Thermodynamics-II

Assignment no. 2
Submitted by
Muhammad Abdullah
(2019-CH-18)
Submitted to
Dr. Muhammad Azam
Saeed

Assignment
Briefly describe the equation of states theoretically and mathematically
• Major equation of state
- Classical Ideal Law
• Cubic equations of state
- Van der Waals equation of state
- Redlich-Kwong equation of state
- Soave modification of Redlich-Kwong
- Pent-Robinson equation of state
- Elliot, Suresh, Donohue equation of state
• Non-cubic equations of state
- Dieterici equation of state
• Virial equation of state
 Different kinds of Equations of State

Classical Ideal Gas Law

The classical ideal gas law can be written as
𝑝𝑉 = 𝑛𝑅𝑇
In the form shown above, the equation of state is thus
𝑓(𝑝, 𝑉, 𝑇) = 𝑝𝑉 − 𝑛𝑅𝑇 = 0

Cubic Equation of States

Cubic equations of state are called such because they can be rewritten as a cubic function of
Volume (V). Cubic equation of states is in fact the simplest equations capable of representing both
liquid and vapor behavior.

1. Van der Waals equation of state

The Van der Waals equation of state was one of the first to perform markedly better than the ideal
gas law. The Van der Waals equation of state can be written as
𝑎
(𝑝 + )(𝑉 − 𝑏) = 𝑅𝑇
𝑉2
𝑅𝑇 𝑎
𝑝= − 2
𝑉−𝑏 𝑉
Where V is molar volume. The substance specific constant a and b can be calculated from critical
properties pc, Tc, Vc (where Vc is the molar volume at critical point). When a and b are zero the
ideal gas equation is recovered. a is called the attraction parameter and b the repulsion
parameter or the effective molecular volume.
2
𝑎 = 3𝑝𝑐 𝑉𝑐
𝑏 = 𝑉𝑐/3
Also written as

27(𝑅𝑇𝑐)2
𝑎=
64𝑝𝑐
𝑅𝑇𝑐
𝑏=
8𝑝𝑐
Since introduction to Van der Waals equation, scores of cubic equations of state have been
proposed
𝑅𝑇 𝜃(𝑉 − 𝜂)
𝑃= −
𝑉 − 𝑏 (𝑉 − 𝑏)(𝑉2 + 𝜅𝑉 + 𝜆)
The generic cubic equation of states, which reduces to appropriate parameters
𝑅𝑇 𝑎(𝑇)
𝑃= −
𝑉 − 𝑏 (𝑉 − 𝜀𝑏)(𝑉 + 𝜎𝑏)

For a given equation, 𝜀 and 𝜎 are pure numbers, the same for all substance, where as parameters
a(T) and b are substance dependent.
Limitation
Is 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.

2. Redlich-Kwong equation of state

The modern development of cubic equations of state was initiated in 1949 by publication of
Redlich-Kwong (RK) equation
𝑅𝑇 𝑎(𝑇)
𝑃= −
𝑉 − 𝑏 𝑉(𝑉 + 𝑏)
1
−
𝛼(𝑇) = 𝑇𝑟 2
It is still of interest primarily due to its relatively simple form.
Limitations
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).
𝑃 𝑇
<
𝑃𝑐 2𝑇𝑐
 3. Soave modification of Redlich-Kwong
𝑅𝑇 𝛼(𝑇)
𝑃= −
𝑉 − 𝑏 𝑉(𝑉 + 𝑏)
1 2
𝛼(𝑇𝑟 , 𝜔) = [1 + (0.480 + 1.574𝜔 − 0.176𝜔2 ) (1 − 𝑇 2 )] 𝑟

Where ω is the acentric factor for the species

In 1972 G. Soave replaced the T-1/2 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.

4. Pent-Robinson equation of state

𝑅𝑇 𝛼(𝑇)
𝑃= −
𝑉 − 𝑏 𝑉(𝑉 + 𝑏)
1 2
𝛼(𝑇𝑟 , 𝜔) = [1 + (0.37464 + 1.54226𝜔 − 0.26992𝜔 2 ) (1 − 𝑇 2 )] 𝑟

The attractive force parameter ‘a’, which was considered to be a constant with respect to pressure
in Peng–Robinson EOS. The modification, in which parameter ‘a’ was treated as a variable with
respect to pressure for multicomponent multi-phase high density reservoir systems was to improve
accuracy in the prediction of properties of complex reservoir fluids for PVT modeling. The
variation was represented with a linear equation where a1 and a2 represent the slope and the
intercept respectively of the straight line obtained when values of parameter ‘a’ are plotted against
pressure.
This modification increases the accuracy of Peng–Robinson equation of state for heavier fluids
particularly at pressure ranges (>30MPa) and eliminates the need for tuning the original Peng-
Robinson equation of state.
5. Elliot, Suresh, Donohue equation of state
The Elliott, Suresh, and Donohue (ESD) equation of state 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.
𝑃𝑉𝑚
= 𝑍 = 1 + 𝑍𝑟𝑒𝑝 + 𝑍𝑎𝑡𝑡
𝑅𝑇
Where
4𝑐𝜂
𝑍𝑟𝑒𝑝 =
1 − 1.9𝜂

𝑧𝑚𝑞𝜂𝑌
𝑍𝑎𝑡𝑡 = −
1 − 𝐾1𝜂𝑌
Non-Cubic Equation of State
1. Dieterici equation of state
𝑎
𝑃(𝑉 − 𝑏) = 𝑅𝑇𝑒 − 𝑅𝑇𝑉
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:
𝑎 𝑎 4𝑏2𝑒2
𝑇𝑐 = =
4𝑅𝑏
𝑉𝑐 = 2𝑏
Virial Equation of State
Virial expression in pressure
𝑍 = 1 + 𝐵′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷′ 𝑃3 + ⋯
Virial expression in volume and density
𝐵 𝐶 𝐷 2 3
𝑍 = 1 + 𝑉 + 𝑉2 + 𝑃3 + ⋯ =1 + 𝐵𝑝 + 𝐶𝑝 + 𝐷𝑝 + ⋯
If no interactions, the terms B/V, C/V2 etc. are zero, because B, C etc. are zero.
𝑍=1 or 𝑃𝑉=𝑅𝑇
In real gases, interactions do exist. As V increases, the contributions of the term’s B/V, C/V2 etc.
decreases. Remember B, C etc. do not decrease, only V increases. In the limit P approaches 0,
again from above equations
Z→1 or PV→RT
Virial Coefficient
Virial coefficient is showing the interaction between the molecules. In ideal gas there is no
interaction so the virial coefficient is zero. If we have two interreacting molecular system than
the viral coefficient is B in case of three we have viral coefficient C and so on.
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.