Suggested Solutions to Tutorial 6 Reaction Kinetics

Self-Check
Question 1

(a)

rate equation /
rate law

The rate equation (or rate law) is a mathematical equation that shows how the rate
of reaction is dependent on the concentration of reactants at a particular
temperature. It relates the rate of the reaction to the concentration of reactants
raised to the appropriate power OR For a reaction such as A + B
products,
m
n
the rate equation is of the form: rate = k[A] [B] .

(b)

rate constant

The rate constant, k, is a constant of proportionality in the rate equation. It is

constant for a particular reaction at a given temperature

(c)

order of
reaction

The order of reaction with respect to a particular reactant is the power to which
the concentration of that reactant is raised in the rate equation.
The overall order of reaction is the sum of the exponents in the rate equation. (If
m
n
rate = k[A] [B] , overall order of reaction = m + n)

(d)

half-life

The half-life of a reaction is the time taken for the concentration of a reactant to fall
to half its initial value.

(e)

ratedetermining
step

The rate-determining step is the slowest step in a sequence of elementary reactions

and it determines the rate at which products are formed in a chemical reaction.

Question 2
rate equation

(a) rate = k[H2O2]

units of k

(b) rate = k [H2][O2]

mol dm s

(c) rate = k[NO2]

1

mol dm s

(d) rate = k

mol dm s

Question 3
Order of
reaction

(i) Graph of [reactant] vs t

[rxt]/ mol dm

(ii) Graph of [product] vs t

[pdt]/ mol dm

C0

C
C

(iii) Graph of rate vs [reactant]

3

rate/ mol dm s

zero

C0
C0

Time/s
[rxt]/ mol dm

Time/s

[pdt]/ mol dm

C
C

C0

[rxt]/ mol dm
3

rate/ mol dm s

first

C0
C0

Time/s

Time/s
[rxt]/ mol dm

[pdt]/ mol dm

C
C

C0

[rxt]/ mol dm
3

rate/ mol dm s

second

C0
C0

Time/s

Time/s
1

[rxt]/ mol dm

Suggested Solutions to Tutorial 6 Reaction Kinetics

Rate = k[A]2[B], original rate = R = k[A]02[B]0 where [X]0 = initial [X]

Question 4

(a)
change

double partial
pressures of A and B

new rate

8R

(b)

(c)

double partial
pressure of A

(d)

double volume of
reacting vessel

4R

reason

doubling partial
pressure doubling
concentration

doubling partial
pressure doubling
concentration

working

new rate
2
= k(2[A]0) (2[B]0)
= 8R

new rate
2
= k(2[A]0) ([B]0)
= 4R

double total pressure

with inert gas

doubling volume
halving concentration

partial pressure of
reactants remain
constant = no change

new rate
2
= k([A]0) ([B]0)
= R

new rate
2
= k([A]0) ([B]0)
=R

Question 5
(i)

Half-life (t1/2) of the reaction is constant.

(ii)

Draw the tangent to the graph at point P (as shown in Fig. 1a).
Find the gradient of the tangent, g1 =

The rate of decrease in concentration of reactant at t = x seconds is g1.

(iii) Draw tangents to the graph at 6 or more different [reactant].
Find the gradients as described in (b). Rate at each [reactant] = gradient.
Plot [reactant] against rate to obtain Fig. 1b.
[reactant] / mol dm
[reactant] / mol dm

C1

P
o

g1
C2

t1

time / s
t2

rate / mol dm

g1

Standard Questions
Question 1
(i)

Comparing experiments I and II, when initial [sucrose] was increased 1.5 times, initial rate
increased 1.5 times rate [sucrose], i.e. reaction is first order with respect to sucrose
Comparing experiments I and III, when initial [HCl] was doubled, initial rate also doubled
rate [HCl], i.e. reaction is first order with respect to HCl
Hence the rate equation is: rate = k[sucrose][HCl].
= 2.40 mol 1 dm3 s 1

Using data from experiment I, k =

Suggested Solutions to Tutorial 6 Reaction Kinetics

(ii)

0.048 = 2.40(0.25)(y)

(iii)

rate = k[sucrose][HCl]

y = 0.08

Since HCl is a catalyst in the reaction, its concentration is effectively constant during the
reaction. The rate equation can then be simplified to: rate = k[sucrose], where k = k[HCl].
The reaction becomes a pseudo first-order reaction with constant half-life:

For experiment II, [HCl] is the same as experiment I.

Hence, t1/2 of sucrose in experiment II = t1/2 of sucrose in experiment I = 3.0 s
For experiment III, [HCl] is double that of experiment I.
Hence, t1/2 of sucrose in experiment III

1.5 s

Question 2
General Strategy
1. Identify which method to use:
(i) continuous method if change in physical property

[reactant] (or [product]) over time

(ii) sampling
2. Perform the experiment and collect data over time.
3. Plot a graph of data against time.
4. Instantaneous rate may be found by drawing a tangent to the curve at that particular time and
finding its gradient, g1. Rate = g1 if data [reactant] while rate = g1 if data [product].
(a)

5C2O42 (aq) + 2MnO4 (aq) + 16H+(aq)

2Mn2+(aq) + 10CO2(g) + 8H2O(l)

Continuous Method
1. MnO4 is violet. Since colour intensity [MnO4 ], the change in the colour intensity of
MnO4 over time may be used to follow the rate of reaction.

2. The colour intensity may be measured by the use of a colorimeter and the readings are
taken at regular time intervals.
3. Colour intensity is then plotted against time.
4. Instantaneous rate is found by drawing a tangent to the curve and finding its gradient g1,
where rate = g1.
(Alternatively, the volume of CO2 evolved may also be measured and monitored over time.)
Sampling
1. The reactants are mixed and the stopwatch is started simultaneously.
2. Aliquots of the reactant mixture are withdrawn and quenched at regular time intervals (e.g.
two-minute interval) using excess KI(aq). I reacts with MnO4 instantaneously and
quantitatively to form I2.

3. The amount of I2 formed in each aliquot is found by titrating against standard Na2S2O3(aq).
4. volume Na2S2O3(aq) amount of I2 formed amount of unreacted MnO4 [MnO4 ]
remaining (since each aliquot has the same volume). Hence a graph of volume
Na2S2O3(aq) against time is plotted, which is similar to a graph of [MnO4 ] against time.

Suggested Solutions to Tutorial 6 Reaction Kinetics

5. Instantaneous rate is found by drawing a tangent to the curve and finding its gradient g1,
where rate = g1
(b)

2H2O2(aq)

2H2O(l) + O2(g)

1. Since a gas is evolved, the change in volume of oxygen evolved over time may be
monitored.
2. Set up the apparatus as shown and measure the
volume of gas collected in the syringe at regular
time intervals.
3. Since volume of O2(g) is directly proportional to
the concentration of oxygen evolved, a graph of
volume of O2(g) against time is plotted and it is
similar to graph of [O2] against time.
4. Instantaneous rate is found by drawing a
tangent to the curve and finding its gradient g1,
where rate = g1.

H2O2(aq)

(Alternatively, withdraw aliquots of the reaction mixture at regular time intervals and quench
with a large volume of cold water. Then titrate the quenched mixtures with standard acidified
KMnO4.)
(c)

CH3CHO(g)

CH4(g) + CO(g)

1. A continuous method is used. The change in total pressure, pT, with time is monitored.
2. Let the initial partial pressure of CH3CHO be pO, and the partial pressures of CH3CHO and
CH4 at time t be x and y respectively.
Then x = pO y and partial pressure of carbon monoxide at time t = y.
pT = sum of all partial pressures = x + y + y = (pO y) + 2y = pO + y
y = pT pO and x = pO (pT pO ) = 2pO pT
3. The total pressure, pT, of the reaction mixture initially (containing CH3CHO at pressure pO)
is measured at regular time intervals using a pressure gauge.
4. Since partial pressure of CH3CHO [CH3CHO], a graph of partial pressure of CH3CHO
(i.e. 2pO pT) is plotted against time. This is similar to plotting a graph of [CH3CHO]
against time.
5. Instantaneous rate is found by drawing a tangent to the curve and finding its gradient g1,
where rate = g1.
Question 3

II
III

Note: The rate of change of [H2O2] in experiment II is the same as that in the original experiment
since the concentration of H2O2 is the same. However, the rate of change of volume of O2 in
experiment II is twice as fast as that in the original experiment.
4

Suggested Solutions to Tutorial 6 Reaction Kinetics

Question 4
(a)

Continuous Method
1. The reactants (i.e. ester and alkali) are colourless while the product, 4-nitrophenoxide ion,
is yellow. Since colour intensity [4-nitrophenoxide], the change in the colour intensity of
4-nitrophenoxide ion over time may be used to follow the rate of reaction.
2. The colour intensity may be measured by the use of a colorimeter and the readings are
taken at regular time intervals.
3. Colour intensity is then plotted against time.
4. Instantaneous rate is found by drawing a tangent to the curve and finding its gradient g1,
where rate = g1.

(b)

[4-nitrophenyl ethanoate] / mol dm

run B: [OH ] = 0.40 mol dm

run A: [OH ] = 0.20 mol dm

(i)

t1/2

t'1/2

11 min

11 min

time / min

For run A, initial rate =

= 2.50 x 105 mol dm3 min1 (3 s.f.)
For run B, initial rate =
= 5.00 x 105 mol dm3 min1 (3 s.f.)

(ii)

rate = k[ester]a[OH]b

Since 2 = 2b, b = 1. Thus, the reaction is first order with respect to OH.
(iii)

From the curve of run B, t1/2 = t1/2 = 11 min, so half-life is constant.

Thus, the reaction is first order with respect to ester.

(iv)

rate = k[ester][OH]

(v)

From run A, 2.50 x 105 = k(0.0010)(0.20) k = 0.125 mol1 dm3 min1

(vi)

[OH] is

times as high as [ester], so the reaction follows pseudo

first-order kinetics. Thus, rate = k[ester], where k = k[OH] and t1/2 = 11 min.
5

Suggested Solutions to Tutorial 6 Reaction Kinetics

k
(c)

mol1 dm3 min1

Step 1 is the rate-determining step. Since the reaction is first order with respect to ester and
with respect to OH, the rate-determining step must be a bimolecular elementary reaction
between 4-nitrophenyl ethanoate and OH.

Question 5
(i)
rate = k[CH3COCH3][H+]; second order
(ii)

Mechanism A fits the observed kinetic data. The slow step, and also the rate-determining step
in the proposed mechanism, is a bimolecular elementary reaction between propanone and the
acid. The rate equation for this reaction is of the form: rate = k[CH3COCH3][H+], which is
similar to the experimentally determined rate equation. The reaction is zero order with respect
to iodine, so iodine is only involved in the fast step (which is not rate-determining).
On the other hand, the rate-determining step in mechanism B involves a bimolecular
elementary reaction between propanone and iodine. The rate equation is of the form:
rate = k[CH3COCH3][I2], which is dissimilar to the experimentally determined rate equation.
Since the rate is found to be independent of [I2], mechanism B is inconsistent with the
observed kinetic data.

(iii)

If the reaction between propanone and bromine proceeds by a similar mechanism, bromine is
not involved in the rate-determining step of the reaction mechanism. The reaction is therefore
zero order with respect to bromine. Consequently, the rate of the reaction is expected to be
identical to that of the reaction between propanone and iodine under the same experimental
conditions.

Question 6
(a)

The given reaction is an autocatalytic reaction with the H+ ions, produced from the dissociation
of CH3CO2H, acting as the autocatalyst.
Initially, the reaction is slow as there is no catalyst.
The reaction rate then increases as the H+ ions produced act as the catalyst.
Towards the end of the reaction, the concentrations of the reactants are very low, so the
reaction rate decreases even though there is an adequate supply of catalyst.

(b)

Platinum acts as a heterogeneous catalyst in the decomposition of NH3 into N2 and H2.
At very low pressures, the active sites on the catalyst surface are not saturated with ammonia
molecules. Hence, the rate of decomposition of ammonia only depends on the partial pressure
of ammonia and the reaction is first order with respect to ammonia.
At moderate or high pressures, most, if not all, of the active sites present on the platinum
surface are taken up by ammonia molecules.
Consequently, any increase in the partial pressure of ammonia has no effect on the rate of
decomposition. The reaction is zero order with respect to ammonia. In this case, the limiting
factor is the availability of active sites for the decomposition reaction.

(c)

A catalyst increases the rate of a reaction by providing an alternative reaction pathway of

lower activation energy.
energy

Ea
Ea
reactants
Ea: activation energy of uncatalysed reaction
Ea: activation energy of catalysed reaction
6

products

Suggested Solutions to Tutorial 6 Reaction Kinetics

progress of reaction
(reaction coordinates)

In the catalysed reaction, since the activation energy is lower than that of the uncatalysed
reaction, there is a greater proportion of reacting particles having energy greater than or equal
to the activation energy than in the uncatalysed reaction. This is shown by the larger shaded
area in the Maxwell-Boltzmann distribution curve.
total no. of particles with
energy Ea

number of particles
with a given energy

total no. of particles with

energy Ea

>

Ea

Ea

kinetic energy

Consequently, the total number of effective collisions (i.e. collisions resulting in a reaction) per
unit time / frequency of effective collision increases accordingly, and hence, the reaction rate
increases.
Lower activation energy also results in the reaction having a larger rate constant, and hence,
the reaction rate is increased.
(d)

As temperature increases, the average speed of the reacting particles increases. This leads to
a higher collision frequency which contributes to an increase in the reaction rate.
However, the large increase in reaction rate resulting from a small rise in temperature is
mainly due to the fact that at a higher temperature, the number of reacting particles with
energy greater than or equal to the activation energy is increased significantly.
This can be seen from the Maxwell-Boltzmann distribution curve below. The proportion of
reactant particles with energy greater than or equal to the activation energy, Ea, as given by
the area under the curve, is significantly larger at a higher temperature.
number of particles
with a given energy

T2 > T1

total no. of particles with

energy Ea at
temperature T1

T2

total no. of particles with

energy Ea at
temperature T2

T1

Ea

kinetic energy

Consequently, the frequency of effective collisions (i.e. collisions which result in reaction)
increases accordingly, and hence, the reaction rate increases.
An increase in temperature also leads to a larger rate constant, and hence, an increase in the
reaction rate.
Question 7
7

Suggested Solutions to Tutorial 6 Reaction Kinetics

(a)

(i)

An enzyme-catalysed reaction is usually a reversible reaction. When the enzyme is

just mixed with the substrate, the concentration of the product is very low, so the rate
at which the product changes back to the substrate is insignificant and can be ignored
in studying the kinetics of the enzyme-catalysed reaction.

(ii)

The reaction is first order with respect to the enzyme and with respect to the substrate.
When [E] and [S] are each doubled, the rate will quadruple. This is only applicable
when there is a large excess of substrate. k' is a second order rate constant.

(iii)

The reaction is first order with respect to the enzyme and zero order with respect to the
substrate. As the enzyme is saturated, adding more substrate will not change the
reaction rate. The rate will only increase when more enzyme molecules are added. k'
is a first order rate constant.

(iv)

rate
2Vmax
rate = k[enzyme]

Vmax
0.5Vmax
0

(b)

(c)

rate = k[enzyme][substrate]
Km

[substrate]

(i)

Refer to (a)(iv).

(ii)

The affinity of an enzyme for a substrate does not change when [E] changes as the
active site of the enzyme has not been altered. Hence, the value of Km would not
change when [E] is varied.

(iii)

Refer to (a)(iv).

(iv)

When there is a build-up of substrates in cells, the enzymes will be able to respond
quickly by changing the substrates into possibly harmless products.

(i)

An inhibitor either prevents the substrate from binding to the active site or deactivates
the enzyme by modifying the shape of the active site. There will be fewer active
enzymes to catalyse the reaction, and hence, the reaction rate will decrease.

(ii)(a) The competitive inhibitor binds reversibly to the enzyme. To reverse inhibition, a higher
concentration of substrate is required. Thus, the substrate concentration at half
maximum rate will increase, and hence, Km increases. Vmax will not change since the
maximum rate is achievable with a high substrate concentration to reverse inhibition.
(ii)(b) The non-competitive inhibitor does not bind at the active site, so the substrate can still
successfully bind to the enzyme at the active site. Therefore, Km does not change.
However, the reaction does not go to completion because the enzyme-substrate
complex is inactive (i.e. does not change to the product). In addition, the enzyme is
deactivated when the inhibitor binds to it. As there will be fewer enzyme molecules to
catalyse the reaction, Vmax will decrease.
Application Questions
Question 1
rate = k[O][O2] = (3.9 x 105)( 3 x1014) (1.3 x 10 4) = 1.52 x 10 22 mol dm3 s1

(a)
(b)

(i)

At sea level, assume that temperature = 25oC

1 mol of air particles contains 0.21 mol of oxygen molecules (as 21% of air is O2).
Volume occupied by 0.21 mol of O2 = 24 dm3
Concentration of oxygen molecules =
8

= 8.75 x 10 3 mol dm 3

Suggested Solutions to Tutorial 6 Reaction Kinetics

(b)

(ii)

The rate of ozone formation will be much faster at sea level.

This is because the temperature at sea level as well as the average kinetic energy of
O2 molecules will be higher such that the number of reacting O2 molecules with energy
greater than or equal to the activation energy is increased significantly. The frequency
of effective collisions increases, and hence, the rate of reaction increases.
Alternative answer
[O2] at sea level is higher than [O2] at stratosphere.
Since the concentration of O2 is higher, the frequency of effective collisions increases,
and hence, the reaction rate is higher at sea level than in the stratosphere.)

(b)

(iii)

The ultraviolet light is blocked by the ozone in the stratosphere. This prevents the
homolysis of the O2 molecules at sea level from occurring such that [O] is so low at
sea level that the reaction cannot proceed.

(c)

(i)

initial pressure of O2 =

(c)

(ii)

Let 2a kPa be partial pressure of O3 at time t.

(200) = 300 kPa

3O2 (g)

2O3 (g)

initial partial pressure / kPa

partial pressure at time t / kPa

pT =

3a + 2a =

a=

pT
=

(c)

3(

3a

2a

pT) = 3pT 2

(iii)
t /min
= 3pT 2
/ kPa

/ kPa
Graph of

10

20

30

40

50

300

234

183

141

111

87

against time

Suggested Solutions to Tutorial 6 Reaction Kinetics

time/ min
st

1 t1/2 = 27 min

(c)

(iv)

(c)

(v)

k=

nd

Since 1st t1/2 = 2nd t1/2 = 27 min,

half-life is constant.
Hence, the reaction is first order
with respect to O2.

t1/2 = 27 min

= 0.0257 min1

Mechanism I:

Mechanism II:

O2 O + O

slow

O2 O + O

fast

O + O2 O3

fast

O + O2 O3

slow

Rate = k[O2]

Rate = k1[O2][O] k[O2]

first order with respect to O2

reaction is not first order with respect to O2

(In fact, rate = k1[O2][O] = k1[O2]k2[O2]1/2 =

.)

Since the reaction is first order with respect to O2, mechanism I is the correct mechanism.
Question 2
(a)

(i)

Mass of C8H18 in 1l = 0.702 x 1000 = 702 g

Amount of C8H18 in 1l =

= 6.158 mol
= 1.68 x 104 kJ

Amount of useful energy =

Mass of CH3CH2OH in 1l = 0.789 x 1000 = 789 g

Amount of CH3CH2OH in 1l =

mol
= 1.52 x 104 kJ

Amount of useful energy =

(ii)

Amount of useful energy liberated from C8H18 per $

Amount of useful energy liberated from CH3CH2OH per $

10

Suggested Solutions to Tutorial 6 Reaction Kinetics

From the above calculations, ethanol is more cost-effective as it liberates more

useful energy per unit dollar.
(iii)

Give 1 advantage and 1 disadvantage of using octane over ethanol.

Disadvantages

Octane

o
o
o

Ethanol

(b)

Less cost-effective
Produces more soot and carbon dioxide
when burnt, leading to air pollution
Non-renewable source (supply runs out if
crude oil reserve is exhausted)

o
o

Better anti-knock properties

Shorter time for production (fractional
distillation of crude-oil)

Lower anti-knock properties

Longer time for production (crops need
time to grow and be processed to obtain
ethanol)

o
o
o

More cost-effective
Burns more cleanly; less air pollution
Renewable energy source (can make
use of Suns energy to grow crops such
as sugar cane or corn)

2C2H5ONa+(ethanol) + H2(g)

(i)

2CH3CH2OH(l) + 2Na(s)

(ii)

On standing, sodium reacts with oxygen in the air to form Na2O. Cutting the metal
fresh ensures that the metal is not coated by the oxide layer and that the metal is
exposed for reaction.

(iii)

(b)

o
o

Advantages

st

nd

nd

1 t1/2
2 t1/2
= 1.4 min = 1.4 min

(iv)

From the graph above, the first half-life is equal to the second half-life (t1/2= 1.4 min).
Since half-life is constant, the reaction follows first-order kinetics.

(v)

Ethanol is used in large excess. The concentration of ethanol remains essentially

constant during the reaction. Hence, the reaction is zero order with respect to ethanol.

(vi)

On extrapolating from the graph, maximum volume of H2 = 60 cm3

= 2.50 x 10 3 mol

Amount of H2 gas evolved at r.t.p. =

(vii)

Amount of sodium metal used

= 2 x no. of moles of H2
11

Suggested Solutions to Tutorial 6 Reaction Kinetics

= 2 x 2.50 x 10 3 mol

= 5.00 x 10 3 mol

Mass of sodium metal weighed out = 5.00 x 10 3 x 23.0

= 0.115 g
(viii)

2H2O(l) + 2Na(s)

2NaOH(aq) + H2(g)

Sodium metal reacts with water to produce sodium hydroxide and hydrogen gas.
As a result, the rate of reaction between sodium and ethanol cannot be investigated
accurately. An inert solvent, such as dimethyl ether (methoxymethane), can be used to
dilute ethanol instead.
(Other possible answers: hydrocarbons and halogenoalkanes)

12