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KINGS
INTERNATIONAL

NEET
Class Xll
I

E
.

hemlstry
Chemical Kinetics +
- Surface Chemistry
 {l

o Chemical Kinetics
o Surface Chemlstry
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 change in concentration of a species LC
rate_=-
Average _^+^_ :
Chemical Kinetics: Chemical Kinetics is the branch of science change in time
-Lt
that deals with the rate of reaction, factors affecting the rate of
reaction and reaction - mechanism. On the basis of rate, chemical reactions are broadly divided into
Different reactions occur at difterent rate. In fact a chemical three categories:
reaction involves redistribution of bonds-breaking in the reactant
(a) Very fast or instantaneous reactions: Instantaneous
molecule(s) and making of bonds in the product molecule(s). The reactions are too fast. Generally these reactions involve ionic
species and known as ionic reactions. These reactions takes about
rate of a chemic al reaction actually depends upon the strength of
1trr4 or 10-16 seconds for completion. Its rate can be measured
the bond(s) and number ofbonds to be broken during the reaction.
It takes longer time for the reactant molecules to acquire higher by employing special methods. So, It is almost impossible to
amount of energy which they do by collision. Hence reactions determine the rates of these reactions.
involving strong bond - breaking occurs at relatively slower rate Examples. Detonation of explosives, acid-base
while those involving weak bond - breaking occur at relatively neutralization, precipitation of AgCl by NaCl and AgNOr.
faster rate. AgNO, + NaCl -+ AgCl + NaNO,
ppt.
Need of chemical kinetics:
(i) Along with the feasibility of a chemical reaction (which BaClr+ H2SO o)BaSOo + z]HCl
can be predicted by thermodynamics) and the extent to ppt.
will proceed (which can be determined
which a reaction HCI+NaOH+NaCl+H2O
from the study of chemical equilibrium), it is equally acid base salt
important to know the rate and the factors controlling the (b) Moderate reactions: These reactions are neither too fast nor
rate of a chemic al reaction for complete understanding of too slow. This type of reactions proceed with a measurable
a chemical reaction. Hence, there is a need of chemical rates at normal temperature. In this a Large number of bonds
kinetics in the study of chemical reactions. have to be broken in reactant molecules and a large number
(ii) In the study of chemical reaction, the rate of chemical of new bonds have to be formed in product molecules.
reaction needed to be known for the following two reasons,
Mostly these reactions are molecular in nature.
(a) In order to predict how quickly a reaction mixture Examples.
approaches equilibrium. (a) Combination ofH, and Cl, in presence of light, hydrolysis
(b) In order to gain an information regarding the of ethyl acetate catalysed by acid,
mechanism of chemical reaction or to discover the
(b) Decomposition of azomethane H, * Cl, + Z}JCI
steps involved in the chemical reaction.
(c) Decomposition of HrO, [Link]) 2H2O * O,
(iii) Chemical kinetics is the subject ofbiolo grcal,environmental
and economical importance and thus, there is a need of
(d) Decomposition of NrO, 2N2O5 + 2NrOo * O,
study of chemical kinetics. (e) Hydrolysis of ester
Rate of a reaction: It is defined as the change in concentration CH3COOC2H5 +NaOH + CH3COONa+ C2H5OH
of a designated species (reactant or product) per unit time. (0 Inversion of cane sugar in aqueous solution
Mathematically, CrrHrrO,, * HrO u* , C6Hr2Ou + CuH ,r.O u

Decrease in the concentration of a reactant (g) Reaction of NO with chlorine

Rate of reaction - Timeinterval NO + Clz+ NOCI,
Moderate reactions are studied in chemical kinetics.
_ lncrease in the concentration of a product (c) Very slow reactions: There are certain reactions which
Time interval are too slow. They may take months together to show any
measurable change at room temperafure.
Average rate: It is defined as the change in concentration of a Examples. Rusting of iron, weathering of rocks.
reactant or product divided by the time interval over which the Reaction between Hz and 02 to form HrO at ordinary
change occurs. temperafure in absence of catalyst.
 I

I
1.2 Chemistry

at room temperature
co +2H2 , cH3oH (i) Rate of formation of ammonia =
The chemical reactions can be slowed down or qpeeded up by dt
changing conditions under which they occur. d[Nr]
(ii) Rate of disappearance of nitrogen = -
For example. dt
CO +2Hz--+ CH3OH
dlnrl
The reaction can be speeded up by maintaining temperature (iii) Rate of disappearance of hydrogen = -
around 400oC, pressure about 300 atm afid using a catalyst dt
containrng ZnO and CrrOr.
Rate-+rd[Nu']=-d[N'] = - ldlHrl
2dt dt 3dt
RATE OF REACTION d[N,]_ 1 a[Nu,]
Thus, Rate = -
During the progress of reaction the concentration of reactants dt2dt
decreases while that (those) of product(s) increases. or rate of formation of ammonia = Twice the rate of
If the reaction occurs fast, the concentration (mole L-') of disappearance of nitrogen
reactant will decrease rapidly while that of product concentration dlNn,
1'e', t l=3[_4t1]l
will increase rapidly.
The rate of reaction is defined as the rate at which the
dt L dt J
The rate of reaction is not uniform. With the passage of timg-the
concentration of reactant decreases or alternatively, the rate at
concentration(s) of reactant(s) goes on decreasing and hence
which concentration of product increases.
according to Law of Mass Action, the rate of reaction goes on
The change in concentration of any of the substance (reactantl
decreasing. Infact, the rate of reaction decreases moment to
product) per unit time during the reaction is called the rate of
moment.
reaction. If dC be the change in concentration of any reactant
Average Rate of Reaction: Change in the concentration of
or any product during the time interval dt then the rate may be
reactants or products per unit time is called average reaction
given as
velocity. Average rate is denoted by R.

Total change in concentration (-) Change in the concentration of reactants

of reactant or product Average velocity =
Rate of reaction Time
- Change in time (in second) (+) Change in the concentration of products
Time
v -+!e
dt
Forareaction A+B
Where dC =change in concentration in a small interv al dt
-[e], )=
[+] sign is used when we refer to product concentration. ^\t
R - [[a], - Lt
[-] sign is used when we refer to reactant concentration. h-t, ) ^[A]
Where [A], = Concentration of reactantAattime t,,
[A], = Concentration of reactant A at time tr.
Product

Reactant
Product
Time
(a) For an reversible reaction

Reactant
€
uint of concentration
Product Unit of average velocity =
uint of time
grammole
Time Litre x Second

- gr&rrl mole litre-r second-r

(b) For an irreversible reaction

Figure: The change in the concentrations of the reactants and Instantaneous Rate of Reaction: The rate of reaction
products. determined at specified concentration or specified time is called
Example. N, + 3H2 -+ 2NH, instantaneous rate.
 Chemical Kinetics 1.3
The instantaneous rate of the reaction can be determined
by measutirrg concentration of reactant or product after fixed
intervals of time and plotting concentration versus time.
1. A gaseous reaction:2A(g) + B(g) -+ 2C(e),
Show adecrease inpressure from lz}mmto I 00mm in I0 min.
The rate of appearance of C is
(1) zmm/min (2) nurn/min
(3) l0 mm/min (4) 12 mm/min

B
2. The term -+dt in the rate expression refers to the

(l) concentration of the reactants

(2) increase in concentration of the reactants
Time (3) instantaneous rate of the reaction
(4) average rate of the reaction
The instantaneous rate at any time is determined by the slope 3. Which of the following expression can be used to describe
of the tangent at a point on the time-concentration curye the instantaneous rate of the reaction?
corresponding to the specified time. 2A+B+ArB
The slope of the tangent at apoint is the limiting value of +.
Lt
.1\ t alel
(1)
\ // -: '^\
\-,
(2)
dlAl
Lc dc 2 dt dt
tt-+o fil dt
In terms of the concentration of reactant, the rate of the
(3)
, dt
1 dl,4rBl
s) -;##
reaction - -dc 4. Which of the following will react at the highest rate?
dt
(l) I mol ofA and I mol of B in a I L vessel
The sign indicates that the concentration of reactant (2) 2 mol ofA and 2 mol of B in a 2L vessel
decreases with time.
(3) 3 mol of A and 3 mol of B in a 3 vessel
In terms of the concentration of product, the rate of the (4) All would react at the same rate

reaction - *d'
dt ITINNI RATE
The + sigR indicates that the concentration ofproduct increases
with time. In the reaction if t
the concentration of
at a time
The slope of the tangent at t - 0 in the plot of concentration vs
time gives the initial rate.
product is x and at time t + dt, the concentration becomes x * dx
then the reaction rate
& Rate of reaction - tanl =+
- dt
dt

For example the rate of reaction: N, * 3HrT- 2NH3 in

terms of the concentrations of N, H, and NH3 can be expressed
AS

I a[NH,]
dt'3 dt 2 dt
t:0 Time
G

Rate of reaction in the form of stoichiometry of a chemical

reaction:
What should be (a) the rate of disappearance of B and (b) the
Let us consider a reaction:
rate of formation of C, if the rate of disappearance of A for the
reaction A + B -> 2C is l0-2 mole/litre/second at a particular mrA * mzB + ------ nrP + nrQ * nrR+ ---------
temperature?

Solution:
Rate of reaction --
I d I B I d P td
(a) Rate of disappearan ce of A= Rate of disappearance of dt dt dt dt
^B

= 10'2 mole/litre/second
Unit of Reaction Rate: Unit of reaction rate = mol L-t time-r i.e.,
(b) Rate of disappearan ce of A= 1 x Rate of formation of C (mol L-r s-r or mol L-r min-t or mol L-' h-')
2 Special Note: For a chemical reaction A + B + P+Q
Rate of formation of C = 2 x Rate of disappearance of A
= 2 x l0-2 mole/litre/second Rate of disappearance of A - -/Adt
1,4 Chemistry

dlBl Solution:
Rate of disappearance of B - - Given,
dt
Order of reaction = n = |
dlPl For 30% completion, t = l0 min
Rate of formation of P =
dt Rate of constant = K=?
dlo) If Elo = 100, lA),= 100 - 30 - 70
Rate of formation of Q - dt
K-rylos'oW
2.303.
to8ro
100
For the reaction: 2N2O5 + 4NO2 + Oz. If the concentration of 10 n
NO, increases from 1.6 x l0-2 M in 4 s. Calculate the following
(i) rate of formation of NO, = 0.2303 log,, 1.429
(ii) rate of formation of O, - 0.2303 x 0.155
(iii) rate of disappearance of NrO,
= 0.357 min-r
(iv) rute of reaction
.'. Rate constant K = 0.357 min-l
Solution:
(i) rate of formation of NOr:
RATE LAW
a[Nor] _ 1.6x10-2
= 4xro_3 Rate law is defined as an experimentally determined equation
dt4 that expresses the rate of a chemical reaction in terms of molar
(ii) rate of formation of Or: concentrations of the reactants.
According to the law of mass action, the rate of a chemical
dlor)_ I [No, ] I reaction is directly proportional to active masses of reactants.
= x 4xro-3 = ro-3
dt44 A+B+products
(iii) rate ofdisappeamnce of\Or: Rate of reaction * lAl [B] = Kl,AltBl
I [xor]=_ 1 d[Nros]_ -d[N2o5 where K is proportionality constant and is called velocity
constant or rate constant or specific reaction rate.
4 dt 2dtdt
For general reaction: mrA * mrB * mtC ----+ products
1 a[Nor]_ 1
- 2dt2 x4xro-3 :2xro{
The rate of reaction - Kllf^'lal^'lCl^
(iv) ruteofreaction = - I d[N'?os ] = 1 x2xl0-3 = 10-3 r = Klt)^'lnl*'lcl*'
2dt2 Unit of rate constant:
I d[Nor] _ 1 dlor)=
or x4xr0{ = r0-3 or 10-3 concentration
- !( [concentratio']''
+m2+m3
4dt4dt time

Rate constant: Is defined as the rate of the reaction when the Note:
molar concentration of each reactant is taken as unity.
Consider a general reaction: (m, * ffir* mr) = r(order of reaction) t

aA + bB + Products +m2+m3
mole ,.(
Rate c fA)'ln\r ^ole)''
lit*r*""d-1([1i".]
.'. Rate - [Link],
where k, the proportionality constan t = rate constant or specifi c
reaction rate constant.
t,
It Et
I mole 1(t-")
I

I litre /
I dl!
Hence, rate - adt - klA)* lu)'
-

The rate constant is constant for a particular reaction at aparticular

It lA) = [B] = I mole/litre, then Rate = ft
temperature and does not depend upon the concentration of the
reactants.
o Rate of a chemical reaction is directly proportional to the
product of the concentration of reactants.
A first order takes 10 minutes to complete 30Yo. Calculate the o The rate law represents the experimentally observed rate of
rate constant for the reaction. reaction which depends upon the slowest step of the reaction.
 Chemical Kinetics 1.5
o Rate law cannot be deduce from the equation for a given FECTORS AFFEcTING THE ReTe oF REAcTIoN
reaction. It can be find by experiments only.
. (i) Concentration: Law of mass action enunciates thatgreater
The rate law may not bear a simple relationship for the
is the conc. of the reactants, the more rapidly the reaction
stoichiometric equation.
proceeds.
o It may not depend upon the concentration of species, which (ii) Pressure (Gaseous reaction): On increasing the pressure,
do not appear in the equation for the over all reaction. volume decreases and conc. increases and hence the rate.
The rate of reaction at any time t is determined in the (iii) Temperature: It is generally observed that, the rise in
following way, temperature increases the reaction rate. It has been found
(i) of any of the reactants or products which
Concentration that the rate is either doubled or tripled for every 10"C rise
ever may be convenient is determined at various time in temperature. Temp. coefficient of reaction rate
intervals.
k' +lo
(ii) Then concentration vs time curve is drawn. >> 2or 3
kr
(iii) A tangent is drawn at the point p of the curve which
colresponds to the time t at which rate is to be determined. Where K, * 10 and k, are the rate constants at two temp.
differing by 10oC.
(iv) The slope of the tangent gives the rate of reaction at the
(iv) Nature of the reactants: The rate depends upon specific
required time as shown below.
bonds involved and hence on the nature of reactants.
(v) Surface area of the reactants: In heterogeneous reactions,
t R, = tanl= -tan(180 - 0) = more powered is the form of reactants, more is the velocity.
CR # [as more active centres are provided]
A (vi) Catalyst: Affects the rate immensely.

For the reaction 2A + B + Products, find the rate law from the
following data.
t Time + Experiment lAllM [B]/M ratelMS-t
I 0.3 0.05 0. 15

II 0.6 0.05 0.30

t - - m 0.6 0.20 1.20
Bt
C What is the rate constant and order of the reaction?

Solution:
A
r,:tan0 --# Given, 2A+B+products
Rates R, = 0.15 ms-r Rr= 0.3 ms-l
0 [A]r= 0.3 M lAfr= 0.6 M
B
o t time + lBlr= 0.5 M lB)r= 0.05 M
Let order of reaction is x for A and y for B, then by rate law,

(C^ and C p denotes concentration of reactant and product q = KlAl: tBli and Rz = KlAl:ln\l,
respectively)
R2 rltlilali
uint of concentration
a

aa

Unit of rate - uint of time

= concentration time-l Rr KlAl: trli
i.e., mole L-l S-t
Rr= .[ffii:)'
[i#)
aa

Applications of rate law: &

(i) By knowing the rate law and the rate constant, the rate of 0.3 ( \'
o.o ( o.s )'
reaction for any given composition of the reaction mixture 0. 15 [*] '[r*J
Fl
can be estimated. ,L-L-lx

(ii) It canbe used to estimate the concentration of the reactants

and the products at any instant during the course of the
.'. E
Thus reaction is 1" order for A
reaction. Similarly:
(iii) By knowing the rate law, the mechanism of a complex R, = 0'3 MS-l Rr= 1.2 MS-r
reactions can be predicted. lAlr= o'6 M lA)r= o'6 M
[B], = o'05 M lB)r= o'2 M
1.6 Chemistry

lAl'= 0.244la lAlr= o'244 M

=( W)' " f I4)'
R,, _ x lelila)i lB)r- 0.16 M lBlr= 0.32 M
4 KlAl:lali [ [,r], .l [. [r], J xtejilnli
r.2 /o.o\' ( o.z Y
R,
=
& KIA):lBli =(tr)"I la1,
lrI, )
0.3 [0.6/ (0.05/
4-4v
o.t2 ( 0.244\'I xl
( 0.32
016
-[ _l

0.244 ) \. 0.16 )'

! =l
a'= af
Thus reaction is l't order for ^8.
The overall order of reaction ! =l
n=nA+nB-l+l-2 Hence reaction is l't order for B
Rate=R- I<TA)lB)
R
Then overall order ofreaction = n = frn* ftB= 2 + I=3
... K- By rate law
lellrl R- KIA)rlBl
_&
lA'ltr, l
... K_ f _ 0.24MS-t

K _o.lsMs-t _
0.15
=10
lel' [r] (0.+ao)'t t"(0.16)M
0.3 x 0.05 0.015
K - 6.3 = M-rS-l Rate constant
K- M-t St
10
Rat_e constant K = l0 M-t S-t

ORDER OF REACTION
It is defined as the sum of powers of concentration (or pressure)
terms involved in rate law expression. i.e., number of molecules
Consider the reaction 2A(g + 2B(g) + 2C + D. From the whose concentration determined the rate of the reaction is called
following data, Calculate the order and rate constant of the order of the reaction.
reaction. The order of L chemical reaction with respect to
Experiment lAlolM [B]o/M rolIVIS-r each reactant is defined as the exponents to which the
I 0.488 0.160 0.24 concentration terms of that rcactant, in the rate law, is raised.
The overall order of reaction is defined as the sum of the
[ 0.244 0.160 0.06
exponents to which the concentration terms in rate law are raised.
m 0.244 0.320 0.12 Explanation:
Write the rate law of reaction. Consider the reaction,
aA+bB+cC+dD
Solution: Rate - k lA)'lBl,
Given, 2A + 28 + 2C + n where, fr is the rate constant for the reaction, x is the order of
Rates: R, = 0.24 MS-t Rr= 0.06 MS-t the reaction with respect to reactant A and-y is the order of the
reaction with respect to reactant B.
lAlr= 0.488 M lAlr= 0.244M
(, + y) is called overall order of reaction (n).
[B], - 0.16 M lBlr= 0.16 Exponents x andy mayor may not be equal to the stoichiometric
Let order of reaction is x for A and y for ^8, then rate law coefficients 'A' and'b' of the reactants and are to be determined
& = KlAlilBl{ and Rz: KlAl;lB){ from experiment, i.e., they are experimental values.
Order is a purely experimental quantity. It may be a whole
& _ xlelila)i
... R2 number or zero or even a fraction.
KIA):lnli Reactions are classified according to the order of reaction.
(a) A reaction is said to be of first order when the one
=[#)"[ffiI concentration term determine the rate of reaction:
Example.
(i) 2N2Os + 4NO r* O,
0.24 ( O.+sg \' ( 0.t60 \' r
0.06 \[Link]+ )
I .-,1 |
-K [NrOr]
[ o.r 60 ) (ii) In the decomposition of HrO,
--l
4=2' -
2H2O2(g) -+ 2H2O(l) + O2(g)
x -2 The rate law for the reaction is found to be,
Hence reaction is 2'd order for A Rate = k [H,O.,]
If R, = 0.06 MS-r Rr= 0.12 MS-t
 Chemica[ Kinetics 1.7
The reaction is first order in HrO , and the overall order is No2(s) + CO(e) -+ No(e) + cor(s)
one because the rate of the reaction is proportional to the first The rate law for the reaction is experimentally found to be
power of HrO, concentration. rate- k [NO2]2 [CO]o
(b) A reaction is said to be of second order when two _k
[No2]2
concentration terms determine the rate of reaction. The reaction is second order in O, and zero order in CO,
Example. hence overall order - 2 * 0 = 2.
(i) Consider the reaction, (i) The order of a reaction is always defined in terms of the
H2(s) + Ir(s) -+ 2HI(g) concentrations of the reactants and not of the products.
for which the experimentally determined rate law is rate (ii) The order of a reaction may be zero, first, second, third
_k
[Hr] [rr]. or fractional value.
The reaction is first order in H, and first order in lz. (iii) Reactions of order higher than three are unknown.
Hence, the overall order of the reaction is The reason is that the collisions in which three or
1+ 1 -2. more molecules all come together atthe same time are
(ii) 2N2o 2N' * O' very unlikely. Such reactions proceed in two or more
r=K NrO], elementary steps.
- CH3COO CrH, +NaOH-+ CH3COONa+ C2H5OH Rate controlling step: The slowest step of the complex reaction
is called the rate controlling step.
(c) A,.;;fr !:Ti3lffi#,Hl"Il., ir three concentration Example. We have a reaction
terms determine its rate.
Example.
2NO2*Fr+2NOrF
(i) The rute law for the reaction, The mechanism of this reaction is as follows
2NO(g; + Or(g) -+ ZNOr(S) NO, * F, -----+ NO2F + F (slow)
is experimentally found to be rate = ft [NO]' [Or] NO, + F -+ NO2F (fast)
The reaction is second order in NO, first order in O,u and
overallorderofthereactionis 2+1 =3 . 2NO2 * F, -+ 2NO2F (overall reaction)
(ii) ZFeClr+ SnCl z1 2FeClr+ SnClo
r=K[FeClrlz [SnCloJ
The order of following reaction is fraction:
(A) ur(s) + Brr(B) -+ 2HBr(g)
Give the following data for the reaction: A + B -? Product.
r - K[H,][nr,1; Experiment No. lAl lBl rate
1124
+1rder= ::,l=} 2224
(B) CHCL + C!+ CC14 + HCI 32416
Which one is the rate law equation?
r =/([cHCl,][cr, 1i
Solution:
3
+ordof =t+1- We know that ratelaw is given by: r - K lAl' lBl, ..(l)
(d) An example of O:"rilrosition of gaseous acetaldehyde put the values of experiment No. 1 and 2 in equatiotr 1, we gets
shows that the reaction may also have a fractional order. 4 l2l,
- K Ul' ..(2)

CH3CHo(e) CHo(e) + Co(e) and 4-Kl2l'l2l, ...(3)

Acetaldehyde Methane Now, Equation(2) is divided by (3), we get
$*f*0.
(1\'
The rute of the reaction is experimentally found to be i'e''x=o
proportional to the concentration of acetaldehyde raised to ':[;.,l
the power 312. Hence, the rate law is, rate - k [CH3CHO)''', Now, put the values of experiment no. 2 and 3 in equation (1),
which indicates that the order of the reaction is 312. we get
(e) Zero order reaction is the reaction whose rate is independent 4 - (2Y Qy ..(4)
ofthe reactant concentration and remains constant throughout t6 = (2). (4Y ...(s)
the course of the reaction. Equation (4) is divided by (5)
Differential rate law for the zero order reaction is given I (r)' i'e''!=2
;=l, ;l
by:

Rate=- kVl'
# -t1 So, order of reaction with respect to x is 0 and with respect to yis 2
and the rate of reaction is
The order of a reaction can also be zero. For example,
consider the reaction, r - K lAlo lB)' - K lB)' i.e., order of reaction = 2
1.8 Chemistry

It is always a whole number and cannot be negative and

fraction.

1. The dimensions of rate constant of a second order reaction

Reactions are classified in terms of molecularity as
unimolecular, bimolecular, trimolecular depending upon the
involves:
number of molecules involved in the reaction.
(1) time and concentration
The molecularity of a reaction cannot always be predicted
(2) neither time nor concentration
from the stoichiometric reaction. It is obtained by compounding
(3) time only
various elementary steps.
(4) concentration only
Example. zHzoz 2H2O * O,
2. The rate constant of a reaction has same units as the rate of
First step HrO, HrO + O (slow step)
reaction. The reaction is of
Secondstep O+O#Oz (Faststep)
( 1) zero order (2) first order
The rate determining step indicates that it involves only one
(3) second order (4) none of these
molecule. So the molecularity is 1.
3. The tate constant of nth order has units
(a) Unimolecular reaction:
(1) litrer- molr-'sec-r (2) molr-' litrer-' sec
PCls-PC13 +Cl,
(3) mol'-" lrtren' sec-' (4) molr-' litre^l sec-r
4. On which of the following factors, the rate constant does not NrOo.
-2NO2
depend?
(1) Temperature (2) Concentration HrOr+HrO*1O,
'2
(3) Presence of catalyst (4) Nature of reactants ' (b) Bimolecular reaction:
Saponification of ethyl acetate

MOLECULARITY CH3COOC2H' + NaOH-CH3COONa + CTHTOH

Two molecules are involved in the reaction hence the

The molecularity of an elementary reaction is defined as the
molecularity of the reaction is 2.
minimum number of molecules, atoms or ions of the reactants(s)
required for the reaction to occur and is equal to the sum of
2HI Hz+ lz (molecularity is 2)
the stoichiometric coefficient of the reactants in the chemical (c) Trimolecular reaction:
equation of the reaction. Thus, the molecularity of some 2FeC1, + SnCl , 2FeCLr+ SnClo
The molecularity of the reaction is 3 since three molecules
elementary reactions are as mentioned below. -
are involved in the reaction while the order of reaction is 2.
Elementary reaction Molecularity
2NO * O, ---) 2NO2
PCls i- PCl3 + Cl, I molecularity + 3
HrO z+ 2H* + 2l- lr* zHzO .
Hr*Ir-=zHI l+l-2 molecularity + 3 -)

Order of reaction Molecularity of reaction

(1) It is the sum of the powers of concentration in terms of the (l) It is the number of chemical species taking part in the rate
reactants in the rate equation. determining step.

(2) It is empirical and must be determined experimentally. (2) It is concerned with the reaction mechanism and is a theoretical
concept obtained from the balanced single step reaction.
(3) It is a whole numb er, zero or fraction (3) Molecularity is a whole number and never zero
(4) It is same for the whole reaction no matter the reaction is (4) It represents a multistep reaction and is expressed for each step.
simple or complex.
(5) It refers to a reactionas a whole irrespective number of (5) It depends upon the rate determining step in the reaction.
involved steps in the reaction.

[Link] Examples:

REACTION (a) CH3COOC2H5 +HrO H* ,CH3COOH+CrHrOH

Such reactions whose order is one but the molecularity is two, are
(b) CrrHrro,, * HrO H* , C6Hr2ou + CuH ,rOu
called pseudo-unimolecular reaction. (c) C6HsNrCl+ HrO C6H'OH+Nr*HCl
(d) R-X+HrO + - ROH+HX
 Chemical Kinetics 1.9

I NIECRATED RATE EQUATIONS (vi) Graphical representation:

(A) Zeno OnoER REAcnoN Zero Order
Reaction in which the concentration of reactant do not change Rate
with time are said to be zerc order reaction.
(i) Reaction:, A Product
Example. Concentration
(a) H, (s) + Cl, @)12HCl(g)
(b) 2NH3 @)1N' (g) + 3H' (s)
(c) Reaction between Acetone and Bromine. Conc.
(d) Dissociation of HI on gold surface.
(e) Decomposition of gas on surface of catalyst. t
(ii) Differential rate equationz A Product

#=koltl'or *=kolAlo
Where x is molar concentration of product attime't'. t
r,,
(iii) Calculation of rate constant: Let us take the reaction
A Product
dlAl
- klA)o = k
dt
(B) Frnsr OnoeR REAcrroN
-'! ale)- !r at
A first order reaction is one whose rate varies as l't power of the
0
concentration of the reactant i.e. the rate increases as number of
- lA),- kt + C
lAl,=Vlronl-0 At
Slope --K times the concentration of reactant is increased.
c _ _lAlo (i) Reaction: A -+ Product.
Put the value of C Example.
-lA),- kt - lAlo
t (a) 2N2Os 4NO2 * O,
-lAl,= lAlo- kt (b) NH4NO2 Nr* 2H2O
Special Note: For zero order reaction the rate of reaction is
(c) CH3COOC2H5 CH3COOH + CTHTOH
equal to rate constant
Time for completion of reaction (d) 2cl2o7 2cl2+ 70'
[A],= lATo- kt (ii) Differential rate equation:
For complete lA),- 0

,__lt)o
IL- #-t,lt)*#-k@-*)
t (iii) Calculation of Rate Constant:
A Product Let us take the reaction.
t=0 a 0 A ----+ Product
After time / a-x x t=0 a 0

dx - ,
v-k(o-r)'-k r,o
After time / (o - x) x
' Here, 'a'be the concentration of A at the start and (a -x) is
dt
x=kt the concentration of,4 after time taken t. i.e., x part of A has
x --Amount of reactants that will change in product. been changed in the product. So, the rate of reaction after
(iv) Unit of rate constant: time / is equal to.
k = mol L-t s-r = unit of rate of reaction. dx (a-x\ -/ .,
, \ o, 4dx:k(a-x\or, dx , ,
fu a

(v) Half-life period: The half life period for a zero order -oc
dt \ '/ dt \ '/ ("-*) -kdt
reaction is directly proportional to the initial concentration
of the reactants. Where k is a specific reaction rate for the first order
o
reaction, 'a' is initial concentration of A and x moles/litre
of A has been decomposed up to the time /.
V_

2
Upon integration of above equation
x-kt=9-kt *" :ltat
'tA
2 |adxr
J ("-x) r
ttrz:i=tr,, x A
1.10 Chemistry

or -ln(a-r)=kt+C (viii) Graphical representation:

x=0on t=0
C--Lna
Put the value of 'C'
-ln (a -x) = kt -ln a
Rate
/ " \
orkt-h! a I
logHl
lo-*)
Concentration t
or k -2'3o3t"r[a)
t \a-x)
a
kt -ln Srope--7sii
" t
rr-.,,'/ t
r,,
-kt-ln\
a-x initial cone /
ros(*)
_A -h
a
c,_ e-ld
co Slope:
log (a - *
C,= Co ru' (Willhalpi equation)
Here Cr+ Concentration on time t=0, C,) Concqntration t
on time /
(iv) Unit of rate constant:
k = second-l A few examples of l't order and their formula for rate
a ln(o-x :_x constants are as under:
kt-ln a-x (a) CH3COOC2H5 +HrO CH3COOH+ C6HpOu
kt-lna-ln (a-x) -J
t 2.3031on ,_ _ ro
(v) Half-tife period: k_ or.
The half life of a reaction is defined as the time needed t -vt
for the reactant concentration to fall to one half of its initial where V, Vr and V." are the volumes of NaOH
value. solution used for titrating a definite volume of the
Putting a - x - al2 and t = tr,rin the integrated rate equation reaction mixture of zero time t and after time infinite
we get respectively.
l. ( a \ ln2
ttrz=
k^lrr)or tuz= ,, tr,ro - 0'693 (b) HrO H* ,C6H12O' + CuH
k CrrHrrO,, * ,rOu)
From the above equation (2) for a first order reaction, 2'303 -'*
half-life period is constant, i.e., it is independent of initial k - t
lor'o
o
concentration of the reacting species. The half life of a first
n-r*
order equation is readily calculated from the rate constant where ro, r,and r* are the polarimetric readings at zero
and vice versa. time, after time t and after time infinitely respectively.
(vi) Time for 314 of the reaction (tr,) (c) 2N2O5 ---) 4NO2 * Oz and [Link]*NO z 1 zHzO* N,

Putting a- x= t = t,o in the integrated rate . los- b-

2.303
iand
4 t-_
equation we get t V* -V,
1'386
tyq=rylog4- where Y,andY*arethe volume ofO, orN, gas collected
kk after time t and after time infinite respectively.
tyo
tr,,
2 (d) HrOr--)HrO*1O,
2L

(vii) Interval formula: 2.303 a-

o- k -'-!ltvt log&-
where x, and xrbe the amounts decomposed up to the time
t, and /, respectively. where Vo and V', are the volumes of KMnOo solution
Special Note: Time required for the completion of definite used for titrating a definite volume of the reaction
fraction of the first order reaction is independent of the mixture in the beginning (at t = 0) and at time t
initial concentration of the reactant. respectively.
 Chemical Kinetics 1.11
Kr= initial rate constant = 3 .7 x 10-5 s-r
T, = initial temperature 273 + 25 - 298 K
Tr= initial temperature 273 + 25 = 298 K
A first order reaction gets 90% completed in 40 minute. Find out
K, = final rate constan t = ?
the half-life period of the reaction.

Solution: los,o*,=ffi: t04x 103 (lo: -298)

2.303x 8.3 l4x298x 300
Suppose that the initial concentration of reactant (a) = 100
t = 40 minute s 90o/o of the reaction get completed in 40 minutes. l04x 103 x 5
= 0.3
Therefore, 2.303 x 8.1314x298x 300
x=90 K2
2.303 -a Kl - antilog 0.3 :1.995 = )
Kl =- t log
a-x
-
Kr=2xKr=23.7 x l0r -7.4x lOa s-r
2.303 -
l^r-
100 Rate constant at 30'C - 7 .4 x 104 s-t
40 " 100-90
K,=ryloglo
'40 -

2.303 The activation energy for a certain reaction is 334.4 kJ mol-r.

= = 5.757 xlQ-2minutes-r How many times larger is the rate constant at 610 K then the rate
40
-xl constant at 600 K?
t,,,= o'6?3 ==lo.3minutes Solution:
x
5.7 57 10-'
Given,
Eo= 334.4 kJ mol-r - 334.4 x 103 kJ mol-t
Tr= 610 k, T, = 600 k
Kzo
Prove with the help of the following datathat hydrolysis of HrO, I

is a first order reaction. Initial concentration in the reaction 25 .0.

Kl
K2 Ea T, -7,
Solution: 1og,
Kt 2.303RT]T,
Time, / (in minutes) 10 20 30
334.4x 103 (0tO - 600)
V 20.0 15.7 12.5
2.303 x 8.3 14x600 x 610
2.303
For a first order reaction, Kl bgL; Hera,o=25 334.4x 103 x 10
t o-x :
2.303x8.314x600x610
Kratt=r0minutes
25 2.303 0.0969 = 2.23x 102
=
TFa* -20= l0 = 0.477 |
K, at t = 20 minutes -x += antil og0.4771-3
Kr(
25
-2303lon x0.2020 = 2.32x10-2
20 "15.7 .-2'303
20
Rate constant increases three times

Kratt=3hminute, = 4f rrr| =#x 0.30 10 = 2.3rx 102

Ir
Constant value of K, shows that hydrolysis of HrO, in aqueous
The rate constant of a first order reaction25"C is 0.24 s-1. If the
medium is a first order reaction.
energy of activation of the reaction is 88 kJ mol-r ,'dt what
temperature would this reaction have rate constant of 4 x 10-2 s-1?

Solution:
The energy of activation for a first order reaction is 104 kJ Given,
mol-l. The rate constantat25"C is 3.7 x 10-5 s-r. What is the rate Kr= 0.24 Kz- 4 x l0-2 s-1,
sa;
constant at 30"C?
Tr= 273 + 25 = 298 K
Solution: E o= 88 kJ mol-r = 88000 J mol-r , Tr- ?
Given,
,^_ K2 E,(Tr-rr)
R - 8.314 lOg, n
"'u -:K, z.3o3RxTrxT,
Eo= 104 kJ mol-r . 104 x 103 J mol-l
l.l2 Chemistry

T, -7, _ 2.303R *, 2. On addition ofAgNO, to NaCl. White ppt occurs

"'u^ (1) Instantaneously
Tr*7, Eo 'os, K,
(2) with a measurable speed
2.30,3 x8.3l4loq,^ 4xl0-2 (3) slowly
=
99000 vrv 0.24 (4) depending on condition
3. The half-life period for a first order reaction is 69.3 S. Its rate
constant is
='''?'=15'o los,o o':aot
88000 (1) 10-2 S-' (2) 10-4 S-'
2.303 x 8.314
(3) lo s-l (4) 102 S-1
(lzzro) 4. For a first order reaction we have k - 100 sec-r. The time for
88000
completion of 50% reaction is
= -1.7 x l0-4 (1) 1 millisec (2) 4 millisec
T_T (3) millisec (4) 10 millisec
'2 'r = -1.7 xlo4 k-r 7
Tr*7, 5. Which of the following is a first order reaction?
(1) 2H2O2@il ,P' >zH2O*Or(s)
T2 - 298 = (2) zHl
- r.7 xl o-4 H2+ 12
298*7,
(3) 2NO2 ---) 2NO * O,
T2 - - 1.7 x 10--4 x 298 x Tr= -0.0 5066 Tz
298 =
(4) 2NO * O, 2NO2
Tr* 0.05066 Tr= 298
6. If a' is the initial concentration
I
and k is the rate constant
1.05066 Tr= 298
of a zero order reaction, the time for the reaction to go to
Fr, 299 completion will be
- 1.0s066
(1): Q)t
k
(3) @) 2,
*
The half-life of first order reaction is 900 min at 820 K. Estimate
its half-life at 720 K if the energy of activation of the reaction is (C) SrcoND OnoeR REAcrroN
250 kJ ms-'. (1 .464 x 10s min) Reaction whose rate is determined by change oftrvo concentration
Kz (4'J terms said to be a second order reaction.
[r,r,r, )
t Kt = (tr,r), ) Example.
(i) 2A Product
Solution: (ii) A+ B -+ Product
Given, (iii) SrOr' +2I- *I,
(,r,r), : 900min, Eo = 250x 10-3 Jmol-r --+2SOl
(iv) H, * 12
\ - 820K, Tz:720K, (rr,r), =? (i) -:zHI
Example:
(a) CH3COOCH3 +NaOH
_ E,(r, -rr) _ 250x 10-3 (tzo- 820) --+ CH3COONa+ CH,OH
log,o (b) zcH3cHo
?, 2.303RTr*7, 2303 x 83 14x820x720 '2CH4+2CO
(c) 2NO2 -+ 2NO*O,
_ -250 x 10-3 x 100 _Z.ZI (d) SroS- +2t- --+2So;- *r,
2.303 x 8.3 14x820 x720 (e) cH3cooH+crHroH oH- >cH3cooc2H5 +Hro
K2
- 2.21- Antilog - [Link] - 6.17 x10{ (ii) Differential rate equation:
Kl - tu11i1og
(a) When A and B have equal initial concentration lsay 'a'
(t,,r), mole/litrel
Since,
$, d)
Kl (t,,r),
;:k@-*)'
(tr,r), 9oo (b) When ,4 & B have two different initial concentration
=
K2 I Kt 6.17 x 10-3=
=l.46x1olmin (say o'
o
& 'b' mole/litre)
d
;-k@-*)(b-x)
(iii) Calculation of Rate Constant:
1. For a first order reaction, the ratio of times to complete 99.9o/o
(a) When concentration of A and B are same.
and half of the reaction is A + B -----+Product
(l) 2 (2) 3.32,3 t=0 a a 0
(3) 6.6s6 (4) t0
t=t (o-x) (a-x) x
 Chemical Kinetics 1.13
(vii) Graphical representation:
*=klAj [r] klo-xllo-*l
=

+=kk-*)'
dt\ Rate I
tAr
On taking the integration of above equation.
Conc.2
t4-fkdtor
t("- x) -
-' +
(a-x)
-kt*c, -

I
att=0; x-0 =C-
On putting the value of C r, ;re equation lla
.11
kt- or
1 x
(o-*) a t o(r- x)

(b) When concentration of A and B are different

The rateofthe reactiofr,A -+ Products is 1.25 x 10-2 M/s
Case l: a> b is when concentrati on of A is 0.45 M. Determine the rate
constant if the reaction is
Then (a) first order in A
(b) second order in A.
Casellzb)q Solution:

Then
. 2.303
k_*log a(t - x) Given: A Products
t(b-a) b("- x) Rate-R- 1.25x l0-2M/s
lAl = 0.45 M
(iv) Unit of rate constant: k = mol-r L s-r (a) Rate constant, k = ? if order is one.
For first order, rate law is, R - k [A)
a

k- R 125x l0-2
I Slope --k . 0.45
(o-x) - 2.'78 x l0-2 S-t
(b) Rate constant, k - ? if order is two.
t For second order, rate law is, R - k [A]'
, R 1.25MS-rx10-2
(v) Half-life period (/,,r): "tt-A1ouo'yo,,
oly-

Putting a - x = al2 and t = tr,rin the integrated rate equation,

we get
- $.173 x 10-2 M-r s-l
t_al2
nttz - kxa(a-alz) Ans.
(a) Rate constant, k - 2.78 x l0-2 s-r
1 1 (b) Rate constant, k = $,173 x l0-2 M-rs-r
trrz = or trtz Q -
-Ka a
Half-life of second order reaction depends upon the
(D) TnrRD OnorR REAcnoN
concentration of the reactant. Reaction in which rate of reaction is determined by three
(vi) Time for 3l4th of the reaction (/r,): concentration term of reactant.
Putting x=1",a-x=iand t=t,o in integrated rate Reaction
equation. (i) A+B+C+ Product
I (ii) A+28 + Product
we get t,o = ?ka or ttto a -
a (iii) 2A + B ----+ Product
(iv) 3A + Product
Special Note: Time required for the completion of (i) Example:
definite fraction of the second order reaction is inversely (a) Reaction of nitric oxide and chlorine
proportional to the first power of initial concentration of
2NO + CL, -----+ 2NOC1
reactant.
t,t4 Chemistry

(b) Reaction of nitric oxide and oxygen (iv) However, the given reaction is generally carried out by
2NO * O, 2NO2 taking water in excess over methyl acetate. Thus, the
(c) 2FeC1, + SnCl z 1 ZFeClr+ SnClo concentration of water [HrO] remains constant.
(ii) Differential rate equation: (v) So the rate of the reaction depends only upon the
When the initial concentration of all the three reactants is concentration of methyl acetate and the order of the reaction
same. becomes one.
dx -/
-: - k(o-*)'
r3 (vi) The new rate law for this reaction can be written as
dt Rate = kICH3COOCHT] ('.' k'lHzol = k)
(vii) Therefore, hydrolysis of methyl acetate taking place in
(iii) Integrated rate equation: excess of water is' called pseudo first order reaction or
-ll
l*-
pseudo unimolecular reaction.
Ex 2. Hydrolysis of sugar
2(o - *)' 2a2
1 Slope : - 2k The other example of pseudo first order reaction is the inversion
x 2a-x (o - x)' of cane sugar (sucrose),
k-
t-2a2 (o- * CrrHrrO,, (aq)+ HrO(l)+C6Hr2Ou (aq)+ C6Hr2Ou (aq)
t Sucrose
(iv) HatfJife period:
Glucose Fructose
As water takes part in the reaction, the true rate law of the
reaction is,
Putting,2a-x -1and t = tr,rinthe integratedrate equation,
Rate - l{ lCrrHrrO,,][HrO]
we get From the above rate law, it appears that the reaction must be
of second order, but [HrO] is constant (similar to the hydrolysis
3
trrz=M or trtzqTI of ester) and thus, the rate law becomes,
Rate =klCrrHrrOrrf
Special Note: Thus, the second order true rate law is converted to pseudo
For a third order reaction, time required for the completion first order rate law.
of definite fraction of the reaction is inversely proportional Ex 3. Hydrolysis of ethyl acetate
to the square of the initial concentration of the reactant. (i) The hydrolysis of ethyl acetate is represented by the
(v) Unit of rate constant: k = mol- 2 L2 s-l equation.
(vi) Graphical representation: CH3COOC2H, (aq)+ HzO(q+ CH3COOH(aq)+ CrH, OH(aq)
Ethyl acetate Acetic acid Ethanol
(ii) The solvent water participates in the reaction. Hence, true
1 rute law of the reaction must be,
Rate
tAr rate = k'[Link] [HrO] ...(l)
(iii) According to the rate law equation (1), the reaction is
t expected to have second order kinetics. However, the
reaction is found to follow the first order kinetics.
(iv) The reason is that, the solvent water is present in such a
large excess that its concentration remains constant during
t
r,, the course of reaction.
(v) Thus, [HrO] = constant = k" ...(2)
lla2 (vi) Substitution of equation (2) into equation (I) gives,
rate = k'k" [CH3COOC2Hs]
- k [cH3cooc2Hs] ...(3)
Pseudo first order reaction: where, k = k'k"
The reactions that have higher order true rate law but are found (vii) The reaction, thus, has the first order rate law as indicated
to behave as first order are called pseudo first order reactions. by the equation (3).
Ex 1. Hydrolysis of methyl acetate (viii) The second order true rate law as indicated by equation (1)
(i) Consider the hydrolysis of methyl acetate (CH3COOCHT) has been forced into first order by the equation (3).
in the presence of an acidic medium. (ix) Hence, the reaction is pseudo first order.

CH3COOH, (aq)+ Hro (/) # CH3OH(aq)+ CH3OH(aq)

Methyl acetate (excess) Acetic acid Methanol DETERMINAIION OF ORDER OF
(ii) The order of the reaction appears to be 2 as the solvent REACTION
(water) participates in the reaction. (a) Integration Method: In this method known quantities of the
(iii) The rate law for the above reaction can be written as: reactants are mixed and the reaction rate is determined by
Rate = ICICH.COOCH3I [H2O] analysing the reaction mixture after different intervals oftime.
 Chemica[ Kinetics 1.15
The values so obtained are substituted, in the kinetic
equations of first, second and third order.
The equation which gives the most constant value for the K
for a series of time intervals is the one corresponding to the
From the following data for the liquid phase reaction A g B,
determine the order of the reaction and calculate its rate constant.
order of reaction:
t, 2.303 .tog(a,
a tls 0 600 1200 1800
Kr = j lAllmol L-t 0.624 0.446 0.318 0.226
Solution:
Given,
At t = 0, lAlo= 0.624 mol L-l
This method can be used only for simpler reactions.
(i) lA1,= 0.446 mol L-t at / = 600 s

(b) Half life Method: 2.303

Kl log,oW
General expression for the half life period for a reaction of t
ntr order is:
2"-t -l 2.303 _ 0.624
trrz : (n *t) 600
loBro
Kno'-' (" -t)
2.303 .
-M46
For first order tr,,n oo =ffilog,ol.4
For second order n=2 tr,,n Ila
_ 2.303 x 0. 146l
For third order n=3 tr,,n Ila2 , 600
In general t
r,,
n lla"-r Kr= 5.5 x 10-4 S-t
(ii) lAl,= 0.318 mol L-t at t = 1200 s

j, 2.303, 0.446
I\a
' -
1200 "'"
lrUEr^
0.319
'
i

2'3o3los,
-

= c"ru ^[Link]
1200
If doubling the initial concentration of reactants half life becomes 2.303x0.2927
half. Then order of the reaction will be? 1200

Solution:
Kr= 5.61 x 10{ S-t

(t,,r), ,r\'-' tr,, zo\'-' (iii) lAl,= 0.226 at t -- 1800 s

-( -(
(t,,r),-lo,) --, t,,,-\o ) Kt:ryloBroW
2

2- (2)"-'+ n- I - 1 + n=2
so, the order of the reaction will be 2 Kt:*log,oY
g00 "'" l 0.226
(c) Graphical Method: If a straight line is obtained by plotting
-2303los,grru^2.761
log (a- x) against +,it is a first order reaction. Similarly, if 1900
a straight line i, ,b!;ned by plott ing(at-x)' or (a-x)'against 2.303x0.441
1 800
!,the
dt
reactions are second and third order respectively.
K, = 5.64 x 104 S-t
K' + K' + K'
(d) The order of reaction can also be determined by Van't Hoff .'. Average rate constant =K- 3
differential method:
5.6x10-4 +5.61x10* + 5.64x10+
ros,o (*)-ros,o (*) 3
n-
log,o xr - log,o x, - 5 .62 x 10+ S-t
As the values of rate expression constant obtained by first
Here x, and x, different initial concentrations. order rate law are constant, t the reaction is of first order.
1.16 Chemistry

Temperature dependence of rate of reactions:

Temperature has very marked effect on the reaction rate. It has Threshold
been found that the rate of most homogeneous reaction are nearly
energy Energy of
doubled or tripled by 10o rise in temperature. E activation
ER
k,*to
_ 2,rr'3 (nearly)
k,
AH Energy evolved
The ratio of the rate constant of a reaction at two different P
temperatures differing by l0o i.e. knrclk,is known as temperature
coefficient of reaction rate.
Thisratio also depends upon temperature and two temperatures
generally selected are 25"C and 35"C. I H* = Summation of enthalpies of reactants
If a reaction has a temperature coefficient of reaction rute IH, = Summation of enthalpies of products
equal to 3, then raising its temperature from 25oC to 65oC, the
AH = Enthalpy change during the reaction
rate will increase by nearly 3 x 3 x 3 x 3 i.e. 81 times.
In order to explain the effect of temperature on the reaction rate.
E o, = Energy of activation of the forward reaction (FR)
Arrhenius proposed a theory of reaction rate which states as follows: E o, - Energy of activation of the backward reaction (BR)
(D A chemical reaction takes place by collision between
the reactant molecules, and collision to be effective. The Note:
colliding molecules must posses some certain minimum
(i) AH - Energy activation of FR - Energy of activation of
energy called threshold energy of the reaction.
BR
(ii) Reactant molecules having energy equal to or greater than (ii) In the diagram mentioned above, FR is exothermic
the threshold energy arc called active rnolecules and those (AH is -ve) while BR is endothermic (AH is +ve). The
having energy less than the threshold are called passive minimum activation energy of FR i.e. any exothermic
molecules. reaction will be zero while minimum activation energy
(iii) At a given temperature there exists a dynamic equilibrium for BR i.e., any endothermic reaction will be equal to
between active and passive molecules. The process of AH.
transformation from passive to active molecules being (iii) Greater the height of energy barrier, greater will be the
endothermic, increase of temperafure increases the number energy of activation and more slower will be the reaction
of active molecules and hence the reaction. at a given temperature.
(i") Rate = Collision frequency x fraction of the total number
Passive molecules Active molecules, AH = *ve
of collision which is effective.
(iv) Concept of energy -of activation (8,)
The extra amount of energy which the reactant molecules
(having energy less than the threshold) must acquire so that of collisions in which K.E. of the colliding molecules
their mutual collision may lead to the breaking of bond(s) equals to E,or exceeds over it
and hence the reaction, is known as energy of activation of Collision frequency is the number of collisions per
the reaction. It is denoted by the symbol 8,. Thus, unit volume per unit time. It is denoted by the symbol
Z. Z is directly proportional to JT. By 10o rise in
E o= Threshold ene rgy - Actual aver age energy
temperature. So, it is the fraction of the total number
E,is expressed in kcals mole-r or kJ mole-t
of effective. collisions that increases markedly by l0o
The essence of Arrhenius Theory of reaction rate is that exists rise in temperature resulting into marked increase in the
an energy barrier in the reaction path between reactant(s) and reaction rate.
product(s) and for reaction to occur the rcactant molecules must
climb over the top of the barrier which they do by collision. The Arrhenius Equation
existence of energy barrier and concept of E o can be understood The variable equilibrium constant of a reaction with temperature
from the following diagram. is described by Van't Hoff equation of thermodynamics which is
Threshold as follows o

_M
dlnKe

Ea
dT RTz
If \ and krbe the rate constant of FR and BR, respectively then
Ko = k,[Link], AH - fiot - Eor. Putting these in the above
equation we get,

dlnkt _dlnk2 _ Eo, _ Eoz

dT dT RT2 RT2
 Chemica[ Kinetics 1.17
Splitting into two parts Activated

dw, _ E.r
+Z 1
dT RT2
Energy Ea

THEORY OF REACTION RATES

/E C+D
Important theories to explain reaction rates are:
(a) [Link]: The important points of this theory are: +B
(i) If two molecules are to react together they must collide
with each other.
(ii) The collision between all molecules do not lead to Progress of reaction
chemical reaction.
(iii) Only those collisions results in chemical reaction in
which the molecules acquire energy greater than the FaCTORS AFFECTING REECTION RNIES
activation energy. (i) Nature of reactants:
The number of" collisions taking place per second In reactions involving higher energy barrier, the reactant
per unit volume of the reaction mixfure is known as molecules require higher energy of activation to cross the
collision frequency and its value is very high, of the barrier and get converted into products. A smaller number
order of 1025 to 1028 in case of binary collisions. of molecules possesses this higher amount of energy hence
(iv) The colliding molecules must posses certain minimum the rate of reaction is slow. In a reactions with lower energy
energy (threshold energy) to make the collision barrier, the reactant molecules require lesser amount of
effective. activation energy to pass the barrier. Hence large number
(v) The additional energy required by the molecules to of molecules possess, this energy and the rate of reaction
attain the threshold energy is called activation energy. will be fast.
It is acquired by the molecules as a result of interchange (ii) Concentration of reactants:
of energies during collisions. The rate of reaction increases with the increase in the
Thus, activation energy = Threshold energy. - Energy of concentration of reactant (except zero order reactions) In
colliding molecules. the reaction A + B -+ AB, if the concentration of A and B
are doubled the rate of reaction will increase to 4 times. '
(b) Transition state theory: The important points are:
(iii) Pressure:
(i) The theory is based on the fact that bond formation and
For a [Link] involving gases an increase in the pressure
bond dissociation involved in a chemical reaction must increases the rate of reaction by increasing the probability
occur continuously.
of collision among the molecules.
(ii) For a reaction to occur, the reactants having sufficient (iv) Temperature:
energy must approach each other to form activated Increase in temperature in most cases increases the rate of
complex. the reaction and the rate constant.
(iii) The energy of activated complex is higher than that of The temperature coefficient of a chemical reaction is defined as
reactants and products. the ratio of the specific reaction rates of a reaction at two different
(iv) The reactants must cross the energy barrier (activated temperature differing by 10oC.
complex formation) before converting into products. *'I'O
(v) The energy barrier has energy equal to the energy of Temperature coefficient - K,
activation.
Its value lies generally between 2 and 3.
The energy changes during exothermic and endothermic
reactions versus the process of reactions are shown below
When the temperature is increased, the kinetic energy

[1*r) of the reacting molecules increase. This shall increase

Activated [2 )
the number of collisions and the rate of reaction shall increase.
t If temperature is raised from 10 to n times then the rate of
Energy a reaction will increase by 2"-t times.
If temperature is raised from 0o to n times then the rate of
Reactants reaction will increase by 2" times. ;

A+B Arrhenius suggested an equation which describes K as a

function of temperature
Product
C+D K - Ae-fr
Progress of reaction
Where K- rate constant
1.18 Chemistry

A - a constant (Frequency factor) In photochemical reaction, each molecule of the reacting

Eo= activation enerry substance absorbs one quantum (single photon) of radiation and
At two temperature T, and Trtaking log of Arrhenius equation is excited to form the product.
For every reactiofl, & certain amount of energy is required.
log" Kt =LogA-+log"e Higher the intensity of light greater will be the rate of reaction.
Rrr ')e For these reactions, the value of AG may be positive or
negative.
tos, Kr:togA Temperature have no significant effect.
?rtog"e

So, log, Kt _ log, Kz = ,,1*r;_

(r_r) Mechanism: Cl, + hv --+ Clr* (activated molecule)
Primary step of reaction: + Cl + Cl
Clr*
_r, ) Secondary step of reaction: H, * Cl+ HCI + H

E' (l*\ clr+ H+HCl +Cl

K, - 2.303R [ \7, )
ron&
" Final step of reaction: Cl +'Cl + Cl

(v) Catalyst: Quantum yield (or quantum efficiency):

A catalyst is a substance which lowers the energy of The quantum efficiency yield @) of a photochemical reaction
may be expressed as
activation of a rcaction. The magnifude of energy barrier is
reduced in presence of catalyst..Hence a greater number of , Number of molecules reacted orproduct formed
reactant molecules can get over the energy barrier and as a Q - N"-b.-f pLt"" rbr;tb.d
result rate of reaction increases.
Application of photochemical reaction :
(i) in photography
(ii) in photo printing
The rate constant for a reaction of 500oC is 1.6103 M-rs-r. What (iii) in photosynthesis '

is the frequency factor of the reaction if its energy of activation (iv) in vision
is 56 kJ,mol-r. (v) in electronic industries
(vi) in many polymenzation reactions.
Solution: Mechanism of Reactions: The most of the reactions occur in a
Given: K - 1.6103 M-t s-t series of steps, some of which may be quite fast while other may
T - 273+500 = 773 K, E o= 56 = 56000 J mol-t be slow.
A=? Van't Hoff proposed that whole kinetics of the reaction
As per Arrhening equation depends upon the rate determining step (the slowest stepof a
reaction is taken as the rate determining step)
lnK-ln A-Eo Examples.
RT
Eo
(i) Reaction between NO and Hr: 2NO + zHz-) N, * 2H2O
2.3031o9,0 - K -- 2.303 log,o A - This reaction involves 4 molecules but it has found to be
RT third order because it occurs in the following steps:
Eo (a) 2NO*Hr+Nr*HrO, (slow)
.'. log,o K - log,o A- (b) Hror* H, -----) 2H2O (fast)
2.303RT
(a) being slow is the rate determining step. The rate is
log,o A- log,o K+
Eo ' Thus
given by: Rate - K [NO]' [Hr]
2.303RT (ii) Reaction between FeCl, and KI:
s6000 ZFeCl, + 6KI ----+ 2FeIr+ 6KCl + 12
-1.6x103+ 2.303x 8.3 14x773 This reaction involves 8 molecules, but it has been found to
be of third order
= 3.204 + 3.784 = 6.988 (a) FeCl, + 2KI ----+ FeI, + 2KCl + Cl- (slow)
.'. [ = Antilog 6.988 = 9.727 x 106 M-r s-r
(b) zKI + 2Cl- ---+ 2KCl * l, (fast)
Frequency factor - 9.729106 M-r s-r
Rate-K[FeClr] [KI]'
This indicates that the reaction is of third order.
PHOTOCH EMICAL REACTION (iii) Reaction between H, and Ir: H, * 12 ;- zHl
(a) Ir+21 (fast)
Reactions wtrich occrrs in the presence of light are photochemical (b) H, * I HrI (fast)
reaction i.e., reaction which do not occur in dark. (c) HrI + I--+
---) zHl (slow)
Example. (iv) Combination of NO, and Fr: 2NO2 * F, 2NO2F
+Cl, hv
(i) H2 ,zHCl (a) NO, * F, NO2F + F (slow)
(ii) Photo synthesis (b) NO,+F NO2F (fast)
(iii) Vision Thus order = 2
 Chemical Kinetics 1.19

reaction.
1. The influence of temperature on reaction rate is predicted by
(1) Kirchhoff's equation
(2) Arrhenius equation
(3) Van der wall's equation
concentration, temperature, catalyst,
(4) Kinetic equation
flfso ,and
2. For the reaction A + B when concentration of A is made
1.5 times the rate of reaction becomes I .837 times. The order
of reaction is
integration,
(1) 1 (2) l.s
.mAy
(3) 2 (4) 2.s
3. What is the order of a reaction which has a rate expression
rate=klAltrzlBl'?
(r) 3l (2)
:called activation enefg)l.::,i ; ,
(3) zerc (4) I
4. The minimum energy needed to convert a reactant into
product is called
(l) Potential energy (2) Kinetic energy
(3) Threshold energy (4) Activation energy
5. Threshold energy in a reaction is equal to
(1) activation enerry
(2) activation energy - nonnal energy
(3) activation energy * normal energy
(4) nonnal energy of reactants only
6. The rate of a chemic al reaction depends on
(l) Atomic Mass (2) Equivalent Mass
(3) Molecular Mass (4) Active Mass
1,20 Chemistry

SOLVED EXAMPLES I

1. Express rate of reaction for the following changes: Rate - k lProroru,T'''

(a) zHIe H, * l, (b) N, * 3Hr-+ 2NH, If the pressure is measured in bar and time in minutes, then
dlHI) dllr) what are the units of rate and rate constants?
Ans. (a) Rate of reaction _ - !zdtdtdt- ry_
Ans. CH3OCHTJ CHo + CO * H,

(b) Rateofreaction :-
dlyrl-- I dlNr)- I dll'{41 :
Rate k[CH3OCH3 f3tz - KlPru,orr,T'''
dt3dt2dt :
unit of rate bar min-r
2. The order of the reaction A -+ B is three. What happens to
the rate of the reaction if concentration of A is doubled?
unit of K : - barr'72 min-r
Ans. It becomes by eight times ffi H
3. A lump of coal burns slowly whereas coal dust burns 10. What is the effect of temperature on the rate constant of
readily. Explain. reaction? How can this temperafure effect on rate constant
be represented quantitatively?
Ans. Coal dust has larger surface area. The more is the surface
area, the more is probability for reaction. Ans. Rate constant of reaction always increases with rise in
temperature. It is quantitatively expressed as:
4. Burning of carbon is highly exothermic process, yet it does
not start of its own. Explain. K - 1n-E'tRr

Ans. The activation ene rW of combustion of carbon is quite high K2 Eo

or 2.303 loe l'r-'r1
and thus, inspite of exothermic nature the reaction starts v Kt - R L rrT, l
only when flame is applied to the heap of carbon content.
where K is rate constant at temperafure T; A is Arrhenius
5. Explain why reactions with molecularity > 3 are rare? parameter and E" is energy of activation which is always
Ans. It is highly unlikely that more than three molecules positive.
will simultaneously collide with the correct energy and LL. Reaction between NO, and F, to give NO2F takes place by
orientation to form an activated complex. the following mechanism:
6. The unit of rate constant depends on order of reaction. NOr,*,* Fr,*, stow , NO2F*, * F,r,
Justi$r it.
NOr,r, * F,r, f"t lNOrF,*,
Ans. Rate - kV)' where r is order of reaction.
Write the rate expression for the reaction.
k - ratelfA)'.
Ans. The slowest step determines the rate of reaction. Thus, rate
unit of k_ (mol litre-r time-r)/(mol litre-r)' - moll-' _ K[NO2] [F2]
litre'-r time-r
12. The rate of change in concentration of C in the reaition;2A
i.e. dependent on the value of n. + B +2C + 3D, was reported as 1.0 mole litre-rsecond-r.
7. What would happen if every collision between reactant Calculate the reaction rate as well as rate of change of
molecules were to form products? concentration ofA, B and D.

Ans. Reaction will go to completion instantaneously. [Link]- 1 dlA)-- dlBl : 1 dlcl I dlpl
8. Reactions with low activation energy are fast, while those 2dtdt 2 dt 3 dt
of high energy 6f activation are slow. - rate of reaction

Ans. Rate depends on rate constant and rate constant 1r-E,tRr. - dlcl: 1.0 mol L-r s-r
Thus if E" is small, rate constant will have higher value and dt
thereby rate of reaction is more for low E,vahue reactions. dlAl :dlcl : l.o mol L-l s-r
g. The decomposition of dimethyl ether leads to the formation dt dt
of CHo , H, and CO and the reaction rate is given by:
dlc) :
-1
dlBT
1.5 mol L-r s-,
Rate - k[CH3OCH,]"' dt2dt
- The rate of reaction is followed by increase in pressure in a dlp) 3 dlcl I 1
closed vessel and the rate can also be expressed in terms of dt
- 2dt2
" - 1.5 mol L-r s-i

the partial presure of dimethyl ether i.e. ,

 Chemical Kinetics [Link]
Ans. N2OH,G) i NrOo,r, * 1 l2Orrr, Given P - ll4 mm
Also, Rate- laPl
2dt After 20 s, total
pressure
Rate -
1, I : 0.5 mol L-r s-l
2 Initialpressure P 0 0

13. For a reaction; 3A + Products, it is found that the rate of (P-P') + P'+ g'D): 133 mm
reaction doubles if concentration of A is increased four
times, calculate order of reaction. Pressure at t - 20 s (P - P') P' P'12

Ans. Rate if [Reactant] - rate: P'12: l9 mm

- k[Reactant]' a, 11

r, : k[a]" P':38
- 4a; rate :
if 2t, mm
[Reactant]
2rr: k[4a]' Thus rateof reaction in terms of change in pressure :38120
: 1.9 mm s-l
t [rl'
,: La] 1.9
760
atm s-l
n- 1
2 Also we have PV - nRT
14. Find the order of reaction for the rate expression rate
- k[A] [B]'[Link] suggest the units of rate and rate constant or n c- P

for this expression. VRT

: P'
Ans. Rate - k [A] [B]"'
change in concentration in 20 second dc - RT
(Change in pressure)
25 :1.67 38
orderofreaction- 1+
J:, - 7 60 x 0.0821 x 400
-r.52xro{M
( ax\
Unit of rate I I is mole litre-r time-l 1.52x l0-3
\dt ) rate of reaction in terms of change in conc. - 20
-v
Unit of rate constant: rate constant ft) \/
dx ldt - 7.61 x l0-5 Ms-l
[reactant]t" 17. The reaction; 2NO Br, + 2NOBr, is supposed to follow the
mol litre-t/-t following mechanism,
mol (i)
\'/2-I No * Br^
fast ' NOBr^
litre
(ii) NoBrr+ No slow ,2NOBr
: mol-2/3 litre*z/z 1isr,-r
Suggest the rute law expression.
15. For the decomposition reaction: NrOo,*l e 2NOrrrtl
the initial pressure of NrOo falls from 0.46 atm to Ans. The rate expression is derived by step II of the mechanism,
0.28 atm in 30 minute. What is the rate of appearance of as it is the slower one
No2? rate - tNOl
k [NOBrr] ...(1)

Ans. Rate of reaction_-

d[N2o4] _ 1 d[No2] However, NOBr, is an intermediate and thus its
dt2dt concentration should be replaced from equation (1)

I dlNo2l_ (0.28 - 0.46) For step (I) Equilibrium constant k. : [NOBrr]

2 dt 30 [NO] [Brr]
I d[No2]_6x10_3 [NOBrr] - k" tNOl ;errJ ...(2)
2 dt Thus by eq. (1) and (2) Rate : k' [NO]';nrrl
dlNo2l 18. Afirst order reaction takes 69.3 minutes for 50% completion.
- 1.2 x 10-2 atm min-l
dt How much time will be needed for 80% completion?
1.6. For the decomposition, NrOrre) J NrOo,r, * llzoz(s), the
initial pressure on NrO, is Ll4 mm and after 20 s, the 0.693: 0.693
Ans. k minute-l (': t''': 69 '3 min')
pressure of reaction mixture becomes 133 mm. Calculate tr,, 69 3
the rate of reaction in terms of (a) change in pressure s-rand 2303
(b) change in molarity s-'. Given that reaction is carried out Now, k - log 100 fif
') L a: 100, x-80 and a-x -20)
at 127"C.
t 20
1.22 Chemistry

2303 (a) 3NO,r, -+ NrO*t * Nr,r,, Rate : k[NO]'

0.693
69.3- t
log 5
(b) HrOr,uo, + 3I1,q) * 2H* + 2H2Os,, + Ir-i
t: 160.97 minutes. Rate: k[Hror] [-]
19. Show that time required to complete 99.9o/o completion of a (c) cH3cHo,r'-+ cH+(e) * co,r't Rate - k[cH3cHo]3/2
first order reaction is about three times to 90%o completion.
(d) CHCL*T * CH,r, + CCI+(') * HCl,*,;
Ans. For [Link] [a]o: 100 la-x|- 0.1
- kICHCL]lclrf'''
Rate

trr.r*: 2.303 .log 100_ 2303xJ A

(e) C2Hsclrrr i CrHo,r, + HCI(s) Rate : k[CrHsCl]
k - k
Ans. (a) Second order ; Litre mol-r time-t
Similarly tsoo:ry,"*#: ry"I (b) Second order ; Litre mol-r time-t
. .'. trr.r*- 3 x tno*. (c) 312 order ; Litrer
t2 mol-uz lipe-r
20. The rate constant for a first order eaction was found to be
(d) 312 order ; Litrettz mol-t/z fims-t
0.082 min-r. If initial concentration of reactant is 0.15 M
how long would it take, (e) First order ; time-l

(a) to reduce the concentration of A to 0.03 M. 23. For the reaction; 2A+ B + C + ArB + C
(b) to reduce the concentration of A by 0.03 M.
The rate - k[A] [B]'with k - 2.0 x 10-6 M-2s-1. Calculate
the initial rate of the reaction when tA] - 0.1 M,
Ans. Case (a): Given k - 0.082 min-r, [A]o:0.015 M, [B] - 0.2 M and [C] - 0.8 M. If the rate of reverse reaction
[A],: 0.03 M. is negligible then calculate the rate of reaction after [A] is
reduced to 0.06 M.
2.303 ,
lAl, 2.303 , 0.15
k '' lA), 0.092 '' 0.03 Ans. Rate - k[A] [B]'
Case (b): Give k - 0.082 min-r, [A]o - 0.15 M; [A]t: 0.15 [A] = 0.1 M, [B] - 0.2M, k - 2-0 x10-6
0.03 - 0. r2}i,[
.'. Initial rate -2.0 x 10-6 x Q. I (0.2)2 - 8 x 10-e mol L'l s-r
2'303 o' 15 :
t- loe
L) 2.72min. 2A+B+C
0.092 0.n
21. The inversion of cane sugar proceeds with constant half
+ArB+C
life of 500 minute at pH - 5 for all concentration of sugar. Initially 0.1 M 0. 2M 0.8 M
However, if pH : 6, the half life changes to 50 minutes.
After time t (0.1-2x) (0.2-x) (0.8-x)
Derive the rate law for inversion of cane sugar.

Ans. At pH : 5, the half life for all concentration of sugar is 500 When [A] is reduced to 0.06 M
i.e., tr,, * [sugar]o which suggest for first order and hence 0.1- 2x- 0.06
rate of reaction for sugar concentration can be given as
x - 0.02
r - k[sugar]t
lBl - 0.2 - 0.02 - 0.18 M
Now if pH is also taken into account
New rate when A is reduced to 0.06 M and B is 0.18 M.
rate - k[sugar]t [H+]m
Rate I 8)'
For tH.] tr,roo [H+1t-m

500 ""[10-s]1-m pH - 5 0 .'. [H.] : 10-s

:l
-,' L" ;:ff]' ::'
24. The rate for the decomposition of NH, on platinum surface
50 - [0-r1t-", pH: 6 [H.] : 10{ is zero order. What are the rate of production of N, and H,
if k - 2.5 x 10-4 mol L-l s-1.
r,
ro: []9]'-'
Lr Ans. 2NH3 -) N, * 3Hr.
-l
I -m-
Thus, I
dlNH3l
- ry: I dlH')
or m:0 Rate of reaction (r) --i
'zdtdt3dt
Thereforc rate law - k [Sugar] [H.]o
22. From the rate expression for the following
reactions,
Rate (r) - K[NHr]o = K (.'. zero order reaction.)

determine their order of reaction and the dimensions of the - 2.5 x 104
rate constants.
 Chemical Kinetics 1.23

o:1T
.'. x mol L-rs-r Ans. (a) t,r: ry = 3.465 x 1o-3 second
ry-r2.5 1o-4
k 200
d(H') :
dt
3r : 3 x 2.5 xl0-4 - 7 .5 xlo-4 mol L-r s-r (b) tr: ryk2 = 0'193 - 3.465 x ro-r minute
25. A reaction is second order with respect to a reactant. How 0.693 0.693
is the rute of reaction affected if the concentration of the (c) - 1.733 x iO-' year
'r2- n4t-

reactant is: 29. The rate constant for a first order eaction is 60 s-r. How
(a) doubled, (b) reduced to ll2? much time will it take to reduce the initial concentration of
the reactant to its lll6'h value?
Ans. Given, rate (rr) : K[A]'
(a) If [A] is doulbed: r, : kl2A12 '. r,
- 4ro Ans.t-2.303 ,
a
,k log'r (a-x)
If a- l then(a-x): 1116
O) If [A] is reduced to half, r,:Ul 41' 1

L2) Z,O 2.303 l

26. A reaction is first order in A and second order in B: t- log 0.0462 s-l
* U 16:
(i) Write rate equation. 30. The rates of most reactions double when their temperature
is raised from 298 K to 308 K. Calculate their activation
(ii) How is the rate affected when the concentration of B is energy.
tripled?
Tr-7,
(iii) How is the rate affected when the concentration of both Ans los -
Eo

A and B is doubled? l?) 2.303 R TrTz

Ans. (i) Rate-k[A]'[B]' - 2;rr:308, r, : zsBK

(ii) ro: k [A]'[B]' ?
r, : k [A]'[3B]'
tog2# 308 x298
10

:9 E 52.903 x 103 J or Eu : 52.903 kJ

"'
fr
"0
^:
31. The half life for radioactive decay of raC is 5730 year. An
(iii) ro: k [A'][B]'
archaeological artefact contained wood had only 80% of the
12: k [2A]'l2Bl' raC found in a living tree. Estimate the age of the sample.

.'. t2:8 * to 2'303 a

Ans. T - LoG
27. The reaction between A and B is first order with respect to k (a- x)
A and zero order with respect to B. Fill in the blanks in the
-x) :
o=:,!?1
following table: troofl4c - 5730 yr;' k: yr';Also A - 100, (a 80
5730
Experiment [A] (mol L-t)
2.303x5730. 100
t-fflos*-1845yr.
I 0.1

II 32. Consider the following data for the reaction:

m 0.4 A+B+Products
ry Run Initial concentration A

[B] (mol L-t) Initial rate (mol L-t min-t) l. 0.10 M

0.1 2.0 x l0-2 2. 0.20 M
0.2 4.0 x l0-2 3. 0.20 M
0.4 Initial concentration B Initial rate (mol s-t)
0.2 2.0 x 10-2 [Link] 2.1 x l0-3
Ans. (ID 0.2;(III) 8 x l0-2;(IV) 0.1 1.0 M 8.4 x 10-3 \

28. Calculate the half life of a first order reaction from their rate 2.0M 8.4x l0-3
constants given below:
Determine the order of reaction with respects A and with
(a) 200 s-'; (b) 2 min-'; (c) 4 yearl respect to B and the overall order of reaction.
1.24 Chemistry

Ans. The rate law may be expressed as: Activation energy in the absence of catalyst (Er) : 30 kJ
mol-r
Rate - k lAl'[B]o :
Activation energy in the presence of catalyst (Er) 24 H
Comparing experiments 2 and 3
mol-r
(Rate)r: k[0.2]o [1.0]o: 8.4 x 10-3 ' (r) /Rr
According to activation energy concep, k, = Ae-E' i
(Rate), : k[0.21n [2.01e: 8.4 x 10r (2)
k,: Ae-q/Rr kz: Ae-E..lrtr
Dividing equation (2)bV (1), we get
k, g(Er -Ez )/Rr
or k, -E, -E,
(Rate), k[0.2]P [2.0]q
-
8.4 x 10-3 kl - k, RT
(Rate), k[0.2]P I I .0]o 8.4 x 10-3
,^ _ k, _ E, -8, (30 - 24)x 103J mol-'
-oU.
q:0 k, 2.303RT 2.303x(8.314 JK-t mol-') x 298 K
l2l, - l2)o or
I k,=
Comparing experiments and 2,
- Antilog 1.0516 : 11.27 or kr: 11 .27 kl
klt
(Rate), - k[0.20]o Il.O1e - 8.4 x 10-3 (3)
Thus, the reaction rate has increased nearly by 11 times.
(Rate), : k[0.101n [1.0]o :2.1 x l0-3 (4)
35. The rate constant for an isomertzation reaction A + B
Dividing equation (3) by (4), we get is 4.5 x 10-3 min-l. If the initial concentration of A is lM,
calculate the rate of the reaction after t hour
(Rate), k[0.20]Pll.0lq _ 8.4x10-3 _ a
Ans. Step I. Calculation of concentration after I hour (60 minut)
(Rate), k[0.10]nll.0lo 2.1x10-'=-+ .

p-2 2.303
l2)r-121, or k_ 6olAIo
so
" t [A],
order with respect to A -2
order with respect to B - 0 ,- -tA[
logm: kt : 4.5 x 1 0-3 min-1x 60 min
tt72e
2S0S ZS0g - o.

over all order - 2

33. The rarte of a particular reaction quadruples when the bg*+

" urlrr\"r o. tt72:
- IAntilos 1.310
temperature changes from 293 K to 3 13 K. Calculate the [AJt
energy of activation of reaction. (R: 8.314 JK-t mol-t)

Ans. ACCORDING TO ARRIIENIUS EQUATION,

tAI, ,[tb=:+
- 1.310 1310
:0.763M

Step II. Calculation of rate after t hour (60 minute).

. k" E l-t tl
lnt L:21 |
: k [A],
Rate after 60 min, : 4.5 x 10-3 min-l x 0.763 M
" k, 2.303R LI --- T, )', :3.4354x10-3Mmin-r.

T,:293K,Tr:313K 36. A + B ko- 101s e-2ooo/r

4 Eo ll C + Dk.- 1014e-roooir
log -:I 2.303x (8 .314 J mol-' K-') 2%- 313
1!99"
6
Temeprature T in K at (ko: k.) is? Ans.
20
I.803
, -
'") = 2303x (8 .314'oJ mol-'=K-')
1oq4 37. From the following dataof initial concentrations and rates,
293 x 313
calculate the order of reaction aA +
products; and its rate
0.6021 -
E' * 20 constant?
2.303x (8.3 14 J mol-r K') 293x 313
._t
[A] mol L-' 0,1 0.2
0.6021x2.303 x 8.3 14x293 x 313 mol 'I
0.4
Eo=
20 Rate mol L-l s-l ) x 10-s 36 x 10-s
Eu: 5.2863 x 104 J mol-r :52.863 kJ mol-t 144 x 10{

34. The actixation energy of a first order reaction is 30 kJ/mol Ans. 2,9.0 x 10-3 mol-l L s-r

at 25"C. The activation energy for the same reaction in the 38. The stoichiometric equation for the oxidation of
presence of a catalystis 24 kJ/mol at25"C. How many times in acid solution
bromide ions by hydrogen peroxide is
the reaction rate has changed in the presence of a catalyst? 2Br +IJrOr+ 2H* + Br, + 2H2O
Ans. Let the constant in the absence of catalyst : k, Since the reaction does not occur in one stage, the rate
Let the rate constant in the presence of catalyst : k, equation does not correspond to this stoichiometric equation
but is u: [HrOr] [H.] [Br]
 Chemical Kinetics 1.25
(a) If the concentration of HrO, is increased by a factor of T, : :293 K
20 + 273
3, by what factor is the rate of consumption of Br ions
increased?
Tr:50 + 273 :323 K

(b) If, undercertain conditions, the rate of consumption of E

log,o 3 -
Br ions is 7.2 x 10 3 moledm-3s-r, what is the rate of 8.31 4x2.303
consumption of hydrogen peroxide? What is the rate of 2.303x8.31 4x323x293x 0.477
consumption of bromine? E
u :
30
(c) What is the effect on the rate constant k of increasing : 28811.8 J mol-t
the concentration of bromide ions?
: 28.8118 kJ mol-r
(d) If by the addition of water to the reaction mixture the
total volume were doubled, what would be the effect
42. The energy of activation for a reaction is 100 kJ mol-l.
Presence of a catalyst lowers the energy of activation by
on the rate of change of the concentration of Br? What
75%. What will be effect on rate of reaction at20"C, other
would be the effect on the rate constant k?
things being equal?
Ans. (a) 3
Ans. K - Ae-E"m
(b) Both rates are 3.S x 10-3 mole dm-3 s-l
absence of catalyst, - Ae-roo/Rr
K,
(c) None
presence of catalyst, Kr- Ae-2s/Rr
(d) Decrease by a factor of 8, none
K^ =
K, 75
A + 2B + C + 2D is run three times. In the ,r, - e75lRr ot 2'303 log *, P,
Z lctl|t.l' a A A r

39. The reaction

second iln, the initial concentration of a is double that in
the first run, and the initial rate of the reaction is double
lnol:
K. 75
that of the flrst run. In the third run, the initial concentration ^"' K, 8.314x10-3 x293x2.303
of each reactant is double the respective concentrations in
K^1
the first run, and the initial rate is double that of the first -2'34x 1ot3
run. What is the order of the reaction with respect to each K1

reactant? K2 12 rate in preffilffi of cataly*

K1 11 rate in abstoe of cdaly$
Ans. 1 w.r.t. A, zeto w.r.t. B
40. The following reaction was carried out in water CLr+ 2l- -> b- -K2 - 2.g4x 1 o1s
Ir* zcl-. The initial concentration of I- was 0.25 mol L-r \K1
and the concentration aftr 10 minutes 0.23 mol L-1. Calculate
43. Thermal decomposition of a compound is of the first order.
the rate of disappearance of I- and appearance of Ir.
lf 50% of a sample of the compound is decomposed in
Ans. A [f] : [I-]r: [I-]i : 0.23 - 0.25_ - 0.02 mol L-r 120 minutes, how long will it take for 90o/o of the compound
to decompose?
At-10-0:10min .

Ans. Half life of reaction : 120 min

a[r- ] (-o .02) _ ,, 0.693=0.693
0.002 mol L-r min-r rr. I
At 10
U
=
-
1ZO - 5.77 x 10-3 mn-r
o 'qo2 : 0.001 mol 2.303 . a
Rate of appearance of I, _ -1{i
2 At - 2
+
t--K
- - logro a-x
L-l min-t _ 1 x l0-3 mol L-r min-l a - 100, x : 90 or (a - x) : 10

41. The rate of a reaction triples when temperature chanes +_ 2.303 ,_..r. 1 0
r' _ -::-: ^-lOO,," .t^_
2.303 :
399min
=
from 20"C to 50"C. Calculate energy of activation for the [Link]-3'-r'ru 5.77x10-3
reaction (R : 8.3 l4 JK-' mol-r)
44. Nitric oxide, NO, reacts with oxygen to produce nitrogen
dioxide
Ans. The arrhenius eq is log,"
"'' 9:
K, = !"^ ^^ t};Il
R x z.3o3l T,T, l -
2NO (g) + Or(s) -) 2NO2

Given, lla -3 R-8.314JK-tmol-l What is the predicted rate law, if the mechanism is
K1

(slow)
1.26 Chemistry

Ans.r-K[NOr]tNOl Time (sec) 0 50

(atm) 0.2
from l'tequation l.: - tTo']-
K^- tNo t
.'. [No3] -K"tNol [o']
Total pressure 0.25

t^i"]t"; "' Calculte the reaction rate when the total pressure is 0.28

= r: KK. [NO], [Or] atm.

Ans. Rate - 5.54 x atm s-l

For the reaction of I, II and III orders, K, : I! : K, when
10-4
45.
concentrations are expressed in mol L-r. What will be the 50. For a reaction zNO, * F, -+ 2NOrF
relation in K,, Iq, Iq, if concentration are expressed in the experimental rate law is r : k[NO21 [Fr]. Propose the
moVmL? mechanism of the reaction.

46. The rate law for the reaction,2ClrO -+ 2clz* Oz at 200"C Ans. The rate law is r - k[NOr]tFrl
is found to be rate - k[Cl ,O)'. Since rate law is proportional to single power of NO rand
single power of F, it implies that only one molecule of NO,
(a) How would the rate change if [Cl2O] is reduced to one- and one molecule of F, are involved in the slow step. Thus,
third of its original value?
the various steps are:
(b) How should the [ClrO] be changed in order to double
the rate?
Step 1. NO, + F, -+ NO2F + F

...(slow)
(c) How would the rate change if [Cl2O] is raised to
threefold of its original value? Step 2. NOr+ F+ NO2F

Ans. (a) r - K[Cl ,O7' ..(fast)

Let new rate be r', so 2NO2+ F' + 2NO2F

r-^L
r,
3 -l
!,
: *fcrzo ]' _-gr ,, :1
I I
...(Overall reaction)
51. If thermal decomposition of dinitrogen pentaoxide is
(b) In order to have the rate:2r, written as

Let the concentration of Cl2O be x 2N2O5 + 4NO r* O,

2r - Kx2 ...( I ) and the rate law is r - k[N, Or]. Propose the mechanism of
reaction.
r: K[ClrO)' ...(2)

(i) 2, _ Kx2 Ans.\O, ---no* )NOr+NOr;\or+NO3 t* )2NO2*o,

(iiJ r K[cl2oT 52. If the decomposition of nitrogen oxide 2NrO, + 4NO2
* Or following a first order kinbtics,

o-
L_
x2 (i) Calculate the rute constant for a0.04 M solution, if the
instantaneous rate is I .{ x l0-{mo1 L-l s*1.
ICLoJ
x2:2lClrOl' x - JZ [Cl2O]
(ii) Also calculate the rate of reaction when the
concentration of NrO, is 1.20 M.
(c) New rate : K[3ClrO]': 9K[ClrO|' - 9r
(iii) What concentration of N, O, would give a rate of
i.e. nine times of the original rate 2.45 x 10_s mol L-r s-r?
47. A radioactive A says to B ool
am half of what you were. Ans. (i) As the given reaction is of first order, therefore,
when you are one fourth of what I was. Moreover I was
1.414 times than what you were." If the half life of A is rute - k [NrOr]
8 days, what is the half life of B? rate .4x104
k_=[Nrou _1
-
Ans. 8 days ] oJ4
48. A first order reaction is 20% complete in 5 minutes. In what IM - Conc. in mol, L-']
time will the reaction be 60% complete?
- 3'5
-J.J^
x 10-s s-1'
lV D

Ans. 20.5 minutes (ii) Now if the concen(ation of N, O, is 1.20 M, then

49. The following rate data were obtained for the thermal rate
decomposition of NrOr(g)
- k [NrOr]
2N2O5 (g) -+ 2N2O(g) + Or(g)
- 3.5 x l0-s x 1.2O -- 4.2 x 10-5mol L-rs-r.
 Chemica[ Kinetics 1,27
(iii) To obtain concentration of N, O, when the rate is 2.45 x (b) Rare at Pr: 0.65 atm
10-5 mol L-r s-r' we note that
Psorct, at total pressure of 0.65 atm: 1.0 - 0.65
*lt" 2.45 x 10-s :0.7
:0.35
[N,o.:
LJK
mol L-r or 0.7 M. atm
3.5 x 10-5

53. The rate data obtained for a hypothetical reaction

Rate - k [N, Or] :2.23 x l]3 x 0.35 :7 .8 x 10a atm s-r
A+B+2Cis

rAltdt rBl gtgl

(mol L-') (mol L-') (mol L-tmin-')

I .0 1.0 3.0 x l0-2

1.5 1.0 4.5 x 10-2

I .5 0.816 3.0 x 10-2

Based on above data derive the rate law expression and also
calculate the value of rate constant k.

Ans. Rate - k tA]tB]',k: 3.0 x 10-2mol -2Lzmin-r.

54. The following rate data was obtained for the first order
themal decomposition of SO, Cl, (S) at a constant volume. :iiliiil!:iiiiliiii:ii!;[Link]

iiiilii#ffiii
SO2Cl2(g) -+ SO, (g) + cl, (s)
(i) Let the rate r be equal to r - k[No]'lHrlu
Experiments Time (sec-l) Total pressusre (atn)
where a and b are the order with respect to NO and H,
l. 0 0.5 Dividing (l) by (z),we have
2. 100 0.6 3x lo-s ( s*lo-3 )'f [Link]-' )' I (tY

Calculate the reaction rate when total pressure is 0.65 atm.

**t=[t*,otj r-.,"t.] =;=l..;J l. "'a:
I

Ans. Let us say that the pressure of SOrCl, decreases by * atm,

Dividing(2) by (3), we get
then the increase of pressure of SO, and Clr: x atm each.
[ '.' 1 mole of SO, Cl, decomposes to give 1 mole of SO,
e lo-s
- = [? f ]
3.6x10-s It0x1o-3 )
x .19
l' o'zs: (o'2)b
\ z
"'b
:l
and 1 mole of Clrl
(ii)r - k tNol[Hr]
SO2C12(g) -+ SO, (g) + Cl, (s)
Pressusreatt:00.5atm 0 0 (iii) f - dm3 mol-r s-l : 2.4 dm3 mol-r s-r
Pressusre at time t, (0.5-x attn) x atm x atm
pressure (iv) Initial rate - (2.4)(8 x 10rX8 x 10-3) mol dm-3 s-r
Since total (Pr) - (0.5 - r) * x * x : 1.536 x 10a mol dm-3 s-l
(Pr):0.5*xorx-Pr-0.5
Hence Psorcr, : 0.5 - (Pr- 0.5) : 1.0 - Pr
Since, at t -100 S, Pr: 0.6 atm

.'. Psorctr: 1.0 - 0.6 :0.4 atm.

(a) Evaluation of k
,_ 2.303 , _
lr:-_lnc
Initial press,rre ;:i, ji:iiliiiiiliii!:!,:iii:iii,i;il riii:

t " Pr essure at time t itiiii#uilii1ii11

(a) The rate law for the first-order reaction is

2.303, 0.5 2.303, .A
- 100lop0.4_ 100 los 1.25 -dW
dt rL r
-r,lA)ork,r =+
Vl "ry
dt
2'303- - For a small finite chage
- x 0.096 ) - 2.23 x 10-3 s-r
100
1.28 Chemistry

k, = _a?=ldi
I
^[/] ^[l[,al),
1
tt:|.So/operminute
)r
0.015 A
kr - - 2.5 x 10* s-'
60s

(b) 0 '693 ^
tvz =0'693 - 77x 103 s - 46min

(c) 2sa3- 100)

\-'l' t kt "loo-go
:6.44x103s=10.7min
-1on :i;::l:itl:::::::i:i:jii:l::::i:ii,i ii::::ii::ii::i

..',;iili. ill|il.;.;.r

:, i.
The hydrolysis of ethyl acetate will be first order if the above
llr-u$r3+Ttrlu 3 data confirm to the equation.
From the following data show that the decomposition of 2.303 . .,oV* -Vo
hydrogen peroxide ii aqueous solution is a first-ord.r reaction.
What is the value of the rate constant?
"r- t -' v* -v,
k.

-l(
Time inminutes 0 10 2A 30 40 Where V0, V, and V* represent the volumes of alkali used at the
cofirmencement of the reaction, after time t and at the end of the
Volume V/(ml) 25.0 20.0 15.7 12.5 9.6 reaction respectively, Hece
Where V is the number of ml of potassium
pefinanganate V." - Vo : 21.05 - 9.62 : 1I.43
reqUiied to,docompose a definite volume of hydrogen peroxide
Time V_-Vt K, :
2.303 ,log v* -I/o
solution. t Vo _u

i:itiriffiirtii] 75 min 21.05 - lz.r0 : 8.95 :2'?93 ro*1-) 1 1 -al :0.003 25gmin-r
The equation for a first order reaction is
7 5 8.95

- -log-a min 2r.0s- : : 0.003 264min-r

\
2.303 I 19 13. 10 7 .ss
#rrt#:
t a- x

The volume of KMnOo used, evidently corresponds to the

183 min 21.05 - 14.75: 6.30 - 2'303lon
g3 t)
1'43 :
1
0.003 254min-r
l 6.30
undecomposed hydrogen per [Link] the volume of KMnOo
used, atzero time corresponds to the initial conc. a and the volume A constant value of kshows that hydrolysis of ethy I acetate is a
used aftertime t, corresponds to (a-*) at the time. Inserting these first order reaction.
values in the above equation, we get
when t: 10 min. k,

2'303 25 in 0.5 N HCI at35"C at various

_ -10 bn
'"" =0.0zz2Y7min-' = 0.0003r4s-r time intervals are given below. Show that the reaction is of
2o.o
first order:
when t: 20 min. k, Time (minutes) 0 10 20 30 40 oo

2.303 .toe#:0.023230min-r
2s Rotation (degree) + 32.4 +28.8 + 25.5 + 22.4 + 19.6 -11.1
- * = 0.0003g7 rs-r
::lji:t::l:::::r:l:ti:::i:lil:::i:j::l:lii:;::l:::::::i::::

when t: 30 min. k, lii$i:ffiUI+ilii:ll,

_ 2.303 .loe#=
2s The inversion of sucrose will be first order if the above data
0.0236gmin-r - 0.0003g4gs-' confirm to the equation,
, .k,: 2.303 ,lo8-
t"o - r@

when t:40 min. k, ' t r,-l*

where r0, r, and r""represent optical rotations at the commencement
- #6r#: o.o23ls7min-r = o.ooo3983s-r of the reaction after time t and at the completion of the reaction
respectively in that case
&o: ro- r_: + 32.4 - (-11.1): +43.5
The constancy of k, shows that the decompostion of HrO, in
aqueous solution is a flrst order reaction. The value of k at different times is calculated as follows:
The average value of the rate constant is 0.0003879 s-1.
 ChemicaI Kinetics 1.29
Time r, r-r
Io
k 0.1 - P': 0.047

l0 min + 28.8 bs#:o.oo8 P' : 0.053

39.9
# 6zsmin-l

2'303 - 43'5': P,oor: 0.1 +

] to ot3) = o. 180 atm.
20 min + 25.5 36.6 o.oo8 625min-r
1/ 'o"u.u
2'303
30 min + 22.4 33.5 bn43'5 : [Link] 6g4min-l
30 - 33.5 Iu-usrn*uo,N I
2.303 43 '5 : For the reaction:
40 min + 19.6 30.7 log 0.008 717 min-r 2NO+ Hr* NrO + HrO
40 30.7
The value of- dpldt was found to be 1.50 torr s-r for a pressure
The constancy of fr, indicates that the inversion of sucrose is a of 359 torr of lto and 0.25 torr s-l for a pressure of 152 torr,
first-order reaction. the pressure of H, being constant. On the other hand, when the
pressure of NO was kept constant, - dpldt was 1.60 torr s-r for
-,:,
,-::i: ::,: , : ,: ,.,, , . a hydrogen pressure of 289 torr and 0.79 torr s-r for a pressure
ILuIJ,$TRATIO,N 6 of 47 1 torc. Determine the order of the reaction.
At 1085oK, the spe(:ific rate constant of the reaction is
3.76,x 103 hourr. At what temperature will it be 1.16 x 104, if
energy of activation is 68400 cal mol-r
:ti:::tr:r::iit:taii:i[Link]i:iiii:ii:::::::l:i:::::i

[Link];iffi
ul,+iiii'i;i;;

P *o(torr) Pu,(ton) -dp/dt (torr sec-r)

.....Sut1...'......
(i) 359 Constant
Log
(t"\
r-r-
E^ (r"-r.t u ,!, (ii) 152 Constant
1.5
0.25
\t', ) 2.303R ( TrT, ) (iii) Constant 289 1.6

( (iv) Constant 147 0.79

log t_
t.t6xloa ) _ 68400 ( r, -ross) For the given reaction, we write
I [Link] x 103 )- Lffi"zl,. to8% .l
+dtl = kPIoP;,
or3.3xl-s- 1 -'oY on solvi'g' we get Tr: ll25'3oK
1085 ,7, For the constant hydrogen pressure, we may write

,,:,, 1.50 torr s-l - k (359 torr)- P;,

Iu-usrnarroru 7
The reaction given below, involving the gases is observed to
0.25 torr s-r- k (l52torr)^ P;,. On dividing, we get
be first order with rate con stant 7 .48 x 10-3 sec-r. Calculate 1.s0 ( tsg\* _l I
the time required for the total pressure in a system containing
0.2s \tsz )
I
-l

A at an initial pressure of0. I atm to rise to 0. l45atm and also

find the total pressure after 100 sec. log(1 50 I 0.25) 0.7782 _ -
(2Ae) + 4B(e) +C(e) orm:---=-
log(359 ltsz) 0.3773
::,:::::::i:::rri:ii,:i:i:i::1:i[Link]i::ii:i::i:: Similarly for the constant nitric oxide pressure we get,
|i1it fqiii,i
log(1 .60 I 0.7e) 0.306s
orn-
2A(e) + 4B(e) + C(e) log(289 lt47)--310.293s
p
^o 00 Thus, the overall order of the reaction - m+n : 3.
Po-P' 2P, P,I2 3P'
f)
I.
total
_
- D -P'+2P'+
r0-P',+2P',+P',l2Po* Juuusrn*rpn
2 9,
For the reaction:
p' : it, t4s- o. 1) = o.o3 atm C2H5I + OH- -+ CTHTOH + I-
the rate constant was found to have value of
k-ry'"r# 5.03
What is the rate constant at 305 K.
x l0-2 mol-rdm3 s-rat 289 K and 6.71mol-rdm3s-r at 333K.

t:
f
-
7y'8"roj
2.303
,"r(#) ::::::
j:ii:::::ii:it:::lii:::t:r::rii::::

iiiiii:ir#$I+iiiiii
ji:r::|:::

t-47.7 sec k, : 5.03 x l0-2 mol-l dm3 s-r at T,: 289 K

-
kr: 6.7 1 mol-r dm3s-latT r.: 333K
Arso,k-
ry,*[05) .lncl ( 6.71 )|
-
E_
u
(tt3-28e)
I |

" ( 5.03 x t0-' ) 2.303 x 8.314 [ 333 x289 )

7.48x103:#,"-(#;)
On solving we get,Eu:88.914kJ
-
 1.30 Chemistry

The rate constant at 305 K may be determined from the relation: t+ffi:iii.t.

ros
e'
k2 _ Eo (t_r) When both N, and Orare in small amount or in large excess, the
kt 2.303R [ 4 T, ) rute law obeyed will be

889 r4 11 Rate cr tAL)lOr] .'.order:1* l:2

10s(-) =
2.303 x 8.314 298 30s When N, is in large excess as compared to O, the rate law will
reduce to
On solving we get,kr:0.35 mol-rdm3 s-r
Rate a lOr].'. order w. r.t O, - 1

, ,fi*,t usTBfittou 10 order w.r.t Nr: 0

Ac has a half-life of 22.0 years with respect to radioactive
?27 Overallorder- 1+0: I
decay. The decay follows two parallel, paths, one leading to So, choice (A) is the correct answer.
?22Thand the other to 223pr. The percentage yields of these two
daughter nuclides are 2.0 and 98.0 respectively. What are the
decay con stnts (tr") for each of the separate paths?
.liriiri:il:ii*ff i:liii:i:iil:iirii:i:::i

iH*ffiifiifi

The rate constant of the decay is

lt-
, _ 0.693:_0.693
tr,, 22
If ktand krarethe rate constants of the reactions leading to222Th
and Ff", respectively we have

t- t_ 0.693 ;.
K,K^ kt
+:- 2
tz 22 kz 98
On solving for krand k, we get
kr:0.03087 f'
kr:0.00063 y-' ,liiiiffiiliili.r:i::

[Link] :k.K- c
l.2x 10-rx l.4xl}a:1.68x 10-6mole-r
L min-r
Rate: Kou,[ NO]'I Hr]
: 1.68 x 10{ x 0.52 x 0.5
- 2.1 x 10-7 mole L -r min-l
So, answer must be choice (A)

:::r:r::il::::ji:r:ii:::::i:l::r:::::ii:l:l:i::::::l:l:l:

ffiunrl1.1l:.
,:ii:;::i::,::::::ii:,:::i::,ir:,i:i::::,i:i,:,:i:i:::

For 4 moles ofNO, forme d,2 moles ofNrOs consumed in a given :iii:iiiffii:iiiiii
time interval, so the rate of consumption of NrO, must be half
In case offirst order reactiofltr,rwill remain constant independent
of the rate of formation of NO, Rate constants w.r.t. these two
of initial concentration so.
rates will also have the same relationship. So. the choice (A) is
the correct answer. 4 mole /-t --@-+ 2 mole St 20min
,l mole tl
20min l
,:'l,iig$ tlz 0.5 mole L
,' trON
The reactiorNr* Or 2NO, follows the kinetics rate o [iV, ]LOrJ . That is, after 60 minutes 0.5 mole L-t ofA will be left unreacted.
The order of reaction when both N, and Orarc in small amount, In case of second order reaction t,,, is inversely proportional to
N, is in large excess as compared to O, and both N, and Orarc initial concentration of reactant i.e., t,,, will go on doubling as
in large excess are concentration of reactant will go on getting half. That is, tr,ra
(A) 2, 2 I and (B) 2,1 and I will be constant, so.

(C) 2, I and 0 (D) 1, 1 and 0 4 mole /-t 2 mole 5-t 20mrn

,l mole L l
-?9ltn+
 Chemical Kinetics 1.31

That is, after 60 min, the concentration of R remaining unreacted I

will be 1 mole L*r I

i

.'. (c)

:ii:iii niliiirii,..tri:i:[Link]

;iitiii#fril*:iitri:: :iiii:iwLiiiE+iilii[:
.iiiiiiii$r,tilt*ii+i

,-Ea/2x5oo - l0{ :. Eo = 11 .5 Kcals

Step II, being r.d.s
.'. Option (B) is the correct choice. Rate of overall reaction : rate of step II : Il, [Or] tO]
Putting the value of [O] from the equilibrium of Stepl.
KilK"lo3)2
Rate -
lorl
.'. (B)

:i:::iiiiiiiji::j::rsi:::i{*iiir:ti:t:i

fi

-Eo -E'o loo 80

...7,= 4ooK
5OO- TI'
RT = - RT' =+

.'. (A)
;iiiiiffil';iiiiciiii:riiii
iriiii:il*ffiEli+i

From 20 Cito 1 .25 Ci, the number of half-lives involved is 4

[Link]: T - 2000
--- -500 Years
n4
A 0.693
s00
.'. (B)
iiirr..!iiii-i.i1,tla:;Y,ri;.!i; jliitii

,i#uffi#Eii,i

The rate data suggests the rate law as follows

Rate oc 1f i.e r u. Artz
.'. order - 0,5
So, D is the
.\ correct choice.

ii,iri
riiii+;*fili+#iiltliii
i+ri

For the given reaction

I dlAl dlbl I dlcl
- rate ofreacton - r-;= - = = LdTDI
; r; 3dt
As ^d[c] 1.0mol lirrsec-r
;:
#*#ffiil:i+t
-dlAl dlcl :1.0
mol lirl sec-r
=
dt dt
K -ryr,rff:ffi,"*#- r.3 86 xlo4s-r
-alal =Ldlcl- I = 0.5 mol rir,se-r
.'. (c) dt zdt 2
 1.32 Chemistry

M- 3 M- 1x1=1.5-mollirlsec-r reaction is
dt zdt 2 carried out in the
Rate - !M= !x I o.5mol lirr sec-l
2dt 2 =
kJ/mol.

riiiiii:ii:ii:li'iii:liiilili:i:ii::iiriiii

,iilXffiiiilil
By Arrhenius equation,
K- Ae-E,'/Rr
Let E^a of the reaction in absence of catalyst - x kJ/mol
.'. E^a for the reaction in presence of catalyst - (x - 20) kJ/mol
(i)
K_AeRx500
_ {i-20) (ii)
K=AeRx4oo
....,..,6.,.:2.:...'.md0,1,4..M By equation (i) and (ii)

Y
^ Rx500-^Rx400-.
-e -5oo-
A
i:!:;a:i:i:li:;rlil:ii:i:ii:!:i:l:li:ari:i:i:i:iirirlr:i

ilf
4oo
.'. x: 100 kJ/mol
,::l:iliiiffi ii:ili i:l

Let, for the reaction 2NO + Cl, + 2NOCI

Rate- K[Clr]- [NO]' (i)
Where m and n are order with respect to Cl, and n respectively
From given data I x 10-3 - K[0.05]'[0.0 5]' (ii)
3 x 10-3- K [0.15]- [0.05]' (iii)
:,:i::i,iii:,:,:,:j:::::::i:lti:ii::::::i;r,:i:::::ii:i

9 x 10-3 - K [0.05]- [0.15]" (iv) illiiliffi n1111i,

By equations 1 (ii) and (iii), m - T,: 30 + 273: 303K, Tr:60 + 273:333K

By equations (ii) and (iv) n - 2 R - 1.987 x 10-3 kcal K- rmol-r = 2 x 1 orKcal K-l mol-r
a) order with respect to NO rs 2, and w.r.t. Cl, is l. rr
r: KlAf' .'. - 2Kr = t
b) Rate expression: R - K [C12]'[NO]' 12
11,19-' El-
itan(K)- (K): . I -= K^ al Tr-7,
c) Rate constan .= -- --og - Kl
litre2mole-2sec-r
ffi=;o*1,p*y 2.303 log
RL T,T,

Eo 333 - 303
d) Rate - K[C1r]'[NO]' + loe(5): 2.303x2x10-3 333 x 303
8 [0.27' x10.4]' :
:0.265 mol lirtsec-l '.E :10.75kcallmol a

:iiii:i:!:iiiii!i:i:!:ii.:[Link]:i:r:il

..;.,..i1'1ffiun+1;il;i;

:l:::::::l:,4:i::::::::l::::,:::::::::::::::i:::::t:it:t:::::::

From the dimension ofthe rate constant it is clear that the reaction ,;.ii:.;1iffi
Untii.;lli:l;

is of flrst order
7U2 s(o)t-' (a : initial concentration)
- K_
2.303 1 For (1) 425 cr (350;rt-'r (i)
t "(t-r)
.'-
For (1) 27 5 u (540)(t-n) (ii)
-loq- 2'3o3los 1 For(iii) 941 cr (158)''- (iii)
.'. 4.5x lo-3 - , . By equation (i) and (i)
tx60^--(t-r)
On solving the equation x - 0.237
Thus after t hour [B] - 0.27 M
#= [#)'-' = LogH= (r - n)'"r#
.'. [A] - l- 0.237 : 0.763 M
: : 3.43 x 10-3 M/min
On usual solution, n -2
tate after t hour k[A]" 4.5 x l0-3 x 0.7 63
 Chemical Kinetics 1.33
:,,:,,,,,:,:,,
,J,LLggrRf;rmx,27 . For a reaction:
Bicyclohexane was found to undergo two parallel first order aA+bB+cC+dD
o Instantaneous rate:

-;lt(dtAI)_
d, )
t(dtBI)_ t(dtct)_ r(ap1\
bl dt )-;l d, )- dl d, )

,:,:::]:':,:,8,:]:r

,,,.'..,.,,1f
r::t,,,:rr::]:,::

[I.,,,
Relationship between rate of reaction and rate of disap-
pearence of reactant (rate of appearance of product).
Kr t Average rate:
Cyclohexene t(^tAI)_ r(^tBf)_ t(^tcr)_ r(4a1)
- ;1,; )- - i[ar )- ;t )- 7l d^, )
Bicyclohexane
^,
+ Graphical method for determining rate:

Methylcyclopentene

Percen tageof cyclohexe

)ne-
Kl
tA
ffix100 tRl

1.26x l0+
x 100 = 77oh
5*, Rr
tBcB
5E
tr(B
.'. o/o
of methycyclopenten :23o/o 8gR^
trq-( t
oo
O

o
(one curie gives

,:ii:iiiii;iiii:iiriiii:ii1;r:iiiiii::'

-xiffiiiiiii
A,

Letwtofl4C-Wg
(t-{
t P1

o tPl
Number of nuclides (N) : y"6.023x10'3 tr
o €
T4 +r) o
6 u
L
+) €o
tr
As -d(N)
L{
= futr/ =0'6932 xN
C)
o
g
a P
dt tr,, o B, o
U
0.6932 W tr t t2
+ 3 .7 xlOro = x-x 6.023x 1023
+
5760 x 365 x24 x 60 x 60 14 time

.'.W - 0.225 E

POINTS TO REMEMBER AvsRate:[H) =ry

o Rate of reaction (ROR)
( oA\ oA'
Rate of disappearance of reactant(appearance of products) Instantaneor
rs rate - -[* *
)= Oy
- + slope of tangent
Stoichiometric coefficient of reactant (products)
1.34 Chemistry

. Important kinetic expression for reaction of type A -+ B:

Order Zero Irt 2"d nth

Differential rate law Rate -k Rate - klAl Rate : k[A]' Rate: k[A]"

[Ao]-[A]:kt
k- [/]o l1 I 11
Integrated rate law 1n kt kt- (n
lAl lAl lAlo -r) Ay-r v);'
tr,, -lAlo Lv2-
+
ln2
tr,, _1 tr,r:
1 zn-r -l
Half life (tr,r) 2k k lAlok k(n - l) @
(tr,) tyo:|.5 tr,, tyo: 2 tr,, t,o: 3 tr,, t,o: (2"-r + l) trn

o Graphs of various order

I
vst
Order Rate vs [Al [Al vs t log [Al vs t lAl

log [A]
Rate tAl I
Zero order
TEJ
IA] t
t t

log [A]
Rate tAl
First order
tAl
tAl t t t

t t
tAl log [A]
Rate
Second order
tAl
tAl t-+ fa

Where t:0 c 0 co=+[Link]-0

[A]o + initial concentration t:t c-x nx c,[Link]-t
[A] =+ concentration at time t t:oo 0 nC C""=COnC.11tt-oo
tr,r) time taken for initial concentration of reactant to finish For any measurable property X proportional to the concentration
by 50% of reaction mixture atvarious times, following relations can be
t,ol time taken for initial concentration of reactant to finish expressed.
by 75% In terms of
o Monitoring kinetics experimently: (i) Xo and x (ii) Xo and X,
The kinetics of reaction can be followed (i.e. order, rate
xo (n-t) xo
constant etc. can be established) by measuring a property k -16 k -1r,
which changes with time. t Xr-x t nXo-Xt
e.g. (iii) X"" and X, (iv) Xo, X,, and X""
(i) Total pressure in a gaseous reaction.
(ii) Volume of a rcagent (acidic, basic, oxidising or k -16 @-t)x* k -1m ( *-- *,\
reducing agent) t n(X* - X,) t [a-x,)
(iii) Volume of a gaseous mixture (V)
where
(iv) Optical rotation (R) x 't'.
For a Reaction - = amount of reactant reacted in time
xo =+ measured property at t - 0
An+nB x t
+ measured property at t - t
 Chemical Kinetics 1.35

\ = measured property &t t : oo 0 e-Ea/Rr- Fraction of collision in which energy is greater

o Examples: (For Monitoring Kinetics Experimently) than 8".
(i) Inversion of cane sugar: r A and Eu are constant i.e. do not vary with temperature
cnlJ^zzoll (ag) +H2o g c6H12ou(a0 + c6Hlrou(aQ) E
lnk-lnA - *
Sucrose Glucose Fructose

dextro-rotatory dextro-rotatory laevo-rotatory Graph: Graphical determination of E.a

(+66.5") (*r )
(Laevo-rotatory)
1 Slope - -E
E-
.
tL-
2.303
,"*[ L -ro\ lnk e
t r*-q )

ro : rotation at time, t : 0
r, : rotation at time, t : t
LIT -+
roo : rotation at time, t : o.,

(ii) Acidic hydrolysis of ethyl acetate Temperature coefficient - t'--

kr
CH3COOC2H,+H2O H* , CH3COOH + C2H5OH
By default T: 298 K
ts-'+,"*( V* -Vo
V* _V,
Variation ofrate cons tarfiwith temparture + n lz - Eo

hR [+-;)
Vo: Volume of NaOH solution used at time, t: 0
o Endothermic and exothermic reactions:
V,: Volume of NaOH solution used at time, t: t
V_: Volume of NaOH solution used at time, t: -
Note: Here NaOH acts as a reagent.
product the amount of which can be found
standard NaOH solution. But being
t [Link]
[Link]
P.E.

AH
o Important characteristics of first order reaction:
r t,,, is independent of initial concentration. (Endo)-
I In equal time interval, reactions finishes by equal fraction.
t:0 t:t t-2t t:31....
Reactant conc. a0 &oX rox' &oX'........
x - fraction by which reaction complete in time 't'.
k t
0 Graph of ln[A] vs t is straight line with slc
)Pe -
2303
P.E. ab

t Graph of [A] vs t is exponentially decreasing.

o Zerc order:
0 tr,, of zero order is directly proportional to initial
concentration. (Exo)-
0 In equal time interval, reaction finishes by equal amount.
t:0 t:tt-2t t-31.....
Co Cr- * Co- 2x Co- 3x.... ALT_E
AII-Daf-Dab tr
o Graph of [A] vs t is straight line.
lAlo
Azerc order reaction finishes in t- o Parallel reactin: MtiB
k )>>c
o Temperature dependence: (i) Rate : (k, * k ) [A] - (differential rate law)
0 Arrhenious equation: k - A.e-Ea/Rr
r Eu :minimum energy over and above the avg. energy of (ii) k., l_Bl
reactant which must be possesed by reacting molecule for ;--rrr
collision to be succesful.
0.693
r A - frequency factor - proportional to number of collisions (iii) t,,,
per unit volume per second. kr+k,
1.36 Chemistry

k, k2
o Pseudo-order reaction:
(iv) o/oofB
- ffix100;% of C - kr+k,
x 100
Rate law + rate - k [A]' [B]'
Pseudo rate law:
rate : k, [A]'
(v) [A] : [A]o eao,+k2)t
[B] assumed constant in two cases:
(i) B in large excess
(ii) B + CATALYST
lffiffi ffiffit
Rate of Chemical Reactions lll (3) a: r, b: iii, c: (iv, ii)
(4) a: i, b: ii, c: (iv, iii)
1. For A + B + C + D; AH -- 10 kJ mol-t. The activation
energy of the fonvard reaction is 85 kJmol-l. The activation 6. According to the Arrhenius equatiofr, & straight line is to be
energy for backward reaction is kJ mol-r. obtained by plotting the logarithm of the rate constant of
( 1) 6s (2) 10s chemical reaction (log k) against
(3) 8s (4) 40 (1) (r) (2) log r
2. For the reaction zNror(s) -+ +Nor(s)
concentration of NO, increases by 2.4 x 10-2 mol L-r in
+ or(g) the
7.
(3)
+ s),"*+
Which plots will give the value of activation energy?
6 seconds. Calculate the rate of appearance of NO, and the
rate of disappearance of NrO,
(1) K versus T (2) |K [Link] T
(1) 4x 10{ mol L-r sec-',2 x l0-3 mol L-rsec-r
(2) 2 x l0-3 mol L-t sec-r ,4 x l0-3 mol L-r sec-r (3) ln K versus T (4) ln K,[Link], lT
(3) 3 x 10-3 mol L-t sec-r,3 X l0-3 mol L-r sec-r
(4) None of these
8. Given that K is the rate constant for some order of any
3. For the chemical reaction 30, + 2C, the rate of reaction at temperature T then the value of lim log K is
r -> 'o
formation of O, is 0.04 mole L-rsec-r. Determine the rate of (1) 2. 303 (2) A
disappearance of Or. (3) 2.303 A (4) log A
(1) 0.04 mol L-1 sec-r
(2) 0.08 mol L-r sec-r 9. From the following data; the activation energy for the
(3) 0. l0 mol L-r sec-r *Ir+ ZHl
reaction (callmol) H,
(4) 0.06 mol L-r sec-r I (in, K) llT, (in, K-') log,oK
769 1.3 x 10{ 2.9
4. For the reaction 2NO(g; + Hr(g) + NrO(g) + HrO(g), at 667 1.5 x 10-3 1.1
900 K following data are obseryed. (1) 4xr0a (2) 2x104
Initial pressure of NO (atm) Initial pressure of H, (atm) Rate (3)8x10a (4)3x104
0.l s 0.40 0.02
0.075 0.40 0.005 10. A study of chemical kinetics of the reaction
0.1s0 0.2 0.01 A+B + Products, gave the following data at 25"C.
Find out the rate law and order of reaction. Experiment lAl IBI d[Productsl/dt
(1) k[P*o]'[P", ]" 3 (2) k[P*o]'[Pr, ft,2 1 1.0 0. 15 4.20xt0-6
(3) k[P*o ]'[P", ]' , I (4) k[P*o ]'[Pr, ]' , o 2 2.0 0.15 8.40 x 10-6
3 1.0 0.20 5.60 x 10-6
5. The half life time for the following reactions are
Calculate the rate law
(i) H* + OH- -+ HrO, tr,r.= 10-r2 seconds
(1) K [A] (2) K [B]
32sK (3) K [A] tBl (4) None of these
(ii) Nro,(aq) ,) 2NO2(g) +
)Or(g),
11. The values of rate constant for the decomposition of NrO'
tr,r= 89 minutes
(iii) H2O(l) '*
NrO, + NrO arc 3.50 x 10-5 and 5 x l0-3 at27oC
CH.COOC2H'(1) + ) ^*).O,
and 67"C, respectively. Calculate the energy of activation?
CH3COOH(I) + C2H5OH(I), tr,r= 1000 days
(1) 14.8 kcal/mol (2) 24.8 kcal/mol
(iv) [Cr(HrO)u ]'* + I- (aq) [Cr(HrO), I]'* (3) 25.00kca1/mol (4) 34.8kcal/mo1
+ HrO(l), tr,r= 2000 years
12. An exothermic reaction A + B has an activation energy of
which is (a) fast reaction (b) slow reaction (c) moderate
17 kJlmol. The heat of the reaction is 40 kJ. Calculate the
reaction?
activation energy for the reverse reaction B + A?
(1) a: i, b: iv, c: (ii, iii)
(2) a: i, b: ii, c: (iii, iv)
(l) 60 kJ (2) s7 kl
(3) 7s kJ (4) e0 kJ
1.38 Chemistry

13. An endothermic reaction X -----+ Y has an activation energy 22. Calculate the order of the reaction inA and B
of I 7 5 kJ mol-r and the heat of reaction is 85 kJ. Find the
activation energy of the reaction Y -+ X. lAl (mol L-1) IBI (mof') Rate
(1) 70 (2) 80 0.05 0.05 1.2 x 10-3
(3) e0 (4) 100 0.10 0.05 2.4 x 10-3
14. For an endothermic reaction where AH represents the
0.05 0.10 1.2 x l0{
enthalpy of the reaction in kJ/mol; the minimum value for (l) I and 0 (2) I and 1
the energy of activation will be (3) 0 and I (4) 0 and 0
(l) Less than AH (2) Zero
(3) More than AH (4) Equal to AH 23. For a chemical reaction A + B -+ product, the order is one
with respect to each A and B. Value of x and y from the
15. The rate of reaction by 2.3 times when the
increases given data is:
temperature is raised from 300 K to 310 K. If K is the rate
constant at 300 K then the rate constant at 310 K will be Rate (moUl/sec.) (A) (B)
equal to 0.10 0.20M 0.0s M
(1) 2K (2) K 0.40 oo; *
(3) 2.3 K (4) 3 K2 0.80 o+tHa
(1) 0.20,0.80 (2) 0.80, 0.40
16. If concentration of reactants is increased by x then the K (3) 0.80, 0.20 (4) 0.40, 0.20
will become
(1) ,r;
KK (2) 24. The following mechanism has been proposed for a reaction.
; 2A+B+D+E
(3) K+x (4) K A+B-+C+D(slow)
A + C + E (fast) The rate law expression for the
17. If the concentration units are reduced by n times then the reaction is
value of rate constant of first order will (1) r=KlAl'[B] (2) r=KtAltBl
( 1) increase by n times (2) decrease by factor of n (3) r = K [A]' (4) r =K tAl tcl
(3) not change (4) none of these
25. The reactions 2NO * O, + 2NO2
18. Which is used in the determination of reaction rates. 2CO * O, zCOz look to be identical, yet the first is
(1) Reaction temperature (2) Reaction concentration faster than -+
the second. The reason is that
(3) Specific rate constant (4) All of these (1) The first reaction has lower enthalpy change than the
second
19. A gaseous reaction, 2A(g) + B(g) ------) ZC(g), shows a (2) The first reaction has lower internal energy change than
decrease in pressure from 120 mm to 100 mm in 10 minutes. the second
The rate of appearance of C is (3) The first reaction has lower activation energy than the
(1) 2mm/min (2) 4mm/min second
(3) 10 mm/min (4) 12 mm/min (4) Nitric oxide is less stable than carbon monoxide
20. For a gaseous reaction, following data is given 26. For which of the following reaction krrolkroo would be
A -+B, kr= lQrs. and C -+ D, maximum?
kr= l0r4 the temperafure at which kr= kzis (1) A+ B + C;8,= 50 kJ
(1) 1000 K (2) 2000 K (2) X + Y -----+ Z;8,= 40 kJ
(3) 868.82 K (4) 434.2K (3) P+ Q --+ R; E, = 60 kJ
(4) E+F--G;E,= l00kJ
21. Forahypothetical reaction;A+ B + C the following data
was obtained in three different experiments:
27 . The rate of a chemical reaction doubles for every l0oc rise
in temperature. If the temperature is increased by 60"C, the
IAI tBI Rate or reaction rate of reaction increases by about
(mol L-1) (mol L-') (mol L-r min-') (1) 20 times (2) 32 times
0.01 0.01 x 10-4
1.0 (3) 64 times (4) 128 times
0.0 r 0.03 9.0 x 10-4
28. At a certain temperafure, the first order rate constant k, is
0.03 0.03 2.70 x l0-3
found to be smaller than the second order rate constant kr.
Suggest rute law
If the energy of activation E, of the first order reaction is
(l) r=KlAl'[B] (2) r=K[A] [B]' greater than the energy of activation E, of the second order
(3) r=K[A] tBl (4) None of these reaction, then as the temperature is raised
 Chemical Kinetics 1.39
(l) krwill increase faster than k, (l) r, Kl/rq Q) r' K'
(2) will increase faster than krbutwill always remain
fr, less (3) II, KrAq (4) II, Kl/I(, + L
than k,
(3) fr, will increase faster than k, and become equal to k, 37. TWo reaction A -+ products and B + products have rate
(4) fr, will increase faster than k, and become great er than k, constant KA and KB at temperature, T and activation
energie s E nand E, reipectively. If Kn) K, and E n a E, and
29, The hypothetical reaction A2 + 82 -> 2AB follows the assuming that A for both the reaction is same then:
mechanism as given below (1) At higher temperature Knwill be greater than K,
Ar3A+A(fast) (2) At lower temperature Kn and K, will differ more and
A+BTJAB+B(slow) Kn) K,
A + B -+ AB (fast) (3) As temperature rises K, and K, will be close to each
The order of the over all reaction is
other in magnitude
(1) 2. (2) I (4) All of these
(3)
+ (4) o
38. The accompanying figure depicts the change in
30. For a reaction of the type A + B -> products, it is observed concentration of species X and Y for the reaction X -+ Y
that doubling the concentration of A causes the reaction as a function of time the point of intersection of the two
rate to be four times greater, but doubling the amount of curyes represents
B does not affect the rate. The rate equation is
(1) Rate = K[A]tBl (2) Rate = KlAl2
(3) Rate = KlAl'[B] (4) Rate = KlAl'[B]'
x
31. Point out incorrect statement.
(l) Rate law is an experimental value
(2) Law of mass action is a theoretical proposal
(3) Rate law is more informative than law of mass action Y
for developing mechanism
(4) Rate law is always different from the expression of law Time Fig.
of mass action. (l) (2) t,o
t,,,
32. The acid catalysed ionrzation of g-hydroxy butyric acid (3) tr,, (4) None of these
proceeds as a reversible reaction. Which is first order in both
the fonvard and backward steps: 39. If the first order reaction involves gaseous reactants and
The rate is given by gaseous productS the units of its rate arc
(l) K,(A) (2) -K,(B) (l) atm (2) atm sec,
(3) K,(A) - Kr(B) (4) A11 of these (3) atm sec-r (4) atm2 sec2
33. For a certain reaction, a plot of against time t, yields a 40. Plot of log(a - x) versus time t is a straight [ine. This
straight line. C, and C are concentrations of reactant at t - 0 indicates that the reaction is of
and t = t respectively. The order of reaction is ( I ) second order (2) first order
(1) 3 (2) Zero (3) zero order (4) third order
(3) I (4) 2
41. The half life period for catalytic decomposition of AB, at
34. The rate law of the reaction A + 28 -> product is given by 50 mm is found to be 4 hr and at 100 mm it is ztv. The order
4H = K[A]'tBl. of reaction is
If A is taken in large excess, the order of (1) 3
dt
L JL J
(2) I
the reaction will be (3) 2 (4) 0
(1) Zerc (2) I
(3) 2 (4) 3 42. For a chemical reaction Y, + 22 -+ Product, rate controlling
step is
35. A drop of solution (volume 0.05 mL) contains 3.0 x 10-6 Y+ Y2Z + Q If the concentration of Z is doubled, the rate
moles of H*. If the rate cgnstant of disappearance of H* is of reaction will
1.0 x 107 mol litre-lsec-1. How long would it take for H* in (1) remain the same (2) lbecome four times
drop to disappear? (3) become 1.414 times (4) ibecorne double
(l) 6 x 108 sec (2) 6 x 10-7 sec
(3) 6 x lO-e sec (4) 6 x 10-10 sec 43. The rate constant of a first order reaction depends on the

36. For a chemical reaction A Products, the rate of

(I )
Concentration of the reactant
(2) Concentration qf the product
disappearance of A is given by:-4 (3) Time
At low Co, the reaction is of the.....order with rate constant (4) Temperature
(Assume K, ,Krare lesser than l)
t.4O Chemistry

44. For the decomposition of NrOr(g) it is given that 52. For a reaction for which the activation energies of forward
ZNrOr(S) -+ 4NO2(g) + Or(S) activation energy = Eo, and reverse reactions are equal:
(1) AH-O (2) AS=0
+ 2No2(g) +
N2os(g) activation energy -E:then
(3) The order is zero
lorrr) (4) There is no catalyst
(1) Eo= 2E: (2) E,> E:
(3) E,<E: (4) E,=Ei 53. An exothermic reaction X + Y has an activation energy of
30 kJ mol-r. If energy change (AE) during the reaction is
45. Rate of formation of SO, according to the reaction -20 KJ, then the activation energy for the reverse reaction is
2SO2 + Oz -+ 2SO3 is 1.6 x 10{ [Link]-r Hence rate at (r) 10kJ (2) 20H
which SO, reacts is (3) 50 kJ (4) -30 kJ
(l) x
1.6 l0-3 kg. min-t (2) 8.0 x 10-4 kg. min-t
(3) 3.2x 10-3 kg. min-l (4) 1.28 x 10-3 kg. min-r 54. The half life of a first order reaction is 10 min. If initial
amount is 0.08 moUlit. and conc. at some instant is
46. The rate constant k, for the reaction,
0.01 moVlit. then / =
N2os(g) + 2NO2(g) + Or(g) is 2.3 x 10-2 s r.
(l) 10 min (2) 30 min
Which equation given below describes the change of [NrOrl (3) 20 min (4) 40 min
with time?
[Nror]o and [NrOr], is conc. of NrO, initially and attime t. 55. For which of the followirg, the units of rate constant and
(1) [NrOr], = fNrOrlo + kt rate of the reaction are same
(2) [Nror]o = [NrOr], - A (I ) First order reaction (2) Second order reaction
(3) log [NrOr], = logro [N2Os] o- kt
(3) Third order reaction (4) Zero order reaction
(4) ln - kt 56. Arrhenius equation may be written as:
.
47 In the first order reaction 7 5o/o of the reactant disappeared in
1.388 h. Calculate the rate constant of the reaction.
(1) 1 s-r (2) 2.8 x lOa s-l
(r)
#(hK)=- # e) #onK)=- #
(3) 17.2 x 10-3 s-r (4) 1.8 x l0-3 s-r (3)
*(hK)-+ # (4)
*(hK):#
48. In the sequence of reaction
*, >C ",>D; 57. A reagent undergoes 90% decomposition in 366 min.
A+B According to first order reaction. Its half life is
K, > K, , K,, then the rate determining step of the
reaction is (,) 366x,oo(#) (D366[ffi)
(l) A-+B (2) C-+D
(3) B+C (4) A+D
(3) (4) 183
*
49. For a general chemical change 2A+ 38 + products, the rate
of disappearance of A is r,. anri of B is rr. The rates r, and r,
58. The half life for a reaction is of temperature
are related as
(1) independent
(l) 3rr=2r, (2) rr=tz (2) increased with increase
(3) 2r, = 3r, (4) rr' = 2r] (3) decreased with increase
(4) increased or decreased with increase
50. From different sets of [Link] of tr,, at different initial
concentrations say 'A' for a given reaction, the lt r,, x af is
59. 2A + Product, follows the first order kinetics. If the
found to be constant. The order of reaction is
half life period of the reaction at [A],,n,"r= 0.2 mol L-t is
(r) 0 (2) 1
20 min. then the value of rate constant would be
(3) 2 (4) 3 (1) 4 sec. (2) 20 sec.
51. The reaction 2NrOr(g) + 4NO ,(g + Or(S)
(3) 4Lmol-l min.-l (4) None of these
is first order with respect to NrOr. Which of the following
graph would yield a straight line:
Factors Affecting Rate of Reaction llr
(1) log(P*,o, ) versus time with -ve slope
60. Dinitrogen pentoxide decomposes as follows:
(2) (P*,o, )-r versus 'time
NrO, + 2NO ,*IO,
Z2
(3) (P*,o, ) versus tfune

(4) log(P*,o, ) versuri time with +ve slope rf d[Nro, ]

ll-
= k'[NrOr]
dt
 Chemical Kinetics t.4t

qP =k"[Nro, )dlo'] = l(" [NrOr] Derive a relation

67. Which of the following statement is correct for a reaction
X+ 2Y + Product
dt dt
(1) The rate of disappearance of X = twice the rute of
in l{, l{' and l{" .
disappearance of Y.
k' k' k"'
\'/ _2 = _3 = 4
fl) (2) (li)' - l{' = l{" (2) The rateof disappearance of X - I2 rate of appearance
of products
(3) 2t{ = t{ - 2l{' (4) k'--+--zk"' (3) The rate of appearance of products
- = + the rate of
2
disappearanceofY
(4) The rate of appearance of products
^ = + the rate of
61. The rate of change in concentration of C in the reaction disappearanceofX 2
2A + B -+ 2C + 3D was reported as 1.0 mol L-t sec-r.
68. Consider a chemical reaction 2A + B
Calculate the reaction rate.
(1) 0.05 mol L-r. sec-r (2) 0.01 mol L-l sec-l reactant A will decrease at:
--+ ArB. The
(3) 0.5 mol L-t sec-r (4) None of these (1) The same rate at which B will decrease
(2) TWice the rate at which B will decrease
62. For a rcaction 3,A,' + products, it is found that the rate of (3) Half the rate at which B will decrease
reaction doubles, if concentration of A is increased four (4) A11 of the above
times, the order of reaction will be
69. For the reaction, NrO, 2NO2 *
'2210,
(1) 1 (2) Iz
d[Nro,] d[Nor]
(3) 2 (4) 3 Given - dt
- Kl[NrOr], dt
=Kr[NrOr]

63. A first order reaction takes 69.3 minute for 50Yo completion. dlo,l
= Kr[NrOt]
How much time will be needed for 80% completion? dt
(1) 160.97 minutes (2) 170.97 minutes The relation between K, ,Krand I! it
(3) 150.97 minutes (4) 10.703 minutes (l) ZKr=Kr=4K, (2) K, = L = K,
(3) 2Kr= 4Kr= K, (4) None of these
64. The reaction -+ 4NO2 + Oz shows an increase in
2N2Os
concentration of NOrby 20 x 10-3 mol L-l in 5 s calculate 70. The rate constant K, of areaction is found to be double that of
the rate of appearance of NOr. rate constant I! of another reaction. The relationship between
(l) 2 x l0-3 mol L-l sec-r (2) 4 x 10-3 mol L-r sec-r coffesponding activation energies of the two reactions at same
(3) I x 10-3mol L -r sec-l (4) None of these temperature (E, and Er) can be represented as
(1) E, , E, (2) E, ( E,
65. Consider the chemical reaction: (3) E, = E, (4) E, = 48,
N2(g) +:Hr(s) zNH,(s)
71. Inthe reaction ofNO byH, itwas observedthat equimolecular
The rate of this reaction can be expressed in terms of time of mixture of gases at 500 mm was half changed in 100
concentration of Nr(g;, Hr(g) or NH3(g). Identiff the correct seconds. In another experiment with an initial pressure of
relationship amongst the rate expressions. 250 ffiffi, the reactions was half completed in 200 seconds.

(1) Rate=-ry=- !dl\; =1dtNl'l Calculate the order of reaction

(1) 1
dt 3dt 2 dt (2) 2
(3) 3 (4) 4
3dly) 2d[NH3 ]
(2) Rate = _ ryf
dt =_
dt - dt 72. For the reaction 2SO2 + Oz -- 2SO3, the rate of
dH'l I I drNIH3I disappearance of O, is 2.0 x 10-4 mol L-rs-1. The rate of
(3) Rate= ry= 2
dt = 3dt dt
appearance of SO, is
(1) 2.0 x 10-4 mol L-r s-r (2) 4.0 x 10-4 mol L-r s-r
dN-H,l (3) 1.0 x l0-4 mol L-r s-r (4) 6.0 x
(4) Rate=_jrryd=_
dt
ry-
dt dt
t0-4 mol L-r s-r

73. For a reaction A + B + C. If the reaction are of first order

then is equal to
6;6. In the formation of sulphur trioxide by the contact process (r) -kzlBl (2) +k [A]
ZSOr(S) + Or(g) + ZSO,(S) The rate of reaction is (3) fr, [A] -K2 tBl (4) k, [A] + K, [Bl

expreSsedaS-ry_2.5x10{[Link] 74. Which of the following rate law has an overall order of 0.5
dt for reaction involving substances x, y and z?
disappearance of (SO2) will be (l) Rate - K (C,) (C,) (C,)
(l) 5 x lOa mol L-r s-l (2) -2.25 x lOa mol L-l s-r (2) Rate - K (C,)o'(Cr)o'(C,)o t
(3) 3.75 x l0{ mol L-l s-r (4) 50.0 x 10a mol L-r s-r (3) Rate - K (C,)" (C,)-'(C,)'
(4) Rate - K (C,XC,)" I (C
r)2
1.42 Chemistry

75. A chemical reaction involves two reacting species. The rate (l) Doubled on doubling the concentration of NaOH
of reaction is directly proportional to the conc. of one of (2) Halved on reducing the concentration of RCI to half
them and inversely proportional to the concentration of the (3) Decreased on increasing the temperature of reaction
other. The order of reaction is (4) Unaffected by increasing the temperature of the
(1) 1 (2) 2 reaction
(3) Zero (4) Unpredictable
82. The decomposition of NrOs occurs as,
76. For the reaction Ur(S) + Brr(g) -+ 2HBr(g), the experimental 2N2O5 + 4NO r* C2, and follows first order kinetics; hence
data suggests, Rate - K [H2] lBrr)%.The molecularity and (1) The reaction is bimolecular
order of reaction for the reaction is l
(2) The reaction is unimolecular
(1) 2 and2 respectively (2) 2 and li resnectively (3) tr,rn ao
(4) None of the above
(3) t)ana2 respectively (4) tlanar] ,.rpectively
83. In a first order reaction the concentration of the reactant is
decreased from 1.0 M to 0.25 M in 20 min. The rate constant
77. Select the rate law that coffesponds to the data shown for of the reaction would be
the following reaction A + B -+ C (1) 10 min-' (2) 6.931 min-'
Experiment lA] IB] Initial rate (3) 0.6931 min-l (4) 0.06931 min-l
I .0120 0.035 0.10
84. In a first order
2 0.024 0.070 1.6
reaction the al(a - x) was found to be 8 after
10 minute. The rate constant is
3 0.024 0.03s 0.20
4. 0.012 0.070 0.80 ,1 \ Q.303 x 3log 2) ,^\ (2.303 x 2log 3)
\r, \Lt
(1) Rate = K[B]t (2) Rate = K[B]o 10 l0
(3) Rate = KlAl[B]' (4) Rate = KlAl'[B]' (3) 10 x 2.303 x2log3 (4) 10 x 2.303 x3log2
78. In a certain gaseous reaction between X and Y, X + 3Y -+ 85. The reaction,
XY, The initial rates are reported as follows:
lxl tYI Rate NrO,(in CClo) + 2NO2 * lOr(g)
"2
0.1 M 0.1M 0.002 Ms-r
is first order in NrO, with rate constant 6.2 x 10{s-r. What is
0.2 M 0.1 M 0.002 Ms-r the value of rate of reaction when [NrOr] = 1.25 mol L-L?
0.3 M 0.2M 0.008 Ms-r (l) 7 .75 x 10{ mol L-r s-r (2) 6.35 x l0-3 mol L-r s-r
0.4 M 0.3 M 0.018 Ms-t (3) 5.15 x 10-5 mol L-rs-r (4) 3.85 x 10{mol L-rs-r
The rate law is
(1) r=K[X][YI' Q) r=K[X]'[Y]' 86. For the reaction 4A + B + 2C + 2D
(3) r=K[X]tYl (4) r=[X]"[Y]' The incorrect statement is:
(1) The rate of disappearance of B is one fourth the rate
79. Select the law that coresponds to date shown for the of disappearance of A
following reaction 2A + B + C+D (2) The rate of appearance of C is half the rate of
Experiment IAI tBI Initial rate (mol L-r min-t) disappearance of B
I 1 (3) The rate of formation ofD is halfthe rate of consumption
0. 0.1 7.5x10-3
ofA
2 0.3 0.2 x l0-2
9.0
(4) The rates of formation of C and D are equal
3 0.3 0.4 3.6 x l0-r
4 0.4 0.1 3.0 x l0-2 87. Which of the following plot is in accordance with the
(1) Rate = K[A]'[B] (2) Rate = K[A][B]' Arrhenius equation?
(3) Rate = KlAltBl' (4) Rate = KlAltBl
(l) (2)

80. The inversion of cane sugar proceeds with half life of 600 log K log K
minute at pH = 5 for any concentration of sugar. However, /
if pH = 6, the half life changes to 60 minute. The rate law T 1

expression for sugar inversion can be written as T

(1) r - klsugarl2 [H*]o (2) r - klsugarl' [H*]o
(3) (4)
(3) r - klsugarJ' [H*]' (4) r - klsugarl0 [H*]'
log K K
81. The rate for the reaction
RCI + NaOH (aq) + ROH + NaCl 1 1

is given by rate = K, [RCl] The rate of the reaction is T T

 Chemical Kinetics !.43

Rate Equation 97. K for a zero order reaction is 2 x 10-2 mol L-r sec-r. If
the concentration of the reactant after 25 sec is 0.5 M, the
88. The minimum energy for molecules to enter into chemical initial concentration must have been
reaction is called
(l) Kinetic energy (2) Potential enerry
(l) 0.s M (2) [Link] M
(3) Threshold energy (4) Activation energy
(3) 12.s M (4) 1.0 M
98. For an elementary process 2X + Y -> Z + W, the
89. An endothermic reaction A ---* B have an activation
molecularity is
energy 15 kcaVmol and the heat of the reaction is 5 kcallmol.
The activation energy of the reaction B A is
(1) 2 (2) I
(1) 20 kcaVmol (2) 15 kcal/mol
(3) 3 (4) Unpredictable
(3) 10 kcal/mol (4) 0 kcal/mol 99. Given that for a reaction of nth order, the integrated rate
90. In a first order reaction A + Products, the ratio of a and equation is: where C and C0 &re the concentration of
reactant at time t and initially respectively. The t,o dnd tr,,
(a - x) was found to be 8 after 60 minutes. Calculate the are related as (t,ois time required for C to become Crl4):
rate of the reaction in moles of A reacted per minute, If its -' + 1]
concentration is 0.1 mol L-l
(1) t,o= tu2l2" (2) tru= tuzlz"- t - l]
(1) 5.566 x 10-3 mol L-rmin-r (3) t,o= ty2l2n *' + 1] (4) t,o= tilzl2" *, + l]
(2) 3.466 x 10-3 mol L min
100. The rateconstant of a first order reaction is- 4 x l0-3 sec-r.
(3) 4.366 x l0-3 mol L-r min-l
At a reactant concentration of 0.02 M, the rate of reaction
(4) 3.466 x 10-3 mol L-rmin-r
would be
91. For a zero order reaction k - I x l0-3 mol L-l s-r. If initial
(l) 8x10-sMsec-r (2) 4x10-3Msec-r
concentration ofthe reaction is 1.0 mol L-', the concentration
(3) 2xlO-tMsec-r (4) 4x l0-tMsec-r
after 10 minutes would be 101. 75% of a first order reaction was found to complete in
(l) 1 x 10-2 mol L-l (2) 0.6 mol L-t 32 min When will 50% of the same reaction complete?
(3) 0.4 mol L-' (4) 1.0 mol L-' (1) 24 min (2) 16 min
(3) 8 min (4) 4 min
92. The reaction
102. A first order reaction has a half life period of 69.3 sec.
2NO + Brr-+ 2NOBr
At 0.10 mol L-r reactant concentration rate will be
follows the mechanism given below (l) l0-4 M sec- (2) l0-3 M sec-r
I. NO + Br, NOBr, (Fast) (3) lO-t M sec-' (4) 6.93 x 10-t M sec-r
II. NOBr, +-NO + 2NOBr, (Slow)
The overall order of this reaction is 103. What fraction of a reactant showing first order remains
(r) 2 (2) I after 40 minute if tr,ris 20 minute?
(3) 3 (4) o
( )
1
(2);
4
93. 99% of a first order reaction was complete in 32 min. (3 )
1
(4) |
When will 99.9% of the reaction complete? 8 6
(U 50 min (2) 46 min
(3) 49 min (4) 48 min 104. For a first order reaction A -> products, the rate of
reaction at [A] = 0.2 M is 1 x 10-2 mol L-tmin-r. The half
94. Time required to complete a half fraction of a reaction life period for the reaction is
varies inversely to the concentration of reactant then the (1) 832 min (2) 440 sec
order of reaction is (3) 416 min (4) 14 min
(r) 0 (2) I
(3) 2 (4) 3 105. The acid hydrolysis of ester is
( 1) First order reaction

95. The rate law for the single step reaction 2A + B -+ 2C, is (2) Bimolecular reaction
given by (3) Pseudo unimolecular reaction
(1) Rate = KlAltBl (2) Rate = K[A]'[B] (4) All of the above
(3) Rate = K[2A]tBl (4) Rate = K[A]'[B]"
106. The half life for the first order reaction
96. For the reaction A + B + Products, it is found that the
* lO, is [Link] 30oC. Starting with
NrO, -+ 2NO,,21 10
order of A is 2 and of B is 3 in the rate expression. When
concentration of both is doubled the rate will increase to g of NrO, how many grams of NrO, will remain after a
(1) 10 times (2) 6 times period of 96 hours?
(3) 32 times (4) 16 times (l) r.25 s (2) 0.63 g
(3) r.77 s (4) 0.5 e
1.44 Chemistry

107. What is the half life of a radioactive substance if 87 .5% (1) 2 (2) 3
of any given amount of the substance disinte grate in (3) 0 (4) 1
40 minutes?
(1) 160 min (2) l0 min 115. The rate constant for a second order reaction is 8 x 10-5 M-t
(3) 20 min (4) 13 min 20 sec min-r: How long will it take a I M solution to be reduced to
0.5 M?
108. For a given reaction of first order it takes 20 minute for (1) 8.665 x 103 min (2) 8 x l0-3 min
the concentration to drop from I M to 0.6 M. The time (3) 1.25 x 10a min (4) 4 x l0{ min
required for the concentration to drop from 0.6 M to
0.36 M will be 116. For a reaction:
(l) More than 20 min (2) Less than 20 min A-+product, rate law is - ry= K(A)o
(3) Equal to 20 min (4) Infinity dt\
The concentration of A left after time / when r = I is
109. When ethyl acetate was hydrolysed in presence of 0.1 N K
HCl, the rate constant was found to be 5.40 x 10-s sec-r. [A]o
(1) (2) (A)o.e
But when 0.1 N H2SO. was used for hydrolysis, the rate e
constant was fond to be 6.25 x 10-s sec-l. Thus, it may be
concluded that (3)ry (4)#
(1) H2SO4 is stronger than HCI
(2) H2SO4 is weaker than HCI
(3) H2SO4 and HCI both have the same strength 117. Unit of frequency factor A in: K - Ae-'''*t is
(4) The data are not sufficient to compare the strength of (1) time-r
H2SO4 and HCl (2) mole litre-l time-r
(3) litre mol-r time-r
K1
B (4) dependent of order of reaction
1lo. For a first order reaction oG C
which of the
following relation is not correct? 118. The steady state concentration of the activated molecules
111 [A*] in the following sequence of steps is given by:
(1) K-K, +L (2) I

[A+A,A*A*,A* +A2A]
t, -r-
Tt x2
(1) k2lAltk' (2) ktl/^)tk2
(3)
*=(*),.[#), (4)
*=+.+ (3) k,kzl[) (4) \ k2tl[7

119. A graph between tr,, and conc. for nft order reaction is a
111. In the following first order completing reactions. straight line. Reaction of this nature is completed 50% in
A + Reagent + Product, B + Reagent + Product l0 minutes when conc. is 2 mol L-r. This is decomposed
The ratio of K,/I(, if only 50% of B will have been reacted, 50% rn t minutes at 4 mol L-t n and t are respectively
When 94% of A has been reacted is
(r ) 4.06 (2) 0.246
(3) 2.06 (4) 0.06
1
ll2. The rate constant for a reaction is tv,

10.8 x l0-5 mol L-r s-r The reaction obeys

( 1) First order (2) Zero order
;-{3) Second order (4) None of these
conc.
113. A A decomposes in solution following the first
substance
order kinetics flask I contains I L of I M. solution of A (l) 0,20min (2) l, 10 min
and flask II contains. 100 ml of 0.6 M solution. After (3) l,20min (4) 0, 5 min
8 hr the concentration ofl in flask I becomes 0.25 M, what
will be the time for concentration ofA in flask II to become 120. For a reaction A + B -+ products, the rate of the reaction was
0.3 M. doubled when the concentration of A was doubled, the rate
(1) 0.4 hr (2) 2.4hr was again doubled when the conc. ofA and B were doubl,ed
(3) 4.0 hr (4) 4.2hr the order of the reaction with respect to A and B are:
(r) 1, 1 (2) 2,0
ll4. The rate constant (K) for the reaction 2A + B + product (3) l, 0 (4) 0, l
was found to be 2.5 x l0-s L mol-r sec-r after 15 sec,
2.60 x 10-5 L mol-r sec-r after 30 sec and 2.55 x 10-s L l2l. Which of the following curves represents a I't order
mol-r sec-r after 50 sec. The order of reaction is reaction?
 Chemical Kinetics 1.45
(1) (2)
(1) l0 2.303 x 10
log (a-x) \ / 2.303R x298x308 (2)
298 x 308R
log (a-x)

f--) ,.\ 0.693R x l0

1/t+ (J,, (4)0.693R x298 x 308
(3) (4) both (1) and (3) 290 308 lo
"
129, Which of the following statement is false?
( 1) A fast reaction has a larger rate constant and short
a+ half life
(2) For a first order reaction, succession half lives are
122. The energy of activation of a forward reaction is 50 kcal. equal
The energy of activation of its backward reaction is (3) For a first order reaction, the half life is independent of
(1) Equal to 50 kcal concentration
(2) Greater than 50 kcal (4) The half life of a reaction is half the time required for
(3) Less than 50 kcal the reaction to go to completion
(4) Either greater or less than 50 kcal
130. For producing the effective collisions, the colloiding
123. If the rate law for a reaction A + B -) product is molecules must posses
rate = K[A]' [B]', which one of the following statements is
. (1) A certain minimum amount of energy
false? (2) Energy equal to or greater than threshold energy
(l) If tBl is held constant while tAl is doubled, the (3) Proper orientation
reaction will proceed trvice as fast (4) Threshold energy as well as proper orientation of
(2) If [A] is held constant while tBl is reduced to one collision
quarter, the rate will be halved
(3) If tAl and tBl are both doubled, the reaction will 131. A reaction is of first order. After 100 minutes 75 g of the
proceed 8 times as fast reactant A are decomposed when 100 g are taken initially,
(4) This is a third order reaction calculate the time required when 150 g of the reactant A are
decomposed, the initial weight taken is 200 gm
124. If the first order reaction involves gaseous reactants and (1) 100 minutes (2) 200 minutes
gaseous products, the units of its rate are (3) 150 minutes (4) 17 5 minutes
(l) atm (2) atm sec
(3) atm sec-r (4) atrrf sec2 132. The activation energy for a chemical reaction depends
upon
125. The expression which gives life of I* order reaction is (l) Temperature
lrn
(2) Nature of reacting species
(1)#,"*1 (2)rylog3 (3) Concentration of the reacting species
(4) Collision frequency
2.303 1
(3) log
K 4 133. For gaseous reaction, rate = f[A] tB]. If volume of

126. The rate ofreaction increases by the increase oftemperafure container is reduced to 1 of initial, the rate of the reaction
4
because will be times of initial.
(1) Collision is increased
(2) Energy of products decreases
(1) (2) 8
*
(Threshold energy) increases
(4) Mechanism of a reaction is changed I
(3) (4) 16
T6
127. The specific rate constant of a first order reaction depends
on the 134. Correct expression for the flrst order reaction is
(1) Conc. of the reactant (2) Conc. of the product (1) c, = co ek" (2) c, ek" = co
(3) Time (4) Temperature
co C,
128. For a certaingaseous reaction a 10o C rise of temperature (3) ln
C,
--ki (4) ln
co
-kJ
from 25" C to 35o C doubles the rate of reaction. What is
the value of activation energy?
1.46 Chemistry

Pseudo First Order:,, Reaction lll 142. The following data were obtained at a certain temperaflre
for the decomposition of ammonia
135. The rate constant; the activation enerry and the Arrhenius p(mm) 50 100 200
parameter of a chemical reaction at 25"C are 3 x l0{ sec-l;
104.4 kJ mol-l and 6.0 x l0r4 sec-r respeetively, the value tr,, 3.64 1.82 0.91

of the rate constant as T + "" is. The order of the reaction is

(1) 2 x sec-'
108 (2) 6 x 1014 sec-r (l) o (2) I
(3) Infinity (4) 3.6 x 1030 sec-r (3) 2 (4) 3
136. The rate of certain hypothetical rqaction 143. A reaction is found to have the rate constant x sec-r by what
A + B + C + products is given by factor the rate is increased if initial conc. of A is tripled
-o!l) = KlAf (1) 3 (2) e
"= dt- r\Lr- 13f tcl+ (3) x (4) Remains same
The order of the reaction is
(1) I (2)
I 144. In a reaction A + B -+ products. Keeping tA] constant
2 if [B] is doubled rate becomes double and keeping tBl
l3 constant if [A] is doubled, rate becomes four times. The
(3) 2 (4)
t2 order of reaction is
137. A substance undergoes a first order decomposition. The (l) 0 (2) I
decomposition follows two parallel first order reaction. (3) 2 (4) 3
The percentage distribution of B and C are
(l) c
8a%B,20oh (2) 76.83%B,23.t7ohc 145. The activation energy for the forward reaction X + Y is 60
(3) 92%8,80 C (4) 6g%B,32ohc kJ mol-r and AH is 20 kJ mol-l. The activation energy for
the backward reaction Y + X is
138. A first order reaction is carried out with an initial (l) 80 kJ mol-r (2) 40 kJ mol-r
concentration of 10 mole per litre and 80% of the reactant (3) 60 kJ mol-r (4) 20 kJ mol-r
changes into the product. Now if the same reaction is
carried out with an initial concentration of 5 mol per litre 146. The rate of reaction A + B + Products is given by the
for the same period the percentage of the reactant changing equation,r-k tAl tBl
to the product is If B is taken in large excess, the order of the reaction would
(r) 40 (2) 80 be
(3) 160 (4) Cannot be calculated (r) 2 (2) I
(3) 0 (4) unpredictable
139. At the point of intersection of the two curyes shown, the
conc. of B is given by . for reaction, A B:
tu -+ Temperature Dependence of a Reaction
t
o 147. In a catalytic reaction involving the formation of ammonia
c
o by Haber's process N2 + 3H, 2NH3 the rate of
O
appearance ofNH, was measured as 2.5 x l0-4 mole L-r s-r.
time
The rate of disappearance of H, will be
nAo
(l) (2) -A' (1) 2.5 x 10-4 mol L-r s-r (2) 1.25 x 10{ mol L-r s-r
2 n-l
(3) 3.75 x l0{ mol L-r s-r (4) 5 x 104 mol L-r s-r
nAo
(3) (4)(*')", 148. Activation energy of a reaction is
n*l
(1) The energy released during the reaction
140. If a reaction with tr,, = 69.3 seconds; has a rate constant (2) The energy evolved when activated complex is formed
l0-2 per second the order is (3) Minimum amount of energy needed to overcome the
(r) 0 (2) I potential barrier of reaction
(3) 2 (4) 3 (4) The energy needed to form one mole of the product

l4l. The reaction mechanism for the reaction P -+ R is as 149. A large increase in the rate of a reaction for a rise in
follows: temperafure is due to

P "' (1) increase in the number of collisions

P + 2Q (fast);2Q + > R(slow)
(2) increase in the number of activated molecules
the rate law for the main reaction (P + R) is
(3) lowering of activation energy
(t) [Q]
K,[P] Q) K,rqlPl
(3) K,rqlPl2 (4) r,r![al (4) shortening of the mean free path
 Chemical Kinetics 1.47
150. Rate of which reactions increases with temperature 160. For a certain reaction of order n the time for half change
(1) Of any reactions tr,ris given by: tr,r= where K is rate constant and Co is the
(2) Of exothermic reactions initial concentration. The value of n is
(3) Of endothermic reactions (1) 1 (2) 2
(4) Of None of these
(3) o (4) 0.s
151. The rate of a chemical reaction doubles for every 10oC rise
in temperature. If the temperature is increased by 60oC, the
161. Which statement is incorrect?
rate of reaction will increase by (1) Half life of a first order reaction is independent of
(1) 20 times (2) 32 times initial concentration
(3) 64 times (4) 128 times (2) Rate of reaction is constant for first order reaction
(3) Unit of K for second order reaction is mol-r L sec-r
152. On introducin g a catalyst at 500 K the rate of a first order
(4) None of the above
reaction increases 2.718 times. If the activation energy in
the presence of a catalyst is 4.15 kJ mol-r, what will be E_ 162. The reaction 2NO * F, + 2NOF is supposed to follow the
in absence of catalyst is (R = 8.3 MKS) mechanism
(1) 4.1s kJ (2) 2.08 kJ
(3) 2.718 kJ (4) 8.3 kJ NO+Er+NOF,
srow
153. The Eo of a reaction in the presence of a catalyst is
NOE + NO ,2NOF
4.15 kJ mol-r and in the absence of catalyst is 8.3 kJ mol-t. The rate of reaction is given by
What is the slope of the plot of ln k vs in the absence of (1) r -K tNol (2) r =K [NoFr] tNol
catalyst? (3) r = K [NO]' [Fr] (4) None
(1) +1 (2) -l
(3) +1000 (4) -1000 163. Sucrose decomposes in acid solution into glucose
and fructose according to the first order rate law, with
154. The rate of disappearance of SO, in the reaction; t
" l/z = 3.0
h. What fraction of sample of sucrose remains
2SO2 * Or# 2SO, is 1.28 x 10-3 g litre-r sec-r, Then after 8 hours?
the rate of formalion of SO, in g litre-t sec-l is;
(l) 0.64 x 10-3 (2) 0.80 x 103
(r) M.
0.1s8 (2) 01.s8 M.
(3) 1.28 x l0-' (4) 1.60 x 10-3 (3) 1s.8 M. (4) 1s8 M.

155. The chemical reaction 2Or+ 30, proceeds as follows 164. In a reaction Nr(S) + :Hr(S) + 2Nq(g) the rate
orSor*o(fast) of appearance of NH, it 2.5x 10-4 mol L-l sec-r. The
O + O, i 2Or(slow) The rute law expression should be Rate of reaction and rate of disappearance of H, will be
(1) r =K [Or]' (2) r =K [Or]' [Or]-' (In mol L-l sec.-l)
(3) r = K [Or] [Or] (4) Unpredictable (1) 3.75 x 104, 1.25 x 10-a (2) 1.25 x 10+, 2.5 x 10-4
156. In a second order reaction, first order in each reactant (3) 1.25 x 10+, 3.75 x 10-a (4) 5.0 x 10*, 3.75x 10-a
A and B, which one of the following reactant mixtures will
165. The rate constant of a zero order reaction is 0.2 mol
provide the highest initial rute?
dm-3 h-r. If the concentration of the reactant after
(l) 0.2 mole ofAand 0.2 mole of B in 0.1 L solution 30 minutes is 0.05 mol dm-3. Then its initial concentration
(2) 0.1 mole ofA and 0.1 mole of B in 0.1 L solution would be
(3) 1.0 mole ofAand 1.0 mole of B in I L solution
(4) 0.1 mole ofA and 0.1 mole of B in 0.2L solution (1) 6.05 mol dm-3 (2) 0.15 mol dm-3
(3) 0.25 mol dm-3 (4) 4.00 mol dm-3
157. For a chemical reaction A + B it is found that the rate of
reaction double when the concentration of A is increased 166. For reaction A + B + C * D, doubling the concentration of
four times. The order in A for this reaction is both the reactants increases the reaction rate by 8 times and
(1) Two (2) One doubling initial concentration of only B simply doubles the
(3) Half (4) Zero reaction rate. The rate law is given as

158. The units for the rate constant of first order reaction is (1) r - klAl tBl (2) r - klAl' [B]
(1) s-r (2) mol L-r s-r (3) r - klAl [B]' (4) r - klA)ttz lBfitz
(3) mol s-l (4) Lmol-r s-r
159. The reaction L + M is started with 10 g of L. After 30 and 167. The half life of a reaction is halved as the initial conc. of
the reactant is doubled. The order of the reaction is
90 minute, 5 g and 1.25 g of L are left respectively. The
order of reaction is (1) 0.s (2) 1.0
(1) 0 (2) 2 (3) 2.0 (4) 0
(3) l (4) 3
1.48 Chemistry

Cottision Theory of Chemical Reactions ill 175. For the reaction:

[Cu(NH r)of'* + H2O [Cu(NHr)rHrOf'* + NH3
168. According to collision theory of reaction rates
(l) Every collision between reactant leads to chemical The net rate of reaction at any time is given by:
reaction net rate =2.0 x l0a[[Cu(NHr)o]'*l [HrO]
(2) Rate of reaction is proportional to velocity of mole- -3.0 x 10s[[Cu(NH,),HrO]*l [NH,]
cules
Then correct statement is (are):
(3) A11 reactions which occur in gaseous phase are zero
( I ) Rate constant for fonvard reaction = 2 x 10-4
order reaction
(2) Rate constant for backrvard reaction - 3 x lOs
(4) Rate of reaction is directly proportional to collision
(3) Equilibriurn constant for the reaction = 6.6 x 10-10
frequency.
(4) All of the above
169. At room temperature the reaction between NO and O, to 176. In the case of first order reaction, the ratio of time required
give NO, is fast while that between CO and O, is slow it is
for 99.9% completion to 50o/o completion is
due to
(1) CO is smaller in size than that of NO
(r) 2 (2) 5
(3) 10 (4) None of these
(2) CO is poisonous
(3) The activation energy for the reaction 177. For the reactionA +B + products, it is found that the order
2NO * O, + 2NO2 is less than
zCO * Or-+ 2CO2 ofA is I and the order of B ir When the conc. of bothA
(4) None of the above ;
and B are increased four times, the rate will increase by a
170. Chemical reaction occurs as a result of collision between factor of
reacting molecules. Therefore, the reaction rate is given by (l) 16 (2) 8
(l) Total number of collisions occruring in a unit volume (3) 6 (4) 4
per second
(2) Fraction of molecules which possess energy less than 178. The reaction 2A+ B + products, follows the mechanism
the threshold energy. i-- A, (fast)
2,A.
(3) Total number of effective collisions Ar*B+P(slow) .
(4) None of the above The order of the reaction is

lT1^ The rate constant is numerically the same for three reactions
(r) l.s (2) 3
of first, second and third order respectively. Which one is
(3) 1 (4) 2
true at a moment for rate of three reaction if concentration 179. Which statement is true for a first order reaction?
of reactants is same and greater than 1 M. (1) The degree of dissociation is equal to (l-e-*')
(1) rt=rz=rt (2) rr)rr)r, (2) The pre-exponential factor in the Arrhenius equation
(3) rr 1rr<- r, (4) All of these has the dimension of time-t
(3) A plot of reciprocal concentration of the reaction v/s
172. For reaction NO, + CO + CO2 + NO, the rate expression
time gives a straight line
is,Rate-K[NOr]'
(4) Both (1) and (2)
The number of molecules of CO involved in the slowest
step will be 180. Azo isopropane decomposes according to the equation
(l) 0 (2) I
(cH3)2cHN =NCH(CH3)2(g)%Nr(s)+
(3) 2 (4) 3
cuH,o(g)
173. The activation energies of two reactions, are Eo and E: It is found to be a first orderreaction. If initial pressure
with E,>E:. If the temperature of the reacting systems is P, and pressure of the mixture at time r is (P) then rate
is increased from Tr to T * predict which alternative is constant K would be
correct? K' are rate constant at higher temperature:

(1)
Ki-K; (2)
KI I\L
Ki (1) K- uo3.
-toeffi,
P.'.

Kr Kz Kr K2
K: Kl
, 2K; (z) K- 2'303 roep.
--o
(3)
Kr K2
(4) "i
Kr K2 t P,

174. If doubling the initial concentration of arcactant doubles t, (3) K- 2303 P

of the reaction, the order of the reaction is _roeffi

(1) ,3 (2) 2
(3) | (4) 0 \ / K- 2'303
(4)
2P
_loe,F;
 Chemical Kinetics 1,49
181. For a chemical reaction A -) B, the rate of reaction 186. The reaction
doubles when the conc. of A is increased 8 times. The CH3COOC2H' +NaOH -+ CH3COONa+ C2H5OH is
order of reaction w.r.t. A is
(l) Bimolecular reaction (2) II order reaction
I (3) Both (1) & (2) (4) None of these
(1) 3 (2)
2
1
187. For the reaction 2NO + Cl, + 2NOCI the following
(3) (4) 0 mechanism has been proposed
3
NO+Clr-NOCI2 (fast)
182. For a first order reaction A + B the reaction rate atreactant
NOCI2 +NO + 2NOC1 (slow)
concentration of 0.01 M is found to be2.0 x 10-5 mol L-r s-r.
The half life period of the reaction is the rate law for the reaction is
(1) 30 s (2) 220 s (1) Rate = K[NO]2[CI2] Q) Rate = K[NO][C12]2
(3) 300 s (4) 347 s (3) Rate = K[NOCl2] (4) Rate = K[NOCI]2
188. The ratio of the times for 99.9% of the reaction to complete
183. For a zero order reaction, the plot of concentration versus and half of the reaction to complete is
time is linear with
(1) 2 (2) 4
(1) +ve slope and zero intercept (3) 8 (4) l0
(2) -ve slope and zero intercept
(3) +ve slope and non-zero intercept 189. If at under different conditions and the activation energy of
reaction 1" and 2od is - 40 J mol-r and = 80 J mol-r. Then,
(4) -ve slope and non-zero intercept
(1) kru k, (2) k,. k,
184. Hydrolysis of ester in alkaline medium is (3) k, = k, (4) k, + k,
(l) First order reaction with molecularity one 190. Correct statement about first order reaction is:
(2) Second order reaction with molecularity two (l)
\ ./ tcompleuon - finite
(3) First order reaction with molecularity two
(4) Second order reaction with moleculaity one (2) tr,rn !
185. Which of the following statement is not correct for the (3) Unit J" is mole L-r sec-r
reaction:4A+B +2C+2D (4) tr,r\ l( = constant at constant temperature
(1) The rate of disappearance of B is twice the rate of
appearance of C l.91.Inthereversib1ereaction2No2#N,oo,therateof
(2) The rate of B is one fourth the rate disappearance of NO, is equal to
disappearance of
of disappearance of A )
(r) (2) 2K,
ZK, [N(
[NOr]' - zK2[NrOo
(3) The rate of formation of D is one half the rate of
consumption ofA
?[No,]'
(3) ZKr[NOr],-K, [NrOo] (4) (2Kr-Iq) [NOr]
(4) The rate of formation of C and D are equal
1.50 Chemistry

Itffi illl
1. The rate of first order reaction is 1.5 x 101 mol L-r min-r (l) 1.73 x l0-4 lvf/min
at 0.5 M concentration of the reactant. The half life of the (2) 1.73 x l0-5 lv{/min
reaction is: (3) 3.47 x 10-4 lvl/min
(l) 7.53 min (2) 0.383 min (4) 3.47 x 10{ lWmin
(3) 23.1 min (4) 8.73 min
10. A reactant (/) forms two products:
2. In a first order reaction, the concentration of the reactant, A k' > B, Activation Energy 8,,
decreases from 0.8 M to 0.4 M in 15 minutes. The time
taken for the concentration to change from 0.1 M to 0.025 M
A1C, Activation Energy Eo,

is: lf E,z: 2E o1,

then k, and k, are related as:
(1) 7.5 min (2) 15 min (1) k, = 2kreEo'tnr Q) k, = kreE"'rnr
(3) 30 min (4) 60 min g) k, = kreEo'rnr
(3) kr: kreE",rnr
3. The rate equation for the reaction 2A + B + C is found to
11. The rate of a chemical reaction doubles for every 10"C rise
be: rate- klA]tB]. The correct statement in relation to this
of temperature. If the temperature is raised by 50oC, the rate
reaction is that the
of the reaction increases by about:
( I ) Rate of formation of C is twice the rate of disappearance
of A.
(l) 32 times (2) 64 times
(3) 10 times (4) 24 times
(2) Half life is a constant
(3) Unit of k must be s-r 12. Activation energy of a chemical reaction can be determined
(4) Value of k is independent of the initial concentrations of by
AandB (1) determining probability of collision
(2) using catalyst
4. The role of a catalyst is to change
(3) determining the rate constant at standard temperature
(l) equilibrium constant (4) determining the rate constants at two temperatures
(2) activation energy of reaction
(3) enthalpy of reaction 13. For the reaction
(4) Gibbs energy of reaction A+28+Product,
the differential rate equation is:
5. The half-life of a radio isotope is four hours. If the initial
mass of the isotope was 200 E, the mass remaining after
24 hours undecayed is: ' -:dlll
(1)
2dt
=-ol:1
dt
- KVllnl'
L

(l) 3.125 g (2) 2.084 g

(3) r.042 g (4) 4.167 s
(2)
\/ :M=ol:l
2 dt dt
- KVllal'
6. For a first order reaction A + B the reaction rate at reactant
concentration of 0.01 M is found to be 2.0 x l0_5 mol L-ls-r.
The half life period of the reaction is:
(1) 220 s (2) 30 s
(3)
#=-+# t{teyat'
(3) 300 s (4) 347 s
(4) +=-i ry r{lellsl'
7 . The rateof reaction between two reactants Aand B decreases dt 2dt
by a factor'of 4 if the concentration of reactant ^B is doubled.
14. A reaction was found to be of second order with respect to
The order of this reaction with respect to reactant B is:
the concentration of carbon monoxide if the concentration
(l) 1 (2) -2
of carbon monoxide is doubled, with everything else kept
(3) I (4) 2 the same, the rate of reaction will:
8. The heat evolved or absorbed during the reaction in the (l) double (2) remain unchanged
presence of a catalyst (3) triple (4) increase by a factor of 4
(I ) increases
15. The following mechanism has been proposed for the
(2) decreases reaction of NO with Br, to form NOBr:
(3) may increase or decrease
NO(g) + Brr(B) + NOBrr(S)
(4) remains unchanged NOBrr(g) + NO(e) + 2NOBr(g)
g. For a first order reactio n, (,4)+ products, the concentration If the second step is the rate determining step, the order of
ofA changes from 0.1 M to 0.025 M in 40 minutes. The tate the reaction with respect to NO(g) is:
of reaction when the concentration ofr4 is 0.01 M is: (1) 2 (2) I
(3) o (4) 3
 Chemical Kinetics 1.51
16. Consider the figure and mark the correct option. 21. The unit of rate constant is mol lirt sec-l. Then the order of
Activated complex reaction will be:
(r) 0 (2) I
(3) 2 (4) 4
t>\ 22. For the first order reaction
bo
l-. C6HsNrCl+ C6HsCl +N2
I Products
>{
rq E2 On doubling the concentration of C6H5N2CI rate of
production of N, becomes:
Reactants (l) Double (2) Three times
(3) remain same (4) Four times
+
Reaction coordinate

(1) Activation energy of both forward and backward 23. For the change A -) Product. If A follows second order
+ kinetics then on doubling the concentration of ,4, Rate of
reaction is Er E2 and reactant is more stable than
reaction changes by a factor of:
product.
(2) Activation energy of backward reaction is E, and
(r) 2 (2) 4
product is more stable than reactant.
(3) u2 (4) U4
(3) Activation energy of forward reaction is Er * E, and 24. Consider the Arrhenius equation given below and mark the
product is less stable than reactant. correct option.
(4) Activation energy of forward reaction is Er * E, and
k _ 4a-Ea/Rr
product is more stable than reactant.
(1) Rate constant decreases exponentially with increasing
17. For the reaction activation energy and decreasing temperafure.
2A+B+3C+D (2) Rate constant increases exponentially with decreasing
Which of the following does not express the reactionrate? activation enerry and decreasing temperature.
(1)
:# (2)
+ (3) Rate constant increases exponentially with decreasing
activation enerry and increasing temperature.
(4) Rate constant increases exponentially with increasing
(3) (4) -1 dlAl
# dt
25.
activation energy and decreasing temperature.

For the reaction H, * I, * zHl the true relationship is

18. Consider the reaction
N2(g) + 3Hr(g) * zNH, (s) (1)-*-*-*
dln,l _d[r,] _d[sr]
The equality relationship between
d []tIH' I and -dllll-l
is: dt dt (2) dlH,l _dlt,l= 1 a[HI]
dt dt 2dt
(l) d[]'IH,] : - Ldlnrl e) a[NH,]
* : - ?dlwrl (3) -2dlH,7:-ru-a[m]
dt 3 dt dt 3dt dt dt dt

(3) *a[Ns,]=-1aln,l 91 gqU=-ry (4) zdlH,)= _ za\,l_ I a[m]

dt 2dt dt dt dt dt 2dt
26. A chemical reaction
19. The tr,rof areaction is halved as the initial concentration of 2A + 28 + C + product follows the rate equation: r p V)
the reactant is doubled. What is the order of reaction? lB)2 then order of reaction is
(1) First order (2) Zero order (r) 0 (2) l
(3) Second order (4) Third order (3)2 (4)3 r

20. Consider a first order gas phase decomposition reaction 27. The units of rate constant of first & second order reaction is
given below: respectively
A,*, B,u, * c,r, (l) time-r, mole-r. litre. time-l
The initial pressure of the system before decomposition of (2) mole ltr', time-r
A was P,. After lapse of time 't' , total pressure of the system (3) mole-r. litre. time-r, time-r
increased by x units and becam. 'P,' The rate constant k for (4) sec-l, litre-t
the reaction is given as

(l) k- 2'3031og.-4 2'303loe- 4

t - (2) k- t
-2Pr+P, -P,*x

(3) k-
+r"*q= (4) k- ryr"s#
1.52 Chemistry

28. A plot of volume of hydrogen released versus time for the (I ) E, is energy of activation
reaction between zinc and dilute HCI is shown in figure. On (2) R is Rydberg's constant
the basis of this mark, the correct option is (3) & is equilibrium constant
(4) A is adsorption factor
vs
v4
34. For the reaction system:
2NO(g;+Or(g)-ZNOr(S)
v3
volume is suddenly reduced to half its value by increasing
the pressure on it. If the reaction is of first order with respect
v2 /
vr to 02 and second order with respect to NO, the rate of
/ reaction will
(1) Increase to eight times of its initial value
/ (2) Increase to four times of its initial value
0 2030 40 s0 (3) Decrease to one-fourth of its initial value
(4) Decrease to one-eighth of its initial value
(l) Average rate up to 40 seconds is
* 35. The rate law for a reaction between substances A and ^B is
V' given by Rate - k lAl' lBl^ On doubling the concentration
(2) Average rate up to 40 second is % - of A and halving the concentration of the ratio of the new
40 -20 ^8,
rate to the earlier rate of the reaction will be as
(3) Average rate up to 40s is % ;% (1) l(n-m) (2) 2(n-m)
40
(3)
\- " ,L (4) (m+n)
- yl
(4) Average rate up to 40 seconds is 1
40-30
2@+")'

36. Which of the following statement is true?

( 1) The rate of a reaction decreases with increase in
29. In the equation Kt - log Co-log C,, the curve between t and concentration of reactant(s).
log C, is (2) The rate of a reaction is independent of temperature
(1) line
a straight (2) a parabola change
(3) a hyperbola (4) none (3) The rate of a reaction decreases with passage of time as
the concentration of reactants decreases.
30. Consider following two reactions (4) The rute of a reaction is same at any time during the
A+ Product+:k,lAl" reaction.
B+ Product+ -k,lBl
Units of k,and k,are expressed in terms of molaity (mol L-l)
37. In a first order reactiono the concentration of the reactant,
and time (sec-l) as
decreases from 0.8 M to 0.4 M in 15 minutes. The time
(1) sec-I, M sec-l (2) M serl,M sec-l taken for the concentration to change from 0.1 M to 0.025 M
(3) sec-I, M-l sec-l (4) M sec-I, sec-l is
(1) 30 minutes (2) 15 minutes
31. H, gas is adsorbed on the metal surface like tungsten. This (3) 7.5 minutes (4) 60 minutes
follows............ order reaction
(l) Third (2) Second 38. The rate equation for the reaction 2A + B + C is found to
(3) Zero (4) First be: rate - k l,A) lBl. The correct statement in relation to this
reaction is that the
32. Incorrect statement about order of a reaction is (1) unit of kmust be s-l
( I ) The order of a reaction can be a fractional number.
(2) t,,rts a constant
(2) The order of a reaction is the sum of the powers of
molar concentration of the reactants in the rate law (3) rate of formation of C is twice the rate of disappearance
expression. ofA
(3) Order of a reaction is experimentally determined (4) value of k is independent of the initial concentrations of
quantity.
AandB
(4) The order of a reaction is always equal to the sum of the
stoichiometric coefficients of reactants in the balanced 39. Consider an endothermic reactionX + Iwith the activation
chemical equation for a reaction.
energies Eu and Erfor the backward and forward reactions,

33. In respect of the equation k - ,ls -unr in chemical kinetics, respectively. In general
which one of the following statement is correct? (1) Eu, E
(2) Eu. E,
 Chemical Kinetics 1.53
(3) there is no definite relation between Eoand E, (3) the fraction of molecules with energy greater than the
(4) Eo: E, activation enerry of the reaction
(4) the energy above which all the colliding molecules will
40. Which of the following expressions is correct for the rate of react
reaction given below?
46. The following mechanism has Qeen proposed for the
5BGl + BrOr,"q) * 6HL, 3Brr,un) + 3H2O.l reaction of NO with Br, to form NOBr:
NO(g) t Br, (g) +NOBr, (s)
(1) {r.]
At
=5f]
6At
(2) 4rl
At -6gl At
NOBr, (g) +NO (g) + 2 NOBr (g)
If the second step is the rate determining step, the order of

(3)
gl {sl
At
-5 At
(4) {rl=6ry1
At5At
the reaction with respect to NO (g) is
(1)
(3)
0
2
(2) 3
(4) I
41.. A reaction involving two different reactants can never be 47 . The energies of activation for forward and reverse reactions
( 1) first order reaction for A, * B, + 2AB are 180 kJ mol-l and 200 kJ mol-l
(2) unimolecular reaction respectively. The presence of a catalyst lowers the activation
(3) bimolecular reaction energy of both (fonvard and reverse) reactions by 100 kJ
(4) second order reaction mol-l. The enthalpy change of the reaction (Ar+ B,12AB)
in the presence of catalyst will be (in kJ mol-l)
42. Can be taken as the time taken for the concentration of a (r) 300 (2) r20
reactant to drop to of its initial value. If the rate constant for (3) 280 (4) 20
a first order reaction is K, t,o can be written as
(1) 0.291K (2) 0.10/I( 48. What is the value of rate constant if rate law for the reaction
. 'B' is doubled, keeping the concentration of 'A' constant?
(3) 0.7stK (4) 0.6etK
(l) quadrupled (2) halved
43. A reaction was found to be second order with respect to the (3) the same (4) doubled
concentration of carbon monoxide. If the concentration of
carbon monoxide is doubled, with everything else kept the 49. Consider the reaction, 2A + B -+ Products. When
same, the rate of reaction will
concentration of B alone was doubled, the half-life of B did
(1) triple (2) increase by a factor of 4 not change. When the concentration ofr4 alone was doubled,
(3) double (4) remain unchanged the rate increased by two times. The unit of rate constant for
this reaction is
44. Which of the following plot represents exothermic reaction? (1) L mol-rs-l (2) no unit
(i) complex (iD Activated (3) mol L-1s-1 (4) s-r

t t 50. For a reaction L e + 28, rate of disappearance of 'A'

a0 2
b0 t<
l-{
0)
0)
tr related to the rate of appearance of 'B' by the expression
>{ 1I]
r! Reactants Products
Reactants (1) _dlAl_ 1 dlBl Q) _dlAl _ dlBl
Reaction -+ Reaction coordinate + dt 4dt dt dt
dlBl
(iii) (3) -dl+ - '
dt dt
{dl') (4)
\-'' -dl\=
dt 2
1
dt
th
bo
51. The half life period of a first order chemical reaction is
t-(
0)
tr 6.93 minutes. The time required for the completion of 99%
rI] of the chemic al reaction will be (1og 2 - 0.301)
Reactants Products
(1) 23.03 minutes (2) 46.06 minutes
Reaction + (3) 460.6 minutes (4) 230.3 minutes

(l) (ii) only (2) (iii) only 52. Which of the following statements is not correct about the
(3) (i) only (4) (i) and (ii) collision theory of chemical reaction?
(1) Collision of atoms or molecules possessing sufficient
45. Rate of reaction can be expressed by Anhenius equation as threshold energy results into the product formation.
equatiofl, E represents
(2) Molecules should collide with sufficient threshold
k - Ae-E/RT,lnthis energy and proper orientation for the collision to be
(1) the energy below which colliding molecules will not
react
effective.
(2) the total energy of the reacting molecule at a (3) It considers reacting molecules or atoms to be hard
spheres and ignores their structural features.
temperafure, T
1.54 Chemistry

(4) Number of effective collisions determines the rate of 55. Which of the following statement is incorrect for the
reaction. catalyst?
(1) It is a substance that does not change the equilibrium
53. For a first order reaction, (A) + products, the concentration constant of a reaction.
of A changes from 0.1 M to 0.025 M in 40 minutes. The rate (2) Itprovides an alternate mechanism by reducing
of reaction when the concentration ofr4 is 0.01 M, is: activation enerry between reactants and products.
(1) 3.47 x l0-4 M/min (3) It catalyses the forward and backward reaction to the
(2) 3.47 x 10-s M/min same extent.
(3) l.'13 x 10-4 M/min (4) It alters AG of the reaction.
(4) 1.73x 10-5 IWmin
56. The value of rate constant of a pseudo first order reaction
54. How much time would it take for 100% completion, if the
first order reaction is 50% completed in 1.26 x lOra s.? (1) depends only on temperature
(1) 1.26 x 10rs s (2) 2.52 x 10ra s (2) depends on the concentration of reactants present in
(3) 2.52 x 1028 s (4) infinite small amount
(3) depends on the concentration of reactants present in
excess
(4) is independent of the concentration of reactants
 Chemical Kinetics 1.55

ilx
These questions consist of two statements. During answering these Questions you are required to choose any one of the following four
responses.

1. Staternent 1: The rate of the reaction is the rate of change 7. Statement 1: Acid catalysed of hydrolysis ethyl acetate is a
of concentration of a reactant or a product. first order reaction.
Statement 2: Rate of reaction remains constant during the Statement 2zWater does not take part in the reaction.
complete reaction.
8. Statement 1: For a first order reactiofr tr,ris independent of
2. Statement 1: The reaction having low value of activation the initial concentration of reactants.
energy are generally fast. Statement 2: For a first order reactiofl tr,ris twice the t,o.
Statement 2: Temperature coemcient for reaction having g. Statement 1: If in a zero order reaction, the concentration of
low activation energy is large. the reactant is doubled, the half:life period is also doubled.
3. Statement 1: Half life period is always independent of Statement 2: For a zero order reaction, the rate of reaction
initial concentration. is independent of initial concentration.

Statement 2: HaIf life period is directly proportional to rate 10. Statement 1: Formation of HI is a biomolecular reaction.
concentration. Statem ent 2z TWo molecules of reactants are involved in
this reaction.
4. Statement 1: The molecularity of a reaction is a whole
number other than zero, but generally less then 3. .11. Statement 1: In a first order reaction the rate constant
Statement 2z The order of a reaction is always whole double on doubling the initial concentration of the reaction.
number. Statement 2z The rate constant varies directly with the
concentration of the reactants in a first order reaction.
5. Statement L: In a reversible endothermic reaction activation
energy of the forward reaction is higher than that of the 12. Statement 1: Two different reactions can never have same
backward reaction. rate of reaction.
Statement 2: The threshold energy of the forward reaction Statement 2z Rate of reaction always depends only on
is more than that of the backward reaction. frequency of collision and Arrhenius factor.

6. Statement 1: The molecularity of the reaction Hz + B., 13. Statement 1: Rate of reaction doubles when concentration
2HBr is 2 of reactant is double if it is a first order reaction.
3 Statement 2: Rate constant also double.
Statement 2: The order of the reaction is
;
1.56 Chemistry

IIffi ffill
1.. An endothermic reaction with high activation energy for the CH3 C OCH, (a$+Brr(aq) -+ CH3 C OCHTBT(aq)+H*(aq)+Br(aq)
reaction is given by the diagram: [AIIMS 20051 These kinetic data were obtained for given reaction
concentrations.
ao
L{
C)
tr Initial Concentrations, M
()
r-(
(l ) cB
. +-(
+) ICH3COCH3I lnrrl [H.]
tr
0)
+-)
o 0.30 0.05 0.05
A
Reaction coordinate
0.30 0.10 0.05
0.30 0.10 0.10

h 0.40 0.05 0.20

bo
k
o Initial Rate, disappearance of Bt* Ms-r
tr
C)
5.7 x 10-5
o) .s
\,.+a
r-{

?1 5.7 x 10-s
H
o)
{-)
o 1.2x 104
p<
3.1 x 104
Reaction coordinate
Based on these data, the rate equation is: [AIPMT 20081
(1) Rate = kICH3COCHTJ [Brr]
h
b0
l-(
o
(2) Rate = [Link][H*]'
tr (3)
() Rate = fr[CH3COCHrllBrr][H.]
(3) (4) Rate = k[CH3COCHT][H.]
EFa
()
P
o
0i 5. For the reaction, N, * 3Hr+ 2NH3, if
Reaction coordinate d[NH3]
=2x10-4 mol L-r s-r, the value of -dlYrl would
dt dt
be: [AIPMT 20091
bo
t-(
0)
(1) | x 104 mol L-l s-r
tr
(l) (2) I x 10-4 mol L-l s-r
r<

(4)
cB
.r-
{-)
(3) l, x 10-4 mol L-l s-r
(4) S x 10+ mol L-r s-r
A
l-{
(l)
{-)
o
F{
6. For the reaction A + B +products, it is observed that:
Reaction coordinate
IATPMT 200e1
(a) on doubling the initial concentration of A only, the rate
For reaction aA + xP. When [,4] : 2.2 Inrn, the rate was
of reaction is also doubled and
2. (b) on doubling the initial concentrations of both ,4 and
found to be 2.4 mMs-r. On,reducing concentration of A to
B, there is a change by a factor of 8 in the rate of the
half, the rate changes to 0.6 mMs-r. The order of reaction
reaction.
with respect to,4 is: [AIIMS 20051 The rate of this reaction is given by:
(l) l.s (2) 2.0
(l) rate = kl,afifl
(3) 2.5 (4) 3.0 Q) rate = klAl2lBl
(3) rate - klAllBl' $) rate - klA)'lBl'
3. The rute constants &, and k, for two different reactions are
7. In the reaction
1016 elwun and 1Ots {t00on) respectively. The temperature at
Bro3-(aq) + 5Br(aq) + 6H* -+3Brr(D + 3H2O(f)
which k, = kris [AIPMT 20081 The rate of appearance of bromine (Brr) is related to rate of
2000 disappearance of bromide ions as following:
(1) Q) 2000 K
n$* IATPMT 200e1

(3)
\ / -looq
2.303
K @) looo K (1)ry=;+
4. The bromination of acetone that occurs in acid solution is
d(r")
represented by this equation (2)
d (srr) 3
dt 5dt
 Chemical Kinetics 1.57

(3)
a(ar,)= _
y(nr-) (,)Ln[#)
dt3dt
a(nr,) a(nr-)
_5
(2) 1r'(r;?r)
(4)
dt3dt
8. Half life period of a first-order reaction is 1386 seconds.
The specific rate constant of the reaction is: [AIPMT 20091 (3)1r,,[a5)
(l) 5.0 x 10-2 s-r (2) 5.0 x l0-3 s-r
(3) 0.5 x 10-2 s-r (4) 0.5 x l0-3 s-l
9. The rate of the reaction [AIPMT 20101
(4)'-rn[#)
2NO + Cl, -+ 2NOCI is given by the rate equation
rate = k[NO1z[Clrl the value of rate constant can be increased
14. Which one of the following statements for the order of a
by: reaction is incorrect? [AIPMT Pre.-20111
(1) Order can be determined only experimentally
(1) Increasing the concentration of NO
(2) Order is not influenced by stoichiometric coefficient of
(2) Increasing the concentration of the Cl,
the reactants
(3) Increasing the temperature
(3) Order of reaction is sum of power to the concentration
(4) Doing all of these
terms of reactants to express the tate of reaction
10. For the reaction N2os(g) + 2No2(g) + the value (4) Order of reaction is always whole number
iorrr)
of rate of disappearance of NrO, ir given as 6.25 x l0_3 15. The unit of rate constant for a zero order reaction is:
mol L-rs-r. The rate of formation of NO, and O, is given IAIPMT Mains-20111
respectively as: [AIPMT 20101 (l) s-r (2) mol L-r s-r
(l) 1.25 x l0-2 mol L-rs-r and (3) L mol-r s-r (4) L2 mol-2 s-l
6.25 x 10_l mol L-rs-r
(2) 6.25 x l0_3 mol L-rs-r and 16. The half life of a substance in a certain eruyme-catalysed
6.25 x 10-3 mol L-rs-r reaction is 138 s. The time required for the concentration
(3) 1.25 x 101 mol L-rs-r and of the substance to fall from 1.28 mg L-r to 0.04 mg L-r:
3.125 x 10-3 mol L-rs-r IAIPMT Mains-20111
(4) 6.25 x l0-3 mol L-rs-r and (l) 276s (2) 4t4s
(3) 552 s (4) 6e0 s
3.125 x 10-3 mol L-rs-r

11.. During the kinetic study of the reaction, 2A + B -+ C * D,

17 . The rate of the reaction 2NrOs -) 4NO2 * O, can be written
in three ways
following results were obtained: [AIPMT 20101
Experiment [A] mol L-t [B] mol L-t Initial rate of -a[N,o,]
formation of D
- k[Nro,]
dt
mol L-rmin-l
I 0.1 0.1 6.0 x 10_3 ry.]
dtt
=K,[N,o,]
II 0.3 0.2 7.2 x l0-2
m 0.3 0.4 2.88 x 10-'
IV 0.4 0.1 2.40 x 101 #:Ko[N'o']
The relationship betwee n k and k' k and k" are:
and,betwee n
Based on the above data which one of the following is IAIPMT Mains-20111
correct? (l) k':k;k"-k (2) k':2k;k"-k
(1) rate - klA)lBl' (2) rate = kIAl'lBl (3) k' :2k; k" : klT (4) k' :2k; k" :2k
(3) rate = klA)Wl g) rate - klA)'lBl'
18. For a first order gas phase reaction [AIIMS 201U
12. For an endothermic reaction, energy of activation is E" A(e) +28(s)+C(e)
and enthalpy of reaction is DH (both of these in kJ/mol). Po be initial pressure ofA and P, the total pressure at time 't'.
Minimum value of E" will be: [AIPMT 20101 Integrated rate equation is
(l) Equal to zero (2) Less than DH (
(3) Equal to DH (4) More than DH (2)2.303 . 2Po

t ros I 3Po-1
13. For a first order reaction, the value of rate constant for the
reaction
A. .--)2B..+C
- -(gas)
--(gas) -(solid)
lArrMS 20101
(3) '3o''o,
t 2Po
Po

- P,
I (4) rybe(
)t\
2Po

ZPo-1
1.58 Chemistry

19. In a zero-order reaction for every 10o rise of temperafure, 26. Activation energy (Eo) and rate constants (k, and k ) of a
the rate is doubled. If the temperature is increased from chemical reaction at two different temperatures (T, and Tr)
10oC to l00oc, the rate of the reaction will become: are related by [NEET 20121
IAIPMT Pre.-20121
(l) times (2) 128 times (1) h?:-+
(3) 256
64
times (4) 512 times [+ ;)
20. In a reaction A + B + Product, rute is doubled when the (2) h?=-+
(t -r)
concentration of B is doubled and rate increased by a factor [q r,)
of 8 when the concentrations of both the reactants (A and B)
are doubled, rate law for the reaction can be written as: (3) m?=-
kt +( :-+l
R(.4 Tr)
IAIPMT Pre.-20121
(1) Rate - kl,A)lB) (2) Rate - klAl'lBl (4) both (2) and (3)
(3) Rate - k tA) lB) (4) Rate - k l,4l'lBl'
27. What is the activation energy for a reaction if its rate doubles
21. Activation energy (E^) and rate constants (k, and kr) of a when the temperature is raised from 20oC to 35oC?
chemical reaction at two different temperaturer (f, and Tr) (R = 8.314 J mol-' K-') [NEET 20131
are related by: [AIPMT Mains-20121 (l) 269 kJ mol-' (2) 34.7 kJ mol-l
(3) l5.l kJ mol-l (4) 342 kJ mol-t
(1) ,"?=-
+( T2 +) 28.
'A
reaction having equal energies of activation for forward
and reverse reaction has [NEET 20131
(2) ntz = '' ( 1_ (r) AG-O (2) AH-O
\ R\. r, +) (3) AH: AG: AS -0 (4) AS : o
(3) ln k2 - -Eo 1 1
29. The activation energy of a reaction can be determined from
ktR i-,, the slope of which of the following graphs? [AIPMT 20151

(4) ln kz - -Eo l1 (1) ln rtrs.1 (2\ T1

\'/ lnkvs '-T
ktR T2 r, T

22. For a reaction r _ K(CH3COCH T)''' then unit of rate of (3) In kvs. T (4) lnk vs .T
reaction and rate constant respectively is: [AIIMS 20121 T
30. When initial concentration of a reactant is doubled in a
(1) mol L-l sec-r, mol-llf sec-r
reaction, its half-life period is not affected. The order of the
_1 _1
reaction is
(2) mol-r L-r sec-r, mol 2L 2 sec-r IAIPMT 20151
I
(1) Second
+-
(3) mol L-r sec-r, mol 2L 2 sec-l (2) More than zero but less than first
(3) Zero
(4) mol I sec, ,[Link]-i sec (4) First

23. tr,rv lS + is a straight line graph then determine the order 31. The rate constant of the reactionA + B is 0.6 x 10-3 mole per
second. If the concentration of A is 5 M, then concentration
of reac tlon lArrMS 20121 of B after 20 minutes is [AIPMT 20151
(1) Zero order (2) First order (l) 0.36 M (2) 0.72M
(3) Second order (4) Third order (3) 1.08 M (4) 3.60 M
24. In a zero-otder reaction for every 10o rise of temperature, 32. The rate of a first-order reaction is 0.04 mol L-r s-r at 10
the rate is doubled. If the temperature is increased from seconds and 0.03 mol L-r s-r at 20 seconds after initiation of
10oC to 100oC, the rate of the reaction will become the reaction. The half-life period of the reaction is
[NEET 20121 INEET 20161
(l) 64 times (2) Stztimes (l) 54.1 s (2) 24.r s
(3) 256 times (4) 128 times (3) 34.1 s (4) 44.t s
25. In a reaction A + B --+ Product, rate is doubled when the 33. The decomposition of phosphine (PH3) on tungsten at low
concentration of B is doubled, and rate increases by a factor pressure is a first-order reaction. It is because the
of 8 when the concentrations of both the reactants (A and B) INEET 20161
are doubled, rate law for the reaction can be written as (1) Rate of decomposition is very slow
INEET 20121 (2) Rate is proportional to the surface covered
(1) Rate - klA)'lBl (2) Rate - klA)tBl (3) Rate is inversely proportional to the surface covered
(3) Rate - k lAl lBl' (4) Rate - k lA)' lBl' (4) Rate is independent of the surface covered
 ChemicaI Kinetics 1.59
34. Mechanism of a hypothetical reaction (1) collision frequency (2) activation energy
xzaYz ---+ 2xY is given below (3) heat of reaction (4) threshold energy
(i) x2 --+ X+X(fast) 40. The half-life for a zero order reaction having0.02 M initial
concentration of reactant is 100 s. The rate constant (in mol
(ii) X+Y2 XY+Y(slow) L-t s-') for the reaction is [NEET 2020 Phase 2l
(iii) X+Y -
-+ xY(fast)
(1) I .0 x l0-2 (2) I .0 x l0-4
(3) 2.0 x l0-4 (4) 2.0 x 10_3
The overall order of the reaction will be INEET 20171 41. In collision theory of chemical reaction, Zo, represents
(1) 2 (2) 0 INEET zl,ifzOPhase 2l
(3) l.s (4) I 1) the fraction of molecules with energies equal to E.
(

(2) the fraction of molecules with energies greater than E,

35. A first order reaction has a specific reaction rate of 10-2 sec-r.
How much time will it take for 20 g of the reactant to reduce
(3) the collision frequency of reactants, A and B
to 5 g?
(4) steric factor
[NEET 20171
(1) 138.6 sec (2) 346.5 sec 42. For a rcaction A # B, enthalpy of reaction is 4.2 kJ
mol-r and enthalpy of activation is 9.6 kJ mol-r. The correct
(3) 693.0 sec (4) 238.6 sec
potential energy profile for the reaction is shown in option.
36. The correct difference between first-and second-order
reaction is that TNEET 20181
(l) the rate of a first-order reaction does not depends on
(1)
t (2)
t
reactant concentration; the rate of a second order B
reaction does depends on reactant concentrations. A
A B
(2) the half-life of a first-order reaction does not depends
on lAlo; the half-life of a second-order reaction does Reaction Progress Reaction Progress
depends on lA)o
(3) the first-order reaction can be catalyzed; a second-order
reaction cannot be catalyzed.
(4) the rate of a first-order reaction does depends on reactant I t B
(3) (4) PE
concentrations; the rute of a second-order reaction does A
A B
not depend on reactant concentrations.

37. When initial concentration of the reactant is doubled, the Reaction Progress Reaction Progress
half-life period of a zero order reaction [NEET 20191
(1) is halved (2) is doubled INEET 20211
(3) is tripled (4) remains unchanged
43. The slope of Arrhenius plot (^* rr, +J of first order
38. The rate constant for a first order reaction is
\. T)
4.606 x 10-3s-r. The time required to reduce Z.0g of the reaction is -5 x 103 K. The value of E" of the reaction is.
rcactant to 0.2 g is: [NEET 2020 Phase 1l Choose the correct option for your answer.
(1) 1000 s (2) 100 s
[Given R - 8.314 JK-' mof'1
(3) 200 s (4) 500 s
(1) 41.5 kJ mol-r (2) 83.0 kJ mol-r
39. An increase in the concentration of the reactants of reaction (3) 1 66 kJ mol-r (4) -83 kJ mol-r
leads to change in: [NEET 2020 Phase 1l INEET 20211
1.60 Chemistry

[fi8

Iffiffi
THEORY t4t. (3) 142. (3) 143. (1) 144. (4) 145. (1)
146. (2) 147. (3) 148. (3) 149. (2) 150. (t)
lrurexr SuesrtoN - 1 151. (3) 152. (4) 153. (4) 154. (3) 155. (2)
1. (2) 2. (3) 3. (1) 4. (4) 156. (1) 157. (3) 158. (1) 159. (3) 160. (4)
161. (2) 162. (3) 163. (l) 164. (3) 165. (2)
lrurexr OuesnoN - 2 1,66. (2) 1,67. (3) 168. (4) 169. (3) 170. (3)
1. (1) 2. (1) 3. (4) 4. (2) t7t. (3) 172. (1) 173. (2) 174. (4) 175. (4)
176. (3) 177. (2) 178. (2) 179. (4) 180. (1)
181. (3) 182. (4) 183. (4) 184. (2) 185. (l)
lrurexr OuesnoN 3 186. (3) 187. (1) I88. (4) 189. (l) 190. (4)
t. (1) 2. (3) 3. (1) 4. (3) 5. (1) tgt. (2)
6. (2)

lrursxr BuesnoN - 4 EXEBGISE 2= MIXED GONGEPT

1. (2) 2. (2) 3. (2) 4. (3) 5. (3) OUESTIONS
6. (4) 1. (3) 2. (3) 3. (4) 4. (2) 5. (1)
6. (4) 7. (2) 8. (4) 9. (3) 10. (4)
11. (t) 12. (4) 13. (3) 14. (4) 15. (1)
EXERGISE 1= TOPIGWISE OUESTIONS 16. (3) l'l . (l) 18. (2) 19. (3) 20. (4)
1. (2) 2. (1) 3. (4) 4. (l) 5. (1) 21. (1) 22. (1) 23. (2) 24. (3) 25. (3)
6. (3) 7. (4) 8. (4) 9. (1) 10. (3) 26. (4) 27. (1) 28. (1) 29. (1) 30. (4)
11. (3) 12. (2) 13. (3) 14. (3) 15. (3) 31. (3) 32. (4) 33. (l) 34. (1) 35. (2)
16. (4) 17. (3) 18. (4) 19. (2) 20. (4) 36. (3) 37. (t) 38. (4) 39. (2) 40. (1)
21. (2) 22. (1) 23. (3) 24. (2) 25. (3) 41. (2) 42. (l) 43. (2) 44. (3) 45. (1)
26. (4) 27. (3) 28. (2) 29. (3) 30. (2) 46. (3) 47. (4) 48. (3) 49. (1) 50. (1)
31. (4) 32. (3) 33. (4) 34. (2) 35. (3) 51. (2) 52. (1) 53. (l) 54. (4) 55. (4)
36. (2) 37. (4) 38. (1) 39. (3) 40. (2) 56. (3)
41. (3) 42. (3) 43. (4) 44. (4) 45. (2)
46. (4) 47. (2) 48. (1) 49. (1) 50. (3)
51. (l) 52. (l) 53. (3) 54. (2) 55. (4) STATEMENT BASED OUESTIONS
56. (3) 57. (2) 58. (3) 59. (4) 60. (4) 1. (3) 2. (3) 3. (4) 4. (3) 5. (3)
61. (3) 62. (2) 63. (1) 64. (2) 65. (l) 6. (2) 7. (3) 8. (3) 9. (2) 10. (1)
66. (1) 67. (3) 68. (2) 69. (l) 70. (4) 11. (4) 12. (4) 13. (3)
71. (2) 72. (2) 73. (3) 74. (3) 75. (3)
76. (2) 77. (3) 78. (2) 79. (2) 80. (2)
81. (2) 82. (3) 83. (4) 84. (1) 85. (1)
86. (2) 87. (3) 88. (3) 89. (3) 90. (4) ARGHIUES
91. (2) 92. (4) 93. (4) 94. (3) 95. (2) 1. (3) 2. (2) 3. (3) 4. (2) 5. (2)
96. (3) 97. (4) 98. (3) 99. (1) 100. (1) 6. (3) 7. (2) 8. (4) 9. (3) 10. (3)
101 . (2) 102. (2) 103. (1) I 04. (4) 105. (4) 11. (l) 12. (4) 13. (2) 14. (4) 15. (2)
106. (2) 107. (4) 108. (3) I 09. (1) 110. (4) 16. (4) 17. (3) 18. (2) 19. (4) 20. (2)
111. (l) tlz. (2) 113. (3) tt4. (1) 115. (3) 21. (4) 22. (l) 23. (4) 24. (2) 25. (1)
tt6. (l) tt7. (4) 118. (2) 119. (2) 120. (3) 26. (4) 27. (2) 28. (2) 29. (1) 30. (4)
tzt. (4) 122. (4) 123. (2) 124. (3) 125. (4) 31. (2) 32. (2) 33. (2) 34. (3) 35. (l)
126. (3) 127. (4) 128. (4) 129. (4) 130. (4) 36. (2) 37. (2) 38. (4) 39. (1) 40. (2)
131. ( 1) 132. (2) 133. (4) 134. (2) 135. (2) 41. (3) 42. (2) 43. (t)
136. (4) 137. (2) 138. (2) 139. (3) 140. (2)
The branch of chemistry which deals with the nature of surfaces residual forces by attractrng and retaining the molecules of
and changes occuring on the surfaces is called surface chemistry. other species. When brought in contact with them. These
Adsorption on solid or on surface of solution are important surface molecules, however, remains only at the surface of the solid
effects which are useful to understand many physical and chemical or liquid and do not penetrate into the bulk. For example,
properties of the substances when a small amount of finely divided charcoal is put into
A boundary separating two phases is called a surface or a vessel containing a gas, it is observed that the pressure of
interface. the gas decreases rapidly at first, and then gradually. The
E.g. A boundary between water and its vapour. This is a decrease in pressure of the gas is due to the accumulation of
liquid gas interface. the gas on the surface of charcoal.
Surfaces differ from the phases in some properties. Also many
properties of solids, liquids or solutions can be explained by the Higher concentration
of molecular species o o
action of their surfaces. OO
oo o
o
o o

E.g. Surface of solid or liquid has strong affinity for the

particles (atoms or molecules) of the substances that are coming
in contact with it.
Solid

ADSORPTION
The phenomenon of higher concentration of molecular
Adsorption is a surface phenomenon. It arises because of the species (gases or liquids) on the surface of a solid than in the
unbalanced forces on the surface of the solids and liquids. bulk is called adsorption.
If we consider a solid, it is observed that a molecule present
in the bulk of the solid is being uniformly attracted from all
sides by the neighbouring molecules. As a result, there is POSITIVE AND NEGATIVE
no net pull on this molecule. However, a molecule which ADSORPTION
lies near the surface (known as a surface molecule) is being
attracted only by the molecules below it. This is because When the concentration of adsorbate is more on the surface of
there ate no molecules above it. Therefore, the surface absorbent as compared to its concentration in the bulk phase, the
molecules experience a resultant downward attractive forces process is said to be positive adsorption. On the other hand, if
within the solid. In other words, the surface is under tension the concentration of adsorbate is less on the surface of adsorbent
due to unbalanced forces. than that in the bulk phase, it is called negative adsorption. This
type of adsorption takes place only in case of solutions. For
Net inward pull example, when concentrated solution of KCl is shaken with
blood charco aL, it shows positive adsorption but shaking dilute
solution of KCl with blood charcoal shows negative adsorption.
The positive and negative adsorptoins are shown in figure.

Uniform force
of attraction from
all sides. No Bulk
resultant force

Similarly inward forces of attraction exist on the surface of Uniform distribution Greater concentration of Greater concentration of

a liquid. As a result, the surface of the solid or liquid tends bulk adsorbate on its surface
throughout the adsorbate in the bulk phase
(Absorption) (Positive Adsorption) (Negative Adsorption)
to satisf,z their residual forces by attracting and retaining the
molecules of other species. When brought in contact, their Absorption and adsorption
2.2 Chemistry

MgCXANISM OF ADSORTION (d) Adsorbate is always present in higher concentration on the

surface of an adsorbent than in the bulk.
It has been pointed out earlier that the molecules at surface of (e) Adsorption depends upon parameters like temperature (of
the adsorbent are not in the same environment as those inside the the surface) and pressure (of adsorbate gas).
bulk. The surface particles possess unbalanced or residual forces. (0 Adsorption helps in heterogenous catalysis.
As a result of these unbalaced forces, the surface of adsorbent
(i) Desorption: The process of removal of an adsorbed
attract the adsorbate molecules and retain them. In certain cases
substance from the surface is known as desorption.
the unutilised valencies present at the surface are also responsible
(ii) Adsorbate: The substance adsorbed on the surface of
for adsorptoin. For example, if we take a transition metal then
another substance is called an adsorbate or adsorbed
the unbalanced forces in it arise due to the presence of unpaired
phase.
electrons in the d-orbitals.
,New'
(iii) Adsorbent: The substance which adsorbs another
substance (adsorbate) on its surface is called an
x/ \x
;
:

x x-.
x
I I

x.--
Breaking
fi -
l.l
.x-x-*-
adsorbent.
(iv) Heat of adsorption: The heat evolved per mole of
adsorbate during the process of adsorption is called heat
i!
of adsorption.
Unbalanced forces increases with the
(v) Absorption: Absorption is defined as the phenomenon
forrnation of new surfaces.
of uniform distribution of one substance throughout
The extent of adsorption increases with the increases of surface the body of another substance. eg. Water vapours are
area per unit mass of the adsorbent at a given temperature absorbed by calcium chloride to form hydrate.
and pressure. For example when a piece of solid is broken or (vi) Absorbate: The substance which is absorbed by
pulverised to a fine powder, new surfaces are formed (Fig.) another substance is called as an absorbate.
leading to an increase in the surface area and the unbalanced (vii) Absorbent: The substance which absorbs another
forces. Consequently, the extent of adsorption also increases. substance is called as an absorbent.
Examples of adsorbents are activated charcoal, Pt,
ErurxAlpy, Erurnopy AND GtBB's ErueRGy Cxarucr Pd, Ni, Silica gel, gelatin, AlrOr: starch.
DURING ADSORPTION (viii)
Enthalpy of Adsorption iil:f T"*u,#ffi,|"', i:T:l,:il:: ffi:11.::
simultaneously.
During adsoption, new forces of attraction came into existence.
As a result, all adsorption phenomena are generally accompanied x
x x
x x x x x x x
by release of energy and are found to be exothermic. The enthalpy x x x x x x x
x X x x x x x
change taking place for adsorption of one mole of adsorbate x
x
x x x
x x x
xx X
xx x
on an adsorbent surface is called enthalpy of adsorption. In x
X
x x x
x x x
x x x
x x x
X x x x x
generaly, enthalpy of adsorption for chemisorption is more x

negative than that of physisorption (see sectoin 5 .2.2).Enthalpy

of chemisorption is of the order of -200 kJ mol-r while that of Adsorption Absorption
physisorption is generally in the range of -20 to -40 kJ mol-l.

Entropy and Gibb's energy of adsorption

During adsorption of gas (or liquid) on solid surface, the freedom
of movement of gas molecules become restricted. As a reasult te
random and entropy of system decreases. In other words, AS or
Sorption
TAS is negative. Thus, we find that for the adsorption process,
both AH as well as AS (or TAS) are negative. Now, for adsorption
to be spontaneous, Gibb's energy change (AG) must be negative. Difference between Adsorption and Absorption
Therefore, from the relation AG : AH - TAS. We can conclude Adsorption Absorption
that enthalpy of adsorption must have large negative value for
AG to be -ve. 1. It involves higher l. It involves uniform
concentration of the gas or distribution of the
liquid at the surface of a molecular species
CmenAcTERISTIcS OF ADSORPTION
substance. throughout the bulk
(a) Adsorption is a surface phenomenon and usually takes place
with the evolution of heat (with some exceptions). 2. It is rapid in the beginning 2. It occurs at a uniform
(b) It involves physical forces (Van der Waal's forces) or and slows down near the rate.

chemical forces (chemical or covalent bonds). equilibrium

(c) In physiosorption, multi layers of adsorbed particles 3. It is a surface phenomenon. 3. It occurs throughout the
are formed on the surface of the adsorbent. While in body of the material.
chemisorption, formation of only single layer (monolayer)
4. It is a fast process. 4. It is a slow process.
takes place.
 Surface Chemistry 2.3
Types of adsorption: On the basis of forces of attachment of that accompanied with the formation of a chemical bond
incoming adsorbate particle with the surface or adsorbent particle and lies in the range 40 to 200 kJ/mol.
may be physical or chemical and hence adsorption is classified as: (f) It involves the formation of mono layer of adsorbed
(i) Physical adsorption or physisorption or Van der Waals particles.
adsorption. (g) Chemical adsorption involves the formation of surface
(ii) Chemical adsorption or chemisorption or activated compound by the combination of gas molecules with the
adsorption. surface. Sometimes the bonding becomes so tight that,
surface compound desorbs instead of original species.
PxvsrcAr ADsoRprroN (pHysrsoRprroN) eg. When atomic oxygen is adsorbed on graphite
surface, formation of carbon monoxide takes place. If
Physical adsorption (physisorption) is defined as the adsorption the surface is heated, after adsorption CO is desorbed
which involves physical or Van der Waal's forces between the but not the atomic oxygen.
particles of adsorbate and adsorbent. (h) Chemisorption occurs at all temperatures but extent of
adsorption increases with rise in temperature.
Characteristics
eg. Chemisorption is observed in the following cases of
(a) These forces are very weak and similar to the forces adsorbate and adsorbent:
which causes the condensation of gaS into liquid. Hence Adsorption of CO on Tungsten W,
the heat released in physisorption is of the same order of Adsorption of H, on Nickle
the magnitude as the heat of condensation of gases. Adsorption of O, on Silver or Gold or Platinum
(b) Physiosorption is relatively weak and under high
pressure, the adsorbate (like gas molecules) may form Comparison of physi-sorption and chemi-sorlrtion
several layers on the surface of adsorbent.
(c) At lower temperature, physiosorption Chemical Adsorption
takes place to a Physical Adsorption
(Activated ad.)
greater extent whereas it decreases as the temperature is
raised. a. It is caused by intermolecular It is caused by chemical
(d) Process of physiosorption reaches the equilibrium Van der waal's forces. bond formation.
rapidly and the process can also be readily reversed. b. t is not specific. It is highly specific.
(e)
c. It is reversible. It is irreversible.
:'h:T*J*JllTln:':,',T*rrace d. Heat of adsorption is low. - Heat of adsorption is high.
eg. physiosorption is observed in the following cases 20 to 10 kJ/mol - 200 to 400 kJ/mol
of adsorbate and adsorbent: e. No appreciable activation High activation energy is
Adsorption of gases like H2,N2,CO, CO, etc. on energy is involved. involved.
charcoal
Adsorption of solution of acetic acid or oxalic acid
f. It forms multimolecular It forms unimolecular
layers on adsorbent surface layer.
on charcoal.
under high pressure.
AcrrvnrED (cH EM rcAL) ADSoRPTToN
(cnEMrsoRPTIoN) Special point: Chemical Adsorption is endothermic -+
E.g.: Glass * H, gas [Exception]
Activated (chemical) adsorption (chemisorption) is defined as the
adsorption which involves chemical (covalent) bonds between
the particles of adsorbate and adsorbent. Factors Affecti ng Ad sorption
l. Nature of adsorbent:
Characteristics Adsorption o< Surface area of adsorbent or free valency
(a) Chemisorption is exothermic (with some exceptions). of the solid.(So, powdered form of adsorbent is more
(b) Chemisorption is highly specific and is possible only effective)
between specific adsorbent and adsorbate. (i) Adsorbent with more free valencies or unbalanced
(c) It involves the formation of chemical bonds between forces show more tendency to adsorb. eg. Transition
adsorbate and adsorbent molecules for which it requires metals like Ni, Pd, Pt, etc.
high activation energy. Therefore, it is also known as (ii) Also solids having porous nature provides large surface
activated adsorption. area for a given mass and are found to be effective
(d) Chemisorption is relatively strong. However, it is a adsorbents. eg. Silica gel, charcoal, etc.
slow process due to the requirement of high activation
energy. 2. Nature of adsorbate:
(e) The heat evolved in chemisorption per mole of A. Adsorption of Gas: Adsorption * T. of gas
adsorbate is nearly of the same order of magnitude as B. Adsorption from solution: Adsorption ". Concentration
of solute in the solution.
2.4 Chemistry

Volurne of Gases at N. Tl P adsorbed by 1 g of Charcoal at 288 K

Gas H2 N2 CO CHn CO, HCI NH, SO,

Critical Temperature, I, (K) 33 t26 134 190 304 324 406 430

Volume adsorbed (mL) 4.7 8.0 9.3 t6.2 48 72 181 380

Critical temperature increase

Ease of liquification increase
Extent of adsorption increase
1.0 pt

3. Effect of temperature: The surface area of adsorbent

(i) Substances like colloidal substances, finely divided
exothermic process. substances, porous substances and substances with
Adsorption is an exothermic process. According to rough surfaces are good adsorbents as they provide
Le-Chatelier's principle, it is favoured at low temperature. large surface atea for a given mass.
As the temperafure of the surface increases, extent of (ii) Adsorption is a surface phenomenon, hence, with the
adsorption decreases increase in the surface area of adsorbent for a given
mass, extent of adsorption increases.
eas adsorbed o.'
( ,.".. amount of v ' ).
I temperaure) Types of adsorption isotherm: The relationship between the
amount of a substance adsorbed per unit mass of adsorbent and
c the equilibrium pressure (in case of gas) or concentration (in case
C o
o ISOBAR ISOBAR of solution) at any constant temperature is called an adsorption
E-+ o-
L-I
oI o isotherm.
al U'
E(u
El
(U (i) Freundlich adsorption isotherm (Physical adsorption):
(U
.9
(o
.9 The empirical equation showing the relationship
o E
.C
o between the amount of an adsorbate (gas) adsorbed by
L -c
o the unit mass of an adsorbent (solid) and the equilibrium
Temperature (T) + Temperature (T) + pressure at a constant temperafure over a limited range
of pressure is called Freundlich adsorption isotherm.
4. Effect of Pressure:
Adsorbent - Solid, Adsorb ate - Gas
At any temperafure, the volume of gas adsorbed increases
with increase in pressure. Therefore, at constant temperafure X
According to this = Kg,trn
the extent of adsorption varies directly with low pressure
range of the gas. However, at high pressure the surface of
adsorbent is almost fully covered by the adsorbed gaseous K & n are constants. Value of K & n depends on the
molecules and hence, the extent of adsorption becomes nature of adsorbent & nature of adsorbate.
independent of pressure. According to this * increase with increase of P but at
Adsorption Isotherm. high pressure * becomes constant.
The extent of the adsorption of a gas on a solid is generally When taking logarithm of equation.

expressed as
x bt:=logK+ltoeP
m
Where:

high P (constant adsorption)

bs#t
1
Slope =
XA n
ml
I

lntercept - log K
But graphically
log P
-+ Saturation
Pressure (P) pressure In solution (liquid + solid)
E.g.: dyes solution + Charcoal ->
x- Mass of adsorb ate,
m - Mass of adsorbent
X o" x 1
Theoretically P KC, C - (Conc' of liquid)
m m
 Surface 2.5

(ii) Langmuir adsorption isotherm (Chemisorption, 6. Which of the following is an example of physical adsorption?
unilayer adsorption): (1) Adsorption of acetic acid in solution by charcoal
Langmuir 1916 postulated that: (2) Adsorption of CO on tungsten
1. The gases being adsorbed cannot form alayer more (3) Adsorption of CO on Ni
than a single molecule in depth. (4) Adsorption of H, on Ni
2. There is no interaction between the adjacent
adsorbed molecules.
3. A dynamic equilibrium exists between the adsorbed
(I ) decrease in temperature
(2) increase in temperature
molecules and the free gas molecules.
(3) decrease in pressure
4. The adsorption sites are equivalent in their ability
(4) decrease in surface area
to adsorb particels.
The constants a and b are characteristic of a
particular system at a particular temperafure. CATALYStS
Xac A catalyst is defined as a substance which when added to the
For Solid + Liquid reacting system alter the rate of the reaction without itself being
m l+bc
consumed in the reaction.
Thus, the phenomenon of changing the rate of a chemical
Applications of adsorption:
reaction with the help of a catalyst is known as catalysis.
1. Production of high vaccum
2. Gas masks A catalyst combines with one or more of the reactant
molecules to form an intermediate which is a complex of reactant
3. Humidity control
and catalyst.
4. Removal of colouring matter from solution
5. Heterogeneous catalysis Reactant * catalyst complex
6. Seperation of inert gases -+
The complex decomposes to yield the products and regenerates
7. Softening of hard water the catalyst.
8. De ionisation of water
9. In curing diseases CompleX --* products + catalyst

10. Cleansing agents Acatalyst do not influence the position of equilibrium ofreversible
11. Froth floatation process reaction, as it increases the rate of forward and backwardreaction
12. Adsorption indicators equally. Hence, value of equilibrium constant is also not affected
I 3. Chrom atographic analysis by the catalyst.
A catalyst if present even in an extremely small amount can
cause considerable increase in the rate of a reaction.
The reactions, the rates of which are accelerated by catalysts
are called catalyzed reactions.
1. The process of removal of an adsorbed substance from the E.g. The thermal decomposition of KCIO, is very slow in the
srxface is known as absence of a catalyst even on heating, However, when a small
(1) desorption (2) sorption amount of MnO, is mixed with KCIO3 before heating, evolution
(3) oxidation (4) reduction of oxygen occurs rapidly.

2. The molecules of the substance which gets adsorbed are

2KC1O3(.)
Potassium
-+#--
chlorate
2KCl(,r
Potassium
* 3orr*r (rapid)
chloride Oxygen
termed as
adsorbate
(1) (2) adsorbent Thus, in above reaction MnO, acts as a catalyst which increases
absorbent
(3) (4) absorbate the rate of decomposition of KCIO3 and can be recovered
unchanged (chemically) at the end of the reaction
3. A substance- which adsorbs another substance
.
on its surface is
called Catalytic reactions are divided into two types.
(l) adsorbate (2) absorbate (a) Homogeneous catalysis: When the reactants and the catalyst
(3) adsorbent (4) absorbent are in the same physical state, i.e. in the same phase, it is
called homogeneous catalysis. For example:
4. In adsorption of acetic acid on charcoal, the acetic acid is (i) Lead chamber process: In this process for the manufacture
of sulphuric acid (H2SOJ, NO (gas) is used as a catalyst.
(I) adsorbate (2) adsorbent
(3) absorbent (4) absorbate 2SOz(g) + Or(g).% 2SO,(g)

(ii) Inversion of cane sugar: In aqueous solution, it is

held on the surface of the adsorbent by weak Van der Waal' s catalysed by dilute acid (Hydrogen ions)
forces. H,sou(aq)
(l) Chemisorption (2) Absorption a,r*f,9,, * Hro , cuH,rou * c6H12o6
(3) Physisorption (4) Biosorption
2.6 Chemistry
(b) Surface catalyst or Heterogeneous catalysis: When the Promoters: Those substances which do not themselves
catalyst and the reactants are not in the same physical state acts as a catalysts but their presence increases the activity
i.e. not in the same phase, it is called heterogeneous catalysis. of a catalyst are called catalylic promoters or catalyst for a
For example. catalyst. Example: In the Haber'process for the synthesis of
(i) Decomposition of HrO , (l): ammonia, Fe is the catalyst while molybdenum (Mo) acts as
a promoter.
2H2O 2(/) 2H2O(t) + O' (g)
-% N,(e) +3Hzfs)
(ii) Habel's process for NH, ffi 2NH,(g)

Nr(g) +3H2tg)r@ 2Mr(g) Catalytic Poison: Substances which inhibit the catalytic
(iii) Synthesis of C{OH activity of a catalyst called catalytic poisons.
are

Cu
Catalytic poison when present (even in trace amounts)
CO(e) + 2Hr(g) ZnO - Cr2O,
cH3oH(/) decrease the activity of catalyst ultimately making it inactive
(i.e., the catalyst is said to be poisoned). Poisoning of a
catalyst results into decrease in the rate of reaction.
TvpeS OF CATALYSTS
E.g.
Catalysts are divided into four types. (i) In the conversion of SO, to SO, platinum is used as
(i) Positive catalysts (ii) Negative catalysts catalyst.
(iii) Autocatalysts (ir,)
Induced catalyst Arsenic compounds acts as a catalytic poison for this
(i) Positive catalysts: The substance which increase the rate reaction.
of a reaction are known as positive catalyst. It decrease the When present even in trace amounts it completely
energy of activation for the reaction. For example: destroys the catalytic activity of Pt catalyst, by forming
platinum arsenide at the surface.
2KClOr(s) 2KC1(s) + 30 r(g
-M,,o'9+ (ii) Carbon monoxide or HrS in hydrogen g&s, acts as a
Fe(s)
N, * 3H, , 2NH3 (g) poison for Fe catalyst in the Haber's process for NH3,
AsrO, acts as poison for Pt asbestos in contact process
(ii) Negative catalysts: The substance which decrease the rate for HrSOo
of chemical reaction is called negative catalyst or inhibitor. It Inhibitors: Those substances which retard the rate of a
increases the activation energy of the reaction. For example. chemical reaction are known as inhibitor. For example: HrPOo,
glycerol or acetamide decrease the rate of decomposition of
NarSo, * ]2L02 -% NarSoo hydrogen peroxide.

I General characteristics of catalysts

c6H5cHo
2
02ryc6H5cooH (i) A catalyst remains unchanged in mass and chemical
composition but can change their physical state.
(iii) Autocatalysts: When one of the products of the reaction
begins to act as a catalyst, it is called auto-catalyst. For (ii) Only a very small amount of catalyst is sufficient to
catalys e a reaction.
example. In the initial stages the reaction is slow but as
soon as the products comes into existence the reaction rate
(iii) A catalyst does not initiate a reaction.
increases
(iv) When a catalyst is a solid, it is usually more efficient when
used in finely divided form.
cH3cooc2Hs + H,o .f,"f;93f * c2H5oH (v) Generally catalyst does not change the nature of products.

2KMnOo * 5C2O4H,
-
* 3H2SO+ €
(vi) A catalysts does not change the equilibrium state of a
reversible reaction but helps to achieve the equilibrium
state or position of equilibrium in lesser time.
Kzsoo * loco2 + 8H'o (vii) The catalysts is generally specific in nature.
'XS"3,11
(viii) Change at rate is constant of reaction.
(iv) Induced catalyst: When a chemical reaction enhances (ix) Does not change free energy of reaction.
the rate of another chemical reaction it is called induced (x) Participate in mechanism of reaction.
catalysis. For example:
Soduim arsenite solution is not oxidised by air. If however, Applications of Homogeneous catalysts
air is passed through the mixture of NarAsO, & NarSO, (i) Industrial applications: Homogeneous catalysts are used
both of them undergo simultaneous oxidation. The oxidation in industrially important reactions like polymerization,
of sodium sulphite, thus influences the oxidation of sodium carbonylation, etc.
arsenite. (ii) Domestic applications: Detergents used for washing
purposes contains enzymes which catalyze the oxidation
NarSo, * ] oz € NarSoo and depolymerization of stains. Metal atoms present
[Link] L air Sod. sulphate
in cleansers act as catalyst and enhance the bleaching
*3*:* .:?: action.

- T,**:.?r
 Surface Chemistry 2.7
Application of Heterogeneous catalysts Adsorption theory: This theory explains the heterogeneous
(i) Heterogeneous catalysts are largely used in chemical catalysis. The role of a solid catalyst in enhancing the reaction
industries because they are easier to separate from the rate is explained on the basis of this theory in the following steps.
products of the reaction than homogeneous catalysts. (i) The reactant molecules are absorbed on the surface of the
(ii) Also many heterogeneous catalysts are expensive metals catalyst at adjacent points. Adsorption leads to higher
such as rhodium, platinum, etc., and cannot be thrown concentration of the adsorbed reactant on the surface of a
away. The heterogeneous catalyst so recovered from one catalyst.
reaction can again be used for another reaction. (ii) As adsorption is an exothermic process, the heat of adsorption
Distinguish between homogeneous and provides the necessary activation energy for the chemical
heterogeneous catalysis. reaction to proceed.
(iii) The adsorbed reactant molecules are tied on the solid surface
No. Homogeneous catalysis Heterogeneous catalysis of the catalyst. The bonds between the atoms of chemisorbed
(i) The catalyst and the The catalyst and the reactant molecules are weakened. The reactant molecules of
form a single reactants are in different
reactants sufficient energy combines together and with the surface of
phase. phases the catalyst to form surface activated complex.
This adsorbed activated complex is decomposed to form
(ii) The catalyst dissolves into The catalyst does not 'products at a definite faster rate.
the gas phase or solution dissolve in the reacting (iv) The product molecules rapidly leave the catalyst surface to
(a reacting mixture). mixture. make room for the other reactant molecules to get absorbed.
(iii) The reaction occurs in the The reaction does not Thus the chemical combination between reactant molecules
goes on at the surface of the catalyst at a much faster rate.
liquid phase or gas phase. occurs in gas or solution
phase but occurs on the
surface of solid catalyst. Catalysts in lndustry: Some of the important processes and
their catalyst are given below.
(iv) The catalyst is often The catalyst adsorbs the
involved in the chemical reactant molecules to form Industrial process Catalyst used
reaction. a chemical bond between
catalyst and the reactant Preparation of O, from KCIO3 (Hetero) MnO,
molecules.
Haber's process for arnmonia (Hetero) Fe: Mo as promoter
(v) The catalyst cannot be The catalyst can be easily
easily separated from the separated from reaction Ostwald's process for HNO3 from Pt Gauge
products. products. NH, (Hetero)
(vi) The rate of the reaction The rate of reaction is Chamber process for H2SO4 (Hetero) Nitric oxide (NO)
does not depends on the proportional to the surface gas
surface atea of catalyst. area of catalyst.
Contact process for H2SO4 (Hetero) vro,
(vii) The homogeneously The heterogeneously
catalyzed reactions are catalyzed reactions are Deacon's process for manufacturing of CuCl,
often little faster than those often slower than those CI, (Hetero)
which are heterogeneously which are homogeneously
cata|yzed, catalyzed. Bosch process for H, (Hetero) FerO, + CrrO,

THEORIES OF CATALYSIS Manufacturing of vegetable ghee Ni, Cy as promoter

(Hetero)
Intermediate compound formation theory: This theory explains
homogeneous catalysis mainly. Hydrolysis of ester (Homo) aq. HrSOo
According to this theory the catalysts combines with one of
the reactants to give an intermediate compound. This compound Aldol condensation of aldehydes (Homo) -oH
intermediately reacts with the other reactants and gives the
product and regenerates the catalyst in its original form. Enolisation of ketones (Homo) H+ or -OH
Thus the reactants do not directly combine with each other,
Cracking of hydrocarbons (Hetero) Zeolites
instead they reacts through the catalyst which provides an
alternative pathway which involves lesser energy of activation.
For example: The function of nitric oxide (NO) as a catalyst in Catalytic activity of d-block metals
the formation of SO, is explained as follows. (i) Metals lying close to the middle of the d-block are most
2NO*O, € 2NO2 active catalysts.
catalyst reactant lntermediate (ii) Strong catalytic activity is observed with d-block metals like
NO, + SO,
fast
SO, + NO iron(Fe), vanadium(V) and chromium (Cr) for the adsorption
reaction
intermediate reactant product catalyst regenerated of various gases like C2, CzHz, CzH4, CO, H2, CO, N, etc.
2.8 Chemistry

(iii) Manganese (Mn) and copper (Cu) are unable to adsorb N, Homogeneous or heterogeneous enzyme catalysed
and COr. reacations
(iv) s-block elements like Mg and Li metal can adsorb only Or.
(i) All biological reactions are catalysed by special catalysts
Enzyme catalysis called enzymes.
Enzyme catalysts are homogeneous biological catalysts (ii) The enzymes forms a homogeneous mixture with the
consisting of large size protein molecules which acts as a catalysts substances taking part in biochemical reactions in the living
for biochemical reactions taking place in the living systems. systems.
E.g. Amylase, Carbonic anhydrase. (iii) Hence, enzyme catalysed reactions are always homogeneous
reactions.
Charaterstics of enzyme catalysis E.g.
(i) Enzymes are high molecular weight (i.e., molar mass (a) Inversion of cane sugar:
ranging between 15,000 to 1,000,000 g/mol) large
complex protein molecules that acts as a homogeneous CrrHrrO,,,, + H2Ool 4 C6H12O6(uq) * CuH,rOutuot
catalyst for biochemical reactions in living systems.
(ii) The enzymes reduce activation energy to much greater (b) Conversion of glucose to ethyl alcohol:
extent than that by other types of catalysts and hence they
are efficient catalysts under very mild conditions. C6H12Oquo 4 2CrHsOH(uq) * zCO zG)
eg. Th e enzyme catalase reduces the activation energy of Glucose Ethyl alcohol

HrO, decomposition from 76 kJ mol-r to 8 kJ mol-r and

rate of reaction increases by a factor of 1015 at298K.
Mechanism of enzyme catalysis
(iii) One molecule of most of the enzymes can act on 20,000 or
more reactant molecules per second. eg. Hydration of CO,
(i) Enzymes are highly specific towards its action. They
in red blood cells to produce bicarbonate ion is catalyzed contains one or more active sites at which a specific substrate
(reactant) molecule fits.
by the enzyme carbonic anhydrase which acts on 600,000
reactant molecules per second.
(ii) The active site acts like a lock into which fits only a specific
(iv) They are highly specific in their action, i.e,, they catalyse key (substrate or reactant).
only a particular reaction of a particular compound. (iii) The structure of active site is flexible and hence it can
(v) High efficiency: Enzyme catalysts increase the speed accommodate more than one type of substrate.
of reactions by 108 to 1,020 times as compared to the (iv) The active site returns to its original state after releasing
uncatalysed reactions. The enzymes are highly efficient the products. This mechanism is called "Lock and key"
and one molecule of enzyme may transforn one million mechanism.
molecules of the reactant per minute. (v) The active site of the enzyme catalyst binds the substrate
(vi) Required in small quantities: Extremely small quantities (reactant) and produces enzyme-substrate complex which
of errzyme catalysts are required and they can increase the then decomposes to give the product of reaction and the
rute of reaction by factors of 103 to 106. eflzyme is recovered.
(vii) Specificity: The enzyme catalysts are highly specific in E+Si-ES+P+E
nafure. Almost every biochemical reaction is controlled
by its own specific erLzyme. eg. Urease catalyses the Where, E and S are enzyme and substrate respectively. ES is
hydrolysis of urea and none of the several thousand other an efizyme-substrate complex and P is the product.
erLzymes present in the cell catalyses that reaction. E.g.
+ H2O Urease
, rA*.3S"gi2o*ia. (i) Decomposition of HrO, using erryme catalase as a
\*aoNH, catalyst:
(viii) Optimum pH: The rute of an enzyme catalysed reaction
.
is maximum at aparticular pH called optimum pH. This is
between pH values of 5 - 7 .
,ft31:P**' H' o' r
:3.:,:'r,

(ix) Control of activity of enzymes: The catalytic activity of (ii) Oxidation of Fe2* ion to Fe3* ion using ferroxidase
enzymes is controlled by various mechanisms. One of the enzyme as a catalyst:
mechanism is inhibits by various organic and inorganic Ferroxidas
molecules.
aFeli*+ 4Hi"d + Or,r, +fei"i + 2H2Osy
(x) Regulated activity: The activity of most enzyme catalysts
is closely regulated.
(xi) Optimum temperature: The rate of an eruzyme reaction
becomes maximum at a definite temperafure known as the
lrurrxr QuEsrloNS 2
optimum temperature. On either side of this temperature,
the enryme activity decreases. E.g. The eruzyme catalysts
L. The phenomenon of increase in the rate of a reaction with the
help of a
are active at moderate temperature 298-310 K and the
(1) reactant (2) product
human body temperature (3 l0 K) is suited for enzyme
(3) catalyst (4) reagent
catalysed reactions.
 Surface Chemistry 2.9
2. A substance that decreases the rate of a chemical reaction is (i) Crystalloid (ii) Colloid
called This classification soon proved to be wrong since a crystalloid
(I ) inhibitor (2) prohibitor could behave as a colloid under different conditions and vice-
(3) promoter (4) reactor versa.
E.g. NaCl behaves as a crystalloid in aqueous medium and
3. The rate of heterogenous catalysed reaction is
(1) proportional to the surface area of the catalyst behaves as a colloid in benzene mediuffi, whereas soap behaves
(2) proportional to the temperature as a typical colloid in water and behaves as a crystalloid in
(3) independent of temperature 30. alcohol.
So new classifications was given based on the size of solute
(4) inversely proportional to pressure
particles.
4. In contact process for manufacfure of HrS O
o, catalyst used (i) True solution: A true solution is referred to as the
for the oxidation of SO, to SO, is homogeneous mixfure of solute and solvent.
(l) iron with molybdenum (2) copper, In true solution, the solute particles have a size that ranges
(3) vanadium pentoxide (4) nickel between 0.1 nm to 1 nm.
5. In the synthesis of ammonia, AlrO, is added and Fe catalyst These solute particles do not settle.
asa E.g. When NaCl (sotute) is dissolved in water (solvent), we
(1) inhibitor (2) promotor obtained as a homogeneous solution/true solution.
(3) retarder (4) activator (ii) Suspension: The aggregates of molecules in which particle
size is larger than 103 nm is referred as suspension.
6. The tendency of catalyst to catalyze the reaction to form The particles of suspension can be seen by naked eye or by
particular product is called as microscope.
( 1) catalytic activity (2) retardation E.g. When sand is stirred into water, it gives a heterogeneous
(3) catalytic selectivity (4) None of these mixture called coarse suspension, in which the solute-like
7. A biological catalyst is particles (sand) settle out.
(1) an amino acid (2) a carbohydrate Components of suspension can be easily separated.
(3) the nitrogen molecule (4) arl enzyme
(iii) Colloidal dispersion: Colloidal dispersion or colloids
- represents an intermediate mixfure between true solution anci
8. Enzyme amylase is found in suspension. In this, the dispersed phase (solute) is suspended
(1) nervous system (2) endocrine system in dispersion medium (solvent).
(3) human digestive system (4) excretory system The colloidal (dispersed phase) particles are bigger than the
- particles of true solution and smaller than the suspension
particles.
COLLOIDAT SOLUTION The size of colloidal particles lies between I nm to 103 nm.
Thomas Graham (1861) studied the process of [Link] of When a substance on treatment with a solvent acquires a
particle size ranging between I nm to 103 nm then it is said
dissolved substances through a parchment paper or an animal
membrane and divided into two classes:
to be in the colloidal state.

Table: Comparison of Tlrre solutions, Colloids and Suspension

[Link]. Property True Solution or Crystalloidal Colloid Suspension
(i) Particle size < 10-7 cm or l0A l0-7 to lO-s cm > l0-5 cm or lffA
orlmpor<1nm or 10A to 1ff4 or 100 mp
or lmp to 100 mp or > 100 nm
or I nm to 100 nm
(ii) Visibility Not visible with any of the optical Visible with ultra microscope Visible with naked eye
means

(iii) Seperation
(a) with filter paper Not possible Not possible possible
(b) with membranes Not possible possible possible

(iv) Diffirsion Diffirses rapidly Diffirse very slowly Does not diffuse
(v) Settling Does not seffle Does not settle but it may Settles under gravity
settle under Centriluge
(vi) Nature Homogeneous Heterogeneous Heterogeneous
(vii) Tyndall effect & does not show shows May or may not show
Brownian moment
2.10 Chemistry

(ii) The particles are so small that they cannot be seen with an
Crystalloidal particles Colloidal particles
ordinary microscope, can pass through ordinary filter papers
ooooo
ooooo
COCC and can be detected by light scatterit g.
ooooo ccoo The medium in which the dispersed phase exists is called a
dispersion medium. It is a continuous phase.
Smaller particles < 10A Particles size 10A to 103 A
Dispersion medium

oooo
Suspensions
(i) Colloidal dispersion is heterogeneous and is a two phase
system. Dispersed substance constitutes one phase while the

oooo
Particles having size
other phase is made up of dispersion medium. This is due to
the presence of definite surface of separation between each
bigger than 10004
particle and the medium.
(ii) The terms dispersed phase and diqpersion medium are
analogous to the terms solute and solvbnt respectively in the
Tvpes oF coLtorDAL soLUTtoNs
ordinary solution. E.g. For a colloidal solution of copper in
A colloidal system is made of two phases. water, copper particles constitutes the dispersed phase and
Dispersion phase water the dispersion medium. Depending on the physical
states of dispersed phase and dispersion medium, colloidal
(i) The discontinuous phase of colloidal particles of the solutions are of eight types
size lying between I nm to 103 nm that are present in the
dispersion medium constitute the disperse phase.

Classification of colloidal systems based on dispersed phase and Dispersion medium

TYpe of Colloidal Solution Dispersed phase Dispersion medium Example

Foam gas Liquid Whipped Cre&ffi, Shaving Cream, Soda water

Solid Foam gas solid Cork, pumice stone, Foam rubber

Liquid Aerosol liquid gas Fog, mist, clouds, insecticide sprays.

Emulsion liquid liquid milk, hair cream, *butter, cold cream.

Gel liquid solid butter, cheese, curd, Jellies, boot polish

Smoke (aerosol) solid gas dust, soot in air

SoI (liquid) solid liquid ink, colloidal gold, paints, cell fluids.
Solid sol solid solid Ruby glass (gold dispersed in glass), alloys
gem stones, minerals.

A colloidal dispersion of one gas in another is not possible since The colloidal systems which have more rigid structures are
the trvo gases would give a homogenous molecular strucfure. called gel. Gelatin behaves both as a sol and a gel.
(i) Sol: A sol is a dispersion of a solid in a liquid or
Classification of colloida! systerns dispersion of solid in a solid. E.g. Milk of magnesia.
l. Classification based on appearance: This colloidal system (ii) Aerosol: An aerosol is a dispersion of a liquid in a gas
has the appearance of a fluid, then it is called a Sol. On the or solid in a gas. E.g. Fog, mist, cloud, smoke.
basis of dispersion medium different types of sols are possible. (iii) Emulsion: An emulsion is a dispersion of a liquid in a
liquid. E.g. Milk.
[Link]. Dispersion medium Name of solution 2. Classification based on interaction of phases:
Lyophilic sols: Colloidal solutions whose dispersed phase
I Water Hydrosol or aquosol has considerable affinity for the dispersion phase, are called
2. Benzene Benzosol
lyophilic sols (solvent - liking).
E.g. Dispersion of gelatin, starch, gum and proteins in water.
3. Alcohol Alcosol Lyophobic sols: Colloidal solutions whose dispersed phase
has no affinity or attraction for the medium or for the solvent
4. Air Aerosol.
are called Lyphobic colloidal (Solvent hating) solutions.
 Surface Chemistry [Link]
Comparision of Lyophobic and Lyophilic sols

Property Lyophilic sol (Emulsoid) Lyophobic sol (suspensoid)

1 Preparation Can be easily prepared by shaking or Can not be prepared easily
warming the substance with solvent Special methods are required

2. Stability are more stable are less stable

3. Reversibility are reversible are irreversible

4. viscocity viscocity is much higher than that of solvent viscocity is nearly same as that of the solvent

5. Surface tension Surface tension is usually low Surface tension is almost same as that of solvent

6. Hydration or solvation These are highly solvated as the particles These are less solvated as the particles have less
have great affinity for solvent affinity for the solvent
7. Charge The particles have little charge or no charge The particles carry a characteristic charge either
at all positive or negative

8. Visibility Particles can not be seen under microscope Particles can be seen under microscope

9. Coagulation or Precipitated by high concentration of Precipitated by low concentration of electrolytes

precipitation electrolytes
10. Tyndall effect Less Scaffering More Scattering
1l Migration in electric may or may not migrate as they may or may migrate towards anode or cathode as these
field not carry charge. particles carrry charge.
t2 General Example Mostly of organic nature Ex. Gelatin, Starch, Mostly of Inorganic nature E.g. Transiton metal
Gum, Albumin & Cellulose Solution salt in water Gold, As etc.

Methods of preparations Metal rods

Lyophilic sols may be prepared by simply warming the solid with + KOH
liquid dispersion medium eg. starch with water. On the other hand
lyophobic sols have to be prepared by special methods. These +
methods fall into two categories lce
A. Dispersion Methods: In this larger macrosizedparticles are
broken down to colloidal size
l. Mechanical dispersion:
The substance to be dispersed is grinded as finely as
possible and then shaken with the dispersion medium
to form a suspension. This suspension is passed through
colloidal mill where the suspended particles are broken
to produce particles of colloidal size.
2. Electro-dispersion (Bredig's arc method) Electro-dispersion
This method is suitable for the preparation of colloidal
solutions of metals like gold, silver, platinum etc. An
arc is struck between the metal electrodes under the 3. Dispersion by ultrasonic vibrations
surface of water containing some stabilizing agent such Claus prepared mercury sol by subjecting Hg to
as a traces of KOH. The water is cooled by irnmersing sufficiently high frequency ultrasonic vibrations as
the container in alice bath. The intense heat of the arc shown in fig. The ultrasonic vibrations produced by the
vapourises some of the metal which condenses under generator spread through the oil and strike the vessel
cold water. containing mercury under water. This produces clouds
E.g.: Pt, Ag, Cu, Au, Sols are prepared by this methpd. of mercury which form the mercury sol.
2.12 Chemistry

2. Chemical method:
Colloidal systems can be obtained by
Water various chemical reactions such as double
decomposition, oxidation, reduction,
Hg hydrolysis, etc
(a) Double Decomposition
oir
A sol of arsenious sulphide is prepared by
Electrical passing HrS gas through a dilute solution
oscillator
of arsenious oxide and removing the
excess HrS by boiling.
Quartz generator
NaCl + AgNO, # AgCl + NaNO,
Fig: Prep. of Hg sol. by ultrasonc vibrations
AS2O33H2S+AS2S3 + 3HrO
4. Peptization (b) Oxidation
The dispersion of a freshly precipitated material into A colloidal sulphur sol is obtained by
colloidal solution by the action of an electrolyte in the oxidation of an aqueous solution of
solution is termed peptrzation. The electrolyte used is hydrogen sulphide with air or sulphur
called a Peptrzing agent. dioxide.
A. few examples of sols obtained by peptization are: HrS +2HNOr+ 2NO2+ S +2HzO
(i) Freshly prepared ferric hydroxide on treatment 2H2S * O, 25 + 2H2O
with a small amount of ferric chloride solution -+
2H2S + SO, --+ 35 + 2H2O
at once forms a dark reddish brown colloidal
solution. Ferric chloride acts as a peptizing (c) Reduction
agent. Sols of metals such as silver, copper, gold
(ii) Freshly precipitated silver chloride can be and platinum are obtained by reducing
converted into a colloidal solution by adding the aqueous solutions of their salts by
a small amount of hydrochloric acid.
non-electrolytes such as formaldehyde,
(iii) Cadmium sulphide can be peptrzed with the tanin, phenyl hydrazine, carbon
help of hydrogen sulphide. monoxide and phosphorus. Zsigmondy
The process of peptization thus involves the prepared the gold hydrosol by reducing
adsorption of suitable ions (supplied by the pottasium aurate with formaldehyde. In
electrolyte added particularly a common this reaction, chloroauric acid, H[AuCloJ.
ion) and electrically charged particles then 4H2O, first formed, is made to react
split from the precipitate as colloidal particles. with potassium carbonate in an aqueous
B. Condensation methods: In this colloidal sized solution to yield potassium aurate:
particles are built up by aggregating single ions or 2H[Au]Cl4l +5KrCO,#
molecules. This method is known as condensation 2KAuOr+5CO2+8KCl+HrO
method. The resulting solution is heated and
1. Physical Methods: a dilute solution of formaldehyde is
(a) By condensing vapours: Sols of sulphur added dropwise when reduction occurs
and mercury can be formed by passing according to the reaction:
the vapours of sulphur and mercury in
cold water containing some NHoNOr. 2KAuO, + 2CH,O * KrCO, ---+
(b) By exchange of solvent: when a true 2Au(sol) + 3HCOTK * KHCOr+ HrO
solution is mixed with an excess of Potassium atttate, KAuO, acts as the
some other solvent in which the solute stabilizer of the red gold sol obtained. The
is insolulble but solvent is soluble, a
colloidal sol is formed. For eg. when a
, miscelle of the gold sol is represented by
the formula
solution of sulphur in alcohol is poured in
excess of water, a colloidal sol of sulphur
(mlAu)nAuOi .@ - x) K.) xK*
(d) Hydrolysis
is formed.
Colloidal sols of heavy metals are
(c) By excessive cooling: molecules of obtained by the hydrolysis of the
certain substances condense together to
solutions of their salts. Thus, when a
form particles of colloidal size. For eg. small amount of ferric chloride is added
colloidal sol of ice in an organic solvent to boiling wat er, a red-brown sol of ferric
like ether or chloroform may be prepared
hydroxide is obtained:
by freezing the mixture of water and the FeCl, + 3HrO Fe(OH), + 3HCl
solvent.
This is because
FeCl, Fe3* + and
 Surface Chemistry 2.13

Fe3* + H2o"- + 3H A 2. Diffusibility: The colloidal particles constituting the

Boiling promotes the reactions because dispersed phase do not readily diffuse through parchment or
HCI formed is removed with water other fine membranes. In fact, it was this property which led
vapours from the system. In this reaction, Thomas Graham to lay the foundation of colloid science, &s
iron oxychloride, FeOCl, formed as a already mentioned.
result of incomplete hydrolysis of 3. Filtrability: The colloidal particles readily pass through
FeClr, is belived to act as the stabilizer. ordinary filter papers along with any dissolved material. This
FeCl, + H2O ---+ FeOCI + 2HCl is because even the finest filter paper has pores bigger than
(e) Exchange of Solvents: the colloidal dimensions.
Sols can also be obtained by exchange of 4. Visibility: It is not possible to see colloidal particles even
solvents. For instance, when a concentrated with the help of a powerful microscope. A gold sol, for
solution of sulphur in alcohol is poured in a instance, appears to be as clear as a true solution of gold
large amount of boiling water, the alcohol chloride in water. The reason for the invisibility of colloidal
evaporates leaving behind sulphur particles particles has already been discussed.
which form nuclei that rapidly grow into a Attempts have been made in recent times to use ultraviolet
colloidal sol. rays or cathode rays for seeing the colloid al parlicles. But,
these rays make no impression on the retina of the eye.
PURIFICATION OF COLLOI DAL However, the images formed by them can be photographed.
The electron microscope, for instance, makes use of a
SOLUTIONS beam of cathode rays and by combination of special types
The presence of impurities, particularly the electrolytes, renders of lenses, images of colloidal particles can be obtained on
the sols unstable. The cause of this instability will be discussed photographic plates.
latter. 5. Colligative Properties: The magnitude of osmotic pressure,
lowering of vapour pressure, depression in freezing point and
Dialysis
elevation in boiling point, depend upon the number of solute
It has already been stated that while particles in the true particles present in a given mass of the [Link], colloidal
solution can easily diffuse through the parchment and other fine particles are not simple molecules. These are physical
membranes, the colloidal particles, being much larger, cannot aggregations of molecules. In arsenic sulphide sol, for
do so [Link] process of separating substances in colloidal instance, each particle is composed of about 1000 molecules.
state from those present in true solution with the help of fine Thus, for a given mass of arsenic sulphide, the number of
membranes, is known as dialysis and the membrane used for the particles in the sol will be only 1/1000 th of the number present
purpose is known as dialyser. Oridinarily, the process of dialysis in true solution. Hence, all colloidal dispersions (unlike true
is quite slow but it can be quickened by applying an electric field solutions) give very low osmotic pressure and show very
if the substance in true solution is an electrolyte. The process is small fueezing point depression or boiling point elevation.
then called electrodialysis. 6. Optical Properties: It was observed by Tyndall, inl869,
Ultrafi!tration that when a beam of light is passed through a true solution,
it cannot be seen unless the eye is placed directly in the path.
The separation of solutes from colloidal systems can also be
However, when the same beam of light is passed through
carried out by the process known as ultrafiltration. Ordinarily,
a colloidal dispersion, it becomes visible as a bright streak.
filter papers have larger pores hence the colloidal particles
This phenomenon is known as the Tyndall effect and the
can readily pass through alongwith the ions or molecules in
illuminated path (streak of light) is known as Tyndall cone.
solutions. But the pores can be made smaller by soaking the filter
This phenomenon is due to the scattering of light from the
papers in a solution of gelatin or collodion Cur[Fe(CN)u] and
surface of colloidal particles. In a true solution, there are no
subsequently hardening them by soaking in formaldehyde. Other
particles of sufficiently large diameter to scatter light and
semipermeable membranes are
hence the beam is invisible. The visibility of dust particles
(a) animal or vegetable membranes
in a semi-darkened room when a sun beam enters or when a
(b) parchment membrane, cellophane membranes
light is thrown from a light projector.
(c) Inorganic gelatinous membranes like silicates of iron, cobalt,
The intensity of the scattered light depends on the difference
nickle. The pores thus become verysmall and the colloidal
between the refractive indices of the dispersed phase and the
particles may be retained on the treated filter paper. The
dispersion medium.
treated filters are known as ultrafilters. This process of
separating colloids from solutes is known as ultrafiltration. Scattered light
(illuminated
path in solution)
PROPERTIES OF COLLOIDAL --|
SOLUTIONS
Beam of
light
+
--+
+
l. Heterogeneous Character: As already stated, colloidal
systems, unlike true solutions, are heterogeneous in Colloidal solution
character. They consist of two phases - the dispersed phase
and the dispersion medium. Tyndal effect diagram
2.14 Chemistry
7. The Brownian Movement: It was found that particles of SnO, + 4H* -----+ Sn# + 2H2O; SnO, / Sn#
lyophobic sols were also in a state of ceaseless erratic and (In acidic medium )(Positive Sol)
random motion similar to pollen grains. This kinetic activity of
particles suspended in a liquid is called Brownian movement. SnO, + 2OH ----) SnOl- + H2O; SnO rlSnOl-
The Brownian movement is due to the bombardment on (In basic medium)(Negative Sol)
colloidal particles by molecules of dispersion medium which
are in constant motion e.g. molecules in a gas.
A list of common sols with the type of charge on their
particles.
8. Surface tension and viscocity: For Lyophobic sols, surface
tension and viscocity are not very different from those of Positively charged Negatively charged
the medium, as there is very slight interaction between the 1. Metallic hydroxides Metallic sulphides like AsrS,
suspended particles and the medium. On the other hand e.g. Cr(OH)3, A1(OH)r Sb2S3, CdS
Lyophilic sols shows a high degree of solvation of the & Fe(OH)r
particles and therefore, the properties of the medium are 2. Basic dye stuff Acid dye stuff example
modified. Thus the viscocity is much higher for the sol than example Congored sols
for the medium. Furthermore the surface tension of the sol is Methylene blue sol Metal like -Au, Ag, Cu, Pt etc.
lower than that of pure medium 3. Proteins in acidic Proteins in basic medium
9. Colour: The colour of hydrophobic sol depends on the medium Sols of starch, guffi, gelatin,
wavelength of the light scattered by the dispersed particles. clay & charcoal
The wavelength of the scattered light again depends on the
11. Electrical double layer: The surface of a colloidal particle
size and the nature of particles. For example the colour of
acquires a +ve l-ve charge by selective adsorption of a layer
silver sol changes with the particle (suspended) diameter in
ofpositive/negative ions around it. This layer attracts counter
solution.
ions from the medium which form a second layer of -ve/+ve
Colour ofAg sol . particle diameter
charges. The combination of the two layers of +ve and -ve
orange yellow 6 x l0-s mm
charges around the sol particle was called Helmh oltz double
orange-Red 9x l0-5mm
layer. According to modern view, the first layer of ions is
purple 13 x 10-5 mm
firmly held and is termed Fixed layer while the second layer
violet 15 x 10_5 mm
is mobile which is termed as Diffused layer.
10. Charge on colloidal particles: Colloidal particles always
The combination of the compact and diffused layer is
carry an electric charge. The mutual forces of repulsion
referred as the Stern double layer. The difftrsed layer is
between similarly charged particles prevent them from
aggregating and settling under the action of gravity. This
only loosely attached to the particle surface and moves in
gives stability to the sol. The charge is due to the preferential the opposite direction under an applied electric field. The
adsorption of either positive or negative common ion present potential difference between the fixed laye'r and the difftrsed
in excess. layer of opposite charge is called Electrokinetic Potential
or Zeta Potential.
o o o
o
Fe3* lons adsorbed
o o +
+ + Mobile layer
o Fe(OH)g o + +
+ +
o o + + Fixed layer
+ +
o Of Negaively charged
OO - Cl- ions in dispersion
medium
[Helmholtz double layer]
Representation of Fe(OH)3 Sol.
12. Electrophoresis: If electric potential is applied across two
Adsorption of charge: platinum electrodes dipping in a colloidal solution, the
colloidal particles move towards'one or the other electrode,
AgI + KI -+ AgI / I-(Negative Sol) due to charge on them.
(Excess) The movement of sol particles under an applied electric
potential is called "Electrophoresis". Depending upon the
AgI +AgNO, + AgI I Ag+ (Positive Sol) direction of movement of particles towards cathode or anode
(Excess) electrophoresis can be called "cataphoresis' or'Anaphoresis'.
Electrophoresis provides an experimental proof to show
FeCl, + H2O + Fe(OH), / Fe*3 (Positive Sol) that the colloidal particles are charged particles.
13. Electro osmosis: The medium will move in opposite direction
FeCl, + NaOH Fe(OH), / Ott- (Negative Sol) to the dispersed phase under the influence of apptied electric
potential. The movement of dispersion medium under the
 Surface 2.15

influence of applied potential is known as 'Electro - osmosis'. molecules, which removes the adsorbed charged layer
(In presence of plasma membrane) from the sol and therefore the sol particles seffle down.
14. Coagulation or Precipitation: The repulsion forces (e) By repeated dialysis: On continuous dialysis, besides
between the charged particles do not allow them to settle. If the electrolytic impurities the adsorbed ions are also
somehow, the charge is removed there is nothing to keep the removed and so the sol gets precipitated.
particles apart from each other. In such cases they aggregate
or flocculate and seffle down under the action of gravity.
The flocculation and settling down of the discharged COAGULATION OF LYOPH I LLIC
sol particles is called coagulation or precipitation. The SOtS
precipitation can be brought about in five ways
(a) By addition of electrolyte Lyophillic sol can be coagulated. This is done
(b) By electrophoresis. (i) By adding electrolyte
(c) By mixing two oppositely charged sols. (ii) By adding suitable solvent.
(d) By boiling. When solvents such as alcohol and acetone are added to
(e) By repeated dialysis hydrophilic sol, the dehydration of dispersed phase occur. Under
this condition a small quantity of electrolyte can bring about
(a) By addition of electrolytes: When an electrolyte is coagulation.
added in excess to a sol, then the electrolyte furnishes
both the types of ionq. in solution. The oppositely
charged ions get adsorbed on the surface of colloidal PnOTECTION OR PnOTEcTIvE AcTIoN
particles this causes neutralisation and there by the srze Lyophobic sols are readily precipitated by small amounts of
and mass of colloidal particle increases and it becomes electrolytes. However, these sols are often stablized by the
a suspension particle. Due to greater volume and greater addition of lyophilic sols.
mass these suspension particles settle down i.e they The properfy of lyophilic sols to prevent the precipitation or
coagulate. The ion responsible for neutralisation of coagulation of a lyophobic sol is called protection.
charge on the particle is called the flocculating ion. The Lyophilic sol used to protect a lyophobic sol from
Hardy Schulze Rule: This rule states that the precipitation is referred to as a protective colloid. Lyophilic sols
precipitating effect of an ion on dispersed phase of form a thin layer around lyophobic sol or around the ions furnished
opposite charge increases with the valency of the ion. by electrolyte and therefore the coagulation can not take place (as
The higher the valency ofthe flocculating ion, the gre ater the size does not increase much). Gelatin, albumin, gum arubia,
is its precipitating power. Thus for the precipitation of potato starch are some of the examples of Protective colloids.
AsrS, sol (-ve) the precipitating power ofAl3*,Ba'*, and The lyophilic colloids differ in their protective power.
Na* ions is in the order The protective power is measured in terms of "Gold number"
introduced by Zsigmondy.
A13*>Baz*>Na* The number of milligrams of a hydrophilic colloid that will
just prevent the precipitation of l0 ml of standard gold sol on
Similarly for precipitating Fe(OH), sol (positive) the
precipitating power of [Fe(CN)u]', SOi- and Cl- ions addition of 1 ml of 1D%NaCl solution is known as Gold number
is in the order of that protector (Lyophilic colloid).
The precipitation of the gold sol is indicated by a colour
tFe(CN)ul'-, SOl- > Cl- change from red to blue when the particle size just increases.
The smaller the gold number of a protective lyophilic
The minimum concentration of an electrolyte in milli colloid, greater is its protection power.
moles required to cause precipitation of I litre sol in
2 hours is called FLOCCULATION VALUE. The
smaller the flocculating value, the higher will be the Lyophilic sol.
coagulating power of the ion. (Protecting colloid)
(b) By Electrophoresis: During electrophoresis the
charged sol particles migrate towards the electrode of Lyophobic sol.
opposite sign. There they deposit their charge and then (Protected colloid)
get coagulated (As the neutral particles can aggregate
and change to suspension particles.) Gold Number of some hydrophilic colloids
(c) By mixing two oppositely chargpd sols: The
coagulation of two sols of opposite charge can be Lyophilic colloid Gold Number
effected by mixing them. For eg. Fe(OH), (positive Gelatin 0.00s - 0.01
sol) and Arsenic sulphide (negative sol) when mixed Egg albumln 0.08 - 0.1
neutralize each other, join and coagulate. Gum arabic 0.10 - 0.15
(d) By boiling: Sols such as sulphur and silver halides Potato - starch 25
dispersed in water get coagulated when boiled due to I
increased collision between sol particles, and water L o<
Protection Caoacitv
" Protection Number (Gold Number)
[Link] Chemistry

o Gelatin and starch have the maximum and minimum (ii) The globules show Tyndall effect and Brownian motion.
protective powers. (iii) The globules migrates in electricfield (electrophoresis) due
Congo rubin number: Ostwald introduced congo rubin to negativechargewhich is present on them.
number to account for protective power of colloids. It is (iv) They get coagulated by the addition of electrolyte containing
defined as the amount of protective colloids in milligrams divalent or trivalent cations.
which prevents colour change red to violet in 100 ml of
0.01o/o congorubin dye to which 0.16 g equivalent of KCI is
added. GELS
A gel is a jelly like colloidal system in which
Eruu$roNs ']
in a solid medium.
a liquid is dispersed

An emulsion can be defined as a colloidal dispersion in which

both the dispersed phase and dispersion medium are liquids. GeLS MAY BE CLASSIFIED lNTo TWo TYPEs
Common examples of emulsions in our everyday life are milk,
butter (molten), milk cream, cold cream, vanishing cream and
(a) Elastic gels: These are those which possesses the property
of elasticity. They change their shape on applying force and
other cosmetics like hair creams, lotions.
return to original shape when the force is removed. Gelatin,
starch and soaps are examples of substances which form
Type of Emulsions elastic gels.
As the two immisible liquids encountered in emulsions are (b) Non elastic gels: These are the gels which are rigid eg.
mostly oil and water, emulsions are classifed into two types: Silica gel. These are prepared by appropriate chemical
action. Thus silica gel is produced by adding concentrated
1. Oil in water type Emulsions hydrochloric acid to sodium silicate solution of the correct
this type of emulsions, oil acts
trn as the dispersed phase and concentration.
water act as the dispersion medium. Some examples of this
type of emulsions are milk, vanishing cream, hair cream and Properties of Gels
most of the ointments. These are easily washable with water 1. Hydration: A completely dehydrated elastic gels can be
and are called aqueous emulsions. regenereted by adding water to it.
2. Water in oil type Emulsions 2. Swelling: Partially dehydrated elastic gels imbibe water
In this type of emulsions, water acts as the dispersed phase when immersed in the solvent. This results in increase in
and oil acts as the dispersion medium. Common examples volume of the gel which is called swelling.
of this type of emulsions are cold cream, milk cream, buffer, 3. Syneresis: Inorganic gels on standing, loose water and
etc. These are also called oily emulsions. shrink. This process is called syneresis.
4. Thixotropy: Some gels revert to liquid sols on agitation.
Properties of emulsions
This reversible sol-gel transformation is called Thixotropy.
(i) Disperse phase particles (globules) are larger in size than the
disperse phase particles in sols.

Tfiles of colloids [Link] to their size

Multi Molecular Macro Molecular Associated colloids

Formation by aggregation of a Formation by aggregation of big These are the substances which behave as nornal elec-
large number of atoms or smaller size molecules. These are polymers trolytes at low concentration but get associated at higher
molecules of substance. with high molecular mass concentration and behave as colloidal solutions. These
E.g. + Gold, Sol, Sulphur sol E.g. -+ Starch, Cellulose, Protein associated particles are also called micelles
(Au) (S,) etc. E.g.+Soap&Detergent

APPLICATIONS OF COLLOI DS leather to hard leather by dipping it in salt water is called

Tanning. Usually chromium salts are used for tanning.
l. Colloids are used in food, medicines, paints, electrical 3. Adsorption indicators: Surface of certain precipitates
precipitation of smoke, Purification of sewage water, such as silver halides have the property of adsorbing some
formation of Delta and Purification of blood. dyes like eosin, fluorescein etc. In the case of precipitation
2. Tanning. Animal leather (skin) is soft due to the presence titration of AgNO3 versus NaCl the indicator is adsorbed
of very fine globules of oils and fats in the pores of skin. at the end point producirrg a characteristic colour on the
These globules are colloidal in nature. When this soft leather precipitate.
(skin) is placed in salt wateE these globules of oils and fats 4. Industrial products. Paints, inks, synthetic plastics, rubber,
coagulate and settle down in water. Now when the animal graphite lubricants, cement, etc are all colloidal solutions.
skin are dried they become hard. This process of making soft
 Surface Chemistry 2.17

5. Colloidal solution of graphite in water is called Aqua dag (3) suspension (4) colloidal solution
while that in Oil is called Oil dag.
6. Gold solution in water is called Purple of cassius. 9. Which of the following is an emulsifier?
7. Colloidion is cellulose nitrate & ethyl alcohol colloidal (1) Soap (2) Water
solution. (3) Oil (4) Linseed oil
Artificial rain:
Can be caused by spraying oppositely charge dust or fine
sand or precipitate like AgI (AgI has a crystal structure NANOMATERIATS
similar to ice) The materials having atleast one-dimension in the range of
Critical Micelle concentration (CMC): I nm to 100 nm are called nanomaterials. Different types of
The concentration at which associated colloids or Micelles nanomaterial are as follows:
are formed is called CMC.
Kraft Temperature (T"): Temperature at which Micelles (i) The nanomaterial with only one dimension between I nm
are formed. and 100 nin are called nanolayers.
(ii) The nanomaterial with two dimensions in the range 1- 100
nm are termed as nanotubes or nanowires.
(iii) The nanomaterials with three dimensions in the range of 1
nm to 100 nm are known as nanoparticles.
1. In colloidal dispersion, particle size (iv) Quantum dots are semiconductor nanoparticles that are
(1) lie between 0.1 nm to 1 nm about 1-10 nm in diameter.
(2) lie between 1 nm to 103 nm
(3) is larger than 103 nm PnoPERTT Es oF NAN9MATERTALS
(4) is smaller than 0.1 nm (i) The nanomaterials have different colours than the bulk
material.
2. Colloidal solution in which the dispersed phase has liule eg. Gold nanoparticles are red whereas bulk gold metal is
affinity for the dispersion medium is called yellow.
(l) lyophilic colloids (2) hydrophilic colloids (ii) The nanomaterials have lower melting points than the bulk
(3) emulsions (4) lyophobic colloids material.
- (iii) The nanomaterials tend to have greater reactivity than the
3. Tyndall effect is useful bulk material.
(1) to identify colloidal dispersions eg. Gold nanoparticles are chemically reactive whereas bulk
(2) to count number of particles in colloidal dispersion. metal is inert.
(3) to determine the size- of the colloidal partioles (iv) The nanoparticles have a substantial percentage of atoms on
(4) all of these the surface and are therefore bound less tightly than those
within the bulk solid
4. Brownian movement is a ffie of property of the colloidal eg. A 5 nm nanoparticle has about 30% of the atoms on its
so1. surface. This property of nanoparticles is responsible for the
(1) electrical (2) optical lower melting point and greater reactivity of nanomaterials
(3) kinetic (4) colligative lhan the bulk solid
(v) When a quantum dot is irradiated with UV light, it emits
5. The migration of colloidal particles under the influence of an visible light, the wavelength of which depends on the size of
electric field is called nanoparticle.
( I ) catalysis (2) electrophoresis eg. A 3 nm cadmium selenide particle emits green light of
(3) Brownian movement (4) Tyndall effect wavelength 520 nm whereas 5.5 nm particle of the same
- substance emits red light at the wavelength of 620 nm.
6. The capacrty of an ion to coagulate a colloidal solution
depends on AppIICATIONS OF NANOMATERIATS
(1) its shape (2) its valence Nanomaterials have numerous applications due to their distinctive
(3) the sign of charge (4) both (2) and (3) optical properties. Some of the applications are as follows:

7 . Which of the following has highest precipitation power? (i) Gold nanoparticles are highly effective as selective oxidation
(l) A1*3 (2) Mg*' catalysts.
(3) Na* (4) K+ (ii) The metal oxide nanoparticles are widely used in the
preparation of sunscreens and cosmetics, stain resistant
8. Cod liver oil is fabrics and dirt repellent paints.
(1) an emulsion (2) solution (iii) The nanotubes of carbon are used as strengthening rods and
toughening elements in structural composite materials.
[Link] Chemistry

(iv) Chemical modification of the surface of a quantum dot is 2. Semiconductor nanoparticles are known as
done by affaching on organic molecule. This modified (1) nanotubes (2) nanolayers
quantum dot targets and forms a chemical bond to specific (3) quantum dots (4) none of the above
biomolecule such as DNA or protein.
(v) Nanomaterials are used to detect human cancer at its earliest 3. Quantum dots have the diameter about
and most curable stages. The uses of several nanoparticles (l) 1 nm (2) 1000 nm
including quantum dots as possible weapons in the fight (3) 1-100nm (4) l-l0nm
against cancer, are under investigation.
4. Gold nanoparticles are highly effective
( 1) as selective oxidation catalyst
(2) as selective reduction catalyst
[Link] QU (3) depending upon temperature
(4) depending upon pressure
l. Nanotubes are dimensional nanomaterial.
(1) zero (2) two 5. Metal oxide nanomaterials find application in
(3) one (4) three (I ) cosmetics and sunscreens (2) stain resistant fabrics
(3) dirt repellent paints (4) all of the these
t
 Surface Chemistry 2.19
l:::l

SOLVED EXAMPLES 1l:i.i,i..l

l,|.iilL,,U.,el,nA#ig::N:' ,f, .,, . ,,

lL,LU,,EiTRATrtrr,:gg, 4,,,,i , ,

The voturne of nitrogen gas at OoC and L0l3 bar required to Discuss the effect of temperature on the degree of adsorption

nitrogen mslecule occupies :]iiiii ffiiiili

:[Link]::irir!:iri:iiiiiii:[Link]:i:
At room temperature, practically there is no adsorption of N, gas
:irfrffixi+ on the surface of iron. At 83 K, nitrogen is physically adsorbed
PV = nRT on the surface of iron. Its degree of adsorption decreases with rise
in temperature and becomes almost nil at room temperature. At
1.013 x 0. 129 = n x0.0821 x 273 773 K and above, there is chemical adsorption of nitrogen on the
surface of iron.
n - 0.00583 mol

Area occupied

- 1.00583
-L x 6.023 x 1023 x 16.2 x 10-20= 568 m'g-' MCH3COOHto
the molarity of acetic acid is
to, surface area of the charcoal
adsorbed by each molecule of acetic acid.

Surface area of charcoal = 3.01 x I A2 m?lg.

: :1::::ii:lj:.:::::::ri:j:::t:::::I,:.:tr::::::r:::.:

il$ii,ffiffififfiu Number of moles of acetic acid initially present

MV 0.5 x 100
= 1000
-_ 1000 =0.05

Number of moles of acetic acid left

Ml/ 0.49 x 100

1000 1000
= 0.049

Number of moles of acetic acid adsorbed

:tii*i:*ij:ii::j:i:::i:rJ:il:!iij:i:

iiilfffiiti lzis catalyst; first step is slow. = 0.05 - 0.049 = 0.01 mol

Number of molecules of acid adsorbed

- J.001 x 6.023 x 1023 = 6.023 x 1020

-f

Area occupied by single molecule of acetic acid

by 25 kJ/mol ar25"C.
Total area 3.01 102x
No. of molecules absorbed
=-0.023x 10il
:! :t!il! t:!!t::! !!.

IiOI.
:
: ::]]]|]:] :: :: : : :

= 5 X l0-1em2
Kp
- I
Ku=Antilos[
L)
[Link] )
I,,L,L,|J EiTRAT,I,B N,,., 6,, .,
25 xl03 t'.30 Cm':of X, gas at STP is adsorbed per gram of silica gel.
= Antilog
2.303 x 8.3 14x298 The area occupied by nitrogen molecule is 0.16 nm2. What is
the surface area per gram of silica gel?
(I/^ =6.023 x 1023)
- 24069 times
 2.20 Chemistry

The lesser is the activation energy, the gre ater is the ease with
r::::i:::;::::::::1::::::::ar::,:::.iiii:::iii:;i:::::::

111,ii# l*r1:,.::,

which the reaction can take place.

Number of N, molecules adsorbed per gram of silica gel
.'. C > B > A (Deceasing case with which the reaction can take
place.)
1'3x6x103
- 22400
= 3.48 x lore

Area of crosssection of molecule = 0. 16 nm2 [Link] 9

= 1.6 x 10-1e m2 The coagulation of 100 mL of a colloidal solution of gold is
completely prevented by adding A.25 g of starch to it before
Surface area covered per gram of silica gel adding 10 mL of 1 0% NaCl solution. Find out the gold number
of starch.
= 1.6 x l0-re x 3.48 x l0re
::::::l:i;::,:::::i:i::::::i:r::::,:: ji:ii:::::::r::::::

= 5.568 m2 lliiiiiffiiliilli.

l0 mL of l0% NaCl solution is added to 100 mL of solution of

gold.
Thus, I mL of l0% NaCl solution has been added to 10 mL
,,,IL,LUSTRATIEN 7, , solution of gold.
Plot of log (xlm) P is a straight line inclined at an angle of 45". Since, 100 mL gold solution required = 0.25 g starch
When the pressure is 0.5 atm and Freundlich parameter, fr is
= 0.25 x 103 mg starch
10, the amount of solute adsorbed per gram of adsorbent will
be:(log5=0.6990) So, l0 mL gold solution required

=x 10
iiar:iiiiiariii:irii:iii:ii::rl::i:l

liiiffiiiiii
According to Freundlich adsorption isotherm:
= 25 mg starch
log = log k + lln log P Thus, by definition, the gold number of starch is 25
When logxlm is xlm plotted against log P, we get straight line of
slope (lln) and intercept (log fr).

lln - tan 45o = I

logk=1og10=l

- k(P)'/n = 10(0'5)' = 5
ii:niii:lEa:r;:!ir!:!:l:il:irii!ii'::ii:i:i

When m=lg,x=59 i*tffiffii*i

Total volume after addition of 5 mL of I M NaCl solution
= 105 mL
A j

";;l'gg'13J'.ET'FIATIEI'N Thus, 105 x molarity of NaCl in colloidal solution - 5x I

In homogeneous catalyic reactions, there are three alternative
paths ,4, B and C (shown in the figure). Which one of the Molarity of NaCl in colloidal solution
e relative case with rvhich the reaction
Concentration in millimole = )( 1000 - 47 .6
aan take place?

t IIuusiTRATIElrt I I :

Potential The number of moles of tead nitrate needed to coagulate 2

energy if
\
mole of colloidal tAgll I is

,,l,[Link].11i.,i.,

zlAell f +Pb2*+PbI2 +2AgI

Reactio$ cs$rdinate *+
Thus, one mole of Pb(NOr), is required to coagulate 2 mole of
.::::::iiiiL::,i:i:i:::::l:ii:,iiii::::i:,iiiii
[AgI] r.
,iiliffifl#jii:l

Activation energy in the different paths lies in the following

sequence:C<B<A.
Iffiffi ffiffil
Adsorption lI 8. Physical adsorption is appreciable at
( I ) higher temperature (2) lower temperature
1. Blue colour of water in sea is due to (3) at room temperature (4) 100"C
(1) Refraction of blue light by impurities in sea water
(2) Refraction of blue sky by water 9. Adsorption is accompanied by
(3) Scattering of light by water ( I ) decrease in entropy of system
(4) None of these (2) decrease in enthalpy
(3) the value TDS is negative
2. The rate of chemisorption (4) all of these
( 1) decreases with increase of pressure
(2) is independent of pressure 10. Pd can adsorb 900 times its volume of hydrogen. This is
(3) is maximum at one atmospheric pressure called
(4) increases with increase of pressure (1) Absorption (2) Adsorption
3. Which of the following is not a characteristic of
(3) Occlusion (4) 2&3both
chemisorption? 11. Smoke is an example of
(1) Adsorption is irreversible (1) gas dispersed in liqiuid
(2) AH is of the order of 40 kJ (2) gas dispersed in solid
(3) Adsorption is specific (3) solid dispersed in gas
(4) Adsorption increases with increase of surface area (4) solid dispersed in solid
4. Tyndall effect is shown by
12. Which of the following is correct?
(l) solution (2) Osmotic solution
Colloidal (1) Langmuir adsorption is highly specific
(3) Isotonic solution (4) Hypertonic solution (2) Van der Waal's adsorption is reversible
5. The amount of gas adsorbed on charcoal increases with (3) Both 1 and 2 arc exothermic
(1) Temperature and pressure (4) All are correct
(2) Temperature and decreases with pressure 13. Brownian movement is found in
(3) Pressure and decreases with temperature (1) Milk (2) Fos
(4) None of the above (3) Blood (4) A11 of these
6. Which plot is the adsorption isobar for chemisorption where
x is the amount of gas adsorbed on mass m (at constant 14. Which one of the following is not a correct statement?
(1) Physical adsorption is reversible in nature
pressure) at temperature T?
(2) Physical adsorption involves Van der waals forces
(l) (2) (3) Rate of physical adsorption increases with increase of
pressure on the adsorbate
(4) High activation energy is involved
I
xlm
15. Which equation represents Freundlich's
T-+ adsorption isotherm (physical adsorption is basis of this
T __-_+ theory)?

(3) (4)
(l) xlm - K (P)'^ where x is amount of gas adsorbed on
mass 'm' at pressure P
(2) log xlm = log K + log P
(3) at low pressure KP - 0 and KP = I at high pressure
(4) All of these

T_f T+ 16. The amount of gas adsorbed physically on charcoal increases

with
7. For adsorption of gas on solid surface, the plots of log xlm vs (I ) rise in temperature and pressure
log P is linear with a slope equal to (2) rise in temperature and decreases with rise in pressure
(1) K (2) log K (3) rise in pressure and decreases with rise in temperature
(3) In K (4) ttn (4) none of these
2.22 Chemistry

17. The extent of adsorption of a gas on a solid depends on 26. 1.30 cm3 of N, gas at STP is adsorbed per gram of silica ge[.
( I ) the nature of gas The area occupied by nitrogen molecule is 0.16 nm2. What
(2) pressure of gas is the surface area per gram of silica gel?
(3) temperature of the system (N^=6.023 x 1023)
(4) all of the above (l) l.6rrf ga (2) 5.568 *'g-'
(3) 3.48 n'g-' (4) 4.42m' g-'
18. The curue showing the variation of adsorption with pressure
27. Which of the following statement is more correct?
at constant temperature is called
( I ) an isoster (2) adsorption isotherm
(1) Catalyst only accelerates the rate of a chemical reaction
(2) A catalyst can retard the rate of a chemical reaction
(3) adsorption isobar (4) all of these
(3) A catalyst can control the speed of a reaction
(4) A catalyst alters the speed of a reaction
19. Adsorption is accompanied by
( 1) decrease in entropy of the system 28. Which one of the following is not the example of
(2) decrease in enthalpy of the system homogeneous catalysis?
(3) TDS for the process is negative (1) Formation of SO, in the chamber process
(4) all of the above (2) Formation of SO, in the contact process
(3) Hydrolysis of an ester in presence of acid
20. Which charateristic of adsorption is wrong? (4) Decomposition of KCIO, in the presence of MnO,
( 1) Physical adsorption in general decreases with
29. The decomposition of hydrogen peroxide can be slowed
temperafure
down by the addition of a small amont of acetanilide. The
(2) Physical adsorption in general increases with
latter act as
temperature
(3) Physical adsorption is a reversible process
(l) Inhibitor (2) Promoter
(4) Adsorption is limited to the surface only
(3) Moderator (4) Posion

30. Efficiency of the catalyst depends on its

21. Which forms multi-molecular layers during adsorption? (1) Molecular weight (2) Number of free valencies
(1) Physical adsorption (3) Physical state (4) Amount used
(2) van der Waals adsorption
(3) Freundlich adsorption
31. Which of the following types of metals make the most
(4) efficient catalysts?
All of the above
(l) Transition metals (2) Alkali metals
(3) Alkaline earth metals (4) Radioactive metals
22. Graph between log (;) and log P is a straight line at an
32. In the reaction,
angle 45o with intercept on y-axis 0.3010. Calculate the
amount of gas adsorbed in gram per gram of the adsorbent KMnO4 + H2SO. * H2C2O 4+Products
when pressure is 0.2 atm Mn2* ions act as
(r) 0.4 (2) 0.6 (1) Positive catalyst (2) Negative catalyst
(3) 0.8 (4) 0.2 (3) Autocatalyst (4) Enzyme catalyst
33. In the Habers process of synthesis of NH3,
23. Sorption is the term used when
(l) Mo acts as a catalyst and Fe as a promoter
(1) adsorption takes place
(2) Fe acts as a catalyst and Mo as a promoter
(2) absorption takes place
(3) Fe acts as inhibitor and Mo as a catalyst
(3) both take place
(4) Fe acts as promoter and Mo as autocatalyst
(4) desorption takes place
34. Tetraethyl lead minimises the Knocking effect when mixed
24. The volumes of gases H2, CH 4, CO2 and NH, adsorbed by with petrol. It aets as a
I g of charcoal at 288 K are in the order: ( 1) positive catalyst (2) negative catalyst
(1) Hr) CHo, COr rNH, (3) autocatalyst (4) induced catalyst
(2) CHo > COr, NH, ) H,
(3) COr.>NH, > H2, CHo 35. In the Ostwald's process for the manufacfuring of HNO,
(4) NH3 > COr, CHo) H, the catalyst used is
(1) Fe (2) Pt
(3) VrO, (4) Mo
Catalyst lll 36. Which of the following acts as negative catalyst?
25. A catalyst lowered the activation energy by 25 kJ/mol at (1) Tetraethyl lead as antiknock compound
25"C. By how many times will the rate slow ? (2) Glycerol in decomposition of HrO,
(1) 24069 times (2) 2406 times (3) Ethanol in the oxidation of chloroform
(3) 240 times (4) 24 times (4) All the above
 Surface Chemistry 2.23

37. Which statement is wrong (I ) Increase (2) Decrease

(1) Haber's process of NH, requires iron as catalyst (3) Remain constant (4) Become infinite
(2) Friedel-Craft's reaction requires anhydrous AlCl3
(3) Hydrogenation of oils requires iron as catalyst 48. Air can oxidize sodium sulphite in aq. solution but cannot
(4) Oxidation of SO, to SO, requires VrO, do so in the case of sodium arsenite. If however, air is passed
through a solution containing both sodium sulphite and
38. In a reversible reaction, a catalyst sodium arsenite then both are oxi dized. This is an example
(1) increases the rate of forward reaction only of
(2) increases the rate of forward reaction to a greater extent (1) positive catalysis (2) negative catalysis
than that of the backward reaction (3) induced catalysis (4) autocatalysis
(3) increases the rate of forward reaction and decreases that
of the backward reaction 49. Zeolites
(4) increases the rate of forward and backward reaction (I ) are microporous aluminosilicates
equally (2) have general formulaNklz [(AlOr),(SiO r)r] mHrO
(3) have pore sizes between260 pm to 740 pm
39. In the manufacture of H2SO4 by contact process, the (4) A11 of the above
presence ofAsrO, acts as
(I catalytic promoter
) (2) catalTrtic poison 50. Zeohtes are used as catalyst in
(3) induced catalyst (4) autocatalyst (1) Petrochemical industries during cracking
(2) In the preparation of HrSOo
40. 'In oxidation of oxalic acid by KMnOo, the colour of (3) In the hydrolysis of ester
KMnOo disappears slowly in the beginning of reaction but (4) All of the above
disappears very fast afterwards. This is an example of
(1) autocatalysis (2) negative catalysis 51. Zeolites are
(1) water softner (2) catalyst
(3) induced catalysis (4) positiv e catalysis
(3) cation exchanger (4) All of these
41. Which is false for catalyst? 52. The activity and selectivity of zeolites as catalyst is based
(l) A catalyst can initiate a reaction on
(2) It does not alter the position of equilibrium in a (1) their pore size
reversible reaction (2) size of their cavities on the surface
(3) Acatalystremains unchanged in quality and composition (3) Both (1) and (2)
at the end of reaction (4) None of the above
(4) Catalysts are sometimes very specific in respect of a
reaction 53. Which is not the correct statement for a catalyst?
(1) It does not alter E,
42. Which of the following statement is incorrect? (2) It provides an alternate mechanism with a lower energy
(l) Enrymes exist in colloidal state of activation
(2 Enrymes are catalysts (3) Catalyst may form intermediates with the reactants
(3) Enzymes can catalyse any reaction (4) Action of enzyme catalyst is always specific
(4) Urease is an enzyme
54. Shape selective catalysts are so called because of
43. Platinized asbestos is used as a catalyst in the manufacture (1) the shape of the catalysts
of
of HrSO4. It is an example (2) the specificity of the catalysts
(1) homogeneous catalyst (2) heterogeneous catalyst (3) the size of the pores of the catalysts which can trap only
(3) autocatalyst (4) induced catalyst selective molecules
(4) their use for only some selected reactions
44. Which acts as a promoter for nickel in the hydrogenation of
oils? 55. Following are various types of colloids. Match column X
(1) Cu (2) Mo with column Y.
(3) Fe (4) Pt X (Cotloids) Y (Classification)
45. Which acts as poison for Pd-charcoal in Lindlar catalyst? I Rain cloud A Sol
(1) BaSOo II Gelatin B Aerosol
Q) Quinoline m Soap suds C Gel
(3) Both (l) and (2) (4) None of these
IV Butter D Foam
46. Enzymes are known to increase the rate of reaction by Correct mathcing is:
(1) 102 times (2) 10-2 times I ililr ry
(3) 105 times (4) l0r2 times (l) A BC D
(2) A CB D
47. When a catalyst increases the rate of a chemical reaction, (3) B AD C
the rate constant will (4) B AC D
2.24 Chemistry

56. Silt in water is 67. Milk represents colloidal solution of

(1) Gel (2) Sol (l) Fat dispersed in water
(3) Aerosol (4) Foam (2) Water dispersed in fat
(3) Fat dispersed in oil
57. Opal (mineral with liquid inclusions) is a (4) None of these
(1) gel (liquid dispersed in solid phase)
(2) solid sol (solid dispersed in solid phase) 68. When a beam of light passed through colloidal solution,
(3) sol (solid dispersed in liquid) ( I ) it gets scattered
(4) foam (gas dispersed in liquid) (2) it gets absorbed
(3) it is refracted
58. Some of the following are true solutions: (4) it undergoes reflection
I : Air II : Sea water
III : Glucose solution IV : Wine 69. Gold number gives the indication of
V : Pearl VI : Blood (1) Gm-molecules of gold per 100 ml of colloidal solution
Select true solutions: (2) Percentage of gold in the suspension
(1) I, II, III, IV (2) II, III, IV V (3) Charge on the colloids
(3) r, rv v vr (4) rr, rv vr (4) Protective power of a colloid

59. In multimolecular colloidal sols, atoms or molecules ar:e 70. Which of the following will have the highest coagulating
held together by power for AsrS, colloid
(1) H-bonding (2) van der Waals forces (1) Poi Q) soi-
(3) Ionic bonding (4) Polar covalent bonding (3) Al3* (4) Na*

60. Tyndall effect is not observed in 71. The coagulation of colloidal particles of the sol can be
(1) Suspension (2) Starch sol caused by
(3) Gold sol (4) NaCl solution (1) Heating
(2) Adding oppositely charged sol
61. Which is a kinetic phenomenon? (3) Adding electrolyte
(1) Brownian motion (2) Tyndall effect (4) All of the above
(3) Both (l) and (2) (4) None of these
72. Which of following process can be used for the purification
62. Which pair is correctly matched? of colloids?
(1) [Fe(OH),]: Fe3* (1) Coagulation (2) Dialysis
(2) [AsrS,]:As3* (3) Peptization (4) All of these
(3) [SnOrl: SnO]- in acidic medium
(4) [AgI]: I-in excess ofAgNO, 73. In which of the following colloidal systems the dispersion
medium is solid?
63. Gold number of haemoglobin is 0.03. Hence, 100 mL of gold (1) Soap lather (2) Smoke
sol will require haemoglobin so that gold is not coagulated (3) Boot polish (4) Clouds
by l0 mL of 10% NaCl solution.
(1) 0.03 ms (2) 30 mg 74. The separation of colloidal particles from those of molecular
(3) 0.30 mg (4) 3 ms dimension with electricity is known as
( electrolysis
1) (2) electrophoresis
64. Which is not the correct matching of emulsions? (3) electrodialysis (4) none of these
(l) Milk: OAM (2) Cold cream: WO
(3) Butter: OAM (4) Vanishing cream: OAM 75. Which of the following is not heterogeneous?
(1) On emulsion (2) True solution
(3) Suspension (4) Colloidal sol
Co[[oids 76. In Faraday-Tyndall effect, the colloidally suspended
65. The random motion of colloidal particles in the dispersion particles
medium is referred to as (l) Scatter the strong beam of light
(1) adsorption (2) coagulation (2) Coagulation
(3) brownian movement (4) tyndall effect (3) Show electrophoresis
(4) Show Brownian movement
66. Tyndall effect in colloidal solution is due to
(1) scattering of light 77. Which of the following indicates the charge on colloidal
(2) reflection of light particles
(3) absorption of light (1) Brownian movement (2) Electrophoresis
(4) presence of electrically charged particles (3) Filtration (4) Tyndall effect
 Surface Chemistry 2.25
78. On adding few drops of dil HCI to freshly precipitated ferric 89. Milk is a colloid in which
hydroxide, a red coloured colloidal solution is obtained. (1) A liquid is dispersed in liquid
This phenomenon is known is (2) A solid is dispersed in liquid
(l) peptisation (2) dialysis (3) A gas dispersed in liquid
(3) protective action (4) dissolution (4) Some sugar is dispersed in water

79. The particle size ranges from in colioidal state 90. Which of the following statement is not correct in respect of
(l) I - 100 nm (2) 200 - 2000 nm hydrophilic sol?
(3) 2000 - 4000 nm (4) 0.1 - I nm (l) The particles are hydrated
(2) They are quite stable and are not easily coagulated
80. If dispersed phase is a liquid and the dispersion medium is a (3) They are irreversible
solid, the colloid is known as alan (4) There are considerable interactions between the
(1) sol (2) sel dispersed phase and dispersion medium
(3) emulsion (4) foam
91. Colloidal particles of soap sol in water are
81. In which of the following states, the particle size is more (l) Negatively charged (2) Positively charged
than 300 mm (3) Neutral (4) Unpredictable
(l) suspensions (2) true solutions
92. In aerosol, the dispersion medium is
(3) colloidal solutions (4) none of the above
(1) Solid (2) Liquid
82. The colloidal solution of two immiscible liquids is called
(3) Gas (4) Any of these
(1) Gel (2) Aerosol 93. The presence of colloidal particles of dust in air imparts
(3) Emulsion (4) None of these blue colour to the sky. This is due to
(1) Absorption of light (2) Reflection of light
83. Lyophilic sols are more stable than lyophobic sols because
(3) Refraction of light (4) Scattering of light
(1) the colloidal particles have positive charge
(2) the colloidal particles have negative charge 94. In colloidal state, particle size ranges from
(3) the colloidal particles are highly solvated (1) ltoloA (2) 20tos0A
(4) there are strong electrostatic replulsions between the (3) 10 to 1000 A (4) 1 to 280 A
negatively charged colloidal particles
95. A sol has positively charged colloidal particles. Which of
84. Metals like silver and copper can be obtained in the colloidal the following solutions is required in lowest concentration
state by for coagulation?
(l) peptisation (2) bredig arc method (1) NaCl (2) Kr[Fe(CN)u]
(3) dialysis (4) coagulation (3) ZmCL, (4) NarSOo

85. The protective power of lyophilic sol is 96. The minimum concentration of an electrolyte in millimoles
(1) dependent on the size of colloidal particles pbr litre required to cause coagulation of a sol is called its
(2) expressed in terms of gold number (1) Coagulation value (2) Protective value
(3) expressed by x/m (3) Gold number (4) Critical value
(4) directly proportional to the magnitude of charge on it
97. Which of following processes best describes the
purification of muddy water by addition of alum?
86. The Brownian motion is due to
(1) temperature fluctuation within the liquid phase
(1) Absorption (2) Adsorption
(2) attraction and repulsion between charges on the
(3) Dialysis (4) Coagulation
colloidal particles 98. In which of following system the dispersed phase and
(3) impact of molecules of the dispersion medium on the dispersion medium are both solid
colloidal particles (l) Foam (2) Dust storm
(4) convective currents (3) Coloured glass (4) Paints
87. Arsenic sulphide sol is negatively charged. Which of 99. An arsenious sulphide sol carries a negative charge. The
the following electrolyte would be most effective in its maximum precipitating power for this sol is possessed by
coagulation (1) KrSOo Q) CaCl,
(1) BaCl, (2) KCI (3) Na,POo @) A1C13
(3) K.[Fe(CN)u] (4) A1C13
100. The number of moles of lead nitrate needed to coagulate
88. Which of the following method is not employed for the 2 moles of colloidal [AgI]I- is
purification of colloids? (1) 2 (2) 1

(l) Electrodialysis (2) Dialysis

(3) Ultracentrifugation (4) Peptisation
(3)
;
(4)
i
2.26 Chemistry

101. The name aquadag is given to the colloidal sol of (2) Arsenious sulphide sol
(1) Copper in water (2) Platinum in water (3) Starch sol
(3) Graphite in water (4) None of these (4) Silver iodide sol
102. Cod liver oil is ll4. Which of the following metal sols cannot be prepared by
(1) Fat dispersed in water Bredig's arc method
(2) Water dispersed in fat (1) Copper (2) Potassium
(3) Water dispersed in oil (3) Gold (4) Platinum
(4) Fat dispersed in fat
115. The number of components in colloidal system are
103. Vanishing cream is an example of (1) One (2) Two
(1) Emulsion (2) Foam (3) Three (4) Four
(3) Lyophillic sol (4) Suspension
116. In which of the following Tyndall effect is not observed?
104. Alcosol is a colloidal system (l) Suspensions (2) Emulsions
(I ) of a solid dispersed in a gas (3) Sugar solution (4) Gold sol
(2) of a gas dispersed in water
(3) in which dispersion medium is benzene 117. The process of separation of colloids by passing through
(4) in which dispersion medium is alcohol semipermeable membrane is called
(1) Filtration (2) Electrophoreises
105. The dispersion medium in gel is (3) Dialysis (4) Ultrafilteration
(1) Solid (2) Liquid
(3) Water (4) Gas 118. Gelatin is often used as an ingredient in the manufacture of
ice cream for
106. Liquid-Liquid sols are known as (1) Causing mixture to solidity
(1) Aerosols (2) Emulsions (2) Improving the flavour
(3) Foam (4) Gels (3) Stabilising the colloidal system and preventing the
crystal growth
107. Purple of Cassius is (4) Preventing formation of colloid
(l) colloidal solution of gold
(2) colloidal solution of silver ll9. The size of colloidal particles lies between
(3) colloidal solution of platinum (1) l0-7 - lO-e cm (2) l0-e - 10-11 cm
(4) oxyacids of gold (3) 10-s - 10-7 cm (4) l0-2 - 10-3 cm
108. Cheese is a colloidof 120. Which type of properfy is the Brownian movement of
(1) Liquid dispersed in solid colloidal sol
(2) Solid dispersed in liquid (l) Electrical (2) Optical
(3) Gas dispersed in solid (3) Mechanical (4) Colligative
(4) Solid dispersed in gas
l2l. Which of the following is not represented by sols?
109. Which of the following can be included in the category of (l) Absorption (2) Tyndall effect
colloids? (3) Flocculation (4) Paramagnetism
(1) Milk (2) Blood
(3) Latex (4) A11 of these 122. The redispersal of a freshly precipitated substance into a
sol by the addition of an electrolyte in common is known
110. A dispersion of AgCl in water is a/an AS

(l) hydrophilic colloid (2) an emulsion (1) Aggregation (2) Condensation

(3) an alcosol (4) hydrophobic sol (3) Coagulation (4) Peptisation

111. Which of the following constitute irreversible colloidal 123. AsrS, sol is
system in water as dispersion medium? (l) Positive colloid (2) Negative colloid
(1) Clay (2) Platinum (3) Neutral colloid (4) None of these
(3) Fe(OH), (4) All of these
124. Peptisation is a process of
ll2. Hydrophilic colloids are stable due to (I ) Precipitation of colloidal particles
(1) negative charged particles (2) Purification of colloids
(2) large size of particles (3) Dispersing precipitate into colloidal sols
(3) small size of particles (4) Movement of colloidal particles in the electrical field
(4) layer of dispersion medium on their particles
125. Choose the false statement
113. Which of the following is a hydrophilic colloidal sol?
(l) Colloidal sols are homogenous
(1) Barium sulphate sol (2) Colloids carry positive or negative charges
 Surface Chemistry 2.27
(3) Colloids show Tyndall effect (2) The magnitude of charge
(4) The size range of colloidal particles is 10-1000A (3) The sign of charge
(4) Both magnitude and sign of charge
126. A liquid is found to scatter a beam of light but leaves no
residue when passed through the filter paper. The liquid 137. Flocculation value is expressed in terms of
can be described as (1) Millimole/litre (2) Mole/litre
(1) A suspension (2) Oil (3) Grams/litre (4) Mole/millilitre
(3) A colloidal sol (4) True solution
138. Which of the following has the maximum protecting
127. The colloidal sols are purified by power?
(1) Peptisation (2) Coagulation (1) Gelating (Gold no. = 0.01)
(3) Dialysis (4) None of these (2) Dextrin (Gold no. = 15)
(3) Potato starch (Gold no. = 25)
128. The separation of colloidal particles from those of
(4) Albumin (Gold no = 0.25)
molecular dimension is known as
(1) Photolysis (2) Dialysis 139. The coagulation of 10 cm3 of Gold sol is completely
(3) Pyrolysis (4) Peptisation prevented by addition of 0.025 g of starch to it. The gold
number of starch is
l2g. The impurities present in rain water possess charge
(1) Positive (2) Negative (1) 0.02s (2) 0.2s
(3) Zero (4) Positive and -negative (3) 2.s (4) 2s

130. Which one of the following substance gives a positively 140. Gelatin protects
charged sol (1) Gold sol (2) AsrS, sol
(1) Gold (2) A metal sulphide (3) Fe(OH), Sol (4) A11 of these
(3) Ferric hydroxide (4) An acidic dye
l4l. Gold number is minimum in case of
131. Which one of the following will have the highest (l) Gelatin (2) Egg albumin
coagulating power for a ferric hydroxide solution? (3) Gum arabic (4) Starch
(1) NaCl (2) BaCl,
142. The gold numbers of four protective colloids O, P, Q and
(3) IlCrOo (4) IK,[Fe(CN).]
R are 0.005, 0.01, 0.1 and 0.5 respectively. The decreasing
132. A metal sulphide sol can be flocculated, by one of the order of their protective power is
following (1) R, Q,P, O (2) O, P, Q, R
(1) [Fe(CN)u]o- (2) So;' (3) P, Q, R, O (4) Q, R, O, P
(3) BeCl, (4) A13*
143. The charge on the colloidal particle of soap in its solution
133. Ferric chloride is applied to stop bleeding because developed
(1) Fe3* ions coagulate blood which is a negatively (1) By prefrential adsorption of ions
charged sol
(2) The effective ion of soap micelle carries negative charge
(2) Cl- ions cause co-agulation of blood (3) The effective ion of soap micelle carries positive charge
(3) FeCl, react with the constituents of blood (4) None of the above
(4) Blood absorbs FeCl, 144. In order to coagulate the impurities present in water. Which
134. A colloidal solution is subjected to an electrical field. The is the most effective ion present in the 'alum'?
particles move towards anode. The coagulation of same (l) K+ (2) soi-
sol is studied using NaCl, BaCl, and AICL solutions. Their (3) Al3* (4) None of these
co-agulating power should be
145. Which is not the property of the hydrophilic sols?
(1) NaCl > BaClr) A1C13
( I ) High concentration of dispered phase can be easily
(2) BaCl, > AlCl, > NaCl
attained
(3) AICL > BaCl, > NaCl
(2) Coagulation is reversible
(4) BaCl, > NaCl > AlCl3
(3) The charge of the particle depends upon the pH
135. Which of the following method is used for sol destruction values of the dispersion medium. It may be positive or
(1) Condensation negative
(2) Dialysis (4) Viscosity and that surface tension are about the same
(3) Diffusion through animal membrane as of dispersion medium.
(4) Addition of an electrolyte
146. If water is chosen as dispersion medium, then the sol
136. The ability of ion to bring about coagulation of a given formed will be called
colloidal solution depends upon (1) Alcohosol (2) Benzosol
(1) Its size of ion (3) Hydrosol (4) Aerosol
2.28 Chemistry

147. Colloids and crystalloids can be separated by animal 159. The capacity of an ion to coagulate a colloidal solution
. membrane using the technique depends on
(1) Electro-osmosis (2) Filtration (1) its shape
(3) Dialysis (4) Electrophoresis (2) the amount of its charge
(3) the sign of the charge
148. Maximum hydrophobic character will be shown by (4) both (2) and (3)
(1) Glycine (2) Stearic acid
(3) Glucose (4) Adenine 160. Gold number is a measure of
(1) The amount of gold present in the colloidal solution.
149. Fe(OH), sol obtained by peptisation when subjected to (2) The amount of gold required to break the colloid.
' electrophoretic effect' (3) The amount of gold required to protect the colloid.
(1) Colloidal particles will migrate towards anode (4) None of the above
(2) Colloidal particles will migrate towards cathode
(3) Colloidal particles remain stationary 161. On addition of 1 ml. solution of l0% NaCl to 10 ml. gold
(4) Colloidal particles migrate towards both the electrode sol in presence of 0.025 g of starch, the coagulation is just
prevented. The gold number of starch is:
150. Which of the following solution is positively charged?
(1) 2s (2) 2.s
(1) AsrS, (2) Fe(OH), (3) 0.2s (4) 0.02s
(3) Au (4) Starch
162. A11 collodial solutions show:
151.. Dispersion ofAgCl in water is called
(1) Very high osmotic pressure
(1) Hydrophilic sol (2) Emulsion
(2) High osmotic pressure
(3) Benzosol (4) Hydrophobic colloid
(3) Low osmotic pressure
152. The stability of lyophilic colloid is due to (4) No osmotic pressure
(1) Charge on the solution particles
(2) Layer of dispersion medium over the solution paricles 163. The gold number ofA, B, C and D are A.04,0.002, 10 and
(3) Smaller size of solution particles 25 respectively. The protective powers of A, B, C and D
are in the order:
(4) Bigger size of solution particles
(l) A>B>C>D (2) B>A>C>D
153. The volume of nitrogen gas at OoC and 1.013 bar required (3) D>C>B>A (4) C>A>B>D
to cover a sample of silica gel with unimolecular layer is
129 cm3 g-t of gel. Calculate the surface area per gram of 164. Which of the following has minimum flocculation value?
the gel if each nitrogen molecule occupies 16.2 x l0-20 m2. (t) Pb2* (2) Pb4*
(l) 568 *'g-' (2) 565 m' g-' (3) St'* (4) Na*
(3) 560 m' g-' (4) 562 rn'g-'
165. The charge ofAsrS, sol is due to the absorbed
154. The number of phases present in colloidal solution is (1) H+ (2) OH-
(1) 2 (2) 4 (3) o,2- (4) 52-
(3) 3 (4) I
166. To coagulate gelatin sol, which of the following is most
155. Butter is a colloid formed when effective?
(1) Fat is dispersed in fat (l) NaCl (2) Na,POo
(2) Fat is dispersed in water (3) AICL $) Alcohol
(3) Water is dispersed in fat
167. An example of micelle is
(4) Suspension of casein in water
(1) AsrO, sol.
156. Lyophobic colloids are (2) Ruby glass
( 1) reversible (2) irreversible (3) NarCO, solution
(3) water loving (4) solvent loving (4) Sodium stearate concentrated solution

157. When freshly precipitated Fe(OH), is boiled with water 168.Brownianmotionshownbycolloida1particleisits-

in the presence of few drops of dil HCl, a hydrated ferric property.
hydroxide sol is obtained. This method is termed (1) Optical (2) Electrical
(1) Dialysis (2) Peptisation (3) Kinetic (4) Chemical
(3) Ultrafiltration (4) Electrodispersion
169. A colloidal solution of Fe(OH), in water is
158. The greater the valency, the higher is the coagulating (l) a hydrophilic colloid (2) a hydrophobic colloid
power of ion. This rule was introduced by (3) an emulsion (4) None of these
(l) Hardy-Schulze (2) Graham 170. In both dialysis and osmosis which particle do not pass
(3) Kossel and Lewis (4) Faraday through SPM?
 Surface Chemistry 2.29
(l) Water (2) Small molecules (1) KCl (2) KNO3
(3) Colloids (4) A11 (3) KrSoo (4) I!F. (CN)u
17L The greater is the protective power of lyophilic colloid, the 183. The colloidal sol of SnClo prefers to adsorb:(in excess of
(l) lesser is its gold no. (2) greater is its gold no. HCl)
(3) either (1) or (2) (4) Neither (1) nor (2) (r) No; (2) K.
172. Hardy-Schulze rule states that
(3) 52- (4) Cr
(l) Non-electrolytes have better coagulating action on 184. On adding AgNO, solution into KI solution, a negatively
colloids than electrolytes charged colloidal sol is obtained when they are in:
(2) Sols are coagulated by effective ions whose charge is (1) 100mLofO.1 MAgNO,* l00mLofO.l MKI
opposite to that of sol and the ions of higher charge are (2) 100 mL of 0.1 M AgNO3 + 50 mL of 0.2 M KI
much more effective than the ions of lower charge (3) 100 mL of 0.1 M AgNO, * 100 mL f 0.1 M KI
(3) Charge of the ions has no effect on the coagulation of (4) 100 mL of 0.1 M AgNO, * 100 mL of 0.15 M KI
a sol
(4) Sols are coagulated only by those ions whose charges 185. Micelles are?
is similar to that of the sol (1) Ideal solution (2) Associated colloids
(3) Adsorbed surfaces (4) Adsorbent solutes
tr73. The correct statement for milk is:
(l) Milk is an emulsion of fat in water 186. Micelles have
(2) Milk in an emulsion of protein in water (1) higher colligative properties as compared to common
(3) Milk is stabilized by protein colloidal sols
(4) Milk is stabilizedby fat (2) lower colligative properties
(3) same colligative properties
174. A colloidal system involves (4) none of the above
( I ) A state of dissolution (2) A state of dipersion
(3) A state of suspension (4) None of these 187. Which of the following sol is formed due to following
reaction: SnO2 + HCl (Excess):
175. The coagulating power of an effective ion carrying the (1) [SnClo] Cr Q) [SnClo]o'
charge opposite to the sol particles has been illustrated by (3) [SnClo]H. (4) None of these
(1) Brownian movement (2) Gold number
(3) Tyndall effect (4) Schulze-Hardy rule 188. Which of followig ion has minimum flocculation value
(r) cl- (2) so;,
176. In electrophoresis (3) POi- (4) [Fe(cN)u]o-
(1) Sol particles move towards opposite electrodes
(2) Medium moves towards opposite electrodes 189. A negatively charged suspension of clay in water needs for
(3) Neither (1) nor (2) precipitation the minimum amount of:
(4) Both (1) and (2) (1) Aluminium chloride (2) Potassium sulphate
(3) Sodium hydroxide (4) Hydrochloric acid
177. Gelatin protects
(l) sol
Gold (2) AsrS, sol 190. Which is not a colloidal solution?
(3) Fe(OH),sol (4) A11 of these (1) Smoke (2) Ink
(3) Air (4) Blood
178. Detergent action of synthetic detergents is due to
( 1) Interfacial area
191. Which one is natural colloid?
(2) High molecular weight (1) NaCl (2) Blood
(3) Ionisation (3) RCOONa (4) Sugar
(4) Emulsiffingproperties 192. Medicines are more effective if they are used in
179. Which is not shown by sols? (1) Colloidal state (2) Solid state
(1) Adsorption (2) Tyndall effect (3) Solution state (4) None of these
(3) Flocculation (4) Paramagnetism 193. Egg albumin is
180. Which of the following is an emulsifier? (1) Reversible colloid (2) Lyophilic colloid
(1) Soap (2) Water (3) Protective colloid (4) All of these
(3) oil (4) NaCl lg4. Which of the following is not an emulsion?
181. Emulsifiers are generally (1) Milk (2) Hair oil
(1) Soap (2) Synthetic detergent (3) Cheese (4) Oil in water
(3) Lyophilic sols (4) A11 of the above 195. Which of the following has maximum flocculation value
182. Which of the following is most effective in causing the of Fe(OH)s sol?
coagulation of ferric hydroxide sol? (1) Po;' (2) soi-
(3) [Fe(CN)u]* (4) Cr
2.3O Chemistry

IIffi ffiil
1. Hardy-Schulze rule explains the effect of electrolytes on (3) the amount of gold required to protect the colloid
the coagulation of colloidal solution. According to this rule, (4) none of the above
coagulation power of cations follow the order
(1) B** > Na* > Al3* 11. Arsenic sulphide sol is prepared by passing HrS through
(2) A13* > Na* > B** arsenic oxide solution. The charge developed on the
(3) A13* > Ba2* > Na* particles is due to adsorption of
(4) B** > Al3* > Na* (1) H+ (2) 52-
(3) OH- (4) C,2-
2. Which of the following reaction gives a colloidal sol?
12. Interface cannot be obtained is
(1) MgCO3-+ MgO + CO,
(2) 2Na +2HrO 2NaOH * H,
(l) Liquid-liquid (2) Solid-liquid
(3) Liquid-gas (4) Gas-gas
(3) 2HNO3 + 3H2S+
- 35 + 4H2O + 2NO
(4) Cu + CuCl, CurCl,
13. At CMC the surfactant molecules
-> (1) decompose
3. Which of the following is not an emulsion?
(2) become completely soluble
(1) Butter (2) Ice cream
(3) associate
(3) Milk (4) Cloud
(4) dissociate
4. Which of the following process does not occur at the inter-
face of phases? 14. Arsenic sulphide is a negative sol. The reagent with least
(l) Homogeneous catalysis (2) Crystallisation precipitating power is
(3) Heterogeneous cata(ysis (4) Corrosion (1) AICL Q) Nacl
(3) CaF, (4) Glucose
5. During adsorption the AH is negative and the magnitude of
negative value 15. Zetapotential (or elecfrokinetic potential) is the
(1) goes on increasing (1) potential required to bring about coagulation of a
(2) goes on decreasing colloidal sol
(3) remains same (2) potential required to give the particles a speed of I cm/s
(4) first increases then decreases in the sol
(3) potential difference between fixed charged layer and the
6. In which condition, adsorption will not take place? diffirsed layer having opposite charge
(1) When AH is negative (4) potential energy of the colloidal particles.
(2) When AH is positive and AS is positive i
16. Extent of physisorption of a gas increases with
(3) AH is positive and AS is negative
(1) decrease in surface area of adsorbent
(4) AG is negative
(2) decrease in temperature
(3) increase in temperature
7. Adsorption is an exothermic process, because during
(4) decrease in strength of van der Waals forces
adsorption
(1) surface energy increase
17. The presence of electric charge on colloidal particles is
(2) surface energy decrease
indicated by
(3) surface engrgy remain same
(4) residual forces of attraction increase
(1) osmosis (2) dialysis
(3) electrolysis (4) electrophoresis
8. At the equilibrium position in the process of adsorption
(1) AH < 0 (2) AH: TAS 18. Which one of the following emulsiffing agents helps in the
(3) AH < TAS (4) AH > TAS formation of w/o emulsion?
(1) Proteins (2)- Gums
9. Which gas would get adsorbed when passed into a solution (3) Insoluble soaps (4) Soluble soaps
of e[.r?
(1) NH, (2) NO 19. The minimum concentration of an electrolyte which is able
(3) CO (4) 02 to cause coagulation of a sol is termed its
(1) emulsification value (2) saponification value
10. Gold number gives
(3) flocculation value (4) gold nrunber
(1) the amount of gold present in the colloid
(2) the amount of gold required to break the colloid
 Surface Chemistry 2.31

20. Extent of adsorption of adsorbate from solution phase 29. A sol has positively charged colloidal particles. Which of
increases with the following solutions is required in lowest concentration
( 1) increaqe in amount of adsorbate in solution' for coagulation?
(2) increase in temperature of solution (1) NaCl (2) KiFe(CN)ul
(3) decrease in surface area of adsorbent (3) ZnCl, (4) NarSOo
(4) decrease in amount of adsorbate in solution.
30. In which of the following states, the particle size would be
21. Cottrell precipitator is a device to greater than 1000 nm?
(1) coagulate the particles of any sol (1) Suspensions (2) True solutions
(2) coagulate the particles of carbon from smoke (3) Colloidal solution (4) None of these
(3) coagulate the mud particles from water
(4) coagulate the dirt particles of sewage water
31. Which of the following in not a colloid?
(1) Foam (2) Cloud
22. Gold number is a measure of
(3) Roohafza syrup (4) Egg

(1) protective action by a lyophilic colloid on a lyophobic 32. Physical adsorption of a gaseous species may change to
colloid chemical adsorption with
(2) protective action by a lyophobic colloid on a lyophillic ( 1) decrease in surface area of adsorbent
colloid (2) decrease in temperature
(3) number of mg of gold in red gold sol (3) increase in temperature
(4) stability of gold sol (4) increase in surface area of adsorbent

23. Which of the following statements is correct? 33. Separation of colloidal particles from those of molecular
(1) True particles are able to pass through filter paper and dimension with electricity is known as
not in semipermeable membrarre. (1) electrolysis (2) electrophoresis
(2) Colloidal particles are able to pass through filter paper (3) electrodialysis (4) none of these
and not in semipermeable membrane.
(3) Both true and colloidal particles are able to pass through 34. Smoke is an example of
filter paper and semipermeable membrane. (1) gas dispersed in liquid (2) gas dispersed in solid
(4) Both true and colloidal particles are not able to pass (3) solid dispersed in gas (4) solid dispersed in solid
through filter paper and semipermeable membrane.
35. The Brownian motion is due to
24. Which one of the following is not applicable to the (1) temperature fluctuation within the liquid phase
phenomenon of adsorption? (2) attraction and repulsion between charges on the
(1) AS<0 (2) AH<O colloidal particles
(3) AH>O (4) AG<O (3) impact of molecules of the dispersion medium on the
colloidal particles
25. Consider the following reactions (4) convection currents
(A) 2SO2 * O, = ,'2SO3 (B) N, * 3Hr. ^ 2NH3
36. Physisorption adsorbent does not show specificity for any
(C) N, * 02 i-"- 2NO (D) H, * 12 zHl particular gas because
The reactions which require a catalyst are
====
( 1) it is a reversible process
(1) (A) and (c) (2) (B) and (D) (2) gases involved behave like ideal gases.
(3) (A) and (B) (4) All of these (3) enthalpy of adsorption is low
(4) involved van der Waals forces are universal
26. Which of following statements is not true for a lyophobic
sol? 37. Colloidal solutions are not purified by
(1) It carries charges (1) dialysis (2) electrodialysis
(2) It can be easily solvated (3) ultrafiltration (4) electrophoresis
(3) It is less stable in a solvent
(4) The coagulation of this sol is irreversible in nature 38. Surface tension of lyophilic sols is
(l) lower than that of HrO
27. The optimum temperature range for the enzyme activity is (2) more than that of HrO
(1) 278 K - 288 K (2) 288 K 2e8 K (3) equal to that of HrO
(3) 2e8 K - 310 K (4) 310 K - 318 K (4) none of these
28. is not a favourable condition for physical
adsorption. 39. Addition of lyophilic solution to the emulsion, forms
(1) High temperature (1) a protective film around the dispersed phase
(2) Negative AH (2) a protective film around the dispersion medium
(3) Higher critical temperature of adsorbate (3) an aerosol
(4) High pressure (4) true solution
2.32

40. An example of absorption is 51. The arsenious solution is negatively charged. The maximum
(l) Hydrogen on finely divided nickel power of precipitating it, is in
(2) Water on calcium chloride (1) NarSOo Q) NarPOo
(3) Water on silica gel (3) AlcL @) Mg(No,),
(4) Oxygen on metal surface
52. Lyophobic sol can be protected by
41. Micelles are (1) By boiling
(1) emulsion cum gel (2) associated colloids (2) By addition of oppositely charged sol
(3) adsorbed catalysts (4) ideal solutions (3) By addition of an electrolyte
(4) By addition of lyophilic sol
42. The isoelectric point of a colloidally dispersed material is
the pH value at which 53. Which of the following statements is correct for Tyndall
(1) the dispersed phase migrate in an electric field effect?
(2) the dispersed phase does not migrate in an electric field (l) Scattering and polanzing of light by small suspended
(3) the dispersed phase has pH equalto 7 particles is called Tyndall effect
(4) the dispersed phase has pH equal to zero (2) Tyndall effect of colloidal particles is due to dispersion
of light
43. Which of the following is a hydrophilic colloidal sol? (3) Tyndall effect is due to refraction of light
(1) Barium sulphate sol (2) Arsenious sulphide sol (4) Zigzag motion of suspended particles
(3) Starch sol (4) Silver iodide sol
54. The coagulating power of an effective ion carrying the
44. At high concentration of soap in water, soap behaves as charge opposite to the sol particles is given by
(1) Brownian movement (2) Gold number
(l) macromolecular colloid (2) lyophilic colloid (3) Tyndall effect (4) Hardy-Schulze rule
(3) molecular colloid (4) associated colloid
55. Choose the false statement.
45. The stability of lyophilic colloid is due to which of the
(1) Brownian movement and Tyndall effect are shown by
following?
colloidal systems.
(1) Charge on their particles
(2) Gold number is a measure of the protective power of a
(2) Large size of their particles
lyophilic colloid.
(3) Small size of their particles r
(3) The colloidal solution of a liquid in liquid is called gel.
(4) A layer of dispersion medium
(4) Hardy-Schulze rule is related with coagulation.
46. Tyndall effect is more pronounced in 56. Freshly prepared precipitate sometimes gets converted to
(1) hydrophilic sols (2) hydrophobic sols colloidal solution by
(3) lyophilic sols (4) both (l) and (3) (1) diffirsion (2) peptisation
(3) coagulation (4) electrolysis
47 . Which of the following is an associated colloid?
(1) Protein * water (2) Soap * water
57. Alum helps in puriffing water by
(3) Rubber * benzene (4) Milk
(1) forming Si complex with clay particles
48. Which of the following will show Tyndall effect? (2) sulphate part which combines with the dirt and removes
(1) Aqueous solution of soap above critical micelle it
concentration. (3) aluminium which coagulates the mud particles
(2) Aqueous solution of sodium chloride. (4) making mud water soluble
(3) Aqueous solution of sugar.
(4) Aqueous solution of soap below critical micelle 58. The dispersed phase in colloidal iron (III) hydroxide
concentration. and colloidal gold is positively and negatively charged
respectively.
49. Which one of the following is correctly matched? Which of the following statements is not correct?
(1) Emulsion: curd (2) Foam: mist (1) Mixing the sols has no effect
(3) Aerosol: smoke (4) Solid sol: cake (2) Coagulation in both sols can be brought about by
electrophoresis
50. Which of the following methods is used for the destruction (3) Magnesium chloride solution coagulates the gold sol
of sol? more readily than the iron (III) hydroxide sol
(1) Condensation (4) Sodium sulphate solution cause coagulation in both
(2) Dialysis sols.
(3) Diffirsion through animal membrane
(4) Addition of an electrolyte
 Surface Chemistry 2.33

59. The volume of a colloidal particle, V. as compared to (2) They are used as cation exchangers
volume of solute particle V, in a true solution could be (3) They have open structure which enables them to take up
small molecules
(1) (2) (4) Zeolites are aluminosilicates having three-dimensional
+=ro-3 t='0, network

68. The values of colligative properties of colloidal solution

(3) (4)
f=' +=1023
are of small order in comparison to those shown by true
solutions of same concentration because colloidal particles
60. Which one of the following electrolytes have maximum
coagulating value for AgU Ag* sol? (1) are comparatively less in number
(l) NarSOo Q) NarPOo (2) form lyophilic colloids
(3) NarS (4) NaCl (3) exhibit enornous surface area
(4) remain suspended in the dispersion medium
61. Which of the following represents homogeneous catalysis?
69. Which one of the following forms micelles in aqueous solu-
(1) Oil + Hr 4 Saturated fat
tion above certain concentration?
(2) Nr,r, + 3Hr,r, 5 2NH3G) (l) Glucose
(2) Urea
(3) CH3COOH + C2HTOH '* ) CH3COOC2H5 + H2O (3) Dodecyltrimethyl arnmonium chloride
(4) None of the above (4) Pyridinium chloride
7A. xlm versus P curve in Langmuir Adsorption Isotherm is:
62. Which of the following statements is not correct? (l) Straight line (2) Parabola
(1) The efficiency of a solid catalyst depends upon its (3) Hyperparabola (4) Cube like
surface area.
(2) Catalyst operates by providing alternate path for the 71. Colloidal solutions show in HrO
reaction that involves a lower energy of activation. (1) Paramagnetism
(3) Catalyst lowers the energy of activation of the forward (2) Scattering of light (Tyndall effect)
reaction. (3) Refraction
(4) Catalyst does not affect the overall enthalpy change of (4) All of these
the reaction.
72. The process responsible for the formation of delta at a place
where rivers meet the sea is
63. In certain cases, the rate of reaction increases with time. (1) Peptisation (2) Emulsification
This phenomenon is known as
(1) induced catalysis (2)
(3) Coagulation (4) Colloid formation
catalytic inhibition
(3) autocatalysis (4) catalytic promotion 73. On adding excess electrolyte what happens to the collides:
( I ) Coagulates (2) Dissolves
64. A colloidal system having a solid substance as a dispersed
(3) Peptizes (4) Disperses
phase and a liquid as a dispersion medium is classified as
(1) emulsion (2) gel 74. Fog is a colloidal system of:
(3) solid sol (4) sol (1) gas in liquid (2) liquid in gas
(3) gas in gas (4) gas in solid
65. Lapis Lazuli is
(l) 75. According to Freundlich adsorption isotherm, which of the
Ferrous sulphate
following is correct?
(2) Copper sulpate
xt
(3) Sodium alumino silicate (l) ^ [Link]
(4) Zinc sulpate m
Xl
(2) o< p'
66. Which of the following forms cationic micelles above -m
certain concentration: xl
(l) Cetyltrimethylailrmonium bromide (3) o< ptt
-m
(2) Sodium dodecyl sulphonate (4) All the above are correct for different ranges of pressure
(3) Sodium acetate
(4) Urea 76. The process not responsible for the presence of electric
charge on the sol particles is
67. Which one of the following statements about the zeolites is
(1) Formation of Helmholtz electrical double layer
false?
(2) Absorption of ionic species from solution
(l) Some of the SiOf units are replaced by AlOf- and (3) Electron capture by sol particles
AIO:- ions in zeolites (4) Adsorption of ionic species from solution
2.34 Chemistry

Itffi
These questions consist of two statements. During answering these Questions you are required to choose any one of the following four
responses.

,'{l} Ifhtr Statement I and Statement 2 are True and the Statement 2 is a correct explanation of the Statement l.
.... rr. If both Statement I and Statement 2 are True but Statement 2 is not a correct explanation of the Statement l.
,(3)
If Statement I is True but the Statement 2 is False.
.ffi) If both Statement I and Statement 2 are False.

L. Statement 1: Langmuir adsorption is a single layer 10. Statement 1: The graphical representation of physical
phenomenon. adsorption with temperature is.
Statement 2z It is due to van der Waals forces.

2. Statement 1: A sol of AsrS, prepared by the action of HrS

Adsorption
on AsrO, is negatively charged.
Statement 2z Due to adsorption of 52- ion on surface of
AsrS, sol. Temp
3. Statement 1: Physical adsorption of molecule on the Statement 2: This is weak adsorption and adsorption is
surface requires activation energy. exothermic process.
Statement 2: Because the bonds of adsorbed molecules are
broken. 11. Statement l: Zeolite is shape selective catalyst.
Statement 2: Size of the pores of the catalyst are such that
4. Statement 1: Filtration of colloidal particles is not possible they can trap only selective molecules.
by filter paper.
Statement 2: Size of colloidal particle is less than filter 12. Statement 1: Lyophilic sols coagulate by adding other
paper pores. solvent.
Statement 2: Lyophilic sol are stable due to hydration
5. Statement 1: A gas mixed with another gas forms a colloidal energy.
solution.
Statement 2: Mixture of gases is homogenous system. 13. Statement lz Catalyst is more effective in powdered form.
Statement 2: Number of free valencies increase.
6. Statement 1: Lyophilic sols is more stable than lyophobic
so1. 14. Statement 1: Amount of charge on hydrophobic sol is more
Statem ent 2: Lyophilic sol have greater solvation ene rW than hydrophilic sol.
then lyophobic sol. Statement 2:Lyophobic sol is inorganic substance lyophilic
sol is organic substance.
7 . Statement L: Associated colloids are formed by aggregation
of large no. of ions in concentrated solution of soap. 15. Statement 1: During physical adsorption multimolecular
Statem ent 2: Because associated colloids have more than layers are formed.
one colloidal particles. Statement 2: For physical adsorption value of AH - -20 to
x -40 kJimol
8. Statement 1: In case of chemical adsorption, first
increase then decrease with temperature. m 16. Statement 1: Aqueous gold colloidal solution is red in
Statement 2: The initial increase is due to the fact that colour.
heat supplied acts as a activation energy. The decrease Statement 2: The colour arises due to scattering of light by
afterwards, is due to the exothermic nafure of adsorption at colloidal gold particles.
equilibrium.
17 . Statement 1: Alcohols are dehydrated to hydrocarbons in
9. Statement 1: Physical adsorption forms multimolecular the presence of acidrc zeolites.
layer. Statement 2: Zeolites are porous catalysts.
Statement 2: It contains covalent bond.
18. Statement 1: The micelle formed by sodium stearate in
water has -COO- groups at the surface.
Statem ent 2: Surface tension of water is reduced by the
addition of stearate.
 Surface 2.35

19. Statement 1: Reaction of SO, and HrS in the presence of 21. Statement 1: Micelles are formed by surfactant molecules
FerO, catalyst gives elemental sulphur. above the critical micellar concentration (CMC)
Statemeht 2: SO, is a reducing agent Statement 2z The conductivity of a solution having
surfactant molecules decreases sharply at the CMC.
20. Statement L: Fe3* can be used for coagulation ofAsrS, sol.
Statement 2: Fe3* reacts with AsrS, to give FerS,

...---.--
2.36 Chemistry

Iffiffi ffiffiI
AIPMT / AIIMS Questions 7. Which one of the following statements is incorrect about
errirp catalysis? [AIPMT 20121
L. Which of the following molecules is most suitable to disperse (1) Enzymes are denatured by ultraviolet rays and at high
benzene in water: [AIIMS 2005] temperature
o (2) Eruymes are least reactive at optimum temperafure
(3) Enzymes are mostly proteinous in nature
(1) O- Na+ (4) Enzymes action is specific

o 8. The protecting power of lyophilic colloidal solution is

Na+ -O expressed in terms of [AIPMT 20121
(2) O- Na+ (1) Critical micelle concentration
o (2) Oxidation number
(3) Coagulation value
(4) Gold number
(3) cHr
9. The ease of adsorption of the hydrated alkali metal ions on
an ion-exchange resins follows the order:

(4) cl IAIPMT Pre. 20121

(1) K* < Na* < Rb* < Li*
(2) Na*< Li* < K* < Rb*
2. The Langmuir adsorption isotherm is deduced using the (3) Li* < K* < Na* < Rb*
assumption. IAIPMT 20071 (4) Rb* < K* < Na* < Li*
(l) The adsorption sites are equivalent in their ability to
adsorb the particles. 10. A colliodal solution is kept in dark and is illuminated by a
(2) The heat of adsorption varies with coverage. beam of light then brightness appears at the right angle of
(3) The adsorption molecules interact with each other. direction of light. This effect is called [AIIMS 20121
(4) The adsorption takes place in multilayers. (l) Tyndall effect (2) Brownian effect
(3) Hardy-Schalze effect (4) None of these
3. Butter is an example of: lArrMS 20101
(1) Water - oil emulsion 11. Which property of colloids is not dependent on the, charge
(2) Solid - liquid colloidal system particles?
on colloidal IAIPMT 20141
(3) Oil - water emulsion (1) Tyndal effect (2) Coagulation
(4) Solid - solid colloidal system (3) Electrophoresis (4) Electro-osmosis
4. If x is amount of adsorbate and m is amount of adsorbent, 12. The addition of a catalyst during a chemical reaction alters
which of the following relations is not related to adsorption which of the following quantities? [NEET 20161
proces [AIPMT Pre. 20111
(1) Activation energy (2) Entropy
(I) xlm - f (p) at constant T (3) Internal energy (4) Enthalpy
(2) xlm - f (T) at constant p
(3) p - f (T) at constant (xlm) 13. Fog is a colloidal solution of [NEET 20161
x (1) Gas in gas
(4) = pxT (2) Liquid in gas
m (3) Gas in liquid (4) Solid in gas
5. Which of the following is incorrect for physio-sorption 1.4. The coagulation values in millimoles per litre of the
lArrMS 201U electroytes used for the coagulation of AsrS, are given
( 1) Reversible
below INEET 20161
(2) Increases with increase in temperature I (NaCl) = 52 II(BaClr) = 0.69
(3) Low heat of adsorption m (BaClr) = 0.69 IV(MgSOJ = 0.22
(4) Increases with increase in surface area
The correct order of their coagulating power is
6. In Freundich adsorption isotherm, thg value of 1 ln is (1) IrI>I>rI (2) r>rr>III
IATPMT 20121 (3) II>r>III (4) III>II>I
(1) I in case of physical adsorption
(2) 1 in case of chemisorption 15. The suspension of slaked lime in water is known as
(3) Between 0 and I in all cases INEET 20161
(4) Betwee n 2 and, 4 inall cases (1) Aqueous solution of slaked line
 Surface Chemistry 2.37

(2) Limewater (a) Pure nitroeen (i) Chlorine

(3) Quicklime I Haber Drocess (ii) Sulohuric acid
(4) Milk of lime kr Contact orocess (iii) Ammonia
(d) Deacon's Drocess (iv) Sodium azide or Barium azide
16. Which one of the following statements in not correct? Which of the following is the correct option?
INEET 20171 (a) (b) (c) (d)
(l) The value of equilibrium constant is changed in the (1) (i) (ii) (iii) (iv)
presence of a catalyst in the reaction at equilibrium (2) (ii) (iv) (i) (iii)
(2) Enzymes catalyse mainly bio-chemical reactions (3) (iii) (iv) (ii) (i)
(3) Coenzymes increase the catalytic activity of enzyme (4) (iv) (iii) (ii) (i)
(4) Catalyst does not initiate any reaction
20. Measuring Zeta potential is useful in determining which
17. On which of the following properties does coagulating property of colloidal solution? [NEET 2020 Phase 1]
power of an ion depend? [NEET 20181 ( 1 ) Size of the colloid al particles

(1) The magnitude of the charge on the alone (2) Viscosity

(2) Size of the ion alone (3) Solubility
(3) Both magnitude an sing of the charge the ion (4) Stability of the colloidal particles
(4) The sign of charge on the ion alone
21. In which of the sols, the colloidal particles are with negative
18. Which mixture of the solutions will lead to the formation of charge? [NEET 2020 Phase 2l
negatively charged colloidal [AgI] I- sol.? [NEET 20191 (1) Hydrated AlrO, (2) TiO2
(1) 50 mL of I MAgNO, * 50 mL of 1.5 M KI (3) Haemoglobin (4) Starch
(2) 50 mL of 1 MAgNO, * 50 mL of2M KI 22. The right option for the statement "Tyndall effect is exhibited
(3) 50 mL of 2 M AgNO, * 50 mL of 1.5 M KI
by", is: [NEET 20211
(4) 50 mL of 0.1 M AgNOr + 50 mL of 0.1 M KI
(l) NaCl solution (2) Glucose solution
19. Match the following: [NEET 20191 (3) Starch solution (4) Urea solution
2.38 Chemistry

ffiffiI
THEORY t{t. (l) 142. (2) 143. (2) 144. (3) 145. (4)
146. (3) 147. (3) 148. (4) 149. (2) 150. (2)
lrurexr OuesnoNs 1
151. (4) 152. (4) 153. (l) 154. (t) 155. (3)
l. (1) 2. (1) 3. (3) 4. (1) 5. (3) 156. (2) 157. (2) 158. (l) 159. (4) 160. (4)
6. (1) 7. (l ) t6t (l) 162. (3) 163. (2) 164. (2) 165. (4)
166. (4) 167. (4) 168. (3) 169. (2) 170. (3)
lrurexr OuesnoNs 2 t7t. (1) 172. (2) 173. (1) 174. (2) 175. (4)
1. (3) 2. (1) 3. (1) 4. (3) 5. (2) 176. (t) 177. (4) 178. (4) 179. (4) 180. (1)
6. (3) 7. (4) 8. (3) 18t. (4) 182. (4) 183. (4) 184. (2) 185. (2)
186. (2) 187. (1) 188. (4) 189. (1) 190. (3)
191. (2) 192. (1) 193. (4) 194. (3) 195. (4)
lrurexr OuesnoNs 3
1. (2) 2. (4) 3. (l) 4. (3) 5. (2)
6. (4) 7. (1) 8. (1) 9. (1)
EXERGISE 2= MIXED CONGEPT
lrurexr OuesnoNs 4
ouEsTtoNs
1. (2) 2. (3) 3. (4) 4. (l) 5. (4)
1. (3) 2. (3) 3. (4) 4. (1) 5. (2)
6. (3) 7. (2) 8. (2) 9. (4) 10. (4)
11. (2) 12. (4) 13. (3) 14. (4) 15. (3)
16. (2) 17. (4) 18. (3) 19. (3) 20. (1)
EXERCISE 1= TOPIGWISE OUESTIONS 21. (2) 22. (1) 23. (2) 24. (3) 25. (3)
1. (3) 2. (2) 3. (2) 4. (1) 5. (3) 26. (2) 27. (3) 28. (1) 29. (2) 30. (1)
6. (3) 7- (4) 8. (2) g. (4) 10. (4) 31. (1) 32. (3) 33. (3) 34. (3) 35. (3)
11. (3) 12. (4) 13. (4) 14. (4) 15. (4) 36. (4) 37. (4) 38. (1) 39. (l) 40. (2)
16. (3) 17. (4) 18. (2) 19. (4) 20. (2) 41. (2) 42. (2) 43. (3) 44. (4)" 45. (4)
21. (4) 22. (1) 23. (3) 24. (4) 25. (1) 46. (2) 47. (2) 48. (1) 49. (3) 50. (4)
26. (2) 27. (4) 28. (2) 29. (1) 30. (2) 51. (3) 52. (4) 53. (l) 54. (4) 55. (3)
31. (l) 32. (3) 33. (2) 34. (2) 35. (2) 56. (2) 57. (3) 58. (1) 59. (2)' 60. (2)
36. (4) 37. (1) 38. (4) 39. (2) 40. ({) 61. (3) 62. (3) 63. (3) 64. (4) 65. (3)
41. (1) 42. (3) 43. (2) 44. (1) 45. (3) 66. (1) 67. (1) 68. (1) 69. (3) 70. (1)
46. (4) 47. (1) 48. (3) 49. (4) 50. (l) 71. (2) 72. (3) 73. (l) 74. (2) 75. (4)
51. (4) 52. (3) 53. (1) 54. (3) 55. (3) 76. (2)
56. (2) 57. (l) 58. (l) 59. (2) 60. (4)
61. (1) 62. (1) 63. (3) 64. (3) 65. (3)
66. (1) . (l) 68. (l) 69. (4) 70. (3)
6',1 STATEMENT BASED OUESTIONS
71. (4) 72. (2) 73. (3) 74. (3) 75. (2) 1. (3) 2. (1) 3. (4) 4. (1) 5. (4)
76. (1) 77. (2) 78. (1) 79. (l) 80. (2) 6. (1) 7. (2) 8. (l) 9. (3) 10. (1)
81. (1) 82. (3) 83. (3) 84. (2) 85. (2) 11. (1) 12. (l) 13. (l) 14. (2) 15. (2)
86. (3) 87. (4) 88. (4) 89. (1) 90. (3) 16. (1) 17. (2) 18. (2) 19. (3) 20. (2)
91. (1) 92. (3) 93. (4) 94. (3) 95. (2) 21. (2)
96. (1) 97. (4) 98. (3) 99. (4) 100. (l)
101. (3) 102. (3) 103. (1) 104. (4) 105. (t)
106. (2) 107. (l) 108. (l) 109. (4) 110. (4) ARCHIVES
111. (4) tlz. (4) 113. (3) tt4. (2) 115. (2)
l. (1) 2. (1) 3. (1) 4. ( 4) 5. (2)
116. (3) tt7. (3) 118. (3) 119. (3) 120. (3)
6. (3) 7. (2) g. (4) 9. ( 4) 10. (l)
t2l. (4) 122. (4) 123. (2) 124. (3) 125. (1)
13. (2) 14. 15. (4)
126. (3) 127. (3) 128. (2) 129. (2) 130. (1) 11. (1) 12. (t) ( 4)

131. (4) 132. (4) 133. (1) 134. (3) 135. (4) 16. (l) 17. (3) 18. (1,2) 19. ( 4) 20. (4)
136. (4) 137. (1) 138. (1) 139. (4) 140. (4) 21. (4) 22. (l)
lt'
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122, Near Glvern ment Hospital, ECR, Mamal lapu ram-603104,Tam i I nad u I SBN 978-93-5350-435-9

Webs ite : vrnaffi i ngsneetu [Link], Emai I : academicsneetu [Link] n gs@g mai [Link] lsBN 93-5350-435-X

fl wlooile: 7305919333, 9747355623

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