Thermodynamic Properties of Fluids

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 he absence of complete experimental information.

Property Relations for Homogeneous Phases

Fundamental Properties

d (nU ) d nU

dQrev dWrev 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.

Define
H = Enthalpy

H U PV
A U TS
G H TS

(2.11)

A = Helmholtz energy

(6.2)

G = Gibbs energy

(6.3)

Based on one mole (or to a unit mass) of a homogeneous fluid of constant composition, they simplified to

dU dH dA

TdS PdV TdS VdP PdV SdT

dG VdP SdT

Maxwells equaitons

T V T P P T V T

P S V S S V S P

Enthalpy and Entropy as Functions of T and P

Temperature derivatives:

H T S T

CP
P

CP T

Pressure derivatives:

S P H P

V T V T

V T

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).

dH dS

C p dT dT CP T

V T V T

V T dP
P

dP
P

(6.20)

(6.21)

Property Relations for Homogeneous Phases

Internal Energy as Function of P The pressure dependence of the internal energy is shown as

U P

V T T P T dU Tds PdV

V P

Property Relations for Homogeneous Phases

The Ideal Gas State

For ideal gas, expressions of dH and dS (eq.6.206.21) as functions of T and P can be simplified to as follows:

PV

ig

RT
ig CP dT

V ig T dP R P

R P (6.23) (6.24)

dH ig dS
ig

dT CP T
ig

10

Property Relations for Homogeneous Phases

Alternative Forms for Liquids Relations of liquids can be expressed in terms of and as follows:
S P H P U P V
T

1
T

TV P TV
11

Property Relations for Homogeneous Phases

Alternative Forms for Liquids Enthalpy and entropy as functions of T and P as follows:
dH dS C P dT dT CP T 1 T VdP ...( 6.28 )

VdP ...( 6.29 )

and are weak functions of pressure for liquids, they are usually assumed constant at appropriate average values for integration.
12

Example 6.1
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) 25 25 50 50 1 1,000 1 1,000 75.305 75.314 18.071 18.012 18.234 18.174

(K-1) 256x10-6 366x10-6 458x10-6 568x10-6

13

14

C p T2 T1 S T2 C p ln T1

T2 V P2 V P2 P 1

P 1

For P 1 bar, Cp 75.305 75.314 2 50 C ,

1

75.310 Jmol 1 K

and for T V

18.234 18.174 18.204 cm3 mol 2 458 568 10 6 513 10 6 K 1 2

15

C p T2 T1 S T2 C p ln T1
1
1

T2 V P2 V P2 P 1
6

P 1

75.310 323.15 298.15 1,883 1,517 3,400 Jmol

513 10

323.15 18.204 1,000 1 10

323.15 75.310 ln 298.15

513 10

18.204 1,000 1 10

6.06 0.93 5.13 Jmol 1 K

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.
16

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 T U V P T

CV T T P T P
V

V
17

 The Partial derivatives dU and dS of homogeneous fluids of constant composition to temperature and volume are

dU dS

CV dT dT CV T

T P T

P T

P dV
V

dV
V

Alternative forms of the above equations are

dU dS

CV dT dT CV T

T dV

P dV

18

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:
G d RT V RT H RT T V H dP dT 2 RT RT G RT P

G RT P

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.
19

Residual Properties
The definition for the generic residual property is:

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.

20

 Residual gibbs energy:

G G

ig

G, Gig = the actual and ideal gas values of the Gibbs energy at the same temperature and pressure. Residual volume:

V V

V V

ig

RT P

RT Z 1 P
21

Fundamental property relation for residual properties

The fundamental property relation for residual preperties applies to fluids of constant composition.
GR d RT VR RT HR RT VR dP RT G R / RT P HR dT ( 6.42 ) 2 RT

( 6.43 )
T

G R / RT T

( 6.44 )
P

22

From Eq.(6.43),

GR d RT VR dP 0 RT
P

VR dP RT

(const T )

GR RT

GR RT

P 0

dP ( Z 1) (6.45) 0 P
P

GR for ideal gas RT

0
P 0

Eq.(6.45 6.44);

HR RT GR RT Z T

P 0

Z T

dP (6.46) P

From

SR RT SR R

HR RT
P 0

So,

dP P

P 0

( Z 1)

dP P

(const T )

(6.48)
23

Enthalpy and Entropy from Residual Properties

Applied to H and S ; H
T

H ig

HR
T

S ig

SR

Integratio n of Eq .( 6.23 )and ( 6.24 ); H

ig

H0

ig

C P dT
ig

S H0
ig T ig

ig

S0

ig

C P dT
ig

T0

T0 T ig CP dT

P R ln P0 ( 6.50 )

Substituti on ; H S S0

HR

T0

C P dT
ig

T0

P R ln P0

S R ( 6.51 )

24

H ig S
ig

H 0ig S0
ig

CP

R ( T T ) H 0 H

( 6.52 ) S R ( 6.53 ) C D 2 ( 4Tam T1T2 ) 3 T1T2 TamTlm C D T1T2

T C P S ln T0
T2 ig CP dT T1

P R ln P0
H

CP

T2 T1 dT CP T T ln( T2 / T1 )
T2 ig
1

CP R

A BTam

CP

CP R

A BTlm

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.
25

Example 6.3 Calculate H and S of saturated isobutane vapor at 630 K from the following information: 1. Table 6.1 gives compressibility-factor data 2. The vapor pressure of isobutane at 630 K 15.46 bar 3. Set H0ig = 18,115 Jmol-1 and S0ig = 295.976 Jmol-1K-1 for the ideal-gas reference state at 300 K 1 bar 4. Cpig/R = 1.7765+33.037x10-3T (T/K)

26

27

Solution 6.3 Eqs. (6.46) and (6.48) are used to calculate HR and SR.
P 0

Z T

dP P

dP ( Z 1) 0 P
P

Plot ( Z/ T)P/P and (Z-1)/P vs. P From the compressibility-factor data at 360 K (Z-1)/P The slope of a plot of Z vs. T ( Z/ T)P/P Data for the required plots are shown in Table 6.2.

28

29

P 0

Z T

dP P P

26.37 10 K
4 R

dP ( Z 1) 0 P
P

0.2596

H By Eq . ( 6.46 ), ( 360 )( 26.37 10 4 ) 0.9493 RT R S By Eq . ( 6.48 ), 0.9493 0.2596 0.6897 R For R 8.314 Jmol 1 K 1 H S
R

0.9493 8.314 360 0.6897 8.314

2 ,841.3 Jmol
1 1

5.734 Jmol K

30

ig CP

R ig CP R Tam Tlm
ig CP ig CP

A BTam A BTlm

1.7765 33.037 10 3 Tam 1.7765 33.037 10 3 Tlm

T0 T1 300 360 330 K 2 2 T1 T0 360 300 329.09 K ln( T1 / T0 ) ln( 360 / 300 )
H

12.679( 8.314 ) 105.41 Jmol 1 K 12.649( 8.314 ) 105.16 Jmol 1 K

Substitute int o Eq .( 6.50 ) and ( 6.51 ) H S 18 ,115 105.41( 360 300 ) 2 ,841.2 21,598.5 Jmol 295.576 105.16 ln( 360 ) 300 8.314 ln15.41 5.734
1

286.676 Jmol 1 K

31

Residual Properties by Equations of State

Residual Properties from the Virial Equation of State
The two-term virial eq. gives Z-1 = BP/RT.
So, GR RT BP RT T (6.54) G R / RT T P B R T dB dT (6.55) (6.56)

HR By Eq.(6.44), RT

SR Substitution int o Eq.(6.47), R

P dB R dT

32

In application is a more convenient variable than V, PV = ZRT is written in the alternative form.
dP P d dZ Z

Z RT ( 6.57 ), dP

RT ( Zd GR RT

dZ ) ( Z 1) d P T

Substitue int o Eq .( 6.49 );

Z 1 ln Z ( 6.58 ) ( G R / RT ) T T
0

HR From Eq .( 6.40 ) and ( 6.42 ), RT 2

Z 1 P

HR Differentition of Eq .( 6.57 ) and ( 6.58 ); RT SR From Eq .( 6.47 ), R ln Z T

0

Z T d

Z 1 ( 6.59 )

Z T

d
0

( Z 1)

( 6.60 )

33

 The three-term virial equation.

Z 1 B GR RT HR RT SR R C
2

is substitued int o Eq.(6.58) through (6.60).

2

3 2B C 2 B dB T T dT ln Z T B T

ln Z C T dB dT 1 dC 2 dT 1 C 2 T
2

(6.61) (6.62)
2

dC dT

(6.63)

Application of these equations, useful for gases up to moderate pressure, requires data for both the second and third virial coefficients.
34

Residual Properties by Cubic Equations of State

Eq .( 3.42 ) devides by RT andsubstitut eV Z Z 1 Z T d (Z-1)
0

1/

, as q given byEq .( 3.51 ).

1 1 1 b b b

(1 q (1

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

b) b) b) d( b ) b )( 1 b)
0

( 6.64 )

dq dT ( 1

The integrals ofEqs. ( 6.58 ), ( 6.60 ); b d( b ) q 01 0 (1 b b Z T d dq dT 0 ( 1

0

b)

d( b ) b )( 1

d To simplify ; (Z-1)

ln( 1

b ) qI ,

Z T

dq I dT

35

The generic equation of state presents two cases.

Case I:

1 ln 1

b b

( 6.65a )

When is eliminated in favor ofZ. bP RT Z I Case II: I P RT 1 whence Z ln Z b 1 b Z

36

b ( 6.65b )

G RT GR RT HR RT SR R

Z 1 ln(1 Z 1 ln( Z Z 1 ln( Z

b) Z qI (6.66a ) ) Z qI (6.66b)

d ln (Tr ) 1 qI (6.67) d ln Tr d ln (Tr ) ) qI (6.68) d ln Tr

37

Ex. 6.4
Find values for the HR and SR for n-butane gas at 500 K 50 bar as given by the Redlich/Kwong Eequation. Solution Tr = 500/425.1 = 1.176, From Table 3.1:

Pr = 50/37.96 = 1.317

Eq.(3.53); Eq.(3.54); q

Pr Tr Tr Tr

1.317 0.08664 1.176

0.09703 3.8689

0.42748 3/ 2 0.08664 1.176

38

39

Eq.(3.52) : Z

Z Z Z

Z 0.09703 1 0.09703 3.8689 0.09703 Z ( Z 0.09703) Solution of this Eq. yields Z 0.6850. Then: I ln Z Z 1 ln Tr , 2 0.13247 d ln (Tr ) / d ln Tr 1 . Then : 2

With ln (Tr )

HR Eq.(6.67) : 0.6850 1 ( 0.5 1)(3.8689)(0.13247) 1.0838 RT SR Eq.(6.68) : ln( 0.6850 0.09703) 0.5(3.8689)0.13247 0.78735 R Thus, HR SR 8.314 500 1.0838 4,505 Jmol 6.546 Jmol 1 K
1

8.314( 0.78735)

1
40

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

41

TWO-PHASE SYSTEMS
G G , dG dG V dP sat S dT V dP sat S dT

dP sat S Re arrangement , dT V Integration of Eq .( 6.8 ); H Thus , S H /T dP sat dT

S S V V T S ( The latent heat of phase transition ) H T V ( 6.71 ) : The Clapeyron equation

dP sat Hl Phase transition from liquid to vapor ; ( 6.72 ) l dT T V RT d ln P sat Hl l l But V Z ( 6.73 ) sat 2 l P dT RT Z The Clapeyron eq. for pure-species d ln P sat Hl or ( 6.74 ) l vaporization d (1 / T ) R Z
42

Temperature Dependence of the Vapor Pressure of Liquids

ln P sat

B T A B

The Antoine eq . : ln P sat

( 6.76 ) T C Antoine cons tan ts are given in Table B .2 , App .B A function of Tr ; ln Pr ( Tr )

sat

1.5

( 6.77 )

where

1 Tr

43

Corresponding-States Correlations for Vapor Pressure

Lee / Kesler correlation : ln Prsat (Tr ) ln Pr0 (Tr )
0 r

ln Pr1 (Tr ) (6.78) 0.169347Tr6 (6.79) 0.43577Tr6 (6.80)

6.09648 where ln P (Tr ) 5.92714 1.28862 ln Tr Tr ln Pr1 (Tr ) 15.2518 ln Prnsat where Trn : The reduced normal boiling point 15.6875 13.4721ln Tr Tr (6.81)

ln Pr0 (Trn )
1 r

ln P (Trn )

Prnsat : The reduced vapor pressure corresponding to 1 atm

44

Ex. 6.6
Determine the vapor pressure for liquid n-hexane at 0, 30, 60 and 90 C: (a) With constants from App. B.2. (b) From the Lee/Kesler correlation for Prsat Solution 2696.04 (a) ln P sat 13.8193
t 224.317
341.9 507.6

(b) Eq.(6.78); From Table B.1, From Eq.(6.81)

Trn

0.6736,

Prnsat

1.01325 0.03350 30.25

=0.298

t/ C Psat/kPa Psat/kPa t/ C Psat/kPa Psat/kPa (Antoine) (Lee/Kesler) (Antoine) (Lee/Kesler) 0 60 6.052 76.46 5.835 76.12 30 90 24.98 189.0 24.49 190.0

The average difference from the Antoine values is about 1.5%.

45

46

47

Two-Phase Liquid/Vapor System

nV V V

n lV l x lV l

nV xV xV

nl

nv

(moles)

x : mass fraction xl 1 xv

(1 x v )V l

The generic equation : M (1 x v ) M l x M (6.82a ) where M V , U , H , S , etc. An alternative form : M Ml x M l (6.82b)

48

THERMODYNAMIC DIAGRAMS

49

GENERALIZED PROPERTY CORRELATION FOR GASES

Pc Pr

dP

Pc dPr ,

TcTr

dT

Tc dTr

substitue int o Eqs.(6.46) and (6.48) : H RTc S R

R Pr R Pr

Tr2
0

Z Tr dPr Pr

Pr Pr

dPr Pr ( Z 1)

(6.83) dPr (6.84) Pr

Tr
0

Z Tr

Pr

50

Z Tr

Pr

Z0 Tr

Pr

Z1 Tr

Pr

HR Eq.(6.83) : RTc HR RTc SR Eq.(6.84) : R

Pr

Tr2
0

Z0 Tr

Pr

dPr Pr
1

Pr

Tr2
0

Z1 Tr

Pr

dPr Pr

HR RTc
Pr

HR RTc Z1 Tr
1

(6.85)

Tr
0

Z
Pr

dPr 1 Pr

Pr

Tr
0

Z1 Tr

Z
Pr

dPr Pr

SR R

SR R

SR R

(6.86)

Table E.5 - E.12

51

52

Analytical correlation of the residual properties at low pressure

The generalized sec ond virial coefficien t correlation forms B BP c RTc B
0

B,

dB dTr

dB 0 dTr

dB1 dTr SR R Pr dB dTr

HR Eqs.(6.55) and (6.56); RTc

dB Pr B Tr , dTr

HR RTc

Pr B

d B0 Tr dTr

d B1 Tr dTr

(6.87)

SR R

d B0 Pr dTr

d B1 dTr

(6.88)
53

B B

0.422 0.083 Tr1.6 0.172 0.139 Tr4.2 0.675 2.6 Tr 0.722 Tr5.2

(3.65) (3.66)

dB 0 dTr dB dTr
1

(6.89) (6.90)

54

HR and SR with ideal-gas heat capacities

For a change from state 1 to 2:
T2 T1

H2

ig 0 0

C dT

ig P

R 2

H1

ig 0 0

ig CP dT

H1R

The enthalpy change for the process, H = H2 H1

T2

H
T1 T2

ig CP dT

H 2R R ln

H1R P2 P 1 S 2R

(6.91) S1R (6.92)

Similarly,

S
T1

ig CP dT

Alternative form

H S

ig CP ig CP

(T2 T1 ) H 2R T2 T1 R ln P2 P 1

H1R S 2R

(6.93) S1R (6.94)

55

ln

56

A three-step calculational 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 (T2,P2).

2ig: Changes in the ideal-gas state from (T1,P1) to

T2

H ig S
ig

ig H2

H1ig
T1 T2

ig CP dT

(6.95) P2 R ln (6.96) P 1

ig 2

ig 1

dT C T T1
ig P

Step 2ig 2: Another hypothetical process that transform the ideal gas back into a real gas at T2 and P2.
H2
ig H2

H 2R

S2

ig S2

S 2R

57

Ex. 6.9
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) Solution

200 273.15 70 Tr 1.127 Pr 1.731 420.0 40.43 Eq.(3.57) and Table E.3 and E.4; Z V Z0 Z 1 0.485 0.191(0.142) 0.512 ZRT 0.512(83.14)(473.15) 287.8 cm 3 mol P 70

58

59

60

 Step (a): Vaporization of saturated liquid 1-butane at 0 C

ln P sat A B T (6.75)

The vapor pressure curve contains both

B the normal boiling po int; ln 1.0133 A 266.9 B the critical po int; ln 40.43 A 420.0 Whence, A 10.126 B 2,699.11

The latent heat of vaporization, where Trn=266.9/420=0.636:

lv Hn RTn lv Hn

1.092 (ln Pc 1.013 ) 0.930 Trn 9.979 8.314 266 .9

1.092 (ln 40 .43 1.013 ) 0.930 0.636 22 ,137 Jmol

1

9.979

61

The latent heat at 273.15 K From H

lv

Tr

273.15 / 420 0.650

H lv Hn
lv

1 Tr 1 Tr

0.38

...( 4.13 )
0.38 1

S lv

0.350 ( 22 ,137 ) 21,810 Jmol 0.368 H lv 21,810 79.84 Jmol 1 K 1 T 273.15

62

 Step (b): Transformation of saturated vapor into an ideal gas at (T1, P1).
B
H RTc
R

Pr B 0 Tr

dB dTr

B1 Tr

dB dTr

(6.87)

0.422 0.083 Tr1.6 0.172 0.139 Tr4.2 0.675 Tr2.6 0.722 Tr5.2

(3.65) (3.66)

S R

dB Pr dTr

dB dTr

(6.88)

dB 0 dTr dB1 dTr

(6.89) (6.90)

Tr = 0.650 and Pr = 1.2771/40.43 = 0.0316

So, H1R S1R ( 0.0985)(8.314)(420) ( 0.1063)(8.314) 344 Jmol
1 1

0.88 Jmol 1 K

63

 Step (c): Changes in the ideal gas state

Eq .( 6.95 ) : H Eq .( 6.96 ) : S
ig

H2 S2
ig

ig

H1 S1
ig

ig

T2

ig CP dT

ig CP

T1 ig T2 ig CP

( T2 T1 )
ig CP

T1

dT T

R ln

P2 P1

ln S

T2 T1

R ln

P2 P1

Tam = 373.15 K, Tlm = 364.04 K, A = 1.967, B = 31.630x10-3, C = -9.837x10-6 Hig = 20,564 J mol-1 Sig = 22.18 J mol-1 K-1

64

 Step (d): Transformation from the ideal gas to real gas state at T2 and P2. Tr = 1.127 Pr = 1.731 At the higher P; Eqs.(6.85) and (6.86) with interpolated values from Table E.7, E.8, E.11 and E.12.
H 2R RTC S 2R R H 2R S 2R H S U 2.294 (0.191)( 0.713) 1.566 (0.191)( 0.726) ( 2.430)(8.314)(420.0) ( 1.705)(8.314) H S H 2.430 1.705 8,485 Jmol
1 1

14.18 Jmol 1 K

21,810 ( 344) 20,564 8,485 34,233 Jmol 79.84 ( 0.88) 22.18 14.18 Jmol 1 K PV 34,233 (70)(287.8) 10 cm3barJ 1
1

32,218 Jmol

65

Extension to Gas Mixtures

yi
i

(6.97) (6.100)

Tpc
i

yiTci (6.98) PPr P Ppc

Ppc
i

yi Pci (6.99)

TPr

T Tpc

(6.101)

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).

66

Ex. 6.10
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.
Solution From Table B.1,

y1 Tpc Ppc

y2

(0.5)(0.224) (0.5)(0.152) 0.188 (0.5)(304.2) (0.5)(369.8) 337.0 K (0.5)(73.83) (0.5)(42.48) 58.15 bar Ppr 140 58.15 2.41
67

y1Tc1 y1 Pc1

y2Tc 2 y2 Pc 2

Whence, Tpr

450 1.335 337.0

68

From Table E.3 and E.4; Z Z0 Z1 0.697 (0.188)(0.205) 0.736

1

ZRT (0.736)(83.14)(450) V 196.7 cm 3 mol P 140 From Table E.7 and E.8; with Eq.(6.85) : H RTpc HR RTpc HR SR R SR
R 0

1.730

H RTpc

0.169 1.762
1

1.730 (0.188)( 0.169) (8.314)(337) 1.762

4,937 Jmol

From Table E.11 and E.12; with Eq.(6.86) : 0.967 (0.188)( 0.330) (8.314)( 1.029) 1.029
1
69

8.56 Jmol 1 K

70