Non-tabular approaches to

calculating properties of real

gases

The critical state

At the critical state (Tc, Pc), properties of
saturated liquid and saturated vapor are
identical
if a gas can be liquefied at constant T by
application of pressure, TTc.
if a gas can be liquefied at constant P by
reduction of T, then PPc.
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
v Tc

2 P
0

2
v T
c

Departures from ideal gas and the

compressibility factor
Pv
1
RT

For an ideal gas

One way of quantifying departure from
ideal gas behavior to evaluate the
compressibility factor (Z) for a true gas:

Pv
v
Z

RT videal

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

gases

The critical state and ideal gas

behavior
At the critical state, the gas is about to
liquefy, and has a small specific volume.
videal vtable
100%
vtable

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 (Pc, ,Tc).

Critical properties of a few

engineering fluids
Water/steam (power plants):
CP: 374o C, 22 MPa
BP: 100o C, 100 kPa (1 atm)

R134a or 1,1,1,2-Tetrafluoroethane (refrigerant):

CP: 101o C, 4 MPa
BP: -26o C, 100 kPa (1 atm)

Nitrogen/air (everyday, cryogenics):

CP: -147o C, 3.4 MPa
BP: -196o C, 100 kPa (1 atm)

Principle of corresponding states

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

Nelson-Obert generalized
compressibility chart

1954

Based
on curvefitting
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
P
constant temperature v 0
Critical isotherm has
a horizontal point of
P
P
inflection: v 0, v 0,
Compressibility factor (esp. at critical state
consistent with experiments on real gases.)
T

Tc

Tc

Some equation of states

Often
Two-parameter equations of state
based
on theory
Virial equation of states
Z=1+A(T)/v+B(T)/v2+. (coefficients can
be determined from statistical mechanics)
Multi-parameter equations of state with
empirically determined coefficients:

Beattie-Bridgeman
Benedict-Webb-Rubin Equation of State

Two-parameter equations of states

Examples:
Van der waals
Dieterici
Redlich Kwong

P RT / (v b) a / v 2
P

RT
a

exp

vb
RTv

RT
a

vb
T v (v b )

Parameters (a, b) can be evaluated from critical

point data using Pv 0, vP 0,
Van der Waals:
2

Tc

Tc

27 R 2Tc2
RTc
a
; b
; Zc 0.375
64 Pc
8 pc

Critical compressibility of real gases

First law in differential form,

thermodynamic definition of
specific heats