CE304, Spring 2014

Lecture 5

Volumetric Properties of Pure Fluids, part 3

Overview:

Virial equations of state an extension of the ideal gas law

o A series expansion of the compressibility
o 2-term virial equation
o 3-term virial equation

Cubic equations of state describing both vapor and liquid phases

o The van der Waals equation of state
o The generic cubic equation of state
o Relating EOS parameters to critical properties of a fluid

Virial Equations of State:

For gases, we know that at constant temperature, the product of pressure and specific volume is
approximately constant. Therefore, we might try to write an equation of state for gases that looks
like:
PV a bP cP 2 dP 3 ...

where the coefficients a, b, c, etc. are functions only of temperature (and not of pressure). This is
an infinite series, but if the PV product is a weak function of pressure, then it can be truncated
after a few terms. We could also write it as

PV a 1 B ' P C ' P 2 D ' P 3 ...

where we have simply re-defined the constants as b = aB', etc.

It turns out that a in the above equation is the same temperature-dependent function for all gases,
though the other constants are, in general, different for each particular gas. Experimentally, as
the pressure becomes very small (mathematically, in the limit that P goes to zero) the pressurevolume product (PV) goes to the same value for all gases. This is used to establish the ideal gas
temperature scale and, in turn, the value of the Universal Gas Constant. If we denote the gasindependent value of PV as the pressure goes to zero as (PV)*, then we can define the ideal gas
temperature scale by assigning the quantity (PV)* to be proportional to temperature

PV * a RT
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Lecture 5

where the proportionality constant is the Universal Gas Constant. R is then defined by setting the
triple-point of water to be at T = 273.16 K and using the experimental value of (PV)* at the
triple-point temperature of water, which is (PV)* = 22711.8 cm3 bar mol-1. This gives
R

22711.8
83.1447 cm3 bar mol-1 K -1 8.31447 m3 Pa mol-1 K -1 8.31447 J mol-1 K -1
273.16

So, this gives us the first term in the virial equation of state - the pressure (and specific volume)
independent term that is the same for all gases. Because it will always be the same, we can move
it to the other side of the equation and write
Z

PV PV

1 B ' P C ' P 2 D ' P3 ...

RT
a

We define Z as the compressibility (also called the compressibility factor), which is equal to 1
for an ideal gas. Variations in Z away from 1 indicate non-ideal behavior. Often, the virial
equation of state is written as an infinite series expansion in inverse molar volume (molar
density) rather than in pressure, in which case the virial coefficients are different.
Z

PV
B C
D
1 2 3 ... 1 B C 2 D 3 ...
RT
V V
V

With some mathematical manipulation, we could relate the two forms of the virial coefficients as
B'
C'

B
RT
C B2

RT 2

and so forth.
In either form (volume-expansion or pressure-expansion) the virial equation will only be useful
for practical applications when the series converges within a few terms. This is true both because
the computations would become inconvenient and because only the first few coefficients are
likely to be available from experiments. So, for practical applications, we will truncate these to a
one-, two-, or three-term form. The one-term form, in which we keep only the first term, is the
ideal gas law:
Z

PV
1
RT

Truncating the pressure-expansion version after two terms gives

Z

PV
BP
1 B'P 1
RT
RT

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Lecture 5

where, in the second version, we have substituted B '

B
. Alternatively, we could truncate
RT

volume expansion as
Z

PV
B
1
RT
V

but the other expression in terms of P is more convenient and more commonly used.
We could also truncate the volume expansion after 3 terms to obtain a 3-term virial equation:
Z

PV
B C
1 2
RT
V V

This equation gives P in terms of V directly, but is cubic in V and therefore if one wants to solve
for V, one generally does so iteratively. Remember that the coefficients B and C are temperature
dependent, and therefore the solution for T in terms of P and V (which we usually don't want to
do anyway) may be simple or complex depending on the temperature dependence of B and C.
Virial coefficients beyond the 3rd virial coefficient are rarely known. If we look at a plot of the
compressibility of a typical substance like this one for CO2, which I've prepared from data
downloaded from the NIST WebBook, we can get an idea of the range over which a 1, 2, or 3term virial expansion may be appropriate. A similar plot for methane is given on p. 87 of SVNA.
Compressibility of CO2
1.4
1.3

Z = (PV)/(RT)

1.2

600 K

1.1
1

400 K
0.9
0.8
0.7
0.6
0

10

20

30

40

50

60

70

80

90

100

Pressure (MPa)

Here is the same plot with the different truncations of the virial equation superimposed on it.

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Lecture 5

Compressibility of CO2
1.4

600 K, 3-term
1.3

600 K, actual

Z = (PV)/(RT)

1.2
1.1

1-term
1
0.9

600 K, 2-term
0.8

400 K, actual
0.7

400 K, 2-term and 3-term

0.6
0

10

20

30

40

50

60

70

80

90

100

Pressure (MPa)

The values of the virial coefficients are obtained from the slope and curvature of the curves as P
goes to zero:
B'
C'

dZ
dP

P 0
2

1d Z
2 dP 2

P 0

For this particular case, we see that at 400 K, the 3-term expansion doesn't work any better than
the 2-term expansion, and both are good to about 10 or 15 MPa (100 to 150 atm). At 600K, the
2-term expansion is only good to about 10 MPa, but the 3-term expansion is good out to more
than 50 MPa. Clearly both the values of the virial coefficients and the range over which a given
expansion is useful depend on temperature.
For precise fitting of measured PVT data, one can use an extended virial equation in which
additional terms are added to the 3-term virial expansion to allow more flexibility in data fitting.
An example is the Benedict/Webb/Rubin (BWR) equation of state:

RT B0 RT A0 C0T 2 bRT a a
c

6 3 2 1 2 exp 2
2
3
V
V
V
V
V T V
V

This has 8 parameters, and some of these are usually taken to have additional temperature
dependence. We will not make use of the BWR equation or other similar many-parameter
empirical equations of state in this course. However, in cases where the parameters are available,
they can provide high accuracy.

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Lecture 5

Example 3.8 from SVNA

Cubic Equations of State:
The ideal gas equation and various virial expansions are most applicable to gases, or supercritical
fluids at gas-like densities (that is, with compressibility relatively close to 1). There are many
situations where one requires an equation of state that describes both the liquid and the vapor
phase of a substance. The simplest and most widely used of such equations are cubic equations
of state. By cubic, we just mean that they are cubic polynomials in the specific volume. The first
(historically) and simplest of these is the van der Waals equation of state.
The van der Waals Equation of State:
This was the first practical cubic equation of state, and it is:
P

RT
a
2
V b V

where a and b are positive. If a and b were both zero, this would become the ideal gas equation
of state.
Some general features of cubic equations of state are illustrated for the van der Waals EOS as
plotted for CO2 below.
van der Waals EOS for CO2
250

Pressure (bar)

200

150

600 K
400 K

100

300 K
50

250 K
200 K

0
0

200

400

600

800

1000

1200

1400

Volume (cm3/mol)

For this, and all cubic equations of state, there is always a single pressure corresponding to a
given volume (at any temperature), but there may be either one or three volumes corresponding

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Lecture 5

to a given pressure. For temperatures above the critical temperature, there is a single volume for
a given pressure (or at least only a single physically meaningful volume, which must be greater
than b). For temperatures below the critical temperature, there are 3. The smallest corresponds to
the liquid phase, while the largest corresponds to the vapor phase.
The generic cubic equation of state:
There are many possible equations of state (and many have been proposed) that have the same
general form as the van der Waals equation of state. An important group of these have the form
P

a T
RT

V b V b V b

In this generic form for a cubic equations of state, a is a function of temperature (as shown
explicitly above) and b is a constant (independent of temperature). a and b are both substance
specific (different for each fluid). The other two constants, and are pure numbers (they don't
have units) and are the same for all fluids for a given equation of state, but different for different
equations of state.
If a is taken to be constant with respect to temperature and if and are both set to zero, this
reduces to the van der Waals equation of state. Several other commonly used cubic equations of
state are obtained by specifying different functional forms for a(T) and different values of and
.
Determination of equation of state parameters:
If one has a good set of PVT data for a substance, then the parameters in the equation of state can
be determined directly by fitting the equation to the data (non-linear regression). However, more
often the equation of state parameters are estimated based on the critical properties of the
substance. To do this, we note that the isotherm at the critical temperature has a point of
inflection at the critical point. That is, its first and second derivatives are both zero:
d 2P
dP

0 at the critical point

dV T dV 2 T

Taking these derivatives of the generic cubic equation of state gives

a T
a T
RT
dP

2
2
dV T V b
V b V b V b 2 V b
d 2P
2a T
2a T
2a T
2 RT

2
3
3
2
2

V b V b V b V b V b 3 V b
dV T V b

Setting these equal to zero at the critical point gives

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CE304, Spring 2014

RTc

Vc b

Lecture 5

RTc

Vc b 3

a Tc Vc b Vc b

Vc b 2 Vc b 2

a Tc Vc b Vc b Vc b Vc b
2

Vc b 3 Vc b 3

Now, if Tc and Vc are known, then this gives us two equations that would allow us to determine
the two substance specific parameters, a(Tc) and b. Remember that the other constants, as well as
the functional form of a(T) are all specified a priori for a given equation of state (that is, we
already know them). If, as is often the case, Tc and Pc are known, rather than Tc and Vc, then we
would also use the equation of state itself to determine Vc from Tc and Pc.
Pc

a Tc
RTc

Vc b Vc b Vc b

As an example, let's apply this general procedure to the van der Waals equation of state. In that
case, we have
Pc

RTc
a
2
Vc b Vc

RTc

Vc b

RTc

Vc b

2a
Vc3
3a
Vc4

0
0

Sparing you the algebra, we can solve these to get

a

27 R 2Tc2
64 Pc

1 RTc
8 Pc

Vc

3 RTc
8 Pc

This implies that if the van der Waals equation of state were strictly correct, then all substances
would have a critical compressibility (Zc = PcVc/(RTc) = 3/8). In fact, different substances have
different values of Zc, and almost all substances have values of Zc that are somewhat smaller than
3/8.
We could similarly solve these equations for other equations of state, and would get, for a(Tc)
and b expressions like
a(Tc )
b

R 2Tc2
Pc

RTc
Pc

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Lecture 5

where and are numbers that are different for each equation of state, but independent of the
substance. Values of these (and other parameters, yet to be discussed) are tabulated for several
equations of state on p. 98 of SVNA.
Summary:
After completing your study of these lecture notes and the associated homework and material
from chapter 3 of SVNA, you should be able to:
PV
.
RT

Define and use the compressibility: Z

Write and use the two-term virial equation of state written either as a series expansion in
pressure or in molar density (1/molar volume)

Write and use the three-term virial equation of state written in terms of molar density

Relate the 2nd and 3rd virial coefficient to the slope and curvature of a plot of
compressibility vs. pressure or compressibility vs. molar density

Write the van der Waals equation of state and recognize that it is the simplest cubic
equation of state and the simplest equation of state that can describe vapor/liquid
coexistence and the volumetric properties of both phases

Write the general cubic equation of state and understand, qualitatively, how the equation
of state parameters are related to the critical properties of a fluid.

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