BMI-102 Basic Chemistry

Internal Assignment III

1. Give the relation between standard free energy and equilibrium constant. What is
the importance of this relationship?
The standard free energy change of a reaction is related to the equilibrium constant by the
reaction:
G0 = - 2.303 RT log Keq
where R = gas constant (= 8.314 J K-1 mol-1); T=temperature in Kelvin.

The free energy change of the reaction in any state, G(when equilibrium has not been
attained) is related to the standard free energy change of the reaction, G0 (which is
equal to the difference in free energies of formation of the products and reactants both in
their standard states) according to the equation.
E=emf of the cell
G= G0 + RT lnQ
Where Q is the reaction quotient
When equilibrium is attained, there is no further free energy change i.e, G=0
and Q becomes equal to the equilibrium constant.Hence, the above equation becomes
G0 = - RT in K(eq) or G0 = -2.303 RT log K(eq) in case of galvanic cells.
Gibbs energy change G is related to the electrical work done by the cell.
G = -nFE(cell) where n = no. of moles of electron s involved
F = the faraday constant
E = emf of the cell if reactants and products are in their standard
States
A spontaneous reaction has negative G and a large K value. A non-spontaneous
reaction has a positive G and small K value. When G is equal to zero and K is
around one, the reaction is at equilibrium. This relationship allow us to relate the standard
free energy change to the equilibrium constant.
2. Explain third law of thermodynamics and discuss its significance.
Ans. Third law of Thermodynamics states that Entropy of a perfectly ordered crystalline
substance is zero at absolute temperature.
Thus, for perfectly ordered crystalline substance S = 0 at T = 0K.
Significance
 It is used to determine the absolute entropy of any substance at any desired
temperature.
Perfectly ordered crystalline substance is heated from 0K to any desired
temperature T. Its entropy increases due to increase in vibrational motion of
molecules.
The increase in entropy is given by
S = ST – S0
Where, ST is absolute entropy of substance at temperature T.
And S0 is absolute entropy of that substance at 0K.
.
. . S0 = 0

S = ST – 0
S = ST
The value of ST can be measured by measuring heat capacity of substance at
various temperatures and using the expression
. T

. . S = ST- S0 = ST = ∫ Cp.dt
0
T