CHAPTER 3

VOLUMETRIC
PROPERTIES OF PURE
FLUIDS
Objectives
Introduce the concept of a pure substance.
Discuss the physics of phase-change processes.
Illustrate the P-v, T-v, and P-T property diagrams and P-v-
T surfaces of pure substances.
Demonstrate the procedures for determining
thermodynamic properties of pure substances from tables
of property data.
Describe the hypothetical substance ideal gas and the
ideal-gas equation of state.
Apply the ideal-gas equation of state in the solution of
typical problems.
Introduce the compressibility factor, which accounts for the
deviation of real gases from ideal-gas behavior.
Present some of the best-known equations of state.
Pure Fluids/ Substance
A substance that has a fixed chemical
composition throughout is called a Pure
Substance.
Pure Substance:
- N2, O2, gaseous Air
-A mixture of liquid and gaseous water is a
pure substance, but a mixture of liquid and
gaseous air is not.

PHASES OF A PURE SUBSTANCE
The molecules
in a SOLID are
kept at their
positions by the
large springlike
inter-molecular
forces.
In a solid, the attractive
and repulsive forces
between the molecules
tend to maintain them
at relatively constant
distances from each
other.
The arrangement of atoms in different phases: (a) molecules are at relatively fixed
positions in a solid, (b) groups of molecules move about each other in the LIQUID
phase, and (c) molecules move about at random in the GAS phase.
Phase-Change Processes of
Pure Substance
Compressed liquid or a subcooled liquid:
A liquid that is not about to vaporize.
Saturated liquid: A liquid that is about to
vaporize.
Saturated vapor: A vapor that is about to
condense.
Saturated liquid-vapor mixture: the liquid
and vapor phases coexist in equilibrium.
Superheated vapor: A vapor that is not
about to condense



2-1




T-v diagram for the heating process of water at
constant pressure.
Phase-Change Processes of
Pure Substance
Saturated temperature, Tsat: At a given pressure,
the temperature at which a pure substance
changes phase.
Saturated pressure, Psat: At a given temperature,
the pressure at which a pure substance changes
phase.
Latent heat: the amount of energy absorbed or
released during a phase-change process.
Latent heat of fusion: the amount of energy
absorbed during melting.
Latent heat of vaporization: the amount of energy
absorbed during vaporization.



Phase changes process
Macromedia 3.3
PVT BEHAVIOR OF PURE SUBSTANCES/ FLUIDS
The 1-2 line, also
known as sublimation
curve is where solid-
vapor is in equilibrium
The 2-C line, also known as
vaporization curve is where
liquid-vapor is in equilibrium
The 2-3 line, also known as
fusion curve is where solid-
liquid is in equilibrium
Triple point, three
phases exist in
equilibrium (F=0)
Critical point highest
combination of pressure and
temperature where the fluid
exist in liq-vap equilibrium
PV diagram
Boundaries in PT diagram becomes
region when illustrate with PV
diagram
Critical point becomes peak of the
curve
Triple point becomes horizontal line
Macromedia 3.4
Compressed liquid region
Saturated liquid line at boiling
temperature
Saturated vapor line at condensation
temperature
Superheated vapor region
T >Tc, the line do not cross the
boundary
Isotherms in sub-cooled/ compressed lliquid
region are steep, because liquid volumes
change little with large changes in pressure
SINGLE PHASE REGION
At single phase regions in PV diagram, there is a relation connecting P,V and T.
This relation known as PVT equation of state; f(P,V,T)=0
If V is considered as a function of T and P, then V=V(T,P)
ility compressib isothermal
T
V
V
ansivity Volume
T
V
V
dP
T
V
dT
T
V
dV
T
P
T P
k
o
o
|
o
o
o
o
o
o

|
.
|

\
|

|
.
|

\
|
|
.
|

\
|
+
|
.
|

\
|
=
1
exp
1
The combination will yield;
4 . 3 dP dT
V
dV
k | =
Because the isotherms on the left side of PV diagram are very steep, both
and are small.
Because of that, the liquid is known as incompressible fluid, where both
constants are equal to zero
However, this is just idealization, and in incompressible fluid, no equation of
state exist, since V is independent of T and P
If, we still want to calculate, for liquids, is positive, and is positive as
well. Integration of 3.4 yield
5 . 3 ) ( ) ( ln
1 2 1 2
1
2
P P T T
V
V
= k |
Check out Ex 3.1
Virial Equation of State
The coefficients a(T), b(T), c(T), and so on, that are
functions of temperature alone are called virial coefficients.
Ideal-Gas Temperature; Universal Gas Constant
Figure 3.4: Plot of PV vs. P for 4 gaseous at triple-
point temperature of water. The limiting value of
PV as P0 is the same for all of the gaseous.
PV* = a = f(T)
Limiting value (asterisk)
This properties of gaseous is the basis for establishing
an absolute temperature scale.

The simplest procedure to define Kelvin scale:
1. (PV)* = a RT
2. (PV)*
t
= R x 273.16K

( )
( )
*
*
*
*
16 . 273 /
16 . 273
/
t
t
PV
PV
K T
K
K T
PV
PV
=
=
|
|
.
|

\
|
3.
(3.9)
(3.8)
In the limit, P0, molecules separated by finite distance
Volumes becomes negligible compare with the total volume
of the gas, and intermolecular forces approach zero
These condition define an IDEAL GAS state & Eq. 3.9 establishes
the ideal-gas temperature scale
The proportionality constant R = universal gas constant
Through the use of conversion factors, R may be expresses in various units.
Commonly used values are given as above table.
2 Forms of the Virial Equation
Auxiliary thermodynamic property =
= Compressibility factor

Z = 1 + BP+CP
2
+DP
3
+
Z= 1 + B/V +C/V
2
+ D/V
3
+
Virial expansion = Eq 3.11 & Eq 3.12
B, C, D , B, C, D = virial coefficient
B = 2
nd
virial coefficient
C = 3
rd
virial coefficientetc
RT
PV
Z
(3.10)
(3.11)
(3.12)
Eq 3.11 & Eq 3.12
) 13 . 3 ( ' a
RT
B
B =
) 13 . 3 (
) (
'
2
2
b
RT
B C
C

=
) 13 . 3 (
) (
2 3
'
3
3
c
RT
B BC D
D
+
=
THE IDEAL GAS
Because the Eq 3.12 arise on account of molecular
interactions, the virial coefficients B,Cetc = 0 were
no such interaction to exist


Phase Rule = Internal energy of a real gas is a
function of pressure as well as of temperature.


RT PV or Z
RT PV or Z

= =
1
1
Macromedia 3.6
THE IDEAL GAS
Equation of state: Any equation that relates
the pressure, temperature, and specific volume
of a substance.
The simplest and best-known equation of state
for substances in the gas phase is the ideal-
gas equation of state. This equation predicts
the P-v-T behavior of a gas quite accurately
within some properly selected region.
R: gas constant
M: molar mass (kg/kmol)
R
u
: universal gas constant
Different substances have
different gas constants.
Ideal gas
equation of state
U = U(T) (Ideal gas) (3.15)
Implied Property Relations for
an Ideal Gas (f(T) only)
Heat Capacity for constant volume, Cv




Eq 2.11 applied to an Ideal Gas
) (
) (
T Cv
dT
T dU
T
U
Cv
v
= =
|
.
|

\
|
c
c
=
) ( ) ( T H RT T U PV U H = + = +
(3.1)
(3.17)
Implied Property Relations for
an Ideal Gas (f(T) only)
P
P
P
C
dT
T dH
T
H
C = =
|
.
|

\
|
c
c

) (
(3.18)
R C R
dT
dU
dT
dH
C
V P
+ = + = =
(3.19)
Heat Capacity for constant pressure, Cp


Useful relation between Cv & Cp
NOTE: This equation does not imply that Cp and Cv are themselves
constant for an ideal gas, but only that they vary with temperature in such a way
that their differences is equal to R
}
}
= A =
= A =
) 21 . 3 ( ) 21 . 3 (
) 20 . 3 ( ) 20 . 3 (
b dT C H a dT C dH
b dT C U a dT C dU
P P
V V
For any of state of an ideal gas, Eq 3.16 and Eq.3.18 lead to:
T
1
& T
2

a---b = Constant volume process
a---c & a---d constant volume
The graph show that the U=
}
dT C
V
Equation for Process
Calculation for Ideal Gas
) 25 . 3 ( ) 24 . 3 (
) 23 . 3 ( ) 22 . 3 (
P
dP
RT RdT dW
P
dP
RT dT C dQ
V
dV
RT dW
V
dV
RT dT C dQ
P
V
+ = =
= + =
Working equation of dQ and dW depend on which pair of these variables
is selected as independent

With P=RT/V,
With V=RT/P and Cv given by Eq 3.19, dQ & dW written as Eq.3.24 & Eq.3.25

With T=PV/R, the work is simply dW=-PdV, and with Cv given by Eq.3.19,
) 26 . 3 ( PdV
R
C
VdP
R
C
dQ
P V
+ =
Isothermal Process
Q=-W
) 27 . 3 ( ) ( ln ln
1
2
1
2
T const
P
P
R
V
V
RT W Q = = =
Isobaric Process
}
= A = ) 28 . 3 ( ) ( P Const dT C H Q
P
Isochoric Process
}
= A = ) 29 . 3 ( ) ( V Const dT C U Q
V
Adiabatic Process; Constant
Heat Capacities
V P P
V P
C C C R
C C
V
V
V
V
P
P
P
P
T
T
to lead Eq Eq to similar
V
V
T
T
V
RdV
C T
dT
V
dV
C
R
T
dT
/
2
1
1
2
/
1
2
1
2
/
2
1
1
2
: 26 . 3 . & 24 . 3 .
1
|
|
.
|

\
|
=
|
|
.
|

\
|
=
|
|
.
|

\
|
= = =
=
} }
) 30 . 3 (
) 30 . 3 ( . ) 30 . 3 ( .
/ ) 1 ( 1
c const PV
b const TP a const TV
=
= =

Also,
V
P
C
C

(3.31)
IMPORTANT: Eq 3.30 are restricted in application to ideal gases with
Constant Heat capacities undergoing mechanically reversible adiabatic
expansion or compression
For ideal gas, the WORK of any adiabatic closed-system process is given by:
T C U W
dT C dU dW
V
V
A = A =
= =
(3.32)
Because RT
1
= P
1
V
1
and RT
2
= P
2
V
2,

1 1
1 1 2 2 1 2

=

V P V P RT RT
W
(3.33)
Elimination of V
2
from Eq 3.33 by Eq 3.30c, valid for
mechanically reversible process, lead to:
( ) ( )
(
(

|
|
.
|

\
|

=
(
(

|
|
.
|

\
|

=

1
1
1
1
/ 1
1
2 1
/ 1
1
2 1 1

P
P RT
P
P V P
W (3.34)
Polytropic Process
) 37 . 3 ( 1
) 1 )( 1 (
) (
) 36 . 3 ( 1
1
) 35 . 3 (
) 35 . 3 (
) 35 . 3 (
/ ) 1 (
1
2 1
/ ) 1 (
1
2 1
/ ) 1 (
1
(
(

|
|
.
|

\
|

=
(
(

|
|
.
|

\
|

=
=
=
=

o o
o o
o o
o
o
o
o
o
P
P RT
Q
P
P RT
W
c const TP
b const TV
a const PV
Isobaric process
Isothermal process
Adiabatic process
Isochoric process
Polytropic Process
APPLICATION OF VIRIAL EQ.
All isotherms originate at Z=1 for P=0
RT
BP
RT
PV
Z + = = 1
(3.38)
Applied to vapors at sub critical temperature up to their saturation pressure
2
1
V
C
V
B
RT
PV
Z + + = =
When the virial equation is truncated to 3 terms, the appropriate form is:
(3.40)
CUBIC EQ. OF STATE
( ) ) (
) (
b V b V
T a
b V
RT
P
o c + +

=
2
V
a
b V
RT
P

=
1. The Van der Waals Equation of state
(3.41)
2. A Generic Cubic Equation of State
(3.42)
3. Determination of Eq-of State Parameters
) 44 . 3 ( 0 ) 43 . 3 ( 0
;
2
2
;
=
|
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
cr T
cr T
V
P
V
P
4. Theorem of Corresponding State: Acentric Factor
7 . 0
) log( 0 . 1
=

Tr
sat
r
P e (3.48)
NOTE: All fluid having the same value of , when compared at the same T
r

And P
r
have about the same value of Z, and all deviate from ideal gas behavior
To about he same degree
e
5. Vapor& Vapor-like Root of the Generic Cubic Eq of state
6. Liquid & Liquid-like Root of the Generic Cubic Eq of state
GENERALIZE
CORRELATION FOR GASES
GENERALIZE
CORRELATION FOR GASES
1. Pitzer Correlation for the
Compressibility Factor
2. Pitzer Correlation for the 2
nd
Virial
Coefficient
3. Correlations for the 3
rd
Virial Coefficient
4. Condition of Approximate Vlidity of the
Ideal-Gas Equation
GENERALIZE
CORRELATION FOR LIQUID
Summary
Pure substance
Phases of a pure substance
Phase-change processes of pure substances
Compressed liquid, Saturated liquid, Saturated
vapor, Superheated vapor
Saturation temperature and Saturation pressure
Property diagrams for phase change processes
The T-v diagram, The P-v diagram, The P-T
diagram, The P-v-T surface
The ideal gas equation of state
Is water vapor an ideal gas?
Compressibility factor
Other equations of state
Thank you
Prepared by,
NMJ