Assignment 4

Chemical Kinetics
1. A reaction is 50% complete in 10 minutes. It is allowed to proceed another 5
minutes. How much of the reaction would be complete at the end of these 15
minutes if the reaction follows zero order kinetics? Exercise 19.4,
page 590, Dogra and Dogra
Answer:
Let [A]0 be 1 x 103 mol dm-3. Half of [A]0 is consumed in 10 minutes so k from
equation is
k = ((1- ) 103 mol dm-3) / 10 min = 50 mol dm-3
Now in further 5 minutes i.e., after 15 minutes.
[A] = [1 x 103 50 x 15] mol dm-3 = 250 mol dm-3

2. Phosphorescence emission of Acetone-d6 (0.05 M) in Acetonitrile at 20C was

measured at 450 nm. Calculate the rate constant for the emission and also
calculate the average life- time of triplet sate of acetone from the following data
t( sec) 20 32 40 60 80 100 120 140
Intensity (I) 5.5 4.6 4.0 2.9 2.1 1.5 1.05 0.75
(Arbitrary units)
Log I 0.74 0.66 0.60 0.46 0.33 0.18 0.025 0.12
Exercise 19.5, page 591, Dogra and Dogra

Log I is plotted vs time in Figure below and slope obtained is 0.72 x 104 s-1.

1.2

0.8
Log I

0.4

0 40 80 120 160
t(S)
 Now k = slope x 2.303
= (0.72 x 104 s1) x 2.303
= 1.66 x 104 s1
Average life of triplet state = 1/k
= 1/1.66 x 104 s1 = 60 S

3. Half-life for disintegration of radium is 1590 years. Calculate the rate constant in s-1
and also how many years will be taken for the disintegration of 80% of the material?
Exercise 19.11, page 597, Dogra and Dogra
Answer:
t = 1590 years = 5.014 x 1010S
Using equation
t = 0.69/k
k = 0.69/(5.014 x 1010S) = 1.376 x 10-11 s-1
Now if [C]0 = 100 mol dm-3, [C] = 20 mol dm-3
And using equation,
k = 1/t ln [C]0/[C]
t = ((2.303 x 1590 years)/0.69) log 100/20 = 3661.8 years

4. The reaction 2A + B C + D goes to completion and follows the following rate law
- d[A]/dt = k [A]2[B]
Fill the gaps left in the following information
10+6 x [A]0 [B]0 x 106 half time
(mol dm-3) (mol dm-3) (s)

300 40 62.6
300 60 -
5 300 625

2
 10 300 -
Exercise 19.12, page 597, Dogra and Dogra

In more than one reactant system, the half-life is the time for the half of the reactant
present in small amount.

In the first set, reactant B is in small amount, the half-life is for reactant B.
Further the rate is first-order with respect to B, so the half-life is independent of initial
concentration, i.e. missing data is 62.6s.
In the second set, the half-life is for reactant A, and rate is second order with
respect to A, the equation
t = 2n-1 1/ (n-1) [C]0n-1 k
Becomes
t = 1/ k [A]0
Now
(t)1/( t)2 = 1/ k [A1]0 x k [A2]0/1
Substituting the values
( t)2 = ( t)1 [A1]0 /[A2]0
= ((625s)(5 x 10-6 mol dm-3) / (10 x 10-6 mol dm-3))
= 312.5 s
5. A reactant R undergoes three first-order parallel reactions to give three products P1,
P2 and P3 write the expression for the rate equation of each species.

k1
R P1
k2
P2
k3
P3
Exercise 19.19, page 605, Dogra and Dogra

Rate of removal of R is
= d[R]/dt = k1 [R] + k2[R] + k3[R]
3
 = (k1 + k2 + k3) [R]
And can be integrated to give
[R] = [R]0 e-kt
Where [R]0 is concentration of R at t = 0 and k = k1 + k2 + k3 = overall first order rate
constant.
Similarly rate expressions for products are
d[P1]/dt = - k1/k d[R]/dt = k1[R] = k1 [R]0 e-kt
After integration with condition that at time t = 0
[P1] = [P1]0 we get
[P1] = [P1]0 + k1/k (1 e-kt) [R]0
Similarly
[P2] = [P2]0 + k2/k (1 e-kt) [R]0
[P3] = [P3]0 + k3/k (1 e-kt) [R]0
if [P1]0 = [P2]0 = [P3]0 = 0, the above equations reduced to
[P1] = k1/k (1 e-kt) [R]0
[P2] = k2/k (1 e-kt) [R]0
[P3] = k3/k (1 e-kt) [R]0
it is clear from equations that the products are formed in the ratios of these rate
constants for respective reactions
[P1]:[P2]:[P3]:: k1 : k2 : k3

6. Isopropyl chloride undergoes hydrolysis in aqueous media by two reaction

mechanisms. Write expression for calculating k1 and k2.

CH3 k1 CH3 +
CHCl CH + Cl Slow
A
CH3 CH3
CH3 CH
+ Fast
CH + OH 3 CHOH
CH3 CH3
B
CH3 k2 CH3
CHCl + OH CHOH + Cl
CH3 CH3
A B

4
 Exercise 19.20, page 607, Dogra and Dogra

The rate determining step in scheme 1 is first one so the differential rate equation for
the total removal of isopropyl chloride will be
d[A]/dt = k1 [A] + k2 [A][B]
The simplest procedure is to write it as
1/[A] d[A]/dt = k1 + k2 [B]
Or
d(ln[A])/dt = k1 + k2 [B]
Plot of d ln [A]/dt vs [B] will be a straight line. Slope gives k2 and intercept gives k1.

7. Isopropyl benzene is alkylated by n-butylamine in presence of hydrogen fluoride in a

two step consecutive reaction as,

k1 k2
Isopropyl-benzene Isopropyl-sec butyl-benzene Isopropyl-di-sec butyl
benzene
If the initial concentration of isopropyl is 100 mol and relative rate constants
k1 : k2 :: 1:0.15, prepare a diagram showing the concentration of each species.
Exercise 19.23 page 610, Dogra and Dogra

Answer:
Let k1 = 4.0 x 10-2 min-1, so
k1 = 0.15 x 4 x 10-2 = 0.6 x 10-2 min-1
as a sample calculation give for t = 10 min
-2(10)
[R1] = 100 e-4.0 x 10 = 100 e-0.4 = 67
-2(10) -2(10)
[R2] = ((100) (4 x 10-2)/(0.6 x 10-2) (4.0 x 10-2) [e-4.0 x 10 - e-0.60 x 10 ]
-2(10) -2(10)
= - 4/(3.4 x 10-2) [e-4.0 x 10 - e-0.60 x 10 ] = 31.76
R3 = 100 67 31.76 = 1.24
Other data can be found out in a similar manner and tabulated as follows:
5
 Time [A] [B] [C] Time [A] [B] [C]
-3 -3
(min) (mol dm ) (min) (mol dm )
0 100 0 0 50 13.53 71.24 15.23
5 81.87 17.85 0.28 60 9.07 71.41 19.52
10 67.00 31.76 1.24 70 6.08 70.15 23.77
15 54.88 42.96 2.16 80 4.08 68.0 27.92
20 44.93 51.48 3.59 90 2.73 65.34 31.92
25 36.79 57.98 5.23 100 1.83 62.41 35.76
30 30.12 62.83 7.05 200 0.0033 35.05 64.95
40 20.19 68.79 11.02

8. With the help of data given in question 8, calculate [B]max and tmax, compare it with
values obtained from the graph obtained.
Exercise 19.24, page 611, Dogra and Dogra

Substituting the respective values in equations

[R2]max = [R1]0 (k2/k1)k2/k1-k2
and
tmax = (ln (k2/k1))/k2/k1
[B]max = (100M) ((0.15 min-1)/(1.0 min-1))0.15/1-0.15
= 71.55 M
tmax = ((ln(1.0/0.15))/(1.0 0.15) min-1) = 55.80 min
The agreement with the Figure holds good.

9. Thermal gas phase reaction between H2 and Br2 has the following mechanism,
Br2 2Br. k1
Br + H2 HBr + H. k2
H + Br2 HBr + Br. k3
H + HBr H2 + Br. k4
Br. + Br. Br2 k5

6
 Write the expression for d[HBr]/dt, d[H.]/dt and d[Br.]/dr
Assuming H. and Br. to be reactive intermediates, solve d[HBr]/dt, in terms of H2,
Br2, and HBr. What will be pseudo-order for the formation of HBr in the initial
stage?
Exercise 19.27, page 613, Dogra and Dogra

The rate expression for three species are

d[H]/dt = k2[Br][H2] k3[H][Br2] k4[H][HBr] = 0
d[Br]/dt = 2k1[Br2] k2[Br][H2] + k3[H][Br2] + k4[H][HBr] 2k5[Br]2 = 0
d[HBr]/dt = k2[Br][H2] + k3[H][Br] k4[H][HBr]
solving the first equations,
[Br] = (k1/k5) [Br2]
[H] = k2(k1/k5)(([Br2][H])/(k3[Br2]+k4[HBr]))
substituting [H] and [Br] in last equation gives
d[HBr]/dt = 2k2 (k1/k5) (([H2] [ Br2]3/2)/(k3 [Br2] + k4 [HBr]
at initial states [HBr] = 0, above equation becomes
d[HBr]/dt = 2 (k2/k3) (k1/k5) [H2] [Br2] = k [H2] [Br2]
Pseudo-order is 3/2, 1 with respect of H2 and half with respect to Br2.
The effective rate constant
k = 2 (k2/k3) (k1/k5)

10. If the activation energy of a reaction is 80.9 kJ mol-1, calculate the fraction of
molecules at 400C which have enough energy to react to form products.
Exercise 19.32, page 618, Dogra and Dogra

Collisions will yield products if the energy possessed by the molecules is equal to
or greater than activation energy. This is given as,
N/Nav = e-Ea/RT = e ( - (80.9 x 103 J mol-1)/ ((8.314 K J-1 mol-1)(673 K))
= e-14.459 = 5.257 x 10-7
i.e. fraction of molecules which have enough energy to go for the formation of
products is very small, i.e. 5.257 x 10-7.
7
11. Consider the unimolecular reaction cyclopropane propylene. The value of log A
for high pressure limit is 15 17. Calculate the value of S# for the reaction. Calculate
the contribution of Strans in the above reaction at 298 K.
Exercise 19.35, page 620, Dogra and Dogra, Physical Chemistry Through Problems
Answer:
According to equation
0#/R
A = (kbT/h)e1-n eS
n = 0
A = (kbTe/h)exp (S0#/R)
Or
S0#/R = 2.303 log A 2.303 log kbTe/h
ekbT/h = ((1.38 x 10-23 JK-1) (298K)(2.718))/(6.62 x 10-34 J s) = 1.70 x 1013
S0#/R = 2.303 log A h/kbTe = 2.303 log (1.479 x 1015)/(1.70 x 1013) = 4.466
S0# = (8.314 J K-1 mol-1) (4.466) = 37.13 J K-1 mol-1
Since the reactant and the product have the same massS0trans = 0. The whole
contribution is due to the internal degrees of freedom.
12. The decomposition of ozone, 2O3 (g) 3 O2 (g)
occurs by the reaction mechanism,
k1
M(g) + O3 (g) O2(g) + O(g) + M(g)
k_1
k2
O(g) + O3(g) 2O2(g)
where M is a molecule that can exchange energy with the reacting ozone molecule
through a collision, but M itself does not react. Use this mechanism to derive the rate
law for d[O3]/dt assuming that the intermediate O(g) concentration can be treated by
the steady-state approximation.
Example 27-5, page 1104, McQuarrie and Simon, Physical Chemistry A Molecular
Approach

Answer:
8
 The rate equations for O3(g) and O(g) are
d[O3]/dt = -k1 [O3][M] + k-1[O2][O][M] k2[O][O3]
and
d[O]/dt = k1[O3][M] k-1[O2][O][M] k2[O][O3]
Invoking the steady-state approximation for the intermediate O(g) means that we set
d[O]/dt = 0. setting d[O]/dt = 0 and solving the resulting expression for [O] gives us
[O] = {k1[O3][M]}/{k-1[O2][M] + k2[O3]}
Substituting this result into the rate equation for O3 then gives us
d[O3]/dt = {2k1k2[O3]2[M]}/{k-1[O2][M] + k2[O3]}

13. In the initial states of the reaction described by

H2(g) + Br2(g) = 2 HBr(g)
The observed rate law is
d[HBr]/dt = kobs [H2][Br2]
Show that this result is consistent with the rate law given in problem 10 and
determine kobs in terms of the rate constants of the mechanism.
Example 27-7, page 1115, McQuarrie and Simon, Physical Chemistry A Molecular
Approach

In the initial stages of the reaction, [HBr] << [Br2]

k-2/k3[HBr][Br2]-1<<1
This result allows us to simplify the denominator of the rate expression, obtaining the
result,

d[HBr]/dt = k2Kc,1 [H2][Br2]

The measured rate constant, kobs, is equal to k2Kc,1

14. The enzyme carbonic anhydrase catalyses both the forward and the reverse reactions
for the hydration of CO2 according to
H2O(1) + CO2(aq) = HCO-3(aq) + H+(aq)

9
Carbon dioxide is produced in tissue as one of the final products of respiration. It
then diffuses into the blood system, where it is converted to the bicarbonate ion by
carbonic anhydrase. The reverse reactions occur in the lungs, where CO2(g) is
expelled. Carbonic anhydrase has a single active site, and its molecular mass is 30
000 g.mol-1. If 8.0 g of carbonic anhydrase catalyse the hydration of 0.146 g of CO2
in 30 seconds at 37C, what is the turnover number of the enzyme (in units of s-1)?
Example 27-9, page 1122, McQuarrie and Simon, Physical Chemistry A
Molecular Approach

Answer:
To calculate the turnover number, we need to determine the ratio of the number of
moles of CO2 that react per second to the number of moles of enzyme present.
The number of moles of enzyme present is
Number of moles of enzyme = 8.0 x 10-6 g/30 000 g.mol-1 = 2.7 x 10-10 mol
The number of moles of CO2 reacted in 30 seconds is given by
0.146 g/44 g. mol-1 = 3.3 x 10-3 mol
Or rate of 1.1 x 10-4 mol.s-1. The turnover number is then
Turnover number = 1.1 x 10-4 mol.s-1/2.7 x 10-10 mol = 4.1 x 105 s-1
Thus, we see that each carbonic anhydrase molecule converts 410 000 CO2
molecules to HCO-3(aq) per second! It is one of the fastest working enzymes
known.

15. Assuming that the following steps are involved in the thermal degradation of acetaldehyde,
derive a rate expression for the formation of CH4. (6
marks)
CH3CHO CH3 + CHO
CH3CHO + CH3 CH4 + CH3CO
CH3CO CH3 + CO
CH3 + CH3 CH3CH3

R = ka [CH3CHO]
10
 R = kb [CH3CHO] [CH3]
R = kc [CH3CO]
R = kd [CH3]2
d[CH3]/dt = ka[CH3CHO] kb[CH3][CH3CHO] + kc[CH3CO] -2kd[CH3]2 = 0 (1)
d[CH3CO]/dt = kb[CH3][CH3CHO] kc[CH3CO] = 0 (2)

1+ 2,
ka[CH3CHO] 2kd[CH3]2 = 0
[CH3] = (ka/2kd)1/2 [CH3CHO]1/2
d[CH4]/dt = kb[CH3][CH3CHO] = kb (ka/2kd)1/2 [CH3CHO]3/2

16. The value of log A for an isomerisation reaction conducted at 298 K was found to be 15.17 in the
high-pressure limit. Calculate the value of S# for the reaction. (5 marks)

According to equation,
A = (kbT/h)e1-n eS#/R
n = 0
A = (kbTe/h)exp (S#/R)
Or
S#/R = 2.303 log A 2.303 log kbTe/h
ekbT/h = ((1.38 x 10-23 JK-1) (298K)(2.718))/(6.62 x 10-34 J s) = 1.70 x 1013
S#/R = 2.303 log A h/kbTe = 2.303 log (1.479 x 1015)/(1.70 x 1013) = 4.466
S# = (8.314 J K-1 mol-1) (4.466) = 37.13 J K-1 mol-1

17. Assume that the rate constant measured kobs = k1k2/k_1, k1, k2 and k-1 are the rate constants of the
elementary steps. The measured activation energy is negative. Derive an expression for the activation
energy in terms of the activation energies of the elementary steps and explain how the overall activation
energy is negative. (5 marks)

11
 At high concentration, kobs = k1k2/k_1. Denoting the experimentally measured values of A and
Ea by Aobs and Ea,obs, we have
kobs = Aobse-Ea,obs/RT
if each step of the reaction mechanism shows Arrhenius behaviour, then each of the rate
constants, k1, k-1 and k2 can be written in terms of an Arrhenius equation,
k1 = A1e- Ea,1/RT
k-1 = A-1e-Ea,-1/RT
k2 = A2e-Ea,2/RT
Substituting these equations into kobs = k1k2/k_1 shows that
Ea,obs = Ea,1 + Ea,2 - Ea,-1
and
Aobs = A1A2/A-1
Overall activation energy can be negative as Ea,obs = Ea,1 + Ea,2 - Ea,-1

12