CK 1

CHEMICAL KINETICS

Syllabus :

Rate of a chemical reaction, factor affecting the rate

of reactions; concentration, temperature, pressure
and catalyst; elementary and complex reactions,
order and molecularity of reactions, rate law, rate
constant and its units, differential and integral forms
of zero and first order reactions, their characteris-
tics and half-lives, effect of temperature on rate of
reactions - Arrhenius theory, activation energy and
its calculation, collision theory of bimolecular gas-
eous reactions (no derivation)
Nuclear Chemistry
Nature of radiations from radioactive substances.
Nuclear reactions; Radio-active disintegration
series; Artificial transmutation of elements; Nuclear
fission and Nuclear fusion; Isotopes and their ap-
plications: carbon-dating.

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
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 CK 2
CONCEPTS

C1A Chemical Kinetics is that branch of physical chemistry which deals with the study of the speed of a
chemical reaction. Such studiesd also enable us to understand the mechanism by which the reaction occurs.
C1B Rate of reaction :
The rate of reaction is defined as the amount of change in concentration divided by the corresponding time
interval or rate is the concentration change per unit time.

Change in conc. dx
Rate of reaction =
time dt
For the reaction aA + bB cC + dD

1 d[ A ] 1 d[B] 1 d[C] 1 d[D]

Instantaneous rate =
a dt b dt c dt d dt

1 [ A ] 1 [ A ] 1 [C] 1 [D]
Average rate =
a t b t c t d t
ve sign. indicates decrease of conc. of reactants with time t.

d[ A ] d[C]
Rate of disappearance of A = , Rate of formation of C =
dt dt
* Rate of reaction and rate of formation or rate of disappearance expression can be same if stoichiometric
coefficient is one.
Practice Problems :
1. In the reaction A + 2B 3C + D which of the following expressions does not correctly describe
changes in the concentration of various species as a function of time ?

d[C] 3d[A ] 3d[D] d[C]

(a) (b)
dt dt dt dt
3d[B] 2d[C] 2d[B] d[A]
(c) (d)
dt dt dt dt
2. Rate of formation of SO3 in the following reaction 2SO2 + O2 2SO3 is 100 kg min1. Hence rate of
disappearance of SO2 will be :
(a) 100 kg min1 (b) 80 kg min1 (c) 64 kg min1 (d) 32 kg min1
[Answers : (1) d (2) b]

C2A Rate law, molecularity and order of reaction

According to the rate law the rate of reaction is directly proportional to the concentration of reactant and
reactants are raise to some power which may or may not be equal to stoichiometry coefficient.
For a reaction :
aA + bB product
rate = k[A]m[B]n ..... [A], [B] are the molar concentrations or active masses.
k = rate contt, specific rate contt. or velocity contt.
Order of reaction w.r.t. A = m, B = n. Overall order of reaction = m + n
molecularity = a + b
molecularity alway a whole number (> O)

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C2B Difference between order and molecularity :
Molecularity Order
1. In elementary reactions, it is the total number 1. The order of the reaction is
of atoms or molecules taking part in the balanced defined as the sum of the
equation, whereas for the complex reactions it has powers of the concentration
no significance. terms represented in the rate
expression of the reaction.
2. It is the theoretical concept based on the number 2. It is an experimental property
of molecules of an elementary equation derived from the experimental
rate law.
3. It will not change with the change in conditions 3. It will change with conditions.
i.e. temperature, pressure etc.
4. It is always an integer i.e. never be zero 4. It may be an integer, fractional
or even zero.
5. For elementary reactions the order and molecularity
may be same or different.
* for Pseudo molecular reaction order and molecularity are different
* units of rate : mol L1 time1
C3A Rate constant :
units of k for reaction of nth order

1 1
k
time [Conc .]n 1
C3B Integrated equation for rate constant of different order reactions :
A Products
Let A0 = initial concentration of reactant.
A0 x = remaining conc. of reactant at time t, x = concentration of reactant decomposed at time t
T50 = half-life period which is the time required by the reaction to undergo 50% conversion into the
[A 0 ]
products. i.e., at t = T50, x = .
2
C3C Zero order reaction :
A Product
at t = 0 A0 0
at time t A0 x x
Rate expression of a zero order reaction as shown as r = k

x
for zero order : k , k has a unit mol lt1 time1
t
for e.g. photochemical reaction like (H2 + Cl2 2HCl) is a zero order reaction.

A0 [A 0 ]
At t = T50, x = , T50 =
2 2k
C3D First order reaction :
A product
at time t = 0 A0 0
at time t A0 x x
Rate law expression for the first order reaction is
r = k[A]

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi 110 018, Ph. : 9312629035, 8527112111
 CK 4
for first order :

2.303 A0 0.693
A t A 0e kt , k log , At t = T50 k , T75% = 2T50%, T99.9% 10T50%
t ( A 0 x) T50
* Amount after n half lives for Ist order
[A]t = [A]0 (1/2)n
Graph of first order reaction :

Practice Problems :

1. Ethylene is produced by C 4 H8
2C 2 H 4 . The rate constant is 2.48 104 sec1. In what time
Cyclobu tan e

will the molar ratio of the ethylene to cyclobutane in reaction mixture attain the value 1
(a) 27.25 minute (b) 28.25 minute (c) 25 minute (d) 20 minute
2. Mathematical expression for t1/4 i.e. when (1/4)th reaction is over following first order kinetics can be
given by

2.303 2.303
(a) t1/ 4 log 4 (b) t1/ 4 log 2
K K
2.303 4 2.303 3
(c) t1/ 4 log (d) t1/ 4 log
K 3 K 4
3. The rate constant of a first order reaction is 4 103 sec1. At a reactant concentration of 0.02 M, the
rate of reaction would be
(a) 8 105 M sec1 (b) 4 103 M sec1
(c) 2 101 M sec1 (d) 4 101 M sec1
4. In a first order reaction, the concentration of the reactant is decreased from 1.0 M to 0.25 M in
20 minute. The rate constant of the reaction would be
(a) 10min1 (b) 6.931 min1 (c) 0.6931 min1 (d) 0.06931 min1
[Answers : (1) a (2) c (3) a (4) d]

C3E Second order reaction :

A product
at time t = 0 A0 0
at time t A0 x x
Rate law expression for the second order reaction is
r = k[A]2

1 1 1 1 1 1
k = t A A , T50 . , for nth order : t 1 / 2
t 0 A0 k [ A]nO1

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi 110 018, Ph. : 9312629035, 8527112111
 CK 5
Practice Problems :
1. Following is the graph between (a x)1 and time t for second order reaction = tan1(0.5)
OA = 2 L mol1.

hence rate at the start of the reaction is :

(a) 1.25 L mol1 min1 (b) 0.5 L mol1 min1
(c) 0.125 L mol1 min1 (d) 1.25 L mol1 min1
[Answers : (1) c]

C4A Experimental determination of rate constant of different first order reaction

(i) decomposition of hydrogen peroxide

1
H 2O 2
H 2O O2
2
hence V0 = volume of KMnO4 at start A0
Vt = volume of KMnO4 at time t (A0 x)

2.303 V
hence for the first order reaction : k log 0
t Vt
(ii) Acid hydrolysis of Ethyl Acetate :
H
CH3COOC2H5 + H2O CH3COOH + C2H5OH
excess
V0 = volume of NaOH at start catalyst [H+], Vt = volume of NaOH at time x + [H+]
V = volume of NaOH at infinite time [A0] + [H+]

2.303 V V0
Hence for Pseudo first order reaction : k log
t V Vt
(iii) Pressure change method :
This is to be used in gaseous phase reaction. As reaction proceeds there may be a change in total
pressure. By measuring initial and total pressure at the start and after time t, value of A0 and
(A0 x) can be determined in terms of pressures.

A( g )
y B(g )
at t = 0 P0 0
at time t (P0 P) yP
Total pressure at time t Pt = PA + PB
Pt = P0 P + yP

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi 110 018, Ph. : 9312629035, 8527112111
 CK 6
Therefore, P0 P (A0 x)
P0 A0

2.303 P0
k log 0
t P P
Practice Problems :
1. For the first order reaction A(g) 2B(g) + C(g), the initial pressure PA = 90 mm Hg, the pressure
after 10 minutes is found to be 180 mm Hg. The rate constant of the reaction is
(a) 1.15 103 sec1 (b) 2.3 103 sec1
(c) 3.45 103sec1 (d) 4.6 103 sec1
2. The reaction A(g) + 2B(g) C(g) + D(g). Initial pressure of A and B are respectively pA = 0.60 atm,
pB = 0.80 atm. When pC = 0.20 atm, the rate of the reaction, relative to the initial rate, is :

1 1 1 1
(a) (b) (c) (d)
48 24 6 4
3. At 1000C, a gaseous reaction A B + 2C; is observed to be of first order. On starting with pure A, at
the end of 14 minutes, the total pressure was found to be 264 mm of Hg. After a long time the total
pressure of the system was 450 mm of Hg. Thus the Initial pressure of A is
(a) 57 (b) 150 (c) 114 (d) 190
[Answers : (1) a (2) c (3) b]

C4B Different methods for determining the order of reaction :

(i) Rate law method
(ii) Half life method
(iii) Integrated rate equation method
Practice Problems :
1. For the reaction, 2A + 2B Products the following initial rates were obtained at various given initial
concentrations
S.No. [A] [B] Rate(mol L1 sec1)
1. 0.1 0.2 0.46
2. 0.2 0.2 1.84
3. 0.2 0.1 0.92
The specific rate constant for the reaction is
(a) 2.3 sec1 (b) 0.46 L mol1 sec1
(c) 2.3 102 L2 mol1 sec1 (d) 1.125 102 L2 mol2 sec1
2. The following data pertains to a reaction between A and B
S.No. [A] mol/lit. [B] mol/lit. Rate
(mol/ lit)
time1
1. 1 102 2 102 2 104
2. 2 102 2 102 4 104
3. 2 102 4 102 8 104
Which of the following influence(s) can be drawn from the above data ?

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New Delhi 110 018, Ph. : 9312629035, 8527112111
 CK 7
4
1. Rate constant of the reaction is 10
2. Rate law of the reaction is K[A][B]
3. Rate of reaction increases four times on doubling the concentration of both the reactants.
Select the correct answer using the codes given below
(a) 1, 2 and 3 (b) 1 and 2 (c) 2 and 3 (d) 3 alone
3. From the following data, the activation energy for the reaction (cal/mol) H2 + I2 2HI
T, K 1/T, K1 log10K
3
769 1.3 10 2.9
3
667 1.5 10 1.1
(a) 4 104 (b) 2 104 (c) 8 104 (d) 3 104
[Answers : (1) d (2) c (3) a]

C5A Effect of temperature on reaction rate :

The rate of chemical reaction generally increases on increasing the temperature.
* Temperature coefficient of a reaction is defined as the ratio of rate
constant at two temperatures differing by 10 K (generally 250 and 350C).
Observed value usually lies between 2 and 3 for most of the reactions.
* Larger the value of Ea, smaller the value of rate constant.
* Larger the value of Ea, greater is the effect of a given temperature on k.
* At lower temperature, increase in temperature causes more change in
the value of k than that at higher temperature.
C5B Arrhenius equation :
Variation of rate constant k with temperature T(K) is given by Arrhenius equation.

Ea Ea
k = AeEa/RT,, lnk = ln A , logk = log A
RT 2.303RT
Where A is called the frequency factor or the pre-exponential factor. Collectively A and Ea are called the
Arrhenius parameters of the reaction.
when T , then k = A
C5C Graph on rate constant :

k2 EA 1 1
* log , where k1 and k2 are rate constants at temperature T1 and T2 respectively.
k 1 2.303R T1 T2

Rate constant (T 10) 0 C

* Temperature coefficient
rate constant at T 0C

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi 110 018, Ph. : 9312629035, 8527112111
 CK 8
Practice Problems :
1. For a gaseous reaction the plot of log k against 1/T gave a straight line with a slope of -8 103.
The activation energy E for the reaction is

8 103 2.303 8 103 R

(a) (b)
R 2.303

8 103
(c) 8 103 2.303 R (d)
R 2.303
2. The rate of reaction is doubled for evergy 100 rise in temperature. The increase in reaction rate as a
result of temperature rise from 100 to 1000 is
(a) 112 (b) 512 (c) 400 (d) 614
3. Milk turns sour at 400C three times as faster as at 00C. Hence Ea in cal (activation energy) of turning
of milk sour is :

2.303 2 313 273 2.303 2 313 273 1

(a) log 3 (b) log
40 40 3

2.303 2 40 2.303 2 40 1
(c) log 3 (d) log
273 313 273 313 3
4. In presence of catalyst Ea is lowered by 2 kcal at 270C. Hence rate will be :
(a) 20 times (b) 14 times (c) 28 times (d) 2 times

1
5. Graph between log k and [k is rate constant (s1) and T the temperature (K)] is a straight line
T
1
with OX = 5, = tan1 . Hence E will be :
2.303 a

2
(a) 2.303 2 cal (b) cal (c) 2 cal (d) none
2.303
6. The rate constant, the activation energy and the Arrhenius parameter of a chemical reaction at 250C
are 3.0 104s1, 104.4 kJ mol1 and 6.0 1014s1 respectively. The value of the rate constant as
T is
(a) 2.0 1018s1 (b) 6.0 1014s1 (c) Infinity (d) 3.6 1030s1
7. For a first order reaction, when log k was plotted against 1/T, a straight line with a slope of 6000
was obtained. The activation energy for the reaction is
(a) 13.8 103 R (b) 27600 cal (c) 114.732 103 (d) 1.14 107

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi 110 018, Ph. : 9312629035, 8527112111
 CK 9
8. The rate constant for the first order decomposition of a certain reaction is given by the equation

1.25 104
ln k (sec 1 ) 14.34 . The energy of activation in cal./mol is
T
(a) 2.5 102 (b) 250 (c) 2.5 103 (d) 2.5 104
[Answers : (1) c (2) b (3) a (4) c (5) c (6) b (7) a (8) d]

NUCLEAR CHEMISTRY
C1A Nuclear Chemistry involves the study of the nuclear changes i.e., the conversion of one element into the
another element. It was observed by various scientists that the atomic nucleus of certain element undergo
spontaneous disintegration into smaller fragments emitting powerful radiations. This phenomenon was
defined as Radioactivity and is always independent of the external conditions such as temperature,
pressure etc.
C1B Active Radiation emitted during the spontaneous disintegration of certain nuclei are :
238 234 4
particles : 92 U
90 Th + 2 He

0
234 234 ( )
particles : 90Th
91 Pa + 1e

rays : 230 230 +

90 Th *
90 Th
Types of Radioactive Decay
Types of Decay Radiation Process Nuclear change Nuclear
At. No. Mass No. Condition

Alpha emission () 4 2 4 Z > 83

2 He

N
Beta emission () 01 e 1
0n 11p 01e +1 0 too large
Z

0 1 N
Positron emission (+) 1e 1p 10n 10e 1 0 too small
Z

1 0 N
Electron capture (Ec) X rays 1 p 1e 10n 1 0 too small
Z
0
Gamma emission () 0 0 0 Excited
nucleus
C1C Group displacement law :
Emission of an -particle (a helium nucleus) lowers the atomic number by two and mass number by four;
emission of a -particle (an electron of nuclear origin) raises the atomic number by one and leaves the
mass number unchanged. Thus, the new element may be displaced either to the left (two places in case of
-emission) or to the right (one place in case of emission) in the periodic table. This displacement is
known as Group Displacement Law.
C2A Process of Radioactive Disintegration :
The atoms of radioactive element are inharently unstable, thus they undergo spontaneous disintegration
and emitting or particles and resulting in the formation of new element which is physically and
chemically different from its parent element.
* Radioactive decay follows first order kinetics.
C2B Rate of radioactive disintegration :
The rate of distingration of a radioactive material the decay rate is directly proportional to the number of
atoms present.

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dN dN
N , N
dt dt

dN
where represents rate of decay in disintegration of atoms per unit time (say second), N the number
dt
of atoms disintegrating at that time and the disintegration constant (also called decay constant).
If N0 is the number of atoms at the start of decay and N the number of atoms at a given time then by first
order kinetics.

0.693
N N 0e t , 2.303 log N 0 , At t = T50 .
t
10
N T50

n
1
Thus half-life period is independent of number of atoms present at a given time then N N 0
2

n
1
and in activity terms A t A 0
2

1 T
The average life period is related to T50 and disintegration constant as : tav = 50
0.693
Practice Problems :
1. The half-life of a radioactive element is 160 days. After 800 day 1 g of the element will reduce to

1 1 1 1
(a) g (b) g (c) g (d) g
10 20 8 32
3
2. Tritium 1 H has a half-life of 12.26 years. A 5.00 mL sample of tritiated water has an activity of
2.40 10 cpm. How many years will it take for the activity to fall to 3.00 108 cpm. ?
9

(a) 6.13 (b) 12.26 (c) 24.52 (d) 36.78

3. Two substances A and B are present such that [A] = 4[B] and the half life of A is 5 min. and that of B
is 15 minutes. If they start decaying at the same instant (first order), then how much time later will
the concentration of both of them would be equal ?
(a) 15 minutes (b) 10 minutes (c) 5 minutes (d) 12 minutes
4. Two I-order reactions have half-lives in the ratio 3 : 2. Calculate the ratio of time intervals t1 : t2 ; t1
is the time period for 25% completion of the first reaction and t2 for 75% completion of the second
reaction.
(a) 0.311 : 1 (b) 0.420 : 1 (c) 0.273 : 1 (d) 0.119 : 1
[Answers : (1) d (2) d (3) a (4) a]

C3 Radio Carbon Dating :

The application of the C-14 dating is based on the fundamental assumption that the intensity of cosmic ray
and hence of 14C in the atmosphere has been remaining constant over many thousands of years. This gives
the initial activity of C-14 corresponding to the time when the plant or animal died and assimilation of
radioactive carbon ceased to continue.

14 1 14 1
7 N 0n
6 C 1H
14
14
6 C
0
7 N 1e
2.303 original activity ( N 0 )
Age log
final activity ( N )

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New Delhi 110 018, Ph. : 9312629035, 8527112111
 CK 11
n
1 t
N N0 where n
2 T50
Practice Problems :
1. Weight of 14C to have radioactivity 1 curie [ (disintegration constant) = 4.4 1012 sec1] is :
(a) 2 104 kg (b) 0.9 104 kg (c) 1.7 104 kg (d) 3.7 1010 kg
2. An old wooden chair shows a 6C14 activity which is 80% of the activity found today. The age of the
sample is. (t of 6C14 = 5770 years).
(a) 1.85 103 (b) 5.22 103 (c) 6.23 103 (d) 7.55 103
[Answers : (1) a (2) a]

C4 Rock Dating :
It is based on the kinetic of radioactive decay. It is assumed that no lead was initially present is the sample
and the whole of it came from the uranium.
Initial radioactivity = [U] + [Pb] = N0 in terms of gram atoms
Final radioactive = [U] = N
We have assumed that due to high value of T50 of Uranium, its amount remains unchanged.

N 0 [U] [Pb] [Pb]

1
N [U] [U]

2.303 N 0 2.303 log 1 [Pb]

Thus t log
T50 N T50 [U]

Practice Problems :
1. Landing on the moon was the giant leap for the manking of the twentieth century. Rock from
238 206 238
there had equal number of atoms of 92 U and 82 Pb . If half life of 92 U is 4.5 109 years, moon
is ...... years old :
(a) 9.0 109 (b) 4.5 109 (c) 2.25 109 (d) none
[Answers : (1) b]

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi 110 018, Ph. : 9312629035, 8527112111
 CK 12
INITIAL STEP EXERCISE

1. When any radioactive substance is subjected to a (c) the time taken for the completion of 75%
vacuum, the rate of disintegration per second reaction is thrice the t of the reaction
(a) increases considerably (d) the pre-exponential factor in the
Arrhenius equation has the dimension of
(b) is not affected
T1.
(c) suffers a slight decrease
5. The rate of a gaseous reaction is given by the
(d) increases only if the products are gaseous expression k[A] [B]. If the volume of the reaction
2. A certain radioactive element A, has a half-life = t vessel is suddenly reduced to 1/4th of the initial
seconds. In (t/2) seconds, the fraction of the initial volume the reaction rate relating to original rate
quantity of the element so far decayed is nearly will be
(a) 25% (b) 29% (a) 1/10 (b) 1/8
(c) 21% (d) 17% (c) 8 (d) 16
3. Which of the following represents zero order reac- 6. The number of nuetrons accompanying the
tion : formation of 13954Xe and 9438Sr from the absorption
of a slow neutron by 23592U, followed by nuclear
fission is
(a) 0 (b) 2
(c) 1 (d) 3
(a) 7. In a first order reaction the concentration of
reactant decreases from 800 mol/dm3 to 50 mol/dm3
is 2 104 sec. The rate constant of reaction in sec1
is
(a) 2 104 (b) 3.45 105
(c) 1.386 104 (d) 2 104
(b) 8. Assume two radioactive substances A and B disin-
tegrating by :

d (A ) 0.693
k A [A] , T50 (A )
dt kA

(c) d ( B) 1
k B [ B]2 , T50 (B)
dt k B [B]0
If both half-life period are equal, rates at the start
of reaction will be in ratio when conc. are also
equal :
(a) 0.0693 (b) T50(A) kA
(c) kB (d) kA/kB
(d)
9. At radioactive equilibrium, the ratio between the
atoms of two radioactive elements A and B was
found to be 3.1 109 : 1 respectively. If T50 of the
4. For a first order reaction element A is 2 1010 years, then T50 of the element
B is :
(a) the degree of dissociation is equal to
(1 + ekt) (a) 6.2 109 years (b) 6.45 years
10
(b) a plot of reciprocal concentration of the (c) 2 10 years (d) 3.1 109 years
reactant vs time gives a straight line

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10. For the reaction 15. The rate constant K1 of a reaction is found to be
double that of rate constant K2 of another reaction.
2 NO Br2
2 NOBr , the following The relationship between corresponding activation
mechanism has been given energies of the two reactions at same temperature
(E1 and E2) can be represented as
NO + Br2 NOBr2
(a) E1 > E2 (b) E1 < E2
slow
NOBr2 NO
2 NOBr (c) E1 = E2 (d) None
Hence rate law is : 16. For the hydrolysis of esters in alkaline medium rate
(a) k[NO]2[Br2] (b) k[NO][Br2] d[Ester ]
expression is; K[Ester ][Alkali]
(c) k[NOBr2][NO] (d) k[NO][Br2]2 dt
11. The rate constant for the reaction In case alkali used is in excess, then the overall or-
2N2O5 4NO2 + O2 der of the reaction is
is 3.0 105 s1. If the rate is 2.40 105 mol L1 s1, (a) Zero (b) First
then conc. of N2O5 in mol L1 is (c) Same (d) Third
(a) 1.4 (b) 1.2 17. Inversion of a sugar follows first order rate
(c) 0.04 (d) 0.8 equation which can be followed by noting the
change in rotation of the plane of polarization of
light in the polarimeter. If r, rt and r0 are the
12. A2 2B
2AB rotations at t = , t = t and t = 0, then, first order
reaction can be written as
d[A 2 ]
[A 2 ] [B]
dt 1 r r
(a) K log e t
0.1 0.2 110 2 Ms 1 t r0 r
0.2 0.2 2 102 Ms 1 1 r r
2 1 (b) K ln 0
0.2 0.4 8 10 Ms t r1 r

Order of reaction w.r.t A2 and B are respectively : 1 r r

(c) K ln 0
(a) 1, 2 (b) 2, 1 t r rt
(c) 1, 1 (d) 2, 2
13. If a is the initial concentration of a substance which 1 r r
reacts according to zero order kinetics and K is rate (d) K ln t
t r r0
constant, the time for the reaction to go to comple-
tion is 18. Following mechanism has been proposed for
(a) a/K (b) 2/Ka reaction,
(c) K/a (d) 2K/a 2A + B D + E
14. Which of the following statement is correct for a A + B C + D.........(slow) A + C E .........(fast)
reaction X + 2Y Products The rate law expression for the reaction is
(a) The rate of disappearance of X = twice (a) r = K[A]2[B] (b) r = K[A] [B]
the rate of disappearance of Y (c) r = K[A]2 (d) r = K[A][C]
(b) The rate of disappearance of X = 1/2 rate 19. For the non-equilibrium process, A + B
of appearance of products products, the rate is first order with respect to A
(c) The rate of appearance of products = 1/2 and second order with respect to B. If 1.0 mol each
the rate of disappearance of Y of A and B are introduced into a 1 litre vessel, and
(d) The rate of appearance of products = 1/2 the initial rate were 1.0 102 mol/litre-sec. The rate
the rate of disappearance of X (in mol litre1 sec1) when half of the reactants have
been used
(a) 1.2 103 (b) 1.2 102
(c) 2.5 104 (d) None

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi 110 018, Ph. : 9312629035, 8527112111
 CK 14
0
20. For the reaction, A + B C + D. The variation of 23. At 250 C, the half life for the decomposition of N2O5
the concentration of the products is given by the is 5.7 hr and is independent of initial pressure of
curve : N2O5. The specific rate constant is
(a) 0.693/5.7 (b) 0.693 5.7
(c) 5.7/0.693 (d) None
24. What fraction of a reactant showing first order
remains after 40 minute if t is 20 minute
(a) 1/4 (b) 1/2
(c) 1/8 (d) 1/6
25. The rate constant for a second order reaction is
8 105M1. How long will it take a 1M solution to
(a) X (b) Y
be reduced to 0.5 M
(c) Z (d) W
(a) 8.665 103 minute(b) 8 105 minute
21. In acidic medium the rate of reaction between
(c) 1.25 104 minute(d) 4 105 minute
(BrO3) and Br ions is given by the expression.
26. For the reaction,

d(BrO )
3
K[BrO3 ][Br ][H ]2 1
dt N 2 O 5 2 NO 2 O 2 . Given,
2
It means :
(a) Rate constant of overall reaction is d[ N 2O 5 ] d[ NO 5 ]
K1[ N 2O 5 ],
4 sec1 dt dt
(b) Rate of reaction is independent of the
conc. of acid d[O 2 ]
K 2 [ N 2O 5 ] and K 3[ N 2O 5 ]
(c) The change in pH of the solution will not dt
affect the rate
The relation in between K1, K2 and K3 is
(d) Doubling the conc. of H+ ions will increase
(a) 2K1 = K2 = 4K3 (b) K1 = K2 = K3
the reaction rate by 4 times
(c) 2K1 = 4K2 = K3 (d) None
22. For a reaction A + B Products, the rate of the
reaction was doubled when the concentration of A 27. In gaseous reactions important for the
was doubled. When the concentration of A and B understanding of the upper atmosphere H2O and
were doubled, the rate was again doubled, the O react bimolecularly to form two OH radicals. H
order of the reaction with respect to A and B are for this reaction is 72 kJ and 500 K and Ea is 77kJ
mol1, then Ea for the bimolecular recombination
(a) 1, 1 (b) 2, 0
of two OH radicals to form H2O and O is
(c) 1, 0 (d) 0, 1
(a) 3 kJ mol1 (b) 4 kJ mol1
(c) 5 kJ mol1 (d) 7 kJ mol1

FINAL STEP EXERCISE

1. Consider the reaction X Y. The figure given (a) t1/2
below depicts the change in concentration of (b) t3/4
species X and Y as a function of time. The point of (c) t2/3
intersection of the two curves represents
(d) data insufficient to predict
2. Two reactions A Products and B products have
rate constant kA and kB at temperature, T and
activation energies EA and EB respectively. If kA >
kB and EA < EB and assuming that A for both the
reactions is same then
(a) at higher temperatures kA will be less
than kB
(b) at lower temperature kA and kB will be
close to each other in magnitude

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi 110 018, Ph. : 9312629035, 8527112111
 CK 15
(c) as temperature rises kA and kB will be ANSWERS (INITIAL STEP
close to each other in magnitude
EXERCISE)
(d) at lower temperature kB > kA
3. Two I order reactions proceed at 250C at the same
rate. The temperature coefficient of the rate of the
1. b 11. d 21. d
first reaction is 2 and that of second reaction is 3. 2. b 12. a 22. c
The ratio of the rates of second to first reaction at
750C is 3. a 13. a 23. a
(a) 7.59 (b) 1.131
4. d 14. c 24. a
(c) 0.296 (d) 3.37
4. Rate of a reaction, A + B product is given as a 5. d 15. d 25. c
function of different initial concentration of A and
B. 6. d 16. b 26. a
[A]/mol L1 [B]/mol L1 rate/mol L1 7. c 17. b 27. c
min1
0.01 0.01 0.005 8. b 18. b
0.02 0.01 0.010 9. b 19. a
0.01 0.02 0.005
10. a 20. b
The order of reaction with respect to A and with
respect to B is
(a) rate = k[A] [B]0
(b) rate = k[A]1[B]1
(c) rate = k[A]2[B]0
(d) rate = k [A]0[B]2
5. A drop of solution (volume 0.05 ml) contains
3.0 10 6 moles of H +. If the rate constant of
disappearance of H+ is 1.0 107 mole litre1 sec1.
How long would it take for H + in drop to ANSWERS (FINAL STEP EXERCISE)
disappear ?
(a) 6 109 (b) 9 109 1. a
(c) 3 109 (d) none
2. c
6. A substance, A decomposes by a first order
reaction. Starting initially with [A] = 2.00 M, after 3. a
200 min [A] = 0.250 M. For this reaction the t is 4. a
(a) 44.44 min (b) 33.33 min 5. a
(c) 55.55 min (d) 66.66 min
6. d
7. Ten grams of an -active radioisotope are
disintegrating in a sealed container. In one hour 7. a
helium gas collected at S.T.P. is 11.2 cm3. The half-
life of the radioisotope is
(a) 1.5856 years (b) 6 years
(c) 8.5 years (d) 5.56987 years

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi 110 018, Ph. : 9312629035, 8527112111
 CK 16
AIEEE ANALYSIS [2004/2005/2006]

1. In a first order reaction, the concentration of the 7. t 1/4 can be taken as the time taken for the
reactant, decreases from 0.8 M to 0.04 M in
15 minutes. The time taken for the concentration 3
concentration of a reactant to drop to of its
of change from 0.1 M to 0.25 M is 4
(a) 30 minutes (b) 15 minutes initial value. If the rate constant for a first order
(c) 7.5 minutes (d) 60 minutes reaction is K, the t1/4 can be written as
[2004] (a) 0.10 / K (b) 0.29 / K
2. The rate equation for the reaction 2A + B C is (c) 0.69 / K (d) 0.75 / K
found to be : rate = K[A] [B]. The correct 8. A reaction involving two different reactants can
statement in relation to this reaction is that the never be
(a) unit of k must be s1 (a) unimolecular reaction
(b) t is a constant (b) first order reaction
(c) rate of formation of C is twice the rate of (c) second order reaction
disappearance of A (d) bimolecular reaction
(d) value of k is independence of the initial [2005]
concentrations of A and B
9. A reaction was found to be second order with
[2004] respect to the concentration of carbon monoxide.
3. Consider the following nuclear reactions : If the concentration of carbon monoxide is doubled,
238 with everything else kept the same, the rate of
92 M XY N 3 42 He; XY N AB L 2
reaction will
The number of neutrons in the element L is (a) double
(a) 142 (b) 144 (b) remain unchanged
(c) 140 (d) 146 (c) triple
[2004] (d) increase by a factor of 4
4. The half-life of a radioisotope is four hours. If the [2006]
initial mass of the isotope was 200g, the mass
238 234
remaining after 24 hours undecayed is 10. In the transformation of 92 U to 92 U , if one
(a) 1.042 g (B) 2.084 g emission in an -particle, what should be the other
(c) 3.125 g (d) 4.167 g emission(s) ?
[2004] (a) One + and one
5. Consider an endothermic reaction X Y with the (b) Two
activation energies Eb and Ef for the backward and (c) Two and one +
forward reactions, respectively. In general (d) One and one
(a) Eb < Ef [2006]
(b) Eb > Ef 11. Rate of a reaction can be expressed by Arrhenius
(c) Eb = Ef equation as :
(d) there is no definite relation between k = A eE/RT
Eb and Ef In this equation, E represents
[2005] (a) the fraction of molecules with energy
6. A photon of hard gamma radiation knocks a greater than the activation energy of the
24 reaction.
proton out of 12 Mg nucleus to form
(b) the energy above which all the colliding
(a) the isotope of parent nucleus molecules will react
(b) the isobar of parent nucleus (c) the energy below which colliding
(c) the nuclide 23
Na molecules will not react.
11
(d) the total energy of the reacting molecules
23 at a temperature, T
(d) the isobar of 11 Na
[2005] [2006]

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi 110 018, Ph. : 9312629035, 8527112111
 CK 17
12. The following mechanism has been proposed for
the reaction of NO with Br2 to form NOBr
NO(g) + Br2(g) NOBr2(g)
NOBr2(g) + NO(g) 2 NOBr(g)
If the second step is the rate determining step, the
order of the reaction with respect to NO(g) is
(a) 2 (b) 1
(c) 0 (d) 3
[2006]

AIEEE ANALYSIS [2007]

13. Which of the following nuclear reactions will 15. A radioactive element gets spilled over the floor of
generate an isotope ? a room. Its half-life period is 30 days. If the initial
(a) -particle emission activity is ten times the permissible value, after how
many days will it be safe to enter the room ?
(b) -particle emission
(a) 10 days (b) 100 days
(c) neutron particle emission
(c) 1000 days (d) 300 days
(d) positron emission
16. The energies of activation for forward and reverse
14. Consider the reaction,
reactions for A2 + B2 2AB are 180 kJ mol1
2A + B Products 1
and 200 kJ mol respectively. The presence of a
When concentration of B alone was doubled, the catalyst lowers the activation energy of both
half-life did not change. When the concentration (forward and reverse) reactions by 100 kJ mol1.
of A alone was doubled, the rate increased by two The enthalpy change of the reaction
times. The unit of rate constant for this reaction is (A2 + B2 2AB) in the presence of catalyst will be
(a) mol L1 s1 (b) s1 (in kJ mol1)
(c) L mol1 s1 (d) no unit (a) 280 (b) 20
(c) 300 (d) 120

ANSWERS AIEEE ANALYSIS

1. a 2. d 3. b 4. c 5. a 6. c 7.
8. a 9. d 10. b 11. c 12. a 13. c 14. c
15. b 16. 20

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi 110 018, Ph. : 9312629035, 8527112111
 CK 18
TEST YOURSELF
1. Consider the reaction 2A + B products
1
when concentration of B alone was a doubled, the (a) n 1, t 1 / 2
half life did not change, when the concentration of k .a
A alone as doubled, the rate increased by two times. 1
The unit of rate constant for this reaction is (b) n 2, t 1 / 2
a
(a) S1 (b) L mol1S1
(c) mol L1S1 (d) unit less 0.693
(c) n 1, t 1 / 2
2. Rate of a reaction can be expressed by Arrhenius k
equation as : K = Ae E/RT . In this equation, (d) none
E represents 7. Two reactions X products and Y products
(a) The energy above which all the colliding have rate constant kA and kB at temperature, T and
molecules will react. activation energies E X and E Y respectively. If
(b) The energy below which colliding KX > KY and EA < EB and assuming that A for both
molecules will not react. the reactions is same then [A is frequency factor]
(c) The total energy of the reacting molecules (a) at higher temperature KX will be greater
at a temperature T than KY
(d) The fraction of molecules with energy (b) at lower temperature KX and KY will
greater than the activation energy of the differ more and KX > KY
reaction. (c) as temperature rises KX and KY will be
3. A reaction involving two different reactants can close to each other in magnitude
never be (d) all
(a) unimolecular reaction 8. For a reaction of 8000C
(b) first order reaction 2NO + H2 N2 + 2H2O
(c) second order reaction
(d) bimolecular reaction 1 d[NO]
[NO] [H2]
4. In Ist order reaction, the concentration of the 2 dt
reactant, decreases from 0.8 M to 0.4 M in 1.5 104 4 103 4.4 104
4
15 minutes. The time taken from the concentration 1.5 10 2 103 2.2 104
4
to change from 0.1 M to 0.025 M is 0.5 10 2 103 0.24 104
(a) 30 minutes (b) 15 minutes The rate constant is
(c) 7.5 minutes (d) 60 minutes (a) 4.88 108 mol2litre2min1
5. aA + bB product. If concentration of A is doubled, (b) 3.12 108 mol2litre2min1
rate is four times. If concentration of A and B is (c) 3.80 108 mol2litre2min1
doubled, rate is eight times, hence (d) 4.30 108 mol2litre2min1
9. The rate constant of a reaction is 1.0 107s1 at 500C
dx d[ A] d[B]
(a) and 2.0 107s1 at 1000C. Ea is
dt dt dt (a) 1.4 104 J/mol
2dx d[ A ] 2d[B] (b) 1.9 104J/mol
(b) (c) 1.1 104 J/mol
dt dt dt
(d) 2.25 104 J/mol
2dx d[ A ] d[B] 10. For IIIrd order reaction
(c)
dt dt dt 2 3
(a) t1/ 2 (b) t1/ 2
2dx 2d[ A ] d[B] 3ka 2 2ka
(d)
dt dt dt 2 3
6. A graph plotted between log t vs. concentration is (c) t1/ 2 (d) t1/ 2
3ka 2ka 2
a straight line. What conclusion can you draw from
the given graph : ANSWERS

1. b 6. c
2. b 7. d
3. a 8. a
4. a 9. a
5. b 10. d

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi 110 018, Ph. : 9312629035, 8527112111