Machine Problem No.

3
EQUATIONS OF STATE

Objective
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.

Theoretical Discussion

Solving equations of state allows the determination of the specific volume of a gaseous mixture of chemicals at a
specified temperature and pressure. By determining the specific volume, the size and therefore, the costof
the plant, including the diameter of pipes, the horsepower of compressors and pumps, and the diameter of
distillation towers and chemical reactors. The specific volume is also the first step in calculating the enthalpy and
vapor-liquid properties of mixtures. Enthalpy is important when making energy balances.

In order to solve equations of state, algebraic equations must be solved. Functions in MS Excel are available
for such calculations. Aspen Plus used modified equations of state to easily and accurately solve problems
involving gaseous mixtures.

The ideal gas equation of state relates the pressure, temperature and specific volume.

= or = where = (3.1)

where 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. This equation is quite adequate when the pressure is low. However, many chemical
processes take place at very high pressure.

Other equations of states have been developed, usually in conjunction with process simulators, to address the
chemical processes at high pressure. One generalization of the ideal gas law is the van der Waals equation of
state:

= (3.2)

In this equation, a accounts for the interaction force between two molecules and b accounts for the excluded
volume.

The Redlich-Kwong Equation of state is a modification of van der Waals Equation of State:

= (3.3)
( + )

where
2 2
= 0.42748 ( ) (3.4)

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= 0.08664 ( ) (3.5)

= (3.6)

1
= (3.7)
0.5

In these equations, Tc is the critical temperature, pc is the critical pressure and Tr is the reduced temperature. is
particular to the Redlich-Kwong Equation of State.

The Redlich-Kwong Equation of State was further modified by Soave to give the Redlich-Kwong-Soave Equation
of State which is common in process simulators.

= (3.3)
( + )

The parameter is given by a different formula.

= [1 + (1 0.5 )]2 (3.8)

= 0.480 + 1.574 + 0.1762 (3.9)

is the acentric factor, which is a tabulated quantity for many substances.

The Peng-Robinson equation is another variation:

= (3.10)
( + ) + ( )

These equations can be rearranged into a cubic function of specific volume. the form of the Redlich-Kwong and
Redlich-Kwong-Soave Equation of State is:

3 () 2 () + ( 2 ) = 0 (3.11)

For a pure component, the parameters a and b are determined from the critical temperature, the critical pressure,
and the acentric factor. For mixtures, it is necessary to combine the values of a and b for each component
according to the composition of the gaseous mixture according to the following mixing rules:

2 2
= 0.42748 ( ) ; = ( 0.5 ) 2 (3.12)

=1

= 0.08664 ( ) ; = (3.13)

=1

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EQUATIONS OF STATE

where
1
= (for Red Kwong) (3.14)
0.5

2
= [1 + (1 0.5 )] (for Redlich Kwong Soave) (3.15)

Illustrative Example

Determining the specific volume of a substance using MS Excel Goal Seek

Find the specific volume of n-butane at 500 K and 18 atm using the Redlich-Kwong Equation of State.

1. Find the critical temperature and pressure. Perrys Chemical Engineers Handbook gives Tc = 425.2 K
and pc = 37.5 atm.

2. Calculate the values of a and b using Equation 3.8 and 3.9.

3. Prepare a spreadsheet for the parameters and results. Supply the cells with the needed formula. Refer to
the equations given in the Theoretical Discussion. Figure 3.1 shows a sample spreadsheet.

Figure 3.1. Sample Spreadsheet

4. Use the Goal Seek command to make f(v) [cell I7] equal to zero by changing cell v [I6]. The Goal Seek
function may be found under Data Data Tools What If Analysis. Figure 3.2 shows the Goal Seek
dialog box.

Figure 3.2. Goal Seek Dialog Box

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5. Figure 3.3 shows the Goal Seek Results, including the value of v.

Figure 3.3. Goal Seek Results

Determining the specific volume of a substance using using Aspen Plus

Find the specific volume of n-butane at 500 K and 18 atm using the Redlich-Kwong-Soave Equation of State.

1. Start Aspen Plus and choose Template. When the New window appears, choose General with Metric
Units. Choose Property Analysis in the Run Type (lower right-hand corner). Figure 3.4 shows the New
window.

Figure 3.4. New Window

2. The Data Browser opens next. On the left pane, the following folders are shown: Setup, Components,
Properties, Reactions, Flowsheeting Options, Summary. Note that in Aspen Plus, folders marked in
red represent incomplete data inputs. Figure 3.5 shows the Data Browser window.

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Figure 3.5. Data Browser Window

3. Choose Component Specifications and enter the name or formula of the chemical (n-butane). If Aspen
Plus does not recognize your chemical, a window appears that allows you to search again, and it will
suggest a number o f possibilities. Note that it is important that there is an entry for the chemical in the
column Component Name. The first column is what you are naming the chemicals but the third column
is what Aspen Plus is using when it gets the physical properties. Note, too, that you no longer need to
look for the properties of your component in the Perrys Chemical Engineers Handbook, since Aspen
Plus has a database for such. Figure 3.6 shows the Components Specification window.

Figure 3.6. Components Specification Window

4. Once the component specifications are complete, choose Property Specifications. Use the following
data:
Process Type: All
Base Method: RK Soave
Property Method: RK Soave
Use True Components: <checked>

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5. On the menus at the top, choose Tools Analysis Property Pure. On the Pure Component
Properties Analysis Window that appears, choose the following:
Process Type: Thermodynamic
Property: V
Phase: Vapor
Selected Components: n-butane
Temperature Units: K
List of Values 500, 510
Pressure 18 atm
Property Method: RK Soave

6. A graph appears with the plotted results. A table is also generated (behind the graph).

Determining the specific volume of a mixture using Aspen Plus

Find the specific volume of a mixture consisting of 630 kmol/h of carbon monoxide, 1130 km/h, 189 kmol/h or
carbon dioxide, and 63 kmol/h of hydrogen at 1 atm and 500 K.

1. Start Aspen Plus and choose Template. Choose General with Metric Units. Choose Flowsheet in the
Run Type.

2. The Process Flowsheet Window appears, as shown in Figure 3.7. Note that the bottom part shows the
Model Library.

Figure 3.7. Process Flowsheet Window

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3. To place a model or unit operation (called block) from the Model Library to the flowsheet, click on the
desired model and click on the screen where you intend to place the block. Blocks may be renamed or
deleted by choosing the right option upon right click. On the Model Library, choose Pressure
Changers, and place a Compressor.

4. To add material streams to and from blocks, click on Material Streams. Click on the flowsheet where
you want the stream to originate and drag the cursor to where you want it to end. When done, click the
arrow on the upper left of Material Streams box. Note that if any red arrows show in the flowsheet, it
means that the block is not properly connected. Figure 3.8 shows a single compressor with material
streams as placed in the flowsheet.

Figure 3.8. Compressor with Material Streams

5. Click on the Data Browser (glasses icon). This brings up the menu much like in the previous example,
only with more folders. Specify the components in the same manner as the previous example.

6. Choose RK-Soave on the Property Specification.

7. On the Streams folder, note that there are two subfolders, 1 and 2. Be careful in specifying the
properties of each stream. Choose Stream 1 Input. Specify the following:
Substream Name Mixed
State Variables Temperature and Pressure
Total Flow Mole
Composition Mole-Flow (kmol/hr) specify flow rates

8. Choose Blocks Specifications:

Type Isentropic
Discharge Pressure 7.09275 bar

9. Once all data are complete, click on Next (N icon). Once the calculations are complete, click the
Results box to return to the regular menu. Look at Results Streams. The stream data will appear in
tabular form.

10. The specific volume can be obtained by dividing the volumetric flow rate by the molar flow rate.

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11. The flowsheet and mass and energy balance may be transferred to a word processing program by select,
copy, paste. The stream table may also be selected and pasted into MS Excel (Results Summary
Stream).

12. Detailed information can be obtained using View Report.

Reference
Finlayson, Bruce. Introduction to Chemical Engineering Computing. New Jersey: John Wiley & Sons,
Inc., 2006.

Preliminary Data

Answer the following problems using the specified tool. Save the file on the mapped network drive using the specified
filename format.

1. Find the molar volume of ammonia gas at 56 atm an d450 K using the Redlich-Kwong equation of state using MS
Excel. Save as MP3A-<No.>-Surname

2. Find the molar volume of ammonia gas at 56 atm an d450 K using the Redlich-Kwong equation of state using Aspen
Plus. Generate the report with the pertinent data and results and save as a MS Word file. Save as MP3B-<No.>-
Surname

3. Consider the following mixture going into a water-gas shift reactor to make hydrogen for the hydrogen economy: CO,
630 kmol/h; H2O, 1130 kmol/h; CO2, 189 kmol/h; H2, 63 kmol/h. The gas is at 1 atm and 500 K. Use MS Excel to
calculate the specific volume of the mixture using (a) ideal gas equation; (b) Redlich-Kwong Equation of State; (c)
Redlich-Kwong-Soave Equation of State; (d) Peng-Robinson Equation of State. Acentric factors: Co 0.049; H2O 0.344;
CO2 0.225; H2 -0.22. Save as MP3C-<No.>-Surname

4. Use Aspen Plus to solve Problem No. 3. Save as MP3D-<No.>-Surname

Reminder

Your final report should explain what problem you have solved and how you solved it. Focus on the
chemical engineering information rather than the detailed step-by-step process of solution.

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