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CHEMISTRY
S T U D Y M A T E R I A L
PHASE - I
CHEMICAL KINETICS &
NUCLEAR CHEMISTRY
IIT-JEE
NARAYANA INSTITUTE OF CORRESPONDENCE COURSES
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2004 NARAYANA GROUP
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PREFACE
Dear Student,
Heartiest congratulations on making up your mind and deciding to be an engineer to serve the society.
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CHEMICAL KINETICS
C O N T E N T S
& NUCLEAR CHEMISTRY
1. Theory
2. Solved Problems
3. Assignments
4. Answers
CHEMICAL KINETICS
& NUCLEAR CHEMISTRY
IIT-JEE Syllabus
Rates of chemical reactions; Order of reactions; Rate constant; First order
reactions; Temperature dependence of rate constant (Arrhenius equation).
CONTENTS INTRODUCTION
Rate of reaction Some chemical reaction occurs within
few micro seconds or milli seconds due
Elementary reaction to formation of reaction intermediate
Integrated rate laws (carbocation, carboanion or free radicals).
But some reaction occur in few year or
Activation energy months because breaking of strong ionic or
metallic bond is a slow process. Under
Kinetics of some complex first order
reactions chemical kinetics we would study that
reaction which occurs at measurable rate.
Methods of determining order
In Chemical Kinetics we would be able to
Nuclear chemistry understand the velocity as well as different
factors which would effect the chemical
Kinetics of radioactive disintegration
reaction. Under this we will be studying
the mechanism of the reaction. Here
mechanism of reaction means how
reactants are converted into product or in
how many intermediate steps reactant is
converted into product. And which
intermediate step is rate determining step.
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1. RATE OF REACTION
Rate of a reaction is defined as the increase in molar concentration of a product per unit
time or decrease in molar concentration of a reactant per unit time. Molar concentration is
normally measured in moles per litre, the rate of a reaction is specified in mole per litre per
time.
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EXERCISE 1
1. For the reaction; 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g), the rate of reaction in terms of
d[NH3 ]
disappearance of NH3 is − , then write rate expression in terms of O2, NO and
dt
H2O.
2. For the decomposition reaction: N2O4(g) → 2NO2(g); the initial pressure of N2O4 falls
from 0.46 atm to 0.28 atm in 30 minute. What is the rate of appearance of NO2?
3. A chemical reaction 2A → 4B + C; in gaseous phase shows an increase in concentration
of B by 5 × 10–3 M in 10 second. Calculate:
a) rate of appearance of B,
b) rate of the reaction,
c) rate of disappearance of A
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2. ELEMENTARY REACTION
An elementary reaction is a single molecular event, such as collision of molecules resulting
in a reaction. The set of elementary reactions whose overall effect is given by the net
chemical equation is called reaction mechanism.
Let us consider an example for the reaction of nitrogen dioxide with carbon monoxide.
NO 2(g) + CO(g)
→ NO (g) + CO 2(g) [net chemical equation] …(i)
Suppose this chemical reaction takes place in two steps
NO 2(g) + NO 2(g)
→ NO3(g) + NO (g) [Elementary reaction] …(ii)
NO3(g) + CO (g)
→ NO 2(g) + CO 2(g) [Elementary reaction] …(iii)
Thus net reaction (i) is obtained by the combination of two elementary reaction (ii) and (iii)
and NO3 is a reaction intermediate as it is produced and consumed during the course of
reaction.
2.1 MOLECULARITY
It is defined as the number of molecules taking part on the reactant side of an elementary
reaction. A unimolecular reaction is an elementary reaction involves one reactant molecule,
a bimolecular reaction is an elementary reaction that involves two reactant molecules.
2.2 DIFFERENTIAL RATE LAW
It is a relationship that relates the variation of rate of reaction with the concentration of
reactants.
Consider the reaction
2A + 3B
→C + D
as we have seen
1 d[A] d[C]
− = ∝ [A]m [B]n
2 dt dt
[law of mass action states that rate of reaction is directly proportional to the product of the
active masses of reactants raised to some powers]
d[C]
So, = k[A]m [B]n
dt
k is known as velocity constant or rate constant or specific reaction rate. m is known as
order with respect to A, n is known as order with respect to B. Sum m + n is known as
overall order of the reaction.
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Note : If a reaction can be written as a combination of several elementary reaction then it’s the
slowest step that governs the rate of reaction i.e. the slowest step is the rate determining step.
Differential Rate Law :
Consider reaction
P + 2Q
→R
The differential rate law is written as
d[P] 1 d[Q]
Rate = − =− = k[P]m [Q]n
dt 2 dt
Value of m and n can be determined by performing the reaction in laboratory i.e. order
w.r.t P is m and order w.r.t. Q is n and overall order will be m + n.
4.4 UNITS OF k
In general rate law for a nth order reaction can be written as
dC
= kCn
dt
Where k is rate constant, k is characteristic of a reaction at a given temperature. It changes
only when temperature changes and n is the order of reaction.
dC / dt
k=
Cn
Units of k: (concentration)1–ntime–1
For a zero order reaction (n = 0)
Units of k = mol/L/s
For a first order reaction (n = 1)
Units of k = time–1
For a second order reaction (n = 2)
Units of k = (mol/l)–1time–1 = l/mol/s
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Illustration 2 :The data given below are for the reaction of NO and Cl2 to form NOCl at 25K
[Cl2] [NO] Initial rate × 103 (mol litre–1sec–1)
0.05 0.05 1
0.15 0.05 3
0.05 0.15 9
a) What is the order with respect to NO and Cl2 in the reaction?
b) Write the rate expression.
c) Calculate the rate constant
d) Determine the reaction rate when conc. of Cl2 and NO are 0.2 M and 0.4 M
respectively.
Solution : For the reaction; 2NO + Cl2 → 2NOCl
Rate = k[Cl2]m[NO]n …(1)
Where, m and n are order of reaction w.r.t Cl2 and NO, respectively.
From the given data:
1 × 10–3 = k[0.05]m [0.05]n …(2)
n=1
r 1× 10−3
c) And rate constant., k = = = 8 litre2 mol–2 sec–1
[Cl2 ][NO]2 [0.05]1[0.05]2
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EXERCISE 2 :
1. The reaction; 2A + B + C → D + 2E; is found to be I order in A II order in B and zero
order in C.
a) Write the rate expression
b) What is the effect on rate on increasing the conc. of A, B and C two times.
2. The reaction; 2NO + Br2 → 2NOBr, is supposed to follow the following mechanism,
fast
i) NO + Br2 NOBr2
ii) NOBr2 + NO
slow
→ 2NOBr
Suggest the rate law expression
3. The thermal decomposition of N2O5 occurs in the following steps:
Step I: N2O5
slow
→ NO2 + NO3
Step II N2O5 + NO3 →
fast
3NO2 + O2
–––––––––––––––––––––––––––
Overall reaction 2N2O5 → 4NO2 + O2-
Suggest the rate expression
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A→ Products
t=0 a
t=t a–x
2.303 a
k= log
t a−x
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Important thing is that in a first order reaction time required for the completion of a definite
fraction is independent of initial concentration of reactants.
2.303
slope = −
2.303 K
log a
time
log(a − x)
H 2O2
→ H 2O + O [slow i.e. rate determining step]
O + O
→ O 2 [fast]
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So Rate ∝ [H 2 O2 ]1
or R = k[H 2 O2 ]
Order = 1
Kinetics of this reaction can be studied by withdrawing a definite volume of reaction
mixture after regular interval of time and titrating it against KMnO 4 solution in presence of
dil. H 2SO4
2KMnO 4 + 3H 2SO4
→ K 2SO4 + 2MnSO 4 + 3H 2O + 5O
[H 2O2 + O
→ H 2 O + O2 ] × 5
––––––––––––––––––––––––––––––––––––––––––––––––
2KMnO 4 + 3H 2SO 4 + 5H 2O 2
→ K 2SO4 + 2MnSO 4 + 8H 2O + 5O 2
Since H2O2 is undergoing self decomposition so quantity of H2O2 present in a definite
volume will also go on decreasing, KMnO4 is reacting with H2O2 so titre value i.e. volume
of KMnO4 used will also go on decreasing.
Let V0 and Vt be the volumes of KMnO 4 used at zero time and after t time respectively.
then V0 ∝ a [a = initial conc. of H 2O2 ]
Vt ∝ a − x [a –x = conc. of H 2O2 after t time]
V0 a
=
Vt a − x
2.303 V
k= log 0
t Vt
Illustration 3 :From the following data show that the decomposition of hydrogen peroxide in
aqueous solution is a first - order reaction. What is the value of the rate
constant ?
Time in minutes 0 10 20 30 40
VolumeV/(ml) 25.0 20.0 15.7 12.5 9.6
where V is the number of ml of potassium permanganate required to decompose a
definite volume of hydrogen peroxide solution.
Solution : The equation for a first order reaction is
2.303 a
k1 = log
t a-x
The volume of KMnO4 used, evidently corresponds to the undecomposed
hydrogen peroxide.
10
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Hence the volume of KMnO4 used, at zero time corresponds to the initial
concentration a and the volume used after time t, corresponds to (a - x) at that
time. Inserting these values in the above equation, we get
2.303 25
when t = 10 min. k1 = log = 0.022287 min-1 = 0.000314 s-1
10 20.0
2 .303 25
when t = 20 min. k1 = log = 0.023230 min -1 = 0.0003871 s -1
10 15.7
2.303 25
when t = 30 min. k1 = log = 0.02369 min -1 = 0.0003948 s -1
30 12.5
2.303 25
when t = 40 min. k1 = log = 0.023897 min -1 = 0.0003983 s -1
40 9.6
The constancy of k, shows that the decomposition of H2O2 in aqueous solution is a
first order reaction.
The average value of the rate constant is 0.0003879 s-1.
11
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Note: t = ∞ indicates that sufficient time is provided to the reaction i.e., the reaction has
practically gone to completion.
Illustration 4 : From the following data for the decomposition of diazobenzene chloride, show
that the reaction is of first order:
Time (min) 20 50 70 ∞
Volume of N2 (mL) 10 25 33 162
Solution : C6H5N2Cl → C6H5Cl + N2
initial concentration a
Concentration of after time t (a – x) x
At ∞ time, i.e., when the reaction is complete, the whole of C6H5N2Cl converts
into N2. Hence volume of N2 at ∞ time corresponds to the initial concentration ‘a’
while volumes of N2 at different time intervals correspond to x as shown above.
2.303 162
For t = 20 min, k1 = log = 0.0032min −1
20 162 − 10
2.303 162
For t = 50 min, k1 = log = 0.0033min −1
50 162 − 25
2.303 162
For t = 70 min, k1 = log = 0.0032min −1
70 162 − 33
The constant of k1 shows that the decomposition of C6H5N2Cl; is a first order
reaction.
rearrangement
isomerism
→
N-chloro-N-phenylacetamide
Cl
N-(4-chlorophenyl)acetamide
Rate ∝ [N-chloroacetinalide]1
order = 1
Kinetics of this reaction may be studied by withdrawing a definite volume of the reaction
mixture after regular intervals of time, adding excess of KI and titrating the liberated
I2 against standard sodium thiosulphate solution.
N-chloroacetinalide reacts with KI and liberates I2 but p-chloroacetinalide does not.
I2 + 2Na 2S2O3
→ Na 2S4O6 + 2NaI
12
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N-chloroacetinalide
→ P − chloroacetinalide
t=0 a 0
t=t a–x x
Let V0 and Vt be the volumes of sodium thiosulphate used at t = 0 and t = t respectively,
then
V0 ∝ a
Vt ∝ a − x
V0 a
=
Vt a − x
2.303 V
k= log 0
t Vt
Illustration 5 : Acetochloracetanilide (N-chloroacetanilide) is converted into p-
chloroacetanilide, it is followed by the addition of KI which acts only on the
former compound. The progress of reactionis studied by titrating the iodine
liberated with standard hypo solution and the following results are obtained.
Time (hour) 0 1 2 6
ml of hypo solution 45 32 22.5 5.7
Show that the reaction is unimolecualr. Calculate the velocity constant of the
reaction and also determine the fraction of N-chloroacetanilide which has
reacted in three hours.
Solution : The velocity constant of the first order reaction is given by
2.303 a
k= log
t a−x
Here the initial concentration ‘a’ corresponds to the volume of hypo used against
liberated iodine at time 0, a = 45, (a – x) corresponds to the volume of hypo used
for titrations at different intervals of time, i.e. when t = 1 hour, (a – x) = 32, and so
on.
Substituting the values in the above equation,
(i) When t = 1 hour, (a – x) = 32
2.303 45
k= log = 0.3411
1 32
(ii) When t = 2 hours, (a – x) = 22.5
2.303 45
k= log = 0.3468
t 22.5
(iii) When t = 6 hours, (a – x) = 5.7
13
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2.303 45
∴ k= log = 0.3443
6 5.7
Since the value of K in all the three cases is nearly same, the reaction must be
unimolecular.
Calculation of fraction that has reacted in 3 hours
Let the amount reacted in 3 hours = x moles
Given a = 45, t = 3 hours, (a – x) = 45 – x
Substituting these values in the reaction
2.303 a
k= log
t a−x
2.303 45
0.300 = log
t (45 − x)
45 – x = 16.03
∴ x = 28.97
28.97
Hence fraction of N-chloroacetanilide reacted in 3 hours = = 0.643
45
i) CH3 CH3
H3C Br
slow
→ H 3C + Br -
CH3 CH3
H3C + OH - →
fast
H3C OH
CH3 CH3
= K[(CH3 )3 CBr]
Molecularity = 2
14
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Order = 1
So the reaction is pseudo unimolecular
V∞ − V0 ∝ a
(V∞ − V0 ) − (Vt − V0 ) ∝ a − x
V∞ − Vt ∝ a − x
V∞ − V0 a
=
V∞ − Vt a − x
2.303 V − V0
k= log ∞
t V∞ − Vt
15
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Illustration 6 :5 ml of ethylacetate was added to a flask containing 100 ml of 0.1 N HCl placed
in a thermostat maintained at 30°C. 5 ml of the reaction mixture was withdrawn
at different intervals of time and after chilling, titrated against a standard alkali.
The following data were obtained :
16
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If some inert liquid is used as solvent then concentration of water can be changed and rate
changes on changing the concentration of water. The reaction then becomes second order.
Rate of this reaction is also proportional to the concentration of catalyst H+. But
concentration of catalyst remains constant during the reaction. If we change concentration
of water as well as that of H+ then reaction becomes 3rd order.
Rate ∝ [C12 H 22 O11 ][H 2 O][H + ]
Fructose
Laevo rotatory
Glucose
Cane sugar
dextro rotatory
Kinetics of this reaction can be studied by taking cane sugar solution in a polarimeter and
measuring the angles of rotation after regular intervals of time.
Let r0 , rt and r∞ be the angles of rotation at 0 time, after t time and at the end of reaction.
0°
rt
r∞
r0
-90° 90°
180°
So, r0 − rt ∝ x …(i)
r0 − r∞ ∝ a …(ii)
17
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(r0 − r∞ ) − (r0 − rt ) ∝ a − x
or rt − r∞ ∝ a − x
r0 − r∞ a
=
rt − r∞ a − x
2.303 r −r
k= log 0 ∞
t rt − r∞
Illustration 7 :The optical rotations of sucrose in 0.5 N HCl at 35°C at various time intervals
are given below. Show that the reaction is of first order :
Time (minutes) 0 10 20 30 40 ∞
Rotation (degree) +32.4 +28.8 +25.5 +22.4 +19.6 -11.1
Solution : The inversion of sucrose will be first order reaction if the above data confirm to
2.303 r −r
the equation , k 1 = log 0 ∞
t rt − r∞
Where r0, rt and r∞ represent optical rotations at the commencement of the reaction
after time t and at the completion of the reaction respectively
n the case a0 = r0 - r∞ = +32.4 - (-11.1) = +43.5
Time rt rt - r∞ k
2.303 43.5
10 min +28.8 39.9 log = 0.008625 min-1
10 39.9
2.303 43.5
20 min +25.5 36.6 log = 0.008625 min-1
20 36.6
2.303 43.5
0 min +22.4 33.5 log = 0.008694 min-1
30 33.5
2.303 43.5
40 min +19.6 30.7 log = 0.008717 min-1
40 30.7
The constancy of k1 indicates that the inversion of sucrose is a first - order reaction.
18
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EXERCISE 3 :
1. From the data obtained for decomposition of H2O2, show that decomposition of a first
order reaction.
Time in minutes 0 10 20 30 40
Volume of KMnO4 (ml) 25.0 20.0 15.7 1.5 9.6
2. From the following data for the decomposition of ammonium nitrite in aqueous solution,
show that the reaction is a first order.
Time in minutes 10 15 20 15 ∞
Volume of N2(ml) 6.25 9.00 11.4 13.65 35.05
3. A certain volume of ethyl acetate was added to a flask containing HCl (as catalyst)./ 5 m l
of reaction mixture was withdrawn at different intervals of time and titrated against a
standard alkali. The following data were obtained
Eb
Products Products
∆H Reactants
∆H
Products
Reactants
Threshold energy
19
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20
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R → Gas constant
E
∫ d nk = ∫ RT 2
dT. {E is supposed to be constant] nK
E
slope = −
E 1 R
nk = − + C
R T
1/ T
E
or nk = − +C …(iv)
RT
on comparing this equation with Y = mx + C
21
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1
k (E ac − E a )
⇒ = e RT
kc
k 1
⇒ log = (Eac − Ec )
k c 2.303RT
k 1
⇒ log = (6 × 103 − 200 × 103 )
k c 2.303 × 2 × 310
k
⇒ log = −9.8
kc
k kc
⇒ = 1.56 ×10 −10 or = 6.3 × 109
kc k
Illustration 9 : A first order reaction A → B requires activation energy of 70 kJ/mol. When
20% solution of A was kept at 25°C for 20 minutes, 25% decomposition too
place. What will be the percent decomposition in the same time in a 30%
solution maintained at 40°C? Assume that the activation energy remains
constant in this range of temperature.
Solution : Note: it does not matter whether you take 20%, 3%, 40% or 70% of A.
At 25°C, 20% of A decomposes 25%
C0
⇒ kt = 2.303log
Ct
100
⇒ k(40) = 2.303log
75
⇒ k(at 25°C) = 0.0143min -1
k 40° Ea T2 − T1
log =
k 25° 2.303R T1T2
k 40° 70 × 103 40 − 25
log =
0.0143 2.303 × 8.31 298 × 313
⇒ k (at 40°C)=0.055min -1
Now calculate the % decomposition at 40°C using first order kinetics
C0
kt = 2.303log
Ct
100
⇒ 0.055 × 40 = 2.303log
100 − x
⇒ x = 67.1 ≡ 67.1% decomposition of A at 40°C.
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High E
200
Low E
100
50
E
nK slope = −
20 R
10
∆T = 1000 ∆T = 87
5
for doubling rate for doubling rate
iii) A given reaction is much more temperature sensitive at low temperatures then at high
temperatures.
EXERCISE 4 :
1. (i) Which reaction will have the greater temperature dependence for the rate constant,
one with small value of Ea or one with large value of Ea
11067
(ii) For a reaction, rate constant is given as lnK(min–1) = 31.33 – . Evaluate, K,E
T
and A for the chemical reaction at 25°C.
2. For a particular first order reaction at 27°C, the concentration of reactant is reduced to one
half of its initial value after 5000s. At 37°C, the concentration is halved after 1000s.
Calculate (a) the rate constant of the reaction at 27°C, (b) the time required for the
concentration to be reduced to one quarter of its value at 37°C, (c) the activation energy
of the reaction.
3. The Arrhenius equations for the rate constant of decomposition of methyl nitrite and ethyl
nitrate are
−152300Jmol−1 −157700Jmol−1
k1 (s −1 ) = 1013 exp and k 2 (s −1
) = 1014
exp
RT RT
respectively. Find the temperature at which the rate constants are equal.
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Potential energy
Rate = k′[Ester] Eb
Reactants
∆H
where k′ = k[H + ]
Products
Now according to the definition of the catalyst are substances which increases the rate of
reaction by their presence but their presence is not required for the reaction to occur. Now
according to this definition, absence of H + should not let the reaction to happen, therefore
the rate of reaction in the absence of H + should be, Rate = K[ester]
If [H + ] < 1 M then rate of reaction would becomes less than the rate which we had in its
absence. In order to avoid above controversies, we are required to go through the
functioning of catalyst.
There are two types of catalyst.
a) Reactant catalyst b) Non-reactant catalyst.
Former increases the rate of reaction by existing in the rate law. Therefore, in the absence
of reactant catalyst the reaction rate will be zero i.e. no reaction will take place.
The non-reacting catalyst on the other hand do not exist in the rate expression. Changing
the concentration of non-reacting catalyst has no effect on the rate. These catalyst increase
the rate of reaction by either decreasing activation energy or by increasing Arrhneius
constant.
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k1 B
k2 C
d [ B]
∵ + = k1 [ A ]t …(i)
dt
d [ C]
∵ + = k 2 [ A ]t …(ii)
dt
d [A ]
∵ − = k 0 [ A ]t …(iii)
dt
d [A] d [ B] d [ C]
∵ − =+ + …(iv)
dt dt dt
Putting equations (i), (ii) and (iii) in equation (iv), we get
k 0 [ A ]t = k1 [ A ]t + k 2 [ A ]t
or, k 0 = k1 + k 2
From equation (i) and (ii), we get
d [ B]
= k1 [ A ]t
dt
or, [ B]t = ∫ d [ B] = k1 ∫ [ A ]t dt …(v)
[ A]0
∴ ( k1 + k 2 ) t = 2.303log
[ A ]t
If k1 and k2 , t and [A]0 is known, then [A]t can be calculated then by solving equations
(vii) and (viii), the concentration of B and C at any time i.e., [B]t and [C]t can be calculated.
(b) Half lives of A in different path of parallel chain reaction.
∵ for parallel chain reaction
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k1 B
k2 C
k0 = k1 + k2
or k0 > k1 and k0 > k2
Let the rate of formation of B is x% rate of decomposition of A.
d [ B] d [A]
∴ + = x% × −
dt dt
⇒ k1 [A]t = x % × k0 [A]t
or, k1 = x% × k0
ln2 x l n2
⇒ = ×
( t1/ 2 )1 100 ( t1/ 2 )overall
100 × ( t1/ 2 )overall
or, ( t1/ 2 )1 =
x
where (t1/2)1 is the half life of A, while it is converting into B and (t1/2)overall is the half life
of A.
k1 mB
k2 nC
[ B ]t mk1
=
[ C ]t mk 2
and koverall = k1 + k2
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d [ B]
(d) Time at which is maximum
dt
2 k
t= ln 2
k1 − k 2 k1
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d [A ]
∴ − = k1 [ A ]t
dt
Illustration 10 : 227Ac has a half-life of 22.0 years with respect to radioactive decay. The decay
follows two parallel, paths, one leading to 222Th and the other to 223Fr. The
percentage yields of these two daughter nuclides are 2.0 and 98.0 respectively.
What are the decay constants (λ) for each of the separate paths?
Solution : The rate constant of the decay is
0.693 0.693
k= =
t 12 22
222
If k1 and k2 are the rate constants of the reactions leading to Th and Fr223,
respectively we have
0.693
k1 + k2 = ;
22
k1 2
=
k 2 98
On solving for k1 and k2, we get
k2 = 0.03087 y−1
k1 = 0.00063 y−1
EXERCISE 5 :
1. An organic compound A decomposes following two parallel first order mechanisms.
B
k1 1
A = and k1 = 1.3 × 10−5 s−1
k2 9
C
Calculate the concentration ratio of C to A, if an experiment is allowed to start with only
A for one hour.
2. For a consecutive first order reaction A
K1
→ B
K2
→C, the values of K1 and K2 are
–1 –1
45 sec and 15 sec respectively. If the reaction is carried out with pure A at a
concentration of 1.0 mol dm–3,
a) How much time till be required for the concentration of B to reach a minimum.
b) What will be the maximum concentration of B.
c) What will be the composition of the reacting system after a time interval of 10
minute.
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x dx t
∫x0 xe − x
= ∫ (k1 + k 2 )dt
0
xe − x0
log = (k1 + k 2 )t
or xe − x
1 x − x0
Or (k 1 + k 2 ) = log e
t xe − x
The equation is similar to first order reaction except that the measured rate constant is now
the sum of the forward and the reverse rate constants.
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or Pt = P0 + x, x = Pt – P0
a – x = P0 – (Pt – P0) = 2P0 – Pt
2.303 P0
Thus, k= log
t (2P0 − Pt )
1 [A]0
K = ln . If for different values of t and [A]t , K comes constant then order of
t [A]t
reaction will be 1 other wise we will switchover to higher order expressions.
1 x
Second order k2 =
t a(a − x)
1 x(2a − x)
Third order k3 = 2
t a (a − x 2 )
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(ii) Graphical Method: In this method the data are plotted according to different
integrated rate equations so as to yield a straight line suppose log (a–x) vs t is a straight
line then order of reaction will be 1.
t t t
1
(a − x)2 Third order
(iii) Half life Method: As we have seen for nth order reaction
1
t1/ 2 ∝
a n −1
Let t11/ 2 be the half life at initial concentration a1 and t 21/ 2 be the half life at intial
concentration a 2 .
1
Then t11/ 2 ∝
a1n −1
1
t 21/ 2 ∝
a n2 −1
n −1
t11/ 2 a
= 2
t 21/ 2 a1
So by knowing half life at two different initial concentrations, order of reaction can be
calculated.
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7. NUCLEAR CHEMISTRY
7.1 INTRODUCTION
In chemical reactions, atoms of the reactants combine by a rearrangement of extra nuclear
electrons but nuclei of the atoms remains unchanged. In a nuclear reaction on the other
hand, it is the nucleus of the atom which is involved.
7.2 RADIOACTIVITY
This can be defined as the spontaneous emission of certain kinds of radiations by some
elements and the elements emitting such radiation are called radioactive elements.
Radiation emitted by radioactive substances are of three types :—
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(i) About 160 stable nuclides have an even number of protons and an even number of
neutrons, for example, 126 C
(ii) About 50 stable nuclides have an even number of protons and an odd number of
neutrons, for example, 25
12 Mg .
(iii) About 50 stable unclides have an odd number of protons and an even number of
neutrons, for example, 199 F .
(iv) Only 4 stable nuclides have an odd number of protons and an odd number of neutrons.
They are 12 H, 36 Li, 105 B, and 147 N .
One theoretical approach to nuclear stability is the nuclear shell theory. In simplest terms,
this theory proposes that the protons and the neutrons each exist in shells within the
nucleus. This is much like the existence of electrons in shells outside the nucleus. The
similarity extends to the special stability associated with the closing of shells, similar to
what is seen with the noble gases in electrons configuration. In the nuclear shell theory, a
special stability is associated with nuclei that have any of the following numbers as
numbers of protons or neutrons.
2, 8, 20, 28, 50, 82, 126
These numbers are called magic numbers because scientists recognized their significance
in relation to nuclear stability before they had developed a theory to explain them.
One observation consistent with these magic numbers is the fact that alpha particles are
very stable; they have 2 protons and 2 neutrons and are ‘‘doubly magic.’’ Another
observation is that tin (Z = 50) has ten naturally occurring stable nuclides, more than any
other element. The magic number of protons (50) seems to allow for a greater variation in
the number of neutrons in the tin nucleus than in others. Also, the uranium-238 radioactive
decay series terminates in the nuclide 20826 Pb ; the uranium-235 series, in 20827 Pb ; and the
208
thorium-232 series, in 82 Pb . All these terminating includes have the magic number 82 in
208
lead (Z = 82); 82 Pb is doubly magic, with 82 protons and 126 neutrons.
A crucial factor in the stability of a nucleus is the ratio of the neutron number (N) to the
proton number (Z). Some nuclides of the lightest elements have an N/Z ratio of 1, and as a
group these nuclides have an average ratio slightly greater than 1. Examples of nuclides in
this group are 42 He, 186 O, 13
27 39
Al, 19 40
K, and 20 Ca . Nuclides with Z > 20 require a large number
of neutrons than protons to moderate the effect of increasing proton repulsions. For
example, the N/Z ratio in 56 133 209
26 Fe is 30/26 = 1.15; in 55 Cs it is 78/55 = 1.42, and in 83 Bi ,
126/83 = 1.52. For nuclides with Z > 83, the protons repulsions are too large to be
overcome by proton-neutron interactions, and the nuclides are all radioactive.
The general pattern for nuclear stability in terms of neutron and proton numbers is shown
in figure, a graph of neutron number (N) versus proton number (Z). All of the naturally
occurring stable nuclides are indicated by dots within the belt labeled the belt of stability.
However, other nuclides in this belt that are not shown are radioactive. Also all nuclides
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falling outside the belt are radioactive, and their mode of decay is one that brings the
nuclides formed in the decay process into the belt. Nuclides above the belt decay by beta
emission, and those below the belt by positron emission and electron capture. Many of the
nuclides in the upper right corner decay by alpha emission. If the numbers 114 and 184 are
also magic numbers, as some scientists think they are, there might be a small island of
stability centered on the nuclide with Z = 114 and N = 184. This nuclide may someday be
synthesized, and there have even been unsuccessful attempts to find element 114 in natural
sources.
118 234
Illustration 11 :Which of the following would you expect to be radioactive, 50 Sn, 91 Pa, 54
25 Mn,
74
30 Zn ?
118
Solution : Sn : This nuclide has 50 protons and (118 – 50) = 68 neutrons. This is an even-
50
even combination, the most common for stable nuclides. Also, the neutron :
proton ratio of 68:50 lies within the belt of stability so 11508 Sn is non-radioactive.
234
91 Pa : Atomic number 91 exceeds the limit for the naturally occurring stable
234
nuclides (Z > 83). 91 Pa is radioactive.
54
Mn : This nuclide has 25 protons and (54 – 25) = 29 neutrons. This is an odd-
25
odd combination found only in four stable nuclides of low atomic numbers. We
should expect that it is radioactive.
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74
30 Zn : This nuclide has 30 protons and (74 – 30) = 44 neutrons. So Z = 30, the
74
upper limit of the belt of stability is at about N = 40. The nuclide 30 Zn lies above
the belt and is radioactive.
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Gama-ray emission : Gamma (γ) rays are a highly penetrating form of electromagnetic
radiation. They consist of photons, and thus they are not particles of matter. They are
emitted by energetic nuclei as a means of reaching a lower energy state. In a nuclear
equation for gama-ray emission, we represent the energetic nucleus by affixing the symbol
m to its mass number. For example, in the radioactive decay of uranium-238 by alpha-
particle emission, 23% of the thorium-230 nuclei formed are in an excited state : 230m
90 Th .
When a decaying nucleus emits a positron, its atomic number decreases by 1 and its mass
number is unchanged. The new nuclide is that of a different element from the decaying
nuclide.
Electron capture : Electron capture (EC) is a process in which the nucleus absorbs an
electron from an inner electronic shell, usually the first or second. An X ray is released
when an electron from a higher quantum level drops to fill the level vacated by the
captured electron. Once inside the nucleus, the captured electron. Once inside the nucleus,
the captured electron combines with a proton to form a neutron.
0
-1 e + 11P ¾ ¾® 1
0 n
Nuclear equations for electron capture usually show the captured electrons as a reactant.
Iodine-125, used in medicine to diagnose pancreatic function and intestinal fat absorption,
decays by electron capture.
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56 Ba140 + 36 Kr 93 + 30 n1
92 U 235 + 0 n1 54 Xe
144
+ 38 Sr 90 + 20 n1
55 Cs
144
+ 37 Rb 90 + 20 n1
It has been observed that during nuclear fission, the sum of the masses of the products
formed is slightly less than the masses of target species and bombarding neutrons. This loss
is known as mass defect. This loss in mass is converted to energy. Loss in lamu produces
931.48 Mev energy.
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Time Time
dN
– ∝N
dt
dN
or – = λN … (i)
dt
λ is known as decay constant or disintegration constant.
If dt = 1 second.
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dN
Then –=λ
N
Decay constant ( λ ) : Thus decay constant ( λ ) is equal to the fraction of radioactive
isotope disintegrating per second.
From equation (i)
dN
∫– N ∫
= λ dt
– log N = λt + C
where C is integration constant
when t = 0; N = No. (initial number of atoms)
–log N 0 = C
So –log N = λ t – log N 0
N0
λt = log
N
1 N
λ = ln 0
t N
2.303 N
λ= log 0
t N
All radioactive decay follows first order kinetics.
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as we have seen
– ln N = λt – ln N 0
N
ln = – λt
N0
N
= e – λt
N0
or N = No e – λt
Half life period (t1/ 2 ) : It is the time after which activity of a radioactive isotope reduces
to half of it’s initial value.
When t = t1/ 2 , N = N 0 / 2
2.303 N
λ= log 0
t N
2.303 N
t1/ 2 = log 0
λ N0 / 2
0.6932
t1/ 2 =
λ
Unit of λ = time –1
Specific activity : This is defined as activity per unit mass of the sample.
Average life (K) : The reciprocal of decay constant is defined as average life of radioactive
isotope.
1
Average life =
λ
1 t
K= = 1/ 2
λ 0.6932
K = 1.44 t1/ 2
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= λ 2 N 2 [λ 2 is decay constant of B]
at radio active equilibrium
Rate of formation of B = Rate of decay of B
But rate of formation of B = Rate of decay of A
So at equilibrium
λ1 N1 = λ 2 N 2
λ1 N 2 0.6932 / T1
= =
λ 2 N1 0.6932 / T2
λ1 N 2 T1
= =
λ 2 N1 T2
1
but λ=
K
λ1 K 2 N T
so = = 2 = 1
λ 2 K1 N1 T2
6 C14
→ 7 N14 + –1β0
Carbon dating is based upon the fact that radio carbon –14 is produced in the atmosphere
by the action of cosmic rays C14 is a β emitter with a half life of 5730 years. It’s rate of
formation has been constant so the atmosphere has an equilibrium concentration of C14
corresponding to nearly 16 disintegration per minute per gram of carbon. All living plants
and animals contains this equilibrium concentration but when a plant or animal dies no
further exchange between it and environment takes place and C14 content start decreasing
as a result of radio active decay. After 5730 years there will remain only 8 disintegration
per minute per gram of carbon. By measuring the activity of a fresh piece and the old piece,
the age of old piece may be determined.
2.303 N
λ= log 0
t N
2.303 λN 0
λ= log
t λN
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Illustration 13 :Radioactive decay is a first order process. Radioactive carbon wood sample
decays with a half life of 5770 years. What is the rate constant in (years)–1 for
the decay? What fraction would remain after 11540 years?
0.693 0.693
Solution : K= =
T1 / 2 5770
= 1.201 × 10–4 year–1
2.303 N
K= log 0
t Nt
2.303 N
1.201 × 10–4 = log 0
11540 Nt
N0
4.002 =
Nt
Nt 1
∴ (Remaining fraction) =
N0 4.002
EXERCISE 6 :
1. The bones of a prehistoric bison were found to have a 14C activity of 2.80 dis/min. g
carbon. Approximately how long ago did the animal live? (t1/2 = 5730 years) 14C activity
of fresh sample = 15.3 dis/min/gC.
2. Potassium contains 9.310 atom % 39K, having mas 38.9637 u; 0.0118 atom % 40K, which
has mass of 40.0 u and is radioactive with t1/2 = 1.3 × 109 y and 6.88 atom % 41K having a
mass of 40.96184u. Calculate the specific activity of naturally occurring potassium.
3. A mixture of 239Pu and 240Pu has a specific activity of 6 × 109 dis/s/g, The half lives of the
isotopes are 2.44 × 104y and 6.08 × 103y specific activity of naturally occurring
potassium.
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SECTION - I
SUBJECTIVE TYPE PROBLEMS
Problem 1: The half life of a chemical reaction at a particular concentration is 100 min. When
the concentration of the reactant is doubled, the half life becomes 50 min, then what is
the order of the reaction ?
n −1
(t1/ 2 )1 a 2
Solution : =
(t1/ 2 )2 a1
n −1
100 2
⇒ =
50 1
⇒ 2 = 2(n–1)
⇒ =n–1
⇒ n=2
Problem 2: An optically active drug has one chiral center and only dextrorotatory isomer is
effective. Moreover it becomes ineffective when its optical activity reduces to 60% of
the original in the equilibrium mixture at 27ºC and at one 127°C, its optical activity
reduces upto 80%. Then find out ∆H of the reaction assuming that the specific rotation
of the isomers remains constant during this temperature range. [log 3 = .477]
Solution : Let the dextrorotatory isomer A and laevoratatory is B
θ0 = initial observed rotation
θt = observed rotation at time t
A !!"
#!! B
t=0 θ0 0
⇒ θ0 – θ –θ
From question,
θ0 = 100, θt = 60
⇒ 60 = 100 – 2θ
∴ θ = 20 = θ0 – θ = 100 – 20
∴ At 27°C,r
[B] 20 1
Keq. = K1 = = =
[A] 80 4
Similarly, at 127°C.
[B] 10 1
Keq. = K2 = = =
[A] 90 9
since
1/ 4 ∆H 1 1
= −
1/ 9 R 300 400
2.30 log =
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9 ∆H 100
⇒ =
4 R 300 × 400
2.303 log
∆H 1
⇒ 2.303 [log 9 – log 4] = ×
R 1200
∆H 1
⇒ 2.303 [2 log 3 – 2 log 2] = ×
R 1200
⇒ 2.303 (2 × 0.477 – 2 × 0.301)
⇒ ∆H = 2.303 [0.954 – 0.602] × 8.314 × 1200
∆H = 8.188 kJ
Problem 3: A mixture of two substances X & Y produces Z simultaneously through parallel chain
reaction as under
I
X
Y
I
The rate constant for the first path is 1.2 × 10 –2 s –1 and of second path is
4 × 10–3 s–1. After 40 seconds, the mole percentage of Z is found to be 36. Find out
its mole-percentage after 60 seconds. Given that antilog (0.208) = 1.6 and Antilog
(0.303) = 2.50.
Solution : Let the total moles of mixture = 100
Initial moles of X = a
∴ Initial moles of Y = 100 – a
Out of “a” moles of X, p moles converts into C and q moles of Y converts into C
Now.
a–p, k1=1.2×10-2s-1
X
C p+q
Y
-3 -1
100–a–q, k2=4×10 s
p 1.2 × 10−2 3
Now, = =
q 4 × 10−3 1
⇒ p = 3q
Again, p + q = 36
4q = 36
∴ q=9
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∴ p = 27
a
Now k1 × 40 = 2.303 log
a − 27
1.2 × 10−2 × 40 a
= log
2.303 a − 27
a
⇒ 0.208 = log
a − 27
a
⇒ = 1.6
a − 27
⇒ a = 72
Now, for 60 seconds, let the amount of “X” converted into Z is p′ and the amount of Y
converted into Z is q′.
1.2 × 10−2 × 60 72
= log
2.303 72 − p'
72
⇒ 0.313 = log 72 − p′
72
2.050 = 72 − p′
p′ = 36.88
q′ = 12.29
∴ mole percentage of Z is = p′ + q′ = 49.17%
Problem 4: What is the amount of activation energy in kilo joules at 298 K for 10–3% molecule to
cross over the energy barrier? Given that, ln10–5 = –11.515.
Solution : Fraction of molecules crossing over the energy barrier = e− Ea / RT
10−3
⇒ = = e− Ea / RT
100
⇒ 10–5 = e− Ea / RT
Ea
⇒ – 11.515 = −
RT
⇒ Ea = 11.515 × 8.314 × 298 Joule
= 28.53 KJ
Problem 5 : The reaction given below, involving the gases is observed to be first order with rate
constant 7.48 × 10−3 sec−1.Calculate the time required for the total pressure in a
system containing A at an initial pressure of 0.1 atm to rise to 0.145 atm and also find
the total pressure after 100 sec.
2A(g) → 4B(g) + C(g)
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2
P′ = (0.145 − 0.1) =0.03 atm
3
2.303 Po
k = log
t Po − P '
2.303 0.1
t= −3
log
7.48 × 10 0.07
t = 47.7 sec
2.303 0.1
Also, k = log
t Po − P '
2.303 0.1
7.48 × 10−3= log
100 0.1 − P '
0.1 − P′ = 0.047
P′ = 0.053
3
Ptotal = 0.1 + (0.053) ≈ 0.180 atm.
2
Problem 6 : For the reaction :
C2H5I + OH− → C2H5OH + I−
the rate constant was found to have a value of 5.03 × 10−2 mol−1 dm3 s−1 at 289 K and
6.71 mol−1 dm3 s−1 at 333 K. What is the rate constant at 305 K.
Solution : k1 = 5.03 × 10−2 mol−1 dm3 s−1 at T1 = 289 K
k2 = 6.71 mol−1 dm3 s−1 at T2 = 333 K
k2 Ea 1 1
log k = 2.303R T − T
1 1 2
k2 88914 1 1
log −2
= −
5.03 × 10 2.303 × 8.314 298 305
On solving we get, k2 = 0.35 mol−1 dm3 s−1
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Problem 7 : The decomposition of Cl2O7 at 400 K in the gas phase to Cl2 and O2 is of I order. After
55 sec at 400 K, the pressure of Cl2O7 falls from 0.062 to 0.044 atm. Calculate :
(a) The rate constant.
(b) Pressure of Cl2O7 after 100 sec.
→
7
Solution : Cl2O7 Cl2 + O
2 2
Mole at t = 0 a 0 0
Mole at t = 55 sec. (a – x) x 7x/2
(a) Since Pressure of Cl2O7 is given and therefore,
a ∝ 0.062
(a – x) ∝ 0.044
2.303 0.062
∵ K= log10
t 0.044
K = 6.23 × 10–3 sec–1.
(b) Let at t = 100 sec, (a – x) ∝ P
2.303 0.062
∴6.23 × 10–3 = log10
100 P
∴ P = 0.033 atm.
Problem 8: A radioactive element A says to B “ I am half of what you were when you are one
fourth of what I was. Moreover I was 1.414 time than what you were. “ If the half life
of A is 8 days, what is the half life of B?
Solution : Let the initial number of nuclide of X be x0
Let the initial number of nuclide of Y be y0
Let the number of nuclide of X after time t be xt
Let the number of nuclide of Y after time t be yt
∴ xt = ½ y0; yt = ¼ x0
x0 = 1.414 y0
Now, xt = x0 e −λ1t = ½ y0 …(1)
yt = y0 e −λ2 t = ¼ x0 ….(2)
Dividing equation. (1) by (2)
x02 (λ 2 −λ1 )t
2= e
y 02
Since x0 = 2 y0
x02 = 2y02
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∴ 2 = 2e(λ 2 −λ1 )t
∴ e(λ 2 −λ1 )t = 1
Since t is not zero, hence λ2 = λ1. Therefore the half life of the other radioactive element is
also 8 days.
Problem 9 : On analysis a sample of Uranium was found to contain 0.277 g of 82Pb206 and 1.667 g
of 92U238. The half life period of 92U238 is 4.51×109 years. If all the lead were assumed
to have come from decay of 92U238, what is the age of the earth?
238
1.667
Solution : 92U = 1.667 g = mole
238
206
0.227
82Pb = 0.227g =
206
mole
0.277
∴ moles of U decayed =
206
1.667 0.277
∴ Total moles of Uranium = + , ie N0-
238 206
1.667
Also N for U238 =
238
1.667 0.277
+
2.803 N 0 2.303 × 4.51 × 10 9 238 206
∵ for U238 t = log = log 1.667
k N 0.693
238
∴ t = 1.143 × 109 yrs .
Problem 10 : An optically active compound A is hydrolysed by dilute acid to give
two optically compounds B and C according to the following chemical equation,
A + H2O → 2B + C. The angle of rotation after 40 minutes was observed to be
26° and that after completion of reaction was 10° at 27°C. Find the half - time of the
reaction assuming it to follow pseudo first order kinetics. The observed rotation per
mole of A,B and C are 60°, 50° and –80°. A plot of logarithm of rate constant of the
above reaction vs T–1 give straight line with intercept equal 15.046 on log K axis.
Calculate at what temperature half - time of the reaction will be 31.1 min.
Solution : A + H 2O → 2B + C
a excess 0 0
(a-x) const. x 2x
0 const. 2a a
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99370 1
∴ – 1.652 – 15.046 = ×
2.303 × 8.314 T
∴ T = 310.80 K
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SECTION - II
SINGLE CHOICE PROBLEMS
Problem 1: !!" nB with time is presented in the figure, the value of n
The progress of the reaction A #!!
is
(a) 2 (b) 3
(c) 4 (d) 5
B
0.6
Con. ol/litre
0.3
A
1 3 5 7
Time/hour
Solution : A !!"
#!! nB
t=0 0.06 0 (initial conc. in mol L–1)
At equi. 0.6 – x nx (conc. at equilibrium)
From the graph
0.6 – x = 0.3
Also from the graph
nx = 0.6
∴n=2
∴ (a)
Problem 2 : For the elementary reaction, 2NO + H2 → N2O + H-2O; the half life time is 19.2 sec at
820°C when partial pressure of NO and H2 are 600 mm of Hg and 10 mm of Hg respectively.
The value of half time at the same temperature when partial pressure of NO and H-2 are
600 mm of Hg and 20 mm of Hg respectively would be
(a) 19.2 sec (b) 10 sec
(c) 830 sec (d) 415 sec
Solution : According to Ostwald isolation method of order determination, the concentration terms of
reactants present in excess remain virtually unchanged and thus can be merged with the
rate constant. In this case, the rate of the reaction depends only on the concentration o f that
reactant which is not present in excess. The reaction is known to be pseudo first order.
The partial pressure of NO is very large in comparison to that of hydrogen. Thus, we may
consider the rate of reaction to be independent of PNO and hence reaction will follow the
rate law.
dp(N 2O)
= k ′PH 2 ; where k ′k(PNO ) 2 = Pseudo first order reaction rate constant.
dt
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Half-life time of first order reaction is independent of initial concentration. Hence the required
half-life time will be 19.2 sec.
∴ (a)
Problem 3 : Two reactions one of first order and other of second order have same values of rate constants
(k1 = k2) when concentration are expressed in mole dm–3. If the concentrations are expressed
in mole ml–1 the relation between their rate constants k′1 and k′2 will be
(a) k′1 = k′2 (b) k′2 × 103 = k′2
(c) k′2 × 10–3 = k′1 (d) k′1 = 10k′2
Solution : Since kα[a]1− n
For first order reaction,
k1α[a]1−1
k1α1
So k is constant and independent of unit of a, Therefore k1 = k′1
For second order reaction
1
k2 ∝
a
1 1
k2 ∝ = −3
a mole dm -3
a × 10 mole ml-1
1
k ′2 ∝ −1
a mole ml
∴ k 2 = k ′2 × 103 = k1′
∴ (c)
B
Problem 4 : For the first order reaction 3A → B
concentration varies with time as shown
in the adjacent graph. The half-life of the Conc.
reaction would be (In M) A
(a) 2 minutes
(b) 4 minutes
(c) 8 minutes 2 4 6 8
(d) 16 minutes Time (in minutes)
Solution : From graph it follows that at time 4 minute from the start of the reaction
[A] = [B]
3A → B
t=0 a
t = 4 min a – x x/3
x 3a
∴ a−x= ⇒x=
3 4
3a a
∴ a−x=a− =
4 4
i.e., in 4 minutes concentration of A has reduced to 25% of the initial value therefore,
t3/4 = 4 min. As t3/4 = 2t1/2 for a first order reaction, so half-life of this reaction = 2 min
∴ (a)
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Problem 5 : The inversion of cane sugar proceeds with half−life of 500 minute at pH 5 for any
concentration of sugar. However if pH = 6, the half−life changes to 50 minute. The rate law
expression for the sugar inversion can be written as
(a) r = K[sugar]2[H]6 (b) r = K[sugar]1[H]0
(c) r = K[sugar]0[H+]6 (d) r = K[sugar]0[H+]1
Solution : Since t1/2 does not depends upon the sugar concentration means it is first order respect to
sugar concentration. t1/2 ∝ [sugar]1.
t1/2 × an-1 = k
( t1/ 2 )1 [H + ]11− n
=
( t1/ 2 )2 [H + ]12− n
1− n
500 10−5
=
50 10−6
10 = (10)1-n
Hence n = 0
∴ (b)
Problem 6 : Two substances A and B are present such that [A0] = 4[B0] and half−life of A is 5 minute
and that of B is 15 minute. If they start decaying at the same time following first order
kinetics how much time later will the concentration of both of them would be same.
(a) 15 minute (b) 10 minute
(c) 5 minute (d) 12 minute
n
1 1
Solution : Amount of A left in n1 haves = [A 0 ]
2
n
1 2
Amount of B left n2 halves = [B0 ]
2
At the end, according to the question
[A 0 ] [B0 ]
= n
2n1 22
4 1
⇒ n1
= n , [[A 0 ] = 4[B0 ]]
2 22
2n1
∴ n2
= 4 ⇒ 2n1 − n 2 = (2) 2 ∴ n1 − n 2 = 2
2
∴ n 2 = (n1 − 2) …(1)
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n1 × t1/ 2(A) n1 × 5 n
∴ =1⇒ =1⇒ 1 = 3 …(2)
n 2 × t1/ 2(B) n 2 × 15 n2
R 2 K(0.4)(0.4) 2 1
= =
R1 (0.6)(0.8) 2 6
∴ (d)
Problem 8 : A first order reaction : A → Products and a second order reaction :
2R → Products both have half - time of 20 minutes when they are carried out taking 4
mole L–1 of their respective reactants. Number of mole per litre of A and R remaining
unreacted after 60 minutes from the short of the reaction, respectively will be.
(a) 1 and 0.5 (b) 0.5 and negligible
(c) 0.5 and 1 (d) 1 and 0.25
Solution : In the case of first order reaction t1/2 will remain constant independent of initial concentration
so.
20 min 2 mole L–1
4 mole L–1 20 min –1 20 min –1
→ → 1 mole L → 0.5 moile L .
That is, after 60 minutes 0.5 mole L–1 of A will be left unreacted.
In the case of second order reaction t1/2 is inversely proportional to initial concentration of
reactant i.e., t1/2 will go on doubling as concentration of reactant will go on getting half.
That is, t1/2 a will be constant, so.
20 min
4 mole L–1 –1 40 min –1
→ 2 mole L → 1 mole L .
That is, after 60 minutes, the concentration of R remaining unreacted will be 1 mole L–1.
Note that t1/2 a = 20 × 4 = 40 × 2 = 80 mole L–1 min, a constant.
∴ (b)
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Problem 9 : The thermal decomposition of acetaldehyde : CH3CHO → CH4 + CO, has rate constant
d[CH3CHOO]
of 1.8 × 10–3 mole–1/2L1/2 min–1 at a given temperature. How would - will
dt
change if concentration of acetaldehyde is doubled keeping the temperature constant?
(a) will increase by 2.828 times (b) will increase by 11.313 times
(c) will not change (d) will increase by 4 times
Solution : Unit of the rate constant mole –1/2L1/2.min1/2 suggests that the reaction obeys kinetics of 1.5
order.
Rate = k [CH3CHO]3/2
K II K C [O3 ]2
Rate =
[O 2 ]
∴ (b)
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SECTION - III
MULTIPLE CHOICE PROBLEMS
Problem 1: Arrhenius equation may be represented as
A Ea d ln k Ea
(a) ln = (b) =
k RT dt RT
Ea Ea k
(c) log A = log k + (d) log − =
2.303RT RT A
Solution : (a, c)
(a) is correct as explained below :
k k −Ea A Ea
k = Ae–Ea/RT ⇒ = e− Ea / RT ln = ⇒ ln =
A A RT k RT
d d d Ea
(b) is not correct (ln A) − (ln k) =
dT dt dt RT
d −Ea
− (ln k) = [ln A does not change with T]
dT RT 2
d Ea
⇒ (ln k) =
dT RT 2
(c) is correct. k = Ae–Ea/RT
Ea
ln k = ln A – Ea/RT ⇒ ln A = ln k + Ea/RT ⇒ log A = log k +
2.303RT
Hence (d) is not correct it follows from explanation of (a), (b) and (c).
Problem 2 : A positive catalyst
(a) increase the average kinetic energy of the reacting molecules
(b) decreases the activation energy
(c) alters the reaction mechanism
(d) increases collision frequency
Solution : (b, c)
(b) is correct because the catalyst lowers down the activation energy by altering the
mechanism.
(c) is correct because it provides alternative short-cut path or mechanism of the reaction.
(a) is not correct because K.E. ∝ T.
(d) is wrong because collision frequency is increased by temperature and pressure.
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[A 0 ] − [A] [A 0 ] − [A 0 ]e− kt
(a) is correct α = = = 1 − e− kt
[A 0 ] [A 0 ]
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3 14
(c) 1H
(d) 6C
Solution : (a, b)
n
(b) is correct ∵ p = 1 but still it is radioactive isotope or phosphorus and emits positron so as
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1 p + −1 e
→ 01 n
1 0
n/p ratio.
(c) β-particle emission leads to decrease in n/p ratio.
(d) α-particle emission leads to increase in n/p ratio but n/p should not be less than 1 in parent
nucleides.
n n
92 U
→ 234 + 24 He; for
238 238 234
e.g., 90Th 92 U is 1.58; for 90Th is 1.60.
p p
Problem 10 : Which of the following are used for measuring radioactivity?
(a) Gieger Muller counter (b) Wilson cloud chamber
(c) Scintillation counter (d) none of these
Solution : (a, b, c)
Geiger Muller Counter, Wilson Cloud Chamber, Scintillation counter are used for measuing
radioactivity ∴ (a), (b), (c) are correct.
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MISCELLANEOUS PROBLEMS
SECTION - IV
COMPREHENSION TYPE PROBLEMS
Write up – I
Nucleus is considered to resemble a liquid drop in which nucleons are present having very rich
density i.e. 130 trillion tonnes m–3 which is about trillion times the density of water. It has high
surface tension of about 1.24 × 1018 times, the surface tension of water. The high surface tension
keeps the nucleons together against the force of repulsion.
4 3
The nuclear volume = πr r α[A]1/ 3 , ∴ V ∝ |A|1/3 where A is mass number.
3
Problem 2 : The radius of nucleus of 12C is equal to
(a) 3.5 × 10–15 m (b) 4 × 10–15 m
(c) 5 × 10–15 m (d) 6.0 × 10–15 m
Solution : Ans. (a)
r = 1.4 × 10–15 (12)1/3 = 1.4 × 10–15 × 2.3 = 3.2 × 10–15 m
Problem 3 : Radius of nucleus is directly proportional to
(a) [A] 2 (b) [A] 1/3
(c) [A] 3 (d) [A]
Solution : Ans. (b)
r α [A]1/3 where ‘A’ is mass number
Write-up II
For a particular first order reaction at 27°C, the concentration of reactant is reduced to one half of
its initial value after 5000s. At 37°C, the concentration is halved after 1000s.
Problem 5 : What is the time required for the concentration to be reduced to one quarter of its value at
37°C?
(a) 1000 s (b) 500 s
(c) 2000 s (d) 1500 s
Solution : Ans. (c)
(T50)310 k = 1000 s
0.693
k2 (310 k) = = 6.93 × 10−4 s −1
1000
T75 = 2 × T50 for first order reaction, (when concentration is reduced to one quarter i.e.. 75%
reaction)
Hence, T75 (310 k) = 2000 s
Problem 6 : The activation energy of the reaction is :
(a) 124.46 kJ/mol (b) 650 kJ/mol
(c) 229.12 kJ/mol (d) 693.15 kJ/mol
Solution : Ans. (a)
2.303 RT1T2 k
Ea = log10 2 = 124.46 kJ/mol
T2 − T1 k1
4 Be + 2 He
→ 126 C + 01 n
9 4
(a) (p) Hydrogen bomb
(b) 24
12 Mg + 42 He
→ 27
14 Si + 0 n
1
(q) Radiolysis in Redox systems
(c) 2
1D + 31T
→ 24 He + 01 n + 17.6 MeV (r) Artificial transmutation
(d) BrO3− + 3I −
NaCl
→ Br − + I 2 + IO3− (s) Induced radio-activity
27
14 Si
→ 13 Al + +1 e
27 0
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Secondary stage : A+ + e– → A
or M + e – → M–
A+ + M– → Å + M
Here NaCl is the one which induces this reaction which is redox reaction.
ASSERTION-REASON TYPE PROBLEMS
The question given below consist of an ASSERTION and the REASON. Use the following key for the
appropriate answers
(a) If both Assertion and Reason are correct and Reason is the correct explanation for Assertion
(b) If both Assertion and Reason are correct and Reason is not the correct explanation for
Assertion
(c) If Assertion is correct but Reason is not correct.
(d) If Assertion is incorrect but Reason is correct.
8. Assertion : Photochemical reactions are zero order reactions.
Reason : Photochemical reactions involve free radicals and they are very fast reactions.
Solution : Photochemical reactions are extremely fast, therefore, lead to completion. Their rate is not
affected by concentration of reactant.
Ans. (a)
9. Assertion : 2FeCl3 + SnCl2 → 2FeCl2 + SnCl4 is a 3rd order reaction.
Reason : The rate constant for third order reaction has unit L2 mol–2 s–1.
Solution : rate = k [FeCl3]2 [SnCl2]1
rate = k[A]3 ⇒ mol L–1 s–1 = k [mol L–1]3
⇒ k = L2 mol–2 s–1
Ans. (b)
10.Assertion : β-particles are emitted by nucleus
Reason : In nucleus, 01 n
→ 11 p + 0
−1 e
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ASSIGNMENTS
SECTION - I
SUBJECTIVE QUESTIONS
LEVEL - I
1. The isomerism of cyclopropane to propene is of first order with k = 8.25 × 10–4 s–1 at 500°C. If
cyclopropane is enclosed in a heated tube at 500°C. What will be the minimum time needed to yield at
least 10% propene in resultant gas sample.
2. For a reaction, A → B + C, it was found that the end of 10 minutes from the start the total optical
rotation of the system ws 50° and when the reaction is complete, it was 100°. Assuming that only B
and C are optically active and dextro rotatory. What would be the rate constant of this first order
reaction.
3. At a given instant thee are 25% undecayed radioactive nuclei in a sample. After 10 seconds the
number of undecayed nuclei reduces to 12.5%. What is the time in which the number of undecayed
nuclei will further reduce to 6.25% of the reduced number.
4. Naturally occurring potassium consist of 0.01% K40, which has a half life of 1.28 × 109 yr. What would
be the activity of 1.0 g sample of KCl.
5. A catalyst lowers the activation energy of a reaction from 20 kJ mole–1 to 10 kJ mole–1. What is the
temperature at which the uncatalysed reaction will have the same rate as that of the catalysed at 27°C.
6. For the first order reaction A(g) → 2B(g) + C(g), the initial pressure is PA = 90 mm Hg, the pressure after
10 minutes is found to be 180 mm Hg. What is the rate constant of the reaction ?
7. The activity of a radioactive sample reduced from 20 Ci to 1.25 Ci in 2000 years. What are the half -
life of the sample and its decay constant.
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LEVEL - II
1. For the following reaction, the rate law has been determined to be
rate = k[A][B]2 with k = 2 × 10−6 mol−2 L2 sec−1
2A + B + C → A2B + C
For this reaction the initial conc of the various species.
[A] = 0.1 mol L−1; [B] = 0.2 mol L−1; [C] = 0.8 mol L−1. Determine the rate after 0.04 mol L−1 of A has
reacted.
2. For the reaction process A + B ——→ products, the rate is first order w.r.t A and second order w.r.t
B. If 1 mol each of A and B were introduced into a 1 L vessel, and the initial rate were 1 × 10-2 (mol/
L)sec-1. Calculate the rate when half the reactants have been turned into products.
3. 10g atoms of an α-active radioisotope are disintegrating in a sealed container. In one hour helium gas
collected at STP is 11.2 litre. Calculate the half-life of the radioisotope.
4. The gas phase decomposition of dimethyl ether follows first-order kinetics.
CH3OCH3(g)
→ CH 4(g) + H 2(g) + CO(g)
The reaction is carried out at constant volume in a container at 500°C and has a half-life of 14.5
minutes. Initially only dimethyl ether is present at a pressure of 0.40 atmosphere. What is the total
pressure of the system after 12 minutes? Assume ideal gas behaviour.
5. In the Arrhneius equation for a certain reaction, the value of A and Ea (activation energy) are 4 × 1013
s–1 and 98.6 kJ mol–1, respectively. If the reaction is of first order, at what temperature will its half-life
period be ten minutes?
6. The reaction 2NO(g) + 2H2 → N2(g) + 2H2O(g) has been studied at 904°C
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1
9. The half-life period for the reaction, N 2 O5
→ 2NO 2 + O 2 is 2.4 hours at 30°C. What time would
2
be required to reduce 5 × 1010 molecules of N2O5 to 108 molecules?
10. For a certain reaction, it takes 5 minutes for the initial concentration of 0.5 mole/L to become 0.25
mole/L and another 5 minutes to become 0.125 mole/L.What is the order and specific rate constant of
the reaction?
LEVEL - III
1. Two I order reactions having same reactant concentration proceed at 25°C at the same rate. The
temperature coefficient of the rate of the first reaction is 2 and that of second reaction is 3. Find the
also of the rates of these reactions at 75°C.
2. In a certain reaction Bm+ is getting converted to B(n+4)+ in solution. The rate constant of this reaction is
measured by titrating a volume of the solution with a reducing agent which reacts only with Bn+ and
B(n+4)+. In this process, it converts Bn+ to B(n–2)+ and B(n+4)+ to B(n-1)+. At t = 0, the volume of reagent
consumed is 25 mL and at t = 10 min, the volume used is 32 mL. Calculate the rate constant of the
conversion of Bn+ to B(n+4)+ assuming it to be a first order reaction.
3. For the reaction
2NO + H2 → N2O + H2O
dp
the value of − was found to be 1.50 torr s–1 for a pressure of 359 torr of NO and 0.25 torr s–1 for
dt
a pressure of 152 torr, the pressure of H2 being constant. On the other hand, when the pressure of NO
dp
was kept constant, − was 1.60 torr s–1 for a hydrogen pressure of 289 torr and 0.79 torr s–1 for a
dt
pressure of 1.47 torr. Determine the order of the reaction.
4. Calculate the value of rate constant and time required for solution to become optically inactive.
Time/min 0.0 7.2 36.8 46.0 68 ∞
Rotation of Polarized light /degree 24.1 21.4 12.4 10.0 5.5 –10.7
5. Decomposition of H2O2 is a first order reaction. A solution of H2O2 labelled as 20 volumes was left
open. Due to this some H2O-2 decomposed. To determine the new volume strength after 6 hours, 10 Ml
of this solution was diluted to 100 Ml. 10 Ml of this diluted solution was titrated against 25 Ml of 0.025
M KmnO4 acidified solution. Calculate the rate constant for decomposition of H2O2.
6. The inversion of the sugar proceeds with constant half life of 500 minute at Ph = 5 for any concentration
of sugar. However, if Ph = 6, the half life changes to 50 minute. Derive the rate law for inversion of
cane sugar.
7. Bi-cyclohexane was found to undergo two parallel first order rearrangements. At 730 K, the first order
rate constant for the formation of cyclohexane was measured as 1.26 × 10–4 s–1 and for the formation
of methyl cyclopentene the rate constant was 3.8 × 10–5s–1. What was the % distribution of the
rearrangement products.
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8. If a reaction A → Products, the concentrations of reactant A are C0, Ac0, a2C0, a3C0.. after time
interval 0, t, 2t, 3t, …. Where a is constant. Given 0 < a < 1. Show that the reaction is of I order. Also
calculate the reaction in K, a and t.
9. For a homogeneous gaseous phase reaction 2A → 3B + C, the initial pressure was P0 while pressure
at time ‘t’ was P. Find the pressure after time 2t. Assume first order reaction.
10. The decomposition of a compound A, at temperature T according to the equation.
2P(g)
→ 4Q(g ) + R (g ) + S(l)
is the first order reaction. After 30 minutes from the start of decomposition in a closed vessel, the total
pressure developed is found to be 317 mm Hg and after a long period of time the total pressure
observed to be 617 mm Hg. Calculate the total pressure of the vessel after 75 minutes, if volume of
liquid S is supposed to be negligible. Also calculate the time fraction t7/8.
Given: Vapour pressure of S(l) at temperature T = 32.5 mm Hg.
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SECTION - II
SINGLE CHOICE QUESTIONS
1. The instantaneous rate of disappearance of the MnO −4 ion in the following reaction is
4.56 × 10–3 Ms–1.
C0 C0 − C t
(a) k = (b) k =
2t t
C0 − C t C0
(c) k = ln (d) k = C
2t t
3. The rate expression for the reaction A(g) + B(g) → C(g) is rate = kC2A C1/B 2 . What changes in the initial
concentrations of A and B will cause the rate of reaction to increase by a factor of eight?
(a) CA × 2; CB × 2 (b) CA × 2; CB+ × 4
(c) CA × 1; CB × 4 (d) CA × 4; CB × 1
4. In an exothermic reaction X → Y, the activation energy is 100kJ mol–1 of X. The enthalpy of the
reaction is –140 kJ mol–1. The activation energy of the reverse reaction Y → X is
(a) 40 kJ mol–1 (b) 340 kJ mol–1
(c) 240 kJ mol–1 (d) 100 kJ mol–1
5. The rate constant, the activation energy and the pre-exponential factor of a chemical reaction at 25°C
are 8.0 × 10–4 s–1, 112 kJ mol–1 and 4 × 1015 s–1 respectively. The value of the rate constant as T → ∞
is
(a) 8 × 1016s–1 (b) 4 × 104s–1
(c) 4 × 1015s–1 (d) 112 × 1012s–1
6. Two first 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
7. Which of the following rate law has an overall order of 0.5 for the reactions involving substances x,y,z?
(a) Rate = k(Cx) (Cy) (Cz) (b) Rate = k (Cx)0.5 (Cy)0.5 (Cz)0.5
R ( Cx )( Cz )
o
8. The reaction A(g) + 2B(g) → C(g) + D(g) is an elementary process. In an experiment, the initial
partial pressure of A & B are PA = 0.60 and PB = 0.80 atm. When PC = 0.2 atm the rate of reaction
relative to the initial rate is
(a) 1/48 (b) 1/24
(c) 9/16 (d) 1/6
9. For a second order reaction of the type rate = k [A]2, the plot of [A]t versus t is linear with a
(a) positive slope and zero intercept
(b) positive slope and non zero intercept
(c) negative slope and zero intercept
(d) negative slope and non zero intercept
10. If concentration are measured in mole/lit and time in minutes, the unit for the rate constant of a 3rd
order reaction are
(a) mol lit–1 min–1 (b) lit2 mol–2min–1
(c) lit.mol–1 min–1 (d) min–1
11. Radioactivity is affected by
(a) Temperature (b) Pressure
(c) State of chemical combination (d) None
12. No. of β – particles emitted during the change a X b →c Yd is
a −d a −d
(a) (b) c + +b
4 2
b−d a −d
(c) c + −a (d) c + −b
2 2
13. For two atoms Z1 X
A1
and Z2 X A 2 where Z1 ≠ Z2 and A1 ≠ A 2 , A1 – 2Z1 = A2 – 2Z2, the species
would be called
(a) Isotonic (b) Isodiaphers
(c) Isoters (d) none
14. Which statement is true about N/P ratio
(a) It increases by β –emission (b) It increases by α –emission
(c) It increases by γ –emission (d) None of these
15. How many α and β particles should be eliminated so that an isodipher is formed
(a) n α , n β (b) n α , (n + 1) β
(c) n α (d) n β
16. 92 U + 0 n1 →92 U 236 → Pr oducts + x 0 n1 + 3.2 × 10−11 J . The energy released when 1 gm of
235
92 U
235
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17. At radioactive equilibrium the ratio between two atoms of radioactive elements A and B are 3×109 :
1. If t1/2 of A is 1010 years. What is t1/2 of B
(a) 30 years (b) 0.3 years
(c) 3.3 years (d) none
18. In the sequence of following nuclear reactions
−α −β −β − nα
92 X
238
→ Y → Z → L →84 M 218 the value of n is
(a) 3 (b) 4
(c) 5 (d) 6
1 4
19. The mass of 1H is 1.0076 amu and that of 2He is 4.0015 amu the energy released in the reaction
41 H1 →2 He 4 + 20 e1 is nearly
(a) 9 meV (b) 27 meV
(c) 36 meV (d) 54 meV
20. Co–60 has t1/2 = 5.3 years the time taken for 7/8 of the original sample of disintegrate will be
(a) 4.6 years (b) 9.2 years
(c) 10.6 years (d) 15.9 years
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SECTION - III
MULTIPLE CHOICE QUESTIONS
1. Molecularity of a reaction can’t be
(a) zero (b) (–) ve
(c) fractional (d) greater than 3 (genrally
st
2. For a 1 order reaction
(a) dx/dt = k(a–x)
2.302 a
(b) K = log
t a−x
2.302 a − x1
(c) t 2 − t1 = k
log
a − x2
10
(c) t 99% = 2t 90% (d) t 90% = t 50%
3
4. Conditions when K =a
(a) Ea = 0 (b) T = 0
(c) T = ∞ (d) all
5. Which are temperature independent?
(a) A (b) Ea
(c) R (d) K
6. Which is true statement
(a) lightest radioactive isotope is tritium
(b) nuclides having at no. > 82 are radioactive
(c) highest degree of radioactive is shown by uranium
(d) all of these are true
7. Primary emission is
(a) α –emission (b) β –emission
(c) γ –emission (d) all
8. A radioactive element present in VIII group of the periodic table. If it emits one α –particle, the
new position of the nuclide will be
(a) VI B (b) VIII
(c) VII B (d) IB
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MISCELLANEOUS QUESTIONS
SECTION - IV
COMPREHENSION TYPE QUESTIONS
Write-up I
In a parallel reaction reactant cobalt which is a transition metal decays by parallel pathways to form
2 products B and C.
B
β - emission (k1 )
58
27 Co
β + emission (k2 ) .
The ratio of concentration of [B] : [C] are 2 : 98 and the half life of Co is 22 years.
Write-up II
Ozone is prepared in laboratory by passing silent electric discharge through pure and dry oxygen in
an apparatus known as ozoniser. This conversion from oxygen to ozone is a reversible and endothermic
reaction. When oxygen is subjected to an ordinary electric discharge, most of the O3 produced will
get decomposed. When any insulating material such as glass, is inserted in the space between the
two electrodes and high current density is applied, silent electric discharge passes on between the
two electrodes. By this process no spark is produced and much less heat is generated, and as a
result the decomposition of the produced ozone is much retarded.
The decomposition of ozone is believed to occur by the following mechanism:
!!!
Kf
O3 #!! "
! O2 + O (fast step)
K b
O3 + O
K1
→ 2O2 (slow)
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7. Column – I Column – II
(a) Decomposition of H2O2 (p) 10t1/2
k 308 K
(b) k 298 K (q) 1st order
k2 E a T2 − T1
(d) t 99.9% (s) log k = 2.303 R T T
1 1 2
8. Column – I Column – II
(a) Rate of reaction (p) Can be fractional
(b) rate constant (q) Will be a whole number
(c) Order of reaction (r) Decreases with increase in concentration
(d) Molecularity (s) Increases with increase in temperature
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9. Assertion : In zero order reaction, the conc. vs time graph is a straight line.
Reason : The rate of change of conc. per unit time in zero order reaction remains constant.
10. Assertion : Photochemical reactions always occur in the presence of light.
Reason : Photochemical reactions do not require activation energy.
11. Assertion : Many of photochemical changes have positive sign of , yet they are spontaneous.
Reason : The activation energy in photochemical reactions is provided by light energy.
12. Assertion : The order of a reaction can have a fractional value.
Reason : The molecularity of a reaction can have a fractional value.
13. Assertion : For a zero order reaction, rate of reaction is independent of conc. of reactants.
Reason : For a zero order reaction, reaction proceeds at a constant rate which is equal to rate
constant of the reaction.
14. Assertion : To separate U-235 from the more abundant, all the uranium converted into UF6
Reason : UF6 is one of the few compounds that exist in gaseous state under ordinary conditions
which helps in separation of U-235 from U-238.
30 40
15. Assertion : Nucleide 13 Al
is less stable than 20 Ca
Reason : Nucleide having odd number of protons and neutrons are generally unstable.
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SECTION - V
(PROBLEMS ASKED IN IIT-JEE)
d [N 2 ] 1 d [H 2 ] 1 d [ NH3 ] d [N2 ] d [H 2 ] d [ NH 3 ]
(c) Rate = − = = (d) Rate = − =− =
dt 3 dt 2 dt dt dt dt
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8. In a first order reaction the concentration of reactant decreases from 800 mol/dm3 in 2×104 sec. The
rate constant of reaction in sec–1 is : (2003)
(a) 2 × 104 (b) 3.45 × 10–5
(c) 1.386 × 10à (d) 2 × 10–4
9. (A) follows first order reaction. (A) → product
Concentration of A, changes from 0.1 M to 0.025 M in 40 minutes. Find the rate of reaction of A when
concentration of A is 0.01 M: (2004)
(a) 3.47 × 10–4 M min –1 (b) 3.47 × 10–5 M min –1
(c) 1.73 × 10–4 M min –1 (d) 1.73 × 10–5 M min –1
10. Which of the following statement for order of reaction is not correct? (2005)
(a) Order can be determined experimentally
(b) Order of reaction is equal to sum of the power of concentration terms in differential rate law
(c) It is not affected with stoichiometric coefficient of the reactants
(d) Order can not be fractional
(a) 17
13 Al + 42 He →15
30
P (b) 6 C +1
12 1
H →14
7 N
(c) 30
→14
15 P
30
Si + e10 (d) 241
96 Am + 42 He →97
244
Bk + e10
2. Decrease in atomic number is observed during : (1988)
(a) alpha emission (b) beta emission
(c) positron emission (d) electron capture
SUBJECTIVE
1. The time required for 10% completion of a first order reaction at 298 K is equal to that required for
its 25% completion at 308 K. If the pre-exponential factor for the reaction is 3.56 × 109 s –1 , calculate
its rate constant at 318 K and also the energy of activation.
[IIT 1997]
2. The rate constant of a reaction is 1.5 × 107 sec –1 at 50°C and 4.5 × 107 sec –1 at 100°C. Evaluate the
Arrhenius parameters A and E a . [IIT 1998]
3. A first order reaction A → B requires activation energy of 70 kJ mol –1 . When a 20% solution of
A was kept at 25°C for 20 minute, 25% decomposition took place. What will be the per cent decomposition
in the same time in a 30% solution maintained at 40°C ? Assume that activiation energy remains
constant in this range of temperature. [IIT 1993]
4. A 1st order reaction is 50% complete in 30 minute at 27°C and in 10 minute at 47°C. Calculate the :
(a) Rate constant for reaction at 27°C and 47°C
(b) Energy of activation for the reaction.
(c) Energy of activation for the reverse reaction if heat of reaction is –50 kJ mol –1 . [IIT 1988]
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5. At 380°C, the half life period for the first order decomposition of H 2O 2 is 360 min. The energy of
activation of the reaction is 200 kJ mol –1 . Calculate the time required for 75% decomposition at
450°C. [IIT 1995]
6. A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in presence of a
catalyst at the same rate, the temperature required is 400 K. Calculate the activation energy of the
reaction if the catalyst lowers the activation energy barrier by 20 kJ mol –1 . [IIT 2000]
7. 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 –
T
Calculate :
(a) The energy of activation
(b) The rate constant at 500 K.
(c) At what temperature will its half life period be256 minute? [IIT 1997]
8. Two reactions (I) A → Products (II) B → Products follow first kinetics. The rate of the
reaction (I) is doubled when temperature is raised from 300 K to 310 K. The half life for this
reaction at 310 K is 30 minute. At the same temperature B decomposes twice as fast as A. If the
energy of activation for the reaction (II) is half that of reaction (I), calculate the rate constant of
reaction (II) at 300 K. [IIT 1992]
9. From the following data from the reaction between A and B,
Calculate :
(i) The order of reaction with respect to A and with respect to B.
(ii) The rate constant at 300 K.
(iii) The energy of activation.
(iv) The pre-exponential factor. [IIT 1994]
10. In the Arrhenius equation for a certain reaction, the values of A and E a (energy of activation) are
4 × 1013 sec –1 and 98.6 kJ mol –1 respectively. If the reaction is of first order, at what temperature will
its half life period be 10 minute? [IIT 1990]
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ANSWERS
EXERCISE - 1
4 d[O 2 ] d[NO] 4 d[H 2 O]
1. − = =
5 dt dt 6 dt
2. 1.2 × 10–2 atm min–1
3. (a) 5 × 10–4 mol litre–1sec–1 (b) 1.25 × 10–4 mol litre–1 sec–1
(c) 2.5 × 10–4 mol litre–1sec–1
EXERCISE - 2
1 2 0
1. (a) K[A] [B] [C] (b) r2 = 8r1
2. rate = K1[NO]2[Br2]
3. (a) 2O3(g) → 3O2(g);
(b) intermediate is O(g);
(c) first step is unimolecular second is bimolecular.
EXERCISE - 3
Do your self
EXERCISE - 4
1. (i) Greater the temperature dependence for reaction with larger value of Ea.
(ii) A = 6.73 × 1011 sec–1 K = 5.10 × 105sec–1 Ea = 92.011 Kj /mol
2. (a) 1.386 × 10–4s–1
(b) 2000s
(c) 124.46kJ mol
3. T = 282 K
EXERCISE - 5
1. 0.537
2. (a) 132 sec (b) 0.58 mol dm–3
(c) [A] = 0, [B] = 0.12 mol dm–3, [C] = 0.88 mol dm–3
EXERCISE - 6
1. 14,000 years
2. Specific activity = 30.69 dis.g–1s–1
239 240
3. Pu = 45.1%, Pu = 54.9%
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SECTION - I
(Subjective Questions)
LEVEL - I
LEVEL - II
LEVEL - III
(2P 0 − P)2
9. PT = 2P 0 −
P0
10. Pt = 268.11 mm Hg, t7/8 = 43.76 min
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SECTION - II
(Single Choice Questions)
1. (d) 2. (b)
3. (b) 4. (c)
5. (c) 6. (a)
7. (c) 8. (d)
9. (b) 10. (b)
11. (d) 12. (c)
13. (b) 14. (b)
15. (c) 16. (c)
17. (c) 18. (b)
19. (b) 20. (d)
SECTION - III
(Multiple Choice Questions)
1. (a, b, c, d) 2. (a, b, c, d)
3. (a, b, c, d) 4. (a, c)
5. (a, b, c) 6. (a, b)
7. (a, b) 8. (a, b, c)
9. (a, c) 10. (a, b, c, d)
SECTION - IV
(Comprehension Type Questions)
1. (a) 2. (c)
3. (d) 4. (a)
5. (b) 6. (a)
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SECTION - V
(Problems asked in IIT-JEE)
SUBJECTIVE
1. K318 = 9.22 × 10–4 sec–1
Ea = 18.3 kcal mol–1
2. Ea = 2.2 × 104 J mol–1
A = 5.42 × 1010
3. 67.21%
4. (a) K1 at 27°C = 2.31 × 10–2 min–1
K2 at 47°C = 6.93 × 10–2 min–1
(b) Ea = 43.85 kJ mol–1
(c) 93.85 kJ mol–1
5. 20.39 min 6. 100 kJ mol –1
7. 24.83 k cal mol–1, 2.35 × 10–5 sec–1; T = 513 K
8. 0.0327 min–1
9. (i) 2 and 1
(ii) 2.66 × 108 litre2 mol–2 sec –1
(iii) 55.33 kJ
(iv) 1.140 × 1018
10. 311.35 K
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