Reaction Kinetics

Chapter 22

Xin Zhong School

Factors affecting reaction rate
 In Chapter 9 you learned why reaction rate is increased when:
• the concentrations of the reactants are increased
• the temperature is increased
• a catalyst is added to the reaction mixture.

 In this chapter you will review the definition of the rate of reaction, and find out about:
• quantitative aspects of reaction rates
• how the data gathered from experiments on rates of reaction can be used to confirm
possible reaction
• mechanisms
• more about how catalysts speed up reaction rates.
Defining rate of reaction
 We calculate rate of reaction by measuring a decrease in concentration of a particular
reactant or an increase in concentration of a particular product over a period of time.
The rate constant and rate equations -1-
The rate constant and rate equations -2-
The rate constant and rate equations -3-
 The third column in Table 22.1 shows that the rate of the reaction is proportional to
cyclopropane concentration (within the limits of experimental error). We can express
this mathematically as:
rate of reaction = k × [cyclopropane]

 Rate equations are generally written without the × sign. For example:
rate = k[cyclopropane]

 Rateequations can only be determined from experimental data. They cannot be

found from the stoichiometric equation. Some experimentally determined rate
equations are shown in Table 22.2.
The rate constant and rate equations -2-

 You can see from:

 equation 1 → the rate of reaction is
proportional to the concentration of
both H2 and I2;

 equation 2 → CO and O2 do not appear

in the rate equation, even though they
are present in the stoichiometric
equation.

 Equations 3 and 4 there is no

relationship between the rate equation
and the stoichiometry of the chemical
equation.
Order of reaction -1-
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.

 When you are writing about order of reaction, you must distinguish carefully between
the order with respect to a particular reactant and the overall order of reaction.
rate = k[H2] [NO]2

 We say that this reaction is:

1) first-order with respect to H2 (as rate is proportional to [H2]1)
2) second-order with respect to NO (as rate is proportional to [NO]2)
3) third-order overall (as the sum of the powers is 1 + 2 = 3).

 Orders of reaction are not always whole numbers. A few reactions have fractional
orders.
Order of reaction -2-
Which order of reaction?
We can identify the order of a reaction in three ways:

1 2 3
Graphs of reaction rate against concentration

Zero-order
2NH3 (g) → N2 (g) + 3H2 (g)
 The rate equation derived from experiment is:
rate = k[NH3]0 → rate = k

First-order
2N2O (g) → 2N2 (g) + O2 (g)
 The rate equation derived from experiment is:
rate = k[N2O]1 → rate = k[N2O]

Second-order
2NO2 (g) + CO (g) → NO (g) + CO2 (g)
 The rate equation derived from experiment is:
rate = k[NO2]2
Graphs of concentration of reactant against time

 Fora zero-order reaction, the graph is a descending

straight line. The rate of reaction is the slope
(gradient) of the graph.

 The reaction proceeds at the same rate whatever

the concentration of the reactant.

 For first- and second-order reactions, the graph is a

curve. The curve for the second-order reaction is
much deeper than for a first-order reaction. It also
appears to have a relatively longer ‘tail’ as it levels
off.
Half-life and reaction rates -1-

 Half-life, t 1 , is the time taken for the

concentration2 of a reactant to fall to half of its
original value.

 Three successive half-lives are shown. Table 22.4

shows the values of the successive half-lives
obtained from Figure 22.11.
Half-life and reaction rates -2-

 We can distinguish zero-, first- and second-order reactions from their successive half-lives (Figure 22.12).
1. A zero-order reaction has successive half-lives which decrease with time.

2. A first-order reaction has a half-life which is constant.

3. Second-order reactions have successive half-lives which increase with time.

 Calculating k from initial concentrations and initial rate

H2O2(aq) + 2I–(aq) + 2H+(aq) → 2H2O(l) + I2(aq)

 Table 22.5 shows the rates of reaction obtained using various initial concentrations of each reactant. The
procedure for calculating k is shown below, using the data for experiment 1.

Step 1 Write out the rate equation.

rate of reaction = k[H2O2] [I–]

Step 2 Rearrange the equation in terms of k

𝑟𝑎𝑡𝑒
k = [H O ] [I–]
2 2

Step 3 Substitute the values

3.50 × 10–6
k = (0.0200) × (0.0100) = 1.75 × 10–2 dm3 mol–1 s–1
Calculating k from half-life

 For a first-order reaction, half-life is related to the rate constant by the expression:
0.693
t1 = , where t1 is the half-life, measured in s
𝑘
2 2

0.693
 We can rewrite this in the form: k= t
1

 So, for the first-order reaction cyclopropane to propene:

0.693
k = 17.0 𝑥 60 = 6.79 × 10–4 dm3 mol–1 s–1 (This value is very close to the ones quoted in Table 22.2.)

Rate constants for zero- and second-order reactions can also be calculated from half-lives but the
calculations are more complex.
We can also use the expression k = 0.693 t to calculate the half-life of a first-order reaction if we know the
rate constant.
The effect of temperature on the rate constant -1-
 In Chapter 9, when studying the Boltzmann distribution curve, we learned that at higher
temperatures a greater proportion of the molecules have energy greater than the activation
energy.

 So the rate of reaction increases at higher temperatures. The rate constant, k, and therefore
the rate of reaction, is proportional to the fraction of molecules with energy equal to or
greater than the activation energy.

 So the rate constant increases as the temperature increases.

The effect of temperature on the rate constant -2-
Deducing order of reaction from raw data

Please refer to the Coursebook!

Kinetics and reaction mechanisms -1-
The rate-determining step

 the iodine did not appear in the rate equation but the H+ ions did.
1. A reactant that appears in the chemical equation may have no effect on reaction rate.

2. A substance that is not a reactant in the chemical equation can affect reaction rate.

 In organic chemistry, you have met the idea that reactions occur in a number of steps.

 We call this the reaction mechanism. These steps do not take place at the same rate. The
overall rate of reaction depends on the slowest step. We call this the rate-determining step.
Kinetics and reaction mechanisms -2-
2N2O5(g) → 4NO2(g) + O2
 reaction rate is = k[N2O5]. The rate equation suggests that a single N2O5 molecule is involved in
the rate-determining step.

 This fits in with the proposed mechanism that suggests that the decomposition of N2O5 to
form NO2 and NO3 is the slow step.

 If there is only a single species in the rate-determining step we call the reaction unimolecular.

 If two species are involved in the rate-determining step, we say that the reaction is
bimolecular.

 Mechanisms that involve a trimolecular step are rare.

Predicting the order of a reaction from reaction mechanisms
 We can predict the order of reaction from a given reaction mechanism if we know the intermediates
present in the rate-determining step (or substances that react together to form the intermediate).

 The slow step involves one molecule of propanone and one hydroxide ion. The reaction is second
order overall, first order with respect to propanone and first order with respect to hydroxide ions.
rate = k[CH3COCH3] [OH–]
Catalysis
 Homogeneous catalysis occurs when the catalyst is in the same phase as the reaction
mixture. For example: hydrogen ions catalyse the hydrolysis of esters.

 Heterogeneous catalysis occurs when the catalyst is in a different phase to the

reaction mixture. For example, the decomposition of aqueous hydrogen peroxide
catalysed by manganese(IV) oxide.
Homogeneous catalysis -1-
 Homogeneous catalysis often involves changes in oxidation number of the ions involved in
catalysis.

 Peroxodisulfate (persulfate) ions, S2O82–, oxidise iodide ions to iodine. This reaction is very
slow.

 The peroxodisulfate and iodide ions both have a negative charge. In order to collide and react,
these ions need considerable energy to overcome the repulsive forces when like charges
approach each other. Fe3+(aq) ions catalyse this reaction. The catalysis involves two redox
reactions.
Homogeneous catalysis -2-

 You should notice that it doesn’t matter what the

order is of the two reactions. The oxidation of Fe2+
ions to Fe3+ by S2O82– ions could happen first:

 This reaction is catalysed by Fe3+(aq) and it is also

catalysed by Fe2+(aq).
Homogeneous catalysis -3-
 In order for this catalysis to work, the standard electrode potentials for the reactions involving
the catalyst must lie between the electrode potentials involving the two reactants (Figure
22.22).

 The use of electrode potentials in this way only predicts that the catalysis is possible. It does
not give any information about the rate of reaction.
Heterogeneous catalysis
 Heterogeneous catalysis often involves gaseous molecules reacting at the surface of a solid
catalyst.

 The mechanism of this catalysis can be explained using the theory of adsorption.

 Chemical adsorption (also called chemisorption) occurs when molecules become bonded to
atoms on the surface of a solid.

 The stages in adsorption of hydrogen onto nickel are:

1. hydrogen gas diffuses to the surface of the nickel

2. the hydrogen is physically adsorbed onto the surface – weak van der Waals’ forces link the
hydrogen molecules to the nickel
3. the hydrogen becomes chemically adsorbed onto the surface – this causes stronger bonds
to form between the hydrogen and the nickel
4. this causes weakening of the hydrogen–hydrogen covalent bond.