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p

p

p

p

V

1. Derive Gibbs Helmholtz equation.

Consider the following relations,

G = HTS (Gibbs free energy)

H = E + PV (enthalpy)

Therefore,

G = E + PV TS

For infinitesimal change,

dG = dE + P dV + V dP T dS S dT .(1)

But according to first and second law of thermodynamics,

dE = dq P dV (first law )

dq = T dS (second law)

Therefore, dE = Tds Pd V (2)

Substituting equation 2 in 1 we get,

dG = TdS P dV + P dV + V dPT dSS dT

Therefore,

dG = V dPS dT ..(3)

At constant pressure dP = 0, equation (3) becomes

dG = --S dT (4)

= --S .(5)

Substituting equation (5) in G = H TS, we get

G = H +

(or) G ---T = H

This is one form of the Gibbs Helmholtz equation.

For any two states of the system the equation (4) may be written as,

dG1 = ---S1dT (initial state)

dG2 = --S2dT (final state)

To get the change

dG2dG1 = --S2dT(--S1dT)

d(G2G1) = -- ( S2S1)dT

At constant pressure the equation (7) becomes

= -- S

But, according to definition of free energy

G = HTS

(Or)

_

S =

Substituting equation (9) in 8, we get

(Or)

= T

= H + T

Similarly A = E + T

This is another form of Gibbs-Helmholtz equation

2. Derive Clausius Clapeyron Equation.

Consider a system consisting of only 1 mole of a substance existing in two phases A and B. The free energies of the substance in two

phases A and B be GA and GB. Let the temperature and pressure of the system be T and P respectively.The system is in equilibrium,

so there is no change in free energy.i.e.,

GA = GB

If the temperature of the system be raised to T + dT, the pressure becomes P + dP and the free energies become GA + dGA and GB +

dGB respectively. Then the equation (1) becomes

GA + dGA = GB + dGB

We know that

G = H TS (Gibbs free energy)

Therefore H = E + PV (enthalpy)

G = E + PVTS

Therefore

dG = dE + P dV + VdP

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