CHEM2056 Rates and rate laws

Formative Workshop Week 9, 2018 worked solutions

1 For the reaction below, it has been determined that the reaction order for BrO3- is one, the
reaction order for Br- is one and the reaction order for H+ is two. In an experiment where all the
reagent concentrations were 0.2 M it was found that the reaction rate for disappearance of
BrO3- was 1.15×10-3 mol L-1 s-1.

BrO3-(aq) + 5Br-(aq) + 6H+(aq) → 3Br2(l) + 3H2O(l)

a. In this experiment, what is the rate of disappearance of Br- ?

R = -1/5 d[Br-]/dt; so -d[Br-]/dt = 5 R = 5.75×10-3 mol L-1 s-1

(or d[Br-]/dt = -5 R = -5.75×10-3 mol L-1 s-1)

b. Determine the rate constant for this reaction.

R = 1.15×10-3 mol L-1 s-1 = k [BrO3-][ Br-][ H+]2 = k (0.2 M)(0.2 M)(0.2 M)2

So k = 7.2×10-1 M-3 s-1 (or mol-3 L3 s-1)

c. What is the effect on the rate constant and on the rate of reaction of increasing all the
reagent concentrations to 0.4 M?

None for rate constant

R = 7.2×10-1 M-3 s-1 (0.4 M)(0.4 M)(0.4 M)2 = 0.0184 mol L-1 s-1
So R becomes 16 times greater (eg. doubling 4 times)

2 The decomposition of nitrogen dioxide in the gas phase occurs according to the following
equation at 50 ºC:
NO2(g)  ½ O2(g) + NO(g)

The rate law for the reaction has been found to be R = 0.543 M–1 s–1[NO2]2 at 50 ºC.

a. Given an initial concentration of 0.0240 M of NO2, what would the half-life for the reaction
be?

t1/2 = 1/(k[NO2]) = 1/(0.543 M–1 s–1 × 0.024 M) = 76.7 s

b. How much NO2 would be left after 50.0 seconds if the starting concentration of NO2 was
0.0240 M?

1/[NO2] = 1/[NO2]0 + kt = 1/0.024 M + 0.543 M–1 s–1 × 50 s; [NO2] = 0.0145 M

 c. Find the relationship between the total pressure, the fraction of molecules that have reacted and
the initial pressure.

NO2(g)  ½ O2(g) + NO(g)

Initial n 0 0
Change -nα ½ nα nα
Overall n - nα ½ nα nα

Total = n + ½ nα = n(1 + ½ α) and therefore p = (1 + ½ α) p0

d. If the initial concentration of NO2 is 0.0240 M, what would be the total pressure in units of atm
at the start of the reaction, after 50.0 seconds and at the end of the reaction? Assume all species
behave as ideal gasses.

Start: α = 0, p = p0 = 0.0240 mol L-1 × 0.08206 atm L mol–1 K–1 × 323 K = 0.636 atm

After 50 seconds: α = (0.0240 mol L-1 - 0.0145 mol L-1)/ 0.0240 mol L-1 = 0.396

p = (1 + ½ α) p0 = 1.198 × 0.636 atm = 0.762 atm

At the end: α = 1; p = (1 + ½ α) p0 = 1.5 × 0.636 atm = 0.945 atm

3 The rate law for the reaction below is R = 0.11 M-1 s-1[CH3COOC2H5][OH-].

CH3COOC2H5 (aq) + OH- (aq)  CH3CO2- (aq) + CH3CH2OH (aq)

0.2 – 0.1 0.5 – 0.1 0.1 0.1

How long would it take for the ester to half its concentration if the starting concentrations were
[CH3COOC2H5]0 = 0.20 M and [OH-]0 = 0.50 M?

1  [B]/[B]o  1  0.4/0.5 
t ln   ln    14s
k ([B]o  [A]o )  [A] / [A]o  0.11M s (0.5M-0.2M)  0.1/0.2 
-1 -1