1.7 Kinetics

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AQA AS Chemistry Your notes
1.7 Kinetics
Contents
1.7.1 Collision Theory
1.7.2 Measuring Rates of Reaction
1.7.3 Maxwell–Boltzmann Distributions
1.7.4 Effect of Temperature on Reaction Rate
1.7.5 Effect of Concentration & Pressure
1.7.6 Catalysts
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1.7.1 Collision Theory

Your notes
Collision Theory
Collision theory
The collision theory states that for a chemical reaction to take place the particles need to collide with
each other in the correct orientation and with enough energy
Collision Theory Table
An ineffective collision is when particles collide in the wrong orientation or when they don’t have
enough energy and bounce off each other without causing a chemical reaction
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Your notes
(a) shows an ineffective collision due to the particles not having enough energy whereas (b) shows an
effective collision where the particles have the correct orientation and enough energy for a chemical
reaction to take place
Increase in reaction rate
The collision frequency is the number of collisions per unit time
When more collisions per unit time take place, the number of particles with energy greater than the Ea
increases
This causes an increase in the rate of reaction
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Activation Energy
For a reaction to take place, the reactant particles need to overcome a minimum amount of energy Your notes
This energy is called the activation energy (Ea)
In exothermic reactions the reactants are higher in energy than the products
In endothermic reactions the reactants are lower in energy than the products
Therefore, the Ea in endothermic reactions is relatively larger than in exothermic reaction
The diagram shows that the reactants are higher in energy than the products in the exothermic reaction,
so the energy needed for the reactants to go over the energy barrier is relatively small
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Your notes
The diagram shows that the reactants are lower in energy than the products in the endothermic
reaction, so the energy needed for the reactants to go over the energy barrier is relatively large
Even though particles collide with each other in the same orientation, if they don’t possess a minimum
energy that corresponds to the Ea of that reaction, the reaction will not take place
Therefore, for a collision to be effective the reactant particles must collide in the correct orientation
AND possess a minimum energy equal to the Ea of that reaction
Catalysts and activation energy
A catalyst is a substance that increases the rate of reaction without taking part in the chemical
reaction by providing the particles an alternative mechanism with a lower activation energy
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Your notes
A catalyst increases the rate of a reaction by providing an alternative pathway which has a lower
activation energy
Exam Tip
The activation energy is the energy needed to ‘activate’ the reactant particles in order for them to
collide effectively and cause a chemical reaction.
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1.7.2 Measuring Rates of Reaction

Your notes
Measuring the Rate of a Reaction
Reaction rate
The rate of reaction is the speed at which a chemical reaction takes place and has units mol dm-3 s-1 or
mol dm-3 min-1
The rate of a reaction can be calculated using:
Worked example
Calculating the rate of reaction
Calculate the rate of reaction, in mol dm-3 s-1, if 0.0440 g of ethyl ethanoate, CH3COOC2H5, (M = 88.0
g mol-1) is formed in 1.00 min from a reaction mixture of total volume 400 cm3
Answer
Step 1: Calculate the amount of ethyl ethanoate in moles:
amount of ethyl ethanoate = 0.0440 g ÷ 88.0 g mol-1

= 0.0005 mol
Step 2: Calculate the concentration of the product:
concentration of ethyl ethanoate = 0.0005 mol ÷ 0.400 dm3

= 0.00125 mol dm-3
Step 3: Calculate the rate:
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rate of reaction = 0.00125 mol dm-3÷ 60 s
rate of reaction = 2.08 x 10-5 mol dm-3 s-1 Your notes

Measuring a rate from a graph
During a reaction, the reactants are used up and changed into products
This means that as the reaction proceeds, the concentration of the reactants is decreasing and the
concentration of the products is increasing
Because of this, the rate of the reaction is not the same throughout the reaction but changes
The rate of reaction during the reaction can be calculated from a concentration-time graph
The isomerisation of cyclopropane to propene is used as an example:
Isomerisation of cyclopropane
The concentrations of reactant (cyclopropane) and product (propene) over time can be measured by
experiment
Concentrations of Cyclopropane & Propene Table
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Your notes
When taking the measurements, the temperature should be kept constant as a change in temperature
will change the rate of reaction
A concentration-time graph for the concentration of propene as well as cyclopropane can be
obtained from the above results
As an example, the concentration-time graph for propene is shown below:
Page 9 of 21
Your notes
The graph shows that the concentration of propene increases with time
Calculating the rate at the start of a reaction
At the start of the reaction, the concentration-time curve looks almost linear
The rate at this point can therefore be found by treating the curve as a linear line and by using:
Using the graph, the average rate of the reaction over the first 5 minutes for propene is:
Page 10 of 21
Your notes
Line a shows the average rate over the first five minutes whereas line b shows the actual initial rate found
by drawing a tangent at the start of the curve. The calculated rates are very similar for both methods
= 0.0009 mol dm-3 s-1

Calculating the rate as the reaction proceeds
The curve becomes shallower with time which means that the rate decreases with time
The rate of reaction can be calculated by taking short time intervals
Eg. you can calculate the rate of reaction from 15 to 20 mins during which the concentration of
propene increases from 0.68 to 0.83 mol dm-3:
Page 11 of 21
Your notes
= 0.0005 mol dm-3 s-1

The smaller the time intervals, the more accurate the reaction rate value is
It is even more accurate to find the rate of reaction at different concentrations of reactant or product
at particular time points
This can be done by drawing tangents at several points on the graph
As an example, the rates of reaction at different concentrations of cyclopropane are calculated by
drawing the appropriate tangents:
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The rate of reaction at three different concentrations of cyclopropane is calculated by drawing

tangents at those points in the graph
Your notes
Rate-concentration graph
The calculated rates can then be summarised in a table to show how the rate of reaction changes with
changing concentration of the reactants or products
Change in rate with Increasing Concentration of Cyclopropane
This data can then be used to plot a rate-concentration graph

The graph shows that the rate is directly proportional to the concentration of cyclopropane
If you double the concentration of cyclopropane the rate of reaction will double too
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Your notes
The graph shows a directly proportional correlation between the concentration of cyclopropane and
the rate of reaction
Exam Tip
To calculate the rate of reaction you can either use the increase in concentration of products (like in the
example above) or the decrease in concentration of reactants.
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1.7.3 Maxwell–Boltzmann Distributions

Your notes
Maxwell-Boltzmann Distribution Curve - Temperature
Maxwell-Boltzmann distribution curve
A Maxwell-Boltzmann distribution curve is a graph that shows the distribution of energies at a certain
temperature
In a sample of a gas, a few particles will have very low energy, a few particles will have very high energy,
but most particles will have energy in between
The Maxwell-Boltzmann distribution curve shows the distribution of the energies and the activation
energy
The graph shows that only a small proportion of molecules in the sample have enough energy for an
effective collision and for a chemical reaction to take place
Changes in temperature
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When the temperature of a reaction mixture is increased, the particles gain more kinetic energy
This causes the particles to move around faster resulting in more frequent collisions
Furthermore, the proportion of successful collisions increases, meaning a higher proportion of the Your notes
particles possess the minimum amount of energy (activation energy) to cause a chemical reaction
With higher temperatures, the Boltzmann distribution curve flattens and the peak shifts to the right
The Maxwell-Boltzmann distribution curve at T oC and when the temperature is increased by 10 oC

Therefore, an increase in temperature causes an increased rate of reaction due to:
There being more effective collisions as the particles have more kinetic energy, making them
move around faster
A greater proportion of the molecules having kinetic energy greater than the activation energy
Exam Tip
The increase in proportion of molecules having kinetic energy greater than the activation has a greater
effect on the rate of reaction than the increase in effective collisions
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1.7.4 Effect of Temperature on Reaction Rate

Your notes
Temperature & Rate of Reaction
Temperature & Rate of Reaction
Increasing the temperature of the reaction mixture increases the rate of reaction in the following two
ways:
At higher temperatures, the particles are moving faster, so collide more frequently. A higher
number of collisions in total mean a higher number of successful collisions
At higher temperatures, a higher proportion of the molecules have the activation energy or more.
This means that a higher proportion of collisions are successful
An increase in temperature causes an increase in the kinetic energy of the particles. The number of
collisions increases and the proportion of successful collisions increases
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1.7.5 Effect of Concentration & Pressure

Your notes
Concentration, Pressure & Rate of Reaction
Concentration
The more concentrated a solution is, the greater the number of particles in a given volume of solvent
An increase in concentration causes in an increased collision frequency and therefore an increased
rate of reaction
The diagram shows a higher concentration of particles in (b) which means that there are more particles
present in the same volume than (a) so the chances and frequency of collisions between reacting
particles is increased causing an increased rate of reaction
Pressure
An increase in pressure in reactions that involve gases has the same effect as an increase in the
concentrations of solutions
When the pressure is increased, the molecules have less space in which they can move
This means that the number of effective collisions increases due to an increased collision frequency
An increase in pressure therefore increases the rate of reaction
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Your notes
The diagram shows a higher pressure in (b) which means that the same number of particles occupy a
smaller volume, resulting in an increased collision frequency and therefore increased rate of reaction
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1.7.6 Catalysts
Your notes
Maxwell-Boltzmann Distribution Curve - Catalyst
Catalysis is the process in which the rate of a chemical reaction is increased, by adding a catalyst
A catalyst increases the rate of a reaction by providing the reactants with an alternative reaction
pathway which is lower in activation energy than the uncatalysed reaction
Catalysts can be divided into two types:
Homogeneous catalysts
Heterogeneous catalysts
Homogeneous means that the catalyst is in the same phase as the reactants
For example, the reactants and the catalysts are all in solution
Heterogeneous means that the catalyst is in a different phase to the reactants
For example, the reactants are gases but the catalyst used is a solid
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The diagram shows that the catalyst allows the reaction to take place through a different mechanism,
which has a lower activation energy than the original reaction
Your notes
Maxwell-Boltzmann distribution curve
Catalysts provide the reactants another pathway which has a lower activation energy
By lowering Ea, a greater proportion of molecules in the reaction mixture have the activation energy,
and therefore have sufficient energy for an effective collision
As a result of this, the rate of the catalysed reaction is increased compared to the uncatalyzed reaction
The diagram shows that the total shaded area (both dark and light shading) under the curve shows the
number of particles with energy greater than the Ea when a catalyst is present. This area is much larger
than the dark shaded area which shows the number of particles with energy greater than the Ea without
a catalyst
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AQA AS Chemistry Your notes

1.7.1 Collision Theory

1.7.2 Measuring Rates of Reaction

amount of ethyl ethanoate = 0.0440 g ÷ 88.0 g mol-1

concentration of ethyl ethanoate = 0.0005 mol ÷ 0.400 dm3

rate of reaction = 0.00125 mol dm-3÷ 60 s

rate of reaction = 2.08 x 10-5 mol dm-3 s-1 Your notes

= 0.0009 mol dm-3 s-1

= 0.0005 mol dm-3 s-1

The rate of reaction at three different concentrations of cyclopropane is calculated by drawing

This data can then be used to plot a rate-concentration graph

1.7.3 Maxwell–Boltzmann Distributions

The Maxwell-Boltzmann distribution curve at T oC and when the temperature is increased by 10 oC

1.7.4 Effect of Temperature on Reaction Rate

1.7.5 Effect of Concentration & Pressure

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