INTERPRETATION OF G AND A IN TERMS OF WORK

What happens when not only mechanical work (PdV) is involved?

dU = dq + dw
dq dSsyst Since Tsurr , then

dU + TdS dw
d (U TS ) dw ( dA)T dw

At constant T, we can write

(dA)T

dw

In a reversible process at constant T the work done on the system is equal to the increase in A. When the system does work on the surroundings in a real process, the work done on the surroundings is less than the decrease in the Helmholtz energy of the system.

Since

dw = PdV + dw nonPV , we can write

dU Pext dV + TdS dw nonPV .

At constant T and Pext, we can write

d(U + PextV TS) dw nonPV

(dG)T ,P dw nonPV

For a reversible process at constant T and P, the change in Gibbs energy is equal to the non-PV work done on the system by the surroundings. When work is done on the system, G increases, when the system does work on the surroundings, G decreases. When the system does work (non PV) on the surroundings in a real process, the work done on the surroundings is less than the decrease in the Gibbs energy of the system.
EFFECT OF TEMPERATURE ON THE GIBBS ENERGY: GIBBS-HELMHOLTZ EQUATION

G = S T P
Since

G = S T P
S = H G , then T

G = H TS

and

 G G H = T P T T .
The left-hand side of the equation can be rewritten using

G 1 G G 2 = T T T T T
so that

G H T = T or T T P
Gibbs-Helmholtz Eqution

G H = 2 T T T P

This equation is particularly important when we consider the temperature dependence of equilibrium constants. We can determine G as a function of T for a process or a reaction, and calculate H from it (no calorimeters are necessary). If we assume that H is T independent, and we know H and G at an initial temperature, we can calculate G at another final T.

EFFECT OF PRESSURE ON THE GIBBS ENERGY

G =V Since: P T ,{ n i }

Then:

G2 = G1 +

P2

P1

VdP

For a solid or a liquid V~constant when P changes (not too much):

G2 = G1 + V (P2 P1 )
we can set 1 as the standard state. For an ideal gas:
P

G = G + nRT

dP P = G + nRT ln P P Pi P
f P

f Gi = f Gi + nRT ln

For a real gas (Lewis) we define fugacity f so that:

G = G + RT ln

lim f = 1 P 0P

APPLICATIONS OF MAXWELL RELATIONS

Using the Maxwell relations, we will show that for an ideal gas
U = 0. V T

We start from constant

dU = Td S pd V

and divide by

dV

while keeping T

U S =T P V V T T

using

S P = T V V T

we obtain:
U P =T P. T V V T

For an ideal gas

R P = , T V V

which gives

U = 0. V T

For a real gas, van der Waals equation is gives

U a = 2 V T V

P=

RT V b

a V
2

, which

, which is different from zero.