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Chemistry 232

Tutorial Set 3 2010


G. Marangoni

Date: Friday February 12, 2010.

1.

The rate of formation of C in the reaction is 2 A + B 2 C + 3 D is 1.0 mol L-1 s-1.


Calculate the rate of reaction for each of the other reaction components.

2.

The rate constant for the first order decomposition of N2O5 is 2.76 x 10-5 s-1.
a) Calculate the half-life of the reaction.
b) For an initial partial pressure of 500 Torr, calculate the partial pressure of N2O5 after
i) 200 s
ii) 6000 s.

3.

The rate constant for the thermal decomposition of an aldehyde was 0.00280 L/mol s at
30.0C and 0.018 L/mol s at 50.0C. Obtain the Arrhenius parameters for the reaction.

4.

For the rearrangement of cis-azoethane in the gas phase, the activation energy is 85.9 kJ/mol
and the pre-exponential factor is 1.4 x 1014 s-1. Calculate the thermodynamic parameters of
activation for the reaction at 253 K.

5.

Bananas are somewhat radioactive due to the presence of substantial amounts of potassium.
Potassium-40 decays by two different paths:
40
40
(89.3%)
19 K 20 Ca
40
19

K 40
(10.7%)
18 Ar

The half-life for potassium decay is 1.3 109 years. Determine the rate constants for the
individual channels.

Please attempt the following questions. Answers will be posted


on the Chemistry 232 Website.
6.

The growth of a bacterial colony can be modeled as a first-order process in which the
probability of cell division is linear with respect to time such that dN dt , where dN is

the number of cells that divide in the time interval dt, and is a constant.
a) Use the preceding expression to show that the number of cells in the colony is given by
t
N N 0 e , where N is the number of cell colonies and N0 is the number of colonies
present at t = 0.
b) The generation time is the amount of time it takes for the number of cells to double.
Using the answer to part (a), derive an expression for the generation time.
c) In milk at 37C, the bacteria lactobacillus acidophilus has a generation time of about 75
min. Construct a plot of the acidophilus concentration as a function of time for time
intervals of 15, 30, 45, 60, 90, 120, and 150 minutes after a colony of size N0 is
introduced to a container of milk.

7.

You are performing an experiment using 3H (half-life = 4.5 103 days) labeled
phenylalanine in which the five aromatic hydrogens are labeled. To perform the experiment,
the initial activity cannot be lower than 10% of the initial activity when the sample was
received. How long after receiving the sample can you wait before performing the
experiment?

8.

For the reaction A- (aq) + H+ (aq) P, the rate constant has been found to be kr = 7.78 x
1014 L/(mol s) x e-9134/T. Calculate the thermodynamic parameters of activation at 30C.

9.

For the decomposition of acetaldehyde in the gas phase at 791 K, at an initial concentration
of 9.72 x 10-3 M, the half-life of the reaction is 328 seconds; when the concentration of
acetaldehyde is halved, the half-life increases by a factor of two.
a) What is the order of the decomposition of acetaldehyde?
b) Calculate the rate constant for the reaction.
c) Given that the rate of reaction increases by a factor of three when the temperature is
increased by 17 K, calculate the activation energy and the pre-exponential factor for the
reaction.

Answers
1.

For the Reaction

2 A + B 2 C + 3 D, the rate of reaction is written as follows

1 d [ A]
1 d [ B] 1 d [C ] 1 d [ D]

2 dt
1 dt
2 dt
3 dt
d [ A]
d [ B]

1.0 mol L1 s 1 ;
0.50 mol L1 s 1
dt
dt
d [C ]
d [ D]
1.0 mol L1 s 1 ;
1.50 mol L1 s 1
dt
dt
vr

2.

The reaction is first order with respect to N2O5.Hence we can write


a)
vr k[ N 2O5 ]
0.693
2.76 105 s 1
2.51104 s

t1/2

b) Using the integrated rate law


i)
P
ln kt
P0
P
ln 2.76 x 105 x 200 s 0.00552
P0
P

e 0.0552 0.994 P 0.994 x 500 Torr


P0
497 Torr

ii)
P
ln kt
P0
P
ln 2.76 105 6000 s 0.1656
P0
P

e 0.1656 0.847 P 0.847 500 Torr


P0

3.

424 Torr
We can use the integrated form of the Arrhenius equation with the assumption that the preexponential factor and Ea are both constant over the temperature range of interest.
k'
E
ln a 1 ' 1
T
T
R
k
Ea
0.018
1
ln
1

303K
8.314 J K 1mol 1 323K
0.0028

ln 6.43

Ea
3.096 103 K 1 3.300 103 K 1
8.314 J K 1mol 1

1.861 8.314 J K 1mol 1


Ea
2.044 104 K 1
Ea 75703J mol 1 75.7kJ mol 1

To calculate A, use either one of the rate constant/temperature data points according to the
Arrhenius equation.
E
ln k ln A a
RT
T 303 K
75703 J mol 1
k'
ln
30.05
8.314 J K 1mol 1 303 K
A
A
A
ln 30.05 e30.05 1.1247 1013
k'
k'
A 1.1247 1013 k ' 1.1247 1013 0.0028 mol L1s 1
3.149 1010 mol L1s 1
T 323 K

75703 J mol 1
k'
ln
287.190
8.314 J K 1mol 1 323 K
A
A
A
ln 28.19 e28.19 1.7495 1012
k
k
12
A 1.7495 10 k 1.7495 1012 0.018 mol L1s 1
3.149 1010 mol L1s 1

4.

Note since this is a unimolecular gas-phase reaction

Ea H RT

H 85900 J mol 1 8.314 J K 1mol 1 253K

83780 J mol 1
83.8 kJ mol 1
ek T S
A B e R
h

Ah
S R ln

ekBT
1.4 1014 s 1 6.626 1034 J s
1
1
8.314 J K mol ln
e 1.38 1023 J K 1 253K

8.314 J mol1 K 1 ln 9.767


18.9 J K 1mol 1

G H T S

83780 J mol 1 253 K x 18.9 J K 1mol 1


78998 J mol 1
79.0 kJ mol 1

Note what follows is a very crude interpretation of the thermodynamic parameters of

activation. The fact that the S is positive, means that the activated complex (transition

state) is associated with bond breaking and an increase in disorder. The H indicates
that the amount of energy that has been input into the bonds is quite a bit smaller than
either that of an N=N bond (~ 420 kJ mol -1) or an N-N bond (~ 160 kJ mol -1). This
indicates that the transition state contains some single-bond character!! A simple picture
may be as follows.
H3C

CH3
N

H3C

CH3

H3C
N

N
CH3

Activated Complex

Of course, this makes sense with respect to the fact that in order to rotate around the double
bond (i.e., to get from cis- to trans-) some lengthening of the bond must occur and there has
to be a rotation of the methyl groups about the double bond. Rotation will only occur with
significant bond lengthening or creation of single-bond character, hence, weakening the
bond.

5.

Since this is a branching reaction, we define kCa as the rate constant for the Ca production,
and kAr as the rate constant for Ar production. Finally, the total 1st order rate constant for K
decay is equal to the sum of kCa and kAr so that:
Ca kCa
k kCa k Ar and
Ar k Ar
Using the definition of the half-life, k is determined as follows:
ln 2
k
5.33 1010 yr 1
1.3 109 yr
Note that the yield of the reaction is defined as
kJ
k
J
J
kCa k Ar
k
kCa
k
; Ar Ar
k
k
Hence,
5.33 1010 yr 1 0.893 4.76 1010 yr 1
Ca

Ca k kCa

k Ar 5.33 1010 yr 1 0.107 5.70 1011 yr 1

6.

Integrate the expression of the number of bacteria in the colony with time.
N
t
dN
a)
N 0 dt
N0
ln N ln N 0 t
N
ln
t
N0
N
e t
N0

b) At the generation time, N = 2N0. Thus,


t
2N0 N0e gen
or
t
2 e gen
ln 2 t gen
ln 2

c)

t gen

The value of for tgen = 75 min can be found.


ln 2

75 min
0.00924 min 1

Hence,
t (min)
15
30
45
60
90
120
150

N/N0
1.148
1.319
1.515
1.741
2.297
3.031
4.000

Plot ln (N/N0) versus time

Plot ln (N/N0) versus time for the number of


bacteria in milk at 310 K
1.60
1.40

ln (N/No)

1.20
1.00
0.80
0.60
0.40

y = 9.246E-03x - 5.419E-04
R = 1.000E+00

0.20
0.00
0

20

40

60

80

100

120

140

t / min

The slope of the line is in agreement with part (b) of this problem.
7.

The rate constant can be found from the half-life:


ln2
0.693
k

t1/2 4.5 103 day

k 1.54 104 day 1


Hence,

8.

A
ln
kt
A
0

1
t
ln 0.10
1.540 104 day 1

t 1.50 104 days 41 years


The activation energy can be calculated form the Arrhenius type expression for kr.

160

Ea
9136 K 1 Ea 9136 K 1 8.314 J K 1mol 1
R
75957 J mol 1

Ea H RT

H 75957 J mol 1 8.314 J K 1mol 1 303K

73438 J mol 1
73.4 kJ mol 1
A

RT ek BT S R

e
po
h

po
Ah
S R ln

RT ek BT

8.314 J K mol

1.00 105 Pa m3

14
1 1
34
1000 L 7.78 10 L mol s 6.626 10 J s
ln
8.314 Pa mol 1 K 1 303K

e 1.38 10 23 J K 1 303 K

8.314 J mol 1 K 1 ln 1.799


4.88 J K 1mol 1

G H T S

73438 J mol 1 303 K x 4.88 J K 1mol 1


71959 J mol 1

9.
a)

72.0 kJ mol 1
Note the half life is dependent on the initial concentration; the rate law is a higher order
then first order.
For a second order process,
1
t1
2
k CH 3CO o

we can clearly see that if the concentration of the starting material is increased by 2, the
half-life will decrease by 2. Hence, the rate law for the reaction is written
2
vr k CH 3CO

t1
2

b)
k

1
k CH 3CO o

1
1

0.313M 1s 1
3
t 1 CH 3CO o 328s 9.72 10 M
2

k Ea 1 1
ln 2

R T2 T1
k1
Ea
1
1
ln 3

1
1
8.314 JK mol 808K 791K
1.099 8.314 JK 1mol 1
Ea 343516 Jmol 1 344kJmol 1
5
1
2.660 10 K

10.