CHEE 310: Assignment 1 Solutions

Date Released: Jan. 13, 2009

Date Due: Beginning of class Jan. 20, 2009

Problem 1 (5 marks): The half-life for the radioactive decay of 14C is 5730 years. A sample of a piece
of wood from an archeological excavation possessed wood that had only 65% of the 14C found in living
trees. What is the estimated age of the sample?

Problem 1 Solution: The decay of radioactive isotopes is well described by a first-order decomposition.
[14 C] =[14 C]0 exp[−kt]
t1/ 2 occurs when [14 C] = 0.5[14 C]0 (2 marks)
ln2
t1/ 2 =
k
First, determine the rate constant k for the decomposition using the given half-life.
ln2 ln2
k= = = 1.2 x 10−4 yrs -1 (1 mark)
t1/ 2 5730 yrs
€
Now, determine the actual age of the sample using the k calculated and the fraction of 14C remaining.
[14 C] =[14 C]0 exp[−kt]
€ 1  [14 C]  1  1 
t = ln 14 0  = −4 −1
ln  = 3560 yrs (2 marks)
k  [ C]  1.21x10 yrs  0.65 
€ ∴the sample is approximately 3600 years old based on the decay of 14C.

Problem 2 (10 marks): The second order rate constant for the following reaction is 0.22 L mol-1 s-1 for
€ the following reaction: CH 3COOEt(aq) + NaOH(aq) → CH 3COONa(aq) + EtOH(aq) .
The initial concentrations of sodium hydroxide and ethyl acetate are [NaOH]0 = 0.25 mol L-1 and
[CH3COOEt]0 = 0.50 mol L-1 (note the typographical error in the original problem – the solution is
shown for the particular conditions states with the acetate in excess) What is the concentration of ethyl
€ 10 s, b) 10 min?
acetate after a)

Problem 2 Solution: For a second order reaction with different initial concentrations, the following
second order rate expression can be used as derived in class (with A = CH3COOEt and B = NaOH).
1  [A][B]0 
ln  = kt
[A]0 − [B]0  [A]0 [B] 
[A] [A]0
= exp{kt ([A]0 − [B]0 )} (2 marks)
[B] [B]0
€ [A] 0.50  L  mol 
a) When t = 10 seconds, = exp0.22 10s 0.25  = 3.47 (1 mark)
[B] 0.25  mol ⋅ s  L 
€ To determine the ethyl acetate concentration, the extent of the reaction x must be determined.

€
 [A]0 − x
= 3.47
[B]0 − x
3.47[B]0 − 3.47x = [A]0 − x
3.47[B]0 − [A]0 3.47 ⋅ 0.25mol ⋅ L−1 − 0.50mol ⋅ L−1
x= =
2.47 2.47
−1
x = 0.15 mol ⋅ L
(2 marks for determining extent of reaction)
The concentration of ethyl acetate after 10 sec is thus [A] = [A]0 – x = 0.35 mol L-1. (1 mark)
€ 
[A] 0.50 L  mol  14
b) When t = 10 min, = exp0.22 600s 0.25  = 4.3x10 (1 mark)
[B] 0.25  mol ⋅ s  L 
To determine the ethyl acetate concentration, the extent of the reaction x must be determined.
[A]0 − x
= 4.33x1014
[B]0 − x
€
4.3x10 [B]0 − 4.3x1014 x = [A]0 − x
14

4.3x1014 [B]0 − [A]0 4.3x1014 ⋅ 0.25mol ⋅ L−1 − 0.50mol ⋅ L−1

x= =
4.3x1014 4.3x1014
x = 0.25 mol ⋅ L−1
(2 marks for determining extent of reaction)
The concentration of ethyl acetate after 10 min is thus [A] = [A]0 – x = 0.25 mol L-1. (1 mark)
€ Problem 3 (10 marks): The composition of a liquid phase reaction 2A → B was followed as a function
of time using a spectroscopic method with the following results for the appearance of product B:
time/min 0 10 20 30 40 ∞
-1
[B]/mol L 0 0.09 0.15€ 0.20 0.23 0.31

Determine the order of the reaction and the value of the rate constant.

Problem 3 Solution: First, the concentration of A at any time must be determined to test for the rate
law. Based on the stoichiometry, [A] = [A]0-2x where x is the extent of the reaction. Also, the extent of
reaction x is simply the concentration of B, [B]. The initial concentration of A, [A]0 can be calculated
from the infinite time limit and the stoichiometry of the reaction. At t = ∞, there should be no A left and
[B]∞ = 0.5[A]0. Thus, [A]0 = 2[B]∞ = 0.62 mol L-1. (2 marks)

The concentration of A is tabulated below from the given data. (5 marks)

time (min) [B] (mol L-1) [A] (mol L-1)

0 0 0.62
10 0.09 0.44
20 0.15 0.32
30 0.2 0.22
40 0.23 0.16
 Attempt a first-order fit to the data with respect to [A] which should be a linear relationship of
ln{[A]/[A]0} versus time t if the reaction is indeed first order. Such a plot should have a slope of –k.

The plot is linear, which suggests the reaction is first

order with respect to A. (2 marks)
The slope will provide the rate constant, which is given as 0.034 min-1. (1 mark)

Problem 4 (10 marks): Cyclopropane isomerizes into propene when heated to 500 oC in the gas phase.

The extent of the reaction for various initial pressures of cyclopropane p0 was followed by gas
chromatography by permitting the reactions to proceed for a time with various initial pressures and then
measuring the partial pressure of cyclopropane, pcyclopropane, of the system. Determine the order of the
reaction and the rate constant.

Time (s) 100 200 100 200 100 200

p0 (atm) 0.263 0.263 0.526 0.526 0.789 0.789
pcyclopropane (atm) 0.245 0.228 0.491 0.456 0.736 0.684

Problem 4 Solution: The pressure is directly proportional to the concentration of the gas: pV = nRT .
Since there is no change in the total number of moles, corrections to the total pressure are not necessary.
We can first test whether the reaction is first order with respect to cyclopropane.
Since the pressure is proportional to the concentration, the pressure of cyclopropane can be written as
follows: pcyclopropane = p0e−kt . (2 marks) €

With the given data, we can test whether the data corresponds to a first order rate law by noting that
 
€ k = 1 ln p0
 should be constant.
t  pcyclopropane 
Time (s) 100 200 100 200 100 200
p0 (atm) 0.263 0.263 0.526 0.526 0.789 0.789
pcyclopropane (atm) 0.245 0.228 0.491 0.456 0.736 0.684
€
(1/t)ln(p0/pcyclopropane) 0.00071 0.00071 0.00069 0.00071 0.00070 0.00071

1  p0 
Note that ln  is nearly constant so it is likely that the reaction is first order (2 marks).
t  pcyclopropane 
The rate constant k is approximately 7.1 x 10-4 s-1 (1 mark).

€
Alternate Solution to Problem 4: The method of initial rates could also have been applied although it
involves a little more work. First, the partial pressure units could be converted to concentration units
using the ideal gas law (temperature is given in the problem). The table below shows the converted
data.
Time (s) Cc (M) when Pc,0 = 0.263 atm Cc (M) when Pc,0 = 0.526 atm Cc (M) when Pc,0 = 0.789 atm
0 4.09 x 10-5 8.18 x 10-5 1.23 x 10-4
100 3.81 x 10-5 7.64 x 10-5 1.15 x 10-4
200 3.55 x 10-5 7.10 x 10-5 1.06 x 10-4

The concentration profiles provide the initial rates of disappearance of cyclopropane from the initial
slopes, Rc,0. The appropriate plot of log Rc,0 versus log Cc,0 will give a straight line with the order of the
reaction from the slope and the rate constant can be extracted from the intercept. The plot is shown
below. (2 marks for converting data into appropriate form).

Cc,0 (M) Rc,0 (M⋅s-1) log Cc,0 log Rc,0

4.09E-05 2.72E-08 -4.39 -7.56
8.18E-05 5.44E-08 -4.09 -7.26
1.23E-04 8.17E-08 -3.91 -7.09

From the plot, the slope gives the reaction as first order (2 marks) and the rate constant k is 6.8 x 10-4 s-1
(1 mark), in good agreement with the previous method.