..
k=.!.. x
t a (a - x)
When the reaction is 20% complete, x = 0.2a
k=_l_. 0.2a 1. 0.2a _ __
.. 500 a (a - 0.2 a) 500 a X 0.8a 2000 a
Suppose it takes t\ seonds for the reaction to go to 60% completion.
N k =1. . 0.6a _ 1 0.6a =1. . l
ow, tl a (a - 0.6a) t 2 a X OAa tJ 2a
1 .-
- 3 =--
or
tl 2a 2000a
t) = 3000 sec.
Ex.4: A second order reaction with two reactants is started with O.IM
concentrations of each reactant. It is 20% completed in 500 seco~ds. How
long will it take the reaction to go to 70% completion?
For a second order reaction when the concentrations are equal, we have
k=.!.. x
t a (a - x)
For 20% completion: a =0.1, x= 0.2 X 0.1 =0.02; t =500
k = _1_ X 0.02 =_1_ X 0.02 =_I_
.. 500 0.1 (0.1 - 0.02) 500 0.1 x 0.01 200
For 60% completion: a = 1; x =0.6 X 0.1 = 0.06; t = ?
k=! X 0.:.::.06=--_
.. t 0.1 (0.1 - 0.06)
1 1 0.06
or -=-x
200 t 0.1 - 0.04
200 x 0.06
or t =Q.l X 0.04 =3000 seconds.
2. CATALYSIS
Problem 1. Define catalyst and catalysis. Mention the types and classifi-
cation of catalysis. Discuss the characteristics of catalytic reactions.
[I] Catalyst and CatalysiS
Berzelius (1835) found that the speed of a number of reactions is in-
creased due to the presence of a small quantity of a foreign substance. He also
252 PHYSICAL CHEMISTRY-I
found that these substances remain chemically unchanged at the end of the
reaction. He termed these substances as catalysts and the phenomenon itself is
known as catalysis. A familiar example is that of the decomposition of
KCI03 . The decomposition of KCl0 3 is very slow even at high temperature,
but a small quantity ofMn02 increases the rate of decomposition to a very great
extent and Mn02 remains chemically unchanged at the end of the reaction.
2KCl03 + [Mn02] ~ 2KCl + 302 + [Mn02]
But later on it was observed that there are certain substances which can
retard the rate of a chemical reaction. Hence. Ostwald defined that.
"A catalyst is a substance which influences the speed of a 'chemical
reaction without itself undergoing any chemical change at the end of the
reaction. "
Catalysis is mainly divided into two types. viz . homogeneous catalysis
and heterogeneous catalysis.
[A] Homogeneous Catalysis
When the catalyst is present in the same phase as that ofthe reactants,
the phenomenon is known as homogeneous catalysis.
(a) Examples of homogeneous catalysis in gas phase
(i) Oxidation of sulphur dioxide (S02) to sulphur trioxide (S03) with
nitric oxide (NO) as catalyst.
2S02 + O2 + [NO] ~ 2S03 + [NO]
Gas Gas Gas Gas
I
2H20 2 ~ 2H20 +02
(ii) Hydrolysis of cane sugar in aqueous solution in the presence of
mineral acid as catalyst.
Catalyst
Other reactions are :
Mn2
(ii) 2KCI03 --~) 2KCI + 302
PtorNO
(iv) 2S02 + O2 ) 2S03
(b) Negative CMaJysis: When the foreign substance retards the
speed of a chemical reaction, it is known as a negative catalyst and the
phenomenon is known as negative catalysis. The following are examples of
this type.
(i) Decomposition of hydrogen peroxide
H,P04
2H20 2 ~ 2H20 + O 2
(ii) Oxidation of chloroform
C,H,OH
4CHCl3 + 302 ) 4COCI 2 + 2Cl2 + 2H20
-
(iii) Tetraethyllead as antiknock
When tetraethyllead. Pb(C2H5)4 is added to petrol. it retards the too
rapid or explosive combustion of the fuel which is responsible for the working
of the engine.
Explanation of Negative Catalysis
The mechanism of negative catalysis could be different for different
reactions, e.g .
(1) By poisoning a catalyst. A negative catalyst may work by poi-
soning a catalyst which already happens to be present in the reaction mixture.
CHEMICAL KINETICS & CATALYSIS 255
For example, the traces of alkali dissolved from the glass of the container,
catalyse the decomposition of hydrogen peroxide (H20 2). However, the ad-
dition of an acid would destroy the alkali catalyst and thus prevents decom-
position.
(2) By breaking a chain reaction. In some cases, negative catalysts
are believed to operate by breaking the chain of reactions. For example, the
combination of H2 and C1 2, which is a chain reaction, is negatively catalysed
by nitrogen trichloride (NCI 3).
Cl2 ~ Cl'+Cl'
Free radicals
A+B ~ C+D
is shown in fig. (6). In the begin-
ning, the concentrations of A and
B are maximum and so the rate of
forward reaction is maximum. As
the time passes, the rate of the re-
action decreases till the equilib-
rium is established. For the reverse Equilibrium
reaction, the initial concentrations
of C and D are zero and the rate of
reaction is lowest. As the time
passes, the rate of reaction in-
creases till the equilibrium is estab- Time--.
lished. Similar curves of the rates
of reactions with the catalyst show
that the rates of the forward reac- :::::: time required for ih:e equilibrium ::::::
tion and the reverse reaction are )t. . . . '.' . . . . . . .~. ~. ~~~~.~~~~:......................... mm
changed equally but the equilib-
rium is established in a much shorter time.
For example, in the Haber's process for ammonia,
Fe
N2 + 3H2
2NH3 ~
the reaction is very slow. In the presence of the catalyst, the equilibrium is
reached much earlier but the percentage yield remains unchanged. The iron
catalyst decreases the time to attain equilibrium but cannot change the per-
centage yield.
Energy considerations also show that the final state of equilibrium
cannot be changed by the catalyst. Suppose the catalyst accelerates the for-
ward reaction more than the reverse reaction. This will shift the equilibrium
point, which cannot happen without the supply of energy to the system. But
a catalyst unchanged in mass and~composition at the end of the reaction,
cannot supply the required energy.
Problem 2. Write notes on the following:
(a) Catalytic promoters (b) Catalytic poisons
(A) Catalytic Promoters
The activity of a catalyst can often be increased by the addition of a
small quantity of a second material. This second substance is either not a
catalyst itself for the reaction or it may be a feeble catalyst.
A substance which, though itself not a catalyst, promotes the activity
of a catalyst is called a promoter or an activator.
[I] Examples of Promoters
(i) In some reactions, mixtures of catalysts are used to obtain the
maximum catalytic efficiency. For example, in the synthesis of methanol
CHEMICAL KINETICS & CATALYSIS 259
(CH 30H) from carbon monoxide and hydrogen, a mixture of zinc oxide and
chromium oxide is used as a catalyst.
Peak
&
-~i-~i-~i-~i-~i- \~
1'% I I
-Ni-Ni-Ni
I I I I I I I I
-Ni-Ni-Ni-Ni-Ni- -Ni-Ni-Ni .;,:
I I I I I I I I ~
-Ni-Ni-Ni-Ni-Ni- -Ni-Ni-Ni U
I I I I I I I I I
-Ni-Ni-Ni-Ni-Ni- -Ni-Ni-Ni-Ni-Ni-
I I I I I I I I I I
IF''''''''''''''''''''''''''''''''''''''''''''"'''''"''"~;?;S,:"""""""''""''""""''''11
~ Distance between
catalyst particles ~
/f I"
:.:.. .:.:.:.:.:.:.:.:. .:.:.:.:.:.:. :.-.:.:.:.:.:.:.:.: . catalyst makes the reaction go faster? ':::'::-:::::": ;.:.: :::::
::::::::::::::-::::::::::::::.........................................................................................................................................................................::}}}:.:;.:
(a) Examples of Catalytic Poisoning
(1) The platinum catalyst used in the oxidation of hydrogen is poisoned
by carbon monoxide.
Pt
2H2 + O2 ----+) 2H20
Poisoned
by CO
(2) The platinum catalyst used in the oxidation of sulphur dioxide
(contact process) is poisoned by arsenic oxide (AsP3)'
Pt
2S0 2 + O2 ----+) 2S03
Poisoned
by AS20 3
(3) The iron catalyst used in the synthesis of ammonia (Haber's process)
is poisoned by H 2S.
Fe
N2 + 3H2 ----+) 2NH3
o o o
II
c,
II
c
II
,
, , , , ,c,
, , ,, ,, , , ,,
Fe + H2S ~ FeS+H2
Problem 3. Discuss the theories of catalysis and also mention the indus-
trial applications of catalysts.
[I] Theories of Catalysis
Many theories have been put forward to explain the catalytic activity
of catalyst. A few important theories are given below :
1. Intermediate Compound Formation Theory
According to this theory, a catalyst first combines with one of the
reactants to form an intermediate compound of activity greater than that of
the reactants. This intermediate compound then reacts with another reactant
fufurm the product and so gives back the catalyst. If A and B are two reactants
and C is a catalyst, then according to this theory. .
A+C~ AC
AC+B ~ AB+C
A+B+[C] ~ AB+[C]
This theory can be fully explained by the following examples :
(1) In the oxidation of S02 by air, NO which acts as a catalyst, first
combines with oxygen to form N0 2 (intermediate compound) which oxidises
S02 and gives back nitric oxide.
2NO + O2 ~ 2N0 2
[S02 + N0 2 ~ S03 + NO] x 2
2S0 2 + O2 + [2NO] ~ 2S03 + [2NO]
(2) In the formation of ether from alcohol, H2S04 which is used as
catalyst first forms an intermediate compound C2H sHS0 4 .
C2HsOH + H2S04 ~ C2HsHS0 4 + HP
C 2HsHS04 + C2HsOH ~ C2HsOC2HS + H2S04
262 PHYSICAL CHEMISTRY-I
!!;,t;i;;;i;;~;:;?~~;.~~~~~~?~~;:::~tg::..
The mechanism of contact catalysis may vary in details, depending on
the nature of the reactants. Consider the example of hydrogenation of ethene
in presence of nickel. In this casse, ethene adds hydrogen in the presence of
nickel as a catalyst to yield ethane.
H H
I I
_N_i.....:(c_a_ta....;ly'-st-'-)~) H-C--C-H
I I
H H
Ethene gas Ethane (gas)
il'::"""'''''''''~'''''''''''''''''''''''''''''''''''''''''M""""""""'":'~
j H/r:I"--H HH/C--C"--HH
)~ @--@ I
:'.! Step 3 Step 4 \
2NO + 02 ~ 2N02
4N02 + 2H20 + 02 ~ 4HN03
4. Manufacture of hydrogen by Bosch's Ferric oxide + Cr203 (as a promoter) at a
process temp. of 400-600C.
(CO + Hz) + H20 ~ C02 + H20
Water gas
5. Manufacture of methyl alcohol from ZnO + Cr203 (as a promoter). 200 atms.
water gas pressure and temp of 450C.
CO+H2 +H2 ~ CH30H
Water gas
(2) Like inorganic catalysts they cannot disturb the final state of equi-
librium of a reversible reaction.
(3) They are highly specific in nature, i.e., one catalyst cannot catalyse
more than one reaction.
(4) They are highly specific to temperature. The optimum temperature
of their activity is 35C to 40C. They are deactivated at 70C.
(5) Their activity is increased in the presence of certain substances,
known as co-enzymes.
(6) A small quantity of enzyme catalyst is sufficient for a large change.
(7) They are destroyed by U.v. rays.
(8) Their efficiency is decreased in presence of electrolytes.
[II] Examples of Enzyme Catalysis
The following are some examples of biochemical or enzyme catalysis.
(1) Manufacture of ethyl alcohol from cane sugar
Glucose Fructose
Zymase
C6H120 6 ) 2C 2H50H + 2C0 2
(2) Manufacture of acetic acid from ethyl alcohol
Maltase
C 12H220 U + H20 ---~) 2C6H l2 0 6
Maltose Glucose
J
CHEMICAL KINETICS & CATALYSIS 267
where kl' k2' k3 are the rate constants for the respective reactions.
The rate of formation of the complex ES is, evidently given by the
following equation,
... (1)
where [E], [S] and [ES] represent molar concentrations of the free enzyme,
substrate and the complex, i.e., bound or reacted enzyme, respectively.
Now [E] cannot be experimentally measured. The equilibruim between
the free and bound enzyme is given by the enzyme conservation equation,
i.e.,
[E]o = [E] + [ES]
d [ES] = 0
dt
268 PHYSICAL CHEMISTRY-I
. 1
Maxlmum rate, 2 Vmax
(ii) If [S] is very large as compared to Km, the factor Km/[S] will be
negligibly small as compared to unity and so the rate of formation
of P, i.e., d [P]/dt will be independent of the concentration [S].
In other words, the reaction will be of zero order with respect to
S (Fig. 13).
(iii) If [S] is very small or very large, the reaction remains of the first
order with respect to the total concentration, [E]o of the enzyme.
Problems 5. mite a short note on acid-base catalysis. (Meerut. 2007)
As a result of the work of Bronsted, Lowry and others, it has become
evident in recent years that a variety of atomic, molecular and ionic species
are capable of catalysing chemical reactions. For some processes, hydrogen
ions appear to be effective, while other reactions are catalysed by hydroxyl
ions, cations of weak bases, anions of weak acids, undissociated molecules
of acids and bases etc. This general acid catalysis involves cases where all
acids act as catalysts, while general base catalysis refers to processes
catalysed by bases of all kinds. In some cases, both acids and bases are
effective, while in others a particular species is effective. General acid-base
catalysis is illustrated by mutarotation of glucose, which is catalysed by
hydrogen, hydroxyl and complex ions, as well as by the acids and bases,
though the most effective catalyst is the hydrogen ion.
270 PHYSICAL CHEMISTRY-I
H H
15. If the plot of 10glO [A] against time is a straight line with a negative slope, the
order of reaction is :
(i) 0 (ii) 1 (iii) 2 (iv) 3
16. In the hydrogenation of oils the catalyst used is :
(i) Iron (ii) Platinum
(iii) Nickel (iv) Molybdenum
17. The effect of a catalyst in a chemical reaction is to change the:
(i) Activation energy (ii) Equilibrium concentration
(iii) Heat of reaction (iv) Final product
18. The catalyst used in the contact process of sulphuric acid manufacture is :
(i) Oxides of nitrogen (ii) Nickel
(iii) Vanadium pentoxide (iv) Manganese dioxide
19. Which of the following is used as a contact catalyst?
(i) Boron (ii) Germanium
(iii) Nickel (iv) U~anium
20. Which of the following statements is universally correct?
(i) A catalyst remains unchanged at the end of the reaction
(ii) A catalyst physically changes at the end of the reaction
(iii) A catalyst takes part in the chemical reaction
(iv) A catalyst can induce chemical reaction
21. The catalyst used for the oxidation of ammonia to nitric acid is :
(i) Cupric chloride (ii) Iron oxide
(iii) Platinum (iv) Manganese dioxide
22. A substance that regards the rate of chemical reaction in the presence of a catalyst
is called :
(i) An inhibitor (ii) A positive catalyst
(iii) An auto-catalyst (iv)A promoter
23. A catalyst poison is essentially:
(i) A homogeneous catalyst (ii) A heterogeneous catalyst
(iii) An inhibitor (iv) An auto-catalyst
24. Catalyst poisons (temporary poisoning) act by :
(i) Chemically combining with the catalyst
(ii) Getting adsorbed on the active centres on the catalyst surface
(iii) Chemical combination with anyone of the reactants
(iv) Coagulating the catalyst
25. Which of the following types of the metal make the most effiCIent catalyst?
(i) Transition metals (ii) Alkali metals
(iii) Alkaline earth metals (iv) Coloured metals
26. Which one of the following statements is incorrect?
(i) Presence of a catalyst does not alter the equilibrium concentration in a
reversible reaction
(ii) Change of temperature alter the rate of catalysed reaction in the same
proportion as of the reaction without catalyst
(iii) Homogeneous catalysis depends upon the nature and extent of the surface
(iv) Change of a catalyst may change the nature of the reaction
27. Enzymes are:
(i) Micro-organisms (ii) Proteins
(iii) Inorganic compounds (iv) Moulds
CHEMICAL KINETICS & CATALYSIS 273
15. In the conversion of urea into ammonium carbonate ................. acts as a catalyst.
16. 2502 + O2 ~ 2S0 3 is an example of .............. catalysis.
He!
17. CH 3COOCH 3 + H20~ CH 3COOH + C 2H50H is an example of .......... .
catalysis.
18. ~ 2NH , Mo acts as ............. .
In N2 + 3H2 ~ 3
19. A catalyst poison is essentially a ............... .
20. The presence of a catalyst ............ the activation energy of the reaction.
True or False
State whether the following statements are true (T) or
false (F)?
1. The value of temperature coefficient is nearly 10.
2. All radioactive emanations are of first order.
3. The inversion of cane sugar by HCI is of second order.
. ,, 4. The reaction rate is proportonal to the surface area of reactant.
15. A catalyst remains unchanged in mass and chemical composition at the end of
a reaction.
16. A large quantity of catalyst is required to bring about a reaction.
17. The substance which increases the activity of a catalyst is called an activator.
18. A promoter decreases the peaks and cracks on the catalyst surface.
19. Enzyme ptyalin present in h)lman saliva changes starch into glucose.
20. The presence of a catalyst increases the activation energy of the reaction.
21. In homogeneous catalysis, the intermediate compound is formed at lower acti-
vation energy.
22. A catalyst cannot be recovered unchanged chemically at the end of the reaction.
ANSWERS
1. (a) ,2. (b) 3. (b) 4. (c) 5. (b) 6. (a) 7. (b) 8. (c) 9. (a) 10. (d) 11. (c) 12. (d)
llWK~~~~~nWm~~~Wn~nWn~u~
25. (a) 26. (c) 27. (b) 28. (b) 29. (c) 30. (a) 31. (c) 32. (a) 33. (d) 34. (d) 35. (a) 36. (c)
37. (b) 38. (c) 39. (c) 40. (c) 41. (b) 42. (d) 43. (c) 44. (b) 45. (d) 46. (a) 47. (c) 48 (d)
49. (d)
True or False
1. (F), 2. (T), 3. (F), 4. en,
5. (T), 6. (F), 7. (F), 8. (T),
9. (T), 10. (F); 11. (F), 12. (T),
13. (T), 14. (F), 15. (T), 16. (F),
17. (T), 18. (F), 19. en, 20. (F),
21. (T), 22. (F)
DOD