Machine Problem No.

2
EQUATIONS OF STATE

Objectives

1. To determine the specific volume of pure substances and mixtures using MS Excel® and Aspen Plus®

2. To compare the calculated specific volume of pure substances and mixtures using different Equations of

State

Summary of Results

For this task, two problems were given; a pure substance component and a mixture. The specific volume

for each problem was determined using the EOS with the help of MS Excel. The following equations of states

were used for the calculation:

Table 1. Equations of State

Equation of State Equation
Ideal Gas Equation 𝑝𝑉 = 𝑛𝑅𝑇 (1)
Van Der Waals 𝑅𝑇 𝑎
𝑝 = 𝑣̂−𝑏 − 𝑣̂ (2)
Redlich-Kwong EOS 𝑅𝑇 𝑎
𝑝 = 𝑣̂−𝑏 − 𝑣̂(𝑣̂+𝑏) (3)

Redlick-Kwong-Soave EOS 𝑅𝑇 𝑎
𝑝 = 𝑣̂−𝑏 − 𝑣̂(𝑣̂+𝑏) (4)

wherein 𝑝 is the absolute pressure, V is the volume, n is the number of moles, R is the gas constant, and T is the

absolute temperature, 𝑣̂ is the specific volume, 𝑎 is for the interaction of forces between the molecules, and b is

accountable for the excluded volume. For each EOS, the calculation of the constants a and b are different. In the

Redlich – Kwong – Soave EOS, a is calculated from the modified Redlich – Kwong EOS. The variables m, and

the accentric factor w is used. The equations used for the calculation of a and b are the following:

Table 2. For the Van Der Waals EOS and Redlich-Kwong EOS
Variable Equation
a 𝑅 2 𝑇𝑐 2
𝑎 = 0.42748 ( )α (5)
𝑃𝑐
b 𝑅𝑇𝑐
𝑏 = 0.08664 ( 𝑃𝑐 ) (6)
Tr 𝑇
𝑇𝑟 = 𝑇𝑐 (7)

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 Machine Problem No. 2
EQUATIONS OF STATE

α 1
α = 𝑇𝑟 0.5 (8)

Table 3. For Redlich – Kwong – Soave EOS

Variable Equation
α α = [1 + m(1 − Tr 0.5 )]2 (9)
m 𝑚 = 0.480 + 1.574 ꙍ + 0.176 ꙍ2 (10)

In case of gaseous mixture, the a and b for each component needs to be considered. It can be calculated using the

following equations:

Table 4. For Gaseous Mixtures

Variable Equation
ai 𝑅 2 𝑇𝑐𝑖 2
𝑎𝑖 = 0.42748 ( )𝛼𝑖
𝑃𝑐𝑖
bi 𝑅𝑇𝑐𝑖
𝑏𝑖 = 0.08664 ( )
𝑃𝑐𝑖

Where Tc is the critical temperature, Pc is the critical pressure, and Tr is the reduced temperature.

Each of these equations were used to solve the machine problem using MS Excel. Results are tabulated

below. Table 5 shows the given and obtained data for the problem and Table 6 shows the calculated parameters

and volume for each EOS.

Table 5. Data and Parameters for Problem 1

Parameter Value Units
P 100 atm
T 573.15 K
R 0.08205 atm-L/K-mol
Tc 512.6 K
Pc 79.9112 atm
Tr 1.118123293 -
ꙍ 0.559 -

Table 6. Calculated Parameters and Volume using Different Equations of EOS for Problem 1
Equation of State Parameters Value Units
Ideal Gas v 0.47027 L/mol

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 Machine Problem No. 2
EQUATIONS OF STATE

Van Der Waals b 0.06578 L/mol

a 9.33879 atm – L2 / mol2
v 0.45614 L/mol
Redlich – Kwong α 0.94570 -
b 0.045600 L/mol
a 8.94906 atm – K1/2 – (L2/mol2)2
v 0.29239 L/mol
Redlich -Kwong - Soave m 1.41486 -
α 0.84413 -
b 0.04560 L/mol
a 7.89792 atm-K1/2-(L2/mol2)2
v 0.33428 L/mol

Table 7 Summary of Results using Aspen Plus for Problem 1

Equation of State Value of Molar Volume (v) (L/mol)
Ideal Gas Equation 0.47015
Redlich – Kwong - Soave 0.32986

For Problem 2, Table 8 shows the given properties and data for the mixture. For one hour operation, Table

9 shows the corresponding mole fraction and constant parameters for each component for the mixture. Table 10-

12 shows the calculated parameters for each equations of state. Using the calculated parameters, the molar volume

is calculated using the EOS. For the determination of the specific volume, the average molar weight from Table

9 and molar volume from Table 10 is used. Table 13 shows the molar and specific volumes calculated.

Table 8. Data for Problem 2

Parameter Value Units
P 100 atm
T 573.15 K
R 0.08205 atm-L/K-mol

Table 9. Parameters and Molar Composition for the Components of the Mixture
Compound No. of Moles Mole Fraction MW Tc Pc Tr
(yi)
CO 100 0.25 28 132.91 34.532 4.312
H2 200 0.5 2 33.2 12.83 17.264
CH3OH 100 0.25 32 513 78.5 1.117
MW Average 16

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 Machine Problem No. 2
EQUATIONS OF STATE

Table 10. Computed Parameters using Van der Waals EOS

Compound ai bi a b
CO 1.45289 0.03948 0.0908 0.00986
H2 0.244 0.02654 0.06100 0.01327
CH3OH 9.5215 0.06703 0.59509 0.01676
SUM 0.74690 0.03989

Table 11. Computed Parameters using Redlich – Kwong EOS

Compound α ai bi a b
CO 0.48155 0.70894 0.02736 0.04431 0.00684
H2 0.24067 0.05951 0.018395 0.01488 0.00919
CH3OH 0.94607 9.12773 0.04646 0.57048 0.01161
SUM 0.62967 0.02765

Table 12. Computed Parameters using Redlich – Kwong - Soave EOS

Compound m α ai bi a b
CO 0.55670 0.16048 0.23617 0.02735 0.01476 0.00683
H2 0.12520 0.36602 0.09049 0.01839 0.02262 0.00919
CH3OH 1.35967 0.84996 8.05028 0.04564 0.50314 0.01141
SUM 0.54053 0.027466

Table 13. Summary of Results for Problem 2 using MS Excel

Equation of State Value of Molar Volume (v) Value of Specific Volume (v’)
(L/mol) (L/g)
Ideal Gas Equation 0.47027 0.02939
Van der Waals EOS 0.50328 0.03146
Redlich – Kwong 0.48637 0.03039

Redlich – Kwong - Soave 0.48782 0.03049

Table 14. Summary of Results using Aspen Plus for Problem 2

Equation of State Value of Molar Volume (v) Value of Specific Volume (v’)
(L/mol) (L/g)
Ideal Gas Equation 0.47653 0.02939
Redlich – Kwong - Soave 0.33632 0.03034

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EQUATIONS OF STATE

Discussion

There are thermodynamic equations that are used in relation between state variables such as pressure,

temperature, and volume. These are called Equations of State (EOS). One of the simplest form of equations of

state is called the Ideal Gas Equation (Equation 1) wherein the gaseous solution is assumed to behave ideally.

Yet, at low temperature and high pressure, real gases depart from ideal behavior. Thus, different kinds of

equations of state were established to account for the deviation. In order to modify the ideal gas EOS to account

to the interaction forces between two molecules and excluded volume, variables a and b are introduced.

Modification of the calculation of these variables were done to accurately account real behavior. The latest and

complex form of Equation of State that were also used in this machine problem is called the Redlich – Kwong –

Soave EOS.

These equations are usually used for the calculation of the volume of a gaseous solution or mixture. In

order to use the EOS, several thermodynamic properties are needed such as critical temperature and pressure.

These can be found from different kinds of sources, most importantly on the Perry’s Chemical Engineering

Handbook. Using the thermodynamic properties and the given data, specific and molar volume were calculated

from problems 1 and 2, as shown in Table 6 and 13. Different results were acquired for each EOS used. Since

these EOS are modified, the latest version, which is the Redlich – Kwong – Soave EOS, obtained the most

accurate result. As stated, the source of deviation observed is the nature of real gases to deviate from ideal behavior

which is accounted by additional parameters to the recent EOS. The volume obtained using these EOS is from

the prediction of the behavior of the gas considering the intermolecular forces and other extensive and intensive

properties.

Two softwares were used to calculate for the required volume in Problem 1, which are MS Excel and

Aspen Plus. These are beneficial for solving implicit and explicit equations. Based from the results, Aspen

Plus® gives more accuracy than MS Excel® since some properties required for the calculation are already

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 Machine Problem No. 2
EQUATIONS OF STATE

provided. On the other hand, in MS Excel®, you are required to input the properties in the spreadsheet.

Consequently, if the value is wrong, the result will also be wrong. In Table 6, the values that were nearest to

each other were those of the molar volumes obtained using van der waals and Redlich-Kwong equations of state

with a percentage difference of 3.59%. In Table 13, specific volumes using Redlich-Kwong-Soave and van der

waals were found to be similar.

The properties and equations are already made available in Aspen Plus when solving chemical engineering

problems. The user must choose which equation is to be utilized from the list. In this Machine Problem,

ideal gas, and Redlich-Kwong-Soave were used in Aspen Plus®.

Conclusion

Equations of state can be used for the calculation of the volume of a gaseous substance. In chemical

engineering, the volume calculated is used in designing, sizing, and costing of plants. The simplest form of EOS

is the ideal gas equation. Real gases, however, do not behave ideally at high pressures and low temperatures. To

account for the deviation from ideal behavior of gases, various equations of state were formed. These equations

of state are modifications of the preceding one. Additional parameters such as a and b were added to account for

the interaction forces between two molecules and excluded volume properties. Other parameters such as α, w,

and m were added to accurately predict the values of a and b. The more recent and complex the equation of state,

the more accurate the results are. To solve this equation of states, thermodynamic properties are needed which

can be obtained from various resources such as textbooks and the Perry’s Chemical Engineering Handbook. For

calculation involving mixtures, the parameters for each component should be considered. Calculations using EOS

can be time consuming and tedious, especially using recent and more complex equations of state. To aid these

calculations, application such as MS Excel and Aspen can be utilized. The necessary data and equations for each

EOS are inputted in MS Excel. Aspen, on the other hand, only needs the input data for the calculations.

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 Machine Problem No. 2
EQUATIONS OF STATE

References

(1) Borgnakke, C. & Sonntag, R.E. (2009). Fundamentals of Thermodynamics, 7ed. New Jersey: John Wiley and

Sons, Inc.

(2) Equations of State. Retrevied at

https://serc.carleton.edu/NAGTWorkshops/mineralogy/mineral_physics/eos.html on February 5, 2017

(3) Chapter 3: Equations of State. Retrieved at http://web.iitd.ac.in/~pmvs/courses/mel140/EOS-vapor.pdf on

February 5, 2017

(4) Smith, J.M., Van Ness, H.C. & Abbott, M.M. (2004). Introduction to Chemical Engineering

Thermodynamics, 7ed. New York: McGraw-Hill Companies, Inc. Seader, J.D., and Henley, E.J. Separation

Process Principles. 2e. New Jersey: John Wiley and Sons, Inc

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