Unit 2
Chemical Equilibrium : Equilibrium constant and free energy, thermodynamic derivation of
law of mass action. Le-Chatelier's principle. reaction isotherm and reaction isochore –
Clapeyron- Clausius equation and its applications.
INTRODUCTION
The reaction rates of the forward and backward reactions are generally not zero, but equal. Thus,
there are no net changes in the concentrations of the reactants and products. Such a sate is known
as dynamic equilibrium.
REVERSIBLE AND IRREVERSIBLE REACTIONS:
Not all chemical reactions proceed to completion .In most reactions two or more substances react
to form products which themselves react to give back the original substances. Thus A and B may
react to form C and D which react together to reform A and B.
A+B→C+D (Forward reaction)
A+B←C+D (Reverse reaction)
A reaction which can go in the forward and backward direction simultaneously is called a
Reversible reaction. Such a reaction is represented by writing a pair of arrows between the
reactants and products.
A+B⇌ C+D
The arrow pointing right indicates the forward reaction, while that pointing left shows the
backward reaction. Some Examples of Reversible Reactions:
A few common examples of reversible reactions are listed below:
N2 + 3H2 ⇌ 2NH3
H2 + I2 ⇌ 2HI
PCl5 ⇌ PCl3 + Cl2
CHEMICAL EQUILIBRIUM:
A+B⇌ C+D
Consider the reaction:
If we start with A and B in a closed vessel,the forward reaction proceeds to form C and D. The
concentrations of A and B decrease and those of C and D increase continuously. As a result the
rate of forward reaction also decrease and rate of backward reaction increases. Ultimately, the
rate of two opposing reactions equals and the system attains a state of equilibrium. Thus “The
state of reversible reaction in which the concentrations of the reactants and products do not
change is called chemical equilibrium”.
Characteristics of chemical Equilibrium:
Some of the important characteristics of chemical equilibrium are follows:
(i) At equilibrium, the concentration of each of the reactants and products becomes constant.
(ii) At equilibrium, the rate of forward reaction becomes equal to the rate of backward reaction
and hence the equilibrium is dynamic in nature.
(iii) A chemical equilibrium can be established only if none of the products is allowed to escape
out.
(iv) Chemical equilibrium can be attained from either direction i.e from the direction of reactants
as well as from the direction of the products.
(v) A catalyst does not alter the state of equilibrium.
LAW OF MASS ACTION
Guldberg and Waage, the two Norwegian chemists put forward a law concerning the dependence
of rate of reaction on the concentration of the reactants. This law is known as Law os Mass
Action. It states as follows: The rate of chemical reaction is proportional to the active masses
of the reactants.
The term active mass used in the above statement implies activity which, for the sake of
simplicity, may be taken as equal to molar concentration.
Consider the following reversible reaction, taking place at constant temperature:
A+B⇌ C+D
According the law of mass action, the rate (r1) at which A and B react is given by the equation
r1 α [A ] [ B]
Where k1 is the proportionality constant, called rate constant of the reaction and the square
brackets indicate molar concentrations. The rate of backward reaction (r 2) is given by the
equation.
r2 α [C ] [ D]
Where k2 is the rate constant of reverse reaction.
Thus ultimately, a dynamic equilibrium is attained when the rate of forward reaction becomes
equal to that of the reverse reaction , i.e., r1 = r2.
LAW OF CHEMICAL EQUILIBRIUM AND EQUILIBRIUM CONSTANT
aA + bB ⇌ cC + dD
Consider the following reversible reaction:
Where a, b, c and d are numerical quotients of the substance, A , B , C and D respectively.
According to law of mass action,
Rate of forward reaction, r1 = k1 [A]a[B]b
Rate of backward reaction, r2 = k2 [C]c [D]d
Since at equilibrium, r1 = r2, it follows that k1 [A]a[B]b = k2 [C]c [D]d
k1/ k2 = kc = [C]c [D]d / [A]a[B]b
kc is known as equilibrium constant and has a fixed value for a certain reaction at a given
temperature and pressure and is independent of the amounts of reactants and products. However,
its value depends on the temperature and types of reactions.
RELATIONSHIP BETWEEN KP AND KC
aA + bB ⇌ cC + dD
For a general reaction,
The equilibrium constant in terms of concentrations (moles/liter) is
kc = [C]c [D]d / [A]a[B]b ---(i)
If the reactants and products are gaseous, then the concentration terms may be replaced
by partial pressure. The equilibrium constant Kp written as,
Kp = Pcc. Pdd/ Paa Pbb ---(ii)
For an ideal gas, PV= nRT
or, P = nRT/V or, P=CRT
Where C is the molar concentration. For different gases A, B, C, D, we may write
PA = CA RT, PB =CBRT, PC =CCRT, PD =CDRT
Putting these values in equation (ii), we get
Kp = (CCRT)c . (CDRT)d / (CART)a . (CBRT)b --- (iii)
Where ∆n = ( c+d )– (a+ b) = [number of moles of products]- [number of moles of reactants]
THERMODYNAMIC DERIVATION OF THE LAW OF CHEMICAL
EQUILIBRIUM
aA + bB ⇌ cC + dD
Let us consider a general reaction,
The chemical potential of a substance in a mixture is related to its activity by the expression
µ = µ0 + RT ln a --- (i)
0
Where µ is the chemical potential of pure substance in standard state of unit activity, R is the
gas constant and T is the absolute temperature.
For a mole of the substance A we can write using the equation (i)
aµ = a(µ0 + RT ln a)
And similarly,
bµ = b(µ0 + RT ln a)
cµ = c(µ0 + RT ln a)
dµ = d(µ0 + RT ln a)
The change in free energy for the reaction is given by
∆G = Gproducts - Greactants
On substitution we get
( cµc +dµd +…) – (aµa +bµb +…)
= [c(µ0c + RT ln ac)+ d(µ0d + RT ln ad)]-[a(µ0a + RT ln aa)+ b(µ0b + RT ln ab)]
