Non-tabular approaches to

calculating properties of real

gases
The critical state
At the critical state (T
c,
P
c
), properties of
saturated liquid and saturated vapor are
identical
if a gas can be liquefied at constant T by
application of pressure, TT
c
.
if a gas can be liquefied at constant P by
reduction of T, then PP
c.

the vapor phase is indistinguishable from
liquid phase
Properties of the critical isotherm
The SLL and SVL intersect on a P-v
diagram to form a maxima at the critical
point.
On a P-v diagram, the critical isotherm has
a horizontal point of inflexion.




0
c
T
P
v
c
| |
|
\ .
=
c
2
2
0
c
T
P
v
| | c
|
\ .
=
c
Departures from ideal gas and the
compressibility factor
For an ideal gas
One way of quantifying departure from
ideal gas behavior to evaluate the
compressibility factor (Z) for a true gas:


Both Z<1 and Z>1 is possible for true
gases






1
Pv
RT
=
ideal
Pv v
v
Z
RT
= =
The critical state and ideal gas
behavior
At the critical state, the gas is about to
liquefy, and has a small specific volume.
100%
ideal table
table
v
v
v
is very large
Z factor can depart significantly
from 1.
Whether a gas follows ideal gas is closely
related to how far its state (P,T) departs
from the critical state (P
c,
,T
c
).
Critical properties of a few
engineering fluids
Water/steam (power plants):
CP: 374
o
C, 22 MPa
BP: 100
o
C, 100 kPa (1 atm)
R134a or 1,1,1,2-Tetrafluoroethane (refrigerant):
CP: 101
o
C, 4 MPa
BP: -26
o
C, 100 kPa (1 atm)
Nitrogen/air (everyday, cryogenics):
CP: -147
o
C, 3.4 MPa
BP: -196
o
C, 100 kPa (1 atm)




Principle of corresponding states
(van der Waal, 1880)
Reduced temperature: T
r
=T/T
cr
Reduced pressure: P
r
=P/P
cr
Compressibility factor:
Principle of corresponding states: All fluids
when compared at the same T
r
and P
r

have the same Z and all deviate from the
ideal gas behavior to about the same
degree.

Generalized compressibility chart
1949
Fits
experimental
data for
various gases
Use of pseudo-reduced specific
volume to calculate p(v,T), T(v,p)
using GCC
Z
Nelson-Obert generalized
compressibility chart
1954
Based
on curve-
fitting
experimental
data
Equations of state
Some desirable characteristics of
equations of state
Adjustments to ideal gas behavior shoujd have
a molecular basis (consistency with kinetic
theory and statistical mechanics).
Pressure increase leads to compression at
constant temperature
Critical isotherm has a horizontal point of
inflection:
Compressibility factor (esp. at critical state
consistent with experiments on real gases.)

0
T
P
v
c
| |
s
|
c
\ .
2
2
0, 0,
c
c
T
T
P P
v v
| | c c | |
| |
c c
\ .
\
=
.
=
Some equation of states
Two-parameter equations of state
Virial equation of states
Z=1+A(T)/v+B(T)/v
2
+. (coefficients can
be determined from statistical mechanics)
Multi-parameter equations of state with
empirically determined coefficients:
Beattie-Bridgeman
Benedict-Webb-Rubin Equation of State

Often
based
on theory
Two-parameter equations of states
Examples:
Van der waals
Dieterici
Redlich Kwong

Parameters (a, b) can be evaluated from critical
point data using
Van der Waals:
2
/ ( ) / P RT v b a v =
2
2
0, 0,
c
c
T
T
P P
v v
| | c c | |
| |
c c
\ .
\
=
.
=
exp
a
RTv
RT
P
v b
| |

\
=
|
.
( )
RT a
v b
Tv
P
v b

+
=
2 2
27
; ; Z
64
0.375
8
c c
c
c c
R T RT
p
a b
P
= = =
Critical compressibility of real gases
First law in differential form,
thermodynamic definition of
specific heats