OCR A2 F325

5.1.1 Rates of reaction

Dr Carl Thirsk
Contents
Rate and orders
The rate equation
Measuring rates and determining orders
Half lives
Initial rates
Effect of temperature
Rate equations and mechanisms
Selected exam questions
 How fast?
Rate graphs, orders of reaction and rate equations
We will be covering: Determining rate constants and orders using data

Grade/Level Success Criteria

Explain and use the term: rate of reaction and order of

C
reaction

Deduce reaction rates from initial rate data and

A/B
concentrationtime graphs

A*/A Relate rate data to reaction mechanisms

Rate and orders
Starter questions
What is meant by rate of reaction?
Which factors affect the rate of reaction?
How do you measure the rate of reaction?
Defining rate
Rate of reaction is the change in concentration of a
reactant or product in a given time:

change in concentration (mol dm3 )

Rate =
time (s)

Rate has units of mol dm-3 s-1

Square brackets, [ ] are used to represent the
concentration, mol dm-3 of a reactant or product.
Measuring rate
As a reaction proceeds, the reactants get used up.
This means that the concentration decreases.
This explains why reactions:
Slow down: fewer collisions are taking place
Stop: when all the reactant has been used up
The rate can be determined by measuring the
concentration of a reactant or product at regular
time intervals.
Measuring rate
When a graph of concentration of reactant is
plotted vs. time, the gradient of the curve is the
rate of reaction.
The gradient of a curve is measured by drawing
tangents.
The initial rate is the rate at the start of the
reaction where it is fastest.
Reaction rates can be calculated from graphs of
concentration of reactants or products as they
change over time.
Concentration change of a reactant during a reaction

(2 1)
=
(2 1)
 (2 1)
Measuring an initial rate =
(2 1)
Measuring the rate from a concentration-
time graph
Sulphuryl chloride decomposes producing sulphur
dioxide and chlorine:

SO2Cl2(g) SO2(g) + Cl2(g)

The concentration of SO2Cl2 was measured and

plotted
 Time/s 0 500 1000 2000 3000 4000
[SO2Cl2]/ 0.50 0.43 0.37 0.27 0.20 0.15
moldm-3

Suppose we want to find the initial rate (t = 0) and the rate as t = 3000:

After t = 0
Rate = Change in [SO2Cl2]/
change in time
blue line = experimental data
Rate = (0.5 0) / (3300 0)
= 1.5 x 10-4 mol dm-3 s-1

After t = 3000
Rate = Change in [SO2Cl2]/
change in time

Rate = (0.38 0.14) / (4000 0)

= 6.0 x 10-5 mol dm-3 s-1
Orders of reaction
What determines whether a collision between two particles
will result in a reaction?
Activation energy - Ea
Only particles that have more energy than Ea will react
when they collide.
If we increase the concentration of a reactant there will be:
A larger number of collisions per second
A faster reaction
By doing a series of experiments we can work out how
concentration of each reactant affects the rate of reaction.
Mathematically this effect is called the order with respect
to a reactant.
Orders of reaction
Take the example reaction:
A+BC
For reactant A, we can say rate is proportional to the
concentration of A:
Rate [A]m
where m is the order of reaction with respect to
reactant A
Order is always defined in relation to concentrations.
There are three common reaction orders.
 Zero order reactions
For the reaction:
A + B + C Products

Zero Order:
If the order is 0 with respect to reactant A, then;

Rate [A]0

The rate is not affected by the concentration of A. We can increase the

concentration of A as much as we like and the rate of reaction will not
change.

This is because any number raised to the power of 0 becomes 1

 First order reactions
For the reaction:
A + B + C Products

First Order:
If the order is 1 with respect to reactant B, then;

Rate [B]1

If we double the concentration of B the rate also doubles

This is because any number raised to the power of 1 is itself

If [B] increases by 2 times, rate increases by 21 times = 2 times

If [B] increases by 3 times, rate increases by 31 times = 3 times
 Second order reactions
For the reaction:
A + B + C Products

Second Order:
If the order is 2 with respect to reactant C, then;

Rate [C]2

If we double the concentration of C the rate quadruples

This is because any number raised to the power of 2 .behaves likes this:

If [C] increases by 2 times, rate increases by 22 times = 4 times

If [B] increases by 3 times, rate increases by 32 times = 9 times
 Combining orders
For the reaction:
A + B + C Products
Let the orders of reaction with respect to the different reactant be as follows:

A = 0, B = 1, and C=2
So the rate is affected by the concentrations of reactant as follows:

Rate [A]0 , Rate [B]1 and Rate [C]2

Combining these expressions gives: Rate [A]0[B]1[C]2

The rate equation
 The Rate Equation and The Rate
Constant, k
For the reaction:
A + B + C Products

The rate constant, k, is a proportionality constant that links the rate of

reaction with the concentration of reactants.

So if:
Rate [A]0[B]1[C]2
We can write a rate equation as follows:

Rate = k[A]0[B]1[C]2

Which simplifies to:

Rate = k[B]1[C]2
since [A]0 = 1.
Summary
For the general reaction:
aA + bB products
The generalised rate equation is:
r = k[A]m[B]n
r is used as the standard symbol for chemical rate
r has units mol dm-3s-1
m, n are called reaction orders
Orders are usually integers 0, 1 ,2
0 means the reaction is zero order with respect to that
reactant
1 means first order
2 means second order
 The Overall Order of Reaction
The overall order of reaction is the sum of the individual orders.

From the example:

Rate = k[B]1[C]2
The overall order is 1 + 2 = 3

VERY IMPORTANT:
The orders have nothing to do with the stoichiometric coefficients in the
balanced equation.

Orders can only be worked out experimentally

 The Rate Equation and Orders of
Reaction
Questions

1) The rate of equation for a reaction between P and Q is:

rate = k[P]2[Q]
How will the rate change if:
(a) The concentration of P is doubled Rate quadruples
(b) The concentration of Q is tripled Rate triples
(c) The concentration of P and Q are both tripled. Rate multiplies by 27

2) In a reaction between R, S and T:

When the [R] is doubled the rate is unchanged
When the [S] is quadrupled the rate increases by 16 times
When the [T] is halved the rate is halved
[R]0 [S]2 [T]1
(a) Deduce the orders w.r.t R, S and T
(b) Hence write down the rate equation for the reaction rate = k [S]2[T] = 3rd order
Key points about the rate constant, k
The units of k depend on the overall order of
reaction and must be worked out from the rate
equation.
The larger the value of k, the faster the reaction
A fast reaction has a large value of k
A slow reaction has a small value of k
The value of k is independent of concentration and
time. It is constant at a fixed temperature.
The value of k refers to a specific temperature and
it increases if we increase temperature.
Finding k and the units of k
The units of the rate constant depend on the
overall order in the reaction.
We can determine the units of k by substituting
units into the rate equation.
For a first order reaction, the rate equation will be:
rate = k[A]1
The units of this will be:
moldm-3s-1 = k x moldm-3
Hence k for a first order reaction has units s-1
Rate constant units
For a 1st order overall reaction the unit of k
is s-1
For a 2nd order overall reaction the unit of k
is mol-1 dm3s-1
For a 3rd order overall reaction the unit of k
is mol-2 dm6s-1
 The Rate Equation and Orders of
Reaction
Question

The reaction between ozone, O3(g), and ethene, C2H4(g), has the rate
equation:
rate = k[O3(g)][C2H4(g)]
5 x 10-8 mol dm-3 O3(g) was reacted with 1.0 x 10-8 mol dm-3 C2H4(g).
The initial rate was 1.0 x 10-12 mol dm-3 s-1
Calculate the rate constant, k, for this reaction and state the units.

k= rate k= 1 x 10-12 = 2000 mol dm3 s-1

[O3][C2H4] (5 x 10-8)(1 x 10-8)
Measuring rates
Half life method
Initial rates
Continuous rate experiments
This is an experiment where the concentration of a
substance is followed throughout the experiment.
This data can be processed by plotting the data and
calculating successive half-lives.
The half life is the time taken for the concentration
of a reactant to half.
The half-life of a first-order reaction is independent
of the concentration and is constant.
If half-lives rapidly increase then the order is 2nd
order.
 Measuring half-lives
The half life of a reactant is the time it takes for the concentration of that
reactant to reduce by half.
The shorter the half life, the faster the reaction is progressing

For a 1st order

reaction:
2N2O(g) 2N2(g) + O2(g) The half-life is
1st order w.r.t to N2O at a constant temp constant
Half-life is the same
regardless of the
concentration
Here half-life is 53
seconds
Half-lives for a zero order reaction

Concentration
decreases at a
constant rate.
Half-life
decreases
with time
Half-lives for a first order reaction

Concentration
halves in
equal time
intervals
Half life is
constant
Half-lives for a second order
reaction

Concentration
decreases
rapidly then
slows down.
Half-life
increases
with time
 Using half-lives
Questions

1) Hydrogen peroxide, H2O2, reacts in a first order reaction with a half-

life of 27 seconds. If the initial concentration of hydrogen peroxide is
1.60 mol dm-3 what is the concentration after 81 seconds?
0.2 mol dm-3
2) Paracetamol has a biological half-life of 380 s. How long will it take
for the level of paracetamol in the body to fall to one 16th of its
original value? 1520 s or 25.3 min
Determining orders from rate-
concentration graphs
Orders can also be determined by plotting
rate against concentration.
Different orders give different shaped
graphs.
The following graphs are of initial rate
against concentration.
It is important to understand and learn the
shapes of these graphs.
Zero order For zero order: the concentration of A has
no effect on the rate of reaction
r = k[A]0 = k

zero-order
Rate is not affected by
changes in conc.
First order For first order: the rate of reaction is
directly proportional to the
concentration of A:
r = k[A]1

first-order
If [A] is doubled then
rate is doubled
Second order For second order: the rate of reaction is
proportional to the concentration of A
squared:
r = k[A]2

second-order
If [A] is doubled then
rate increases by 22 =
4 times
Relating concentration vs. time and
rate vs. concentration graphs
Zero order

Measure half-lives Measure initial rates

Relating concentration vs. time and
rate vs. concentration graphs
First order

Measure half-lives Measure initial rates

Relating concentration vs. time and
rate vs. concentration graphs
Second order

Measure half-lives Measure initial rates

Determining initial rates
The preceding graphs of initial rate against
concentration show the different orders.
The initial rate may have been calculated from
taking gradients from concentration vs. time graphs
at t=0s
For a rate concentration graph to show the order of
a particular reactant, the concentration of that
reactant must be varied whilst the concentrations
of the other reactants should be kept constant.
Another way to determine initial rates is to use
clock reactions
Clock reactions
Clock reactions produce some kind of distinct change after a
certain period of time:
appearance of a precipitate
disappearance of a solid
a change in colour
During these types of reactions you are measuring the rate
for the initial period of the reaction.
This means that there will not be a significant change in
concentration so we can assume that the rate is just 1/t.
In clock reactions, experiments are repeated with different
concentrations of one reactant, then again with another
reactant.
Graphs are plotted for each reactant to determine the order.
Sodium thiosulphate and
hydrochloric acid reaction
The reaction is:
Na2S2O3(aq) + 2HCl(aq)2NaCl(aq) + S(s) + SO2(aq) + H2O(l)
The experiment is repeated with different [HCl] and
then again with different [Na2S2O3]
Graphs are plotted for each
The reaction produces sulfur, which is
formed as a suspension
This causes the solution opacity to
increase
The rate of reaction is measured by
seeing how long it takes for a cross
placed under the beaker to vanish
 Can you write the rate equation for this reaction?
Na2S2O3(aq) + 2HCl(aq) 2NaCl(aq) + S(s) + SO2(aq) + H2O(l)
Results Rate = k [Na2S2O3]1 [HCl]0

Rate = k [Na2S2O3]

Na2S2O3 HCl

As the concentration doubles the rate This reactant has no effect on

also doubles, as the concentration the rate.
triples, the rate triples. The rate continues at a steady
The rate and concentration are in pace.
direct proportion to each other.
Working out orders from
experimental initial rate data
Normally, to work out the rate equation we do a series
of experiments where the initial concentrations of
reactants are changed (one at a time) and measure the
initial rate each time.
In questions, this data is normally presented in a table.
To calculate the order for a particular reactant,
compare two experiments where only that reactant is
being changed
If conc. is doubled and rate stays the same: order= 0 w.r.t
that reactant
If conc. is doubled and rate doubles: order= 1
If conc. is doubled and rate quadruples: order= 2
 Worked example
Work out the rate equation for the following reaction,
A + B + 2C D + 2E, using the initial rate data in the table:

For reactant A compare For reactant B compare For reactant C compare

between experiments 1 between experiments 1 and between experiments 1
and 2 3 and 4
 Worked example

The overall rate equation is r = k[A][B]2

The reaction is 3rd order overall and the unit of the rate
constant = mol-2dm6s-1
Reactant concentrations are
changed simultaneously
In most questions, it is possible to compare
between two experiments where only one
reactant has its initial concentration
changed.
If, however, both reactants are changed then
the effect of both individual changes on
concentration are multiplied together to give
the overall effect on rate.
Reactant concentrations are
changed simultaneously
In a reaction where the rate equation is:
r = k [A] [B]2
If the [A] is x2, that rate would x2
If the [B] is x3, that rate would x32= x9
If these changes happened at the same time then
the rate would x2 x9 = x18
In these questions, you will have to consider the
combined effect different reactants have on the
rate constant to figure out the orders
Worked example
Work out the rate equation for the reaction,
between X and Y, using the initial rate data in the
table:

For reactant X, compare between experiments 1 and 2

For reactant X as the concentration doubles (Y staying
constant) so does the rate
Therefore the order with respect to reactant X is first order
Worked example
Work out the rate equation for the reaction,
between X and Y, using the initial rate data in the
table:

Comparing between experiments 2 and 3:

Both X and Y double and the rate goes up by 8
We know X is first order so that will have doubled rate
The effect of Y, therefore, on rate is to have quadrupled it.
Y must be second order
Worked example
Work out the rate equation for the reaction,
between X and Y, using the initial rate data in the
table:

The overall rate equation is r = k [X] [Y]2

The reaction is 3rd order overall and the unit of the rate
constant =mol-2dm6s-1.
Calculating a value for k using
initial rate data
To do this, choose any one of the experiments and put
the values into the rate equation that has been
rearranged to give k.

Using experiment 3:
r = k [X][Y]2,
k = r / [X][Y]2
k = 2.40 x 106 / 0.2 x 0.22 = 3.0 x 10-4 mol-2dm6s-1
Effect of temperature
 The Effect of Temperature on k
The key factor in the rate of reaction is the number of collisions that exceed
the activation energy, Ea.

Rate increases with temperature by much more than can be explained just from
an increased frequency of collisions.

rate = k [NO]2[O2]

In the above reaction, the rate increases sharply with increasing T even if the
concentrations are unchanged. Obviously the temperature cannot change the
concentrations of the reactants, so this shows that k must change with T.

Increasing T speeds up most reactions by increasing the value of k

For many reactions the rate doubles as T increases by 10C, demonstrating
that a greater number of particles are above Ea
 The Effect of Temperature on k

Rate of reaction can be measured at different temperatures and k calculated for

each temperature. The rate constant, k, increases with increasing temperature

Increasing temperature
increases the rate constant k.
The relationship is given by the
Arrhenius equation k = Ae-(Ea/RT)
where A is a constant, R is the
gas constant and Ea is
activation energy.
You do not need to know this
equation, just be aware that
the relationship between k and
T is not directly proportional
but is as shown on the graph
Rate equations and
mechanisms
Rate determining step
Rate equations and mechanisms
A mechanism is a series of steps through which the
reaction progresses, often involving intermediate
compounds.
If all the steps are added together they will add up
to the overall equation for the reaction.
Each step can have a different rate of reaction. The
slowest step will control the overall rate of reaction.
The slowest step is called the rate-determining
step (r.d.s.)
Rate equations and mechanisms
The molecularity (number of moles of each substance)
of the molecules in the slowest step will be the same as
the order of reaction for each substance.

r=k[A]m

If m=0, the reaction is zero order w.r.t A and A is not

involved in the r.d.s. A must be involved in a fast step.
If m=1, the reaction is first order w.r.t A and 1 mole of A
is involved in the r.d.s. of the mechanism.
If m=2, the reaction is second order w.r.t A and 2 moles
of A feature in the r.d.s of the mechanism
 Predicting mechanisms from rate
equations
NO2(g) + CO(g)NO(g) + CO2(g)

The overall balanced equation tells us that:

1 mol NO2(g) reacts with 1 mol CO(g) to produce 1 mol NO(g) and 1 mol CO2(g)

The overall equation does not tell you anything about the mechanism. To do this we
need to carry out some rate experiments.

If these experiments are carried out the rate equation is found to be:

rate = k[NO2]2
What are the orders of reaction with respect to the two reactants?

[NO2] = second order [CO] = zero order

 Rate-Determining Step and Molecularity
NO2(g) + CO(g ) NO(g) + CO2(g) r = k[NO2]2

If a reactant appears in the rate equation then it must participate in the r.d.s.
The order with respect to that reactant tells you how many particles of that
reactant are involved in the r.d.s. (i.e. its molecularity)

What possible mechanism is consistent with both the rate equation and the
overall equation?
Rate-Determining Step and
Molecularity
Overall Reaction: r = k[NO2]2
NO2(g) + CO(g) NO(g) + CO2(g)
Mechanism:
Step 1: NO2 + NO2 NO + NO3 slow
Step 2: NO3 + CO NO2 + CO2 fast
NO3 is a reaction intermediate.
NO2 appears twice in the slow step so it is second order.
CO does not appear in the slow step so is zero order.
Example 1
Overall reaction:
A + 2B + C D + E
Mechanism:
Step 1: A + B X + D slow
Step 2: X + C Y fast
Step 3: Y+BE fast
C is zero order as it appears in the mechanism after
the slow step
r = k[A][B]
Example 2
Overall reaction:
A + 2B + C D + E
Mechanism:
Step 1: A + B X + D fast
Step 2: X + C Y slow
Step 3: Y + BE fast
We can write from this mechanism:
r = k[X][C]
However, X is an intermediate. We must therefore replace it
in the rate equation with the substances it was formed from
in the step A + B X + D
r = k[A][B][C]
 rate equation tell us the slow step

Example 3 (r.d.s.) will involve two molecules of

NO and one molecule of H2

Using the rate equation rate = k[NO]2[H2] and the

overall equation 2NO(g) + 2H2(g)N2(g) + 2H2O(g), the
following three-step mechanism for the reaction was
suggested. X and Y are intermediate species.
Step 1: NO + NO X
Step 2: X + H2 Y
Step 3: Y + H2 N2 + 2H2O
Which one of the three steps is the r.d.s?
Step 2. H2 appears in the rate equation and combining
steps 1 and 2 gives the correct molecularity
Example 4
Suggest a rate equation for the reaction whose
mechanism is shown below:

CH3CH2Br + OH- CH3CH2OH + Br- slow

The rate equation is r = k[CH3CH2Br] [OH-]
This is called an SN2 reaction. Substitution,
Nucleophilic, 2 molecules in the r.d.s
 The same reaction can also occur via a different
mechanism:
Overall Reaction:
(CH3)3CBr + OH (CH3)3COH + Br
Mechanism:
(CH3)3CBr (CH3)3C+ + Br- slow
(CH3)3C+ + OH (CH3)3COH fast

Write the rate equation and draw the curly arrows

mechanism for this reaction
What would this reaction be called if the other was
SN2?
r = k[(CH3)3CBr)]
SN 1
Example 5
Carbonyls can be reduced by hydrides, such as
sodium tetrahydroborate, NaBH4
An example reaction is:
C3H6O + NaBH4 + H2O C3H8O + NaBH3.OH
A student suggests the rate equation for this
reaction is:
r = k[H2O][C3H6O]
Using your knowledge of the mechanism for this
reaction, state whether or not you agree with this
and why.
Questions
1) The following reaction is first order w.r.t. H2 and first order
w.r.t ICl.
H2(g) + 2ICl(g) I2(g) + 2HCl(g)
a) Write the rate equation for this reaction.
b) The mechanism for this reaction consists of two steps.
i) Identify the molecules that are in the r.d.s. Justify you
answer.
ii) A chemist suggested the following mechanism:
2ICl(g) I2+Cl2 slow
H2(g) + Cl2(g) 2HCl(g) fast
Suggest, with reasons, whether this mechanism is likely to be
correct. [5 marks overall]
Questions
2) The reaction between HBr and oxygen gas occurs
rapidly at 700 K. It can be represented by the equation
4HBr + O2 2H2O + 2Br2
The rate equation was found by experiment to be:
r = k[HBr][O2]
a) Explain why the reaction cannot be a one-step
reaction.
b) Each of the 4 steps in this reaction involves 1 molecule
of HBr. Two of the steps are the same. The r.d.s is the first
one and results in the formation of HBrO2. Write
equations for the full set of 4 reactions.
Hint: HBrO is another intermediate.
Solution to 2b
The rate equation shows that one molecule of HBr is
involved in the r.d.s. However, there are 4 molecules
in the balanced equations. 3 other molecules of HBr
must be involved in other (fast) steps, so the reaction
cannot just be one-step.
Overall mechanism:
Step 1: HBr + O2 HBrO2 slow (r.d.s.)
Step 2: HBr + HBrO2 2HBrO fast
Step 3: HBr + HBrO H2O + Br2 fast
Step 4: HBr + HBrO H2O + Br2 fast
Further questions
Further questions
Orders and rates for simultaneous reactions
Answers
Selected exam questions
June 2010
Jan 2012
June 2013