Chemical

Kinetics

Key Concepts
Moderate
INTRODUCTION TO KINETICS 2H2O2 h 2H2O + O2

Thermodynamics deals with the feasibility of the reaction but

kinetic deals with the rate of the reaction. [P]
Thermodynamics deals with the initial and final state of
the reactants and products but kinetics deal with the path by [R]
which reaction is taking place.
P.E.
? (kinetics)
Simple reaction P.E.
Complex reaction Those chemical reactions which
Simple reaction takes place in a single step are
R DH known as simple reaction.
P aA + bB Æ P R P
time
a b
r = K[A] [B] Reaction coordinate
CLASSIFICATION OF Complex
CHEMICAL REACTION Those chemical reactions which take in more than one step.
P.E.
Very fast Very Slow
I*
NaCl + AgNO3 Æ AgCl Ø+ NaNO3 1 25∞C
Fe + O 2 æææ Æ FeO
HCl + NaOH Æ NaCl + H2O 2 R P
Conc. [O]
Cellulose æææ
25∞C
Æ CO 2 + H 2O
[P] Reaction coordinate
Conc. aA + bB Æ P
r = k[A]m [B]n
[R]
[R] (m, n) π (a, b)
Time
Rate of reaction
[P] DC
(1) Average Rate:
Time Dt

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 Conc. Rate Rate
[P] 98°F
[P] t2
[R] t1
[P] t1
[R] t2 [R] O
O temperature
t1 t2 temperature (K)
Time (Biological Enzyme)

DC È[ R]t2 - [ R]t1 ˘ [ P]t2 - [ P]t1 At T Æ ; maximum rate

= -Í ˙= For majority of the reaction; on increasing temperature
Dt Î t2 - t1 ˚ t2 - t1
by 10°C rate of the reaction increases two to three times.
–Ve sign indicate decrease in concentration of reactant (4) Catalyst
moles
Units of reaction rate: or M/sec–1 P.E. (–) ve catalyst
- sec
Without catalyst
Conc. (+) ve catalyst

C R
P
O
Reaction
R
t1 Time Catalyst increases the rate of reaction
O T
(5) Solvent
Ê dc ˆ OC Solvent
ÁË ˜¯ =
dt t = t1 OT
Polar Non-Polar
In general, rate of reaction changes with time C6H6
Protic Aprotic n-C6H14
Conc. Conc. SN1 SN2
H2 O CH3
T¢ H C N (DMF)
[P] O¢ Time EtOH
O CH3

t1 Time C (6) Surface area

O
For reaction involving solid surface area,
Ê dc ˆ CO¢ rate μ surface Area
ÁË ˜¯ =
dt t = t1 O¢T ¢ (7) Radiation
25∞C
CH4 + Cl2 æææ
hv
Æ CH3 – Cl + H – Cl
Factors affecting rate of the reaction:
25∞C
(1) Nature of reactants CH4 + Cl2 æææ
Dark
Æ NO reaction

700∞C Rate Constant (K)/Velocity constant/Specific reaction

C (graphite) + O 2 æææÆ CO 2 K1 > K 2 \ r1 > r2
K 1 rate
700∞C Rate constant is defined as the rate of the reaction. When con-
C (diamond) + O 2 æææ
K
Æ CO 2
2 centration of each reactant is unity.
(2) Concentration or volume or pressure aA + bB h P
n P
aA(g) + bB(g) Æ P [ A] = A = A rate = K[A]m [B]n
V RT
If [A] = 1 M
Rate = K [ A] [ B]
m n
and [B] = 1 M
K then rate = K
= ( PA ) m ( PB ) n
( RT ) m + n Characteristic of Rate constant (K)
(3) Temperature Rate constant for any particular reaction is constant at con-
Rate of the reaction generally increases with the in- stant temperature. It does not change with concentration vol-
creases in temperature. ume, pressure, time, etc.

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 Chemical Kinetics 1.3

Catalyst increases rate constant ‘k’. Molecularity

K depends on temperature. For a single step reaction: Molecularity is defined as number
Ea
- RT of reactant molecules participating in balanced chemical re-
K = Ae action. Molecularity of reaction is generally 1 or 2. For few
K reaction it is also observed to be 3.
Molecularity cannot be more than 3 because probability
A
of more than 3 molecules colliding at the same instance is
almost zero.
Molecularity cannot be –ve, zero, or fraction.
Time For complex reaction : each step has its own molecularity
RhP
KT +10 If mechanism R h P* + Q*
Temperature Coefficient (m) = = 2 to 3
KT P* + Q* h I*
Higher the value of rate constant; more will be the rate of I* h P
the reaction
but overall molecularity has no significance.
Higher value of rate constant; suggest reactant is kineti-
For elementary reaction; molecularity and order are same.
cally unstable.
Molecularity of a single step reaction can be obtained by
Graphite at 700°C is kinetically unstable than diamond
reaction stoichiometry.
Units of rate const. (K)
Example (1) A h B
RhP or
Rate = K[R]m Order of reaction(m) A h B + C Molecularity = 1
Moles Ê mole ˆ
m Example (2) 2A h P
= KÁ ˜¯ or
- sec Ë
A+BhP
1- m
Ê moles ˆ 1 M 1- m or
K =Á ˜¯ ◊ =
Ë sec sec A h 1/2 P Molecularity =2
Example (3) 3A h P
Rate Law or
aA + bB h cC + dD A h 1/3 P
1 Ê d [ A] ˆ 1 Ê d [ B ] ˆ 1 Ê d [C ] ˆ or
Rate = Á- ˜ = Á- ˜ = Á+ ˜ 2A + B h P Molecularity = 3
a Ë dt ¯ b Ë dt ¯ c Ë dt ¯
Unimolecular: N2O5 h N2O3 + O2
1 Ê d [ B]ˆ
= Á+ ˜ = k[ A] [ B]
m n
Bimolecular: H2 + Cl2 h 2HCl
d Ë dt ¯
Tri/ter molecular: 2H2 + O2 h 2H2O
d [ A]
- Æ rate of disappearance of A. Order of the reaction
dt In the expression of rate law, order is defined as (coefficient)
d [C ] of active mass.
+ Æ rate of formation of C.
dt aA + bB h P
m Æ order w.r.t. A. Rate = K[A]m [B]n
n Æ order w.r.t. B. m = Order w.r.t. A
m + n Æ overall order of the reaction. n = Order w.r.t. B
(m + n) = overall order of reaction
Relation between different rate constants Order of any reaction can be obtained only by experimen-
d [ A] tal methods.
- = K ◊ a[ A]m [ B]m = K A [ A]m [ B]n
dt Order of reaction may have –ve, +ve, zero or fractional
d [ B] value.
- = K ◊ b[ A]m [ B]m = K B [ A]m [ B]n
dt Order of reaction is related with reaction mechanism.
d [C ] reaction mechanism may change with experiment condi-
+ = K ◊ c[ A]m [ B]m = KC [ A]m [ B]n
dt tion order may also change with reaction condition:
d [ D] SN1
+ = K ◊ d [ A]m [ B]m = K D [ A]m [ B]n H2O R Nu + X \ Rate = K[R–X]
–
dt R X + Nu(–)
SN2 R Nu + X– \ Rate = K[R–X] [Nu–]
K K K K (2°)
K= A= B = C = D DMF
a b c d

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 Zero order reaction K [ A]
A Æ P If [A] >> K¢ then, Rate =
[ A]
t=0 a —
t (a – x) x (2) Half-life of zero order reaction
A Æ P
- d [ A] + d [ P] (i)
Rate = = = K [ A]∞ t=0 100 –
dt dt t = 10 min 50 50
- d [ A] + d [ P] t = 15 min 25 75
=K [or] =K t = 17.5 min 12.5 87.5
dt dt
a- x f x t Form the above information, reaction is zero order re-
Ú - d [ A] = K Ú dt Ú dx = K Ú dt action.
1
0 0 0 0
We know t1/2 μ n-1
(a – x) – a = –Kt x = Kt (ii) a
(a – x) = –Kt + a n -1
(t1/2 ) I Ê aII ˆ
[A]t = –Kt + [A]0 (iii) =
(t1/2 ) II ÁË aI ˜¯
Half-life of zero order reaction n -1
x = Kt 10 Ê 50 ˆ 1- n
fi =Á ˜ =2=2
at t = t½ = t50% = when x = a/2 5 Ë 100 ¯
a fi n = 0.
t1/2 = (iv) (3) Zero order reaction is 100% completed.
2K
(4) For zero order reaction in the same time interval, equal
Ê 1 ˆ amount of reactants are consumed and concentration
ln t1/2 = ln a + ln Á
Ë 2 K ˜¯
(v)
of reactants at the same time intervals are in A.P. with
Time of completion for zero order reaction. C.D. –Kt.
x = Kt AhP
t=0 a
a
= 2 ¥ t1/2 or 2 ¥ t50%
t100% = t a – Kt
K 2t a – K(2t)
Few graphs related to zero order reaction 3t a – K(3t)
Conc.
x = Kt
Conc.
[A]t [P] Examples:
[A]0
(1) Photochemical reaction
hv
H2 + Cl2 ææÆ 2HCl
Time (2) Reaction taking place at the solid catalyst surface.
Time
Ni
C2H2 + H2 ææÆ C2H6
Conc. Rate
AÆ P First order reaction
–K A h P
K t=0 aM —
K t (a – x) x
t50% t100% Time Time - d [ A] + d [ P]
Rate = = = K [ A]1 (i)
dt dt
a- x t
lnt1/2 - d [ A]
t1/2
45° Ú [ A]
= K Ú dt
Slop = ½ K a 0

fi ln(a – x) – ln a = –Kt
ln(1/2K)
fi ln(a – x) = –Kt + ln a (ii)
lna
a a-x
ln = - Kt fi a - x = a e - Kt
Characteristics of zero order reaction a
(1) Rate is independent of concentration and does not a
changes as the reaction progress. ln = Kt (iii)
a-x
K [ A]
Rate = 2.303 a
[ A] + K ¢ K= log10 (iv)
t a- x

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 Chemical Kinetics 1.5

Few graph related to first order reaction Half-life of first order reaction
Conc. [A]0 Conc. a = [A] 2.303 a
0 K= log
[P]t t a-x
[P]
2.303 a 2.303
K= log fiK= log 2
[A] t1/2 a - a /2 t1/2

Time Time 0.693 ln 2 1

fi t1/2 = = or t1/2 μ 1-1
K K a
(a – x) = ae–kt
x = a(1 – e–kt) t1/2
Degree of dissociation of first order reaction
A h P a
a — 1.0 0.693/K
a–x
a(1 – x/a)
x a
a= = 1 - e - kt A h P
a
t t=0 100 —
t = 10 min 50 50
ln[A] t = 20 min 25 75
Slope = –K t = 30 min 12.5 87.5
ln[A]0
Characteristic of first order reaction
(1) In first order reaction, in equal time interval, same frac-
time tion of reactants are consumed and concentration of re-
actants at same time interval are in GP with a common
log[A]t ratio e–Kt.
A h P
Slope = –K/2.303 t=0 a
log[A]0 t ae–Kt
2t ae–K(2t)
time 3t ae–K(3t)
Since [A]t = [A]0 e–Kt
ln a/a-x (2) Rate μ [A]t
1 0.693
Slope = K (3) t1/2 μ 1-1
and t1/2 =
a K
Examples of first order reaction
time H+
(1) CH3COOEt + H2O ææÆ CH3COOH + EtOH
log a/a-x (2) 2H2O2 h 2H2O + O2
(3) All nuclear reaction
Slope = K/2.303 (4) Decomposition of N2O5
Second order reaction
Case I: When concentration of both reactants are same
time
A h P
t=0 a –
Rate
t=1 a–x x
x
dx 1 È 1 1 ˘
(a - x) - n =
dt Ú0
or -
(n - 1) ÍÎ (a - x) n -1 a n -1 ˙˚
time x t
dx -2
Rate = K[A]t = K[A]0 e –[Kt]
dt
= K (a - x) 2 So Ú (a - x) dx = Ú K dt
0 0

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 1 1 1 1 Eq. (2) – (1) = Eq. (3) – (2)
fi Kt = - = -
a - x a [ A]t [ A]0 1 1
= Kt = -
Half-life of second order reaction [ A]2t [ A]t
1 Examples of second order reaction
t1/2 =
K ◊a (1) Hydrolysis of ester in basic medium
(2) Decomposition of actatdehyde
Graphical representation of second order reaction CH3CHO h CH4 + CO

Rate Rate = K[A]2 Case II: When concentration of both reactants are
Conc. AÆP different
A + B Æ P
t=0 a b –
t=t a–x b–x x
[A]
dx
Time Time = K (a - x)(b - x)
dt
x t
dx
Ú (a - x)(b - x) = K Ú dt
1/[A]t
Slope = K 0 0
t1/2 x
1 È (a - x) - (b - x) ˘
(a - b) Ú0 ÍÎ (a - x)(b - x) ˙˚
fi dx = K (t - 0)
Slope = 1/K
1/[A]0
1 È ˘
x x
1 1
time t 1/a fi ÍÚ dx - Ú dx ˙ = Kt
since a 1– x = Kt +
1 1 1
Since t1/2 = K ¥ a (a - b) ÍÎ 0 (b - x) 0
(a - x) ˙˚
a
1 È b a ˘
fi ln - ln = Kt
ln t1/2 (a - b) ÍÎ b - x a - x ˙˚
45°
1 È b (a - x) ˘
fi ln ◊ = Kt
(a - b) ÎÍ (b - x) a ˚˙
ln(1/K)

Special case
ln a
If concentration of A is too greater than B.
ln t1/2 = ln(1/K) + ln(1/a) [A] >> [B]
ln t1/2 = ln(1/K) – ln a a–x a
Characteristics of second order reaction: 1 b
K ¢ = ln 1st order w.r.t. [B]
A h P t b-x
(1) Rate = K[A]2
Rate = K[A]0[B]1
1
(2) t1/2 μ 2 -1 H+
a H2O + CH3COOC2H5 ææÆ EtOH + CH3COOH
A h P (excess) Rate = K¢[ester]1 (Pseudo unimolecular)
t=0 100 –
t = 10 50 50 Nth order
t = 30 25 75 A h P
t = 70 12.5 87.5 t=0 a –
(3) At equal time interval, concentration of reactants are in t=t a–x x
H.P. dx
1 1 = K (a - x) n
K (t ) = - (2) dt
[ A]t [ A]0 x
dx
t

1 1 Ú (a - x)n = K Ú dt
K (2t ) = - (1) 0 0
[ A]2t [ A]0 1 È 1 1 ˘
Kt = Í n -1
- n -1 ˙
K (3t ) =
1
-
1 (3) (n - 1) Î (a - x) a ˚
[ A]3t [ A]0

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 Chemical Kinetics 1.7

Half-life of nth order reaction (2) Using integrated rate equation (Hit and Trial)
1 È 1 1 ˘ A Æ P
Kt1/2 = -
(n - 1) ÍÎ (a - a /2) n -1 a n -1 ˙˚ t=0 a –
t1 a – x1 x1
1 2 n -1 - 1 C t2 a – x2 x2
t1/2 = = n -1
K (n - 1) a n -1 a : :
: :
2 n -1 1
C= for n π 1\ t1/2 μ n -1 Zero order reaction
K (n - 1) a x x x x
K= fiK= 1 = 2 = 3
Graph related to nth order reaction t t1 t2 t3
1 1 2.303 a
(i) n -1
= (n - 1) Kt + K= log if K1 = K2 = K3 … first order
[ A]t [ A]0n -1 t a-x
1 1È 1 1 ˘ if K = K = K … second order
K= Í -
t Î a - x a ˙˚
1 2 3
[A]tn–1 Slope = (n – 1)K
(3) Graphical method using concentration
1
[A0]n–1 [A] ln[A]
time
1
(ii) t1/2 = C ◊ n -1
a O I

t1/2 t t

1/[A]t 1/[A]n – 1
2n–1 – 1
Slope = C =
K(n – 1)
II nth order
1
an–1 t t
(iii) ln t1/2 = ln C – (n – 1) ln a
(4) Graphical method using half-life
ln t1/2
Slope = 1 – n ln t1/2

ln C Slope = 1 – n
ln a
ln a
Prediction of order of the reaction
(1) Initial rate method or different method (5) Half-life method
For nth order reaction:
A+BhP
dx C
Rate = = K [ A]m [ B]n t1/2 =
dt a n -1
n -1
Exp. No. [A]0 [B]0 Initial Rate (M sec–1) t1 Ê a2 ˆ
=
1. x y z t2 ÁË a1 ˜¯
2. 2x y 4z t1
ln
t2 ln t1 - ln t2
3. 2x 2y 8z = n -1fi n =1+
ln
a2 ln a2 - ln a1
4. p q x
a1
z = K(x)m (y)n (i)
Concentration terms replaced by other terms in first
m n
4z = K(2x) (y) (ii) order integrated equation.
8z = K(2x)m (2y)n (iii) A ææææ
ÆP
Ist order

m = 2, n = 1 t=0 aM –
Rate = K[A2][B] t=t a–x x

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 a [ A]0 (n A )0 (WA )0 (No. of A) at t = 0 V0 μ H+ (i)
= = = =
a - x [ A]t (n A )t (WA )t (No. of A)at t = t Vt μ H + + x (ii)
( PA )0 V μ H+ + a (iii)
= for gas since P μ n (If V and T const.)
( PA )t V – V0 μ a (iv)
V – Vt μ a – x (v)
(1) Concentration term replaced by partial pressure
2.303 È a V - V0 ˘
A(g) Æ B(g) + C(g) K= log Í =
t Î a - x V - Vt ˙˚
t=0 P0 – –
t=t P0 – p p p (4) Inversion of cone sugar
PT = (P0 – p) + p + p optical rot. (+ r10 ) + r20 - r30
PT = P0 + p
C12H22O11 + H2O h C6H12O6 + C6H12O6
p = PT – P0
(G) (F)
\ P° – p = P0 – (PT – P0) = 2P0 – PT
t=0 a – – –
P0 μ a and P0 – P μ (a – x)
t=t a–x – x x
2.303 P0 tÆ – – a a
K= log
t 2 P0 - PT | r20 | < | r30 |
a P0 P0 r 0 = ar10
= = (i)
a - x P0 - p 2 P0 - PT
r = (a -
t
x)r10 + xr20 - xr30 (ii)
(2) Concentration term replaced by volume of reagent
used in titration r = ar20 - ar30 (iii)
Stdandard KMnO4 From (i) and (ii); (i) and (iii)
V0 V0 μ a -r t t + r 0 r0 - r
Vt μ a – x = x and =a
r10 - r20 + r30 r10 - r20 + r30
rt - r
a-x=
r10 - r20+ r30
Vml sample
a r -r 0
H2O2 =
a - x rt - r
1st order
2H 2O 2 ææææ Æ 2H 2O + O 2
2.303 r0 - r
t=0 a – k= log t
t=t a–x x t r -r
2.303 V0
K= log Parallel Reaction
t Vt
K1 K1 B
A B
V0 Æ Vol. of KMnO4 used in titration against V ml
OR A K2
sample of Solution of H2O2 at t = 0. A
K2
C C
(3) Hydrolysis of ester in acidic medium
H+ - d [ A]
CH3COOC2H5 + H2O ææÆ CH3COOH + EtOH Rate of decomposition of ‘A’, = K1[A] + K2[A]
a – – – dt
= [K1 + K2][A]
a–x – x x
1 [ A]
– – a a K1 + K 2 = ln 0
t [ A]t
[ A]t = [ A]o ◊ e -[ K1 + K 2 ] ¥ t
d [ B]
Std. NaOH Rate of formation of ‘B’= = K1[ A]
V0 dt
d [C ]
Rate of formation of ‘C’= = K 2 [ A]
dt
d [ B] K1 [ B] K1
V m1 = = fi =
d [C ] K 2 [C ] K 2

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 Chemical Kinetics 1.9

K1 - K1[ A]0
% yield of B = ¥ 100 at t = 0, [B] = 0 fi C =
K1 + K 2 K 2 - K1
Concentration of [B] at any time
K2
% yield of C = ¥ 100 K1[ A]0 e( K 2 - K1 )t
K1 + K 2 e K2t [ B ] =
K [ A]
- 1 0
K 2 - K1 K 2 - K1
[A]0 = [A]t + [B]t + [C]t
K1[ A0 ] - K1t
eg: [ B] = [e - e - K 2t ]
K1
K 2 - K1
K1 2B or A 2B
d [ B] K1[ A]0
A K2 A
K2
3C = [- K1e - K1t + K 2e - K 2t ] = 0
3C dt K 2 - K1
K1 and K2 are dissociation constants of A fi K1e- K1t = K 2 e- K 2t
K
-
d [ A]
= [ K1 + K 2 ][ A] e( K 2 - K1 )t = 2
dt K1
[ B]t [C ]t 1 K
[ A0 ] = [ A]t + + fi tmax = ln 2
2 3 K 2 - K1 K1
d [ B] If K2 >> K1, then concentration of [B] is very small and
= 2 K1[ A] = K B [ A]
dt practically becomes constant.
dC d [ B]
= 3K 2 [ A] = 0 fi K1[ A] - K 2 [ B] = 0
dt dt
[ B] 2 K1 2 K1 K
= and % B = ¥ 100 fi [ B] = 1 [ A]
[C ] 3K 2 2 K1 + 3K 2 K2
3K 2 Reversible reaction
%C = ¥ 100 Kf
2 K1 + 3K 2 H 2 + I2 2HI
Kb
Reaction in series
K K
r = K f [H 2 ][I 2 ] - Kb [HI]2
A ææ
1
Æ B ææÆ
2
C
1 d [HI]
- d [ A] r=
Rate of decomposition of A = = K1[ A] 2 dt
dt d [HI]
Rate of formation of B = K1[A] – K2[B] = 2[ K f [H 2 ][I 2 ] - Kb [HI]2 ]
dt
Rate of formation of C = K2[B]
d [H 2 ] d [I 2 ] d [HI]
r= = =
dt dt 2dt
[Conc]
C Kinetics for reversible reaction
When I order opposed by I order
Kf
B A B
A Kb
t
t=0 a –
dB dB
= K1[ A] - K 2 [ B] fi + K 2 [ B] = K1[ A]0 e- K1t t=t a–x x
dt dt
at equilibrium a – xe xe
On multiplying by e K2t on both sides d [ A] - d [a - x] dx
d [ B] - = =
e K2t ◊ + K 2e K2t [ B] = K1[ A]0 e( K2 - K1 )t dt dt dt
dt dx
= K f (a - x) - Kb ( x)
d [e K2t [ B]] dt
= K1[ A]0 e( K2 - K1 )t
dt dx
at equilibrium =0
d [e K 2t [ B]] = K1[ A]0 e( K 2 - K1 )t ◊ dt dt
On integration Kf(a – xe) = Kbxe
K1 ◊ [ A]0 ( K 2 - K1 )t K f (a - xe )
e K2t [ B] = e +C Kb = (i)
K 2 - K1 xe

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 1.10

Kbxe = Kfa – Kfxe Activation energy (Ea)

(Kf + Kb)xe = Kfa It is the extra amount of energy required by reactant mol-
ecules to reach up to the threshold energy.
Kf ◊a
K f + Kb = (ii) Activated complex
xe Ethres.
Ea
From Eq. (i), E
K f (a - xe ) ◊ x EP
dx DH
= K f (a - x) - ER
dt xe
dx K f Reaction Coordinate Æ
= [axe - xxe - ax + xxe ]
dt xe Ea = Ethreshold – ER
dx È K f ˘ = Eactivated complex – ER
=Í a ˙ ( xe - x)
dt Î xe ˚
(b) Orientation Barrier
dx In order to have effective collisions, the reactant molecules
= ( K f + Kb )( xe - x)
dt must collide in the proper direction.
On integration, Factor affecting rate of reaction
dx (i) Physical state
Ú ( xe - x) = ( K f + Kb )Ú dt Solid < Liquid < gas
(ii) Particle size
–ln(xe – x) = (Kf + kb)t + C
Smaller is the size if particle, more will be the rate of reaction
at t = 0; C = –ln xe because effective surface area increases.
–ln(xe – x) = (Kf + Kb) t –ln xe (iii) Temperature
1 xe For both endo- and exo-thermic reactions, rate of reaction
(K f + K b ) = ln increased on increasing the temperature.
t (xe - x )
On increasing the temperature by 10°C generally rate of
Arrhenius collision theory reaction becomes 2 to 3 times.
1. This theory is mainly applied to bimolecular collision. Rate = z ¥ e–Ea/RT
2. When reactant molecules collide among themselves zμ T
then, only they can convert themselves into product if
Effective collision occur. On increasing the temperature by 10°C, rate of reaction
3. Collision frequency is generally very high but number changes mainly because of fraction of effective collisions,
of effective collision or active molecules are compara- i.e., e–Ea/RT which becomes almost 2 to 3 times.
tively low. Temperature coefficient (m)
4. For any collision to be effective, there are two barriers. It is the ratio of two rates when temperature is increased by
(a) Energy barriers 10°C.
In order to have effective collisions, reactant molecules must R K
possess some minimum amount of energy known as thresh- m = t +10∞C = t +10∞C = 2 to 3.
Rt ∞C K t ∞C
old energy. DT
R2 K 2
= = ( m ) 10
Fraction R1 K1
of molecules
Effect of temperature on rate constant (K)
A/C to Arrhenius equation;
Ethreshold K = Ae–Ea/RT
Energy Æ
A Æ Arrhenius constant or pre-exponential factor or frequen-
Shaded area represents the fraction of active molecule cy factor.
which are having energy ≥ Ethreshold Ea
f = e–Ea/RT [fraction of active molecules] ln K = ln A -
RT
Ea Æ activation energy Ea
log K = log A -
R Æ Gas constant 2.303 RT
T Æ temperature

IIT JEE PC-V2_01.indd 10 5/13/2017 10:25:59 AM

 Chemical Kinetics 1.11

For example manufacture of NH3 by Haber’s process:

Fe(S)
+ve catalyst N2(g) + 3H2(g) æææ Æ 2NH3(g)
Energy Ea Ea > Ea¢ (3) Auto Catalysts:
Ea¢
In these reactions, one of the products formed act as a
catalyst during the reaction.
H + (aq)
Reaction Coordinate Æ
CH3COOC2H5(aq.) + H2O ææææ Æ
CH3COOH(aq.) + C2H5OH(aq.)
Ea (autocatalyst)
log K 2 = log A -
2.303 RT2 Photochemical reactions
Ea These are reactions which occur in presence of light and ra-
log K1 = log A - diation.
2.303 RT1
hv
For example H 2 + Cl2 ææÆ 2HCl
K2 Ea È 1 1˘
log = Í - ˙ These reactions follow zero order kinetics.
K1 2.303R Î T1 T2 ˚
rμI I = intensity of light
r=f◊I
Note: f = quantum efficiency or quantum yield.
1. As the activation energy of reaction increases, rate of Number of moles of reactant reacted
reaction decreases. f=
Number of moles of photon absorbed
2. For two different reactions:
Ea1 > Ea2 Reaction mechanism
DT fi identical (T1 = T2) In order to find the rate expression from the given reaction
mechanism, there are two methods:
Ê K2 ˆ Ê K2 ˆ
fi ÁË K ˜¯ > ÁË K ˜¯ (1) R.D.S. method (Rate determining step method)
1 1 1 2 (a) Select the R.D.S. from reaction mechanism which
is slowest step.
(b) Write the rate expression from the R.D.S. taking it
Catalyst
as elementary.
Positive catalyst speed up the reaction by providing alternat-
(c) If there is any intermediate then, remove it.
ing path of both for the reaction. In which energy of activated
For example,
complex is lesser, so activation energy is lesser. Hence, rate
Ex (1) Reaction: 2NO2 + F2 h 2NO2F
of reaction increases.
Mechanism:
K
+ve catalyst
NO2 + F2 ææ
1
Æ NO2F + F; (slow)
K
Energy Ea
Ea¢
Ea > Ea¢ F + NO2 ææÆ 2
NO2F; (fast)
r = K1[NO2][F2]
(2) Reaction: 2O3 h 3O2
Reaction Coordinate Æ Mechanism:
Negative catalyst or inhibitor decrease the rate of reaction O3 KC
O2 + O; (fast)
by providing an alternating path in which activation energy
K
increases. O3 + O ææÆ 2O 2 ; (slow)
Types of catalysis r = K[O3][O] (i)
(1) Homogenous catalysis: [O 2 ][O]
When reactants and catalysts are present in the same KC =
[O3 ]
phase.
here (O) is intermediate.
For example by lead chamber process
K [O ]
2SO2(g) + O2(g) æææÆ 2SO3(g)
NO(g) \ [O] = C 3
[O 2 ]
(2) Heterogeneous catalysis: From (i)
When reactants and catalyst are present in different phase.
For example Æ manufacture of H2SO4 by contact pro- [O3 ]2
r = K ◊ KC
cess [O 2 ]
V O (s)
2SO2(g) + O2(g) ææææ
2 5
Æ 2SO3(g) r = K ◊ KC [O3 ]2 [O 2 ]-1

IIT JEE PC-V2_01.indd 11 5/13/2017 10:26:00 AM

 1.12

(2) Steady state approximation method Velocity: a < b < g

This method is based on the fact that net rate of forma- Penetration power: a<b<g
tion of intermediate is zero. Ionisation power: a>b>g
1 - d [NO 2 ] Radioactive disintegration
r= ¥
2 dt All radioactive decay follow first order reaction:
- d [NO 2 ] Rate of disintegration or activity (A)
= K1[NO 2 ][F2 ] + K 2 [NO 2 ][F]
dt - dN
= μN
According to steady state approximation method. dt
d [F] Where N = (Number of radioactive nuclei left at given time)
= 0 = K1 ◊ [NO 2 ] ◊ [F2 ] - K 2 [NO 2 ] ◊ [F] - dN
dt = lN
fi K1 ◊ [NO2] ◊ [F2] = K2[NO2] ◊ [F] dt
N = N0e–lt
d [NO 2 ]
fi - = 2 K1[NO 2 ] ◊ [F2 ] N = Number of radioactive nuclei taken initially
dt
1 d [NO 2 ]
fi r= ¥ = K1[NO 2 ] ◊ [F2 ] N
2 dt
Reation of fractional order:
(i) H2 + Br2 h 2HBr Rate = K [H2] [Br2]1/2
(ii) COCl2 h CO + Cl2 Rate = K [COCl2]3/2 t
(iii) CO + Cl2 h COCl2 Rate = K [CO]2 [Cl2]1/2 1 N 1 A
l = ln 0 l = ln 0
(iv) Para H2 h Ortho H2 Rate = K [PH2 ] 3/2 t N t A
n
(v) Thermal decomposition of acetaldehyde 1 m Ê 1ˆ
l = ln 0 and Nt = N o Á ˜
Rate = K [CH3CHO]3/2 t m Ë 2¯
m0 : mass of nuclei initially n = Number of half-lite used
RADIOACTIVITY Nt m È1˘
n
\ = =
N 0 m0 ÍÎ 2 ˙˚
It is a spontaneous nuclear phenomena in which certain ra-
Half-life period (t1/2):
diations like a, b, g are emitted by the nuclei of radioactive
0.693
substances. t1/2 =
Radioactivity is independent of physical conditions like l
temperature, pressure etc. ttotal = n ¥ t1/2
a-rays Average Life: (tavg.)
These consist of helium nuclei (He+2). Due to each a-particle 1 t
decay, atomic mass number decreases by 4 whereas atomic tavg. = = 1/2
l 0.693
number decreases by 2. = 1.44 ¥ t1/2
A- 4
A
Z X ææ
Æ Y +a N = N 0 e - lt
Z -2

1
b-rays t = tavg =
These are composed of electrons. l
N0
–1e fi A = 0, Z = –1
0
at N= = 0.37 N 0
e
0 n ææ
Æ 1P1 + -1e0
1
It is time in which 37% of the initial radioactive nuclei
remain, i.e., 63% decay.
During the b-decay, there is no change in mass number but
atomic number increases by 1 due to the conversion of neu- Units of activity
tron into proton and electron. SI units: Disintegration per second (dps) or Becquerel (Bq)
g-rays Other units:
These are electro-magnetic radiation. Due to their emission, Curie (Ci) fi 1 Ci = 3.7 ¥ 1010 dps
there is no change in mass number and atomic number de- Rutherford (Rd) fi 1 Rd = 106 dps
creases the energy level in nucleus. Specific activity
It is the activity of 1 g radioactive substance.

IIT JEE PC-V2_01.indd 12 5/13/2017 10:26:01 AM

 Chemical Kinetics 1.13

Definitions (1) Up to Z = 20; n/p ratio is 1 for most stable nuclei but
(1) Isotopes : Same atomic number but different mass number above Z = 20, n/p ratio for stable nuclei increases because
(2) Isobars : Same mass number but different atomic number as the number of proton increases, electrostatic repulsion be-
(3) Isotopes : Same number of neutrons : [A – Z] Æ constant tween these increases. In order to overcome these repulsive
(4) Isodiaphers : (n – p) fi same OR forces, neutrons increase number.
Above Z = 83; there is no stable nuclei.
(A – 2Z) fi same
Among the stable nuclei, n/p ratio is maximum for Bi bis-
Radioactive disintegration series muith (1.5).
There are four natural disintegration series. Those nuclei which have number of neutron protons equal
Series Name Starting Stable End to magic number Æ 2, 8, 20, 28, 50, 82, 126 are more stable.
Element Product Maximum number of stable nuclei have even number of
neutrons and even number of protons whereas very few sta-
4n Thorium series Th – 232 Pb – 208 ble nuclei have odd noumber of neutron and proton.
4n + 1 Neptunium series Np – 237 Bi – 209 Favourable condition for disintegration
4n + 2 Uranium series U – 238 Pb – 206
Type of Favourable Effect
4n + 3 Actinium series U – 235 Pb – 207 decay condition
Application of radioactivity n
Age determination of minerals, rocks or the earth for age 1. a-decay Z > 83 ≠
p
determination, minerals or rock sample is analysed for the
amount of radioactive substance and its stable end product. for (heavy un-
92 U
238
ææ
Æ 90Th 234 + 24a
When age of the mineral can be obtained from the formula. stable nuclei
1 a n
l = ln 2. b-decay high n/p Ø
t a-x p
t = age of mineral 6C
14
h 7N14 + –1e0
a = initial amount of radioactive substance n n
Age determination of dead animals and plants or carbon = 1.33, = 1.0
p p
dating
3. g-decay high-energy decrease the energy level.
7N + 0n h 6C + 1P
14 1 14 1
level in nuclei
This method is based on ratioactive decay of 14C, which formed
in the upper part of atmosphere according to above reaction.
At the same time, C14 disintegrates so that ratio of radioactive Positron n n
4. low ratio ≠
carbon and non-radioactive carbon becomes constant. This decay p p
ratio is available in all living animals and plants. After the
(b+ decay) h 6C13 + 1e0
7N
13
death of animal or plant, this ratio changes due to disintegra-
n/p = 6/7 n/p = 7/6
tion of C14. The age can be determined from the formula:
5. k-capture 1P1 + –1e0 h 0n1
1 a
l = ln
t a-x It is the phenomena in which lighter unstable nuclei having
low n/p ratio capture the e– from the nearest shell (i.e., K-
Accuracy for this method is not good, when it is applied for n
very small or long time period. shell) in order to increase the ratio.
p
Cause of radioactivity
Those nuclei whose n/p ratio is in the range 1 to 1.5 are gen-
7
4 Be + -1e0 ææ
Æ 37 Li
erally stable. This range is called stability belt. n 3 n 4
For unstable nuclei, disintegrate in order to reach to the = =
p 4 p 3
stability best.
Nuclear reactions
Reactant nuclei + Bombarding particle Æ product nuclei
n + emitted particle
Representation
Reactant nucleus (bombarding particle, emitted particle)
product nucleus.
11Na + 1P h 12Mg + 0n
24 1 24 1

20 p 24
11Na (1P1, 0n1) 12Mg24

IIT JEE PC-V2_01.indd 13 5/13/2017 10:26:03 AM

 1.14

E = Dmc2
3 Li (a 2 , 2 He)3 Li
7 4 3 8
Example
1 amu = 931.5 MeV
Example 94 Be(g 0 n1 )84 Be
A1 - A2
During the nuclear fission and fusion, large amount of energy Number of a particle emitterd =
4
is released because of mass defect.
Dm = mass defect = mR – mP No of b particle emitted = 2a – [Z1 – Z2]

Solved Examples

1. At 10°C for any reaction rate constant = K, what will be

rate constant at 90°C (given temperature coefficient 2) [NH3] 0.6

R2 K 2 DT 0.4
Sol. = = ( m ) 10 = 28 K
R1 K1 0.2
5 10 20
2. (a) For the following reaction write down rate law: Time (sec) Æ
N2 + 3H2 h 2NH3
D[NH3 ] 0.2
12 g - = = 0.04 M/sec -1
(b) If rate of dissappearance H2 is . What is Dt 5
- sec
the rate of appearance of NH3. 1 0.2
r= ¥ = 0.01 M/sec -1
2 10
1 Ê - d [N 2 ] ˆ 1 Ê - d [H 2 ] ˆ
Sol. (a) Rate = Á ˜= Á ˜ 5. 2N2O5 h 4NO2 + O2, the variation of concentra-
1 Ë dt ¯ 3 Ë dt ¯ tion of N2O5 with time can be expressed by [N2O5] =
1 + [dNH3 ] [N2O5]0 e–Kt and K = 10–4 sec–1. If initially 1 mole of
= = K [N 2 ]m [H 2 ]n
2 dt N2O5 taken calculate.
(i) Rate of disappearance of N2O5 at t = 104 sec.
d [NH3 ] 2 Ê - d [H 2 ] ˆ 2 12 moles (ii) Rate of reaction during first 104 sec.
(b) = ÁË ˜¯ = ¥ =4 (iii) Variation of concentration of NO2 with time.
dt 3 dt 3 2 - sec
d [N 2O5 ]
= 4 ¥ 17 = 68 g
gram (i) Rate = - = K [N 2O5 ]0 e - Kt
- sec dt
-4
¥104
= K [N 2O5 ]0 e -10
3. For the reaction, 2A Æ 3B + 4C, the number of moles
of B increases by 6 ¥ 10–3 moles in 10 sec in a 10 L 1
= K [N 2O5 ]0 ¥
container. Calculate: e
(a) rate of appearance of B and C. 1
= 1 ¥ 10-4 [1] ¥
(b) rate of disappearance of A e
DConc. 6 ¥ 10-3 We know a =
x
= 1 - e - Kt for first order.
Sol. (a) rB = = = 6 ¥ 10-5 a
Dt 10 ¥ 10
1 - 1/e 1
rC rB 4 (ii) R = ¥
= fi rC = ¥ rB = 8 ¥ 10-3 104 2
4 3 3
(iii) 2N2O5 Æ 4NO2 + O2
rA rB 2 1 – –
(b) = fi rA = rB = 4 ¥ 10-5 1–a 2a a/2
2 3 3
2 mole
4. For the reaction; 2NH3 Æ N2 + 3H2, the curve is plot-
ting between concentration of NH3 v/s time. Calculate
(a) rate of decomposition of NH3 between 5 to 10
seconds. [NO2]
(b) rate of reaction between 10 to 20 seconds.

Time

IIT JEE PC-V2_01.indd 14 5/13/2017 10:26:04 AM

 Chemical Kinetics 1.15

6. For the given gaseous reaction A Æ 2B + C pressure 0.0453

after sufficient time was found to be 300 mm and after x= ¥ 238 = 0.05234
206
time 2.303 sec, it was found to be 200 mm calculate.
0.693 1 Ê 1.05234 ˆ
(i) rate constant (ii) half-life = ln Á ˜
A Æ 2B + C 4.5 ¥ 109 t Ë 1 ¯
t=0 P0 – – = 3.29 ¥ 106 yrs.
t=t P0 – x 2x x
t= – 2P0 P0 10. An old piece of wood have 25% of C14 as much as or-
P fi 300 = 3P0 fi P0 = 100 mm dinary wood today has. Find the age of wood given t1/2
P0 + 2x = 200 mm of C14 is 5760 yrs.
Ans. t = 2 ¥ t1/2 = 2 ¥ 5760y
x = 50 mm
11. For the elementary reaction 2A + B2 h 2AB. Calcu-
2.303 P late how much the rate of reaction will change if the
K= log 0
t P0 - x volume of the vessel is reduced to one third of its origi-
2.303 100 nal volume?
K= log = 0.3010
2.303 50 Ê dx ˆ
Sol. 2A + B2 h 2AB Á ˜ = K[A]2[B2]
Ë dt ¯ 1
0.6932 0.6932
(ii) t1/2 = = = 2.303
K 0.3010 V
if V is decrease to
234
disintegrates to gives 82pb206 as the final prod- 3
7. 20Th
uct. How many a and b particles emitted. fi Ê dx ˆ Ê dx ˆ Ê dx ˆ
ÁË ˜¯ = [3 A] [3B ] ÁË ˜¯ = 27 ÁË ˜¯
3
234
h 82Pb206 + x24a + y-01b dt 2 dt 2 dt 1
Sol. 20Th
reaction increases by 27 times.
A2 - A1 234 - 206
OR a= = =7 [OR] 12. In the reaction 2H2O2 h 2H2O + O2 rate of forma-
4 4 tion of O2 is 3.6 M min–1.
A fi 234 = 206 + 4x fi x = 7 b = 2 ¥ a – [Z1 – Z2]
(a) What is rate of formation of H2O?
Z fi 90 = 82 + 2x – y fi y = 6 = 2 ¥ 7 – [90 – 82]
(b) What is rate of disappearance of H2O2?
= 14 – 8 = 6 d O2
8. Activity of 1 g of Radium is found to be 0.5 Ci. Calcu- Sol. 2H2O2 h 2H2O + O2 = 3.6 M min–1
late the half-life period of radium and time required for dt
the decay of 2 g to 0.25 g. [A = 226] (a) Rate of formation of H2O
Sol. Activity = l ◊ N d H 2O
= l ¥ n ¥ NA = 2 ¥ 3.6 = 7.2 M min–1
dt
1 d H 2O 2
=l¥ ¥ 6.022 ¥ 1023
226 = 7.2 M min–1
1 dt
= 0.5 ¥ 3.7 ¥ 1010 = l ¥ 6.023 ¥ 1023 13. A certain organic compound A decomposes by two par-
226
allel first order mechanism
0.693
t1/2 = k1 B
l A
k2
l = 69.417 ¥ 10-13 C

= 9.9 ¥ 1010 sec. If k1 : k2 = 1 : 9 and k1 = 1.3 ¥ 10–5 s–1

Calculate the concentration ratio of C to A, if experi-
3
m 0.25 1 Ê 1 ˆ ment is started with only A and allowed to run for one
= = =Á ˜
m0 2 8 Ë 2¯ hour.
Sol. Given:
ttaken = 3 ¥ t1/2 = 3 ¥ 9.9 ¥ 1010 sec.
9. The final product of U238 is Pb206. A sample of pitch- k1 1
= , k1 = 1.3 ¥ 10–5
gland is 0.0453 g of Pb206 for every gram U238 present k2 9
in it, assuming that the pitch gland formed at the time k2 = 9k1
of formation of the earth didn’t contain any Pb206.
Calculate the age of earth, t1/2 for U238 = 4.5 ¥ 109 yrs. [ A] = [ A]0 e - ( k1 + k2 )t
ln 1.05234 = 0.051. k2 [ A]0
[C ] = [1 - e - ( k1 + k2 )t ]
Sol. a – x = 1 g fi mpb = 0.0453 g k1 + k2
a=1+x
[C ] k2 9k
0.0453 = [e( k1 + k2 )t - 1] = 1 [e10 k1t - 1] = 0.537
U238 h Pb206 [ A] k1 + k2 10k1
206

IIT JEE PC-V2_01.indd 15 5/13/2017 10:26:06 AM

 14. The reaction k1 k
k1
17. For the mechanism A + B C C ææ
3
ÆD
+ + k2
cis–Cr(en)2(OH)2 trans–Cr(en)2(OH)2
k2 Derive the rate law using the steady-state approxima-
is first order in both directions. At 25°C, the equilibri- tion to eliminate the concentration of C. Assuming that
um constant is 0.16 and the rate constant k1 is 3.3 ¥ 10–4 k3 << k2, express the pre-exponential factor A and Ea
s–1. In an experiment starting with the pure cis form, for the apparent second-order rate constant in terms of
how long would it take for half the equilibrium amount A1, A2 and A3 and Eal, Ea2 and Ea3 for the three steps.
of the trans isomer to be formed? k1 k
14. k = 0.16, k1 = 3.3 ¥ 10–4 Sol. A + B C , C ææ
3
ÆD
k2
so k2 = k1/k = 2.0625 ¥ 10–3 r = k1[A] [B] – k2[C]
k1 + k2 = 0.0023925
d [C ]
k k [ A] = k1[A] [B] – k2[C] – k3[C] = 0
[ B]eq. = 1 [ A]eq. = 1 0 dt
k2 k1 + k2
k [ A][ B ]
[ B]eq. k1[ A]0 [C ] = 1
Given [ B] = = k 2 + k3
2 2(k1 + k2 )
d [ D] k [ A][ B ]
k [ A] = r = k1[ A][ B ] - k2 ¥ 1
and [ B] = 1 0 [1 - e - ( k1 + k2 )t ] dt k 2 + k3
k1 + k2 k1k3[ A][ B ]
1 r=
so = 1 - e - ( k1 + k2 )t (k1 + k2)t = ln 2 k 2 + k3
2 since k2 >> k3
t = 289.71 sec. = 4.82 min.
k1k3
15. An optically active compound A upon acid catalysed knet =
hydrolysis yield two optically active compound B and k2
C by pseudo first order kinetics. The observed rotation A1 A3
of the mixture after 20 min was 5° while after comple- so Anet =
A2
tion of the reaction it was –20°. If optical rotation per
mole of A, B and C are 60°, 40° and –80°, calculate half (Ea)net = Ea1 + Ea3 – Ea2
life and average life of the reaction. 18. The decomposition of a compound P, at temperature T
Sol. A h B + C according to the equation 2P(g) h 4Q(g) + R(g) + S(l)
t=0 a – – is the first order reaction. After 30 minutes from the
t = 20 min. a–x x x start of decomposition in a closed vessel, the total pres-
t= – a a sure developed is found to be 317 mm Hg and after a
60(a – x) + 40x – 80x = 5 long period of time the total pressure is observed to be
and 40a – 80a = – 20 617 mm Hg. Calculate the total pressure of the vessel
on solving a = 0.5, x = 0.25 after 75 minute, if volume of liquid S is supposed to be
so t1/2 = 20 min. negligible. Also calculate the time fraction t7/8.
Average life = 1/K = 1.443 ¥ t1/2 = 28.86 min. Given : Vapour pressure of S(l) at temperature T = 32.5
mm Hg.
k1
16. For the reaction A P . Following data is pro- Sol. 2P(g) h 4Q(g) + R(g) + S(l)
k-1
duced: t=0 P0
Time/Hr. 0 1 2 3 4 t = 30 min. P0 – P 2P P/2
%A 100 72.5 56.8 45.6 39.5 30 t= – 2P0 P0/2
Find k1, k–1 and Keq. so P0 – P + 2P + P/2 = 317 – 32.5
Sol. At t = when equilibrium is established i.e., P0 + 1.5P = 284.5 (i)
[ P] 7 and 2.5P0 = 617 – 32.5 = 584.5
k= = = 2.33 so P0 = 233.8
[ A] 3
P = 33.8
k1 233.8
and = 2.33 fi k1 = 2.33 k–1 k ¥ 30 = ln fi k = 0.0052
k-1 200
k2 [ A]0 At t = 75 min
[ A] = [1 - e - ( k1 + k2 )t ] 233.8
k1 + k2 0.0052 ¥ 75 = ln
P0 - P
k–1 = 4.16 ¥ 10–5 sec–1
k1 = 2.33 k–1 = 9.7 ¥ 10–5 sec–1 P0 – P = 158.23 fi P = 75.57
PT = 32.5 + P0 + 1.5P = 347.155 + 32.5

IIT JEE PC-V2_01.indd 16 5/13/2017 10:26:08 AM

 Chemical Kinetics 1.17

PT = 379.65 mm Hg 67.7
(ii) 0.0052 ¥ t = ln 8 = ¥ 0.1 = 0.09575 mg
70.7
t = 399.89 min.
19. In a nature decay chain series starts with 90Th232 and 21. 84Po218 (t1/2 = 3.05 min) decay to 82Pb214 (t1/2 = 2.68
finally terminates at 82Pb208. A thorium ore sample was min) by a-emission, while Pb214 is a b-emitter. In an
found to contain 8 ¥ 10–5 mL of helium at STP and 5 experiment starting with 1 g atom of pure Po218, how
¥ 10–7 g of Th232. Find the age of ore sample assuming much time would be required for the number of nuclei
that source of He to be only due to decay of Th232. Also of 82Pb214 to reach maximum.
l l
assume complete retention of helium within the ore. Sol. 84 Po
218
ææ
1
Æ82 Pb 214 ææ
2
Æ 83Bi 214
(Half-life of Th232 = 1.39 ¥ 1010 Y)
Number of nuclei of Pb214 at time t are N2 =
Sol. 90Th232 h 82Pb208 + 6 2He4 + 4 –1b0
l1 N 0
t=0a [e - l1t - e - l2t ]
time t a – x 6x (l2 - l1 )
given: dN 2
For max. value of N2 =0
5 ¥ 10-7 dt
a–x= = 2.155 ¥ 10–9 mole
232 1 l
so t= ln 2
8 ¥ 10-5 (l2 - l1 ) l1
6x = fi x = 5.9523 ¥ 10–10 mole
22400 0.693 0.693
so a = 2.75 ¥ 10–9 when l2 = , l1 = ,
2.68 3.05
0.693
k= on putting these values
1.39×1010 3.05
a t = 31.87 ln = 4.12 min
k ¥ t = ln 2.68
a-x
22. A sample pitch blende is found to contain 50% Ura-
0.693 ¥ t 2.75 ¥ 10-9 nium (U238) and 2.425% Lead. Of this Lead only 93%
= ln = 0.2438
1.39 ¥ 1010
2.155 ¥ 10-9 was Pb206 isotope, if the disintegration constant is 1.52
¥ 10–10 yr–1. How old could be the pitch blende deposit?
t = 4.89 ¥ 109 year
Sol. Let the mass of sample in a g and initial mass of U238 is
20. A sample of 131 53 I , as iodine ion, was administered to w g, then
a patient in a carrier consisting of 0.10 mg of stable U238 h Pb206
iodide ion. After 4.00 days, 67.7% of the initial radio- t=0 w
activity was detected in the thyroid gland of the patient. 206
What mass of the stable iodide ion had migrated to the t w–x x
238
thyroid gland? (t1/2 = 8 days.) given w – x = 0.5a
0.693 206 x 2.425a
Sol. k = = ¥ 0.93 = 0.0225525a
8 238 100
A 0.693 A x = 0.026a
kt = ln 0 = ¥ 4 = ln 0
A 8 A so w = 0.526a
A
= 0.707 w
A0 lt = ln
w- x
Total activity is 70.7% of the original activity but only 0.526a
67.7% found in the thysoid so mass of stable iodide ion 1.52 ¥ 10–10 ¥ t = ln
0.5a
had migrated to the thyroid gland is t = 3.33 ¥ 108 year.

IIT JEE PC-V2_01.indd 17 5/13/2017 10:26:10 AM