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IPUE208b-Equations of State

Equations of state (EoS) relate the pressure, temperature, and volume of a substance and allow prediction of these properties. Common EoS include virial equations, cubic equations like van der Waals, and empirical equations. Cubic EoS can represent both gas and liquid states but require solving cubic equations. Group contribution methods estimate properties by summing contributions from functional groups.

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Randy Sooknanan
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63 views

IPUE208b-Equations of State

Equations of state (EoS) relate the pressure, temperature, and volume of a substance and allow prediction of these properties. Common EoS include virial equations, cubic equations like van der Waals, and empirical equations. Cubic EoS can represent both gas and liquid states but require solving cubic equations. Group contribution methods estimate properties by summing contributions from functional groups.

Uploaded by

Randy Sooknanan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Equations of State (EoS)

Previously we learnt that the compressibility factor z,can be


introduced into the ideal gas equation so that the latter, can
be used to predict properties of real gases.

Equations derived from theory or experiment can be fit


from experimental data and used to solve for p, V, n and T
for real gases.

Another way of predicting p, V, n and T for real gases


( either pure components or mixtures) is by using equations
of state (EoS).

The simplest example of an equation of state is the ideal


gas law itself. Equations of state can be just empirical
relations selected to fit a data set or they can be based on
theory, or a combination of the two.

An equation of state (EoS) is an analytical expression


relating the pressure p, to the temperature T and the volume
V.
They are important because:

- they permit a concise summaryof a large mass of


experimental data and also permit accurate
interpolation between experimental data points.
- They provide a continuous function to facilitate
calculation of physical properties based on
differentiation and integration of p-V-T relationships.
- They provide a point of departure for the treatment of
the properties of mixtures.

Advantages using an EoS versus other prediction


methods are:
1) Values of p-V-T can be predicted with reasonable
error in regions where no data exist.
2) Only a few values of coefficients are needed in the
equation to be able to predict gas properties versus
collecting large amounts of data by experiment
3) The equations can be manipulated on a computer
whereas other methods cannot.

Disadvantages
1) The form of an equation is hard to change to fit new
data
2) Inconsistencies may exist between equations for p-V-
T and equations for other physical properties.
3) Usually the equation is quite complicated and may not
be easy to solve for p-V or T because of its non
linearity.

Examples of equations of state are outlined in Table 15.1

There are roughly three different classes of EoS, each


being represented in Table 15.1

First, the virial equation, which can be derived from


molecular theory, but is limited in its range of
applicability. It is a polynomial in p or 1/V (or density)
which when sequenced to the second and third order
term can represent modest deviations from ideal gas
behavior, but not liquid properties. Eg, Holborn,
Kammerlingh-Onnes

Secondly, semi theoretical(analytical) EoS which are


cubic in volume and whose volumes can be found
analytically from specified p and T data,these equations
can represent both liquid and vapour behavior over
limited ranges of temperature for many but not all
substances. Eg, van der Waals, Peng Robinson, Soave-
Redlich-Kwong, Redlich-Kwong.

Thirdly, several empirical EoS in which volume cannot


be found analyticallyreferred to as non analytic equations
are applicable over broader ranges of p and T than are
the analytic equations but they usually require many
parameters that require fitting to large amounts of data of
several properties.These models include empirical forms
of original and modified Benedict-Webb-Rubin
(MBWR).

One feature of the cubic equations of state listed in


Table 15.1, is in solving for n or V you must solve a
cubic equation that might have more than one real root as
indicated in Figure 15.2.
The van der Waals equation can be easily solved for p :

p= (nRT/V– nb) – n2a/V2


However if you want to solve for V (or n) the equation
becomes cubic and can have multiple roots. One wants a
positive real root in the gas phase. In Fig, 15.2b the
smaller root pertains to the pressure of the liquid.

An alternative graphical technique for finding the roots


of a function of a single variaqble such as f(V) is to
substitute into the function a series of values of V and
find the value of V that causes the value of f(V) to cross
the horizontal axis f(V) =0 as V changes. Refer to Figure
15.3.

Application of the van der Waals equation to calculate a


temperature

A cyclinder 0.150m3 in volume containing 22.7 kg of


propane C3H8 stands in the hot sun. A pressure gauge
shows that the pressure is 4790kPa gauge. What is the
temperature of the propane in the cyclinder? Use van der
Waals equation.

The group contribution method has been successful in


estimating p-V-T properties of pure components (as well
as other thermodynamic properties). The idea is that
compounds can be constructed from combinations of
functional groups, the contribution of each group to a
property can be tabulated, and the group contributions
can be correlated and or summed to give the desired
property of the compound.
The assumption is that a group such as –CH 3 or OH
behaves identically no matter what the molecule may be
in which it appears. This assumption is not quite true, so
that any group contribution method yields approximate
values for gas properties. UNIFAC and UNIQUAC are
widely used group contribution methods.

We have discussed predicting p-V-T properties of pure


components. One needs to know how one should treat
mixtures of gases.
Mixtures of gases are treated by devising, mixing rules.
That is rules to weight the coefficients for each pure
component so that the weighted coefficient can be used
in the same equation of state as used for a pure
component.

Eg.one set of mixing rules for the Soave-Redlich –


Kwong equation suggests:

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