Equation of state

In physics and thermodynamics, an

equation of state is a thermodynamic
equation relating state variables which
describe the state of matter under a given
set of physical conditions, such as
pressure, volume, temperature (PVT), or
internal energy.[1] Equations of state are
useful in describing the properties of
fluids, mixtures of fluids, solids, and the
interior of stars.
Overview
The most prominent use of an equation of
state is to correlate densities of gases and
liquids to temperatures and pressures.
One of the simplest equations of state for
this purpose is the ideal gas law, which is
roughly accurate for weakly polar gases at
low pressures and moderate
temperatures. However, this equation
becomes increasingly inaccurate at higher
pressures and lower temperatures, and
fails to predict condensation from a gas to
a liquid. Therefore, a number of more
accurate equations of state have been
developed for gases and liquids. At
present, there is no single equation of
state that accurately predicts the
properties of all substances under all
conditions.

Another common use is in modeling the

interior of stars, including neutron stars,
dense matter (quark–gluon plasmas) and
radiation fields. A related concept is the
perfect fluid equation of state used in
cosmology.

Equations of state can also describe

solids, including the transition of solids
from one crystalline state to another.
In a practical context, equations of state
are instrumental for PVT calculations in
process engineering problems, such as
petroleum gas/liquid equilibrium
calculations. A successful PVT model
based on a fitted equation of state can be
helpful to determine the state of the flow
regime, the parameters for handling the
reservoir fluids, and pipe sizing.

Measurements of equation-of-state
parameters, especially at high pressures,
can be made using lasers.[2][3][4]

Historical
Boyle's law (1662)
Boyle's Law was perhaps the first
expression of an equation of state. In
1662, the Irish physicist and chemist
Robert Boyle performed a series of
experiments employing a J-shaped glass
tube, which was sealed on one end.
Mercury was added to the tube, trapping a
fixed quantity of air in the short, sealed
end of the tube. Then the volume of gas
was measured as additional mercury was
added to the tube. The pressure of the gas
could be determined by the difference
between the mercury level in the short end
of the tube and that in the long, open end.
Through these experiments, Boyle noted
that the gas volume varied inversely with
the pressure. In mathematical form, this
can be stated as:

The above relationship has also been

attributed to Edme Mariotte and is
sometimes referred to as Mariotte's law.
However, Mariotte's work was not
published until 1676.

Charles's law or Law of Charles

and Gay-Lussac (1787)

In 1787 the French physicist Jacques

Charles found that oxygen, nitrogen,
hydrogen, carbon dioxide, and air expand
to roughly the same extent over the same
80-kelvin interval. Later, in 1802, Joseph
Louis Gay-Lussac published results of
similar experiments, indicating a linear
relationship between volume and
temperature:

Dalton's law of partial

pressures (1801)

Dalton's Law of partial pressure states that

the pressure of a mixture of gases is equal
to the sum of the pressures of all of the
constituent gases alone.
Mathematically, this can be represented
for n species as:

The ideal gas law (1834)

In 1834, Émile Clapeyron combined Boyle's

Law and Charles' law into the first
statement of the ideal gas law. Initially, the
law was formulated as pVm = R(TC + 267)
(with temperature expressed in degrees
Celsius), where R is the gas constant.
However, later work revealed that the
number should actually be closer to 273.2,
and then the Celsius scale was defined
with 0 °C = 273.15 K, giving:

Van der Waals equation of

state (1873)

In 1873, J. D. van der Waals introduced the

first equation of state derived by the
assumption of a finite volume occupied by
the constituent molecules.[5] His new
formula revolutionized the study of
equations of state, and was most
famously continued via the Redlich–
Kwong equation of state and the Soave
modification of Redlich-Kwong.
General form of an equation
of state
For a given amount of substance
contained in a system, the temperature,
volume, and pressure are not independent
quantities; they are connected by a
relationship of the general form

An equation used to model this

relationship is called an equation of state.
In the following sections major equations
of state are described, and the variables
used here are defined as follows. Any
consistent set of units may be used,
although SI units are preferred. Absolute
temperature refers to use of the Kelvin (K)
or Rankine (°R) temperature scales, with
zero being absolute zero.

, pressure (absolute)
, volume
, number of moles of a substance

, , molar volume, the volume of 1

mole of gas or liquid

, absolute temperature
, ideal gas constant ≈
8.3144621 J/mol·K
, pressure at the critical point
, molar volume at the critical point
 , absolute temperature at the critical
point

Classical ideal gas law

The classical ideal gas law may be written

In the form shown above, the equation of

state is thus

If the calorically perfect gas approximation

is used, then the ideal gas law may also be
expressed as follows
where is the density, is the
adiabatic index (ratio of specific heats),
is the internal energy per unit
mass (the "specific internal energy"), is
the specific heat at constant volume, and
is the specific heat at constant
pressure.

Cubic equations of state

Cubic equations of state are called such
because they can be rewritten as a cubic
function of Vm.

Van der Waals equation of

state
The Van der Waals equation of state may
be written:

where is molar volume. The

substance-specific constants and can
be calculated from the critical properties
and (noting that is the molar
volume at the critical point) as:

Also written 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 is called
the attraction parameter and 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.

The van der Waals equation may be

considered as the ideal gas law,
"improved" due to two independent
reasons:

1. Molecules are thought as particles with

volume, not material points. Thus
cannot be too little, less than some
constant. So we get ( ) instead of
.
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
the material, but surface molecules are
attracted into the material from the
surface. We see this as diminishing of
pressure on the outer shell (which is used
in the ideal gas law), so we write (
something) instead of . To evaluate this
‘something’, let's examine an additional
force acting on an element of gas surface.
While the force acting on each surface
molecule is ~ , the force acting on the

whole element is ~ ~ .
With the reduced state variables, i.e.
Vr=Vm/Vc, Pr=P/Pc and Tr=T/Tc, the
reduced form of the Van der Waals
equation can be formulated:

The benefit of this form is that for given Tr

and Pr, the reduced volume of the liquid
and gas can be calculated directly using
Cardano's method for the reduced cubic
form:
For Pr<1 and Tr<1, the system is in a state
of vapor–liquid equilibrium. The reduced
cubic equation of state yields in that case
3 solutions. The largest and the lowest
solution are the gas and liquid reduced
volume.

Redlich-Kwong equation of
state
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 (reduced pressure) is less
than about one-half of the ratio of the
temperature to the critical temperature
(reduced temperature):

Soave modification of Redlich-

Kwong
Where ω is the acentric factor for the
species.

This formulation for is due to Graboski

and Daubert. The original formulation from
Soave is:
for hydrogen:

We can also write it in the polynomial

form, with:

then we have:

where is the universal gas constant and

Z=PV/(RT) is the compressibility factor.
In 1972 G. Soave[6] replaced the 1/√T term
of the Redlich-Kwong equation with a
function α(T,ω) involving the temperature
and the acentric factor (the resulting
equation is also known as the Soave-
Redlich-Kwong equation of state; SRK
EOS). The α function was devised to fit the
vapor pressure data of hydrocarbons and
the equation does fairly well for these
materials.

Note especially that this replacement

changes the definition of a slightly, as the
is now to the second power.

Volume translation of Peneloux

et al. (1982)

The SRK EOS may be written as

where

where and other parts of the SRK EOS is

defined in the SRK EOS section.
A downside of the SRK EOS, and other
cubic EOS, is that the liquid molar volume
is significantly less accurate than the gas
molar volume. Peneloux et alios (1982)[7]
proposed a simple correction for this by
introducing a volume translation

where is an additional fluid component

parameter that translate the molar volume
slightly. On the liquid branch of the EOS, a
small change in molar volume
corresponds to a large change in pressure.
On the gas branch of the EOS, a small
change in molar volume corresponds to a
much smaller change in pressure than for
the liquid branch. Thus, the perturbation of
the molar gas volume is small.
Unfortunately, there are two versions that
occur in science and industry.

In the first version only is

translated,[8][9] and the EOS becomes

In the second version both and

are translated, or the translation of
is followed by a renaming of the
composite parameter b − c.[10] This gives
The c-parameter of a fluid mixture is
calculated by

The c-parameter of the individual fluid

components in a petroleum gas and oil
can be estimated by the correlation

where the Rackett compressibility factor

can be estimated by
A nice feature with the volume translation
method of Peneloux et al. (1982) is that it
does not affect the vapor-liquid
equilibrium calculations.[11] It should be
noted that this method of volume
translation can also be applied to other
cubic EOSs if the c-parameter correlation
is adjusted to match the selected EOS.

Peng–Robinson equation of
state
In polynomial form:
where is the acentric factor of the
species, is the universal gas constant
and is compressibility
factor.

The Peng–Robinson equation of state (PR

EOS) was developed in 1976 at The
University of Alberta by Ding-Yu Peng and
Donald Robinson in order to satisfy the
following goals:[12]

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.[13] The departure functions of the
Peng–Robinson equation are given on a
separate article.

The analytic values of its characteristic

constants are:

Peng–Robinson-Stryjek-Vera
equations of state

PRSV1

A modification to the attraction term in the

Peng–Robinson equation of state
published by Stryjek and Vera in 1986
(PRSV) significantly improved the model's
accuracy by introducing an adjustable pure
component parameter and by modifying
the polynomial fit of the acentric factor.[14]

The modification is:

where is an adjustable pure
component parameter. Stryjek and Vera
published pure component parameters for
many compounds of industrial interest in
their original journal article. At reduced
temperatures above 0.7, they recommend
to set and simply use .
For alcohols and water the value of
may be used up to the critical temperature
and set to zero at higher temperatures.[14]

PRSV2

A subsequent modification published in

1986 (PRSV2) further improved the
model's accuracy by introducing two
additional pure component parameters to
the previous attraction term
modification.[15]

The modification is:

where , , and are adjustable pure

component parameters.

PRSV2 is particularly advantageous for

VLE calculations. While PRSV1 does offer
an advantage over the Peng–Robinson
model for describing thermodynamic
behavior, it is still not accurate enough, in
general, for phase equilibrium
calculations.[14] The highly non-linear
behavior of phase-equilibrium calculation
methods tends to amplify what would
otherwise be acceptably small errors. It is
therefore recommended that PRSV2 be
used for equilibrium calculations when
applying these models to a design.
However, once the equilibrium state has
been determined, the phase specific
thermodynamic values at equilibrium may
be determined by one of several simpler
models with a reasonable degree of
accuracy.[15]
One thing to note is that in the PRSV
equation, the parameter fit is done in a
particular temperature range which is
usually below the critical temperature.
Above the critical temperature, the PRSV
alpha function tends to diverge and
become arbitrarily large instead of tending
towards 0. Because of this, alternate
equations for alpha should be employed
above the critical point. This is especially
important for systems containing
hydrogen which is often found at
temperatures far above its critical point.
Several alternate formulations have been
proposed. Some well known ones are by
Twu et all or by Mathias and Copeman.
Elliott, Suresh, Donohue
equation of state

The Elliott, Suresh, and Donohue (ESD)

equation of state was proposed in
1990.[16] 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:

and

is a "shape factor", with for

spherical molecules
For non-spherical molecules, the
following relation is suggested:
 where
is the acentric factor
The reduced number density is

defined as

where

is the characteristic size parameter

is the number of molecules
is the volume of the container

The characteristic size parameter is

related to the shape parameter through

where
 and is Boltzmann's constant.

Noting the relationships between

Boltzmann's constant and the Universal
gas constant, and observing that the
number of molecules can be expressed in
terms of Avogadro's number and the molar
mass, the reduced number density can
be expressed in terms of the molar volume
as

The shape parameter appearing in the

Attraction term and the term are given
by

(and is hence also

equal to 1 for spherical molecules).

where is the depth of the square-well

potential and is given by

, , and are constants in the

equation of state:
for spherical molecules
(c=1)
 for spherical molecules
(c=1)
for spherical molecules
(c=1)

The model can be extended to associating

components and mixtures of
nonassociating components. Details are in
the paper by J.R. Elliott, Jr. et al. (1990).[16]

Cubic-Plus-Association

The Cubic-Plus-Association (CPA)

equation of state combines the Soave-
Redlich-Kwong equation with an
association term from Wertheim theory.[17]
The development of the equation began in
1995 as a research project that was
funded by Shell, and in 1996 an article was
published which presented the CPA
equation of state.[17][18]

Non-cubic equations of state

Dieterici equation of state

where a is associated with the interaction

between molecules and b takes into
account the finite size of the molecules,
similar to the Van der Waals equation.
The reduced coordinates are:

Virial equations of state

Virial equation of state

Although usually not the most convenient

equation of state, the virial equation is
important because it can be derived
directly from statistical mechanics. This
equation is also called the Kamerlingh
Onnes equation. If appropriate
assumptions are made about the
mathematical form of intermolecular
forces, theoretical expressions can be
developed for each of the coefficients. A is
the first virial coefficient, which has a
constant value of 1 and makes the
statement that when volume is large, all
fluids behave like ideal gases. The second
virial coefficient B corresponds to
interactions between pairs of molecules, C
to triplets, and so on. Accuracy can be
increased indefinitely by considering
higher order terms. The coefficients B, C,
D, etc. are functions of temperature only.

One of the most accurate equations of

state is that from Benedict-Webb-Rubin-
Starling[19] shown next. It was very close to
a virial equation of state. If the exponential
term in it is expanded to two Taylor terms,
a virial equation can be derived:

Note that in this virial equation, the fourth

and fifth virial terms are zero. The second
virial coefficient is monotonically
decreasing as temperature is lowered. The
third virial coefficient is monotonically
increasing as temperature is lowered.

The BWR equation of state

where

p is pressure
ρ is molar density

Values of the various parameters for 15

substances can be found in K.E. Starling
(1973). Fluid Properties for Light Petroleum
Systems. Gulf Publishing Company.

SAFT equations of state

Statistical associating fluid theory (SAFT)
equations of state use statistical
mechanical methods (in particular
perturbation theory) to describe the
interactions between molecules in a
system.[20] The idea of a SAFT equation of
state was first proposed by Chapman et al.
in 1989,[20] but since then many different
SAFT equations of state have been
proposed.[21] Often SAFT equations
represent molecules as collections of
spherical particles that interact with one
another.[20] One popular SAFT equation
represents molecules as chains
composed of spherical segments (PC-
SAFT).[22] In general, SAFT equations give
more accurate results than traditional
cubic equations of state, especially for
systems containing liquids or solids.[23][24]
Multiparameter equations of
state
Helmholtz Function form

Multiparameter equations of state (MEOS)

can be used to represent pure fluids with
high accuracy, in both the liquid and
gaseous states. MEOS's represent the
Helmholtz function of the fluid as the sum
of ideal gas and residual terms. Both
terms are explicit in reduced temperature
and reduced density - thus:
where:

The reduced density and temperature are

typically, though not always, the critical
values for the pure fluid.

Other thermodynamic functions can be

derived from the MEOS by using
appropriate derivatives of the Helmholtz
function; hence, because integration of the
MEOS is not required, there are few
restrictions as to the functional form of
the ideal or residual terms. Typical MEOS
use upwards of 50 fluid specific
parameters, but are able to represent the
fluid's properties with high accuracy.
MEOS are available currently for about 50
of the most common industrial fluids
including refrigerants. Mixture models also
exist.

Other equations of state of

interest
Stiffened equation of state

When considering water under very high

pressures, in situations such as
underwater nuclear explosions, sonic
shock lithotripsy, and sonoluminescence,
the stiffened equation of state is often
used:

where is the internal energy per unit

mass, is an empirically determined
constant typically taken to be about 6.1,
and is another constant, representing
the molecular attraction between water
molecules. The magnitude of the
correction is about 2 gigapascals (20,000
atmospheres).

The equation is stated in this form

because the speed of sound in water is
given by .
Thus water behaves as though it is an
ideal gas that is already under about
20,000 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 when
changing from 20,001 to 20,002
atmospheres (2000.1 MPa to
2000.2 MPa).

This equation mispredicts the specific

heat capacity of water but few simple
alternatives are available for severely
nonisentropic processes such as strong
shocks.

Ultrarelativistic equation of
state

An ultrarelativistic fluid has equation of

state

where is the pressure, is the mass

density, and is the speed of sound.

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, and Tc is
the critical temperature at which a Bose–
Einstein condensate begins to form.

Jones–Wilkins–Lee equation
of state for explosives (JWL
equation)

The equation of state from Jones–

Wilkins–Lee is used to describe the
detonation products of explosives.

The ratio is defined by using

= density of the explosive (solid part)
and = density of the detonation
products. The parameters , , ,
and are given by several references.[25]
In addition, the initial density (solid part)
, speed of detonation , Chapman–
Jouguet pressure and the chemical
energy of the explosive are given in
such references. These parameters are
obtained by fitting the JWL-EOS to
experimental results. Typical parameters
for some explosives are listed in the table
below.

Material
(g/cm3) (m/s) (GPa) (GPa) (GPa) (GPa)

TNT 1.630 6930 21.0 373.8 3.747 4.15 0.90 0.35 6.00

Composition
1.717 7980 29.5 524.2 7.678 4.20 1.10 0.35 8.50
B

PBX 9501[26] 1.844 36.3 852.4 18.02 4.55 1.3 0.38 10.2

Equations of state for solids

and liquids
Common abbreviations:

Tait equation for water and other liquids.

Several equations are referred to as the
Tait equation.
Murnaghan equation of state

Birch–Murnaghan equation of state

Stacey-Brennan-Irvine equation of
state[27] (falsely often refer to Rose-
Vinet equation of state)

Modified Rydberg equation of

state[28][29][30] (more reasonable form for
strong compression)
Adapted Polynomial equation of
state[31] (second order form = AP2,
adapted for extreme compression)

with

where = 0.02337 GPa.nm5. The total

number of electrons in the initial
volume determines the Fermi gas
pressure , which provides for the
correct behavior at extreme
compression. So far there are no known
"simple" solids that require higher order
terms.
Adapted polynomial equation of
state[31] (third order form = AP3)

Johnson–Holmquist equation of state

Mie–Gruneisen equation of state (for a

more detailed discussion see ref.[32])

Anton-Schmidt equation of state

 where is the bulk modulus at

equilibrium volume and

typically about −2 is often related to the

Grüneisen parameter by

See also
Gas laws
Departure function
Table of thermodynamic equations
Real gas
Cluster Expansion

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