PROF.

RAKESH RATHI’S CHEMISTRY TUTORIALS

The expression of reaction quotient is similar to that of equilibrium constant, the only difference is that the
equilibrium constant involves equilibrium concentrations or partial pressure of products and reactants.
Where as expression of Q is in term of concentrations or partial pressure other than equilibrium values.
For example, for the reaction
aA + bB → cC + dD
The reaction quotient is given by
[C]c [D]d PCc ×PDd
Qc = or Q p =
[A]a [B]b PAa ×PBb
Where the values of concentration or partial pressures are other than equilibrium values.

At equilibrium G = 0 and Q = K, the equation becomes

0 = Go + RT lnK
Go = −RT lnK
Go = −2.303 RT log10K.
This equation gives the relationship between standard Gibbs energy of the reaction and its equilibrium constant.

Third law of thermodynamics

It states that the entropy of a perfectly ordered crystalline substance is zero at absolute zero of
temperature.
Thus, S = 0 at T = 0, for any perfectly ordered crystalline substance

If a crystal contains some impurities or the molecules of the substance have different orientations at 0K, the
substance is not perfectly ordered. In such a case the entropy of the crystalline substance is greater than zero at
T = 0 due to the disorder associated with the substance. This entropy of solid greater than zero at T = 0 is called
the residual entropy of the substances.

The importance of third law is that it allows to determine the absolute entropy of any substance either in solid,
liquid or gaseous state at any desired temperature.
For example, if a perfectly ordered crystalline substance with S = 0 at T = 0 is heated from 0 K to any
temperature T, the entropy increases.

The increase in entropy is given by ∆S = ST − S0

where ST is the absolute entropy of the substance at temperature T and S0 its value at T = 0.
Because, S0 is zero, ∆S = ST.

The value ST can be determined by measuring heat capacity of the solid at various temperatures and using the
expression.
T C .dT
∆S = ST − S0 = ST = 
p

O T
Similarly absolute entropies of liquids and gases can also be determined.

As the perfectly ordered crystalline substance is heated from T = 0, its entropy increases gradually due to an
increasing disorder. At the melting point of solid, the increase in entropy is more due to the formation of liquid.
Further heating increases the entropy of liquid. At the boiling point of liquid, there is substantial increase in
entropy due to the formation of gas.

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