I.

Free-Response Questions for Kinetics

1. The following reaction was studied:

NO2(g) + CO(g) Æ NO(g) + CO2(g) ΔH° = –339 kJ mol-1

The results obtained from the experiment at 35°C are as follows:

Time (s) [NO2] (mol L-1)

0 0.500
1200 0.444
3000 0.381
4500 0.340
9000 0.250
18000 0.174

(a) Determine the rate law of the reaction.

(b) Calculate the rate constant k at the temperature the experiment was conducted.

(c) Calculate the half-life of the reaction.

(d) Calculate the concentration of NO2 3.7 × 103 seconds after the reaction was initiated.

(e) The experiment was repeated at different temperatures. The results obtained are as follows:

Temperature (°C) Rate constant, k

20 2.0 × 10-5
30 7.3 × 10-5
40 2.7 × 10-4
50 9.1 × 10-4
60 2.9 × 10-3

(i) The chemist intends to the use the data to determine the activation energy. He constructs an Arrhenius plot:
y-axis

x-axis

Label the x and y axis and include units if necessary.

II. Answers and Explanations to Free-Response Questions

1
1. The following reaction was studied:

NO2(g) + CO(g) Æ NO(g) + CO2(g) ΔH° = –339 kJ mol-1

The results obtained from the experiment at 35°C are as follows:

Time (s) [NO2] (mol L-1)

0 0.500
1200 0.444
3000 0.381
4500 0.340
9000 0.250
18000 0.174

(a) Determine the rate law of the reaction.

From the results table, one can conclude that the reaction rate is dependent on the concentration of NO2 and not
CO. Thus, the reaction must be zero order, first order, or second order with respect to NO2. By analyzing the
graphs of [NO2], ln[NO2], and 1/[NO2] versus t, we can determine the reaction order:

Time (s) [NO2] (mol L-1) ln[NO2] 1/[NO2] (L mol-1)

0 0.500 –0.693 2.00
1200 0.444 –0.812 2.25
3000 0.381 –0.965 2.62
4500 0.340 –1.08 2.94
9000 0.250 –1.39 4.00
18000 0.174 –1.75 5.75

0.400
[NO 2 ]

0.200
0.000
0 5000 10000 15000
1/[NO2 ]

Time (s) 4.00

2.00
-0.693 0 5000 10000 15000
ln[NO2 ]

-1.193
-1.693 Time (s)
-2.193
0 5000 10000 15000

Time (s)

The graphs reveal that the line of 1/[NO2] versus t is a linear line while the graph of [NO2] and ln[NO2] are not
linear. Thus, the reaction is in second order overall and is also second order with respect to NO2.

The rate law is thus written as follows:

Rate = k[NO 2 ]2
(b) Calculate the rate constant k at the temperature the experiment was conducted.

2
 The rate constant k is the absolute value of the slope of the graph with a linear line. Since we discovered in part
(a) that the reaction is in second order, the slope of the graph of 1/[NO2] versus t is calculated as follows:

Δy
k=
Δx
L L
5.75 − 2.00
k= mol mol
18000 s − 0 s

k = 2.08 × 10 −4 L mol -1 s -1

Alternatively, it can be calculated using the second-order integrated rate law:

1 1
= kt +
[ NO 2 ] [ NO 2 ]0
1 1
−
[ NO 2 ] [ NO 2 ]0
=k
t
L L
−
0.381 mol 0.500 mol = k
3000 s

k = 2.08 × 10 −4 L mol -1 s -1
Although the alternative method will allow you to arrive at the same answer, using the former method
(calculation of the slope) is more accurate because it takes the average of all the concentrations at all times. The
second method requires calculation of the concentration of [NO2] at a specific time, leaving a margin for error.
An accurate calculation of the rate constant using the second method would require averaging the values of k for
all six concentrations in the experiment.

(c) Calculate the half-life of the reaction.

The half-life of a second-order reaction is calculated as follows:

1
t1 =
2
k[ NO 2 ]0
1
t1 =
⎛ −4 L ⎞⎛ mol ⎞
2
⎜ 2.08 × 10 ⎟⎜ 0.500 ⎟
⎝ mol ⋅ s ⎠⎝ L ⎠

t 1 = 9615 seconds
2

(d) Calculate the concentration of NO2 3.7 × 103 seconds after the reaction was initiated.

Calculation of [NO2]t can be accomplished using the integrated rate law:

3
 1 1
= kt +
[ NO 2 ]t [ NO 2 ]0
1 ⎛ L ⎞ L
= ⎜ 2.08 × 10 − 4 ⎟(3700 s ) +
[ NO 2 ] ⎝ mol ⋅ s ⎠ 0.500 mol
1 L
= 2.77
[ NO 2 ] mol

[ NO 2 ] = 0.361 mol L-1

(e) The experiment was repeated at different temperatures. The results obtained are as follows:

Temperature (°C) Rate constant, k

20 2.0 × 10-5
30 7.3 × 10-5
40 2.7 × 10-4
50 9.1 × 10-4
60 2.9 × 10-3

(i) The chemist intends to the use the data to determine the activation energy. He constructs an Arrhenius plot:
ln(k)

1/T (K)

Label the x and y axis and include units if necessary.

An Arrhenius plot is always a plot of the natural logarithm of k versus the reciprocal of the temperature in
Kelvin.