Chemistry Handout 15 REF #: 015

Rates of Reaction

Chemical reactions vary greatly in the speed at which they occur. Some are essentially instantaneous, while others may
take years to reach equilibrium. Compare a combustion reaction to a rusting reaction, or the formation of stalactites and
stalagmites (made of calcium carbonate) to the precipitation of silver chloride on adding hydrochloric acid to silver
nitrate.

The Reaction Rate (or rate of a reaction) for a given chemical reaction is the measure of the change in concentration of
the reactants or the change in concentration of the products per unit time, at a stated temperature.

Measuring Rates of Reaction

During any reaction, the concentration of the reactants decreases at the same rate as the concentration of the products
increase. The rate of a chemical reaction is defined as the measured change of a specific property of a reaction per unit
time.

Changes in concentration are not always easy to measure directly. Property change which can be measured more easily
include:

- Volume of a gaseous product

Hydrogen peroxide decomposes to produce oxygen:

The volume of oxygen produced can be measured using the

gas syringe method. The gas collects in the syringe, pushing
out against the plunger. The volume of gas that has been
produced can be read from the markings on the syringe. This
change in volume can be converted to a change in
concentration (Δ[C]), and dividing this by the time of the
reaction (Δt) will yield an average reaction rate.

- Colour intensity- only in cases where coloured reactant is consumed or new coloured product formed

- Amount of a precipitate formed

- In a reaction in which a precipitate is formed, the amount of precipitate formed in a period of time can be used
as a measure of the reaction rate. For example, when sodium thiosulphate reacts with an acid, a yellow
precipitate of sulfur is formed. This reaction is written as follows:
One way to estimate the rate of this reaction is to carry out the investigation in a conical flask and place a piece
of paper with a black cross underneath the bottom of the flask. At the beginning of the reaction, the cross will be
clearly visible when you look into the flask. However, as the reaction progresses and more precipitate is formed,
the cross will gradually become less clear and will eventually disappear altogether. By using a stopwatch to time
how long it takes for the cross to disappear, and then massing the amount of precipitate formed during this
time, an average reaction rate can be calculated. Note that it is not possible to collect the SO 2 gas that is
produced in the reaction because it is highly soluble in water.
Chemistry Handout 15 REF #: 015

- Decrease in mass (if a gas is evolved)

if only one solid is used up

- could remove periodically and weigh it:

- if one gas is produced and escapes, measure mass of what’s left in container

Suitable for reactions giving off oxygen or carbon dioxide but not hydrogen as the mass loss is too small to be
accurately measured.

Collision Theory for Reactions

There is another big idea for rates of reaction called collision theory. The collision theory says that as more collisions in a
system occur, there will be more combinations of molecules bouncing into each other. If you have more possible
combinations, there is a higher chance that the molecules will complete the reaction. The reaction will happen faster
which means the rate of that reaction will increase. 

Think about how slowly molecules move in honey when compared to your soda even though they are both liquids.
There are a lower number of collisions in the honey because of stronger intermolecular forces (forces between
molecules). The greater forces mean that honey has a higher viscosity than the soda water. 

In order to react:

1. Particles of the reacting substances must collide with each other to break old bonds in the reactants and form
new bonds in the products.
2. The colliding particles must produce sufficient energy (called activation energy) to break the old bonds in the
reactants.

Note: Not all collisions produce this required energy, therefore, not all collisions result in a reaction occurring.

3. Reactant particles must collide with the correct orientation so that the energy produced by the collision can be
passed onto the bonds to be broken.

Factors affecting Reaction Rates

Although a balanced chemical equation for a reaction describes the quantitative relationships between the amounts of
reactants present and the amounts of products that can be formed, it gives us no information about whether or how
fast a given reaction will occur. This information is obtained by studying the chemical kinetics of a reaction, which
depend on various factors: reactant concentrations, temperature, physical states and surface areas of reactants, and
solvent and catalyst properties if either are present. By studying the kinetics of a reaction, chemists gain insights into
how to control reaction conditions to achieve a desired outcome.

Reaction rates can be affected by:

- Concentration of reactants
 Increasing the concentration increases the rate of reaction
 Explanation: Two substances cannot possibly react with each other unless their constituent particles
(molecules, atoms, or ions) come into contact. If there is no contact, the reaction rate will be zero.
Chemistry Handout 15 REF #: 015
Conversely, the more reactant particles that collide per unit time, the more often a reaction between them
can occur. Consequently, the reaction rate usually increases as the concentration of the reactants increases.
Increasing concentration increases the number of particles per unit volume- frequency of collision increases.

e.g If zinc is placed in dilute HCl, it reacts to produce bubbles of hydrogen and zinc chloride.

If the reaction is repeated with concentrated acid, the hydrogen is evolved much more quickly, making the liquid fizz.
This is because the rate of a reaction depends on how frequently the molecules of the reacting substances collide. The
concentrated acid has more molecules for a given volume than the more dilute acid. Because there are more molecules
moving about, the frequency of collisions is greater, and the reaction occurs faster.

e.g (2) when Sodium Thiosulphate reacts with hydrochloric acid sulphur is produced. The sulphur forms in very small
particles and causes the solution to cloud over and turn a yellow colour. This causes the cross to fade and eventually
disappear.

- Pressure (affects gaseous reactants only)

 Increasing the pressure, increases the rate of reaction
 Pressure is due to the collisions of the particles with: each other and the walls of the container. The
more frequent the collision, the greater the pressure will be. When the pressure of a gas increases, at a
constant temperature, the volume decreases, because the molecules come close together (Boyle’s law).
An increase in pressure therefore causes an increase in the concentration of the gas (particles are closer
together), and so they collide more frequently. Therefore, an increase in pressure of a reactant causes
an increase in the reaction rate. Industrial reactions are often carried out at a high pressure to increase
reaction rate.

- Temperature
 The rate of reaction increases with an increase in temperature
 Increasing the temperature results in an increase in the kinetic energy of the particles, causing them to
move faster. Consequently, the particles collide more frequently. Not all collisions lead to a reaction. For
a collision to lead to a reaction, the molecules must be properly oriented and must have enough energy
to react (the activation energy). At high temperatures, the particles collide with more energy so that
more collisions produce sufficient energy to break bonds in the reactants.
 For example, magnesium ribbon hardly reacts at all with cold water.
Mg (s) + H2O (l)  Mg(OH)2 (s) + H2 (g)
However, if water is heated to boiling point before the magnesium is added, it fizzes quite vigorously as
the hydrogen gas evolves.
 KI (aq) reacts with acidified H2O2 (aq) to form iodine which turns blue in the presence of starch.
2KI (aq) + H2O2 (aq) + 2H+ (aq)  I2 (aq) + 2K+ (aq) + 2H2O (l)

Na2S2O3 delays the formation of blue colour. Repeat reaction using the same quantity of Na 2S2O3 each
time, but at different temperature and measure the time taken for the blue colour to appear.

- Particle size/Surface area (of a solid reactant)

 Decreasing the particle size causes an increase in the rate of reaction
 For a reaction involving a solid, the reaction can only happen at its surface. If more surface area is
available, the reaction will happen faster, as more area is available for collisions.
 For example, Calcium carbonate in the form of marble chips reacts with dilute HCl to produce carbon
dioxide.
CaCO3 (s) + 2HCl (aq)  CaCl2 (aq) + H2O (l) + CO2 (g)
Chemistry Handout 15 REF #: 015
Suppose you start with one 10 g lump of marble. Instead of using it as it is, you break it up into 10 1 g
lump. You have the same amount of marble but much more surface area is available for the acid to act
upon. Consequently, the reaction is faster. Infact, the reaction would be even faster if the marble was
powdered. Warning, Finely divided solids catch fire more readily than larger pieces of the same solid,
e.g, in flour mills, there is a danger of the flour burning explosively.

- Catalyst
 Adding a catalyst alters the rate of a reaction- can increase or decrease depending on the type of
catalyst used
 A catalyst is a chemical which alters the rate of a chemical reaction but do not get used up themselves-
that is, they can be used over and over again.
 Catalysts provide an alternative pathway for a reaction with a lower activation energy. The reaction
therefore takes place more readily as more particles will have the sufficient energy to collide and react.
 For example, potassium chlorate is a white solid. When heated strongly, it first melts and then
decomposes to give off oxygen.
KClO3 (s)  3O2 (g) + 2KCl (s)
Manganese (IV) oxide is a black powder and acts as a catalyst for this reaction. If a small amount is
mixed in with the potassium chlorate before it is heated, then the oxygen is evolved much more quickly,
even before the potassium chlorate melts. The temperature takes place more quickly and at a lower
temperature because of the catalyst. The manganese (IV) oxide will not have been used up during the
reaction and may be used again.
 Catalysts are specific, in that one type of catalyst can catalyze only a specific type of reaction. Catalysts
in biological systems are called enzymes and these are very specific.
 Not all catalysts speed up reaction rates. Some catalysts called inhibitors, slow down a rate of chemical
change. Inhibitors are added when canning food to slow down certain reactions which make the food go
bad. Inhibitors such as tetra ethyl lead (IV) Pb(C 2H5)4 is added to petrol to help stop premature ignition
(knocking)

- Light
 Exposure to light increases the rate of some reactions.
 Light is a form of energy, which on absorption causes bond to break in the reactants. Reactions such as these are
called photochemical reactions and are photosensitive.
 For example, the light dependent stage of photosynthesis- the photolysis of water – to oxygen and H 2
 The combination of Hydrogen and chlorine does not occur in darkness but under bright light, the reaction is so
fast that it is explosive.
H2 (g) + Cl2 (g)  (light) 2HCl (g)

Rate Curves

When the change in concentration of a reactant or product is plotted against time, a rate curve is obtained.

The rate of any reaction is greatest where the graph is steepest i.e, at the beginning of the reaction. The rate of any
reaction decreases as the reaction proceeds. The concentration of the reactants is at its highest at the start of the
reaction, therefore the number of collisions between particles is at its highest. As the reaction proceeds, the
concentration of the reactants decreases, therefore, the number of collisions between particles decreases.