RATES

OF REACTION

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 1. RATE OF REACTION

The rate of a reaction is the change in concentration of a reactant with time:

Rate = change in conc reactants

Change in time

The concentration of the reactants will decrease with time. Rate may also be calculated by measuring the
change in concentration of products over time: this will increase over time.

2. MEASURING THE RATE OF A REACTION

There are a number of different methods for doing this.

REACTIONS WHICH INVOLVE GASES

Measuring the volume of a gas produced

This method is a continuous method (as opposed to initial rates method)

In a reaction in which a gas is given off, the progress of

the reaction can be measured by monitoring the rate at
which the gaseous product is given off.

This can be done by use of a measuring cylinder (less

accurate) or a gas syringe (more accurate) and
measuring the volume of gas given off at set time
intervals.

Then plot a graph of the total volume of gas produced

against time to show how the rate of reaction changes.
By changing the reaction conditions - for example the
concentrations of the reactants or the temperature - you
can investigate how these factors affect reaction rates.

Examples

Calcium carbonate (chips or powder) and acid (not H2SO4 why not?)
Magnesium and acid
Decomposition of diazonium ions to nitrogen and phenol (see notes on nitrogen compounds)
List ways in which this experiment may be inaccurate.

Measuring change in mass

This method is continuous and is typically this is done with the reacting mixture placed in a conical flask on
a balance and change in mass measured over set time intervals. If a gas is produced the mass will decrease.
Care must be taken that splashes of liquid are not lost during the course of the reaction, so a loose swab of
cotton wool is placed in the mouth of the flask to prevent splashes being lost whilst the gas can still escape.

Examples

Same as above for CO2 and not H2 (why?)

List ways in which this experiment may be inaccurate

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 REACTIONS WHICH INVOLVE COLOUR CHANGE

Using a Colorimeter

This method is continuous. A colorimeter may be used to measure changes in the intensity of colour during
the course of a reaction, for example as a result of the appearance or disappearance of iodine or bromine.
The reaction between bromine and methanoic acid which is described later is investigated using this
method. In another investigation, the reaction of potassium iodide with potassium peroxodisulfate is
carried out in a colorimeter. As the oxidation takes place and iodine is produced, the brown colour of the
iodine is monitored extremely precisely in the colorimeter. The change detected by the colorimeter is far
more subtle than the human eye could observe.

The Iodine Clock Method

This experiment is an initial rates method and can be done for any reaction which produces iodine. Two
colourless solutions are mixed and at first there is no visible reaction, but after a short time delay the liquid
suddenly turns dark blue as a result of the reaction between the starch and iodine. The time, l, is measured
from mixing until the first formation of the blue colour. The rate of
reaction disproportional to t.

The sodium thiosulphate is added to delay the appearance of the

blue colour (it reacts with the iodine formed). When it is used up
then the blue colour will appear.

H20 2(aq) + 21-(aq) + 2H+(aq) à 2H20(I) + I2(aq)

The equation for the reaction with sodium thiosulphate is

I2(aq) + 2S2032-(aq) à 2I-(aq) + S4062-(aq)

This reaction is very quick and has no effect on the overall rate.

The experiment can be performed using different concentrations

(usually by dilution with water), a table of initial rates can be constructed and the order of reaction
deduced.

Titrimetric methods

This method can be used either for initial rates or for the continuous method. It usually involves reactions
which produce or use up iodine. For example the reaction between propanone and iodine, with an acid
catalyst:

CH3COCH3 (aq) + I2 (aq) ð CH2ICOCH3 (aq) + H+ (aq) + I- (aq)

Portions of a reacting mixture may be removed at intervals during the course of the reaction, these
portions are then ‘quenched’ either by putting into a large amount of water, or by adding a reagent which
effectively halts the reaction (for example, in the propanone/ iodine reaction addition of some sodium
hydrogencarbonate will stop the effectiveness of the acid catalyst).

HCOOCH3 + OH-ð HCOO- + CH3OH

Titrating portions of this reacting mixture with acid will allow the remaining amount of hydroxide to be
worked out.

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Conductimetric Measurements

Where changes in numbers of charged particles occurs during the course of the reaction, changes in
conductivity may map the reaction rate. For example

H2O2 (aq) + 2H+ (aq) + 2I-(aq) ð 2H2O(l) + I2 (aq)

This would be a continuous method of measuring the rate of a reaction

3. ORDER OF REACTION AND RATE EQUATIONS

The rate of a reaction is going to depend upon the individual reactants. Some reactants decrease in
concentration in a directly proportional manner, whilst the concentration of others may not affect the rate
of the reaction at all. The way in which the rate of a reaction depends on the concentration of the reactants
is expressed in terms of the orders of the reaction.

For reaction xA + yB ð products

It can be found experimentally that rate depends on [A] and [B]

i.e. rate α [A]n[B]m

\ rate = k[A]n[B]m
this is the RATE EQUATION
where k = rate constant (varies with temperature)
and n & m are REACTION ORDERS
In this case the reaction is order n with respect to A and m with respect B and n+m overall.
n and m usually have values 0, 1 or 2 BUT these cannot be predicted but must be determined
experimentally.

FIRST ORDER REACTIONS

In this type of reaction the rate is directly proportional to the concentration of the reactant.

i.e. rate = k[A]

If [A] doubles, the rate doubles

If [A] trebles, the rate trebles etc.

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Units of k (1st order) = s-1

Results from rates can also be

plotted as concentration against
time. Graphs of this sort may also
be used in working out order of
reaction.

A plot of [A] against time results in

an exponential decay.

The rate of a reaction at a given

time may be calculated from this
type of graph by drawing a tangent
and calculating the gradient.

HALF LIVES AND FIRST ORDER KINETICS

When plotting a curve of concentration against time for a first order reaction, it can be noted that the curve
is exponential. .

All first order reactions have constant half lives

This means that the time taken for the concentration of a reactant to
fall by half is a constant in any first order reaction. This is a The time taken for the
convenient way of working out that a reaction is first order. concentration to fall to
half its original value is
If it is possible to work out the half-life from a conc vs. time graph by
called the half-life of the
taking 2 or 3 readings of half-life from the graph and taking an
reaction
average value for the half life.

Mathematically it can be shown that:

t1/2 = ln2
k

where k is the rate constant for the reaction

and t1/2is the half-life for the reaction as derived
from the graph.

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SECOND ORDER REACTIONS

In this case rate = k[A]2

or

If [A] doubles, the rate quadruples

If [A] trebles, the rate increases ninefold etc.

Unit of k (second order) = mol-1dm3s-1

NOTE A plot of [A] vs. time appears to have a similar form

to 1st order BUT t1/2is not constant.

ZERO ORDER REACTIONS

Rate = k

This is independent of [A] ([A]0 = 1)

Units of k = s-1

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SOME EXAMPLES

1. Example 1 ð for the following reaction

A + B ð C
The rate may be found to be simply dependent on the concentration of A and not on the
concentration of B at all. In this case:
Rate of reaction = k[A]
In this instance the order of the reaction with respect to A is 1st order
The rate is zero order with respect to B (effectively [B]0)
And the overall order of reaction is 1
2. Example 2 ðIn another case
D+EðF
it may be found that the rate of the reaction depends on the concentration of both D and E so thatð
Rate = k[D][E]
In this instance the order of the reaction with respect to D and E is 1st order.
The overall reaction is therefore second order
3. Example 3 ð A more complicated instance G + H ð I, the reaction is found to depend upon the
concentration of G (first order with respect to G) and the square of the concentration of H (second
order with respect to H), and third order overall, giving the rate equation:
Rate = k[G][H]2

Deriving Unit of the Rate Constant

The unit of the rate constant k also must be calculated in a manner analogous to a mathematical
calculation.
Example 1
Rate of reaction = k[A]
k = Rate/[A]
So the units = mol dm-3 s-1
moldm-3
= s-1
Example 2
Rate = k[D][E]
It is worth noting the units
for rate constants:
So the units = mol dm-3 s-1 1st order s-1
2nd order mol-1 dm3 s-1
mol2dm-6 3rd order mol-2 dm6 s-1
= s-1
mol dm-3

Or more simply = mol-1dm3s-1

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 4. DERIVING THE RATE EQUATION FOR A REACTION

A general note about reaction kinetics ð investigations into rates of reactions are all based on
experimental evidence, since the order of the reaction is dependent upon the reaction mechanism rather
than the equation for the reaction.

For example potassium peroxodisulphate reacts with potassium iodide to form iodine:

S2O82- + 2I-ð I2 + 2SO42-

The rate equation is found to be

Rate of Reaction = k[S2O82-][I-]
So the reaction is first order with respect to both peroxodisulphate and iodide ions, although from the
equation you might think that it was second order (involving two ions) for the iodide.

There are two main experimental techniques which may be used to deduce the order of a reaction with
respect to a particular reactant , these are the continuous method and the initial rates method.

The Continuous Method

Bromine and methanoic acid react together:

Br2(aq) + HCOOH (aq) ↓ 2Br-(aq) + 2H+(aq) + CO2(g)

Since the colour of the bromine decreases during the course of the reaction the rate of this reaction with
respect to the concentration of bromine can be followed using colorimetry.

Plot this data on a graph and note the shape of the curve as the
Time/s [BR2]/MOL DM-3
concentration of the bromine decreases during the course of the
reaction. Note that doubling the concentration of the bromine results 0 0.0100
in time being halved.
30 0.0090
Plot time (x axis) against concentration (y axis) 60 0.0081
An exponential curve is produced which can be used to deduce the 90 0.0073
order of reaction.
120 0.0066
The shape of the graph for this experiment shows that the reaction is 180 0.0053
first order with respect to bromine. This can be confirmed in two
ways. 240 0.0044
Firstly by determining whether there are constant half-lives: use the 360 0.0028
graph to determine whether this reaction has at least two constant 480 0.0020
half-lives.
600 0.0013
Secondly the rate of reaction can be calculated by plotting a tangent
to the graph at different points and calculating the gradient where:

Gradient = change in conc/change in time

= rate of reaction

To draw a tangent, hold a ruler to the curve so that it just touches the curve at the time required. Draw
along straight line - a large triangle is required to get accurate results.

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 In this example the rate at 400 minutes is -1.09 x 10-3moldm-3min-1.

Do this at enough points to plot the rates graph. Then plot a second graph of rate (y axis) against conc (x
axis). The shape of this line gives the order of reaction with respect to a certain reactant. In this reaction
your rates graph should show that the reaction is first order wrt bromine:

Rate of Reaction = k[Br2]

The Initial Rates Method

An alternative way to measuring rate by measuring change in concentration is to measure the initial rate of
reaction using different concentrations of reagents.

Study the table on the next page of the initial rates of reaction for different experiments in the reaction
between hydrogen and nitrogen oxide:
2H2(g) + 2NO(g) ð 2H2O(g) + N2(g)

Exp Initial conc NO(g) Initial concH2(g) Initial rateN2(g)

/mol dm-3 /mol dm-3 /mol dm-3s-1
1 6 x 10-3 1 x 10-3 3 x 10-3
2 6 x 10-3 2 x 10-3 6 x 10-3
3 6 x 10-3 3 x 10-3 9 x 10-3
4 1 x 10-3 6 x 10-3 0.5 x 10-3
5 2 x 10-3 6 x 10-3 2.0 x 10-3
6 3 x 10-3 6 x 10-3 4.5 x 10-3
• What happens to the initial rate, when the initial concentration of hydrogen is doubled in
experiment 2 compared to experiment 1?
• What happens to the initial rate, when the initial concentration of hydrogen is trebled in
experiment 3 compared to experiment 1?
• How does the reaction rate depend upon [H2(g)]
• What is the order of the reaction with respect to hydrogen?
• Using the concentrations of NO and H2 and the initial rate of reaction in experiment 1, determine
the value of k from the rate equation:
Rate = k[NO]2[H2]
• What are the units of k in this case?
• Carry out the same process for the other experiments
Deducing the order of reaction using the initial rates method

This can be done either by using data in which the initial rate has been measured in different experiments,
with different concentrations of reactants.
If the concentration is doubled and the rate is doubled, then the reaction is first order with respect to that
reactant.

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If the concentration is trebled and the rate also trebles then the reaction is first order with respect to that
reactant.
If the concentration of a reactant is doubled or trebled and there is no change in rate, the reaction is zero
order with respect to that reactant
If the concentration of the reactant is doubled and the rate quadruples, the reaction is second order with
respect to that reactant
If the concentration of the reactant is trebled and the rate increases ninefold, then the reaction is second
order with respect to that reactant.
When asked to deduce the order of reaction with respect to a particular reactant
you must ALWAYS give your reasoning

5. AN IMPORTANT PRACTICAL

THE KINETICS OF THE REACTION BETWEEN IODINE AND PROPANONE IN ACID SOLUTION

The reaction between iodine and propanone follows the overall equation:

The reaction is acid catalysed. This reaction could be studied by using a colorimeter to measure the rate at
which the iodine is being decolourised. This method is INITIAL RATES.

Method

An attempt is made to estimate the rate of change of concentration of iodine, Riodine at the start - that is,
the initial rate. When the reactants are first mixed, the concentration of a reactant will decrease almost
linearly with time, whatever the order of the reaction; it is only later that any differences become
significant. In this method, therefore, the
concentrations of each of the three reactants
are varied systematically in the four 'runs' and
a direct estimate of Riodine made from the
relationship:

1 In 100 cm3 conical flasks, make up four mixtures of hydrochloric acid, propanone solution and water
according to the table below. Label the flasks A, B, C, and D.

2 Measure out into four test tubes, from a burette, the volumes of iodine solution required for each run.
Label the tubes a, b, c, and d.

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3 Start the first run by adding the contents of test tube a to flask A. At the same time, start the timer and
measure the time taken in seconds for the colour of iodine to disappear.

4 Repeat step 3 for the other three runs.

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 6. TEMPERATURE, ACTIVATION ENERGY AND THE RATES CONSTANT
Temperature and activation energy

An increase in the temperature has two effects which result from the fact that increase in temperature
causes an increase in the kinetic energy of the particles:

Since the particles are moving more quickly the chances of a collision increases.

Since the kinetic energy of the particles is increased, when collisions do occur they do so more
energetically, thus increasing the likelihood of bond fission (the first step in reaction of the particles) ð the
particles are more likely to have the necessary activation energy.

This second effect is more important than the first.

A reaction profile diagram shows the changes in energy in a reacting mixture during the course of a
reaction. The mixture starts off at a certain energy level, then energy is put into the system in order to
break bonds and start the reaction, this is the activation energy EA. When all the bonds are broken, new
ones are formed and energy is given off (line XY). The difference between Ea and energy given off when
bonds are formed is the enthalpy of the reaction, DH.

The first diagram represents an exothermic reaction when more

energy is given off when bonds are formed than was needed to
break the bonds. The second represents an endothermic reaction
ð more energy is needed to break the bonds than was given off
when bonds were formed.

Activation energy and the Rates Equation

The magnitude of the rates constant k may be widely

variable for different reactions and depends upon the
activation energy ð the higher the activation energy
the smaller the constant.

The relationship between the magnitude of the constant and

the activation energy was investigated by Arrhenius, who
derived the following equation called the Arrhenius
equation:
k = Ae-Ea/RT
Where

A = the Arrhenius constant (a collision frequency and orientation

factor in the reaction rate)
k = the rate constant
e-Ea/RT = an activation state factor ( R is the gas constant, T is temp in K)
e = constant with a value of 2.71828. The function ex so defined is called the exponential function, and its
inverse is the natural logarithm, or logarithm to base e.
Rewriting the Arrhenius equation in logarithmic form gives:
ln(k) = ln(A) - Ea/(RT)

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 7. THE CONCEPT OF THE RATE-DETERMINING STEP
When considering the rate of the reaction
4HBr(g) + O2(g) ðH2O(l) + Br2(g)

it may be considered that the rate is dependent upon a collision between 4HBr molecules and 1 O2
molecule, which is an unlikely occurrence. In fact the reaction occurs through a series of steps known as the
reaction mechanism.

The rate equation for this reaction is Rate = k[HBr][O2]: this implies that a collision between one HBr and
one O2 is important.. When these two molecules collide they form the intermediate compound, HBrOO.
This first step is a ‘bottleneck’, but once the HBrOO has formed the following steps in the production of
water and bromine occur quickly. The first step is known as the slow step or the rate limiting stepð
the step which determines the overall rate of reaction, and therefore the rate equation.

In organic chemistry reactions, the slow step, or rate determining step is usually the first step in which the
intermediate carbocation or carbanion is formed, or the free radical in the initiation stage of a free radical
reaction (the steps in which energy input is required to break bonds and initiate the reaction), thereafter
the reaction proceeds very fast as a result of the instability of the intermediates. It is therefore possible to
predict the rate equation by considering the reaction mechanism. Alternatively rates experiments can be
used to deduce the mechanism of a reaction. For example in an SN2 reaction should be shown to be first
order with respect to the hydroxide ion and the halogenoalkane, since a collision between these two leads
to the formation of a transition sate in the reaction, whereas in an SN1 reaction the rate equation should
include only the concentration of the halogenoalkane.

Make sure that you can apply your knowledge of reaction mechanisms to predict or work with rates
equations.

Below is an example of an SN2 reaction. You can see that the slow step is the first step and involves
collisions between two different particles. This means that the reaction will be first order with respect to
each of these reactants, the haloalkane and hydroxide ion.

The transition state is the intermediate carbanion: this species is unstable and will quickly form the
reactants: this is the fast step and therefore not included in the rate equation.

An SN1 reaction involves the spontaneous dissociation of the haloalkanes and thus the slow step or step
involving bond breaking only involves one particle so an SN1 reaction will be first order with respect to the
haloalkanes only.

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The reaction of iodine with propanone is another example which shows that it is not possible to deduce the
rate equation from the balanced equation for the reaction.

Experiments show that the reaction is first order with respect to propanone and first order with respect to
hydrogen ions but zero order with respect to iodine. The iodine concentration does not affect the rate of
reaction. This shows that iodine is not involved in the rate-determining step of the reaction mechanism.

In the presence of hydrogen ions propanone molecules can react to form an intermediate species with a
double bond and an -OH group. This involves a slow step followed by a fast step. The concentrations of the
chemical species involved in the rate-determining step appear in the rate equation.

In two further steps the intermediate rapidly reacts with iodine. These two steps do not control the overall
reaction.

These mechanisms
should be learnt.

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 8. CATALYSIS

Catalysis may be homogenous, when the reactants and the catalyst are in the same phase, i.e. all gas or
aqueous, or heterogeneous when the reactants are in a different phase to the catalyst for example the
catalyst is solid and the reactants are gases. This latter is usually the case when transition metal elements
act as catalysts.

It is worth taking a look at the effect a catalyst has on the transition state during a chemical reaction.

The Transition State

This is the high energy state through which the reactants must pass in order to become products. They cannot be
isolated since they are
generally very unstable –
carbocation and
carbanion in organic
reactions are examples
of transition states.
Introducing a catalyst
will result in a different
transition state which
has been produced with
less input of energy thus
allowing the reaction to
proceed more quickly.

HETEROGENEOUS CATALYSIS

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 THE HABER PROCESS
The transition metal elements act as
catalysts through a process known as
chemisorption. The catalysts provide an
alternative reaction pathway – for
example at the surface of the finely
divided iron in the production of
ammonia, NºN and H-H are chemisorbed
onto the surface of the iron and their
bonds are weakened or broken as a
result, this will allow them to react with
each other to form ammonia. This
provides a simplified picture a fairly
complex process.

Important Examples of Transition Metals as Catalysts

Process Catalyst

Production of margarine (saturation of C=C) Platinum or nickel

Contact Process (SO2 D SO3) Vanadium pentoxide
Manufacture of nitric acid Platinum/ rhodium gauze
Haber process ð Production of NH3 Finely divided iron (traces of K2O and Al2O3)

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 THE CATALYTIC REMOVAL OF OXIDES OF NITROGEN FROM THE EXHAUST GASES OF CAR ENGINES
This diagram shows chemisorption at the surface of a catalytic converter:

THE CATALYTIC REMOVAL OF OXIDES OF NITROGEN FROM THE EXHAUST GASES OF CAR ENGINES

A catalytic converter is a device used to reduce the toxicity of emissions from an internal combustion
engine. A catalytic converter provides an environment for a chemical reaction wherein toxic combustion
by-products are converted to less-toxic substances.

HOMOGENOUS CATALYSIS

THE CATALYTIC ROLE OF FE 2+ OR FE 3+ IN THE I – /S 2 O 8 2– REACTION

As aqueous ions the transition metals may also act as homogenous catalysts: the oxidation of I- by S2O82-
can be used as an example of catalytic behaviour in homogeneous systems. The redox reaction

S2O82-(aq) + 2I-(aq) ð 2SO42-(aq) + I2 (aq)

Is accelerated by the presence of a number of transition metal compounds. Iron II and iron III compounds,
for example, are found to be effective. A study of the relevant redox potentials suggests a possible
explanation.

System Eq/V
1 ½ S2O82-(aq) + 2e-D SO42-(aq) +2.01
2 Fe3+(aq) + e-D Fe2+(aq) +0.77
3 ½ I2 (aq) + 2e-D I-(aq) +0.54

17

Comparison of Steps 1 and 3 confirm that the uncatalysed reaction is able to go to completion but, as
always, such considerations tell us nothing about rate. A possible catalysed reaction pathway, having lower
activation energy, involves two steps. If Fe2+(aq) is present as catalyst the first step is:

Fe2+(aq) + ½ S2O82-(aq) ð Fe3+(aq) + SO42-(aq)

And the second is

Fe3+(aq) + I-(aq) ð Fe2+(aq) + ½ I2 (aq).

Reference to the Eq values shows that these reactions are energetically feasible and also that the Fe2+(aq) is
regenerated in the process. The Fe3+(aq) will also act as a catalyst but in the reverse fashion.

An explanation of this catalysis is the suggestion that the uncatalysed reaction has a high activation energy
since it involves a collision between two negative ions, whereas the catalysed reaction involves
collisions between oppositely charged ions.

THE CATALYTIC ROLE OF ATMOSPHERIC OXIDES OF NITROGEN IN THE OXIDATION OF

ATMOSPHERIC SULFUR DIOXIDE
Nitric oxide (NO) reacts with oxygen to produce nitrogen dioxide:

2NO(g) + O2(g) à 2NO2(g)

NO2 dissolves in rain to form a mixture of nitric(v) and nitric(III) acids:

2NO2(g) + H2O(l) à HNO3(aq) + HNO2(aq)

This is a redox reaction, more specifically disproportionation.

NO and NO2 have a catalytic role in the conversion of atmospheric sulfur dioxide to sulfur trioxide:

2NO(g) + O2(g) à 2NO2(g)

SO2(g) + NO2(g) à SO3(g) + NO(g)

DEFINITIONS

Rate constant is the constant of proportionality in the rate expression. It connects the rate of reaction with the
concentration of reaction. Its value increases with increasing temperature and decreases with decreasing temperature.
It decreases with increasing activation energy.

Rate of a Reaction is the rate of change of the concentration of the reactants.

Order of a reaction (sometimes called partial order) is the power to which the concentration of the given
reactant is raised in the rate equation.

Overall order is the sum of the powers to which the reactant concentration terms are raised in the rate equation eg
for the reaction A + B à products

Rate = k [A]x[B]y

Where k= the rate constant; and the reaction is x order wrt A, y order wrt B and x+y order overall

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Rate determining step is the slowest step of a reaction mechanism which determines the overall reaction rate.
The reagents that appear in the rate equation are those involved in the rate determining step or the slow step – any
reactant NOT in the rate equation takes part in one of the fast steps).

Transition state is the high energy state through which the reactants pass after collision in order to become
products. They are unstable species such as carbocations or carbanions.

Half-life is the time taken for the concentration of a reactant to reach half that of its original value
or the time taken for the rate of the reaction to half. The half-life for a first order reaction is
constant.

Activation Energy Ea or Eact is the minimum amount of energy that the colliding molecules must have in order for
that collision to result in a reaction.

The Initial Rate of a reaction is the rate of a reaction at the time when the reactants are mixed. Its value can be
estimated by measuring the concentration of a reactant at the start and after a short time period. If this time is
sufficiently short then initial rate = change in concentration/time.

APPENDIX: YR 12 RATES NOTES

1. FACTORS WHICH AFFECT CHEMICAL REACTIONS

Chemical reactions may occur at different rates that is, some can happen slowly or quickly depending on a
number of factors. These factors may be explained with the collision theory.

The rate of a reaction will depend upon ð

The rate of collision of particles

The energy with which the particles collide.

The factors which The factors which affect
In
affect collision rate activation energy are
are
Temperature Temperature
Pressure Presence of a catalyst
Concentration
Surface area
liquids and gases particles are in rapid random motion and will
therefore often collide with each other. If two particles collide in a
reacting mixture, for example if a molecule of chlorine collides with
a molecule of hydrogen then a reaction will occur, but only if the
particles have sufficient energy to break the covalent bonds in these two molecules ð this energy is known
as activation energy, EA.

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Concentration

A solution of hydrochloric acid of concentration 1 mol dm-3 has 6 x 1023 hydrogen ions in 1 dm3 of solution.
A 2 mol dm-3 solution has 12 x 1023 particles of H+ in 1 dm3 of solution. The rate of reaction of a 1 mol dm-3
solution of a reacting mixture of HCl and CaCO3 will be doubled if the concentration is doubled from 6 x
1023 particles to 12 x 1023 particles of H+ in 1 dm3. Increasing the concentration of a reactant causes a
doubling of the collision rate and hence the doubling of the rate of a reaction.

Pressure

For a reacting mixture of gases the number of particles per unit volume can be expressed in terms of either
concentration, which is equivalent to (in terms of pressure) the partial pressure of individual gases in the
mixture, or alternatively to the total pressure of a gaseous system..

Increasing the partial pressure of one of

the gases will cause an increase in the
reaction rate proportionally according to
the increase in partial pressure.

Increasing the total pressure of the

reacting system will increase the total
number of collisions and therefore
increase the reaction rate.

Surface Area

The reaction between a solid and a liquid

will occur at a faster rate if the surface
area of the solid is increased, since
increase in surface area will allow
proportionally more collisions to occur.

Temperature

An increase in the temperature has two

effects which result from the fact that
increase in temperature causes an
increase in the kinetic energy of the
particles:

Since the particles are moving more quickly the chances of a collision increases.

Since the kinetic energy of the particles is increased, when collisions do occur they do so more
energetically, thus increasing the likelihood of bond fission (the first step in reaction of the particles) ð the
particles are more likely to have the necessary activation energy.

This second effect is more important than the first.

Catalyst

A catalyst is something which speeds up the rate of a reaction without itself being changed. It does this by
providing an alternative reaction pathway which has a lower activation energy, so less energy is needed to
initiate the reaction and the reaction can proceed at a faster rate.

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 2. ACTIVATION ENERGY

A reaction profile diagram shows the changes in energy in a reacting

mixture during the course of a reaction. The mixture starts off at a
certain energy level, then energy is put into the system in order to
break bonds and start the reaction, this is the activation energy EA.
When all the bonds are broken, new ones are formed and energy is
given off (line XY). The difference between Ea and energy given off
when bonds are formed is the enthalpy of the reaction, DH.

The first diagram represents an exothermic reaction when more energy

is given off when bonds are formed than was needed to break the
bonds. The second represents an endothermic reaction ð more energy
is needed to break the bonds than was given off when bonds were
formed.

3. THE MAXWELL BOLTZMANN DISTRIBUTION

Phenomenon

For a 10K rise in temperature the reaction rate of a reacting

mixture approximately doubles.

Explanation

This doubling is not explained simply by an increase in

kinetic energy of the particles. It is explained using a
distribution curve of molecular energies, called the

Maxwell-Boltzmann distribution. In any given

chemical system at a given temperature, T1, most
particles have low energy, some moderate and
fewer have high energy. This is shown as a
skewed curve, with the area under the curve
equal to one. If the temperature is increased by
10K, T2, the shape of the curve changes,
becoming flatter, but with a greater spread of
molecular energies. In a reacting mixture the
particles need activation energy, EA, for the reaction to proceed. For a 10K increase in temperature it can be
seen that the area under the curve roughly doubles ð the proportion of particles having EA roughly doubles
and so the reaction rate doubles.

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 Key Points when drawing a sketch graph of the MB distribution
Accurate drawing of graph Axes labelled
Both curves originating at zero Ea marked on graph at a point well after the peak
Curve T1 peaks before curve T2 Area under the curve for T2 at Ea is roughly double the
area under the curve T1 at Ea.
Curve T1 peaks higher than curve T2 Graph is clearly labelled

Writing a good explanation

The area under the graph to the right of Ea is greater for T2 than for T1
Therefore a greater proportion of molecules have an energy equal to or greater than Ea
Therefore there will be a higher the rate of successful collisions
And a faster (roughly double) reaction rate

4. CATALYSIS
A catalysed reaction works by offering an alternate reaction pathway with a lower activation energy than
the uncatalysed reaction, A + B ð AB

This may be illustrated by showing catalysis in terms of the

formation of an intermediate compound in the following
manner:

A + Catalyst ð A¾Catalyst

A¾Catalyst + B ð A¾B + Catalyst

The larger activation energy for the uncatalysed reaction A +

B ð A¾B is, in this case, replaced by two smaller activation
energies for the catalysed reaction

THE MAXWELL BOLTZMANN DISTRIBUTION AND CATALYSIS

The Maxwell Boltzmann distribution can be used to explain how catalysis increases the rate of a reaction.

Key Pointsð

Draw an accurate diagram, showing Ea for the uncatalysed

reaction well to the right of the peak and Ea for catalysed
reaction to the left of this, still to the right of the peak.

Labelled shading as in above diagram

Greater proportion of particles have enough energy to

react

Therefore there are a greater number of successful

collisions / second

And a faster rate of reaction

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