Chapter 3

VOLUMETRIC PROPERTIES OF
PURE FLUIDS

 PVT Behavior of Pure Substances

 Virial Equations of State

 Application of the Virial Equations

 Generalized Correlations for Gases

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 1

 3.1 PVT BEHAVIOR OF PURE SUBSTANCES
PT Diagram  Line 1-2: Sublimation Curve
 Line 2-3: Fusion Curve
 Line 2-C: Vaporization Curve
 Point 2: Triple Point
 Point C: Critical Point (Pc, Tc)
Point where the densities of liquid
T > Tc
and vapor become equal and the
interface between the two vanishes.
Supercritical
Above this point, only one phase can
exist.
 Beyond dashed lines : Fluid
Region
 Pt and Tt of water: 0.00603 atm
Fig 3.1 : PT diagram for pure substance & 0.0098oC
http://www.sv.vt.edu/classes/MSE2094_NoteBook/
96ClassProj/examples/triplpt.html
2006/2007 II BKF2413 Chemical Engineering Thermodynamics 2
PV Diagram
Subcool Superheated
liquid vapour

Fig 3.2: PV diagrams for a pure substance .

a) Showing solid, liquid and gas regions.
b) Showing liquid, liquid/vapour regions with
isotherms
2006/2007 II BKF2413 Chemical Engineering Thermodynamics 3
Critical Behaviour

Fig 3.3 : PT diagram for pure fluid showing the vapor-pressure curve
and constant-volume line in the single-phase regions.
2006/2007 II BKF2413 Chemical Engineering Thermodynamics 4
Single-Phase Region
 From the regions of the diagram where a single phase
exists , implies a relation connecting P and V and T which
may be express by function equation :
f (P,V,T)=0
 e.g. The simplest equation of state is for an ideal gas law :
PV = RT
 Normally one quantity is solved in term of another two
quantities for example , V = f ( P , T )
 Partial derivative in the equation :
 V   V 
dV    dT    dP
 T  P  P  t

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 5

 1  V 
  
V  T  P
 Volume expansivity
 Isothermal compressibility    V1  VP 
T
 Hence, the equation becomes:
dV
 dT  dP
V
V2
ln   T2  T1    P2  P1 
 After integration, V1

 For liquid phase, it is known as incompressible fluid

because  and  are very small until almost zero.

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 6

Example 3.1
For liquid acetone at 200oC and 1 bar,
ß = 1.487 x 10-3 oC-1;  = 62 x 10-6 bar-1; V = 1.287 cm3·g-1
For acetone, find:
 P 
 
a) The value of  T V at 20oC and 1 bar.
b) The pressure generated by heating at constant V from
20oC and 1 bar to 30oC.
c) The change in volume for a change from 20oC and 1
bar to 0oC and 10 bar.

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 7

Solution 3.1
a) The derivative (dP/dT)v is determined by application of Eq. (3.4)
to the case for which V is constant and dV = 0:
 P   1.478  10 3
ß dT — κ dP = 0 (const V) or      24bar o 1
C
 T V 
6
62  10

b) If ß and  are assumed constant in the 10oC temperature interval,

then the equation derived in (a) may be written (V const):

P and
  PT2 = P241 +10ΔP
  =1+ 240 = 24l bar
240bar


c) Direct substitution into Eq. (3.5) gives:

ln
V2
V1
   
 1.487  10 3  20   62  10 6 9   0.0303

V2 / V1 = 0.9702  V2 = (0.9702)(1.287) = 1.249 cm3·g-1

Then, V = V2 - V1 = 1.249 - 1.287 = -0.038 cm3·g-1

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 8

3.2 VIRIAL EQUATIONS OF STATE
PV = a + bP + cP2 + ….
 If b = aB’ , c = aC’ etc.
PV = a( 1 + B’P + C’P2 + D’P3 +…)
 A useful auxiliary thermodynamic property is defined by
the equation : Z  PV
RT
 Z is called compressibility factor. With the definition and
with a = RT :
Z = 1 + B’P + C’P2 + D’P3 +…
 An alternative form to express Z is as follows:
B C D
Z  1   2  3  ...
V V V
2006/2007 II BKF2413 Chemical Engineering Thermodynamics 9
 Both of these equations are known as virial
expansions.
 B’ , C’ , D’ , B, C , D etc. are called virial
coefficients and only depend on temperature.
B C  B2 D  3BC  2 B 3
B'  C'  D' 
RT RT  2
RT 3
 Second term is on account of interaction between
pair of molecules.
 Third term is on account of three-body interaction.
 Rapid decrease of higher term in contribution to Z.

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 10

3.3 THE IDEAL GAS
 Viral expansion arise on account of molecular
interaction .
 For ideal gas, no interaction molecular is assumed.
Hence
Z=1
PV = RT

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 11

3.4 APPLICATION OF THE VIRIAL EQNS.
PV BP
Z  1
 A common form is often applied: Z = 1 + B’P RT RT
(3.38)
 to vapors at subcritical Ts up to their saturation Ps.

 as approximation for gases at higher T up to a P of several bar.

PV B
Z   1
RT V
 Equation may be truncated to 2 terms for low P.
(3.39)
 For higher pressure but below the critical pressure , the virial equation
PV B C
truncated toRT
Z  3 terms.
 1  2
V V

C0
 Extended virial RT
equations
B0 RT isAillustrated
0 
T 2 by the
bRT  a Benedict/Webb/Rubin
a    
P     c  1   exp
equation: V V2 V3 V6  V2  V2

where A0, B0, C0, a, b, c, α and γ are all constants of a given fluid. Use
in petroleum & natural gas industries and other common gases.
2006/2007 II BKF2413 Chemical Engineering Thermodynamics 12
 ~~Examples 3.8~~
Reported values for virial coefficients of isopropanol
vapor at 200oC are :
B = –388 cm3·mol–1 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) Equation (3.38).

c) Equation (3.40).

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 13

Solution 3.8
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
RT 83.14 473.15
V    3,934cm 3 mol 1
P 10

b) Solving Eq. (3.37) for V gives:

RT
V   B  3,934  388  3,546cm 3 mol 1
P

Hence, Z
PV

V

3,546
 0.9014
RT RT P 3,934

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 14

Solution 3.8 (cont.)
c) To facilitate iteration, write Eq. (3.39) as:
RT  B C 
Vi 1  1   
P  2 
Vi Vi 

where subscript i denotes the iteration number.
For the first iteration, i = 0, and
RT  B C 
V1  1   2 
P  V0 V 0 
where V0 = 3,934, the ideal-gas value.
 388 26,000 
Numerically, V  3,934 

1  1 
3,934 3,934    3,539 2

The second iteration depends on this result:

RT  B C 
V2  1   2 
P  V1 V1 

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 15

Solution 3.8 (cont.)
 388 26,000 
c) Whence, V2  3,934 1   2 
3,539 3,539 
 3,495

Iteration continues until the difference V i+1 - Vi is
insignificant, and leads after five iterations to the
final value,
V = 3,488 cm3·mo1-1
from which Z = 0.8866. In comparison with this
result, the ideal-gas value is 13% too high and
Eq. (3.37) gives a value 1.7% too high.

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 16

3.5 CUBIC EQUATION OF STATE
 To represent the PVT behaviour of both liquids and
vapours.
 It must encompass a wide range of temperatures and
pressures and must not be complex.
 Polynomial equations that are cubic in molar volume offer
a compromise between generality and simplicity.
 Cubic equations are the simplest equations capable of
representing both liquid and vapour behaviour.
RT  V   
P 
V  b V  b V 2  V   
where  , , b,  and are parameters which is general
depend on temperature and (for mixture) composition.
2006/2007 II BKF2413 Chemical Engineering Thermodynamics 17
The Van der Waals Equation of State
 The equation above reduces to van der Waals
RT a
P  2
V b V
where a and b are positive constants.
 3 volume roots, of which 2 may be complex. Meaningful values should be
real, positive and larger than constant b.
 Fig. 3.11, any isotherm at T > Tc, only one root.
 At critical isotherm (T = Tc), only 1 root too, except at Pc, all 3 roots = Vc.
 For isotherm T < Tc, 1 or 3 real roots depending on P.
 Roots are real and positive, they are not stable states for portion of an
isotherm lying between saturated liquid and saturated vapour. Only Vsat (liq)
and Vsat (vap) at Psat are stable states.
 For other pressures, smallest root is a liquid or “liquid-like” volume, and the
largest is a vapour or “vapour-like” volume.
 The third root is of no significance.
2006/2007 II BKF2413 Chemical Engineering Thermodynamics 18
A Generic Cubic Equation of State
 Several hundred cubic equations of state have been proposed. All are
special cases of the equation:-
RT  V   
P 

V  b V  b  V 2  V   
 An important class of cubic equations results from the preceding
equation with the assignments:
η = b; θ = a(T); κ = (є + σ)b; λ = єσb2
RT aT 
P 
V  b V  b V  b 

For the given equation , ε & σ are pure numbers (the same for all
substances); parameters a(T) is specific to each equation of state.

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 19

The Van der Waals Equation of State
 The equation above reduces to van der Waals when η = b , θ = a , κ
= λ = 0. RT a
P  2
V b V
where a and b are positive constants.

A Generic Cubic Equation of State

 An important class of cubic equations results from the preceding equation with the
assignments:
η = b; θ = a(T); κ = (є + σ)b; λ = єσb2

RT aT 
P 
V  b V  b V  b 
For the given equation , ε & σ are pure numbers (the same for all substances);
parameters a(T) is specific to each equation of state.

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 20

A Generic Cubic Equation of State
 An important class of cubic equations results from the
preceding equation with the assignments:
η = b; θ = a(T); κ = (є + σ )b; λ = єσb2
RT aT 
P 
V  b V  b V  b 
 For the given equation, ε and σ are pure numbers, the
same for all substances, whereas parameters
a (T) is specific to each equation of state.
 The Redlich/Kwong (RK) equation :
RT aT  1
P 
V  b V  b V  Tr   Tr 2

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 21

 Theorem of Corresponding States: Acentric
Factor 
 Experiment observation shows that compressibility factor
Z for the different fluids exhibit similar behavior when
correlated as a function of reduced temperature Tr and
reduced pressure Pr; as defined: P  P T  T
r r
Pc Tc

 This is the basis for the 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
ideal-gas behavior to about the same degree .
2006/2007 II BKF2413 Chemical Engineering Thermodynamics 22
 Two-parameter Theorem ONLY very nearly exact for
simple fluids (SF) like argon, krypton, xenon. For
complex fluids, systematic deviations are observed.
 This systematic deviation can be proven by plotting a
graph of log Prsat vs 1/Tr. If all pure substances show same
behavior, then the plot of these species will all fall on the
same line. However, only SF shows this characteristic.
 To improve the correlation, third corresponding-states
parameter (besides Pc Tc),  was introduced to consider
the characteristic of molecular structure.

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 23

 Theorem of Corresponding States: Acentric Factor
 Pitzer noted that all vapor-pressure data for the simple
fluids (Ar, Kr & Xe) lie on the same line.
log Prsat = –1.0 when Tr = 0.7
≡ log Prsat(SF)Tr=0.7 – log (Prsat)T =0.7
r

 Acentric factor,  is defined as the

difference evaluated at Tr = 0.7.
 = –1.0 – log (Prsat)Tr = 0.7
 It measures the departure of
molecules from perfectly
spherical nature.
  = 0 for SF (reference point) Fig. 3.13: Approximate temperature dependence of
the reduced vapor pressure
2006/2007 II BKF2413 Chemical Engineering Thermodynamics 24
 This is the basic premise of the following three-parameter
theorem of corresponding state :
All fluids having the same value of , when compared at
the same Tr and Pr, have about the same value of Z, and
all deviate from ideal-gas behavior to about the same
degree.

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 25

3.6 GENERALIZED CORRELATIONS FOR
GASES
 Generalized correlations find widespread use. Most popular are correlations
of the kind developed by Pitzer and co-workers for Z and B.
(i) Pitzer Correlations for the Compressibility Factor Z
 The correlation for Z is
Z = Z0 + Z1
where Z0 and Z1 are functions of both Tr and Pr.
 When  = 0  simple fluids
 The second term in the above correlation represents a relatively small
correction and its omission does not introduce large errors.
 To use that correlations, values developed by Lee and Kesler has found
greatest favour. It takes the form of tables which present values of Z0 and Z1
as function of Tr and Pr.  (Refer Tables E.1 to E.4)
 The work of Lee/Kesler provides reliable results for gases which are
nonpolar or only slightly polar.

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 26

 Quantum gases (hydrogen, helium & neon) do not conform to the same
corresponding-states behavior as do normal fluids. Treatment of
temperature-dependent effective critical parameters is required. ( is zero)
 e.g. for Hydrogen ONLY:
43.6
TC / K 
21.8
1
2.016T
20.5
PC / bar 
44.2
1
2.016T

3 51.5
1
VC / cm mol 
9.91
1
2.016T
2006/2007 II BKF2413 Chemical Engineering Thermodynamics 27
(ii) Pitzer Correlations for the Second Virial
Coefficient B
 The simplest form of the virial equation:
BP  BP  Pr BPc
Z  1  1   c  RTc
RT  RTc  Tr
 Thus , Pitzer and co-worker proposed a second correlation , which yields
values for
BPc
 B 0  B 1 :
RTc
 Together these two equations becomes
Pr P
Z  1 B0  B 1 r
Tr Tr
 Comparison of this equation: Z  Z 0   Z1

0 Pr 0 Pr
Z  1 B Z 1  B1
Tr Tr

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 28

Expand the equation results in:
(0) Pr (1) Pr
z  1 B  B
Tr Tr

 Pr 
IF z  1  Br 
T 
 THEN Br  B ( 0)  B (1)
 r 

(0) 1.6
B  0.083  0.422 / T r
To calculate B and
(0)

B(1), use:
(1) 4.2
B  0.139  0.172 / T r

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 29

Fig. 3.15 : Comparison of correlation for Z0. The virial-coefficient correlation is
represented by the straight lines: the Lee/ Kesler correlation, by the points. IN the
region above the dashed line the two correlations differ by less than 2%.
2006/2007 II BKF2413 Chemical Engineering Thermodynamics 30
Conditions of Appromixate Vialidity of the Ideal-Gas
Equation
 When the ideal-gas equation may be used?
 Fig 3.15 is a guide.

Fig. 3.16 : Region where Z0 lines between 0.98 and 1.02 , and the ideal-gas
equation is a reasonable approximation
2006/2007 II BKF2413 Chemical Engineering Thermodynamics 31
~~Examples~~
 In a case where air at 100 psia fills a SCUBA tank of 0.1 m3
volume at 25oC, what is the value of z?
Solution:
The critical properties of air can be well estimated by
the mole fraction of N2 (79%) and O2 (21%), yielding:
Tc = 132 K Pc = 37.4 bar  = 0.036
Calculate: B(0) = - 0.032 B(1) = 0.133 Br = - 0.027
As such, z = 1 + BrPr/Tr = 0.998

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 32

 Find the volume occupied by 23.2 g of n-butane at 258.3oC,
30 bar.
Solution:
 The molecular weight of n-butane is 58; there is 23.2/58 =
0.4 mol. The critical properties are:
Tc = 425.5 K Pc = 38.0 bar  = 0.201
Calculating Tr and Pr, then proceed to calculate B(0) and B(1)
yield B(0) = - 0.212, B(1) = 0.072 and Br = - 0.198
Then, z = 1 + (-0.198) x 0.79/1.25 = 0.875
The volume is then V = znRT/P = 515.6 cc

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 33

~~~More Example~~
 Example 3.10 (TEXTBOOK)
Determine the molar volume of n-butane at 510 K and 25 bar by each of
the
following:

(i) The ideal-gas equation.

(ii) The generalized compressibility-factor correlation.
(iii) The generalized virial-coefficient correlation.
Solution 3.10:
(a) By the ideal-gas equation,

RT 83.14510 
V    1,696.1cm 3 mol 1
P 25

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 34

(b) From values of Tc and Pc in App. B

510 25
Tr   1.200 Pr   0.659
425.1 37.96
Interpolation in Tables E. 1 and E.2 then provides:

Z0 = 0.865 Z1 = 0.038

Thus, by Eq. (3.54) with w = 0.200,

Z  Z  Z  0.865  0.200 0.038  0.873

0 1

and
ZRT 0.87383.14 510
V    1,480.7cm 3 mol 1
P 25
2006/2007 II BKF2413 Chemical Engineering Thermodynamics 35
 If Z1, the secondary term, is neglected, Z =Z0=0.865. This two-parameter
corresponding-states correlation yields V = 1,467.1 cm3 mol-1, which is less
than 1 % lower than the value given by the three-parameter correlation.
(c) Values of B0 and B’ are given by Eqs. (3.61) and (3.62):

B0 = -0.232 B1 = 0.059

Equations (3.59) and (3.58) then yield:

BPc
 B 0  B 1  0.232  0.200 0.059   0.220
RTc

from which V = 1,489.1 cm3 mol-1, a value less than 1% higher than
that given by the compressibility-factor correlation. For comparison,
the experimental value is 1,480.7.

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 36

3.7 GENERALIZED CORRELATIONS FOR
LIQUIDS
 Generalized equation are available for estimation of molar volumes
of saturated liquids. The simplest equation proposed by Rackett
is an example: sat 1Tr 0.2857
V  Vc Z c
 Lydersen , Greenkorn and Hougen developed a two-parameter
corresponding-states correlation for estimation of liquid
volumes. It provides a correlation of reduced r as a function of
reduced temperature
. and pressure. By definition,
 Vc where c is the density at the critical point
r  
c V

 r1 where V2 = required volume, V1 = known volume,

V2  V1
 r2 and ρr1, r2 = reduced densities read from Fig. 3.16

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 37

 Fig. 3.17 : Generalized density correlation for liquids.

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 38

Example 3.13

For ammonia at 310K , estimate the density of :

(a)The saturated liquid ;

(b)The liquid at 100 bar

Solution 3.13:

(a) Apply the Rackett equation at the reduced temperature,

310
Tr   0.7641
405.7
With Vc = 72.47 and Zc= 0.242 (from App. B),

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 39

 0.2359  0.2857
V sat
 Vc Z c 1Tr 0.2857
 72.470.242 3
 28.33cm mol 1

This compares with the experimental value of 29.14 cm3 mol-1,

and differs by 2.7%.

(b) The reduced conditions are:

100
Tr  0.764 Pr   0.887
112 .8
Substituting the value, r = 2.38 (from Fig. 3.17), and Vc into Eq.
(3.64)
gives:
Vc 72.47
V    30.45cm 3 mol 1
r 2.38
In comparison with the experimental value of 28.6
cm3 mol-1, this result is higher by 6.5%.

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 40

If we start with the experimental value of 29.14cm3 mol-1 for
saturated liquid at 310 K. Eq. below may be used. For the
saturated liquid at Tr = 0.764, r1 = 2.34 (from Fig. 3.17).
Substitution of known values into Eq. below gives:

 r1  2.34 
V2  V1  29.14   28. 65cm 3
mol 1

 r2  2.38 

This result is in essential agreement with the experimental value.

2006/2007 II BKF2413 Chemical Engineering Thermodynamics 41