Exercises of Chemical Reaction kinetics

k
1. The reaction A B
1 k C, (1). derive the expression for formation of B in term of k 1, k2 and [A]0
2

by LAPACE transform method. (2).show that the maximum concentration of B occurs at tmax=

k
ln 2 /( k 2 k1 ) . (3). If k1=10-8s-1 and k2=1s-1, estimate the time t when the concentration of
k1
B reaches 0.9[B]max.What is the implications of this result.
k1

2. In the reaction A B C ,
k2
the equilibrium is subjected to a small disturbance and the system

relaxes to a new equilibrium position where the concentrations of A, Band C are [A]e, [B]e and.
[C]e respectively, derive the expression of the relaxation time, in term of k1, k-1, [A]e, [B]e and.
[C]e
k1 k2

3. Derive rate equation of the reaction A

B
C by determinant (matrix) method
k 1 k 2

4. In the reaction between A and B the variation of half-life of A with initial concentrations of A
and B is given in the following table
[A]0 /mol.dm-3 0.01 0.01 0.02
-3
[B]0 /mol.dm 0.500 0.250. 0.250
T1/2 /min. 80 160 80
2
(1). Show differential rate equation R=k[A] [B]
(2). What is the rate constant

5. Evaluate the activation energy of the reaction CH3-H + CF3 CH3 + H-CF3 by BEBO method.
Bond length: CH3-H, r1s = 1.09 H-CF3, r2s = 1.095, H3C-CF3 r3s = 1.54.. Bond energy:
CH3-H, D1s = 105.5KCal.mol-1, H-CF3, D2s = 107.0KCal.mol-1 , H3C-CF3 D3s = 84.4KCal.mol-1 .
Morse parameter : 3= 1.94-1, L-J parameter: ELJ(Ne-He) = 38.0 Cal.mol-1 rm(Ne-He) = 2.99
. Calculate the potential energies, V(n2) for n=0, 0.1, 0.2, 0.3, 0.4, 0.45, 0.5 and plot the
variation of potential energy with n2

6. The experimental activation energies for reaction C 2H5 + H2 -C2H6 + H have been
reported(Can. J. Chem., 60,3039(1982)): 350-550K, 50KJmol -1, 800-1100K, 71 KJmol-
1
.Eveluate the parameters m and E b for k=ATmexp(-Eb/RT)

7. Evaluate the pre-exponential factors A for gas-phrase reactions

(1) mono-atomic molecule + diatomic molecule linear activated complex.
(2) linear poly-atomic molecule + non-linear poly-atomic moleculenon-linear activated
complex

8. Evaluate S for gas-phrase diamolecuar reaction at 573K, A=7.41010dm3 mol-1s-1, standard

state:1mol.dm-3
9. Evaluate k2/k-1 when ku=80%k and [M]+10-4mol.L-1for unimolecular reaction. The

,
k1
Lindemanns mechanism: A M * k
A M A*
2
P
k 1

10. Rate constants for gas-phrase dimerization of cyclic pentylenes and the bimer decomposition
at 373K are as follows:
Dimerized: k2=106.1exp(-16700x4.184/RT)dm3mol-1s-1
Decomposed: k1=1013.1exp(-35000x4.184/RT)s-1
Evaluate S for forward and back reaction. What activated complex is shown?

11. The expression of k for the unimolecular reaction at 500K is k

=5.21014exp(437004.184//RT)s-1. how many degees ,S of vibrational freedom are there at
least if ku is still equal to k at P=150mmHg? Derivation with RRK theory. The cross sectional
area AA= (1.0nm)2, molecular weight, mA=160

12. Derivate the rate constant of unimolecular reaction at high pressure limit with kRRKM,
theory.

13. The decomposition reaction of acetaldehyde is CH3CHO CH4 + CO. The reaction
mechanism is listed below:
Initial CH3CHO CH3+ CHO
Propagation CH3+ CH3CHO CH4 + CH3 + CO
Termination 2CH3 C2H6
(1). Determine the production rate of CH4 with the steady state approximation for the CH 3
intermediate.
(2). Evaluate the activation energy for the initial step., when the activation energies for the
overall reaction, the propagation step and termination step are given, E exp=192.5, Ep=33.5,
ET=0KJmol-1, respectively.

14. Suggest plausible mechanism for the thermal decomposition of acetone

1.CH3COCH3 CH3CO + CH3 84Kcalmol-1
2. CH3CO CH3 + CO 16
3. CH3 + CH3COCH3 CH4 + CH2COCH3 15
4. CH2COCH3 CH3 + CH2CO 48
5. CH3 + CH2COCH3 C2H5COCH3 5
(1). Derive the expression for the thermal decomposition rate equation of acetone in terms of
ki(i=1-5) and [CH3COCH3]
(2). Estimate the activation energy of the overall reaction.

15. The mechanism for the reaction H2 + Br2 2HBr is as follows:

Br2 2Br E0=192KJmol-1
Br + H2 HBr + H E1=72KJmol-1
H + Br2 HBr + Br E2=5KJmol-1
H + HBr H2 + Br E-1=5KJmol-1
2Br Br2 ET=0KJmol-1
Estimate the activation energy of the overall reaction Eexp. when
(1). In the initial
(2). In the end

16. (1) Derive the expression for the rate equation of the overall reaction H 2 + I2 2HI. The
mechanism :
k1

I2
2I
k 1
fast

k2

I + H2 H2I
k 2
fast
k3
H2I + I 2HI slow
(2). What is the expression if the mechanism:
k0
I2 2I
k1
I + H2 HI + H
k2
H + I2 HI + I
kT
2I I2