Chemistery 11 (English Part II)
Chemistery 11 (English Part II)
Chemistery 11 (English Part II)
Unit 7
redox reactions
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which hydrogen has been replaced by oxygen 2 HgO (s) 2 Hg (l) + O2 (g) (7.8)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
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.
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
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.
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.
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.
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)
– –
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),
+2 0 +2
O = C = C*= C = O
Structure of C3O2
(carbon suboxide)
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+
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
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
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.
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)
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).
Unit 8
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.
(b)
Ethane Ethene
(c)
Ethyne Methanol
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
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
Fig. 8.2
Fig. 8.1 Wedge-and-dash representation of CH4
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
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.
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 CH2CH 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 CH3CH2CHCCH2CH2CH3
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
CCCCCCCCC 1 2 3 4 5 6 7 8
CH3 — CH2—CH—CH2—CH2—CH—CH2 —CH3
C CC
CH2CH3 CH3
9 8 7 6 5 4 3 2 1
CCCCCCCCC 6. The branched alkyl groups can be
named by following the above mentioned
C CC 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
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.
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
2-Chloro-1-methyl-4-nitrobenzene
(not 4-methyl-5-chloro-nitrobenzene)
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:
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.
Fig.8.8 Distillation under reduced pressure. A liquid boils at a temperature below its
vapour pressure by reducing the pressure.
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.
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.
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
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.
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
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
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
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.
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 :
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
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
–
(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 9
Hydrocarbons
(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)
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
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
(3,3-Diethyl-5-isopropyl-4-methyloctane)
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
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
Chloromethane Methane
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
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
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
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
Fig. 9.5 Orbital picture of ethene showing formation of (a) π-bond, (b) π-cloud and (c) bond angles and
bond lengths
(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)
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,
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
Solution
. Homolysis .
(ii) C 6H5+H–Br C6H3+ B r
(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
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)
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.
(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.
(9.69)
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)
(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)
(9.77)
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
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).
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
Unit 7
7.25 15 g
Unit 8
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
∆
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)
(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.
9.20 (i)
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.
Notes