Chapter 6: Thermodynamic Properties of Real Fluids

The Four Fundamental Property Relations

 Consider 1 mol of a material undergoing an infinitesimal reversible
change from an equilibrium state to another:

The Four Fundamental Property Relations

 1st law: dU = dq + dw = dqrev + dwrev = TdS – PdV
dU = TdS- PdV

 But dU = TdS – PdV contains only properties (state functions) which

don’t depend on the path, so it is valid for reversible, as well as,
irreversible processes

 Eleminate U in terms of H (using U = H – PV) to get

dH = TdS+ VdP

 Eleminate H in terms of G (using G = H –TS) to get:

dG = -SdT+ VdP

 Eleminate U in terms of A (using A = U –TS) to get:

dA = -SdT- PdV
 Alternative Gibbs Fundamental Property Relation

Exercise:
Starting from d(G/RT) and using G = H – TS and dG = -SdT + VdP, show
that:
 G   V   H 
d  dP   2 
dT
 RT   RT   RT 

This is an alternative fundamental property relation in terms of the

dimensionless Gibbs energy, G/RT. Another feature, is that it has H rather
than S, as in dG = -SdT + VdP
 Maxwell’s Relations
If dy = M(x,y) dx + N(x,y)dy is exact, then:
(∂M/∂y)x = ∂N/∂x)y
Apply exactness criteria to obtain Maxwell’s relations

 T   P 
   
dU = TdS- PdV  V S  S  V
All of these are exact differentials

 T   V 


Maxwell’s Relations
dH = TdS+ VdP    
 P S  S P

 V   S 
dG = -SdT + VdP     
 T P  P T

dA = -SdT - PdV  P   S 
    
 T  V  V T
Can this figure help you remember the four fundamental relations
and Maxwell’s relations?
 Thermodynamic Derivatives in Terms of P,V,T, and CP

 To transform any derivative, like (∂H/ ∂ P)T, (∂T/ ∂ P)S, etc. in terms of
P,V,T, and CP, remember the following:

1. If the derivative involves one of U, H, G, and A, in the denominator or the

numerator get it directly from the corresponding fundamental property
relation. [e.g., to find (∂H/ ∂ P)T, work with dH = TdS+ VdP, to get: (∂H/
∂ P)T=T (∂S/ ∂ P)T + V]

2. If any of U, H, G, and A appears as a constraint (subscript) in the

derivative, use Euler’s chain relationship first, for example:
(∂T/ ∂ P)H= - (∂T/ ∂ H)P (∂H/ ∂ P)T=-(1/CP) (∂H/ ∂ P)T

 If the derivative involves ∂S in the numerator or the denominator, get it

from one of Maxwell’s relationships. [e.g., (∂S/ ∂ P)T = -(∂V/ ∂ T)P
 Enthalpy (H) and Entropy as functions of T and P
H(T,P) and S(T,P)
Exercise
Considering H = H(T,P) and S = S(T,P)
a) Show that:

1 𝜕𝑉
b) Express the above two expressions in terms of 𝛽 𝛽 = and κ
𝑉 𝜕𝑇 𝑃
1 𝜕𝑉
𝜅=−
𝑉 𝜕𝑃 𝑇
c) Qualify the above results for a) an ideal gas, and b) an incompressible
liquid Note: see your textbook page 213-215
 Internal Energy (U) and Entropy as functions of T and V
U(T,V) and S(T,V)
Exercise
Considering U = U(T,V) and S = S(T,V)
a) Show that:

1 𝜕𝑉
b) Express the above two expressions in terms of 𝛽 𝛽 = and κ
𝑉 𝜕𝑇 𝑃
1 𝜕𝑉
𝜅=− and show that
𝑉 𝜕𝑃 𝑇

c) Qualify the above results for a) an ideal gas, and b) an incompressible

liquid Note: see your textbook page 217-218
 (CP-CV) as functions of (T,V) or (T,P)

Exercise
a) Show that:

b) Qualify the above results for a) an ideal gas, and b) an incompressible

liquid Note: see your textbook page 217-218
 Thermodynamic Derivatives in Terms of P,V,T, and CP (Cont’d)

• Example:
Joule-Thomson coefficient (µJ-T) is defined as: µJ-T = (∂T/ ∂ P)H
Find an expression for µJ-T in terms of P,V, T, and CP for a gas using RK-EOS
Solution: Can be + or –
 T   T   H  1   V    RT 2  Z  (cooling or heating)
μ J T          T    V     

 P  H  H  P  P  T C P   T  P   C p P  T  P
Need to evaluate (∂V/ ∂ T)P from RK EOS
Always + (cooling)
RK EOS:
RT a R 2T 2.5 RT
P  a  0.42748 c b0.08664 c
V b V(V b) T P P
c c
With pressure explicit EOS, it is easier to find (∂P/ ∂V)T and (∂P/∂T)V.
Therefore, using Euler chain relation we can write:
1
 V   V   P   P   P 
           
 T  P  P T  T  V  V T  T  V
 Thermodynamic Derivatives in Terms of P,V,T, and CP (Cont’d)

 P  RT (2V  b)a/ 2  P  R 1 aT 3/2

        
 V T (V  b) 2 V 2 (V  b) 2 
 V
T (V  b) 2 V(V  b)

1   V   1    P  1  P   
μ J T  T
    V    T        V
CP   T  P  CP    V T  T  V  
   1
 

1  
T   
RT

 2V  b  a/ T  R

  
1 aT 3/2   
    V
  V V  b   V  b 2 V V  b 

   
V  b
2 2 2
CP  

Now, µJ-T is expressed in terms of T, V (or P), and CP. Given T and P, besides
CP, use RK EOS to find V then you can calculate numerical values for µJ-T
Also, at a given P, we can calculate T at which µJ-T = 0 (i.e., the inversion
temperature)

Exercise: Use Excel to compute µJ-T from the RK EOS for CO2 at 35 oC and
pressures from 200 to 600 psia (Hint: solve for V using equation 3.52)
Example:
The speed of sound in any medium (a) is defined as: a2 = (∂P/∂ρ)S. Find an
expression for “a” in terms of P,V, T, and heat capacities in any medium (s, l, g)
and then qualify it to incompressible flow, and an ideal gas media.

 P   P    P   S     P   T   S   T  
a 2     V2     V2         V2          
  S  V S   S  V  V  P    T  V  S  V  T  P  V  P 
  P   T   C P   T    P 
  V            - V 2   Remember that V must be in m3kg -1
2

  T  V  CV   T   V  P   V T
(8.314 J mol-1 K -1 ) T (K) mol 103 g T/K
For an ideal gas: PV  RT or V (m /kg) 
3
   (8314 /MW)
P (Nm-2 ) MW g kg P/Pa
 P   8314   -T   8314 
Hence: a 2  - V 2    - V 2    2    T

 T
V  MW   
V  MW 
1/2 1/2
 8314   8314 
The speed of sound in air at 1 bar and 300 K, therefore, is: a    ( T )    (1.4  300)
1/2 1/2

 MW   29 
 347 m s-1
 P  -1 1 finite
For an incompressible fluid,    and hence a 2   V     
 V T κV κ 0
 Enthalpy and Entropy Changes for Real Gases

• For ideal gases undergoing a change in state from (T1,P1) to (T2, P2), it has
been shown previously that:

T2 T2
CigP P2
ΔH   C dT and
ig ig
P ΔS  
ig
dT  Rln
T1 T1
T P1

Also, note that, in view of the text’s nomenclature, H and S stand for molar
(or specific) enthalpy and entropy

• For a real gas, ∆H and ∆S are corrected by adding a (residual) term to take
into account the deviation from ideal gas behavior.
 Residual (Departure) Properties
• Residual Properties are defined as the difference between a property M of a
real material at T and P and the property M at the same T and P if that material
were an ideal gas, i.e.,:

• MR (T,P) = M(T,P) – Mig(T,P)

ZRT RT RT
V  T,P  = V  T,P  - V  T,P  =
R ig
- =  Z-1
P P P
• GR (T,P) = G (T,P) – Gig (T,P)
• HR (T,P) = H (T,P) – Hig (T,P) UR = U – Uig SR = S – Sig,…
• Note that a real gas at low P and high T, behaves as an ideal gas, so its VR →
zero. However, at cryogenic (very low) temperature, a real gas doesn’t behave
ideally, even at low P. In this case (i.e., low P and low T) VR = V –Vig = ∞ - ∞
(indeterminate), or
RT 0
R ig
V = V - V = ZRT/P - RT/P =  Z-1 = (indeterminate)
P 0
Hence, to get V R apply L'Hopital Rule: V R = RT  Z/P  P0
const (low)T

However, UR, and HR are both zeros when P → 0 regardless of temperature.

   G R /RT   HR
GR = constant independent of T as P → 0 Remember: 
 T
 =-
 RT 2
=0
Find VR at 178 oC and the corresponding Psat (957.36 kPa) for both the saturated
liquid and the saturated vapor
Vig = RT/P = (83.14 cm3-bar-mol-1-K-1*451.15 K)/9.57361 bar = 3917.92 cm3mol-1
= 217.66 cm3-g-1
 Residual Properties (Continued)

It can be easily shown that:

 GR   VR   HR   V R   G R /RT   HR   G R /RT 
d   dP   2 
dT   =  and   =-T  
 RT   RT   RT   RT    P T  RT    T P
Therefore at constant T:

 G R   VR   G R  P  VR 
R

 Z 1 
G /RT P
d  
=  dP   d   
 dP    dP  Constan T 
0
 RT   RT  (G R /RT)P=0 
RT  0  RT  P 
Hence, at constant T:
 G R  G R P
 Z 1 
    +  dP (constant T)
 RT   RT  P=0 0  P 
 HR    GR 
P
 Z  dP 

 RT


  T
T

 RT

P
  T 
0
  
T  P 
(constant T)

Note that (G R /RT) P=0 (the limiting value of (G R /RT) as P  0) is NOT zero
as might come to mind firstly. It is a constant independent of T, which can be
set at zero (because usually changes in G are needed).
 Residual Properties (Continued)
Hence, once Z is known as a function T and P, an expression for GR/RT can be
derived directly. An expression for HR/RT can be found by direct
differentiation of the resulting expression for GR/RT.
 VR   Z 1 
  
 RT   P 
 G R  P  Z 1 
    dP
 RT  0  P 
 HR    GR 
P
 Z  dP 
   T    T    
 RT  T  RT P 0
T  P 
Once G R /RT and H R /RT are there, SR /R and U R /RT can be computed from:
 SR   H R   G R 
 =  -   Remember: G = H - TS
  
R RT   RT 
 U R   H R   PV R 
 = -   Remember: U = H - PV 
 RT   RT   RT 
 Residual Properties (Continued)
Methods to compute GR, HR and SR:
Note that we need Z(T,P) [or Z(T,V)] to derive expressions for any MR:
1) If Z is given as Z(T,P)
A: Virial EOS Z=1 + BP + CP 2 +.. = 1 +
BP

C-B2

P 2 
 ..
 RT 
2
RT
VR

Z-1
=B+CP =
B

C-B2
P
 
 RT 
2
RT P RT
GR
P
 Z-1 C 2 B C-B2 2
RT
= 0
P
dP = BP+
2
P =
RT
P+
2RT
P

HR   G R /RT
= - T
  
RT  T 
 P
      dC dB   
  T
P
dB
-B    2
 P   dT
T -2B 
 - C-B
2
 
=-T    dT
    dT  
 R  T2 2R  T2 
   

  
    
   
SR HR GR UR HR PV R
= - = -
R RT RT RT RT RT
 3.57

3.66

3.67
 Residual Properties (Continued)
B:
Expressions for HR/RT, UR/RT and SR/R for a real gas obeying the
generalized Virial EOS [presented in equations 3.61-3.66. See also pages 232-
233]
Z = 1 +  B +ωB1 
Pr o
Tr
dBo 0.675
B  0.083  0.422/T
o 1.6
r   2.6
dTr Tr
dB1 0.722
B  0.139  0.172/T
1
r
4.2
  5.2
dTr Tr
V R  Z-1  Bo
+ ωB1
 R
 Bo
+ ωB1

RT
=
P
=
Pr
PTr
 Bo
+ ωB1
 =
PcTr

V
RTc
=
Pc
HR  o dBo  1 dB1  
 Pr  B  Tr  ω  B  Tr 
RTc  dTr  dTr 

SR  dBo dB1 
  Pr  ω 
R  r
dT dTr 
 Residual Properties (Continued)

C:
Using the Lee-Kessler generalized correlation for Z:
Z = Zo + ωZ1
This will give rise to a generalized correlation for HR/RTc and SR/R as shown
below [for derivation, see pages 230-231:

H R (H R ) o (H R )1
 ω
RTc RTc RTc
SR (SR ) o (SR )1
 ω
R R R

Where: (HR)o/RTc, (HR)1/RTc, (S)o/R, and (SR)1/R are tabulated or graphed in

terms of Tr and Pr. (Appendix E, tables E-5 to E-12)
 Residual Properties (Continued)

2) If Z is given as Z(T,V) [e.g., cubic EOS and the ρ-form of Virial EOS]
In this case the expression GR/RT = ∫[(Z-1)/P] dP become inconvenient and a transformation to
an integral in terms of dV (or dρ) is preferred.

Exercise: Show that the previous defining equations for GR/RT, HR/RT, and SR/RT become as
follow when Z is given as Z(T,V) [See eqs. 6-57 to 6.63]

Remember: P = ZRT  lnP = lnRT + lnZ + ln

P=P
ρ=ρ
 d dZ 
P Z=Z
GR dP
RT
=   Z-1
0
P
= 
P=0
 Z-1 
 
+
Z 

ρ=0
Z=1
ρ V
GR dρ dV
= Z - 1 - lnZ + 0  Z-1 = Z - 1 - lnZ -   Z-1
RT ρ 
V
dρ dV
Remember: =-
ρ V
ρ
 Z  dρ  Z  dV
V
HR
= Z - 1 - T   = Z - 1 + T   
RT 0  T   ρ   T V V
ρ ρ
 Z  dρ  Z  dV
V V
SR dρ dV
= lnZ - T    - 0  Z-1 = lnZ + T   T   V +   Z-1
R 0
T  ρ ρ 
V
 Residual Properties (Continued)
Z(T,V) Continued
Exercise: Find expressions for GR/RT, HR/RT and SR/R for a real
gas obeying the ρ-form of Virial EOS: Z = 1 + Bρ + Cρ2 [see eqs.
3.61-3.63]
Direct integration yields:
GR 3
=2Bρ + ( ) Cρ 2 + -lnZ
RT 2
HR  B dB   C 1 dC  2 
=T  -  ρ +  - ρ 
RT  T dT   T 2 dT  
SR  B dB  1  C dC  2 
= lnZ - T  +  ρ +  +  ρ 
R  T dT  2  T dT  
Expressions for B, C, dB/dT, and dC/dT are recoverable from eqs. 3.63 – 3.71
 Residual Properties (Continued)
Z(T,V) Continued
Example: Find expressions for GR/RT, HR/RT and SR/R for a real gas obeying
the generic cubic EOS (equation 3.42)

Express the pressure-explicit cubic EOS as Z = Z(T,V) by multiplying both

sides by V/RT. Then integrate as before.

Direct integration yields equations 6.66 and 6.69 (refer to Chapter 3 for cubic
EOS terminology)
GR
= Z - 1 - ln  Z - β  - qI Consult Table 3.1 for generic cubic EOS
RT parameters. e.g., For RK EOS:
HR  dlnα(Tr )  α(Tr) = Tr-1/2
=Z-1+  -1 qI Hence, d ln(α(Tr))/dlnTr = -1/2
RT  dlnTr 
SR  dlnα(Tr )  1  Z + σβ 
= ln  Z - β  +   qI with I = ln  
R  dlnT r  σ - ε  Z + εβ 
or I = β/Z in the case of VDW EOS
 Residual Properties (Continued)

 Now HR and SR can be computed for any real gas once T and P are known.
How will these be used to compute ∆H and ∆S for a real gas.
 Note that, since MR (T,P) = M(T,P) – Mig(T,P) then
 M(T,P) = Mig (T,P) + MR (T,P) and ∆M = ∆Mig+ ∆MR, i.e.,
ΔM  M 2 (T2 , P2 ) - M1 (T1 , P1 ) 
  
 M ig2 (T2 , P2 )  M R2 (T2 , P2 )  M ig1 (T1 , P1 )  M1R (T1 , P1 ) 
 ΔM ig  (M R2  M1R )
T2
ΔH   CigP dT  (H R2  H1R ), and
T1
T2
CigP P2
ΔS   dT  Rln  (SR2  S1R )
T1
T P1
∆Sig
Extension of Residual Properties to Mixtures

Use simple mixing rules to generate pseudocritical parameters Tpc and

Ppc , compute pseudoreduced parameters Tpr and Ppr to replace Tr and Pr

ω=  yi ωi
i

Tpc =  yi Tci Tpr =T/Tpc

i

Ppc =  yi Pci Ppr =P/Ppc

i
 Two-Phase Pure Material System
• Two phases, α and β, in equilibrium at T and P must have the same molar Gibb’s
free energy, i.e., Gα = Gβ (e.g., α = L, β = V).
• This results from dG = VdP – SdT, applied to (α+β) at constant T and P. β:
Vapor
• For a phase change at constant T and P: dS = dqrev/T Sαβ = Hαβ/T.
α:
Liquid
G α  Gβ  dG α  dGβ
V α dP  Sα dT  Vβ dP  Sβ dT
dP Sβ  Sα ΔS dP ΔH αβ
    Clapeyron Equation
dT Vβ  V α ΔV dT α β transition T V αβ

• Clapeyron eq. is valid for any phase transition (l-v, l-s, s-v).
• Exercise:
Using Clapeyron eq., explain why is the solid-liquid co-existence line for water
has a negative slope in a P .vs. T phase diagram
• Hint: the change in volume in going from ice to water is negative (ice floats in
water).
Gl = 313.9-348.15*1.0154 = -39.6 kJ/kg
Gv = 2635.4-348.15*7.6835 = -39.6 kJ/kg
The Clausius-Clapeyron Equation (α: Liquid and β: Vapor)
Simplifications:
When Vv >>Vl : ΔV lv  V v  V l  V v
If the gas is further assumed an ideal gas, then Vv=RT/P and
Clausius-Clapeyron equation results:

dP ΔH lv ΔH lv
 
dT l-v trransition T V lv
T Vv

dP P.ΔH lv

dT RT 2
dP ΔH lv dT ΔH lv 1
  d 
T
2
p R T R
dlnP ΔH lv

d(1/T) R
• The Clausius-Clapeyron equation is useful for computing ΔHlv
from a plot of ln P .vs. 1/T.
• If ΔH lv is constant, integration from (T1 ,P1sat ) to (T2 ,P2sat ) gives:
 P2sat  ΔH lv  1 1 
ln  sat  =-  - 
P R  T2 T1 
 1 
• It is also useful for determining the vapor pressure P2sat at T2 given
ΔHlv and the vapor pressure P1sat at T1 e.g., when T1 = Tn and P1sat  1 b
and ΔHlv are known, Psat at any other T2 can be found

B
• This analysis shows that ln(Psat) goes linearly with 1/T: lnPsat =A-
T
• This has given rise to the more celebrated Antoine Equation:
B
lnPsat =A- (See Appendix B.2 for typical Antoine constants)
T+C
Corresponding-State Correlations for Vapor Pressures

Lee-Kesler correlation: nonpolar, non-associating liquids

lnPrsat =lnPro +ω×lnPr1
o 6.09648
lnP = 5.92714 -
r - 1.28862×lnTr + 0.16934×Tr6
Tr
1 15.6875
lnP = 15.2512 -
r - 13.4721×lnTr + 0.43577×Tr6
Tr
sat
lnPr,@T -lnP o
r @Tn /Tc ln 1.01325/Pc in bar  -lnPro@Tn /Tc
ω= n
1
=
lnP r @Tn /Tc lnPr1@Tn /Tc
(If Tn is not known, use the familiar ω from Appendix B.1)
Problem 6.17
Problem 6.40
Problem 6-40 Continued

HR2 – HR1
Problem 6.42
Problem 6.46
Problem 6.54

Ideal gas 273 K; 101.33 kPa Sat liquid 370 K; 1435 kPa
∆H1 ∆H3
∆H2
Ideal gas 370 K; 1435 kPa Sat (real) vapor 370 K; 1435 kPa
Problem 6.56

Real gas 127 oC; 38 bar Ideal gas t2 = ?; 1 bar

Ideal gas 127 oC; 38 bar ∆H = -HR(Tr1,Pr1) + ∆Hig = 0

Fugacity of a species in a gaseous or liquid mixture obeying a cubic EOS
b
ln i   i  Z  1  ln  Z     qi I
b
Z : Compressibility factor of the mixture at T, P, y1...y N or  x1...x N 
N
b =  yi bi   = bP/RT
i=1

1 Z   
I= ln (if    ) =  if    
   Z   Z  
 a b 
qi = q  1  i  i 
 a b
1/ 2

a =  yi y j  a i a j 
N N

i=1 j=1

ai = -a +2 y j  a i a j 
N
1/ 2

j 1
For example for a binary liquid mixture at given T, P, and x1o obeying
RT a (T )  (Tr ) R 2Tc2 RTc
RK EOS: P =  with a =  and b = 
V  b V V  b  Pc Pc
b = y1b1 + y 2 b2
a  y12a1 + 2y1y 2 a1a2 + y 22a2
a1 = -a +2y1a1 + 2y 2 a1a2
a2 = -a +2y 2a 2 + 2y1 a1a2
a
q= and  = bP/RT
bRT
 a b   a b 
q1 = q  1  1 - 1  and q2 = q  1  2 - 2 
 a b  a b
b1
ln 1    Z  1  ln  Z     q1I
b
b
ln  2   2  Z  1  ln  Z     q2 I
b