Energy Landscapes

Always remember that thermodynamic diagrams have several independent parameters. The potential is therefore described by a surface, sometimes called a landscape.

Helmholtz Energy
We changed internal energy via:

H =U −

 
∂U ∂V ∂U ∂S

V
S

Next we want to remove the entropy dependence on internal energy:

F =U −

 

S
V

=U −T S dF =dU −T dS −S dT =T dS − P dV −T dS −S dT =−S dT − P dV

Gibbs Energy
Lets remove both the entropy and volume dependence on internal energy:

G =U −

   
∂U ∂S S−
V

∂U V ∂V S

=U −T S  PV dG=dU −T dS −S dT  P dV V dP =−S dT V dP =− N s dT  N v dP = N  −s dT v dP  =N g T , P 

Principle of Minimum Energy
Referring to our original rubber band problem, what thermodynamic state was being sought when the rubber band was released?

∆U = ∆Q - ∆W Under what conditions is which variable changing? For an isolated system, ∆U = 0. → we should maximize entropy. For a open system, ∆U ≠ 0. → we should minimize energy.

Maxwell's Relations
dU =T dS− P dV

 

∂U =T ∂S V

 
∂T ∂P =− ∂V S ∂S
V

∂U =−P ∂V S

     
∂F =−S ∂T V

dF =−S dT −P dV

 
V

∂F =−P ∂V T

   
∂S ∂P = ∂V T ∂T

Maxwell's Relations
dH =T dS V dP

 

∂H =T ∂S P

 
∂T ∂V = ∂P S ∂S
P

∂H =V ∂P S

( ) ( )

dG=−S dT V dP

 

∂G =−S ∂T P

 
P

∂G =V ∂P T

   
∂S ∂V =− ∂P T ∂T

Maxwell's Relations
dU =T dS− P dV  dA

 
∂ ∂V

=?
A ,S

∂U = ∂A

 
A ,S

S ,V

  
∂ ∂V

∂ U = ∂V ∂ A A ,S

2

S

 
∂U ∂V

=−P

 
∂ ∂V

=−
A ,S

 
∂P ∂A

S ,V

Maxwell's Relations
dF =S dT −P dV +α dA

 
∂ ∂V

=?
A,T

∂F = ∂A

 

T ,V

  
∂ ∂V

∂2 F = ∂V ∂ A A,T

T

 
∂F ∂V

=−P
A ,T

 
∂ ∂V

=−
A,T

 
∂P ∂A

T ,V

Maxwell's Relations
dH =T dS +V dP+α dA

 
∂ ∂P

=?
A,V

∂H = ∂A

 
A,S

S ,P

  
∂ ∂P

∂2 H = ∂P∂A S ,A

S

 
∂H ∂P ∂ ∂P

=V

 

=−
A, S

 
∂V ∂A

S,P

Maxwell's Relations
dF =S dT −P dV +α dA

 
∂ ∂T

=?
A,V

∂F = ∂A

 

T ,V

  
∂ ∂T

∂ F = ∂T ∂ A V,A

2

V

 
∂F ∂T

=−S
A ,V

 
∂ ∂T

=−
A,V

 
∂S ∂A

T ,V

Equation of State
dU =T dS− P dV UT  ST =T −P VT VT

       

∂U ∂S =T −P ∂V T ∂V T

∂U ∂P =T −P ∂V T ∂T V

Using this equation, determine how U changes with volume for an ideal gas at constant T. Using this equation, determine how U changes with volume for a van der Waals gas at constant T.

n RT a n2 P= − V −n b V 2

Equations of state
P = P(T,V)

dP=

 
∂P ∂T

dT 

V

 

∂P dV ∂V T

dP=

nR n RT dT − 2 dV V V

S = S(P,V)

dS=

( )
∂S ∂P ∂V ∂T

dP+

V

( ) dV
∂S ∂V
P

=−

( )

dP+
P

( ) dV
∂P ∂T
V

Mechanical properties
Isobaric volume expansion

=

1 ∂V V ∂T

Isothermal compressibility

1 ∂V T =− V ∂P 1 ∂V  S =− V ∂P

Isentropic compressibility

     
P

=

1 ∂ ∂G V ∂T ∂ P

 
T S

T

T

1 ∂ G = V ∂ P2
2

S

1 ∂ H = V ∂ P2

   
2

V =V  P ,T  dV =

 

∂V ∂V dP ∂P T ∂T

 

dT
P

dV =−V  T dP dT
Page 92

Gibbs-Helmholtz
U  T ,V  = F  T , V  −T

 
∂F ∂T

V

       
∂U ∂T ∂F ∂F ∂2 F = − −T ∂T V ∂T V ∂T 2 V ∂2 F n C V =−T ∂T2 ∂2 G n C P =−T ∂T 2

U  T ,V  =−T
V

2

∂ F  T ,V  ∂T T

 

V

 

V

 

P

∂ G T , V  H  T , V  =−T ∂T T
2

P

Mechanical properties
S =S  V , T  dS=

S =−

     
∂S ∂V dV 
T

∂S ∂T

dT
V

∂F ∂T

V

∂2 F ∂2 F dS=− dV − dT 2 ∂V ∂T ∂T V dS=  dT dV n C V T T

  

Mechanical properties
S =S  P , T  dS=

S =−

     
∂S ∂S dP ∂P T ∂T ∂G ∂T
P

dT
P

∂2 G ∂2 G dS=− dP− dT 2 ∂ P ∂T ∂T P dS=−V  dPn C P dT T

  

Problems
Find β and κT for an ideal gas.

=

1 ∂V V ∂T

 
V=

P

T =−

1 ∂V V ∂P

 

T

n RT P

 
= = 1 nR V P 1 T

∂V nR = ∂T P P

 

∂V n RT =− 2 ∂P T P

=

1 P

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