CHEMICAL EQUILIBRIUM

When a chemical reaction takes place in a closed container which prevents the entry or
escape of any of the substances involved in the reaction, the quantities of these
components change as some are consumed and others are formed. Eventually this change
will come to an end, after which the composition will remain unchanged as long as the
system remains undisturbed. The system is then said to be in its equilibrium state, or more
simply, at equilibrium
i.e. A state of a chemical reaction in which rate of forward reaction ( rf ) becomes equal to
the rate of backward reaction ( rb ).
The direction in which we write a chemical reaction (and thus which components are
considered reactants and which are products) is arbitrary. Thus the equations
H2 + I2
2HI
synthesis of hydrogen iodide
and
2HI
H2 + I2 dissociation of hydrogen iodide
represent the same chemical reaction system in which the roles of the components are
reversed, and both yield the same mixture of components when the change is completed.
NOTE: A chemical reaction is in equilibrium when there is no tendency for the quantities of
reactants and products to change.
TYPES OF REACTIONS
a) Reversible reactions attain equilibrium state
b) Irreversible reactions do not attain equilibrium state
A chemical equation of the form A
B represents the transformation of A into B, but it
does not imply that all of the reactants will be converted into products, or that the
reverse reaction B
A cannot occurs. In general, both processes can be expected to
occur, resulting in an equilibrium mixture containing all of the components of the reaction
system. (We use the word components when we do not wish to distinguish between
reactants and products.) If the equilibrium state is one in which significant quantities of
both reactants and products are present (as in the hydrogen iodide example given
above), then the reaction is said to incomplete or reversible.

If it is desired to emphasize the reversibility of a reaction, the single arrow in the equation is
replaced with a pair of hooked lines pointing in opposite directions, as in A
B. There
is no fundamental difference between the meanings of A
B and in A
B,
however some older text-books even use A = B.
A reaction is said to be complete when the equilibrium composition contains no significant
amount of the reactants. However, a reaction that is complete when written in one
direction is said not to occur when written in the reverse direction.

In principle, all chemical reactions are reversible, but this reversibility may not be
observable,
if the fraction of products in the equilibrium mixture is very small,
Or if the reverse reaction is kinetically inhibited.
EXAMPLES OF REVERSIBLE HOMOGENEOUS REACTIONS:
A. Examples of Gaseous reactions in a closed vessel
a)
b)
c)
d)
e)

H2 + I2
N2 + 3H2
2SO2 + O2
PCl5
N2 + O2

2HI
2NH3
2SO3
PCl3 + Cl2
2NO

B. Liquid phase reaction

CH3COOH (l) + C2H5OH (l)

CH3COOC2H5 (l)

C. Solid phase reaction

C (diamond)
C (graphite)
EXAMPLES OF REVERSIBLE HETEROGENEOUS REACTIONS:
A. Heterogeneous reactions in a closed vessel.
a)
b)
c)
d)

CaCO3 (s)
C (s) + H2O (g)
3Fe (s) + 4H2O (g)
NH4HS (s)

CaO (s) + CO2 (g)

H2 (g) + CO (g)
Fe3O4(s) + H2S (g)
NH3 (g) + H2S (g)

EXAMPLES OF IRREVERSIBLE REACTIONS

a) Decomposition reaction
2KClO3 (s)

2KCl (s) + 3O2 (g)

b) Precipitation reaction
NaCl (aq) + AgCl (aq)

AgCl (s) + NaNO3 (aq)

c) Neutralisation reaction
NaCl (aq) + HCl (aq)

NaCl (aq) + H2O (aq)

d) Combustion of a gas
CH4 (g) + 2O2 (g)

CO2 (g) + 2H2O (l)