Chemistery 11 (English Part II)

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redox reactions 235

Unit 7

redox reactions

Where there is oxidation, there is always reduction –


Chemistry is essentially a study of redox systems.

After studying this unit you will be


able to Chemistry deals with varieties of matter and change
of one kind of matter into the other. Transformation of
• identify redox reactions as a class
of reactions in which oxidation matter from one kind into another occurs through the
and reduction reactions occur various types of reactions. One important category of such
simultaneously; reactions is Redox Reactions. A number of phenomena,
• define the terms oxidation, both physical as well as biological, are concerned with
reduction, oxidant (oxidising redox reactions. These reactions find extensive use in
agent) and reductant (reducing pharmaceutical, biological, industrial, metallurgical and
agent); agricultural areas. The importance of these reactions is
• explain mechanism of redox apparent from the fact that burning of different types of
reactions by electron transfer fuels for obtaining energy for domestic, transport and
process;
other commercial purposes, electrochemical processes
• use the concept of oxidation for extraction of highly reactive metals and non-metals,
number to identify oxidant and manufacturing of chemical compounds like caustic
reductant in a reaction;
soda, operation of dry and wet batteries and corrosion of
• classify redox reaction into metals fall within the purview of redox processes. Of late,
combination (synthesis),
decomposition, displacement
environmental issues like Hydrogen Economy (use of
and disproportionation liquid hydrogen as fuel) and development of ‘Ozone Hole’
reactions; have started figuring under redox phenomenon.
• suggest a comparative order
7.1 CLASSICAL IDEA OF REDOX REACTIONS –
among various reductants and
oxidants; OXIDATION AND REDUCTION REACTIONS
• balance chemical equations Originally, the term oxidation was used to describe the
using (i) oxidation number addition of oxygen to an element or a compound. Because
(ii) half reaction method; of the presence of dioxygen in the atmosphere (~20%),
• lear n the concept of redox many elements combine with it and this is the principal
reactions in terms of electrode reason why they commonly occur on the earth in the
processes. form of their oxides. The following reactions represent
oxidation processes according to the limited definition of
oxidation:
2 Mg (s) + O2 (g) → 2 MgO (s) (7.1)
S (s) + O2 (g) → SO2 (g) (7.2)

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236 chemistry

In reactions (7.1) and (7.2), the elements broadened these days to include removal
magnesium and sulphur are oxidised on of oxygen/electronegative element from
account of addition of oxygen to them. a substance or addition of hydrogen/
Similarly, methane is oxidised owing to the electropositive element to a substance.
addition of oxygen to it. According to the definition given above,
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l) (7.3) the following are the examples of reduction
processes:
A careful examination of reaction (7.3) in
which hydrogen has been replaced by oxygen 2 HgO (s) 2 Hg (l) + O2 (g) (7.8)
prompted chemists to reinterpret oxidation (removal of oxygen from mercuric oxide )
in terms of removal of hydrogen from it and, 2 FeCl3 (aq) + H2 (g) →2 FeCl2 (aq) + 2 HCl(aq)
therefore, the scope of term oxidation was (7.9)
broadened to include the removal of hydrogen
from a substance. The following illustration is (removal of electronegative element, chlorine
another reaction where removal of hydrogen from ferric chloride)
can also be cited as an oxidation reaction. CH2 = CH2 (g) + H2 (g) → H3C – CH3 (g) (7.10)
(addition of hydrogen)
2 H2S(g) + O2 (g) → 2 S (s) + 2 H2O (l) (7.4)
2HgCl2 (aq) + SnCl2 (aq) → Hg2Cl2 (s)+SnCl4 (aq)
As knowledge of chemists grew, it was
natural to extend the term oxidation for (7.11)
reactions similar to (7.1 to 7.4), which do (addition of mercury to mercuric chloride)
not involve oxygen but other electronegative In reaction (7.11) simultaneous oxidation
elements. The oxidation of magnesium with of stannous chloride to stannic chloride is
fluorine, chlorine and sulphur etc. occurs also occurring because of the addition of
according to the following reactions : electronegative element chlorine to it. It was
soon realised that oxidation and reduction
Mg (s) + F2 (g) → MgF2 (s) (7.5)
always occur simultaneously (as will be
Mg (s) + Cl2 (g) → MgCl2 (s) (7.6) apparent by re-examining all the equations
given above), hence, the word “redox” was
Mg (s) + S (s) → MgS (s) (7.7) coined for this class of chemical reactions.
Incorporating the reactions (7.5 to Problem 7.1
7.7) within the fold of oxidation reactions
In the reactions given below, identify
encouraged chemists to consider not only
the species undergoing oxidation and
the removal of hydrogen as oxidation, but
reduction:
also the removal of electropositive elements
as oxidation. Thus the reaction : (i) H2S (g) + Cl2 (g) → 2 HCl (g) + S (s)

2K4 [Fe(CN)6](aq) + H2O2 (aq) →2K3[Fe(CN)6](aq) (ii) 3Fe3O4 (s) + 8 Al (s) → 9 Fe (s)
+ 2 KOH (aq) + 4Al2O3 (s)
is interpreted as oxidation due to the removal (iii) 2 Na (s) + H2 (g) → 2 NaH (s)
of electropositive element potassium from
Solution
potassium ferrocyanide before it changes to
potassium ferricyanide. To summarise, the (i) H 2 S is oxidised because a more
term “oxidation” is defined as the addition electronegative element, chlorine is added
of oxygen/electronegative element to to hydrogen (or a more electropositive
a substance or removal of hydrogen/ element, hydrogen has been removed
electropositive element from a substance. from S). Chlorine is reduced due to
addition of hydrogen to it.
In the beginning, reduction was considered
as removal of oxygen from a compound. (ii) Aluminium is oxidised because
However, the term reduction has been oxygen is added to it. Ferrous ferric oxide

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redox reactions 237

For convenience, each of the above


(Fe3O4) is reduced because oxygen has
processes can be considered as two separate
been removed from it.
steps, one involving the loss of electrons
(iii) With the careful application of the and the other the gain of electrons. As an
concept of electronegativity only we illustration, we may further elaborate one of
may infer that sodium is oxidised and these, say, the formation of sodium chloride.
hydrogen is reduced.
2 Na(s) → 2 Na+(g) + 2e–
Reaction (iii) chosen here prompts us to
think in terms of another way to define Cl2(g) + 2e– → 2 Cl–(g)
redox reactions. Each of the above steps is called a half
reaction, which explicitly shows involvement
7.2 REDOX REACTIONS IN TERMS OF of electrons. Sum of the half reactions gives
ELECTRON TRANSFER REACTIONS the overall reaction :
We have already learnt that the reactions
2 Na(s) + Cl2 (g) → 2 Na+ Cl– (s) or 2 NaCl (s)
2Na(s) + Cl2(g) → 2NaCl (s) (7.12)
Reactions 7.12 to 7.14 suggest that half
4Na(s) + O2(g) → 2Na2O(s) (7.13) reactions that involve loss of electrons are
2Na(s) + S(s) → Na2S(s) (7.14) called oxidation reactions. Similarly, the
are redox reactions because in each of these half reactions that involve gain of electrons
reactions sodium is oxidised due to the addition are called reduction reactions. It may not
of either oxygen or more electronegative be out of context to mention here that the
element to sodium. Simultaneously, chlorine, new way of defining oxidation and reduction
oxygen and sulphur are reduced because to has been achieved only by establishing a
each of these, the electropositive element correlation between the behaviour of species
sodium has been added. From our knowledge as per the classical idea and their interplay
of chemical bonding we also know that sodium in electron-transfer change. In reactions (7.12
chloride, sodium oxide and sodium sulphide to 7.14) sodium, which is oxidised, acts as
are ionic compounds and perhaps better a reducing agent because it donates electron
written as Na+Cl– (s), (Na+)2O2–(s), and (Na+)2 to each of the elements interacting with it and
S2–(s). Development of charges on the species thus helps in reducing them. Chlorine, oxygen
produced suggests us to rewrite the reactions and sulphur are reduced and act as oxidising
(7.12 to 7.14) in the following manner : agents because these accept electrons from
sodium. To summarise, we may mention that
Oxidation : Loss of electron(s) by any species.
Reduction : Gain of electron(s) by any species.
Oxidising agent : Acceptor of electron(s).
Reducing agent : Donor of electron(s).

Problem 7.2 Justify that the reaction:


2 Na(s) + H2(g) → 2 NaH (s) is a redox
change.
Solution
Since in the above reaction the compound
formed is an ionic compound, which may
also be represented as Na+H– (s), this
suggests that one half reaction in this
process is :
2 Na (s) → 2 Na+(g) + 2e–

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238 chemistry

and the other half reaction is: At this stage we may investigate the state
H2 (g) + 2e– → 2 H–(g) of equilibrium for the reaction represented by
equation (7.15). For this purpose, let us place
This splitting of the reaction under a strip of metallic copper in a zinc sulphate
examination into two half reactions solution. No visible reaction is noticed and
automatically reveals that here sodium attempt to detect the presence of Cu2+ ions
is oxidised and hydrogen is reduced, by passing H2S gas through the solution to
therefore, the complete reaction is a produce the black colour of cupric sulphide,
redox change. CuS, does not succeed. Cupric sulphide has
such a low solubility that this is an extremely
7.2.1 Competitive Electron Transfer
sensitive test; yet the amount of Cu2+ formed
Reactions
cannot be detected. We thus conclude that
Place a strip of metallic zinc in an aqueous
the state of equilibrium for the reaction (7.15)
solution of copper nitrate as shown in Fig.
greatly favours the products over the reactants.
7.1, for about one hour. You may notice
that the strip becomes coated with reddish Let us extend electron transfer reaction
metallic copper and the blue colour of the now to copper metal and silver nitrate solution
solution disappears. Formation of Zn2+ ions in water and arrange a set-up as shown in
among the products can easily be judged Fig. 7.2. The solution develops blue colour
when the blue colour of the solution due to due to the formation of Cu2+ ions on account
Cu2+ has disappeared. If hydrogen sulphide of the reaction:
gas is passed through the colourless solution
containing Zn2+ ions, appearance of white zinc
sulphide, ZnS can be seen on making the
solution alkaline with ammonia.
The reaction between metallic zinc and the (7.16)
aqueous solution of copper nitrate is :
Here, Cu(s) is oxidised to Cu 2+ (aq) and
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) (7.15)
Ag+(aq) is reduced to Ag(s). Equilibrium greatly
In reaction (7.15), zinc has lost electrons favours the products Cu2+ (aq) and Ag(s).
to form Zn2+ and, therefore, zinc is oxidised. By way of contrast, let us also compare
Evidently, now if zinc is oxidised, releasing the reaction of metallic cobalt placed in nickel
electrons, something must be reduced, sulphate solution. The reaction that occurs
accepting the electrons lost by zinc. Copper here is :
ion is reduced by gaining electrons from the zinc.
Reaction (7.15) may be rewritten as :

(7.17)

Fig. 7.1 Redox reaction between zinc and aqueous solution of copper nitrate occurring in a beaker.

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redox reactions 239

Fig. 7.2 Redox reaction between copper and aqueous solution of silver nitrate occurring in a beaker.

At equilibrium, chemical tests reveal that both However, as we shall see later, the charge
Ni2+(aq) and Co2+(aq) are present at moderate transfer is only partial and is perhaps better
concentrations. In this case, neither the described as an electron shift rather than a
reactants [Co(s) and Ni2+(aq)] nor the products complete loss of electron by H and gain by
[Co2+(aq) and Ni (s)] are greatly favoured. O. What has been said here with respect
This competition for release of electrons to equation (7.18) may be true for a good
incidently reminds us of the competition for number of other reactions involving covalent
release of protons among acids. The similarity compounds. Two such examples of this class
suggests that we might develop a table in of the reactions are:
which metals and their ions are listed on the H2(s) + Cl2(g) → 2HCl(g) (7.19)
basis of their tendency to release electrons and,
just as we do in the case of acids to indicate
CH 4(g) + 4Cl2(g) → CCl4(l) + 4HCl(g) (7.20)
the strength of the acids. As a matter of fact
we have already made certain comparisons. In order to keep track of electron shifts
By comparison we have come to know that in chemical reactions involving formation
zinc releases electrons to copper and copper of covalent compounds, a more practical
releases electrons to silver and, therefore, method of using oxidation number has
the electron releasing tendency of the metals been developed. In this method, it is always
is in the order: Zn>Cu>Ag. We would love to assumed that there is a complete transfer
make our list more vast and design a metal of electron from a less electronegative atom
activity series or electrochemical series. to a more electonegative atom. For example,
The competition for electrons between various we rewrite equations (7.18 to 7.20) to show
metals helps us to design a class of cells, charge on each of the atoms forming part of
named as Galvanic cells in which the chemical the reaction :
reactions become the source of electrical 0 0 +1 –2

energy. We would study more about these 2H2(g) + O2(g) → 2H2O (l) (7.21)
cells in Class XII. 0 0 +1 –1
H2 (s) + Cl2(g) → 2HCl(g) (7.22)
7.3 OXIDATION NUMBER
–4+1 0 +4 –1 +1 –1
A less obvious example of electron transfer is
realised when hydrogen combines with oxygen CH4(g) + 4Cl2(g) → CCl4(l) +4HCl(g) (7.23)
to form water by the reaction: It may be emphasised that the assumption
2H2(g) + O2 (g) → 2H2O (l) (7.18) of electron transfer is made for book-keeping
Though not simple in its approach, yet purpose only and it will become obvious at
we can visualise the H atom as going from a a later stage in this unit that it leads to the
neutral (zero) state in H2 to a positive state in simple description of redox reactions.
H2O, the O atom goes from a zero state in O2 Oxidation number denotes the oxidation
to a dinegative state in H2O. It is assumed that state of an element in a compound
there is an electron transfer from H to O and ascertained according to a set of rules
consequently H2 is oxidised and O2 is reduced. formulated on the basis that electron pair

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240 chemistry

in a covalent bond belongs entirely to more bonding state of oxygen but this number
electronegative element. would now be a positive figure only.
It is not always possible to remember or 4. The oxidation number of hydrogen is +1,
make out easily in a compound/ion, which except when it is bonded to metals in binary
element is more electronegative than the compounds (that is compounds containing
other. Therefore, a set of rules has been two elements). For example, in LiH, NaH,
formulated to determine the oxidation and CaH2, its oxidation number is –1.
number of an element in a compound/ion. 5. In all its compounds, fluorine has an
If two or more than two atoms of an element oxidation number of –1. Other halogens (Cl,
are present in the molecule/ion such as Br, and I) also have an oxidation number
Na2S2O3/Cr2O72–, the oxidation number of the of –1, when they occur as halide ions in
atom of that element will then be the average their compounds. Chlorine, bromine and
of the oxidation number of all the atoms of iodine when combined with oxygen, for
that element. We may at this stage, state the example in oxoacids and oxoanions, have
rules for the calculation of oxidation number. positive oxidation numbers.
These rules are: 6. The algebraic sum of the oxidation number
of all the atoms in a compound must be
1. In elements, in the free or the uncombined
zero. In polyatomic ion, the algebraic sum
state, each atom bears an oxidation
of all the oxidation numbers of atoms of
number of zero. Evidently each atom in
the ion must equal the charge on the ion.
H2, O2, Cl2, O3, P4, S8, Na, Mg, Al has the
Thus, the sum of oxidation number of three
oxidation number zero. oxygen atoms and one carbon atom in the
2. For ions composed of only one atom, the carbonate ion, (CO3)2– must equal –2.
oxidation number is equal to the charge By the application of above rules, we can
on the ion. Thus Na+ ion has an oxidation find out the oxidation number of the desired
number of +1, Mg2+ ion, +2, Fe3+ ion, +3, element in a molecule or in an ion. It is clear
Cl– ion, –1, O2– ion, –2; and so on. In their that the metallic elements have positive
compounds all alkali metals have oxidation oxidation number and nonmetallic elements
number of +1, and all alkaline earth metals have positive or negative oxidation number.
have an oxidation number of +2. Aluminium The atoms of transition elements usually
is regarded to have an oxidation number of display several positive oxidation states. The
+3 in all its compounds. highest oxidation number of a representative
3. The oxidation number of oxygen in most element is the group number for the first
compounds is –2. However, we come two groups and the group number minus 10
across two kinds of exceptions here. (following the long form of periodic table) for
One arises in the case of peroxides and the other groups. Thus, it implies that the
superoxides, the compounds of oxygen in highest value of oxidation number exhibited
which oxygen atoms are directly linked to by an atom of an element generally increases
each other. While in peroxides (e.g., H2O2, across the period in the periodic table. In the
Na2O2), each oxygen atom is assigned an third period, the highest value of oxidation
oxidation number of –1, in superoxides number changes from 1 to 7 as indicated
(e.g., KO2, RbO2) each oxygen atom is below in the compounds of the elements.
assigned an oxidation number of –(½). A term that is often used interchangeably
The second exception appears rarely, i.e. with the oxidation number is the oxidation
when oxygen is bonded to fluorine. In state. Thus in CO2, the oxidation state of
such compounds e.g., oxygen difluoride carbon is +4, that is also its oxidation number
(OF2) and dioxygen difluoride (O2F2), the and similarly the oxidation state as well
oxygen is assigned an oxidation number as oxidation number of oxygen is – 2. This
of +2 and +1, respectively. The number implies that the oxidation number denotes the
assigned to oxygen will depend upon the oxidation state of an element in a compound.

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redox reactions 241

Group 1 2 13 14 15 16 17
Element Na Mg Al Si P S Cl
Compound NaCl MgSO4 AlF3 SiCl4 P4O10 SF6 HClO
Highest oxidation +1 +2 +3 +4 +5 +6 +7
number state of
the group element

The oxidation number/state of a metal in a The idea of oxidation number has been
compound is sometimes presented according invariably applied to define oxidation,
to the notation given by German chemist, reduction, oxidising agent (oxidant), reducing
Alfred Stock. It is popularly known as Stock agent (reductant) and the redox reaction. To
notation. According to this, the oxidation summarise, we may say that:
number is expressed by putting a Roman Oxidation: An increase in the oxidation
numeral representing the oxidation number
number of the element in the given substance.
in parenthesis after the symbol of the metal in
the molecular formula. Thus aurous chloride Reduction : A decrease in the oxidation
and auric chloride are written as Au(I)Cl and number of the element in the given substance.
Au(III)Cl3. Similarly, stannous chloride and Oxidising agent: A reagent which can
stannic chloride are written as Sn(II)Cl2 and increase the oxidation number of an element
Sn(IV)Cl4. This change in oxidation number in a given substance. These reagents are
implies change in oxidation state, which in called as oxidants also.
turn helps to identify whether the species Reducing agent: A reagent which lowers the
is present in oxidised form or reduced form. oxidation number of an element in a given
Thus, Hg2(I)Cl2 is the reduced form of Hg(II) Cl2. substance. These reagents are also called as
Problem 7.3 reductants.
Using Stock notation, represent the Redox reactions: Reactions which involve
following compounds :HAuCl4, Tl2O, FeO, change in oxidation number of the interacting
Fe2O3, CuI, CuO, MnO and MnO2. species.
Solution Problem 7.4
By applying various rules of calculating Justify that the reaction:
the oxidation number of the desired
element in a compound, the oxidation 2Cu2O(s) + Cu2S(s) → 6Cu(s) + SO2(g)
number of each metallic element in its is a redox reaction. Identify the species
compound is as follows: oxidised/reduced, which acts as an
HAuCl4 → Au has 3 oxidant and which acts as a reductant.
Tl2O → Tl has 1 Solution
FeO → Fe has 2 Let us assign oxidation number to each
Fe2O3 → Fe has 3 of the species in the reaction under
CuI → Cu has 1 examination. This results into:
CuO → Cu has 2 +1 –2 +1 –2 0 +4 –2
MnO → Mn has 2 2Cu2O(s) + Cu2S(s) → 6Cu(s) + SO2
MnO2 → Mn has 4
We therefore, conclude that in this
Therefore, these compounds may be reaction copper is reduced from +1 state
represented as: to zero oxidation state and sulphur is
HAu(III)Cl4, Tl2(I)O, Fe(II)O, Fe2(III)O3, oxidised from –2 state to +4 state. The
Cu(I)I, Cu(II)O, Mn(II)O, Mn(IV)O2. above reaction is thus a redox reaction.

Unit 7.indd 241 10/10/2022 10:37:04 AM


242 chemistry

here that all decomposition reactions are not


Further, Cu2O helps sulphur in Cu2S to
redox reactions. For example, decomposition
increase its oxidation number, therefore,
of calcium carbonate is not a redox reaction.
Cu(I) is an oxidant; and sulphur of Cu2S
+2 +4 –2 +2 –2 +4 –2
helps copper both in Cu2S itself and
Cu2O to decrease its oxidation number; CaCO3 (s) CaO(s) + CO2(g)
therefore, sulphur of Cu2S is reductant. 3. Displacement reactions
In a displacement reaction, an ion (or an
7.3.1 Types of Redox Reactions atom) in a compound is replaced by an ion
(or an atom) of another element. It may be
1. Combination reactions
denoted as:
A combination reaction may be denoted in
X + YZ → XZ + Y
the manner:
A+B → C Displacement reactions fit into two
Either A and B or both A and B must be in categories: metal displacement and non-metal
the elemental form for such a reaction to be displacement.
a redox reaction. All combustion reactions, (a) Metal displacement: A metal in a
which make use of elemental dioxygen, as well compound can be displaced by another metal
as other reactions involving elements other in the uncombined state. We have already
than dioxygen, are redox reactions. Some discussed about this class of the reactions
important examples of this category are: under section 7.2.1. Metal displacement
0 0 +4 –2 reactions find many applications in
C(s) + O2 (g) CO2(g) (7.24) metallurgical processes in which pure metals
are obtained from their compounds in ores. A
0 0 +2 –3
few such examples are:
3Mg(s) + N2(g) Mg3N2(s) (7.25)
+2 +6 –2 0 0 +2 +6 –2
–4+1 0 +4 –2 +1 –2
CuSO4(aq) + Zn (s) → Cu(s) + ZnSO4 (aq)
CH4(g) + 2O2(g) CO2(g) + 2H2O (l) (7.29)
2. Decomposition reactions +5 –2 0 0 +2 –2
V2O5 (s) + 5Ca (s) 2V (s) + 5CaO (s)
Decomposition reactions are the opposite
of combination reactions. Precisely, a (7.30)
decomposition reaction leads to the breakdown +4 –1 0 0 +2 –1
of a compound into two or more components TiCl4 (l) + 2Mg (s) Ti (s) + 2 MgCl2 (s)
at least one of which must be in the elemental
(7.31)
state. Examples of this class of reactions are:
+1 –2 0 0 +3 –2 0 +3 –2 0

2H2O (l) 2H2 (g) + O2(g) (7.26) Cr2O3 (s) + 2 Al (s) Al2O3 (s) + 2Cr(s)
(7.32)
+1 –1 0 0
In each case, the reducing metal is a
2NaH (s) 2Na (s) + H2(g) (7.27)
better reducing agent than the one that is
+1 +5 –2 +1 –1 0 being reduced which evidently shows more
2KClO3 (s) 2KCl (s) + 3O2(g) (7.28) capability to lose electrons as compared to
It may carefully be noted that there is no the one that is reduced.
change in the oxidation number of hydrogen (b) Non-metal displacement: The non-
in methane under combination reactions metal displacement redox reactions include
and that of potassium in potassium chlorate hydrogen displacement and a rarely occurring
in reaction (7.28). This may also be noted reaction involving oxygen displacement.

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redox reactions 243

All alkali metals and some alkaline earth Cu>Ag. Like metals, activity series also exists
metals (Ca, Sr, and Ba) which are very good for the halogens. The power of these elements
reductants, will displace hydrogen from cold as oxidising agents decreases as we move
water. down from fluorine to iodine in group 17 of the
0 +1 –2 +1 –2 +1 0 periodic table. This implies that fluorine is so
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g) reactive that it can replace chloride, bromide
(7.33) and iodide ions in solution. In fact, fluorine is
0 +1 –2 +2 –2 +1 0 so reactive that it attacks water and displaces
Ca(s) + 2H2O(l) → Ca(OH)2 (aq) + H2(g) the oxygen of water :
(7.34) +1 –2 0 +1 –1 0

Less active metals such as magnesium and 2H2O (l) + 2F2 (g) → 4HF(aq) + O2(g) (7.40)
iron react with steam to produce dihydrogen gas: It is for this reason that the displacement
0 +1 –2 +2 –2 +1 0
reactions of chlorine, bromine and iodine
using fluorine are not generally carried out in
Mg(s) + 2H2O(l) Mg(OH)2(s) + H2(g)
aqueous solution. On the other hand, chlorine
(7.35)
can displace bromide and iodide ions in an
0 +1 –2 +3 –2 0 aqueous solution as shown below:
2Fe(s) + 3H2O(l) Fe2O3(s) + 3H2(g) (7.36) 0 +1 –1 +1 –1 0
Many metals, including those which do not Cl2 (g) + 2KBr (aq) → 2 KCl (aq) + Br2 (l)
react with cold water, are capable of displacing (7.41)
hydrogen from acids. Dihydrogen from acids 0 +1–1 +1 –1 0
may even be produced by such metals which Cl2 (g) + 2KI (aq) → 2 KCl (aq) + I2 (s)
do not react with steam. Cadmium and tin are (7.42)
the examples of such metals. A few examples As Br2 and I2 are coloured and dissolve in CCl4,
for the displacement of hydrogen from acids can easily be identified from the colour of the
are: solution. The above reactions can be written
0 +1 –1 +2 –1 0
in ionic form as:
Zn(s) + 2HCl(aq) → ZnCl2 (aq) + H2 (g) 0 –1 –1 0
(7.37) Cl2 (g) + 2Br (aq) → 2Cl (aq) + Br2 (l) (7.41a)
– –

0 +1 –1 +2 –1 0 0 –1 –1 0
Mg (s) + 2HCl (aq) → MgCl2 (aq) + H2 (g) Cl2 (g) + 2I (aq) → 2Cl (aq) + I2 (s) (7.42b)
– –

(7.38) Reactions (7.41) and (7.42) form the basis


0 +1 –1 +2 –1 0
of identifying Br– and I– in the laboratory
Fe(s) + 2HCl(aq) → FeCl2(aq) + H2(g) through the test popularly known as ‘Layer
(7.39)
Test’. It may not be out of place to mention
Reactions (7.37 to 7.39) are used to here that bromine likewise can displace iodide
prepare dihydrogen gas in the laboratory. ion in solution:
Here, the reactivity of metals is reflected in 0 –1 –1 0
the rate of hydrogen gas evolution, which is Br2 (l) + 2I – (aq) → 2Br– (aq) + I2 (s) (7.43)
the slowest for the least active metal Fe, and
The halogen displacement reactions have
the fastest for the most reactive metal, Mg.
a direct industrial application. The recovery
Very less active metals, which may occur in
of halogens from their halides requires an
the native state such as silver (Ag), and gold
(Au) do not react even with hydrochloric acid. oxidation process, which is represented by:
2X– → X2 + 2e– (7.44)
In section (7.2.1) we have already discussed
that the metals – zinc (Zn), copper (Cu) and here X denotes a halogen element. Whereas
silver (Ag) through tendency to lose electrons chemical means are available to oxidise Cl–,
show their reducing activity in the order Zn> Br– and I–, as fluorine is the strongest oxidising

Unit 7.indd 243 10/10/2022 10:37:04 AM


244 chemistry

agent; there is no way to convert F– ions to F2 fluorine shows deviation from this behaviour
by chemical means. The only way to achieve when it reacts with alkali. The reaction that
F2 from F– is to oxidise electrolytically, the takes place in the case of fluorine is as follows:
details of which you will study at a later stage. 2 F2(g) + 2OH–(aq) → 2 F–(aq) + OF2(g) + H2O(l)
4. Disproportionation reactions (7.49)
Disproportionation reactions are a special type (It is to be noted with care that fluorine in
of redox reactions. In a disproportionation reaction (7.49) will undoubtedly attack water
reaction an element in one oxidation state to produce some oxygen also). This departure
is simultaneously oxidised and reduced. shown by fluorine is not surprising for us as
One of the r eacting substances in a we know the limitation of fluorine that, being
disproportionation reaction always contains the most electronegative element, it cannot
an element that can exist in at least three exhibit any positive oxidation state. This
oxidation states. The element in the form means that among halogens, fluorine does not
of reacting substance is in the intermediate show a disproportionation tendency.
oxidation state; and both higher and lower
oxidation states of that element are formed in Problem 7.5
the reaction. The decomposition of hydrogen Which of the following species, do not
peroxide is a familiar example of the reaction, show disproportionation reaction and
where oxygen experiences disproportionation. why ?
+1 –1 +1 –2 0 ClO–, ClO2–, ClO3– and ClO4–
2H2O2 (aq) → 2H2O(l) + O2(g) (7.45) Also write reaction for each of the species
Here the oxygen of peroxide, which is present that disproportionates.
in –1 state, is converted to zero oxidation state Solution
in O2 and decreases to –2 oxidation state in Among the oxoanions of chlorine listed
H2O. above, ClO4– does not disproportionate
Phosphorous, sulphur and chlorine because in this oxoanion chlorine is
undergo disproportionation in the alkaline present in its highest oxidation state that
medium as shown below : is, +7. The disproportionation reactions
0 –3 +1 for the other three oxoanions of chlorine
P4(s) + 3OH–(aq)+ 3H2O(l) → PH3(g) + 3H2PO2– are as follows:
(aq) +1 –1 +5
(7.46) 3ClO– → 2Cl– + ClO–3
0 –2 +2
+3 +5 –1
S8(s) + 12 OH (aq) → 4S (aq) + 2S2O32–(aq)
– 2–
6 ClO2– 4ClO3– + 2Cl–
+ 6H2O(l) +5 –1 +7
(7.47) 4ClO–3 → Cl– + 3 ClO4–
0 +1 –1
Cl2 (g) + 2 OH– (aq) → ClO– (aq) + Cl– (aq) + Problem 7.6
H2O (l) Suggest a scheme of classification of the
(7.48) following redox reactions
The reaction (7.48) describes the (a) N2 (g) + O2 (g) → 2 NO (g)
formation of household bleaching agents.
The hypochlorite ion (ClO –) formed in the (b) 2Pb(NO3)2(s) → 2PbO(s) + 4 NO2 (g) +
reaction oxidises the colour-bearing stains O2 (g)
of the substances to colourless compounds. (c) NaH(s) + H2O(l) → NaOH(aq) + H2 (g)
It is of interest to mention here that whereas (d) 2NO2(g) + 2OH–(aq) → NO2–(aq) +
bromine and iodine follow the same trend NO3– (aq)+H2O(l)
as exhibited by chlorine in reaction (7.48),

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redox reactions 245

Solution reaction (c), hydrogen of water has been


In reaction (a), the compound nitric displaced by hydride ion into dihydrogen
oxide is formed by the combination of gas. Therefore, this may be called as
the elemental substances, nitrogen and displacement redox reaction. The reaction
oxygen; therefore, this is an example (d) involves disproportionation of NO2
of combination redox reactions. The (+4 state) into NO2– (+3 state) and NO3–
reaction (b) involves the breaking down
(+5 state). Therefore reaction (d) is an
of lead nitrate into three components;
therefore, this is categorised under example of disproportionation redox
decomposition redox reaction. In reaction.

The Paradox of Fractional Oxidation Number


Sometimes, we come across with certain compounds in which the oxidation number of a particular
element in the compound is in fraction. Examples are:
C3O2 [where oxidation number of carbon is (4/3)],
Br3O8 [where oxidation number of bromine is (16/3)]
and Na2S4O6 (where oxidation number of sulphur is 2.5).
We know that the idea of fractional oxidation number is unconvincing to us, because electrons
are never shared/transferred in fraction. Actually this fractional oxidation state is the average
oxidation state of the element under examination and the structural parameters reveal that the
element for whom fractional oxidation state is realised is present in different oxidation states.
Structure of the species C3O2, Br3O8 and S4O62– reveal the following bonding situations:

+2 0 +2
O = C = C*= C = O
Structure of C3O2
(carbon suboxide)

Structure of Br3O8 (tribromooctaoxide) Structure of S4O62– (tetrathionate ion)


The element marked with asterisk in each species is exhibiting the different oxidation
state (oxidation number) from rest of the atoms of the same element in each of the species.
This reveals that in C3O2, two carbon atoms are present in +2 oxidation state each, whereas
the third one is present in zero oxidation state and the average is 4/3. However, the realistic
picture is +2 for two terminal carbons and zero for the middle carbon. Likewise in Br3O8, each
of the two terminal bromine atoms are present in +6 oxidation state and the middle bromine
is present in +4 oxidation state. Once again the average, that is different from reality, is
16/3. In the same fashion, in the species S4O62–, each of the two extreme sulphurs exhibits oxidation
state of +5 and the two middle sulphurs as zero. The average of four oxidation numbers of sulphurs
of the S4O62– is 2.5, whereas the reality being + 5,0,0 and +5 oxidation number respectively for
each sulphur.
We may thus, in general, conclude that the idea of fractional oxidation state should be taken
with care and the reality is revealed by the structures only. Further, whenever we come across
with fractional oxidation state of any particular element in any species, we must understand that
this is the average oxidation number only. In reality (revealed by structures only), the element in
that particular species is present in more than one whole number oxidation states. Fe3O4, Mn3O4,
Pb3O4 are some of the other examples of the compounds, which are mixed oxides, where we come
across with fractional oxidation states of the metal atom. However, the oxidation states may be in
fraction as in O2+ and O2– where it is +½ and –½ respectively.

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246 chemistry

(a) Oxidation Number Method: In writing


Problem 7.7 equations for oxidation-reduction reactions,
Why do the following reactions proceed just as for other reactions, the compositions and
differently ? formulas must be known for the substances
Pb3O4 + 8HCl → 3PbCl2 + Cl2 + 4H2O and that react and for the products that are
formed. The oxidation number method is now
Pb3O4 + 4HNO3 → 2Pb(NO3)2 + PbO2 +
best illustrated in the following steps:
2H2O
Solution Step 1: Write the correct formula for each
reactant and product.
Pb 3 O 4 is actually a stoichiometric
Step 2: Identify atoms which undergo
mixture of 2 mol of PbO and 1 mol of
change in oxidation number in the reaction
PbO2. In PbO2, lead is present in +4
by assigning the oxidation number to all
oxidation state, whereas the stable
elements in the reaction.
oxidation state of lead in PbO is +2. PbO2
thus can act as an oxidant (oxidising Step 3: Calculate the increase or decrease
agent) and, therefore, can oxidise Cl– ion in the oxidation number per atom and for
of HCl into chlorine. We may also keep in the entire molecule/ion in which it occurs. If
these are not equal then multiply by suitable
mind that PbO is a basic oxide. Therefore,
number so that these become equal. (If you
the reaction
realise that two substances are reduced and
Pb3O4 + 8HCl → 3PbCl2 + Cl2 + 4H2O nothing is oxidised or vice-versa, something
can be splitted into two reactions namely: is wrong. Either the formulas of reactants or
2PbO + 4HCl → 2PbCl2 + 2H2O products are wrong or the oxidation numbers
have not been assigned properly).
(acid-base reaction)
+4 –1 +2 0
Step 4: Ascertain the involvement of ions if
PbO2 + 4HCl → PbCl2 + Cl2 +2H2O the reaction is taking place in water, add H+ or
OH– ions to the expression on the appropriate
(redox reaction)
side so that the total ionic charges of reactants
Since HNO3 itself is an oxidising agent and products are equal. If the reaction is
therefore, it is unlikely that the reaction carried out in acidic solution, use H+ ions in
may occur between PbO 2 and HNO 3. the equation; if in basic solution, use OH– ions.
However, the acid-base reaction occurs Step 5 : Make the numbers of hydrogen
between PbO and HNO3 as: atoms in the expression on the two sides
2PbO + 4HNO3 → 2Pb(NO3)2 + 2H2O equal by adding water (H2O) molecules to the
It is the passive nature of PbO2 against reactants or products. Now, also check the
HNO3 that makes the reaction different number of oxygen atoms. If there are the same
from the one that follows with HCl. number of oxygen atoms in the reactants and
products, the equation then represents the
7.3.2 Balancing of Redox Reactions balanced redox reaction.
Two methods are used to balance chemical Let us now explain the steps involved in
equations for redox processes. One of these the method with the help of a few problems
methods is based on the change in the given below:
oxidation number of reducing agent and the Problem 7.8
oxidising agent and the other method is based
Write the net ionic equation for the
on splitting the redox reaction into two half
reaction of potassium dichromate(VI),
reactions — one involving oxidation and the
K2Cr2O7 with sodium sulphite, Na2SO3,
other involving reduction. Both these methods
are in use and the choice of their use rests in an acid solution to give chromium(III)
with the individual using them. ion and the sulphate ion.

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redox reactions 247

Solution Problem 7.9


Step 1: The skeletal ionic equation is: Permanganate ion reacts with bromide
Cr2O72–(aq) + SO32–(aq) → Cr3+(aq) ion in basic medium to give manganese
dioxide and bromate ion. Write the
+ SO42–(aq)
balanced ionic equation for the reaction.
Step 2: Assign oxidation numbers for
Cr and S Solution
+6 –2 +4 –2 +3 +6 –2 Step 1: The skeletal ionic equation is :
Cr2O72–(aq) + SO32–(aq) → Cr(aq)+SO42–(aq) MnO4–(aq) + Br–(aq) → MnO2(s) + BrO3– (aq)
This indicates that the dichromate ion is Step 2: Assign oxidation numbers for
the oxidant and the sulphite ion is the Mn and Br
reductant.
+7 –1 +4 +5
Step 3: Calculate the increase and MnO4–(aq) + Br–(aq) →MnO2 (s) + BrO3– (aq)
decrease of oxidation number, and make
this indicates that permanganate ion
them equal: from step-2 we can notice
is the oxidant and bromide ion is the
that there is change in oxidation state
reductant.
of chromium and sulphur. Oxidation
state of chromium changes form +6 to Step 3: Calculate the increase and
+3. There is decrease of +3 in oxidation decrease of oxidation number, and make
state of chromium on right hand side of the increase equal to the decrease.
+7 –1 +4 +5
the equation. Oxidation state of sulphur
changes from +4 to +6. There is an increase 2MnO (aq)+Br (aq) → 2MnO2(s)+BrO3–(aq)

4

of +2 in the oxidation state of sulphur on Step 4: As the reaction occurs in the


right hand side. To make the increase and basic medium, and the ionic charges are
decrease of oxidation state equal, place not equal on both sides, add 2 OH– ions
numeral 2 before cromium ion on right on the right to make ionic charges equal.
hand side and numeral 3 before sulphate 2MnO4– (aq) + Br– (aq) → 2MnO2(s) +
ion on right hand side and balance the BrO3–(aq) + 2OH–(aq)
chromium and sulphur atoms on both the
Step 5: Finally, count the hydrogen atoms
sides of the equation. Thus we get
and add appropriate number of water
+6 –2 +4 –2 +3 molecules (i.e. one H2O molecule) on the
Cr2O72–(aq) + 3SO32– (aq) → 2Cr3+ (aq) + left side to achieve balanced redox change.
+6 –2
2MnO4–(aq) + Br–(aq) + H2O(l) → 2MnO2(s)
3SO42– (aq)
+ BrO3– (aq) + 2OH–(aq)
Step 4: As the reaction occurs in the
acidic medium, and further the ionic (b) Half Reaction Method: In this method,
charges are not equal on both the sides, the two half equations are balanced separately
add 8H+ on the left to make ionic charges and then added together to give balanced
equal equation.
Cr2O72–(aq) + 3SO32–(aq)+ 8H+→ 2Cr3+(aq) Suppose we are to balance the equation
+ 3SO42– (aq) showing the oxidation of Fe2+ ions to Fe3+ ions
by dichromate ions (Cr2O7)2– in acidic medium,
Step 5: Finally, count the hydrogen
wherein, Cr2O72– ions are reduced to Cr3+ ions.
atoms, and add appropriate number of
The following steps are involved in this task.
water molecules (i.e., 4H2O) on the right
to achieve balanced redox change. Step 1: Produce unbalanced equation for the
reaction in ionic form :
Cr2O72– (aq) + 3SO32– (aq)+ 8H+ (aq) →
Fe2+(aq) + Cr2O72– (aq) → Fe3+ (aq) + Cr3+(aq)
2Cr3+ (aq) + 3SO42– (aq) +4H2O (l)
(7.50)

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248 chemistry

Step 2: Separate the equation into half- Step 7: Verify that the equation contains the
reactions: same type and number of atoms and the same
+2 +3 charges on both sides of the equation. This
Oxidation half : Fe2+ (aq) → Fe3+(aq) (7.51) last check reveals that the equation is fully
+6 –2 +3 balanced with respect to number of atoms
Reduction half : Cr2O72–(aq) → Cr3+(aq) and the charges.
(7.52) For the reaction in a basic medium, first
Step 3: Balance the atoms other than O and balance the atoms as is done in acidic medium.
H in each half reaction individually. Here the Then for each H+ ion, add an equal number of
oxidation half reaction is already balanced OH– ions to both sides of the equation. Where
with respect to Fe atoms. For the reduction H+ and OH– appear on the same side of the
half reaction, we multiply the Cr3+ by 2 to equation, combine these to give H2O.
balance Cr atoms. Problem 7.10
Cr2O72–(aq) → 2 Cr3+(aq) (7.53) Permanganate(VII) ion, MnO4– in basic
Step 4: For reactions occurring in acidic solution oxidises iodide ion, I– to produce
medium, add H2O to balance O atoms and H+ molecular iodine (I2) and manganese
to balance H atoms. (IV) oxide (MnO2). Write a balanced ionic
Thus, we get : equation to represent this redox reaction.
Cr2O72– (aq) + 14H+ (aq) → 2 Cr3+(aq) + 7H2O (l) Solution
(7.54) Step 1: First we write the skeletal
Step 5: Add electrons to one side of the half ionic equation, which is
reaction to balance the charges. If need be, MnO4– (aq) + I– (aq) → MnO2(s) + I2(s)
make the number of electrons equal in the
Step 2: The two half-reactions are:
two half reactions by multiplying one or both
half reactions by appropriate number. –1 0
Oxidation half : I–(aq) → I2 (s)
The oxidation half reaction is thus +7 +4
rewritten to balance the charge: Reduction half: MnO4–(aq) → MnO2(s)
Fe2+ (aq) → Fe3+ (aq) + e– (7.55) Step 3: To balance the I atoms in the
Now in the reduction half reaction there oxidation half reaction, we rewrite it as:
are net twelve positive charges on the left hand 2I– (aq) → I2 (s)
side and only six positive charges on the right
hand side. Therefore, we add six electrons on Step 4: To balance the O atoms in the
the left side. reduction half reaction, we add two water
molecules on the right:
Cr2O72– (aq) + 14H+ (aq) + 6e– → 2Cr3+(aq) +
MnO4– (aq) → MnO2 (s) + 2 H2O (l)
7H2O (l) (7.56)
To balance the H atoms, we add four H+
To equalise the number of electrons in both ions on the left:
the half reactions, we multiply the oxidation
MnO–4 (aq) + 4 H+ (aq) → MnO2(s) + 2H2O (l)
half reaction by 6 and write as :
As the reaction takes place in a basic
6Fe2+ (aq) → 6Fe3+(aq) + 6e– (7.57)
solution, therefore, for four H+ ions, we
Step 6: We add the two half reactions to add four OH– ions to both sides of the
achieve the overall reaction and cancel the equation:
electrons on each side. This gives the net ionic MnO–4 (aq) + 4H+ (aq) + 4OH–(aq) →
equation as :
MnO2 (s) + 2 H2O(l) + 4OH– (aq)
6Fe2+(aq) + Cr2O72–(aq) + 14H+(aq) → 6 Fe3+(aq) +
Replacing the H+ and OH– ions with water,
2Cr (aq) + 7H2O(l) (7.58)
3+

Unit 7.indd 248 10/10/2022 10:37:05 AM


redox reactions 249

the resultant equation is: (ii) If there is no dramatic auto-colour change


(as with MnO4– titration), there are indicators
MnO4– (aq) + 2H2O (l) → MnO2 (s) + 4 OH– (aq)
which are oxidised immediately after the
Step 5 : In this step we balance the last bit of the reactant is consumed,
charges of the two half-reactions in the producing a dramatic colour change. The
manner depicted as: best example is afforded by Cr2O72–, which
2I– (aq) → I2 (s) + 2e– is not a self-indicator, but oxidises the
MnO4–(aq) + 2H2O(l) + 3e– → MnO2(s) indicator substance diphenylamine just
after the equivalence point to produce an
+ 4OH–(aq)
intense blue colour, thus signalling the
Now to equalise the number of electrons, end point.
we multiply the oxidation half-reaction by
(iii) There is yet another method which is
3 and the reduction half-reaction by 2.
interesting and quite common. Its use is
6I–(aq) → 3I2 (s) + 6e– restricted to those reagents which are able
2 MnO4– (aq) + 4H2O (l) +6e– → 2MnO2(s) to oxidise I– ions, say, for example, Cu(II):
+ 8OH– (aq) 2Cu2+(aq) + 4I–(aq) → Cu2I2(s) + I2(aq) (7.59)
Step 6: Add two half-reactions to This method relies on the facts that
obtain the net reactions after cancelling iodine itself gives an intense blue colour with
electrons on both sides. starch and has a very specific reaction with
6I –(aq) + 2MnO4–(aq) + 4H2O(l) → 3I2(s) + thiosulphate ions (S2O32–), which too is a redox
2MnO2(s) +8 OH–(aq) reaction:
Step 7: A final verification shows that I2(aq) + 2 S2O2– 3
(aq)→2I–(aq) + S4O62–(aq) (7.60)
the equation is balanced in respect of I2, though insoluble in water, remains in
the number of atoms and charges on solution containing KI as KI3.
both sides.
On addition of starch after the liberation
7.3.3 Redox Reactions as the Basis for of iodine from the reaction of Cu2+ ions on
Titrations iodide ions, an intense blue colour appears.
In acid-base systems we come across with a This colour disappears as soon as the iodine
titration method for finding out the strength is consumed by the thiosulphate ions. Thus,
of one solution against the other using a the end-point can easily be tracked and the
pH sensitive indicator. Similarly, in redox rest is the stoichiometric calculation only.
systems, the titration method can be adopted 7.3.4 Limitations of Concept of Oxidation
to determine the strength of a reductant/ Number
oxidant using a redox sensitive indicator.
The usage of indicators in redox titration is As you have observed in the above discussion,
illustrated below: the concept of redox processes has been
evolving with time. This process of evolution
(i) In one situation, the reagent itself is
is continuing. In fact, in recent past the
intensely coloured, e.g., permanganate
oxidation process is visualised as a decrease
ion, MnO4–. Here MnO4– acts as the self
in electron density and reduction process as
indicator. The visible end point in this case
is achieved after the last of the reductant an increase in electron density around the
(Fe2+ or C2O42–) is oxidised and the first atom(s) involved in the reaction.
lasting tinge of pink colour appears at 7.4 Redox Reactions and Electrode
MnO4– concentration as low as 10–6 mol dm–3
Processes
(10–6 mol L–1). This ensures a minimal
‘overshoot’ in colour beyond the equivalence The experiment corresponding to reaction
point, the point where the reductant and (7.15), can also be observed if zinc rod is
the oxidant are equal in terms of their dipped in copper sulphate solution. The
mole stoichiometry. redox reaction takes place and during the

Unit 7.indd 249 10/10/2022 10:37:05 AM


250 chemistry

reaction, zinc is oxidised to zinc ions and are represented as Zn2+/Zn and Cu2+/Cu.
copper ions are reduced to metallic copper In both cases, oxidised form is put before
due to direct transfer of electrons from zinc the reduced form. Now we put the beaker
to copper ion. During this reaction heat is containing copper sulphate solution and the
also evolved. Now we modify the experiment beaker containing zinc sulphate solution
in such a manner that for the same redox side by side (Fig. 7.3). We connect solutions
reaction transfer of electrons takes place in two beakers by a salt bridge (a U-tube
indirectly. This necessitates the separation containing a solution of potassium chloride
of zinc metal from copper sulphate solution. or ammonium nitrate usually solidified by
We take copper sulphate solution in a beaker boiling with agar agar and later cooling to a
and put a copper strip or rod in it. We also jelly like substance). This provides an electric
take zinc sulphate solution in another beaker contact between the two solutions without
and put a zinc rod or strip in it. Now reaction allowing them to mix with each other. The
takes place in either of the beakers and at the zinc and copper rods are connected by a
interface of the metal and its salt solution in metallic wire with a provision for an ammeter
each beaker both the reduced and oxidized and a switch. The set-up as shown in Fig.7.3
forms of the same species are present. These is known as Daniell cell. When the switch is
represent the species in the reduction and in the off position, no reaction takes place in
oxidation half reactions. A redox couple is either of the beakers and no current flows
defined as having together the oxidised and through the metallic wire. As soon as the
reduced forms of a substance taking part in switch is in the on position, we make the
an oxidation or reduction half reaction. following observations:
This is represented by separating the 1. The transfer of electrons now does not
oxidised form from the reduced form by take place directly from Zn to Cu2+ but
a vertical line or a slash representing an through the metallic wire connecting the
interface (e.g. solid/solution). For example two rods as is apparent from the arrow
in this experiment the two redox couples which indicates the flow of current.
2. The electricity from solution in one beaker
to solution in the other beaker flows by
the migration of ions through the salt
bridge. We know that the flow of current
is possible only if there is a potential
difference between the copper and zinc
rods known as electrodes here.
The potential associated with each
electrode is known as electrode potential.
If the concentration of each species taking
part in the electrode reaction is unity (if any
gas appears in the electrode reaction, it is
confined to 1 atmospheric pressure) and
further the reaction is carried out at 298K,
then the potential of each electrode is said
Fig.7.3 The set-up for Daniell cell. Electrons to be the Standard Electrode Potential. By
produced at the anode due to oxidation convention, the standard electrode potential
of Zn travel through the external circuit (E) of hydrogen electrode is 0.00 volts. The
to the cathode where these reduce the
electrode potential value for each electrode
copper ions. The circuit is completed
inside the cell by the migration of ions process is a measure of the relative tendency
through the salt bridge. It may be noted of the active species in the process to remain
that the direction of current is opposite to in the oxidised/reduced form. A negative E
the direction of electron flow. means that the redox couple is a stronger

Unit 7.indd 250 10/10/2022 10:37:05 AM


redox reactions 251

reducing agent than the H+/H2 couple. A information from them. The values of standard
positive E means that the redox couple is a electrode potentials for some selected electrode
weaker reducing agent than the H+/H2 couple. processes (reduction reactions) are given in
The standard electrode potentials are very Table 7.1. You will learn more about electrode
important and we can get a lot of other useful reactions and cells in Class XII.
Table 7.1 The Standard Electrode Potentials at 298 K
Ions are present as aqueous species and H2O as liquid; gases and
solids are shown by g and s respectively.
Reaction (Oxidised form + ne– → Reduced form) E / V

F2(g) + 2e– → 2F– 2.87


Co 3+
+e –
→ Co2+ 1.81
H2O2 + 2H+ + 2e– → 2H2O 1.78
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O 1.51
Au3+ + 3e– → Au(s) 1.40
Cl2(g) + 2e– → 2Cl 1.36

Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O 1.33


O2(g) + 4H+ + 4e– → 2H2O 1.23
MnO2(s) + 4H+ + 2e– → Mn2+ + 2H2O 1.23
Br2 + 2e– → 2Br 1.09

NO3– + 4H+ + 3e– → NO(g) + 2H2O 0.97

Increasing strength of reducing agent


Increasing strength of oxidising agent

2Hg2+ + 2e– → Hg22+ 0.92


Ag+ + e– → Ag(s) 0.80
Fe3+ + e– → Fe2+ 0.77
O2(g) + 2H+ + 2e– → H2O2 0.68
I2(s) + 2e– → 2I 0.54

Cu+ + e– → Cu(s) 0.52


Cu2+ + 2e– → Cu(s) 0.34
AgCl(s) + e– → Ag(s) + Cl– 0.22
AgBr(s) + e– → Ag(s) + Br– 0.10
2H+ + 2e– → H2(g) 0.00
Pb2+ + 2e– → Pb(s) –0.13
Sn2+ + 2e– → Sn(s) –0.14
Ni2+ + 2e– → Ni(s) –0.25
Fe2+ + 2e– → Fe(s) –0.44
Cr3+ + 3e– → Cr(s) –0.74
Zn2+ + 2e– → Zn(s) –0.76
2H2O + 2e– → H2(g) + 2OH– –0.83
Al3+
+ 3e –
→ Al(s) –1.66
Mg2+ + 2e– → Mg(s) –2.36
Na + e+ –
→ Na(s) –2.71
Ca2+ + 2e– → Ca(s) –2.87
K +e
+ –
→ K(s) –2.93
Li + e
+ –
→ Li(s) –3.05

1. A negative E means that the redox couple is a stronger reducing agent than the H+/H2 couple.
2. A positive E means that the redox couple is a weaker reducing agent than the H+/H2 couple.

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252 chemistry

SUMMARY

Redox reactions form an important class of reactions in which oxidation and reduction
occur simultaneously. Three tier conceptualisation viz, classical, electronic and oxidation
number, which is usually available in the texts, has been presented in detail. Oxidation,
reduction, oxidising agent (oxidant) and reducing agent (reductant) have been viewed
according to each conceptualisation. Oxidation numbers are assigned in accordance with a
consistent set of rules. Oxidation number and ion-electron method both are useful means in
writing equations for the redox reactions. Redox reactions are classified into four categories:
combination, decomposition displacement and disproportionation reactions. The concept of
redox couple and electrode processes is introduced here. The redox reactions find wide
applications in the study of electrode processes and cells.

EXERCISES

7.1 Assign oxidation number to the underlined elements in each of the following species:
(a) NaH2PO4 (b) NaHSO4 (c) H4P2O7 (d) K2MnO4
(e) CaO2 (f) NaBH4 (g) H2S2O7 (h) KAl(SO4)2.12 H2O
7.2 What are the oxidation number of the underlined elements in each of the following
and how do you rationalise your results ?
(a) KI3 (b) H2S4O6 (c) Fe3O4 (d) CH3CH2OH (e) CH3COOH
7.3 Justify that the following reactions are redox reactions:
(a) CuO(s) + H2(g) → Cu(s) + H2O(g)
(b) Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g)
(c) 4BCl3(g) + 3LiAlH4(s) → 2B2H6(g) + 3LiCl(s) + 3 AlCl3 (s)
(d) 2K(s) + F2(g) → 2K+F– (s)
(e) 4 NH3(g) + 5 O2(g) → 4NO(g) + 6H2O(g)
7.4 Fluorine reacts with ice and results in the change:
H2O(s) + F2(g) → HF(g) + HOF(g)
Justify that this reaction is a redox reaction.
7.5 Calculate the oxidation number of sulphur, chromium and nitrogen in H2SO5, Cr2O72–
and NO3–. Suggest structure of these compounds. Count for the fallacy.
7.6 Write formulas for the following compounds:
(a) Mercury(II) chloride (b) Nickel(II) sulphate
(c) Tin(IV) oxide (d) Thallium(I) sulphate
(e) Iron(III) sulphate ( f ) Chromium(III) oxide
7.7 Suggest a list of the substances where carbon can exhibit oxidation states from –4
to +4 and nitrogen from –3 to +5.
7.8 While sulphur dioxide and hydrogen peroxide can act as oxidising as well as reducing
agents in their reactions, ozone and nitric acid act only as oxidants. Why ?
7.9 Consider the reactions:
(a) 6 CO2(g) + 6H2O(l) → C6 H12 O6(aq) + 6O2(g)

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redox reactions 253

(b) O3(g) + H2O2(l) → H2O(l) + 2O2(g)


Why it is more appropriate to write these reactions as :
(a) 6CO2(g) + 12H2O(l) → C6 H12 O6(aq) + 6H2O(l) + 6O2(g)
(b) O3(g) + H2O2 (l) → H2O(l) + O2(g) + O2(g)
Also suggest a technique to investigate the path of the above (a) and (b) redox
reactions.
7.10 The compound AgF2 is unstable compound. However, if formed, the compound acts
as a very strong oxidising agent. Why ?
7.11 Whenever a reaction between an oxidising agent and a reducing agent is carried out,
a compound of lower oxidation state is formed if the reducing agent is in excess and
a compound of higher oxidation state is formed if the oxidising agent is in excess.
Justify this statement giving three illustrations.
7.12 How do you count for the following observations ?
(a) Though alkaline potassium permanganate and acidic potassium permanganate
both are used as oxidants, yet in the manufacture of benzoic acid from toluene
we use alcoholic potassium permanganate as an oxidant. Why ? Write a balanced
redox equation for the reaction.
(b) When concentrated sulphuric acid is added to an inorganic mixture containing
chloride, we get colourless pungent smelling gas HCl, but if the mixture contains
bromide then we get red vapour of bromine. Why ?
7.13 Identify the substance oxidised reduced, oxidising agent and reducing agent for
each of the following reactions:
(a) 2AgBr (s) + C6H6O2(aq) → 2Ag(s) + 2HBr (aq) + C6H4O2(aq)
(b) HCHO(l) + 2[Ag (NH3)2]+(aq) + 3OH–(aq) → 2Ag(s) + HCOO–(aq) + 4NH3(aq)
+ 2H2O(l)
(c) HCHO (l) + 2 Cu (aq) + 5 OH (aq) → Cu2O(s) + HCOO (aq) + 3H2O(l)
2+ – –

(d) N2H4(l) + 2H2O2(l) → N2(g) + 4H2O(l)


(e) Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
7.14 Consider the reactions :
2 S2O32– (aq) + I2(s) → S4 O62–(aq) + 2I–(aq)
S2O32–(aq) + 2Br2(l) + 5 H2O(l) → 2SO42–(aq) + 4Br–(aq) + 10H+(aq)
Why does the same reductant, thiosulphate react differently with iodine and
bromine ?
7.15 Justify giving reactions that among halogens, fluorine is the best oxidant and among
hydrohalic compounds, hydroiodic acid is the best reductant.
7.16 Why does the following reaction occur ?
XeO64– (aq) + 2F (aq) + 6H+(aq) → XeO3(g)+ F2(g) + 3H2O(l)

What conclusion about the compound Na4XeO6 (of which XeO4–


6
is a part) can be
drawn from the reaction.
7.17 Consider the reactions:
(a) H3PO2(aq) + 4 AgNO3(aq) + 2 H2O(l) → H3PO4(aq) + 4Ag(s) + 4HNO3(aq)
(b) H3PO2(aq) + 2CuSO4(aq) + 2 H2O(l) → H3PO4(aq) + 2Cu(s) + H2SO4(aq)
(c) C6H5CHO(l) + 2[Ag (NH3)2]+(aq) + 3OH–(aq) → C6H5COO–(aq) + 2Ag(s) +
4NH3 (aq) + 2 H2O(l)
(d) C6H5CHO(l) + 2Cu (aq) + 5OH (aq) → No change observed.
2+ –

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254 chemistry

What inference do you draw about the behaviour of Ag+ and Cu2+ from these
reactions ?
7.18 Balance the following redox reactions by ion – electron method :
(a) MnO4– (aq) + I– (aq) → MnO2 (s) + I2(s) (in basic medium)
(b) MnO4– (aq) + SO2 (g) → Mn2+ (aq) + HSO4– (aq) (in acidic solution)
(c) H2O2 (aq) + Fe2+ (aq) → Fe3+ (aq) + H2O (l) (in acidic solution)
(d) Cr2O72– + SO2(g) → Cr3+ (aq) + SO42– (aq) (in acidic solution)
7.19 Balance the following equations in basic medium by ion-electron method and
oxidation number methods and identify the oxidising agent and the reducing agent.
(a) P4(s) + OH–(aq) → PH3(g) + HPO2– (aq)
(b) N2H4(l) + ClO3–(aq) → NO(g) + Cl–(g)
(c) Cl2O7 (g) + H2O2(aq) → ClO2–(aq) + O2(g) + H+
7.20 What sorts of informations can you draw from the following reaction ?
(CN)2(g) + 2OH–(aq) → CN–(aq) + CNO–(aq) + H2O(l)
7.21 The Mn3+ ion is unstable in solution and undergoes disproportionation to give Mn2+,
MnO2, and H+ ion. Write a balanced ionic equation for the reaction.
7.22 Consider the elements :
Cs, Ne, I and F
(a) Identify the element that exhibits only negative oxidation state.
(b) Identify the element that exhibits only postive oxidation state.
(c) Identify the element that exhibits both positive and negative oxidation states.
(d) Identify the element which exhibits neither the negative nor does the positive
oxidation state.
7.23 Chlorine is used to purify drinking water. Excess of chlorine is harmful. The excess
of chlorine is removed by treating with sulphur dioxide. Present a balanced equation
for this redox change taking place in water.
7.24 Refer to the periodic table given in your book and now answer the following questions:
(a) Select the possible non metals that can show disproportionation reaction.
(b) Select three metals that can show disproportionation reaction.
7.25 In Ostwald’s process for the manufacture of nitric acid, the first step involves the
oxidation of ammonia gas by oxygen gas to give nitric oxide gas and steam. What is
the maximum weight of nitric oxide that can be obtained starting only with 10.00
g. of ammonia and 20.00 g of oxygen ?
7.26 Using the standard electrode potentials given in the Table 8.1, predict if the reaction
between the following is feasible:
(a) Fe3+(aq) and I–(aq)
(b) Ag+(aq) and Cu(s)
(c) Fe3+ (aq) and Cu(s)
(d) Ag(s) and Fe3+(aq)
(e) Br2(aq) and Fe2+(aq).

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redox reactions 255

7.27 Predict the products of electrolysis in each of the following:


(i) An aqueous solution of AgNO3 with silver electrodes
(ii) An aqueous solution AgNO3 with platinum electrodes
(iii) A dilute solution of H2SO4 with platinum electrodes
(iv) An aqueous solution of CuCl2 with platinum electrodes.
7.28 Arrange the following metals in the order in which they displace each other from
the solution of their salts.
Al, Cu, Fe, Mg and Zn.
7.29 Given the standard electrode potentials,
K+/K = –2.93V, Ag+/Ag = 0.80V,
Hg2+/Hg = 0.79V
Mg2+/Mg = –2.37V. Cr3+/Cr = –0.74V
arrange these metals in their increasing order of reducing power.
7.30 Depict the galvanic cell in which the reaction Zn(s) + 2Ag+(aq) → Zn2+(aq) +2Ag(s)
takes place, Further show:
(i) which of the electrode is negatively charged,
(ii) the carriers of the current in the cell, and
(iii) individual reaction at each electrode.

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256 chemistry

Unit 8

Organic Chemistry – Some Basic Princi-


ples and Techniques

In the previous unit you have learnt that the element


carbon has the unique property called catenation due to
which it forms covalent bonds with other carbon atoms.
After studying this unit, you will It also forms covalent bonds with atoms of other elements
be able to
like hydrogen, oxygen, nitrogen, sulphur, phosphorus
• understand reasons for and halogens. The resulting compounds are studied
tetravalence of carbon and under a separate branch of chemistry called organic
shapes of organic molecules; chemistry. This unit incorporates some basic principles
• write structures of organic and techniques of analysis required for understanding the
molecules in various ways; formation and properties of organic compounds.
• classify the organic compounds;
• name the compounds according
8.1 General Introduction
to IUPAC system of nomenclature
and also derive their structures Organic compounds are vital for sustaining life on earth
from the given names; and include complex molecules like genetic information
• understand the concept of bearing deoxyribonucleic acid (DNA) and proteins that
organic reaction mechanism; constitute essential compounds of our blood, muscles and
• explain the influence of electronic skin. Organic compounds appear in materials like clothing,
displacements on structure and fuels, polymers, dyes and medicines. These are some of
reactivity of organic compounds; the important areas of application of these compounds.
• recognise the types of organic Science of organic chemistry is about two hundred
reactions; years old. Around the year 1780, chemists began to
• learn the techniques of distinguish between organic compounds obtained from
purification of organic plants and animals and inorganic compounds prepared
compounds;
from mineral sources. Berzilius, a Swedish chemist
• write the chemical reactions
proposed that a ‘vital force’ was responsible for the
involved in the qualitative
formation of organic compounds. However, this notion
analysis of organic compounds;
was rejected in 1828 when F. Wohler synthesised an
• understand the principles
involved in quantitative analysis
organic compound, urea from an inorganic compound,
of organic compounds. ammonium cyanate.
NH4CNO NH2CONH2
Ammonium cyanate Urea
The pioneering synthesis of acetic acid by Kolbe
(1845) and that of methane by Berthelot (1856) showed
conclusively that organic compounds could be synthesised
from inorganic sources in a laboratory.

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organic chemistry – some basic principles and techniques 257

The development of electronic theory of Thus, in H2C=CH2 molecule all the atoms
covalent bonding ushered organic chemistry must be in the same plane. The p orbitals are
into its modern shape. mutually parallel and both the p orbitals are
perpendicular to the plane of the molecule.
8.2 TETRAVALENCE OF CARBON:
Rotation of one CH2 fragment with respect
SHAPES OF ORGANIC COMPOUNDS
to other interferes with maximum overlap
8.2.1 The Shapes of Carbon Compounds of p orbitals and, therefore, such rotation
The knowledge of fundamental concepts of about carbon-carbon double bond (C=C) is
molecular structure helps in understanding restricted. The electron charge cloud of the π
and predicting the properties of organic bond is located above and below the plane of
compounds. You have already learnt theories bonding atoms. This results in the electrons
of valency and molecular structure in Unit 4. being easily available to the attacking
Also, you already know that tetravalence of reagents. In general, π bonds provide the most
carbon and the formation of covalent bonds reactive centres in the molecules containing
by it are explained in terms of its electronic multiple bonds.
configuration and the hybridisation of s and p
orbitals. It may be recalled that formation and
Problem 8.1
the shapes of molecules like methane (CH4),
ethene (C2H4), ethyne (C2H2) are explained How many σ and π bonds are present in
in terms of the use of sp3, sp2 and sp hybrid each of the following molecules?
orbitals by carbon atoms in the respective (a) HC≡CCH=CHCH3 (b) CH2=C=CHCH3
molecules.
Solution
Hybridisation influences the bond length
and bond enthalpy (strength) in compounds. (a) σC – C: 4; σC–H : 6; πC=C :1; π C≡C:2
The sp hybrid orbital contains more s (b) σC – C: 3; σC–H: 6; πC=C: 2.
character and hence it is closer to its nucleus
and forms shorter and stronger bonds than Problem 8.2
the sp3 hybrid orbital. The sp2 hybrid orbital What is the type of hybridisation of each
is intermediate in s character between sp carbon in the following compounds?
and sp3 and, hence, the length and enthalpy
of the bonds it forms, are also intermediate (a) CH3Cl, (b) (CH3)2CO, (c) CH3CN,
between them. The change in hybridisation (d) HCONH2, (e) CH3CH=CHCN
affects the electronegativity of carbon. The
Solution
greater the s character of the hybrid orbitals,
the greater is the electronegativity. Thus, a (a) sp3, (b) sp3, sp2, (c) sp3, sp, (d) sp2, (e)
carbon atom having an sp hybrid orbital with sp3, sp2, sp2, sp
50% s character is more electronegative than Problem 8.3
that possessing sp2 or sp3 hybridised orbitals.
This relative electronegativity is reflected in Write the state of hybridisation of carbon
several physical and chemical properties of in the following compounds and shapes
the molecules concerned, about which you of each of the molecules.
will learn in later units. (a) H2C=O, (b) CH3F, (c) HC≡N.
8.2.2 Some Characteristic Features of π Solution
Bonds
(a) sp2 hybridised carbon, trigonal planar;
In a π (pi) bond formation, parallel orientation (b) sp3 hybridised carbon, tetrahedral; (c)
of the two p orbitals on adjacent atoms is sp hybridised carbon, linear.
necessary for a proper sideways overlap.

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258 chemistry

8.3 STRUCTURAL RepresenTATIONS Similarly, CH3CH2CH2CH2CH2CH2CH2CH3


OF organic COMPOUNDs can be further condensed to CH3(CH2)6CH3.
8.3.1 Complete, Condensed and Bond-line For further simplification, organic chemists
Structural Formulas use another way of r epr esenting the
structures, in which only lines are used.
Structures of organic compounds are
In this bond-line structural representation
represented in several ways. The Lewis
of organic compounds, carbon and
structure or dot structure, dash structure,
hydrogen atoms are not shown and the
condensed structure and bond line structural
lines representing carbon-carbon bonds are
formulas are some of the specific types. The
drawn in a zig-zag fashion. The only atoms
Lewis structures, however, can be simplified
specifically written are oxygen, chlorine,
by representing the two-electron covalent
nitrogen etc. The terminals denote methyl
bond by a dash (–). Such a structural formula
(–CH3) groups (unless indicated otherwise by
focuses on the electrons involved in bond
a functional group), while the line junctions
formation. A single dash represents a single
denote carbon atoms bonded to appropriate
bond, double dash is used for double bond
number of hydrogens required to satisfy the
and a triple dash represents triple bond. Lone-
valency of the carbon atoms. Some of the
pairs of electrons on heteroatoms (e.g., oxygen,
examples are represented as follows:
nitrogen, sulphur, halogens etc.) may or may
not be shown. Thus, ethane (C2H6), ethene (i) 3-Methyloctane can be represented in
(C2H4), ethyne (C2H2) and methanol (CH3OH) various forms as:
can be represented by the following structural (a) CH3CH2CHCH2CH2CH2CH2CH3
formulas. Such structural representations are |
called complete structural formulas. CH3

(b)

Ethane Ethene

(c)

Ethyne Methanol

These structural formulas can be further


abbreviated by omitting some or all of the
dashes representing covalent bonds and by
(ii) Various ways of representing 2-bromo
indicating the number of identical groups
butane are:
attached to an atom by a subscript. The
resulting expression of the compound is
called a condensed structural formula. Thus,
(a) CH3CHBrCH2CH3 (b)
ethane, ethene, ethyne and methanol can be
written as:
CH3CH3 H2C=CH2 HC≡CH CH3OH
(c)
Ethane Ethene Ethyne Methanol

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organic chemistry – some basic principles and techniques 259

In cyclic compounds, the bond-line formulas


may be given as follows:
(b)
Solution
Condensed formula:
Cyclopropane (a) HO(CH2)3CH(CH3)CH(CH3)2
(b) HOCH(CN)2
Bond-line formula:
(a)

Cyclopentane

(b)

chlorocyclohexane

Problem 8.6
Problem 8.4
Expand each of the following bond-line
Expand each of the following condensed formulas to show all the atoms including
formulas into their complete structural carbon and hydrogen
formulas. (a)
(a) CH3CH2COCH2CH3
(b) CH3CH=CH(CH2)3CH3

Solution (b)

(a)
(c)

(b) (d)

Solution
Problem 8.5
For each of the following compounds,
write a condensed formula and also their
bond-line formula.

(a) HOCH2CH2CH2CH(CH3)CH(CH3)CH3

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260 chemistry

Molecular Models
Molecular models are physical devices
that are used for a better visualisation and
perception of three-dimensional shapes
of organic molecules. These are made of
wood, plastic or metal and are commercially
available. Commonly three types of molecular
models are used: (1) Framework model, (2)
Ball-and-stick model, and (3) Space filling
model. In the framework model only the
bonds connecting the atoms of a molecule
and not the atoms themselves are shown.
This model emphasizes the pattern of
bonds of a molecule while ignoring the size
of atoms. In the ball-and-stick model, both
the atoms and the bonds are shown. Balls
represent atoms and the stick denotes a
bond. Compounds containing C=C (e.g.,
ethene) can best be represented by using
8.3.2 Three-Dimensional
springs in place of sticks. These models are
Representation of Organic referred to as ball-and-spring model. The
Molecules space-filling model emphasises the relative
The three-dimensional (3-D) structure of size of each atom based on its van der Waals
organic molecules can be represented on radius. Bonds are not shown in this model.
paper by using certain conventions. For It conveys the volume occupied by each atom
example, by using solid ( ) and dashed in the molecule. In addition to these models,
computer graphics can also be used for
( ) wedge formula, the 3-D image of a
molecular modelling.
molecule from a two-dimensional picture
can be perceived. In these formulas the
solid-wedge is used to indicate a bond
projecting out of the plane of paper, towards
the observer. The dashed-wedge is used to
depict the bond projecting out of the plane of
the paper and away from the observer. Wedges
are shown in such a way that the broad end of
the wedge is towards the observer. The bonds Framework model Ball and stick model
lying in plane of the paper are depicted by
using a normal line (—). 3-D representation of
methane molecule on paper has been shown
in Fig. 8.1

Space filling model

Fig. 8.2
Fig. 8.1 Wedge-and-dash representation of CH4

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organic chemistry – some basic principles and techniques 261

8.4 Classification of Organic (homocyclic).


Compounds
The existing large number of organic
compounds and their ever -increasing
numbers has made it necessary to classify
them on the basis of their structures. Organic Cyclopropane Cyclohexene Cyclohexane
compounds are broadly classified as follows:
Sometimes atoms other than carbon are
also present in the ring (heterocylic).
Tetrahydrofuran given below is an example
of this type of compound:

Tetrahydrofuran
These exhibit some of the properties similar
to those of aliphatic compounds.
(b) Aromatic compounds
Aromatic compounds are special types of
compounds. You will learn about these
compounds in detail in Unit 9. These include
benzene and other related ring compounds
(benzenoid). Like alicyclic compounds,
aromatic comounds may also have hetero
atom in the ring. Such compounds are called
I. Acyclic or open chain compounds hetrocyclic aromatic compounds. Some of
the examples of various types of aromatic
These compounds are also called as aliphatic
compounds are:
compounds and consist of straight or
branched chain compounds, for example: Benzenoid aromatic compounds

CH3CH3
Ethane

Isobutane
Benzene Aniline Naphthalene
Non-benzenoid compound

Acetaldehyde Acetic acid


II C y c l i c o r c l o s e d c h a i n o r r i n g
compounds
(a) Alicyclic compounds Tropone
Alicyclic (aliphatic cyclic) compounds contain
carbon atoms joined in the form of a ring

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262 chemistry

Heterocyclic aromatic compounds so because it is found in citrus fruits and the


acid found in red ant is named formic acid
since the Latin word for ant is formica. These
names are traditional and are considered
as trivial or common names. Some common
Furan Thiophene Pyridine names are followed even today. For example,
Organic compounds can also be classified Buckminsterfullerene is a common name
on the basis of functional groups, into families given to the newly discovered C60 cluster (a
or homologous series. form of carbon) noting its structural similarity
8.4.1 Functional Group to the geodesic domes popularised by the
famous architect R. Buckminster Fuller.
The functional group is an atom or a group Common names are useful and in many
of atoms joined to the carbon chain which is cases indispensable, particularly when the
responsible for the characteristic chemical alternative systematic names are lengthy and
properties of the organic compounds. The complicated. Common names of some organic
examples are hydroxyl group (–OH), aldehyde compounds are given in Table 8.1.
group (–CHO) and carboxylic acid group (–
COOH) etc. Table 8.1 Common or Trivial Names of Some
Organic Compounds
8.4.2 Homologous Series
A group or a series of organic compounds each
containing a characteristic functional group
forms a homologous series and the members of
the series are called homologues. The members
of a homologous series can be represented by
general molecular formula and the successive
members differ from each other in molecular
formula by a –Ch2 unit. There are a number
of homologous series of organic compounds.
Some of these are alkanes, alkenes, alkynes,
haloalkanes, alkanols, alkanals, alkanones,
alkanoic acids, amines etc.
It is also possible that a compound contains
two or more identical or different functional
groups. This gives rise to polyfunctional
compounds.
8.5 NOMENCLATURE OF ORGANIC
COMPOUNDS
Organic chemistry deals with millions of 8.5.1 The IUPAC System of Nomenclature
compounds. In order to clearly identify
A systematic name of an organic compound
them, a systematic method of naming has
is generally derived by identifying the parent
been developed and is known as the IUPAC
hydrocarbon and the functional group(s)
(International Union of Pure and Applied
attached to it. See the example given below.
Chemistry) system of nomenclature. In this
systematic nomenclature, the names are
correlated with the structure such that the
reader or listener can deduce the structure
from the name.
Before the IUPAC system of nomenclature,
however, organic compounds were assigned
names based on their origin or certain
properties. For instance, citric acid is named

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organic chemistry – some basic principles and techniques 263

By further using prefixes and suffixes, the In order to name such compounds, the names
parent name can be modified to obtain the of alkyl groups are prefixed to the name of
actual name. Compounds containing carbon parent alkane. An alkyl group is derived
and hydrogen only are called hydrocarbons. from a saturated hydrocarbon by removing
A hydrocarbon is termed saturated if it a hydrogen atom from carbon. Thus, CH4
contains only carbon-carbon single bonds. becomes -CH3 and is called methyl group. An
The IUPAC name for a homologous series of alkyl group is named by substituting ‘yl’ for
such compounds is alkane. Paraffin (Latin: ‘ane’ in the corresponding alkane. Some alkyl
little affinity) was the earlier name given to groups are listed in Table 8.3.
these compounds. Unsaturated hydrocarbons Table 8.3 Some Alkyl Groups
are those, which contain at least one carbon-
carbon double or triple bond.
8.5.2 IUPAC Nomenclature of Alkanes
Straight chain hydrocarbons: The names
of such compounds are based on their chain
structure, and end with suffix ‘-ane’ and carry
a prefix indicating the number of carbon
atoms present in the chain (except from CH4
to C4H10, where the prefixes are derived from
trivial names). The IUPAC names of some
straight chain saturated hydrocarbons are
Abbreviations are used for some alkyl
given in Table 8.2. The alkanes in Table
groups. For example, methyl is abbreviated as
8.2 differ from each other by merely the
Me, ethyl as Et, propyl as Pr and butyl as Bu.
number of -CH2 groups in the chain. They are
The alkyl groups can be branched also. Thus,
homologues of alkane series.
propyl and butyl groups can have branched
Table 8.2 IUPAC Names of Some Unbranched structures as shown below.
Saturated Hydrocarbons CH3-CH- CH3-CH2-CH- CH3-CH-CH2-
  
CH3 CH3 CH3
Isopropyl- sec-Butyl- Isobutyl-
CH3 CH3
 
CH3-C- CH3-C-CH2-
 
CH3 CH3
tert-Butyl- Neopentyl-
Branched chain hydrocarbons: In a Common branched groups have specific
branched chain compound small chains of trivial names. For example, the propyl groups
carbon atoms are attached at one or more can either be n-propyl group or isopropyl
carbon atoms of the parent chain. The small group. The branched butyl groups are called
carbon chains (branches) are called alkyl sec-butyl, isobutyl and tert-butyl group.
groups. For example: We also encounter the structural unit,
–CH2C(CH3)3, which is called neopentyl group.
CH3–CH–CH2–CH3 CH3–CH–CH2–CH–CH3
   Nomenclature of branched chain alkanes:
CH3 CH2CH3 CH3 We encounter a number of branched chain
alkanes. The rules for naming them are given
(a)(b) below.

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264 chemistry

1. First of all, the longest carbon chain in separated from the groups by hyphens
the molecule is identified. In the example and there is no break between methyl
(I) given below, the longest chain has nine and nonane.]
carbons and it is considered as the parent 4. If two or more identical substituent
or root chain. Selection of parent chain as groups are present then the numbers
shown in (II) is not correct because it has are separated by commas. The names of
only eight carbons. identical substituents are not repeated,
instead prefixes such as di (for 2), tri
(for 3), tetra (for 4), penta (for 5), hexa (for
6) etc. are used. While writing the name
of the substituents in alphabetical order,
these prefixes, however, are not considered.
Thus, the following compounds are
named as:
CH3 CH3 CH3 CH3
    
CH3-CH-CH2-CH-CH3 CH3 C CH2CH CH3
1 2 3 4 5 1 2 3 4 5
2,4-Dimethylpentane 2,2,4-Trimethylpentane
2. The carbon atoms of the parent chain are
numbered to identify the parent alkane H3C H2C CH3
and to locate the positions of the carbon  
atoms at which branching takes place due CH3CH2CHCCH2CH2CH3
to the substitution of alkyl group in place 1 2 3 4 5 6 7
of hydrogen atoms. The numbering is CH3
done in such a way that the branched 3-Ethyl-4,4-dimethylheptane
carbon atoms get the lowest possible
numbers. Thus, the numbering in the 5. If the two substituents are found in
above example should be from left to right equivalent positions, the lower number
(branching at carbon atoms 2 and 6) and is given to the one coming first in the
not from right to left (giving numbers alphabetical listing. Thus, the following
4 and 8 to the carbon atoms at which compound is 3-ethyl-6-methyloctane and
branches are attached). not 6-ethyl-3-methyloctane.
1 2 3 4 5 6 7 8 9
CCCCCCCCC 1 2 3 4 5 6 7 8
  CH3 — CH2—CH—CH2—CH2—CH—CH2 —CH3
C CC  
CH2CH3 CH3
9 8 7 6 5 4 3 2 1
CCCCCCCCC 6. The branched alkyl groups can be
  named by following the above mentioned
C CC procedures. However, the carbon atom
3. The names of alkyl groups attached of the branch that attaches to the root
as a branch are then prefixed to the alkane is numbered 1 as exemplified
name of the parent alkane and position below.
of the substituents is indicated by the
4 3 2 1
appropriate numbers. If different alkyl
CH3–CH–CH2–CH–
groups are present, they are listed in
alphabetical order. Thus, name for the  
compound shown above is: 6-ethyl-2- CH3 CH3
1,3-Dimethylbutyl-
methylnonane. [Note: the numbers are

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organic chemistry – some basic principles and techniques 265

The name of such branched chain alkyl group Cyclic Compounds: A saturated monocyclic
is placed in parenthesis while naming the compound is named by prefixing ‘cyclo’ to the
compound. While writing the trivial names corresponding straight chain alkane. If side
of substituents’ in alphabetical order, the chains are present, then the rules given above
prefixes iso- and neo- are considered to be are applied. Names of some cyclic compounds
the part of the fundamental name of alkyl are given below.
group. The prefixes sec- and tert- are not
considered to be the part of the fundamental
name. The use of iso and related common
prefixes for naming alkyl groups is also
allowed by the IUPAC nomenclature as long
as these are not further substituted. In multi-
substituted compounds, the following rules
may aso be remembered:
• If there happens to be two chains of equal
size, then that chain is to be selected which
contains more number of side chains.
3-Ethyl-1,1-dimethylcyclohexane
• After selection of the chain, numbering (not 1-ethyl-3,3-dimethylcyclohexane)
is to be done from the end closer to the
substituent. Problem 8.7
Structures and IUPAC names of some
hydrocarbons are given below. Explain
why the names given in the parentheses
are incorrect.

2,5,6- Trimethyloctane
[and not 3,4,7-Trimethyloctane]

5-(2-Ethylbutyl)-3,3-dimethyldecane
[and not 5-(2,2-Dimethylbutyl)-3-ethyldecane]

3-Ethyl-5-methylheptane
[and not 5-Ethyl-3-methylheptane]

Solution
(a) Lowest locant number, 2,5,6 is
lower than 3,5,7, (b) substituents are
5-sec-Butyl-4-isopropyldecane in equivalent position; lower number is
given to the one that comes first in the
name according to alphabetical order.

8.5.3 Nomenclature of Organic


Compounds having Functional
Group(s)
A functional group, as defined earlier, is an
atom or a group of atoms bonded together in
5-(2,2-Dimethylpropyl)nonane a unique manner which is usually the site of

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266 chemistry

chemical reactivity in an organic molecule. class suffix. In such cases the full name of the
Compounds having the same functional parent alkane is written before the class suffix.
group undergo similar reactions. For example, For example CH2(OH)CH2(OH) is named as
CH 3OH, CH 3CH 2OH, and (CH 3) 2CHOH — ethane–1,2–diol. However, the ending – ne of
all having -OH functional group liberate the parent alkane is dropped in the case of
hydrogen on reaction with sodium metal. compounds having more than one double or
The presence of functional groups enables triple bond; for example, CH2=CH-CH=CH2 is
systematisation of organic compounds into named as buta–1,3–diene.
different classes. Examples of some functional
groups with their prefixes and suffixes along Problem 8.8
with some examples of organic compounds Write the IUPAC names of the compounds
possessing these are given in Table 8.4. i-iv from their given structures.
First of all, the functional group present
in the molecule is identified which determines
the choice of appropriate suffix. The longest
chain of carbon atoms containing the
functional group is numbered in such a way
that the functional group is attached at the Solution
carbon atom possessing lowest possible • The functional group present is an
number in the chain. By using the suffix as alcohol (OH). Hence the suffix is ‘-ol’.
given in Table 8.4, the name of the compound • The longest chain containing -OH
is arrived at. has eight carbon atoms. Hence the
In the case of polyfunctional compounds, corresponding saturated hydrocar-
one of the functional groups is chosen as the bon is octane.
principal functional group and the compound • The -OH is on carbon atom 3. In
is then named on that basis. The remaining addition, a methyl group is attached
functional groups, which are subordinate at 6th carbon.
functional groups, are named as substituents Hence, the systematic name of this
using the appropriate prefixes. The choice of compound is 6-Methyloctan-3-ol.
principal functional group is made on the basis
of order of preference. The order of decreasing
priority for some functional groups is:
-COOH, –SO3H, -COOR (R=alkyl group), COCl,
-CONH2, -CN,-HC=O, >C=O, -OH, -NH2, >
C=C<, -C≡C- . Solution
The –R, C6H5-, halogens (F, Cl, Br, I), –NO2, The functional group present is ketone
alkoxy (–OR) etc. are always prefix (>C=O), hence suffix ‘-one’. Presence
substituents. Thus, a compound containing of two keto groups is indicated by ‘di’,
both an alcohol and a keto group is named hence suffix becomes ‘dione’. The two
as hydroxyalkanone since the keto group is keto groups are at carbons 2 and 4.
preferred to the hydroxyl group. The longest chain contains 6 carbon
For example, HOCH2(CH2)3CH2COCH3 will atoms, hence, parent hydrocarbon is
be named as 7-hydroxyheptan-2-one and not hexane. Thus, the systematic name is
as 2-oxoheptan -7-ol. Similarly, BrCH2CH=CH2 Hexane-2,4-dione.
is named as 3-bromoprop-1-ene and not
1-bromoprop-2-ene.
If more than one functional group of the
same type are present, their number is
indicated by adding di, tri, etc. before the

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organic chemistry – some basic principles and techniques 267

Table 8.4 Some Functional Groups and Classes of Organic Compounds

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268 chemistry

Solution (iii) Six membered ring containing a


Here, two functional groups namely carbon-carbon double bond is implied
ketone and carboxylic acid are present. by cyclohexene, which is numbered as
The principal functional group is the shown in (I). The prefix 3-nitro means
carboxylic acid group; hence the parent that a nitro group is present on C-3.
chain will be suffixed with ‘oic’ acid. Thus, complete structural formula of the
Numbering of the chain starts from compound is (II). Double bond is suffixed
carbon of – COOH functional group. functional group whereas NO2 is prefixed
The keto group in the chain at carbon functional group therefore double bond
5 is indicated by ‘oxo’. The longest gets preference over –NO2 group:
chain including the principal functional
group has 6 carbon atoms; hence the
parent hydrocarbon is hexane. The
compound is, therefore, named as
5-Oxohexanoic acid.

(iv) ‘1-ol’ means that a -OH group is


Solution present at C-1. OH is suffixed functional
The two C=C functional groups are group and gets preference over C=C
present at carbon atoms 1 and 3, while bond. Thus the structure is as shown
the C≡C functional group is present at in (II):
carbon 5. These groups are indicated by
suffixes ‘diene’ and ‘yne’ respectively. The
longest chain containing the functional
groups has 6 carbon atoms; hence the
parent hydrocarbon is hexane. The name
of compound, therefore, is Hexa-1,3-
dien-5-yne.
(v) ‘heptanal’ indicates the compound
Problem 8.9
to be an aldehyde containing 7 carbon
Derive the structure of (i) 2-Chlorohexane, atoms in the parent chain. The
(ii) Pent-4-en-2-ol, (iii) 3- Nitrocyclohexene, ‘6-hydroxy’ indicates that -OH group is
(iv) Cyclohex-2-en-1-ol, (v) 6-Hydroxy- present at carbon 6. Thus, the structural
heptanal. formula of the compound is: CH3CH(OH)
Solution CH2CH2CH2CH2CHO. Carbon atom of –
CHO group is included while numbering
(i) ‘hexane’ indicates the presence of
the carbon chain.
6 carbon atoms in the chain. The
functional group chloro is present at
carbon 2. Hence, the structure of the 8.5.4 Nomenclature of Substituted
compound is CH3CH2CH2CH2CH(Cl)CH3. Benzene Compounds
(ii) ‘pent’ indicates that parent
For IUPAC nomenclature of substituted
hydrocarbon contains 5 carbon atoms
benzene compounds, the substituent is
in the chain. ‘en’ and ‘ol’ correspond to
the functional groups C=C and -OH at placed as prefix to the word benzene as shown
carbon atoms 4 and 2 respectively. Thus, in the following examples. However, common
the structure is names (written in bracket below) of many
substituted benzene compounds are also
CH2=CHCH2CH (OH)CH3. universally used.

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organic chemistry – some basic principles and techniques 269

Substituent of the base compound is


assigned number1 and then the direction
of numbering is chosen such that the
next substituent gets the lowest number.
The substituents appear in the name in
Methylbenzene Methoxybenzene Aminobenzene alphabetical order. Some examples are given
(Toluene) (Anisole) (Aniline)
below.

Nitrobenzene Bromobenzene 1-Chloro-2,4-dinitrobenzene


(not 4-chloro,1,3-dinitrobenzene)
If benzene ring is disubstituted,
the position of substituents is defined
by numbering the carbon atoms of the
ring such that the substituents are
located at the lowest numbers possible.
For example, the compound(b) is named
as 1,3-dibromobenzene and not as
1,5-dibromobenzene.

2-Chloro-1-methyl-4-nitrobenzene
(not 4-methyl-5-chloro-nitrobenzene)

(a) (b) (c)


1,2-Dibromo- 1,3-Dibromo- 1,4-Dibromo-
benzene benzene benzene
In the trivial system of nomenclature
the terms ortho (o), meta (m) and para (p) 2-Chloro-4-methylanisole 4-Ethyl-2-methylaniline
are used as prefixes to indicate the relative
positions 1,2;1,3 and 1,4 respectively. Thus,
1,3-dibr omobenzene (b) is named as
m-dibromobenzene (meta is abbreviated as
m-) and the other isomers of dibromobenzene
1,2-(a) and 1,4-(c), are named as ortho (or
just o-) and para (or just p-)-dibromobenzene,
respectively.
For tri - or higher substituted benzene 3,4-Dimethylphenol
derivatives, these prefixes cannot be used
and the compounds are named by identifying When a benzene ring is attached to an
substituent positions on the ring by following alkane with a functional group, it is considered
the lowest locant rule. In some cases, common as substituent, instead of a parent. The name
name of benzene derivatives is taken as the for benzene as substituent is phenyl (C6H5-,
base compound. also abbreviated as Ph).

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270 chemistry

different carbon skeletons, these are referred


Problem 8.10
to as chain isomers and the phenomenon is
Write the structural formula of: termed as chain isomerism. For example,
(a) o-Ethylanisole, (b) p-Nitroaniline, C5H12 represents three compounds:
(c) 2,3 - Dibromo -1 - phenylpentane,
(d) 4-Ethyl-1-fluoro-2-nitrobenzene. CH3

Solution
CH3CH2CH2CH2CH3 CH3−CHCH2CH3
Pentane Isopentane
(2-Methylbutane)
CH3

CH3 C CH3
(a)  (b) 
CH3
Neopentane
(2,2-Dimethylpropane)

(ii) Position isomerism: When two or


more compounds differ in the position of
(c) (d) substituent atom or functional group on
the carbon skeleton, they are called position
8.6 ISOMERISM isomers and this phenomenon is termed
as position isomerism. For example, the
The phenomenon of existence of two or more molecular formula C3H 8O represents two
compounds possessing the same molecular alcohols:
formula but different properties is known
as isomerism. Such compounds are called OH
as isomers. The following flow chart shows 
different types of isomerism. CH3CH2CH2OH CH3−CH-CH3
Propan-1-ol Propan-2-ol
8.6.1 Structural Isomerism
Compounds having the same molecular (iii) Functional group isomerism: Two or
formula but different structures (manners more compounds having the same molecular
in which atoms are linked) are classified as formula but different functional groups
structural isomers. Some typical examples are called functional isomers and this
of different types of structural isomerism are phenomenon is termed as functional group
given below: isomerism. For example, the molecular
(i) Chain isomerism: When two or more formula C3H6O represents an aldehyde and
compounds have similar molecular formula but a ketone:
Isomerism

Structural isomerism Stereoisomerism

Chain Position Functional Metamerism Geometrical Optical


isomerism isomerism group isomerism isomerism
isomerism

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organic chemistry – some basic principles and techniques 271

in understanding the reactivity of organic


O H compounds and in planning strategy for their
  synthesis.
CH3−C-CH3 CH3−CH2—C= O
In the following sections, we shall learn
Propanone Propanal
some of the principles that explain how these
(iv) Metamerism: It arises due to different reactions take place.
alkyl chains on either side of the functional
8.7.1 Fission of a Covalent Bond
group in the molecule. For example, C4H10O
represents methoxypropane (CH3OC3H7) and A covalent bond can get cleaved either by : (i)
ethoxyethane (C2H5OC2H5). heterolytic cleavage, or by (ii) homolytic
cleavage.
8.6.2 Stereoisomerism
In heterolytic cleavage, the bond breaks
The compounds that have the same in such a fashion that the shared pair of
constitution and sequence of covalent bonds electrons remains with one of the fragments.
but differ in relative positions of their atoms After heterolysis, one atom has a sextet
or groups in space are called stereoisomers. electronic structure and a positive charge and
This special type of isomerism is called as the other, a valence octet with at least one lone
stereoisomerism and can be classified as pair and a negative charge. Thus, heterolytic
geometrical and optical isomerism. +
cleavage of bromomethane will give C H3 and
8.7 F UNDAMENTAL C O NCE P TS IN Br– as shown below.
ORGANIC REACTION MECHANISM
In an organic reaction, the organic molecule
(also referred as a substrate) reacts with an A species having a carbon atom possessing
appropriate attacking reagent and leads to sextext of electrons and a positive charge is
the formation of one or more intermediate(s) called a carbocation (earlier called carbonium
and finally product(s) ion). The H3 ion is known as a methyl cation
or methyl carbonium ion. Carbocations are
The general reaction is depicted as follows :
classified as primary, secondary or tertiary
Attacking depending on whether one, two or three
Reagent [Intermediate] Product(s)
Organic carbons are directly attached to the positively
molecule charged carbon. Some+ other examples of
(Substrate) Byproducts carbocations are: CH3C H2 (ethyl cation, a
+
primary carbocation), (CH3)2C H (isopropyl+
Substrate is that reactant which supplies cation, a secondary carbocation), and (CH3)3C
carbon to the new bond and the other reactant (tert-butyl cation, a tertiary carbocation).
is called reagent. If both the reactants Carbocations are highly unstable and
supply carbon to the new bond then choice reactive species. Alkyl groups directly
is arbitrary and in that case the molecule on attached to the positively charged carbon
which attention is focused is called substrate. stabilise the carbocations due to inductive
In such a reaction a covalent bond and hyperconjugation effects, which you will
between two carbon atoms or a carbon and be studying in the sections 8.7.5 and 8.7.9.
some other atom is broken and a new bond is The+ observed+ order of carbocation
+
stability
+
formed. A sequential account of each step, is: C H3 < CH3CH2 < (CH3)2CH < (CH3)3C. These
describing details of electron movement, carbocations have trigonal planar shape
energetics during bond cleavage and bond with positively charged carbon+ being sp 2
formation, and the rates of transformation hybridised. Thus, the shape of C H3 may be
of reactants into products (kinetics) is considered as being derived from the overlap
referred to as reaction mechanism. The of three equivalent C(sp2) hybridised orbitals
knowledge of reaction mechanism helps with 1s orbital of each of the three hydrogen

Unit 8.indd 271 10/10/2022 10:37:33 AM


272 chemistry

atoms. Each bond may be represented as curved arrow. Such cleavage results in
C(sp 2)–H(1s) sigma bond. The remaining the formation of neutral species (atom or
carbon orbital is perpendicular to the group) which contains an unpaired electron.
molecular plane and contains no electrons. These species are called free radicals. Like
[Fig. 8.3(a)]. carbocations and carbanions, free radicals are
also very reactive. A homolytic cleavage can be
shown as:

Alkyl
free radical
Alkyl radicals are classified as primary,
secondary, or tertiary. Alkyl radical stability
increases as we proceed from primary to
Fig. 8.3 (a) Shape of methyl carbocation tertiary:
The heterolytic cleavage can also give a
,
species in which carbon gets the shared Methyl Ethyl Isopropyl Tert-butyl
pair of electrons. For example, when group free free free free
Z attached to the carbon leaves without radical radical radical radical
Organic reactions, which proceed by
homolytic fission are called free radical or
electron pair, the methyl anion is homopolar or nonpolar reactions.
formed. Such a carbon species carrying a 8.7.2 Substrate and Reagent
negative charge on carbon atom is called Ions are generally not formed in the reactions
carbanion. Carbon in carbanion is generally of organic compounds. Molecules as such
sp3 hybridised and its structure is distorted participate in the reaction. It is convenient to
tetrahedron as shown in Fig. 8.3(b). name one reagent as substrate and other as
reagent. In general, a molecule whose carbon
is involved in new bond formation is called
substrate and the other one is called reagent.
When carbon-carbon bond is formed, the
choice of naming the reactants as substrate
and reagent is arbitrary and depends on
molecule under observation. Example:

(i) CH2 = CH2 + Br2 →


Fig. 8.3 (b) Shape of methyl carbanion
CH2 Br – CH2Br
Substrate Reagent Product
Carbanions are also unstable and reactive
species. The organic reactions which proceed
through heterolytic bond cleavage are called (ii)
ionic or heteropolar or just polar reactions.
In homolytic cleavage, one of the electrons
of the shared pair in a covalent bond goes
with each of the bonded atoms. Thus, in
homolytic cleavage, the movement of a
single electron takes place instead of an Nucleophiles and Electrophiles
electron pair. The single electron movement Reagents attack the reactive site of the
is shown by ‘half-headed’ (fish hook: ) substrate. The reactive site may be electron

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organic chemistry – some basic principles and techniques 273

deficient portion of the molecule (a positive


reactive site) e.g., an atom with incomplete Problem 8.11
electron shell or the positive end of the dipole Using curved-arrow notation, show the
in the molecule. If the attacking species is formation of reactive intermediates when
electron rich, it attacks these sites. If attacking the following covalent bonds undergo
species is electron deficient, the reactive site heterolytic cleavage.
for it is that part of the substrate molecule (a) CH3–SCH3, (b) CH3–CN, (c) CH3–Cu
which can supply electrons, e.g., π electrons Solution
in a double bond.
A reagent that brings an electron pair to
the reactive site is called a nucleophile (Nu:)
i.e., nucleus seeking and the reaction is then
called nucleophilic. A reagent that takes away
an electron pair from reactive site is called
electrophile (E+) i.e., electron seeking and the
reaction is called electrophilic. Problem 8.12
During a polar organic reaction, a Giving justification, categorise the
nucleophile attacks an electrophilic centre following molecules/ions as nucleophile
of the substrate which is that specific atom or electrophile:
or part of the substrate which is electron
deficient. Similarly, the electrophiles attack
at nucleophilic centre, which is the electron
rich centre of the substrate. Thus, the
electrophiles receive electron pair from the Solution
substrate when the two undergo bonding Nucleophiles: HS–,C2H5O–,(CH3)3N:H2N:–
interaction. A curved-arrow notation is used These species have unshared pair of
to show the movement of an electron pair electrons, which can be donated and
from the nucleophile to the electrophile. Some shared with an electrophile.
examples of nucleophiles are the negatively + + +
Electrophiles: BF 3 ,C1 H 3 –C =O,N O 2 .
charged ions with lone pair of electrons such Reactive sites have only six valence
as hydroxide (HO– ), cyanide (NC–) ions and electrons; can accept electron pair from
carbanions (R3C:–). Neutral molecules such a nucleophile.
as etc., can also act as
nucleophiles due to the presence of lone Problem 8.13
pair of electrons. Examples of electrophiles Identify electrophilic centre in the
+
include carbocations (C H 3 ) and neutral following: CH3CH=O, CH3CN, CH3I.
molecules having functional groups like Solution
carbonyl group (>C=O) or alkyl halides * *
A m o n g C H 3 H C = O , H 3 C C ≡N , a n d
(R 3C-X, where X is a halogen atom). The *
H3C –I, the starred carbon atoms are
carbon atom in carbocations has sextet
electrophilic centers as they will have
configuration; hence, it is electron deficient
and can receive a pair of electrons from the partial positive charge due to polarity of
nucleophiles. In neutral molecules such as the bond.
alkyl halides, due to the polarity of the C-X
bond a partial positive charge is generated 8.7.3 Electron Movement in Organic
on the carbon atom and hence the carbon Reactions
atom becomes an electrophilic centre at which The movement of electrons in organic
a nucleophile can attack. reactions can be shown by curved-arrow

Unit 8.indd 273 11/10/2022 15:21:53


274 chemistry

notation. It shows how changes in bonding 8.7.5 Inductive Effect


occur due to electronic redistribution during
When a covalent bond is formed between
the reaction. To show the change in position
atoms of different electronegativity, the
of a pair of electrons, curved arrow starts
electron density is more towards the more
from the point from where an electron pair is
electronegative atom of the bond. Such a shift
shifted and it ends at a location to which the
of electron density results in a polar covalent
pair of electron may move.
bond. Bond polarity leads to various electronic
Presentation of shifting of electron pair is effects in organic compounds.
given below : Let us consider cholorethane (CH3CH2Cl)
(i) from π bond to in which the C–Cl bond is a polar covalent
adjacent bond position bond. It is polarised in such a way that the
carbon-1 gains some positive charge (δ +)
(ii) from π bond to and the chlorine some negative charge (δ–).
adjacent atom The fractional electronic charges on the two
(iii) from atom to adjacent atoms in a polar covalent bond are denoted
bond position by symbol δ (delta) and the shift of electron
Movement of single electron is indicated by density is shown by an arrow that points from
a single barbed ‘fish hooks’ (i.e. half headed δ+ to δ– end of the polar bond.
curved arrow). For example, in transfer of δδ+ δ+ δ−
hydroxide ion giving ethanol and in the CH3→CH2→Cl
dissociation of chloromethane, the movement 2 1
of electron using curved arrows can be In turn carbon-1, which has developed
depicted as follows: partial positive charge (δ + ) draws some
electron density towards it from the adjacent
C-C bond. Consequently, some positive charge
(δδ+ ) develops on carbon-2 also, where δδ+
symbolises relatively smaller positive charge
as compared to that on carbon – 1. In other
words, the polar C – Cl bond induces polarity
8.7.4 Electron Displacement Effects in in the adjacent bonds. Such polarisation of
Covalent Bonds σ-bond caused by the polarisation of adjacent
σ-bond is referred to as the inductive effect.
The electron displacement in an organic This effect is passed on to the subsequent
molecule may take place either in the ground bonds also but the effect decreases rapidly
state under the influence of an atom or a as the number of intervening bonds increases
substituent group or in the presence of an and becomes vanishingly small after three
appropriate attacking reagent. The electron bonds. The inductive effect is related to the
displacements due to the influence of ability of substituent(s) to either withdraw or
an atom or a substituent group present in donate electron density to the attached carbon
the molecule cause permanent polarlisation atom. Based on this ability, the substitutents
of the bond. Inductive effect and resonance can be classified as electron-withdrawing or
effects are examples of this type of electron electron donating groups relative to hydrogen.
displacements. Temporary electron Halogens and many other groups such as
displacement effects are seen in a molecule nitro (- NO2), cyano (- CN), carboxy (- COOH),
when a reagent approaches to attack it. ester (COOR), aryloxy (-OAr, e.g. – OC6H5), etc.
This type of electron displacement is called are electron-withdrawing groups. On the other
electromeric effect or polarisability effect. hand, the alkyl groups like methyl (–CH3) and
In the following sections we will learn about ethyl (–CH2–CH3) are usually considered as
these types of electronic displacements. electron donating groups.
­

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organic chemistry – some basic principles and techniques 275

benzene cannot be adequately represented


Problem 8.14 by any of these structures, rather it is
Which bond is more polar in the following a hybrid of the two structures (I and II)
pairs of molecules: (a) H3C-H, H3C-Br called resonance structures. The resonance
(b) H 3 C-NH 2 , H 3 C-OH (c) H 3 C-OH, structures (canonical structures or
H3C-SH contributing structures) are hypothetical
and individually do not represent any
Solution
real molecule. They contribute to the actual
(a) C–Br, since Br is more electronegative structure in proportion to their stability.
than H, (b) C–O, (c) C–O Another example of resonance is provided
Problem 8.15 by nitromethane (CH 3NO 2) which can be
In which C–C bond of CH3CH2CH2Br, the represented by two Lewis structures, (I and
inductive effect is expected to be the least? II). There are two types of N-O bonds in these
structures.
Solution
Magnitude of inductive effect diminishes
as the number of intervening bonds
increases. Hence, the effect is least in the
bond between carbon-3 and hydrogen.
However, it is known that the two N–O
8.7.6 Resonance Structure bonds of nitromethane are of the same
length (intermediate between a N–O single
There are many organic molecules whose bond and a N=O double bond). The actual
behaviour cannot be explained by a single Lewis structure of nitromethane is therefore
structure. An example is that of a resonance hybrid of the two canonical
benzene. Its cyclic structure forms I and II.
containing alternating C–C single The energy of actual structure of the molecule
and C=C double bonds shown (the resonance hybrid) is lower than that of
is inadequate for explaining its Benzene any of the canonical structures. The difference
characteristic properties. in energy between the actual structure and the
As per the above representation, benzene lowest energy resonance structure is called the
should exhibit two different bond lengths, resonance stabilisation energy or simply
due to C–C single and C=C double bonds. the resonance energy. The more the number
However, as determined experimentally of important contributing structures, the
benzene has a uniform C–C bond distances more is the resonance energy. Resonance is
particularly important when the contributing
of 139 pm, a value intermediate between the
structures are equivalent in energy.
C–C single(154 pm) and C=C double (134
pm) bonds. Thus, the structure of benzene The following rules are applied while writing
cannot be represented adequately by the resonance structures:
The resonance structures have (i) the same
above structure. Further, benzene can be
positions of nuclei and (ii) the same number of
represented equally well by the energetically
unpaired electrons. Among the resonance
identical structures I and II. structures, the one which has more number
of covalent bonds, all the atoms with octet
of electrons (except hydrogen which has a
duplet), less separation of opposite charges, (a
negative charge if any on more electronegative
atom, a positive charge if any on more
Therefore, according to the resonance electropositive atom) and more dispersal of
theory (Unit 4) the actual structure of charge, is more stable than others.

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276 chemistry

Problem 8.16 Solution


Write resonance structures of CH3COO– The two structures are less important
and show the movement of electrons by contributors as they involve charge
curved arrows. separation. Additionally, structure
I contains a carbon atom with an
Solution
incomplete octet.
First, write the structure and put
unshared pairs of valence electrons on 8.7.7 Resonance Effect
appropriate atoms. Then draw the arrows
The resonance effect is defined as ‘the polarity
one at a time moving the electrons to get
produced in the molecule by the interaction
the other structures.
of two π-bonds or between a π-bond and
lone pair of electrons present on an adjacent
atom’. The effect is transmitted through the
chain. There are two types of resonance or
mesomeric effect designated as R or M effect.
Problem 8.17 (i) Positive Resonance Effect (+R effect)
Write resonance structures of In this effect, the transfer of electrons is away
CH2=CH–CHO. Indicate relative stability from an atom or substituent group attached
of the contributing structures. to the conjugated system. This electron
displacement makes certain positions in the
Solution
molecule of high electron densities. This effect
in aniline is shown as :

Stability: I > II > III (ii) Negative Resonance Effect (- R effect)


[I: Most stable, more number of covalent This effect is observed when the transfer of
bonds, each carbon and oxygen atom has electrons is towards the atom or substituent
an octet and no separation of opposite group attached to the conjugated system.
charge II: negative charge on more For example in nitrobenzene this electron
electronegative atom and positive charge displacement can be depicted as :
on more electropositive atom; III: does
not contribute as oxygen has positive
charge and carbon has negative charge,
hence least stable].
Problem 8.18
Explain why the following two structures,
I and II cannot be the major contributors The atoms or substituent groups, which
to the real structure of CH3COOCH3. represent +R or –R electron displacement
effects are as follows :
+R effect: – halogen, –OH, –OR, –OCOR, –NH2,
–NHR, –NR2, –NHCOR,
– R effect: – COOH, –CHO, >C=O, – CN, –NO2

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organic chemistry – some basic principles and techniques 277

The presence of alternate single and system or to an atom with an unshared


double bonds in an open chain or cyclic system p orbital. The σ electrons of C—H bond of the
is termed as a conjugated system. These alkyl group enter into partial conjugation with
systems often show abnormal behaviour. the attached unsaturated system or with the
The examples are 1,3- butadiene, aniline unshared p orbital. Hyperconjugation is a
and nitrobenzene etc. In such systems, the permanent effect.
π-electrons are delocalised and the system To understand hyperconjugation effect, let
develops polarity. +
us take an example of CH3 C H2 (ethyl cation) in
8.7.8 Electromeric Effect (E effect) which the positively charged carbon atom has
It is a temporary effect. The organic compounds an empty p orbital. One of the C-H bonds of
having a multiple bond (a double or triple the methyl group can align in the plane of this
bond) show this effect in the presence of empty p orbital and the electrons constituting
an attacking reagent only. It is defined as the C-H bond in plane with this p orbital can
the complete transfer of a shared pair of then be delocalised into the empty p orbital
π-electrons to one of the atoms joined by a as depicted in Fig. 8.4 (a).
multiple bond on the demand of an attacking
reagent. The effect is annulled as soon as the
attacking reagent is removed from the domain
of the reaction. It is represented by E and the
shifting of the electrons is shown by a curved
arrow ( ). There are two distinct types of
electromeric effect.
(i) Positive Eelctromeric Effect (+E effect) In
this effect the π−electrons of the multiple
bond are transferred to that atom to which
the reagent gets attached. For example:
Fig. 8.4(a) Orbital diagram showing
hyperconjugation in ethyl cation

This type of overlap stabilises the


carbocation because electron density from
(ii) Negative Electromeric Effect (–E effect) In the adjacent σ bond helps in dispersing the
this effect the π - electrons of the multiple positive charge.
bond are transferred to that atom to which
the attacking reagent does not get attached.
For example:

When inductive and electromeric effects


operate in opposite directions, the electomeric
effect predominates.
In general, greater the number of alkyl
8.7.9 Hyperconjugation groups attached to a positively charged carbon
Hyperconjugation is a general stabilising atom, the greater is the hyperconjugation
interaction. It involves delocalisation of interaction and stabilisation of the cation.
σ electrons of C—H bond of an alkyl group Thus, we have the following relative stability
directly attached to an atom of unsaturated of carbocations :

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278 chemistry

Problem 8.19 +
Explain why (CH 3) 3C is more stable
+ +
than CH3C H2 and C H3 is the least stable
cation.
Hyperconjugation is also possible in Solution
alkenes and alkylarenes. +
Hyperconjugation interaction in (CH3)3C is+
Delocalisation of electrons by +
greater than in CH3C H2 as the (CH3)3C
hyperconjugation in the case of alkene can +
has nine C-H bonds. In C H3, vacant p
be depicted as in Fig. 8.4(b).
orbital is perpendicular to the plane
in which C-H bonds lie; hence cannot
+
overlap with it. Thus, C H 3 lacks
hyperconjugative stability.

8.7.10 Types of Organic Reactions and


Mechanisms
Organic reactions can be classified into the
Fig. 8.4(b) Orbital diagram showing following categories:
hyperconjugation in propene (i) Substitution reactions
(ii) Addition reactions
There are various ways of looking at the (iii) Elimination reactions
hyperconjugative effect. One of the way is to (iv) Rearrangement reactions
regard C—H bond as possessing partial ionic
character due to resonance. You will be studying these reactions in
Unit 9 and later in class XII.
8.8 Methods of Purification of
Organic Compounds
Once an organic compound is extracted
from a natural source or synthesised in the
laboratory, it is essential to purify it. Various
methods used for the purification of organic
compounds are based on the nature of the
compound and the impurity present in it.
The common techniques used for
purification are as follows :
(i) Sublimation
(ii) Crystallisation
(iii) Distillation
(iv) Differential extraction and
(v) Chromatography
Finally, the purity of a compound is
ascertained by determining its melting or
boiling point. Most of the pure compounds
have sharp melting points and boiling points.
The hyperconjugation may also be New methods of checking the purity of an
regarded as no bond resonance. organic compound are based on different

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organic chemistry – some basic principles and techniques 279

types of chromatographic and spectroscopic carefully. On boiling, the vapours of lower


techniques. boiling component are formed first. The
vapours are condensed by using a condenser
8.8.1 Sublimation
and the liquid is collected in a receiver.
You have learnt earlier that on heating, some The vapours of higher boiling component
solid substances change from solid to vapour form later and the liquid can be collected
state without passing through liquid state. separately.
The purification technique based on the above
principle is known as sublimation and is used
to separate sublimable compounds from non-
sublimable impurities.
8.8.2 Crystallisation
This is one of the most commonly used
techniques for the purification of solid organic
compounds. It is based on the difference in
the solubilities of the compound and the
impurities in a suitable solvent. The impure
compound is dissolved in a solvent in which it
is sparingly soluble at room temperature but
appreciably soluble at higher temperature.
The solution is concentrated to get a nearly
saturated solution. On cooling the solution,
pure compound crystallises out and is
removed by filtration. The filtrate (mother
liquor) contains impurities and small quantity
of the compound. If the compound is highly
soluble in one solvent and very little soluble
in another solvent, crystallisation can be Fig.8.5 Simple distillation. The vapours of a
satisfactorily carried out in a mixture of these substance formed are condensed and
the liquid is collected in conical flask.
solvents. Impurities, which impart colour to
the solution are removed by adsorbing over
activated charcoal. Repeated crystallisation Fractional Distillation: If the difference
becomes necessary for the purification in boiling points of two liquids is not much,
of compounds containing impurities of simple distillation cannot be used to separate
comparable solubilities. them. The vapours of such liquids are formed
within the same temperature range and are
8.8.3 Distillation condensed simultaneously. The technique of
This important method is used to separate fractional distillation is used in such cases. In
(i) volatile liquids from nonvolatile impurities this technique, vapours of a liquid mixture are
and (ii) the liquids having sufficient difference passed through a fractionating column before
in their boiling points. Liquids having condensation. The fractionating column is
different boiling points vaporise at different fitted over the mouth of the round bottom
temperatures. The vapours are cooled and flask (Fig.8.6, page 280).
the liquids so formed are collected separately. Vapours of the liquid with higher boiling
Chloroform (b.p 334 K) and aniline (b.p. 457 point condense before the vapours of the
K) are easily separated by the technique of liquid with lower boiling point. The vapours
distillation (Fig 8.5). The liquid mixture is rising up in the fractionating column become
taken in a round bottom flask and heated richer in more volatile component. By the

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280 chemistry

unit in the fractionating column is called a


theoretical plate. Commercially, columns
with hundreds of plates are available.
One of the technological applications of
fractional distillation is to separate different
fractions of crude oil in petroleum industry.
Distillation under reduced
pressure: This method is
used to purify liquids having
very high boiling points and
those, which decompose at
or below their boiling points.
Such liquids are made to boil
at a temperature lower than
their normal boiling points
by reducing the pressure on
their surface. A liquid boils
at a temperature at which its
vapour pressure is equal to
the external pressure. The
pressure is reduced with
the help of a water pump
or vacuum pump (Fig.8.8).
Glycerol can be separated from
Fig.8.6 Fractional distillation. The vapours of lower boiling spent-lye in soap industry by
fraction reach the top of the column first followed by using this technique.
vapours of higher boiling fractions.

time the vapours reach to the top of the


fractionating column, these are rich in the
more volatile component. Fractionating
columns are available in various sizes and
designs as shown in Fig.8.7. A fractionating
column provides many surfaces for heat
exchange between the ascending vapours
and the descending condensed liquid. Some
of the condensing liquid in the fractionating
column obtains heat from the ascending
vapours and revaporises. The vapours thus
become richer in low boiling component. The
vapours of low boiling component ascend
to the top of the column. On reaching the
top, the vapours become pure in low boiling
component and pass through the condenser
and the pure liquid is collected in a receiver.
After a series of successive distillations, the
remaining liquid in the distillation flask gets
enriched in high boiling component. Each
Fig.8.7 Different types of fractionating columns.
successive condensation and vaporisation

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organic chemistry – some basic principles and techniques 281

Fig.8.8 Distillation under reduced pressure. A liquid boils at a temperature below its
vapour pressure by reducing the pressure.

Steam Distillation: This technique is 8.8.4 Differential Extraction


applied to separate substances which are When an organic compound is present in an
steam volatile and are immiscible with water. aqueous medium, it is separated by shaking
In steam distillation, steam from a steam it with an organic solvent in which it is more
generator is passed through a heated flask soluble than in water. The organic solvent and
containing the liquid to be distilled. The the aqueous solution should be immiscible
mixture of steam and the volatile organic with each other so that they form two distinct
compound is condensed and collected. The layers which can be separated by separatory
compound is later separated from water using funnel. The organic solvent is later removed
a separating funnel. In steam distillation, by distillation or by evaporation to get back
the liquid boils when the sum of vapour the compound. Differential extraction is
pressures due to the organic liquid (p1) carried out in a separatory funnel as shown in
and that due to water (p2) becomes equal to Fig. 8.10 (Page 282). If the organic compound
the atmospheric pressure (p), i.e. p =p1+ p2. is less soluble in the organic solvent, a very
Since p1 is lower than p, the organic liquid large quantity of solvent would be required
vaporises at lower temperature than its to extract even a very small quantity of the
boiling point. compound. The technique of continuous
Thus, if one of the substances in the extraction is employed in such cases. In this
mixture is water and the other, a water technique same solvent is repeatedly used for
insoluble substance, then the mixture will boil extraction of the compound.
close to but below, 373K. A mixture of water 8.8.5 Chromatography
and the substance is obtained which can Chromatography is an important technique
be separated by using a separating funnel. extensively used to separate mixtures into
Aniline is separated by this technique from their components, purify compounds and
aniline – water mixture (Fig.8.9, Page 282). also to test the purity of compounds. The

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282 chemistry

Fig.8.9 Steam distillation. Steam volatile component volatilizes, the vapours condense
in the condenser and the liquid collects in conical flask.
name chromatography is based on the Greek
word chroma, for colour since the method
was first used for the separation of coloured
substances found in plants. In this technique,
the mixture of substances is applied onto a
stationary phase, which may be a solid or a
liquid. A pure solvent, a mixture of solvents,
or a gas is allowed to move slowly over the
stationary phase. The components of the
mixture get gradually separated from one
another. The moving phase is called the
mobile phase.
Based on the principle involved,
chromatography is classified into different
categories. Two of these are:
(a) Adsorption chromatography, and Fig.8.10 Differential extraction. Extraction of com-
(b) Partition chromatography. pound takes place based on difference
in solubility
a) Adsorption Chromatography: Adsor-
ption chromatography is based on the fact
that different compounds are adsorbed on distances over the stationary phase. Following
an adsorbent to different degrees. Commonly are two main types of chromatographic
used adsorbents are silica gel and alumina. techniques based on the principle of differential
When a mobile phase is allowed to move adsorption.
over a stationary phase (adsorbent), the (a) Column chromatography, and
components of the mixture move by varying (b) Thin layer chromatography.

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organic chemistry – some basic principles and techniques 283

Column Chromatography: Column The glass plate is then placed in a closed jar
chromatography involves separation of containing the eluant (Fig. 8.12a). As the
a mixture over a column of adsorbent eluant rises up the plate, the components of
(stationary phase) packed in a glass tube. the mixture move up along with the eluant to
The column is fitted with a stopcock at its different distances depending on their degree
lower end (Fig. 8.11). The mixture adsorbed of adsorption and separation takes place.
on adsorbent is placed on the top of the The relative adsorption of each component
adsorbent column packed in a glass tube. of the mixture is expressed in terms of its
An appropriate eluant which is a liquid or a retardation factor i.e. Rf value (Fig.8.12 b).
mixture of liquids is allowed to flow down the Rf = Distance moved by the substance from base line (x)
column slowly. Depending upon the degree to Distance moved by the solvent from base line (y)
which the compounds are adsorbed, complete
separation takes place. The most readily
adsorbed substances are retained near the top
and others come down to various distances
in the column (Fig.8.11).

Fig.8.12 (a) T h i n l a y e r c h ro m a t o g r a p h y .
Chromatogram being developed.

Fig.8.11 Column chromatography. Different


stages of separation of components Fig.8.12 (b) Developed chromatogram.
of a mixture.
The spots of coloured compounds are
Thin Layer Chromatography: Thin layer visible on TLC plate due to their original colour.
chromatography (TLC) is another type of The spots of colourless compounds, which are
adsorption chromatography, which involves invisible to the eye but fluoresce in ultraviolet
separation of substances of a mixture over light, can be detected by putting the plate under
a thin layer of an adsorbent coated on glass ultraviolet light. Another detection technique
plate. A thin layer (about 0.2mm thick) of is to place the plate in a covered jar containing
an adsorbent (silica gel or alumina) is spread a few crystals of iodine. Spots of compounds,
over a glass plate of suitable size. The plate which adsorb iodine, will show up as brown
is known as thin layer chromatography plate spots. Sometimes an appropriate reagent
or chromaplate. The solution of the mixture may also be sprayed on the plate. For example,
to be separated is applied as a small spot amino acids may be detected by spraying the
about 2 cm above one end of the TLC plate. plate with ninhydrin solution (Fig.8.12b).

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284 chemistry

Partition Chromatography: Partition spot on the chromatogram. The spots of the


chromatography is based on continuous separated colourless compounds may be
differential partitioning of components of observed either under ultraviolet light or by
a mixture between stationary and mobile the use of an appropriate spray reagent as
phases. Paper chromatography is a type discussed under thin layer chromatography.
of partition chromatography. In paper
8.9 Qualitative Analysis of Organic
chromatography, a special quality paper
Compounds
known as chromatography paper is used.
Chromatography paper contains water trapped The elements present in organic compounds
in it, which acts as the stationary phase. are carbon and hydrogen. In addition to
A strip of chromatography paper spotted these, they may also contain oxygen, nitrogen,
at the base with the solution of the mixture is sulphur, halogens and phosphorus.
suspended in a suitable solvent or a mixture 8.9.1 Detection of Carbon and Hydrogen
of solvents (Fig. 8.13). This solvent acts as the Carbon and hydrogen are detected by heating
mobile phase. The solvent rises up the paper the compound with copper(II) oxide. Carbon
by capillary action and flows over the spot. The present in the compound is oxidised to
paper selectively retains different components carbon dioxide (tested with lime-water, which
according to their differing partition in the develops turbidity) and hydrogen to water
two phases. The paper strip so developed is (tested with anhydrous copper sulphate,
known as a chromatogram. The spots of the which turns blue).
separated coloured compounds are visible at C + 2CuO 2Cu + CO2
different heights from the position of initial 2H + CuO Cu + H2O
CO2 + Ca(OH)2 CaCO3↓ + H2O
5H2O + CuSO4 CuSO4.5H2O
White Blue
8.9.2 Detection of Other Elements
Nitrogen, sulphur, halogens and phosphorus
present in an organic compound are detected
by “Lassaigne’s test”. The elements present
in the compound are converted from covalent
form into the ionic form by fusing the
compound with sodium metal. Following
reactions take place:
Na + C + N NaCN
2Na + S Na2S
Na + X Na X
(X = Cl, Br or I)
C, N, S and X come from organic compound.
Cyanide, sulphide and halide of sodium so
formed on sodium fusion are extracted from
the fused mass by boiling it with distilled
water. This extract is known as sodium fusion
extract.
(A) Test for Nitrogen
Fig.8.13 Paper chromatography.
Chromatography paper in two different The sodium fusion extract is boiled with
shapes. iron(II) sulphate and then acidified with

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organic chemistry – some basic principles and techniques 285

concentrated sulphuric acid. The formation bromine and a yellow precipitate, insoluble
of Prussian blue colour confirms the presence in ammonium hydroxide shows the presence
of nitrogen. Sodium cyanide first reacts of iodine.
with iron(II) sulphate and forms sodium X– + Ag+ → AgX
hexacyanidoferrate(II). On heating with X represents a halogen – Cl, Br or I.
concentrated sulphuric acid some iron(II)
If nitrogen or sulphur is also present in the
ions are oxidised to iron(III) ions which
compound, the sodium fusion extract is
react with sodium hexacyanidoferrate(II)
first boiled with concentrated nitric acid to
to produce iron(III) hexacyanidoferrate(II) decompose cyanide or sulphide of sodium
(ferriferrocyanide) which is Prussian blue in formed during Lassaigne’s test. These ions
colour. would otherwise interfere with silver nitrate
6CN– + Fe2+ → [Fe(CN)6]4– test for halogens.
3[Fe(CN)6]4– + 4Fe3+ Fe4[Fe(CN)6]3.xH2O (D) Test for Phosphorus
 Prussian blue The compound is heated with an oxidising
(B) Test for Sulphur agent (sodium peroxide). The phosphorus
(a) The sodium fusion extract is acidified present in the compound is oxidised to
with acetic acid and lead acetate is added phosphate. The solution is boiled with nitric
to it. A black precipitate of lead sulphide acid and then treated with ammonium
indicates the presence of sulphur. molybdate. A yellow colouration or precipitate
indicates the presence of phosphorus.
S2– + Pb2+ → PbS
Black Na3PO4 + 3HNO3 → H3PO4+3NaNO3
(b) On treating sodium fusion extract with H3PO4 + 12(NH4)2MoO4 + 21HNO3 →
sodium nitroprusside, appearance of Ammonium
a violet colour further indicates the molybdate
presence of sulphur. (NH4)3PO4.12MoO3 + 21NH4NO3 + 12H2O
S2– + [Fe(CN)5NO]2– → [Fe(CN)5NOS]4– Ammonium
Violet phosphomolybdate
In case, nitrogen and sulphur both are 8.10 Quantitative Analysis
present in an organic compound, sodium
Quantitative analysis of compounds is very
thiocyanate is formed. It gives blood red colour
important in organic chemistry. It helps
and no Prussian blue since there are no free
chemists in the determination of mass per
cyanide ions.
cent of elements present in a compound. You
Na + C + N + S → NaSCN
have learnt in Unit-1 that mass per cent of
Fe +SCN
3+ –
→ [Fe(SCN)]2+ elements is required for the determination of

Blood red emperical and molecular formula.
If sodium fusion is carried out with excess The percentage composition of elements
of sodium, the thiocyanate decomposes to present in an organic compound is determined
yield cyanide and sulphide. These ions give by the following methods:
their usual tests.
NaSCN + 2Na → NaCN+Na2S 8.10.1 Carbon and Hydrogen
(C) Test for Halogens Both carbon and hydrogen are estimated in
one experiment. A known mass of an organic
The sodium fusion extract is acidified with
compound is burnt in the presence of excess
nitric acid and then treated with silver nitrate.
of oxygen and copper(II) oxide. Carbon and
A white precipitate, soluble in ammonium
hydrogen in the compound are oxidised to
hydroxide shows the presence of chlorine,
carbon dioxide and water respectively.
a yellowish precipitate, sparingly soluble in
ammonium hydroxide shows the presence of CxHy + (x + y/4) O2 → x CO2 + (y/2) H2O

Unit 8.indd 285 10/10/2022 10:37:37 AM


286 chemistry

Fig.8.14 Estimation of carbon and hydrogen. Water and carbon dioxide formed on oxidation of substance
are absorbed in anhydrous calcium chloride and potassium hydroxide solutions respectively
contained in U tubes.

The mass of water produced is determined 8.10.2 Nitrogen


by passing the mixture through a weighed There are two methods for estimation of
U-tube containing anhydrous calcium chloride. nitrogen: (i) Dumas method and (ii) Kjeldahl’s
Carbon dioxide is absorbed in another U-tube method.
containing concentrated solution of potassium (i) Dumas method: The nitrogen containing
hydroxide. These tubes are connected in series organic compound, when heated with copper
(Fig. 8.14). The increase in masses of calcium oxide in an atmosphere of carbon dioxide,
chloride and potassium hydroxide gives the yields free nitrogen in addition to carbon
amounts of water and carbon dioxide from dioxide and water.
which the percentages of carbon and hydrogen
CxHyNz + (2x + y/2) CuO →
are calculated.
Let the mass of organic compound be x CO2 + y/2 H2O + z/2 N2 + (2x + y/2) Cu
m g, mass of water and carbon dioxide
Traces of nitrogen oxides formed, if
produced be m1 and m2 g respectively;
any, are reduced to nitrogen by passing the
12 × m2 × 100 gaseous mixture over a heated copper gauze.
Percentage of carbon=
44 × m The mixture of gases so produced is collected
2 × m1 × 100 over an aqueous solution of potassium
Percentage of hydrogen = hydroxide which absorbs carbon dioxide.
18 × m Nitrogen is collected in the upper part of the
Problem 8.20 graduated tube (Fig.8.15).
On complete combustion, 0.246 g of an Let the mass of organic compound = m g
organic compound gave 0.198g of carbon Volume of nitrogen collected = V1 mL
dioxide and 0.1014g of water. Determine
Room temperature = T1K
the percentage composition of carbon
and hydrogen in the compound. 1 1 × 273
PV
Volume of nitrogen at STP =
Solution 760 × T1
12 × 0.198 × 100 (Let it be V mL)
Percentage of carbon =
44 × 0.246 Where p 1 and V 1 are the pressure and
= 21.95% volume of nitrogen, p1 is different from the
atmospheric pressure at which nitrogen gas
2 × 0.1014 × 100 is collected. The value of p1 is obtained by
Percentage of hydrogen =
18 × 0.246 the relation;
= 4.58% p1= Atmospheric pressure – Aqueous tension
22400 mL N2 at STP weighs 28 g.

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organic chemistry – some basic principles and techniques 287

Fig. 8.15 Dumas method. The organic compound yields nitrogen gas on heating it with
copper(II) oxide in the presence of CO2 gas. The mixture of gases is collected over
potassium hydroxide solution in which CO2 is absorbed and volume of nitrogen
gas is determined.

28 × V
V mL N 2 at STP weighs = g 28 × 41.9
22400 41.9 mL of nitrogen weighs = g
22400
28 × V × 100
Percentage of nitrogen = 28 × 41.9 × 100
22400 × m Percentage of nitrogen =
22400 × 0.3
Problem 8.21 = 17.46%
In Dumas’ method for estimation of
nitrogen, 0.3g of an organic compound
gave 50mL of nitrogen collected at 300K
temperature and 715mm pressure. (ii) Kjeldahl’s method: The compound
Calculate the percentage composition containing nitrogen is heated with concentrated
of nitrogen in the compound. (Aqueous sulphuric acid. Nitrogen in the compound
tension at 300K=15 mm) gets converted to ammonium sulphate
(Fig. 8.16). The resulting acid mixture is then
Solution
heated with excess of sodium hydroxide.
Volume of nitrogen collected at 300K and The liberated ammonia gas is absorbed in
715mm pressure is 50 mL an excess of standard solution of sulphuric
Actual pressure = 715-15 =700 mm acid. The amount of ammonia produced is
273 × 700 × 50 determined by estimating the amount of
Volume of nitrogen at STP sulphuric acid consumed in the reaction. It
300 × 760
is done by estimating unreacted sulphuric
41.9 mL
acid left after the absorption of ammonia by
22,400 mL of N2 at STP weighs = 28 g titrating it with standard alkali solution. The
difference between the initial amount of acid

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288 chemistry

Fig.8.16 Kjeldahl method. Nitrogen-containing compound is treated with concentrated H2SO4 to get
ammonium sulphate which liberates ammonia on treating with NaOH; ammonia is absorbed
in known volume of standard acid.
taken and that left after the reaction gives the 14 × M × 2(V − V1 / 2) 100
amount of acid reacted with ammonia. Percentage of N = ×
1000 m
Organic compound + H2SO4 → (NH4)2SO4
1.4 × M × 2 (V − V / 2)
Na2SO4 + 2NH3 + 2H2O =
m
2NH3 + H2SO4 → (NH4)2SO4
Kjeldahl method is not applicable to
Let the mass of organic compound taken = m g compounds containing nitrogen in nitro and
Volume of H2SO4 of molarity, M, azo groups and nitrogen present in the ring
taken = V mL (e.g. pyridine) as nitrogen of these compounds
Volume of NaOH of molarity, M, used for does not change to ammonium sulphate
titration of excess of H2SO4 = V1 mL under these conditions.
V1mL of NaOH of molarity M
Problem 8.22
= V1 /2 mL of H2SO4 of molarity M
Volume of H 2 SO 4 of molarity M unused During estimation of nitrogen present
= (V - V1/2) mL in an organic compound by Kjeldahl’s
method, the ammonia evolved from
(V- V1/2) mL of H2SO4 of molarity M 0.5 g of the compound in Kjeldahl’s
= 2(V-V1/2) mL of NH3 solution of estimation of nitrogen, neutralized 10 mL
molarity M. of 1 M H2SO4. Find out the percentage of
1000 mL of 1 M NH 3 solution contains nitrogen in the compound.
17g NH3 or 14 g of N Solution
2(V-V1/2) mL of NH3 solution of molarity M 1 M of 10 mL H2SO4=1M of 20 mL NH3
contains: 1000 mL of 1M ammonia contains 14 g
14 × M × 2(V − V1 / 2) nitrogen
gN
1000 20 mL of 1M ammonia contains

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organic chemistry – some basic principles and techniques 289

14 × 20 Percentage of halogen
g nitrogen
1000 atomic mass of X × m1g
=
14×20×100 molecular mass of AgX
Percentage of nitrogen = = 56.0%
1000×0.5
Problem 8.23
8.10.3 Halogens In Carius method of estimation of
Carius method: A known mass of an organic halogen, 0.15 g of an organic compound
compound is heated with fuming nitric acid in gave 0.12 g of AgBr. Find out the
the presence of silver nitrate contained in a hard percentage of bromine in the compound.
glass tube known as Carius tube, (Fig.8.17) Solution
Molar mass of AgBr = 108 + 80
= 188 g mol-1
188 g AgBr contains 80 g bromine
80 × 0.12
0.12 g AgBr contains g bromine
188

80 × 0.12 × 100
Percentage of bromine =
188×0.15
= 34.04%

8.10.4 Sulphur
A known mass of an organic compound is
heated in a Carius tube with sodium peroxide
or fuming nitric acid. Sulphur present in the
compound is oxidised to sulphuric acid. It
is precipitated as barium sulphate by adding
excess of barium chloride solution in water.
The precipitate is filtered, washed, dried and
weighed. The percentage of sulphur can be
Fig. 8.17 Carius method. Halogen containing calculated from the mass of barium sulphate.
organic compound is heated with fuming
nitric acid in the presence of silver
Let the mass of organic
nitrate. compound taken = m g
and the mass of barium
in a furnace. Carbon and hydrogen present in sulphate formed = m1g
the compound are oxidised to carbon dioxide 1 mol of BaSO4 = 233 g BaSO4 = 32 g sulphur
and water. The halogen present forms the 32 × m1 × 100
corresponding silver halide (AgX). It is filtered, m1 g BaSO4 contains g sulphur
233 × m
washed, dried and weighed.
32 × m1 × 100
Let the mass of organic Percentage of sulphur =
compound taken = m g 233 × m
Mass of AgX formed = m1 g
1 mol of AgX contains 1 mol of X
Mass of halogen in m1g of AgX Problem 8.24
atomic mass of X × m1g In sulphur estimation, 0.157 g of an
= organic compound gave 0.4813 g of
molecular mass of AgX

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290 chemistry

percentage composition (100) and the sum of


barium sulphate. What is the percentage
the percentages of all other elements. However,
of sulphur in the compound?
oxygen can also be estimated directly as follows:
Solution A definite mass of an organic compound is
Molecular mass of BaSO4 = 137+32+64 decomposed by heating in a stream of nitrogen
gas. The mixture of gaseous products containing
= 233 g
oxygen is passed over red-hot coke when all
233 g BaSO4 contains 32 g sulphur the oxygen is converted to carbon monoxide.
32 × 0.4813 This mixture is passed through warm iodine
0.4813 g BaSO4 contains g pentoxide (I2O5) when carbon monoxide is
g sulphur 233
oxidised to carbon dioxide producing iodine.
32 × 0.4813 × 100 Compound  heat
→ O2 + other gaseous
Percentage of sulphur = products
233 × 0.157
2C + O2 
1373 K
→ 2CO]× 5 (A)
= 42.10%
I2O5 + 5CO → I2 + 5CO2]× 2 (B)

8.10.5 Phosphorus On making the amount of CO produced in


A known mass of an organic compound is equation (A) equal to the amount of CO used
heated with fuming nitric acid whereupon in equation (B) by multiplying the equations
phosphorus present in the compound is (A) and (B) by 5 and 2 respectively; we find
oxidised to phosphoric acid. It is precipitated that each mole of oxygen liberated from
as ammonium phosphomolybdate, (NH4)3 the compound will produce two moles of
PO 4 .12MoO 3 , by adding ammonia and carbondioxide.
ammonium molybdate. Alter natively, Thus 88 g carbon dioxide is obtained if 32 g
phosphoric acid may be precipitated as oxygen is liberated.
MgNH4PO4 by adding magnesia mixture which Let the mass of organic compound taken be m g
on ignition yields Mg2P2O7. Mass of carbon dioxide produced be m1 g
Let the mass of organic compound taken ∴ m 1 g carbon dioxide is obtained from
= m g and mass of ammonium phospho 32 × m1
molydate = m1g g O2
88
Molar mass of (NH4)3PO4.12MoO3 = 1877g 32 × m1 × 100
∴Percentage of oxygen = %
31 × m1 × 100 88 × m
Percentage of phosphorus = %
1877 × m The percentage of oxygen can be derived
from the amount of iodine produced also.
If phosphorus is estimated as Mg2P2O7,
Presently, the estimation of elements in
62 × m1 × 100 an organic compound is carried out by using
Percentage of phosphorus = ×%
222 microquantities of substances and automatic
where, 222 u is the molar mass of Mg2P2O7, experimental techniques. The elements,
m, the mass of organic compound taken, carbon, hydrogen and nitrogen present in a
m1, the mass of Mg2P2O7 formed and 62, the compound are determined by an apparatus
mass of two phosphorus atoms present in the known as CHN elemental analyser. The
compound Mg2P2O7. analyser requires only a very small amount
of the substance (1-3 mg) and displays the
8.10.6 Oxygen values on a screen within a short time. A
The percentage of oxygen in an organic compound detailed discussion of such methods is beyond
is usually found by difference between the total the scope of this book.

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organic chemistry – some basic principles and techniques 291

Summary

In this unit, we have learnt some basic concepts in structure and reactivity of organic
compounds, which are formed due to covalent bonding. The nature of the covalent bonding
in organic compounds can be described in terms of orbitals hybridisation concept,
according to which carbon can have sp3, sp2 and sp hybridised orbitals. The sp3, sp2 and sp
hybridised carbons are found in compounds like methane, ethene and ethyne respectively.
The tetrahedral shape of methane, planar shape of ethene and linear shape of ethyne can
be understood on the basis of this concept. A sp3 hybrid orbital can overlap with 1s orbital
of hydrogen to give a carbon - hydrogen (C–H) single bond (sigma, σ bond). Overlap of a sp2
orbital of one carbon with sp2 orbital of another results in the formation of a carbon–carbon
σ bond. The unhybridised p orbitals on two adjacent carbons can undergo lateral (side-
by-side) overlap to give a pi (π) bond. Organic compounds can be represented by various
structural formulas. The three dimensional representation of organic compounds on paper
can be drawn by wedge and dash formula.
Organic compounds can be classified on the basis of their structure or the functional
groups they contain. A functional group is an atom or group of atoms bonded together in a
unique fashion and which determines the physical and chemical properties of the compounds.
The naming of the organic compounds is carried out by following a set of rules laid down by
the International Union of Pure and Applied Chemistry (IUPAC). In IUPAC nomenclature,
the names are correlated with the structure in such a way that the reader can deduce the
structure from the name.
Organic reaction mechanism concepts are based on the structure of the substrate
molecule, fission of a covalent bond, the attacking reagents, the electron displacement effects
and the conditions of the reaction. These organic reactions involve breaking and making
of covalent bonds. A covalent bond may be cleaved in heterolytic or homolytic fashion.
A heterolytic cleavage yields carbocations or carbanions, while a homolytic cleavage gives
free radicals as reactive intermediate. Reactions proceeding through heterolytic cleavage
involve the complimentary pairs of reactive species. These are electron pair donor known as
nucleophile and an electron pair acceptor known as electrophile. The inductive, resonance,
electromeric and hyperconjugation effects may help in the polarisation of a bond making
certain carbon atom or other atom positions as places of low or high electron densities.
Organic reactions can be broadly classified into following types; substitution, addition,
elimination and rearrangement reactions.
Purification, qualitative and quantitative analysis of organic compounds are carried out
for determining their structures. The methods of purification namely : sublimation, distillation
and differential extraction are based on the difference in one or more physical properties.
Chromatography is a useful technique of separation, identification and purification of
compounds. It is classified into two categories : adsorption and partition chromatography.
Adsorption chromatography is based on differential adsorption of various components of a
mixture on an adsorbent. Partition chromatography involves continuous partitioning of the
components of a mixture between stationary and mobile phases. After getting the compound
in a pure form, its qualitative analysis is carried out for detection of elements present in it.
Nitrogen, sulphur, halogens and phosphorus are detected by Lassaigne’s test. Carbon and
hydrogen are estimated by determining the amounts of carbon dioxide and water produced.
Nitrogen is estimated by Dumas or Kjeldahl’s method and halogens by Carius method.
Sulphur and phosphorus are estimated by oxidising them to sulphuric and phosphoric acids
respectively. The percentage of oxygen is usually determined by difference between the total
percentage (100) and the sum of percentages of all other elements present.

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292 chemistry

Exercises

8.1 What are hybridisation states of each carbon atom in the following compounds ?
CH2=C=O, CH3CH=CH2, (CH3)2CO, CH2=CHCN, C6H6
8.2 Indicate the σ and π bonds in the following molecules :
C6H6, C6H12, CH2Cl2, CH2=C=CH2, CH3NO2, HCONHCH3
8.3 Write bond line formulas for : Isopropyl alcohol, 2,3-Dimethylbutanal, Heptan-4-one.
8.4 Give the IUPAC names of the following compounds :

(a) (b) (c)

(d) (e) (f) Cl2CHCH2OH

8.5 Which of the following represents the correct IUPAC name for the compounds
concerned ? (a) 2,2-Dimethylpentane or 2-Dimethylpentane (b)
2,4,7-Trimethyloctane or 2,5,7-Trimethyloctane (c) 2-Chloro-4-methylpentane or
4-Chloro-2-methylpentane (d) But-3-yn-1-ol or But-4-ol-1-yne.
8.6 Draw formulas for the first five members of each homologous series beginning with
the following compounds. (a) H–COOH (b) CH3COCH3 (c) H–CH=CH2
8.7 Give condensed and bond line structural formulas and identify the functional group(s)
present, if any, for :
(a) 2,2,4-Trimethylpentane
(b) 2-Hydroxy-1,2,3-propanetricarboxylic acid
(c) Hexanedial
8.8 Identify the functional groups in the following compounds

(a) (b) (c)

8.9 Which of the two: O2NCH2CH2O– or CH3CH2O– is expected to be more stable and
why?
8.10 Explain why alkyl groups act as electron donors when attached to a π system.
8.11 Draw the resonance structures for the following compounds. Show the electron shift
using curved-arrow notation.
+
(a) C 6 H 5 OH (b) C 6 H 5 NO 2 (c) CH 3 CH=CHCHO (d) C 6 H 5 –CHO (e) C 6 H 5 –CH 2
+
(f) CH3CH=CH C H2
8.12 What are electrophiles and nucleophiles ? Explain with examples.
8.13 Identify the reagents shown in bold in the following equations as nucleophiles or
electrophiles:

(a) CH3COOH + HO → CH3COO–+H2O

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organic chemistry – some basic principles and techniques 293


(b) CH3COCH3+ CN → (CH3)2C(CN)(OH)
+
(c) C6H6 + CH3CO → C6H5COCH3
8.14 Classify the following reactions in one of the reaction type studied in this unit.
– –
(a) CH3CH2Br + HS → CH3CH2SH + Br
(b) (CH3)2C = CH2 + HCI → (CH3)2CIC – CH3
– –
(c) CH3CH2Br + HO → CH2 = CH2 + H2O + Br
(d) (CH3)3C– CH2OH + HBr → (CH3)2CBrCH2CH2CH3 + H2O
8.15 What is the relationship between the members of following pairs of structures ?
Are they structural or geometrical isomers or resonance contributors ?

(a)

(b)

(c)

8.16 For the following bond cleavages, use curved-arrows to show the electron flow and
classify each as homolysis or heterolysis. Identify reactive intermediate produced
as free radical, carbocation and carbanion.

(a)

(b)

(c)

(d)

8.17 Explain the terms Inductive and Electromeric effects. Which electron displacement
effect explains the following correct orders of acidity of the carboxylic acids?
(a) Cl3CCOOH > Cl2CHCOOH > ClCH2COOH
(b) CH3CH2COOH > (CH3)2CHCOOH > (CH3)3C.COOH
8.18 Give a brief description of the principles of the following techniques taking an
example in each case.
(a) Crystallisation (b) Distillation (c) Chromatography
8.19 Describe the method, which can be used to separate two compounds with different
solubilities in a solvent S.
8.20 What is the difference between distillation, distillation under reduced pressure and
steam distillation ?

Unit 8.indd 293 10/10/2022 10:37:40 AM


294 chemistry

8.21 Discuss the chemistry of Lassaigne’s test.


8.22 Differentiate between the principle of estimation of nitrogen in an organic compound
by (i) Dumas method and (ii) Kjeldahl’s method.
8.23 Discuss the principle of estimation of halogens, sulphur and phosphorus present
in an organic compound.
8.24 Explain the principle of paper chromatography.
8.25 Why is nitric acid added to sodium extract before adding silver nitrate for testing
halogens?
8.26 Explain the reason for the fusion of an organic compound with metallic sodium for
testing nitrogen, sulphur and halogens.
8.27 Name a suitable technique of separation of the components from a mixture of
calcium sulphate and camphor.
8.28 Explain, why an organic liquid vaporises at a temperature below its boiling point
in its steam distillation ?
8.29 Will CCl4 give white precipitate of AgCl on heating it with silver nitrate? Give reason
for your answer.
8.30 Why is a solution of potassium hydroxide used to absorb carbon dioxide evolved
during the estimation of carbon present in an organic compound?
8.31 Why is it necessary to use acetic acid and not sulphuric acid for acidification of
sodium extract for testing sulphur by lead acetate test?
8.32 An organic compound contains 69% carbon and 4.8% hydrogen, the remainder
being oxygen. Calculate the masses of carbon dioxide and water produced when
0.20 g of this substance is subjected to complete combustion.
8.33 A sample of 0.50 g of an organic compound was treated according to Kjeldahl’s
method. The ammonia evolved was absorbed in 50 ml of 0.5 M H2SO4. The residual
acid required 60 mL of 0.5 M solution of NaOH for neutralisation. Find the percentage
composition of nitrogen in the compound.
8.34 0.3780 g of an organic chloro compound gave 0.5740 g of silver chloride in Carius
estimation. Calculate the percentage of chlorine present in the compound.
8.35 In the estimation of sulphur by Carius method, 0.468 g of an organic sulphur
compound afforded 0.668 g of barium sulphate. Find out the percentage of sulphur
in the given compound.
8.36 In the organic compound CH2 = CH – CH2 – CH2 – C ≡ CH, the pair of hydridised
orbitals involved in the formation of: C2 – C3 bond is:
(a) sp – sp2 (b) sp – sp3 (c) sp2 – sp3 (d) sp3 – sp3
8.37 In the Lassaigne’s test for nitrogen in an organic compound, the Prussian blue
colour is obtained due to the formation of:
(a) Na4[Fe(CN)6] (b) Fe4[Fe(CN)6]3 (c) Fe2[Fe(CN)6] (d) Fe3[Fe(CN)6]4
8.38 Which of the+ following carbocation+
is most+ stable ? +
(a) (CH3)3C. C­­­­­­­ H2 (b) (CH3)3C­­­  (c) CH3CH2C­­­  H2 (d) CH3C­­­  H CH2CH3
8.39 The best and latest technique for isolation, purification and separation of organic
compounds is:
(a) Crystallisation (b) Distillation (c) Sublimation (d) Chromatography
8.40 The reaction:
CH3CH2I + KOH(aq) → CH3CH2OH + KI
is classified as :
(a) electrophilic substitution (b) nucleophilic substitution
(c) elimination (d) addition

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Hydrocarbons 295

Unit 9

Hydrocarbons

Hydrocarbons are the important sources of energy.

After studying this unit, you will be


able to
• name hydrocarbons according to The term ‘hydrocarbon’ is self-explanatory which means
IUPAC system of nomenclature; compounds of carbon and hydrogen only. Hydrocarbons
• recognise and write structures play a key role in our daily life. You must be familiar
of isomers of alkanes,
with the terms ‘LPG’ and ‘CNG’ used as fuels. LPG is the
alkenes, alkynes and aromatic
abbreviated form of liquified petroleum gas whereas CNG
hydrocarbons;
• learn about various methods of
stands for compressed natural gas. Another term ‘LNG’
preparation of hydrocarbons; (liquified natural gas) is also in news these days. This is
• distinguish between alkanes, also a fuel and is obtained by liquifaction of natural gas.
alkenes, alkynes and aromatic Petrol, diesel and kerosene oil are obtained by the fractional
hydrocarbons on the basis of distillation of petroleum found under the earth’s crust.
physical and chemical properties; Coal gas is obtained by the destructive distillation of
• draw and differentiate between coal. Natural gas is found in upper strata during drilling
various conformations of ethane; of oil wells. The gas after compression is known as
• appreciate the role of compressed natural gas. LPG is used as a domestic fuel
hydrocarbons as sources of
with the least pollution. Kerosene oil is also used as a
energy and for other industrial
applications;
domestic fuel but it causes some pollution. Automobiles
• predict the formation of need fuels like petrol, diesel and CNG. Petrol and CNG
the addition products of operated automobiles cause less pollution. All these fuels
unsymmetrical alkenes and contain mixture of hydrocarbons, which are sources of
alkynes on the basis of electronic energy. Hydrocarbons are also used for the manufacture
mechanism; of polymers like polythene, polypropene, polystyrene etc.
• comprehend the structure of Higher hydrocarbons are used as solvents for paints. They
benzene, explain aromaticity are also used as the starting materials for manufacture
and understand mechanism of many dyes and drugs. Thus, you can well understand
of electrophilic substitution
the importance of hydrocarbons in your daily life. In this
reactions of benzene;
• predict the directive influence of
unit, you will learn more about hydrocarbons.
substituents in monosubstituted
9.1 CLASSIFICATION
benzene ring;
• learn about carcinogenicity and Hydrocarbons are of different types. Depending upon
toxicity. the types of carbon-carbon bonds present, they can
be classified into three main categories – (i) saturated

Unit 9.indd 295 10/10/2022 10:37:52 AM


296 chemistry

(ii) unsaturated and (iii) aromatic of the general formula for alkane family
hydrocarbons. Saturated hydrocarbons or homologous series? If we examine the
contain carbon-carbon and carbon-hydrogen formula of different alkanes we find that
single bonds. If different carbon atoms are the general formula for alkanes is CnH2n+2. It
joined together to form open chain of carbon represents any particular homologue when n
atoms with single bonds, they are termed is given appropriate value. Can you recall the
as alkanes as you have already studied in structure of methane? According to VSEPR
Unit 8. On the other hand, if carbon atoms theory (Unit 4), methane has a tetrahedral
form a closed chain or a ring, they are termed structure (Fig. 9.1), in which carbon atom lies
as cycloalkanes. Unsaturated hydrocarbons at the centre and the four hydrogen atoms lie
contain carbon-carbon multiple bonds – at the four corners of a regular tetrahedron.
double bonds, triple bonds or both. Aromatic All H-C-H bond angles are of 109.5°.
hydrocarbons are a special type of cyclic
compounds. You can construct a large
number of models of such molecules of both
types (open chain and close chain) keeping
in mind that carbon is tetravalent and
hydrogen is monovalent. For making models
of alkanes, you can use toothpicks for bonds
and plasticine balls for atoms. For alkenes,
alkynes and aromatic hydrocarbons, spring
models can be constructed. Fig. 9.1 Structure of methane
In alkanes, tetrahedra are joined together
9.2 ALKANES
in which C-C and C-H bond lengths are
As already mentioned, alkanes are saturated
154 pm and 112 pm respectively (Unit 8).
open chain hydr ocarbons containing
You have already read that C–C and C–H σ
carbon - carbon single bonds. Methane (CH4)
bonds are formed by head-on overlapping of
is the first member of this family. Methane is 3
sp hybrid orbitals of carbon and 1s orbitals
a gas found in coal mines and marshy places.
of hydrogen atoms.
If you replace one hydrogen atom of methane
by carbon and join the required number of 9.2.1 Nomenclature and Isomerism
hydrogens to satisfy the tetravalence of the You have already read about nomenclature
other carbon atom, what do you get? You of different classes of organic compounds
get C2H6. This hydrocarbon with molecular in Unit 8. Nomenclature and isomerism
formula C2H6 is known as ethane. Thus you in alkanes can further be understood with
can consider C2H6 as derived from CH4 by the help of a few more examples. Common
replacing one hydrogen atom by -CH3 group. names are given in parenthesis. First three
Go on constructing alkanes by doing this alkanes – methane, ethane and propane have
theoretical exercise i.e., replacing hydrogen only one structure but higher alkanes can
atom by –CH3 group. The next molecules will have more than one structure. Let us write
be C3H8, C4H10 … structures for C4H10. Four carbon atoms of
H H H C4H10 can be joined either in a continuous
replace any H by - CH3 chain or with a branched chain in the
H—C—H H—C—C—H or C2H6
following two ways :
H H H I
These hydrocarbons are inert under
normal conditions as they do not react with
acids, bases and other reagents. Hence,
they were earlier known as paraffins (latin :
parum, little; affinis, affinity). Can you think Butane (n- butane), (b.p. 273 K)

Unit 9.indd 296 11/10/2022 15:24:01


Hydrocarbons 297

II isomers. It is also clear that structures I and


III have continuous chain of carbon atoms
but structures II, IV and V have a branched
chain. Such structural isomers which differ
in chain of carbon atoms are known as chain
isomers. Thus, you have seen that C4H10
2-Methylpropane (isobutane) and C5H12 have two and three chain isomers
(b.p.261 K) respectively.
In how many ways, you can join five Problem 9.1
carbon atoms and twelve hydrogen atoms of Write structures of different chain
C5H12? They can be arranged in three ways isomers of alkanes corresponding to the
as shown in structures III–V molecular formula C6H14. Also write their
III IUPAC names.

Solution
(i) CH3 – CH2 – CH2 – CH2– CH2– CH3
n-Hexane
Pentane (n-pentane)
(b.p. 309 K)

IV
2-Methylpentane

3-Methylpentane

2-Methylbutane (isopentane)
(b.p. 301 K)
2,3-Dimethylbutane
V

2,2 - Dimethylbutane

Based upon the number of carbon atoms


attached to a carbon atom, the carbon atom is
2,2-Dimethylpropane (neopentane) termed as primary (1°), secondary (2°), tertiary
(b.p. 282.5 K) (3°) or quaternary (4°). Carbon atom attached
Structures I and II possess same molecular to no other carbon atom as in methane or to
formula but differ in their boiling points and only one carbon atom as in ethane is called
other properties. Similarly structures III, IV primary carbon atom. Terminal carbon
and V possess the same molecular formula atoms are always primary. Carbon atom
but have different properties. Structures I and attached to two carbon atoms is known as
II are isomers of butane, whereas structures secondary. Tertiary carbon is attached to
III, IV and V are isomers of pentane. Since three carbon atoms and neo or quaternary
difference in properties is due to difference in carbon is attached to four carbon atoms. Can
their structures, they are known as structural you identify 1°, 2°, 3° and 4° carbon atoms in

Unit 9.indd 297 10/10/2022 10:37:53 AM


298 chemistry

structures I to V ? If you go on constructing compounds. These groups or substituents


structures for higher alkanes, you will be are known as alkyl groups as they are derived
getting still larger number of isomers. C6H14 from alkanes by removal of one hydrogen
has got five isomers and C7H16 has nine. As atom. General formula for alkyl groups is
many as 75 isomers are possible for C10H22. CnH2n+1 (Unit 8).
In structures II, IV and V, you observed Let us recall the general rules for
that –CH3 group is attached to carbon atom nomenclature already discussed in Unit 8.
numbered as 2. You will come across groups Nomenclature of substituted alkanes can
like –CH 3, –C 2H 5, –C 3H 7 etc. attached to further be understood by considering the
carbon atoms in alkanes or other classes of following problem:

Problem 9.2
Write structures of different isomeric alkyl groups corresponding to the molecular formula
C5H11. Write IUPAC names of alcohols obtained by attachment of –OH groups at different
carbons of the chain.
Solution
Structures of – C5H11 group Corresponding alcohols Name of alcohol

(i) CH3 – CH2 – CH2 – CH2– CH2 – CH3 – CH2 – CH2 – CH2– CH2 – OH Pentan-1-ol

(ii) CH3 – CH – CH2 – CH2 – CH3 CH3 – CH – CH2 – CH2– CH3 Pentan-2-ol
| |
OH

(iii) CH3 – CH2 – CH – CH2 – CH3 CH3 – CH2 – CH – CH2– CH3 Pentan-3-ol
| |
OH

CH3 CH3 3-Methyl-


| | butan-1-ol
(iv) CH3 – CH – CH2 – CH2 – CH3 – CH – CH2 – CH2– OH

CH3 CH3 2-Methyl-


| | butan-1-ol
(v) CH3 – CH2 – CH – CH2 – CH3 – CH2 – CH – CH2– OH

CH3 CH3 2-Methyl-


| | butan-2-ol
(vi) CH3 – C – CH2 – CH3 CH3 – C – CH2 – CH3
| |
OH
CH3 CH3 2,2- Dimethyl-
| | propan-1-ol
(vii) CH3 – C – CH2 – CH3 – C – CH2OH
| |
CH3 CH3

CH3 CH3 OH 3-Methyl-


| | | | butan-2-ol
(viii) CH3 – CH – CH –CH3 CH3 – CH – CH –CH3

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Hydrocarbons 299

Table 9.1 Nomenclature of a Few Organic Compounds

Structure and IUPAC Name Remarks

Lowest sum and


1 2 3 4 5 6
(a) CH3– CH – CH2 – CH – CH2 – CH3 alphabetical
(4 – Ethyl – 2 – methylhexane) arrangement

Lowest sum and


8 7 6 5 4 3 2 1
(b) CH3 – CH2 – CH2 – CH – CH – C – CH2 – CH3 alphabetical
arrangement

(3,3-Diethyl-5-isopropyl-4-methyloctane)

1 2 3 4 5 6 7 8 9 10 sec is not considered


(c) CH3– CH2– CH2– CH– CH– CH2– CH2– CH2– CH2– CH3 while arranging
alphabetically;
isopropyl is taken
5-sec– Butyl-4-isopropyldecane
as one word
1 2 3 4 5 6 7 8 9
(d) CH3– CH2– CH2– CH2– CH– CH2– CH2– CH2– CH3
Further numbering
to the substituents
of the side chain

5-(2,2– Dimethylpropyl)nonane
1 2 3 4 5 6 7
(e) CH3 – CH2 – CH – CH2 – CH – CH2 – CH3
Alphabetical
priority order
3–Ethyl–5–methylheptane

Problem 9.3 important to write the correct structure


from the given IUPAC name. To do this, first
Write IUPAC names of the following
of all, the longest chain of carbon atoms
compounds :
corresponding to the parent alkane is written.
(i) (CH3)3 C CH2C(CH3)3 Then after numbering it, the substituents are
(ii) (CH3)2 C(C2H5)2 attached to the correct carbon atoms and
(iii) tetra – tert-butylmethane finally valence of each carbon atom is satisfied
by putting the correct number of hydrogen
Solution atoms. This can be clarified by writing the
(i) 2, 2, 4, 4-Tetramethylpentane structure of 3-ethyl-2, 2–dimethylpentane in
(ii) 3, 3-Dimethylpentane the following steps :
(iii) 3,3-Di-tert-butyl -2, 2, 4, 4 - i) Draw the chain of five carbon atoms:
tetramethylpentane C–C–C–C–C
If it is important to write the correct ii) Give number to carbon atoms:
1 2 3 4 5
IUPAC name for a given structure, it is equally C –C –C –C –C

Unit 9.indd 299 10/10/2022 10:37:53 AM


300 chemistry

iii) Attach ethyl group at carbon 3 and two Longest chain is of six carbon atoms and
methyl groups at carbon 2 not that of five. Hence, correct name is
3-Methylhexane.
7 6 5 4 3 2 1
1 2 3 4 5
C – C– C– C– C
(ii) CH3 – CH2 – CH – CH2 – CH – CH2 – CH3

iv) Satisfy the valence of each carbon atom


by putting requisite number of hydrogen Numbering is to be started from the
atoms : end which gives lower number to ethyl
group. Hence, correct name is 3-ethyl-5-
methylheptane.
CH3 – C – CH – CH2 – CH3
9.2.2 Preparation

Petroleum and natural gas are the main
Thus we arrive at the correct structure. sources of alkanes. However, alkanes can be
If you have understood writing of structure prepared by following methods :
from the given name, attempt the following
problems. 1. From unsaturated hydrocarbons
Dihydrogen gas adds to alkenes and alkynes
Problem 9.4 in the presence of finely divided catalysts like
Write structural formulas of the following platinum, palladium or nickel to form alkanes.
compounds : This process is called hydrogenation. These
(i) 3, 4, 4, 5–Tetramethylheptane metals adsorb dihydrogen gas on their
surfaces and activate the hydrogen – hydrogen
(ii) 2,5-Dimethyhexane bond. Platinum and palladium catalyse the
Solution reaction at room temperature but relatively
higher temperature and pressure are required
with nickel catalysts.
(i) CH3 – CH2 – CH – C – CH– CH – Pt/Pd/Ni
CH 2 =CH 2 + H 2 CH 3 −CH 3
CH3
EthenePropane (9.1)
Pt/Pd/Ni
CH 2–CH=CH 2 + H 2 CH 3−CH 2CH 3
PropanePropane
   
(ii) CH3 – CH – CH2 – CH2 – CH – CH3 (9.2)
Pt/Pd/Ni
Problem 9.5 CH 3–C≡ C–H + 2H CH 3−CH 2CH 3
Writ e stru ctu r es fo r each o f t h e PropynePropane
following compounds. Why are the given
(9.3)
names incorrect? Write correct IUPAC
names.
2. From alkyl halides
(i) 2-Ethylpentane
i) Alkyl halides (except fluorides) on reduction
(ii) 5-Ethyl – 3-methylheptane with zinc and dilute hydrochloric acid give
Solution alkanes.
(i) CH3 – CH – CH2– CH2 – CH3 +
Zn,H
CH–C1+H2 CH4+HC1 (9.4)

Chloromethane Methane

Unit 9.indd 300 11/10/2022 15:25:29


Hydrocarbons 301

C2H5–C1+H2 Zn,H
+
C2H6+HC1 alkane containing even number of
Chloroethane Ethane (9.5) carbon atoms at the anode.
− +
2CH3COO Na + 2H2O
CH3CH2CH3+CH1
+
CH3CH2CH2C1 + H2 Zn,H

1-Chloropropane Propane Sodium acetate


(9.6) ↓ Electrolysts
ii) Alkyl halides on treatment with sodium CH3 − CH3 + 2CO2 + H2 + 2NaOH
(9.9)
metal in dry ethereal (free from moisture)
solution give higher alkanes. This reaction The reaction is supposed to follow the
is known as Wurtz reaction and is used following path :
O
for the preparation of higher alkanes
– + – +
containing even number of carbon i) 2CH3COO Na 2CH3 – C – O +2Na
atoms.
ii) At anode:
CH3Br+2Na+BrCH3 dry ether CH3+2Na
O O
Bromomenthane Ethane – –02e– .
(9.7) 2CH3 –C–O 2CH3 – C – 2CH3+2CO2↑
C2H5br+2Na+BrC2H5 dry ether C2H5–C2H Acetate ion Acetate Methyl free
free radical radical
Bromoethane n–Butane iii) H3C + CH3 H3C–CH3↑
(9.8) iv) At cathode :
What will happen if two different alkyl halides
are taken? H2O+e–→–OH+
2 →H2↑
3. From carboxylic acids
i) Sodium salts of carboxylic acids on Methane cannot be prepared by this
heating with soda lime (mixture of sodium method. Why?
hydroxide and calcium oxide) give alkanes
9.2.3 Properties
containing one carbon atom less than the
carboxylic acid. This process of elimination Physical properties
of carbon dioxide from a carboxylic acid is Alkanes are almost non-polar molecules
known as decarboxylation. because of the covalent nature of C-C and
– + CaO
C-H bonds and due to very little difference
CH3COO Na +MaOH ∆ CH4+NaCO3 of electronegativity between carbon and
Sodium ethanoate hydrogen atoms. They possess weak van der
Waals forces. Due to the weak forces, the first
Problem 9.6 four members, C1 to C4 are gases, C5 to C17
Sodium salt of which acid will be needed are liquids and those containing 18 carbon
for the preparation of propane ? Write atoms or more are solids at 298 K. They are
chemical equation for the reaction. colourless and odourless. What do you think
about solubility of alkanes in water based
Solution upon non-polar nature of alkanes? Petrol
Butanoic acid, is a mixture of hydrocarbons and is used
– +
CH3CH2CH2COO Na + NaOH CaO as a fuel for automobiles. Petrol and lower
fractions of petroleum are also used for dry
CH3CH2CH3+Na2CO3 cleaning of clothes to remove grease stains.
On the basis of this observation, what do
you think about the nature of the greasy
ii) Kolbe’s electrolytic method An aqueous substance? You are correct if you say that
solution of sodium or potassium salt of grease (mixture of higher alkanes) is non-
a carboxylic acid on electrolysis gives

Unit 9.indd 301 10/10/2022 10:37:53 AM


302 chemistry

polar and, hence, hydrophobic in nature. It is reducing agents. However, they undergo
generally observed that in relation to solubility the following reactions under certain
of substances in solvents, polar substances conditions.
are soluble in polar solvents, whereas the
1. Substitution reactions
non-polar ones in non-polar solvents i.e., like
dissolves like. One or more hydrogen atoms of alkanes
can be replaced by halogens, nitro group
Boiling point (b.p.) of different alkanes are
and sulphonic acid group. Halogenation
given in Table 9.2 from which it is clear that
there is a steady increase in boiling point with takes place either at higher temperature
increase in molecular mass. This is due to the (573-773 K) or in the presence of diffused
fact that the intermolecular van der Waals sunlight or ultraviolet light. Lower alkanes
forces increase with increase of the molecular do not undergo nitration and sulphonation
size or the surface area of the molecule. reactions. These reactions in which hydrogen
atoms of alkanes are substituted are known
You can make an interesting observation
as substitution reactions. As an example,
by having a look on the boiling points of
three isomeric pentanes viz., (pentane, chlorination of methane is given below:
2-methylbutane and 2,2-dimethylpropane). It Halogenation
is observed (Table 9.2) that pentane having hv
a continuous chain of five carbon atoms has CH2 + C1 CH3C1 + HC1
the highest boiling point (309.1K) whereas Chloromethane (9.10)
2,2 – dimethylpropane boils at 282.5K. With
increase in number of branched chains, CH3C1 + hv
CH2 C12 + HC1
the molecule attains the shape of a sphere.
Dichloromethane (9.11)
This results in smaller area of contact and
therefore weak intermolecular forces between CH2C12 hv
CHC13 + HC1
spherical molecules, which are overcome at
Trichloromethane (9.12)
relatively lower temperatures.
hv
Chemical properties CHC13 + C12 CC14 + HC1
As already mentioned, alkanes are generally Tetrachloromethane (9.13)
inert towards acids, bases, oxidising and
Table 9.2 Variation of Melting Point and Boiling Point in Alkanes

Molecular Name Molecular b.p./(K) m.p./(K)


formula mass/u
CH4 Methane 16 111.0 90.5
C2H6 Ethane 30 184.4 101.0
C3H8 Propane 44 230.9 85.3
C4H10 Butane 58 272.4 134.6
C4H10 2-Methylpropane 58 261.0 114.7
C5H12 Pentane 72 309.1 143.3
C5H12 2-Methylbutane 72 300.9 113.1
C5H12 2,2-Dimethylpropane 72 282.5 256.4
C6H14 Hexane 86 341.9 178.5
C7H16 Heptane 100 371.4 182.4
C8H18 Octane 114 398.7 216.2
C9H20 Nonane 128 423.8 222.0
C10H22 Decane 142 447.1 243.3
C20H42 Eicosane 282 615.0 236.2

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Hydrocarbons 303

hv steps are possible and may occur. Two such


CH3–CH3 + C12 CH3–CH2C1 + HC1
Chloroethane (9.14) steps given below explain how more highly
haloginated products are formed.
It is found that the rate of reaction of . .
alkanes with halogens is F2 > Cl2 > Br2 > I2. CH3C1 + C  1 → C  H2C1 + HC1
. .
Rate of replacement of hydrogens of alkanes is : C  H2C1 + C1– C1 → CH2C12 + C  1
3° > 2° > 1°. Fluorination is too violent to
be controlled. Iodination is very slow and a (iii) Termination: The reaction stops after
reversible reaction. It can be carried out in the some time due to consumption of reactants
presence of oxidizing agents like HIO3 or HNO3. and / or due to the following side reactions :
The possible chain terminating steps are:
CH4+I2 CH3I+HI(9.15) . .
(a) C  1 + C  1 → C1–C1
HIO3+5HI→312+3H2O(9.16) . .
(b) H3 C   + C   H3 → H3C– CH3
. .
Halogenation is supposed to proceed via (c) H3 C  1 + C  1 → H3C–C1
free radical chain mechanism involving three
Though in (c), CH3 – Cl, the one of the
steps namely initiation, propagation and
products is formed but free radicals are
termination as given below:
consumed and the chain is terminated. The
Mechanism above mechanism helps us to understand
(i) Initiation : The reaction is initiated the reason for the formation of ethane as a
by homolysis of chlorine molecule in the byproduct during chlorination of methane.
presence of light or heat. The Cl–Cl bond 2. Combustion
is weaker than the C–C and C–H bond and
Alkanes on heating in the presence of air or
hence, is easiest to break. dioxygen are completely oxidized to carbon
hv
. dioxide and water with the evolution of large
C1–C1 homolysis C H3 + C1 amount of heat.
Chlorine free radicals CH4 (g) + 202 (g) → CO2 (g) + 2H2O(1);
(ii) Propagation : Chlorine free radical Äc Hè − 890kJ mol-1
attacks the methane molecule and takes the (9.17)
reaction in the forward direction by breaking
C4H10 (g) + 13/2O2 (g) → 4CO2 (g) + 5H2O(1)
the C-H bond to generate methyl free radical
with the formation of H-Cl. Äc Hè = −2875.84kJ mol-1
+
(a) CH4 + C1 hv +
C H3 + H–C1 (9.18)
The general combustion equation for any
The methyl radical thus obtained attacks alkane is :
the second molecule of chlorine to form  3n + 1
CnH2n+2 +  O → nCO2 + (n + 1)H2O
CH3 – Cl with the liberation of another chlorine  2  2
free radical by homolysis of chlorine molecule. (9.19)
(b) CH3 + C1–C1 hv
CH3 – C1 + C1 Due to the evolution of large amount of
heat during combustion, alkanes are used as
The chlorine and methyl free radicals fuels.
generated above repeat steps (a) and (b) During incomplete combustion of alkanes
respectively and thereby setup a chain of with insufficient amount of air or dioxygen,
reactions. The propagation steps (a) and carbon black is formed which is used in
(b) are those which directly give principal the manufacture of ink, printer ink, black
products, but many other propagation pigments and as filters.

Unit 9.indd 303 10/10/2022 10:37:54 AM


304 chemistry

CH4(g) + O2(g)
incomplete
C(s)+2H2 O(1) pressure in the presence of oxides of vanadium,
combustion
molybdenum or chromium supported over
(9.20)
alumina get dehydrogenated and cyclised to
3. Controlled oxidation benzene and its homologues. This reaction is
Alkanes on heating with a regulated supply known as aromatization or reforming.
of dioxygen or air at high pressure and in the
presence of suitable catalysts give a variety of
oxidation products.
3
(i) 2CH4 + O2 Cu/523K/100atm 2CH OH
Methanol
(9.21)
Mo2O3 (9.26)
(ii) CH4 + O2 HCHO + H2O
∆ Toluene (C 7H8) is methyl derivative of
Methanal
benzene. Which alkane do you suggest for
preparation of toluene ?
(9.22)
(CH3COO)Mn 6. Reaction with steam
(iii) 2CH3CH3 + 3O2 2CH3COOH
∆ Methane reacts with steam at 1273 K in the
 Ethanoic acid presence of nickel catalyst to form carbon
 + 2H2O monoxide and dihydrogen. This method is
(9.23) used for industrial preparation of dihydrogen
(iv) Ordinarily alkanes resist oxidation but gas
alkanes having tertiary H atom can be Ni
oxidized to corresponding alcohols by CH4 + H2IO CO + 3H2(9.27)

potassium permanganate.
KMnO4 7. Pyrolysis
(iCH3)3 CH Oxidation (CH3)3 COH Higher alkanes on heating to higher
2-Methylpropane2-Methylpropane-2-01 temperature decompose into lower alkanes,
alkenes etc. Such a decomposition reaction
(9.24) into smaller fragments by the application of
4. Isomerisation heat is called pyrolysis or cracking.
n-Alkanes on heating in the presence of
anhydrous aluminium chloride and hydrogen
chloride gas isomerise to branched chain
alkanes. Major products are given below.
Some minor products are also possible which
you can think over. Minor products are (9.28)
generally not reported in organic reactions. Pyrolysis of alkanes is believed to be a
free radical reaction. Preparation of oil gas
CH3(CH)2)4CH3 Anhy, AICI / HCI 3

or petrol gas from kerosene oil or petrol


n-Hexane involves the principle of pyrolysis. For
CH3CH–(CH2)2–CH3+CH3CH2–CH–CH2–CH3 example, dodecane, a constituent of kerosene
oil on heating to 973K in the presence of
CH3 CH3 platinum, palladium or nickel gives a mixture
2-Methylpen tane 3-Methylpenatone of heptane and pentene.
(9.25)

5. Aromatization C12H26 Pt/Pd/Ni


973K C7H16 + C5H10 Other
Products
n-Alkanes having six or more carbon atoms Dodecane Heptane Pentene
on heating to 773K at 10-20 atmospheric (9.29)

Unit 9.indd 304 10/10/2022 10:37:54 AM


Hydrocarbons 305

9.2.4 Conformations 1. Sawhorse projections


Alkanes contain carbon-carbon sigma (σ) In this projection, the molecule is viewed
bonds. Electron distribution of the sigma along the molecular axis. It is then projected
molecular orbital is symmetrical around the on paper by drawing the central C–C bond
internuclear axis of the C–C bond which is as a somewhat longer straight line. Upper
not disturbed due to rotation about its axis. end of the line is slightly tilted towards
This permits free rotation about C–C single right or left hand side. The front carbon is
bond. This rotation results into different shown at the lower end of the line, whereas
spatial arrangements of atoms in space the rear carbon is shown at the upper end.
which can change into one another. Such Each carbon has three lines attached to it
spatial arrangements of atoms which can corresponding to three hydrogen atoms.
be converted into one another by rotation The lines are inclined at an angle of 120° to
around a C-C single bond are called each other. Sawhorse projections of eclipsed
conformations or conformers or rotamers. and staggered conformations of ethane are
Alkanes can thus have infinite number of depicted in Fig. 9.2.
conformations by rotation around C-C single
bonds. However, it may be remembered that
rotation around a C-C single bond is not
completely free. It is hindered by a small
–1
energy barrier of 1-20 kJ mol due to weak
repulsive interaction between the adjacent
bonds. Such a type of repulsive interaction
is called torsional strain.
Conformations of ethane : Ethane Fig. 9.2 Sawhorse projections of ethane
molecule (C2H6) contains a carbon – carbon
single bond with each carbon atom attached 2. Newman projections
to three hydrogen atoms. Considering the In this projection, the molecule is viewed at the
ball and stick model of ethane, keep one C–C bond head on. The carbon atom nearer
carbon atom stationary and rotate the other to the eye is represented by a point. Three
carbon atom around the C-C axis. This hydrogen atoms attached to the front carbon
rotation results into infinite number of spatial atom are shown by three lines drawn at an
arrangements of hydrogen atoms attached to angle of 120° to each other. The rear carbon
one carbon atom with respect to the hydrogen atom (the carbon atom away from the eye) is
atoms attached to the other carbon atom. represented by a circle and the three hydrogen
These are called conformational isomers atoms are shown attached to it by the shorter
(conformers). Thus there are infinite number lines drawn at an angle of 120° to each other.
of conformations of ethane. However, there are The Newman’s projections are depicted in
two extreme cases. One such conformation Fig. 9.3.
in which hydrogen atoms attached to two
carbons are as closed together as possible is
called eclipsed conformation and the other in
which hydrogens are as far apart as possible
is known as the staggered conformation. Any
other intermediate conformation is called a
skew conformation.It may be remembered
that in all the conformations, the bond angles
and the bond lengths remain the same.
Eclipsed and the staggered conformations can
be represented by Sawhorse and Newman
projections.
Fig. 9.3 Newman’s projections of ethane

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306 chemistry

Relative stability of conformations: As the first member, ethylene or ethene (C2H4)


mentioned earlier, in staggered form of ethane, was found to form an oily liquid on reaction
the electron clouds of carbon-hydrogen bonds with chlorine.
are as far apart as possible. Thus, there are
9.3.1 Structure of Double Bond
minimum repulsive forces, minimum energy
and maximum stability of the molecule. On the Carbon-carbon double bond in alkenes
other hand, when the staggered form changes consists of one strong sigma (σ) bond (bond
–1
into the eclipsed form, the electron clouds of the enthalpy about 397 kJ mol ) due to head-on
2
carbon – hydrogen bonds come closer to each overlapping of sp hybridised orbitals and
other resulting in increase in electron cloud one weak pi (π) bond (bond enthalpy about
–1
repulsions. To check the increased repulsive 284 kJ mol ) obtained by lateral or sideways
forces, molecule will have to possess more overlapping of the two 2p orbitals of the two
energy and thus has lesser stability. As already carbon atoms. The double bond is shorter in
mentioned, the repulsive interaction between bond length (134 pm) than the C–C single
the electron clouds, which affects stability of bond (154 pm). You have already read that
a conformation, is called torsional strain. the pi (π) bond is a weaker bond due to poor
Magnitude of torsional strain depends upon sideways overlapping between the two 2p
the angle of rotation about C–C bond. This orbitals. Thus, the presence of the pi (π) bond
angle is also called dihedral angle or torsional makes alkenes behave as sources of loosely
angle. Of all the conformations of ethane, the held mobile electrons. Therefore, alkenes are
easily attacked by reagents or compounds
staggered form has the least torsional strain
which are in search of electrons. Such
and the eclipsed form, the maximum torsional
reagents are called electrophilic reagents.
strain. Therefore, staggered conformation is
The presence of weaker π-bond makes alkenes
more stable than the eclipsed conformation.
unstable molecules in comparison to alkanes
Hence, molecule largely remains in staggered
and thus, alkenes can be changed into single
conformation or we can say that it is preferred
bond compounds by combining with the
conformation. Thus it may be inferred that
electrophilic reagents. Strength of the double
rotation around C–C bond in ethane is not –1
bond (bond enthalpy, 681 kJ mol ) is greater
completely free. The energy difference between
than that of a carbon-carbon single bond in
the two extreme forms is of the order of 12.5 –1
–1 ethane (bond enthalpy, 348 kJ mol ). Orbital
kJ mol , which is very small. Even at ordinary
diagrams of ethene molecule are shown in
temperatures, the ethane molecule gains
Figs. 9.4 and 9.5.
thermal or kinetic energy sufficient enough to
–1
overcome this energy barrier of 12.5 kJ mol
through intermolecular collisions. Thus, it
can be said that rotation about carbon-carbon
single bond in ethane is almost free for all
practical purposes. It has not been possible to
separate and isolate different conformational
isomers of ethane.

9.3 Alkenes
Alkenes are unsaturated hydrocarbons
Fig. 9.4 Orbital picture of ethene depicting
containing at least one double bond. What
σ bonds only
should be the general formula of alkenes? If
there is one double bond between two carbon 9.3.2 Nomenclature
atoms in alkenes, they must possess two For nomenclature of alkenes in IUPAC system,
hydrogen atoms less than alkanes. Hence, the longest chain of carbon atoms containing
general formula for alkenes is CnH2n. Alkenes the double bond is selected. Numbering of the
are also known as olefins (oil forming) since chain is done from the end which is nearer to

Unit 9.indd 306 11/10/2022 15:26:35


Hydrocarbons 307

Fig. 9.5 Orbital picture of ethene showing formation of (a) π-bond, (b) π-cloud and (c) bond angles and
bond lengths

the double bond. The suffix ‘ene’ replaces ‘ane’


of alkanes. It may be remembered that first Solution
member of alkene series is: CH2 (replacing (i) 2,8-Dimethyl-3, 6-decadiene;
n by 1 in CnH2n) known as methene but has (ii) 1,3,5,7 Octatetraene;
a very short life. As already mentioned, first
(iii) 2-n-Propylpent-1-ene;
stable member of alkene series is C2H4 known
as ethylene (common) or ethene (IUPAC). (iv) 4-Ethyl-2,6-dimethyl-dec-4-ene;
IUPAC names of a few members of alkenes
Problem 9.8
are given below :
Calculate number of sigma (σ) and pi (π)
Structure IUPAC name
bonds in the above structures (i-iv).
CH3 – CH = CH2 Propene
CH3 – CH2 – CH = CH2 But – l - ene Solution
CH3 – CH = CH–CH3 But-2-ene σ bonds : 33, π bonds : 2
CH2 = CH – CH = CH2 Buta – 1,3 - diene σ bonds : 17, π bonds : 4
CH2 = C – CH3 2-Methylprop-1-ene σ bonds : 23, π bond : 1
| σ bonds : 41, π bond : 1
CH3
CH2 = CH – CH – CH3 3-Methylbut-1-ene 9.3.3 Isomerism
|
CH3 Alkenes show both structural isomerism and
geometrical isomerism.
Structural isomerism : As in alkanes, ethene
Problem 9.7
(C2H4) and propene (C3H6) can have only one
Write IUPAC names of the following
structure but alkenes higher than propene
compounds:
have different structures. Alkenes possessing
(i) (CH3)2CH – CH = CH – CH2 – CH C4H8 as molecular formula can be written in

the following three ways:
CH3 – CH – CH
| I. 1 2 3 4
C2H5 CH2 = CH – CH2 – CH3

(ii) But-1-ene
(C4H8)
(iii) CH2 = C (CH2CH2CH3)2
(iv) CH3 CH2 CH2 CH2 CH2CH3 II. 1 2 3 4
| | CH3 – CH = CH – CH3
CH3 – CHCH = C – CH2 – CHCH3
| But-2-ene
CH3 (C4H8)

Unit 9.indd 307 10/10/2022 10:37:55 AM


308 chemistry

III. 1 2 3 In (a), the two identical atoms i.e., both


CH2 = C – CH3 the X or both the Y lie on the same side
| of the double bond but in (b) the two X or
CH3 two Y lie across the double bond or on the
2-Methyprop-1-ene opposite sides of the double bond. This
(C4H8) results in different geometry of (a) and (b) i.e.
disposition of atoms or groups in space in
Structures I and III, and II and III are
the two arrangements is different. Therefore,
the examples of chain isomerism whereas
they are stereoisomers. They would have the
structures I and II are position isomers.
same geometry if atoms or groups around
Problem 9.9 C=C bond can be rotated but rotation around
C=C bond is not free. It is restricted. For
Write structures and IUPAC names of
understanding this concept, take two pieces
different structural isomers of alkenes
of strong cardboards and join them with the
corresponding to C5H10.
help of two nails. Hold one cardboard in your
Solution one hand and try to rotate the other. Can
(a) CH2 = CH – CH2 – CH2 – CH3 you really rotate the other cardboard ? The
answer is no. The rotation is restricted. This
Pent-1-ene
illustrates that the restricted rotation of atoms
(b) CH3 – CH=CH – CH2 – CH3 or groups around the doubly bonded carbon
Pent-2-ene atoms gives rise to different geometries of
(c) CH3 – C = CH – CH3 such compounds. The stereoisomers of this
| type are called geometrical isomers. The
CH3 isomer of the type (a), in which two identical
2-Methylbut-2-ene atoms or groups lie on the same side of the
double bond is called cis isomer and the
(d) CH3 – CH – CH = CH2 other isomer of the type (b), in which identical
| atoms or groups lie on the opposite sides of
CH3 the double bond is called trans isomer . Thus
3-Methylbut-1-ene cis and trans isomers have the same structure
(e) CH2 = C – CH2 – CH3 but have different configuration (arrangement
| of atoms or groups in space). Due to different
CH3 arrangement of atoms or groups in space,
these isomers differ in their properties like
2-Methylbut-1-ene melting point, boiling point, dipole moment,
Geometrical isomerism: Doubly bonded solubility etc. Geometrical or cis-trans isomers
carbon atoms have to satisfy the remaining of but-2-ene are represented below :
two valences by joining with two atoms or
groups. If the two atoms or groups attached
to each carbon atom are different, they can
be represented by YX C = C XY like structure.
YX C = C XY can be represented in space in
the following two ways :

Cis form of alkene is found to be more


polar than the trans form. For example,
dipole moment of cis-but-2-ene is 0.33 Debye,
whereas, dipole moment of the trans form
is almost zero or it can be said that

Unit 9.indd 308 10/10/2022 10:37:55 AM


Hydrocarbons 309

trans-but-2-ene is non-polar. This can be (ii) CH2 = CBr2


understood by drawing geometries of the two
forms as given below from which it is clear (iii) C6H5CH = CH – CH3
that in the trans-but-2-ene, the two methyl (iv) CH3CH = CCl CH3
groups are in opposite directions, Threfore,
dipole moments of C-CH3 bonds cancel, thus Solution
making the trans form non-polar. (iii) and (iv). In structures (i) and (ii), two
identical groups are attached to one of
the doubly bonded carbon atom.

9.3.4 Preparation
1. From alkynes: Alkynes on partial
reduction with calculated amount of
cis-But-2-ene trans-But-2-ene dihydrogen in the presence of palladised
(µ = 0.33D) (µ = 0) charcoal partially deactivated with poisons
In the case of solids, it is observed that the like sulphur compounds or quinoline give
trans isomer has higher melting point than alkenes. Partially deactivated palladised
the cis form. charcoal is known as Lindlar’s catalyst.
Alkenes thus obtained are having cis
Geometrical or cis-trans isomerism
geometry. However, alkynes on reduction
is also shown by alkenes of the types
XYC = CXZ and XYC = CZW with sodium in liquid ammonia form trans
alkenes.
Problem 9.10
Draw cis and trans isomers of the
following compounds. Also write their
IUPAC names :
(i) CHCl = CHCl (9.30)
(ii) C2H5CCH3 = CCH3C2H5

Solution

(9.31)
Pd/C
iii) CH≡ CH+H2 CH2 =CH2 (9.32)
Ethyne Ethene
Pd/C
CH3–C≡ CH+H2 CH3–CH =CH2
iv)
Propyne Propene
(9.33)
Wi l l p r o p e n e t h u s o b t a i n e d s h o w
Problem 9.11 geometrical isomerism? Think for the
Which of the following compounds will reason in support of your answer.
show cis-trans isomerism? 2. From alkyl halides: Alkyl halides (R-X) on
(i) (CH3)2C = CH – C2H5 heating with alcoholic potash (potassium
hydroxide dissolved in alcohol, say,

Unit 9.indd 309 10/10/2022 10:37:55 AM


310 chemistry

ethanol) eliminate one molecule of halogen takes out one hydrogen atom from the
acid to form alkenes. This reaction is β-carbon atom.
known as dehydrohalogenation i.e.,
removal of halogen acid. This is example
of β-elimination reaction, since hydrogen
atom is eliminated from the β carbon atom
(carbon atom next to the carbon to which
halogen is attached).
(9.37)
9.3.5 Properties
Physical properties
Alkenes as a class resemble alkanes in
physical properties, except in types of
isomerism and difference in polar nature.
(9.34) The first three members are gases, the next
Nature of halogen atom and the alkyl fourteen are liquids and the higher ones are
group determine rate of the reaction. It solids. Ethene is a colourless gas with a faint
is observed that for halogens, the rate is: sweet smell. All other alkenes are colourless
iodine > bromine > chlorine, while for alkyl and odourless, insoluble in water but fairly
groups it is : tert > secondary > primary. soluble in non-polar solvents like benzene,
petroleum ether. They show a regular increase
3. From vicinal dihalides: Dihalides in
in boiling point with increase in size i.e., every
which two halogen atoms are attached
– CH2 group added increases boiling point by
to two adjacent carbon atoms are known
20–30 K. Like alkanes, straight chain alkenes
as vicinal dihalides. Vicinal dihalides on
have higher boiling point than isomeric
treatment with zinc metal lose a molecule
branched chain compounds.
of ZnX2 to form an alkene. This reaction
is known as dehalogenation. Chemical properties
Alkenes are the rich source of loosely held
CH2Br–CH2Br + Zn CH2=CH2+ ZnBr2 pi (π) electrons, due to which they show
(9.35) addition reactions in which the electrophiles
CH3CHBr–CH2Br + Zn CH3CH=CH2 add on to the carbon-carbon double bond to
form the addition products. Some reagents
+ZnBr2 also add by free radical mechanism. There
(9.36) are cases when under special conditions,
4. From alcohols by acidic dehydration: alkenes also undergo free radical substitution
You have read during nomenclature of reactions. Oxidation and ozonolysis reactions
different homologous series in Unit 12 are also quite prominent in alkenes. A brief
that alcohols are the hydroxy derivatives description of different reactions of alkenes
of alkanes. They are represented by R–OH is given below:
where, R is CnH2n+1. Alcohols on heating 1. Addition of dihydrogen: Alkenes add
with concentrated sulphuric acid form up one molecule of dihydrogen gas in
alkenes with the elimination of one water the presence of finely divided nickel,
molecule. Since a water molecule is palladium or platinum to form alkanes
eliminated from the alcohol molecule in (Section 9.2.2)
the presence of an acid, this reaction is 2. Addition of halogens : Halogens like
known as acidic dehydration of alcohols. bromine or chlorine add up to alkene to
This reaction is also the example of form vicinal dihalides. However, iodine
β-elimination reaction since –OH group does not show addition reaction under

Unit 9.indd 310 11/10/2022 15:27:11


Hydrocarbons 311

normal conditions. The reddish orange


colour of bromine solution in carbon
tetrachloride is discharged when bromine
adds up to an unsaturation site. This
reaction is used as a test for unsaturation.
Addition of halogens to alkenes is an
example of electrophilic addition reaction
involving cyclic halonium ion formation (9.42)
which you will study in higher classes. Markovnikov, a Russian chemist made a
generalisation in 1869 after studying such
reactions in detail. These generalisations
led Markovnikov to frame a rule called
Markovnikov rule. The rule states that
negative part of the addendum (adding
(9.38) molecule) gets attached to that carbon atom
which possesses lesser number of hydrogen
atoms. Thus according to this rule, product
I i.e., 2-bromopropane is expected. In actual
practice, this is the principal product of the
reaction. This generalisation of Markovnikov
(9.39) rule can be better understood in terms of
mechanism of the reaction.
3. Addition of hydrogen halides: Hydrogen
halides (HCl, HBr,HI) add up to alkenes Mechanism
to for m alkyl halides. The order of Hydrogen bromide provides an electrophile,
+
reactivity of the hydrogen halides is H , which attacks the double bond to form
HI > HBr > HCl. Like addition of halogens carbocation as shown below :
to alkenes, addition of hydrogen halides is
also an example of electrophilic addition
reaction. Let us illustrate this by taking
addition of HBr to symmetrical and
unsymmetrical alkenes
Addition reaction of HBr to symmetrical
alkenes
(a) less stable (b) more stable
Addition reactions of HBr to symmetrical
primary carbocation secondary carbocation
alkenes (similar groups attached to double
bond) take place by electrophilic addition (i) The secondary carbocation (b) is more
mechanism. stable than the primary carbocation
(a), therefore, the former predominates
CH2=CH2+H–Br CH3–CH2–Br (9.40)
because it is formed at a faster rate.

CH3–CH=CH–CH3+HBr CH3–CH–CHCH3 (ii) The carbocation (b) is attacked by Br ion
to form the product as follows :
Br
(9.41)

Addition reaction of HBr to unsymmetrical


alkenes (Markovnikov Rule)
How will H – Br add to propene ? The two 2-Bromopropane
possible products are I and II. (major product)

Unit 9.indd 311 10/27/2022 2:19:43 PM


312 chemistry

Anti Markovnikov addition or peroxide


effect or Kharash effect
In the presence of peroxide, addition of HBr
to unsymmetrical alkenes like propene takes
place contrary to the Markovnikov rule. This
happens only with HBr but not with HCl
The secondary free radical obtained in the
and Hl. This addition reaction was observed
above mechanism (step iii) is more stable than
by M.S. Kharash and F.R. Mayo in 1933 the primary. This explains the formation of
at the University of Chicago. This reaction 1-bromopropane as the major product. It may
is known as peroxide or Kharash effect be noted that the peroxide effect is not observed
or addition reaction anti to Markovnikov in addition of HCl and HI. This may be due
rule. to the fact that the H–Cl bond being
–1
(C6H5CO)2O2 stronger (430.5 kJ mol ) than H–Br bond
CH3 – CH=CH2+HBr CH3–CH2 –1
(363.7 kJ mol ), is not cleaved by the free
radical, whereas the H–I bond is weaker
CH2Br –1
(296.8 kJ mol ) and iodine free radicals
1–Bromopropane combine to form iodine molecules instead of
adding to the double bond.
(9.43)

Mechanism : Peroxide effect proceeds via Problem 9.12


free radical chain mechanism as given below: Write IUPAC names of the products
obtained by addition reactions of HBr to
(i)
hex-1-ene
(i) in the absence of peroxide and
(ii) in the presence of peroxide.

Solution

. Homolysis .
(ii) C 6H5+H–Br C6H3+ B r

4. Addition of sulphuric acid : Cold


concentrated sulphuric acid adds to
alkenes in accordance with Markovnikov
rule to form alkyl hydrogen sulphate by
the electrophilic addition reaction.

Unit 9.indd 312 10/10/2022 10:37:56 AM


Hydrocarbons 313

ketones and/or acids depending upon the


nature of the alkene and the experimental
conditions

(9.49)
+
KMnO4/H
CH3 – CH=CH–CH3 2CH3COOH
(9.44) But-2-ene Ethanoic acid
(9.50)
7. Ozonolysis : Ozonolysis of alkenes
involves the addition of ozone molecule to
alkene to form ozonide, and then cleavage
of the ozonide by Zn-H 2O to smaller
molecules. This reaction is highly useful
in detecting the position of the double
(9.45) bond in alkenes or other unsaturated
5. Addition of water : In the presence of a compounds.
few drops of concentrated sulphuric acid
alkenes react with water to form alcohols,
in accordance with the Markovnikov rule.

(9.51)
(9.46)
6. Oxidation: Alkenes on reaction with cold,
dilute, aqueous solution of potassium
permanganate (Baeyer’s reagent) produce
vicinal glycols. Decolorisation of KMnO4
solution is used as a test for unsaturation.

(9.52)
(9.47) 8. Polymerisation: You are familiar with
polythene bags and polythene sheets.
Polythene is obtained by the combination
of large number of ethene molecules at
high temperature, high pressure and
in the presence of a catalyst. The large
molecules thus obtained are called
(9.48) polymers. This reaction is known as
b) Acidic potassium permanganate or acidic polymerisation. The simple compounds
potassium dichromate oxidises alkenes to from which polymers are made are called

Unit 9.indd 313 10/10/2022 10:37:57 AM


314 chemistry

monomers. Other alkenes also undergo are named as derivatives of the corresponding
polymerisation. alkanes replacing ‘ane’ by the suffix ‘yne’.
High temp./pressure
n(CH2 =CH2) Catalyst
—( CH2–CH2 —
) The position of the triple bond is indicated
Polythene by the first triply bonded carbon. Common
and IUPAC names of a few members of alkyne
(9.53) series are given in Table 9.2.
n(CH3 –CH=CH2)
High temp./pressure
—(CH–CH2 —
)n You have already learnt that ethyne and
Catalyst
propyne have got only one structure but
there are two possible structures for butyne –
CH3
(i) but-1-yne and (ii) but-2-yne. Since these
Polypropene two compounds differ in their structures
(9.54) due to the position of the triple bond, they
Polymers are used for the manufacture of plastic are known as position isomers. In how
bags, squeeze bottles, refrigerator dishes, toys, many ways, you can construct the structure
pipes, radio and T.V. cabinets etc. Polypropene for the next homologue i.e., the next alkyne
is used for the manufacture of milk crates, with molecular formula C5H8? Let us try to
plastic buckets and other moulded articles. arrange five carbon atoms with a continuous
Though these materials have now become chain and with a side chain. Following are the
common, excessive use of polythene and possible structures :
polypropylene is a matter of great concern for Structure IUPAC name
all of us. 1 2 3 4 5
I. HC≡ C– CH2– CH2– CH3 Pent–1-yne
9.4 Alkynes 1 2 3 4 5
Like alkenes, alkynes are also unsaturated II. H3C–C≡ C– CH2– CH3 Pent–2-yne
hydrocarbons. They contain at least one triple 4 3 2 1
bond between two carbon atoms. The number III. H3C–CH–C≡ CH 3-Methyl but–1-yne
|
of hydrogen atoms is still less in alkynes as
CH3
compared to alkenes or alkanes. Their general Structures I and II are position isomers
formula is CnH2n–2. and structures I and III or II and III are chain
The first stable member of alkyne series isomers.
is ethyne which is popularly known as
acetylene. Acetylene is used for arc welding Problem 9.13
purposes in the form of oxyacetylene flame Write structures of different isomers
th
obtained by mixing acetylene with oxygen corresponding to the 5 member of
gas. Alkynes are starting materials for a large alkyne series. Also write IUPAC names of
number of organic compounds. Hence, it all the isomers. What type of isomerism
is interesting to study this class of organic is exhibited by different pairs of isomers?
compounds.
Solution
9.4.1 Nomenclature and Isomerism th
5 member of alkyne has the molecular
In common system, alkynes are named as formula C6H10. The possible isomers are:
derivatives of acetylene. In IUPAC system, they
Table 9.2 Common and IUPAC Names of Alkynes (CnH2n–2)

Value of n Formula Structure Common name IUPAC name


2 C2H2 H-C≡CH Acetylene Ethyne
3 C3H4 CH3-C≡CH Methylacetylene Propyne
4 C4H6 CH3CH2-C≡CH Ethylacetylene But-1-yne
4 C4H6 CH3-C≡C-CH3 Dimethylacetylene But-2-yne

Unit 9.indd 314 10/27/2022 2:18:58 PM


Hydrocarbons 315

(a) HC ≡ C – CH2 – CH2 – CH2 – CH3


Hex-1-yne
(b) CH3 – C ≡ C – CH2 – CH2 – CH3
Hex-2-yne
(c) CH3 – CH2 – C ≡ C – CH2– CH3
Hex-3-yne

3-Methylpent-1-yne

4-Methylpent-1-yne

4-Methylpent-2-yne
Fig. 9.6 Orbital picture of ethyne showing
(a) sigma overlaps (b) pi overlaps.

orbitals of the other carbon atom, which


undergo lateral or sideways overlapping to
3,3-Dimethylbut-1-yne form two pi (π) bonds between two carbon
atoms. Thus ethyne molecule consists of one
Position and chain isomerism shown by
C–C σ bond, two C–H σ bonds and two C–C
different pairs.
π bonds. The strength of C≡C bond (bond
-1
enthalpy 823 kJ mol ) is more than those
–1
9.4.2 Structure of Triple Bond of C=C bond (bond enthalpy 681 kJ mol )
–1
Ethyne is the simplest molecule of alkyne and C–C bond (bond enthalpy 348 kJ mol ).
series. Structure of ethyne is shown in The C≡C bond length is shorter (120 pm)
Fig. 9.6. than those of C=C (133 pm) and C–C (154
pm). Electron cloud between two carbon
Each carbon atom of ethyne has two sp
atoms is cylindrically symmetrical about the
hybridised orbitals. Carbon-carbon sigma (σ)
internuclear axis. Thus, ethyne is a linear
bond is obtained by the head-on overlapping
molecule.
of the two sp hybridised orbitals of the two
carbon atoms. The remaining sp hybridised 9.4.3 Preparation
orbital of each carbon atom undergoes
1. From calcium carbide: On industrial
overlapping along the internuclear axis with
scale, ethyne is prepared by treating
the 1s orbital of each of the two hydrogen
calcium carbide with water. Calcium
atoms for ming two C-H sigma bonds.
carbide is prepared by heating quick lime
H-C-C bond angle is of 180°. Each carbon
with coke. Quick lime can be obtained by
has two unhybridised p orbitals which are
heating limestone as shown in the following
perpendicular to each other as well as to the
reactions:
plane of the C-C sigma bond. The 2p orbitals
of one carbon atom are parallel to the 2p CaCO3 ∆ CaO + O2 (9.55)

Unit 9.indd 315 11/10/2022 15:27:49


316 chemistry

CaO + 3C CaC2 + CO (9.56) the sp hybridised carbon atoms whereas


2
Calcium they are attached to sp hybridised carbon
3
carbide atoms in ethene and sp hybridised carbons
in ethane. Due to the maximum percentage of
CaC2 + 2H2O Ca(OH)2 + C2H2 (9.57) s character (50%), the sp hybridised orbitals
of carbon atoms in ethyne molecules have
2. From vicinal dihalides : Vicinal dihalides
highest electronegativity; hence, these attract
on treatment with alcoholic potassium
the shared electron pair of the C-H bond of
hydroxide undergo dehydrohalogenation.
ethyne to a greater extent than that of the
One molecule of hydrogen halide is 2
sp hybridised orbitals of carbon in ethene
eliminated to form alkenyl halide which 3
and the sp hybridised orbital of carbon in
on treatment with sodamide gives alkyne.
ethane. Thus in ethyne, hydrogen atoms
can be liberated as protons more easily as
compared to ethene and ethane. Hence,
hydrogen atoms of ethyne attached to triply
bonded carbon atom are acidic in nature. You
may note that the hydrogen atoms attached
to the triply bonded carbons are acidic but
not all the hydrogen atoms of alkynes.
– +
HC ≡ CH + Na → HC ≡ C Na + 1/2 H2
9.4.4 Properties
Monosodium
Physical properties ethynide
Physical properties of alkynes follow the same
(9.59)
trend of alkenes and alkanes. First three – + – + – +
members are gases, the next eight are liquids HC ≡ C Na + Na → Na C Na ≡ C Na + 1/2 H2
and the higher ones are solids. All alkynes Disodium ethynide
are colourless. Ethyene has characteristic
(9.60)
odour. Other members are odourless. Alkynes + –
are weakly polar in nature. They are lighter CH3 – C ≡ C – H + Na NH 2
than water and immiscible with water but ↓
– +
soluble in organic solvents like ethers, carbon CH3 – C ≡ C Na + NH3
tetrachloride and benzene. Their melting Sodium propynide (9.61)
point, boiling point and density increase with
These reactions are not shown by alkenes
increase in molar mass.
and alkanes, hence used for distinction
Chemical properties between alkynes, alkenes and alkanes. What
Alkynes show acidic nature, addition reactions about the above reactions with but-1-yne and
and polymerisation reactions as follows : but-2-yne ? Alkanes, alkenes and alkynes
A. Acidic character of alkyne: Sodium follow the following trend in their acidic
metal and sodamide (NaNH 2) are strong behaviour :
bases. They react with ethyne to form sodium
acetylide with the liberation of dihydrogen i) CH ≡ CH > H2C – CH2 > CH3 –CH3
gas. These reactions have not been observed ii) HC ≡ CH > CH3 –C≡ CH >> CH3 –C≡C–CH3
in case of ethene and ethane thus indicating
that ethyne is acidic in nature in comparison B. Addition reactions: Alkynes contain a
to ethene and ethane. Why is it so ? Has triple bond, so they add up, two molecules of
it something to do with their structures dihydrogen, halogen, hydrogen halides etc.
and the hybridisation ? You have read that Formation of the addition product takes place
hydrogen atoms in ethyne are attached to according to the following steps.

Unit 9.indd 316 10/10/2022 10:37:57 AM


Hydrocarbons 317

The addition product formed depends


upon stability of vinylic cation. Addition in
unsymmetrical alkynes takes place according
to Markovnikov rule. Majority of the reactions
of alkynes are the examples of electrophilic
addition reactions. A few addition reactions
are given below: (9.66)
(i) Addition of dihydrogen (iv) Addition of water
HC≡CH+H2 Pt/Pd/Ni
[H2C = CH2] H2
CH3–CH3 Like alkanes and alkenes, alkynes are also
immiscible and do not react with water.
(9.62) However, one molecule of water adds to
Pt/Pd/Ni
alkynes on warming with mercuric sulphate
CH3–C≡CH + H2 [CH3–CH=CH2] and dilute sulphuric acid at 333 K to form
Propyne Propene carbonyl compounds.
↓H2
CH3–CH2–CH3
Propane
(9.63)
(ii) Addition of halogens

(9.67)

(9.64)
Reddish orange colour of the solution
of bromine in carbon tetrachloride is
decolourised. This is used as a test for
unsaturation.
(iii) Addition of hydrogen halides (9.68)
Two molecules of hydrogen halides (HCl, HBr, (v) Polymerisation
HI) add to alkynes to form gem dihalides (in (a) Linear polymerisation: Under suitable
which two halogens are attached to the same conditions, linear polymerisation of ethyne
carbon atom) takes place to produce polyacetylene or
H–C≡C–H+H–Br [CH2 = CH–Br]→ CHBr2 polyethyne which is a high molecular
Bromoethene weight polyene containing repeating units of
CH3 (CH = CH – CH = CH ) and can be represented
1,1-Dibromoethane as —( CH = CH – CH = CH)n— Under special
(9.65) conditions, this polymer conducts electricity.

Unit 9.indd 317 10/10/2022 10:37:58 AM


318 chemistry

Thin film of polyacetylene can be used as but in a majority of reactions of aromatic


electrodes in batteries. These films are good compounds, the unsaturation of benzene ring
conductors, lighter and cheaper than the is retained. However, there are examples of
metal conductors. aromatic hydrocarbons which do not contain a
(b) Cyclic polymerisation: Ethyne on benzene ring but instead contain other highly
passing through red hot iron tube at 873K unsaturated ring. Aromatic compounds
undergoes cyclic polymerization. Three containing benzene ring are known as
molecules polymerise to form benzene, which benzenoids and those not containing a
is the starting molecule for the preparation of benzene ring are known as non-benzenoids.
derivatives of benzene, dyes, drugs and large Some examples of arenes are given
number of other organic compounds. This is below:
the best route for entering from aliphatic to
aromatic compounds as discussed below:

Benzene Toluene Naphthalene

(9.69)

Problem 9.14 Biphenyl


How will you convert ethanoic acid into
benzene? 9.5.1 Nomenclature and Isomerism
The nomenclature and isomerism of aromatic
Solution hydrocarbons has already been discussed in
Unit 8. All six hydrogen atoms in benzene
are equivalent; so it forms one and only one
type of monosubstituted product. When two
hydrogen atoms in benzene are replaced by
two similar or different monovalent atoms or
groups, three different position isomers are
possible. The 1, 2 or 1, 6 is known as the ortho
(o–), the 1, 3 or 1, 5 as meta (m–) and the 1,
4 as para (p–) disubstituted compounds. A
few examples of derivatives of benzene are
given below:

9.5 Aromatic Hydrocarbon


These hydrocarbons are also known as
‘arenes’. Since most of them possess pleasant
odour (Greek; aroma meaning pleasant
smelling), the class of compounds was Methylbenzene 1,2-Dimethylbenzene
named as ‘aromatic compounds’. Most of such
compounds were found to contain benzene (Toluene) (o-Xylene)
ring. Benzene ring is highly unsaturated

Unit 9.indd 318 11/10/2022 15:28:31


Hydrocarbons 319

Friedrich August Kekulé,a German chemist was born in 1829 at Darmsdt in


Germany. He became Professor in 1856 and Fellow of Royal Society in 1875. He
made major contribution to structural organic chemistry by proposing in 1858 that
carbon atoms can join to one another to form chains and later in 1865,he found
an answer to the challenging problem of benzene structure by suggesting that
these chains can close to form rings. He gave the dynamic structural formula to
benzene which forms the basis for its modern electronic structure. He described
the discovery of benzene structure later as:
FRIEDRICH
“I was sitting writing at my textbook,but the work did not progress; my thoughts
AUGUST KEKULÉ
were elsewhere. I turned my chair to the fire, and dozed. Again the atoms were
(7th September
gambolling before my eyes. This time the smaller groups kept modestly in the
1829–13th July
background. My mental eye, rendered more acute by repeated visions of this
1896)
kind, could now distinguish larger structures of manifold conformations; long
rows,sometimes more closely fitted together; all twisting and turning in snake like motion. But look! What
was that? One of the snakes had seized hold of it’s own tail, and the form whirled mockingly before my
eyes. As if by a flash of lightning I woke;.... I spent the rest of the night working out the consequences of
the hypothesis. Let us learn to dream, gentlemen, and then perhaps we shall learn the truth but let us
beware of making our dreams public before they have been approved by the waking mind.”( 1890).
One hundred years later, on the occasion of Kekulé’s centenary celebrations a group of compounds
having polybenzenoid structures have been named as Kekulenes.

was further found to produce one and only one


monosubstituted derivative which indicated
that all the six carbon and six hydrogen atoms
of benzene are identical. On the basis of this
observation August Kekulé in 1865 proposed
the following structure for benzene having
cyclic arrangement of six carbon atoms with
1,3 Dimethylbenzene 1,4-Dimethylbenzene alternate single and double bonds and one
(m-Xylene) ( p-Xylene) hydrogen atom attached to each carbon atom.
9.5.2 Structure of Benzene
Benzene was isolated by Michael Faraday
in 1825. The molecular formula of benzene,
C6H6, indicates a high degree of unsaturation.
This molecular formula did not account for
its relationship to corresponding alkanes,
alkenes and alkynes which you have studied
in earlier sections of this unit. What do you The Kekulé structure indicates
think about its possible structure? Due to the possibility of two isomeric
its unique properties and unusual stability, 1, 2-dibromobenzenes. In one of the isomers,
it took several years to assign its structure. the bromine atoms are attached to the
Benzene was found to be a stable molecule doubly bonded carbon atoms whereas in the
and found to form a triozonide which indicates other, they are attached to the singly bonded
the presence of three double bonds. Benzene carbons.

Unit 9.indd 319 10/10/2022 10:37:58 AM


320 chemistry

unhybridised p orbital perpendicular to the


plane of the ring as shown below:

However, benzene was found to form only


one ortho disubstituted product. This problem
was overcome by Kekulé by suggesting the
concept of oscillating nature of double bonds
in benzene as given below.

The unhybridised p orbital of carbon atoms


are close enough to form a π bond by lateral
overlap. There are two equal possibilities of
Even with this modification, Kekulé
forming three π bonds by overlap of p orbitals
structure of benzene fails to explain unusual
of C1 –C2, C3 – C4, C5 – C6 or C2 – C3, C4 – C5,
stability and preference to substitution
C6 – C1 respectively as shown in the following
reactions than addition reactions, which
figures.
could later on be explained by resonance.
Resonance and stability of benzene
According to Valence Bond Theory, the
concept of oscillating double bonds in benzene
is now explained by resonance. Benzene is a
hybrid of various resonating structures. The
two structures, A and B given by Kekulé are
the main contributing structures. The hybrid
structure is represented by inserting a circle
or a dotted circle in the hexagon as shown
in (C). The circle represents the six electrons
which are delocalised between the six carbon Fig. 9.7 (a)
atoms of the benzene ring.

(A) (B) (C)


The orbital overlapping gives us better
picture about the structure of benzene. All
2
the six carbon atoms in benzene are sp
2
hybridized. Two sp hybrid orbitals of each
2
carbon atom overlap with sp hybrid orbitals
of adjacent carbon atoms to form six C—C
sigma bonds which are in the hexagonal
2 Fig. 9.7 (b)
plane. The remaining sp hybrid orbital of
each carbon atom overlaps with s orbital Structures shown in Fig. 9.7(a) and (b)
of a hydrogen atom to form six C—H sigma correspond to two Kekulé’s structure with
bonds. Each carbon atom is now left with one localised π bonds. The internuclear distance

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Hydrocarbons 321

between all the carbon atoms in the ring has (i) Planarity
been determined by the X-ray diffraction to (ii) Complete delocalisation of the π electrons
be the same; there is equal probability for the in the ring
p orbital of each carbon atom to overlap with
(iii) Presence of (4n + 2) π electrons in the ring
the p orbitals of adjacent carbon atoms [Fig.
where n is an integer (n = 0, 1, 2, . . .).
9.7 (c)]. This can be represented in the form
of two doughtnuts (rings) of electron clouds This is often referred to as Hückel Rule.
[Fig. 9.7 (d)], one above and one below the Some examples of aromatic compounds are
plane of the hexagonal ring as shown below: given below:

(electron cloud)

Fig. 9.7 (c) Fig. 9.7 (d)


The six π electrons are thus delocalised
and can move freely about the six carbon
nuclei, instead of any two as shown in
Fig. 9.6 (a) or (b). The delocalised π electron cloud
is attracted more strongly by the nuclei of the
carbon atoms than the electron cloud localised
between two carbon atoms. Therefore, presence
of delocalised π electrons in benzene makes
it more stable than the hypothetical
cyclohexatriene.
X-Ray diffraction data reveals that benzene
is a planar molecule. Had any one of the above
structures of benzene (A or B) been correct,
9.5.4 Preparation of Benzene
two types of C—C bond lengths were expected.
However, X-ray data indicates that all the Benzene is commercially isolated from coal
six C—C bond lengths are of the same order tar. However, it may be prepared in the
(139 pm) which is intermediate between laboratory by the following methods.
C— C single bond (154 pm) and C—C double (i) Cyclic polymerisation of ethyne:
bond (133 pm). Thus the absence of pure (Section 9.4.4)
double bond in benzene accounts for the (ii) Decarboxylation of aromatic acids:
reluctance of benzene to show addition Sodium salt of benzoic acid on heating
reactions under normal conditions, thus with sodalime gives benzene.
explaining the unusual behaviour of benzene.
9.5.3 Aromaticity
Benzene was considered as parent ‘aromatic’
compound. Now, the name is applied to all the
ring systems whether or not having benzene (9.70)
ring, possessing following characteristics.

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322 chemistry

(iii) Reduction of phenol: Phenol is reduced (ii) Halogenation: Arenes react with halogens
to benzene by passing its vapours over in the presence of a Lewis acid like anhydrous
heated zinc dust FeCl3, FeBr3 or AlCl3 to yield haloarenes.

(9.71) Chlorobenzene
9.5.5 Properties (9.73)
Physical properties (iii) Sulphonation: The replacement of a
Aromatic hydrocarbons are non- polar hydrogen atom by a sulphonic acid group in
molecules and are usually colourless liquids a ring is called sulphonation. It is carried out
or solids with a characteristic aroma. You are by heating benzene with fuming sulphuric
also familiar with naphthalene balls which are acid (oleum).
used in toilets and for preservation of clothes
because of unique smell of the compound
and the moth repellent property. Aromatic
hydrocarbons are immiscible with water but
are readily miscible with organic solvents.
They burn with sooty flame.
Chemical properties (9.74)
Arenes are characterised by electrophilic
substitution reactions. However, under (iv) Friedel-Crafts alkylation reaction:
special conditions they can also undergo When benzene is treated with an alkyl halide
addition and oxidation reactions. in the presence of anhydrous aluminium
chloride, alkylbenene is formed.
Electrophilic substitution reactions
The common electrophilic substitution
reactions of arenes are nitration, halogenation,
sulphonation, Friedel Craft’s alkylation and
acylation reactions in which attacking reagent
+
is an electrophile (E )
(i) Nitration: A nitro group is introduced (9.75)
into benzene ring when benzene is heated
with a mixture of concentrated nitric acid
and concentrated sulphuric acid (nitrating
mixture).
(9.76)

Why do we get isopropyl benzene on


treating benzene with 1-chloropropane
instead of n-propyl benzene?

(v) Friedel-Crafts acylation reaction: The


reaction of benzene with an acyl halide or
(9.72) acid anhydride in the presence of Lewis acids
(AlCl3) yields acyl benzene.
Nitrobenzene

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Hydrocarbons 323

(9.77)

In the case of nitration, the electrophile,


nitronium ion, is produced by transfer of
a proton (from sulphuric acid) to nitric acid
in the following manner:
Step I
(9.78)
If excess of electrophilic reagent is used,
further substitution reaction may take place
in which other hydrogen atoms of benzene Step II
ring may also be successively replaced
by the electrophile. For example, benzene
on treatment with excess of chlorine in
the presence of anhydrous AlCl 3 can be Protonated Nitronium
chlorinated to hexachlorobenzene (C6Cl6) nitric acid ion
It is interesting to note that in the process
of generation of nitronium ion, sulphuric acid
serves as an acid and nitric acid as a base.
Thus, it is a simple acid-base equilibrium.
(b) F o r m a t i o n o f C a r b o c a t i o n
(arenium ion): Attack of electrophile
results in the formation of σ-complex or
3
(9.79) arenium ion in which one of the carbon is sp
Mechanism of electrophilic substitution hybridised.
reactions:
According to experimental evidences, SE (S =
substitution; E = electrophilic) reactions are
supposed to proceed via the following three
steps:
sigma complex (arenium ion)
(a) Generation of the eletrophile
The arenium ion gets stabilised by
(b) Formation of carbocation intermediate resonance:
(c) Removal of proton from the carbocation
intermediate

(a) Generation of electrophile E : During
chlorination, alkylation and acylation of
benzene, anhydrous AlCl3, being a Lewis acid
⊕ ⊕
helps in generation of the elctrophile Cl , R ,

RC O (acylium ion) respectively by combining
with the attacking reagent.

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324 chemistry

Sigma complex or arenium ion loses its chemical equation:


aromatic character because delocalisation of
3 CxHy + (x + ) O2 → x CO2 + H2O n (9.83)
electrons stops at sp hybridised carbon.
(c) Removal of proton: To restore the 9.5.6 Directive influence of a functional
aromatic character, σ -complex releases group in monosubstituted benzene
3
proton from sp hybridised carbon on attack
– When monosubstituted benzene is subjected
by [AlCl4] (in case of halogenation, alkylation
– to further substitution, three possible
and acylation) and [HSO 4 ] (in case of
disubstituted products are not formed in
nitration).
equal amounts. Two types of behaviour are
observed. Either ortho and para products or
meta product is predominantly formed. It
has also been observed that this behaviour
depends on the nature of the substituent
already present in the benzene ring and not
on the nature of the entering group. This is
known as directive influence of substituents.
Reasons for ortho/para or meta directive
nature of groups are discussed below:
Addition reactions
Ortho and para directing groups: The
Under vigorous conditions, i.e., at high
groups which direct the incoming group to
temperature and/ or pressure in the presence
ortho and para positions are called ortho and
of nickel catalyst, hydrogenation of benzene para directing groups. As an example, let us
gives cyclohexane. discuss the directive influence of phenolic
(–OH) group. Phenol is resonance hybrid of
following structures:

Cyclohexane
(9.80)
Under ultra-violet light, three chlorine
molecules add to benzene to produce benzene
hexachloride, C6H6Cl6 which is also called
gammaxane.

Benzene hexachloride,
It is clear from the above resonating
(BHC) structures that the electron density is more on
(9.81) o – and p – positions. Hence, the substitution
Combustion: When heated in air, benzene takes place mainly at these positions. However,
burns with sooty flame producing CO2 and it may be noted that –I effect of – OH group also
H2O operates due to which the electron density on
15 ortho and para positions of the benzene ring
C H6 + O2 → 6CO2 +3H2O is slightly reduced. But the overall electron
6 2 (9.82) density increases at these positions of the
General combustion reaction for any ring due to resonance. Therefore, –OH group
hydrocarbon may be given by the following activates the benzene ring for the attack by

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Hydrocarbons 325

an electrophile. Other examples of activating In this case, the overall electron density
groups are –NH2, –NHR, –NHCOCH3, –OCH3, on benzene ring decreases making further
–CH3, –C2H5, etc. substitution difficult, therefore these groups
In the case of aryl halides, halogens are are also called ‘deactivating groups’. The
moderately deactivating. Because of their electron density on o – and p – position
strong – I effect, overall electron density on is comparatively less than that at meta
benzene ring decreases. It makes further position. Hence, the electrophile attacks on
substitution difficult. However, due to comparatively electron rich meta position
resonance the electron density on o– and resulting in meta substitution.
p – positions is greater than that at the
9.6 Carcinogenicity and Toxicity
m-position. Hence, they are also o – and p –
directing groups. Resonance structures of Benzene and polynuclear hydrocarbons
chlorobenzene are given below: containing more than two benzene rings
fused together are toxic and said to
possess cancer producing (carcinogenic)
property. Such polynuclear hydrocarbons
are formed on incomplete combustion of
organic materials like tobacco, coal and
petroleum. They enter into human body
and undergo various biochemical reactions
and finally damage DNA and cause cancer.
Some of the carcinogenic hydrocarbons are
given below (see box).

Meta directing group: The groups which


direct the incoming group to meta position are
called meta directing groups. Some examples
of meta directing groups are –NO2, –CN, –CHO,
–COR, –COOH, –COOR, –SO3H, etc.
Let us take the example of nitro group.
Nitro group reduces the electron density in
the benzene ring due to its strong–I effect.
Nitrobenzene is a resonance hybrid of the
following structures.

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326 chemistry

SUMMARY

Hydrocarbons are the compounds of carbon and hydrogen only. Hydrocarbons are mainly
obtained from coal and petroleum, which are the major sources of energy. Petrochemicals
are the prominent starting materials used for the manufacture of a large number of
commercially important products. LPG (liquefied petroleum gas) and CNG (compressed
natural gas), the main sources of energy for domestic fuels and the automobile industry, are
obtained from petroleum. Hydrocarbons are classified as open chain saturated (alkanes)
and unsaturated (alkenes and alkynes), cyclic (alicyclic) and aromatic, according to their
structure.
The important reactions of alkanes are free radical substitution, combustion, oxidation
and aromatization. Alkenes and alkynes undergo addition reactions, which are mainly
electrophilic additions. Aromatic hydrocarbons, despite having unsaturation, undergo
mainly electrophilic substitution reactions. These undergo addition reactions only under
special conditions.
Alkanes show conformational isomerism due to free rotation along the C–C sigma
bonds. Out of staggered and the eclipsed conformations of ethane, staggered conformation
is more stable as hydrogen atoms are farthest apart. Alkenes exhibit geometrical
(cis-trans) isomerism due to restricted rotation around the carbon–carbon double bond.
Benzene and benzenoid compounds show aromatic character. Aromaticity, the
property of being aromatic is possessed by compounds having specific electronic structure
characterised by Hückel (4n+2)π electron rule. The nature of groups or substituents attached
to benzene ring is responsible for activation or deactivation of the benzene ring towards
further electrophilic substitution and also for orientation of the incoming group. Some of
the polynuclear hydrocarbons having fused benzene ring system have carcinogenic property.

EXERCISES

9.1 How do you account for the formation of ethane during chlorination of methane ?
9.2 Write IUPAC names of the following compounds :
(a) CH3CH=C(CH3)2 (b) CH2=CH-C≡C-CH3

(c) (d) –CH2–CH2–CH=CH2

(f) CH3(CH2)4 CH (CH2)3 CH3

(e) CH2 –CH (CH3)2


(g) CH3 – CH = CH – CH2 – CH = CH – CH – CH2 – CH = CH2
|
C2H5
9.3 For the following compounds, write structural formulas and IUPAC names for all
possible isomers having the number of double or triple bond as indicated :
(a) C4H8 (one double bond) (b) C5H8 (one triple bond)
9.4 Write IUPAC names of the products obtained by the ozonolysis of the following
compounds :
(i) Pent-2-ene (ii) 3,4-Dimethylhept-3-ene
(iii) 2-Ethylbut-1-ene (iv) 1-Phenylbut-1-ene

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Hydrocarbons 327

9.5 An alkene ‘A’ on ozonolysis gives a mixture of ethanal and pentan-3-one.


Write structure and IUPAC name of ‘A’.
9.6 An alkene ‘A’ contains three C – C, eight C – H σ bonds and one C – C π
bond. ‘A’ on ozonolysis gives two moles of an aldehyde of molar mass 44
u. Write IUPAC name of ‘A’.
9.7 Propanal and pentan-3-one are the ozonolysis products of an alkene? What
is the structural formula of the alkene?
9.8 Write chemical equations for combustion reaction of the following
hydrocarbons:
(i) Butane (ii) Pentene
(iii) Hexyne (iv) Toluene
9.9 Draw the cis and trans structures of hex-2-ene. Which isomer will have
higher b.p. and why?
9.10 Why is benzene extra ordinarily stable though it contains three double
bonds?
9.11 What are the necessary conditions for any system to be aromatic?
9.12 Explain why the following systems are not aromatic?

(i) (ii) (iii)


9.13 How will you convert benzene into
(i) p-nitrobromobenzene (ii) m- nitrochlorobenzene
(iii) p - nitrotoluene (iv) acetophenone?
9.14 In the alkane H3C – CH2 – C(CH3)2 – CH2 – CH(CH3)2, identify 1°,2°,3° carbon
atoms and give the number of H atoms bonded to each one of these.
9.15 What effect does branching of an alkane chain has on its boiling point?
9.16 Addition of HBr to propene yields 2-bromopropane, while in the presence
of benzoyl peroxide, the same reaction yields 1-bromopropane. Explain
and give mechanism.
9.17 Write down the products of ozonolysis of 1,2-dimethylbenzene (o-xylene).
How does the result support Kekulé structure for benzene?
9.18 Arrange benzene, n-hexane and ethyne in decreasing order of acidic
behaviour. Also give reason for this behaviour.
9.19 Why does benzene undergo electrophilic substitution reactions easily and
nucleophilic substitutions with difficulty?
9.20 How would you convert the following compounds into benzene?
(i) Ethyne (ii) Ethene (iii) Hexane
9.21 Write structures of all the alkenes which on hydrogenation give
2-methylbutane.
9.22 Arrange the following set of compounds in order of their decreasing relative
+
reactivity with an electrophile, E
(a) Chlorobenzene, 2,4-dinitrochlorobenzene, p-nitrochlorobenzene
(b) Toluene, p-H3C – C6H4 – NO2, p-O2N – C6H4 – NO2.
9.23 Out of benzene, m–dinitrobenzene and toluene which will undergo nitration
most easily and why?
9.24 Suggest the name of a Lewis acid other than anhydrous aluminium chloride
which can be used during ethylation of benzene.
9.25 Why is Wurtz reaction not preferred for the preparation of alkanes
containing odd number of carbon atoms? Illustrate your answer by taking
one example.

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Answer to Some Selected Problems

Unit 7

7.25 15 g
Unit 8

8.32 Mass of carbon dioxide formed = 0.505 g


Mass of water formed = 0.0864 g
8.33 % fo nitrogen = 56
8.34 % of chlorine = 37.57
8.35 % of sulphur = 19.66

Unit 9

9.1
.
Due to the side reaction in termination step by the combination of two C H3 free
radicals.
9.2 (a) 2-Methyl-but-2-ene (b) Pent-1-ene-3-yne
(c) Buta-1, 3-diene (d) 4-Phenylbut-1-ene
(e) 2-Methylphenol (f) 5-(2-Methylpropyl)-decane
(g) 4-Ethyldeca –1,5,8- triene
9.3 (a) (i) CH2 = CH – CH2 – CH3 But-1-ene
(ii) CH3 – CH2 = CH – CH3 But-2-ene
(iii) CH2 = C – CH3 2-Methylpropene
|
CH3
(b) (i) HC ≡ C – CH2 – CH2 – CH3 Pent-1-yne
(ii) CH3 – C ≡ C – CH2 – CH3 Pent-2-yne
(iii) CH3 – CH – C ≡ CH 3-Methylbut-1-yne
|
CH3
9.4 (i) Ethanal and propanal (ii) Butan-2-one and pentan-2-one
(iii) Methanal and pentan-3-one (iv) Propanal and benzaldehyde
9.5 3-Ethylpent-2-ene
9.6 But-2-ene
9.7 4-Ethylhex-3-ene
CH3 – CH2– C = CH – CH2–CH3
|
CH2–CH3

Answers.indd 328 10/27/2022 2:32:20 PM


answers 329


9.8 (a) C4H10(g)+13/202(g) 4CO2(g) + 5H2O(g)

(b) C5H10(g)+15/202(g) 5CO2(g) + 5H2O(g)

(c) C5H10(g) + 17/2 O2(g) 6CO2(g) + 5H2O(g)

(d) C7H8(g) + 902(g) 7CO2(g) + 4H2O(g)

cis-Hex-2-ene trans-Hex-2-ene

The cis form will have higher boiling point due to more polar nature leading
to stronger intermolecular dipole–dipole interaction, thus requiring more
heat energy to separate them.
9.10 Due to resonance
9.11 Planar, conjugated ring system with delocalisation of (4n+2) π electrons,
where, n is an integer
9.12 Lack of delocalisation of (4n +2) π electrons in the cyclic system.
9.13 (i)

(ii)

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330 chemistry

(iii)

(iv)

9.14

15 H attached to 1° carbons
4 H attached to 2° carbons
1 H attached to 3° carbons
9.15 More the branching in alkane, lower will be the boiling point.
9.16 Refer to addition reaction of HBr to unsymmetrical alkenes in the text.

All the three products cannot be obtained by any one of the Kekulé’s
structures. This shows that benzene is a resonance hybrid of the two
resonating structures.
9.18 H – C ≡ C – H > C6H6 > C6H14. Due to maximum s orbital character
in enthyne (50 per cent) as compared to 33 per cent in benzene and
25 per cent in n-hexane.
9.19 Due to the presence of 6 π electrons, benzene behaves as a rich source of
electrons thus being easily attacked by reagents deficient in electrons.

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answers 331

9.20 (i)

Br2 alc, KOH NaNH2


(ii) C2H4 CH2–CH2 CH2=CHNr

Br BR

(iii)
CH3
|
9.21 CH2 = C – CH2 – CH3 2-Methylbut-1-ene

CH3
|
CH3 – C = CH – CH3 2-Methylbut-2-ene

CH3
|
CH3 – CH –CH = CH2 3-Methylbut-1-ene
9.22 (a) Chlorobenzene>p-nitrochlorobenzene> 2,4 – dinitrochlorobenzene
(b) Toluene > p-CH3-C6H4-NO2 > p-O2N–C6H4–NO2
9.23 Toleune undergoes nitration most easily due to electron releasing
nature of the methyl group.
9.24 FeCl3
9.25 Due to the formation of side products. For example, by starting with
1-bromopropane and 1-bromobutane, hexane and octane are the side
products besides heptane.

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332 chemistry

Notes

Answers.indd 332 10/10/2022 11:12:18 AM

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