9.

Kinetics I
Collision theory

Energy
Reactions can only occur when collisions take place Activation
between particles having sufficient energy. The energy is Energy:
usually needed to break the relevant bonds in one or EA
either of the reactant molecules. reactants
This minimum energy is called the Activation Energy

∆H
The Activation Energy is defined as the minimum
products
energy which particles need to collide to start a reaction

Maxwell Boltzmann Distribution Progress of Reaction

The Maxwell-Boltzmann energy distribution shows the spread of energies that
Learn this curve
molecules of a gas or liquid have at a particular temperature
carefully

Emp this is the most

probable energy (not the
same as mean energy) The area under the curve
represents the total number of
A few have low particles present
energies because
collisions cause some
Fraction of molecules

Most molecules have energies

particles to slow down between the two extremes but the
distribution is not symmetrical (normal)
with energy

Only a few particles

have energy greater
than the EA
Emp Collision energy 
EA

The energy distribution

The mean energy of The energy distribution should
should go through the
the particles is not at never meet the x axis, as there is
origin because there are
the peak of the curve no maximum energy for molecules
no molecules with no
energy

Q. How can a reaction go to completion if few particles have energy greater than EA?
A. Particles can gain energy through collisions

Increasing Temperature As the temperature increases the distribution shifts

towards having more molecules with higher energies

At higher temps both the Emp and mean energy shift to higher energy
Fraction of molecules

Lower temperature
values although the number of molecules with those energies decrease

T= 25OC
Fraction of molecules
with energy

higher temperature

T= 1067OC
with energy

mean

Collision energy 
Ea
Collision energy 
The total area under the curve should remain constant
because the total number of particles is constant At higher temperatures the molecules have a wider
range of energies than at lower temperatures.

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 Measuring Reaction Rates

The rate of reaction is defined as the change in concentration of a substance in unit time
Its usual unit is mol dm-3s-1

When a graph of concentration of reactant is plotted vs

time, the gradient of the curve is the rate of reaction.

concentration
The initial rate is the rate at the start of the
reaction where it is fastest. rate = gradient of
tangent to curve
Reaction rates can be calculated from graphs of
concentration of reactants or products, by drawing a
tangent to the curve (at different times) and calculating
the gradient of the tangent.
time

In the experiment between sodium thiosulfate and hydrochloric acid we usually measure reaction rate as
1/time where the time is the time taken for a cross placed underneath the reaction mixture to disappear due
to the cloudiness of the sulfur . Na2S2O3 + 2HCl  2NaCl + SO2 + S + H2O
This is an approximation for rate of reaction as it does not include concentration. We can use this because
we can assume the amount of sulfur produced is fixed and constant.

Effect of Increasing Concentration and Increasing Pressure

At higher concentrations(and pressures) there are more particles per

unit volume and so the particles collide with a greater frequency
and there will be a higher frequency of effective collisions.

Note: If a question mentions a doubling of concentration/rate

then make sure you mention double the number of particles Higher concentration
Number of molecules

per unit volume and double the frequency of effective

collisions.
lower concentration
If concentration increases, the shape of the energy distribution
with energy

curves do not change (i.e. the peak is at the same energy) so

the Emp and mean energy do not change

They curves will be higher, and the area under the curves will
be greater because there are more particles
Collision energy 
EA
More molecules have energy > EA (although not a greater proportion)

Comparing rate curves

Need to calculate/ compare
Amount of initial moles of reactants to
product e.g. A
distinguish between different
Volume of B finishing volumes.
gas
e.g. the amount of product is
Different volumes of the C proportional to the moles of
D
same initial concentrations reactant
will have the same initial
rate (if other conditions are Time (secs)
the same) but will end at The higher the concentration/ temperature/
different amounts surface area the faster the rate (steeper the
gradient)

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 Effect of Increasing Temperature

Fraction of molecules
At higher temperatures the energy of the particles Lower temperature
increases. They collide more frequently and more
often with energy greater than the activation energy.

with energy
More collisions result in a reaction
higher temperature
As the temperature increases, the graph shows
that a significantly bigger proportion of particles
have energy greater than the activation energy,
so the frequency of successful collisions
increases Collision energy 
EA

Effect of Increasing Surface Area

Increasing surface area will cause successful collisions to occur more frequently between the
reactant particles and this increases the rate of the reaction.

Catalysts
Definition: Catalysts increase reaction rates without getting used up.

Explanation: They do this by providing an alternative route or mechanism with a lower

activation energy

Activation
Energy:
Comparison of the activation energies for an uncatalysed
uncatalysed reaction and for the same reaction with
a catalyst present. reactants EA catalysed

∆H
products

Progress of Reaction

If the activation energy is lower, more

particles will have energy > EA, so
there will be a higher frequency of With a lower activation
effective collisions. The reaction will be energy more particles have
Fraction of molecules

faster energy greater than the

activation energy
with energy

Collision energy 

EA EA un catalysed
catalysed

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Heterogeneous catalysis
Adsorption of reactants at active sites on the surface
A heterogeneous catalyst is in a different may lead to catalytic action. The active site is the place
phase from the reactants where the reactants adsorb on to the surface of the
catalyst. This can result in the bonds within the reactant
molecules becoming weaker, or the molecules being held in
Heterogeneous catalysts are usually solids
a more reactive configuration. There will also be a higher
whereas the reactants are gaseous or in solution. concentration of reactants at the solid surface so leading to
The reaction occurs at the surface of the catalyst. a higher collision frequency.

Effect of pressure on heterogenous catalysis.

Increasing pressure has limited effect on the rate of heterogenous catalysed reactions because the reaction
takes place on surface of the catalyst. The active sites on the catalyst surface are already saturated with
reactant molecules so increasing pressure wont have an effect.

Industrially catalysts speeds up the rate allowing lower temperature to be used

(and hence lower energy costs) but have no effect on equilibrium.

Environmental benefits of catalysts

Catalysed reactions can occur at lower temperature so less fuel needed and fewer emissions from
fuels.
Catalysed reaction enables use of an alternative process with higher atom economy so meaning
fewer raw materials needed and less waste products are produced

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