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Lecture 3a

Lecture 3a: Thermal Equations of State -

Non-Ideal & Tabular Form
Non-Ideal Thermal Equations of State
The ideal gas law is not a good predictor of the P − v − T behaviour of gases when

• the gas has high enough density that molecular interaction forces become large and
the molecules occupy a significant portion of the volume; this happens near the
vapour dome typically, or
• the temperature is high enough to induce molecular dissociation (e.g. N2 + N2 ⇌ 2N +
N2)

One alternative is a corrected thermal equation of state.

van der Waals

The van der Waals equation is an equation of state for a fluid composed of particles that
have a non-zero volume and a pairwise attractive inter-particle force (the van der Waals
force). It was derived in 1873 by Johannes Diderik van der Waals, who received the Nobel
Prize in 1910 for "his work on the equation of state for gases and liquids". The equation is
based on a modification of the ideal gas law and approximates the behavior of real fluids. For
the van der Waals equation of state, one has

RT a
P= − ,
v−b v 2

2
27 2 T c 1 T
with a= R , b= R c
64 Pc 8 Pc

Redlich-Kwong
The Redlich–Kwong equation of state is an empirical, algebraic equation that relates
temperature, pressure, and volume of gases. It is generally more accurate than the van der
Waals equation and the ideal gas equation at temperatures above the critical temperature. It
was formulated by Otto Redlich and Joseph Neng Shun Kwong in 1949. The Redlich–Kwong
equation has undergone many revisions and modifications, in order to either improve its
accuracy in terms of predicting gas-phase properties of more compounds, as well as in better
simulating conditions at lower temperatures, including vapor-liquid equilibria. For the
Redlich-Kwong equation of state, one has:

RT a
P= −
v−b v (v +b) √ T
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Lecture 3a

2T 5c /2 Tc
with a=( 0.42748 ) R , b=(0.08664) R
Pc Pc

Compressibility factor
In some cases, more detail is needed to capture the behaviour of the gas, especially near the
vapour dome. Another commonly used approach to capturing this behaviour is to define the

• COMPRESSIBILITY FACTOR: the deviation from idealrity of a gas as measured by

Z=Pv /RT

Figure 3.1: Compressibility of Nitrogen.

For ideal gases, Pv=RT , so Z=1. Experiments show the behaviour of real gases, and this
can be presented in graphical form, as shown for N2 in Fig. 3.1. Note

• For all T , Z → 1as P → 0. Thus, one has ideal gas behaviour at low pressure
• ForT > 300 K , Z ∼1 for P<10 MPa.
• Hold at P=4 MPa and decrease temperature from300 K; we see Z decrease below
unity. Now
Pv P P
Z= = , ρ=
RT ρRT ZRT

Since Z<1, the density ρ is higher than we would find for an ideal gas with Z=1.
Thus, in this region, there is an attractive force between molecules.
• For P>30 MPa, we find Z>1. Thus, a repulsive force exists in this regime. The forces
are complicated.

Note that generalized compressibility charts have been developed for general gases. These
are based on the so-called reduced pressures and temperatures, Pr and T r, where
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P T
Pr = ,T r=
Pc Tc

The reduced pressure and temperature are dimensionless. Values with the c subscript are the
critical constants for the individual gases. Appendix A gives generalized compressibility
charts.

Tabular thermal equations of state

Often equations are too inaccurate for engineering purposes. This is generally because we
may be interested in behaviour under a vapour dome. Consider that the surface for steam is
well represented by that shown in Fig. 3.2.

Figure 3.2: P–v–T surface for a substance that (a) expands on freezing (b) contracts on freezing.

In such cases, one should use tables to find a third property, given two independent
properties. We can say that the thermal equation of state is actually embodied in the tabular
data.

We lay down some rules of thumb for this class:

• If steam, use the tables.

• If air or most other gas, use the ideal gas law, but check if the pressure is high or the
properties are near the vapour dome, in which case use compressibility charts or non-
ideal state equations.

Let us look at how the tables are organized.

Saturated liquid-vapour water, temperature tables

For water, the most important table is the saturated steam table. If the water is a two-phase
mixture, tables of this type must be used as the equation of state. Recall, for two-phase
mixtures, pressure and temperature are not independent thermodynamic variables. Two
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Lecture 3a

properties still determine the state, but quality x is now important. So for two-phase mixtures
we allow

• T =T (v , x) ,
• P=P(v , x ) ,∨¿
• v=v (T , x ) ,

for example. But P ≠ P(T , v ) as for ideal gases. Consider the structure of saturation tables, as
shown in Table 3.1. Data from the steam tables is sketched in Fig. 3.3. We have the notation:

f =¿ Saturated liquid, v=¿ Saturated vapour

Table 3.1: Saturated liquid-vapour water tables, temperature entry

We define v fg as

v fg ≡ v g −v f

Recall the quality x is

mvap
x=
mtotal

Consider a mass of fluid m in total volume V. We

must have

V =V liq +V vap ,

m=mliq + mvap Figure 3.3: Vapor dome for H2O with data
for v f , v g , and v fg atT =15 ℃ .
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Now, use the definition of specific volume and analyze to get

mv=m liq v f +m vap v g ,

mliq m vap
v= vf+ v ,
m m g

m−m vap m vap

v= vf + v ,
m m g

v=(1−x)v f + x v g ,

v=v f + x (v
⏟ ¿ ¿ g−v f ) . ¿
¿ v fg

We get the final important results

v=v f + x v fg

v −v f
x=
v fg

Saturated liquid-vapour water, pressure tables

Sometimes we are given the pressure of the mixture, and a saturation table based on the
pressure is more useful. An example of a portion of such a table is shown in Table 3.2.

Table 3.2: Saturated liquid-vapour water tables, pressure entry

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Superheated water tables

The superheat regime is topologically similar to an ideal gas. For a superheated vapour, the
quality x is meaningless, and we can once again allow pressure and temperature to be
independent. Thus, we can have v=v (T , P). And the tables are in fact structured to give
v(T , P) most directly. An example of a portion of such a table is shown in Table 3.3. This
portion of the superheated tables focuses on a single isobar, P=10 kPa. At that pressure, the
saturation temperature is 45.81 ℃ , indicated in parentheses. As long as T > 45.81 ℃, we can
use this table for P=10 kPa water. And for various values of T > 45.81 ℃ , we find other
properties, such as specific volume v, and properties we have not yet focused on, internal
energy u, enthalpy h, and entropy s.

Table 3.3: Superheated water tables

Compressed liquid water tables

Liquids truly have properties which vary with both T and P. To capture such variation, we
can use compressed liquid tables as an equation of state. If compressed liquid tables do not
exist, it is usually safe enough to assume properties are those for x=0 saturated liquid at the
appropriate temperature.

Saturated water, solid-vapour

Other types of saturation can exist. For example, below the triple point temperature, one can
have solid water in equilibrium with water vapour. The process where ice transforms directly
to water vapour is known as sublimation. Saturation tables for ice-vapour equilibrium exist as
well.

Tables for other materials

For many materials similar tables exist, e.g., ammonia, NH3, superheated ammonia vapour.
Other tables in BS, include those for carbon dioxide, CO2, a modern refrigerant, R-410a,
another common refrigerant, R-134a, diatomic nitrogen, N2, and methane, CH4.