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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 A = U - TS

Gibbs free energy G = H - TS

we’ve introduced all our state functions. For closed systems,

U (S ,V ) ⇒ dU =TdS − pdV

H (S , p ) ⇒ dH =TdS +Vdp

Fundamental equations
A (T ,V ) ⇒ dA = −SdT − pdV

G (T , p ) ⇒ dG = −SdT +Vdp

∂A ⎞ ⎛ ∂A ⎞ dV
From dA = ⎛⎜ ⎟ dT + ⎜ ⎟
⎝ ∂T ⎠V ⎝ ∂V ⎠T
⎛ ∂G ⎞ ⎛ ∂G ⎞
and dG = ⎜ ⎟ dT + ⎜ ⎟ dp
⎝ ∂T ⎠ p ⎝ ∂p ⎠T

⎛ ∂A ⎞ = −S ⎛ ∂A ⎞ = − p
⎜ ⎟ ⎜ ⎟
⎝ ∂T ⎠V ⎝ ∂V ⎠T
⎛ ∂G ⎞ ⎛ ∂G ⎞
⎜ ⎟ = −S ⎜ ⎟ =V
⎝ ∂T ⎠ p ⎝ ∂p ⎠T

∂ 2A ∂2A ∂ 2G ∂2G
The Maxwell relations: = and =
∂V ∂T ∂T ∂V ∂p ∂T ∂T ∂p

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

⇒ ⎛ ∂S ⎞ = ⎛ ∂p ⎞ ⎛ ∂S ⎞ ⎛ ∂V ⎞
⎜ ⎟ ⎜ ⎟ ⎜ ⎟ = −⎜ ⎟
⎝ ∂V ⎠T ⎝ ∂T ⎠V ⎝ ∂p ⎠T ⎝ ∂T ⎠ p

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 ⎞ ⎛ ∂S ⎞ ⎛ ∂p ⎞
⎜ ⎟ =T ⎜ ⎟ − p =T ⎜ ⎟ −p
⎝ ∂V ⎠T ⎝ ∂V ⎠T ⎝ ∂T ⎠V
→ U and H from equations of state!
⎛ ∂H ⎞ ⎛ ∂S ⎞ ⎛ ∂V ⎞
⎜ ⎟ =T ⎜ ⎟ +V = V −T ⎜ ⎟
⎝ ∂p ⎠T ⎝ ∂p ⎠T ⎝ ∂T ⎠ p

• For an ideal gas pV = nRT

⎛ ∂p ⎞ nR p ⎛ ∂U ⎞
⎜ ⎟ = = ⇒ ⎜ ⎟ =0
⎝ ∂T ⎠V V T ⎝ ∂V ⎠T
⎛ ∂V ⎞ nR V ⎛ ∂H ⎞
⎜ ⎟ = = ⇒ ⎜ ⎟ =0
⎝ ∂T ⎠ p p T ⎝ ∂p ⎠T

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
RT a
p= − 2
V −b V

⎛ ∂U ⎞ RT a
⎜ ⎟ = −p = 2 ≠0 ⇒ U( T, V )
⎝ ∂V ⎠T V − b 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!

⎛ ∂G ⎞ ⎛ ∂G ⎞
S = −⎜ ⎟ , V =⎜ ⎟
⎝ ∂T ⎠ p ⎝ ∂p ⎠T

⎛ ∂G ⎞
H = G +TS ⇒ H = G −T ⎜ ⎟
⎝ ∂T ⎠ p

⎛ ∂G ⎞ ⎛ ∂G ⎞
U = H − pV ⇒ U = G −T ⎜ ⎟ − p⎜ ⎟
⎝ ∂T ⎠ p ⎝ ∂p ⎠T

⎛ ∂G ⎞
A = U −TS ⇒ A =G − p⎜ ⎟
⎝ ∂p ⎠T

∂S ⎞ ⎛ ∂2G ⎞
C p =T ⎛⎜ ⎟ ⇒ C p = −T ⎜ 2 ⎟
⎝ ∂T ⎠ p ⎝ ∂T ⎠ p

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

• G ( T, p ) for liquids, solids, and gases (ideal)

⎛ ∂G ⎞
From V =⎜ ⎟
⎝ ∂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

p2 RT p
G (T , p2 ) = G (T , p1 ) + ∫ dp = G (T , p1 ) + RT ln 2

p1 p p1

Take p1 = p o = 1 bar

p
G (T , p ) = G o (T ) + RT ln or G (T , p ) = G o (T ) + RT ln p
p0
(p in bar)

⎛ ∂G ⎞
From S = −⎜ ⎟ ⇒ S (T , p ) = S o (T ) − R ln p
⎝ ∂T ⎠ p