Chapter 3:

Thermodynamic Properties of Fluids

Assoc.Prof.Dr.Sininart Chongkhong “A Dao”

ChE. PSU.

1
Chapter 6 in the textbook
Purpose of this Chapter
• To develop from the first and second laws the
fundamental property relations which underlie the
mathematical structure of thermodynamics.
➢ Derive equations which allow calculation of
enthalpy and entropy values from PVT and heat
capacity data.
➢ Discuss diagrams and tables by which property
values are presented for convenient use.
➢ Develop generalized correlations which provide
estimated of property values in the absence of
complete experimental information.

2
Property Relations for Homogeneous Phases
Fundamental Properties

d (nU ) = dQrev − dWrev

d (nU ) = Td (nS ) − Pd (nV ) (6.1)
✓ Although this equation is derived from the
special case of a reversible process, it not
restricted in application to reversible process.
✓ It applies to any process in a system of constant
mass that results in a differential change form
one equilibrium state to another.
✓ The system many consist of a single phase or
several phases; may be chemically inert or may
undergo chemical reaction.
3
Define

H = Enthalpy H  U + PV …(2.11)

A = Helmholtz energy A  U − TS …(6.2)

G = Gibbs energy G  H − TS …(6.3)

4
Based on one mole (or to a unit mass) of a
homogeneous fluid of constant composition,
they simplified to
Maxwell’s equations
dF = Mdx + Ndy  T   P 
  = − 
 V  S  S V
dU = TdS − PdV  T   V 
  = 
dH = TdS + VdP  P  S  S  P
dA = − PdV − SdT  P   S 
  = 
dG = VdP − SdT  T V  V T
 V   S 
  = − 
 T  P  P T 5
 Enthalpy and Entropy as Functions of T and P

The most useful property relations for the enthalpy

and entropy of a homogeneous phase result when
these properties are expressed as functions of T and P
(how H and S vary with T and P).

  V  
dH = C p dT + V − T    dP  (6.20)
  T  P 
dT  V 
dS = C P −  dP  (6.21)
T  T  P

6
Property Relations for Homogeneous Phases

The Ideal Gas State

• For ideal gas, expressions of dH and dS

(eq.6.20-6.21) as functions of T and P can
be simplified to as follows:
 V ig
 R
PV = RT  
ig
 =
 T  p P
dH ig = C Pig dT …(6.23)

dT
dS ig = C Pig − RdP …(6.24)
T

7
 Property Relations for Homogeneous Phases

Alternative Forms for Liquids

• Enthalpy and entropy as functions of T and P as

follows:

dH = C P dT + (1 −  T )VdP  (6.28)
dT
dS = C P − VdP  (6.29)
T
•  and  are weak functions of pressure for
liquids, they are usually assumed constant at
appropriate average values for integration.

 =Volume expansibility (ค.สามารถในการขยาย)

 =Isothermal compressibility (ค.สามารถในการอัด) 8
Example 1

Determine the enthalpy and entropy changes of liquid

water for a change of stage from 1 bar 25C to
1,000 bar 50C.

T( C) P(bar) Cp(Jmol-1K-1) V(cm3mol-1) (K-1)

25 1 75.305 18.071 256x10-6

25 1,000 … 18.012 366x10-6
50 1 75.314 18.234 458x10-6
50 1,000 … 18.174 568x10-6

9
10
H = C p (T2 − T1 ) + (1 − T2 ) V (P2 − P1 )
T2
S = C p ln − V (P2 − P1 )
T1
For P = 1 bar ,

75.305 + 75.314
Cp = = 75.310 Jmol −1 K −1
2

and for T = 50C ,

18.234 + 18.174
V= = 18.204 cm3 mol −1
2
458 + 568
= 10 −6 = 513 10 −6 K −1
2
11
  cm3bar 
H = C p (T2 − T1 ) + (1 − T2 ) V (P2 − P1 )  
 mol 
T2  cm3  bar 
S = C p ln − V (P2 − P1 )  
T1  mol  K 

H = 75.310(323.15 − 298.15) +
1 − (513  10 )(323.15)(18.204)(1,000 − 1)
−6

10 cm3barJ −1
= 1,883 + 1,517 = 3,400 Jmol −1

S = 75.310 ln
( )
323.15 513  10−6 (18.204 )(1,000 − 1)
−
298.15 10
= 6.06 − 0.93 = 5.13 Jmol −1K −1

Note that the effect of P of almost 1,000 bar on H and S of

liquid water is less than that of T of only 25C.

12
Property Relations for Homogeneous Phases

Internal Energy and Entropy as Function of T and V

• Useful property relations for T and V as

independent variables are

 S  CV
  =  (6.30)
 T V T
 U   P 
  = T  − P  (6.31)
 V T  T V
 P  
  =  (6.34)
 T V 

13
• The Partial derivatives dU and dS of homogeneous
fluids of constant composition to temperature and
volume are
  P  
dU = CV dT + T   − P  dV
  T V 
dT  P 
dS = CV +  dV
T  T V

• Alternative forms of the above equations are

  
dU = CV dT + T − P  dV
  
dT 
dS = CV + dV
T 
14
Property Relations for Homogeneous Phases

The Gibbs Energy as a Generating Function

• An alternative form of a fundamental property relation as

defined in dimensionless terms:

อีกรู ปแบบหนึงของสมการความสัมพันธ์ของสมบัติพืนฐาน G/RT

จาก G = H - TS
dG = VdP - SdT, G=G(P,T)\
ค.สัมพันธ์เมือเขียนด้วยหลักทางคณิ ตศาสตร์
d(G/RT) = (1/RT)dG – G(dT/RT2) ...(6.37)

15
  G  V H
d = dP − 2
dT
 RT  RT RT
V   (G RT ) 
= 
RT  P T
H   (G RT ) 
= −T  
RT  T P

พลังงานกิบส์เมือให้เป็ น f(T,P) ซึ งเป็ นค่าทีวัดได้และควบคุมได้

ทําให้ G มีศกั ยภาพในการนําไปใช้ประโยชน์กบั สมบัติตวั อืนๆทีเหลือ
𝑆 𝐻 𝐺 𝑈 𝐻 𝑃𝑉
= − & = −
𝑅 𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇

16
•The Gibbs energy when given as a function of T and
P therefore serves as a generating function for the
other thermodynamic properties, and implicitly
represents complete information.

•เมือสามารถเขียน G/RT = G(T,P) ได้ จะสามารถคํานวณสมบัติ

อืนได้ดว้ ยวิธีทางคณิ ตศาสตร์อย่างง่ายๆ โดยจะใช้พลังงานกิบส์เป็ น
พลังงานก่อกําเนืดสําหรับสมบัติตวั อืนๆ ซึงการหาค่า G หายากมากจึง
ต้องให้เขียน G ในรู ปค.สุ มพันธ์กบั ฟช. อืนทีสามารถหาได้จากการ
ทดลอง จึงเกิด ฟช. ใหม่ทีเรี ยกว่า พลังงานกิบส์ตกค้าง และสมบัติตวั
อืนๆก็สามารถนิยามได้ลกั ษณะเดียวกัน

17
Residual Properties

• The definition for the generic residual property is:

M  M −M
R ig

• M is the molar value of any extensive

thermodynamics property: V, U, H, S, G.
• M, Mig = the actual and ideal gas properties which
are at the same temperature and pressure.

18
• Residual gibbs energy:

G R  G − G ig
• G, Gig = the actual and ideal gas values of the
Gibbs energy at the same temperature and
pressure.

• Residual volume:
RT
V R  V − V ig = V −
P
RT
V =
R
(Z − 1)
P
19
Fundamental property relation
for residual properties

• The fundamental property relation for residual properties

applies to fluids of constant composition.

 GR  V R HR
d   = dP − 2
dT  (6.42)
 RT  RT RT

(
V R   G R / RT 
=
)
  (6.43)
RT  P T

HR (
  G R / RT 
= −T 
)
  (6.44)
RT  T P
20
  GR  V R
From Eq.(6.43), d   = dP (const T )
 RT  RT

GR  GR  PV
R
P dP  GR 
=   +  dP =  ( Z − 1)  (6.45) for ideal gas   = 0
RT  RT  P =0 0 RT 0 P  RT  P =0

HR P  Z  dP
Eq.(6.45 + 6.44); = −T     (6.46)
RT 0 T P
 P

S R H R GR
From = −
RT RT RT

SR P  Z  dP P dP
So, = −T    −  ( Z − 1) (const T )  (6.48)
R 0 T
 P P 0 P

21
Enthalpy and Entropy from Residual
Properties

Applied to H and S ; H = H ig + H R S = S ig + S R
Integration of Eq.(6.23)and (6.24);
T T
P
H = H +  C dT
ig ig
0
ig
P S = S +  C dT − R ln
ig ig
0
ig
P
T0 T0
P0
T
Substitution; H = H 0ig +  C Pig dT + H R  (6.50)
T0
T
P
S = S +  C dT − R ln + S R
ig
0
ig
P  (6.51)
T0
P0

22
H = H 0ig + C igP (T − T0 ) + H R  (6.52)
H

T P
S = S 0ig + C igP ln − R ln + S R  (6.53)
S T0 P0
T2

 dT
ig
C P
T1
C igP C D
C igP  → H
= A + BTam + 2
(4Tam − T1T2 ) +
H T2 − T1 R 3 T1T2
T2
dT
 CP
ig

T1
T C igP  D 
C igP  → S
= A + BTlm + TamTlm C + 2
S ln(T2 / T1 ) R  (T T
1 2 ) 

The true worth of the Eq. for ideal gases is now

evident. They are important because they provide a convenient
base for the calculation of real-gas properties.

23
Residual Properties by Equations of State
Residual Properties from the Virial Equation of State

• The two-term virial eq. gives Z-1 = BP/RT.

G R BP
So, =  (6.54)
RT RT

By Eq.(6.44),
HR
= −T 
( )
  G R / RT 
=
P  B dB 
 −   (6.55)

RT   T P R  T dT 
SR P dB
Substitution int o Eq.(6.47), =−  (6.56)
R R dT

24
In application  is a more convenient variable than V,
PV = ZRT is written in the alternative form.

dP d dZ
P = ZRT  (6.57), dP = RT ( Zd + dZ )  = +
P  Z

GR d
Substitue int o Eq.(6.49); =  ( Z − 1) + Z − 1 − ln Z  (6.58)
RT 0 
H R Z − 1  P    (G R / RT ) 
From Eq.(6.40) and (6.42), =   − 
RT 2 P  T    T 

HR  Z  d
Differentition of Eq.(6.57) and (6.58); = −T    + Z − 1  (6.59)
RT 0  T  

 
SR  Z  d d
From Eq.(6.47), = ln Z − T    −  ( Z − 1)  (6.60)
R 0
T    0 

25
• The three-term virial equation.

Z − 1 = B + C 2 is substitued int o Eq.(6.58) through (6.60).

GR 3
 = 2 B + C 2 − ln Z  (6.61)
RT 2
HR  B dB   C 1 dC  2 
= T  −  +  −    (6.62)
RT  T dT   T 2 dT  
SR  B dB  1  C dC  2 
= ln Z − T  +  +  −     (6.63)
R  T dT  2  T dT  

Application of these equations, useful for gases up to

moderate pressure, requires data for both the second and
third virial coefficients.

26
Residual Properties by Cubic Equations of State

Eq.(3.42) devides by RT and substitute V = 1 /  , as q given by Eq.(3.51).

1 b
 Z= −q
1 − b (1 + b)(1 + b)
b b
Z −1 = −q  (6.64)
1 − b (1 + b)(1 + b)
 Z   dq  b
  = − 
 T    dT  (1 + b)(1 + b)
The integrals of Eqs.(6.58), (6.60);
  
d b d (  b ) d ( b)
0 (Z - 1)
 0 1 − b b
= − q 0 (1 + b)(1 + b)
 
 Z  d dq d ( b)
0  T    dT 0 (1 + b)(1 + b)
  = −

 
d  Z  d dq
To simplify;  (Z -1)
0

= − ln(1 − b) − qI , 0  T    dT I
  = −

27
The generic equation of state presents two cases.

1  1 + b 
Case I :    I = ln    (6.65a )
 −   1 + b 
When ρ is eliminated in favor of Z.
bP P 
= Z= whence = b
RT RT Z
1  Z +  
I= ln    (6.65b)
 −   Z +  
b 
Case II :  =  I= =
1 + b Z + 

28
With evaluation of the integrals, Eqs. (6.58)
through (6.60) reduce to:

GR
= Z − 1 − ln(1 − b) Z − qI  (6.66a )
RT
GR
= Z − 1 − ln( Z −  ) Z − qI  (6.66b)
RT
HR  d ln  (Tr ) 
= Z −1+  − 1 qI  (6.67)
RT  d ln Tr 
SR d ln  (Tr )
= ln( Z −  ) + qI  (6.68)
R d ln Tr

29
Ex. 3
Find values for the HR and SR for n-butane gas at 500 K
50 bar as given by the Redlich/Kwong Eequation.

30
31
 These results are compared with those of other
calculation in Table 6.3.

32
 TWO-PHASE SYSTEMS

G = G  , dG = dG  → V  dP sat − S  dT = V  dP sat − S  dT

dP sat S  − S  S 
Re arrangement , =  =
dT V − V  V 
Integration of Eq.(6.8); H  = TS  (The latent heat of phase transition)
  dP sat H 
Thus, S = H /T  =  (6.71) : The Clapeyron equation
dT TV 
dP sat H l
Phase transition from liquid to vapor; =  (6.72)
dT TV l
l RT l d ln P sat H l
But V = sat Z  = 2 l  (6.73)
P dT RT Z The Clapeyron eq.
for pure-species
d ln P sat H l vaporization
or =  (6.74)
d (1 / T ) RZ l

33
 Temperature Dependence of the Vapor
Pressure of Liquids

B
ln P sat = A −
T
B
The Antoine eq. : ln P sat = A−  (6.76)
T +C
Antoine cons tan ts are given in Table B.2, App.B
A + B 1.5 + C 3 + D 6
A function of Tr ; ln P (Tr ) =
sat
 (6.77)
1−
r

where   1 − Tr

34
35
Two-Phase Liquid/Vapor System

nV = n lV l + n V  n = nl + nv (moles)

V = x lV l + x V  x : mass fraction

V = (1 − x v )V l + x V  xl = 1 − xv

The generic equation :

M = (1 − x v ) M l + x M   (6.82a )
where M  V , U , H , S , etc. An alternative form :
M = M l + x M l  (6.82b)
36
THERMODYNAMIC DIAGRAMS

37
GENERALIZED PROPERTY
CORRELATION FOR GASES

P = Pc Pr → dP = Pc dPr , T = TcTr → dT = Tc dTr

substitue int o Eqs.(6.46) and (6.48) :
P
HR 2  Z  dPr
r

= −Tr     (6.83)
RTc 0
Tr  Pr Pr
Pr P
SR  Z  dPr r dP
R
= Tr 0  Tr 
 Pr Pr
−  ( Z − 1) r  (6.84)
0
Pr

38
  Z   Z 0   Z 1 
Z = Z + Z → 
0 1
 =   +   
 Tr T
 Pr  r  Pr T
 r  Pr

H R  2 r  Z 0  dPr   Pr  Z 1  dP 
P

Eq.(6.83) : = − Tr     −  Tr2    r

RTc   Tr  P Pr    Tr  P Pr 
 0 r   0 r 

HR
=
HR( )
+
HR
0
( ) 1

 (6.85)
RTc RTc RTc

SR  r dPr   Pr  dP
P
 Z 1   Z 1 
R  0
Eq.(6.84) : = − Tr   + Z − 1
0
 − Tr   + Z 1  r
T
 r  Pr Pr  0  Tr  Pr  Pr
   

SR
=
SR( )
+
0
SR ( ) 1

 (6.86)
R R R

Table E.5 - E.12

39
Analytical correlation of the residual properties
at low pressure
The generalized sec ond − virial − coefficient correlation forms

 BP d B dB 0 dB1
B = c = B 0 + B1 , = +
RTc dTr dTr dTr
  
R  R

H d B S dB
Eqs.(6.55) and (6.56); = Pr  B − Tr , = − Pr
RTc  dTr  R dTr
 
 
  
  1 
HR d B 0
d B
 = Pr  B − Tr
0
+   B − Tr
1   (6.87)
RTc  dTr  dTr 
  
  
 
SR  d B0 d B1 
= − Pr  +   (6.88)
R dT
 r dT r 
  40
 0.422
B = 0.083 − 1.6
0
 (3.65)
Tr
0.172
B1 = 0.139 −  (3.66)
Tr4.2
dB 0 0.675
= 2.6  (6.89)
dTr Tr
dB1 0.722
= 5.2  (6.90)
dTr Tr

41
HR and SR with ideal-gas heat capacities

➢ For a change from state 1 to 2:

T2 T1

H 2 = H 0ig +  CPig dT + H 2R H1 = H 0ig +  CPig dT + H1R

0 0

➢The enthalpy change for the process, H = H2 – H1

T2

H =  C Pig dT + H 2R − H1R  (6.91)

T1
T2
P2
Similarly, S =  C Pig dT − R ln + S 2R − S1R  (6.92)
T1
P1

➢ Alternative form

H = C Pig (T2 − T1 ) + H 2R − H1R  (6.93)

H

T2 P
S = C Pig ln − R ln 2 + S 2R − S1R  (6.94)
S T1 P1
42
43
A three-step calculation path
Step 1→1ig: A hypothetical process that transforms a
real gas into an ideal gas at T1 and P1.

H1ig − H1 = − H1R S1ig − S1 = − S1R

Step 1ig →2ig: Changes in the ideal-gas state from
(T1,P1) to (T2,P2).
T2

H ig
= H −Hig
2
ig
1 =  C Pig dT  (6.95)
T1
T2
dT P
S = S − S =  C Pig
ig ig
2
ig
1 − R ln 2  (6.96)
T1
T P1

Step 2ig →2: Another hypothetical process that

transform the ideal gas back into a real gas at T2 and P2.
H 2 − H 2ig = H 2R S 2 − S 2ig = S 2R
44
Ex. 5
Estimate V, U, H and S for 1-butane vapor at 200C, 70 bar
if H and S are set equal to zero for saturated liquid at 0C.
Assume: Tc=420.0 K, Pc=40.43 bar, Tn=266.9 K, =0.191
Cpig/R=1.967+31.630x10-3T-9.837x10-6T2 (T/K)

45
46
 Extension to Gas Mixtures

   yii  (6.97 ) T pc   yiTci  (6.98) Ppc   yi Pci  (6.99 )

i i i

T P
TPr =  (6.100 ) PPr =  (6.101)
T pc Ppc

These replace Tr and Pr for reading entries from the

table of App. E, and lead to values of Z by Eq.(3.57),
and HR/RTpc by Eq.(6.85), and SR/R by Eq.(6.86).

47
Ex. 6
Estimate V, HR, and SR for an equimolar mixture of
carbon dioxide(1) and propane(2) at 450 K and 140 bar by
the Lee/Kesler correlations.

48
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