Chemical reactions

7.1 Speed of reaction

Some reactions are very fast, e.g. the formation of silver chloride precipitate when silver
nitrate and silver chloride solutions are mixed. Other reactions are very slow, e.g. the
rusting of iron.
Factors affecting speed of reactions:

Particle size (surface area)

Concentration
Temperature
Presence of catalyst
Light

Measuring the speed of a reaction that produces a gas:

Take for example the reaction between magnesium and excess dilute hydrochloric acid.

The speed of the reaction can be followed by measuring the volume of gas evolved over a
period of time using the apparatus below:

The flask is divided into 2 compartments. The acid is put into one compartment and the
metal into the other. The reactants are separated whilst setting the apparatus so that the
starting time of the reaction can be accurately determined. When the flask is tipped up, the
reactants mix and start producing the gas. The gas pushes its way out of into the syringe;
the plunger of the syringe is forced back. Readings of the volume are taken every minute,
using the scale marked on the side of the syringe.

The reaction is much faster at the start: 12 cm3 are produced during the first minute, but
only 3 cm3 during the fifth minute (33 cm3 30 cm3 = 3 cm3).
Notice that the curve is steepest at the start: after nine minutes it has gone completely flat.
That means that the reaction is complete.

The collision theory:

The collision theory is the most common one used to explain the facts concerning the
speed of reactions.
The two main statements of this theory are:
Particles must collide before they can react.
The colliding particles must contain enough energy to cause bonds to break.
Effect of particle size (surface area):
The effect of particle size can be examined by doing 2 experiments, A and B.
The experiment using the divided flask can be done with calcium carbonate and acid.
HCl of the same concentration is added in excess to:
Powdered marble in A
Marble chips in B

1. Curve A is steeper than curve B showing that the reaction was faster in case of powdered
marble. This explains why mixtures of air and coal dust in mines sometimes explode.
2. 40 cm3 of CO2 were produced in both the two experiments: in 1.5 minutes in A, but in 5.5
minutes in B.
Conclusion:
The speed of a reaction increases with increase of the surface area of a solid reactant.
This is because a reaction can only take place at the surface of a solid. Breaking a solid into
smaller pieces increases its surface area, allowing more collisions with other reactants.
This also results in explosions in flour mills and coal mines where flour and coal are
powdered and the surface area in contact with air is huge.
Effect of concentration:
The effect of concentration can be examined by doing 2 experiments A and B. Hydrochloric
acid of different concentrations (1 M in A and 0.5 M in B) is added in excess of equal masses
of Magnesium ribbon (e.g. 0.06 g)

The acid in B is twice as

concentrated as in A. Both
sets of results are shown on
the same graph.
1. Curve A is steeper than
curve B showing that the

reaction is faster in the case of 1 M acid.

2. 60 cm3 of hydrogen was produced in both experiments: in 60 seconds in A, but in 120
seconds in B.
Conclusion:
The speed of the reaction increases with the increase of the concentration of the
reactants.
Reason:
This is because increasing the concentration of reactants increases the number of particles
in a given volume and so increases the number of collisions between the reactants which
means an increase in successful collisions.
Effect of temperature:
The speed of the reaction increases with an increase of temperature.
A rise of 10 degrees C approximately doubles the speed of the reaction.
Reason:
This is because increasing the temperature makes the particles move faster and increase
the number of successful collisions.
The reverse decreases the rate of the reaction. This is what fridges do, by lowering the
temperature, lowers the rate of food decay.
Effect of catalyst:
A catalyst is a substance which speeds up reactions, but remains chemically unchanged at
the end of the reaction. Enzymes are biological catalysts.
Some industrial reactions need high temperatures in order to give good yield or products. If
a powerful catalyst is used, the reaction will take place faster and at a lower temperature.
The decreases fuel costs and lower the cost of eventual products.
For example:
A finely divided iron catalyst in Habers process to produce ammonia
Vanadium (V) oxide in the contact process to process sulphuric acid.
Catalysts are mostly transitional elements or their compounds.

Since catalysis takes place at the surface of the catalyst; the catalyst must be finely divided
in order to increase the surface area in contact with the reactants.

E.g. At room temperature, Hydrogen Peroxide decomposes into water and oxygen, but very
slowly. Using manganese (IV) oxide, the reaction speeds up.

This reaction is done twice, once without the catalyst and once with the catalyst:

If the manganese (IV) oxide is filtered off at the end of the reaction, washed, dried and
reweighted, it will be found that its mass has not changed.
Effect of light:
The speeds of some reactions are increased by exposure to light. Light, like heat, is a form
of energy. Therefore, light has a similar effect to an increase temperature.
The reactions which are speeded up by light are called photochemical reactions.
Examples:
A mixture of Hydrogen and Chlorine explodes in light forming hydrogen chloride
(Hydrochloric acid in water).

 Photography:
The darkness of a silver bromide coating on a film in a camera when a light is shown
on it is the basis of photography.
The photochemical reaction that takes place is:

It takes place in two steps:

Oxidation
And
Reduction
Photosynthesis:
It is the process by which plants make glucose from water (in the soil) and carbon
dioxide (in the air) by using sunlight energy, which is absorbed by chlorophyll present
in the chloroplast in the plants cells. The chlorophyll here is a catalyst.

Photosynthesis is an endothermic reaction, in which the energy of sunlight is

transformed into the energy of the chemical bonds in the glucose.
Respiration:
On the reverse, it is an exothermic reaction, in which the energy in glucose is
released by oxidizing it with atmospheric oxygen in animal cells.

7.2 Reversible Reactions

Most chemical reactions can only go in one direction.
Example:

There is no way that the reverse reaction would occur. Hydrogen will not react with
magnesium chloride to make magnesium and hydrochloric acid.
Some reactions, however, are reversible.
A reversible reaction is a reaction that can go in either direction from the left to the right
and vice-versa, depending on the conditions of the reaction.
The sign

in an equation show that the reaction is reversible and is at equilibrium.

Some examples:
When blue copper (II) sulphate crystals are heated, the water of crystallization is
driven off. The blue crystals become white crystals of anhydrous copper (II) sulpahte.
( )

( )

When water is added to the copper sulphate, the reverse happens, so the
used instead of the forward arrow sign.

sign is

When ammonium chloride crystals are heated, the ammonium chloride decomposed
into ammonia gas and hydrogen chloride gas. As the gas cools the reverse happens.

Hot iron reacts with steam forming iron oxide and hydrogen

The reverse can also happen; hot iron oxide is reduced to iron and steam by passing
dry hydrogen over it.
An interesting consideration now is what would happen if the four chemicals were
together in a seal container.
Iron would react with steam forming iron oxide and hydrogen, but at the same time
iron oxide would be reacting with hydrogen to make iron and steam.
After some time the reactions stops, which is said to be at a state of equilibrium,
where the rate of the forward reaction equals the rate of the backward reaction.

Equilibrium means:
Le Chateliers Principle:
For any system in equilibrium, any change in an external factor such as temperature,
pressure or concentrations), the equilibrium moves to oppose the change.
The effect of temperature:
Exothermic reactions are favored by decreasing the temperature and opposed by
increasing the temperature, which is because exothermic reactions give out heat.
The reverse happens with endothermic reactions.
The effect of pressure:
This applies only to reactions involving gases.
Reactions accompanied with a decrease in volume (produce less molecules) are
favored by increasing the pressure, and opposed by decreasing it.
e.g. the formation of ammonia in the Habers process:

1 Mol 3 Mols 2 Mols

On the left side 4 volumes and on the right 2 volumes
The reverse happens with reactions accompanied with pressure.
Effect of concentration
For a system in equilibrium, if the concentration of one reactant is increased, the
equilibrium will move in the direction which tends to decrease the concentration of
the substance.
The reverse happens when the concentration of one substance is decreased or if it
is removed, where the equilibrium would move to direction that would produce
more of that product.

7.3 Oxidation and reduction

Oxidation is the gain of oxygen or the loss of electrons.
Reduction is the loss of oxygen or the gain of electrons.

OIL RIG of electrons

Oxidation is Loss and Reduction is Gain
1. Oxidation:
Oxidation is the gain of oxygen or the loss of electrons.
An oxidizing agent is a substance that will add oxygen to other substances during a reaction.
It gives oxygen to other substances
Takes hydrogen from other substances
Takes electrons from a substances
Common oxidizing agents are:
Oxygen
Hydrogen peroxide
Potassium manganate (VII)

Potassium dichromate (VI)

Chlorine
Sulphuric acid
Nitric acid

Oxidation is:
The addition of oxygen:
Example:

The oxygen here is added to the copper, so the copper is oxidized

Removal of Hydrogen:
Example:

Hydrogen was removed from the HCl by oxidation.

Loss of electrons:

The increase in oxidation state

What is an oxidation state?

It is the number of electrons lost or gained during a chemical reaction to form an octet
configuration.
Group
1
2
3

Oxidation State
+1
+2
+3

Valency
1
2
3

4
5
6
7
8/0

4
-3
-2
-1
0

4
3
2
1
0

Rules for the oxidation state:

The oxidation state on any atom in the elemental state is 0
E.g. Na, Mg, Cl
The sum of oxidation states of all atoms in a molecule is 0
E.g. Cl + Cl -> Cl20
The oxidation state of an ion is the charge on the ion
E.g. Cl-1, Na+1, NO3-1
The oxidation state of Hydrogen is +1, for example, in HCl is H+1 Cl -1.
When it combines with metals to form hydrides, the oxidation state is -1.
Oxidation state of oxygen is -2, except when it forms peroxides, for example, H2O2
Transitional elements show variable valency so they have variable oxidation states,
for example, Iron (II) and Iron (III).
2. Reduction:
Reduction is the loss of oxygen or the gain of electrons.
A reducing agent is a substance that will remove oxygen from other elements.
Takes oxygen from other substances
Gives hydrogen to other substances
Gives electrons to other substances
Some examples are:
Hydrogen
Carbon
Carbon monoxide

 Metals
Reduction is:
The loss of oxygen:
Example:

Addition of hydrogen:
Example:

Gain of electrons:
Example:

Decrease in oxidation state

REDOX Reduction and Oxidation in the same time

In redox reactions, reduction and oxidation occur together.
If one substance is oxidized the other is reduced.
Example:

 Copper (II) oxide here is reduced into Copper. It had lost oxygen, so it is the oxidizing
agent.
Hydrogen is oxidized. It had gained oxygen, so it is the reducing agent.
Conclusion:
The substance oxidized is the reducing agent and the one reduced is the oxidizing agent.
Example:
( )

Identification of redox reactions:

1. Change in oxidation state:

Since oxidation is the loss of electrons, the oxidation of the reducing agent would increase,
which means more protons and less electrons.
e.g.
Fe2+ Fe 3+ + eSince reduction is the gain of electron, the oxidation state of the element would decrease.
Fe3+ + e - Fe 2+
2. Change in colour:
Potassium Iodide K+I- solution turns from colorless to brown when the iodide ions are
oxidized by a oxidizing agent into iodine (Brown)
Potassium manganate (VII) KMnO4 solution (acidified with dilute sulphuric acid) turns
from purple to colourless when the manganate (VII) ions are reduced by a reducing
agent into manganese ions Mn Potassium dichromate (VI) K2Cr2O7 solution (acidified with dilute sulphuric acid) turns
from orange to green when the dichromate ions are reduced by a reducing agent to
chromium (III) ions Cr3+