Virial Equation of State

The y axis shows the pressure P in pascal, and the x-axis shows the volume
Vm of one mole of a substance in cubic metres. Two curves are shown:

• The blue curve shows the ideal gas equation: P=RT/Vm

• The red curve shows the virial equation of state incorporating terms up
the the second virial coefficient. P=RT/Vm+B(T)RT/Vm2

The curves shown correspond argon at a temperature of around 570 K. Notice

that:

• Both curves are qualitatively similar.

• The pressures are modestly high: around 200 atmospheres at the top of
the graph.
• At this temperature (570 K) the pressure according to the virial
equation is slightly higher than one would expect from the ideal gas
equation. This is not always the case. At lower temperattures, the
pressure predicted by the virial equation falls below that predicted by
the ideal gas equation. This effect is illustrated in the movie below.
• The animation below shows the effect of heating argon gas from 270 K
up to 570 K. In this range, the virial equation predictions deviate from
experiment by only a few parts per million. Notice that at high
temperatures, the pressure is slighly greater than would be expected
 from ideal gas theory. However, at low temperatures, the pressure is
slighly less than would be expected from ideal gas theory.

The equations below show how the graphs were produced in Graphing
Calculator

Equation of state - Examples of Equations of State

In the following equations the variables are defined as follows, any

consistent set of units can be used although SI units are preferred:
P = Pressure V = Volume n = number of moles of a substance Vm = V/n
= Molar volume, the volume of 1 mole of gas or liquid T = Temperature
(K) R = Ideal Gas Constant (8.314472 J/mol·K)

Equation of state - Classical Ideal Gas Law

The classical ideal gas law may be written:
The ideal gas law may also be expressed as follows
where ρ is the density, γ the adiabatic index, and e the internal energy. This
form is purely in terms of intensive quantities and is useful when simulating
the Euler equations because it expresses the relationship between internal
energy and other forms of energy (such as kinetic), thus allowing
simulations to obey the First Law.

Equation of state - Van der Waals equation

, note that Vm is molar volume.
Where a, b and R are constants that depend on the specific material. They
can be calculated from the critical properties as:
Proposed in 1873, the van der Waals equation of state was one of the first
to perform markedly better than the ideal gas law. In this landmark
equation a is called the attraction parameter and b the repulsion parameter
or the effective molecular volume. While the equation is definitely superior
to the ideal gas law and does predict the formation of a liquid phase, the
agreement with experimental data is limited for conditions where the liquid
forms. While the van der Waals equation is commonly referenced in text-
books and papers for historical reasons, it is now obsolete. Other modern
equations of only slightly greater complexity are much more accurate.
Van der Waals equation may be considered as Ideal Gas Law, "improved"
due to two independent reasons:
1) Molecules are thought as particles with volume, not material points.
Thus V cannot be too little, less than some constant. So we get (V - b)
instead of V.
2) While Ideal Gas molecules do not interact, we consider molecules
attracting others within a distance of several molecules' radii. It makes no
effect inside material, but surface molecules attract to inside. We see this as
diminishing of pressure on the outer shell (which is used in Ideal Gas Law),
so we write (P + something) instead of P. To evaluate this 'something', let's
examine addition force acting on an element of gas surface. While force
acting on each surface molecule is ~ρ, the force acting on the whole
element is ~ρ2~

Equation of state - The Virial Equation

Although usually not the most convenient equation of state, the Virial
Equation is important because it can be derived directly from statistical
mechanics. If appropriate assumptions are made about the mathematical
form of intermolecular forces, theoretical expressions can be developed for
each of the coefficients. In this case Bcorresponds to interactions between
pairs of molecules, C to triplets, and so on.

Equation of state - Redlich-Kwong Equation of State

R = Ideal Gas constant (8.31451 J/mol·K)
Introduced in 1949 the Redlich-Kwong equation of state was a considerable
improvement over other equations of the time. It is still of interest primarily
due to its relatively simple form. While superior to the van der Waals
equation of state, it performs poorly with respect to the liquid phase and
thus cannot be used for accurately calculating vapor-liquid equilibria.
However, it can be used in conjunction with separate liquid-phase
correlations for this purpose.
The Redlich-Kwong equation is adequate for calculation of gas phase
properties when the ratio of the pressure to the critical pressure is less than
about one-half of the ratio of the temperature to the critical temperature.
Equation of state - The Soave Equation
R = Ideal Gas constant (8.31451 J/(mol·K))
Where ω is the acentric factor for the species.
for hydrogen:
In 1972 Soave replaced the a/√(T) term of the Redlich-Kwong equation with
a function α(T,ω) involving the temperature and the acentric factor. The α
function was devised to fit the vapor pressure data of hydrocarbons and the
equation does fairly well for these materials.

Equation of state - The Peng-Robinson Equation of State

R = Ideal Gas constant (8.31451 J/mol·K)
Where ω is the acentric factor for the species.
The Peng-Robinson Equation was developed in 1976 in order to satisfy the
following goals:

1. The parameters should be expressible in terms of the critical

properties and the acentric factor.
2. The model should provide reasonable accuracy near the critical point,
particularly for calculations of the Compressibility factor and liquid
density.
3. The mixing rules should not employ more than a single binary
interaction parameter, which should be independent of temperature
pressure and composition.
4. The equation should be applicable to all calculations of all fluid
properties in natural gas processes.

For the most part the Peng-Robinson Equation exhibits performance similar
to the Soave equation, although it is generally superior in predicting the
liquid densities of many materials, especially nonpolar ones.

Equation of state - The BWRS Equation of State

Main articles: Benedict-Webb-Rubin, and [[{{{2}}}]], and [[{{{3}}}]], and
[[{{{4}}}]], and [[{{{5}}}]] ρ = the molar density
Values of the various parameters for 15 substances can be found in:
K.E. Starling, Fluid Properties for Light Petroleum Systems. Gulf Publishing
Company (1973).

Equation of state - Elliott Suresh Donohue

The Elliott, Suresh, and Donohue (ESD) equation of state (EOS) was
proposed in 1990. The equation seeks to correct a shortcoming in the Peng-
Robinson EOS in that there was an inaccuracy in the van der Waals repulsive
term. The EOS accounts for the effect of the shape of a non-polar molecule
and can be extended to polymers with the addition of an extra term (not
shown). The EOS itself was developed through modeling computer
simulations and should capture the essential physics of the size, shape, and
hydrogen bonding.
Where:
c = a "`shape factor"' η = bρ q = 1 + 1.90476(c − 1)
Reference: Elliott & Lira, Introductory Chemical Engineering
Thermodynamics, 1999, Prentice Hall.

Equation of state - Stiffened equation of state

When considering water under very high pressures (typical applications are
underwater nuclear explosions, sonic shock lithotripsy, and
sonoluminescence) the stiffened equation of state is often used:
p = ρ(γ − 1)e − γp0
where e is the internal energy per unit mass, γ is an empirically determined
constant typically taken to be about 6.1, and p0 is another constant,
representing the molecular attraction between water molecules. The
magnitude of the correction is about 20000 atmospheres.
The equation is stated in this form because the speed of sound in water is
given by c2 = γ(p + p0) / ρ.
Thus water behaves as though it is an ideal gas that is already under about
20000 atmospheres (2 GPa) pressure, and explains why water is commonly
assumed to be incompressible: when the external pressure changes from 1
atmosphere to 2 atmospheres (100 kPa to 200 kPa), the water behaves as
an ideal gas would do when changing from 20001 to 20002 atmospheres
(200.01 kPa to 201.02 kPa).
This equation mispredicts the specific heat capacity of water but few
alternatives are available for severely nonisentropic processes such as
strong shocks.

Equation of state - Ultrarelativistic equation of state

An ultrarelativistic fluid has equation of state
where p is the pressure, μ is the energy density, and cs is a constant
referred to as the sound speed.

Equation of state - Ideal Bose equation of state

The equation of state for an ideal Bose gas is
where α is an exponent specific to the system (e.g. in the absence of a
potential field, α=3/2), z is exp(μ/kT) where μ is the chemical potential, Li is
the polylogarithm, ζ is the Riemann zeta function, andTc is the critical
temperature at which a Bose-Einstein condensate begins to form.

Other related archives

The Virial Expansion

The virial expansion, also called the virial equation of state, is the most
interesting and versatile of the equations of state for gases.. The virial
expansion is a power series in powers of the variable, n/V, and has the form,

(1) .

The coefficient, B(T), is a function of temperature and is called the "second

virial coefficient. C(T) is called the third virial coefficient, and so on. The
expansion is, in principle, an infinite series, and as such should be valid for all
isotropic substances. In practice, however, terms above the third virial
coefficient are rarely used in chemical thermodynamics.

Notice that we have set the quantity pV/nRT equal to Z. This quantity (Z) is
called the "compression factor." It is a useful measure of the deviation of a real
gas from an ideal gas. For an ideal gas the compression factor is equal to 1.

The Boyle Temperature

The second virial coefficient, B(T), is an increasing function of temperature

throughout most of the useful temperature range. (It does decrease slightly at
very high temperatures.) B is negative at low temperatures, passes through zero
at the so-called "Boyle temperature," and then becomes positive. The
temperature at which B(T) = 0 is called the Boyle temperature because the gas
obeys Boyle's law to high accuracy at this temperature. We can see this by
noting that at the Boyle temperature the virial expansion looks like,

(2) .

If the density is not too high the C term is very small so that the system obeys
Boyle's law.

Alternate form of the virial expansion.

An equivalent form of the virial expansion is an infinite series in powers of the

pressure.
(3) .

The new virial coefficients, B', C', . . . , can be calculated from the original
virial coeffients, B, C, . . . . To do this we equate the two virial expansions,

(4)

Then we solve the original virial expansion for p,

(5) ,

and substitute this expression for p into the right-hand-side of equation (4),

(6a)

(6b)

Both sides of Equation (6b) are power series in n/V. (We have omitted third and
higher powers of n/Vbecause the second power is as high as we are going here.)
Since the two power series must be equal, the coefficients of each power
of n/V must be the same on both sides. The coefficient of (n/V)0 on each side is
1, which gives the reassuring but not very interesting result, 1 = 1. Equating the
coefficient of (n/V) 1 on each side gives B = B'RT and equating the coefficients
of (n/V)2 gives

(7) .

These equations are easily solved to give B' and C' in terms of B, C, and R.
(8) .

Useful exercises would be:

1. Extend the two virial expansions to the D and D' terms respectively and
find the expression for D' in terms of B, C, and D.

2. Find B' and C' in terms of the van der Waals a and b constants. (You
were asked, in the homework to find the virial coefficients B and C in
terms of a and b so you already have these.)

The word "virial" is related to the Latin word for force. Clausius (whose name
we will see frequently) named a certain function of the force between
molecules "the virial of force." This name was subsequently taken over for the
virial expansion because the terms in that expansion can be calculated from the
forces between the molecules.

The virial expansion is important for several reasons, among them: It can, in
principle, be made as accurate as desired by keeping more terms. Also, it has a
sound theoretical basis. The virial coefficients can be calculated from a
theoretical model of the intermolecular potential energy of the gas molecule

http://www.chem.arizona.edu/~salzmanr/480a/480ants/VIRIAL/virial.html

Virial Equations of State

Virial equations are a family of equations of state of the general form:

The parameters in the equation (B,C,D = ci) are called "virial coefficients". If
ci=0 for i>0, the virial equation reduces to the ideal gas equation. Just as with
the ideal gas equation, the temperatures and pressures used must be absolute.

The accuracy required determines the number of terms that are kept -- more
terms makes the equation more accurate, but also more complicated to work
with. Virial coefficients are different for each gas, but other than that are
functions of temperature only.

Coefficients are normally obtained by making measurements of P, V, and T,

and fitting the equation. These values are then published so that others may use
them.

Many forms of the virial equation exist. Often, we will truncate the virial
equation to

A number of methods (correlations, etc.) are available to determine B. In order

to improve accuracy and capture more behaviors, additional parameters are
sometimes added. One example is the Benedict-Webb-Rubin (BWR) equation
of state.

All the constants must be supplied if you are to use this equation for a
particular gas. It isn't always easy to find BWR coefficients for the
gas you are interested in.

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