Advanced Thermodynamics

Thermodynamic Properties of Fluids

Property relations for homogeneous phases

First law for a closed system

d (nU ) dQ dW

a special reversible process

d (nU ) dQrev dWrev
dWrev Pd (nV )

dQrev Td (nS )

d (nU ) Td (nS ) Pd (nV )

Only properties of system are involved:

It can be applied to any process in a closed system (not necessarily
reversible processes).
The change occurs between equilibrium states.

d (nU ) Td (nS ) Pd (nV )

The primary thermodynamic properties: P, V , T , U , and S

H U PV

The enthalpy:
The Helmholtz energy:
The Gibbs energy:

A U TS
G H TS

For one mol of homogeneous fluid of constant composition:

dU TdS PdV
dH TdS VdP
dA PdV SdT
dG VdP SdT

V
T

T
V

Maxwells equations

Enthalpy, entropy and internal energy change calculations f (P,T)

H
H
dT

dP
T P
P T

dH
H

CP
P

dH TdS VdP
H

P
H

S
T

T
P

S
dH C P dT T

V dP

V
dH C P dT V T

dP

S
S
dS
dT
dP
T P
P T
S

CP
T

dT V
dS C P

dP
T T P
H U PV

P
U

P
T

T
T

V
T

P
T

Determine the enthalpy and entropy changes of liquid water for a

change of state from 1 bar and 25C to 1000 bar and 50C. The data
for water are given.
H1 and S1 at 1 bar, 25C
H2 and S2 at 1 bar, 50C

V
dH C P dT V T

H3 and S3 at 1000 bar, 50C

volume expansivity

dP

1 (513 10
H 75.310(323.15 298.15)
dS C P

dT V

dP
T T P

dH C P dT 1 T VdP

H C P (T2 T1 ) 1 T2 V ( P2 P1 )
6

)(323.15) (18.204)(1000 1)
3400 J / mol
10
S C P ln

T2
V ( P2 P1 )
T1

323.15 513 10 6 (18.204)(1000 1)

S 75.310 ln

5.13 J / mol
298.15
10

Internal energy and entropy change calculations f (V,T)

U
U
dT
dV
T V
V T

S
S
dT
dV
T V
V T

dU
U

CV
V

S
T

S
dU CV dT T

P
T

P dV

dU CV dT T

dS

P dV

T
V

CV
T

dT P
dS CV

dV
T T V

Gibbs energy G = G (P,T)

dG VdP SdT

Thermodynamic property of great potential utility

1
G
G
dG
dT

2
RT
RT
RT

G H TS dG VdP SdT

V
H
G

dP

dT

2
RT
RT
RT

V
(G / RT )

RT
P

G (G / RT )
(G / RT )

dP
dT
P
T
RT
T

H
(G / RT )
T

RT
T

G/RT = g (P,T)
The Gibbs energy serves as a generating function
for the other thermodynamic properties.

Residual properties
The definition for the generic residual property:
M R M M ig
M and Mig are the actual and ideal-gas properties,
respectively.
M is the molar value of any extensive thermodynamic
properties, e.g., V, U, H, S, or G.

The residual Gibbs energy serves as a generating

function for the other residual properties:
GR V R
HR

d
dP
dT
2
RT
RT
RT

 GR V R
HR

d
dP
dT
2
RT
RT
RT

GR V R

d
dP
RT
RT

const T

R
PV
GR

dP
0
RT
RT

V V V
R

P Z
HR
T

0
RT
T

S R H R GR

R
RT RT

dP
P

H
(G / RT )
T

RT

ig

P
GR
dP
( Z 1)
0
RT
P

P Z
SR
T

0
R
T

ZRT RT

P
P

const T

dP P
dP
( Z 1)
0
P
P

const T
Z = PV/RT: experimental measurement .Given PVT data or an appropriate equation
of state, we can evaluate HR and SR and hence all other residual properties.

Z dP
H H H H C dT RT

T0
0

T
P

P Z

dP
ig
2
H 0 R ICPH (T0 , T ; A, B, C , D) RT

T
P

P Z

dP
ig
ig
2
H 0 C P T T0 RT

H
0

T
P

ig

ig
0

ig
P

P Z

H 0ig R MCPH (T0 , T ; A, B, C , D ) T T0 RT 2

dP

T
P Z

dT
P
dP P
dP
S S ig S R S 0ig C Pig
R ln R T

(
Z

1
)

T0
0
0
T
P

T
P
P

P
0

P Z
ig

P
dP P
dP
S 0 R ICPS (T0 , T ; A, B, C , D) R ln R T
( Z 1)

0
0
P0
P
T P P

P Z
ig

T
P
dP P
dP
ig
S 0 C P ln R ln R T
( Z 1)

S
0
0
T
P

T
P
P

P
0
0

P Z

T
P
S 0ig R MCPS (T0 , T ; A, B, C , D) ln R ln R T

0
T
P

0
0

dP P
dP
( Z 1)
0
P
P

Calculate the enthalpy and entropy of saturated isobutane vapor at 360

K from the following information: (1) compressibility-factor for
isobutane vapor; (2) the vapor pressure of isobutane at 360 K is 15.41
bar; (3) at 300K and 1 bar, H 0ig 18115 J / mol S 0ig 295.976 J / mol K (4) the
ideal-gas heat capacity of isobutane vapor: C Pig / R 1.7765 33.037 10 3 T
P Z
HR
T

0
RT

P Z
dP S R
T

0
P R

dP P
dP
( Z 1)
0
P
P

Graphical integration requires plots of

P Z
HR
T

0
RT

P Z
SR
T

0
R

/ P and (Z-1)/P vs. P.

P

dP
(360)(26.37 10 4 ) 0.9493
P

H R 2841.3 J / mol

dP P
dP
( Z 1)
0.9493 (0.02596) 0.6897
0
P
P

S R 5.734 J / mol K

H H 0ig R ICPH (300,360;1.7765,33.037 E 3,0.0,0.0) H R 21598.5

S S 0ig R ICPS (300,360;1.7765,33.037 E 3,0.0,0.0) R ln

J
mol

15.41
J
S R 286.676
1
mol K

Residual properties by equation

of state
If Z = f (P,T):
P Z
HR
T

0
RT
T

dP
P

P Z
SR
T

0
R
T

dP P
dP
( Z 1)
0
P
P

The calculation of residual properties for gases

and vapors through use of the virial equations and
cubic equation of state.

Use of the virial equation of state

P
GR
dP two-term virial equation
( Z 1)
0
RT
P
P Z
HR
T

0
RT
T

dP
P

Z 1

BP
RT

Z 1

BP
RT

G R BP

RT RT

P
HR

BP
T
(1
)
0
RT
RT
T

dP
P

P P 1 dB
HR
B
T
2
0
RT
R T dT T

H R P B dB

RT R T dT
S R H R GR

R
RT RT

SR
P dB

RT
R dT

dP
P

Three-term virial equation

Z 1 B C 2

GR
3
2 B C 2 ln Z
RT
2

P
GR
dP
( Z 1)
0
RT
P
P Z
HR
T

0
RT
T

P ZRT

dP
P

B dB
HR
C 1 dC 2
T

RT
T 2 dT
T dT

S R H R GR

R
RT RT

Application up to moderate pressure

Use of the cubic equation of state

The generic cubic equation of state:
RT
a(T )
P

V b (V b)(V b)

d ln (Tr )
H
Z 1
1 qI
RT
d ln Tr

a (T )
q
bRT

d ln (Tr )
SR
ln Z
1 qI
R
d ln Tr

bP
RT

1
b
Z
q
1 b
(1 b)(1 b)

( Z 1)

d
ln(1 b) qI

d
dq

dT

d ( b)
(1 b)(1 b)

const T

Find values for the residual enthalpy HR and the residual entropy SR
for n-butane gas at 500 K and 50 bar as given by Redlich/Kwong
equation.
P
(Tr )
500
50
3.8689
1.317 r 0.09703 q
1.176 Pr

T
T
r
37.96
425.1
r

Tr

0
Z
Z 1 q
( Z )( Z ) 1
I

d ( b)
(1 b)(1 b)

const T

Z 0.685
I

Z
1
0.13247
ln
Z

d ln (Tr )
HR
Z 1
1 qI
RT
d ln Tr

H R 4505

J
mol

d ln (Tr )
SR
ln Z
1 qI
R
d ln Tr

S R 6.546

J
mol K

Two-phase systems
Whenever a phase transition at constant
temperature and pressure occurs,
The molar or specific volume, internal energy, enthalpy,
and entropy changes abruptly. The exception is the
molar or specific Gibbs energy, which for a pure
species does not change during a phase transition.
For two phases and of a pure species coexisting at
equilibrium:

G G
where G and G are the molar or specific Gibbs energies of the individual phases

G G

dG dG
dG VdP SdT

V dP

sat

S dT V dP

dH TdS VdP

sat

S dT

dP sat S S
S

dT
V V
V

H TS
The latent heat of phase transition

dP sat
H

TV
The Clapeyron equation dT
V V v

RT
P sat

Ideal gas, and Vl << Vg

d ln P sat
H R
d (1 / T )
lv

The Clausius/Clapeyron equation

dP sat
H

dT
TV
The Clapeyron equation: a vital connection between the properties of different phases.

P f (T )
ln P sat A

ln P sat A

ln Prsat

B
T

For the entire temperature range from the triple point

to the critical point

B
The Antoine equation, for a specific temperature range
T C

A B 1.5 C 3 D 6 The Wagner equation, over a wide

temperature range.
1

1 Tr

Two-phase liquid/vapor systems

When a system consists of saturated-liquid and
saturated-vapor phases coexisting in equilibrium,
the total value of any extensive property of the
two-phase system is the sum of the total properties
of the phases: M (1 x v ) M l x v M v
M represents V, U, H, S, etc.
e.g., V (1 x v )V v x vV v

Thermodynamic diagrams and tables

A thermodynamic diagram represents the temperature,
pressure, volume, enthalpy, and entropy of a substance on
a single plot. Common diagrams are:
TS diagram
PH diagram (ln P vs. H)
HS diagram (Mollier diagram)

In many instances, thermodynamic properties are reported

in tables. The steam tables are the most thorough
compilation of properties for a single material.

Fig. 6.2

Fig. 6.3

Fig. 6.4

Superheated steam originally at P1 and T1 expands through a nozzle to an

exhaust pressure P2. Assuming the process is reversible and adiabatic, determine
the downstream state of the steam and H for the following conditions:
(a) P1 = 1000 kPa, T1 = 250C, and P2 = 200 kPa.
(b) P1 = 150 psia, T1 = 500F, and P2 = 50 psia.

Since the process is both reversible and adiabatic, the entropy change
of the steam is zero.
(a) From the steam stable and the use of interpolation,
At P1 = 1000 kPa, T1 = 250C:
H1 = 2942.9 kJ/kg, S1 = 6.9252 kJ/kg.K
At P2 = 200 kPa,
S2 = S1= 6.9252 kJ/kg.K < Ssaturated vapor,
the final state is in the two-phase liquid-vapor region:
S 2 (1 x2v ) S 2l x2v S 2v

6.9252 1.5301(1 x2v ) 7.1268 x2v

x2v 0.9640

H H 2 H1 315.9

kJ
kg

H 2 (1 0.964)(504.7) (0.964)(2706.3) 2627.0

(a) From the steam stable and the use of interpolation,

At P1 = 150 psia, T1 = 500F:
H1 = 1274.3 Btu/lbm, S1 = 1.6602 Btu/lbm.R
At P2 = 50 psia,
S2 = S1= 1.6602 Btu/lbm.K > Ssaturated vapor,
the final state is in the superheat region:
H 2 1175 .3 Btu / lbm

T2 283.28 F
H H 2 H1 99.0

Btu
lbm

A 1.5 m3 tank contains 500 kg of liquid water in equilibrium with pure water
vapor, which fills the remainder of the tank. The temperature and pressure are
100C, and 101.33 kPa. From a water line at a constant temperature of 70C and
a constant pressure somewhat above 101.33 kPa, 750 kg of liquid is bled into
the tank. If the temperature and pressure in the tank are not to change as a result
of the process, how much energy as heat must be transferred to the tank?
Energy balance:

d (mU ) cv
Q H m
dt

d (mU ) cv
dm
Q H cv
dt
dt

Q (mU ) cv H mcv
H U PV

Q (mH ) cv ( PmV ) cv H mcv

Q (m2 H 2 ) cv (m1 H1 ) cv H mcv

At the end of the process, the tank still contains saturated liquid and
saturated vapor in equilibrium at 100C and 101.33 kPa.

Q (m2 H 2 ) cv (m1 H1 ) cv H mcv

H 293.0

kJ
kg

saturated liquid @ 70 C

kJ
kg

saturated liquid @ 100 C

H cvl 419.1

H cvv 2676.0

kJ
kg

saturated vapor @ 100 C

From the steam table, the specific volumes of saturated liquid and saturated
vapor at 100C are 0.001044 and 1.673 m3/kg , respectively.
( m1 H1 ) cv m1l H1l m1v H1v 500( 419.1)
m2 500

1.5 (500)(0.001044)
(2676.0) 211616 kJ
1.673

1.5 (500)(0.001044)
750 m2l m2v 1.5 1.673m2v 0.001044m2l
1.673
(m2 H 2 ) cv m2l H 2l m2v H 2v 524458kJ

Q (m2 H 2 ) cv (m1 H1 ) cv H mcv 524458 211616 (750)(293.0) 93092kJ

H
T
0
RT

P Z
SR
T

0
R
T

dP
P

P Pc Pr

T TcTr

dP P
dP
( Z 1)
0
P
P

Pr Z
HR

Tr2
0
RTc
Tr

Pr Z
SR

Tr
0
R
Tr

Pr

Pr

dPr
Pr

Pr
dPr
dP
( Z 1) r
0
Pr
Pr

Z Z 0 Z 1
0
Pr Z
HR
2

Tr
0
RTc
Tr

0
Pr Z
SR

Tr
0
R
Tr

Pr

Pr

S R S R

SR

R R
R
0

Pr

dPr

Pr

Pr
Pr Z
dPr
dPr
0

Tr
( Z 1)
0
0
Pr
Pr

Tr

HR HR
HR

RTc RTc
RTc
0

Pr Z
dPr
2

Tr
0
Pr

Tr

Pr

Pr
dPr
dPr
1

( Z 1)
Pr 0
Pr

HRB(TR, PR, OMEGA)

SRB(TR, PR, OMEGA)

Table E5 ~ E12

T2

H 2 H C Pig dT H 2R
ig
0

T0

T1

H1 H C dT H
ig
0

T0

ig
P

R
1

T2

H C Pig dT H 2R H1R
T1

H C Pig

T2

S 2 S C Pig
ig
0

T0

dT
P
R ln 2 S 2R
T
P0

dT
P1
S1 S C
R ln S1R
T0
T
P0
ig
0

T1

ig
P

(T2 T1 ) H 2R H1R

S C Pig

dT
P
R ln 2 S 2R S1R
T
P1

S C Pig

ln

T2

T1

P2
S 2R S1R
P1

Estimate V, U, H, and S for 1-butene vapor at 200C and 70 bar if H and S are
set equal to zero for saturated liquid at 0C. Assume that only data available are:
Tc 420 K

Pc 40.43 bar

0.191

Tn 266.9 K (nomal boiling pt.)

C Pig / R 1.967 31.630 10 3 T 9.837 10 6 T 2

Tr 1.127

Pr 1.731

Z Z 0 Z 1
0.485 (0.191)(0.142)
0.512

ZRT
cm 3
V
287.8
P
mol

Assuming four steps:

(a) Vaporization at T1 and P1 = Psat
(b) Transition to the ideal-gas state at (T1, P1)
(c) Change to (T2, P2) in the ideal-gas state
(d) Transition to the actual final state at (T2, P2)

Fig 6.7

Fig 6.7

B
ln 1.0133 A
266.9

Step (a)

ln P sat A

B
T

B
ln 40.43 A
420

For = 273.15K,
Psat = 1.2771 bar

H nlv 1.092(ln Pc 1.013)

9.979
The latent heat at normal boiling point:
RTn
0.930 Trn
The latent heat at 273.15 K:
S lv 79.84

Step (b)

H TS

J
mol K

H
H nlv
lv

H lv 21810

1 Tr

1 Tr
n

0.38

J
mol

Tr 0.650 Pr 0.0316

HR HR
HR

RTc RTc
RTc
0

S R S R
SR

R R
R
0

HRB(TR, PR, OMEGA) 0.0985 H 1R 344

SRB
(
TR
,
PR
,
OMEGA
)

0
.
1063

1 0.88

J
mol
J
mol K

Step (c)
J
mol
70
S ig 8.314 ICPS (273.15,473.15;1.967,31.630 E 3,9.837 E 6,0.0) 8.314 ln
1.2771
J
22.18
mol K
H ig 8.314 ICPH (273.15,473.15;1.967,31.630 E 3,9.837 E 6,0.0) 20564

Step (d)

Tr 1.127 Pr 1.731

HR HR
HR

RTc RTc
RTc
0

S R S R
SR

R R
R
0

Total

2.430

H 2R 8485

J
mol

1.705

S 2R 14.18

J
mol K

J
mol
J
S S 79.84 (0.88) 22.18 14.18 88.72
mol K
J
U H PV 34233 (70)(287.8) / 10 32218
mol
H H 21810 (344) 20564 8485 34233

Gas mixtures
Simple linear mixing rules
yii TPc yiTci PPc yi Pci
i

Estimate V, HR, and SR for an equimolar mixture of carbon dioxide and propane
at 450K and 140 bar
TPc yiTci (0.5)(304.2) (0.5)(369.8) 337 K
i

PPc yi Pci (0.5)(73.83) (0.5)(42.48) 58.15bar

i

yii (0.5)(0.224) (0.5)(0.152) 0.188

i

Tpr 1.335

Z 0 0.697

Ppr 2.41

Z 1 0.205

Z Z 0 Z 1 0.736

1
0
1
ZRT
cm3 H R H R 0

HR
S R S R
SR
V
196.7

1.762
1.029
R
R
R
RT
RT
RT
P
mol

pc
pc
pc

H R 4937 J / mol

S R 8.56 J / mol K