Equations of states
Persamaan Keadaan
concept
• The term equation of state is used for the relation between
temperature, pressure, volume and of substance in an analytic form,
i.e.
• Given that volume is an extensive quantity, we can write the equation
of state as a relation between three variables:
• Equations of states are uasually written in the form
1. Ideal/Perfect gas
2. Virial expansion
3. Pressure virial expansion
4. Van der waals
5. Redlich – Kwong
6. Benedict – Web – Rubin
7. Corresponding states theorem
1. Ideal / Perfect Gas
• Historis:
Ideal Gas
This equation is commonly applied for gases at low reduced pressures and
high reduced temperatures.
Its strengths consist in its simplicity and universal character (no constants
characterizing the substance are needed).
The accuracy of the equation depends on the kind of substance, temperature
and pressure.
For gases at a normal boiling point (pressure 101 kPa), e.g., the error in
volume determination is about 5 percent.
2. Virial Expansion
• The virial expansion is an equation of state in which the compressibility
factor is expressed in the form of a power series of 1/Vm, or in the powers
of c
• Quantities B, C, . . . are called virial coefficients; B is the second virial
coefficient, C is the virial coefficient, etc.
• B(T), C(T) we indicate that in a pure substance, the virial coefficients are
functions of temperature only (while in a mixture they also depend on
composition).
Virial Expansion
• This is a theoretically grounded equation of state, which means that
accurate relations between the virial coefficients and intermolecular
forces are known.
• In practice it is applied in such a way that the virial coefficients are
substituted by empirical relations (usually polynomials in 1/T). With a
large number of constants
• This equation allows for a good description of the behaviour or both
gases and liquids.
Boyle Temperature
The temperature at which the second virial coefficient is zero, B = 0, is
called the Boyle temperature, TB
At this temperature and in its vicinity, the approximation z = 1 (the
equation
of state of an ideal gas) is fulfilled with a high accuracy even at
relatively high pressures. At temperatures T < TB, B < 0; at T > T, B > 0.
3. Pressure Virial Expansion
• The pressure virial expansion is an equation of state in which the
compressibility factor is expressed in the form of a powers series of p
• Quantities B’, C’, . . . are termed the pressure virial coefficients, and
they are functions of temperature. The relation between the virial
and pressure virial coefficients is given by
Pressure Virial Expansion
• This equation is usually applied only with the second virial coefficient.
In this case it is used in the same range as the equation of state of an
ideal gas, but it provides more accurate results.
The second virial coefficient of ammonia at 298.15 K is -261 cm3
mol-1. Calculate the molar volume and the compressibility factor
of ammonia at this temperature and a pressure of 0.5 MPa.
Assume that at the given temperature and pressure, the terms
with higher virial coefficients in are negligible.
B’ equals the second virial coefficient
4. Van der Waals
Parameters a and b are the constants of the van der Waals equation of
state. Their values depend on the kind of gas being described. They
can be obtained from experimental data on state behaviour, or they
can be estimated from the critical quantities of substances
Van der Waals
For the second virial coefficient, the van der Waals equation yields
For the Boyle temperature, the van der Waals equation of state yields
Its only historical, it is usually not applied in practice.
Its simplicity predetermines it for use in teaching.
5. Redlich - Kwong
Parameters a and b are the constants of the Redlich-Kwong equation of
state. Their values are different for every substance. They can be
obtained from experimental data on state behaviour, or they can be
estimated from the critical quantities of substances using the relations
5. Redlich - Kwong
• The constants of the Redlich-Kwong’s equation of state are not identical
with the identically denoted constants of the van der Waals equation.
• One of the most popular equations of state for gases. Some of its
modifications are applied in current practice.
• For the second virial coefficient, the Redlich-Kwong equation yields
• For the Boyle temperature, the Redlich-Kwong equation gives
6. Benedict – Web - Rubin
• The equation contains eight adjustable constants A0, B0, C0, a, b, c, α,
β, γ which are obtained from experimental data on state behaviour.
6. Benedict – Web - Rubin
• One of the best equations of state for the gas range. However, it is
little accurate in the range of liquid, where it is substituted by its
modifications with a larger number of constants (20 and even more).
7. Corresponding State Theorm
• The theorem of corresponding states says that the compressibility
factor is a function of reduced quantities Tr, pr or Tr, Vr which is
independent of the substance
7. Corresponding State Theorm
• Based on experimental data on state behaviour of gases, a diagram of
the compressibility r factor dependence on reduced variables has
been drawn allowing for convenient and generalized (i.e.
independent of the substance) estimation of state behaviour.
• The theorem of corresponding states may be also applied in such a
way that the sought for compressibility factor zA of a substance A is
determined using the compressibility factor zR of a reference
substance R whose state behaviour is known
Corresponding State Theorm
• The compressibility factor of a reference substance for a given Tr and
pr is most often calculated using an equation of state. The results of
this procedure are the better the more similar is the reference
substance to the one under investigation.
• The two-parameter theorem (Tc and p) allows for estimating state
behaviour with an error of about 5 percent.
