October 2, 2001

Reading: Chapter VI
Homework: 6.1, 6.3, 6.5, 6.7, 6.9, 6.10
The changes in Gibbs free energy:
Consider a reaction at T:
Reactants A+B

AB Products
T

T0
A+B

AB

H (T ) = H (T0 ) + C P dT
T0

(C P = C PAB C PA C PB = C Pproducts C Preac tan ts )

S (T ) = S (T0 ) +

T0

C P
dT
T

G (T ) = H (T ) + TS (T )
T
T C

P
= H (T0 ) + C P dT T S (T0 ) +
dT
T0
T0 T

Enthalpy change involving phase changes in Reactants and/or Products:

Suppose phase changes occur in A and AB at TA and TAB, respectively.
Let, T>TAB>TA>T0
A()+BAB()
TAB

A()A()

T
AB()AB()

TA

T0
A()+BAB()

H (T0 ) = H AB ( ) (T0 ) H A( ) (T0 ) H B (T0 )

H AB ( ) (T ) = H AB ( ) (T0 ) +

TAB

T0

C PAB ( ) dT + H AB ( ) (T AB ) + C PAB ( ) dT
TAB

TA

T0

TA

H A( ) (T ) = H A( ) (T0 ) + C PA ( ) dT + H A( ) (T A ) + C PA ( ) dT
T

H B (T ) = H B (T0 ) + C PB dT
T0

H (T ) = H AB ( ) (T ) H A( ) (T ) H B (T )
Note that at the transition temperatures TA and TAB, we have

G A (T A ) = G A (T A )
H A T A S A = H A T A S A
So,
S A = S A S A =

H A H A H A
=
TA
TA

Similarly,

G AB
(T AB ) = G AB
(T AB )

H AB
(T AB ) T AB S AB
(T AB ) = H AB
(T AB ) T AB S AB
(T AB )

So,

S AB
= S AB
S AB
=

H AB H AB H AB
=
T AB
T AB

Entropy change involving phase changes in Reactants and/or Products:

A()+BAB()
T
AB()AB()
TAB

A()A()
TA

T0
A()+BAB()

S (T0 ) = S AB (T0 ) S A (T0 ) S B (T0 )

S AB (T ) = S AB (T0 ) +

TAB

C P AB
T

T0

S A (T ) = S A (T0 ) +

C PA

TA

T0

C PB

T0

S B (T ) = S B (T0 ) +

C PAB

TAB

dT + S AB (T AB ) +

dT + S A

C PA

TA

(T A ) +

dT

dT

dT

Then,

S (T ) = S AB
(T ) S A (T ) S B (T )
The above treatment is based on both H and S being state functions. Thus, even if the
actual process is irreversible, one can always choose a hypothetical reversible path.
Suppose the reaction A+BAB is at equilibrium at Teq. Then GA+GB=GAB. Now suppose
the step at T0, i.e., A+BAB is not at equilibrium. Then one can determine H(T0) and
S(T0). For simplicity, assuming no phase transition in reactants and/or products.
T0

H (T0 ) = H (Teq ) + C P dT

(I)

Teq

Similarly, also suppose at T, A+BAB is not at equilibrium.

T0

H (T ) = H (Teq ) + C P dT

(II)

Teq

From (I),
T

Teq

Teq

T0

H (Teq ) = H (T0 ) C P dT = H (T0 ) + C P dT

(III)

From (II) and (III)

Teq

T0

Teq

H (T ) = H (T0 ) + C P dT + C P dT
Teq

H (T ) = H (T0 ) + C P dT
T0

Note that in the above, the reaction A+BAB is not at equilibrium at either T0 or T.
It is important to realize that the above result is based on two important properties of H:
(1) it is a state function that allows one to choose a hypothetical reversible path for an
actually irreversible process. (2) H is additive.
Similar is true for S as well. Also, it is readily shown that the general features are
equally applicable when the reactants and/or products undergo (equilibrium) phase
transition over the temperature range of interest. Therefore, if we know the change in

enthalpy and/or entropy of reaction at any given temperature T1, we can calculate the
change at any other temperature T2.

Third Law of Thermodynamics:

Nernsts postulate:
T C
S T = S 0 + P dT
0 T
T 0, S 0 0
Plancks refinement:
Complete internal equilibrium remove residual configurational entropy