Chem 338

Homework Set #10 solutions November 30, 2001

From Atkins: 10.1, 10.3, 10.4, 10.6, 10.7, 10.11, 10.15, 10.19, 10.20, 10.23

10.1) The rate of formation of C in the reaction 2A + B → 3C + 2D is 2.2 mol L-1 s-1.

State the rates of formation and consumption of A, B, and D.

rate of consumption of A = 2/3 (rate of formation of C) = 1.5 mol L-1 s-1
rate of consumption of B = 1/3 (rate of formation of C) = 0.73 mol L-1 s-1
rate of formation of D = 2/3 (rate of formation of C) = 1.5 mol L-1 s-1

10.3) If the rate laws are expressed with (a) concentrations in molecules m-3, (b)
pressures in kPa, what are the units of the 2nd order and 3rd order rate constants?
In both cases, the units of the rate itself must be in concentration or pressure per
second:
a) For 2nd order: r = k[A]2, k has units m3 molecules-1 s-1
For 3rd order: r = k[A]3, k has units m6 molecules-2 s-1
b) For 2nd order: r = k(PA)2, k has units kPa-1 s-1
For 3rd order: r = k(PA)3, k has units kPa-2 s-1

10.4) The following initial rate data were obtained on the rate of binding of glucose
with the enzyme hexokinase present at a concentration of 1.34 mmol L-1. What is
(a) the order of reaction with respect to glucose, (b) the rate constant?

[C6H12O6] (mmol L-1) 1.00 1.54 3.12 4.02

Initial rate (mol L-1 s-1) 5.0 7.6 15.5 20.0

 Chem 338 Homework #10

The reaction of interest is: C6H12O6 + HK → C6H12O6–HK

The rate law is assumed to have the form: r = k [C6H12O6]x[HK]y

In the method of initial rates, this rate law becomes: r0 = k [C6H12O6]0x[HK]0y
There are two ways to go about this problem, taking simple ratios and graphically.
1) For each possible combination of experiments, construct the ratio of the intial
rates:
x
r01 [C 6 H12 O6 ]01
e.g., = (the k’s and the HK concentrations cancel out)
r02 [C 6 H12 O6 ]x
02
x
r01 5.0  1.00 × 10 −3 
= =
r02 7.6  1.54 × 10 −3 

 5.0   1.00 × 10 −3 
ln = x ln  
 7.6   1.54 × 10 −3 
x = 0.97
For the other combinations:
r01/r03 , x=0.99
r01/r04 , x=1.00
r02/r03 , x=1.01
r02/r04 , x=1.01
r03/r04 , x=1.01

AVG order with respect to glucose = 0.998 = 1 (1st order in glucose)

The effective 1sts order rate constant is obtained by substitution for each
combination, AVG k = 4920 mol-1 L s-1 (assumes the enzyme is in excess)
2) For a graphical (better) solution, plot ln r0 vs. ln[C6H12O6]. After fitting to a
straight line, the slope will be x and the y-intercept will correspond to lnk.
 Chem 338 Homework #10

3.2
2
y = 8.5021474 + 0.99855324x R = 0.99993075

2.8

2.4
ln(r )
0

2.0

1.6

-7.0 -6.5 -6.0 -5.5 -5.0

ln[C H O ]
6 12 6

Therefore:
x=0.9986 = 1 and k = exp(8.50215) = 4925 mol-1 L s-1
(Note that these agree with the values obtained with the ratio method)
10.6) The rate constant for the 1st order decomposition of N2O5 in the reaction 2N2O5
(g) → 4NO2(g) + O2(g) is k = 3.38 x 10-5 s-1 at 25ºC.

a) What is the half-life of N2O5 ? What will be the total pressure, initially 500
Torr for the pure N2O5 vapor, a) 10 s, b) 10 min after initiation of the reaction?
ln 2
a) For a 1st order reaction, t 1 =
2 k
ln 2
So, t 1 = −5
= 2.05 × 10 4 s
2 3.38 × 10
b & c) For a 1st order reaction, [A] = [A]o e − kt , or in the present case if we assume
t =o − kt
the volume and temperature are held constant: PN 2O5 = PN O
2 5
e since then

pressure is directly proportional to the number of moles of N2O5 (perfect gas).

 Chem 338 Homework #10

After 10 s, the pressure due to N2O5 will be reduced to:

PN 2O5 = (500 Torr) e − kt = (500) exp[ −(3.38 × 10 −5 )(10)] = 499.8 Torr

From the stoichiometry of the reaction, a loss of 0.2 Torr of N2O5 will be
accompanied by an increase of 5/2 x 0.2 Torr = 0.5 Torr for the products
P(total) = 499.8 + 0.5 = 500.3 Torr (essentially unchanged)

After 10 min = 600 s,

PN 2O5 = (500) exp[ −(3.38 × 10 −5 )(600)] = 490 Torr

The loss of 10 Torr of N2O5 is matched by an increase of 5/2(10) = 25 Torr in the

products.
P(total) = 490 + 25 = 515 Torr
Note that you could also work this problem in terms of the fraction of N2O5
dissociated.

10.7) In the oxidation of ethanol, the molar concentration of ethanol decreased in a

first-order reaction from 220 mmol L-1 to 56.0 mmol L-1 in 1.22 x 104 s. What
is the rate constant of the reaction?
For a 1st order reaction, [A] = [A]o e − kt or ln[A] = ln[A]o − kt
Hence,
1
k= (ln[A]o − ln[A])
t
1
= 4[
ln(220) − ln(56)] = 1.12 × 10 −4 s-1
1.22 × 10
 Chem 338 Homework #10

10.11) The formation of NOCl from NO in the presence of a large excess of chlorine is
pseudosecond-order in NO. In an experiment to study the reaction, the partial
pressure of NOCl increased from zero to 100 Pa in 522 s. What is the rate
cosntant of the reaction given that the initial partial pressure of NO is 300 Pa?
The balanced reaction is: NO + 12 Cl2 → NOCl
d [NOCl]
The rate for the production of NOCl is: = k[NO]2 , where k is the
dt
pseudo 2nd-order rate constant and Cl2 is in large excess.

kt[NO ]20
Using the integrated rate law for a 2nd-order reaction: [NOCl] =
1 + kt[NO ]0
But for constant volume, the partial pressures are directly proportional to the molar
concentrations, so we can use these directly in this expression:
2
ktPNO,0
PNOCl =
1 + ktPNO,0

Solving for the rate constant k,

PNOCl 100 Pa
k= =
( 2
t PNO,0 − PNOCl PNO,0 ) ( )
522 300 2 − (100)( 300)
Pa
= 3.19 × 10 −6 2
= 3.19 × 10 −6 Pa -1 s -1
s Pa
 Chem 338 Homework #10

90
10.15) The half-life for Sr = 28.1 yr. How much of 1.00 µg will remain after (a) 19

yr. and (b) 75 yr.

Each half-life decreases the concentration by 1/2:

( )n
[A]t = 12 [A]o , where n is the number of half-lives

Taking the natural log of both sides: ln[A] = n ln 12 + ln[A]o

a) 19 yr = 0.6762 half-lives
ln x = (0.6762) ln 12 + ln(1.00) = −0.4687
x = 0.63 µg
b) 75 yr. = 2.669 half-lives
ln x = (2.669) ln 12 + ln(1.00) = −1.832
x = 0.16 µg

10.19) A rate constant is 1.78 x 10-4 L mol-1 s-1 at 19ºC and 1.38 x 10-3 L mol-1 s-1 at
37ºC. Evaluate the Arrhenius parameters of the reaction.
Starting from the relation derived from the Arrhenius equation (note: you should be
able to easily derive this yourself!)
k E  1 1
ln 1 = a  − 
k2 R  T2 T1 

k1 1.78 × 10 −4
R ln (8.3145) ln
Ea =
k2
= 1.38 × 10 −3
 1 1  1 − 1 
 −   310 292 
 T2 T1 
= 85.63 × 10 3 J / mol = 85.6 kJ / mol
using the 19ºC data:
k 1.78 × 10 −4
A= E
= 3 = 3.70 × 1011 L mol -1 s-1
− a 85.63×10
−
e RT e (8.3145)(292 )
 Chem 338 Homework #10

10.20) The activation energy for the decomposition of benzene diazonium chloride is
99.1 kJ/mol. At what temperature will the rate be 10% greater than its rate at
25ºC?
k E 1 1
Starting with the relation: ln 2 = a  − 
k1 R  T1 T2 

1.10 k1 E  1 1
if k2 = 1.10(k1): ln = ln(1.10) = a  − 
k1 R  298 T2 

Rearranging to solve for T2:

Ea
T2 =
Ea
− R ln 1.10
298
99.1 × 10 3
= = 299 K
99.1 × 10 3
− (8.3145) ln 1.10
298

10.23) Food rots about 40 times more rapidly at 25ºC than when it is stored at 4ºC.
Estimate the overall activation energy for the processes responsible for its
decomposition.
rate @ 25ºC = 40 x rate @ 4ºC :
40 k4 Ea  1 1 
ln = −
k4 R  277 298 
R ln 40
Ea = = 1.21 × 10 5 J / mol = 121 kJ / mol
 1
−
1 
 277 298 