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LOGO THERMODYNAMICS 1

Volumetric Properties of Pure Fluids

Department of Chemical Engineering, Semarang State University

Dhoni Hartanto S.T., M.T., M.Sc.
 Application of the Virial Equation
Originate value at Z = 1 for P = 0

The tangent to an isotherm at P = 0

is good approximation

 Z 
  T ; P  B
 P  Z
Tangent line eq. : Z  1  BP

PV BP
Z  1
RT RT

PV B
Z  1
RT V
 Application of the Virial Equation
The pressure above the range eq.
in previous slide but below critical
pressure
 three term virial equation give
excellent result

PV B C
Z  1  2
RT V V

Value of C and B depend on the gas

and on temperature

In figure 3.11, the trends are

similar
 Application of the Virial Equation
Ideal gas Equation of State

Virial EoS
B C D
Z  1   2  3  .........
V V V
If:
P0 or V 

Z 1 or PV  RT

Assumption : no molecule interaction

Good approximation for gas : in very low pressure or high
temperature (large volume)
 Application of the Virial Equation
 Internal energy for ideal gas

U  U T , P for real gas

P depend on molecule interaction

In ideal gas, no molecule interaction occured (V= infinite)

U  U T 

 Enthalpy for ideal gas

H  U  PV
H  H(T )
H  U  RT
 Application of the Virial Equation

 Heat capacity for ideal gas

 U 
CV   
 T V
CV  CV ( T )
U  U T 

 H 
CP   
 T P CP  CP ( T )
H  H T 

 The relation between CP and CV for ideal gas

dH  dU  d ( PV )
C p  CV  R
C p dT  CV dT  RdT
 Application of the Virial Equation
Extended virial equation (Benedict/Webb/Rubin Equation)

RT B0 RT  A0  C0 / T 2 bRT  a a c    
P      1   exp
V V2 V3 V6 V3T2  V2  V2

Where : A0 , B0 , C0 , a, b, c,  ,  are all constant for a given fluid

This complex equation are used in the petrolium and natural-gas industries
(light hydrocarbon and a few gas)
 Application of the Virial Equation
Example

The virial coefficients of isopropanol vapor at 200 oC :

B = -388 cm3 mol-1 ; C = -26000 cm6 mol-2
Calculate V and Z for isopropanol vapor at 200 oC and 10 bar by using :
a) The ideal-gas equation
b) Eq.3.37 (Smith Van Ness Handbook 6th ed)
c) Eq.3.39 (Smith Van Ness Handbook 6th ed)

Solution :
The absolute temperature is T = 473.15 K, gas constant (R) = 83.14 cm3 bar mol-1 K-1
d) Ideal gas, Z = 1
RT (83.14)( 473.15)
V   3934 cm3 mol-1
P 10
 Application of the Virial Equation
RT
b) Solving eq. 3.37 for V : V  B  3934  (388)  3546 cm3 mol-1
P
PV V 3546
Z    0.9014
RT RT / P 3934

c) Solving eq. 3.39, rearrange equation to facilitate iteration, yield :

RT  B C 
Vi 1  1   2 
P  Vi Vi 
 388 26000 
V  3934 1   
 V V 
2

Using goal seek in M. Excel to obtain V , then V = 3488 cm3 mol-1
PV V 3488
Z    0.8866
RT RT / P 3934

The ideal gas value is 13% too high and no (b) is 1.7% too high
compare with this result
 Cubic Equation of State

- More theoritically derivative

- Can be applied for gas and liquid property (VLE Application)

 P   2P 
   0;  2   0
 V Tc  V Tc
1. Van der Waals EoS (1873)

P
C
RT a
P  2
V b V
Cair+Uap Tc
volume T<Tc T>Tc

Intermolecular attraction VL VV
V
If b=0 dan a/V2=o, then 27 R 2Tc2 RT
this eq. become ideal gas eq. a ;b  c
64 Pc 8 Pc
Cubic Equation of State

The Van der Waals EOS

Generic Cubic EOS

Isotherm as given by a cubic EOS

 Other Cubic EoS

1873-1923, van der Waals

RT a
(vdW) P  2
V b V
1949, Redlich-Kwong (RK) RT a
P  12
V  b T V  b V
1972, Soave-Redlich-
RT a T 
Kwong (SRK) P 
V  b V V  b 
1976, Peng-Robinson
RT a T 
(PR) P  2
V  b V  2bV  b 2
 Generalized correlation

2-parameter corresponding state principle (CSP)

Z  Z  Tr , Pr  Valid untuk simple fluid (Ar, Kr dan Xe)

dimana
T P
Tr  ; Pr 
Tc Pc
Two-parameter theorem of corresponding states:

All fluids, when compared at the same reduce temperature and reduce
pressure, have approximately the same compressibility factor, and all
deviate from ideal-gas behavior to about the same degree
• For simple fluids (Ar, Kr and Xe), it is very nearly exact.
• Systimatic deviations are abserved for complex fluids

Introduction of “w” by K. S. Pitzer and coworkers

 Theorem of Corresponding State ; Acentric Factor

All fluids, when compared at the

same reduced temperature and
reduced pressure, have
approximately the same
compressibility factor, and all
deviate from ideal-gas behavior to
about the same degree

Approximate temperature dependence of the reduced vapor pressure

Generalized correlation

3-parameter corresponding state principle (CSP)

Z  Z  Tr , Pr , 
Pitzer and Curl correlation (1955, 1957)

Z  Z 0  Z 1

Dimana Z0 dan Z1 fungsi (Tr=T/Tc) dan (Pr=P/Pc)

The values can be determined from The Lee/Kesler
Generalized-correlation Tables (Lee and Kesler, AIChE
J., 21, 510-527 (1975) provided in App. E, p. 645 (pdf.
Page 667)
 Generalized Correlation for Gases
The Lee/Kesler correlation provides suitable results for gases
which are nonpolar and slightly polar

The nature of The Lee/Kesler correlation for Z0 = F0 (Tr,Pr)

 Generalized Correlation for Gases

For quantum gases ex. Hidrogen, helium and neon, temperature-dependent

effective critical parameters proposed by Prausnitz:

T is absolute temperature in K
 Generalized for second Virial Coefficient

Pitzer Correlation for the Second Virial Coefficient :

The most popular and reliable

correlation for the second Virial
correlation is provided by
Tsonopoulos, et al., 1975, 1978,
1979, 1989, 1990, 1997.
Where: (see p. 4.13-4.17, Poling et al.2001
0.422 “The properties of gases and liquids
B 0  0.083 
Tr0.422 5th ed. MCGRAW-HILL Int. Ed.)
0.172
B1  0.139 
Tr4.2
 Comparisons between Lee/Kesler and generalized Virial eq.

Lee/Kesler corr (points)

(straight lines)

<2% differ

Comparison of correlation for Z0. The virial-coefficient is represented by the straight lines;
the Lee/Kesler correlation, by the points. In the region above the dashed line the two
correlation differ by less than 2%
Ideal-gas Approximation

Region where Z0 lies between 0.98

and 1.02, and the ideal-gas equation
is a reasonable approximation

Ideal gas
approximation is
reasonable
Z===1
 Generalized Correlation for Liquids

 Rackett equation (Racket, J. Chem. Eng. Data, 15 (1970) 514-517:

estimation of molar volume of saturated liquids

Generally, the accuration was 1-2%

 Lyderson, Greenkorn and Hougen:
estimation of liquid molar volume
 Generalized Correlation for Liquids

Figure 3.17 Generalized density correlation for liquids

 Example 3.12

Example 3.12

For amonia at 310 K, estimate the density of

a)The saturated liquid density
b)The liquid at 100 bar
Solution:
a. Using Rackett eq.
Saturated Liquid Tc= 405.7 K, Vc= 72.47Zc= 0.242 from App. B

(1Tr ) 0.2 87
V sat
 Vc Z c  28.33 cm 3mol 1
This compared to the exp. Value 29.14 cm3/mol and differ 2,7%

b. Compreesed liquid density:

Reduced Condition Tr= 0.764 K, Pr= 0.887

From Fig. 3.17  r  2.38

  r  2.38 This compared to the exp. Value 28.6 cm3/mol and differ 6,5%
72.47
V  VCr   30.45 cm 3 mol 1
2.38

Other method:
For saturated liquid
at Tr = 0,764
2.3 then density is 2,34
8 
V2  V1 r1
r 2
 2.34 
V2   29.14  
 2 .38 
V2  28 .65 cm 3 mol 1

The result is agreed with

the exp. data.