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PE2000 Manual
PE2000 Manual
Preface
The first preliminary Windows release of PE had been shown at the 8th International
Conference on Properties and Phase Equilibria for Product and Process Design at
Noordwijkerhout, The Netherlands, on April 30th, 1998 (Pfohl et al., 1998a).
The first official Windows release of PE was finished in July 1998 and shown at the
17th European Seminar on Applied Thermodynamics at Vilamoura, Portugal (Petkov et
al., 1999) and on the International Workshop on Scientific Computing in Chemical
Engineering II at Hamburg, Germany, (Petkov et al., 1999a / Pfohl et al., 1999a).
From 1998 on, the actual releases of PE could be downloaded via internet from
http://vt2pc8.vt2.tu-harburg.de for free. Meanwhile more than 50 different research
groups use PE for the calculation of fluid-phase equilibria.
The first edition of the present book, which had been entitled Usage of PE – A
Program to Calculate Phase Equilibria, had been published in December 1998 (Pfohl
et al., 1998b).
In order to meet the needs of the users, continuous efforts led to significantly improved
versions of PE. The latest PE version, released February 2000, additionally enables the
users to include new equations of state by their own very easily (see Chapter 4).
-1-
Preface, Contents, Survey, and Introduction
Contents Page
Survey 4
Introduction 5
3 Mixtures .........................................................................................……............... 54
3.1 Mixture Calculations 56
3.1.1 Binary Phase Equilibrium Calculations 59
3.1.2 Ternary Phase Equilibrium Calculations 60
3.1.3 Calculating Phase Equilibria 62
3.1.4 Density Calculations 63
3,2 Optimisation of Binary Interaction Parameters 64
3.2.1 Optimising Parameters (Simplex-Nelder-Mead Method) 65
3.2.2 Scanning Parameters (Grid) 66
3.3 Graphical Output of Mixture Equilibria 68
3.3.1 Pxy- / yP-Diagrams (Binary) 68
3.3.2 Gibbs’ Triangles (Ternary and Quaternary) 71
3.4 Solid-Gas Equilibria 72
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Preface, Contents, Survey, and Introduction
Appendix ...............................................................................................….……...... 94
A1: EOS Implemented in PE 94
A2: Mixing Rules for Simple EOS 137
Literature..............................................................................................……........... 143
-3-
Preface, Contents, Survey, and Introduction
Survey
The program PE ( = Phase Equilibria ) has been developed in Professor Brunner’s
research group at the Technical University of Hamburg-Harburg, starting in 1985. PE
was built in order to obtain an efficient tool to correlate phase equilibria - especially
those at high pressure that are related to gas-extraction processes.
PE 2000 released 2/2000 runs on IBM compatible PC with Windows NT 4.0, Windows
95/98 or Windows 2000. It uses all features supplied by Windows: mouse control,
menu bars, dialog boxes as well as text and graphical output to commercial programs
like Word, Powerpoint, and Corel Draw. PE offers about 40 different equations of state
(EOS) with up to 7 different mixing rules for correlating phase equilibria.
Pure-Component Properties
PE offers subroutines to determine pure-component EOS parameters based on pure-
component vapour pressures and densities at saturation conditions. Graphical output
routines allow a visual comparison of experimental and calculated data of the vapour
pressure curve and PvT data.
A useful feature when correlating phase equilibria related to gas-extraction processes is
the possibility to enforce pure-component EOS parameters that reproduce the critical
temperature and pressure of the supercritical solvent during the pure-component EOS
parameter optimisation.
Mixture Data
PE offers subroutines to determine optimum binary interaction parameters for all EOS
in order to reproduce the phase behaviour of binary and ternary systems with a given
set of EOS and mixing rule, best. Further, PE offers the possibility to calculate phase
equilibria and densities with given interaction parameters at any conditions. Graphical
output routines provide plots of the miscibility gaps in binary and ternary systems in a
quality suitable for publications.
Warranty
Although many efforts have been made in order to supply a program without bugs, no
warranty is given for any of the results obtained with PE due to the size of the
program. Further, the users are encouraged to check results carefully. Most errors will
occur due to a wrong input of data by the user, usage of EOS and mixing rules that are
not appropriate for the investigated system, and convergence problems when using
inadequate initial guesses.
-4-
Preface, Contents, Survey, and Introduction
Introduction
The calculation of phase equilibria may serve as a cheap alternative compared to the
measurement of phase equilibria. This is especially true for high pressure where the
necessary equipment to measure phase equilibria is more expensive than at low
pressure. The calculation may often serve as a fast alternative compared to
measurements, also.
However, the calculation of phase equilibria requires suitable EOS or gE-models for
the system under investigation. When modelling high-pressure fluid-phase equilibria
with supercritical components, the use of EOS is advantageous compared to the use of
gE-models, because the latter require arbitrary reference points for the pure
supercritical compounds. Unfortunately, the successful use of all EOS is limited to
certain groups of compounds and certain process conditions, making necessary the use
of different EOS for different problems. So-called predictive methods are advanta-
geous, if hardly any information is known about the system under investigation. One
example of such predictive EOS is the PSRK model (Holderbaum, 1991, Fischer,
1993, Fischer and Gmehling, 1995/1996) which is based on the UNIFAC group
contributions. On the other hand such predictive models are inferior to other models
with individual adjustable parameters if sufficient is known about the system under
investigation. In such case the adjustment of these parameters can be used to make the
EOS accurately represent what is already known in order to use the EOS with these
parameters afterwards for calculating what is not known from experiments, yet.
The program PE was developed for modelling phase equilibria with non-predictive
EOS, excluding the necessity to build, handle and maintain large data bases - but
enabling best possible correlations, if sufficient is known about the system. PE offers
more than 40 different EOS, allowing the user to choose the one which best fits his
needs. PE also offers powerful routines to determine the above mentioned adjustable
parameters for pure components and mixtures by correlating experimental data and
subroutines to use these parameters for predictions of equilibria not necessarily
investigated experimentally yet.
The use of the EOS that best fits the users needs is the most important step for
achieving good results. The choice of the most suitable EOS for a given problem is up
to experience. The choice of the most elaborated, complicated and physically sound
EOS does not necessarily guarantee best results. One further key to success is the input
in order to determine the adjustable EOS parameters. „Garbage in, garbage out“ is also
true, here. This manual is intended to give users all necessary information to handle the
program PE, which might be seen as the third and final necessity before receiving the
desired correlation results. The manual does not intend to solve the first two
challenges.
-5-
Chapter 1: Input Files Containing Experimental Data
RT a
P= − 2 (1.1)
v −b v
N N
a = ∑ ∑ ξi ξ j ai a j (1 − k ij ) (1.2)
i =1 j =1
N N bi + b j
b = ∑ ∑ ξi ξ j (1 − lij ) (1.3)
i =1 j =1 2
Pure Components
The pure-component parameters ai and bi describe the PvT behaviour and phase
equilibria of the pure component of type i. These parameters ought to be derived from
pure-component properties of component i, only. Chapter 1.1 shows how experimen-
tally determined pure-component properties are stored by PE and how these properties
have to be entered in PE for each compound of interest. Chapter 2 shows how these
data can be used to obtain pure-component parameters for each EOS and how these
experimental results can be compared to results calculated with an EOS. Chapter 2 also
shows how properties of pure components can be predicted based on the pure-
component EOS parameters.
Mixtures
The calculation of mixture parameters (a and b) is based on the mixture composition
(mole fractions ξi), the pure-component properties (ai and bi ∀ i) and interactions
between unlike molecules (i≠j). Mostly, the interactions between unlike molecules are
expressed through deviations of the real mixture behaviour from an artificial mixture
behaviour with the same composition and a kind of standard interactions. It is common
practice to use so-called binary interaction parameters (like kij and lij in Eq. 1.2 and
1.3) in order to express the deviation from standard interactions (kij=lij=0) in each
binary system. These binary interaction parameters ought to be derived from binary
properties, only. The binary parameters determined this way can be used for
calculations in multicomponent systems assuming that binary interactions add up to the
multicomponent behaviour. Chapter 1.2 shows how experimentally determined mixture
data are stored by PE and how these data have to be entered in PE. Chapter 3 shows
how binary (and ternary) data can be used to obtain the binary interaction parameters,
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Chapter 1: Input Files Containing Experimental Data
how these data can be compared to the calculated results and how predictions can be
obtained that are based on these interaction parameters.
Isotherms (n= 2)
================
-7-
Chapter 1: Input Files Containing Experimental Data
0.400000E+03 0.114968E+04
0.500000E+03 0.116759E+04
0.750000E+03 0.120504E+04
0.100000E+04 0.123557E+04
3 0 1 Peng-Robinson
Tc 0.304130E+03
Pc 0.737700E+02
omega 0.225000E+00
info >Parameters describe CO2 well and (obviously) match Tc and Pc
7 1 24 SAFT-Conventional
u0/k 0.311490E+03
v00 0.260360E-01
m 0.842600E+00
eps/k 0.000000E+00
kap 0.000000E+00
eta/k 0.400000E+02
sites 0
info >Parameters match Tc and Pc, but m<1 (not reasonable) –> do not use !
7 1 24 SAFT-Conventional
u0/k 0.216080E+03
v00 0.135780E-01
m 0.141700E+01
eps/k 0.000000E+00
kap 0.000000E+00
eta/k 0.400000E+02
Sites 0 0 0
info >Parameters do not match Tc and Pc but describe CO2 well -> recommended
3 0 25 PC-SAFT
u0/k 0.152478E+03 [K]
d00 0.256674E+01 [A]
m 0.255961E+01 [-]
info >Parameters do not match Tc and Pc but describe CO2 well
---------------------------------------------------------------------------------------------------------
Figure 1.1a: Contents of the PCFILE CARBONDIOXIDE.PC.
Each PCFILE consists of a header, data for the vapour pressure curve, optional PvT
data, and optional pure-component properties for different equations of state.
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Chapter 1: Input Files Containing Experimental Data
The header
The header contains the name of the component, the source of the data (typically
„Author, Year“), the date when the user created the PCFILE, the molecular weight, the
critical temperature, and pressure of the compound, the acentric factor (Pitzer et al.,
1957). If the latter three properties are not known from experiment, they have to be
estimated, somehow.
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Chapter 1: Input Files Containing Experimental Data
for the compound “carbondioxide” by PE. Note that the EOS parameters would not be
used for the compound “carbon dioxide” in this example, because the filename without
the extension “.pc” is used herefore by PE.
This EOS parameter database saves a lot of typing efforts, because once a set of
parameters is stored here, it has never to be keyed in, again.
It is possible to store more than one EOS parameter set for each EOS in a PCFILE, but
only the last one for each EOS will be used by PE. This enables storing old parameters
which should not be used any more without the possibility that PE ever selects the
wrong set. In this example, there are two parameter sets for SAFT-Conventional and
only the latter one would ever be used by PE. The information stored together with the
parameters tells all users why the first EOS parameter set should not be used.
In general, users are urged to specify additional information together with the saved
parameters in the “info” line, so that all users can see what the saved parameters are
good for.
The EOS parameter data are stored in the format shown in Figure 1.1b and explained,
below.
---------------------------------------------------------------------------------------------------------
7 1 24 SAFT-Conventional
u0/k 0.216080E+03
v00 0.135780E-01
m 0.141700E+01
eps/k 0.000000E+00
kap 0.000000E+00
eta/k 0.400000E+02
Sites 0 0 0
info >Parameters do not match Tc and Pc but describe CO2 well -> recommended
---------------------------------------------------------------------------------------------------------
Figure 1.1b: EOS parameter block of the PCFILE CARBONDIOXIDE.PC.
The first line of the data block contains the number of lines containing any parameters
for this equation of state (here “7” lines) as well as the number of these lines which are
used for saving the number of association sites (here: “1” of 7 lines), and the internal
number of the equation of state in PE (here: “24” for SAFT-Conventional, compare
Appendix 1), and the name of the EOS (“SAFT-Conventional”)
The 6 lines with the EOS parameters are self explanatory because saved with the
parameter names and units.
The 7th line “Sites 0 0 0” means that there are neither (+)-sites, (-)-sites nor (COOH)-
sites on this molecule, i.e. that the total number of sites is 0, here. In previous versions
of PE, only the total number of sites was saved, leading to sites combinations which
could not be chosen. The table below “translates” the interpretation of lines in old
- 10 -
Chapter 1: Input Files Containing Experimental Data
format (starting with “sites” instead of “Sites”, also compare both SAFT data sets in
Figure 1.1a) by the new version of PE.
Figure 1.1c: Format of the sites line. The new version of PE reads old and new format.
- 11 -
Chapter 1: Input Files Containing Experimental Data
Selecting FILE/NEW/PURE-COMPONENT DATA from the main menu will cause creating
a new file containing pure-component properties (Figure 1.1d).
Figure 1.1e: Input of some data for the header of a new PCFILE.
Header
First, the user will be asked to enter the data necessary for the header of the PCFILE
(compare section 1.1.1, see Figure 1.1e). In order to enable the use of other data bases,
later, it is recommended to select a component from the data base /PE/NSTOFF.DAT or
add a new compound to the data base by pressing the [...]-button. After pressing the
[...]-button, the dialog box shown in Figure 1.1f will appear. Pressing the button
SELECT there, will select the highlighted component from the data bank and pressing
ADD NEW allows to add new components to this data base.
- 12 -
Chapter 1: Input Files Containing Experimental Data
In order to enable finding the desired compound in the data base quickly, PE provides
the possibility to search for compounds in the data base by pressing FIND. The search
can either be by COMPONENT NAME or BY CHEMICAL FORMULA (Figure 1.1g). A
search by NAME will not be „sharp“ or case sensitive, i.e. searching for „CARBON“
will find „carbon dioxide“, „carbon monoxide“ and similar. Searching by CHEMICAL
FORMULA will be case sensitive and „sharp“, i.e. searching for „H2“ will not find
„H2O“. The chemical formula has to be entered like in the list of the appendix by Reid,
Prausnitz and Poling (1987), i.e. „C2H6O“ instead of „C2H5OH“ for ethanol. The
button FIND AGAIN repeats the search for the next data base entry matching the search
criteria.
PE allows for new components to be added to the data base together with their
chemical formula, molecular weight, and pure-component properties such critical
pressure, critical temperature, normal boiling temperature, acentric factor when
pressing the button ADD NEW. In the case that the latter properties are not known but
the user knows the chemical structure of the new substance, they can be estimated
using group contribution methods (see chapter 1.2.4).
- 13 -
Chapter 1: Input Files Containing Experimental Data
Figure 1.1g: Searching for a compound in the pure-component data base NSTOFF.DAT.
Figure 1.1h: Adding further data for the header of the PCFILE and setting the units for
the input of the vapour pressure curve data.
- 14 -
Chapter 1: Input Files Containing Experimental Data
Note: In case saturated vapour densities/volumes are not known, the vapour volumes
(densities) should be set to arbitrary high (low) values like 1d+99 (1d-99).
Arbitrary low (high) vapour volumes (densities) would lead to undesired
program crashes during optimisations. „Good guesses“ for vapour densities
could be interpreted as experimental data and used for pure-component
parameter optimisations by other users, later. Therefore such guesses should be
avoided.
The flag PARAMETER OPTIMISATION indicates, if this data point should be used for
pure-component parameter optimisations later, VAPOUR PRESSURE DIAGRAM /
PV-DIAGRAM indicate, if the point should be plotted in diagrams showing the vapour
pressure curve / PvT data, later. Please, compare sections 2.1, 2.2, and 2.3. It is
recommended to use the default, i.e. set all flags for all points. However, for usual
compounds, for points closer than approximately 5 K to the critical temperature, the
flag PARAMETER OPTIMIZATION should not be set in order to improve convergence in
the calculations.
By pressing ADD, the point will be added to the PCFILE and PE will prompt for the next
point. By pressing ADD+EXIT after having entered the last point, the point will be
added to the PCFILE and PE will prompt for no further points on the vapour pressure
curve. Afterwards PE will ask if the user wants to enter PvT-data (see next section).
PvT data
The last step in creating a new PCFILE is the (optional) input of PvT data. These PvT
data are not used for pure-component parameter determinations / optimisations. They
are only used for graphical output purposes (section 2.3).
- 15 -
Chapter 1: Input Files Containing Experimental Data
The PvT data have to be entered using isothermal blocks, i.e. isotherms (Figure 1.1j).
Selecting NO there, will close the PCFILE and finish the creation process. At the
beginning of the input of each new isotherm, the temperature of the isotherm and the
units for the input of data for the isotherm have to be specified - similar to the input of
the vapour pressure curve (Figure 1.1k). Different input units can be used for different
isotherms.
Figure 1.1j: Starting the input of a new isotherm or finishing the creation of the
PCFILE.
Figure 1.1k: Setting the temperature and the units for the input of the next isotherm.
- 16 -
Chapter 1: Input Files Containing Experimental Data
- 17 -
Chapter 1: Input Files Containing Experimental Data
Alternatively to the way described in the above section 1.1.2, a PCFILE can also be
created very quickly using the pure-component data compilation by Daubert and
Danner (1989). This data compilation contains coefficients for functions describing
different pure-component properties like vapour pressure and liquid density. Selecting
“FILE/NEW/PURE-COMPONENT DATA, D+D” from the main menu will allow for
creating a new PCFILE containing pure-component properties (Figure 1.1m).
Using the dialog box shown in Figure 1.1n, data from the data compilation by Daubert
and Danner have to be entered in the sections MAIN DESCRIPTION, LIQUID DENSITY,
and VAPOUR PRESSURE. The units for this dialog box are the same as used by Daubert
and Danner in order to simplify the typing procedure.
So far, Daubert and Danner use their “equation 105” for liquid densities, while they
use “equation 101” for vapour pressure correlation:
B
Equation 101 by Daubert and Danner: Y = exp A + + C ln T + DT E
T
A
Equation 105 by Daubert and Danner: Y = T D
1+ 1−
C
B
- 18 -
Chapter 1: Input Files Containing Experimental Data
Figure 1.1n: Dialog box for the input of coefficients from the data compilation by
Daubert and Danner in order to generate a PCFILE using PE.
In order to specify the temperature range of the data points to be written to the PCFILE,
the minimum and maximum temperature as well as the step size have to be entered in
the section TEMPERATURE RANGE. All point written to the PCFILE will automatically
have all flags set for PARAMETER OPTIMISATION, VAPOUR PRESSURE CURVE DIAGRAM,
and PV-DIAGRAM (compare Figure 1.1i). Like explained in the previous sections, the
maximum temperature should be sufficiently below the critical temperature (normally
about 5K) in order to be able to achieve convergence, later. The temperature range
chosen here, has to be within the ranges where the coefficients / equations by Daubert
and Danner are valid.
The optional subsequent input of PvT data is identical to the input described in section
1.1.2.
- 19 -
Chapter 1: Input Files Containing Experimental Data
Figure 1.1p:
- 20 -
Chapter 1: Input Files Containing Experimental Data
The Header
The header contains the name of the system, the source of the data (typically: author,
year), the date when the file was created, and complete information about the literature
source of the data (typically: authors’ names, manuscript title, journal, vol., no., year ).
Pure-Component Data
The pure-component data section includes the number of components (02, here), the
names of the components, and pure-component properties (like molecular weight,
normal boiling temperature, critical temperature, critical pressure, acentric factor, and
solid density for solid-gas-equilibrium calculations). They latter are stored in such a
way that one line contains a given property of all components in the form of an alpha
numerical identifier (five letters) and the values for each component.
- 21 -
Chapter 1: Input Files Containing Experimental Data
---------------------------------------------------------------------------------------------------------
>CO2 + p-Cresol <
>Pfohl, 1998 <
>created on 1998-06-01 at 14:36<
Literature
----------
>Dissertation, <
>TU Hamburg-Harburg, <
>Thermische Verfahrenstechnik <
> <
6 properties
gmg 0.440100E+02 0.108140E+03
Tb 0.022222E+02 0.011111E+03
Tc 0.304130E+03 0.704650E+03
Pc 0.737700E+02 0.515000E+02
omega 0.225000E+00 0.513000E+00
s.dns 0.000000E+00 0.100000E+04
03 0 01 Peng-Robinson
Tc 0.304130E+03 0.704650E+03
Pc 0.737700E+02 0.515000E+02
omega 0.225000E+00 0.513000E+00
interaction parameter
---------------------
EOS= 1 MR=42 BL= 1 saved on 1998-06-01 at 14:36
0.10205
0.00000
0.05305
0.00000 0.00000
0.00000 0.00000
0.00000
0.00000
---------------------------------------------------------------------------------------------------------
Figure 1.2a: Contents of the EXFILE CO2_PCRESOL.EX
- 22 -
Chapter 1: Input Files Containing Experimental Data
- 23 -
Chapter 1: Input Files Containing Experimental Data
- 24 -
Chapter 1: Input Files Containing Experimental Data
do i = 1, N-1
write k(i,j) (j= i+1, N)
end do. Where: N = number of components in the system.
The order of appearance is: k(i,j), l(i,j), λ(i,j), s(1,j), s(j,1), kε(i,j), kκ(i,j). The s(i,j)
parameters are only used for the Dohrn-Prausnitz-polar EOS (number 6 in appendix
A1). They are saved in a format like:
Figure 1.2b: Selecting the menu entry to generate a new EXFILE with mixture data.
- 25 -
Chapter 1: Input Files Containing Experimental Data
Header
First, the user will be asked to enter the data necessary for the header of the EXFILE
(see section 1.2.1). The dialog box for this is shown in Figure 1.2c. The user also has
to decide if the input of composition will be in mole fractions or weight fractions. PE
will save the original numerical input to the EXFILE and do the conversions at the time
of phase equilibrium calculation.
Pure-Component Data
Second, the user will be prompted for an input of all component names and molecular
weights (Figure 1.2d). The [...]-BUTTONS allow access to the same pure-component
data base /PE/NSTOFF.DAT as already described in section 1.1.2 GENERATING
PCFILES.
- 26 -
Chapter 1: Input Files Containing Experimental Data
Figure 1.2d: Input of names and molecular weights of all components in the EXFILE.
Finally, the user is prompted for the input of pure-component properties and pure-
component EOS parameters.
Pure-component information from the data base will be used as default values for pure-
component properties for the header of the EXFILE (Figure 1.2e). If no experimental
pure-component data are available for Tc, Pc, Tb, and ω, these can be estimated by
pressing ESTIMATE (details in section 1.2.4).
Mixture calculations with a given EOS can only be performed if all necessary
parameters for this EOS and all components are entered. Some simple EOS like van-
der-Waals, Peng-Robinson and Soave-Redlich-Kwong, which only depend on the
parameters Tc, Pc, and ω, will use this information in the pure-component property
block for calculation routines as long as no block for the EOS itself is present. EOS
parameters for each EOS can be entered after double-clicking the appropriate EOS in
the dialog box shown in Figure 1.2f.
Boxes like the ones shown in Figure 1.2g will appear for each compound. If a PCFILE
with the name of one of the components in the EXFILE exists, PE will try to retrieve
EOS parameters from this file as default parameters for the dialog box in Figure 1.2g.
Selecting SAVE+EXIT in Figure 1.2f will lead to the next step - the input of the phase
equilibrium data.
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Chapter 1: Input Files Containing Experimental Data
Figure 1.2e: Input of pure-component data. Figure 1.2f: Selecting an EOS for the
input of pure-component parameters.
- 28 -
Chapter 1: Input Files Containing Experimental Data
The correct order for a binary system is: (compare Figure 1.2k):
1) T1 / P1 \
2) T1 / P2 > block 1
3) T1 / P3 ... /
4) T2 / P4 \
5) T2 / P5 > block 2
6) T2 / P6 /
7) T3 ... > block 3 ...
Those data in a block which should not be used for the calculation of the OBJECTIVE
FUNCTION, have to be marked as PLOT, ONLY.
The first equilibrium in each block will be used as INITIAL GUESS for the CALCULATION
OF ADDITIONAL POINTS (section 3.1). If this first point is not an experimentally
determined point, or if it should not be used for the calculation of the OBJECTIVE
FUNCTION for a different reason, the first point can be marked as INITIAL GUESS with
the appropriate radio button. See section 1.2.1 (Tables 1.1 and 1.2) for details. It is not
possible to add any data with flag=0 to a block except the INITIAL GUESS. The flags of
all equilibria can be changed by loading the EXFILE with an ASCII editor of the PE-
Viewer, later.
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Chapter 1: Input Files Containing Experimental Data
Figure 1.2h: Dialog box for the input of one phase equilibrium in an EXFILE block.
For each phase equilibrium, the type of equilibrium has to be specified. There are four
possibilities: a) L1-V, b) L2-V, c) L1-L2, and d) L1-L2-V. Figure 1.2i and Figure 1.2j
provide guidance to choose the correct types of equilibrium for each phase equilibrium.
The difference between L1-V and L2-V equilibrium becomes important, if different
miscibility gaps are encountered in one isothermal phase equilibrium block. If the
types of miscibility gaps are not chosen correctly, the plot programs will connect the
wrong tie lines in order to receive binodals in diagrams, later.
Pressing the button ADD will add the phase equilibrium to the EXFILE and ask for
further equilibria. Pressing the button ADD+EXIT will add the phase equilibrium to the
EXFILE and finish the generation of the EXFILE.
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Chapter 1: Input Files Containing Experimental Data
New:
If one phase composition edit box per phase is left empty in the dialog box shown in
Figure 1.2h, PE will automatically set the composition for this edit box so, that the sum
of fractions in this phase becomes unity and ask the user to confirm this setting.
Phase: L1
Phase: L2
Phase: V
Phase: L2
Phase: L1 Phase: V
three-phase region
- 31 -
Chapter 1: Input Files Containing Experimental Data
Figure 1.2k: Selecting a menu entry in order to add equilibrium data to an existing
EXFILE.
- 32 -
Chapter 1: Input Files Containing Experimental Data
Tc / K = 535 lg ∑ ∆T
Group Implementation in PE ∆T
− CH 3 -CH3 1.79
− CH 2 − -CH2 1.34
= CH − =CH-- 1.40
>C = >C= 0.89
≡ CH =3=CH 1.79
≡C− =3=C- 2.46
=C = =C= 1.03
- 33 -
Chapter 1: Input Files Containing Experimental Data
− NH − -NH- 3.04
− NH − (aromatic ) -NH- (aromatic) 7.64
> NH − (aromatic ) >N- 0.89
> N − (aromatic ) >N (aromatic)- 0.89
>N− >N- 4.74
−N = -N= 4.51
−S −S − -S-S- 9.83
−S− -S- 4.91
− SH -SH 5.36
−F -F 2.10
− F (aromatic ) -F (aromatic) 0.45
− F ( perfluoro ) -F (perfluoro) 0.54
− Cl -Cl 4.20
− Cl (disubstitu ted ) -Cl (disubsituted) 3.71
− Cl (trisubstit uted ) -Cl (trisubsituted) 3.17
− Br -Br 5.58
−I -I 8.04
− I (aromatic ) -I (aromatic) 10.77
Three − membered ring 3-membered ring 0.45
Five − membered ring 5-membered ring 2.23
Six − membered ring 6-membered ring 2.68
Heteroatom in ring Heteroatom in ring 0.45
Substituti on on carbon in a Subst. on C in a DB nonar. 0.58
double bound (nonaromati c)
Orthosubst itution in a benzene ring o-Subst. in a benzene ring 1.16
Conjugatio n, per double bound Conjugat. per double bond 0.13
CH * * − adjacent pairs of > CH − CH ** adjacent pairs of >CH- 0.76
- 34 -
Chapter 1: Input Files Containing Experimental Data
Tb / K = 198 + ∑ ∆Tb
Tb / K
Tc / K =
0,584 + 0,965∑ ∆Tc − (∆Tc )
2
1
Pc / bar = ,
(0,113 + 0,0032n − ∑ ∆P )
A c
2
- 35 -
Chapter 1: Input Files Containing Experimental Data
If the user did not already enter the required parameters he will be asked to do this:
Figure 1.2l.
Figure 1.2l: Input of parameters for estimating the critical temperature according to
the equation by Klincewicz.
- 36 -
Chapter 1: Input Files Containing Experimental Data
where
Tr is the reduced temperature T / Tc .
Prsat is the reduced vapour pressure P sat / Pc .
The calculation method for the acentric factor implemented in PE uses the Lee-Kesler
vapour pressure relation (Reid et al., 1987):
6,09648
α = − ln Pc / atm − 5,92714 + + 1,28862 ln θ − 0,169347θ 6
θ ,
15,6875
β = 15,2518 − − 13,4721 ln θ + 0,43577θ 6
Tb
where θ = .
Tc
- 37 -
Chapter 1: Input Files Containing Experimental Data
1.2.4f Implementation in PE
The group contribution methods in PE can be reached by selecting the menu entry
FILE/DATABASE in order to edit the pure-component data base nstoff.dat (Figure
1.2m).
If the user chooses the ADD NEW button in the occuring dialog box (Figure 1.1f),
another dialog box is displayed where the parameters for the new component can be
entered (Figure 1.2n). By pressing the ESTIMATE button in this dialog box, the required
property can alternatively be estimated according to the procedures described above.
Figure 1.2n: Dialog box with estimate buttons for group contribution methods.
- 38 -
Chapter 1: Input Files Containing Experimental Data
Using the Fedors or Joback method, the dialog box shown in Figure 1.2p is displayed.
This dialog box is the same for all group contribution methods – only, the list of groups
in the list box on the right side differs depending on the method chosen. There is an
example defining the structure of 2,2,3-trimethylpentan in the dialog box, below
(Figure 1.1p). 2,2,3-Trimethylpentan contains five methyl groups ( − CH 3 ), one − CH 2
group, one − CH , and one − C group.
- 39 -
Chapter 1: Input Files Containing Experimental Data
Figure 1.2p:
- 40 -
Chapter 2: Pure-Component Calculations
2 Pure-Component Calculations
PE offers two calculations modes: the pure-component mode and the mixture mode.
All calculations in the pure-component mode are based on the experimental data in the
PCFILES (section 1.1) and can be accessed by the options from the menu entry PURE
COMPONENT (Figure 2a).
- 41 -
Chapter 2: Pure-Component Calculations
isotherm with the experimentally determined critical temperature has a point of inflection
at the experimentally determined critical pressure. This way the calculated critical
temperature and pressure exactly match the experimentally obtained critical temperature
and pressure. Such parameters are said to “enforce (the correct reproduction of
experimentally determined) Tc and Pc”, below. Further EOS parameters might be chosen in
such a way that the calculated critical volume matches the experimentally determined
critical volume (Deiters, 1981) or that the temperature dependence of the vapour pressure
curve is reproduced well (Soave, 1972).
2) EOS parameters can be chosen in such a way that properties which are calculated with the
EOS reproduce certain experimentally determined properties best. The properties to be
matched are chosen to be similar to the properties that will be calculated with the EOS,
later. For calculating phase equilibria it is common practice to choose the liquid molar
volume and the pressure at saturation conditions (Huang and Radosz, 1990). Working with
physically sound EOS, the reproduction of the molar liquid volume is also a good measure
for liquid densities at higher pressures. However, it is no good measure, if empirical
temperature dependent volume translations are used and if the EOS parameters have been
adjusted to match the saturated liquid volumes, only (Chou and Prausnitz, 1989, Ji and
Lempe, 1997). In general, vapour volumes are not included in the optimisations, because
they depend on the ideal gas law to a high extent and because they are not strongly
correlated to molecular parameters, therefore.
3) EOS parameters can be obtained by using correlations that are based on EOS parameters of
similar compounds that are determined by one of the first two methods (Dohrn and
Brunner, 1994).
Figure 2.1a: Dialog box to choose if EOS parameters should match Tc and Pc.
The EOS parameters will be determined to allow the best possible reproduction of the
pure-component vapour pressure curve in the PCFILE of interest. Only points where the
o-flag in the PCFILE is set to „1“ are considered (compare section 1.1.1).
- 42 -
Chapter 2: Pure-Component Calculations
Enforcing EOS parameters that exactly reproduce the experimental values of Tc and Pc
from the PCFILE during the optimisations, restricts the choice of parameters
significantly. In such case, the first two parameters of the EOS will be set to values so
that Tc and Pc from experiments are reproduced exactly, automatically. For certain
EOS this procedure can significantly affect the quality of the reproduction of the
vapour pressure curve and densities (compare Figures 2.1f - 2.1j).
The dialog box shown in Figure 2.1b is the main input form for the optimisation of
pure-component parameters. The entries are explained below. If the reproduction of Tc
and Pc is enforced and the first two pure-component EOS parameters of the selected
EOS are Tc and Pc, the input of both is disabled (Figure 2.1c). If the reproduction of Tc
and Pc is enforced and the first two pure-component EOS parameters of the selected
EOS are not Tc and Pc, the input of both is enabled for the input of initial guesses - the
procedure for this case is described by Pfohl et al., 1998.
- 43 -
Chapter 2: Pure-Component Calculations
Figure 2.1c: Dialog box for an optimisation of pure-component EOS parameters with
an EOS where Tc and Pc are the first two parameters and where the correct
reproduction of Tc and Pc should be enforced.
Substance
With the button SUBSTANCE, the PCFILE with the pure-component data is selected. By
default the directory PE\PCFILE is selected but the user can open any PCFILE on every
disk and directory.
EOS
With the button EOS, the EOS to be used is selected (compare section 1.2.2).
Parameters
The section PARAMETERS displays the EOS parameter names and units. The values for
the parameters will be used as initial guesses for the optimisations. It is advisable to
give good estimates based on method 3 from above in order to ensure rapid
convergence. It is also advisable to use initial guesses which do not underestimate the
critical temperature, otherwise the optimisation procedure might not start at all.
- 44 -
Chapter 2: Pure-Component Calculations
Sites
The use of EOS which explicitly account for association like SAFT and the CPA-EOS
enforces the input of the number of interacting sites. For one molecule, either COOH-
sites can be selected or any combination of (+)- and (-)-sites. (+)-sites will only affect
calculation results, if any (-)-sites are present within the system - and vice versa.
One COOH-site is used for simple carboxylic acids (dimer formation, only); one (+)-
site and one (-)-site are used for simple alcohols (chain formation); two (+)-sites and
one (-)-site might be used for water (clusters formation). Two (+)-sites and two (-)-
sites may also be used for water (compare with Huang and Radosz (1991) and Fu and
Sandler (1995)). Also compare section 1.1.1.
Optimize
Parameters where the OPTIMIZE boxes are checked will be optimised using a Simplex-
Nelder-Mead algorithm (compare Nelder and Mead, 1965).
Grid
One parameter can be selected to be varied on a grid, that is specified by the lower and
upper border as well as the grid increments. The one-dimensional output lists can be
visualised, later (section 2.1.1). It might be useful to generate such plot in order to
judge about the magnitude of the influence of a certain EOS parameter on the
calculation results. A parameter can be either optimised or put a grid.
Running an Optimisation/Grid
An optimisation can be interrupted by selecting the STOP button from the toolbar. The
STOP button and STOP menu entry are only visible during optimisations/grid. After
each successful optimisation the achieved results will be displayed in a dialog box
(Figure 2.1d).
Figure 2.1d:
Optimisation results: Reproduction of
vapour pressure curve in the PCFILE.
- 45 -
Chapter 2: Pure-Component Calculations
The averaged relative errors in vapour pressure, liquid density, and vapour density are
shown as well as the value of the OBJECTIVE FUNCTION which was minimised during
the optimisation. The OBJECTIVE FUNCTION is the mean of the deviation in vapour
pressure and liquid density. The differences between the calculated and experimentally
determined critical temperature and pressure are also shown.
Such calculation is also available at PURE COMPONENT / CALCULATE DEVIATION.
Figure 2.1e: Setting the limits of the plot axis and determining the points to be shown.
Figure 2.1f and 2.1g show diagrams for carbon dioxide and the Peng-Robinson EOS,
enforcing and not enforcing experimentally determined Tc and Pc. The diagrams are
similar because the constraint to enforce Tc and Pc is not severe, here. It can be seen
that the acentric factor has a pronounced influence on the calculation of the vapour
- 46 -
Chapter 2: Pure-Component Calculations
pressures but not on liquid volumes. Figure 2.1h shows that the volume translation
added to the Peng-Robinson EOS (EOS 10 in appendix A1) has no influence on the
calculation of vapour pressures, because it was designed to have no influence on it
(Peneloux et al., 1982).
Figures 2.1i and 2.1j show diagrams for carbon dioxide and SAFT, also enforcing and
not enforcing experimentally determined Tc and Pc. The diagrams look very different,
because the constraint to enforce Tc and Pc is very severe, here. The choice of the chain
length m has a pronounced influence on calculated vapour pressures and liquid
volumes.
Figure 2.1f & 2.1g: Deviation analysis for CO2 described by the Peng-Robinson EOS,
when the correct reproduction of experimentally determined Tc and Pc is enforced (left
side) or not (right side). Vapour pressure deviation: - - - , Density deviation: -----.
Figure 2.1h: Deviation analysis for CO2 described by the PR EOS with volume
translation by Peneloux, when the correct reproduction of experimentally determined
Tc and Pc is enforced. Vapour pressure deviation: - - - , Density deviation: .
- 47 -
Chapter 2: Pure-Component Calculations
Figure 2.1i and 2.1j: Deviation analysis for CO2 described by SAFT, when the correct
reproduction of experimentally determined Tc and Pc is enforced (right side) or not (left
side). Vapour pressure deviation: - - - , Density deviation: .
- 48 -
Chapter 2: Pure-Component Calculations
Figure 2.2b: Dialog box for the calculation of a vapour pressure curve.
- 49 -
Chapter 2: Pure-Component Calculations
Figure 2.2c: Vapour pressure curve of carbon dioxide with liner axis.
Figure 2.2d: Vapour pressure curve of carbon dioxide with logarithmic axis
- 50 -
Chapter 2: Pure-Component Calculations
ρ-Diagrams
2.3 Calculation of Pρ
A complete Pρ-diagram can be calculated by selecting the menu bar entry PURE
COMPONENT / PVT DIAGRAM (Figure 2.3a). The limits for the ρ-axis have to be
specified (Figure 2.3b). First, the extend of the vapour-liquid two-phase region is
calculated, then isotherms will be calculated. The minimum accessible temperature is
the minimum temperature specified in the box similar to Figure 2.2b. For each
temperature of an isotherm specified in the PCFILE, one isotherm will be calculated.
Additional isotherms can be calculated by specifying them in the dialog box shown in
Figure 2.3b.
Figure 2.3b: Specifying limits for the ρ-axis in the Pρ-diagram and selecting
additional isotherms to be calculated.
- 51 -
Chapter 2: Pure-Component Calculations
ρ-Diagrams
2.3.1 Graphical Output of Pρ
The last Pρ-diagram which has been calculated according to the description in the
above section can be displayed by selecting the menu item PURE COMPONENT / PVT
DIAGRAM / PLOT. The limits of the ρ-axis specified at the time of calculation will be
used. The limits of the P-axis have to be specified at the time of the generation of the
diagram (Figure 2.3c). A Pρ-diagram for carbon dioxide is shown in Figure 2.3d.
- 52 -
Chapter 2: Pure-Component Calculations
After selecting PURE COMPONENT / CALCULATE DEVIATIONS from the menu, the
VAPOUR PRESSURE CALCULATION DIALOG BOX will appear. The VAPOUR PRESSURE
CALCULATION DIALOG BOX asking for the EOS, PCFILE and EOS parameters is the
same as already shown in Figure 2.2b. Because it is handled the same way as already
described in Sections 2.1/2.2, this description is not repeated here. In this dialog box,
the edit box for the minimum temperature is always disabled when calculating
deviations, because all data in the PCFILE with O-FLAG=1 (Section 1.1.1 and 2.1) are
used independently from this setting.
The calculation results, i.e. deviations between experimental and calculated data are
shown in the well known deviation dialog box which has already been shown in Figure
2.1d.
- 53 -
Chapter 3: Mixtures
3 Mixtures
PE offers two calculations modes: the pure-component mode and the mixture mode.
All calculations in the mixture mode are based on the experimental data and EOS
parameters in the EXFILES (section 1.2). After having chosen an EXFILE to work with
by selecting FILE/OPEN, the menu entry MIXTURE will appear (Figure 3a) and the most
important information about the next calculations will be displayed in the tool bar of
the main window of PE (Figure 3b).
Figure 3a: The menu MIXTURES appears after an EXFILE has been opened.
Figure 3b: Information about the mixture mode in the tool bar of the main window.
The first line in the tool bar of the main window displays the number of components in
the system (2 = binary system), the EOS (simple Peng-Robinson, appendix A1),
mixing rule (Mathias-Klotz-Prausnitz with 3 parameters, appendix A2), and the data
block in the EXFILE which should be the basis for the next calculations. The second line
in the tool bar of the main window displays the name of the EXFILE and the system
name in the EXFILE.
- 54 -
Chapter 3: Mixtures
It is important to note that PE can exclusively calculate mixture properties with the
EOS parameters in the EXFILE and that PE can only perform phase equilibrium
calculations at the conditions of a single block in an EXFILE. For binary systems such a
block contains isothermal data (section 1.2) in order to enable the calculation of Pxy-
diagrams. For ternary systems, such a block only contains data at identical temperature
and pressure (section 1.2), so a Gibbs triangle can be calculated for T and P of the
block. Future routines will enable additional calculations, also.
In case phase equilibrium calculations should be performed at conditions not identical
to one of the blocks in the EXFILE, one further block has to be added to the EXFILE with
the conditions where the calculations should be performed. The block should have one
entry, which will be used as INITIAL GUESS, i.e. starting value, for calculations with
ADDITIONAL POINTS (see section 1.2).
After selecting an EXFILE by FILE/OPEN, the EOS, mixing rule, and the data block in
the EXFILE for the next calculations can be chosen (Figure 3c – 3e).
The EOS drop down combo box exclusively contains EOS where all necessary pure-
component parameters are given in the EXFILE. If calculations should be performed
with an EOS not displayed in the combo box, the pure-component EOS parameters
have to be determined according to section 2.1 and keyed in the EXFILE by using FILE /
ADD / PURE-COMPONENT EOS PARAMETERS (compare 1.2.3).
The mixing rule drop down combo box only contains mixing rules which can be used
for the selected EOS. For some EOS only one mixing rule exists, this one is named
„Standard“, then.
If the user either changes EOS, mixing rule or data block, PE will prompt if the binary
interaction parameters should be kept constant or should be set to zero. In case
interaction parameters for the new combination EOS + mixing rule + data block are
stored in the EXFILE, there is also the possibility to load those. Instead of using the
combo boxes for changes, the [...] button on the tool bar can also be used.
- 55 -
Chapter 3: Mixtures
Figure 3e: Selecting an data block of the EXFILE for the next calculations
- 56 -
Chapter 3: Mixtures
Figure 3.1a: Input of interaction parameters for binary and multi component systems.
- 57 -
Chapter 3: Mixtures
tally. In the latter case the phase not determined experimentally should be unchecked
so that PE uses the values for this phase in the EXFILE as starting values for the
iterations, only. The dialog box PHASES (Figure 3.1c) also allows to choose the
formula according to which the average deviation is calculated. The buttons are
equivalents for the following, where ξi = mole fraction of component i:
2
1 n exp 1 n ξiexp − ξicalc
absolute ∧ 2 = ∑
n i =1
(ξi − ξicalc )
2
relative ∧ 2 = ∑
n i =1 ξiexp
1 n 1 n ξiexp − ξicalc
absolute = ∑ ξiexp − ξicalc relative = ∑
n i =1 n i =1 ξiexp
At the end of the calculations the dialog box shown in Figure 3.1d will display the
difference between experimentally determined and calculated mole fractions.
- 58 -
Chapter 3: Mixtures
Start Calculations
In order to start calculations with the settings from above, the menu entry MIXTURE/
CALCULATE has to be selected (Figure 3a). PE will display different dialog boxes,
depending on the number of components, hereafter. This is described in the sections
3.1.1 and 3.1.2, below.
OUPUT FILE
The calculation results will be stored in the selected output file PE_1...9.OUT in the
directory /PE/.
DEBUG INFO
PE can be forced to create additional output files that enable the programmer and
experienced users to determine the reasons for convergence problems, change the input
appropriately, and improve the program due to this information. Creating this debug
information can significantly slow down the program. Setting the debug information to
MINIMUM is recommended.
Warning: Excessive output of MAXIMUM DEBUG INFORMATION may lead to a reduced
lifetime of the harddisk.
- 59 -
Chapter 3: Mixtures
ADDITIONAL POINTS
PE will
- either calculate at the conditions of all equilibria of the current block in the EXFILE,
that are marked with flag=1 (compare section 1.2) and determine a deviation between
them and the calculated results
- or calculate at the first equilibrium of the current block in the EXFILE (independent of
the flag) and try to use this equilibrium as starting point for subsequent ADDITIONAL
CALCULATIONS in order to generate a complete Pxy-diagram or similar.
By checking ADDITIONAL POINTS, PE can be forced to do the latter calculations. After
the calculation of the first equilibrium, the pressure will be increased by the value of
FIRST STEP. The pressure will be increased further, until convergence of the iterations
fails - then the step size is reduced. After the step size has been reduced several times,
the calculations will stop and start at the starting point again, but continuously reducing
the pressure by FIRST STEP, now - and decreasing the step size if iterations do not
converge any more. Calculations stop after the step size has been reduced several
times, again.
Using ADDITIONAL CALCULATIONS, PE will not calculate at pressures higher than the
product of MAXIMUM PRESSURE FACTOR times the highest pressure of the points with
flag=1 in the EXFILE equilibrium block. This enables to obtain diagrams in a certain
pressure range, if the miscibility gaps remain open at high pressure, so that phase
equilibrium calculations always converge.
- 60 -
Chapter 3: Mixtures
ADD COMPONENT
ADDITIONAL CALCULATIONS start at the first equilibrium in the current EXFILE block,
like for binary calculations. The tie line which will be calculated afterwards, will be
close to this equilibrium. By using ADD COMPONENT, the user tells PE which
component has to be added most significantly in order to reach the next tie lines. For
example, starting with a tie line extremely rich in components 2 and 3, ADD
COMPONENT should be set to 1. Choosing the right value here can speed up
calculations, choosing the wrong value, might stop calculations at all. If any ternary
ADDITIONAL CALCULATIONS do not work well, it is advisable to change ADD
COMPONENT to another value and check if calculation performance is improved.
- 61 -
Chapter 3: Mixtures
EXP.
Left box: The position of the phase equilibrium in the EXFILE BLOCK that is calculated,
is shown here. In case ADDITIONAL POINTS has been checked for additional
calculations, the counter will proceed to increase by a step of one for each additional
calculation. Right box: The number of experimental points in the block of the EXFILE is
indicated here during the calculation without ADDITIONAL POINTS.
T, P
Temperature and pressure of current calculations.
Z
Mole fraction of component 1 in the feed for the flash (Bünz et al., 1992).
X, X’, Y,TYPE
In the upper row the initial guesses for the isothermal isobaric flash calculations are
displayed. x, x’, and y are the mole fractions of component 1, TYPE indicates the type
of equilibrium expected: 1: V-L1, 2: V-L2, 3: L1-L2, 4: V-L1-L2. In the lower row,
the last successfully calculated equilibrium is displayed, using the same output
variables.
TRY
TRY indicates the number of the actual attempt to calculate the current phase
equilibrium. If calculations are not successful with the initial guesses, PE itself
changes the initial guesses or selects a different kind of miscibility gap, and increases
TRY by one each time a new initial guess is tried. Depending on the version of PE, PE
tries a different number of times to calculate one equilibrium.
- 62 -
Chapter 3: Mixtures
Figure 3.1i (left side): input of mixture properties for the calculation of densities.
Figure 3.1j (right side): output of the calculated density.
- 63 -
Chapter 3: Mixtures
- 64 -
Chapter 3: Mixtures
- 65 -
Chapter 3: Mixtures
kij λij
-0,20 -0,30; -0,29; ... +0,39; +0,40
-0,19 -0,30; -0,29; ... +0,39; +0,40
... ...
... ...
+0,49 -0,30; -0,29; ... +0,39; +0,40
+0,50 -0,30; -0,29; ... +0,39; +0,40
Figure 3.2c: Choosing the binary subsystem of a ternary system for GRID parameters.
- 66 -
Chapter 3: Mixtures
- 67 -
Chapter 3: Mixtures
- 68 -
Chapter 3: Mixtures
PLOT FILES
It is possible to check a box corresponding to a PE_1..9.OUT file, if this file contains
binary phase equilibrium data (otherwise the check box will be disabled). Checking a
box will cause graphical output of the calculated data of this file and the corresponding
experimental data from the EXFILE. It is possible to check more than one file for
graphical output in order to receive a diagram with more than one set of experimental
+ calculated data.
DISPLAY
The compositions of the coexisting phases can be either plotted in mole fractions or
weight fractions.
ENLARGEMENT
By checking ENLARGEMENT, the regions with the fractions of component 1 ranging a)
from 0 to an upper bound and b) from a lower bound to 1 are enlarged, if a PXY-
DIAGRAM is plotted. This option is useful, if the miscibility of the components is low:
compare Figure 3.3b with Figure 3.3c.
Further Options
- It is possible to show the experimental points corresponding to the first (left) selected
PE_?.OUT file, only. This option is used if different EOS or parameters are used in
order to correlate the same experimental data to avoid multiple different symbols for
the same data.
- It is possible, to suppress the output of the calculated data in order to present the
experimental results from the EXFILE, alone.
- Using the yP-DIAGRAM (see below), it is possible to choose a logarithmic axis for the
composition. This option is useful for supercritical extractions of solids for example,
where the solubility of the solid in the gas phase can cover many orders of magnitude.
Types of diagrams
It is either possible to create a PXY-DIAGRAM or a yP-DIAGRAM. Figure 3.3b, 3.3c and
3.3d demonstrate the different graphical outputs.
- 69 -
Chapter 3: Mixtures
- 70 -
Chapter 3: Mixtures
Quaternary System
Trying to display equilibria of quaternary systems will result in ternary projections of
the equilibria onto the Gibbs’ Triangle without the fourth component. The composition
fractions of the first three components are normalised so that the sum is unity again.
This type of projection is useful, if only traces of the fourth component are present in
all phases (compare Pfohl et al, 1996, 1996a, 1997).
ENLARGEMENT
Checking ENLARGEMENT will cause the enlarged display of the triangle corner with
more than the specified amount of the specified COMPONENT.
- 71 -
Chapter 3: Mixtures
If this check box is checked by the user, an algorithm for calculating solid-gas
equilibria is been used instead of the vapour-liquid flash:
Where: f = fugacity
ϕ = fugacity coefficient
y = mole fraction in gas phase
P = system pressure and Psat = saturation pressure
T = system temperature
R = universal gas constant
Mw = molecular weight
ρS = solid density (S.DNS from EXFILE)
2 = component 2 = solid compound
V = vapour phase
S = solid phase (pure compound 2)
sat = state of saturation
- 72 -
Chapter 4: Implementation of New EOS by Users
Because PE is designed in such a way that PE.EXE starts density and phase
equilibrium calculations using one standard interface for all EOS, these EOS
subroutines have a standard format.
With such an EOS standard subroutine, PE can do all calculations with the given EOS,
which are implemented in PE:
Pure component calculations:
- calculate and plot Pv-diagram
- calculate and plot vapor pressure curve
- test and optimize pure-component parameters
Multicomponent mixture calculations:
- density calculations
- calculate and plot Px-diagrams (LLE/VLE/SGE)
- calculate and plot Gibbs triangles (LLE/VLE/VLLE)
- optimize interaction parameters
Such EOS standard subroutine can be written by anyone using a standard F77 compiler
and the guidelines listed in this chapter. Researchers who are familiar with FORTRAN
will be able to set up an EOS standard subroutine for simple EOS like Soave-Redlich-
Kwong within one day. These standard files can be tested and used by the users
themselves using the normal dialog boxes provided by PE.EXE the same day by
following the description of the program EOS_on_DISK.EXE in Section 4.7.
Upon request, such an EOS standard subroutine will be implemented in PE.EXE for
free, if a MS-Word file with an appropriate description for appendix1 is attached. A
fixed implementation in PE will speed up all subroutine calculations by a factor of
~100 compared to the use of EOS_on_DISK.EXE.
Such implementation will enable all users world wide to work with the new EOS, test
it and speed up the publication of its beneficial capabilities. This is seen as the major
benefit of the PE 2000 project.
- 73 -
Chapter 4: Implementation of New EOS by Users
- 74 -
Chapter 4: Implementation of New EOS by Users
!==================================================================
! Standard EOS subroutine for PE
!
! 2000-01-30 by Oliver Pfohl
!
! This subroutine does all calculations with the Peng-Robinson EOS:
! a) P(rho,T,x)
! b) rho(P,T,x)
! c) phi(P,T,x,phase)
!==================================================================
- 75 -
Chapter 4: Implementation of New EOS by Users
!==========================================================
! INITIALISATION (calc_what = 0)
! -------------------------------
!
! Here the "save" variables for Peng-Robinson are initialized.
! I.e. constants and parameters that are only depending on
! temperature (not on composition, density, pressure) are calculated
! from pure-component parameters and temperature.
!
! In order to obtain a "global" character of the variables, the
! values of the parameters are stored via "save"
!
! input: pure-component EOS parameters: ´PuCoPa´ (and T)
! intermediate output: Tc, Pc, omega
! final output: ai(i,i), bi(i,i)
!==========================================================
if (calc_what.eq.0) then
do i = 1, nco
tc(i) = PuCoPa(1,i)
pc(i) = PuCoPa(2,i)
omega(i) = PuCoPa(3,i)
tr(i)=t/tc(i)
ac(i)=0.457235529d0*r*r*tc(i)*tc(i)/pc(i)
bi(i,i)=0.077796074d0*r*tc(i)/pc(i)
xo = 0.37464d0+1.54226d0*omega(i)-.26992d0*omega(i)**2
xt = 1.d0+xo*(1.d0-dsqrt(tr(i)))
ai(i,i)=ac(i)*xt**2
enddo
endif ! INIT (calc_what=0)
- 76 -
Chapter 4: Implementation of New EOS by Users
!==========================================================
! CALCULATE PRESSURE P(x,rho,T) (calc_what = 1)
! ----------------------------------------------
!
! input: T, rho, iphase/iphaseerr AND (ax,ay,bx,by,cx,cy)
!
! output: pp(rho,T), dp(rho,T)
!
!==========================================================
if (calc_what.eq.1) then
rt = r * t
if (iphaseerr.eq.1) then
if (iphase.eq.1) then
iphase = 0
else
iphase = 1
endif
endif
! GAS PHASE
!----------
if (iphase.eq.0) then
do i = 1, nco
! mole fractions: not used here but maybe for other EOS
xa(i) = yi(i)
enddo
am = ay
bm = by
! c: not used here
cm = cy
! LIQUID PHASE
!-------------
else
do i = 1, nco
xa(i) = xi(i)
enddo
am = ax
bm = bx
! c: not used here
cm = cx
endif
if (iphaseerr.eq.1) then
if (iphase.eq.1) then
iphase = 0
else
iphase = 1
endif
endif
! just an abbreviation
rbm = rho * bm
! thet = (Z-1)/rho
thet = bm/(1.d0-rbm)-am/rt/(1.d0+2.d0*rbm-rbm*rbm)
! dthet = d_thet / d_rho
dthet = bm*(bm/ dexp(dlog(1.d0-rbm)*2.d0) +
& 2.d0*am/rt*(1.d0-rbm)/
& dexp(dlog(1.d0+2.d0*rbm-rbm*rbm)*2.d0))
- 77 -
Chapter 4: Implementation of New EOS by Users
!==========================================================
! CALCULATE FUGACITIES phi(x,P,T) (calc_what = 2)
! ------------------------------------------------
!
! input: T, P, xi, yi
!
! output: rhol, prhol, phil(), errliq
! rhog, prhog, phig(), errvap,
! for pedens: rhomx
!
!==========================================================
if (calc_what.eq.2) then
p = pp
rt = r * t
- 78 -
Chapter 4: Implementation of New EOS by Users
! ar
!---
arx=-dlog(1.d0-bx*rhol)+ax*arax
ary=-dlog(1.d0-by*rhog)+ay*aray
! d(ar)/d(b)
!-----------
arbx=rhol/(1.d0-bx*rhol)+ax/bx/bx/rt2sq *rll-ax/bx*
& rhol/r/t/(1.d0+2.d0*bx*rhol-(bx*rhol)**2)
arby=rhog/(1.d0-by*rhog)+ay/by/by/rt2sq *rlg-ay/by*
& rhog/r/t/(1.d0+2.d0*by*rhog-(by*rhog)**2)
! (Z-1)/rho
!----------
thetx=bx/(1.d0-bx*rhol)-ax/rt/(1.d0+2.d0*bx*rhol-(bx*rhol)**2)
thety=by/(1.d0-by*rhog)-ay/rt/(1.d0+2.d0*by*rhog-(by*rhog)**2)
suphiax=0.d0
suphiay=0.d0
suphibx=0.d0
suphiby=0.d0
do i=1,nco
suphiax=suphiax+xi(i)*arax*dadx(i)
suphiay=suphiay+yi(i)*aray*dady(i)
suphibx=suphibx+xi(i)*arbx*dbdx(i)
suphiby=suphiby+yi(i)*arby*dbdy(i)
enddo
do i=1,nco
zett=p/(rhol*r*t)
philogl(i)=arx+arax*dadx(i)+arbx*dbdx(i)-suphiax-suphibx+
& zett-1.d0-dlog(zett)
zett=p/(rhog*r*t)
philogg(i)=ary+aray*dady(i)+arby*dbdy(i)-suphiay-suphiby+
& zett-1.d0-dlog(zett)
phil(i)=dexp(philogl(i))
phig(i)=dexp(philogg(i))
enddo
endif ! CALC FUGACITIES (calc_what=2)
end
- 79 -
Chapter 4: Implementation of New EOS by Users
! parameters
!-----------
integer nsteu, mixrule, nco, nmax
double precision r, t, ai(100,100), bi(100,100), ci(100,100),
& k(nmax,*), l(nmax,*), la(nmax,*),
& xi(*), yi(*),
& ax, ay, dadx(nmax), dady(nmax),
& bx, by, dbdx(nmax), dbdy(nmax),
& cx, cy, dcdx(nmax), dcdy(nmax),
& asx(nmax,nmax),asy(nmax,nmax)
! counter
!--------
integer ii,jj
!-----------------------------------------------------
! Set all mixture parameters (and derivatives) to ZERO
!-----------------------------------------------------
ax=0.0d0
ay=0.0d0
bx=0.0d0
by=0.0d0
cx=0.0d0
cy=0.0d0
do ii=1,nco
dadx(ii)=0.0d0
dady(ii)=0.0d0
dbdx(ii)=0.0d0
dbdy(ii)=0.0d0
dcdx(ii)=0.0d0
dcdy(ii)=0.0d0
enddo
!-----------------------------------------------------
! calculation of parameter "a" (quadratic mixing rule)
!-----------------------------------------------------
do ii=1,nco
do jj=1,nco
ai(ii,jj) = (1.d0-k(ii,jj))*dsqrt(ai(ii,ii) * ai(jj,jj))
asx(ii,jj) = ai(ii,jj)
asy(ii,jj) = ai(ii,jj)
ax = ax+xi(ii)*xi(jj)*asx(ii,jj)
ay = ay+yi(ii)*yi(jj)*asy(ii,jj)
dadx(ii)=dadx(ii)+2.d0*xi(jj)*ai(ii,jj)
dady(ii)=dady(ii)+2.d0*yi(jj)*ai(ii,jj)
enddo
enddo
!----------------------------------------
! calculation of parameter "b" (standard)
!----------------------------------------
do ii=1,nco
do jj=1,nco
bi(ii,jj) = (1.0d0-l(ii,jj))*(bi(ii,ii)+bi(jj,jj))/2.d0
bx=bx+xi(ii)*xi(jj)*bi(ii,jj)
by=by+yi(ii)*yi(jj)*bi(ii,jj)
dbdx(ii)=dbdx(ii)+2.d0*xi(jj)*bi(ii,jj)
dbdy(ii)=dbdy(ii)+2.d0*yi(jj)*bi(ii,jj)
enddo
enddo
end
---------------------------------------------------------------------------------------------------------
Figure 4.3a: demo file pes_EOS_by_User.FOR
- 80 -
Chapter 4: Implementation of New EOS by Users
Definition of θ
Z −1
Θ[T , ρ , z ] =
ρ
P
with Z =
ρRT
ρ =1 / v
a r [T , v, z ]
~
i.e. a [T , v, z ] = = ∫ Θ[T , ρ , z ]dρ
r
RT ρ =0
Calculation of P, using Θ
P ideal [T , ρ , z ] = ρRT
- 81 -
Chapter 4: Implementation of New EOS by Users
dP dΘ
= RT * 1 + ρ * 2 * Θ + ρ *
dρ T , z dρ T , z
f i Ph = z iPh * ϕ iPh [T , ρ Ph , z Ph ] * P
ψk are different parts of the EOS (not necessarily parameters) which depend on
composition. Their individual choice is up to the programmer. All ψk together must
cover all parts of the EOS which depend on composition, when ρ and T are given and
held constant. For the PR-EOS (see below) it is sufficient to use ψ1=a and ψ2=b. For
SAFT, Huang and Radosz (1990-1993) used 8 different parts in order to minimize the
size of the resulting single equations. A good parameterization saves a lot of
programming work: In the limit when the programmer sets ψ= a~ r , no simplification is
achieved at all.
Calling the subroutine with calc_what=2, the fugacity coefficients for both phases are
calculated. Because for phase equilibrium calculations, there is mechanical and thermal
stability between the phases, T and P are given in order to calculate the fugacity
coefficients for both phases.
This enforces the calculation of ρL=ρ(T,P,x,iphase=1) and ρG=ρ(T,P,y,iphase=0) prior
to the fugacity coefficients. The information of iphase has to be included here, because
of the van-der-Waals loop in the calculated isotherms.
Because it is hard work to derive analytical expressions for ρ(T,P,z) for most
(complicate) EOS, PE offers an algorithm for finding the solution numerically. This
- 82 -
Chapter 4: Implementation of New EOS by Users
algorithm pedens was written by Topliss (1985) and slightly adjusted in order to meet
the needs of PE. This algorithm repeatedly calls the above described routine for the
calculation of P(T,ρ,z) with calc_what=1 (section 4.3.2) similar to routines for finding
roots of normal equations.
Because T and z do not change during these iterations, those parts of the EOS that only
depend on T and z should be calculated once before doing these iterations and stored in
local variables using the save-paragraph (compare example with PR-EOS, below):
1) Doing the initialization (calc_what=0), all variables that only depend on
temperature T are set.
2) The variables that depend on composition z are set just before running the iterations
by calling pedens when calling the subroutine with calc_what=2. All these
variables have to be saved – see PR-example, below.
Finally, P, T, x {FORTRAN: xi}, y {yi}, ρL {rhol}, ρG {rhog} are known and the
fugacity coefficients ϕi,L {phil(i)} and ϕi,G {phig(i)} can be calculated.
4.4 pes_EOS_by_User.FOR
The FORTRAN file pes_EOS_by_User.FOR (Figure 4.3a, see above) serves as an
example for an EOS standard subroutine. The file contains the simple Peng-Robinson
EOS with the simple quadratic mixing rule.
The below sections 4.4.1 – 4.4.6 describe the specific parts of the subroutine, so that
the implementation of the Peng-Robinson EOS can be understood by anyone trying to
implement another EOS.
- 83 -
Chapter 4: Implementation of New EOS by Users
- 84 -
Chapter 4: Implementation of New EOS by Users
Important: In case, only the pressure P(ρ,T,z) should be calculated, PE calls the
subroutine with calc_what=0, first. Then the subroutine is called with calc_what=2
and pp=-1 (negative!). This ensures that the parameters ax, ay... are set and present at
the subsequent call with “calculate pressure” (calc_what=1, see EOS_P_TEST.FOR as
example). On the other hand, pp=-1 prevents the superfluous calculation of ρ(P,T,z)
and ϕ(P,T,z) in the call with calc_what=2 because of the statement “if (p.lt.0) return”.
- 85 -
Chapter 4: Implementation of New EOS by Users
The documentation of the mixing rules and their parameters is in appendix A2.
Mix_abc calculates ax, ay, bx, by, cx, cy and their derivatives with respect to the mole
fractions which are needed for the calculation of the fugacity coefficients according to
the parameterization by Topliss (see above).
- 86 -
Chapter 4: Implementation of New EOS by Users
For these two programs it is necessary to use the save-statement like in PE.EXE and
NOT the subroutines read_eos_save and write_eos_save like in EOS_on_DISK.FOR –
thus the variable called_by_EOS_on_DISK is set to false. Thus, for these tests, the
subroutines read_eos_save and write_eos_save can be dummy subroutines.
1) Because the new FORTRAN files should work independently of the compiler used,
please, do only use standard FORTRAN 77 with two exceptions:
a) in order to avoid the use of labels, try to write
do i=1,10
enddo
instead of
do 123 i=1,10
123 continue
b) Try to use “implicit none” instead of “implicit logical a-z” in order to guarantee
that all variables have been defined correctly.
2) Please do start the program lines in column 7 according to F77 standard although
the compiler might allow to start with the FORTRAN code in column 1. Please, do
not use “Tabs” – please use “Spaces”.
3) Please, do use double precision variables and the appropriate functions “dsqrt”,
“dlog”, “dexp”, “double”. Example: if “r” and “s” are double precision and “i” is an
integer, do not write “r=i*s“, but “r=double(i)*s“.
4) Please do not write “a=b**3.d0“ but “a=b**3“, because for b<0 the latter one is
interpreted as a=b*b*b by some compilers while the former leads to runtime errors
for b<0.
5) Please do use the predefined constants R, Pi, NAv, and TAU and do not redefine
them.
- 87 -
Chapter 4: Implementation of New EOS by Users
4.7 EOS_on_DISK.FOR
After having performed (and passed) the above test programs EOS_P_TEST.FOR and
EOS_PHI_TEST.FOR, the FORTRAN file EOS_on_DISK.FOR allows the user to
connect the new EOS in the pes_EOS_by_User.FOR file with PE.EXE within a few
minutes and without the necessity of having any other FORTRAN code of the PE
project.
- 88 -
Chapter 4: Implementation of New EOS by Users
The pure-component parameter names and units can be supplied in the file
EOS_on_DISK.in placed in the directory of PE.EXE. The included file for the “Simple
Peng-Robinson” EOS in the subroutine User_EOS in the file pes_EOS_by_User.FOR
is shown in Figure 4.7c. Line 1 and column 1 and 2 are used for documentation.
Column 3-7 contain the parameter names, column 8 is blank, column 9-17 contain the
units of the parameters. Please fill all lines for all parameters with blanks up to column
17 in order to prevent I/O-errors for your EOS. These parameter names and units are
displayed in the appropriate PE dialog boxes, then (Figure 4.7d).
name- unit-----
1 Tc [K]
2 Pc [bar]
3 omega [-]
4 - -
5 - -
6 - -
7 - -
Figure 4.7c:
file EOS_on_DISK.in Figure 4.7d:
Parameter names and units from file
EOS_on_DISK.in
- 89 -
Chapter 4: Implementation of New EOS by Users
Further, the name of parameter 1 and 2 must not be Tc and Pc if the calculated critical
properties are not equal to these parameters: compare the use of Tc’ and Pc’ for the
Anderko-EOS or the PR-CPA-EOS.
The binary interaction parameters kε and kκ should be used for interaction between
sites for the same reasons. kij (λij) should be the first (second) parameter to fit aij and
uij, i.e. energy parameters. lij should be used to fit bij, i.e. volume parameters.
Please note, that kij=kji, lij=lji, kεij = kεji, kκij=kκji but λij = - λji.
- 90 -
Chapter 4: Implementation of New EOS by Users
It is important to note, that for one single flash calculation, PE will call the user
subroutine with the EOS (placed in EOS_on_DISK.EXE) once with calc_what=0 and
several times with calc_what=2. Each call with calc_what=2 (and P>0) will lead to 2
calls of pedens, each leading to about 10 calls of EOS_on_DISK.EXE with
calc_what=1.
Thus for 20 points on a vapor pressure curve, EOS_on_DISK.EXE will be called about
20 x (1 + 10 x 2 x 10) = ~ 4000 times – so be patient.
Parameter optimizations will lead to multiple calls in the range 50 x 4000 = 200.000
and can not be recommended, therefore. Submission of the source code for fixed
implementation is recommended, then.
- 91 -
Chapter 5: Export of Data
5 Export of Data
PE allows the export of all graphics in Windows metafile format and any printer
language like Postscript or HPGL. Each graphic window has its own menu bar offering
EXPORT / WINDOWS METAFILE, EXPORT / PRINT and EXPORT / PRINT TO FILE (Figure
5a). Selecting EXPORT / WINDOWS METAFILE will create a Windows metafile file
(*.wmf). Selecting EXPORT / PRINT TO FILE will use any available printer driver to
create a file. Many Postscript and HPGL printer drivers come along with Windows.
Thus, using a Postscript printer driver will create Postscript files (*.ps / *.eps), and
using an HPGL / HPGL II printer driver will create HPGL / HPGL II files (*.hgl).
These formats allow the export of all graphics to commercial programs like Microsoft
Word, Microsoft Powerpoint, Corel Draw, Picture Publisher, and similar. Selecting
EXPORT / PRINT will print the graph directly to the printer.
Note: In order to keep the efforts to generate different files low, standard printer driver
interfaces are used. When generating Postscript files, these files will have a header and
footer not appropriate for file processing other than direct printing. It is therefore
necessary to delete header and footer. In PE the user can give the file to be generated
the extension *.PS and then select the brandnew file with the next file selector box,
again. The second selection will start a program, to erase header and footer so that the
file can be loaded by CorelDraw, for example.
- 92 -
Chapter 6: Future Developments
6 Future Developments
The first preliminary Windows release of PE was shown at the 8th International
Conference on Properties and Phase Equilibria for Product and Process Design held at
Noordwijkerhout, The Netherlands, on April 30th, 1998 (Pfohl et al., 1998a). The first
official Windows release of PE was finished in July 1998 and shown at the 17th
European Seminar on Applied Thermodynamics at Vilamoura, Portugal, (Petkov et al.,
1999) and on the International Workshop on Scientific Computing in Chemical
Engineering II at Hamburg, Germany, (Petkov et al., 1999a, Pfohl et al., 1999a). The
present manual describes the PE version released in February 2000.
The Windows versions of PE are based on the latest (and last) hp-UNIX version of PE
finished by Pfohl (1998) in December 1997. Although enormous efforts have been
made, the Windows version of PE does not contain all routines from the UNIX
version, yet. The first future development will be the implementation of the remaining
routines, especially:
- pure-component EOS parameter optimisations for more than one parameter when
enforcing critical temperature and pressure.
- advanced output of data and warnings / error messages to screen and files.
If users desire special routines or special EOS, these can also be built in.
- 93 -
Appendix A1: EOS in PE
0. Van-der-Waals EOS
The van-der-Waals EOS is the simplest EOS implemented in PE. It should only be
used in order to demonstrate the abilities and inabilities of simple EOS. Use of the van-
der-Waals EOS only requires the input of Tc and Pc - corresponding to a and b - for
each component.
EOS:
RT a
P= − 2
v−b v
PURE-COMPONENT PARAMETERS:
R 2Tc2
a = 0,421875
Pc
RTc
b = 0,125
Pc
** It is important to note, that these are not necessarily identical to the experimentally determined properties of a
pure compound.
- 94 -
Appendix A1: EOS in PE
MIXTURE PARAMETERS:
The mixture parameters are calculated according to the mixing rules shown in
Appendix A2.
LITERATURE:
van der Waals (1899)
1. Peng-Robinson EOS
The Peng-Robinson EOS is the EOS most widely used in chemical engineering
thermodynamics. It is known to give slightly better predications of liquid densities than
the Soave-Redlich-Kwong EOS by Soave (1972). The EOS requires three inputs per
compound: Tc, Pc and the acentric factor ω. Different modified Peng-Robinson EOS
with volume-translations and modified alpha functions are listed in sections 10-19.
EOS:
RT a (T )
P= − 2
v − b v + 2bv − b 2
PURE-COMPONENT PARAMETERS:
R 2Tc2
a (T ) = a (Tc ) ⋅ α (Tr , ω ) with a (Tc ) = 0,45724
Pc
( )
2
α (Tr ,ω ) = 1 + κ (1 − Tr ) with κ = 0,37464 + 1,54226ω − 0,26992ω 2
RTc
b = 0,0778
Pc
- 95 -
Appendix A1: EOS in PE
MIXTURE PARAMETERS:
The mixture parameters are calculated according to the mixing rules shown in
Appendix A2.
LITERATURE:
Peng and Robinson (1976)
2. Hederer-Peter-Wenzel EOS
The Hederer-Peter-Wenzel EOS was presented in the same year as the Peng-Robinson
EOS. The EOS needs three inputs per pure compound: Tc, Pc and α. α is a measure
for the slope of the vapour pressure curve. In case α=-0.5, the simple Redlich-Kwong
EOS (Redlich and Kwong, 1949) is obtained.
EOS:
RT a (T )
P= −
v − b v( v + b)
PURE-COMPONENT PARAMETERS:
R 2Tc2
a (T ) = a c ⋅ Trα with ac = 0,42747
Pc
RTc
b = 0,08664
Pc
MIXTURE PARAMETERS:
The mixture parameters are calculated according to the mixing rules shown in
Appendix A2.
LITERATURE:
Hederer, Peter, and Wenzel (1976)
- 96 -
Appendix A1: EOS in PE
3. Soave-Redlich-Kwong EOS
The Soave-Redlich-Kwong EOS was the first modification of the simple Redlich-
Kwong EOS where the parameter a was made temperature dependent in such a way
that the vapour pressure curve could be reproduced well. The EOS requires three input
parameters per pure compound: Tc, Pc and ω. Different modified Soave-Redlich-
Kwong EOS with volume-translations and modified alpha functions are listed in
subsections 30-39.
EOS:
RT a (T )
P= −
v − b v( v + b)
PURE-COMPONENT PARAMETERS:
R 2Tc2
a (T ) = a c ⋅ α (T ) with a c = 0,42747
Pc
( ( ))
2
α (T ) = 1 + m 1 − Tr with m = 0,48 + 1,574ω − 0,176ω 2
RTc
b = 0,08664
Pc
MIXTURE PARAMETERS:
The mixture parameters are calculated according to the mixing rules shown in
Appendix A2.
LITERATURE:
Soave (1972)
- 97 -
Appendix A1: EOS in PE
4. Redlich-Kwong EOS
The Redlich-Kwong EOS by Redlich and Kwong (1949) is a modification of the van-
der-Waals EOS. Similar to the van-der-Waals EOS it should only be used in order to
demonstrate the abilities and inabilities of simple EOS, because better EOS exist. Use
of this EOS only requires the input of Tc and Pc - corresponding to the parameters a
and b - for each component.
EOS:
RT a/ T
P= −
v − b v ( v + b)
PURE-COMPONENT PARAMETERS:
R 2 Tc2.5
a = 0.42747
Pc
RTc
b = 0,08664
Pc
MIXTURE PARAMETERS:
The mixture parameters are calculated according to the mixing rules shown in
Appendix A2.
LITERATURE:
Redlich and Kwong (1949)
5. Dohrn-Prausnitz, nonpolar
The Dohrn-Prausnitz EOS is based on the repulsive term of hard spheres by Carnahan
and Starling (1969) for pure compounds and the reference term by Boublik (1970) and
Mansoori et al. (1971) for mixtures instead of on the van-der-Waals repulsive term.
The EOS in not cubic in the volume, therefore. The attractive term of the Carnahan-
Starling-vdW EOS (Carnahan and Starling, 1972) was modified in such a way that
critical isotherms of many compounds can be reproduced well. The EOS needs three
inputs for each pure compound: Tc, Pc and ω.
- 98 -
Appendix A1: EOS in PE
EOS:
Z = Zref + Z pert
Zref =
1 + ( 3DE
F − 2)η + ( 3E 3
F2 F +1 η −
− 3 DE 2
) E3
F2
η3
(1 − η )3
N
with D = ∑ ξ iσ i
i =1
N
E = ∑ ξ iσ i2
i =1
N
F = ∑ ξ iσ i3
i =1
1
3 bi 3
σi =
2 π ⋅ NA
π ρ N
η=
6
N AF ⋅ ρ =
4
∑ξ bi =1
i i
aρ bρ bρ
2
PURE-COMPONENT PARAMETERS:
(
a = a c a (1) tanh(a ( 2) Tr − 1
0.7
) +1 )
with a (1) = 0,367845 + 0,055966ω
a ( 2 ) = ( −1) m ⋅ ( 0,604709 + 0,008477ω )
R 2Tc2
a c = 0,550408
Pc
(
b = bc b (1) tanh(b ( 2 ) ln Tr
0.8
) +1 )
with b(1) = 0,356983 − 0,190003ω
b( 2 ) = ( −1) m ⋅ (1,37 − 1,898981ω )
RT
bc = 0,187276 c
Pc
and m=1 for Tr≥1
m=0 for Tr<1
- 99 -
Appendix A1: EOS in PE
MIXTURE PARAMETERS:
The mixture parameters are calculated according to the mixing rules shown in
Appendix A2.
LITERATURE:
Dohrn and Prausnitz (1990)
LITERATURE:
Dohrn and Prausnitz (1990, 1990b)
7. Elliott-Suresh-Donohue EOS
For non-associating fluids the ESD EOS is a cubic in volume. The non-spherity of
molecules is taken into account by the theory of Prigogine (1957). The proposed
extension to associating fluids has not been implemented in PE.
EOS:
Pv 4cη zm qηY
= 1+ −
RT . η 1 + k1 ηY
1 − 19
PURE-COMPONENT PARAMETERS:
ε 1 + 0.945(c − 1) + 0134
. (c − 1) 2
a= = Tc **
k 1.023 + 2.225(c − 1) + 0.478(c − 1) 2
. ω + 0.533ω 2
c = 1 + 3535
** It is not clearly stated in the original paper, if the formulas for a and b are analytical solutions in order to
obtain the point of inflection at Tc and Pc or if the formulas are correlations. There is some evidence that these
formulas are correlations.
- 100 -
Appendix A1: EOS in PE
k1 = 1.7745
k2 = 1.0617
k3 = 1.90476
zm = 9.49
q = 1 + k3(c-1)
MIXTURE PARAMETERS:
∑ ξi vi*
η=
v
4∑ ∑ ξi ξ j (cv * ) ij
4cη =
v
∑ ∑ ξi ξ j (qv * ) ij Yij
qηY =
v
ci v *j + c j vi*
(cv ) ij =
*
2
qi v *j + q j vi*
(qv ) ij =
*
2
ε ij = ε i ε j (1 − kij )
ε ij
Yij = exp( ) − k2
kT
qηY
ηY =
∑ ξi qi
LITERATURE:
Elliott, Suresh, and Donohue (1990)
- 101 -
Appendix A1: EOS in PE
8. Sako-Wu-Prausnitz
The Sako-Wu-Prausnitz EOS is a modification of the Soave-Redlich-Kwong EOS,
where a fourth parameter c is used to explicitly account for non-spherity of molecules.
EOS:
RT ( v − b + bc ) a
P= −
v ( v − b) v( v + b)
α 0 (1 − TR2 ) + 2TR2
with α (T ) =
1 + TR2
α 0 = 11920
, + 0,11060 ln(1000Vw ) + 0,30734Vw
(1 − 2 D 0 + 2 cD 0 + D 20 − cD 20 )(1 + D 0 ) 2 R 2 Tc2
ac = ⋅
3(1 − D 0 ) 2 ( 2 + D 0 ) Pc
D 30 + ( 6 c − 3) D 20 + 3D 0 − 1 = 0
D 0 RTc
b= ⋅
3 Pc
Vw is the van der Waals volume and can either be calculated by the group-contribution
method of Bondi (1968) or treated as adjustable parameter.
- 102 -
Appendix A1: EOS in PE
MIXTURE PARAMETERS
The parameters a and b are calculated according to appendix A2. The parameter c is
the arithmetic mean of the ci
LITERATURE:
Sako, Wu, and Prausnitz (1989)
EOS:
RT a (T ) ~
P = ~ ~ − ~2 ~ ~ with v~ = v + c and b =b+c
v − b v + 2b v~ − b 2
PURE-COMPONENT PARAMETERS:
R 2Tc2
a (Tc ) = 0,45724 with a(T ) = a(Tc ) ⋅ α (Tr , ω )
Pc
~ RTc
b = 0.0778
Pc
- 103 -
Appendix A1: EOS in PE
10 (PR-VT, Peneloux):
κ = 0,37464 + 1,54226ω − 0,26992ω 2
( )
2
α (Tr ,ω ) = 1 + κ (1 − Tr )
EXFILE EOS PARAMETER INPUT:
4 0 10 PR-VT, Peneloux
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000
~
c/b 0.000000 0.000000 [ratio of c / b ]
LITERATURE:
Peng and Robinson (1976)
Peneloux, Rauzy, and Freze (1982)
11 (PR-VT, Mathias):
κ = 0,37464 + 1,54226ω − 0,26992ω 2
if Tr<1: (
α (Tr ) = 1 + κ (1 − Tr ) − p1 (1 − Tr )(0.7 − Tr ) ) 2
α (T ) = ( exp(c(1 − T ))) d 2
if Tr>1: r r
κ
c = 1+ + 0.3 p1
2
c −1
d=
c
EXFILE EOS PARAMETER INPUT:
5 0 11 PR-VT, Mathias
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000
p1 0.000000 0.000000
~
c/b 0.000000 0.000000 [ratio of c / b ]
LITERATURE:
Peng and Robinson (1976)
Peneloux, Rauzy, and Freze (1982)
Mathias (1983)
- 104 -
Appendix A1: EOS in PE
12 (PR-VT, Stryjek-Vera):
κ = 0.378893 + 14897153
. ω − 017131848
. ω 2 + 0.0196554ω 3
( )
α (Tr ) = 1 + (κ + κ 1 (1 + Tr )(0.7 − Tr ))(1 − Tr )
2
13 (PR-VT, Melhem):
(
α (Tr ) = exp m(1 − Tr ) + n(1 − Tr ) 2 )
EXFILE EOS PARAMETER INPUT:
5 0 13 PR-VT, Melhem
Tc 0.000000 0.000000
Pc 0.000000 0.000000
m 0.000000 0.000000
n 0.000000 0.000000
~
c/b 0.000000 0.000000 [ratio of c / b ]
LITERATURE:
Peng and Robinson (1976)
Peneloux, Rauzy, and Freze (1982)
Melhem, Saini, and Goodwin (1989)
- 105 -
Appendix A1: EOS in PE
14 (PR-VT, Thorwart-Daubert):
κ = 0,37464 + 1,54226ω − 0,26992ω 2
2
(1 − Tr )
α (Tr ) = 1 + κ (1 − Tr ) + n
Tr
EXFILE EOS PARAMETER INPUT:
5 0 14 PR-VT, Thorwart-Daubert
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000
n 0.000000 0.000000
~
c/b 0.000000 0.000000 [ratio of c / b ]
LITERATURE:
Peng and Robinson (1976)
Peneloux, Rauzy, and Freze (1982)
Thorwart and Daubert (1993)
15 (PR-VT, Boston-Mathias):
κ = 0,37464 + 1,54226ω − 0,26992ω 2
if Tr<1: (
α (Tr ) = 1 + κ (1 − Tr ) − p1 (1 − Tr )(0.7 − Tr ) ) 2
2
1
if Tr>1: α (Tr ) = exp (1 − )(1 − Trd )
d
κ
d = 1+ + 0.3 p1
2
EXFILE EOS PARAMETER INPUT:
5 0 15 PR-VT, Boston-Mathias
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000
p1 0.000000 0.000000
~
c/b 0.000000 0.000000 [ratio of c / b ]
LITERATURE:
Peng and Robinson (1976)
Peneloux, Rauzy, and Freze (1982)
Boston and Mathias (1980)
MIXTURE PARAMETERS:
The mixture parameters are calculated according to the mixing rules shown in
Appendix A2. In order to avoid inconsistencies the parameters lij are set to 0. The
parameter c is the arithmetic mean of the ci
- 106 -
Appendix A1: EOS in PE
EOS:
ar m n λi
= c ∑ ∑ aij ~ j
RT i =1 j = 0 T
~ T τv 0 π 2
T = *, η= , τ= = 0.74048... (closest packing fraction)
T v 6
MIXTURE PARAMETERS
N N
T * = ∑ ∑ ξi ξ j Ti *T j* (1 − k ij ) with kij = kji
i =1 j =1
3
N N v 01/,i3 + v 01/, 3j
v0 = ∑ ∑ ξi ξ j
i =1 j =1 2
N
c = ∑ ξi ci
i =1
LITERATURE:
Pfennig (1988)
- 107 -
Appendix A1: EOS in PE
21. BACK
The BACK EOS for pure components was proposed by Chen and Kreglewski (1977).
Chen and Kreglewski used the reference term for hard convex bodies by Boublik
(1975) and the dispersion term by Alder et al. (1972) with refitted constants in order to
obtain better representations of real fluids (Alder et al. fitted the constants to molecular
dynamics data). For each component four parameters are needed: the core volume V00,
the potential depth u0/k, α for characterising non-spherity and η/k influencing the
temperature dependence of the potential depth.
Later, Simnick et al. (1979) as well as Machat and Boublik (1985b) extended the
BACK EOS to mixtures by proposing different mixing rules. Pfohl and Brunner (1998)
proposed a new mixing rule and claimed it to be more efficient as the best mixing rule
„Set B“ by Machat and Boublik (1985b). The „Set B“ mixing rule by Machat and
Boublik (1985b) and the mixing rule by Pfohl and Brunner (1998) are implemented,
here.
It should be noted, that using the EOS number 23 in PE, i.e. „SAFT-ConveyBody“ and
setting all parameters m=1 the BACK EOS is also obtained. The pure component
results are the same as obtained here. Using SAFT-ConvexBody, setting all m=1,
offers two further mixing rules, whereof the „van-der-Waals mixing rule“ is even
better than the two supplied for EOS 21, here (compare: Pfohl and Brunner, 1998).
EOS:
Z = Zh + Za
1 3α s y s α s2 y s2 (3 − y s ) π 2 Vs0
Zh = + + with ys =
(1 − y s ) (1 − y s ) 2 (1 − y s )3 6 Vs
m
u V
4 9 0 n
Z = ∑ ∑ mDnm s s
a
n =1 m=1 kT Vs
- 108 -
Appendix A1: EOS in PE
3
3u 0
V = V 1 − 0,12 exp −
0 00
kT
MIXTURE PARAMETERS
Vs0 = ∑ x iVi 0
1
0 ∑ i
αs = ⋅ x (α iVi 0 ) 3 ∑ x i (α iVi 0 ) 3
1 2
Vs
LITERATURE:
Alder, Young, and Mark (1972)
Boublik (1975)
Chen and Kreglewski (1977)
Simnick, Lin, and Chao (1979)
Machat and Boublik (1985a,b)
Pfohl and Brunner (1998)
- 109 -
Appendix A1: EOS in PE
22. SAFT-Pfennig/Pfohl
This EOS is a modification of SAFT and was derived by Pfohl. It is not published, yet.
It uses the original SAFT equations by Huang and Radosz (1991, compare section 23)
but uses the term for the attractive interactions between spheres from the Pfennig EOS
(Pfennig, 1988, compare section 20) instead of the term from the BACK EOS.
The SAFT-Pfennig/Pfohl EOS therefore needs one pure-component parameter per pure
component less than the original SAFT EOS:
- T* = depth of the potential
- v0 = volume of one sphere
- m = the number of spheres in one molecule
- same parameters for association as SAFT
The implementation of this EOS in PE has not been tested thoroughly, yet. It was not
shown yet that the use of this EOS is advantageous compared to the use of original
SAFT, yet. Therefore the use of this EOS is not recommended at this state.
- 110 -
Appendix A1: EOS in PE
23. SAFT-ConvexBody
The SAFT-ConvexBody EOS is a modification of original SAFT by Huang and
Radosz (1990-1993) presented by Pfohl and Brunner (1998). This EOS allows to mix
the sphere chains from original SAFT with convex bodies from original BACK. Thus,
each molecule can either be modelled as a sphere chain with the possibility of
association or as a convex body. In case no convex body is present, the EOS exactly
reduces to original SAFT by Huang and Radosz (1991). In case no sphere chain is
present, the EOS exactly reduces to original BACK (see section 21).
Table A1.1: parameters for pure components, either sphere chain or convex body.
Parameter sphere-chain (SAFT) convex body (BACK)
potential depth u0/k u0/k
core size v00 v00
chain length m m≡1
T-dependence of u/k η/k η/k
convex parameter α≡1 α
number of asso. sites sites sites≡0
asso. Potential depth εA no association possible
asso. Volume κA no association possible
Note: it is clearly shown in Table A1.1, that either m or α has to equal unity in order to
chose the SAFT or BACK model for each molecule. Further, it is not possible to create
convex bodies with α≠1 and association sites.
EOS:
- 111 -
Appendix A1: EOS in PE
a hs 6 ξ 23 + 3ξ1ξ 2ξ 3 − 3ξ1ξ 2ξ 32 ξ 23
= − ξ − − ξ
ξ 32
ln(1 )
RT π ⋅ N A ρ ξ 3 (1 − ξ 3 ) 2 0 3
π
with ξ 0 = N Aρ ⋅ A A = ∑ X i mi = m
6
π
ξ1 = N Aρ ⋅ B B = ∑ X i mi (α i 3 d i )
1
6
π
ξ2 = N Aρ ⋅ C C = ∑ X i mi (α i 3 d i ) 2
1
6
π
ξ3 = N Aρ ⋅ D = η D = ∑ X i mi d i
6
j
u η
i
a disp 4 9
= m∑ ∑ Dij
RT i =1 j =1 kT τ
a chain N
= ∑ X i (1 − mi ) ln gij
RT i =1
2
1 3ξ 2 di d j 2ξ 22 d i d j
with g ij = + +
1 − ξ 3 (1 − ξ 3 ) 2 d i + d j (1 − ξ 3 )3 d i + d j
a asso N sites (i ) 1 − X Ai
= ∑ X i ∑ ln X Ai +
RT i =1 Ai =1 2
1
with X Ai = N sites( j )
1+ N Aρ ∑ ∑ X j X
Bj Ai B j
∆
j =1 B j =1
ε Ai B j
= gij exp − 1σ ij3κ Ai B j
Ai B j
∆
kT
σi + σ j
σ ij =
2
ε = ε Ai ε (1 − kε ij )
Ai B j Bj
κ = κ Ai κ (1 − kκ ij )
Ai B j Bj
- 112 -
Appendix A1: EOS in PE
3
3u 0
V = V 1 − 0,12 exp −
0 00
kT
1
2
3
d = V 0
NA
u u0 η
= 1 +
k k kT
- 113 -
Appendix A1: EOS in PE
MIXTURE PARAMETERS
SAFT-ConvexBody offers two mixing rules for the parameter u/k. Both mixing rules
require two binary interaction parameters per binary system and exactly reduce to the
original SAFT mixing rules by Huang and Radosz (1991) if all λ=0. The advantages of
these two-parameter mixing rules are explained in detail by Pfohl and Brunner (1998).
∑∑ X X m m
ui u j
u( 0 ) (1 − k ij )Vij0
=
i j i j kT
with
kT ∑∑ X X i j mi m jVij0
3
1
u (1)
=
∑ ∑ X i X j mi m jVij0 (∑ X i mi )
2
kT
u ui u j
= ∑∑ fi f j (1 − kij ) + ∑ f i ∑ f j
λij
kT kT kT
X k mkVk0
with the volume fraction fk =
∑ X i miVi 0
LITERATURE:
Chapman et al. (1986-1990)
Huang and Radosz (1990-1993)
Pfohl and Brunner (1998)
Boublik (1975, 1981)
Chen and Kreglewski (1977)
Alder, Young, and Mark (1972)
Wertheim (1984-1987)
- 114 -
Appendix A1: EOS in PE
24. SAFT-Conventional
This EOS is identical to SAFT-ConvexBody (section 23) but it does allow no use of
convex bodies (i.e. all α=1). This implementation allows to save different sets of pure
component parameter sets (and kij) in the same EXFILE - one with convex bodies using
EOS 23 and one without convex bodies using this EOS. This way it is easy to compare
calculation results, later. This implementation of SAFT should be used, if calculations
are intended with original SAFT by Huang and Radosz (1990-1993) in order to keep
calculations as easy as possible.
The Perturbed-Chain SAFT EOS was proposed by Groß and Sadowski (1999). Similar
to original SAFT, molecules are assumed to be chains composed of spherical
segments. In the dispersion term of the original SAFT model, the chain-like structure
of polymer compounds is not taken into account, since a hard-sphere reference is used.
Whereas, in the PC-SAFT model, the dispersive forces are accounted for applying a
perturbation theory of second order (Barker and Henderson), using an expression for
the radial pair distribution of a hard-chain reference fluid.
- 115 -
Appendix A1: EOS in PE
Three pure component parameters are required for each non-associating component:
the segment number m, the segment diameter σii , and the attraction parameter εii. The
association expression of the SAFT-model is used for associating compounds. The
additional association parameters are then: the number of association sites, the
association potential depth, and the association volume.
EOS:
Besides the association part, which is identical to original SAFT, the Helmholtz energy
of the EOS is split in a hard-chain contribution and a perturbation contribution:
A A hc A pert
= +
NkT NkT NkT
Hard-Chain Contribution:
A hc A ideal A hs
− =m⋅ − ∑ xi (1 − mi ) ln g iihs (σ ii )
NkT NkT N S kT i
1 3ζ 1ζ 2 ζ2 ζ 23
3
A hs
with = + + − ζ ⋅ ln (1 − ζ )
N S kT ζ 0 (1 − ζ 3 ) ζ 3 (1 − ζ 3 ) 3 ζ 3
2 0 3
2
1 dd 3ζ 2 did j 2ζ 2 2
and g =hs
+ i j +
(1 − ζ 3 ) d i + d j (1 − ζ ) 2 d + d (1 − ζ ) 3
ij
3 i j 3
π
where ζ m = ρ ∑ x i mi d i
m
6 i
Perturbation Contribution
A pert A1 A2
= +
kT N kT N kT N
A1 ε ij 3
with = −2πρ ⋅ I 1 (η , m ) ⋅ ∑∑ xi x j mi m j σ ij
kT N i j kT
−1
ε ij
2
A2 ∂Z hc
= −πρ ⋅ m ⋅ Z hc + ρ ⋅ I 2 (η , m ) ⋅ ∑∑ xi x j mi m j σ ij
3
and
kT N ∂ρ i j kT
The one-fluid mixing concept is applied to the compressibility term of the second order
perturbation term, i.e.
- 116 -
Appendix A1: EOS in PE
In these equations, the integrals over the radial pair distribution function of chain-
molecules were replaced by power series in density of sixth order
6
m −1 m −1 m − 2 i
I 1 (η, m ) = ∑ a 0i + a1i + a 2i ⋅ η
i=0 m m m
6
m −1 m −1 m − 2 i
I 2 (η, m ) = ∑ b0i + b1i + b2i ⋅ η
i=0 m m m
with the universal constants a0i, a1i, a2i and b0i, b1i, b2i :
PURE-COMPONENT PARAMETERS:
di is the temperature dependent segment diameter of component i:
ε
d = σ ⋅ 1 − 0.12 ⋅ exp − ii
kT
i ii
- 117 -
Appendix A1: EOS in PE
σ ij =
1
(σ ii + σ jj )
2
and
ε ij = ε ii ε jj (1 − k ij )
LITERATURE:
Groß and Sadowski (1999)
Groß and Sadowski (2000)
Chapman et al. (1988)
Barker and Henderson (1967)
27 PHSCT
Perturbed Hard-Sphere-Chain Theory was developed by Song, Lambert, and Prausnitz
(1994) in order to obtain an EOS for normal fluids and polymers. In PHSCT each
molecule is modelled as a chain of chemically bonded spheres similar to SAFT
(compare section 23/24). PHSCT was extended to copolymers by Song, Lambert, and
Prausnitz (1994b), later. The latter extension is not included in PE. Thus, for each
component only v00 and ε, which characterise one sphere as well as the number r of
spheres in a molecule have to be known.
EOS:
N N N ρ N N
Z = 1 + ρ ∑ ∑ ξi ξ j ri r j bij gij − ∑ ξi (ri − 1)( gii − 1) − ∑ ∑ ξi ξ j ri r j aij
i =1 j =1 i =1 kT i =1 j =1
- 118 -
Appendix A1: EOS in PE
Fa ( x ) = 0.717 + 19003
. exp( − 0.5152 x )
Fb ( x ) = 0.5849 exp( − 0.4772 x ) + 0.4151 1 − exp − 10669
. [
x −1/ 4 ( )]
s(r) is calculated from a FORTRAN function obtained from Professor
Prausnitz, University of California at Berkeley.
MIXTURE PARAMETERS
kT kT
aij = 4vij00 Fa ( ) Fa ( ) ε i ε j (1 − k ij )
ε i s(ri ) ε j s( r j )
3 3
3 v 00 + 3 v 00 3 b +3 b di + d j
, bij =
j
=
i j i
vij00 , d ij =
2 2 2
3 ζ ij 1 ζ ij
2
1
gij = + +
1 − η 2 (1 − η) 2 2 (1 − η) 3
ρ N
η= ∑ ξi ri bi
4 i =1
bi b j ρ N
ζ ij = ∑ ξ k rk bk2 / 3
ij 4 k =1
b
LITERATURE:
Song, Lambert, and Prausnitz (1994)
- 119 -
Appendix A1: EOS in PE
EOS:
RT a (T ) ~
P= ~ ~−~ ~ ~ with v~ = v + c and b =b+c
v − b v (v + b )
PURE-COMPONENT PARAMETERS:
R 2Tc2
a (T ) = a c ⋅ α (T ) with a c = 0,42747
Pc
~ RTc
b = 0.08664
Pc
- 120 -
Appendix A1: EOS in PE
30 (SRK-VT, Peneloux):
m = 0,48 + 1,574ω − 0,176ω 2
(
α (Tr ) = 1 + m(1 − Tr ) ) 2
31 (SRK-VT, Mathias):
m = 0,48 + 1,574ω − 0,176ω 2
if Tr<1: (
α (Tr ) = 1 + m(1 − Tr ) − p1 (1 − Tr )(0.7 − Tr ) ) 2
α (T ) = ( exp(c(1 − T ))) d 2
if Tr>1: r r
m
c = 1+ + 0.3 p1
2
c −1
d=
c
EXFILE EOS PARAMETER INPUT:
5 0 31 SRK-VT, Mathias
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000
p1 0.000000 0.000000
~
c/b 0.000000 0.000000 [ratio of c / b ]
LITERATURE:
Soave (1972)
Peneloux, Rauzy, and Freze (1982)
Mathias (1983)
- 121 -
Appendix A1: EOS in PE
32 (SRK-VT, Schwartzentruber-Renon):
m = 0,48508 + 1,55171ω − 0,15613ω 2
( )
2
if Tr<1: α (Tr ) = 1 + m(1 − Tr ) − p1 (1 − Tr )(1 + p2Tr + p3Tr2 )
2
1
if Tr>1: α (Tr ) = exp (1 − )(1 − Trd )
d
m
d = 1 + − p1 (1 + p2 + p3 )
2
EXFILE EOS PARAMETER INPUT:
7 0 32 SRK-VT, Schwartzentruber-Renon
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000
p1 0.000000 0.000000
p2 0.000000 0.000000
p3 0.000000 0.000000
~
c/b 0.000000 0.000000 [ratio of c / b ]
LITERATURE:
Soave (1972)
Peneloux, Rauzy, and Freze (1982)
Watanasiri and Gallier (1988)
Schwartzentruber, Renon (1989)
Schwartzentruber, Renon, and Watanasiri (1990)
Aspen Plus 9.3 Handbook, model: „SR-polar“
- 122 -
Appendix A1: EOS in PE
33 (SRK-VT, Thorwart-Daubert):
m = 0,48508 + 1,55171ω − 0,15613ω 2
2
(1 − Tr )
α (Tr ) = 1 + m(1 − Tr ) + n
Tr
EXFILE EOS PARAMETER INPUT:
5 0 33 SRK-VT, Thorwart-Daubert
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000
n 0.000000 0.000000
~
c/b 0.000000 0.000000 [ratio of c / b ]
LITERATURE:
Soave (1972)
Peneloux, Rauzy, and Freze (1982)
Thorwart and Daubert (1993)
34 (SRK-VT, Peneloux-3P):
m = 0,48 + 1,574ω − 0,176ω 2
(
α (Tr ) = 1 + m(1 − Tr ) ) 2
RTc
c = 0.40768 (0.00385 + 0.08775ω )
Pc
EXFILE EOS PARAMETER INPUT:
3 0 34 SRK-VT, Peneloux-3P
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000
LITERATURE:
Soave (1972)
Peneloux, Rauzy, and Freze (1982), model „RSKc3“
- 123 -
Appendix A1: EOS in PE
35 (SRK-VT, Boston-Mathias):
m = 0,48 + 1,574ω − 0,176ω 2
if Tr<1: (
α (Tr ) = 1 + m(1 − Tr ) − p1 (1 − Tr )(0.7 − Tr ) ) 2
2
1
if Tr>1: α (Tr ) = exp (1 − )(1 − Trd )
d
m
d = 1 + + 0.3 p1
2
EXFILE EOS PARAMETER INPUT:
5 0 35 SRK-VT, Boston-Mathias
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000
p1 0.000000 0.000000
~
c/b 0.000000 0.000000 [ratio of c / b ]
LITERATURE:
Soave (1972)
Peneloux, Rauzy, and Freze (1982)
Boston and Mathias (1980)
MIXTURE PARAMETERS:
The mixture parameters are calculated according to the mixing rules shown in
Appendix A2. In order to avoid inconsistencies, the parameters lij are set to 0. The
parameter c is the arithmetic mean of the ci.
40 3P1T
The 3P1T EOS by Yu and Lu (1987) contains three EOS parameters (=3P) whereof
one is temperature dependent (1T). The EOS is the result of the work by Yu et al.
(1986) who evaluated the abilities of many different cubic EOS to correlated different
properties of the first 10 members of the homologue series of n-alkanes. The use of
this EOS requires Tc, Pc and ω as pure-component parameters for each pure compound.
A brief comparison of this EOS and the Peng-Robinson EOS by Pfohl et al. (1997a),
Pfohl et al. (1998), and Pfohl (1998) showed that this EOS correlated pure-component
properties as well or slightly better than the PR EOS but gave slightly weaker mixture
correlations.
EOS:
RT a
P= −
v − b v( v + c ) + b(3v + c )
- 124 -
Appendix A1: EOS in PE
R 2Tc2
a c = ( 0,46863 − 0,0378304ω + 0,00751969ω ) 2
Pc
RTc
b = ( 0,0892828 − 0,0340903ω − 0,00518289ω 2 )
Pc
c
= −1,29917 + 0,648463ω + 0,895926ω 2
b
MIXTURE PARAMETERS
The mixture parameters are calculated according to the mixing rules shown in
Appendix A2.
LITERATURE:
Yu and Lu (1987)
Yu, Adachi, and Lu (1986)
- 125 -
Appendix A1: EOS in PE
41 Anderko, linear
The Anderko EOS implemented in PE is the EOS proposed by Anderko (1989 and
1989a) applicable to model systems containing any number of associating and inert
compounds. This AEOS (association + equation of state) uses the 3P1T EOS (section
40) as a so-called „physical“ part in order to model non-specific interactions between
molecules and a linear association model by Kempter and Mecke (1940) according to
the chemical theory in order to explicitly account for association (Eq. 32 in Anderko,
1989a).
The EOS therefore requires the same parameters as the 3P1T EOS for non-associating
(„inert“) compounds and as much as six pure-component parameters for each
associating compound. If association theory is included to model a pure compound, the
critical temperature calculated with the EOS is not longer Tc and Pc used as input for
the physical part of the AEOS, i.e. the 3P1T EOS. The inputs required for the 3P1T
part of the AEOS have therefore renamed into Tc’, Pc’, and ω’ by Anderko in order to
prevent confusion.
In addition to these three pure-component parameters, the input of ∆H 0 , ∆S 0 , and ∆C p0
which characterise hydrogen bonds is required for each associating component.
EOS:
r r r r r r r RT N 2ξi
P = P 3 P1T − EOS (T , v , ξ , Tc = Tc' , Pc = Pc' , ω = ω ' ) + ∑
v i =1 RT N
1+ 1+ 4 ∑K ξ
v j =1 ij j
T
b) − RT ln Kˆ i = ∆H 0 + ∆C 0p (T − T 0 ) − T (∆S 0 + C p0 ln )
T0
Note (also true for PE V1.0):
In order to be compatible with Anderko (1989-1992), the unit of K̂ is [atm], so
that K = 1.01323 Kˆ , because the unit of K is [bar].
- 126 -
Appendix A1: EOS in PE
MIXTURE PARAMETERS
The mixture parameters for the physical part given by the 3P1T EOS are calculated
according to the mixing rules shown in Appendix A2. The cross association constants
Kij are zero if either i or j is an inert compound, otherwise:
Kij = Ki K j (1 − kε ij )
N N ci + c j
c = ∑ ∑ ξi ξ j
i =1 j =1 2
LITERATURE:
Anderko (1989-1992)
Yu and Lu (1987)
Kempter and Mecke (1940)
Dolezalek (1908)
50 CPA-SRK-Tassios
Kontogeorgis, Voutsas, Yakoumis, and Tassios (1996) presented an EOS named
Cubic-Plus-Association EOS. Similar to Anderko (1989, section 41) they used a simple
cubic EOS as a reference system for physical interactions and added a second part to
this cubic EOS in order to account for association. Their proposed CPA EOS is based
on the Soave-Redlich-Kwong-EOS (Soave, 1972, section 3) and uses the powerful
association part from SAFT (compare section 23).
However, Kontogeorgis et al. (1996) use 4 pure-component parameters for each non-
associating compound although they use the Soave-Redlich-Kwong EOS, that
generally only requires 3 pure-component parameters. They use the parameters a0, b,
c1, and TcEXP , whereof TcEXP is set equal to the experimentally determined critical
temperature of the pure component.
Instead of using the radial distribution function for pure compounds for mixtures like
Tassios et al. did, the version implemented in PE uses the gij for mixtures by Boublik
(1970) and Mansoori et al. (1971).
EOS:
RT a (T ) RT ∂a~ asso
P= − + ρ
v − b v ( v + b) v ∂ρ
a asso N sites ( i )
1 − X Ai
~
a asso
= = ∑ X i ∑ ln X + Ai
RT i =1 Ai =1 2
PURE-COMPONENT PARAMETERS:
ai (T ) = ai0 (1 + ci1 (1 − T / TcEXP
,i )) 2
πd i3
bi = 4 N A
6
1/ 3
b
σi = i Note: σ i ≠ di
N Av
- 128 -
Appendix A1: EOS in PE
MIXTURE PARAMETERS:
The mixture parameters for the physical part (i.e. the SRK EOS) are calculated
according to the mixing rules shown in Appendix A2. The association equations are
essentially identical to the ones of SAFT.
1
X Ai = N sites ( j )
1+ N Aρ ∑ ∑ X j X
Bj Ai B j
∆
j =1 B j =1
ε Ai B j
= gij exp − 1σ ij3κ Ai B j
Ai B j
∆
kT
with
σi + σ j
σ ij =
2
ε = ε Ai ε (1 − kε ij )
Ai B j Bj
κ = κ Ai κ (1 − kκ ij )
Ai B j Bj
2
1 3ξ 2 di d j 2ξ 22 d i d j
g ij = + +
1 − ξ 3 (1 − ξ 3 ) 2 d i + d j (1 − ξ 3 )3 d i + d j
π N
ξk = N A ρ ∑ X i d ik
6 i =1
LITERATURE:
Kontogeorgis, Voutsas, Yakoumis, Tassios (1996)
Yakoumis, Kontogeorgis, Voutsas, Tassios (1997)
Voutsas, Kontogeorgis, Yakoumis, Tassios (1997)
Soave (1972)
Pfohl (1998)
- 129 -
Appendix A1: EOS in PE
51 CPA-SRK
Kontogeorgis et al. (1996, compare section 50) use 4 pure-component parameters for
each non-associating compound although they use the Soave-Redlich-Kwong EOS,
that generally requires 3 pure-component parameters, only. EOS 51, 52, 53, and 54 are
designed in such a way that only three parameters are necessary for the physical part of
the EOS, i.e. the cubic SRK, PR, or 3P1T EOS. These three parameters are named Tc’,
Pc’ and ω’, here. The prime (‘) indicates that the critical temperature (Tc), critical
pressure (Pc), and acentric factor (ω) calculated with the EOS are not longer identical
or even similar to the inputs of the physical terms, if association is included (compare
section 41).
Because the incorporation of association can lead to Tc’<<Tc and thus easier to Tc’<T,
the alpha functions of the SRK and PR EOS 51 and 52 have been extended to
„supercritical temperatures concerning the physical term“ for T>Tc’ according to the
approach by Boston and Mathias (1980, compare section 15 and 35 with p1=0).
The equations of EOS 51, 52, 54 concerning the physical part are thus identical to the
ones described in section 35, 15, and 40, respectively. The equations for the
association part are those listed in section 50.
- 130 -
Appendix A1: EOS in PE
52 CPA-PR
This EOS is practically identical to the one described in section 51. The only difference
is that the cubic EOS describing the physical part is the PR EOS from section 15
instead of the SRK EOS from section 35.
53 CPA-PR (a,b,om)
This EOS is essentially identical to the one described in section 52. The only difference
is that a0 (=a(Tc’)) and b are used as first two parameters instead of Tc’ and Pc’ and
that the alpha function by Mathias (1983) is used (compare EOS 11 with p1=0). It is
recommended to use EOS 52 (CPA-PR) because much better convergence can be
achieved at pure-component parameter determinations.
- 131 -
Appendix A1: EOS in PE
54 CPA-3P1T
This EOS is practically identical to the one described in the previous sections 51 and
52. The only difference is that the cubic EOS describing the physical part is the 3P1T
EOS from section 40.
90 SAFT-HR/vdW
This is the SAFT EOS by Huang and Radosz (1990-1991). The EOS 90 is a very old
implementation of SAFT in PE using the van-der-Waals mixing rule. The new
implementation by EOS=23/24 should be preferred, because it is much faster. This
implementation can be used to double check the implementation of EOS 23/24.
- 132 -
Appendix A1: EOS in PE
MIXTURE PARAMETERS:
The mixture parameters are calculated according to the way described by Huang and
Radosz (1991) which is nearly identical to the way described for EOS 23. However,
the second binary interaction parameter lij used here, is used to modify „m“ and not
used to modify „u“:
N N mi + m j
m = ∑ ∑ ξi ξ j mij with mij = (1 − lij )
i =1 j =1 2
N N
∑∑ ξ ξ i j mi m j u ij vij0 3 v0 + 3 v0
3
vij =
i =1 j =1 i j
u= with 0
and uij = ui u j (1 − k ij ) ∇
N N
∑∑ ξ ξ
2
i j mi m j vij0
i =1 j =1
91 SAFT-HR/vf
This is the SAFT EOS by Huang and Radosz (1990-1991). The EOS 91 is also a very
old implementation of SAFT in PE. The new implementation by EOS=23/24 should be
preferred, because it is much faster. In contrast to EOS 90 it uses the volume fraction
mixing rule.
MIXTURE PARAMETERS:
N N mi + m j
m = ∑ ∑ ξi ξ j mij with mij = (1 − lij )
i =1 j =1 2
N N
ξ i mi vi0
u = ∑∑ f i f j u ij with fi = N
and uij = ui u j (1 − k ij )
∇
i =1 j =1
∑ξ
j =1
j m j v 0j
That means γ = 1 for volume fraction according to Huang and Radosz (1991).
∇ The formulas for deriving „u“ had been wrong in the manual for PE V1.0. The program had been correct.
- 133 -
Appendix A1: EOS in PE
94 Deiters
Deiters (1981, 1981a, 1982) constructed an EOS based on perturbed hard chain theory
with the aim to obtain an EOS which yields correct critical temperatures, pressures,
and densities of pure components. Calculations of phase equilibria of mixtures under
elevated pressure may be affected by the wrong representation of the pure components’
critical points, seriously (compare: Pfohl et al., 1998). However, the extension of this
EOS to mixtures is difficult - leading to an implementation in PE for pure components,
only. Deiters (1982) proposed an extension to binary mixtures. Because the EOS
originally proposed by Deiters (1981) could not be integrated analytically, Deiters
(1982) exchanged a part by a polynomial series. The EOS with the polynomial function
Ft is implemented in PE. The three pure-component parameters needed for the Deiters
EOS are: a, b, and c.
EOS:
4ξ − 2ξ 2 abρ
3 − 2 (h0γ ψ ( T ) + Fi +1 )
~
Z = 1 + cc0 2
(1 − ξ ) c T
3 6 10
~
with Ft = ∑ ∑ ∑ pijk (c − 1) k T − j (bρ ) i t
k = 0 j = 0i = 0
~ ~ ~
ψ (T ) = T (exp(T −1 ) − 1)
γ = 1 − 0.697816(c − 1) 2
~ ckT π 2
h0 = 7.0794046 , c0 = 0.6887 , T = ,ξ= bρ
ε 6
MIXTURE PARAMETERS
The EOS implemented in PE is for pure compounds, only.
LITERATURE:
Deiters (1981, 1981b, 1983)
Pfohl et al. (1998)
- 134 -
Appendix A1: EOS in PE
95 PHCT
The Perturbed Hard Chain Theory by Beret and Prausnitz (1975) was the first attempt
to construct a hard chain EOS which should cover the whole density region from ideal
gas to close packing and all kinds of molecular complexity by incorporation of
Prigogines factor c also covering other than translational degrees of freedom
(Prigogine, 1957). However, the original paper by Beret and Prausnitz is restricted to
pure components - and so is the implementation of PHCT in PE. Many groups did pick
up the idea by Beret and Prausnitz afterwards. An early extension of PHCT to mixtures
is the one by Donohue and Prausnitz (1978). The modification of PHCT by Pfennig
(1988) which is also applicable to mixtures is described in section 20. The EOS 95
needs three inputs for a pure compound: <eqk>, <rv*>, and <c>.
EOS:
4η − 2η 2 4 9 mA
nm
Z = 1 + c 3 + ∑ ∑ ~m ~n
(1 − η) n =1m=1 v T
v~ −1 = rv * ρ
~ cT
T=
εq / k
MIXTURE PARAMETERS
The EOS implemented in PE is for pure compounds, only.
LITERATURE:
Beret and Prausnitz (1975)
Donohue and Prausnitz (1978)
Carnahan and Starling (1969)
Prigogine (1957)
- 135 -
Appendix A1: EOS in PE
96 LJ-SAFT, Kraska
This EOS is the Lennard-Jones SAFT by Kraska and Gubbins (1996). The
implementation in PE only works for pure components, yet.
97 LJ-SAFT, JZG
This Lennard-Jones SAFT is similar to that by Kraska and Gubbins (1996, see above
section). The only difference between both EOS is that EOS 97 uses the equation of
Johnson, Zollweg, and Gubbins (1993) instead of the equation of Kolafa and Nezbeda
(1994) to describe the LJ-contribution. This implementation in PE suffers the same
deficits like EOS 96, because most equations are the same.
- 136 -
Appendix A2: Mixing Rules for Cubic EOS
N N
a = ∑ ∑ xi x j aij (A2.1)
i =1 j =1
N N
b = ∑ ∑ xi x j bij (A2.2)
i =1 j =1
All mixing rules offer three adjustable binary interaction parameters, except the simple
quadratic mixing rule which only offers two adjustable parameters per binary system.
One binary interaction parameter is used to adjust the mixture parameter b, the other
parameters are used to adjust the mixture parameter a.
It should be noted that the Adachi-Sugie-, Panagiotopoulos-Reid-, Melhem-, and
Stryjeck-Vera mixing rule suffer the so-called Michelsen-Kistenmacher-Syndrome
(Michelsen and Kistenmacher, 1990). Using them yields different calculation results if
λ≠0 and the mole fraction xi of one component is arbitrarily split into two mole
fractions xi’ and xi“ with xi’+xi“=xi. The use of these mixing rules is not recommended,
because this theoretical disadvantage is strongly correlated to inabilities to model real
systems as shown by Mathias et al. (1991), Pfohl (1998), and Pfohl et al. (1999).
Instead, it is recommended to use the Mathias-Klotz-Prausnitz mixing rule which does
- 137 -
Appendix A2: Mixing Rules for Cubic EOS
not suffer this deficit, although it is identical to all above mixing rules for binary
systems. The MKP-WS mixing rule is a modification of the Mathias-Klotz-Prausnitz
mixing rule which also reproduces the quadratic dependence of the second virial
coefficient enforced by theory, correctly.
bi + b j
bij = (1 − l ij ) with l ji = l ij (A2.4)
2
bi + b j
bij = (1 − l ij ) with l ji = l ij (A2.6)
2
- 138 -
Appendix A2: Mixing Rules for Cubic EOS
bi + b j
bij = (1 − l ij ) with l ji = l ij (A2.9)
2
The original formula for the calculation of parameter a proposed by Adachi and Sugie
(1986) is shown in Eq. (A2.10).
1
Equations (4), (5), (6), (13), and (14) in this publication. It should be noted that these equations are different
from the equations (7) and (8) in this publication, although Adachi and Sugie claim that they are identical.
Equations (7) and (8) would lead to λijAS = + λ AS
ji and therefore to a complete elimination of this parameter in
k ijSV k SV
ji
aij = ai a j (1 − ) with λijSV := k ijSV − k SV
ji = − λ ji
SV
(A2.11)
xi k ijSV + x j k SV
ji
bi + b j
bij = (1 − l ij ) with l ji = l ij (A2.12)
2
xi
aij = ai a j (1 − k ijM + λ ijM ) with λijM = k ijM − k jiM = − λ Mji (A2.13)
xi + x j
bi + b j
bij = (1 − l ij ) with l ji = l ij (A2.14)
2
2
Equation (13) in this publication.
3
Equation (12) in this publication.
4
Equation (6) in this publication.
5
Equations (4), (5), (6), (12), and (13) in this publication.
- 140 -
Appendix A2: Mixing Rules for Cubic EOS
binary systems, so that binary interaction parameters regressed from binary systems in
literature can be used for this mixing rule without the necessity to optimise the
parameters, again (compare A2.8).
( )
1/ 3 3
N N N N
a = ∑ ∑ xi x j ai a j (1 − k ijMKP ) + ∑ xi ∑ x j ai a j λ MKP
i =1 j =1
ji
i =1 j =1
bi + b j
bij = (1 − l ij ) with l ji = l ij (A2.16)
2
Mathias et al. (1991) used the abbreviation lij instead of λij in Eq. A2.15.
a N N N N a
b− = B = ∑ ∑ xi x j Bij = ∑ ∑ xi x j b − (A2.17)
RT i =1 j =1 i =1 j =1 RT ij
( )
1/ 3 3
N N N N
a = ∑ ∑ xi x j ai a j (1 − k ijBP ) + ∑ xi ∑ x j ai a j λ BP (A2.18)
i =1 j =1
ji
i =1 j =1
bi + b j
( )
1/ 3 3
N N 1 N N
b = ∑ ∑ xi x j (1 − l ij ) + ∑x ∑x ai a j λ BP (A2.19)
i =1 j =1 2 RT i =1 i j =1 j ji
- 141 -
Appendix A2: Mixing Rules for Cubic EOS
- 142 -
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