Chapter 3

Volumetric Properties
of Pure Fluids


Objectives of Chapter 3
To apply the energy balance to a system of interest
requires knowledge of the properties of the system and
how the properties are related.

The objective of Chapter 3 is to introduce property relations
relevant to engineering thermodynamics.

We will focus on the use of the closed system energy
balance introduced in Chapter 2, together with the property
relations considered in this chapter.

Outline of chapter 3
PVT Behaviour
Equation of state
1. Ideal gas equations
2. Virial equations
3. Cubic equation of state
- van der Waals equation
- modified van der Waals equations
Generalised correlation
1. gas
2. liquid
PVT Behaviour
PVT relationship is between three important properties of
pure substances: pressure, specific volume, and
temperature.

Generally is given in the form of a phase diagram, in
which the different regions of phase state (solid, liquid,
and vapor and their combinations) are shown.

Understanding of such diagrams is essential to
thermodynamics because there will be many occasions
in which you will have to refer to a phase diagram in
order to obtain needed property information.
PVT - 3D diagram
PVT Diagrams
Red lines: isobars
Blue lines: isotherms
Green areas: two-phase regions
Yellow areas: single phase
regions
isochoric
Isothermal
Isobaric
P-T diagram
Fusion curve = melting curve
isochoric
Supercritical fluid region

When T > Tc and P > Pc
Properties are combination of liquid and gas
fluid
Density is close to liquid density but with higher
diffusivity and lower viscosity
Attractive in extraction as it evaporates easily
without leaving much residue
P-V Diagram
Isothermal
Saturation curve
T-V Diagram
Isobaric
C = Saturated liquid

E = Saturated vapour

Tc = boiling point
T-V Diagram
Red : saturated liquid curve

Green: saturated vapour curve

Meeting point = critical point
Subcooled region
Superheated region
(between boiling point
and supercritical region)

Eg: wet steam and super-
heated steam
Eg: specific volume
specific volume v - it could be any number between vf and vg

In the two phase region, the liquid phase is always saturated
liquid and the vapor phase is always saturated vapor.
The two phase mixture is simply a mixture of saturated liquid
and saturated vapor.
Quality
liquid vapor
vapor
total
vapor
m m
m
m
m
x
+
= =
Quality is the fraction of the total mass in a
vapor-liquid system that is in the vapor phase.

Quality - derivation
The total mass M of material in the vessel:
(1) M = ML + MV
Total volume V of the vessel
(2) V = V
L
+ V
V
Relation between specific volume v and total volume V
(3) V = vM
Now consider the liquid phase.
(4) V
L
= vfML
By the same argument, we can write for the vapor phase:
(5) V
V
= vgMV

Substituting (3), (4) and (5) into (2) and (1) yields:
(6) v = {MV/(MV + ML)}vg + {ML/(MV + ML)}vf

At this point the quality x is defined as

(7) x = M
V
/(M
V
+ M
L
)

Equation of state (EOS)
PVT data can be measured using Beattles
apparatus

PVT data can be fitted to algebraic equations called
equation of state.

Equations are mostly obtained empirically and very
few from molecular theory

Advantage of EOS: data reduction during
calculations
Equation of state

Relates PVT of pure homogeneous fluid in equilibrium state

Previously - Boyle Law
- Charles Law
- Daltons Law
- Van der Waals
- Ideal Gas Law

In the gas region, when pressure is decreased and
temperature is increased Ideal Gas behaviour can be
considered

As behaviour moves away from ideal gas, various EOS are
derived depending on properties



1) The Ideal Gas constant volume
Definition for ideal gas: simplified model of real gas behaviour
1) PV=RT
2) U = f (T) only (if no intermolecular force exist)

Constant volume (Isochoric)

The Ideal Gas constant pressure
Constant pressure (Isobaric)
The Ideal Gas constant temperature
Constant temperature (Isothermal)








The Ideal Gas constant heat
Adiabatic

Continued
No heat
transfer
between
system and its
surroundings
The Ideal Gas 3 adiabatic relationships
T and V
T and P
P and V
Polytrophic process
Polytropic processes are internally reversible. Useful in
Carnot cycle calculations where ideal gas is assumed.
Some examples are vapors and perfect gases in many non-
flow processes. The polytrophic obeys:

PV
o
= constant

o=0 P=constant isobaric process.
o=infinity v=constant isochoric process.
o=1 Pv=constant isothermal process for an
ideal gas.
o= reversible adiabatic process for an ideal
gas.

Polytrophic process
The Ideal Gas polytrophic process
Polytropic process adiabatic reversible process

More polytropic equations: textbook pg 78-79 add into your notes!!!
Ideal gas: example
An ideal gas undergoes following reversible processes in a closed system:
(a) From 70
o
C and 1 bar, it is compressed adiabatically to 150
o
C.
(b) The gas is cooled from 150
o
C to 70
o
C at constant pressure.
(c) The gas is expanded isothermally to its original state.
Calculate W, Q, AU and AH for each of the processes and for the entire
cycle.Take C
v
= 3/2 R
Ideal gas: solution
Adiabatic, Q = 0
Ideal gas: solution
For
ideal
gas
Ideal gas: solution
AU = CvdT
AH = CpdT
Both are zero as the
start and end point is
the same. Q = -W
Ideal gas: irreversible
Repeat calculations for the same state changes but accomplished
irreversibly. Assume that the efficiency of each process is 80% compared
with the equivalent reversible operation.

Solution: The property changes for the steps will be the same (i.e. AU and
AH are the same as for reversible). However Q and W are not

Irreversible: solution
Work done on system
Work done by system
Why not divide?
because the work
should be less
Compare reversible and irreversible
What is observed?
Even though irreversible step has 80% efficiency,
Total work (883/167 = 5.2) is five times more!
2) Virial equations
The virial equation is important because it can be
derived directly from statistical mechanics.

Virial equation is expressed as a dimensionless
ratio, called compressibility factor, Z

Z= pV/RT as a power series in density (reciprocal
volume)

Extended parameters B and C are called 2nd
and 3rd virial coefficients (functions of T) and
increases accuracy

Used mostly for low to moderate pressures

Virial equations


Virial Equation is used when:
1) Series converges rapidly - not more than 2 or 3 terms are used
eg: during low pressure
2) Used for VLE correlations and predictions
Where B, C, D are virial coefficients

For Ideal Gas, Z = 1, as PV = RT
Virial equations applications
For cases when convergence is rapid, simplification is
carried out
P 0, tangent line can be applied,
2
0
1 1
' 1
'
V
C
V
B
RT
BP
RT
PV
Z
P B Z
B
P
Z
P
+ + = + = =
+ =
=
|
.
|

\
|
=
o
o
Validity: 1) Vapours at subcrticial temperatures up to their
saturation pressures
2) Gases with low pressure (several bars)
3) Cubic* equation of state
1) Van der Waals equation






a = Attractive forces between molecules
b = Correction for volume occupied
by the molecules
*Cubic refers to the volume
Validity: For T>Tc the van der Waals equation is an
improvement of the ideal gas law. For lower temperatures
the equation is reasonable for the two phase state at low
pressure
2) Modified van der Waals equation
Van der Waals: rough approximate of the two
phase region

Starting point for the development of many
equations representing PVT data in this region

Some modifications:
a) Redlich-Kwong
b) RK-Soave
c) Peng-Robinson
2. (a) Redlich and Kwong Equation


Validity:
Adequate for calculation of gas phase properties
when the ratio of the Pr< 0.5 Tr or
*Note Pr = P/Pc and Tr = T/Tc
(b) Redlich-Kwong-Soave Equation
The o function was devised to fit the vapor pressure
data of hydrocarbons and the equation does fairly well
for these materials.
(c) Peng-Robinson Equation
The equation provides reasonable accuracy near the critical point,
particularly for calculations of compressibility factor and liquid density

The equation performance is similar to the Soave equation, although it
is generally superior in predicting the liquid densities of many
materials, especially nonpolar ones

The equation should be applicable to all calculations of all fluid
properties in natural gas processes

Acentric Factor

Van der Waals and Redlich-Kwong: two parameters Tr and Pr

Soave-RK and Peng Robinson: three parameters Tr, Pr and
acentric factors o (Tr, e)

The acentric factor, e is defined as the difference evaluated
at Tr=0.7 :




Further numerical assignments for parameters: Table 3.1 pg 98
Values for w, Tc, Pc, Vc, etc can be obtained from App. B
Generalized Correlation
Equations where Z (dimensionless, reduced quantity) is
expressed as reduced temperature (Tr) and reduced pressure
(Pr) generalised correlations

Why? Because of general application to all liquid and gas:
All fluids, when compared at the same Tr and Pr have
approximately the same compressibility factor, and all
deviate from the ideal gas behaviour to about the same
degree.

Compressibility factor, Z = PV/RT = Z (Tr, Pr, Zc)

Generalised correlation - Gas
Most popular type: Pitzer correlation

Uses compressibility factor, Z and second virial coefficient,
B
Values for Zo and Z1 (functions of Tr and Pr, can be referred from the
Lee Kesler Tables in App E1-E4 through interpolation)

Validity:
1) Non-polar or slightly polar gases
Example: CO2, 02, H2, N2 and hydrocarbons
2) Low to moderate pressures
Generalised correlation - Gas
Pitzer correlation for the second virial coefficient

Objective: simplify calculations as compared to Zo and Z1

only T of functions are B and B
T
B and
T
B where
B B B
RT
BP
B t coefficien virial ond reduced the where
T
P
B Z
r
r r
c
c
r
r
1 0
2 . 4
1
6 . 1
0
1 0
172 . 0
139 . 0
422 . 0
083 . 0

, sec

1
= =
+ =
=
+ =
e
For the third virial coefficient, refer to pg 103 of the textbook
Examples: EOS problems
Problem 3.10

Determine the molar volume of n-butane at 510K and
25 bar using the following methods:

a) The ideal gas equation
b) The generalised compressibility-factor correlation
c) The generalised correlation for



B

Problem 3.10 (a)

Ideal gas law: PV = RT
Problem 3.10 (b)
Generalised compressibility factor correlation
Problem 3.10(b)
Problem 3.10(c)
2 . 4
1
6 . 1
0
1 0
172 . 0
139 . 0
422 . 0
083 . 0

1
r r
c
c
r
r
T
B and
T
B where
B B B
RT
BP
B where
T
P
B Z
= =
+ =
=
+ =
e
Examples of EOS problems
Question 3.11:

What pressure would be generated if 1 1b-mol
methane were stored in a volume of 2 ft
3
at 122
o
F.
Make use of :

(a) The ideal-gas law
(b) The Redlich-Kwong equation
(c) A generalized correlation

3.11 (a) ideal gas law
3.11(b) Redlich-Kwong
From Equations in pg 94 and App B1 (Tc and Pc),
3.11(c): A generalised correlation

We have the option of compressibility factor Z method or
virial correlation B.

Which should we use?
- Check pressure value small or large?
- Methane is non-polar

Looking at (a) & (b) answer, P is rather high (moderate)
and the gas in non-polar,
So we can use either one of the generalised correlation

So let us try using Z method: P=ZRT/V
3.11(c): A generalised correlation
As P is unknown, Pr cannot be determined but Pc can be
obtained for methane in App B1



Start assuming values for Z, start with Z = 1,
Use properties of Pr and Tr based on Z=1
Compare with Z = Zo + eZ1.(Eq 3.57)
Stop when guessed Z is the same as Z in (Eq 3.57)
3.11(c): A generalised correlation
Z = 0.89 gives the equivalent results
Discussion
1) Both Redlich Kwong and generalised correlation gave the
same results = 189 atm
2) This is similar to experimental value
3) Ideal gas equation gave a result almost 15% higher.
Optionally you can try the second virial generalised correlation
Generalized Correlation for Liquids
Though molar volumes of liquids can be estimated by generalized cubic
equations of state, result are not very accurate for saturated liquids.

Generalized equations available for estimating molar volumes of
saturated liquids.

By Rackett






Only critical constant data is required

] ) 1 ( 1 [
7 / 2
Tr
c
r
r
Z
T
P
Zsat
+
=
Fig 3.16 : Generalised density
correlation for liquids
Two parameter corresponding-states correlation for liquid volume estimation
Saturated
Liquid
Example of EOS problems
Question 3.13

For ammonia at 310K, estimate the density:
(a) The saturated liquid
(b) The liquid at 100 bar
Phase: liquid/gas?
Bond: polar/non-polar?
3.13(a) saturated liquid
Data can be found in Appendix Table B.1 for Tr, Vc and Zc
3.13(b) liquid at 100 bars
You can use two methods by using Fig 3.16
From notes, 1
st
option:







1)
r2
r1
V1 V2
ns calculatio liquid saturated
using

=
=
from data volume e approximat ely alternativ or
V
V
r
C
2)
Additional notes:
Relates PVT of pure homogeneous fluid in equilibrium state
Volume expansivity, |
Isothermal compressibility, K