2007

ChE 505
Homework No. 2

1.

A reaction has the following stoichiometry:

A + 2B = 2P

Suppose that initially in a batch system there are 0.28 mol of A, 0.39 mol of B,
and 0.13 mol of P.
a)
After a certain time 0.18 mol of A remains. What is the extent of reaction
and what are the amounts of B and P at that time?
b)
What is the extent of reaction if the process goes to completion?
2.

Reaction stoichiometry is:

2A + B = 3P
If the initial rate of consumption of A is 3.36 x 10-4 (mol/Ls), what is the rate of
consumption of B? What is the rate of formation of P and what is the rate of
reaction ( intrinsic rate)?

3.
The stoichiometric equation for the oxidation of bromide ions by hydrogen
peroxide in acid solution is
2Br- + H2O2 + 2H+ = Br2 + 2H2O
The intrinsic rate of reaction is:
r = k [H2O2][H+][Br-]
a)

If the concentration of H2O2 is increased by a factor of 3, by what factor is

the rate of consumption of Br- ions increased?
b)
If, under certain conditions, the rate of consumption of Br- ions is
7.2 x 10-3 mol dm-3 s-1, what is the rate of consumption of hydrogen
peroxide? What is the rate of formation of bromine? What is the rate of
reaction?
c)
If by the addition of water to the reaction mixture the total volume were
doubled, what would be the effect on the rate of change of the concentration
of Br-? What would be the effect on the rate of reaction?

4.

A reaction obeys the stoichiometric equation

A + 2B = 2P

The rate of formation of P at various concentration levels of A and B is listed in

the table below:
[A] (mol/L)
[B] (mol/L)
r (mol/Ls)
____________________________________________
3.5 x 10-2
2.3 x 10-2
5.0 x 10-7
-2
-2
7.0 x 10
4.6 x 10
2.0 x 10-6
9.2 x 10-2
4.0 x 10-6
7.0 x 10-2
If the rate of formation of P can be represented by

RP = kP [A ] [ B]

What values do and have and what are they, and what is the value of rate
constant kP?
What is the numerical value of the rate constant k for the intrinsic rate.
5.

A substance decomposes according to first-order kinetics, the rate constants at

various temperatures being as follows:
Rate constant, k/s-1

Temperature/ C

4.18 x 10-6
7.62 x 10-6
1.37 x 10-5
2.41 x 10-5
5.15 x 10-5

15.0
20.0
25.0
30.0
37.0

Calculate the activation energy.

6.
Based on the Lindemann-Christansen model of unimolecular reactions calculate
the ratio k2/k-1 knowing that at reactant concentration of 10-4 (L/mol) k1 has reached 80%
1
of its limiting value k .
7.

Alkylperoxynitrates RO2NO2, can be presumed to decompose according to the

following mechanism:
1

RO2 NO2
RO + NO2
2
2

RO2 + RO2 2RO+ O2

4

RO + NO2 RONO2
Let us assume that a sample of RO2NO2 decomposes in a batch reactor and its decay is
observed. We want to estimate k1 from that rate of disappearance. To analyze the
system we assume that both RO2 and NO2 are in pseudo-steady state and that
[RO2 ] [NO2 ].
Show that the observed first-order rate constant for RO2NO2 decay is related to the
fundamental rate constants of the elementary reactions of the above mechanism by

k2
k obs = k11

k2 + k3
Thus, given kobs and values for k2 and k3,k1 can be determined.
8.
The primary reaction occurring in the homogeneous decomposition of nitrous
oxide is found to be:
1
N2 O = N2 + O2
2
with rate
2
k1[N2 O]
RN 2 O =
1+ k 2 [N2 O]
Devise a mechanism to explain this observed rate.
Experiments reveal that in the above rate form
k1 = 1019.39 e 81,800 / RT (L mol min)
k 2 = 108.69 e 28,400 / RT (L mol min)
What is the activation energy for this reaction?
9.

The formation and decomposition of phosgene has the following stoichiometry:

CO + Cl 2 = COCl2

Forward reaction:
Reverse reaction:
a)

rf = k f [Cl 2 ]

3/2

rb = kb [Cl 2 ]

1/ 2

[CO]

[COCl2 ]

Are these rate expressions thermodynamically consistent?

3

b)
Determine which of the following mechanisms is consistent with these
experimentally found rates. How are the rate constants of the elementary reactions in the
proposed mechanism (see the two proposed mechanisms below) related to kf and kb?
MECHANISM I:

Cl 2
2Cl*

k
k1

fast, at equilibrium

k2

Cl* + CO COCl*

fast, at equilibrium

k2

COCl* + Cl2
COCl2 + Cl* slow and rate limiting

k
k3

MECHANISM II:

Cl 2
2Cl*

fast, at equilibrium

Cl* + Cl 2
Cl *3

fast, at equilibrium

k1

k2

2
k3

Cl 3 + CO
COCl2 + Cl
k
3
10.

slow and rate limiting

Consider the following reaction systems:

k1
A
B
k2
B + M
C

Assume M is present in great excess, so that [M ] constant. The concentration of B

and C are zero at t = 0 while initial concentration of A, [ A]0 is given.
a)

Derive analytical expressions for the exact dynamic behavior of this batch system
over time. Show mathematically under what conditions the pseudo-steady
approximation (PSSA) can be made for [B ].

b)

Use the PSSA to derive a simpler set of equations for the concentrations of A, B,
and C.

c)

Draw a graph (on log-log paper) that compares the exact behavior of the system to
calculations based on the PSSA for the following three sets of conditions. Discuss
your results.
Set 1
[M ] = 105
[A ]0 = 102
k 1 = 10-5
k 2 = 10-6

Set 2
[M ] = 105
[A ]0 = 102
k 1 = 10-3
k 2 = 10-6

Set 3
[M ] = 105
[A]0 = 102
k 1 = 10-1
k 2 = 10-6

Note that the above quantities are presented in consistent units. Concentrations [M], [A]0
are in (mmol/m3), k1 is in (1/s), and k2 in (m3/mmol s).