6.

1
Collision Theory and
Rates of Reaction
ESSENTIAL IDEA AND NATURE OF
SCIENCE
Essential Idea Nature of Science

 The greater the  The principle of Occam’s

probability that molecules
will collide with
sufficient energy and
proper orientation, the
higher the rate of
reaction.
razor is used as a guide to
developing a theory
 although we cannot directly
see reactions taking place
at the molecular level, we
can theorize based on the
current atomic models.
Collision theory is a good
example of this principle.
UNDERSTANDINGS AND APPLICATIONS
AND SKILLS
Understandings Applications and Skills

 Species react as a result of collisions of  Description of the kinetic theory

sufficient energy and proper in terms of the movement of
orientation. particles whose average kinetic
energy is proportional to
 Concentration changes in a reaction temperature in Kelvin.
can be followed indirectly by
monitoring changes in mass, volume  Investigation of rates of reaction
and colour.
experimentally and evaluation of
the results.
 Activation energy (Ea) is the minimum
energy that colliding molecules need in
order to have successful collisions
leading to a reaction.
MEASURING REACTION RATES
 The method depends on  You can use changes in:
the reaction as we are
looking for the easiest 1. Volume of gas produced
way. In most reactions the
concentration of reaction
is measured indirectly. 2. Mass of reaction

 Data loggers can be used 3. Transmission of light /

to measure for any of colour
these changes.
4. pH

5. Electrical conductivity
1. CHANGE IN VOLUME OF GAS
PRODUCED
 This is the easiest if one of the
products is a gas. Collect the gas and
measure the change in volume at
regular time intervals enables a gas to
be plotted of volume against time.

 A gas syringe can be used for this

purpose, or it can be collected by
displacement of water from an
inverted burette or measuring cylinder.

 Remember that water displacement

can only be used with gases with low
to no solubility in water.
AN EXAMPLE
 The rate can be monitored in this way during the reaction
between magnesium and hydrochloric acid.
 CHALLENGE YOURSELF
 Most gases are less soluble in warm water than in cold water, so using warm water
may help to reduce a source of error when collecting a gas by displacement of water.

 But what new error might this cause?

 Why are gases less soluble in warmer water?

 Answers

 Collecting gases over warm water will cause its temperature and therefore its volume to
increase.

 Solubility decreases as temperature increases . The physical reason for this is that when most
gases dissolve in solution, the process is exothermic. This means that heat is released as the gas
dissolves. This is very similar to the reason that vapor pressure increases with temperature.
Increased temperature causes an increase in kinetic energy. The higher kinetic energy causes
more motion in the gas molecules which break intermolecular bonds and escape from solution
or the equilibrium moves to favour the gas molecules as temperature increases.
2. CHANGE IN MASS
 Many reactions involve a change in mass,
and it can be easily measured directly if
the reaction is giving off a gas, the
corresponding decrease in mass can be
measured by placing the mixture on a
balance.

 This method is not suitable for measuring

changes in gases like hydrogen as the
mass is too small for significant changes
in mass.

 This allows for continuous readings and so

can be plotted directly mass against time.
AN EXAMPLE
 The rate can be monitored in this way during the reaction
between calcium carbonate (marble) and hydrochloric
acid.
LIGHT:
COLOURIMETRY/SPECTROPHOTOMETR
Y
 This can be used if one of the reactants or products in coloured
and so gives a characteristic absorption in the visible region
(wavelengths 320-800 nm) or an indicator can be added to
generate a coloured compound that can be followed.

 A colorimeter works by passing light of selected wavelength

through the solution being studied and measures the intensity of
the light transmitted by the reaction components.

 As the concentration of coloured compound increases, it absorbs

proportionally more light, so less is transmitted. A photocell
generates an electric current according to the amount of light
transmitted and this is recorded on a meter or connected to a
computer.
 WHAT IT LOOKS LIKE AND HOW YOU
MEASURE?

 This method allows for continuous readings to be made, so a

graph of absorbance against time can be plotted directly.

 It is possible to convert the absorbance values into concentrations

using a standard curve based on readings of known concentration.

 However, often it is sufficient to record absorbance (or the

inversely proportional transmittance) as a function against time.
AN EXAMPLE
 The reaction between the dye crystal violet and sodium
hydroxide solution can show this:

 CV+ + OH-  CVOH

 The initial solution is coloured but this slowly changes to

a colourless solution as the product is formed.

 So the rate can be determined by measuring the decrease

in absorbance that occurs as the coloured reactant is
depleted.
WHAT IT WOULD LOOK LIKE?
4. CHANGE IN CONCENTRATION
MEASURED USING TITRATION
 In some reactions the concentrations can be measured by
titration against a known standard. This technique is harder
to do because this involves a chemical changing reaction
mixture and so can’t be done continuously as the reaction
proceeds.

 So samples are withdrawn from the reaction mixture at

regular time intervals and the titrated. The problem is
titration takes time during which the mixture is still reacting.

 To overcome this a technique known as quenching can be

used. This is where a substance is added to stop the reaction
(like taking a freeze frame).
AN EXAMPLE
 The reaction between H2O2 and acidified KI yields I2,
which can be titrated against sodium thiosulfate (Na2S2O3),
to determine its concentration.

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

 Na2S2O3(aq) + I2(aq)  2I-(aq) + S4O62-(aq)

 Sodium carbonate is used to quench the reaction by

neutralising the acid.

 2H+(aq) + Na2CO3(aq)  2Na+(aq) + H2O(l) + CO2(g)

5. CHANGE IN CONCENTRATION
MEASURED USING CONDUCTIVITY
 The total electrical conductivity of a solution depends on the
total concentration of its ions and on their charges.

 If this changes between reactants and products, it can provide

a convenient method to follow the progress of a reaction.

 Conductivity can be measured directly using a conductivity

meter which involves immersing inert electrodes in the
solution.

 The values can be changed into concentration, if the apparatus

is calibrated with solutions of known concentration.
AN EXAMPLE
 The reaction between:

 BrO3-(aq) + 5Br-(aq) + 6H+(aq)  3Br2(aq) + 3H2O(l)

 There is a sharp decrease in concentration of ions (12 on

the reactants side and 0 on the products side) will give a
corresponding decrease in the electrical conductivity of
the solution as the reaction proceeds.
6. NON-CONTINUOUS METHODS OF DETECTING
CHANGE DURING A REACTION: ‘CLOCK REACTIONS’

 Sometimes it is difficult to measure the continuous

change in a reaction (as we have seen!), so it may be
easier to measure the time taken for a reaction to reach a
fixed end point.

 The time to reach this point for the same reaction under
different conditions can then be compared and used as a
means of judging the different rates.

 The limitation of this method is data is only an average

rate and therefore not fully representative of a normal
reaction!
AN EXAMPLE
 This kind of reaction can be done in two ways:

 By measuring the time take for a piece of magnesium ribbon to

react completely with dilute acid, until it is no longer visible:

 Mg(s) + 2HCl(aq)  MgCl2(aq) + H2(g)

 By measuring the time taken for a solution of sodium

thiosulfate to become opaque by precipitation of sulfur, so that
a cross viewed through the solution is no longer visible.

 Na2S2O3(aq) + 2HCl(aq)  2NaCl(aq) + SO2(aq) + H2O(l) + S(s)

KINETIC MOLECULAR THEORY
 Itis kinetic energy which allows particles to
move and these particles move randomly. This
kinetic energy is different for particles of the
same type although they are similar.

 This means an average has to be taken when

describing the kinetic energy of a substance.

 The kinetic energy of a substance is directly

related to its absolute temperature (measured
in Kelvin's).
TEMPERATURE
 Increasing temperature therefore increase the average kinetic
energy of the substance.

 As a substance is supplied with extra energy through heating

it, we raise the average kinetic energy of particles and so also
raise its temperature.

 The comparison the behaviour of the particles in the three

states of matter from solid to gas, the differences are a result
of this increase in the average kinetic energy of the particles.
THE MAXWELL-BOLTZMANN DISTRIBUTION
CURVE
 Particles in a gas at a particular temperature show a
range of values for kinetic energy. The numbers of
particles with each different kinetic energy can be shown
by a Maxwell-Boltzmann distribution curve.

 Like other distribution curves, this shows the number of

particles that have a particular kinetic energy plotted
against kinetic energy. The area under the curve
represents the total number of particles in a sample.
HOW REACTIONS HAPPEN
 All particles contain kinetic energy so when reactants are
placed together they will collide with each other.

 The energy at which these collisions happens can result in

some bonds between broken and other new bonds forming.

 This means that the rate of reaction will depend on the number
of collisions between particles which are ‘successful’.

 However, it is important to remember that not all collisions

will be successful. There are two reasons which influence this:

 The energy of the collision

 The geometry of the collision.
ENERGY OF THE COLLISION
 For a reaction to happen the particles must collide with a
enough kinetic energy. The energy is required to overcome the
repulsion between the molecules and to break the bonds in the
reactants.

 When this energy is supplied the reactants form a transition

state from which the products can form. The energy required
represents an energy barrier for the reaction and is known as
the activation energy.
ACTIVATION ENERGY
 The activation energy (Ea) is defined as
the minimum value of kinetic energy
which colliding particles must have
before they are able to react.

 Ifthe particles do not have this energy

they collide but do not react. If the
particles have more than this energy they
can cause a reaction.
 ACTIVATION ENERGY AND RATE
 Activation energy is a threshold and determines which particles react and which do
not. So only particles greater than the activation energy will have successful
collisions.

 Therefore rate of reaction depends on the proportion of particles that have values for
kinetic energy greater than the activation energy.

 The graph can be used to help determine the rate of reaction as the rate depends on
the proportion of particles that have values of kinetic energy greater than the
activation energy.
 GEOMETRY OF THE COLLISION
 As collisions are random they occur in different orientations. In
some reactions this can be crucial in determining whether or not
collisions will be successful.

 The diagrams above represent how a reaction can be affected by

the geometry of the collisions.
ACTIVATION ENERGY AND REACTIONS
 Differentreactions have different activation
energies and the magnitude of the value helps to
determine the rate of a reaction.

 Ingeneral, reactions with high activation energy

proceed more slowly than those with low
activation energy.
COLLISION THEORY SUMMARY
 Collision theory can be summarised as
follows:

The rate of reaction depends on the frequency

of the collisions that occur between particles
possessing both:

 Values of kinetic energy greater than the activation

energy.

 Appropriate collision geometry.