Rates of Reaction

The rate of a reaction is a measure of how quickly a reactant is used up, or a product is
formed.

Collision theory
For a chemical reaction to happen:

● reactant particles must collide with each other

● the particles must have enough energy for them to react

A collision that produces a reaction is called a successful collision. The activation

energy is the minimum amount of energy needed for a collision to be successful. It is
different for different reactions.

There are different ways to determine the rate of a reaction. The method chosen usually
depends on the reactants and products involved, and how easy it is to measure changes
in them.

The mean rate of reaction can be calculated using either of these two equations:

Graphs

The rate of reaction can be analysed by plotting a graph of mass or volume of product
formed against time. The graph shows this for two reactions.
The gradient of the line is equal to the rate of reaction:

● the steeper the line, the greater the rate of reaction

● fast reactions - seen when the line becomes horizontal - finish sooner than
slow reactions

Rates, Concentration and Pressure

The greater the frequency of successful collisions, the greater the rate of reaction. If
the concentration of a reacting solution or the pressure of a reacting gas is
increased:

● the reactant particles become more crowded

● the frequency of collisions between reactant particles increases
● the rate of reaction increases

Note that the mean energy of the particles does not change. However, since the
frequency of collisions increases, the frequency of successful collisions also increases.

Rates and Surface Area

For a given mass of a solid, large lumps have smaller surface area than smaller lumps
or powders. If a large lump is divided or ground into a powder:

● its total volume stays the same

● the area of exposed surface increases
● the surface area to volume ratio increases

The greater the frequency of successful collisions, the greater the rate of reaction. If
the surface area to volume ratio of a reacting solid is increased:

● more reactant particles are exposed at the surface

● the frequency of collisions between reactant particles increases
● the rate of reaction increases

Note that the mean energy of the particles does not change. However, since the
frequency of collisions increases, the frequency of successful collisions also
increases.
Rates and Temperature
The greater the frequency of successful collisions, the greater the rate of reaction. If
the temperature of the reaction mixture is increased:

● reactant particles move more quickly

● the energy of the particles increases
● the frequency of successful collisions between reactant particles increases
● the proportion of collisions which are successful increases
● the rate of reaction increases

Catalysts
A catalyst is a substance that:

● increases the rate of a reaction

● does not alter the products of the reaction
● is not chemically changed or used up at the end of the reaction

A catalyst provides an alternative reaction pathway that has a lower activation energy
than the uncatalysed reaction. This does not change the frequency of collisions.
However, it does increase the frequency of successful collisions because more particles
have energy greater than the activation energy, therefore there are more successful
collisions.
Energetics
When a chemical reaction happens, energy is transferred to or from the surroundings.
When energy is transferred to the surroundings, this is called an exothermic reaction,
and the temperature of the surroundings increases. Examples of exothermic reactions
include:
● combustion reactions
● many oxidation reactions
● most neutralisation reactions

Everyday uses of exothermic reactions include self-heating cans and hand warmers.

When energy is taken in from the surroundings, this is called an endothermic reaction
and the temperature of the surroundings decreases. Examples of endothermic reactions
include:

● thermal decomposition reactions

● the reaction of citric acid and sodium hydrogencarbonate

Everyday uses of endothermic reactions include instant ice packs which can be used to
treat sports injuries.

Reaction Profiles

An reaction profile shows whether a reaction is exothermic or endothermic. It shows

the energy in the reactants and products. It also includes the activation energy,
which is the minimum energy needed by particles when they collide for a reaction to
occur. The activation energy is shown as a 'hump' in the line, which:

● starts at the energy of the reactants

● is equal to the difference in energy between the top of the 'hump' and the
reactant

The overall change in energy in a reaction is the difference between the energy of the
reactants and products.
Exothermic reaction

Endothermic reaction
Explaining Energy Changes - Breaking and making bonds
Energy is transferred when bonds are broken or are formed.

The energy change in a reaction can be calculated using bond energies. A bond
energy is the amount of energy needed to break one mole of a particular covalent
bond.

Different bonds have different bond energies. These are given when they are needed
for calculations.

During a chemical reaction:

● bonds in the reactants are broken
● new bonds are made in the products

The difference between the energy needed to break bonds and the energy released
when new bonds are made determines the type of reaction.

A reaction is:
● exothermic if more heat energy is released in making bonds in the products
than is taken in when breaking bonds in the reactants
 ● endothermic if less heat energy is released in making bonds in the products
than is taken in when breaking bonds in the reactants

Calculating Energy Changes

To calculate an energy change for a reaction:

● add together the bond energies for all the bonds in the reactants - this is the
'energy in'
● add together the bond energies for all the bonds in the products - this is the
'energy out'
● energy change = energy in - energy out
Example

Hydrogen and chlorine react to form hydrogen chloride gas:

H−H + Cl−Cl → 2 × (H−Cl)

Use the bond energies in the table to calculate the energy change for this reaction.

Energy in = 436 + 243 = 679 kJ mol-1

Energy out = (2 × 432) = 864 kJ mol-1

Energy change = in - out

= 679 - 864

= -185 kJ mol-1

The energy change is negative. This shows that the reaction is exothermic.