Simulis Thermodynamics

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Thermodynamic properties and phase equilibria

calculation server

Properties and equilibria calculation service

Version 1.3

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Simulis Thermodynamics
Version 1.3
Copyright 2004-2008 by ProSim SA

Simulis Thermodynamics
Contents - 1
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CONTENTS
1. INTRODUCTION -----------------------------------------------------------------------------------------------------------------------------------1
2. HOW TO USE ------------------------------------------------------------------------------------------------------------------------------------ 2
2.1. Accessibility and availability .................................................................................................................. 2

3. MaiN WINDOW --------------------------------------------------------------------------------------------------------------------------------- 3

3.1. Modifications.......................................................................................................................................... 4
3.2. Unit systems .......................................................................................................................................... 4
3.3. Sessions ................................................................................................................................................ 4
3.4. Help ....................................................................................................................................................... 4
3.5. Data ....................................................................................................................................................... 5
3.5.1. The mixture composition ............................................................................................................... 5
3.5.2. The calculation list ......................................................................................................................... 5
3.5.2.1. The critical properties calculation ..............................................................................................................................5
3.5.2.2. The equilibria calculation...........................................................................................................................................6
3.5.2.3. The kvalues and surface tension calculation .............................................................................................................7
3.5.2.4. The phase envelop calculation ..................................................................................................................................8
3.5.2.5. The phase envelop deviation calculation...................................................................................................................9
3.5.2.6. Physical-Chemical properties calculation ................................................................................................................10
3.5.2.7. Reid vapor pressure calculation ..............................................................................................................................11

3.6. Estimation and results ......................................................................................................................... 12

3.6.1. The copy of results ...................................................................................................................... 12
3.6.2. The Excel export.......................................................................................................................... 12
3.6.3. Trace the results chart................................................................................................................. 13
3.6.3.1. The 2D chart ...........................................................................................................................................................13
3.6.3.2. The ternary diagram................................................................................................................................................13

4. EXAMPLES-------------------------------------------------------------------------------------------------------------------------------------14
4.1. Example of critical properties calculation ............................................................................................ 14
4.1.1. Data ............................................................................................................................................. 14

Simulis Thermodynamics
Contents - 2
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4.1.2. Results......................................................................................................................................... 14
4.1.3. Charts .......................................................................................................................................... 15
4.2. Example of equilibria calculation ......................................................................................................... 16
4.2.1. Data ............................................................................................................................................. 16
4.2.2. Results......................................................................................................................................... 17
4.2.3. Charts .......................................................................................................................................... 17
4.3. Example of kvalues and surface tension calculation........................................................................... 18
4.3.1. Data ............................................................................................................................................. 18
4.3.2. Results......................................................................................................................................... 19
4.3.3. Charts .......................................................................................................................................... 19
4.4. Example of phase envelop calculation ................................................................................................ 20
4.4.1. Data ............................................................................................................................................. 20
4.4.2. Results......................................................................................................................................... 21
4.4.3. Charts .......................................................................................................................................... 21
4.5. Example of phase envelop deviation calculation................................................................................. 22
4.5.1. Data ............................................................................................................................................. 22
4.5.2. Results......................................................................................................................................... 24
4.5.3. Charts .......................................................................................................................................... 24
4.6. Example of physical-chemical properties calculation. ......................................................................... 25
4.6.1. Data ............................................................................................................................................. 25
4.6.2. Results......................................................................................................................................... 26
4.6.3. Charts .......................................................................................................................................... 27

Simulis Thermodynamics
Introduction - 1
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1. INTRODUCTION
Simulis is our new range of software-oriented components. This range includes 3 products today:
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Simulis Conversions: system of management of units conversion of physical quantities,

also including two tools, one for conversion and one allowing to create new quantities
and/or units.

Simulis Properties: (Simulis Conversions included) properties server (constants or

temperature dependent) of pure substances.

Simulis Thermodynamics: (Simulis Properties included and thus Simulis

Conversions) server of thermodynamic properties and fluid phase equilibria for mixtures.
This server offers a great CAPE-OPEN compatibility: "thermodynamic socket"
implementation and abilitity to generate "property packages".

This service, included in Simulis Thermodynamics identifies all possible calculations on a

thermodynamic calculator.
Features are described in this document.

Simulis Thermodynamics
How to use - 2
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2. HOW TO USE
2.1. Accessibility and availability
The calculation service can be open from the thermodynamic calculator editor thank to the
Calculate action vailable in the Services menu.

Simulis Thermodynamics

Main window- 3

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3. MAIN WINDOW
The main screen of the tool contains of the following areas:
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Modifications.
Unit systems.
Sessions.
Help.
The data.
The results.

Simulis Thermodynamics

Main window- 4

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3.1. Modifications

Allows you to cancel or renew changes made.

3.2. Unit systems

See the documentation about the unit system editor

3.3. Sessions

Its possible to create different calculation sessions on the same thermodynamic calculator.
To a session is associated:
- A name (By default, New session)
- A calculation typel (By default, the physical-chemical properties calculation).
This menu allows you to launch the calculations on the current session or on all the sessions
defined by the user.

3.4. Help

Give access to the user manual.

Simulis Thermodynamics

Main window- 5

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3.5. Data
3.5.1. The mixture composition
To characterize the mixture composition its necessary to specify:
- The points of the mixture composition (ex : Ethane from 0 to 1 in 11 points),
- The compound which composition is automatically calculated,
- The values type : fractions or quantities,
- The composition type: molar ou mass.
3.5.2. The calculation list
Six distinct calculations are available:
- The critical properties.
- The equilibria.
- The kvalues and surface tension.
- The phase envelop.
- The phase envelop deviation.
- Physical-Chemical properties.
- The Reid Vapor Pressure.
3.5.2.1. The critical properties calculation

First its necessary to specify the calculation conditions:

- The model to use: the calculator or the predictive model.

Simulis Thermodynamics

Main window- 6

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- The mixture composition.

3.5.2.2. The equilibria calculation

First its necessary to specify the calculation conditions:

- The equilibrium property to calculate,
- The data necessarye for calculating that may be the temperature, the pressure, the vapor
ratio, the volume, the enthalpy, the entropy, the internal energy.
- The mixture composition,
- If the flash is automatically initialized or not.
- The results type: molar or mass.
- The compound for the Henry Constant calculation.

Simulis Thermodynamics

Main window- 7

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3.5.2.3. The kvalues and surface tension calculation

First its necessary to specify the calculation conditions:

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The properties and derivatives to calculate,

The physical state: automatically defined, vapor-liquid, dew point, bubble point,
The associated system,
The temperature and pressure,
The mixture composition.

Simulis Thermodynamics

Main window- 8

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3.5.2.4. The phase envelop calculation

First its necessary to specify the calculation conditions:

- The properties necessary for calculating: The temperature, the temperature step, the
pressure, the pressure step, the vapor ratio, the stop criterium and the number of points.
- The critical temperature and pressure if provided, else they are calculated,
- The mixture composition.

Simulis Thermodynamics

Main window- 9

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3.5.2.5. The phase envelop deviation calculation

First its necessary to specify the calculation conditions:

- The temperature, the temperature step, the pressure, the pressure step, the vapor ratio, the
stop criterium and the number of points.
- The critical temperature and pressure if provided, else they are calculated,
- The mixture composition.
- The experimental points to calculate the deviation.

Simulis Thermodynamics

Main window- 10

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3.5.2.6. Physical-Chemical properties calculation

First its necessary to specify the calculation conditions:

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The properties and derivatives to calculate,

The physical state: automatically determined, liquid, vapor, dew point, bubble point,
The associated system (if necessary),
The temperature and pressure,
The mixture composition,
The results type: molar or mass.

Simulis Thermodynamics

Main window- 11

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3.5.2.7. Reid vapor pressure calculation

First its necessary to specify the calculation conditions:

- The type of Reid vapor pressure calculation,
- If necessary, the temperature and the reference temperature,
- The mixture composition,

Simulis Thermodynamics

Main window- 12

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3.6. Estimation and results

The results may be copied, exported to Excel or traced on a chart.
Example

3.6.1. The copy of results

This button allows you to copy the results grid to the clipboard.
3.6.2. The Excel export

Select the file for the Excel export, a page called with the session name and containing the results
is created. If the page exist, you will have to confirm the export in this page.

Simulis Thermodynamics

Main window- 13

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3.6.3. Trace the results chart

A wizard is at your disposal to create a chart and to analyse the results.

You may have to choice between a Classic 2D chart and a ternary diagram.
The ternary diagram is available only if the calculation is made on three compounds.
3.6.3.1. The 2D chart
You have to specify at the different stages of the wizard:
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The chart title.

The title of the X axis.
The data for the X axis.
The title of the Y1 axis.
The data for the Y1 axis.
The title of the Y2 axis.
The data for the Y2 axis.
3.6.3.2. The ternary diagram

You have to specify:

- The points.
- The lines.
- The areas.

Simulis Thermodynamics
Examples - 14
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4. EXAMPLES
4.1. Example of critical properties calculation
4.1.1. Data
The thermodynamic calculator:
- Compounds: Ethane, Methane
- Mode: Soave-Redlich-Kwong (SRK)
- Binaries: Automatically generated
Data necessary for calculating:
- The model : The calculator model
- The fractions type : Molar
- The mixture composition: Ethane from 0 to 1 with a step of 0.1 (11 points)

4.1.2. Results

The critical properties: the temperature, the pressure, the volume, the compressibility factor and the
molar density are calculated for the different mixture compositions.

Simulis Thermodynamics

Examples- 15

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4.1.3. Charts
Lets trace the chart for the pressure function of the temperature
Click on the button
Specify at the differents steps of the wizard:
- The data for the X axis: The temperature
- The data for the Y1 axis: The pressure

Simulis Thermodynamics

Examples- 16

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4.2. Example of equilibria calculation

4.2.1. Data
Thermodynamic calculator:
- Compounds: Water, Ethanol
- Model : NRTL
- Binaries : Automatically generated
Data necessary for calculating:
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The equilibrium property to calculate: Bubble and dew temperature (for example)
The pressure: 1 atm.
The mixture composition: Water from 0 to 1 with a step of 0.1 (11 points)
Automatic initialization.
The results type: Molar.

Simulis Thermodynamics

Examples- 17

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4.2.2. Results

The liquid and vapor fractions, the equilibrium constants are calculated with the bubble and dew
temperatures.
4.2.3. Charts

The equilibrium charts of the temperatures (bubble and dew) and of the vapor fractions are traced
automatically.

Simulis Thermodynamics

Examples- 18

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4.3. Example of kvalues and surface tension calculation

4.3.1. Data
Thermodynamic calculator:
- Compounds: Water, Ethanol
- Model : NRTL
- Binaries : Automatically generated
Data necessary for calculating:
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The properties to calculate: Surface tension, Kvalues

The physical state: automatically determined
The associated system: vapor-Liquid
The pressure: 1 atm
The temperature: 298.15 K
The mixture composition: Water from 0 to 1 with a step of 0.1 (11 points)

Simulis Thermodynamics

Examples- 19

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4.3.2. Results

The vapor ratio, the liquid and vapor fractions are calculated with the surface tension and Kvalues.
4.3.3. Charts
Lets trace the chart for the surface tension function of the mixture composition.
Click on the button
Specify at the differents steps of the wizard:
- The data for the X axis: Mixture composition - WATER
- The data for the Y1 axis: The surface tension

Simulis Thermodynamics

Examples- 20

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4.4. Example of phase envelop calculation

4.4.1. Data
The thermodynamic calculator:
- Compounds: Ethane, Methane
- Mode: Soave-Redlich-Kwong (SRK)
- Binaries: Automatically generated
Data necessary for calculating:
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The temperature: 298.15 K

The temperature step: 0.1 K
The pressure: 1 atm
The pressure step: 0.1 atm
The vapor ratio: 1
The stop criterium: 5
The number of points: 50
The critical temperature and pressure and calculated.
The mixture composition: Ethane at 0.5

Simulis Thermodynamics

Examples- 21

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4.4.2. Results
The critical point and all the points of the phase envelop are calculated.

4.4.3. Charts
At the end of the calculation the phase envelop chart is automatically generated.

Simulis Thermodynamics

Examples- 22

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4.5. Example of phase envelop deviation calculation

4.5.1. Data
The thermodynamic calculator:
- Compounds: Ethane, Methane
- Mode: Soave-Redlich-Kwong (SRK)
- Binaries: Automatically generated
Data necessary for calculating:
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The temperature: 298.15 K

The temperature step: 0.1 K
The pressure: 1 atm
The pressure step: 0.1 atm
The vapor ratio: 1
The stop criterium: 5
The number of points: 50
The critical temperature and pressure and calculated.
The mixture composition: Ethane at 0.5
Enter the experimental points

Simulis Thermodynamics

Examples- 23

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Example of experimental points

173,097
179,041
184,986
190,883
196,781
202,678
207
214,192
219,809
224,2
230,668
235,817
240,778
247,1
250,045
256,1
258,096
263,7
264,789
269,4
270
270,7
266,928
261,124
255,694
250,546
245,584
239,5
235,849
232,5
226,113
220,4
216,284
211,322
206,267
201,212
196,064
190,822
185,486
180,056
174,533
168,917
163,3
157,59
151,786
145,982
140,084
133,1
128,289
122,9

1
1,43621
2,01183
3,1
3,68499
4,85361
6,26931
7,95999
9,95471
12,2844
14,9327
17,9135
21,2422
24,9386
28,8
33,2559
37,5
42,67
47,5
53,1882
58,8902
62,5316
67,5
66,6158
63,8
60,8178
57,4574
53,9996
50,467
46,9171
43,3925
39,9257
36,4787
33,8
29,8714
26,7503
23,7374
20
18,1179
15,5485
13,1613
11,6
9,01663
7,27007
5,73479
4,9
2,9
2,43052
1,4
1,1691

Simulis Thermodynamics

Examples- 24

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4.5.2. Results
The deviation and all the points of the phase envelop are calculated.

4.5.3. Charts
At the end of the calculation the phase envelop chart is automatically generated.

Simulis Thermodynamics

Examples- 25

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4.6. Example of physical-chemical properties calculation.

4.6.1. Data
Thermodynamic calculator:
- Compounds: Water, Ethanol
- Model : NRTL
- Binaries : Automatically generated
Data necessary for calculating:
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The properties to calculate: Isobaric specific heat.

The physical state: automatically determined
The associated system: Vapor-Liquid
The pressure: 1 atm
The temperature: From 300 K to 400K with a step of 5 (21 points)
The mixture composition: Equimolar, Water at 0.5
The results type: Molar

Simulis Thermodynamics

Examples- 26

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4.6.2. Results
The vapor ratio, the liquid and vapor fractions, the equilibrium constants are calculated with
selected properties, in this case, the isobaric specific heat.

Simulis Thermodynamics

Examples- 27

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4.6.3. Charts
Lets trace the chart for the isobaric specifc heat function of the temperature.
Click on the button
Specify at the differents steps of the wizard:
- The data for the X axis: The temperature
- The data for the Y1 axis isobaric specifc heat liquid and vapor

Simulis Thermodynamics

Examples- 28

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4.7. Example of Reid vapor pressure calculation.

4.7.1. Data
Thermodynamic calculator:
- Compounds: Methane, Ethane, Propane, Isobutane, n-Butane, n-Pentane, n-Hexane, nHeptane, n-Octane, n-Nonane, n-Decane, n-Dodecane, n-Docosane, Water, Hydrogen,
Nitrogen
- Model : Peng Robinsorn (PR)
- Binaries : Automatically generated
Data necessary for calculating:
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Calculation type: RVP API 5B1.1 (naphta).

The temperature: From 150 F to 200 F with a step of 5 (11 points)
The reference temperature: 100 F
The mixture composition:
METHANE
ETHANE
PROPANE
ISOBUTANE
n-BUTANE
n-PENTANE
n-HEXANE
n-HEPTANE
n-OCTANE
n-NONANE
n-DECANE
n-DODECANE
n-DOCOSANE
WATER
OXYGEN
NITROGEN

0,0346
0,1434
0,0932
0,0665
0,1234
0,0495
0,1001
0,0032
0,0223
0,1227
0,0197
0,1485
0,0729
0
0
0

Simulis Thermodynamics

Examples- 29

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4.7.2. Results
The Reid vapor pressure is calculated for each temperature step.

Simulis Thermodynamics

Examples- 30

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4.7.3. Charts
Lets trace the chart for Reid vapor pressure function of the temperature.
Click on the button
Specify at the differents steps of the wizard:
- The data for the X axis: The temperature
- The data for the Y1 axis: The Reid vapor pressure calculated.