CHEMICAL KINETICS & CATALYSIS 251

Here, a =0.00005; x =0.0005 x (40/100) =0.0002

1 0.0002 26 661't I -1 -1
. . k = 50 x 0.0005 (0.0005 _ 0.0002) = . I mo e mID .

Ex. 20: A second order reaction where a = b is 20% completed in 500

seconds. How long wiU it take for the reaction to go to 60% completion?
Sol. For a second order reaction, where a = b,

..
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

(ii) Decomposition of acetaldehyde (CH 3CHO) with iodine (1 2) as cat-

alyst.

Vapour Vapour Gas Gas

(b) Examples of homogeneous catalysis in solutiop-pbase
Many reactions in solutions are catalysed by acids (J-r) and bases
(OH-).
(i) Decomposition of hydrogen peroxide (H20 2) in the presence of
iodide ion (r) as catalyst,

I
2H20 2 ~ 2H20 +02
(ii) Hydrolysis of cane sugar in aqueous solution in the presence of
mineral acid as catalyst.

Cane sugar Glucose Fructose

(iii) Hydrolysis of an ester in the presence of acid or alkali.
+ -
H/OH
CH3COOC 2Hs + H20 --~ CH3COOH + C2H50H
Ethyl acetate Acetic acid Ethanol
CHEMICAL KINETICS & CATALYSIS 253

[8] Heterogeneous Catalysis

When the catalyst is in a different phase than that of reactants, the
phenomenon is known as heterogeneous catalysis.
Some examples of heterogeneous catalysis with reactants in the gas,
liquid or the solid phase are given below.
(a) Heterogeneous catalysis with gaseous reactants (contact
catalysis)
(i) Oxidation of ammonia to nitric oxide (NO) in the presence of a
platinum gauze (a stage in the manufacture of nitric acid),
4NH3 + 502 + [Pt] ~ 4NO + 6H20 + [Pt]
Gas Gas Solid
(ii) Combination of sulphur dioxide (S02) and oxygen in the presence
of finely divided platinum or vanadium pentoxide, V 20 5, (contact process for
sulphuric acid).
2S02 + O2 + [Pt] ~ 2S03 + [Pt]
Gas Gas SolId

(iii) Hydrogenation reactions of unsaturated organic compounds are

catalysed by finely divided nickel.
H2C=CH2+ H2 + [Ni] ~ H3C-CH3 + [Ni]
Ethene (gas) Gas Solid Ethane
Vegetable oils are tri-esters of glycerol with higher unsaturated acid
(oleic acid). When hydrogen is passed through the vegetable oils in presence
of nickel, the carbon-carbon double bonds of the acid portions are hydrogen-
ated to yield solid fats (vanaspati ghee).
(iv) Combination of nitrogen and hydrogen to form ammonia in the
presence of finely divided iron, (Haber's process for ammonia).
N2 + 3H2 + [Fe] ~ 2NH3 + [Fe]
Gas Gas Solid
(b) Heterogeneous catalysis with liquid reactants
(i) The decomposition of aqueous solutions of hydrogen peroxide
(H20 2) is catalysed by manganese dioxide (Mn02) or platinum in colloidal
form.
2H20 2 + [Pt] ~ 2H20 + O2 + [Pt]
Liquid Solid
(ii) Benzene and ethanoyl chloride (CH3COCI) react in the presence
of anhydrous aluminium chloride to form phenyl methyl ketone
(CJI5 COCH3)
C614 + CH3COCI + [AICI3] ~ C6H5COCH3 + HCI + [AICI3]
Liquid Liquid Solid
(c) Heterogeneous catalysis with solid reactants
The decomposition of potassium chlorate (KCI0 3) is catalysed by man-
ganese dioxide (Mn02).
254 PHYSICAL CHEMISTRY-I

2KCI03 + [Mn02J ----) 2KCI + 302 + [Mn02J

Solid Solid
The above reaction is heterogeneous. though both reactants are in the
same phase (solid). because the solid forms a new phase.
[II] Classification of Catalysis
Catalytic reactions are of the following four types:
(a) Positive catalysis
(b) Negative catalysis
(c) Auto-catalysis
(d) Induced catalysis
(a) Positive Catalysis: When the catalyst used accelerates the speed
ofa chemical reaction, it is known as a positive catalyst and the phenomenon
is known as positive catalysis. For example. the rate of decomposition of
hydrogen peroxide increases in the presence of colloidal platinum 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

H' + Cl2 ~ HCl + Cl'

.NCI3 breaks the chain of reactions by absorbing the propagating species
(CI') and the reaction stops.
I
NCl3 + CI ~ "2N2 + 2Cl2

(c) Auto-Catalysis: When one of the products formed in the reac-

tion itself acts as a catalyst, the
substance is known as an auto-
catalyst and the phenomenon is
known as auto-catalysis.
tI ---------------------
Completion of reaction

In auto-catalysis the initial c

.Q
rate of the reaction rises as the
catalytic product is formed, in-
stead of decreasing steadily (See
i
Sigmoid curve
fig. 5). The curve plotted between
reaction rate and time shows a
maximum when the reaction is
complete.
Time---+
(i) For example, hydrolysis
of ethyl acetate by water is an Fig. S : Curve showing the rise
auto-catalytic reaction, since ace- of rate of reaction with time.
tic acid liberated in this reaction
acts as a catalyst.
CH3COOC2Hs + H20 ~ CH3COOH + C2HsOH
Auto-catalyst

(ii) The oxidation of oxalic acid by acidic KMn04 is catalysed by the

presence of Mn2+ ions formed in the solution. In the beginning, the colour of
KMn04 disappears slowly, but as Mn2+ is formed in the solution, the colour
discharges rapidly. So, Mn2+ ions acts as auto-catalyst.
256 PHYSICAL CHEMISTRY-I

2Mn04" + 5C20~- + 16W ~ 2Mn2+ + lOC0 2 + 8H20

Violet Colourless

(iii) The free arsenic produced by the decomposition of arsine (AsH3)

auto-catalyses the reaction.
2AsH3 ~ 2As + 3H2
Catalyst
(d) Induced Catalysis: When one reaction influences the speed of
other, which is not possible under ordinary conditions, the phenomenon is
known as induced catalysis.
For example, sodium sulphite solution is readily oxidised in air but
sodium arsenite solution is not oxidised by passing a current of air through
it. However, if air is passed through a mixture of sodium sulphite and sodium
arsenite solution, the oxidation of both take place. Here the oxidation of
sodium sulphite acts as a catalyst for the oxidation of sodium arsenite solution.
[III] Characteristics of Catalytic Reactions
Although there are different types of catalytic reactions, the following
features or characteristics are common to most of them. These features are
often referred to as the criteria of catalysis.
(1) A catalyst remains unchanged in mass and chemical composition
at the end of the reaction.
Qualitative and quantitative analysis show that a catalyst undergoes no
change in mass or chemical composition. However, it may undergo a physical
change. Thus, granular manganese dioxide (Mn02) used as a catalyst in the
thermal decomposition of potassium chlorate is left as a fine powder at the
end of the reaction.
(2) A small quantity of catalyst is generally needed to produce
almost unlimited reaction.
Sometimes, a trace of a metal catalyst is required to affect very large
amounts ~f reactants. For example, one ten-millionth of its mass of finely
divided platinum is, however, needed to catalyse the decomposition of hy-
drogen peroxide.
On the other hand, there are catalysts which need to be present in
relatively large amount to be effective. Thus, in Friedel-Crafes reaction,
Anhy. Alel3
C6H6 + C 2HsCi ) C6H5CzH5 + HCI
Anhydrous aluminium chloride functions as a catalyst effectively when
present to the extent of 30 percent of the mass of benzene.
(3) A catalyst cannot, in general, initiate a reaction.
In most cases, a catalyst speeds up a reaction already in progress and
does not initiate (or start) the reaction. But there are certain reactions where
the reactants do not combine for very long period (perhaps years). For exam-
ple, a mixture of hydrogen and oxygen, which remains unchanged almost
CHEMICAL KINETICS & CATALYSIS 257

indefinitely at room temperature, can be brought to reaction by the catalyst

platinum black in a few seconds.
Room temp
) No reaction
Ptblack
2H2 + O2 ) 2H20
It is thus now considered that the catalyst can initiate a reaction.
According to this view, the reacting molecules (in the absence of catalyst) do
not posses minimum kinetic energy for successful collisions. The molecules
rebound from collisions without reacting at all.
(4) A catalyst is more effective when finely divided.
_ In heterogeneous catalysis, the solid catalyst is more effective when in
a state of fine sub-division than when used in bulk. So, a lump of platinum
will have much less catalytic activity than colloidal or platinised asbestos.
Finely divided nickel is a better catalyst than lumps of solid nickel, because
former occupies greater surface area than the latter.
(5) A catalyst is specific in its action.
While a particular catalyst works for one reaction, it will not necessarily
work for another reaction. Different catalysts, moreover, can bring about
completely different reactions for the same substance. For example. formic
acid gives carbon dioxide and hydrogen when passed over hot copper.
eu
HCOOH ~ CO 2 + H 2 ,
However, with hot aluminium oxide, formic acid gives carbon monox-
ide and water.
Al,O.
HCOOH ~ CO + H2 0
(6) Change of temperature changes the rate of a catalytic reaction
as it would do for the same reaction without a catalyst.
We have already studied the effect of temperature change on reversible
reactions under Le-Chatelier's principle. Some catalysts are, however, phys-
ically altered by a rise in temperature and hence their catalytic activity may
be decreased. This is particularly true with colloidal solutions like that of
platinum, since a rise in temperature may cause their coagulation. In such a
case, the rate of reaction increases up to a certain point and then gradually
decreases. The rate of reaction is maximum at a particular temperature
which is known as the optimum temperature.
(7) A catalyst does not alter the final position of equilibrium, al-
though it decreases the time required to establish it
It means that in a reversible reaction the catalyst accelerates the forward
and the reverse reactions equally. Thus, the ratio of the rates of two opposing
reactions, i.e., the equilibrium constant, remains unchanged.
The effect of a catalyst on the time required for equilibrium to be
established for the reaction
258 PHYSICAL CHEMISTRY-I

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.

(ii) Molybdenum (Mo) or aluminium oxide (Ali-03) promotes the ac-

tivity of iron catalyst in the Haber's synthesis for the manufacture of ammonia.
Fe
N2 + 3H2 ~ 2NH3
+Mo

[II] Explanation of Promoter's Action

The theory of promotion of a catalyst is not clearly understood. It may
be due to:

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

(1) Increase of peaks and cracks. The presence of the promoter

increases the peaks and cracks on the catalyst surface. This increases the
concentration of the reactant molecules and hence the rate of reaction.
(2) Change of lattice spacing. The lattice spacing of the catalyst is
changed thus enhancing the spaces between the catalyst particles. The ad-
sorbed molecules of the reactant (say H 2) are further weakened and cleaved.
This makes the reaction go faster. The phenomenon of promotion is a common
feature of heterogeneous catalysis.
(8) Catalytic Poisons
Very often a heterogeneous catalyst is rendered ineffective by the pres-
ence of small amounts of impurities in the reactants.
A substance which destroys the activity of the catalyst to accelerate
a reQction, is called a catalytic poison and the process is called catalytic
poisoning.
260 PHYSICAL CHEMISTRY-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

(b) Explanation of Catalytic Poisoning

(1) The poison is adsorbed on the catalyst surface in preference to the
reactants: Even a monomolecular layer makes the surface unavailable for
further adsorption of the reactants. The poisoning of iron catalyst by H2S
comes in this class.
(2) The catalyst may combine chemically with the impurity: The
poisoning of iron catalyst by H2S comes in this class.
CHEMICAL KINETICS & CATALYSIS 261

o o o
II
c,
II
c
II
,
, , , , ,c,
, , ,, ,, , , ,,

~~;i;l Fig.9: Poisoning of platinum catalyst ~~~

by carbon monoxide.

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

(3) Fonnation of methyl benzene, C6H5CH3 by reaction between ben-

zene (C6H6) and methyl chloride (CH3CI) using anhydrous aluminium chlor-
ide. AICI 3, as catalyst (Friedel-Craft's reaction).
AICI)
C6H6 + CH3CI ~ C6H5CH3 + HCI
Mechanism:
CH3CI + AICI 3 ~ [CH3 [AICI4 f t
Intermediate
compound
C6~ + [CH3t [AICI 4f ~ C6HSCH3 + AICI 3 + HCI
(4) Thermal decomposition of potassium chlorate (KCI0 3) in the pres-
ence of manganese dioxide (Mn02)'
MnO,
2KCI03 ~ 2KCI + 302
Mechanism:
2KCI0 3 + 6MnOz ~ 6Mn03 + 2KCI
Intermediate
compound
6Mn03 ~ 6MnOz + 30 2
It may be noted that the actual isolation of intermediate compounds
which would prove their existence is very difficult. As already stated, by their
very nature they are upstable. In general, the intermediate compounds sug-
gested as being formed are usually possible rather than proved.
2. Adsorption Theory or Modem Theory of Heterogeneous Catalysis
Adsorption theory explains the mechanism of a reaction between two
gases catalysed by a solid (heterogeneous or contact catalysis). According to
this theory, the catalyst acts by adsorption of the reacting molecules on its
surface. Generally speaking, four steps can be put forward for heterogeneous
catalysis. For example, for the following reaction,
Catalyst
A(g) + B(g) ~ C(g) + D(g)
the steps are as follows :
Step 1. Adsorption of reactant molecules. The reactant molecules
A and B strike the catalyst surface. They are held up at the surface by weak
vander Waals forces (physical adsorption) or by partial chemical bonds (clle-
misorptioll).
Step 2. Formation of activated complex. The particles of the re-
actants adjacent to one another JOIn to form an intermediate complex
(A - B). The activated complex is unstable. It has only a fleeting existence.
Step 3. Decomposition of activated complex. 'The activated com-
plex breaks to form the products C and D. The separated particles of the
products are held to the catalyst surface by partial chemical bonds.
CHEMICAL KINETICS & CATALYSIS 263

Step 4. Desorption of products. The particles of the products are

desorbed or released from the surface. They are stable and can lead to an

r''N... . . ,. . . . ". . . . . . . . . . . . . '. .

independent existence.
;;;~; . . . . . . . . . ..
1 ''''~;;;''''''''''''''''''".S2,,''
Catalyst
2 """"""""~"''''''''''''''
Catalyst
."

:~; 3 """""''' """ """"''''' 4 """'''''''''''''''''''''''''''''''''''''''''',.

!!;,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)

The catalyst functions according to the following steps.

Step 1. Adsorption of hydrogen molecules. Hydrogen molecules
are adsorbed on the nickel surface due to the residual valence bonds of the
nickel atoms.
Step 2. H-H bonds are broken. The H-H bond is smaller (0.74
A) than Ni-Ni bond. Therefore, the H-H bond of the adsorbed hydrogen
molecule is stretched and weakened. The weakened bond breaks, separating
the hydrogen atoms. The separated hydrogen atoms are held to the nickel
surface by chemical bonds.
Step 3. Formation of the activated complex. The chemisorbed
hydrogen atoms then attach to ethene molecule by partial chemical bonds.
Therefore, unstable activated complex is formed.
Step 4. Decomposition of the activated complex and desorption of
ethane molecule. The unstable activated complex decomposes to form
ethane molecule. The freed catalyst surface is again available for further
action.
264 PHYSICAL CHEMISTRY-I

il'::"""'''''''''~'''''''''''''''''''''''''''''''''''''''''M""""""""'":'~

:1 H,,-- /H H,,-- 2;'--H I

I
Step 1 Step

j H/r:I"--H HH/C--C"--HH
)~ @--@ I
:'.! Step 3 Step 4 \

:::.:\::\U\ '~i~: .~~ ;.~~~~~ ~~.~~~ ~;~~~~~~~~~~. ~~. j/:::;:i{::::U/!:::::.

\u:=::nt} .......... ...~~~.e~e..o.~. ~i.~~.~~.~~r:r~c~'....................I)/\/(I(U::
The adsorption theory explains the catalytic activity as follows:
(1) Metals in a state of fine sub-division or colloidal form are rich in
free valence bonds and hence they are more efficient catalysts than
the metal in lumps.
(2) A promoter increases the valence bonds on the catalyst surface by
changing the crystal lattice and thereby increasing the active cen-
tres.
(3) Catalytic poisoning occurs because the so-called poison blocks the
free valence bonds on its surface by preferential adsorption or by
chemical combination.
[II] Industrial Applications of Catalysts
Tht" presence of a catalyst is very useful in many industrially important
reactions, which are either very slow or take place at a very high temperature.
:.', .......:.<::.. ,,-:.:.:::- :-:-:: ',':::.: '';'' ',' ... ,',::-::-:,:::::::::,:':':-:::':::':,:',.;::.:::,:,:;:;::::';::'';;';''':-:-':;:::';''::::''\:{
:;:>'
."" .
 CHEMICAL KINETICS & CATALYSIS 265

Hence. to decrease the cost of production it is essential to make use of a

suitable catalyst. A few important examples of heterogeneous catalytic reac-
tion of industrial applications are given as follows:

Reaction Catalyst and other favourable

conditions
1. Haber's process for the manufacture of Finely divided Fe + molybdenum (as
ammonia promoter) 200 atm. pressure and
N2 + 3H2 ~ 2NH3 temperature.400-450C.
2. The manufacture of chlorine by Deacon's Cupric chloride + excess of air at a
process temperature of 500C.
4HCI + 02 .~ 2H20 + 2Cl2
3. Ostwald's process for the manufacture of Platinised asbestos + excess of air (as
HN0 3 promoter) and temp. 300C.
4NH3 + 502 ~ 4NO + 6H20

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

6. Chamber process for the manufacture of Nitric oxide

H2S04
ZS02 + 02 + [NO] ~ 2S03 + [NO]
S03 + H20 ~ H2S04
7. Acetic acid from acetaldehyde
2CH3CHO + 02 ~ 2CH3COOH

Problem 4. What is biochemical or enzYme catalysis? Discuss the char-

acteristics and some examples of enzYme catalysis. Discuss the kinetics of
enZJme catalysis.
Or Explain enZJme catalysed reactions. (Meerut 2006, 2004)
Biochemical or Enzyme Catalysis
Enzymes are complex nitrogeneous organic compounds. They are pro-
duced in the living cells of plants and animals. On dissolving in water they
form the colloidal solution. hence they behave as very active catalysts in
certain biochemical reactions and are known as biochemical catalysts and
the phenomenon itself is known as biochemical catalysis.
[I] Characteristics of Enzyme Catalysts
(1) Enzymes form a colloidal solution in water and hence they are very
active catalysts.
1
266 PHYSICAL CHEMISTRY-I

(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

C2H50H + O2 Mycoderma aceti C CO H 0

) H3 0 + H2
(3) Conversion of starch into maltose
Diastase
2(C~1005)n + nH20 --~ nC 12H220 II
Starch Maltose

Maltase
C 12H220 U + H20 ---~) 2C6H l2 0 6
Maltose Glucose

(4) In the estimation of urea

Urease enzyme completely converts urea into ammonium carbonate.
/,NH2
/' Urease
O=C",- + 2H20 ~ (NH4hC0 3
"'- NH2
(5) In digestive tract
(a) In stomach, pepsin enzyme converts proteins into peptides, whereas
in intestines, pancreas trypsin converts proteins into amino acids by hydrol-
ysis. These amino acids are absorbed by blood and are used in the building
of tissues.
(b) The enzyme ptyalin present in human saliva converts starch into
glucose.
Ptyalin
) nC 6H l2 0 6
Gluco;e

J
CHEMICAL KINETICS & CATALYSIS 267

[III] Kinetics of Enzyme Catalysis or Michaelis-Menten

Equation
A reactant in an enzyme catalysed reaction is known as substrate.
According to the mechanism of enzyme catalysis, the enzyme combines with
the substrate to form a complex, as suggested by Henri (1903). He also
suggested that this complex remains in equilibrium with the enzyme and the
substrate. Later on in 1925, Briggs and Haldane showed that a steady state
treatment could be easily applied to the kinetics of enzymes. Some photo-
chemical reactions and some enzymic reactions are reactions of the zero order.
With S representing substrate, E the enzyme, ES an enzyme-substrate
complex and P the products, the mechanism of the enzyme catalysed reaction
is presumed to be adequately represented by
kj k
E+S~ ES~E+P
k2

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,

d[!S] = 0 = kl [E] [S] - k2 [ES] - k3 [ES]

... (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]

where [E]o refers to the total enzyme concentration. So,

[E] = [E]o - [ES]

On substituting the value of [E] in equation (1), we get

d ~S] = kl {[E]o - [ES]} [S] - (k'l + k3) [ES] =0 ... (2)

As the reaction proceeds, the intermediate complex formed in accor-

dance with the suggested mechanism, decomposes instantaneously according
to the same mechanism. On applying the steady state principle, we have

d [ES] = 0
dt
268 PHYSICAL CHEMISTRY-I

At the stationary state, equation (2) may be written as,

k\ {[E]o - [ES]} [S] = (k2 + k 3) [ES]
or k\ [E]o [S] = {(k2 + k3) + k\ [S]} [ES]

[ES] = k\ [E]o [S]

(k2 + k3) + kI [S]
[E]o [S]
=
k2 + k3 + [S]
kI
The rate of formation of the product, P, i.e., r is represented by the
equation,

r = d [P] =k3 [ES] ... (3)

dt
Substituting the value of [ES] in equation (3), we get
d [P] k3 [E]o [S]
r=--=
dt k2 + k3
k;-+[S]
. (k2 + k3)
The quantIty k is known as Michaelis constant and may be
denoted by Km. Therefok,
d [P] _ k3 [E]o [S]
... (4)
dt - Km + [S]
Equation (4) is known as Michaelis-Menten equation.
Further simplification of equation (4) can be made. If it is assumed that
all the enzyme has reacted with the substrate at high concentrations the
reaction will be going on at maximum rate. No free enzyme will remain so
that [E]o = [ES]. So, from equation (3), we get
rrnax = Vrnax = k3 [E]o
where "'max reters to maximum rate, using the notation of enzymology. So,
Michaelis-Menten equation can also be written as,
Vmax [S]
r=
Km + [S]
If r = Vma J2, i.e., if the rate of formation of product is equal to half of
the maximum rate at which the reaction proceeds at high concentration of
substrate, then
Km = [S]
Thus, Michaelis COli stant is equal to that concentration of substrate,
S at which the rate of formation of the product is half the maximum rate
obtained at a high cOllcentration of substrate.
CHEMICAL KINETICS & CATALYSIS 269

From equation (4), we can draw the following conclusions:

(i) If [S] is very small as compared to Km, the factor Km/[S] will be
very large as compared to unity and so the rate of formation of
P, i.e., d [P]Idt will be directly proportional to [8]. In other words,
the reaction will be of the first order with respect to S (Fig. 13).

. 1
Maxlmum rate, 2 Vmax

Vmax [SJIKm (first order)

Substrate concentration (S) _

(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

Mechanism of acid-base catalysis: It is accepted that acid-base

catalysis involves a reversible acid-base reaction between the substrate and
catalyst. This is in agreement with the protonic concept of acids and bases,
since acid catalysis depends on the tendency of the acid to lose a proton, while
base catalysis depends upon the tendency of the base to gain a proton. The
mechanism of reaction involving Wand OIr ion catalysis may be expressed
as follows. by taking the example of hydrolysis of esters.
(a) With W ions as catalyst
ORO R 0 R
II I n+
I I+ HO
'
I+ I
CH,-C-O + n ---> CH,-C-O -H -'---> CH,-C/\H

H H

(b) With OS- ions as catalyst

ORO R 0 R
II I I I I I
CH3-C-O + OIr ~ CH3-C-O+ ~ CH3-C-O+-H
I I
H-O H-O
~ CH3COOH + ROH
The rate of reaction is given by
dx
-d = kH+ C H+ Cester + kOH- C OH Cester + kH,o CH,o Cester
t - -
where kH+ and koH- are the catalytic coefficients of hydrogen and hydroxyl
ions.

MULTIPLE CHOICE QUESTIONS

1. The dimension of first order rate constant is :

(i) time-1 (ii) time
(iii) time x conc (iv)time-l x conc- l
2. The dimension of second order rate constant is :
(i) times x conc (ii) time- l x conc- l
(iii) time x conc-1 (iv) time-1 x conc-2
CHEMICAL KINETICS & CATALYSIS 271

3. The hydrolysis of methyl acetate by acid is of :

(i) Zero (ii) First order
(iii)
Second order (iv) Third order
4. The hydrolysis of ethyl acetate by NaOH is of :
(i) Zero (ii) First order
(iii)
Second order (iv) Third order
5. The reaction rate of a reaction 2A ~ 3B is given by :
(a) _ d [A] (b) _! d [A]
~ 2 ~
(c) + ~ d ~~] (d) + d ~]
6. For a reaction A + B ~ Products, the reaction rate is given by, :
dx = k[A] [Br
dt
The order of reaction with respect to A and B are :
(i) 1,0 (ii) 1, 1 (iii)O. 1 (iv) 2, 0
7. The half life period of a first order reaction is 20 min. The time required for the
concentration of the reactant to change from 0.4 M to O.I,M is :
(i) 20 min (ii) 40 min (iii) 60 min (iv) 80 min
8. The ratio of the time required for 75% of a first on':,,! rr,ction to complete to
that required for 50% of the reaction is :
(i) 4: 3 (ii) I : 2 (iii)2: I ' (iv)3: 2
9. The time required to decompose half of the reaction for a n'h order reaction is
also doubled. The order of reaction is :
(i) 0 (ii) 1 (iii) 2 (iv) 3
10. The minimum energy required for reactant molecules to enter into chemical
reaction is known as :
(i) Kinetic energy (ii) Potential energy
(iii) Activation energy (iv) Threshold energy
11. A first order reaction is 75% completed in 32 minutes. For 50% completion, it
will take: :
(i) 4 min (ii) 8 min
(iii) 16 min (iv) 32 min
12. The elementary step of the reaction 2Na + Cl 2 ~ 2NaCI is found to follow
third order reaction kinetics. The molecularity of the reaction is :
(i) 0 (ii) 1
(iii) 2 (iv) 3
13. In a reaction A ~ B, the reaction rate is doubled on increasing the concen-
trations of reactants four times. The order of reaction is :
(i) 0, (ii) 1 (iii) 2 (iv) 3
14. On plotting loglok against Iff, the slope of the straight line is given by::
. Ea " Ea
(1) R (n) -R
E
(iii) 2.30; R
272 PHYSICAL CHEMISTRY-I

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

28. A pho~chemical reaction is :

(i) Catalysed by light
(ii) Initiated by light
' .. (iii) Accompanied with emission of light
1;
1
(iv) Accompained with absorption of light
29. Platinised asbestors is used as catalyst in the manufacture of H2S04, It is an
~ example of :
(i) Homogeneous catalyst (ii) Auto-catalyst
(iii) Heterogeneous catalyst (iv) Induced catalyst
30. The enzyme ptyalin used for digestion of food is present in :
(i) Saliva (ii) Blood
(iii) Intestine (iv) Adrenal gland
31. A catalyst is a substance with :
(i) Increase the equilibrium concentration of the product
(ii) Change the equilibrium constant of the reaction
. (iii) Shortens th time to each equilibrium
(iv) Supplies energy of the reaction
32. An example of auto-catalytic reaction is :
(i) The decomposition of nitroglycerine
(ii) Thermal decomposition of KCl0 3 Mn02 mixture
(iii) Break down of 14C6
(iv) Hydrogenation of vegetable oil using nickel catalyst
33. The efficiency of an enzyme in catalysing a reaction is due to its capacity:
(i) To form a strong enzyme-substrate complex
(ii) To decrease the bond energies in the substrate molecule
(iii) To change the shape of the substrate molecule
(iv) To lower the activation energy of the reaction
34. A catalyst:
(i) Increases the energy change in a reaction
(ll) Increases the free energy change in a reaction
(iii) Neither decreases nor increases the free energy change in a reaction
(iv) Can increase or decrease the free energy change in a reaction but it depends
on the catalyst
3? Starch is converted into disaccharide in the presence of :
(i) Diastase (ii) Maltase
(iii) Lactase (iv)Zymase
36. Glucose or fructose is converted into C2H50H in the presence of :
(i) Invertase (ii) Maltase
(iii) Zymase (iv) Diastase
37. A ~talyst increases the rate of a chemical reaction by :
(i) Increasing the activation energy
(ii) Decreasing the activation energy
(iii) Reacting with reactants
(iv) Reacting with products
38. Which of the following statement is correct?
(i) Enzymes are in colloidal state (ii) Enzymes are catalysts
(iii) Enzymes catalyse any reaction (iv) Urease in an enzyme
274 PHYSICAL CHEMISTRY-I

39. A catalyst is used:

(i) To vaporise the compound (ii) To kill the enzyme
(iii) To alter the velocity of reaction (iv) To balance the reaction
40. Enzymes Il.re :
(i) Substances made by chemists to activate washing powder
(ii) Very active vegetable catalysts
(iii) Catalysts found in organisms
(iv) Synthetic catalysts
41. Which of the following catalysts is used for preparing toluene by reacting
benzene with CH 3Cl?
(i) Ni (ii) Anhydrous AlCl 3
(iii) Pd (iv) Pt
42. The rusting of iron is catalysed by which of the following?
(i) Fe (ii) O2
(iii) Zn (iv) H+
43. In which of the commerical process, a catalyst is not used?
(i) Haber's process (ii) Deacon's process
(iii) Solvay process (iv) Lead chamber process
44. Which of the following statements is correct for a catalyst?
(i) It supplies energy to the system (ii) It alters the rate of the reaction
(iii) It alters the equilibrium constant (iv) It is used up in the reaction
45. Organic catalysts differ from inorganic catalysts in :
(i) By acting at very high temperature (ii) By acting at low temperature
(iii) Being used up (iv) Being proteneous in nature
46. Which one of the following statements regarding catalyst is not true?
(i) A catalyst can initiate a reaction
(ii) A catalyst remains unchanged at the end of the reaction
(iii) A catalyst does not alter the equilibrium in a reversible reaction
(iv) Catalysts are sometimes very specific in terms of reactions
47. Which statement is incorrect for heterogeneous catalysis?
(i) Catalyst is absorbed on the surface
(ii) Active centres are found on the surface of catalyst
(iii) Catalyst increases the energy of activation
(iv) None of these
48. Which of the following is used as a contact catalyst?
(i) Boron Oi) Nickel
(iii) Germanium (iv) Uranium
49. Which one of the following statements is incorrect in the case of heterogeneous
catalyst?
(i) The catalyst lowers the energy of activation
(ii) The catalyst actually forms a compound with the reactant
(iii) The surface of the catalyst plays a very important role
(iv) There is no change in the energy of activation

Fill in the Blanks

1. A first order reaction is 15% complete in 20 min. It will take ............ min to be
60% complete.
2. The rate ofreaction is nearly doubled on increasing the temperature by .......... .
 CHEMICAL KINETICS & CATALYSIS 275

3. Order of reaction for the hydrolysis of ethyl acetate by HCI is ............ .

4. For a reaction A ~Products, the rate law is ~ = k [A]/2. The order of
reaction is ...... ... . t
5. The order of reaction of decomposition of H20 2 is ............... .
6. If the rate constant, k = .! . -x()' the order of reaction is ............. .
t a a-x
7. If the rate constant has tl-te UnIt sec-\ the order of reaction is ............. .
8. The equation k = Ae- EIRT is known as ................... equation.
9. In equation k = Ae- EIRT, A is known as ............... .
10. The hydrolysis of ethyl acette in acidic medium is ............. order reaction.
11. A substance which changes the rate of reaction is known as ............... .
12. The substance which retards the reaction rate is known as ................. cataryst.
13. The ................. of a catalyst increases when it is finely divided.
14. The substance which increases the efficiency of a catalyst is known as ............ .

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.

5. The half life period of a first order reaction is O.~93.

6. Order of reaction and molecularity are similar.
7. Order of reaction can even be 4 or more.
8. Most of the reactions are of first and second order.
hv
9. The reaction H2 + Cl 2 ~ 2HCI is of zero order.
10. The rate of zero order reaction depends on the concentration of the reactant.
11. A catalyst is a substance which can only increase the reaction rate.
12. When one of the products formed in the reaction itself acts as a catalyst, the
phenomenon is called auto-catalysis.
13. A catalyst is specific in action.
14. A catalyst can change the position of equilibrium.
276 PHYSICAL CHEMISTRY-I

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)

Fill in the Blanks

1. 112.8 min 2. W'C 3. (F) one 4. 112
5. one 6. two 7. one 8. Arrhenius
9. Frequency factor 10. First 11. Catalyst 12. negative
13. efficiency 14. promoter 15. Urease 16. homogeneous
17. autolhomogeneous 18. promoter 19. inhibitor 20. decreases

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