2105370 Chemical Engineering Thermodynamics I

2547

..

Equation of State
()
, ()
Equation of State

f ( P ,V , T ) = 0

Gibbs Phase Rule

,
1 100C 1 1 cm3 (
1 1673 cm3)
Degree of Freedom 2 (, )
2 Equation of
State
P = f (T ,V )

V = f (T , P )

T = f (V , P )

Equation of State Ideal gas model ( Ideal gas law)

P=

RT
V

Ideal gas law Boyles law Charless law

Ideal gas
Ideal gas law
(1-2 ) ( 0C)
Ideal gas law Equation of State
,
Equation of State

Equation of State
van der Waals (vdW)

1873

P=

RT
a
2
(V b) V

parameter a b
-
-
P
=0

V T =Tc , P = Pc

2P

=0
2
V T =Tc , P = Pc

b=

a=

Virial equation
(proposed by Thiesen)

1885

Z=

27 R 2Tc2
64 Pc

PV
B C
D
= 1+ + 2 + 3 +K
RT
V V
V

RTc
8 Pc

Ideal gas law parameter

a, b Interaction (
)
:

-
- parameter a, b
: -
vdW Zc
0.375 Zc
0.24
0.29
Equation of State Statistical
mechanics infinite series
:

- ()
- Interaction

: - parameter B, C

Equation of State
Beattie-Bridgeman

1928

Benedict-Webb-Rubin
(BWR)

1940

Redlich-Kwong (RK)

1949

1 b
Z = 1 + B0 2
V V

P=

P=

C A0 1
a

2
1
3
VT RT V V

2
RT B0 RT A0 C 0 T
bRT a a
+
+
+ 6
2
V
V
V3
V

c

+ 3 2 1 + 2 exp 2
V T V
V

RT
a

(V b) V (V + b )T 1 2

vdW a b

- Virial equation
- P-V-T
BWR
Beattie-Bridgeman
:

- Equation of State

- K

: - parameter 8 ,
- , ,
Critical point,

van der Waals

- , vdW
- Zc vdW
-

Equation of State
Redlich-Kwong (RK)
()

Wilson

a = 0.42748

1964

P=

2.5
c

R T
Pc

b = 0.08664

RT
a

(V b) V (V + b )

RTc
Pc

: -

-
- Redlich-Kwong Reduced
temperature acentric factor*

= Tr 1 + (1.57 + 1.62 ) 1
Tr

Soave-Redlich-Kwong
(SRK)

1972

P=

RT
a

(V b) V (V + b )

Redlich-Kwong
:

= [1 + (0.48 + 1.574 0.176 2 )(1 Tr0.5 )]

* acentric factor, ()
= log 10

P(Tr = 0.7 )
1.0
Pc

-
( 1 bar)
-
nonpolar

Equation of State
Soave-Redlich-Kwong
()

Peng-Robinson (PR)

1976

P=

: -

- 10
torr
- Critical point

- long
chain molecule polar
-

Redlich-Kwong

RT
a

(V b) V (V + b ) + b(V b)

= [1 + (0.37464 + 1.54226 0.26992 2 )(1 Tr0.5 )]

-
SRK
-
6 10 (
)
: -

- 10
torr

Equation of State
Peng-Robinson (PR)
()

Patel-Teja (PT)

1982

P=

RT
a
2
(V b) V + (b + c )V bc

: - Critical point

- long
chain molecule polar
-

parameter 3 (a, b, c)
:

-
SRK PR
- polar (
parameter )
: - polar

- parameter c

vdW
- Mixing rule


- Introduction to Chemical Engineering Thermodynamics, 6th Edition, J. M. Smith, H. C. Van Ness and
M. M. Abbott, McGraw-Hill, 2001
- Models for Thermodynamic and Phase Equilibria Calculations, edited by S. I. Sandler, Dekker, 1994
- Equilibrium-Stage Separation Operations in Chemical Engineering, E. J. Henley and J. D. Seader,
Wiley, 1981
- J. J. Martin, Cubic Equations of State Which?, Industrial & Engineering Chemistry Fundamentals,
18[2], 81-97, 1979