THERMODYNAMIC RELATIONS

Open systems: chemical potential

U =U ( S , V ) dU=TdS− pdV
U =U ( S , V , n ) dU=TdS− pdV + μdn

μ= ( δUδn )
S, V
→Chemical potential

Energetic representation

Gibbs equation

dU =TdS−pdV + μdn
Euler equation

U =TS− pV + μn
Gibbs-Duhem equation

U =TS− pV + μn → dU=dTS +TdS−dpV − pdV +dμn+ μdn=TdS−pdV + μdn

0=SdT −Vdp+ ndμ→ ndμ=Vdp−SdT → dμ=~v dp− ~s dT
Internal energy as thermodynamic potential

Thermodynamic potential: magnitude which, expressed as a function of its independent

natural variables, allows to obtain complete information of the system.

Closed system:

U =U ( S , V ) dU=TdS− pdV
First derivatives

δU δU
( ) ( )
δS V
=T
δV S
=− p

Second derivatives
−1
δ 2U δT δT dT T δ2 U
( ) ( ) ( ) (
δ S2 V
=
δS V
=T
TδS V
=T = → C V =T
C V dT C V δ S2) ( ) V

−1
δ 2U δ2U
( ) ( ) {
δV S2
=−
δp
δV S
= χ S=
−1 δV
V δp ( )} S
=
1
V χS
→ χS= V
δV2[ ( )] S

Other magnitudes

δT δT δ 2U δ2U
T =T ( S , V ) → dT = ( ) ( )
δS V
dS+
δV S
dV = ( ) (
δ S2 V
dS+
δS δV
dV)
 δp δp δ2 U δ2U
p= p ( S , V ) → dp= ( )
δS V
dS+ ( )
δV S
dV =− ( δV δS
dS +) ( )
δV2 S
dV

Obtaining χ T

δ 2U
δ2 U δ2 U
− ( δS δV ) dV
dT = ( ) (
δ S2
dS +
δS δV )
dV =0 dS=
δ2 U
V
( ) δ S2 V

δ 2U
δ 2U δ 2U dp δ2 U ( δS δV )+ δ U
2
dp=− ( δV δS ) ( )
dS +
δV2 S
dV
dV
=
δV δS ( ) δ2 U ( )
δV2
V V
( ) δ S2 V
S

2
δ U
−1 δV −1 ( ) δ S2
χT =
V δp ( ) =
V δ U2 2
δ U 2
V

δ2U
T
( δV δS ) ( )( )
V
+
δV2 S δ S2 V

Helmholtz potential

Magnitude obtained after replacing S by its conjugated variable T with a Legendre

transformation on U:
n
Legendre ( f ) → g=f − ∑
i= p+i
( δδfx )
i x j ≠i
xi

Legendre ( U=U ( S , V , n ) ) → g=U−S ( δUδS ) V

dU =TdS−pdV + μdn → ( δUδS ) =T

V

g=U−TS F=U −TS

dF=dU−SdT −TdS=TdS− pdV + μdn−SdT −TdS=− pdV + μdn−SdT
F=F (T , V ,n)
Obtainable info (closed systems)

First derivatives

( δFδT ) =−S ;( δVδF ) =− p

V T

Second derivatives
 δ2F δS −1 TδS −C V δ2 F
( ) ( )2
δT V
=−
δT V
= ( )
T δT V
=
T
→ C V =−T
δ T2 ( )
V

−1
δ2F δ2 F
( ) ( )
δV2 T
=−
δp
=
1
δV T V χ T
→ χ T = V
δV2 [ ( )] T

Physical interpretation

F plays in isothermal process the same role as U in isentropic processes.

d F=− pdV −SdT −( dF )T =pdV

Enthalpy

Magnitude obtained after replacing V by its conjugated variable p with a Legendre

transformation on U:

Legendre ( U=U ( S , V , n ) ) → g=U−V ( δδUV )

S

dU =TdS−pdV + μdn → ( δδUV ) =− p

S

g=U + pV H=U + pV
d H=dU + p d V +V d p=TdS−pdV + μdn+ p d V +Vdp=TdS+ μdn+Vdp
H=H ( S , p , n)
Obtainable info (closed systems)

First derivatives

( δHδS ) =T ; ( δHδp ) =V
p S

Second derivatives
−1
δ2H δT δT T δ2 H
( ) ( ) ( )=
δ S 2 p δS p
=T =
TδS p C p
→C p =T
δ S2 ( ) p

δ2H δV −1 δ 2 H
( ) ( )
δ p2 S
=−
δp S
=−V χ S → χ S =
V δ p2 ( ) S

Physical interpretation

H represents the heat exchange in isobaric processes as U does in isochoric processes.

d H=TdS+Vdp ( d H ) p=( TdS ) p=( δQ ) p=C p dT

 C p= ( δHδT ) p

Gibbs potential

Magnitude obtained after replacing S and V by its conjugated variables, T and p with a
Legendre transformation on U:

( δUδS ) −V ( δUδV )
Legendre ( U=U ( S , V , n ) ) → g=U−S
V S

δU δU
dU =TdS−pdV + μdn → ( ) =T ; (
δV )
=− p
δS V S

g=U−TS+ pV G=U −TS+ pV

dG=TdS− pdV + μdn−TdS−SdT + pdV +Vdp=μdn−SdT +Vdp
G=G( T , p , n)
Obtainable info (closed systems)

First derivatives

( δGδT ) =−S ;( δGδp ) =V

p T

Second derivatives

δ 2G δS 1 T δS −C p δ 2G
( ) ( ) ( )
δ T2 p
=− =
δT p T δT p
=
T
→C p =−T
δ T2 ( ) p

δ 2G δV −1 δ 2 G
( ) ( )=
δ p2 T δp T
=−V χ T → χ T =
V δ p2 ( ) T

Physical interpretation

Considering a control volume and neglecting the potential energy:

c 22 c 21
( )(
h 2+ − h1 + =q−ws
2 2 )
If the evolution is also isothermal:
2
c 21 c2
q=∫ TdS=T ( s2−s 1 ) ws = g1 +
1
( 2 )( − g2 + 2
2 )
Maxwell relations

They allow to replace the partial derivatives where entropy appears by relations between
magnitudes more easily measurable.
dU =TdS−pdV → ( δpδS ) =−( δTδV )
V S

δp δS
dF=− pdV −SdT → ( ) =(
δT δV )
V T

δV δT
dH =TdS+Vdp → ( ) =(
δS p δ p) S

δV δS
dG=−SdT +Vdp → ( ) =−( )
δT p δp T

Evolution criteria in non-static processes

Considering a closed system. Applying the first and second laws:

TdS> dU + pdV
- S=cte ;V =cte → Natural potential U
dU < TdS− pdV dU <0
U decreases →the final state of equilibrium is a minimum dU =0 ; d 2 U > 0
- U =cte ; V =cte → Natural potential S
1 p
dS > dU+ dV dS >0
T T
S increases →the final state of equilibrium is a maximum d S=0 ; d2 S <0
- T =cte ; V =cte→ Natural potential F
d F<−S d T − pdV d F< 0
F decreases →the final state of equilibrium is a minimum d F=0 ; d 2 F >0
- S=cte ; p=cte → Natural potential H
d H <TdS+Vd p dH <0
H decreases →the final state of equilibrium is a minimum d H=0 ; d 2 H >0
- p=cte; V =cte → Natural potentialG
d G<−S d T +Vd p d G< 0
H decreases →the final state of equilibrium is a minimum d G=0 ; d 2 G>0