veprocessesoccurnamassspectrometer.
1 lfitisnOI alreadyagas,theelement lsvap;:>ri.sedinanoven .
2 Electrons are fired 31 the gaseous morns. These knock off Olher electrons from
3 The gaseous ions are acceleroted by passing them through an electric field (31 a
voltageofS-lOkV).
4 The fast-mming iOfls are deflected by an electromagnet. The larger the charge
on the ion. the larger is the deflection . On the Olber hand. the he:ivier the ion,
the smaller is the deflection . Overall, the deflections are proponional to the ions'
charge-to-mass ratios. If all ions have a + I charge (which is u5Ually the case), the
=tents of deflectiOfl will be inversely proportional to their masses
5 The deflected ions pass through a narrow slit and are collected on a metallic plate
connected to an amplifier. For a given strength of magnetic field. only ions of a
ceitainmasspassthroughtheslit and hitthecollectorplate. Asthe(positive)ions
hit the plate, they cause :, curTent to flow through the amplifier. The more ions
there:ire , thebrgerthecurrent.
The ions may travel a metre or so through the spectrometer. In order for them
to do this without hining t<X> m:iny air molecules (which would deflect them
from their course), the inside of the spectrometer is evacumed to a ,ery low
pressure. Whenthesitu:ition is such that a ste:idy stre:im of ions is being
produced. thecurrentthroug htheelectromagnet is changed at a steady rate . This
causes the magnetic field to change in strength. and hence allows ions of different
m:isses to p:,ss successively through the slit . A m ass s p L'Ctrum is produced,
which plots ion current against electromagnetic current . This is equiv:ilent to
relative :ibund:ince against m:,ss number. Figure 2.6 shows the mass spectrum
of krypton .
A mass spectrum enables us to an:ilyse the propoltions of the v:uious isotopes in
:in element . However. by far the main use of the mass spectrometer now:idays is in
:inalysingtheformul:ieandstructuresoforganicandinorg:inicnx,lecules. \Veshall
return to this applirntion in Topic 2'}.
Flgure2.6 M.1111op!.'(trumofKrwtori
78 0.3
80 2.3
82 11.6
83 11.5
84 56.9
86 17.4
24
Worked example 1
CMorinemnsistsoftwoisotopes,withmassnumbersJSand37,andwithrelativeabundilna.>s
76% and 24% ,e;.pectively. Calculate the average relative atomic mass of chlorine.
Answer
The percentages tell us that ii we took 100 {hlorine atoms at random, 76 of them would
have a mass of 3S units, and 24 of them would have a mass of 37 units
total mass ol the 100 random atoms = (35 x 76) + (37 x 24)
3
1 Chromiumhasfourstab~isotopes, 10 average mass of one atom~ :
1
withmassnumber150,52,53andS4,
andrelativeabundances4.3o/o,8J.8o/o,
9.S%and2.4%respectively.Calrukne thatis, A, = 35.5
theaveragere!ativeatomicmassof
chromium Worked example l
2 Usethefiguresinla~e2.2(po,ge22)
tocalrn!atetheaveragerelativeatomic Calculate the average relative atomi{ ma11 of krypton from the ta~e in Figure 2.6
milSSl'S of boron, neon and magnesium
Answer
tol decimal~ace
We {an extl'fld the 100-random-atom idea from Worked example 1 to include fractions of
J (Harder)lridiumhastwoi10topes.with
atoms. Thus the average mass of one atom of krypton
mass numbers 191 and 193,andits
averagerelativeatomicmassis 192.23 {78x0.J) + (80x2.3} + {B2x 11.6)+(83x 11.S} + (84x56.9) + (86x 17.4)
Calrn!atetherelativeabundaocesof 100
the two isotopes
2.6 Chemical energy

The concept of energy is central to our undersmnding o f how changes come
about in the physical world . Our .study of chemical reactions depends o n energy
concepts
Ch e mica l e n ergy is made up of two components - kinl' tic e n ergy. which is a
me:isure of the motion of atoms. molecules and ions in a chemical sub.stance. and
JX)te ntia l e n ergy, which is a measure of how .strongly these panicles anract one
Kinetic energy
Kinetkenergyincreasesasthetemperatureincreases.Chemi.stsuseascaleof
temperature rnlled the a bsolute te m era m re sca le. and o n this scale the kinetic
energyisdirealyproportionaltothetemperature(seesection4.13).
Kinetic energy can be of th...,., different types. The simplest is energy due to
tran s la tio n . that is, movement from pbce to place. For monatomic gases (gases
made up of single ato ms. for example helium and the other noble gases). all
the kinetic energy is in the form of translational kinetic energy. For molecules
conrnining two or more atoms, however. there is the possibility of Yibratio n
and rota tio n as well (see Figure 2.7). Both these forms o f energy involve the
movement of atoms, even though the molecule as a whole may stay still . In
diatomic gases. the principal form of kinetic energy is translation. but in more
complex molecules, such as ethane. vibration and rotation become the more
imponantfoctors.
Flgure2.7 Thetwoatomsinadiatomkgas
mok>rule. sucha1nitrogen. behave 61though
they6rejoirn>dbyasl)fing.wtikhletsthem
vibr.itelnandout.Thetwoatoms{analso
mtateabautthecmtreofthebond
25
PHYSICAL CHEMISTRY
In solids. thepaiticles are fixed in position.and !heoolyfonnofkineticene,gyis

vibration. In liquids. the pan:icles can tllO'Ve from place to place, though fllOfe .slowly than
ingases.and.soliquidpanicleshavetrnnslationaLrocationaland,ibmtionalkineticene,gy.
Potential energy
lnstudyingchemicalenergy,wea..,-usuallymoreinter<,stedinthepotentialenergy
ofthesystemthaninitskineticenergy. Thisisbecausethepo1ential energy g ives us
irnponam quantitative informmion about the strengths of chemical bonds. At normal
temperatures, potential energy is much larger than kinetic energy.
POlential energy arises because morns, ions and molecules attract and repel
one anO!her. These attractions and repulsions follow from the basic principle of
electrostatia,. that unlike chaiges attract and like charges repel. Ionic compounds
contain panides with clear po.sitive 3nd negmive charges on them. Two positively
charged ions repel each cxher, a.s do two negatively charged ions . A po.sitivc ion and
a negative ion attract each cxher. Atoms and molecules, which have no overall charge
on them. also anrac! one ancxher (see section 3.17) .
h requires energy to pull apan a sodium ion. Na . from a chloride ion. Cl. The
pocential energy of the syscem increases because we need to apply a force F (equal
to the force of anraction becw=n the t,vo ions) for a distanced (see Figure 2.8). In
Flgure2.8 Tosep.irateoppo-;ite!ycharged a similar way. we increase the JX)lential energy of a book if we pick the book up off
iomthroughadi5t.Jriced,afofCefisrequired the floor and put it on a desk(see Figure 2.9).
Flgure 2.9 nergyi11lt.'!.'(}@dtoltftabook

fromtheMoorandputitonthedesl:
T
In contrast. if we stan with a sodium ion and a chloride ion separated from each
Ol:herandthenbringthemtogether.thepo!emialenergydecreases. \Vealsodecrease
the JX)lential energy of a book if we 3llow it to fall from the desk to the floor.
As we shall see in Topic S. chemists are usually interesccd in the change in
chemicalenergythacoccursduringareaction. Thischangeisrepresentedbythe
symbols !J.E - the Greek leuer delta, A. being used to mean "change. If we look
atenergychangesthacoccurmconscam pressure.whichisnormallythecasein
che la boratory, we use the symbol AH, which represents the c mhalpy change of
3 reaction. The m0.51 commonly used uni! of energy in chemistry is the "-' mor'
(kilojoule per mole). where l kJ = JOOOJ .
2.7 The arrangement of the electrons -

energy levels and orbitals
On page 21 we concluded that the 3tom is made up of3 ve,y dense, ve,y s,nall nucleus
containing1hepro1:oruandneutrons.andamuchlargerregionofsparearoundthe
nucleus that contains the electrons . \Ve now tum our ancntlon to these electrons. We shall
see that they are nOI: distributed randomly in this region of spare. They occupy specific
volume regions. called o rbitals. which have specific energies associaced with them.
26
Energy levels and emission spectra

When gaseous atoms are given energy, richer by heating them up to several hundred
degr=s. or by passing an electric cu,n,.nt through them, the electrons become e x cited
and move from lower energy levels ro higher levels. Electrons in gase,:,us atoms can al.so
move from lower to higher energy levels by absorl,ing specific frequencies of ligh!. This
leaves dark absorption line-sin the spectrum of light transmined through the gas . h was
these ab.sorp!ion lines thac provided the first evidence for a new element discovered in
the oucer regions of the Sun . h ,vas named helium. after the Greek ,vord for the Sun.
helios. The technique of atomic absmption spectroscopy is widely used today co measu....-
accurately. for example. the coocentrations of calcium and sodium in a blood romple. or
theelementscontainedinasampleofasteelaUoy(seeF1gure2.10).
EvemuaUy.cheexciledelectronsloseenergyagainbyfallingdo,.vncok,,,,,-erenergylevels.
During thisprocesstheyradiatevisibleorultravioletligh!inspecificamountsas'packets'
called photo n s. We can analyse the radiated light with a device called a spectroscope. shown
in Figure 2.11. lbe c m isskln spectrum shows that only a very few specific frequencies
are en1ined. and these are unique to an individual element. All the atoms of a panicular
element radiate at the same set of frequencies. which a"' usually different from those of
Flgu re 2.10 An.itomicabsorption aU other elements (see Figu"' 2.12). This is the process that is "'.sponsible for the flame
spectrometer colours d the elements of Groups l and 2 (see Topics 10 and 19). The obsewation of line
spectra. implying that photons of only specific energies are emitted or ab.'>Clrbed by atoms.
corutitutes.strongevidencefortheexistenceddiscrefeelectronicenerg ylevdswilhinatoms.
Figure 2.11 Outline diagram showing how a
1pectmsrnpewo!',;1
Flg u re2.12 a Whitelight1.pectrnm a white light

b Sodiumemis1ion1opectrum
fre quency/10"Hz
c Cadmiumemi1SKln1.pectrnm
wavelength/nm
b sodiumvapour(yellovv)
fre quency/10"Hz 4.29
wavelength/nm
c cadmiumvapour(turquoisegre en)
fre quency/10"Hz 4.29
wave length/nm
27
PHYSICAL CHEMISTRY
The energy E of a phOlon of light is related to its f~uency,f by Planck's equation:
E = hf
If phowns of a panicular frequency are being emitted by an atom. this means that
the acorn is losing a panicular amount of energy. This energy r<,presents the difference
between two Slate.s of the acom. one more energetic than the Olher (see Figure 2.13).
Flgure 2 .H Aphotooi1emitteda1the
atommove1bern.wnl1atef1 ;md1tatef1
photon emitted,withenergy
The spectrum of the simplest atom , hydrogen. shows a serie.s of lines at different
frequendes(seefigure2 . l4). Thissuggeststhatthehydrogenatomrnnlosedifferent
amounts of energy. which in turn suggests thm it rnn exist in a range of energy states
Transitions between the various energy states cause phOlons to be emined al various
frequencies. lheseenetg)'statescanbeidentifiedwithsituationswhen,thesinglehydrogen
electron is in cenain oibitals, at specific distances from the nucleus, as we shall see.
Flgure2.14 P.irtoftheh)l{Jrogen
1pectrum,1howingthernrre5p0nding
energytr.irisiboris
============~ =::! . , )
ex<itedelectron
fallston:2
a photon is released
freque ncy,fllO"Hz
28
Quantum theory
Thefactthatonlycettainfrequende-sof lightan,emined.ratherthanacontinuous
spectrum. is compelling evidence that the energy of the hydrogen atom can t:1ke only
cenain v:i.lues. ncx a continuous range of values. This is the basic notion d the quantum
thC'Ory. We say that the energy d the hydrogen atcon is quantised (rather than
continuous). It rnn k>Se (or gain) ene,gy only by losing (or gaining) 3 qu.'llttum of ene,gy.
A good analogy is a staircase. When you climb a st:lirrnse. you incn,ase your height
by cenain fixed values (the height of each step). You can be four steps from the bonom,
or five steps , but no1 four and a half steps up. By comrnst. if you wen, w:ilking up a
ramp, Y01J coukl choose to be at any height you liked from the bonom. It rums 01Jt that
theene,gyofaU"'*ctsisdistributedinst:1ircase.sratherthaninramps.butiftheobject
is large en01Jgh. the height of each step is vanishingly smaU . lhe energy values then
seem to be almost continuous. rather than stepped. It is only when we look at very small
objects like atoms and molerule-s that the height of each step become.s significant.
Thesiz.eofanenergyquantum (theheig htofeachstep) is notfixed , hmvever.
It depends on the type of energy we are considering. We shall return to this point
in Topic 29 when we study spectroscopy. \Ve can use the methods of quantum
mechanics to calculate not only the energies but also the probability distributions
oforbitals (seeFigure.s 2. l 6 3nd2.18 .page3Q).
Energy levels in the atom

Hydrogen is a very small spherical atom with only two particles 3 prcxon and an
electron. Apan from energy of movement (translational kinetic energy) . the only
energy it can have is that associated with the electrostatic 3llraction between its two
particles (seepage26). Thedifferentenergylevels an,then,foreduetodiffen,nt
electrostatic potential energy s t:ltes. when, the el=tron is at different distances from
theproion (seeFigun,2.15).
Flgure2.15fnergyagaimte!l.'ctron--proton
distaocelorthehydrogenatom.Thered
cuiverepre'il'rltshowthepotentialenergy
ofthehydrogenatomwookJvarywith
elec:troo-protondistanceiltheenergyrnuld
takeonanyvalue.a1predictedby1imple
electrostatic theory.But.a1wehave!il'!'n
aboYe,tnepotenti.1lenergyisquantlsed.and
G1nonlytakeoncertainvalue1.shownin~ue
Thefl'foretheelec:tronG1nonlybeatcert:ain
(average)distancesfrnmthemKleu1. These
arethee!ectrooicorbital1.aridaregrventhe
symbollls,21.etcNotethatthei>nergyof
theproton-ek>ctroosystemi1u1uil1lydefined
asbeingzemwhenthetwoparticlesorean
infinitedi'itana>apartAs,;oonastheystart
gettingclosertogether.theyattracteachother
andthisullSl'lthepotentialef\efgyofthe
system todeoease. Toil i1whytheenergy
valuesoothe_v-axi1areal l negative
~-
Table2.3 Toenumberofortiitalsine.1ehlhe!I These energy levels. associated withdiffen,ntdistancesoftheelectron from the
nucleus. an, called orbit:il'>. by analogy with the orbits of the planets at diffen,nt
Pr1nclp.il shel l Number of
orbltills The orbitals are arrang ed in she lls . Each shell contains orbitals of roughly the
same energy . The shell with the lowest energy (the one clo.sest to the nucleus)
con tains only one orbital. Shells with higher energies. funher out fro m the
nucleus , contain increasing ly l3rge numbers o f orbitals, acco rdin g to the
formula :
number of orbitals in mhshell = n 1
Table 2.3 shows the number of orbitals in each shell. according to this equation.
29
PHYSICAL CHEMISTRY
2.8 Subshells and the shapes of orbitals

Electron probability and distance from the nucleus
Unlike a pbnet in a circular orbit, whose distance from the Sun does n{){ change.
anelectroninanorbitaldoesno1remainatafixeddistancefromthenucleus.
Although we can calculate, and in some cases measure, the average electron--
nucleus distance. if we ,vere co take an insrnntaneous snapshOI of the atom. we
would be quite likely to find the electron either funher away from or closer to the
nucleus than this average distance. The graph of probability of finding the electron
against its distance from the nucleus for a typical orbital is shown in Figure 2 .16.
3nd by contrast 3 similar one for the E3nh--Sun distance is shown in Figure 2.17 .
Ncxice that. because of the gradual falling-0ff o f the electron probability, there is a
finite (but ,ery small) ch3nce of finding an electron a very long way from the centre
tr,....i,:1.s~10"1cm
Flgure2.16Theelectronprobability
disttibution for.12100Jital
Flgure2.17Thepmbabilitydistributioofor 1.0 ~ 10" 2.0 ~ 10"

thefarth--Sundistance
The first shell - s orbital

The single oibital in the first shell is spherically symmetrical. This means that the
probability of finding the electron a t a given distance from the nucleus is the same no
maner what direction fron, the nucleus is chosen . This orbital is called the I s orbital.
The second shell - s and p orbitals

Of the four orbitals in the second shell. one is spherically symmetrical. like the
orbital in the first shell. This is called the 2s orbital. Its probability curve is shown
in Figure2.l6. Theotherthreesecond-shellorbitals point along the three mutually
perpendicularx-.y-and z-axes . These are the 2porbital'>. They are called.
respectively. the 2p_... 2py and 2p~orbitals. They do nOI: overlap with one another.
Forexample.anelectroninthe2p,,orbitalhasahighprobabilityofbeingfound
onorneartothex-axis. but a zeroprobabilityofbeingfoundoneitherthey-axis
or the z-axis. These two different cypes of orbitals - the 2s and the 2p - are of
r.,,:0.22nm slightly different energies . They make up the cwo subshclls in the second shell of
Whenanelectronislocatedinansorbital.thereisafairchanceoffindingitright
at the centre of the acorn. at the nucleus. Bue the distribution curve for the 2p orbital
in Figure 2.18 shows that there is a zero probabiHty of finding a p electron in the
Flgure2.18Theelectronprobability centre of the atom. This is general for all p orbitals. Electrons in these orbitals tend to
di1tfibtrtionfo1a2porbit.1I occupytheouterreachesofatoms.
In three dimensions, an s orbital can be likened to a soft sponge ball, whereas a p
orbital is like a long spongy solid cylinder. constricted around its centre to form two
lobes,asshownin Figure2. l9.
30
Flgure 2.19 Theshape-;of a the2sorbitJI

and b the thrl'e 2p ortiit.111 The third shell - s, p and d orbitals
Frornthen1 formulaonpage29wecanpredictthattheff"willbenineorbirnlsinthe
third shell. One of these. the 3s orbital. is spherically symmetrirnl. just like the Is and
2s orbitals. Three 3P orbitals. the 3p~, 3p1 and 3p, orbitals, each have two lobes,
p;:>inting along the axes in a similar fashion to the 2p orbitals. The o ther five have a
different shape. The mOSI common interpretation of the mathematical equations thm
d e scribe their shape suggests thm four of these o rbimls each consist o f four lobes in
the same plane as one anO{her. and pointing mutually at right angles, whereas the
fifth is best represented as a two-lobed orbital surrounded by a 'dough nut' of electron
density around its middle. They are called the 3d orbitals, iJJustrated in Figure 2 .20.
So the third shell consi.sls o fthreesub.shells the 3s , the 3p 3nd the 3d subshells.
Flgure2.20 Toe1hape1aflhefive3d
arbitl!s.Foura f themh.ivethe1ame1hape.
butindiffell'nladent.1tiom . Thefiflhhasl
ditfe1ent1hape.aslllawnin e
d 3d_.>-,> z
The fourth shell - s, p, d and f orbitals

The process can be continued. In the founh shell. we predict that there will be 4 2 = 16
Flgure2.21 Toe1hapeolar.e4farbit.il orbitals . One of these will be the 4s orbirnl. three will be the 4p orbitals. five will be
:~:eare efght klbes pointing out Imm the the 4d orbitals. leaving seven oibitals of a new type. They are called the 4 f orbila ls.
Each consists of many lobes JX}inting away from one anocher. as shown in Figure 2.21.
Shells and orbitals in summary

The number and type of orbitals within the different shells are s ummarised in Table 2.4.
Table 2.4 The numberandtypeoforbit.i11 Shell number, Number of orbitals N1.n1ber of orblt.ils of each type
in each shell wtthlntheshell,n' (thatls,n1.n1berolorblt.ilslneachsubshell)
31
PHYSICAL CHEMISTRY
Worked example
Wh at is the total mimbef of o rbitals in t he fifth shell? How many of these are d o rbitals?
How many0<bitalswill bein: Answe r
il lheSpsubshell Totalnu mber of orbital s = Sl = 25.0f these, 5 aredo rbita ls.(Therearelivedorbita lsin
b theSf5U~I? everyshell above t hethirdshell.)
2.9 Putting electrons into the orbitals

The atoms of different elements contain different numbers of electrons. A hydrogen
morn contains just o ne electron. An atom of uranium contains 92 electrons. How
theseelectronsarearrangedinthevariousrnbitalsiscalledtheatom's ek-ctronlc
configuratio n . This is a key feature in de!ennining the chemical =ction.s of an element.
The electrons around the nucleus of an atom are most likely to be found in the siruation
of lowest possible energ y. That is, they wiJJ occupy orbitals as close IO the nucleus as
po,s,;ible. lhe single electron in hydrogen "'~U theref"' be in the ls otbital. The electronk
configuration of hydrogen is written as ls' (and spoken as 'one ess one'). The next
element, helium, has two electrons, so its electronic config uration is ls 1 ('one ess t,vo').
For re:,sons that we shall l<X>k at later, we find that each orbital, no mauer what
shell or subshell it is in, cannOI accommodate more than two electrons . The third
electron inlithium,therefore,hastoocrupytheotbitalofnextlo""'stene-rgy,the
2s. The electronic configuration of lithium is ls' 2s1. Beryllium (ls'2s') a nd boron
(ls 2 2.s1 2p 1) followpredictably.
When we come to catbon (ls 22s' 2p1), we need to differentia te between the three
2potbitals. Becauseelectronsareallnegativelycharged,theyrepeloneanOlher
electrost:itically. The three 2p orbitals a re all of the same energy. Therefore we
would expect the two p electrons in catbon to occupy different 2p otbirnls (for
example, 2p~ and 2p_,,) . as far away from one another as possible . This is in fact what
happens. Likewise, the seven electrons in the nitrogen morn aminge themselves
is22s'2p/2p_,,' 2p/. It is only when we arrive at oxygen (ls1 2s'2p/2p_,,' 2p/) that
the 2p otbitals .s1an to become doubly occupied. For many purposes. however, there
is no need to distinguish between the three 2p otbirnls, and we can abbreviate the
electron icconfigurationofoxygento ls1 2s1 2p 4.
This process continues until element number I& argon. With argon, the 3p subsheU is
fiUed, andwewoukiexpectth:itthenextelectron shouldsmntooccupythe3dsubshell.
But here the e,;:pectation is OOI what happens. Instead, the ninet=nth electron in the next
element, pou.ssium, occupies the 4s subshell . We shall now explain why this is the case.
2.10 Shielding by inner shells

lnasin gle-electron momlikehydrogen,thep;:Xentialenergyisdueentirelytothe
single electrostatic attraction between the electron a nd the prown. When we move to
the two-electron morn helium, two changes have occurred .
I The nucleus now contains two protons, and has a charge of + 2. It will therefore
auracttheelectronsmore,andreducethepocentialenergyofthesystem,thatis,
2 Howe\'er, the second electron in the atom wiJJ repel the first (and vice versa). This
makes the decrease in po{ential energy described in I above less than it wou ld
This has a dear effect on the ionisation energies of the two elements.
The ionisation e nergy ofanatom(orioo)isdelineda1theenergyrequiredtoremove
completelyamcleofelectronsfrornamcleofga1eOU1atoms (orioos). Thatis,the
ionisatiooenergyistheenergydiange!Oftheloilowingproc:ess
X(g)--.+X'\g) + e-
32
Forhydrogenandheliumtheionis:11ionenergiesare:
H(g)---+H\g) + e- LlH = l312kJmol- 1
He(g)---+He+(g) + e- LlH = 2372kJmoi- 1
NOie that Ml is the symbol chemists use for emhalpy change. The emhalpy change of
a processisthcencrgychangeth.uoccurswhentheprocessiscarricdoutatconsum
pressure(seeTopic5).
h ukes more energy to remove an electron from a helium atom than from a
hydrogen atom. This shows that. compared with the energy when the electron is at
infinity. the energy of the ls orbital has become more negative in helium (sec Figure
2.22)thaninhydrogen(sce Fig urc2. IS. pagc29).
Flgure2 .22 Theeriergyneededtoremove

anelectronfrnmahydrogenatomanda
helium.itom
L_,, ,rnmo,-t
Hi = i',J-/:2372kJmot" 1
"
This decrease in energy for the Is orbital continues as the prown number increases
(sec Figure 2.23). The decrease in energy is also true for O!hcr orbiuls . The reason
istha! asthenumbcrofprotonsinthcnucleus increases. the electrons in a palticular
orbiul arc anracted to it more. The decrease in energy is nOI regular. however. and is
nOI the same for all orbitals . This is due to 1,vo factors
Flgure2.23V.iri.itionoftheenergyolthe
11orbital11ithprnton11umber
33
PHYSICAL CHEMISTRY
The average disrnnce of a p orbital from the nucleus is larger than that of the
correspondingsrnbirnlinthesamt"sheU(seeFigure:s2.16and2.18,page30).
Electronsinprnbitalsthereforeexperiencelessofthesmbilisingeffectofincrea.sing
nuclearchargethanelectronsinsoibitals. Forasirnilarreason,clectronsindorbitals
experienceevenlessoftheincreasingnudearchargethanelectronsinprnbitals.
All electrons in outer shells are to some extent shielded from the nuclear chaige by
the electrons in inner shells . This shielding has the effect of decreasing the effective
nuclear charge. In the case of lithium. for example. the outem10st electron in the 2s
orbital does not experience the full nuclear charge of + 3 (see Figu"' 2.24). The two
electrons in the filled Is orbirnl mask 3 good deal of this charge. Overall. the
Flgure2.24Thelithiumnucleusandinner cffccth"l' nuclear charge experienced by the 2s electron in lithium is calculated
1hell tobe + l.3, whichisconsiderablylessthanthe3ctualnuclearchargeof +3 .
A plot of orbital energy against promn number for several orbitals is shown in
Figure2 .25 .
F1g u re2.25 GraphofortJitalenergy.iga inst
protonnumbe1for1hellnumber11-5(1ee
Tab4e24,page31)
34
ltcanbeseenthm,foreachshell,theelearonsinthesorbitaldecrease!heirenergy
fasterthanelectronsintheporbitals.Electronsintheporbitalsintumdecreasetheir
energyfasterthanelearonsinthedorbitals, andsoon. lnpanicular.electronsin
che4s and4potbitalsdecreasetheirenergyfa.sterthanelectronsinthe3dorbitals.
So much so.that by the time 18electronshavebeenadded(itsohappens),thenext
most srnble orbiml is the 4s rather than the 3d. The orbital filHng continues after
p;:,tassiumintheorder4s.----3d--4p---5s.----4d- 5p----6s-4f- 5d-6p--7s. reOeaingthe"lagging
behind ' of the d and f orbitals. This is due to the effective shielding, by filled inner
electron shells . of these orbitals from the increasing nuclear charge .
The simple mnemonic diagram in Figure 2.26 will help you to remember the order
inwhichtheorbitalsarefilled.
2.11 Electron spin and the Pauli principle

Electrons are all identical. Theonlyway o fdistinguishingthemisbydescribing
howtheirenergiesandspatialdistributionsdiffer. Thus an electron ina ls orbital
isdifferentfromanelectron in a 2sorbital because it occupies a different region of
space closer to the nucleus, causing it to have less potential energy. An electron in
3 2p,,, orbital differs from an electron in a 2py orbital because although they have
exactly the same potential energy. they occupy different regions of space.
Two electrons with the same energy and occupying the same orbital must be
distinguishableinsocne,vay.orelsetheywould.infacc.beoneandthesamepanicle.
Experiments by Otto Siem and Walther Gerlach. in Germany in the 1920s, showed
thatanelectronhasa magneticdipolemon,ent . Aspinningelectricallycharged
Figure 2.26 Mnemooic fOf the order of filling sphere is predicted to produce a magnetic dipole - it acts like a tiny magnet. with a
ortJitJII north and a south pole . Therefore the most common explanation for the results of the
Siern---Gerlachexperimentisthattheelectron isspinningonitsaxis. and the direction
of spin can be either clockwise (let us say) or anticlockwise. These two directions of
spin produce magnetic moments in opposite directions. often described as up" (given
thesyrnboli) and'down ' (giventhesyntbol.J..).
We could therefore distinguish between two electrons in exactly the same orbital
iftheyhaddifferentdirectionsofspin.Allelectronsspinatthesamernte,andthere
are only two possible spin directions. Therefore there are o nly two possible ways of
describing electrons inthesameoIDital(forexample, Jsiand Js..l.). So there can only
be two electrons in each orbital. and they must have opposite directions of spin. A
third electron would need to have the same spin direction as one of the two already
there. which would make it indistinguishable from the similarly spinning one.
lbe situation is neatly summarised by the Pauli exclusion prlncllc. "ttich states that:
No JTIOfe than two electrons can occupy the same orbital, and if two electrons are in the
sameorbital,theymusthaveoppositespim
2.12 Filling the orbitals

Wearenowinapositiontoformulatetherulestouseinordertopredicttheelectronk
configuration of the atoms of the elements. and also the iOfls derived from them.
Collecting together the conclusions of sections 2.7- 2.11. we arrive at the following.
I \Vork out. from the element "s prown number (and the charge, if an ion is being
considered). the total number of electrons to be accommodated in the orbitals .
2 Taking the orbitals in order of their energies (see Figure 2.26), fill them from the lowest
energy (ls) upwards. making sure that no orbital contains more than two electrofls.
3 Forsu b.shellsthatcontainmorethanoneorbitalwith thesacneenergy(thep.dand
fsubshells). placetheelectronsintodifferentorbitals, untilallaresinglyoccupied .
Only then should funher electrons in that subshell scan doubly occupying orbitals
For example. place one electron into each of 2p,. 2py and 2p~ before putting two
electronsintoanyporbital.
4 Two electrons sharing the same orbital must have opposite spins.
This procedure is known as the Auftxm or building-up ' principle.
35
PHYSICAL CHEMISTRY
The electronic configurations of atoms and ions can be represented in a variety of

,vays. These are ilJustmted here by using sulfur (pro1on number 16) as an example.
One way is as an etectrons--in-OOXes' diagram. as shown in Figure 2.'I?.
Flgure2.27 Eled:ronHn-boxesdiagr.im
1howirigtheek.>ctronicrnnfigurationofrnlfur
Notethattheboxe5G1nalsobe,aridu1Ual!y
3
Pl1_;1~1! I
are,arr,mgedinooerr.m,withno'steps'to
,, [ii]
indkateeriergyk>vels(asinfigure2.2Bbeklw)
Pl1;11;11;1
2
,, [i_j]
h [i_i]
An alternmive is the long linear form. specifying individual p orbitals:
ls 22s'2p/2p/2p/3s' 3p/3p,.' 3p,'

Below is the shonened linear form. which is the most usual representation:
ls 22s'2p63s1 Jp4
(Nel3s'3p4
where(Ne)representsthefilled shells in the neon atom. ts'2s 1 2p6.
Sometimes. if we are only concerned with whkh shells 3re filled. rather than which
sub-shells,theelectfOflconfigurationofthesulfuratornc3nbedescribed as2.8.6,
me3ning 2electronsinthefirstshell;8dectronsinthesecondshell:3nd6dectrons
Worked example
the 'electronYin-boxes represe<1tation of the silicon atom

b the shortened line.ir form of the electro nic configuration of the magnesium atom
c theloogline.irformoftheelectronicconfigurationofthefluorideioo
Answer
Silicon hits proton number 14, so there are 14electrons to ilCcommodate, as shown
inFigure2.28.Notethat thelasttwoelectronsgointothe3P,;and3pyorbitals,with
unpa ired spins
Flgure2.28
b Magnesium has proton number 12. The 12 electrons doubly occupy the six orbitals lowest
in energy
Writeoottheloogline;irformofthe
11"2si2p6 3sl
electronkrnofiguratkmofeachofthe
following atoms Of ions c Fluorinehasprotonnumber9.TheP--ionwillthereforehave(9 + 1) ~ 10electrons
1N 2 Ca 3 All+ 1i2si2P,;l2p/2p/
2.13 Experimental evidence for

the electronic configurations of
atoms - ionisation energies
A m3jor difference betv."een electrons in different types of orbital is their energy. We
rnn investig:,te the electronk configurations of acorns by measuring =perimentally
the energies of the electrons within them . This rnn be done by measuring: ionis3tion
cmrgics (seepage32).
36
Ionisation energies are used to probe electronic configurations in two ways:
e successiveionisationenergiesforthesameatom
firstion isation energiesfordifferentatoms.
Successive ionisation energies

We can look at 3n 3Com of a p<1rticul.tr element. and measure the energy required to
removee3chofitselectrons,oneby o ne :
X{g) ---+X'"(g) + c- ll H = IE1

x (g} ---+ Xl+{g) + c- llH = IE1
x 1 (g} ---+Xl+{g) + c- llH = IEj
These s u cce ss ive ionis m io n e n ergies show clearly the arrangement of electrons
in shells around the nucleus. lf we take the magnesium atom as 3n example, 3nd
me3suretheenergyrequiredtoremovesuccessivelythefirstelectron.thesecond.the
third, and soon. weobtaintheplO{showninFigure2.29.
F1gure 2.29 GraphofthetwelveKl!lt<.ation

energie1ofmagnesiumac:;al11,tek>ctron
number Theelectronicrnnfiguratiooof
magriesiumis1s'21'2p"31' first
she ll
second
she ll
Successive ionisation energies are bound to increase because the remaining electrons
are closer to, and Jess shielded from , the nucleus . But a larger increase occurs when
the third electron is removed . This is because once the two electrons in the ou ter
(third) shell have been removed. the n=t has to be stripped from a shell that is very
much nearer to the nucleus (the second shell) . A similar. but much more enormous ,
jump in ionisation energy occurs when the eleventh electron is removed . This has
to come fron, the first. innermost shell. right next to the nucleus. These two large
jumps in the series of suca,-ssive ionisation energies are very good evidena,- that the
electrons in the mag nesium aton1 =ist in three different shells .
37
PHYSICAL CHEMISTRY
The jumps in success;_.,, ionisation energies are more apparem if we plOI: the
logarithmoftheionisationenergyag:,in.s1prownnumber,asinfigu..,2.30. (faking
thelog:,rithmisascaling devicethachastheeffectofdecreasingthedifferences
betwl"enadjacentvaluesforthelargerionisatiOflenergies.sothejumpsbetweenthe
shells become more obvious.)
Flgure2.30 Graphoflogafithmsofthe
twelvekmi1ationenergiesofm..griesium
agalnst!'k>ctroo number
Worked example
Thelirstfive~ccessiveionisationenergiesofe~tXa1e631,1235,2389,7089and
8844kJmol- 1.
How m,my electrons are in the outer shell of element X?
Answer
The differencesbetwei!nlhesuc:ces~veionisationenergiesareasfollows
2 - 1 1235 - 631 ~ 604kJmot-1
3 - 2: 2389 - 1235 ~ 1154kJmor-1
Decide which group element Y is in, 4 - 3: 7089 - 2389 ~ 47001:JmoJ-1
basedonthefcilowingsua:essive S - 4: B844 - 7089 = 175Sk.lmot-1
ionix1tioneoergies The largest jump comes between the th ird and the fourth ionisalkln energies, therefore X
590, 1145,4912,6474,8144kJmol- 1 hasth1e{'electronsinitsooter1hell
First ionisation energies

The second way that ionisation energies show us the details of electronic configuration
is 10 look 31 how the first ionis:11ion energies of elements vary with proton number.
Figure2.31 isap]O(forthefirst40elements.
This graph shows us the following.
I All ionis:11ion energies 3re strongly endothermic - it takes energy to separate an
2 As we go down a panicular group, for example from helium to neon to argon. or

from lithium to sodium to potassium, ionisation energies decrease . The larger the
3tom,theeasieri!istoseparate3nelectronfromit.
38
FJgu re 2 .31 fir-;tiooi'i.otionenergH'1f0<the

fif';l40eleml.'r115
proton number
3 The ionisation energies generally inc..,ase on going across a period . The Group l
elements (the alkali mernls) have the lowest ionisation energy within each period,
and the noble gases have the highest.
4 This general increase across a period has two excep1ions. Por the first two periods.
these occur between Groups 2 and 13 and between Groups 15 and 16.
We shall comment on each of these femu..,s in tum .
1Theendothermicnatureofionisationenergies
This is due to the eleetro5tmk attraaion between each electron in an morn (even
the outermOSI one. which is always the easiest to ..,nx,ve) and the po.sitive nucleus.
It is wonh remembering thm this applies even to a lkali metals like sodium. which
we usually think of as wanting' to form ions . We must bear in mind . however. thm
ionisation energies as ploued in Pig ure 2.31 apply to the ionisation of isolmed atoms
in the gas phase. Ions ""' much more stable when in solid lattices or in solution. We
shall be lookingmthisindernilinTopic20.
2Thegrouptrend
The nuclear charge =perienced by an outer el=tron is the cffl.'Ctivc nuckar
charge, Zeff. It rnn roughly be equated to the number of protons in the n u cleus,
P. minus the number o f electrons in the inner shells , E. As we explained when
consideringtheionisationenergyoflithiumon page 34. in ner shells shield the
effea of the increasing nuclear charge on the outer el=trons. Because of this,
the outer elearons o f elements within the same group experience roughly the
same effective nuclear charge no m atter what period the element is in. W'hat does
chang e as we go down a g roup. however. is the atomic radius (see Pigure 2 .32).
The larger the radius of the atom. the larger is the d istance between the outer
el=tron and the nucleus. so the electrostatic attraction between them is smaller.
39
PHYSICAL CHEMISTRY
F1g u re2.32Theeffectivenucle.ird!arge.
z,ff,andlizesofthecore1ofthreealkali
~l1.Thec0<e,rl'pre1eotl.'dbytheblue
ci1cle1,compri~thenucleu1plu1all
theinne11hell1ofelectron1 . De1pitethe
inue~seinZo11, theioni1ationenergH'1
decreas.e from mhium to 1XJla11ium. owing
totheinoeasedelectroo-nude111di1taoce
lith ium ,odium potassium
1j 1~~2~ 1~~2~~~
ioni,atio n energy/
kJm o1- >
3Theperiodictrend
As we f1P across a period, we are, for each element, adding a prolon to the nucleus, and
an electron !o the ou termost sheU. lne extra prolon wUL of course. rnuse the nucleus
to attrna all the electrons more strongly. Electrons in the same shell are m (roughly) the
same dist:ince from the nucleus a.s one ano{her. 1bey are the,do"' no1 p<1rtkubrly good
atshieklingoneanotherfromthenudearcharge. Asa,.,Sllltofthis,theeffectivenuclear
chaigeinc=ises. Thisrnusestheelectrostaticanraction becw=ntheionisingelectron
and the nucleus to inc=ise too. Table 2.S Ulustrmes this for the second period.
Tab le2.5 Comparingthevaluesof(.P - f) Nu mbe r o f

andlm>effKtivenlJClearcha19e,Z,M,for protons, P s h&l l electrons, E charge,Z.,w
::0~; ~-;i1notexacttyequalto(.P - f)for
1 1
1 Ek>ctromin1orbitalspenetratethelnner
orbitals to a certain exten~ and are therefore
le111hieldedbythemthanooemighthave
prl.'dictl.'d
2 Ek>ctrominthes.amesllell do,toacl.'rtain
exten~ shield Of\!' aoother from the nlJCletJS
Thi1effectbecomeslarge1.11theouter1hel l
bec:ome1morefullofelectrom,andsothe
disul'p,lm:ybetweenZo1rand(P - f)incre.ise1
a1wecm11aperKld
4Theexceptions
The two exceptions 10 the general increase in ionisation energy across a period (see
Figure2 .3\)arisefromdifferemrnuses.
ln boron ( ls' 2s 2 2p 1), the ou termost electron is in a 2p orbital. The average
distancefromthenucleusofa2poibitalisslightly laigerthan !hatof a 2sorbital(see
Figures 2.1 6 and 2.18). W"e w o uld therefore expect the outermost electron in boron to
experience Jess electrostatic anmct:ion than the outermost 2s electron in beryJHum . So
the ionisation energy of boron is Jess
The other exception is the decrease in ionisation energy fron, nitrogen to oxygen
This occurs when the founh 2p elearon is added, and is relmed to the faa that there
are just thr= 2p orbitals. As we have seen before, because they are of the same
electrical charge, electrons repel oneancxher. The three successive electrons added to
the series of atoms boron - rnrlxm - nitrogen are therdore most likely 10 go into the
thr= orbirnls 2p~, 2py and 2p,.. These orbitals are of equal energy and m right angles
to one ancxher. so allowing the electrons to be as far ap<1rt as possible. They wiJJ
therefore experience the leas! elearostatic repulsion from o ne another, and so, overall,
the a1omic sy.stem will be the mo.st st:ible. In oxygen, however, the founh 2p electron
has to be accommodated in an orbital that already cont:iins an electron. These two
electrons\\-illbesharingthesameregionofsp<1ce(bythePauliprinciple,ofcourse,
their spins will have to be in opposite direaions). and they will therefore repel each
Ol:her qui!e .strongly. This repulsion is larger than the extra anmaion experienced
by the new electron from the additional proton in oxygen's nucleus. So the energy
40
Flgure2 .33 fir-;tiooi'i.otionenergya~imt

pmtonnumberfmPeriod2
o,penodioni>otlonooorgy _ _ __
/lno imor..itronropukion
needed to remove the electron from the oxygen atom is Jess than the ionisation energy
of the nitrogen atom. Similar repulsions are experienced by the additional electrons in
the fluorine and neon atoms. so the ionisation energy of each of these elements is, like
oxygens, about 430kJmol 1 Jess than one might have expected (see Figure 2.33).
Once the second shell has been filled. at neon, the next additional electron (in
sodium) has to occupy the 3s orbital. and stans to fill the third shell. This is funher
out from the nucleus than the 2p electron in neon (remember. electrostatic anraction
decreaseswithdistance). ltisalsomoreshieldedfromthenucleus - bytwoinner
shells. rather than the one in neon - hence Zdl for sodium is only 2.5. On bol:h
accounts. we would expect a large decrease in ionisation energy from neon to
sodium. which we indeed observe (see Figu,.,. 2.31).
2.14 The effect of electronic

configuration on atomic radius
At firs! sight, the radius of an atom might seem an easy quantity to visualise. Bm. as
we saw in Figures 2.16 and 2.18 (page 30). the outer reaches of atoms have an ever-
decreasing electron probabiHty.whichisstiJJgreaterthanzeroevenaclargedistances.
A filled orbital is a preny elusive affair chat can easily be squashed or polarised. We
muse therefo..,- be prepa..,,J to accep! that the value of the atomic radius will nOI be a
fixed quantity. but wiJJ depend on the atom's environment.
Keeping this in mind. however. we can use the theories developed above to p..,,Jict
how the atomic radius mighc change with promn number. We have seen that we might
expecl two major influences on the size of an atom . One of these wiJJ be the number
of shells - the more shells. the bigger the atom should be. We should see this effect
as we go down a group . The <Xher influence will be the effective nuclear charge - the
larger the charge. the more the orbitals are pulled in cowards the nucleus. and so the
smaller the atom should be. We should see this effect as we go across a period. These
two factors combine to produce a predictable panern in the plOI of atomic radius
against promn number. which is borne out by experimental observations (see Figure
2.34). Weshallre1urntothetrendsinatomicradiusinsection 10.3.
41
PHYSICAL CHEMISTRY
decreuingradius
0" 0 0 0 0 0 0
Ms
0"' 0 0 0 0 0 0
'
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Rb Sr
00 OOO 0 0
Figure 2.34 Atoms get larger down a group, as the number of 1hl'lls inrn>ase5. They get 1moller acr05s a peliod, as the effec:We nuclear diarge
pullstheetectronsdosertothenudeu1
All atoms are made of the same three sub-atomic particles - Chem ica l energy has two rnmponl'f1ts - the kinet ic energy
the electron,the proton andthe neutron olmovingparticles,andthe potentla l ene rgy dueto
e Theirrelativeelectrkalchargesare,res.pectively, - 1,+1 andO electfO'itatkattractions
e T~eirmasses{relativetothatoftheproton)aie, respectively, Theelectromarearrangedaroundthenud etriofanato min
"i"ai61and1 energy~vels,or orb ita ls
e The protonnumber(atomicnumber)isthenumberolprotons Whefi an electron movl.'5 from a higher to a lower enefgy level
containedinthenucleusofanelemenl'latoms.lttellsusthe {o rbital},a quantum olenergyisrell'ilsedasaphotonoflight
orderoftheeli>mentinthePeriodicTable ('i0metime1visible,butoftenultravioietlight}
e Isotopes are atoms of the same elemeot (arKi thereftxe with the Thenumberofpossibleorbitalsinthenth'ihellisn1.Each
sameprotonnumber)butwithdifferentriumber:sofneutrons orbital can hold a maximum of two electrons
e The mass number of an atom is the sum of the numbers of Thefirsts.hellconta irisootyoneorbital, whichisansorbital
protonsandneutronsitcontains Thesecondshell rnntainsonesandthreeporbitals,thethird
e The full symbol !Of an atom shows its mass numbef as a shell o nes,threepandliveda<bitals,andsoon.
superscriptanditsatomic(proton)numberasasubscript Theelectrominanatomocrnpythelowestenergyorliitalsfirst
For exam~e. 1lc s.liows a cartxm atom with mass number 12 Orbitalsofequalenergyareocrnpiedsingtywheneverpossib~
andprotonnumber6 Successiveiooisationenl'fgiesofasing~atom,andthetrertds
Masse5andrelativeabundancesofisotope5canbeme.-15Ured inthefirstionisatiooenl'fgk>softheelementacrossperiods
using the mass spectrometer anddowngroups,giveusinforrnationabouttheelectronic
coofiguratioosofatoms
42

Pleaseseethedata5ectionoftheCDforanyA,.valuesyou Copyandcompletethefollmvingtableshowingthe
may need. maximum number of electrons which can be found
within each region (3(
1 Althoughtheactualsizeofanatomcannotbemeasured
exactly, it i5 possible to measure the distance between the [ Region
nuclei of two atoms. For example, the 'c011alent radius' of l a2porbital
theClatomisas.sumedtobehalfofthedistancebet.veen
I
i ttie311ub-1hell I
thenude1inaClimolecule.Similarly,the'metallicradius'is
half of the distance between two metal atoms in the crystal l the4thshell
I
latticeofametal.Thesetwotypesofradiusaregenerally
known as 'atom ic radii'. d ThemodernPeriodicTablearrangestheelementsin
Thetablebelowcontainstheresultingatomicradiifor the orderoftheiratomicnumber.
elementsof Period3ofthePeriodicTable,NatoCI. Explain what is meant by the term periodicity. (1]
e lnthispart,youneedtorefertothePeriodicTab/eofthe
f Element j Na I Mg IAI Si IP IS I CI f/ementsinthedatasectionontheCD.
1:::nm l0.186 10 160 10.143 o.111 10.110 10 104 10.0<:19 From the first 18 elements o nl y, choose an element
which fits the following descriptions.
i Anelementwithanisotopethatcanberepresented
a i Explainqualitativelythisvariationinatomicradius.
as~X (1]
ii Suggestwhyitisnotpossibletousethe5amelypeof
ii The element which forms a 3- ion with the 5ame
measurement for argon, Ar. (4)
electron structure as Ne. (1(
b i Use the data section on the CD to complete the
iii The element which has the smallest third ionisation
following table of radii of the cations and anions (1(
formed by 'iOme of the period three elements
iv The element with the first six succes~ve ionisation
energies Ylown below, in kJmol- 1 [1]
[ RadlusofC.11tlon/nm Radlusolanlon/nm I
[ Na I Mg' [ Af'+ pJ.- I s'- [ ci-- I
I I I I I I {OCR Chemistry A UnitF321 QI May 2011]
ii Explain the differences in ~ze between the cations and 3 Tin mining was common practice on Dartmoor (UK) in
the corresponding atoms pre-Roman times. Most of the tin extracted was mixed
iii Explain the differences in ~ze between the anions and with copper to produce bronze.
the corresponding atoms (SI a The table belmv shows the sub-atomic particles of an
[Cambridge International AS & A Level Chemistry 9701, i50topeof tin.
Paper 23 QI a & blune 2012]
2 Thisquestionisaboutamodelofthestructureoftheatom
a A model used by chemists includes the relative charges,
therelativemassesandthedistributionofthesub-atomic
particlesmakinguptheatom. i Copyandcompletethetable (1(
Copyandcompletethetablebelow. (1( ii In terms of sub-atomic particles, how would atoms of
1
iosndifferfromatomsof 118Sn? (1]
R&latlYecharge Rebtlve b The relative atomic mass of tin is 118.7. Define the term
relative atomic mass. (3]
proton c A bronze-age shield found on Dartmoor contained
2.08kgoftin
Calculate the number of tin atoms in this bronze shield.
Giveyouranswerto three significantfigures. (2]
d Tin ore, known as cas.siterite, contains an oxide of tin
b EarlystudiesofionisationenergieshelpedKientiststo This oxide contains 78.8% tin by mass
develop a model for the electron structure of the atom. Calculate the empirical formula of this oxide. You must
Define the term fir'it ionisation energy [3) show your working. (2]
c A modern model of the atom arranges electrons into {OCR Chemistry A UnitF321 QI May2010]
orbitals,sub-shellsandshells.
43
AS Level
Physical chemistry
3 Chemical
molecules
bonding in simple
This topic is the first of two in which

we look at how atoms bond together
Learning outcomes
to form molules and compounds, Bytheeodofthistopicyoushouldbeableto
and how those particles arrange 3.2a) describe,indudingthe us.eof'dot-and-cross'diagrams,rnvalent bond ing(as
themse/vesintolargerstructuresto inhydrogeo,oxygen,chlorine,hydrogenchloride,carbondioxide,methi!ne,
form a// the matter we see around us. ethene)andrn-ordinate{dativemva~t)booding{asintheformiltionofthe
Here we describe the various types ammonium ion and in the AliC'6 molecule)
of covalent bond, and explain some 3.2b) describecovalentbor.dingintermsoforbitalove<lap,givingoand1tlxmds,
ofthepropertiesofsimplecovalent indudingthemoceptofhybrklisahontolormsp,5fliandsp'orbitals(seealso
molecules. Topjc14)
3.2c) explaintheshapesol,andbor.danglesin,moleculesbyuslngthequalitative
~olelectron-pa irrepuls.ion(includ ing lonepa irs),usingasslmpleex.amples
BFi (trigonal), CO., Oine<1r), CH 4 (tetrahedral), NHi (pyramidal), H10 {noo-linNr),
SF 6 {octahedral),PF 1 (trigonalbipyramidal)
3.2d) predkttheshapesof,andboodanglesin,rnoleculesar.diomanalogousto
those">peCifiedin l.2b) {seealsoTopic14)
3.la) describe hydrogen bonding. using ammonia and water as slm~e ex.am~es of
molecules containing N- H and 0-H groups
3.lb) unde!'stand,inslm~eterms,thernnceptolelectronegativityandapplyit
toexplainthepropertiesolmolecu lessuchasbondpolarityandthedipole
mome!lts of molecules {part, see also Topk 10)
3.lc) explain the terms bond energy, bond length and bond polarity and use them to
comparethereactivitiesolcovalentbor.ds{seealsolopic 15)
3.ld) describeintermolecularforces(vanderWaals'lorces),basedoopermaneotar.d
induceddipoles,asinCHCl1(1),Br1{1}andtheliquklGroup18e~nts
3.Sc) show understanding of chemical reiKt ions in terms of e!lergy transfers associated
withthebreakingandmakingofchemic.albonds{seealsolopic 14)
3.1 Introduction
Of the wrnl number of individual. chemically-pure substances known to exisi,
several million are com pounds , fonned when two or more elements are
chemically bonded together. Less than JOO substances are clcm C' n ts. Only six of
these elements consist of free. unbonded atoms at room temperature . These are
the noble gases in Group 18. All O!her elements exist as individual molecules. or
giant molecules. or metallic lattices . ln all three cases. the atoms of the element are
chemically bonded to one another.
This shows that the natural Slate of atoms (that is. the state whe..,- they have the
lowest energy) is the bonded Slate. Atoms prefer' to be bonded to one anO!her.
rather than to be floating free through space. They give out energy when they fom1
bonds. On the O!her hand. it always requires an input of energy to break a chemical
bond - bond -breaking is an ende1hem1ic process (see Figure }. l).
44
Chemical bonding in simple molecules I
Flgure3.1 Soodbl!'akingi1emlothe11Tiic
~ j
, eparate atoms - , - ~ ~ - -
'""';"'"
The bond strength is related to the value of AH in Figure 3.1, that is. the enthalpy
change th.at occurs when one mole of bonds in a gaseous compound is broken
forming gas-phase atoms (see section 5.5). The larger AH is. the stronger is the bond .
We saw in Topic 2 that the negatively charged electrons in an atom are attracted
tothepositivelychargednucleus: an electron in an atom haslesspo(emialenergy
than an electron on its own outside an atom . It therefore requires energy to remove
an electron from an atom. In this topic we discover a similar reason why atoms bond
together to form compounds. This is because the electrons on one atom are attracted
to the nucleus of ancxher. causing the bonded system to have less po(ential energy
than in its unbonded state. (The three major types of bonding - covalent. ionic and
metallic - differ from one an(){her only in how far this attraction to an(){her nucleus
overcomes the attraction of the electron to its own nucleus.)
4' 3.2 Covalent bonding-the hydrogen

molecule
We shall look first at the simplest pos.sible bond. that belw=n the two hydrogen atoms
in the hydrogen molecule. Imagine two hydrogen atoms, initially a large distance
apatt.approachingeach<Xher. Astheygetclosertogether,thefirsteffeawLilbeth.at
the elearon of one atom wiU =perience a n,pulsiOfl from the electron Ofl the (){her
atom, but this will be compensated by the attraction it will experience tmvards the
other atom"s nucleus (in addition to the attraction it always =perience-s from its own
nucleus). Remember that the electron in an atom spends some of its time at quite a large
distance from the nucleus (see Figure 2.16, page.30). Asthe hydrogen atoms get closer
still. the 1,vo elearons will encounter an even gn,-:,ter attraction to the opposite nucleus,
but \\ill also coruinue to repel each <Xher. Eventually. when the two nuclei become
vetyclosetogether,theyinturnwill.'itatttorepeleachather.sincetheybathh.avethe
same (positive) charge. lbe most stable situation will be when the attractions of the
t,vo electrons to the two nuclei are ju.'it balanced by the electron-electron and nucleus-
nucleus repulsions. A t'Ovalcnt bond has formed. The decrease in potential energy at
this point from the unbonded state is called the bond encrgr. and the nucleus-nucleus
distance at which this occurs is known as the bond le ngt h (see Figure 3.2).
Flgure3.2Potentialenergyagainst
internucleardi1taocef01"thehydrogen
molecule
436kJmo1- 1
45
PHYSICAL CHEMISTRY
Being anracted to lxxh the hydrogen nuclei, the two electrons spend most of their
time in the region half-way between them. and on the axis that tCJins them . This is
wherethehighestelearondensity(orelectron probability)occursinasinglecovalent
bond (see Figure 3.3).
The two electrons are therefore shared between the two adjacent atoms. As we
maximumelectronden,ity mentioned in sectiOfl 2.7. we use the word (atomic) o rbita l to describe the region of
Flgurel.l Amolec:u!arorbitali1aregion spacearoundthenudeusofanatomthatisoccupied bya panicularelectron. lna
betweentwobondedatom11\tle1Ethe similar way, we can use the cerm m o lecula r o rbit a l to describe the region of space
electmndensityi1coocentrated within a molecule where a panicular electron is to be found .
3.3 Representing covalent bonds

Depending on the information we want to convey. we can use various ""Y" to
represent a covalent bond, as listed below.
ThedOl -and--crossdiagrnm:
The da1 -and--Cf05s diagram including Venn diagram boundaries - this is preferred
for more complicated molecules. as it allows an easy check to be made of exactly
The line diagram (one line for each lxmd) - this is not very informative for small
simple molecules, but is of!en less confusing than drawing ou! individual electrons
for larger, more complex molecules .
H + H ---t H- H
3.4 Covalent bonding with second-row

elements
Bonding and valence-shell electrons
When an atom bonds with Olhers. it is normally only the electrons in the outermost
shell of the atom tha! take pan in lxmding. The ou!ermost shell is called the vale n c e
s hcll. Allelectronsinthevalenceshellcanbeconsideredtogetherasagroup.W'hen
we look in simple terms al the bonding, we can ignore the distinction between the
various types of otbitals (s, p. d, etc .) in a shell. The number of electrons in the
valence shell is the same as the group number of the element in the Periodic Table
(see Topic 10).
lf an atom has more than o ne electron in its valence shell, it can form more than
one covalent bond to Olher atoms . For example , the beryJHum atom has a pair of
2s electrons. When forming a compound such as beryJHum hydride. BeH,, these
can unpair themselves and form two lxmds with two Olher atoms . The boron atom
(2s 2 2p 1) can form three lxmds. The bonding in beryJHum hydride and boron hydride
is shown in FigureJ.4.
Rgurel .4Dot-anckrossdi.lgrarmshowhj
bery1liumhydricie.BeH,.andboroohydrde.BH1
{ltisworthremembe!ingthatalelectron'iare
Klentical. no matter which atom they came Imm
OlJ"rep!l'Sefltirigthema1dot1ar!d=is H : se ; H
merelyforouro11Tlbenefit,tomahitdeartou1
whidtatomtheywereorigin,ljlyassodatOOwilh)
The carbon a!om in methane has four electrons in its valence shell (2s22p 2) , and so
46
Flgurel.5 Dot-aml-005sdiagramfor
methane. CH., (Often. fDfdarity.bonding
diagram1 show ooly the electrom in the outer
shell.omittingtheinner1hel1'iforrnmpali!.0n,
bothdiagromsformethoneareshownhere)
Thegenemlruleisthat:
Elements with one t o four electrons in their valence shells form the same number of
covalentbondsasthenumberof valeoce-she!lelectrons
lmponamly. carbon 3toms form .strong bonds to Ol:her carbon atoms (as do a few
Flgurel.6 Dot-and-crossdiagromfDf other elements) . This allows the millions o f organic con1JX>unds to be stable. The
eth;me.C,H 0 sintplestmoleculewithararbon--carbonbondisethan e(seeFigureJ.6).
More than four valence-shell electrons

When the number of valence-.sheU electrons is greater than four. the max imum po,;sible
number of bonds is 00! always formed. This is becau se atoms of the elements d the
second row of the Periodic Table have only four orbitals in their valence shells (2s, 2p~,
2p_.. 2p.) and so cannot accommcxlate mo"' than four pairs of electrons. The number of
boocLs they form is restricted by this overall maximum of eight electrons, because every
new bond brings anOffler electron into the valence shell. For ex:imple. n itrogen has five
valence-shell electrons. In the moleaJle of ammonia (NH 3) the"' a"' three N- H bonds.
Theseinvolve thesharingofthreenitrogenelectronswiththreefromthehydrogen
atoms . These three additional electrons bring the valence .shell total to eight. The outer
sheU is therefore filled. with a full octt.'t of electrons. No funher bonds ran form. The
F1gurel.7 Dol-,md-cl05sdiagram remaining Nm of the five electrons in nitrogen"s valence sheU remain unbonded. 3 S a
fDfammonla.NH 1 lone pair. occupying an orbital associated with only the nitrogen atom (see figure 3.7).
The general rule is that :
Elemeots o fthesec:ondperiod with morethanfour electronsinthe ir o uter~lsfmm

(8 - n ) rn~a!ent bonds, where n = the number of valence.shell electrons
Similarly. oxygen (2s 1 2p~), "ith six electrons in its valence shell. can form only two
covalent bonds, with cwo lone pairs of electrons "'maining . Fluorine ( 2s22ps:J, with
seven valence-shell electrons. can form o n ly one bond. leaving three Jone pairs
arou ndthefluorineatom (SC<."'Figu,.,3.8).
Flgurel.8 Dot-and-crossdiagramsforw.1ter.
H,O.andhydrogenftooride.HFOxygenc:an
formtwobonds(8-6=2)andMuminejust H : F
one{8-7=1)
Worked example
Draw d iag rams showing the bonding in nitrogen trifluofid e, NFi , and hydrogeri peroxid e, HiO.,
Answe r
Flgurel.9
Drawdiagramsshowir,gthebor.dingin
t hefo llowingmoJecules
1 BF1 2 N1H4
3 CH10H 4 CHif1
,,o,
47
PHYSICAL CHEMISTRY
3.5 Covalent bonding with third-row

elements
Unlike elements in the second row of the Periodic Table. those in the third and
subsequent rows can use their d orbitals in bonding, as well as theirs and p orbitals.
They rnn the..,-fore form more than four covalent bonds to other atoms. Like nitrogen.
phosphorus(ls 2 2s'2p63s'3p 3)hasfiveelectronsinitsvalenceshell.ButbeC3use
3s. three Jp and one 3d) it can use all five of
ii can make use of five oibitals (one
itsvalence-shellelectronsinbondingwithfluorine. It therefore forms phosphorus
pentachloride.PFs,aswellasphosphorustri(luoride.PF1 (seeFig ure3 .10).
Flgure3.10D0tand-uo11diagramsfur
phmphorustrifluOfide,PF"andphosphorus :..;.
pentafluOOde,P'f,
p : F:
: F: : ;...
In a simibr way. sulfur can use all its valence-shell electrons in six orbitals (one js.
thr= 3p and two 3d) to form sulfur hexafluoride. SP6. Chlorine does nOl form ClP 7,
however. The chlorine atom is too small for .seven Ouorine atoms to assemble aro1.md
it. Chlorine does, though. form ClF 3 and ClF5 in addition to ClF.
Worked example
Orawadiagrnmtoshowthebonding inchlorinepeotafluoride,CIF 5
Answer
Ftgure3.11
1 Sulfurformsatetrafluoride, SF 4 .0rawadiagramtoshowitsbooding.
2 ii How many valeoce4el l ~ectrons does chlorine use for bonding in chlorine
trifluoride.CIF1?
b So how many e~rons are ~ft in the valences.hell?
c So how many !one pairs of e~rons are there on the chlorine atom in chlorine
trifluoride?
3.6 The covalency table

As =plained in sections 3.4 and 3.S, the number of covalem bonds formed by an atom
depends on the number of electrons available for booding. and the number of valence-
shell orbitals it can use to put the elect!Ofls into. Formanyelements,thenumberof
bonds formed is a fixed quantity and is termed the covalcncy oftheelemeru. It is often
related to its group number in the Pericx:lk Table. As shown above, elements in Groups
lSto17inthethirdandsubsequentrU<\'softhePeriodkTable(Pericx:13andhigher)c:m
use a variable number of elecrrons in bonding. They can therefore display more than one
covalency. Table j.l shows the fll05t usual covalendes of .some common elements
48
Symbo l Cova len cy
hydrogen
bel)'llium
nitrogen
phosphorus
Worked example
1 Whataretheformulaeofthethll.'e What could be the formulae of compounds formed from the following p;1i11 of elements?
possibleoxidesofsulfur? 11 boronandnitrogen b phosphorusandoxygen
2 Uselable3.1towritethel04'mulae
ofthesim~estrnmpoundslormed
Answer
The elements must combine in rudi a ratio that their total covaleocies are equal to e.-ich othef
between
11 Thecovalencie1ofboronandnit1ogenareboth3,sooneatomofboronwill
11 carbonandhyd1ogen
combine with one at om of nitrogen . The formula is therefore BN (3 for 8 = 3 for N)
b oxyge nandfluo rine
b Thecovaleocyofoxygeoi12,andthatofphosphoruscanbeeither3orS.We'WOuld
c borooandchlorine
therefore expect two possible phosphorus oxides: P;i03 {2 x 3 for P ~ 3 x 2 104' O) and
d nitrogenandbrom ine
P20 5 (2x5forP = Sx21orO)
e carbooandoxygl'fl
3.7 Dative bonding

So far. we have looked al covalent bonds where each atom provides one electron
co form the bond. his possible , however. for jusi one of the acorns co provide both
bonding electrons . This atom is rnlled the donor atom. and the two electrons it
provides come from a lone pair on that atom. The cther atom in the bond is called
the acccp1or atom. It must contain an empty orbital in its valence shell . This kind of
bonding is called datlve bonding or co-0rdlnme bonding. The apparent covalency
ofeachatorncanincreaseasare.sultofdmivebonding.
For example. when gaseous ammonia and gaseous boron trilluoride react together,
a white solid is formed, with the fomrnla NH.lBF.l . The nitrogen acorn in ammonia
has a lone pair. and the boron atom in boron trifluoride has an empty 2p orbital.
The nitrogen 's Jone pair rnn overlap with this empty orbital. as shown in Figure J .l 2.
Flgure3.12 formirigadative(co--0rdinate)
bondln NH,BF, : F : : F;
: F; ; F:
The dative lxmd. once formed. is no different from any <Xher covalent bond. For
=ample. when g aseous ammonia and gaseous hydrogen chloride reaa, the white
solid ammonium chloride is formed . The Jone pair o f electrons on the nitrogen aton1
of ammonia has formed a dative bond with the hydrogen atom of the hydrogen
49
PHYSICAL CHEMISTRY
chloride molecule (see Figure 3 .13). ( At the same time. the H-Cl bond breaks, and
the electrons thm were in the bond form a fourth Jone pair on the chlorine atom.
With 18 electrons and only 17 procons. this now becomes the negatively charged
chloride ion. Ionic bonding is covered in detail in Topic 4 .)
Flgurel.1l Formi11ganionicbondi11
ammoniumchlolicie,NH,CI
!
H I: N :,---..,. H:i; Cl : -~ N : H
The shape of the ammonium ion is a regular tetrahedron, the same as that of
me1hane molecule (see Figure 3 .14). All four N- H bonds are exactly the same. It is
nOI po65ible to tell which one '""' fanned in a dative way.
Flgurel.14 The ammonium ion am!
methane are both tetrahedral
[
H/C~H
3.8 Multiple bonding

Double and triple bonds
Atoms can share more than one electron pair with their neighbours. Sharing two
electron pairs produces 3 double bond , 3nd s h.tring three produces a triple bond . The
covalencies still conform to those in Table J. 1. Examples d oxygen. nitrogen
and caibon atoms forming multiple bonds are shown in Figure J .15.
Flgurel.15Dot-aml-c:rmsdiagram1foro,.
N,,mdethene,c,H,
Flgurel.16 Worked example

Draw a dot-and-cross diagram and a line diagram of the carbon dioxide molecule, C01
0 ; C Answer
Thernva lendesofm,;ygenandcarbonare2and4res.pectively.Theonlypos,;iblebonding
arrangemeot is therefore O=C=O, and the electrom are shated as shown in Figure 3.16
Draw line di a.grams and dot-and-cross d~rams to show the bonding in the lollOW1ng
molecules
50
3.9 The shapes of molecules
One of the major advances in chemistry occurred in 1874, when the Du cch chemist
Jacobus van"! Hoff suggested for the first time that mo lecules posses,ed a definite.
unique, three-dimensional shape. The shapes o f molecules are determined by the
angles between the bonds within them . In tum. the bond a ngles are de!ennined by
chearrangernentoftheelectronsaroundeachatom.
VSEPR theory
Bernuse o ftheirsimilar (negative) charge.electronpairsrepeleachoiher. The
electron pairsintheouter (valence) shellof anatomwiJJexperiencetheleast
repulsion when they are as far apan from one ancxher as possible. This applies both
to bonded pairs and to non -bonded (lone) pairs. This simple principle allows u s to
predict the shapes of simple molecules . The theory. developed by Nevil Sidgwick
and Herbcn Powell in 1940. is known as the rn lc n c<'-sh c ll eleclron-pa ir rqmlsio n
th<'ory (or VSEPR for shon). In order to work out the shape of a molecule. the
theoryisappliedasfollows .
I Draw the dOl--and--cro.ss structure of the molecule. and hence count the number of
electronpairsaroundeachacorn .
2 These pairs will take up positions where they are as far apan from one ancxher as
possible. The angles between the pairs will depend on the number of pairs around
theatom (seefigureJ.17).
Flgure l .17 The1ha~1inwhi::hn molecule s hape numbe r of dH cription

electrool)dir1.irmmdacentralatomarr,mge e leclronpairs
themselves.withn = 2.3.4.5aftd6
:- < tr iangu lar pl anar

(trigona lplanar)
.;f--' tr iangularbipyramidal
(trigona lbipyramidal)
51
PHYSICAL CHEMISTRY
.1 Orbitalscontaininglonepairsarelargerthanthosecontainingbondedpairs. and
mke up mo..._.. s pace around the central atom. They the..,fore "'Pel the oiher pairs
that surround the atom more strong ly. This causes the angle between two Jone
pairs to be laiger than the angle between a Jone pair and a bonded pair, which in
turn is larger than the angle bet,veen two bonded pairs :
(LP---LPangle) >(LP---BPangle)> (BP- BPangle)
4 Although they a"' very importam in determining the shape of a molecule, !he Jone
pairs are nOI: included when the molecule's shape is described . For example, the
nx,lecules CH 4, NH 3 and H,O all have four pairs of electrons in the valence shell
ofthecentrnlatom (see Fig ure3.l8). Thesefourpairsarrangethemselvesina
(roug hly) tetrnhedral fashion . But only the methane molecule is described as having
a tetrahedral shape . Ammonia is pyramidal (ic has only three bonds), and water is
described as a bem molecule (it has only two bonds).
Flgure3.18The1hape1ofmethane,
ammoniaandwaterare.11predictl.'dfrom
the irfourpairsofelectmnsalU\/ndthecentral
Q Q
atom.Looepai11repelotherelectroopair1
morestronglythantlood irigpairsdo,,;othe
bondangl!"iinammooiaandwateraieslightly
sm;illerthanthetetrahl.'dralangleof109.5
H<-\.,H
107' ~
,<v
104.S' H
Worked example
WOO<outtheshapl!softhefollowingmolecules.
CCl4 b 8F1 c PF1
Answer
Flgure3.19 Thevalenc:es.hellofthecarbonatominCCl4
1
cootaimeightelec:tmm,arrangedinfour
bondedp.i irs .ltthereforetakesup aregular
tetrahedralsliapi!,justlikemethane{see
Figure3.19) .
c1<__\c1
C1
,09.5
b Flgure3.20 Thevalenceshelloftheboronatom in8F 1

rnntainssixelectrons,arrangedinthree
bondedpairs{nolonepairs - seepage47).
ltthustakesuparegulartriangularplanar
sliapl!,withall bondang le1beingequalat120
(seeFigure3.20)
Workoottheshapesof thefollowing ' "'"'"'" ~- Thevalence-Jie llofthephosphorusatominPF1

containstenelectrons:fivelromptiosphorus,
andoneeachlromthefivefluorineatoms(see
molecules
f-J,. ,).:f,20 page48).Theshapl!wi llbearegulartrigonal
I"'
1 8eH1
bipyramid,withbondang\esol120"and90'
2 CIF1 (Explainwhythi1 i1calleda {seeFigure3.21).
'T-s.haped'molecule.)
3 SF 6
Double bonds and VSEPR

,.,. When a molecule contains a double bond, the four electrons in this bond count as
one group of electrons, as far as the VSEPR theo,y is concerned. For example, the
:?#~ ~: carbon in carbon dioxide, which is doubly bonded to each of the oxygen atoms,
Flgurel.22Cartiondioxick>i1alinear issurroundedbyjusttwo electrongroups. ltisthereforepredictedtobea linear
mote rule m o lecule(seeFigure3.22).
52
Worked example
Predicttheshapeofthesulfurdioxidemolecule
Answer
Sulfur shares two of its valence-she ll electrons with l'iKh of the two oxygen atoms, forming
twodooblebonds.lthastwoelectronsleftover,whichformalonepair.Thereare
thereforethreegroupsofelectronsaroundthesulfuratom,andthesewillarrange
:.~Q?.~ themselves approximately into a triangular planar shape. The so, molecule is therefore
bent, as shown in Figure 3.23 {remember that lone pa irs are ign!lfed when the shape is
described),witha0 - S-Obondangleofabout120.(ln fact,theangleisveryslightly
Flgure l.2l Sutfurdioxidei1abentmoiernle less.at119,owingtotheextrarepulsionbythelonepair.)
Predicttheshapesoftr>l'followingmoJecules
{Notethatatriplebond,like adoublebond,c.anbeconsideredasasinglegroupof
electrons.)
Later in this topic we shall see how ""' can predict the shapes o f molecules such as
ethene and carbon dioxide by studying their bonding (see section 3.15).
Summary: the shapes of molecules

Table J .2 summarises how the numbers of bonded and non-bonded electron pairs
deiermine the shapes of molecules.
Table3.2 Toesh~ofmoleculesas Total number of Number of Number of Shape Example

determinedbythenumbmofbomlirig electronpalrs bondlngpalrs lonepalrs
and non-bondingelectronpair1
triangu!arplariar 8f1 (seefigure3.20)
H,0{1!.'!'figure3.18)
triangu!arpyramidal NH1 (1!.'!'figure3 .1 8)
CH,(l!.'!'figure3.18)
Xef,(ll'l'figure3.24)
Sf, (seefigure3.24)
trigooal bipyramidal Pfs(seefigure3.21)
Flgurel.24 Toesh~ofXef,.C lf,andSf,

areall determinedbythefivepair1of elect10111
amundthecentralatom
3.10 Electronegativity and bond polarity

The essential feature of covalent bonds is that the electrons forming the bond are
shared between the two atoms. But that sharing does nOI have to be 3n equal one .
The electronegativity ofanatomis Unless bcxh aroms are the .same (for example in the molecules of hydrogen. H,. or
ameasureofitsab ilitytoattractthe oxygen. 0 1). it is more than likely that they have different dcctroncgmivities, and
electronsinarnvalentbondtoitself thisleadstounequalsharing.
53
PHYSICAL CHEMISTRY
Several chemistshavedevelopedquantil3tivescalesofelectronegativityvalues.
One of the most commonly used is the scale devised by the American chemist
Linus Pauling in 1960. Numericalvaluesofelectronegativityon this scale range
from fluorine. with a value of 4.0, to an alkali metal such as sodium, with a
valueof0 .9.
Figure 3.25 shows the elearonegativity values o f the elements in the first
three rows of the Periodic Table . NO{ice that the larger the number, the more
electronegative (electron anmcting) theatomis.
Flgurel.25 Electrorn.>g.itivitiesofelementsin
thefir,;tthreeraNSof thePeriodicTable
Be 1.s B 2.0 C 2.s N 3.0 O H F 4.0
Mg 1.2 Al 1.s Si 1.8 p 2.1 S 2.s Cl 3.o
Theelectronegativityvaluedependsonthe<"ffectivenuclearcharge. Thisis
similar to the way that ionisation energies depend o n the effective nuclear charg e,
and the reason is also similar. The nucleus of a fluorine atom (electronegativity
value = 4.0), for example, contains more pfOl:ons and a higher effective nuclear
charg e than !hat of a rnrbonatom (electronegativityvalue = 2.S), and sois able
to attract electrons more strongly than carbon. In the C- F bond. therefore. the
Flgurel.26 Thecarbon-ft umin e electrons will be found. on average, nearer to fluorine than to carbon . This will
bondi'ipo!ar cause a partial movement o f charge towards the fluorine a!om. resulting in a
p o la r bo n d (see Fig ure 3.26).
This partial c h arge sep aration is represented by the Greek letter O (delta).
followed by + or - as appropria!e. The cross-and-arrow' symbol in Figure 3.26 is
also sometimes used to show the direction in which the electrons are attracted
moreSlrongly.
Most covalent bonds between different atoms are polar. If the electronegativity
difference is large enough. one atom can attract the bonded electron pair so much
that i! is comple!ely transferred. and an ionic bond is formed (see section 4.6).
Worked example 1
Usethl'l'iKlrof)l'galivilil'5inFigure3.2Stopredictthl'directionofpolari5ationinthl'
following bonds.
ii C- 0 b 0-H c Al-Cl
Whichofthesethrel.'bondsi5themostpoklr?
Answer
il /i,C-0&- electmnl'Qillivitydifferencl.'~3.5
Which is the most poklr of the following b &-o-HM electfonl'Qiltivily differenCI' ~ 3.5
thrl.'ebonds? c /i,AI--C i&- electronl'QiltivitydifferenCl'z3.0
S-C I A!-C I is the most polar of these thrl.'e bonds.
3.11 Polarity of molecules

Dipoles of molecules
The drift of bonded electrons to the more electronegative atom results in a separation
of charge, tenned a d ipole. Each of the polar bonds in a molecule has its own
dipole associated with it. The overall dipole of the molecule depends on its shape.
Depending on !he relative angles between the bonds. the indhidual bond dipoles
caneitherreinforceorcanceleac hoiher. lfrnncellation iscomple!e.theresulling
molecule wiJJ have no dipole. and so will be non-polar. If the bond dipoles reinforce
each oiher, m o lecules with very large dipoles can be formed .
54
For example. boih hydrogen. H2. and (luorine. F,. are non-polar molecules. but
hydrogen (luoride has a large dipole due to the much larger electronegmivicy of
(luorine(seeFigure3.27).
Flgure3.27Theelectrooegativltydiffel!'nce
giveshydrogenftuorideal.irgedipole
The two C=O bonds in carbon dioxide are pobr, but because the angle between
them is 180, exact rnncellmion occurs. and the molecule o f co, is non-polar.
A simibr situation occurs in tetrachlorometh.rne. but not in chloromethane (see
Figure3.28).
Flgurel.28 Thedipolescancelincarbon
diaxide.indtetrachlorometh;me,butnotin
Worked example
Which of the molecules in Figure 3.29 has no dipole moment?
&~
Flgure3.29Toedkhklrobenlefle1
' 0
Answer
Compound C, 1.4-dichlorobenlefle. In compound C, the C-CI dipoles are oo opposite ,;ides
ofthebenzenering,sotheirdipo!esopposeeachotherl'{Jual!y.lnrnmpoonds Aand B,the
C-CI dipoles are, more or less, on the same o;ide of the ring
1 Which of the two compounds A and B, in the worked example above, will have the
larger dipole moment, and l'hly?
2 Wo rk out the shapes of the following molecules and decide which of them are polar.
ii CiH6 b CHiCli c CH10H d SF,
Lone pairs and dipoles

Polarity of mol=ules is also mused by the presena,- of a lone pair of electrons o n
one side on the a,-ntrnl atom. This is an area of negative charge and so it forms the
&-- end of a dipole . In the ammonia molecule, this dipole reinforces the dipoles due
to the N- H bonds. resulting in a highly polar molecule. A similar situ ation occurs
withwmer(seeFigure3.3()).
Figure 3.30 Ammooi.a and water .ire highly

polarmclec:ules
55
PHYSICAL CHEMISTRY
Table 3.3 The dipole moments of some Comparing dipoles

rnmmoncOYalentmok>c:ul!.'5
The strength of a dipole is measured by its dipo le momC' nt . which is the product
Dipole momenUD of the separated electric charge. 6+ or&--, and the distance betw<"en them. Dipole
moments can be measured. and they can also be calculated. Table 3.3 lists the dipole
moments of some common molecules. The debye unit. D (named after the chemist
Peter Debye) , has the dimensions of coulomb-metre . If. as in an ionic bond. a full
electron charge were separated by a distance of 0.15nm, the dipole moment would
be 7.0D. It rnn therdore be seen th31 even the most p;:>lar of covalem bonds. such
as H- P, are still a long way from being ionic .
3.12 Induced polarisation of bonds

A bond's n31ural polarity, caused by the different electronegativities of the bonded
atoms , can be increased by a ne:irby strong electric field. A nemby electric field
can also produce a polarity in a bond that was originally non-polar. This induced
polarity is often followed by the breaking of the bond. The nearby electric field can
be due to an area of concentrated electron density, o r an electron-<leficiem acorn. or a
small highly-charged cation. Examples of each of these cases are as follows:
the polarisation o f a bromine molecule by an ethene molecule, as shown in

Figure3.31 (see Topic 14)
Flgure3.31 Polarisationofbromineby
"""'"
the polarisation of a chlorine molecule by aluminium chloride. as shown in

Figure3.32(seeTopic25)
Flgurel.32Polari!.ltionofch1Dfineby
aluminium chloride
the polarisation of the carbonme ion by a Group 2 metal ion, as shown in

Figure3.33(seeTopic20).
Flgurel.33Po!arisationolthecartxmate
ionbyaGmup2metalion
The induced polarisation of m o lecu les, and the effect this has on intermolecular
attractions, is discussed later in this topic. in.section 3.17.
3.13 lsoelectronic molecules and ions

l soclt'Clronic means having the same number of electrons' . The term can be applied
co molecules or ions which have the same tornl number of electrons, or to molecules
or ions that have the same number of electrons in their valence shells . Because the
distribution of electrons in the valence shell determines the shape of a molecule
molecules or ions that are isoelectronic with one an{){her have the same basic shape,
often with identical bond angles too. For example:
the tetmhydridobomte(U[) ion, BH.i- , methane, rn 4, and the ammonium ion, NH/,
are all regular tetrahedra, with H- X - H angles of 109.5
56
the borate ion, Bo/-, the carlxmate ion. co/- . and the nitrate io n, No3- , are all
triangular planar, with 0 -X-O angles of 120
the oxonium ion, H 3o+. 3nd ammonb, NH 3, 3re l:xxh trbngular pyramids with
H- X- H 3ngles of 107.
Counting the electrons in the valence shell aro,rnd 30 atom is therefore a useful
way of predicting the sha.pe of a molecule .
Worked example
Predicttheshape1ofthefoll01Ningion1
themethy!ution,CH]'
b themethy1anion,CH1-
Givelltheinformationthatsulfurtrioxide
c thenitron iumulkln,NO/
istriangularplanar,thesulfiteanion,
so/- ,isalfi<mgularpyramid,andthe Answer
sulfateion,so/- istetrahedrnl,predict a CH]'i1isoelectronicwithBH1 (sixelectrons intheoutershell),andsoiti1atfiilngular
theshapesofthefollowingions pjanarion
b CHi- is isoelectronicwith NH 3, so it is a triangular pyramidal ion
1 Clo1- 2 PO}- 3 PO/-
c NOiisisoelectronicwithCO.,,soitisalir.earion
3.14 The overlap of orbitals - cr bonds

A single bond is produced when a pair of electrons is s hared between two atoms .
The electron pair occupies a molecular orbital formed by the overbp of an atomic
oibital on each atom . The atomic orbitals can be s orbitals or p orbitals, or a mixture
ofthetwo (seeFigure}.yl) .
Flgu rel .34 Thes.hapesofmolecularortiilals

fomwdbytheol'!.'flapofatomicortJitals
region of overlap
region of overlap
region of overlap
The resulting area of electron density is in the region between the bonded atoms ,
with the brgest density on the 3Xis joining the atom centres . Looked at end on ',
these orbitals have a circular symmetry (see Figure 3.35).
F1gure l .35 TheC -<: singlebond

(acrbond)
,/'/:, J',,/
A ,,,
By analogy with the spherically symmetric s orbitals of atoms, these are termed
(J (sigma) orbitals, (J being the Greek letter corresponding to s. The resulting bond
is called a (Jbond.
57
PHYSICAL CHEMISTRY
Hybridisation of orbitals
\Ve saw on page 51 that the electron pairs which surround a central atom arrange
themselves in such a ""Y as to minimise the repulsion between them . If there are
threeelectronpairs, theyarrangethemselvesin atriangularplanararrangement.and
if there are four electron pairs, they arrange themselves tetrahedrally. What molecular
orbitals can be used bytheelectronstopointinthesedirections?
In Topic 2 we saw that. for second -row elements. the orbitals available for bonding
are the spherical 2s otbirnls and the three dumbbell-shaped 2p orbitals
Figure 3 .34 shows how two 2p orbitals can overbp to produce a o molecular
orbital. But. as can be seen inFigureJ.34. this molecular orbital points in the same
direction as the original p atomic orbitals . So molecular orbitals formed from the
2p..., 2p_,, and 2p~ orbitals would be pointing along the x -, y- and z-axes, thm is, at
right angles to one anO!her. But for the triangular planar geometry of three electron
pairs, there need to be three orbitals that are JX)inting at 120 from one anOl:her, and
in the !etmhedral case of four electron pairs, there need to be four orbitals JX)inting
at 1()9.5 from o ne anO!her. Suitable orbitals that point in the right directions can be
fonned by mixing, or h y bridising, the s and p atomic orbitals.
lfthe2s, 2p.,and 2pyrnbitalsarehybridisedtogether,theresultisthreeidemical
orbitals JX)iming at 12<1' from one anO!her - which is =actlywhac we want! This rype
of hybridisation is called s p ' (pronounced 'ess pee two'), and the three hybrid atomic
orbitals arecalledsp'orbitals.
Similarly , ifthe2sorbitalis hybridised withallthreeofthe 2porbitals, fours p '
("ess P"" three') hybrid orbitals are formed, which point at 109.5 from one ancther.
Figure 3.36 shows what sp' and sp 3 orbitals look like.
Flgure3.36 The1p'and1p'orbita!s
one ,andtwoporbitals three'fl 2 hybrid

orbital,(trigonalplanar)
four,p 1 hybrid
orbital,(tetrahedra l)
3.15 Localised rr orbitals-the formation

of rr bonds
We now look at the orbitals that are used to form double bonds. We shall see that the
way double bonds are formed can explain their shape and many of their propenies.
In figure 3 .34 we have shown two p orbitals overlapping end-on' to form a
CJ bond. But it is also possible for !wo p orbitals to overlap sideways, to produce a
molecular orbital which has two areas of electron density, one above and one below
theaxis joiningthetwoatomcentres(seeFigureJ.37).
58
Flgurel .37 Sidewayo;overlapoftwo
porbital1tofo11Tiarorbital
The "end-0n'view of this orl:,ital kx,ks very like an momic porbital. It is rnlled a It (pi)orbital.
it being the Greek lener corresponding top. and the re-suiting bond is called a ,: bond
Flgure3.38The11 bo!ldbetweentwo
c;1rbonatorm
0
6
This sideways overlap of mu p orbitals is always accompanied by the end-on overlap of
mu other rnbitals on the same atoms. So. although it is possible to t<Xn mu atoms with
only a o lx>nd. it is no1 p;:,ssible to t<Xn tvm atoms with only a It bond. A d o uble bond
consists of a o bond and a II bond between the same mu atoms (sec Figure J.39).
Flgurel.39 Aurbori-c;irbondouble
oood
<f-- c~
~c---
(:.:)
The bonding in ethene
The stronger of the mu bonds in a double bond is usually the o bond formed by end-on
overlap. and the weaker bond is the It bond . The following data for ethane and ethene
demonstrate this (assuming th:n the o bond has the same strength in bol:h compounds) :
strength ofC-C (single, o) bond in ethane, CH 3-CHi = 376kJmol=:

strength ofC=C (double. o + It) bond in ethene, CH,=<:H, = 7'1JJkJmol
Therefore.
1
extra strength due to the It bond in ethem,. CH,=<:H, = )44kJmol-
The full picture of the bonding in the ethene molecule rnn therefore be coru;tructed as
follow:s. Each rnrlxm acorn shares three electrons (one with each of the two hydrogen
atoms. and one with the other rnibon atom). These form five O lx>nds (using sp' hybrid
orbitals on carboo). The fourth electron in the valence shell Ofl each caibon atom occupies
an atomic p~ orbital. These orbitals overlap with each other to fonn a it orbital. The it bond
forms when the founh electron on each atom is .shared in this II orbital (see Figure 3.40)
Flgure3.40The bondinginethene
" ~ ' "

,/ ()j()""'-,
59
PHYSICAL CHEMISTRY
Mutual repulsion of the electrons in the three cr bonds around each carbon atom
tends to place them as far apan from o ne anOlher as possible (..,.,. page 51 ). The
predicted angles (H-C- H = H -C-C = 120") are very dose to chose obsern,d
( H -C- H = l 17, H -C-C = 121.5).
The It bond confers various properties on the ethene molecule.
Being the weaker of the two, the It bood is more reaaive than the o bond . Many
reactionsofetheneinvolveonlythebreaking oftheitbond.theobond=iningintact.
The two areas of overlap in the It bond (lxxh above and below the plane of the
nx,lecule) cause ethem, to be a rig id molecule. with no easy rofation of one end
with respect to the O{her (see Figure 3.41 ). This is in contrast to e thane, and le:ids
to the existence of cis----trans isomerism in alkene s
These features are developed funher in Topics 12 and 14.

Flgure l .41 Thexbcmdpreventsmtation
arou!ldthecaitxm--carboodoublebond
" ~ /"
,/()(_)"'-,
rotation possible around no rotat ion possible
the single bond
Trip le bonds
Triple bonds are formed when two p orbitals from each o f the bonding atoms o verbp
sideways. forming two II orbitals (in addition to the CJ orbital formed by the end-0n
overlap of the third p orbital on each mon,). This occurs in the ethyne molecule.
C,H 2. andinthenitrogenmolecule. N, (seeFigureJ.42) .
Flgure3.42Triplebo!ldsln a nitrogen;md aN,

b ethyne
Pr+P, Pr+P,
b C,H,
,.,. .. ,.,
A s ing le carbon atom can also use two of its p orl,itals to form II orbirnls with ra.o
separate bonding atoms . This occurs in the carbon dioxide molecule . co, (see
FigureJ.43).
Fl g ure l .43ThetwonbondsITTcarboo
dioxide
60
Worked example
Desc:ribethebondir,ginandtheshapeolthemoleculesol
a h~rogencyanide,HCN
b metharial. CH10 .
Answer
The left-hand side of the HCN molecule is the same as one end of the ethyne molecule,
and the right-hand side is the same as one end of the nitrogen molecule. HCN is linear,
Desc:ribethebondir,ginandtheshapeof with one single bond and one triple bond. {One o bond between Hand C, one o bond
eachof thefollowir,gmolecules between C and N, and two it bonds between C and N.)
b Theleft-handsideoftheCH10moleculeisthesameasoneendol t heetheoemolec:ule,
1 chlomethene,CH;z=CHCI andtheright-handsideis thesameasoneendof thecaibondioxidemolecule.The
:Z di-imide,HN = NH moleculeistriar,gularp(anar,withbondanglesofapproximat ely120
3.16 Delocalised rr orbitals

Delocalisation in benzene
Just as two p orbitals can overlap sideways 10 form a It bond. so two (or more) It
bonds can overlap with each ()(her to produce a more =tensive !t bond . The classic
=ample is benzene. C.,H 6 whose molecule contains a planar, six-membered ring of
sp1 -hybridised carbon acorns. The unhybridised p o rbitals of the carbon acorns could
overlap as shown in Figure 3.44a to produce three C=C double bonds between
atoms 1 and 2.3and4and Sand 6 ofthering, orjust aslikely.overlapasshown in
Figure 3.44b to produce double bonds between atoms 2 and 3, 4 and S, and 6 and I
ofthering . lnfact.bcthoccur.
Flgure l.44 AllemativevteW1ofbonding

betweencarbonpairsinbenzene
All six p offiitals overlap with each neig hbour in an equal fashion. to produce a set
of cwo dou g hnut-shaped ring orbitals (see Figure 3.45). This sec of It offiitals can
accommocbte six electrons. none of which can be said to be localised between
any two panicular atoms . These !t electrons are described as being dclocaJL,;c d
around the ring . All six C-C bonds are the same length (shoner than a C-C single
bond, but longer than a C=C double bond) and the shape of the ring is a regular
hexagon. with every C-C- C angle being 120. The imerescing chemical propenies
that this ring of delocalised electrons g ives benzene are discussed in Topic 25 .
Flgure l .45 Thedelocali<oedbondingln

benzene
61
PHYSICAL CHEMISTRY
Delocalisation in the carboxylate ion

AnOl:her example of delocalisation occurs in the carboxylace anion (see Topic 18),
which is sometimes re-presented as follows:
0
- c I'
'o-
Here a lone pair of electrons in a p mbital on oxygen overlaps with the It orbital
of an adjacent carbonyl group. Because of the symmeuy of the sySlem. the
delocalisation is complete, resulting in each oxygen finishing with exactly half an
electronic charge. on average. Also. each C--0 bond has the same length. which is in
between the lengths of the C--0 single bond and the c=o double bond .
This structu"' can be derived from the simple localised model as follows . The
c=o double bond consisls of the usual CJ bond + Jt bond pair. The singly bonded
oxygen(whichhasanextraelectron. makingitanionic) containsth..,.,lonepairs
of electrons . lfoneofthelonepairs isin aporbirnl(seeFigure3.46a).thisfilledp
orbital can overlap with the end of the it orbital on the rnrbon atom . The Jone pair is
thus panblly donated, as a dative It OOfld (see Figure 3.46b).
Because carbon cannot havemorethaneightelectronsin its valence shell.this
panialdonationbythelonepairononeoxygen wiJJcausethe it electrons in the
c=o bond to drift towards the second oxygen atom. So the four II electrons (that is.
the two in the c=o OOfld. and the two in the lone pair) become delocalised over the
chreeatoms (seeFigure3.46c).
Figure 3.46 Delocalhatkminthe

carboxylateKlfl
Delocalisation is sometimes represemed by t,vo (or more) localised structures joined

by double-headed arrows. asin Figure3.47 .
Flgurel.47 The repre1entationof

deloc.li'iationofchargeinthecarboxylatekm
_rJ:!:-
- c~ :
The double-headed arrow should be read as 'the actual structure is somewhere

between the two extremes drawn here' . The curly arrows represent the movements of
electronpairsthatcorwettoneextremeintotheOl:her.
The curly-arrow convention is often used when describing the movement of
electrons. and the formation and breaking of bonds, during the reactions of o rganic
compounds. See section 12.8 for a full description of what it me-:ins .
62
Worked example
All three C-0 bonds in the carbonate ion are the same length. Use the kle.i of
delocalisationtodescribethebondingintheCO/-anion,andtopredictitsshape
Answer
lfa llthebondsinthecarbonateionwerelocalised.itwoold rnnsistolacarbonylg roupto
whichareattached(bymeansofs.ingleornvalentbonds)twooxygenatoms,eachof
whichhasitsvalenceshelllilledbyanextrnelectron, givingitanegativecharge(see
Figure3.48}
Flgurel.48 L(){alisedtxmd inginco,'-
Just as in the carboxylate ion, ea<h of the two singly bonded oxygen atoms has an extra
electron, making it anionic. So ea<h of these atoms contains three lor.e pairs of e~rons.11
oneofthelor.epairsisinaporbital,thisfilledporbitalcanoverlapwiththeendofthe11
orbitalonthecentralcarbonatom. Thelonepairisthuspartiallydonated,asadativeit
bond.Theporbita lonea<hoxygenatomcanove!'lapwiththe11 orbitaloftheC=Ogroup,
creatingafoor-centredelocalised11 orbital.ThereisnothirigtodistinguishoneC-Obond
fromtheothertwo,soallthreeareofequ.allength. andeachoxygenatomcarries,on
average,folanegativecharge(overallcharge 3 3x-1:~ - 2}. Theshapewillbe
triangular planar, with all 0 - C- 0 bond angles 120" (see Figure 3.49)
Flgurel.490fbltaloverlapleadingto
deloGilisedbondinginco/-
All three N-0 bonds in the nitrate ion, No1-, are the s.ame length, and the ion has a
triangularplanarshape.Oescribethebondinginthenitrateion.(Hint:therearethree
typesofbondhere - s.ingle(o)bonds,datives.ing~(o)bonds,anddelocali sed11bonds.)
63
PHYSICAL CHEMISTRY
3.17 Intermolecular forces

Most of the covalently bonded particles we have looked at in this topic are simple
covalent molecules . They differ from gfant covalent, ionic and meiallic lanices
(see Topic 4) by having very low melting and boiling points . They are often gases
or liquids at room temperature . This is because. although the covalent bonding
within each molecule is very strong, the lntl'nnolccular attractions between
one molecule and ancxher are comparatively weak. When a substance consisting
of simple covalent molecules melts or boils. no covalent bonds within the
molecules are broken. The increased thermal energy merely overcomes the weak
intennolecular forces . This requires little eneigy, and hence only a low temperature
is required .
\Vhy a"' these molecules attracted to one anO!her at all? There are three main
categories of intemx,lecular anmction, which we shall lcok at in turn . All are
electrostaticinorigin,asareallforce.sinchemislry. Strictly.speaking, theycanall be
grouped under the umbrella tenn van der W3als " forces. although this term is now
often used to describe only the instamaneous dipole force (see below).
Permanent dipole-dipole forces

As we saw on page 54, the uneven distribution of electronic charge within
some molecules results in their having a permanent dipole . The positive end of
one molecule 's dipole can attma the negative end of amxher's, resulting in an
intermolecular anmction in the region of 1--3kJ nx,l- ' (that is. at least 100 times
weaker than a typical covalent bond). Such attractions are called permane nt
dipok-dipok forcl'S, and an example is shown in Figure 3.50.
Flgurel.50 Dipole-diprnef01ces inh)'d10ge11 6+ r,.... 6+ r,.... I>+ r,....

chloride H- - CI ------ H- - CI ------H----- CI
Instantaneous dipole forces

Being much lighter. the electrons within a molecule are much more mobile than the
nuclei. This constant movement of negative charge produces a fluauating dipole. If
at any one instant a non-polar molecule posse.s.ses such an ins tantancous dipok
(owing to there being at that iostant more electrons on one side of the molecule than
the other) , it wiJJ induce a corresponding d ipole in a nearby molecule . This wiJJ re.suit
in an attmaion between the molecules , called an ins tamancous dipole forcc or an
induced dipole force (also termed a \':Ill dcr Waals" force). The situation is similar
to a magnet picking up a steel nail by inducing a magnetic nK>mem in the nail, and
hence attracting it
An instant later, the first molecule might change its dipole through another
movement of electrons within it. so the original dipole attraction might be
destroyed . This changed dipole will induce new d ipoles in molecules thm surround
it. however, and so intermolecular attraction will continue. The strength of the
attraction decreases rapidly with distance (F ~ 1/rD:J. and so it is only a very
shon -range force . Its magnitude depends on the number of electrons within a
molecule, because the more electrons a molecule has, the larger the chance o f an
instantaneous dipole. and the larger that dipole is likely to be. Its magnitude also
depends on the molecular shape, becausethegreaterthe'areaofclosecontacr',the
larger the force. Induced d ipoles occur in all molecules, whether or not they have a
permanem dipole, and whether or not they hydrogen bond with one another (see
below). The magnitude of the instantaneous d ipole force, as mentioned above,
64
Table 3.4 Boil in g poinll of some molerul.ir Bol llngpolntl"C
e~at::1~
elementsaridrnmpoulld1.Noneofthes.e
:~~ru:il~~=~/:;;~::ii~;\othe
largerimtantar+eous dJk>5
f-'~i~::- --1---'1---'~-----, :::h:r~l~~ ~:=o~:~rom
inm a'>!.'5 goin g down the group, from 10 in
CH,to 18in5iH,
All ofthese arelilll'ar diato mi::molec:ules.OOWl\
>-,~,,- - - 1 - - - ' f - - - - - - - , th egroopthe number of ek>ctrons iocrea'il.'5,
>-'-- - - l - - - ' f - - - - - - - , from18 in F,to 34inCl,and70in8 r,
I-':~~;-, - - - +~ ---I :Or!: :a;{~;/~ir:~~~ o~ ;ont.Kt)

1 1
~ ~- - - - - - - , f - - - - - - - , and rnntainmo1Eelectrnm{an e:,;tra8fo r each

>-'~
'"~- - - - + - - - - - - - 1 CH, group)
C, H,o
TH,
CH, - T- CH,
!:=m:. ::;fi~~!::ra~:r:l~m
0
a:~:
sp!leric:alif theelectrondou dsaround the
CH, atoms aretakenintoacrn,mt - andthesecoml
f - - - - 1 - - - ' f - - - - - - - , i'i 's..u1age 1haped'.Thearea ofclosernntacti1
CH,CH,CH,CH,CH,CH, the refDfegreatl>finthesecoodone
depends on the size of the molecule. but is approximately 5-15 kJ mol ' . The effect
of !his force is ...,.,n in the trends in tx,iling points shown in Table 3.4 - the greater
!he insrnnrnneous dipole force, the higher the ooiling point .
Hydrogen bonding
\Vhen a hydrogen atom bonds to anO!her atom , its single Is electron is taken up
in bonding, and so i! is located in a CJ bonding orbital between it and the atom
Flgure l .51 Hyorogenbondinginammon ia it is bonded with . Its O!her side. the,dore. contains no electronic charge. It is a
barepro1on.witha significant S+ charge. TheJX>5itivechargeiseven g reaterifthe
hydrogen is bonded to an electronegative mom such as nitrogen. oxygen or fluorine .
This highly S+ hydrogen can experience a particularly strong anmction from a lone
pair of electrons o n an adjacent molecule. creating an intennolecular anmctive force
of abouc 20-lOOkJmor'. Such a force is called a hydroge n bond . It is roughly 10
times as strong as the dipole-dipole force or the in.stantaneous dipole foree. and is
only a bou t 10 times weaker !han a typical covalent bond. Aton1s that contain Jone
pairsofelearonsinorbitalsthatan,smallenoughrointeractwiththese &+ hydrogen
atomsalsohappentobenitrogen,oxygenandfluorine. Soitisbetweenthese
elements that hydrogen bondi ng tends to occur(...,., Figure 3.51).
As a result of hydrogen bonding :
the boiling points of ammonia. NH!; water. H20 ; and hydrogen fluoride. HF: are
considembly higher than that of methane , CH 4 (see Figure 3.5 2)
the boiling points of ammonia . water and hydrogen fluoride are also considembly
higherthanthoseof<Xherhydrides intheir g roups(...,.,Figure3.53)
e proteinsfoldinspecificways, g iving themspecificcatalyticpropenies (seeTopic28.
secondary and tenia,y scructure of proteins)
in nucleic adds , the bases form bonds with s pecific partners. allowing the genetic
code to be replicated without errors of transcription (...,., Figure 3.54) (see Topic 28.
double helix)
the boiling points of alcohols are considerably higher than those of alkanes with
the same number of electrons. and hence roug hly the same van der Waals' force
(seeTable 3.5).
65
PHYSICAL CHEMISTRY
Flgurel.52Theenhancl.'dbornrigpointsof
NH1,H,OandHf
,,o
Flgurel.53Boilingpointsofthehydrkle1of
Group,; 14to17
,,o
Group16
period
figure 3.54 Thymine, adenine. cyt01irie

a!ldguanine.ireba<,e<;lnONA.Thehydrogen
boridingbetweenthemalklwstheONA
N ~O:~
~eru~ to rl'plic:ate (make nfNI m1ne1 of
itse!f) and al:s.o allo\\~ the genetic: rnde to be
""'*~,dioesyo<hesoof1p><~~ ~
- N ,o~NA
chain
to DNA
N
- --
-
chain
to ON chain .
chain thymine adenine cytosine guan,ne
66
Table l .5 Compar inglheboillrigpoint1of Bol ll ngpol ntt"C
akoholsand alk.me1
CH 1- CH,
CH 1- CH,- CH 1
CH 1- CH,-oH
CH1- CH,- CH,- CH1 34
'Mlter s hows several unusual properties owing to the brge degree ol hydrogen
bonding within it. These are described in section 4.4.
Worked example
Describe all the intermolecular forces that can ouur between the molecules in each of the
follo1\~ng liquids, arid heme piedict which will have the lowest boil irig poirit, and which w ill
have the highest
A CH1CH 2CH 2CH, B CH,CICH,OH C CH1CHCl1
Answe r
Molecules of A will experience only vari der Waals' (ind uced dipole) forces. Molecules of B
will experience dipole---di~e forces {due to the C- CI ,md C- 0 polar borids), and
h'jl)rogenbonding(duetothe - 0 - Hgroups),aswellasvanderWa.als'forces.Molecules
of Cwillexperienced ipole---d ipoleforces{duethedipolesoftheC-C lbondsnotcancell ing
eachotherout)iriadditioritovanderWa.als"forces
Therefore A wi ll have the least iritermolecular attraction, and hence the lowest boilirig
point,andBwillhavethehighest
1 Describe the intermolecular forces iri the foHowing compoonds. and place them in
orderofiricrwsingbo.lingpcirits
CH 10H-C H10H CH 1Br-C H1Br CH,CI--C H,CI
2 Suggestarea'iCmwhythedifference1betweenthebo.lingpcint1ofthealkane1and
alcohols in Table 3.S become sma ller as the chain length increases. (Hirit: think of how
theiritermolecularlorcesothertharihydmgeribondingarecharigingaschain~gth
inc=.)
Chem ica lbondlng 1esultsfromtheattractionofoneatom"s The shape of a covalent molecu~ is determined by the number
electronsbythenucleusofaootheratom. ofelectronpairsthereareinthe valenceshelloftheceritral
Atoms are mote stable when they are bonded together than atom,accordingto VSEPRtheory.
--
when they are free lftwobondedatomsdifferin electronegativity, the shared
A rovalentbond isduetotwoatomssharingapairof electroripairisclosertothemoreelectronegativeatom.This
resultsirithebondhavinga dipole
Ari atom can often form as many bonds to other atoms as ii Complete molecules can have dipole moment s if their bond
haselectronsinits va lenteshell, withtheexceptionthat, dipolesdonotcanceleachotherout
if the element is in Period 2. it canriot have moll! than eight lsoeledronic molecules arid ions usually have the same shape
electronsiri its valenceshell as one another.
Valence-shellelectronsnotinvolvedinbondingarrange Theoverlapofatomicorbitalsonadjacentatomsresults inoor
themse!vesirito lonepalrs aroundtheatom 1tmolecularorbitals
Datlvebond ing (co-ord inatebond lng )occurswhenoneof The!earethreetypesof intermo lecu la r forces:permarient
the bondedatomscontributesboththebondingelectrons dipole.induceddipolearidhydrogen bonding.Theirstrengths
Dou~e and triple bonds can occur if two atoms share two or increase in this order.
threeelectronpairsbetweerithem Thestll!ngthsofinteITT10lecu!arforcesdeterminethephys.ical
propertiesofasubstarice,suchasitsbo.lingpcirit
67
PHYSICAL CHEMISTRY

Piea5e<;e('thedataSKtionoftheCDforanyA,vah-.;you c Methanolandwarerarecompletely~bleintachother.
may""' i \\ohich intermolecular force ecists between methanol
molecules and water molecules that makes these two
1 This question is about different models of bonding and
liqLids50lubleineachother7
molecular shapes.
ii Oraw a diagram that dearly shows this intermolecular
a Magnesium sullide shows ionic bonding.
force. Your diagram should show any lone pairs or
i What is meant b'f the term ionK bonding?
dipoles present on either moleC\Ae that you comidef
ii ?raw a ~1-and-c~' diagram to show the booding
to be important. [41
m magnesium sutf1de. Show outer electron !ihells only.
d When equal volumes of ethoxyethane, C1HsOC 2Hs. and
b 'Dot-and-cross' diagrams can be used to predict the
water are mixed, shak:en.andthenaUo....edtostand, two
'ihapeofcovalentmolecules.
layers are formed
Fluorinehasacovalento~idecalled dilluorineoxide, Fz(l.
Suggest why ethoxyethane dots not fully dissot...e in
The oxygen atom is cOYalently bonded to each fluorine
water. Explain your answer. [2]
"=
i Draw a 'dot-and-cross' diagram of a molecule of FiO.
{Cambridge International AS & A Level Chemistry 9701,
Paper 2 QI June2008]
Show outer electron shells only.
3 Linus Pauling was a Nobel prize winning chemist who
ii Predict the bond angle in an F20 molecule. Explain
devistdascaleofelectronegativity. Some Pauling
your answer.
electronegativityvaluesareshowninthetablt.
{OCR ChemstryA UnitF321 03 (part)January2010}
2 The structural formulae of water, methanol and
methoxymethane, CH~CH 3, are given below.
/0'-_ /0'-_ /0'-_

H H H3C H Hie' CH1
a i How many lone pairs of electrons are there around the

oxygen atom in methoxymethane 1 a Whatismeantbythetermtlecrronegawity7 [2]
ii Suggest the size of the C----0--C bond angle in b Sho.v, l.&ng S+ and &- symbols, the permanent dipoles
oneachofthefollowingbonds.
rnetholcymethane. 121
N~F N---ilr [1]
The phys,ical propertiM of a covalent compound, ~ il5 its
melting point. boiling point, vapour pressure, or ~ubility, c Boron trifluoride, BF). amm<>r.a, NH). and sulfur
hexafluoride, Sf6' are a11 C011alent compounds. The
arerelatedtothestrengthofattractiY'tforcesbetwttnthe
shapesoftheirmoleculesaredifferenl.
molecules of that compound.
i StatetheshapeofamoleculeofSF" [IJ
The5erelativelyweali:attractivelorcesartcanedintermolecular
ii U5ing outer electron shells only, draw 'dot-and-cro:.s'
for~ They differ rl ~r strength and include the following:
diagrams for molecules of BF 3 and NH 3.
A 1nteract10ns invoh'mg permanent dipoles
Use your diagrams to explain why a molecule of BF1
B interactionsinvoh'ingtempo<aryorinduceddipoles
has bond angles of 120" and NH 3 has bond angles
c hydrogen bonds 01107". [SI
b ~yusing the letters A, B, or C, state the stro ngest
iii MoleculesofBF3 containpolarbonds, but the
mtermolecularforcepresentineac h ofthefollowing
molecules are non-polar.
compounds.
Suggestanexplanationforthisdifference. [2]
i ethanal.CH 3CHO
{OCR Chemistry A Unit F321 03 January 201 I]
ii ethanol. CHlCHiOH
iii methoxymethane. CH30CH3
iv 2-methylpropane, (CH]}1CHCH 1 14)
68
AS Level
Physical chemistry
4 Solids, liquids and gases

In Topic 3 we saw how atoms
bond together covalently to form Learning outcomes
molecu/es.Wefinishedthattopic Bytheeod ofthistopicyoushouldbeableto
withabrief/ookathowthe 3. 1a) describe icmic (electrovalent} bonding, as in sod ium chloride and magriesium oxide,
molecules themselves might attract includingtheuseof"dot-arid-cross'diagrams
oneanother.lnthistopicweexamine 3.4a) describemetalli cbonding inll'fmsofalatticeof posiliveiomsurrounded by
how these attractions between delocalisedelectrons
molecu/es,andbetweenother 3.Sa) describe,interpretandp<edictthe effectofdifferenttypesofbonding(icmic
partic/es,canhelptoexplainthe borid ing,covaleritborid ing,hydrogenbonding,other inll'fmohKular interKtions,
differences between solids, liquids meta llicbonding)o n thephysical propefliesofrubstances
and gases. We explore the giant 3.Sb) ded uce thetypeolbondingpresentfromgiveninformation
structuresthatatomsandionscan 4.1a) statethebasic assu mptionsof thekineticthroiyasapplied toanide-alg.as
form, in which it is impossible to say 4.1b) expla inqualit ativelyin ll'flTl1of intermolecula r forresandmolecularsizethe
whereonestructuralunitfinishes conditionsnl'Cessaryforagastoappro.x:hide-albehaviour.aridthelimitations
andthenextonestarts-.Wethentake ofide-alityat veryhigh presrull!sandverylowll'!TlPl'fillU!l!S
ac/oserlookatgases,andseehow 4.1c) stateandusethegeneral gasequationpV = nRTin ca lrnlat ions. includingthe
thesimpleassumptionsofthekinetic determinationof M,
theoryofgases/eadustotheidea/ 4.2a) describe, usirig a kinetic:-molernla1 model, the liquid state, melting, vaporisaticm,
gas equation, pV = nRT. Finally we vapourpresrull!
see how the behaviour of real gases 4.3a) describe,insimpleterm1,thelatticestructureof acrysta llinesohdwhichi1icmic
can differ markedly from that of an {as in sodium chloride, magnesium oxide), simple molecular {as in iodine and the
idea/gas. fu llerl'!lea llotropesofcarbon - C60 aridnanotubesonly),giant molecular(as in
si licon(IV)oxideandthegraphite,diamondandgraphenea llotropesofcarbon),
hydrogen-bonded(as inice)ormetallic(as incopper)
4.3c) outli ne theimportanceofhyd1ogenbond ing tothephysicalp<opertiesof
substances,iricludingicearidwater (l0<example,boilingaridmeltingpoint1,
viscosity arid surface tension)
4.3d) rugge51fromquotedphysical data the typeofstructureandbond ingpresentin
a llJbstance
4.1 The three states of matter

There are three states of ma!ter - solid, liquid and gas (ig noring plasmas. which
only form under extreme conditions). These are sometimes called pha ses . If we
consider a substancethatweexperienceeveryday in allthreestaces. such as
water. we can appredace that the solid phase (ice ) occurs al cold temperatures
( T< 0C): the liquid phase (water) occurs at intermediace tempemmres
(0C < T< 100C); and the gaseous phase (steam) occurs at high temperatures
(100C < n. We can see that in order to change a solid into a liquid, or a liquid
into a gas. weneedtogiveitenergy. intheformofht"at(thermalenergy).
This energy goes into overcoming the anmctions between the panides. If we
supply heat to a block of ice at a constant rate, and me3sure its temperature
continuously. we obtain a graph liketht"ont"shown in Fi gure 4.1.
69
PHYSICAL CHEMISTRY
Flgure4.1Thechangeinll'r11peratureover
timeasabkx:kofkei1heated
Changes in the molecular behaviour in the five reg ions of this g raph can be described
Between A and 0 , the ice is wanning up . The H 20 molecules are fixed in the ice
lattice (see page 71 ) . but are vibrating more and mo"' energetirnlly from A to H.
Ac B. the ice begins to melt. Here, the molecules are vibrating so strongly that they
can begin to break away from their neighbours and move about independently.
Between ll and C, H 20 molecules continue 10 break away from the lanice.
Although heat is still being absorbed by the ice-water mixture, the temperature
does not rise. This is because any =tra energy that the molecules in the liquid
phase may pick up is soon transferred by colHsion to the ice Janice, where ii causes
another H20 nx,lecule to break away from the ice laaice . Not until all the ice has
becomeliquidwilltheternperaturesrnntorise3g3in.
From C to D . the liquid water is warming up. As the temperature increases. the H,O
molecules gain more kinetic energy. and move around faster. In cold water there
are small closely knit groups of H,O molecules. containing S-12 molecules in each
group, and. as the water warms, the extra energy 3lso causes these to break up .
At D. the H20 molecules 3re moving so fast that they can overcome the remaining
forces (mostly hydrogen bonds) that hold them together. The water stoins to lx>il.
The molecules evaporate to become single H,O molecules in the gas phase,
separated by distances of many molecular diameters. Just as in the region II to C,
the ternperarure remains constant until the last H,O molecule has boiled away .
From E to F. the individual H,O molecules in the steam gain more and more kinetic
energy. so they travel faster and faster. If the steam is in an endo.sed volume, this
will cause the pressure to increase, as the molecules hit the walls of the container
\\ith increasing speed. lf. on the cxher hand. the pressure is allowed to remain
constant,thevolumeofgaswillexpand.
Worked example 1
A mole of liquid water has a volume of 18an3, and a mole of steam at 100( and room
pres!,Ure has a volume of 33dml. By how many times has the volume increased?
Answer . 33 xl0'
Thevolumehasincreasedby - - 3 1833 times.{Remember, 1dm1 ~ 11Yan3.)
18
Worked example 2
Assuming that all the H10 molecules in liquid wale< are touching one another, roughly how
many molecu lar diameters are they apart in steam?
Answer
Theincreaseinl ineardistancebetweenthemoleculesisthecuberootoftheinae<tSein
volume. 5o in steam the molecules are 3',in .. 12 molecu~r diameters apart
70
Solids,liquidsandgases l
Table4. lsummarises!hediffe..,ncesbetweensolids.Hquidsandgases.
Ta ble 4.1Toepo!itionsandrnovementofthe Re latllle position of p;;irtlcles Relative movament of partldes

partic~sin!i0lid1,llquid1alldgases
toochingooeaoother fixedinan.>gularthll'!.'-dimensKJriallattke:can
on!yvibrateaboutfixedposilions
IKjuid toochingooeaoother movingr,mdomlythroughtheliqukl,oftenin
weaklyb-Oodedgmups ofo;eve1almolecule1ata
time:vibration, rotationandtramlatiooal motion
are allowed
far apart from one anothe! in dividual molecuk>s moving randomly at Mgh
speeds,collidingw;th,andboundngoff,ooe
anolhl'fandthewallsoftheircontainer
4.2 Lattices
For mos! subsrnnces, the solid and liquid phases usually have about the ~me density .
This is because in born solids and liquids the panicles ar<, touching one ancxher.
with little space in betv,een them . As we have just mentioned , the major diffe..,nce
between solids and liquids is whether or n<X the pankles have translational motion .
In liquids, the panicles move fairly randomly and ar<, continually sliding over one
another. In solids, on the cxher hand. the panides do ncx move around from one
place to ancxher. They can only vibrate around fixed positions.
There are two major types of solids - crystalHne and non-crystalline solids
In n o n,.c11-stallh1c (or amorphous) solids. the p<inides are r>OI arranged in any order,
or pattern. 1bey are fixed in random positions. If you took a ,ideoofa liquid. shov,ing
Flgure4.2 The1tructu1eofa
noo-crystalli ne(amorphollS)!did the p<irtides moving around chaotically, and froze a frame from thm video, the pktu..,
Toeparti::lesareinarandom would be indistinguishable from that of a non-crysulline solid. Many non-crystalHne
arrarigemenl solids.forexampleglass, ar<,o/iencalJedsupem:,oledliquids' (seeFigu..,4.2).
In c111,1alline solids. the panicles are arranged in a regular three-dimensional
panernorarray. This is called a latticc(see Figu..,4.}). Everylatticecanbethought
of as being made up from l<Xs of subunits or building blocks stacked one on top of
the Ol:her. in rows 3nd columns. These repeating units are called unit cells . Once we
have understood the geometry of the unit cell. and how the acorns are joined cogether
in it, we ar<, well o n !he way to understanding what gives crystalHne solids their
shapes, and theircxher physical propenies .
Flgure4.3 The1tructu reofacrystalline!i0lid .
zir,c(left). Toepartide1of1odiumc:hl0fide
(right)areinaregularlatticearrangement

-
-
4.3 The building blocks of lattices

The uhima!e building blocks of matter are , of course , atoms . The lattices of most
elements are composed simply of individual atoms . We can distinguish thr<,e types of
monato mlc mo!CCT1lar lattices. such as in solid argon and the Nher noble gases
nm cromola .ilar covalent lmticcs. s uch as in diamond and silicon
m L'talliclatticcs.suchasinironand3ll<Xhersolidmetals.
71
PHYSICAL CHEMISTRY
In addition, some eleme nts th31 form polyatomic molecules. such as the non-mernls
in Groups 15. 16 and 17(e.g. P4. ~ and 12)exisl as slmpll'molccular lattices.
The lanice build ing blocks of solid compounds comain more than one element .
There are three types:
s imple m oR>cular lattices. such as in ice

gia nt molec ular L-itticcs. such as in siHcon(IV) oxide
ionic lattices. such as in sodium chloride and calcium caibonate.
Each type of lattice confers different physirnl propenies upon the substanceth31
has it . We shall explore these propenies in the sections thm follow.
4.4 Simple molecular lattices

In simple molecular lankes, including molecular atomic lattices, there is no chemical
bonding belween the panicles, ju.'il dipole-dipole forces, instantaneous dipole forces
or hydrogen bonding anmctions, which are comparatively we-:,k . Figure 4.4 shows
examples of simple momk and molecular bnices . The molecules or atoms ar<, packed
tightly, but only a small amo1.mt of thermal energy is required to overcome the
intermolecular forces and break the lattice. Sub.stances containing this type of lattice
therefore have low melting points (and low boiling p;:>ints). As we saw in section 3 .17.
boiling JX>ints depend on the strength of the intermolecular bonding. The same is true
formeltingpoims(seeTable4.2).
F1gure4.4 lnrnMarqoo,a~mpk>atomk
lattke,theontyintermolec:u!arfoo:esateweak
imtantarieou1d ipoleforcesln1,0 lklhydmgen
chlolide,a1 implemolernlarlattice,thereare
dipole-dipoleforcesSolidiodineha-;strong
inltant.lneou1dipoteforce1
sol idhydrogenchloride -
dipole-dipoleforce,s ~lid iodine - strong
dipole forces
Table 4.2 1ntermok.>cularfo1u1,mdmelting

point5 for !i0me1ubstances ==of Intermolecular
weakimt.mt;meou1dipole
Metting polntl"C
hydrogen chloride dipole-dipole

,,o hydrogen bonding
stmn9imt.intan eou1dipole
C12H,,o,, stmo9hy<lrogenbondio9
The properties of water are in ...,vernl ways rather different from tho.se of cxher
simple molecular substances. Unlike the molecules of cxher comJX>unds rnpable of
forming hydrogen bonds, water has two Jone pairs o f electrons together with two
&t hydrogen morns . This means that it can form two hydrogen bonds per molecule
on average. whereas alcohols , ammonia and hydrogen fluoride can only form one
72
::~ ;:;:::T:E:.n~:'.::~:;~;:u~:ns~ ~~:c1:::::h:~:~Jo~:::~:;:::~:

~ 50 ::rii::l~'!r;';::f ~~!.er is much higher than those of ammonia and hydrogen
4
~ 0 Liquid water has a high suiface tension. The strongly hydrogen-bonded molecules
J; _50 form a lanice across the surface of w:uer, allowing objects which you might expect
] to sink in ,,,ater, such as pond skaters and even coins (if you are careful), to float'
- 100 onwater (seeFigures4.6 and4. 7).
::: ,--- \ \--o '\

15 16 17
,---( r \
O
p
r '\
~'\, r
Flgure4.5 Thebo ilingpointsofNHs.H,O
and HF
: \-a'\,
,' --J:
>-~ r \-o '\
I r'\
\--o '\ r
'> -- 1 r I r'\
'- --', ,),-a'\ \--o '\, r
,___ r I r'\
Flgure4.6 Hydr09ffiboodingoothe1urface
ofwaterformsahexagonalarraywhich
r a watermol ecule
1
0- H ---o- 0---- ahydrogenbond
between hydrogen
andoxyg<'n
pmvides.i high1urfacetemion
Flgure4.7 Toesu rfac:etemlooof water

supports the pond 1kater-the '>Uffa{e ~
depre1'>1.'dbtitthehydrogenbond1holdil
together
73
PHYSICAL CHEMISTRY
Ice is less dense than liquid water. The hydrogen bonds between the water
mol=ules in ice are positioned roughly tetrahedrally around each oxygen atom .
This produces an open lanice , with emp1y spaces between some water molecules
(see Figure 4 .8). The more random arrangement of hydrogen bonds in liquid water
mkesuplessspace .
Flgure4.8 1nice,themoll'Culesarehydmgen
bonded in atetrahl.'dr.ilarrangemen~ which
make5ic:elessdemethanliquidwater
0 o ahydrogenbond
For examples of carlxm-co maining simple lattices. see section 4.12, page 87 .
4.5 Giant molecular lattices

These are sometimes refem,d to as macromolecular laaices . They consist of thre-e-
dimensional arrays of atoms. These atoms C3n be either all of the rome type. as in the
elements C3rbon (diamond. graphite or gmphene. see page 8-0 and silicon. or of two
different elements. such as in silicon(]\') oxide or l:xxon(III) nitride. The atoms are all
joined to Ofle ano1her by covalent lxxl<ls . So a single crystal of diamond or quaaz is in
fact a single molecule. containing maybe I x to'l atoms . For atoms to become fr= from
the lattice. these strong bonds have to be broken. Subcrnnces conmitting this type of bttice
therefore have veiy high melting JX>ints and also high boiling points (see Table 4.J).
Table4.1 Meltir,gandboilingpoint1all' high Metting BolllngpolntlC

for1ub1tam:eswilhagiaotcova lent!attice polntlC
(Notethatbomn(lll)nitridernbl imes-it
change1str.iighl fmma10Mtoaga1when giantrnv.ilent
lle.ited,rnitsmeltingarldboilingpointsare 1ili::oo(IV)oxide SiO:, giantrnv.ilent
thes..,me)
boroo(lll)nitride giant covalent
giant covalent
Flgure4.9 Giantmolecu!a1!attice1have
1troogcovalentbond1inthreedimemiom
,ilkon(IV}oxidelattke
The properties of giant covalent lanices (the tem1s "giant molecular' and 'macrocovalent'
are also used to describe these laaices) result from their si:rucrure and bonding.
Their melting points are high. as described alxwe.
They are electrical insulators. because all their valence electrons are involved in
localised covalent bonds. and so are unable to move when a JXXential difference
is applied .
They are hard , strong and non-malleable, beC3use their covalent bonds are lxxh
strong and point in fixed directions. towards each adjacent atom .
74
Ceramics are inorganic compounds (usually oxides) that are hard and inen, with high
melting points. They are often good electrical and thermal insubtors. and find uses
in furnaces. high volmge insulators and hem-re.sistant tiles (e .g . on the surface of the
space s huttle). Common ceramics include the giant covalem silicon dioxide and the
giant on c magnesum oxide a d alurn num c /de.
What happens to the va lencies on the edge of

a diamond crystal?
Although the caibon atoms inside a diamond cry51al a"' all joined to four cxher
morns , and so have their full complement of covalent bonds, those on the (be
surface of the side of a crystal ha,.._.. only three carbon atoms joined to them. They
have a spare valency. Those atoms occupying positions along a crystal edge or at
anapexarelikelytohavetwospa,.,valendes.
How the spare valencies are 'used up' was a mystery for many years . Some
thought that they joined up in pairs to fonn double bonds. However. this would
mean th.u the surfa= carbon atoms would have to be sp1 hybridised. rather than
sp1 3stheyan,intheinsideofthecrysul. ThemysceryWllssolved by studying
thesurfaceofverycle3ndiamondcryst3lsusingsensitive!echniquessuch3s
ph01:oelectronspectroscopy3ndscanningrunnellingelectronmicroscopy.
Thespan,valenciesareusedupbybondingwithatomsctherthancarbon. lt WllS
discovered thac under nom13l conditions the surface of a diamond cryst3[ is coven,d
with hydrogen atoms , e3ch atom singly bonded to a carbon atom. Diamond is
therefore not an element in the true sense, but a hydrocarbon (a polycyclic alkane)
withaveryhighcarbon-to-hydrogenrntio!
Byheatingadiamondcrystaltoatemperatun,of\000Cin3nextremelyhigh
vacuum. itispo.ssibletodriveoffthehydrogenmoms. Then,sultingsurfaceishighly
reactive. and can lx>nd strongly to OUler atoms. such as oxygen. amine (- NH,)
groups.cthercarbon-eontainingmoleculessuchas alkenes and even some large
Figure 4.10 The calbon atoms on the edges biological nx,lecules such :is DNA . Then, is hope that new molecular semiconducting
of a d i.imond crystal have hydrogeo .itoms devices might be constructed on wafer-thin diamond surfaa,-s in the fucun,. making
hooded to them computers even smaller and mon, JX>Werful.
4' 4.6 Ioni c bond in g - m onatomi c ions

Ionic bonds are typically fonned between a metallic element and a non -mecallic
element . Unlike covalent bonds, which involve the sharing of one o r mon, pairs
of electrons be!ween two atoms. ionic bonding involves one acorn (the metal)
!otally g iving away one or more electrons to the non-metallic atom . This n,sults in
electrically charged a!orns , called Ions, being fonned(see Figun, 4 .11).
Flgure4.11 lonk lithiumflooridei~formed

bythetransferofanelectron
overallcharge:
t
0
We shall delay taking a detailed look at the energetics of ionic bond formation until
Topic 20 (though the panel on page 77 gives a brief account). It is instructive at
this stage !o cornpan, the formation of an ionic bond with that of a covalem bond .
We saw in section 3.11 that bonds between atoms of diffen,nt electronegativities
an, polar, with an uneven dis!ribution of electrons , and hence of electrical charge .
75
PHYSICAL CHEMISTRY
We can consider ionic bonding to be an extreme case: when the electronegativity

diffe,.,nC<." between the two morns is large enough. the bonding electrons will become
compielely !r:rnsfcrred to !he more electronegative atom. and an ionic bond results
(seeFigure4 .12).
Flgure4.12 lonkbood1areformedbetwl'!'n
atormolhfghelectmnl'gativitydifference H: F:
When forming ionic bonds, metals usually Jose all their 01Jter-shell el=trons. Their
ionic valency therefore equals their group number. Likewise, non-metals usually accep{
a sufficient number d electrons to fill their outer shells. Their ionic valency therefore
is (18 - g ) where g is the group number. (See Table 4.4 , page 79. for a comp,.,hensive
list of ionic valencies.) The resulting ions combine in the correc! propon.ions so 3S to
cancel their ch3rges. The compound is therefore electrirnlly neutral overall.
In lithium oxide. for example. each lithium ion loses the electron in its second shell.
3nd the oxygen 3tom accep1s two electrons (one from e3ch of two lithium atoms),
forming a full octel in its second shell (see Figure 4.13). Its empirical formub is
thereforell,O.
Flgure4 .13 ThefurmationofllthlumoxKM'
l' . J
Worked example
Oraw dot-and-cross diagrams shmving the electronic configuration and charges in
magnesium fluoride.
Answer
The 12 electrom in magnesium are arranged in the configurat ion 2.8.2. The Mg1 ion has
losttwoouter-shellelectrons,soithastheconfiguration2.8.
Thenineejectronsinlluorineareinthernnfiguration2.7.TheF- ionhasgainedan
electron,soithastheconfiguration2.8.Weneed2 >< F- {seeFigure4.14)
Flgure4.14
l' . 'J
Drawdot-and-crossdia,grnmswith
l' . 'J
chilrgesshowingtheiookbond ingin (Notethesimplifiedrepresentationolelectronicconfigurntionuse<lhere.Magnesiumis
magnesium oxide, MgO, lithium nitride, 111 211 2p 6311,1hmvna12.8.2byg10upjngtogethertheelect1onsineachshell.Similarly,
Li 3N,andaluminiumoxide,Ali01 fluorine is 1s1 2s12p1, which becomes 2.7.)
76
Energet ics of ioni c bond forma tion - a brief summary

Ionic bonding involves a separation of charge. which is usually an unfavourable
endothermic process. The reason why it becomes more favourable with metals is
their comparatively low ionisation energies . In lithium fluoride. LiF, for example,
the outer electron is fairly easily lose fron, the lithium acorn. and becomes more
attracted to the fluorine nucleus than to its original lithium nucleus . The benefits of
total electron transfer are completed by the resulting electrostatic attraction between
the cation attd anion thac are formed . Look carefully at the state symbols in the
equations below. (For funher descriptions of the terms used here, see Topic 20 .)
Li(g) ---> Li (g) + e - AH 9 = +513kJ mol - ' (ionisation energy)

F(g) + e - ---> F- (g) Af-/ 9 = - 328kJmoJ - '(electronaffinity)
Therefore. in the g:,s phase:
Li(g:) + F(g)---> Lt(s} + F"(g) Af-/ 9 = 513 - 328 = + 18 5 kJmoJ-
The fact that Af-/ 9 is positive means that this is an energetically unfavourable process.
But when the ions fom, a solid lattice, the ions attract one anot her. and much
energy is released :
Af-/ 9 =- 1031kJmol- '(laniceenergy)
So the o,oerall energy change. from gas-phase atoms to solid compound. is :
Li(g:) + F(g) --->Ltr(s)
The complete process is seen to be hig hly exothermic, and therefore favourable.
4.7 Ionic bonding - compound ions

The ions that make up ionic compounds are not always monatomic (that is. they do
not always contain only o"e atom). Several common ions contain groups of atoms
which are covalently bonded together. and which have an o verall JX>,Sitive or negative
charge. He re are a few =amples, some of which we came across in Topic 3.
The ammonium ion, NH/

\Ve first mentioned the ammonium ion in Topic 3 ( pages )() and 55). It is formed from
one nitrogen atom and four hydrogen atoms. minus one electron (see Figure 4.15).
F1gure4.15 Theformation ofthe

ammooiumloo
An alternative way o f l<X>king at its c reation is by forming a dative bond from an

ammonia mo lecule to a prown (see page 50). Fig ure 4 .16 shows this approach.
Fl gure4.16 Thefotmatioooftheammonium
io11 - adiffert>ntview
77
PHYSICAL CHEMISTRY
Either description can be used - the first method emphasises that all four bonds are
exactly the same. while the second is a better representation of how the ammonium
ion is usually formed, by "'acting ammonia with an acid :
NHl(g) + HCl(g) ----+ NH/Cr{s)
The carbonate ion, co/-

To undersrnnd the bonding in polyatomic anions. it is often easier to look first al their
corresp;:mding acids. Chemically, carbonate ions are formed by reacting carbonic acid
with a base , thm is , by removing hydrogen ions from the acid. If this is done. we can
see that the two hydrogen atoms leave their electrons on the c:ubona!e ion. giving it
a-2chaige(seeFigure4 .17).
The delocalisation that occurs in this ion was discussed in section 3.16.
Flgure4.17 Thecarboooteion
H : 0
The sulfate ion, so/-

To study the sulface ion. let us look first at the corresponding acid. The bonding in
sulfuric acid is best described as follows. The sulfur atom has six electrons in its outer
shell. It can use four of these to form two double bonds to 1,vo oxygen atoms (just as
sulfur dioxide. so,. see section 3.9). The other cwo electrons in the outer shell of sulfur
can fOl1ll mu single boods to the Olher two oxygen atoms . lnese singly-bonded oxygen
atoms then in tum form single lx>nds 10 two hydrogen atoms (see Figure 4 .18) . ("Ibis
bonding arrangemem fits in with the respective covalendes given in Table 3.1, page 49.)
Flgure4.18 Themtfateioo
Hf.O~ s;o
t
f-o/s\ !~l-
Hf.R{~:
We can form sulfate ions by remming two hydrogen ions from sulfuric acid . Ju.st as in
Figure 4.19 In the iu!fate loo, the charge ii the carbonate ion. delocalisation occurs. making all four S--0 bonds equivalem. The
delocali<;ed. and the bonds are .i ll equivalent shape of the so/- ion is a regular tetrahedron (see Figure 4.19).
Worked example
Deduce the formula of the ioo fOfmed by the loss of the W ioos Imm boric acid. HJ!lOi
b What will betheovefa llchargeoothision,andheocethechargeooeachoxygeriatominit7
c Suggestashapeforthekm
Answer
a If all three hydroge<1 atoms are lost as W ioos, the remfting ioo will be Bo/-
b The overal l chargewill there!Ofe be -3. and each oxygen will have a chargeof - 1.
c Boronuse1allitselectron1 inlxmdir.gwiththeoxygenatom1,sotheshape'Willbe
triangu la1 planar(seeFigme4.20)
Flgure4.20
78
Predicttheshapeofthekmsderivedfromthefollowir,gacids,andworkoutthefr3etional
chargeone;ichoxyget1alomin&Khion
1 phosphonicacid, H3P03
2 chloric(V)acid,HCIOi
3 chloric(Vll)acid,HCI0 4
4.8 The ionic valency table

The ionic valency of a single atom from Groups L 2 and 1}--17 rnn easily be worked
OIJI from its group number. Howen,,., it is nOI so e asy to predict the ionic valency of
a transition metal. or of a compound ion. Table 4.4 includes all the valencies you wiJJ
hydrogen hydride
potas~um
Ag'
rnppel{I) o'-
,,.
Mg'
w-
Ba' hydroxide
rnppel(II) Cu' nitriteOfnitfate{III) NO,-
~"""
Zn' nitrateornitfateM NO,-
iron(II) hydrogenLlrtxmate HCo,-
hydrogemulfate Hso,-
""
iroo(III)
~
Al"
,,, 1ulfiteor1ulfate(IV)
1ulfateor1ulfatl'(VO
co/-
so,"
so?
me' phosphate ro,
Ionic inorganic compounds are named according to the following general rules.
l lhe name of the compound is urually made up of two words, the first of which is
the name of the cation (the posi!ive io n). and the second is the name of the anion
(the negative ion) .
.? The oxidation state' (ox idation number) is the formal charge on a particular
element in a compound or ion. Where elements can exist in different o xidation
sta!es (see section 7.2), the panicubr oxidation state it shows in the compound
in que.stion is represented by a Roman numeral. Therefo.., iron(III) represents
iron with the oxidation number + 3 (Fel->), and so iron([[[) chloride is FeCl3 . This
is panicularly useful when ..,ferring to compound ions - the nitrogen atom in the
nitra!e(ll[) ion, No,- . has an oxidation number of +3. whe..,as the nitrogen in the
nitrate(\!) ion. No1- . has an oxidation number of +5.
3 Anions containing just a single atom have names ending in "-ide'. Anions containing
oxygen as well as another element have names ending in -ace'. If there is mo"'
than one anion containing a panicular element combined with oxygen, the
oxidationnumberofthatelementisindicatedasinrule2.
79
PHYSICAL CHEMISTRY
'1 For some anions, the ending -i!e' isusedinthetraditional nametoindirnte

that the particular elemem is combined with some oxygen, but nOI its maximum
amount of oxygen. The recommended name uses the oxidmion number insiead.
1 Uselable4.4towritethec0frect
formula for For example:
a irofl{ll)fluoride NO,- iseithernitriteornitrnte(II[)
b magnesium nitride NOJ- isnitra!eornitmte{V)
c rnppel'\l)oxkle
d irofl{lll)hydroxkle
so/-;s .,i!hersulfiteorsulfate(JV)
e calciumphos.phate
S0 42-issulfmeorsulfa1e(VJ)
f ammoniumsulfate
g rnppel'\ll)nitrate .
2 WritethenamesoftheloHowingKlnk: Worked example
compounds
Usetheiooicvall'ncytable(seeTable4.4}topredicttheformulaof
a H!S0 4
a zincnitrnte
b BaS
b aluminiumsulfate .
C Mg(HC01).,
d KN0 1 Answer
l Whichofthefojlowingf01mulaeare ii Zir.c iom are Zn1 , and nitrate ions are No 3- . To obtain a compound that is electrically
inoorrect ?Foreachincorrectformula. neutraloverallweneedtwonitrateiomtoeveryooezincion
writethecOffectooe
Zn1 + 2NOi - ---t Zn(NOlh
Ago
b Sit(OH)i b Aluminium ions are All+, and suffate ions are so/- , so we need two All+ {total
c Pb(NOi li charge = ~) for ewry three so/- {total charge = - 6):
d Alli 2Al 3*+ 3So/- ---t Al 2(S04' 3
e Fei{S0 4h
4.9 Ionic lattices

Co-ordination number
The sections above have described how individual ions form; we now consider
how they collect tog ether in a lanice. Clearly. opposiiely charged ions will attract
each cxher; also, ions of the same charge will repel each cxher. Each ca!ion in
an ionic lattice will therefore be surrounded by a number of anions as its doses!
neig hbours. and each anion will be surrounded by a number of cations. We never
find two cations adjacent to each cxher. nor can two anions be adjacent to each
other. The number of ions that surround ancxher of the opposite charge in an ionic
lattice is called the co-0rdimnion numtx>r of that central ion . The co-ordination
number depends on two things - the relative sizes of the ions. and their rela!ive
charges .
lhe relativesizes oftheions

If one of the ions is very small, there wiJJ ncx be room for many oppositely charged
ions around it. With Zn'\ for example. the maximum co-0rdination number is usually
4 . If the cations and anions are nearly equal in size. one ion can be surrounded by
eight cxhers . The intermediate case of six neighbours occurs. as might be expected.
when one ion is bigger than the cxher, but ncx by very much.
lherelativechargesoftheions
To gain electrical neutrality. a cation with a charge of +2 needs twice as many - I iOfls
asdoesacationofcharge + I. \VethereforefindthattheCa 2* ionincakiumchloride,
CaCl1, is surrounded by tv.-ice as many Cl ions as is the i.,.. ion in lithium chloride. LiCJ.
These two faaors are detailed in Table 4.S. Two of the ionic lattices from the
table - those of sodium chloride , NaCl. and caesium chloride. CsCl - are shown in
Figure4.21 , whichclearlyillustrntesthedifferingco-ordination numbersoftheionsin
80
Tabte4.5 Them-ooiiriatioonumberdeperids
Compound Anion Anionradius Co-ordination
ontherelatives.ize1andthecha1gesonthe rildlus/nm
lominvolwd Cationradius ~~t:':tof
MgO
Caf,
Figure 4.21 Model'; of the !attic~ of sodium

chloride.N.;Cl(aand b )andcaesiu mchloride.
CICI (c and dl: b ,md d s.how more clearly the
alternatinglayersoflom ~
- /
x/ ~
"
o, " ~
,- );.-:;yt;Q:;~~ ~
;),*J/~
-: xf : -
- j -
- l ; ' -
. j '. t -
Flgure4 .22a Crysta1'iof50diumchlolide

andbclearrubkoy1tal1ofc.lciumfluoride
mixed with white dolomite
Ion polarisation and charge density

'We saw in section J . l I that many covalent bonds involve a slight separation of charge,
due to the different electronegativities of the t"u atoms involved in the bond. This
confers a small degr= of ionic characrer on the covalent bond.
81
PHYSICAL CHEMISTRY
Starting from the cxher extreme. we find th31 a small degree of covalent character
is apparent in some ionic bonds. This is due to polarisation of the (negative) anion
by the (JX>5itive) cation . lt occurs to !he gre:uest extent when a small or highly
charged cation is bonded to a large anion. The outer electrons around the large
anion are nOI veiy firmly held by its nucleus, and can be attracted by the strong
electricfieldaroundthesmall. highly charged cation. This causes an increase
inelectrondensitybetweenthetwoions,thatis,adegreeoflocalisedcovalent
bonding (see Figure 4.23).
Flgure4.2l lonpolari'>.llionbetweena'>ffiall,
highlychargedc:atKlnand a large;mkm
0 0
The idea of ion polarisation is imponam in explaining the thermal decomposition of
metalcarbonatesandnitrates(seesection!0.4).
Thestrongelectricfieldaroundsmall. highlychargedrntions31tractsnOl:onlythe
o uter-shell electrons in anions, but also the Jone pairs on polar molecules such as
water. We shall see in Topic 20 that the enthalpy changes of hydration of small ions
are much more exOl:hermic than those of larger ions.
Theconceptofchargedensityisausefuloneforexplainingtheinfluencethatan
ion(usuallyacation)hasontheelectronsinadjacentionsormolecules.
Imagine two + I ions. one with a radius ofO.lnm and one with a radius of 0.2nm.
For each ion.the + ! chargeisspreadoverthesurfaceofa sphere,forwhichthe
first ion has a surfaceareaof0.125nm'(41tr',withr = 0.1). Thesurfaceareaofthe
second ion is 0.50nm', which is four times as large as the first (area~ r 1 ).
The charge dcn..,;ity (sometime-s called s ~rfacc charge den sity) is the amount
ofchargeperunitareaofsurface. This is - = 8electronunitspernm 2 inthefirst
\ 0.125
case, and Q.5 = 2 electron units per nm' in the second. The extent of polarisation
(and hence the attraction) of the electrons in adjacent anions, Jone pairs and bonds
depends on the charge density of the cation.
Small.highlychargedions(suchasAJl->)haveagreaterchargedensitythanlaige,
singlychargedions(suchases ).lftwoionshavesimilarchargedensities.thisoften
re.sultsintheirhavingsimilarpropetties
4.10 Properties of ionic compounds

Melting and boiling points
In an ionic lattice, there are many strong electrostatic attractions between oppositely
chargedions.Wethereforeexpectthationicsolidswillhavehighmehingpoints.
On melting. although the reg ular lattice is broken down. there will still be
significant attractions between the ions in the liquid . This should result in high
boiling points also. As we shall see in Topic 20. the ionic attractions are larger when
the ions are smaller. or possess a larger charge. This is apparent from Table 4.6.
Table4.6 Sma ll,highlydla rgedkmstxmd Compou nd Ca ti on A ni on Meltin g

strongly, ~adingto high melti ng points
13d!us/nm ,,,.,,, po[ n tJ"C
MgF,
MgO
82
Strength and brittleness

!fan ionic lattice is subjected toa shear or bending force, that is , a force that anempts
to break up the regular amiy of ions. this wiJJ inevitably force ions of the same charge
do...,r to each other (see Figure 4 .24). The Janke resists this strongly. Ionic lattices are
thereforequitehardandstrong. If, however, theshearingfon:ceisstrongenough, the
lattice does not give. but breaks down catastrophically - the crystal shauers into tiny
pieces. The strength of an ioniclankeisan"all-or- nothing ' strength .
Flgu re 4.24 Ashea1ingfoKewill1hotte1on

ionicaystal
Electrical conductivity
The conduction of electricity is the movement of electrical charge. The individual ions
that make up ionic compounds have a net overall electrical charge. If they are able to
move. as they can when the compound is either molten or dissolved in water. then
an electric curTeflt can flow . When in a solid lauice, however. the ions are fixed . Solid
ionic compounds do not conduct electricity.
The electrical conductivity of a solu tion of an ionic compound increases as its
concentration inctea...,s. because there are more ions to carry the current . Similarly.
for the same concentration (say lmoldm-J). a salt solution that contains highly
charged ions. such as aluminium chloride, conducts bener than a salt solution with
ionsofasmallcharge.suchassodiumchloride.
lbe conduction of electricity through metals and other solid conductors is due to
the movement of electrons (see below). When ions that are tnCNing in a solution give
uptheirchargetoa:solidconductorplacedinthesolution (an electt"Ode ). interesting
chemical reactions take place. This process. called e lcctrolysis, is described in Topic 23.
4.11 Metallic lattices

Table 4.7 Metallk:bondingi1much1tronger All metals conduct electricity. They are also m a llea ble (easily beaten or rolled into
thanthe imt,mla<il'Ousdipolelorre1ina1gon, sheets), duc tile (easily drawn into rods, wires and tubes) and s hh1y . The..., propenies
butnotas1tronga1bondinginthegiant are due to how the atoms of the metal interact with their neighbours in the la nice.
rnvalentlatticeofc.irbon
In a pure metallic element. all the atoms are identical. If we lCX>k closely at most
metallic lattices we find that the aton1s are arranged in a very similar way to the argon
Melt1ngpo1nuc
atomsinsolidargon.witheachatombeingsurroundedby\2others (s=Figure4.4,
page 72) . But dearly there are greater anractions between them. for the typical
melting point of a metal is at least l000C higher than that ofargon(seeTable4.7).
On the other hand. an element whose aton,s are strongly bonded in a macromolecular
covalentlattice.suchascarbon.hasameltingpoint2000Chigherthanthetypical
metal. So metallic bonding is strong, but not as strong as .some covalent bonding .
A due to the nature of metallic bonding comes from looking at the atomic
propenies of metallic elements - they all have only one. two or three electrons in
their 01Jter shells , and have low ionisation energies. The bulk property that is most
characteristic of metals - their dectrkal conducti,ity - often increases as the number
ofionisable outer-shell electrons increases . Electricalconducti,ityitselfdepends on the
presenceolrnobilecarriersofelectriccharge. Wecanthereforebuildupapictureof
:, metal structure consisting of an array of atoms, with at least some of their outer-shell
electronsrernovedandfreetomovethroughoutthebnice(seeFigure4.2Sa). These
d elocaliscd dearon s (see section 3.16) an, responsible for the various characteristic
physicalpropeniesofmetals,asdetailedbelow.
83
PHYSICAL CHEMISTRY
Figure 4.25 aThestructureofametallic

lattke.bWhe11a1hearirigforcei'iapplled,
adjacentlayersofcatiomc.msldeaierooe
aMther, andthemetallattkeGV1bedefOfmed
wilhoot1h.itteling
After some electrons have be<,n ..,.moved from the metal atoms, the atoms are lefc
as positive ions. The anmction between the delocalised electrons and these positive
ions is responsible for the strengths of the metallic bttices, and for their fairly high
meltingJX}ints
Electrons are very small. and move fast. When a po{ential difference is applied
acrosstheendsofametalHcconductor,chedelocalisedelectronswiJJbeanracted
to, and move towards, the positive end. This movement of electrical charge is what
The panially ionised acorns in a metal lattice are all positively charged . But they
are shielded from each oiher's repulsion by the 'sea' of delocalised electrons in
bem..,en them. This shielding is still present no maner how the lanice is di.stoned.
As a result of this. and unlike ionic bnices. metal lanices can be deformed by
bendingandshearingforceswithoutshanering(seeFigure4.25b). Metalsare
e lheshininessandhighreflectivityofthesurfacesofmetalsisalsoapropertyas-
sociated with the delocalised electrons they contain. As a photon of light hits the
su,faceofametal.itsoscillatingelectricfieldcausestheelectronsonthemetal"s
su,face ro oscillate too. This allows the photon to bounce off the surface without
any loss of momentum.
Allot ropesaretwo(ormofe)fonnsof
4.12 Graphite and the allotropy of carbon
thesameelemeot, inwhichtheatomsDf On page 74 we looked at the macfOllX>lecular covalent structure of diamond . Carbon's
moleculesarearrar)ged indiffeirotway.; O!hercommon allotrope. graphite. is very different in its properties (,..,.,. Table 4.8).
Tab le4 .8 Thepropertiesofdiamondaml Gr.iphtte

graphite
cokl\irle,;sandtramparmt blacka!ldDpaque
veryhard - thehardestnaturally verysoftandslippeiy - oversoo

ocrurfings.ohd time1softl'rthandiamond
verygoodalongtheloyer1
(IE:Si1tMty .. sx1o-""ocm)
density 3.Slgcm-' 2.27gmi-'
84
These differences in properties are due to a major difference in the bonding

between the carbon atoms in the two allotropes . In diamond. each carbon atom
is tetrahedrally bonded to four others by single. localised covalent bonds . A
three-dimensional network results . In graphite, on the other hand . each carbon
atom is bonded to only three others (using planar sp' orbitals. see section 3 .14).
A two-dimensional sheet of carbon atoms is formed . Each carbon atom has a
spare 2p orbital. containing one electron . These can overlap with one another
(just as in benzene. see section 3 . 16) to form a two-dimensional delocalised
It orbital spreading throughout the whole sheet of atoms. A graphite crystal is
composed of many sheets or layers of atoms, stacked one on top of another
(see Figure 4.26). fach sheet should be though t of as a single molecule . There
is no bonding between one sheet and the next . but the instantaneous dipole
anractionbetweenthemisquitesubstantial,becauseofthelargesurfacearea
involved .
Flgure4.26The1tructureofgr.iphite
de/:;,7.::
e lectrons
between the
layers
Owing to its layered nature. graphite is an a niso trOJl iC material. which means
that its properties are not the same in all directions . These properties o f graphite
can beclearlyrelatedtoits structure. and result in a variety of uses. ou tlined
below .
The use of graphite as an electrical conductor - whether as electrodes for

electrolysis or as brushes in electric motors - is well known . Owing to its
delocalised electrons. graphite is a good conductor along the layers. But because
electrons keep to their own layer. and cannot jump from one layer to the next.
graphite is a poor conductor in the direction at right angles to the layers . The
same is true for the conduction of heat. Graphite therefore finds a use in large
crucibles , where the conduction of heat along the walls needs to be encouraged.
but the transference of heat directly through the bonom is not wanted (see
Figure4.27)
85
PHYSICAL CHEMISTRY
Flgure4.27 Grap!litecooduct1heatakl!ig
tJJ
itsiaym
layers of graphite
ooa~, \ ~
up,idesofrnxibl~ H
!T
The weak bonding between the layers 3lJows them to slide over one 3nother
easily. One of the first uses of graphite (named from the Greek gropbo, meaning 10
draw') made use of this property - layers of carbon morns could easily be rubbed
off a Jump of g raphite, leaving a black tra= Oil paper or parchment. Apan from its
continued use in pencils. graphite is also used today as a component of lubricating
greases . The easy sliding of the layers over one anoiher combines with a strong
compression strength across the layers . This pren,ms a weight -be:iring axle from
grindingintothesurfaceofitsbearing(see Figure4.28).
Flgure4 .28 Graphitelayer11lideoverone

an.other,malingilau'il'fullublicant.
As well as diamond and graphite, carbon also forms Ol:her allOl:ropes . The structure of
one of these, buckminsterfullerene, is compared with those of diamo nd and graphite
infigure4.29.
Flgure4.29The1tructure-;ofadiamond,
bgr.iphiteandcbuckminrterfu lk>fene, c..,
Singlesheetsofthegmphirelanicea,.,.called graphcnl'. Graphite,fullerenesand

graphene all have one thing in common: delocalised electrons . Unlike dianxmd
therefore, they are capable of conducting electricity, although with the smaller simple-
molecular fullerenes this would only be around the surface of the molecule itself.
FU!lcrcnc is the generic name applied to simple molecular forms of carbon in
the form of a hollow sphere. an elHpsoid or a tube . A whole series of fullerenes is
86
now known. The first of these to be discovered was c;... It was obtained by firing a
p;:,werl'ullaser3lasampleofgraphiteatatemperatureof!0000C.ltsdiscoverers,
Harold Kroto, Roben Curl and Ricrulrd Smalley, ,vere awarded the 1996 Nobel Prize
in Chemistry for their work. lney named Coo buckmlnstcrfullercnc in honour of
the an::hitect R. Buckrninster Fuller. who used the principle of the geodesic dome in
m:rnyofhis buildings. (Thealcernming ) - and 6-mernbered rings in C.S.:,give a bonding
panern simibr to the struts in a geodesic dome - see Figure 4.30.) Other known
fullerenes rulve the formube C20 , c,,,. C.,,,, G,s, Csi, ~ and c,;... More are likely to be
synthesisedasthise=itingnewareaofchernistrydevelop.s.
Flgure4.30Geode1i::domesot theEden
Pmjecti11Comwall.England
~itselfisahighlysymrnetric:ilsphericalfOO{ba]l-srulpedrnolecule(seeFigure4.31).
Mastofthehigherfullerenesarederivedfrornthisbasicshapebyinseningringsof
caibon atoms arotmd the centre. Eventually. nanometre-sized tubes of carbon moms
are formed. Sincethesurl'aceofafullereneiscoveredbyacloudofdelocalised
electrons (as in graphite), these caibon nanotubes (CNTs) may find applications as
small-scaleconductors(seepage88).
Flgure4.31The'i'tructure of
buckmin'i'terfulk>rene
Adding functional group.s to spherical fullerenes. such as c 60 . allows them to interac!

with biological syscems. and they are finding uses in cancer therapy and the targeted
delivery of antibiotics . In the electrical field,theyareshowingprorniseashigh
temperatu,.,.superconductors
lngraphene.asingraphite,thec:irbonatomsareamingedinaregubrtv.o-
dimensional hexagonal Janice (see Figure 4.32). Graphene is the thinnest ma!erial known
butisalsoextrernely.s1tong. ltisanexcellentconductorofbothelectricityandheat.
Single sheets of graph ite were thought not to be stable on their own - it was
assumed they would spontaneously clump together to re-form g raphite. but in 2003
they were produced in quantity at the University of Manche.s1er (UK) by Andre Geim
87
PHYSICAL CHEMISTRY
and Ko.stya NovoselO\' . Geim and Novoselov were awarded the 2010 Nobel Prize in
Physics for their work. BiJJions of dollars are presently being invested in graphem,
research : the material has many JX)lential applications, such as llexible touch screens
for mobile phOlles: electrcxles in lightweight batteries: and single molecular sensors.
Graphene can be rolled into tubes. or two sheets rnn be combined to form bilayer
grapbee. The sheets can also be doped' with <Xher acorns and ions, for example
pomssium, K . All of these forms have interesting electrirnl propenies, and are now
finding uses in nanosizedelectronkdevices.
Fi gure 4. 32 Gr.iphel\l' a ling~ 11\eetof

carbon atoms
Carbo" nanoto,bes (CNTs) are tubes whose walls a"' made of grnphene sheeis joined
Table 4.9Acomp.risonoftheterislle
1trengthofsome material1 edge-to-edge. lbey could be considered either as forms of graphene. or as extended
open-endedfuUerenes,buttheirpropettiesaresufficientlyuniquetoclassthern
Tensile separately from either. The longest nanorubes that have been made have a length
strength(GPa) approaching20cm.butwithadiame1erofonlyapproximacelylru11,theirlength-to-
diameter ratio becomes an enormous 2000'.)000. lbe wa lls of some CNTs are just one
1ingle-walledn,motube 33 sheet thick, whereas OUlers have "11lls composed of two. three or more g raphene
sheets,concentricallyarranged. Theyarefindingusesinelectronics(asfield-effect
trnn.sistors, FETs) and optics, and their high thermal conductivity will encourage their use
in other applications. They are al.so remarkably strong, as the data in Table 4.9 show.
lnapartkular ca rbonnarmtubeof length20an,thewa llconsi51sofringsof 5ixhexagons,

w a partirnlar ~ice throogh the wa ll contains 12 carbon atoms. If the di51anc:e along the
tubebetweeneachringof12carbonatomsis0.10nm, whatis
ii the 1~.-itive molecular mass, M ,, of the carbon nanotube
b itsmassingr.-ims?
Graphene and CNTs are being developed for several imponant energy applications.
The use of CNTs in place of graphite at the positive electrcxle in lithium ion
batteries. This will allow a much shoner recharge time.
The use of CNTs for the storage of hydrogen gas in fuel cells. and in hydrogen
The use of CNTs, coupled with fullerenes and conducting polymers, to enhance the
effidency,and reducethecost,ofphotovoltaicsolarcells.
The manufacture of ultrncapacitors that can store electrical energy more effectively
than baneries. lbese capacitors will nO{ only have as much electrical Slorage capacity
as lithium ion baneries. but they will be able to be recharged in only a few minutes
88
4.13 The ideal gas equation

Experiments on gases - volume, pressure and
temperature
Some of the first quamicative investigmions in chemistry. in the seventeenth and
eighteenth centu ries, were into the behaviour of gases. Air in panicular was readily
available. and its volume was easily and accurately measurable . SdentiSls including
Roben Boyle, Jacques Charles and Joseph-Louis Gay-Lussac .studied how the volume
of a fixed amount of air changed when either the pressure on the gas. or the
temperatureofthegas,wasalcered.
Their results are su mmarised below.
Boyle's law
The volume Vof a fixed mass of gas at a constant temperature is inversely proportiona l to
thepressurep oo thegas
v~ "i, o r pV ~ constant
The graphs in Figure 4.33 show three ways of plouing the Boyle"s Law relation.ship
betweenthevol u meandthepressureofagas.
Flgure4.33 These threegraph1all 100Nthe

lloyle"slawrelation'i.hlp
89
PHYSICAL CHEMISTRY
Charles's Law (also called Gay-Lussac's Law)

ThevolumeVofafixedmassofgasataconstantpressureisdirectlypropoflionaltoits
temperature 7:
f ~ constant
The units of pressure

The rcssu ~ of a g as is the force it exens on a given area of its container. The SI
unit of press ure is the p asca l. Pa. which "'suits from a fon:e of Ofle newton acting
on anareaofone.squaremetre:
On this scale , the pressuretheatmosphereexertsonthesurfaceofthe

Earth at sea level is about I x IO~Pa . The atmospheric pressure 31 a particular
point on the Earth 's surface , howe ver, changes with the weather. It also
decreases with height above sea level. The variation with weather can be 10%
or so , rang ing from 0.95 x tO'Pa during a depression to I.OS x IO~Pa o n a fine,
high -pressure' day.
Sdemisls have defined s t:mda nl atmospher<' as a pres.sure o f 1.01325 x J(i'i Pa .
For most purposes , hmvever, theapproxitll3tion
is adequate. The unit LOO x IO~Pa has been given the name b a r . The bar is now
repbcingthestandardatmosphereasthemostconvenientunitofpres.sure.
Boyle would have measured his pressures with a mercury barometer (see
Figure 4.34). The pressure of the atmosphere can support a column of mercury
alx>uc 0.75m high . srnndard atmosphere" was orig inally defined as the pressure
that would suppon a column of mercury exactly 76o mm high . This is why the
conversion factor from atmospheres to pascals is nOl an exact power of 10.
Rgure4.34 As.implebarometerOeft)aridthe
Yemier=leusedtore.tdtheheighttothe
nearestO .lmm
Atmospheres. bars and pascals are all used today as pressure units. The first is more
oftenusedbychemicaleng in=rs.whereasbboratoryscientistsusuallyusepascals.
Two olhera' s are n common u : car ty"-"" pressures are ofr t1 me:, ured n
pounds per square inch (]bin -') . or in kilograms per square metre (kgm- ').
90
Absolute zero and the kelvin temperature scale

When the volume of a gas is plotted againSI its tempemtun, using the Celsius
temperature .scale, a straight line of p;:,sitive s lope is obtained . If this line is extrnpolated
back to the point where it cros.,;es the temperature axis, we find the temperature at
which the volume of gas woukl be zero. Aca,rate me-:isun,ments show that this point
occurs at ~273.15 C (see Figure 4.35). The same temperature is found no matter what
volume of gas is used. or at what pressure the experiment is carried out. What is more.
the same extrnpolated temperature is found no matter whm gas we use.
F1gure4.35 Thi1gr.iphillu1trate1Ch.ir~1>
Lawand1howsthetheoretic.ilderivationof
temperat urerc
This is a universal and fundarnenrnl point on the temperature scale. Below this
temperatun,, Charles's Law predicts thm gases would have negmive volumes. That
is dearly impossible . So presumably it is impossible to attain temperatu res lower
than - 273 . ISC. This p;:>int is known as the abs o lute :r.ero of !emperature, and
experiments in many {)(her branches of chemistiy arrive al the same conclusion. and
the same value for the absolute zero of temperature . NO{ only is it impossible to anain
temperatures lower than absoluce zero. it is impossible even to equal it.
Chemists use a temperature scale which stans at absolute zero. As mentioned in
section 2.6. it is called the a b s o lllle te m pcrntun.' scak . and its u nit is the kelvin ( K).
On this scale , each degr= is the same size as a degree on the Celsius scale. so the
con on betw=n the two easy:
temperature/K = temperature/C + 273. IS

or.moreus ually:
temperature/K = temperature/"C + 273

Figure 4.36 shows the Charles's Ltw relationship of volume plO(ted against temperature
...
Flgure4.36Toerelatklnshipbetweentlle
atJ50lutetemperatureKale.iridlheCel1iu1
91
PHYSICAL CHEMISTRY
Worked example
Wh at are the following temperatures o n the absolute temperature Kille?
a 2sc
1 Co nvert thefollowingtempe r<1t ures b ---0.sc
from dl'g rees Celsius to kelvin
a - 197(
b +273C Answer
2 Convert t hefollowi ngfrom keMn to ln eachcase,weiidd273to thetempe rature inC
degrees Celsius a Absolute temperature = 273 + 2S - 298K
a 198 K b Ab50lute temperature = 273 - 0.5 =272.5K
b 500 K c Absol ute temperature = 273 - 1S~ 258K
Amount of substance and volume

One ()(her clear influence on the volume of a gas is the amount of gas we are
studying . If we perform experiments on 2.0g of gas rather than I.O g , we expect that
under the same conditions of temperature and pre.s.sure !he firSI sample wiJJ have
twice the volume of the second. This is found to be the C3Se""
The vclume of gas, under idetitkal conditions of temperature and pre'iSUre, is proportional
totheamount(inmok!s)ofgaspresent:
Arriving at the ideal gas equation

We can combine all three influences on the volume of a g:,s into one rebtionship :
\Ve can conven this rebtionship into an equation by introducing a constant of

proportioruility. This is the g:L,; con s ta nt. Chemists h.tv e given it the symbol R.
This equation is the ideal gas equ a tion . The definition of an idC'a l ga.,; is one which
follows this equation =acrly , under all conditions of pressure and temperature . The
beh.tviours of many real gases. such as air. and its main components nitrogen and
oxygen. together with hydrogen. helium and neon, do fit in with the equation fairly
accurately . Some cxher g:,ses. however. follow the equation only approximately when
=periments are carried out at low temperatures or high pressures. The n=t section
will look at why th is is the case.
One surprising discovery was that all gases. no mauer how they differ in their
chemical reacrions. or in the sizes or shapes of their molecules. obey the equation (at
least approximately). Their points of zero volume ( T~ are all-273.15C, and R has
the same numerical va lue for all of them. ruimely 8 .31J 1' 1mol- ' .
To understand why this is the case. we must return to the major difference between
liqu ids and gases. We saw in section 4 .1 that water expands 1833 times when it forms
steam at l00C. This means that water molecules take u p only one pan in 1833 of
steam (the molecules themselves do not expa nd when convening from the liquid to
the gaseous state). The rest. which amounts to 99 .95', of the volume (= 100 x ; :~: ) ,
is empty space. This empty space is common to a ll gases. no mauer what son of
molecules tOC,y contain . The propcnies of gases are not the propcnies of empty space,
of course. They arise from the molecu les moving about and colliding with one another
within that empty space. But as long as the different molecules of various gases move
and bump into o ne anOUler in a simib r way, the values of Rand T- will be the same .
92
Worked example
Calculate the volume t aken up by 1 mol of an ide;il gas at room temperature and pressure
(2SCand1.01x10 1Pa)
Answer
WerearrangetheidealgaseqUiltionto
v ~ !!!!"!_ n~ 1.0mol
P R= 8.31J K- 1 mot- 1 [= 831NmK- 1moi- 1]
73273 + 25 = 298K
p = 1.01 x101Pa [= 1.01 x101Nm- 1)
V = 1.0x 8.31 Y 298
1.01 x 10'
=2.45 x10-lm1
=24.Sdm1
Note that when {arrying out cakulatiom using the ideal gas equation, volumes must be in
rnbk metres. In cakulatkms we often use the approximate va lue of 24dm 3 {2.4 x 10_;;,mi)
forthevolumeof1mololanidealgasat roomtemperatureandpressu re
How many moles of ide.il gas are there in the fol lowing l'Olumes?
1 2.8dmlofgasata pressureof 1.01 x 105Paand atemperature of 10C
2 54dml of gas at a pressure of S.O x 101 Pa and a temperature of 600(
3 92cmlofgasatapressureof9.S x 104Paandatemperature of 100C
Avogadro's Law
One consequence of the faet that all gases consist mostly of empty space is that the
volume of a gas does noc depend on the type o f molecules it contains. lhe Italian
chemist Amedeo Avogadro was the first to realise this general propeny. and it can
Under the same conditioo1 of temperature arid pre1SUre, equal volumes of all ga'il'1 w ill
cootainequalnumber1ofmolecule1
4.14 The behaviour of real gases

Assumptions about ideal gases
It is possible to derive the ideal gas equation from the basic principles of mechanics. 1he
k inetic th C.'Or)'Of gasl'S starts by making the following assumptions about an ideal gas.
The molecules of an ideal gas behave as rigid spheres.

There are no intermolecular fonces bet,v= the molecules of an ideal gas.
Collisions between m o lecules of an ideal gas are "perfectly elastic" - that is. there is
no loss ofkineticenergyduringcollision
The molecules of an ideal gas have no volume.
Thetheorythencon.sidersthat thepressureexenedbythegasisduetothe
bouncing of the gas molecules off the sides of the container. It rnlculatesthe
magnitude of this pressure by assuming that the molecules are in constant random
mOl:ion. and that no kinetic energy is lost during collisions with one anOl:her or with
thewalls of thecontainer.
None of the a bove four assumptions is 100% true for real gases. however. \Ve saw
in Topic 2 that atoms. and hence molecules. are n<X rigid. but are rather fuzzy around
the edges. And we saw in Topic 3 that there are various ways in which intermolecular
forces can arise. &:xhofthesefaetorswillcauseinelaSliccollisions.Finally. itis
cle:irly the case that molecules do have a volume greater than zero.
93
PHYSICAL CHEMISTRY
How some real gases behave

The behaviour of some real ga,...s is compared with th31 o f a n ideal gas in Figu re 4 .37.
As we might =pecc. the ,vays in which real g a.ses depan from ideal gas behav iour
arediffe..,-mforeach g as , becauseth eirnx,lecules a ..,- d ifferent shapesa ndsizes. ln
generaL though,wecanseethatt hedevfationsbecomegreater athighpres.sures.
Flgure4.37 Somerealgasesdepartffom
idealbehavlour,p.irtkulartywhenthepressure
ls high
If we now look at how o ne panicular gas behaves as a ..,-su it of cha nging the tempernrure
(seefigure 4.3,8)wcseethatthedeviation isgreate.st31 lowtemperaru n,s.
Flgure4.38Thebehavioorofni~n
departsfromk!ealbehaviourto.1greate1
e:r;tentasthete~atureislowered
\Ve ca n su m marise these findings as follows:
The beh aviour of re.ii gases is least like that of ,m ideal gas at low temperatures and high
94
Explaining deviation from ideal behaviour

When we increase the pressure Oil a gas, we decrease its volume (Boyle's Ltw).
\Ve are forcing the molecules closer together. and the empty s pace betw=n them is
becoming less. let us take our example of sceam. which is 9').95% empty space at
atmosphericpres.sure. lgofwateroccupieslcm 3, andthisexpandscol833cm 3
when it forms ste:im at 100 C (see section 4 .1). lf,ve co mpress I.O g of steam to
:fixet~:1::~:::i~::; /2,,:,f=h=~g:~ ::.,:::~::::~",::~::u:: :u~=

20 atmospheres (which is about the pressure inside the boiler of a steam Jocomcxive),
100 = 1.1%. When compressed , the molecules occupy a higher percentage
ofthegasthanthe0.05% theyoccupyatatmospheric pres.sure.
The main rea'iOn why gases behave ll'Ss ideally at high pll.'SSUre1 is because the volume
of their molecules becomes an inaeasingly signifiamt proportion of the overall vciume
of the gas
Looking now at the effect of temperature , we know that decreasing the temperature
ofagas3lsodecreasesitsvolume(Charles'sLaw) and hence reduces the empty
space between the molecules . But. in addition, decreasing the temperature of a gas
3lso decreases the kinetic energy the molecules posses.s . They travel more slowly, and
bounce into one another with Jes.s force. The les.s the lxxmdng force of collision, the
Themainreasonwhygasesbehaveless more significant will be the forces of anmc tion that exist between the molecules. If
ideallyatlowtempernturesisbecausethe they are nx,ving more slowly, they are likely to stick to one 3nother more effectively.
intenolecularlorcesolattrilclionbecome This causes the collisions to become Jess elastic . Evemually, on funher cooling, the
comparablein'iizetothebooOOnglorces intermolecular forces become larger than the bouncing force, and the molecules
themoleculesexperience.Thiscausesthe spend more time stickin g together than moving between one another. This is the
collisionsbetweenthemoleculestobe m o lecular explanation of why a gas condenses to 3 liquid when it is cooled to below
inelastic its boiling poim .
1 Explainthelollowingobservationintermsoftheslzesofthemoleculesandthe
intermolecularlorcesbetweeothem
Atroomtemperatult',carboodioxidecanbeliqueliedby1ubjectingittoapressult'
of 10atm. Nitrogen, however, cannot be liquefil.'d at room temperature, no mattef
howmuchPfessureisapplied.
2 Plac:ethelollowinggasesinorderofdecreaslngideality,withthemostid&1llirst
Explainyourreasonsforyourorder.
CH 4 CH 38r Clz HCI Hz
Themajordiffefencesbetweenthestructuresolsolids,liquids Ml'talsandgraphitecooductelectricitybecauseofthe
andgasesarewhetherornotthelrpartidesaretouchingone delocalisedelectroostheycontain
another,andwhethertheyarelixedinposilionormoving Metalliclatticesare ma lleab le , ductile,andhavereasona~y
Crysta lll ne solidsarecomposedof lattices,whichcanbe highml'ltingpoints
simple mo lecular, macromolecular, metallic or Ionic. The Graphiteisan anisotroplc matefial,owingtothelayernaturl'
majorphysicalpropertiesofasoliddependonthetypeoflattice of its lattice
it has The Idea l gas equation,pV ~nRT,canbederivedbyapplying
Simple molecular lattkl's have low melting points, and are the simple priOOples of mechanics to a rnllectioo of gas
l'lectricalinsulatorsunderall conditioos partides
Macromolecularlatticl'shavehighml'lting points,andare Atthooghthebehaviourofmanyrealgasesapproximates
electricalinsulatorsunderallconditioos roughlytothatofanidl'algas,realgasesarl.'leastlikelyto
Ionic compounds are formed between (usua lly) meta llic cations behavelikeanidealgasatlowtemperaturesandathigh
andnon-metallicanioos
loniclatticeshavehighmeltingpoints,arl'briltle,andonly
conductelectricitywhenmoltenor insolution
95
PHYSICAL CHEMISTRY

Ple-seethedatasectiotlof theCDforanyA,va1uesyou
""'""'
1 A new method of making very light. flexible batteries using
nanotechnology was announced in August 2007. Read the
p,assageandanswertheql.lMtionsrelatedtoit.
Researchers have de...eloped a newfflt'fgy-storage device
thatcouldeasilybemistakenforasimplesheetofblack
paper.Thenaoo-engineeredbatteryis lightweigl,t.
ultra-thinandcompletelyflexible. ltisgeMedtowaJds
a ffom your knowledge of the different structures of
meeting the d;fficult deiign and energy requirements of
carboo, suggest which of these is used to make
tomorrow's gadgets, such as implantable medical devices
nanotubes. Ill
andevenvehides.
b Suggestapropertyofthisstructurethatmakesitsuitable
Researcherssoaked'paper'inank>nic liquidelectrolyte
formakingnanotubes. [1]
whichcarriesthecharge.Theythentreateditwithaligned
c Carbon in its bu lk form is brittle like most non-metallic
carbonnanotubes,whichgivethedeviceitsblackcolour.
solids. Suggest\\tlytheenergystoragedevicedescribecl
Thenanotubesactaselectrodesandallowthestorage
canberolledintoacylinder. [1]
devices to conduct electricity. Thedevice,engineered
d Name an example of an "ionic liquid electrolyte' (not a
tofunctionasbothabatteryandasuperc;apacitor,can
solution). [1]
provide the long, steady power output comparable to a
{Cambridge Jntemarional AS & A Le11el Chemisrry 9701,
convention~ battery, as well as a supercapacitor's qUKk
Paper 4 I 08 November 2009]
burstofhighenergy.Thede..;cecanberol~.twisted,
2 So1idsexistas1atticestructures
folded, or cut into shapes with no loss of strength or
a Giantmetalliclatticesconductelectricity. Giantionic
effKiency. The'paper'batteriescanalsobestacked.likea
lattices do not. If a giant ionic lattice is mehed, the
pileofprinterpaper,toboostthetotalpoweroutput.
molten ionic cornp(Mld will cooduct electricity.
conventlo~lb.ittery 'p;iper'b;ittefY Explain these obseNations in terms of bonding, structure
and particles present. [3]
rn "'" , b The solid lattice structure of ammonia. NH3, contains
hydrogen bonds.
.
i Draw a diagram to show hydrogen bonding between
- two molecules of NHl in a solid lattice. ndude
rel~antdipok'Sandlonepairs. [2]
ii Suggest \my ice has a higher melting point than solid
ammonia. 12]
-rn c SolidSiOi melts at 1610C. So1idSiC1~ meltsat-70C
electrolyte electrolyte
Neither of the liquids formed conducts electricity.
Conventional batteries produce electrons through a Suggestthe typeoflatticestructureinsolidSiOlandin
chemical reaction between electrolyte and metal. solidSiCl 4 ande:,:plainthedifferenceinmeltingpointsin
Chemicalreactioninthe'paper'batteryisbetwef'n terms of bonding and s tru cture . [SI
elect rolyte and carbon nanotubes. {OCR CllemistryA UnitF321 05 May2011]
Electrons collect on the negati~ terminal of a battery.
Electrons must flow from the negat~ terminal, through
the external circuit to the positive terminal for the chemical
reaction to continue.
"
AS Level
Physical chemistry
5 Energy changes in chemistry

Chemistry Is the study of how atoms combine and
recombine to form differen t compounds. Energy changes
Learning outcomes
take place during these rNctions. In this topic, the Bytheeodof th istopicyoushouldbeableto
importance of energy changes in chemirtry is discussed. 5.1a) explain that some chemical l&Ktions are <1crnmpanied by
Measurement of them allows us to find out why chemical energychanges,principaltyintheformofheate<iergy;
reactions ta/ceplace in the way rhattheydo, and also ltieenefgychangl.'scanbeexothermicfoJ-lisnegative)Df
to discover the strengths of the bonds that hold atoms endothermk:W! ispmltive)
tos,ether. 5.1b) exp!a inanduse t hetermsentha/pychangeof rruction
and standitrd conditions, with pa rticular reference to
formatioo, combustioo,h'iUrntion,solution,neutral isation,
atomisation;a ndbonden ergy(Aflpositive,i.e. bood
bre<1king)(part.~als0Topk20)
5.1c) cakukiterot halpyd1,mgesfromappropriateexperimental
results, including t heu'il'ofthe~atiomhip: enthalpy
change, Afi3 ~fl'KA7
5.2a)a pplyHes1"slawtornnstructsimpleenergycycle1,
andcarryout calculationsinvo!vingsudicydes and
relevantenergyterms,withparticularreferenceto
determiningentha lpychanges that canrot befoundby
di!l'ctexperiment.e.g.anent halpychi!ngeol l0<mation
fmmrothalpychangesof combusti oo.andaverag e bond
energies(pa rt. - alsoTo~c20)
4' 5.1 Chemical energy revisited -

introducing enthalpy
\Ve saw in sectio n 2.6 tha! chemical energy is a combination of kinetic energy and
JX)!ential energy . The JXXential energy is made up of the electro.srntic a ttractions
betw=nthepaniclesand, undertheusualconditionsoftemperatureandpressure,is
usuallythelargerofthetwo.
Enthalpy and enthalpy changes

The total c hemical energy of a s ubstance is rnlled its e ntha lpy (or h e a t co nte nt).
Va lues of e nthalpyarelargebecausethe particles attract o ne another strongly ,
and it is measured for a very large number of particles . usually for one m o le
(6.0 x 10:u. see section 1.5). If this same number of particle s is considered in each
case , then a c omparison of the enthalpies o f different s ub.stances g ives a valid
contparisonoftheforces ofanractionthat e xistbetwee ntheparticles in the se
97
PHYSICAL CHEMISTRY
lnchemicalreactionstherearechangesinchemicalenergyandthereforechanges
in enthalpy. An e ntha lpy c h a n ge is given the symbol AH. The Gr=k Jener delta. A,
means change', and His the symbol for enthalpy.
If the pn:xluas of a reaaion have gremer energy than the reactants, then AH is
positive. For =ample. we rnn represent the pulling a pan of the ions in one mole of
scxlium chloride(,..,.,. section 2.6) by the following equation:
Becausethepo1entialenergyofthesy.s1ernisincreased.Af-fislargeandpositive(see
Flg u re5.1 !felll'fgyisaodedtothesy1tem, Figure 5.1). It has a value of 500000 foules per mole . This is wrinen as :
Afli1poo;iliveTheproduct1havemorel.'rlergy
th.inthereactanl5 AH = -+500kJmol 1
lf the energy of the system is decreased. AH is negative, for example when a mole of
scxlium ions and a mole of chloride ions react mgether in the reverse of the process
above(seeHgure 5.2).
This is shown by the following equation:
Afi =- 500\cJmoi- 1
When dealing with enthalpy changes, it is irnporrnnt to specify the physical state of
eachspeciesinanequation: asthealx,veequationshows , changesofstatecanbe
associatedwithve1ylargechangesofenthalpy.
Gaseoussodiurnandchlorideionsexistonlyatextremelyhightemperntures,so
theycannOlbe.studiedundernorrnal lalx>ratoryconditions. They can be studied in
Figure 5.2 If el\l'l"gy is removed from the solution, however. We can represent the dissolution of sodium chloride in water by
1y1tem. Ml i'i negative. The products have~ the following equation
elll.'l"gythanthereactants
Twoquestionscanbeaskedatthis.stage.
How has this value of+4kJmol- ' been measured?

e \Vhyisthisenthalpychangesomuchsmallerthantheenthalpychangeforthe
gas-phasereaaion?
The first question is answered in section S.2 . The second question requires a
knowledge of how sodium and chloride ions pack together in the solid and how
they associate with water m o lecules when in solution . These points are discussed
in Topic 20.
Worked example 1
Whattypeofkinetkenergyilpre1entinke?Explainyourreasoning.
Answer
Ice is a solid. and the atoms are fixed in position (see 1ectioo 2.6). The ooly motioo is
vibration, sotheatomshavevibrational kinetic energy.
Worked example 2 .a
State the sign of Ml when ke changes to water. Explain your answer.
Answer
Wheo ice melts. some intl'fmolecular bonds are broken, 10 enl'fgy is taken in and Afl is
positive.
98
Energy changes in chemistry I
5.2 Measuring enthalpy changes directly
Exothermic and endothermic reactions
Th1.> Law of Conservati o nofEnergy stat1.>1that1.>nergycanootbecreatedordestroyed;
itcanonlybeconvertedintoanotherlormolenergy.
The enthalpy change of a reaction usu3lly appears as he31. which nte3ns that there is
3 temperaturech3nge.lf theprcxluctsh3velessenth3lpyth3nthereactants,thereis
3n e nthalpy decre3se d u ring the reaction (AH is neg:,tive) and 3n equ ivalent amount
ofhe:,tenergymust begivenoutbythere3ction;thereactioniss:iidtobe
cxothcnnic. The he:,t given out is passed to the s urroundings - that is. the
environment around the re:,ction - where it can be me3sured. Most chemical
reactions are exothermic, but there are some in which the enthalpy increases (Af-/ is
p;:,sitive), and the re3ction is then said to be cndothcrmic. These reactions take in
heat fromthesurroundin gsbernusetheenthalpyoftheprcxluctsismorethanthe
For exothermicreactions,Af/is enth3lpyofthereactants.
negative.Thetemperatureofthe It is not surprising that most chemical reactions 3re =othennic. In everyday life,
surroundings increases and the
the ch3nges ,ve obsef\'e 3re usually those in which the potential energy decreases
potential1.>nergyofthesystem(that
3nd the kinetic energy increases in the form of heat. lf we push a book to the side
i1,thereactingch1.>micals)dl.'creases
For endothermicreactions,Afi is of a desk. we =pect to see it fall from the desk to the ll<X>r (its potential energy
positive. Thetemp1.>ratureofthe therefore decreases). \Vewouldbe verysurprised ifitsuddenlyrosebackupagain
surroundingsdl.'creasesandthe (its p0lenti31 energy wou ld increase) . Both processes are pos.sible in theory. as they
potential1.>nergyofthesystl.'m(the do not break the Law of Conservation of Energy.
reactingch1.>micals)increases. The direction of a chemical change is determined by the relati ve energy levels
ofthereacrnnts andprcxlucts. lftheenthalpyofthe reacta nts is higher than that
of the products (=othermic. Ml negative). the reaction is thcrmody namirn lly
possible . It might not. howe,'<'r. take place because the rate is too slow; it is then
said to be kinctically controlled. The5C kinetic factors are con sidered in Topic 8).
Measuring temperature changes and

calculating t,H
Th1.> enthalpychangeofareaction ,tJ.H. If we measure the heat g ive n ou t or taken in during a reaction. we can find this
isthechang1.>in entha lpyaccompanying enthalpy change . The simplest way o f measurin g it is to use the energy to heat (or
thecompleteconver..ionofonemol1.>ol cool) some water or 3 solution . We need to make the following measurements:
reactants into products.
e themassofthereactants
the mass of water. m (or its volume. since its density is l.OOgcm- 3)
the rise (or fall) in temperature of the water or solution. AT.
\Ve also need to k now the amou nt of energy needed to raise the temperature of
water by one degree. This is known as the s pccific h c at ca pac ity of water and is
gi,'<'n the symbol c. It has the value 4 .18J g- ' K"" ' . (Ncte that we can measure the
temperarure change using a thermometer marked in degrees Celsius, bec3use a
change in temperature is the same on either the Celsius or the kelvin scale .)
lfwerepresentth eheat changeasq, weha vethefollowi ngequation:
q = mcAT
If"""' are dealing with 3queous solutions rather than pure water. ii is the mass of
poly,tyre ne cup waterinthesolutionthatshouldbeindudedasthe"m'inth isequation. Sincethe
solutions are often quite dilute . and since the volume and heat capacity of a dilu te
solu tion a re about the same 3S those of the water it contains. ""' normally use the
following equation :
q = 4.18 xvx AT. wherev = volumeofthesolution incm 1
Flgure5.3 Abasiccalorimeter.usedlor Figure S.3 shows a simple apparatus that can be used measure the heat change. The
simpleheatexperimenl5 =panded polystyrene cup has a lid to keep he:,t losses to 3 minimu m .
99
PHYSICAL CHEMISTRY
Under!heseconditions3lltheheatproduced isusedtoraisethetempemtureof
the contents of the plastk C\JP, which therefore behaves as bolh the system and the
surroundings. An apparatus used for measuring heat changes in this way is rnlled a
To find the enthalpy change of solution of

ammonium nitrate
The enthalpy change of solution, Afl..,i, of a sub.stance is the enthalpy change
when one mole of the sub.stance is dissolved in water. Ammonium nitrate is used
in this e xperiment because the tempemtu..,- change when it dissolves is quite large.
A known volume of water is placed in the calorimeter and the initial temperature is
measured. lbe finely powdered solid is weighed in a beaker and then tipped into the
water. The water is stir,.,.,J until all the solid has dissolved. and the lowest temperature
is recorded. The worked example below shows how the enthalpy change of solution
may be calrulaced from measuring a cempemture change in this way.
Worked example
Some powdered ammonium nitrate was added to water in a plastic beaker and the
followingresultswereobtained.Cakulate the enthalpychangeofsolution,tJ.H,,.,of
mass of water ~ 100g

s.pecili(heatcapac:ityolwater = 4.18Jg- 1 K- 1
mass of ammonium nitrate = 7.10g
initial temperature = 18.2(
final temperature
Answer
q = mcA.T
= 100x4.18x(12.8 18.2) (rememberthat'A'me;ins'final initial')
=-2260J
M,(NH 4N0Jl = 14.0 + 4.0 + 14.0 -t 48.0
M ~ 80.0gffiOl1
n(NH4NOJl~ s= ~ = 0.089mol
0.089moltakesin2260J
so 1.0moltakesin i . : = 2Sx11YJ
Becauseheatistakenin,thereactionisendothermkandtJ.H,,.ispositive
tJ.H,,. =+25k.Jmol 1
ltisusualtoshowthesignol tJ.H,evenwhenitisposilive.
Measuring other enthalpy changes

The e ntha lpy c h a ngc of neutralisation . Aff..,.,, of :in add is the enthalpy change
:iccompanying the neutralisation of an :idd by a base to give one mole of w:iter.
To find it. a known :,mount of add in solution is placed in a polystyrene cup :ind
its temperature is recorded . An equiv:ilent :,mount of base is :idded and the rise in
temperatureisme:i.sured.
100
Worked example
50{m 3 ol 2.0moldm__, soditJm hydroxide wlution '!Nereadded to S0cm 3 of 2.0moldm- 1
h'jl'.!rochk>rkacidinapo!ystyreoecup.
HCl(aq} + NaOH(aq} ---+ NaC~aq) + H10(l)
Thelollowingresultswereobta ined:
initialtemperatureofHCI =17.S"C
initialtemperntureofNa0H = 17.9"C
final temperature ~ 31 .0C
Cakulatetheenthalpychangeofrieutralisation,Af/'"'"1,forthi:sreaction.
Answer
AveragetemperatureoftheHClandNaOH317.7 C
(Wecantaketheaveragetemperaturebecausethevolumesolacidandbasesolutions
arel!{Jual.Becausethesolutionisverydilute,itsspecilicheatcapacityistakeritobethe
sameasthatofwater,namely4.18Jg- 1K-1. Thisapproximationisalwaysusedin
cakulatk>mirwolvingreactionsindiltJteaqueoussolution.)
q = mc.AT
~(SO + S0) x 4.18x(31 .0 - 17.7)
~S560J
n(HCl) : n{NaOH}~ c x V(in dm1} (se.! section 1.12)
so
~2 .o x 1000 30.10mol
0.10molgivesoutS560J
so 1.0molgivesout~ = S6x1&J
Because heat is evclved, we know that the re.-iction is exothermic .-ind Ml"""' is ri~ive
Aflr>i. = -56 kJmo l- 1 (that is, permoleofwaterformed)
lnasimilarway , theternperanirechange canbe!JK"asuredforavarietyofreactiOfls

which take place on mixing, and AH can be calrula!ed. If o ne of the reactants is
in excess, it is then only nece.ssaiy to know the exact amount of the reactant that
is completely used up. as it is this reactant that determines the energy change. For
example. if magnesium ribbon is dissohed in excess hydrochlo ric add . it is the quantity
of magnesium that detennines the energy change. The actnal amount o f hydrochloric
add has no effect on the amount of heat gh'en out. The mass d the ,;olution must,
however, be known in o rder to measure the heat evolved, using the formula q = mcAT.
1 2Scmlof1.0moldm- lriitricacid,HNOi,wereplaced inaplasticcup.Tothiswere

added 2Scm 3 ol 1.0moldm-J potassium hydroxide, KOH. The initial temperature of
both solutions was 17.5(. The maximum temperature re;iched after milOng was
24.1 (
a Calrnlatetheheatgivenoutinthereaction
b Calculatethenumber-olmolesofnitricacid
t Her.cec.-ikulateAHlorthenrutralisation
:Z 7Scml of 2.0moldm- l ethanoicacid, CHiCOiH, weieplaced in a plastic cup. The
temperature was 18.2C. To this were added 75cml of 2.0moldm-J ammonium
hydroxide, NH40H, whose temper.-iture was 18.6C. After mixing, the highest
temperaturewas31.0 C.Calrnlatel'J.Hfortheneutralisation
3 0.48golma,gnesiumribbonwasi!ddedto200cm 3 ofhydrochioricaddinaplastic
beaker. The temperature at the start was 20.0 (, and after the magnesium ribbon had
dissolvedthetemperatureroseto21.2 C
a Writeanequationlorthereactionofmagnesiumribbonwithdilutehydroc:hloric
acid
b CalrnlatetJ.Hlorthisreaction
101
PHYSICAL CHEMISTRY
5.3 Enthalpy changes of combustion

The enthalpychangeofcombustion,Af/0 0/a,;ubstaoceistheenthalpychange
accompanying the complete combU51ion of one mole of the substance in oxygen
MOS! organic compounds burn readily and give off a IOI of heat . This provides our
mainsourceofenergyforhomesandforindu.stry.
Energy so urces
Fossi1fuels
Our main source of energy is the combustion of fuss ii fuels, namely coal oil and
natural gas. They g ive out large amounts of energy when burnt. but the"' an, two main
disadvanmges to their use. The fir,;1 is that supplies are finite and may run out in the
foreseeablefuru,.,.. lbeseo:ondisthatthiscornbustionproducescarlxmdioxide.which
contributestothegreenhouseeffecr(seesection 13.4). and alsoOlherpollutant.s.
Oxtl, oil and natural gas are respecth'<'ly solid. liquid and gaseous fuels. The
following considerations are made when choosing which to use.
Easeofcombustion - solidfuelsa..,-difficulttoigniteanddo
nOI burnataconstantrate. Forthisreason,coalisoften
powdered before being injected into a furnace.
Slorageandeaseoftranspon - forlocaluse.naruralgasdoes
notneedtobestored. asitisrnrriedbypipelinefromthe
source. OUisea.silystoredandrnnalsobedistnbutedby
pipeline . [nlxxheases.=pensivepipelinesmustbebid. Coal
hasthedisadvantagethatitneedstobernrried byroadorrailto
where it wUJ be used. To tr:rnspon methane without a pipeline.
itmustbeliquefied.which"'(luires=pensiverefrigeration.
lbismakesnaturalgasoflimiteduseasavehiclefuel.though
propaneandbutanearemoreusefulastheyrnnbeliquefied
by pressure alone(andarethenealled liquefied petroleum
gas. IJ>G) . IJ>G is an imponam fuel for cooking and heating in
ruralareaswithoutpipednaturalgas. Asincreasingnumbers
ofpipelinesfornaturalgasareinsta.lledthroughouttheworld.
for example in India and O,ina. the use of LPG in faaories and
hornesisgmduallybeingphasedout. BucitwillstiUbethefuel
of choice in most rural are-:is of the world. The use of coal for
driving steam engines and trains ,vas once imponam but is now
ofOfllyhistoricalinterestthroughouttheworld.
Pollution - coal contains many impurities and. when burnt.
givesoffmuchsulfurdioxide (seeseaion 10.6). The same is
true of oil. unlessitisrnrefullyrefinedbeforeuse. Crude oil
is nOl:orious for the environmental damage caused by spiJJage
fromtankersorfromtheoilextractionandflaringofthe
associated natural gas .
Economic and political considerations - the relative prices
of c=l. oil and gas must take into account the costs of
transpon. storage and pollution-reducing measures, as
Figure 5.4 A coal-buming power station. Co.ii has the highest well as political expediency. and are subtect to wide local
energyderisityalthelo11 ilfuels.givingout76kJafroergyfor a t"ons. Fuel taxes ra serevenuefgovemments, and
eac:hcm'olm.ilbumt
the resulting increased priceoffossilfuelsmayencourage
people to reduce their energy consumption.
Becausethereareseriousproblemsassociated with burning fossil fuels. much
research has been carried out to find alternative energy sources. These are
increasing ly imponam. but it is unlikely that they will provide more than a quaner
of our energy demands during the next few years. Many alternative energy sources
are ren ewa ble - they can be replaced as fast as they are used.
102
. . . . . . . . . . . . . . .1111 Alternative e ne rgy sources
1 Alternative energy sources do nOl rely on the
combustion of fuels. The following an, someofthose
llydrock'l.'trk J>Owcr - the"' are many places

intheworldwhererivershavebeendanuned
andtheresuhingdifferenceinw:uerlevelusedto
provide energy to generate electricity. for example
at Kariba on the Zambezi river between Zimbabwe
and Zambia. at haipu on the Pamna river between
Brazil and Paraguay. and the Three Gorges dam on
the Yangtze river in China. The la.st two examples
al<>ne"genera!eover6x l0 17Jofenergyperyear.
thee,quivalentofbuming6x 107 tonnesofcoal
in a coal-fired pm,.= .station. This saves pumping
millionsoftonnesofcatbondioxideintothe
atmosphel'<". However.the,.,canben,sultant
Rgure5.5Windfa1mS provide pollubon-freee/\l'lgy,buthaveavisualeffect damagetotheenvironment.whichneedstobe
oothela!ld5eape con.sideredasitmaybeunacceptable.
Tidal:md wan power- these are little used, even though the large-scale tidal po,;,.er
generator at Ul Rance in northern France first produced eJe.aricity SO year,; ago.
Wind power - the use of wind tmbines is increasing, although there is some
~ i o n to the construaiOfl of large windmills in isolated regions as they ha,..,
a dramatic effect on the landscape . The wind speed is no{ always high enough
totumthebladesinsununer,butitusuallyisinwinter,whenthedemandfor
dectridty is highest. AnOlher difficulty is that the places which are the most windy
(andthereforethemostsuitablefortheproductionofwindpower) areoftennOI
the most populous, so the pcm,'er has to be transponed to where it is needed or
powerlinesconstructedtolinktoanationalgrid.
Geothermal power - pO!entially this could be :in easy way to provide energy for
home heating , though it can only be carried out at sites with panicular geological
features. Water is pumped from deep under the ground and =mes to the surface at
atemperntureneartolx>ilingpoint.ltisno{usu:,Uypossibletousethisholwmer
toproduceelectricity,bernusesuperhe:itedsteamisneededinordertoobrnina
reasoruible energy conversion. Hov.'e\-'er, the Philippines, New Zealand and C06la
Rica obrnin a reasonable ptoponion of their energy from this .'iOIJra,.
Solar panels - the direct conversion of sunlight into electricity using solar cells
used to be quite expensive, but the application of conducting polymers has
reducedthecostofthese,and insunnyplaces, forexampleinCalifomia, Spain
andlndia,solarenergyisnoweconomicallyviable
Nnclc:ir power - the use of nuclear re:iaors based on fiss ion reactions, in
which large nuclei split into two smaller nuclei and give ou! nuclear energy, has
sharply declined as a result of accidents such as that at Chernobyl in 1986. There
is much debate over the long-tern, implications of the disposal of nuclear waste,
andmostcountriesh:idcutbackontheirnucle:irprogrammesuntilafewyears
ago.when concern fortherisein:itmosphericcarbondioxidecaused a rethink.
There is the possibility that reaaors using fusion reactions, in which lighter
nuclei join to fom1 :, heavier one, may be de,..,loped in the next few decades.
These provide the best hope for a long-term solu tion to the energy problem,
becausetheyaredeaner' anddon<Xproduceradioactivewaste
Renewable fue ls
Mo&oftheahem:iti,..,energySOJra,slisted:ibovearerenewablebecausetheyare
powered by the Sun, and so are always av:,ilable. Some fuels are made out of resourr-es
that can be replaced quickly. For example, tropical countries such as Braz.ii can grow
103
PHYSICAL CHEMISTRY
fu.st-ripeningcropssuchascomorsugarcanewhichcanbeusedcoproduceethanol
cheaply (see section 16.4) and this can be used mixed with petrol in mcxorvehicles.
HydrogenisanO{herrenewableenergyresource.lthastheadvantageofbeing
pollution free. since its combustion produces water only. and can be used in fuel
cells (see section 23.6) . Its great disadvantage is the difficulty of trnnsponing it (being
much lighter than nmuml gas. it is difficult to contain it), th01Jgh there is hope thac
the use of metal hydrides (compounds of transition mernls with hydrogen) may
overcome this problem.
For special applications, forexampleinspacerockets(seepage 107),specbl
syntheticfuelsarebeingdeveloped.
Standard enthalpy changes

Wecanmeasureenthalpiesofcombustionve,yaccurntely.andtheygiveus
informmion about the forces of attraction that exisc between the atoms in molecules
The conditions of the reaction need to be Slated vety precisely. For example, the
following equation shows the combustion CA methane:
The enthalpy change for this reaction at room temperature is 3bout l(b gremer th3n
it is 31 200C. By convention, it has been agreed that standard conditlons of lxxh
Thesta ndardenthalpy change of reactantsandprcxluctsareata pressure of either l bar(IO'P3)orl atm
combustion , t,H~ is the enthalpy change (1 .013 X 10' Pa) and. unless otherwise specified, 31 3 temperature CA 25 C. The bar
when ooe mole of the 'i'Jbstance is and atm are so nearly the same that interchanging them usually makes no significant
completely burnt in ex{esl oxygen al 1 difference to quoted Slandard thermodynamic data. Under these conditions. the
b..r or 1 aim pressure and at a specified enthalpy change is known as the sta ndard e ntha lpy c hange o f t-ombus tio n and is
temperature (usually 2SC). given the symbol AH:. the c indirnting combustion 3nd the e indicating that it was
ltisalsoimponanttospecifyexactlytheamountofsubstanceinvolvedin the
change. Two con1mon ways of writing the con,bustion of hydrogen are as follows:
H 1(g) +Io 1(g) ---+ H ,O(L)

2 H 1(g) + Oz(g) ---+ 2HzO(L)
The first equation. in which one mole of hydrogen gas undergoes con1buS1ion ,
represents AH:'. The enthalpy change forthe second reaction is 2 x AH':.
The bomb calorimeter

Highly accurate values ofAH':rnn befoundonlybyusinga specially
con structed 3pparatus called a bomb ca lo rime te r , shown in Figures 5.6 and
5.7. The bomb' is a sealed pressure vessel with steel walls. The fuel is placed
in the crucible and the bomb" filled with oxygen at a press ure of !Satm. The
"bomb ' is then placed in an insulated rnlorimeter containing a known mass of
water. Thefuelisignitedbyanelectriccurrentandthetemperaturechange
measured to within 0 .01 K . To eliminate heat losses. the rnlorimeter is placed in
another water bath whose temperature is raised with an electric heater so that
it juSI matches the average temperature in the calorimeter. The app3ratus is first
calibrated using benzok 3cid. the enthalpy of combustion of which is recognised
as a standard and whkhcanbereadilyobtained in a hig h state o f purity. There
are a number of small co rrections which must be applied to the results, but
values accurate to0. 1% canbeobtained.
FlgureS.6 Bomb uklrimeters.iremed

tomeasu rethe energyrnnten tootonly
al fuelsb!lt alsoaffoodl
104
Fl g ureS .7 lnabombcaklrimeter, accurate
value1 ofthemthalpy chanqeof combu1tion mete r_
canbeme;r;u1ed becau1eheat kl1sestothea ir
'-=: -
-
- -
I oxygen under pressure
.-
to ignite sampl
f
[1[ [
I
::I ~ -
To measure !lH ~
A simple apparatus
Figure ).8 shov.-s a simple 3ppamtus to measu re the e ruh3 lpy change of co mbustion
for a fuel such as methanol. A known volum e of water is placed in 3 copper
calorimeter 3nd its temperature is measured. The calori meter is damped so thm its
l:xise is ju st a few centimetres 31:,ove a s pirit bu rner, which contain s the fuel. The
spirit bu rner is weighed. placed under the calorimete r and lit. The water in the
calorimeter is stirred with the thermometer. \Vhen the temperature has risen 3lx,ut
10C, the flame is p ut ou t. the temperature is ncted and the spirit burner re-weighed .
Flg u reS .8 A1impleapparatu1u1edto

mea1Ureenthalpych.:mge,;ofrnmbu51km
thetmometet _
calo ~opper_
105
PHYSICAL CHEMISTRY
Thi emann 's fu el ca lorimet er

When determining Af-/':_ using a copper calorimeter. there are rv,o matof sources
the methanol is nOI: all completely burnt to carbon dioxide and water (some
incomplete combustion takes place)
nOl:alltheheat givenoffispassedtothewater.
These errors can be reduced by means of Thlema nn 's fuel ca lo rimete r (see
Figure 5.9). The fuel is burnt in a stream of oxygen to ensure complete
combustion, and the gases are sucked through a copper spiral placed in water
(aheatexchanger)sothmveiylinleheatislosttotheair.
Measurements simibr to those with the simple copper calorimeter experiment
are made. The cap is replaced on the spirit burner afler putting ouc the flame
to reduce losses of fuel by evaporation before re-weig hing. The oxygen should
be supplied fast enough so th31 the fuel burns with a clear blue name . The
suction pump is uslmlly fully on. but it may need to be turned down if the
suction is so vigorous th31 the name is pulled off the spirit burner. Thiemann"s
apparatus can give results to within 80,b of quOl:ed values .
oxygen
,upply
Flgure5.9 ln Thiemonn'sfuelGJlmimeter,
a1upplyofoxygenmrnre1co~ete
combustio11,,mdheatlos1tothe.iirisreduced
Worked example
In an experiment to detl'fmine ~ IOI methanol, CH 30H, the following readings Wl'fe
obta ined. Calculate ~for methariol
massofwaterincalorimeter z 200g
massofmethanolandburneratstart = 532.68g
massofmethanolandburneratend = S31.72g
temperatureofwateratstart 518.3(
temperatureofwateratend
Answe r
Wesh all igrioretheheattakeninbythecakirimeter.
temperatureriseolwatl'f~11.3K
q = fl'KAT
= 200 x 4.18x11.3 = 9447J
mass of methanol burnt = 0.96g and M,(CH 30H}
so amountofmethanolburnl = m5o.030mol
S{'{ause heat is eYO!ved, we know that the reactioo is exothermic and Afr,is negative
,lH''t= ~ ~ = 315x10JJmot- 1 or -3151tJmo l 1
1 a What i:s meant by 'standard cood itiom"?

b Whyi1itnec.essarytospecifythernnditionsofareaction?
2 A burner conta ining hexanol. CGH,iOH. had a mass ol 32S.68g. It was lit and
placed undl'f a copper calorimeter containing 2S0cml of water. The temperature
of the wa ter rose from 19.2 c to 31.6 C. Afterwards the burners mass was
324.37g.Cakulate
a theheatevo!ved
b Af-1,fOfhexariol.
3 a State the two main sources of l'ffOf in the experiment described in question 2
b Exp~in how these two l'ffOfS are made as =II as possible in Thiemann"s apparatus
106
Rocket fuels
To launch a rocket into space. an explosive fuel railed a J)1"0J)Cllant is needed. All
propellants have two main components
anm:idising agent (oxidam).
In the atmosphere. the oxidant is o xygen from the air, but since a rocket operates
in space it needs to rnrry its own oxidisin g agent. When the fuel combines with the
oxidising agent. it gives out a large amount o f heat. which rnuses the gases produced
to e xpand. This expansion provides thru.st for the rocket . The efficiency o f the rocket
engine is determined by the temperature and volume of the gaseous products .
The fuel and oxidant of a rocket motor make up mo.st o f the mass of the rocket.
The main function of the propellant is to produce as much energy for a given mass
as possible. Cost may be of secondary importance to the heat evolved per kilogram .
So. while rnrs that operate in the atmosphere use a cheap fuel (see Topic 13), rocket
fue lsareoftenexpensivechemicals.
There are two rypes of rocket fuels - liquid and solid .
Liquidfuelsareoftenrelativdycheapbutmayneedrefrigeratio n. so therocket
rnnonlybefuelledimmediatelybeforelih-off.
Solid fuels have the advantage that they rnn be.stored in the rocket . They are used
insmallrockets.forexamplefireworks,aswell asinlargelauncherrockets,for
example the space shuttle. Theyhavethedisadvantagethattheyproducesolid as
well as gaseous products. and this limits their power o utput.
Flg ure5 .1 0 Thesolkll\!l'ltJoostersolthis

1op,Kec:raft bumammooiumchlorate{Vll)and
aluminium. Cloud:sol aluminiumoxideare
producedaswell asthega1e1that propelthe
craft into space
107
PHYSICAL CHEMISTRY
Liquid propellants
Liquid propellants may contain rebtively common chemicals, such as liquid oxygen
with a hydrocarbon or liquid hydrogen fuel. They must be refrigerated and have a
relativelyJX)Orpo,.ver-to-weightratio
More excxic liquid fuels are also used . The lunar module used to transJX)fl
astronauts from the Apollo command mcxlule to the Moon's surface was powered
with liquid dinitrogen tetraoxide. N,04, and dimethylhydmzine, (CHl),NNH1. These
2N,O.(l) + (Oi}),NNH,(l) ----> 2co,(g) + 3N,(g) + 4H,<Xg)

!JJ-1 =-1800kJmoJ- ' = ----6980kJ(kg of reagents}""'
Fuels with an even higherpov,er-to-weightmtiohavebeeninvestigmed (for

example, Ouorine and OOl"on hydride), but they are too crude for use on the ground.
6F,(g) + B2H/g)----> 6HF(g) + 2BFfg)

AH 9 = - 2000kJ mol- 1 = - 10900kJ(kg of reagents}""'
Solid propellants
The most familiar of .solid propellants is the mixture of carbon, sulfur and potassium
nitra!e known as gunpowder or black powder' that is used in fireworks. The
simplified chemical equatiOfl for the reaction is as follows:
3C(s) + S(s) + 2KNOis) ----> K;,S(s) + 3C0g) + N,(g)

Ml =-230kJmol- ' =- 1040kJkg- '
The booster srnge of the space shunle used a mixture of ammonium chlorate(VII),
N~Cl0 4, and aluminium powder:
IOAl(s) + 6NHClOb) ----> SAl,0/s) + 3N,(g) + 6HCl(g) + 9H,O(g)

Afl =- 32S0kJmol- ' =-98S0kJkg- '
5.4 Hess's Law and enthalpy change of

formation
Introducing Hess's Law
There are ve,y few reactions who,;e enthalpy change can be measured directly by
mea.suringthechangeintemper:uu,.,inacalotimeter. Fomrnmely,wecanfindenthalpy
changes for Olher re:ittions indirectly. To do this we m:,ke use of llcss's l1lw. which Sla!es
that the value of Ml for a reaction is the same whether we crny out the re:i<1ion in ooe
steporinm:,nysteps,providedthattheinitialandfinalSla!esorcooditionsarethesame.
Hess's lawstatesthat theeothalpychaflql',Afl, forareactiooisindepeodentofthepathtaken
This law is illustrated in Figure S.11. lf (llJ-1 1 + Ml, ) was g reater than AH, we would
be a bleto getenergy'fornOl:hing' bygoingroundthecycle: rea<1ants, intermediate,
products, reactants . This would break the Ulw of Conserv:UiOfl of Energy ( pag e 99).
An example o f the use of Hess's L:iw allows us to find Ml for the decompositiOfl of
This reaction is slow and requires a high temperature to bring it about. Direct
products measurement of the !emperature change is therefore impracticable . We can,
however, carry out two reactions that rnke place readily at room temperature
figure 5.11 Hes1's Law: Ml 11 indepe!ldeot of and use their enthalpy change s IO find the Ml value that we want. These are the
the path take n, and Afl = Af/ 1 + Ml, reactio ns of calcium catbonate , and of calcium o xide , with dilute hydrochloric acid:
108
CaCOJ{) + 2HCl(aq) ----+ CaCl 1(aq) + H 10(L) + C0 1(g}
.1H't =- 17kJmor1 (l)
C aO(s) + 2HCl(aq) ----+ CaCli(aq) + H 10(1) llH! = - 195 kJ moi-1 (2)
There are tV.'O ways in which we can use these values to find !he enthalpy change for
the decomposition of calcium carbonme .
Method1 :Subtracting equations

If we subtract equation (2) from equation (1). we have:
CaCOis) - CaO(s) ----+ CO/g) Afi .. =- 17 - (- 195) = + 178kJmor 1
This equatiOfl is equivalent to CaCO/s) ----> CaO(s) + CO/.g_). which is the equation ,ve
In this method we have taken away '2HCJ(aq)' from the left-hand sides of
equations (1) and (2) and 'CaCJ/aq) + H,0(1)' from the right -hand sides. These
IE,2';,Jl-- ~ - - ~~!.IB~ terms are associated with a fixed amount of energy, and we are rnking away this
same amount of energy from both equations. so this has no effect on the final
Method2 :Constructinga Hess's law diagram

This method is preferred with more complirnted examples. We draw a diag ram like
that in Figure5. l2toindicatethetworoutesbywhkhthereactioncanbecarried
out. The diagram is nOI intended to give any indirntion of the actual energy levels
(that is why Hess's Ltw diagrams are nOI drawn venically).
In order to go from "CaCO/s)" to eacl:,(aq) + H,0(1) + CO:,(g)' , we can go either
directly or via "CaO(s) + CO,(g)".
Considering the enthalpy change involved for boih routes give.s us AH:
Flgure S.12 Hes1"1L;p,ycyc:lefortlle
dec:ompmition ofcakium carbonate. All figures AH + (- 195) = - 17
a reinkJmot-' .so AH =- 17 - (-195) = +178kJmol- '
To determine the enthalpy change w hen

copper(II) sulfate is hydrated
The equation for the hydration of copper([[) sulfate is as follows:
CuS0 4(s) + 5Hz0(1) ---+ CuS0_, .5HzO(s)

The enthalpy change for this reaction cannOI be found directly: if we add five moles
of water to one mole of anhydrous copper([[) sulfate. we do not produce hydrated
coppenJ[) sulfate aystals. These can only be made by crystallisation from a .solution.
The enthalpy change can. however. be found indirectly by determining the enthalpy
change of .solution of boih anhydrous coppe,OI) sulfate and hydrated copper([!)
sulfate(seeFigureS.13)
According to Hess"s Law,AH1 = AH + AH,. O.\Omol of anhydrous copper([!)
sulfate is added to l()()cm1 of water in a plastic cup, fined with a lid and a
thermometer. When the .solid has dissolved, the change in temperature can be used
to calculate AH, .
Figure 5.13 Hess~Lawcyc:letofi!ld The experiment is repeated using O. \Omol of powdered hydrated copper([!)
theenthalpychal\{}ewhenanhydrnus sulfate. but using only 91 cmJ of water (because the hydrated salt already contains
rnpper(ll)sult.teoystal1.irehydrated 9cm1 (O.Smol) of water). The change in temperature when the hydrated copper
sulfatedissolvescanbeusedtocakulateAH,.
The required enthalpy change of reaction AH is ghen by AH = AH, - AH, .
109
PHYSICAL CHEMISTRY
To find the enthalpy change of decomposition of

sodium hydrogencarbonate
Onheating,sodiumhydrogencarbonatedecomp;:,ses:
The enthalpy change for this decomposition may be found by measuring the
enthalpychangewhensodiumhydrogencarbonateandsodiumcarlxmatereact
sep<1mtelywithhydrochlorkacid(seeFigureS. l4) :
N aH COJ() + H Cl(aq) ----+ NaCl(aq) + H 10{1) + C01(g) Aff 1

Na 1C0 3(s) + 2H Cl(aq) ----t 2NaCl(aq) + H 100) + C0 1(g) Affz
Figure 5.1 4 He,;1~l.awcydefor!he

decompo'iifonof,;odiumh~roger1urbooatl'
NO{ethatM-/1 is multipliedby2in Figu,.,S.14. Thisisbernusethefirstequ3lion

must be multiplied by 2 in order for the equations to subuact correctly . IOOcml
of dilute hydrochloricacidareplacedina plastic cup, finedwithalidand
thermometer. O.OS mol of sodium hydrogencarlxmate is added . lhe cemperature rise
is used to calculate M-11 The value of AH, is found by repeating the experiment
using 0.05mol of anhydrous sodium carbonate. The ~uired enthalpy change can
then be calculated , asAf-/ = ll>,J-{1 - Ml,.
Enthalpy change of formation

Althoughactualvaluesoftheenthalpycontained inindividualsubstaneesarenOI.
known. it is po.s.sible to obtain accurate values of a quantity that is related to it.
namely the s tandard entha lpy c hange of forma tion. MIT-
The standard enthalpy change of formation of a sub'itance, ti.HT, is the enthil lpy
change when orie mole of the substance is formed from its elements in their standard
states.Asubstanceinit11tandardstatei1at apressure of 1.0baror 1.0atmandata
specifiedtemperature,often298K
The values of MIT fora few compounds. such as oxides, can be delennined
=perimentaUy but those for most otlier compounds must be caku lated using Hess's Law.
ThevalueofMIToftheoxideoften hasthesamevalueasMl':oftheelement.
For example.for carbon:
C(s) + 0 2(g) ---+ co,(g) Aff't(COz(g)) = dft!(C(s)) = - 393 .Sk.Jmol-!

and for hydrogen:
H /g) + i'Oz(g) ---+ H 100) .1H'f(H 100)) = llH!(H 1(g)) =- 285.91.Jmoi-1
In O!her =amples , the two are 11111 the same because the two processes are
represented by different equations. For example, for aluminium :
llH't =- 1675.71.Jmoi-1
ilH': = - 837.81.J mor1
110
The value of Aff';(Al 2 0/s)) is twice that of Aff':(Al(s)).
\Ve can use values of Ml'; to calculate AH for a reaction . On page 109 we
shmved how 10 use Hess 's Law to find the v:ilue of /J..H for the reacrion:
CaCOl(s) ---+ CaO(s) + COi(g)
AnOl:her methcxl uses standard enthalpy changes of formation in a different cycle to

findthisenthalpychange,Aff,asshowninFigure5.15.
Flgure5.15Hess"sL.JiYcydetofiridthe
enthalpychangefmtl!edl'C:ompositionof
caldumcarbonateu1irig1t.indardenthalpy
chall(Jl'Sofformation
Aff';(CaCO/s)) + !J..H = AH';(CaO(s)) + Aff';(C02 (g))

- 1206.9 + Aff. = -635.5 + (-393.5)
AH = - 1029.0 - (-12o6.9) = + l77.9kJmol- 1
lfanelementinitsstandardstateappe:,rsintheequation. it can be ignored in the

calculation because its Aff'; value is zero. For example. to calculate Aff for the
Flgure5.16Hes1"1L.JiYcyc:leforthe wehavethecydeshownin FigureS.16.

rnnversionofnitrogenmonoxidetonitrogen
dioxide.Theenth.ilpyofforrnationofthe Aff';(NO(g)) + Aff = Aff';(N0 2(g))
ell'mentoxygenlszem.so!histermcanbe +9().4 + !J..H = +33.2
ignored !J..H = +33.2 - (+90.4) = - 57.2kJmol 1
5.5 Bond enthalpies

Average bond enthalpies
When two atoms come together. they may form a bond (see section 3.2). To break
this bond and separate the two atoms requires energy (/J..H is JX>5itive). This is
becauseaforceisrequiredtopulltheatomsapan.whkhincreasesthepo{ential
energy of the syscem. For example, to break the bond in a chlorine molecule requires
242kJmol 1:
tlH =+2421.Jmol- 1
The situation is more complkaced if the molecule contains more than two atoms.
but fonunately we find that the e nergy needed to break a pankubr type of bond
between the same atoms is about the same even in different molecules . This value
is called the avc rngc bon d e n t h a lpy (or average bon d e n ergy) . If a bond joins
an atom of X to an atom of Y. the bond enthalpy is represemed by the symbol
E(X- Y ).
The average bond entha lpy, f(X- Y), is the enthalpy change when one mole of bonds
between atoms of X and atoms of Y are broken in tr>e gas phase:
XY(g)---+X(g) + Y(g) illi = f(X- Y)
111
PHYSICAL CHEMISTRY
Explaining reaction enthalpies - the formation of

hydrogen chloride
The average bond enthalpies of many bonds have been collected together in tables of
data . We can use these valuc,s of bond enthalpies to explain why some reactions give
out so much energy. For example, consider the reaction of hydrogen and chlorine to
give hydrogen chloride:
H 1(g) + Cli(g) ----+ 2HC!(g)

H- H + Cl-Cl ----t H- Cl + H- Cl
We can break the reaction down into three steps. as shown in Figu"' S.17 .
Flgure5.17 TheboOO-b1eakirig,mdbond- allmoleculessplit intoatom,

mabngstepsinthesynthesisofh)'{l1ogen
chloride.Thefigu1e1arepubli1hedbond
enthalpies,lnkJmoi- 1
chlorinemoleculessplitintoatoms
hydroge nchloridemol<'cules
The change.scan be represe-nted by equations:
H/g) ----t 2H{g) Aff = E(H- H) = +436 kJ mor 1

Cl:(&) -+ 2Cl(g) llli = E(CI--Cl) = + 242kJmor 1
2H(g) + 2Cl(g) ----t 2HC1(g) llli =-2E(H- Cl) =-2 X 131 =-8621.:Jmoi-1
(The first two changes represent bond breaking, an endothermic process, and thus
the Af-/values are positive . The third change represents bond making, an exothermic
process,andthusAffisnegative.)
We can use Hess's Law to add these three equations , to obtain
H 1(g) + Cl1(g) ----t 2HCl(g) Aff =- 1811.:Jmol- 1
If we study the values of the bond enthalpies above. we see that while the H- H and
H---Cl bonds are strong and have similar values, the Cl-CJ bond enthalpy is much
smaller. It is the weakness of the Cl-CJ bond that is the principal reason why the
NOlice that in this reaaion we broke two bonds (the H- H and Cl-CJ bonds) and
fonned two bonds (two H---Cl bonds), and that Ml equalled the bond enthalpies
of the bonds broken minus the bond enthalpies of the bonds formed. For m0.51
reactions, the number of bonds broken equals the number of bonds fonned .
Af/fora reaction ~ thebondenthalP4es ofthe bonds brokenminmthebondentha lP4es of

the bonds formed
Number of bonds broken ~ mimber of bonds formed
The combustion of hydrogen

Consider a more complicated example, the combustion of hydrogen, whose
measuredemhalpychangeisasfollows
2H 1(g) + 0 2(g) ----t 2HzO(g) tlH =-183kJmor 1

H- H + H - H + O=O ----t H- 0--H + H- 0 - H
112
Notice th31 we specify H20(g) and nOI the usual Slate of water under standard
conditions, which is H,O(l). Liquid water has intermolecular forces between the
molecules and these have to be formed as well as the O -H bonds, making the
energy of H 20(l) lower than that of H,O(g). Bond enthalpies are always quoted for
thegasphasesothat intennolecularforcesdonct havetobernken into account.
If we consider forming H,O(g), we can look up the following bond enthalpies:
bonds broken bonds formed

2B'.H-H) = 2 x 436kJ moJ- ' 4E(O-H) = 4 x46okJmol- '
B'.O=O) = 497 kJ mol 1
tornl4 bonds
Ml = enthalpy of 1:xmds broken - enthalpy of bonds formed
= 1369 - 1840
= --47lkJmol 1
Thiscakulacedvaluefortheenthalpychangeisslighclydifferentfromtheaccura1e
experimental value (-483kJ mol- '), showing chat we must n(){ always expect exact
agreement between me-asured energy changes and those cakubted from bond
emhalpy values. However. this exercise e113b[es us to suggest why the reaction is so
exothermic. At first sight all the bonds appear to be of simibr strength, but th.u for
oxygen is for two bonds. so th.u the average for one bond is onlyT kJ moJ- 1. It is the
we:ikness of the O=O bond th31 is the principal reason why combustion reactions
aresoexothermicandthereforesoimpormntassourcesofenergyineveryday life .
Worked example 1
Explain what is mea nt by the H- I bond enthalpy.
b WritethesymbollortheH-Ibondentha lpy.
c WriteanequationthatshowstheCTlangebroughtaboutindetl'fminingtheH- ibond
enthalpy.
Answe r
i1 Thisi:stheenergyrequir edtobreakonemoleolH- 1bondsinthegasphase.
b f(H - 1)
c HI(g) ..... H(9) +I(g)
Worked example 2
a Write an equation to show the breakdown of methane, CH4(g), into at oms.
b Howist!.HlofthisreactioncalculatedusingtheC- Hbondentha lpy?
Answe r
CH4(g) ..... C(g) + 4H(g)
b t!.H ~ 4 x E(C - H}
5.6 Finding bond enthalpies

Enthalpy change of atomisation
One useful pie= of data in chemistry is the sta ndard c ntlmlpy change of
atomisatio n . Aff':,. This is the energy required to produce gaseous atoms freon an
eleme-nt or compound under standard conditions. It is a quantitative indication of
the strength of the bonding in the sub.stance. If a solid breaks up into atoms. it may
first melt (accompanied by the sta ndard c ntlmlpy change of fusion . AH!.). then
evaporate (accompa nied by the s tandard emhalpy c h a nge ofvaporisadon. AH!'a.,)
andfinaUy,inthegas phase,anyren,aininglx>ndsbreak(thesumofallthebond
enthalpies).So:
Ml'!, = Ml!, + Afi'!ap + bond energy terms

113
PHYSICAL CHEMISTRY
For elements, AH'!, is the enthalpy change when one mole of morns is produced.
For compounds, it is the enthalpy change when one mole of the substance is broken
down completely into atoms.
The standardenthalpychange ofatomisati o n,Af/~1,lor

an element is the entha lpy change that occurs when ooe mole of gaseous atoms is
producedfromtheelement in it11tamlardstateunderl1andardrnnditions
compoundsistheenthalpychangetoconvertonemoleoftherubst<1ncein itsl1ar.dard
state intogaseousatomsunderstandardconditioos
Using enthalpy changes of atomisation, we can find bond e nergies in simple
Finding the bond enthalpy in simple molecules

The entha lpy change of momisation o f a compound includes the b o nd e ntha lpie.
for all bonds in the subsrnnce. This emhalpy change can be found. using Hess 's Law,
from the enthalpy change of fom,ation of !he sub.slance and the enthalpy changes
of atomisa tion of the elements it contains. For exam p le to calcu late the e nthalpy
change of atom isation of methane. we rn n con struct the Hess"s Law diagram shown
inFigureS.18.
Mli(CH.J
CN +2H(gl
Afl';(CH.) + Afl ':,(CH 4) = Afl ':,(C) + 4Afl'!,(H)

- 74.8 + Ml'!, =+714.7 + 4 X + 218
Ml'!, = 7l4.7 + ffl 2 + 74.8
= +l 66J.5kJmol 1
This enthalpy is the energy needed to break four moles of C- H bonds. Because the
four bonds in methane are identical. it is reasonable to allocate + ~ kJ mol 1 for one
mole of bonds. Th is g ives a value for the average bond enthalpy of the C-H bond in
methane, E(C- H). of 415kJmol- '.
The same calculation can be carried out for tetrachlorometha ne, CCJ.i. to find
E(C- d). The bonds need to be broken in gaseous tetmchloromethane. rather than
the liquid . which is its normal Slate u nder standard conditions. This means that
we m u st include the enthalpy change of vaporisation of tetmchloromethane in the
calculation. Figure5.19showsthe Hess"sl.awcycleused.
Flgure5.19Hes1"5L.Mtcycletofindthe
averagebo!ldenthalpylntetrachloromelh.ine (c,c1,,<,iJ----
. -"c"''1-------tc~> 4c~;>
-----='""';;<
AHfiguresareink.Jmor'.
Afl1(CC[j) + Af-/~(CCl4) + Ml ':,_(CCl.i) = Afl'!,(C) + 4Afl':,(Cl)

- 135.5 + 12.7 + Ml':, = +714.7 + 4 X 121.l
Afl '!, = 714.7 + 484.4 + 135.5 - 12.7
=+1321.9kJmol- 1
This g ives a value for B::C--Cl) of 13 2 1.9 = 330kJmoJ '.

4
114
ManyOl:hercovalent sub.srnncesareliquidsunderstandardcond itions.and itis
essential to remember to include an enthalpy change of vaporisation term in the
calcubtion of lxmd enthalpy.
Worked example
Whatdat aa re requiredtocak ulatetheaverageboode<ithalpyoft heN- Hboodin
ammo nia,NHi?
b CakulatetheaverageborKientha lpy,f(N- H)
Answe r
a Thed atarequiredare
Af-/f{NHi(9ll ~ - 46.0kJmor 1
Af-/';~H) ~ 21s.ok.Jmor1
Af-/';~N) ~ 472.7k.Jmor 1
b Figure 5.20 shows the Hess'1 Law diag ram
Flgure5.20 NH~ f---- - -

'~'''~'"~l _ ___,~ 3H(g1
Cak:ulatetheaveragebood e<it halpiesof
thefollowingbonds,using thedatagiven
beiow{all ink.Jmoi- 1)
1 H- Br
2 0- H
l P-CI
[Af-/'/'(HBr{g}} =-36.2;
AH1(HiO{l)) 3 - 285.9; Afi'r(NHi) + Af-/,NHi) ~ Afi!JN) + 3Afi!~H)
AH~PCli(l)) - - 272.4; Af-/:,(NHJl ~ Af-/:,(N) + 3Af-/,H) - Af-/'r(NHi)
AH':.i,(HiO) = +44.1; AH':.i,(PCli) = +30.7; ~ 472.7 + 3x218.0 + 46.0
AH~~H) = +218.0; Af-/:,(Br) ~+ l 11.9; z +1172.7k.Jmol""" 1
AH~~O) 3 +249.2; Af-/:,(P) = +333.9;
Thisgivesavaluefor f (N - H)of 11 ~2 -7 = 391kJrno 1-1.
AH~ 1(Cl) = +121.3]
Finding a bond enthalpy using other known

average bond enthalpies
So far ,ve have considered how to find the lxmd enthalpy in molecules thm contain
only one type of bond . !,.!any molecules contain several types of bonds. To calculate the
bond enthalpies of all of them. ""' muSI make the assumption that the bond enthalpy
ofa bond is the same even though it may be in a different molecule . Bond enthalpies
do vary slightly from molecule to molecule so we cannO{ rnke their values as being
con.slant to more than a fe,.v per cent. Howes.'er. the universal nature of average bond
energiesmakesthem,eryusefulincakulatingenthalpiesofmanydifferentreaaions.
Consider the 0---H lxmd. We rnn cakubte its strength from the enthalpy of
atomisation of wacer (see Figure 5.21).
Figure 5.21 Hess~lawcy(le to firtdthe

enthalpy(h.ingeof.itomisatiooofw.iter
""''
M,j'(H 20(1))+'1H:_.,(H, O)
Aff11}{ 20(l)) + Aff!.p{H,O) + Aff'!,(H,O) = Aff'!,(O) + 2Aff'!,(H)

- 285 .9 + 44 .l + Aff'!.{H,0) = +249.2 + 2 X 218.0
Aff'!.{H,O) = 249 .2 + 436.0 + 285 .9 - 44.1
= 927kJmol 1
1(5
PHYSICAL CHEMISTRY
This gives a value for B'.O -H) of 7= 464kJmol- ' .

We can now use this value to find the strength d the 0----0 bond in H,O, (see
Figun, 5.22) .
Flgure 5.22 Hess'sl;p,ycycletofindthe

enthalpychange of.itomi'iation ofH,o,
AfiT( H,0 2(1)) + Afi'!.p(H,O,) + AH'!,(H,0,) = 2Aff':,(O) + 2Aff'!,(H)

- 187.6 + 52 + Aff!,(H,O:,) = 2 X 249 .2 + 2 X 218
AH'!, = 498.4 + 436 + 187.6 - 52
= l070kJmor'
H 20 1 contains two 0---H bonds and one 0----0 bond. If we assume that the value of
E(O--H) is the same as thac in water.
2 X 464 + E(O-O) = 1070

a:o--o) = 142kJmor'
This low value explains why tt,o, so readily breaks down into water and oxygen.
e The entha lpychange ofareactionisthedifferer,ceinenthalpy Some key definitions

betweeflthereactantsandtheproducts Standardcondit lons alt'1.0bilror1.0atmpressureanda
The e nt ha lpyc hangeofso lution ,tiH~,istheenthalpy specifil.'dtemperatult'.usually298K
change when or.e mole of the substance is com~eteJy dissolved e lhe standardenthalpychange ofareaction,!J.H,isthl.'
in water. entha lpy change when moles of till' reactants as indicated by
Enthalpychangescanbefoondd irectJybymeasuringtheheat theeqUiltionalt'completelyconvertedintoproductsunder
givenolltortakeo induringareaction,usinga ca lorimeter. 51:andardconditions
What is measured is the temperatult' chang1.>; the re51 is Thl' enthalpycha ngeofneutra li sation ,!J.Hnt<Jtisthe
calculated according to the equation q ~ mcAT, where m is the entha lpychangewhenanacid isn1.>utralisedbybasetogiveonl.'
mass of water in grams (or the YOlume of solut km in cm3l, mole of water.
cistheo;pecificheatc.apacityofwaterandtJ.Tisthechangein The standardenthalpychangeofcombustion.!J.H't,isthl.'
temperaturl.'. entha lpy change when one mole of till' sub51ance is completely
Theenthalpychangeisgivenbytheequation!J.H =-q/n,whefe bumtinoxygenunder51andardcond itions
nisthenumbl.'fofmolesofreactanttakingpartinthereaction, The standardenthalpychangeofsolution,!J.H':,,isthl.'
ormolesofprodllCtformed entha lpy change when one moll.' of till' sub51ance is completely
Foran eKotherm ic reaction!J.His negative;foran e ndothe nn ic dissolved in water.
rl.'iKtion!J.HispositiVI.' Thl.' standardenthalpychangeofformation,!J.HT', isthl.'
Mostreactionsareexothennic,withrll.'gative!J.H entha lpychangewhenonemoleofthesub51anCl.'isformed
Hess'slaw statesthat!J.Hforarl.'iKlionisindependeotofthe fromitselernentsunderstandardconditions
pathtaken.lf!J.Hforareactioncannotbemedlureddirectly,it e lhl.' averagebondentha lpy,f{X- Y},istheenthalpychange
mayoheobefoundusingHess'slaw. when On!.' mole of bonds between atoms of X and Y are broken
Theenthalpychangeforarl.'iKtioninthegasphaseisequal in the gas phase
tothebondentha lpiesofthebondsbrokenminusthebond
X- Y(g)---> X{g) t Y(g) AH ~f{X- Y)
eothalpiesofthebondsformed
Astudyofbonderithalpiesindicatesw!iy!J.Hforsomere..ictiom The standardenthalpychangeofatomlsation,AH!bof
is so large an element is the enthalpy changl.' when On!.' mole of atoms is
Entha lpychangesofatomisationcanbeusedtocakulatebond formed from the element in its 51:amlard state
eothalpies
116
Energy change, in chemistry I
Please5ee the data SKtion of the CD for any A, values)O'J d CarbondiSlAfidereactswithnitrogen~ide.NO,ina
maynttd. 1:2 molar ratio . A yelloN solid and two colourless gases
are produced.
1 With the prospKI that fossil fuels will become increasingly
i Construc:t a balanced equation for the reaction
scarce in the future, many compounds are being considered
ii Wh.atisthechangeintheoKidationnumberof
for use in internal combustion engines. One of these is DME
SlAfurinthisreaction7 [3]
or dimetl?tt ether, CHJO(H 3. OME is a gas which can be
[GJmbridge International AS & A Level Chemistry 9701,
synthesised from methanol.
Paper 23 01 Jvne2013}
Methanolcanbeobtaioedfrombiomass,suchasplant
3 Manyorgani5msusetheaerobicrespirationofglucose,
waste from agriculture.
C6 HuO..,torelease usefu1eoergy.
a Define, withtheaidofanequationthatindudesstate
a TheoveJall e quatiooforaerobicrespirationisthesameas
5Yfllbo!S, the standard enthalpy change of combustion,
for the complete combustion of c~,,OG.
lvl~forOMEat298K. [3]
i Write the equation for the aerobic respiration of C~H.,06-
b DME may be synthesised from methanol. Relevant
[1 [
ent halpychangesofformation,lv/f,forthisreaction a re
ii Explain, in terms of bond breaking and bond forming,
givenin thetablebelow.
why this reaaion is exothermic [2]
b The table shows some enthalpy changes of combustion,
AH,.
Usethesevaluestocalcvlatelvl:...,.,.,torthe,;ynthesis
of OME, using the following equa1ion. lndude a sign in
'"'
H,(g)
CoH,Ah)
)'Ola"answer
2CH,0H(1)-+ CH10CH3(g) + H20(f) [3]
i \oVhat is meant by the tenn enrhalpy c:hange of
combvsoon,M-1,1 [2]
{Cambridge lnternationiJ/ AS & A Level Cherriwy 9701, ii The enthalpy change of formation. t.H1 of glucose,
Paper 13 03 a&blurlt' 2012/ C~uOt.. cannot be determined directly. The equation
2 Carbon disulfide, CSz, is a volatile. flammable liquid which for this enthalpy change is shown below.
isproducedinsmallqlJill"ltitiMinvolcanoes
a ThesequenceofatornsintheCS 1 moleculeissulfurto 6C(s) + 6H2(Q) + 302(9) --t C6H12~(s)
cbontosulfur. Suggest why the enthalpy change of formation of
i Or.JWa'dot-and-cross'diagramofthecarbondisulfide C.H 12 ~ca nno t bedetermineddirectly. (1]
molecule. Show outer electrons only. iii UsethetJ-11 valuesinthetabletocalcu1atethe
ii Suggesttheshapeofthemoleculeandstatethebond enthalpy change of formation of C,H,,O&- [3]
angle. [3) {OCR Chemistry A Unit F321 01 May 2011}
b Carbon disulfide is readily combusted to give CO, and
so,.
i Construa a balanced equation for the complete
combustion of CS,
ii Define the term standard enthalpy c;hange of
c:ombustion,tJ-1!. (3)
c Calculatethestandardenthalpychangeofformation
ofCS 2 fromthefollowingdata. lncludeasigninyour
answer.
standard enthalpy change of combustion of
C$i=-11 101<.Jmot" 1
standard enthalpy change of formation of
CO,= -39S kJ mo1-1
standard enthalpy change of formation of
so,= -298 kJ mot 1 [3]
117
AS Level
Physical chemistry
6 Acids and bases

In this topic the Bronrted-lowry
theory of adds and bases is
Learning outcomes
introduced. This theory describes By theeodofthistopicyoushouldbeableto
substances asacidsorbaseswhen 1.Sa) writeandconstructb.Jlancedequat iom{seealsoTopK:1)
disso/llf!dinwaterandalsoinother 1.Sb) perform cabilat kms, iriduding use of the mole concept, involvirig volu ml'S arid
solvents. Theimportantquantitative concentratiomof solutk>ns,and relatethe numberofsigriifk.ant fig uresinyoor
techniqueoftitrationisdiscussed. answerstothosegiwnoraskedlor int:hequestion(part,seealsoTopicl)
A detailed explanation of the mole 1.Sc) deduce1toichiometricrel ation1hipslromcakulatioossucha1thosein 1.Sbl
conceptintitrationca/culationsis 7.2a) showunder51andingof,andu5e,lheSrn n51ed-Lowrytheoryofacidsandbases,
given,inc/udingtheuseofthemole irxludingtheuseoftheacid-I base-I,acid-n ba'il'-Il corxept
inmorecomplextitrations, which 7.2b) exptainq ualitat ively thediffe rences inbeh aviour between51rorigandweakacids
adds emphasis to ill importance. andbasesandthepHvaluesoftheiraqueoussollllions intermsoftheexteotof
dissociation
6.1 The Arrhenius theory

What is an acid?
Two hundred years ago. sub.srnnces were called adds if they ta.sted sour (the Ultin
for sour is acidus) or if they changed the colour of some plant =tracts (see
Figure 6.1). The essential feature of their chemistry wa.s unknown and it wa.s many
years before the present--day definition of an add was recognised . The following is a
brief history of how the modem idea of an add developed . As you can see. it was 3
veryinternationalqueSl.
ins - because most non -metallic oxide.s dissolved in water to g ive acidic solutions.
the Frenchman Antoine Ulvoisier prqx,sed that all 3cids contain oxygen. This is
why he chose the name for the gas oxygen - the word comes from the two Gr=k
Flgure6.1 lemonjuiceisanatura lly words axys, meaning "acidic. or sharp tasting' and gonos, meaning generator'.
cx:rntringadd . likeothera<lds,itc:hangesthe 1816 - the British chemi.st Humphry Davy showed that Lavoisier's view was
colourof!.OO'leplant1,Ubst,mces,fmexamp4e incorrectwhenheprovedthathydrochloricaddcontainedhydrogenand
thi1!1.'dcabbageleafextr..ct
chlorine only.
1884 - the German Ju.stus von Liebig suggested that acids react with metals to
give hydrogen .
1884 - as a result of his work on the conductiviry of electrolytes, the Swedish
chemist Svante Arrhenius defined an add a.s a .sub.stance that gives hydrogen ions
Arrhenius th01Jght that the hydrogen ion was simply H~. but we now know that this
ion. which is just a pro!On. Oflly =ists by i15elf in a vacuum. 'When dissolved in water.
a hydrogen ion will be datively lxmded to a water molecule to give an o x o nium io n .
HJO~ (which is also called the h ydrox o nlum Io n ). This is funher hydrated by
hydrogen lxmding (see Figure 6.2). In chemical equations. it is beSl to avoid writing
ju.st tt . but instead to write HJo or H30"'(aq) or H"'(aq).
118
Acids and bases I
Flgu re 6.2 The1 irnplehydrog1.>nioninitially 0H,
1
forrnsad.itiveboodwithaw.iterrnoleculeto
gM'theoxoniumioo.whic:tii1thenfurther
hydratedbyhydrogenbondingtogrl'emainly -- , - 0+ / H,'
H,o,+andH,,0/ ,,o
"H,,
furtherhydr tion ' oH,
Bases and alkalis

The- ,vord alkali' come-s from the- Arabic al qaliy. which is the- calx. or calcine-d ashes.
forme-d when some- mine-rals or plane or anim:il mate-rfal have- been strongly heated in
:iir. The- :ishe-s wo uld have com:iined potassium carbon:ite- (pot-:ish) and the- oxide-s
of various metals. All of the-Se" n<""Utra lise- :icids. forming s:ilts. Alkalis we re imponam
in the- ancient world be-cauS<"" soaps we-re m:ide by heating anim:il fats with the ashes
from pbnts such as wormwood. (The- :ilkali hydrolysed the glyce-ryl e-sters in the fats ,
to g ive the sodium or pot a.s.sium s:ilts of long-chain carlx>xylic acids. which are the
constitue-ntsofsoap.)
The word "base- w:is origin:iUy applied to chemistry by the French che-mist Guillaume
Fran0)is Roudle- in 17S4. for substances that reacted with volatile- acids to change the-m
imosolidsalts. hwasthenconsideredto be-anysub.stancethmreducedthe-sourness
of:in:icid. Arrhe-niuslimitedbase-stosubst:mcesth:it reacrwithacids(the-hydroge-n
ion) to g ive the non-:icidic product wate-r. This me:int thm on his definition only metal
oxides :ind hydroxide-s were OOS<""s. We would now conside-r anything that ne-utralise-s
:inacidtobe-:ib:ise-andso,.,,uuldinclude-cxhersubstances.suchascarbonates.
Today, espe-d:illy in common us:ige-. the- words ':ilkali" :ind oo,... (and the-
adje-ctives :illmline" :ind "basic') are inte-rch:ingeable-, :ilthoug h the following syste-m
e Ab:iS<""is:i s ubst:inceth:itre:ictswith:inacid.
e Anallmliisa OOS<""thmissolubleinwate-r. Allmlisindudethe-hydroxide-softhe
Group I ele-mems (the :ilkali m<""lals). the- soluble hydroxides of the Group 2 elem<""flts
(the- allmline e:inh me-tals) , :immoni:i and the- soluble- org:mic amines .
All allmlis produce a pH be-twe-e-n 7 and 14 when dissolved in water.

Some- s:ilts. such as the- carbonates and rnrboxybtes of the alkali me-tals. also
producesolutions inwhichthe-pH is greaterth:in7 , be-cauS<""the-yproducehydroxide
ions by re:iction "ith wmer:
co/-(:iq) + H10(l) .=' HC03-(aq) + OH-(aq)

R-co,- (aq) + HzOO) .=' R--C0 1H(aq) + ott- (aq)
The-yare.the-refore-. allmlisaswell asba.S<""s.
Ionic equations
The- fonnmion of ionic com1x,,mds w:is discussed in Topic 4 . Many ionic compounds
dissolve- in water to form solutions in which the ions se-p:irate from one- :incxhe-r and
:ittracr w:ite-r mole-cules. for example-:
NaCl(s) + water ~ N:i"'{aq) + CJ-(aq)

The- '(:iq)" indicates thm the- ions :ire in aqueous solution and are hydrated. that is.
surrounde-d by water mole-cules . The-se- solutions conducr electricity.
Many of the reactions unde-rgone- by ionic compounds in .solution are in fact
reactions of the individual ions rather than of the- compound :is :, whole. An example-
is the common test for the- chloride- ion , in which :, white- pr=ipitate is forme"d when
silver nitrate- is added to a .solution of a chloride. for example- sodium chloride-:
AgNOl:iq) + NaCl(aq) ~ NaNO/aq) + AgCl(s) 0)
)19
PHYSICAL CHEMISTRY
The white predpirnte fom1s when aqu=us silver nitrate is added to a solutio n of
anJ' c hloride, for example mag nesium chloride:
Moreover, the silver sah does nOI have to be the nitrate: any soluble silver salt wiJJ
give the s ame reaction . For example:
Ag 1S0 4(aq) + 2KCl{aq) ----t K1S0_,(aq) + 2AgCl(s) (3)
The reaction is therefore seen to be one becween the cwo ions Ag\aq) and Ci-(aq)
only : any solu ble silver salt wiJJ react \\-ith aJ' soluble chloride to give the white
precipitate,thmis:
Ag(aq) + cJ- (aq) ----t Agel(s)
This is the io n le equ atio n for the reaction .
Deriving ionic equati o ns from fu ll chemica l eq uatio ns

Theprocedureconsistsofthefollowing S1eps.
Write the full balanced chemical equation. including srnte symbols .

For any ionic co mpound in aqueous solution. repbce the full formula with those
oftheseparateaqueousions.
'Cancel ' any ions that appear on lxxh sides o f the equation. These do not take
pan in the reaction. andaredescribedas spectalorions.
What is left is the ionic equation for the reaction .
Worked example
Oerivetheionkequation!OfredC!km{1)above
Answe r
There are three aqueous ionic compounds in this equation: AgNOi(aq) and NaCl(aq) on
theleh-handskle,andNaN01{aq)ontheright-handside. Theseformulaearereplacedby
thoseofthe irseparateions
Ag+(aq) + NOiiaq} + Nil+(aq} + CJ-{aq)--> Na*(aq) + NOiiaq) + AgC~s)
(Note that AgCl{s} is not writtro as its separate ions, since the Ag ' and c1- ions do not
existindeperidentlyasindivklualionsinthesolkl,butareasmciatedwithoneanotherina
lixedlattice.)
The 'spectator ions' common to both sides of the equation, Na*(aq) and NOi- (aq), are
cancelled
Ag*(aq) +~ (aq) ~ (aq) + c1 - (aq) ~ (aq) ~ - (aq) + AgCl(s)
Sothererultingionicequationis
Ag+(aq) + CJ-(aq)--tAgCl(s)
The sco pe of ionic equations

There are three areas in chemisuy where ionic equations an, useful :
precipitation n,actions (as in the worked example above)
n,dox reactions. includ ing add-metal and ,vater- metal reactions.
The following "urked examples cover each of these an,as in tum. In each case.
the ionic equation is simpler. yet more universal. and s hows mon, dearly than the
full chemical equation how reactions are related .
120
Acids and bases I
Precipitation reactions
Worked example
Write the ionic equation for the reaction betweeo barium chloride and potassium sulfate
Answer
Thefullbalar,cedequatklnis
Separateallaqueoosioniccompounds intotOOrseparn teions,andcancelthespectator

Writetheionicequationsfor,andlistthe ionsthatappe;ironbothsides
s.pecta!Ofionsin, thert!dctiombetween
aqueoos'iOllltionsofthelollowingpairs
of compounds
1 'iOdiumcarbooateandc.alciumchkiride
Whatremainsistheionic!!qualion:
2 lithiumhydroxideartdmagnesium
sutlate B,i(aq) + so/-{aq} ----, BaS0 4(s}
Acid-base reactions
Worked example
Write the ionic equation for the reaction betweeo nitric acid and sodium hydroxide
Answer
Thefu llb.Jlar.cedequatklnis
HN01(aq) + NaOH(aq) _. NaNOiaq) + Hi00)
Separateallaqueoosionkcompounds intotheirseparnteiom,andcancelthespectator
ionsthatappe;ironbothsides:
=~:~~:::i:.i~::i::~:;::
aqueousso!utioosof thefollowingpairs
H+(aq) +~ (aq) ~ (aq)+ OW(aq) ~ (aq) ~ - (aq) + HzOO)
of compounds What remains is the iooic: equatioo:

l hyd rochloric: acid and limewater H1aq) + Of1(aq)---> HiO(ll
(Ca{OH)z(aq)) (Note that H10 is almost completely a cova~t compoor,d: only two molecules in
2 s,Muricacidandpotassiumhydroxide _ ,ooo
_ m.illio " "' " "'" ' ~ "'
- '"'
O
H_.) _ _ _ __ _ _ _ __
Redox reactions
Worked example 1
Writetheionic:equat ionlorthelollowingreaction
chlorinewater + potassiumiodide--->iodine + pota'isiumchloride
solutioo so!utioo solution
Answer
Thefullbalar,cedequationis
Cl1{aq) + 2Kl(aq) ---> 2KCl{aq) + I1{aq)
Separateallaqueoosioniccompounds intotheirseparn teions,andcancelthespectator
ionsthatappe;ironbothsides
Cl 1(aq) ~ (aq) + 21 - (aq) ~ (aq) + 2c1 - (aq) + 11(aq)
(Note that it is ooly the K*laq) ions that are common to both sides the r(aq) iom have
beenoxidisedtol1(aq).)
Whatremainsi1theionic:equatioo
Cl1{aq) + 2r(aq)--->2Cl-{aq) + I1(aq)
121
PHYSICAL CHEMISTRY
Worked example 2
Writetheionicequatioolorthereactionbetweromagnesiumanddilutesulluricadd
A05wer
Thefullbalancedequatkmis
Mg(s) + HiS0 4(aq)--->MgSO.i{iKJ) + Hi(g)
Separatealla,qurou:sionicrnmpoundsintotheirseparnteions,andcancelthespectator
icmsthatappe;ironboth~es:
Mg(s) + 2W(aq) +~ - (aq) ---> Mg1+(aq) +~ - (aq) + H1(g)

Writetheiooic:equationforthefollo1\~ng
Whatremainsistheionicequation
zincmetal + hydrochloricacid----t Mg(s) + 2H*(i!Q}--->Mg1'iaq) + Hz(g)
zincchloridesohJtioo + hydrogeogas
lonicequationsforredoxre:ictionscan3lsobewrinenusingredoxhalf-Juations,
which are often lisied in books of data (see section 7.1 for a description of this methcxl).
Representing acid-base reactions

We now recognise that in an add---O<lse re:,ction, as in some (){her reactions (see
pages 120-122)theionsmakingupthesaltaresp C'Ct a tor lon s - theydonotrnke
pan in a chemical reacrion . We can therefore repre.sent these reactions by an ionic
equation which on1its such spectator ions. For example, in the equation for the
neutralisation of hydrochloric add with sodium hydroxide. the ionic equation is:
H\aq) + OI-r(aq) ---t Hp{l)
Using simplified ionic equations in this way has the advantages of showing which
bonds are being broken and which are formed. and of showing that many apparently
different add-base reactions are, in facr, identical.
According to the Arrhenius theory. add-base reacrions can be divided into three
main types:
bet,veen an add and an insoluble metal oxide. for example copper([[) oxide or
2H+(aq) + CuO(s) ---t H 10{1) + Cu'+(aq)

6H\aq) + Al,Ol(s) ---t JH 10{1) + 2Ai*(aq)
between an add and an insoluble metal hydroxide. for example magnesium

hydroxideoriron(II[)hydroxide:
2H\aq) + Mg{OH),(s) ---t 2H,O(l) + Mgl+(aq)
JH+(aq) + Fc(Ott)/s) ---t Jtti)(l) + Fc*(aq)
Worked example
WrrtethefullequatioooodtheionicequatioolortheiKtionofnitricaddonma,gnesiumoxkle.
Answer
Theproductsaremagnesiumnrtrateandwater.Thefullequationis
Writefullequationsandionicequations
forthefoUowir.greactioos MgO(s) + 2HN01(aq} --+ Mg(N01)i{aq) + Hi0(1}
1 sulluricacidwithsodiumhydroxide TheNo1- (aq)ionsareunchangedandcanbeomittedintheionicequation,but the

2 hydrochlorici1Cidwithiron(11) Mg1ionchangesfromthesolidtotheaqueousstateandmu:.tbeinduded
hydroxide
MgO(s} + 2W(aq}--+M\,11aq} + H10(1}
l nitricacidwithzincoxide
122
Acids and bases I
4' 6.2 The Bronsted-Lowry theory
Donating and accepting protons
The Arrhenius theory can o n ly be applied to reactions in aqueous solution . Many
similar reaction s cake p lace in solvems Ofher tha n water or u nder anhydrous
conditions . For example. the reaction:
C uO(s) + 2H Cl(g) ---t CuCl1(s) + HzO (\)
is very similar to:
C uO(s) + 2HCl(aq) ---t CuCl1(aq) + HzO(\)
The Danish chemisl Joha nnes Bmnsced and the English chemist Thomas Lowry were
TheBronsted-Low rytheory of acid s workingindependem lybut bol:hrealised thattheimportantfeatureofanacid-base
and bases reaction was the tran sfer of a prown from an acid to a base. T hey therefore defined a n
Mac id isaprotondonor. acid a s a substance that could donate a proton and a base as a sub=nce that could
A ba seisaprotonaueptor. accep1aprown .
Accordin g to this theory, we m ight e x pect that any sub.siance containi ng a
hydrogen atom cou ld act as an add . In practice, a substa nce behav es as an add only
if the hydrogen atom already carries a slig ht po5itive charge. - X&---H 6+. This is the
case if it is bonded to a highly electronega tive a tom. such as oxygen . nitrogen, sulfur
or a halog en, which are fou nd on the rig ht-h and side o f the Periodic Table.
In order to accept a prown. a base must contain a lone pair of electrons that it can
use to form a dative bond with the prol:on (see section 3.7). So. like an add. a base
must contain a n atom from the right-ha nd sid e of the Periodic Table .
In general. therefore . an add---base reaction is usu ally the transfer of a pro1:on from
one electronegative atom to ancxher electronegative atom.
Conjugate acid-base pairs

When an acid such as hydrochloric acid loses a promn . a b ase suc h as c i- is fom, ed
(although in this case c i- is q u ite a weak base). A prolon could retu rn 10 this base
a nd re-form HCJ. This HCVci- system is known as a conjuga t<' acld---lxl!!e pa ir. The
cha nges can be represented by the equations :
H--i- Cl ---t H+ + :c 1- and :c1-+ H+ ---t H --i- C l

!''"" >nj_ . , 1 - baoe proton oonjucat<od d
Hydrochloric add can donate just one prolon - it is called a m o n o protlc acid.
Some adds ca n donate more than one prol:on . For example, sul fu ric acid is di\n-otlc
can lose two proion s in two different steps :
H,so, ---t HS0 4- + tt + s tep l

Hso, - ---t s o/- + tt+ step 2
Similarly, somebasescanaccep1morethanonepro1:on. T hecarbonateionis

diprot ic - it can gai n two prolons in t,vo different steps :
co/- + tt+ ---t HCOJ- s tep l

HCOJ- + H+ ---t H 1C 0 1 s te p 2
Acids that can donate a maximum of one, two or thr~ protoos are cal~ moooprotic,
d iproticortriproticrespective!y.
Bases that can receive a maximum of one, two or three protons are ulled moooprotic,
diproticortriproticrespective!y.
\V.ucrisancxceptionalsub.sia nceas itcanbehavcbol:hasanaddandasabase.

Such a substance is called a n a mpholyte a nd shows a mpho!<'r ic beha, iour.
H 10 + H+ ---t HJO+ watc-rbeh avingllS a b.uc

H 20 ---tH+ + oH- watc-rbchavingllS an acid
123
PHYSICAL CHEMISTRY
Worked example 1
Showthebondingintheconjugatebaseofhyd rogensulfide,H1S
1 Showtheboodingintheconjugate Answer
IMsesofthefollowingilCids H'jl}roget1sulfidebehavesas,rnacid
a HBr
b HNOi H+ S+ H----+H + s:-+ w
c H1S04
d HS0 4-
andHS- istheconjugatebase
e Hs-
Worked example 2
2 Showtheboodingintheconjugate
acidsolthelollowin gbases ShowthebondingintheconjugaleilCidoltheethanwteion,CHJCOi-
, ,-
b Hs- Answer
c co/- Theethimoateionbehavesasabase
d Hso,- cH,co + o :- + w_.cH,co + o + H
e H10
f NH1 andethanoicadd,CHiCO.,H,istheconjugateacid.
6.3 Bn21nsted-Lowry acid-base reactions

When an acid gives up its prown to a base. a proton. tran.'!fe r reaction has rnken
place . This is a Bronsted- Low,y acid----base reaction.
An example is dissolving hydrogen chloride in water. The hydrog en chloride is the
add, andwateractsasa base:
HCl----tH+ +CJ-
H 10 : + H + ----) H 3Q +
I- f""Cfl c<>njupt<ac;d
The change can be shown by 'curly arrows' . Each curly arrow shows the movement
of a pair of electrons: the tail' shows where the pair of electrons are positioned at
the sun of the reaction, and the arrow head' shows where they finish . These two
changesrnnberepresemedasfollows:
A A
H + Cl ~tt++ : cl - and H 10 : tt + ~tt10 +
The H 30 * ion is produced by the water molecule fom1ing a dative lxmd with the
proton:
H
~o : ~tt+
H
But, just as all four bonds in the ammonium ion, NH.t, are equivalent (see section 3.7),
so are the three lxmds in the H10 + ion :
So we have two half-cqumk>ns which represent proton mo,..,ments that happen

during the reaction :
HCJ ----)H+ + cr and H 10 + H+ ----) H 10 +
acid! bose-1 bueII acidII
124
Acids and bases I
These can be combined to give the complete equ3tion:
HCl(g) + Hp(l) --+ Cr(aq) + Hp+(aq)
acid! 6-11 b-,.1 acidII
Notice that there must be four species in the equation: two conjugate add-base pairs.
If the add or base is diprotk, there are tv.'O possible neutralisation reactions. For
=ample. in the neutralisation d sulfuric add with sodium hydroxide. the following
reactions may happen:
HzSO, --+ 2H + + so/- reaction 1, when acid: base ratio~ 2
HzSO, --+ H+ + Hso, - rcaction 2, whcnacid,bascratio~ I
This gives two possible neutralisation reactions, depending on the proponions d add
and base present in the reaction.
HzSOiaq) + 20W(aq)--+ so/- (aq) + 2H,O(O

acid! k-Il 1,w.1 .cicf.n
The HSo,- (aq) ion acts as base in reaction (1) but it can also act as an acid (th.~t is, it
isamphOl:eric):
Worked example 1
Thecarbonateiooi1dipmtic.Writetwooveralliooicequationsfofthereac:tionofdilute
nilricaddwithaqueoussodiumcarbonate,withanexcessofeilhe<acidorcarbonate
Answer
Withanexcessofacid
Withanexcessofcarbonate
H/Ylaq) + CO/iaq) ---> HCOiiaq) + HiO(ll
Worked example 2
Writetherele~anthalf-equatioo1andtheoverallionic:equation1forthepo1siblereactions
wheosolidsod iumchloridei1treatedwithconcentratedrutluricacid
Answer
Thehalf-equatioo1area1follow1
\\Cithanexcessofacid
H1504 ---> HS04-+ H' and CJ- + W--->HCI
\\Cithanexcessolbase
H1S04--->S0/-+ 2H'" and CJ- + W--->HCI
Theoverallequationsa1easfollows
Foreac:holthefollowingequatioos,
decidewhethertheunde!-linedspecies \\Cithanexcessofacid:
i:sactiJlQasanacidOfabase,andstate
whichspedesi1i11conjugatebase
Of acid
\\Cithanexcessolbase
1 Br + Hso,- _.HBr + so/-
2 H1S04 + ~ ---> HS0 4-+ H1NO/
3 NHi + l::!i9_--->NH 4'+ 011
125
PHYSICAL CHEMISTRY
6.4 Strong and weak acids

According to the Arrhenius theory, a stron g acid is one that is completely ionised
inaqueoussolution,ornearlyso,whilea wcak acld isonethac isionisedtoonlya
smallextem(p;:,ssiblylessthanl ()}f,).
According to the Bronsted- Lowry theory, a s t ron g acid is one that gives up a
proton more easily than the H3o+ ion does . This means that when a strong acid
such as hydrogen chloride is dissolved in water, the following reaction takes place
HCl(g) + Hz00) ----t ttp+(aq) + Cr(aq)
A similar reaction rnkes place with oiher strong acids such as sulfurk acid and nitric
acid. lftheacidisstrong,ithasagreattendencytogiveupapromn.andsoits
conjugatebasemustbeveryweak.asithasverylittletendencytoaccep! apl'O{on . In
the above example, the Cl- is a very weak base.
A wea k acid is one that gives up a prown Jes,; easily than the H3o iOfl does . So if a
weak acid such as eihanoic acid. CH 3C01H. is dissolved in water. it hardly ionises at all:
Sinceethanoicacidhasliuletendencytogiveupaproton. itsconjugatel:xise.the
ethana,teion.mustbeafairly.s1rongbase,becauseithasatendencytoaccepta
For adds at equal concentrations. the pH values of aqueous solutions of weak

adds are higher than those of strong acids, since the concentration of H~(aq) ions
By observing that stronger acids have a tende ncy to donate protons to the
conjugate bases of weaker acids. an approximate order of add strength can be
found. as shown in Table 6. 1. A quantitative basis for this order is discussed in
Topic22
Table 6.1 Samernmmonac:idsafldbasesin Strength Strength

orderofthei11t1Engths
H,SO, ve,y1trong(pH<O) Hso,-
""'
e,o
I "",-
e,o
l""'
\\'!'ak
HS04-
CH1CO,H
'l '"'""""'' so,"
rn,co,-
I
H,co, Hco,- less weak
NH,+
Hco,-
e,o
r"''
ve,ywe ak(pH7)
'"'
co,>- j
"'"""
The direction in which an acid-base reaction takes place is governed by energy
changes (see Topic 5) . just as with any other chemical reaction . The energy
chan geisgreate.s1whenastrongacidreactswithastrongbase,andtheseare
therefore the ones that react together most readily. If a weak acid reacts with a
weak base. the reaction will not go to completion (see Topic 9) , and there will
be a significant proportion of the original acid and base remaining at equilibrium .
For example:
126
Acids and bases I
6.5 Solvents other than water
The Bronsted--Lowry theory can be applied to acids in solvents {){her than water. One
of the firs! solvents 10 be used insce-:id of wacer was liquid ammonia. with a ooiling
JX)im of - 33C. Ammonia. like water. is an ampholyte and can behave as an add or
NHl + tt+---tNH/
So in liquid ammonia. ammonium chloride, NH ..CI . behaves as a strong add. and

.sodamide, Na'NH,- , behavesasa strong base .
Writethefullbalancedequationandtheio11ic equatio11I01"thereacfo 11 betweef1

ammonium chloride and sodamide in liquid ammonia.
An{){her solvent that may be used for add--base reactions is concentrated sulfuric
add. Thisisusedlxxhasan acid and as a solventinthenitrationofbenzene (see
section2S.3). Verystrongaddssuchaschloric(VH) add protonatethesolventsulfuric
where-:isbases' suchas,vaterdeprotonatethesolvent:
6.6 Acid-base titrations

Calculations involving acid-base reactions
Quantitative information about acid--base reactions can be found by titratlon (see
Figure6.3). Thisisatechniquethat isoftenusedinanalyticalchemistrytome-:isure
with a high degr= of accuracy the concentration of an add or base in a sample, by
comparing it to the concentration of base or acid in a s tandard solution (a solution
in which the concentration of solu te in moldm- J is known accurately).
A known volume of a solution of one reactant is me-:isured using a pipeae. Into
this is run a solution of the cxher reaaant from a burette. until the reaction betw=n
the two substances is jusc complete. For an add-base reaaion, the completion of
thereacrion isusuallyfoundbyn{){ingacolourchangeofanindicatorthathasbeen
addedtothereactionmixture .
F1gure6.3The1tageo;i11canyingouta
t1tratioo
~ea~itl.ird '>Olutioo i1 made up of one
b A meas.ured volume of this 1!:.lndard solut,011

isputi11toafta1ka11dasoMioooftheother
reactanti1runinfromaburette
clheendpointisdetectedU1inganindicator.
amlthevolumeisreadofftheburette
127
PHYSICAL CHEMISTRY
The results of a titration can either be used to find the concentration of one of the
solutions or to establish the s toichlo=try of a chemical reaction, thac is, to find
how many moles of o ne subscance react with one mole of ancxher sub.siance.
Bo!:h o f these u""s require calculations involving the following two equations,
which we met in Topic I.
Thebas icequationsusedintitrations
n ~+ n~ amoont{in mol), m ~ mass(in g}, M~ molar mass (in gmol- 1)
n~cV c~rnr.centration(inmoldm-l), V~YOlume(indmlJ
Sometimes volumes are measured in cml rather than dm 3. Since l cm 3 = I ~ dm3, the
following equation is used in place of the second equmion above:
HXX>
Here, c is the concentration in moldm- 3 and vis the volume in c m 3. This equation
isoftenusedinthefonn:
The first step in a titrntion is usually to make a .standard solution. This is done by
dis.solvinganaccuratelyweighedamountofthepuresubstanceinpurewater.and
making the solu tion up co a known volume (of!en 250cm3) in a calibrated flask. It is
essentialthatthesolutioniswell mixed. Don(){dothisbyshakingbutbyturningthe
flaskupanddownatleastfivetimes.
Worked example 1
0.360g of sodium hydroxide was made up to 250cm 3 in a ca li brated flask. What is the
concentration of the solution?
Answer
The molar mass of sodium hydroxide, NaOH, is {23.0 + 16.0 + 1.0) = 40.0gmol- 1
0 360
n = !!!..= = 9.00x10-Jmol
M 40.0
1000 1000
c= xn: x9.00x10- 3
, 250
= 3.60 x 1o-'2moldm--l or 0.0360moldm--l
lntitrat ioncakulations,itisusualtowOO<to3signilicantfigures
Worked example 2
1.778g of hydrated ethanedioic add, H1C10 4.2H10, Wl'fe made up to 100cm3 in a
cali bratedfiask.Whatisthe rnocentrationoft hesolution?
Answer
Calculatetheconcentratkmofeochofthe The molar mass of H1C10 4.2H10 is (2.0 + 24.0 + 64.0 + 2 x 18.0) ~ 126.0g mo1- 1
fol!owingsolutklns
1 1.SOgofpotas'iiumhydrogensulfate,
fl = E- = ;;:~ = 1.41 X 1o-1mol
KHS04, in250cml c ~ lOOO xn = lOOO x 1.41 x 10-1

2 2.4Sgol potassiumhydrogenphthalate, , 100
C8H50 4K, in 100cm3 of solutkln =1.41 x 10- 1moldm- 3 or0.141moldm--l
Carrying out a titration

Having made a standard sol ution. the next step is to carry out the titration using this
solu tion and the solution whose concentrntion we want to find. One of the solutions
(usually the add) is placed in the burroe. and a known volume ol the other solution is
128
Acids and bases I
placed in a conical =aion flask using an accurately calibrated pipette. Before their use.
theburroeandthepipettea,.,thoroughlycleanedandthenrinsedoutwiththesolutions
they wiJJ eventually contain. to ensure that the concentrations remain constant. A few
dropsoftheindicatorareaddedtothefla.sk,andthesolutionfromtheburene(called
thetitrant)isslowlyadded,withshaking,u ntilthefirS1permanentcolourchangeis
no{ed (this is the end-point). The"' are several points to nOl:e about the procedure:
The first and final readings of the bu,.,tteshould be recorded(Figure 6.4).

Readings should be recorded to the nearest O.OScml, which is the approximate
volume of one drop. Sore:idingsarerecordeda.s. for example. 25.00, 25 .0Sand
26.00cmJ.
DuringthefirS1titration. theend-JX)intisoften missedthroughovershOOl:ing, that
is . addingslightlymoretitrantthanisnecessaryjusttochangetheindicatorcolour.
However. the reading should SliJJ be recorded as a rough' titration.
Funher titrations should then be done so that the results of two consecutive
titrations differ by no more than O.!Ocml.
Flgure6.4 Whenreadingaburette.lhe
YOlumenotedi1theiel'l'lofthebottomofthe
meni1eu1.\.\'hatarethetwob<Jrettereading1.
Indicators
and what volume has bee!\ run out of the The two mo.st common indicators that are used in titrations are methyl orange and
buretteshowninthephotograph17 phenolphthalein. Their colour changes are shown in Table 6.2 and Figure 6.5.
Table6.2 Thecoloorchange1oftwo colourchangewhenacld colourchangewhenalkall

rnmmoolyusedlndkatoo lsrunfromtheburette lsrunfromtheburette
methyl orange yellowtofir1t tingeoforange redtofirst tingeolorange
phenolphthatein pinktojustrnklurl!.'5s colourle11to jmtpink
Finding the concentration of a solution

We are provided with two solutions, A and B. which react together. Solution A, is a
standard solution and so its concentration is known. The t"u volumes used in the
titration. one from the pipette and o ne from the bureue. are found by experiment.
The balanced chemical equation shows how many mole.s of B react with o ne
To find the concentration of solution B. the knmvn values can be set o ut as shown
in Table 6.3. The steps a"' as follows.
First work ou t the amount (in moles) of reactant A:
129
PHYSICAL CHEMISTRY
~ I
(__
Figure 6.5 The colour changes of methyl orange {;;i----, b ;md c----, d) and phenolphthalein (e----; f and g----, h) at the end-point
rnnc:entr.iticm known = c,. rnocentrabontobelound c, = 7

vo lumefromtitralion = v,. YOlume frnmtitratKl n = v,
.imoun t(in moles) = n,.-------;;.. amount{in mok>s) = ns
Then use the chemical equation to find the number of moles of B th31 react with
In this way you can calculate the amoum (in moles) dB used in the titration .
Finally. workout c 0 using theequa!ion:
Worked example 1
2S.00cm1 of 0.0500moldm-1 sod ium hydrOJlide neutralised 20.00cm1 of hydrochloric acid
Whatisthernncentrationofthehydrochloricacid?
Answer
First1\'0<1<ootn(NaOH):
ll = C XlQOO
25 0
~ o.osoox 1.25x 10- 1 mol
1000
130
Acids and bases I
Nextwriteab.llaocedequation
NaOH(aq) + HCl(aq}-.. NaC~aq) + H10(l}
This shows that 1 mol of Na OH reacts with 1 mol of HCI. To f ind c(HCI), use
C=~xn
1
= :ix1.25x10- 1
: 0.0625moldm-l
Worked example l
23.6Scm1 of O.OSOOmoldm-1 hydrochloric add l\'efe neutralised by 2S.00cm1 of a solution
ofsodiumcarbooateaccordingtotheequatk>n:
2HCKaq} + Na1CO:i(aq) ---+ 2NaCl(aq) + H10(l) + COil!J)
Whati1thernncentrationofthesodiumcarboriatewlution7
Answer
n(HC1l = CX1~ = 0.0800x ~~ = 1.892x10- 1mol
Since 2 mol of HCI react with 1 mol of Na1C0 3,
n(Na1C01) =1 x1.892x ,o-l= 9.46x 1o-4mol
1000
so ctNa1CDY = 7 xn
~ ~~ x9.46x10-~
=0.0378moldm- 3
Finding the purity of a substance, or the amount

of water of crystallisation
One use of titmtions is to find the purity of a chemical or to find the number of
molecules o f water of crystallisation in a substance . The following worked examples
iJJustmtetheseuses.
Worked example 1
0.982g of an impure sample of sodium hydroxide was made up to 250cml. A 25.00cml
pipette-fullofthi1solutioowa1neutralisedby23.50cmlof0.100moldm-l hyd1ochlork
acidruninfromaburette.Whatisthepercentagepurityofthesodiumhydroxide?
Answer
n(HCl) ~c x ,ciii ~ 0.100x ~~ ~ 2.35x 10- Jmol
Since 1 mol of Na OH reacts with 1 mol of HCI,
n{NaOH) in 25cml ~ 2.35 x 10-i mol
n(NaOH}in250cml = 2.35x 10-ix ~

~ 2.35x 10-1 mol
SinceM(NaOH) = 40.0gmol- 1,
mass of pure NaOH ~ 2.35 x lo-" x 40.0 ~ 0.940g
Hence.
perceotagepurityofN aOH = ~:=~ x100 =95.7 %
131
PHYSICAL CHEMISTRY
Worked example 2
Washing soda hits the formtJla NaiC01.xHiO. A mass of 1.4280g of washing soda was
made up to 2S0cml. 25.0cm1 of this solution were nelllralised by 20.0cm1 of
O.OSOOmoldm-lhydrochloricacidrnninfrnmabtJrette
TheeqtJationlorthereactionis
NaiCOi(aq) + 2HCl(aq) --+ 2Ni!C~aq) + C0 1(g) + HiO{I)
Findthevalueofx,andthelormtJ!aolwashingsoda
1 1.250gofconcrotratedsulluricacid Answer
l\'efe dissolved in water and made up to 2
n(HCll = cx ~ = 0.0SOOx : = 1.00x10-1 mol
250cm1.A25.0cmlpipette-lullofthis 1 1
sohitioriwasneut ral isedby24.8Scm1 Since 1molofHCl1eact1withtr'lofNaiCOi,
of0.102moldrr.lsodiumhydroxide
Theequa tioriforthereactionis: n(Na.,C01) in the pipette = ; x 1.00 x 10-1 = 5.00x 1o-4mol
HiS0 4(aq) -t 2NaOH(aq) ---+ Na1S04(aq)
+ 2H 10(1) n(Na.,C01)in 2S0cm1 ~ 5.00x 10-4 x ~ ~ S.00x 10-1 mol
Whatisthepurityoltheconcentrated SinceM(NaiC01) ~ 106.0gmol- 1,
sulluricacid?
2 Ethanedioici1Cidhasthelormula mass of anhydrotJs Na 1C01 in 2S0cm1 ~ 5.00 x 10-i x 106.0 = O.S30g
H1C10 4.xH10.0.900goftheacidwere massofwa terinthewash ingsoda = {1.4280-0.S30) = 0.898g
madeupto250cml.25.0cm1 ofthis SinceM(HiO)z18.0gmol -1,
sohitioriwereneutralisedby26.75anl
of0.0532moldm- 1 'i00iumhydroxide n(Hi0) = ~ : = 4.99xlo-"mol
Theequatioriforthereactionis: So S.OOx 10...imol of NaiC01 comb ine with 4.99 x 10_;;, mol of H10
H1C10.i(aq} + 2Ni!OH{aq)---->
Therefore 1 mol of Na1C01 combines with : : : : ;~: = 9.98mol of H;P
Na1C104(aq) -t 2Hi00}
What is the value of x, and hence what So, to the nearest whole ntJmber, 1 mol of NaiC0 3 combines with 10mol of HiO
istheformulaofethanedioicacid? Therelorex =10 andthelormulaofwashingsodais Na 2 C0 3 .10H 20
Finding the stoichiometry of a reaction

TitratiOfl can also be used 10 work out the si:oichiomeuy of an acid-base reaction. If lxxh
the acid and the base are monoprctic. then one mole of the acid mU.51 =et with one
mole of the lxise. Bue if one of them is diprotic, there are two JX>SSible neucmlisation
..,.:,ctions. For eornmple. sulfuric acid and sodium hydroxide could react in two ways:
H 1SO-t<aq) + NaOH{aq) ---t NaHSO.(aq) + Hp(O

H 1S0-1{aq) + 2NaOH{aq) ---t Na1SO-t<aq) + 2Hp{l)
By making standard solutions of lxxh the acid and the base, the stoichiometry can be
found by titration.
Worked example
25.0cml of0.10Smoldm-l soditJm carbonate neutralised 24.SOcml of0.213moldm- 1
hydrochloricadd,usingmeth~orangeasanindicator.ConstrnctaneqtJationlorthe
reactionofsod itJmcarbonatewithh'jl}mchk>ricaddundertheseconditions
Answer
n(Na.,C01) = cx ~ = 0.10Sx : ~ = 2.62Sx 10-lmol
1
n(HC1l = CX1~ ~ 0.213x~~ = S.2185x10-lmol

25.0cm1 of0.0765moldn.lpotassium
carbonate, K1C0 3, neutralised22.3Sdml 5 8
ol0.08S0moldm- 1 hydrochlorkadd, So 1molofNaiCOi reacts with / ; : : , ;~' = 1.988molofHCI.
2
usingpher.olphthaleinasanindica!Of. Therefore 1 mol of Na 1C03 reacts with 2mol of HCI (to the nearest whole number).
Constructanequatiooforthereactioo The equation is
betweenpotas'iiumcarbooateand
hydrochloricacidundertheseconditions
132
Acids and bases I
6.7 Back titrations
Sometimes there is no definite end-p;:,irn to a reacrion . One example is when calcium
carlx>nateisbeingusedasthebase. Becauseitisinilubleinwater.it reactsveryslowly
with add and this means that there is no sharp end-poim when an indicator is used .
To overcome this difficulty, a known number of moles of add. which is cakubted
to be an excess of thm required !O react with all the CaCOJ is added ro the rnkium
caibonate. After the reaction has finished. the amount of add left m er can be found
Back titration
by titration againstasolublebasesuchassodiumhydroxide. Theaddusedupbythe
(addused) = {acid at start) calcium c:itbonate is the total add added at the scan minus the add left at the end .
- {acid leftateod) This method is known as hac k titration .
Worked example 1
0.765g of an impure sample of cakium carbonate was dissolved in 25.0cm1 of
1.00moldm- 1 h'jlirochloric acid . The resulting solution was made up to 250cm 3 in a
ca librated flask 25.0cml of this solution were neutra lised by 24.3Scm 3 of O.OSOmoldm-J
sodiumhydroxide.Wh atisthepurityofthecakiumcarbonate?
Answe r
Fif'>l findtheamountofacidatthestart
n{HCl)itdded = cx ~ = 1.00x : ~ = 2.SOx 10-1 mol
1
Theniindtheamoontofacidleftattheeod
~ O.OSOx ~ 1.2175x 10-3 mol
24 35
amoontof NaOH used = cx ~
1000 1000
Since 1 mol of NaOH reacts with 1 mol of HCI,
n{HCl)leftoverin250cm 3 1!ask = ~><1.2175x10-1
2S
~ 1.2175>< 1o-"mol
Now find the amount of acid used up in reiKtion with cakium carbonate
n{HCl)usedbyCaCOi 2.SOx 10-1 - 1.2175>< 10-1
51.2825x 1o-"mol
Theequat ionforthe re.-ictionis
CaCO:i(s} + 2HCl(aq) ---t CaClz(aq} + H10(1) + CO.,(g)
Since 1 mol of HCI reacts with imolof CaC0 3,

n{CaC0 1) - ix 1.2825 x 10-1 ~ 6.413 x 10-imol
Since M(CaCOi} ~ 40.1 + 12.0 + 48.0 = 100.1 gmot-1.
massofpureCaC0 1 insample z 6.413x10-1 x 100.1 = 0.6419g
0.6419
and purityolCaCOi Q.765 x 100 =83.9 %
Worked example 2
3.920g of an oxide of formula MO .vere completely dissolved in 30.0cm1 of 2.00moldm-J
sulluric acid. The resulting solution was made up to 100cm1. 25.0cml of this solution were
neutra lised by 27.SOcml of 0.100moldm- 1 sodium hydroxide. What is the relative atomic
mass of M? Ident ify the metal.
Answe r
Fif'>l lindtheamountofacidatthestart:
n{H1S04)added 3 cx ~32.00x~ 6.00x1o-"mol
1
Thenfindtheamoontofacidleftat theeod
n{NaOH)~cx ~ = 0.100>< ~~ = 2.75 x 10- 11001
1
AstheH1S04 i1inexcess,theequation f0fthereactiooi1
H1S0,i(aq} + 2NaOH(aq)---tNa1S0 4(aq) t 2H10(1)
133
PHYSICAL CHEMISTRY
S.rxe 1 mol o f NaOH neutralises .!.mol of H1S04,

1
1 100
n{H 2S0 4) left over in 100cm1 fla!.k = l x 2.75 x 10--1 x 25
= 5.SOx 10-1 mol
Now find the amount of add used up in reoctioo with MO
n(H1S0 4) used by oxide = 6.00 x 10-2 - 5.50 x 10-3 = 5.45 x 10-1 mol
The oxide MO reacts with H1S0 4 as follows
MO(s) + H1S0 4(aq) ~ MSOiaq) + H10{1)
We know that 5.45 x 10-1 mol of H1S0 4 reacted with the oxide. Sirxe one mole of acid
reactswfth ooe mole of oxide, the amount olOJlide used is 5.45x 10"""'mol, which has a
M= =s
massof3.920g
= s.:;~2~o_, = 71.9gmoi-1
A,{M) + A,(O) = 72 (to nearest \mole number)
A~M} = 72-16 =56
The metal is iron
1 A 0.789g 5ample of impure magnPSium oxide, MgO, was dissolved in 25.0anl of

1.00moldm- 1 sulfurk add . The resulting 'iOlution was made up to 100cm1 with water.
25.0cm1 of this final solution were neutralised by 27.80cm1 of O. lOOmoldm- 3 sodium
hydroxide. Cabilate the percentage purity of the magnesium o xide
2 A 0.421 g sample of hydrated lithium hydroxide, liOH.xHiO. was dissolved in water
and made up to 250anl. 25.0cml of this :;elution were neutralised by 20.0Scml of
O.OSOOmojdm- l hydrochloric acid. What is the ~alue of x?
3 (Harde<) A 10.00g sample of a fertiliser which contained ammonium sulfate, (NH 4 )1S04 ,
was boiled with 25.0cml of 2.00moldm-l sodium hydroxide. The ammonium StJlfate
rek>asedammoniaass.hownbythelclkiwingequation
(NH 4 )iS0 4{s} + 2NaOH{aq) --+ Na 1S0 4(aq) + 2NH.l{g) + 2H 10(1)
The resulting :;elution was made up to 250cml. 2S.Ocm.l of this final sollllion were
neutralised by 24.5San 3 of O.OSOOmoldm-.l hydrochloric acid. What is the percentage
by mass of ammonium StJlfate in the fertiliser'
Accord ingtothe Bronst ed-lowrytheory ofacidsandbases, Key reactions and s kill s

an acid isaprotondonoranda base isaprotonacceptor. Youneedtoknow,ortobeabletoworkolll,equationsforthe
Astrongacidhasaweak conjugatebase,anda'Nei!kacidhasa reactions ofhydrochloric,nilricandsulfurkacidswith
strong conjugate base soluble hydroxides. !.Uch as sodium hydroxide. NaOH, or
Someacidsare di protk,andcandonateuptotwoprotons(for ammonium hydroxide, NH 40H
example, sulfuric acid}. Some b.Jses are diprotic, and can accept insolub~ hydroxides, StJch as magnesium hydroxide,
uptotwoprotons{lorexample,thecarbonateion} Mg(OH}.,,oriron(lll}hydroxide.Fe(OH},
The end-po int atwhichanacidisexacdyneutralisedbyabase inwlub~oxides.suchas copper{ll}oxide,CuO,oriron(III}
canbedeterminedusingan indicator suchasmeth~orangeor oxide.fe:iOi
phenclphthalein wlublecarbonates,suchassodiumcarbonate,Na1CO.l
A standard so lution is a solution made up such that its insolub~carbonat:es,Slic:hascalciumcarbonate,CaCOi
concentration in moldm l is known You need to be able to use the loHawing mathematic.ai formulae in
lna tltratlon .astandardsolutiontakespartinanelllralisation litrationc.akJ.Jlations:
reaction. Thevolumesofbothsolutionsaremeasuredaccurately,
wt- n = amount {in mol), m = mass (in g}
sothat,forexample,theunknownconcentrationoftheother
and M = motar mass (in gmot- 1)
solution may be calculated
lna backtitration,thetitrationisusedtocakutatetheamount wt- c = concentration (in moldm-.l} and
ofacidorbaselefti nawlution afterreactionwilh.forexamp~. V ~ volume of :;elution (in dml)
a solid reactant
n5cx
1~ and c~1ooo x;'-
wherec:concent1ation(inmoldm-.l}andv=YOlumeof
wlution{incml)
134
Acids and bases I
Please <;e(' the data SKtion of the CO for any A,. value5 you c After carrying out the titration in b , the student left
::::f ~~ at::;:'.a of
may need the resulting solution to crystallise. White crystals were
1 ~5~~1 carries out eJq>eriments using acid;, b.J~and Na2SO .xH20 and a molar
1
a ~:~a~~~~!:~~~l~tr~t~by i 'Mlattermisgiventothe'.xH20'pariofthelormul~~l
reacting dilute nitric acid, HN03, with the base calcium ii ':;;: : :.molar mass of the crystals, calculate the 121
hydmicide,Ca(OH)z.
:i ~:,i:~:=t~::~:~~::!0~:VS:dilute (t] 2 a i ut~:~=:z:;:::~~:a~::=.~IO]

~;~~ and calcium hydroxide. Include state [l) :~ta:it;:~:;;;~~~~~:.;~ ~ng
i i :~~:::::.:::~:;d~: :;:~1:1:~~~i~:
nitric acid. [I)
~~:;H-:-+ e-
ii Using the symbol to represent a BroostedLowry
base, write equations which show the following
b Astudentcarriesoutatitrationtolindtheconcentrat ion
substancesactingasBr011sted-Lowryacids.
ofsomesulfurica,cid.
NH1 +-+
The student finds that 25.00cm 3 of 0.0880moldm- 1
CH10H+-+ [4]
aqueous sodium hydroxide, NaOH, is neutralised by
{Cambridge /ntemati0118/ AS & A level Chemi5try;
17.60cm3 ofdilutesulfuricacid, H2S0 4 .
9701, Paper-4103a~2013}
H2SO.(aq) + 2NaOH(aq)--+ Na1S0.(aq) + 2H;iO(I) 3a Explain~ismecW1tbythe8ronsted-l.owrytheofyofacidi
and bases. [2]
i Calculate the amount, in moles, of NaOH ~ . [I)
{Cambridge Jntemarion.,/ AS & A level Chemistry.
ii Determine the amount, in moles, of H2SO, 115ed. [11
9701, Pdpef4Q1 aJu~2009/
iii Cak:ulatetheconcentration,inmoldm-1,ofthe
sulfuricacid. (1(
13S
AS Level
Physical chemistry
7 Oxidation and reduction

In Topic 6, acid-base reactions were shown to involve
proton transfer. In this topic we show that oxidation- Learning outcomes
reduction (redox) reactions involve e/ectron transfer. The By theeod ofthistopicyou shouldbeableto
concept of oxidation number is introduced and used to find 4.3b) disc:ussthe finite natureofmaterialsasa resoo rce ,m dthe
theoxidationstateofanelement. Thisenablesustowrite importance of recycling processes
half-equations and, from these, full balanced equations. 6.1a) calculate o xidation numbers of elemetits in compotmds
Volumetric analysis using either potassium manganate(V/1) and ions
or iodine can be used to find the number of electrons 6.1b)desc:ri beand explain redoxprocessesintemi s of elect ron
transferred in a reaction. trnnsfera r.d char,ges in oxidatiooriumber
6.1 c) use changes inoxklatklnnumbersto help balance
chemical equations
7.1 What are oxidation and reduction?

Losing and gaining electrons
Oxidation and reduction processeshavebeeninuseforalx>ut7000yearsin the
=traction of metals from their ores, as well as !o de!ermine the colours of g lazes
for eanhen wa"' po!S. O ne of !he fir.s1 iextbooks " alx>ut the extraction of metals. De
Re /lfcta//ica, was written by the German sdentiSI Georg Agricoh and published in
1556 after his death . As long ago as 1741. the word reduce was used to describe the
processofextractingmetalsfromtheiror<,s. Red ucti="..,ferredtothefactthatthe
mass decreased when the or<, was con vened imo its metal. In the eighteenth century,
the French nobleman Antoine Lavoisier =ognised that these ores wer<, oxides, and
bythebegin n ingofthenineteenthcentUJytheideathatreactivemetalswereeasily
Theseob.servationsformed thebasisoftheoriginaldefinitionsofoxidationas
the addition of oxygen and reduction as the removal of oxygen. With the use o f
electrolysis for the extraction o f reactive metals such as sodiu m and aluminium from
their or<,s, this definition beca me 100 limited. The reduction of a n oxide by heating it
withhydroge-norcarbon.and itsreductioninanelectrolyticcellaresimilarchemical
processes - bcxh involve the addition of electrons to a positively charged metal ion.
The modern definition of oxidation . therefore, is the removal of electron s from a
substan ce. while redu ction is the addition of electrons to a substance. Red uctiOfl
takesplaceatthe negativeelectrode(cath od<-) ofa n electrolyticcell. and oxidation
takesphceatthepositiveelectrode(a n ode ) .
Ox id ati o n i1theremovalofelectrons
Reductlon istheadditionofelectrons
During electrolysis
oxidatklntakesplac:eattheanode - theaoodeac:ceptstheelectrons
reductiontak!!Splaceatthe ca thode - the cathode provklestheelectrons.
136
Oxidation and reduction I
Half-equations and redox reactions
The processes of oxidation and n,duction happen at the same time in oxidation-
reduction reactions (also called n'dox M'actions) - one substance is oxidised
while the other is reduced. Redox reactions can therefore be broken down into two
half-reactions. represented byhalf-equationsthatshowtheelectron loss or gain . For
example. for the combustion of magnesium to fonn magnesium oxide:
half-equation I (oxidation): Mg ---+ Mgz+ + 2c- or Mg - 2c----+ Mg"+

half-equation 2 (reduction): 0 1 + 4c----+ zol-
These half-equations are similar to those used to describe acid-base reactions in

Topic 6.
The oxidation half-equation above is written in two ways. The first method
shows more dearly that charge is being conserved. while the second method
shows more dearly that electron loss is taking place. We will generally use the
first method.
To balance the two half-equations together. the number of electrons lost from the
magnesium must be the same as the number gained by the oxygen. This can be
achieved in two ways:
add 2 x (half-equation I) to (half-equation 2) so that 2mol of magnesium re:ict with

lmolofoxygen:
2Mg(s) + 0 1(g) ---+ 2MgO(s)
lnaredoxre.action,thenumberof
:~! \~:1:;:;e~: to f x (half-equation 2) so that I mol of magnesium reacts
electrooslost = thenumberolelectrons
gained . Mg(s) + fo 1(g) ---+ MgO(s)
The complete equation for the combustion of magnesium could easily have been
written without using half-equations. With more complicated redox examples. this
would be much harder. For example. consider the reduction o f aqueous iron(ll[)
sulfate by metallic zinc. The first stage is to identify the oxidised and reduced species
The Fe~aq) ions are reduced to Fe(s) while the Zn(s) is oxidised to Zn'\aq) ions
Wecannow\\-Titetherelevanthalf-equations
oxidation: Zn ---t znH + zc-

reduction : FcH + 3e- -+Fe
We must multiply the first equation by 3 and the second equation by 2 in order to
3Zn ---t3Zn1+ + 6c-

2Fcl+ + 6c----+ 2Fc
Adding these together gives:
JZn(s) + 2FcH(aq) ---+ 3Zn"\aq) + 2Fc{s)
This reaction proceeds because Zn(s) is a more p;:>werful reducing agent than Fe(s).
Alternatively. we can say that Fe>\aq) is a more p;:>werful oxidising agent than
Zn'\aq). This can be found out qualitatively by car,ying out the reaction in a test
rube : if powdered zinc is added to a yellow-brown solution of Fe~aq) ions. the
grey zinc dissohes, to be replaced by black specks of iron metal. the brown solu tio n
fades to colourless as the Fe>\aq) ions are replaced by Zn'\aq) ions. and the tube
becomes wann as the exothermic reaction takes place.
To compare strengths of oxidising and reducing agents quantitatively. we need to
combine the two half-reactions into an electrochemical cell and measure the voltage
produced.asweshallseein Topic 23 .
137
PHYSICAL CHEMISTRY
Worked example 1
ii Whkhspecie<;hasbeeooxklisedandwhichhasbeeoreducedinthelolkiwingl&lction?
b Writethetworelevantha!f-equationsforthereactioninpart il.
Answer
a Zti(s)isoxidised,a ridcui*{aq)isreduced.(NotethatitisnotCuS04(ilQ}thatisreduced.)
b Oxidation: Zn ---+ Zn1 + 2e- ;Reduction : Cu1+ 2e---. Cu
Worked example 2
lneachofthefo llowingreactions,identify whethertheunde<l inedspecieshasbeen
oxid ised,reducedorneither.
~ + ~rz(ll--->Al8r]\s)
b 2Mg(s) + _!!Qz(s)-..2MgO{s) + TKs)
c ~+Ct-(aq)--->AgCMs)
d ~ + SnCl1(a q) ----tSnCl 4(aq}
Answer
Oxidised b Reduced c Neit her d Reduced
1 Write ha,t-equi!lioos and theo lull equatk>ns for the l&lctioos that take place between
a aqueous sulfurk add and magnesium metal
b liquidbromineandlithiummetal
c oxyget1gasandaluminiummetal
d zincmetalandaqueoossilvernitrate
2 In ead1 of the loHowing reactiom, identify wh ich s.pecies has beefl oxidised and which
has been reduced
Fe<s) + S(s) ---> H'S{s)
b Mn~(s) + 4HCl(aq) ---->MnCli(iKJ) + Cl1(g} + 2H 10(1)
c 2FeCl 1{aql + Cl1(g)---->2FeCli(aq}
d CuO(s} + Cu(s)---->Cu10(1}
l lnead1olthelolklwingrNction1,identifywhetheftheunderlinedspecieshasbeen
oxidised,reducedorneither
a CuO(s} + HiS0 4(aq) ----> CuS04(aq) + Hi0(1}
b Pbeih} t 4HCMaq) ----> PbCl1(aq) + Cl1(g) + 2H10{I)
c 4Fe{OH}.,(s) + Oi(g) t 2H10{l) ---->4Fe{OHlJ(s)
d ~s) t 2V11aq} ----> Zn1(aq} + 2v11aq)
7.2 Oxidation numbers

So far we h3ve restricted oxidmion and reduction to elements 3nd their ionic
compounds. For redox reactions of this type , it is quite cJe3r which species 3re losing
or gaining electrons. However. nuny compounds contain cov3lent bonds 3nd for
these 3 simple ionic tre3tment is in3ppropriate.
Oxidation number and simple ionic compounds

To get round this difficulty. the concep( of oxidation number ruts been developed.
This ide3 applies to bol:h ionic 3nd covalent compounds. For simple ionic
compounds. the oxidation number of the element is the s:ime as the charge on the
species conrnining the element. together with its sign . This means thm 3[1 elements
h.tve the oxidmion number 0, c3tions h3ve positive oxidmion numbers and 3nions
h.tve neg mive oxidation numbers . The oxid3tion number is wrinen in Arnbk numbers
in brackets, immediately 3fter the species ( without 3 space). So Clg) cont3ins Cl(O) ,
Feel, contains Fe(+2) 3nd MgO contains 0(-2).
138
The convention is helpful when a metal can =ist in mo"' than one o xidation
stall'. Iron. for example, can have oxidation numbers of + 2 and +3, which are
distinguished in their fonnulae by using roman numerals; for =ample. FeS04 is
iron(IJ)sulfateand Fe/SOJiisiron(ll[)sulfate.
Oxidation number and covalent molecules

The only covalem substances thac comain lxmds with no ionic character al all a"'
m o leculesthatcontainonlya singleelement.suchashydrogen.H,,orsulfur.~
The atoms of such substances a"' given an oxidation number of O. All oiher covalent
bonds have some ionic character. whose magnitude depends on the electronegativity
difference becween the two bonded atoms (see section J .10). Oxidation numbers
a"' assigned as though the lxmd is con1pletely ionic. rather than panially ionic. For
=ample, in carbon dioxide, co,, oxygen is more electronegative than carbon . Each
oxygen is given the oxidation number - 2. justasinanionicmetal oxide. Jn order
10 maimain electrical neutrality. the carbon must be assigned the oxidation number
+4. Jn this case it is helpful to include the + sign. as in other compounds carlxm
can have Ol:her oxidation numbers. including -4. Of course. we do not suggest tha!
carbon dioxide is actually composed of one c" and two i f ions. but the convemion
indicatesthattheoxidationofcarbontocarbondioxideisequivalenttoafour-
With a few =ceptions that will be discussed later, oxygen in its compounds always
has an oxidation number of - 2. Similarly, in most of its compounds. hydrogen has an
oxidation number of + I. This often helps in working out the oxidation numbers of
other elements in covalent compounds.
Theoxidationnumberofatoms inapureelementisO.
lnacompound,themoreelectronegativeelementisgivenanegativeoxidationnumber
(llu0finea1wayshasoxidationnumber - 1)
Thesumolalltheoxidatioonumbers inamoleculeisO.
lnmostcompounds,theoxidationnumberofoxygenis - 2andthatofhydrogenis + 1
Worked example 1
Whati1theoxidationnumberolcarbonineachofthefollowingcompound1?
CH4
ii b CCI, c CHiCli
Answer
a Carboni1mo1eelectronegat ivethanhyd rogen.Eachhydrogenha1oxidatioonumber + 1,
'iOlhat of carboni:s -4
b ChlOfineismo reelectronegativethancarbon.Ea.chchlorinehasoxidation
number - 1.Let theoxidationnumberofcarbonbex.Thenx + 4{- 1) ~ 0,'i0theoxidation
numberofcarbon is +4
c lftheoxidation numberolcarbon isx,wehavex + 2(+1) + 2(- 1)z0,'i0lheoxidation
numberofcarbonis O.
Worked example 2
Whatistheoxidationnumberoftheunderlinedspeciesineachofthelollowing
Whatistheoxidationnumberofthe compou nds?
underlinedelementine;ichofthe a .S:01 b ICI c f:i01
following compounds?
Answer
, Q,o, lneachcase letthe unknownoxidationnumberbex.
2 .eFi x + 3(- 2) ~ 0,givingx ~ -t6, soS = +6
3 -'HCI, b x + (- 1) = 0,givingx =+l,'iO I =+1 .
4 fuH, c 2x + 3{- 2) = 0, givingx ~ +3, 'iO P~ +3 . {Notice that each atom has itsownoxidatioo
S NHiOH number - soruchPhasanoxidationnumbero/ +3.)
139
PHYSICAL CHEMISTRY
Oxidation number and 'complex' ions containing

covalent bonds
Many ions are nOl simple. but are made up of several covalently bonded atoms . A
famiHar example is the sulfate ion. so/- . The oxidation number of each oxygen is ~2.
but it is nOl immedi3tely clear whm the oxidmion number of the sulfur atom is. We
can. however. work out the oxidation number of sulfur in pomssium s ulfate, K,S04
because the sum of all the oxidation numbers is O. If the m:idation number of sulfur is
x, then 2(+1) + x + 4(~2) = 0. givingx = ~ . This must also be the oxidation number of
lnanioo,therumoftheoxidation sulfur in the sol- ion . It rnn be found directly by letting the sum of the oxidation
numbersequal:sthechargeoothekm numbers equal the charge on the ion: x+ 4(~2) =- 2. giving x = -t{i as before.
Worked example 1
WhatistheoxidationntJmberof
CrinCrio/ -
ii b VinVOi?
Whati1theoxidationnumberof
Answer
a AlinAloi- b PinHPO/- LetthetJnknownoxidationntJmbefbex.
c VinVo1 d CinC1ol- ii2x + 7{- 2)= - 2,gMr,gx = +6
PbinPbCI/- f SninSn(OH) 61- ? b x + 2(- 2) = 1,givingx =+5
The oxidation numbers of oxygen and hydrogen

Oxygen is the second m0.51 electronegative element , and in most of its compotJnds it
has an oxidation number-2. There a"' two exceptions
As fltJorine is more electronegative than oxygen. compotJnds of oxygen and

fluorine are known as oxygen fluorides rather than fluorine o xides. (The names of
compounds usually stan with the least electronegative element .) For example. in
the fluoride OF,. each fluorine has an oxidation number of - 1 and oxygen has an
Peroxides contain the 0---0 bond . In both the peroxide ion. o,>-. and in covalent
peroxides such as hydrogen peroxide, H,o,. eac h o xygen atom has an oxidation
In most of its compounds , hydrogen is joined to a mo"' electroneg ative element

such as carbon or oxygen. so in these compounds the oxidation number of hydrogen
is +l . But there are also comi:x><mds in which hydrogen is con,bined with a metal
that is kss electronegative than hydrogen (for example. lithium hydride. UH). In these
compounds. the oxidation number of hydrogen is - 1.
The usefulness of oxidation numbers
In quantitative work. particularly volumetric analysis (as we shall see later in the
topic) , it is necessary to know the stoichiomeuy of the reaction being studied. and
this is most easily found using oxidation numbers
\Vhen convening one compound into another. it is = = r y to know if the reaction
involves oxidation and reduction. This is most easily found by using o xidation numbers .
Oxidation numbers can readily be calculated if the compound is mx too complicated.

For example. the o xidation number of each carbon in ethane. C1 Hi;. is -3. For
propane.C#f 6, the average oxidation number of carbon is - ? that is. - 2f This is
not very meaningful. If we calculate the oxidation numbers d the individual carbons,
itis - Jforthetwoendcarbonsand - 2forthemiddleone.eventhoughtheyareall
considered to be in very similar chemical environments to those in ethane .
We can therefore see that calculating oxidation numbers in organic compounds
does mx tell us very much . However. cha'1ge.s in oxidation numbers in organic
compounds can be useful.
140
C 1H 6 + Br1 ---+ CzH 5Br + HBr
it is nOl very helpful to state that the (average) oxidmion number of the carbon atoms
has increased from - 3 to -2. lt does show that a cv.o -dearon transfer reaction has
taken place, but this is more easily established by nOling that the cwo Br{O) morns
have changed their oxidation number co - 1. If we calculate the oxidation number o f
each carbon atom separately, we see cha! the ---CH 3 carbon remains unchanged at - 3 ,
but the -----CH 2Br carl>on has increased from -3 to - I (.x + 2 - I = 0, sox = - 1).
In mo"' complicated redox reactions, which may nOI: be quantitative, (OI is often
used to indicate the addition of oxygen and IHI the addition of hydrogen. In this way,
the oxidation d ethanol to eihanok acid can be represented by:
which shows that a four-elecrron transfer ..,-action has taken place (2!0] + 4e----+ 20(- 2)) .
Similarly, the reduction of propene to propane can be represented by:
ClH 6 + 2[H] ----+ CJHs

whkh shows that a two-electron transfer reaction has taken place (2!HI ----> 2H(+ I) + 2e).
As we saw above with propane, it is best to avoid fracrional oxidation numbers.
If a simple cakulation gives a fractional oxidation number for one type of acorn in a
fommla, this usually me,ins thac some 31oms have one integer oxidatiOfl number and
O!her a!onis have anO!her. In Fe30 4, for example. the average oxid31ion number of iron
is +:4. bm a better description is 10 assign one iron atom as Fe(+2) and c,vo as Fe(+J).
7.3 Balancing redox equations

An imponant use of oxidation numbers is to help establish the sioichiometry of an
unknown redox reaction . The overall reaction can be found by combining the half-
equations for the oxidation and reduction reactions .
Writing the half-equations

Some half-equations a"' easy to work out. for example the oxidation of iron(]]) ions
toiron(IH)ion.s:
Others are nx,re difficult. for example the oxidation of nitrite ions to nitrate ions in
acid solution . The following stages le,id to the relevant half-equation .
Workout oxidation numbers - nitrite, NO,- , is N(+3) and nitrate. N03- , is N(+ 5).
Balance for redox - we know that this is a two-electron transfer reaction from the
oxidation numbers given (N(+3)---+ N(+S) + 2e):
N0 1-----+ Nol- + 2c-
Balance for charge - because the reaction is being carTied out in acid solution. we
add tt ions to one side of the equation. We need 2tt on the right -hand side of
theequationsothattheoverallchargeisthesameon hothsides. in this case - 1:
NOz-----+ Nol- + 2c- + ztt+
(If the reaction had been carTied ou t in alkaline solution. we would balance by
addingOH- ionstoonesideoftheequation.)
Balance for hydrogen - this is done by adding water to one side of the equation.
We need to add H,O on the left-hand side of the equation to balance the 21-r on
the right-hand side:
Check for oxygen - the half-equation is now balanced , but it is a good idea to
checkthatitiscorrectbyconfinningthattheoxygenatomsbalance.
141
PHYSICAL CHEMISTRY
Toproduteabalancedhalf-equation
Workoutoxidationnumbers
Balanceforredox - addthecorrectnumberofe- 1oacrnuntforthedifferencebetween
the twooxidatioo states
Balanceforcharge - i!ddthecorrectnumberolH'{or011)toonesideoftr>!!equahon
sothatthetot.-ilchargeisthesameonbothsides
BalanceforH - i!ddthecorrectnumberofH10toonesideoftheequationsothatboth
sides have the same number of H atoms
Check for O there should oow be an equal number of O atoms on both sides of the
equation
Worked example
Produce a balanced half-equation for the reductioo of manganate(VII) kms to manganese {II)
ionsiniKid'iOlution
Answer
WOO<outoxidation
numbers Mn0 4- is Mn{+7 ) and Mril is Mn(+2).
Balance!Ofredox Mn0 4+ se----+Mri1
Balance for charge Mno 4- + se- + BW---+ Mril
{In acid solutioo, soxH ' ioosareaddedtoonesideoftheequation
tobalance/Ofcharge: - 1 t {- S) + x{+1): +2, givingx ~ 8.)
BalanceforH Mno 4-+ se-+ 8H'---->Mri1 + 4H10
{Thisisdonebyadding yH10toonesideoftheeq uation.WithBH
on theleft-handside,weneed4H 10ontheright-handside.)
ChedlorO Tr>l'feare40onbothsidesoftheequation
Producehatf-equationsforthefollowingchar,ges
1 theoxidationofCl'\OH)itoCrO/- inalkal ine'iOlutioo
2 thereductionofVO;,_ tolf- inacidsolution
3 theoxidationofH1C10 4 toC01 inacidsolution
4 thereductionofCr10,1- 1ocr>+inadd'iOlution
5 thereductionofIOi- loI1 inacid'iOlution
6 thereductionofoxygenina lkalinesolution
7 thereductionofH 10 1 towater inacid'iOlutioo
8 theoxidationofH10;itooxygenina lkalinesolution
Producing a full equation from two

half-equations
A full equation can be wriaen by adding the two half-equations for the oxidised
andreducedspecie.stogether.ltises.sentialthatthedeeuonsbalancebecweenthe
!WO half-equations, and to this end one (or bol:h) of them may have to be multiplied
throughoutbyanappropriatefactor.
Afteraddingthehalf-equationsrogether,themolesofanysubstancethatappears
onbol:hsidesoftheequation(forexample. water)canbecancelled.
Toproduceafullequation
Write dawn the two half-equations
Multiplyeachequationsothatthenumberofelectronsbeinggivenbythereducing
agentequalsthenumberofelectroosrequiredbytheoxidisingagent
Addthehatf-Pquationstogether.
Simplifyilpossible.
Checkthattheequationbalancesforcharge.
Add'>latesymbols
141
Worked example
Produceabalanc.edequatioolortheoxidabonofiron(ll)ionswithacidiffedmallQilllille(Vll)ioJ1S
Answer
Thetworelevanthatf-equatioosare
oxidatioo: Fe"--tFe' + e--
reduction: Mno 4-+ Se-+ 8H'--tMn1+ 4H10
Wemustmu!tiplythefirsthalf-equatioobySsothattheelectronswillcancel:
Onaddition,wethenhave
Checking for charge. there are 17positivechargesoobothsidesoftheequation.Finally,we

add the state symbols
Mno 4- (aq} t SFe1(aq) t BH'{aq)--> Mn1(aq) t SFe3*{aq) t 4H10(0
1 Produceb.Jlancedequatioosforthefollowingreactions
a thereductionofiodate(V}ions.10 1- ,toiodine,11.byiodideionsinacidsolution
b the oxidatioo of No.,- to No1- with manganate{Vll) ioos, Mno4- , in acid solution
c the reduction of vo 1 to 1/- with meta llic zinc in acid solutioo
d theoxidationofFe(OH) 1 toFe(OHhbyoxygen
2 (Harder}Writebalancedequationslorthefollowingre.-ictions:
a the reduction of Cr1o/- to Cr3+ with metall ic magnesium in acid solution
b the reduction ol riitrate(V} to ammonia 1\ith metallic aluminium in alkali rie solution
c the oxidatioo of Cr(OHh to Cro/- by H10 1 in alkaline solution.
Disproportionation
If an element has three or more oxidation sta!es. then it can act as its own oxidant
(oxidising agent) and reducrant (reducing agent). Usually. the higher the oxidation
state of the element, the more JX>Werful an oxidant it is. If a compound that contains
the element in a high oxidation state is mixed with a compound !hat contains the
element in a low oxidation state. the result is that the intermediate oxidation state is
formed. For =ample. if vanadium(+S) is mixed with vanadium(t 3), the result is a
compound containing vanadium(+4):
V0 2+(aq) t yl+{aq) ---t 2VO H{aq)
If iodine( +5) is mixed with iodine(~ I). the product is iodine(O) (see Figure 7.1).
Flgure7.10:00ationofiodide.J-,by
iodateM.10,- The diagram sho1\~ that one
iodateioooxidisesfivekxlidelom
143
PHYSICAL CHEMISTRY
Measu rements of the voltages of electrochemical cells (see Topic 23) can show why
thehighoxidationstateoxidisesthelowoxidationstate .
Ocrnsionally. the intermediate oxidation state is a more powerful oxidant than
chehigheroxidationstme. This is becausetheintermediatestatehasa strucrure
that makes it unsrnble . The intermediate srnte then dis p topot"tionatl'S and breaks
down to a mixture of the substances in the hig her and lower o xidmion states . A
fomiliar example is hydrogen peroxide. H,0 2, containing 0(- 1). This sponmneously
breaks down co oxygen, 0(0) . and water, which contains 0(-2) (see Figure 7 .2).
Flg ure 7.2 Thedisproportkmationof oxidat ion,tateof oxyge n

hydrogenperoxide,H,o, Thedi.11]1amshows
thateac:hmoH!ruleofH,O:,i'iconvertedinto
- - - ~ - - - Jo,
oneH,Oa ndfo,
- - - - ~ - - , ,o
Some more =amples of disproponionation are described in section 11 .2.
7.4 Redox titrations

Redox tilrations involve calculations similar to those described for add-base titrations
(seesection6.6).
Thebas icequation s usedintitrations-areminder

n~~
M
1000
n- cx - c= xn
1000 ,
n ~ amount{in mol}, m~ mass (ing}, M ~ molar mass (in gmoJ-1).
c - rnncentration {in moldm- l), v~ volume (in cm3l
todeterrni nethe.s1oichiometryofaredoxreaction andhencetosuggest a likely

equation for the re:iction .
If the concentration of a solution is unknown and is to be found by a redox

titration. a standard solution (o ne whose concentration is known) that reacts with
the unknown solution is requ ired . The balanced equation g ives the number of moles
thatreacttogether. Afterhavingcarriedoutthetitration.thestagesin thecakulation
are as shown in Table 6.3 , page 130. The balanced chemical equation allows us to
calculate the number of moles of B from the nu mber of moles of A. This then leads
If, instead. the stoichion1eay of the reaction is to be found. then the concentrations
o f lxxh .solutions A and B muse be known. The volumes from the titration enable us
to calcu late the numbers o f moles thac react together.
Although a wide range of oxidising agents can be used in redox titrations. we shall
concentrate on two - potassium manganace(Vll) and iodine.
144
Titrations using potassium manganate(VII)
as the oxidant
Usually pornssium manganme(VH) titrations are carried out in acid solution . Under
theseconditions.thefollowing half~uationisrelevant:
You wiJJ meet this equation often in redox reactions. and it is a good idea to learn it .
The d=p purple manganace(Vll) ion is used as its own indicator. This solution
is run into the Oask from the burene. and in the course of the reaaion the colour
changes from purple to colourless as nearly colourless manganese([[) ions are
produced . At the end-point. the first extra drop of manganate{V][) ions makes the
solution tum pink . The following =perimental details should be noted .
POl:assium manganace(VI[) is nOI: very soluble , and the hig hest concentration used is
0.02moldm- 3.
The reaction is carried out in the presence of sulfuric acid at approximately I mol.dm- 3.
It is usual to read the top, rather than the bouom. of the meniscus of po{assium
manganate(VI[) in the burette because the deep purple colour obscures the reading
Flgure 7.3 ThetopoflhemeniKustsread
whenusingpotassiummanganate(Vll)ina at the bouom (see Figure 7.3). Because the volume delivered is the difference
t1tratioo. Comparetheread ingswithtllose in between the readings, it does not matter whether we read the top or lxxtom of the
Hgu1e6.4(page12<J) meniscus. aslongaswedothesameforlxxhreadings.
If the titration is carried out too quickly, the solution may tum brown (see
Figure 7.4) . This is due to the formation of manganese([V) oxide. MnO, . This can
be avoided either by increasing the acidity of the solution or by wanning it.
Flgure 7.4 Toavoidthe,;olutiontum ing
brown,warmthesolutionDfuseptenty
ofaod
Worked example 1
lnatitration,25.0cm1 ofasolutionofiron(ll)sulfaterequired22.4cm 1 ol0.0200moldm- 1
potassium manganate(VII) !iOlutioo at the end-point. What is the concentration of the
solutionof iron{ll)sulfa te?
Answe r v _
22 4
n(KMn0 4 ) = C)( = 0.0200)( = 4.48)( 10--tmol
1000 1000
oxidation: Fe"---,Fel++e-
reduction: Mno,- + se- + BW---, Mni + 4Hi0
To balance the electrons, Smol of Fei+ react with 1 mol of KMn0 4 Therefore
n(Fei)usedis ~ S)(4.48)( 1o-4 = 2.24)(10-1 mol
1
c(Fe1)z ~)(n
z::)(2.24)(10-1
=0.0896moldm-l
145
PHYSICAL CHEMISTRY
Worked example 2
25.0cml of a 0.0200moldm-1 solution of ethanedioic ilCid, H1C10 4, reacted with 20.0cm1
of 0.0100moldm- 3 potassium manganate{VII) solution
How many moles of ethanedioic add re.-ict with 1 mol of potassium manganate{VII)?
Suggestalikelyequationlorthereaction
Answer
n{KMnOJ~cx ~
1000
~ 0.0200x lS.O = 5.00x 1o-4mol = O.Q100 x lO.O = 2.00 x 1o-4mol

1000 1000
Therefore Smol of H1C10 4 rwct with 2 mol of KMn0 4 (or 2imol redd with 1 moll. We
know from the hall-equafon for manganate(VII) that 2 mol of KMn04 receive
2 x S = 10mol of electroos, so Smol of H1Ci0 4 donate 10mol of electrons, and 1 mol o f
HiC104 donateSZ = 2mol ol electrons
TheoxidatiooriumberofCinH 1C10 4 is +3.0uririgtheoxidation,2Close2electrons,so
each char.ges oxidation riumber from +3 to +4. This sugge51:s that C01 may be produced
We'iha ll writethehalf-equationassumingthis
oxidation: H1C10 4 ---+ 2C01 +2e- + 2H*; reduction : Mno4-+ se- + 8W ---t Mn1-+ 4H10
We mult iply the first half-equation by Sand the second by 2, and add them together
2Mno,- t SH1C104 t 16H*---t 2Mn1* t 8Hi0 -t 10C:Oi -t 10H*
Simplifyingandaddingstatesymbols
2Mno, (aq) t SH1C10.iliKJ) t 6H*{aq) ---t 2Mn1*{aq) t 8Hi0{1) t 10COi{g)
(Checkthechargesbalance:fourpositivechargesonbothsides.)
1 Asteelnailwithamassof2.47gwasdissolvedinaqueoussulluricacidand
thesolutionmadeupto250cmlinastandardflask.25.0cmlofthissolution
reacted with 18.7 cm1 of 0.01 OS mol dm- l potassium manganate(VII) solution
Calculate
il theconcentrationoftheiroosollllion
b themassofironpresentinthe250cmlflasl:.
c thepe<cent.igebymassofironinthesteelna il
2 25.0cm 3 of acid ified 0.0370moldm- 3 sodium nitrate(III). NaN01, solution reacted with
23.9cm 3 of O.OlSSmoldm- 1 potassium manganate{VII) solution .
ii Calculate the number of moles of sodium nilrate(III) that redcl with 1 mol of
manganate(VII)
b Sugge5ta likelyequationforthereaction
1 A 1.31 g sample of hydrated potassium ethanedioate. K1C10 4.xH10. was dissolved
in acid and made up to 250cml in a 5tancfard flask. 25.0cm1 of this solutioo reacted
with 28.S cm1 of 0.0100moldm- l potassium manganate(VII) solution. Calculate
ii theamountofpotassiummanganate(Vll)in25.0cm1 ofsolution
b theamountofpotass.iumethanedio.Jtein250cm1 of'>Olution
c M,{K1C104.xH10)
d thevalueofx
Titrations using iodine as the oxidant

Iodine is a weak oxidising agent. but it is often used to oxidise the thiosulfate ion.
S1o 3>--. to the tetrnthionate ion , s.0 6>-- :
This is another reaction that you will meet often. so it is helpful to know the
equation well.
146
The colourless thiosulfate solution is placed in the burette. The iodine solution
is initially brown in colour. 3nd as the thiosulfate is added it fodes to pale yellow
(see Pigure 7 .5). Pinally at the end-point the solution becomes colourless. The
end -point is rather indistinct and it is usual to add a few drops of starch solution .
This forms an intense blue colour with iodine . The end-point is then a sharp
dl3nge from blue to colourless , when all the iodine has been used up. The srnrch
solution is not 3dded until the iodine solution is p3le yellow - if it is added at the
siarc of the titration. dumps of blue solid m3y be formed which are difficult to
breakup.
This titration is nOI often used juSI to find the concentration of an iodine solution.
There is a large number of oxidising agents th31 oxidise iodide ions to iodine. and
the iodine titration is used mainly to analyse such reaaions . If 3n excess of aqueous
potassium iodide is 3dded to the oxidising 3gent. the 3mount of iodine liberated is
directly rebted to the amount of oxidising 3gent used . T3ble 7.1 lists some of the
oxidising agentsthatmaybeestimatedinthisway.
Flgure 7.5 Theendpointofaniodifl!'

titratiooi1madem uch1harperusi11gst.m:h.A
fewdrop1of1ta rchsolutiooareaddedwhen
ttiesolubonispaleye lklw;theend-point
\.
ocrurswhenthe inten'oeb luecolour
justdis.Jppears
1
Table7.1 S.0meoxid ilingage11t1thatca 11 be oxidising agent Equation

' \
n(thiosulfate)
l".l~matedusingiodinelthiowtfateEachrnole
ofiod inere..ctswithtwomo le1ofthi01ulfate n(oxidisingagent)
Cl, Cl 2 + 2r--+ 2Cl- + 1,

Br, + 1l---+ 2Sr + I,
cu' cu:,, + 2r --+ Cul + I,
147
PHYSICAL CHEMISTRY
Thiosulfate oxidation numbers

The thiosulfate ion, s,o/- , is an example of the inappropriate use of oxidation
numbers.
The equation:
shows that the half-equations are as follows
oxidation: 2S1 o/- o/- + 2e-

----t S 4
rcduetion: 11 + 2e-----+ 21
So e:ich thiosulfate ion ""'eives one electron. Some books suggest that the oxidation
number of each sulfur atom has changed from +2 to +1. Others compare the s,o/-
ion with the so/- ion, and as.sign S(~) to the central sulfur atom and S(- 2) to the
oo:herone. On oxidation. the S(-2) atom then becomesS(- 1). This may show what is
takingplaceduringthereactionmor<,accurately.
0 0 0 0
-o- ~- s- + -s- M- o- ~
_,.- II
-o- s- II
s- s- s- o-
11 II 11 II
0 0 0 0
As can be seen, oxidation numbers cease to be useful when applied to the thiosulfate
ion. All that needs to be known is that each s,o/- ion loses one electron when it
it is mx necessary to know the oxidation number of each sulfur
Worked example
Althooghtheactive ingredientinarnmme/Cial bleachischlorateO)ions,CIO-,the
rnnceotrationisofteoquoted in terms offfeechlorine.Thisisbecausethernncentrationis
estimated by liberating iod ine from potassium iodide. 10.0cml of the bleach were made up
to250.0cm 1 inastandMd flask.2S.Ocm1 of this solution wereitddedtoanexce11of
aqueoospotassiumiodide
Theiod inelibefatedreactedwith22.0cm 3 of0.10Smoldm-lthio1ulfatesolution
Cakuklte
a thernncentrntionof'chlorine'inthe dilutedble.-ichsolution
b thernncentrationof'chlorine' ingdm-linthernmmercialbleach.A,lCl) z 3S.5
Answer
a Firstweca lculatetheamountofthiosullateused
n(S.,O/-) ~ cx ~ z 0.105x:~ ~ 2.31 x10-1 mol
1
Theratio inlable7.1(page147) tellsusthat n(Cli) in25.0cm 1 of dilutedbleach
solution is
~x2.31 x 10-i31.15Sx 10--lmol
Therefore:
1
dCli) ~ ~ xn = ~~ x1.15Sx10-l
~0.0462 moldm-3
b M,(Clil = 2x3S.Sgmol- 1.Theoriginal blNchwasdiluted25time1.Theref0<ethe
concentrationofchlorineintheb!Nchis
2Sx{2x35.S)x0.0462 ~82.0g dm-l
148
1 A 2S.Ocm1 sample of 0.0210moldm-l potassium pernxodisulfate(VI), KiS.,0 8, was
tre.itedwithanexcessofpot,w;iumk>dide.Theiodirteliberatedreactedwith21.0cm 1
of O.OSOOmoldm-1 thiosulfate. Cakulate
the amount of S.,Os1-, and the amount of 1- u500 by the peroxodisulfate
b the amount of r that reacts with 1mol of Siol-
t Suggestalikelyequationl0fthere<KtionbetweeoK1S10 8 andKI
2 A 1.00g sampleofbrass(anaHoyofcopperandzinc)wasdisscil'edin nitrica,c:idand
made upto 250cm 3 in a standard fl<1s.k . To a 25.0an 3 sample of this 'iOlution was
a<ldedanexcessolaqueouspotassiumiodide.
Cu1*+ 2r ---->CUI -t 'ili
Theiod im.>liberated1eocted1, ith27.8cm1 of0.0425moidm-lthiosulfate
Calculate
ii theconcentrationolC1l* inthesciutioo
b thetotalmassofcopperdis'iOlved
t thepercentageofcopperinthesampleolbrass.
7.5 Some uses of electrolysis

The electrolysis of brine
lfconcentrated3queousS<Xliumchlorideiselectrolysed. hydrogenis g ivenoffatthe
H 10(1)----+ H+(aq) + OW(aq)

2 H+(aq) + 2~- ----+ H1(g)
Because hydrogen ions 3re being used up, hydroxide ions are left behind . Adding
the equations:
The products,therefore,arehydrogen,chlorine3ndsodiumhydroxide:
2NaCl(aq) + 2H 10(1) ----t2NaOH(aq) + Cl1(g) + H 1(g)
Formostpurp;:>SeS , the c hlorine , hydrogenandsodiumhydroxide solution need to

be collected ,...parately, which can be done using a d ia phragm ccll (see Figu re 7.6).
This concains an asbesto.s diaphrag m that allows the ions to flo w from the 3node
co mpanmem to the cathode companment. This now is esrnblished by having the
level of the electrolyte higher on the anode side of the diaphragm than o n the
Theincomingsolutionissarura1edbrinecontaining 31x,ut25% sodiumchloride

The outgoing solution contains 3bout \ Oti, sodium hydroxide and 15% sodium
chloride . This solution is evaporated lo about one-fifth of its volume, when nearly all
thesodiumchlorideciystallisesout, leavinga solutioncontainingSCM, ofalmostpure
sodium hydroxide. This can be used as a solution o r evaporated 10 dryness to give
chesolidproduct.
Modern plants use a membrane rather than a diaphragm in the cell (see Figure 7 .7).
The membrane is made of a polymer containing PTFE (see section 2S.1), which
allows cations but not anions ro pass through it . The resulting sol ution is pure sodium
hydroxide, uncontaminated by sodium chloride . Thechlorineandhydrogengasesare
collected separately.
The principal uses o f the thr= chemicals are listed in Table 7 .2.
149
PHYSICAL CHEMISTRY
Flgure7.6 Ou~inediagramofthediaphragm Cl,(g>

cel l usedfortheek>ctmly;isofbfine
NaOH(>qJ+
cn...J---- f=l,(p)+ e- NaC~>qJ
Flgure7.7 Modemplanl5useamembral\l'
rathe1thanadiaph1agminthecell. Thi'iyfeld1
very pure sodium hydroxide
Table7.2Principalusesoftheproduct1of Sodium hydroxide Hydrogen

theelectmly1i1ofbrine
making "PI and deter genii in making ammonia forster ili">ationandbk>a.c:hing
rnnvertedinto'>Odium fDftheh)'drogenatKlflof
carbonote o ils (seesectkm14.3)
USl'dinrefiningaluminium inweklingusing;m tomake!.dveot11uch
oxkle(seebelow) oxy--hydrogenftame asdi::hloromettianea!ld
for making paper tomakeCK1{see1ection15.1)
tom.ikePVC(see'>l'd:ion 18.1 )
The extraction of aluminium

Most mohen aluminium compounds do nOI condua electricity. Molten aluminium oxide.
Al,0 1, is a conductor. so its electrolysis )ields aluminium. However. it has an exu.,mely
h igh melting point (2o6o 0 C). lbe oxide is therd'ore dissolved in mohen cryolite ,
sodium hexafluOfO<llumin:ue, N3i,AIF6, which has 3 melting poim knver th:rn 1000C.
There are three main srnges in the manufacture of aluminium:
the=traction andpurific:11ionoftheore, bauxite

the preparation ofcryoli!e
e electrolysis.
150
Bauxite is a relatively abundant ore. It is mainly aluminium oxide. but its principal
impurity is hydrated iron([[!) oxide; it may conrnin siHca and tirnnium oxide as well .
The bauxite is dis.solved in l(Wo aqueous sodium hydroxide under 4 atm pressure
at 150'C. Theimpuritiesarelargelyinsolubleandcanbefiltered off as a sludge.
Aluminium hydroxide, Al(OH)J. is then precipitated from the dear solution by C<X>Jing
it for three days. This precipirntion is accelerated by seeding' the solution with a
crysi:al of aluminium hydroxide . The hydroxide precipitate is filtered off and heated to
conven it into pure aluminium oxide .
Al 20 1{hydrated) + 20H- (aq) + JH 10(l) ---t 2Al(OH) 4-{aq)cther impurities are

Flgure7.BPaulHemult(1863-1<J14)and insoluble
CharlesHall(1863-1914).de1ignersofthe Al(OH) 4-(aq) ~ Al{OHh(s) + OW{aq) precipirntiononc<X>ling
e~ctmlytk proces1 to produce aluminium 2Al{OHh(s) ---t Al 10 1{s) + 3H 10(g) dehydration on heating
The sludge is composed of iron oxide and Ol:her impurities. It is washed free of
sodium hydroxide before being buried . This treatment is imponant as untreated
sludge is an unattractive brown colour and leaves the soil too alkaline for plants to
grow. The sodium hydroxide produced during the precipirntion is recycled and used
Ctyolite is made by dissolving NaAl(OH)4 in hydroOuoric acid and precipimting the

product with sodium carbonate:
The electrolysis is carried out in a si:eel box whose Ooor is lined with carbon. This
acts as the cathode connection (see Figure 7.9).
Flgure7.9 OU1Jinediagramoftheelecttolytk
cellusedtopmduc:ealuminium
I I I I I I
electrolyte
-
I I I I I I I I
- ~~~,'cryolite
graphite lining- containing5 %
ofAl 2 0 1
aluminiu m
run off
The anodes are blocks of graphite suspended in the molten cryolite . Because
aluminium is more dense than cryolite, it sinks to the bottom of the cell as
it is formed. creating a molten pool which acts as the cathode. Periodically
the aluminium is removed and more aluminium oxide added to maintain a
concentration of 5%.
Theexactnatureoftheelectrolyteisunknown - ithasbeensuggesi:edthat
the principal ions present are Alo+ and Alo,- . lhe reactions taking place at the
electrodes may be written as follows. although this is cenainly a simplification
at the cathode: 2AIH + 6c- ---t 2Al(l)

attheanode: 30l- ---tl~ 2(g) + 6c-
The oxygen given off at the anode reacts with the carbon, producing carbon dioxide.
Thegraphiteblocksthereforehavetoberenewedregularly.
The process requires enormous amounts of electricity - up to IS kWh are needed
to produce I kg of metal. A typical cell operates at 4.5 V and 3 x 10' A. and two-thirds
151
PHYSICAL CHEMISTRY
Figure 7.10 Alumin ium i,; the mmtabtmdaot

metalinthefarth'scrust,ocrurringlargely.tS
theorebauxile . ttlhighextractioornst1mea11
th.itrecycli11gi1amuchmorel'ConomiGllway
ofprodocing'new'metal.Toephotograph
shows the effect of aluminium extract,On on
thelaridsc.pe
of the energy goes in heating the cell. Fortunately, aluminium is e:isy to recycle and
this requires only S% of the energy required to produce it from bauxite. Up to 6cm
of aluminium used in Europe is from recycled material.
Aluminium is the second mo.si used metal after iron. h has a good srrength-to-
weight ratio and is resi51ant to colT05ion. especblly when anodised (th31 is, covered
with a thin pro{ective oxide film by anodic oxidation) . Its principal uses are as
follows:
in lightweightalloystobuildcars,ships. aeroplanes,etc
for building work. such as for window frames
to make packaging.such ascans,foil,ecc.
The purification of copper

A major use of copper is for electrical wiring . As the conductivity of cOpJX'"r
increases ten -fold when it is more than 99.9% pure, impure copper is purified
to this high degree by electrolysis. The impure copper is made the anode of
an electrolysis celL and a small strip of pure copper the cathode. A po!ential
difference of about 0.2--0.4 V is applied . Ions of copper and any more 1tactive
metals go into solution from the anode but the more reactive ions are not
discharged and slay in solution as the copper ions gain electrons and are
discharg ed onto the cathode.
Any metals chat a1t less reactive than copper do not dissolve from the ancxle .
These mecals drop off the ancxle as the copper around them dissolves, and fall to
thebcxtomas'ancxlesludge".Thiscontainsrareandusefulelements,suchassilver,
gold and selenium. Subsequently this sludge is removed and the rare elements
Oxidation istheremovalofelectrons; reduction is the addition half-equations,suitablyrnmbinedtogether,givethewhoje

of electrons oxidation-reduction equation
lna redoxreaction ,thenumbe r ofelectronslost z thenumbef Tltrations u1nbeu1rriedoutbasedonredoxrl'dctions.The
of electrons gained m05limportantredoxtitrntionsusepotasliummanganate(Vll)or
Toworkoutthenumbefofelectronsl05torgained, oxidatlon iod ine
numbers maybe used Electrolysls isusedinmanyindu!ilrialprocesses,suchas
Oxidationnumberscanalsobeusedtoworl:outtheoxidation theelectroly;isofbrine,theextraction ofaluminiumandthe
arid reduction half-equations for a rndox reaction. The two purifiu1tionofrnpper.
152
Pleaseseethedata5ectionoftheCDforanyA,.valuesyou 2 Chlorine is manufactured by electrolysis from brine,
may need. concentrated aqueous sodium chloride
a i Describe,withtheaidofafullylabelleddiagram,the
1 RadiumwasdiscoveredintheorepitchblendebyMarieand
industrialelectrolys.isofbrineinadiaphragmcell.
PierreCuriein1898,andthemetalwasfirstisolatedby
State what each electrode is made of and show dearly
them in 1910.
theinletforthebrineandtheoutletsfortheproducts
Themetalwasobtainedbyfirstreactingtheradiumpresent
ii Writeahalf-equation,withstatesymbols,forthe
~-
inthepitchblendetoforminsolubleradiumsulfatewhich
reaction at each electrode.
was converted into aqueous radium bromide. This rnlution
anode
wasthenelectrolysedusingamercurycathodeanda
carbon anode
iii Namethechemicalthat is produced insolution inthis
a During their electroly5ls of aqueous radium bromide, the
electrolytic process [7]
Curies obtained radium at the cathode and bromine at
{Cambridge International AS & A level Chemistry,
the anode. Write half-equations for the two electrode
9701, Paper22Q4June2011]
reactionsthattakeplaceduringthiselectroly!.is (2)
Paper 21 Q2 b November 2009]
153
AS Level
Physical chem istry
8 Rates of reaction
Topic 5 looked at enthalpy changes
for reactions. While theJ/gnof
Lea rnin g outcomes
t>H may indicate the direction By theendofthi1topic:yooshouldbe able to:
ofchemlatlchange,/tg/vesno 5.2b) comtruct aOO interpret a R>actiori pathway diagram , in tef ms of the enthalpy
inform11tlononhowfast11reactlon changeoftherMCtioo andoltheactivation el'le(gy
occurs. Thlscanonlybefoundoutby 8.1a) exptainandusethetermrafeofte.Klion
experiment. Therateofareactlon 8.1b) explainqualitatively, interm5 of ccl lisions, theeffectof conceo trationchangeson
depends on II number of factors. e.ich thernteof areaction
of which c.tn be studied separately. It 8.2a) expla inanduse t hetermactivittionenergy,includ ingreferenceto theBoltzmann
/sfoundthat,.forarHctlontotake distribution
place, not only must the molecules of 8.2b) explain qualitatively, in term\ both of the Boltzmann dist ri bution and of coni';ion
thereactantscollide,buttheymun freq ueoc:y, theeffect oltemperaturecha,rigeon t herateofareaction
collidewithsufflclentenergytoget 8.3a)explai n and usetheterm c.JI~
oW!ranactivationenergybarrltr.lna 8.3b) explain t hat c.ata ly5ts c.an be homogeneous or heterogeneous
typical chemic.JI rHclion, only a tiny 8.3c) explain t hat, in the presence of a cataly5t, a reaction has a different mechanism,
fractionofcol/isionsanieffectl..-.ln i.e.one of lower aclivi!tionenergy,andinterpretthiscatalyticeffectintermsof
bringing abotJt chem/ail change. theBoltZlllilllndistribution
8.3d) describe enzymes as biological c.atalysts (proteins) which may have specificity.
8.1 Why do reactions take place at

different rates?
How qu ickly a r=clio n 8'""" that is, the ntc of a reaClion, is defi n ed and
measutt'd in terms of how q u ic kly a reaciam is used up, or how quic kly a prod uci
forms. lbe rate o f reaciion varies g rea tly for differem reaCllons, and under different
conditions
Enthalpy of reaction revisited

Jn To p ic 5, it was seen th at the sig n o f !J.H ind ic.. tes the like ly direction in w h ich
a re action will take place. Mo st re actio ns arc ex01 her mk, tha t ls, 1111 negative , and
very few are e ndOlherrnic, that is, l!.H pos itive. \t'e mlght be tem pted to th in k th at
if a reaction is highly e x othe rmic,soth at theenergyof the products is muc h less
than the e n e rgy of the reacta nts, then it will take p lace very rapidly. Th is, however.
is nOI necessarily the case. For exa m p le, a mixture of methane and oxygen s h ows
n o sign of reaction at room temperature and pressu re even though (!JI for the
reaction is -89(1 kj mor '. On the Olher h:i nd, the reaction between hydroch loric acid
and sodium hydroxide takes pbve ,..,ry rapklly, even though (!J/ for thi, reaction is
only-S6kJmor'. lbe srudy of the rate5of chemical reactions is called kl1K'tlcs. while
the srud y o f ~ changes is called the r mody n a m ics (as we saw in Topic 5).
The activation energy barrier

flH cannot indicate the rate of r=ction benuse there is an energy barrier bcfwecn
the reactants and products that ha,; to be overcome. This can be thought of a,;
154
Rates of reaction I
similar to a ridge along the edge of a desk. over which a book must be pushed
before it will fall to the floor. Before the book will fall. we first have to push it
harder for it to rise over the ridge . In chemical reacrions. this ridge is called the
acrivation e n ergy. and it is given the symbol E,_. The size o f the activation energy
(the height of the ridge) does not depend on the size of Ml (the height of the desk
off the fl oor) .
We can draw an energy diagram for a reaction. as shown in Figure 8.1. Such a
diagram is sometimes called a reacr>On profile . The reacrants are hig her in energy
than the prcxlucts, but the top of the acrivationenergy peak is higher still .
Flgure8.1Reactionprofilesforthe
rnmbustkmofmethaneandtheneutralii.ation
reactionbetweensodiumhydroxideand
hydrochloric:acid.The!abel'progres1o f no activation energy
1eactioo"iftdK.ltestllechang.efrnmreactant1
loptoductsovertime
NaOH(aqJ+HCl("'ll
- 56kJmol_, i NaCl("'l)+H ,O(IJ
-890kJmol-'
progres.sofreaction progress of reaction
There are therefore two factors that determine whether a reaction takes place or not -
thesignofAflandthevalueof E,_.
e lfAflispositive.thereactantsarelowerinenergythanthe products . The reactants

are said to be thcmIOdynamlcally stable with respect to the prcxlucts. Such
reactionsareunlikelytotakepbce.
Even if Ml is negative, the reaction may stiJJ not be observed to take place because
it has a hig h activation e nergy. Because of this. the rate of the reaction is negligible
at room temperature. The reactants are said to be kinetically inen (or kinetically
s table).
Table 8.1 summarises the effecr of the four combinations of AH and E. o n the rate
Table8.1 Therateofareactklndepef1d:loo
boththeenthotpyc:t,angeondtheactivaboo
,.
usuo llynoreactKlfl.reactantlarethermodynamic:ally1t~e
high usuallynoreactkln.reactant1arethermodyriamic..allyandkinetK.llly1table
reac:tklnl ikely
high usu al lynoreactkln.reactantsarekinetk:allystable
4' 8.2 Measuring rates of reaction
to discover the best conditions to make the reaction go as quickly as possible

to gather information about the mechanism of a reaction. that is. how the reaction
acruallytakesplace.
155
PHYSICAL CHEMISTRY
In this topic, the factors controlling rates are considered, while reaaion
mechanisms are looked at in more detail in Topic 21. Reaction mechanisms are
particularly imponant when studying organic reaaions .
This section deals with how the rates of reactions are measured.
What to measure?
Simple obsetvation tells us that some reactions go faster than Olhers, but to measure
the precise rate it is necessary to find out how fa51 one of the products is being
produced or how fast one of the reactants is being used up. This can be achieved
using either a physical methcxl or a chemical method of analysis . A physical method
can be more conveniem than a chemical method. because ii does nO! diS1urb the
reaction being studied . It depends on there being a cha.nge in some physical propeny
such as volume. mass or colour during the course of the reaction .
Physical methods of analysis - measuring the

volume of a gas given off
The reaction between hydrochloric acid and calcium carbona!e may be Sludied using
a physical method of analysis:
CaCOi) + 2HCl(aq) ---+ CaC\ 2(aq) + HzO(l) + C0 2(g)

The reaction gives off a gas. whose volume can be measured. A suitable apparatus
is shown in Figure 8.2. lf we plO! a graph of the volume o f carlxm dioxide collecced
againSI time (see Figure 8.3), the rate of the reaction is given by the slope (or
gradient)ofthegraph. TheSleeper!he gradient. the higher is the rate. The race
isgreatestattheS1an,thendecreasesandfinallybecomeszeroattheendofthe
Flgure8.2Apparatususedtostudytherate
ofa1eactiooth.1tgive1offa9a1
-: . 1 ...... .
,mall gas syringe
test tube
.
caco,w

\. HCl1aq1
Flgure8.l Atypic.ilgraphofvolumeagaimt
timelorareactioothatgiYe1offag.11.Toe
tt:
gradientgivestherateofreactionatthat
pointTheratel1greatestattlle1t.1rt,then rate at start
decreas.esandfinallyreacheszeroattheendof
the reaction
]
'
156
Rates of reaction I
Physical methods of analysis - measuring the
decrease In mass
An alternative method of monitoring the same reaction involses canying out the reaction
in an open flask placed Ofl a top-pan l:xilance. As the gas is giwn off. the mass of the
flaskdecreases.lfweplaagraphofmassagain.sttime,therateofthereactionisthe
negative gradient of the graph(,,.,., Figure 8.4). Note that rates of re-:iction must always be
pasitive, since a negative rate woukl mean that the reaction was going l:xickwards. The
gradientinFigure8.4isnegative. .soifwietakeitsnegativevalue.wegetapasitiverate.
Flgure8.4 Atypicalgraphofm.assagaiml
timeforareactionthatlosesagastothe The rate of this re-:iction can be me-:isured under d ifferent conditions. for example
atmosphere.Toerateolthereactioni1the by changing the temperature. the concentration of add or the surface area of calcium
negativegradil'lltofthegraph caibonate.toinve.stigatetheconditionsunderwhich it will proceedthefaste.st.
Physical methods of analysis - measuring a change

in colour
Sometimes a change in colour of a solution can be used to me-:isure the rate of a
reaction . An example of a re-:iction whose rate can be measured in this way is the
oxidation of aqueous JXXassium iodide by aqueous JXXassium peroxcxlisulfate(VI),
K,S,08-. during which iodine is rele-:ised:
lcxlinedissolvesinanexcessofp;:Xassiumiodidetogiveli- ions.whicharebrown:
11(aq) + r(aq) ---+Il- (aq)

bro=
Allotherchemicalspeciesinthisreactionarecolourless.
lbe intensity of the brown colour may be measured using an instrument called a
colorillli.'lc_'I" (see Figure 8.5). In this device, light from a light .source passes through
a fiher that selects just one colour of light. This then shines onto a cell containing the
reactionmixlure,aodadetectormonitorstheamournoflightpassingthroughthesolution.
Flgure8.5 Ollllill!'diagramolarnklrimeter
~,~;oo
vi,ible
light source
<;;
lcxline solution is brown because it absorbs in the blue pan of the spectrum and
transmits cxher wawlengths. We therefore select a blue filter for this experiment
(see page 412). The colorimeter is first adju.sted to zero using water in the cell .
The colorimeter provides readings of absorbance , which is proportional to the
concentration of the iodine. A graph of absorbance against time (see Figure 8 .6) is
obrnined. which is similar in shape to the volume-against-time graph in Figure 8.3.
l~
Flgure8.6 Atypic.ilgraphofab,;orba11Ce
-
Chemical methods of analysis - sampling and
'clock' reactions
Chemical methods of analysis interfere with the reaction being studied. Because of
this. either a new reaction mixture needs to be set up for each measuremern rnken.
against time. This Is equivalent to the vrnume- or small amounts of the reaction mixture. called sa mpl~. can be extracted and
against-time graph in Figure B.3 analysed. Unless something is done to stop the reaction. it will continue to rnke place
inthesamplewhileit is being analysed. Therefore, itisnecessarycofreez.e"the
reaction in the sample as soon as it has been extracted. This can be carried out in one
of 1,vo ways : either by suddenly cooling the reaction (for example. by running the
157
PHYSICAL CHEMISTRY
sample onto ice) or by neutralising a catalyst (for example. hydrogen ions) that may
be present. BO!h methods are time consuming and a"' avoided if possible.
An altern ative is to use a cJock ' method. The rate of the reaction between
pornssium peroxodisulfate(VI) and pornssium iodide described above may be followed
in this way. A separate experiment is se1 up for each determination of rate . The
two re-act:rnts a"' mixed in the P"'sence of a known amount of sodium thiooulfate.
Na,S10,, and a little starch . The sodium thiosulfate "'acts with the icxline prcxluced.
converting it back to iodide, in the "'action we met in section 7.4 :
The atrK>Unt of sodium thiO<Sulfate P"'""nt is much smaller than the amounts of all
theother,.,.agents.Whenallthesodiumthiosulfatehasbeenusedup, theicxline
(which is Siill being prcxluced by the reaction) "'acts with the starch to give an
intensebluecolour (seeFigure8.7). ForafixedatrK>Untofsodiumthiosulfate,the
faS1er the reaction. the shorter the time, I. this takes . The rate of the "'action is
then approximately proportional to 1/ 1 (see Figure 8.8). A "dock" reaction is very
convenient but can only be used with a limited number of ,.,.actions .
FlgureB.7 Carryjngollla'dod::"reactkln
Figure 8.8 Thegraphss.howtworeactlom

AandB.Theymayva!)'in,lorexample,
rnocentratkmortemperature.Aty,allthe
sodiumthioo;utfatehasbeenu'>l'dupand
theiod inereacts1\ilhlhe1ta1t:h.Therateof
reactiooAisappmximatelyequaltay/t,,and
therateofreactionBisaPPfoximate!yequal
toytt,_ Thismeamlhatlheratklofthetimes
t.1kenforthe"dod"tostopgivesthera~oof

theratesrateofA~!o_
rateofB t,
Worked example
Hyd1ogenperoxkleredctswithpotas.sium Suggestmethod1ofmedSU1ir.gtherate1oftheloH01\~r.g1eactioo1
manganate(VII) as follows: a zincpowderwithaqueou1coppe1"1utfate
b h'jdrogenperoxidedecomposingtogivewaterandoxygen
2M1104-+ SH 10 1 + 6H'
c (CHil:iCBr + H10 --+ {CHil:JCOH + W + Br
----t 2Mn1 + 501 + BH10
Sugg.estrwophysiulmethodsof Answer
mea~ring the rate of this 1&1ction. For a Allaw the zinc to sett~. then measure the change in rokiur of the solution using a
eachmethod,sl:etchagraphshowir,g colorimeter.
how the physical quantity you mearnre b Measure the volume of gas gWl'll off, or measure the decrease in mass
wooklchangl.'overtime c Measurethecooductivilyofthesolutioo
158
Rates of reaction I
8.3 Making a reaction go fa ster -
increasing the collision rate
At the molecular leveL the rem, of reaction depends on two factors:
e whmproportionofthecollisionshavesuffidentenergytoovercometheactivation
energy barrier.
The effect of concentration

We can increase the rate at which the reactant panicles collide in several ways. lbe
simplest is to increase the con centratio n of the reactants. At a higher concentration.
the reactant molecules are closer together and so will collide more frequently. The same
is uue if""' incn,ase the p rcssu fi' for gaseous reactions - the volume gets smaller and
so the molecules are closer together. However, changing the pr,,ssure has vinually no
effectonreaaionsinthesolidorliquidphase.becausetheirvolumechangesverylittle
whenputunderpressure.sotheirparticlesdonotmoveclosertogether.
The concentrntions of the reaaams decrease during the course of a reaction and so
the rate also goes down with time (see Rgure 8.3). At the end of the reaction. at least
oneolthereactantshasbeenused upcompletelyandtherateisthenzero.
lfwerepe31thereactionusingmoreconce ntratedreactants.theinitialrateof
the reaction will be hig her. However. ii must nOI: be assumed that if. for example.
we double the concentration, the rate will be twice as high . The actual size of the
increase in rate is impossible to predict and can only be found by experiment. This
study of quanti!ative kinetics is explored in Topic 21 .
Worked example
Wheo lg (an excess) of powdered ukium carbonate were added to 50an3 of
0.10moldm-l hydrochloric add, the results shown in Table 8.2 were obta ined
Voh.meof CO,glYenoff/c m 25
a Plotagraphoftheseiesults.
b Usethegraphtofindtherateatthe'>lartofthereaction
c Explaintheshapeolthegraph
Answer
FtgureB.9
159
PHYSICAL CHEMISTRY
b The gri!diellt of the graph at the beginning shows that 2Scm1 would be giveo off
in10s.Thisisarateof2 .5 cm 3r 1
c Theratedecreases{thereactioo'ilawsdown}asthereactionproceeds, becausetr>l!add
becomes more dilute. The reaction fir.a lly stops when all the ilOO has beefi used up
1 The experiment in the worked example above was repe.ned a using 50an 3 of
0.20moldm-1 hydrochlork add and b using S0cm 3 of O.OSOmoldm-1 hydrochlork
acid. Draw sketches of the graphs you might expect to be pmdtKed and commeot on
thedifferencesbetween&1ehgraphandthatinF~ure8.9.
2 Solutionsofpotassiumiodideandpotassiumperoxodisutlate(Vl)wefemixedtogethef
and a clock started. A sample of the mixture was placed in the cell of a colorimeter
andtheabsorbanceme<1SuiedatsuitabletimeinteNals.TheresultsshowninTa~e8.3
wereobta inl.'d
a Plotagraphofabsorb,mceagainsttime
b Findtherateofthereactkln i after60sand ii after120s
c Expklinwhythesetworeactiooratesdiffer.
3 Whenhydrochloricacidisi!ddedto'i00iumthiosulfate,Na.,S 10 1(aq),alineprecip itate
ofsulfurappe;irs
2HCl(aq) -+ Na 1S.,Oiaq)----> 2NaCMaq) -+ H10(1) + SOi(aq) + S{s)
Thisgradual!ymakesthe'iOlutioJlopaque. Therateofthereactioomaybedetermined
by ffil'ilsuriflg how long it takes for the solutioJl to become so opaque that a cross
marl<edoJ1apieceofpaperplacedunde1thebeakercontaiJ1ingthereactionmixture
justbecomesinvisible(seeFigureB.10)
Theresu!tsshowJlinTable8.4wereobtained
Experiment m.niber Concentratlon/ mol dm-
10.40
10.30
10.20
10 10
a Plotagraphofthereciprocaloltime(lltime)agaiflsttheconcentratioJlof'iOOium
thiosulfate
b ExplaiJ1whytheratechanges1\iththecoocentrationofsodiumthiosulfate.
c Estimate the coJlCentration of sodium thiosuttate that would give a time of 601.
The effect of changing the amount of reactants

If we keep the coJlcentrations of all the reactants the same but. for example,
double their amounts , the actual rate of the reaction will be unaffected although
the amount of product will be doubled . This means that if we measure the
rate from the vo lume of gas evolved or the mass l0.51 , we will obtain different
results for the rate . The actual rate of reaction between calcium cartxmace and
hydrochloric acid is Uflaffected if we double the mass of calcium carboJlate and
double the volume of the acid even though twice the volume of gas is evolved.
However,ifweareusingtheapparatusiflFig ure8 .2(page IS6) chemeasuredrate
of re action will appear to be twice as great because twice as much gas is evolved
in the same time. For quamitative work. it is imponant co define what we mean by
the rate of reaction more carefully, and this is considered funher in Topic 21 .
160
Rates of reaction I
Flgu re 8.1 0 Thereactioobetween
hyd!tXhlmk:a,cidandsodiumthiosulfate
producesaprecipilateol1ulfurThi1allow1u1
tostlldytherateofthereactkm - whenthe
cro11isnolongervilible.thedockil1topped
The effect of temperature

\Ve can increase the rnteofcollisionbyrnisingthetemperature. This causes the
particles to move faster (increases their kinetic energy) and so they collide more
frequently. The increased rate of collision hasonlyaveiysmalleffectontherate
ofreaction:themaineffectofincreasedtemperatureisfromtheincreaseinenergy
whichwillbeconsideredlaterinthistopic.
Particle size
Many reactions are h ornogen C'Ous. that is. the reactants are uniformly mixed. either
as gases or in solution . Others are heterogen eous - there is a boundary between the
reactants(forexample. bet"'eenasolidandasolution). In such reactions. the rate
ofcollisionwillincrea.seifwemakethesurfa cearcaofthisboundaryaslargeas
p;:>SSible. For example. powdered sugar dissoh'es faster than Jump sugar. water drops
evaporate faster than a large puddle , and powdered zinc dissolves in add faster than
Jumps of zinc do. The size of the boundary bern..,en the reactants in a heterogeneous
reaction is described by the state of division - for example. a powdered solid is
describedasfinelydivided ". The efficiency of solid catalysts is also increased if they
arefinelydivided(seepagel66).
Worked example
W~ 2g (an excess) of lump calcium carbonate 1\<e<e added to S0cm1 of0.10moldm...i
h'jl)rochk>ricacid,theresultsshowninlable8.Swereohtained
Volume of CO a given off/cm' s
How does the rate rnmparewith that found in the worked example on page 159?
b El<painwhytherateisdifferent
c What would be the final vciumeol carbon dioxide? El<pain your amwer.
Answer
a Therate islower.
b The surface area of lump cakium carbonate is smaller than that of powdered calcium
carbonate,sotherearefewerrnllis.ionstakingpl3Ceeverysecond
c The final volume of carbon dioxide would be 80cm 3. The final amount of carbon dioxide
isdeterminedbytheamountofilCid,becausethecakiumcarbonateispresentinexcess
161
PHYSICAL CHEMISTRY
8.4 Making a reaction go faster -

overcoming the activation energy barrier
On page 161 it was stated that the energy of the colHsions between reacting particles
is ,nore impormnt than the rate of collision. Even if a reaction has a small activation
energy. only a tiny fmctiOfl of the collisions that rnke pbce hn'<' enough energy to
overcome it . These collisions a"' the c ffcctivc collision s . A typical fraction might
be one in ten thousand million (1 in 10 1}. This is the reason why many reactions are
slow at room temperature . There are c,vo ways in which we rnn increase this fraction :
e givethecollisionsmoreenergy
findan01herro1.newitha lower activation energy.
Giving the collisions more energy

The usual way of increasing the energy of the collision s is to raise the temperature .
Although this increases the rate of collision. the main effect is that 3 hig her
proportion of the collisions now have enough energy to get over the activation
energy barrier - there is 3 greater number of effective collisions. If we raise the
temperature from 25C to 125C. for example. the incre3se in the rate of collision
goes up by a factor of o nly l .2. but the fraction of re3ctam molecules able to get
over the energy barrier could increase by 1000 times . A useful working rule is to
s3y th3t 'a 10C rise in temperature doubles the rate of re3ction' . So, for 3 rise in
tempernture from 25C to 125C. the rate might incre3se by 2 10 or 1024 times .
Finding another route with a lower activation

energy
The second way of increasing the number of collisions that have sufficient energy to
overcome the activation energy barrier is to lower the height of the barrier. This is
moste-:isilyachievedbyusingarntalyst.
A cata lyst is a substan{e that speeds up a chemical reaction withoot being {hemically
used up itself.
The rntalyst provides an alternative pathway for the reaction. and this pathway has 3
lmver activation energy than thatoftheunc:llalysed reaction(see Figure8.11)
Flguree.11 Theenergyprofiteforare..ctkm,
w ithandwrthoutacatalyst uncata lyse d
progrPSs of , ~action
162
Rates of reaction I
Theheightoftheactiv3lionenergybarriermayalsobechanged if a different solvent
is used for the reaction. Many inorganic reactions are carried out using water as a
.solvem, buttn05lorganicsubsrnncesareinsolubleinwaterandsomustbedissolved
in a different solvent. This has a marked effect on the rate of reaction .
Worked example 1 1
Retum to your graph plotted from Table 8.2 (page 159) for the re.iction between
hydrochloric acid and calcium carbonate, which was carried out at 25 C. On the same
axes, sketchthegraphyoumight1.>xpectiftheexperiml'fltwererepeatedat35Crather
thana12s 0 c
Answer
Thegrnphshouldshowaninitialgradienttwiceassteep,sincetheratewillbeabout
twice as fast. The final volume will be the same, because there is the same amount of
hydroch!orkacid
Worked example 2
Sketch an er.ergy profile for a slow reddion with a large negative Ml
Answer
Sincetr.t!redclionisslow, t hefewil l beahighactivationenergy.SinceAflislargeand
negative,theprod uctsaremuchlowerinenergythanthereactants
1 ii Add to your graph from Worked example 1, above, a sketch of the graph you might
expectiltheexperimentwerecondlictedat1SCratherthanat2SC
b Expklinthedifferencesandsimilaritiesinthegraphs
2 Sketcheoergyprolilesforthefollowingreactions:
ii a filSlieactionwithAflsmall andnegative
b afair!yfastreaction\MthAflsma llandpositive.
8.5 The collision theory

Rates of collision
Ashasbeendiscus.sed,inorderforareactiontot.tkeplice, thereactantmolecules
mustfirstcollideandsecondlyhavesufficientcombined energytogetoverthe
activation energy barrier.
For gaseous re:ictions. it is possible to cakubte how often the molecules collide.
Thisdependsonthreemainfactors:
thesizeofthemolecules - thebiggerthemolecule:s.thegre:,terthechanceofcollision
the mass of the molecules - the larger the mass. the slower the molecules move at
agiventemperatureandthefewerthecollisions
the temperature - as the temperature is raised. molecules move faster and the rate
Bigger molecules have lirger masses. so the first two factors tend to cancel out . The
colHsion rate therefore depends liigely on temperature. So, at a given temperature.
most molecules have similar colHsion rates. At room temperature and pressure. in
each cubic decimetre of gas there are about I >< loi" colHsions every second . If every
one of these collisions produced a reaction. all gaseous reactions would be over in a
For molecules in liquids. there is no simple way to estimate their rate of collision .
\Ve would =pect the rate to be lower than in gases. because the molecules are
moving more slowly and because the solvent molecules get in the way. On the other
hand , there are situations when reactant molecules can become trapped in a 'cage' of
solvent molecules and this increases their chance of colHsioo . The two effects tend to
163
PHYSICAL CHEMISTRY
rnnceleachOlherout. SrndiesOflreactionslxxhasgasesand in solution sugge.stth31

theratesareoftennOlmuchdifferentfrornoneanOlher.
Energy of collision - the energy distribution curve

The molecules in a sample of gas have a range of energ ies. In order to estimate
whm fraction of collisions will have sufficient energy to gee over the a ctivation
energy barrier, we need to know how many molecules in a sample have various
different energies - in Ol:her words. whac their Cl}('rgy distribmkm is . This was first
calculated by James Clerk Maxwell and Ludwig &ltzmann (Figure 8.12). The c nl'rgy
FlgureB.12 Jame-;ClerkMaxwell,1831-79,
distribution curve is shown in Figure 8.13. We rnn see that there are very few
Oeftlaridl11dwigBoltzmann, 1844-1906(riglt)
molecules \\-ith very low energy values . Mo.st molecules have a moderate amount of
energy. as shown by the highest point on the graph - this shows the most probable
energy. There are a few molecules with very hig h energy values.
F1g u re8.13 TheMaxwell-6oltzmarmenergy

d11tributionrurve
At agiventemperarure , theshapeofthec1.,r,eisthesameforallgases,asitdepends
only on the kinetic energy of the moleaJles, which (as we ha,e mentioned) depends
only on temperarure. The area under the graph gives the total number of moleaJles .
The line E, is marked. showing a hig h activation energy for a panicular reaction. The
shaded area shown is the fraction of molecules with energy g reater than this ...
If we increase the temperarure. the curve has a similar shape but the maximum
movestotheright.showingthatthemo.stprobableenergyincreases. The energies
become more spread ou t. so there will be fewer molecules with the most probable
energy and the maximum is slig htly lower. Figure 8.14 shows the effect of raising
the temperature by 100C. We can see that the shaded area showing the fraction of
moleculeswithenergygreaterthanE,_ismuchlargeratthehighertemperarure.
Flgure8.14Theeffect ontheern>rgy
di1trlbutionrnrveoflncre.11in9thetemperature
byl00C.ThernlYl'move1 totllerightasthe
temperature rise1. The rurveis1lighttyflatter,
rnthatthea1eauride1itremaimrnmtlnl
164
Rates of reaction I
1 a Sketch a graph of the er.e<gy distribution of gas molecu les at morn temperature.
LaOO the graph T. Draw a line to show the ilctivation roergy, E.. of a reddion
b 0nthesameaxes,s.l:etchtheene<gydi5tributionatatemperatureofabout
100( below room temperature. LaOO the graph 'T - 100'. Shade the arNs
thatsh01Nthefractionsolmoleculeswithenergygreaterthanf.atthetwo
temperatures
2 Sketchaoothergraphoftheenergydistributionofgasrnolec:uk>satroom
temperature
b Orawalir.eto<Jiowtheactivationenergy,f., ofareaction.
c Ori!Wanotherlinetos.hcr,,.,f, foracatafysedreaction,inwhichtheactivationeoergy
is halved
d Expla inwhythecata!ysedreactionissomuchfaster t hantheuncatafysed
reildion
3 Expla in why the rnHisioo rate is approximately the same for all gases at room
temperature .
8.6 Catalysts
A ca t a lys r speeds up a r<"actiOfl by providing a pathway \\ith a lower activation
energy. The effect can be readily shown on the energy distribution gra ph . On
Figure 8.13, if E,. is made smaller, the shaded area is much larger and so the rate is
Catalysts may be h onx,gcn cous. that is, unifonnly mixed with the reactants. or
h e terogen eous. in which case the cataly.s1 and the reactants are in different physical
states. There is also an important class of biochemical cataly.s1s called e nzy m es .
These three classes will be considered separately.
Homogeneous catalysis
Homogeneous catalysis occurs in bcxh the gas phase and in solution.
The production of the harmful gas ozone from oxygen near the ground is catalysed
bynitrogendioxide.whichisproducedincarengines:
Oz{g) + NOc(g) ---+ NO(g) + 01(&)
NO(g) + t o 1(g) ---+ N0 1(g)
Nitrogen dioxide may also catalyse the oxidation of sulfur dioxide to sulfur
trioxide in the atmosphere. and hen= speed up the production o f acid rain (s=
section\0.6):
N0 1(g) + S0 1(g} ---+ S01(g} + NO(g)
NO(g) + fo 1(g) ---+ N0 1(g)

The presence of chlorine morns from CFCs in the upper atmosphere is responsible
forthecatalyticdestructionofozone(seesection 15.4).
The rates of many redox reactions are increased by the use of cataly.s1s. usually
transition metal compounds. Some of these are considered in section 24.6.
Many reactions are catalysed by the H-X:aq) ion. Examples are the formation and
hydrolysisofesters.forexamplemethylethanoate:
W(aq)
The overall mechanism is explained in detail in Topic 18.

Enzymes are homogeneous cataly.s1s. These are described below and in
section28.4.
165
PHYSICAL CHEMISTRY
Hete rogeneous cata lysis

Two imporrnnt examples of the use of solid heterogeneous rnmlysis are in the
Contact process and the Haber process(,..,._.. Topic 10), in which both reagents and
products are g aseous. The reaction rnkes place on the smface of the catalySl. which
should ideally be in the form of a fine powder. This is often imprnaicable because
the catalyst would then be lost in the flowing stream of gas. The catalyst is therefore
usuallymadeintopellas.agauzeorafluidisedbed.
Jn the Contact process, the vanadium in the catalyst changes its oxidmion state. The
mechanism is considered in more deL~il in section 10.6. The Haber process for the
manufacture of ammonia involves a hydrogenmion reaaion (see section 10.5) . Other
hydrogenation reactions include those of the alkenes (see Topic 14) and carlxmyl
compounds (,..,.,. Topic 26). l,.lany transition metals catalyse hydrogenation reactions.
FlgureB.1 5 Acatalystintheformof a
gauzeThi1provide5ala rgestJrf..c:eafl'a.but for example platinum and nickel (see section 14.J). This is because thL,y are able
prevent1thecata!y1t~rig1weptawayinthe to absorb large quantities of hydrogen and form interstitial h y drides. lo these
1treamofga1e1 hydrides , hydrogen atoms are held in the spaces between the metal atoms in the
lattice. The.se hydrogen atoms are able to add on to the multiple bond of a molecule
that becomes a d sorb e d on to the metal sutface nearby. There are three stages in
catalysis in,ulvingsurfaceadsorption .
Adsorptio n - the reactants are first adsorbed onto the sutface of the catalyst . The
metalcatalystchosenmustadsorbthereactantseasilybutnotsoscrong lythat
the products do not come off again . Once adsorbed. the bonds in the reacting
React io n - the reactants are held on the surface in such a position that they can
readily react together.
IX'Sorptlo n - the products leave the surface. as the bonds between the product
andthecatalystareveryweak.
The rate of the reaction is controlled by how fast the reactants are adsorbed and
how fast the products are desorbed . When the catalyst su,face is covered with
molecules,therecanbenoincreaseinreactionrateevenifthepressureofthe
gaseousreactants sncreased.
The clli.ciency of the catalyst depends on the nature of the catalyst"s surface . This is
shown by the following effects .
Poisoning - many catalysts are rendered ineffective by trace impurities . For

example, hydrogenation catalysts are poisoned by traces of sulfur impurities. This
is one reason why nickel is preferred to platinum as a catalyst. Nickel is relatively
inexpensive: if a large amount of nickel is used. even if some of it is deactivated
by poisoning, enough will remain for it still to be effective. However. platinum is
expensive, if a small quantity of platinum is used. all of it might he poisoned .
Promotion - the spacing on the surface of a catalyst is important . For example. it
is known that only some surfaces of the iron crystals act as effective catalysts in the
Haber process (,..,.,. section 10.5). The addition of traces of Ol:her substances may
make the catalyst more efficient by producing active s ites where the reaction take.s
place most readily.
The three-way catalytic converter

Ideally. the hydrocaibons in unleaded petrol are convened completely into carlxm
dioxide and water when burned in a vehicle engine. These are non-polluting
products. though the additional carbon dioxide probably has an effect on the Eanh"s
climate (see section 13.4). In practice. however. three other products are formed
which are immediately harmful :
unbumthydrocarlxms
carbon and carlxm monoxide, from incomplete combustion of the fuel
oxide.s of nitrogen formed from the nitrogen in the air.
166
Rates of reaction I
Theam01Jntofeachimpurityprcxluceddependsonthetype 3ndeffidencyofthe
engine. When staning up a nd when idling. the proponions of impurities are higher
than when driving on the open road. Diesel e ng ines produce higher quantities of
caibon panicles than petrol engines do. To redu ce the 3mounts of these impurities.
engines are fitted with catatrtlc converters (see Figure 8.16). These catalyse the
following reactions-
CO(g) + NO(g) ---t co,(g) + }Nz(g)
co(g) + t o,(g) --+ co, (g)

hydrocarbons + 0 1(g) ---t C0 2(g) + H 10(g)
The exhaust gases are passed through the convener. which contains metals such as
platinum a nd rhcxlium supponed on a honeycomb suppon . Because lead poisons
thiscataly.s1.itisessentialtouseunleadedpetrol in3car fitted with a catalytic
Flgure8.16 Acatatylicrnnverter
Enzymes
Chemical reactions that take place in living cells are ve ry fast. even though they take
place at just a bove room temperature and at low concentmtions. This is because they
are catalysed by efficient catalysts called e nzymes. Enzymes are proieins. which are
p;:>lymers made up of units called amino acids . These units are trnned in a chain. like
beads in a necklace, to make a polymer. A typical enzyme m3y contain SOO amino
addsandhavearelativemolecularmassof SOOOO.
Enzymes are globular proteins. In this rype of protein. the amino-add chain
coils into an approximately spherical s hape (see Figu re 8. 17). Globular proieins
are soluble in water. but if their g lobular s tructure is c hanged. they become
insoluble . An example o f this process. which is called d e naturing, is the setting
of egg white when the e gg is boiled . Because globular prcxeins are water soluble ,
they 3re homogeneous catalysts, although their mechanis m of 3ction resembles
heterogeneous catalysis in that the reaction takes place at a specific point o n their
surfac e.calledthe at'lh>cs itc .
Flgure8.17Pmtl'imarelikeanec:klac:eof
beads-anenzymemayrnntainSOOamioo
acids. Theenzymefoldsintoaglobularshape,
butili1ea5ilydenotu/l'd,fo,rexamplebyheat.
\\1lenitbec:ome1ineffec:tivea1acataly1t
unfolded enzyme in its globular form
167
PHYSICAL CHEMISTRY
Most enzymes carnlyse only one reaction. or one group of similar reactions
A reactant molecule will only anachtotheactivesite if it has therighc size
andshape. Onceintheactivesite,thereactantmoleculeisheldinthecorrect
orientation to reac! and form the products of the reaction . The products leave
the active site and the enzyme is then ready to act asa rntalyst ag ain . This
mechanism of action of an enzyme is described as the lock . and. k ey h y p o thC'Sis,
. . . .,;, .
~
illustmtedinFig ure8.18. Thereacl3ntthatfitstheenzyme'sacrivesiteiscalled
thesu bstrntl'.
Some' examples of enzyme-catalysed reactions are as follows.
!to active site

(like a keyin a lock)
Yeast contains a mixture of l'nzymes called zymasl' , which convens sucrose into
ethanolandcarl>ondioxide:
C12HnOn(aq) + H10(l) ---t 4C2HsOH(aq) + 4COi{g)
~
~complex
"--"~""" ethanol
Hydrogen peroxide is harmful 10 cells. h is produced in many metaOOHc reactions

butismpidlydecomJX)Sedtowaterandoxygen inthepresenceofthecatalyst
[rt;oo
. .. ...
- produ<t,luve
~ ,;,.
When ethanol is metabolised. it is first converted into ethanal by removing two
hydrogen atoms in the presence of an enzyme called a dl'hy drogl'nasC'
C 2HsOH{aq) ---t CH,CHO(aq) + 2[HJ
GD
ethanol ethanal
Every living cell contains at least 1000 different enzymes, each catalysing one ofche
many different chemical reactions th,u take place inside the cell. Some enzymes are so
F1gure8.18 Onlyamoleculeofthecorrect efficiern that one molecule can catalyse the reaction of 10000 reactant molecules every
sizeand1hapecanattachtotheactive1iteand second . This meanstha1,irtuallyeverycollisionofthesubstm1ewiththeactivesite
beconvertedintaproduc:B leads to reaction. showing that enzyme--rntalysed reactions have very low activation
energies.
In many industrial processes, the enzymes are extracted from the organisms in
which they were made (usually a bacteria) This allows specific reactions to be carried
out,suchasthefollowing:
conversion of glucose to the sweeter-tasting fructose, using g lucose isomemse

manufacture of new antibicxics, using penicillin G aeylase
manufacture of laundry detergents. using proteases .
Recently. new enzymes have been made using genetic engineering , and these
enzymes are now used on the industrial scale. The following COfllp;:>unds are now
made industrially with genetically engineered enzymes:
l.3-propanediolformakingp;:>lymers
sitag liptin.usedinthetreatmentofrype2diabetes
paditaxel(Taxol)forthetreaunentofbreastcancer
e estersusedincosmetics.
FlgureB.19 Formulaeofthreecompaunds
Hi:1HH F-l-Q O
oowmadeindustriollybytheuseofgerietic.illy
eng ineered enzymes \! \! , ,-<: )'.', 7-0 O o,
,.,-/ '-,(''-o, ~"J-, !" o'~
I\
orco
0
F;y ~H, g D j ~
H F OH~J'
1.3-propanediol ,itaglyptin podit nel
168
Rates of reaction I
8.7 The effect of light on chemical
reactions
A few re-actions are affected by light . These a re called phomch c mlcal reac tions ,
and the yfall imot,vo ma intypes:
endothermic re actions in w h ich lighc provides the e nergy inpuc

e exOl:hermic reactions th at arestanedoffbylig ht.
i\.lOS1 ph01:ochemica l reactions are o f the firsttype. l11e yuse theenergyof

the lig ht to bring about the reac tion . Examples include the breakd own of silver
c hloride to silver a nd c hlorine, and the b romination o f alkanes. The most imponam
photochemica l reactionis ph01:osynthesis (see p age 21 0).
Flgure8.20 Photoc:hromk:1ungla1se1whk:ti
d.arhnonexposuretolight
Black-and-wh ite photography

The effect of light on silver chloride was obse1ved by Roben Boyle in the
seventeenthcentury. Allthesilverhalidesundergoa phOl:ochemicalreactionin
which the halide slowly decomposes into silver and halogen :
A reaction similar to this forms the basis of black-and-white phOl:ography. In a black-

and-white film. the usual halide is silver bromide. g rains of which are suspended in
an emulsion of gelatin. On exposure to light. the silver bromide underg oes a
phOl:ochemical change. lt absorbs a phOl:on of light. and an electron is transferred
from the bromide ion to the silver ion (see Figure 8 .21), leaving the silver bromide
in a high-energy state. represented by AgBr' .
WhenaphOl:ographistaken.theareasoffilmexJX>.""'(lto Hg htthereforeha,'e
high-energy silver bromide on them. The film is then "develo ped '. The first stage in
Ager the development process is reduction of the high-energy silver bromide to sil,'er.
This is carried out using a reducing agent. and alkaline benz.ene- 1,4--diol (old name
hydroquinone)isthemostcommon:
Flgure8.21 Electrontramferin!ilver
bromide
2AgBr + H0 - 0 - 0H---,, O V - 0 + 2Ag + 2HBr
169
PHYSICAL CHEMISTRY
Caremustbernkenoverthetimingofthissrngeofthede,elopmentprocess. lfthe
reducing agent is left in contact with the film for too lOflg, some of the unexposed
silver bromide may be reduced and the film becomes fogged'.
The film is then fixed' by being treated with a solution of sodium thiosulfate.
Na,S10/aq). which photographers call "hypo'. This dissolves any unchanged silver
bromide, preventing it from reacting funher when the film is =posed to light:
The film is washed thoroughly at this srnge to remove all the silver-thiosulfate
comp]= . 'What remains is a negative' of the image, with light areas of the image
showingasdarksilverareas.
Chain reactions
A few phOlochemical reaaions are chain !"<'actions. These are exothermic re-actions
that have a high activation energy. The light breaks a bond homolytically in one
of the reactants. forming an atom. This fr= atom is energetic enough to re3ct with
3nother re3ctam nx,lecule and produce another free 3tom
The process then repeats. building up imo a chain reat'tion . The light has
provided the energy to overcome the activation energy barrier. Examples of chain
reactions include the reaction of hydrogen with chlorine, and the chlorination of
3lkanes(,..,.,.sectionl3.5)
Klnetics isthesttidyoltheratesofreitclions The rate inue;is.es if the rea<tants are made more
The rate olaredC!iooisdefinedashowfastaproductappe;1rs coocentrated,bec.ausethemoleculesrnllidemoreflequent!y.
orhowfastaredctantdisappears F0<thesamereaSClll,inaeasingthepresrureofagaseous
Therateofarl'itd:iooisdeterminedbytheheightolthe reitclionincre.isestherate
activationenergybarrier,andnotbythevalueofAfl. The rate inue.Jses if the temperature is raised, mainly because
Physicalmethodsollindingtherateofreactkminclude therearemorernllisionswlthsufficielltenergytoreact
measuring the volume of gas given oft over time A 10( rise in temperature often doubiesthe rate of redclioo
measuringachangeinmassOVl'flime The area under the energy distribution curve shows the
lollowingachangeincolourovertimeU5ingarnlorimeter. fractiooofmoleculeswithinacertainenergyrange .
Chemical methods of find ing the rate of reaction include On!ythelractionofmolecu~wlthenl.'fgygre.iterthanthe
removing samples at timed intervals. 'freezing' them and itclivationenergy,f., canre<ICI.Theseareshownbytheareato
thenusingchemicalanalysis,forexamp~titration therightoff, ootheenergydistributionrnrve
using a 'clod' method A catalyst providesanalternativepathwayofloweractivatioo
Therateofredetiooatagiventimeisshownbythegradiellt energy.
ofthegraphofamountofproductagainsttime(0<the Therateofarea<tioninsolutionisusual!ychangedif a
ne,gativegradientofthegraphofamountofredclant different solvent is used .
against time) Somereactionsgofasterinthepreseoceoflight
170
Rates of reaction I
Please<;e('thedataSKtionoftheCOforanyA,.value5you a i Draw a new distribution curve, dear~ labelled T' for
the 'lame mixture of gases at a higher temperature, T';
ii Maric.dear~.asH,thepositionoftheactivationenergy
1 catalrstsspeeduptherateofareaction"ithoutbeing
of the reaction at the higher temperal\lre, T'. [3]
comumedbytheoverallreaction.
b Explain the meaning of the term actMlOO'I ene,w. [2]
a Chlorineradicalsinthestratosphereactasacatalystfor
c The reaction between nitrogen and hydrogen to produc:e
ozone depletion.
ammonia in the Haber process is an el0mple of a
i Researchchemistsh-proposedpossible reaction
Jarge-scalegaseousreactionthatiscatalysed
mechanisms for ozone depletion. The equations below
i Statethecatalystusedandgive the operating
representpartofsochamechanism.
temperatureandpressureofthe
Completetheequatioos
Haber process
Cl+Oi-+ ii On the energy axis of the graph, mark the position,
CIO+ ................. +Oz (2) clearly labelled(, of the actflatiooenergyolthe
reactionwhenacatalystisused.
ii Writeanequationfortheoverallreactionini. (1)
iii Use your answer to ii to explain hON the use of a
b Oneofthecatalysedreactioosthattakesplace ina
catalyst results inreactioosoccurfingatafaster
catalyticconverterisshownbelow.
rate. [3]
2CO(g) + 2NO(g)-+ Ni(Q) + 2COi(g) d TworeactionsinYOlvingaqueousNaOHaregivenbelow.
CH1CHBrCH1 + NaOH-+ CH1CH(OH)CH3 + NaBr reaction 1
Thecatalystusedisplatinumlfhodiumattachedtoa
HCI + NaOH-+ NaCl+ H10 reacti o n 2
ceramic surface.
In order for reactio n 1 tooccur,thereagentsmustbe
Outlinethestagesthattakeplaceinacatalyticcooverter
heated together for some time.
toallowCOtoreactwithNO [4J
On the other hand, react io n 2 is almost instantaneous at
t Explain,usinganenthalpyprofiled~ramanda
room temperature .
Bolttmann distribution, how the presence of a cataly.,t
Suggest brief explanations why the rates of these two
i~stherateofreaction. [7]
reactionsareverydiffe~t. [4]
d Explain why many industrial manufactixing proc= use
{Cambridge lnremarional AS & A level CherTmr,y,
catalysts
9701, Paper 21 02 June2010}
lndude in your answer ideas about sustainability,
3 In many countries, new cars have to comply Y.ith regulations
@<:onomio and pollution control. [4]
which are intended to reduce the pollutants coming from
{OCR Chemistry A unit F322 Q4 (port)January 201 I}
their internal combustion engines. Two pollutants that may
2 The diagram below shows. for a ~ n temperature T,
be fom,ed in an internal combustion engine are carbon
aBoltimanndistribvtionofthekirieticenergyofthe
monoxide, CO, and nitrogen monoxide, NO
molecules of a mixture d two gases that wil react together,
a Outline how each of these pollutants may be formed in
suc;hasnitrogen and hydrogen. The activation energy for
an intern.al combustion engine.
the reaction.Ea. is marked .
b Statethemainhazardassociatedwitheach ofthese
pollutants [4]
{Cambridge International AS & A level Chemistry;
o,mb.,,f 1 /'\. 9701, Paper22Q2 eNovembe,2010]
molornlo , ~
energy '
171
AS Level
Physical chemistry
9 Equilibria
Many chem/a/ reactions do not
go to completion. They stop at a
Learning outcomes
point called the equilibrium position, By theendolthistopicyoushouldbeableto
1'n11,.borhreactantsandproducts 7.1a) expla in, in terms of rates of the forward and revef'ie reactions, what is meant by a
are preient but there seems to be reversible reaction and dynamk equilibrium
no further reaction. In this topic. 7.1b) 51ateleChatehef'1Pnncipleandapplyittodeducequalitatively(fromappropriate
Wi' study how a change in reaction infomiation)theeffects of changesintemperature,concentratiooor pressureoo
conditions brings about a change a system at equilibrium
inthepositionofequilibriumofa 7.1c) 51:atewhetherchangesincoocentratkm,pressureortemper<>tureortheprese<ice
ofacataly51affectthe~alue of the equilibriumamstantforareactioo
7.1d) deduceexpiess.ioo1forequ ilibriumrnnstantsinterm1ofconcentratkms,K,,and
partialpre1sure1,K,
7.1e) u1kulate the va lues of equilibrium (onstants in temis of (on(entrat kms or partial
pressures from appropriate data
7.1f) u1kulatethequantitiespresentatequilibrium,givenappropriatedata
7.1g) desc:ribeandexpla inthe(onditionsusedintheHaberprocessandtheContilcl
proces1,asex.ample1oftheimportanceofanunderstand ingofdiemiu1I
equilibriuminthed\emkalindustry.
9.1 Reversible reactions

Many chemical reactions. such as combustion. appear to go completely,
convening all the reactants to products. If methane is burnt in an excess o f
oxygen. no methane is left over. Reactions such as these go to completion
bemuse they are highly exothem1ic. that is , AH is large and negative . But there
are many reactions , panicularly in organic chemistry, for which AH is small . These
reactions may not go to completion - at the end o f the reaction a detectable
amount of reactant remains, mixed with the product. Such reactions are called
reversible rcacdon s.
To decide whether a reaaion is reversible or n(){. the concentrations of reactant
and produa need to be carefully measured . A conunon laboratory methcxl o f analysis
may detect reactants in the final mixture if they are present in as high a proponion as
1%. but more refined techniques can be many times more sensitive.
Thereaaionofa strong add and a.strong base:
appears to go to completion but this is not actually the case. as is shown by the fact
that pure di.stiJJed water has a slight electrical conductiviry. This conductivity is due to
indicating that the reaction can go in either direction . Only two molecules in every
1()9 molecules ionise and so the ionisation can usually be ignored. but it becomes
important when we .study the pH scale of acidity (see Topic 22).
172
Equilibria I
A reaction is considered as having gone to completion if any re-:iaams in the final
mixrure are present at such low concentrations that they do nOI affect any tests or
re:iaions that are carried out Ofl the produas. In practical terms. this means that if the
re-:iaion is more than 99% complete. it can be regarded as having gone to completion.
9.2 The position of equilibrium

Dynamic equilibrium
A reversible reaaion appears to stop when no overall change is taking place; the
reaaion is said to be in equilibrium. For =ample. a reaaion may come to be in
equilibrium when 75% of the re:ictants have changed into products. Under these
conditions, the composition of the equilibrium mixture is 75% products and 2So/o
reactants, and this composition is known as the o s ilion of cqulllbrium.
At equilibrium, there is no overall change from reactants to products and it seems
as though the reaction has stopped. This is nOI actually the case. There is no re:ison
why the lorward reaction. that is. the reaaion between the reactants. should nOI
continue,sincetherearestill reactantspresentinthemixrure. The reason why there
is no overall change is that the bac k reaction . which turns the products back into
reactants. is now going at =actly the same rate. A reversible reactiOfl in which
the forward a nd back reactions are lxxh taking place at the same rate is termed a
dynamic cqullibrium .
--
Forareve~biet&Ktion
reactanto; ~ products
Thedooble-headedarrow ~ indkatesa reactionthatgoestoequilibrium

Atequilibrium,tr>ernte oftr>!!forward re.-ictionequalstherateolthebad<.re.-ictioo.
Demonstrating dynamic equi librium

A panicularly effective way of showing that an equilibrium is dynamic is to use
isotopic laDClllng. In the Haber process. nitrogen and hydrogen gases are allowed
to come to equilibrium with ammonia:
N{g) + 3H,(g) ~ 2NHlg)
If deuterium (a heavy iSO!ope of hydrogen) is substituted for some of the hydrogen

gas in an equilibrium mixture of the gases. son,e deuterium becomes incorporated
into the ammonia. as can be shown by analysis of the mixture by mass spectroscopy.
This shows that the forward reaction is continuing to take place, and this must be
balancedbyanequalrateofbackre-:ictioninorderthacthesamepositiond
equilibrium is maintained(seeFigure9.1).
Flgure9.1 lf deutl.'l"iumi1substitutedlor
someolthehydrogengasinthee quiliblium
mixture. some deuterium becomes borided to
NH,D
nitrogeninammaniamolec:ules
NH,D
A similar experiment may be carried ou t with lead chloride. PbCl, . labelled

with radioactive lead. Lead chloride is only slightly soluble in cold water. and a
saturated solution of the radioactive sale can easily be made. If unlabelled lead
chloride is stirred into the saturated solution. no more of the solid can dissolve
overall but ii is fou nd that some of the radioactive lead still ends up in the solid
173
PHYSICAL CHEMISTRY
(se,, Figure 9 .2). This shows that some of the radioactive lead ions in the solution
have been precipitated into the solid. and an equal number of lead ions from the
solid must have dissolved to keep the solution satumted .
Rgure9.2!f solidleadchklridei'iplac:edin
asaturatl'dIDlutKl!lofleadchloridelabelled
withradioactiveleadiom,Pb'(1howni11red),
theso lidbecol1ll";radklactive
solution Occ
of lead
chloride
Worked example
a Whatisme;intbyareversiblereactioo?Giveanexampleofareversiblereaction.
1 State,givingareason,whetherAHfor
b How could you show t hat it is reversib~?
areversiblereactionislargeorsmall.
2a Whatismeantbydynamic Answer
equil ibrium? a Areversiblel&Ktionisooeinwhichit isposs.ibletodetectunchangedreact.-mtsinthe
b Expkci inwhyitistl.>,Honabletothink equilibriummixture,andinwhichboththeforwardandbackreMtionstakeplace.One
that chemkal equilib!ium is dynamk exampleisthenelllralisatiooolastrorigac:idwithastrongbase
rntherthanstatic
H4aq) + Of1{aq) s='- Hi0(0
c De1cribe an experiment which
shows tha t achemicalequili briumis b The reaction in part must be reversible because pure water conducts e~ridty, to a
dynamicrathefthanstatic small extent
Moving the position of equilibrium

In Topic 8, the effects of concentration. pre.s.,ure of gases, temperature , state of division
of solids, and catalysis on the rate of re:iaion were studied. We sh.tll nmv consider
whac effect (if any) these factor,, may ha,'<' on the JX)Sition of equilibrium ofa n,-aaion.
Some examples of reversible reactions

and equilibria
If acid is added to a yellow solution containing c.o/- ions, the solution turns
orange owing to the fonnmion of Cr10-,,_ ions . The re:iction can be reversed by
!he addition of alkali.
W (aq)
2cr0/-(aq) + 2H+(aq) ~ CrzO/-(aq) + H,0{1)
~llow 01-r~orani:e
If alkali is added to a brown solution of iodine, the colour fades owing to the
fonnmion of colourless 10- ions . The colour returns on the addition of acid.
If a mixture of the brown gas NO, and the almo.s1 colourless gas N,o. a! equilibrium
is suddenly compres.sed, the mixture darkens and then the colour slowly fades . The
initial increase in colour is due to the increase in concentration of NO/g) as the
volume decreases, but this decre:ises as the equilibrium moves in the direction of
174
Equilibria I
If a pink solution of cobalt chloride is warmed. the solution goes blue. It changes
--~
back to pink on cooling. The foiward reaction is endothe-rmic.
Co(H 10)/+(aq) + 4Cnaq) ,=====: CoCl/-(aq) + 6H 10(1)

piruc ooolini: hl=
The changes in position of these equilibria can be predicted from l.c Chat('Jicr"s Princ llc .
LeChatelier's Principle statesthatiftheconditK>n1ofasy1teminequilibriumarechanged

(forexomple,bychangingtheconcentrationorp!l'ssureortemperatull'),thepositiooof
equilibriummOYessoastoreducethatchar,ge
9.3 Changing the concentration

If we increase the concentration of one of the reactants of a reaction in equilibrium
the rate of the forward reaction increases and more products form. The resulting
increase in the concentration of the products will then lead to an increased rate of the
backreactionumilanewp;:,sitionofequilibriumissetup.
The position of equiHbrium has moved !O the right (see Figure 9.3). with slightly
more product being present th.~n at the original position of equilibrium. This is in
agreementwithLeChatelier'sPrinciple.
Flgure9.3Anincrease inthernncentratioo
reactant1 + reactant2 ~ product ,ystem in equilibrium
olonereactantconvertsmoreoftheother
reactanttoproductandmovesthepo'iibon
ofequil ibliu mtother,ght
reactant, + reacta nt2 ~ product "ncre,n e"nconcentrat"onofreactant,
reactant1 + reactant 1 ~ product equilibriummovestothe right
In a similar way. if the concentration of one or more of the reactants is reduced (or
the concentration of the pr<Xiucts is increased) , the position of equilibrium moves to
-~
the left. The situation may be summarised as shown in Table 9.l.
Tabte9.1 Theeffectonthepositionof Con<entratlonof Dlnictlon of moveme nt o f
equilibriumofchangingtheconcentr.ition theposttlonofeq ullbrlum
ofthereactant1ortheproducts
I to the right
I
l iocreall.'d
to the right
Worked example 1
What istheeffectofiocreasir.gthecoocemrationofhydrogenioosonthefo!lawingreactK>n?
CH 3Coi-+ W ,=' CH 3CO.,H
Answe r
The equilibrium is pushed over to the right, that is, more ethanoic add, CH 3CO.,H, is formed .
Worked example 2
Consider the fo llowing equ ilibrium
1 Con~derthefol\owingequili brium CHiCOiH + CiHsOH .=' CHiCOiHs + HiO
Hi(g} +Ii(g) ,=' 2HI(g)
Howwill t hepositionof equilibrium Expl.-iin why removing water leads to more ester being formed in the eq uilibrium mixture
alterwhene."Khofthelo! lowing
Answe r
changes is brought about?
Initially, removing water means that the rate of the back reaction is decreased while that of
a addingmoreiodine the forward reddion stays the s.ame. Le Chatelk>r's Principle predicts that the po~tion of
b add ing more hydrogen iodide equilibriumwillmovetoopposethechangeintheequilibriummixture.Hencetheposition
c removing hydrogen ofequ ilibriummovestotheright,producingmoreesterandwater
175
PHYSICAL CHEMISTRY
9.4 Changing the pressure

Jn3gaseousreaction. achangeinpressuremayaffectthepositiOflofequilibrium
in a way similar to changing the concentration in an aqueous re:iction . However. for
a mixture of gases. an increase- in pressure may incre:ise the concentration of lxxh
re-actantsandprcxluctstothesameextentandmaythereforehavenoeffectonthe
position of equilibrium. This occurs if there are the same number of gas molecules on
the left-hand and right-hand sides of the equation. An example is the decomposition
of hydrogen iod ide:
Here there are cwo molecules of gas on lxxh sides of the equation, so changing the
pressurewillnDlchangethepositionofequilibrium.
At a lower temperature, hydrogen iodide decomposes as follows. producing solid
Now two gas molecules on the left form only one gas mo lecule on the right . Because
pressure affects only the gaseous components of the mixture, an increase in pressure
now will speed up the forward reaction more than the back reaction, so that the
equilibrium moves to the rig ht. This again agrees with the prediction from Le
Ch:uelier'sPrinciple,becausetheincreaseinpres.surecan be reduced if the
equilibrium moves in the direction in which fewer gas molecules are formed. We can
summarise the situation as shown in Table 9.2.
T.ible 9.2 Theeffl'Ctonthepos.ibonof
Number of gaseous Number of gueous Direction of movement of the position
eqvilibrivmolincreasingthepre1su1e reacbnt molecules product molecules of equilibrium when the pressure Is
Increased
to the right
no change
Whateffect(ifany)will therebeone.Kh
Worked example
of t he followir,gequilibriawhenthe Whati1theeflectofanincrea1einpre1sureonthe1ynthesi1ofammonia?
pressu re is increased?
1 2HBr{g} .=e Hi{g} + Bri(g) Answer
2 PCl]lg) + Cl1{g) ,=' PCl 1(g) In this reactkln, four molecules of gas become two molecules of gas. An increase in
l Hi00) "F HiO(g) ;xessurefavours theprodLJCt s,asthesecontain fewergasmolecu les.Soincreasingthe
,4 CaC01(s} .=e CaO(s) + C01(g) ;xessure result s in an equilibrium mixture containing m0<e ammonia
9.5 Changing the temperature

LeChatelier'sPrinciplecanalsobeusedcopredicttheeffectofatemperaturechange
on the position of equilibrium. The most imponam factor is whether the forward
re:iction is exOlhermic (AH negative) or endothermic (AH posith,e). If the temperature
is raised, the equilibrium will move in the direction which will tend to lower the
temperature. that is , the endOlhermic direction. The effect is summarised in Table 9.3.
Tabl e 9.l Theeffectonthepositionof SlgnofMlforforward Direction of movement of

equilibliumofchangingthetemperature
~""'" theposttlonofequllbt1um
to the right
to the rig ht
176
Equilibria I
Careful control of temperature is important in the Contact proce.s.s and the Haber
process.asweshallse-elater.
Worked example
Whatistheeffectofraisingthetemperatureonthelollowingequilibrium?
H1(g) + I1(g) .... 2Hl(.g) Af1 =- 12kJmol- 1
Answer
The reaction is exothermic (gives out hwt). On raising the temperature, the equil ibrium will
move in the direction that reduces the temperature, that is, in the endothermic direction
Theequili briumwillthereloremovetotheleft
What will be the effect of lowering the temperature on each of the following equilibr~?
1 Ni(g)+3H1(.g)~2NH 3(g) Af1 =-92kJrnot- 1
2 HiO(I) "F W(aq) + OW(aq) Af1 ~+S8kJrnot- 1
9.6 State of division and the addition

of catalysts
State of division
In a he1erogeneous reaction, a small particle size speeds up a reaction by increasing
thesurfacearea . lfthereaction is in equilibrium. l:xxhtheforward and back reactions
willbe speededupwhcnthesUJfaceareais increased. Thisincreaseinspeedisthe
same for l:xxh reactions . If. for example. the surface area of a liquid was doubled , the
rate at which molecules leave this surface would be doubled. but so too wo uld the
rate at which they joined the surface again. The position of equiHbrium is therefore
unchanged (see Figure9.4).
n
Flgure9.4 ln.1and b therei1thesame
amoontofwater.buttllernrfac:earea in .11
is twice that in b The rate<;ofevaporatkm
andcooden1atkmarebothtwlceasfastin
r1 1
a asin b .butthepmitkmofequilibriumis
um:h anged
1 11
1111
Catalysts
The effect of adding a catalyst to a mixture in equilibrium is similar to that of
increasing the surface area . Born the forward and backreactionsarespeededup
by the same amount. and the position of equiHbrium is unaltered . lt may no( be
immediately obvious why this should be the case, but it can be demonstrated by the
following thermodynamic argument. If an eXOlhermic reaction was in equilibrium
and then a catalysi was added which made the reaction faster in the exothermic
direction o nly, energy would be obtained. This energy could not have come from
the catalyst (which. by definition , is left chemically unchanged at the end). \Ve would
have obtained energy from nowhere. which is contrary to the Law of Conservation of
Energy (see Figure9.5).
177
PHYSICAL CHEMISTRY
Flgure9 .5 Areac:tioninequ ilibriumis

placedinrnntactwithacatalystbyopenlng
thetrapdoor.rt"thischangedthepos.itkm
of equilibrium, thepi'itonwouldmoveupor
down,dl'peridingoowhetherthecataly1t
shiftl.'dthl'equilibfiumintheendothermkOf
exothermkdirecti:m.Thismoveml'ntolthe
pistoncouldbeusedtodosethetropOOO!, piston
andtheprocesswouldthenberepeated
Petpetualmotionwouldhavebeencreated,
whkhisimpossible
cat alyst
4' 9.7 The equilibrium constant Kc

We have just shown how the JX)Sition of equilibrium changes when the external
cond itions are altered . Changing thesrnte of division or adding a catalyst affects the
rate of the reaction , but does nOI affecc the position of equilibrium. The factors th31
do affect the positionofequiHbriumare:
the concentrations of the reactants and prcxlucts

the temperature.
lnthissectiOflweshallstudyquantitativelytheeffectofchangesinconcentrationon
theJX)Sitionofequilibriurn.
Forareactioninequilibriurn.forexarnple.
itcanbeshownthat,atagiventernperature.
[NO,(g )J!,.. (N0,) 2

I(,, = [N,O./ g)l"""' whichisusuallysimplifiedto (N,O,I
where K 0 is a constant, called the <'quilibrium con s tant.

The square brackets( lindicatemolecularconcentrationsatequilibrium in
rnoldm- 3 . The subscript c' indicatesthatthisequiHbriurnconstant is calculated
usingconcentrationsandcan. therefore. be distinguished fromanO!herequilibriurn
constant. Ki,. which uses pressures. asweshallseelaterinthetopic.
Forthegeneral fl>iKtion
A +B~ C + D
the equilibriumco nstant isgiveobytheexpress ion
K, ~ ::!:~]] \~t: i~t

=
Unlike the position of equiHbriurn. the value of the equilibrium constant does nOI
change with concentration; that is why it is termed a 'constant". The only factor that
affectsitsvalueistemperature.
Thesquaredterrninthe=pression
K., = (NO,(g)J!,..
(N 20,(g)I..,..
178
Equilibria I
arises because there are !WO NO, in the reaction products. We could have written the
Then the equilibrium consrnm would have been written as :
There are several ways in which this expression can be derived. The most
fundame ntal is by mea ns of the rmodynamics. but it can be approached through
experiment or by way of kinetics .
Deriving equilibrium constants

By experiment
Thefollowingreactionranbestudied:
A range of mixtures containing different amounts of reactants and products ""' made
up . The mixtun,s are left to come to equilibrium and are then analysed, for example
by determining the amoum of ethanok add present by titration. For a wide range of
mixtures.itisfoundthmtheratio:
(ett,co,c,HjlH,O]
[CH 3CO,HJC 2HjOHI
Ki neti c ap proach
If the kinetics of the forward and back reactions are known, the equilibrium conSlant
can be nelaced to the rate constants. For the following re:iction :
rate of forward reacrion at equilibrium = kJN,04)

rate of back n,-action atequilibrium = I.\JNO,f
where bi and ~ are the rate cotlSlants for the forward 3nd back n,-actions
re.spectively (seeTopic2\foranexpbnationofthesernte=pressions).
Atequilibrium.thecworntesareequal,therefore:
At a given temperature. the two rate consi:ams are fixed. and
Th e uni ts of Kc
FDf the reaction CH1COiH + CiH 50H .=" CH1CO.,CiH 1 + Hi 0, the exp,-ession for K, has
t\vo concentration temis on the top and two on the bottom
[CH,CO,C,H,IH,O] {moldm-' )(rnoldm-'}
[CH,CO,H IC,H,OH] units: (moldm-')(rnoldm-') = 1
Theuni11topandbottomt:hewon,air,cej,andtheresulti:sthatKchxthisreactionhasnounits
But for the redC!ion Ni0 4(g) .==- 2NOi(g), the expression for K, has two temis on the top
andonetermonthebottom
K z [N0,(9)]' {moldm-')' _1
units: (moldm-') ~moldm
' !NP,(g)]
179
PHYSICAL CHEMISTRY
Worked example
WritetheexpressionlorK::andstateitsunitsloreachofthefollowingreactiom
I1foq) -tr(aq) ~ 11-{aq)
b Ni(g) + 3H 1(g) ~ 2NH3(g)
Answer
ii K,~ [I~\i1-i; units are mot- dm
1 3
1 6
b K, [!~]~~']'; units are moldm
1 WritetheexpressionforK,,mdstateitsunits/Ofe;ichofthelollowingreactions
2CrOt1iaq) + 2W(aq) "F CriOl-{aq) + HiO{I)
(Note:HiOisthesolvrot;itsrnncentrationisrnmtant,soitscoocentratioodoesnot
appearintheexpressionforKcJ
b !i(aq) -t 2Fe1*laq) ~ 2r{aq) -t 2Fe1foq}
Evaluating K, for a reaction

In order to determine the value of an equilibrium consrnnt, known amounts of
reactants are allowed to come 10 equilibrium . The am01Jnt of one of the substances in
the equilibrium mixture is found by experiment . The amounts of the cxhers rnn then
be worked out from the stoichiometric equmion. as shown in the following worked
=ample.
Worked example 1
2.0mol of ethanoic acid and 2.0mol of ethanol are mixed and allowed to come to
equilibriumwiththeethy1ethanoateandwatertheyhaveproduced.Atequilibrium,the
amount of ethaooic acid present is 0.67mol. Cakulate K,
Answer
We start by working out the amounts, and hroce the cor-.c:rotrations, of the four
substances present at equil ibrium from the stoichiometric equat ion:
CH 3 COiH + CiH 50H -;,= CH 3COiCiH 5 + H1 0
molesat1tart/mol{given) 2.0 2.0 0 0
moles at equ ilibrium/mol (giveo)
moles at equ ilibrium/mol (2.0 - 0.67)(2.0 - 0.67)
0.67mol 0.67mol 1.33mol 1.33mol
0.67 0.67 1.33 1.33
cor-.c:entrationsatequilibrium
V V v v
where Vis the total volume of the mixture
K = [CH,CO,C,H,IH,O]: 1.33/Vx1.33N
' [CH,CO,H]!C,H,OH] 0.67/V x 0.67/V
3 4.0 {oounits)
K,hasnounitsbecausetherearethesamenumberofmolecules onboths.idesofthe
equation. Thisalsomeans t hatthe volume, \/,cancels. Theva lueofKc,andtheposilionof
equ ili brium, do oot depl!nd on the volume of the reddion mixture
180
Equilibria I
Worked example 2
0.30mol of dinitrogeo tetra oxide, N10 4, is allowed to come to equili brium with nitrogen
dklxide, N01. The amount of nitmgert dioxide at equilibrium is 0.28mol. Cakulate:
theamountofdinitrogentetraoxideatl'quil ibrium
b the value of K, at the temperature of the experiment, given that the YOlume of the
conta iningvesselis10.0dm 3
Answer
N104W,1 .,. 2N01{Sll
molesatstartlmol 0.30 0
mok>s at equilibriumlmol (0.30 - f x0.28) 0.28
mok>sofN10 4 atequiliOOum = 0.1 6 mol
b K ~ [NO,]' ~ {0.28/lO)' 0.049m oldm-l

' (N,O,] 0.16/10
1 Wheo iodk acid is disso~ed in water, it Klni'il"i slig htty accord ing to the following
equilibrium:
H!Oi(aq) ~ H1aq) + 101- {aq}
In a O.SOmoldm- J solution of HJ0 3, the rnr.centration of W ions is found to be
0.22moldm- 1
ConstructanexpressionfOfK,,cakulateitsvalueandstateitsunits
2 Whefiaqurousammoniaisaddedtoasolutiooofas.i!verx1lt,thefollowingequilibrium
is set up
When equal vclumes of 0.1 moldm-1 Agiaq} and 0.2 moldm- 1 NHi(aq} were mixed,
the equili brium concentration of (Ag(NHi.\.,Jiaq) was found to be 0.03Smoldm-1
ConstructanexpressionlorK,,cakulateitsvalueandstateitsunits.
9.8 Using equilibrium constants

Finding the composition of the equilibrium
mixture
An equilibrium constant rnn be used to calculate the composition of an equiHbrium
mixmre. For =ample. the equilibrium consrnnt for the re-action :
is 4.0. If we sian with 2.0mol of ethanok add and 2.0mol of etha nol. the
composition of the equilibrium mixture can be found by me-:ins of some simple
algebra as follows.
1.ettherebexmolofethylethanoateatequiHbrium:
CH,oo,H c,H,OH CH,oo,c,H, H,o

moles at start/mob 2.0 2.0 0 0
molesat e qui~brium/mol: (2.0 - x) (l.0 - x)
(2.0 - x) (2.0 - x)
concentr-.tioruatequi~brium/mol: - v- --
v-
181
PHYSICAL CHEMISTRY
Kc 1::::~;::!7~~)
(xiv/
(2.0 - xiv)'
The volume terms cancel out. This give.s us :
(2.0x- :,:)' = 4.0
Takingsquareroo(sofbolhsides ,
At 700 K,thevalueofK,forthefollowing
- - = 2.0
(2.0 - x)
H1(g) +Ii(g) "F- 2H I(g)
O.SmololHi{g)andO.SmolofI.i(g)were Either x = -+4 .0 - h so x =l. 33
mixedat 700Kandalkiwed to reach x = ---4.0 + 2x so x = 4.o
equilibrium. The second value must be rejected as it is imJX>ssible to produce more than 2.0mol
Wh atisthecompositiooolthe
of produa . Therefore, 31 equilibrium there are l .jmol of ethyl ethanoate, l.jmol of
equ iliOOummucture?
water. 0.7mol of eihanoic add and 0.7mol of ethanol.
9.9 The equilibrium constant Kp

Forgaseousequilibrfa, theconcentrationsofreactantsand producrscanbeexpressed
in terms of the pressures of the different components. lf the reaction mixture behaves
as an ideal gas. the ideal gas equationpV= nRT(M:e section 4.13) can be u.sed . The
molecular concentration, [X), which is n/V, is then equal top/ RT. This shows that, at a
given temperature when T is constant, the pressure of a component is proportional to
Thus the equilibrium cot151am can be written in tem1s of the pressures of the
different components rather than their molecular concentrations. For the equilibrium
H 1(g) + Iz(g) ~ 2HI(g)

for example, the equiHbrium consmnt can be wriuen
~ = PH~)~'
where PH, . PH, and A, are the pressures o f the different components, called their
partial pt'('SSUn.<s. If no other gases are present . the sum of their partial pressures
willequalthetcxalpressureP.
If PH, = 0.SOatm and PH, - A, = 0.30atm, we have
~ = PH~=)~' = 0.;~;.30 = 2.78

As there are two partial pressure terms on the top and two on the boitorn, KP has
no units (which is also true for K,, as it has t"u concentration terms on the top and
two on the bottom). This means that increasing the torn[ pressure "ill have no effect
on the position of equilibrium. If we had used pascals for the panial pressures, we
would have had the same results because we would have multiplied each term by
1.013 x JO' and the four 1.013 x 10' terms would have cancelled out. The situation
is more complicated if the number of molecules is different on each side of the
equation.Forexample,fortheequ ilibrium
the equilibrium constant is
182
Equilibria I
If PNo = 0.50atm andPN,o, = 0.3Qatm.
1
~ =~ = 0.50' = 0.83atm
P,,z0, 0.30
KP wo uld also equal 0.83 x 1.013 x \Ol = &1.4 kPa.
lnthiscase,changingthetotal pressurewillaffectthepositionofequilibrium.
It does not change the value of~. however. If. for example. the torn[ pressure is
doubled by compres.sing the mixture. initblly ~ would increase by 4 times while
P,; 204 would only double. In order to keep KP consrnm. p,,01 must then decre:ise and
PN,o must increase . The position of equilibrium has moved to the left. in accordance
4
withLeChacelier'sPrindple.
Worked example
Thekeyre<1ctionintheConla{tprocessformamifacturingsulfurkacidistherea(tion
between SO., and Di
Writeilllexpressioofortheequi'ibnumconstant.Ki,.forthisreaction,anddecidewhat
conditionsoft~atureandp<e5sure1\'0UdlaYOUrtheforwalreaction.Explainyouranswef.
Answer
'"'
Kp~ p,,},xpo,
According to Le Chatelier's Principle, high pressure and low temperature would favour the
fofward1edClion.Thisisbecametherearefewergasmolecule1ootheright-h,mdsideof
theequation,andthereactiooisexothermk
TheHaberproc:essfortheindustrialmanufactureofammoniausesthefollowingfl'ilction
Ni(g} + 3Hi{g}"F2NH1(g) tJ-/3 - 93kJmot- 1
Write an expression for the equil ibrium coostant, Kp, for this reaction, and decide what
conditions of temperature and pressure would favour the lcxward reoctioo. Explain yoor
Manychemicalreoctioosdonotgotornmp~tioo:theytakeup F0< a reaction A + B "F C + D, there isan equ ilibrium

aposiliooof dynamicequ lll brium. constant K::ruchthat
This positionofequilibrium maychangeifttiereoctioo
rnnditionsarechanged.Thedirectiooofchangecanbe
predictedming l eChatelier'sPrinc ip le
K,=\~~i~i
where[]areconcentratioosinmoldm- 1 .Thevalueofthis
e lncre.-isingtheconcentrationofareactantmovesthepositiooof coostantdoesnotchangewithchangesinrnncentration:itonly
equilibiiumtotheright changeswithchangesintemperature
lncreasingthepressureinagaseousr&Klioomovesthe lftherrectioncomponentsareallgases,theequilibrium
equilibrium in the direction that has fewer gas molecules coostantcanalsobeexpre1sedintermsofthepartialpres1Ures
P1,,PB,PcandPoasfollow1
K,~::::
Increasing the temperature moves the positioo of equ ili brium in
theendothermicdirectioo
Redocingthepartidesize0<inueasingthe1urfaceareaspeeds
upareac:tion,butdoesnotchangethepositionofequilibrium
e Theadd itk>nofacataly1tdoe1notaffectthepositionof
equilibrium,onlyhowqukklyequil ibriumisreac:hed
183
PHYSICAL CHEMISTRY

PleaseSttthedatasectionoftheCOforanyA,valuesyou b i Calculate the amounl in moles, of NaOH used in the
may ..... titration.
ii What amount. in moles. of this NaOH reacted with the
1 When hydrocarbons such as petrol or paraffin wax are
hydrogen chloride?
burnedinane)(cessofairinalaboratory,carbondioJlide
iii Write a balanced equation for the reaction between
andwateraretheonlyproducts.
ethanoic acid and NaOH.
When petrol is burned in a car engine, nitrogen
iv Hence calculate the amount. in moles, of NaOH that
monoxide. NO. is also formed. reactedwiththeethanoicacid. [4]
NO is also formed when nitrosyl chloride, NOCI,
c i Use your results from b to calculate the amount, in
dii500atesaccording to the following equation
moles,ofethanoicacidpresentatequilibrium. Hence
2NOCl(g)-+ 2NO(g) + Cli(g) drawandcompletethetabiebelo.v.
Different amounts of the three gases were placed in a

dosed container and allowed to come to equilibrium at
230 (. Theexperimentwasrepeatedat465C.
Theequilibriumconcentrationsofthethreegasesat
Equilibrium
eachtemperaturearegiveninthetablebelow.
ii UseyourresultstocalculateavalueforK<forthis
reaction . [3]
NOCI Ia, d Estersarehydrolysedbysodiumhydroxide.O urir.gthe
titration,sodii.mhydroxidereactswith ethanoicacidand
2.33><10-1 l .46><10-1 1,.1sx10-' thehydrogenchloride,butnotWTththeester.
Suggestareasonforthis. [11
3.68><10"' 7.63><10-1 12.14><10""" e What would be the effect. if any, on the amount of ester
present if all of the water were rerTIOYed from the flask
a Write the expression for the equilibrium comtant, I(., and the flask kept for a further week at 25"C1
for this reaction. Give the units. Explain your answer. [2]
b Calculate the value of K, at each of the temperatures /Cambridge International AS &AL~ Chemistry 9701,
giYl:'fl. Paper 22 01 June201 IJ
/Cambridge International AS & A Level Chemimy 9701, 3 Ammonia is one of our most important chemicals, produced
Paper 2 Q3 c June 2008] in enormous quantities because of its role in the production
2 Ethanoicaddcanbereactedwithakoholstolormesters, offertili~.
an equilibrium mixture being formed Much of this ammonia is manufactured from nitrogen and
hydrogen gases ~ng the Haber process. The equilibrium is
CH3C01H + ROH 'F CHJC01R + Hi() shmmbelow.
Thereactionisusuallyca!'riedoutinthepresenceofanacid Nz(g) + 3Hz(g) ;= 2NH1(Q) t.H - -92 k.l mor 1
ra<a""
a Writeanexpressionfortheequilibriumconstant,K,,for a i WriteanexpressionforK, forthisequilibrium. (1)
thisreaction,clearlystatingtheunits. (2] ii OeducetheunitsofK,forthisequilibrium. (1)
In an experiment to determine K,. a student placed together b A research chemist was investigating methods to improve
inaconicalflasl::0.10molofethanoicacid,0.10molof the synthesis of ammonia from nitrogen and hydrogen at
an alcohol ROH, and O.OOSmol of hydrogen chloride soo c
0
[41
ra<a"" The chemist mixed together nJtrogen and hydrogen

The flask was sealed and keptat25"C for seven days. and pressurised the gasessothattheirtotalgas
After this time, the student titrated all of the contents of volumewas6.0dml.
the flask with 2.00rnoldm-1 NaOH using phenolphthalein The mixture was alcr.Yed to reach equilibrium at constant
ind~tor. temperature cWld without changing the total gas YOlume.
At the end-point, 22 .s011 1 of NaOH had been used.
184
Equilibria I
Theequilibriummixturecontained7.2molN 1 and i ExplainintermsofleChatelier'sPrinciplewhythe
12.0molHi equilibrium yield of ammonia increased (2)
At500C,thenumericalvalueofK,forthis ii Explain in terms of K, why the equilibrium yield of
equilibriumis8.00x10- 1. ammonia increased. (3)
Calculate the amount, in mol, of ammonia present in the [OCR Chemistry A Unit F325 Q5 (part)June 2010]
equilibriummixtureat500C. [4)
c Theresearchchemistdoubledthepressureofthe
equilibriummixturewhilstkeepingallotherconditions
the s.ame. A5 expected the equilibrium yield of ammonia
increased.
185
AS Level
Inorganic chem istry
1 Q Periodicity
A modern form of the Periodic
Tableisstudiedinthistopic. We Learning outcomes
shallseehowitcanbeusedto F the thirdperiod{sodiumtoargon),bytheeodofthistopjcyoushouldbeableto
showpatternsinthepropertiesof 3.3b) understand, in simple terms, the rnrxept of electronegatMty ,md apply it to exp ain
someofthechemica/elementsit thebehavioorol0Jlideswithwater(part,seealsolopic3)
contains. The changes in properties 9.1a) desc1ibequal itatively(andindiu1tetheperiodicityin) thevariatioosinatomicriidius,
in crossing a period (from sodium ionicri!dius,meltingpointar.delectricalrnrnluctivityoltheelements
to argon) or in going down a group 9.1b) expjainqua litat ivelythevariationinatomicrad iusandicmicrad ius
(from magnesium to barium) are 9.1 c) inteqxetthevar;afoninmeltingpcintartdinejectrk.alconductivilyintemisofthe
related to the changes in the piesence ol 'iimple mciecular. giant mciecular or meta llic bonding in the ejements
e/ements'atomicstructures. Two 9.1d) explainthevariationinfirstionisationenergy
other common elements, nitrogen 9.1e) explainthestieogth,highmeltingpointandelectricalimulatingpropertiesof
andsu/fur,area/sostudied. ceramics in terms of their giant structure; to include magne'iium oxide, aluminium
oxideand'iilicondioxide
9.2a) describe the redclions, if any, of the ejements with oxygen (to give Na.iO. MgO,
Al10 3, P40 10, SO.,, S0i), chlorine (to give NaCl. MgCl1, Al1C'6, SiCl 4, PCl1) aml
water(NaandMgonly)
9.2b) stateandexpla inthevariationinoxidationnumberoltheoxides{sodiumtosulfur
only)andch!orides{sodiumtophosphorusonly)intermsoftheirva~shellelectrons
9.2c) describetheredclionsof theoxkleswithwater
9.2d) descnbeandexp!a intheiKkllbasebeha'<iourofoxidesandhydroxides,including.
whererejevant,amphotericbeha'<iourinreactionwithsodiu mhydroxideandacids
9.2e) describearidexplainthereactionsofthechlorideswit hwater
9.2f) interpretthevariationsandtrendsin 9.2b), cl,d) and e) intermsof bonding
andelectronegativity
9.2g) wggest the types of chemical bonding present in chlorides and oxides from
oble!Vationsoftheirchemicalartdphysical properties
9.3a) predktthecharacteristicpropertiesof anejementinag ivengroupbyu'iing
knowledge of chemical periodicity
9.3b) deduce the nature, poosiblepositionin thePeriodic Tabk>, and identity of unknown
elementsfromg iveninfoonationaboutphysic.alandchemical propeflies.
FGroup2(milgne'iiumtobarium),youshouldbeabk>to
10.1a) describetheredclionsol theelemelltswithoxygen,waterandd iluteadds
10.1b) describethebeha'<iouroftheoxkles,hydroxidesandcarbonateswithwaterand
withdiluteilCids
10.1 c) describethethermaldecompo'iitionoft henitratesandcarbonates
10.1d) interpret, and milkepredictionsfrom, thetrendsinphysicalandchemicalproperties
oftheek>rnentsandtheir compounds
10.1 e) statethe variationinthe~ubHitiesolthehydroxidesandS1.Jlfates
10.2a) describeandexplain theuseofcakiumhydroxideandcalciumcarbonate
(powderedlimestooe}inagriculture
Fnitrogenandsutlur,youshouldbeableto
13.1a) explaintheli1Ckofredctivityolnitrogen
13.1 b) describe and explain the basicity of ammonia, the structure of the ammonium ion
anditsfOfmiltionbyaniKid-basereaction, and t hed isplacementofammonia
from its salts
186
10 Periodicify l
13.1c) state the iridu5lrial importarice of ammonia ar.d nitrogeo compounds derived
fromammooiil
13.1d) stateandexp!aintheerwironmentalrnnsequencesoftheuncontrolleduseol
nitrate fertilisers
13. 1e) state and explain the natural and man-made ocrnm!flces of oxide-; of nitrogen
and their catalytic removal from t he exhaust gases of iritemal combustion
er.gmes
13.1f) expjainwhyatmosphericoxidesofnitrogeoarepollutants,includingtheir
ca ta lyticroleintheoxidationofatmosphericsulfurdioxide(seeal'iOTopjc21)
13.2a) describe the formatioo of atmospheric sutfur dioxide from the combustion of
sulfur-rnntam inatedfossill~s
13.2b) statetheroleofsulfurdioxkleinthelorrnationofacidrainanddesaibethe
mainenvironmentalconsequrocesoli!Cidrain
~ 10.1 Background
150 years ago, when about SO elements had been discovered, anernpts were made
to find patterns in their properties. The following three attempts were particularly
imponant.
In 1829, the German Johann Dobereiner JX}inted out that some similar elements
forrnedgroupsofthree(whichhecalled "triads"). Thentiddleelementshov.ed
propeniesintennediateberneenthoseoftheothert,vo. Examples of these triads
includedlithium.sodiumandpotassium,cakium,strontiumandbarium:and
chlorine, bromine and iodine.
In 1864, the Englishman John Newlands shov.ed that if the elements are arranged
in order of their relative a!omic masses. many show propenies similar to the
element that is eigh! places further on . He called this the Law of Octaves, after the
eighc white nO!es o n a piano which make up an octave. Examples include sodium
and potassium: magnesium and calcium; boron and aluminium, oxygen and sulfur,
nitrogen and phosphorus: and fluorine and chlorine.
lhe firs! periodic table was independently produced by the German LO!har Meyer
and by the Russian Dmitri Mendeleev in 1870. LO!har Meyer was the firs! to put his
ideas down on paper, but publicatiO!l of his rnanuscrip! v:as delayed for rno years.
andsoMendelccvisof!engivcn sole credit.
Two features of Mendcleev's classification were particularly significant.
Flgure10.1 OmilriMemleleev(1834-190n He left gaps in his table for elements which were unknown at thac time. and
rnllectedlnforrnation.lbout!heek>mentsand hesucces.sfullypredicredtheexistenceoftheelementsscandium,galliumand
11rotethemdownonG1rds.whk:tihearranged germanium, all of which we"' discovered a few years later. He used Sanskrit
accordirigtorl'latrl'eatomicm~ssandtothe prefixestoidentifyhis"missingelements': forexample,hisnameforgermanium
propertiesoftheelements.AloogW1thloth.ir was eka-silicon. meaning one place below silicon" in his table.
Meyer,heformedthePetio:!kTableweuse
today. He reversed the order of cobalt and nickel. and of tellurium and iodine, from the
order shown by their r<,lative a!ornic masses. Subsequent ,vork showed that this
reversal was correct. He had put the elements in the order of their pro(on numbers:
the facr that their relative atomic masses were in the wrong order was due to the
proportionsofisompesintheelements(seesection2.4).
10.2 A modern form of the Periodic Table

Groups and periods
Amodemforrnoftheperiodictableisshownin Figu"' 10.2.
Elements placed under one another in a column are in the same group and show
rnanysimilaritiesintheirphysical and chemical properties . Elements are also arranged
187
INORGANIC CHEMISTRY
pblock
1 1 2 Group 13 14 15 16 17 He
B C N O F Ne
Figure 10.2 A modem form of the Periodic in rows or pl'rlods across the cable . The elements in a period have differem physical
Table.Theell.'mentsshownlnreda regood and chemical propenies. bu t trends become apparent in these properties as we move
rnnduc:torsofelectncity,aridtheoneo;s.hown
inbluearepoorconductor,;_Toepinksh.lding
across a period .
im!kate1thattheprincipalformofthel'lement
isa~kond!ldor. ruonlyafewatomsofthe The s, p, d and f blocks
elemen ts at theendofthePeriodk Tableh.ive The first 1,vo groups form the s block (Groups I and 2). These have the outer
beenmade,thPSehavebeenleftwh ite electronic configurations ns 1 and ns', respectively, where" is the number of the
shell . The last six groups form the p block (Groups 13 to 18). in which the p
sub-shell is being progres.sively filled . These elements have the outer electronic
configumtionsns'np 1 tons'np6.
In belween the sand p blocks is the d block (Groups 3-12). in which the d
sub-shellis beingprogressivelyfilled. Ourstudy o fthedblockislargelyrestricted
to the elements scandium to zinc. and these elements have the ou ter electronic
configurations4s'3d'to4s1 3d 10, asweshallseeinTopic24.
About a quaner of the known elements belong to the fblock . The first row. the
4f. includes all the elements from cerium (Ce) to lutetium (Lu) inclusive . In this block.
thefsub-shellin thefounh principal s hell is being progressively filled. In the past,
these elements were called the rare eanhs'. This was a misnon,er. as their abundance
in the Eanh's crust is fairly large - for some it is co mparable to that of lead . However,
itistruethattheyaremosdyquitethinlyspread,sominingthemisquiteexpensive.
They are now called the lanthanolds , as their propenies are similar to thO!'ie of the
element lanthanum (La) that precedes them in the Periodic Table. Although they are
nctpanicularlyrare.thelanthanoidsaredifficulttopurifyfromoneanctherbecause
their chemical propenies are nearly identical. The elements of the second row of the
f block, the Sf, are called the a c tinoids. All the actinoids are radioactive, and most
havembemadeanificially.
10.3 Periodic trends in the elements of

the third period (sodium to argon)
In this section we shall look at the trends in the properties of the elements and their
compounds in the third period of the Periodic Table .
Appearance
The elements on the lefi of the Periodic Table have low values of ionisation energy
and electrone.gativity. and so they show the propenies associated with metallic
bonding (see section 4 .11), for example. they are shiny and conduct electricity . ln
the middle of the Periodic Table. elements with higher values of ionisation energy
and electrone.gativity are semiconductors: they have a dull shine to them and are
poor conductors of electricity (typically 10-" times that of a metal) . The elements
on the rig ht of the Periodic Table, with the highest values of ionisation energy and
electronegativity, are dull in appearance and are such poor conductors that they are
used as electrical insulators (their conductivities are only about 10- >s times that of
a metal) .
188
10 Periodicify l
.,
Meltlngpolnu c
Flrstlonlsatlonenergy/kJ mol-1
Electronegatlvlty
Electrkal conductlvlty/ Scrrr' 2.1x10' 2.3 x10' 3.8x10' 2.Sxlo-" l.Ox10- 11 5.0x10-
(0.190)
Table 10.1 Somephyskalpropertfe5ofthe

elements intheth irdpeliod
lnteratomic and interionic radii
The term 'atomic radius' does not mean the same thing for every element. Although
wecanfoirlyeasilymeasurethedistancebetweencwoadjacentnucleiinan
element (see Figure 10.3), if we are to use those disrnnces to compare one elemem
with anOlher. we must be aware that the interatomic bonding mig ht differ in the
two elements. For =ample. tables of interatomic radii include th,..,.,. values for
sodium: its covalent radius is 0.1)4nm; its metallic radius is 0.186nm. and its van
der Waals ' radius is 0. 230 nm. The only radius listed for a rgon is its van der Waals'
radius (0.190 nm), since it does 1101 form compounds . If we are to compare the
sizes of the atoms in a sensible way. we need to compare radii of the same type.
Comparing the van der Waals" radii of the two elements shows that the sodium
atom (0.230nm) is larger than the argon atom (0.190nm), as we might expect. since
the nuclear attraction for the outer electron shell increases with profon number
across the group.
Flgure10.3 Theatomicradiu1i1halftlle
intemucle.ir distance
011 the left - meullk radius 011 the right - <ovalent radius ::~~ eori~!I~ radiU<
In crossing the third period of the Periodic Table. the pn:xon number increases from
l l to 18. This means that the 3s and 3p outer electrons become more firmly attracted
to the nucleus andasaresulttheirdisrnnceawayfromthenucleusbecomes less.
This is the reason why the atomic radii decrease from sodium to chlorine (see Figure
10.4). As memioned above, the somewhat larger value of 0.19()nm listed for argon in
Table 10.1 is the van der Waals ' radius. which is half the distance between the two
Sodium. magnesium and aluminium are metals and form Na\ Mg"" and AI.J.o. ions.
These ions all have the electronic structure ls 2 2s1 2p6. As the pro(on number increases
from 11 with sodium to 13 with aluminium. the attraction for the ou ter electrons
increases and they become drn,vn in closer to the nucleus. This means that the ionic
radii get smaller (Na 0.095nm. Mg' O.o6S nm. Al.J.o. O.OSOnm)
Melting points
The melting poim of an elemem that has a giam s tructure is high because many
imeratomic bonds must be broken for melting to take place . The atomic radii
become smaller from sodium to silicon and so the bonding becomes stronger
and the melting poims become higher. as the bonding electrons are closer to the
adjacemnuclei.
189
INORGANIC CHEMISTRY
Figure 10.4 Atamtcradiu1a!ldprntoo

number
"'
proton number
Phosphorus , sulfur and chlorine all form small covalent molecules, P4. Si. and
Cl, respectively . When these sub.stances rndt. it is only neces.sary to break weak
intermolecular bonds and nOI: strong interatornic attractions. The melting points
decreaseintheordersulfur>phosphorus>chlorine(,..,.,Figure 10.5).the
intermolecular bonds becoming weaker as the molecules become smaller.
The melting point of argon is low. as the attraction betw=n the argon morns is
very small .
proton number
F1gure10.5 Vori.itionofmeltingpolntwith
protonnumtie, Electrical conductivity
Sodium , magnesium and aluminium are metals. They have delocalised electrons that
arefreetomoveinthebniceofrntions (see section 4. ll). Siliconisaserniconductor.
The O!her elements in the third pericxl form covalent bonds with no free electrons,
and so are insubtors w ith 3[moS1 no electrical c onductivity.
190
10 Periodicify l
Ionisation energies
The first ionisation energies genera lly increase from sodium to 3rgon as the
proton number increas.,.s. In two insrnnces, this increase does not take pbce:
between magnesium and aluminium. and between phosphorus and sulfur (see
Figure!0.6).
Flgure10.6Variationoffirstioni'iati,m
l'!lergywithprotonnumber
proton numbe r
Worked example
1 Thetwoelementss.iliconand Suggest why:
gemi aniumhavehighermeltingpoints the ionisatioo energy of aluminium is le'iS than that of magnes.ium
thanthel100ghbours{seeFigure 10.S) b theionisationenl'fgyofsulfuris~sthanthat of phosphorus.
a Suggestthebond ingandstructure in
germarnum Answer
b Wouklyouexpectgermaniumtobe a Thisisbecausetheouterelectroninalum iniumisin the3porbital,ar.dsofurther from
acooductOf,asemicooductororan thenudeusar.dlessstrong!yhejdthantheouterejectroninmagnesium,whichisinthe
insulat or? 31orbital
2 Sogge5t'Mlythemeltingpointof b This is because the ejectron that is being n>moved from su lfur comes from a
~enium(protonnumber:04)isMghef doubly-occupiedorbital,inwhich itsuffersinter-electronrepulsionfromtheotherelectron
thanthatolarsenk(protoonumber33) occupying that orbital.
The reactions of the elements with oxygen,

chlorine and water
Apan from chlorine itself and argon , all the elements in the third period react directly
and exodiermically with oxygen and with chlorine, but they often need .s1rong initi.tl
heating to overcome the energy barrier !o reaction.
191
INORGANIC CHEMISTRY
withoxygC'n
2Na0) + to 1(g) ----+ Na 10(1) Na(l) + tclz(g) ----+ NaC!(s)

M g(s) + to/g) ----t MgO(s) M g{s) + C11(g) ----+ M gC1 1(s)
2Al(s) + tpi{&l ----+ Alp 1{s) 2A!(,) + 3Cl2's) ----t A11C~(s)

Si(s) + 0 1(g} ----t Si0 2(s) Si(s) + 2Cl 1(g) ----+ SiCl_,(1)
limi t e d = limiwlchlo,iru,
P4(1) + 30 2(g) _________,,. P.,0 6(s) Pi1) + 6Cl1(g) ~ 4PCI/I)
P 4(l) + 50 2(g} ----+ P 40 1o{s) P_,(l) + 10Cl1(g) ----t 4PCl5(s)
S(l) + 0 1(g) ----t SO,(g)
so,(g) + fo 2( g ) ~ s o1 (g)
The oxidation numbers of the elements in their oxides and chlorides are equal to
the numbers of electrons in the u = 3 shell. For the ionic compounds, Na,O, NaCl.
MgO , MgCl, and Al,01, the metals have formed Na~, Mg,. and Al l+ ions by loss of all
the outer electrons. The O!her oxides and chlorides ar<, covalent. In these covalent
compounds, the oxidation number of the element can be found by g iving chlorine an
oxidation number of - 1 and oxygen an oxidation number of - 2. With the excep1ions
of so, and PCl;, the oxidation number of the elemem is the same as the number
ofelectronsinitsoutershell. Thisisbecausealloftheelectronsareusedtomake
bonds. In so,, two of the electrons of the sulfur atom form a Jone pair. and only four
are used in bonding to oxygen. This then gives sulfur an oxidation number of +4.
Electronegmivity increases across the period (see Table 10.1); the difference in
electronegativity between the Pericxl 3 element and oxygen or chlorine is high
31the left-hand side and gets less and lessgoin gacrossthepericxl. ForNa,O.
NaCl. MgO. ,\lgCl 2 and Al,0 1. the electronegativity difference is high and so the
salts are ionic; they have high melting points and in the molten srnte they conduct
electricity. TheelectronegmivitydifferencesbetweenAl. Si. Pand Sand oxygen.
and between Si. P and S and chlorine. are low. which suggests covalent bonds. The
low melting points of the oxides and chlorides suggest small cov:ilent molecules-
o, is a gas. S0 3 is a low melting point solid and P~0 , 0 sublimes when he:ited
l2CJ,;readily sublimes. SiC[. is a liquid and PC[s decomposes on melting to give
PCJ 3 .whichisaliquid.
Only sodium and magnesium react with water. Sodium re:icts with water in the
cold. but magnesium needs to be red hOI: to react with steam:
Na{l) + ttp(l) ---+ NaOH{aq) + {H 1{g)
M g(s) + H 20(s) ---+ MgO(s) + H 2{g)
Magnesium reacts very slowly with cold w:iter: it mkes several hours to collect a test
tube of hydrogen .
The reactions of the oxides with water

When an oxide of an element M reacts with water. an M--0--H bond is formed . This
bond may ionise in 1,vo ways :
In the first case the M-0--H lxmd is behaving as a soun,e of basic hydroxide ion; in
the second case, it is behaving as a pro!on donor - an add. If the element M has a low
electronegativity (< l.5).thefirstreactiontakesplaceandthehydroxideisOOsic. lfM
hasahighelectronegativity(>2.1).1hesecondreactiont:1kesplaceandthehydroxide
behavesasanacid. lfMhasanelectronegativitybetweenl.5and2. l.lxxhre:ictions
are possible and the hydrox:ideisamphOl:eric.
192
10 Periodicify l
Sodium oxide (electronegativity 0.7) easily dis,ol.ves in water to give an alblioe solution:
Magnesium oxide (elearonegativity 1.2) d issolves slightly in water to give a solution

that is just alkaline:
Aluminiumoxidedoesnotdis.solveinwater.butitshydroxide(electronegativity 1.5)
isarnphOl:eric: itdi.s,;olvesinbothacidsandalkalis.
Al(OH)h) + JH\aq)----+ Al{aq) + 3Hz0(1)

Al(OH},{s) + O W (aq) ----+ Al(OH)4-{aq)
SiO, is a weakly acidic oxide. It is the srnning material for g lasses and ceramics
because, when molten, it reacts with bases such as sodium carbonate and rnlcium
P40, 0 and S02 (elearonegativities 2.1 and 2.5) react with water !O fom, the we:ik
adds, HiPO and H:,50 3, while S03 forms the strong acid. H,S0 4:
P.Ouh) + 6Hz0(1) ----+ 4HiPOiaq)

SOz(g) + HzOO)----+ H 1S0 3(aq)
SOh) + HzO(I)----+ H1S04(aq)
10.4 Group 2
Properties of the elements and general trends
The elements of Group 2 show typical memllk behaviour. They fonn compounds
containing M'" ions. and the reactivity of the mernls increases down the g roup.
Table 10.2 Somephyslcalpropertfl'Softhe Mg

elements in Group 2
Meltlngpolnu c
Bollln gpolnu c
Fl rst lonlsatlone nergy/ kJmol- 1
Secondl onl s;tlon energy/ kJmo t-- 1
lon lc rad lu sof M' 1on/nm
On going from calcium 10 barium. the first and second ionisation energies decrease.
This is because the outer electrons become funher away from the nucleus and are
Jess firmly mcracted to it . Thus the reactivity of the mernls increases from calcium to
barium. as shown by their reactions with oxygen and water.
Reactions with oxygen

\Vhen heated. the Group 2 metals catch fire and form while oxides. For e,mmple
magnesiumgives,\lgO:
2Mg0) + 0 1(g} ----t 2MgO(s)
Of all the metals, magnesium cacches fire the most easily as it has the lowe.sl
melting point. It bums with a brilliant white light . Calcium bums with 3 brick-red
fbme, strontium bums with a crimson fbme and barium wi th a gr=n !lame (see
section 19.6).
Reactions with water

As mentioned 3bove, magnesium reacts very slowly with w:iter in the cold to give the
oxide3ndhydrogen. lnste3m at red he-:it.the reaction is rapid :
Mg(s) + Hp(g) ---t MgO(,) + Hh)

193
INORGANIC CHEMISTRY
It does not give the hydroxide, as magnesium o xide is almost insoluble in water.
Because their oxides are soluble in water, calcium. strontium and barium all g ive the
hydroxide and hydrogen . Calcium reacts slowly . .slrofltium more quickly and barium
even more quickly:
Ba{s) + 2H 10(1)----+ Ba{OH)z + H,(g)

Magnesium oxide is only slig htly soluble in water. This means that when it is shaken
with water. the pH of the resulting solution is just above 7 . However. calcium oxide.
Writeabalancedequationloreachofthe CaO, strontium oxide, S!O, and barium oxide , Ba0, are all readily soluble in water.
fol!owing1&1ctioris Whentheyareshakenwithwater.theydissolveandthesolutionhasahighpH(>l3).
1 cakium + oxygen For example :
2 strontium + water
CaO(s) + ttp(l)----+ Ca'(aq) + 20H-(aq)
Thermal decomposition of the carbonates

and nitrates
On heating, the Group 2 carbonates decompose to give the oxide and carbon
dioxide. For =ample, calcium carbonate decomposes as follows:
On going down the group, the carbonates become mo..,. stable to heat: magnesium
carbonate decom!X>S"s at S00C, and so can be decomposed in the heat of a Bunsen
flame, but barium carbonate needs a temperature of over 1000C before much caibon
dioxide is produced .
The Group 2 nitrntes also decompose on heating, to give the oxide, nitrogen
dioxide (a brown gas) and oxygen. For example, magnesium nitrnte decomposes
2Mg{N01)z(s)---t 2MgO{s) + 4N0 1(g) + 0 2(g)
Like the carbonates, a higher temperature is n=ded to decompose the nitrates of the
metals at the bouom of the group compared to those at the top, although all can be
decomposedusingaBunsenbumer.
Solubility of sulfates and hydroxides

Thesolubilityofthesulfatesdecreasesasthepro1on numberincre-:,ses,that is they
are in the order MgS04 > CaS0 4 > SrS0 4 > BaS04. The solubility of the hydroxides
changes in the opposite direction, that is Mg(OH 2) < Ca(OH,) < S!(OH,) < Ba(OH,).
Uses of Group 2 compounds

Economically, the most imponant compound of a Group 2 element is calcium
carbonate. Largequantitiesofitarefound intheformoflimestone, a soft rock which
is attractive and is easily carved and decorated . The rock is widely used as a building
material althoug h it is readily attacked by adds and dis.solves in polluted air, which
oftencomansn t cadd:
CaCO,{s) + 2HNOhq)---+ Ca(NOV1(aq) + H,O{l)
As mentioned above , heating calcium carbonate. in the form of limestone or

chalk. breaks it down into calcium oxide (called quicklime) and carbon dioxide,
CaCO,{s)---+ CaO{,) + C0 1(g)
On standing in moist air, the quicklime takes up water and is convened into calcium
hydroxide(slakedlime):
CaO(s) + H 10(1) ---+ Ca(OHh(s)
194
10 Periodicify l
Slaked lime is the main constituent of simple monar. which has been used since
ancient times to bind .stones and bricks iogether in buildings. On standing, calcium
hydroxide slowly absorbs caibon dioxide from !he air and is convened into calcium
caibonate. As calcium carbonate cakes up a larger volume than calcium hydroxide,
the resulting expansion binds the stones and brickstogeiher.
Ca{OH) 1(s) + C0 1(g}----+ CaCOis) + H,00)
Write an equation for This reaction forms the basis for the Hrnewater test for carbon dioxide (see
section 19.5).
iithel&Ktionbetweeflcalcium The various forms of lime are used lo neutralise acidic soils . The addition of slaked
u1rbonateandanacidinscil
lime rapidly neutralises the soil, but if too much is added the soil may become
b thereactionbetweencarbondioxide
alkaline. Calcium caibon.ate, in the form of powdered limestone or chalk, acts more
andbariumhydroxidesolutkln
slowly: even an excess will leave the soil approximately neutral.
10.5 Nitrogen
Unreactivity
Nitrogen makes up 78)1, by volume of diy air. The element is very unreactive, for two
reasons . Firstly. the N, .N bond is veiy strong (945kJ mol- 1) and so its reactions with
other elements are usually endothermic. For example , with oxygen:
i'IH = + 181 kJ moi-1
Secondly, the strong N- N bond means that reactions involving nitrogen have a veiy bigh
acti,dtion energy, and as a result will be very .slo,,, even if they are exothennk: this is the
reason why the Haber process to make ammonia requires such extreme conditions.
Ammonia
Nitrogen combines witb hydrogen to make ammonia, NH 3:
N1(g) + 3Hz(g}----+ 2NH1(g) i'IH =- 921.:Jmoi-1
The ammonia molecule is a trigonal pyramid in shape. There are four pairs of
electrons around the nitrogen atom - three bonding pairs and one Jone pair. The
presence of a lone pair makes the H-N-H angle slightly less than the tetrahedral
angleof109.s''; theactualvalueisl07(,..,.,.figure10.7).
Flgure10.7 lonepair- txmdirigpairrepulsi:J11

maKe,;thebo!ldar,gle.iammonia 107
The Jone pair easily combines with a pro{on, making ammonia a weak base. lhe
resulting ammonium ion is exactly tetrahedral. It can be thought of as being formed
either by the Jone pair o f electrons from the nitrogen being donated to the pro{on
(see Figure 10.8a), or by an W ion (isoelectronic with ca rbon) forming four bonds
withhydrogenatoms (seeFigurelO.Sb).
Flgure10.8 The
~therberegarded;r;
beingfonned a by !
thed:Jnatbnofapair
olek>ctrornfromthe
nrtrogentoaprotoo
N !,r--..._ Hj: Cl
: -~ "' N ;, H
rn b bycombining
fourhy{Jrogt>!latom5
with an Wion
195
INORGANIC CHEMISTRY
The ammonium ion reacts with strong bases such as NaOH to give ammonia, an
alkalinegasthatturnsmoi.stredlitmuspaperblue.
NH/(s) + OW(aq) ----t NHh) + H200)
The Haber process

Even though the synthesis of ammonia is exOlherrnic, it is a very slow reaction. There
ar<,threew ys nwh"chthra!ecanbe"ncreased: an ncreasenp, ,sure.an ncrease
intemperarureandtheuseofacatalyst.Allthreea..,usedintheHaberprocess. A
typical plam uses a pressure of 250 atmospheres , a temperature of 400C and an iron
camlyst. promOled with tmce.s of <>1her metals ( sec, section 8.6). A lower temperature
would increase the pera,ntage of ammonia in the equilibrium position ( remember. the
reaaion is exOlhermic) but in practice a low cempemture would make the reaction too
slow to be economic. This is why a compromise temperature of 400C is used . At this
temperature. a yield of IS% is obrnioed in a rebtively short time: the ammonia is then
removed and tbe gases continuously recycled to produce further conversion . Although
a higher pressure would produce a g reater yield of ammonia. and at a faster rate. this
high pressure is =pensive to produce and maintain (extra -thick pipes and reactor
,vallswouldbeoeeded).aod makeforalesssafeprocess
The nitrogen is obtained from the air and the hydrogen from the reaction between
methane and water over a metal catalyst (usually nickel) . The overall reactions may
be approximately represented by the following .-quations:
CH-,{g) + 2Hp(g) ---t C0 2{g) + 4Hi{g)

tfair isfour-fifthsnitrogeoandor.e-fifth
oxygeo,balancethelollowirigcombined 20 2{g) (plus N,(g)) + CH 4{g) ---+ C0 1(g) + 2Hp(g) (phu N 1{g))
equatiootos.howtheproductionofNi
Th.- first reaction is endotbennic: the second reaction is =othermk. The beat e-volved
andHiina1:3rafo:
during the second ,.,.:,ction can be us.-d to beat th.- catalyst in the first reactiOfl. The two
Oi + 4Ni + . CH4 + ... H10---->
C01 + ... H1 + ... N1 reacrionsareadjustt"dsothattheresultioggas (afiertbecarbondioxid.-hasb.-en
retnO\....d) contains approximately on.- volume of nitrogen to thcee volumes of hydrog.-o .
Uses of ammonia
Ammonia fonns the basis of nitroge-n f.-rtilisers and of explosiv.-s .
ln acidic soils , ammonia is inj<"ctt"d directly into th.- ground, in Ol:her soils. it is u...-d
nth.- f cm of amnxmum sulf te , ammon um n "trate or urea .
Ammonia can be catalytically oxidi...-d by air to give NO and NO,. which are
dissok.-d in Wat<"r to g ive nitric add. HN0 3.
=plosin,s. such as TNT. dynamic.- and con:lit<" .
10.6 Sulfuric acid and sulfur dioxide

Th.- principal us.- of sulfur dioxide is to mak.- sulfuric add . This process has three
stages: th.-firstisbumingsulfurinairat 1000Ctogiv.-sulfurdioxide.th.-s.-condis
th.- oxidation of sulfur dioxide to sulfur trioxid.- , in a r.-action known as th.- Con tact
prot't'ss. and th.- third is dissohing th.- sulfur trioxide in ,vm.-r co give sulfuric add:
S(s) + Oz(g) ---tS0 1(g} Aff =- 308kJmol- 1
so,{g) + fo,(g) ~ S0 1(g) Aff =- 96kJmor 1
S01{g) + H 10(1)---tH 1S0 4(1) Aff =- 130kJmor1
The s.-cond Mage is rev.-rsible and relatively slow. To speed up the reaction. a
catalyst of vaoadium(V) o xide. V,Os, is us.-d and the equilibrium is d isplaced to
196
10 Periodicify l
the righc by using about three times more air than is needed by the equation . Le
Chatelier's Principle also indicates that the yield would be improved by increasing
the pres.sure and using a low cemperature . In practice , a temperature of at JeaSI
400C muse be used, as the catalyst becomes ineffective at temperatures lower
than this, The pressure is only slightly above atmospheric bemuse the yield is
already high. and the =tra expense of high pres sure would not be economically
wonhwhile. The s ulfur trioxide is not dissolved in water d irectly, because this
reaaion is so exothermic that che water would evaporate and a difficuh -to-.::ondense
mist of concentrated sulfuric add would be formed. In practice, the sulfur trioxide
is dissolved in concentrated sulfuric 3dd. and then water is 3dded with cooling, to
keeptheconcentrationconsl3nt:
e paintsandpigments
e deteigentsandsoaps
e dyestuffs .
Acid rain
Sources of sulfur d ioxide and nitrogen oxides
Sulfurdioxideisproduccd wheneversulfu r--conrniningcornpounds are burnt.
Three--quanersofit isproducednaturally(seeT3ble 10.Jand Figure 10.9).
"&Ible 10.3 Amounts of s.utfur doxide produced glooaly from Offerent soo rces. Dimethyl su tlide is
prcxlucedfromorgaoi1ms in th esea.andi1readllyoxidisedto1uffur dioxide
M; ssof sulfurdloxldeprod uced/ mllllontonn esperye; r
Flgure10.9 Aswellao;the phr;kal

de1tructKl!lc.au1ed by a volG1niceruption,
di methy!1u!lide
hugeamounts of suttur dioxideare ats o p<mer1t.itiom
givenoutinto theatmosphere
Nitrogen combines with oxygen only at high temperatures or in the presence of

sparks, suchaslightnin g(Fi gu re 10.10). lnitiallynitrogenmonoxideisformed.but
this reacts slowly with oxygen to give nitrogen dioxide. The mixture of n itrogen
oxides is often written as NOx to indicate its variable composition . Most of this is
producedbyhumanactivity (seeTable\0.4).
"&Ible 10.4 Amounts of NOx pmduced gklbalty from different 10U rce1
MassofNOxproduced/mllllontonnesperyear
p<me11tatiom
industry
Pollution and acid ra in

The presence of dry sulfur dioxide and nitrogen dioxide gases in the atmosphere
is harmful. The principal adverse effects 3re respiratory problems (pankularly
inbabies.theelderlyandbronchitissufferers)anddamagetotreesandOl:her
vegetation . Nitrogen dioxide also carnlyses the fo rmation of ozone , which is a
dangerous pollutant at ground level.
Flgure10.10 lighlning prOYide5 the In moist air. sulfur dioxide is readily oxidised to g ive the strong acid sulfuric add :
energyto tumnitrogen a!ldoxygen inthe
atmosphere to nitroge n oxides
197
INORGANIC CHEMISTRY
Nitrogen dioxide dissolves in water IO give a mixture of nitrous and nitric adds
Nitric and sulforic acids are strongly acidic. When present in rainwater they
produce acid rain. This is rainfall with a pH lower than 5. Nitrogen dioxide may
exacerbate add-rain formmion from sulfur dioxide by carnlysing its oxidation to
sulfurtrioxide:
SOz(g) + NOz{g) ----t S03'g) + NO(g)
NO(g) + toz<&) ----t NOc(g}

Acidraincausesthefollowingproblems.
ll causes aluminium ions in the soil to dis.solve. A high concentration of these
ions is poisonous to most forms of aqumk life, in panicular fish. However,
algaeflourishundertheseconditions, pankularlyifthewateralsocontains
highconcentrationsofphosphateand nitrate ions as a resuhofexcessiveuse
of fenilisers . When the algae die, their decomposition uses up 3lJ the oxygen in
the 'l\':lter, so th.u it rnn no longer suppon 3ny form of life . The W3ter is said to
h3ve undergone c mro1lhirn Ho n.
The stonework of buildings is 3fi3eked by the acids (see Figure 10.11) . Much
renovation work h3s been necessary on old buildings recently bernuse of pollu-
tiOflgenemtedoveronlytheList hundredyeHs .
The h.trmful effects of add rain pollution ean be minimised by rnking the following
prec.tu tions:
ren10ving sulfur dioxide from the emissions of power sutions 3S they pass up the
chimneysrncks
removingsulfurfromdieselfueJ3nd petrol
using c3talytic conveners in c3rs to destroy NOx (see section 8 .6).
Rgure10.11 Theeffect1ofacidra in
ooa'itotue
198
10 Periodicify l
AlltheGroup2ek>mentsaremetals Elementswithwater:
Their atomk {meti!ll k) and iook radii incrt>ase down the group
Nil(l) + H10(1)---->NaOH(aq) + -! 1(g)
Their ionisatiooenergiesandelectrooegativitiesdecrNSedown
the group M(s) + 2H10(1) ----> t.1(0H}.,(s) + Hi(g) M = Mg,Ca,
Group 2 metals form M1 ions Sr,Ba(Bagives
Their nitrates ar.d c.aibmates become themia lly moro 51:able at 8a(OH)1(aq).)
thebottomofthegroup Cl1(aq) + H10(1).-HCKaq) + HCIO(aq)
Nitrogenisaveryunreactivegasandspecialcooditionsare
Oxidesandhydroxides1\ ilhwaterora,cid
iequired to make ammonia by the Haber process
Nitrogeocompour.dsarew,oelyusedasfertilisersandinthe Na10(s) + H10(1)---+2Na0H(aq)
mamifactureolexpjosives NaOH(aq) + W(aq)---->Na*laq)+H 10(1)
Sulfurisusedtomakesulluricacidbythe Contactp rocess
MO(!) + H10(1)---+ t-A(OHli(aq) M = Ca, Sr, Ba
Sulluricaddisusedinthemanufactureofawidevarfetyof
sub5tances M(OH).,(s) + 2H*(aq)----> M 1*laq) + H10(1) M = Mg, Ca,
e Theoxidesofnitrogenandsulfuru1use ac idra ln wtikhis Sr,Ba
harmfultol ife,,mdattacksbl.J ildings AKOHl:i(s) + 3H*jaq)---+Al'*\aq) + 3H10(1)
ICeyreactlonsyoushouldknow (Also A ~OHh(s) + 011(aq)---+ Al(OH) 4- (aq))
EJementswithoxyge<i P40 1o(s) + 6H10(0---+4H 3PO,i{iKJ)
2Na(l} + ,J01{g}---+Na 10(s)
S01(g) + H10{1)---->H1S0i{aq)
M(s} + i:Oi(Q)---->MO(s) M ~ Mg,Ca, Sr,Ba
SOi(g) + H10{1) ---->H1 S0iaq)
2Al(s) + 1~g)---->Al10 1(s)
CarbondioxidewithGroup2hydroxides
SKs) + 0 1(g) ---+ SiOi(s)
M(OH).,(aq) + Cai(g)---+ MCOi{s) + H10{I) M = Mg, Ca,
P.i(l) + SOi(g) ---+ P401o(s) Sr,Ba
S(l) + Oi{Q) S0i(g} MC03(s) + C01(g) + H10(1)---+ M(HC0 3}.,(aq) M c Mg, Ca
limited"4'!'1Yofoxygen (in hard water)
S{1) + 1feli(Q)~SO:i(g) HeatonGroup2carbonatesandnitrate1
400"C,V1D.;catalyst MC1Ji(s) ---->MO(s) + C01(g) M = Mg,Ca,Sr,

S01(g)+";:01(g) p,essure :> 1atm Ba(morestab~
down the group)
Elementswithchlorine
M(NOJh(s) ----> MO(s) + 2N01(g) + i:O.,(g) M = Mg, Ca, Sr,
Na(l) + tli(g)---+NaCKs) Ba(morestable
M(s) + Cl1(g)---->MCli(s) M = Mg, Ca, Sr, Ba (C)., rnukl be down the group)
replacedbyBt1 orI1.) e TheHaberprocess
2Al(s)+3Cli(g)---+Al 1Cl.(s)
Ni(g) + 3Hi(g)~2NHi(Q)
SKs) + 2Cl 1(g)---+SiCl 4 (1) H'ca!aly;I
P,i(I) + 10Cl1(g)---+4PCl1(s)
Acid ra in on buildings
CaCOih) + 2HNO_i(iKJ) ---+ Ca(N0 3li(aq) + C01(g) + H10(1)
199
INORGANIC CHEMISTRY
Examinati on practice questi ons

Pleaseseethedata5ectionoftheCDforanyA,valuesyou
may need.
Mg Al Si Cl Ar
1 This question refers to the elements shmvn in the portion of iii In thesequenceoffluoridesabove, the oxidation
the Periodic Table given above. number of the elements increases from NaF to SF6 and
a From this table, identify in eac h case one element that thenfallsatCIF5.
has the property described. Give the sy mbo l of the AttemptstomakeCIF7 havefailedbutIF 7 hasbeen
element in each case. prepared
i The element that has a molecule which contains Suggest anexplanationfortheexistenceofIF 7 andfor
exactly eight atoms. thenon-existenceofCIF 7. [4]
ii The element that forms the largest cation {Cambridge International AS & A Level Chemistry 9701,
iiiAnelementthatfloatsonwaterandreactswithit. Paper21 Q3June2010]
iv An element that reacts with water to give a solution 2 Radium was discovered in the ore pitchblende by Marie and
thatcanbehaveasanoxidisingagent. Pierre Curie in 1898,andthemetalwasfirsti50latedby
v An element whose nitrate gives a brown gas on them in 1910
thermal decomposition (SI The metal was obtained by first reacting the radium present
b i Give the formula of the oxide of the m05t in the pitchblende to form in50luble radium sulfate which
electronegative element was converted into aqueous radium bromide. This 50lution
ii Several of these elements form more than one acidic was then electrolysed using a mercury cathode and a
oxide.Give the formulae of two such oxides formed by carbon anode
the sa me element. (3] a Radium has chemical reactions that are typical of Group 2
The formulae and melting points of the fluorides of the metals and forms ionic compounds
elements in Period 3, Na to Cl, are given in the table. i What is the characteristic feature of the electronic
configurationsofa11Group2 metals?
For mula of ii Radium sulfate is extremely in50luble. from your
fl uoride Naf Mgf1 AIF1 Sif, CIF, knowledge of the simple s.alts of Group 2 metals,
suggestanotherveryinsolubleradiumsalt. [2]
b i Describe what you would see when magnesium reacts
m.p./K withcoldwater,andwithsteam
ii Writeanequationforthereactionwithsteam. [SI
c Radiumreactsvigorouslywhenaddedtowater.
i Suggest the formulae of two fluorides that could
i Writeanequation,withstatesymbols,forthis
possibly be ionic.
reaction.
ii WhatistheshapeoftheSf 6 molecule?
ii State two observations that could be made during
this reaction
200
10 Periodicify l
iii SuggesttheapproximatepHoftheresulting solution. b Magnesium chloride, MgCli, and silicon tetrachloride,

iv Willthereactionbemoreorlessvigorousthan SiCl 4,eiKhdissolveinorreactwithwater.
the reaction of barium with water? Explain your SuggesttheapproximatepHofthesolutionformedin
(6( eac h case.
{Cambridge lntemational AS & A Level Chemistry 9701, Explain, withtheaidofanequation, the difference
Paper 21 Q2 a, c & dNovember 2009] betweenthell'\!Ovalues. [SI
3 a Chlorine is very reactive and will form compounds by {Cambridge lnternatiofldl AS & A Level Chemistrv 9701,
direct combination with many elements. Paper 2 Q3 d & e November 2008]
De5Cribe what you would see when chlorine is passed
c,;erseporateheatedsamplesofsodiumandphosphorus.
In eac h cao;e write an equation for the reaction (4]
201
AS Level
Inorganic chemistry
11 Group 17
In this topic, we study the trends

in the properties of the Group 17
Learning outcomes
e/emenD, the halogens. They are Bytheeodofthistopicyoushouldbeableto
non-metalsandshowdecreasing 11 .1a) describethernloursandthetrendinvolatilityofchlorine, bromine and
reactivity with increasing proton iodine
number. 11 .1 b) interprettheYO!atilityoftheelementsintermsolvandefWaals'forces
112a) describ{>therelativereactivityoltheelementsasoxidisingagents(seealso
Topic23)
11 .2b)describeandexplaintherMctionsoftheelementswithh~rogen
11 .2c) desc:ribeandexpla in t herelativethermalstabHitiesolthehydrides,andinterpret
thl'serelativestabil itJ!.'Sinlef!Tlsolboodenergies
11 .3a) describ{>andexplainthe rNCtionsolhalideions\Mthaqueous'>ilveriom
lol!owedbyaqueousammonia,andwithcoocentratedsutluricadd
11 .4a) describeandinte1pret,intermsolchangesoloxidatioonumbef,there<Ktionol
chlorir.ewithcoid.andwithhot,aqueoos50diumhydroxide
11 .Sa) explaintheuseolchlorir.e inwaterpurilicatioo
11 .Sb) statetheindustrialimportanceandeovironmental'>ignificanceofthehalogens
andtheircompound1(e.g.lorblMChe1,PVC,halogenatedhydrocarboo1as
solveot1,refrigerant1andinaerosols)(seealsoTopic15)
11 .1 Physical properties of the elements

Table 11.1 Somephysic:olPfopertiesofthe Halogen
elements In Group 17. The import,mce of the
stonda1dek>ctrooepotl.'ntial1 isdi5russedln Meltlngpolnt!C
Topic23 BolllngpolntlC
Appearance at room yellow-green gas rl.'d-brnwn liquid nearly black solid
temperab.Jre
E(X- X)/kJ mo1-1
(H- X)/kJmoi 1
potentlalN
Melting points and boiling points

The halogens exist as di3tomk molecules. X, . The two atoms are bonded together
covalently in the solid. liquid and gaseous states. On melting. the van der Waals '
forces between the molecules are pani3Jly overcome. and on boiling they are almost
completely broken. On descending Group 17. the melting points and boiling points
increase. This is because the intermolecular forces become stronger as the number of
easilypolarisableelectronsrises(seesectionJ.17).
202
11 Group17 1
Colour
Each halogen absorbs radbtion in the near ultraviolet - visible region of the
spectrum. The JX)Sition of the absorption determines the colour of the halogen (see
Table ll .2).
Table 11.2 Cokl\lrsarld.ipproximate

Halogen Wavelength Colour of halogen
wavek>n gth1ofthe.bsorpbonballd1 in the
near ultraviolet;mdvi'iibk>regiomlorthe absorbed/nm
halogem yellow-grl'l'll
The colour of iodine in solutiOfl varies with the soln,m . In non -polar solvents (for
e,mmple, tetraehloromethane or hexane), it is the same colour as the gas. In more
JX>lar solvents (for =ample. etha no l). it is brown because the polar solvent affects
the wavelength 31 which maximum absorption rnkes place .
11.2 Some reactions of the elements

Displacement reactions
The oxidising .slrength of the halogens is in the order CJ, > Br, > 12 . A halogen that
is a more pmverl'ul oxidising agem displaces one that is less powerful. So chlorine
displaces bromine from solutions of bromide ions. for example :
a,(aq) + lBr-(aq) ---t 2Cr(aq) + Br1(aq)
Worked example
Statew!ietherOl"notareactionwouldtakepklceifsollllionsof thelollowingsubstances
were mixed
bromine + iodideioos
b iodine + chlorideiom
c chlorine + iodideiom
WriteanequahonforNd1reoctionthattakesp!ace
Answer
What obsefvations wou ld yoo make iiYes:Bri(aq) + 2I-{aq)-.+2Br{aq) + Ii(aq)
duringea,choftheexperimentsdescribed b No
in the worked example? c Ye1:Clifoq) + 2r {aq)-.+2CJ-(aq) + Ii(aq)
Reactions with hydrogen

All the halogens can react with hydrogen. but the conditions for the reaction vary
going down the group. as shown in Table 11.3.
Table 11.3 Reactioncood1tionsnece11aryfor

Halogen Eqwitlon
thehalogem're;ictiomwilhhydrogen
explodeswhenexposedtoultravio~tlight H,(g) + Cl:,(g) ---; 2HC~g)
H2(g) + 8r2(g) ---; 2HB1{g)
H,(g) + I,(g) s='lHl(g)
The reactivity with hydrogen decreases down the group because the decreasing
.slrength of the H- X bond (see Table I I . I) makes the reaction less exothem1ic.
203
INORGANIC CHEMISTRY
Worked example
Usethebooder.ergie19iveoinTable11.1,andavalueof4:l6kJmol- 1 fortheH - Hbond
energyinHi(g),tocalrnlatetheenthalpychangeforthereactionbetwt>i!nhydrogenand
chlorine,andbetweenhydrogenandiodine
Carryoutthesamecakulatiooforthe
reactioobetwl'ffihydrogenandbromine Answer
gases.DoesyourresuH:litthetrrod ForHi + Cli--->2HCI, Nl = 436 + 242-2x431 ~-184 kJm ol-1
described above? ForHi + l 1 --->2Hl, !JH = 436+ 151-2 x 299=-11 kJm o 1~1
Thermal stability of the hydrogen halides

The strength of the H-X bonds also determines the thennal stability o f the hydroge n
halides. This is readily iJJustmted by the o bservations that are made when they are
heated (a convenient methcxl in the bboratory is to insen a ha1 metal wire into a test
tube of the gas). All the hydrogen halides are colourless gases. Hydrogen chloride
does nct decompose on heating. so the teSI tube remains col01Jrless; hydrogen
bromide decomposes slightly and the gas turns brown: hydrogen iodide decomposes
almo.st completely and the gas turns purple (see Table l 1.4).
~=l~: 11.4 Rl'5ultsofhealiflgthehydrogen r"'~-= - - t~

"'~
K~
oo~(~"~
' "Y~)- - +==- - - - - - +
HC ~g) ood!.>c:ompos.iUoo
2HB1(g)a=" H,{g) + Br,{g) somedecomposmon andgasappears
shghtlybrown
2Hl(g) -+H 1 (g) + I,(g) almo'il complete decomposition a!ld gas
appe.ir;deeppurple
Reactions of chlorine with sodium hydroxide

When chlorine gas is pasaed imo cold. dilute aqueous sodium hydroxide , the
following reaction takes place and two salts are formed :
C1 1{g) + 2N aO H(aq) ---t NaCl(aq) + H 10(1) + NaCIO{aq)
The ionic equation is:
Chlorine itself, being an elemem. h:is the oxidation number O. In the chloride ion. it
has an oxidation number of - 1. Oxygen has an oxidation number of -2 so that. in
the ClO- ion, the chlorine must have an oxidation number of + I in order to give an
overall charge of - l 011 the ion. The c10- io n is therefore rnlled the c hlorate(!) ion.
The -a te' indicates that the chlorine is combined with oxygen. and the '(0" shows
its oxidation number. NaClO is properly rnlled sodium chlorate(J) but sometimes its
common name. "sodium hypochlorite ". is used .
\Vhen c hlorine is passed imo hot. concentrated aqueous sodium hydroxide. a
differemreacriontakesplace:
JCl,{g) + 6NaOH{aq)---t 5NaCl(aq) + JH,O(l) + NaC!Oiaq)
1 He;itingsodiumchlorate Maboveits The ionic equation is

~tingpointc.ausesittoundergo JC\z{g) + 60t-r(aq) ---t 5Cr{aq) + JH,O(L) + C\01-(aq)
anotherdisproportionationredctioo,
giving a mixture of NaCl and NaCI0 4 In the Clo 3- ion , each oxygen has an oxidation number of - 2. The three oxygens
Useoxklationnumberstowritea give a total of - 6. The chlorine must have an oxidation number of + S to give an
balancedequatiooforthisredctioo overall charge of -1 on the ion. The ion is called the chlorate(V) ion and NaCl0 3 is
2 Potassiumiodide,KI,andpotassium called sodium chlorate(\'): it is sometimes incorrectly rnlled just 'sodium chlorate".
iodate(V},KI01,redcttogetherin
These reactions of chlorine with sodium hydroxide are examples of disproportion -
acidsolutiontoformiodine,Ii.Write
ation . This term is applied to a reacrion in which one element has been lxxh oxidised
abalancedionicequationlOfthis
and reduced, so that its oxidation number goes up and down at the same time.
Thehaloge11salsoreacrdirectlywithhydroc:ubo11s (seesectio11s IJ .Sa nd 14.J).
204
11 Group17 1
4' 11.3 Some reactions of the halide ions

Test with aqueous silver nitrate
Most metal halides are soluble in water. but two imp;:mant metals th31 fonn insoluble
halides are silver and lead. lf a few drops of aqueous silver nitrate ""' added to a
solution of a halide, a silver halide precipitate is formed . The silver halide precipirntes
are of different colours and have different solubilities in aqueous ammonia, as shown
in Table 11.5.
Tab le 11.5 ldentific:.itionofthehalideiom AppN r.1nceandformul.1 So lubl lty ofprec lp ttate lnNH.(aq)
usir,g..queousslll'l'rnitr.ite of prec ipi tate
while,AgCI solubleind iluteNH,(..q)
aeam,AgBr solubleinrnncentratl'dNH1(aq)
yelklw,Agl insolubleinrnnc:entratedNH1{aq)
Flgure 11.1 Thecolour;ofthesll\lerhajides

areu51.'dintestsforthehalkleiom
Worked example
Write lulfy bakmced, and ionic, equatioos fOf the redd:iom between
a HClandAgN01
b KiarKlAgN01
Answer
Write fultybakmc:ed,andionk,eq\Jillions HCI t AgN01 ---+ AgCI t HN01
fOf the rNCl:ioo between aqueous sollltioos Ct-(aq) t Agiaq)---+AgCl(s)
ofrragr.esiumbrom;de,M9Br2,aridsitvef b Kl t AgN01 ---+ Ag! t KN01
!iUlfate,Ag;;,S04. r{aq) + Agiaq)---+Agl(s)
The solubilities in water of the precipitates AgCL AgBr and Ag! d=rease from AgCl to
Ag!. This =plains why they react differently with aqueous amnx>nia (see Table l 1.5)
Aqueous silver ions reac! with ammonia to form the ion Ag(NHl) / . By Le
Chatelier's Principle , in order to dissolve the silver halide precipi13te, enough
ammonia has to be present to drive the following two equilibria over to the
rig ht-hand side:
AgX(s) a== Ag+(aq) t x-(aq)

Ag\aq) t 2NH1{3q) a== Ag(NH1)/(aq)
If AgX is very insoluble, the first equilibrium lies well over to the left-hand side, and
Explaininwordshowthei!dditionof so a large concentration of NH,(aq) is needed to pull the Ag' ions into solution .
NHJ(aq)canCi!useAgX(s)todiOOve Silver iodide is so insoluble that even in concentrated ammonia solution, the
concentration of ammonia is n(){ high enough to pull the Ag' ions into solution . For
205
INORGANIC CHEMISTRY
silver chloride, however. which is 1000 times more soluble than silver iodide, even
the small concentration in dilu te ammonia is suffi.dem to drive the equilibria over to
the right-hand side .
Reaction with concentrated sulfuric acid

When concentrated sulfuric add is added to a solid metal halide. the hydrogen halide
is produced.
With sodium chloride. Sleamy fumes o f hydrogen chloride are evolved and sodium
hydrogensulfateisformed :
NaCl(,) + H,so..(1) ----t NaHSOl) + HCl(g)

(At room temperature, o nly one of the two H~ ions available in H,S04 reacts: heating
cancausethesecondonetoreacl. givingNa,S04.)
Concentrated sulfuric acid is a strong oxidising agent. 1t is unable to oxidise HCL
but ii can oxidise HBr and HI. Hence, only a Hnle HBr is formed when concentrated
sulfuric acid is added to sodium bromide, the principal prcxlucts being bromine and
sulfurdioxide(seeFigurell.2):
NllBr + H 2SO,{l) ---+ NaHSO, + HBr(g) small yield

2HBr{g) + HzSO,{l)---+ Br1{1) + 2Hz0{1) + S0 2(g)
Hydrogen iodide is so easily oxidised that only a trace of it is found . The sulfuric
acid is reduced nOI: only to sulfur dioxide, but funher to sulfur, and even to hydrogen
sulfide
Flgure11.2 Bmmineoriodirll'arethe
prindp.ilproduc:tswtienrnncentfatedsulfurk 2Hl(g) + HzS0 4{1)---+ 11(,,) + 2Hz0{1) + S0 1{g)
acidisaddedtoa'iOlidbromideOflodide Hl(g) + H 1S0 4{l)---t 11(s) + 2Hz0(1) + S(s) (nOl:balanced)
Hl(g) + HzS0 4{1)---+ 12(,,) + 2Hz0{1) + H 1S(g) (nOl:balanced)
These reactions demonstrate that the strength of the hydrogen halides as reducing
agents is in the order HI;, HBr;, HCl. This is due to their bond strengths being in the
reverse order, H- 1 < H-Br < H- Cl (see Table I I .I) and shows the ease with which
the bonds are broken toghe the free halogens .
Worked example
Useoxklatk>nnumrn!rstohelpyoo Statethechangesinoxidationnumbersofbromirieandsulfurinthereactionb{>twe{'n
balancetheequationsl0<thetwo BriandHiS04
reaction1ofHiwithH1S04'ihownabove. Answer
onegivingS(s)andtheothergivingHiS. BrominechangeslromBl"(O)toBr(-1);sullurchangesfromS{+6)toS(+4).
11.4 Manufacture and uses of chlorine

The manufacture of chlorine
Chlorine is an imponant industrial chemical. and is manufactured by the electrolysis
of brine. The Ol:her prcxlucts are hydrogen and scxlium hydroxide, lxxh of which are
imponam high-value industrial chemirnls:
2NaC!(aq) + 2H 10{1) ---+ 2NaOH{aq) + C\1(g) + H 1(g)
This electrolysis process is described in section 7.5.
Water purification
Before being used for drinking, water is first filtered and then harmful micro--
organisms are killed by adding a disinfectant . Chlorine is an effective disinfectant
at concentrations as low as one part in a million but higher levels are often
206
11 Group17 1
used to provide a safety margin. If the level exceeds three pans per million.
however. the water then has an unpleasam rnste and smell
The added chlorine dissolves and then reacts with the water lo produce
hydrochloricacidandchlork(I)acid:
C1 1(aq} + ttp(l) a=' HCl(aq) + HCIO(aq)
It is thought that the chloric(O acid produced is the active disinfecrnm. As acid has
b=n produced by the above reaction. the pH must be raised by adding alkali (often
Ca(OH):,). The optimum value is berv.-een pH 7 and pH 8 .
Other uses of chlorine

As well as being a disinfectant, chlorine is also a powerful bleach. and is often used
in the manufacture of paper and fabrics 10 whiten them. It must be used with care as
it anacks most fabrics and can produce poisonous by-products such as dioxin (see
section 25.4). The aaive bleaching agent is most likely the chlomte(I) ion. and so
.sodiumchlomte{l)isoftenusedinsteadoffreechlorine.
A large amount of chlorine is used to make chlorinated organic compounds (see
section 13.S). Examples are the plaS1ic PVC (polyvinyl chloride. properly called
polychloroethene). used for water pipes and window frames. and solvents such as
dichloromethane. used to remove paint and to dernffeinate coffee. Many of these
organic compounds have low boiling points and rnn be used in aerosols or in
refrigera!Ors . One of these is chlorodi(luoromethane. HCP1Cl (boiling point 8 .9C) .
which is also an important Slaning material for the manufacture of tetrafluoroethene .
Tetrafluoroethene is used IO make PTFE (polytetrafluoroethene) . which has many
uses. including for coating non-Slick cookware and for bridge bearings.
AdisadvantageofthesechlorohydrocarbonsisthattheydeS1roytheozonelayerif
they are allowed to escape into the atmosphere (see section 13.4). Their use is now
restricred and oiher low boiling point compounds , such as propane and butane. are
A more complicated halogen compound is haloihane, CFJCHBrCl. which is widely

used as an anaesthetic .
Thehalogensarenon-metalsthatbec:ome!essreactivewith Reactioowithhydrogen
incre;is.ingprotonnumbef. Xi(g) + Hi(g)--->2HX(g) X = Cl,8r,I
Thepropertiesofchlorine,brom ineandiod inearesimilar,and CoocentratedsulfllricMidoosolidhalide
show a steady trend X-{s) t H1S0il} ---> HX(g) + HS0 4-{s) X = Cl, Br. I
AgoodtestlorhalideionsisthereMtionwiths.ilvefnitrate 2HX(g) t H1S04(1}---> Xi(g) t S0i(g) t 2Hi0{1) X = Br, I
solution,fojlowedbytheadditiooofammonia. 8HX(g) t H1S0il}--->4Xi(g) t H1S(g) t 4H10{1)
Theeaseofoxidationofthehydrogenhalidesisintheordef
Testswiths.itvernitrate
HCI < HBr < HI, as shown by their reactioos with coocentrated
Ag'{aq) + X-(aq)--->AgX{s)
HiS04(seebelow)
Chiorinehasseveraloxidationstates Disproportiooatiooreactioosofchlorine
Chiorineiswidelyusedasadis.infectantandb~ingagent Cl1(g) t 2Na0H(aq)---> NaCl(aq} t H10(1) t NaCIO{aq}
3Cl1(g) +6 NaOH(aq)--->5NaCl(aq) + 3H10(1) + NaCI01(aq)
Keyreactionsyous hould know
Displacement reactions
C~(aq} t 2Brlaq)--->2Cliaq) + Br1(aq} Cl1 displacesBri,
andBr1 displacesl1
207
INORGANIC CHEMISTRY

Ple-seethedatasectiotlof theCDforanyA,values'pOU i What term is used to describe a redo~ reaction in
which an element is both O)(idised and reduced? [1]
""'""'
1 Chlorine and bromine are elements in Group 17 of the
ii Write equations fCK these !WO reactions of chlorine
withsodiumhydroi(ide [3]
Periodic Table. iii Chlorine forms another chlorate called sodium
a Chlorineisusedinwatertreatment
chlorate(Vll),usedinthemanufacttM"eofmatches.
State one a~antage and o n e disadvantage of u5ing
Suggest the fCKmula of sodium chlorate(VII). Ill
chlorine in water treatment. [2]
{OCR Chemist,yA Uni! F321 04Jant.Jd,y 2010}
b Theelectroncoof19Urationofbmminecontains
2 Each of the Group VII elements chlorine, bromine and
outermostelectroosinthe4thshe11
iodineform5ahydlide.
U5ing your kno11.1edge of Group 17 elements, complete
a i Outline how the relative thermal stabilities of these
the eJectron configuration of bromine.
hydrideschangefromHCltoHJ.
2 2 5
1s 2s 2p 3l3pi (1] ii Explainthevariationyouhaveoutlinedin l [3]
b Hydrogeniodidecanbemadebyheatin9together
c Di5Place ment reactions can be used to detect bromide
hydrogen gas and iodine vapour. The reaction is
ions in solution.
incomplete.
A student has a solution that contains bromide ions. The
Hi{g) +I1{9)F2Hl{9)
studentcarriesoutthefolla,.yinge:iq;,eriment
WriteanexpressionforK, andstatetheunits. [2]
Ste pl c For this equilibrium, the numerical value of the equilibrium
She bubbles some chlorine gas through a 5ample of
constant!(, is 140at 500 Kand S9at6SO K
the solution UsethisinfOm'lationtostateandexpjaintheeffectofthe
Themiicturechangescoloor. followin9charigesontheequilibriumposition
Step2 i increasingthepressureappliedtotheequi!ibrium
Thestudentthenaddsanorganicsolvent, ii decrea5ing the temperature of the equilibrium [41
cyclohexane,tothemhnure. d Amixtureof0.02molofhydrogenand0.02molof
SheshakesthecootentsandaloNsthelayerstoseparate. iodine was placed in a 1 drn 3 flas!,: and allc:,wed to come
i Writethe io nic equationforthereactionthattakes to equilibrium at 650 K. Cala.olate the amount, in moles,
plac.einstepl [1]
ofeachsubstance l)fesentintheequi~briummixtureat
ii What colour does the cydohexane layer turn in
6SOK.
~ep2 7 [1]
d Chlorinereactsdifferentlywithdiluteandconcentrated 2HI(9)
aqueoussolutionsofsodiumhydroxide. initial moles 0.02 0.02 0 [4]
When chlorine reacts with dilute sodium hydroxide,
(Cambridge lnremarional AS & A level Chemisrl)'.
one of the products is sodium cNorate(I). This is the
9701, Pape,2102Novernber2012}
reactionthatisusedtomanufactlM"ebieach.
When chlorine is reacted with hot concentrated
sodiumhydroxide,adifferentreactiontakesplace.
One of the products is NaCI0 3, used as a ~killer.
In each reaction, chlorine has been both oxidised and
reduced.
208
AS Level
Organic chemistry
12 chemistry
Introduction to organic
Thistopk;mdthosethatfollow/ookat
there;1etionsillldprope,tif!'iofthevast
Learning outcomes
numberoforgdlliccompound<; - lhe Bytheeodofthistopicyoushouldbeableto
cova/entcompoundsofcatbon.The 1.Sb) performcak:ulations,includinguseofthemoleconcept,irwolvingredcting
/iJtge va~ty of organic compounds is masses(part, seealsoTo!)4c1)
described,ronW'f!tKJflsfornaminglhem 14.1 a) interpretar.dusethegeoeral,structural, displayedar.dskeletalformulaeofthe
anddrilWingtheirfrxmulaeMeexplainro, dassesofcompoundsdiscussedinTopjcs 13- 18
andtheclillificiltionoforgdflicf'f!iKtiorl'i 14.1 b) understand and use sy;tematk nomendature of simple al iphatic o.-ganic molecules
is introduced. withfunctiooalgroupsme<1tioriedin 14.1a),uptosO(carbooatoms(st,;plussix
!Ofestersandamides,stra~htcha imooly)
14.1d) deduc:ethepossibleisomersforanorgankmolKuleolknownmolecu!arformula
14.1e) deduce the molecular formula of a compound, given its structural, displayed
or skeletal formula
14.2a) interpretandusethefollowingtermiooiogyassociatedwithorganicredclions:
lunctionalgroup,homo~candheterolyticfission,ffeeri!dK".i!l,nucleophile,
~ectrophile,a<ldition,lllbstilution,~iminatioo,hydrolysis,oxidatiooand
reduction (part,seealsolopics13---18 )
14.4a) describestructuralisomeris.m,andit1divis.ionintochain,pos.itionaland
lunctionalgroupi'>Omerism
14.4b) describe stetroisomeris.m, and its division into geometrical {ds-trans) and
optical isomerism
14.4cl describecis-transisomerismina lkene1,andexplainit1originintermsof
restrictedrotatk>nduetothepreseoceof xbonds (see al'>Olopic14)
14.4d) explain what is me;int by a chiral centre and that such a centre normal!y gives
rise to optical isomerism
14.4e) identify chiralcentresandos-lJ"ansi'>Omeris.minamoleculeofgivenstructural
formula
12.1 Introduction
At one time there were thought to be two emirely differem classes of chemical
substances. Those compounds that had been isobted from the living world. from
org:rnisms. were called organic substances. On the Ol:her h3nd, those elements
3nd compounds occurring in rocks 3nd minerals. or made from them by chemic:il
reactions. were c:illed in organ ic substances .
h was dear thac both types of substances were made from the same elements . For
example. the c:irbon dioxide produced by the ferrnenmtion of glucose:
C6H1106---+ 2C,HsOH + 2co,
3nd tha! obtained from burning the alcohol that is also produced during fermentation :
were the same compound as th.~t ob!ained by heating limestone:

Caco, ---+ Cao + C01
209
ORGANIC CHEMISTRY
Carbon dioxide is :in inorganic compound. It was aca,pted !hat ioorganic compounds
coukl be rnade from organic compounds. b ut for m any years the reverse process was
consideredtobeimpossible. Manyancierudoctrinesincludedtheconcep1of'vitalism',
by which it was believed - withOIJt much justification - that a vital 'life' force was needed
to make organic compounds. so they could only be synthesised within living rngani.sms .
Credit for the s hmtering of this belief is norm:illy given to the German chemist
Friedrich W6hler. who in 1828 transfonned the essentially inorg:ink salt :i mmonium
cyanace imo the organic compound rntbamide (urea) (which is used by the body for
nitrogenexcretionintheurine),bysimplyheating thecrystalsgently :
NH/ OCN - ~ --+
The two branches of chemistry .s1iJJ ..,-main distina , however. and are .s1iJJ siudied
sep<1mtely 31 A level and beyo nd . Organic co mpounds are compounds o f carbon
Nher than its oxides. Today. although several important organic chemicals :ire still
isolated from the living world (penicillin is an =ample) , the majority of the organic
compounds we use have been synthesised anificblly. Sometimes the staning point is
an inorganic chemical, but mos! of!en it is a component of crude oil or coal. Boih of
these are the remains of living orga nis ms, Jong since dead , decayed and chemically
transformed imo hydrocarbons. The ultimate o rigin of all organic chemicals. in nature
and in the laboratory. is the inorganic compound carbon dioxide. This is convened
imo glucose by the transformations of photosynthesis. which require the Sun"s
energy. Biochemistsandorga nicchemistshaveonlyrecentlyunravelled the details o f
these reactions. The overall process is-
6C01 + 6H 10 -+ C6H 1106

,_ + 601
fo llowed by:
blochemlctlpathway,,
glucose - - - - polysaccharides. pro{eins. nucleic adds. etc .
12.2 The stability and variety of organic

compounds
Today. organic chemicals (anificially made or naturally occurring) outnumber
inorganic o nes by 80: I. and n u mber well over 10 million different compounds.
Hundreds of thousands of new compounds are being made each year. Why are
there so many of them? There are two main re:isons
carbon atoms form sirong bonds with cxher carbon atoms

in general. organic compounds are kinetically siable.
We shall look ateachofthesere:isonsinturn.

Table12.1 Thest.ibil ityol!hecarbon-carbon
txmd The ability of carbon to form strong bonds to
Bond enth .1 lpy/kJmot- 1 other carbon atoms
Carbon--earbon bonding allows chains and rings o f carbon atoms to be produced

by a process called cmc n a tlon (from the Latin word calena. meaning chain').
What is more. the 4 -valent nature of the carbon atom allows branched chains
to occur. and the attachment of O!her atoms, increasing funher the number of
structures possible .
210
12 Introduction to organic chemistry I
There are four different ways in which we can arrange four linked carbon atoms
(seeFigurel2.1).
Flgure12.1 fourwaysoflinkingfourcarbon
atoms
[! y
!
With five carbon atoms there are !en different arrangements, and with six carlxm
morns there are no fewer than 17. In a molecule containing 30 carbon atoms. there
aremorethan4x Ja9differentwaysofarrnngingthem.
Worked example
Olthetl.'flpossiblewif'lsofboodingfivecarbooatomstogether,threeareopen-chain
structures {that is, they do not contain a ring of u1rbon atoms). Draw diagrams of these three
Answer
Onestructurewillcontainachainoffivecarbonatoms
If we take o ne carbon atom from the end and join it to the middle of the cha in, we produce
ariotherstructure:
C
c- !- c- c
If we do thi ooce more, we arrive at the third of the three open-chain structures
c- j- c
Note that the first struct ure above represents the same chain as any of the following
c-c-c-1
This is becausethecarbonatomsin achainarenotarranged in a straight line, but are in
fact positioned in a zig-zag manner, with each C- C- C angle being 109.5" {le{' al'iO
Draw out the five open-chain structures section 12.6). All of the above are imperfect Wil"/S of drawing the five-carbon chain in the
containing s.ix carbon atoms. two dimensions of a page, but each shows that there is a chain of live carbon atoms
The stability of organic compounds

The second reason why there are so many organic compounds is a more sulxle
one - once they have been formed. organic comp;:,unds are remarkably .stable. This
stability is more kinetic than thermodynamic. For example. although methane is
thermodynamically .stable with respect to its elements:
CHig} ---t C(s) + 2Hig) tl.H .. =+751.:Jmol- 1
it isunstableinthepresenceofoxygen:
But methane. along with Ol:her hydrocarbons (and most Ol:her organic compounds),
does nOI: react with oxygen unless heated to quite a high temperature - the ignition
point. This low rate of reacrion at room temperature is a result of the high activation
energy that many rnganic reactions possess (see section 8.4). This, in tum. is due to
the .strong bonds that carbon forms to it.self and to (){her elements . These bonds ha,e
to be broken before reacrion can occur. and breaking strong lxmds requires much
energy. Thusmethaneinoxygeniskineticallystable
211
ORGANIC CHEMISTRY
The fir:st stage in the combustion of methane involves the breaking of a C- H bond:
This involves the input of 439kJ of energy per mole - a large value.
Oiganic compounds are thermodynamically unsrnble 1101. only with respect to
oxidmion, but often also with respect to olher transformations. For =ample. the
hydrationofethenetoethanolisexOl:hennic,as isthejoiningofthreemoleculesof
ethynetofom,benzene:
lllf& = -43kJmoJ-l
&H.. = -635kJmo[- l
And yet ethene gas can be collected over water. and e thyne has no tendency to form
benzeneundernom1alconditions. lftherig ht conditionsandcatalystscanbefound.
however. it is possible to conven one stable' organic comJX>und into anOl:her 'stable'
compound . It is even possible to use the same reagent (hydroxide ions) on the same
compound (a bromoalkane) to produce two diffe..,-m products, depending on the
conditions ofsolvem used(seesection 1).3 for details):
i................
C H 1C H BrCH 10) + NaOH(in e thanol) ~ Nafu + H 10 + C H z=C HCH 1 (2)
Figure 12.2 Reactklnpmfilesfor'typkat

organicreact,001.f, ,andf,,aretheactrl'atkm
enl'l'giesforreactioo11.irid2,reo;pective!y
Theactivat,Onenergyistheenergythat
there.Kt.mt1needinDfdertou!ldergothe
reaction
progr~ssof ruaion
Organic compounds can be considered as occupying scable low-energy valleys',

with high-energy 'hills' in between them. One rntalyst, or set of conditions, can
afford a low activation energy 'mountain pass' to a valley next d<X>r, whe..,-as a
differemcamlystcanopenupa newlow-energyrou teintoanOl:hervalleyonthe
12.3 The shapes of organic molecules

AfterWOhler'sconceptualbreakthroughin\828,thenext )()yearssawatremendous
increase in acrivity by organic chemists, making many new com1x><mds and
determining their empirical and molecular formulae. However. it ""s nOI: until after
the work of Joseph Le Bel. Jacobus van't Hoff and Friedrich Kekule in the period
186o----7S that chemists staned co think of organic compounds as being made up of
separate , three-dimensional molecules. After this pericxl chemists applft:iated that
the molecular formula was merely a summary of the structure of the molecule, rather
thantelHngthewholestory.
212
We now firmly believe that all organic (and inorganic) molecules possess a
three-dimensiOflalstructure.andthatthevariousa!Omsarefixedintheirrelative
positions. The shapes of organic molecules depend ultimately on bond lengths and
angles. Bond angles are governed by the murnal repulsion of electron pairs (see
section3.9).
Table 12.2 Bondangle1in,;omeorganic: Bond angle Examples Hybrldlsa tl on(seeS&Ctlonl .1 4)

rnmpwnd1
In each of the molecu les c:ubon dioxide and hydrogen cyanide, in the fir.st row of
Table 12.2, the three atoms are collinear (they all lie on the same straight line). In
the molecule of ethene. in the second row. all six atoms a"' coplanar (they all lie
in the same plane). Ethene is a "two-dimensional' molecule. Methane. however. is a
three-dimensional molecule, and its shape cannOI be easily represented o n a cwo-
dimensional page. \Ve use a s tercochc mlcal formula to show this. as in the last
row of Table 12.2. The dashed line represents a bond behind the plane of the paper.
whereas the solid wedge represents a bond coming out in front of the plane of the
paper.Ordinarylinesrepresentbondsthat areintheplaneofthepaper.
12.4 The different types of formulae

There are six types of formulae that are used to represent organic compounds
We shall iJJustmte them using the examples of ethanoic acid, the acid occurring in
,inegar. and "iso--octane , oneoftheconstituentsofpetrol.
The empirical formula

The infonnation that the empirical lonnula gives about a compound is limited to
stating which elements are contained in the comJX>Und. and their relative ratios. The
empirical formula of ethanoic acid is CH,O. and that ofiso--octane i s ~ In section
1.8. we saw how empirical fonnulae can be calculated from mass or percentage data for
comJX>Unds.
The molecular formula

The lllOk.'Clllar fonnul:i tells us the aaual number of atoms of each element present
in a molecule of the comJX>Und. This is ah.vays a whole-number multiple (xl. x2. ><3.
etc.) of the empirical fom,ula. The molecular formulae of ethanoic acid and iso--octane
are C:,H.P, and Ci!H 13, respectively. Although glucose has the same empirical fom,ula as
ethanok acid. CT-1,0, its molecular formula, c,,tt,p,,_ is six times its empirical formula.
The structural formula

The s tructural formula shows us how the atoms are joined together in the
molecule. The struauml formula of ethanoic acid is CT-1 3C0 2H. or CH1COOH, and
that of iso--octane is (CT-1 1) 1CCT-1 2C H(C H1),. Structural formulae are used to distinguish
between structural isomers (see section 12.6). c=c double bonds are always shown
in structural formulae, and sometimes also C=O and C--C bonds. where this makes
the structure dearer.
213
ORGANIC CHEMISTRY
The displayed formula

Similar to the structural formula. the display! lunnula is tnOR, complete. It sho,vs
ncronlywhichatomsar<,bonded!ogether.butalsothetypesofboods(single,doubleor
dative).Thedi.splayedfonnulaeforethaooicaddandiso--octanearesho,,,,ninFigure 12.3.
Fig u re 12.3 Displayedformu!aeshowthe

"
txmdingintllemolec:ull'
H
-!-H
"j " ""
__ L_J_J_L
!
H- - H
j ! H--H
j !
! !
The stereochemical formula
Although the displayed formula tells us much about a molecule, it indicates noo:hing
about its shape. It is difficult to represent the shape of a thret'-dimensional molecule
on a two-dimensional page. so we use the conventions o f ster<'oc h c mical formulae
iJJustrntedinFigurel2.4.
Figure 12.4 Stereoctiemlc:alfonnulae

reprrnmtthethree-dimerisiooallhapeola
moterute.Thed.ishl.'dlinerPpre1entsabond
toanatombehindthep!aneofthepaper,and
1
w_....,c\:H
the'wedge-s.haped'lil\l'rl'pl'esentsabondto
anataminfrnmoftheplaneofthep.iper.
methane,CH 4 ethanol,C,H,OH
ethano ica<id,CH 1CO,H isooctane,(CH1)1CCH 2CH(CH,),
The sten,ochemical fomrnla for iso--octane in Figure 12.4 illustrates how this type of
fonnub can become too complicated and unwieldy for any molecule with more th:in
:,bout five carbon atoms. Quite often, however, you will come across :, displayed
fonnub in which just a pan has been drawn out to show the stereochemistry around
:, panicubr mom and the resi: left :is :, structural fomrnla .
The skeletal formula

The previous five types of formulae have become increasingly more complicated.
The skdt)ta! fonnul:1 moves in the other direction. lt pares the molecular structure
down to its bare minimum, omitting all carbon morns and :ill the hydrogen atoms ;oined
to carlxm atoms, and the,dore shows only the ca1bon--011W1 bonds. It is an e,;:cellent
,v:iy of describing larger and more complicated molecules. lbe true skeletal fommla
214
Flgure 12.5 Skeletaltarmul..e
aridmodelsof a ethonrn,
b ethanok..c:idand c iso-oc:tane
shows only the caiboo----carbon bonds. but, especially before you beamx, familiar with
theiruse,i!willbeclearertoyouifyouincludeabigdo!torepresemeachcarlxmmom.
Figure 12.5 shows the skeletal formulae of three of the four compounds shown in
Figure 12.4, together with pictures of the com,sponding molerular models.
The skeletal formula of iso--ocrnne shows mo"' clearly than any of the Olber
fomrnlae how the carbon atoms are toined together. This type of formula will be used
in later topics to show the shapes oi. and bonding in, the larger molecules we shall
come across. Its use for smaller molecules is limited. however. as the skdeial formula
formethaneisadOl. and that for ethane is a straight line!
Worked example l 1
What are the molecular and empirical formu!ae of the following rnmpoom!s?
a propane, CH 3CH1CHi b ethane-1,2-diol (glycol), HOCH1CH10H
c dkhioreth,mokacid,CHCl1CO.,H
Answer
a Forpropane,themolecularformulaisC1 H1,whichdoesnotreducefurther,sothe
empiricalfOfmulaisalsoC 3 H1 .
b For ethar,e-1,2-diol, themolern!arformllla of C2 ~02 tedtJCesto CH3 0 as the empirical
formula .
c For dichloroethanok add, the molecular formula of C2H20 2Cl2 redoces to the empirical
IOfmulaCHOC I
Worked example 2
What are the strut:lllral and molernkcir formulae of the following compollnds?
~ ' ~ , ~o~
Answer
Stmcturnl fotmu@ CH3 COC H3, molecu@r formula C1 H60
b Structural formu@ CH3 CH2CH(CH3)i, molecular formu@ C5H 12
c Structural formula CH3 C0 2 CH2 CH3 , molecular formu@ C.Ha0 2
1 WOfk oot the strnctural, molecular and empirical formulae of the following compounds
0
~ ~Br HO~OH
2 Drawtheskeletal foorulaeof thecOfTl)OlJJldswiththefollowingstructurajforrnulae

(CHJCHihCHCH==CHCI b (CH1)iC(OH)CH1CH(CH1KOiH
c CICHiCH1CH(C01H)i
215
ORGANIC CHEMISTRY
The representation of carbon rings in formulae

Rings of morns are often represented by their skeletal formulae. Common examples
areshowninFigure12.6.
F1g u re 12.6s.l::eletalandstructuralformulae
atld model1 of a cydoprnpane, b cydopentane, cydopropane f::::,,
ccyc:Johexane,dcydohexeneandebenzene
c1{,H,
\..,1,,
cy<,oomoO
<y<lohexene
0
Benzene and cyclopropane are planar rings. but the Ol:her three rings in Figu"' 12.6
are all puckered to some degree. The most common arrangement of cyclohexane is
called th.- 'chair' form, which allows the C-C---C bond angles to b.. the preferred
109.5(seeFigurel2.7).
Fig u re 12.7 The 'dial~ form of cydohex;me

minimi~bondstfain
216
Cyclopropane is a highly .strained (and hence re-active) compound . Its bond angles
are constrained to be 60 - far removed from the preferred 109.5. No such problems
arise with benzene, however. The internal angles in a (planar) reg ular hexagon are
120, which is ideal for c:ubon atoms surrounded by three electron pairs .
Worked example
Whatarethemolecularlormulaeofthefollowingcompounds?
CX'' Cl
Answer
Cydohexane is (CHi),,. or C6H11. Two hydrogen atoms have bem replaced by cMorines, w
thelormulais'6H10Cl2
b 6enzeneisC 6Hi;.Onehydrogl'llatomhasbeeoreplacedbyCH 3,andanotherbyC01H
ThemolecularformulaisC1H80 2
What are the molecular formulae of the foOowirig compoor.ds?
' Cl
c(o, lei
12.5 Naming organic compounds
As was mentioned eadier. cxg:utic compounds were originaUy eXlfacted from living
cxganistn.5. The sensible way d naming them incorpormed the name (alien the Latin
version) of the plant or animal concerned. Some common =amples are given in Table 12.3
Table 12.3 Theorig imoftheriame1ol<oome

f\aturalorganiccomprnmm
HCO,H
co,H apples
I
CH{OH)
I
'"
I
co,,
peppemiint
~o,
CH{CH 1),
co,H
I
co,H
217
ORGANIC CHEMISTRY
Table12.4 Stemnames andthenumber5 As nK>re and more organic compounds were discovered during the eighteenth and
ofcarbonatom1theyrep resent.From5 nineteenth centuries. this naming system became increasingly unsatisfactory for two
upwa rd1,the1teml1anatibfeYiatkmofthe
cmrespo!ldin gGreekword fo r thenumber
it could nOI: be applied to those compounds made anificially in the laboratory
the feat of memory required for a chemist to be able to n,late a structure to each
narnewasbecomingtoogreat.
So, inthelanerpanofthe nineteenthcentury,chemiS1sbegantodevisea
sy.stemmic, logical form of nomenclature in which it was possible to translate names
into the corresponding structural fomrnlae, and vice versa, for previously unknown
compounds . The latest version has be<,n adopted by the International Union of Pure
3nd Applied Chemistry ([UPAC), 3nd is (with only a few modifirntions) completely
pent-
intem31ion3l. Chemists throughout the world use it, and undersrnnd one another, no
m3Uer wh3t their first bng uage is . (It has to be said, however, that the true bnguage
hep! of org3nic chemisay is the skeleml formub . Sit next to 3 couple of organic chemists
t3lking'shop ' inarnf<'-.andyouwillseethatinnotimeatallthemenuc3rdor
p3per rnbledoth will be scribbled over with the curious hieroglyphics of skelernl
fonnube .)
All organic compounds contain c3rbon. and vinually 3l[ of them also cont3in
Table12.5 Stem-1uffixl.'5alldtl\ei1 meaning1 hydrogen . A system3tic ruime for 3n org3nic con1JX>Und is often oosed on the 'p3rent'
hydroc3Jbon. E3ch n3me consists of the components listed below ( nOI: 3Jl m3y be
Mean ing
present, however: it depends on the complexity of the compound).
allC-C singlebond'i
I A stem - this specifies the number of carbon morns in the longest rnrlxm ch3in
(see Table 12.4). If the rnibon atoms are trnned in 3 ring, the prefix 'cyclo' is
added .
2 A Mem-suff1I - this indirntes the type of rnrbon----c3rbon bonds that occur in the
ol\l'C -C tripfebond con,pound (sec Table 12.5).
So,
Q-1 3--CH 3 isethanc

Q-1 3--CH=CH, is propene
Q-l=CH--CH=CH 2 is but.1diene.
Arabic numerals may be added before the stem suffix to show the position of
3ny double lx>nd, etc. For example, the"' are two compounds with the n3me
Q-1,=CH--CH=CH, is burn -1,}-diene

Q-l,=G=Q-I--CH 3 is bum - 1.2-<liene.
3 A ~u,.x - thisindic3tesanyoxygen-eonrnininggroupthmmightbepresent (see

fable\2.6).
Table12.6 Sti ffixe1aridthe11 me,ming:s

Mea ni ng
0
an aldehyde group 1
/ ',
0
.iketonegr()\)p II
C
/ '
anakoholgroup _J_OH
I
acarboxyhcacklgr()\)p
218
CTf 3---CHOisethanal
CH 3---CH,---C0 2H is propanoic add
rn 3---CO-CH,-CT-11 is burnnone .
4 One or more p~fixcs - these indicate non-oxygen-containing groups. which

maybe(){hercarl:xm(alkyl)groups.orhalogenatomswhicharesubstitutedfor
hydrogen along the carbon chain (see Table 12.7). The prefixes may also include
subsidbryoxygen-containing groups . Prefixescanbecombinedwithoneanother.
and they might in tum be prefixed by "di' or "tri' to show multiple substitutio n .
The position of a substituem along the carbon chain is indicated by an Arabic
numeral before the prefix . The carbon acomsinthe longe.s! carbon chain an,
numbered s uccessively from the end that results in the lowest overall numbers
in the name. So CH 3- CHCl- CH,Cl is 1,2-dichloropropane (numbering from the
right), and na 2.3-dkhloropropane ( numbering from the left).
T;ibte 12.7 Prefixeo;a!ldtnl'irmeaning1
Mean ing
methyl- CH 1-
ethyl- CH1CH,-
CH1CH,CH,-
hydroxy-
These four simple pan-names allow us to describe a multitude of compounds . The

following e,mmples "ill s how how the pans are pieced together.
a Cl - CH 1 - CH1 - CHO is 3-chluwpropanal
pretix
T 7T~ stem stem-~ffix ~fftx
lf\
stem stem-suffix suffix
''7'71
c CH i - CHO - CH(CH 1 ) 1 is
prdixs>, stem stem-suffix
c~1
/C = CH - CH10H
CH,
prd,x
r r1\ stem stem-suffix suffix
NOl:e that the compound in a is nOI: called 1-ehloropropanal. If a compound is named

as an aldehyde. the aldehyde group is always at carbon atom number I. NOl:e also that
the compound in c could e qually w e ll have been called }-chloro--2-methylbuune (that
219
ORGANIC CHEMISTRY
is. numbering from the right). But the name 3-methyl-2-chlorobutane would have been
incorrect. because-thesubstituentsshould be listed alphabetically .
Worked example 1
Answer
a 2-methylpmpan-2-ol
b 1,2-dimethylcydohex,me
1 Name the following compounds
c but,m-2-ol
a (CH,hCCH(OH}-CHiCHi
b CHr-CH=CH--CHi Worked example 2
Write the structural formulae of the following compounds
a 3-methylbutan-1-ol
b 1,3-dichloropropane
2 Drawstructuralformulaeforthe
following compounds. Answer
a (CHi)1CHCH1CH 10H
2-methyl-2,3-dibromopeotane
b 2,2-dimethylpropane b CICH1CH1CH1CI
12.6 Isomers
Isomerism is the property of two or more compounds (ca lled iso mers ) that have the same
molecular formula but difle<rot arrangements of atoms, and hence different structural
formulae
Isomerism in organic con1p;:>unds can be clas.sified into five different types, according
to the scheme shown in Figure 12.8. Some d these are dealt with in de1ail when they
arise in later topics. but all are included here in summaiy form .
Figure 12.8 The five types of isomerism
Structural isomerism
Therearethreerype.sofSlructurnlisomerism.
220
Chain isomerism
Chain isome rs have the same number of carbon atoms as one ancxher, but their
caibonbackbones are different . Forexample.pentaneand2-methylbucanea..,-
isomers with the molecular formula C~H 12:
CH 1 - 1H- CH 1 - CH 1
CH,
is no1 anOlher isomer: this is just anoiher way of writing the formula of penrnne. Ncxe
CH,
CH 1 - CH 1 -C
tI
CH,
is no1 anOlher isomer. This is anoiher way of writing the formula of 2-methylbutane .
Remember th31 carbon chains are naturally zig-zag arrangements, and that there
is completely free rorntion arou nd any C- C single bond ; however, structural
formulae are often drawn as flat. with 90 bond angles . The formulae in Figure 12.9
all repre""nt differem conformations of the molecule penrnne, and at room
temperature a pankular molecule will be constantly changing its shape from one
Ftgu re12 .9 Cooformatiomofpentane
Positional isomerism
J
This is o ften included under the general umbrella of struauml isomerism. Positional
isom ers have the same rnibon backbone. but the positions o f their funaional
group(s) differ. Their systematic name.s reflect this . For example, there are cwo
alcohols comain ing three rnibon aton1s:
OH
I
CHJ- CH 1- CH 1 - 0 H CHJ- CH- CHJ
and there are t"u compou nds with the formub C:,H.i<:1 2:
(Remember that the rnrbon chaifl is numbered from the end tha! produces the smallest
number prefi=s in the name, so CH.l---cHCl, is ncx railed 2,2-0ichloroetha ne.)
When a carbon chain contains a double bond. the position of the bond can give
rise to isomerism. For =ample. there are c,vo bu!enes:
C H J--CH =CH --C H 3
Positional isomerism also occurs in ring systems. as shown in Figure 12.10.
221
ORGANIC CHEMISTRY
Figure 12.10 Pasitionali'iomer1inring

mok!ru~s Note that the carbon atoms in
thering1atenumberedsta1tingator.eofthe
1ub5titutedone1,,mdthatincycklhexanoliti1
thecarbonatomattadiedtothe---OHgroup
thati'icarbonnumberl
1,2-dimethylbenzene 1,3..::limethylbenzene
Q
'",
1,4-dimethylbenzene
2bromocydoheunol
&.
3brom<><y<lohuanol 4-bromocydoheunol
Functional group isomerism

In func tlonal group isom e ris m . the isomers are more different than in the types
of isomerism considered so far. Compounds that contain different functional group.s
often have veiy different reactions, as we shall see in sectiOfl 12.7. However. if their
molecular formulae are the same, then they are cbssed as isomers.
For example. the carboxylic acid CHiCH,CO,H ( propanoic add), the e.ster
CH 3C01CH 1 (methyl ethanoate) and the ketone----,alcohol CH 3COCH,OH
(hydroxypropanone) a.._. all isomers, all having the molecular formula C 3H 60 1.
Stereoisomerism
Stcreoisomcrs are very clO!'iely related to each other. They conrnin the same 3toms
bonded to one another, and the bonding and functional groups are identical. They
differ only in the way the atoms are arranged in three-dimensional space ("stereo"
is derived from the Greek word stereos. meaning solid'). There are two types of
stereoisomerism - gcomctrlra l and optical.
Geometrical isomerism
This occurs \\ith alkenes thac do r>OI have two identical groups on both ends of the C = C
double bond. It arises because. unlike the m.se of a C--C single lx,od. it is r>OI i,ossible
torotateoneendof3 C=Cdouble bond with respecttothe(){her(seesection 14.1).
The following two fonns of but-2-ene are therefo,., distinct and -""parate isomers :
CHJ H
'C = C/
H/ ' G-1,
The isomer with both methyl groups on the same side of the double bond is called
the cis isomer (from the Latin word cis. meaning on this side'). and that with the
methyl groups on opposice sides is called the /ram isomer ( tram meaning 'on the
other side"). An alternative name for geometrical isomerism is cls-trans isomerism .
Note that the carbon acorns on bol:h ends of the double bond must each be bonded
to two non -identical groups. The following compou nds do >1ot exhibit geometrical
isomerism because one end. or both ends. of the double bond have two identical
atomsorgroupsanached :
Cf 3 /C H3 C Hi - CHi H Cl H
C= C ' c = C/ 'C= C /
/
CHJ 'H CH/1 'H Cl / 'H
222
Geometrical isomerism also occurs in ring systems . For e xample. there a"' two
isomers of l ,3--dime1hylcydobutane . s hown in Fig ure 12. l l . (Rotation around a sing le
bond is preve nted by linkage in a ring.)
">o<"
Flgure12.11 Geometrkalirnmer-;of
1,3-<limethykyc:lobutarie
H1C CH 1
ci>-1,3dimethylcydobut.ane tr.ar,r.1,3-<limethyl<ydobutane
Optical isomerism
Optica l i-.om crism is the mo;1 5Ubde of the five forms of isomerism. as vinuaUy every
physical or c hemical propelty of the isomers concerned is identical. lbe o ne way in which
theycan be distinguishedisbytheireffertOflthepassage of plane-polarisedlight.hence
the name opocal'. The in.suument used 10 measure this effect is called a polarimeter.
The polarimeter
A poL'lrilll<'tcr is used to distinguish optical isomers. The device consists of six pans,
shown in figure 12. 12. A monochromatic light source (that is, one that prcxiuces liglu
of a single wavelength) and a slit produce a thin beam of light. which then pa.sse-s
through a polarL'!Cr. This may be a pie= ol Pobroid (the material from which Pobroid
sunglasses are made); it contains long straight molecules all lined up in the same
direction and only allows through ph(){Ofls whose electric field is oscillating in this same
Flgure1 2.12 Outlinediagramofapol.irimeter
lbe polarised beam now emers the sample, which is a solution of the comJXXmd under
investigation, held in a tube 10cm long. As it come-s out ol the other end, the be:im
passes through anoiherpieceolPolaroid. the anatrser , and then into the phO{oce]l
whichproducesanelcctrkcurrentproponionaltotheintensiryollightthatfullsuponit.
The instrument is calibrated by filling the sample tube with pur<, solvent, and
turning the analyser around its axis until the output from the phOl:ocell is a minimum.
This occurs when the analyser is at right angles to the polariser. (Electronically. it is
mo"' accurate to adjust to a minimum output than to a maximum output .) The angle
onthescaleisrecorded.
The sample tube is now filled with the sample under investigation, and the analyser
is turned until the output from the photocell is again a minimum . The new angle on
the scale is =orded. The rorntion caused by the compound is the difference between
thetwomeasu..,dangles.
The actual rofation depends on four factors - the optical path length (the dist:ince
through the solution), the coocentration of the compound in the solution. the
wavelength of light used. and (to a small extent) the ten1peratur<,. Once these have all
been allmved for, the intrinsic routing pmver of the compound can be compared with
that of others.
223
ORGANIC CHEMISTRY
Theoriginsofopticalisomerism
Optical isomerism arise-s from the inhe-rem asymmetry of the molecules that make up
each isomer. If a molecule has no plane or centre of symmetry. it is called a c hiral
(pronounced "k--eye-rnll' , from the Greek word meaning "handed ') molecule . Chiral
moleculesaren(){identirnltoeachother,butarerelatedasamirrorirnageis!Oits
object.
Flgure12.13 Yourhondla rec:hiral. They
arenotsuperimpos..bleooeac:hother,oro11
theirmirrorimages,butooei11uperim~ble
oothemimximageoftheother.Trythis
experiml'fll. Had your ~ft h;md, outstTetc:tied
andpalmaw;fffrom)'Ou,lnfrootofamirrDf
NowhokJyourrighthand,ootstretchl.'dand
palmtoward1yo11,nexttothem irrnr.The
imageofyourletthalldoowlooK1identicalto
(i'isuperimposableon)yourrealrighthandl
r
c ..,
HO,C_-, " ~:
The most common ca.ses of chimlity occur when a molecule contains a tetrahedral
carbon atom surrounded by four different g roups or 31oms. Such a!oms are !ermed
chiral caibon atoms. or chiral centres . There are two ways of arrnnging the four
Figure 12.14 The two mok>c:uk-; are optical groups around a chiral tetrahedral a!om. and these two a1Tangements produce
isomers - mirror im.ige1 of each other. molecules th31 are mirror images of each cther (see Figure 12.14).
Optica l isomer ism most rnmmoofy occurs when a carbon atom has lour diffeteot atoms
orgroupsattachedtoit.
Two molecules chat are non-superimJX)Sable mirror images o f each other are called
cnantio=rs. They are distinguished by the prefixes (+)- or (- ), or the leners d - or
1-, in front of their names. The letters derive from the Latin words dextro and /a(JIJ(),
meaning "right' and "left', respectively. This relates to the d irection in which each
isomer rorntes the plane of polarised light - either clockwise or anticlockwise (see the
panel opposite)
The angles through which the (+) and (- ) isomers rotate the plane of polarisation
are equal. but they are in opposite directions . A SO : SO mixture of the two isomers
therefore has no effect on the passage of plane-polarised lig ht . The clockwise rotation
caused by the(+) isomer is exactly cancelled by the anticlockwise rotation caused by
the (- ) isomer. This equal mixture of the two isomers is called a raccmic mixtufi' or
Sugars. amino acids and most other biologically important molecules are chiral.
Usually only one of the two isomers, (+) or(-) . is made in nature (but see the
panel opposite for some exceptions). Many pharmaceutical drugs that are desig ned
to interact with living systems also have chiral centres . Enzymes will usually react
with only one of the mirror-image isomers. However. when a compound is made
in the laboratory, it is usually produced as the racemic mixture of the two mirror-
image forms. Nct only is this a po{ential waste of 50% of an expensive product, bm
it can also cause unforeseen problems if the mixture is 3dministered (see the panel
onthalidomideOllpage226). Muchresearcheffonisthereforeputinto produdng
drugs c ontaining molecules of juSI one o ptirnl isomer. Optical purities o f g reater
chan 99.S% arethe aim .
Some naturally occurring enantiomers

Thecan,ones
You wUJ know the taste of speannint. whether in the fonn of ch=ing gum or to:i1:hpasie.
You may also know the taste of cara\\-"aY seeds (Persian cumin or sheerna t""rakam). The
samecompound,carvone. isresponsibleforbothtastes (seeFigu,._..12.15).
Flgure12.15 Enantiomer1afL11VOne
(- H:arvone (+)-<arvone
(spearmint) (caraway)
The lact ic acids
~
The common name for 2-hydroxypropanoic add is lactic add . h derives its name from
the Ultin word for milk' ( ladis). It is fonned when milk is fem,erned by cenain micro-
organisms . Unusually, the acid seems to be produced 3S a racemic mixture of the two
H1C CO,H enamiomers. This is in contrast to the lactic acid produced in our muscles when we
=erdse anaerobically. The product here is pure (+}-bctic acid (see Figure 12.16).
Flgure12.16 (+).!acticac:kli1prodtJCedin
muscle The am ino acids
Except for glycine. all naturally occurring amino adds are chiral. In almo.st all cases,
the amino acids have the same configuration around their chiral rnrbon atom (see
Figures12.17and\2.18).
Flgure12.17 Aminoadd1a1echiralmok>cuH'1
(R = 1iciec:hain;seealsolopk27)
Flgure12.18 Models of
(+)-al,m ineand{-}-alanine (+)-a l;mlne (-)-a lanine
The cell walls of some bacteria consist of chains of mucopeptides. Tbese are co-
polymers of amino acids and sugars. Some of the amino acids used by bacteria.
hov,ever. are of the opposite configuration 10 those thm nonnally occur in nature. This
has turned out to be their downfall. The antibiotic penidl~n interferes with the synthesis
of these mucopeptides. by competing with amino acids of the opposite configuration
for the active sites of enzymes. Tbe inhibited enzymes can oo longer carry oul their
function of repairing damaged cell walls or synthesising new ones. so the bacteria die.
225
ORGANIC CHEMISTRY
The thalidomide tragedy
0Q;60 0 "
Rgure 12.1 9 Th.ilklomide
Many tranquilisers have been developed whose molecules have been based on the
barbituric add ring system . One of these was thalidomide. shown in Figure 12. 19.
Originally it seeme-d to be a very successful. non-toxic sed31ive with no known
side-effects . In the early 1960s, however, it was realised that ,vomen who had been
prescribedthesedativetotreatnauseainearlypregnancy("morningsickness') went
on to deliver badly deformed babies. The drug was withdrawn immediately.
Rese-:irch showed th31 while the(+) isomer was an effective and safe tmnquiliser,
the (-) isomer was the culprit in damaging the foetus. Originally ii was thought that
the problem had been due 10 contamination by the(-) isomer in some production
batches. but subsequent research has .shown that raremisation of the pure(+) isomer
occurs rapidly as soon as it enters the bloodstream: racemisation is over 5()li, complete
within 10 minutes. Thalidomide will never be marketed again. althOOJgh analogues that
a,.,chirallystablearebeinginvcstigatedaspos.sibleanti-inflammalrnydrugs.
Worked example 1
Draw and name the lour alkene isomers with the molecular formula C4H8.
Answer
CH 1- CH 2- CH = CH 2 butlene
2methylpropene
Worked example 2
There are four structural Of positional isomers of C4H~OH. Draw them, name them, and
specify which one of them Gtn exist as a pair of optiGtl isomers (that is, which one is chiral).
Answer
CH 1CH 2CH,CH,OH
CH 1 -CH,-1:-CH1
butan-2-ol(thisischiral)
c~
1 Thereare!iixalkeneswiththe
;H-CH,OH 2-methylpropan-1-ol
molecul<1r formula C5H 10. Draw their
skeletalformulaeandnamethem.
'",
2 Drawtheskeletalformulaeof
the four positional isomers of
dichloropropane (C 1H6Cl 1). Name
r
CH 1 - , - 0 H
them,andspecifywhichcontaina
chiral centre. '", 2-methylpropan2-ol
226
4' 12.7 The different types of organi c
reactions
MO!Slorganiccornpoundscanberepresentedas:
R-Fg
where l'g represents the funaional g roup and R represents the rest of the molecule.
MOS! organic re:ictions are those of functional groups. By definition, the rest of the
molecule does nOI change under the conditions of the reaaion thm changes the
funcrional group. (lf it did change , it would have become a functional group itselfl)
Many functional grouP5 have chamaeristic reactions , which are covered in detail in
Topics 13!0 !Sand 26to28.
Table 12.8liststhetypesoforganicreactionswesh:illbecrn'ering.
Table 12.8 Reactkmtypes inorgaik:chl'rnistry
Rextlontype Functlonalgroup Eumple

CH, + Cl;1 ----; CH1Cl + HCI
2 electrophilkrubsliluticm
3 nudeophili::'>Ubstitutkm h.iklgenoalkane
CH 10H + HBr ----; CH 18r + H,O

4 electrophilicaddition CH,-C H1 + Br, _. BrCH1CH,Br + H,O
5 nudeophilic,;ubstitubon aldehydeorketone(carbooyQ
c~,
/C = O+HO/ ----t
rn,
6 hyrlroly;i1 CH,co,cH, + H, o -- cH,CO,H + CH,OH
CH,CONH, + H,o -- cH,CO,H + NH,

aldehy{!eOfketone{c.irtxmyO c~,
c~,
/C = O+H,N - R ~ /C = N - R+H,O
rn, rn,
CH,CH,Br + Ol-f" -- cH,..,cH, + Br- + H,O
akil'hydeDfketone(c.irbooyO
CHa<)H + (OI _. CH,O + H,O
aldehyrle CH,O + (Oj _. HCO,H
The meanings of some of the terms used in T3ble l 2.8 3re given below.
1 R3dirn l- this is an atom or group of morns that has an unpai!ro electron (that is. it
has an odd number of elecrrons). Radic:ils (sometimes c:iUed free radicals) are highly
reactiveandareirnermediatesinmanyofthereacrionsofalkane:s. Tht,,yhavethesame
numberofprotons3selearons . .soareelectricallyneu!ml(unlikecationsoranions).
2 Electrophi!C' - this is an atom or group of atoms that reacts with electron-rich
centres in Ol:her molecules . Electrophiles possess either a positive charge or an
227
ORGANIC CHEMISTRY
emp{y oibital in their valence shell, or they contain a JX>Lu bond producing an
morn with a panial charge. shown as &+.
3 NuclcophHc - this is an morn or group of morns that reacts with electron-deficient
centres in molecules (such as the c&. in d'------<:J~ compounds). All nudeophiles
posse.s.s a lone pair of electrons, and many a"' anions. Nucleophiles are called
ligands when they ..,-act with transition metals (see section 24.4)
4 Subs titution - this is a reaction in which one morn or group replaces anO!her morn
or group in a molecule.
5 Addition - this is a reacrion in which an organic molecule (usually cornaining a
double bond) reacts with aoother molecule to give only one producr: A + B ~Conly.
6 lly drolys i'! - this is a reacrion in which a molecule is split into two by the action
ofwater(oftenhelpedbyOJ-rortt asarnrnlyst).
7 Condc n s mion - this is the opposite of hydrolysis . Two molecules come together
lO form a bigger molerule, \\-ith the elimination of a molecule of water (or Ol:her
small mol=ule, such as HCl).
8 Eliminatio n - this is a reaction th31 fonns an alkene by the removal of a molecule
of H,O from a molecule of an alcohol. or a molecule of HCI from a molecule of a
9 Reduction and oxidation (10) - these have their usual meanings. Reduction is a
reaction in which the sum of the oxidation numbers of the atoms in the funcrional
group decreases . Oxidation is the reverse.
Worked example
Class.ifythefo!lowingreactions intoone{ormore!)ofthefollowings.ixca tegories:
substitution,addition,h'jl)ro~sis,reduction,condens.ation,oxklation
a CHiCONH1 + H10----tCH1C01H + NHi
b (CHi)1C=O + H-NH1 ----> {CHi).,C= NH + H10
c CHiCH0 + 2[H)----tCH 3CH10H
Answe r
Thisisthesplittingofamo!eculeintotwobytheitclionofwatef - ah'jl)ro~11eilction.H:
could also be considered as a substitution reaction, in which -NH1 is replaced by-OH
b Thisr&Ktionistherever'il'proces.s - itisacondensationreaction
c lhisisbothanadditionreactionandareduction
The scheme in figure 12.20is a noutlineof a synthesisofthekx:alanaesthetic

benzocaine, starting from 4-nitromethylbenzene. Cl assify each of the reactions I,
II and Ill into one of the six categories in the worked example.
Flgure12.20
12.8 The different ways of breaking

bonds, and how they are represented
Chemical reactions involve the breaking of bonds and the fonn31ion of new bonds.
In the topics th31 follow, we shall be looking 31 the mechanisms of some organic
reactions. By m cchanL,;;m we mean a detailed description of which bonds break and
which fom,, and in what order these processes occur. A mechanism also includes a
228
description of how any catalyst thac might be involved in a reaction works. The,., are
thr= differen! ways in which a covalem bond ro a carbon atom may break. Each way
produces a diffe..,-m carbon species.
Homolysis
Bond h o m o lysls. often called h o moly tic fiss io n . results in carbon radicals (see
Figure 12.21). Homolysis is the splitting of a bond g iving an equal share of bonding
electrons to each particle (from the Greek word homo. meaning 'the same') . In
Figure 12.21.thecarbonand hydrogen atornsrnkeoneelectroneach. The curly
arrowswithonlyhalfa head('fish-h<X>k' arrows) representhoweachelectron in
the bond moves when the bond breaks . The carbon atom in the methyl radical
CHJ has only seven electrons around it . Methyl radicals are highly reactive. and
readily form bonds with Ol:her atoms or mol=ules to regain their full octet of
Flgure12.21 Bondhomoly,;is
H !
H : c :-' H- ~ H : c ,
.. :
,:
..
Bond heterolysis forming carbocations

llctcrolysis involves the splitting of a bond giving an unequal share of bonding
electrons to each particle (from the Greek word betero meaning 'Ol:her'. or different').
In Figure 12.22, the chlorine atom has taken both the bonding eleclrofls, leaving the
carbon atom with none. lbe curly arrow describes the tllO'"emem of the bonded pair
of electrons to the chlorine atom . Chlorine. being more electronegative than carbon.
has already attracted the bonding electrons partially. forming a bond dipole ~--cJll--
(see section j .11). This movement of the electron pair results in the caibon atom in the
methyl rarhocation ha,ing only six electrons in its outer shell, and a single positive
charge. hisastrongelectrophile.
Flgure12.22 Bondhetero!y;i1fa rminga

carboutioo
H-!-+<1 - ~ H-r
! !
Bond heterolysis forming carbanions
This method of splitting a bond to caibon is much Jess common than that forming
carbocations. Carbon is quite electropositive. Only when it is bonded to an even more
electl'OJX)Sitive element will its bonds split to form carba nions . Metals are highly
electl'OJX)Sitive. and some of them form covalent bonds \\-ith carbon . Methyl lithium is
thesimplestexample(seeFigure\2.23).
229
ORGANIC CHEMISTRY
Flgure12.23Bo1ldheterolysislormi11g
aG1rtianioo
H : ~' : u - ~ H : ~' : -
t,
H-c+ u - ~ H-C
i
! !
The methyl c:ubanion formed contains a full octel of electrons in the outer shell
ofcarbon. [tsstrongnegativechargemakesi!ahighlyreactivenucleophile. [twill
reactwithvim,allyeverythingthatcontainsa 6t acom.Thecurlyarrowdescribesthe
mon,ment of the bonded pair of electroos to the carbon morn.
The use of curly arrows

The ,,---.. symbol is a useful shonhand which represents the mm'ement of a pair of
electronsfromtheJX)Sitionmthetailofthearrowiotheposition at the head . Its
meaning is very exact. and it should nOl be used to imply anything more. or Jess,
An example of the use of curly arrows is the reaction that occurs when hydrogen
chloridegasdis.solvesinwate-r:
The movemem of electrons in this "'action may be represented as follows :
H - O: " ' H I'ct -----} H - 0 - H + :Cl-

l I
H H
This equation is a highly condensed way of saying:
A pair of electrons moves from a Jone p<1ir of oxygen in water !O the sp<1ce
betw=n that oxygen and the hydrogen of the HCl molecule, to form a new
O-H bond . A! the same time, the two electrons in the H--Cl bond move
towards the chlorine atom and become a lone pair on !hat aeon, . Since oxygen
stanedoffwith'fulluse'ofalonepair,andhasfinishedupwithonlyahalf-
sha"' of the electron p<1ir making up the O- H bond. its charge has dec..,ased
byoneelectronicunit(Oto+l). Since the hydrogen beingtrnn.sferred staned
"ith a half-sha"' of the electron pair making up the H-d bond. and has
finished with a half-share of the electron pair making up the new 0---H bond.
its charge has "'mained the same (zero). Since chlorine .staned with a half-sha"'
Use curly arrows to describe what of the electron pair in the H--Cl bond, and has finished with full use of its own
happens to the electrons when {ionic) lone p<1ir. its charge has inc..,:,sed by one electronic unit (0 to - 1).
ammonium chloride is made from From the length of the p<1rag raph alxNe. you will appreciate how much shorter the
ammonia and hydrogen chloride: description using curly arrows isl But every time you write out mechanisms using
NH, + HCI ----> NH 4CI them. try 10 "'member how this paragraph was translated into curly arrows. Their use
must be very exact if they""' to describe electron movements co,..,ctly.
12.9 Homologous series

ComJX>Unds containing the same functional group of!en form homologous scrles.
the molecular formulae of adjacem members of !he series differ by a fixed unit
(usually CH,)
the physical propenies. such as boiling JX)int and densiry. vary regularly from one
comJX>Undtoanother
the molecular formulae of members of the series fie the same general fonnula .
230
Two examples of homologous series are shown in Table 12.9. Their ooiling points
show a regular trend, as shown in Figure 12.24.
Tab le 12.9 Somepropertiesofthelower Alkanes (g-..al formula C,,H,,...:,) Alcohols (general formula C~H..,.,OH)
alkanesamlalcohol,
Bolhngpoln tl"C Bolllngpolntl"C
'"
c;;, C,H,OH
C,H, propanol C,H,.OH
c,H,0 c,HPH
pentane c,H,, pent:;mol c,H ,, OH
Flgure12.24 Boilingpoint,ofalK;mesand
alcohols
1 ,+ -~~,----~~---,-~---=~==-~-----,--
~ 0
'
For three different homologous series, Worked example

the formulae of the first two members Thefirstandthirdmembe!'sofahomologousserK!ShavethemolecuklrformukleC1H,
areas follows: andCi\;
1 CH10, CiH40 Whatistheformulaof thefourthmembefof theserf!!S?
2 C1H,N, c,HsN b Whatisthegeneralformulaoftheserie<;?
3 C6Ht;,C,Ha
Foreachseries,state: Answer
il themolecularformulaofthefifth a ThediffeieocebetweenthetwomolecularformulaeisC1H4,whichis2xCHi.Thefourth
member member will thefefore have the formula C4'"~ + CH1, which is C5Ha
b thegeneralformula. b Theger.eral formulilisC,,H:z,,..z
12.10 Calculating yields in organic

reactions
\Vhen rnrried out in the labora!01y, rnganic n,actions do nOl always go to cornpleiion.
This may be due either to the n,action n,aching equiHbrium, or to it being so slow that
it would take an age to cornpleie. Some organic n,actions compete with one anOlher
(seepages2\2and275),andsoby-productsan,formedalongwiththemajorproduct.
Even if a re:iction goes to completion. that is, every molecule of .staning material is
convened into a molecule of product, the recovered yield "ill nOl be 100%. This is
due to material being 106! during the purification procedures. For example, if a solid
has been purified by r=rystallisation, some will inevitably be left in the cold saturated
solutionafterthecrystalshavebeenfilteredoff. [fa liquidhasbeendistilled,asmall
amount ol it will remain in the distillation Oask. or on the sides of the condenser.
The JlCr ccntagc y ield is a comparison of the actual yield with the theoreti ca l
}'IC'ld- the yield that might have been expected if the reaction t<X>k place according
to the stoichiomeiric equation, and there was no loss of product in the purification
stages.
231
ORGANIC CHEMISTRY
Forwelldesignedre:ictions, intheh3ndsofanableexperimenrnlchernist.yieldsof
morethan 95%arepossible. Moreus ually.yieldsof6o----8o,!,areoblained .
Worked example
The redetion of 10.0g of b{>nzoyl chkiride with concentrated ammonia solution produced
S.63gofpurerecrystallisedbenzamide.Cak:ulatethepercentageyield
o~c/cl o~c_,....NH,
6 '"", _, 6 """
benzoylchlorlde
Answe r
WefirstcalrnlatethenumberofmolesofbenzoylchlOOdeused(seesectiool.7)
M,{C6H1COCI}~ 7 x 12 + 5 x 1 + 16 -t 35.S~ 140.S
n~M
n(C6H sCOCI) = 1~.s = 0.07117mol
From the equation, 1 mol of bell~ chloride produces 1 moj of benzamide. Thefefore
n(C 6H5CONHi) = 0.07117mol
M,(C6H1CONH1)~ 7 x 12 + 7 x 1 + 16 + 14 = 121
so m(C6H5CONH1)=0.07117 x1 21 = 8.61g
andpercentagey,eld =act=~;~~%
100
=5. 63x8.61
Calculate the percentage yield from each of the following reactions.

1 Onoxidation,5.0g ofethanolproduced4.Sgolethanok:add
C1H50H + 2[0)--> CH 3COiH + Hp
2 Reacting 10.0gofpropanolwithanexcessofhydrogenbromidepmduced 12.Sgof
bromopropane
c,H,OH + HBr--> C3H7Br + H10
Carbonformsstrongbondstoitselfandtomanyothefatoms There are five types of isomeri sm shown by organic
-
This allows organk: compounds to be kinetk:al!y stable. Ol\ing to compounds - cha in, positiona l, functlona l group ,
thehighactivationb.Jrriertof&Klion,eventhoughttieymaybe geomtrica l and optica l.
thermodynamically unstable Mostorganic:reactionscanbeclassifiedintooneoftengeneral
ThereMesixtypesofformulausedtorepresentorgank:
compounds - empiri ca l, mo lec ula r, structura l, d isplayecl , Manyorgank:t&Ktiom do not give a 100% yield of product. The
stereochem ica l and ske leta l. percentage yield is a measure of how efficient a reactkm is
All organk: compounds can be named systematicaHy. using a
logical system based on the riumber of carbon atoms in their
longest chain.
232
12 lnlroduction lo organicchemislry I
--
Ple-seethedataSKtionof the CD foranyA,valuesyou
1 Compound X has the molecular formula C.ti, Oi

a ThemoleculeofXhasthefollowingfeatures
The carbon chain is unbranched and the molecule is
notq,:lic.
3 The structtM"al formulae of si x different compounds. P - U,
are given below.
CH 1CH:CHCH1CH1
p
CH 1CH1COCH1CH1
CH1CH1CH2CH1CH20H
s
HOCH2CH1CH(OH)CH1
Q T
No0()9fflatt:misattachedtoaT'lfcarbonatomwhichis
CHz=CHCH1CH1CH1 CH1CH1CH10C H2CH1
if'!VOl,,,edin,:boodiog.
No c.artx,n atom has more than one oxygen atom joined
R u
a i Whatisthe ernpiricalfOOTIU!aofcomJ)Ol.,ndn
toit .
ii Draw the skeletal formula of compound 5. 12]
TherearefivepossibleisomersofXwhichfitthesedata
b i Compounds 5 and U are isomers .
Four of these isomers exist as two pairs of stereoisomers.
What type of isomerism do they show7
i Draw displayed formulae of eac h of these two pairs
ii Two of the six formulae P- U can each be drawn in
ii These lour isomers of X show two types of
two forms which are known as stereoisomers
stereoisome<ism Which two compounds have formulae that can be
State which type of isomerism each pair shows [6)
drawn in two forms?
{Cambridge International AS & A level Cherristry 9 701,
What type of stereoisomerism does each show7
Paper 21 05 b November 2012]
Identify each compound b',' its letter. [3]
2 When0.42gofagaseoushydrocarbon A is$1o\\fypas.sed c Compound 5 cao be converted into compound R.
overalargequantityofheatedcopper(IQoxide,CuO, A i Whattypeofreaction isthis?
is comple tely CU(idised. The products are ccilected and it is ii Whatreagentw0Jldyouuseforthisreaction7
found that 1.32 g of C02 and O.S4 9 of H20 are formed iii Write the structtM"al formula of the compound formed
Copper is theontyotherp,oductofthereaction. when T undergoes the same reaction using an excess
a i Calculatethemass ofcarbonpresentin1.32gofC0 2. of the reagentyouhaYeused in c ii. [3]
Usethisvaluetocakulatetheamo1.M1t.inmoles, of {CambridgelntemaOOnalAS &A Level Chemistry 9701,
carbonatomspresentin0.42gof A Paper23 04a.b& c ~ l 0 1 1 }
ii CalaAatethemassofhycnigenpresentin0.54gofH1 0.
Use this value to calculate the amount. in moles, of
hydrogenatomspresentin0 .42gof A
iii ltisthoughtthatAisanal.-ratherthananalkane.
Use your answe,s to (i) and (,~ to deduce whether this is
COITect. Explainyouranswer. (SI
b Analysis of another orga~ compound, B, gave the
follov.ingcorr,positionbymass:
C, 64.86%; H, 13.50%, 0, 21 .64%
i Use these values to calculate the empirical formula of B.
ii TheempirKalandmolecularformulaeof B are
the same. B isfoundtobechiral. Draw displayed
fOfmulae of the two optical isomers of t his compound,
indicating with an asterisk() the chiral carbon atom.
iii There are three other structural isomers of B which
are not chiral but which contain the same functional
group as B. Draw these isomers. (7)
{Cambridge International AS & A Level Chemirtry
9701 , Paper 13 02 November 2011]
m
AS Level
Organic chemistry
13 Alkanes
Fun ctional group:
Learning outcomes
Bytheeodofthistopicyoushouldbeableto
In this topic the properties and 1.Sb) perlOfm c.alrnlatkms, includ ir.g use of the mole coocept, invoMng YOlumes of
reactionsofthesimplestofthe gases(part,seealsolopic1)
homologous series, thea/kanes,are 14.1a) interpretandusethegeneral,structural,displayedands.keletal foonulaeofthe
discussed. Their extraction from crude alkanes(part,seealsoTopk12)
oil and how they are transformed 14.2a) interpret and use the following terminology assodated with organic re<Ktions
into fue/sandfeedstocksforthe homoiytkfission,freeradkal,initiation,propagation,termination
chemical industry are described, 15.1a) unde!stand the general unrNctivity ol alkaries, indudir.g towards polar re.igents
andtheirreactionswithoxygen, 15.1b) describe the d1emistiy of alkaries as exemplified by the following reactions of
chlorine and bromine are studied. ethane:combustion,andsubstitutionbychlorine andbybrom ine
Theircharacteristicreactionofradica/ 15.1c) describe the mechanism of free-radkal substitution at methyl groops with
substitutionisexplainedindetai/. particularrefefencetotheinitiation, propagation and termina tion rMCtion s
15.1d) explaintheuse ofcrudeoilasasoorceofbothaliphaticandaromatic
hydroc.arbons
15.1e) suggesthowcrackingcanbeusedtoobtainmoreusefulalkane1andalkeriesof
lower M, from larger hydroc.arbon molec:u~
15.3a) desc:ribe and expla in how the combustion rMCtions of alkanes Ired to their use
as lu~sinindustiy,inthehomeandintrans.port
15.3b) recognisetheenvironmentalconsequencesof-
carbonmoooxide,oxide1ofnitrogenandunbumthydrocarbonsarisingfrom
theinternalcombustionengineandoftheircata!yticremoval
e gasesthatcootributetotheenhancedgreenhooseeffect
15.3c) outlinetheuseofinfraredspectrossopyinmooitoringair po! lution(seealso
Topic29).
13.1 Introduction
The alka n C'S are the simplest of the homologous series found in organic chemistty.
They coma in only two types of bonds. both of which are strong and fairly non-polar
(see Table 13.1). (See section 3.10 for an explanation of bond polarity.)
Table13 .1 Carbofl-Glrbonandc.rbon- lklndenth.Jlpy/kJmol ' Polar1ty (dlffent nce ln

hydrogentxmd1arestrongandnon-polar electro negatMty)
Consequently. the alkanes a re nOI: particularly reactive. Their old name (the
paraffins") reflected this "little (JH1 rum ) affmity'. What few reactions they have
however. are o f immense imp;:mance to us. They constitute the major patt of crude
oil. and so are the stalling point of vinually eveiy Ol:her organic con1JX>und made
industrially.Apanfromtheiru tilityasafeedstockforthechemicalindustiy.their
major use is as fuels in internal combustion engines. jet engines and JX>Wer stations.
We shall be looking at their role in combustion reactions in detail later in this topic.
13 Alkanes l
The straig ht-chain alkanes form a homologous series with the general formula
C,,H,,,_.2. A,;thenumberofrnrbon atoms inthemoleculeincreases,the vander
Waals' anmcrions between the molecules become stronger (see section 3. 17) . This
has a clear effect on the boiling points and the ,iscosities of members of the series (see
Figul"-" 13.1 andTable14.l , page252)
Fl gure1 3.1Theboilingpointsandvisrn'iit~
olthe.ilkanes
F1gure1 3.2Sp..cefi llinga!ldball-an(i.stid:

mocielsofethane,C,H 0 {aand b )andbut;me,
c,H,, (c to f}_ The 1p,Ke-filling models show
theoverall shapeoftllemo1eculebutthe
ball-and-1ti::kmodelsshowthepoloibort5of
theatormmoredearly. Notethateand f are
identkalta c and d ,a1theya1eformedbyfree
mtabonolthecentralC-Cbond
13.2 Isomerism and nomenclature

As was mentioned in section 12.S. the first .step in naming an alkane is to identify
the longest carbon chain. whichgivesthestem . Sidebranches3rethen identified by
prefixes. Eachprefixis derivedfromthe stem113meden01ingthenumberofc3Jbon
3tomsthe sidechainconrnins. 3ndispreceded by3 numberdenO!ingthep;:>Sitionit
occupies o n the longest rnrbon chain . Two examples will make this clear.
Example\
The longest carlxm chain contains four rnrbon amms. so the alk:rne is a derivative
of burnnC'
There is just one side branch. containing one rnrbon morn (and hence called methyl).
235
ORGANIC CHEMISTRY
Thebranchistoinedtothesecondcarbonatomofthebutanechain.
lhe name of the alkane is 2-methylbutanC'.
Example2
The longe.s1 carbon chain consi.sls of six carbon atoms (hexane).

lhere are 1,vo one-earbon side branches (two methyl groups. dimcthyl).
These are on po5itions 2 and 4 of the hexane chain. (We count from the right-hand
side : counting from the left would put the methyl groups on positions 3 and 5. so
we choose to count from the end that gives the lower numbers.)
The name of the alkane is 2.4.dimcthylhcxanC'.
The main type of isomerism shown by the alkanes is chain isomerism. although
some of the more complirnted struaures are capable of exiSling as optical isomers.
Worked example 1
What is the alkane of lowe51 M, (rel ative mo~lar mass) that cont aim a chiral centre {se{'
section 12.6)? Give its systematic Mme and molecular formula
Answer
Tobeadiiralcentre,acarbonatommU51:havefourdiflerentgroupsattachedtoit.The
fourlowestM,groupsthataieall differenttoooeanoth&areH,CH1,CiH 1 andC1H1.The
alkane is theiefore CH1CH 1- CH(CH1)- CH 1CH 1CHi, whose molecular formula is C1HH
Applyingtheruleslistedinsectioo 12.S,theloogestchaininthiscompoundcontainssix
carbonatoms,andthesidegroup(methyl)isonthethirdcarbonatomofthechain.Hence
itsnameis3- methylhexane
1 Givethesystematicnamesofthefcllowingcompounds
(CzHshCH
b (CH1)iCH-C{CH1li-CH(CH1b
2 Draw the structural and skeletal formulae of the following compounds, and also give
their molecular formulae.
a 2,2,3,3-tetramethylpentane
b 3,3-diethylhexane
As the number of carbon morns in an alkane increases, " does the number of
possible structural isomers . There are two isomers of CiH, 0. three of~H.,, and five
of CJ-1, 4 (see Table 13.2). By the time we reach C,oJ-1,.,. there are no fe"'<'r than 75
isomers. and for C;,ott., the number of isomers has been calculated to be in excess
of300000!
Structural (chain) isomers of alkanes undergo the same chemical reactions . They
differ slightly in the following two re.spects. however.
The more branches an isomer has. the more compact are its molecules. with a
smaller surface area of contact between them. This muses the van der Waals'
bonding between the molecules to be weaker. The con.sequence of the weaker
imermolecular forces is that the boiling JX}ints of branched isomers are lou'et' than
!heirstraight-<:haincoumerpans(seeTable 13.2).
The isomers that are more branched do nOI: pre-ignite so easily in imernal
combustion engines. They are therefore much preferred for use in modern
high-<:ompression petrol engines.
236
13 Alkanes l
Table 13.2 Thebo ilingpoint10!10me Bolling

isomersofc,H,,andC 0H14,si1011inghow
theboilingpointinoease1withcdfbon-Ulain
""'"""" polnttc
length,butdema'>!.'5withbfam:hing peot,me C,H,, ~
~
1-methylbutane C,H,,
1.2-dimethylpropane C,H,,
~
C,H,. ~
~
3-methylpentane C,H ,.
2-methylpentane C,H ,.
~
2,3-dimethylbutane
~
C,H ,.
2,2-dimethyfbutane C,H,.
)c,,
13.3 The processing of crude oil

Origins
Crude oil. like coal, is a fossil fuel. h was formed millions of years ago when plant
(and some animal) remains were crushed and subjeded to high !emperatures in
the ab.sence of air. Under these extreme chemically reducing conditions, oxygen
and nitrogen were l'ftll<Ned from the carbohydrates and pro{eins that had made up
theorganisms,andlongcarbonchain.sforme<l. ltisestimmedthatmostoftheoil
fanned in this way, deep underground. has since be<,n transponed to the surface
by geologirnl movements, and has evaporated. The amount left is (or was) still
considerable. however.
M0.51 crude oil is found trapped in a .stratum (layer) of porous rock, rnpped by a
dome-shapedlayerofimperviousrock.ltisextmctedbydrilHngthroughthecap
rock, whereupon the natural high pressure of the oil forces it up to the surface. If
suchpressureisinsufficient,waterispumpedimotheoilresef\uirand forces the oil
Flgure 13.3'Bottlebrush'extractklnofoll
upwards (seeFigure\3.3).(0ilislessdensethanwa!er.)
from rock strata
Fractional distillation
Crude oil is a mixture of many hundreds of hydrocarlxms, ranging in size from
one to 40 or so carlxm atoms per m o lecule . The first srnge in its processing is a
fractional distillation carried out at atmospheric pressure (see figure 13.4). The
boiling point of crude oil ranges continuously from below 20C to over 300C,
and many fractions could be coll=ted, each havin g a boiling point range of
only a few degrees . In practice, the most useful procedure is to co ll=t just four
fractions from the primary distillation . Each fraction can then be funher purified
or processed, as required. Table 13.3 lists these fractions (and the residue) ,
togetherwiththeirmajoruses.
237
ORGANIC CHEMISTRY
FJgure1 3 .4 ThefractklnaldMi llotionof

audeoil
Bolll ngpolnt Pen:entage

range/"C ofaudeoll
refinery gas luel, petrochemkal
feedstock
gaso line fuel for petrol en gines,
petmc:hemiulfeedstod:.
aeroplane fu ej, paraffi n,
oac:kl>dtagivl'moreg.i'>Oline
gasod fuellordiesel engines,
uac:kedto givemDfe
ga1oline
lub ric ating oil.power
statkl n fuel,bitumenlor
road1,u..ckedtogivemofe
g,mlline
Cracking - breaking long-chain molecules into

shorter ones
Over 9()% of crude oil is burnt as fuels of one son or anOl:her. Less than l ()Yo is used
asafeedswcktoproducethehostoforganicchemicals(pla.stics,fibres,dyes,paints,
pham1aceuticals) that are derived from crude oil. The relative dema nd for petrol (and
hence for the gasoline fraction) far outstrips the supply from the primary distillation -
abou t tv>'ice as much is required as is contained in crude oil. Consequently, methods
have beendeq,Jopedtoconven the hig her boiling, and m<>re abundant , fractions
into gasoline. This is done by c rac kin g the long-chain molecules into shorter units .
Two alternative processes are used - thermal cracking and catalytic cracking. We can
iJJustrate the diffe..,-nce belw=n these using as an =ample dodecane (boiling JX>int
216C), a typical component of the kerosene fraction .
238
13 Alkanes l
Thermal cracking
Therm a l crack in g involves heating the alkane mixture to about 800C and at
moderate pressu..,-. in the ab..ence of air but in the presence of steam . After only a
fraction of a second at this temperature, the mixture is rapidly cooled. By this means
dodecane might typically be broken into hexane (ooiling point 69C) and ethene:
Thehexaneisrequiredforfuelbut theetheneby-productisnotwasted. asitis

a keyfeedstockfortheplastics. fibresandsolventsindustries:theconditionsfor
thermal cracking are often chosen so as to op1imise ethem, production .
The he-:,t energy at 8XlC is sufficient to break the C---C bonds into two carbon
free radicals. Long-ehain radicals readily split off ethene units. eventually producing
Verylittlerearrangement ofthechainsoccursduringtherrnalcracking .
Catalytic cracking
Catal)1 lc cracking involves heating the alkane mixture to a temperature d about
S00C and passing it under slight pressure over a catalyst made from a porous mixture
d aluminium and silicon oxides (called zeolites). The catalyst causes the carbon chains
to undergo internal rearrangements before forming the final producrs.
A typical set of products from catalytic cracking is shown in the following equation .
The branched-ehain alkanes produced by catalytic cracking are useful components

ofhigh-0ctanepetrol (seefigure 135).
Re-forming
The demand for branched-ehain. cyclic and aromatic hydrocarbons as components
of high-Octane petrol is funher satisfied by ~ -forming straight-ehain alkanes. The
Flgure1J.5 lnacatalytk:aacker(a'cat
uacker'),k>ng-<tiainmok>cute-;areconverted vaporised alkane mixture is passed over a platinum-eoated aluminium oxide catalyst
into!l10fter-diainmo1eru~1whITTlhavemore at S00C and nxxlerately high pressure. For example, heptane can be re-formed as
shown in Figure IJ.6.
Flg u reB.6Straight-chainalkaneo;are
re-forml.'dintobranchl.'ddia in,cyc:licand
aromatkh)'Oroca!bom.(Se!'Topic2Sfora
de'>Criptkmofaromatichydrocarbons.)
+4 H,
methykydohexane
In general. re-forming changes straight-ehain alkanes intobranched-ehain alkanes and
cyclic hydrocarbons without the loss d any carbon atoms, but often with the loss of
hydrogen acorns.
13.4 Energy sources

Modern society has an almos t inexhaustible thirst for energy. in the fom1s of
electridcy, spaceheatingorairconditioningforhomesandoffices,andenergyfor
transpon. byroad. rail. sea and air.
Aswesawin section5.J. theenergysourcesavailabletouscanbedivided into
two categories - renewable and non-renewable. The forme r catego,y includes the
renewable fuel e thanol, oblained from the fermentation of starch-rich plants such
as sugar cane. and the alternative energy sources such as wind power. wave power
239
ORGANIC CHEMISTRY
and tidal JX>Wer. Ethanol from ferment31ion can be used as a renewable fuel for cars
and.cOflceivably. in power stations. just like the hydrocarbon fossil fuels. lnsuch
situations, similar types of p;:>Jlution could result from its burning . Nevenheless , in
practice. ittcndstobea "cleancr'fuel thanhydrornrbons.
The alternative energy sources produce no chemical pollution. Their disadv:rnrnges
arethmtheyareoftenseasonalandcanbeunreliable, and theya..,.notreadily
transpormble, and so cannot be used for mobile vehicles. Their energy also cannOI
bestoredforfutureuse. Energyfromthesealtemativesourcesisusua llytransfom,ed
immediately into electrical eneigy. Progress is being m:ide to solve these problems.
however. One IX)SSibility is to use altemmive sources of energy to split ,,,:i ier into
hydrogen and oxygen (see section 23.6). The hydrogen can be transp;:med and stored
for future use :isa pollution -free fuel
The non-renew:ibleenergysources include the hydrocarbons nmuralgas and crude
oil. :ind thecarlxm-richcoal. These:ire called foss llfucls . h:iving been produced
m:rny milJions of years ago from trees, giant ferns and marine org:rnisms buried
bene:ith !heE:irth 'ssu,face.
Uranium, the primmy fuel for nuclear reactors. was produced an even longer time in
the past. when the elements of the Solar System were synthesised in the centres of dying
stars billions of years ago. In a sense. i! tex> is a non-~v,able energy source. Nucle:ir
reactors produce linle chemical poUutiOfl. but the risks of radiation pollution from their
use :ind from the reprocessing of their spent fuel have caused them to fall from favour.
Some power st3lions :ire now being designed to burn domestic :ind industrial
,v:iste . Althoughthis s h01Jlddecreasetheam01Jntofwastegoingtolandfillsitesor
pollutingtheenvironment,careh:iscobetakenlOensurethat po{enti:illypolluting
combustion products an, trapped . AnOl:her way of recycling combustible waste is
to he:it it in the absence o f oxygen . This produces oil or solid combustible m:,terial.
Flgure 13.7 Nitrogenoxid{>,;rnntributeto
which can be used as fuel in a conventional power station .
klw-level ozolll' and smog Low-level ozone
cau,;e,;respiratoiyproblems, aridperoxyacet~ There an, five m:iin pollurnnts thm are formed when fossil fuels are burnt:
nitrate (PAN). a major (omponent of smog, is carbondioxide (this isnOl:strictlyaJX>llutant , sinceitoccursinnatun,. but its
harmfultop!ant1andhumaflS.ThereactiD111 overproduction can muse problems)
N0 2 ----;NO + O carbon monoxide
0 + 0,---->0, e unburmhydrocarbons
hydmcarbom + o, + t,.1() 2 + light-> PAN e nitrogenoxides (seeFigurel3.7)
e sulfurdioxide.
Allthe,.,,pollutantgase:s:ibsorbinfraredradiationatspecificandcharacteristic
fn,quencies.and.sotheirpresenceandtheirconcentrationsingaseousemiromnents
(e.g.:iutomobileexhausts, dtystreets,thegeneralatmosphere) canbefllOflitoredusing
infraredgassensors. Theprinciplesofinfrnredspectroscopy:in,describedinsecti0fl29.3 .
With the exception of carlxm dioxide and su lfur d ioxide. these can all be
removed from vehicle emissions by:, carnlytic convener (see section 8 .6). FIU C'-gas
d e s ulfuris:i tio n ( FG D) is used in power st3lions to reduce the amount of sulfur
dioxidere:ichingtheatmosphere. lnthisprocesstheflueg:isesarep:issed through:,
slurry of calcium carbonate. Calcium carbonate (limestone) is che:ip, :ind the calcium
sulfate produced can be sold :is gypsum. a c omponent of pbster.
CaC0 1{,) + S0 2(g) -+ CaS01(s) + C0 1(g)
The use of the more expensive magnesium carlxm:itC' :illows the sulfur dioxide to
be regenerated and usedtomakesulfuric:idd.
~
MgO{,) + S0 2(g) - - - - ~ MgSOis)
bbgnesium carbon:ite is used because both it and magnesium sulfite an, more easily
decomp;:,sedbyheacthanthecorn,sponding calciumsaltsare(seesectionl0.4).
240
13 Alkanes l
The greenhouse effect and carbon dioxide

Whatis thegree nho useeffect?
A gr=nhouse is a building constructed mainly of g la.ss, which is used to hasten the
gro"1h of plants in colder climates. by providing a wam,er atmosphere for them .
Apan from its obvious role of pro{ecting the contents from the weather, the glass
in a greenhouse also warms the inside by means of the gt"C('llhOlL~ e ffect. Glass
is transparent to visible light, and allows tTK>St of the sunlight through . The light is
absorbed byobjectswithinthegreenhouse(iftheobjectshappentobeplants,useful
phOl:osynthesis results - but even a plant-free greenhouse stiJJ shows the greenhouse
effect). This absorption of light energy causes the objects to warm up. Warn, objects
emit radiation of a much longer wavelength than the visible speccrum - they give out
infmred radiation . Glass is opaque to infrared radiation, so it absoibs it, 3nd warms
upintheprocess.So,muchoftheenergyfromthevisiblelightistrappedinsidethe
greenhouse, wh 'ch becomes warmer and warmer.
Flgure 13.8 lti!iwarmerimkleagr!!!!nholJS!'
thanoolside Sun',radiation,mainlyin
the vi<ible partofthe
spectrum,passesthrough
the gla ..
a,,oilandplant,warmup,theyemitlonget
wav..lengthinfruedradiationwhi<hdoesnot
pas,throughthe glass
The atmosphere around the Earth acts to a certain extent like the glas.s in a
g reenhouse. The Sun's rays - visible, ultraviolet and infmred - pas.sthrough the
atmosphere to the surface of the Earth . Absorption of this energy at the sutface causes
the bnd and sea to warn, up. They begin to emit infmred radiation. much of which
passes straight through the atmosphere and is lost to outer space. But a proportion
isabsorbedbythegaseousmoleculesintheatmosphere,andsothispanofthe
energyisnOl:lost,butre-radiatedbacktotheEanh'ssurface(seeFigure 13.9). By
thismeansthesu1faceiskep1atareasonablyconstant,wam1temperaturedayand
night, summer and winter. (Contrast this with the situation on Mars, which has little
atmosphere, and where night-time temperatures can be JOO"C lower than those
during the day.)
Increasing the greenho use effect of the atmosphere
The greenhouse effect of the atmosphere is essential to provide the right stable
environment for life. ButthereisafinebalancetobestruckbetweennOlenoughof
the effect, in which case more of the incident solar energy will be lost, cooling the
Eanh to another ice age, and t<X> much greenhouse effect, in which case the Earth
will become t<X> warm. This could result in melting icecaps, raised sea levels 3nd
cha~ s ncl'mat 'ca rcrculat 'on.
Carl:xm dioxide is a natural atmospheric component that is responsible for the
greenhousepoientialoftheatmosphere.ltsproductionfromtheburningoffossil
fuelsforheating,tmnspon andelectricitygeneration,causes3n increase in that
potential. The present concentration of carbon dioxide in the atmosphere is only
0 .035%. But 300 years ago it was only 0 .028%. This 25% increase has contributed to
anaverageincreaseinglobaltempemtureof0.5C.
241
ORGANIC CHEMISTRY
Flgure13.9 Toegrl'l'nhomeeffectwarms
theE;irth
The olher major natural greenhouse gas in the au:nosphere is water vaJX>Ur. It has
been suggesced thm a runaway' effect might begin 10 operate - as global wanning
increases. the warmer aunosphen, will be able 10 absorb more water vapour. which
in tum will lead to a greater greenhouse effect. increasing global warming even more.
Bol:h C02 and H,O absorb infrared radiation by increasing the vibrational energy of
their bonds (see Figun, IJ.10).
Flgure13.10 Cartxmdklxk!earidwoter
molec:uk-iabsorbinfraredradiationby
vibfatinglheirbonds.Thi1i1howthl.'ylrn:rea'>I'
thegfl.'1'11houseeffect
There are many natural ways of reducing atmospheric carbon dioxide.
Wmer in the se-as dissolves millions of tonnes (but Jess now than it did. since the
averageoceantemperarnrehasincreased by0.SCinthebst lOOyears,andgases
arelesssolubleinhoithanincoldwater).
Plankton can fix the di.s,;o[ved caibon dioxide into their body mass by
phoiosynthesis.
Trees fix more atmo,;pheric carOOfl dioxide per acre th:in grass :ind oiher
vegerntiondo.
Bhnket pe31 bogs. which co,.er ground in temperate clirnates th31 h:ive a brge
annual rainfall. store a brgequantityofcaibon.
Moreintensive agriculture,especiallycanle-re:iring.forex:impleinAustraHa.:ilso
producesgreenhouseg:isessuchasmeth:ine,whichistentimesaseffectiveinthis
role :is rnrbon dioxide. But methane is produced in sm:iller quantities than rnrbon
M:iny of the cxher pollutant gases th31 modern society h:is used have :in even
greater pcxentfal - for example, CFCs :ire over 5000 times as effective as greenhouse
gases :is rnibon dioxide is but, like methane. they are produced in much smaller
quantities. (Their m:iin environment:,[ effect. however, is in destroying the
stratosphericozonebyer.:iswesh:illseeinsection 15.4.)
The case against rnrbon dioxide is nOI comlly proven. but it """ms increasingly finn.
242
13 Alkanes l
13.5 Reactions of alkanes

Apart from cracking and re-forming. there are two important reactions of alkanes,
namely combustion and halogenatiOfl . We shall look at each in tum .
1 Combustion
Fuels
Asmentionedatthestanofthetopic,mostofthealkanesthatareproducedfromerude
oa are burned as fuels. Their complete combustion is a highly exOlhermic process:
1
:~~ + 20/g} ----t COh} + 2Hp(l) ~H! = ---8901.:Jmol-
Afi! =- 13J68k.Jmoi- 1
Methi!ne(nattJralgas)isreplacingcrudeoilandco;ilasthefuelinsomepo,Ne<st<1tions,in
an attempt to ctJt down on greeohouse gas emissions
UsetheeqtJationsabovetoG1lrnlatethepercentagereductioninG1rbondioxide
prodtJcedperkJwhennattJralgasreplacesfueloilinapowerstation
Answe r
Thecombu51ionofcoalinacoal-fired
For methane. the equat ion tell tJs that sgokJ of ene<gy are r~eased when 1 mol of G1rbon
powefstationcanberepresentedas
dioxide is formed:
follows: 1
carbondmXJde produced pedJ = B90 = 1.12 x 10-1 mciU- 1
C(s} + 0;,(9)---->COi(g)
<Vr, ~-"94kJmot- 1
For fu~ oil. 13 368kJ of energy are r~e..sed when 20mol of carbon dioxide are formed
2
Assumingthatcoalis100%carbon, carbondioxideproducedpe<kJ = ~ = 1.S0x10- 1 molkJ- 1
13 3
whatwouklbethepercentageteductioo
Thepercentagereductionisthereforegivenby
incarbondioxkleproducedperkJif
naturalgasreplacescoalinapowl'f 100x 150 - 1.1 2 = 25%
1.50
station?
Using quantitative combustion data in the determination of empirical

andmolecularformulae
Under the right conditions, combustion of a hydrocarbon can be rnrried out
quamirntivdy(tlutis ,in 1()(1,i,yield). Thequantitiesofthereaaantsand products can
bemeasuredtoahighdegreeofprecision, bymeasuringeithertheirvolu,nesortheir
masses. The following worked example shows how this can be put to use in finding
outtheformulaeofhydrocarbons
Worked example
10cm1 of a gaseous alkane were mixed with 100cml of oxygen and sparked to came
complete combustion. On cooling to the original temperature (290K), the volume of gas
was found to be 75cml. This redtJced to 3Scm1 on shaking with conceotrated aqtJeom
soditJmhy<lroxide.Whatistheformulaofthea lkane?
10cm1 ofagaseousa lkanewefemixed
with1S0cm1 ofoxygenandsparked. Answe r
Oncoolingtothe0<iginaltemperature At 290K, all the water prodoced on combustion w ill be a liquid. The 75cm1 of gas must
{290K),thevolumeof gaswaslound therelorebecomposedolc<1rbondioxide,alongwithanexcessofunre..ctedoxygen.The
tobe120cm1.Thisreducedto70cm1 carbondioxidewill beabsorbedbytheaqueoussodiumhydroxide,so40anl(7S-35)of
onshakingwithrnncentratedaqueoos carbondioxidewereproduced.Usir,gAYDgadro'slaw(seesection4.13),if10cm1 ofalkane
wdiumh'jOroxide.Wha t istheformulaof prndlJ{e40anlofc<1rbondioxide,thenl moleculeofalkaneprodoces4moleculesolcarbon
thealkane? dioxide.The<eforethea lkanecontains4carbonatoms,soitsformulaisC 4H10
243
ORGANIC CHEMISTRY
Incomplete combustion
lf the air supply is limited, the combustion of alkanes is incomplete . The hydrogen
atoms in the alkane are always oxidised to \\':Iler. but the carbon acoms either remain
as elemental carlxm (producing a black SOO{y name), or undergo panial oxidmion to
carbon monoxide. Bo!:h reactions are less exO{herrnic than comple1e combustion:
C 6H 11 + 90 1 ----+ H 10(1) + 6C0 1(g) llH 9 = ---4160kJmol- 1

C6H11 + 601 ----+ 6H 10(1) + 6CO(s) llH .. = - 2470 1,,J mor 1
C 6Hiz + 0 1 ----+ 6H 10(1) + 6C(g) il.H,. = - 18001.:J mol- 1
2 Halogenation
Alkanes undergo substitution reaaions with halogens :
CH; + Xz ----+ CH,X + HX
Methanere:ictsvigorouslywithfluorine.eveninthedarkandmn:x>mtempernture.
With chlorine and bromine. noreacrionocrursunlessthereact:antsareh<-atedor
exposed to ultraviolet light. With iodine, no reaction occurs 31 all . The trend in the
cakulated AH of the reactions macches tha! of the C- X bond energies (see T3ble 13.4).
Table13 .4 Bomienthalpi!.'5andenthalpli.-;of
c- x bond e nth.i lpy/kJnlOl 1 Aflfortherextlon/kJrnol- 1
reactionf'halogen1ub'itilutionreactiomwith
methane
The mechanism of the halogenation reaction

The halogen31ion re3ction involves radicals (see section 12.8). When initia!ed
(staned) by ultraviolet light. experiments h3ve shown that one phOlon can muse the
production of many thousands of molecules of chloromethane from chlorine and
meth3ne . Once the photon has staned the re3ction off, the re3ction rnn continue
on its own for 3 Jong time. Siudies on the effectiveness of various frequencies of
ultravioletHghthavesuggestedth31thephoton initiatesthereactionbyspliningthe
chlorinemoleculehomolytically(seesection 12.8):
0)
We can predict the next step of the reaction by simple bond enthalpy calculations.
The chlorine atoms formed by the splitting of the chlorine molecule are highly
reactive. They 3re lihly to re3ct with the next molecule they collide with . In the
mixcure we have juSI chlorine molecules and methane molecules. Reaction of a
chlorine31omwithachlorinemolecule:
a: ~ a ------) c1-c1 + c1 ,,,

might well occur, but it does n{){ lead anywhere. lt merely uses up one chlorine atom
toproducean{){her.
Reaction with methane could conceivably occur in one of two ways:
H H
ct ...... H -=
="'c~- H ------} H- a + ~- H
I I (3)
H H
~ .,,, H
Cl - C.....__ +H 0
H (4)
244
13 Alkanes l
In r,,action (3), a C- H bond has b=n broken, and a H---Cl bond has been formed.
B'.C- H) = 413kJm0! 1
El'.H---Cl) = 43lkJmol'
Overall.
Affw = 413 - 431 = -1 8"-Jmor-'

U5ethefollowir,gbondentha lpiesto
calculatetheAflvaluesolreactions In reaction (4), a C- H bond has been broken, and a C---Cl bond has been formed.
{3)and(4)usingbromine insteadof
B'.C---Cl) = 338kJmor'
cMorine.lsreactk>n(3) stillmo,elikelyto
occurthan(4)ifchlorineisreptacedby
bromine?
E{C- Br) = 276kJmot-1
E(H - Br) = 366kJmor1 So reaction (3) is slightly exOl:hermic, whereas reaaion (4) is highly endOl:hermic.
Reaction (3) is therefore much more likely to take place
The methyl radical formed in reaction (3) is equally as reaaive as a chlorine atom .
It is likely to reacr with the first molecule it coJHdes with. If it collides with a chlorine
molecule, the following reaction is possible:
H
I
H- C - Cl + CJ' (5)
I
H
Ml = act-cl) - a::c---cl) = 242 - 338 = - 96 }rJmor'

Ther<"3ctionishighly=cxhermic,soitislikelytooccur.lfthemethylradic3l
coJHdes with 3 meth,me molecule, the following re-action" could occur:
H H H H
H - ~ ,,..---.. "H'_:::-c!; _ H --4 H- ~ - H + ~ - H (6)
I I I I
H H H H
Reaction (6), like re3ction (2), does ncx lead us anywher<". A hydrogen atom has
been transferred from a methane molecule IO a methyl radical. forming a methane
moleculeandancxhermethylradical!
Let us now take stock of the situation. In the initiation reaction (1), we have
produced two reactive chlorine atoms. On energetic grounds. the two most likely
reactionsafterthatare(3)and (5):
Cl' + C H4 ---t C H3 + HCI

CHj + C11 ---t C HJCI + Cl' ,,,
(3)
Afterthesetwore-actionshavetakenplacewehave:
used up one molecule of methane, and one molecule of chlorine

produced one molecule of chloromethane, 3nd one molecule of hydrogen chloride
used upa chlorineatom,butregeneratedancxherone.
lf we add equations (3) and (5) cogether, the Cl' radical on the left-hand side of
equation (3) 'cancels' with the Cl' radical on the right-hand side of equation (5). The
same is true of the CH j radical. So the sum of r<"actions (3) and (5) is:
Cl' + C H_, + CHj + C11 ---t C H j + HC! + C H3 Cl + Cl'

andtheoverallequationforthereactionis:
245
ORGANIC CHEMISTRY
The chlorine atom has aaed as a homogeneous catalyst (see section 8 .6). It has
taken pan in the reacrion, but has nOI been used up during it.
Re:ictions (3) and (5) together constitute a never-ending c h ain R'aa ion. They
could,intheory.continueuntilallthernethaneand c hk>r:inehadbeenconvened
into chloromethane and hydrogen chloride. This s itumion does no1 occur in practice.
however. As was mentioned above, one photon initiates the production of many
thousandsofmoleculesofchlo rometh:rne - butonlythousands, nOlmillions . Eventually
the chain re:iaion comprising reactions (3) and (5) Slops. because there is a (small)
chancethatt,voradicalscouldcollidewitheachother.10 fom,astablemolerule:
Cl' + Cl' ----t Cl1 (7)

CHj + C l' ----t C HJCI (8)
CHj + CH3 ----+ CH,- CHl (9)
Any of these reactions would use up the carnlysis' Cl' and rn;. and so stop the chaifl
reaction. It would require anolher phcxon ro split another chlorine molecule in order
co resmn the chain. Overall. the chlorination of methm-,., is an example of a radical
s u bst itution reaction . The different stages of the chain reaction are named as follows:
C11 ---t2C!'
Cl' + C H_, ---+ CH j + HCl

CH3 + Cli ---+ C H 3Cl + Cl'
l propat,2tion
Cl' + Cl' ---+ Cl, )

CHj + Cl' ---+ CH 3Cl tmhi.u Wn
CHj + CH j ---+ CH 3--C H 3
By-productsofthehalogenationreaction
As the reaction takes place , the concentration of methane is being reduced , and
the concentration of chloromethane is increasing . Chlorine atoms are therefore
increasingly likely to colHde with molecules of chloromethane. cau s ing the following
re-actions to take place :
Cl' + CH 3C1 ---+ HC! + ' CH 1Cl

' CH 1C\ + C11 ---+ CH 1C1 2 + Cl'
Further substitution. giving dichloromethane. trichloromethane and eventually
tetrachloromethane , is therefore to be expected. A mixture is in fact formed.
Ancther intere.sting set of by-products are c hlorinated ethanes. These arise from the
ethane produced in termination reaction (9) undergoing a similar set of sub.stitution
Cl' + CH1 C H 3 ---+ HCI + CH 1CH{

CH 3CH i + Cl 1 ---+ CH1 CH 1Cl + Cl'
These chloroethanes are produced in only very small amounts, as might be
expected , since only a small quantity of ethane is produced in reaction (9). But their
presence amongstthereactionproducts addsweig httothemechanis mdescribed
here : without the formation of ethane from two methyl radicals. c hlorinated ethane
Co mmercially, the chlorination of methane is important for the production of

degreasing and cleansing solvents. The mixture of products is readily separated by
frac tional distillation (see Table 13.5). If only o ne product is required. it can be made
to predominate by mixing Cl, and CH.i in suitable proportions .
Tabte13.5 Thedifferentbo ili ngpointsofthe llolllngpo[ntr c

chlommetharie-;all owthemtobeseparatedby
fractionaldi1t1l!abon CH 1CI
rn,q,
CHCI,
246
13 Alkanes l
Halogenation of higher alkanes

A useful way of classifying organic halide.s. alcohols, radicals and rnrbocations is
to place them in one of the three categories primary. secondary and IC'rtiary,
depending on the number of alkyl groups joined 10 the central carbon atom. Table
JJ.6describesthisdassification.
Table 13 .6 Pr imary, ,;econdarya11dterti.iry

ce11tres.Themethy!gro11pCH,- i1al'io
Number
ofayl
Typeof
centre
..........
cla11ifiedasapr imarycl.'fltre
"""" R--<: H1- CH1CH,CI chloroethane

CHiCH,CH, ' theprop-1-ylradlcal
5!.'CO!ldary R,CH-
tertiary R,C-
'",
I
CH 1- ~ - CI 2..:hloro-2methylbutane
CH,CH 1
'"
I
CH 1- C' the 2methylprop2ylradical
I
'"
There are two mOflochloropropane isomers : 1--chloropropane, CH 3CH,CT-1 2CL and
2--chloropropane. CH 3CliCJCH 3. When propane reacrs with chlorine, a mixture of the
two monochloio- compounds is produced . This is because the chlorine atom can
abstract either one of the primary (end-earbon) hydrogens or one of the secondary
(middle-carlxm)hydrogens:
Cl' + CH1- CHz-CH1 ----+ CH 1- CH 1-CH ;' + H-CI
Becausetheratioofprimaryhydrogens1osecondaryhydrogensis6: 2,or3 : I, it
might be expected on probability grounds that the ratio of 1-ehk>ropropane to 2-ehloio-
propane in the produa should also be 3 : I . However, this assumes that the ab5traaion
ofa primaryhydrogenandofasecondaryhydrogenarebothequallylikely.
In fact, it is found thattheratioofl-ehloropropaneto2-ehloropropaneisne-:irly
I : I, which suggests thac the secondary hydrogen atoms are three times more likely to
beabstmcted,andthiscancelsouttheprobabilityeffect.
With bromine, the effect is even more pronounced . Here che ratio of
l -bromopropane to 2-bromopropane is I : 30. showing that the bromine atom is far
more selective as to which hydrogen atom ii abstracts . Because of the inductive
cffectofthealkylgroups(seepage248),thesecondaryprop-2-ylradicalismore
stable than the primary prop- l -yl radical. and is therefore more likely to form :
CH3----CH- - -CH3
prop-l,yl<3dical:ooe:dr,-lgroup
247
ORGANIC CHEMISTRY
The inductive effect of alkyl groups

C---C bonds are essenti3lly non -pobr, owi n g to the equal electron egativities of
thernrbon a!ornsac each end. lfoneof thecarbon atoms is electron deficient
insomeway(forexample,bybeingsurroundedbyonlysevenelectrons, asin
a radical), the other carbon atom rnn panially compensate for this deficiency
by acting as an electron reservoir'. This reservoireffectisnotsoapparentwith
C- H bonds. because the bonding electrons are much closer to the hydrogen
So the methyl radical: H

I
,..,c :.__
H H
H
. /
is much less stable than the ethyl rad ical: C H 1 --- C "-.
H
H
/
which in tum is less stable than the prop-2-yl radical: C H i --- ' C
"c:H,
(The arrow on the bond represents the drift of electrons away from
theCH 1 group.)
experiencesanevengreatersrnbilisation.owingtotheinductiveeffectof
rbrrealkyl groups.
The same effect is n{){iced with carbocations. Por ex3mple.
+ / rn1
it is much easier to form the 2-methylprop-2-yl cation: C H 1---- C ' \
H G-1,
I
than it is to form the methyl cation: ; c.. . _
H H
(See Topic 14. p age2S83ndTopic t5.page272.)
248
13 Alkanes l
Worked example
Predict the major product formed during the mooobromination of
CHiCHiCH1CH1
b (CH1l1CH --C H1
Answer
Of the N/0 possible rad Kais looned by hydroge<1 abstractioo from bl.Jtane, the secondary
radical CH1CHiC H"CHi is more sta~e thari the primary radK".i!I CH1CH1CH1CH / , so
2-bromobutane is the most likely product
b AlthotJghtheratioofprimaryhydrogenstotertiaryhydrogeois9:1 in
2-methyfpropane, the tertiary radical (CH 3)1C' is much more stable than the primary
radical (CHiliCH- CH/ , so 2-bromo-2-methyfpropane is the most likely product
Draw al l the possible mooobromoalkaf)l'S derived from the re;ictkm between bromine and
2-methyfbutane, (CHi)iCH-C H1CH1, arid predict, with a r&JSOO, which one will be the
majorpmduct
Alkanes formthehomciogousseriesofgeoeralformula Keyreactions youshou ldknow

C,,Hi,..1 Combustion
They show structural {chain) isomerism ,md, in wme case-;, c 0 Hy + (n + *)Oi .... neo., +fHiO
optical isomerism
Fiee-radicalwbstitution:
TheycanbeextractedfromcrudeoHbylractionaldistiltation
Theycanbe cracked and re-formed toproduceusefull~s c.Hi,..;;, + Xi--tC0Hin.1X + HX fX = ClorBr)
arid petrochemical leedstod1
Their main use is as a source of !'llergy by combustion.
Theyreactwithchkirineorbrominein free-radica l
substitution reactioo1,givingchkiro-orbromoatk,mes
Thereaiethreestagestoari!dK.alchainreaction - initiatlon ,
propagation and term ination
249
ORGANIC CHEMISTRY

Pleaseseethedata5ectionoftheCDforanyA, valuesyou 2 A reaction mechanism shows the individual steps that take
may need. plac:eduringareaction.
a Methanereactswithbromineinthepresenceof
1 Crude oil is a nat urally occurring flammable liquid which
ultravioletrad iationtoformseveralproducts.
cons.istsofacomplexmixtureofhydrcx:arbons. lnorder Two of these products are bromomethane and hydrogen
to separate the hydrocarbons the crude oil is subjected to bromide.
fractionaldi!.tillation.
a Explainwhatismeantbythefolla,vingterms. i Writeanequationforthereactionbetweenmethane
and bromine to make bromomethane and hydrogen
i hydrocarbon
bromide [1]
ii fractionaldistillation 121
ii Nameoneotherbromine-containingorganic
b Undecane, C11 H1~. isalongchainhydrocarbonwhich is
productwhichisformedwhenmethanereacts
present in crude oil
with bromine. (1]
SlKh long chain hydrocarbons are 'cracked' to produce
iii The mechanism for this reaction is called radical
alkanes and alkenes which have smaller molecules.
substitution
i Give theconditionsfor two diffe rent processesby
De5Cribe the mechanism for the radical substitution of
which long chain molecules may be cracked
methane by bromine to make bromomethane
ii Undecane,C ,, H,.,canbecrac:kedtoformpentane,
Use the mechanism to suggest why a small amount of
C,H,,,and a nalkene.
ethane is also formed. [7]
Construct a balanced equation for this reaction (3)
Pentane, C5Hu, exhibits structural isomerism. {OCR Chemistry A Unit F322 Q4 (part) January 2010]
c i Draw the three structural isomers of pentane.
ii Thethreei'iOffiersofpentane have different boiling
points.
Whichofyouri50!Tler5hasthehighestboilingpoint?
Suggestanexplanationforyouranswer. (6)
The unsaturated hydrocarbon, E, is obtained by cracking
hexaneandisimportantinthechemical industry.
Thestandardenthalpychangeofcombustionof E is
- 2059kJmol"""1.
d Define the term standard enthalpy change of
combustion . 121
When 0.47 g of E was completely burnt in air, the heat
producedrai5edthetemperatureof200gofwaterby
27.5C.Assumenoheatlossesoccurredduringthis
experiment.
e i Use relevant data from the data section on the CD
tocalculatetheamountofheatreleasedinthis
experiment.
ii Use the data above and your answer to i to calculate
therelativemolecularmass,M"of E. (4)
f Deduce the molecular formula of E. ( 1)
{Cambridge International AS & A Level Chemistry 9701, Pdper
22 Q3 November 2010]
250
AS Level
Organic chem ist ry
14 Alkenes
Functlon al g~:
Learning outcomes
',-, / By thi!idofth is topicyou shouldbeableto
/ '
Anotherc/auofhydrocarbon, the
14.1a) interpretandusethe geoeral. strl.ld:ural.displa)'edaridskeletal formul.:teofthe
allames
a/kenet,lsdim.Jssedlnthlstop/c. 14.3a) describeandexplainthes.ha pesof. and boodangles i1\thee tl1 aneandethene
Alkenescontalnacarbon-<arbon moleculesinterms ofoandn bonds. andpredictthes.hapesof,andbood
double bond, which Is much more ang~ in,otherrelated molecules
reactive thanacilrbon-<arbons/ng/e 1 5.2a) describe the chemistry of al~enes as exemp li fied, whefe relevant, by the
bond. The characteristic react/on followi ngreactions ofethene arn:l propene(indlld ing the Mart.ovnil:ovaddition
ofa/keneslselectrophl//caddltlon. ofasyrnmetric electro~ Hes toa lkenesvsingp,openeasanexample}:
Manya/kenes,ejpe<:la//yetnene,are addition of h~rogen. steam.hydrogenhalidesandhalogens
w,y lmporranr Industrial chemkals oxidatioobycold.dilute.Midifiedmangana\e(Vl)ionstofofm thediol
The additi on polymerisation of oxidatioobyhot,concentrated.acidifiedmanganate<vl)lonsleading tothe
a/kenes and of wbfrlrured etheMs ruptu re of t hec;irbon-<arbondoublebondinordertodeterminethepoi.ition
results in many ~fr.ii plastics. of all:ene linkages inlargermoleo.iles
pol)merr.;ation<-alsoTo?(28)
15.2b) describe the mechaniYn of electro~ ilic addition in alkenes, using bromine/
ethene andh~rogenbromidw'propeneasexamples
15.2d describe ardexplaintheinductiveeffectsofalkylgroupsonthestab~ityof
c;itior"61ormedduringelectrophikaddition
1S.2dl describe the characteristics of addition polymerisatioo as exemplified by
poly(ethene) ardPvC
15.2e) deducetherepeat unit ofanaddilionpolymerobtainedfromagivenmollOmef
Csee alsolopic2 8)
15.21) identify the mooomerb) p,esent in a given section of an addition polymer (500
a~ Topic 28)
15.2g) recognisethediffirulty ofthed~lofpoly(alkene)s,i.e. noo-biodegrada bil ity
andharmful combustion p,oducts
14.1 Introduction
The sm, ight--ch3in alkclK'S form 3 hom ologous series with the geneF.ol fomm la C,.,Hz,,.
They h." -e many reac tiOfls i n = = with the a lhnes ( 3lkenes with th~ or more
a ubon a toms conta in both C-H and C--C bonds. ju st like a lk:ines). a nd their
physical ~ n ies. s uc h as boiling points. 31"C veiy simila r (see Table 14.1). Re:ictions
d the double bond arc very different , however, and these domin a1e alke ne d,emistl)".
tile double bond being m uch "'"' re.ani,e ttun a C--C single bond.
251
ORGANIC CHEMISTRY
Table 14 .1 B01lingpoif1B of some alk.enes

a!ld.i lk.;mes
Bol llngpolntl"C Bol llngpolntlC
2-methWfopane 2-methy~opene
penlal\l' pent-1-ene
Fi gure 14.1 Twasp 2 carbonatom1canfonn

aabondandaxbondinethene
Wesawinsection3 .15that!hebondingin
ethene consists of a cr-bonded framework
c~.~ ~ ... H
of two carbon atoms bonded to each
<Xherandtothefourhydrogenatoms
H
;:~ ~CH1 (see Figu.., 14. la). Thisleavesaporbital
on each carbon morn. which can then
overlapsideways,giving theitbond
(seefigurel4 . lb)
The presence o f the It bond confers cwo
specfalcharacteristics onthestructureand
..,.activityofalkenes:
reactionwithelectrophiles .
Hindered rotation
Unlike the C---C o bood in ethane, which
alk>wsa:xnpletefreedomofra:ationatr<n111
temperature, the II bond in ethene fixes the
two ends d the molecule in their relative
orientations.lnordertotwisioneendwith
=pea co the a1her, it would be necessary
to break the II bond and then re-fom,
it . lbiswouklrequireaninpu!ofabout
degree of rotation 3()()kJmor- 1, whichisfarbeyondtheenergy
Flgure14.2 Hinderedmtatiooaroundthe avaUableatnor:m altemper.uure.s. Therefore,
c ~ -c OOubk>bond in tile blil-2-enes noroutionoccur,;aroundtheC=Cdouble
bond (seeFigure\4.2).Thislargeenergy
252
14 Alkenes l
requi=i.>ent contraSls with a barrier to rotation of Oflly 12kJffiOl 1 in ethane. which is =dily
avaibble to molecules from thennal ene,gy at room temperature. The"' is therefore almos1
completely !OCil freedom of ro1ation about the C---C bonds in alkanes.
Hinde!ro ro1:ation allows the e,:isience of geometrical (cis----tmns) =
= (see section 12.6.
and also the next section in this topic). Notice from Figure 14.2 that the Imus isomer of
but-2-ene is more stable than the cis isomer by 4kJffiOl 1. This differeoce in stability occurs
withmostiso mersofalkenes.andissignifieantin.somenaruralalkenes (see thepanelbelow
for two examples).
Cis- trans isomerism in nature

Double lxmds that occur in panicular compounds in nature are usually of a fixed
geometry. Whether the double bond is cis or trans is imponant to its biological
function . Two examples are described here.
Polyunsaturated oils
The unsaturated fatty adds in cenain vegetable oils are considered to
behealthierforusthanthesaturatedfattyaddsfound in animal fats.
However, it is not so much the degree of unsaturation that is imponant.
but the type of isomerism that exiSls around the double bonds. Cis
double bonds are considered to be more healthy than trrms ones. fany
adds contai ning trans double bonds are thought to be no healthier than
the fully saturated adds. One of the most healthy is cis--cis-linoleic add.
~co,,
- ;, "' which rnn be converted in the body into an unsaturated prostaglandin
(seeFigurel4 .3)
The correct balance of the various prostaglandins found in the body
is essential for healthy circulation, effective nerve transmission and for
o- o - ~ maintainingthecorrectionicbalancewithincells.
l, o, Ret ina l
Q,-~- ~CO,H The essential process that converts the arrival of a photon on the
l.0 ~ t o- o
retina of the eye into a nerve impulse to the brain involves a molecule
called rhodopsin. Pan of the molecule is a protein (called opsin) and
partisan unsaturated aldehydernlled 11-cis-retinal. This aldehyde
absorbsHghtS1ronglyatawavelengthof500nm,nearthemiddle
o I of the visible spectrum. Within a few picoseconds of the absorption
of a photon, the cis isomer of retinal isomerises to the trans isomer
~''" (see Figure 14.4). Thiscausesthealdehydeendofthe molecule to
move about 0.5 nm away from the hydrophobic hydrocarbon end.
which in tum blocks the movement o f sodium ions through cell
OH H OH H
membranes, and triggers a nerve impulse. (A single photon can block
aprostaglandin the movement of more than a million sodium ions.) Once it has been
Flgu re 14.3 Conver'>ionold'i-cis-linoleic formed. the /rans-retinal diffuses away from the opsin pl'O{ein. and
acidtoanurn.aturatedpimtaglandin takes several minutes to be re-isomerised to the cis isomer.
Flgure 14.4 Canversionaf

a'>-rebnaltatran5relirialby
theabl.orptiooafaphoton
of light
253
ORGANIC CHEMISTRY
Reaction with electrophiles

The ethene molecule is flat - bol:h caJbon atoms and all four hydrogen atoms lie in
the same plane . The electrons in the It lxmd protrude from this plane. both abo,"'
and below (see Figure 14. lb). This ready availability of electron density anmcts a
variety of elearophiles (see section 12.7) 10 an alkene molecule, allowing a much
greaterrnngeofreactionsthanoccurswithalkanes.

The principles of nomenclature for alkenes are similar co those used lO name alkanes .
The longesc carbon chain that contains the c=c bond is first identified, and then
the side bmnches are named and positioned along the longeSI chain. Then, are two
additional pieces of infonnation that the name needs to convey:
the position of the double bond along the chain
if appropriate. whether the groups around the d01Jble bond a"' in a cis o r a /rans
arrnngemem.
The position of the double bond is designated by including a number befo"' the
"--ene' at the end of the name , cor"'sponding to the chain po.sition of the first carlxm
in the c=c bond.
ci<-pent-2--ene 3-propylhex- l--ene

(NOie th31 although the lo ngest carbon chain conrnin s seven atoms , this chain does
not contain the c=c bond. and so is disregarded .)
In addition to the chain (and optical) isomerism shown by the alkanes, alkenes
show two Ol:her types of isomerism: position31 and geometrk3l. Bec3use of these
two additirnrnl types of isomerism, there are m:,ny more 3Jkene isomers th3n 3Jk3ne
isomers with 3 given number of rnrbon 3!oms. For example, 3Jthough there 3re only
two alkanes with the fonnula GiH, 0, there 3re no fewer than four 3[kenes with the
fonnulaGiH 8 (,..,.,.Figure 14.5).
Figure 14.5 !somersoffoor-carbooalkalll.'5

anda lKeries
>-
2-methylprop~ne
ApMI from 3-methy!pent-1-ene, thl'l'e

are 14otheralkeneisomerswiththe
c, alkeoes
r
2-methylpropene
molecularfOfmulaCGH1i
Worked example
Alt hough the first alkane to show optical isomerism has the molecuk11 formula C7H16 (see
1 Threeofthesehavethesamecarbori
the worked ex.-imple on page 236). the first chiral alkene has the molecular formu!a C6H11
skeletooas3-methylpeot-1-ene.Oraw
Oraw it s structural formula, and rame ii.
theirstructurallormulae,andname
them Answe r
2 Oftheother11,fivehavethextme Thelour diffe rentgroupsthatarenecessaryloracarbonatomtobeachiralcrotrearein
carbonskeletooashex.ane,five thiscaseH,CH1,C1H1 andCH=CH 1. Thestructureistherelore:
havethes.amecarbonsl:eleton
as2-methylpent.-me,andooe '",
I
hasthesamecarboosl:eletooas CH 1- CH, - C- CH = CH,
2,2-dimethylbutane.Orawolltthe
ske\etalformulaeof theseother i
11isomefs
Thealkene'1namei1 3-methylpent-1-ene.
254
14 Alkenes l
14.3 Reactions of alkenes

The double bond in a lkenes is composed of a strong o bond and a relatively we:ik
It bond. The CJ bond has its electron density betwl"en the atoms but the It bond
electrons an, on the surface of the molecule and so they are readily available. Alkenes
react by using these 11-bond electrons to form new CJ bonds to Ol:her atoms. leaving
the original CJ bond intact. Nonnally, this re.suits in only one molecule of product
being produced from two molecules of reactant. that is . an addition reaction (...,.,.
section\2.7):
CH 1=CH 1 + A - B ----+ A-CHI- C H , - B
AdditiOfl reactions of alkenes are invariably exOl:hermic. The energy needed to break
the It bond and the A- B bond is Jess than that given out when the C- A and C- B
bondsarefom,ed.Forexample:
CH 1= C H 1 + H - H ----t C H 1-CH 1 tl.H .. = - 137 kJmoC 1
Afi .. =-901,:J mol- l

Bemuse they are able to absorb' (that is, react with) funher hydrogen atoms
in this way , alkenes are sometimes referred to as uns aturate d hydrocarbons .
Alkanes, 011 the other hand, which h.tve all the spare valencies of their carbon
atoms used up by bonding with hydrogen atoms, are termed s aturated
hydrocarbons .
1 Hydrogenation
Alkenes can be hydrogenated to alk.tnes by reaaing them with hydrogen gas. The
reaaio11does11aocrurreadilywithoutaGit.1lyst, butwithplatinumitproceeds
srnoothlyatl'<X>!llternperarureand pressure. CornrnercLdly,alkencsthernselves
are11everhydrogenatedtoalk.t11es(thealke11esarevaluablefeedstocksforfunher
reaaions,whereasthealk.tnes producedhavevalueonlyasfuels). But the reaction
isimponaminthernanufactureofsolidorserni-solidfats(margarine)frornvegetable
oils . In the commercial reaction the less effective, but cheaper, metal nickel is used as
arntalyst,under a hig her pressure:
R--CH= CH- R' + Hz ________. R- CH 1- C H z- R'
Flgure14.6 P.irtial hydmgenationof

1unfloweroilproduce1thesemi-1~ id1Pfead
255
ORGANIC CHEMISTRY
2 Addition of bromine
Unlikealkanes , alkenesreactwithbrornineatroomternperature, andeveninthe
dark . The reaction cakes pbce either with bromine water. or with 3 solution of
bromineinanorganicsolventsuchashexaneor!richloroethane:
roomtrmper~rur,,m ~
CH 1=CH, + Br, Br-CHr-CH 1- Br
With bromine water, the major product is 2-bromoethanoL B.CH,CH,OH. The

reaction is very fast - the orange bromine solution is rapidly decolorised . This is an
excellent test for the presence of a c=c double bond, since few O!:her comJX>unds
decolorise bromine water so rapidly.
Fig u re 14.7 Alke11e1d!.>colorisebrom ine
water
"-~
~- ~ ---"
,..----c.:)----.."
s,... The mechanism of the addition of bromine to an alkene

~. The reaction is an e kctrophillc addition. like most of the reactions of alkenes . A.s
Br'- we have seen, the pro!ruding It bond of cthene is an electron -rich area . This &-- area
figure 14.8 The electron-rich K bond imluc!"i (see section 3.12) induces a dipole in an appl'O<lching bromine molecule , by repelling
a dipole in the bromine molecule the electrons of the Br--Br bond (see Figure 14.8).
Eventually , the Br--Br bond breaks completely, heterolytically (see section 12.8). to
form a bromide ion . The It electrons rearran ge to form a CJ bond from one of the
carbon atoms to the neares! bromine. The movemem of electrons away from the
other carbon atom resuhs in the production of a carbocatio n (see Figure 14.9) .
F1gure14.9TheBr-1lr bondbl!'aks.<mda
carbocationi1lorml.'d
There is a small amount of evidence 10 su ggesc that in some cases a lone pair of
electrons on the bromine atom can form a dative bond to !he cationic carbon atom.
spreading out the charge (see Figure 14.10).
Figure 14.10 Thelonepaironbrominecan

form a dative bond
Finally. the bromide ion acts as a nucleophile and forms a (dative) bond to the
rnrbocation(seeFigure 14.11).
256
14 Alkenes l
Flgure14 .11 TheffeebmmideKlnbondsto

thecarbocatian
,,
H. ...._, I ,,.-
t- c
H......... 1:H
Other nucleophiles rnn also 31tack the carbocation. In bromine water. for example,
the water molecule is present in a much higher concentration than the bromide ion.
so is more effective as a nudeophile (see Figun,- 14.12).
Flgure14.12 lnbrominewate1,thl'wate1
molecu~ acts as the mKleophi~ H-b/H
L ,.
H
. . . . . \ ,H
The incorp;:>ration of a water molecule. and the consequent produaion of the
bromoakohoL is good evidena,- for this suggested mechanism via an intermediate
caibocation. Anoiher piece of evidence that suppons the two-step mechanism is
the incorporation of foreign ' anions when bromination is carried out in an aqueous
solutio n containing a mixture of various salts :
The ratio of CICH 2CH 2Brto 0 1NOCH,CH,Br in the products reflects the (Ci-) : (NOJ- 1
ratiointhesolution,showingthmthecaibocatioo picksupthefirstanionitcollides
with,aswouldbe=pectedforacatiooofsuchhighreactivity.
3 Addition of hydrogen halides

The hydrogen halides HCl. HBr and Hl all react with alkenes to give halogenoalkanes.
Eitherthe (gaseous) hydrogen halide is bubbled directly through thealkene. or
ethanoicaddisusedasasolvent.(Aqueous solutionsofhydrogen halides such a s
hydrochloricaddcann01:beusedforthisreactionbecausetheycausetheproduction
ofalcohols,asweshallsee.shonly.)
The mechanism o f this electrophilic addition reaction is s imilar to that of

bromination , but in this case the electrophile already has a permanent dipole . The
Hi.. end of the H-Br molecule is attracted to the It bond in the initial step shown
inFigurel4 .13.
Flgu re 14.13 Theelec:trophilicadditk>oof

hydrogl.'nbromidetoether.e
257
ORGANIC CHEMISTRY
The positionofthe bromineatom

With the reaction between hydrogen bromide and propene, cwo different . isomeric,
products could form:
B,
CH,- !H - CH,
-f
l-bromopropme
CHJ- CH = CH 1 + HBr
CHJ- CH 1- CH 1 - Br
l-b=oprop,ne
When the reaction is rnrried out, it is found that 2-bromopropane is by far the mator
product: almost no 1-bromopropane is fonned. This can be =plained as follows
The position of the bromine atom along the chain is detennined by the position of
thep;:,sitivechargeintheintem1edi3ternrbocation:
CHJ- CH +- CH 3 + Br-
secondaryprop-2.yl
crboction
CH 3 - CHi - CH 1 + + Br- CH 3 - CH 1 - CH 1 - Br
primarvproplyl
carbocation
This. in tum. is determined by which end of the double bond the HIit of the HBr attaches
itselfto.Wesawinthepanelonpage248thattheinduaiveelectron-donatingeffectof
methyl gl'OIJps causes the prop-2-yl radical !O be more stable than the prop-l -yl radirnl.
The effect is even mo..,. pronounced with caibocations, which have a carbon atom that
is surro1mded by only six electrons. The secondary prop-2-yl carlxx:ation is much mo..,.
stable than the primary prop--1 -yl caibocation, and so the ~ adds on to position l of
the double bond, rather than position 2 (see Figu..,. 14.14).
Flgure14.14 Whentllehydrogenadd1 CH1---- CH ---- r,

ontoposit,Onl,thel!\Ofe1table!ol'Cond.iry
carbOG1tiani1f01ml.'dThebl\!l'arrnws
representtheinductrl'eeffectsoftheallyl .. B;-
CH1- CH~CH, CH,- r ---- cH,
~t)
Teniaryrnrbocationssuchas
1;-
a..,.evenmorestablethansecondarycarbocations.So2-methylpropene..,.actswith
hydrogen bromide lo give 2-bron,o-2-methylpropane:
Cf1 Cf, /CH1

/C = CH1 + HBr ---t /c,
CH, CH1 Br
258
14 Alkenes l
Markovnikov'srule
In 1869 the Russbn cherni51 Vladimir Markovnikov formulated a rule to predia the
Markovnikov's rule states that when HX orientationoftheadditionofahydrogenhalideroan unsyrnmetricalalkene(that
addstoadoublebond: is, one in which the two ends of the d01Jble bond a"' nOI the same, with one end
theh'jl]rogenatomattachestothe having more hydrogen morns 31tached to the C=C group than the cxher). He stated
carboothatalre.-idyhasthemost that when HX adds to an unsymmetrical alkene. the hydrogen attaches itself to the
hydmgens,or least substituted end of the C=C double bond (that is, the end that already has
thee~rophHeaddsintheorientation the most hydrogen atoms). A bener formulation . based on what we now know of
thatproducesthemoststab!e the mechanism, states that an electrophile adds to an unsymmetrical alkene in the
inte<mediatecation. orientation that produces the most stable intermediate carlx>cation.
Worked example
Predictandnametheproductsofthelollowingreactions
CH1=CH-CH1-CH1 + HCI ---> b {CH 3).,C=CH-CH3 + HBr--->
Answer
The reaction could produce ~ther CH 3-C"H-CH1CH 3 or cH 1-CH1-C H1CHi
astheintermediatecation.Thefirstoneismorestable,beingasecoodarycarbocation
This will ~ to the formation of CH 3CHCICH 1CH1, 2-chlorobutane, as product
b The tertiary carbocation (CH 3)iC-C HiCHi is more stable than the secondary
carbocafon {CH 3)iCH- C H-CH3, so the product will be {CHi}.,CBr- CH1CHi,
2-bromo-2-rnethylbutane
PredictandnametheproductsoftheloHowingreoctioos
/CH,
2 CH,CH,CH,CH = C,
CH,CH,
4 Hydration
In the presence of an acid. water undergoes an dearophilic addition reaction with
alkenes to produce alcohols. In the laboratory. this is rnrried out in two stages.
Ethene (for example) is absorbed in concentrated sulfuric acid. with cooling. to form
ethylhydrogensulfate:
CzH, + tt,so~ ---t C1H,-O--S01H
The sulfuric acid therefore acts as a catalyst. The sodium salts of long--chain alkyl
hydrogensulfate.s finda useasanionicdetergems.
Industrially. the hydration of alkenes is the major way of manufacturing ethanol,
propan-2-01 and butan-2--ol. The alkene and steam are passed over a phosphoric acid
catalyst absorbed onto porous pumice (to give it a large surface area) at a pressure of
70atmandatemperamreof30()C:
Phosphoricacidisusedbernuse. likesulfuricacid. itis anon -volatile add . Although

sulfuricacidisthecheaperofthetwo.itisanoxidisingagent.sosomeby-products
259
ORGANIC CHEMISTRY
are formed with it. The mechanism is 3n elearophiHc addition. \\-ith W (from the
add)astheinitialelectrophile(seeFigurel4.15). H'"isregenemtedinthelaststep,
andsocanbeusedagain.
Flgure14.15 Thehydrationofethene
Worked example
The hydratioo re;iction follows Markovn ikov's rule. What will be the strncture of the alcohol
formed from the hydration of e;ich of the following?
a pmpene b 2-methylbut-2-{'ne
Predkt which akohols will be formed Answe r

fromthehydrationofeachof the a The most stable carbocatioo formed from CH1- CH=CHi and W is CH~ H-CH 3,
followinga lkenes soprnpan-2-o!willbeproduced
1 2-methy!but-1-erte b Likewise, CH 3CHr-C(CHi)., is the most stable carbocatkm formed from
2 2-methylbut-2-ene 2-methylbut-2-{'ne,so2-methyl butan-2-olwill be theproduct
As can be seen from pan a of the worked example alx,ve. the hydration of alk- l--enes
always produces albn-2--ols, rather than alkan- 1--ols. The primaiy alcohols have to
be made by a different route . This is reflecu,d in their cos! - primaiy alcohols co.st at
leas! cwice as much per litre a.s do the corresponding secondaiy alcohols. (Alcohols
are veiy useful intermediates from which a varieiy of organic compounds can be
made . Some of their reactions are described in Topic 16.)
5 Oxidative addition with potassium

manganate(VII)
A pan from the decolorisation of bromine water, another veiy good test for the
presence of a carbon-carbon double bond is the reaction between alkenes and dilute
acidified potassium manganate{Vll). KMnO/aq) . When alkenes are shaken with the
reagent. its purple colour disappears. Identification of the product shows that a diol
hasbeenfom>ed:
([OJ represents an oxygen atom that has been given by the manganate{V]l).)
The reaction occurs rapidly at room temperature, whereas potassium
manganate{V]l) will only oxidise other compounds (such as alcohols and
aldehydes) slowlyundertheseconditions. ltisthereforea useful test for the
presenceofanalkene.
Testsfor a lkenes
Alkeoesrapidly decokirisebrominewater(seepage256)
Alkeoesrapidlydernkirisedilutepotass.iummar,ganate{VII).
6 Oxidative cleavage with hot potassium

manganate(VII)
When heated with acidified potassium manganate( Vll). the c=c double bond splits
completely. The products from the oxidation depend on the degre,, of substitution on
thec=c l:xmd(.seeTable 14.2).
260
14 Alkenes l
Tab1e 14.2 ProdlJCtslmmthecle.iv.ig.eof

ll thedoublebondcarbon ls: TIMtntheDJ11dls.:lproductw lll be :
double bonds by pot.11sium m;mganate{Vll)
co,
CH,:
'
0
R- C,,1-
'o,
Two examples are shown in Figure 14.16.
Flgure 14.16 Produ(tsof oxidativecleavage

bypotassiummanganatl'(VII)
will give
Worked example
Use Table 14.2topredictthl'productsoftheoxklativede;ivagebypotassium
m3nganate(VII) of the following compounds
Answer
i1 Splittingthedooblebornlinthemidd!egives
O '", O -'",
which, according to Table 14.2, 'Wi ll give carbon dioxide, COi, andcydohexaoorie
0 0
b Similarsplittinggives
e3'", _. G(",
whicheventualtywillprodoce
Geraniolisanalcoholthatoccurs
inoilofroseandotherllower
essences. lt s51:ructurallormulais
{CH i ).,C==CHCHiCHiC{CH,)=CHCHiOH
Whatarethestnicturesofthethree
compoonds/Ofmedbyoxidationwithhot
acid ifiedpotassiummanganate(Vll)?
Ct
261
ORGANIC CHEMISTRY
;;:;::;::;:::::7;~".!:'~:,:~'.'.'::. 14.4 Addition polymerisation

~ 1t: ;r:~ymerisca lled anaddition Formation of poly(ethene)
ln 1933, chemists working 31 !Cl in Britain disco,,.,,.,,J by c hance th31 when ethene was
subjectedtohighp=sure.sinthep..,senceof atrnceofoxygen , itproducedasoftwhite
solid . This solid was poly(ethene), and this ,vas the stan of the enonnous (multimiUion
dollar and multimillion tonnage worldwide) indusuy based on addition polymers.
H H
t J1
I I
c- c
~ n (o > 5000)
p:,ly{ethe<><)(LDl'E)
Po ly(ethene), commonly called polythene. is termed an additio n polyme r bc,,cause

one molecule is made from many ethene units (mono mC'rs) adding together. without
the co-production of any small molecule (contrast the process of condensation
polymerisation - see section 28.J). Jusc as in all Ol:her addition ..,-actions of ethene. the
c=c double bond is r,,placed by a C-----C single bond, and two carbon atoms make
two new single bonds to OUler morns. The original reacrion conditions are still used
with little modification to produce low.d<'n s it y potr(eth<'n e) or I.DPE. Sometimes
anorganicperoxideisused instead of oxygen asaninitiatoroftheradicalchain
reaction . Using a different catalyst. developed by Karl Ziegler and Giulio Nana in
19S3. ethene can be polymerised at much lmver pressures to produce high.dC'nslty
poly(<'thc nC') or HDPE .
H H
t J1
I I
c- c
~ nO> nXOOJ
poly(ethtn<)(HDl'E)
The major differences between the strucrures of LOPE and HOPE are that:
the average chain length of LOPE is much shoner than that of HOPE
thechainsofLOPEarebrnnched.whereasthechainsofHDPEareunbrnnched.
These differences have an effect on the physical propenies, and hence the uses, of
the two different types of poly(ethene) (see Table 14.J). So. by altering the chain
length and the degree of branching, the physical propenies ofpoly(ethene) can be
alteredtosuitthepurposeforwhich itistobeused.
Table14.3 Prnpeftie,;anduse1oflDP'E
Property or use Polymer
andHDPf
density Mgh
melting point approx. no 0 c
temi le 'itrength higher
flexibility very flexible muchll)()fer'9,d
polyth ene bags.electrical b0We1. buckets.oate1
imul.ition.dus tbin liners
Addition polymerisation of other alkenes

The physical propenies of a polymer can be changed by altering the structure
of the monomer. This is discussed in Topic 28. Here we shall briefly mention just
three other common polymers made from substituted ethene molecules, in which
262
14 Alkenes l
one of the hydrogen atoms has been replaced by anOl:her morn or group. The three
are polypropene. polystyrene (polyphenylethene) and polyvinyl chloride. PVC
(polychloroethene). Table 14.4 lists their scrucrures and some o f their uses .
Table 14 .4 Structure1andu1e1of Polymer (show ing two repeat units)
polypropene,polyc:hl()f{)ethene;md
polyphenylethene pofypmpene packaging,rnntainer1,
rope-;, tarpets, thermal
- r"Y',--1-
underwearandfleec:i,s
- CH1 C~,
polyc:hkxoethene{pofyvioylchlorkle,l'VC) guttering,waterpipe1,
'!'y")'t
window ffame1, Moor
CH,=C HCI
-' Cl C~
pt,enyletherie polyphenylethene(polyst)'fene) pmtectivepackag ing,

mooelkit1,heatimu!abon
The disposal of polymers

NOi: only an,- plastics and polymers very useful materials for a host of applications. the
energyrequilftllentsfortheirmanufacnm,a,.,farlessthanforequh,alernproducts
made from such materials as aluminium, glass or st=L With all these materials, however,
we are then left with the problem of how to dispose of them at the end of their u.seful
life. For =ample. metals from old cars can be recycled and glass can be re-worked. but
lxxh of these require a large input of energy. Similady JX>lymers need a .suitable method
of disposal. which needs to be safe and envirorunentally friendly. l>lethods are nOY."
availableth:itfilthisde.scription.andwhichrequirelittleornoenergyinput.
Polyalkenes. being effectively very long-chain alkanes, are chemically inert . They
biodegrade only very slowly in the environment. Although there are baaeria that can
Table 14.5 Terti<HY C-H txmds are weaker metabolise straight-chain alkanes once they have been funaionalised' by oxidation
than primary C- H bond1 somewhere along the chain, they find branched-chain alkanes more difficult to
BondenthalpylkJmol- 1 degrade. Therefore. they can attack HOPE more easily than LOPE. On the other hand.
LOPE is more sensitive to being broken down by sunlight . The Jess compaa nature
of the chains. and the presence of the weaker teniary C-H bonds (see Table 14.5),
H1C--H
allows ph01o-oxidation to cake place more readily (see Figure 14.17).
--
'"-' ~ R~c - o---+-o- H
,/ '
Flgure14 .1 7Photo-<Jxklotionofl1.'rliary
po!yalkane-; Poly(chloroethene) is Jess inen. The C---Cl bond can be attacked by alkalis
(see seaion 15.3) and can undergo rupture in ultraviolet lig ht (C---Cl bond
enthalpy = 338kJmol 1).
Despite these possible methods of degradation. most addition polymers can
p;:,tentially cause environmental problen1s when their useful lives are over. There are
four methods that are used, or are being developed, to allow their safe disposal.
1 Incin erat io n - the enthalpy change of combusiion of all polymers is strongly
=01hem1ic. Under the right conditions. incineration can provide useful energy
263
ORGANIC CHEMISTRY
for space heating or power generation. The process requires a high. rnrefully
controlledtemperntu..,.iftheforrnatiOflofpollutantssuchasthep;:,isonousgases
carbon monoxide and phosgene. COCl,. is to be avoided. Poly(chloroethene) is a
particular problem, as the highly dangerous compound 'dioxin' (see section 25.4)
can be formed unle.s.s the conditions are carefully controlled. The chlorine atoms
in poly(chloroethene) have to end up somewhere. of course. The preferred
combustion product is hydrogen chloride gas, which can subsequently be absorbed
2 Recycling - many polymers can be melted and re-moulded . For this process to
produce m:uerfals th31 industry can use, at a price thac is competitive with newly
made mmeriaL the recycled polymer has to be clean. and of Ofle type (for example,
all polyalkene, or all poly(chloroethene)) .
.l Dcp o lym crisatio n - heating polymers IO high temperatures in the absence of air
oroxygen(pyrolysis) cancausetheirchainstobreakdown intoalkeneunits . The
processissimilartothecrackingoflong-ehain hydrocarbons intoalkenes(see
section \J .3). The monomers produced can be sepamed by fractional distillation
4 Bacte ri a l fer m e nt at io n - under the rig ht conditions, and with an optimal strain
of bacteria, some polymers ( mainly the polyalkenes and the polyesters, see
section 26.4) can be degraded quite rapidly. The solid polymer is usually firsi:
fragmented into very small pieces, and panially phowlysed . Useful combusi:ible
gases areproducedduring thefermentation, which can be used asan energy
14.5 Preparing alkenes

1 Cracking of alkanes
Thesmaller a lkenesethene. propeneand butadienea..,-madecommert:iallyby
cracking, as we saw in section 13.3. The methcxl is ncx of great use for preparing a
specific alkene in the laboratory, however, because it gives a random selection of
alkenes . Forexample:
hutwithoteamat800C
C HiC H 2}ioCHJ C HiCH 2hC Hl + CH1C H=CH 1 + 2CH 1=CH 1
Flgure 14.18 Alkelll'Sareprodu(edby

thecrackirigoflong-cha in alkan!.'5(1ee
sectjon13.3)Crudeoillsheatedafldpa11ed
throughthe1ecatalyticu..d:ingtowers
264
14 Alkenes l
2 Dehydration of alcohols
This is the reverse- of the hydration reaction on page 2S9. Heating ethanol with
concentrated sulfuric acid to 180C produce.s ethene. Concentrated phosphoric acid
may also be used. Alcohols also dehydrate when their vapours are passed over
strongly heated aluminium oxide:
eon<.H,S0 1 lllS0"C
CH1-CH 20H - - - - - - - CHrCH 2 + H 10
oonc.H1PO,iot.!OO"C
"'""'-,.,...~i......iAJ,o,
3 Elimination of HCI or HBr from chloro- or

bromoalkanes
This reaction is described in Topic 15. page 275 . For example:
t...t ............1
KOH + CH 1- CHCI---CH 1 _______. CH 1---CH=CH 1 + KC\ + H 10
Sometimes an elimination reaction like the dehydration or elimination of a hydrogen

halide described above results in more than one alkene product. For example
l...t witl,KOH
CH1CH,CHBrCH, dwo'-lmod.. ...l CH1CH=~HCH1 + CH1C~CH=CHi
U.stmlly, the more substituted alkene (that is. the one with the more alkyl groups
mtached to the C=C d01Jble bond) is more stable than the less substitu ted alkene.
So it is the more substituted alkene that is most likely to be formed , and 8())6 of the
productisbut-2--ene.
A lkenes contain a C=C dou~e bond, and have the general formula C..Hin
In addition to chain isomerism, alkenes show positiooal isomerism, and also geometrical (cis-trilfls) isomefism due to the restricted rotation
aroondttiedoublebond.
The ir characteristic reactKln is e lectrophi li c add ition . Unsymmetrical electrophiles add in accordance with Markovn ikov's ru le, with
the most slable carbocation being formed as intermed~te
Testsfofthepresenceofadoublebondincltx!ethedecoloris.-itionofbwminewate<,andthed~orisatiooofdiluteaqueous
potassiummanganate(VJI)
Ethenearidothl'falkenesformimpoctarit add itionpolymers suchaspolyther.e,polystyreneandPVC.
Keyreactionsyoushouldknow
Catalytich~rogenatioo(addifon)
"
CHi=CH- R+ Hi --. CH1-C Hi- R
Electrophilic addition~
in !hedark
CHi=CH- R + Br1 _______... CHiBr-C HBr- R
CHi=CH-R + HBr _______... CHi-CHBr- R
OxidatKJm:
ooldKMn04
CHi=CH- R+ (O) + H10 - - - CH1{0HKH(OH)- R
hotKMn04
CHi=CH- R+ 5[0] _______... COi + HOiC- R (+ HiO)
Poiymefis.-itioo
0.,atlOOOatrn
nCH1=CH- R______.. (CHi- CHRln
0<AIR3
265
ORGANIC CHEMISTRY

Ple-seethedatasectiotlof theCOfOfanyA,values'pOU d Poly(chloroethene)hastherepeatunitbelo.v.
""'""' are a ...ery useful series of hydrocarbons used

1 AlkenH widely
in~thesis.Alkenesaremorereactivethanallcanes
a What is the name of the pro:~ used to corwert
long-chainalkanesintofllOteusefulshorter<hain
alkenes1 [1]
b Etheneandsteamcanbeconvertedintoethanol. This repeat unit can be written as --CHz(HCI-
The equilibrium is srown below. One way to dispose of poly(chloroethene) is to react
C1H4(g)+H10<9) ;=. C1HsOH(g) AH,.--46kJmol- 1 itwith oxygenathightemperature. Thisiscal~
incineration.
LeChatelier's Principlec.lnbeusedtopredicttheeffect i Complete the following equation that shows the
of changing cond itions on the position of equilibrium. reaction taking place during incineration
i Namethecatalystusedinthisreaction (1)
iiStateLeChatelier'sPrinciple. (1) --C H1CHCI - + ... 02 -+ ... (Oz+ ... HiO + ... HCI
iii Ur.ingleChatelier'sPrinciple,predictandexplainthe 111
conditions that would g~ the maximum equilibrium ii Researchchemistshavereducedtheenvironmental
yield of ethanol from ethene and steam (3) impact of incineration by removing the HCI formed
iv Theactualcooditionsusedare60atmospheres from the waste gases.
pre ssure at300 C in the presence of a catalyst. SuggestatypeofreactantthatcouldbeU5E'dto
Comparethesecoriditionswithyouranswerto iii remove the HCI. [11
and comment on why these conditions are used. {3] e The di!>pOwl of potymers causes environmental damage
c Alkenesareusedtomakeadditionpolvmers. The repeat Researchchemistsaredevelopingpolymersthat
~it for an addition polymer is shown below. will reduce this environmental damage and flen'ase
sustainability.
De5cribe t\\"O Wil'fS in which chemists can reduce this
environmental damage. [2]
{OCR Chemistry A Uflir F322 05JanUiJf'/ }010/
What is the name of the monomer used to make this

polymer? [1)
266
AS Level
Organic chemistry
15 Halogenoalkanes
Functional group:
Learning outcomes
,. ~~-t Bytheeod ofthistopicyoushouldbeableto
14.1a) interpretandusethegetieral,strlidural,disp!ayedandske!etalformul<1eolthe
halogeooa lkanl's,amif)l'S(primaryon!y)andnitriles
X = F, CI, Br, I 16.1 a) recallthechemistryofhalogenoalkanesasexemplifiedby
Therearese veralfunctiona/groups the foHowing mideophilic substitution reactions of bromoethane: h~rolysis,
thatcon tainatoms(cal/edhetero fonationofnitriles,format ionof primaryaminesbyredctioowit hammooia
atoms)otherthancarbonand the el imination of hydroge<i bromide ffom 2-bromopropar.e
hydrogen. In this topic, compounds 16. 1 b) de,;cribe the ~ 1 ,md ~2 mechanisms of nudrophilk substitution in
containingaha/ogenatom-the hak>genoalkilne1indudir.gtheindtJctiveeflectsofal~groops(seeTopjc14)
ha/ogoenoa/kanes-arediscussed. 16.1cl recall that primary halogeooalkanes tend to reitcl via the ~2 mechanism; tertiary
Theha/ogenoa/kanesareareactive hak>genoa lkanes via the ~ 1 mechanism; and seamdary halogenoalkanes by a
and important class of compound mixtureofthetwo,depend ingonstructtJre
muchusedinorganicsynthesis. Their 16.2a)interpretthedifferentreactivitiesolhalogenoa lkanes{withparticularrefereoce
characteristicreactionisnuc/eophi/ic tohydrolysisandtotherelativestrengthsoftheC - Halbonds)
substitution. 16.2b)explaintheu,;esoffluoroalkanesandlloorohalogenoalkanesintermsoftheir
relative chemical inertness
16.2cl recognisethernocemabouttheeffectofch!orofllJOfoalkanesootheozooelayer.
15.1 Introduction
There are only a few nmumlly occurring organic halogen compounds. The mo.st
important is thyroxine, the hormone secreted by the thyroid gbnd . Synthetic org:,nic
halogen compounds have found m:tny uses. however. One of the mOISl imponam
uses is as imermedbtes in rnganic syntheses: they are readily formed from common
mmerfals. but can equally easily be tmnsfonned imo compounds containing many
differentfunctio=lgroups .
Flgure15.1 Thymxirie
,_~ h ",-!-co,
_y o--P-' '", ,
CFCs (chlorof\uoroc,ubons) are inert. vobtile liquids that at one time found favour as
the circubting fluids in refrigerators and air-conditioning units. They are now being
phased ont of use because of their destructh'e effect o n the oz.one byer, as we shall
see in section 15.4. Hal{){hane , CF 3CHB.Cl. is an impo,unt anaeS!hetic. a successor
to chloroform, CHC13. which was one of the first anaesthetics , introduced in the
early nineteenth century . The halons. such as CB.ClF,. are useful fire extinguishers.
Many polychloroalbnes are used as solvents. The nse of certain organochlorine
compounds as herbicides and insecticides is described in section 25.4.
Halogenoalbnes are generally colourless liquids. immiscible with and heavier
than water, with sweetish smells. Compared with the albnes, their boiling points are
267
ORGANl1.. CHEMISTRY
higher. with the boiling point rising from each chloroalkane to the corresponding
icxloalkane(se<."'figure 15.2). The main interntolecularforceinhalogen=lkane.sis
the van der Waals" induced dipole force. Therefon, their boiHng JX}ints incn,ase with
chainlength,justliketho.seofthealkanes.
Fig u re 15.2 B~lingpointsofthe

halogeooalkarie,;
Furthermore, as we would expect, the trend in boiling JX}int with halogen (Rd< RBr <
Rl) reflects the greater number of electrons available for induced dipole attraction from
chlorine to icxline (see section 11.1). In acklition. there is a small amount of permanent
dipole-dipole attrnction between molecules. This will be most imponant for the
chloroo.lkanes. becoming lesssoforthebromo- andicxloalkaflf"s(see Figure 15.J).
Flgure15.3Pennanentdipole-d ipole R.. - Ct'- R.. - c, Rk - Cfit R"* - cl'"

attractiomlnhak>geooa lkane1

Halogenoalkanes show chain. positional and optical isomerism. There are. for
example. five isomers with the formula Ctfi~r, as shown in Figure 15.4.
Flgure15.4 l'iomersofC,H.,Br
CH,........_cH;'CH,.........._CH,/B, CHysr
CH 1 CH 1
'
A and the 0--E pair an, positional isomers of one another. B and C an, also positional
isomers of each cther. B and C an,chain isomersofthectherthree. D and E an,
optical isomers of each O!her. They form a non-superimposable mirror-image pair
(seesection12.6).
A halogenoalkane is classed as primary . so.,xundary or te rtiary (see Table 13.6,
page 247) , depending on how many alkyl groups are attached to the carbon atom
joined to the halogen a!om :
R
I
R- C - Cl
I
R
a primuy bromoolbne ><CO<Wr)" loooilbne ttluy chloroolbne
268
15
In Figure 15.4. isomers A and B are primary, D and E are secondary, and C is
enl 1 1n
I
ceniary.
When a compound conmins two halogen a!OfllS , the number of positional isomers
increases sharply. There are only two chloroprop<lnes
Cl
I
CH 3 - CH1 - CH 1- Cl CH3 - CH- CH3
l-chloropropan~ 2-chloropropane
But ther<, are five dichloropropanes, two of which fom, mirror-image pairs with each Ol:her.
Worked example
Draw skeletal formulae of the five dkhloroprop.-mes, and explain which two form a mirror-
Answe r
Howmanypositiooalisomersarethere
Flgure15.5
:~ ;zCI
X
th e abovethree i>mersarenotchiral
~Cl
Cl~CI
of chlorobromoprop,me, CiH.BrCI? How

manyofthesearecapa~eofformin g (+)and(- )forms
optic:ali'iOmer,;?Orawtheirstructures
The naming of halogenoalkanes follows the rules given in Topic 12. The longest
caibonchainthatcontainsthehalogenatomistakencobethestem. Otherside
chains are added. and finally che prefix fluoro, chloro. bromo' or 'iodo' is included
together with a numeral showing the position of the halogen atom in the chain:
CH 3CH 2CHClCH3
ClCH 2CH(CH.i)CH,CH3 is l-chloro-2-methylbutane
CH 3-CCl3 is I.I.I -trichloroethane.
Worked example
Drawthestructurallormulaofeachof
thefollowingcompotmds. Name the following compounds
1 1,1,2-trkhloropropane
2 2-chloro-2-methylpmp.-me
'Jy" yy
Cl Br
Figure 15.6 B;ill-and..stic~ models of the
frYelsomersofC,H 0CIToemo1esp!ll'licalthe
Answe r
mok>cuk>, theloweristheOOlingpolntbec:au'>!' a 2,3-dichlorobutane
ofweakerv;indl'fwaa!s'bonding(st>esectioo b 2-bromo-4-chloropentaneor4-bromo-2-chloropentane
13.2) What type of isomerism !s exhibited t,y
isoml'r5 b ;mdc.7Whalcy;Jeisexhibitl'dby d
a!ld e7
b (+).2-chklrobtrtane. c (-).2-cMorobutane. d 1-chloro-2-me~ne. e 2-0lloro-2-methylprop.irie.

b.p.78C b.p.1s 0 c b.p.69C b.p.sooe
269
ORGANl1.. CHEMISTRY
15.3 Reactions of halogenoalkanes

Nucleophilic substitution reactions
Halogens 3re more electronegative than rnrbon. and so the C- H3I bond is strongly
pobrised d'< - Hall>-. During the re3ctions of halogenoalkanes, this bond breaks
heterolytirnllytogivethehalideion:
( 13)
The C* formed is then liable to attack by nudeophiles - anions or neutral molecules

th31po.s.sess3 lonepairofelectrons:
(lb)
OflenthenudeophileNU- willanac ktheCg, rnrbonbeforethehaHdeion has left:
The dominant reaction of habgenoalk:rnes is therefore nucleophilk substitutioIL The

"'
halide ion is replaced by 3 nudeophile . Whether mechanism (la + lb) or mechanism
(2) is followed depends on the structure of the haloge-noalkane (p rimary . .secondary or
teniary), the nature of the solvent, and the nature of the nude ophile. The panel below
describes the mechanisms o f nudeophilic substitution reactions. Table I S. I iUuscrates
how some common nudeophiles react with 3 halogenoalkane such as bromoethane.
Table 15 .1 Common nucleophi l!.'5 that react
wilhhalogenoalkan!.'5 fC'=~=- = '"~ - ~ - ~ _ _ , Produc.tswhen reacta:lwlth bromoethane
H,6 CH:,CH,OH + HBr
CH 1CH,OH +B r-
NH, CH,CH,NH, +H8r
cyankleK)(l CH:,CH,CN + 6r
CH,--0- CH 1CH,-O-CH1 + 8r
methylam ine NH,- CH, CH,CH, - NH - CH, + HBr
The differe nt mechanisms of nucleophilic substitution

reacti ons
If we rnny out kinetics experiments of the kind described in Topic 21 on the
hydrolysis of bromoalkanes by sodium hydroxide. we find two different extremes .
Th e SN1 reaction
The hydrolysis of 2-bromo-2-methylpropane is a f, rs1-ordc r re-action (for an
explan.~tion of the order of a reaction. and the rateeqo,ation, see Topic 21):
CHJ CHi
I I
CH3 - C - Br + OH- --4 CH 1 - C - OH + Br-
1 I
CH 3 CHJ
rate = k 1(RBr) (where Rilr is (Oil),CBr)

This means th3t the rate doubles if we double IRBrl. but if we double (or halve)
IOH""). the rate does not change at 3ll. The rate depends only on the concentration of
the bromoalkane; it is independent of the hydroxide concentration. Hydroxide ions
rnnnot therefore be involved in the rate.determining s te p - that is. the step in the
270
15 H,'enr' ,n I
overall reaction that is the slowest: the one that limits the overall rate of reactiOfl.
The first o f the two mechanisms given on page 270 (equation (13 + lb)) fits the
kinetics equation shown. The mechanism is shown in Figure IS.7.
Flgure 15.7 TheS"lhydrnly<;isof2-bromo-2-

methylpropane
CH 1
HC - J- cH, ~
CH 1
H,c- J- cH, .. :a,- ~ H

r
C- 1:-CH
1 1
"&;~ ~ w
The first step involves only the heterolysis of the C-Br bond. forming the
caibocation and a bromide ion. This is the slow Slep in the reaction. and hydroxide
ions do not take pan in it. If 101-fl were doubled, the rate of the second step
(carbocation + 01-r) might also double. Bue this second step is already faster than
the first one, sotherateoftheoverall reactionisnOl:affected .
This sequence of events is called the s ,.. 1 mechanism (Sub.siitution. Nucleophilic.
unimolecular). The re-:iction profile of the S,,l reaction is shown in figure 15.8.
The activation energy of the first step. .,. is high. owing to the energy required to
progresofruction break bonds - this is why this is the slm11 step. That of the second step. E.:,. is low -
Flgure15.8 ReactionprofilefortheS..1 oppositely charged ions anraa each other strongly.
hydrnlysisof2-brnmo-2-methy1prnpalle
TheSN2 reaction
The hydrolysis of bromomethane is a second.order reaaion:
CH 1 -Br + 01-t --> Oi 3 - 0H + Br

rate = k,IRBr]IOHl (where RBr is Oi 3 Br)
Dcx.Jbling either [RBrl or (01-t) wUJ double the rate of this reaction. (Doubling h;xh [RBrl
and IOE-r] wouk:I iocrease the rate four. fokl.) The hydrmdde ion concentration has as
much influence on the rate as the bromomethane concentration. We can therefore deduce
that both bromomethane arx:I hydrox:ide are invoh'ed in the rate-<letennining step
The second mechanism given on page 270 (equmion (2)) fits this kinetic
relationship. The mechanism is shown in Figure 15.9.
Flgure15.9 ToeS,.2hydrolylisof
bromomethane
The reaction is a continuous ont,Slep process. The complex shown in square

bracketsisnOl:anintermediate(unlikethecaibocationintheS,,l re-actiOfl)buta
tran..,;ition state. It is a half. way stage in the reaction. where the C-Br bond is stiJJ
getting longer and the O - C bond getti ng shoner.
This sequence of events is called the s,..2 mechanism (Substitution,
N ucleophilic. bimolecular). The e nergy profile of the S,,2 reaction is shown in
FigurelS.10.
Flgure15.10 ReactKlnprnfilefortheS,..2
hydroly'iis of bromomettiane [SO ,,r
.
R ROH+Br
progres,ofre.,dion
271
ORGANl1.. CHEMISTRY
Fig u re 15.11 Reaction profiles for the S"l How t h e re lat ive rates of Sr,i 1 and SN2 reactio n s depe n d
hydro!yl.isofprimaryandtertiarybromoallGlnes
We saw in Topic 13, page 248. and Topic 14, page 2S8. that alkyl g roups donate
electronsmcarlxx,ationsandradicalsbytheinductiveeffect. Thestability
primary c+ of rn rlxx,a tions increases in the order primary < secondary < tertiary . As the
0
tertiary c+ ~:~:i~n}:;:e:se: ;:g:~eb~~-- :~;. a;:~;~t:;:f:;ee:~P:: :::t r;;;;t:t: ~t:~:g
S,.I reaction will increase in the order primary< secondary< tertiary . (See
Topic 8 for a description of the relationship between the mag nitude of the
activationenergyandtherate o fa reaction .) Some observed relative rates are
given in Table 15. 2.
prog ress of reaction No carbocations are formed during the S,.2 reaction. and oiher factors now come
into play. The transition state has five groups arranged around the central rnrbon
Table 15.2 The S" 1 reaction is fastest with a morn. 1t is therefore more crowded than either the starting bromoa lkane or the
tertiary bromoa llGlne alcohol pnxluct. each of which has only four g roups around the central carbon
Co mpoun d Type
Hydrogen atoms are much smaller than alkyl groups. We therefore expect
SN1reactl o n
that the more alkyl groups there are around the central carbon atom. the more
CH,C H,Br
crowdedwillbechetransitionstate(seefigure 15.12), andthe higherwill be the
(CHi), CH8r sec:ond.iry activ:,tion energy E. (see Figure 15. 10). This will slow down the reactio n ( see
(CHi) 1CBr tertiary Table 15.3).
8~ 8~
Rg ure 15.1 2 TheS "2tramition'ila te ismore
crowded with a tertiary bromoaliGlfll'
-<=-- --C
-
e
Br Br
Table 15.3 The S,..2reac tioni1

la1te1twith ap rimary bro moalkane
~
Compou nd Type These two effects rei nforce each o ther - the S,.l reaction is faster with tertiary
halogenoalkanes than with primary h:ilogenoalk:rnes. whereas the S,.2 reaction is
CH1CH,8 r prim.iry 1000 faster with primary halogenoalkanes than with tertiary halogenoalkanes. Overall.
{CH,):,CH 8r ,,eamdary 10 we expect primary halogenoalkanes to react predominantly by the S,.2 mechanism.
tertiary halogenoalkanes to react predominantly by the S,.1 mechanism. and
(C Hi)1CBr tertiary
secondary halogenoalkanes to react by a mixture of the two (see Fig ure 15.13) .
Rg ure 15.1 3RelativeratesofS,..1andS,.2

hydrolysisre..ctiomfo r pfimary. secondary
alldterti .iryhalogenoallGlnes
primary ,ocondary tertiary
m
15 H,'enr' ,n I
1Hydrolysis
Some halogen0<1lkanes a..,- reactive enough to be hydrolysed to form alcohols just
byheatingwithwater(inpractice,amixedethanol- watersolventisusedbecause
halogenoalkanes are immiscible with water. but the ethanol is miscible with bol:h):
CH,
I
CH 3 - C - OH+HCl
I
CH,
The hydrolysis is quicker if it is carried out in ha1 aqueous sodium hydroxide:
boJunder"'n""'
CH1CH 1Br + NaOH(aq) - CH 1CH 10H + N aBr(aq)
The relative rates of hydrolysis of chloro-, bromo- and iodoalkanes can be studied by
dissolving the halogenoalkane in ethanol and adding aqueous silver nitrate. As the
halogen=lkane slowly hydrolyses, the halide ion is released. and forms a precipitate
R- X + HzO + Ag+ ----t R - OH + H~ + AgX(s)

Table IS.4showstheresultsobtained.
1::~:'.sli!vernitratecanbeusedtodistinguishbetweenofQi!nicchlorides, bromides and I

T.ible 1 5.4 Si~erhalkleprl'Cipi!Jtesformed Compoood Observation on ructio n with Colou r ofpntc:lpltillte
wtthhalogeooalkanes.Thecolou,.;ofthese AgN0 1 + H,O ln elhill nol
predpitatelaate1hownioffgu1E11 .1,page205
(CH.),CH-CI slightdoudinessafter1 hour
(CH.),CH-llr cloud inessappears.ifterafewminvtes paleueam
(CH,l,CH-I thickpredpitateappearswilhin.1minute pale yellow
Table 15.5 Comparingthecarboo--haloge11 lodoalkanesarethereforesecntobethemostreactivehalogenoalkanes,and

bood1tmigth1 chloroalkanes the least reactive. Fluoroalkanes do nOI react al all . This Group 17
llonde nt halpy/kJITIOl 1 trend corresponds to the strengths of the C- X bond . The weaker the bond (that is,
thesmallerthebondenthalpy) .theea.sierit istobreak(seeTable 15.5).
The bromoalkanes are the halogenoalkanes most often used in preparative organic
chemistry. Chloroalkanes react too slowly; iodoalkanes can be too reactive and slowly
decompose unless stored in the dark. ln addition. iodine is a much more expensive
element than bromine . We shall use hromoethane to illustrate subsequent reactions of
halogenoalkanes.
2Withammonia
The ammonia molecule contains a lone pair of electrons. The lower electroneg ativity
of nitrogen compared with oxygen makes ammonia a stronger nudeophile than
water. The reaction is as follows :
H/J- C~i + : Br -
CH,
;,:=: Hi N - C~i + NH/

CH,
ethylamine
273
ORGANl1.. CHEMISTRY
Because ammonia is a gas, the reaaants (in solution in ethanol) need !O be heated in
a sealed tube, to prevent the ammonia escaping.
The produa is called cthylamlnC'. Like ammonia itself. ethylarnine possesses a
Jone pair of electrons on its nitrogen atom. The electron-donating ethyl g roup makes
ethylamine even mo...- nudeophilic than ammonia . So, if an excess of bromoethane is
used, funherreactionscanoccur:
CHJC H1}lHi + CH,CHiBr ~ CH,C~ i CHiCHJ ( + HBr)

1
~H
diethy[;omine
ni~thvlamine
Finally. even triethylamine po,,;.sesses a Jone pair of electrons on its nitrogen atom. It
To avoid these funher reactions. an excess of ammonia is used . The propenies and
reactions of amines are described in Topic 27 .
3Withcyanide ions
Whenahalogenoalkaneisheatedunderrefluxwithasolutiondsodium (or
JXX3ssium) cy:,nideinethanol. anucleophilicsubstitu tionreactionoccursandthe
halogen is replaced bythecyanogroup:
The product is called propa nC'nltri!C'. Its name shows that it contains three carbon
atoms , although we staned with bromoethane, which has just two. The use of
cyanide is a goo:l method of increasing the length of a carbon chain by o ne carbon
atom. which can be useful in the synthesis of organic compounds. Nitrites can be
hydrolysed to carboxylic acids (see Topic 18) by heating under reflux with dilute
CHjCH 1- C ""' N + 2H 10 + W ---t CH1C H 1C0 1H + NH/

prop>n<>ic~
Nitriles can also be reduced to amines (,..,., Topic 27) by hydrogen with a nickel or
platinum catalyst:
Reflux
Heating under rdlux means to heat a flask so that the solvent boils continually. A
condenser is placed vertically in the neck d the flask to condense the solvent vapour
(see Figure 15.14) . This method allows the temperature of the reaction mixture to be
kept at the boiling point of the solvent (that is, the hig hest possible temperature for
that panicular solvent, so that slow organic reaaions can be speeded up as much as
1X>S5ible) withoutthesolventevaporating away.
15 H,'enr' ,n I
Flgure15.14 A reflux apparatus
e lectrical he at ing mantle

~~~~~~~~~
Elimination reactions of halogenoalkanes

Nucleophiles are electron-pair donors, donming to a positive or panially positive
caibonatom. Bas.,.sarealsoelectron-pairdonors. dOflatinga pairofelectronsma
positive hydrogen atom.
The hydroxide ion can act as a nucleophile :
The hydrogen atoms anached to carlxm a"' slig htly 5+ (see the rnble of
electronegativities on page S4). They are therefore wry slightly acidic . When a
halogen=lkane is reaaed with hydroxide ions under cenain conditions , an add-base
reaction can occur at the same time as the carlx>n---halogen bond is broken:
HO- H
An alkene has been formed by the cllmlna tlo n of hydrogen bromide from the
bromoalkane. The same =gent (hydroxide ion) can therefo.., carry out c,vo differern
types of reaction (subsiirutiOfl or elimination) when reacted with the same bromoalkane.
Bo{h reacrions do in fact occur at the same time, but the proportion of bromoalkane
moleculesthatundergodirninationcanbevaried.ltdependsOflthreefuctors:
the n ature o f the broma,lkane (primary. secondary or tertiary)

the streng th and physkalsi:z.eof thebase
thesolvemusedforthe re-:,ction .
In general , nucleophiHc substitution to form 3[cohols is favoured by:
primarybromoalkanes
bases o f weak o r medium .slrength. and small size
polarsolvemssuchaswater
e low tempe-rarure.
275
ORGANl1.. CHEMISTRY
On the {)(her hand. elimination to form alkenes is favoured by:
1eniarybromoalkanes
strong, bulky bases (such as potassium 2-methylprop-2-oxide. (CH_i),C-0-K')
less polar solvents such as ethanol
high temperature.
The m05I comnxmly used reagem is pornssium hydroxide dissolved in ethanol

and heated under reflux . PO!assiumhydroxideisusedbecauseitis moresoluble
in ethanol than is sodium hydroxide. Table IS.6 shows the results of a study of the
effects of solvent and halogenoalkane structure on the elimination :substicution ratio
Table15.6 EliminationsubsMution.{EIS)
r.itiainbromaalkane1
Forrnulaol
bromoa lkane
,,,...,
bro moalku,e
Ratio,
(CH,):,CHBr secondary 2.0moldm- OW in 60% ethanol '"

(CH,},CHBr secondary 2.0moldm- OW in 80% ethanol
(CH,},CHBr sernndary 2.0moldm- 1 00-inlOO'loethanol
{CH,}1C8r tertiary 2.omoldm-1 00-inlOO'loethanol
Comparing rows l lO 3 of Table IS.6 . we can .see that the elimination :substirution
ratio inc,.,.ases as the solvent becomes richer in ethanol. Comparing rows 3 and 4, ,ve
can see that the elimination :substitution ratio inc,.,.ases when we replace a secondary
bromide by a ieniaryone.
For e.Kh of the followirig comb1Mtions of rNgeots arid cooditioris, suggest whether
sub1titutiorioreHmiflillioriwillpredomiMle.StatetherNsonsloryourdioice
ii f1l'iltirigCH 3CH1CH1B1withNaOH(aq}
b he.Jtirig (CHi) 3CBr with NaOH iri ethanol
Givethestructurnllormulaafthe C fll'iltirig (CH1l1CHBr with {CH,>.ic - o - K
main productafNdiofthefollowir,g
Answer
Substitution predomiriate1 with a primary bromoa lkane ,md Of1 iri a polar soweflt.
1 (CH1}.,CH-CH1Br + Na0Hinethanol b Elimiriation predominatl".5 with a tertiary bromoalkane and Df1 iri a rioo-polar so,',oerit
2 CH1CH 1CHBrCH1CH1 + NaOH(aq) c Elimiflilli oo predominates with a secondary bmmoalkane arid a bu lky base
15.4 Chlorofluorocarbons and the

ozone layer
The c hklrofluorocarbons (CFCs) have almost ideal propenies for use as aerosol
propellants and rdrigeram heal -transfer fluids. They are chemically and biologically
inen (andhencesafetouseandhandle),andtheycanbee-:isilyliquefiedbypressure
a linleaboveatmosphericpressure. Althoughfairlyexpensivetoproduce (compared
to {)(her refrigerants like ammonia). they rapidly replaced <Xher fluids tha! had been
used. In the early 19705. however. concern was expressed that their very inenness was
a g lobal disadvantage . Once released into the environment. CFCs remain chemically
unchanged for ye-:irs. Being volatile. they can diffuse throughout the atmosphere ,
and eventually find their way into the stratosphe,.,. (alx x.n 20km above the Eanh's
su1face). Here they are exposed to the stronger ultraviolet rays of the Sun. Although
the carlxm-fluorine lxmd is very strong, the caibon--chlorine lxmd is weak enoug h lO
be split by ultraviolet light (.see Table IS.S). This forms atomic chlorine radicals. which
can upsel the delicately balanced equilibrium between ozone formation and ozone
ulttaviolfili:;ht
C F J C I - CF 3' + C l'
276
15 en,',n l
Some stratospheric chemistry
I Production of oxygen 3torns: o, ~ 20
(by absorp1.ion of UV light at 2S0nm "11velength)
Once oxygen atoms have formed. they can react with oxygen molecules to
produce ozone. which by absorption of ultraviolet light decomposes co re-form
oxygen atoms and oxygen molecules .
.? Natural ozone formation : 0 + 0 1 ~ Oi

.l Natural ozone depletion : 0 1 ~ o, + 0
(by absorp1.ion of UV light at 300 nm wavelength. thus reducing the levd of shon-
wavelength ultraviolet radiation from the Sun's rays al the Eanh's surface)
A steady state is set up in which the rate of production of ozone equals the rate of
its breakdown. Chlorine acoms disrupi the balance of this steady Slate by acting as a
homogeneous catalyst (see section 8.6) for the destruction of ozone :
<1 c1 + oi ----> cto + o,

S Cl0" + 0---->Cl" + 0 1
Reaction 5. in which chlorine 31oms are regenerated, involves the destruction of

the oxygen atoms needed !O make more ozone by the natural formation reaction (2).
In this way, chlorine atoms have a doubly depleting effect on oz.one concentration in
the atmosphere .
It has been estimated that one chlorine a!onl c:,n de.stroy over 105 oz.one molecules
before it eventually diffuses back into the lower atmosphere. There it can react with
water vapour to pnxluce hydrogen chloride, which can be flushed out by rain as
diluiehydrochloricacid .
Once the ozone hole' above Antarctic:, was discovered in 1985, g lobal agreements
were signed in Montreal (1989) and London (199()). As a resuh, the global production
of CFCs has been drastically reduced. In many of their applirntions they can be
replaced by hydrocarbons such as propane . It willstilltakeseveralderndesfor
natural regeneration reactions to allow the oz.one concentration to recover. but that
reco,..,ry is now well underway. Other .stratospheric pollutants such as nitric oxide
from high -(lying aircrafr also destroy ozone.
Flgure15.15 Theozooe'hole'l1an.lfeaolli'r
Antarctica where ozooelel'l'ls.iredepleted,
partirularlylns.prin9.A1imilardepletiooi1
ocrnrfingovertheAfctkaswell
277
ORGANl1.. CHEMISTRY
Flgure15.16 Depletionoftheozorie!a)'I?(
putshumomatir1oeasedri1kofs.kinconcer
a!lddamagetotheeyesby1hcirt-waveH'ngth
Wradiation(UV-8)
15.5 Preparing halogenoalkanes

1 From alkanes, by radical substitution
As we saw in section 13.5. this reaction works well with chlorine and bromine. It has
limitations in organic synthesis. ho,vever. since it is essemially a random process. It gives
3 mixture of isomers. 3nd multiple substitution often occurs. Nevenhde:s.s. it is often
usedindu.'itrially.wherefrnctionaldistillationcanseparntethedifferemproducts.Alkanes
that can form only one isomer of 3 nxmochloroalkane are the most suitable starting
materials .
0 + Cl 1 - - - - - - } u a
+ HO
g'CH, + Cl, ~ g 'CH,Cl + HCI
2 From alkenes, by electrophilic addition

\Ve saw in section 14.3 that the addition of chlorine or bromine to alkenes gives
1,2-dihalogenoalkanes:
The 3ddition of hydrogen h3lides to alkenes g ives monohalogenoalkanes. The

orientation of the halogen follows Markovnikov's rule (page 259). The reaction
works with hydrogen iodide as well as with hydrogen chloride and hydrogen
278
15
3 From alcohols, by nucleophilic substitution

These re-actions are co,,ered in dernil in secrion 16.3. There are several re-agents thac
can be used :
ronc. H 1SOf -t N~fu -t heat

CH1CHiOH + HBr CH1CHiBr + H 10
Ha logenoa lkanes conta ina &+- carbonatom.

Their ma 51: common redetioo is nucleophllit substitut ion . They also undergo eli mination re.actklns to give alkenes.
Their reactivity increase-; i11theorder C- F<C - Cl<C - Br<C - 1
e Fluoro-andchloroalkanesareusedassolve11ts,aerosolpropellantsar.drefrigerants.CFCsdamagetheozonelayerbybei11gphotolysed
to chlorine atoms, whic:h initiatecha inreactionsdestroyingozone
Halogenoalk,mes can be made fmm alkanes, alkenes and alcohols
(R = prirnary,secorKlaryortertiaryalkylunle11iotherwisestated.Allreactionsa!soWO<kwithClinsteadof8r,butmuchmoreslowly.)
Elimifliltion
R-CHi-CH1-Br -t OW - - - -- R-CH=CH1 + H10 + Br-

Nudeophilksub51itutiom
J>eatwtthNitOOlnwall'f
NH 3 ine!harciunde<pn-;su,e
R- Br+2NH 3 R- NHi + NH 48r
heat1tthNaCNlnetharci
R- CE N + Br-
R- C~H < ' R- CH1NHi
279
ORGAN!! HEMI RY

Pleasese('thedata,;,ectionoftheCOforanyA,.valuesyou For example, 1-bromopropane reacts with ammonia to
may-d
/-: : ~~'"'
form Pfop'flamine, CH3CH2CH2NH2.
1 Halogenoalk-havemanychemicaluses,particul.arly CH1CH2CH2Br + 2NH1 ~ CH1CH2CH2NH2 + N~Br

asintermediatesinorganicreactions. Three reactions of
i lodoethane is reacted with ammonia. Write an
1-brornobutane. CH~H2CH2CH2Br, areshoNn below.
equationlorthisreaction. [2]
"~~~~=~
ii The fint step in the mechanism of the reaction
between CH3CH2CH28r and NH1 is shoNn below. It is
incomplete
""r.::::o, Completethemechanis.m. lncluderelevantdipoles,

lonepairs,curly;,rrowsandthemissingproduct. [3]
CH3CH2CH=CH2
b A~udentinvestigatestherateofhydrolysisofsix
a For eac h reaction.statethereagentand50Mntused. [6] halogeooalkanes.
3
Thestudentmixes5cm ofetha!"IO!withlivedropsof
b \rVhen 1-iodobutane. CH~H2CH2CH2L is reacted under
thesameconditionsasthoseusedinreaction 1, halogenoalkane. This mixture is warmed to so c in a
butan- 1-ol is formed. waterbath.Thestudentadds5cm 1 ofaqueoussilver
\rVhatdifference.ifany.11:ouldtherebeintherateofthis nitrate, also heated to50C. tothehalogeooa1kane .
reaction compared to the reaction of 1-bromobutane? The time taken for a precipitate to form is recorded in a
Use appropriate data from the data section on the CO to results table
explain~answer. [3] The student repeats the whole experiment at 60 (
insteadofSO QC.
Dichlorodifluoromethane,CC12F:i,isanexampleofa
chlorofluorocarbon (CFC) that was formerly used as an
aerosol propellant. In Septembef 2007, at the Montreal
sUITVTlit. approximately 200 COI.Xltries agreed to phase out
theuseofCFCsby2020 . CH.CH,Cfii:CHz(I
c State two properties of CFCs that made them suitable as
aerosol propellants. [2]
d When CFCs are present in the upper atmO!iphere,
homolyticfis.siontakesplaceinthepresence ofultraviolet
light
i What is meant by the te!lll homo/ytic fiS5ion7
ii Suggestanequationforthehomolyticfissionof
CCl1F2 [2) Oescribeandexplainthefactorsthataffecttherateof
e The most common replacements f0< CFCs as aerosol hydrolysis of halogenoalkanes. Include ideas about
propellantsarehydrocarbonssuchaspropaneand the halogen in the halogenoalkanes
butane the groups attached to the C<lrbon of the
Suggest one disactvantage of these compounds as C<lrbon-halogen bond (the type of halogenoalkane)
aerosol l)fopellants. [1) the temperature of the ~drolysis.
{Cambridge /nternarion;,/AS &A Leve-I Chemi~ry9701, lnyouransweryoushouldlinktheevidencewithyour
P;,per 22 Q4 November 2010} explanation. [7]
2 This question is about halogenated tr,drocarbons. {OCR Chemistry A Unir F322 05 {lrr) January 2011 j
a Halogenoalk- undergo nucleophilic substitution
reactions with ammonia to form amines. Amines contain
the - NH2functionalgroup.
280
AS Level
Organic chemistry
16 Alcohols
Fu nctiona l group:
,_ Learning outcomes
0 '-.a+ By theeodofthistopicyoushouldbeableto
......._a+/
C H 14.1a) interpret andusethegeneral, structural,d isplayed and
/ : skeletal lormulaeof the akOOols (indudir,gprimary,
secondary ,md tertiary)
The - OH (hydroxyl) group occurs in many organic 17 .1 al recall the chemistry of akoliols, exemplifi ed by ethanol in
compounds. In addition to the alcohols, it forms a// or part thefo llowingreactio ns:rnmbu1tioo,1ubstitlllioo tog ive
ofthefunctiona/groupinsugars,phenolsandcarboxylic hal ogeooalkanes,reactioowith'>Odium,oxidatiooto
acids. In this topic we look at the reactions of the hydroxyl carbonylrnmpoundsandcarboxylicacids,dehydration
group when it is the only functional group in the molecule, to alkenes, lormationof estersbyesterifi cat ioowith
in the alcohols. The hydrogen atom attached to oxygen is ca rboxylkacids(part,'il'e alsolopic26)
slightly ad die, and the Ii+ nature of the carbon atom makes 17.1b) classifyhydroxyrnmpoundsi ntopri mary,secoodary
itsusceptibletonuc/eophi/icsubstitutionreactions. Primary andtertia ryalcohcl1, andsuggestcharacteristic
andse<ondarya/coholsa/soundergooxidation. disting uishingf&lctions, e.g. mildoxidatioo
17.1c) deduce the preseoceofa CH1CH(OH)- groupina n
akohol fromitsreactioowith alkal ineaqueousk>d ineto
form tri-iodomethane
16.1 Introduction
The alcohols form a homologous series with the general formula C,.H,,..,OH. They
occupy 3 cemral p;:>Sition in organic function3l g roup chemistry: they can be readily
convened to aldehydes 3nd carboxylic acids by oxidation, 3nd can be formed from
them by reduction; 3nd they can be convened to 3nd from halogenoalka nes by
nudeophilicsubstitution .
Alcohols are useful solvents themselves, but they 3re 3lso key intermediates in
the production of esters, which are important solvents for the paints and plastics
The polar -OH group readily forms hydrogen bonds to similar groups in (){her
molecu les . This accounts for the following major differences between the alcohols
3nd the corresponding 3lkanes.
The lower alcohols (C 1, C1, CJ and some isomers of C,) 3re totally miscible with
,v:uer, owin g to hydrogen bonding between the alcohol molecules and water
molecules(seeHgure 16.1).As thelengthofthealkylchainincreases,vander
Waals' attractions predominate between the molecules of the alcohol, and so the
miscibility with water decreases .
Flgure16.1 Hy{lmgenbondlngbetwl'l.'n
CH, 1t,, _,.....H ..
eth.ioolandwater
c< "t o,_
.. H _,.....H ..
"1
""
281
ORGANIC CHEMISTRY
The boiling points of the alcohols are all much higher than the corresponding
(isoelearonic) 3[kanes, owing to strong intermol=ular hydrogen bonding (see
Figure\6.2).
Figure 16.2 lntermo~rularh)\'.lrogen
txmd in g inethanDi H- lCH,- CH 1
/H,- 0, ..H- 0\
CH 1 H6 CH,- CH 1
Table 16.1 and Figure 16.3 show this large difference. A,; is usual in homologous
series. the boiling points increase as the number of catbon 3toms increases.
owing to increased van der Waals' attractions between the longer alkyl chains. The
enhancement of boiling point due to hydrogen bonding also d=reases, as the longer
chainsbecomemorealkane-like .
Tabte16.1 BoWrigpo inB of,;omeakohols

Enh .1nceme nt
anda lKaries electro ns In f-c-~-""~.,~,,~.,,- + - ~ " r.,~,,-,,----, ofbolll ng
the molecule pol n tl"C pol ntl"C pol n ttc
C,H, CH10H
C1H1
c,H, 0
C,H,,
C,H ,, OH
C7H, 0
Figure 16.3 Boilingpoint1ofsome.ilrnhol1

anda lK,mes
The electron pairs around the oxygen atom in alcohols are arranged in a similar way
to those around the oxygen acorn in the water molecule, as both have two lone pairs
ofelectrons (seeFigure\6.4).
0:-,[)
6
R 105 H As was mentioned in section 12.S. the alcohols are named by adding the suffix -or to
the al kane .stem of the compound . The longes! carbon chain thac contains the --OH
Figure 16.4 Toeoxygenatomln ,makohol group is chosen as the .stem. A numeral precedes the '-ol" to describe the position of
ha1twol011epair.;ofelectm111 the --OH group along the chain .
282
16 Alcohols I
Figu re 16.5 Mo~rul.irmodel1ofameth,m~. a - - - - - - - - -
bethanol,cpmpan1-ol, d p.-c::m-2-olarid
ebtrtan-1-ol
Worked example
Name the following compounds
CHi-CH(OH}-CHi-CH1
b CH1=CH-CH10H
c CHi-CH1-CH(CHil-CH10H
Answer
a Thelongest(andonty)carbonchaincontainsfourcarbooatoms.The - OHisonthe
secondatom,'iOlhealmholisbutan-2-ol
b Theth--carbonbaseisprope,ne.Takirigthe-OHgrouptobeonpositionl,thename
isthusprop-2-en-1-ol
c The longest chain contains four urbon atoms, with a methyl group on position 2 and the
-OH group on po~tioo 1. The compound is 2-methylbutan-1-ol
Alcohols show chain. positional 3nd optirnl isomerism (see section 12.6).
Alcohols are cbssed as primary, secondary or terti3ry, depending on the
number of alkyl groups that are anached to the carbon atom joined to the - OH
group. Of the five isomers with th.- formula G 1H 90H, two (A and 8 below) are
primary alcohols, two (C and D ) are secondary alco hols, and one (E) is a teniary
1 Describe the type of isomerism shown

bythefo!lowingpa irsofakohols,
whose structures are shown A
ii Aand B b B and E
c AandC d Cand D
2 Namethefivealrnholswhose
structures are shown. (Note: akohols C
and D willhavetheSdlTlename.)
The ethers
Et h ers are isomers of alcohols, but they do not contain the --OH group and so have
none of the reactions of alcohols, and do not form intermolecular hydrogen bonds.
283
ORGANIC CHEMISTRY
Hence they are fairly inen compounds with boiling points Jo,,,e, than those of the
isomeric alcohols. For example:
. . . . ., , a. . __,, ~o-........
H
diethyl ether, c.,Hl(,O, b.p. JS"C butan-l-ol. C 4H 100, b.p. l JS"C
They are quite good 31 dissolving organic con1pounds, and so are often used as
solvents
16.3 Reactions of alcohols

1 Combustion
All alcohols bum well in air, but only !he combustion of ethanol is of everyday
imponance :
The use of ethanol as a fuel has b=n mentioned in section IJ.4 .

For its uses as a fueL and as a common solvent . ethanol is marketed as methylated'
or 'rectified ' spirit . This contains about 9(m ethanol, together with 5% wa ter, 5%
me1hanoL and pyridine. The poisonous methanol is added to make it undrinkable,
and hence exemp! from the large excise duty that spirits attract . The pyridine gives it
abiuertaste,which makes it unpalatable.
The other reactions of alcohols can be divided into thr= groups :
reactions involving the breaking of the O -H bond

reactions involving the breaking of the C---0 bond
' / H
reactions of the C group (tertiary alcohols rnnnot show this group of
/ ""-oH reacrions).
2 Reactions involving the breaking of the

0 - H bond
With sodium metal
The hydroxyl hydrogen in alcohols is slig htly acidic, just like the hydrogen atoms in
w:iter. but the alcohols ionise to a lesser extent:
H - 0 - H ~ H--0- + H ~ K.,, = l.Ox 10- '"'mol1 dm~

R--0- H ~R--0- + H + K = l.Ox 10-16 mol 2 dm~
Alcohols liberate hydrogen gas when tre-:ited with sodium metal :
CH 3CH 10H + N a ---+ CHJCH 10~a+ + !Hz(g)
The reaction is less vigorous than that between sodium and water. The product
is called sodium ethoxide (compare sodium hydroxide. from water). This is a
white solid , which is soluble in ethanol and in water (to give a strongly alkaline
solution) .
All compounds containing -OH groups liberate hydrogen gas when treated with
sodium. The fizzing chm ensues is a gcxx1 tesc for the presence of an -OH group
(aslongaswaterisabsem).
0
Esterificat ion II
r,st~rs are compounds that contain the - C- 0 - group.
They rnn be obrnined by reac ting alcohols with rnrboxylic adds or with acyl
chlorides(seeTopics !Sand 26).
284
16 Alcohols I
alcohol + rnrboxylk acid ----> ester + water
For example:
0 0
CH1CH20H + CH3~ - 0H ::: CH1- ~ - 0 - CH1CH1 + HiO
It has been found that the oxygen in the water comes from the caiboxylic acid , and
the ---0--- in the ester comes from the alcohol. The methcxls of ester preparation w ill
bedealt withindeiailinTopics 18and 26
Estersa,.,usefulsolvents,andsevemlarealsoused, in small quantities, as
flavouringagentsinfruitdrinksandswects .
3 Reactions involving the breaking of the

C- 0 bond
Although the C- 0 bond is polarised cf'---or'.-, it is a strong bond. and does nOI: easily
breakheterolytirnlly:
I I
- C - OH -+ - C+ + - OH
I I
If, however, the oxygen is prownated, or bonded to a sulfur or phosphorus atom
the C- 0 bond is much more easily broken. As a rt,sult. alcohols undergo several
nud cophillc su bstitutio n re-actions.
Reaction with hydrochloric acid

Tertiary alcohols react easily with concentmted hydrochloric 3dd on sh.tking at room
ternperatun,. The n,3crionproceedsviatheS,.I mech.tnisrn (seesection 15.3):
CH, CHJ H
CH - b - O ~ H+ ~ CH
I
- c+ o
/
' I ' J I -.. o' '
CH 1 H CHJ H
CH, CH,
I I
c HJ- c +..-.: c1 - CHJ- T - Cl
1
CH, CH,
Secondary and prit113ry 3lcohols also n,3ct with concentrated hydrochloric add , but
at a slower mte. Anhydrous zinc chloride needs to be added as a catalyst. and the
mixrnn,n,quin,sheating :
This n,action is the basis of the I.u rns tes t to distinguish between primary. secondary
and tertiary 3kohols (see Table 16.2). It relies on the fact that alcohols an, soluble
in the reagent (concentmted HCl and ZnCl,) whereas chloroalkanes are not . and
therefore produce a doudinessinthesolution .
Typeofakohol Observatlo n onildd ln gcOll(.H C-tZ nCI,

R1COH (terti ary) immediatedou dines1appear1 inthe,;olution
R,CHOH {secondary) do udine11app.irentwithin5minutes
RCH,O H (primary) oodoudirll'ISappa1entunle11warmed
285
ORGANIC CHEMISTRY
Reactionwithphosphorus(V)chlorideorsulfurdichlorideoxide
Both of these reagents conven alcohols into chloroalkanes (see section 15.5). and in
bcxh rnses hydrogen chloride is evolved . This fizzing with PCls, and the production of
miscyfurnes.canbeused asatestforthepresenceofanalcohol(aslongaswateris
absent). Both reaaions occur on gently warming the reagents .
CH1C H 10H + PCls ----t CHlCH 1Cl + POC13 + HCl

CHjCH 10H + SOC\ 1 ----t CHlC H 1Cl + S0 1 + HCI
Reaction with hydrogen bromide

Alcohols can be convened into bromoa lkanes by reaaion with either concentrated
hydrobromk add o r a mixture of sodium bromide, concentrated sulfurk add and
water (50%). These react to give hydrogen bromide:
CHJ- CHz- o f H+
H
Reactionwithredphosphorusandbromineoriodine
These halogens react with phosphorus to give the phosphorus trihalides:
2P + 3Br 1 ----t 2PBr1

2P + 31 1 ----t 2Pl1
The phosphorus trihalides, for example phosphorus triicxlide, then react with alcohols
Reactionwithconcentratedsulfuricacid
Ethanol and concentrated sulfuric add react iogether to give the compound ethyl
hydrogensulfa!e:
0
II
CH 1 - CH 1- 0 H + H- 0 - ~- 0 - H ;.:::!::
0
0
II
G-:l1 - CH 1- 0 - h - O - H + H 10
The ethyl hydrogensu lfate can then undergo an elimina!ion reaction !o form
t ;;LCH ....!._'6 - SOJ--1

' '.
~ CH1= CH1+ H '+ HS04-
i
H1S04
As the sulfuric add is regenem!ed on elimination, i! is essentially a catalyst for the
286
16 Alcohols I
Concentrated phosphoric add also acts as a rntalyst for the ""'ction. This is often
preferredbecause , unlikesulfuricadd , itis nOlalsoanoxidi.singagent.andsothe
fom,mion d by-product.s is minimised .
hea1withH1POi
CHjCHiOH ----------t CH 2=CH 1 + H 10
A third method of dehydration is to pass the vaJX>ur of the alcohol over strongly
Al,o, .. J50"C
CHjCHiOH ----------t CH 1=CH 2 + H 10
Tenbry alcohols dehydrate very easily on warming with an add . The reaction goes
via the rnrbocation. which then l<:J6es a proton:
CH1 G-1 1 H
CH
1
- ~-
I
0-...
,
w .,..-
____,_ CH
1
- ~1..1..C(
...... ,
~
-H,O
CH 1 H G-11 :
(' 'fH,
CH1 - <(
- H+
~ rnl-r 1'CH1
CH,
CH,
Worked example
Dehydrating longef-d1a in alcohols {an give a mocture of alkroes. Suggest stnictures for the
alkenes possible from the dehydration of the alcohol 1-methykydohexanol
Whicha lkenewil lbethemoststable?
Answe r
The H and the OH of the water which is eliminated come from adjacent carbon atoms,
forming the C=C bond between them. There are three pos~bilities
Drawallthepossiblealkenesthatcould
beobtainedbythedehydrationof
6 c5 c5
AarKl Bareidl'lltical(rotatir.gAby180aroundaverticalaxisproduces B),sothereare
3-methylhexan-3-ol.Whichislikelyto twopo11iblea lkroes.Alker.e A/ Bisthemo1t1tablebecauseithasthreealkylgroups
bethe/ea.tstableofthesealkenes? around the dou~e bond, whel"l'dS alkene Chas only two {see al~o section 14.S)
4 Reactions of the >CH(OH) group

Oxidation
Prirnaryandsecondaryalcoholsaree:isilyoxidisedbyheatingwithanacidified
solution of pornssium dichromme(VI). The orange dichromate(VI) ions are reduced to
green chromium(Jll) ions. Teniary alcohols. however. are nOI easily oxidised .
287
ORGANIC CHEMISTRY
Secondary alcohols are m:idised toketones (see Topic 17):
CH 3 OH C H,
K,c,,o, H,S0.(oa) 'c=O
~c~ /
CH 1 H CH,
?")p n-2-ol
Primary alcohols are oxidised to aldehydes, which. in turn. are even more easily
oxidisedtocaiboxylicacids:
CH3CH2CH 10 H K,c,,;_: ~,so.i..i C H1C H2CH = O ~

propan- l-ol propanal
propanoicacid
As soon as any aldehyde is formed it can be oxidised further by the oxidising

agem.tothecarboxylicacid. and sospecfaltechniquesareneededtostop
the oxidation at the aldehyde stage. One such method makes use of the lower
volatility o f the alcohol (due to hydrogen bonding) compared with the aldehyde.
The reaction mixture is warmed to a temperature that is above the boiling point of
the aldehyde. bu t below that of the alcohol. The aldehyde is allowed to distil out
as scxm as it is formed. thus avoiding any funher contact with the oxidising agent
(sceFigurel6.6).
Flgure16.6Apparatusfordistillingoff
theakiehydea,; ltisformedbytheoxidation
of an alcohol
at te,mperature
highet thanb.p.
of aldehyde
H,SO.,<"'l)
Usinganexcessofoxidisingagent.ontheotherhand. and he:itingthereactionunder

reflux to p,.,-venc any escape of the aldehyde befo.., distillation. allows the alcohol 10
be oxidised all the way IO the carboxylk acid.
This oxidation reaaion can be used to distinguish between primary, secondary and
1eniary alcohols(seeTable 16.J).
288
16 Alcohols I
Tabl e 16.3 Theuseofpotassium "fypeofalcohol Observation on Etfectofdlstlllateonunlversal
dichromate(Vl),mdmtfurica<ldtodistinguish
warm ln gwlthreagent
bern.wnprimary,sec:ondaryartdtertiary
olrnhol1 R,C--OH (tertiary) staysorarige fll'Utfal(1tay1green)
- onlywaterisproducl.'d
R,CH---OH ('>l'Comlary) turmgrl.'!'n fll'Utfal(staysgreen)
- ketooeisprodocl.'d
RCH~H (pfim,ny) l\lJmgreen acidi::(gol.'511.'d)
- carboxylkaddisproduced
5 The tri -iodomethane (iodoform) reaction

Alcohols that contain the group CHJCH(OH}-, that is. those that have a methyl
group and a hydrogen acom on the same carbon atom that bears the OH group, can
be oxidised by alkaline aqueous iodine to the corresponding carl:xmyl compound
CH 30:0)- . This can then undergo the tri -iodomethane reaction :
TheresultisshowninFigure 16.7.
Excep1forethanoL allthealcoholsthmundergothisreaction are secondary
alcohols, with the OH group on the second caibon ato m of the chain, that is , they
are alkan-2--ols . The =ception, ethanol , is the only primary alcohol to give the pale
yellow pt'(.'Cipitme of tri-iodomethane (iodoform) with alkaline aqueous iodine:
The trf.io d omct hane (lodofonn) r eat'lion is thus a very specific test for the
CH 3CH(OH}- group (or the CH,C=O group)
Worked example
Whkhoftheseakoholswillundergotheiodoformreactioo?
OH
Figure 16.7 Thetri-io:!omethane1e..ctioo
>-<" A
Answe r
Only alcohols A and D conta in the grouping CH1CH(OH )- , so these are the only two to
give iodoform. B is a tertiary alcohol, whilst C is a primary akohol.
P, Q and R are three isomeric alcohols with the formula CsH110H. All are oxidised
bypotassiumdichromate{Vl)andaqueous!.lllfuricacid,butoo!y P givesanacidic
distillate. When treated with alkaline aqueous iodine, Q gives a pale yellow
precipitate, but P and R donotreact.Whatarethestructuresof P, QandR?
289
ORGANIC CHEMISTRY
16.4 Preparing alcohols

As we would expect from their central position in org:rnic synthesis, alcohols can be
preparedbyavarieryofdifferentmethods.
1 From halogenoalkanes, by nucleophilic

substitution
See section IS.3fordetailsofthis reaction.
2 From alkenes, by hydration

See section 14.3 for details. This is the preferred method of making ethanol industrially:
The hydration can al.so be carried oul in the lalx>ra1ory by absorbing the alkene in
concenmued.sulfurkacid.andthendilutingwithwater:
CHi=CH, + H1so. ----t CH1CHc-OSO,H
CH1CHz--OS01H + HzO ----t CHJCH10H + H1so.
3 From aldehyde, or ketones, by reduction

See section 17.3 for details. There are three common methods of reducing carbonyl
compounds
By hydrogen on a nickel catalyst:
H, + Ni
CH1CHzCH0 - - - - - - 4 CH,CH 2CH 20H
By sodium tetrahydridoborate(ll[) (sodium borohydride) in albline methanol:
By lithium tetrahydrid0<1lumi113te{lll) (lithium aluminium hydride) in dry ether:

LAIHiin
CH1COCH1 d,yethtt CH1CH(OH)CH1
Lithium tetrahydridoaluminate(I[[) is a dangerous reagent, producing heat and

hydrogen gas (which usually catches fire) with any ,vater, and ether is a hazardous
solvent being very volatile and flammable. Hence this method is usually avoided.
4 Preparing ethanol by fermentation

In many pans of the world, the fermentation of sugar or starch is only used to
produce flavoured aqueous solutions of ethanol for drinks. But in some countrit,-s,
for example BmziL where petroleum is scarce and expensive. ethanol produced by
fem,entation is used as a fuel for vehicles . The ethanol can be used either alone or as
a 25% mixture with petrol. This could become incre-:isingly imp;:mam for the rest of
the world, once oil reserves become depleted.
YeaSlS are micro-organisms of the genus Saccharomyces. They contain enzymes
that nO{ only break glucose down into ethanol and carbon dioxide, but also break
down starch or sucrose (from cane or beet sugar) into glucose. They can therefore
coriven a variery of mw materials into ethanol :
,m
{C6H100Y. + nH10 ~ nC6H1106
otord. g\uco..
Ci1H,10n + H10 ---t C6H1106 + C6H1106
g\ucoo,e fructote
C6H1106 ---t C6H1106
fructOR g\ueo90
290
16 Alcohols I
The conditions required for successful fermentation are:
yeast nutrients (ammonium phosphme is ofien used)

e wamuh (atempemtureof30Cisideal)
absence of air (with oxygen present, the ahanol can be panblly oxidised to
ethanoicacid,orcompletelyoxidisedtocarbondioxide).
The reactiOfl is carried out in aqueous solution . Assuming etlOIJgh glucose is present,
itstops when the ethanol concentration reaches about IS%. Abon, this concentration
the)'l"astcellsbecornedehydmted.andtheyeastdies.Aherfiltering offthedeadyea.st
cells, the solution is fractionally distilled. The discUbte consists of 9:,% ethanol and 5%
water. If f<'CJUired. the remaining 5% water can be removed chemically, by adding either
quicklime (cakiumoxide):
C 11.0 + H,o----+ C11.{0H)z
or metallic magnesium
F1gure16.8 .iAnelec:tronmicrographof Mg + 2Hz0 ----t Mg{OHh(s) + H 1(g)
yeastce ll1. b Hhanolcan~u1edonit1own
ora1anadditrl'etopetroltopowervehicle1
c Wineprcxfaction
For most chemical and industrial purpose.s, however, 9~o ethanol i.s perfectly
acceptable.
Apart from the economic advantage of this method of producing alcohol (and
hencefuel), theuseofethanolas afuelhasanenvironmentaladvamage. Aswas
mentioned in section 13.4. fermentation-ethanol is a renewable fuel. lt returns to
the atmosphere exactly the same number of molecules of co, as were used in its
production byphO{osynthesisandfennentation:
(1)
~tmon
-
C6H1106 ~ 2C 1HsOH + 2C0 2 (2)
2C 1HsOH + 60 1 ~ 6H 10 + iC0 1 (J)
The carbon dioxide balance is therefore maintained. Indeed, if we add together

the thr= equations (1 ), (2) and (3) we find no net change in any substance. We
have obrninedtheenergywerequireemirelyfromtheSun,indirectlythroughthe
intermediates glucose and ethanol.
291
ORGANIC CHEMISTRY
Alcoho ls canbepreparedfromhalogeooalkanes,alkenesand e Esterification

G1rbonylcompounds hea1..;mconc.H,so,
Animportantwurceofethaoolistheferml'f1tationolstaKhor R--OH + HO.,CR'
sucrosebyyeast
Akoholsareimportantintermediatesinorganksynthesisand NtJdeophihcsubstittJtions
all!usefulsolvents R---OH + PCl 5 -, R- CI + POCl1 + HCI
Allakoholsbumtogivecarbondioxideandwater.Thelower
membersareusedasadditivesinpetrol R---OH + S0Cl1 -, R--CI + 501 + HCI
Akohol:scanredctgenerallyinthreediflefefltways:bytxeokir,g R---OH + HCl(conc.)-,R--C l + H10(be51withR 3 tertiaryalky!)
theO-Hbood,bybfeakingtheC-Obood,andbybfe,akir,g
theC- H bond next to the-OH group r>eatwtthNallr+fl,SO/H,O
Twogoodtestsforthe-OHgrooparetheeffetvesc:enceof
HCI when reacted with PCI.-,. Of the effe!Ve5cerxe of H1 wheo Eliminations
rrectedwithsodiummetal.
Primary, secondaryandtertiaryalrnholscanbedistinguished Al 1 0 1 a!350"<
eitherbythe irdifferentoxidatiooproductswithK1Cr10 7 and R-C H1- CH 10H -----------;)o R- CH==CH1 + H10
H1S0 4 orbyusingthe l ucasreagent {concentratedHC1and
ZnCl1}.
e lheiodolormreactionisatestforthepreseoceolthegroups
CH1CO- or CH1CH(OH )- in a molecule. The products are Oxidations
k>doformandasoditJmcarboxylatewithorlefewercarboo
atomsthantheoriginalalcoholorketone heatwllh/llii,Cr,O,+H,SO,(.lq)
R--C H==O--->RC(}.,H
KeyreactionsyotJshotJ ldknow
(R,R' ~ f)Omary,secondaryortertiaryalkyltJnlessothemise51ated.) heatwtthNa,er,o,+fl,SO,(.iq)
Combustion
he~1v,;thNa,c,,o,+H,SO,(aq)
C1H50H + 301 ---> 2C(}., + 3H10
e Redox
R---OH+Na-,R---O- Na + ~1

PleaseseethedatasectionoftheCDforanyA,valuesyou iii What is formed when compound E undergoes the
may need. samereaction~nganexcessofthesamereagent?[3]
c Compound A may be converted into compound B in a
1 The structural formulite of six different compounds, A~ F,
t1'\!0-stagereaction.
are given below. Each compoundcontainsfourcarbon
Stlgl'[ stage II
atoms in its molecule.
CH 3CH = CHCH1 ~ intermediate ~ CH 3CH 2COCH1
CH1CH = CHCH1 CH1CH1COCH1 CH1=C HCH1CH 3
i What is the structural formula of the intermediate
A B C
compound formed in this sequence?
CH 3CH1CH(OH)CH1 HOCH1CH1CH 1CH10H CHt:H1')CH2CH1
ii Outlinehmvstagelmaybecarriedouttogivethis
D E F
intermediate compound.
a i What is the empirical formula of compound E? iii \Vhatreagentwouldbeusedforstagell? [4]
ii Draw the skeletal formula of compound D. d Compounds D and F are isomers. What type of
iii Structural formulae do not shmv all of the isomers that isomerism do they shmv? [1]
may exist for a given molecular formula. Which two {Cambridge /memational AS & A Level Chemistry 9701,
compounds each show differe nt types of isomerism Paper 21 Q4 November 2009]
and what type of isomerism does each compound
show? Identify each compound by its letter. (4)
b Compound D may be converted into mmpound C.
i Whattypeofreactionisthis?
ii Whatreagentwouldyouuseforthisreaction?
292
16 Alcohols I
2 The alcohols are an example of an homologous series. d Alcohols,suchasmethanol,canbeusedasfuels.
Thetableshowstheboilingpointsforthefirstfour
members of straight-chain alcohols.
i Writeequationsforthecompleteandincomplete
combustion of methanol. ,,,
I"""" 1 Structura l formu Li l &o1 11ngpo1ntrc I
ii Suggest what conditions might lead to incomplete
combustion of methanol ,,,
I methanol I CH,OH I es I iii In addition to its use as a fuel, methanol can be
I ethanol l cH,CH,OH I I usedasasolventandasapetroladditivetoimprove
l propan-1-ol I '" I combustion.
l butan-1-ol
I CH 1 CH,CH,OH
I CH 1 CH,CH,CH10H "
1 118 I
Stateanot herlarge-scaleuseofmethanol.
e Butan-1-olcanbeoxidisedbyheatingunderrefluxwith
[1]
a i What is the general formula of a member of the excessacidifiedpotas.siumdichrornate(VI}

akOOol homologous series?
ii Deduce the molecular formula of the alcohol that has
111 Writeanequationforthereactionthattakesplace
Use[O)torepresenttheoxidisingagent. ,,,
13 carbon atoms per molecule. (1) f Butan-1-olisoneofthestructuralisomersofC, H100.
b Alcohols contain the hydroxyl functional group.
What is meant by the term functional group 7 ,,, i Writethenameanddrawthestructureofthe
structural isomer of C, H,,O that is a tertiary alcohol.(2]
ii Draw the structure of the structural isomer of C4Hio0
c i At room temperature and pressure, the first four
members of the alcohol homologous series are that can be oxidised to form butanone. (1]
liquids whereas the first four members of the alkanes {OCR Chemistry A UnitF322Q2 May2011]
homologous series are gases. Explain this difference.(3)
ii Methylprop<m-1-olandbutan-1-olarestructural
i50mers. Methylpropan-1-olhasalO\verboilingpoint
thanbutan-1-ol.Suggestwhy. (2)
293
AS Level
Organic chem ist ry
17 Aldehydes and ketones

Functlor1,1lgroup5:
Learning outcomes
0 1- oa- By t heendofthis topicyoushooldbeableto:
!a+
/,
J1+
1, 14.1a) inte<pretanduse thegene,al. structural,displa~andsl:~eta l
C H C C formulaeofthe aldehydesandketooes
18.1a) describe the IOfmation of aldehydes and ketooes from primary
alde hyde andsecoodaryakoholsrespectivelyus.ingCr20 1l-n-r, the
The carbonyl group, >C""'O, contained in 11/dehydes red uc:t kmof aldehydesandketol'll!S.
and ketones /s borh more polarised, and more e.g.us.i ngNaBH, 0tUAIH4.,andthereactiooofaklehydesand
po/arisablr,, than the C- 0 single bond In alcohols ketooes withHCNandNaCN
and phenols. This topic Introduces the last of 18.1b) descri be the me(MnPSfTI of the nudeopNllc addition reactions of
our f our main re.tctlon mechanls~ nuc/eophilic hydroge ncyanide \\ithaldehydesandl:etooes
addition. This Is the cho1racter/stic way in which 18.1d describetheus.eof2.4-dnitrophenylhyd(azine
carbonyl compovnds react and Is dr.Ht to the highly (2.4-DNPH)reagenttodetectthepresenceof
6t carbon atom that they cont II If\ combin&d with carbonyl compounds
their unsaturatlon. Aldehydfl ,re intermediate in 18.1d) dedua!thenature(aldehydeorketone)ofan unknown carbonyl
oxidation state berween alcohols and airboxylic compoundfromtheresultsofsimpletests(Fehling'sandTollens"
acids and can undergo both oxidiltion and reagents.ease of oxidation)
reduction react~ but ketones can only undergo 18. l el describe the react.ion of CHJCO- compounds with alkaline
reduction reactions. aqueousiodinetogivetri-iodomethilne.
17.1 Introduction
Collectin,ly. aldehyde-s and ketone-s arr known "5 ca rbo nyl cnmpo untls. The c.ubonyl
group. >C=O. isa subunil of many other functional groops(se,e Table 17.1). bu1 !he t=n
'c:ubonyl compo,mds' is ..,.,..,,.,.ro for thOS<! compounds in which it appe-Jrs on ils own.
Tabl e 17.1 Some functlonitl groups

containin9thec.irbori~g1oop
,...., ci.sofcompound
calbon~compool\d
R-C
:,. 0
0 alboqhc.w:ld
R- ~H
R- C~ R'
R- C~
0
"""
""'
R- C#'
0
""'"""'
' e1
294
17 Aldehydesandketones l
The propenies of aldehydes and ketones are very similar to each cxher: almost all the
reactions of ketones are also shown by aldehydes. Bue aldehydes show additirnrnl
reactions aS50Ciated with their lone hydrogen a!Om.
The lxmding of the carbonyl group is similar !O that of ethene (see section 14.1)
Here. the double bond is formed by the sideways overlap of two adjacent p oibitals,
one on carlxm and one on oxygen . Because of its higher electronegativity , oxygen
anracts the bonding electrons (in bol:h the CJ and the It lxmds). creating an electron-
deficient carbon acorn (see Figure 17.l ). This unequal distribution of electrons is
Flgure17.1 Ox)'Ql'nattr..ctsthetxmding responsible for the 1,vo ways in which carlxmyl compounds react.
ell.'ctrom ;may from the ca!bon atom
lhe oxygen of the c=o bond can be promnated by strong adds.
The carbon of the c=o bond. on the Ol:her hand, is susceptible to atrnck by
nudeophiles. Nu:
:c+- 0 - H
I
Nu - c - o -
1
The molecules of carbonyl compounds cannOI: attract one anOl:her through

intermolecular hydrogen bonds. because they do not contain hydrogen atoms that
have a large e1101Jgh &+ charge . They can. however. internet with water molecules
through hydrogen bonding . The lmver members of the series are therefore quite
soluble in w:iter(ahhough less so than the corresponding alcohols)
The boiling points of carbonyl compounds are also lmver than those- of the
corresponding alcohols. though significantly higher (by about 40-50C) than those of
the corresponding alkenes. This is due to the d ipole-dipole attractions between the
molecules (see Figure 17.2). Table 17.2 lists some of these properties
Flgure17.2 Dipole-dipoH'attractionsln
carbonylrn~OO'i
Table17.2 Propertiesofsomeaklehyde1arid
ketone;rnmparedwiththo'>!'ofalkenesand
alrn!ml1
Correspo ndin g carbonyl compou nd Correspond ing ako hol

Bolling Bolling So lublll ty ln Bollin g Solubllity ln
polntl"C polnUC 100gof w ater/g poln tl"C 100g of water/ g
CH1CH=ocCH, CH1CHO CH1CH,OH
CH1CH,CH=CH, CH1CH,CHO CH1CH,CH,OH
CH,CH,CH,CH-C H, 30 CH 1CH,CH,Cl-,O 76 CH1CH,CH,CH,OH
Carbonyl compounds have distinctive smells . Ketones smell sweeter' than aldehydes -
almostlikeesters.Aldehydes have an astringent smell , butoftenwitha fruity'
overtone - ethanal smells of apples. for example. The simplest aldehyde. methanal.
hasanunpleasant.choking smell . ltsconcentratedaqueoussolution.formalin,is
used to preserve biological specimens. Aldehydes and ketones of higher molecular
masshaveimponantusesasflavouringandperfuntingagents.Fig ure25.8(page419)
includes two carbonyl compounds with benzene rings, vanillin and benzaldehyde.
that are used as navouring agents. Some Ol:her carbonyl compounds with pleasant
smells are shown in Figure 17.3.
295
ORGANIC CHEMISTRY
Figure 17.3 Someplea:sant-1mellingrnbonyl

rnmpwnd1,;mdonethatocnJr1n.aturalfyin
mu1k(theba1isforperfume1)
menthone ionone
(spe,umint) (peppermint) (violet,)
d>o camphor
O''"o
be nzaldehyde
(almonds)
a=QH,)10

In one respecl. aldehydes and ketones can be cons idered as positional isomers
of each cxher: in propanal. CH 3CH1CHO, the functional group (carbonyl) is on
position l of the chain. whereas in propanone , CH 3COCH 3, it is on position 2.
Because of significant differences in their reactions, however. aldehydesand
ketones are named differently. and are considered as two separate classes of
compounds.
Aldehydes are named by adding ' -al' to the hydrocarbon stem:
Ketonesarenamedbyadding'-one ' tothehydrornrbon.stem. ln higherketones,the

1X>Sitionofthecarbonylgroupalongthechainnecdstobespedfied:
Worked example
DrawstructuresfOfthefo llowirig
2-methylpentanal
b hexan-2-ooe
Answer
ii Thelive-carboochaini1numbemd1tartingatthealdehydeend
C~3 /~1/HO
CHi IH
'"'
296
Namethefollowiflgcompounds
, 0 '
6 (CH 1)1C- CHO (CH 1CH 2CH,),C = O
17.3 Reacti ons of aldehydes and ketones

These reactions can be divided into three main groups
reactions common to bol:h aldehydes and ketones

"""ctionsofaldehydes only
reactions producing tri-iodomethane.
Reactions common to both aldehydes and ketones

Nucleophilic addition of hydrogen cyanide
ln!hepresenceofatraceof sodiumcyanideascacalyst (orofa base such as sodium
hydroxide to produce the salt), hydrogen cyanide adds on to carbonyl compounds:
The product is 2-hydroxypropanenitrile. Like the reaction between sodium cyanide and
halogena,lkanes(seesection 15.J).thereactionisa useful methodofaddingacarbon
morn to a chain. which can be valuable during oiganic syntheses. Cyanohydrins can be
hydrolysedto2-hydroxycarboxyHcacids(seeTopic 18)byheatingwithdilucesulfuric
acid.andcanalsobereduced to2 -hydroxy:,mines(,..,.,.Topic27):
The mechanism of the addition of hydrogen cyanide to carbonyl compounds

Hydrogen cyanide is neither a nudeophile nor a strong add. Therefore it cannOl react
with the carbonyl group by either of the routes shown on page 295. However. as we
saw in Topic 15. the cyanide ion is a good nudeophile. It rnn arrack the S+ carbon of
the C==O bond:
297
ORGANIC CHEMISTRY
TheintermedbteanionisaSlrOngbase. and can abstract a prcxonfromanun-ionised

m o leculeofhydrogency3nide:
So we see that althoughthecyanideionisused in thefirststep.icis..,-generntedinthe

second. h is acting as a homogeneous catalyst in this nucleophilk a ddition reaction.
The reductionofcarbonyl compoundsbycomplexmetalhydrides

Two complex hydrides. sodium borohydride and lithium aluminium hydride. were
disco vered in the 194().s, andhaveprovedveryusefulasreducingagentsinorganic
chemistry. They are ionic compounds which co ntain the tetrahedral anion (Mtt 4 r.
Table 17.3 lists some of their propenies and how they are used .
IDdium borohydride lithium alumin ium hyrlride

Tabl e 17.l Somepropertf!"iofco~ex
lnorgonicmetal hydrklesuseda1redU(ill9 Systematic n.ime ,;odium tetfahydridoborate(III) lithium tetfahydrkJoaluminate(III)
agent1 i11organi::chemi1try NaBH, liAIH,
methanol-water mixture, room totallydiyether,room
temperature or warming temperature oratreftux(35C)
Howtheproduct ls addiflg ..cidandextractingthe addingwater(withcare),then
s~atad productfrom theaqueousmixture add,andseparatingtheether
withanoJanic 'iOlventsucha1 solulioooftheproductfromthe
Hilzill'dsdi. lng use -

re!ativelys.ifeinolkalinesoluUoo,
butevotveshydrogengaswith
aqueousl.iyer
cancatchfirewithwaterorwhen
wet,andethersolventsform
acids explosive mixtures with air
Functlonillgroups carbonylcompounds{to.ilrnhols) cat!Jonytrnmpounds(toakohols)
lhiltcanbe esters(toalcot.ols)
niduca:l,andwhilt cat!Joxyhc acids{toakohol1)
theyue reduca:lto amkw1(toamine1)
nitriles{toamines)
As the table indicates, the prefem,d reagent for the reduction of aldehydes and ketones
is NaBH., . Although LiAll-1., will carty out the reduction as efficiently, it is both more
haz:rn:io us and more expensive than NaBH 4. However, as the more powerful reductant,
itcanbeusedtoreducecarlx>xylicacidsandtheirderhonives,unlikeNaBH.,.
Each reagent works by transferring a nudeophiHc hydrogen atom (with its
electrons) to the &t carl:xm of the carbonyl group, forming an intermediate metal
alkoxide,whichislaterdecompo,edtothealcohol
I
R'
"-
4 R C = O+MH4- -----) [ (
R' \
H
...__C-0
R
I
4
l
) M --------)
+H+
+H,O
R' \
.._C-OH+M(OH
H
R
I
h
Aldehydes g ive primary alcohols, while ketones g ive secondary alcohols:
Because these reagents are nudeophilic, needing a &t carbon to react with, they do
nOI: reduce c=c double bonds, in contrast to catalytic hydrogenation.
298
Catalytic hydrogenation
Like alkenes, caibonyl compounds can be reduced by hydrogen ga.s on,r a nickel or
platinumcamlyst:
The mechanism is similar co heterogeneous catalysis (see section 8.6).
Worked example
Suggest the strnctural formulae of the intermediates and products of the foHowing reactions
HCN+N.C:tl .... atwlthH,SOJ"
CH,CH,CHO---------> W ---------'----- X
b ~'"'~ , ~m.sw, ,
Answer
o, o,
I I
CH 1CH,CHCN CH 1CH,CHCO,H
Zls(v(CH = CH,
1 Suggestrnaqeotsforsteps l ar.d ll ine.x:hofthelollowingtransfonnations,andthe

structures oftheintemiediatl".SAandB:
(CH 1),C = O ~A~ CH 1 - CH = CH,
2 Suggestrnaqeotsandconditionsforthefollowir,gieoctions
a CHr-CH=CH-CHO----tCHr-CH=CH-CHiOH
b CHr-CH=CH-CHO ----t CH1-CH1-CH1-CH10H
Condensation reactions
Nitrogen nudeophiles readily add on to carlxmyl compounds. But usually, the
initially formed addition compounds cannOI be isolated . They easily lose water
to give srnble compounds containing a C=N bond:
Reactions that form water (or any other inorganic small-mol=ule compound) when
two organic compounds react with each other are rnlled condensmlon reactions .
299
ORGANIC CHEMISTRY
The mo.st imponam condensation reaction o f carbonyl compounds is th31 with

2,4-din itrophenylhydrazine (2.4-DNPH). The products are called hydraz.ones and
are cry51alline orange solids. which predpirnte out of solution rapidly. They can be
purified rebtivelyeasilybyr<,ery.stallisation.
The formation of an or arig e preci pitate when a solution o f 2,4- DNPH is added t o an
unknownrn mpotmd isa good testfor the pr-nce ofacarbonylrnmpound.
lf the melting point of a recrysrnllised sample is measured and compared with

tables of known values, the carbonyl compound can be uniquely identified . This is
especially useful if the carbonyl compounds have similar boiHng points, and so would
oiheiwise beeasilyconfused(.....,Table 17.4).
Table17.4 Themeltingpoif1Bofsome carbonyl compound Meltlngpolntof2,4-dlnltrophenylhydruone

2.4DNPHderivativesofGirtJonylrnmpoumls derlv;tlvelC
C H1C H, CH, CH, CHO
C H1C H, CCX: H,C H1
C H1CH, CH,CO CH1
Flgure17.4 Ethanalreactingwith2,4-DNPH
a atthe1tartofthereaction;thisform1an
01 arige2.4-DNPHprecipilate,b
Two isomers G and H have t he molecula r

fOffilulaC4HgO. G formsan Ofange
Pfe<:ipitate with2,4- DNPHwhe1&11 H
does oot. H decolorises brom inewater,
OOtG doe1 not.Ont1&1t meot wit h
hydrogenandnkkel,both G and H give
thes.,mecompound,butan-1 -oi
Suggeststructure1forG and H
Reactions undergone only by aldehyde,
Aldehydesaredistingu ishedfrornketonesbyhavingahydrogenatomdirectly
anached to the carbonyl group. This hydrogen a!Om is nO{ in any way acidic. but the
C- H bond is significantly weaker than usual. The -CHO group is readily oxidised
to a --C(X)H g roup, making aldehydes mild reducing agents. This oxidation,
specifictoaldehydes.hasbeenusedtodesignthefollowing teststhatwilldistin guish
aldehydesfromketones .
Oxidation by acidified potassium dichromate(VI) solution

h was mentioned in section 16.3 thac aldehydes are more easily oxidised than
alcohols. The reacrion takes place on gentle warming, and the colour o f the reagent
changesfrom o rangeto g reen.
300
ReductionofFehling'ssolution
The brig ht blue FC' hling's solut ion is a solution of Cu "" iOfls . complexed with
salts of tanaric add. in an aqueous a lkaline solu tion . \Vhen warmed with an
aldehyde, the Cu '- ions are reduced to Cu+ ions, which in the alkaline solution
fonn a red predpirnte o f copper{J) oxide . The aldehyde is oxidi.sed to the salt of the
corresponding carboxylic add:
C H 1C H O(aq) + 2Cu 2\aq) + 50 H- (aq) ----t C H 3C0 1-{aq) + Cu,0{) + J H ,O{l)

blu e tolu tion -I precipitate
Formationof asilvermirrorwithTollens' reagent

To llc ns' reagent contains silver ions, complexed with a mmonia. in an aqueous
alkaline solution. These silver ions are readily reduced co silver metal on gentle
wam1ing with an aldehyde. The metal will often sil ver-plate the inside o f the !e.st tube.
Once again. the aldehyde is oxidised to the salt of the corresp;:mding carboxylic acid:
A dilu ce solu tion of the aldehyde sugar, g lucose. was o nce used co make mirrors for
dome.sticusebymea nsof thisreaction .
Flg u re17.5Al\a1dehydeproducesasllYl'r
mirrorwilhTollem'iEagent
Aldehydescanbedi51inguishedfrom
ketone,by oneofthefollowingtests
. aklehydes prod liCearedprecipitateon
warm ingwithFehling'ssol ution
aklehydesproduceasilvermirroron
warm ing with Tollens' reagent
The tri-iodomethane (iodoform) reaction

Ketones that contain the grou p - COC}-{ 3 (that is. methyl ketones) undergo the tri -
iodomethane (iodoform) reaction o n treatment with an aqueous alkaline solution
of iodine . Tri-iodometha ne, CHJ 3, is a pale yellow insoluble solid. with a sweet
amiseptic"hospital'smell :
C!;1 _ _
/C = O + 31! + 40H ---4 CH1COJ + CHl1 + 31 + 3H,Q
CH pai, y,Uow
l pttc;pita<,
There is o ne aldehyde. ethanal. that also u ndergoes the tri-iodomethane reaction :
Figure 16.7 shows the results of the iodoform reaction.

The tr!.lodom L1 lrn n c (lodofor m ) N.""actio n is thus a veiy specific test for the
CH3CO- group (or the CH 3CH(OH)- group - see Topic 16).
301
ORGANIC CHEMISTRY
Worked example 1
Compound A has the molecular formula C4H80. It re.xii with Fehling's solution. On
treatment with sodium tetrahydridoborate(III) it gives B, which oo warming with
concrotrated">Ulluricacidgives2-methylprope<ie
ldeotifyAand B
Answe r
ApositiveFehl ing'ssolutiootestmeansthatAi:sanaklehyde.SodiumtetrahydridOOOfate{III)
teducesan aldehydetoapriffiilryakohol.Concentratedsulfurkaddconvertsthistothe
Des{ribeatest{adilfereotoneine;ich alkene.ThetefoH!'
case)thatyoornuldu'i!'todistinguish
betweeflthefol\owingpairsof
c~, c~ c~
compounds CH - CHO /CH - CH,OH /C=CH1
/
1 CH1CHiC HO and CH 3COCH1 '" '" '"
2 CH1=CH--CH10H and CH 3CH1CHO A2methylpropanal 8 2-methylpropan-1-ol 2methylpropene
Worked example 2
Which of these carbonyl compounds will undergo the iodofmm reactioo?
Twocarbooylcompounds E and F have
0
themoll'<:ularfOfmulaC 4H80. E gave
a yellow precipitate whl!fl tre;ited with
alkalinea,queousiodine,but F doesnot
>-< A
Suggest,witha reasoo, structuresfor
E and F.Suggestadiffereottest,other
than the tri-iodomethane mactkm, that Answe r
coukldistinguishbetwe{>nthesetwo Only ketooes A and D contain the grouping CH1CO- , so these are the only two to give
compounds iodoform. B rnntains the grouping CH 3CH1CO- , whilst C is an aldehyde
17.4 Preparing carbonyl compounds

From alcohols, by oxidation
See section 16.3 for details of this re3aion . For example:
K,ec,0 1 + H 1so,( ..1
H OH 0
'c/ II
y'rn, +[0]
yCt:H,
As explained in Topic 16, if an aldehyde is being prepared. the oxidant is added

slowly to 3n excess of the alcohol 3nd the 3ldchyde is distilled off as it is fom1ed
in order to prevent funher oxidation to the add . (As their molecules 3re not
hydrogen bonded to one another, aldehydes generally h3ve lo wer boiling points
that the corresponding 3Jcohols.) If. however. it is the add that is required. the
reactionmixtureisheacedunderrenuxsothmanyaldehydethatmightbeformed
rem3ins in contact with the oxidising a gent. and all is eventually oxidised to the
carboxylicadd .
302
Carbonyl compounds are those compotmds in which the e Nudeophihcadditioos:

u1rbonylgroupisnotassociatedwithothefhetem-atomsin
thesamefuoctiooalgroup. Therearetwotypesofcarbonyl
rnmpoonds - ketones and aldehydes
Theird1aracteristk:re.-ictiontypeis nucleoph il ltaddition.
Theycanbereducedtoakohols,andaldehydescanbeoxidised
R1CO - '" R1CH(OH}
Condensationreaction
tocarboxylicilCids
R1CO + H1N---R'-R1C=N----R' + H10
e TheyuJldergo condensation reactions
(H 1N-R' = 2,4-0NPH)
e lheconden1,otionreactionwith2,4-dinitropheny!hydrazine,
givinganorangepredpitate,isagoodtestforthepreseoceofa Oxidation reactions
carbonylcompoundinasample RCHO c,,o,' +H,ll RC0 H
e Aldeh'iUescanbedistinguis.hedfromketonesbytheireffectson 1
Feh ling'sso lution (deep~uesolution---->red-brownp redpjtate) RCHO flln,,~>OIL.Cion(C u' ' I RCO., - + Cu 0
1
,md Tollens' reagent {de..rcolourlesssolLJtion----tsilvermirror)
e lheiodoformreactionisatestforthepresenceofthegroups
CH1CO- or CH1CH(OH )- in a molecule. The products are RCHO Tolon'""'}O<l1IA<J ' )
""""
RCO., - + ~trmirror)
k>doformanda'iOOiumcarboxylatewithor.efewerc.arboo
atomsthantheOOginalalcoholorketooe Thetri-iodomethanereac:tion:
1, ~-o+!(oq)
Keyreactlonsyoushouldknow RCOCH1 - Rcoi + CHl1
{Allre.-icbonsundergonebyR1COarealsoundefgooebyRCHO.)
Cata!ytich~rogenation:

Please see the data section of the COforanyA,.valuesyou c Gisformedfrom F instepll.
may need. Use your answers to a and b to suggest
i whattypeofreactionoccursinstepll
1 Propanone, CH,COCH,, an important industrial solvent, can
iiareagentforstepll. (2]
beconvertedintoanotherindustriallyimportantsolvent,
d The production of MIBK from G in step Ill involves the
MIBK,bythefolla,vingsequence.
hydrogenation of the ;,C=C< group and is carried out
20!,C = O~C,,H,,O,~CH, - C= O catalytically. A mixture of compounds is formed because
L, F L = C(CH,),
the;,C=Ogroupisalsoreduced.
Whatreagent(s)andsolventarenormallyusedina
G(C,,H,oO) laboratorytoreducea:>C=Ogroupwithoutreducinga
1~pll ;,C=C<grouppresent inthesamemolecule7
G has a number of structural isomers.
(2]
CH,, = O e Draw the displayed formulae of a pair of structural

CH 2CH(CH,), isomers of G which contain the CH,CO- group and
M IBK which exhibit cir-tram isomerism
l..abeleachstructurecisortransandgiveyourreasoning.[3]
a When F i5 formed in step I no other compound is produced.
Suggest a structural formula for F, which contains one
-OH group. [1) Paper 2 Q5June 2009]
b Compound G has two functional groups
Name o ne functional group present in G and sh01v how
you would identify it [3]
303
ORGANIC CHEMISTRY
2 Compound Q, heptan-2-one, is found in some blue cheeses b Write the structural formula of the organic compound
CH1(CHiJ.iCOCH1 formedwhenQisreactedseparatelywitheachreagent
compound Q under~itableconditions. lfyouthinknoreactionoccurs,
a Compound Q may be reduced to R. Compound R may write 'NO REACTION'.
be dehydrated togivell'llOdifferentproducts, Sand T
i Draw the structural formulae of R, S, and T .
t-,-, ,-,,0/H
- . -t-------t------J [SI
c Thefirststageofcheesemakingistoproduce
2-hydroxypropanoic acid {lactic acid) from milk
CH 1CH(OH}CD 1H
lactic acid
OtherthantheuseofapHindiGator,whatreagentcould
youusetoconfirmthepresenceofwmelacticacidin
asampleofheptan-2-one?Statewhatobsefvationyou
would make [2]
{Cambridge International AS & A level Chemistry,
9701, Paper23Q4June2013]
ii Statethereagent5that1'\!0uldbeusedforeach of
these reactions in a school or college laboratory.
reduction
dehydration IS]
304
AS Level
Organic chemistry
18 Carboxylic acids and esters

Fun ct io na l group s:
Learning outcomes
o" By theeod ofthis topicyoushouldbeable to
,f
R- >+c "-~ - ~ 14.1a) interpreta ndusethegetieral,strlidural,disp!ayed andske!etalformul<1eolthe
carboxylic ilCidsandesters
14.2a) interpreta r.dusethetermrnndensafon in~ ation toorg ankrei!ctions
ca rboxyl icacids 19.1a) describethe fonnatkmofca rboxylic ilCidsfromak:ohols,aklehydes and nitriles
lnthistopicwe/ookatthemajor 19.1b) describethe reactioos olca rboxylicacidsintheformationolsalts(bytheuse
c/assoforganicacids, thecarboxylic olieactive metals, alkalisorca rbonates),a lky! esters,and akohols(bytheuse
acids, and at some of the compounds of liAIH 4)
derived from them. Apart from 19.3a) de,;uibethe acidandbas.ehydroiysisof este!'S
acid-basereactions,theirchemistry 19.lb) state the major commercial uses of esle!'S, e.g. soll'eflts. per/lJme1, fl aYOllrings
is dominated by nudeophi/ic
substitution reactions, owing to
thel\+carbonatomin thecarbonyl
18.1 Introduction
\Vhen the carbonyl g roup is directly joined to an o xygen morn. the carboxy l group
is formed . This occurs in carboxy lic ac ids and esters.
0 0 0 0
,f ,f
- c, - c CH i - C~ CH 1 - C~
'0 - 0- H O - CH 1
caJbonyli""'P c~rboxyl- c~rboxyl ic acid:
(ethanoicacid) (methyleth~t)
The reactions of the carbonyl group are drastically changed by the presence of
the electronegative o xygen 31orn. These compounds have virtually none of the
reactions of carbonyl compounds as described in Topic 17. The same is true of two
other classes of compounds in which the carbonyl group is directly attached to an
electronegative acorn. namely the a cyl c hlorides and the a mides:
O-<
0
0
,f
CH 1 - c,
Cl NH,
acvlchloride:
(ethanoylchloricle)
The reactivity of carlx>xylic adds is dominated by the tendency of the O - H bond

to ionise to g ive hydrogen ions. hence the incorp;:,ration of the word "add" in their
name. The extent of ionisation is s mall, however. For example. in a I.Ornoldm- 3
.solutio n of ethanoic add , about o ne molecule in 1000 (0.1 %) is ionised:
305
ORGANIC CHEMISTRY
Carboxylic acids are therefo,., classed as we ak acids (see section 6 .4).

lne 0---H lx>nd breaks heterolytically far mOf'e easily in carlxcylic acids than in
alcohols or in phenols (see section 25.5). The negative chaige formed by heterolysis
can be delocalised over two electronegative o xygen 31oms in the carboxylate ion . This
spreadingoutofch:trgeinvariablyleadstoastabilisationoftheanion (seefigure 18.1
and FigureJ.46. page62). Theeffectthac changes in thestrucrureofacarboxylic acid
have on the stability of its anion. and hence its acidity. is dealt with in section 26.l .
..
F1gure18.1 Thedwgel1spreadlnthe
carbaxylateanion,stabllisingtheion
,
The rnrboxylic acid g roup is a strongly hydrogen -lxmded one. boih to carboxylic add
groups on cxher carboxylic acid trK>lecules and to solve nt molecules such as water.
This has effects on two imp;:>nant propeJties - boiling JX)ints and solubilities. Table 18.1
.
Table 18.1 Hydrogen bonding inuea'i!.'5 the
boilingpointland1Dlub ilitie1incarboxylic
~
compares these properties for carboxylk adds and the corresponding alcohols.
Cuboxylkacld
Boding Solubility Bolling So lubUlty
poln tlC ln100gof polnUC ln100gof
water/ g water/g
HCO, H
CH,CH,OH CH,CO,H
CH1CH,CH,OH CH1CH,CO,H
CH, CH,CH,CH,OH CH,CH,CH,CO,H
CH1CH,C H,C H,C H,OH CH1CH,CH,CH,CO,H
Both in the pure liquid state, and in solution in non-hydrogen -bonding solvents such
as benzene. carlx:ylic acids can fonn hydrogen-bonded dimers (see Figure 18.2)
Figure 18.2 Ca rb oxylicacidsdim eri,;eao;two

moll'rnH'1hydrogenbondtoe.1ctiother
In water, lxxh o xygen morns and the -OH hydrogen atom of carboxylic acids can
hydrogen bond with the solvent (see Figure 18.3).
Flgure1B.1 CarboxylicacidshydrogenDO!ld 0- H
towatermolernle1 j
CH - ~ o:
1
H ~p - H :d/
"-o- H '\H
306
18 (;. b Xy1Cati

Catboxylic acids 3re named by finding the longest carbon chain that contains the acid
functional group, andaddingthesuffix'-oicacid'tothestem. Sidegroup.soffthe
chain are named in the usual way:
0
H - C~
OH
2-rnethylpropanoicacid
0-oo,H p-co,H
a
Estersarenamedasalkylderivmivesofacids,similarmthenamingofsalts:
ethylethanoate
The isomerism shown by acids is nOl usually associated with the functional group.
but occurs in the carbon chain to which it is attached. as in the following two isomers
withtheformulaC..H 80,:
(CH,)1CHC0 1H
1-mtthvipropmoio~
Esters, however. can show a panicular form of isomerism. depending on the number
of catbon atoms they have in the acid or alo:,hol pan of the molecule. Two isomers
of C.~01 3"' shown below. Ncte that 31though the add pan is usually written first in
the formula. by convention. it appears last in the name :
0
CHJG-:l 1 - c,J'
0 - CHJ
methylpropanoat
Worked example
Draw the structures of the other two isomeric esters with the formula C4H80.,, and name
them
Answe r
Draw and name possible ester isomers 0 0
with the formula CsH100i. How many H- C~ H- C,f'
esterisomersaretherewiththisformula? 0 - CH1CH,CH1 "o - CH(Cf\~
lndic.ateinyouranswerwhichofthe
estef5arech iral pmp-1-ylmethanoate prop-2-ylmethanoate
307
ORGANIC CHEMISTRY
18.3 Reactions of carboxylic acids

Reactions of the 0-H group
The acidity of carboxylic acids has already been mentioned . They show most of the
typical reactions of acids.
With metals
Ethanoic add reacts with sodium metaL liberating hydrogen gas (compare with
alcohols , section l 6.3,andphenols, ,.....c,ion25 .5):
They also react with <Xher reactive mernls , such as calcium and magnesium.
With sodium hydroxide

Like phenols, but unlike alcohols, carboxylicaddsfonnsaltswith alkalis:
Salts are often much more soluble in water than the carboxylic acids from which
they are derived. l'or example. solu ble aspirin rnblets contain the calcium salt of
ethanoylsalicylicadd (seesection25.6):
2~
IA,'co,H
OCOCH1
+ Ca(OH ) 1 ---t O
(IA,'co,- )
OCOCH1
Cai+ + 2H 10
~, hanoylnlicyl ic cid{Aspi,in ) nlcium e tha noylsalicylate
With sodium carbonate and sodium hydrogencarbonate

Liketheusualinorganicacids, bu c unlikelxxhakoholsand phenols,carboxylicacids
re:ict withcaibon ates, libemtingcaibondioxidegas:
A s imilarreaction occurswithsodiumhydroge ncaibonate :
Acids, phetiolsarKlakohol scanbe

distinguis.hl!dbythl'irreactiom with These th,..,.,. reactions form the basis of a series of tests by which alcohols, phenols
sod iummetal, aqueous sod iumhydroxide
and carl>axylic acids can be distinguished from o ne anOl:her, a nd from Ol:her
and aqueous sod ium G1rbonate
functionalgroups (s=Hgure 18.4).
308
18 C b Xy cau
Figure 18.4 Howtodis~nguish between dryu nknowi ubst ance X

akohol1,phenolsandcarboxyli::acids
addsodiummetalto liquidormohen X
doe,c z
r
addNaOHca,q1toX
Xdoesnotcontain--OHgroup
- o. a;,ws.,, d.,.,. nr~t

Xi, a n a lcohol
1
addNa,CO]("'l)toX
fine, does lot

fizz
j
Xi,acuboxylicadd Xi,aphenol
Reactions of the C~ OH group

There 3re two main reactions which replace the -OH group in rnrboxylk adds with
other atoms or g roups .
Withphosphorus(V)chlorideorsulfurdichlorideoxide
Carboxylk acids react with these reagents in exactly the same way as do alcohols
(seesecrion 16.3). Acylchloridesareproduced:
CH 1 - c,
., 0
+ PCl 5 ~ CH1- C,
., 0
+ P0Cl1 + HCI
OH Cl
0
Q-c~ +so 1 + HCl
Cl
Acy] chlorides are used to make amide. Further reactions a nd propenies of acyl
chlorides are described in Topic 26 .
Withalcoholsinthepresenceofanhydrousacids
Carboxylk adds react with alcohols (but not with phenols) in an add-eatalysed
equilibriumreacliontogivee.sters:
0 0
CH 1 - C~ + CH 1CH,OH ~ CH 1 - C~ + HiO (I)
OH 0 - CHiCH i
309
ORGANIC CHEMISTRY
The fonnation of an ester is an example of a condensation reaclio>1. This is when two

molecules join together with the elimination of a small molea,Je (alien water) (see also
sections26.4and23.2).
Typical reaction conditions are:
heatamixmreofcarlx>xyHcacidandalcoholwithO.lmolequivalentof
concentratedsulfuricacidunderrefluxfor4hours.or
e heatamixmreofcarlx:ylicacidandalcoholunderre(luxfor2h01Jrs,while
passingdiyhydrogenchloridegasthroughthemixture.
The reaction needs an add catalyst and. like any equilibrium reaction. it can
be made to go in either direction depending on the conditions. To encourage
esterification, an excess of one of the reagents (often the alcohol) is used, and
the water is removed as it is fonned (often by the use of concemrated sulfuric
acid):
H,so, + HcO----+ H30+ + HS04-
This drives equilibrium (1) over to the right (,..,., .section 9.3). To encourage the
reversereaction(thehydrolysisofthee.ster). theesterisheatedunderrefluxwitha
dilute solution of sulforic acid. This provides an =cess of water to drive equilibrium
(l)overtotheleft.
If an ester is made from an alcohol whose -OH group is labelled with an
oxygen-18 atom. it is found that the '60 is 100, incorporated into the ester. None of
it appears in the water that is also produced. Therefore the water mu.st come from
combining the -OH from the carboxylic acid and the -H from the alcohol. rather
than vice versa. That is.
0
,;,
R - C, +R' - 180H ~
OH
The following mechanism =plains why this is the case.
Themechanismofesterificationfhydrolysis
In a .strongly acidic medium. both the alcohol and the carboxylic acid can undergo
reversible pl'O{onation. However. only the prownated caiboxylic acid undergoes
R-C,
,,
( 0-H
0)
( .p - H
The pl'O{onation of the carboxylic acid in .step (I) produces a highly &+ carbon atom
which can undergo nucleophilic anack by a Jone pair of electrons on the oxygen
atom d an alcohol molecule:
~6- H
R-C /0-H
( .'o-H ~ R-C
R'- t ,
H
I '-O - H
;o, "'
R' H
310
18
The !hree oxygen morns in this intermediate rntion are ,e,y s imibr in basidty. Any
one of them could be atrnched to the proton. and prown transfer from one to anO!her
canoccurread"ly:
/H /H
0 0
I I /H
R- C - 0 - H :;;:::::! R- C - 0
I I . ,
;o, / 0: H
R' H R'
This new cation can undergo a carbon-oxygen bond breaking . which is essentially
the rever"" of reaction (2). to give a molecule of water, along with the pra1onmed
R- C
,,6- H
R'
>
Lastly,thecationlo.sesaprolontoregeneratethett'"carnlyst, and form the ester
product :
R- C
,,+o1H ~ R- C
,, 0
+ H+
'o - R' 'o - R'
Draw the mechanism for the add
catalysed hydrolysis of methyl As mentioned alxNe, the re:iction is reversible . So is the mechanism. With an excess
methano.Jte of water, esters undergo add-catalysed hydrolysis. The steps in the mechanism for the
hydrolysis reaction are the reverse of the above steps for esterification.
Reduction of the --C0 2 H group

Carboxylic adds can be reduced to alcohols by reaaing with lithium
tetmhydridoo.luminate(IIO (lithium aluminium hydride) , LiAlH 4, in dry ether.
0 LlAIH 4
R - C~ ----t R- CH 1 - 0H
dl"f<the<
0- H
The reaction requires the powerful reducing a gent LiAIH 4: neither NaBH 4 nor
H, + Ni are strong enough to reduce carboxylic adds. LiAlf-1.i wiJJ also reduce esters
(toalcohols)and amides (toamines seeTopic27).
18.4 Esters
Properties of esters
Esters have the functional group :
H Q'
'o
R- C
'o - R'
311
ORGANIC CHEMISTRY
Many esters are liquids with sweet, fruity' smells. They are immiscible with, and
usually less dense than , water. Despite conrnining two oxygen atoms. they do mx
form strong hydrogen lxmds with water molecules. Neither do they fom, hydrogen
bonds with Olher ester molecules (because they do n{){ contain &+ hydrogen atoms).
Their mat<>' intem,olecular bonding is van der Waals. supplemented by a small
dipole-dipole contribution. Their boiHng JX}ints are therefon, a few degrees hig her
than those of the alkanes of similar molecular mass. The position of the carboxyl
groupalongthechainhaslinleeffectonthestrengthofintem10Jecularbonding. and
hence boiling poim(seeTable 18.2).
Table 18.2 E51e~h.iveboilingpoint-;alittle

higherthantho,;eofrnnespondingalka nes
hexane~
" llolllngpolnU"C
0
pmpylmeth,moate II
H/C"-o/'..../
'c/o'-../
ethylethanoate !
0
methylpropaooate II
-..............c,o,......
Reactions of esters
The most common type of reaction that esters undergo is nudeophilk substitution.
iJJusumedherebytheirhydrolysis.
The hydrolysis of an escer is a slow process, caking several hours of heating under
refluxwithdiluteaqueousacids
#0 heat...rthH1SO,(oq) /,/0
CHJ- c: +Hi O ~ CH1-c, + C1 H50H
0 - CH 1CH1 OH
The mechanism of this acid-catalysed hydrolysis has be<,n discussed in section 18.3: it
is the reverse of the acid-catalysed esterifirntiondescribedthere.
Ester hydrolysis can also be carried out in alkaline solution. The reaction
is quicker than in acid solution: OH- is a stronger nudeophile !han water.
Additionally , it does no! reach equilibrium. but goes to completion. This is
because the carboxylic add produced reacts with an excess of base to form the
carboxylateanion:
f'o 1-,e,.....,thN.ott(av f'o

CH1 - c, + Na+oH- ~ CH1 - c, _ +CH 1CH10 H
Suggestamechanismfo r this
re.-iction,using0'1astheinitial O - CH 1CH1 ONa+
nudeophile,andCiHso- as the
baseinthelaststep.
The alkaline hydrolysis of esters has an imponant application in the manufacture of
soap. Fats are glyceryl trie.sters of long-chain rnrboxylk adds . Heating fats wi!h strong
aqueous sodium hydroxide causes hydrolysis of the triesters. The sodium salts of the
long-chain carboxylic adds are precipitated by adding salt (NaCl) to the mixture. and
this solid is then washed and compressed into bars of soap (see Figure 18.S). Perfume
andcolourarealsoadded.
312
18
Uses of esters
Esters with small molecular masses find many uses as solvents for paints and
varnishes, and also for removing caffeine from coffee and tea to make decaffeinated
beverages. Many natural perfumes. fbvours and aromas are esters, and many of these
are now manufactured commen::fally to flavour fruit drinks and sweets. 1t is the ethyl
esters formed from alcohol and the various adds in wines that accoum for much of
their"nose',oraroma . inthegbss .
Some of the naturally-occurring esters now made synthetically and u.sed as anifidal
flavours in foodstuffs are shown in Figure 18.6.
Figure 18.6 Somee1tersu1eda-;flavouring
''"'"
methylbutanoate (apple ) pentylethanoate(pur)
2-methylpropylmethanoate (ra,pberry) 3-methylbutyleothanoate(bainana)
18.5 Preparing carboxylic acids

Catboxylk adds may be pre-pared by the following reactions .
By the oxidmion of primary alcohols or aldehydes :
Na,CC,0., + H,SO,(,q) + he>t
Na,CCP., + H1SO,(aq) + heot
By the hydrolysis of org:rnic cyanides (nitrites):

he<o:withH 1SO,(,q)
CH i - C == N ----------} CHiC01H
By the hydrolysis of add derivatives such as e.sters, acyl chlorides and amides (see
Topics 27 and 28) . Althoug h these reactions proceed in high yields, they are nOI:
normally useful preparative reactions : add derivatives are usually made from the
rnrboxylic adds in the first place, so their hydrolysis forms no compounds of
313
ORGANIC CHEMISTRY
By the oxidation of aryl side chains. When treated with hot alkaline po1as.sium
manganace(VII), aryl hydrocarbons produce benz.oic acids by oxidation:
rf"VCH,
lv hutwithKMn(\ -t OH-{:oi)
O'CO,H
The ca rboxylic aclds,RCO.,H,afl'weakadds,iooisingtothe RC(}.,H + Na0H---->RC01 Na + H10
extentof1%orlessinwater. 2RC01H + Na1COi----> 2RC01 Na + C01 -t H10
Carboxylk:addsr&1ctwithalcoholsto!Ofm esters,andwith RCO.,H + SOCl1 ----> RCOCI + S01 + HCI
phosphorns(V)chloridetoform acyl ch lorl des RCO.,H + PCl 5 ---->RCOCl + POC1i + HCI
Estersundergo<Kid-Ofbase-catatysed hydrolys ls
RC(}.,H + R'OH heat1<ithcooc.W RC(}.,R' + HiO
e Carboxyhcackls.
RC0 1H + Na----> RC0 1 Na + ~H1
RCO.,R' heat with Hf)' or OH"""(aq) ) RCOiH + R'OH

PleaseseethedatasectionoftheCDloranyA,valuesyou i Usethesedatatodeduc:ethenumberofcarboxylic
acid groups present in one molecule of W .
""''""""' ii SuggestthedisplayedfOfmulaofW [SI
1 Isomerism occurs in many organic compounds. The two
main forms of isomerism are structural isomerism and
Paper21 Q5June2010]
stereoisomerism. Many organic compounds that occur
2 a Draw and complete the following reaction scheme which
naturally have molecules that can show stereoisomerism,
startswithethanal.
that is cis-tram Of optical isomerism.
lneac h e m ptybox,writethes tru ctura l fo rmula
a i Explain what is meant by structur.tl isomerism
ofthe0fganiccompoundthat1'\l0uldbef0fmed.
ii Statetwodifferentfeaturesofmoleculesthatcangive
risetos tereo iso me ri sm (3)
Unripe fruit often contains polycarboxylic acids, that is acids
with more than one carboxylic acid group in their molecule.
One of these acids is commonly known as tartaric acid,
HO,CCH(OH}CH{OH)CO,H.
b Give the structural formula of the Ofganic compound
produced when tartaric acid is reacted with an exces:. of
NaHC0 1 (1)
Anotheracidpresentinunripefruitiscitricacid,
o,
I
HO,CCH,cfH,CO,H
co,H
c Does citric acid show optical isomerism? Explain your
answer. (1)
Athirdpolycarboxylicacidpresentinunripefruitisa
colourlesscry:stallinesolid,W,whichhasthefollovving
composition by mass: C, 35.8%; H, 4.5%; 0, 59.7%.
d i Show by calculation that the empirical formula of W is
ii The M, of W is 134. Use t his value to determine the

molecularformulaofW. [3)
A sample of W of mass 1.97 g was dissolved in water and
the resulting solution titrated with 1.00moldm- 1 NaOH.
1
29.4cm were required fOf complete neutralisation.
314
18
b Write the structural formula for the organic compound c Compound B is chiral. Draw displayed formul<1e of the
formedwhen,undersuitableconditions, ll'llOopticali50mersofcompound B,indicatingwithan
i compound C reacts with compound D, asterisk{*}thechiralcarbonatom [3]
ii compound C reacts with compound E. [2) {Cambridge International AS & A Level Chemistry 9701,
Paper 2 Q41une 2009]
315
AS Level
Advanced practical skills (Paper 3)
19 Practical work
In this topic, we look at some simple
practical techniques that are used in
Suggested skills
thelaboratory,suchastitrationsand Yourpractkalworkwillbehe lpedif yooa/l'ableto
thefamiliar'wet'testsforfinding takereadingswithanacruracydetetminedbytheapparatusOOr.guse<l
outwhichcationsandanionsare produceanumericaliesultrnrrectedtoanappropriatenumberofsignifk.antligures
present in an unknown sample in the (youarenotexpectedtousestatistkillmethodsofanalysisoratredtmentoferrors)
test tube. Nowadays these methods reco.-ddearlyandcondselyrelevantobservations(indudingnegativeones)
areveryrarelyusedinanalytica/ drawvaliddeductionsfromtheseobservations
laboratories because modern physical arriveata likelyoverallident ificationofthesubstanceunderinvestigation
methodsaremuchmoresensitive ifappropriate,1ugge1tadditioralexperiments(indudingphysic:almethodsofa nalysis)
andselective,andcanreadilybe toconfirmyourcoodusion
automated, making them less labour
intensive. The methods do, however,
bringtogethermuchofthechemistry
that has already been met so they
provideausefulalternativewayat 19.1 Thermometric measurements
/ookingatinorganicandorganic
chemistry. Measuring enthalpy changes directly
Some reactions, for example neutralisation reactions, rnke place very quickly. The
heatevolved (orabsorbed)inthesere3ctionscan bemeasureddirtly\\-itha
thermometer, using 3n expanded polystyrene cup as a calorimeter.
ExamplesofsuchreactionsareincludedinsectionS.2.
Measuring enthalpy changes indirectly

Other reacrions take place slowly or may require a high temperature to bring them
about. The enthalpy change of such a reacrion is determined indirtly by carrying
out several rapid reactions and then using Hes.s's Law.
Examples of such reactions are included in section 5.4.
19.2 Titrations
Acid-base titrations
The most common type of titration is the neutralisation of an 3cid by a base u sing an
indicator to show the equivalence point.
Examples of such titrations are included in sections 6.6 and 6.7.
Potassium manganate(VII) titrations

For example:
The pomssium manganate(VI[) solution is placed in the burene. As it is run into the
3cidified Fe'\aq)solutionintheconkalflask, its purple colour disappears. The
316
19 Practical work I
end -point is when the solution permanently remains pink (that is, pale purple) when
thelastdropofthernanganme{V]I)solutionisadded.
Examplesofsuchtitrationsareincludedinsection7.4.
lodine-thiosulfate titrations
Ii(aq) + 2s10 /- (aq) ----+ 2r(aq) + s.,oi-(aq)
The sodium thiosulfate solution is added from the burette. The disappearance of the
yellow-brmvn colour of the iodine shows the end -point of these titmtions. This end-
JX>int is madenxm, obvious by adding a little starch near the end-point, this convens
the pale yellow colour into an intense blue colour.
Examples of such titrations are included in section 7.4 .
19.3 Appearance
Inorganic
MOISI inrngank compounds are made up of separate ions , and so they show
characreristicreacrionsassocimedwitheachcypeofiontheycontain.Analysinga
compound, therefore. involves the separate analysis of cations and of anions .
Since mo5t inorg:mic compounds are ionic. they are u.suaUy solid 31 nx,m temperature.
Much infom1m:ion can be gained from their appearance . Us,rnlly. the substance is in the
form of a powder. It may be either amorphOOJs. which suggests that it is insoluble in
water and has been made by precipitation, or it may be made up of small crystals, which
show that it must be soluble. having been prepared by crystallisation from solution.
Crystals may absorb moisture from the air - they may be hygroscopic. lf they are so
hygroscopictha1theydis.solveinthemoistureintheair.thcyare1errneddcli{(lK'SCCnt.
Some crystals become covered with fX>""der owing to cfflon>Seence , that ls. the Joss of
waterofcrystallisationinadryatrnosphere (seeTable 19.1).
Tab le 19 .1 lnfo1rnationthatc.mbegainl'od Type of powder Posslbletypeofsubstance

from001erv;rigtheappeoranceof.ipowder
amorphous made by precipitation insoluble.e.g.oxideorarbonate
oystolline madebycry'itallisation ,;olu~e. e.g. Group 1 rnmpound1.
nilrates,mostru!fate1andchlolide1
hygm~opk cationofhigh chargedemity Li+a!ldmostdoubleandtliply
rnntoinsmll(hwaterof Na,co,.10H,O.alum1
crystallisation
If the substance is made up of colOOJrless crystals or a white p;:,wder. we may infer

that we are dealing with a compound from the s block. or JX>SSibly from the p or d
Table 19 .2 lnformatiooth.itcanbegainedby Posslblelonsorsubst."lnaiprtsenl

obseivingthecolourofarnmpound
s-bloc:kelements;Al".Pb';d'ord' 0 KJm.e.g.cuorzn1
cu 1,wY..co'
pale green fe 1.Nf'
dark green cu"'.cr'
purple cr".Mno,-
pale violet fe' (goesyellow-brownin'iOlution)
pink Mn1.co'
yellow cr0,>-.Pb0.S
er,o,'-.l'bo
Pb,o,.cu,o
PbO,.Fe'.Fe,o,
CuO.MnO:,
317
ADVANCED PRACTICAL SKILLS (PAPER 3)
bloc k . A colou red compound probably indicates the presence of a transition metal
(see section 24.5) or an oxide.
Organic
If the substance is a liquid , it is probably organic. Some organic subsrnnces o f higher
molecular weight are solid. but the most common ones are liquid .
19.4 Solubility in water

When finding out if a s ub.srnnce is soluble in water. only a tiny amount or a drop of
the sub.stance should be shaken with \cm 1 ofwater. lftoo rnuchsubstanceisused . it
isdifficultto.....,whetheranyhasdi.ssolved.
Inorganic
Thesolubilityofaninorganicsubstancedependsontherelativevalues ofits lanice
enthalpyandemhalpychangeofhydration(seesections20.I and 20.2).
Organic
When a drop of an org:rnk liquid is shaken with water. it may form either a cle-ar
solution or a cloudy emulsion. This shows whether the substance is soluble in water
o r not. and ghes an indication of what functional groups are presem (see Table 19.3).
Tabte 1 9.3 lnfarmationthatm.aybededuced
Sol ublll ty ln wate r Poss lbl e fun ctlon.ll l gro up present
abolitanDfg<mic1ubstmcefromit11olubility
in water rnffVetelywluble klwerakohol.c.irboxyhc<Kid.aldeh)'de.ketone
1lightly'>Oluble higherakohol
h)'Oroc.irbon
haklgeooalkane
19.5 Detection of gases

A common analytical test is !O observe whether a gas is given off durin g a reaction
and. if so, to identify it. It is imponant to consider how the gas was produced and , if
possible. to write an equation for the reaction. Tab le 19.4 lis!s the mo.st likely gases
produced. SomeofthetestsareiJJustrntedin Figure 19.1.
Tab le19 .4 Themostrnmmoogases Appearanceandpropertk!s ll!s t andequatlon

prodllCeddurtnganaly1ts.Otherleo;1rnmmon
gase1l11cl!ideN,,CO,S03,N;,O,t,10,Br,andI, 0, rnlou rless.odoorless glowingsplintglows morebrightlyandmayberekindled
H, rnlou rless. odoorless when Ii~ bumsatmouthof testtube
2H,{g} + O,(g) -+ 2H 1 0(Q
co, rnlourless. almOII odourless limewater turns milky
Ca(OH),(aq) + C01 (g) -+ Ca<:O,(s} + H,O(I)
H,o rn!ldensesonrncierpartof bluecobalt chloridepaperturmp ink
test tube coc ~'-(aq) + 6H,0{0 -+ Co(H,O).'(aq) + 4C r-{aq)
so, rnlourles1.choking,acidic acidifiedK,cr,O,tumsgreen
Cr,O,'i.lQ) + 2W{aq) + 3S0:,{g) -+ 2Cr'"'\aq) +
H,O(Q + 3S0,,_(aq}
Hcl rnlourless. choking. acidic forms while fume, with ammonia gas
steamy fumes in moi'it air NHi{g) + HC ~g) -+ NH4C~1)
Cl, pale gri.'i'fl. very choking moist litmus paper is bleadied (it may tum red first)
Cl,(g) + H10(1) -+ C~..q) + HCIO(aq)
NO, brown. choking. acidic moist litmus paper turns red
NH, rnlourless. choking. pungeot the only rnmmon alkaline ga1: fmm, white fumes with
HCI: NH1{g} + HC~g) -+ NH,C~s)
"When !"I". hydrogen bUms with a qule~ rolourless llame . lUs nearl\,' atway; mt<edwtth ai" and heoce bUm,
with~ mid e;q,k,sk,n. The flame ~ ohm tinged wlth~low from the sod!Ym loos in the glass oi the test rube
' 1-JSrandl-ligM'thesame tem3sflCl.bUtarenearl\,'atw~,g1Yer,oHinthep<eSenceofelthefbromineor
kxllne.whkhareea~~lde,n11fledbythelrcoloors
318
19 Practical work I
Flgu re 19.1 Positivele<;lsfora{atbon
dioxide,bwatervapour, cchloririea!ld
I
dammonia
/ /
before
n n
(
The source of the gases is imponant because it tells us something about the substance
under investigation. Table 195 lists the most common sources of these gase.s.
-
Tab le 19 .5 ?o11iblesource5of'>Om!'commoo
o, + NO,
{H,Oifnitrate
is hydrated)
H1
Llkelysource
heating nitrates
HC~aq) on met.al
Typlcalequ.itlon
Ca(N01),(1) ----; Cao(1) + i o,(g) + 2No,(g)
Mg(s) + lHC~aq) ----; MgCl,(aq) + H1(g)

co, heatingG1rbonatesor cuco,{1) ----; CuO(s) + CO,(g)
HC~aq) on c.artxmatl.'5 caco.{1) + lHC~aq) ---+ cacl,(aq) + H,0(0 + co,(g)
H,O heatinghydratedsatts CuS04.5H10(1) ----> CuS0..(1) + SHP{g)
SO, HC~aq) on sulfill"i Na1S01(I) + 2HC~aq) ---+ 2NaC~aq) + H,0(0 + S01{g)
HCI H,SO,O)oochlorkles KC~1) + H,S0,{l)---->KHSO,(s) + HC~g)
Cl, HC~aq) with oxidi~r,g 4HC~aq) + Mn0,(1) ----; MnCl,{aq) + Cl1{g) + 2H,O(Q
agent1
NH1 NH.. ;md N.lOH(;,q) NH,C~aq) + N.lOH(;,q) --+ NaC~;,q) + NH1(g} + H,O(I)
19.6 Flame tests

Some cations, panicularly those of the s block, give characteristic colours in the
flame of a Bunsen burner. A nichrome wire o r porcelain rod is first deaned by
dipping it into concentrated hydrochloric add and heating it in the blue pan of
the Bunsen burner flame until there is no persistent yellow colour (due to sodium
impurities). A speck of the solid to be tested is mixed with a drop of concentrated
hydrochloric add o n the end of the wi"' or rod and heated . The function of
thehydrochloric addistoconvennon-volatilesub.stancessuchasoxidcsand
carbonates into the mo"' volatile c hlorides. Typical flame colours a"' listed in
Table 19.6 andsho wnin Figu"' 19.2 .
319
Tabte19 .6 Sometypk:alfl;mietestcoloor;
Llkelylonpresent
uorsr'
per1i1tent,intemeyelklw
palegreeo Ba'
bhie-green Cu'
Flgure19.2 Flameteru
All substances emit light at various visible frequencies, which appear as lines
in the spectrum (s=section 24.5). Often the lines are distributed across the
spectrum and there is no overall predominant colour. Sodium h as a single line
at 590nm. which can easily be identified with a direct vision spectroscope. A.fany
subsrnnces conrnin sodium as an impurity and it is difficult to eliminate the yellow
colour entirely. lts effect can be panially masked by viewing the colours through
blue cobalt gbss.
4' 19.7 Precipitation reactions for cations

Hydroxides, except those of Group 1 and ammonium. are insoluble in water and
oftenhavecharacteristicappearances.SomeareamphOl:ericanddiS50lvein=cess
sodium hydroxide; cxhers diS50lve in =ress ammonia to form a complex ion . The
addition of aqueous sodium hydroxide (see Table 19.7) or aqueous ammonia (see
Table 19.8)toanaqueoussolutionoftheuoknown(thetestsareuselessonthesolid)
gives valuable information about the cations p"'sent.
320
19 Practical work I
Reactions with aqueous sodium hydroxide
Table 19.7 Afl'W'drop1ofaqueoo1sodium
Onaddltlonofafew On add ition of excess
hydrc:i:idea readdl.'dtoasolutionofthe
dropsolNaOH(aq) NaOH(aq)
un known.H'ap1Kipitatefattm,furthe1
sodiumhydmxfdei1addeduntiliti'iinexc:e1s NH/ ooppt,butsme llofNH1,
especiallyonwarrning
Group1 LJ+> ,Na+,K+ oopp<
Group2 Mg'.ca' w hite ppt
sr'... ea'.. oopp<
Groups13and14 Al3<-,Pb>+ w hite ppt
dbloc k
'"'
Mn'
~,.
greenppt
off-wtiileppt'
pa~greenppt'
~,. braNnppt
co' pink0<blueppt
Ni'+ greenppt
Cu' bl\/l'ppl
zn' w hite ppt
"". brow'nppt
"lfthesolutloosa<ecOOCPn!Jated, u, S."andea>+may,;,e~~l<j\!Jl!Pdplta!ebecause !helrhydr<mdesare
ootvery~bie(seeSl'Ctk!n10.4).
'Ooexpo,u,..toai",theofl-whltepreclpltateofMl>{OH),rum,tobrownMr,O.Ol-1,and!hegreenp,eclpltateof
fe(Ol-1),nx,,,tobrownf<.>O.OH
Flgure19.3 Hydmxklep1edpitatecoloors
Canyoudeterrninethecatioopre,;ent ineach
olthesesolulioml
Summary of equations
ForNH./ions
ForAg ions-
FordivalemM' ;ons:
321
lfthepredpitateissolubleinexcess:
Fortrivaleml>fions:
MJ+{aq) + 301-r(aq) ----+ M(OH)3's)
lfthepredpimteissolubleinexcess:
M(OHl}(s) + OI-r(aq) ----t M (OH).- (aq)
Reactions with aqueous ammonia

Table 19.8 A few drops ol a,qlJ!.'Clusammonia Onaddttlonofafew On addition of excess
ateaddedtoa!iOlutKl!loftheunkMwn. lfa dropsofNH 1(aq) NH1(aq)
prl'C~tateforms,furtherammoniao;olutionis
U', Na,K oopp<
addeduntilitisITTexc~s >-'-" ~
" '-' --t-'-~--t-'-~---+----------i
Group 2 Mif' whiteppt
ca"-.sr'.aa' ooppt
Groups 13 and14
,,.
Al",Pb' w hite ppt
greenppt sllghtly!ialuble
~~
Mn' off-whileppt
p.legreenppt
brownppt
c& pinkOfblu e ppt
NP'+ greenppt
Cu' paleblueppt
Zn' whiteppt
Ag brownppt
"Bl'Gl<M!heOI-J-ronceotralloolslow,S<" aodlla' ion<doMtproduceapredpltate.Acoocentratedsolutloo
olca'1oo,mayg;,,eatailtpreclpltate
The arnmoni3 acts in two ways:
as a weak base , giving a low concentration of Of> ions, though nct sufficient to
producehydroxycomplexes
as a complexing agent, with NHJ acting as the ligand .
Summary of equations
For Ag~ ions
2Ag\11.q) + 20I-r(aq) ----t Agp(s) + Hp(I)

Wi:h excess aqueous ammon a
FordivalentM1 ~ ions:
Wi:h excess aqueou ammon a :
C u(OH)z(s) + 4NHhq) + 2H 10(aq) ----t [Cu(NH 1)iH 10hf\aq) + 20I-r(aq)
Zn{OHh(s) + 4NH1(aq) ----t :,7~),!::~:: deepbluetolution

+ 20I-r(aq)
FortrivalentMJ.+ioos:
MJ.+{11.q) + 301-r(aq) ----t M(OHh{)
32l
19 Practical work I
19.8 Action of acids
Hydrochloric acid
Table 19.9 lists the most common gases given off as a result of treating a solid with
aqueous hydrochloric acid.
Table 19 .9 Common ga1e1 given off when a Ll kelyanlonpresent l)'plu l equ.itlon

solKJistreatedwithaqueoushydroc:Mori::ac:KJ
co, carbonate, co/- Of CuC0,(1) + 2HC~aq) _. CuCl,(aq) + CO,(g) + H,0(1)
hydrngeocarbooate, N.iHC0.(1) + HC~aq) _. N..C~..q) + CO,{g) + H,O(~
Hco,-
SO, sulfite, so,'- Na:,S0 1(s) + 2HC~aq} _. 2NaC~aq) + SO,{g) + H,O{I}
SO,(+ S) lhirnult.te, s,o/- N.1:,S,Oa{1) + 2HC~aq) _. 2NaC~;,q) + 50,(g) + S(g) +
H,O(I)
NO, + NO nitrite, No,- 2KNO,(s) + 2HCl(aq) _. 2KC~aq) + NO,(g) + NO(g) +
H,O(I)
Hydrogencarbonmes can be distinguished from carbonmes. as heming a solid

hydrogencarbonategiveswateraswellascarbondioxide:
The colourless nitrogen monoxide obrnined when nitrite is tre:ited with aqueous
hydrochloric add reacts with oxygen in the air to give more of the brown nitrogen
dioxide:
If the solid is insoluble in water but dissolves in aqueous hydrochloric acid, it may be
arnrbonme (ifcarlxmdioxideisgivenoff) , a sulfite(ifsulfurdioxideisgivenoff)or
it may be an insoluble basic oxide. The colour of the resulting solution may help to
idemifythecation.
Sulfuric acid
If there is no reaction with aqueous hydrochloric add. a fresh sample of the solid
may be treated with a few drops of concentrated sulfuric add. The reaction must be
carried out in a fume cuplxxird. The mixture may be carefully warmed if there is no
reaction in the cold. Table 19.10 shows the likely g:,ses that may be detected.
Table 19 .1 0 Commongasesevolvedwhena
Uke lyanlon ~p[caleqwitlon
solKJistfe.itedwithcoocentratedrnlluricac:id
present
chlorkle.Ct"" MgCl,(s) + 2H,S0, (0 -+ Mg(HSOJ:,{s) + 2HC~g)
H8r + 8r, + SO, bromkle.Br KSr(s) + H,S0..(0-+KHSO..(s) + HBr{g)
2H8f((J) + H,S0..(0 -+8r,{g) + SO:,((J} + 2H,O(O
HI(verylittle) + iodide.r Nal(s) + H,SO..(Q -+ NaHS0,(1) + Hl(g)
12 + SO, + H1S 2Hl(g) + H1SO,(s) -+i,(g) + SO:,((J} + 2H,O(I)
{+ 5) andotherreactKlm
nitrate.No,-
methanoate.Hco,- HCO,H(l) -+ CO(g) + H,0(0
CO + CO, ethanedioate.c,0, 2-- H,C,O,(s) -+ CO(g) + CO,(g) + H,O(Q
CH1CO,H ethaooate.CH1CO,- CH1CO,K{1)+H,SO,{l) -+ KHSO..(s) + CH1CO,H(g)
In these reactions. concentrated sulfuric add acts as a strong non- volatile ackl.
displacing more volatile adds as gases. With bromkles and iodides. it also acts as an
oxidisingagent.WllhmethafXXltesandethanedioates.ital,oactsasadehydrntingagern.
Bromine gas is red-brown and iodine vapour is purple. Nitric add vapour is usually
f"'le brown as it decomposes s lightly to nitrogen dioxide. It coodenses on the cooler pan
323
ofthetestrubeas anoilyliquid.Caibonmoo o xideiscok>urlessandburnsquietlywith

an intense blue flame. Ethanoic add, CHJCO,H, am be identified by its smeU of vinegar.
19.9 Precipitation reactions for anions

Aqueous barium chloride
Aqueous barium chloride (or barium nitrnte) gives a p,.,dpirnte with a large number of
ions,indudingcarlxmace.sulfiteandsulface. lnthepresenceofaqueoushydrochloric
add (oraqueousnitricacid),onlysulfateions g ive adensewhiteprecipitate.Soifthe
addition of aqueous hydrochloric acid and aqueous barium chloride to a solution of
theunknownsubstance g ivesadensewhiteprecipitale, sulfateionsarepresent.
Aqueous silver nitrate

Aqueous silver nitrale g ives predpirntes with a large number of ions, including
carbonate, chromace(VI) (Cro/-) , hydroxide, chloride, bromide and iodide . However,
in the presence of aqueous nitric acid as welL only chlorides, bromides and icxlides
ghe precipitation (see Table 19.11). The colours of these precipitates and their
solubilities in aqueous ammonia d istinguish them from one another.
Pntc lplblte
solubleind iluteNH1 (aq)
aeamorpaleyellow solublei11rnncl'flt1atedNHa(aq)
det>pyellow insolubleinrnncentratedNH1 (;,q)
Typical equations
Cr(aq) + Ag\aq) --+ Agel(s)
Agel(s) + 2NH 1(aq) --+ Ag{NH1)/(aq) + Ci-(aq)
Thedifferemcoloursand.solubilitiesofthesilverhalides a,.,.discussedinseaion ll .3.
Worked example 1
Substance A is a white amorphous powder. It is insoluble in water. A dimllws in aqueom
h'jl)rochlorkMid,witheffeivescence. togivearnlourless'iOlution B. Thegasevolved. C,
turns limewater milky. When aqueous sodium hydroxide was added to solutioo B, a faint
white precipitate was formed that did not dissolw in excess. On addition of aqueous
ammooia to solution B, no precipitate was formed. Substance A rnloured a Bunsen burner
f!amegreen.Expla inalltheseobsetvations,identify A, B andC,aridgiveequationslorthe
reactioosthat takepklce
Answer
The inferences that can be drawn from the obsetvatioos are summarised in Table 19.12. {It
is relatively easy to identify the substance as barium carbonate. However. to answer the
questionlully,itisimportanttoexpla inal l theobsetvat iom.)
while. amorp hous powder

ootGroupl;notNo,-
suggest1co/- {orHco,/
gas turns limewater milky CO:,producedlromco,'- {orHCO,- )
'>Olution B +NaOH{aq)grl'esala iritppt sr' orBa' pn.>sent
'>Olution B +NH1{aq)givesnoppt Sr'orBa"pn.>sent
flame test green
324
19 Practical work I
A is barium carbonate, 8aC01{5). {It is not Ba(HC01)i, became it is insoluble.)
B isbariumchloridewlution,BaCli(aq)
Ciscarbondioxide,COi{g)
Theequationforthereactionsareasfollows:
BaC01(s) + 2H'(aq)--;H10(l) + COil!J) + Ba1*(aq}
CO.,(g) + Cit(OH).,(aq) --t CaC01(s) + H10(1}
Ba 1*laq} + 20Hiaq) --t 8a{OH)zh)
(fa.ntwtJ
1 D isahygroscopicbrowrisolid.ltisreadilysolubleinwatertogiveagreensolution.
Withaqueoussodiumhydroxide,this'>Olutkmgivesadarkgreenprecipitate, E,that
doesnotdissclveinanexcessofthereagent. Etumsbrownonexposuretoair. D
showsnore<1CtionwrthaqueoushydrochlOOcacid,butwithconcentratedrnlfuricacid
it frothed and gave off an acidic gas, F, as well as a red-txown gas, G. When moi51 air
is blown over the mouth of the test tube, F gil'eS steamy fumes, and it alw gives dense
white fumes whefi a drop of ammonia on a glass rod is brought near. The addition
ofaqueousnitricacidands.ilvernitratetoasollllionof D producedaprec:ipitatethat
turned green when aqueous ammonia was added
Explain a ll these observations, identify D, E, F and G, and write eqLJatiom for the
reactions that take place
2 H is a white amorphous powder. It is insoluble in water but dissolves readily in
aqueoushydrochloricacid,withnoevolutionofgas,togiveacolourlesssolution l
To a portion of H, aqueous md ium hydroxide is added . A white precipitate forms
thatd issolvesinanexcessofthereagent.Toasep.-irateportionof H,aqueous
ammonia is added. This also gWe1 a white precipitate that d issolves in an excess of
thereagent.Aflametestonasampleof l isnegative
Expla ina lltheseobservations,identify H and l.and1uiteequat ionsforthereactions
that take place.
19.10 Organic tests

The solubility of an organic substance in ,vater gives an indication of wha! group i!
contains (seesection 19.4). Furtherspedfictestscanthenbeusedtoprovidemore
Table 19.13 Some common tests u'oed in evidence(seeTable 19.13).
organic chemistry
Posslble fu nctlon.il grouppresen t

shake with bromine water (see page 256)
addsmall pieceoflO<liummetal(seepages284and308) H1(g)evolvl.'d alrnhol.carboxyhcadd
addsolidPCl,(seepage1286and309) alrnhol.carboxyhcadd
warm with acidiff!.'d pot;mium dichromate (see pages 287- 289) goes from Ofange to green primaiyorsernndaiyalcohol.
aldeh)'Oe
addsodiumc arbonate(seepage308) co,evolved carboxyhcacid
addafewdrDpsofrnklacidified KMn04 (1ee page260) goesfrompu!J)~tobrownto
coklurH',s
add2.4DN?H(seepage300) orangeppt ;ildehyde.ketone
warmwithfehlifl9~solution(seep age 301) redppt aldehyde
gentlywarmwithTo lk>ns"reagl'flt(seepage301) aldehyde
boil u!lder reflux with NaoH(aq) and test with HNO/AgN0 1 pptforms chloride.bromide.iodide
(seepage273)
warm with NaoH(aq) and I,{aq) ye lklwpptforms methy!ketoneorCH1CH(OH/
Alltheseflmct,onolgrooptell1aredesrnbedindeto1l1nsectK>1130.S
325
Worked example
A colourless liquid J dissolves easily in water. Liquid J gives ste;imy fumes when t reated with
PCl 1. It does not redd: with sod ium carbonate. When warmed with acidified potassium
dichromate, the solutioo tums gfei!n. When this grEi!n solution is distilled, the distillate I(
gives a precipitate with 2,4-0NPH but does oot give a 'iHver miml4' with Toll em' reageot.
Explainall th!'seobsefvations,ideotily J and K,andwriteequationslo1the1edclionsthat
taKeplace
Answe r
The inferences that can be drawn from the observations are summarised in Table 19.14
lowerakohol,carboxyticacid,aldehyrleorketooe
givesfumes1\ilhPCI, ak:oholorcartxJxyli:: add
no!l'actionwithNa,co, notadd,thereloreakohol
potass iumdkhromategoe5green primaryor'il'(of\daryakohol
distillatereactswith2,4-0N?H aldehyde or ketone
nol!'actionwithTolleos'rea.gent not aldehyde
Therefore J isasecondaryalcohol.ltisprobablypropan-2-ol,CH3CHOHCHi,ashigher
seamdaryalcoholsareonlyslightlymlubleinwater. K wooldthenbeprop;inooe
CHiCOCHi.
Theequatiomlorthereactioosarea1follow1
CH 3CHOHCH 3 + PCl 1 -+ CH 3CHCICHi + POCl 3 + HCI
CH 3CHOHCH 3 + [OJ-+ CH 3COCH 3 + H10
1 Acoloorlessl iquid l wasinsolubleinwaterandhildadensitygreaterthanl.ltdid

not de<:olorise bromine water. When boiled under reflux 1'1-it h sodium hydroxide,
50me of the liquid dis501ved. When the aqueous layer was treated with an excess
of nitric acid and silver nitrate, a pale yellow precipitate M was formed that was
50lubleinconcentratedammonia.
Suggestthegrouppresentin Land1'1-'l"iteanequationfortheactionof
concentrated ammonia on M.
2 A coloorless liquid O was 50luble in water. It gave fumes when treated 1'1-ith PCl 5
When wa rmed with acidified potassium dichromate, there was no change in colour.
Withsodiumcarbonateiteffervescedandgaveoffagas.
Suggestthegrouppresentin O andwriteequationsforitsreactionswithPCl 5 and
sodium carbonate.
Enthalpychangescanbemeasuredwithacalorimeter,eitherdirectlyorindirectly.
The thre{' most common types of titration are acid-base, redox with potassium manganate(VII} and iodine-thiosulfa te
e Catiooscanbeidentifiedby:
e thecolourofthesalt
flametl.'51:s
theactiooofaqueoussod iumhydroxideandaqueousammoniaonasolution
Anionscanbeidentiliedby
e theactiooofheatoothe50lid
theactiooofHCl{dq)andH1S0,i{l)onthesolid
theactiooofAgiaq)ionsOf8a1*{iiq}ionson50lutions
Organicsubstaocescanbeideotiliedbytheirsolubilityinwaterandbyarangeolspecilic tests
326
19 Practical work I
Please5ttthedatasectionoftheCOforanyA,val~you iii how you would control the factors in the heating 50
may..,. that diffe>nt carboniltM can be compared. [4]
e State a hazard that must be considered when planning
1 The carbonates of Group 2 in the Periodic Table decompose
the experiment and describe precautions that shouJd be
on heating forming an oxide and carbon diaooe .
taken to keep risks to a minimum [2]
XisanyGroop2anion (e.g. Mg2,.
f Draw a table with appropriate headings to show the data
XCOJ -+ XO+ C02 you would record when carrying out your eiq>eriments
and the values you would cakulate in order to comtruct
Thisde<:ompositionoccursbecausethe positiv~ycharged
agraphtosupportorrejectyourpredictionin a . The
cations polarise (distort) the C- 0 bor'ld in the carbonate
headings m ustincludetheappropriateunits. [2]
ion causing the ion to brealc up. The charge density of the
g Thiss.impjeexperimentislik.elytoproduceonly
Group 2 cations de<:reases down the group. Th.s affects the
approximate results
decomposition rate.
Suggestanimpn;,,oementto~apparatusoranalternative
You are to plan an experiment to investigate how the rate
apparatrnthatmayimprovethereliabilitjoltheresults. [1]
of decomposition of a Group 2 carbonate varies as the
{Cambridge /ntemariona/ AS & A Le~/ Chemistry 9701,
groupisdescended.Theratecanbecoovenientlyme~red
Paper SI QIJune201,;
by finding the time taken to produce the same volume of
2 Hydrated iron(II) sulfate can be represented as FeS04 .xH 10
carbon dioxide from each carbonate.
where x is the number of molecules of Hz() for each FeS0 4 .
a i Predict how the rate of decomposition of the Group 2
When the compound is heated, it loses the molect.1les
carbonateswillchangeasthegroupisdescended.
ofwaterleavinganhydrousiron(IQS1.Mate
Explain this prediction in termsofthechargedensity
A suggested equation is:
of the cation as the group is descended.
ii Display your prediction in the form of a ~etch graph, FeS04.xHlO(s)-+ FeSO,(s) + xH20(9)
dearlylabellingthea:(es. (3]
An experiment is carried out to attempt to determine the
b In the experiment you are about to plan, identify the
valueofx.
followi119:
An open crucible is weighed and the mass recorded .
i theindependentvariable Asampleofhydratediron(IQsutfateisaddedtothe
ii the dependent variable. [2] crucibleandthenewmassrecorded
c Draw a diagram of the apparatus and experimental Thecruciblewithhydratediron(11)sutfateisheate d
5el up you would use to cany out this eiq>erimenL stronglyforfiveminutesandallowedtocoolbad:to
Your apparatus ~ d use only standard items found roomtef11)el"ature.
inaschoolorcollegelaboratoryandsho.vclearlythe Thecruciblewiththecon1entsis re10,'eighedandthe
follc:minsr mass recorded
i theapparatususedtoheatthecarbonate a Calculate the rela~ formula masses, M of FeS0 4
ii howthecarbondioxidewillbecollected. andHlO
Labeleachpieceofapparatusused, indicating its size [A,:H, 1.0;0, 16.0;S,32. I; Fe, S5.8] [1]
or capacity. [2] b Theresultsofseveraloltheseeiqi,erimentsarerecordedon
d Us.ing the apparatus shown in c design a laboratory thefollowingpage.Copythetableandprocesstheresults
experimenttotestyourprediaionin a . tocalculateboththenumberofmolesofanhydrousiron(U}
lnadditiontothestandardap~ratuspresentina sulfoteandthenumberofmolesofwater.
laboratory)OUarel)l"O'videdwiththelollowingmaterials: Recordthesevaluesintheadditionalcolumnsolthe
s.Ynpiesofthecarbonatesofmag-,esio..m,calcium,strontium table. You may use some or all of the columns. Masses
and barium. a stop-watctvdock with second hand. should be recorded to t wo dec imal places, while
Give a step-by-step description of how you would carry the numbers of moles should be recorded to three
outtheexperimentbystating signili ca ntli g ures. Labelthecolumnsyouuse. Fofeach
i the gas volume you wouJd colJect from each carbonate columnyoouseincludeunit:swhefeappropriateand
ii how you would calculate the mass of each carbonate an expres.s.ion to show how )'OUr" values are calculated.
toensurethatthisvol...-oeofcarbondioxideis You may use the colurm heaa:ngs A to G for these
produced expressions(e.g . A-11) .
m
1n,1ssof mas of
cruclbkt+ cruc:lble+
FeSO,.xH,O FeSO,
lg lg lg
121
c Plotagraphto!.h01vtherelationshipbetween the f Commentonthereliabilityofthedataprv.idedin b. [1]
number of moles of anhydrous iron(II} sulfate, FeS0 4 g i Usethevalueoftheslopeofyourgraphcalculated
{x-axis), and the number of moles of water (y-axis). Draw in(e)to!.Uggestthecorrectformulafor hydrated
the line of best fit. It is recommended that you do not iron{ll}!.Ulfate.
includetheorigininyourchoiceofscaling [3) ii Explainyouranswerto i. [2]
d Circle and label on the graph any point{s) you consider to {Cambridge lntemational AS & A Level Chemistry 9701,
be anomalous. For each anomalous point give a different Paper51 Q21une2013]
reason why it is anomalous dearly indicating which point
you are describing (3)
e Determine the slope of the graph. You must mark dearly
on the graph any construction lines and ~mv dearly
in ;,:iur calculation how the intercepts were used in the
calculation of the slope. (3)
328
A Level
Physical chemistry
2 Q Further energy changes

In Topic 5, we showed how we
could measure the standard enthalpy
Learning outcomes
change,Afr, ofareaction,andat Bytheeodofthistopicyoushouldbeableto
how this value is determined by 2.3g) explainandusethetermelectronaffinity(part,seealsoTopk:2)
there/ativebondstrengthJinrhe 5.1b) expla inandusethetermlatticeenergy//,.Hnegative,i.e.gaseousionstosolid
reactantsandintheproducts.lnthis lattice){part,1eeals0Topk:S)
topic, we look how the tJ.H values 5.1d) explain,inqualitativeterms.theeffectofionicchargeandofionicradiu1onthe
forionicreactionsaredetermined numericalmagnitudeofalatticeenergy
by the forces of attraction between 5.2a) app~Hes1"1Lawtoconstructsimpleenergycycles,andc.arryoutcakulations
the ions. We then show how en~ involving suchcyclesandrelevantenergyterms, wilhparticularreferenc:etothe
considerationscanexplalnsome formation of a simple iooic solid and of its aqueous solution, and Born-Haber
trends in the properties of Group 2 cydes (indudingionisationenergyandelectronaffinity) (part,seealsoTopicS}
compounds. ThecdteriarhatilH 5.3a) explainthatrotropyisameasureofthe'disorder'ofasystem,andthatasystem
is negative cannot be used frx becomes more stable wheri its energy is spread out in a m0<e disordered state
endothermicructions. The concept 5.3b) expla inthel.'l"1tropychangesthatouurduringachangeinstate,e.g.(s)-->(I};
of entropy as a measure of disorder is 0)-->(g);(s)-->(aq),duringatemperaturechange,andduringareactiooin
introducedandthefactthatthetotal whichthereisachangeinthenumberolgaseousmolecules
entropychangemustbepositivefor 5.3c) predictwhethertherotropychangeforagivenprocessispositiveornegative
aspontaneousproceJSisdiscussed. 5.3d) cakulatetheentropychangef0<areilction,iti,giventhestandardl.'l"ltropies,
Forchemic;i/changes, the concept of s.ofthereactantsandproducts
Gibbsfreee,..rgyprovidesasimpler 5.4a) definestandardGibbsfreel.'l"lergychangeofrwctionbymeamoftheequation
method of determining the feasibility aG,,,.,H - rtJS
of a reaction. 5.4b) cakulatet.Gt0<areactionusingtheequatioot.G:tlH- ras
5.4c) statewhetherareaction0<processwillbespontaneousb','usingthesignofAG
5.4d) predicttheeffectoftemperaturechangeonthespontaneityolareactioo,given
standardrothalpyandl.'l"ltropychanges
10.1f) interpretandexplainqualitativelythetrendinthethermalstabilityofthe
Group2nilratesandcarbonatesintermsofthechargedensityofthecationand
thepolaris..ibHityofthelargeanion
10.1g) interpretandexplainqualitativelythevarlationin solubilityoftheGroup2
hydroxidesandsulfatesintermsofrelativemagnitudesofthel.'l"lthalpychange
ofhydrationandthecorres.pondinglatticeroergy.
20.1 The Born-Haber cycle -finding the

strengths of ionic bonds
Lattice enthalpy
In Topic 5 we saw that the following entha lpy c hanges are measures of the strengths
of different types o f bondin g:
M{s)---+MO) enthalpy change of fusion, Mi'!,

MO)---tM(g) e nthalpychangeofvaporisation,liH!..,
329
PHYSICAL CHEMISTRY
M{s) ----+ M (g) enthalpy ehang,, of atomisation, llH !
X- Y(g) ----+ X{g} + Y{g} bond enthalpy, E(X- Y)
In the same way , we could use the entha lpy change for the following process:
as a me-a sure of the strength of ionic bonding. It d oes not measure the strength of a
single ionic bond bet"'<'en two ions, because there are many ionic bonds of different
strengths in all directions in an ionic lattice (in NaCl , for e,mmple, each Na~ ion is
surroundedbysixcl - ions , and ic isattractedtoeachofthem) . butnevenhelessit
allows useful comparisons to be made . The conve ntion usually used is IO quote the
enthalpy change for the reverse process, that is, the enthalpy change when one mole
of ionic solid is fonned from its isolated gaseous ions . This quantity is kno"'Jl as the
latt icccnthalpy(LE) (orlatticeenergy). lt has a laigenegmivevaluebecausethe
fonnation of an ionic c ompound is a strongly exOl:hermic process. For =ample. for
scxliumchloride:
N a+(g) + Cl - (g) ---t NaCl(s) LE =- 787kJmor1
The lattice enthalpy is the enthalpy change when one mole of the solid is !Ofmed from
it1isolatedionsinthegasphase
Lattice emhalpies are calculated in a similar way co lxmd enthalpies. except that the
additional factor of electron transfer must be taken into account . For scxlium chloride.
the energy associated with this proce.s.s is the sum of the following two energies:
the ionisation energy (IE) o f scxlium. for the process Na(g)-+ Na\g) + e -
the electron affinity (EA) of chlorine . for the process Cl(g) + e - ---t cr(g).
We met ionisation energies in section 2.13. The definition of electron affinity is as

follows.
The electronaffinity {EA}ofanatom{orion)isdelinedastheenergychangethatoccurs

when one mole of electrons combines wfth one mole of gaseous atoms (or ions). That is,
theelectronaffinftyistheenergychangeforthefo llowingprocess
X(g) + e--+ X-{g)
lfthereisaspaceinanatom'soutershellforanextraelectron.theeffectivenucle-:ir
charge usually attracts an electronsufficientlystronglytomakeitselectron affinity
=othermic. However. a second electron affinity is always positive because the
negativechargeontheion repels thesecondelectron . Forexample , foroxygen:
O(g) + e----t O - (g) .1H =- HlkJmor 1

o - (g) + e- ---t 0 1- (g) .1H =+790kJmol_,
Addingthesetv.ogives:
O(g) + 2e----t O'- (g) .1H =+619kJmoi- '
Flgure20.1 TheBom---Haber~lefDf Figure 20.1 shows how the lattice enthalpy of scxlium chloride may be worked out .
1odiumffikxide Such a cycle co nstructed to find a lattice enthalpy is called a Born-HaDCr cycle .
The values of all the terms in this Born-Haber cycle can be measulft!. with the
=cep1.ion of the lattice enthalpy . (Jc is nOI: physically possible to produce a mole
of isolated gaseous ions - the electrostatic fonces would be too great - let alone
330
20 Funher energy changes I
condensethemintoamoleofsolid lattice.) Butthelaniceenthalpycanbecalculated
Afl:(Na) + Afl!:(Cl) + IE(Na) + EA(Cl) + LE(Nad ) = Afll'(NaCl)

+1 07.3 + 121.3 + 495.8 + (-348.6) + LE(NaCJ) = ---4ll.2
LE(NaCJ ) = ---411.2 - (+375.8)
=-787kJmol 1
The situation is slightly more complicated if the ions carry more than one charge. For
example, for magnesium chloride. the energy change associated with the process:
is the sum of the first and second ionisation energies of magnesium (it is nol just
the second ionisation energy of magnesium). In addition. as the formula is MgCl,
we need to produce two ITK)]es of chloride ions. The Born- Haber cycle is shown in
Figure20.2.
Aff'",/Mg) + 2 X Afl!(C]) + 1st IE(Mg) + 2nd IE(Mg) + 2 X EA(C]) + LE(/l-lgC] 2)

= Afir{MgCl,)
+147.1 +2 x 121.3 + 737.7 + 14S0.7 + (2x - 348.6) + LE(MgCl,)
=-641.3
LE(MgCl,) = ----641.3 - (+1 880.9)
=--- 2522kJmoJ- '
Flgure20.2 TheBorn--ttabercy<lefDf
magne,;iumchlorkle
Coostnict a Bom---Haber cyde for each of the following compounds, and use it to
G1lrnlatethelatticeroergy.UsethedatagivenbelowinyoorG1kulations(allinkJrnot-1).
1 Na10
2 MgO
[IE(Na)~ +494; IE{Mg) ~ +736; IE(Mg*) ~ + 1450; EA(0) ~---141; EA(0-) =+790;
Af/l'(Na 10) 3 ---414; Af/l'(MgO} = ---602; Af/:i(Na) = + 107; Mr,'1(Mg) = + 147;
f(0=0) = +496]
The magnitude of the lattice enthalpy

The value of the bnice enthalpy of magnesium chloride is much larger than that
for sodium chloride. There are two reasons for this. The first is that there are more
cation-co-anion attractions bemuse there are twice as many chloride ions. The second
reason is that each of these anractions is much stronger. because the magnesium ion
carriestwicethechargeofthesodiumion.
There are Ol:her factors that determine the size of the Janice emhalpy. The most
imJX)flalll of these is how closely the ions approach each O!:her (the sum of their ionic
radii). The effects on the lanice enthalpy o f the di.stance becween the ions and the
chargesontheionsareillustmted inTable20 . I.
Table 20.1 For ioolc compounds of the Compound lnter-lonk dlstu,ce/rvn Charges on Ions L.attke energy/kl rno,1
sametype.lhe1horll'rtheinter-ionkdi1t;mce.
theg1eote1thevalueofthelotticel'fllhoi!)y. 1.1
Compoundsrnntainir,gdoublyortriply
chargedionshavemudi!argl'l"vo luesoflaltice
MgCI,
Li,O
MgO
331
PHYSICAL CHEMISTRY
latticeeoth alpiesaredeterminedbythemagnitudesol:
thechargesootheions
the inter-iooic distan{e
thetype ofJa-ttice.
Worked example
Writeanequationthatrepre51.'fltsthechemicalchangeassoci.-itedwiththelattice
eothalpyolcalciumlluoride
b Whicht\voelerneflts, ooelrom Group 1 ,mdtheotheffromGroup 17, loon a compound
withthemostnegativevalueoflatticeenthalpy?
Answer
cai*{g) + 21'ig)---->CaFi(1)
b Lithiumandlluorine,becaus.etheyhavethesmallestiookradii
1 Draw a Bom---Habef cycle for barium sulfide, BaS

b Us.ethefci lowingvalues {allinkJmor1)tocalculatethelatticeenthalpyofbarium
sulfide
Af/,,(Ba} =-t180;Afi.,(S) = t 249.2; 1stlE(Ba) =t502; 2ndlE(8a) = 966;
1stEA(S) = - 141.4;2ndEA(5) =+790.8;Afli(Ba5) = - 595.8
2 Explain why the following substance-; have diffell'nl values of lattice enthalpy from that
of sodium chloride
potassium chloride b magnesium ">U!lide c ulcium chlOOde
Ceramics
Cerantlcs 3resubstanceswith giantstrucruresthatconrnineitherstrongcovalent
bonds with some ionic characrer (e.g. SiOz) or strong ionic bonds with some
C0\-"3lent character (e.g. MgO and Al,Ol). They are hard but brittle. They are hard
bec3use of the strong interaton1ic forces that hold the crysrnl together, and brittle
because any deformation brings similarly charged ions closer together and leads to
increased repulsion . lftheionsh3vemultiplecharges.thelattia,-energy. melting
point and Young modulus (a measure of stiffness) all increase. as Ta ble 20 .2 shows.
Tab le 20.2 Theproperlie<;of'>Oll1eiooic Lattl ceenergy/ Meltlngpoln t!C Youngmodulu s/

subst.mces kJmol 1 GNm--2
MgO
The high melting points mean that a,-ramics are used for furnace linings. The linings
for blast furnaces are made of bricks with a high content of aluminium oxide. and
those for steel comerters are mainly magnesium oxide. made by heating magnesium
carbonate(seesection\0.4).
As the ch3rges in the ionic substa~ increase. so does the covalent character of
the bonds. By the time the charge reaches +4. as in sf'-. the bond can be considered
to be almost totally covalent. Ceramics such 3S silicon([\') oxide. SiO,. silicon([V)
nitride. Si 3N4. silicon([V) caibide. SiC, and tungsten carbide. WC. have high Young
moduli. and are useful in 3dding stiffness to plastics or metals. For =ample:
glassfibre.sembeddedineJXIXyresin.s('glass-reinforccd plastic".GRP) areusedi n
thetile.scoveringthespaceshuttleconrninsiHcon(IV)oxidefibres
thebladesinsomejetenginesarestiffenedwithsilicon([V)caibide.
332
. .; _,,.. __ ,,.
-- -
Flg ure 20.3 Ceramic1prol'idem,mytJSeful
properties Some cemmks ran lose their electrical resistance completely when cooled and act
a Finec:hln.1i1hardb!ltbrittJe
as superconduc tors while stiJJ at rdatively hig h temperatures cornf"'red to tb<:>Se"
b ThetilescOYl.'fin9the1pace~utUehave
anextranelyklwthermalrnndtxtivity,and near to absolute zero that are needed to cause .superconductivity in metals. These
1oimutatetheimideofthe1huttlefromthe ceramics a"' mixtures of metal oxides, usually including copper oxide . One of them.
heatatr~try. with the approximate formula YBa 2Cu 30 7, is a superconductor at 90K. In the future,
cGRPi1toughanddoeo;notrnmxie,and10 these superconduaing ceramics could be used to transmit electricity over large
l'iusedextensivelyi11boat-b11i1ding
disrnnces without any loss in energy. o r to make highly efficient electrical devices
20.2 Enthalpy changes of solution and

hydration
Enthalpy change of solution
The solubilities of salts in water show wide variations, with no obvi01Js panem . One
of the facrors deiermining solubil ity is whether the e nthalpy change o f solution.
Af-1..,i, ofthesahisJX)Sitiveornegative. Thisenthalpychangeistheenergyassociated
withtheproce.s.s-
We must be careful to specify the dilution of the final solution when quoting this
enthalpy change. On dilution, the ions in a solution become more extensively hydraced
(an exothermic proces.s) and also move funher apan (an endothermic proces.s). The
relative imponance of these two effects changes with dilution. affecting the values of
Af-foo1 in a complicated way. A quoo:ed single value of AH.,,i rd'ers to an "infinitely dilute '
solution . This value cannol be detennined directly by experiment and must be found
by a proce.s.s of eXlrapolation. In practice. the..,- comes a point when funher dilution has
no measurable effect on the value of Af-1..,i, and this may be taken as infinite dilution.
The enthalpy change of solution, Ml,,., is the e nthalpy change when one mole of solute
dissolves in an infinite vd ume of wall.'!".
If AH.,,i is positive, the salt is likely to be insoluble or of veiy low solubility. lf Af-f,o1 is
approximatelyz.eroornegative.thenthesalcislikelytobesolubleorveiysoluble.
Enthalpy change of hydration

The value of Af-f,o1 depends on two energy changes. The first is the energy that holds
thelanicetogether, thatis,thelankeenergy. Thesecondistheenergygivenoutwhen
gaseous ions a....- hydrated . This is called the enthalpy change of hydr:ition, A/-fhyd .
The enthalpy change of hydration , Af/"fd, is the entha lpy change when one mo"' of
gaseous ions dissolves in an infinite vdume of wale<
m
PHYSICAL CHEMISTRY
For sodium chloride. we can construct the cycle shown in Figure 20.4 . The value
ofthelatticeenthalpyisfoundusing theBom- Habercycle (seeFigure20. l ): itis
- 787 kJ mol- ' . M-1..,i rnn be found =perimentally: its value is +3 .9kJ mor' . Therefore
J:i..Aflny.iJ = LE( NaCI) + Afl..i(NaC])

=-787 + 3.9
=-783.lkJmol'
where JX.M-11,y<V = Aflny,{Na') + Afi~Ci-) .

We can now see why similar substances can show wide variations in solubility .
Flgure20.4 He11~l.awcydeforthe Boththelatticeenthalpyandtheenthalpychangeofhydmtion arelargenegmhe
dis'>O!viriginwaterofsodiumchlolide quantities.Asmallpercenmgechangein eitherofthesehasaveiylargeeffectonthe
difference between the 1,vo terms : a O.~% change in LE would alter M-1..,i by 100%. for
=ample. These variations can be used to explain the differences in solubility of some
compounds of Group 2 (see section 20.6).
Table20 .3 Amoluteenthalpydlarigesof The Hess"s Law cycle does nOI: enable us to find AH~ for the individual ions.
hydrotionfmIDmecommon iom becauseitprovidesonlythesumoftheemhalpychangesofhydrationforthecation
and anion. In order to find their indi,~dual values. we must assign a value lo one of
Aflt.,..i/kJmor-'
the ions . The value for the H~ ion is generally agreed to be - l l20kJmol 1 and. by
using this value , we can calculate the a bsolut e e nthalpy c hange o f h y dration of
ions.as shown in Table20.3.
The values in Table 20.3 show that the absolute enthalpy change of hydration
Mg' depends on the ability of the ion to attract water molecules . Small. highly charged
ea' ions have the mos! negative value.sofM-/hyd (seesection4.9).
Erltha lpychangesofhydrationaremorenl'giltive
iftheionissmall
iftheionhastwoor threeunitsofchargeon ii
Worked example
Oraw an energy cycle to show the connectioo between solid magnesium chklride, its
gasrousionsandilsil<Jueousions
b Use the loHowing va lue s to u1lrnlate the value of Af/h\'d(MgCli)
LE(MgOi) 3 - 2375 k.Jmol1; AH,o,{MgCli) ~ -155.1 k.Jmol- 1
c Comparethisvaluewiththevalueobta inedfromtheseparateabsoluteenthalpychanges
of hydrat ionforMgl andClinTable20.3
Answer
a SeeFigure20.5
b FromFigure20.5
Af/~MgOi) = Af/~Mg*) + 2Af/"1 0(CI-)
~ LE + t.H,a
~-2375 - 155.1
~-2530k.Jmol 1
c FromTa ble20.3:
Af!~Mg"') + 2m~a-)3 - 1980 + 2x(- 339}
Flgure 20. 5 3-2658kJmol1
This va lue ag rees with that in b to within 5%: a lair agreement
334
1 Draw a Som- Haber cyde !Of aluminium fluoride, AIFfiS)
2 Use the following values (a ll in k.Jmot-1) to calculate the lattice energy of aluminium
fluoride:
Mlf(AIF1) ~ - 1504.1 ; Aflf(Al) ~ 324.3; AHf(F)~ 79.0; 1st IE{AI} ~ S77;
2r.dlE(A0 ~ 1820; 3rd IE(Al) ~ 2740; EA(Cl) ~- 328
3 Draw an ene<gy d~ram to show the rnm1ectioo between AIFis), its gaseous kins ,md
itsaqu{'()(Jsions
4 UsethefiguresinTabie20.3andthelatticeenthalpyva lueobtainedin ? tocabilate
AH,a(AIF1)
20.3 The concept of entropy

Spontaneous and reversible processes
A s pont a nL'OlL'! cha nge is one that. in the absence of any barrier. such as activation
energy. mkesplacenatumllyinthedirectionsrnted. NOlallchemkalchanges
thac occur sponrnneously are exOlhermk, and so the principle that Ml is negative
cannOI always be used as the criterion of feasibility. In order to find a mo"' general
principle, which will enable us IO predia if a reaction is spontaneous or nOI:, we need
toconsiderwhathappenstotheenergytha1 isreleasedorabsorbedinachemical
Spontaneous processes often take pbce because the JX)lential energy of the system
decreases - for example, a weight falls to the ground or an electric current flows
through a resislor from a point of hig h JX)lential to one of lower po1ential. ln lxxh
theseexamples, thereductioninJX)lentialenergyisaccompaniedbyanincreasein
heac.whichisrandomkineticenergy. Potentialenergyismuchmoreorderedthan
heal energy. In po1ential energy the energy mostly moves in a definite direction: in
heal energy the energy is random and moves in every direction . Random motion is
much more probable than direaed motion and that is why systems lend to become
The measure of this disorder is called e ntropy. and is given the symbol S. Formally
a change of entropy is defined using the equation AS = q/ T, where q is the amount
of heat 1ransferred al an absolute temperature T. We can se,, why the temperature is
important. An amount of random heat energy q added 10 a relatively ordered system
at a low temperature T1 causes more disorder than if the same amount of heat was
added to a much less ordered system at a higher temperature T2. An analogy that has
beenusedisthatasn=zeorcoughcausesmoredistuibanceinaquietlibraiythana
sneeze or cough in a noisy. busy street.
The general principle for a spontaneous change is that the to ta l e ntrop y c h a n ge
AS.o1 is p os lti\"C . This is known as the Second Law of Them,cxlynamics (the Law of
Conservation of Energy being the first).We know that heal spontaneously flows from
a hot body at ten1perature T, to a cold t:ody at temperature T1. The removal of an
amount of energy at temperature T, is accompanied by an entropy decrease
--q! T, . The addition of this energy to a cold t:ody at temperature T, is accompanied
by an entropy increase of +q! T, . The total entropy change is - q! T, + q/ T, (see
Figure 20.6). This is positive if T, > T,, which agrees with the observation that heal
flows spontaneously fonn a hot to a co ld body. If T, = T1, the system is in equiHbrium
but any heat transfer is so infinitely slow tha1 no useful work can be obtained from it.
This special condition when ilSio1 = 0 is known as a reversible c h a n ge
335
PHYSICAL CHEMISTRY
Flgure20.6Whenaquantityofheatqflows
from ahotbodyattemperature r,toacold
bodyattemperaturer,.~=---{lT,+rtT,
Thi1ispo:s.itiveifT,>T,
I
---F~,~~-~
coldbodyttemper ture T, I entropychange+q{T,
Entropy values
Unlike H. Scan be given an absolute value. Using the Third Law of Thermodynamics.
which st31es that :it a bsolute :r.cro thc e n trop y o f a pure, crystalline su bstancl'
ls :r.cro, we have a base from which we can measure absolute entropy values. This
law fits in with our idea that under these conditions a system is 31 the most ordered
that it can be; it also has experimental support from measurements at vety low
temperatures. Values for some elemems are listed in Table 20.4 . As entropy change is
q/T,itsunits areJmol 11s 1.
Table20.4Valuesofabsoluteentropil.'55" C{diamond} C(graphite) Na Mg fe

forsOOll'elements. These are at298K.irid
s1Jrnoi-'i.' 126.o 154.7
lf we look at Table 20.4. we can find some trends about absolute e ntropies. These
may be summarised as follows. S" values :
ncrease:i.sA, ncreases
increasefromsolidstoliquidstogases
e decreaseiftheelementissoft .
We find similar trends in the entropies o f the compounds listed in Table 20.5
Table20.5V.iluesofabsoluteentropiesfor
Compound Nac~1) Na,co,(1) KC~I) H,0(1) c,H,00(1) CO(g) CO:,(g)
some compounds
s1JmoJ'i.' 12.1 160.7
Some entropy changes

Anemropychangeisdefined:i.sqtT. Wecanusethistocalculatetheincreasein
emropy when lOkJ of heat flows from a hOI: body al SOOK to a cold body at 400K.
\Ve have :
entropy change of hOI: body = - l~000 =- 200Jmol- 'K- '
What is the entropy change whe<1 30kJ of emropy change of cold body = + ~OOO = + 2SOJ mo1- 1ir-1
heatflowsfromahotbodyat100Ctoa
ccldbodyat27C? total emropy change = - 200 + 2SO = + SOJ mol-' ic-'
AnOl:her example when it is easy to calculate the entropy change is the melting of a
solid at its melting point or the evaporation of a liquid at its boiling point. Under
these conditions the change is .._.versible and so AS.at is zero. This means that
/J.S = q/ T. where q is the molar lacent heat . Al 273K. the latem heat of fusion o f ice is
6.01 kJ mol- 1.This gives the entropy change as 6010/273 = 22.0J mol-' ir-' .
1 Thelatenthe.ltofvaporisiltklnofwater
is2260Jg- 1.Whatisitsentropych,mge Entropy change of a chemical reaction
of evaporation at 100C inJrnol-1 K-1?
The emropy change of chemical reaction can be calculated in a similar ""Y to that
2 Thelatentheatoffusionofleadis
23.0Jg- 1 at327C.Whatisitsentropy used for calculating emhalpy changes. But we must remember that although the
of fusion? standard emhalpy change of formation of elemems is zero. their standard entropies
336
Worked example
What is i15 !Of the reddion 2NaM + Cl1(g} ----> 2NaCl(s)?
Answer
Figure20.7showstheeotropychangesforthereactioo
Flgure 20.7 Cakulatingtheentropychange

fo r theformationol'>OdiumchlorkleAtOK,
!JS = OastJSforallthembstaoces = O
Whatisi1.sforthefo llowingl{'actions?
FromFigure20.7:
1 CaCO:i(s} ----> CaO(s)+C01(g}
2 >< 51.2 + 165.0 + A.5 = 2 x 72.1
2 C 1H~{g) + H10(1} ----> C 1H50H(I)
d.5 = 142.2 - 267.4 =- 125.2
3 Ni(g)+3Hi{Q) ---+ 2NH1(g)
= - 125.2Jmol 1K-1
[tJStJmot1K- 1:CilCOi{s)92.9;CaO(s)
~.7;H10(1)69.9;C 1H50H(l)160.7; lt isnotsurprisingthat the reac:tionisacrnmpaniedbyan1.>ntropydecreaseasagasisbeing
H10(g}130.6;Hi{g)B0.6;Ni{g)191.6; usedup.Thisentropydecreaseisonlypo~blebe<:ausethereoctionissoexothermicthat
NH1(g)192.3;C1Hh)219.S] theentropyoftheheatgivenoffmorethimrnmpensatesforthisdecrease.
Some Olher examples of emropy changes for different types of reactions are given in
T3ble20.6
Tab le20.6 Someexa~esolentropy Example .4S"/JK 1mot- 1 Typeofch ; i,ge
ch;mge-;
mixingtwogase1(onemok>ofe;,ch)
CoH,(s) _. CoHo{l) metling
evaporation
K(s)+l1(1) _. K1(1)
MgC01{1) _. Mg0{1) + CO,(g) dec:ompoo;ition
Nac~s) _. Na(aq) + cl -(aq)
ca'(aq> + co,>-(aq) _. caco,{s) prl.'Cipilatkm
20.4 Gibbs free energy

In a chemical reaction. we have 10 consider the entropy changes that take place both
inthesystem(thac is the reaction that ishappening)andinthesurroundings(which
ab.soIDs or gives out heat). Many chemical reactions are exoihermic and the entropy
increase in the surroundings more than compensates for any entropy decrease that
maybeiakingplaceinthesystem. Wehave:
Af",ui = Af"'l"'= + M " ~
M".......... dins> =i =-;

It is always possible to cakulaie the !Olal entropy change from these cwo terms but it
is more convenient if they are combined cogether in a single function . This function
is called the Gibbs free energy function after Josiah wmard Gibbs (see Figure 20.8) is
given the symbol AG.
Ftgure 20.8 .iosiahWl\ardGibbs(18J9.---1903),

theratherofffil'mical thermocfynamiG
337
PHYSICAL CHEMISTRY
h isa me:isureofthe101alentropyincreaseassociated withthereacrionand isa

measu,.,.ofthedriving forceofthatreaction.lfthereactionhasadecreaseinf.....,.
energy.itisfe:isible.Wehave:
This equation can be wriuen in the more familiar form:
\Ve can use this equation as follows :
ifAGisnegative,thereactionisfeasible
if AG" = 0. the reaction is in equilibrium
if AG" is positive, the reaction will n{){ go spontaneously to completion.
Theentropyincreaseassociatedwithadecreasein/1G"rnn begivenanOlher
imerpretation. Whereas - AH" is a measure of the total heat energy q lost from the
system, - AG" is the maxim!<m anx,unt of that 10ml energy that is available to do
work . Usually AG is Jess negative than AH but occasionally the reverse is true.
Calrulating ti.G 6
We can calculate AG for a reaaion in a similar way to that we calculated AH, using
free energies of formation rather than enthalpies of formation .
Worked example
Answer
Figure20.9showsthefreeefll'fgie1olformationf()(therNCtion.
Flgure 20.9 CalculatingAG"from

AG'fva llJ!.>I
AG",<C,flo(g)) 3~&G",<H,O(I))
(- 32.9kJmol- 1) (3~ - 237.2kJmol-')
CalculateAG"/0< FromFigure20.9
1 thecombustionofpropane - 32.9 + ,i.G~ - 788.8 - 711.6
[t.G'f(C1H3(g)): - 23.4kJmol- 1] AG' =- 1500.4 - (-32.9)
2 thechlorinationofethanetogiveethyl = - 1467 .SkJmo l-1
chloride (We shouldnotbesu rprisedthatt:.Gisso largeandnegative.The1eactioni1high~
(AG'!A.lmol- 1:C 1He;{g) - 32.9;CiH 5Cl(g) exothermicandthi1morethancompemate1forl'lS'"beingnegativebecauseofthe
- S2.9;HCl(g) - 95.2] r~uctioninthenumberofgasmolecules.)
Variation of LiG 6 with temperature

The values of AH and AS for a reaaion vary slightly with changes in temperature,
but the effect is very small compared to the effect that changes in temperature
have on AG. Increasing temperatu,._.. makes the TAS term increasingly important .
For example, over the temperature range 29.'IK to !SOOK. AH and AS for the
d=omposit:ion of calcium carbonate change by only a few per cent but AG changes
from+131kJmol""" 1 at 29.'l. to+16kJmoJ- 1 at IOOO K and--04kJmol- ' at !SOOK. To a
good approximation, we can regard AH and AS as constant and calculate how AG
changes with temperature using the equation AG = AH - T!J..S .
338
Worked example
FOfthereddionCiH 4(g) t HCl{g)----tCiH 5Cl(g), at298K,
Mr = - 96.7 kJmol -1 and t.G =-25.9 kJmol -1.
Calcu late the va lue of AG" at 1000K
Answer
,i.G~Afr - T!lS'"
At298K, - faS =-25.9 - (- 96.7) +70.SkJmot-1
t,.S'" z - 70800 ~-B9Jmol-l K-I
At 1000/~GE - 96.7 - (1ooox ~~)

= +142kJmol1
This shows that as the temperature increases, the addition reaction becomes less feasible
1 Calculate the tem peratult' at which tJG"' f01 the additioo of HCI to etheoe becomes
2 When KN0 1 dis'iO!ves in water at 298K, Mr 3 +34.8kJmol- 1 and AG'" = +O.JkJmot- 1

i1 Calrnlatell5.
b Calrnlatet'lG"'at 320K
t Comment oo the effect of temperature oo the solubility o f KN0 1
l Heptaneiscoovertedi ntomethylbeozene industriaHy:
C1H u;O) ----> C1Hall)+4Hi(g)
At 300 K, Af1 = +211kJmoj- 1 and t.G" +110k.JmoJ-1
EstimateAG"at
, 600K
b 900 K
t Expklinwhyyourl'51:imatedvalueswillrn>unreliilble
Applying free energy changes

The free enngy of a reaaion tells us whether the reaction proceeds spontaneously
and this depends on the signs and m agnitudes of lxxh l'!Jf9 and ~ for the reaction.
As Afi9 and Af can each be positive or negative, then, are four possibilities .
.D.H6 and .D.5 6 both positive

These re-actions are ~id to be entropy drivet1. These endOl:hennk n,actions. which
may nOI: be feasible al room temperatun,, become feasible if the temperature is raised
(Le Chatelier's Principle). The following are some examples:
melting and boiling

decomposition re-actions
e dectrolysis
dissolving(insomecases).
It is easy to see why lxxh AH and Af an, positive for melting and boiling (see
Figun, 20.10). The change is endOl:hermk because imem10lecular bonds an, being
broken. Thereisanincn,aseintheet1tropybecausedisorderincn,asesfromsolidto
liquid togas.
i\.lOS!decompo,sitionre-actions(forexample.thecrackingolalkanesandthe
thermal decomposition of calcium carbonate) an, endOl:hermk because the tOl:al bond
enthalpyintheproduasislessthanthatinthereactants. The energy required to
break relatively strong bonds is nOI recovered by the formation of fewer or weaker
bonds. Decom]X>Sition n,aaions an, accompanied by an increase in entropy because
the change in numberolmolecules.An.ispo,sitive.
339
PHYSICAL CHEMISTRY
Flgure 20. 10 MlandMboth

=:e: a melting ke and b boiling
Decompo.sitiOfl may be brought about by electrolysis rather than by heating. The

re-action can then take pbce at a temperature at which t,.e,9 is positive, because it is
beingdrivenbythepassageofanelectriccurrentthroughapo1entialdifference. For
the electrolysis of water. the minimum ,ultage needed to bring about decomposition
is l .2JV. This point is discussed in more detail in Topic 23 .
Liquids of similar polarity (for example. hexane and heptane) mix together in all
proportions. If the p;:,larity of the liquids is differem. hmvever. M-/ 9 becomes so large
and po.s~ive that they may be only panially miscible(for example. butan-1--ol and water).
The solubility then increases if the temperaru"' is raised . This is usually the .situation
when a covalent solid dis.solves in a liquid (for example, benzoic acid in water).
ThedissolvingofiOflicsolidsinwaterisanextremelycomplexproce.s.s.Because
ions hydrate to a gremer extent in dilute solution, dissolving an ionic solid in water
may be =othermic when the solution is dilute, buc endoihermic when it becomes
saturaced . Two entropy terms operate:
an entropy increase because the ions in the solid are free to move in solution
an entropy decrease because water molecules that were originally fr= to move
become restriccedbyhydrationoftheions .
This comp]= interplay between enthalpy and entropy faaors makes it ve,y difficult to
=plain why some ionic compounds are very soluble in wacer while O!her.s are hig hly
insoluble. Forionswithasinglecharge,theoverallentropychangeisusuallyp;:,sitive
and this means that compounds of Group l are water soluble, even when the enthalpy
of ,oJutiOfl is positive . For ions with a multiple charge. the overall entropy change is
usually negative. Many compounds in Group 2 han, a positive enthalpy of solution and
combining this \\ilh an adverse entropy cerm makes them insoluble (see page 345).
t:.H 9 and t:.5 9 both negative

These reactions are said to be enthalpy driven . These exothermic reactions are
feasible at low temperatures . Here are some common examples:
condensalion and freezing(see Figure 20. ll )

addition and combination reaaions
precipitation.
340
These re:ictions are the reverse of the reacrions in which both Af-/ 9 and AS
are positive. Although addition and combination reactions are feasible at f<X)fl}
temperatun,, it may be that the rate of reaction is then so slow that a catalyst has co
beused.Anexarnpleofthisisthecatalytichydrogenationofan alkene .
Flgure20.11 ,<,Haml"'5bothrn>gative
aformationofamowuystal.ind !J.H 6 negativeand85 6 positive
brain from clouds
These reactions are feasible at all temperatures. The reactants are said to be
mct astablcunderallconditionsbecausetheyexistonly becausetheaaivation
energy of the reaction is so high . They are them1cxlynamically utlSlable. but
kinetically inen . The following are some examples-
a few decomposition reactions

organiccombusi:ionreactions
combustion ofexplosives (see Figure 20 .12andthepanelonpage343).
Flgure20.12l!J-/negative
andAS"po1iliveafim\'tlfh
andbexpi01iwdecompositioo
olammoniumnitrate
341
PHYSICAL CHEMISTRY
Some substances decornJX)S<' excxhermically because the tcxal lxmd emhalpy in the
products is higher than that in the reactants. Examples include the decomposition of
ozoneanddinitrogenoxide:
Oh) ----t l-~01(g) - 142 .7 +<:i8.7

1
N p(g) ----t N 1(g} + 20/g) ---82.0 +74.1
This means th31 ozone and dinitrogen oxide rnnn<X be synthesised directly by the
tt"Verse of the reactions above. Oz.one is made by the combination of oxygen atoms
with oxygen molecules. and dinitrogen oxide is made by the thermal decomposition
lfthereactionrapidlygivesofflargequantitiesofgasathightemperaru..,,an
explosion may result. An example is the decomposition of propane-1.2,3-trinitrate
(commonly called nitroglycerine):
tl.H ../kJmol- 1 iiS 9 /)~ 1 mol 1

1
2C 3H 1N.i0 9 ----+ JN 1 + 5H 10 + 6C0 1 + f'z - 3617 + 1840
l!.H 6 positiveandti.5 6 negative

Reacrions of this type are nOl sponrn neously feasible and have to be driven. An
e,mmple is phomsymhesis (see Figure 20.13), which must be continuously supplied
with energy from sunlight.
llH ../KJmoi- 1 llS ../]K"" 1mol- 1
6C0 1(g) + 6Hp(l) ---+ C 6H 1p 6(s) + 60 2(g) +2803 - 225
F1gure20.131!,Hpositivea!ldAS"negative
photo,;ynthe1islnchloropla'its
342
Worked example
FOf the fo llowing processes, explain why AH ar.d i15 have the sigm {positive or negative)
showo.
Mg{s) + 0 1{g)--+MgO(s) tJ.H - ve,AS - ve
b C1H sOH(l)---->C1H,(g) + HiO(ll Af! +ve,AS -we
Answer
a AH is negative because relatively 1veak bonds in magnesium and oxygen are
converted into strong ionic bonds in magnesium oxide. i15 is negative because
M =- 1.
b Af.1 is positive because a relatively weak
II bond is being formed. AS is positive
bernuseAn =+1.
For the fo llowing processes, e~ain why t,H and a5 have the sigm {positiVI' or
negatiw)shown
1 C1H4(g) + H1!!l)--tC1H,;(g) t,,H - ve,tJS - ve

2 H10{s}--+ H10{g) ,lli +ve, a5 +ve
3 H101{1}---> H20(I) + 01(9) t,,H - ve, Af1 +ve
4 NH 4NOi{s) + (aq} ---> NH/ {aq} + N01iaq) t,,H +ve, dS - ve
Explosives
An =plosion is a chemical reaction that produces sound. as ""'JJ
as a great deal
ofheatandlight.Soundis producedifthespeedoftheejectedgasesexceedsthe
speedof sound,33()ms- 1 inair,resultinginthepropag:,tionofashockwave.
Some explosions are produced by propella nt s, fuels used to drive rockets
(Figure 20 .14a) or to set in ma1ion a shell or bullet in the barrel of a gun. These
reactions muSI take place quickly and smOO(hly. This is achieved by using a source
ofheatnearonesmall pan of the propellanttoinitiatethereactionandthentheheat
produced by the reaaion here sets off the propellant in contact with it . The speed
of propagation is comparatively slow, probably only a few metres per second, and
lastsallthetimethebulletorshell isinthebarrelofthegun. Propag:,tionofthe
explosion by heat is a characteriSlic of low CXJliosi\es. Common examples o f low
explosi,es include gunJX>wder (used in firework rockets) and cellulose trinitrate
(usedascorditeinthecartridgesofshellsorbullets).Lowexplo.sivesmaybeset
off using a match and fuse, or by being hit with a pereussion cap . The simplified
equationsforthedecomp;:,sitionsareasfollmvs:
3C(s)
.......
+ S(s) + 2KNOJ/s) ----t K1S{s) + 3COig) + N 1(g)
::::~~':~~) ----t 4i"co(g) + l~COi(g) + ~Hp(g) + 1iN,(g)
Cellulose trinitrate contains enough oxygen for all the products to be gaseous. The
caibon monoxide produced bums to form carbon d ioxide in the air around the
explosion .
Other types of explosive are set off by a shock wave . This process is called
d e tonation and is charaaeriSlic of high e xplosh-cs (see Fig ure 20.14b). The whole
explosion is nearly instantaneous as the shock wave travels at the speed of sound.
which in a solid can be as high as IOOOms- . The explosion produced is much more
intense than that from a low explosive. High explosives are used in mining, for the
demolition of buildings and in the warheads of shells. A high explosive would be
disastrous if used in the canridge of a rifle - the explosion would be so violem that
the gun would explode instead of the bullet being sent ou t of the barrel.
343
PHYSICAL CHEMISTRY
,/~ :
I
Flgure 20.14 a AriallelO(ket.Liqukl Common examples o f high explosives include TNT (see section 25 .3) and propane-
h)'Orogen is l1Sl'd a1fuelin themdetengin e L2.}-trinitrate. Thelam,r, by itself. is highly dangerous and sensitive to s hock . Alfred
Thetworocket boosterseither sideofthe main Nobel made his fame and fonune by showing that when it was absorbed in day, a
bodyaddtothethrustoftheen gine. bHigh
expl05ivei1u'>!.'dtodemolishthi1 warehouse much more stable explosive is produced. called dynamite. Propane-1.2,3-trinitrate
c Airbag1 inc:.mrequirerapidreleaseof contains enough oxygen for complete combustion. but TNT needs additio113I
nitmgen to inflate oxygen. o ften supplied by ammonium nitrate . A simplified equation representing the
decomp;:,sitions o f ~ and ammonium nitrate is as follmv~:
C 7H 1Np 6(s) + ~N H 4NOJ(s) ----+ 7CO(g) + 5N 1(g) + 9z H,O(g)
Hig h explosives must be sel o ff with a detonator. This contains a s mall quantity o f
ahighexplosive,suchas mercutyfulrninateorleadaz.ide , tha! is very sensitive to
shock . Detonatorscanbeusedtosetoffeitherhighexplosivesorlowexplosives.
becausetheshockwaveproducedissufficiendyintensetoset offa high explosive
and enough heat is given out to set o ff a low explosive .
Hg{CNO),(s) ---t Hg(l) + 2CO(g) + N ,(g)
m ....., . . . ~
This rapid release of nitrogen is used to inflate airbags in cars, using sodium azide.
NaN1 (seeFigure20.14c).
The manufucmN' of cx plos h l..'S ls , -cry dangc rous and thc>se che mical,; have
caused many fatal accidcm s. On no acco unt s hould their prcparation be
attc mptc d in the laboratory.
20.5 Trends in Group 2 compounds

Thermal stability of the carbonates and nitrates
We have already pointed out tha! the carbonates and nitrates of Group 2 require
increasingly higher temperatures befo.., they break down (see section 10.4). If we
look at the general reactions
MCOis) ..... MO{s) + co,(g)
wecanseethattheentropychangesforlxithreactionswillbepo,sith'ebecauseonemole
ofeachofthecarlxxiates g ivesoffonemoleofg:,sandonemoleofeachofthenitrates
gives off 2Yi moles of gas. Because the number of moles of gas evolved is the same for
allthecarbonates.theirentropychangeofdecompositlonshouldbesirnilar, asitnilar
a,gument applies to the entropy change of decomposition for all the nitrates. This means
that the ease of decomposition of the carlxxiates and nitrates is largely determined by
their enthalpy changes. This is shown by the data in Tables 20.7 and 20.8 .
344
Tabte20.7Val\11'5oftlli,t.Gandl!.5forthe Mg
decompositionoftheGroop2carbonates
Table20.8Value5ofAfl,t.G.indl!.5for Mg
thedernmpOS1tkmofanhydmu1Group2
nitrates. Group2 nitfatesareusuallyobt~r.ed
~hydratedsatts,whic:h\\i ll maKetheactual
valuesd ifferent,butthegener.iltrendshould
remain the same
At room temperature AG for all the reactions is po5ithe. lf we assume thm the
valuc,s of Ml and l'!.S do nOI: change much with temperarure, AG will approach zero
when TM .. AH. The cemperarure at which this occurs will be loweSI when AH
has the smallest po.sith'e value , that is at the top of the group . This agrees with the
obserrntion th31 the carbonates and nitrates at the top of the group decompose at a
lower temperature than those at the bouom .
The reason why AH becomes more positive as the proton number increases is
becausethesizeofthecatiOflincreases. Duringdecomposition.thelaigecaibonateand
nitrate ions become convened into oxide ions a t the same time as caibon dioxide or
nitrogen dioxide and oxygen are being given off. The e-:ise with which this happens is
affected by the cations thac are next to the carbonate or nitrate ions. The cwo chaiges
on the small magnesium cation create a much stronger electro6latic field than the two
chargesonthemuchlargerbariumcatiOfl. Wesaythatthemagnesiumionhasahigher
charge density. lltis high chaige density changes the shape of the anion making it more
like the shapes of the products(Rgure 20.15). Thischangeinshapeofthe anion is
most marked when the anion is laige and its electrons are no1: so fim,Jy anracted to the
nudeus . Wesaythatthecarbonateandnitrateionsareeasilypolarised.
Figure 20.15 The small magnesium Kl!\ h.11

ahighc:hargedeffiity;mdchange1the1hape
oftheG1rbooatekmtoagreate1degreethan
doeo;themuchl.;rgerbariumKln.Asimilar
diangeinlhapeh~enswiththenilrateion
Assuming that Ml and AS remain constant, use the data in Table 20.7 to calculate the
temperatures at which AG lot" the decomposit ion of magnesium Gtrbonate and barium
Gtrbonate becomezern
Solubility of Group 2 sulfates and hydroxides

The solubility of the sulfaces in Group 2 is in the order MgS04 > CaS0 4 > SrS04 >
BaS04 (see section 10.4). These are determined by the fr= energy of solution.The
entropy changes for the dissolving will be very similar as in all cases MSO.i(s) is being
convened into M' and so/- ions. The solubility changes are. therefore , Jaigely
de1ermined by the enthalpy changes of solution. These can be calculated using the
thermochemical cycle shown in Figure 20.16. This shows us that:
Forthesulfates.thevaluesoflatticeenergiesaredominated bythelaigesulfateion.
so there is a comparatively small change from magnesium to barium: they vaiy by
only S00kJ mol- ' from magnesium sulfate to barium sulfate (see Table 20.9). The
Flgure20.16 Thl'rmochemiulcyclefarthe enthalpy changes of hydration change to a greater extent (by 617kJmoJ') from the
'idubilityofGrouplsulfateo; small magnesium ion to the much Jaiger barium ion. The value for Aff'"i.y.lSO/-)
345
PHYSICAL CHEMISTRY
1
is constam, - t 16okJ mol . So the general m,nd is for Af-1'!, 1 co become mon,
1X>Sitive(by l17kJn,ol- 1)goingdownthegroup . Thisistheprindpalreasonforthe
decreasingsolubiHty.
Table 20.9 Thermoffiemicaldataforthe -LE(Mso.)I Ml....,CM 21/ Aflfotd(S0/11 l>H,,,i/ Solublltty/mol In

1olubilitie1of!heGmuplsulfate1 kJIIIOl 1 kJrno/- 1 kJmot- 1 kJrnot- 1 100gofwater
Mg 2.2x10-1
1.5x10-1
7.lxl~
1.lxlo-"
Thesolubilityofthehydroxidesisintheoppo.siteorder.thatisMg<Ca <Sr<Ba . lf,ve

apply a similar Bom----Haber cycle lo the hydroxides as we did for the sulfates. we have:
M-1..i = Afft,y,{M' *) + 2Mlt,y,{OH""") - LE(MOH)
2 x IVlny,/01-r) has the constant value - I IOOkJ tn0l 1. The lanice enthalpies for
the hydroxides change more down the g roup than do the lattice enthalpies for the
sulfates.andthisisthereasonforthere,oersedtrend in solubility(seeTable'lf').10).
Table20 .1 0 Thetm()(hemicaldataforthe
-LE(M(OH).}/ AH"1d(M 21/ Solubl lty/mol ln
1olubilitiesoftheGroup2hydroxides kl rnor kl rno1~ 100gofwater
Mg l.6x10-
2.s x 10- 1
3.4xHr'
4.1xm->
Because the hydroxide ion is small, the laaice enthalpies of the Group 2 hydroxides
are sensitive to changes in size of the cation and vary in value by 673kJ mol- 1 from
magnesium hydroxide to barium hydroxide. The changes in Air~~!''') are less than
this (617kJmoJ- 1). So in contraSI to the sulfates, AH'..,,_becomes more negative, by
S6 kJ mol' , on descending the group and the solubility increases.
Experimenta lly-deril'OOla tticeentha lpiescanbefoundusinga becomes incteasingly unfavourabie. The reverse effect is shown
Born-Haber cycle bytheGroup2h~roxides
The entha lpychangeofso lution isdetemiinedbythe lattice
Some key definitions
entha lpyand the entha lpychangeofhydration
The lattlceentha lpy,lf,istheenthalpydKmge whenone
Po!arisationofthela rgeanionbythedoublychargedcatioo
mole of the wlid is formed from its iwlated ions in the gas
dete<minesthestabilityof theGroup2nitratesandcarbonates
pha~
The<eisanentropychangeASwhenaqUilnl ityolheat qis
The ion isationenergy, IE,istheminimumenergychange
p;1ssedatanabsolllle temperatureT.
required to remove one mole of e~rons from one mole of
The<e is an entropy increas.e when a system becomes more
atoms inthegasphas.e
disordered,foreXilmplemelting,boiling,andincreas.einthe
The electron affinity, EA, is the energy ch ange when one mole
numberof gasmo~ules
olelectronsisi!ddedtoonemoleolatomsinthegasphas,e
Thetotal entmpyofthesy51emplussurround ingsmustincreas.e
The enthalpychangeofsolution,AH:,,istheenthalpy
fora spontaneous reaction
change when ooe mole of so lute is dissolved in an infinite
ThistotalentropyincreaseisrelatedtotheGibbsfreeenergy
~umeofwater.
AG.ThemorenegativeAGis,theg reaterthedrivingforceof
The enthalpychangofhydratlon,AH~istheenthalpy
the reaction
change wheo one mole of i'iOlated ions in the gas phase is
ThewluM ityofGroup2sulfatesdecreasewithincreasing
dissolvedinaninfinitevolumeofwat er.
protonnumber. Thisi1becaus.etheenthalpychangeof'iOlution
346
Examination practice questions b Theenthalpychangeof50lutionforMgC/1,Afl",..
(MgCli(s)},isrepresentedbythefollowingequation.
Please seethe data 5ectionoftheCDforanyA,.valuesyou MgCli{s} + aq ~ Mg1"'{aq) + 2c1- - (aq}
may need. Describethesimpleapparatusyoucoulduse,andthe
1 Calcium chloride, CaCl1, is an important industrial chemical measurements you would make, in order to determine a
usedinrefrigerationplants,forde-icingroadsandforgiving valueforAH",..{MgCli(s))inthelaboratory. [4]
greater strength to concrete. c Thetablebelmvlistsdatarelevanttotheformationof
a Show by means of an equation 1'1/hat is meant by the MgCl 1(aq).
latticeenergyofcakiumchloride. (1( entha lnvc Vi lue/kJmot""1
b Suggest,withanexplanation,howthelatticeenergies
of the following salts might compare in magnit ude with
that of calcium chloride
i cakiumfluoride,CaF1 ii calcium!.Ufide,CaS[3) latticeenergyofMgCli(s}
c Use the following data, together with additional data
from the data 5ection on the CD, to calculate the lattice
energyofCaCl1. Byconstructingrelevantthermochemicalcycles,usethe
standardenthaV}'change - 7%klmot- 1
aboYedatatocalculateavaluefor
i AH",..(MgCl 1 (s}),
off01mationofcac1,
ii~(cl-(g)}. [31
staml.irdenthaVJ' change +178kJmot- 1
d Describe and explain how the 50lubility of magnesium
ofotomi1abono!Ca(I)
sulfatecomparestothatofbariumsulfate. [4]
electron affinity per mole - 349kJmot- 1 {Cambridge International AS & A Level Chemistry 9701,
Paper42Qllune2012]
3 a Describeandexplainhowthe50lubilitiesofthesulfates
of the Group 2 elements vary down the group [3]
b Thefollowingtablelists50meenthalpychangesfor
magnesium and strontium compounds.
Enthalpych.1nge
(3( magnes ium/
kJmot-' kJmot-'
d When a !iOlution of CaCl1 is added to a solution of the
l.illiceenth.ilDvolM(OH):,
dicarboxylic acid, malonic acid, the 5aJt calcium malonate
enttlaV:,' dlangeofhY{lration
isprecipitatedasawhitesolid.Thesolidhasthe
ofM'()
following composition by mass: Ca, 28.2%; C, 25.2%;
enttlalpych.ingeolhydration
H, 1.4%; 0, 45.2%
ofOl-f")
i Calculate the empirical formula of calcium malonate
from these data i UsetheabovedatatocalculatevaluesofAfi:,.for
ii Suggestthestructuralformulaofmalonicacid. (3) Mg(OH), and Sr(OH}i.
[Cambridge International AS & A Level Chemistry 9701,
Paper 41 Q2 November 2009]
2 a i What is meant by the term enthalpy change of
hydration,Afft,.i7
iiWriteanequationthatrepresentsthe~ofthe
Mglion
iiiSuggestareasonwhy~oftheMg1ionisgreater
than~oftheci ion
iv Suggest why it is impossible to determine the enthalpy
changeofhydrationoftheoxideion,<Y-. (5)
347
PHYSICAL CHEMISTRY
ii Use your results in i to suggest whether Sr(OHh is neutralisation. Cakulatethe[OW(aq)]andthe

more or less soluble in water than is Mg(OH}i. State (Cil*'(aq))inthesaturatedsolution,andhence
any assumptions you make . calculateavalueforK,r,.
iii Suggest whether Sr(OHh would be more or less soluble iii Howwouldthe50lubilityofCa(OHhin 0.1 moldm- 1
inhotwaterthanincold.Explainyourreasoning. [SI NilOH rompare with that in water7 Explain your anw,,,er.
c Calcium hydroxide, Ca(OH}i, is slightly soluble in water. 161
i WriteanexpressionforK,r,forcakiumhydroxide,and {Cambridge International AS & A Level Chemistr_v 9701,
state its units. Paper 42 Q2 June 2010]
ii 25.0cm1 ofasaturatedsolutionofCa{OH)irequired
21 .0cm1 of O.OSOOmoldm- 1 HCI for complete
348
A Level
Physical chemistry
21 Quantitative kinetics
Topic 8 gal an overview of how

tomeasurerafllsofreaction,and
Learning outcomes
what factors increase the number Bytheeodofthistopicyoushouldbeableto
ofcollisions!Mthenoughenergy 8.1c) expla in ,md use the terms rate equation, order of roodion, rate const;int haff-life
too.-en:omerheactivationenergy of.-ireadion, rate-determiningstep(seealsolopic8)
barrler.lnthistopic.welookat 8.1d) rnmtruct arid use rate equations of the form rate = l:[Al"'[Br (forwhichm and n
ratesofreactionquantitatively.The are0, 1 or2),induding
ana/ysisofrhecol/isiontheory,rhe deducingtheorderofareaction,orthernteequatioofora1&1ction,from
simp/eJt model to explain kinetic concentration-timegraphsorfromexpe!imeritaldatarelatingtotheinitialrates
data, is developed. Analysing the mettiodandhalf-lifemethod
effflctsofconcen!Tationchangeson interp!Ningexpeml['fltaldataWlgraphicalfoon, indOOingcoocrotration---timeand
rhereactionrahPenable1u1towrifll rat~tralion!Japhs
a rate equation, and from this we ulcu!atinganinitialrateusingconc:entrationdata
can obtain information about the 8.1e) showunclerstandingthat thehalf-lifeofafirst-orde11l'3ctionisindependentof
mechanism of the reaction. concentrationandmethehalf-lileofafirst-order~actioninulculations
8.1f) cakulatethenumericalvalueofarateconstant,forexamplebyusingtheinitial
rates or half-l ife method
8.1g) foramu!ti-1tep1&1ction,suggesta1&1ctionmechani1mthati1con1istentwiththe
rateequationandtheequationlortheovera llreoctionandpredicttheorderthat
woo Id result from a given rl'3ction mechanism {and vke versa)
8.1h)deviseasuitableexperimentaltechniquelorsttidyingtherateofareaction. from
given information
8.2c) expla inqtJalitativelytheeffectoftemperaturechangeonarateconstantand
hencetherateofareaction
8.3e) outline the different diaracteristics and modes ol action of homogeneous,
heterogeoeousarKlenzymecatalysts.inc:ltJdingtheHaberprocess,thecatalytic
removal of ox& of nitrogen from the exhaust gases of car engines (..ee also
Topjc13),thecatalyticroleofatmosphericoxidesolnitrogenintheoxidationof
atmospheric1Ulfu1dioxide(seealsolopic 10),thecata!yticroleofFe1orf-eJ+ inthe
r1;io/-reaction,andthecatalyticroleofenzymes(incltJdingthe explanationof
~ilidtyusingasimplekx:kandkeyrnodelbutexdtJdinginhibition).
21.1 The rate of a reaction

An expression for the rate of a reaction
In Topic 8. several different ways to measure the rate of a re-action were seen.
E,rnmples included the gradient of a graph of volume of gas produced again.s1 time
(seepagelS6)andthegradientof3graphofabsorbanceag3insttime(seepagelS7).
In order to .study rates of reaction quantit:11ively, a precise definition of rate is needed.
This m3y be expressed either as how the concentration of a product P increases with
time , or how the concentration of a re-acrnm R decreases \\-ith time.
349
PHYSICAL CHEMISTRY
changeinconcentration ofa product
- change in mrationofareacunt
The negative sign in the second expressio n reOeas the fact that the concentration o f
thereactantis d ecreasin g andthereforeproduces apositivevaluefortherate,asit
should. The expressio ns a bove may be wrinen:
rate = Ll.:I or rate = -:Rl

Using cakulusncxacio n.thisbecomes:
ral = dlP) or rate = - dlR)
dt dt
Rate is measured in units of conce ntration per unit time. moldm- 3 s- '.
Calculus notation
Although we are nct going to use calculus in this topic. its nOlation is useful in
representing the s lope of a line at a particular point.
The expression ~ means th31 during the time ime,val I'll (which may be of any
length. for =ample I second. 20 minutes. etc.) , bet""'""
the two times 11 and 12 the
concentration of P. wriuen as IPL has changed from (P), to (PI, :
~ = ((Pl, - (PJ,)
I'll (1, - 1, )
~ therefore measures the au1rnge rate of reaction over this time interval. As
we decrease the time interval fit to sm:iller and smaller v:ilues, the v:,lue of A{PJ wiJJ
become smaller and sm:iller too, :ind the ratio ~ will approximme more and more
to the exact slope of the concentration-time graph at a panicubr point . In the limit.
when fit is (vinually) zero, the ratio becomes the exact rate at a p:icticular point . The
=pressionisthenwrittenas~ .
Measuring rates by physical and chemical analysis

Before investiga ting the rate of:, p:icticubr reaction. we need to know the overall
(stoic hiometric) equ:ition so th31 we can decide what method can be used to follow
it. Fo r =ample, if w e were studying the following esterifirntion re:iction :
CH1COzH + c,H50H -+ CH3C01CzH5 + H10

eth..noic acid ethanol ethyleth..noate
the decrease in the :,mo unt o f eth:inoic acid , a s found by titration, c ould be followed.
The rate at a giventimelisthe n :
- A{CH 1C0 2H] or - dlCH i CO,HI
"' "
Wecouldal.soexpress therateas any o fthe following
- d[C, H 0HI o r + dlCH 1co,c,H 5 1 or + d[H 20}
1
di di d/
All of these w o uld g ive the same numerirnl v:ilue o f the rate.
2NO,(g)
nitro:e,;dial::ide
howeve r,
- dlN,O, J ~ + dlNO,J
di di
becausetu:o molesof nitrogendioxideareproducedfor e ach o ne m o le of d initrogen
tetraoxideusedup. Whenthereare d ifferentcoefficientsintheequ:itionlikethis,itis
usual to define the rate in terms o f the substance with :, coefficient of I .
350
21 Quantitative kinetics I
[NO,]
rate = - dlN,O+J = .!_ dlN0,1
dt 2 di
Figun,21.lillustratesthispoim.
As we mentioned in Topic 8. although chemical analysis can be used to follow
how the amrnmt of one subsrnnce changes in a reaction. physical methods are
usually preferred . For the reaction alx,ve. for example, we could follow the change
involumeifwewerecarryingoutthereactioninthegasphase, becausethenumber
of moles of gas is changing. Alternatively. if we carried out the reaction in solution,
we could follow the change in co lour (dinitrogen tetraoxide is J)<lle yellow. while
nitrogen dioxide is dark brown).
The escerification re:iaion is diffirult to follow using a physical method because
there is no obvious change in a physical property as the reaction prixeeds. Here we
would have to use a chemical method of analysis . Samples of the r<,action mixture
ar<, extracted at measured time intervals aod the amo1mt of e1hanoic acid remaining
is found by titration with alkali. One problem with this methcxl is that the re-:iaion
continues to take place in the sample until the titration is complete, so thm the
concentration of ethanoic acid m time t is difficuh to me-:isure accurately. This reaaion
iscarriedoutusinganacidcataly.s1.andthereactionintheromple-scanbeeffectivdy
stopped by immedimdy adding the exact a,noum of alkali needed to neutralise the
(N,O,I acid catalyst which was added to the reaction mixture at the stan of the reaction. Other
L __ _ ----r-----'CCS-'---- re-:ictions can be Slopped by appropriate methOOs, such as rapid c<X>ling of the samples.
Factors affecting the rate of a reaction - a

Flgure 21.1 Thl'rateofthereaclklnattime quantitative approach
ri1 the gradlentofthernrxentra!ion-time
~ai:,i:v~t~~!~!:,~: is erther
In Topic 8. we looked at the various factors that determine the rate of a reaction . In
this topic. we examine quantitatively how some of these faaors affect the rate. This
quantitative data often gives information about how the re-action takes place, that is,
about the m ech a n ism of the reaction . This allows us to Sludy chemical reactions at
We have already discus;ed qua litatively how the following factors affect the rate of
concemration (orpressureforgasre-:ictions)
temperature
catalysts
light.
For convenience, when we cany out kinetics experiments in the laboratory. we

usually study homogeneous reaaions in aqueous solution . The principal factors that
we can study under these cond itions are the effects of concentration, temperature and
homogeneous catalysts. These wilJ now be considered in some detail.
21.2 The effect of concentration

In this section we shall Sludy a single reaction - the iodination of propanone - but
theprincipleseSlablishedcanbeappliedtornanyotherreaaions.
In acid solution. iodinereactswithpropanoneasfollows:
The stoichiometric equation c,mnot be
CH 3COCH/aq) + l 1(aq) ---t CH 11COCH/aq) + H\aq) + naq)
usedtopredicthO'Wconcentration
affect1therateofareaction It would be tempting to predia that the rate of the reaction depends on the
KinetkdatamlJS!befoundby concentration of bcxh the icxline and the propanone but, as we shall see, this is
experimeot nO{ the case . Information alxx.n the kinetics of a reaaion can be found only by
=periment, and does nO{ always agree with what might be =pected from the
stoichiometric equation.
351
PHYSICAL CHEMISTRY
The .stoichiometric equation is used to decide which sub51ance we are going to

follow during the reaction in order to measure the rate. In this case, the concentration
of iodine is mo.st easily measured, either using a colorimeter ( see section 8 .2) or by
titration with .sodium thi=ulfatc (see section 7.4). lt is much more difficult to foll=
the change in concentration of either propanone or the products of the reaction .
Because""' are investigating the effect d concentration on the rate of the reaction,
aUa1herfactorstha1mightaffectthemteshouldbekep1:constant. Accurate control
of cemperature is es.sentfal. The reaction should be carried out in a water 00th whose
temperature is controlled 10 within l K. For veiy accurate work, thermostatic water
bathswhoseternpemrurevariesbylessthan0. lKareavailable (seeFigure21.2). 0nce
the reaction has staned, the reactants ""' shaken well in order to mix them thoroughly.
Flgure2 1.2 Atherrnostatic:waterbathkeep1

thetemperatureofthereactioncoostant.
removingonefactarthatmighlaffecttherate
lnitialinvestigationsshowthatthereactionisnOI affected by light. but that itis

affected by 1-f'(aq) ions. which act as a c at.tly.st. As this is a homogeneous carnlysc. we
shall treat 1-f'(aq) ions in the s:ime way as we treat the other two react:rnts. We now
h.tve three sub.srnnces whose concentration may affect the rate: I,(aq) . CH 3COCH/aq)
and 1-f'(aq). In order to find out how each of them affects the rated the reaction.
we must vary each in turn while keeping the O{her two constant . There are two main
waysofdesigningexperimentstoachie vethis
keeping allreactantsinexcessexcepttheonebeing .studied
Keeping all reactants in excess except one

lf the concentrations of propanone and hydrogen ions are chosen to be much hig her
than th.tt o f iodine. then during the course of the reaction , their concentrations vary
solinlethattheymaybet.tken asco n.stant. Table21.1 illu.strateswhythisis the c a.se.
Table21.1 Atypkal">etofrnnc:entratiom Reactant concentratlonatstarU Concentratlonatend/

usedto1tudythekxlinaUooofprnpaMrie motdrrr' moldrrr'
TI!{'rnncentra~ooofhydrogen km1inc:reases
bec:au">eas\\1ell asbeingacatJly1t,iti1al10
beingproducedbythereaction CH,COCH, 1.00
l-'--'~ -'+,~.~~~~~+c-'~~~---1
A mixture d propanone and sulfuric add is placed in a them10statically controlled
water bath . The solution of iodine is also placed in the bath in a se-parate cont.liner.
At the stan of the experiment. the two solutions are mixed. shaken well and a
stop-dock .staned. At regular times. the conce ntration of iodine is found. and a g raph
is ploned of iodine concentration again.st time (see Figure 21.3).
The graph is a straight line. This shows that the rate, g iven by the negative gradient
of the graph, is constant. The rate does nO{ change as the iodine concentration falls -
the rate is independent of the iodine concentration .
352
Analysing the results - the order of the reaction
with respect to each reactant
The order of reaction with r<,spect to a r<,acrnnt. X, i.,lls us to what =tent the
concentrationofthatreactanthasaneffecconthereactionra!e . lnthiscase , sincethe
rate of the reaction is independent of the iodine concentration. we can write :
rate = - :~!,I =k. a constam

Wecanindicatethefactthat therateisncraffectedbytheicxlineconcentrationbywriling:
rate = k(Izf
Any term raised to the po"'<'r of zero is equal to I , so the !em, could be omined
altogether. We include it to emphasise that the effect of iodine concentration on the
ra!e has been studied and found to be zero order. This "'suit may seem su rprising.
and emphasises the point that ""' can not P"'dict which "'acmnts determine the
reaction ra!e by looking at the stoichiometric equa!ion .
Ofcou rse , therateisnotindependentofallthereactants. and the concentration of
t ime/
Flgure 21.3 Graphofiod inernn{entratkm
The order with "'spect to each "'acL~nt can be found by studying concentration--
agaimttimelortheiodinatiooofpropaoorie
time graphs like the one obtained for iodine. The three common types of rate
dependenceareshowninFigure21.4 .
>~ :
Flgure2 1.4 Thl't!neemostrnmmootypes
ofrnncerrtration-timegr~1: a zeroorder.
~o~~:n~;~~~ a~~ r~r

l:::t '------- :l:::t_, _______ _
{Rb i1 the
L time"'t E 1
"~ t; t;
1
(t;,) , (t;,),
The first example, Figure 21.4a, is like Figure 21.3 for iodine . The graph is a straight
line and the rate is constant . This shows tha t the rate is zero order with respect to that
reactant.sothatrate = k(Rl. (SincelRI = I . rate = k .)
In the second example, Figure 21.4b, the curve is a n exponential. a nd has a
The half-life of a r&Ktion is the time
constant half-life, tv,- By constant half-life ' we mean that the successive half-lives
takenfor theconcentration olare..ct.-mt
to decr&1seto halfit1inilial value. are the same. That is. the time taken for the concentration of the reactant to decrease
from [Rio to ~[Rio is the same as the time taken for the concentration to decrease from
f!Rlgto1(Rlo, and soon .
lnthe thirdexample , Figure21.4c.successivehalf-livesbecomelonger. This
ind icatesanordergreaterthan 1.Sinceordershigherthan2aremostu n usual. the
rateislikelytobeseco ndorder,that is,rate = k[Rf' .
lnordertoconfirmthat the..,actionisoftheordersu ggested by the concentration--
time graph. the resu lts can be used to plot a graph that is a straight line. For a zero--
order reaction. the graph of !Rl against time is a stmight Hne , a first-order reaction
givesastraightlineforagraphoflog , 0 1R)against time.a nda second-order reaction
gi,..,sastraight-Hnegraphwhen 111.R)isplottedagainsttime (seeFig u re21.)).
Fl gure 21 .5 S1raight-l inegraph1areobtained

forthefollowingplotl
a zero order:!R)againsttime
b firstorder:log, 0 (Rlagaimttime
c sernndorder1/IR)agaimttime
353
PHYSICAL CHEMISTRY
AnO{her. less reliable. way to check the order is IO me3sure the gradient of the
concentration-lime graph at vari01Js times in order to find the rates . These rates
can then be ploned against concentration: Figure 21.6 shows how this distinguishes
between the three possible orders .
lfitisfoundbyexperimentthat
rate~k(X] 1
th1.>ntheoroefwithrespectt0Xis 1
lfitisloondthat
rate ~ k(X] 1
thentheordefwithrespecttoXis2
Thefe are some 1&1ctions where changing the concentration of a reactant has no effect
ootherate.lnthi1u1sewecanwrite
rate~klXl
'"'
Flgure21.6 Rate-mocentrationgrapllsc.m
beusedtodislinguishbetweenzem-0rder,
and we saythat theorderwith respect to Xis zem. (Notethatn ~ 1, a rnmt,mt, no
matterwhatthe valueofn. )
first-o!derandsecond-orderreactioos.Toe
zero-orde1graphi1a1traightlineparallelto
thex-axis.Thefir,;t--onJergraphi1astraight The initial-rates method
linep;mingthmughtheorfginThe!ie<:ond- Analysingtheeffectofconcentrationofa reaaantontherateofare:ictionbythe
ordergraphis.iparabolastartingattheolig in
method of keeping all reactantsexceptoneinexcesshastheadvantagetha t a large
amount of data can be collected from each experiment. The results may be ploued
so that a straight-line graph is obtained. possibly up to the point when the ..,-action is
9(Wocomp leted. lfthisisthecase. wecanbeconfidentthattheordersuggestedby
Sometimes. however. it is nOI possible for all the reaaants to be in exce.s.s. In the
icxlin ation of propanone experiment. for example, the iodine concentration must
always be small. as this is the reactant who,;e concentration we are following during
the course of the reaction . AnOlher method is therefore needed to find the order of
re:iction with respect to the propanone and with r<,spect to the add.
Thisisdonebycarryingout aseriesofexperimentsinwhich theinitialconcentration
o f all thereactantsiskep1thesameexceptfortheoneunderinvestigation .whose
concentmtion isvaried. Atthestanofeachexperiment. the lnltialratl' isfoundfrom
the g radient of the concentration-time graph (see Figu re 21 .7) . By studying how the
initialmtechangeswhentheconcentration ofthisonereaa.~ntisvaried. wecanfind
the order with r<,specttothatreactant.
The init ia lrate ofareactklnistheslope(tangent) ofthecoocentration-timegraphatthe

startoftheredctioo,whent = O.
Flgure21.7 Theinitialrateisfoundfmmthe
gradie!\tatthest;irtofthere.ictklo,thatis,
whent=O
354
Table 21.2 shows 3 typical set of r,,sults for the iodinmion of propanone, in which
thec0flcentrationsolfirs1hydrogen ions and thenpropanonewerevaried . From
experiments L 2and3. asiH+lisreducedin!heratio 5: 3 : 1, sotheiniti3lrate
decre:ises in the ratio S : 3 : 1. Therefore. the reaction is first order with respect to IHi.
Table 21.2 Atypkalsetofre1ult1f0fthe Experiment [W]/ [I,]/ [CH 1COCH 1]/ lnltlalrate/
lodin.itiooofpropanone.lnitialrateswere
cakul.itedfromtheOOinernncentrafon---time
grapll.Becausetheo!Ol>fo f thereactkmwith
mo1- moldm- moldm---3 moldm-r
2 .0x10-<
re,pecttoiodinehao;alreadybeenlound,itis 1.2x10-'
notnl'Ces,arytovary[l1]
!I,Jiskept1mallerthan!heconcentratlom 4.0x1o-"
oftheotherre..ct,mtsbecausethechangein 1.2x10-'
!I,JisbeingusedtomO!lilorthereactkmrate
4.0xlo-"
Notethat.itth1'1tartof thereactkln,when
the initial ratei1me.1SUred.!I,]i'icomtantat
0 .002moldm- From experimems 1, 4 and 5, as [a-! 3COCH,) is reduced in the ratio 5:3 : I. so the
ra!eag:,indec..,-asesintheratio5:3 : I . Therefore.the reaction isalsofirs1orderwith
respect !O {CH 3COCH,) .
In the cased the icxlination d propanone experimem, it is easy to obtain an
accuratevaluefortheinitialratebecausethegraphd!l,Jag:,insttisastraightline.
This is nOI usually the case. and then the determination d the initial rate. found from
the gradiem when t = 0 , is much more difficuh .
Sometimes the initial rate may be found by a 'dock' method. The initial rate of the
reaction between peroxcxlisulfate( VI) ions and icxlide ions :
can be found by adding a known small amount of thiosulfate ions and a little starch .
lnitiallytheicxlineprcxlucedreactswiththethiosulfateions:
but, as we saw in section 8.2. after the thiosulfate ions have been used up, the iodine
reacts with the starch to give a blue colour. The time taken, I, for this colour to
appear may be used as an approximate measure of the initial rate. If. for example.
(S,0 32-I = 0.003Qmoldm- 3, the equation shows that this will be used up when
!I,) = O.OOl5moldm- 3. Suppose that the time taken, t. is 6os. Then:
"ni~ "al rate of react"on = - ti.l I,J = O.OOIS
., 00
= 2.5x 10- 5 moldm- 3 s- '
This is only an approximate value because it assumes that the concentration-time

graph is a straight line nOI only near the origin. but up to the p;:>int when the blue
colour appeared (see Fig ure 21.8). The approximation is reasonable provided the
reaction is only a small way towards completion .
Flgu re 21. 8 A'ckx:k'methodgiwsa

valL!!'fDfthei nitialratelhatiskl\\'l'rlhan
thetruevalue, becau,;eita11umesthatthe
rnncentratKm-timegr.iphisa1traighl li neuntil
the'ckx:k'1top,; [I]:0.0015
~en cfoc~ n ---------- -------
stops)
355
PHYSICAL CHEMISTRY
21 .3 The rate equation

Arriving at the rate equation
Whentheorderofareactionwithrespec!toeachreactanthasbeenfound, the
re.suits are combined together in the form of a rate equa tion . For the icxlination of
propanone, we have the following resu lts-
rate ~ 11,J" rate~ (H *J' rate ~ (CH 3COCH,J'
These may be combined to give the following equation:
rate = kfl,!I W l'(CHiCOCHJI'
The constant I, is known as the rate con stan t. Strictly speaking. it is nOI necessary
to include the 11,J term (which is equal IOI) , and the exponent"\ ' after IJ--1 and
[CH 3COCHJI could be omined . It is , however. sometimes useful to include these
terms in the rate equation as they emphasise the effect of vaiying the concentration
of each reactant .
The reaction is now described as follows . It is :
zero order with respect to (I,!

first o rder with respectto[H*I
first o rder with respect to [CH 3COCHJI
of torn[ order 2, or second order o verall.
The total order is the sum o f the exponents from the rate equation . In this case, the
Finding the rate constant

In order to work out a value for the rate con51anl . k, we rnn use a set o f re:idings
such as those in Table 21.2. For example , if we use the figures in experiment I.
including the units:
rate = kfl,f'[H~]1(CH 3COCH,J'
2.0 x 10- lmoldm- ls- 1 = k x I ( no units) x O.S Omoldm- 3 x O.SO moldm- 3
k 2.0xlO-lmoldm- ls- '

l x O.SOxO.SOmol'dm-,;
graphof abvt = 8 .0x 10- lmol- 'dm1 s- '
Theunitsfor therateconstantdependonthetotalorderofthere:iction.
Unitsofk
overallfir51-orderreaction >1
overall5eeor.d-olerre<Ktioo: mot- 1dm1> 1
overall third-order rwction moridm6:,I
The first-Order case is imeresting because k has no units of coocentrntion. This means
graph of (ab - ab. ) v t that it can be detennined directly from a change in a physical property such as volume
or colour. As long as it is known tha! this property is proponional to the concemration , it
t ime.t is r>ot necessary to use the acrual concentration. For example. the rate of decomposition
Fig ure 21.9Graphsho1\lnghowaproperty of hydrogen peroxide may be studied by measuring the volu me of oxygen evolved. and
ofare..ctanl.l1Kh altheamorti.-mce.c:hange1 the rate of bromination of methanoic acid by measuring the decrease in absorl:xmce of
withtimefo1afir1t-Ofderreaction . Thefinal thebromine. Onekeyreadingmustbedeterminedasaccuratelyasp;:,s.sible:thisisthe
read ingab.mayootbezero. 'i0thi1value final reading, when the reacrion is complete. This enables us to construct a graph of
ha1tobe1ubtracted fromall tllereading1. An how the coocemration of a reactam (or the volume of gas , or the ab50rbance) decreases
example~ u1ing a rnklrimeter to measu re the
dec:re;r;e inab-;orbanceofbromineasltreacB with time. which finishes at zero. Such a graph can be used to evaluate the rate conslant
withmethanoicacid forafirst-orderreacrion(seeFigures21.9and21.10).
356
v_ These exponential concentration'--time graphs for firs1-0rder reactions can be
used to find the half-life of the reaction, which is related to the rate constant by the
following equation :
The rate equation shows how the rate changes with the concentration of the reactants
(and the concentration of a homogeneous catalyst. if one is present). The rate
constant is unaffected by changes in these concentrations . That is why it is called a
rate cons/an/. lfweexdudeheterogeneouscarnlystsand light,theonlyfactorthat
changesthevalueofarateconstantistemperature.
time,t
Flgure21.10 Graph1howinghowap,-operty
of a product, suchao;thl'volumeofag.r;,
changeswithtimeforafirst-Orderreaction The rateoonsta ntistheconstantofproportionalityinarateeqtJation
Thevclumereading1areeach1ubtractl'd ltisunaffectedbychangesinconcentration
fmmthefinalvolumetoprod ucetherequired ltchangeswithtemperature.
exponenti.ilcurve.Anex.i~ei1thevo lumeof
oxygenprodocedduringthedernrrisilkmof
hyrlrogenperoxide
Worked example
In tetradiloromethane at 4SC, dinitrogen pe<itilOxide, N1Q.;, decomposes as follows
NiOs---> 2NOi + ~ol
The rate of the r&Ktion was measured at different times. The results are shown in
Table21.3.
Table21.3 Rate1andreactantconcentration1 [N, OJ/ moldm-

atdifferenttime1. 1mol = 1a-mol
a Sugge-;tamethodoffo!klwingthereKlion
b Plotagraphofrateagainst(N 10 1].
c Useyourgraphtofindtheordefofthere.-ictionwithrespecttoN10 1.
d Cakukcitetherate rnmtant,givingitsunits
e Whatwillbethes.hape ofthegraphof[N 10 5] against time?
Answer
a Either measure the voltJme of oxygen g iven off, or measure the abso<b.lnce, 'iince
nitrogeodioxideisrnloured
b SeeFigure21.11.
Flgure21.11
;-=~
.15
0
{
"' 5
0
0 0.5 1.0 1.5 2.0 2.5
(N,0 5Jmoldm-
c Thegraphisastraightlinepas1ingthroughtheorigin,sothereilclioni1fir51order.
d Rat e = k!N10 5]w.l: = ~ - gradientofgraph =1.0 x 10-r1
e Thegraphwills.howanexponentialdecaywitharnnstanthall-lile.
357
PHYSICAL CHEMISTRY
In alkaline sclution, iodkle iom react with {hlorate(I) iom as follows
The r&ld:ion can be loHowed by measuring the absorbanc:e of IO-(aq) ions at 400nm in a
colorimell'f. Tab~ 21.4 shows a seriesol =red initial rates
...
Experlmlnt
,~
[,(aq))lmoldm-J [Cl<r(aq)]/mold m- 1 ln ttlal rat11/
moldm-s-
4.5x10-'
6.2x10-'
8.7x10-
4.6x10-'
8.6x10-'
1 Calrnlate the order ol the reactioo with respect to r(aq) icms and COiaq) ions
Explain your answer.
2 Writearateequatklnforther&ld:ion
3 Calrnlatetherateconstant,statingtheunits
21 .4 Reaction mechanisms
Proposing a mechanism
The rate equation is often used as abasisforsu ggestinga likely mechanism for the
reaction . ,\lose reactions can be broken down imo a number of steps. one of which
has a high activation energy that decermines the overall rate of the reaction . This
step is called the rote-determining SIC )). An analogy is a g roup of people buying
:, p:ipermtheloc:ilnewsagent. lfoneperson arrives,itrnkes them I second to pick
up the paper, 10 seconds to p:iy for it :ind I second to le:i,.., the shop . If ten people
:irrive 31 the same time, it t:ikes 10 seconds for them all to pick up their paper :ind
]()()seconds forthem:illtop:iy, but they still take only I secondeachtole:ive
the shop. There will be aqueuetopickupthep:iper:ind at the checkout.but not
on the ,v:iy out of the shop . Any step th:it rnkes place after the rate-determining
step has no effect on the overall rate. In the r:ite equmion for the iodin:ition of
iodine does n ot :ippe:ir in the rate equation. so any step involving iodine must come
:iftertherate-determiningstep. ltis:ilsore:isonableconcludethmthefirststepisthe
reaction of a proion with propanone. :is lxxh H :ind CHJCOCHJ appear :is first-order
terms in the rate equ:ition . This re:iction is an acid---1:xise re:iction . Such reaaions are
usu:illy fast and reversible (1-r exists :is HJo in aqueous solution). So we write:
C~~lHJ C~~/CHi
II II
Q. H H "',H + H,O
V ~ :
H
The second step. involving the breaking of a C-H bond. prob:ibly controls the rate
of the re:iaion: C-H bond bre:iking is known to be much slower than 0--H bond
bre:iking . In this step. a water molecule could act as :, base, taking :, prolon off the
358
protonated propanone and re-forming H 30~. A possible second step is therefore :
Iodine reacts rapidly with compounds conrnining the c=c group, so a fast Slep follrnvs:
Adding up all the individual steps in the mechanism. we arrive at the overall
stoichiometric equation :
Mechanistically we can define a homogeneous catalyst as a subsrnnce that appears in

therateequationbutnOlinthestoichiometricequation. Ifweconsiderjustthefirst
two steps, of which the secood is the rate--detennining .step, H3(r is a homogc ~us
catalyst.
NOie , however. that the laS1 of the three steps described abo,"' produces W{aq),
which. as we have seen . is the carnlyst for the firs t 1wo steps. A reaction which
produces its own catalyst like this is called autocatalytlc reaction.
are known as intermediates, be<:ause they are produced during the reaction buc are
nOlpanofthefinalproducrs.
Testing the mechanism

\Ve have now put foiward a possible mecha nis m for the reaction. which is consistent
with the kinetic data . We do nct yet know if this mechanism is the most likely one
and so we need to carry o ut funher experiments to confim, the mechanism. Some o f
thetechniquesusedarelisted below.
Use a wick.'!" range of conce ntrations - the experimentally determined rate equation
may hold over only a Hm~ed range of concentrations. For example. the proposed
mechanism for the iodinat:ion of propanone predicts that at very low coocentrat:ions
ofiodine, thezero-orderdependenceoftheiodinechangestofirst-orderdependence.
lhis is because the rate of the last reaction will be given by the =pres.sion :
rate = kTI J CH ,=c(OH)CH,)
where k' is the ra!e conSlant for the third Slep shown above , and so this ra!e will
decrease as flil decreases . At very low concentrations of iodine. the third Slep could
359
PHYSICAL CHEMISTRY
become so slow th31 ii effectively becomes the rate-determining step. This has been
shown to be the case, which fits in with the mechanism we have sugges1ed above.
Use sophis ticate d analytic te chniques - these may be able co detect the
presence of the suggesced intermediates. The use of nuclear magnetic resonance
(see Topic 29) shows that acidified propanone contains about one molecule
in 106 of the enol form. CH,=<:(OH)CH 3, an intermediate proposed by the
mechan sm.
Do experime nts o n the lntc mlCdlat cs - some intermediates are Slable enough
for experiments to be carried out o n them. For example, some organic halides form
tenfarycarbocations (seesection 14.})that can be isolated.
USC' i,;otoplc la belling - if an atom is labelled with an isOlopc (nOl necessarily a
mdioactive one). the label may indicate which bond has been broken in a reaction
For example. when some esters labelled with '8a are hydrolysed, the '8a appe:,rs
in the alcohol and not in the add group. This shows that the acyl oxygen bond,
and not the alkyl oxygen bond, is the one that is broken :
,,a
+ Hp ---4 CH 1 - c,
OH
Kinetic i,;oto pc c ffl'c t - deuterium behaves slightly differently from hydrogen:

for example, the G--D bond is slightly harder to break than the G--H bond . This
means that if this bond is broken during the rate-determining step , a compound
containing G--D bonds reacts betw=n 5 and 10 times as slowly as one with
G--H bonds. This is the case with the iodination of propanone: CDiCOCD1 reacts
On the other hand, the fact thm Cef-16 and QD 6 nitrate at the same rate sh=s that
the rate--detennining step is the initial anack by the NO;, ion (see sectiOfl 25 .J), and
nottheeliminationofthe proton.
C hange the soh 't'lll - the rate of ionic reactions change.s with the polarity of the
solvent . For example, the rate of hydrolysis of 2-bromo-2-methylpropane is raised
by the addition of sodium chloride. The sodium chloride increases the polarity of
On the other hand, the addition of sodium bromide reduces the overall rate . This is
because the ionisation of(CHi)iCBr is suppressed by the high cona,-ntmtion of Br
ions (Le Chatelier's Principle). and this can be larger than the positive effect caused
by the increased polarity of the solvent.
No amount of experimental work can ever prove that the proposed mechanism is the
correct one. In panicular. the role of the solvent is always uncenain. as there is no
way in which its cona,-ntration can be varied withou t changing the overall polarity.
Order and molecularity

Some complex reactions have orders that are negative or fractional. Other reaetions
have an order that changes with concentration, and only a detailed mathematical
treatment shows why this is so.
While the order of reaction may be non-integral , the molecularity of a reaction is
integral. The m o lecularit y is the number of s pecies in the rate-determining ste-p. This
must be integral. probably I or 2 . For many reaaions, the order and molecularity are
the same, and this can cause confusion bern=n them.
360
Worked example
1 Foread1oftheloHowingre.-icbons, H~rogen cyanide, HCN, adds on to ethanal, CH 3CHO, to give CH 3CHOHCN. Two
suggest a mechanism that is compatible mechanismshavebeeoproposedforthisrl!dclion:
withtherateequatioo CH 3CHO + W ----> [CH1CHOHr and [CH 3CHOHJ + CN-----> CH 3CHOHCN {1)
a H10i(aq) + 3riaq} -t 2W(aq)
----> 2H10(1l +I1-{aq}
rale = k!H 10i{aq)][r{aq))
b cio-{aq}+r(aq) Therateequationisrale = k[cN - ][CHiCHO][H'J 0
----> !0-{aq} + Cr-{aq}
a Whichmechanismiscons.istentwiththerateequalkln?Explainyoorans11'ef.
rate ~ k(OO-(aq)l[r{aq)l[OHiaq)J- 1 b Which step in this mechanism is the rate,<letermining step?
(H int:[OW]!H'"]isaconstant.)
c BrOiiaq) + SBr-{aq) + 6H*laq) Answer
----t3H 10(1) + 3Br1foq}
a Mechanism{l)isexduded becau'il' [H'] is in the lirstequation and so would appear in
rnte ~ k(H*laq)l!Briaq)l!BrOi- (aq)]
therateeq uation. Mechanism(2)iscons.istentwiththeral e!!QtJationbecause t hestep
2 Suggestwhythefollowingreactions
invoMr,gH'appearsahe<therate-determiningstep
havetwot&msintheirrnteeqtJations
b Thefirststepistherate-determiningstep
a C1H sC01CHi + H10
---+ C1H5C01H + CH,OH
rate ~ k 1(C 1H1CO.,CHij[W] +
k1!C1HsC01CHi ][OH-J
b H1{g) + I1(g)~2HI(g} 21.5 Reaction profiles
rale = k1fH1l!I1l - k1[HI]1
(Hint:wtiattworeactionsaretaking Intermediates and transition states
plarnineac:hca,;e?)
If we draw the reaction profile for a multi-step reaction such as that outlined in
section 21.4 , it is imponam !o distinguish an imC'nnediatC' (symbo l I), which
has an energy minimum , from a trans ition state (symbol TSt) . at the top of
the energy curve , which ha s an energy maximum . An intermediate is a definite
chemirnl species that exists for a finite length o f time. A transition state has no
permanent lifetime of its own - it exists for ju SI a few femtoseconds ( 10- 15 s)
when the molecules are in contact with each other. Even a reactive intermediate,
with a lifetime of only a microseco nd , has a long lifetime in co mparison with the
time that colliding molecules are in contact.
A simple one-step reaction. for example the S,.2 hydrolysis o f a primary
halogenoalkane (seesectionlS.2) .hasasingleenergyrn:iximum(seeFigure2\ .12) .
Flgu re 21.12 There.ictionprofileforaone-

stepreaction. Thefeisa'>irigletramition'itate
attheel\l'l'gymaximum
progr~ssof reaction
361
PHYSICAL CHEMISTRY
Ftgure2 1.13The1e..ctiooprofHeforatwo-
1tepreaction.Therei1anintl'nnediateland
atsotwotramitionstates.ln.1,thefir-;t1ti_>pi1
ratedetermin ing;in b. thewrnndstepisrate
determining
progressofr Ndion progres.sofr udion
If the reaction has two steps. on the other hand, there is an intermediate, I, and two
transition states.Anexampleisthehydrolysisof2-brorno-2-nx-thylpropane, which is
an S,.1 reaction(,..,., .section 15.2). The firs1 step is rate decermining and so has the
higheraetivationenergy(seefigure21.13a).
The structure of the transition state

It is possible to guess the structur<, of the transition state using H a m rnond's
p ostula te . This scaces thac the structure of the transition state will resemble thm of
theintermediatenearesttoit inenergy . lnFigure21.13a,thestructuresofthetwo
transition smtesr<,semblethatof theintermediate, 1. ln Figure21.l3b. thestructureof
thefirsttransition stateresemblesthat oftheinterrnediate,whilethatofthesecond
will be somewhere between that of the intermediate and the product .
WhileitisnO{possibletofind theexactenergyofthetransition stateexceptby
experiment,somecomrnon -senserulescanbefollowed. l'orexarnple, if the stage
involves bond bre3king, the activation energy is high, bu t ifthest3ge is 3 reaction
between ions o f opposite ch3rge. the 3ctivation energy is low .
Step swithhighactivationenergy:
betweentwoneutralrnolecules
betweenkmsofsimilarcharge
ifabor.dhfeakstoformffeeriidkals
Steps w ithlowactivationenergy:
betweentwofreeradkals
betweenionsofoppositecharge
add---basereactions
21.6 Some examples of catalysis

The Haber process
The Ha ber process produces ammonia by combining hydrogen gas with nitrogen gas.
The temperature 3nd pressure required to bring about the reaction are discussed in
section 10.5, butitisalsoessentialtouseacamlyst. Thecatalyst isrnadeofironthat
has traces of pornssium oxide and aluminium oxide in it . These impurities improve
362
the efficiency of the catalyst and are called promoters. Because the iron is a solid
and is in a differnu phase from the reactants, which are g ases, it is a hctC'rogelH.'Ous
cata lyst . Because the reaction rnkes place on the surface of the catalyst. it is essentfal
chm the iron is finely dhided so as to make the smface area as large as possible. This
canbeachievedbyreducingi:xw,dered ironoxidewithhydrogentornaketheiron
camly.s1.
The way the catalyst works is nOl completely underSlood. It is thought th31
the hydrogen and nitrogen are adsorbed onto the surface of the iron. where the
imeratornk bonds are weakened sufficiently for the hydrogen atoms to add omo the
nitrogen atoms in three steps. Breaking the nitrogen-nitrogen triple bond needs a kx
of energy and is thought to be the rate-determining step.
The three-way catalytic converter

This has been covered in section 8.6 . page 166.
Oxidation of sulfur dioxide: the formation

of 'acid rain'
A mixture of sulfur dioxide 3nd 3fr is very slowly convened imo sulfur trioxide . In the
presence of oxides of nitrogen. the reaction proceeds rapidly. the nitrogen monoxide
3cting as 3 homogeneous rnrnlyst by the following mechanism:
NO(g) + iz(g) ---+ NO,(g)

N0 1(g) + S0 1(g) ---+ SOJ(g) + NO(g)
Sulfur dioxide dissolves in water to give sulfurous 3cid, which is a weak acid. but
sulfurtrioxideformssulfuricacid.whichisastrongacid:
so,(g) + HzOO) ---t H1SO,(aq)

SOJ(g) + Hz00) ---+ H 1S0/aq)
Being a strong acid , sulfuric acid attacks buildings much more rapidly than
sulfurous acid . It is also much more damaging to plants because it makes the soil
veryac d c.
The iodide-peroxydisulfate(VI) reaction

lcxlide reacts slowly with aqueous peroxydisulfate{VI) ions to prc~:luce icxline and
The reaction is catalysed by the addition of some transition metal cations, for
exampleF.>"(aq):
2Fe,...(aq) + 21(aq) ---t 2Fe'\aq) + l,(aq)

2FeH(aq) + S 10 81-(aq) ---+ FeJ(aq) + 2so/-(aq)
Cons.ideringionkattrild:ion1andrepul1ion1,expjainwhyFe~orFelspeooupthe
redclion between r and S1o/-, where<tS voi-, c10- and No1- are not effective
catalysts
363
PHYSICAL CHEMISTRY
The rate ofaredetionisgiveflbythefollowingexpressions

rate = ~orrate3-a[R)
at at
Theunitsofratearemoldm- 1 .,--1
The order of the reaction with respect to a redctant shows how the coocrotration of that reactant affects the rate of the reilction .
Theorderfo<e.xhreactantisfoundbyexperirnent,and t heseordersarecomb4nedtogetherina rateequat ion.
Theproportionalityconstantintherateequat ionisca lledthe rateconstant.Thernteconstantdoesnotvarywithconcentratklnbut
itdoesvarywithtemperature.
A ho mogeneo us catalyst does not appe;ir in the overa ll :.toichiometrk equation, but its concentration does appear in the rate
equation
If the reactants and their coefficients in the rate equation are the same as those in the stoichiometric l'QUatioo, the t&Ktion may take
pklceina'ilnglestep
lf thereactantsandtheircoeffidentsinthernteequatklndifferfromthoseinthestoichiometricequatkln,thereiKtiontakesplacein
morethanonestl'f)
The51:Ppwiththehighe51:activationenergyisthe rate-determin ingstep .ThentJmberofspeciesthattakepartintherate-
dete<mining 51:l'fl is known as the mo lectJ la ri ty al the reaction
Reactants whose concentrations appear in the rate equat ion react before or at the rate-dete<mining 51:ep. Reactants whose
concentrationsdonotappearintherateequationbutdoapp&1r inthe5loichiometrkequationreactafte<therate-determiningstep
Tnmsition states aft' at the maxima in the energy profile of a redclion
lntermed iates areatthem inimaintheenergyprofileofareaction
A heterogeneous cata lyst is one t hat is in a different phase from the reactants. Hete<oger.eoos catalysts are important in many
well-knownindtJstrial reaction1 .

PleaseseethedatasectionoftheCDforanyA,valuesyou A study was carried out in which both [H 10z) and [WI were
mayoee<l. kept constant at 0.05 mol dm- 1, and n-1was plotted against
time. The following curve was obtained.
1 In the late 19thcenturythetwopioneersofthestudy
ofreactionkinetics,VernonHarrnurtandWilliamE5son,
studiedtherateofthe reactionbet1veen hydrogen peroxide o~=+r,.-'s-+--+--+--+--+--+--+--+-+---,
and iodideionsinacidicsolut ion .
H10z + 21- + 2H' --) 2H1 0 + 11
This reaction is considered to go by the following steps.
st e p 1 Hi0 1 + r--+ 10- + HzO

st e p2 10-+ W -+ HOI
st e p3 HOI + H~ +l-+ I 1 + H10
The general form of the rate equation is as follows.

0 30 60 90 120 150180210240270300
rate = k!H10zl'[r-flH'f timek
a Suggesthowtheappearanceofthesolutionmight lf.vou are aiming for a top-level grade you will need to
changeasthereactiontakesplace. [1]
draw relevant construction lines on the graph to 'illa-N
b Suggestvaluesfortheordersa,bandcintherate your working. Draw them using a pencil and ruler.
equationforeachofthefollowingcases c Cakulatetheinitialrateofthisreaction a ndstateits
units (2]
d Use half-life data calculated from the graph to show that
I 1,
the reactionisfirstorderwith respect to [1 ] (2]
1tepli1theskJwestOYefall I I
1tep2istheskJwe1tD1'l'fall
I I
1tep3i1theslowe51:0Yerall I I
131
364
e Usethefollowingdatatodeducetheorderswithrespect w
to (Hi0 1) and [W], explaining your reasoning. (2) CHi(:HO + 2CH10H ~ CH 3CH(OCH 3h + H10
l [H ,O,)/moldm- l [H*)/rnold m-
10.os 10.os a When the initial rate of this reaction was measured at
1 1.0 I various starting concentrations of the three reactants, the
10.07 10.os 1 1.4 I following results were obtained
10.09 I O.o7 11.s I
Expe ri ment [CH1CHO]/ [CH10 H]/ [H'"]I
f Fromyourresults,ded1Kewhichofthethreestepsisthe numbe r moldrn___, mold rrr 1 moldm-
slo1vest(rate-determining)step. (1)
{CiJtnbridge International AS & A Level Chemistry 9701,
Paper 4 Q2 November 2008]
2 a The reaction between iodide ions and persulfate ions,
Sio/-, isslovv.
2r- + sp/- ---+ 11+ 2so/- i UsethedatainthetabletodeterminetheOfderwith
The reaction rnn be speeded up by adding a miall amount
respect to each reactant.
of Fe1~ or Fel> ions. The following two reilCtiom then take ii Useyourresultsfrompart i towritetherateequation
pli!Ce.
for the reaction.
iii State the units of the rateconstantintherateequation
iv Calculate the relative rate of reaction for a mixture in
whichthestartingconc:entrationsofallthreereactants
are0.20moldm- 1. [6]
i \\lhattypeofcatalysisisoccurring here?
b The concentration of the acetal product Wil'i measured
ii Theratesofreactions2 and3 are both faster than that 1vhen experiment number 1 was allowed to reach
ofreaction 1.Byconsideringthespecies involvedin equilibrium.Theresultisinc:ludedinthefollmvingtable
thesereactions,suggestareasonforthis.
iii The following reaction pathway diagram shows the [CH,CHO]/ [CH10 H]/ [H']/ [acetal A ]/ [H 20 ]/
mol mol mol mol mol
enthalpy profile of reaction 1. d rrr 1 d m- d m___, d m___, d rrr'
(0.20 - x)
equilibrium
2r+s,&.- equilibrium
oo '"'e,~
1,+2s&.- i Copyandcompletethesecondrmvofthetable
intermsofx,theconc:entrationofacetalAat
equilibrium. You may wish to consult the chemical
progr.,.,ofreaction equation above.
ii Usingthe[acetal A]asgiven, 0.025moldm- 1,calculate
Usethesameaxestodrawtheenthalpyprofilesof theequilibriumconc:entrationsoftheotherreactants
reaction 2 follmved by reaction 3 starting reaction2 andproductsandwritetheminthethirdrmvofthe
atthesameenthalpylevelasreaction 1. (4) table.
b The oxidation of SOi to S0 1 in the atmosphere is iii Write the expression for the equilibrium constant fOf
speededupbythepresenc:eofnitrogenoxides thisreaction,K,,statingitsunits
i Describe the environmental signific.anc:e of this reaction. iv Use your values in the th ird row of the table to
ii Describe a majOf source of S02 in the atmosphere. c.akulatethevalueofK,. [9]
iii By mearn; of suitable equations, show how nitrogen {Cambridge International AS & A Level Chemistry 9701,
oxidesspeedupthisreaction [4) Paper41 Q2 November 2011]
{Cambridge International AS & A Level Chemistry 9701, 4 a Catalysts c.an be described as homogeneous Of
Pitper4 Q41une 2009] heterogeneous.
3 Acetalsarecompoundsformedwhenaldehydesarereacted i What is meant by the terms homogeneous and
withanakoholandanacidc.atalyst. The reaction between heterogeneous?
ethanalandmethanolwasstudiedintheinertsolvent ii By using iron and its compounds as examples, outline
dioxan. the different modes of action of homogeneous and
heterogeneous catalysis
365
PHYSICAL CHEMISTRY
Chooseon eexampleofeac:htype,andforeach
example you should
statewhatthecatalystis,andwhetheritisactingas
a homogeneous or a heterogeneous catalyst,
write a balanced equation for the reaction,
outlineha,vthecatalystyouhavechosenworksto
decrease the activation energy. [BI
b The reaction between S01, N01 and 0 1 occurs in two
steps
N0 1 + so, ----+ NO + so, Afl'i =-B8KJmol- 1
NO + fa, ----+ N01 Afi'; =- 57 KJ mo1- 1 121

Theactivationenergyofthefirst reaction, . , is higher
1 {Cambridge lntemational AS & A Level Chemistry 9701,
than that of the second reaction, E. .
1 Paper41Q3November2012]
Constructafully-labelledreactionpathwaydiagramfor
thisreaction,labellingf01 ,01 ,Afl':andAfl';.
366
A Level
Physical chemistry
2 2 Quantitative equilibria
lnthistopicweuseequilibrium
constantstoprovideaquantitative
Learning outcomes
measure of the acidity of adds and Bytheeodofthistopicyoushouldbeableto
bases. The relationship between 7.2c) explain the terms pH, K., pK,, Kw ar.d use them in G1kulations
the pH scale and the hydrogen 7.2d) cak:ulate(H*(aq)]andpHvalues forstror,gand weakac:idsandstror.gbases
ionconcentrationinaso/utionis 7.2e) expla inthechokeofsuita~eindicator1foracid-basetitratiom,g iver1
described. Thissca/ecoventhe appropriate data
wholerangeofacidityfoundin 7.2fl desaibethechanges inpHduringacid-basetitr<1tioosandexplainthesechimge1
the laboratory. Wea/so/ookatthe intermsofthestreogthsof theadchandbases
concepts of solubility product and 7.2g) expl ainhowbuffersoluticmsrnntrolpH,anddescribeandexplaintOOruses,
partitioncoeffidents. induding thero leofHC01- incontrolli ng pHinblood
7.2h) cak:ulatethepHofbuffersolutions,given ap propriatedata
7.2i) s.howundefSlandingof,arKluse,thecorKeplof solubilityproduct,K'I'
7.2j) calculateK'l'fromcoocentrahonsarKlviceve!'Sil
7.2k) s.howundemandingof thecommooioneffect
7.3a) statewhat i:smeantbypartifoncoeflident;calrnlatearKluse apartitioo
coefficient !Of a sy,tem in which t he solute is in t he same molecular state in the
two solvents
22.1 The dissociation of weak acids

An add. HA. dissociates in water as follows:
HA and H10 ~ are Bronsted- Lowty adds (see section 6.2) - they can donme a prawn.
H,O and A- are their conjugate bases - they can accept a proton . lfthe equilibrium lies
over to the left. H10 * is a stronger add than HA, and HA is said to be a we a k acid .
We may write the equilibrium =pression (see section 9.7) for this re-action as follows:
K = (H ;O . (aq)JA-(aq))
' !H,O(l)JHA(aq)I
Pure water has a molar mass of 18.0gmol' and a density of l.OOgcm- 1 . Becau.se l dm 3
of water has a mass of 1000g.
!H,O(l)l = ~ = SS.Smoldm- 1
18.0><l
In any dilute aqueous solution, (H,0(1)1 is very little different from this value and
so may be taken as a constant. The value of SS.Smoldm- J rnn be combined with
the equilibrium constant, K.,. and a new constant can bedeftned. called the a c id
dissoc latlo n co n s ta nt . K, . as follows :
K, = (H +~:~:q~~aq))
367
PHYSICAL CHEMISTRY
Table 22.1 lists the K , values for some common weak acids.
Equll lbr1 um KJ moldm_,
HNO:, s=> NO:,-+ H"' 5.6xHr'

H,co,,=,HCO,-+ W 2 .0xHr'
HCO:,H,='HCo,-+ W 1.6x10- 4
CH,CO,H r= CH,co,-+ W 1.7x10-'
h)'{Jmcyank:ac:id HCN ,=' CW + W 4.<JxH/ 10
K, values rnn be used to calculate the concentration of hydrogen ions in solutions of

weak acids . For example , if a solution of 0 .020moldm- 3 ethanoic acid is made up.
some of it will dissocbte co produce xmoldm- 3 of bol:h H"'(aq) and A-(aq):
IHA(aq) ) ltt+Caq)J
initiaVmoldm- 3 0.020 0
equiHbrium/ moldm- l (0.020 - x )
K, = -x- = l.7x 10-1moldm-3

(0.020 - x)
To avoid having to solve a quadratic equation, the solution to this equ3lion rnn be
simplified by assuming th31 x is small. so th31 (0 .020 - x ) .. 0 .020 . This is usually
jusi:ified because the degree of ionisation of a weak acid is very small. Hence:
(Without the approximation. the answer would have been '.).7'.) X 10---lmoldm- 3. The
differenceisinsignificambecauseitiswithinthelimitsoftheaccuracytowhichthe
data is given.)
Fora weak acid : For an add whose dissociation constant is K, and whose initial concentration is
(H'] ~ ..J{K, xc) cmoldm-l. we may use the formula {HJ = ..J( K, x c). NO{ice that this equation can
only be used if there are no added H'{aq) ions or A-(aq) ions : it cannot be used for
cakulationsinvolvingbuffersolutions(seesection22.3).
Worked example
Usir,gK,va luesfromTable22.1,cakulate
thehydrogenionrnncentrationineach CakukltethehydrogenionrnrKenlrationinaqueousO.OOSO moldmlhydmfluo ricilCid,
ol t helollowir,gaqueoos'iOlutions lorwhichK, = 5.6 x 10-4moldm- 1.
1 0.0036m~dm- J methanok acid Answer

2 1.3moldrr.1 hydrocyanic ilCid [H ] = ..J{K, x d = ..J (5.6x 10- 4 x 5.0 x 10- 1) ~ 1.7 x 10--lmo ldm --l
22.2 The ionic product of water (Kw)

and the pH scale
The ionic product of water
Pure water conducts electricity slightly, so it must be ionised to a small extent :
For this equilibrium:
368
22 Quantitative equilibria I
Because (H,o(l)) is a constant, we can define a new con.srnm called the Ionic product
of wa t<'r , K.,. such thm K., = IHP*(aq)l{OW(aq)J. Ek-cause [HP1 = [H*(aq)J (hydrogen
ions in water are all hydrated), this expression is often simplified to K., = [H')OHl.
Experimentally, K., is found 10 have a value of 1.0 x 10- 14 mol'drn--{i at 25C.
The ionicproductofwate r, Kw
Kw:[ W)[OW )= 1.0x 10- 14 mof! dm--6at 25'C
This expression shows that in an acidic solution the..,- wiJJ be a few hydroxide
ions, and th.~t in an alkaline solution there will be a few hydrogen ions. Even in a
concentrated solution of sodi um hydroxide. the"' are siill some hydrogen ions - the
equilibrium of the reaction
H_iO*{aq) + OW(aq) -.='- 2Hp(1)

is displaced to the right by the hydroxide ions added, brn a few H 30\aq) ions "'main.
Worked example
Calculate the hydrogen ion concentration, [H 3o]. in a 2.0 mojdm- J '>Olution of sodium
h~mxide
Answer
[H,0 ] = (;~] = l.O :.rr"= 5 X 10-" moldm-
In a n c mral solmion, the concentrations of H 3o and OH- are equal:
K.. = JHpuowJ = [Hp J'
{H 3o )' = 1.0 x 10- 14 mol 2dm~

(H 3o J = ,/(1.0 X 10- ") = LOX t0- 7moldm-J
The pH scale
The hydrogen ion concentration is a measure of the acidity of a solution . In different
solutions, thehydrogenionconcentration,[H1,canhavea \\-idernngeofvalues
(from about l moldm- 3 to LO x 10- 14 moldm- 3). To make the numbers representing
oddity easier to deal with, the pH sca le was intrcxluced. This scale is defined by the
expression:
pH = - log,o(Hi
(or, more precisely, as pH = - log, 0 ([Hl/moldm- 3), because logarithms can only be
cakenofaquantitywithoutunits)
So in a ncutr.il solution , in which (Hi = LO x 10- 7 moldm-3,
log,olHJ = - 7.0
pH = 7 .0
We can calculate the pH of an acidic solution , for example o ne in which

{Hi = j.O x 10- 2 moldm -3, as follows :
CalculatethepHof wchofthefollowing (H J = 3.0 x 10-'moldm- 3
wlutiorw
log, 0 [WJ = L52 (taking log, 0)
1 a0.002moldm -JsolutionofHO(aq)
pH = L52 (changing sign)
2 coocentratedHCl{aq),inwhich
[HCl] = 18moldm-l.
369
PHYSICAL CHEMISTRY
To find the pH of an a lka linC' solut ion , for example one in which
[OHl = 2.5 x 10-Jrnoldm-3_ we must first ,vork out IH1 using K.,:
{tt ]IOHl = 1.0 X 10- ' 4 moJ 2dm---(;
1
(ttI = ;~: ~:-~: = 4.0 x 10 "moldm-J
log, 0[HJ =- ll.40

pH = ll.40
The pH of strong acids and bases

\Ve can calculau, the pH of a solution of a strong acid or a strong base if we assume
it to be completely ionised. For a monoprcxic acid. that is, one that releases only one
tt + ion per molecule of add, IH+I = lacid]. For a monoprcxic base, thm is, one that
re:icts with only one H'" ion. IOH -) = (base[.
For a strong diprcxic acid such as sulfuric add, the situmion is complicated by the
factthmalthoughthefirst ionisation isthmofastrongacid.thesecond isnOI::
tt,so, .=" tt+ ttso ..- K.vcr,largc

ttso~ - ~ tt + so/- K. = LOX I0- 1 moldm- l
As an approximmion. we rnn ignore the second ionisation and treat sulfuric acid as a
strongmonopro(icacid.
For strong diprotic bases such as barium hydroxide, Ba(OH),. we may assume
complete ionisation and so (OW] = 2 x (basel.
pH and pK,
The symbol p means '- log, 0 '. Jc can also be used with K, and other similar
equilibrium constants:
pK;. = - Jog,oK.. (or. more strictly. pK, = - loglO(KJmoldm- 3))
For ethanoic add. K, = 1.7 x 10-~moldm- 3 and pK, = 4.76. Sometimes "pOH' is used
to represent - log, 0 (0HT. NOl:ice that pH + pOH = 14.
Worked example 1
CalcutatethepHofeachofthelollowingsolut ions
iia0.0S0moldm- 1 solutklnofhydriodicacid,HI (astrongadd)
b a0.30moldm-lsolutionofhydrofluoricacid, HF{K, = 5.6xlo--<lmoldm- 1 )
c a0.40moldm- lsolutiooofsodiumh~roxkle
Answer
a 8ecauseHii1astror.gacid,
[HI) = [H'] = O.OSOmoldm- 1
log10 [H+)E-1.3and pH ~1.3
b [H+] = -J(K, x d~ -J{S.6 x 10---<1 x0.30) ~ 1.30 x 10-1 moldm- 1
log,o[H']z-1.9ar.dpH~ 1.9
c Because[H'IOW] = 1.0x 10- 14 mol 1 dm---1;,
[H'] = l.O~-~O-" = 2.S x 10-"'moldm-'
log10 [H')E-13.6and pH ~ 13.6
CalcutatethepHof eachofthefollowingsolutklns
1 O.Smoldm- 1 HCI
2 2.Smoldrr.1 KOH(aq)
3 O.Smoldm- 1 benzok acid (Use the K, ~alue from TabJe 22.1.)
370
22.3 Buffer solutions
What is a buffer?
Many =periments, p<1tticularly in biochemistry , need to be carried ou! in solu!ions
of consrnnt pH . Alth01Jgh it is impossible to make a solution whose pH is tornlly
unaffected by the addition of small quantities of acid or alkali. it is possib le to make a
solution. called a buffer so lut ion . whose pH r<,m:,ins almost unchanged . A moderately
concentratedsolutionofastrongaddoralkalibehavesinthisway,andcanbeused
to provide solutions of nearly consta nt pH in the 0-2 or 12- 14 ranges. Dilute .solutions
ofS1rongacidsandbasesareusele.s.sasbuffersbe tv,eenpH 2andpH12. bemuse
the addition of small quantities of acid o r alkali changes their p H considerably. This
intennedbteran geofpHisve,yuseful , patticularlyforbiochernicalexperiments, and
so Ol:her means of making buffer solutions in this range have bet,,, devised.
A ,veak acid. by itself, aas as a poor buffer solution because its p H drops sharply when
a small quantity of add is added. A mixture of a weak acid and o ne of its s:ilts. however.
behaves as a good buffer solution. In such a mixture. then,isa high concentration of
A-(aq) from the salt. as well as the undissodated add. So the equilibrium:
~~of~id ~H+{aq) + ~ o f i , _
is well over to the left. which inc""15e"S the pH of the solution. When a small amount of
5trollg acid is added. mrnt of the =trn W{aq) ions =a with the reservoir of K (aq), and
so the equilibriu m moves to the left to remove the added H . This tends to minimise the
decrease in p H. When a small amoum of strong 1:xise is added. mos1 of the extra 0 1-t(aq)
ions =a with the reservoir of HA(aq) . and this tends to minimise the increase in p H.
Worked example
Write equatiom to show how the buffer solution desc ribed above removes
a addedWions b addedOWions
Answer
Aiaq} + H1aq} -t HA(aq) b HA{aq ) + OW (aq) -tA-(aq) + Hi O{I)
Finding the pH of a buffer solution

To calculate the p H of a buffer .solution of known composition., wie ruin with the equation.:
K _ (H' (aq)I A- (aq))..
. - [HA(aq)J..,
Because the presence of excess A-(aq) suppresses the ion isation of HA. the
equilibrium concentrations of A -(aq) and HA(aq). (K(aq)l.,q and [HA(aq)l.,q. are
almost idemical to their initial concemrations. IA -(aq)I., and (HA(aq)].,. which were
K, = (H'~: ::;)rq)).,
[H' (aq)) = K, (HA(aq) L.,.
(A- (aq)).,
This is the equation used for buffer solution calculations: notice that the equation
{ttI = ~(K, x c) must not be used in this case . because IHJ ~ (Al.
A buffer so lution isonewhosepHremaimnearlycoo stantootheadditiooofsmall

quantilies of;w::id or base.For;ibuf/ersolution:
[H'{ilq)] D K[~~~~l.,
For abuffer so lution, notethat:

[H*{aq)) ~ ~{K, xc}
371
PHYSICAL CHEMISTRY
Worked example
Cakukcite the pH of a solution made by mixing 100cm1 of O.lOmoldm- 1 ethanoic: add
(K, = 1.76x 10- 5 moldm- 1)with 100cml of 0.20moldm- 1 sodium ethaflO<lle
Answer
Aher mixing, the volume is 200cm1 and so the solution conta ins O.OSOmoldm-J ethanoic
addar.d0.10moldm-1 sodiumethanoate
(H'"(aq)] =Ki~~:~11 ~ 1.76x1:,'0x0.050 8.Sx10-'moldm-'
pH = 5.1
1 Calculate the pH of the buffer solution formed by adding 0.003 mol of NaOH to
100cm1 ol0.1moldm-1 methanokacid(K, = 1.6x 10--4moldm-1)
2 A buffer solufon is made by mixing 100cm1 of 0.20moldm- 1 NaiHP04 'With SOOcml of
0.30moldm -l NaH1P04. For the equ ilibrium
H1P0 4- (aq) ~ W(aq) + HPO/ - (aq)
K, 3 6.3 x 10- 7moldm- 1. Calculate the pH of the solution.
3 (Hilrdef)Calculate the change in pHwhl'fl O.OSOanl of 1.00moidm- 1 hydrochloric Mid
is added to
100cml of a solution of0.00010moldm- l hydrochloric Mid
b 100cml of a solution thatconta ins0.10moldm- 1 ethanoic acid and 0.10moldm- l
soditJmethaooate
K, forethaooicacidis 1.7x 10- 1moldm- 1.
(Hint: assumethatallthehydrochlorkacidreactswithethanoateions.)
Using buffer solutions

There are many situa!ioos where it is essential to control the pH . lo the following
examples , just the addition of an acid or an alkali is sufficient to keep the pH in the
required range without buffering .
lo s"Wimming pcx>ls. sterilisation is usually carried out using chlorine . This makes
the ,vater acidic (see section 11.4). Solid calcium hydroxide is added to bring the
pHtojustalx>ve7.
Acidic soils are treated with calcium catbooate or calcium hydroxide.
For add-loving plants, ammonium sulfate may be added to the soil. This acts as
a weak acid and can bring the pH of the soil !O pH 4, which is suitable for many
In O!:her cases, more acrura!e control of pH is essential. In the human body, the
production of catbon dioxide by respiration lowers the pH of the blocxl from aOOu!
pH7.5 to pH7 .3. The pH ofblocxl does not fall below !his value because blocxl acts
as an efficient buffer. There are several ways in which this buffering is accomplished ,
of which the following are the most imp;:>rtant.
Pl'O{eins are made up of amino acids (see Topic 27) . These contain bol:h acidic and
basic groups and can therefore act as buffers , removing H3o+ or OH- ,
R- NHz + H+ ---+ R- NH/
R-C0 1H + OH- ---+ R- C0 1- + H 10
Writeequationstoshowhowthe lhe acid H2C03 , derived from dissolved carbon dioxide. is buffered by the
H1C01/HCOi- buffersystemreacts presence of the hydrogencarborl3te ion. HC0 3- .
w.<h
Many {)(her processes. including the use o f shampoos and {)(her hair treatments.
il addedtt+ions
developing phO(ograph.s. medical inie"tions and fermentation. all require strict pH
b added011ions
control. This is achieved by the use of an appropriate buffer solution .
372
22.4 Titration curves and indicators
Titration curves for different acids and alkalis
During a titration, acid is usually pm into the burroe and run into alkali in the p r e = of
an indicator. This indicator suddenly changes colour at the end-point. which is the point
at which the number of moles of add is exactly balanced by the same amooJtU of alkali.
As we shaU see, this does nOI: always me:in that the solution m this point has a pH of 7 .
Flgure22.1 lnthisexpl!rimentalset-upto
recordtitrationrnrve1,thell'.ictioomixturei1
1tirll'dmagnetiG1ltyandthechafl9einpHis
rernrdedonthemeter.
Flgure22.2 ThegraphsshowthepH
charigeo;as10moldm-1 acidisruninto
;~: oj~~~~~~(t~~~~ :!:nl'll~~nt

1 Either the add or the alkali, or both. may be strong or weak. so that there:,..,- four possible
Toe purpo,;e of making the add ten times a1 combinations. If an acid is run into an alkali, the pH changes as .shown in Figure 22.2.
concentrateda1thealkaliistoemu1Ethereis
verylittlepHdi;mgeduetodilution
strong alkali
strong add
6 8 10 12 14 6 8 10 12 14
Y<llu meof adda<ldedkm1 Y<1lumeofa.clda<ldedlcm 1
strong add
6 8 10 12 14 6 8 10 12 14
Y<llu meof adda<ldedkm1 Y<1l umeofa.clda<ldedlcm1
373
PHYSICAL CHEMISTRY
With a st!Oflg alkali. such as sodium hydroxide, the pH scans at 13 and then decreases
slowly until 10cm1 ofacidhavebeenadded. Althispoint.the ('(JUlva}encepo!nt.the"'is
a sharp drop in pH - to about pH3 with a strong acid or to aboOJt pHS with a weak acid.
With a weak alblL such as ammonb. the pH stans at about 11 and falls with an
S-shaped curve to about pH7 until l0cm1 of add have been added . At this point
there is a drop - sharply with a strong acid to about pH 2 and slowly with a weak
Tab le22 .2 The~itabilityofmethylorange add to aOOut pH 5 .
andpheoolphthall'ina1i11dic~tor.;fortitrabom
To find the equivalence point accurately. an indicator must be cho.sen which
betwPe111troog,mdweak..c:id1andalkali1
changes colour when the curve is steepest. The colour will then change when only
one funher drop of add is added . Two common indicators are methyl orange and
strong 1trong methyl owige or phenolphthalein. Methyl orange changes colour over the pH range 3.2 !O 4.4 and
phenolphthalein phenolphthalein over the pH range 8.2 to 10.0. The titration curves show us that
strong phenolphthalein methyl orange is suitable for titrations between a strong or weak alkali and a strong
add, and phenolphthalein is suitable for titrations between a strong alkali and a strong
strong methyloror,ge
or weak add . Neither indicator gives a dear end-point with a distinct colour chang e in
a titration between a we-:ik alkali and a weak acid . This is summarised in Table 22.2.
Figure22.3showsthetitrationcurveswhenalkali is added co acid. rather than the
oo:her way around . The pH ranges over which methyl orange and phenolphchalein
change colour are also shown.
The steep portions of Figures 22 .2 and Figure 22.3 are the pans where the pH
changesmostrapidlywithadded alkali or acid . ltisatthesepointsthatanindicator
will change colour most rapidly. The pH range over which an indicator changes
colou r is usually abou t 2 pH units. so ii is imponam !O choose an indicator whose
F1gure 22 .3Trtra00nrnrves!itartir,gwith
100cm'of010moldm- 1 addand.idd ing colou r-change range is covered by the steep ponion of the titration cul"\'<'.
l .Omoldm- 1 alkali . Thernrve1aneareflectio11 Conversely. the flat ponions of the graphs show where the pH changes most
oftho'i!'lnFigure22.2.Therarige1ofthe slowly on addition of add or alkali. These flac portions are, therefore. where the best
indicator;are1hownbe1idethe!iteepportion1 buffering action occurs.
oftherurves
14 rtronga<ld 14 WNk;ocld
rtrongalUII mongalkall
phonolphthalel~ phenolphthalel~
I methyl orange
6 8 10 12 14 6 8 10 12 14
volumeofalkaW<m 1 volumeof alkaW<m1
14 WNk;ocld
wNk alkall
phenolphthalel~ phenolphthalel~
I methyl orange I methyl orange
6 8 10 12 14 6 8 10 12 14
volumeofalkaW<m1 volumeof alkaW<m1
374
Worked example
Some 0.10moldm- l sodium h~roxide is added to 25.0{m 3 of 0.10moldm- 1 h~rochk>rk
acid.CakulatethepHoftheresultingsolutiooafter theadditionof:
a 24.9{m 3 ofa lkali b 50.0cm1 ofalhli
Answe r
49
AmoontofHCI remajnir,g = c~ ~ = 0.10x (lS.~~ . ) 1.0x 10-5mol
1
Volume of solution ~ 25.0 + 24.9 = 49.9cml
1
[H'"] = ; = ;~~ : : , = 2.0x 10---<lmoldm- 1 and pHz 3.7
9
b Theacidha1nowallreacted,o;oweneedtocak:ulatethepHfromtheconcentrationof
h'jl}roxideiominthe50lution
Amotml of NaOH rema ining = c x ~ = 0.10x (SO.~~S.O) 2.Sx 10-'moi

1
Volumeofsolution = 25.0 + 50.0 = 75.0cml
(Of.] =;=:~~:\~:, =0.033moldm-'

{H') = [;;)=~~~: = 3.0x 10-
11 moldm- l and pH = 12.5
22.5 Solubility of salts

An imponant example of heterogeneous equilibrium is dissolving an ionic substance
in water. Take. for example. solid silver chloride in contact with:, saturated solution:
At a given temperature, the IAg~Clls)J term is a constant. iITespective of the amount

of silver chloride present . We can absorb this IAg+cl-(s)l term into the equilibrium
constam and define a new equilibrium constam:
~= IAg\aq)JCll3q)]
where K"I' is called the solubility product. For AgCJ(s). the value of K'f' is
1 x 10- 10 nx,l 2 dm--0. In a saturated solution of silver chloride in w:iter,
(Ag\aq)J = {cl-(;,q) h since their produce is I x 10- 10 mol 2dm--O, each of them mu.st
equal ,/(1 x Hr'O) = Ix 10- lmoldm--3.
Worked example 1
Calculate the solubility of Sr504. fllf which K'l' = 5.0 x 10- 1 mol1dm - 6.
Answe r
K'l' = [Sr1]!so/-J= s.o x 10-1mol1dm--0
So in a saturated solution
[Sr"*] = {So/- J= ,/(S.Ox 10- 7)
= 7.1 x 10""'4moldm-1
One mole of SrS0 4 dissolves to give or.e m~e of sr" ions, so the wlubility of SrS0 4 is
7.1x10--7moldm--l
The situmion is n>eoe complex if the s:ilt h3s ions wilh different chaiges. for example
rnlcium hydroxide . The solubility of Qi(OH), is I.) x 10-'moldm- 3. But here one mole
of C:,(OH)2 dissolves to give one mole of C:, 2* ions 3nd two moles of OH- ions.
375
PHYSICAL CHEMISTRY
Let (Ca(OH),J in the saturated solution be x . Then (Ca"J = :x and [OHl = 2x. The
solubilityproductisgivenby:
K.., = [Ca'1(0Hf
= xx (a)2
= 4:l
= 4 x(l. S x 10-2;-J = 1.35 x IO--Smol 3 dm--9
The connection between solubility 3nd sol ubility produa is summarised in

Table22.3
Table22.3 Therelatklmhipbetwt>en the Chargeont.lltlon C ~ on anlon Exa mp le ExpresslonforK
sol ubil ily(Kmrndm- ')aridsrnubilityprodtJCtfo r
s.iltswithdifferl'fl!Kl!lictype1 AgBr x'mol'dm--,;
MgC01 i'mof'dm_,,
1 The50lubilityofnkkelhydroxideis1.0 x 1o---lmoldm- 1.Whatisits:.olubility

product?
2 The solubility product of silver sulfate is 1.6 x 10- 5mol1dm--1l. What is its solub ility?
These connections between solubility and solubility product can only be used if no
O!:her ions have been added which would disturb the equilibrium . If, for example
we have a saturated solution of silver chloride, its solubility w ill be decreased if we
increase either the IAg"'(aq)] or the (Ct""(aq)J term. for example. by adding silver nitrate
or sodium chloride . This would cause sih'er chloride to precipitate out of the solution.
by what is known as the common ion c ffecc
Worked example
Aqueoussodiu mhydroxideisaddedto lfsodiumchlorideisaddedtoasaturatedsolutionofsilverchloride,sothat
aqurouscaldumchlorkletoprecipitate [Cl-{aq)) = 0 .10moldm-l, what is the maximum value for [Ag{aq)) in t he solution?
u1kiumhydroxide.Thefinalconcentr<1tion [K.,,(AgCJ) = 1.0 x 10- 10 molldm- 6)
ofhydroxklekmsisO.SOrnoldm- 1
Whatisthesolubilityol thecalcium Answer
hydroxide remaining in solution? K~~[Agtci-J so [AgJ ~~ 31.o;/::' = 1.0 x 10-9 moldm-l
[K!!'Ca(OHh = 1.4x 10-1molldm- ll]
22.6 The partition coefficient

A special case of equilibrium is how a solute divides between two immiscible liquid
phases . lfwetakeasolutesuchasicxline.whkhissolubleinavarietyofsolvents.
it isnOl:surprising tofindthatitisnOl:equallysolubleinallthesolvents. Taking the
two immiscible solvents water and hexane , we find that iodine is much more soluble
in hexane than it is in water. Methanol. on the other hand , is much more soluble in
waterthanitisinhexane.
Consideringtheva1iousinteITT10~ularlorcesthatmightopera te,expla inwhyiod ineis

more sduble in hexane than it is in water, whereas methanol is more sdub le in water.
376
Flgure22.4kldinepartitionedbetween
watera!ldhexane
When some iodine crystals are shaken with a mixture of hexane and water until no
funherchangetakesplace,andthetwolayersallowedtoseparate(seeFigure22.4),
wefindthmtheratiooftheconcentrationsofiodineineach layerisaconsrnnt.
This is true if we use only a small amount of i<:xline, or a much larger amount. This
constant istheequilibriumcon.stantforthechange:
11(aq) ~ I/hcxanc)
K = !l,(hexane)J
(l,(aq))
K is the panilion c ocff,clc nt of iodine between hexane and water. An alternmhe
phrase is dis tributio n C()('ff1clc nt . Like all equilibrium constants, the value of a
partition coefficient changes with temperature.
h is important always to \\-Tile an equation alongside a value of a panition
coefficient. Following the usual equilibrium consrnm =pression:
K = lpr<Xlucts)
(reactants!
we need to know which solution is the product ' and which is the reacrnnt '. There is
no universally accepted convention , but usually the organic solution is the "product"
on the right-h3nd side.
The equilibrium is a dynamic one: iodine molecules are consrnndy crossing the
imerfacebetweenthetwosolvents.Equilibriumisestablishedwhentheratesofthese
two processes are equal:
rateofleavingaqueouslayer = k,{[,(3q)]
Flgure22.5 Atequilibrium,theratesat
rateofleavinghexane = k,11;,(hexane)]
whichl,~ave1eachlayerareequal
(k,andk,arerateconstants).
AtequiHbrium.
[X(inS)J
k 1[[,(aq)) = k,([,(hexane)J
11,(hexane)] _ !!;__ = K
11,(aq)J k,
Notice that panitioncoeffidentsdonOl:usuallyhaveunits.
The technique of s ohcnt e xtrac tion depends on panition. This is used when
an organic comJx>Und is =tracted from an aqueous solution by an organic solvent.
[X(aq)J
which is immiscible with water. Examples would be if the aqueous solution contained
a perfume component or a pham,aceutirnl extracted from a plant, or conrnined the
377
PHYSICAL CHEMISTRY
productformedduring3syntheticreactioncarriedoutinalaborntory. lfweknow
the value of the partition coefficiem for the compound, we can calculate how much
would be extmcced imo the organic byer.
lndustrially,octan-l-0lisoftenusedastheorganicsolvem.
Worked example
ThepartitioncoeffkieotfOfthedistributionofcydohexanonebetw~nwaterarKl
octanolis24
0(aq) :;;::= 0(inoctanol) K = 24
Cakukite the mass of cydohexanone that would be extracted ii 20cm1 of octanol was
shakffiwith 100anlofanaqueou:ssolutioncontaining2.Sgofcydohexanone
Answer
Let [X] be the concentration of cydohexanone expressed in gcm -l; let the mass of
cydohexanone extracted be xg; the mass remaining in the aqueous layer will thefelore be
(2.5 - x)g
K = (X(octanol)]
{X(aq)]
[X(octanol)] = [X(aq)]xK
"fci=(2;5~/)x24
5x = (2.S - x)x24
X=2 .07g
Thisprocesshasextractedabout83%ofthe2.5gofcydoheXilnonethatwasinthewater.
lfwewantedtoextractmorecyclohexanone,wecooldrepe;ittheprocess.BtJtthis
wotJld reqtJire another 20cm1 of octanol. However, ii we were to split the original 20cml of
octanolintotwo1 0cmlportions,andtJSetheseforruccessiveextractions,omyi~dof
extracted material would increase. The following caktJlations will make this dear.
1 Let the mass ofcydohexanone extracted by the first 10an3 portion ofoctanol beyg. The
mass remaining in the water wi ll there!= be (2.S - y)g
{ac(\ 5
~Y)x24
10y = {2.S - y}x24
10y=60 - 24y
Y= 1.765g
Thislirstextractionresultsin2.S 1.765 = 0.735gofcyclohexaooneremaininginthe
aqueous layer
2 We can naw calculate hO'W much of this remaining cycloheXilnone Gin be extracted by
usingthesec:ond10cm 3 portionofoctanol
Let the mass of cydoheXilnone extracted by the sec:ond 10cm1 portion of octanol be
zg. The mass remaining in the water will be (0.735 - z)g
fo=(0.713!- z)x 24
Z=0 .519g
Thetotalmassolcycloliexaooneextractedisy + z = 1.765 + 0.519=2.28g
The tJse of two suc:cessiw extractions has naw raised the perceritage extrKted from
83o/oto1oox(W)=91%
tfahigherdegreeofextractionisrequired{whendealingwithexpensiveperfumery
components, fOf example), the process am be automated into a continuous extraction
apparatus
378
Wheo 100cm1 of an aqueous sollltioo rnnt.-iining 4.0g of ketone Y was shaken with
2Scm1 ofhexane ,3.0gof Ywasextractedinto thehexane
ii CalrnlatethepartitioornefficientofYbetweeohex.anearKlwater.
II What YOlume of hexane woo kl lH> needed to extract 90% of Y from the 100cm1 of its
i!QueoussohJtioo,usingonlyor.eextraction?
lndiluteaqul'O\.ls'iOlution,[H10Jisarnnstant, 55.Smoldm-l. Whenanacidistilratedwithbase,thereisarapklchangeinpH

F0< a wwk acid, HA, its degree of iooisation may be cakulated attheequivalencepoint.Anappropriate ind lcator canbeused
usingthefOfmula tolindthisequivalencepoint
K,3!~J:i-] When a solkl x1lt Mx- is in equil ibrium with its 5i!lurated solution,
theproduct(M[X-Jisaconstant,the solu billtyproduct, ~
Whenanacidistilratedwithbase,thereisarapklchangeinpH
e lnaqueoussolution,theproduct(W](OW)isaromtant,
attheequivalencepoint.Anappropriate ind lcator canbeused
the ion It product of water, K.,.. whose ~aloe is tolindthisequivalencepoint
1.0 x 10-14 mo11dm- 6 at roomtemperatu~
tfeitherexcessM'ionsorX-ionsareadded, the'iOlubilityofthe
pH ~ -iog 10 [W) x1ltdl'CredSl'S;thisiscalledthe commonioneffect.
FOfastrongacidorb.Jse,[H'"]or[OW] = c,whe<ecisthe When a substance X dis'iOlves in two immiscible liquids A and 8,
coocentrationoftheacidorbase the ratio:
Forawwkiteid,(W] ,. ,J(K,xc)
solubilityofXinsolventA
A buffersolution isor.ethatresistschangesinpHoothe
additklnofs.mallquantitiesofaddsOfbases. solubilityofXin'iOlventB
Abuffero;oluhonisusua llyamuctureofawe;ikacidandthesalt isacon1tant;thisconstanti1calledthe partitioncoefficient
ofthatweakilCid. ThepHolthebuffersolutioncanbefound
usingthefoonula
[H']3K[~~~
379
PHYSICAL CHEMISTRY

PleaseseethedatasectionoftheCDloranyA, valuesyou 2 a i Withtheaidofafully-labelleddiagram,describethe
standard hydrogen electrode.
""''""""'
1 a The K. values for some organic acids are listed below. ii Use the Data Booklet on the CO to calculate the
standard cell potential for the reaction betweener~
K0 /mo ldrrr' ionsandCr,o/- ions inacid50lution,andconstructa
CH1CO:,H 1.7xlo-s balancedequationforthereaction.
CICH,CO:,H Ux10-' iii Describe what you would see if a blue solution of cr1
Cl,CHCO,H 5.0x10-> ions was added to an acidified solut ion of Cr,o/- ions
until reaction w as complete.
i Explainthetrend inK0 valuesintermsofthestructures b A buffer solution is to be made us.ing 1.00 mol dm-:i
of these acids ethanoic acid, CH,CO,H, and 1.00 mol dm- :i sodium
ii CalculatethepHofa0.10moldm- 1 solutionof ethanoate, CH ,CO,Na.
CICH,CO,H. Calculate to the nearest 1 cm' the volumes of each
iii Useacopyof thefollowingaxesto~etch thetitration solution that 1'\!0uld be required to make 100 cm' of a
curve you vvould obtain when 20cm1 of 0.1 Omol dm- 1 buffersolutionwithpHS.SO.Clearly'>h01vallstepsin
, :1111
NaOH is added gradually to 10cmlof0.10moldm- 1 your working
CICH 1C01H. Ka (CH ,CO,H) = 1.79 x 10-5 mol dm- > [4]
c Write an equation to show the reaction of this buffer
solution with each of the follcming
i addedHCI
ii addedNaOH 121
d Choose o ne reaction in organic chemistry that is
catalysed by an acid, and1\lfitethe structural formulae of
the reactants and products. [3]
Paper42Q2June2013]
O 10 15 0
181
b i Write suitable equations to show how a mixture of
ethanoic acid, CH,CO,H, and sodium ethanoate acts
as a buffer rnlution to control the pH when either an
acidoranalkaliisadded.
ii CalculatethepHofabuffersolutioncontaining
0. 10moldm- 1 ethanoic acid and 0.20moldm- 1
sodiumethaooate. (4)
{Cambridge lntemational AS & A Level Chemistry 9701,
Paper 4 QI b & c June 2009]
380
A Level
Physical chemistry
2 3 Electrochemistry
lnthistopi<,westudyhowa
chemlca/reactioncanproduce
Learning outcomes
electricity. The standard electrode By theend of this topic:youshouldbeable to:
potential, E, of an electrode system 6.2a) state.-mda pplythe relatiori5hip F LebetweentheFarcldayconstant.the
isameasureof theeaseof reduet!on Avog adroconstant and ttmchargeontheeJectrori
of anatomor/on. The difference 6.2b)predictthe ideotityoft r>!!substance liberatedduringe~trolysisfromthestateof
between two electrode porent/11/s electrol yte (molteo or aq ueous),positionintheredoxseries(electrodepotential)
givesri5etaacel/potentla/,E~ and concentration
thesizeands/gnofwhlchlndlcates 6.2c) ralculate the quantityof chilrgepassedduringelectrolysis, and the mass
the f e1uibi/ityof 11reactlon.ln artdlorvolu me ol 5Ubstanceliberatedduringe!ectrolysis,includif1gtlx>sein the
contrut.manyreact/onsth1Harenot electrolys6 of H1S0Jaq) and of NaiSO_.{aq)
otherwisefeas/b/ecanbecarrledout 6.2d) describethedeterminationolavalueolth.eAvogadroconstantbyane!ectrolytic
by electrolysis - by passing an electric
current tMough the reacrion ml1tture. ="""'
6.3a) define the termsstanciKd electrode (redo,,:) potentlal and ru~rd eel potential
By choosing appropriate conditionf,, 6.3b) desaibethestandardhydrogenelectrode
a wide variety of USflful chemkah can 6.3c) desaibemethodsusedtolTK'il5Urethestandardelectrodepotentialsofmetalsor
be manufiKtured. non-metalsincontactwiththeirionsinaqueoussolution,andionsofthesame
element indifferentOl!idationstates
6.3d) ralculateastandardcellpotentialbycombiningtwost\dardelectrodepotentiak
6.3 ) usestandardcelpotentialstoexplainldeducethedirectionofelectronflowina
~lecell,andpredictthefe..JSi!j6tyofareaction
6.3f) deduce from~ values the relative reactivity of elements of Group 17 (the
halogens)asoKidkingagents
6.39) cnnstructredoxequationsu~ngtherelevanthatf-equatlons(seealsoTopic24)
6.3h) plroict qll<llitatively how the value of an electrode potential varies with the
concentrationsoftheaqueousions
6.3i) us.e the Nem51.eq uation,e.g.f .. E-+(0.0591z)log==:topredict
quantitatively~wthev<llueofan electr<Xiepotentialvaries withthe
conc:ffi trationsof the aqueousions;eMmplesindudeCu(s)+2e",;,=oi(aq),
Fe1+{aq) + e-~ Fe11aq),Cl.z(g) + 2e-,;,=2Ct"(aq)
6.4a) 51.atethepossi bleadvantagesofdevelop ingoth.e<typesofcell. e.g.theH/01 fuel
celland t henickel-metal hydrideand lithium-ionrechargeablebatteries
4' 23.1 The electrochemical cell

Measuring electrode potentials
If a metal. for example zinc. is pb~ in a solution conuining its ions. a n equilibri um
[s,l>e"lup:
lni1iallytheme1albeginstodi.s.solveinlhesolutionasmetalions.leavingthe
electrons on the undissolv,ed me1:1.l. This leaves the mt'l::tl negatively ch:,rg,:-d. Soon
anequilibriumisestablishedinwhichtherateofdissolvingisbabnc'll'dbyiorul
381
PHYSICAL CHEMISTRY
recovering electrons and ,.,_forming the mernl (see Figure 2}.1). The more reactive
themetal,thefunhertotherightisthep;:>:'litionofequilibriumandthelargeristhe
negmive charge on the metal. Therefore measuring this charge gives us a measure of
thereactivityofthemetal.
Flgure23.1 Theequilibriume-;tablishedtl'j
zJncmetalincoot.Ktwithit1fOm.Ado11ble
la)'l'rofcharge1i1forml.'datthemrfaceofthe
"""' ""''
Zn 2 (aq)
This chaige cannof be measured by connecting one tenni113J of a voluneter to the meml
because a vohme1er measures potential difference (p.d.) and needs its olher terminal
tobeconnectedtoasecondelectrodeatadifferentelearicalpo1.emial.hwouklbe
convenient if this .second electrode COOJld be made by purring an inen metal. such as
phtinurn. into the solution. Unfomrnately this does no1 help, as platinum sets up its own
po1emial which varies from experiment to =perimem, depending oo the solution it is
immersed in. so inconsis!ent results are obuined. Anolher approach must be used .
The solution to the problem is to reg:,rd the zjnc/zinc ion system as a h a lf-ecll and
connect it to ancxher half-eell . This will allow us to measure the pcxential difference
betwl"'en !hl"' two half-eells accurately and consistently. This means tha! we can only
compare reaaivities, rather than ml"'asuring them absolutely. The cxher half-e....Jl could
be. for example, acopper/copperionsy51em(see Figure23.2).
Flgure23.2 lWohatf-c:e!lsarecombinedto higlwesistance electronkvoltmeter

make;melectroc:hemic:alcell
~ - - - - - - { V)-- - - ~
,all bridge
The voltage produced by the two half-eells depl"'nds on the conditions. As long as
a high-resi51ancevoltmelerisused,sothatonlya verysrnallcurrentist:ikenfrom
the cell , and iftheconditionsar<,st:indard (298K. l .OObaror l .OO atm,solutions
of I.OOmoldm- 1), the volt:igl"' is the sta ndard CC' ll e.m .f.. E!,ll. (If an appreciable
currem is drawn from the celL the measured voltage would be smaller than this.)
The need for a salt bridge

As mentioned above, the voltage is measured using a hig h-resistance electronic
voltmeter. Evenso.someelectronsmustflowand.becausezincismorere:ictivethan
copJ)l"'r,thefollowinghalf-reactionst:ikeplacetoasmallextem
382
23 Electrochemistry l
at the zinc electrode Zn(,,) ----+ Znz+(aq) + 2c-

atthccoppcrdcctrode CuH(aq) + 2c-----+ Cu(s)
This means that the zinc solution becomes positively charged. with an exces,; of
Zn'*(aq) ions, and the copper sol!<tion becomes negatively charged. with an excess
ofSo4>--(aq)ions,forexample. ifcoppersulfacehasbeenused. Because of this.the
current would cease unless the circuit ,vere completed by electrically connecting the
two solutions . This rnnnOI: be done with a piece of wire, which passes only electrons,
because ""' neM to move positive ious one way and negathe iom the O!:her. ( It
does nOl matter which ions actually move. because very few of them are transferred
compared with those 3lready in the solutions.) The circuit is completed by 3 salt
bridge dipping imo the two solutions. Salt bridges are made from either a strip of
filterpapersoakedinanelectrolyte(seeFigure23.3) orabenttubepackedwithan
electrolyte jelly, with fX>fOUS plug s at the ends that allow ions to flow while minimising
the mixing of the electrolytes by diffusion . The electrolyte in the salt bridge is usually
Figure 23.3 Copper an d li ne ha ~-ce lls potassium nitrate. This is used because all potassium compounds and all nitrates 3"-""
connectl.'dtogether ,oluble. and so no p....-cipitate will form with any ions in contact with it.
The standard hydrogen electrode

The convention for determining the sign of the e .m.f of a cell is
E':.1 = E~-haodck<uodc - Etrt-hondd<d.o<1e

For the copper/ zinc cell shown in Figure 23.2. E!.,1 = - l .07SV. the negative sign
showing that the zinc electrode is more negative than the coppe,- electrode . This
fits in with what we know of the relative reactivities of copper and zinc : zinc ions
are much less readily reduced to the metal than copper ions . This value tells us
the voltage of a standard zinc half-cell compared with a standard copper half-cell .
Conventionally. it has been agreed to compare all half-cells against an electrode
called the s tandard hydroge n electrode (SH E). By international ag reement. this
has been assigned 9 = O.OOV. The reaction is :
H+(aq) + c- ~ }Hz(g)
The standardhydrogenelectrode is
thehatf-cell representedbytheeqliillion This n,-action is very slow to reach equiHbrium. and to speed it up the hydrogen
H"(aq} + e-s=' {Hi(g},Ptunder is bubbled over a platinum catalyst . The platinum su,face is platinisi - it has a
spongy layer of platinum electrolysed onto it. which increases its effective surface
st.-mdardconditk>ns.
area . The platinum is also an inen electrode. and transfers electrons to and from the
St,mdardconditklnsare: circuit without taking pan in any chemical reaction .
p = 1.00atm, 7 = 298Kar.dall Figure23.4showsthestandardhydrogenelectrode. Its half-cell ....-action is
concentratiom = 1.00moldm- l. represented as:
Flgure23.4 The1t;mdanl h)'d rogen electrode

PHYSICAL CHEMISTRY
Standard electrode potential, 9

Allhalf-eell reactionsarewritteninthefollowingformat. withtheelectronsontheleft
o:xidUCd form + ne - ~ reduced form
lfthevolrngeproducedbya half-cellismeasuredagain.stthesrnndard hydrogen

electrode.the cell voltage is
Butsince.E'"ldl--huK!dertrod< = O.OOVfortheSHE,
and the cell voltage is the s tandard elec trode pote ntial. 9 of the half-cell .
The reduced form of the sub.stance is not necessarily the fr= element - it may
be the element in a lower oxidatiOfl state. For =ample, in a solution containing
1.00moldm- 1 of Fez.(aq) ions and I.OOmoldm- 3 ofFeJ>(aq) ions, electrons are
tootand ard V transferred from the Pe2'"(aq) ions to the Fel>(aq) ions . In order to measure the
:r::~e: voltageforthishalf-<:ell.theseelectronscanbecarriedawayonaplatinumwire
placed in thesolution . Ashinyplatinum wireisusedforthiselectrode. because it is
nOI: acting as a cataly.s1 . The half-cell is wrinen :
wit bridge
Fcl+(aq) + c- ~ FcH(aq),Pt
and a diagram of it is shown in figure 23.5 .

A common error is to draw this cell with two electrodes. one dipping into Fe"\aq)
ions and the other dipping into Fel>(aq) ions . However, both ions need to be in the
same solution so that the electrode pot:ential of the mi.xto,re can be measured relative
[Fe'<,q)] Many standard electrode potentials have been measured. and a few of the more
,: {fe 1'("'U)
l .OOmol dm- 1 imponant ones a re Ji.sled in Table 23.1.
These Slandard electrode pot:entials are sometimes called fi'dox potentia ls . A
large negative value of Ee indicates a highly reactive metal that is easily oxidised . A
large positive value of Ee indicates a highly reactive non-metal that is easily reduced.
Flgure23.5 Thehalf.cellU1edtome.11ure
f"forthefe'lfe'system.Here,{Fe"land The order of these Ee values matches the obsef\'ed chemical re-activity of the
{fe'Jare1how'na11oomoldm-1 Thi'ii1not subSlancesconcemed.thoughthelargenegativevalueforlithiumissurprising.since
es'>l'ntial-theimpartantfeaturei'ithatthey chemically it is the leaSI reactive of the Group I elements .
are equal
Cell d iagrams
Instead of sketching the two half-cells. a ce ll di.'lgrant can be drawn . Cell diagrams
are nOI: really diagrams at all : they are an indication of all the chemical species
involved in the whole cell make-up (including state symbols and inen electrodes
whereused).wrinenouton asingleline.
Figure 23 .2 (page 382) is a picture of a cell in which a zinc half-cell is compared
with a copper half-<:ell . The cell diag ram for these two half-cells is:
C u (1) l cu"\aq) z nH(aq) IZn(s)
The solid venical line.s indicate a phase boundary. with the reduced forms on the
outside,andthedottedlinerepresentsthesaltbridge. (Sometimesadoubledotted
line is used for the salt bridge.) The concentrations of the solutions are assumed to
be I.OOmoldm- 3 unless a different concentration is sho"m underneath the ions. The
e.m.f. ofthiscellisthepot:entialdifferencesbetweenthez.incrod(right-handhalf-<:ell)
and thatofthecopperrod(left-handhalf.,:ell).
384
Table 23.1 Valuesoff&for,;orne

0 /V
commonhatf-1eactioml n w.iter,inwhich
11-f'(aq)) = 10-7 moldm- 1 (that is, the rnnditkms strongest
~
are non-standard), E{H/~H,) = -0.41V .;nd oxkli!.ing fl.'dlKing
f{-P:,itt,0) = ..0.82V agenll agents
u(;,qJ
'"
K*(aq)
Na*{aq) Na(s)
Mg'*(aq) Mg(s)
Al''(aq)
Zn'*{aq) "''
Zll(s)
fe'*(aq) R>(s)
h
- (g),f't
Cu(s)
r(aq),PI
Fe'(aq),?t
""''
8r{aq),PI
H,O(I)
Cr-{;,q),PI
Mn''(;,q),PI
r-{aq),Pl
'itrongest weakest
oxklil.ing redlKing
agents agent\
Worked example
Writeacelldiagramfor
amagriesiumelectrodecomparedwiththestandardhydrogeoelectrode
Write cell diagrams for: b aFel+Jaq)IFe1*{aq)half-cellcomparedwithazinchalf-cell
1 aCr31aqYCr"*(aq)hall-cell compared Answer

withacopperhatf-cell
2 anAl,.(aqYAMs)half-cellcomparedwith a Pt, ~i{g} IH1aq) iMg1*foq) I Mg(s)
a chlorine half-cell
3 a [Mno,-{aq) -t 8H1aq)JIMn'*(aq) half- (Note:sometextbooksuse'Pt[1H1(g)]'rathefthan'Pt,1Hilg)'.}
cell compared with a bromine hall-cell
(includeH*(aq)iomandH,0(0) b Zr,(s)IZril*laq) iH!l+{aq},Fe1+jaq)IPt
4 an [01{g) -t 2W{aq]hall-cellcompared Hefe, H!l+{aq) and H!l+jaq) are sep.irated by a comma because they are in the same phase
with the SHE half-cell
Calculating the standard e.m.f. of a cell , ~ 11

The values o f 9 shown in T3ble 23 . l can be used to work out the srnnd3rd e.m.f.
of a cell. E'".,.u. Conventionally this is the voltage of the rig ht-hand half-<:ell measured
3gainS1theleft-h3ndh3[f-<ell.So:
The sta nd ard e .m.f. of acell
385
PHYSICAL CHEMISTRY
Worked example
a Cakulatefr.110facopperelectrodecomparedwithazincelectrod1.>
b Cakulatefr. 1t0fthefolkiwingcell:
PtlH!1*{aq},Fe31aq) !Ag*laq}IAg(s)
Answer
a E"'co1 = t0.34 - (---0.76) = +1.1 0V
(ltisagoodideaatwaystoincludeth1.>s.ign.)
b E"'ce1 = t0.80 - (t-0.77} = +-0 .03V
Draw ttie experimental set-up, write the cel l diagram and calrnlate f~ for each of the
following cells
1 a magnesium electrode compared 1\ilh a zinc electrode
2 achl00neelectrodecompared1\ithabromineelectrode
3 anoxygeoelectrodecomparedwithacopperelectrode
23.2 Using E ~ell values to measure the

feasibility of reactions
When the two electrodes of a cell are connected co each other, electrons flow from
the neg:11ive electrode to the positive electrode. Chemical changes take pbce at each
electrode that reduce the voltage produced by the cell (the !<,rminal p.d .). 3nd finally
the reacrion stops bemuse the two electrodes 3..,- at the same electrical JX>lential. If
E!,. is positive. the reacrion com,:sponding to the cell diagram takes place from left
to right . For example. the cell diagram :
Zn(s) I Zn~aq) ! Cu~aq) I Cu(s) E!.:1 =+1.lOV
corn,-spondstothe reaction :
Zn(s) + CuH(aq} ---t znH(aq) + Cu(s)

and. as E!,n is JX>5itive. the n,-action is feasible and should take place if zinc is added
to copper sulfate solution. In this case. experiment confirms that the prediction is
correct. In cxher cases. this does ncx happen. There an,- two reasons why this may be
so,andweshalll<X>kat eachinturn.
Non-standard conditions
When determining E'!,1. all solutions have a concentration of I.OOmoldm- 3. This is
unlikelycobethecaseifthereactioniscarriedoutinatesttube. For the zinc/copper
sulfate n,-action, the voltage is so large and positive that changing the concentrations
has no effect. However. the situation is diffen,-nt if E'!,1 is less than +-0.2 V - under
these conditions. a fairly small change in concentration could make the volmge
become negative and the reaction is then nOI feasible. Non-standard conditions are
discussedfunherinsection 23.3.
386
High activation energy

Manyre3ctions, panicularlythoseinvolvinggasesandsolutions, have a high
activation energy. AlthoughtheE!,1 valuemayindirn1.-1hmchereactionisfeasible,
it is often so slow that no change is observed if it is carried out in the test tube. For
example, ~ 1 for Cu'~/ Cu is +o .34 V. This suggests thm hydrogen gas should "'act
withcoppersulfatesolution.butnoreactionisobservedwhen hydrogen is bubbled
through a solution of copper sulfate. The slowness of the conversion of gases
imo ions is the reason why platinised platinum is used in the standard hydrogen
Just as the conversion of Hz{g) to H"'(aq) ions has a high activation energy, so t<X>
does the reverse process. This me-ans tha! the prcxluaion of hydrogen (and oxygen
as well) by electrolysis often requires a gremer voltage than is prediaed by the E"<.'dl
values. This means that hydrogen and oxygen often need an ovcrvoltagc before they
arc discharged.
Worked example
Use fvalues from Table 23.1 tocakulate fro1 for the following reactions, and hence
predictwhetheftheyarefeasible
a Zn(s) + Mgi*laq)---,Zll*laq)+Mg(s)
b Cl1(aq) + H10{l) ---,foi4J) + 20-(aq) + 2H*laq}
Answer
a ~'"=f"lMg1/Mg) - f"(Zn 1rz.n} =-2.37 - (- 0.76} =-1.61V
Thereoctionisnotfeasible
b ~'"~ f~fqta-) - f"lf0 11HiO}~ +1.36 - (+1.23} = +-0 .13 V
The reaction is fllilSib~. 0- and HiO are the reduced forms
1 Use fvalues from Tab~ 23.1 tocalrn!ate Ero11and hence p!"edictwhetherthe

fo!lowing1&1ctionsarefe.1Sib~.
(Hint: you may find section 7.1 helpful in writing the relevant half-eqlliltions.)
a fH 1{g} + Ag"'(aq}---,W(aq) + /vj.1}
b Mno4- (aq) + 5ctiaq} + 8H*laq) ---,Mn1*laq} + 4H 10(1) + 2fq<aq}
t Fe(1) + 2Fe3*(aq) ---, 3Fe1*laq)
d Ag(aq) + Fei*laq)---,Fe1*jaq)+Ag(s)
2 1odidereact1slowfywithaqueous~i1U!fate(Vl)ionstoprod~iodineand1U\fate
2Iiaq) + 2sios1- (aql---, 11{aql + 2so/-<aql

lthasbeenfoundthatthebestcatalystslorthisreoctionaretransitionmetalcation-
pairs whose f values he between those of Ii/r(+-0.54V) and s.,os1-1Sol- (+2.01 V)
ThlJ:5 Fel+/Fe1 1,f~ +o.77V), Ce4+/CeJ+ (~ ~ + 1.70V)and CoJ+/C.oi (~ = +1.81V)
are all effective. Anion-pairs lllch as c10-1a- (f = +o.89V) are not effective, however.
a Suggestwhyther&Ktioncanbecatatysedbycations.OOtnotbyanions
b Use the f data given above to cakulate ~ for each of the two redox 1&1ctions, and
henceshowthateachreactionisfeasible
387
PHYSICAL CHEMISTRY
Co rrosion
All reactive metals con-ode - they reaa with oxygen and water in the 3ir. Some. for
example aluminium and chromium. form a thin layer of oxide th31 prolects them
from funher attack. Iron readily rusts to form hydrated ironOII) oxide. Fe1 0 3.H10
or FeO.OH. Unlike the oxides of aluminium and chromium. this does nOl stick well
to the tn<'tal surface. It easily flakes off and exp;:,ses more of the surface to funher
Rustingisacomplexelectrochernicalprocess th31takesplacemO!Slreadilyunder
the following conditions:
some of the iron is in contaa with air while ()(her regions are ncx
the iron is in contact with water conrnining salt or other ionic sub.stances.
Jn conrnct with air, the following reaction takes place:
1I1 + JH 10 + 6c- ----+ 60H- E,. =+0.81VatpH7

lntheair-fre,,n,gion, iron dissolves
2Fe ---t 2Fel+ + 6e- E* = --0.0'iV
The overall equations are
Flgure23.6 Anuntreatedimngateru1t1
2Fe(,) + tf) 1(g) + 3Hp(D---t 2Fel+ + 60H-
whenexpo'il'dtoair,mdwater 2Fel+ + 60tr ---+ 2Fe0.0H(s) + 2H 10
The electrons flow in the metal fron, the air-rich to the air-fr= region. This takes
place more quickly if the resistance of the solution that completes the circuit is
loweredbytheadditionofsalt.
Corrosion can be minimised in several ways. These include:
paintingorcoveringtheiron inplastictoexdudeair
e coatingironwithanoihermetal,forexamplezinc,tinorchromium
alloyingtheiron.forexamplewithchromium
fixing a more reactive metal. such as magnesium. to the iron. The reactive metal
preferemiallydissolvesandtheproressisthereforecalledsacrlficia l protcction
or anodic protection. Magnesium dissolves. having a more negative 9 value
(~2.J7V) than iron, keeping the iron negative and discouraging the reaction:
Fe ---t Fel+ + Je-
23.3 The Nernst equation

Non-standard conditions
In Figure2J .2.weshoweda zinchalf..cellconnectedtoacopperhalf..cell. Under
standard conditions. E!u = + I.IOV and. when the cell passes currem. electrons flow
from the zinc to the copper rod. If ,ve now reduce the concentration of the zinc ions
inthezinchalf..cell.theequilibrium
is displaced ro the left and the negative charge on the zinc rod becomes bigger.
Qualitatively this can be predicted from Le Chacelier's Principle (see section 9.2). and
it always happens when the concentrntion o f the oxidised form is reduced below the
standardvalueofl.Omoldm- l .
This change in the value of E!,u from non-standard cond itions can be calculated
Flgure23.7WoltherNemsl using the Nernst equation. named after Walther Nemst (Figure 23.7).
388
Forahalf-cellagain.stastandardhydrogenel=trodeat=temperature.this
eq uationcanbewrittenas:
f = f"'+(0.059/z)log!:':a::!
where z is the number of electrons added to the oxidised species to form the reduced
species.
A ten-fold change in concentration only affects the E'9value by 0.059V for a single
electron transfer and 0.030V for the transfer of two electrons. These are very small
changes and this is the reason why values are such a good guide to the feasibility
of the reaction, even under non-standard conditions.
Worked example 1
What is E for a copper electrode dipping into a solution of 0.00010moldm-l cui(aq) ions?
{Cui+ 2e-,=:,, Cu E" = +0.34V]
Answer
f = f + {0.059/z)log==
Thereducedspeciesismetalliccopperwhichisalsothereducedspeciesinthestandard
electrodepotet1tial.Thisme;imthatthevalueof[reducedspecies]hasbeenincorporated
intof"andcanbeignored
b-+0.34 + T1og1.o x 10---4
x-+0.34 + ~
= -+0.34 - 0.118 ~ -+0.22
However if the concentration change.s are very large, the change in E~ becomes
significant. We will look at the following three examples:
forasparinglysolublesah
for changes in pH
for the formation of complex ions. (This will be considered in section 24.4.)
Sparingly soluble salt
Worked example 2
A silver electrode dips into a sat urated solution of silver bromide which has a solu~lity of
1 K'4'forAgClis2.0x 10- 10 mcl 1dm- 6.
7.1 x10--1moldm-J. Whatisfforthi1half-cell?
Whatis ffora'iilverelectrodewtienit
[Ag + e-s=' Ag E" = 0.80V]
is placed in
asaturntedsolutionol'iilverchloride Answer
b inasolutionofsilverchloridein
f = f + (0.059/z)log=::i
0.10moldm- 1KCI?
2 (Haroef)Brineissaturated'i0dium Thevalueof[reducedspecie1JisincO(porated infandi1ignored
chloridesolution,whosernncentratkm
[Ag] = 7.1 x 10-1 moldm- l
isO.SOmoldm- l. When this solufon
iselectrolysed,chlO!inegasislomied f = O.BO + ~ x (- 6.15)
untilasaturatedsolutiooislormed
+-0 .44 V
Becausechlorinereactswithwater,
theconcl.'f1trationoffreechlorine
ina'i<lturntedsolutiooisonly
0.030moldm- l.Cak:ulateflorthe Changes in pH
reactionCl 1(aq)+2e- ~ 2Ct-(aq)undef A typical pH meter consists of a glass electrode (which allows the passage of H ions)
thesecornlitioris attached to a referenceelectrodebyasaltbridge. Frequentlythett concentration
varies between I.Omoldm- 3 (e.g.l.O moldm- 1 HCJ) and 10- 14 moldm- 3 (e.g.
1.0rnoldm- 1 NaOH). This has a profound effect on the .,,nvalue.s and forms the basis
389
PHYSICAL CHEMISTRY
for the accurate measur,,ment of pH . Because pH = - JoglH~L we can write the Nernst
e quatiOflintheforrn
....ti = E~1 - 0.059xpH
Worked example 3
Usingthesame e1ectrodesystemasin The refe reoceelectrodeinapHmeterisa silver/ silverchloride electrodewit h
t heexampje above, 1vhiltisthef,a1value ~ c<Nl ~-t0.23V
whentheglasse1ectroded ipsintoa What is the f ~ va lue when it and a glass elect rode dip into a so lution of pH 3?
wlutionof
1 0.0Smoldm- 1 NaOH
Answe r
2 0.10moldm-1 et hanoic acid f ,~1~ f ~ - 0.059xpH
(K, ~ 1.8x10- 5 moldm- l)? f,~ 1= -t-0.23 - 3 x 0.059
= +o.053V
23.4 The Faraday constant

When cu,,.,.nt flows from the copper/ zinc cell, the following c hanges take pla=:
at thcncgativcclcetrode: Zn(,) ----t znH(aq) + 2c-
a t thcpositivcclcetrodc: Cuz+(aq) + 2c-----t Cu(s)
During electrolys is, however, current is forced through the cell in the other direction
andthereverseprocessestakepbce:
at t h e cathode : z nH(aq) + 2e- ----t Zn(s)
a t the anode : Cu(s) ----t CuH(aq) + 2c -
In order to deposit o ne mole of zinc and dissoln, one mole of copper. two moles of
electronsneedtobepassedthroughthecell. Onemoleofelectrons rnrries a charge
of-% 500 C. Thisisthesamechargeasthechargeononeelectron, l. 6o3x 10- 19 c.
multiplied by the Avogadro constant , 6 .022 x toUmoJ' . Numerirnlly, the same
amount of charge is rnITied by one mole of protons ; this quantity is called the
Farnday con.m:mt , F, and has a value of 96 500Cmol- ' .
The cou lomb (symbol C) is the unit of electrical charge. One coulomb is the
amount of charge that is passed when one ampere flows for one second. Hence the
amount of charge passed in time/is:
Flg ure23.8 Mi<hae1Farad.ay(1791-1867)

One of his many .Khiwementi; was ta establish
The amount of charge on one mole of z+ ions is zF, and so the number of moles
aquontit.1tivebasisforelectrochemistry.
deposited is given by:
charge passed /xlmo l

chargepermoleofions zF
where z is the charge on the ion, I the current in amperes and I the time in seconds.
The amount liberated may be converted to a mass by multiplying by the molar
mass. Alternatively. if the prcxlucts are gaseous, the amount may be multiplied by
24dm3 to obiain the volume of gas prcxluced al room temperature and pressure .
Electrolysis may also be used to find the value of the Avogadro constam . The
value of the Faraday constant is first determined from an electrolysis experiment, for
=ample by depositing copper from a solution contain ing Cu~aq) ions. A steady
current , /, is passed for a measured time, I (in seconds) , and the mass, m , o f copper
depositedismeasured . Wehave :
m I XI
63-5 = -
The electrolysis =periment gives a value for the Faraday constant of 96 SOOCmoJ'.
that is, 96 500C is one mole of electrons. Experiments in physics have s hown that the
chargeone:,chelectronist.6o x 10- 19 c.
390
LX i.6oJx 10- ' 9 = 96500

1 Calrnlatethemassofaluminium
produced when a current of 1000Ais
passedthroughacell cootainingAIJ+
kmsfuflhour.
L= l.:::>9
= 6.03x toUmol 1
2 ii Showthat0.0016molofoxygeois
producedwhenacurrentol 1.0Ais
p;issedthroughsu lhiricacidIDlution Worked example
forlOminutes Calculate the mass of coppe< th<1t dissolves wheo a current of 0.7SA is passed through a
b Calrnlatethevolumeofoxygenthat zinc/copperce!lfor4Sminutes.[A,{Cu) = 63.5)
should be liberated
t SuggestwhytheactUi!lvolume Answer
rnllectedmaybelessthanthis 0.75 x 4Sx 60 ~ O.OlOSmol
l Explainwhy:
il hydrogenandoxygenareevolved
'"'
amount =--;;:
2x96S00
massofcopper 0.0105x63 .530.67g
whenaqueoussodiumh'jl}roxideis
electrolysed
b whenaqueousrnpperrutlateis
electrolysed with platinum electrodes, 23.5 Electrolysis
the cathode becomes plated with
coppe1andoxyge<1isevolvedatthe
anode
Pushing the cell reaction in the opposite direction
t whenaqueouscopperrutlateis If the electrodes of 3 cell 3re connected together. electrons flow from the neg:11ive
electrolysed with copper electrodes, to the positin, lerminal. If, instead. the 1ermin3ls are c onnected to an exiemal
thear.odedissolves voltage supply and the applied voltage is g radually increased. electrons stiJJ flow as
before until the ex1ernal voltage equals I;,,1 . At this voltage no current flows. If the
external voltage is increased still funher. current flows in the opposite direction and
c lcctrolysistakesplace(seeFigure23.9).
FlgureH .9 Voltage-c:urrentgraphfOfa
rnpperlzinca>II. Atl lOV,nornrrentflows
AboYe1.10V,electrnly,;istakesplac:e. Toe
reactionruminll'Verseanditi1Zn'(.iq)that electrolysis
isredlJCed
exte rnalp.dJV
actinga,ace ll
During electrolysis. positively charged ions, called catio n s. gain electrons at the
negatively charged electrode (the ca!hodc). At the same time negatively c harged ions.
called a n ion s. give up electrons at the posilively charged electrode (the a n ode).
E"'ll therefore is the minimum voltage required to bring aboU! electrolysis. ln
practice , the voltage used for electrolysis is ah.vays greaier than this minimum. There
lhe cell has resistance, so an additional voltage is needed to drive currem through
the cell .
The cell discharge often requires an overvo lta ge" to overcome a hig h activation
energy associated with the discharge . This is panicularly imponant when hydrogen
or oxygen is being prod uced by electrolysis of aqueous solutions.
391
PHYSICAL CHEMISTRY
Molten salts
When solid, a salt will n<X conduct electricity because the ions are not free to move.
When molten, however, the ions can move and the salt stans to conduct electricity.
Theconductivityoftenincre-:,sesas!he!emperatureisraisedbecausethereis le.ss
visco us drag on the ions lo limit how fast th<,>y can move.
The electrolysis of molten salts is used to produce reactive elements. such as the
alkalimernls,tha1cann01:beformedbyelectrolysingaqueoussolutions,becausethey
re-accwith,.,,ater.Forexample:
electrol,,,emo!t, ... NaO
2NaC!(l) 2Na(1) + Qz(g)
Selective discharge
In an electrolysis cell. the electrolyte may contain several cations or anions. Under
these circumstances, the one that is discharged is the one that requires the least
energy. This is called sd cctin dL..ch arge . For example, if a mixture of copper
chloride and zinc chloride is electrolysed, copper rather than zinc is deposited at the
cathode. This is because 9 for the Cu'+;cu half-cell is closer in value to E for the
Cl,/d- half-cell than 9 for the Zn:u/zn half-cell is. This shows that copper requires a
smallerix,tentialdifferencetobedischargedthanz.incdoes(seeTable2J.2).
Table H .21naso lutionrnntainingcopper

chlorideandzincchl01kJe.copperr.itherthan
,,.
zinctsdeposill'dattheuthodebecallSl'a f"(J.n'YZn) = --0.76V f"(t:1,10-)
smal1ervoltageisneededtobr ingaboutthe f-----+--------+----------l
eie,::tro!y1is f"(Cu'!Cu) = ..0.34V f"(~b/0-)
In aqueous solutions, HlO' (aq) and OH-(aq) ions are present and so selective
discharge takes place. lfdilutesulfuricacidiselectrolysed.forexample,hydrogenis
liberated at the cathode because the only cation present is the HlO'{aq) ion. There
are, however, bo!h Ofr(aq) ions and so/-(aq) ions in solution. A study of E values
(see Table 23.J) predicts that oxygen should be liberated at the anode:
TableH .1 Thef~o1va lue1prl.'dktthat

hydrogenandoxygen.lfel'Y{lf\tl.'d inthe
electrolysis cl dilute ~u!furk add f"(WltJ,) ~/OW =+1.13V
(Ot-r) = lO-"moldm-1
E"(W11',) fs,o.'-1So/-= 1.01v
Because bo!h hydrogen and oxygen have a highovef\ultage, they are often not
discharged e ven though E& values suggest that they should be. For example, the
electrolysisofbrineusuallyyieldschlorineratherthanoxygenandit is possible in
aqueous solution to electroplate objects with metals (for =ample. nickel) that have
negativevaluesofE"fortheirhalf-cells.
23.6 Other types of cells

Fuel cells
When the gases heated byburningafossilfuelareusedtodriveapistonortoturn
the blades of a tuibine, the overall efficiency is always low. no maner how well the
plant is designed. The typical efficiency of a mOl:or car is 200',. and that of a power
station is 40,6. This is a thermodynamic limitation: the only way to raise the efficiency
is to use a higher operating temperature. This in turn produces fresh problems.
392
In order to achieve higher efficiencies. efforts have been made to convert the fuel
directly into electrical energy by means of a fucl ce ll. The obvious pollution-fre,,
fuel is hydrogen. which can be bum! in air to prcxluce water. The reactions are the
reverse of the electrolysis of water. In acidic solution , we have:
at the negative plate H 1(g}----t 2H +{aq) + 2e-
at thc po1itivc platc: ~0 1 + ztt+ + 2e- ----+ H 10(1)
In alkaline conditions:
at the negative plate H 1(g) + 20H- (aq) ----t 2H 100) + ze-
atthcpoitivcpla1c: tJ, + H 10(1) + 2c-----+ 20H-(aq)

The problem is thac the reacrions at the electrodes are slow. even when the
electrodes are made of platinum. which acts as a catalyst. There is a fonher
complication for cars in that the hydrogen must be transponed, either in heavy
cylinders or at very low temperatures as a liquid. Effons are being made to carry
thehydrogeninthe formoftransitionmetalhydrides,butthesearecostlyandrnn
absorb only 3 limited amo,mt of hydrogen.
As an alternative to transporting hydrog en to fuel cars, methanol is a fuel that is
easytornrryandcanbebrokendowntoproducernrbondioxideand hydrogen .
This introduces an additional stage in the process, and there is also the danger
that somepoisonousrnrbonmonoxidemaybeproducedinadditionto thecarbon
dioxide. Attempts are therefore being made to produce fuel cells that use methanol
directly,butthesecellsa..,-onlypaniallysucces.sfulastheyhavetobeoperated
abover<X>mtemperarure.
lnthefinal3nalysis,fuelcellsa..,-..,-allyonlyanotherformofstoragebattery.
lnthefirstplace.thehydrogenmusthaveb=nproducedchemically,p;:,ssiblyby
electrolysis. and this process is not pollution-free. At p..,-sem, a promising line of
development is to use a hybrid system, running the car on electricity in towns where
pollutionisthemainproblem,andthen,on the open road,usinga traditional fuel to
rechargethebaneries.
Rechargeable batteries
Theoretically, most cells can be ..,-charged when they run down, but in practice there
are difficulties if the recharging is rnrried out quickly. The problem may be that
metalsarenotre-Oepositedin anevenlayer,orthat g aseous hydrogen and oxygen
are given off.
The familiar lead-add accumulator (the tradition.al rnr battery') has lead plate.s
dipping into moderately concentrated sulfuric add . After the first charging, the
positive plate becomes covered with a layer of lead(IV) oxide. During discharge, the
following reactions take place:
atthcncgativc p!atc Pb(s) + H 1S0iaq) ----t PbSO_,(,,) + 2H\aq) + 2c-

Flgure2l.10 Rechargeablebatteries.The
ctiemk:al reactioosthatto kepl.Keateach
elec:trodemustbel!'verslb le. Sidereactiom
limitthenumbe1ofrechal{Jingcydeo; thatG1n During recharging, the reactions 3..,- reversed . Bemuse sulfuric add is a good
be..c:hievl.'d - forl'n()';tcellsthis i1about1000 conductor of elcctridty, the internal resistance of the lead-add cell is very low . This
means that it can produce very large curTents, making it suitable for powering the
Slatter motor in a car. Its disadvantage is its low power-to-weight ratio and the fact
thatthebanerymustbekep1.upright.
Becauselead-addcellsaresoheavy,ctherrechargeablecellsha,eb=ndeveloped
which are more =penshe but which give a bener power-to-weight ratio. A common
one is the n ickel-hydride or NiMH cell . NiMH cells have largely taken over from the
older nickel-cadmium cells because they have about three times the storage rapacity.
Likethenickel-cadmiumcell,thepositiveelectrodeisnickelhydroxideandthe
electrolyte is potassium hydroxide. The main difference is that instead of rndmium
393
PHYSICAL CHEMISTRY
(whichishighlytoxic),thenegativeelectrodeisamernlMthaccanabsorbhydrogen
tomakeahydride. Whenchaiging,thefollowingchangestakepla=:
at the po,itivc dectrode, Ni(OH), + OI-r ----t NiO(OH) + H 10 + .,-
at the negative electrode: H,O + M + e-----+ OI-r + MH
The metal M is either a mixture of rare eanh mernls or a mixture of transition metals .
A big advantag e of NL'dH cells is th31 when they are fully charged any oxygen g iven
off combines with the metal hydride to form water. A cell can. therefore. be sealed
andusedinanyp;:>Sition. Adisadvantageisthmthechargeleaksawayandafcera
fottnight a cell will ban, lost about half of its charge.
Other modem rechargeable cells are based on lithium . They have the following
advanrngesoverthelead----addcell: theyarelight.theyprodua,-alargevoltage
and they can be used in a sealed container. Their disadvantages are th31 they are
expensiveandmustbetreatedcarefullyastheycontainveryreacrivechemicals.
In these cells. lithium ions move from the positive to the negative electrode ( n(){
electrons as in the lead-acid cell). The negative electrode is a mixed lithium-transition
metal oxide such as LlCo01. The positive electrode is graphite and the electrolyte is a
lithium salt dissolved in an organic solvent.
'When c harging, the following reacrions take place:
at the po,itivc electrode: LiCo0 1 ----t Co0 2 + Li+ + c-
at th e negative electrode: Li+ + c- + graphite ----t Li(graphitc)
At the positive electrode. some of the cobalt changes from Co(IIO to Co(IV). releasing
electrons (which go to the JX)ISitive terminal of the charger) and lithium ions (which
migratethroughtheelectrolytetothenegativeelectrode). Atthenegafr,,eelectrode,
lithiumionsareattractedbythefreeelectronsinthelayersofgmphiteandform
lithium atoms sandwiched between the layers of graphite . The electrons are supplied
bythenegativetem1inalofthecharger.
During discharge. the reverse of the cha rging reactions takes place. At the negati,e
electrode each lithium atom gives up its outer electron to form lithium ions . These
electrons llow through external circuit, giving up their energy . At the same time,
lithium ions move through the electrolyte and combine with eoo, to give LlCoO,
This process requires the addition of the electrons which have moved through the
external circuit. Other transition metals. such as iron. manganese and nickel. are also
usedinsteadofcobaltintheJX)ISitiveelectrode.
In a discussion about the merits of each type o f rechargeable cell, the following are
Co.si : lead-acidisthecheapest.
Power-to-,veightratio: lithium is the best .
Safety: NiMH can be used in any position and the chemicals they contain are
relatively safe.
394
Ametaldippingintoasolutionofitsionsfrxmsa ha lf-ce ll. Electro lysis istheprncessofdrMngareactionthatisnot

Whenthisisrnnnectedtoaoothefhalf-cellbymeansofsalt thennodynamicallyfl'dSibiebypassinganelectricrnrrent
brklge,an e lectrothem ica l cell issetup.Undefstandard through it
cooditioos,thevoltagesetupbythisceHisthe standardcell e lheionsthataredischargedinelectrolys.isaretheonesthat
e .m.f.,f~,lorthecell requirethek>astenergy.
Theamountofsubstanceinmolesdissolvedordepositedduring
e\ectrolysi:sisgtvenby
lfthe~ft-handhalf-cellisthe standardhydrogenelectrode, amount = 1 x 7
thestandardceOe.mJ.isthe standarde lectrodepotentlal,
f,fo<theright-handhalf-cell wherelisthecurrent,tthetimeinseconds,zthechargeonthe
The value off" measurestheoxidising/reducingpowerofthe ion ,mdFtheFaradayconstant
half-cellsystem,andtheleasibilityofredoxreild:ionscanbe tleisthecharge on an electron. thenLe~F
predictedfromf"'a,,1values
A redox rNCtioo that is predicted to be leasi~e from fro1 values
mightoottakeplaceinpractke,eitherbecau..ethecor,ditioos
arenon-standardorbecausetheiKlivatkmenergyisveryhigh
e lfthecooditionsareoon-standard,the Nernstequation in
thel0fmf=fl+(0.0S9/z)log==:Cilnbeusedto
caku!atethecellvoltage.

Please seethe data 5ectionoftheCDforanyA,.valuesyou 11iSuggestwt?;thebluecolouroftheelectrolytesl01vly
may need. fadesastheelectrolysisproceeds. [7]
b Mostofthecurrentpassedthroughthecellisusedto
1 Theelectrolyticpurificationofcoppercanbecarried out in
dissolvethecopperattheanodeand precipitate pure
an apparatus similar to the one ~1m below.
copper onto the cathode. H01vever, a !.mall proportion
ofitis'wasted'indissolvingtheimpuritiesattheanode
which then remain in 50lution. When a current of 20.0A
waspassedthroughthecellfor10.0hours,itwas
foundthat22Sgofpurecopperwasdepositedonthe
;.,,,.,o,,u=tflf-ooo '"'"'"""'"-' cathode.
i Calculate the following, u~ng appropriate data from
the data section on the CD
CuSO,(aq)
anode "sludge' number of moles of copper produced at the
cathode
number of moles of electrons needed to produce
The impure copper anode contains m.all quantities of
this copper
metallicnickel,zincand~lver,togetherwithinertoxides
number of moles of electrons that passed through
and carbon resulting from the initial reduction of the copper
the cell
ore with coke. The copper goes into solution at the anode,
ii Hencecalculatethepercentageofthecurrentthrough
but the ~lver remains as the metal and falls to the bottom
thecellthathasbeen'wasted'indissolvingthe
aspartoftheanode 'sludge'. The zinc also dissolves
a i Write a half-equation including state symbols for the impu rities at the anode [4[
reaction of copper at the anode. c Nickeloftenoccursinoresalongwithiron.Afterthe
initialreductionoftheorewithcoke,anickel---ironalloy
ii Use data from the data section on the CD to explain
is formed. Use data from the data section on the CD to
why silver remains as the metal
explainwhynickelcanbepurifiedbyasimilarelectrolysis
iii Use data from the data section on the CD to predict
techniquetothatusedforcopper, using an impure
whathappenstothenickelattheanode
nickel anode, a pure nickel cathode, and nickel sutlateas
iv Write a half-equation including state symbols for the
theelectrolyte.Explainwhatwouldhappentotheiron
mainreactionatthecathode
during this process [2]
11 Use data from the data section on the CD to explain
whyzinc:isnotdepositedonthecathode
Paper41 Q3November2010]
395
PHYSICAL CHEMISTRY
2 Chlorinegasandiron(ll)ionsreacttogetherinaqueous 3 a StatetherelationshipbetweentheFaradayconstant,
solution as follows. F, thechargeontheelectron, e,andtheAvogadro
2 number,L. [1]
C~+2Fe --4 2CI +2Fe3-+
b lfthechargeontheelectron,theA,andthevalencyof
:n
a The following diagram shows the apparatus needed to copper are known, thevalueoftheAvogadronumber
measurethefto1fortheabovereaction can be determined experimentally. This is done by
passing a known current for a known time through a
copper electrolysis cell, and weighing the mass of copper
deposited onto the cathode.
i Drawadiagramofwitableapparatusforcarrying
outthisexperiment.Labelthefollowing:povver
supply {with + and - terminals); anode; cathode; and
ammeter.
Statethecompositionoftheelectrolyte
Thefollowingaretherewltsobtainedfromonewch
experiment.
i ldentifywhatthefivelettersA- E intheabove
curreotpassedthroughthecell = O.SOOA
diagram represent.
timecurrentwaspassedthroughcell = 30.0min
ii Use the data section on the CD to calculate the~..
initialmassofcoppercathode = 52.243g
forthisreaction,andhencedecidewhichdirection
final mass of copper cathode = 52.5429
(lefttoright,orrighttoleft)electronswouldflow
through the voltmeter V when switch Sis dosed [7) ii Usethe5edataandrelevantinformationfromthedata
b lron{lll)chloridereadilydissolvesinwater. sectionontheCDtocalculateavalueofL to
3sig nifi ca n t fig u res . [9]
c U5erelevantinformationfromthedatasectiononthe
i Usethefollowingdatatocalculatethestandard CD to identify the wbstances formed at the anode and
enthalpychangeforthisprocess. atthecathodewhenaqueoussolutionsofthefoll01ving
compounds are electrolysed. [SI
! Species IM1i1urno1- I
I Fed,(1) l - 399.5 I ! compound I Prod uct at a node I Prod uct at cathode I
1Fe1 '(aq) l --48.5 I I Age I I I
0-(aq)
ii A solution of iron(III) chloride is used to dissolve
IFeso, I I I
unwanted copper from printed circuit boards. When
I MgBr, I I I
acopper-coatedprintedcircuitboardisimmersedin {Cambridge /memational AS & A Level Chemistry 9701,
FeC~{aq),thesolutiontumspaleblue. Paper42 Q3June 2011]
Suggestanequationforthereaction between copper
andiron(lll)chlorideandu5ethedata5ectiononthe
CDtocalculatethefforthereaction. (4)
Pape 4 QI June 2008]
396
A Level
Inorgan ic chemistry
24 The 3d block
In this topic we study the 3d block, which includes many familiar metals such as
iron and copper. The chemical properties of these metals and their compounds
contrast with those of the metals in the sand p blocks. For example, the 3d-block
elements can exist in several oxidation states and their ions are coloured,
whereas the s- and p-block elements usually show only one oxidation state and
have colourless Ions. The complicated chemiitryof the 3d block can be explained
in terms of their electronic configurations and in particular by the closeness in
energyofthe3d, 4sand4porbitals.
Learning outcomes
Bytheeodofthistopicyooshouldbeableto
12.1a) explain what is meant by a transition element, in te<ms of d-bkx:k elements !Ofming ooe or more stable ions with incomplet e
dorbitals
12.1b) ~etchtheshapeofadorotal
12. 1c) state the electronic configuratk>n of each of the first row transition elements and of their ions
12.1d) contrast,qualita tively,themeltingpointsanddensitie5ofthetransitionelementswiththoseofcak:iumasatypicals-blockek>ment
12.1e) desc:fibethetemJencyoftransit ionelementstohavevariableoxidationstates
12.1f) ;xedktfromagivenelectronicconfiguration, the likely oxidation statesofatransitionelement
12.2a) describe and explain the reactions of transition elements with ligands to form complexes, indtJding the complexes of coppef\11}
andcobalt{ll)ionswithwaterandammoniamclecule-;andhydroxideandchlorideions
12.2b) define the term ligand as a species that contains a lone pair of eleclfons that forms a dative bond to a central metal atoml'!On
indtJding monodentate, b4denli!te and pol'jl'.!entate ligands, define the ten complex as a molecule or ion formed by a central
metalatom/ionsmrotJndedbyoneormoreligands.describetrnnsitionmetalcomplexesaslinear.octahedral.tetrahedralor
sqllilre planar, and state what is meant by co-ordination ntJmber and predict the formula and charge of a complex ion, giYen the
metalion,itscharge,theligandanditsco-ordinationntJmber
12.2cl explain qualitatively that ligand exchange may occur, incltJding the complexes of copper{II) ions with water and ammonia
mo~ulesandhydroxideandchlorideiom
12.2d) describe and explain the tJse of H!J+/Fe2*, Mno4-/Mn 2* and Cr,o/-tc r3* as eX.ilmpk>s of redox systems (see also TOf)4c 23)
12.2e) predkt,tJsing~values,thel ikelihoodolredoxreoctions
12.3a) desc:fibethesplittingoldegeneratedorb4talsintotwol'nergylevelsinoctahedralandtetrahedralcomplexes
12.3b) explaintheoriginofcolourintransitionelementcomplexesrl'Sllltingfromtheabso<ptionoflightl.'flel'Qyasanl'k!ctroomoYes
betweml\vonon.degeneratedorbitals
12.3c) desc:fibe.inqllillilativeterms,thl'effect1oldifferentligandsonabso1ption,andhencec~our,usingthecomplexesofcopper{II)
ions with water and ammonia mo~ules and hydroxide and chloride ions as eX.ilmples
12.3d) applytheaboveidedsofligandsandcomplexestoothermetals,giveninformation
12.4a) describe the types of stereoisomerism shown by complexes, indtJding those associated with b4dentate ligands: ds-lTans
isomerism, e.g. cis- and tram-platin Pt(NH 3)1Cli, and optical isomerism, e.g. [Ni(NH1CH 1CH 2NH1liJ1
12.4b) desc:fibetheuseofcisplatinasananticancerdrtJganditsactionbybindingtoDNAincancercells,preventingcell division
12.Sa) describe and explain ligandexchangesintermsofcompetingeqtJilibria(alsoseeToP4c22)
12.Sb) state that the stability constant, K,,. 0, of a complex ion i1 the eqtJilib!ium constant for the formation of the complex ion in a
solveotfromitsconstittJentionsormoRtJles
12.Scl deduceexpressionslorthestabilltyconstantofaligandstJbstitlllion
12.Sd) explain ligand exchange in terms of stability constants. K,tib and tJnderstand that a large Krui, is due to the formation of a stable
complexion
397
INORGANIC CHEMISTRY
24.1 Introduction
The elements from sc:,ndium to zinc inclusive comprise the 3d block. The 3d
subshell contains five orbitals. each able to accommocbte two el=trons (see Topic 2),
and so this block contains ten elements. The electronic configuration of scandium is
1Arl3d 1 4s' and that of zinc is (Ar)3d 10 4s 1 . A 3<1-block element is sometimes defined as
one of the elements in which the 3d .sub.shell is being progre.s.sively filled . This is nOI:
strictly speaking correct . becausecopperhastheelectronicconfigumtionlAr) 3d' 0 4s 1
It is more accurate to srnte th31 the 3d block contains elements with electronic
configumtionsfromlAr) 3d 1 4s'to1Ar)3d 10 4.s'inclusive.
Originally this block was known as the "transition metals', because some of
their propenies show a gradual change between those of the reactive metal
calciurninGroup2tothernuch lessreactivernetalgalHurninGroup 13. Thetem,
trans it ion metal is now reserved for those rnecals in the block thm show properties
charncterislicallydiffe..,-mfromthoseinthesandpblocks:theycanexistinrno..,-
than one oxidation stale. and cir ions 3..,- ofcen coloured . We e=lude OOh scandium
andzincfromthedassoftrnnsitionrnetals.forthefollowingreasons.
Scandium forms only the colourless 0 ion. which is isoelectronic with the Ca "'"
ion and hasnoelectronsinthe3d subshell.
Zinc forms only the colourless Zn"'" ion. which is i.soelearonic with the Gal-+ ion
and has !Oelearonsinthe3dsubshell.
h istheelernentsthat formions withsomeelectronsinthe3dsubshell that exhibit

the special properties of transition metals .
Theldelementsa ndthetransitionmetals
The 3d block contains elements in which the 3d subshell is be;ng progressively filled
The 3d block includes all the elements with the electronic configurations [Ar]3d 1 4s 1
to (Ar] 3d 10 4s 1 ind usive
The transition metals fofm some compounds containing ions with an incomplete
dsubshell.
The4ssubshellisfilledbeforethe3dsubshellbecauseitislowerinenergy(.see
section 2.12), even thoug h the 4s subshell is pan of a shell whose average distance
is further away from the nucleus. The diffe..,-nce in energy between 4s and 3d is very
small. however. which means tha! both s and d electrons may be involved in bonding .
The order of energy levels 4s < 3d holds only as far as calcium. With che increasing
nuclear charge from 21 in scandium to 30 in zinc. the energy levels of OOh the 4s
and3dorbitalsdecrease.butthe3dleveldecreasesfasterthanthe4s (seeFigure24 . I
and Figu..,-2.2S. page34).Atscandiurntheirenergylevelsa..,-almost thesarne. but
subsequentlytheorderchangessothat3disslightlylmverthan4s. When an ion is
fom1ed.the4selectronsa..,-rernovedbefo..,-the3delearons . The reason for this
reversalinenergylevelsisdiscussedinthenextsection.
Flgure24.1 The3dand4seriergylwel5
oocro5singthe3dblod . Thegraphisootto
scale
"
nudear charge
398
24 The3dblock l
24.2 Properties of the metals

Table24.1 Toemainprnpertie1of thee lement1 inthe3dbkxk
Ele ctronl cconflgur; tl o n[Ar] 3d 141' 3d'41' 3d' 41' 3d'4s1 3d'4s' 3d"4s' 3d 741' 3d'4s' 3d'4 s1 3d ' 4s'
Meltlngpolnu c
Bolllngpolnuc
Den slty/gon---3
Conducttvlty/ m Srrr- 1
M'' r; dlus/ nm
M>+ r; dlus/ nm
FlrstlE/kJmot- 1
SecondlE/ kJmo l-1
ThlrdlE/ kJmor- 1
E"(M 2' / M )/V
ElectronegatMty
Electronic configuration
As the proton number increases by one unit. an extra electron is us,rnlly added to the
3d subshell . There are two exceptions to this general trend :
chromium is (Ar]3d~4s 1 and no1 (Arl3d"4s2
Thissuggeststhm3d1 (withahalf-filled subshell)and 3<1 10 (withafullsubshell)a,.,.

energetically preferred configurations, avoiding the inter-electron repulsion in the
4s orbital that occurs with the 4s 2 configuration. Both these config urations have a
symmetrical 3d cloud of electrons that screens the nucleus more effectively than Ol:her
configurations.
Melting points, boiling points and conductivities

The melting and boiling points of the 3d-block metals an, generally much higher th,m
those of the s- and p--block metals . This indkates that nOl only the 4s electrons but
also the 3d electrons are involved in the metallic bonding . When melting and boiling
p;:>ints are ploued against proton number, bcxh graphs have two maxima, with an
intermediate minimum at manganese (see Figure 24.2). These minima suggest that the
half-filled subshell of 3d electrons is not n,adily available for metallic bonding. We
might expect the same effect in chromium. but it occurs to a lesser degn,e because
thenuclearchargeislower.
Theconductivitiesofthe3d -blockmetalsan,similartothoseofcalcium
(29.2 mSm- 1); the conductivity of copper is particularly high.
Metallic radii , ionic radii and densities

Themetallicradiitendtodecrease acl'065theblockastheincreasingnuclearchaige
attracts the ou ter electrons more strongly. There an, minor variations to this trend
that can be rationalised in terms of the different strengths of the metallic bonding
- forexample,themetallicradii ofbothcopperand zincarelargerthanthose
of the preceding metals , and their meta llic lx>nding is weaker. as shown by their
comparatively low melting points . This decrease in metallic radius means that the
densitiesofthetransitionmetalsarehigherthanthatofcalcium(l .55gcm- l);thoseat
399
INORGANIC CHEMISTRY
Flgure24 .2 Meltingaridboilingpointsofthe
30.blcx:kmeta!s boiling point
the end of the block have the highest densities, as they ha_.,, the smallest atomk radii
andthehig hestrelativemomicmasses.
There is no obvious trend in the !>I ,. ionic radii. but the MJ.o- ionic radii tend to
decre:iseacrosstheblock3sthenudearchargeincreasesandattractstheelectrons
more strongly. This decrease in ionic radius is accompanied by an increase in charge
density of the ion, leading to an increased stability of the compl=es formed towards
the right of the block .
Ionisation energies
A graph of ionisation energies ag ainst proton number (see Figure 24.3) shows three
Flgure24.31oni'i.lhone11ergie1ofthe
3d-bkx:kmeta!s
_ _ _ _ _ _ _ _ _ _ _ .econdlE
----------- firstlE
The first and second ionisation energies increaseonlyslightlyacrosstheblock.

The second ionisation energies are only slig htly higher than the first.
The third ionisation energies are sig nificantly higher. and show a characteriscic
d--subshellpanern.
Tbe firs! ionisation energies involve the removal of a 4s electron . This is outside the 3d
subshellandispanfaUyscreenedbyic.Asthenudearcha,geincreasesacrosstheblock.
theadditionaldelectronsshieldtheeffectoftheincreasingnuclearchargesothacthe
4s electron =periences only a small extra anmction. Tbe same effect is shown by the
se=nd ionisation energies, with the =cep1.ion of those for chromium and =pper -
thesehaveratherhighersecondionisationenergiesbecausethese=ndelectronbeing
removed is a 3d electron, which does =perience the increased nuclear charge.
The third ionisation energies involve the removal of a 3d electron . The pattern
of five values sceadily rising, followed by a drop and then five more .s1eadily rising,
mirrors the ionisa!ion energies involving the removal of 2p electrons on crossing
400
24 The3dblock l
the second period (see Figure 2.33, P"8 " 41). The drop from manganese to iron is
a reflection o f the fact thac two electrons in the same o rbirnl repel eac h oiher (,..,.,
Figure 24 .4).
Flgure 24.4 Thl'e~ronkrnnfigurationsof ,,
~
mangane1ea11dimn. ThelonnatkmoltheFe' (Ar)
ion invotl'l'5theremovalofane1ectrnnfrom
adoublycxrnpied3dortiital; thi11'1ectronis
moree.11ilyremovedbecauseiti1repe lll.'dby Mn' (Ar)
theotherelectfoointheorbital
Mn' (Ar)
~
1
"
(Ar)
" 1
Fe' (Ar)
Fe' (Ar) 1
3dand4senergylevels
The relative energies of the 3d and4s orbitals change on crossing the block (see
Figure 24 .1). Up co calcium, the energy of the 4s rnbical is lower than th31 of the
3<L even tho ugh. on average. the electron is further away from the nude-us. This
is because the 4s electron spends some time very near to the nucleus , where it
experiencesthefullattrnctionoftheunscreened nuclearcharge . A4selectronissaid
to be more penetrating than a 3d electron .
Aftercakium , the4selectronsarescreenedfromtheeffectoftheincreasing
nuclear charge by the addition of the 3d electrons. which are nearer to the nucleus.
The energyofthe 4selectrons therefore decreases only slightly on crossing the 3d
block. This small decrease in energy explains the s mall increase in first and second
ionisation energies on crossing the 3d block from scandium to zinc. The 3d electrons.
however. are nOI: screened to the same extent and so experience a g reater effective
nuclear charge. beco ming progressively more tightly held by the nucleus. The energy
ofthe3delectronsthereforedecreases significantlyoncrossingthe3dblock.asis
shown by the sharper rise in the third ionisation energies (see Figure 24 .3). (From
scandium to zinc. the second ionisation energies increase by 400',. whereas the third
ionisation energies increase by 6o,6.)
Worked example 1
Using[Ar]torepresenttheargoncore,givetheelectronkconfigurationsofthefollowing
""''~
Cr b cui+ c l/1-
Answer
ii [Ar]3(Jl4s 1 b [Ar]3<fl c [Ar]3d 3
1 1..fsing[Ar]torepresenttheargoncore.givetheelectronicconfigurationsofthe
following species
ii Cu b Co1 c Til+
2 Brieflyexplainthefollowing
i1 Thesec:ondionisat ionmergyofcopperishi9hefthanthesecondio nisationene<gy
of zinc.
b lt isdifficufttooxidiseMn1+(aq}toMnJ+(aq)
c Onpassingfromscandiumtotitanium,the incre<tSeinthe thirdionisationenergyis
muchlargefthantheirxreaseinthefirstionisationroergy.
401
INORGANIC CHEMISTRY
Worked example 2
Br~fly ex~ain the following observatklm
Thefirstionisatklnenergyolrnbaltisonlyslightlylargerthanthefirstkmisationenergyof
b lhethirdionisatione,nergyofironismuchlowerthanthethirdiooisationroergyof
manganese
c Themetallicrad ius of vanadium is'iffiill~th anthat oftit.-mium .
Answer
Their,aeaseinnucle.lrchargefrom26to27isscreeoedbytheadditiooofanextra
3de\ectron.TheeffectivenucJearcharge,andher.cetheattractionofthe4sell'Clrons,
thereforeinaeasesonlyslightly.
b The third electron is being lffilOYed from a~ configuration, which tm two elect!Olls in one
d oroitill. These two elect!Oll1 n>pel each other, making eoch one e.-1\.K.'r to remoYe
c Their,ae,aseinnuclearchargelrom22to23milkestheinnerdoudsole!l'dronscontract,
andtheri!ditJsoftheatomdeaeases
24.3 Variable oxidation states

Table 24.2 shows the more familiar oxidation Sl31es of some of the 3d elements. Many
Ol:her oxidmion states are known which can be srnbilised under special conditions.
Table24.2 Themorefamiliaroxidatkmstates
ofsomeofthe3delementsaremorkl.'d other
oxidatklnstatesarekoownbutareformedonly
uriderspecialcooditions. Alltheelementshave
anoxklationstateofOinthemetal
Table24.2showsthefollowingmainfeatures
Chromium and manganese show their highest o xidation state in era/- and Mn04- .
In these. their oxidation numbers are equal to the sum of the numbers of 3d and 4s
eleccrons: this shows that all of these electrons are used in the bonding .
Manganese. iron. copper and zinc all form M"' ions by loss of the 4s' electrons .
Chromium and iron form M3<- ions as their third ionisation energies are relatively low.
Copper fonns Cu(]) compounds as it has a sing le 4s electron .
The presence of a high and a low oxidation state in chromium, manganese and iron
means that these elements have imponant uses in redox c hemistry. as is shown by
thevaluesofE 9 inTable24 .J .
Table 24 .1 Valuesoffforthreernmmoo
Redox system
redoxsystems.Theuseofm;mganate(Vll)and
aciddkliromate(Vl)isdiscus'>edinTopicl6
;~::n;tirig Mno,- aredimJ1sl'd in
lntitratiom,dichromate(Vl)andmanganate(Vll)areah.vaystJsedinaddicsolution.
1 Write the half-equation (i.e. induding e!l'drons) showing the reduction of each of these
oxidantsinacidic10lution.
2 Writethebalaocedionicequationforther&Ktionbetweene.1choftheseoxidantswith
Fei* ions,andukuli!tethef~valueforeachreaction
402
24 The3dblock l
24.4 Complex formation

Ligands
The 3d metal ions are relatively small and have a high charge density. They therefore
attract groups containing lone pairs of electrons. These groups are known as ligan d s .
Ligandsarebases,and alsonudeophiles (seeTable 15.L page270\andtheirabiliry
to be attracted to mernl ions follows a simibr p31tern to the nudeophilk strength
found in organic chemistry. For common ligands an approxim3le order of attrnctiOfl is
as follows :
H,o < h.~Hde ions < NH 3 < C~
The ligand bonds to the metal ion to form a comple x io n . Six. four or two
ligands combine with one mernl ion. so the formation of a complex ion may be
represented as the donation of six or four or cwo pairs of electrons to the metal
ion . A dative covalent bond (co-ordinate bond) is formed between each ligand and
Ligands contain atoms of p -block elements that are more electronegative th.m the
3<1-block mon, . This means thm the ligand anracts the electrons of the bond away
from the mernl. The result is thm the metal morn is approximately neutral. and the
charge is spread to the outside of the ion (see Figure 24 .5).
Flgure 24. 5Theformabonolaco~exion
Wateri1showna1theligand inthi'iexample
ToemetalioncouldbeM''ratherthanM"
,.
H,O f+
H,o: ( OH, .OH,
1
H,o:f\ M* f\:oH, to- M,(__ b~,I
H,o:J l :oH, :;/ ,,o.I
In the e,rnmple in Figure 24.5. the oxidmion number of the mernl is simply the same
as the charge on the complex ion. If the ligand is charged. for example a Cl ion.
the oxidation number of the meml is found in the same way as in any Ol:her ion(,..,.,.
section 7.2). If the oxidmion number of copper in the CuCl 4,_ ion is x. then :
x + 4x (- \) =- 2 and .x = +2
So the oxidation number of copper in this complex ion is +2. If a simple formula
does nOI: make it dear which groups are attached to the metal ion. it is common
practice to enclose the complex ion in square brackets. An example of this is
C!{H10 )i;Cl 3. which doe.s nOf make it dear which ligands are mtached to the
chromium ion. lt could. for example. be (C!{H 20).JCl.l (which has no chlorine ligands
but has three free chloride ions) or ICr(H10hCllCl,.H,O (which has one chlorine
ligand and two free chloride ions).
A oompleK io n is formed when li gand s donate a pair of ~ectrons to a metal ion

The 3d-biock metal s form stabKc complex ions'' the loHc,wing r=ns
e lheirionsarelffiilllandhal'eahigh chargedeosity.
They have 3d o rbitals of low eflef!ly that can accommodate ~ectrons donated by
the ligands
403
INORGANIC CHEMISTRY
The shapes of complex ions

The number of atoms surrounding a central atom is called the c0-0rdin a tk>n number.
Thus a complex such as IC!(H,O)? has a co-ordination number of 6. A complex of
formub ML/* has six pairs of electrons and its shape using VSEPR arguments(,..,.,.
section3.9)isaregubroctahedron(seeFigure24.6).
Flg ure24 .6The1hape1ofrnmplexiom

wtth1ixligand1,withfourligand1andwith
twolfg.lnds
lf the complex contains two ligands (co--ordinmion number 2), it is linear: examples
are the CuCJ,- and (Ag(NHJhl~ ions. With four ligands, VSEPR arguments predict tha!
the complex is tetrahedral and this is usually the rnse: examples are the CoCl/- and
IZn(NHi).J" ions. However, there are complexes with f01Jr ligands th31 are square
planar, which shows that factors other than electron repulsion must be taken into
account . An e,mmple of a square planar comp]= is dsplatin. which is discussed on
page 410.
Bonding in complex ions

In aqueous solution, Cu '* ions hydrate ro give the Cu(H,O)i;' * ion. Each water
molecule is bonded lo the central Cu'* ion by a dative covalent bond . In order to
form this ion. there need 10 be six empty orbitals to receive the six lone pairs from
the six water molecules . There are also nine 3d electrons in the free Cu'* ion that
need five orbitals to accommodate them. Thus at least l l orbitals are n,quired in all.
These are obtained by hybridising the six ligand Jone-pair orbitals, cogether with the
one 3s. the three 3p and the five 3d orbitals of the metal ion.
The energies and geometries of all of the resulting orbitals need not concern
us. except for one imponant outcome: under the influence of che ligand Jone
pairs. the five 3d orbicals split intotwogroupswithdifferentenergies. lnthe
simple Cu" ion. che five 3d orbitals all have the same energy (they are said to be
dege n era te). but in the presence of six ligands spaced octahedrally , the orbitals
divide into two groups - a group of two. called the e 8 and a group of three,
calledthe1, 8 (see Figure 24 .7) . The lobesofthethreet, 8 orbitalsaredirecced
in between thesixligands(see Figure 24 .8) . and theirenergyisonlyslightly
increased when the complex is formed . The !WO e 8 orbitals. however. have lobes
which point in the direction of the six ligands; this means that any electrons in
these orbitals will =perience inter-electron repulsion with the ligand Jone pairs
when the complex is formed, and so their energy is higher than that of electrons
inthec 23 orbitals.
Flgure24 .7 The~littingoftheJdorbit.ilsin
anoctahedr.ilfield
M"* ioninanoctahedralcomplex
404
24 The3dblock l
FJgure24.BThe1hape1ofthethreet,.
amltnetwoe,orbital1.Thet, 0 orbit.1l1polnt
inbetwee11theligand1;thee,00Jital1point
towarrl1theligand1
lntetrahedrnlcomplexes.thechangesintheenergylevelsofthee8 andt 28 orbirnls

is reversed. The 128 orbirnls now point towards the ligands. This means that they
can be used to form Slrong bonds, bu t it als.o means that any electrons that are
already in the orbitals will be s trongly repelled. The e 8 orbitals now lie between
the ligands and any electrons in them are rebtively unaffected by the forma tion of
a complex.
Ligand-exchange reactions
When ammoni3 is added to a solu tion conrnining aqueous Cu'~ ions. four of the
water molecules are substituted by ammonia, producing the cuprammonium ion .
This is an example of a ligand..cx clmnge reaction. the substitution of one ligand
by another:
This is a ..,-versible ..,-action and if !he purple complex IOJ(NHi)/H,O),J"(aq)J

is diluced . the pale blue colour of the [Cu(H,O)J"'(aq)J ion is re.sto..,-d . The..,- is
competition between the H,O and NH 1 molecules to anach themselves to the copper
ion. We ha,.._.. an equilibrium with a constant given by the exp..,-ssion :
((Cu(NHJMH,o),J"JIH,or'
{Cu(H,0)6''*!NH/
As (H,O) is in large excess and vinually a constant. we can include it in the

equilibrium constant and write:
([Cu(NH.i)4(H,O),f 1
1Cu(H,04[(NH.lf'
where Kot,b is known as the stability constant Strictly speaking, the..,- a"' stability
constantsforeachoftheequilibriaas H,Omoleculesa..,-prog..,-ssivelysubsti!uted
by NHi molecules. but he..,- we will o nly consider the overall constant. The value of
K,,_, depends o n how firmly the ligands bind to the metal atom. In general. atoms
with high electronegativity l:xmd weakly and those with lower electronegativity bind
mo..,- strongly . Thus w:l!er (which binds via the very electronegat:h.._.. oxygen atom)
forms weak l:xmds while the C~ ion (which binds via the carl:xm atom thac has
much lov.er electronegativity) forms strong OOnds and wiJJ have a large value of K;., b
(see Table 24.4). A hig h charge on the metal ion also makes Kot, b larger: compare
\!:~~!~~ I and l;::=.~I~
405
INORGANIC CHEMISTRY
Tabl e 24 .4 values of K~.i, fDf ,;ome

Complex logK,..i,
canplexi.-;. Thevalues;.,eusuallysol..rgeth.at
theyareoftengivenintheformlogK~.i, [CudJ,_ 4.1x10'
{Cu(NH,),)'+ 1.3x10"
{fe{CN),J'- 10x10'1
{fe{CN),,t'- 1.0x10'4
{Ag{NH 1},f 1.7x107
1 A solution of copper wlfote had ammonia added until [NHil = O.OSOmoldm-l.

Calrnlate the ratio of [Cu(NH1MH10)if' to [Cu(H10li;] under these conditions.
2 (Hardef - usetheNemstequationonpage389.)
f",~ 110fFel+ + e-~ Fe1 ist-0.77V
Calculatef",~ 1/or(Fe(CN),,Jl-- + e-.=:, [Fe(CN,,})4-.
A more complicated ligand-exchange reaction occurs when concentrated hydrochloric

add is added 10 aqueous Cu ,._ ions. Here , four H,O ligands are replaced by ci-
ions, but the remaining two water molecules are expelled, lening the tetrahedral
tetmchlorocopper{ll)ion (seeFigure24 .9):
Cu(Hp)/+(aq) + 4Cnaq)----t [CuC1J 2-{aq) + 2Hp(l)
Flgure 24.9S.Olutio111rnnt.1in irig.ithe

Cu(H,o),'ion.ind b the{Cucl,J>-ion
Deprotonation reactions
The water molecules in the hydrated compl= ions play an imponam role. \Vhen
sodiumhydroxidesolutionisaddedtoasolutioncomainingfei..(aq)ions. a
predpit:ue of iron([![) hydroxide. Fe(OJ-1)/s), is fom>ed. At fir.si: this looks like a
simple precipitation reaction:
This equation suggests th31 the reaction is simibr to the precipitation of, for =ample.
barium sulface when so/-(aq) ions and Ba 2\aq) ions are mixed together:
BaH(aq) + so/-(aq)----t BaS0 4(s)
406
24 The3dblock l
However, this ignores the role of the water molecules. The positive charge of the
Fe(H 20 \;i.. ion is partially spread over the surface of the comp]= . This enables the
Fe(H,O\;i.. ion to aa as a weak add (K, = 10- ~moldm- 3) and to undergo an add-
If the H10+ ions are removed by the addition o f a Slrong base such as sodium
hydroxide. funheradd-1:xisere:ictionscantakeplace:
[Fc(H 10)sOH]'\aq) + H 100) --+ [Fc(H 10>.(0H)1_i+(aq) + H 10+(aq)

[Fe(H 10l.{OH)z]\aq) --+ Fc{OHh{s) + tt,o+(aq) + 2H 200)
The overall reaction with hydrm:ide ions is :
The result is that the Fe(H,O)?" ion has been d e protonated by a S<"ries of add-base
reactionsandwaterligandshavebeenreleased.
Worked example 1
a StatethenumberofdelectronsintheFe1ion.
b Show, using curly arrows, the formation of the Fe(H10) 61* km
c Writeanequationforthl'convers.ionofFe(H 10)/'intothe(Fe(CN)i;]4-ionontheadditioo
ofaqueousKCN
d StatethetypeofrNctioorepresentedbythisd1arige
.,
Answer
b SeeFigtJre24.10
Flgure24.10
c ~H10)/*laq) + 6CN"""(aq) ---> [Fe(CNM4- (aq) + 6H100)

d Thisisaligand-exchangereactioo
Worked example 2
Writeooequatioofortheactiooofaqueoussodiumhydroxideoo theCu(H10\,l*laq)ioo
b StatethetypeofrNctioothat isrepresl.'fltedbythischarige.
Answer
a Cu(H 20)/*laq) + 20H"""(aq)---> Cu(OHli(s) + 6H 20(1}
b Thisisadeprotooationoradd---basereactioo.
Complex ions nomenclature

When naming a comp]= ion, the following rules apply.
A ration ruts the usual metal name, for ex:imple, copper.

An anion ruts the mernl name with an ate' ending , for =ample. chromate.
The oxidation state is indirnted in the usual way, for ex:imple. iron(lll).
The ligands are given specific names. for example. chloro (Cl"""), aqua (l-{10).
hydroxo (OH"""), ammine (NH 3). cyano (CN"") .
lhe number of ligands is indirnted by the prefixes di-, tri-. tetrn -. penta -. hexa-.
So the complex ion Fe{H,O\?< is the hexaaquairon(lll) ion. and Cu(NH 3)/+ is
tetrnamminecoppe1{11).
407
INORGANIC CHE MISTRY
Worked example
Name the following rnm~ex ions
Fe(CNlt;1-
b [Cu(NH1MH10).,f
c [Fe(HiOl,;OHf
Answer
hexactanofeffate(lll)ion
b tetraamminediaquacopper{ll)ion
c pentilil(Juahydroxoiron(lll)ioo
Name the follo1'11ing complex ioos.

11 C!'\NH1)i;l-+
b cua/-
c Zo(OH)/-
d (CrCl1(H10).J'"
Che Iates
Bidentate ligands
Ligands such as H,O and C~ ar<, anached by one coordina!e bond to the mernl ion .
If the ligand contains two groups that have a lone pair of electrons, it may form two
,, bonds to the metal atom, forming a ring. Such a ligand is called a c h ela te, a name
derived from the Greek word for a crab's claw. Stable complexes result if five- or six-
HiC--~\ memberedringsareproducedbythechelateandthemernlion.
I
H1C--~I
'" Two ligands thm readily form chelates 3re L2-<li3minoetlume , H,NCH 2CH,NH,, 3nd
,, the eth3nedi0<1te ion, - o,cco,- . These fonn five-membered rings (see Figure 24.11)
3nd are rnlled bide nt a te ligands because they join by two bonds.
Flgure24.11 Five-memtieredring;formed Chelates form panicularly stable comp]= ions, panly because they fonn strong
betwee11l,l-diaminoethaneandthecu'ion, bonds to the meml ion, buc also bernuse there is an additional entropy effect that
a!ldbetweentheethanedioateioo,md the
adds to their stability. For example, a chelate is formed in which three ethanedi0<1te
Fe'km
ions bond to Fe}<-. Four species become seven after the reaction, so the formation of
this chelateis3ccompaniedbyanincre-aseinemropy:
Fc{H 10)/+ + 3C10/- -+ Fe{Cz0 4)1l-- + 6H 10

Ancther way of visualising the incre:ise in entropy is 10 consider the effect after one
end of the chelate has become bonded to the metal ion. Once this end is secured, it
becomes much more likely that the cther end wiJJ be in the right p;:,sition 10 bond too.
Multidentateligands - edta
Some chelates form more than two bonds with the metal io n. A panicularly imponam
one is ethylene diamine t etraacetic acid. abbreviated as edm. which is used in the
fonnofitsdisodiumsalc,containing (edtaH 2)1- .
408
24 The3dblock l
This has six pairs of electrons able to bond to a mernl ion, and so forms a
h=adenta!e chelate. edrn is used to remove Ca:u and Mg" iOfls from hard water.
C11.{H,O)/+(aq) + (edtaHi-(aq)----+ Ca(edta) 1-(aq) + 2H+{aq) + 6Hz00)

This trapping of metal ions is rnlled S<'qU(.'Stcring. h alters the chemical properties of
the metal ions. and can be used to counteract the effect of poisoning by heavy me1al
Analysing tap water

The formation of stable complexes between edta and Mg 2* and Cau ions is used
to estimate the hardness of water by titratio n with edta . A sample o f the water
be ing tested is mixed with a buffer solution at pH 10. A few drops of an indicator,
solochrome black. are added and a solution of edrn is run in from the burette .
Solochrome black forms a red complex with magnesium ions. If solochrome black
isrepresentedasHln,__(aq),there:ictionis
red comple x
During the titration , the free calcium and magnesium ions first react with the edt.1:
\Vhen all the free calcium and magnesium ions have reacted with edm, the colour
changes from red to blue as the Mgln- (aq) complex breaks down .
Worked example
A few drops of mlochrome ~ack indic.atorwere added to 50.0cm1 of tap water. A
0.0100mo!dm- J solution of edta in a butfe1 at pH 10was added from a burette and the
indicato1 changed from red to ~ue alter the add~ion of 7.5Scm1
Suggest two substances that could be used to make the buffer mlutioo
b Calcukite the tot.-il coocefltratioo of cakium and magnesium ions in the sample of hard
Answer
a Ammonia and an ammonium salt, for example, ammonium chloride (see section 22.3)
b n(edta)3c x ~
1000
= 0.0100x~
1000
~ 7.SSx 10-smol
This amount of edta re.x:ted with 50.0cml of tap water. Since one mole of calcium or
magnesium ions reacts with one mole of edta, the concentration of calcium and
magnesiumionsinthetapwaterisgivenby
c(Cal + Mgl)3 1 ; xn
= 1000 x7.5Sx10- 1
50
- 1.51x10-1moldm-1
Isomerism in complex ions

Some of the types of isomerism found in organic chemi51ry (see section 12.6) are also
found in complex ions . An example of Slructurnl isomerism occurs in compounds of
formula CrCl 3.6H10 . Three such compounds are known with different properties(...,.,.
Table 24.5). ln particular, they have different numbers of free er ions (as shown by
their reactions with Ag~ ions) and free water molecules (as shown by the number of
water molecules that are easily removed by dehydration).
409
INORGANIC CHE MISTRY
Table24.5 Theproperti1'1ofthetl!rl'!'i,;omers
ofCrCl,.6H,O >--"""
- '- - - + - - - - - +"~o_=_ "'-"'-5 --+-~-----<
purp,e O [Cr(H,0).3'13CI
blue-grl.'!'n [Cr(H,O).;Of' 2CI.H,O
(cr(H,01,o,rc1-.m,o
Complexes can also show Slereochemisuy. A good example of this is the complex
ion INi(en):,(NHJ),J' , where 'en' is used as an abbreviation for 1.2--diaminoethane,
NH,CH,CH1NH1. This complex can exist in cis and /rans forms. The cis form (but
nOl:the lmns)hasa chiralcentre(thenickelatom)andcanberesolved into optical
isomers(sce.Figure24.12) .
Flgure24.12Thestl'reochemistryof
[N~en),(NH,):,12'
,, H,C/H,C-......_NH,
H,c - H,N ..... I __...N H, - cH, ,J I ,,

I "cV I
H,c......_H,N / l,"""NH,-cH,
H,1
;;::-'1
'(,,
H2C'-...H,c/NH2
Ni" also forms a complex with th..,.., 1.2--dbminoethane ligands. This has o nly the cis
fonn as the distance is too large for the ligand to stretch across the rransposi!ions
The ds form can also be resolved into optical isomers (see Fig ure 24.13).
Flgure24.130ptKalisomerisminthe
{Ni(NH,CH,CH,NH 1),f'+ion
Cis- and trans-platin

An important example of cis/lram isomerism is the drug dsplatin. This has a Pc atom
joined IO two chlorine atoms and t,vo ammonia molecules. h is a .square planar
cornplexandcan.therefore,exlsiinbol:hcisand /ram forms.
Cl
I
NH3 - ~t - NH3
Cl
<1,,pbtin
Cis-platin (but nOI: /rans-platin) is very effective in treating some forms of cancer. One
of the chlorine a!Oms in cis-platin is easily hydrolysed to give the l(NH,)1Cl(H,O/'" ion .
This ion binds to one of the four bases in DNA, usually guanine (see Topic 27. page
489), to give the [PtCl(guanine-DNAXNHl),l'" ion. This ion can cross-link with ancxher
DNA chain by displacement of the chlorine from the complex. lbe cross-linking inhibits
410
24 The3dblock l
DNA replication. panicularly in cancer cells thac are undergoing rapid cell division.
and the cell d ies. There is no obvious reason why rn:ms-pbtin is ineffective: one
theory is that it becomes deaaivmed before it can anach itself to DNA.
24.5 Colour in the d block

The origin of colour
All atornsandmoleculesabsorbintheu ltrnvioletregionofthespectrumbecausethis
radiation has enough energy to =cite their outer electrons. lhe ultrnviolei region is
outsidethevisiblerangeofthespectrum.soabsorpl:ionintheultravioletleavesa
substance colourless . Some substances. however. also have outer elearon levels that
are sufficiently close cogether for visible radiation ro have enough energy to bring alxx.n
electronic excitation. Under these circumstances. the sub.stance appears coloured. lhe
resulting colour""'"" is white light minus the colour being absorbed. The colour we"""
is therefore the complcm e nt a11 colour co the colour being absomed (see Figure 24.14).
To absorb in the visible regiOfl. the substance muSI have two eneigy levels that
are vecy close together. Close energy levels come about in two ways. namely c h arge
tran s fer and d-1o--d tr:m s itio n s .
Flgure24.14Thernlour1Dbservedwhen Example Absorption spect rum

absorptiont..ke5placeinthevisibjeregi0!1of (comple me ntary)
the1pl.'d:rum
<Moo, ~i[~D~ purple
,,c.o.A
~~
cuso,.sH,o - -.f
l -~-~,
w'"""lengt hlnm
~6
~, -
00
~
Charge transfer
If a substance contains bonds which are o n the borderline between iOflic and
covalent. it may change from one bonding type to anOl:her by absorbing visible
light. This effect is shown by some solids which are coloured (for example PbO
which is orange, and Ag[, which is yellow) even thou gh the iOfls they contain are
colourless . In the d block. anOl:her example is CuO . which is black even though the
Cu'~ iOfl is blue.
d-to-d transitions
In the d block. colour usually arises because of d -to--d electronic transitions . lne tig and
theegorbicalsarecloseinenergy,andelectronsinthet,gorbitalsmaybeexdtcdimo
the eg orbitals by the absorptiOfl of a phol:Ofl of visible light. Using the Planck equation.
f'>E = hf
thefrequencyassociatcdwiththeenergydifferencebetwccn theorbitals(Min
Figure24 .7) corn,spondstothefrequendesof visiblelight .
411
INORGANIC CHEMISTRY
Ions that have no 1,3 electrons. for example Sc(H,O)?', are colourless because
there are no t,g electrons io prom{){e. Similarly d 10 ions, for example Zn(H 20)/'". are
alsocolourlessbecausethereisnoemptyspaceinthee3 Jevelcoreceiveanextra
electron(seefigu..,24.15).
Figure 24.15 Thee~ctronkstructuresofthe

Sc(H,O).'andZn{H,O)/iom ,,.
h is fairly easy to explain the colours of the Cu'~ complexes. This is because there
is only a single space in the e 8 orbirnls 10 receive an excited electron, and as a result
there is only one absorpi:ion band. The ab.sorpi:ion is a band rather than a sharp line
(as happens with atomic spectra in the gas phase) because the t"u energy levels are
spread out under the inOuence of the adjacent ligands . The colour of the complex
then depends on where the maximum of this absorption is in the ,isible spectrum.
For the simple o.," ion (anhydrous OJSO.). the ligands create such a ve,y weak
field that the two energy levels are nearly the same; absorption is then in the
For the (Cu(H,O)J"" ion. absorption is panially in the red end of the spectrum and
thecomplexappearspaleblue.
For the (Cu(NHl).(H,O),:J" ion. the absorption is in the green pan of the spectrum
andthecolourisamoreintensepurple.
Thischangeinthepositioooftheabsoq,tioo OOndiscrnsed by the increase in

theelect!O!ltaticfieldcreatedbytheligands,whichresultsinalargersplininginthe
energylevels(llinFigure24.7)andahigherfrequencyofabsorption(seeFigure24.16).
Figure 24.16 Coklursofr.ome Cu'

rnmpD\/!ld1 . ruthelfgandfieldbecome1
11fonger,thes.plittingbetweenthed0fbital1
i11crea1e5andtheabso1ptionmove1fromthe
inlraredintothevisitJleregKl!lofthespectrum
ligarid H,O H2NCH,CH,NH,

ab'>Ol'ptionmao:imumtnm 800
colour paleblue "'
purple
24.6 Catalytic properties

The transition metals often act as catalysts. In the Haber process (see section 10.5)
andtheContactprocess(seesection 10.6). thecamlystsareinthesolidstate
Transition metals can also act as catalysts in solution. A good example is the oxidation
of iodide ions by peroxcxlisu lfate(VI) ions:
2r(aq) + sps'- (aq) ---t 2so/- (aq) + I 1(aq)
This reaction is nonnally quite slow, most likely because the negatively charged ions
repel each {)(her. However. it is catalysed by the addition of a number of d-block
metal ions. for example Fe1\aq). A possible mechanism is:
2 FcH(aq) + S 10 81-(aq) ---t 2FcH(aq) + 230 41-{aq)
2 FcH(aq) + 2r(aq) ---t 2Fcl+(aq) + l 1(aq)
412
24 The3dblock l
Table 24.6 Rel!.'Y;mtvaluesoff" forcata~s Each of the two pans of this mechanism involves a r<,action between two ions of
byfe'iom opposite charge. which is a favourable s ituation .
System E"IV Boihtheoryandexperimentrnnbeusedtosupportthismechanism.
The relevant values of standard electrode po(entials are given in Table 24.6. These
Fe"!Fe' show thac the po.stubted mechanism is thennodynamirnlly feasible .
1,121--- 2Fe 1\aq) + S 10 81-(aq) ----+ 2FcH(aq) + S 10/-(aq) E'!,n = + l.34 V
2 FeJ+(aq) + 2,(aq) ----t 2Fc1\aq) + ! 1(aq) E'!.u = +-0.23V
The two reactions rnn be tested experimentally. If a solution of S10 8,_ ions is
added to Fez. ions, Fe>< ions are produced . If Fel<- ions are added to 1- ions, iodine
Th1.> 3dblock includestheelemeotsfromscandiumtozinc: The elements chromium and manganese have a maximum
inclusive. oxidationnumberequaltothe'illmofthenumbersof3dand
The elements titanium to copper show features il:Ssociated 4selectrons.
with trans itionmeta ls,thatis,variableoxk!ation51:atesand Theionsofallthe3d-blockelementslorm comp lex ion s by
~ouredions. receMngelectronslromtwo,lourorsix ligand s
e lheelementsofthe3dblockhavehighmeltingpoint1,boiling Complex ions may exist in different forms (isomerism) and in
points and densities differentshapes(stereoisomefism)
e lhefirstandsecondionisatiooenergiesincrwseoolyslightly Thestabilityofthecomplexismea'illredbythestability
acrosstheblockfromscand iumtozinc,as41electronsare constant,K,ta1>
beingremovedwhichares.hieldedfromthenudearattractioo S.Ome ligands join onto the metal ions by more than one pair of
bytheirmer3de~roos.Thethirdiooisationef">l'fgiesincrease electrons.Theseform che lates ,whichareespeciallystable
more rapidly as a 3d e~ron is being removed e rf'andd 10 ionsarecolourk>ss.Otherd-blockionsarecoloured
Most of the elements form M 1 ions by loss of the 41 e~rons. becatJSeof d-to-dtransitions inthevisibleregiooofthe
and some form Ml+ ions as well spectrum

Please seethe data section of the CDforanyA,.valuesyou b The following graph shows the absorption spectrum of
may need. two complexes containing copper.
1 a Explain what is meant by the term tramition element. (1)
b Completetheelectronicconfigurationof blue green ye llow red infra-re d ----
i the vanadium atom, 1s2 2s2 2p 6 ...
ii thecu' ion. ,s12s12p 6 ... (2(
c Listthefour mostlikelyoxidationstatesofvanadium. [1)
d Describe what you would see, and explain 1\/hat happens,
when dilute aqueous ammonia is added to a solution
containing Cu1 ions, until the ammonia is in an excess. [SI
e Copperpowderdissolvesinanacidified50lutionof 500 600 700 800
!iOdium vanadate(V}, Navo,, to produce a blue solution wave length/nm
containingVo1 andCu1 ions.
By using suitablehalf-equationsfromthedatasectionon i Statethecoloursofthelollowingcomplexions
the CD, oonstruc:tabalancedeqtJationlorthisreaction. [2) [Cu(H10)f.J1'
{Cambridge International AS & A Level Chemistry 9701, (Cu(NH,}~H 10)i)1
Paper 4 Q3 June 2009] ii Usingthespec:traabovegivetworeasons1'11hythe
2 Coe major difference between the properties of compounds of colour of the (Cu(NH,1'(H 10)i)1 ion is deeper {more
the transition elements and those of other compounds is that intense)thanthatofthe(Cu(H 10}6]1 ion.
thecompoondsofthetransitionelementsareoftencoloured.
a Explain in detail why many transition element
compounds are coloured. (3(
413
INORGANIC CHEMISTRY
iii Predicttheab50fptionspectrumofthecomplex hot cone.

MnO,i+W
[Cu(NH 1}i(H 10).J2 , and sketch this ~trum on a
copy of the graph. (6)
c Copper forms a complex with chlorine according to the
following equilibrium.
i Writeanexpressionfortheequilibriumconstant,K,,
forthisreaction,statingitsunits.
ii ThenumericalvalueofKcis4.2 x 105.
Calculatethe[[CuCli1- )l[Cu1~Jratiowhen
[cl- J= 0.20moldm- 1. (3)
{Cambridge lnte!Thttional AS & A Level Chemistry 9701,
Pdper 41 Q3 November 2009]
3 a Completetheelectronicstructuresofthecr3 andMn1
14]
Crl+ 1s1 2s1 2p6 ... e KMnO~ and K1Cri0 7 are the reagents that can be used
o~"x'"o
Mn1 1s1 2s1 2p6 .. [2)
tocarryoutthefollowingtransformation.
b i Oe5eribe what observatiom you would make when
diluteKMnO.i{aq)isaddedslmvlyandwithshakingto
anacidifiedsolutionofFeS0~{aq)untiltheKMn04 isin
a large excess
ii Construct an ionic equation for the reaction that
occurs. [4)
y ~' o,
c Byselectingrelevantfdatafromthedatasectionon '
theCDexplainwhyacidifiedsolutionsofFe"~aq)are
i Draw the 51ructure of intermediate E
relativelystabletooxidationbyair,whereasafreshly
ii Suggestreagentsandconditionsforreaction I, and for
prepared precipitate of Fe{OHh is readily oxidised to
reaction II [3]
Fe{OHl]underalkalineconditions. 141 {Cambridge International AS & A Level Chemistry 9701,
d Predicttheorganicproductsofthefollowingreactions
Paper42 Q4June 2010]
and draw their 51ructures. You may use structural or
">keletalformulaeasyouwish
414
A Level
Orga nic chemist ry
2 5 Arenes and phenols
_
Functlon11l groups;
Learning outcomes
H X .... By t hl!eodolthistopicyou~u~beableto:
6 h 14.1a) interpret anduse theg.e neraf,strucll;ral.displayed
"*" . ~.
and ~~etalfom1uli11! ol the loll owingdassesof
~
compoond:arenes, hal ogenoarenesandphenols{part,
H H
H ...XmCI.Br.t 14.1c)
seealsoTopk12)
1.mdemand and use 5Yrtematic nomenclature of simple
aromaticmolecvfmwithooebenzene ringandooeor
moresimplesubstitueots
n,. .,..MS- group of hydrocarbon,~ mo/KlffS

contlin tM benzene ring. Although m.y um.turh!d,
14.3a)describeandexplainthe Wpeof,andbondanglesin,
benzenemoleaJlesintermsof o and1tbonds
15.4a) describe the chemistry of arenes as 11XempWfied by the
they do nor show the typic.JI rHCtion$ of t.nn. Their followiogreactionsofbenzeneandmethylbeniene:
char,1ct.rhtl< rHCtion is eJectrophilk wbstlMion. Phenols substitutionreactionswithchlorineandwithbromine,
cont11/n hydroll)' group (-oH} join.d dlrrly to nitration,friedel-Craftsalkylationandacylation,
t>.nnrlfl rlnr,. The pres,enc of th ring modifi.s the t)pica/ completeoxldationoftrH! side-rnain togiveabenzolc:
,1/cohol-1/b rtKtions of the -OH 'J'OIJP, Wt.-lH, the acid. andh)(lrogeratioooft hebenl:llfleringtoforma
P,tHnct of tl'Ht - OH group modififu th rypk / ,,.,,../i/re cydohexane ri rig
rtKtlons of the "-nz11"" ring. Th p,.wnc of rt,, /u,nune 15.4b) describe themediani 51Tl olelec:trophil ic:substitution in
ring Hvtf't/y ntduc.s the rNctivityof th e,,rbon-h4/0gtln arenes.asexe mpliliedby the forma tiooofnitrobeozene
bondlt!Mlor,.no.,,nes. andbromobenzeoe, 509 gertthe mechanismof o1her
electroptiilicsubstitutioor&lcticm,givendata.and
describetheeffectofthedelocalis.!tionofelectronsin
arenesios.uchreactions
15.4<) ioterpretthedifferenceinreactivitybetween
halogenoalkanesanddiloroberuene
15.4d) predictwhetherhalogenationwilloccurintheside-
chainorlnthearomatic:rioginarenesdependingon
reactioncooditions
15Ae) applyknowiedge relat ingtopositionof substitutionin
theelectrophilicsubst itutkmolare<ies
17.2a) recall thechemistryolphenol,asexempl ifiedby the
followiogreactions: withba'il's, with sod ium . wi th
diazooiumsalts(seealO Topic27).andnitratlonof,
andbfomlnationof,thearom aticriog
17.2b) describeandexplainthe relati...-aciditiesofwater,
phenolandethand.
4' 25.1 Introductio n

The structure of th e benzene ring
Arcncs are hydrocarbons that ront.~in one or more benzene rings. Ben7.ene was first
isoh tedandidentifi ed by theHnglishehemistMichaelFaraday in 1825. ltsstructure
posed a problem for ni neteenth-centu,y che mists. Comparing its molecular formu la,
415
ORGANIC CHEMISTRY
Cq\;, toth31 of the alkane hexane. Cqf 14 , it can be seen thm benzene is highly
deficient in hydrogen . Other compounds with very low hydrogen-to-carbon ratios
,vere all known to be highly unsaturated. conrnining many c=c double OOflds: !hey
re:idily decolorise KMn04(aq) and Br,,{3q) . and react with HBr, and with H,O in the
presence of adds . Benzene showed none of these reaaions . Funhennore. it was
Lade nburg's,tructure apparentthmallsixhydrogenatornsin benzenewereequivalenttoeach<Xher, in
(1865) (1869)
th31 only one isomer of chlorobenzene, c,,Hsd , C01Jld be made. There were three
Flgure25.1 Two1tructure1thatwere isomers of dichlorobenzene. CqI.ct,. howen,r. No open-chain scructure would show
propo!ol'dforbe11ze11einthenineteenth these properties. butsevernlstruaurescontainingringsweresuggestedinthe 1860.s.
century
Those pl"OJX>""(l by the German chemists Alben Uldenburg and August Kekul<" are
showninFigure25 . J.
1 Draw the structtJral formtJlae of all possible isomers of Cr,H 40z tJsing the Ladenbrng
structtJre, andthtJs s.how thatthere areoo!y t hreeof them
2 Oraw thestructtJral formtJlaeof allpossibleisomersofC 6H40zmingtheKe ktJli!
structtJre, andthtJss.how t hat t here are fou r of the m
If two hydrogens 3re replaced by chlorines, to form dichlorobenzene. it is found that

three (3nd only three) isomers of CefliCl, rnn be m3de (see section 25 .2). Although
this finedwithLadenbu rg'sstructure. Kekule"sstructuredidn01:quite3ccountfor
this observation: his proposed structure implied that there should be cwo isomers o f
1,2-dichlorobenzene :
Cl a
,},/'
()'a'"' v
In fact. there is only one 1.2--dichlorobenzene. To overcome this d isagreement with his
structure. Kekuli' proposed that the bonding in the benzene ring alternated between
Flgure2 5.2 TheGermandtemist f riedrilti twoequiv:,lentstructures:
Augu1tKekulllvo11Stradooitz(1829-96)was
::~:eto1uggestthatbenzer.eh.K!ari11g O 0
Now th3t we accept that It electrons can become delornlised in m 3ny-mom It o IDitals.
formed by the o verlapping of p oIDitals on adjacent atoms. we have no need to
postulate this alternation between the two Kelruli' fom1s . The true bonding in benzene
has sometimes been described 3S being in between the two =tremes represented by
the t,vo Kelruli' forms. We represent this 'in-bet,veen' state by a do11ble-headed arrow
joining the two formulae:
0 0
h is importam to understand the me3ning of the double-headed arrow, <--->. This states
that there is o nly o ne structure, which is in between the two classical" structures
drawn either s ide of the arrow. The =istence of a struc!Ure which rnnncx be
0
representedbyasingle'dassical " structure,butwhichisimermediatebetweenseveral
of them. is known 3S mC'Some rism (from the Latin/Greek work meso, meaning
middle"). The classirnl structures are calle d mesomers .
An e arly representation of the mesomeric structure of benzene was proposed by
Flg ure2 5. 3Therepre'il'lltationofthe the German chemist Johannes Thiele in 1899 (see Figure 25 .3); this is very similar to
benzenemoleculeprnpo<,edbyThiele in 18<J<J thedelornlisedstructurewedrawtoday.
416
25 Arenesandphenols l
Thestructureofbenzene,vasdescribedindetailinsection 3.16. It consists of six

carbon atoms arranged in a regular hexagon. each joined to a hydrogen morn and to
its neighbours by O" bonds. The,.,. are six spare p orbirnls, one on each carbon atom.
allparnlleltoeachcxherandperpendkulartotheplaneofthering. Eachporbirnl
overlaps equally with both its neighbours. forming a delocalised six-centre molecular
~orbital(s=Hgure 25.4).
Flgure25.4Thedelocali'ied1tbondi11
bel\Zene
/ ,o --------0,_,
0- ' c -::a.cn
,_y;,;:
e; ccc oJ{-"
OJ----C
,' Q _____ Q'>{,0
All the bond angles in benzene are 120. All the C---C bonds have the same length,
0 .139nm. This is intermediate becween the length of the C -C lxmd in an 3lkane
(0.154nm) and the c=c double lxmd in an alkene (0.134 nm).
Theusualrepresemationusedforbenz.eneiseitherthesymmetricalskelernl
fomrnla(derived fromtheThielestructure)orthe Kelrull'structure,eitherskeletalor
structural. Figure 2S.5 shows these representations. The benzene structure is normally
represented by the skeletal formula. as in figure 25.Sa. When we want to show in
Flgure25.5Threell'pre,;entatiomofthe
benzene molecule a tlleThfete1keletal detail how the It electrons move during reactions, however. we may sometimes use a
formula,btheKekul~s.kelet.ilformu!a,cthe Kelrull' structure, as in Figure 25 .Sb or 2S.Sc. Figure 25.6 shows models of the Kekule
sttucturalfDfmulaforbenzene and Thiele.structures.
Flgure25.6 a Ball-af'Ki.stic:landb elec:tron-

densitymolerularmodelsofbenzene
In the skeletal formula. each corner of the hexagon is assumed to contain a carbon
atom. 10 which is anached a hydrogen acom. unless cxherwise Slated. For example.
6
The Kekull' Slructure fined in with the chemical bonding ideas of the t86os, but
wasclearlyincorrectinoneimponantrespect. ltpredictsthatbenz.eneishighly
unsaturated - the formula suggeS1s that the molecule contains three double bonds.
It ought to undergo addition reactions re-:idily. juSI like an alkene. In fact. benzene is
inen to most reagents that readily add o n to alkenes (see Table 25.1).
Table 25.1 A rnmparisoo of some 1eactiom Reagent Cydohexene

ofbenzeneandcydohexene
1haKingwilhKMnO,{aq)
1haKingwilhBr,(aq)
H,(g) inthepreseJl(eofnidel veryslowreactionat100 c rapidreactiooat20Cand
and100atm
417
ORGANIC CHEMISTRY
Under more severe conditions. benzene can be made co react with one of these
reagents. bromine . But now the reaction follows a different course - a substitution
reaction occurs. rather than addition. and the necessary reaction conditions are much
(VJ + Br 0)
2
_ _A_<a~, - ~_ _ _,
The stability of benzene

The six-centre delocalised It bond is responsible for the following physical and
chemical propeniesofbenzene.
e ltcausesaUC---Clx>ndlengthsto be"'lual , c=tingaplanar.regularhexagonal

shape.
h prevents benzene undergoing any of the normal addition reactions that alkenes
The II lxmd also makes benzene more stable than expected . NOi: only is benzene
much less r<,active than cyclohexene, it is also them1cxlynamically more stable. We
can demonstrate this by comparing the actual and the 'calculated ' enthalpy changes
of hydrogenmion. The hydrogenation of alkenes is an excxhermic process:
l'i.H .. = - 137 kc] moi- 1
Forrnanyhigheralkenes,theemhalpychangesofhydrogen31ionareverysimilar
to each cxher, and average about l l8kJ mol- 1 Furthermore. for dienes and trienes
(comaining two and three double bonds , respectively) , !he emhalpy changes of
hydrogenation are simple multiples of this value (see Table 25 .2). So we migh! expect
benzenetofollowthesametrend.
Table25.2E ntha'pjchangesof
l>J(>~/
hydrogenation of1omealkene1
emor-'
CH 1--<:H-C H-CH1
cydohexef\l'
0
CH,=<:H-C H=CH,
cydohexadiene
'cydohexatriene'
0 (- 354] 1- 118)
0 {p<edicted) (as'>Umed)
lf we measure the experimemal enthalpy change of hydrogenation of benzene,

we find that it is far les s exodiermic than that predicted for 'cyclohexatriene' in
Table2S.2 :
g + 3H;,1 -> 0 l'i.H:.-.,...._ - - 205 kJ mor'
418
010-~1
Flg u re25 .7fnthalpychange1of
hydrogenation of benzene and the
cydohexeries
00
! Smm;
,, r'''""mo-
0 1
- 232 -205
actual
ocy,,o,mo,
So benzene is more smble than cydohexatriene' by 354 - 205 = 149kJ mol- 1 (see
Figun,25.7).
The stabilisation of 149kJ mor' is known variously as the stabilisation e n ergy,
the dcloca lisation cnl'rgy or the resonance energy.
Other arenes
Compounds that contain rings of delocalised electrons are called aroma tic
compounds . The name was originally applied to cenain natural products that had
strong. pleasant aromas. such as vanilla -bean oil. clove oil. almond oil, thyme oil
and oil of winterg re.,-n. All of these oils conrnined compounds whose structures were
found io include 3 benzene ring. The tern, "arommic' eventually bec3me 3ssoci.tted
with the presence of the ring itself, whether or nOI the compound had 3 ple3sant
3roma(seeFigures25.83nd25.9).
Flg ure25 .8Someplea1ant-1mellingnaturalty

ocrutringammaticrnmpourid:I
oc::,CH,
methylsali<ylate if)(CH,-CH=CH,
benuldehyde ~CH(CHJ, (oil of w inte rgreen)
(oil of almonds)
,A) ,,,;y
OCH,
vanillin thymol eugenol
(oil of vanilla bean) (oil of thyme) (oilof<lovu)
F1g u re25 .9Sane110t-10-pk>.is.ant..-;melling

aromaticcompoundsmadeinthelaboratory
phenylamine(aniline)
(musty,tarlike)
6
thiophenol
(burnt rubber)
benzoylchloride
(acidic and nause ating)
There 3re two ways in which benzene ring.scan join together. Two ring.s could be
joined by a single bond. as in biphenyl :
419
ORGANIC CHEMISTRY
Or the two rings could share two caibon atoms in common (with their It electrons) .
3sinnaphthalene:
00
Mo..,- rings can fuse together, giving such compounds as anthracene and pyrene:
N01:icetha1 witheachsucce5,5iveringfusedtogether,thehydrogen-to--carlxm ratio

decreases, from I : l in benzene to S :8 in pyrene . Eventually. as many more rings fuse
together. a sheet of the g raphite bttice (graphem,) w ould result (see Topic 4).
Manyofthemultiple-ringarenes, suchaspyrene.arestronglycarcinogenk
(rnncerprcxludng).Evenbenzeneitselfisahighlydangeroussubstance.causing
anaemia and cancer o n prolonged exposure to its vapour. In the past it was used as
a labomtrny sohent, bU! its use is now severely restricted. although it is still added to
some brands of unleaded petrol to increase their anti-knock rating.
Physical properties of arenes

Benzene and most 3lkylbenzenes are strongly oily-smelling colourless liquids,
immiscible with, 3nd Jess dense than, water. They are non-polar, 3nd the only
imermolecular lxmding is due to the induced dipoles of van der W33[s' forces. Their
boiling poims 3re similar to those of the equivalem cyckxilkanes (see Table 25 .3) , and
increasesteadilywithrelativemolecularmassasexpected.
Table 25.3 BoWr,gpoinl5 ol!iOme

cydohexonesandall'!1l"i
'"""""'
cydohexal\l' C0H11
8ol ll 1111
po1 n11c
Compound
C0H0
Bol lin g
polntlC
methylcydohexane C, H,. methylbenzene C,H

ethylbenzene CoH10
propylbenzene C,.H ,,

Aromatic compounds with more than one substituent on the benzene ring can e xist
as positional isomers. There are three dichlo robenzenes:
Cl Cl
oCl Q Cl
The terms ortlx,..., me/a - and para - are sometimes used as prefixes to represent the
relative orientations o f the groups(s=Table 25.4).
420
Tabte25.4 Orientationsof1ubstituentson
the benzene ring
'"'"' Eumple
If the two sub.stituents are different. one of them is defined as the "roof group, in the
following order of precedence
---CO,H ;,, -OH > ---Q-{ 3 > - halogen > -NO, (NO, is called the nitro group)
3nd the ring carbons numbered from the carbon morn holding that group. For example:
&CD,H s ,-me<h,Jb<"rokadd
&B, ls3-b="o=h,Jb<"u"e
~ Js4 -"J<=hJorobe",e"e.
Cl
Worked example
Answer
There are six isomers . Their names and formulae are as follows
o, o,
6( ~" ";6["
2,3-dlbromophenol 2,4-d lbromophenol 2,5-0lbromophenol
o,
How many isomers are there of

"t6r" ~" .)&"
trkhloromethylbenzene,Ci;HiOiCHi)?
What are their names? 2,&.dlbromophenol
"
3,4-dl bromophenol 3,5-0lbromophenol
421
ORGANIC CHEMISTRY
lfthebenzenering is3 substituent' onanalkyl o ralkenylchain,itis giventhename

phenyl:
25.3 Reactions of arenes

Combustion
Benzene and methylbenzene (who,;e o ld name, toluene, is still in use) are
components of many brands of unleaded petrol. In sufficient oxygen, they bum
cornplecelytocarbondioxideandsteam:
If liquid arenes are set alight in the Jaborato,y, they burn with veiy smoky fbmes.
Much soot is produced because there is insufficient oxygen for complete combustion .
A StlK}kyflame isan indication ofa cornJX>und with a high C : H ratio.
Just as with hydrogenation, the enthalpy of combustion of benzene is less exothermic

thanexpected , becau.seofthestabilityduetothesixdelocalisednelectrons .
Electrophilic substitution in benzene

In a similar way to the It bond in alkene.s, the delocalised It bond in benzene is an
area of high electron density, above and below the six-membered ring . Benzene
chereforereactswithelectrophiles. Becauseoftheexcrastabilityofthedelocalised
electrons. however. the species that re-act with benzene have to be much more
poweiful electrophiles than those that react with ethene. Bromine water and aqueous
Theelectrophilesthat reactwithbenzeneareallposithelycharged. with a strong

electron-atcracting tendency. TheO(hermatordifferencebetween benzene and
alkenesiswhac happensaftertheelectrophile hasanacked then lxmd. lnalkene.s. an
anion "adds on" to the carbocation intermediate. In benzene. on the cxher hand. the
carborntion imermediate loses a proton. so as to re-form the ring of II electrons . This
demonstrates how stable the delocalised system is .
B,
6
422
Al kenesreactby electrophilicaddition
Arer.esreactby electrophilicsubstitution.
Bromination
Benzene wiJJ react with non-aqueous bromine on ,varrning in the presence of
anhydrous aluminium chloride or aluminium bromide, or iron([[[) chloride. or even
justironrnetal.lnthelauercase.aninitialreactionbetweenironandbromine
providestheiron(Hl) bromide catalyst:
2Fe{s) + JBr1(1) ----t 2FcBr 3{s)
Anhydrous aluminium or iron(lll) halides contain electron-deficient atoms . They can

react w ith the bromine molecule by accepting one of the Jone pairs of electrons on
B, B,
I I_
Br - Br : ..-...At - Br Br - Br - Al - Br (la)
I I
B, B,
This causes strong pola1faation o f the Br--Br bond. weakening it. and eventually
Jeading toitshe1erolyticbreaking:
B, B,
I
B, + s,- 11- B, Br" +Br - Ai - Br (lb)
V I I
B, B,
The bromine cation that is formed is a powerful electrophile. 1t becomes attracted to
the It bond of benzene. It eventually breaks the ring of electrons and forms a CJ bond
to one of the carbon atoms of the ring :
(2)
Two of the six It electrons are used to form the (dative) bond to the bromine atom .
The O!her four It electrons are spread over the remaining five carbon atoms of the
ring, inafive-cemredelocalisedorbital (seeFigure 2S .10).
Figure 25.10 The four~ eH!ctrons are

debc:alisedol'l.'ffivecarbons
The distribution of the four It electrons is nOI: even . They are associated more with
caibon atoms 3 and 5 than with atoms 2. 4 and 6. The positive charge is therefore
d istrib uted over atoms 2. 4 and 6 . This is be.st represented by the following classical
423
ORGANIC CHEMISTRY
orientation effects on page 427.

The intem,edi3te carbocation then loses a prown. to re-fonn the sextet of
1telearons:
H B,
y(,
~
(3)
The final stage n,g enerates the carnlyst. by the reaction between the prol:on formed in
step(3) withthe1AlBr.tfformedinstep(lb):
tt+ + A\Br" - ----t HBr + A1Br1
Funher substitution rnn occur with an excess of bromine, to fonn dibromobenzene,
and even tribromobenzene. For the reactions of bromobenzene, see section 25.4 .
Chlorination
Justaswithbromine.chlorineinthepresenceofanelectron-accep{orsuchas
alurniniumchloridewillsub.stituteintothebenzenering:
Cl
rA
V + Cli
A<a
--;;;!--+ 6 + HCI
The propenies and reactionsofchlorobenzene are discussed in section 25.4 .
Nitration
Benzene does nOl react with nitric acid , even when the acid is concentrated.
Bui a mixture of concentrated nitric and concentrated sulfuric acids produces
g + HNO, '";';~'::'' 6' + H,O
Funher nitration to dinitrobenz.ene (and also some oxidation) rnn occur unless the
temperature is controlled co be below 3bouc SS 0 C.
The role of the concentrated s u lfuric acid in this reaction is to produce the
p o werful electrophile needed to nitra te the benzene ring. By analogy with
g +B
,
424
we might expect the electrophile for nitration to be NO/:
andthisindeedseernstobethecase.
Over the years . variouspiecesofevidencehavebeencollectedtosub.stantiate the
claim of No, (known as the nitryl cation or nitronium ion) to be the electrophile .
Smblesaltsconminingthenitrylcationexi.st , forexamplenitrylchlorace(VII),
NO(Clo,-, and nitryl tetm(luorobomte(lll\ N0 2'BF4-. Each of these, when
dissolvedinaninensolvent,nitratesbenz.enesmOO!hlyandinhighyiddto
givenitrobenzene.
The infrared spectrum of a compound tells us about the types of bonds in the
compound, and its shape . The infrared spectrum of a solution of nitric acid in
sulfuric acid shows a strong absorbance at 2350cm- . This absorbance is also
present in the spectra ofnitryl salts, but is noc present in that of nitric add in
the absence of su lfuric acid . It is almost identical to a similar absorbance
in the spectrum of carbon dioxide. C01 and NO/ are isoelectronic linear
molecules (see section J . ]j). and so would be expected to have similar
infraredspectra.
Various physico--chemica l data (for example , the depression of freezing point) show
that when one molecule of HN0 3 is dissolved in concentrated sulfuric acid.four
particles are formed. (fhe freezing point of a liquid is lowered if substances are
dis.solved in it. and the amount of the depression depends upon the mole ratio of
solute to solvent.)
These three pieces of evidence suggest that the following reaction occurs when the
The mechanism of the nitration of benzene

Sulfuricacidisastrongeracidthannitricacid. ltissostrongthatitdonatesa prown
!Onitric acid . In this reaction. nitricacidisactingasabase!
The protonated nitric acid then loses a wacer molecule. and this is then protonated
byanother molecule o fsulfuricacid:
H 2NO/ --+ H,O + NO,*

H,SO, + H,O --+ ttso,- + H30'
The nitronium ion then anacks the benzene ring in the usual ,vay. forming the
carbocation intermediate.which subsequently loses a proton:
The nitration of benzene and other arenes is an imJX}ltanl reaction in the prcxluction
ofexplosives(seeFigure25. ll)
425
ORGANIC CHEMISTRY
Figure 25.11 Th1eepowerfulexplO'i!ve1that

arepoly-nitmrnmpoumll
trinitrobenzene (TNB) trinitromethylbenzene trinitrophenol

(trinitrotoluene)(TNT) (picricadd)
Also, vfa subsequent reduction, nitration is an imp;:mam route to 3romatic 3mines,

which are used 10 make a variety of dyes (see Topic 27).
dy~
fttnybmlne
Alkylation (the Friedel-Crafts reaction)

In 18n the French chemist Charles Friedel and his co-v.orker. American chemist
James Crafts, discovered thm when benzene is he31ed with a chloroalkane in the
presenceofaluminiumchloride, thealkylgroupatrnchestothebenzenering.
The reaction goes vfa the formation of an intermediate catbocation.
Thecarbocation is the electrophile.
Acylation (Friedel-Crafts acylation)

lfanacylchloride (se,,section26.3,page442) isu.sedinsteadofachl=lkanein
the Friedel----Craftsreacrion.a phenylkeconeis produced .
CHJ'c~O
+CH,COCI =, 6 +HCI
The reaction between an acyl chloride and aluminium chloride produces the acylium
ion. The imermediate is formed from the anack of the acylium ion on the benzene
ring.
426
0
~ +Atq --------) cHJ- C= o + A1c1;
CH{' 'et ;macyliumion
+ w
Worked example
Draw the stru{tural formulae of the products you would expect from the reddion of
benzeoeandaluminiumchioridewith
a CHiCHid
b (CH1}zCH--COCI
WhatorganochlO!ir.ecompoundsare
neededtosynthesisethefollowing
Answer
compoor.dsfromb{>nzene?
Electrophilic substitution in substituted arenes -

the orientation of the incoming group
When methylbenzene is treated with nitric and sulfuric adds, the three possible
mono-nitro compounds are formed in the following ratios:
ONO, ONO, Q
NO,
If the NO ( electrophile had acrncked the ring in a purely random way, the
distribution should have been 40 :40 : 20 (there being two 2-po.sitions and two
3-po.sitions. but only one 4-position). This non-random 31tack is seen in Ol:her
reactionstoo(seeTable 25 .5).
427
ORGANIC CHEMISTRY
Table25.5 Olil'ntatklnin1omeek>ctroph ilic Percentage of product htlo

substitutioo!l'actions
,~-l '-,-f,'-,:-----< (ortn;;:araJ
f-~-.,-,- ,-'~~
6 .,-o,~ 6-,o,
OH OH
6 " 6-,o, 0 ,~
The data in Table 25.5 rnn be imerpre!ed as follows .
The orienmtio n of the incoming g roup (N01 or Br) depends o n the substitue nt
alreadyinthering.3nd nOlontheelectrophile .
Some substituents favour both 2- 3nd 4-substitution. whereas Olher substituents
favour3--substitution.atthe=penseoflxxh2 - and4-substitution
If we look clo sely 31 the types of substituents that are 2.4-directing. we find chm
either they are capable o f donating ele.:,trons to the ring by the induc tive e ffect , o r
they have a lone pair o f elearons on the atom joined to the ring. This Jone pair
can be incorporated into the n system by sidew3ys ove rlap of p orbitals (see
Figure 25.12 D00C.lli 1~tio11of the lon.e pair
Figure25 .12).
i112,4-directin91ub1titurot1
On the (){her hand. all those substituents that favour 3-substitution have a 0-+ atom
joi neddirectlytothering(seeTable 25.6).
Table 25.6 SUbstituents.indtheireffectson 2- ~nd 4-dlrectlng substltuents 3-dlrectlngsubstltuents

the benzene ring
H- if}_A,
H,ff-~- Ar
428
The orientation effects of different substituents

To explain why electron-donming .substituents are 2,4--directing, and why electron-
withdrawing groups are 3--directing, we need to return to the electron distribution in
the caibocation intermediate, mentioned on page 423.
In the bromination of benzene, the intermediate can be represented as follows.
O s,
-----.
so'H OH (}.H
4 ,,,:;2
Br f-----)
+
Br ~
~
Br
;
The + charge (thm is. the electron deficiency) is due to only four It electrons being
spread over five carbon atoms . But the + charge is nOI evenly spaced. As can be
seen aOOve, it is mainly on carbon atoms 2. 4 and 6 .
Electron-donating groups at these positions will therefore be mor<, effective at
stabilisingtheintermediate,byspreadingoutitscharge,thaniftheelectron-<lonating
group were in position 3 or S, one rnrbon removed from the + charge:
Thebrominatiooofrtitrobenzene
producesmainty3-bromonitrobenzene
Draw out the mesomers of the
ri:.,
y
intermediatecarbocationar.duseasimilar
argume<1ttotheoneabovetoexplain CH,
wtiypmductionof3-bromooitrobenzene
islaYOuredoverthato/2-0f !fthemeth)igroopi!lsirutedln1he 2-oc lf1hemeth)-Jgrouplss!tuatedinthe~~
'0-positDtrelativetotheb<omlneatcxn,the 1ebtlveto 1hebrom!ne:otom,!helntermedlatel,
4-bromonitrobenzene
:..'":~O::U,'"~m:::.i~=..~: :1:.:=.":"the"'::.-~;;~t;;,.,
Addition reactions of the benzene ring

\Vhen it reacts with electrophiles, ben7.ene ah.vays undergoes s ubstitutio n. Howeve r,
under some c o nditions it can be forced to undergo addition reactions . One of these is
the addition of hydrogen.
Ethene adds on hydrogen o ver a nickel catalyst readily at room temper.llur<, and slight
pressur<,. Benzene, being more stable , requ ir<,s an elevated temperature and pressure:
rg + 3H
l
---------,
N,
l(XJ 'C aad}(J;o;,n
0
Substitution in the side chain
Methylbenzene and cxher alkylbenz.enes very readily undergo radical substitution
with chlorine or bromine in the presence of ultraviolet lig ht (just like a lkanes
section 13.5), orby boiling in the absence of ultraviolet lig ht.
Just as with alkanes, mo re than one chlorine atom rnn be substituted . But s ubstitution
occurs o nly in the side chain during th is reaction , nOI in the ring.
429
ORGANIC CHEMISTRY
In ethylbenzene, the hydrogen acorns on the carlxm morn adjacem to the benzene
ringaresubstirutedrnuchmorereadilythanthethreehydrogensonthecxhercarbon,
sothefollowingreactiongivesag<XXiyieldoftheproduct:
+ HCl
Oxidation of the side chain

When alkylbenzenes are tremed with hot alkaline potassium manganme(VII),
oxidation of the whole side chain occurs, leaving the carbon a!Om clo6est to the ring
asacarboxylateorcarlx>xylicaddgroup:
Worked example
Threi! h'iOrocarboris A , B ,md C with the fo<mula CgH 1i were oxidised by hot potassium
manganate(VII)
Hydrocarbon A gavebeozokildd, e HydrocarbonCgavebeozene-1,2,4-triok.
C6H1C01H oco
l-lrocarboo B gavebeozme-1,2-dfOK
add
rr'Vco,, ~co,,
~CO,H
co,,
Suggestthestructuresof A, B ar.dC
Answer
6",I
Sugg,eststructuresforthearomatic ~nee A gave benzok add, al three 'extra' Glrboo atorm must be in the 5ilffil' side chain. So A is:
u1rboxylk.<KidswhichwillbeprodlJced
when the following compounds are
oxidisedbyhotpotassiummar,ganate(VII)
(Allthesecompoundsareisome!'Swith
c5",'",
themolecularformulaC11H1d
Compound B must contain two side chains, since two carboxylic add groups are left after
oxidation.Whatismore,thechainsmustbeonadjacentcarbominthering,asa
1,2-dicarboxylicaddisformed.So B is
Sysimilarreasoning,Cmustbe
430
25.4 Halogenoarenes
We saw on pages 42}--424 how bromobenz.ene and chlorobenzene can be made from
benzene. The reaaions of the ring in halogenobenzenes are similar !Othose of benzene.
Halogen0<1renesundergoelectrophilicsub.stitution, andrnnbenitrated :
Cl Cl
Flg u re25 .13De1cx:ali'iationofthelooepa lr

inclllorobenzene 6 oonc. HNO,oooc . H, so,
Q NO,
However. unlike halogenoalkanes, halogeooarenes cannOI be hydrolysed, even
by boiling in aqueous sodium hydroxide. The carlxm----halogen bond is stronger
inhalogenoarenesthan itis in halogenoalkanes, possibly due to anoverlapofp
electrons similar to th.~t in phenol (see Figure 25.13, and compare it with Figure 25.12).
lnadditiontothis.thecarlxmanachedtothehalogenisncx3ccessibletotheusual
nudeophilicre-agent.sthatattackhalogenoalkane,;,sinceits 6t chargeisshieldedbythe
negative it cloud of the ring. This means that halogenoarenes are inen to all nudeophUes.
Cenain halogenoarenes find important uses as insecticides and heibicides (se-e the
panel below).
Organochlorine insecticides and herbicides

Insecticides
Chlorobenzeneusedtobemadeinlargequ3ntitiesasanintermediateinthe
production of the insecticide DDT:
Cl TCll
o~6~ Cl
JO(CH'O Cl
,-,
4.4'-dic.hloro.liJlhtnyhrichloroethant
Flgure25.14 Mala riaiscamed by a The use of chlorinated insecticides is now banned in many countries . These
microsrnpk paras ite thatis1p1ead bythebite compounds are quite inert IO biodegradation. so they stay in the environment
of theAnophelesmos quilo.M alariaa ffects
for many years. What is more. being non-hydrogen-bonded covalent substances.
over300m illioopeop~wDfldwkiearid kil!s
arn,md3millicmayear.DDTtreatmentofthe theyareinsolubleinwater.butsolubleinfatsandoils. They tend co concentrate
Anopheles me1quito saves millions of human in the fany tissue o f animals. especially those higher up the food chain . Birds of
lives, 'iO the erw;mnmental price is coosklered prey were especially vulnerable . At o ne time, the shells of their eggs were so thin
worth paying thattheycrackedduringanemptedincubation. with disastrous consequences for
their populations. DDT may stiJJ be used in pans of Africa and Asia to control the
malaria mosquito. as the advantages to human health are considered to outweigh the
disadvantages co the environment .
Herbicides
The con1pounds 2.4..dichlorophenoxyethanoic add (2.4-D) and
2.4,S-trichlorophenoxyethanoic acid (2.4,5-T) have been successfully used for many
yearsasselectiveweedkillersforbroad-leavedweeds . Theyhaveliuleeffecton
narrow-leaved plants such as grass and cereals. andsocanbeused as lawn o r field
w=dkillers. Their action mimics that of the natural plant growth hormone indole
431
ORGANIC CHEMISTRY
ethanoic add (indoleacetk add, !AA). They are members of a group of compounds
called hormone weedkillers . Their scrucrures are shown in Fig ure 25.15.
Flg ure 2 5.1 5 The structure1of1omeho<1oorll'

wl'edkill m{herbkiDl.'5)
rt=\ro-cH;"co,H ":O:o-cH;"co,H QrcH{co,H
Cl~CI Cl Cl ~N)
2,4-D 2,4, S..T "

2 ,4-D and 2.4.S-T were components of "Agent Orange ', sprayed as a jungle
defoliant by the US army during the Vietnam war. It was during this large-scale
use th31 an unforeseen problem rnme to light . During the manufacture of the
intermedia!echlorinatedphenol. asmallquantityofahighlytoxicimpurity.
tetmchlorod ibenz.odioxin (or "dioxin') was also produced (se,, Fi gure 25.16). The
temperature of the reaction has to be controlled very carefully if the amount of dioxin
istobekep1ata low level.
Unlike 2.4 -D or 2.4.5-T, dioxin is nOI: solu ble in water. If ingested. or absorbed
through the skin or lungs, ii becomes coocentra!ed in the fatty tissues of the lxxty. It has
":0:0:0:"
Cl O Cl
now been discovered that dioxin is one of the most poi.,o;:,nous chemimls known - it is
stronglyrnrcinogenic (rnncerproducing),tera1ogenic(producesmalformmion ofthe
foetus)and mumgenic(causes mutations). hrnuse.sskin burns and ulcers that heal
only very slowly. Improved methods of production of 2.4-D and 2.4.5-T an,- now in
tetrachlorodibenzo1,4-dioxin
(TCDD,'dioxin ') place , but theriskofacddenmllyproducingbrgequantitiesofdioxinisstiJJ pn,-sent
unlesseffectivecontrolsan,-in place. Othernon-ehlorine-eontaininghormone
Rg ure25 .1 6 Dioxin - ahighly toxicmoleru~ weedkillersan,-preferred - theyan,-equallyeffective,butmon,-=pensive.
Theuseofchlorinatedherbiddesisnowseverelyn,-stricred , justasistheuseof
chlorinatedinsecricides.
25.5 Phenols
P hen o ls contain two functional groups - the -OH group of the alcohols. and the
phenyl ring of the arenes. Their reactions are for the most pan the sum of the two
sets,butwithsignificantnxxlifications.
Nomenclature
!>!any o f the compounds iJJustmted in Figure 25 .8 (page 41 9) are phenols. If the only
Ol:her g roups on the benzene ring are halogen atoms, nitro. amino or alkyl g roups,
the compounds are named as derivatives of pheno l itself:
CH OH OH
Q CH,
O NO, Q'Cl
Cl
i -m<thylp>tnol 2-nltrophenol 2.4-lichlorofhenol
{p-methylif...-.ol) (o-nltrophenol)
If. however, the other g roup is an aldehyde , ketone or c arboxylic add g roup, the
phenolic -OH becomes a 'hydroxy' s ubstituent:
432
J.tt}dro:qbt=Jclehydt -hydroxybtNXJicocid
(boloown"' (alsol"""'""'
J-hydroxybt~billthydt) H1.ydror,btn.,.noc>ma:(ylic acid)
Worked example
DrawthestructtJrallormulaeofthe
following compounds
b hco,,
Name the following compounds
CIOCI
b
CH,
1 2,4,6-trimethylpheool Answer
2 3,4,5-trihydroxybenzoicacid
ii 3,5.<lidilorophenol b 2-hydroxy-4-methylbenzoicacid
Reactions of the - OH group

The C---0 bond in phenol is very strong, as a result of the delocalisation of the Jone
pair of electrons on oxygen over the arene ring . There are no reactions in which it
breaks. unlike the situation with the alcohols (see section 16 .3).
Reactions of the 0 - H bond

Acidity
K , - l.OxlO_, &moldm--,1
The negative charge of the anion can be delocalised over the benzene ring . Fig ure 25 .17
shows various ways in which this can be represented .
Flgure25.17 Repre=tationsa f thepheool
r~ r 433
ORGANIC CHEMISTRY
Consequently, phenol nOI: o nly reacts with sodium metal. giving off hydrogen gas-
OH 0 - Na+
6 + N, _, 6 +!H,1,1
IOOiumph<ao:illt
( whltuolid)
but,unlikealcohols,italsodissolvesinaqueoussodiumhydroxide:
OH 0 - Na+
6 + N,OH _, 6 + H,O
Phenol is visibly acidic: the pH ofa O.lmoldm- 3 solution in water is 5.4. so it will
turn universal indicacor sol ution yellow. An old name for phenol is carbolic acid (see
section25 .6).
Esterification
Because of the de localisation over the ring of the Jone pair on the oxygen atom,
phenolisnOl:nudeophilicenoughtoundeigoesterHicationintheusualway, that is,
by heating with a carboxylic add and a trace of concentrated sulfuric add (for the
mechanismofesterification. see section 18.3).
Phenol can, however,beesterifiedbyaddingan acylchloride:
O OH
+CHCOCl
3
+ N.ott
"'Pl'<idi"'
00'
O C
II
,,,-CH 1
+HCl
0
fbenylethanoatt
See section 26.Jfor a fullerdescriptionoftheconditions used for this reaction .
Substitution reactions of the benzene ring

As we mentioned on page 428. phenols an, mon, susceptible to electrophilic anack
than benzene. owing to the de localisation of the lone pair of electrons o n oxygen .
This allows phenol 10 react with reagents that an, mon, dilute. and also to undergo
multiplesubsiicutionwithease.
Nitration
When tn,a!ed with d,'l.,te aqueous nitric add (no sulfuric add is needed) phenol gives
amixtureof2- and4-nitrophenols :
OH OH
6 diluteHNO,ot,oomt<mpat1>rt
6rNO,
NO,
434
Bromination
Phenol decolorises a dilute solution of bromine in wa!er at room temperature, ghing a
white precipitate of 2.4.6-tribromophenol . No aluminium bromide is needed . Contrast
this with the conditions needed for the brominmion of benzene on page 423.
6
OH OH
+ 38,,<a> ~ B , * B , + 3HB,
B,
A similar product. formed by the action of chlorine water on phenol , is used in dilute
solutionastheantisep(icTCP (seepage436).
OH OH
6 + 3Cl,<~> ~ C l * O + 3HCI
Cl
Coupling
Phenolscouplewithdiaz.oniumsalts(seesection'I?.3) tofonnazodyes:
A specific test for phenols

When a dilute solution of iron(IIJ) chloride is added to a dilute solution o f a phenol.
a coloured comp]= is formed . The colour depends on the substituents on the ring .
With phenol itself, a purple coloution is observed :
25.6 Some important phenols

Antiseptics
A dilute solution of phenol in water ( known as rnrbolic add) was one of the
first disinfectants to be used in medicine, by Joseph Lister in Glasgow, Scodand,
in 1867. Phenol itselfisunfortunatelytoocorrosivetobeofgeneml use as an
antiseptic. Many chloro derivatives have been found to be more potent antiseptics
than phenol itself. They can be used in much lower concentrations. which reduces
their corrosive effecc . Two of the most common are trichlorophenol (fCP) and
chloroxylenol (see Figure 25.19). Thymol occurs in oil of thyme. and is an excellent
non-toxic antiseptic, as well as being a fungicide.
435
ORGANIC CHEMISTRY
FJgure25 .18ToeScotti!ohdoctor.Joseph
Lister(1827-1<J12)wasthefirrttausepheool
asana11tiM.>p~cduri11gsurgeiyOeath1fmm
infectiomfollowingoperatiomweremurn
reduced as a re'iUI~ thO\lgh the{orro1ive
natureofphenoldidnathelptheskintohe.il
A "~" Ao,
Flgure25.19Threeantieptie5lhatare
defivativesolphenol
'"Ar''", 9 ~
chloroxylenol('Dettol') 2,4,6-trkhlorophenol thymol
Analgesics
A significant number of pharmaceutical drugs contain phenolic groups. or are derived
from phenols.
The painkilling and fever-reducing propenies of an extract of willow bark
havebeenknowninmanycountriessinceatleastthesixteenthcentury. ln
thenineteemhcentury , theactiveingredient.salicylicadd(2 -hydroxybenzoic
add), was isolated and purified (the name 'salicylic' derives from the Latin name
for willow, Sa/ix) . The therapeutic use of salicylic add was limited, however.
because it caused vomiting and bleeding of the stomach. In 1893 an ester
derivedfromsalicylicaddande!hanoicaddwasfoundtohaveforfewer
1-hydroxybemoicacid ethanoy12.hydroxybemoicacid
(,.licylic~) (a,pirin)
Aspirin is the most widely used of all analgesics. However. it stiJJ ..,-rnins some of the
s!Omach-irrimting effects of salicylic add. A less problematic painkiller is paracetamol
whichisanO{herphenol.
436
25.7 Preparing arenes and phenols

Benzene and methylbenz.ene a"' formed during the cracking and re-forming of
fmctionsfromthedistillationofcrudeoil (seesection 13.3).
lhe -OH group of pheno ls can be introduced om o an arene ring by the following
sequence(...,.,.section27.3fordetails):
Ar,mes arehydrocarbonsthatcootilinooeormon>benzmerings
Thebenzeneringcontainsadekx.alisedgroupolsixite~rons.ThisrnnfersgreatstabHityoothesystem
Desf)4te their unsaturatioo, arene-; do not undergo the usual addition re.-ictiom associated with alkeoes. Their preferred reactioo type is
eledrophilicsubstitution
Aromatlc compoundscanbehalogeoatedineithertherir,gorthesidechain,deperidingoothecooditionsused
AromatK compounds with alkyl side chains can be oxid ised by potassium manganate(VII) to benzenecarboxy!ic ilCids
Underlorcir,gconditionswithhydrogen, theberizerteringcanundergoadditiooratherthanwbstitution
Phenols are more acidk than akohols, and can only be 1'51:erified by using ~ chlorides
TheC -O bondinpheoolsisverystrong,andnoreactionsoccurinwliichittxeaks
Thebenzeoeringinpheoolismuchmoresusceptibletoelectrophihcattackthanistheringinbenzeneitself.
Likealcoholsandcarboxylicadds,phenolreactswithsodium .Unlikeakohols. ilreactswithsodiumhydroxide;unlikecarboxy!icacids,
itdoesnotreactwilhcarbonates
ICeyreactlon s you shouldknow
e Electrophilicsubstitutions
Q +", o,-,.,, 0-"+'"

Q +CI, ~ 0-Cl +sCI
0 +a-Cl - - "'"- -, 0-s +sCI

(11 - CH.CH,CO.otc.)
e S4de-chainreactions
437
ORGANIC CHEMISTRY
e Reactk>nsofpheools
0 - - 0H + RCOCI Q-acoR +HCI

Please see the data section of the CD for any A,. values you Use the above information to dr.iw relevant structural
'" D D
may need. formulae. ISI
1 The substituted benzene compound
0)KMnO,+OW
O"'"", A '"'--"'--------
IO<Moo,,o,-
D
can be further substit uted (ii)H
lfYi5anelectron-withdrawinggroup,thenext!.Ubstitution J
will be inpo!.ition 3.
9A D~
tl Y isanelectron-relea!.inggroup,thenextsubstitutionwill
bem05tlyinpmition4. ,o,.
H,so, '"'"""
~
A -~
Ylx "'"A"'"
0 --,:.., 00
~
0 '
{Ctmbridge International AS & A Level Chemistry 9701,

Paper 4 Q6 June 2008]
X
The follo1'11ing table lists some electron-withdrawing and

electron-releasingsubstituents
Electron-wlthdr.iwlnggroups Electron-releulnggroups
- NO,
1-<:H,ar I
-CO,H 1- NH, I
438
2 Cyclohexanol and phenol are both solids with low melting d Chooseoneofthefivereagentsthatcouldbeusedto
pointsthatarefairfysolubleinwater. distinguish bell'veen cyclohexanol and phenol. Describe
Q-o, the observations you would make with each compound.

[2[
{Ctmbridge lnteTTldtional AS & A Level Chemistry 9701,
a Explain why the5e compounds are more soluble in
waterthanthefrparenthydrocarbonscydcl.exane
and benzene [2)
b Explain why phenol is more acidic than cyclohexanol. (2)
c Foreac h ofthefollowingreagents,drawthestructural
!Ofmula of the product obtained for each of the two
compounds. lfnoreactionoccurswritenoreactio11. (7)
11.Hgent
NaOH(aq)
Br,(aq)
I,(aq) + Ol-f"(aq)
anexc:e11ofa<ldifiedcr,o,'iaq)
439
A Level
Organic chemistry
Carboxylic acids - derivatives

26 and further reactions
Fun ctiona l gro up s:
Learning outcomes
By theeod ofthis topicyoushouldbeable to
14.1 a) inletpret anduse thegenerill,structural,displayed and
sl:eletilllomiulaeoftheacylchlorOO
17.1a) recall the chemistry of alcohols, exemplified by
carboxyHc add acyllhlorlda ethanol,intheformationofe stersbyac:ylat kmwithacyl
chloridesusing ethyl ethanoateandphenylbe nzoate
t<--->--l
as exampll'S
19.1 b) describethereactionsof carboxylicildds inthe
forrnatiooof iKyjchlorides
19.1cl recog nise th at someurboxylicacidsum belurther
oxid ised:theoxidationof meth armkiKid, HC01H,
polyester
with Fehling'sarKlToHem 're<19ffils,andtheoxida tioo
of eth,medKlic add, HO.,CCOiH, with warm addified
lnthistopicwelookattheeffectofrtructureonthe mang anate(Vll)
acidity of car boxy lie acids, and at further reactions of their 19.1d) exp lai n there!at ive ilCid itie sofca rboxylic ilCids,pheools
derivatives. and alcohol s
19.1 e) use the conceptofelectronegativity toexpla in the
itdditiesof chlori ne-substituted eth,moica cids
19.2a) describe the hydrolysis of ac.ylchlorides
19.2b) describethereactioos of ac.yl chlorideswith akohols,
phenols, ammonia and primary amines
19.2c) explainthe relat iveeaseof hydrolysisof ac.ylchlorides,
alkylchloridesand aryl chlorklesiric lud ingthe
condensafon (add ition-elimination) mech anism for the
hydrolysisof ac.ylchlorides
26.1 The effect of structure on acid

strength
As we saw in Topic 18. carlx>xylic adds are weak adds. and d issociate to a small
=tentwheninaqueoussolution:
They are more acidic than alcohols because the negmive charge o n the anion can be
delocalisedovertv.oelectronegativeoxygen 31oms.(seeFigure 26 .t ).
The increasing acidities of alcohols. phenols and carboxylk adds are explained
bytheincreasingabilityofthemolecularstructuresiodelornlisetheneg:,tivecharge
in the alkoxide. phenoxide and carboxylate anions. Their relative acidities are
demonstrated by their different reactions with sodium. sodium hydroxide and sodium
carbonate(seeTable 26. t ).
440
26 Cartoxylic acids-derivatives and further reactions I
Tobie 26.1 The llSl'of Na, NaOH arid Na,co, Reagent
toillu1tratethere lativeadditiesofak oho l1,
phenojandc.rboxylkadds ! Phenol I Hexanokadd
Na(I) H,(g)evolved I H,(g}evolved I H,{g)evolved
NaGH(aq) I dissolve,;
Na,CO:,(aq) I no reaction l co,{g}evolved
Atoms or groups that draw electrons away from the -co,- group will help the anion
toform. and this causes the acid to be more dissociated (that is, to become a stronger
add) .Onthe01herhand, groupsthmdo na1eelectronsmthe---CO,- g roupwill
cause the add to become weaker (see Table 26. 2).
;o-
Flgure26.1 1nthec..rboxy!ateanion,the
chargei11prea.d, incre.11ingthe1tabilrtyof
thelo n R-/0 ,.. -c'\, R
"0 --!- H
V
Electron-donating groups decrease the acid 51:rength of carboxy!k acids, whereas electron-
withdrawing groups inc:rease their ilcid strength.
Table 26.2 The .iddityol'i0mecarboxy1k

acids . RememberfromTopkl2that
.
, Pen:entigedlssoclatlon ln
1.0moldm-1 aqueoussolutlon
pK, =-klg 10K., where K, = !1-f"i~\aq)I
foracidsundergoingthedissociatioo
HA ,=,. W + A-
0
,}'
CH, ~ c...,_OH
0
,}'
CI - CH, - c,OH
Cl 0
> H- C~
Cl OH
Cl 0
' ,}'
c1 --;.c - c,
Cl OH
Worked example
ThepK,oflluomethanoicacidi12.57.
iiOoe-;thi1me<"1nitisastroogeroraweakeracidthanchloroethanoicilcid?Expklin
your answer.
b What pK, woukl you expect for difluoroethanoic acid?
441
ORGANIC CHEMISTRY
Answer
The lower the pK., the larger is K,. This meam t hat the acid is more dissociated, and
1 Usethedata inTable26.2topredkt thereforestronger.Hmcefluoroethanoic addisastrongeracidthanchloroethanok
thepK,valuesof: acid.Thisisduetothegreaterelectron-withdrnwir,gabilityolthehigh!yelectrooegative
a (CH1)1C- C01H fluorine atom
b CI- CH1- CHi - CO.,H b Oifluoroethanok ocid would be expected to have a klwer pK, than dichloroethimok acid
ExplainyotJrr&1SOO ing - about 1.0
2 ExplainwhythepK,valuesof
2-chlorobut,mokacid(pK, = 2.86)and
4-chlorobutanokacid(pK, = 4.53) The effect o f electron-<lonming or electron-withdrawing groups is seen even when
differ'iOmuch.PredictthepK, value such groups are situated on the opposite side of a benzene ring to the -CO,H group
for 3-c:hlombutaooic add (seeTable'.26.3).
pK, Peruntage dls!,OCl.ltlon In

1.0rnoldrTr'aqueoussolutlon
CH,-0-co,H
Table26.3 Theeffl'CtonpK.forbenzoicadd
ofelectron-do""1ingandl'll.'C:tron-withdra1\ing c1-0-co,H
26.2 The further oxidation of some

carboxyl ic acids
Unlike ocher aliphatic carboxylk adds. mct h anoic acid does nOI: contain an alkyl
chain anached to the - CO,H group . Instead. the H- CO group, consisting of a
hydrogen atom attached to a carbonyl group, has some reactions in common with
aldehydes. ln pankular. it undergoes oxidation with common oxidams such as
addifieddkhromate{Vl).
JH- C0 1H + Crp/-(aq) + stt(aq) ---t 2Cr1(a.q) + JC0 1(g) + 7H 10(1)
h also reacts with both Fehling"ssolution andTollens' reagent(seepage.301 ).
H - C0 1H(aq) + 2Cu' (aq) + 60H- (aq) ---t C0 1'-(aq) + Cu10(s) + 4H 10(0
Etlmncdoic acid contains two adjacent carbonyl groups. The proximity of two
Ii+ carbon atoms weakens the G--C bond sufficiently for the molecule
to be readily
oxidised by warm acidified manganate{Vl[).
This forms the basis of an accurate volumetric methcxl of analysing solutions

containingethanedioicaddoritssalts.
In a similar type of reaction. 11-kctoacids are oxidised by alkaline H,o, with the
26.3 Acyl chlorides

In section 18.3 we saw how acyl chlorides can be prepared from carboxylk adds.
Most acid derivatives are prepared from carboxylic adds by the reactions described in
this topic . Figure 26.2 shows a chan summarising the interrelationships belween the
aousde"at" s.
442
Flgure26.2 111termnver1iombetween
carboxylicaddsandtheirderivative,;
~/MM
Copy<hedartioFs,ce26.2. ar.dwriteone.acharrowthecorrectreag1>11tsand
rnr.drt1onsforeachreaction
Properties of acyl chlorides

Acyl chlorides are usually liquids which fume in moist air. They are immiscible with
water, but react slowly with it and eventually dissolve (see below) . They are not
hydrogen bonded : their main intermolecular attractions are a combination of
van der Waals' forces and dipole-dipole forces (see Figure 26.3) .
Flgure26.1 Oipole-d1poleattr;ictiaminacyl
chlolide1
R- C,j/O
""
The extra dectron-withdrawing effect of the carbonyl group. resulting in extra
dipole-dipole anmctions, has the effect of increasing the boiling JX)int by about
I0-15C compared with the boiling point of the halogenoalkane with similar shape
(seeTable26.4).
Tab le 26.4 Strongdipol1'-dipoleattractkm1

M', Bol ing Acyl chl orlde M', Bo llng Difference
inaea'i1'theboilingpoinllin..cylchloride1 polntlC po ln tlC 1C
A Cl
'-<Cl
'--<o
Cl
Reactions of acyl chlorides

The electronegativity of the oxygen. and the easily JX>larised C=O double bond.
have a dramatic effect on the reactivity of acyl chlorides compared with that of
With water
Acylchloridesreactreadilywithwater:
roomtemperature.complelewtthlnmlnutes
CH 3-COC! + H 10 CH 3-COOH + HCl
Compare this with the conditions for the hydrolysis of a halogen0<1lkane:
As a result of the speedy reaction with water acyl chlorides prcxluee steamy fumes of
HCl(g) when a few drops of water are added to them. This is a go;:xl test for them.
443
ORGANIC CHEMISTRY
Together with wh31 we have already seen in sections 15.3 and 25.4. we nOle th31 in
Gathertogetheralltheinlormatioogivefl
insec:tions15.3,25.4andthissectkm
R---Cl + HzO ----t R--OH + HCl
towriteanexplariationofwhythe therelativeratesofhydrolysisareasfollows:
ratesofhydrolysisofthesethreechloro
,,o
0~
compoundsdifferinthi:swif'/.Wouldyou
expectthesame1e!ativerateswithNH1or
CH1 - c, >CH1CH2 - 0> Cl
NaOHasthereagent,insteadofHiO?
Cl
With alcohols or phenols

Acy] chlorides reaa readily with alcohols or phenols. forming esters :
0
+ HOCH 1CH1 --------) CH 1C: + HCI
O - CH 1 G-l1
+ HCl
As mentioned in secrion 25.5. phenols are not so nucleophilic as alcohols. because the
Jone pair on the oxygen atom is delocalised over the ring. The acylation of phenols
is therd'ore usually rnrried out under basic conditions (NaOH or pyridine have been
used), when the more nudeophilic phenoxide ion is formed as an intennediate:
phtnylttharoatr
Because phenols do nO{ reacc directly with carboxylic adds, this is the only method
forpreparing phenylescers (seeTopic25, page434).
With ammonia and amines

Acy] chlorides react with ammonia, forming amides . The reaction is vigorous. and
white smoky fumes of NJ-4Cl(s) are often seen if an excess of ammonia is used .
They react with primary amines (see Topic 27), forming sub5tituted amides :
0 0
# #
CH1 - c, + CHJCHiNHl ~ CH1 - c, + HCI
Cl NHCH1CH1
The hydrogen chloride produced reacts "ith anO{her molecule of amine or ammonia
R- NH 1 + HCl-+ R- NH 1+c1-
Theref ce an exce, of am ne or ammon a u d to en re complece react"on.

The reactions of amides are described in section 27.S.
444
The mechanism of the reactions of acyl chlorides
The carbonyl group in acyl chlorides rnn undergo nudeophilic addition in a similar
mannertornrbonylcomJX>Unds
: ff
I
R - C - Cl
I
N"
Unlike carbonyl compounds, however, acyl chlorides are provided with an easily
removed leaving group, the chloride ion:
Nucleophilic sub.stitution has taken place, by a m=hanism involving addition,

followed by elimination.
If the nudeophile is water. the carboxylk add is formed:
Worked example
Draw the mechanism for the reaction betwe{'n ammonia and beozoyl chloride
Q-cacl +2NH, --4 Q-coNH, +NH,CI
Answer
o-l-C,
H/ !'l.,H
:er
l'ledictthepmductsof, andsoggestamec:hanismfor, thereactionbetwl>i!npropan-1-ol

andpropar,oylchloride
445
ORGANIC CHEMISTRY
Explaining th e relative reactivity of acyl chlorides,

chloroalkanes and chloroarenes
Aswesawinsectioo25.4,chlorobenz.enedoe-sno1undergohydrolysiswithwater,or
even"ithconcentrntedsodiumhydroxide-solution.duetotheoverlapofthelooepairOfl
chkxine making the C---0 lx,n,d suonger. Acy] chlorides, on the Offierhand. re:ia much
more readily than chloroalkanes with water or hydroxide. There a"' two reasons for this.
I As we saw in the panel on page 445, the unsaturated natun,- of the C=O bond
allows the C---OH bond to be formed before the C---Cl bond has broken . This
a dditlon-C'liminat k m mechanism therefore has a lower aaivation energy than the
stmightS,.2reaction.
2 The carbon atom in acyl chlorides is auached to two electronegative atoms (oxygen
and chlorine), and so is polarised Ii+ to a greacer extent than the carbon atom in
chloroalkanes. This allows it to attract nudeophiles more strong ly.
26.4 Polyesters
Formation of polyesters
When a diol is esterified with a diacid (for example, by heating with hydrogen
chloride gas). orreactedwithadiacylchloride, a polyeS!erisproduced. Figure26.4
shows the general reaction for e51erification with a diacyl chloride. Here the yellow
rectang lesrepresemtherestofthediolmoleculeandthegreencirclesrepresentthe
benzeneringinthediacylchloride.
Flgure26.4 Format~nofapolye1Wfroma
diacylchlolide
0 01
nHo- - - - 0 - - oH + nc1 -
~
c--O-c -
~
-c
c1
p
+ o----O--o- 1--o-L-
o"
c-
'a- - 0/
alternates along the chain.
PolyeS!ers are examples of a class of polymers known as co ndC'11Satlon olynicrs.
When monomers join together to form a condensation polymer, a sm all molecule such
a1H 20, HClorNHii1alsoproduced
The most commonly used polye51er is Terylene. produced by polymerising ethane-

1.2-dioland benzene 1.4--dicarboxylicacid. as shown below.
01
t 0 - CH,CH,
OII
- o - c--0-c
II
n
446
The polymer can be drawn imo fine fibres and spun into yam . Jointly wo ven with
cotton or wool. it is a component of many everyday textiles . Material made from
Terylene is hard-wearing and strong, but under .strongly alkaline or acidic conditions
the ester bonds can be hydrolysed, causing the fabric to break up.
Fig ure 26.5 Some prodlJCts made from

polye1ters
Funher condensation p;:>lymers such as nylon and pro1eins are discussed in Topic 28.
The add stl'l'f1!lth of carboxylk adds, RCOiH, depeods oo their 51:ructures. In partkular, electron-withdrawing chkirine atoms oo the alkyl
chainnNrtotheCO;,Hgroupincrease itsilCidstrength
Methanoic ,md ethanedok adds can m> oxidised forthef to COi
'
Acy I chlorides are useful intermediates, forming esters with akohol:s phenols, and amides with amines
Acylchloridesaremuchmoreeasilyhydrolysedthanchkiroalkarn.>S
Polyesters arefoonedbythecondensationofadk>lwitheitheradicarboxylicaddoradiitcylchloride
e AcylchlOOdes
RCOCI -t HiO --t RCOiH -t HCI
RCOCl -t R'OH--tRCOiR' + HCI {R' = alkylorary!)
RCOCI -t 2R'NHi --t RCONHR' -t R'NH 3CI
Condensationpolymerisatkm
nHo- -oH -tnHo,c- -co,H --t + a - -oco- -co-t,;
447
ORGANIC CHEMISTRY

Pleaseseethedata5ectionoftheCDforanyA,valuesyou iiiWhensubstance C isextractedfromtheproduct
may need. mixture, it is found that it does not decolourise
Bri(aq),butitdoesformapaleyellowprecipitatewith
1 a Describe and explain how the acidities of CHC/iCOiH
alkaline aqueous iodine.
and CHiCI COiH comp;1re to each other, and to the
Suggest a structure for C that fits this new information.
acidityofethanO.cacid (3]
iv SuggestaconfirmatOl)'testforthefunctionalgroup
b For each of the following pairs of compounds, suggest
inthestructureyouhavedrawniniii. Yourans1ver
onechemicaltest(reagentsandconditions)that would
shouldincludethereagentyouwoulduseandthe
distinguishbetweenthem.Statetheobservationsyou
would make with each compound, writing 'none' if
observation you would make. 161
b Thefollmvingdiagramrepresentsasectionofanother
appropriate.
polymer.
observation observation
compound compound (reagents and with first with second
conditions) oompou,d compound
CH 1CH 2COCI CH 1COCH,CI

i Copy and draw brackets, [],around the atoms that
CH1CH,CHO CH1COC H1 makeuptherepeatunit ofthispolymer.
ii Name the functional group in polymer D.
17]
iii Suggest and draw the structure of the monomer, E,
{Cambridge International AS & A Level Chemistry 9701, thatcouldformthispolymer.
Pdper42 Q5 a & blune 2012] iv What type of polymerisation is involved in making
2 a Polyvinyl acetate, PVA,isausefuladhesiveforgluing polymer D from its monomer?
together articles made from wood, p;iper or cardboard. v What is the relationship between the repeat unit of
The monomer of PVA is ethenyl ethanoate, B. polymer D and the repeat unit of PVA? [SI
0 t Monomer E exists a s two stereoisomers. Heating either
CH:--0. . . . . . isomer wit h A/i0 1 gives a mixture of two unsaturated

carboxyl ic acids F and G, 1vhich are stereoisomers of
PVA is formed from B by '

the process of addition
each other.
i Name the type of stereoisomerism shown by
polymerisation. compound E.
i DrawasectionofthePVAmoleculecontainingatleilSl2 ii Suggeststructuresfor F and G,andnamethetypeof
monomer molerules, and identify dearly the repeat unit. stereoisomerismtheyshow.
D "'' 00
ii Theester B canbehydrolysedintheusualw~.
.
accordingtothefollowingequation.
,-~
0 0
CH: :0 .....-...... + Hp ---- CH;l-OH +
' G 141
C(C H 0) {Cambridge International AS & A Level Chemistry 9701,
Usethisinformationto5Uggestapos.siblestructurefor
Canddrawit
448
A Level
Organic chemistry
2 7 Amines, amides and

amino acids
Fun ct iona l groups:
Lea rnin g outcomes
By theend of thistopicyoushouldbe ableto:
14.1a) inte rpreta ndtJsethegeneral, structtJral. displayed andskeletal lormtJlaeof the
amides and amino acid s
20.1a) describetheformati onof alkyl amine sStJchas ethylam ine(by thereaction
of ammon ia with halog enoa lka nes; the redtJction of amides with UAl~; the
redtJctionof nitri le1 with liAlH 4 or Hi/N i) andofphl!flyl amine(bythereduction
0 0 ol nitrobenzenewithtinlcoocentratedHCI)
N g H _,. w g 20.1b) describe andexplainthebasic:ityol amines
H/ J ' c~
2 \:/ .,- H/ J ' c~ 'a-
1
20. 1c) expla in the relative basidties of am monia, ethylamine and phenylamine in terms
oltheir structmes
20.1d) describe t hereactionofphenylamine wit h aq tJeOtJs bromine,and with nitrom
add to givethe diazonitJ mlillt and phenol
20.1e) describe t hecouplingofbenzenediazonitJmchlorideandphenol
Aminesareorganicbases. They 20.2a) describe the formati on of amides from the re<Ktion between NHi or RNH1 and
reactwithacidstoformsa/ts,and R'COCI
aminesthatareso/ubleinwaterform 20.2b) recog nise thatamides are neutral
a/kalinesolutions. Thereactionof 20.2c) describe am idehydrotysi s on lfl'ilt ment wit haqtJeOtJsalkali oriKid, anddescribe
ary/amineswithnitrousacidisthe t hereductionof am ides wilh liAl H4
firststepinmakingdyes. 20.la) describe t he acidlbase propertie1olaminoacids and theformationol
zwitterions
Amides are neutral compounds 20.lb) describe t hefor mationof peptidebond1between amino acids to givedi-and
formed when ammonia or an amine
t ri -peptides
reactswithanacy/ch/oride. 20.lc) describesimply theprocessofelectrophoresis and theeffectofpH,using
Amino acids contain both the peptides and amino acid sasexamples
basic - NH1 group and the acidic
- C01H group; they are therefore
amphoteric,reacting withboth
acids and bases. Amino acids are the
buildingb/ocksoftheimportantc/ass 27.1 Introduction
o f biological polymers known a s the
From prehistoric times. people have been aware that the le-:, ves or seeds of cena in
polypeptides, or proteins.
plants were pharmacologically active. in alleviating pain. reducing fever or causing
Thetopicconc/udeswithalookat euphoria . In the early days of organic chemistry. when chemists were extracting,
synthetic po/yamides, including the purifying and anempting to identify the hundreds of compounds that ocrur in
various types of nylon.
natural organisms, they d iscovered that many of these compounds were insoluble
in water, but dissolved in dilu te adds. They called these the a lka loids ("alkali-like") .
Many of the alkaloids =trncted from pbnts were found to have strong physiological
and psychological effects on humans and oiher animals. These included hypnoiics
suchasmorph "ne. narc()( cssuch ascorn ne. a drnrd"acpoisonsuch astry hn"ne.
All alkaloids contained at least one nitrogen acorn. and all belonged to the class o f
compounds we now call a mines. Figure 27 . l illustrates some of their structures .
449
ORGANIC CHEMISTRY
Flgure27.1Thestructuresofs.omenoturally
oc:rnrringalk.iloids
q uin ine
1 Apart fromthenttrogen atoms,wtiat
ftmctkmalgro tJpsarecontainedin
ii thequinir.emolecule
b thecocainemolecule?
'~1;_!,:;o
2 WorKout themolecular formulaof ~00
a qlllrnne
b caffeine
3 Themoleculeolnkotineisc hiral.Draw
outthestructure,s.howingwhd1 atom
is t he chiral one
Mostalkaloidshaveabinerta.ste.butaret<X>involatile(thatis.theyproducet<X>
little vapour) to have an odour. Those amines tha! are volatile haVl" di51inctive smells
The shott-ehain amines have an astringent ammonia -like smell. but this is replaced
by a strong fishy odour in bucylamine and Jonger-ehain amines. Ary] amines such as
phenylaminehaq,amore'oily'smell.
The amines can be derived from arnmoni3 by replacing one or mon, of the
hydrogen aton1s in NH 3 by organic groups: replacing the amine hydrogen atoms rnn
often be carried out in the laboratory.
H H
H- N- H
H
I
6
phenylamint
The carbon-nitrogen bond. althoug h quite .s1rongly JX>larised. is fairly inen and it is
nOI so easily broken as the C--0 bond in alcohols (see Topic 16. page 282). There
are few reaaions in which the c &. atom takes pan. The key point of reactivity in
the amines is the Jone pair of electrons on the nitrogen atom. which is more readily
don ated than a Jone pair o n oxygen . This lone pair is nudeophilic towards c &. and
basic towards H&.. Amines form sttong hydrogen bonds to hydrogen-donor molecules
Flgure27.2 Intermolecular such as ,v:uer. Those amines that contain N- H bonds also form strong intermolecular
hyd!O(jffitxmdingln..nlnes hydrogen bonds (see Figure 27 .2).
The shon--chain amines are therefore water soluble and their boiling JX)ints are
higher than those of the coITesponding alkanes (see Table 27 .1 and Figure 27.3).
The effect o f hydrogen bonding on boiling point is nOI so pronounced as it is in the
alcohols, however (compare Table 27.l with Table 16. t. page 282).
Table 27.1 Brnlirigpoin~of,;ome alkanes
andrnrre1pcmdingomine1 ln<reue ln
electrons In + - - - ~..,
- ,-,.,- ---i bollng
Bolling
the molecule polnt/ 0 ( polntloc polntf'C
CH, NH,
C:,H ,NH,
CJ-1, NH,
C, H,,
C, H,, NH,
C 7 H 10
450
27 Amines, amides and amino acids I
Figure 27.l Boilingprnnt1of10me
.ilkane1andcooespomlingamlnes

The mo.st imponant feature of the amine mol=ule is the nitrogen atom . This is
reflected in the nomencb ture of amines . The simpler ones. such as dimethylamine
and phenybmine shown opposite, are named as though they are derived from
ammonia . Up to three hydrogen atoms in ammonia rnn be replaced by organic
groups. Successive replacement forms primary, seco ndary and tertiary amines
(see Table 27 .2). Note that it is the branchingthac mkes place at the nitrogen
atom, rather than at the carbon atom atrnched to it, that determines whether an
amine is primary, secondary or tenbry . This is nOI the same as in the case of the
alcohols :
CH, CH,
CHJG-l 2 CHi
' cH - OH ~CH - NH1
/
CH,
'/ N- H
CH, CHJG-I 1 CH1
Table27.2 Someprim.iry.l,@rnndaryand
terti.iryamine1
-- p<OfW'l-l-<>l
Prim ary a mi nes

l-arnlnop<>paae
prlm..,.ami<>t
5erond.1 ry a ml nes
diprop,-bmlne
OK<>ndary:unlne
Terti ary ami ne

CH,CH,NH, (CH,CH,),N H (CH:iC H,),N
ethyl.imine diethylamine trH'thylamifll'
cs,-oN,, 0;-0 O N~CH,
"
4-rnethylphenyl.imine
d~ enylamine
'"'
N.N.<Jimethrohenylamine
o N,, CN-,
cydohexylamin e p~ kline OY
451
ORGANIC CHEMISTRY
An alternative way of naming amines is used when the chain becomes more
branched, or when Olher functional groups are pr,,.sent . This views the - NH1 group
as a sub.stiruem. called an a m ino group:
?H1 ~ H
C H, CH
/ , /"
CH1 CH 1 NH1
NH,
l.2-dl:uninotthane
(often'*'ll'"1:ndto'en')
Apart from the usual structural or positio,rnl isomerism that can occur in the carbon
chain. amines also demonstrate structural isomerism around the nitrogen acorn.
throughtheforrnationofsecondaryandtettiaryaminesaswellasprirnaryamines.
Worked example
How ffi<lny isomers are there with the formula C1H~N?
Answe r
There are four i'iClffil'fl. Structural iMlmerism in the propyl group allows two primary
(CH1l1CH-NH1
prop)'amifl!'(l -amooopropane) 2amioopropafl!'
Fourtee<1olthei'iOfnefswiththef01mula In additioo to these, we can split the three-carboo chain into two or three eh aim, to form a
CsH, 1N contain a nitrogen atom directly secondary amine
boodedtoabenzenering.Drawtheir
structures,ar.dstatewh ichareprimary,
secoodaryand te<tiaryamines
and a tertiary amine
t,imethylamir>e
The nitrogen atom in amines is pyramidal. as it is in ammonia . Although the

secomLuy amine ethylmethyLtmine could exist as a mirror-image pair o f compounds
(seeFigure27.4).inpracticethenitrogen3lomunde,goesarapidinversion.likean
Flgure27.4 Theoretical enantiomersof umbrelb turning inside out , causing a 50 : 50 mixture of the two forms to exist at
ethylmeth~am in e r<X>ln!emperarure(seeFigure27 .5).
,,,Q, ))...
( Q ) ,, C,H,~/:,,,.,'",_.H
(c,H(' C,H,-N~ )
Flgure27.5 lnversKJnatthenitrogenatom
prmllJCesaracemi::mixture
\ CH,
(j " 0
27.3 Reactions of amines
Basicity
Amines are basic . They react with acids to form salts:
+/ H
CH,CH 1NH1+Ha --t CH,G-:l1 - N ~H + : c1
H
The alkylammonium chlorides , sulfates and nitrates are white crystalHne solids.
solubleinwater.butinsolnbleinorganicsolvents.
452
Those amines that are soluble in water form weakly alkaline solutions. just as
ammonia does. due to pani3[ reaction with the solvent, prcxludng 01-r ions:
..
Table n .3 lists some amines. with values of their dissociation equilibrium constants,
Tabl e2 7.3 Theb.11i<:ityofIDmeamin~
Kb,forthefollowingequilibrium :
/mold m- R1N + H 10 ;:c="c R1NH+ + Otr

[R 1NH+J[OH- ]
phenylamineO-NH,4.lxl0- 10 Kt. = ~
The larger Kb is. the stronger is the base . Ammonia is included for comparison .
NH 1 1.8x10-'
From Table 27.3 we can see th31 electron-donating alkyl groups anached to the
ethylamine CH1CH,NH, 5.1 xlo-' nitrogen acom increase the l:xisidty of amines. This is expecced. since the l:xisidty
d~thylamine (CH1CH,}:,NH 1.0x10-1 depends on the availability of the Jone pair of electrons on nitrogen to form a dative
bond with a prol:on (see Figure nii). Electron donation from an alkyl g roup wiJJ
encourage dative bond formation .
Flgure 27. 6 Whenanamineactsasaba..e,

thenilrogenlonep.iirformsadativebandw;th
a proton
The nx,st dramatic difference in basidties to be seen in Table n .3 is betwe.,n that of

phenylamine (Ki, .. 10- ') and the alkyl amines (Ki, .. 10--'). Taking two compounds of
abou t the same relative molecular mass and shape, we see that phenylamine is about
a million times Jess basic than cydohexylamin.,,
This is because in phenylamine , the Jone pair of electrons on the nitrogen arom is
delornlised over the benzene ring. The bonds around the nitrogen atom can take
upa planar arrangement. withthenitrogen'slon.,pairina porbital. so thatextra
stability can be gained by overlapping this p orbital with the delocalised It bond of
thebenzenering (.....,Figure27.7).
Flgure2 7.7 Oelocalio;atkmofthenltrogen

kmepa irinphenylamlne
This overlap, causing a drift of dearon density from nitrogen to the ring, has two
effectsonthereactivityofphenylamine.
hcausesth., loneP3irtobemuch lessbasic(seeabove) andalsomuchless

nudeophilic .
hcausestheringtobemoreelectronrich.and so toundergoelectrophilic
substitutionreactionsmuchmorereadilythanbenzene. The enhanced reactivity of
phenylamine in this regard is similar to that of phenol (Stt- Topic 25 , P3ge 43'1) . an
453
ORGANIC CHEMISTRY
example being the ease with which phenylamine decolorises bromine wmer:
A
lV-1 + 3Br 1{q) -----} y
B,AB,
+ 3HBr
B,
We shall see a similar drift of electron density from nitrogen when we look at amides
insection27 .5
Only the shoner-ehained amines ( with five or fewer carbon atoms) are soluble
in water, but the ionic natur<, of their salts allows all amines to dissolve in dilute
aqueous acids . This is a very useful way of purifying amines from a mixture with
non-basic compounds . The amines can be regenerated by adding an excess of
aqueous sodium hydroxide to the solution, after the non-basic impurity has been
extracted with an organic solvent (see the experiment below).
The separation of codeine and paracetamol from

a medicine tablet
This separation makes use of the fact thm codeine is basic. fonning water-soluble
salts with acids , but paracetamol is slightly acidic, and is insoluble in water (see
Figures27.8and'Z7.9).
Flgure27.8flowchartforthee~rimmtal
procedure to be followed Grindupthetablet with a norga nicsolvent,uchasdichloromethane .
Then,hake the,olutionwithdilute hydrochlork acid, a ndallow
the twola)'ffto.eitle .
I :: ~~~~~o~! ~~~ei~yr.o:~~:::r~~~d. I ~J.Fo~~~:~~';~~~ill di,,otve in the I
I I
Addanexce,sofaqueou.,odiumhydroxide
tone utralisethehydrochloricacid.and
I ~::~::;~~-e ,otvent to 1..- pure I
shake withanewsampleofdichloromethane .
I Ev poratethesolventtoleave pure codeine.
q_:~1::-:::::t~,~:;,,
Flgure27.9S1.1ge1 ,,o, oo,
inthesePJalKmathe
firstM.'p,lrationremovl.'I
a;;o,.,,a,~Mo,;,~
thepa<acetamolinthe
add containing
codeine hydrochloride ~ ,,.,,;a,~
aqueou.layer
org.w1K:!ayer.b'i0dium
hy<lroxkJeneutrali1,1_>1 dichloromethanelayer dichloromethane
the aq\ll'Olll !aye~ containing paracetamol
andc:theun-Klllised lay";,:~~~:\~;
codeinei1re-fooned hydrochloride
anddi1'iOIYl.'linthe dichloromethane laye r
organic!ayer contain ing paracetamol
454
Reactions as nucleophiles
AnO{her similaritybet""'"" amines and ammonia is their nudeophilicity. The lone
pair on the nitrogen atom of amines makes them good nudeophiles. They react with
alkyl and acyl halides (see page 274 in Topic 15 and page 444 in Topic 26).
CH1CH 1NH 1 + CH1C0Cl ~ CH 3C,

,.
0
+ HCl
NHCH1CH1
ln!hepresenceofanexcessofa brotn<X1lkane. aminescanbesuccessivelyalkylated.

first to secondary and then co teniary amines. These are stiJJ .s1rongly nudeophilic,
and are readily alkybted to qua!ernaiy ammonium salts
CH1CH 1NH 1 + CH1CH 1Br ----t {CH 1CHz}1NH + HBr

{CH 1CH 1)zNH + CH,CH 1Br ----+ {CH 1CH 2hN + HBr
{CH 1CH 1)1N + CH 3CH 1Br----+ (CH 1CH:J 4N'"B,-
Quanernary ammonium salts are water-soluble solids. with no basic character

at all. because the..,- is no lone pair of electrons on the nitrogen morn. An
imponant naturally occurring ammonium salt is choline . Phosphatidylcholine is a
key phospholipid component of cell membranes . Acetylcholine is an imponant
neurouansminer, allowing a nerve impulse co pass from the end of one nerve to the
stattofthenextone(seeFigures27.10and27. l\) .
Fi gu re 27.10 Some import.ml naturally

occu11irigquate11wyammonium'>.llt1
CH1
"-.~/ "-,<
o CH,
"-;ic,,,c,-
acetykholinechloride
Flg ure2 7.11 .iAcetyknolinetransmiB

anerve impulo;efmmonel'f!dofanerve
toanotherata1ynapseortoamu1de
atamotorendplatl'.b Curare.adea<lly
polo;oousedbySouthAmerkanlridiam
ontheirarrowbps.bkx:kstheactKlf\of
acetykholine
phosphatidylcholine
455
ORGANIC CHEMISTRY
Reaction with nitrous acid (nitric(III) acid)

Nitrous acid, HNO,, is un51able , and has to be made as requil'ro by reacting together
sodiumnitriteandhydrochloricacid:
NaNOi + Hd----+ NaCl + HN0 1

Aromatic and aliphmic amines differ markedly in their reactions with nitrous acid.
Primary aliphatic amines react in warm aqueous acidic solution to g ive nitrogen gas
andakohols :
Ary! amines, however. fom, fairly 51able diazonium salts al low temperatures. Under
these conditions nitrogen is nol evolved. but a solution of the diazonium sah is formed:
Ary] diazonium salts are unstable and explosive when dry. but can be kep( for several
daysinsolutioninarefrigemtor.
Reactions of diazonium salts

1 Adding a solution of a diaz.onium salt to h(){ water causes decompo.sition. and
produces phenol:
-
Q-N = Nc1- + H10 ~::;~ Q-0H+N 1 +Hc1
This is the analogous product to the alcohol produced when an aliphmic primary
2 The tn06I imporumt =icrions of diazonium salts an, their use in the fonnatiOfl of 37.0
dyl'S (see panel opposite). When a solutiOfl of a diaronium rolt is added to 3n alkaline
solutiOfl of a phenol. an electrophilic substitution reactiOfl ( kncw.n as a coupling
rcactio n ) takespbce:
Q-oH + OH- N:tOH(,ql Q - o- +Hp
27.4 Preparing amines

The two main methods of preparing alkyl amines both sun with halogenoalkanes .
By nudeophilk substitution with ammonia (see Topic 15. page 273):

he>tin<th,no\
CH3CH1Br + 2NH3- - - - CH3CH1NH1 + NH.Br
underprenu<e
As long as an exces,; of 3mmonia is used. funher substitutions giving secondary and

tertiary amines can be avoided (seepage 444) .
456
Azo dyes
A chromophore is a groop whkh, The azo group, - N=N- , is called a chromoph~. Compounds containing this
espec:iilllywheojcined to other unsaturated group are highly col01Jred . Their colours range from yellow and orange to red, blue
groups, causes a compound to ab'iorb and green. depending on what other groups are au ached to the benzene rings .
visible light, ilnd so become coloured The common add-base indicator methyl orange is an azo compound, made by the
coupling reaction shown in Figure 27.12.
Flgure27.12 Methyl orange is

anazocompoundformedbya
rnuplingreactKln
Many dye molecules used for dyeing clothes do n(){ easily .stick to the fibres of the
material by themselves. This is especi3lly the case if their main method of
intermolecular bonding (for example, van der Waals ', hydrogen bonding, ionic forces)
does ncx match thac of the molecules that make up the material. Mordants are often
used to help the dye molecules stick. A mordam is a JX>lyvalem metal ion. such as
A[l+ orFe* .whichcanformco-ordinationcomplexesbol:hwiththedyenx,leculeand
with --OH . -CO or - NH groups on the molecules that make up the fibres of the
material. By this means the dye molecule and the fibre molecule are permanently
held together by the metal ion. A g reat number of dyes for c[O{hes. colour printing
and food colouring (Figure 27 .13) are azo dyes. Figure 27 . 14 shows two examples.
Flgure27.13foodcoloursottenrnnt.1inazo
"'"
Flgure27.14 S.Omeazodyi.-;u'ied
rnmml.'fdally
,,o,s-0-\~
S0 1Na
Carmoisine (red)
1 Draw the structures of the two compotmds from which Sunset Yellow can be made by
arouplingrei!Clion .
2 WhatarethestructuresofthetwocompoundsthatcoupletolormCarmcisine?
457
ORGANIC CHEMISTRY
By nucleophilic substitution with .sodium cyanide, follmved by reduction using

either lithium te1rahydridoaluminate(U[) (lithium aluminium hydride) or hydrogen
over a nickelcarnlyst(seeTopk 15. page27-0:
heatin~ol H 1 + Ni
CH,CH 1Br + NaCN ---------> CH 1CH 1CN ---------> CHJCH 1CH 1NH 1
NO!:ke that during this reaction the carbon chain length has been =tended by one
Amines are also produced when amides are reduced by lithium

tetrahydridoaluminme(ll[) (catalytic hydrogenmion only succeeds under conditions
of high pressure and temperature). This allows amines to be synthesised from
carboxylicadds:
{Wnylmtthyl:omlne
Ary] amines are most commonly prepared by the reduction of aromatic nitro
compounds (,..,.,. Topic 2S , page 424):
To produce the f,.,.,. amine, excess sodium hydroxide muSI be added after the
reduction is completed.
Worked example
The'goodfeeling'factorif1chocol.itehasbeenidentiheda12-pheoylethytamirie,
Suggest two Wil'fS ol milkir.g bu~amine
Ct;HsCH1CHiNH1.Suggestasyothesi:softhi:srnmpoundfromchloromethylbetizene,C.,H,;CHi(I
{CHiCH1CH1CH1NH1), each method
startingfromacompoundcootaininga Answer
difleteotriumberofCilrbonatoms The target amir.e has ooe more carbon atom than the 'iUggested starting material. so the
cyankleroutei:sre,quired
27.5 Amides
Properties of amides
Amideshavethefunctionalgroup:
Draw diagrams to show the hydrogen

bond ing between
ii 11\umoleculesofethanamkle, Rand R'canbealkyl. arylorhydrogen .
CH1CONH1 Amides are extensively hydrogen bonded, having lxxh H&. atoms (on nitrogen) and
b a molecule of ethanamide and two Jone pairs of electrons (on oxygen and nitrogen). ,\lo& amides are .solids at room
molecu~ofwater.
temperature, and quite a number are soluble in water.
Unlike amines, amides fonn neutral solutions in water, and can be prcxonated only
by strong adds. The site of prcxonation is unusual. and explains why amides are such
458
Figu re 27.15 De!ocali<;~tion of the nitrogen
kmepairintheamkiegmup
;o
R- C~
_. NH,
The Jone pair o n the nitrogen atom in amides is in a p orbital. and can overbp with
the 1torbitaloftheadjacemcarbonylgroup: theelectronsareattractedtothe
electronegative oxygenatorn(se,,figure27.15). This confersconsidembledouble-
bond characteristics co the C-N bond. including restricted rolation about it (compare
with the alkenes, see Topic 14 page 252). This has grem sig nificance for the
stereochemistry o f p;:>lypeptide chains in pro1eins. which we shall meei later in
Topic 28. Po lypeptide chains contain secondary amide groups
The propenies of synthetic polyamides such as nylon are co vered in section 28.2 .
When amides react with strong adds. it is the oxygen atom. rather than the
nitrogenatom.thatisprcxonated:
0 [O' H' OH
"NH,
R- c, .. R- C:f' R- C,
/
' NH, NH,

Profonmion of the nitrogen atom would result in a positively charged nitrogen
adjacent to the 6t carlxm of the carbonyl group - an unfavourable situation . On the
other hand , prol:oruuion of the oxygen atom allows the ~sitive charge on the cation
to be delocalised m er three atoms - an energetically favourable situation:
~0- H
R- C
"
( ~H,
So. although amides are more basic (chroug h their oxygen atom) than <Xhn carbonyl
con1pounds (bemuse of the electron donation fron, nitrogen). chey are still much less
basicthanconventionalnitrogenbasessuchasamines.
Preparation and hydrolysis of amides

Amides are most readily prepared by reacting acyl chlorides (see section 26.3) with
The HCl formed reacts with an excess of amine to produce a s:ih
459
ORGANIC CHEMISTRY
Reactions of amides
With water
Because of the high deg,..,., of positive cha,ge on the carbon atom in prolOna!ed
amides, they are susceptible to nudeophiHc acrnck . Hydrolysis is usually carried out
indilutesulfuricacid. ltis.stillquitea slow reaction. hmvever - heatingunderreOux
forsevemlhoursisus1.mllyrequired:
0 0
R- C~ + H 10+H " h<at..;thH,so,i"'ll R- C~ + NH/
NH 1 OH
Amides can also be hydrolysed under basic conditions, by heating with NaOH(aq)
0
CH1 - C~ + Na + OH - 1-tw;thN.oH(oql
NHCH1
The mechanism of the hydrolysis of amides

The mechanism is very similar to that of the hydrolysis of esters, described in
section 18.3. The initial reaction is the proionation of the amide by the mineral add
(this occurs on the oxygen atom. as described above). The pro1:onated amide is
then attacked nucleophilically by a water molecule . Prolons rearrange themselves
amongst the oxygen and nitrogen atoms, and eventually the C- N bond cleaves,
and a proionisthentmnsferredtoNH 1 (see Figure 27 .16).
Ftgure27.16 Thehydroly;.isofanamkle
+o- H
,_ ,~0
~ "NH,
H/ "H
+;)_H' \
R-
~
C" OH + NH,
..
Amides are intermediates in the hydrolysis of nitriles to carboxylic acids-
1 Writeabalancedequationlmthe
cooversiooofethaneoitrile,CH 3CN,
intoethaooicacidbyheatingwith
hydrochloric acid
2 (Diffirnlt!) Draw oot the mechanism of Reduction to amines
thehydrolysi:sofanitriletoanamidl'
Amides can be reduced to amines by lithium tetrahydridoaluminate(II[) (lithium
(H int:thenitrogeoatomhastobe
protonatedtwice,intwos.eparateste,ps aluminium hydride):
olthemechanism.) 0
R- C~ UAIH,O'ldr,-etht, R- C!;i
NH 1 NH 1
460
Worked example
Suggest products of thefollowingreactions
,jO ~X~Y~Z
CH1CH, - c,OH
Answer
ii X is CH1CH 1COCI Y is CHiCH1CONH1 Z is CH1CH 1CH1NH1
b Ais V - COCI
Suggesttwo-stagesynthesesof thefollowingcompounds,fromthestatedstarting
materials
27.6 Amino acids

AminoaddshavetwofunctiOflalgroups:
The 2-amino acids (a -amino acids) form an interesting class of compounds, apan
from their great imponance as the building blocks of proleins. In many compounds
containing two or more functional groups. the reaaions of one g roup can be
considered independently of those o f the cther group. They are often widely
separated. and dis.similar to each Olher. In 2-amino acids, however. the two groups
are near to each cxher. Whm is more. they are of opposite chemical types : the - NH,
group is basic, whilst the - CO,H group is acidic. Interaction be!ween the tv.'O is
Physical and chemical properties

Whilsc alkyl amines and the small-chain aliphatic carboxylk adds an, liquids, the
amino acids :,n, all solids . They have high melting points (of!en decomposing befon,
they can be heated to a sufficiently high temper:11un, to melt them) , and are soluble
in water. In another contrast to amines and c:iiboxylic acids, they are insoluble in
org:,nksolventssuchas methylbenzene.
461
ORGANIC CHEMISTRY
Tab le 27 .4 A rnmpari'ioo of some properties

K.lrnol drrr 1
ofsimpjeamioo..dd1(glycill!'andalanine)
wilhlho'>t'ofasimpleam ineanda1imple """"'""'
g!yone H,NCH,CO,H
Meltlngpol nU"C
1.4x10-10
Kb/rno ldrrr'
2.4x10- 12
c.arboxyhcacid H,NCH(CHi}CO,H 9.Bx10- 11 2.2x10-"
ethylamine H,NCH,CH, 5.lxlo-'
prnpanokadd CH 1CH 1CO/i 1.] ~ 10-
Table 27.4 compares the propenies of the two simplest amino adds with those of a
simple amine and a simple rnrboxylk acid. Apan from their extremely high melting
points. anOl:her dear difference between the amino acids and their mono-funaional
countell}ans is their much reduced basidty and acidity. Glycine is 200 miJHon times
Jes.sbasicthanethylamine:
H 1NCH 1C0 1H + H 10 ~ H 1N+CH 1C01H + OH- Ki, = 2.4 X 10- 11 moldm- l

CH1CH 1NH 1 + H 10 ;:c="c CH1CH 1NH/ + OI-r Ki, = 5.1 X 10-mo!dm-l
Likewise. alanine is over IOOOOOtimeslessacidicthan propanoicacid:
H1NCH(CHVCOzH + HP ~ H1NCH(ctt;,co,- + ttp+

K,. = 9.Sxl0-11 moldm- l
This large reduction in basicity and acidity is readily explained by the idea that the
acidic and basic groups within an amino acid molecule have already reacted with
R R
I
CH 0 H ~H O
f.( 'c,1- ';{ 'c.f'
/1 I / I I
H H OH H H o-
The product is an "internal salt'. called a zwittc rio n (from the German word Ztl'iller,
meaning 'hybrid' - zwinerionic Slructures were first proposed by the German chemist
Kiisterin 1897).
A zw itterion is a molecule that contains both a cationic group and an anionic group
The salt-like nature of zwinerions also explains the high melting points and the
solubility characceristics of amino acids. It is thought that all amino acids exi51 as
zvdtterions (or dipolar ions) in solution and in the solid lattice. Their low acidity is
therefore due to prolOn donation from the ammonium group rather than from the
carboxylicacidgroup:
This ,11lue is directly comparable with the ionisation of O!her ammonium salts
K, = .5.6 X 10-IOmoldm-l
One funher characteristic property of 2-amino acids is their optical activity. All except
glycinei:x,ssessachiralcarbonatom,havingfourdifferentatomsorgroupsanached
10 it. There are two diS1inct and different ways in which these four groups can
arrangethemselvesaroundthecentralcarlxmatom.asshowninFigure27.17(see
also page 224). All amino acids derived from the hydrolysis of proteins have the/
configuration.
462
Flgure27.17 /.andd-a lanine
r
H,w-__...c\-H H7 J~ NH 2
co,H HO,C
Reactions of amino acids

Because the dipolar form of amino acids is in equilibrium with a small amoum of
the un -ionised form. amino adds show many of the typical reactions of amines and
carboxylicacids.
I The amino group can beacylated(see page455)andreactswithnitrousacid(see
page4S6):
/NHCOCH1
R - CH + HO
~
/NH1
R- CH ' C01H
'co,H ~ /OH
R - CH + Nz(irl + H10
' C01H
.? Thecarboxylicaddgroupcanbeescerified:
/NH1
R- CH + H10
'co,cH1
.i Amino acids act as buffers. srnbilising the pH of a solution if excess acid or alkali is
added (see section 22.3).
On adding acid:
On adding alkali :
-i In addition 10 the r,,action.s of the -NH, and the ---C02H groups. amino acids with
side chains that contain functional groups also s how the reactions of that group .
Figure 27 .18 shows the side chains of some amino adds. For example , serine reacts
with pho.sphoru,(V)chloridetoforma chloroalkylsidechain. and tyrosine reacts
with bromine,,,:nerjust as phenoldoes(seeTopic2S.page43S).
Drawthe51ructureoftheproductoleac:hofthelollowingre<Ktions(seeFigure27.18)
a1 Tyrwith811foq)
b lyswithane)((essofhydroc:hloric<Kid
t Glu when heated with an excess of CH 30H and a trace of concentrated H1S0 4
d SerwithanexcessofCH3COCI
463
ORGANIC CHEMISTRY
Flgure27.18 A'>l'leclionofamioo
acids,wilhtheirnamesandthe
three-~tter codesbywhi::htheyare
kMw"
gly<ine,Gly alanine.Ala valine,Val
rA{CHr-CH( '"'
)VJ COiH
,o
phenyla lanine,Phe tyrosine,Tyr
lysine,L)'t cysteine,Cys ser"ne,Ser
a'Pa rticadd,Asp glutamicadd,Glu arginine,Arg
'i Pe-pi:ide lx,n,d fonnation- two or nx,re amino acids can unde,go condensation ..,-actions
becv,=n themselves to form amides, which. if formed from amino acids, are called
peptide.. If the pepi:ide is comp;:,sed of two amino acids ii is called a dipeptide.
HiNCtt,co,H + H1NCH(CH~COlH ----+ H1NCHzCONHCH(CH1)COzH + HP

thcdipcptide O\y- Ala
NOlice !hat the dipeptide Ala----Gly is nOl the same as Gly-Ala : it is a structural
thedipcptidc A!a- 0\y
If three amino acids join together, a tripep1ide is formed .
H,N, 1
+ T 'OH
Gly AS
l-m,o
H,NJ _l ,NH'CO
NH,,. "'l( OH
O OH
the tripeptide Gly - Ala - Ser
NOlice that the prefixes di- and tri- refer co the number of amino adds in the pepiide,
andnoi:thenumberofpeptidebonds.
Worked example
How many possi~e tfipeptides can rn> formed from t he three amino acids Gly, Ala and Ser,
ifeadi tripeptidernntainsall three amirmacids?
Answer
There are six isomeric tripeptides: Gly- Ala- Ser, Gly- Ser- Ala, Ala- Ser- Gly, Ala- Gly- Ser,
Ser- Gly- Ala andSer- Ala- Gly.
We1hal lmee t peptidesagaininlopjc28,inthedesc riptiooof proteins.
27.7 Electrophoresis of amino acids and

peptides
The principle of electrophoresis is best explained by looking first at how the simple
amino add, glycine, behaves al different pH values. This is because of the amphOl:eric
propenies of amino acids. If we have a solution of an a mino add in wmer. the
average charge on the many molecules of amino acid in the solution depends on
the pH of the solution. The pH at which the net overall charge is zero is called the
L'iOClcctric p oint ofth31 amino acid. For glyci ne. this is pH 6.07 .
+ H+ - H+
"'N H,C H 2C0 2H ~ "'NH,CHz COZ ~ N H iC H 1COZ
at pH < 6.07 at p H 6.07 at pH > 6.07
In solution 31 pH< 6 .07, the average charge on glycine molecules becomes positive.
At pH>6 .07. themoleculesbecomeneg31ivelycharged.
Depending on the side groups, different amino adds have different tendencies
to form cations or anions in solu tion. and so their isoelectric points \\-ill occur 31
different pH values . Themorebasiconessuchaslysine,whichhavea !endencyto
fom1 cations if dissolved in water. wiJJ have their isoelectric points at a more alkaline
pH than mo.sl . On the cxher hand. the acidic amino acids such as a.spank acid will
have their isoelectric points at a more acidic pH than mo.st (see Table 27.5).
Tab le 27 .5 The iM>l'lec:tricpainBofsome
lsoelectrkpol ntO EPJ
amino adds
glyone
- KH,), NH,
a1opartic add - CH,CO,H
If all three of these amino acids were dissolved together in the same buffer solu tion
kept at p H 6 .07. on average. the molecules of g lycine would be electrically neutral.
themoleculesoflysinewould be positively cha rged ,
andthemoleculesofa.spa nicacidwouldbenegativelycharged.
465
ORGANIC CHEMISTRY
Flgure27.19Electr()jlhoresi11eparate1 lfadropofthebuffersolutionat pH6.07containingthesethreearninoacidswas

lysine,ai.particacidaridg!yc:ine spottedontoagel-coatedplate.imrnersedinaconductingliquid, and a po(entbl
diffe..,-nce applied. the lysine would move to the cathode. the aspanic acid ,vould
move to the ancxle, and the glycine, having no overall electrical charge, would nOl
moveat all(seeFigure27 .19).
This sepamtiOfl of a mixtun, in an electric field is called <'lcctrophor<.'sL'!. The
electropho..,-1ic mobiHty depends n{){ only on average charge but also on the size and
shape of a molecule:
EZ
spot placed here F
where I! = velocity , E = electric field (voltage applied), Z = average charge and
The frictional resistance is con1p;:,sed of various factors:
the size of the JX)l"es in the gel suppon. (the smaller the pores, the slower the
sample moves)
the shape of the molecule (Luge, spiky molecules travel slower than small
spherical ones)
the size/ molecular mass of the molecule (larger molecules travel slower than smaller
ones).
Other factors that can affect the speed at which the components of a sample move
duringelectrophon,sisan,:
the pH of the buffer solution (the average number of charged groups on an

amphoteric molecule depends on pH ; as the pH incn,ases, the average charge
becomesmon,negative/ lessp;:>Sitive)
the n,mpemtun, of the apparatus (the speed of movement increases with temperatun,).
Electrophoresis is used n,gularly to separate and identify not o nly mixtun,s of amino
acids, but mixtun,s o f pepiides obrnined from pro!eins, and even mixtures of pro1eins
themselves (see Figure 27 .20). By this means, abnormal proteins can be identified in
patients suffering from genetic disorders, and possible tn,atments moniton,d .
Flgure27.20 Elect1ophoresi1ofproteln1
27.8 Synthetic polyamides (nylons)

SynthC'tiC polymnid(.'!l (nylons) an, an imponant class of manufactun,d polymer.
They are condensation polymers (see section 28.2). usually formed by the reaction
betweenadiamineandadicarboxylicadd:
Values of >1 and m vary from 4 to 10.
466
Diacylchloridescanalsobeused,inareac tionsimilartothepreparntion o f simple
arnides(seesectio n 26.3) .
0 0
% 4'
H1N---{CH 1r,;-NH 1 + /C---{CHi);;-C'\
Cl Cl
Funher information about polyamides can be found in Topic 28
Amlnes arewNkorganicbases,reactir.gwithacidstofomisalts,andd issolvinginwatertogivealkalinesolutions

There are three types of amine - primary, RNH1, secondary, R1NH, and tertiary, R3N
Ar/, amines ll!act with nitric{III) acid (nitroos acid) to fOfm diazonium sa lts, from whkh many useful azo dyes are manufactured
Am ino acids contain the - NH1 and -C O.,H functional groops adjacent to each other. In solution and in the solid they exist as
zwitteri o ns, ' NH1CHRco.,-
Mostam ino<Kklsa rechiral.Tho..eisolatedfromnaturalproteinshavethe'fconfiguration.
Electropt10resiscar1Dl'usedtoseparateaminoac:idsarKlfl{'ptides
Synthetic polyamides such as nylon are made by condensing diaminl'S with diurboxylic acids .
(R = alkylorarylunle11othem'ise1tated.)
Amines
Alkylation
R- NHi + CH 3Br---tR--NHCH 3 + HBr
Acylat km
R- NHi + CHiCOO---t R- NHCOCHi + HCI
Withnitroosadd(nilric(lll)acid)
atroomtemperarure
alkyl-NHi + HNOi - - - - - - - - - } alkyl-OH + Ni{g) + Hi()
atf < 5 ' C
aryl- NHi + HNC}., + W ~ aryl- Ni*+ 2HiO
Amides
H)'droJysi1
heatwithW
RCONHi + HiO ~ RCOiH + NH 4+
heat with OW
RCONHi + HiO ~ RCOi-+ NHi
Reductkln :
U.l>/l-4inethef
RCONHi ~ RCHiNH 1
Polymerisation
467
ORGANIC CHEMISTRY
Examination practice questions 2 a Desc:ribethereagentsandconditionsrequiredtoforma

nitro compound from the following
Pleao;eseethedata5ectionoftheCD1oranyA,valuesyou
i methylbenzene
may need.
1 Phenolandchlorobenzenearelessreactivetowards
certain reagents than similar non-aromatic compounds
Thushexan-1-olcanbeconvertedintohexylaminebythe
following two reactions,
ii phenol
I
CH)("CH;z).;OH _________,,.. CH)("CHzlsC/--------;,. CHi{CH 1~NH 1
hexan-1-ol 1-c:hlomhexane hexylamine
whereas neither of the following two reactions takes place 131
b Draw the structure of the intermediate organic ion

a i Suggestreagentsandconditionsfor formedduringthenitrationofbenzene. 111
reaction I c Write the reagents needed to convert nitrobenzene into
reaction II phenylamine [1]
iiWhattype ofreactionisreactionll? d Phenylaminecanbeconvertedintotheorganic
iiiSuggestarea'iC>nwhychlorobenzeneismuc:hles.s compounds A and B.
reactive than 1-c:hlorohexane. 141 i SuggestthestructuralformulaeofAand B.
b Phenylaminecanbemadefrombenzenebythe ii Suggestsuitablereagentsandconditionsfor step 1.
following two reactions.
'l l c1-
i Suggestreagentsandconditionsfor
6'"'~ stepl
6"
]",la~ j6a
reaction Ill
reaction IV
ii Statethetypeofreactionfor
reaction Ill
reaction IV ISI 131
c Suggestareagentthatcouldbeusedtodistingui~
e Whenphenylamineistreatedwithpropanoylchloridea
phenylaminefromhexylamine.
white crystalline compound, C, C9H11 NO, is formed.
reagent and conditions
i Name the functional group formed in this reaction
observationwithphenylamine
ii Calculate the percentage by mas.s of nitrogen in C
observationwithhexylamine 121
d Phenylamineisu5edtomakeazodyes.Drawthestructural iii Drawthestructuralformulaof C 131
fOflllula of the intermediate D and of the azo dye E.
Paper42Q31une2013]
iA("NH,~
V T<5"C
121
{Cambridge lnte!Thttional AS & A Level Chemi5try 9701,
Paper 4 Q6 June 2009]
468
A Level
Organic chemistry
28 Addition
polymers
and condensation
Functional groups:
Lear ning outcomes
Bythemdofthistopicyooshouk:l beableto:
21 .fa) desoibethefofmationofpolyeste rsaridpolyamides
21 .1 b) describe the cha racteristics of condensation
polymerisation in polyesters as exempl ified byTeryjene.
inpolyamidesasexemplifiedbypolypeptides,prot~ns.
This topic t.ikes a more detailed look at the addition nylon6,oylOf16.6andKMilr
po/ymerlsation of alkenes, fint met In Topic IA, and at 21 .1c) deducetherepeatu,nitolarondensationpotymef
condemation polymerisation to form polyesters .ind obtained from a given monomer Of pair of monomers
poly.imldes. met in Topia 26 and 27 rMpttvely. 21 .ld) identify the monomef(s) present in a given section of a
condensation polymer molecule
21.b) predictthetypeolpolymemationreactionloragiven
monomer or pair of monomer.
21 .2b) deducethetypeofpolymem.Jtionre.xtionwhich
producesagivenwctionofapolymi!rmolec~e
21 .3a) disc:vss thepropert~and'itructureofpof)ffibasedon
theirmethodsofformatioo(addifonorror.der1sation.see
alsoTopic14)
21 .3b) discusshowthepresenceofside-chainsar.d
intermolecl.llarforcesaffectthepropertiesofpolymeric
materials(e.g. polyalkeries, PTFE CTeflori), )(ev\ar)
21 .3c) explainthesigoifici:IOCeofhydrogen-boodioglntne
pairlngofbasesinDNAinrelationtothereplkationof
genetic Information
21 .3d) distioguishbetwoontheprimal");secondary(u-heband
!3--sheet)andtertiarystructuresoflJ"oleinsandexplain
thestabitisationofsecondarystructure(throoghhydrogen
bondingbetweenc - oand~boodsolpeptide
groops)and tertiarystructure(through interacti0!1s
betweenR-groups)
21 .3e) describe how polymers have been designed to act as non-
solvent based ildhesives, e.g. epoxyresins and s.uperglues.
ar.dasconductingpolymers,e.g.polyacetylerie
21.4a) recognise that polyalkenes are chemically inert and can
then!forebedifficutttobiodegrade
21 .4b) recognisethatanumberolpolymerscanbedegradedby
the action of light
21.4c) recognisethatpolyestersandpolyamidesare
biodegradablebyh~~s
21.4d) desaibethehydrc,ly!.isoflJ"oleins.
469
ORGANIC CHEMISTRY
28.1 Addition polymers

We saw in Topic 14 how ethene could be polymerised in different ways to prcxluce
low-density poly( ahene) , LOPE, and high-density poly(ethene) , HOPE . Addition
ix>lymers with a variety of propenies can be made by polymerising other comp;xmds
containing double bonds.
P rop c n <" (obtained by catalytic cracking) can be polymerised in a similar way to
ethene, usingtheZiegler- Nanacarnlyst (seesection 14.4):
tc-c71
\1''
H
I
H
I
?Jly{proptnt)

During polymerismion. the propene subu n its line up in a regular head-to-tail

arrnngemem . because as each propene molecule is added to the growing chain. the
more stable secondary carbocation (see page 248) is formed as an intermediate (see
Figure 28. l). Note tha! only two o f the three carbon morns in propene become pan
ofthechain: thethirdoner<,mainsasamethylsidegroupatthe'tail'. Thetrieihyl
aluminium is an dectrophile, actin g as a honx,geneous catalyst.
~ _ .~ _r r .
'", '", r r
(C,H.JiAI CH 2= CH ---.... (C,H.JiAI - CH, - CH CH,= CH- CH 1---.... (C,H,)iAI - CH, - CH - CH, - CH
I I I I
Flgure28.1Theprnpeneunit51ineuphead
to tail
Phc n y lct h cnc can be JX}lymeri.sed to form poly(phenylethene) , O{heiwise known as

polysty..,ne:
,rn,-c(dl
I!~J
H
p:,ly{if,enylet he<><)
(p:,lf!tyftn<)
Phenylethene is obtained commercially by =cting together ethene and benzene

followed by dehydrogenation. It is an imix>rtant component of the co--p;:,lyrners SBR and
ABS (see the panel on pages 471- 472).
The mechanism of this p;:>lymerisation is similar to that of the ix>lymerisation of
propene, but it involves radicals as intermediates, rather than cations. The more
stable secondary radical is formed at e:ich stage and the polymer forms in a reg ular
head-to-tail chain (see Figure 28 .2). The initial alkoxy radical is formed when the
,veak 0--0 lxmd in the peroxide is broken by heat.
470
28 Addition and condensation polymes I
Flg u re28 .2 lnphe11)'1ethene,themooomef
unit1lineupheadtat.1il
R- O" ~ CH
Poly(phenylethene) is used for packag ing (for example. egg boxes). and nxxlel kits
(becausewhenitismouldeditcandepictfinedetailsexactly). Whenaninengasis
bubbledthroughthephenyletheneasitisbeingp;:>lymerised.thefamiliarwhite.veiy
light, solid known as e x pa n dC'd p o trstyrclH' is formed . This is used as a pro!ective
packaging. andforsoundandheatinsulation.
Rubber - natural and synthetic co-polymers

The rubber tree is indigenous to South America. but large plammions han, been
established in India and Malaysia . When its bark is stripped. it oozes a white
sticky liquid called la tex. which is an emulsion of rubber in water. Purification
of this prcxluces rubber. In its natural state, rubber is nOI: pankubrly useful. lt
has a low melting point, is sticky and has a low tensile streng th. In 1839, Charles
Goodyear discovered the process of vu lca nisa tio n , which invo lves heating
natural rubber wi th sulfur. This produces a substance with a higher melting point
and of greater strength . Rubber is an addition polymer of 2-methylbutadiene
(isoprene)(seeFigure28.J) .
Fl g ure28 .31soprEneunden;oes.iddition
polymerisation to form rubber. c~ / \
l -', ,, o, I\
isoprene
(2 methylbutadie ne)
NOl:e that when a diene unde-rgoe:s addition polymerisation, a double lx>nd is still
present in the producr . This double lx>nd may be cis or /rans. In natural rubber, the
long chain is cis across all the double bonds. From different tr=s. a naturally occurring
Fig u re 28.4 A rubbe r tree bein g lapped. The substance called gutta percha can be obtained, this is an isomer of rubber in which aU
while latex ii rnnverted to rubber 1uit.ibl e for double bonds are /rans. Guna percha is harder than rubber, and in the 19th centuiy
IYft>1bythep10Ce11of vukani1abon wasusedas a coating forgolf OOlls.
471
ORGANIC CHEMISTRY
The presence of the double bond in rubber allows further addition reactions
to cake place. If liquid rubber is hemed with sulfur, sulfur atoms add across some
of the double bonds in different chains. cr=s-Hnking the rubber molecules (.see
Figure 28.S). This is what happens during the vulcanisation process. It .stops the
chains from moving past each Olber, and gives the mmerial more rigid ity.
(' Yr \
V J \_; \_;
i\r r
. . . .~ .
.... ~ ..
Flg u re28.5Wkanis..tJOOofrutJber
NO{ all double bonds have sulfur added to them. lbat would make the substance too
hard. About 5% sulfur by mass is adequate to give the desired properties. Many millions
oftonnesofvulcanisedrubberan,madeeachyearforthemanufactureofcartyres.
Synthetic rubber-like polymers were developed when rubber was in short supply
during the Second \\brld War. The one most commonly used ccxlay is a co-polymer
ofphenyletheneand butadiene,calledSIIR (styrene-butadienerubber).
A co.polrm.er is formed when two or more different alkenes are polymerised
together. Even if the ratio of monomers is SO:SO. there is no guarantee th31 the
monomer fragments will alternate along the chain. The order is fairly random (in
contraSI to condensation co-polymerisation - see sections 28.2 and 28.3).
The product SER 51j]J contains a double bond. and so can be vulcanised just like
Anodier co-polymer involving phenylethene and butadiene as reagents. along with

acrylonitrile. is the tough.rigid plastic AIIS .oracrylonitrile---butadiene---styrene:
fh<nyltthme
Once again. the monomers join together in a fairly random manner. so the drawing
of a particular repeat unit' does not imply a regular order. ABS is used for suitcases,
telephones and odier objects that need to be strong and hard. but not too brinle.
472
Flgure 28.6 Product5marn!fromrubber, S8R andABS
Addition polymerisation of other ethene

derivatives
Most comJX>Unds containing the >C=C< group will undergo polymerisa!ion. Several
important polymers a"' made from monomers in which some or all of the hydrogen
morns in ethene have been replacc,d by oiher atoms or groups. Some of them. with
theiru.ses,arelisled inTable28. I.
Table2 8.1 Strvctu re-;am!u>l'5of,;orne

Po ly mer
additklnpolymm
poly{chlornethene) guttering,waterpipes,
CH, - CHCI (po!yvinykhklride,PVC) winoow5,HOOfrnvelings
tetrafluoroetherie poly<tetraflooroethene) no11-1td{ookware,bridge
CF:, ..., CF:, {Tefkln,PTfE) bearings
methyl 2-methroropenoate poly{methyl 2-methylprnpermate) protective 'glass. ur rea r
CH, - C(CH1)CO,CH1 {Perspex) l~hl1,1hop1igm
methyl 2-cy,mopropenoate poly{methyl 2-cy,mopropermate) instant superglue
CH, - C{CNKO:,CH1 {cyano..crylate)
cyanoethel\l' poly{cy,moeth1>1ie) co-polymerised with
CH, - CH-CN {acrylic:) COfr4>00entsof 'aoyfk'
fibre1,ABS
Worked example 1
Draw t w o repeat units of the poiyrnef formed from each of the following monomers or
p;1irofmonomer1
a CH 1 = CH-OCOCH1
b CH 1 = CCI-C H= CH 1
c CHi = CHCI ar.d CHi = CH-C Hi
Answer
_.,c;~_,...CH.z_ ,.
r 1H
OCOCH1 OCOCHi
473
ORGANIC CHEMISTRY
The following are sections of addition polymen. Draw the mooomer{s) from which they are
fom.e<l
ii <H1- CH(CN )-C H1-C H(CN)-C H1
b -CH1- C(CN) = CH-C H(CN)-C H1-C (CN}=CH -C H(CN}-CHr
Answer
Suggest the mooomer(5) from which the following polymers have beeri made
o.
oo
28.2 Condensation polymers
There are two strategies for making condensation polymers. Each strategy results in a
diffe,.,nttypeofpolymer.
The first Slrategy, producing type I polymers, starts with a monomer containing
two different functional gl'OIJps that can condense together to form either escer o r
amidegroup.s(seeFigure28.7).
Flgure28.7 Formafonoftypel
rnmlemationpolymefl
nHo- 0 -co,H
ahydroxyadd
nH,N- - D - CO,H
\ ;/
\,--o-<
HN- - D - C O
apolyamide
474
The second strategy, forming ty pe II polymers, stans with two different
monomers , one containing two carboxylic add g roups or two acyl chloride
g roups, and the other conrnining two alcohol groups or two amine groups (see
Figure28.8 ).
\-0-o\ --Q-/1o
Flgure28.8 Forma!Klnoftypell
rnnderisationpolymer,;
nH0-0-0H nHo,c- - Q -co,H -nH,o

I \
adicarboxylicacid a polyester
NH,-----C)-----NH,
adia,cylchloride apolyamide
The two types of polymer differ in the direction of successive funcrional groups along
the chain. In type I polymers, the d in,ction of each escer or amide linkage is the same
(see Figure 28.9:,), whereas in type II polymers, the direction of the ester or amide
Hnkagesalcemates (seeFigure28.9b).
Table 28.2 lists some common condensation polymers. The different nylons
(polyamides) a"' named according to the number of caibon atoms conrnined within
each monomer: the firSI number is the number of carlxm morns in the diamine, 3nd
thesecondisthenumberofrnrbonmomsinthedbcid.
~
Flgure28.9The0fientationofadjac:entester
linkageslnaatypelpolye1terandbatypell
polye1te1 0
rY'',,
II
~
0
C
il''-o,A._)
rY'-oII c~ o
rY''- ,A._)
',,, ,A._)
c c- ~ o
o c-~o
\ -0-0---c c----o
0 \ --0- ;/
;/ \ -0-o~c
\ --o-/
0
/I \
475
ORGANIC CHEMISTRY
Ta ble 28.2 The monome~ of some For mu la(e)ol monorner(s) Type of polymer
rnnder1S.lboopo~m
Polyesters
HOCH 2CH 10H

HO,C -C ,H.-C O,H
po~ acticaod(PlA)
Po/yam/des
HOCH{CH,}CO,H
""''
NH,-{CH,). -NH,
nyloo6,6
HO,c -{CH,),- co,H
NH,-{CH,).-NH,
""'"
nyloo6,10
HO,c -{CH,).-co,H
""'"
"""''
polypeptklt>S(prnteim)
NH,-{CH,),-C O,H
""''
NH,-C HR-C O:,H (R = various side chaim)
""''
Worked example
Drawtherepeatunitof thecha inof
a nyloo6,10
b nyloo6
Answe r
The repeat unit is the sma llest unit from whkh the po~mer chain can be buitt up by
repetition. That of nylon 6,10 wi ll include one molecule of each of the two monomers,
while that of riylon 6 will rnntain jmt the one monomer tmit
.i I
[N H
/c~ ft!? /c~, / N~
CH, CH1 CH1 !/C'\z f~ /c'\, /c~
CH1 CH1 CH,
)1
CHz n
b j f~
[N H
/c~
CH
1
/,~l1
CH
1
n
nylonG,10
"'""'
1 K~arisapo~ whichisfivetirnesstror.gerthansteejooanl!<Jual-weightbasis.lt
isusedinbkydetyres,racings.ail sandbodyarmourbecauseofitshighteosile
51:rength-to-weightratio
Kevlar is made Imm t he followir.g two mooomers
Ho,c-0-co,H
a OrawtherepeatunitofthepolymerKevlar.
b OeddewhethefKevlaroratypeloratypellpolymer.
2 A biodegradable co-polymer can be made from !actk. add, CHiCH(OH}CO.,H, and
3-h'jdroxypropanoicadd,HOCHiCHiCO.,H.Orawtherepeatunitolthisco-polyrner.
Like simple e.sters and amides, polyesters and polyamide.s rnn be hydrolysed by
strong adds or alkalis . ~fany common fibres used for clcthing, such as nylon.
JX>lyesters.w1X>Jandsilk ( bcxholwhicharepro{eins).rnnbedis,;olvedacddentally
by careless s plashes of laboratory adds or alkalis .
476
28 Addition
. an d condensation polymes I
Flgure28.10 Someu,;esofnylon
ORGANIC CHEMISTRY
The tensile strength of Kevlar is five times that of steel. on a weight-for-weight basis
(its densi!y is small: about i.Sgcm--3), yet it is quite fl=ible. It finds uses in tyres for
cars and bicycles, bullec-proof vests and the 'skins' Ofl modern drumheads
Nomex is a related polymer, made from 1,3-diam inobenzene ar,d benzeoe-1,3-dk.-irbooyj

chloride,whichisusedinfire-proofdothing
rArCOCI
~COCI
ii Draw the stnicture of part of a chain of Nomex, shm\ ing two tepe<1l units, ar.d suggest
howthestreogthoftheinterrhainhydrogl.'flboodsmightdifferfromthat inKevlar.
Explainyoorrea'iOlling
b How might the flexibility of Nomex compare to that of K~ar?
A dramatic use of Kevlar, together with glass-reinforced polyester, is illustra!ed by

thefOOlbridgeatAberfeldyinScotland(seeFigure28.12). Thiswasthefirstbridgeto
use composite materials and W3S built in 1992. It was much lighter th3n the po,;sible
31ternatives made from steel or concrete. and was built for only a third of their cost.
Flgure2B.12TheAberfekfyloot!Jlidgeis
madefromgla1s-reinforcedpolye,;terltsc:ables
aremad.efrnmKevlar
Cross-linked polymers
E3rlier in this topic we saw how rubber was vulcanised through the cross-linking of
the chains of the rubber molecules with sulfur atoms . This made the rubber harder,
stronger. less flexible and Jess sticky'. The imerchain hydrogen bonding in Kevlar
has a similar effect in that Kevlar is more rigid and stronger than polyamides such as
nylon 6 .6or nylon 6, 10
The imerchain bonding in Kevlar produces two-dimensional sheets. which can
bend and slide over each other. More rigidity can be produced if the polymer chains
are cross-linked by covalent bonds into a three-dimensional Janice . One of the first
p;:>lymers to have these propenies was b a kc litc. developed in 1907 in New York by
the Belgian chemist Leo Baekeland. Bakelite was the world's first symhetic plastic,
478
made from phenol and methanol, and its manufaaure marked the stan of the plastics
a ge. h is a thermoset ting condensation polymer: as the monomers are heated
!Ogether. the mixture becomes mor<, and more viscous and eventually Sels solid.
Funher heating does ncx melt the polymer, but causes it to char. Bakelite is quite
brinle , butstrongenoughtobeusedinmanyapplicationswhereahard, electrically
insulating.heat-re.sistantmmerialisn,,quired .
The main molecular requirement for cross-linking is for the polymer chain to
containsidegroupsthatrnn linktoolherchains (seeFigures2S.13and 28.14).
As can be seen in Figure 28 .13, the add-<:atalysed reacrion betw=n phenol
and methanal produces intermediate A. which has three ---CH 20H groups on the
phenolic benzene ring in the 2-, 4- and 6-positions (a similar orientation to that
found during the bromination of phenol. see Topic 25). E3ch of these is able to
undergo a condensation reaction with an(){her phenol molecule (for simplicity.
only one group is shown in the figure as reacting) co give intermediate n. The
newly mrnched phenol ring can then react with more methanal. giving intermediace
C, which can condense with another phenol. giving intermediate D. Reaction of
D with two more methanal molecules produces intermediate E. O:ompound E
contains five -CH,OH groups, two of which are needed to continue the linear
chain, leaving three available for condensation with three new phenol molecules
(seeFigure28.14).
Flgure 28.1 3Thebuild ingupofthe

linearchaiminbokelite
{F (9}- ?I()~-- .
- -:-p~- o, Q--oy o,
/",o ;.,.,.,a;,.,,
HO ~OH
OH OH
intumediat<' D HO 0
479
ORGANIC CHEMISTRY
Rgure28.14 Thefonnatiooolcross-linKs
inbake lite
Each of these new phenolic benzene rings rnn now scan two chains. independently
of the original one . You can see how complicated maners can become! Although the
strucrure of bakelite can become veiy involved. it is rebtively ea~,' to work ou t the
ratio of phenol to methanal that is needed to make it.
Worked example 1
ii Cakulatethephenol:methanalratioinbakelite.
b Statetheassumptioosyoomadeinyourcakulatioo
Answer
One way would be to write out the formuki of a section of the bakelite molecule, and
count the number of ptienol rings and methanal --C Hi- groups. AA e,nier Wi1'f is to
recognise that each pheool is joir.ed to three -CHi- groups derived from methanal,
and e<Kh - CHi- group is joined to two pheoolic rir.gs. So the pheool:methanal ratio
is2:3.
b The main assumption is that e;ich phenol reacts with the maximum number of methaflill
mo~ules that it cari (three}. It is also assumed that the sample of bakeHte is so large that
the 'bouridaryeffects', ofpheoolk.ririgsattheedgesolthepolymerootOOrigjoiriedto
other - CHi- groups, are very small.
Crnss-Hnking of polymers does nO{ have to result in such an inflexible solkl as bakelite,
buc cross-linking is ofren introduced to provkle added si:rength to a flexible polymer.
For =ample. if a small amount of a tri- or tetra-hydroxy akohol (see Figure 2&15) is
added to the monomer mix for a polyester, a .sironger crnss-Hnked polymer can fonn
(seeFigure28.16,l.
Flgure28.15 Twopolyhy{lroxy.ilrnhol1
o,
HO~OH
propanl!--1,2,~triol 2,2bis(hydroxymethyl)propanl!--1,3..:liol
(glycerol) (per,ta~rythritol)
480
Fl gure28 .1 6 Cros1-linkingin
rnmlemotioopolymers HO /)'O OH
)c--Q-cf' HOA"o,
2Ho - - 0 - 0 H + 4
/ \,, + 1
'ta
PTFE
The opposite effect is nOl:iced with polytetrafluoroethene, P1FE (see Topic 14). Here ,
all of the hydrogen morns in the polymer ha,e been replaced by fluorine atoms.
~1uorineisthem05lelectronegativeelementinthe PericxlicTable. andSlrongly
anracrs the electrons in covalent bonds attached ro it. This means that the electrons
are held finnly and are nct easily polarised. This results in veiy weak van der Waals'
forces between PTFE molecules and e:ich O(her and. more imprn1antly, bet,veen PTFE
molecules and cxher molecules. It is the intennolecular fonces that cause molecules to
stick together. andsoPTFEisusedasa non-stick surfaceonc<X>kware. and also for
thebearingsattheendsofbridgesthmmightexpandandcontractwithchangesin
the environment's temperature.
'Ecopolymers'
Until recently, the raw materials for most polymers came from the products of the
refining of crude oil. which is a finite, non-rene"rable and diminishing resource .
Also, the disposal of polymeric materials after their useful life has caused problems
of pollutio n, since many are non-biodegradable. Both of these problems have been
panially overcome by an increase in the recycling of polymers: thermal cracking
of polyethene can conven it into its monomer, ethene, which can then be reused;
the polyethylene -terephthalate (PET) from plastic bottles can be convened into a
wool-like material for fleeces and other clothing.
An alternative solution is to use renewable plant material to make polymers that
are also biodegradable. The mos! commonly used is poly(2-hydroxypropanoic add)
(poly(lactic add), PL\).
0
II ? 1H' ?
HOCHc.. . . .OH ~ _.oCHc, .,....c~.,....o,CHc. __
0
I I II I
CH, CH 1 0 CHi
hydroxypropaooi<1Kid
Hydroxypropanoic acid is a naturally occurring compound, which is made industrially

bythefem1entationofcornscarchorsugar.P!Aisea.silyhydrolysed,rither
chemically or by escerase enzymes, to r<,-form hydroxypropanoic acid, which is
readily metabolised by all living matter into C01 and water.
481
ORGANIC CHEMISTRY
The uses of PL\ include replacing conventional plastics in the manufacrure of

boules. disposable cups and textiles, buc it is also used in applications where its slow
The repeat unit of another biodegradable biodegradability is an advanrngc. For example, in medicine it has found uses as a
polymer is as fo llows componem of self-dissolving stitches and for implants in the form of screws and pins
to keep bones in place whilst they heal (see Figure 28.17)
Drnwthestructu/l'sof theproducts ofthe

hydro!ysisofthismooorner.
Flgure28.17 A~odegradableso=
made of PI.A
Conducting polymers
R R R R Graphite is a conductor of electricity bemuse within each of its layers of carbon
morns there are delocalised electrons covering eveiy atom within the layer. Thus.
, ,J~,. . .J~I/J~r--L~I/ when a po1enti3l difference is applied 31 opposite ends of the layer, the delomlised
~
Some long-dU1i11 polymer molecules act as molecular wires'. They conmin
conjugatC'd doubk> bonds , which means that the lt bonds on adj3cent alkene units
overlap. and the lt electrons become delocalised throughout the whole length of the
polymerchain(seeFigure28.18).
Flgure28.18The1tructureofa Just as with the three-dimensional delocalised electrons in metals. or the two-
'ffirnerul.irwire dimensional dekx:alised electrons in the sheets of graphite or graphene, these one-
dimensionaldekx:alisedelectronscanconduct3curremwhen3po{entfaldifference
is applied to the ends of the polymer. An eventual aim is to construct micro-miniature
circuits th31 mn lead electrical signals to "molecular microchips' in the hean of computing
de\-icesth3twillbethousandsoftimessmallerthantoday'ssilicon-basedunits
Three main classes o f conducting polymers 3re the polyace1ylene.s. the
polyphenylene vinylenes and the polythiophenes(see Figure 28.19).
Flgure28.19Threetypesofconducting
polymer
polyuetylene(polyethyne) asubstitutedpolythiophene (PT)
adisubstitutedpolyphM)'le ne vinyle ne(PFV)
482
These polymers are nOI used as ordinary conductors - their conductivity is less than
that of copper, for example - but as semiconductors. for use in organic polymer
light-emitting diodes (OP-LEDs) and phOlovolrnic (sobr) panels , for convening
electricalenergyintolight.orlightintoelectricalenergy. FortheiruseinOP-LEDs,
by altering the nature of the side groups R and OR the molecules can be made to
electroluminesce(thacis,emitHghtwhenanelectrodepcXenti31isapplied)inany
pan of the spectrum. from red, through yellow and green. 10 blue. An everyday use
ofOP-LEDsisfortrnfficlights(seeFigure28.20)
Flgure2B .20 Red,yellow.111dgll.'e110P-Lrn

usedi11tlaffi{light1
Polymer glues
MO!SlgluesachievetheirstickinessthroughthevanderWaals' fon,esthatexisl
between their molecules and the molecules of the two sUJfaces they stick together.
To be 3n effective and strong glue. the other propeny they need is for their own
molecules lO stick 10 each other strongly. If they are polymeric. consisting of long
molecules. 1his bst quality is fairly ,vell assured . There are two important types of
polymer glue, one is an addition polymer and the cxher is a condensation polymer. In
each case, the setting of the glue is a resuh of its continued polymerisation "in situ ". in
otherwordswhilstitisinconmctwiththesUJfacesbeingstuck.
Addition polymer adhesives

A common addition p;:,lymer 3dhesive has already been mentioned in Table 28. l.
poly(cyano:,ctyla!e). or "superglue'. Because of its two electron-withdra\\-ing groups at
one end d the ethene C= C, it has the unusual property of its polymerisation being
rntalysed by nudeophiles. such as water (this is why it is .so dangerous if it is in contact
with the skin or the eyes). The glue is applied as the lmv-M, low-viscosity monomer,
which spreads well into uneven su,faces. Once the c,vo surfaces are brought together.
the polymerisation of the monomer is rntalysed either by nudeophilic groups on the
sUJfaces (for example, -OH groups) or by moisture in the air(see Figure 28.21).
Flgure28 .2 1 Thepolymeris.Jbooofmethyl
cy~ooac:rylatetoform'l\lpergllie
483
ORGANIC CHEMISTRY
Condensation polymer adhesives

A common group of condensation polymer adhesives are the epoxy re.sins. These
are supplied as separate tubes of the two components, which are thoroughly mixed
immediately prior to use. One component consisls of a mixture of a medium-length
polymer containing erx,xy groups (compound P in Figure 28.22), and the Olber
component (called the "hardener') contains a diamine which opens up the epoxy
rings by nudeophiHc atrnck. and allows cross-linking co take place. The result is an
inen thennosetting adhesive of tremendous strength. Figure 28.22 shows a simplified
outlineofthisprocess.
Flgure28.22 An outl ine

of the aoss~inking of epoxy
rnmpoumlsbyaminestofmrn
a hard epoxy-resin adhesive
compoundP(n:1S--25)
28.4 Proteins
There 3re three main classes o f polymers thm occur in nmure: the proleins, the
nucleic acids, andthepolysacrharidessuchas.starchandcellulose. In this section and
the following section we shall look a t some of the propenies of the fir.st two of these.
Flgure 2B. 23 Somelmportantpmtein-
rnnto iningfood:I
Pro{eins make up alx>ut 16% of the human lxxly. They noc only occur as components
of blood , skin, bone. nails. hair. nerves, muscles and tendons. but also are responsible
for the smocxh workings of the lxxly in their roles as enzymes. r=pi:ors and homlOl"\es
Pro1ein-containingfoo:ls,suchasmeat.beans.ch=se,eggsandrnilk,aretherefore
importantconstiruentsinourdie1(seefigure28.2J). Theirimpottancetousisemphasised
by their name, which is derived from the Gr=k proteios. meaning foremo st or primary.
The structure of proteins

The backbone of a pro{ein is one or more chains made up of polymers of amino
adds . Some pro{eins also have non-amino-add groups called prosthe tic groups (for
example. the haem group in haemoglobin). The shape and physical and biochemical
propeniesofa proieinarethedirect resultofthenurnber.typeandsequenceofthe
amino acids that make it up. This amino acid sequence is determined by the gen e.
the sequence of organic bases in the length of DNA th,u codes for the protein . Amino
acids do not trnn together to form proteins randomly. but join in a well-ordered and
predetermined sequence.
The amino adds are trnned by amide lxmds between the amino group of one
acidandthecaiboxylgroupofancxher(see Fig ure23.24). Proteinsaretherefore
corn!X>S"d of polyamides , and are condensation polymers. As we saw in section 27.6,
when an amide lxmd is formed between two amino acids. it is called a pcptid<-
bond. and simple proteins (those that contain jusi one chain , and no proS!hetic
groups) are also known as polypeptides .
Flgure 28.24 StructureofapalypeptkJ.e
- 2Hi0
,
N"c~c.. .I
. ___ Ic 101 ~ c~ ci("c........___
! ! ~
peptide g roups
!
485
ORGANIC CHEMISTRY
The formulae of pep(ides are often described by the following shonhand . The
customaiy th..,..,-lener abbreviations for all the amino adds in the chain are written
down. staning with the N te rminal (the end of the chain thac has a free - NH,
group) on the left. and finishing with the C te rmina l (the end that has a fr= -C0 2H
group) ontheright.
Worked example
Convert the following structuralformulaintothecOfrectshorthand:
NH1--CH1--C O- NH-CH(CH 3)-C01H
Answer
Thi:s51:ructurecont aimooepeptidebondinthemiddle,IDitisa dipeptide,conta inir,gtwo
amino add residues. Theresiduetotheleftofthepeptidebondisglycine(Gly)andthatto
therighti:salanine(Akci){set!Figure27.18).Theshorthandformulaisthefefore
GJy-Ala
Notethatthisi1adifferentcompoundfromAla--Gly,becauseoftheleft-to-rightdirection
ofthepeptidebond.ThestructuralformulaofAla-Glyis
NH1-CH(CH)-CO-NH - CH1-C01H
1 Draw the strnctural formulae of the follO\Mr,g two tripeptides (use F'9rne 27.18 to help
yoo)
a Val- Ser- Tyr
b Tyr- Ala-G~
2 Use the cU51:omary three-letter abbreviatiom to describe the following tetra peptide
CH 1C01H CH(CH 3)1
O I H )lo ~H OH
HiN 'cH_).___N.,....cyN,cH
1
N.,.... Y
I H O H O
CHpH
The amide (pepcide) bonds in proi:eins can be hydrolysed by the same reagents as
hydrolyse simple 3mides: hot aqueous add or hOl 3queous alkali. They can also be
hydrolysed by 3 variety of prOleolytic enzymes. Many of these (for example , trypsin
and pep.sin) are found in the digestive sys!em. where they help to break down the
proteins in our f<:x xl into smaller peptides and amino adds, which can then readily be
3b5orbedthroughtheintestinalw:ill.
Biochemistsrecognisevariouslevelsofpro!einstructure.
Primary structure
Theprim:irystructureofproi:einsisthesequenceofaminoadds. covalently joined by
peptide bonds. m:iking up the polypeptide chain. as described alx,ve. This sequence
is detennined by the aITangement of organic bases in the section of ONA that codes
fortheprOlein.
Secondary structure
The amino add chain that constitutes a polypeptide is quite flexible. with cwo-
thirds of the bonds within the chain being single bonds. 3round which free
rotation is allowed . The other third of the bonds in the chain are the C- N bonds
within peptide groups . Because of the overlap between the Jone pair of electrons
on the nitrogen atom (in a p orbital) and the It bond of the mrbonyl group next
toil.the peptide group is rigid and planar. It exists inthetr,msaITangement (see
Figure28.25).
Flgure28.25 OVerlapofpo!bitatsmake,;
thepeptklegrouppl,mar
\ -E-
freerotat~o~~
",
/f
',--E- ~.
~oo,o"fo"
6-+N t_/
H/freerotation\
This inflexibiHty of the peptide group allows parts of the polypeptide chain 10 cake
up an .- h e lica l arrangcnicnt (see Figure 28.26). This lends strength and rigidity to
some pro1ein structures . Strong hydrogen bonds rnn form betv,een the N- H of one
peptide group and the C = O of amxher one three/ four amino adds along the chain.
Flgure28.26The11helixillproteim
the polype ptide

--- the hy<lrogenbondbetw<!en
the C= OandN--Hgroups
The a-helix confers one-dimensional rigidity to the p;:>lypeptide chain. An(){her type
of secondaiy structure is the ji-pkated sheet. This is formed by the C = O group
of one chain hydrogen bonding to the N- H group in the same chain, or anOlher
chain, but separated by many amino add residues. The resulting sheet o f anti-parallel
hydrogen-bonded chains confers a degree of two-dimensional rigidity to the
p;:>lypeptide chain. The chains are described as anti-parallel because adjacent chains
run in opposite directions, as shown in Figure'11',.'Z7.
Flgure28.27Thei3-pleatedsheetinproteim
(Thetetr.ihed1.il,mangementofboodsarnund
the!,Jl'carboointhed!ainmeansthattheR
group11tickovtabover:11belowtheplanar
sheet.)
Tertiary structure
Even if a particular polypeptide chain contains regions of et-helices or ~-ple:ited
sheets, there will be many amino adds nOl involved in these regions. Other
interactions can occur between the side groups of these amino acids, which cause the
chaintotwistandfold.
\Ve can recognise four different interactions between side chains, which are
associatedwiththeirdifferentstrucrures.
487
ORGANIC CHEMISTRY
Van der Waals' anrnaions occur between nonpobr side chains, for example,
glycine,alanine,valineand phenyblanine.
Hydrogen bonding occurs between side chains that contain -OH (for example.
serine and tyrosine), - NH:,/- NH/ (for example. lysine) and -C0 2J-I/---C0 2- (for
example.aspanicacidandglutamicacid).
H
O= C/ ' O: -- H ' C=O
'rn-CH 'o--0-cfi
1
NH~ ; NH
e lonicanractionsoccurbetweensidechainsconrniningfunctionalgroupsthatexist
in their anionic form at pH7 (for example, aspanic acid and glutarnic acid) and
thosethatexistintheircationkform(forexample.lysineandarginine).
Disulfide bridges rnn form between the side chains of two cysteine residues.
/
oxidation
O= C
~
- rn ~CH- CH1 - s, C= O
NH, adoolf>.Itllri~ S- CH 1 - CH~ NH
/
The IC'rtiary s tructure confers some thret'-Olmcnslonal rigidity to the JX>lypeptide.
and is important in determining lxxh the overall sh:ipe and the function of the
protein. l'or example. trumy enzymes :ire globubr (fairly spherical) proteins ih,u are
soluble in water. In these. the non-polar side chains :ire of!en poiming !owards the
cencral hydrophobic part of the molecule. whereas the hydrogen -1:xmding and ionic
groups are on the outside, where they can be solvmed by wa!er molecules.
The .strongest of the tettiaiy interactions is the disulfide bridge. Once these are formed.
byanoxidationrea<1ion.thev:iriouspansofthech:iinaredrnwntogether.andthisaUows
the other imern<1ions 10 pby their pan in creating the overall three-dimension:,] strucrure.
28.5 DNA
The genes of all org:inisms are composed of chains of deoxyrilxmucleic acid, DNA. It
storestheinfonnmion neededtom:ikespecificproteinsinthecell.
Like proteins. DNA consists of:, prim:iry strucmre. which comprises the covalent
bonds joining the monon,ers together. and a secondary strucmre. which is formed by
hydrogenbondingbetweenthech:iins.
The monomer units of DNA are called nucleoside phosphates. These consist o f
the sugar molecule deoxyribose. which has a cyclic oig:inic base lxmded !O carbon
31om I. and :, phosphate group bonded to c:itbon 31om 5. All DNA molecules conrnin
just four different bases . In:, p:inicular DNA molecule. these :ire arranged in a
specificorderalongthechains.
488
Figure 28.28 shows the strucrures of the four bases and Figure 28.29 shows how
adenine forms the monomer unit adenosine phosphate.
Flgure28.28 ThefourbasesofONA
(',~~ ,,,~'"
~Ao
guanine 1 cytosine thymine 1
1
th...., molecul e< are based the<e mol~ulesare ba"'d
on the purine ske leton on the pyrimidine skeleton
(ineachcase the sugari,attachedtothenitrogenofthebottomNHgroup)
Figure 28.29 Tot> mooome1 unit ..denosine

phmphate
Many thousands of monomer units join up in a specific sequence of bases to form a

Hnearcondensationp;:>lymer.
':~,,,,,
Flgure28.30 Partola'iingte1trandofDNA
showingthefourbasesA,C,GandT
. 1:' I )
I
O = P- 0
b._
Ho H H CN NH1
O=LO
' c-,-o--J
0-- H~ \
r H
N~
<(
N
I NH
N.;_NH1
G
=e- o , d
6- "
l "J
O= P- 0
l.,/NH
H
NAa
6-~
I
0
3
"
489
ORGANIC CHEMISTRY
Just as with proleins. DNA has a hydrogen-bonded secondary structure. A DNA

moleculeconsistsofadoublehelixoftwosugar-phospha!estrnndscoiledaround
eachcxher.withthepurineandpyrirnidinebases(lxxhofwhichareplanar
molecules) arranged in hydrogen-bonded pairs, one from each chain. stacked abo,..,
The pairing of the bases is unique: adenine (A) always pairs with thymine (D. and
guanine(G)alwayspairswithcytosine(C).
As can be seen from their molecular structures. a purine molecule. with its two
rings of atoms, is larger than a single-ring pyrimidine molecule. To allow the distance
betweenthesugar-phosphatechainstobeconsrnnt.thebasepairsmustconsist
ofonepurineandonepyrimidine (seeFigure28.28): thereisnOl:enoughspace
between the chains to accommodate two purines, and two pyrimidines would nOI: be
close enough to hydrogen-lxmd with each oiher.
But why should adenine pair with thymine and nOI: with cytosine. or guanine pair
with cytosine and nOI: with thymine? The answer lies in the number of hydrogen
bonds that can form between the bases , and the directional sense of those hydrogen
bonds. figure 28 .31 shows the hydrogen bonding that occurs.
Flgure28.11ToehydrO(Jffibandedbase
p.irsT-Aa!ldC---G(Rrepri.>Seotsthe
deoxyriboseringtowhk:htheb.-iseispned.)
"I
\-/ __,_\_/";
( } - H---< )-Nm'\
N--<o \,=N ~

The overall structure is shown in Figure 28.32.
28.6 Distinguishing between addition

and condensation polymers
We c:in recognise which type of JX>lymer will be formed from given monomers by
looking at their structures.
If each of the monomers contains a C= C g roup, they are likely to produce an

addition JX}lymer (even if they also contain add. ester or amide groups).
If the monomers contain two different functional groups (caiboxylic acid or acyl
chloride , amine or alcohol) at the end of a chain of carbon atoms, they are likely to
produce a condensation polymer.
We c:in recognise what type of JX>Jrmerisation has produced a JX>lymer by looking at

a section of the backbone chain.
If the chain contains only carbon atoms, the polymer is an addition polymer (even
ifanysidechainscontainesteroramidegroups).
Flgure28.12 A'il'Cliooofthedouble- If the chain contains hetero aton1s (that is atoms that are no1 carbon usually
1trandedONAmolecule oxygen or nitrogen), the polymer is a condensation JX>lymer.
Worked example 1
Predict the type of polymeriSillion that each of the following pairs of molecules will
undergo,anddrawthestructureoftherepeatunit.
a CH 1= CH-CONH1 and CH10CH = CH 1
b NH 1CH1CH1NH1 and CICOCH 1CH(CH1)COCI
490
Answe r
a These two mooomers will form an addition polyme r, because each mono me< cootains a
C= Cgroup.The repeatunitiseither
t
0
or
/
f ' / f'1'
CH ' " ' CH
CH1 CHz
Whkh one is formed deper.ds on the or~tation of the mooomers
, I
b These two monomers will form a condensation polymer, because each monomef contains
twoltmctioflill groups.Therepe,atunitis
I NH......_ /CHz_ /C"- /CH...._

CH 1 NH CH 1
r! n
[demifying the monomers th31 h3ve produced a condensation polymer is relatively

straightforward: the chain is broken al the ester or amide bonds. an H 3torn is added
to the - O or - NH grou ps so fom,ed, 3nd an -OH is added to the -CO groups.
Worked example 2
Draw the structures of the monomers used to make the following section of a co-polymer
Answe r
Splittingtheco-pciymersectionatthee1tergroupsproduce1threehydroxyacidmol1.'CUle1,
of whkh two are identical, 50 the monomers are 2-hydroxypmpanok acid and 3-hydroxy-2-
methy!prop,moic add
)~
H + OH
or
H + OH 1 ot o ~
H+ OH
~~~~~~~~,
H+OH
,) yo" , o~ o, ,o f 0
,
2-hydroxypropanolcadd 3-hy<lroxy-2-methylp>panolcacld 2-hy<lroxypropanolcacld
Identifying the monomers that have produced an addition polymer can be a little
more difficult . If !here are no C=C bonds in the chain. the carbon chain is split into
two-carbon sections. Each of these will have been formed from 3 subsiitu!ed ethene
as monomer. If. however, the rncbon chain contains C=C bonds. these are likely to
have come from burndiene-like monomers, so the chain is split into a four-cacbon
unit at this point, with the C=C bond in the middle of the four--caibon unit.
491
ORGANIC CHEMISTRY
Worked example 3
Draw the structures of the monomers used to make the following section ol a co-polymer
1H1
_,c,
,,-CH.z_ /CH.z_
IHI
d H
CH2
d
L
/CH.z_ /CH.z_ /
IH
g
Answer
Thepolymercontainsadooblebond,mitissplitintoalou1-carbonunitatthispoint.All
single-bondedlengthsaresplitintotwo-carbonunits
rl
; .; CH.z_ ;../Hz ;P'C'-.. % CH.z_ %CH{__ ;.;
L
IHI
Cl " l
CH1 IH
Cl g
- - - - - - -~
"lCl ~
2-methylbut.i-1,J-Olene
"l Cl c\
pheoylethene
Thu:sthemonomersarechloroetheoe,pheti~ethenear.d2-methylbuta-1,3-diene
Identify the monomers used to make the following sections of polymer molKules
' 0
___ o~o,,,.lo...............o, __
28.7 The disposal of polymers

We saw in section 14.4 how p;:>lyalkenes can be disposed of. by incineration.
recycling. depolymerisation or bacterfal fermentation. Some polymers can also be
broken down by ultraviolet rays or .strong sunlight. Because of the radical-stabilising
effect of alkyl groups , the lxmd between a hydrogen atom and a ceniary carbon atom
is weaker th3n the u s ual C-H bond (bond eneigy 420kJ mol- ').
492
R R R
"c - H ~ 'c_/ +H 6.H = 404kJmo[- l
Rit k
Oxygen molecules (which are di-radicals) can readily react with ceniary C-H groups.
R R 0- H
'c - H + o - cf ----t "c - cf 6.H =-90kJmo[- l
R/i R/l
The hydroperoxides formed by this reaction can undergo further lxmd breaking and
molecubr rearrnngements , resulting in smaller molecules that can be more easily
metabolised bybacteriaintheenvironment.
The main way that condensation JX}lymers are broken down in the environment is
bythehydrolysisoftheireSleroramidelxmds.
-R---Co--OR'- + H 1o ~ -R---CO!H + HO-R'-

-R---CO-NHR'- + H 10 ~ - R -C0 2H + H 1N-R'-
Esteraseand pep(idaseenzymesinsoilbacteriarnncarryoutthesetrnnsformations.
Many different add ition polymers can be made by polymefising etheoe molecules in which one or more h'jl}rogen atoms have
beenre~acedbyothefatomsorgroups
Co-polymers are polymers made from m0<e than ooe type of monome<.
Condensation po lymers ail'usuallyeitherpolyestersorpolyamides
CondensationpolyrnerscanbedividedintotwocategOfies - t ype l and type ll - dependingootherelativeOOentatkmoladjaceot
lunctionalgroupswithinthechain
Thepropertiesanduse1ofvariou1polymer1dependootheirchemical1tructures,andthebondingbetwernthechains
Proteins and nudek acids aie two important natural examples of coodensatioo polymers
Addition and coodeosatioo polymers can be distinguished, and the strlictures of their monomers determiried, by studying the
make-upofthebac:kbonechain
Ky reactions youshou ldknow
Addition polymerisation
nCHi = CH - R+ nCHi = CH-R' ----> [-CHi-C HR--C Hi-CHR'- ]n
(The proportioos of CHi = CHR and CHi = CHR' can be varied.)
Condensationpolyrnerisationtogivepolyesters
nHO- -OH + nHOiC - -CO:iH----) +o- -oco- e -co+,;
Condensationpolymerisationtogivepolyamides
493
ORGANIC CHEMISTRY

Pleaseseethedata5ectionoftheCDforanyA,valuesyou 2 1nrecentyearstherehasbeenconsiderableinterestina
may need. range of polymers known as 'hydrogels'. The5e polymers
arehydrophilicandcanabsorblargequantitiesofwater.
1 Proteins exist in an enormous variety of sizes and structures
a The diagram sho..vs part of the structure of a hydrogel.
inlivingorganisms.Theyhaveawiderangeoffunctions
I
whicharedependentupontheirstructures.Thestructure
and properties of an individual proteinarearesultofthe
a, ,,,.,,a
primarystructure-thesequenceofaminoacid5thatform
the protein. - CH, - 1H- CH 1 -
\
CH -
a Proteinsaredescribedascondensationpolymers.
i WriteaDillanc:edequationforthecondensation O;C-....._I
reildion bet\'veen two glycine molerules, H1NCH 1C01H.
ii Draw the ~eletal formula for the organic product. (2)
b X-ray analysis has shown that in many proteins there
IH'
HO - CH 2- , - CH 2- 0H
areregionswitharegulararrangementwithinthe
polypeptidechain.ThisisG111edthe5e<:ondarystructure IHz
andexistsint1vomainforms
i Statethet\'11oformsof5ee0ndarystructurefoundin a,r.,..o
proteins
- CH 1 - CH- CH 2- iH -
ii Draw a diagram to illustrate o ne form of secondary
141
c There are around 20 different common amino acids O/ ""'a
found in humans most of which have the x1me general I
The hydrogel is fcmied frcm chains of one polymer which
arecros">-linkedusinganothermolecule.
i Draw the structure of the monomer used in the polymer
chains
ii Statethetypeofpolymerisationusedtoformthese
The nature of the group R affects which bonds are formed chains.
asthesecondarystructureoftheproteinisfurtherfolded iii Drawthestructureofthemoleruleusedtocr05s~inkthe
togive thetertiatystructure. polymer chains
Copyandcompletethetableindicatingthetypeof te rtiary iv During the cros">-linking, a small molecUe is fomled as a
bonding that each p;iir of the amino acid residues is likely to byi)roduct.ldentifythismolecule. [5]
-~
produce. b Onceahydrogelhasabsorbedwater,itcanbedried
and re-used many times. Explain why this is possible,
typeoftm:lary
referringtothestructureabove. 121
--tjN(H(CH,cH,cH,cH,oo,)CO-- --tjNCH(CH,cH,co,H)CO-- c Noteveryavailablesidechaininthepolymeriscross-
linked,andtheamountofcr05s-linkingaffectsthe
propertiesofthehydrogel.
i The amount of cros">-linking has little effect on the ability
ofthegeltoabsorbwater.Suggest~thisisthec.ase.
--tjNCH(CH,C0 1H)CO-- iiSuggest onepropertyofthehydrogelthatwillchangeif
more cross-linking takes place. Explain how the increased
141 cross-linkingbringsaboutthischange. [3]
{Cambridge lntemational AS & A Level Chemistry 9701, {Cambridge International AS & A Level Chemistry 9701,
Paper41 Q6 November 2011] Paper42 QBJune 2013]
494
A Level
Organic chemistry
2 9 Techniques of analysis
lnthistopicwelookatvarious
methods used to separate mirtures Learning outcomes
of compounds and identify their Bytheeod ofthistopicyoushouldbeableto
components. We a/so explain the 22.1a) expjainandusethetermsR1va lueinth inlayerchromatographyaridretrotkm
principles and applications of timeinga H iquidchromatographyfromchromatograms
three major analytical techniques 22.1 b) interpret ga!;-hquid chromatograms in terms of the percentage composit ioo of a
usedtoinvestigatethestructureJ mixture
ofmolecu/es:mass spectromet,y, 22.2a) analyseaninfraredspectrumof asimplemoleculetoidentifyfunctionalgroups
infrared spectroscopy and nuclear 22.la) deduce the molecular mass of an organic mo~ule from the molecular ion pe;ik
magnetic resonance spectroscopy. in a mass spectrum
22.lb) dedoce the number of carbon atoms in a compound using the M-t 1 pe.1k
22.lcl deducethepresenceof bromineandchlorineatoms inarompoundmingthe
M-t2pe ak
22.ld) suggest t he ide ntity of molecules formed by simple lragrnentatioo in a given
mass spectrum
22.4a) analyse a carbon-13 NMR spectrum of a simple mo~ule to deduce the diffell'nl
environmentsofthecarbonatomspreseot,and t hepossiblestructuresfDfthe
molecule
22.4b) pred ict the number of peaks in a carbon-13 NMR spectrum !Of a given mo~ute
22.5a) ana!yseand interpretaprotonNMRspectrumofasimplemo!eculetodeduce
thediffwe nttypesofprotonpresentusingchemicalshiftvalues,thereknive
numbers of &Kh type of proton Pfesent from relative peak are;is, the number
of non-equivalent protonsadjacl.'flttoagivenprot onlmmthesplittingpattern,
usingthen -t 1 rule,andthepossiblestructureslDfthemo!ecule
22.5b) p<ed ictthechemicalshift1 and splittingpattwn1oftheproton1 inagiven
mo lecule
22.Scl describe the use of tetramethylsilane, TMS, as t he 11:andard !Of chemical shift
medS\Jfl'!Tlenls
22.Sd) state the r.eed tor deuterated so~ents, e.g . CDC11, when obtaining an NMR
-rum
22.Se) describetheidl'ntilicatkmof().......HandN--Hprotonsbyprotonexchange
using[}.,O
4' 29.1 Chromatography

The name 'ehromatogrn phy'. coming from two Greek words meaning 'colour image.
was invented by the Russbn scientist Mikhail Tsvet. He den,Joped the technique
aroundthestartofthetwentiethcenturytoseparntethecaro{enes.chlorophyll
and xanthophylls thac are the coloured pigments in plants. Today. however. most
chromatography is carried out to separate colourless compounds, which can then be
identified bya variety of methods.
We shall look at three types of chromatography:
paper chromatography(PC)
thin layerchromatogrnphy(I'LC)
gas chromatography (GC). olherwise known as gas-liquid chromatography (GLC).
495
ORGANIC CHEMISTRY
Each type of chromatography relies Ofl the rome overall principle for separating the
com!X'fX'fllS of a mixture: the compounds are di.stribrned between a mobile (or modnli)
pbase(a liquid or a gas) and aslationa,yphase. lhe stationary phase may be a solid
whichadsotbsthernixtu..,-solutes.orathinfilmofliquidonthesu,faceofaninensolid.
Paper chromatography (PC)

Although it may appear dry to the t01Jch. chromatography paper (which is like
smOO{h filter paper but with an accurate and constant thickness) contains water
molecules hydrogen-1:xmded to the OH gl'OIJps on its cellulose molecules. This layer
of water molecules is the stationary phase. The moving phase is chosen to be less
pobr than water. It is usually an organic solvent. or a mixmre of solvents: ethanol or
anethanol- watermixru..,-isoftenused.
Flgure29 .1 Separatioobypartition
_ J . t .c - - - - stationaryliquidphue
~ ,olutemolernlesdissolved
inthe mobileliquidphase
A sp<X of the solution of the mixture to be analysed is placed about I cm from the
edge of a ..,-ctangular sheet of chrommography paper (often about 20cm x 20cm),
along with other sp<Xs of reference compounds at the same distance from the
edge.Afterthemixturesolvemhasevaporated.theedgeofthesheetisplacedin
a chromatography "tank' and immersed in the moving phase solvent. making sure
thesp<Xsarealx>Vethesmfaceofthesolvent. Thesolventisdrawnupthesheet
bycapillaryaction. Asitpassesthepointwherethespotshavebeenapplied. the
compounds in the mixture are partitioned between the stmionary water layer and
the moving solvent, depending on their polarity (Figure 29. 1). Although the process
iscontinuallychangingandneverreachesequilibriumbecausefreshsolventis
constantly sweeping up the paper. how quickly the spcx.s move up the paper is
determinedbythevaluesoftheirpartitioncoeffidentsbetweenthesolventandwater.
The more polar a compound is. the smaller is its partition coefficient. This means it
will spend more time dissolved in the water layer on the cellulose than in the moving
solvent. and it will progress more slowly up the paper.
Whenthesoh,enthasalmostreachedtheendofthesheetofpaper.thepaperis
takenoutofthetankandallowedtodry. Asthesolventevaporates.thesoluteswill
stayattheplacestheyhadreachedonthepaper. lftheyarenoialreadycoloured.
they can be made ,isible by spraying the paper with a specific developing agent.
which reacts with the compounds in the s p<Xs to form a coloured product. Specific
agents have been developed for particular classes of compound: ninhydrin for amino
==er= . , ,.
Flgure29.2 A paper chromatogram of
anaminoacidmOO:urewithfive'refereocp,;'
spottedalongside,beforearldafter
developmentwithninhydrin
496
29 Techniques of analysis I
3cids(Figure29.2);Tollens ' orFehling'sreagentsforreducingsugars.Agenernl
visualising agent for most organic comp;xmds is icxline: when the paper is pbced in
a tank conrnining iodine vapour, the kxline is ab=rbed preferentially by the organic
compounds in the spots, turning them brown.
lhe usual way of identifying the compounds that make up the various spO!s
on a chromatography sheet is to me-asu"' their retardation facto!' Xfvalues
D
(Figun, 29.3). These are compared with the Rrvalues of known 'reference' compounds,
spots of which ""'re appl ied to the sheet al the same time as the mixture.
Flgure29.3 Theretord.ibool..ctor,R1
rt,rt,o~-H,om
'" rnarttocentr<ofspot
(a)
R .. ~,,22mm,,o.ss
t b 38 mm
The retardation factor, Rr, is defined by the equation :

Ri = a distance moved by solute
b disrnncemovedbysolvent
Each compound has a chamcterislk R1 value for a given solvent. but occasionally
different compounds can have veiy similar f4 values in a particular solvent, and so it
is not easy to separate them. If a new solvent - one with a different polarity - is used
the comp;:,unds are likely to have different f4 values to each Ol:her. so they can now
be separated.
This is applied in two--dlm~nskmal c hro matography . This technique uses two
movingphasesolventsofdifferentpolarities. lnthistechniqueasp;:xofthemixiure
of comp;:,unds is placed at a corner of a square sheet of chromatography paper. The
sheet is placed in atankcontainingthefirstsohent,and is lefcuntilthesolventfront
reaches the far edge of the sheet. The sheet is removed from the tank. and allowed to
diythoroughly. It is then turned through90" and placed in a different tank containing
thesecondsolvent,sothatthespotsthathavebeenpartiallyseparatedbythefirst
solvent He along the bottom of the sheet, just above the level of the second solvent
inthetank.Whenthesecondsolvent fronthasreachedtheendofthesheet.itis
removed. dried and sprayed with the developing agent (Figure 29.4). The Rr values
in each solvent can be measured, and compared with those of reference compounds.
This type of chromatography has been used to identify the amino adds obrnined from
the hydrolysis of proteins.
Flgure29.4 l\\'o-Oimensicmalchromatography
=~~,; ; ,o~:,,,., D!I [

I .J

applied
__ here -- ~
'
- through90" -+ ----- -+-----_!_____
::i::~tn,ng,nf,m ~::::':,~~~fin :!::;~tning in se<ond
{two pa in of overlapping (a ll,potsnOYVseparated
spots) from each other)
497
ORGANIC CHEMISTRY
Thin layer chromatography (TLC)

ThetechniqueofthinlayerchromaK>graphyissirnilartothatofpaperchromatography.
bucthetheorybehinditisrathndiffelftlt. n.c..,Jiesonthefactthattheanra<1iveforres
that cause different compounds to be adsrnbed orno a solid surface differ from one
compoundtoanother(Figure'.29.5).ThesolidusedisusuaUyJX>wde=:lsUicacralurnina.
withthesmallsizeofthepartide:sprovidingalargesurfuceareapergram.anditis
coatedontoaglass.plasticorthinalurniniumplate.
Flgure29.5Separatf0nby ad'iorption
= =~- -:~'~:::~:~~: surtau,of the

stationary phase
. - - - - solutemolerules di,solved
inthe mobile liquidphase
The method used is almos! identical to thm of paper chromatography. Spots of the
mixturetobeanalysed.alongwithany..,-fencncecompounds. are applied close co
the lower edge of the 11.C pbte and aUrn,,ed to diy. The place is then placed in a tank
coruainingthesolvent.rnakingsurethatthesolventlevelisbelowtheSJXl(.
As the solvent ascends the plate by capillary action, and passes over the
compounds which have been adsorbed on!O the solid particles, the compounds
will partially dissolve in the solvent . How readily this occurs depends on bol:h how
soluble a particular compound is in the solvent, and how strong the anraction is
between the compound and the solid s up!X'fl . This is how separation is achieved .
Oncethesolventfrontisnearthetopoftheplate.theplateisremoved.allowed
to dry, and the spots can then be made visible. The ways in which spots of
colourless compounds on a 11.C plate are made visible can be similar to those
used for paper chromatography. but an additional technique is often used for
compounds conmining aromatic ring,;, or other systems that absorb ultraviolet (UV)
radiation . The solid suppon is pre-impregnated with an insoluble compound that is
fluorescent : it absorl:,s UV light and re-emits it as visible light. When placed under
a lamp which shines only UV light. the plate emits a bright white light unless a
panicular spot contains a comp;:>und that absorbs UV light. These spo(s wiJJ show up
11.C has several advantages over paper chromatography: the plates are quicker
to run; better separation of the components of a mixture can be achieved; and
its results are usually more reproducible. This is be-cause the plates can be made
very precisely, with constant very small particle size and moisture content . It is the
technique of choice for synthetic chemists wanting to observe the progress of their
Gas chromatography (GC)

In gas chromatography (GC) the mobile phase is an inert gas such as helium or
nitrogen . This is passed throug h a column made of glass or meml. which is between
l m and 3m in length. The column is packed with fine solid particles (brick dust is
often used), caited with oil that has a high boiling point (Figure 29 .6).
498
Flgure29.6 Diagramofga1
chmmatography~aratu~
The components of mixtures tha! are separated by gas chrommography must have a
reasonable vapour pres.sur<, al the temperature of the oven. which can be up to about
250C. The mor<, volatile components spend more time in the VaJX>Ur phase. and so
travel through the column faster: they have shoner ~te ntio n tillK'S . Less volatile
compounds spend more of their time dissolved in the oil in the column. and so take
longer !O be carried through the column by the flowing gas: their retention times are
longer.
Themixturetobeanalysedisfirstinjectedthroughaself-se-alingdisc(a rubber
septum) into a small chamber. It is heated to maybe 50C above the temperature of
the oven. where it is vaporised. The mixture then passe.s through the column. and
separation occurs. The gas emerging from the column passes through a detector. which
records the presence and amount of each comp;xtent on a chan recorder or computer.
Use of gas chromatography in analysis

After a mixture has been separated by gas chromatography its components must
beidentified. lfasampleisbeinganalysedforthepresenceofknownorsuspected
compounds. such as illegal recreational or performance-enhancing drugs. or
the presence of known contaminants in foodstuffs. reference samples of these
compounds wiJJ be used. If all variables are kept constant throughout the sampling of
the mixture and the running of the reference compounds through the same machine.
a simple comparison of retention times wiJJ allow an identification to be made.
Thevariablesthatmustbekeptthesameare:
the flow rate of the mobile solvent or the carrier gas

e thecemperarureoftheoven
thelengthanddiameterofthecolumn
thechemicalmake-upofthesolvem
the polarity of the stationary phase
This technique can routinely be coupled to an in-line mass spectrometer. The mass
spectrum of each component in a sample can then be found. which enables further
verification of the identity of the component. If. on the Olher hand. the sample is an
unknown compound, the mass spectrum can allow its identification. Other physical
methods of analysis that can be coupled to gas chromatography machines are infrared
Speclro5COpyandultraviolet-visiblespectro5COpy.
Examplesoftheuseofthistechniqueare:
testingathletesforresiduesofperformance-enhancingdrugsintheirbkxxlorurine
detection of explosive residues on skin or dOlhing
comparing caffeine contents of various natural and decaffeinated coff=s
detection of pesticide residues in fresh and processed foodstuffs
499
ORGANIC CHEMISTRY
29.2 Mass spectrometry

In Topic 2 it was explained how a mass spectrometer can be used to determine the
iSOlopic masses of individual atoms.
l>fass spectrometry is used in four main ways to determine the structures of organic
compounds:
I finding the molecular formula d a comJX>und by measuring the ma.ss of its
nx,leculariontoahighdegreeofaccuracy
2 findingthenurnberofcarlxmatomsina moleculebyrneasuringtheabundance
ratio of its molecular ion (M) peak and the M+I peak
3 finding whether a compound conrnins chlorine or bromine atoms, and if so, how
many of each. by measuring the abundance ratios of the M+ 2. M-t4 and M+6 peaks.
4 ,vorking out the structure of a molecule by looking at the fragments produced
when an ion decomposes inside a mass spectrometer.
Analysing the molecular ion

lf we vaporise an organic molecule and subject it to the ionising conditions inside
a mass spectrometer. the mass/charge ratio (m/e) for the molecular ion can be
measured. and hence the relative molecular mass can be found.
For example, one of the non -bonding electrons on the oxygen atom of propanone
can be removed by electron bombardment, to give an ionised molecule :
The m/e ratio for the resulting molecular ion is (3 x 12 + 6x l + 16) : I. which is SS.
Using ,-cry h igh N'!!Olutlon m ass spec1rom ctry. we can measure m/e ratios to
an accuracyoffivesignificamfigures(l pan in 100000). By this means, itisnctonly
possible to measure the M, value of a compound (its relative molecular mass). but
also to determine its molecular formula . \Ve can do this because the accurate atomic
masses of individual atoms are nct exact whole numbers.
Worked example
The three compounds in Table 29.1 all have an approximate M, of 70
Table29.1 Th ree{ompoundswithM, of
app roximatl'ly70
pentene CH,CH1CH,CH-CH1
2-aminopropanenitrile CH 1CH(NH,}CN
CH,=<:HCOCH, C,HoO
Use the folkiwing acrurate relative atomic masses to uku!ate their aaurate M,values, i!fld
decide haw sensitive the mass spec:tmmete< needs to be in oroef to distinguish bet1\wn them :
H ~ 1.0078
Answer
AcompoundhasanaccurateM,of TheaccurateM,valuesareaslolk>ws:
60.068. Use the accurate relative atomic C1H10 = Sx 12.000 + 10x 1.0078
massesgiveoabovetodecidewhether C1Ht;N, = 3x 12.000 + 6x 1.0078 + 2x 14.003
thecompoondisl,2-diaminoethane, C4H60 = 4 x 12.000 + 6x 1.0078 + 15.995
HiNCHiCHiNHi,orethaookilCid, The last two are quite close together. They differ by 11 parts in 70000, or about 0.16%
CH 3COiH. However. this is well within the capabilities of a high re'iOlution mass spectromete<.
500
The M+1 peak
There are two stable iSOl:opes of c arbon. "c and '-'c. Their rebtive abund~nces are
98.9}, for llc and 1.1% for '3<:. This means th31 01Jt of every JOO methane (CH 4)
m o lecules. CH 4, about 99 molecules will be "CH 4 and just one molecule wiJJ be
UcH 4. For ethane, c,H 6, the chances of a molecule containing one 'le morn will
have increased to about 2 in 100, because each C 31cm has a chance of l in JOO to
be 13 C, and there are two of them . By measurin g the ratio of the M to M+ l peaks. we
can thus ,vork out the number of carlxm atoms the molecule contains. The formula
relating the (M+l )/M ratio to the number of carlxm 31oms is:
n = ..!.22. x AM +t
I.I AM
A., .. = the abundance of the M+l peak, and

A." = the abundance of the m o lecular ion peak.
The abundances of the Mand M+ l peaks are sometimes quO!ed as percentages ,

and sometimes as the actual heights of the 1,vo peaks on a printou t of the mass
spectrum, in arbitraiy units. The units do nOI: matter, however, as it is only the ratio
that is important .
Worked example
The molecular ion pea k ol a compound has anm/eva lue of 136, wit h a relative abundance
A rnmpoor,d contains C, Ha nd O at oms. of 17%, and an M+ 1 peak at m/e 137 whe re the rejative abundance i1 1.5%. How many
ltsmassspectrumhasape;ik atm/e ca rbonatom1 areinthemolecule?
132witha rel ativeabundanceof 43.9
and a pwkatm/e 133witharelative Answer
abundanceo/2.9
Calrulate thenumberofcaibooatoms n = TJ x W- = 8.02
in&1ehmolecule,andsuggestitsmolecular
Arnoleculeofthecompound t hefelorecont ain1 8carbonatom1
forITTJ la.
The M+2 and M+4 peaks

Although fluorine and iodine each have only one stable isotope, c hlorine and
Table 29.2 The.Ovlldance1ofthei!i0tope1

olc:tilDfirn><mdbromine
. ..,.
bromine have two . Their natural percentage abundances are shown in Table 29.2.
Approx lmater.11110
"Cl
81 8r
Any compound containing one c hlorine atom, therefore, will have two molecular
ion" pe:,ks. one due to molecules containing J5cl and the O!:her due to mo lecules
containing J7cl. For =ample, the mass spectrum of chloromethane, CHJCl. will have
peaks at m/ e 50 (12 + 3 + 35 = 50) and at m/ e 52 (12 + 3 + 37 = 52) , corresponding
to the s pecies CH/5cJ and CH/ 7c1 . The relative abundances of the two peaks will
be in the ratio 3 : 1 which is the ratio o f the two d isotopes.
A similar situation occurs with bromine, although in this case the two molecular ion
peaks willbeofequalheights , sincetheisotopicabundanceratioisneartol : I.
Mass s pectra are slightly more con1plicated when the molecule contains more than
one halogen. The simplest situation is that for two bromine atoms. Take the molecule
J ,2--dibromoethane. C,H.iBr, . Each carbon can be attached to either a 79 Br or a 8'Br
atom,andthereisa(roughly) equalchanceofeither. Wethereforearriveatthe
p;:,ssibilitiesinTable29.J,eachofwhichisequallyHkely.
501
ORGANIC CHEMISTRY
"'BrCH 2CH,"'Br
"'BrCH1CH 1"'Br
"'sreH,CH,"'Br
There will thus be three molecular ion peaks, with relative abundances of I : 2 : I .
Worked example
Wori<outthem/evallil'Sandtherelativeabundancesolthemolecularionpe;iksfor
dkhloromethane,CHiCli
Answe r
Just as with dibrnmoethane above, there will be four possible formulae. Their m/e values
aregiYe11inthelollowingtable
cH,"ci"cl
cH,"cf''cl
CH/'CJ"CI
CH,"Cf' 7CI
Theabtmdanceratiooliona:ion b is3:1 (becauseofthe 31Cl: 17Clratio)

Theabundanceratioofionc:ioo d isalso3:1
The abtmdance ratio of ion a: ion dis 9: 1, because each of the two chlorine atoms
has3timestheprobabilityof beingl 5Clratherthanl7CI
Theoverallprobabilitiesaretherefu<e
iridMdualprob.lb il iUes
total mm of probabili ties
Analysing molecular fragments

If the ionising electron beam in a mass spectrometer has enough energy, the
m o lecular ions formed by the Jo.s.s of an electron can undergo bond fission. and
molecular frag ments are formed (see Figure 29.7). Some of these will carry the
JX)ISitive charge. and therefo,., appear as further peaks in the mass spectrum .
Flgure29.7 loniclr.igmentsformedfrom
0
HC>::-
1
1 : /CH 3
(a)(b)
Somo"''~
at(a) '=o ~ "''"=,'"
0
IT
~CH
1
+ ~ ...._
'"'
(m/~ :43)
,,, _.........c: +CH1+
(m/e :15)
502
We therefore expect the ma.ss spectrum of propanone to contain peaks 31 m/ e = 15
and 43, as well as the molecular ion peak at 58 (,..,.,. Figure 29.8).
FLgure29.8Mass~umofpropanooe Flgure29.9 Mas11pectrumofpropanal
The fragmentmion panern can "'adily distinguish between isomers. Compare Figure 29.8
with Figure 29.9. which shows the mass spectrum of propanal. Here the..,- is no pe-:,k
31 m/ e = 15, nor one a! m/ e = 43. Instead. there is a peak 31 m/ e = 57 and several from
m/ e = 26 10 29. This is re:idily explained by the fragmentations shown in Figu"' 29.10.
Figure 29.10 Kmic fragment\ fOfmed from
prcp;mal TI
/''--.
'"'~' t t"
-/ '\::--.,
CH:,CH/ or +~....._ w+ or H+
H CH,CH,---c
- H
,_M<~w.,
inmo,ssp,octn,m)
J
CH,CH,' - --- CH,CH - -"-- CHCH'
r....1. . 28}
Worked example
Use the following atomic mass data to calculate the accurate M, values for the two ionic
fragments at m/e 29 in the mass spectrum of propanal. Would a mass spectrometer with a
seJlsilivityof 1 part in 10000beabletodistinguishbetweenthem?
H~ 1.0078 c~ 12.000 o ~ 15.995
Answe r
CiH 5 is2 x 12.000 + 5x 1.0078
CHO is 12.000 + 1.0078 + 15.995
Suggestthelormuldeoltheicmsat
Thesemassesdifferby36in290030f1partifl80S6,sothis{fair'riflacrnrate)
m/evalue-;26,27and28inthemass
spectrometerwouldjustbeabletodistiflguis.hbetweenthem
~nimofpropanal,andsuggestan
explanatiooofhowtheymightarise.
Depending on whm type of cleavage occurs at (a) and (b) in Figure 29.10. one
or cxher or both o f each pair of ion fragments may appear. The peaks of highes!
abundance in che m:iss spectra of organic compounds are asso daced with panicubrly
stablecations.suchasacyliumandceniaiyrnibocations:
503
ORGANIC CHEMISTRY
The interprelation of the fragmentmion panern in the mass spectra of organic

compounds is therefore an imponant t<X>l in the elucidation of their structures. A
further example will show the power of the technique
Worked example
Figure 29.11 shows the m<M spectra of two compounds with the molecular formula
CiH 40.,. One is methyl methanoate, and the othef is eth,mok acid. Decide which is which
by assignir,g structures to the major fragments whose m/e values are indicated.
Flgure29.11 Mas.s,pectraofmethyl
!Tl{'thanoateandetharmkacid.Whkhi1
i~
whKh7
r
1
I" 11 .b
mu,number
lo
i~
Answe r
'1;
1
30
mas.snumber
.b
Jr lo r
Apart from the molecular ioo at m/e ~ 60, the major peaks in spectrum a are at m/e values
of1S,29and31.Thesernuldbedueto
CH 3 (m/e = 15)
C1H10f CHO (m/e = 29)
CHiO (m/e~31 )
Thisfitswiththestructuieofmethylmethanoate(sei!Figure29.12).
[Jt+,J
Flgure29.12 looicfragml.'fltsfotmedfrom
methy!methanoate
0""' 7 <>1 ~ ''"

H-g. + :;;;,c3~1 H;;;;eg;;~ +mJ;~t 15
(abse nt because it
do...notformaoion)
504
The pe;ik at mle = 29 can come only from methyl methanoate, and not from ethanoic add
The major peaks in Figure 29.11b, apart from the molecular ioo at mle ~ 60, are at mle
valuesof28,43and45.Thesecouldbedueto
co(m/e = 28)
CH 3co(rnte = 43)
C01Hi.,nte~4S)
Thesearisefromthefragmentationss.howninFigure29.13
Figure 29.13 kmk fragment5 lormed from

ethanok..cid
Acompoundofmolecukirformula
C1H?li has major peaks at m/e = 27, 28,
29,45,S7,73and74.Suggestformulae
forthesefragments,andastructurefor
the compound The pe;ik at mle = 43 can come only from ethanoic add, and not from methyl met haooate
29.3 lnfrared spectroscopy

Mastorgankmoleculesab.sorbinfraredradiation. The frequencies that are absorbed
depend on the stiffness of their OOnds and the masses of the atoms at each end.
and the intensity of an absorption depends on the change in dipole momem as the
bond ,ibrates. So bonds to electronegative 31oms .such as oxygen. th31 are found in
.Dk
alcohols (0-H) and carbonyl compounds ( c=o) show very Slrong absorptions.
Although an infrafro spectrum shows a series of abSOf"J}tions (see Figure 29.14) , these
arealwaysreferredtoaspeaksratherthantroughs .
Flgure29.14 The infwedspectrumof

hexan-1-ol
1:
.E
1.,
l,,~
0 0- H C- H C--0
The process is imponant in that it is small molecules in the atmosphere (especially

C01, CH 4, H,O and CFCs) that are responsible for the greenhouse effect : they
absorb infrared radiation that is emined from the surface of the Eanh. thus
preventing it from being lost to space. In consequence . the amount of heat lost
is Jess than that gained from solar radiation. and the Eanh warms up (see the
greenhouseeffecr.page241) .
The infrared spectrum of a compound can allow us to identify the funcrional
groups it contains, as each funcrional g rouphas a characteristic absorption frequency
or range of frequencies. The data are listedinTable29.4.
505
ORGANIC CHEMISTRY
Table 29 .4 Somei nfrared(IR)abIDrption

Type of bond FreqUfflCyofabsorptlon
frequer1Cfe<;fo r organicgroup1 (wav1number)lcm- 1
(The ex..c:tffequencyol absorptKlfl
ofagr()(lpdependsonitsmolecular
environment, and c,m be socm- or m o-tt(hyorogenbonded)
higherorlowerthanthe frl'quenc:fesgiven
here.) bo!ld1tohydrogen
o-tt in RCO,H (1trongly
hydrogenbomll.'d)
tfiplet>oods
C=OinRCO,R
doubletxmd1tooxygeo
c - oinRCO,H
c- oinR,co
1ing~txmds
Worked example
Compounds T and U are isomef'i with the molecular formula C1H60.,. Suggest their
structuresbased oothespectra'i.howninFigures29.1S,md29.16
Flgure29.15 lnlrared(l,QspectrumofT
!~ w.rvenumberkrrrl
Flgure29.16 IRspectrumofU
Answer
Both T and U 'ihow a C=O absorption in their spectrum at about 1700- 1800cm-1. and a
C- 0 absorption at about 1250cm-1. T shows a broad hydrogro -booded 0 - H band from
3300to 2S00cm 1, wtiil:.t U shows no 0 - H b,md at all
So T is CH3CH2C0 2H (propanok acid) and U could be either the ester CH3C0 2CH3 (methyl
ethanoate}ortheester HCO:;iCH2CH3 (ethylmethanoate)
506
CompotJnd V(C 3H60) gives a silver mirror when warmed with Tol~s reagent. It am be
rnrwerted to compound W by reagent X. Use the spectra iri Figures 29.17 and 29.18 to
identifythefonctkmalgroopspieseotinVandW,andsuggesttheidefitityofre;igentX.
wavenumber/cm-1
Flgure29.17 lnfrared(IR)spectrumofV
Flgure29.1BIRspec:trumofW
29.4 Proton (1 H) nuclear magnetic

resonance (NMR) spectroscopy
The basis of NMR spectroscopy
'We cannot see molecules with our naked eyes. but some of the mo.si direct evidence
for their .struaures and shapes comes to us from nuclear magnetic resonance (NMR)
spectroscopy. Eveiy aspect of an NMR spectrum demands an exaa interpretation. and
thereisusuallyauniquernolecularstructurethat gives rise to a panicularspectrum.
NMR is po1entially the m05! powerl'ul technique at the disposal of the structural
organic chemist.
Like electrons. nucleons (protons and neutrons) have spin . If an atom h3s an
evennumberofnucleons , thespinsc3ncelout3ndthereisnoo,,erallmagnetic
moment. If. however. 3n atom has an odd number of nucleons. there is an overall
magnetic moment. As a result. the nucleus can take up one of 1,vo orientations. In
the absence of a magnetic field. the energies of the two orientations are the same.
butinthepresenceof3nexternalmagnetkfield o neorientationhasaslightlyhigher
energy than the other. This splitting into two energy levels forms the basis of NMR
spectroscopy: nucleons can be persuaded to flip from the lower energy spin state to
thehigherspinstate(i.e . toresonate) byirradiating3samplewithelectromagnetic
507
ORGANIC CHEMISTRY
radiation of the right frequency. The absorption of this frequency is detected by the
NMRspectrometer.
The extent of the splining is proponional lO the .strength of the excemal field : co
increase the splitting, very brge external fields a..,- used. The strength of the applied
magnetic field is measured in !<.'Sill, T, one tesb is about 10000 times as sirong as the
Eanh'smagneticfield. Manymachinesuseafieldstrengthof9.4T.
For a hydrogen atom. this creates an energy difference ofO.l6J . The Pbnck
equation. E= hf. shows that this corresponds to a frequency of 400MHz. which is in
the UHF (uhm high frequency radiow:ives) region of the electrom:,gnetic spectrum.
An NMR spectrometer therefore detects the absorption of UHF mdiation by a sample,
in a simibr fashion to any cxher spectrometer. The principal difference is th31 the
sample is also subjected to a sirong magnetic field . Compounds cont.lining hydrogen
31oms therefore show a nuclear m:,gnetic resorurnce absorption 1:xind at 400MHz. The
frequencies absorbed by cxher common atoms that have an odd number of nucleons
areshowninTable25).) .
Table29.5 Theab1otp1:Klftfrequer1de1,in,m
external field of9.4T, fDf ,ome rnmmon atoms
1tudiedwithnuc~armagrieticre,;ooanc:e
(NMR}lnthi1topi::wearelooKingat'Harid
"Cmagrieticre,;onance
Flgure29.19 ThisNMRspectr=ter
measurl'Stl!eabIDrbanceofUHf
r.idtofrequern:yradiationbyhydmgenatoms
(whktihaveanoodnumberofnudeom -just
oneproton)inanexterrialmagnetic:liekl.The
absorptionf1eqlJl>flcyvaries1lightlydepe/\ding
on the chemical l'nvironment of the hydrogen
atom,allowingidentifkationofhydrogen-
rnnt.1lnirigrnmpmmds
The absorpi:ion is very weak, because the popubtions of atoms at each of the two
energy levels are almost the same. At r<X>m temperature for a hydrogen atom. the
popubtion of the upper level differs from the lower end by only I pan in 30000. so
that absorption is ne:irly always rnncelled ou t by re-emission. The sicumion is even
worse for carbon- 13. bearnse carbon conmins only 1% of this iscxope. ln order to
m:iketheabsorbanceasimenseaspossible:
the sample is c<X>led. which increases the population difference

aslargeamagneticfieldaspassibleisused.toincreasethesplitting
the absorption is measured many times and the results are averaged by computer.
NMR is often used to detect the hydrogen atoms in ,v:uer. and the analysis of ,vater in
the hum:,n lxxiy forms the basis of magnetic resorutnce imaging (MR[) (see the panel
onpageS09)
508
Magnetic resonance imaging (MRI)
Because the human body is made up mostly of water, it responds to nucle:ir
magnetic resonance. By suitable scanning. an image of the wa!er discribution in the
body can be built up, which is invaluable in the diagnosis of various illnesses. in
particular brain disorders. The word "nuclear' has been dropped from the name of
the cechnique magnetic resonance imaging (MRI), to avoid suggesi:ing to
patientsthmnudearradiationisinvolved.
The MRI scanner is large. because the magnetic field must pass through the
human body. A fine beam of radiation is applied, giving the absorption pattern of a
cross-section of the body about l cm thick . Within this cross-section. water molecules
can be .studied in differ em pans of the body, as follov.s :
The mag netic field is nOI: uniform but varies from one side to ancther. As the
frequency of the radi3tion is changed, water at differem depths inside the body
responds to the signal. This enables a one-dimensional picture to be built up.
The mdi3tion beam is rcxated through 360. This enables a computer to produce a
two-dimensional image - a slice".
Atypical bminscancontaining20-30slicescanbeobrained in less than \Ominutes.
More subde analysis of the data makes it possible to distinguish belween water held.
for example. in grey or white tissue or in cancerous or normal cells . The technique is
invaluable in the diagnosis of bmin tumours or Alzheimer's disease . It has the g reat
advanmge of being non-invash.-,. and the UHF mdiation is much safer than X-rays.
which are used in alternati~.., techniques .
A refinemem of MRI is to detect phosphorus--31 rather than prowns. Areas of
the brain that are actively in userequireATP(adenosinetriphosphate) fortheir
biochemical reactions . It is therefore possible to locate the regions of the brain that
are most actively involved when differem mental procesaes (for example, sight.
reasoningorspatialwork) are being carried out .
Figure 29 .20 A magnetk re1ooarn:e imaging (MRI) 1eonner grl'es a three-dimensional pktuie
oftheinsideofthebody.a llowingnooinv;i1iwdiagoosisofm;inydisea,e1
FLgure29.21 lmage1froma11MRl1c.inofa
human head
509
ORGANIC CHEMISTRY
Analysing organic molecules

Both 1H and '\: nuclear magnetic resonance (NMR) spectroscopy are imponam in
the analysis of organic compounds. We shall look firs! at 'H NMR.
Magnetic resonance spea=py would be of little value in chemical analysis if
all hydrogen atoms absorbed the same frequency of radiation. The electron clo ud
around the hydrogen atom panblly screens the nucleus from the external magnetic
fieldthroughthe'diamagnetkeffect' .
The electrons within molecule.s - lxxh bonded and non-bonded electrons - are
usually"paired' (thacis.theyocruraspairsofelectronsspinninginoppositedirections).
\Vhen a molecule is placed in an exiemal field. the electron pairs l'OC:lte in their otbits
insuchawaythattheyproducearnagneticfieldwhichopp;:,sesthe e xtemalfield. This
phenomenon is called d iam agn ciism (see Figure 29.22). lbe effect is 10 shield ne:irby
promns from the excernal field . This in rum reduces the frequency :l1 which they absotb
energy when they flip from their lower to their hig her energy SLite.
Flgure29.22 lnanextemal magneticlield,
O~
theeleruonpai~mtateinsuchaw.rtthal
theyprod uceanoppo,;ingmagneticfi ekl
external(applied)
-;;{Q_
-
-'
-- --
a;,K,;ooo<,o,,.;oo
ofeledronpairin
magnetic field their orbital
magnetic field produced
Q :nucleu,
o : e lectron
:i:~::!~e":~~~:7rom
the applied fi eld
When. ho wever, a protOfl is near an electronegative atom (or group) within a molecule.
the bonding electrons are drawn aw:,y from the proron to the elearoneg:,tive atom. The
pro1:onislessshie ldedfromthe=1em:ilmagneticfield.andhenceitabsorbsradimionat
a higher frequency. Tbeeffectisverypronouncediftheprotonisanachedcoabenz.ene
ring. Jn this situation the mobiledelomlised nelectrons intheringrancre-:iteastrong
di:im:igneticeffect.opposingthe=ternalfield. Thish:is theeffectol'.strft18theningthe
magnetic field in the vicinity of the promns (see Figu"' 29.23).
Flgure 29.2llntlenzene.the fiekl(fl'ated external (applied)- - - - - - - !

byt!lerotation ofthe11elec:tromn>inlorcl.'Sthe
applied lfekl
magneticfie ld / ....,,. ,IHo , ,,._
(~ i~
The extent to which a prol:on is de-shielded from the e xternal magnetic field is
measuredbyitschemicalshift.
Chemical shift
For convenience, the hydrogen atoms in the compound tetramethylsilane. (CH}) 4Si
(known as TMS). are used as a reference. The s:imple being investigmed is mixed
with a drop of TMS and the frequency of the abS01"ption,f is measured relative to
thm of TMS , Jn., . There are a number of re-:isons why this compound is used .
All the hydrosen acorns in ThlS are equiv:ilem. so it gives a single ab.sorp{ion peak .
Most(){her g roupsabsorbac higher frequencies than TMS. This is because the
prolOns in Th1S are ne-:ir the electropositive silicon atom. which does n(){ draw the
electrons away from the hydrogen atoms as much as carbon acoms.
510
The extent of the difference in frequency of absorption. is called the c hemical
shift . symbol .S (delta) . It is defined as :
.S = I06x(J ~ fTl,l3)
f=
Values of ii ar<, quOled in parts per million (ppm). Because chemical shifts a"' very
s mall. the magnetic field muSI be identical througho ut the sample. To achieve this, the
superconducring magnets used in modem machines are very ca..,-fully constructed.
As mentioned above, the chemical s hift increases as the electronegativity of the
atom anached to the hydrogen incn,-ases. For example, in a h:ilogen0<1lkane, a
c:iibon atom atw.ched to :, Ouorine atom is more electron-withdrawing than :, catbon
:itom an:iched to an icxline :itom. This is due to the inducrive effect of the h:ilogen
31om. which in cum depends on its electronegmivity (see section 3.10). The more
elecrron-withdmwing c:iIDOfl atom h:is :, gremer effect in dr:iwing the electron cloud
:iw:iy from :in :in:iched hydrogen atom. reducing the screening and incre:ising the
absorption frequency (seeT:ible 29.6).
Table29.6 ChemK.ilshittlvarywiththe
ElectroMgattvtty of atom Ii/ppm
partialdiargeO!lthecarbonatomatt.Khed attachedtotill"bon
totheh)'Orogen.Acartxmatomatt.idiedto
ahighlyelectronegatiwatomsuchao;Muorine F- CH1
hao;a!argerpartialchargethanaQrbonatom CI - CH1
attadiedoolytohydrogenatorm
Br - CH1
I- CH1
H- CH1
The values of some chemical shifts for hyd rogen a!oms within different organic
Table29.7 Somelhemk:al1hift1.f'rotons
arnx:iatedwtthpartk:ulargrnup1ab1Drnlna
regiooofthespectrumratherthanatadefinite
groups are g iven inTable29.7 .
Proton type
tetramet~1ilalll'(TMS)
&ppm ...,.
frequency. endolalk~chain
middle of alkyl chain
adja(enttoc ....c
-C{O) -C tt- adja(enttoC -O(kelofll.'S.
esters.acids)
CJ-l, - CH - adjacenttoarenering
adja(enttooxygen
(alcohol1.ether1.ester1)
alken~
CJ-l,-H (bef\lef\!') aryl
-C{O) -H aldehydk:
phenols
Gitboxylicackls
'The1e5va lue<;a1everydependentoothenatureandacidityofthesolventarid theextentof

hydrogen bonding betwl'!'n mo~ru le1 and the solvent
Low and high resolution NMR spectroscopy:

splitting patterns
%en the 'H NMR s pectrum of ethyl ethanO<lte is scanned at low resol ution
(Figure 29.24) , three peaks :ire observed. corresponding to the three different
chemical environments of the prol:ons in the molecule.
511
ORGANIC CHEMISTRY
Figure 29.24 Nudear magnetic reso11,mce

(NMR)s.pectrumolethylethanoateat
0
lowresoltrtion.Noteth.itthe6scafe,by
rnnwntkm,ha1itszemo11therightof C~1- ~- o----c1,----c~3
thex-axi1
' '
chemicalshift(ifppm '
~ - incre,,.ingfrequer,cyof absorption
Flgure29.25 NMRspectrumofethyl
ethaooateathighresoluboo
' ' '

chemkal,hittaJppm
Theareasunderthethreepeaksareinthemtio2:3 :3,beingproponionalcothe
number of protons at each chemical environment. On published NMR spectrn, the
relative 31"'3 under each pe-:,k is sometimes shown by a number above the peak as
canbe5ee11infigu..,.2,;u5. A1higherre.solution(seefigu..,.29.25), f""'ksAandCare
seentobemultiplepe-aks.althoo.JghBremainsasinglepe-ak. Thisisbec:iusethenucbr
spins of the proi:ons in the ethyl group, r<,sponsible for peaks A and C, interaa with
each other. This is called s pill-lipin coupling. and it is a general phencxne11011 obsen'ed
whenever prorons 011 adjacent carlxx-t atoms are in different chem kal emirornnerus. lbe
splittingofthepeak3risesbecausethemagneticfieldexperieocedbyaprol011isslightly
altered due to the orientation of the magnetic moments (the spin 5tates) of the prolOns
011theadjacentcirlxx-tatom. Considerthepro1onsi11theCH1 group of theethylchai11.
The field they =perience wiU depend 011 the orientation of the magnetic motne'l'lts of the
-CH,- pro1011s, as shown in Figure 29.26
Figure 29.26 Thedill'(tiomofthemagnetk

moments of the --CH,- protom h;ive ~n
effl'ctonthe----CH1 Pfotom
In situations 2 3nd 3, the magnetic moments of the cwo -CH,- prowns ca ncel
each cxher out, so the field experienced by the -CH1 group prcxons will be the
same as the applied field. ln situations I and 4, howe,..,r, the magnetic moments of
the -CH,- prcxons reinforce each cxher. Consequently the field experienced by the
prcxons of the -CH 3 group will be, respectively. higher and lower than the applied
field. There should therefore be a tcxal of three frequencies a! which these -CH1
512
protons absorb. What is more. the probabilities of the four states 1 to 4 are equal,
so overall there is twice the chance of the -CH 3 prons experiencing no change
in field (situmions 2 and 3) as then, is for the -CH 3 procons to experience either an
enhanced field(situation l)ora reducedfield(situation4). We therefore expect the
intensitiesofthelinesinthetripletoflinestobeintheratio 1 : 2 : l .
A similar argument can be applied to the mcxlifimtion of the magnetic field
experienced by the -CTf,- group prorons, by the prowns in the adjacent -CH3
group. In thiscaseweexpectaquanecoflines , in the ratio of 1 :3:3:1.
Worked example
By considering the different combinations oft and J. magnetic moments of the - CH1
protons,exp!ainhawtheratiol:3:3:1 arises
Answer
Thepossiblecombinationsofthethree----CH 3 protomareshowninFigure29.27
Ftgure29.27 HI HI Ill
tit
tit HI
I\\ HI
Predictthesplittingpattem(thenumber
.,.,
oflif){'Sar,dtherelativeintensitiesofthe .,
~nes) for a proton adjacent to
a oneotherproton There are th ree times as many combinations giving a riet magnetic moment of t 1 or - 1,
Ii fourotherprotoos comparedwith t 3or - 3
The general rules concerning the spliaing of the resonance peak of a pro!On by cther
protons are as follows.
Protons in identical chemical environments do nct split each oo:her's peaks.

The peak of a proton adjacent to " protons in a different environment is split in!O
(n t l)lines.
The relative intensities of the (>1 + I) lines are in the pan em shown in Table 29.8.
The interaction between promns separated by more than thr= bonds is usually too
,veaktocauseanysplittingofeach(){her'speaks.
Table29.8 Thelplittingofapeatfor Numberofprotonsadjacent Numberofllneslnspllt Relatlvelntensltlesolllnes

aprotonnexttoprotoo1inadiftl'fent toreson~tlngproton peaks
chemic:alerwirooment
Peaksthacaren(){splitarereferredtoassinslets(s). !fa peakissplitintotwolinesit

isadoublel (d);threelinesisatn"plet(t): fourlinesaquartet(q\etc . lfthereareso
manylinesthatitisdifficulttocountthem.thepeakisreferredtoasamu/1,"p/el(m).
The use of 'heavy water' , 0 20

Protons directly attached to oxygen or nitrogen atoms can appear almost anywhere in
an NMR spectrum. The field strength at which they resonate depends on the acidity
and hydrogen-bonding ability of the solution. Because of easy proton exchange
with cther 0-H or N-H prctons in the sample, these protons often do nct cause
the splitting of the peaks of adjacent protons. They can, however, be identified by
d c m e rium exchange . If the compound containing them is dissolved in D,O (heavy
water', D = 'H), the pro1:ons are exchanged with deuterium atoms in the water. The
peaks due IO the -OH or -NH1 protons disappear (deuterium atoms, ha,ing an
even number of nucleons, don(){ resonate):
CH,CH,--OH t D,O ~ CH,CH,-OD t HOO

513
ORGANIC CHEMISTRY
Flgure29.28 NMRspectraofethaoola a ethanol

showing the-OH peak, and b 11ith D,o CH1CH10 H
med
' s
chemical,hift,Yppm
bethanol+DiO
' s
chemical shift II/ppm
Worked example
Figure 29.29 shows the nuclear magnetic resooarxe (NMR) spectrum of an acid with the
molecularformukc!CsH 80., . Worl<.outitsstructure. {UsethelivaluesinTable29.7,page511
to help you.)
Flgure29.29
' ' s
chemical,hiftltlppm
514
Answe r
ThehighC:Hratiointhemolecutarformulasuggeststhepresenceofabeozenering,and
this iscoolirmed by the pe;ik at 6 = 7.6. The bm.-id peak at 6310.8 is typical of the 0 - H
h'jl)rogen of a carboxylic add. The two-proton single peak at 6 = 3.7 is a CH1 group flanked
bybothanarylringandaCO.,Hgroup,bothofwhichwooldcauseahigh-fields.hiftin
resonance(byabout16uniteach).
ThestructureistherefoteCiH5-CH:r-C02H.
1 Apartfromethylethanoate{seeFigure29.2S)thefeareatleast1Sotherisomersof
C4H80.,. The 1H NMR spectra of two of them, Wand X, are shown in Figure 2930
Expla inthesplittingpattemsseeointhesespectra,andusethespectratosuggestthe
structures ofWaridX
<hemicalshift6Jppm
3H,t
2H,q
<h emical,hift&'ppm
Flgure29.30 NMRs.pectraofcompoundsWandX
515
ORGANIC CHEMISTRY
2 F'9ure 29.31 shows the NMR spectnim of compound Y, whose molecular formula is
C3Hi;01.Suggestapossible51:ructurefor Y,withreasoris
' ' s
chemi<alshiftlJppm
Figure 29.31 Nude.ir magnetic resonance (NMR) spectrum of rnmprnmd Y
3 F'9ure 29.32 shows the 1H NMR spectrum of an alcohol Z

Suggestthestructureof Z, expla inthe~littingpattem,andpredktwhichpe,ak
woulddix1ppe.-irwheo[}.,Oi1i!dded
6H,d
2H,d
chemk lshiftalppm
Figure 29.12 NMR ~rum ofrnmpo1.mdZ
13
29.5 ( Nuclear magnetic resonance
(NMR) spectroscopy
A 13 C NMR spectrum is simpler than a 1H spectrum. This is not only because there
are usually fewer carbon a!oms in a molecule than the"' are hydrogen atoms. but
alsobecausetheabscxbancesina 13 Cspectrumusuallyappearassingleis - they
are nOl split into muhiplets by adjacent atoms as are many lines in a 1H spectrum.
516
Because of the n,ry small nmuml abundance of ' 3c atoms (1 .1%). the chances of two
adjacent rnrbon atoms in a molecule lxxh being 0 c atoms is only ju.st over I in 100,
and so the splining of a peak due to adjacem ' 3c atoms is very unlikely . Although
the spin-intemaion between ' 3c atoms and 1H atoms is very laige, usually when a
He spectrum is run. the 'H- '\: coupling is removed by irradbting the sample with
broad -frequency'whitenoise' . Althoug hthisgreatlysimplifiesthespectrum. it has
the disadvantage th31 the imensities of the peaks are nOI dependent on the number
of carbon atoms. and so it is nOI po.ssible to decermine the number of carbon atoms
associatedwithapankularabsorbance.
Each carlxm atom in a diffen,nt chemical environment produces a single-peak
absorbance at a different chemical shift. Table 29.9 shows some chemical shift values
for 1'Cindifferentchemicalenvironmems.
Table29.9 Some"Cchemical shifts Envlronmentol "c Chemltalshtftrange(ppmlromTMS)

C{alkane)
C{alk.ene)
C{a')'I)
Cin----COX(X O.N)
The ''C NMR spectrum of ethyl ethanO<lte is illustrated in Fig ure 29.33.
200 180 160 140 120 100 80

chemkalohift61ppm
F1gure29.33 " CNMRspectrumofethyl eth.anoate.CH,C02CH2CH,
The spectrum in Figure 29-33 shows four peaks. o ne for each of the carbon atoms in
the molecule . From Table 29.9 we can see that the peak on the left of the spectrum.
atl71ppm.isforcaibon2inFig ure29.34.andthepeakat6oppmisforcarl:xm;iin
Flgure29.34 Ethy!eth;moate Figure29.34.
his a little more difficult 10 assign the oiher cwo peaks. at 13 and 22ppm. but
because the CT-1 3 next to the c- o is likely to be more de.shielded due to the
electron-withdrawing effect of the c- o. we can identify carbon I with the peak at
22ppm.leavingthepeakat13ppmassociatedwithcarbon 4 .
517
ORGANIC CHEMISTRY
Two isomers of ethyl ethanoate are propyl methanoate and prop-2-y! meth.-moate. Their
11 C spectra are shown in Figure 29.35. Decide which compound gives which spectrum
<h<'mical,hifti\Jppm
Flgure29.35 "Cspectraofthetwopropylmethano.Jte1,HCO,c,H,
Paperchromatography(PO u'il'stheprinc:ipleof partition to Use of the M+2 peak in m;m spectrometry enables us t o
separatecompone<it solamixttJre determine the number of chkirine and/or bromir.e atoms in a
ComponentsofamixtureareSl'f}<lratedin thin layer molecule.
chromatographyffiC) throughtheprincipleof adsorption The fragmentation pattern in mass spectrometry helps us to
Components are separated in gas chromatog raphy (GC) by determinethestructureofmolecules
theirrejativevolatilitiesandattractiontothenoo-polarm.Jting e lnfrared(IR) spectrosc:opycanidentifythefunctionalgroups
onthe'>Olidsupport wilhinamciecule
TherootineusesofgaschrOOliltographyinana!ysisirxludethe Nuclearmagneticresonance(NMR) spectrosc:opyG1nbe
detectiooofakohol,drugs,foodadd itivesandimpuriliesand G1rriedoutoocompoundsthatconta inatomswchas 13Cand
expiosiverl'Sidul.'S 1H, which have magnetic moments that take up orientatioos
Medsurir,gtheacrnratemassofthemolecularionp&ikin mass withdifferentenergiesinanexternalmagneticfield

spectrometry allows us to work out the molecular formula of a Boththe chemicalshift {li)valuesandthesplittingpatterns
compound ina 1HNMRspectrumalkiwustodeterminethestructures of
UseoftheM+l peakinmassspectrometryenablesusto molecules
dete<mine the numrn!r of Glrbon atoms in a molecule The 13Cspectrumcanallowmtodetermir.ethenumberand
environment of G1rboo atoms within a molecule
518
Pleaseseethedata5ectionoftheCOforanyA,valuesyou iii Compound L reacts with sodium metal. The NMR
may need. spectrumofcompound l isgivenbelOIY.
1 This question is about the modem techniques of analysis
which may be used to determine molecular structures.
a NMR spectro'iCopy, in contrast to X-ray crystallography, is
frequentlyusedtoexamineprotonsinorganicmolecules
i Whatfeatureofprolon5enablestheirdetectionby
NMR~troscopy?
ii The NMR ~ctrum below was obtained from a
compound X, C, HyO,. In the mass spectrum of the
compound, the M : M+ 1 ratio was found to be 25:2
Oeterminethevaluesofx,yandzintheformulaof
Xanddeduc:eapossiblestructureforthecompound,
explaininghowyouarriveatyourcondusion ',-','hati*>estheNMRspectrumtellyouabouttherumberof
protoosin l andtheirc:hemicalenvironments?
iv Usetheinformationgivenandyouransvverstoi, ii and
iii todeduceastructurefor l. Ex pl a in how you arrive
at your answer. [7]
b ThemolecularformulaC,H 6 representsthecompounds
propeneandcydopropane.
1
: 1/!~1
!---!
&'ppm (6) cyclopropane
{Cambridge lntemationa/ AS & A Level Chemistry 9701, i Suggeston edifferenc:einthefragmentationpatterns
Paper41 Ql c November 2009] ofthemassspectraofthesecompounds.
2 The techniques of mass spectrometry and NMR ii Suggesttwodifferenc:esintheNMRspectraofthese
spectrosc:opy areusefulindeterminingthestructuresof compounds. [3]
organic compounds. {Cambridge International AS & A Level Chemistry 9701 ,
a Thethreepeaksofhighestmassinthemasss.pectrumof Paper42Qllune2013]
organic compound L correspond to masses of 142, 143
and 144. The ratiooftheheightsofthe M : M+1 peaks
is43.3 :3.35,andtheratioofheightsoftheM : M+2
peahis43.3 : 14. 1.
i Use the data to cakulate the number of carbon atoms
presentin l.
ii Explain1'11hatelementisindicatedbytheM+2peak
519
A Level
Organic chemistry
30 Organic
analysis
synthesis and
Many of the commercial

applications of organic chemistry
Learning outcomes
involve the synthesis o f By theeodofthistopicyoushouldbeableto
pharmaceutical compounds. This 23.1a) statethat mostch iral drugsextractedfromn aturnlsourcesoftencontainonlya
topiclooksathowthereactionsthat singteoptical isomer
havebeenintroducedintheprevious 23.1b) state r=nswhythesyntheticprep;irationof drugmolecu~ofteorequires
topicscanbeusedtosynthesise the production of a single optical isomer, e.g . better therapeutic activity, fewef
organicmolecu/es ofspecifk side effects
structurei;.howdrugmolecu/esare 23.2a) foranorganicmoleruleconta iningseveralfunctiooalgrou p1:kleotilyorganic
designed; and how the reactions lunctional groupsusingtherea ction1 inthesyl labus,andp<edictpropertiesar.d
covered canbeusedtoidentifythe reactions
functiona / groups inanunknown 23.2b) devisemulti-stagesyntheticroutesforpreparingorganicmok!culesusingthe
molecule. reactions in the syllabus
23.2c) analyse a given synthetic route intermsof typeofll'actionandreagentsused
lore.-ich stepolit,andpossibleby-products
30.1 The synthesis of organi c compounds

Simple molecul es
Many organic compounds have important uses as pham,aceutirnls, pesticides.
perl'umes and dyes. These compounds alien have quite complicated structures, and
mostofthemaremanufacturedbyorganicchemistsfrornmuchsimplerstarting
materials . The science of organic synthesis is rather like building with molecular
Lego"' : a compound is constructed by combining a sequence of reactions - from 1,vo
to perhaps 20 or so - which stan from known. readily available chemirnls and end
up\\iththetargetmolecule.
Flgurel0.1 Alaboratorywtiererieworganic
rnmpmmdsaresyntllesi'>l'd
Organic synthesis requires much an and craft as well as science. lf you have
auempted an organic preparation in the laboratory you wilJ know that the yield
and purity of your product wiJJ often vaty from those given in the recipe'. Skill and
practiceareneededtoperl'ectpracticaltechniques. The reagents and conditions
520
30 Organicsynthesisandanalysis l
that give an excellent yield with one compound may nOl be as effeain, for ancxher
compound with an identical functional group.
Nevenheless, it is possible to devise a multi-step method for synthesising a given
organic compound by piecing cogether successive standard organic transformations.
\Ve shall iJJustmte this by making use of the reactions summarised in Chans A--G (see
section3().8),a ndTable 3().l,pages53S-536).
For example, suppose we needed to devise a synthesis of ethanok add. staning
from bromoethane:
The strategy is as follows:

1 Use Chan B (page 536) to work out the .structur<,s of all the compounds that can be
madefrombromoethaneinone51ep.
2 Nexc we use Chan D (page 537) to work out the structures of all the compounds
thmcouldbeusedtomakeethanoic acid.
3 Then we see whether there is a compound that is common between bolh chans.
fromChartD
The compound L1 lm n o l is common 10 both, so a vi3ble synthetic rou ce would have
Finally, from Table 30.1, we find the reagents and conditions required co carry out
these two transformations:
Steps I and 2 above using Chart.s A-G may n=d to be repeated if a common
compound is n{){ found.
Worked example
Answer
Chart A (page 5:l6), shows that there are lour reddions of etflffie that may be useful
~~~:~~:~H
CHi = CH1 ~ CH1- CH1
"'>, CH1(0H)CH1 (0H)
fromChartA
Next, coo side ring the target molecule, we can see from Chart F (page 538) that there are
threemethodsofmilkingamine1
CH 1CH1CH1Br~
1 1 1 1
CH : : : : ~ : / CH CH CH NH
1
fromChartF
521
ORGANIC CHEMISTRY
Norie of the three 51:arting materials for makirig propylamine is the xime as the four
prnducts from etheoe, so the synthesis will need another step. Therefore we take each of
thefourproductsderivedfrometheoe,ar.dusethechartstocarryoutthesameanalysison
those products - what compounds can we make from each or.e in tum?
We stop immediately at Chart 8, as we can see that there is a compound in common

betweeoChart8(pageS36)andChartF(pageSJ8):thatis,propanenitrill',CH1CH 2CN
The syntheticroutethere/Ofeindudestwointermediates
CH 2 - CH 2 -------> CHiCH 2Br-----> CH 1CH 2CN-----> CHiCH 1CH 1NH1
Addingthereagentsar.dconditions,thewholesynthe'iiscanbedescribedasfollows
CH 1 = CH 1 ~ C H1CH 1Br
1
""'"'' CH 3CH 1C N ~ C H1CH 1CH 1NH 1
(Notethata's.hortcut'tothl'processhe<eisgivenbythelactthat thechain oftheproduct

contains one more carbon atom than the starting material: the synthesis must ha~ had a
stepinvclvinganitrile.)
Devise syntheses for the following compounds, starting with the specified compounds
1 CHJCH(OHKNlromCHiCHiBr(threesteps)
2 CHJCO.,CHi from CHiCN and CHiOH (two steps)
3 CH 1CHi - C~
/o-0 from CHiCHiCHiOH and phenol (three steps).
4 c1---Q-coiH Imm methy!benzene (two steps)
The synthesis of more complicated organic

molecules
Many pharmaceutirnl compounds are made by joining together two or more
organic parts, that are first synthesised separately. An example is the compound
phenylethanamidethathasbeenusedasapharmaceuticalcalledantifebn"n
F1g u re30 .2 Phenylethanamkle (Figure 30.2)
Worked example
Oevis.easynthesisofpheoylethanamide,startinglrnmetheneandbenzene.{Bothare
readHy available industrial chemicals that are derived from petrnleum.)
Answer
As its name sugge51:s, phenylethanamide is an amide. Amides are formed by r&Kting
togethefaminesandacylchlorides.PhenylethanamidecanbemadeasfoHmvs
522
Thesynthesisistherefo reinthreeparts,asshowninFigure30.3
Flgun,30.3Synthesi1of Ste p Aethene toethanoylchloride

phenylethanamidefrometheneand
benzene
Step Bbenzenetophenylamine
cs,coc, } s_1epCamide formation --0
HiN--0 ----------- CH3CONH
0
Step A Chart D {p.-ige 537) shows that iKyl chk>rides are made frnm carboxylk acids:
Ca rboxylic adds can be made from akohols, which in tum can be made from alkenes
Sotheoverallsynthesisolethanoylchloridefrometheneisasfollows
heatwlthane)((ess
CH1 = CH1 H,so,(a,q) at R.T. CHiCH10H ofNa,Cr,o, + W CHf:OzH Pd, + heat CHJCOCI
Step B Chart G (page 538) sh01vs a two-step synthesis of phenylamine Imm benzene
-"" J: <on<.HCl+heatg
o~oln+ J;,
1 Suggestasynthesisoftheesterprop-2-ylphenylethanoate,C6H1CH1C01CH(CH 3}.,,
ffommethylbeozer.earidpropeoe(fivestepsinall)
2 5ugge51asynthesisofethyl2-hydroxypropaooate,CH 3CH(OH)C01CH1CH1,from
ethaool(foursteps)
3 Devise a synthesis of N-phenylmet hylbenzamide (Figure 30.4) with all its carboo atoms
coming from met hylberizene, C6H5CH1 (five steps iri all)
Flgure30.4 N-phenylmethyHiefl.lamkle
30.2 Design of drugs

A drug is a chemical substance !ha! interacts with the organs in the lxxly !o produce
a physiological response . A drug may occur naturally or be symhetic. Namrally
occurring drugs may be made within our own lxxlies by our own metabolism (e.g.
honnones. nerve transmitters. endorphins), or may be extracted from some (){her
organism. most ofien a plant or a fungus.
523
ORGANIC CHEMISTRY
The effect of a panicular drug Oil the body can be quite varied . In general. we can
classify drugs as follows-
1 those aimed (usually lethally) at organisms thm are foreign to our bodies, that is,
bacteria,virusesandfungi
l those aimed at cancer cells within our own bcxlies (again. hopefully, in a lethal
manner)
.~ those aimed at changing the physiology of our own cells. and hence our physical
(andsometimespsychological),vell-being.
Most commonly. drugs interact with enzyme and receptor proi:eins. EnZ)'lllC'S are
re.sponsibleforcatalysingmo.s1ofthechernicalreactionsthatocrurwithin the cell.
Little can be done to speed up an enzyme-catalysed reaction (apan from the usual
chemical effects o f increasing concentration and temperature). but they can be
slowed down by using inhibitors . Some drug s have therefore been designed to act as
such inhibitors. to treat illnesses that might be caused by an excess of the products of
a panicular enzyme-earnlysed reaction. or to slow down the removal of an imponant
compound from the body. For example, the drug phenelz.ine (Figure 30.5) inhibits the
enzyme monoamine oxidase. This inhibition slows down the metabolism of the nerve
transmitter noradrenaline, and thus the concentration of noradrenaline in the nef\'e
synapses can increase. This drug is a succes5ful treatment for depression caused by a
defidencyofnervetransminers.
Flgure30.5Phenetzineandnoradre11ali11e
ph=elzine
The Ol:her main role of pro{eins in cells is to act as ~cxptors . Receptors are pro{ein
molecules that are often found within cell membranes. l>foch of their influence on
thecell"sphysiologyisduetotheoppo.singphysicochemicalnaruresofthecell
membrane and the cytoplasm. Cell membranes are hydrophobic because of the long
alkyl chains in their phospholipid molecules. whereas the cytoplasm is aqueous and
henceishydrophilic(Figurej,(1 .6).
Flg u re30 .6 SiTTifllediagramoface ll,

1howirigthehydrophobicl(lidbll.iyer
membr.me, the h)'{lmphilic: cytop~m. arid l
valietyof1eceptor1inthecell wall
Unlike enzymes. recep1ors do nOI: catalyse chemical reactions. but when activated'
they produce one of the following physiological responses-
They stimulate a membrane-bound enzyme .

They cause the release of secondary messengers "ithin the cell"s membrane. These
migrate to O{her pans o f the membrane. and either activate or inhibit funher enzymes .
They open ion channels through the membrane. allowing hydrophilic ions to pass
through the hydrophobic membrane.
524
Receptorshaveaaivesitesjustlikeenzymes. W'henthenaturalsubstratefor
a receptor binds with its active site. it changes the shape of the whole recep!or
molecule.his this change of shape that causes the physiological ..,-sponse. Drugs
han, been de.signed !O interact with receptors in either of the following two ways:
I They rnn mimic the natural substrate - sometimes causing an even stronger
physiological re.sponse through a b,ger change in shape. The.se drugs are called
agonists .
2 They can bind with the active site - often mo"' strongly than the n31uml substrnle.
andhenceblockingthebindingofthenaniralsubstrate - buttheydonotchange
the receptor's shape in the right way co cause a physiological response . These
drugs are called a magonist s . They are inhibiting the receptor"s normal function.
Various methods are used to d=ide which molecules may be useful as drugs.
Thes1<,reo--.,lectronicshapeoftheactivesiteoftheenzymeorreceptorcanbe
determined by methods such as nuclear magnetic resonance (NMR) and X- ray
cry.stallography. AcomJX>Undisdesignedcofitimoit.
The natural substrate can be used to suggest con1JX>Unds that could mimic its effect.
If the molecular suucrure of a traditional remedy. such as the active ingredient of a
plant extract. is known. that .structure can be used as a basis for further development .
Figure 30.7 shows some examples of drug molecules whose .structures have been
developed in these ways.
Tradition alpla nt ntract Synthetic drug
HO~~,
,o
)0. '"'
ephedrine
~ ~N(CHJ!1
acetykholine
psilodn sumatriptan
Flgurel0.7 Thl're!atkm:s.hipbetweenthl'
chemkal1tructure1ofthenatural~bstrateo;,
traditiooalplantextracl5andsome1ynthetic
ldentifythekeystructural similaritybetweenthemoleculesof
'""' b
adrenaline,ephedrir.eandsa lbutamol
acetykholir.e,muKarir.eandbet hanechol
When a comJX>Und has been idemified as having some of !he therapeutic propenies
desired of the drug. pharmaceutical chemists begin to work on modifying its
molecular structure to enhance its beneficial properties and minimise undesirable side
effects . Many hundreds of compounds may be synthesised before one is found 10
ha,etherightmixofcharacteri.sticstoqualifyitforfurtherdinicaltrials.
525
ORGANIC CHEMISTRY
30.3 Synthesis of chiral molecules

Almostwithoutexce-ption,theactivesitesofenzymesand=epi:orsarechiml:they
are made up from naturally occurring amino acids. all of which (except glycine) are
themselves chiral (see Topic 27). ConS<"quendy. if a drug molecule which contains
a chiral centre interacts with an enzyme or receptor. it is almost cenain that only
one of its ste=isomers will internet. The other s!ereoisomer will prol:mbly n<X have
the desired physiological effect, or could even have a detrimental effect o n another
receptorelsewhereinthelxxly.
Apan from any possible harmful side effects the other' stereoisomer might
have,theco.stisan{){herincentiveforsynthesisingjustoneenantiomerofachiral
compound - if only 5006 of the drug is going to be useful pharmacologically, ii is
Some examples of pharmaceuticals whm;e enantiomers have different physiological

effects are shown in Figure 3().8 (the chiral centres are circled in red). The modem
conventionforlabellingthetwodifferentenantiomersistousetheprefixes R andS .
Flgure 30.8 Diffl'rentenantiomro(anhave
diffell'fllphyliologicaleffect1
propranolol
Ri,abetabl<><k erforthehearl
Sis a contraceptive
B COiH
HS NHz
penicillamine
Risanti-arthriti<
Sishighlytoxi<
If ,ve synthesise a chiral compound from oon--chirnl staning materials. ""' always olxain
ther.K'"l'tll.ic m lxm R'ofenantiomers (seepage224insection\2.6). ltistherefore
important to ensure that our taiget compound, if chiral, is just the ooe enantiomer that we
want. Phannaceutiml chemists have developed ways of preparing drug molecules in a
== caJly pure .state. These methods c,n be divided into the folk,,,,ing strategies.
I Stan with a chiral comrx,und that is already en:mtiomerically pure. This will usually
be a naturally occurring compound. The synthesis is c,refuUy designed to make sure
that the optical activity of the starting material is transferred to each intermediate and
to the final target comrx,und. by a process known as 3S}"llunctric indnt't lo n .
2 A chiral reagent is used to induce chiraliry into a molecule at some step during
the synthesis. A common method is to use a chiral reducing agent to reduce a
symmetric carbonyl compound to just one enantiomer of a chiral alcohol:
R +llHJaddedb<!ow R 0 - H
'c =o ~ '-c/
RI R,/ 'H
.l A racemic mixture (either of the final product. or of an intermediate) is resoh -cd

into its two different enantiomers (see panel on page 527). This often means that
the half of the mixture that is the unwanted isomer is wasted. so. economically, the
earlier this is done during a long synthesis the better.
4 An enzyme is used to catalyse one of the reactions leading to the target compound.
If the product of the enzyme-catalysed reaction is chiral. usually only one isomer
\\ill beproducedsincetheenzymeitselfischiral.
526
5 In a similar (but more wa.steful) manner, an enzyme is used to react with (e. g.
break down) the unwanted isomer. leaving the desired isomer intact .
Resolving enantiomers
There are two main methods of "'solving a mixture of erl3ntiomers.
The first, now used increasingly. is co pass a solution of the rncemk mixture
through a column of a solid suppon which is itself chirnL a chiral statiOflary phase
(CSP). Originally cellulose (a polymer of ( +)D-glucoae) was u.sed, but now many
semi-synthetic derivatives of cellulose (e.g . cellulose cribenzoate) or O!:her optically
active p;:>lymers and resins are used . The column preferentially absorbs one of
the isomers, Jening the O!her through at a quicker rate. They are thus separated,
and a good yield of each isomer can be recovered .This called C'namiosclective
chromatography.
The second method uses an optically acthe compound to form an adduct with the
racemic mixtu re. The two adducts are no longer enantiorners. but dia51ereoisorners.
Theyhavedifferentphysirnlpropeniesth:itcanbeusedtoseparatethem.
Diast e reoisomcrs are 51ereoisomers that are not mirror images of each other. They
usually comain more than one chiral cemre.
For =ample. if the racemic mixture is a carboxylic acid. forming a salt with an
optically active natural base. such as strychnine. will prcxluce the following:
(+)acid + (-)acid + 2 (+)base ------t [(+)acid-(+)base] + [(-)acid,(+)base]
ThediastereoisomerswiJJoftenhavedifferentsolubilities. andsornnbeseparated
by fractional crystalHsation. The free carboxylic acids can then be liberaced from the
saltsbyreactionwithdiluteHCl(aq).
Otheradductsthachavebeenusedindudecarboxylicesterswithanoptically
active alcohol such as menthol. or. if it is the alcohol that required resolution. with
an optically active acid such as tanaric acid .
Flgu re l0 .9 (-}-mentholand(+)-tartaricadd
,,,+:/<: (-}-me nthol

HOiC, HYCH
X ..
" o,
COiH
(+)tartaric add
30.4 The use of prodrugs

Even if a drug molecule has all the right propenies to make it effecthe in vitro (in
the te51 tube). it mig ht still not be clinically useful. This is bemuse there are so many
obstacles betw=n its JX>int of entry into the body and its intended destination .
For =ample. if a drug is taken orally. it must be able 10 survive the sirongly acidic
conditions in the 51omach and the multitude of hydrolytic enzymes in the intestines.
To get into the bloodstream. it mu51 be non-JX>lar enough to diffuse through the
hydrophobic cell walls of the intestines. but JX>lar enoug h to dissolve in the bkx xl .
If its target is the brain. it must have an =tremely non-JX>lar form in order to pass
through the bkx xl---Orain barrier. On the way it is likely to pass through the liver.
where it will encounter many enzymes whose function is to rid the lxxly of foreign
moleculesassoonaspossible .
There are several ways the pharmaceu tical chemi51 can overcome these problems .
One is to create a compound , called a rodrug. that is inactive by itself but can be
broken down into the active drug once inside the body. The prodrug is designed
either to be stable to the extreme chemical conditions in the digestive tract. or to be
HpophiHc enough to pass through the intestinal cell walls. or both .
527
ORGANIC CHEMISTRY
Worked example
An tmwekome side effect of the non-steroidal anti-inflammatory drug (NSAID) ibuprofen is
irritatklnofthegastro-intestinaltract.ThiscanberedocedbyrNCtingitwith
pheoyjmethanoltof01maprodrug
Ibuprofen phenylmeth aool
Theresultingrnmpoundhi!Slheaddedad~antageolbeingmoreeasilytrans.ported
through the intestinal cell wa lls into the ~oodstream .
Whattypeofcompoundwilltheprodrugbe?
b Suggestreageotsandrnr.ditionslormakingtheprodrug
c Drawthestructureoltheresultingcompound.
d Suggest why the prodrug is more redd ily absorbed through the cell walls than is
ibuprnlro
e Whattypeofreactioncanoccurwithinthetargetcelltore-formibuprofeofromthe
prodrug?
Answers
a Theprodrugwillbeanester.
b HeatibuprofenandthealcoholinthepreseoceofasmallquantityofconcentratedHiS04.
'~ c-o'-0)
d The ester is mudi less likely to hydrogen-bood with water than ibuprofen, which is a
catboxylic acid. It is also more lipophilk, because the extra benzene ring allows it to
form mOfe van der Waals' attractions to the long al kyl eh aim within the phosph~ipid
membraneofthecellwall.
Thee-;tercanbe hydrolysed backtoibuprofen,byanesteraseenzyme
Compourid A {Figull! 30.10) has exc.eHmt in vitro activity as an antibacterial ilgl'lll, but its
in11i10(inthebody)activityispoorbecauseitistoopola1tobeabsorbedthrougha>ll wa lls
Flgure30.10 CompoundA
ii Name four polar functional groups in the molecu~ of A
II SuggestreagentsandconditionsfufmaskingNChofthesepo!arlunctionalgroupsto
makeaprodrug.Drawtheresu lting51ructureoftheprodrugyousuggest.
4? 30.5 Chemical tests for functional groups

Here we bring together the tests that h:,ve been described in the v:,rious topics of the
org:1nic sections of this book.
528
Alkanes (Topic 13)

These bum with a non-smoky flame. are immiscible with water, and Jess dense than
water. They do n ot decolorise bromine water or dilute potassium rnanganme{Vll).
Alkenes (Topic 14)

These bum with a slightly smoky flame. are immiscible with water. and less dense
than water. They decolorise bromine water and dilute pornssium manganme(VI[) at
Alcohols (Topic 16)

These are neutral to litmus solution and (if insoluble in water) do nOI: dissoke in
aqueous sodium hydroxide or sodium carlxmate. They effervesce with sodium
metal (giving off hydrogen) and with phosphorus(\') chloride (giving off hydrogen
chloride). Primary, secondaryandteniaryalcoholsaremosteasilydi.s1inguished
from each cxher by attempted oxidation with acidified dichromate{V]), followed by
distilbtionandpe1formanceoftestsot1the products(seeFigure30.ll).
Flgurel0.11 HowtowDfkoutwhetheian
alcolloli1primary, sern!ldaryortertiary. (UI,
unrl'ersalindicator)
Carbonyl compounds (Topic 17)

Bothaldehydesand ketonesproduceornngepredpitateswith
2.4--dinitrophenylhydrnzine (2.4-DNPH) (Figure 30.12). They m.ay be distinguished
from each cxher by warming with Tollens" reagem (ammoniarnl silver nitrn!e solution)
orFehHng"ssolution(alkalinecopper{ll)solution). Aldehydesreducethesereagents.
toasilvermirror(Figure3Q.13). ora red predpitateofcopper{l)oxide,respectively.
whereas ketones have no effecl upon them .
Flgure30.12Aldehyde1andketone;gr\tea
pll'C~tatewith2.4-0NPH.;Ethanalreacting
and,bfDfminganorangePfl'(~t.1te
529
ORGANIC CHEMISTRY
FJgure l 0.13 Akiehydesgivea1i!vermirror

wilhTo ltem'reagent
Carboxylic acids (Topic 18)

When a drop of a rnrboxylk add is added to a solution of universal indicator.
the solu tion cums red . ( NOl:e that some acid derivmives such as acyl chlorides
and acid anhydrides will also tum universal indicator red because of their
hydrolysis.) Carboxylk adds dfef\'esce with sodium (giving off hydrogen) and with
phosphorus(V) chloride (giving off hydrogen chloride). They also dissolve in aqueous
sodium hydroxide and sodium carl:xmate (giving off carbon dioxide in the process).
Phenols (Topic 25)

These are usually insoluble in water, but wiJJ dissolve in aqueous sodium hydroxide.
They do nOl dissolve in aqueous sodium carbonate. They effervesce with sodium
(giving off hydrogen). When a phenol is added to a dilute neutral solution of
iron(lll) chloride. a violet coloration is prcxluced. Phenols react with bromine ,vater.
decolorising it, and producing a white precipitate of the
di- ortri-bromophenol.
Acyl chlorides (Topic 26)

These react with water to produce acidic solutions which tum universal indicator red,
often giving off fume.s of HCl(g) during the process. They may be di.s1inguished from
carboxylic adds by their not reaaing with sodium metal or phosphorus(V) chloride.
Esters (Topic 18)

These are neutral. s-weet-smelling liquids that are immiscible with water. They do nct
react with sodium metal or phosphorus(V) chloride. or with 2,4-DNPH . On heating
with dilute adds or alkalis, however, they are hydrolysed to alcohols and carboxylic
adds . These produas can be tested for in the usual way.
Amides (Topic 27)

These are neutral. but wiJJ evolve the alkaline gas ammonia (test with cnoiSI red
litmus paper) when boiled with NaOH(aq)
Amines (Topic 27)

These either dis.solve in water to give alkaline solutions (if of low M,), or if in.soluble
inwater,theywiJJdis.solveindilu teHCl.
530
The triiodomethane reaction (Topics 16 and 17)

This is a useful teSl for the presence of the groups CH 30i(OH)- or CH 3CO- in a
molecule. When alkaline aqueous iodine is added to a compound containing one of
these groups (ethanol. ethanaL methyl secondary alcohols or methyl kecones), a pale
yellow precipitate of triiodomethane (kxloform) is formed .
30.6 The use of functional -group tests to

deduce structures
If the molecular formula of a compound is known. its Slructu"' rnn often be deduced
on the basis of the results of various funcrional -group tests. An example will make
Worked example 1
Threl! compounds, J, K arid L, are i~omers with the molecular formula C4H80 1. Use the
informationbelowtoidentifythecompounds J-Q,aridwriteequationslorallreactions
thatocrnr.
a Compound J is unaffected by hot dilute su~uric acid, but re.-icts with sodium metal,
H!hling'ssolutionandalk<llinea,queousiodine
b Both K ar.d l rt.'ilct'Withhotdilutesulfurkacid.Undertheseconditionscompoond K gives
M (CH10i) and N (C 3H80 ) and compound Lgives P (C1H40i) and Q (CiH,;0)
Both M and P effervescewithsodiumcarbooatesolution

N and Q both 1Mct with sodium metal, and are both oxidised by acidified potassium
dichromate(l/1)
Theoxidatiooproductfrom N givesanorangep!l'cipitatewith
2,4-dinitrophenylhydrazine, but does not produc:e a si!ver mirror when warmed with
ammoniiKalsilvernitrate
Theoxidatiooproduc:tfromQisidenticaltocompoond P
Answer
a Compound Jisnotanester(becauseitdoesnotreactwithhotdilutesulfuricadd)bl/1
itcooklbeanalcoholoracarboxylicacid(fl'i!ctionwithsodium).ReactionwithFehling's
solutionsuggestsanaldehyde,andreactioowithalkalineaqueolJSiodinesuggeststhe
group CH 3CH(OH}- or CH1CO-
We now consider the secood oxygen atom in the formula . Since at least one of the two
oxygenatomsistakenupbythealdehydegroup, J cannotbeacarboxylicacid.ltmmt
therefore be an alcohol (reaction with sodium). So J cootains the groups CH1CH(OH}-
and - CHO, and must therefore be CH 3CH(OH)CH 2CHO
Equations
CH 3CH(OHlCHiCHO + Na ----> CH1CH{ONa)CHiCHO + H1
CH 3CH(OHlCHiCHO + [O]----t CH 3CH{OH)CHiC01H
CH iCH(OHlCHiCHO + 4Ii + 60H - ----> CHl1 + - OiCCHiCHO + SI + SH10
b Bothcompounds K and l areestl'f5(reactioowithhotdilutesulluricacid ),being
hydrolysed to acids (M and P) and alcohols {N and Q}. M and P have unique structures for
their molecular formulae. M is methanoic acid, HC01H, and P is ethanoic add, CH 3COiH
BothacidswilleffervescewithaqueolJSsodiumc.arbonate,givingoffcarbond ioxide
Theakohol:s N andQarebothoxidisedbyacidifiedpotassiumdkhromate(Vl)sollllion,
soneitherisatertiaryakohol. N prodlKl.'Saketoneoooxidatioo(orangeprecipitatewith
2,4-0NPH, bl/1 no silvef mirror with Tollens' reagent). So N is the secondary akohol,
propan-2-ol. Qmustbeethanol,whichisoxidisedtoethanok.acid(P)
531
ORGANIC CHEMISTRY
l'\Jtting all this together shows that K must be prop-2-yl methanoate, and L must be ethyl
ethanoate(Figu!l'30.14)
Flgun!30.14 HCOiCH(CHJ!i ~ HCOiH
Deducethestructu!l'softhefoOowingrnmpounds,explainingyourreasooirl!r
1 Compound R has the mo~u!ar formula C8H80. It effervesces with '>Odium met.-il, but
not with phosphorus(V) chloride. It dernlorises bromine water, giving a white
predpitate.lt a!sodecolorisesdiluteaqueouspotassiumm,mganate(Vll)IDlution
2 Compcxmd S has the molecuklr formu la C6H1i0.,. It is unaffected by hot dilute sulfuric
add and also by hot <Kidified did1romate, b u t ~ with both ,;odium metal and
alkal ir.eaqurouskxline.ltformsanorangep/l'Cipitatewith2,4-din itrophenylhydrazine,
butdoesnotreactwithFehling's'iclution
Functional-group tests are also useful for distinguishing between isomers. The
following examples illustrate this.
Worked example l
For e.Kh of the following pa irs of isomers, suggest a test that will di51inguish between the
two compounds
CHiCHiCH1CHO and CHiCH1COCHi
b (CH 3)iCOH ar.d (CH 3}iCHCH10H
c CH1=CHCH10H and CHiCHiCHO
Answer
Oneofthepairisanakjeh'i\W,andtheothefisamethylketooe.Werouldmeeither
Fehling's'iOlutioo (redpiecipitatewiththeakjehyde,nochang.ewiththeketone)oralkal ine
aqurousiodine(yellowpfl'Cipitatewiththemethylketooe,nochangewiththeak>ehyde}.
Note that 2,4-DNPH would not di51ingui5h these: both will give ornnge precipitates
b Both compounds are alcohols, so sodium met.-il or phosphorus(V) chloride would not
di51inguish between them. One is a tertiary alcohol, 'iO would not be affected by warming
with acidified pot.-issium dichromate(VI). The other is a primary alcohol, which would turn
acidifieddichromate(Vl)lromorangetogreen
c Several tests could be used tor this pair. The first compound is an alker.e akohol, 'iO it would
l&lct with aqueous brom ine, mid potassium manganate(VII) solutioo, sod ium metal or
phosphorus(V) chloride. None of these reagents would re.Kl with the second compound
Being an aldehyde, however, this secood compound would re.Kl with 2.4-DNPH, Fehl ing's
solution or Tolll'f1S' rwgent. Note that both compounds would be oxidised by warm
acidified dichromate(VI), so this reqnt would not distinguish between them
532
StJggestteststhatcouldbecarriedoutooe;ichofthefollowingpairsolisomersthat
would distinguish between them
rvc '"'
4 CH:,--CHi--COCI and CHJ--CHCI--CHO
30.7 Predicting the reactions of

multifunctional compounds
Just as we can deduce the functional groups in a comp;:>und from its reactions. so
we can work out how a panicular multifunaio,rnl compound reacts with a panicular
reagent . The reactions of many multifunctio nal compounds can be considered to
be the sum of the reaaions of each of the functional groups they conrnin, and so a
particular compound may react with several different reagents, or a panirular reagent
mayreactwithseveralgroupsinamolecule.
Here are some examples .
Worked example
Predicttheproductof the reactiombetweeotheloH011~ngrnmpour.dsandreagent1
+ hotHCl(aq)
Answer
a lheB1i{aq)willreactwithboththealkeneandthepheool
Aro"
Br~Br
533
ORGANIC CHEMISTRY
b Hot NaOH will hydrolyse both the este< ar.d the amides, and produce the carboxylate and
thepheooxideiomoftheproduct
~ o- ,,
Na+-oM
c The HCl(aq) will hydro~ the ester, but will also form the salt from the amine
c, -
H,N'"MOH
d The sod ium metal will rNCt with both the carboxylic acid and the alcohol
Some functional groups in multifunctional compounds might even re-act with each
oo:her under certain conditions. For =ample. reacting HOCH1CH10i 2CO,H with
concentrated H,SO muses the molecule to undergo an internal esterification to
produce a cyclice.51er(rnlled a lactone).
CCOiH hutwidtH,SO,(cooc. ) CC=OHp +

OH 6
P.>dicttheproductsAto EofthefollowingreKtkms.
+ Br,(aq) --------} B
~ C ( C, H, 0,)
trac olH,SO.(conc.f
4 CH 1CH(OH}CO,H ~ D ((,; H10J

trac~olH,SO,(cor,cJ
~ ~co,H
534
30.8 Summary of organic transformations

Reagents for organic reactions
Reference Reagentsa ndtondltlons Reactlon m.niberonc hart
(see key r , - - ~ ~ - ~ - - ,C~hart
- D~ ~
,hart
- ,- ~ - ~ ~ - - - t
below) Aldehydes Methyl
andxlds ketones
Cl 2(g) + AlCI,
Br 20) + AIBr,
HBl'((J}alR.T.
H2S0,(aq).itR.T
rnoc. HN01 + rnoc.H,so,

at.:ssc
R'Cl + AICl 1 + heat
R"COCl + AlCl 1 + he.it
x,(g) + light(X- ClorBr)
N;iOH(aq) + heat
NH1 inettla nol + heat

11nderprern1re
HBl'{rnnc)orNaBr +
rnncH,SO, + heat
SOCl:,orPCls + heat
R'---OH + rnncH, so, +
"'"
phenol + NaQH (aq) inthe
H1S0,(aq) + heat
R'NH,atR.T.
Na,cr,O,{aq) +
H1S0.,(aq) + heat
KMnO..(aq)at R.T.
KMnO.,(rnnc) + H,SO,(..q)
+ heat
KMnO.,(cooc.) + OHiaq)
+ heal
H,(g} + Ni cata!ystatR.T.
NaBH, inaq Ul'Olll

methanol + heat
liAIH,indiyether
Sn + cooc HC~aq) + heat
Al:,O, + he.it
535
ORGANIC CHEMISTRY
Reference Reagentsandcondltlons Reactlonnumberonchart

(see key
ChartA Chart( ChartD ChartE
below)
Alkenes Bromo- Akohols Aldehydes Methyl
alka nes andaclds ketones
rnncH,SO, + heat
I2(aq) + OW(aq) + warm
HNO,{OfNoNO, + HCI(..q))
R'CO,H + coocH,504 +
"'"
Table 30.1 Reagents for o,-ganic react:iom E, ele.:,trophilic reagents: P, fre<'-radiral re-agents; N, nudeophiHc reagents; O,
oxidising agents: R. reducing agents; X. eliminmion re-agents: M, miscellaneous:
R.T., roomtemperature
Charts for organic syntheses

ChartA: Syntheticroutes involvingalkenes
ChartB: Syntheticroutes involving bromoalkanes(or chloroalkanes)
R- OH--._____ii 1 B4 R- OH
;;;-.......... ~ R ' C H= CH2
R- H e2 IR- e, I~
R'CH ==CH i ~ ~ :=::,
536
30 Qrganicsynthesisand analysis l
O,art C: Synthetic routes involving alcohols
Chart D: Synthetic routes involving aldehydes and carboxylic acids
ChartE: Syntheticroutesinvolving methyl ketones
537
ORGANIC CHEMISTRY
ChartF :Synthetic routes involvingamines
R----Br~ ~ R- NHR'
R'--------CN I R- NH 2 1 (R:Horalkyl)
R'CONH 1~ ~R"CONHR
Chart G: Synthetic routes involving arenes
(R:hydrogenormethylorotheralkylunless<tatedotherwise)
Generalorganicsyntheticreactionscanbeusedtomake Variousmethodsareava ilablefOfthesynthesisol optically

a large variety of orga nic rnmpotmds from sim~er, easi~ pure compoondsfOfuseasdrugs
availablecompoorids Koowledgeoftheredetiomoforganiclunctionalgroupsa llows
Pharmaceutical ~ecules can be de'iigned to target specific theidetititiesoforganiccompmmdstobedeterminedand
e<izyme-;and/orreceptors,totr&itavarietyofdiseasesand isomers to be distinguished
illnesses
Theuseof prodrugs isamethodolprotectir,gdrugmolecules
fromdegradationbeforetheyreachtheirsiteolaction
538

Please seethe data section of the CDforanyA,.valuesyou 2 Compound Chas the molecular formula C7H140. Treating
may need C with hot concentrated acidified KMnO~(aq) produces two
1 a Describeandexplainhowtheaciditiesofethanoland compounds, D, C4H80, and E, C3H40,. The results of four
phenol compare to that of water. (4] tests carried out on these three compounds are shmvn in
b Complete the follmving equatiom showing a ll the the following table.
productsofeachoftheo;e reactions of phenol. Include ~~~~~~~~~~~~~
reaction conditions where appropriate. If no reaction tHtrugent

compoundC compoundD compoundE
cx:curswrite110reactio11.
(5.-. ""'
1,(aq)+OW(aq)
)'ellow
p,ecipitate
yellow
predp<tate
(5.,.o, 2,4-dinitr~hydrazir>e
o,ange
p,ecipilate
a Statethefunctionalgroupswhichtheabovefour
ora.,.ge
predp<tate
6
reagents test for.
i Br1(aq)
ii Nab)
.cs,co,, - - - ii i li(aq) + OW(aq)
iv 2,4-dinitrophenylhydrazine (4(
6",
c Theanalgesicdrugp;irac:etamolcanbesynthesisedfrom
[SI
b Ba5edupontheresultsoftheabovetests.~ggest
structures for compounds D and E.
c Compound C exists as t1vo stereoi50mers. Draw the
(2(
structural formula of each of the two i=ers, and state

thetypeofstereoisomeri=involved (3)
phenolbythefollmving route. Suggest reagents and
{Cambridge lntemational AS & A Level Chemirtry 9701,
conditionsfortheeac:hofthree steps, and suggest the
structure of the intermediate H.
6
step1 i
D
step2i
~'"'
step3i
~ NHCOCH1
paracetamol (4]
539
Index
3dblockelements 397--414 adenine 489--90 ammonia 65,66,127,1~
catJl}tlcpropenles 412- 13 adh<>s!n-s 483---.J reactions 273.320. 322.444
adsorpilon 166,498 ammonium ton 50, 77---f',
,nmplexformat!on 40}-ll asonl.sls 525 amorphoos(non-.crystaU!n.e)sol!ds 71,317
properties 399---402 alcohols 231 . 281---93,308-9. 440-1 . 529. amoumofreactants 16o
varlableoxldatlonSlates 402 53'>---{;.537 ampholytes 123
bol11n 8 po1n1s 65,67,282,306 analsestcs 436
a,-k<'loaclds 442 dehydratlonof265 anal)tlcaltechnigues 495-519
fl-pleatedsheets 487 lsomertsmandnomendature 282--4 chromatasraphy 49';-9
xbood.s~l,252--4 nudeophlUcsubstltutlon 279, 285-7 lnfraredspectrosropy 505-7
delocallsed 61- 3 oxidation 287---9,302 massspectromel!y 499,500-5
xorbltal'l 5,S---9 preparinB 29)---1 NMRspectro,;copy 507- 18
abonds 57---8,59---{i(),252
Aberfeldyfoe1'bridge 478 reductionofcarboxyUcactds10311 predpltatlonr,aactlonsfor 324--5
aldehyde, 288,294-3()4,529--30,535---{;.537 anlSO!roplcmaterlal.s 85
absoluteenthalpychangeofhydration 334 tsornertsmandnomenclature 296 anode 136,149,151,391
absol.uteTemperarurescale 25,91- 2 preparinB 302 anodlc(sactifictal)protect:lon 388
reactions 297- 302 amasonlsts 525
reduction 290,298 amlsepilcs 43'H'i
absorp!lonspectra 4ll - l2 alkaUnesolutlons 370 appearance 188,317- 18
accep1oramm 49 alkaUs 119 arenes 415-32,538
acet}ichoHne 455 seealsobas<>s isomerism and nomenclature 420-2
add-basen>acllOflS 120, 121 alkaloids 449--50 physlcalpropenles 420
representing 122- 5 preparlns 437
add-basetltratlons 127- 3,i,J16,J7}-5
adddl.ssocta!lonronsiants 367--8.370 ,,,_.
alkan.es 65, 67,231,234-50. 255. 529, reactions 422-30
addlcsolut!ons 369 cracklnB 238----9. 264 aroma!lcrompounds 419--20

addl!y isomerism and nomenclature 235-7
amlnoctds 462 radlcalsubstltutlon 278 Arrhenlw!heory 118-22
phenols 43}-4 reactions 24}--.a aspanlcadd 465---{;
add rain 197---8, 363 alkel>l':'l 251--4i,529,53'H'i aspirin 436
add, ll&-35,SJ'Hi addltlonpol}mertsatlon 262--4 asymmeutclnducllon 526
carboxyllcseecarboxyUcadds elearophlUcaddltlon 278 atmospherlcpressur,a 90
practlcalt<'Chnlques 32}-4 hydration 259--60,290 atcmlcabsorptionspectmscopy 27
suonsandweak 126 tsom.ertsmandnom,enclature 253. 254
seealsouaer1,11tlv/aua/<acl<ts preparlns 264-5 aTcmlcmassun!!S 6
reactions 25'H'il atcm!cnumberseeptttonnumber
act!va!lonene'BY 212,362 alktia!lon 426 aTcmlcradH 41 - 2, 189,190
barrlerndrateofreactlon 154-5,16~3 aUO!ropyofcaJbon 84---fl atcm!cstrucrur,a 20-43
hlghandelectrolysls 387 ahematlveen.ergysou= 103,239-40 elearonlcronfisuratlon 32--42
acUveskes 166,167---t! alumlnlumextractlon 150-2 enersrLewls 29--36
acylatlon 426---7 amides 305.444. 4~1 . 530 lsotopes 22- 5
acylchlorldes 305,30'),442--{,,530 syntheticpolyamides 466--7,474--7 orbitals 26,29,30---{i
properties 443 amines 449-58,530,53'H'i,538 sub-atomlcpartldes 20-2
r,aactlons 44}-5 lsom.ertsmandnom,enclature 451 - 2 atcm!sation,enthalpychangeof ll}--15
addlt!onpolymer.s 262---4 . 47()-.j preparation 456----8 atcms 1
adhesives 483 reactions 444.452---Q == ,_.
dlspo,al 492- 3 reductionofamldesto 46o---l slz.es 4--5
dlstingulshlngfromrondensatlon amlnoactds 225,461---Q,485 Aufurnprlndple j'>-{i
polymer.s 49)---2 elearophoresls 46'H'i autoca!alytlcr,aacllons 359
addlt!onrl'actloru 227,228,340,341 physlcalandchem!calpropertles 461---3 averaB"bondemhalpy(averasebondene'BY)
reactions 46}-5 111.115-16
benzene 429 amlnosroup 452 A,ogadroronstant 7,390---1
Index
A,ogadro'sLlw 93 bnlnscannlng 509 cellmembranes 524
azodyes 456,457 brine 149-50 ceramic., 33Z-3
backreacrion 173 brittleness 83 CFG'l(chlorotluorocarbons) 242,267,
backUtratlons 133---4
bo.crerialfermenta!lon 264
bo.kelke 478--80
bromlnatlonreactlons 256---7.42}-4.435
pollltlond!hebromlneaTOminthe
"""
Chad,.,1ck,James 21
chain!somerlsm 2al,22l
balaoced<>quaUons 11- 13.17 reacrionbelweenhydrogenbromideand chainreacrions 170,246
redoxreacrlons 141--4 aJke"'-'S 2:5,8 chargedenslty 82,345
baduntchloride 324 hromoolkanes 265,53H chargetransfer 411
""" .,
bases 118-35
hromobenzene 423-4
Bronsted---{.owry!heory 12}-7
Charles'slaw 90,91
chelate,i 408---9
actd-basereacrlons 124---5 chemical energy 2H.97
buckmlns!ertiJlJerene 86---7 ene'BYchangesseeene'BYchanges
buffersoluUons 371- 2,463 chemicalshlfts 510-11
butane 235 chlr.ilmoJecuJes 244---{i
aminoactds 462 caldumcarbonaTe 194----5 synthesis 526-7
baux!!e 150-1.152 caldumhydroxlde(slakedllme) 194----5 chlorina1ede1hanes 246
benzene 216,217,4l5--l9,5l0,53H calrulusnO!aUon 350
addltionreactlons 429 calodme!ers 99-100,1()4---{i manufacrureanduses 2o6-7
delocall'lat!on 61,416--17,418 cancertreaunem 410-ll reacrions 191- 2.204.244---{i,424
ek>crrophllicsubs!l!u!lonln 422---{i caffianlons 229----30 chloroalkanes 265,446
stability 418-19 carbocatlons 229 chlorobenz.ene 424,431.446
benzene ring intermediate 256---7,258,42}-4,429 chlordluorocarbons(CFG'l)242,267.
carbon 46---7
structure 415--18
seea/soarenes,pheooks
b!dentatel!gands 4(t!
allouopy 84-8
carbon-13NMRspecrroscopy 'i08.510,
"""
chlordlydrocarl>ons 207
chloromeihanes 244---{i
b!layergrapbene 88 516--18 chromatography 495----9
black-and-whltepho!ogr.iphy 169-70 carbona!elon 63,78 cluomophorell 457
blodegradablepol)mers 481- 2 carbona!es 194.344---5 cls-platln 410-ll
oomng 339,340 carbo11--01rbonbonding 210-ll cts-mms(geomelrlcal)lsomedsm 2al,
bomngpolnts 65,66. 67.73,74,82 carbondioxlde 240,241-2 222- 3.253
3dblock 3!.19.400 carbonnano1ubes(CNfs) 4,Si',88 'clock'reacrlons l';S. 355
acylchlorldes 443 carbo11--0xygenbond 284.285--7 coal 102
alcohol, 282.306 carbonrlngs 210-ll codeine 454
alkanes 235,236,237,2:52.282,450-l representlnginformulae 216--17 collision
carbonylcompounds 294---{i,529-30,53H ene'BYci 162,164
amines 450-l seea/soaldeh}'dell:ke!ones r.i!esof 159-{il.16}-4
~""
carbonylrompounds 295
caffimqfate!on 62
carbox)igroup 305
theoryandratescireacrlon
colorlmeter 157
16}-5
carboxyllcctds 306 carboxyllcactds 305--11 . 530,537 colou r 157.317- 18

esters 312
halogenoolkanes 268
halogens 202
,.,_,
effecrofs!rucrureonaddstrength halogens 203
combinat!onreacrlons 340. 341
Boltzmann.Lud,.,1g 164 !som,ertsmandnomendarure 307 combustion
bombcalortme!er 104---5 preparing 31}--14 alcoools 284
bondangles 213 alkanes 243-4
bondene'BY 45 caivones 225
bondenthalpJes lll - 16 ca!alase 168 enthalpychangesof 102---8
average lll,ll5--l6 ca!alysts 162.165--8,362- 3 hydrogen ll2- l3
finding ll}--16 be!erogeneous 165,166. 362- 3 common Jon effect 376
bonding homogeneous 165,359 complememarycolours 411
carbon---.carbon 210-11 andpollltlonof<>qumbrtum 177---8 compJexlons 40}-ll
lncompJexions 404-5 tr.insklonmeu!s 412- 13 bondlngln 404-5
rovalemseecovalembondlng ca!alytlcconvener.i 166--7 isomerism 409-11
hydrogen 65--7,72--4 ca!alytlccracklng 239 nomenclature 407---8
ionlcseelonicbondlng
lnslmpJemolecuJes 44-68
ca!alytlchydrogenatlon 299
ca!enat!on 210 """"'.,.
compJexmeialhydrldes 298
bondJength 45 cathode 136.149,151,391 compollltlon d an equmbrlum mlxlure 181- 2
Bom-Haber cycle 329-33 compoundions 77---9
predpl!a!lonreacr!onsfor 320-2 compounds 2,44
Boyle 's law 89 celldlagr.ims 384. 385
541
Index
cydoperuane 216 Faradayronstaru 390---l
changlngandtheposltlond<>qu!hbrlum cydopropaue 216.217 Nerrutequatlon 388-90
standan:lelearodepotentlal 384 , 385
"'
equllibrtumcoru1arnx,, 178--82 Dalton,John l.20
daUvebondlng 49--50. 453
standan:le.m.f. 382.385-8
findlngusingtltratlons 127---tl,129---31 , seea/soelearolysl:5
'"'
mol.esand 16--17
elearod>enti,uy 381-96
elearodepoten!lals 381- 2
,,,_..,
andratesofreactlon !59-{,(),351- s, seea/so3dblockelernents
DDT 431
standan:l JM . 385
elearolys!.s 83,136,J39,340. 3S\l,391 - 2
roncernratlorHlmegraphs 351.353,354 decompo,!Uonreactlons l,339,341.342 usesof 149--52
rondensaUon 340. }il Group2rompounds 194. 344----5 elearonafflnlty(E.A) 330---l
rondensatlonpolymer.i 446,447,474---7 degenera!eorbltals 404 elearon-donatinggroups 441- 2
adhes!n>s 483,484 dehydrat!ondalrohols 265 elearooegaUvl!y 53-4. 7H
dlstingulshlngfromaddltlonpolyme"' dehydrogenase 168 elearonlcronfigura!lon 32-12
deUquescence 317 .J,dblockelements 398,399. 401
disposal 492- 3 delocaU.saUonenergy 419 effectonatomkradius 41- 2
rondensatlonreactloru 227, 22&309---10 delocaU.sed1<bonds 61- 3,416-17.418 expertmemalev:ldence 36-41
aldehydesandkeion,es 299-300 D<>mocrl!us 20 elearonprobab!lltyd!.'l!rlbu!lon 30
ronductlngpolymers 482- 3 denamrtngofpro!elns 167 elearoru 21,22
ronductMtles SH,399 densltle.s 399---400 arrangernentlntheatorn 26--36
ek>arlcal 83,85,190 deoxyribormdelcadd(DNA) 488-90 loslngandgalnlnglnoxldatlonand
depolymerlsa!lon 264 reduction 136
ronjugateadd--basepal"' 12}-4 deproo:onat!onreaalons 4C6---7 measurlnglonlsa!lonenergles 36-41
ronjugateddoublebonds 482 de!onatlon 343. 3-'4 spin 35
ronserntlondene'By 99 00\Jterlurnexchange 513--16 elearon-wkhdrawlnggroups 441- 2
ronservatlondmass ll diamagne!lsm 510 elearophlles 227-8. 254
Contaaproces.s 166, JS(i diamond 75 , S>-5, s6 elearophll!caddi!lon 2Z7,256-7, Z78
co-ordlnate(da!lve)boodlng 49--50,453 diaphragrncell 149. 150 elearophll!csubstlrutlon 2Z7
co--ordlnatlonnumber f0--1 . 404 d!astereolsornel!l 527 lnbenzene 422---{;
co-polyme"' 4n-J diazonlurnsalts 456,457 lnsub:stl!utedarenes 427-9
ropperlonromplexes 412 dichloroberuene:s 420 elearophoresl:5 465---{;
ropperpurlficatlon 152 dioxin 432
ropper(ll)sulfate 109 d!polemornem56 eUmlnaUonremlons 227, 228. 275---{)
corrosion 388 dipoles 54---{; eUmlnatlone,ub:s!lmtlon(E/5)ratlo 276
roukmb'i 390 d!protlcacld.s/bases emls.slonspectra Zl-8
roupllngreacllons 4}5,456 d!.splacernentreaalons 203 emplrlcalforrnulae 10,213,243
rovalencles 8,4&-"9 d!.splayedformulae 214 enantlomers 22H,526
rovalernbond!ng 44-4! d!.sposalofpolyme!!i 263-4. 492- 3 r,>solvlngamlxtureof 526,5Z7
1tbonds 58--{;J.252---4 d!.sproponlona!lon 143-4,204 enan!loselealvechromatography 527
obonds 57-8. 59--{i(l. 252 d!.ssoda!londweakadds 367-8 endahermlc processes 38, 39, 99. 339-40
dative 49--50,453 d!.ssoMng 339,340 bond-breaking 44--5
delocallsatlon 61 - 3 d!strlbutlon(panlt!on)roeffidents 376--9,4\16 endpo!m 129. 130. 373
lrnermolerularforces 64----7
1.soelearonkmoleculesandlons '>6---7
d!.sulfidebrldges 488
DNA (deoxyrlbonucleicadd) 488-90 "~""'
chemical 25---{),';II
mol.ecular shape 51- 3 DOberelnoer,Johann 187 <nnservatlonof99
multiple 50 donoratom 49 ene'B)'changes 97- 117,329--48
oxldatlonnumber.s 139---40 dorblta!.s 31 - 2,34. 35 seea/soemhalpychanges, entropy
polarity S4-{, doi-and-cros.sdlagram 46 changes
representing 46 doublebonds50. ~ ene'B)'d!agrams(reaalonprdiles) 155,
wkhserond-rowelements 46---7 andV5EPR 5J--3 361- 2
w!!hthlrd-rowelements 47 double-headedarrows 62. 416 ene'B)'d!.'ltrlbutionrurve 164
cracking 238----9. 264 drugsymhes!.s 523-8 ene'B)'levels
CfOSll-Unked polymer.s 478,---t!l d-!o--dtransl!lons 411- 12 .J,dblockelements 398,401
crudeollproo,s.slng 237-9 dyes 456,457 lntheatom 29--36
crrotue 150,151 dynam!cequ!Ubrlum 173-4 andemlssionspectra 27---f',
cryS1allinesollds 71.317 eropolymers 481- 2 e!le'B)'SOOfCeS 102-4, 239-42
crystallisauon.wa!erd 131.132 effeaiwroJUslolls 162 emhalpy ';TI
C!ermlnal 4s6 effeai,enudearcharge 34,39-40 bondenthalples 111- 16
rurlyarrows 62. 124,230 efflorescence 317 emhalpychanges 26,33,45,97- lll,154
cyanide 274 elearlcalronductl\ity 83,85,lS\l 339-43
cydohe:une 216,417 datomi'latlon 113--15
cydohe"'-""" 216 elearod>emlcal cell 381-91 dromhus!lon 102-8
"'
Index
ciformallon 110-11 flavourlogagems 313 lsomerismaodnomendature 268----9
cihydrallon 333---4 flue-gasdesulfurlsat!on(FGD) 240 nudeophlllcsubSlkutlon 270-5,290
cihydrogenallon 41&-19 forbltals 31- 2. 35 preparing Z78,-9
la!!lceernhalpy 329---33. 334 forma!lon,eruhalpychangeof 110-11 reactions 27o--f,,290
measurlngdlrealy 99--101 fom1ulae 2. 7-8 halogeooarenes 431- 2
ci""-'U!rallsat!on 100-l displayed 214 halogens 202-8
cisolu!lcm 100. 333 empirical 10.213,243 Hammood'spos1ula!e 362
standm:l 104, llO-ll, ll}---15 molecular ll,213,243 heatronductlon 85-6
thermometric measurements 316 repn>sentingo'!lanlcrompounds 21}---17 heavywater 51}---16
ct,11portsatloo 113,114---15 skeletal 214---17 , 218 heUum 32- 3
emhalpy-<irlvenreaclloos 340-1 stereochemlcal 213,214 herbicides 431- 2
emropy 335--7 structural 213
emropychanges 336-7,339--43 fo,wanlreaalon 173 Hess'sLaw l0&-ll, ll5-l6
emropy-drlwnreaaloru 339---40 fO&Sllfuels 102.240 heterogeneouscatalysts 165. 166,362- 3
enzymes 165,167-8. 524 fractlonaldlsUUatlon 237-8 heterogeneousn>actioru 161
epoxyreslru 484 fre,el.'flef8}" 337-44 heterolysl:5,bond 229---1(1
equalloru ll - 13 freeZlng 340. 341 hexane 376--7
balanced 11- 13,17,141-4 frtctiooaln>slstance 466 h!gh-deosltypoly(etheoe)(HDPE) 262
Frledel-Craft.sacylation 426---7 h!ghexploshes 343-4
uslngthemoleinmasscalculatloos Frledel-Craft.sreaalon 426 h!ghn>soluUonNMRspectrosropy 511- 13
1}---15 fuelceUs 392- 3 h!nderedrola!lon 252- 3
equU!brla 172-85 fuels102.240. 243 homogeneou.scatal)'S!S 165.359
dynamlcequU!brlum 17}-4 fullerenes 1'16-7 homogeneousreactlons 161
po,lt!ondequUlbrlum 17}--il funalonalgrouplsornertsm 220. 222 homologousserl<>s 2.30---l
quant!tatlveapproach 367-8J funalonal-grouptests 528-34 homol.ysls,bond 229
equU!brlumroostants 178-83 predlctlngreactlooscimuhlfuoctlonal hybrtdlsatlonoforbltals 58
K,, 17S-82 OJD1JX1UndS 53}-4 hydration
x. 182---3 reagents 535-6 alkeoes 259-00,290
using 181- 2 use!ndeducings!ructures 531---3 emhalpychangeci 333-4
equU!brlumm!xlure,rompos!!lond 181- 2 gaschromatography(GQ 498-9 hydrochlorlc acid 285,323
equt,,alencepolm 374 gasronstam 92 hydroeleartcpower 103
esteflficaUon 284-5,309---ll,43'1.444 gases 69-71.89-95 hydrogen 32---3
estel"S 284-5,J05---{i,Jll - l3,530 behavlourdn>algases 9}---5 combustion llJ-13
isomerism and nomenclature 307 detection 3H!-19 co,11lembondiog45-6
ethane 235 ldealgasequa!lon 89---93 emls,lonspecrrum 28
measurlngvolumeciagasgtvenoff 156 ene'B)'Lewls 29
ethanolc actd 504-5,521 molellci 15 fuelcells 393
ethanol 240,284,29)-1,514 Gelger,Haos 21 oxldatlOflnumber.s 140
geometrlcal (cls- rrans)isomerlsm 220, protonNMRspectrosropy 507- 16
addltionpolymerlsa!lcmciethene 222-3,253 reactionswithhalogens 203---4
derlvattws 470-4 geoihermal power !03 hydrogenatlon m
bondlngln 59---) Glbb'l,JoslahWUlanl 337 alkeoes 255
ether., 283-4 Glbb'lfre,eene'BY 337-44 emhalpychangeci 41&-19
ethylam!oe 274 globularprole!ns 167 hydrogenbondlng 65---7 , 72-4
ethyleoedlamlnetetraacetlcactd(edta) glycine 465-6 !mercha!nhydrogenbonds 4n, 478
grapheoe B6.87-8 hydrogenbromide 286
ethylethaooate 511- 13. 517 graph!!e SHi hydrogenchlortde 112
eutrophlca!lon 198 greenhouseeffect 241 - 2 hydrogenq11nlde 297-8
excessreaaants 352-4 Group2compounds 344---{; hydrogenfluorlde 65, 66
exct!edelectrons 27,28 Group2elements 19}-5 hydrogenhaUd<>s 204
exothermlcreactlons 99,340-1 Groupl7elements(halogens) 202-8 eUm!natlonreaaloru 265
expandedpolystyrene 471 groups 187-8 reactionswithalkeoes 257---9
exploslw,i 341.342,343-4,425-6 guanine 489---9) hydrolysis 227,228
ex!enslwpropenles 3 Haber process 166, 173.196. 362- 3 amides 460
Faraday. Michael 390. 415 half-cells 382 esters 311,312- 13
Faradayrorutant 390---l half--equa!loru lU---5,137-8,141- 3 halogenoalkaoes 273
fblock 188 half-Ufeciareaalon 353.357 hydroxides 194
FehUng'ssolutloo 301.302 haUdeloru 20H Group2 345-6
fermematlon 264. 290-l Hall,Chades 151 hydroxonlumlon ll&-19
fir.stlonlsat!onenerglell 37,38-41 halogeoat!onofalkaoes 244---9 hygro,ropy 317
fir.st--Ordern>actlon.s 270-l,353---4,356---7 halogeooalkaoes 257---9,267---3) Ibuprofen 528
flameteSls 319--20 CFCs 242,267,276----8 ldealgasequatlon 89---93
543
Index
ldealgases 92 lysine 465---{;
assumpUonsabout 93 M+lpeak 500,501
!gnklonpolm 211 carboxyHcactd.sand<"Sler.i 307 M+2peak 500,501- 2
!mmlsdblesolvent.'l 376--9 lncomplexlons 409--11 M+4peak 500,501- 2
lnclneratlon 26}-4 geometrical 220,222---3.253 macromolerularco,-alemlmlces 71.72. 74--5
!ndlc:itors 129,130,373---4 halogenoalkanes 268----9 magn,es!um 37~
!nduceddlpoleforces 64---5 Opllca] 22(),222,223--{),410,462- 3 magn,eticresonancelmaglng(MRI) 508.'i-09
lnduce<lpolartcy 5,6 S!en>oi.somerism 22(),222---{;,410 malar:lamosqulto 431
!nductlveeffectcialkylgroups 247---9 structural 220-2,l9-JO manganese 401
lnfraredspectrosropy 5()5.-7 wlngfuoct:1onal-groop1eststodlstlngulsh Markovnlkov'srule 2'i9
!nlllal-ratesmethod 352,354-5 belween&lm,ers 532- 3
!nol)pnlccompounds 209---10 lsolopes 22- 5
appearance 317- 18 lsolop!clabeUlng 173-360
solubilkylnwa!er 318 Kelruk',August 416
l!ISl'Ctlddes 431 Kelruli's!ructureofbenzene 416.417 measur:lngd<'Cfeaseln 157
!nslantaneowdlpoleforces 64---5 kelvin!emperaturescale 25,91- 2 molecules 5---{;
!ntens!vepropenles 3 kelones 288.294--304,529,53'>--6,537 sub-amntlcpanldes 22
lnt<'flltcm!c radH 189 l.somert.sm and nomenclatun.> 296 u.slngthemolelnmas.scalculatloos
!mercha!nhydrogenbonds 477,478 preparing 302 l}--15
!nterlonlcradl! 189 reactions 297- 300 mas.s/charge(mle)ra!los 500--5
!ruermedlatecarbocat!on 256--7,2';8.42}-4 reduction 290,298 mass number 23
"'
tru<'f1Dl'dlates 359,360
andtrarult!onstates 361 - 2 klnetlcaUystable(lnen)reactants
mas.ssp,,arome1er/spectrome1ry 5,23-5
analytlcaltechnlque:s 499,500-5
mas.ssp,,arum 24
!ruermoll'rularforces 64-7 klnetlcenersy 25-6
!nterstklalhydrtd<>s 166 klneUclSOlopeeffecr 360 classifying 2---3
lodlde--peroxydlsulf:ne(VI)reacUon 363 klnetlctheoryofgases 93-5 lrnenslwandenens!vepropenles 3
Iodine 146---9,376--7 kryp!on 24 Maxwell,JamesClerk 164
reacrlonwtthpropanone 35l-6,3ss-6o meltlng 339,340
todlne----1hlosulfate11tratloru 317 Ladenburssuucrureofbenzene 416 melting points 72, 74. 82
lodoform(trl-lodomethane)reacUon 289, lamhanolds 188 3dblockelements 3!.19. 400
301. 302. 531 lanlceenthalpy(LE) 329--33,334 amlnoactds 461,462
lonlcbondlng 50,75-fl3 lanlces 70,71- 5 halogens 202
compoundlons 77---9 thlrdpertodelements
findlngstrength'ldlonlcbonds 329--33 macromolerularroovalem 71,72, 74--S Mendeleev,Dmltrl 187
metaUic 71 ,8}-4 mesomert.sm 416
lonlccompounds slmplen'"-'cular 72-4
oxldatlonnumbers 13&-9 LawdConservatlonofE""'BY 99 meulUclattlces 71,8}-4
propenles 82---3 LawdConsetVatlonofMass II meulUcradll 399---400. 402
solubility 375---{) lead--addacrumulator:'l 393. 394 me!als 308. 309
lonlcequatloru 119--22 LeChateller'sPrtndple 175,176 melastablllty 341
lonlclattlces 72.00-2,82---3 l!gand-exchangereacUoos 405-6 methane 244---{;
lonlcproducrdwater 368---9 ligands 403 methanolcadd 442
lonlcradll 399---400 methanol 393
lonlcvalendes 76,79---KI seealsocomplexloru me1hylke1ones 535--4537
lonlsatlonenergtes 32- 3. 77,330 Uglu 169-70 methylme1hano:ne 504-5
3dblockelements 399,400-1 . 402 linedlagram 46 methylorange 129.130,374,457
measurtngandelectronlcconfiguratlon UquldpropeUants 107,108 MeJ,er,lo(har 187
36-4> Uquld.'l ($---71
thlrdpertodelements 191 molarmas.s 6--7
lonpolarlsatlon 81- 2 Uster.Joseph 435,436 molerularformulae ll,213.243
lithium 32,34 molerularfragments,analyslng 501
romplex 40}-ll lllhlumalumlnlumhydride 298 502- 5
contalnlngrovalembonds 140 Uthlumrecharseablecell:s 394 molerularlon.analyslng 50()
Iron 401 lock-and-keyhypothesls 168 molecularity 360
1.soelearlcpolnts 465 lonepalrs 47,52 molerularorbltal 46
1.soelecrronlcmolerulell/lons 56---7 anddlpoles 55
l.som,er:lsm 22()---{; low-densltypoly(ethen<.>)(LDPE) 262 masses 5---{;
lowexploslves 343 polarity >HJ
aldehydesandkeiones 296 lowresoluUonNMRspearoscopy Sll - 13 shapesof 5l - 3,2U- l3
alkanes 235-7 lubrtcatlon 86 slmpleseeslmplemolecules
alkenes 253,254
Index
..... ._,
andcompounds 8--10
h.tlofjen<:Glhnes
nucleu5 21
270-S.2')1) oxygen 40-1
oxl<btlan nwnber.i \,j()
andooocenln>tk>m 16--1 1 eledron-nudeu1dloUnce 30 re:ocllons 191- 2.193
ofgases 15 nylons 466-7,474---7 Oilygen---hydrogenbond 284---S
u.slnglnma55calrulat1oru l}--15 oil 102 oionelayerdepletlon 276-8
mon:nomlclons 75-7 cnideotlprocesslng 237--9 paperchromJtogrnphy(PC) 496-7
mooomcrs 262-3 oll-dropexperlmem 3,4 p,,ro- 420-1
disllngUlshlngbelweenadd!tlonand
condensaltonpolymers 490---2
..,_,
opUcall5omerl'lm 220.222,22}-6,410. par.,Oc'{amol 436,454
panlalcha'B"sepantlon 54
monoprollcodds/bueri 123 ofbltals 26.29.46 panl:l!pressum'l 182-3
mordanu 457 bonding In complex lom 404-S panlde..iz,, 161.1n
mosqukoes 431 eledronlcronfigunlioo 32-6 panlllonroefficleNs 376-9.496
mulllde'llt1tellgands ~ overl:ipot s7---{i3 P""""J,; 90
roollifuna~Jcompounds,predktln(j sublhells:andtheshapeaof j()-2 Paullexduslanprlndple 35
n!U'!lonsd 53J-4 otdcrofreactlan 3S3-4,3'.i6 pbkx:k 188
multiple bonds 50 fi~,on;lerre:ocllons 270-l,3S3-4,3~7 peptldebonds "64----S,48S
1n.1klple-rlngorer,es 419-,-20 :tndmoll'C\ll.U\ly 3t') pep!kle, 46f..---5,@5
n>.nOll'IClr'Cll 3 second-ordern,,u:tloru 'Dl,3S3-4 elea.roploresis 46s-6
narnralgas 102 IOU} 356 perceruageylekl 231-2
zcro-onlNreaa:lons 3S3-4 Perlod!cTable 1116---201
Nernst.w.ikhcr 368 organlccompounds 209--33 .l,dbloclcelement., 397-114
Ncrrutequa1lon 388-90 appearance 318 Group2 19}-S
ncutr..11.satlon,enrholpyrhangeof 100-1 fuoctlonal-grouptests 52ll--34.S3s-6 Group 17 202---fj
ncutr.ilsoloUons 369 modernfonn 187-8
ll\15S5pectromeUylOde!ermlneSU\ICtl.ll'e5 thlrdper1nd 188-93
Newlands.Jolin 187 perlnds 187---fj
nldreL-hydrlde(Nl\1H)cell,; 393-----i molecuhr5h:ipe 212- 13 petrrWl<'Ndlpole---dipoieforces 64
n1tr:11es 194.3'1._5
""
rumtng 217- 20
nltr.ulon 424-6.434 aolubllkylnw:ater 318 dabuffersoluclon 371-2
nnrogcn '0--1,195-6
nltrogcnoxtdes 197,198,2..0
1Ublliryandv:1.1lety 210-12
1ypesoffcnnulae 21}-17 ,.,.,,,
dunges ln and the Nerrut equa1lon
nltrousadd(nltrlc(lll)add) 456 organlcpolymerllglu-<>rnltllngdlodes cha118"slntltr.1.1lon 37}-S

nltryl caUon(nllronlumlon) 425 (OP-Ll!Do) 483 369-70
...,,.i..
nomcnclalure organlcreactions 2'D- 32
alcohol! 262-4 cakulallng)'lelds 231- 2 phc1111lphthalei11 129,130,374
aldchydesandketoo.l'l'l 296 mechanism, 228-30 phennls~,432-8,440-1.5.30
aJkallCI 235-7 re.igeN5forS3s-6 nonieocbture 432-3
alkcnes ~ l)'pe52Z7-8 prepllrlng 43'7
amine., 451-2 oipnlcsynthe,a S20--6 ,...._cr1oru; 43}-S.4.U
arenes 420-2 ch:insforS36-8 t('S(for 43S
arboxyllcaddsande,;ier,i J1J7 drug~S2J-8 phenyl 422
oomplcx\oN 4i07-tl Smplerm>lecules S20-2 phenybmine 4S}-4
tulogcnoalbnes 268-9 org,.nlc leots 32s---{i,S28-34,S3'Hi phen)iedurumlde ~-3
organic oompounds 217- 20 ortenta!lon 4V-9 phen)ielhene 470-1
phenols 432-3 phnsphoru,(V)chlor!de266,~
non-ayslalllne(amorphous)solld, 71.317 overvoltage 387 phnsphoru,trlhaHdl'l'l Z86
non-rcnewableenc'll)'sourcell 102.239---4(1 oxkbllo n t 36-S3, 2I7.22!! phOlochi'ntlcalreactlans 169-70
non-,1u ndard coodkkm, 386,388-90 alrohc>l'l 287--9. 302 phOlogr.iphy 169-70
Ntetmlnal 406 aldehyde,, 300 photoru 'D-8
nuck.-armagne1kresononce(NMR) cuboxyUcaclds 442 photmynthesls 342
spe,:uoscopy )00.507-18 sldechalnC-arenes 430 PI.A 481-1
lwuof 507-6 s11lroredm:re:oct1ons;redm:U:r.1tlons
c;ubon-13 5(8.510.516--18 Pbnd<'seqoalion 28.SOS
,,....,
oxldalioonuml>es:s(<nldatlan..at"") 79.00.
-"
lowandhlghm.!Olutlon 511 - 13 pull.nlsedpl:lttnomelecuode 383
proton 5()7-16 3delemenls ,1()2
nuclearpowcr 103 thlowlf:m,1on 148 pol.Jrbond 54
nuclclcaclds 65.66 pol.Jrlmeler 223
nucloophllcl! 221:1,<i55 mkhUveoddlllon 2(,() pol>ffl:illon 81 - 2
111.'eaisoligands mlcbtlvede vage 26o---l polrtty 54---{;
nudoophlllcaddklo n 2I7,'l97---fj mldei 192-3 pollution 197---fj. 240
nucloopllll(c5ub:!tltllllon 227 oxldi.<,!ngagem (oxldant) 107 IX)lyamldes 466---7,474---7
alcohol! 27';1,28$--7 oxontumlon 118-19 IX)lychloroethen<.'(PVC) 2(,3
545
Index
polyestel:5 446---7,474---{i propylam!ne 521- 2
poly(ethen<>) 262 pro,thel:lcgrouJliS 485
polymer.i 469-94
addltionsuaddltlonpolymer.s
pro(elns 48H
globular 167 ,,, _.,
renewableene'Bfsource:s
_
102, l0}--4,
biodegradable 481- 2 Le,elsofstrucrure 486--8 resonanceen.ergy 419

conden.sationsHroodensa!lonpolymer, structure48H rl'lardatlonfactor 497
conducllng 482- 3 pro(onNMRspectrosropy S,07- 16 reierulontlmes 499
cro,s-Unked 471HH pro(onnumber 23,189,190 re!lnal 253
disposal 263---4. 492- 3 orbltalen<.>rgYand 33--5 fl'\'er.slbleprocesses 335
dlstingulshlngbetweenadd!!lonand pro(OOS 21,22 rever.slblereactloru 172---3.174-5
conden.sationpolpners 490-2 donattngandacreptlng 123 seealsoequJUbrta
gh"'-'S 48J-.j pro(on-transterreactlons 124-5 rockelfuels 107-8,343,}'4
Kevlar 477--8 PTFE(polyte1ralluoroe1hene) 481 rolatlon 25---{)
PTIE 481 purification hindered 252- 3
polypepilded!alns 459 copper 152 rubber 471 - 3,478
polypepildes 485--8 water 206--7 rusting 388
polyprop<>ne 263 purlnemolerules 4m-S\l Rutherford,Emest 21
polyst}Tene(polyphenyle!hene) 263 purltydasubstance 131,133 sacrlfidalprotea!on 388
expand<>d 471 PVC(polychlOfOl'\hene) 263 sal!q,ilcadd 436
polyunsaturatedoUs 253 p)'rlm!dloemolecules 489--90 saltbrtdges 382---:3
pornltals 3(}---2. 34,35,36 quaruumtheory 29
posltlonall'lomerlsm 220,221 - 2 quatemaryammonlumsalts 455 moltenandelearolysts 392
posltlondequ!Hbrlum 173,--8 racemlcmlxmres 224-5,526,527 solubility 375---{)
moving 174---tl sampling 157-8
po1asslumd!d!romate{VJ) 287--9,300 radlcalsubstltutlonreact!ons 227,244--6,278 satura!edhydrocarbons 255
po1asslummanganate{VJI) 14H radloact!ve!sotopes 22
r,aactlonofalke11esw:l!h 26o---1 ratecoostaru 356---fl
tkratlons 316--17 ra!e-de!erm!nlngsteps 270-1,358 SBR 472 . 473
po1entlaldlfference 382 rateequatlon 356---fl secondaryalcohols 287---9
po1entlaleoc'BY 25. 26 ratesofreact!on 154--71,349-66 secondaryam!nes 451- 2
praclicaltechn!ques 316--28 catal)'S!sseecatalysts secondarycentres 247-9
acrlonofadd.s 32}-4 colUston theory 163--5 secondaryhalogenoalka!lell 268----9
appe,raoce Jl7- l8 cooceruratlonand 159-l. 351- 5,359--{,(J secondarystrucrureciprotoru 486-7
del..alonofgases 3lS-l9 effectofHght 169-70 SecondL:iwo(Tu.ermodynamlC'l 335
flametesl.'l 319----20 factor.saffectlng 159-{il,351 second-orderreactloru 271,353-4
organ!ctests J2H halogenoalkanes 272 second-rowelements 46-7
predpltaUonr,aaCTlons 320-2. 324-5 in,rreastng 159-63 selectt,edlscharge 392
solubilltylnwa!er 318 measuring l5H,35(H Sl.'OatUlomers 526
thermometrlcmeasuremems 316 reactlonme<:han!sms 351,358,--{;1 sequestering 409
tkratlons J16--17 r,aactlonprofiles 155,361- 2 shells 29
predplta!lonreoclions 120.121 elearonkronfiguratlon 32---{i
foranloru 324---5 amourud 16o shleldlnsbylnnersheUs 32- 5
forcatloru Jb}---2 excess 352-4 subshellsandtheshapesofoJbltals 3(}---2
pn,fixes 219 klne!lcall)'stable 155 side chains
pressure thermodynamlcall)'stable 155 alkylbeni.enes 429-30
changlngandpo,ltlondequUlbrium react!onfeas!billtJ' 386---.s amlnoactds 463-4
reactlonme<:han!sms 351,35&--{il s!gnlficantfigures 5
"'
equlllbrtumrons1amK,,
gases 89---90,94---5
182---3 react!onprotiles 155,361- 2
reagentsforoqpn!creactlons 535---{)
sUverhaUde:'l Z&,----7
sUvermlrror 301
prlmaryaJCOOOls 287---9 recepmr.s 524---5 sUvernltrate 2&,----7,324
prlmaryam!nes 451- 2 rechargeablebanerles 393---4 slmplemolecularlan!ces 72--4
prlmarycentrell 247---9 rec)'cUng 264 slmplemoleculB'l
prlmaryhalogenoalkanes 268---9 redoxpo1e11Uals 384.385 chemlcalbondlng 44---I
prlmarystructureofpro:eins 486 redoxreactloos 120,121- 2. 137-8 findlngbondl.'tlthalpyln 114-15
prodrugs 527---tl halandngll'doxequatloru 141--4 syrnhestsoforgan!ccompounds 520-2
promoler.s 362- 3 redoxtltratlort'i 144---9 skeletalformulae 214-17,218
propanal S-03 reduction 1.36-53,227,228 S,.lreactlon 270-1,272
propanenltrlle 274 dcarl:>on)'lcoo1pounds 290,298 s,.ireactlOfl 271.272
propanone S-0~3 soap 312- 13
reactlonwlthlodlne 351---{i,358-{,() re-fo1111lngstratght-chainalkanes 239 sodlum 41,284
propeUants 107-8,343,}'4 relatlveatcm!cmass 5---{) sodlumboroh)'drtde 298
propene 470 relatlvefommlamass 9 sodlumcarbonaTe 308,309
Index
sodlumchlorlde 149--50 smedd!vls!on 161,1n !f'ttlaryamlnes 451- 2
sodlumhydrogencaJbona!e 110,308,309 Sla!estmbols 12 !f'ttlarycentres 247---9
sodlumhydroxlde Sla!esofmaner 69--71.98 !f'ttlaryhalogenoalkanes 26/l.--9
pn,dpka!lonreacUonsforca!lon.s 320 seea/sogases;Uqulds;soUds !f'ttlaryS!ructuredpro:e!ns 487----tl
321 - 2 Terylene 446-7
reacUonwtthchlor!ne 204 Siem-suffixes 218-19 ceslas 508
reacUonswlthcaJboxyUcadds 308,309 Slereochem!cal formulae 213,214 tetramethylsUane(fM5) 510----11
solarpanels 103 Slereolsomerlsm 220,222,-{i,410 thalldOfll!detragedy 226
solkl., 69--71 S!em-G<>dachexperlmem 35 theoretlcalyleld 231 - 2
!onlcbond!ngsee!onlcbond!ng Sloichlometrtcequat!on 350,351.352 thermal crack!ng 239
la!tlcesseela!tlces Sloichlometry thermal decomposlt!on 194,204.344-5
solldpropeUam, 107,108 calculatlon.slnvolvlng 17- 18
solubU!ty tkrat!onsandfindlng 128,132.144 thermodynam!caUystablereactants 155
dsalts 375--{, Slratosphere n6--7 thermodynamics I~
separat!onofam!nesandflOll-baslc Slrength thermometrlcrneasurements 316
compounds 454 add strength 440----2 thermosettlngrooden.sat!onpolymers 479
sulfate:sandhydroxldes 194,}6--{i danlonlrlanlre 83 thermo61a!lcwa!erbaths 352
tes!lnsfor!nwa!er 318 Slronsadds 126,370 Thlele,Johannes 416
solubU!typroducr 375--{, Slrongbases 370 Thi<>les!ructureofbenzene 416,417
Slructuralformulae 213 Th!<>mann'sfuelcalorlmeter lo6
emhalpychangedsolm!on 100. 333 Slructural!somerism 220----2,409-10 th!nlayerchromamgraphy(TLC) 498
mole:'land<nnrentra!lons 16--17 th!osulfa!e!on 146--7
solwnteX!ra<llon 3n-s :nom!c 20-----43
sol,ents 127, 360 deductng1LSlngfuncUonal-group'SI.S Th!rdLawoflbem1odynam!cs 336
lmmlsctble 376---9 531----3 th!rdperlodelements 188----93
sorbltals 30----2,33,35,36 pro:elns 48';-8
splorbkals 58 sub-a!om!cpan!d,_,s 20----2 Thomson,JJ . 21
splorbkals 58 seealso<>l<'<lrons,neutrons,pro:ons three-waycatalytlcconvener.i 166----7
sparlnglysolublesalts 389 subsheUs 3(}----2 thymine 489---90
spedfichea!capad!y 99 substku!edareoes 427----9 tldalpower 103
spectator!ons 122 substku!lonreacUons 227. 228 tltratlons 316--17,373----5
spectroscope 27 phenols 434-----5 add-base 127- 34. 316,373-5
sldechalnsdareoes 429---3() back 133---4
atom!cabsorp!lon 27 successl.-elon!sat!onenergle'l 37----tl CUJV<'S 373----5
lnfrared 505-7 suffixes 218-19 !ndlcator.i 129,130,373-----4
NMR 360,507- 18 sulfa!<>lon 78 redox 144----9
sulf:nes 194, 345--{, Tollen.s'reagent 301
<>learons 35 sulfur 36 totalorderolreactlon 356
nucleons 507-B sulfurdlchlorldeoxlde 286,309 tr:msklonmetals 398
spin-,;pincoupl!ng 512 sulfurdloxlde 196----8. 240 catalytlcpropenle:s 412- 13
spll!Ungpauern.s 511 ---- 13 actd rain 197----t!,363 seea/so3dblock<>lements
spontaoeousprocesses 335 sulfurlcacld 1-r,, 196----8,323-----4 tr:ms!Uon61a!es 'r/1 , 361- 2
Slab!Usa!lon<>ne'Bf 419 react!onwtthalrohols 286-7 transla!lon 2<;--{i,71
Slablllly rea<l!onofhalld<>!oruwlthroocentrated tnms-plat!n 410----ll
benzene 418-19 206 trt-lodomethane(lodofonn)reactlon 289,
superconductor,; 333
o'Ban!ccompounds 211 - 12 'superglue' 483 trtplebonds 50,6o---1
th<>m10dynamlc 155 surfac<>tenslon 73 Tswt,Mlkhall 495
Slabllllyconstaru 405--{, symbols 7-----8 cwo-d!menslonalchromatography 497
Slandardaunosphere SO e:x!end!ngtolndudelsornpell 23 typelrondens:nlonpolymers 474-----5
Slandardrelle.m.f. 382.38';-8 syruhetlcpolyamldes (nylons) 466-7. 474-----7 !ypellcondensat!onpolymer.i 475
Nernstequat!on 38&--90 syruhetkrubber 472- 3 unkrells 71
1LSlnsiorneasuref<>as!bilkydreactloru !f'mperature unsnura!edhydrocarbons 255
"""
absolmetemperaturescale 25,91 ----2
Slandard<>lectrodepaentlals 384 , 385 behiourdgasesand W-S0,91 . 94-----5 ,-aLence-shellelectron-pa!r repuls!ontheory
Slandardenthalpychange chansesandposlt!ondequmbrlum (VSF..PRtheory) 51----3
d:nomlsa!lon ll}----15 176--7 nlence-shellelearons 46--7
rneasurlnsiemperamrechanges 99----101
dforma!lon 110----11 andra!f'solreactlon 161 ontheedgedadlamoodcrysial 75
Slandardform 4-----5 varlatlonofGlbbsfree<>ne'Bfwlth ,-an der\Vaals' forces 64
Slandardhydrogenelectrode(5HE) 383 338----9 ,-apodsaUon. <>tUhalpychanged 113,
Slandardsolutlon 127, 128 !f'ttlaryalcohols 287---9 114-----15
547
Index
veryh!ghff'solut!onmassspectromeuy 500 purlflc:nlon 2o6---7 weakactds 126
vibration 25--6,71 reactlonsciacylchlorklesw:lth 443---4 carboxyllcactdsseecaibox}11radds
viscosity 235 "'actlonsciamldes"'1th 46o dissociation 367---il
reactions ci Group 2 elelll<'1lts "'ith wind power 103
gases 89----90,91,92,95 193---4 Wohler,Frleddch 210
gasesg!nnoff 156 reactlonsciox:ldesw!th 192---3 wordequatloru 12
vulcanlsa!lon 471. 472. 478 reactlonscithlrdpertodelementswtth yeas! 290---1
water 65,66. 67,123. 376---7 191- 2 ytelds,lnorgan!cr<'llctlon.s 231- 2
analyslnghardnesscitapwater 409 testlngsolubilltyln 318 z.ero..orderreaclloru 353---4
effecr.,dhydrogenbondlng 72---4 waterdcrysiaUlsatlon 131,132 ZWITterloru 462
lon!cproductd 368---9 watervapour 242 zymase 168
phases (;f}--70 wavepower 103

Cambridge International As and A Level Chemistry

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International AS and A Level !i; f!.~!~!.!?o~o~

Gc1;erphoroby C> km!raga}.i - ForoUa

Topic 5 Energy changes in chemistry ......................................................................................................................... 97

Topic 6 Acids and bases .......................................................................................................................................... 118

Topic 7 Oxida tion and reduction ............................................................................................................................. 136

Topic& Rates of reactton .............................................................................................................................. l i 4

Topic9 Equilibria ................................................................................................................................................... 172

Topi c 10 Periodi city ..................................................................................................................... 186

Topi c 11 Group 17 .. . ....... 202

Topi c 12 Introdu ction to orga nic chemist ry ............................................................................................................. 209

Topic 13 Alka nes .................................................................................................................................................... 234

Topic 14 Alkenes 251

Topi c 15 Halogenoalkanes 267

Topi c 16 Alcohols ................................................................................................................................................... 281

Topic 17 Aldehydes a nd ketones ............................................................................................................................. 294

Topic 18 Carboxylic acids and esters 305

Advanced practical skill s (Paper 3)

Topic 19 Practica l work .. . ............... 316

Topic 22 Quantita tive equili bria....................................................................................... 367

Topic 23 Electroc hemistry .. ........ .. ...... .. 381

Topic 24 The 3d block.. . .................................... 397

Topic 25 Arenes and phenols . .. 41 5

Topic 27 Amines, amides and amino acids 449

To pic 28 Addition and condensation polymers 469

Topic 29 Techniques of analysis . . ...................... 495

chcmistiy is based on the very simplest idc-a of e le.:trostatic,i i-,owlMC~ml:lridgeLe.J.rn irigoutcomesarecoveredbytlle30TOpics

1 Chemical formulae and moles

Figure 1.2 Sameexamplesofthel'Cllnomic,

Classifying matter - elements, compounds and

1.2 Intensive and extensive properties

The oil-drop experiment

=l.4 x 10-7 cm ( l.4x10- 9 m)

1.3 The sizes of atoms and molecules

Sign ificant figures

1.4 The masses of atoms and molecules

1.5 The mole

Fig u re 1.5 O!\!'-tenthofamoleofeach

a Al2.7g b S3.2g(~mo1S.) c 8r8.0g(~moj8r,) d Pb20.7g

relative atomic mass of magnesium = 24 .0

-"'M- ""' {11

number of atoms~ L x number of moles

1.6 Atomic symbols and formulae

the symbol for hydrogen is H

thefonnubdsodiumnitrnteisNaN03 (ooe,;ocl;umion. Na. combined \\ithonenitrate

1.7 Moles and compounds

M, = 2A.(C) + 6A,(H) + A.(O)

Flgure 1.6 One-tenthofamoleof

a H,01 .Sg b K,cr,0,29. 4 g c: CuS04 5H,025.0g

~ 72.0 + 12.0 + 96.0

1.8 Empirical formulae and molecular

2 Divideeachofthefiguresobmined instep I bythesmallestofthosefigures

Calcu!a tetheempiric.alf0<mulaoleac:hol Answer

The mo lecula r fo rmulatellsustheactualnumberofatom1of&Khelementpresentin a

The conservation of mass

Flg ure 1.7 During theformabonollead(II)

lead(!]) nitrate + potassium iodide ----) solid lead(]]) + po1assium nitrate