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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
and
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.
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.
B.
Observable properties of the system such as pressure, concentration, density etc. remains
invariant with time
C. Dynamic in nature:
a. Reaction takes place in both the directions even after the achievement of equilibrium
state.
b. Equilibrium state can be displaced in either direction by change of factors like
pressure, concentration and temperature.
D. G = 0
E. It can be achieved from any direction
F. Use of catalyst does not affect the equilibrium state but time taken for the attainment of it
can be altered.
Soln:
NOTE: For pure solids and pure liquids active mass is taken to be unity.
For a homogeneous reversible gaseous reaction:
Kx : unitless, always
Where n = (number of moles of gaseous products) - (number of moles of gaseous reactants)
in a balanced chemical equation of the reaction.
Note: 1 atm = 101.325 kPa
1 bar = 100kPa
1 atm = 1.013 bar
[Pa = Pascal]
Now suppose at 700 K, we put a mixture of above three gases in a closed vessel such that at
that instant
Qc < Kc, the above mixture is not at equilibrium and reaction will go in the forward direction
to from more HI till Qc becomes equal to K.
Answer:
NOTE: In all the above calculation dealing with kp, kc relation take R = 0.082 L atm k-1 mol-1 and T
in terms of Kelvin
5. Significance of equilibrium constant
Generally if kc > 103 (products predominate) if k < 10-3 (reactant predominate) but if k is in the
range 10-3 to 103, then appreciable concentrations of both products and reactants are present
at equilibrium.
Le Chateliers Principle
Le Chateliers principle states that when a system in chemical equilibrium is disturbed by a
change of temperature, pressure, or a concentration, the system shifts in equilibrium
composition in a way that tends to counteract this change of variable.
The three ways that Le Chateliers principle says you can affect the outcome of the equilibrium
are as follows:
These actions change each equilibrium differently; therefore you must determine what needs
to happen for the reaction to get back in equilibrium.
Example involving change of concentration:
In the equation
If you add more NO(g) the equilibrium shifts to the right producing more NO2(g)
If you add more O2(g) the equilibrium shifts to the right producing more NO2(g)
If you add more NO2(g) the equilibrium shifts to the left producing more NO(g) and O2(g)
Example involving pressure change:
In the equation
an increase in pressure will cause the reaction to shift in the direction that reduces pressure,
that is the side with the fewer number of gas molecules. Therefore an increase in pressure will
cause a shift to the right, producing more products. (A decrease in volume is one way of
increasing pressure.)
Example involving temperature change:
In the equation
An increase in temperature will cause a shift to the left because the reverse reaction uses the
excess heat. An increase in forward reaction would produce even more heat since the forward
reaction is exothermic. Therefore the shift caused by a change in temperature depends upon
whether the reaction is exothermic or endothermic.
Firstly, the reaction proceeds with a decrease in volume. Therefore, an increase in pressure
should favour the forward reaction. The equilibrium between nitrogen, hydrogen and ammonia
at 200C has been studied at different pressures and the following data has been obtained.
The most favourable pressure range for the production of ammonia is found to be 152000 684000 mm of Hg pressure.
Secondly, the reaction is exothermic; therefore the Le Chateliers principle predicts lower
temperature to be favourable for the forward reaction.
Since at low temperature, the reactions tend to be slow due to kinetic effects, an optimum
temperature (450C) should give the most favourable results.
Thirdly, since the reaction involved two gases, the use of a suitable catalyst should accelerate
the reaction in the forward direction.
Manufacture of sulphur trioxide (Contact Process)
During the manufacture of sulphuric acid (Contact process), sulphur trioxide is prepared by the
oxidation of sulphur dioxide in accordance with the reaction,
This reaction proceeds with a decrease in volume. Therefore, high pressure will favour the
forward reaction.
Secondly, the reaction is exothermic; hence low temperature will be favourable for higher yield.
Thirdly, if the reaction is carried out under excess of oxygen, the equilibrium shifts in a
direction so as to give larger amount of SO3, due to the effect of increased concentration of one
of the reactants. The optimum conditions for the reaction between SO2(g) and O2(g) are: a
pressure of 1140 - 1292 mm of Hg and temperature 420C - 450C.
Formation of Nitric oxide (Birkland-Eyde process)
is one of the initial reactions in the Birkland - Eyde process for the manufacture of nitric acid.
The reaction is characterised by,
Due to endothermic nature of the reaction, an increase in temperature will favour the
forward reaction i.e., more nitric oxide is formed at higher temperature.
Actually, nitrogen and oxygen are made to combine at 3000C by means of an electric arc.