KINETICS
RATE LAWS, REACTION ORDERS AND HALF LIFE
1. The decomposition of NOCl gas has an E a of 1.00 x 102 kJ/mol and k of 0.286
L·mol-1·s-1 at 500K. Determine the rate constant at 450K. (4)
In k1/k2 = Ea/R (1/T2 – 1/T1)
R = 8.314 Jmol-1K-1
In 0.286 L·mol-1·s-1/k2 = 1.00 x 102 kJ/mol/8.314 Jmol-1K-1 (1/450K – 1/500K)
(3 marks)
In k2 = In (0.286 L·mol-1·s-1) – [1.00 x 102 kJ/mol/8.314 Jmol-1K-1 (1/450K –
1/500K)]
In k2 = -3.924 L·mol-1·s-1
k2 = 0.0197 L·mol-1·s-1
2. Consider the kinetic study data obtained for the reaction below:
2 N2O5 => 4NO2 + O2, by graphical methods, determine if
the reaction is 1st or 2nd order. NB: The two graphs must be plotted on the
graphs paper. Show all the data that you used to plot the graph.
(9)
Time (s) [N2O5] (mol/L)
0 0.0365
600 0.0274
1200 0.0206
1800 0.0157
2400 0.0117
3000 0.00860
3600 0.00640
Time (s) [N2O5] (mol/L) In [N2O5] 1/[N2O5]
0 0.0365 -3.31 27.39
600 0.0274 -3.60 36.50
1200 0.0206 -3.88 48.54
1800 0.0157 -4.15 63.69
2400 0.0117 -4.45 85.47
3000 0.00860 -4.75 116.28
3600 0.00640 -5.05 156.25
Data (2 marks)
The In [N2O5] vs time graph is a linear curve and therefore the reaction follows 1 st
order kinetics
3 marks for each graph plotted
3. The initial concentration of a reactant in a zero order reaction is 0.75 M with a
rate constant, k, of 0.015 M·min-1
a. What will be the concentration after 900 s? (2)
900 s/1 x 1 min/60 s = 15 min (1)
[A]t = - kt + [A]0
= - (0.015 M/min) (15 min) + 0.75 M
= 0.525 M (1)
b. How long will it take for the concentration to be reduced to 0.06 M? (3)
t= ?
[A]0 = 0.75 M k = 0.015 M·min-1
[A]t = - kt + [A]0
0.06 M = - (0.015 M/min) (t) + 0.75 M
0.06 M -0.75 M = - (0.015 M/min) (t)
0.69 M/-0.015 M = t
t = 46 mins
4. Determine order of the reaction and the initial concentration of a reactant that
took 4.7 mins to reach a final concentration of 0.15 M with a rate constant, k, of
0.0025 M-1·s-1
(4)
General formula for order determination is M 1-n ·t-1, where n is the order of the
reaction.
the units of k is s-1, therefore, it is second order.
Convert time from min to seconds
4.7 min/1 x 60 s/1 min = 282 s
1/[A]t = kt + 1/[A]0
1/0.15 M = 0.0025 M-1·s-1 (282 s) + 1/[A]0
6.667 = 0.705 + 1/[A]0
5.962 = 1/[A]0
[A]0 = 0.1677 M
5. Sulfuryl chloride, SO2Cl2, decomposes when heated according to the reaction
below:
SO2Cl2 (g) → SO2 (g) + Cl2 (g)
In an experiment, the initial concentration of SO 2Cl2 was 0.0248 mol/L. if the rate
constant is 2.2 x 10-5 s-1, determine the concentration of SO2Cl2 after 2.0 h. (3)
The units for k is s-1, therefore it is first order.
In [A]t = - kt + In [A]0
In [A]t = - 2.2 x 10-5 s-1 x 172800 s + In (0.0248 M)
[SO2Cl2] = 0.02117 M
6. Determine the half life of a reaction with a rate constant, k, of 0.0045 s -1 (4)
7. Which of the following is statements is false? (1)
a. Half-life of a 1st order reaction does not depend on the concentration of the
reactants.
b. The half-life of a zero order reaction is constant.
c. The rate constant, k, is inversely proportional to the half-life of a 2 nd order
reaction.
d. The half-life of a zero order reaction is directly proportional to the
concentration of the reactants
8. Which of the following plots correspond to a 1st order reaction? (2)
a. [A] vs t, -k
b. In [A] vs t, -k
c. 1/[A] vs t, +k
d. [A] vs t, +k
e. In [A] vs t, +k
9. The decomposition of dinitrogen pentoxide has the rate constant, k, of 2.8 x 10 -3
s-1 at 50ºC. The initial concentration of N2O5 is 1.58 M.
a. Calculate the mass of N2O5 consumed after 6 min if the volume of the reaction
vessel is 2000 mL (6)
The units for k is s-1, therefore the reaction is first order
Convert time to seconds
6 min/1 x 60 s/1 = 360 s
Convert volume to Litres
2000 mL/1 x 1L/1000 mL = 2.00L
In [A]t = - kt + In [A]0
In [A]t = - 2.8 x 10-3 s-1 x 360 s + In (1.58 M)
[A]t = 0.576 M
Molar mass of N2O5 is 108.01 g/mol
Mass of N2O5 consumed = (1.58 M – 0.576 M) x 2.00L x 108.01 g/mol
= 216.7g of N2O5
b. Determine the half life of the reaction (2)
t1/2 = In 2/k
t1/2 = 0.693/ 2.8 x 10-3 s-1
= 247.5 s
10. Which of the following could represent the units of the rate constant, k, for a
reaction that is 3rd order overall?
a. M2·s-1
b. M-2·min-1
c. M1·days-1
d. hr-1
11. In basic solution, ClO2 reacts to give ClO3- and ClO2- ions according to the
reaction:
2ClO2(aq) + 2OH-(aq) → ClO3-(aq) + ClO2-(aq) + H2O(l)
The following experiments were conducted and for each, the initial rate of the
reaction of ClO2 was determined.
Experiment Initial concentrations (mol/L) Initial rate (mol·L-1s-1)
[ClO2] [OH-]
1 0.060 0.030 0.0248
2 0.020 0.030 0.00276
3 0.020 0.090 0.00828
Determine the rate law for the reaction (6)
R1/R2 = [ClO2]1x/[ClO2]2x
0.0248/0.00276 = 0.060x/0.020x
32 = 3x
x=2
R3/R2 = [OH-]3y/[OH-]2y
0.00828/0.00276 = 0.090y/0.03y
3 = 3x
y=1
Therefore, Rate = k[OH-][ClO2]2
