1

TOPIC 4
NON-IDEAL FLUID BEHAVIOR
2

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.
3
THE CRITICAL POINT

Critical point: The maximum pressure and

temperature where a pure material can exist in
vapor-liquid equilibrium. Beyond T
c
and P
c
, 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.
4
Supercritical
P-T phase diagram for a pure material.
C - critical point
5
P-V phase diagram for a pure
material. C - critical point.
V
nRT
P
At high T we expect the
isotherms to conform to
the ideal gas law, i.e., P
is inversely proportional
to V.
6
P-V phase diagram for pure
H
2
O.
7
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.
8
Schematic isotherms in the two-phase field for a pure fluid.
A
X Y
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).
B
P Q
9
MOST GENERAL EQUATION OF
STATE
dP
P
V
dT
T
V
dV
T P

,
_

,
_

dP dT
V
dV

Two special cases:
a) Incompressible fluid
= = 0
dV/V = 0 (no equation of state exists)
V = constant
b) and are temperature- and pressure-independent
10
VIRIAL EQUATION OF STATE
The most generally applicable EOS
PV = a + bP + cP
2
+
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.
11
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 (cm
3
atm g-mol
-1
) = a
So a is the same for all gases. It is in fact, RT!
12
I. THE COMPRESSIBILITY FACTOR
13
THE COMPRESSIBILITY FACTOR
Z PV/RT = 1 + BP + CP
2
+ DP
3
+
or
Z = 1 + B/V + C/V
2
+ D/V
3
+
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/V
2
arises due to interactions among three
molecules, etc.
14
The constants for the two versions of the virial
equation are related by the equations:
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.
RT
B
B '
( )
2
2
'
RT
B C
C

( )
3
3
2 3
'
RT
B BC D
D
+

15
SOME APPROXIMATIONS
Low pressure (0 - 15 bars at T < T
c
)
Becomes valid over greater pressure ranges as
temperature increases. Easily solved for volume.
Moderate pressure (0 - 50 bars)
Only B and C are generally well known. At higher
pressures, other EOSs are required.
RT
BP
RT
PV
Z + 1
2
1
V
C
V
B
RT
PV
Z + +
16
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:
RT
BP
Z + 1
17
The compressibility factor
as a function of pressure
for various gases. Z
measures the deviation
from the ideal gas law.
18
II. EQUATIONS OF STATE
19
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.
20
VAN DER WAALS EQUATION (1873)
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 b V
V
a
P

,
_

+
2
( )
2
V
a
b V
RT
P

21
P/P
c
V/V
c
The van der Waals
isotherms (labelled with
values of T/T
c
.
The van der Waals
equation predicts the shape
of the isotherms fairly well
in the one-phase region,
but shows unrealistic
oscillations in the two-
phase region. The theory
fails because it only
considers two-body
interactions.
22
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.,
Solving these equations we get:
0

,
_

T
V
P
0
2
2

,
_

T
V
P
b V
c
3
bR
a
T
c
27
8

2
27b
a
P
c
375 . 0
8
3

c
c c
c
RT
V P
Z
23
CRITICAL CONSTANTS OF GASES - I
Gas P
c
(atm) V
c
(cm
3
mol) T
c
(K) Z
c
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
H
2
12.8 65.0 33.2 0.305
O
2
50.1 78.0 154.8 0.308
N
2
33.5 90.1 126.3 0.291
F
2
55 ---- 144 ---
Cl
2
76.1 124 417.2 0.276
Br
2
102 135 584 0.287
24
CRITICAL CONSTANTS OF GASES - II
Gas P
c
(atm) V
c
(cm
3
mol) T
c
(K) Z
c
CO
2
72.7 94.0 304.2 0.275
H
2
O 218 55.3 647.4 0.227
NH
3
111 72.5 405.5 0.242
CH
4
45.8 99 191.1 0.289
C
2
H
4
50.5 124 283.1 0.270
C
2
H
6
48.2 148 305.4 0.285
C
6
H
6
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.
25
We can rearrange the previous equations to get the
van der Waal parameters in terms of the critical
parameters:
where
Note that, the actual measured value of V
c
is not used
to calculate a and b!
2
3
c c
V P a
3
c
V
b
c
c
c
P
RT
V
8
3

26
VAN DER WAALS CONSTANTS FOR
GASES
Gas a b Gas a b
He 0.03412 2.370 Cl
2
6.493 5.622
Ne 0.2107 1.709 CO
2
3.592 4.267
Ar 1.345 3.219 H
2
O 5.464 3.049
Kr 2.318 3.978 NH
3
4.170 3.707
Xe 4.194 5.105 CH
4
2.253 4.278
H
2
0.2444 2.661 C
2
H
4
4.471 5.714
O
2
1.360 3.183 C
2
H
6
5.489 6.380
N
2
1.390 3.913 C
6
H
6
18.00 1.154
a - dm
6
atm mol
-2
; b - 10
-2
dm
3
mol
-1
27
SOME OTHER EOSs
Bertholet (1899)
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)
, , A and l are correction factors.
( ) RT b V
V T
a
P

,
_

+
2
( )

,
_

V RT
a
e
b V
RT
P
( )
2
) (
l V
A
e V
RT
P
V

28
BEATTIE-BRIDGEMAN (1927)
a, b, c, A
0
, B
0
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 P
calc

P
exp
, then adjust V accordingly and recalculate P.
( )
2 2
) 1 (
V
A
B V
V
RT
P +

( ) V a A A 1
0
( ) V b B B 1
0
3
T V
c

29
Rearrangement of the Beattie-Bridgeman equation
gives:
Where
This shows the B-B equation to be simply a truncated
form of the virial equation.
4 3 2
V V V V
RT
P

+ + +
2
0 0
T
Rc
A RTB
2
0
0 0
T
c RB
aA b RTB +
2
0
T
bc RB

30
BEATTIE (1930)
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.
( ) ( )
RT
A
B V + 1
( ) a A A 1
0
( ) b B B 1
0 3
T
c

P
RT

perfect gas volume
31
SOME MORE EOSs
Jaff (1947) - a modification of the Dieterici EOS
Wohl (1949)
( )
( )
( )

,
_

,
_

V RT
c
e
b V
TT R
b V
RT
P

1
2
1
2
2 2
4
e P
T R
c
c

2
e P
RT
b
c
c

( ) ( )
3
V
c
b V V b V
RT
P +

2
6
c c
V P 4
c
V b
3
4
c c
V P c
32
McLeod (1949)
where
and a, A, B, and c are constants.
Benedict-Webb-Rubin (1940) - specifically devised
for hydrocarbons. Useful for both liquids and
gases. Define
RT b V ) ' (
2
V
a
P +
2
' + c B A b
V
d
1

[ ] ( )
( )
1
]
1

+
+ +
+ +

2
2
2 3
6
3 2 2
0 0 0
1
d
e
T
d cd
d a
d a bRT d T C A RT B RTd P

33
Martin-Hou (1955)
Introduces the reduced temperature: T
r
= T/T
c
Like many others, this EOS is also a version of the
virial EOS.
5
5
4
4
3
239
3 3 3
2
238
2 2 2
) ( ) (
) (
) (
) (
) (
) (
b V
T B
b V
A
b V
e C T B A
b V
e C T B A
b V
RT
P
r r
T T

+ +
+

+ +
+

34
35
REDLICH-KWONG (1949)
This has been one of the most useful to geology
where
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.
) ( ) (
2
1
b V V T
a
b V
RT
P
+

c
c
P
T R
a
5 . 2 2
42748 . 0

c
c
P
RT
b
08664 . 0
3333 . 0
3
1

c
Z
36
MODIFICATIONS OF THE R-K EOS
de Santis et al. (1974)
but b is a constant and a(T) = a
0
+ a
1
T.
Peng and Robinson (1976)
where
and
is a parameter for the fluid called the acentric factor.
) ( ) (
2
1
b V V T
a
b V
RT
P
+

) 2 (
) (
) (
2 2
b V b V
T a
b V
RT
P
+

( ) [ ]
2
2
1
1 1 ) (
r
T m T +
2
26992 . 0 54226 . 1 37464 . 0 + m
37
Carnahan and Starling (1969) - hard-sphere model
Kerrick and Jacobs (1981) - Hard-Sphere Modified
Redlich-Kwong (HSMRK)
a(P,T) = an empirically-derived polynomial.

,
_

+ +

3
3 2
) 1 (
1
y
y y y
V
RT
P
V
b
y
4

) (
) , (
) 1 (
1
2
1
3
3 2
b V V T
T P a
y
y y y
V
RT
P
+

,
_

+ +

2
) ( ) (
) ( ) , (
V
T e
V
T d
T c T P a + +
3
3 2 1
) ( T z T z z T z + + where z = c, d, or e
38
LEE AND KESLER (1975)
1
1
]
1

,
_

,
_

+ +
+
+

+
+

+ +

,
_

+ +
+
+

+
+

+

,
_

,
_

2
1
2
0
2
1
1
2 3
14
5
1
12 11
2
3
13
1
12 11
3
14
2
13
1
12 11
2
0
0
2 3
04
5
1
02 01
2
3
03
1
02 01
3
04
2
03
1
02 01
1
1
r
r
V
r r r r
r
r
r r
r
r r r
V
r r r r
r
r
r r
r
r r r
e
V V T
c
V
T d d
V
T c T c c
V
T b T b T b b
e
V V T
c
V
T d d
V
T c T c c
V
T b T b T b b
Z

39
DUAN, MOLLER AND WEARE (1992)

,
_

,
_

+ + + + + +
2
2 2 5 4 2
1
r
V
r r r r r r
e
V V
F
V
E
V
D
V
C
V
B
Z

3
3
2
2 1

+ +
r r
T a T a a B
3
6
2
5 4

+ +
r r
T a T a a C
3
9
2
8 7

+ +
r r
T a T a a D
3
12
2
11 10

+ +
r r
T a T a a E
3

r
T F
c
c
r
RT
VP
V
c
r
P
P
P
c
r
T
T
T
This is just a modified form the the Lee and Kesler EOS.
40
CALCULATING FUGACITY
COEFFICIENTS BY INTEGRATING AN
EOS
Using the van der Waals equation:
( )
2
V
a
b V
RT
P

,
_

P
P
P RT
V
0
1
ln
RT
V P
RT V
a
b V
b
b V
V
ln
2
ln ln

+
,
_

41
Using the original Redlich-Kwong equation:
) ( ) (
2
1
b V V T
a
b V
RT
P
+

,
_

P
P
P RT
V
0
1
ln
RT
V P
b V
b
V
b V
b RT
a
V
b V
b RT
a
b V
b
b V
V
ln ln
ln
2
ln ln
2
3
2
3

,
_

+

,
_

+
+

,
_

+
,
_

42
Using the HSMRK EOS of Kerrick and Jacobs (1981)
V b RT
e
V
b V
b RT
e
b RT
e
V
b V
b RT
d
b V RT
d
b V
V
b RT
c
b V V RT
e
b V V RT
d
b V RT
c
RT
V P
y
y y y
2 3
2 2
2
3
3 2
2
3
2
3
2
3
2
3
2
3
2
3
2
3
2
3
2
3
ln
2
ln
ln
) ( ) (
) (
ln
) 1 (
3 9 8
ln
+
,
_

,
_

+
+

,
_

+
+
+

+

43
Activities in CO
2
-H
2
O mixtures predicted by a MRK EOS after
Kerrick & Jacobs (1981).
44
Predicted H
2
O and CO
2
activities in H
2
O-CO
2
-CH
4
mixtures at 400C
and 25 kbar. Calculated for X
CH
4
= 0.0, 0.05 and 0.20. Dotted curves
imply a miscibility gap of H
2
O-rich liquid and CO
2
-rich vapor.
After Kerrick
& Jacobs
(1981).
45
CO
2
-H
2
O solvus at 1 kbar. The solid line is a fit of a MRK EOS to
experimental data (solid dots). After Bowers & Helgeson (1983).
46
Effect of 12 wt. % NaCl on
the CO
2
-H
2
O solvus at 1
kbar. After Bowers &
Helgeson (1983).
47
III. CORRESPONDING
STATES
48
PRINCIPLE OF CORRESPONDING
STATES
Reduced variables of a gas are defined as:
P
r
= P/P
c
T
r
= T/T
c
V
r
= V/V
c
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.
49
The reduced compressibility factor vs. the reduced pressure
50
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
Reduced pressure
Reduced pressure
Z
Z
Generalized compressibility
chart. Medium- and high-
pressure range.
RT
PV
Z
51
EXAMPLE: Calculate the specific volume of NH
3
at
500C and 2 kbar using the reduced Z chart and
compare to the ideal gas law prediction.
Ideal gas law
Corresponding states: T
r
= (773 K)/(405.5 K) = 1.91;
P
r
= (2000 atm)/(111 atm) = 18.02.
1
1
mol L 0310 . 0
atm) (2000
) K 773 )( mol L atm 080256 . 0 (

P
RT
V
) K 773 )( mol L atm 080256 . 0 (
V atm) (2000
62 . 1
1
Z
1
mol L 050 . 0

V
52
53
54
55
56
Measured compressibility factors for H
2
O vs. those obtained from
corresponding state theory
57
Measured compressibility factors for CO
2
vs. those obtained from
corresponding state theory
58
Generalized density correlation for liquids.
r
= /
c

59
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:
but the L-V curve terminates at the critical point where T
r

= P
r
. So a = b and
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.
r
sat
r
T
b
a P log

,
_

r
sat
r
T
a P
1
1 log
60
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 P
r
sat
= -1 at T
r
= 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.
The acentric factor is:
can be determined from T
c
, P
c
and a single vapor
pressure measurement at T
r
= 0.7.
( ) 000 . 1 log
7 . 0


r
T
sat
r
P
61
Slope -3.2
(n-octane)
Approximate temperature-dependence of reduced vapor pressure
62
ACENTRIC FACTORS FOR GASES
Gas

Gas

Gas

Ne 0 Cl
2
0.073 methane 0.011
Ar -0.004 Br
2
0.132 ethylene 0.087
Kr -0.002 CO
2
0.223 ethane 0.100
Xe 0.002 CO 0.049 benzene 0.212
H
2
-0.22 NH
3
0.250 toluene 0.257
O
2
0.021 HCl 0.12 n-heptane 0.350
N
2
0.037 H
2
S 0.100 propane 0.153
F
2
0.048 SO
2
0.251 m-xylene 0.331
63
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 T
r
and P
r
.
The simplest correlation is for the second virial
coefficients:
The quantity in brackets is the reduced 2nd virial
coefficient.
r
r
c
c
T
P
RT
BP
RT
BP
Z

,
_

+ + 1 1
1 0
B B
RT
BP
c
c
+

,
_

64
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 = Z
0
+ Z
1
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!
6 . 1
0
422 . 0
083 . 0
r
T
B
2 . 4
1
172 . 0
139 . 0
r
T
B
65
Generalized correlation
for Z
0
. Based on data for
Ar, Kr and Xe from
Pitzers correlation.
66
Generalized correlation
for Z
1
based on Pitzers
correlation.
67
EXAMPLE -1
What is the volume of SO
2
at P = 500 atm and T =
500C?
According to the ideal gas law:
Using the acentric factor: =0.273; T
r
= 773/430.8 =
1.79; P
r
= 500/77.8 = 6.43.
From the charts: Z
0
= 0.97; Z
1
= 0.31.
Z = 0.97 + 0.273(0.31) = 1.055
1
1
mol L 124 . 0
atm) (500
) K 773 )( mol L atm 080256 . 0 (

P
RT
V
) K 773 )( mol L atm 080256 . 0 (
V atm) (500
055 . 1
1
Z
-1
mol L 0.131 V
68
Line defining the region where generalized second virial
coefficients may be used. The line is based on V
r
2.
saturation
69
EXAMPLE - 2
What is the volume of SO
2
at P = 150 atm and T =
500C?
According to the ideal gas law:
Using the acentric factor: =0.273; T
r
= 773/430.8 =
1.79; P
r
= 150/77.8 = 1.93.
1
1
mol L 414 . 0
atm) (150
) K 773 )( mol L atm 080256 . 0 (

P
RT
V
083 . 0
79 . 1
422 . 0
083 . 0
6 . 1
0
B
124 . 0
79 . 1
172 . 0
139 . 0
2 . 4
1
B
70
V
c
= 0.122 L mol
-1
V
r
= 0.392/0.122 = 3.25
049 . 0 ) 124 . 0 ( 273 . 0 083 . 0
1 0
+ +

,
_

B B
RT
BP
c
c

947 . 0
79 . 1
93 . 1
) 049 . 0 ( 1 1 +

,
_

+
r
r
c
c
T
P
RT
BP
Z
) K 773 )( mol L atm 080256 . 0 (
V atm) (150
947 . 0
1
Z
-1
mol L 0.392 V
71
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.
72
I. We can use this equation together with the generalized
Z charts.
1) Look up P
c
and T
c
of gas
2) Calculate P
r
and T
r
values for desired Ts and Ps
3) Make a Table of Z from the generalized charts at various
values of T
r
and P
r
. Of course, we must have P
r
values from
0 to the pressure of interest at each temperature.
4) Graph (Z-1)/P
r
vs. P
r
for each T
r
.
5) Determine the area under the the graph from P
r
= 0 to P
r
= P
r

to get ln .
II. Used generalized fugacity charts.

,
_

r
P
r
r
dP
P
Z
0
1
ln
73
74
75
USE OF TWO-PARAMETER
GENERALIZED FUGACITY CHARTS
EXAMPLE 1: Calculate the fugacity of CO
2
at 600C
(873 K) and 1200 atm.
T
c
= 304.2 K; P
c
= 72.8 atm
T
r
= 2.87; P
r
= 16.48
From the chart 1.12
so
f = (1.12)(1200) = 1344 bars
76
EXAMPLE 2: What is the fugacity of liquid Cl
2
at 25C
and 100 atm? The vapor pressure of Cl
2
at 25C is 7.63
atm.
For the vapor coexisting with liquid:
T
c
= 417 K; P
c
= 76 atm
T
r
= 0.71; P
r
= 0.10
from the chart 0.9
f = (0.9)(7.63) = 6.87 atm
Now we must correct this to 100 atm.
V = 51 cm
3
mol
-1
; assume to be constant.
f
2
= 8.36 atm
) ( ln ln
1 2 1 2
P P
RT
V
f f
77
THREE-PARAMETER CORRELATIONS
FOR FUGACITY ETC.
Fugacity:
Enthalpy:
Entropy:
Density:
Tables for these correlations can be found in Pitzer
(1995) Thermodynamics. McGraw-Hill.
) 1 ( ) 0 (
log log log

,
_

,
_

P
f
P
f
P
f

) 1 (
0
) 0 (
0 0

,
_

,
_

c c c
RT
H H
RT
H H
RT
H H

P
R
S S
R
S S
R
S S
ln
) 1 (
0
) 0 (
0 0
+

,
_

,
_

) 91 . 0 89 . 1 ( ) 1 ( ) 1 ( 85 . 0 1
3
1

+ + +
r r
c
T T
78
IV. GASEOUS MIXTURES
79
IDEAL GAS MIXTURES

Mixture as a whole obeys:

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.
RT V P
80
DALTONS LAW VS. AMAGATS
LAW
Daltons Law: P
i
= X
i
P
T
Amagats Law: V
i
= X
i
V
T
These two laws are mutually exclusive at a given
pressure and temperature.

i T
P P At constant V
T
and T

i T
V V
At constant P
T
and T
81
THERMODYNAMICS OF IDEAL
MIXING - REVISITED
We have previously shown that:
using Daltons Law we can derive:
and for entropy we have:

i
i i mix ideal
X X RT G ln

i
T
i
i mix ideal
P
P
X R S ln

i
T
i
i mix ideal
P
P
X RT G ln
82
NON-IDEAL MIXTURES OF NON-
IDEAL GASES
For a perfect gas mixture:
For an ideal mixture of real gases:
For a real mixture of real gases:
i T
o
i i
o
i i
X RT P RT P RT ln ln ln + + +
i
o
i
o
i i
o
i i
X RT f RT f RT ln ln ln + + +
T i i
o
i i i
P X f X f
i
o
i i
f RT ln +
T i i i
o
i i i i
P X f X f
Lewis Fugacity Rule
Correction for
non-ideal mixing
Correction for
non-ideal gas
83
DALTONS LAW AND
GENERALIZED CHARTS
Calculate reduced pressure according to:
i c
i
i r
P
P
P
,
,

RT Z n V P
A A T A
RT Z n V P
B B T B

RT Z n V P
C C T C

( ) ( )
( )
RT Z n
RT Z X Z X Z X n
RT Z n Z n Z n V P P P
mix T
C C B B A A T
C C B B A A T C B A

+ +
+ + + +
84
AMAGATS LAW AND
GENERALIZED CHARTS
Calculate reduced pressure according to:
i c
T
i r
P
P
P
,
,

RT Z n V P
A A A T
RT Z n V P
B B B T

RT Z n V P
C C C T

( ) ( )
( )
RT Z n
RT Z X Z X Z X n
RT Z n Z n Z n V V V P
mix T
C C B B A A T
C C B B A A C B A T

+ +
+ + + +
85
PSEUDOCRITICAL CONSTANTS
A
B
X
A
1
X
A
2
L - V c u r v e f o r B
L - V c u r v e f o r A
P
T
86
KAYS METHOD
Assumes a linear critical curve between the critical
points for A and B.

i
i c i c
P X P
,
'

i
i c i c
T X T
,
'
When answers are near the critical point for the
mixture, we cannot be certain that we are not
dealing with a liquid-vapor mixture.
87
JAFFS METHOD
For binary mixtures only.
B c B B A c A A
mix
c
c
P X P X
P
T
, ,
'
'
+

,
_

[ ]
B A B A B B A A
mix
c
c
X X X X
P
T
3
4
1
2 2
3
1
3
1
'
'
+ + +

,
_

i c
i c
i
P
T
,
,

88
MIXING CONSTANTS IN
EQUATIONS OF STATE
Van der Waals and simple Redlich-Kwong EOS:

n
j
j j mix
b X b
1

n
j
n
k
jk k j mix
a X X a
1 1
( )
2
1
k j jk
a a a
Use if no mixture data
are available.
89
Beattie-Bridgeman EOS:
2
1
, 0 , 0 1
]
1

n
j
j j mix
A X A

n
j
j j mix
a X a
1

n
j
j j mix
b X b
1

n
j
j j mix
B X B
1
, 0 , 0

n
j
j j mix
c X c
1
90
Benedict-Webb-Rubin EOS:
2
1
, 0 , 0 1
]
1

n
j
j j mix
A X A
3
1
3
1
]
1

n
j
j j mix
a X a
3
1
3
1
]
1

n
j
j j mix
b X b

n
j
j j mix
B X B
1
, 0 , 0
3
1
3
1
]
1

n
j
j j mix
c X c
2
1
, 0 , 0 1
]
1

n
j
j j mix
C X C
3
1
3
1
]
1

n
j
j j mix
X
2
1
1
]
1

n
j
j j mix
X
91
Virial Equation of State:
Z = 1 + B/V + C/V
2
+ D/V
3
+

n
i
n
j
ij j i mix
B X X B
1 1

n
i
n
j
n
k
ijk k j i mix
C X X X C
1 1 1
92
PREDICTION OF CRITICAL
CONSTANTS
Critical Temperature:
I. All compounds with T
boil
(1 atm) < 235 K and all
elements: T
c
= 1.70T
b
- 2.00.
II. All compounds with T
boil
(1 atm) > 235 K.
A. Containing halogens or sulfur
T
c
= 1.41T
b
+ 66 - 11F
F = No. of fluorine atoms
B. Aromatics and napthenes
T
c
= 1.41T
b
+ 66 - r(0.388T
b
- 93)
r = ratio of non-cyclic carbon atoms to total carbon atoms.
93
C. All other compounds
T
c
= 1.027 T
b
+ 159
Critical Pressure:
where T
c
is in K and V
c
is in cm
3
g
-1
.
Critical Volume:
where is a parameter called the Sugten Parachor.
9
8 . 20

c
c
c
V
T
P
2 . 1
) 0 . 11 377 . 0 ( + P V
c
P
94
SUGTEN PARACHOR VALUES FOR
ATOMS AND STRUCTURAL UNITS
C 4.8 S 48.2 triple bond 46.6
H 17.1 F 25.7 16.7
N 12.5 Cl 54.3 11.6
P 37.7 Br 68.0 8.5
O 20.0 I 91.0 6.1
O (esters) 60.0 double bond 23.2

i i compound
P n P