NON-IDEAL FLUID BEHAVIOR

 Homogeneous fluids are normally divided into

two classes, liquids and gases (vapors).
Gas: A phase that can be condensed by a reduction
of temperature at constant pressure.
Liquid: A phase that can be vaporized by a
reduction of pressure at constant temperature.
The distinction cannot always be made
unambiguously, and the two phases become
indistinguishable at the critical point.

THE CRITICAL POINT

Critical point: The maximum pressure and
temperature where a pure material can exist in
vapor-liquid equilibrium. Beyond Tc and Pc, the
designation of gas vs. liquid is arbitrary.
At the critical point, the meniscus between phases
slowly fades and dissappears.
If one moves around the critical point, it is possible
to get from the liquid to the vapor field without
crossing a phase boundary.
3

Supercritical

C - critical point

P-T phase diagram for a pure material.

P-V phase diagram for a pure

material. C - critical point.

nRT
P
V
At high T we expect the
isotherms to conform to
the ideal gas law, i.e., P
is inversely proportional
to V.

P-V phase diagram for pure

H2O.

THE P-V DIAGRAM

We can use the lever rule on a P-V diagram to
determine the proportion of vapor vs. liquid at any
given pressure.
The bending of the isotherms in the vapor field
from the ideal hyperbolic shape as the critical
point is approached indicates non-ideality.
The P-V diagram illustrates the difficulty in
developing an equation of state for all regions for
a pure substance. However, this can be done for
the vapor phase.
7

Schematic isotherms in the two-phase field for a pure fluid.

For fluid of density

A, the proportion
of vapor is Y/
(X+Y) and the
proportion of liquid
is X/(X+Y).
For fluid of density
B, the proportion of
vapor is P/(P+Q)
and the proportion
of liquid is Q/
(P+Q).

X
8

MOST GENERAL EQUATION OF

STATE
V
V
dT

dP
T P
P T

dV

dV
dT dP
V

Two special cases:

a) Incompressible fluid

==0
dV/V = 0 (no equation of state exists)
V = constant
b) and are temperature- and pressure-independent
9

VIRIAL EQUATION OF STATE

The most generally applicable EOS
PV = a + bP + cP2 +
a, b, and c are constants for a given temperature and
substance.
In principle, an infinite series is required, but in
practice, a finite number of terms suffice.
At low P, PV a + bP. The number of terms
necessary to accurately describe the PVT
properties of gases increases with increasing
pressure.
10

The limit of PV as P 0 is independent of the gas.

T = 273.16 K = triple point of water

lim (PV)T, P 0 = (PV)T* = 22.414 (cm3 atm g-mol-1) = a

So a is the same for all gases. It is in fact, RT!

11

I. THE COMPRESSIBILITY FACTOR

12

THE COMPRESSIBILITY FACTOR

Z PV/RT = 1 + BP + CP2 + DP3 +
or
Z = 1 + B/V + C/V2 + D/V3 +
The virial equation of state is the only one which has
a firm basis in theory. It follows from statistical
mechanics. It can be used to represent both liquids
and gases.
The term B/V arises due to pairwise interactions of
molecules.
The term C/V2 arises due to interactions among three
molecules, etc.
13

The constants for the two versions of the virial

equation are related by the equations:
B
B'
RT

C B2
C'
RT 2

D 3BC 2 B 3
D'
RT 3

Disadvantages of the virial equation of state:

1) Cumbersome, many variables
2) Not much predictive value
3) Difficult to use for mixtures
4) Only really useful when convergence is rapid, i.e.,
at low to moderate pressures.
14

SOME APPROXIMATIONS
Low pressure (0 - 15 bars at T < Tc)
PV
BP
Z
1
RT
RT

Becomes valid over greater pressure ranges as

temperature increases. Easily solved for volume.
Moderate pressure (0 - 50 bars)
PV
B C
Z
1 2
RT
V V

Only B and C are generally well known. At higher

pressures, other EOSs are required.
15

Compressibility factor
diagram for methane.
Note two things:
1) All isotherms
originate at Z = 1where
P 0.
2) The isotherms are
nearly straight lines at
low pressure, in
accordance with the
truncated virial
equation:

BP
Z 1
RT
16

The compressibility factor

as a function of pressure
for various gases. Z
measures the deviation
from the ideal gas law.
17

II. EQUATIONS OF STATE

18

THE OBJECTIVE IN THE SEARCH

FOR AN EOS
The objective is to find a single equation of
state:
1) whose form is appropriate for all gases
2) that has relatively few parameters
3) that can be readily extrapolated
4) that can be adapted for mixtures
This objective has only been partially
fulfilled.
19

VAN DER WAALS EQUATION (1873)

a
P 2 V b RT
V

The a term accounts for forces of attraction between

molecules (long-range forces).
The b term accounts for the non-zero volume of
molecules (short-range repulsion).
At low pressures real gases are easier to compress
than ideal gases; at higher pressures they are more
difficult to compress (see Z plot).
An alternate form is:
RT
a
P

V b

V2
20

The van der Waals

isotherms (labelled with
values of T/Tc.
The van der Waals
equation predicts the
shape of the isotherms
fairly well in the onephase region, but shows
unrealistic oscillations in
the two-phase region. The
theory fails because it
only considers two-body
interactions.

P/Pc

V/Vc

21

THE VAN DER WAALS

PARAMETERS
We can determine how to calculate the a and b parameters
by setting the 1st and 2nd derivatives of the van der
Waals equation to zero at the critical point (an inflection
point), i.e.,
2P
P

0
2
V T
V T
Solving these equations we get: Vc 3b

8 a
Tc
27 bR

a
Pc
27b2

PcVc 3
Zc
0.375
RTc 8
22

CRITICAL CONSTANTS OF GASES - I

Gas Pc (atm) Vc (cm3mol) Tc (K)

Zc

He

2.26

57.8

5.21

0.306

Ne

26.9

41.7

44.4

0.308

Ar

48.0

73.3

150.7

0.285

Xe

58.0

119

289.8

0.290

H2

12.8

65.0

33.2

0.305

O2

50.1

78.0

154.8

0.308

N2

33.5

90.1

126.3

0.291

F2

55

----

144

---

Cl2

76.1

124

417.2

0.276

Br2

102

135

584

0.287

23

CRITICAL CONSTANTS OF GASES - II

Gas Pc (atm) Vc (cm3mol) Tc (K)

Zc

CO2

72.7

94.0

304.2

0.275

H2O

218

55.3

647.4

0.227

NH3

111

72.5

405.5

0.242

CH4

45.8

99

191.1

0.289

C2H4

50.5

124

283.1

0.270

C2H6

48.2

148

305.4

0.285

C6H6

48.6

260

562.7

0.274

The van der Waals equation does better than the ideal gas law
but is not great. No two-parameter EOS can predicts all these
gases.
24

We can rearrange the previous equations to get the

van der Waal parameters in terms of the critical
parameters:

a 3PcVc2
where

Vc

3RTc
Vc
8Pc

Note that, the actual measured value of Vc is not used

to calculate a and b!

25

VAN DER WAALS CONSTANTS FOR GASES

Gas

Gas

He

0.03412 2.370

Cl2

6.493 5.622

Ne

0.2107

1.709

CO2

3.592 4.267

Ar

1.345

3.219 H2O 5.464 3.049

Kr

2.318

3.978 NH3 4.170 3.707

Xe

4.194

5.105

H2

0.2444

2.661 C2H4 4.471 5.714

O2

1.360

3.183 C2H6 5.489 6.380

N2

1.390

3.913 C6H6 18.00 1.154

CH4

2.253 4.278

a - dm6 atm mol-2; b - 10-2 dm3 mol-1

26

SOME OTHER EOSs

Bertholet (1899)

a
V b RT
P
2
TV

The higher the temperature, the less likely particles

will come close enough to attract one another
significantly. a and b are different from VdW.
Dieterici (1899)
Keyes (1917)

RT
P
e
V b

RT
V

RT
A
P

2
V
(V e ) V l

, , A and l are correction factors.

27

BEATTIE-BRIDGEMAN (1927)
RT (1 )
A
V B 2
P
2
V
V
A A0 1 a V

B B0 1 b V

VT 3

a, b, c, A0, B0 are constants

We usually dont know V, but we know P, so an
iterative approach is required: calculate A, B and
with an assumed V value and compute P. If Pcalc
Pexp, then adjust V accordingly and recalculate P.
28

Rearrangement of the Beattie-Bridgeman equation gives:

RT

P
2 3 4
V
V
V
V
Where

Rc
RTB0 A0 2
T
RB0bc
RB0c

RTB0b aA0 2
2
T
T to be simply a truncated
This shows the B-B equation
form of the virial equation.

29

BEATTIE (1930)
A
V B 1
RT
A A0 1 a

B B0 1 b
RT

T 3

perfect gas volume

a, b, and c are the same as for the B-B EOS

One can use the Beattie equation to obtain a first
guess for the Beattie-Bridgeman equation, which is
more accurate because it allows for the variation of
A, B and with volume.
30

SOME MORE EOSs

Jaff (1947) - a modification of the Dieterici EOS

RT
R TTc
RT
V

P

1 e

V b V b

4 R 2Tc2
RTc

b
2
Pc e
Pc e 2
1

Wohl (1949)

RT

c
P

3
V b V V b V

6 PcVc 2

b Vc 4

c 4 PcVc3
31

McLeod (1949)
where

(V b' ) RT

a
P 2
V

b ' A B c 2

and a, A, B, and c are constants.

Benedict-Webb-Rubin (1940) - specifically devised
for hydrocarbons. Useful for both liquids and
gases. Define
d 1
V

P RTd B0 RT A0 C0 T 2 d 2 bRT a d 3
3
2

cd
1

d
6
d 2
ad
e

2
T

32

Martin-Hou (1955)
Introduces the reduced temperature: Tr = T/Tc

RT
A2 B2T C2 (eTr
P

(V b)
(V b)2
A4
B5T

4
(V b)
(V b)5

238

A3 B3T C3 (eTr

(V b)3

239

Like many others, this EOS is also a version of the

virial EOS.
33

34

REDLICH-KWONG (1949)
This has been one of the most useful to geology
RT
a
P
12
(V b) T V (V b)
where
0.42748R 2Tc2.5
0.08664 RTc
1
a
b
Z c 0.3333
Pc
Pc
3
The R-K EOS is quite accurate for many purposes,
particularly if the a and b parameters are adjusted
to fit experimental data. However, there have been
a number of attempts at improvement.
35

MODIFICATIONS OF THE R-K EOS

RT
a
de Santis et al. (1974) P
12
(V b) T V (V b)

but b is a constant and a(T) = a0 + a1T.

Peng and Robinson (1976)
RT
a (T )
P
2
(V b) (V 2bV b2 )
where

(T ) 1 m 1 Tr

m 0.37464 1.54226 0.26992 2

and
is a parameter for the fluid called the acentric factor.
36

Carnahan and Starling (1969) - hard-sphere model

RT
P
V

1 y y2 y3

3
(1 y )

b
y
4V

Kerrick and Jacobs (1981) - Hard-Sphere Modified

Redlich-Kwong (HSMRK)

RT 1 y y 2 y 3
a ( P, T )

1
P
3
2
V
(1 y )
T
V (V b)

a(P,T) = an empirically-derived polynomial.

a ( P, T ) c(T ) d (T )
z (T ) z1 z2T z3T

e(T )

V2

where z = c, d, or e

37

LEE AND KESLER (1975)

b01 b02Tr1 b03Tr2 b04Tr3 c01 c02Tr1 c03Tr3

Z 1

2
V
V
r
r

1
02 r
5

d 01 d T

Vr

c04
0
3 2 0 2 e
Tr Vr
Vr

0
Vr2

b11 b12Tr1 b13Tr2 b14Tr3 c11 c12Tr1 c13Tr3

1

2
V
V
r
r

1
12 r
5

d11 d T

Vr

c14
1
3 2 1 2 e
Tr Vr
Vr

1
Vr2

38

DUAN, MOLLER AND WEARE (1992)

B C
D
E
F

Z 1 2 4 5 2 2 e
Vr Vr Vr Vr Vr
Vr

Vr2

B a1 a2Tr2 a3Tr3

C a4 a5Tr2 a6Tr3

D a7 a8Tr2 a9Tr3

E a10 a11Tr2 a12Tr3

F T

3
r

VPc
Vr
RTc

P
Pr
Pc

T
Tr
Tc

This is just a modified form the the Lee and Kesler EOS.
39

CALCULATING FUGACITY
COEFFICIENTS BY INTEGRATING AN
EOS
Using the van der Waals equation:
P

RT
a
2
V b V
P

1
V
ln
P
RT P
0

V
b
2a
PV
ln ln

ln

RT
V b V b V RT
40

Using the original Redlich-Kwong equation:

RT
a
P
12
(V b) T V (V b)
P

1
V
ln
P
RT P
0

V
b
2a
V b
ln ln

ln

3
2
V b V b RT b V

a V b
b
PV
ln
ln

3
2
RT
RT b V V b
41

Using the HSMRK EOS of Kerrick and Jacobs (1981)

8 y 9 y 3y
PV
c
ln
ln

3
3
(1 y )
RT RT 2 (V b)
d
e

3
3
2
RT V (V b) RT 2V 2 (V b)
2

c
V
d

ln

3
3
2
2
V

b
RT
b
RT
Vb

d
V b
e

ln

3
3
2
2 2
2
V
RT
b
RT
2
b

e
V b
e

ln

3
3
3
2
2 2
V
RT
b
RT
bV

42

Activities in CO2-H2O mixtures predicted by a MRK EOS after

Kerrick & Jacobs (1981).

43

Predicted H2O and CO2 activities in H2O-CO2-CH4 mixtures at 400C

and 25 kbar. Calculated for XCH4 = 0.0, 0.05 and 0.20. Dotted curves
imply a miscibility gap of H2O-rich liquid and CO2-rich vapor.
After Kerrick
& Jacobs
(1981).

44

CO2-H2O solvus at 1 kbar. The solid line is a fit of a MRK EOS to

experimental data (solid dots). After Bowers & Helgeson (1983).
45

Effect of 12 wt. % NaCl on

the CO2-H2O solvus at 1
kbar. After Bowers &
Helgeson (1983).

46

III. CORRESPONDING
STATES

47

PRINCIPLE OF CORRESPONDING
STATES
Reduced variables of a gas are defined as:
Pr = P/Pc
Tr = T/Tc
Vr = V/Vc
Principle of corresponding states - real gases in the
same state of reduced volume and temperature
exert approximately the same pressure. Another
way to say this is, real gases in the same reduced
state of temperature and pressure have the same
reduced compressibility factor.
This fact can be used to calculate PVT properties of
gases for which no EOS is available.
48

The reduced compressibility factor vs. the reduced pressure

49

Reduced pressure

Generalized compressibility
chart. Medium- and highpressure range.

PV
Z
RT

3.0
2.8
2.6
2.4

2.2

2.0
1.8
1.6
1.4
1.2
1.0
Reduced pressure

50

EXAMPLE: Calculate the specific volume of NH3 at

500C and 2 kbar using the reduced Z chart and
compare to the ideal gas law prediction.
Ideal gas law

RT (0.080256 atm L mol1 )(773 K )

V

0.0310 L mol1
P
(2000 atm)

Corresponding states: Tr = (773 K)/(405.5 K) = 1.91;

Pr = (2000 atm)/(111 atm) = 18.02.
(2000 atm)V
Z 1.62
(0.080256 atm L mol1 )(773 K )

V 0.050 L mol1
51

52

53

54

55

Measured compressibility factors for H2O vs. those obtained from

corresponding state theory

56

Measured compressibility factors for CO2 vs. those obtained from

corresponding state theory

57

Generalized density correlation for liquids. r = /c 58

PITZERS ACENTRIC FACTOR

The acentric factor of a material is defined with reference
to its vapor pressure.
The vapor pressure of a subtance may be expressed as:
log Prsat a b

Tr

but the L-V curve terminates at the critical point where Tr

= Pr. So a = b and
log Prsat a 1 1
Tr

If the principle of corresponding states were exact, all

materials would have the same reduced-vapor pressure
curve, and the slope a would be the same for all
materials. However, the value of a varies.
59

The linear relation is only approximate; a is not defined

with enough precision to be used as a third parameter
in generalized correlations.
Pitzer noted that Ar, Kr and Xe all lie on the same
reduced-vapor pressure curve and this passes through
log Prsat = -1 at Tr = 0.7. We can then characterize the
location of curves for other gases in terms of their
position relative to that for Ar, Kr and Xe.
sat

log
P
The acentric factor is:
r Tr 0.7 1.000
can be determined from Tc, Pc and a single vapor
pressure measurement at Tr = 0.7.
60

Slope -3.2
(n-octane)

Approximate temperature-dependence of reduced vapor pressure

61

ACENTRIC FACTORS FOR GASES

Gas

Gas

Gas

Ne

Cl2

0.073

methane

0.011

Ar

-0.004

Br2

0.132

ethylene

0.087

Kr

-0.002 CO2 0.223

ethane

0.100

Xe

0.002

CO

0.049

benzene

0.212

H2

-0.22

NH3 0.250

toluene

0.257

O2

0.021

HCl

N2

0.037

H2S 0.100

F2

0.048

SO2 0.251 m-xylene 0.331

0.12

n-heptane 0.350
propane

0.153

62

PRINCIPLE OF CORRESPONDING
STATES - REVISITED
Restatement of principle of corresponding states:
All fluids having the same value of have the same
value of Z when compared at the same Tr and Pr.
The simplest correlation is for the second virial
BPc Pr
coefficients:
BP
Z 1

RT

RTc Tr

The quantity in brackets is the reduced 2nd virial

coefficient.
BPc

B 0 B1
RTc

63

0.422
B 0.083 1.6
Tr
0

0.172
B 0.139 4.2
Tr
1

The range where this correlation can be used safely is

shown on the chart on the next slide.
For the range where the generalized 2nd virial
coefficient cannot be used, the generalized Z charts
may be used:
Z = Z0 + Z1
These correlations provide reliable results for non-polar
or only slightly polar gases. The accuracy is ~3%. For
highly polar gases, the accuracy is ~5-10%. For gases
that associate, even larger errors are possible.
The generalized correlations are not intended to be
substitutes for reliable experimental data!
64

Generalized correlation
for Z0. Based on data
for Ar, Kr and Xe from
Pitzers correlation.

65

Generalized correlation
for Z1 based on Pitzers
correlation.

66

EXAMPLE -1
What is the volume of SO2 at P = 500 atm and T =
500C?
According to the ideal gas law:
RT (0.080256 atm L mol1 )(773 K )
V

0.124 L mol1
P
(500 atm)

Using the acentric factor: =0.273; Tr = 773/430.8 =

1.79; Pr = 500/77.8 = 6.43.
From the charts: Z0 = 0.97; Z1 = 0.31.
Z = 0.97 + 0.273(0.31) = 1.055
(500 atm)V
Z 1.055
(0.080256 atm L mol1 )(773 K )

V 0.131 L mol-1
67

saturation

Line defining the region where generalized second virial

coefficients may be used. The line is based on Vr 2.
68

EXAMPLE - 2
What is the volume of SO2 at P = 150 atm and T =
500C?
According to the ideal gas law:
RT (0.080256 atm L mol1 )(773 K )
V

0.414 L mol1
P
(150 atm)

Using the acentric factor: =0.273; Tr = 773/430.8 =

1.79; Pr = 150/77.8 = 1.93.
0.422
B 0.083
0.083
1.6
1.79
0

0.172
B 0.139
0.124
4. 2
1.79
1

69

 BPc

B 0 B1 0.083 0.273(0.124) 0.049

RTc
BPc Pr
1.93

Z 1
1 ( 0.049)
0.947
1.79
RTc Tr
(150 atm)V
Z 0.947
(0.080256 atm L mol1 )(773 K )

V 0.392 L mol-1
Vc = 0.122 L mol-1
Vr = 0.392/0.122 = 3.25
70

CORRESPONDENCE PRINCIPLE
FOR FUGACITY
Correspondence principles and generalized
charts exist for fugacity and other
thermodynamic properties.
For fugacity, both two- and three-parameter
generalized charts have been developed.
Again, these are to be used only in the
absence of reliable experimental data.
71

ln

Pr

Z 1

dPr
Pr

I. We can use this equation together with the generalized

Z charts.
1) Look up Pc and Tc of gas
2) Calculate Pr and Tr values for desired Ts and Ps
3) Make a Table of Z from the generalized charts at various
values of Tr and Pr. Of course, we must have Pr values from 0
to the pressure of interest at each temperature.
4) Graph (Z-1)/Pr vs. Pr for each Tr.
5) Determine the area under the the graph from P r = 0 to Pr = Pr
to get ln .

II. Used generalized fugacity charts.

72

73

74

USE OF TWO-PARAMETER
GENERALIZED FUGACITY CHARTS
EXAMPLE 1: Calculate the fugacity of CO2 at 600C
(873 K) and 1200 atm.
Tc = 304.2 K; Pc = 72.8 atm
Tr = 2.87; Pr = 16.48
From the chart 1.12
so
f = (1.12)(1200) = 1344 bars
75

EXAMPLE 2: What is the fugacity of liquid Cl2 at 25C

and 100 atm? The vapor pressure of Cl2 at 25C is 7.63
atm.
For the vapor coexisting with liquid:
Tc = 417 K; Pc = 76 atm
Tr = 0.71; Pr = 0.10
from the chart 0.9
f = (0.9)(7.63) = 6.87 atm
Now we must correct this to 100 atm.

V
ln f 2 ln f1
( P2 P1 )
RT

V = 51 cm3 mol-1; assume to be constant.

f2 = 8.36 atm

76

THREE-PARAMETER CORRELATIONS
FOR FUGACITY ETC.
Fugacity:
Enthalpy:
Entropy:
Density:

log

f
f
log
P
P

( 0)

H H H H

RTc
RTc
0

S S S S

R
R

( 0)

log
P

( 0)

(1)

H H

RTc
0

S S

(1)

(1)

ln P

1 0.85(1 Tr ) (1 Tr ) 3 (1.89 0.91 )

c

Tables for these correlations can be found in Pitzer

(1995) Thermodynamics. McGraw-Hill.

77

IV. GASEOUS MIXTURES

78

IDEAL GAS MIXTURES

Mixture as a whole obeys: PV RT
Two such mixtures are in equilibrium with each
other through a semi-permeable membrane when
the partial of each component is the same on each
side of the membrane.
There is no heat of mixing.
The gas mixture must therefore consist of freely
moving particles with negligible volumes and
having negligible forces of interaction.
79

DALTONS LAW VS. AMAGATS

LAW
Daltons Law: Pi = XiPT

PT Pi

At constant VT and T

VT Vi

At constant PT and T

Amagats Law: Vi = XiVT

These two laws are mutually exclusive at a given pressure and

temperature.

80

THERMODYNAMICS OF IDEAL
MIXING - REVISITED
We have previously shown that:

Gideal mix RT X i ln X i
i

using Daltons Law we can derive:

Gideal mix

Pi
RT X i ln
PT
i

and for entropy we have:

Sideal mix

Pi
R X i ln
PT
i

81

NON-IDEAL MIXTURES OF NONIDEAL GASES

For a perfect gas mixture:
i io RT ln Pi io RT ln PT RT ln X i
For an ideal mixture of real gases:
i io RT ln f i io RT ln f i o RT ln X i
f i X i f i o X ii PT Lewis Fugacity Rule

For a real mixture of real gases:

i io RT ln f i
f i X i i f i o X i ii PT
Correction for
non-ideal mixing

Correction for
non-ideal gas

82

DALTONS LAW AND

GENERALIZED CHARTS
Calculate reduced pressure according to:
Pi
Pr ,i
Pc ,i

PAVT n A Z A RT

PBVT nB Z B RT

PCVT nC Z C RT

PA PB PC VT n AZ A nB Z B nC ZC RT
nT X A Z A X B Z B X C Z C RT
nT Z mix RT
83

AMAGATS LAW AND

GENERALIZED CHARTS
Calculate reduced pressure according to:
PT
Pr ,i
Pc ,i

PTVA n A Z A RT

PTVB nB Z B RT

PTVC nC Z C RT

PT VA VB VC n A Z A nB Z B nC Z C RT

nT X A Z A X B Z B X C Z C RT
nT Z mix RT
84

PSEUDOCRITICAL CONSTANTS

B
XA

X A2

L- V c u r v e f o r A
L- V c u r v e f o r B

T
85

KAYS METHOD
Assumes a linear critical curve between the critical
points for A and B.

Pc ' X i Pc ,i
i

Tc ' X iTc ,i
i

When answers are near the critical point for the

mixture, we cannot be certain that we are not
dealing with a liquid-vapor mixture.
86

JAFFS METHOD
For binary mixtures only.

Tc '

P'
c

Tc '

Pc '

X A A Pc , A X B B Pc ,B
mix

X A X B 14 A B X A X B
2
A

2
B

mix

Tc ,i
i
Pc ,i
87

MIXING CONSTANTS IN
EQUATIONS OF STATE
Van der Waals and simple Redlich-Kwong EOS:
n

bmix X j b j
j 1

amix X j X k a jk
j 1 k 1

a jk a j ak

Use if no mixture data

are available.
88

Beattie-Bridgeman EOS:

A0,mix

amix X j a j
j 1

B0,mix X j B0, j
j 1

X
j 1

A0, j

bmix X j b j
j 1

cmix X j c j
j 1

89

Benedict-Webb-Rubin EOS:

A0,mix

j 1

A0, j

j 1

X
j 1

mix

X
j 1

bj

j 1

j 1

aj

cmix

amix

bmix

C0, j

B0,mix X j B0, j
j 1

C0,mix

X
j 1

mix

cj

90

Virial Equation of State:

Z = 1 + B/V + C/V2 + D/V3 +
n

Bmix X i X j Bij
i 1 j 1

Cmix X i X j X k Cijk
i 1 j 1 k 1

91

PREDICTION OF CRITICAL
CONSTANTS
Critical Temperature:
I. All compounds with Tboil (1 atm) < 235 K and all elements:
Tc = 1.70Tb - 2.00.
II. All compounds with Tboil (1 atm) > 235 K.
A. Containing halogens or sulfur
Tc = 1.41Tb + 66 - 11F
F = No. of fluorine atoms
B. Aromatics and napthenes
Tc = 1.41Tb + 66 - r(0.388Tb - 93)
r = ratio of non-cyclic carbon atoms to total carbon atoms.
92

C. All other compounds

Tc = 1.027 Tb + 159
Critical Pressure:

20.8Tc
Pc
Vc 9

where Tc is in K and Vc is in cm3 g-1.

Critical Volume:

Vc (0.377 P 11.0)

1.2

where P is a parameter called the Sugten Parachor.

93

SUGTEN PARACHOR VALUES FOR

ATOMS AND STRUCTURAL UNITS
C

4.8

48.2 triple bond 46.6

17.1

25.7

16.7

12.5

Cl

54.3

11.6

37.7

Br

68.0

8.5

20.0

91.0

6.1

O (esters) 60.0 double bond 23.2

Pcompound ni Pi

94