9

CATALYSIS*
9.1. CATALYSIS-A GENERAL INTRODUCTION
9.1.1. WHAT IS CATALYSIS?
A clalysI IN a Nubalemce that changer (usually Increuserj the rale ofu reuctin hut 1: recovere

chemlcally unchnged at the end of the reactinn und the phenomennn it called catalysis. hng a
Catnlyst is not consumed, it docn cnter into the chemical rCactin but is subswaquaitly reyeatAan, 2s W

bo discumncd lutor in thin chapter.

9.1.2. POSITIVE AND NEGATIVE CATALYSIS
calledu
positive calalyst and the phenomenn
f4 ceatalysi Inereanen the rale afa reaction, it in beleru
called posllve calalyriw. A few examples of prnitive catalysis pyvn
arc

cualys.
() Decomowitlon ofpotauhum chlorale in prerenee ofMn),
ur

2 KCIO, (u)
N) caalyst
(0) Oxhdatlon of S4), to $), ming
ar

o, (e)*0,( r ) ,5,2) catalyst

Haher 'i pro.eM U:ing, funely di vded iron ax

(/) Mamufucture ofammonla hy

N () +3 H,K) 2NH, ()
ucetate in presence of n acid or an ulkali as catalyst
(iv) Hydrolysls ofethyl
CH,COOCy}1, +,0. CHCOOH CHO
1E called A
I1 nEgative catalyst and the phenmenon
Ifa catalyst decreasen the rale ofa reuction,
of negative catalys15 arc given belrw;
fcw cxamples
Ixcalled negalive calalysis. A

() Decompsotion of0 ,
ix retarded in the prerence oftrace: ofacetanilide
Auctanilid
2H,02 2H,O+0
() Ocidatlon of chloroform
is relarded in the prerence ofa small quantity ofethyl alcoho!
Calsof
CHC+02
2g 2 COC%2 2 HCI
Chloroform Phongene
ir added to petrol o stup chain reactionr vhich couse knnr iien
(n Tetraethyl lead (anti-knock)
always means positive catalysis.
The term'catalysis' used without any prefix
included in the K.U MDU syllabius alongwith surface churris1ry

467
 9.1.3. AUTOCATALYSiS
7 a reaction, one ofthe products acts as a catalystfor
1he reaction, the
phenomenon i
called autocatalysis. For example,
) n the titration of hot oxalic acid solution against acidified KIMnO4 solution, the pink colon
s aischarged first slowly and then rapidly as the reaction proceeds. 1his 1S because the Mn?
1ons formed during the reaction actas autocatalyst for the reaction.
2 MnO,+ 16 H* +2 C,O2- 2Mn2* +10 cO+8 H,O
(Autocatalyst)
(i) The hydrolysis of ester by water is slow in the beginning but the acid formed during the
reaction acts as an autocatalyst and subsequently the reaction is speeded up.
RCOOR+ H,0 RCOOH +R'OH
(Autocatalyst)
9.1.4. GENERAL CHARACTERISTICS OF A CATALYST
) A catalyst remains chemicallyumchangedat theend ofthe reaction. It may, however, undergo
a change in physical state, colour etc. For example, MnO2 used as catalyst in the decomposition
of KCIo3 changes from coarse powder to fine powder at the end of the reaction.
(i) A small amount ofthe catalyst is sufficient to bring about a large change in the speed ofthe
reaction eg traces of platinum as catalyst are sufficient for large volumes of H2 and O, to
combine to form H,O.
(in) A catalyst is specific in nature. A particular substance may act as a catalyst for one reaction
but the same substance may not act as catalyst even for a similar reaction.
(v) A catalyst does not initiate a reaction. It simpiy changes the speed of the reaction.
()A catalyst does not disturb the state of equilibrium ofa chemical reaction. This is because
it increases the speed of forward and backward
IN ABSENCE
reaction to the same extent. OF CATALYST
(vi) A catalyst shows maximum activity at a IN PRESENCE
particular temperature, called optimum OF CATALYST|
temperature.
9.1.5. HOW DOES A CATALYST WORK ?
A catalyst decreases the activation energy of the reaction
REACANTS
i.e., lowers the energy barrier and thus makes the reaction
fast, as shown in Fig. 9.1. However, it may be noted that in a
reversible reaction, the catalyst decreases the activation energy PRODUCTSs
of the forward reaction as well as that of the backward reaction PROGRESS OF REACTION

by the same amount. Thus both the forward and the backward FIGURE 9.1.
reactions are accelerated to
same extent. As a result,i
thebut Activation energy diagram
for
cquilibrium is attainced quickly is not disturbed. uncatalysed and catalysed reactions
9.1.6. PROMOTERS AND INHIBITORS (CATALYTIC POISONS)
Sometimes the presence of some other substances which are not necessarily catalysts increases the
efficiency ofa catalyst. Such substances thus act as catalystfor the catalyst and are called promoters or
activators. Molybdenum acts as a promoter tor the iron catalyst in the manufacture of ammonia by Haber's
process. Similarly, the synthesis ofmethyl alcohol from CO and H, is catalysed by zinc oxide mixed with
chromiun oxide and other oxides as promoters.
Pradeep's PHYSICAL CHEMTSTRYVOL:L
468
 In some cases, the presence of small quantities of impurities in
the reacting substances ina
catalyst inactive. Such substances are called
catalytic poisons or inhibitors. Catalystic
also poisonous to organisms. Arsenious oxide and hydrogen cyanide are twoof themostpoiso werful catal
powerful catalytic
by
poisons. Arsenious oxide poisons
poisons. Arsenious platinized asbestos used as catalyst in the manufacture of H,SO4
contact process
9.2. HOMOGENEOUS AND HETEROGENEOUS CATALYSIS
9.2.1. HOMOGENEOUS CATALYSIS
1t 1s c u e u
When in a reaction, the catalyst is present in the same phase as the reactants,
homogeneous catalysis.
Examples of homogeneous catalysis taking place in the gaseous phase
oxide (NO)
) Reaction between SO, and to O, 1o form SO in presence ofnitric

2 SO, (g)+0, () 2 SO, ) NOCg

iodine vapours
(i) Decomposition of acetaldehyde in the presence of

CH,CHO () CH, g)+CO (¢)

gaseous ofNO at 1000 K in presence of
traces
of chlorine gas
(ii) Decomposition of
Cl2 (g) (8)
2N,O() 1000K2N)+0,
in presence ofN0 N,O or

(v) Decomposition of
ozone

NO(g)
208) or N205 (8)
>30, (8)
alcohol in presence ofHBr gas
Gas phase dehydration of
tert-butyl
v)
HBr
-
OH (CH),C CH +H,O
(CH),C 2-Methyl propene
tert-butyl alcohol
number of examples
place in the liquid phase. A large
catalysis taking divided into
Examples of
Homogeneous
in the liquid phase (solutions). These may be
been studied
of homogeneous catalysis have
two categories. catalysis in the solution are those
of homogeneous
Most of the examples
catalysis.
MA) Acid-Base
base e.g, of cane-sugar
catalysed by an acid or a ihe presence oj a mineral acid (Inversion
(sucrose) im
cane-sugar
(t) Hydrolysis of
R , CH,0, (ag) +CgH20, (aq)
C2H20(aq) + H,O () Glucos Fructose

Sucrose acid or a base

acetate by a n
i ) Hydrolysis ofmethyl
H* (aq)
CH,COOH(aq)+ CH,OH (aq)
()
CH,COOCH, (ag) H,O
+ or OH- (ag)

469
 1.e., it is a first order reaction vith
very low value of K
In the presence of
HBr, the rate equation is observed to be
R a t e d | t -BuOH] L, [HBr]
d
[-BuOH] -

i.e., it is a second order reaction with high value

of k2.
This suggests that a possible mechanism for the catalysted reaction is

Slow
(CH) C-OH+ HBr > (CH,), C-Br +H,O ...Rate determining step

(CH), C-Br (CH,), C = CH, +HBr

s is supported by the fact that t-butyl bromide is found to be an intermediate.
(3) Kinetics ofthe General Acid-Base Catalysed Reactions. A large number ofreactions are catalysed
by acids and bases. Here acids and bases can be taken as substances defined on the bas1s of
any of the
acid-base concepts i.e., substances that
yield H* and OH ions in aqueous solution (Arrhenius concept),
proton donors and acceptors (Bronsted concept) or electron acceptors and donors (Lewis
In an acid-catalysed reaction, the first
concept).
step is the transfer of a proton (H* ion) from the acid HA to
the substrate S (i.e., one of the reactant
molecules)
K1
S+HA SH+A
This is then followed by one of the two possibilities i.e., either
proton transfer to the solvent (protolytic
mechanism) e.g.

SH*+H0 P+H,0* (P-Product) .i)

or proton transfer to the base A (prototropic mechanism) i.e.,
SH* +A P +HA
..ii)
Taking reaction () as the first step and reaction (fi) as the second step, then
rate determining step, the reaction rate is given by taking the latter as the

dS-k, [SH*]
dt .iv)
But the rate of reaction of [SH°] is given by
d[SH*] =
Rate of formation of SHt from S and
dt HA
-

Rate of reaction of SH* with

H,O
=
{k [S] [HA] -

K ISH*] LA]} k, SH'J}

-

The steady state condition implies that the rate of change of concentration of
be zero. [SH*] with time should

i.e. d(SH)0.
dt
Thus & IS] [HA]- &; ISH'I [AJ-k, [SH"]=0
or
[SH] {k; A] +k%} =k, [S] [HA]
472 Pradeen's D E se
 or ISH 1S[HA]
k[A]+k
Putting this value iniequation (iv), we get
dS)}
dt
[S]HA] .vi)
k[A]+k
Ifk< k [A], cquation (ví) becomes

d[S] kk [STHA]
dt k [A-]
But for the weak acid HA,
HA +HO A+H,O*
so that the equilibrium constant for this acid-base reaction is

KA][H,0*] ..vii)
[HA]
[HA] [H0+]
K
or [A-]
we get
Substituting this value in eqn. (vi),
dS S] [H,O .ix)

derived rate expression for the catalysed

acid-base reaction is in equilibrium, the
Thus when the derived rate expression, we
order H3O". Since
in the species H,O appears inthe
reaction becomes first
is H,0t specifc.
say that the catalysis
reduces to
condition, when k2 >> k; [A-], cqn. (ví)
In the reverse

d(S=k,
dt
S] [HAJ
order in HA. Now as HA appears
brought about by the species
HA and
1s first acid HA.
The catalysis is general, sinceit occursfor any
now

expression, the catalysis IS Said tobe

as the second step,
in the derived rate tirststep and reaction
) as
the
possibility i.e., taking reaction step, the rate equation will be
For the second the rate determining
reaction (in) as
then taking the
dS=k,
dt
ISH]IA"
now will be
for (SH")
The rate equation
ds=k, IS] (HA] - k; [SH][A]-k2 [SH*] [A-1
dt
conditions,
steady-state
and for the
d[SH=0
dt
[SH*][A]=0
[SH°] [A]-k2
.e., k S][HA] - k; 473
 However, this proces
k [S][HA]
or
SH'A= k+k2
Substituting in eqn. (Fi), we get
d[S] kk2 [S][HA]
dt k +k2 CH
As the concentration [HA] appears in the derived rate expression, hence it is a case
of general acid
talysis.
In a base-catalysed reaction,the firststep is the transfer of a hydrogen atom from thesubstrate
base
In the presenceof a
i.e., SH +B S ++ BH*
and each makes its own
S then further reacts. The expressions for the rate be obtained in
t
can a manner exactly similar to
of the acid-catalysed reactions. (d[CH COO0