PERTEMUAN 2

Chapter 6: Thermodynamics properties of fluids

APPLY and DEVELOP property relations for
homogeneous phase, residual properties, residual
properties by equations of state, two-phase system,
thermodynamic diagrams, tables of thermodynamics
properties, GENERALIZE property correlations for
gases.
 OBJECTIVES
• Develop fundamental relations between
commonly encountered thermodynamic
properties and express the properties that
cannot be measured directly in terms of easily
measurable properties.
• Develop the Maxwell relations, which form the
basis for many thermodynamic relations.
• Develop general relations for cv, cp, du, dh, and
ds that are valid for all pure substances.
• Develop a method of evaluating the ∆h, ∆u, and
∆s of real gases through the use of generalized
enthalpy and entropy departure charts.
 6.1. 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 , H , and S
The enthalpy: H  U  PV
The Helmholtz energy: A  U  TS
The Gibbs energy: G  H  TS

For one mol of homogeneous fluid of constant composition:

 T   P  Maxwell relations are

dU  TdS  PdV      extremely valuable in
 V  S  S V thermodynamics because
dH  TdS  VdP  T   V 
they provide a means of
    determining the change in
 P S  S P entropy, which cannot be
dA  PdV  SdT measured directly, by simply
 P   S  measuring the changes in
dG  VdP  SdT    
 T V  V T properties P, v, and T.
fundamental property relations: These Maxwell relations are
 V   S 
general equation for a      limited to simple
homogeneous fluid of constant  T P  P T compressible systems.
composition
Maxwell’s equations
Enthalpy, entropy and internal energy change calculations f (P,T)

 H   H   S   S 
dH    dT    dP dS    dT    dP
 T  P  P T  T  P  P T
 H  dH  TdS  VdP  S  C  V   S 
   CP    P     
 T P  T  P T  T  P  P T
 H   S 
   T   V
 P T  P T dT  V 
dS  CP   dP
 H 

 S  T  T  P
  T  
 T  P  T  P

  S  
dH  CP dT   T    V dP H  U  PV
  P T 

 V   S 
 H   U   V 
          P  V
 T  P  P T  P T  P T  P T

  V    U   V   V 
dH  CP dT  V  T   dP    T    P 
  T  P   P T  T  P  P T
 Problem 6.1
Determine the enthalpy and entropy changes of liquid
water for a change of state From 1 bar and 25oC to
1,000 bar and 50oC. Data change are given in the
Following table.
  V 
   V
  V    T P
dH  CP dT  V  T   dP dH  CP dT  1  T VdP
  T  P  volume expansivity

H  CP (T2  T1 )  1   T2  V ( P2  P1 )

H  75.310(323.15  298.15) 
1  (513 10 6

)(323.15) (18.204)(1000  1)
 3400 J / mol
10
dT  V  T2
dS  CP   dP S  C P ln   V ( P2  P1 )
T  T  P T1

S  75.310 ln 
 
323.15 513 106 (18.204)(1000  1)
 5.13J / mol
298.15 10
Gibbs energy G = G (P,T)

dG  VdP  SdT Thermodynamic property of great potential utility

 G  1 G
d  dG  dT
 RT  RT
2
RT
G  H  TS dG  VdP  SdT
 G  V H  G   (G / RT )   (G / RT ) 
d   dP  dT d   dP    dT
 RT  RT RT 2
 RT   P T  T P

V  (G / RT ) 
 
RT  P T
H  (G / RT ) 
 T   G/RT = g (P,T)
RT  T P

The Gibbs energy serves as a generating function

for the other thermodynamic properties.
 6.2. 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  VR HR
d    dP  2
dT
 RT  RT RT
  GR  VR HR const T  GR  VR
d    dP  2
dT d    dP
 RT  RT RT  RT  RT

GR PV
R
 dP
RT 0 RT
ZRT RT
V R  V  V ig  
H  (G / RT ) 
P P
 T  
HR P  Z  dP RT  T P GR dP
 T  
P
   ( Z  1)
RT 0
 T  P P RT 0 P const T

S R H R GR SR P  Z  dP P dP
   T      ( Z  1)
R RT RT R 0
 T  P P 0 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.
 ig R
T0
 

ig
0
2
0
 T
P
ig

 P

P  Z  dP 
H  H  H  H   C dT   RT  
T

P


 P  Z  dP 
 ig
0
2

 H  R  ICPH (T0 , T ; A, B, C , D)   RT  

 
 0
 T P P 


 H  C
ig
0
ig
P H T  T0 
 2
P  Z  dP 
  RT  
 

P

 0 T P 
 P  Z  dP 

 H  R  MCPH (T0 , T ; A, B, C , D)T  T0 
ig
0 
  RT  
2


 
 0
 T P P 
 T dT P  P  Z  dP P dP 
S  S ig  S R  S 0ig   C Pig  R ln   R  T      ( Z  1) 
 T0 T P0  0
 T P P 0 P 
 ig P  P  Z  dP P dP 
 S 0  R  ICPS (T0 , T ; A, B, C , D)  R ln   R  T      ( Z  1) 
 P0   0
 T  P P 0 P
 ig T P  P  Z  dP P dP 
 S 0  C Pig ln  R ln   R  T      ( Z  1) 

S T0 P0   0
 T P P 0 P
 T P  P  Z  dP P dP 
 S 0ig  R  MCPS (T0 , T ; A, B, C , D) ln  R ln   R  T      ( Z  1) 
 T0 P0  0
 T P P 0 P 
 6.3. 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, (4)
the ideal-gas heat capacity of isobutane vapor:
H 0ig  18115 J / mol S 0ig  295.976 J / mol  K
CPig / R  1.7765  33.037 103 T

HR P  Z  dP SR P  Z  dP P dP
 T     T     0 ( Z  1)
RT 0
 T P P R 0
 T P P P
 Z 
Graphical integration requires plots of   / P and (Z-1)/P vs. P.
 T  P

HR P  Z  dP
 T     (360)( 26.37 104 )  0.9493 H R  2841.3J / mol
RT 0
 T  P P
SR P  Z  dP P dP
 T      ( Z  1)  0.9493  (0.02596)  0.6897 S R  5.734 J / mol  K
R 0
 T P P 0 P

 
H  H 0ig  R  ICPH (300,360;1.7765,33.037 E  3,0.0,0.0)  H R  21598.5
J
mol

 
S  S 0ig  R  ICPS (300,360;1.7765,33.037 E  3,0.0,0.0)  R ln
15.41
1
 S R  286.676
J
mol  K
 Residual properties by equation of
state
• If Z = f (P,T):
HR P  Z  dP SR P  Z  dP P dP
 T     T     0 ( Z  1)
RT 0
 T P P R 0
 T P 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
BP
GR P dP two-term virial equation Z 1  RT G R BP
  ( Z  1) 
RT 0 P RT RT
BP
Z 1 
HR P  Z  dP RT HR P  BP  dP
 T     T   (1  )
RT 0
 T  P P RT 0
 T RT  P P

HR P   P  1 dB B   dP
 T      2  
RT 0
  R  T dT T   P P

H R P  B dB 
   
RT R  T dT 
S R H R GR SR P dB
  
R RT RT RT R dT
Three-term virial equation Z  1  B  C 2 P  ZRT

GR P dP GR 3
  ( Z  1)  2 B  C 2  ln Z
RT 0 P RT 2

HR P  Z  dP HR  B dB   C 1 dC  2 
 T     T        
RT 0
 T  P P RT  T dT   T 2 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 ) 1 b
P  Z q
V  b (V  b)(V  b) a(T ) 1  b (1  b)(1  b)
q
bRT

 d
H R
 d ln  (Tr ) 
 Z 1    1 qI 
bP 
0
( Z  1)

  ln( 1  b)  qI
RT  d ln Tr  RT   Z  d dq
SR  d ln  (Tr )    
 T   
 I
 ln Z       1 qI dT
0

R  d ln Tr   d ( b)
I  const T
0 (1  b)(1  b)
6.4. 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.

500 50 P  (Tr )
Tr   1.176 Pr   1.317    r  0.09703 q   3.8689
425.1 37.96 Tr T r

Z   0
Z  1    q Z  0.685
( Z   )( Z   )  1
 d ( b) 1  Z   
I  const T I ln    0.13247
0 (1  b)(1  b)     Z   

HR  d ln  (Tr )  J
 Z 1    1 qI H R  4505
RT  d ln Tr  mol

SR  d ln  (Tr ) 
 ln Z     
J
 1 qI S R  6.546
R  d ln Tr  mol  K
 6.4. 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 α and β of a pure species coexisting at
equilibrium:

G  G 
where Gα and Gβ are the molar or specific Gibbs energies of the individual phases
G  G  dG  dG 
dG  VdP  SdT
    dP sat S   S  S 
V dP sat
 S dT  V dP sat
 S dT   

dT V V V 

dH  TdS  VdP H   TS 

The latent heat of phase transition
dP sat H 

The Clapeyron equation dT TV 

RT
V   V v 
P sat
Ideal gas, and Vl << Vg

d ln P sat
H   R
lv

d (1 / T )
The Clausius/Clapeyron equation
dP sat H 

dT TV 
The Clapeyron equation: a vital connection between the properties of different phases

P  f (T )

B For the entire temperature range from the triple point

ln P sat  A 
T to the critical point

B
ln P sat  A  The Antoine equation, for a specific temperature
T  C range

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

ln Prsat 
1  temperature range.

 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
 6.6. 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 ΔH for the following
conditions:
(a) P1 = 1000 kPa, T1 = 250°C, and P2 = 200 kPa.
(b) P1 = 150 psia, T1 = 500°F, 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 = 250°C:

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 ) S2l  x2v S 2v 6.9252  1.5301(1  x2v )  7.1268x2v

x2v  0.9640
kJ
H  H 2  H1  315.9 H 2  (1  0.964)(504.7)  (0.964)(2706.3)  2627.0
kg
(a) From the steam stable and the use of interpolation,
At P1 = 150 psia, T1 = 500°F:

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:

T2  283.28 F H 2  1175.3 Btu / lbm

Btu
H  H 2  H1  99.0
lbm
6.7. 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
100°C, and 101.33 kPa. From a water line at a constant temperature of 70°C
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  d (mU ) cv  dm

 Q  H  cv
dt dt dt

Q  (mU )cv  H mcv

H  U  PV
Q  (mH )cv  ( PmV )cv  H mcv

Q  (m2 H 2 )cv  (m1H1 )cv  H mcv

At the end of the process, the tank still contains saturated liquid and
saturated vapor in equilibrium at 100°C and 101.33 kPa.
Q  (m2 H 2 )cv  (m1H1 )cv  H mcv kJ
H   293.0 saturated liquid @ 70 C
kg
kJ
H cvl  419.1 saturated liquid @100 C
kg
kJ
H cvv  2676.0 saturated vapor @100 C
kg

From the steam table, the specific volumes of saturated liquid and saturated
vapor at 100°C are 0.001044 and 1.673 m3/kg , respectively.

1.5  (500)(0.001044)
(m1 H1 ) cv  m1l H1l  m1v H1v  500(419.1)  (2676.0)  211616kJ
1.673
1.5  (500)(0.001044)
m2  500   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  (m1H1 )cv  H mcv  524458  211616  (750)(293.0)  93092kJ

 P  Pc Pr T  TcTr Pr  Z
H R
 Z  dP HR  dPr
 Tr2  
P
 T    
RT 0
 T P P RTc 0
 Tr  Pr Pr
SR P  Z  dP P dP SR Pr  Z  dPr dP
 T   0
Pr
  ( Z  1)  Tr      ( Z  1) r
R 0
 T  P P P R 0
 Tr  Pr Pr 0 Pr

Z  Z 0  Z 1

H R  2 Pr  Z 0  dPr   Pr  Z 
1
dPr 
  Tr        Tr  
2
 
RTc 

0
 Tr  Pr Pr   0
 Tr  Pr Pr 

SR  Pr  Z 
0
dPr Pr dPr   Pr  Z 
1
dPr Pr dPr 
  Tr      ( Z  1)
0
    Tr      ( Z  1)
1

R  0 
 r  Pr r
T P 0 Pr   0 
 r  Pr r
T P 0 Pr 
  

HR  HR

 0


HR 
1
 
  HRB (TR, PR, OMEGA)
RTc  RTc RTc 

SR  SR

 
0


SR     SRB (TR, PR, OMEGA)
1
Table E5 ~ E12
R  R R 
 T2
H 2  H   C Pig dT H 2R
ig
0 T2
H   C Pig dT H 2R  H1R
T0

T1 T1
H1  H   C dT H
ig
0
ig
P 1
R
T0

H  CPig (T2  T1 )  H 2R  H1R

H

T2 dT P
S 2  S   C Pig
ig
0  R ln 2 S 2R
T0 T P0 T2 dT P
S   C Pig  R ln 2 S 2R  S1R
dT
T1 P1 T1 T P1
S1  S   C
ig
0  R ln S1R
ig
P
T0 T P0
P2
S  C Pig ln  S 2R  S1R
S P1
6.8. Estimate V, U, H, and S for 1-butene vapor at 200°C and 70 bar if H and S
are set equal to zero for saturated liquid at 0°C. Assume that only data available
are:
Tc  420 K Pc  40.43 bar   0.191 Tn  266.9K (nomal boiling pt.)
CPig / R  1.967  31.630 103 T  9.837 106 T 2

Tr  1.127 Pr  1.731 Assuming four steps:

(a) Vaporization at T1 and P1 = Psat
Z  Z 0  Z 1
(b) Transition to the ideal-gas state at (T1, P1)
 0.485  (0.191)(0.142) (c) Change to (T2, P2) in the ideal-gas state
 0.512 (d) Transition to the actual final state at (T2, P2)
ZRT cm3
V  287.8
P mol

Fig 6.7
Fig 6.7
Step (a) B
ln 1.0133  A 
B 266.9 For = 273.15K,
ln P sat  A 
T B Psat = 1.2771 bar
ln 40.43  A 
420
H nlv 1.092(ln Pc  1.013)
The latent heat at normal boiling point:   9.979
RTn 0.930  Trn
0.38
H lv  1  Tr 
The latent heat at 273.15 K:  
H n  1  Trn
lv 

J H   TS  J
S  79.84
lv
H lv  21810
mol  K mol

Step (b) Tr  0.650 Pr  0.0316


 
HR  HR
0


 
HR 
1

  HRB (TR, PR, OMEGA)  0.0985  H1  344

R J
RTc  RTc RTc  mol


 
SR  SR
0


SR     SRB (TR, PR, OMEGA)  0.1063
1
 S  0.88
R J
mol  K
1
R  R R 
Step (c)
J
H ig  8.314  ICPH (273.15,473.15;1.967,31.630 E  3,9.837 E  6,0.0)  20564
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
Step (d) Tr  1.127 Pr  1.731
HR  HR

 0


 
HR 
1

  2.430 H 2R  8485
J
RTc  RTc RTc  mol

SR  SR

 
0


SR     1.705
1
S  14.18
R J
mol  K
2
R  R R 

Total J
H  H  21810  (344)  20564  8485  34233
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
 Gas mixtures
• Simple linear mixing rules
   yii TPc   yiTci PPc   yi Pci
i i 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 T pr  1.335
i Z 0  0.697
PPc   yi Pci  (0.5)(73.83)  (0.5)( 42.48)  58.15bar Ppr  2.41 Z 1  0.205
i

   yii  (0.5)(0.224)  (0.5)(0.152)  0.188

i
Z  Z 0  Z 1  0.736

ZRT cm3 H R  H R 0 HR 

1
S R  S R 
0
SR 
1

V  196.7     1.762     1.029

P mol RT pc  RT pc RT pc  R  R R 
H R  4937 J / mol S R  8.56 J / mol  K