Anda di halaman 1dari 17

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
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.

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

B. Liquid phase reaction


C. Solid phase reaction

EXAMPLES OF REVERSIBLE HETEROGENEOUS REACTIONS:


A. Heterogeneous reactions in a closed vessel.

EXAMPLES OF IRREVERSIBLE REACTIONS

CHARACTERISTICS OF CHEMICAL EQUILIBIRUM

A. Rate of forward reaction is equal to the rate of backward reaction

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.

LAW OF MASS ACTION


(Norwegian chemists (and brothers-in-law) Cato Guldberg and Peter Waage)
Berthelots ideas about reversible reactions were finally proved by experiments carried out by
others, most notably the Norwegian chemists (and brothers-in-law) Cato Guldberg and Peter
Waage.
During the period 1864-1879 they showed that an equilibrium can be approached from either
direction (see the hydrogen iodide illustration above), implying that any reaction aA + bB
cC + dD is really a competition between a forward and a backward reaction. When a
reaction is at equilibrium, the rates of these two reactions are identical, so no net
(macroscopic) change is observed, although individual components are actively being
transformed at the microscopic level.
Guldberg and Waage showed that the rate of the reaction in either direction is proportional to
the active masses of the various components:
rate of forward reaction = kf[A]a[B]b
rate of reverse reaction = kb[C]c[D]d
in which the proportionality constants k are called rate constants and the quantities in square
brackets represent concentrations. If we combine the two reactants A and B, the forward
reaction starts immediately, but the formation of products allows the backward process to get
underway. As the reaction proceeds, the rate of the forward reaction diminishes while that of
the backward reaction increases.
Eventually the two processes are proceeding at the same rate, and the reaction is at
equilibrium:
Rate of forward reaction = Rate of backward reaction
Kf [A]a [B]b = kb[C]c [D]d
Rate at which a substance reacts is proportional to its active mass and overall rate of reaction
is proportional to the product of active masses of the reactants.
Rate of reaction: Change in concentration per unit time
Unit: molL-1time-1
Active mass: Molar concentration
Unit: mol L-1
Example:
64 gm of HI(g) are present in a 2 litre vessel. Calculate the active mass of HI i.e. [HI]
(Atomic mass H = 1 & I = 127)

Soln:

NOTE: For pure solids and pure liquids active mass is taken to be unity.
For a homogeneous reversible gaseous reaction:

Where kf and kb are rate constants


Therefore, at equilibrium rf = rb
So, K (equilibrium constant =

Types of Equilibrium constants

Units of equilibrium constants:


Since active mass or activity is generally defined by specifying a standard state of a substance
which is either 1.0 molar concentration or 1.0 bar pressure at a constant temperature to be
specified, therefore it must be a unitless quantity for example a pressure of 2 bar in terms of
standard state is 2bar/1bar = 2 only. As such equilibrium constant Kc or kp must be unitless.
However for particle purposes we express concentrations in terms of mol-1L and pressure in Pa,
kPa , bar or atmosphere. Hence units of equilibrium constants are:

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]

Predicting the direction of a reaction


(Concept of reaction quotient, Q)

Where concentrations and partial pressure correspond to that instant of reaction:


(i) If Qc>Kc ; the reaction proceeds in the backward direction
(ii) If Qc < Kc ; the reaction proceeds in the forward direction, till equilibrium is attained.
(iii) If Qc = Kc ; the reaction is already in a equilibrium state.
Example:

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.

CHARACTERISTICS AND FACTORS AFFECTING EQUILIBRIUM


CONSTANT
1. Temperature:

heat or enthalpy of reaction in the

temperature range T1 and T2 (T2>T1)

2. Stoichiometry of the reaction

3. Standard free energy change (Go) for the reaction


for any reaction

4. Relation between Kp, Kc and Kx

Problem: At 27oC, kp for the reaction

is 0.1 atm. Calculate kc.

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.

FACTORS NOT AFFECTING EQUILIBRIUM CONSTANT

Time taken in the attainment of equilibrium


Presence of catalyst
Concentration of reactants and products involved.
Pressure

CALCULATION OF EQUILIBRIUM CONSTANT AND AFFECTS OF


SOME FECTORS ON THE EQUILIBRIUM STATE.
For Gaseous Reactions

Problem: 2 moles of H2 and 4 moles of I2 are mixed in a vessel of 2.5L capacity at a


constant temperature to attain equilibrium. If at equilibrium it is found that only 0.5 mole
of H2 has been used up, then the molar concentration of HI at equilibrium is-

(a) Effect of change of concentration


If [H2] or [I2] or in general concentration of a reactant is increased then
equilibrium shifts in the forward direction i.e. to form more products.
(b) Effect of change of pressure
For n=0 type of gaseous reactions, there is no change on the equilibrium state.
(c) Effect of change of temperature
The given reaction is exothermic hence increase of temperature at equilibrium
state will shift the equilibrium in backward direction.

(d) Effect of introducing inert gas at equilibrium


(i) at constant volume: No effect for any type of gaseous reaction.
(ii) at constant pressure: No effect for n=0 type of gaseous reaction.

Expression of kp and kc for


B. n > 0 type gaseous reaction

Where V and P are volume and pressure equilibrium at constant


temperature.
C. n< 0 type gaseous reaction

Factors favouring more of information of NH3


i. increasing concentration of N2 or H2
ii. high pressure
iii. low temperature
iv. use of catalyst (Fe - powder with Mo as promoter)
Expression of equilibrium constant for a heterogeneous reaction
Problem: for the reaction
NH2COONH4(s) 2NH3(g) + CO2(g); the equilibrium constant kp = 2.9 x 10-5 atm3.
The total pressure of gases at equilibrium when 1.0 mole of reactant was heated,
will be
(A) 0.0194 atm
(B) 0.0388 atm
(C) 0.0580 atm
(D) 0.0667 atm

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:

Changing concentrations by adding or removing products or reactants to the reaction


vessel.
Changing partial pressure of gaseous reactants and products.
Changing the temperature.

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.

An increase in pressure on a system where liquid-vapour equilibrium exists


According to the Le Chateliers principle, this will make the system move in a direction of lower
volume. An increase in pressure on the system will result in the condensation of vapours to
give liquid, since; liquids have lower volume as compared to vapours. The equilibrium will shift
towards left. On the other hand, if the pressure is decreased, more and more liquid will get
converted into vapours.
The effect of increase in temperature where liquid-vapour equilibrium exists
According to the Le Chateliers principle, this will make the reaction move in a direction which
absorbs heat i.e., the endothermic process will be favoured. As vaporization (liquid g vapours)
is an endothermic process, a rise in temperature will favour the process of vaporization i.e.
more liquid would get converted into vapours.
As a result of these effects an increase in temperature and decrease in pressure, shall favour
this process Liquid
Vapour to proceed in the forward direction.
For example, during the preparation of carbonated drinks such as Cola or beer, a large amount
of CO2 is dissolved in the solution under high pressure. When these bottles are opened, the
pressure decreases and the dissolved carbon dioxide escapes out.
Manufacture of ammonia (Habers Process)
Ammonia can be synthesized from nitrogen and hydrogen in accordance with the reaction.

The equilibrium constant of this reaction may be written as,

The characteristics of the reaction are:

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)

The endothermic reaction,

is one of the initial reactions in the Birkland - Eyde process for the manufacture of nitric acid.
The reaction is characterised by,

No change in volume i.e. n = 0

An endothermic reaction i.e., heat is absorbed during the reaction.

As a result of Le Chateliers principle,

The equilibrium state is not affected by any change in pressure.

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.

Formation of nitric oxide is favoured by taking any of the reactants, N2 or O2 in excess,


(concentration effect).

Actually, nitrogen and oxygen are made to combine at 3000C by means of an electric arc.