Red Highlight = MUST Remember Green Highlight = Optional

Table of contents
6 Chemical Kinetics​ 1
6.1 Collision theory and rates of reaction​ 1
6.1.1 Collision theory and activation energy​ 1
6.1.2 The Maxwell–Boltzmann distribution​ 2
6.1.3 Rates of Reaction​ 2
6.1.4 Measuring rates of reaction experimentally​ 4
6.1.5 Factors that affect rates of reaction​ 6
6.1.6 The role of a catalyst​ 7
6.1.7 Checklist​ 7
16 Chemical Kinetics​ 8
16.1 Rate expression and reaction Mechanism​ 8
16.1.1 Rate expressions​ 8
16.1.2 Determining the order of reaction graphically​ 8
16.1.3 Reaction Mechanisms​ 9
16.1.4 Checklist​ 10
16.2 Activation Energy​ 11
16.2.1 The Arrhenius equation​ 11
16.2.2 Graphical determination of activation energy​ 12
16.2.3 Checklist​ 12

6 Chemical Kinetics
6.1 Collision theory and rates of reaction
6.1.1 Collision theory and activation energy
Collision theory is based on the idea that for a chemical reaction to occur between two or more reactant particles, they
must collide.

6.1.2 The Maxwell–Boltzmann distribution

The Maxwell–Boltzmann distribution shows that the kinetic energy of the molecules is spread over a range of values.

Maxwell–Boltzmann distributions for the same gas at

different temperatures
As the temperature increases, the particles gain kinetic energy
and the curve flattens out. The area under each curve is the
same because the number of particles is constant, however,
the most probable value of kinetic energy has increased (the
highest point on the curve has moved to the right).
The graph shows that, as the molar mass of the gas increases,
the average molecular speed decreases. All of these gases
have the same amount of kinetic energy.

Distribution of molecular speeds for different gases at

the same temperature
Red Highlight = MUST Remember Green Highlight = Optional
At the same temperature, all gasses have the same amount of kinetic energy, but the speed of the particles depends on
the molar mass of the gas. Gas particles with lower molar masses will have a greater speed and particles with a larger
molar mass will have a lower speed.

6.1.3 Rates of reaction

The rate of reaction is the change in concentration of a reactant or product per unit of time. The unit for rate of reaction
is usually mol dm–3 s–1.

Measured by the increase in the concentration of a product

Δ[𝑃𝑟𝑜𝑑𝑢𝑐𝑡]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛＝ Δ𝑇
Measured by the decrease in the concentration of a reactant
Δ[𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛＝ー Δ𝑇
Change in concentration of reactant against time Change in concentration of product against time.

Instantaneous rate
The instantaneous rate of reaction is the rate of reaction at any particular point in time. It is measured by taking the
gradient of a tangent of the graph at a particular time.

Average rate
Average rate of reaction is the rate of reaction averaged over a certain time period.
𝑦2−𝑦1
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 𝑥2−𝑥1
Left: Determining the average rate of reaction graphically Right: The gradient of the curve decreasing over time
Red Highlight = MUST Remember Green Highlight = Optional

How the rate of a reaction changes with time

The rate of reaction decreases over time.
1. At the start of the reaction, the concentration of reactants is at its highest, which means that there will be a high
frequency of collisions between reactant particles; so the gradient is the greatest.
2. As the reaction proceeds, the concentration of reactants continues to decrease and there are fewer collisions between
reactant particles so the gradient decreases.
3. Once all the reactants have been used, there is no more product formed, and the line plateaus.

6.1.4 Measuring rates of reaction experimentally

Ways to measure progression in reaction
1.​ Decrease in mass of reactants when the products escape the system
2.​ Increase in volume when gas is produced
3.​ Change in electrical conductivity
4.​ Change in pH
5.​ Change in temperature

Measuring the production of a gas

Common reactions that produce gasses are the reactions of metals and metal carbonates with acids such as HCl.

Method 1
A gas syringe is used to collect the carbon dioxide produced in the reaction between calcium carbonate and
hydrochloric acid. The volume of gas produced is recorded at set time intervals and the results are plotted on a graph.

CaCO3 (s) + 2HCl (aq) → CaCl2 (aq) + H2O (l) + CO2 (g)
Red Highlight = MUST Remember Green Highlight = Optional

Method 2
The rate of production of a gas can also be measured using a mass balance. In this experiment, the change in mass per
unit time is measured as the carbon dioxide escapes from the conical flask. Note that the cotton wool is used to prevent
any acid spraying from the flask; it does not prevent the gas from escaping.

Measuring the change in ion concentration

Where a reaction involves ions, we can determine the rate of reaction by using a
conductivity meter to measure the change in ion concentration of an aqueous
solution. Reactions that involve aqueous ions include acid-base reactions (which
involve changes in hydrogen ion concentration). The increase or decrease in
hydrogen ion concentration can be measured using a pH probe.

Measuring the time taken for the formation of a precipitate

The reaction between hydrochloric acid and sodium thiosulfate is an example of a clock reaction in which the time
taken for a reaction to reach a certain point is measured. In this reaction, it is the formation of a precipitate of yellow
sulfur which hides a cross drawn under the reaction mixture. By varying either the concentration or temperature of the
acid or sodium thiosulfate solution, the effect of the change can be measured by recording the time taken for the cross to
be obscured.

Na2S2O3 (aq) + 2HCl (aq) → 2NaCl (aq) + SO2 (g) + H2O (l) + S (s)

Measuring the change in concentration by titration

The final method we will look at is quenching or stopping a reaction. This involves removing a sample of the reaction
mixture and quenching the reaction by placing it in cold water. We can then determine the concentration of either
reactant or product by titrating with a standard solution.
Red Highlight = MUST Remember Green Highlight = Optional

An example of a reaction that can be analyzed by redox titration is the one between iodine and propanone. These
substances react in the presence of a sulfuric acid catalyst according to the following equation:

CH3COCH3 (aq) + I2 (aq) → CH3COCH2I (aq) + HI (aq)

Samples of the reaction mixture are removed at regular time intervals and quenched with sodium hydrogencarbonate
solution. This removes the acid catalyst, quenching the reaction. The amount of iodine remaining can then be
determined by titration with sodium thiosulfate solution, with a starch indicator.

6.1.5 Factors that affect rates of reaction

Factors affecting rates of reaction summary
1.​ Concentration of reactants → number of particles available for collision to occur increases → frequency of
collisions between the particles increases → greater probability of a successful collision resulting in a chemical
reaction
2.​ Temperature → higher average kinetic energy → higher frequency of collision and the number of particles
with energy greater than the activation energy for the reaction increases.
3.​ Pressure of reactions involving gasses → number of gas particles in a given volume is greater →
concentration is greater → higher frequency of collisions
4.​ Particle size → smaller particles of the same quantity have a larger surface area → will be in more contact with
the other reactants → higher frequency of collision
Particle size only has an effect when the solid is being reacted directly, not when it is dissolved in solution as
concentration is not dependent on particle size.
5.​ States of reactants → gas faster than liquid faster than solid → higher entropy → higher frequency of collision
6.​ Presence of a catalyst → provides an alternative reaction pathway with a lower activation energy → a greater
proportion of reactant particles have energy equal to or greater than the activation energy → increase in the
frequency of successful collisions between reactant particles and an increase in the rate of reaction.

Only the catalyst and temperature affect the kinetic energy

Temperature
1.​ With an increased temperature, the reactants gain more kinetic energy.
2.​ This increases the frequency of collisions between reactant particles.
3.​ A greater proportion of reactant particles have energy equal to or greater than the activation energy for the
reaction.
Red Highlight = MUST Remember Green Highlight = Optional

Effect of temperature on the shape of the Maxwell–Boltzmann distribution

1.​ The peak of the distribution curve shifts to the right, so there is an increase in the most occurring value of the
kinetic energy of the particles. Hence, the average kinetic energy of the particles increases.
2.​ The curve flattens, becoming broader so that the total area under it remains constant. This is logical as there is
the same number of particles in the sample.
3.​ A greater proportion of particles have energy equal to or greater than the activation energy due to an increase in
the area under the curve to the right of the activation energy.

6.1.6 The Role of a Catalyst

Catalysts provide an alternative pathway with lower activation energy.
Activation energy is the minimum energy needed for colliding particles to react.

By providing an alternative reaction pathway with a lower activation energy (shown as Ea(cat)), a greater proportion of
reactant particles now have energy equal to, or greater than, the original activation energy for the reaction. This results
in an increase in the frequency of successful collisions between reactant particles and an increase in the rate of reaction.

It is important to note that a catalyst remains chemically unchanged at the end of the reaction and is sometimes reused.

6.1.7 Checklist
1.​ Describe the major points of the collision theory of reaction rates.
2.​ Explain that for a reaction to take place the particles colliding must be in the correct orientation and have
kinetic energies greater than the activation energy for the reaction.
3.​ Sketch the potential energy profile of a reaction, showing the activation energy.
4.​ Explain how the population of molecules in a sample of a gas, liquid, or solution has a spread of kinetic
energies that is described by the Maxwell–Boltzmann distribution curve.
5.​ Describe how the characteristics of the Maxwell–Boltzmann distribution are altered by changing temperature,
meaning that a greater proportion of particles will have energy greater than the activation energy at a higher
temperature.
Red Highlight = MUST Remember Green Highlight = Optional
6.​ Explain how a catalyst (or an enzyme) speeds up a chemical reaction by providing an alternative reaction
pathway of lower activation energy.
7.​ Describe how the rate of a reaction is defined as the rate of change of concentration or amount of a reactant or
product in unit time.
8.​ Describe how the rate of a reaction varies as the reaction proceeds and how this is illustrated graphically.
9.​ Deduce the rate of reaction at a given time during the reaction by drawing a tangent to the curve representing
the course of the reaction.
10.​ Describe how the kinetics of a reaction can be followed by tracking the concentration of a particular reactant or
product with time.
11.​ Explain how changing various conditions of a reaction – concentration, surface area of a solid or pressure of a
gas – alters the rate of a reaction by increasing the frequency of collisions between reacting particles.
12.​ Explain how the effect of increased temperature on the rate of a reaction is twofold: the rate is increased
because the particles collide more frequently; and, more importantly, the particles have greater kinetic energy,
so a greater proportion of the collisions have energy exceeding the activation energy of the reaction.

16 Chemical Kinetics
16.1 Rate expression and reaction mechanism
16.1.1 Rate expressions
Order of reaction (sometimes called partial orders of reaction) is the power to which the concentration of a reactant is
raised in the rate expression.
It can only be determined from experimental data and cannot be deduced from the coefficients in the balanced equation.

a b
E.g. rate = k [W] [X]
The superscripts a and b are the orders of reaction with respect to reactants W and X.
The overall order of the reaction is the sum of individual orders of reaction.
The rate constant (k)is a constant at a particular temperature for a reaction. It changes with the temperature and with the
presence of a catalyst.

The order of reaction with respect to a particular reactant

Zero order: when the reactants do not affect the rate of reaction.
First order: when the reactants’ concentration is doubled, the rate is doubled
Second order: when the reactant’s concentration is doubled, the rate is quadrupled

The rate expression (also known as the rate law or rate equation) gives the relationship between reactant concentrations
and the rate of reaction.

An experiment was carried out to determine the order of reaction between one of the isomers of C3H7Cl and
aqueous sodium hydroxide. The following results were obtained.

Determine the rate expression from the results, explaining your method.[3]
Red Highlight = MUST Remember Green Highlight = Optional
1.​ Rate = k [C3H7Cl] [OH-]
2.​ «[OH−] held constant and» [C3H7Cl] triples AND rate triples «so first order with regards to C3H7Cl»
3.​ [C3H7Cl] doubles AND [OH-] doubles AND rate quadruples «so first order with regards toOH-»

16.1.2 Determining the order of reaction graphically

Rate-concentration graph
Zero order First order Second order

A zero-order reactant will produce a horizontal straight-line graph, as the concentration of the reactant does not affect
the rate of reaction.
A first-order reactant will show a straight line due to the directly proportional relationship between the concentration
and the rate of reaction.
A second-order reactant will show a parabolic curve.

Concentration-time graph
Zero order First order Second order

Half-life and first-order kinetics

The half-life (t1/2) is the time it takes for the concentration of a reactant to
decrease by half.
Half-life is only measured for first-order reactions.
First-order reactions have a constant half-life.

16.1.3 Reaction mechanisms

Reaction mechanisms
The rate-determining step is the slowest step in the reaction mechanism
which has the highest activation energy (has the lowest potential energy).
Red Highlight = MUST Remember Green Highlight = Optional

Elementary reaction: A reaction that takes place in a single step.

Non-elementary reaction: A reaction that takes place in multiple steps.

Experimental rate expressions only support the theory of reaction mechanisms but cannot prove them. (i.e. It is
important to note that a reaction mechanism is only a theory about how a reaction takes place; it cannot be proved. )

Molecularity
Molecularity of a reaction shows the number of reactant particles in an elementary step.
Unimolecular is when only one particle is involved in the elementary step. Unimolecular steps involve either the
decomposition or dissociation, of a molecule into two or more smaller species.
Bimolecular is when two reactant particles are involved.
Termolecular is when three reactant particles are involved.

Examples of elementary steps and rate expressions

Molecularity Elementary step Rate expression

Unimolecular A → products rate = k[A]

Bimolecular A + A → products rate = k[A]2

A + B → products rate = k[A][B]

Termolecular A + A + A → products rate = k[A]3

A + A + B → products rate = k[A]2[B]
A + B + C → products rate=k[A][B][C]

Reaction intermediates and transition states

An intermediate is a species that is formed from the
reactants in a chemical reaction which then gets used up in
latter steps in the reaction mechanism to form the products.
Reaction intermediates do not appear in the overall equation.

A transition state (or activated complex) is the highest

energy state during a reaction which indicates a point at
which new bonds are being formed at the same time as old
bonds are being broken.

E.g. energy profile on the right

Transition state 1 has the highest activation energy so this is
the rate-determining step. This transition state is unstable

Catalysts
Catalysts are chemically unchanged in a chemical reaction; thus, are not considered to be reactants or products.
Catalysts appear in the elementary steps of a reaction mechanism and in the rate-determining step but not in the overall
balanced equation for the reaction.
A catalyst works by increasing the value of the rate constant k – in addition to temperature.

16.1.4 Checklist
1.​ Understand how to write the rate expression for a reaction showing how the rate of a reaction is dependent on
the concentrations of the various reactants,
2.​ Understand that the proportionality constant in the rate expression for a reaction is known as the rate constant,
k, for the reaction,
3.​ Understand that the rate constant is constant for a particular reaction at a particular temperature and is
Red Highlight = MUST Remember Green Highlight = Optional
independent of the concentration of the reactants,
4.​ understand that the order of reaction with respect to a given reactant is the power to which the concentration of
that reactant is raised in the rate expression,
5.​ understand that the overall order of reaction is the sum of the individual orders of reaction,
6.​ understand that the order of reaction with respect to any reactant, and hence the rate expression, must be
determined experimentally,
7.​ outline the meaning of the terms zero-order, first-order and second-order in terms of how the rate of reaction
varies with concentration in each case,
8.​ outline how the order of reaction with respect to a particular reactant can be determined by studying the initial
rate of reaction under varying concentration of the reactants,
9.​ outline the different graphical methods for determining the order of reaction, the rate constant, and hence the
rate expression for a reaction,
10.​ calculate the rate of reaction or the rate constant given appropriate concentration data,
11.​ understand that many reactions are multi-step reactions, taking place by a sequence of elementary steps where
the slowest step is the rate-determining step,
12.​ distinguish between unimolecular and bimolecular reaction steps,
13.​ understand that the rate expression for a multi-step reaction contains only those species taking part in the
rate-determining step,
14.​ understand the involvement of a catalyst in speeding up a chemical reaction and how the catalyst appears in the
rate expression when it participates in the rate-determining step of the reaction,
15.​ understand the role of a catalyst in increasing the rate of a chemical reaction by providing an alternative
pathway with a lower activation energy, and
16.​ understand how kinetic studies help in suggesting possible mechanisms for a given reaction.

16.2 Activation Energy

16.2.1 The Arrhenius equation
Temperature and catalysts affect the value of k constant

Temperature and the rate constant

When the temperature is increased, the rate of reaction also increases – for many reactions, an increase in temperature
of just 10°C can double the rate of reaction. This is because of more frequent and more energetic collisions between
reactant particles. The rate constant k is temperature-dependent, which means that its value depends on the temperature
at which the reaction occurs.
𝐸𝑎
− 𝑅𝑇
𝑘 = 𝐴𝑒 (see booklet)

A is the Arrhenius constant, also known as the pre-exponential factor or the frequency factor.
Ea is the activation energy (J mol−1).
T is the absolute temperature in kelvin (K).
R is the universal gas constant (8.31 J K−1 mol−1).
e is a mathematical constant, also known as Euler’s number.

The Arrhenius constant is a constant that takes into account the frequency of collision and the orientation of collisions
of reactant particles needed for the reaction to successfully occur.

Catalysts and the rate constant

The use of a catalyst provides an alternative pathway with a lower
activation energy.
With lower activation energy, the fraction of molecules with energy
greater than the activation energy (e−Ea /(RT)) increases, and the rate
constant increases.
Red Highlight = MUST Remember Green Highlight = Optional

E.g.
without catalyst:
Ea = 50 kJ mol-1
e−50000 / (8.31 × 273) = 2.71 × 10−10
with catalyst
Ea = 25 kJ mol-1
e−25000 / (8.31 × 273) = 1.64 × 10−5

16.2.2 Graphical determination of activation energy

By taking the natural log of the Arrhenius equation, we
get:
𝐸𝑎
𝑙𝑛𝑘 =− 𝑅𝑇
+ 𝑙𝑛𝐴 (see booklet)
How to determine the activation energy
1.​ Carry out the reaction at different temperatures
to get the respective rate constant.
2.​ Plot ln k against 1/T
3.​ The gradient of the line is equal to –Ea/R
4.​ −Ea = gradient × R

Gradient = −Ea/R
16.2.3 Checklist
1.​ Understand that the temperature dependence of
the rate constant is given by the Arrhenius
equation,
2.​ understand that the Arrhenius equation is an exponential expression involving the rate constant (k), the
activation energy (Ea), the frequency factor (A) and, the absolute temperature (T), and
3.​ describe how the Arrhenius equation can be expressed in a logarithmic form which is useful in providing a
method of calculating the activation energy of a reaction graphically.