CHEMICAL KINETICS

Kinetics is the study of rates of chemical processes in an effort

to understand what it is that influences these rates and to

develop theories which can be used to predict them.

Knowledge of reaction rates has many practical applications,

for example in designing an industrial process, in

understanding the complex dynamics of the atmosphere and in

understanding the intricate interplay of the chemical reactions

that are the basis of life.

Chemical kinetics, also known as reaction kinetics, is the

study of rates of chemical processes. Chemical kinetics

includes investigations of how different experimental

conditions can influence the speed of chemical reaction

and yield information about the reactions mechanism

and transition states as well as the construction of

mathematical models that can describe the

characteristics of chemical reaction.

Chemical kinetics deals with the determination of

Reactions rates

Activation Energy

Arrhenius equation

Concentration

Temperature

Catalyst
Rate of Reactions

Rate of reaction is the speed at which a reaction happens.

Products have a positive slope, because they are being formed

in the reaction. For the hypothetical example reaction

A + 2B 3C

Rate of reaction, r, is defined as to be the slope of concentration

time plot for a species divided by the stoichiometric coefficient of

that species. Additionally, if the specy is a reactant, the negative

value of the slope is used, because the slope is negative and a

positive rate is desired. For example shown above

Rate of reaction = r = - d [A] = - 1 d [B] = 1 d [C]

dt 2 dt 3 dt
Factors affecting the rate of chemical reactions
The effect of concentration
If the concentration of any reactant in a solution is increase, the rate
of reaction will increase.
Increasing the concentration increases the rate of probability of a
collision between reactant particles because there are more
particles in the same volume and so increases the chance of
fruitful collision forming products.
increasing the concentration of reactant A or B will increase the
chance or frequency of a successful collision between them and
increase the speed of product formation.
Slower => faster illustrated below.
The effect of Pressure
If one or more of the reactants are gas then increasing
pressure will effectively increase the concentration of the
reactant molecules and speed up the reaction.
The particles are, on average, closer together and
collisions between the particles will occur more frequently.
The A and B particle diagrams above could represent
lower/higher pressure, resulting in lesser or greater
concentration and so slower or faster reaction all because of
the increased chance of a 'fruitful' collision.
Solid reactants and solutions are NOT affected by change
in pressure, there concentration is unchanged.
The effect of Stirring
doing rate experiments with a solid and solution reactant e.g.
marble chips-acid solution or a solid catalyst like manganese(IV)
oxide catalyzing the decomposition of hydrogen peroxide solution,
it is sometimes forgotten that stirring the mixture is an important
rate factor.
If the reacting mixture is not stirred evenly, the reactant
concentration in solution becomes much less near the solid, which
tends to settle out at the bottom of the flask.
Therefore, at the bottom of the flask the reaction prematurely
slows down distorting the overall rate measurement and making
the results uneven and therefore inaccurate. The 'unevenness' of
the results is even more evident by giving the reaction mixture the
'odd stir'! You get jumps in the graph!!!
 Stirring cannot affect a completely mixed up solution at the
particle level i.e. two solutions of soluble substance that react
together are unaffected by stirring.

=>
The effect of surface area particle size of a reactant
If a solid reactant or a solid catalyst is broken down into
smaller pieces the rate of reaction increases.
The speed increase happens because smaller pieces of the
same mass of solid have a greater surface area compared to
larger pieces of the solid.
Therefore, there is more chance that a reactant particle will
hit the solid surface and react. The diagrams below illustrate
the acidmarble chip reaction (slower => faster, but they could
also represent a solid catalyst mixed with a solution of
reactants.
The effect of temperature
When gases or liquids are heated the particles gain kinetic
energy and move faster (see diagrams below).
The increased speed increases the chance (frequency) of
collision between reactant molecules and the rate increases.
BUT this is NOT the main reason for the increased reaction
speed, so be careful in your theory explanations if investigating
the effect of temperature, so read on after the pictures!

Most molecular collisions do not result in chemical change.

 Before any change takes place on collision, the colliding
molecules must have a minimum kinetic energy called the
Activation Energy shown on the energy level diagrams below
(sometimes called reaction profile/progress diagrams - shown
below).
Going up and to the top 'hump' represents bond breaking on
reacting particle collision.
The purple arrow up represents this minimum energy needed to
break bonds to initiate the reaction, that is the activation energy.
Going down the other side represents the new bonds formed in
the reaction products. The red arrow down represents the
energy released - exothermic reaction.
It does not matter whether the reaction is an exothermic or an
endothermic in terms of energy change, its the activation energy
which is the most important factor in terms of temperature and
reaction speed.
 Now heated molecules have a greater average kinetic energy,
and so at higher temperatures, a greater proportion of them have
the required activation energy to react.
This means that the increased chance of 'fruitful' higher energy
collision greatly increases the speed of the reaction, depending on
the fraction of molecules with enough energy to react.
For this reason, generally speaking, and in the absence of
catalysts or extra energy input, a low activation energy reaction is
likely to be fast and a high activation energy reaction much slower,
reflecting the trend that the lower the energy barrier to a reaction,
the more molecules are likely to have sufficient energy to react on
collision.
1. With increase in temperature, there is an increased
frequency (or chance) of collision due to the more 'energetic'
situation - but this is the minor factor when considering why rate
of a reaction increases with temperature.
2. The minimum energy needed for reaction, the activation
energy (to break bonds on collision), stays the same on
increasing temperature. However, the average increase in
particle kinetic energy caused by the absorbed heat means that
a much greater proportion of the reactant molecules now has
the minimum or activation energy to react.
3. It is this increased chance of a 'successful' or 'fruitful' higher
energy collision leading to product formation, that is the major
factor, and this effect increases more than the increased
frequency of particle collision, for a similar rise in temperature.
4. This is usually only fully discussed at AS-A2 level, but it may
impress the teacher for GCSE coursework if you look up the
Maxwell-Boltzmann distribution of kinetic energies, its quite
difficult to get over some of these ideas without considering
graphs of probability versus particle KE, but that's up to you!
There is also the Arrhenius Equation relating rate of reaction and
temperature - but this involves advanced level mathematics.
The effect of catalyst
The word catalyst means an added substance, in contact with
the reactants, that changes the rate of a reaction without itself
being chemically changed in the end.
There are the two phrases you may come across:
a 'positive catalyst' meaning speeding up the reaction (plenty of
examples in most chemistry courses)
OR a 'negative catalyst' slowing down a reaction (rarely
mentioned at GCSE, sometimes at AS-A2 level, e.g. adding a
chemical that 'mops up' free radicals or other reactive species).
Catalysts increase the rate of a reaction by helping break
chemical bonds in reactant molecules and provide a 'different
pathway' for the reaction.
This effectively means the Activation Energy is reduced,
irrespective of whether its an exothermic or endothermic reaction
(see diagrams below
 therefore at the same temperature, more reactant molecules
have enough kinetic energy to react compared to the
uncatalysed situation. The catalyst does NOT increase the
energy of the reactant molecules!
Although a true catalyst does take part in the reaction and may
change chemically temporarily, but it does not get used up and
can be reused/regenerated with more reactants. It does not
change chemically or get used up in the end.
 Black manganese(IV) oxide (manganese dioxide) catalyzes the
decomposition of hydrogen peroxide.
hydrogen peroxide ==> water + oxygen
2H2O2(aq) ==> 2H2O(l) + O2(g)
The manganese is chemically the same at the end of the reaction
but it may change a little physically if its a solid e.g.
In the hydrogen peroxide solution decomposition by the solid
black catalyst manganese dioxide, the solid can be filtered off
when reaction stops 'fizzing' i.e. all of the hydrogen peroxide has
reacted-decomposed.
After washing with water, the catalyst can be collected and added
to fresh colourless hydrogen peroxide solution and the oxygen
production 'fizzing' is instantaneous! In other words the catalyst
hasn't changed chemically and is as effective as it was fresh from
the bottle!
The effect of Light

Light energy (uv or visible radiation) can initiate or

catalyze particular chemical reactions.

As well as acting as an electromagnetic wave, light can be
considered as an energy 'bullets' called photons and they have
sufficient 'impact energy' to break chemical bonds, that is,
enough energy to overcome the activation energy.
The greater the intensity of light (visible or ultra-violet) the more
reactant molecules are likely to gain the energy react, so the

reaction speed increases.

 Examples:

Silver salts are converted to silver in the chemistry of

photographic exposure of the film.
Silver chloride (AgCl), silver bromide (AgBr) and silver
iodide (AgI) are all sensitive to light ('photosensitive'), and
all three are used in the production of various types of
photographic film to detect visible light and beta and
gamma radiation from radioactive materials.
Each silver halide salt has a different sensitivity to light.
When radiation hits the film the silver ions in the salt are
reduced by electron gain to silver
Ag+ + e- ==> Ag (X = halogen atom, Cl, Br or I)
 Photochemical Smog:

This is very complex chemistry involving hydrocarbons,

carbon monoxide, ozone, nitrogen oxides etc.
Many of the reactions to produce harmful chemicals are
catalyzed or promoted by light energy.
Rate of Reaction
Kinetics is the area of chemistry concerned with reaction rates.
The rate can be expressed as:
rate = change in substance/time for change to occur (usually in
M/s)
There are several factors that determine the rate of a specific
reaction and those are expressed in the "collision theory" that
states that for molecules to react, they must:
1. collide
2. have the right energy
3. have the right geometry
The reaction rate can also be expressed by using a "rate law"
and is written as follows:
For the general reaction: aA + bB + ... ----> gG + hH + .....
the reaction rate can be calculated by:
Reaction rate = k[A]m[B]n ....
Where:
[A], [B], etc. are the concentrations of the reactants
k is the rate constant or rate coefficient, a value dependent on
temperature. m,n, etc. are exponents that correspond to a, b,
etc. The concentration is raised to the power of its coefficient in
the balanced equation.
First order
If a reaction rate depends on a single reactant and the value of
the exponent is one, then the reaction is said to be first order.

For example, in the reaction of aryldiazonium ions

with nucleophiles in aqueous solution
ArN2+ + X ArX + N2,
the rate equation is r = k[ArN2+],
where Ar indicates an aryl group.

Another class of first-order reactions is radioactive

decay processes which are all first order. These are, however,
nuclear reactions rather than chemical reactions.
Second order
A reaction is said to be second order when the overall order is two. The
rate of a second-order reaction may be proportional to one concentration
squared , or (more commonly) to the product of two concentrations . As
an example of the first type, the reaction
NO2 + CO NO + CO2 is second-order in the
reactant NO2 and zero order in the reactant CO. The observed rate is
given by, and is independent of the concentration of CO.
The second type includes the class of SN2 (nucleophilic substitution
bimolecular) reactions, such as the alkalinehydrolysis of ethyl acetate
CH3COOC2H5 + OH CH3COO + C2H5OH.
This reaction is first-order in each reactant and second-order overall:
r = k[CH3COOC2H5][OH]
If the same hydrolysis reaction is catalyzed by imidazole, the rate
equation becomes
r = k[imidazole][CH3COOC2H5].
Zero order
For zero-order reactions, the reaction rate is independent
of the concentration of a reactant, so that changing its
concentration has no effect on the speed of the reaction.
This is true for many enzyme-catalyzed reactions, provided
that the reactant concentration is much greater than the
enzyme concentration which controls the rate. For
example, the biological oxidation of ethanol to
acetaldehyde by the enzyme liver alcohol dehydrogenase
(LADH) is zero order in ethanol.
Rate constants and rate equations
You will remember that the rate equation for a reaction between two
substances A and B looks like this

The rate equation shows the effect of changing the concentrations of

the reactants on the rate of the reaction. What about all the other
things (like temperature and catalysts, for example) which also change
rates of reaction? Where do these fit into this equation?
These are all included in the so-called rate constant - which is only
actually constant if all you are changing is the concentration of the
reactants. If you change the temperature or the catalyst , for example,
the rate constant changes. This is shown mathematically in the
Arrhenius equation.
Arrhenius Equation
The Arrhenius equation is a simple, but remarkably accurate,
formula for the temperature dependence of the reaction rate
constant, and therefore, rate of a chemical reaction.
Arrhenius Equation states that:

Where:
A is a constant related to the geometry needed,
e is a constant, approximately 2.7281
Ea is the activation energy,
R is the gas law constant, 8.314 J/mol-K
T is the temperature in kelvins
If it is a simple geometry to attain, A will be large. If a large Ea is
needed then the exponent becomes more negative and therefore
decreases k. If the temperature increases then the exponent
becomes less negative and therefore increases k.
The following are two (2) energy profile graphs that help
demonstrate energy changes during a reaction.
What the various symbols mean
Starting with the easy ones . . .
Temperature, T: To fit into the equation, this has to be measured in
kelvin.
The gas constant, R: It comes from an equation, PV=nRT,
Activation energy, EA: This is the minimum energy needed for the
reaction to occur. To fit this into the equation, it has to be expressed
in joules per mole - not in kJ mol-1.
e: This has a value of 2.71828 . . . and is a mathematical number,
a bit like pi. You don't need to worry exactly what it means,
although if you have to do calculations with the Arrhenius equation,
you may have to find it on your calculator. You should find an ex
button - probably on the same key as "ln".
The expression, e-(EA / RT): This expression counts the
fraction of the molecules present in a gas which have
energies equal to or in excess of activation energy at a
particular temperature.
The frequency factor, A: You may also find this called the
pre-exponential factor or the steric factor.
A is a term which includes factors like the frequency of
collisions and their orientation. It varies slightly with
temperature, although not much. It is often taken as
constant across small temperature ranges.
Collision Theory
For a reaction to occur the reactant particles must collide. Only
a certain fraction of the total collisions cause chemical change;
these are called successful collisions.
Key Points
The collision theory is based on the kinetic theory of gases;
therefore we are only dealing with gas-phase chemical
reactions. Ideal gas assumptions are applied. Furthermore, we
also are assuming:
All molecules are traveling through space in a straight line.
All molecules are rigid spheres.
The reactions concerned are between only two molecules.
The molecules need to collide
Collision Frequency:
The rate at which molecules collide which is the frequency of
collisions is called the collision frequency, Z. The units of Z are: #
of collisions/ unit of time.
Given a box of molecules A and B, the collision frequency
between molecules A and B is given by:

where
NA and NB are the number of molecules A and B, and is directly
related to the concentrations of A and B.
is the mean speed of molecules.
is the averaged sum of the collision cross sections of
molecules A and B. The collision cross section represents the
collision region (area of region=) presented by one molecules to
another.
KB is the Boltzmanns constant