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
Pure Fluids/
Fluids/ Substance
Substance
A
Asubstance
substance that
that has
has aa fixed
fixed chemical
chemical

composition
composition throughout
throughout is
is called
called aa Pure
Pure
Substance.
Substance.
Pure
Pure Substance:
Substance:
-- N
N2,2,O
O2,2,gaseous
gaseousAir
Air
-A
-Amixture
mixture of
of liquid
liquid and
and gaseous
gaseous water
water is
is aa
pure
pure substance,
substance, but
but aa mixture
mixture of
of liquid
liquid and
and
gaseous
gaseous air
air is
is not.
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
Phase-Change Processes
Processes of
of
Pure
Pure Substance
Substance
Compressed
Compressed liquid
liquid or
or aa subcooled
subcooled liquid:
liquid:

A
Aliquid
liquid that
that is
is not
not about
about to
to vaporize.
vaporize.
Saturated
Saturated liquid:
liquid: A
Aliquid
liquid that
that is
is about
about to
to
vaporize.
vaporize.
Saturated
Saturated vapor:
vapor: A
Avapor
vapor that
that is
is about
about to
to
condense.
condense.
Saturated
Saturated liquid-vapor
liquid-vapor mixture:
mixture: the
the liquid
liquid
and
and vapor
vapor phases
phases coexist
coexist in
in equilibrium.
equilibrium.
Superheated
Superheated vapor:
vapor: A
Avapor
vapor that
that is
is not
not
about
about to
to condense
condense

2-1

T-v diagram for the heating process of

water at constant pressure.

Phase-Change
Phase-Change Processes
Processes of
of
Pure
Pure Substance
Substance
Saturated
Saturatedtemperature,
temperature, TTsat
sat:: At
At aagiven
given pressure,
pressure,

the
thetemperature
temperatureat
atwhich
whichaapure
puresubstance
substance
changes
changesphase.
phase.
Saturated
Saturatedpressure,
pressure,PPsat
sat:: At
Ataa given
giventemperature,
temperature,
the
thepressure
pressureat
at which
whichaapure
puresubstance
substancechanges
changes
phase.
phase.
Latent
Latent heat:
heat: the
theamount
amount of
of energy
energyabsorbed
absorbed or
or
released
releasedduring
during aaphase-change
phase-changeprocess.
process.
Latent
Latent heat
heatof
offusion:
fusion: the
theamount
amount of
of energy
energy
absorbed
absorbed during
duringmelting.
melting.
Latent
Latent heat
heatof
ofvaporization:
vaporization: the
theamount
amount of
of energy
energy
absorbed
absorbed during
duringvaporization.
vaporization.

Phase changes process

Macromedia 3.3

PVT BEHAVIOR OF PURE SUBSTANCES/ FLUIDS

Critical point highest
combination of pressure and
temperature where the fluid
exist in liq-vap equilibrium

The 2-C line, also known as

vaporization curve is where
liquid-vapor is in equilibrium

The 1-2 line, also

known as sublimation
curve is where solidvapor is in equilibrium

Triple point, three

phases exist in
equilibrium (F=0)

The 2-3 line, also known as

fusion curve is where solidliquid is in 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
Superheated vapor region
Saturated vapor line at condensation
temperature
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)

V
V
dV
dT
dP

T
1 V
Volume exp ansivity

V T P

1 V

V T

isothermal compressib ility

The combination will yield;

dV
dT dP
V

3 .4

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

ln

V2
(T2 T1 ) ( P2 P1 )
V1

Check out Ex 3.1

3 .5

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 triplepoint temperature of water. The limiting value of
PV as P0 is the same for all of the gaseous.
Limiting value (asterisk)

PV* = a = f(T)
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

(3.8)

3.

PV *
T /K

*
PV
273.16 K
t

PV
T / K 273.16
PV *t

(3.9)

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+CP2 +DP3 +
Z= 1 + B/V +C/V + D/V +
2

Virial expansion = Eq 3.11 & Eq 3.12

B, C, D , B, C, D = virial coefficient
B = 2nd virial coefficient
C = 3rd virial coefficientetc

PV
Z
RT

(3.10)

(3.11)
(3.12)

Eq 3.11 & Eq 3.12

B
B'
(3.13a )
RT
C B2
C'
( RT ) 2

(3.13b)

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

(3.13c)

THE IDEAL GAS

Because the Eq 3.12 arise on account of molecular interactions, the virial coefficients B,C

etc = 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.

Z 1 or PV RT
Z 1 or PV RT

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 idealgas equation of state. This equation predicts
the P-v-T behavior of a gas quite accurately
within some properly selected region.
Ideal gas
equation of state

R: gas constant
M: molar mass (kg/kmol)
Ru: universal gas constant
U = U(T) (Ideal gas)

(3.15)

Different substances have

different gas constants.

Implied Property Relations for

an Ideal Gas (f(T) only)
Heat Capacity for constant volume, Cv

U
Cv

dU (T )

Cv (T )
dT

(3.1)

Eq 2.11 applied to an Ideal Gas

H U PV U (T ) RT H (T )

(3.17)

Implied Property Relations for

an Ideal Gas (f(T) only)
Heat Capacity for constant pressure, Cp

CP

dH (T )
CP
dT

(3.18)

Useful relation between Cv & Cp

dH dU
CP

R CV R
dT dT

(3.19)

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

For any of state of an ideal gas, Eq 3.16 and Eq.3.18 lead to:

dU CV dT

(3.20a )

U CV dT

(3.20b)

dH C P dT

(3.21a )

H C P dT

(3.21b)

T1 & T2
a---b = Constant volume process
a---c & a---d constant volume

The graph show that the U=

dT

Equation for Process

Calculation for Ideal Gas
Working equation of dQ and dW depend on which pair of these variables
is selected as independent
With P=RT/V,

dV
V
dP
dQ C P dT RT
P
dQ CV dT RT

dV
V

(3.22)

dW RT

(3.24)

dW RdT RT

(3.23)
dP
P

(3.25)

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,

CV
CP
dQ
VdP
PdV
R
R

(3.26)

Isothermal Process
Q=-W

V2
P2
Q W RT ln R ln
V1
P1

(const T ) (3.27)

Isobaric Process
Q H C P dT

(Const P) (3.28)

Isochoric Process
Q U CV dT

(Const V ) (3.29)

Adiabatic Process; Constant

Heat Capacities
dT
R dV

T
CV V

dT
1

T
CV

V1
RdV
T2

V
T1
V2

C P / CV

similar to Eq.3.24 & Eq.3.26 lead to :

T2

T1

P2

P1

R / CP

V1
P2

P1
V2

C P / CV

Also,

TV 1 const. (3.30a )
PV const (3.30c)

TP (1 ) / const. (3.30b)

CP

CV

(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:

dW dU CV dT
W U CV T

(3.32)

Because RT1 = P1V1 and RT2 = P2V2,

RT2 RT1 P2V2 P1V1

1
1

(3.33)

Elimination of V2 from Eq 3.33 by Eq 3.30c, valid for

mechanically reversible process, lead to:
P1V1 P2

W
1 P1

1 /

RT1

1
1

P2

P1

1 /

Polytropic Process
PV const

(3.35a )

TV 1 const

(3.35b)

TP (1 ) / const
RT1 P2

W
1 P1

(3.35c )
( 1) /

( ) RT1 P2

Q
( 1)( 1) P1

( 1) /

(3.36)

(3.37)

(3.34)

Polytropic Process
Isobaric process

Isothermal process
Adiabatic process
Isochoric process

APPLICATION OF VIRIAL EQ.

All isotherms originate at Z=1 for P=0

PV
BP
Z
1
RT
RT

(3.38)

Applied to vapors at sub critical temperature up to their saturation pressure

When the virial equation is truncated to 3 terms, the appropriate form is:

PV
B C
Z
1 2
RT
V V

(3.40)

CUBIC EQ. OF STATE

1. The Van der Waals Equation of state
RT
a
P
2
V b V

(3.41)

2. A Generic Cubic Equation of State

RT
a(T )
P

V b V b (V b)

(3.42)

3. Determination of Eq-of State Parameters

P

0 (3.43)
T ;cr

2P

2
V

0 (3.44)
T ;cr

4. Theorem of Corresponding State: Acentric Factor

1.0 log( Prsat )Tr 0.7

(3.48)

NOTE: All fluid 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 he same degree

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 2nd Virial
Coefficient
3. Correlations for the 3rd 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