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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008

Lecture #13

page 1

The Gibbs Free Energy

With the free energies Helmholtz free energy Gibbs free energy

A = U - TS G = H - TS

weve introduced all our state functions. For closed systems,

U (S ,V A (T ,V

dU =TdS pdV dH =TdS +Vdp dA = SdT pdV dG = SdT +Vdp

H (S , p )

) G (T , p )
From and
dA =

Fundamental equations

A A dV dT + T V V T G G dG = dp dT + T p p T
A = S T V G = S T p A = p V T G =V p T

The Maxwell relations:

2A 2A = V T T V

and

2G 2G = p T T p

now allow us to find how S depends on V and p.

S = p V T T V S V = T p p T

These can be obtained from an equation of state.

5.60 Spring 2008

Lecture #13

page 2

We can now also relate T and H to p-V-T data.

U =T V T H =T p T S p =T V T p p T V

S V +V = V T T p p T

U and H from equations of state!

For an ideal gas

pV = nRT
U =0 V T H =0 p T

nR p p = = T T V V nR V V = = p T T p

This proves that for an ideal gas U(T) and H(T), functions of T only. We had assumed this was true from Joule and Joule-Thomson expansion experiments. Now we know it is rigorously true.
p + a V b = RT V 2

For a van der Waals gas

p=

RT a 2 V b V

RT a U p = 2 0 = V V T V b

U( T, V )

5.60 Spring 2008

Lecture #13

page 3

The special role of G(T,p):

If you know G(T,p), you know everything!

S =

G , T p

V =

G p T G T p G G p T p p T

H = G +TS

H = G T

U = H pV

U = G T

A = U TS

A =G p

G p T

S C p =T T p

Cp = T

2G 2 T p

Can get all the thermodynamic functions from G(T,p)!

G ( T, p )
From

for liquids, solids, and gases (ideal)

V =
G p T
p2

G (T , p2 ) = G (T , p1 ) + Vdp
p1

Liquids and solids

V is small

G (T , p2 ) = G (T , p1 ) +V ( p2 p1 ) G (T , p1 )

G (T

5.60 Spring 2008

Lecture #13

page 4

Ideal gases
G (T , p2 ) = G (T , p1 ) +
p2

p1

p RT dp = G (T , p1 ) + RT ln 2 p p1

Take p1 = p o = 1 bar
G (T , p ) = G o (T ) + RT ln p p0
or G (T , p ) = G o (T ) + RT ln p

(p in bar)

From

G S = T p

S (T , p ) = S o (T ) R ln p