Volumetric Properties of

Pure Fluids

1
 Equation of State (EOS)
EOS is the equation that represents the state of system

An equation of state exists relating pressure, molar or

specific volume, and temperature for any pure
homogeneous fluid in equilibrium states.

Ideal gas equation is the equation of state for gas

PV n RT

2
 Compressibility factor (Z)
V
Z
V ideal
Vm = molar volume or volume per mole

If Z < 1 molar volume of real gas is less than ideal gas -

- molecular attraction is dominant

Z > 1 molar volume of real gas is larger than ideal gas

molecular repulsion is dominant

RT
Substitute
V ideal

P
V PV
Z
RT P RT
Compressibility factor (Z)
 Virial EOS
The compressibility factor: Z
PV
RT
the virial expansion: Z (1 BP C P 2 DP 3 ...)
B C D
Z (1 2 3 ...) (alternate form)
V V V
the parameters B, C, D, etc. and B, C, D are virial
coefficients, accounting of interactions between molecules.
B and B are second virial coefficients and C and C are third
virial coefficients etc.
These are function of temperature only.

B C B 2
D 3 BC 2 B 3
B
'
, C' , D'
RT RT 2
RT 3
 Virial EOS (at low pressure)
A more common form of this equation results from the substitution:

PV BP
Z 1
RT RT
At lower pressures the Virial equation may be truncated to two terms

(up to 15 bars): PV B
Z 1
RT V
Below the critical pressures, the virial equation truncated to three
terms often provided excellent results. Thus the appropriate form
is (15 50 bars):
PV B C
Z 1 Figure 3.10

RT V V2
 Example
Reported values of the virial coefficients of isopropanol vapor at
200oC are:

B = -388 cm3/mol C = -26,000 cm6 mol-2

Calculate V and Z for isopropanol vapor at 200oC and 10 bar by:

(a)The ideal-gas equation

(b) virial equation

The absolute temperature is T = 473.15 K and the appropriate value

of the gas constant is

R = 83.14 cm3 bar mol-1 k-1

 (a) For an ideal gas , Z =1, and
V
RT

83.14473.15 3934
cm 3
P 10 mol
(b) Using virial equation
PV BP V
Z 1 Z ideal
0.9014
RT RT V
RT
V B 3934 388 3546 cm 3 / mol
P
Alternate form
RT C
V 1 B
P V V 2

To facilitate iteration this eqn may be written as

RT B C
Vi 1 1
2
P Vi Vi
where subscript i denotes the iteration number. For the first
iteration, i = 0, and
 RT B C
V1 1
2
P V0 V0
where V0 = 3,934, the ideal gas value. Numerically,

388 26,000
Vi 3,934 1 3,539
2
3,934 3934
The second iteration depends on the result:
RT B C
V2 1
2
P V1 V1
388 26,000
V2 3,934 1 3,495
2
3,539 3,539
Iteration continuous until the difference Vi+1 Vi is insignificant,
and leads after five iterations to the final value,

V = 3,488 cm3 mol-1 and Z =0.8866

 Limitation of the Virial equation of state (VEOS)

The Virial equation of state is accurate only at

(limited to) low to moderate pressure (upto 50
bar).

The intermolecular forces are summed in the

VEOS

The problem also lies in the two-phase region

for real gases.
10
 Van der Waals EOS
Since the VEOS is limited to low to moderate pressure and
the problem also lies in the two-phase region for real gas,
we need another equation of state which approximates P-V-
T behavior at high pressure and accounts phase changes.

All real gases can be liquefied and depending on the gas

this might require compression and/or cooling.

The Van der Waals EOS accounts liquefaction, critical

point, and unlike the Virial equation, it works in high
density region.

11
 Van der Waals equation

another attempt to find equation of state for real gas

To correct whats wrong in kinetic molecular model, Van

der Waals proposed

P m easu red
P P
i deal

molecular attraction reduces impact force to wall

Vmeasured Videal V
12
 Van der waals equation

volume of gas is the space where gas can travel in a

container

ideal gas has no molecular volume, volume of gas is

volume of container

real gas has molecular volume (repulsion), space that

gas can travel is less than volume of container
P (rate of collision) x (impact force)

n n

V V
Attraction reduces rate of collision and impact force
2
n
Reduction in pressure (due to attraction) a
V
From ideal gas equation

nRT
P
V
 real gas volume is less than ideal gas, Given b as
molecular volume

Vreal V nb

Substitute V in the ideal gas eqn. with V - nb

 then

2
P a n V nb nRT
V

Van der waals s equation

a, b= Van der Waals parameter (obtained from experiment)

Since Van der Waals equation comes from

modification of kinetic molecular model

(theory) while a, b comes from experiment

Van der waals equation is semi-empirical

virial equation is empirical

18
19
 Concluding remarks

The Van der Waals EOS accounts the presence of critical point,
works at higher pressure (density) regions and unlike the Virial EOS
the attractive and repulse terms are incorporated separately.

It can be reduced to the ideal gas EOS when volume is very large.

It suggests Zc = 0.375 which generally is higher than experimentally

observed values (0.24-0.3).

It has a Virial expansion from that gives the second Virial coefficient
in terms of the Van der Waals constants a & b.

It provides the principle of two-parameter corresponding state.

20
 A Generic Cubic Equation of state

Since the time of Vander der Waals hundreds of

cubic EOS have been developed but most of them
were abandoned. Those which found widespread
use have the general form

RT
P attractive term
V b
 A Generic Cubic Equation of state

In their comprehensive format all cubic EOS can

be written as:

RT V
P
V b V b V k V
2

Where b, , k, and are parameters which in general depend on

temperature and (for mixtures) composition.

It reduces to the Van der Waals EOS when = b, = a, and k = = 0.

 A Generic Cubic Equation of state

An important class of cubic equations results from the preceding

equation with the assignments:

= b, = a(T), k = ( + )b, = b2.

RT a T
P
V b V b V b

Thus the generic cubic equation of state may be written as .

 A Generic Cubic Equation of state

For a given equation

and are pure numbers, the same for all substance

a(T) and b are substance dependent.

The temperature dependence of a(T) is specified to

each equation of state.

For Van der Waals equation a(T) = a is a substance-

dependent constant, and = = 0.
24
25
 Redlich-Kwong EOS

The Redlich-Kwong equation is adequate for calculation of gas phase

properties when the ratio of the pressure to the critical pressure

(reduced pressure) is less than about one-half of the ratio of the

temperature to the critical temperature (reduced temperature):

26
 Soave-Redlich-Kwong EOS

, and is the acentric factor for the species.

27
 Peng-Robinson EOS

, and is the acentric factor for the species.

28
Theorem of corresponding states; Acentric factor

Experimental observation shows that compressibility factors Z for

different fluids exhibit similar behavior when correlated as a
function of reduced temperature Tr and reduced pressure Pr;

By definition
P T
Pr , Tr
Pc Tc

This is the basis for two-parameter theorem of corresponding states

All fluids, when compared at the same reduced temperature and

reduced pressure, have approximately the same compressibility
factor, and all deviate from the ideal-gas behavior to about the same
degree.
29
30
van der Waals type equations:
van der Waals equation

Dotted lines
for vdW EoS

31
 Although this theorem is very exact for the simple fluids (argon,

krypton, and xenon) systematic deviations are observed for more

complex fluids.

Appreciable improvement results from the introduction of a third

corresponding-state parameter, characteristic of molecular

structure; the most poplar such parameter is the acentric factor

introduced by Pitzer and coworkers.

The acentric factor for a pure chemical species is defined with

reference to its vapor pressure.

32
 Corresponding states principles

Two-parameter corresponding states principle:

For the same reduced temperature and reduced pressure,
the compressibility factor is the same.

Three-parameter corresponding states principle:

For the same reduced temperature and reduced pressure
and the same third parameter such as critical
compressibility factor, acentric factor, or Riedel alpha the
value of the compressibility factor is the same.

33
 Vapor & vapor-like root of the generic cubic
equation of state

the generic cubic equation of state may be written as

RT a T V b
V b
P P V b V b

Solution of V may be by trial and error, iteration, or with the solve

routine of a software package.

An initial estimate for V is the ideal-gas value RT/P.

For iteration, this value is substituted at the right side of the equation.

The resulting value of V is then returned to the right side, and the
process
34 continue until the change in V is suitably small.
 Vapor & vapor-like root of the generic cubic equation
of state

In terms of compressibility factor the generic cubic equation of state

may be written as

Z 1 q
Z
Z Z
bP P a ( T ) Tr
r , q
RT Tr b RT Tr

iterative solution starts with Z =1 substituted on right side.

the calculated value of Z is returned to the right side and the process
continuous to convergence.

the final value of Z yields the volume root through V = ZRT / P.

35
 Liquid & Liquid-like root of the generic cubic
equation of state

The generic cubic equation of state may be solved for the V in the numerator
to the final fraction to give

RT bP V P
V b V b V b
a(T )
Solution of V may be by trial and error, iteration, or with the solve routine of
a software package.

An initial estimate for V is V =b.

For iteration, this value is substituted at the right side of the equation.

The resulting value of V is then returned to the right side, and the process
36
continue until the change in V is suitably small.
 Liquid & Liquid-like root of the generic cubic
equation of state

An equivalent equation for Z and can be written as

1 Z
Z Z Z
q

Solution of Z may be by trial and error, iteration, or with the solve

routine of a software package.

An initial estimate for Z is Z = .

The calculated value of Z is returned to the right side and the process
continuous to convergence.
the
37
final value of Z yields the volume root through V =ZRT / P.
 Parameter Assignments for Equation of state

EOS (Tr) Zc

VdW 1 0 0 1/8 27 / 64 3/ 8

RK 1 1 0 0.08664 0.42748 1/3

Tr 2
SRK SRK(Tr:)* 1 0 0.08664 0.42748 1/3

PR PR(Tr:)** 0.07780 0.45724 0.3074

1 2 1 2

* SRK:

** PR:
38
 Example

Given that Pvap of n-butane at 350K is 9.4573 bar, find the molar
volumes of (a) saturated-vapor and (b) saturated-liquid n-butane at
these conditions as given by the Redlich/kwong equation.

P 9.4573 T 350
Pr 0.2491 , Tr 0.8233
Pc 37.96 Tc 425.1

1 3 3

Tr 2
Tr 2
0.42748 0.8233 2
q 6.6048
Tr 0.08664

pr (0.08664) (0.2491)
0.026214
Tr 0.8233
39
 Example

(a) For the saturated vapor, write the RK from

Z
Z 1 q
Z Z
Which results upon substitution of appropriate values for and from Table

Z
Z 1 q
Z Z
Iteration with an initial value Z = 1 converges on Z = 0.8305. Thus,

Z R T 0.8305 83.14 350

Vv 2 ,555 cm 3 mol 1
P 9.4573

An experimental value is 2,482 cm3 mol-1

40
 Example
(b) For the saturated liquid , apply RK from

1 Z
Z Z Z
q
1 Z
This becomes Z Z Z
q
1.026214 Z
or Z 0.026214 Z Z 0.026214
6. 6048 0 . 026214
The initial step is substitution of Z = on the right side of this equation.
Iteration leads to converges on the value Z = 0.04331. Whence,

Z R T 0.0433183.14350
Vl 133.3 cm 3 mol 1
P 9.4573

An experimental value is 115.0 cm3 mol-1

41
 For comparison, values of Vv and Vl calculated for the
conditions of this example by all four of the cubic EOS
considered here are summarized as follows:

Vv / cm3 mol-1 Vl / cm3 mol-1

Exp. VdW RK SRK PR Exp. VdW RK SRK PR

2,482 2,667 2,555 2,520 2,486 115.0 191.0 133.3 127.8 112.6

42
 2-parameter/3-parameter E.O.S.

Express Z as functions of Tr and Pr only, yield 2-parameter

corresponding states correlations:

The van der Waals equation

The Redlich/Kwong equation

The acentric factor enters through function (Tr;) as an

additional paramter, yield 3-parameter corresponding state

correlations:
The Soave/Redlich/Kwong (SRK) equation

The Peng/Robinson (PR) equation

43
 Pitzer correlations for the second Virial coefficient

The tabular nature of the generalized compressibility-factor is a

disadvantage, but the complexity of the functions Z0 and Z1

precludes their accurate representation by simple equations.

Approximate analytical expressions to these functions for a

limited range of pressures can be given. The simplest correlation

is for the second virial coefficients:

BP BPc Pr
Z 1 1
44
RT RTc Tr
 The quantity in brackets is the reduced 2nd Virial coefficient.

BPc
B B
0 1

RTc
Together, these equations become
P P
Z 1 B B
0 r 1 r

T Tr r

Comparison of this equation with the Pitzer correlation for Z provides

the following identifications:

0.422 0.172
B 0.083 1.6
0
B 0.139 4.2
1

Tr Tr
45
 Pitzer correlations for the second Virial coefficient

The simplest form of the virial equation has validity only at low to

moderate pressures where Z is linear in pressure.

The generalized virial-coefficient correlation is therefore useful

only where Z0 and Z1 are at least approximately linear functions of

reduced pressure.

For reduced temperatures greater than Tr ~ 3, there appears to be

no limitation on the pressure.

Simple and recommended.

Figures 3.13 & 3.14
46
Most accurate for nonpolar species.
Other virial type equations:
Beattie-Bridgeman EoS

Walas

47
Other virial type equations:
Beattie-Bridgeman EoS

Walas
 Other virial type equations:
Benedict-Webb-Rubin (BWR) EoS

Requires the values of 8

coefficients, however,
good to correlate data of
both liquid and gas, and
pvT properties near
critical point.

49
 Other virial type equations:
Benedict-Webb-Rubin (BWR) EoS

Felder and Rousseau, Elementary Principles of chemical processes, 2nd edition

For more compounds, See Table E5 of Walas

50
 Other virial type equations:
Benedict-Webb-Rubin (BWR) EoS
Problem: Two gram-moles of N2 are placed in a 3
liter tank at -150 oC. Estimate the tank pressure
using BWR equation.

P = 6.19 atm.

51
 Generalized correlations for gases

Pitzer Correlations for the compressibility factor

The correlation for Z takes the form

Z Z Z 0 1

Where Z0 and Z1 are functions of both Tr and Pr.

= 0 , as is the case for the simple fluids, the second the disappears,

and Z0 becomes identical with Z.

52
 Pitzer Correlations for the compressibility factor

Z Z Z 0 1

This equation is a simple linear relation between Z and for given

values of Tr and Pr .

Experimental data for Z for nonsimple fluid plotted vs. at constant Tr

and Pr do indeed yield approximately straight lines, and their slopes

provide values for Z1.

53
Generalized correlation for Z0. Based on data for Ar, Kr and Xe from Pitzers correlation.

Z0 represents the compressibility of a compound with = 0 (simple fluids)

Almost all compounds have an acentric factor that falls between 0 and 1.
54
Fundamentals of Chemical Engineering Thermodynamics by Kevin and Donald
 Generalized correlation for Z1. (correction for the effect of non-spherical inter-
molecular forces) from Pitzers correlation.

Z1 represents the difference between Z0 and the Z that would be expected for a
hypothetical compound that had an = 1.
55
Fundamentals of Chemical Engineering Thermodynamics by Kevin and Donald
 Generalized correlations for gases

Of the Pitzer-type correlations available, the one developed

by Lee and Kelser has found greatest favor.

Its development is based on a modified form of the

Benedict/Webb/Rubin equation of state.

It takes the form of tables which present values of Z0 and Z1 as

functions of Tr and Pr.

Values of Z0 and Z1 as functions of Tr and Pr are given in

Appendix E, Table E.1 (Text book) .

Use of these tables often requires interpolation.

56
 Generalized correlations for gases

These Lee/Kesler correlation provide reliable results for

non-polar or only slightly polar gases. The accuracy is

(error of no more than) ~ 2-3%.

For highly polar gases, and the gases that associate, the

even larger errors are possible (accuracy is ~5-10%).

The generalized correlations are not intended to be

substitutes for reliable experimental data!

57
Lee-Kesler analytical equation

58
Lee-Kesler analytical equation

59
 Use of Pitzer (Lee-Kesler method) method

Estimate the specific volume for CO2 (in cm3/g) at:

a) 310 K and 8 bar,

b) 310 K and 75 bar.

The experimental values at these conditions are 70.58 cm3/g and

3.90 cm3/g, respectively. Use Pitzer method (Lee-Kesler method).

60
 Corresponding states method

Two-parameter corresponding states method describes that

for the same reduced temperature and pressure
compressibility factor (Z) is the same. The two-parameter
method (based on Tr and pr) is less accurate compared to
three- or four-parameters methods. In a three-parameter
method, critical compressibility factor (Zc) and Pitzer
acentric factor () are commonly used. Riedel alpha as
the third parameter is not common. Lydersen et al.
(Lydersen method) uses critical compressibility factor
method while Pitzer et al. (Pitzer method) applies acentric
factor (). Lee-Kesler method is a modification of Pitzer
method.
61
 Lydersen method

Lydersen and coworkers used critical compressibility

factor as the third parameter. Critical compressibility
factor can be calculated using pc, Tc, and vc data.

Z at the critical point, i.e., Zc is usually in the range of

0.27 to 0.29. For most substances, it is 0.27.

62
 Lydersen method

We need Tr = ratio of temperature of interest to critical

temperature of substance and pr = ratio of pressure of interest
to critical pressure of substance to locate Z for a constant value
of Zc.

T p
Tr pr
Tc pc

If two charts at, say, Zc = 0.27 and Zc = 0.29 are given, then
two Z values using Tr and pr can be viewed from each of these
charts. If the Zc value for the component or mixture of
components lies between the above two Zc values, then the
required Z can be calculated using two-point interpolation
(between two Zcs and two Zs). 63
 Lydersen method

High pressure region

Low pressure region 64

(Zc = 0.27)
 Lydersen method
Zc = 0.27

High pressure region

Low pressure region

65
 Lydersen method
(Zc = 0.29)

66
 Use of Lydersen method

100 moles of ethylene at 50C and 40 atm is

present in a container. Compute the volume of the
container using the Lydersen method. Use Tc = 283
K, pc = 50.5 atm, and Zc = 0.276.

Hint:
Tr = (50+273.15)/283 = 1.142
pr = 40/50.5 = 0.792
For Zc = 0.27, Z = 0.81
For Zc = 0.29, Z = 0.80
Now interpolate 67
Lydersen method: Alternate approach [11]

68
Lydersen method: Alternate approach [11]

69
 Use of Lydersen (alternate) method

Determine the compressibility factor of water at

700C and 25 MPa pressure by using the Lydersen
generalized technique. Compare your answer with
the value of Z = 0.97 derived from experimental
data. Use Tc = 647.3 K, pc = 22.12 MPa, and Zc =
0.234.

70
 Generalized equations and
correlations for liquids

The generalized cubic equation of state (low accuracy)

Lydersen method

The Lee/Kesler correlation includes data for subcooled

liquids
Suitable for nonpolar and slightly polar fluids

Estimation of molar volumes of saturated liquids only

Rackett, 1970: V sat

V Z c
( 1Tr )0.2857

c
Gunn-Yamada correlation
71
Gunn-Yamada correlation

or

and

Vsc =

Vsc is a scaling parameter (cm3/mol), Vr(0) = function of Tr.

- Quite accurate for nonpolar and slightly polar fluids (Tr 1)

- Both equations give error within 1 percent for non-polar compounds
 Generalized correlations for liquids
Generalized density correlation for liquid (Lydersen, Greenkorn,
and Hougen, 1955)

- A two parameter corresponding states correlation for

estimation of liquid volume

V
c
r
V c

c is the density at the critical point

The generalized correlation is shown by the Fig. in the next

slide. This figure may be used directly with the above equation
for
73 determining Vl if Vc is known.
 It provides a correlation of r as a function of Tr and Pr i.e.
r = f(Tr, Pr)

74
 A better procedure is to make use of a single known liquid volume

(state 1) by the identity

V V r1

2
1

r2

V2 = required volume

V1 = known volume

r1 and r2 = reduced densities read from the Figure 3.16, text book,

(given in the previous slide)

75
Problem:
The specific volume of iso-butane liquid at 300 K and 4 bar is 1.824
cm3/g. Estimate the specific volume at 415 K and 75 bar.
 Problem: Estimate the density of saturated liquid ammonia at 37 oC

using the following relations

a) The Gunn-Yamada correlation

b) Rackett equation

And compare with the experimental value (0.5834 g/cm3).

77
 Mixing rules for generalized charts for
compressibility factor
1- Kay method (1938)

Find Pci, Tci and Zci then use Lydersen approach

2- Prausnitz and Gunn method (1958)

Find Vci, Tci, Zci then Pci use Lee/Kesler approach

3- Lorentz-Berthelot type method (for binary system)

4- Mean compressibility factor and Daltons law

Find pi (Daltons law), pri, Tri then Zi then ZiYi

78
 Mixing rules for generalized charts for
compressibility factor

- Above equations can used for both gas and liquid phases.
79
k12 cross coefficient factor of different
compounds for LB equation
k12 cross coefficient factor of different
compounds for LB equation
 Activity

A gaseous mixture at 25C (298K) and 120 atm

(12,162 kPa) contains 3.0% He, 40.0%Ar, and 57.0%
C2H4 on a mole basis. Compute the volume of the
mixture per mole using the following:
a) generalized compressibility factor method
(Lydersen method),
b) generalized compressibility factor method (Pitzer
method using Lee-Kesler charts).

82