UNIT 2

CHEMICAL KINETICS

ADNAN CHOWDHURY
CHEMISTRY TEACHER

UNIT 2: CHEMICAL KINETICS

The rate of a chemical reaction is the change in the concentration of a reactant or product over time.
Rate of Reaction =

( )
()

Units of rate: moldm-3 s-1.

Rate of Reaction =

[]

The negative sign is given because the concentration of reactant decreases with time.

Rate of Reaction =

+[]

The positive sign is given because the concentration of product increases with time.

To determine the reaction rate, the concentration of a reactant or product is measured at regular
time intervals and a graph of concentration against time is plotted.

The slope (gradient) of the tangent at a given point on the curve is the rate of reaction at that point.

The slope is calculated by the change in concentration divided by the time difference.

The initial rate of reaction is the rate of 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 period of
time. If the concentration has not changed by more than 10%:

ADNAN CHOWDHURY

UNIT 2: CHEMICAL KINETICS

Collision Theory:
Chemicals cannot react unless they collide. The theory of reaction rates is therefore called collision theory.
When thinking about reaction rates, molecular level is taken into consideration when collisions occur
The important factors are:

the number of collisions per unit time - the collision frequency

the energy with which the particles collide - the collision energy

the orientation in which the particles collide - particularly important for large molecules. Particles
must collide in such a way that their reactive parts come into contact.

The molecules must collide. The rate of a reaction depends on the frequenry of collision.

A collision will only be successful if the colliding molecules have kinetic energy equal to or greater
than the activation energy. A fast reaction has a low activation energy, so a greater proportion of
collisions will be successful than in a reaction with a higher activation energy. low a6ivation energy
means a fast reaction; a high activation energy means a slow reaction or even one that does not occur
at room temperature.

The molecules must collide with the correct orientation. In a reaction involving complex molecules,
fewer collisions will have the correct orientation than in a reaction between simpler molecules

Activation Energy:
The minimum amount of kinetic energy particles need to react is called the activation energy. The particles
need this much energy to break the bonds to start the reaction. Reactions with low activation energies
happen pretty easily. But reactions with high activation energies don't. Particles must be given extra energy
by heating them.

ADNAN CHOWDHURY

UNIT 2: CHEMICAL KINETICS

The factors that control the rate of a chemical reaction include:

the concentration of the reagents (for reactions in solution)

the pressure (for reactions in the gas phase)

the surface area of any solid reagents

the temperature of the reaction system

the presence of a catalyst

Concentration:
Increasing the concentration of reactants in a sotution means the particles are closer together on average. If
they're closer, they will collide more often. More collisions mean more chances to react.

Collision frequency increases with concentration in a liquid system. The distance between colliding
species is reduced, so there is less distance to travel before encountering another molecule.

The average kinetic energy is independent of the concentration, so as the collision frequency is
higher, the frequency of successful collisions is also higher, so the rate of reaction is faster.

Example 1:

At high concentration of HCl

At low concentration of HCl

Pressure:
For a homogeneous reaction of gases, an increase in pressure, at constant temperature, results in an increase
in reaction rate. Pressure can be increased by reducing the volume of the container or pumping more
reactant gas into the container.

Collision frequency increases with an increase in pressure in a gaseous one. In each case, the distance
between colliding species is reduced, so there is less distance to travel before encountering another
molecule.

The average kinetic energy of the particles remains the same, so the same proportion of collisions will
result in reaction. However, as there are more collisions per second, the rate increases.

Particle Size/Surface Area:

For heterogeneous reactions involving a solid, a larger surface area of the solid results in a faster reaction.

Collision frequency increases with surface area for a solid reagent. In this case, the increased area
raises the probability of a molecule in the other phase (gas or liquid) colliding with the solid.
ADNAN CHOWDHURY

UNIT 2: CHEMICAL KINETICS

Temperature:
An increase in temperature always causes an increase in reaction rate.

Molecules have a higher average kinetic energy at the higher temperature. This means that a greater
fraction of the molecules possess the energy necessary to react on collision.

Collision frequency increases with temperature. The molecules are moving faster and so travel the
necessary distance more quickly.

Maxwell Boltzmann Distribution:

The effect of heating a gas or a solution is to make the molecules or ions move faster and, therefore, to have
a greater average kinetic energy. This increases the fraction of colliding molecules with a combined energy
equal to or greater than the activation energy, which results in a greater proportion of successful collisions.
There are several points to note about these graphs.

All graphs start at the origin.

The distribution is skewed.

The higher temperature graph has its peak at higher energy, but the peak is lower than the graph for
a lower temperature. This is because the area under the graphs must be the same, since this area is
proportional to the total number of molecules. Number of molecules is independent on the
temperature.

Catalyst:
A catalyst speeds up a reaction by providing an alternative path with a lower activation energy.
There are two types of catalysts:
1. Homogeneous
2. Heterogeneous
Homogeneous Catalyst:
A homogeneous catalyst is one that is in the same phase as the reactants. An example is the Fe2+ ion catalyst
in the oxidation of iodide ions, I-, by persulfate ions, S2082-:
S2082-(aq) + 2I-(aq) 2SO42-(aq) + I2(s)
A homogeneous catalyst works by reacting with one of the reactants to form an intermediate compound:
S2082-(aq) + 2Fe2+(aq) 2SO42-(aq) + 2Fe3+(aq)
The intermediate compound then reacts with the other reagent to reform the catalyst:
2Fe3+(aq) + 2I-(aq) 2Fe2+(aq) + I2(s)
The route using the catalyst avoids the necessity of collisions between two negative particles.
ADNAN CHOWDHURY

UNIT 2: CHEMICAL KINETICS

Heterogeneous Catalysts:
A heterogeneous catalyst is one that is in a different phase from the reactants.
One example is iron when used in the Haber process:
N2(g) + 3H2(g) 2NH3(g)
A heterogeneous catalyst usually promotes a reaction through its active sites. These are places on the
surface of the catalyst to which the reactants can bond. The sequence of reactions is:
gaseous reactants + active sites adsorbed reactants
adsorbed reactants adsorbed products
adsorbed products gaseous products + free active sites
There are fewer active sires than there are reactant molecules, so an increase in pressure does not alter the
rate of reaction because all the active sites are already occupied.
Another example is platinum when used in the addition of hydrogen to alkenes
C2H4(g) + H2(g) C2H6(g)

Catalysts are not used up during a reaction. It can be proved by weighing the catalyst with the help
of a mass balance at the start of reaction. When the reaction is complete, the catalyst is filtered,
dried and re-weighed. It will be seen there will be no change in mass.

Maxwell-Boltzmann Distribution:

A catalyst works by providing an alternative route with a lower activation energy. Thus, at a given
temperature, a greater proportion of the colliding molecules will possess the lower activation energy of the
catalysed route and so the reaction will be faster.
The area under the graph beyond catalysed activation energy is greater compared to the uncatalysed.
This increases the fraction of colliding molecules with a combined energy equal to or greater than the
activation energy, which results in a greater proportion of successful collisions.
ADNAN CHOWDHURY

UNIT 2: CHEMICAL KINETICS

Summary:

In homogeneous gas-phase reactions, an increase in pressure causes an increased frequency of

collision and hence an increase in the rate of reaction.

For reactions in solution, an increase in the concentration of a reactant increases the frequency of
collisions and so increases the rate of reaction.

In heterogeneous reactions, an increase in surface area of the solid reactant increases the number of
collisions in a given time between the solid and the gaseous or dissolved reactant, and hence
increases the rate of reaction.

A rise in temperature increases the average kinetic energy of the molecules. This results in more of
the colliding molecules having energy equal to or greater than the activation energy, Ea. Therefore, a
greater proportion of the collisions are successful and hence the rate increases. The rate also
increases slightly because of the increase in the frequencv of collisions.

A catalyst speeds up a reaction by providing an alternative path with a lower activation energy.
Addition of a catalyst causes more molecules to have energy equal to or greater than Ecat, than have
energy equal to or greater than Euncat. Therefore, the proportion of successful collisions increases
and hence the rate increases.

Enzymes are biological catalysts.

Thermodynamic Stability & Kinetic Stability:

For an exothermic reaction, reactants are at a higher energy level than products. So products are
more thermodynamically stable than reactants. So reaction is said to be thermodynamically feasible
(will take place).

For an endothermic reaction, reactants are at a lower energy level than products. So reactants are
more thermodynamically stable than products. So reaction is said to be thermodynamically non
feasible (will not take place).

For an exothermic reactions, if the activation energy is too high that the reactant molecules cannot
attain it then reactant becomes kinetically more stable than products.

Experimental Methods:
The rate of a reaction can be estimated in a number of ways. A common method is to measure the time, t,
for a certain amount of the mixture to react or the time for a certain amount of product to be formed. The
assumption is then made that 1/t is a measure of the rate. This is not strictly accurate because the rate will
have been decreasing from the moment that the reactants were mixed. It is only a fair assumption if the
concentrations of the reactants do not change significantly during the time of the experiment.

Measurable physical changes:

There are a number of physical changes that can be used to estimate the rate of a chemical reaction.
Production of a gas:
If a gas is given off in a reaction, then the volume of the gas can be recorded at regular intervals of time
either by using a gas syringe or measuring cylinder.

ADNAN CHOWDHURY

UNIT 2: CHEMICAL KINETICS

Gas syringe can be used for collecting acidic, alkaline as well as neutral gases.

Measuring cylinder can only be used for collecting neutral gases as acidic or alkaline gases will react
with water and the yield of the gas will be low.

The advantage of using measuring cylinder over gas syringe is that it is user friendly, as volume of gas
is recorded from the downward displacement of water, and removes any impurities present in the gas.

Example 2:
CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)
CO2 is only slightly soluble in water so it can be collected using measuring cylinder.

This is also a suitable method for measuring the decomposition of hydrogen peroxide using, for example,
either different catalysts or different concentrations of hydrogen peroxide:

This method is also suitable for studlng the effect of temperature on the rate of reaction between
magnesium and hydrochloric acid:

Change in mass:
If a gas is given off in a reaction, the system will lose mass. The change in mass can be recorded at regular
intervals of time using a mass balance.

ADNAN CHOWDHURY

UNIT 2: CHEMICAL KINETICS

Colour Change:
The change in colour of either a reactant or a product is measured using a colorimeter.
The rate of the reaction between acidified potassium dichromate(VI) solution and an alcohol can be studied
by measuring the intensity of the colour of the solution, which changes from orange to green as the
dichromate(VI) is reduced by the alcohol.
Production of a Solid:
The time taken to produce enough solid to hide a cross on a piece of paper under the reaction apparatus or
on the side ofthe apparatus can be measured.
This method is used to measure the decomposition of sodium thiosulfate by acid. The solutions are mixed and
placed in a boiling tube that has a felt-pen cross marked on the side. The time taken for enough sulfur to be
produced to hide the cross, when viewed from the other side of the boiling tube, is measured. The
experiment can then be repeated, for example, with either different concentrations or at different
temperatures.

ADNAN CHOWDHURY