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
A substance
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
-A mixture
mixture of of liquid
liquid and
and gaseous
gaseous water
water isis aa
pure
pure substance,
substance, but but aa mixture
mixture ofof 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
A liquid
liquid that
that is
is not
not about
about toto vaporize.
vaporize.
 Saturated
Saturated liquid:
liquid: AA liquid
liquid that
that is
is about
about toto
vaporize.
vaporize.
 Saturated
Saturated vapor:
vapor: A A vapor
vapor that
that is
is about
about toto
condense.
condense.
 Saturated
Saturated liquid-vapor
liquid-vapor mixture:
mixture: thethe liquid
liquid
and
and vapor
vapor phases
phases coexist
coexist inin equilibrium.
equilibrium.
 Superheated
Superheated vapor:vapor: A A vapor
vapor that
that isis not
not
about
about toto condense
condense
 T-v diagram for the heating process of water at
constant pressure.
2-1
 Phase-Change
Phase-Change Processes
Processes of
of
Pure
Pure Substance
Substance
 Saturated
Saturatedtemperature,
temperature, TTsat
sat:: At
At aagiven
givenpressure,
pressure,
the
thetemperature
temperatureat atwhich
whichaapurepuresubstance
substance
changes
changesphase.
phase.
 Saturated
Saturatedpressure,
pressure,PPsatsat:: At
Ataa given
giventemperature,
temperature,
the
thepressure
pressureat at which
whichaapure
pure substance
substancechanges
changes
phase.
phase.
 Latent
Latent heat:
heat: the
theamount
amount of of energy
energyabsorbed
absorbedor or
released
releasedduring
during aaphase-change
phase-changeprocess.
process.
 Latent
Latent heat
heatofoffusion:
fusion: the
theamount
amount ofof energy
energy
absorbed
absorbed during
duringmelting.
melting.
 Latent
Latent heat
heatofofvaporization:
vaporization: the theamount
amount ofof 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

Triple point, three

phases exist in
The 1-2 line, also The 2-3 line, also known as
equilibrium (F=0)
known as sublimation fusion curve is where solid-
curve is where solid- liquid is in equilibrium
vapor 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  P  T T
1  V 
   Volume exp ansivity
V  T  P
1  V 
    isothermal compressibility
V  T T
 The combination will yield;

dV
  dT  dP 3.4
V

Because the isotherms on the left side of PV diagram are very steep, both β
and κ 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, β is positive, and κ is positive as

well. Integration of 3.4 yield

V2
ln   (T2  T1 )   ( P2  P1 ) 3.5
V1

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 P0 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 3.  PV *  T /K
 
* 

2. (PV)*t = R x 273.16K (3.8)  t  273.16 K
PV

T / K  273.16
 PV 
*

(3.9)
 PV  *t
•In the limit, P0, 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
PV
 Auxiliary thermodynamic property = Z (3.10)
 = Compressibility factor RT

 Z = 1 + B’P+C’P2 +D’P3 +…
(3.11)
 Z= 1 + B/V +C/V + D/V +…
2 3

 Virial expansion = Eq 3.11 & Eq 3.12 (3.12)

 B’, C’, D’ …, B, C, D = virial coefficient
 B’ = 2nd virial coefficient
 C’ = 3rd virial coefficient…etc
Eq 3.11 & Eq 3.12

B
B'  (3.13a )
RT
C  B2
C'  (3.13b)
( RT ) 2

D  3BC  2 B 3
D'  (3.13c)
( RT ) 3
 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 ideal-
gas 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
Different substances have
U = U(T) (Ideal gas) (3.15) different gas constants.
Implied Property Relations for
an Ideal Gas (f(T) only)
 Heat Capacity for constant volume, Cv

 U  dU (T ) (3.1)
Cv      Cv(T )
 T  v dT

 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
 H  dH (T ) (3.18)
CP      CP
 T  P dT
 Useful relation between Cv & Cp
dH dU
CP    R  CV  R (3.19)
dT dT

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)

• T 1 & T2
• a---b = Constant volume process
• a---c & a---d ≠ constant volume

The graph show that the ∆U= CV 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 dV
dQ  CV dT  RT (3.22) dW   RT (3.23)
V V
dP dP
dQ  C P dT  RT (3.24) dW   RdT  RT (3.25)
P P
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 (3.26)
R R
Isothermal Process
 Q=-W
V2 P2
Q  W  RT ln   R ln (const T ) (3.27)
V1 P1

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
C P / CV
dT 1 RdV T2  V1 
 T  CV  V  T1   V2 
similar to Eq.3.24 & Eq.3.26 lead to :
R / CP C P / CV
T2  P2  P2  V1 

 P  
V 

T1  1  P1  2 
Also,

TV  1  const. (3.30a) TP (1 ) /   const. (3.30b)

PV   const (3.30c)
 CP
  (3.31)
CV
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
W 
 1  1 (3.33)
 Elimination of V2 from Eq 3.33 by Eq 3.30c, valid for
mechanically reversible process, lead to:
  1 / 
P1V1  P2   RT  P    1 /  
W     1  1
 
2
 1 (3.34)
  1  P1     1  P1  


Polytropic Process
PV   const (3.35a )
TV  1  const (3.35b)
TP (1 ) /   const (3.35c )
( 1) / 
RT1  P2  
W     1 (3.36)
  1  P1  

( 1) / 
(   ) RT1   P2  
Q    1 (3.37)
(  1)(  1)  P1  

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 (3.38)
Z  1
RT RT
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 (3.40)
RT V V
 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   2P 
   0 (3.43)  2   0 (3.44)
 V T ;cr  V 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