Chapter 3 Volumetric Properties of Pure Fluids UTAS

Thermodynamics I
ENCH2102
Chapter 3
Volumetric Properties of Pure Fluids
Dr Rajan
Thermodynamics I
ENCH2102
Chapter 3
Volumetric Properties of Pure
Fluids
2
University of Technology and Applied Sciences - ‫جامعة التقنية والعلوم التطبيقية‬
Volumetric Data or PVT Data
Thermodynamic properties, such as internal
energy and enthalpy, from which one
calculates the heat and work requirements
of industrial processes, are often evaluated
from volumetric data.
3
Volumetric Data or PVT
Relationship
• 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.
4
PVT - 3D diagram
5
PVT terminology
Saturation temperature: temperature at which vaporization
takes place at a given pressure (saturation pressure)

Saturation pressure = 0.1 MPa
Psat L
Example: water at 99.6oC
Or water at 0.1 MPa  Saturation temperature = 99.6 C
o
V
Vapor-pressure curve: relationship between saturation
T
temperature and saturation pressure
Subcooled liquid: material exists at temperature lower Superheated

than the saturation temperature at a given pressure
T Sat. L Sat. V
Saturated liquid: material exists as liquid at the saturated
saturation temperature and pressure Tsat
Saturated vapor: material exists as vapor at the subcooled

saturation temperature and pressure V (m3/kg)
Superheated vapor: material exists at temperature greater than the saturation
temperature.
Saturated water or saturated mixture: material exists as liquid + vapor at the
saturation temperature
3-6 I
Thermodynamics
P-T diagram
7
Critical Point
• Critical Point represented by Critical
temperature and pressure points.
• They are the maximum temperature and

pressure at which a pure chemical species
is observed to exist in vapor liquid
equilibrium.
8
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
9
Liquid, Gas and Fluid Regions
• A Phase is considered as Liquid if
vaporization results from pressure reduction
at constant Temperature.
• A phase is considered as Gas if

condensation from temperature reduction at
constant pressure
• In Fluid region, the behaviour is the

combination of liquid and gas phases.
10
PV Diagram
11
Saturation Pressure and
Temperature
• The pressure at which the liquid and vapor
phases coexist in equilibrium is called the
saturation pressure and the temperature
corresponding to this pressure is called
saturation temperature.
12
Superheated Conditions
• When the pressure is lowered to a value
less than the saturation pressure at
constant temperature or when the
temperature is increased above the
saturation temperature at constant
pressure, the vapor gets superheated.
13
Vapor and Gas
• If the temperature is less than the critical temperature,
the substance to the right of the saturated vapor line is
called vapor.
• A vapor can be condensed to a liquid at compression

at constant temperature or by cooling at constant
pressure.
• If the temperature is above the critical temperature,

the substance is called a gas.
• A gas can be condensed by cooling at constant

pressure only.
14
Tables of Thermodynamic Properties: Steam
tables
Thermodynamic Tables: give temperature, pressure, volume, enthalpy, internal
energy, and entropy in tables
Table F.1 (Page 716): gives properties of saturated steam (water)
• 1st and 2nd columns represent Tsat in oC and K, respectively.

• 3rd column represents the corresponding saturated pressure, Psat (kpa)
• 4th column: specific volume of saturated liquid, Vl (cm3/g), at Tsat
• 6th column: specific volume of saturated vapor, Vv (cm3/g), at the same Tsat
• 5th column: Vv – Vl = Vlv (cm3/g), at the same Tsat
• Next three columns: represent Ul, Ulv , and Uv (kJ/kg), at the same Tsat
• Next three columns: represent Hl, Hlv , and Hv (kJ/kg), at the same Tsat
According to the degrees of freedom, only one state variable

(normally either Tsat or Psat) needs to be specified for the two
phase region in order determine all other thermodynamic
properties
15
16
Superheated vapor
According to the degrees of freedom, for superheated vapor:
 = 1; N = 1; F=2-+N=2–1+1=2
 Two variables must be fixed in order to determine the intensive state

of the system, or in order to determine all other thermodynamic
properties. Normally these are temperature (T) and pressure (P).
Table F.2 (Page 722): gives properties of superheated steam (water)

For each P, large set of temperatures are given for determination of
thermodynamic properties
Tables are also available, in other texts, for compressed liquid (at different T
and P) and for saturated solids to determine thermodynamic properties
17
18
Determination of state of material
The steam table can be used to check for the state of material.
Recall the isothermal and isobaric PVT diagrams:
T2 < T1 < Tc < T

T2 < T1 < Tc < T
T
V (cm3/g)
• For a given P and T: If Psat (@ T) > P Material is superheated vapor
If Psat (@ T) < P Material is subcooled liquid
• For a given T and V: If Vv (@ T) < V Material is superheated vapor

If Vl (@ T) > V Material is subcooled liquid
If Vl < V < Vv Material is saturated steam
19
Home Work
Determine whether water at each of the following states is compressed liquid, a
superheated vapor or a mixture of saturated liquid and saturated vapor:
(a) T = 120oC & P = 150 kPa Get Psat and compare with P
(b) P = 0.3 MPa & V = 400 cm3/g Get Vl and Vv compare with V
(c) T = 160oC & V = 400 cm3/g
(d) T = 110oC & P = 200 kPa
(e) T = 300oC & V = 10 cm3/g
(f) T = 10oC & P = 5 kPa
20
Single-Phase Region
if V is considered a function of T and P
Dividing by V on both sides
21
Mathematical representation of
PVT behavior
• The thermodynamic state of a single
homogeneous fluid may be specified by
properties such as pressure, temperature
and volume.
• The mathematical expression called PVT

equation of state is a functional
relationship between these variables and
may be represented as
)0
f ( P,V , T 22
Equation of state - application
1. Ideal gas
2. Real gases
a) Virial equation of state
b) Cubic equation of state – two parameters
c) Compressibility factor equation
d) Cubic equation of state – three parameters
3. Liquids
1. Ideal gas

Ideal Gas
Ideal gas:
sufficiently dilute (low density)
molecules on average far apart
best at large V (low density)
occurs at low P and high T
rule of thumb - density less than 1/4 of critical density
For engineering purposes, all gases in the

neighborhood of atmospheric pressures are
treated as ideal.
25
Processes involving Ideal gases
• Constant Volume Process

• Constant Pressure Process
• Isothermal Process
• Adiabatic Process
• Polytrophic Process
26
Constant-volume process (isometric
process)
H   C P dT W    PdV  0
,
U   CV dT
Q  U   C v dT
27
Constant-pressure process (isobaric
process)
W   R(T2  T1 )
Q  H   C p dT
28
Constant-temperature (isothermal
process)
P  V 
Q   RT ln  2   RT ln  2 
 P1   V1 
V  P 
W   RT ln  2   RT ln  2 
 V1   P1 
U  H  0
29
Adiabatic process
• An adiabatic process is one for which there is no heat
transfer between the system and its surroundings;
PV   constant
 P1V1  P2V2  constant
 1  1
T2  V1   P2  
Hence, 
 
  

T1  2
V  1
P
Work of an adiabatic process is given by
 1  1
   
P1V1   P2    RT 
1   P  

W  1 
 

1

2


 1   P1    1   P1  
   
30
Adiabatic process
31
Polytropic process
PV n  cons tan t
Where n is the constant
Polytropic means "turning many ways:' polytropic

process suggests a model of some versatility.
If n = 0 , the process is constant pressure

If n = 1 , the process is isothermal
If n= ∞, the process is constant volume
If n = γ, the process is adiabatic.
Generally n varies from 1 to γ , meaning the process varies

between isothermal and adiabatic . 32
Real Gases
2 (a)Virial equations of state
Isotherms for gases and
vapours lying on the right
of of fig 2.3 are simple
curves for which V
increases as P
decreases. The product
PV can be expressed as
a power series in P:
PV  a (1  B ' P  C ' P 2  D ' P 3  ......)
33
Virial equations of state
' '
a, B , C , etc
are constants for a given
temperature
and chemical species
PV  RT (1  B ' P  C ' P 2  D ' P 3  ......)
34
Two forms of Virial Equation of
State - Compressibility factor
• Compressibility Factor is defined as
PV
Z 
RT
• Constants B’ & B; C’ & C; D’ & D are

related by
35
2(b) Cubic EOS – Two Parameters
• Virial equations cannot represent thermodynamic
systems where both liquid and vapor are present.
• Two parameters – when acentric factor is not taken

(or spherical shape is assumed)
• A "cubic" EOS is needed when vapour and liquid

are present:
(i) Van der Waals

(ii) Redlich Kwong
Cubic equations of State
(i) Van der Waals equation
 a 
 P  2 V  b  = RT
 V  a
27R 2 Tc2 RTc

a b
64Pc 8Pc
37
Redlich Kwong
(ii)
RT a
P  1/ 2
V  b T V (V  b)
38
2 (c) Compressibility factor equation
• Virial and cubic equations of state are accurate but not
convenient.
• A good compromise is a generalized compressibility
factor equation.
• According to the "Law of Corresponding States" a few
properties are the same for all gases when expressed
in terms of deviation from the critical point.
• Thus, a generalized compressibility factor chart can be used

to get z once we have the reduced temperature and
pressure
Law of Corresponding States
• All fluids, when compared at the same reduced
temperature and the reduced pressure, have
approximately the same compressibility factor
(Z) , and all deviate from ideal gas behavior to
about the same degree.
40
Generalised compressibility factor
graph
Moran & Shapiro

2(d) Cubic EOS – Three Parameters
• Acentric factor gives an

indication of the deviation
from spherical symmetry
in a molecule SF
• In simple fluids, in which

the molecules have
spherical symmetry, the
acentric factor is zero. It
is observed that in simple
fluids we have log10 sat
= −1 (Pr at sat = 0.7)

Cubic EOS – Three Parameters
In a general fluid, the acentric factor is defined
as

(i) Soave Redlich Kwong (SRK):
Modification of RK

(ii) Cubic EOS: three parameters -
Peng Robinson
RT a
P 
V  b V (V  b)  b(V  b)
a  a c (1   (1  Tr )) 2
0.45724 R 2Tc2
ac 
Pc
  0.37464  1.54226   0.26992  2
0.07780 RTc
b
Pc
Comparison of Two and Three
parameter corresponding EOS
Two parameters
• works well for simple fluids (small, nonpolar species
like Ar, N2, CH4, etc.)
Three parameters
• good for normal fluids (nonpolar or weakly polar
species, independent of size)
• simple fluids, paraffins, other weakly polar organic or
inorganic species
• can also be used to find virial coefficients

(ii) Redlich/Kwong equation
RT a
P 
V  b   
T V V  b 
0.42748 R 2Tc2 0.08664 RTc

a b
Pc Pc
47
Generalized Correlations for
Gases
Pitzer Correlations for the
Compressibility Factor
Combining these equations
48
Generalized Correlations for
Gases
49
3. Liquids
Correlation are available for estimating molar volumes of
saturated liquids like the Rackett correlation:
(1- T r )0.2857 sat Pr [1+ (1- T r )2/ 7 ]
V sat = V c .Z c Z = Z c
Tr
Two-parameter corresponding states correlation (Lydersen,

Greenkorn and Hougen) for estimating liquid volumes:
 Vc
r  
c V
Read from plot for

a given Pr & Tr

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Thermodynamics I

• Generally is given in the form of a phase diagram, in

• Understanding of such diagrams is essential to

Subcooled liquid: material exists at temperature lower Superheated

Saturated vapor: material exists as vapor at the subcooled

• They are the maximum temperature and

• When T > Tc and P > Pc

• A phase is considered as Gas if

• In Fluid region, the behaviour is the

• A vapor can be condensed to a liquid at compression

• If the temperature is above the critical temperature,

• A gas can be condensed by cooling at constant

• 1st and 2nd columns represent Tsat in oC and K, respectively.

According to the degrees of freedom, only one state variable

 Two variables must be fixed in order to determine the intensive state

Table F.2 (Page 722): gives properties of superheated steam (water)

Recall the isothermal and isobaric PVT diagrams:

T2 < T1 < Tc < T

• For a given T and V: If Vv (@ T) < V Material is superheated vapor

(c) T = 160oC & V = 400 cm3/g

(d) T = 110oC & P = 200 kPa

(e) T = 300oC & V = 10 cm3/g

(f) T = 10oC & P = 5 kPa

Dividing by V on both sides

• The mathematical expression called PVT

University of Technology and Applied Sciences - ‫جامعة التقنية والعلوم التطبيقية‬

For engineering purposes, all gases in the

• Constant Volume Process

Where n is the constant

Polytropic means "turning many ways:' polytropic

If n = 0 , the process is constant pressure

Generally n varies from 1 to γ , meaning the process varies

• Constants B’ & B; C’ & C; D’ & D are

• Two parameters – when acentric factor is not taken

• A "cubic" EOS is needed when vapour and liquid

(i) Van der Waals

27R 2 Tc2 RTc

• Thus, a generalized compressibility factor chart can be used

Moran & Shapiro

University of Technology and Applied Sciences - ‫جامعة التقنية والعلوم التطبيقية‬

• Acentric factor gives an

• In simple fluids, in which

University of Technology and Applied Sciences - ‫جامعة التقنية والعلوم التطبيقية‬

University of Technology and Applied Sciences - ‫جامعة التقنية والعلوم التطبيقية‬

University of Technology and Applied Sciences - ‫جامعة التقنية والعلوم التطبيقية‬

University of Technology and Applied Sciences - ‫جامعة التقنية والعلوم التطبيقية‬

0.42748 R 2Tc2 0.08664 RTc

Combining these equations

Two-parameter corresponding states correlation (Lydersen,

Read from plot for

University of Technology and Applied Sciences - ‫جامعة التقنية والعلوم التطبيقية‬

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