PE2000 Manual

Preface, Contents, Survey, and Introduction
- 1 -
Preface

PE 2000: A Powerful Tool to Correlate Phase Equilibria

The first preliminary Windows release of PE had been shown at the 8
th
International
Conference on Properties and Phase Equilibria for Product and Process Design at
Noordwijkerhout, The Netherlands, on April 30
th
, 1998 (Pfohl et al., 1998a).

The first official Windows release of PE was finished in July 1998 and shown at the
17
th
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).

The newest version of PE will be shown at the ACHEMA at Frankfurt, Germany, in
May 2000 and at the 18
th
European Seminar on Applied Thermodynamics at Kutn
Hora, Czech Republic, in June 2000 (Petkov et al., 2000).

February 2000 Oliver Pfohl
Stanimir Petkov
Gerd Brunner
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Contents Page
Survey 4
Introduction 5

1 Input Files Containing Experimental Data .................................................. 6
1.1 Pure-Component Data 7
1.1.1 PCFILES 7
1.1.2 Generating PCFILES 12
1.1.3 Generating PCFILES using the data compilation by Daubert&Danner 18
1.1.4 Saving EOS parameters to a PCFILE 20
1.2 Mixture data 21
1.2.1 EXFILES 21
1.2.2 Generating EXFILES 25
1.2.3 Editing EXFILES 32
1.2.4 Estimating Pure-Component Parameters 33

2 Pure-Component Calculations .................................................................... 41
2.1 Determination of Pure-Component EOS Parameters 41
2.1.1 Visualisation of Grids/Optimisations 46
2.2 Calculation of Vapour Pressure Curves 48
2.2.1 Graphical Output of Vapour Pressure Curves 49
2.3 Calculation of P-Diagrams 51
2.3.1 Graphical Output of P-Diagrams 52
2.4 Calculation of Deviations 53

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
- 3 -
4 Implementation of New EOS by Users ....................................................... 73
4.1 Introduction 73
4.2 Files Used for Implementing New EOS in PE 74
4.3 The File pes_EOS_?.for 75
4.3.1 Initialization (calc_what=0) 81
4.3.2 Calculate Pressure (calc_what=1) 81
4.3.3 Calculate Fugacity Coefficients (calc_what=2) 82
4.4 pes_EOS_by_User.FOR 83
4.4.1 Subroutine Parameters 83
4.4.2 Parameters for Simple Peng-Robinson EOS (FORTRAN: save) 85
4.4.3 Initialization (calc_what=0) 85
4.4.4 Calculate Pressure (calc_what=1) 86
4.4.5 Calculate Fugacity Coefficients (calc_what=2) 86
4.4.6 Subroutine si_mix_abc 86
4.5 EOS_P_TEST.FOR, EOS_PHI_TEST.FOR Programs 87
4.6 FORTRAN Language 87
4.7 EOS_on_DISK.FOR 88
4.7.1 Running EOS_on_DISK.EXE 88
4.8 Some Details 90
4.8.1 Enforcing T
c
and P
c
during Optimization 90
4.8.2 Using Sites and Interaction Parameters 90
4.8.3 The File EOS_on_DISK.sav 91

5 Export of Data ............................................................................................... 92

6 Future Developments ................................................................................... 93

Appendix ...................................................................................................... 94
A1: EOS Implemented in PE 94
A2: Mixing Rules for Simple EOS 137

Literature......................................................................................................... 143
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Survey
The program PE ( = Phase Equilibria ) has been developed in Professor Brunners
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.
- 5 -
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 g
E
-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
g
E
-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.
Chapter 1: Input Files Containing Experimental Data
- 6 -
1 Input Files Containing Experimental Data
The use of EOS in order to model phase equilibria requires pure-component and
mixture parameters. The van-der-Waals EOS (Eq. 1.1) with one-fluid mixing and
combining rules, (Eq. 1.2 and 1.3), serves as a simple example to demonstrate this.

P
RT
v b
a
v
=

2
(1.1)
a a a k
i j i j
j
N
i
N
ij
=
= =

1 1
1 ( ) (1.2)
b
b b
l
i j
i j
ij
j
N
i
N
=
+

= =

2
1
1 1
( ) (1.3)

Pure Components
The pure-component parameters a
i
and b
i
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
i
), the pure-component properties (a
i
and b
i
i) and interactions
between unlike molecules (ij). 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 k
ij
and l
ij
in Eq. 1.2 and
1.3) in order to express the deviation from standard interactions (k
ij
=l
ij
=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,
- 7 -
how these data can be compared to the calculated results and how predictions can be
obtained that are based on these interaction parameters.
1.1 Pure-Component Data
1.1.1 PCFILES
Pure-component data are stored in so-called PCFILES (= pure-component files) in the
subdirectory /PE/PCDATA. Each PCFILE contains experimental data for one compound.
A typical PCFILE is shown below. This PCFILE contains data for carbon dioxide.
---------------------------------------------------------------------------------------------------------
component a30 : carbon dioxide
data source a30 : Span and Wagner, 1996
data input a30 : created on 1998-07-02 at 16:30
Mw, g/mol e13.6e2 : 0.440100E+02
Tc, K e13.6e2 : 0.304130E+03
Pc, bar e13.6e2 : 0.737700E+02
omega, - e13.6e2 : 0.225000E+00
Vapour Pressure Curve
=====================
T = 0 ! 0=K, 1=C, 2=F
P = 0 ! 0=bar, 1=MPa, 2=Torr, 3=atm
? = 0 ! 0=density, 1=volume
m = 3 ! 0=mol, 1=kmol, 2=g, 3=kg
v = 2 ! 0=cm3, 1=dm3, 2=m3
ovP T____________ P____________ RhoL_________ RhoG_________
111 0.216590E+03 0.517960E+01 0.117846E+04 0.137610E+02
111 0.224000E+03 0.706210E+01 0.115140E+04 0.185300E+02
111 0.234000E+03 0.103630E+02 0.111308E+04 0.269360E+02
111 0.244000E+03 0.146900E+02 0.107213E+04 0.381840E+02
111 0.254000E+03 0.202170E+02 0.102772E+04 0.531440E+02
111 0.264000E+03 0.271340E+02 0.978510E+03 0.731240E+02
111 0.274000E+03 0.356420E+02 0.922300E+03 0.100320E+03
111 0.284000E+03 0.459780E+02 0.854740E+03 0.139090E+03
111 0.294000E+03 0.584430E+02 0.764090E+03 0.201060E+03
001 0.300000E+03 0.671310E+02 0.679240E+03 0.268580E+03
001 0.301000E+03 0.686830E+02 0.658690E+03 0.286150E+03
001 0.302000E+03 0.702680E+02 0.633690E+03 0.308150E+03
001 0.303000E+03 0.718900E+02 0.599860E+03 0.339000E+03
001 0.304000E+03 0.735550E+02 0.530300E+03 0.406420E+03
Isotherms (n= 2)
================
T= 250.000 K; (n=20); (code=K0032)
P____________ Rho__________
0.500000E+00 0.106340E+01
0.100000E+01 0.213630E+01
0.200000E+01 0.431200E+01
0.300000E+01 0.652920E+01
0.500000E+01 0.110970E+02
0.100000E+02 0.234350E+02
0.200000E+02 0.104688E+04
0.300000E+02 0.105102E+04
0.400000E+02 0.105501E+04
0.500000E+02 0.105886E+04
0.600000E+02 0.106259E+04
0.750000E+02 0.106796E+04
0.100000E+03 0.107642E+04
0.150000E+03 0.109177E+04
0.200000E+03 0.110547E+04
0.300000E+03 0.112930E+04
- 8 -
0.400000E+03 0.114968E+04
0.500000E+03 0.116759E+04
0.750000E+03 0.120504E+04
0.100000E+04 0.123557E+04
T= 300.000 K; (n=20); (code=K0032)
P____________ Rho__________
0.500000E+00 0.884340E+00
0.100000E+01 0.177300E+01
0.200000E+01 0.356360E+01
0.300000E+01 0.537230E+01
0.500000E+01 0.904560E+01
0.100000E+02 0.185790E+02
0.200000E+02 0.394200E+02
0.300000E+02 0.633760E+02
0.400000E+02 0.919650E+02
0.500000E+02 0.128400E+03
0.600000E+02 0.182310E+03
0.750000E+02 0.733900E+03
0.100000E+03 0.801620E+03
0.150000E+03 0.865820E+03
0.200000E+03 0.905570E+03
0.300000E+03 0.959700E+03
0.400000E+03 0.998350E+03
0.500000E+03 0.102894E+04
0.750000E+03 0.108656E+04
0.100000E+04 0.112945E+04
Pure-Component EOS Parameters
=============================
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 !
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.
- 9 -
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.
The data for the vapour pressure curve
The data block for the vapour pressure curve begins with the definition of the units of
the data. In the above example the units for temperature and pressure are Kelvin and
bar, respectively. The densities/volumes of the coexisting liquid and vapour phase are
given as densities in kg/m
3
(compare legend in the unit definition block).
The below lines contain the data: temperature, saturation pressure, liquid density and
vapour density. The data points have to be listed by ascending temperature. 1 or 0
in the first column indicates if the data of this line should be used for pure-component
parameter optimisation (section 2.1) or not. 1 or 0 in the second and third column
indicate, if the data of this line should be displayed in plots of the vapour pressure
curve and P-diagrams (section 2.2 and 2.3, respectively).
It is recommended that this list includes at least three vapour pressures, that are
selected to be used for optimisations, and that these data cover a large representative
range of the vapour pressure curve. In order to prevent confusion, later, the 1/0 in
the first two columns of each line should be identical. For commonly used compounds,
it is not recommended to select data for optimisations which are closer than about 5 K
to the critical temperature, because convergence there is slow and not always
successful. In the above example the data, that are closer than 10 K to T
c
are disabled
for optimisations, therefore.
Optional PvT data
The third block of the above file contains PvT data in blocks of isothermal data. These
data are optional, because they are not used for any parameter optimisations. These
data can only be displayed together with calculation results in P-diagrams (section
2.3.1). The header of the PvT-data block contains the number of isotherms. The header
of each isotherm contains the temperature of the isotherm, the number of points on the
isotherm, and a code for the definition of the units. The code (from left to right) uses
the same digits as the code from the vapour pressure curve units block (from top to
bottom). The input of temperature has to be in Kelvin.
Pure-component EOS parameters
Pure-component EOS parameters can be saved in PCFILES using PE. The EOS
parameters saved here, will be used as default parameters for filling blank edit boxes
- 10 -
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.

---------------------------------------------------------------------------------------------------------
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 7
th
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
- 11 -
format (starting with sites instead of Sites, also compare both SAFT data sets in
Figure 1.1a) by the new version of PE.

Old format New format
sites 0 Sites 0 0 0
sites 1 Sites 0 0 1 = one (COOH) site
sites 2 Sites 1 1 0 = one (+) and one (-) site = alcohol
sites 3 Sites 2 1 0 = two (+) and one (-) site = like water
sites 4 Sites 2 2 0 = two (+) and two (-) sites = also like water

Figure 1.1c: Format of the sites line. The new version of PE reads old and new format.

- 12 -
1.1.2 Generating PCFILES

Selecting FILE/NEW/PURE-COMPONENT DATA from the main menu will cause creating
a new file containing pure-component properties (Figure 1.1d).

Figure 1.1d: Selecting FILE/NEW/PURE-COMPONENT DATA to generate a new PCFILE.

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.

- 13 -
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.

Figure 1.1f: Selecting a compound from the pure-component data base.

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).
- 14 -

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.

Vapour Pressure Curve
After choosing the component, the user has to select the units for the input of the data
of the vapour pressure curve and the data (Figure 1.1h).
Afterwards, the vapour pressure curve data have to be entered by ascending
temperature. Each data point on the vapour pressure curve consists of a temperature,
the saturation pressure, the densities (or molar/specific volumes) of both coexisting
phases and three flags indicating what the data should be used for (Figure 1.1i,
compare section 1.1.1).
- 15 -
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).

Figure 1.1i: Adding a new point to the vapour pressure curve.

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).
- 16 -
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.

Each point on an isotherm at a given temperature consists of a pair [pressure, density]
or [pressure, volume] (Figure 1.1l). Pressing the button ADD adds the point to the
isotherm and asks for the next point on the same isotherm. Pressing ADD+EXIT adds
the point to the isotherm and asks if other isotherms should be entered (dialog box 1.1j,
again).
The isotherms should be sorted by ascending temperature. The points on the isotherms
have to be sorted by ascending pressure.

- 17 -

Figure 1.1l: Input of a point on an isotherm.

- 18 -
1.1.3 Generating PCFILES using the data compilation by Daubert
and Danner

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).

Figure 1.1m: Selecting FILE/NEW/PURE-COMPONENT DATA, D+D in order to generate
a new PCFILE using the data compilation by Daubert and Danner.

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:

Equation 101 by Daubert and Danner:
+ + + =
E
DT T C
T
B
A Y ln exp

Equation 105 by Daubert and Danner:
+
=
D
C
T
B
A
Y
1 1

Further equations will be build in PE upon request.
- 19 -

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.

- 20 -
1.1.4 Saving EOS parameters to a PCFILE
In order to append pure-component EOS parameters to an existing PCFILE using the
dialog box shown in Figure 1.1p, the menu entry PURE COMPONENT/SAVE
PARAMETERS TO PC-FILE has to be selected: Figure 1.1o.

Figure 1.1o: Selecting PURE COMPONENT/SAVE PARAMETERS TO PC-FILE in order to
append pure-component EOS parameters to an (existing) PCFILE.

Figure 1.1p:

Dialog box for appending pure-
component EOS parameters to a
PCFILE.

One line with information has to
be saved together with the para-
meters.

- 21 -
1.2 Mixture Data
1.2.1 EXFILES
Mixture data are stored in so-called EXFILES (= files with experimental mixture data)
in the subdirectory /PE/EXDATA. Each EXFILE contains experimental data for one
system with at least two components. A typical EXFILE is shown in Figure 1.2a. This
EXFILE contains some data for the binary system p-cresol + carbon dioxide.
Each EXFILE consists of a header, pure-component data, pure-component EOS
parameters, phase equilibrium data of mixtures, and optional binary EOS interaction
parameters.
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.
- 22 -
---------------------------------------------------------------------------------------------------------
>CO2 + p-Cresol <
>Pfohl, 1998 <
>created on 1998-06-01 at 14:36<
Literature
----------
>Dissertation, <
>TU Hamburg-Harburg, <
>Thermische Verfahrenstechnik <
> <
02 components: pure component data
----------------------------------
>carbon dioxide <
>p-cresol <
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
system data, 1 (mol)
--------------------
01 point(s), T= 290.00
----------------------
0 EQ=L1L2, P= 100.0000
carbon dioxide 0.9969000000 0.3160000000
p-cresol 0.0031000000 0.6840000000
06 point(s), T= 323.15
----------------------
1 EQ=L1L2, P= 100.0000
carbon dioxide 0.9969000000 0.3160000000
p-cresol 0.0031000000 0.6840000000
1 EQ=L1L2, P= 150.0000
carbon dioxide 0.9822000000 0.4200000000
p-cresol 0.0178000000 0.5800000000
1 EQ=L1L2, P= 200.0000
carbon dioxide 0.9729000000 0.4470000000
p-cresol 0.0271000000 0.5530000000
1 EQ=L1L2, P= 250.0000
carbon dioxide 0.9645000000 0.4910000000
p-cresol 0.0355000000 0.5090000000
1 EQ=L1L2, P= 301.0000
carbon dioxide 0.9557000000 0.5210000000
p-cresol 0.0443000000 0.4790000000
1 EQ=L1L2, P= 348.0000
carbon dioxide 0.9480000000 0.5480000000
p-cresol 0.0520000000 0.4520000000
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
- 23 -
Pure-Component EOS Parameters
The pure-component EOS parameter section includes all pure-component EOS
parameters (like v
00
/dm
3
mol
-1
from SAFT) for calculations with this EXFILE. They are
stored in such a way that one line contains a given property of all components in the
form of an alpha numerical identifier (maximum: five letters) and the values for each
component. All EOS parameters for one given EOS are stored in one block with a one-
line header. 03_0_01_Peng-Robinson stands for a block containing the pure-
component parameters for the Peng-Robinson EOS (number 01 in PE, appendix A1)
with 03 lines containing the parameters and similar whereof 0 lines contain the number
of association sites (compare EOS 23 - 24, 50 - 54, and 90 - 91 in appendix A1).
A list of the properties, numerical codes and properties is given in Appendix A1
together with the different EOS available in PE. When generating an EXFILE, these
lines are generated for all properties entered by the user automatically. Appendix A1
only becomes important, in case that additions should be made to the EXFILE, later - or
that numerical inputs should be double checked.
Phase Equilibrium Data
The phase equilibrium data (SYSTEM DATA) are stored in blocks. The usage of weight
fractions or mole fractions for phase compositions in the EXFILE is indicated in the line
SYSTEM DATA. Each block has its own header, containing the total number of
equilibria in the block and common properties of all equilibria in the block (like the
temperature for a block containing isothermal data, here).
Each entry for an equilibrium consists of a one-line header and one line for each
compound which contains the mole or weight fractions of the compound in all
equilibrium phases. The header contains the type of equilibrium (either V_L1, V_L2,
L1L2, or VL12), properties that might be different from the properties of the next
equilibrium (like the pressure in an isothermal block of a binary system, here), and
flags indicating what the equilibrium will be used for, later (Table 1.1).

Table 1.1: Flags characterising the use of single equilibria in an EXFILE.
Flag Usage of equilibrium in PE
0 This equilibrium will not be used for the calculation of the Objective
Function. This equilibrium will not be plotted in diagrams.
1 This equilibrium will be used to compare calculation results with
experimental data, i.e. for calculating the Objective Function. The
equilibrium will also be plotted in diagrams.
2 This equilibrium will not be used for the calculation of the Objective
Function, but this equilibrium will be plotted in diagrams.
- 24 -
Table 1.2: Usage of flags for single equilibria in an EXFILE

Flag Usage in case:
0 a) If equilibrium calculations should be performed at conditions where no
experimental data are available using ADDITIONAL POINT CALCULA-
TIONS (section 3.1), the creation of a block with an INITIAL GUESS for the
calculations is necessary. Block 1 (T=290K) in Figure 1.11 contains an
INITIAL GUESS, only. The INITIAL GUESS was obtained from T=323.15K
(compare block 2).
b) If thermodynamic models are poor, not all experimental data can be
correlated, because the flash algorithm does not converge any more. The
model might predict a one phase region where two or three phase regions
have been measured experimentally. In this case it is advisable to mark
the point where the model does not yield calculated data as point not to
be used. Running optimisations with such EXFILES are much faster,
because not all points are used to optimise the parameters any more.
Especially the calculations where no convergence can be achieved (and
that need a long time therefore) are avoided.
c) In case binary interaction parameters are varied using a large GRID in
order to find a suitable pair of binary parameters to start an
OPTIMISATION (section 3.2), it is advisable to mark all except one point
with 0 (or 2) in order to speed up the grid calculations. The point
excluded from the calculations this way should be included again before
doing the optimisations, afterwards - if possible.
1 This is the normal selection for any experimental equilibrium where all
system components are present in all phases (at least traces).
2 a) In binary systems, the vapour pressure points of the pure compounds are
often added in order to see them in the binary diagrams, later. Because
binary calculations can not be done at pure-component tie lines and
optimisations of binary interaction parameters can not be done based on
pure-component data, these data must be marked as PLOT, ONLY.
b) In ternary systems the tie lines of the binary subsystems are often included
in the EXFILE in order to display them in the same graph as the ternary
data (see section 3.4). On the other hand, it might be desired to calculate
errors only in the calculated mole fractions of the true ternary tie lines in
order to judge about the capabilities of EOS to predict ternary data based
on interaction parameters of regressed from binary data (compare section
3.1). Relative errors can not be calculated based on zero mole fractions
anyway (division by zero!).
- 25 -
Binary Interaction Parameters
This section contains binary interaction parameters for the EXFILE system and different
EOS and mixing rules. When creating a new EXFILE, no binary interaction parameters
are stored. After regressing binary interaction parameters (section 3.2) these
parameters can be appended to the EXFILE.
Each interaction parameter block contains an one-line header and the binary
parameters. The header includes the number of the EOS, mixing rule, and system data
block for which the parameters have been saved. A list of EOS and mixing rules is
given in appendices A1 and A2. This way different interaction parameters can be used
for calculating different system data blocks. The parameters are stored in loops like

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), (i,j), s(1,j), s(j,1), k(i,j), k(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:

write s(1,j) (j= 1, N)
write s(j,1) (j= 1, N).

1.2.2 Generating EXFILES
Selecting FILE/NEW/MIXTURE DATA from the main menu initiates the creation of a
new EXFILE containing mixture data (Figure 1.2b).

Figure 1.2b: Selecting the menu entry to generate a new EXFILE with mixture data.

- 26 -
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.

Figure 1.2c: Input of data for the header of a new EXFILE.

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.

- 27 -

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 T
c
, P
c
, T
b
, and , 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 T
c
, P
c
, and , 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.

- 28 -

Figure 1.2e: Input of pure-component data. Figure 1.2f: Selecting an EOS for the
input of pure-component parameters.

Figure 1.2g: Input of pure-component parameters for different EOS.

- 29 -
Phase Equilibrium Data
For binary systems, the phase equilibrium data have to be supplied in blocks containing
isothermal data. For ternary systems, the phase equilibrium data have to be supplied in
blocks containing experimental data at identical temperature and identical pressure -
only varying in the composition of the coexisting phases. PE will assist in generating
such blocks in the EXFILE, if the input of the data is in the correct order. Selecting the
check box NEW BLOCK will create a new block (Figure 1.2h).

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 ...

The correct order for a ternary system is:
1) T1 / P1 / equilibrium A \ block 1
2) T1 / P1 / equilibrium B ... /
3) T1 / P2 / equilibrium C \ block 2
4) T1 / P2 / equilibrium D ... /
5) T2 / P3 / equilibrium E \ block 3
6) T2 / P3 / equilibrium F ... /
7) T3 ... > block 4 ...

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.
- 30 -

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.

If a three-phase region was observed experimentally at a given temperature and
pressure, this phase equilibrium should be entered as the first in the block. This speeds
up the calculation of ADDITIONAL POINTS enormously (section 3.1) and prevents the
(wrong) calculation of tie lines through the three phase region. If a three phase region
is likely to occur / to be calculated - but was not found by experiment - the first
equilibrium in the block should be an INITIAL GUESS containing a three phase region.

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.

- 31 -
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.

Figure 1.2i: miscibility gaps in a binary system.

Figure 1.2j: miscibility gaps in a ternary system.
Phase: L1
Phase: L2
Phase: V
Phase: V
Phase: L2
Phase: L1
three-phase region
- 32 -
1.2.3 Editing EXFILES
Selecting FILE/ADD/EQUILIBRIUM DATA and FILE/ADD/PURE-COMPONENT EOS
PARAMETERS allows to add equilibrium data and pure-component parameters to an
existing EXFILE, respectively (Figure 1.2k).
Note: in order to use an edited EXFILE, that was opened for mixture calculations by PE
during editing, for calculations afterwards, the EXFILE has to be reopened (compare
3.1) PE will ask for reopening such a fle, automatically.

Figure 1.2k: Selecting a menu entry in order to add equilibrium data to an existing
EXFILE.

Adding pure-component EOS parameters
Selecting FILE/ADD/PURE-COMPONENT EOS PARAMETERS from the main menu
allows to add further pure-component EOS parameters to an existing EXFILE and
allows to change existing pure-component EOS parameters in an EXFILE.
A dialog box (Figure 1.2f) will ask for the EOS for which the parameters should be
added/changed. Double clicking an EOS will ask for the new parameters of all
compounds for this EOS (Figure 1.2g). Existing EOS parameters will be displayed as
defaults. Selecting SAVE+EXIT will save the data to the EXFILE, selecting ABORT will
terminate the input without changes in the EXFILE.

Adding mixture data
Selecting FILE/ADD/EQUILIBRIUM DATA from the main menu allows to add further
mixture data to an existing EXFILE. The input of data is arranged in blocks like
described in section 1.2.2 GENERATING EXFILES.

- 33 -
1.2.4 Estimating Pure-Component Parameters
When generating the pure-component data block for a new EXFILE (Figure 1.2e), it
might occur, that the properties T
c
, P
c
, T
b
, and are not known from experimental
sources, because of thermal decomposition or experimental difficulties.
In order to enable calculations with some simple equations of state, that only need the
critical pressure, the critical temperature, and the acentric factor as pure-component
parameters (like the Peng-Robinson EOS), PE offers some methods for estimating
these properties using group contribution methods or empirical relations.

1.2.4a Group Contribution Methods
If the chemical structure of a compound is known, this compound can be split into
defined chemical groups whereof each is thought to contribute to a certain pure-
component property to a certain extent.
The authors of the methods built in PE, have investigated many substances and have
determined the average contribution to a certain property for each group. Based on this,
the pure-component properties can now be estimated as a sum of the determined
contributions of each group in the molecule.
The two group contribution methods implemented in PE are the well known ones by
Joback and by Fedors for estimating T
c
, P
c
and T
b
(Reid et al., 1987).

1.2.4b The Method by Fedors
This method is used for estimating the critical temperature, T
c
, only. The method does
not require additional data except the tabulated T-values listed below and stored by
PE. The Fedors relation can be written as:

= T K T
c
lg 535 /

Table 1.3: group contributions according to Fedors

Group Implementation in PE
T
3
CH
-CH3 1.79

2
CH
-CH2 1.34
> CH
>CH- 0.45
< > C
>C< -0.22
2
CH =
=CH2 1.59
= CH
=CH-- 1.40
= > C
>C= 0.89
CH
=3=CH 1.79
C
=3=C- 2.46
= = C
=C= 1.03
- 34 -
COOH
-COOH 10.72
) (anhydride OC O CO
-CO-O-OC- (anh.) 7.95
O CO
-CO-O- 5.32
) (oxalate O CO OC O
-O-OC-CO-O- (oxalate) 6.25
CO
-CO- 5.36
O
-O- 1.56
) (aromatic O
-O- (aromatic) 2.68
OH
-OH 5.63
) (aromatic OH
-OH (aromatic) 9.65
CHO
-CHO 5.49
N C
-CN 8.49
) (aromatic N C
-CN (aromatic) 9.38
2
NH
-NH2 4.56
) (
2
aromatic NH
-NH2 (aromatic) 9.20
NH
-NH- 3.04
) (aromatic NH
-NH- (aromatic) 7.64
) (aromatic NH >
>N- 0.89
) (aromatic N >
>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
) (aromatic F
-F (aromatic) 0.45
) ( perfluoro F
-F (perfluoro) 0.54
Cl
-Cl 4.20
) ( ted disubstitu Cl
-Cl (disubsituted) 3.71
) ( uted trisubstit Cl
-Cl (trisubsituted) 3.17
Br
-Br 5.58
I
-I 8.04
) (aromatic I
-I (aromatic) 10.77
ring membered Three
3-membered ring 0.45
ring membered Five
ring membered Six
ring in Heteroatom
Heteroatom in ring 0.45
) (

c nonaromati bound double
a in carbon on on Substituti

Subst. on C in a DB nonar. 0.58
ring benzene a in itution Orthosubst
o-Subst. in a benzene ring 1.16
bound double per n Conjugatio ,
Conjugat. per double bond 0.13
> CH of pairs adjacent CH * *
CH ** adjacent pairs of >CH- 0.76

- 35 -
1.2.4c The Method by Joback
The method by Joback has been developed for estimating the critical temperature T
c
,
the critical pressure P
c
, the critical volume, and the normal boiling temperature T
b
. The
method for estimating the critical volume is not implemented in PE. The formula used
in PE are:

+ =
b b
T K T 198 /

( )
2
965 , 0 584 , 0
/
/
c c
b
c
T T
K T
K T
+
=

( )
2
0032 , 0 113 , 0
1
/
+
=
c A
c
P n
bar P ,

where n
A
is the total number of atoms in the molecule.

Table 1.4: group contributions according to Joback

Group Implementation in
PE
b
T
c
T
c
P
3
CH
-CH3 23.58 0.0141 -0.0012

2
CH
-CH2- 22.88 0.0189 0
> CH
>CH- 21.74 0.0164 0.0020
< > C
>C< 18.25 0.0067 0.0043
2
CH =
=CH2 18.18 0.0113 -0.0028
= CH
=CH- 24.96 0.0129 -0.0006
= > C
>C= 24.14 0.0117 0.0011
= = C
=C= 26.15 0.0026 0.0028
CH
=3=CH 9.20 0.0027 -0.0008
C
=3=C- 27.38 0.0020 0.0016
) (
2
ring CH
-CH2-(ring) 27.15 0.0100 0.0025
) (ring CH >
>CH-(ring) 21.78 0.0122 0.0004
) (ring C < >
>C<(ring) 21.32 0.0042 0.0061
) (ring CH =
=CH-(ring) 26.73 0.0082 0.0011
) (ring C < =
=C<(ring) 31.01 0.0143 0.0008
F
-F -0.03 0.0111 -0.0057
Cl
-Cl 38.13 0.0105 -0.0049
Br
-Br 66.86 0.0133 0.0057
I
-I 93.84 0.0068 -0.0034
) (alcohol OH
-OH (alcohol) 92.88 0.0741 0.0112
) ( phenol OH
-OH (phenol) 76.34 0.0240 0.0184
) (nonring O
-O- (nonring) 22.42 0.0168 0.0015
- 36 -
) (ring O
-O- (ring) 31.22 0.0098 0.0048
) (nonring O C = >
>C=O (nonring) 76.75 0.0380 0.0031
) (ring O C = >
>C=O (ring) 94.97 0.0284 0.0028
) (aldehyde CH O =
O=CH- (aldehyde) 72.24 0.0379 0.0030
) (acid COOH
-COOH (acid) 169.09 0.0791 0.0077
) (ester COO
-COO- (ester) 81.10 0.0481 0.0005
) ( above as except O =
=O (exept as above) -10.50 0.0143 0.0101
2
NH
-NH2 73.23 0.0243 0.0109
) (nonring NH >
>NH (nonring) 50.17 0.0295 0.0077
) (ring NH >
>NH (ring) 52.82 0.0130 0.0114
) (nonring N >
>N- (nonring) 11.74 0.0169 0.0074
) (nonring N =
-N= (nonring) 74.60 0.0255 -0.0099
) (ring N =
-N= (ring) 57.55 0.0085 0.0076
CN
-CN 125.66 0.0496 -0.0101
2
NO
-NO2 152.54 0.0437 0.0064
SH
-SH 63.56 0.0031 0.0084
) (nonring S
-S- (nonring) 68.78 0.0119 0.0049
) (ring S
-S- (ring) 52.10 0.0019 0.0051

1.2.4d The Method by Klincewicz
A simple relation derived by Klincewicz can also be used for estimating the critical
temperature. This relation requires the normal boiling temperature and the molecular
weight only:

K T mol g M K T
b w c
/ 41 , 1 ) / /( 16 , 0 2 , 50 / + =

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.
- 37 -
1.2.4e Calculation of the Acentric Factor

The definition for the acentric factor is:

1 ) 7 , 0 ( lg = =
r
sat
r
T P ,

where
r
T is the reduced temperature
c
T T / .
sat
r
P is the reduced vapour pressure
c
sat
P P / .

The calculation method for the acentric factor implemented in PE uses the Lee-Kesler
vapour pressure relation (Reid et al., 1987):

6
6
43577 , 0 ln 4721 , 13
6875 , 15
2518 , 15
169347 , 0 ln 28862 , 1
09648 , 6
92714 , 5 / ln

+ =
+ + = atm P
c
,

where
c
b
T
T
= .

- 38 -
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).

Figure 1.2m: Selecting FILE/DATA BASE.

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.

- 39 -
If the normal boiling temperature is known from experiment, it is strongly
recommended that this value is entered in the appropriate edit box, because the
subsequent estimate of the critical temperature will be more precise when using the
methods according to Joback or Klincewicz, hereafter. If the normal boiling
temperature is not known, it can be estimated with the method of Joback.
Depending on the property which should be estimated, the standard dialog box with
different radio buttons for the different estimation methods will show those methods
disabled, that can not be used (Figure 1.2o).

Figure 1.2o: Choosing a method in order
to estimate T
c
.

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 (
3
CH ), one
2
CH
group, one CH , and one C group.

Using the GROUP SELECTOR BOX
1) Selecting a group in the right list box, the user is asked to enter the amount of
groups that should be used for the estimation. Afterwards, this group is shown in
the left list box together with the amount chosen for this group.
2) If a group should be removed from the left list of groups to be used for the
estimation, the user has to click on the selected group in the right list box again and
enter 0 for the amount of groups. Hereafter, the group is automatically deselected
in the right list box and removed from the left list box.

- 40 -

Figure 1.2p:

Group selector box for
group contribution
methods.

1.2.4g Calculation of the Acentric Factor
The Lee-Kesler method for estimating the acentric factor requires knowledge of the
normal boiling temperature, the critical temperature, and the critical pressure. The
calculation of the acentric factor is performed by pressing the CALCULATE button
(Figure 1.1n). PE will display an additional dialog box (Figure 1.1q) allowing to
change the input parameters before they are used for calculation. In this dialog box, the
user can change these parameters in order to calculate with other parameters than those
in the database dialog box (Figure 1.1n). When pressing OK, the calculated value for
the acentric factor will be placed in the database dialog box (Figure 1.1n).
If the check box UPDATE PARAMETERS was checked (Figure 1.1q), the parameters T
b
,
T
c
, and P
c
in the database dialog box (Figure 1.1n) are additionally replaced by the
ones used to calculate .

Figure 1.2q: Dialog box for
parameter input when estimating
the acentric factor.

Chapter 2: Pure-Component Calculations
- 41 -
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).

Figure 2a: Menu entries for PURE-COMPONENT subroutines.

The entries allow:
1) to DETERMINE EOS PARAMETERS, that reproduce a vapour pressure curve best and
to PLOT diagrams giving evidence about the suitabilities of EOS and parameters to
model certain compounds (Section 2.1).
2) to calculate complete VAPOUR PRESSURE CURVES and to PLOT calculated and
experimentally determined vapour pressure curves (Section 2.2),
3) to CALCULATE PVT DATA and to PLOT the calculated and experimentally determined
PvT data in P-diagrams (Section 2.3),
4) to CALCULATE DEVIATIONS between calculated and experimentally determined
properties of the vapour pressure curve (Section 2.4).
5) to append EOS parameters to the file containing the experimental data (Section
1.14)

2.1 Determination of Pure-Component EOS Parameters
The calculation of pure-component properties and mixture properties with EOS
requires pure-component EOS parameters to describe the pure compounds. There are
several methods to obtain these parameters:
1) EOS parameters can be determined from the critical data of the pure component. For cubic
EOS it is common practice to choose two parameters in such a way that the calculated
- 42 -
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) T
c
and P
c
, 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).

The menu entry PURE COMPONENT/DETERMINE PARAMETERS allows to determine
EOS parameters according to method 1 and 2. Selecting this menu entry, the user will
be asked, if calculations with the EOS parameters to be determined should match the
critical temperature and critical pressure determined experimentally (Figure 2.1a).

Figure 2.1a: Dialog box to choose if EOS parameters should match T
c
and P
c
.
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).
- 43 -
Enforcing EOS parameters that exactly reproduce the experimental values of T
c
and P
c

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 T
c
and P
c
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 T
c

and P
c
is enforced and the first two pure-component EOS parameters of the selected
EOS are T
c
and P
c
, the input of both is disabled (Figure 2.1c). If the reproduction of T
c

and P
c
is enforced and the first two pure-component EOS parameters of the selected
EOS are not T
c
and P
c
, the input of both is enabled for the input of initial guesses - the
procedure for this case is described by Pfohl et al., 1998.

Figure 2.1b: Dialog box for an optimisation of pure-component EOS parameters.
- 44 -

Figure 2.1c: Dialog box for an optimisation of pure-component EOS parameters with
an EOS where T
c
and P
c
are the first two parameters and where the correct
reproduction of T
c
and P
c
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.
- 45 -
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.

- 46 -
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.

2.1.1 Visualisation of Grids/Optimisations
The results of pure-component parameter determinations can be visualised, if there was
a GRID on one parameter - or if T
c
and P
c
have been enforced during the determination
by selecting PURE COMPONENT/DETERMINE PARAMETERS/PLOT from the menu. These
deviation diagrams allow to judge about the influence of a certain parameter on the
quality of the reproduction of the properties on the vapour pressure curve (compare
Pfohl et al., 1998).
The dialog box shown in Figure 2.1e allows to set the limits of the axis in the diagram
and allows to select the range of points to be shown in the diagram. Figures 2.1f-2.1j
show examples of such deviation diagrams.

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 T
c
and P
c
. The diagrams are
similar because the constraint to enforce T
c
and P
c
is not severe, here. It can be seen
that the acentric factor has a pronounced influence on the calculation of the vapour
- 47 -
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 T
c
and P
c
. The diagrams look very different,
because the constraint to enforce T
c
and P
c
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 CO
2
described by the Peng-Robinson EOS,
when the correct reproduction of experimentally determined T
c
and P
c
is enforced (left
side) or not (right side). Vapour pressure deviation: - - - , Density deviation: -----.

Figure 2.1h: Deviation analysis for CO
2
described by the PR EOS with volume
translation by Peneloux, when the correct reproduction of experimentally determined
T
c
and P
c
is enforced. Vapour pressure deviation: - - - , Density deviation: .

- 48 -

Figure 2.1i and 2.1j: Deviation analysis for CO
2
described by SAFT, when the correct
reproduction of experimentally determined T
c
and P
c
is enforced (right side) or not (left
side). Vapour pressure deviation: - - - , Density deviation: .

2.2 Calculation of Vapour Pressure Curves
A complete vapour pressure curve, starting from a MINIMUM TEMPERATURE (to be
specified) and ending at the critical point, can be calculated by selecting the menu bar
entry PURE COMPONENT/VAPOUR PRESSURE CURVE (Figure 2.2a). The settings for the
MINIMUM TEMPERATURE must not be too low, otherwise calculations might not
converge. The dialog box items (Figure 2.2b) are practically identical to the ones from
the dialog boxes described above and therefore not described here.

Figure 2.2a: Selecting to CALCULATE A VAPOUR PRESSURE CURVE.
- 49 -

Figure 2.2b: Dialog box for the calculation of a vapour pressure curve.

2.2.1 Graphical Output of Vapour Pressure Curves
The last vapour pressure curve which has been calculated according to the description
in the above section can be visualised by selecting the menu item PURE COMPONENT /
VAPOUR PRESSURE CURVE / PLOT. The vapour pressure curve can be either displayed
with linear axis or as log(P
SAT
) against 1/T (Figure 2.2c - 2.2d).
- 50 -

Figure 2.2c: Vapour pressure curve of carbon dioxide with liner axis.

Figure 2.2d: Vapour pressure curve of carbon dioxide with logarithmic axis

- 51 -
2.3 Calculation of P -Diagrams
A complete P-diagram can be calculated by selecting the menu bar entry PURE
COMPONENT / PVT DIAGRAM (Figure 2.3a). The limits for the -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 2.3a: Selecting to calculate a P-diagram.

Figure 2.3b: Specifying limits for the -axis in the P-diagram and selecting
additional isotherms to be calculated.

- 52 -
2.3.1 Graphical Output of P -Diagrams
The last P-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 -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 P-diagram for carbon dioxide is shown in Figure 2.3d.

Figure 2.3c: Input of limits for the P-axis of the P-diagram.

Figure 2.3d: P-diagram for carbon dioxide.
- 53 -
2.4 Calculation of Deviations
In order to judge about the quality of given pure-component EOS parameter sets or
find good initial guesses for pure-component parameter optimisations, it is possible to
calculate the deviation between the experimental vapour pressure curve data in a
PCFILE and calculated properties using an EOS by selecting PURE COMPONENT /
CALCULATE DEVIATIONS from the main menu (Figure 2.4a).

Figure 2.4a: Selecting CALCULATE DEVIATIONS from the PURE-COMPONENT menu.

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.
Chapter 3: Mixtures
- 54 -
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.
Chapter 3: Mixtures
- 55 -
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.

Figure 3c: Selecting an EOS for mixture calculations.

Chapter 3: Mixtures
- 56 -

Figure 3d: Selecting a mixing rule for mixture calculations.

Figure 3e: Selecting an data block of the EXFILE for the next calculations

3.1 Mixture Calculations
Mixture calculations using PE are phase equilibrium or density calculations. The
calculation of densities is described in section 3.1.4. The phase equilibrium
calculations are described in sections 3.1.1 - 3.1.3. The phase equilibrium calculations
are carried out for either of the following reasons:
1) compare the calculation results with experimental data from the EXFILE,
2) calculate at conditions not investigated experimentally yet, using the phase
equilibria supplied in EXFILE as starting values / initial guesses for the calculations.

Binary Interaction Parameters
First, the binary interaction parameters have to be keyed in for the next calculations by
selecting MIXTURE / SET PARAMETERS (Figures 3a, 3.1a, and 3.1b). If interaction
parameters are stored in the EXFILE for the selected EOS, mixing rule, and block
(compare section 1.2.1), these parameters can be used as defaults, otherwise only the
values from before.

Chapter 3: Mixtures
- 57 -

Figure 3.1a: Input of interaction parameters for binary and multi component systems.

Figure 3.1b: Input of interaction parameters for a ternary system.

Type of deviation calculated
After the interaction parameters have been specified and in case of calculations for the
above type 1, the type of deviation between calculated and experimentally determined
data has to be specified by selecting MIXTURE/OBJECTIVE FUNCTION (Figure 3a). The
deviation calculated by PE is based on the mole fractions of the coexisting phases at
the temperature and pressure of the data points in the EXFILE.
The dialog box PHASES (Figure 3.1c) enables to select the coexisting phases where the
deviations should be calculated and averaged. In general, all phases are of interest, but
sometimes only the composition of one of the phases has been determined experimen-
Chapter 3: Mixtures
- 58 -
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
i
= mole fraction of component i:

( ) absolute
n
i i
calc
i
n
=
=
2
1 2
1

exp
relative
n
i i
calc
i
i
n
=

=
2
1
2
1

exp
exp

absolute
n
i i
calc
i
n
=
=
1
1

exp
relative
n
i i
calc
i
i
n
=

=
1
1

exp
exp

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.

Figure 3.1c: Selecting the type of deviation to be calculated.

Figure 3.1d: Calculated difference between experimental and calculated results.

Chapter 3: Mixtures
- 59 -
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.

3.1.1 Binary Phase Equilibrium Calculations
Starting binary calculations, the dialog box shown in Figure 3.1e will prompt the user
for input. The entries are explained below.

Figure 3.1e: Starting binary calculations.

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.

Chapter 3: Mixtures
- 60 -
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.

3.1.2 Ternary Phase Equilibrium Calculations
Starting ternary calculations, the dialog box shown in Figure 3.1f will prompt the user
for input. The entries are explained below.

Figure 3.1f: Starting ternary calculations.
Chapter 3: Mixtures
- 61 -
OUTPUT FILE, DEBUG INFO, ADDITIONAL POINTS
These three entries have the same meaning as explained for binary systems, above.

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.

FIRST STEP / LENGTH
Similar to the binary system, the user has to tell PE the size of the step from the first to
the second tie line. The value is the ratio of the STEP from the middle of the first tie
line to the middle of the second tie line divided by the LENGTH of the first tie line
itself. In general, values between 1% and 5% work best. If convergence problems
arise, this value should be decreased.

Three Phase Calculations
In order to obtain best calculation results for ADDITIONAL POINTS, the first equilibrium
in an EXFILE block should be a three phase region if any was determined experimen-
tally and calculation converge there. If no three phase region was detected experimen-
tally, but the user knows that there is a three phase region, an INITIAL GUESS for the
three phase region should be added to the block in the EXFILE as first point, in order to
obtain nice looking diagrams (see section 1.2).
Chapter 3: Mixtures
- 62 -
3.1.3 Calculating Phase Equilibria
The status of the last phase equilibrium calculation is shown in the dialog box
CALCULATION STATUS shown in Figure 3.1g. The entries are explained below.

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 (Bnz 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.

Figure 3.1g: Status of Calculations

Chapter 3: Mixtures
- 63 -
3.1.4 Density Calculations
Selecting MIXTURE / CALCULATE DENSITY from the main menu (Figure 3.1h) allows
for the calculation of mixture densities for a given temperature, pressure, and
composition, i.e. mole fractions (Figure 3.1i). Some calculation results are displayed in
Figure 3.1j.

Figure 3.1h: choosing to calculate mixture densities.

Figure 3.1i (left side): input of mixture properties for the calculation of densities.
Figure 3.1j (right side): output of the calculated density.
Chapter 3: Mixtures
- 64 -
3.2 Optimisation of Binary Interaction Parameters
The optimum representation of phase equilibria in mixtures with an appropriate set of
EOS, mixing rule, and pure-component parameters also depends on the correct choice
of mixture parameters. PE uses so-called binary interaction parameters as a measure of
mixture parameters, as it is common practice in chemical engineering thermodynamics
(compare appendix A1 and A2).
Theory enforces the adjustment of the pressure-independent binary interaction
parameters for an optimum representation of the binary phase equilibrium data, only.
Calculations in mixtures with more components should be performed with the so-
derived parameters, guaranteeing self-consistent data, and making these calculations
predictive. However, it is common practice to adjust the binary parameters to mixtures
with more than two components for several reasons. One reason might be that the
predictions for the ternary system are not good enough, if they are based on the
parameters derived from the binary systems. Another reason might be that no (or not
enough) binary information is available to derive the parameters based on these.
Therefore, PE allows the optimisation of binary interaction parameters based on binary
and ternary phase equilibrium data, although it is recommended to use binary
information, only.
However, in cases where no binary experimental phase equilibrium data can be
obtained for one binary system at the conditions where the ternary system exhibits
miscibility gaps, adjusting the parameters for this system to ternary information might
be the only way to obtain a good representation of the ternary phase behaviour at all.
Adding carbon dioxide to the homogeneous system 2-propanol + water leads to
miscibility gaps at 300 K and 10 MPa and serves as an example, here. The ternary
miscibility gaps can not be predicted accurately enough with interaction parameters
from the binary systems with many cubic EOS, if the system 2-propanol + water at the
same temperature at low pressure is used to regress the parameters of this system.
Using parameters for this binary system that are optimised to represent the ternary
system, calculations can come close to the experimentally determined equilibria
(compare Adrian, 1997).
Using PE, optimisations of interaction parameters can be done according to one of two
different ways. Using a Simplex-Nelder-Mead algorithm in order to obtain the
optimum interaction parameters is the standard method. However, the Simplex-Nelder-
Mead algorithm requires initial guesses for the interaction parameters and will not find
the way from one local optimum to another optimum. Therefore a second method - the
so-called grid - enables to find initial guesses and different minima on the expense of
increased time consumption. The application of both methods is explained in section
3.2.1 and 3.2.2.
Chapter 3: Mixtures
- 65 -
3.2.1 Optimising Parameters (Simplex-Nelder-Mead Method)
Selecting MIXTURE / OPTIMIZE from the main menu enables the optimisation of binary
interaction parameters for the selected system, EXFILE block, EOS, and mixing rule,
using a Simplex-Nelder-Mead algorithm (Nelder and Mead, 1965). The user is
prompted for the input of the initial guesses of the parameters and for any binary
parameters to be held constant during optimisations (Figure 3.2a). By checking
OPTIMIZE in the dialog box, the user chooses to optimise the appropriate parameter
with the given value as an initial guess. By unchecking OPTIMIZE in the dialog box, the
user chooses to hold the value of this parameter constant during the whole
optimisation. The results of the last calculation are stored in the specified OUTPUT FILE.
The optimisation is stopped when the given TOLERANCE is reached. If VISUALIZATION
DURING OPTIMIZATION is checked, a graphic window is shown during the
optimisation. A trace of the optimisation is stored in the file PE/PAROPT.OUT. If the
optimisation is successful the optimised parameters can be stored to the EXFILE by
selecting MIXTURE/SAVE PARAMETERS (Figure 3a and 3.2b and section 1.2).

Figure 3.2a: Input of interaction parameters for optimisation.

Figure 3.2b: Saving interaction parameters to the EXFILE.
Chapter 3: Mixtures
- 66 -
3.2.2 Scanning Parameters (Grid)
Selecting MIXTURE/GRID from the main menu enables finding good sets of binary
interaction parameters for the selected system, EXFILE BLOCK, EOS, and mixing rule by
calculating deviations between experimental points and calculated points with different
binary interaction parameters on a rectangular grid, automatically. For a ternary system
the binary interaction parameters from one binary subsystem can be varied on a GRID
(Figure 3.2c) while holding all other parameters constant. The dialog box shown in
Figure 3.2d prompts for three inputs per binary parameter: the lower and upper bound
of the grid interval and the step between two different calculations.
In general, this method requires a lot of computing time. Using a step width of 0,01 for
k
ij
and
ij
and the limits shown in Figure 3.2d enforces ( |-0,2 - 0,5| / 0,01 + 1 ) ( |-
0,3 - 0,4| / 0,01 + 1) = 5041 calculations:

k
ij

ij

-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.

Chapter 3: Mixtures
- 67 -

Figure 3.2d: Input of binary interaction parameters for calculations on a GRID

ENABLE TIME LIMIT
Because many parameter sets will be tested that will not lead to convergence of the
flash calculations, it is possible to enable a TIME LIMIT for each calculation of a block
in the EXFILE. If convergence is not achieved within this time for all equilibria of the
block, the calculations with the current set of parameters is interrupted and the
calculated deviation between experimental and calculated points is set to arbitrary high
values around 1000%. The required time is depending on the number of experimental
points in the EXFILE BLOCK, the complexity of the EOS (especially weather explicitly
accounting for association or not), the number of components, and the performance of
the PC.
If the purpose of the GRID is to find starting values that allow convergence at all points
for an optimisation according to section 3.2.1, it can be advisable to mark only the
point at which convergence is most difficult with flag=1 in the EXFILE (section 1.2) in
order to speed up the GRID significantly.
The parameter sets and results with these parameters are stored in the file GRID.OUT.

Chapter 3: Mixtures
- 68 -
3.3 Graphical Output of Mixture Equilibria
The calculation results for mixtures are stored in the files PE_1..9.OUT (compare
section 3.1). The calculation results can be displayed in form of different diagrams
together with the data from the EXFILE, which are not marked with flag=0 (section 1.2).
Depending on the number of components in the system of interest, which is displayed
in the menu bar (section 3.1), different graphs are possible. The different kinds of
graphical routines are described in sections 3.3.1 - 3.3.3.

3.3.1 Pxy- / yP-Diagrams (Binary)
Selecting MIXTURE / PLOT from the main menu will display the dialog box shown in
Figure 3.3a if the two-component mode is active and prompt for input of the plot
parameters that are described below.

Figure 3.3a: Input of plot parameters for binary systems.

Chapter 3: Mixtures
- 69 -
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.

Chapter 3: Mixtures
- 70 -

Figure 3.3b: Pxy-diagram without enlargement

Figure 3.3c: Pxy-diagram with enlargement at 0-0.7 and 0.9-1

Figure 3.3d: yP-diagram (here: with logarithmic axis)
Chapter 3: Mixtures
- 71 -
3.3.2 Gibbs Triangles (Ternary and Quaternary)
Selecting MIXTURE / PLOT from the main menu will display the dialog box shown in
Figure 3.3e, if a ternary or quaternary system is selected in the menu bar. This box
prompts for input of the plot parameters, which are identical to the ones described in
section 3.3.1 for the binary systems.

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.

Figure 3.3e: Input of plot parameters for a ternary or quaternary system.

Chapter 3: Mixtures
- 72 -
3.4 Solid-Gas Equilibria
Using PE, it is possible to calculate solid-gas equilibria in binary systems. For these
calculations it is necessary that the density of the solid to be dissolved in the gas is
given in the pure-component data block of the EXFILE (compare Figure 1.2a / Section
1.2.1). The solid component has to be component 2 in the EXFILE. If a suitable value
for s.dns of component 2 is stored in the pure-component data block of the EXFILE,
the check box SOLID in the dialog box for binary calculations (Figure 3.4a) will be
enabled.

Figure 3.4a: Binary calculations for solid-gas equilibria

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:

S V
f f
2 2
= , i.e.
( )

=
RT
Mw P P
P P y
S
sat
sat sat S
2
2 2
2 2 2 2
exp

Where: f = fugacity
= fugacity coefficient
y = mole fraction in gas phase
P = system pressure and P
sat
= saturation pressure
T = system temperature
R = universal gas constant
Mw = molecular weight

S
= solid density (S.DNS from EXFILE)
2 = component 2 = solid compound
V = vapour phase
S = solid phase (pure compound 2)
sat = state of saturation
Chapter 4: Implementation of New EOS by Users
- 73 -
4 Implementation of New EOS by Users

4.1 Introduction

PE 2000 has been designed in such a way that for each equation of state (EOS) only
one subroutine in one single FORTRAN file is necessary. This modular structure
allows to implement new EOS very easily without the necessity to know anything
about flash, isofugacity equations, vapor pressure calculations and so on.

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.

- 74 -
4.2 Files Used for Implementing New EOS in PE
Users willing to implement new EOS in PE are encouraged to do so and will receive
help by the authors of this book in addition to what is written here.
When installing the program PE, a directory PE/FORTRAN will be created in addition
to the program PE. This directory contains all FORTRAN files necessary for
implementing a new EOS in PE. But, only two of these files (pes_EOS_by_User.FOR
and pes_RW_EOS_save.FOR) have to be modified when programming a new EOS.

1) File containing the EOS
pes_EOS_by_User.FOR

2) Files necessary for testing the EOS without connection to PE.EXE
pes_EOS_by_User.FOR see above
EOS_TEST.FOR main program
EOS_P_TEST.FOR subroutine for testing P(T,rho) calculation
EOS_PHI_TEST.FOR subroutine for testing (T,P) calculation
EOS_TEST_epk interface for subroutine pedens do not change !
pes_dens_1.FOR interface for pedens2.FOR ignore all historic lines for the
Peng-Robinson-EOS, here. These lines are not used ! Do not change !
pes_dens_2.FOR subroutine iteratively solving (T,P) do not change !
pes_RW_EOS_save.FOR subroutines handling the save-parameters. These
subroutines could be dummy subroutines for testing, here.

3) Files necessary for building EOS_on_DISK.EXE (testing with connection to
PE.EXE)
pes_EOS_by_User.FOR see above
pes_dens_1.FOR see above and do not change !
pes_dens_2.FOR see above and do not change !
EOS_on_DISK.FOR main program called by PE.EXE do not change !
pes_RW_EOS_save.FOR subroutines handling the save-parameters. These
subroutines have to be adjusted by the user depending on the EOS, here.
pes_RW_EOS_para.FOR subroutines handling the parameter list of the
User_EOS, i.e. the file transfer between PE.EXE and EOS_on_DISK.EXE -
Do not change !
EOS_DISK_pepres.FOR interface for pedens do not change !

4) files necessary for running EOS_on_DISK.EXE
EOS_on_DISK.EXE program with User EOS and I/O subroutines
EOS_on_DISK.in optional file with names and units of parameters for User EOS
EOS_on_DISK.sav will be created by EOS_on_DISK.EXE, contains save-
variables
EOS_on_DISK.par will be created by PEINT.EXE and EOS_on_DISK.EXE,
contains all parameters of the subroutine User_EOS with the User EOS.
- 75 -
4.3 The File pes_EOS_?.FOR

The EOS standard subroutines used by PE are in files named pes_EOS_?.FOR where
? stands for the name of the EOS being in this file. The subroutine in this file
contains 3 different parts, which are used, depending on the value of the variable
calc_what in the parameter list (see section 4.3.1 4.3.3).
A demo file pes_EOS_by_User.FOR which is in the PE/FORTRAN directory contains
the simple Peng-Robinson EOS. The file is shown in Figure 4.3a.

!==================================================================
! 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)
!==================================================================
subroutine User_EOS ( calc_what, nsteu, mixrule, nco,
& nmax, NAv, Tau, Pi, R, T, rho, PuCoPa, sts,
& k, l, la, kep, kkap,
& pp, dp, iphase, iphaseerr, mode,
& xi, rhol, phil, errliq,
& yi, rhog, phig, errvap, fk, called_by_EOS_on_DISK)
implicit none
! parameters of subroutine EOS_from_DISK - DO NOT CHANGE !!
!----------------------------------------------------------
logical called_by_EOS_on_DISK
integer calc_what, nsteu, mixrule, nco, nmax, mode,
& iphase, iphaseerr, errliq, errvap,
& sts(nmax,0:3)
double precision r, t, Nav, Tau, Pi, rho, PuCoPa(7,*),
& k(nmax,*),l(nmax,*),la(nmax,*),kep(nmax,*),kkap(nmax,*),
& pp, dp, xi(*), yi(*), rhol, rhog, phil(*), phig(*), fk(*)
! parameters of Subroutine PengRobinson
! (CHANGE ACCORDING TO YOUR EOS)
!-----------------------------------------------------------
double precision ai(100,100), bi(100,100), ci(100,100),
& ax, ay, bx, by, cx, cy, tc(100), pc(100), omega(100)
! keep in mind the "global" variables for Peng-Robinson
! after exiting the subroutine. Remember for next call
!------------------------------------------------------
save tc, pc, omega, ai,bi,ci, ax,ay,bx,by,cx,cy
- 76 -
! temporary "local" variables
!----------------------------
integer i, ierr
double precision ac(nmax),tr(nmax),xo,xt,
& thet, dthet, am, bm, cm, rbm, rt,
& pideal, zett, xa(nmax),
& p, rhomx, pold, prho, dprho, prhol, prhog,
& sq2, rgp, rgm, rlp, rlm, rll, rlg, rt2sq,
& arax, aray, arx, ary, arbx, arby, thetx, thety,
& suphiax, suphiay, suphibx, suphiby,
& dadx(nmax), dady(nmax), dbdx(nmax), dbdy(nmax),
& dcdx(nmax), dcdy(nmax), philogl(nmax), philogg(nmax)
! read all save parameters from the file EOS_SAVE.DAT if
! EOS_on_DISK.EXE calls the subroutine (then save does not work)
!----------------------------------------------------------
if (called_by_EOS_on_DISK)
& call read_eos_save(nco,tc,pc,omega,ai,bi,ci,ax,ay,bx,by,cx,cy)
!==========================================================
! 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)
- 77 -
!==========================================================
! 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)
!
!==========================================================
rt = r * t
if (iphaseerr.eq.1) then
if (iphase.eq.1) then
iphase = 0
else
iphase = 1
endif
endif
! GAS PHASE
!----------
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
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))
! pressure from ideal gas law
pideal=rho*rt
! pressure with Peng-Robinson
pp=pideal*(1.0d0+rho*thet)
! dp = d_P / d_rho (used for Newton method)
dp=rt*(1.0d0+rho*(2.0d0*thet+rho*dthet))
endif ! CALC PRESSURE (calc_what=1)
- 78 -
!==========================================================
! 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
!
!==========================================================
p = pp
rt = r * t
! determine mixture parameters
!-----------------------------
call si_mix_abc ( nsteu, mixrule, nco,nmax, R, T,
& ai, bi, ci, k, l, la, xi, yi,
& ax, ay, dadx, dady, bx, by, dbdx, dbdy, cx, cy, dcdx, dcdy )
! write all save parameters to the file EOS_SAVE.DAT if
!-----------------------------------------------------------------
& call write_eos_save(nco,tc,pc,omega,ai,bi,ci,ax,ay,bx,by,cx,cy)
if(p.lt.0.0) return
! determine liquid phase density
!-------------------------------
iphase=1
rhomx=1.d0/bx ! max. density (1/covolume) so that p -> infinity
pold=p
call pedens(rhomx,pold,rho,prho,dprho,ierr,
& pi,r,t,nsteu,iphase,mode,ax,ay,bx,by,
& iphaseerr, mixrule, nco,nmax, nav, tau,
& PuCoPa, sts, k, l, la, kep, kkap,
& xi, yi, rhol, rhog, phil, phig, errliq, errvap)
rhol=rho
prhol=prho
errliq=ierr
! determine vapour phase density
!-------------------------------
iphase=0
rhomx=1.d0/by ! max. density (1/covolume) so that p -> infinity
pold=p
call pedens(rhomx,pold,rho,prho,dprho,ierr,
& pi,r,t,nsteu,iphase,mode,ax,ay,bx,by,
& iphaseerr, mixrule, nco,nmax, nav, tau,
& PuCoPa, sts, k, l, la, kep, kkap,
& xi, yi, rhol, rhog, phil, phig, errliq, errvap)
rhog=rho
prhog=prho
errvap=ierr
! abbreviations
!--------------
sq2=dsqrt(2.d0)
rgp=by*rhog*(1.d0+sq2)+1.d0
rgm=by*rhog*(1.d0-sq2)+1.d0
rlp=bx*rhol*(1.d0+sq2)+1.d0
rlm=bx*rhol*(1.d0-sq2)+1.d0
rll=dlog(rlp/rlm)
rlg=dlog(rgp/rgm)
rt2sq=rt*2.d0*sq2
! d(ar)/d(a)
!-----------
arax=-1.d0/(bx*rt2sq)*rll
aray=-1.d0/(by*rt2sq)*rlg
- 79 -
! 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)
! write all save parameters to the file EOS_SAVE.DAT if
!-----------------------------------------------------------------
& call write_eos_save(nco,tc,pc,omega,ai,bi,ci,ax,ay,bx,by,cx,cy)
end
subroutine si_mix_abc ( nsteu, mixrule, nco,nmax, R, T,
& ai, bi, ci, k, l, la, xi, yi,
& ax, ay, dadx, dady, bx, by, dbdx, dbdy, cx, cy, dcdx, dcdy )
!============================================================
! subroutine of program pe (calculates phase equilibria)
! calculates the mixture parameters a,b,c for most cubic EOS
!
! nco = number of components
! R = universal gas constant
! T = temperatue [K]
! ai, bi, ci = pure-component parameters
! k, l, la = binary interaction parameters
! ax, ay, bx, by (c) = a and b for liquid and gas phase
! dadx, dady, dbdx, dbdy (c) = derivatives of a and b for mole fr
!
!============================================================
implicit none
- 80 -
! 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
! avoid compiler warnings
!(these variables are not used in this mini-version)
!---------------------------------------------------
if ((nsteu.eq.-1).or.(mixrule.eq.-1).or.(R .eq.-1) .or.
& (T .eq.-1).or.(ci(1,1).eq.-1).or.(la(1,1).eq.-1)) continue
!-----------------------------------------------------
! 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
- 81 -
4.3.1 Initialization (calc_what=0)

PE calls the EOS subroutine using the pure-component parameters PuCoPa
(1:7,1:100) containing up to 7 different pure-component parameters (1:7) for up to 100
compounds in a mixture (1:100). Doing the initialization, these parameters are copied
to local variables (named T
c
, P
c
, omega or a, b, c for example) which are stored within
the subroutine using the FORTRAN save-command.
Further, all EOS parameters (or parts of the EOS) which are not depending on
composition, density and pressure should be saved in save-variables. These save-
variables (which may only depend on pure-component properties and temperature
according to the above definition) will be kept constant during (isothermal) flash and
density calculations, speeding up the calculations enormously for most EOS, because
there is no necessity to recalculate the variables again and again in each iteration.

4.3.2 Calculate Pressure (calc_what=1)

Most EOS are written in a pressure-explicit form P=P(T,v,z), where P is pressure, T is
temperature, v is the molar volume and z the molar composition of a phase. For
calc_what=1, this calculation is performed as well as the calculation of (P/)
T,z

using the parameters from the save-paragraph and the information which phase is
looked at (iphase=0 means gas phase, i.e. P=P(T,v
G
,y). iphase=1 means liquid phase,
i.e. P=P(T,v
L
,x)).
Because the formula for the residual Helmholtz a
r
energy is needed for the calculation
of fugacity coefficients later anyway, the calculation of P(T,v,z) and (P/)
T,z
in PE is
generally done using the abbreviation (Topliss, 1985). But: this way of calculation is
not mandatory.

Definition of

1
] , , [

=
Z
z T
with
RT
P
Z
=
i.e.
=
=
= =
v
r
r
d z T
RT
z v T a
z v T a
/ 1
0
] , , [
] , , [
] , , [
~

Calculation of P, using

RT z T P
ideal
= ] , , [

]) , , [ * 1 ( * ] , , [ ] , , [ z T z T P z T P
ideal
+ =
- 82 -
Calculation of (dP/d )
T
, using and (d /d )
T

+ + =
z T z T
d
d
RT
d
dP
, ,
* * 2 * 1 *

4.3.3 Calculate Fugacity Coefficients (calc_what=2)

The isofugacity equation for the determination of equilibria enforces the knowledge of
fugacity coefficients
i
given by

P z T z f
Ph Ph Ph
i
Ph
i
Ph
i
* ] , , [ * =

Here: f
i
Ph
= fugacity of component i in phase Ph
z
i
Ph
= mole fraction of component i in phase Ph

i
Ph
= fugacity coefficient of component i in phase Ph

Ph
= density of phase Ph

According to the parameterization used by Topliss (1985), the fugacity coefficient is
derived very easily by the following formula.

Z Z
dz
d
d
a d
z
dz
d
d
a d
a
n
j b a
k j
k
k
r
j
b a
k i
k
k
r
r
i
ln 1
~ ~
~
ln
1 ... , ... ,
+
+ =

= = =

k
are different parts of the EOS (not necessarily parameters) which depend on
composition. Their individual choice is up to the programmer. All
k
together must
cover all parts of the EOS which depend on composition, when and T are given and
held constant. For the PR-EOS (see below) it is sufficient to use
1
=a and
2
=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 =
r
a
~
, 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
L
=(T,P,x,iphase=1) and
G
=(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 (T,P,z) for most
(complicate) EOS, PE offers an algorithm for finding the solution numerically. This
- 83 -
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,,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},
L
{rhol},
G
{rhog} are known and the
fugacity coefficients
i,L
{phil(i)} and
i,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.

4.4.1 Subroutine Parameters
The subroutine parameters are the same for all different EOS and the list of parameters
must not be changed:
- numerical constants:
- n
max
is the maximum number of components and is set outside of the subroutine
- N
Av
= 6.022045 D+23 (Avogadro number)
- Tau = 1/6 * * 2 = 0.74048... (closest packing fraction)
- Pi = = 3.1415926535897932385...
- R = 0.0831439 (universal gas constant. Unit in PE: bar * dm / mol / K)
- n
steu
= number of EOS to be used (vdW=0, PR=1, SRK=3, EOS_on_DISK=99...)
- mixrule = number of mixrule to be used. The chosen mixrule must have no influence
on calculated pure-component properties. Calculations with mixrule=0 have to be
possible.
- 84 -
- n
co
= number of compounds in mixture (1=pure, 2=binary, 3=ternary ...), n
co
n
max
!
- T = Kelvin temperature [Unit = K]
- PuCoPa = up to 7 pure-component parameters for each compound
- sts(i,0:3) number of association sites selected for the pure components i:
(i,1)= number of (+)-sites, (i,2)= number of (-)-sites,
(i,3) = number of (COOH)-sites,
(i,0) = sum of entry 1,2,3 = total number of sites on molecule i.
- Calc_what (CW) determines what should be calculated in the subroutine
- CW=0: initialization, input: PuCoPa, sts, T as well as numerical constants
output: temperature-dependent parameters which are saved.
- CW=1: calculate P[rho,T,iphase,(xi or yi), (k,l,la,kep,kkap) and save-
parameters].
The save-parameters are set before by calling CW=0 and CW=2
- CW=2: calculate
L
(T,P=pp,x) and
G
(T,P=pp,y) by:
a) set save-parameters that depend on composition
b) set rhomx that is the maximum density for the given EOS, T and z
c) calculate
L
(T,P=pp,x) and
G
(T,P=pp,y) with pedens, iteratively
d) calculate
L
(
L
,T,P=pp,x) and
G
(
G
,T,P=pp,y)
- binary interaction parameters with k
ii
= l
ii
=
ii
= k
ii
= k
ii
= 0
- k: k
ij
=k
ji

- l: l
ij
= l
ji

- la:
ij
= -
ji
(i.e. asymmetric!)
- kep: k
ij
= k
ji

- kkap: k
ij
= k
ji
- pp = P(T,rho) =
1) output of calculation with calc_what=1 [unit = bar]
2) input for calculation with calc_what=2 [unit = bar]
- dp = P/(T,) = output of calculation with calc_what=1 [unit = bar /(mol/dm)]
- rho = input of density for P(T,rho) calculation (calc_what=1) [mol/dm = kmol/m]
- iphase determines which phase should be used for calculations with calc_what=1
iphase=0: gas phase, iphase=1: liquid phase
- iphaseerr = error flag set outside the subroutine. It inverts the meaning of iphase.
- mode = variable for pedens, set outside to a value of 3 (see pedens header)
- x
i
, y
i
= mole fractions of the coexisting phases (x: liquid, y: gas)
- rhol, rhog = density results of calc_what=2 calculations,
i.e.
L
(T,P=pp,x) and
G
(T,P=pp,y) [mol/dm = kmol/m]
- errliq, errvap = error flags which are set if pedens was not successful
(see pedens header)
- phil, phig = fugacity coefficients: results of calc_what=2 calculations,
i.e.
L
(
L
,T,P=pp,x) and
G
(
G
,T,P=pp,y)
- called_by_EOS_on_DISK = logical flag which is true if the subroutine was called by
EOS_on_DISK.EXE. Then the parameters from the save-command have to be
read from a file and saved to the file EOS_on_DISK.sav (see below and
example). Otherwise the flag is false.
- 85 -
4.4.2 Parameters for Simple Peng-Robinson EOS
(FORTRAN: save)
In order to speedup calculations, the equations within the subroutine blocks
(calc_what=1,2,3) are arranged in such a way, that multiple calculations of variables
that do not change within iterations are avoided: The equations for calculating the
pressure P(T,,z) (calc_what=1) are constructed in such a way that single parts of the
equations that only depend on temperature and composition - but not on density - are
calculated and stored in save-variables before the iterations in pedens are started. There
are three types of possible save-variables
1) pure-component parameters like T
c
, P
c
, (they need not be saved, here, but
demonstrate how it could look like for other EOS like SAFT).
2) Pure-component parameters like a
i
, b
i
, c
i
that do not depend on composition but
may depend on temperature (c
i
is not used for the PR-EOS, here)
3) Mixture-parameters that also depend on composition but not on density (ax, ay, bx,
by ...)

Variables of type 1 and 2 which do only depend on temperature are set at
initialization (calc_what=0). The variables of type 3 are set at calculate fugacities
(calc_what=2) directly before the FORTRAN statement if (p.lt.0) return which is
directly placed before the calls of pedens.
The FORTRAN save-statement ensures that the variables which are set once, can be
used in the next calls of the subroutine, again, i.e. that they are not forgotten. The save-
statement can only be used, if the subroutine is directly included in the PE.EXE /
PE_INT.EXE files or in EOS_P_TEST.FOR / EOS_PHI_TEST.FOR. Save can not be
used by EOS_on_DISK.EXE (see Section 4.7).

Important: In case, only the pressure P(,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 (P,T,z)
and (P,T,z) in the call with calc_what=2 because of the statement if (p.lt.0) return.

4.4.3 Initialization (calc_what=0)
In case of calc_what=0, there have to be done two things:
a) store the pure-component parameters PuCoPa(), which come from PE.EXE in local
variables, which have to be saved if they should be used for calc_what0 calls,
again.
b) In order to speedup calculations, all variables (or parts of the EOS) which only
depend on temperature but not on composition, density or pressure should be set
here. For the Peng-Robinson EOS, all a
i
(T) and b
i
are set here. These variables have
to be saved, because they are used for calc_what0 calls later, again.
- 86 -
4.4.4 Calculate Pressure (calc_what=1)
Here, either P(T,
L
,x) or P(T,
G
,y) is calculated. Iphase (and iphaseerr) are used by PE
to decide which of either has to be done. Depending on iphase (and iphaseerr) the
variables am/bm (a and b for mixture) are set equal to ax/bx or ay/by. (Note: ax, ay, bx,
by are set in the section calc_what=2 before the statement if(p.lt.0)return).
Afterwards, {thet}, / {dthet}, P {pp}and P/ {dP} are calculated. {pp} and
{dp} are returned to PE via the parameter list.
4.4.5 Calculate Fugacity Coefficients (calc_what=2)
First, mixture parameters that only depend on temperature and composition but not on
density (ax, ay, bx, by...) are calculated. Afterwards, there are two possibilities:
1) For P>0,
L
(P,T,x),
G
(P,T,y),
i,L
(P,T,x), and
i,G
(P,T,y) should be calculated:
first, rhomx is determined. Rhomx is the maximum achievable density for the given
EOS, i.e. the density for which the EOS calculates P. Rhomx is required by
pedens. Afterwards, pedens is called. Pedens will call the subroutine again multiple
times with calc_what=1. Therefore the saved parameters ax, bx, ay, by have to be
present. Within PE.EXE and EOS_P/PHI_TEST.EXE this is achieved using the
save-statement. Two calls of pedens determine
L
(P,T,x),
G
(P,T,y). Afterwards
i,L
(P,T,x), and
i,G
(P,T,y), i.e. {phil(i)} and {phig(i)} are calculated and returned
to PE together with {rhol, rhog, errliq, and errvap}.
2) For P<0, the subroutine has only been called in order to set the mixture parameters
{ax, ay, bx, by} that are needed for a call of calculate pressure (calc_what=1),
later. Afterwards the subroutine is finished, by the statement if(p.lt.0)return. P<0
is obviously (mis)used as a flag here: see EOS_P_TEST.FOR.
4.4.6 Subroutine si_mix_abc
Si_mix_abc is a simplified subroutine of the subroutine Mix_abc used in original PE.
The parameter list is the same, thus the subroutines are interchangeable. The
subroutine Mix_abc is used for practically all cubic EOS in PE and should be used for
all new (cubic) EOS, also. This saves enormous amounts of listing, because Mix_abc
contains many different mixing rules which can be chosen by selecting the appropriate
value for the variable {mixrule}:

Mixrule=0 Quadratic Mixrule=4 Panagiotopoulos-Reid
Mixrule=1 Adachi-Sugie Mixrule=42 Mathias-Klotz-Prausnitz
Mixrule=2 Melhem Mixrule=43 Mathias-Klotz-Prausnitz, Wong-Sandler
Mixrule=3 Stryjek-Vera

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).
- 87 -
4.5 EOS_P_TEST.FOR, EOS_PHI_TEST.FOR - Programs

The (sub)programs EOS_P_TEST.FOR and EOS_PHI_TEST.FOR called by
EOS_TEST.FOR demonstrate the use of the subroutine User_EOS in the file
pes_EOS_by_User.FOR. These two little programs should serve as first tests for new
written subroutines in pes_EOS_by_User.FOR files. The files are self explanatory. The
results can easily be compared with calculation results obtained with other programs.

- EOS_P_TEST.FOR demonstrates the calculation of P(T,,x).
- EOS_PHI_TEST.FOR demonstrates the calculation of
L
(T,P,x) and
G
(T,P,y) as
well as
L
(
L
,T,P,x) and
G
(
G
,T,P,y).

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.

4.6 FORTRAN Language

In case one likes to implement the EOS routines in PE.EXE, later, please follow the
below instructions for the FORTRAN language, that avoid typical errors:

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, N
Av
, and TAU and do not redefine
them.
- 88 -
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.

Important: Because EOS_on_DISK.EXE is a program (and not a subroutine) which
repeatedly calls itself, the FORTRAN save-command does not work here in the same
way as it is used in the above sections. In order to compensate for the loss of this save-
buffer, EOS_on_DISK.EXE uses the subroutines read_eos_save and write_eos_save
in pes_RW_EOS_Save.FOR which have to be adjusted for each EOS so that all save-
parameters are written to (and read from) the file EOS_on_DISK.sav (compare
example with PR-EOS). Setting the variable called_by_EOS_on_DISK to true in
EOS_on_DISK.FOR, will automatically lead to calls of read_eos_save and
write_eos_save in pes_EOS_by_User.FOR.

4.7.1 Running EOS_on_DISK.EXE

Choosing the equation EOS_on_DISK in PE.EXE, PE.EXE will call
EOS_on_DISK.EXE written by the user and placed in the same directory as PE.EXE
instead of calling the internal EOS subroutines: Figure 4.7a and 4.7b.

Figure 4.7a Choosing EOS_on_DISK for mixture calculations

- 89 -

Figure 4.7b: Choosing EOS_on_DISK for pure-component calculations

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
- 90 -
4.8 Some Details

4.8.1 Enforcing T
c
and P
c
During Optimization

The PE feature of optimizing pure-component parameters while simultaneously
enforcing the correct reproduction of T
c
and P
c
, requires that the first two parameters
are the major parameters of the EOS.
1) Parameter 1 must be a parameter closely connected to T
c
or an energy (T
c
, T
c
, a,
u
0
/k ...).
2) Parameter 2 must be a parameter closely connected to P
c
or a volume (P
c
, P
c
, b, v
00

...).
3) Parameters connected to non-spherical shape (, , c from Prigogine, chain length
m) or purely empirical fit parameters (p
1
in the PR-Boston-Mathias EOS) must not
be parameter 1 or 2.
Please, compare the choice of parameters with the choice of EOS parameters for EOS
already implemented in PE.

Further, the name of parameter 1 and 2 must not be T
c
and P
c
if the calculated critical
properties are not equal to these parameters: compare the use of T
c
and P
c
for the
Anderko-EOS or the PR-CPA-EOS.

Generally, parameters which are closely related to experimental properties and
parameters with simple units should and be preferred, so that the user can easily find
initial guesses for parameter optimisations. For the Peng-Robinson EOS, T
c
and P
c
are
used instead of a(T
c
) and b, for example. For the volume-translated PR- and SRK-EOS
c/b is used instead of c, because this simplifies finding initial guesses, because c/b can
believed to be between 20% and + 20%.

4.8.2 Using Sites and Interaction Parameters

Using sites, parameter 4 and 5 should be used to describe the property of the sites,
because these parameters are enabled if sites are used and disabled if the number of
sites is set to zero in PE.EXE.

The binary interaction parameters k and k should be used for interaction between
sites for the same reasons. k
ij
(
ij
) should be the first (second) parameter to fit a
ij
and
u
ij
, i.e. energy parameters. l
ij
should be used to fit b
ij
, i.e. volume parameters.

Please note, that k
ij
=k
ji
, l
ij
=l
ji
, k
ij
= k
ji
, k
ij
=k
ji
but
ij
= -
ji
.

- 91 -
4.8.3 The File EOS_on_DISK.sav

Because EOS_on_DISK.EXE will run as a program and call itself, it is not possible to
benefit of the FORTRAN save-command. Instead, the subroutines read_eos_save and
write_eos_save have to be used. All save-parameters have to be saved in the file
EOS_on_DISK.sav which serves as (slow) save-buffer.
The subroutines read_eos_save and write_eos_save in the file
pes_RW_EOS_Save.FOR are used to handle this buffer. These two subroutines have
to be modified according to the needs of a new EOS in order to read/write all save-
variables.

In the beginning of the EOS standard subroutine in pes_EOS_by_User.FOR,
read_eos_save has to be called. At the end of the subroutine write_eos_save has to be
called in order to save the parameters. One additional call of write_eos_save has to be
placed just in front of the calls of pedens / the statement if (p.lt.0.0) return.

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.

Using the included EOS_on_DISK.EXE file, each call of EOS_on_DISK.EXE will
lead to one DOS window opening and closing automatically in order to show that
PE.EXE and EOS_on_DISK.EXE are working.

Chapter 5: Export of Data
- 92 -
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.

Figure 5a: Export of graphics to files and printers.
Chapter 6: Future Developments
- 93 -
6 Future Developments
The first preliminary Windows release of PE was shown at the 8
th
International
Conference on Properties and Phase Equilibria for Product and Process Design held at
Noordwijkerhout, The Netherlands, on April 30
th
, 1998 (Pfohl et al., 1998a). The first
official Windows release of PE was finished in July 1998 and shown at the 17
th

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.

Further future developments might also include:
- improving the performance of the flash, including further stability tests
- improving three-phase calculations for binary systems
- improving azeotropic calculations for binary systems
- improving the quality of the graphical output
- implementing further possibilities to calculate other phase diagrams
(Txy diagrams, composition tetraeders for quaternary systems)
- implementing four-phase algorithms for ternary systems
- implementing new EOS, like SAFT-Dimer and EOS with near-critical corrections
- implementing export of data to Microsoft Excel.

If users desire special routines or special EOS, these can also be built in.
Appendix A1: EOS in PE

- 94 -
Appendix A1: EOS Implemented in PE

Appendix A1 lists all EOS implemented in the program package PE. The numbers of
the sections are identical to the numbers that are used by PE to address the different
EOS for internal data processing.
This appendix also contains the names of the different pure-component and mixture
parameters for each EOS used in PE. This appendix also contains the syntax used in
the pure-component parameter blocks in the EXFILES.
For many EOS the first two PE parameters have been chosen to be the critical
temperature and critical pressure calculated by the EOS
**
. PE calculates two real EOS
parameters (like a and b) from this information. Setting these PE parameters equal to
the experimentally determined values of T
c
and P
c
might allow sufficient calculations
with many of these EOS. However, it is common practice to fine tune the real EOS
parameters, in order to reproduce special properties with the EOS, best. PE allows this
by optimising T
c
and P
c
to be calculated with the EOS - i.e. changing the real
parameters a and b.

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 T
c
and P
c
- corresponding to a and b - for
each component.

EOS:
P
RT
v b
a
v
=

2

PURE-COMPONENT PARAMETERS:
a
R T
P
c
c
= 0 421875
2 2
,

b
RT
P
c
c
= 0125 ,

**
It is important to note, that these are not necessarily identical to the experimentally determined properties of a
pure compound.

- 95 -
EXFILE EOS PARAMETER INPUT:
2 0 00 van der Waals
Tc 0.000000 0.000000
Pc 0.000000 0.000000

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: T
c
, P
c
and the acentric factor . Different modified Peng-Robinson EOS
with volume-translations and modified alpha functions are listed in sections 10-19.

EOS:
( )
P
RT
v b
a T
v bv b
=

+
2 2
2

a T a T T
c r
( ) ( ) ( , ) = with a T
R T
P
c
c
c
( ) , = 0 45724
2 2

( )
( ) ( )
,
T T
r r
= + 1 1
2
with = + 0 37464 154226 0 26992
2
, , ,

b
RT
P
c
c
= 0 0778 ,

3 0 01 Peng-Robinson
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000

- 96 -
MIXTURE PARAMETERS:
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: T
c
, P
c
and . is a measure
for the slope of the vapour pressure curve. In case =-0.5, the simple Redlich-Kwong
EOS (Redlich and Kwong, 1949) is obtained.

EOS:
P
RT
v b
a T
v v b
=

+
( )
( )

a T a T
c r
( ) =

with a
R T
P
c
c
c
= 0 42747
2 2
,

b
RT
P
c
c
= 0 08664 ,

3 0 02 Hederer-Peter-Wenzel
Tc 0.000000 0.000000
Pc 0.000000 0.000000
alpha 0.000000 0.000000

MIXTURE PARAMETERS:
Appendix A2.

LITERATURE:
Hederer, Peter, and Wenzel (1976)


- 97 -
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: T
c
, P
c
and . Different modified Soave-Redlich-
Kwong EOS with volume-translations and modified alpha functions are listed in
subsections 30-39.

EOS:
P
RT
v b
a T
v v b
=

+
( )
( )

a T a T
c
( ) ( ) = with a
R T
P
c
c
c
= 0 42747
2 2
,

( ) ( )
( ) T m T
r
= + 1 1
2
with m= + 0 48 1574 0176
2
, , ,

b
RT
P
c
c
= 0 08664 ,

3 0 03 Soave-Redlich-Kwong
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000

MIXTURE PARAMETERS:
Appendix A2.

LITERATURE:
Soave (1972)


- 98 -
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 T
c
and P
c
- corresponding to the parameters a
and b - for each component.

EOS:
P
RT
v b
a T
v v b
=

+
/
( )

a
R T
P
c
c
= 0 42747
2 2 5
.
.

b
RT
P
c
c
= 0 08664 ,

2 0 04 Redlich-Kwong
Tc 0.000000 0.000000
Pc 0.000000 0.000000

MIXTURE PARAMETERS:
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: T
c
, P
c
and .

- 99 -
EOS:
Z Z Z
ref pert
= +

( ) ( )
Z
ref
DE
F
E
F
DE
F
E
F
=
+ + +
1 2 1
1
3 3 3
2 3
3
3
2
3
2

( )

with D
i i
i
N
=
=

1

E
i i
i
N
=
=

2
1

F
i i
i
N
=
=

3
1

i
i
A
b
N
=
|
\
|
.
|
3
2
1
3

= =
=
6 4
1
N F b
A i i
i
N

Z
a
RT
b b
pert
= +
|
\
|
.
|
|
\
|
.
|
|

1 141
4
5 07
4
2
, ,


( )
a a a a T
c r
= +
( ) ( )
.
tanh( )
1 2
0 7
1 1
with a
(1)
, , = + 0 367845 0 055966
a
m ( )
( ) ( , , )
2
1 0 604709 0 008477 = +
a
R T
P
c
c
c
= 0 550408
2 2
,

( )
b b b b T
c r
= +
( ) ( )
.
tanh( ln )
1 2
0 8
1
with b
(1)
, , = 0 356983 0190003
b
m ( )
( ) ( , , )
2
1 137 1898981 =
b
RT
P
c
c
c
= 0187276 ,
and m=1 for T
r
1
m=0 for T
r
<1

3 0 05 Dohrn-Prausnitz, nonpolar
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000

- 100 -
MIXTURE PARAMETERS:
Appendix A2.

LITERATURE:
Dohrn and Prausnitz (1990)

6. Dohrn-Prausnitz EOS, polar
The implementation of this EOS is not released for official use, because no tests have
been carried out, yet.

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
RT
c z q Y
k Y
m
= +

+
1
4
1 19
1
1
.

a
k
T
c c
c c
c
= =
+ +
+ +
1 0 945 1 0134 1
1023 2 225 1 0 478 1
2
2
. ( ) . ( )
. . ( ) . ( )

**

b v
RT
P
c c
c c
c
c
= =
+ +
+ +
*
. . ( ) . ( )
. ( ) . ( )
0 0312 0 087 1 0 008 1
1 2 455 1 0 732 1
2
2

c = + + 1 3535 0533
2
. .

**
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 T
c
and P
c
or if the formulas are correlations. There is some evidence that these
formulas are correlations.

- 101 -
k
1
= 1.7745
k
2
= 1.0617
k
3
= 1.90476
z
m
= 9.49
q = 1 + k
3
(c-1)

3 0 07 Elliott-Suresh-Donohue
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000

MIXTURE PARAMETERS:

=

i i
v
v
*

4
4
c
cv
v
i j ij

=
( )
*

q Y
qv Y
v
i j ij ij

=
( )
*

( )
*
* *
cv
c v c v
ij
i j j i
=
+
2

( )
*
* *
qv
q v q v
ij
i j j i
=
+
2

ij i j ij
k = ( ) 1

Y
kT
k
ij
ij
= exp( )
Y
q Y
q
i i
=

LITERATURE:
Elliott, Suresh, and Donohue (1990)


- 102 -

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:
P
RT v b bc
v v b
a
v v b
=
+

+
( )
( ) ( )

PURE-COMPONENT EOS PARAMETERS:
a a T
c
= ( )

with

( )
( )
T
T T
T
R R
R
=
+
+
0
2 2
2
1 2
1

0
11920 0 11060 1000 0 30734 = + + , , ln( ) , V V
w w

a
D cD D cD D
D D
R T
P
c
c
c
=
+ + +
+

( )( )
( ) ( )
1 2 2 1
3 1 2
0 0 0
2
0
2
0
2
0
2
0
2 2

D c D D
0
3
0
2
0
6 3 3 1 0 + + = ( )

b
D RT
P
c
c
=
0
3

V
w
is the van der Waals volume and can either be calculated by the group-contribution
method of Bondi (1968) or treated as adjustable parameter.


- 103 -
4 0 08 Sako-Wu-Prausnitz
Tc 0.000000 0.000000
Pc 0.000000 0.000000
c 0.000000 0.000000
v00 0.000000 0.000000 [dm3/mol]

MIXTURE PARAMETERS
The parameters a and b are calculated according to appendix A2. The parameter c is
the arithmetic mean of the c
i

LITERATURE:
Sako, Wu, and Prausnitz (1989)

10-19. Modified Peng-Robinson EOS
The Peng-Robinson EOS (Peng and Robinson, 1976) was modified by several
researchers. Peneloux et al. (1982) suggested a volume translation which does not
affect the calculation of vapour pressures. Many researchers proposed new alpha
functions, introducing a new temperature dependence of the parameter a(T).
All modified PR EOS implemented in PE include the possibility of a volume
translation according to Peneloux et al. (1982). Temperature dependent volume
translations like those by Chou and Prausnitz (1989) or Ji and Lempe (1997) are not
included in PE, because they lead to unphysical behaviour in the high density region
(Pfohl, 1999). The only differences between the different modifications are the
different alpha functions with a different number of adjustable parameters.

EOS:
P
RT
v b
a T
v b v b
=

+
~
~
( )
~
~
~
~
2 2
2
with
~
v v c = + and
~
b b c = +

a T
R T
P
c
c
c
( ) , = 0 45724
2 2
with a T a T T
c r
( ) ( ) ( , ) =

~
. b
RT
P
c
c
= 0 0778

- 104 -
10 (PR-VT, Peneloux):
= + 0 37464 154226 0 26992
2
, , ,
( )
( ) ( )
,
T T
r r
= + 1 1
2

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:
Peneloux, Rauzy, and Freze (1982)

11 (PR-VT, Mathias):
= + 0 37464 154226 0 26992
2
, , ,
if T
r
<1: ( ) ( ) ( ) ( )( . ) T T p T T
r r r r
= + 1 1 1 0 7
1
2

if T
r
>1: ( ) ( )
( ) exp ( ) T c T
r r
d
= 1
2

c p = + + 1
2
0 3
1
.
d
c
c
=
1

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:
Mathias (1983)


- 105 -
12 (PR-VT, Stryjek-Vera):
= + + 0 378893 14897153 017131848 00196554
2 3
. . . .
( )( ) ( )
( ) ( )( . ) T T T T
r r r r
= + + + 1 1 0 7 1
1
2

5 0 12 PR-VT, Stryjek-Vera
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000
kap_1 0.000000 0.000000
c/b 0.000000 0.000000 [ratio of c b /
~
]
LITERATURE:
Stryjek and Vera (1986)

13 (PR-VT, Melhem):
( ) ( ) exp ( ) ( ) T m T n T
r r r
= + 1 1
2

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:
Melhem, Saini, and Goodwin (1989)


- 106 -
14 (PR-VT, Thorwart-Daubert):
= + 0 37464 154226 0 26992
2
, , ,
( ) ( )
( )
T T n
T
T
r r
r
r
= + +

|
\
|
.
|
|
1 1
1
2

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:
Thorwart and Daubert (1993)

15 (PR-VT, Boston-Mathias):
= + 0 37464 154226 0 26992
2
, , ,
if T
r
<1: ( ) ( ) ( ) ( )( . ) T T p T T
r r r r
= + 1 1 1 0 7
1
2

if T
r
>1: ( ) exp ( )( ) T
d
T
r r
d
=
|
\
|
.
|
|
\
|
.
|
1
1
1
2

d p = + + 1
2
0 3
1
.
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:
Boston and Mathias (1980)

MIXTURE PARAMETERS:
Appendix A2. In order to avoid inconsistencies the parameters l
ij
are set to 0. The
parameter c is the arithmetic mean of the c
i

- 107 -
20. Pfennig EOS
The EOS by Pfennig (1988) is a modification of PHCT by Beret an Prausnitz. The
EOS is based on the hard sphere repulsion term by Carnahan and Starling (1969),
Boublik (1970), and Mansoori et al. (1971). Instead of using the polynomial series by
Alder et al. (1972) for attractive forces like in PHCT, Pfennig developed a polynomial
series in

=
1
in order to obtain a pole at closest packing (=1), automatically.
The EOS has three input parameters for pure compounds: the core volume v
0
, the
potential depth characterised by T
*
, and the parameter c after Prigogine (1957)
characterising deviations from spherical shape.

EOS:

a
RT
c a
T
r
ij
i
j
j
n
i
m
=
= =
~
0 1

~
*
T
T
T
= ,

=
v
v
0
,

= =
2
6
0 74048 . ... (closest packing fraction)

For the Pfennig EOS no conversion formulas are needed.

3 0 20 Pfennig
T* 0.000000 0.000000
v0 0.000000 0.000000
c 0.000000 0.000000

MIXTURE PARAMETERS
T T T k
i j i j ij
j
N
i
N
* * *
( ) =
= =
1
1 1
with k
ij
= k
ji

v
v v
i j
i j
j
N
i
N
0
0
1 3
0
1 3
3
1 1 2
=
+
|
\
|
.
|
|

= =

,
/
,
/

c c
i i
i
N
=
=
1

LITERATURE:
Pfennig (1988)

- 108 -
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 V
00
,
the potential depth u
0
/k, for characterising non-spherity and /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 Z Z
h a
= +
Z
y
y
y
y y
y
h
s
s s
s
s s s
s
=
1
1
3
1
3
1
2
2 2
3
( ) ( )
( )
( )

with y
V
V
s
s
s
=
|
\
|
.
|
2
6
0

Z mD
u
kT
V
V
a
nm
s
n
s
s
m n
m
=
|
\
|
.
|
|
\
|
.
|
= =

0
1
9
1
4

with the universal constants D
ij
:
D
11
= -8,8043 D
21
= 2,9396 D
31
= -2,8225
D
12
= 4,164627 D
22
= -6,0865383 D
32
= 4,7600148
D
13
= -48,203555 D
23
= 40,137956 D
33
= 11,257177
D
14
= 140,4362 D
24
= -76,230797 D
34
= -66,382743
D
15
= -195,23339 D
25
= -133,70055 D
35
= 69,248785
D
16
= 113,515 D
26
= 860,25349
D
27
= -1535,3224 D
41
= 0,34
D
28
= 1221,4261 D
42
= -3,1875014
D
29
= -409,10539 D
43
= 12,231796
D
44
= -12,110681


- 109 -

u
k
u
k kT
= +
|
\
|
.
|
0
1

V V
u
kT
0 00
0
3
1 012
3
=
|
\
|
.
|
|
\
|
.
|
, exp

4 0 21 BACK
u0/k 0.000000 0.000000
v00 0.000000 0.000000
alpha 0.000000 0.000000
eta/k 0.000000 0.000000

MIXTURE PARAMETERS
V x V
s i i
0 0
=

s
s
i i i i i i
V
x V x V =

1
0
0 0
1
3
2
3
( ) ( )

Set B by Machat and Boublik, 1985b:

u
k
x x
u
k
u
k
k
s
i j
i
j
ij
=

( ) 1

Set B by Pfohl and Brunner, 1998:

u
k
x x k V
x x V
s
i j
u
k
u
k ij ij
i j ij
i
j
=

( ) 1
0
0
with: V
V V
ij
i j 0
0 0
3
1
3
1
3
2
=
+ |
\
|
.
|
|
( ) ( )

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)


- 110 -
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.

- 111 -
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).

A molecule in SAFT-ConvexBody is described by either of the following pure-
component parameter sets in Table A1.1.

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 m1
T-dependence of u/k /k /k
convex parameter 1
number of asso. sites sites sites0
asso. Potential depth
A
no association possible
asso. Volume
A

no association possible

Note: it is clearly shown in Table A1.1, that either m or 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 1 and association sites.

EOS:

a a a a a
r hs disp chain asso
= + + +


- 112 -

a
RT N
hs
A
=

|
\
|
.
|

|
\
|
.
|
6 3 3
1
1
2
3
1 2 3 1 2 3
2
3 3
2 0
2
3
3
2 3

( )
ln( )

with

0
6
= N A
A
A X m m
i i
= =

1
6
= N B
A
B X m d
i i i i
=

( )
1
3

2
6
= N C
A
C X m d
i i i i
=

( )
1
3
2

3
6
= = N D
A
D X m d
i i i
=

a
RT
m D
u
kT
disp
ij
i
j i
j
=
|
\
|
.
|
|
\
|
.
|
= =

1
9
1
4

a
RT
X m g
chain
i i ij
i
N
=
=
( ) ln 1
1

with g
d d
d d
d d
d d
ij
i j
i j
i j
i j
=
+
+
+
+
|
\
|
.
|
|
1
1
3
1
2
1
3
2
3
2
2
2
3
3
2
( ) ( )

a
RT
X X
X
asso
i
A
i
A
i
A
i
sites i
i
N
= +

(

= =
ln
( )
1
2 1 1

with X
N X X
A
i
A j
B
j
A
i
B
j
B
j
sites j
j
N
=
+
= =
1
1
1 1

( )

A
i
B
j
ij
A
i
B
j
ij
A
i
B
j
g
kT
=
|
\
|
.
|
|

(
(
exp

1
3

ij
i j
=
+
2

A
i
B
j A
i
B
j
ij
k = ( ) 1

A
i
B
j A
i
B
j
ij
k = ( ) 1

The constants D
ij
are listed in section 21 (BACK EOS)

- 113 -

V V
u
kT
0 00
0
3
1 012
3
=
|
\
|
.
|
|
\
|
.
|
, exp

d V
N
A
=
|
\
|
.
|
0
2
1
3

u
k
u
k kT
= +
|
\
|
.
|
0
1

8 1 23 SAFT-ConvexBody
u0/k 0.000000 0.000000
v00 0.000000 0.000000
m 0.000000 0.000000
eps/k 0.000000 0.000000 [
A
]
kap 0.000000 0.000000 [
A
]
eta/k 0.000000 0.000000 [/k]
alpha 0.000000 0.000000 []
Sites 0 0 0 0 0 0


- 114 -
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 =0. The advantages of
these two-parameter mixing rules are explained in detail by Pfohl and Brunner (1998).

2-parameter van-der-Waals mixing rule

u
kT
u
kT
u
kT
= +
( ) (1) 0

with
u
kT
X X m m k V
X X m m V
i j i j
u u
kT ij ij
i j i j ij
i j
( )
( )
0
0
0
1
=

( )
u
kT
X m X m V
X X m m V X m
i i j j ij
u u
kT ij
i j i j ij i i
i j
(1)
=
|
\
|
.
|
(

0
3
0
2
1
3

2-parameter volume-fraction mixing rule

u
kT
f f
u u
kT
k f f
u u
kT
i j
i j
ij i j
i j
ij
= +
|
\
|
.
|
|
(
(

( ) 1
1
3
3

with the volume fraction f
X m V
X mV
k
k k k
i i i
=
0
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)


- 115 -
24. SAFT-Conventional
This EOS is identical to SAFT-ConvexBody (section 23) but it does allow no use of
convex bodies (i.e. all =1). This implementation allows to save different sets of pure
component parameter sets (and k
ij
) 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.

u0/k 0.000000 0.000000
v00 0.000000 0.000000
m 0.000000 0.000000
eps/k 0.000000 0.000000 [
A
]
kap 0.000000 0.000000 [
A
]
eta/k 0.000000 0.000000 [/k]
Sites 0 0 0 0 0 0

25. Perturbed-Chain SAFT

The FORTRAN code for the EOS in PE and this description have been supplied by:

J. Gro, F. Tumakaka, G. Sadowski, and W. Arlt
TU Berlin
Institut fr Verfahrenstechnik
Forschungsgruppe Polymerthermodynamik
Sekr. TK 7
Strae des 17. Juni 135
10623 Berlin
Germany

The Perturbed-Chain SAFT EOS was proposed by Gro 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.

- 116 -
Three pure component parameters are required for each non-associating component:
the segment number m, the segment diameter
ii
, and the attraction parameter
ii
. 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:

NkT
A
NkT
A
NkT
A
pert hc
+ =

Hard-Chain Contribution:

( )
ii
i
hs
ii i i
S
hs ideal hc
g m x
kT N
A
m
NkT
A
NkT
A
= ln ) 1 (
with ( )
(
(

|
|
.
|
\
|
+
=
3 0 2
3
3
2
3
3 3
3
2
3
2 1
0
1 ln
) 1 ( ) 1 (
3 1

kT N
A
S
hs

and
3
3
2
2
2
2
3
2
3
) 1 (
2
) 1 (
3
) 1 (
1

|
|
.
|
\
|
+
+
|
|
.
|
\
|
+
+
=
j i
j i
j i
j i hs
ij
d d
d d
d d
d d
g
where
=
i
m
i i i m
d m x
6

Perturbation Contribution

N kT
A
N kT
A
N kT
A
pert
2 1
+ =

with
|
|
.
|
\
|
=
i j
ij
ij
j i j i
kT
m m x x m I
N kT
A
3
1
1
) , ( 2

and
|
|
.
|
\
|

|
|
.
|
\
|
+ =
i j
ij
ij
j i j i
hc
hc
kT
m m x x m I
Z
Z m
N kT
A
3
2
2
1
2
) , (

The one-fluid mixing concept is applied to the compressibility term of the second order
perturbation term, i.e.

[ ]
|
|
.
|
\
|

+
+
+ =
|
|
.
|
\
|
+
2
4 3 2
4
2
) 2 )( 1 (
2 12 27 20
) 1 (
) 1 (
2 8
1

m m
Z
Z
hc
hc


- 117 -

In these equations, the integrals over the radial pair distribution function of chain-
molecules were replaced by power series in density of sixth order

i
i
i i i
a
m
m
m
m
a
m
m
a m I |
.
|
\
|
+
+ =

=
6
0
2 1 0 1
2 1 1
) , (
i
i
i i i
b
m
m
m
m
b
m
m
b m I |
.
|
\
|
+
+ =

=
6
0
2 1 0 2
2 1 1
) , (
with the universal constants a
0i
, a
1i
, a
2i
and b
0i
, b
1i
, b
2i
:

i a
0i
a
1i
a
2i
b
0i
b
1i
b
2i

0 0.79198281 -0.62311554 -0.06777556 0.79198281 -0.62311554 -0.06777556
1 1.07148651 0.48573437 0.02837411 2.14297303 0.97146874 0.05674823
2 0.91474661 1.12485267 0.09612281 2.74423982 3.37455809 0.28836841
3 -7.81060651 -2.09485016 0.06815027 -31.2424260 -8.37940062 0.27260110
4 25.7855977 9.45049823 0.05980187 128.927988 47.2524911 0.29900933
5 -56.9822877 -17.1027262 0.28660979 -341.893726 -102.616357 1.71965874
6 41.9308941 7.77610281 -0.74701698 293.516259 54.4327197 -5.22911885

d
i
is the temperature dependent segment diameter of component i:
|
.
|
\
|
|
.
|
\
|
=
kT
d
ii
ii i

exp 12 . 0 1

6 1 25 PC-SAFT
u0/k 0.000000 0.000000 [
ii
]
d00 0.000000 0.000000 [
ii
, unit: ]
m 0.000000 0.000000
eps/k 0.000000 0.000000 [
A
for association]
kap 0.000000 0.000000 [
A
for association]
Sites 0 0 0 0 0 0
MIXTURE PARAMETERS
The PC-SAFT EOS is applied to mixtures using one-fluid mixing rules. Conventional
combining rules are employed to determine the parameters between a pair of unlike
segments


- 118 -
( )
jj ii ij
+ =
2
1

and

) 1 (
ij jj ii ij
k =

LITERATURE:
Gro and Sadowski (1999)
Gro and Sadowski (2000)
Chapman et al. (1988)
Barker and Henderson (1967)

!
For further in-depth information, please contact the authors at
http://pcitr4.fb10.tu-berlin.de/pc-saft/pc-saft-home.html

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 v
00
and , which characterise one sphere as well as the number r of
spheres in a molecule have to be known.

EOS:
Z r r b g r g
kT
r r a
i j i j ij ij i i ii
i
N
i j i j ij
j
N
i
N
j
N
i
N
= +
= = = = =
1 1 1
1 1 1 1 1

( )( )


- 119 -
a v F
kT
s r
a
= 4
00
(
( )
)
b v F
kT
s r
b
= 4
00
(
( )
)

d T b ( )
3
6 4
=

( ) F x x
a
( ) . . exp . = + 0717 19003 05152
( )
( )
[ ]
F x x x
b
( ) . exp . . exp .
/
= +

05849 0 4772 041511 10669
1 4

s(r) is calculated from a FORTRAN function obtained from Professor
Prausnitz, University of California at Berkeley.

3 0 27 PHSCT
eps/k 0.000000 0.000000
v00 0.000000 0.000000
r 0.000000 0.000000

MIXTURE PARAMETERS
a v F
kT
s r
F
kT
s r
k
ij ij a
i i
a
j j
i j ij
= 4 1
00
(
( )
) (
( )
) ( )

v
v v
ij
i j
00
00
3
00
3
3
2
=
+
|
\
|
.
|
|
, b
b b
ij
i j
=
+
|
\
|
.
|
|
3 3
3
2
, d
d d
ij
i j
=
+
2

g
ij
ij ij
=
1
1
3
2 1
1
2 1
2
2
3
( ) ( )

=
= 4 1
i i i
i
N
r b

ij
i j
ij
k k k
k
N b b
b
r b =
|
\
|
.
|
|

= 4
2 3
1
/

LITERATURE:
Song, Lambert, and Prausnitz (1994)

- 120 -
30-39. Modified Soave-Redlich-Kwong EOS
The Soave-Redlich-Kwong EOS (Soave, 1972) was modified by several researchers.
Peneloux et al. (1982) suggested a volume translation which does not affect the
calculation of vapour pressures. Many researchers proposed new alpha functions,
introducing a new temperature dependence of parameter a(T).
All modified SRK EOS implemented in PE include the possibility of a volume
translation according to Peneloux et al. (1982). Temperature dependent volume
translations like those by Chou and Prausnitz (1989) or Ji and Lempe (1997) are not
included, because they lead to unphysical behaviour in the high density region (Pfohl,
1999). The only differences between the different modifications are the different alpha
functions with a different number of adjustable parameters.

EOS:
P
RT
v b
a T
v v b
=

+
~
~
( )
~
(
~
~
)
with
~
v v c = + and
~
b b c = +

a T a T
c
( ) ( ) = with a
R T
P
c
c
c
= 0 42747
2 2
,

~
. b
RT
P
c
c
= 0 08664


- 121 -
30 (SRK-VT, Peneloux):
m = + 0 48 1574 0176
2
, , ,
( ) ( ) ( ) T m T
r r
= + 1 1
2

4 0 30 SRK-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:
Soave (1972)

31 (SRK-VT, Mathias):
m = + 0 48 1574 0176
2
, , ,
if T
r
<1: ( ) ( ) ( ) ( )( . ) T m T p T T
r r r r
= + 1 1 1 0 7
1
2

if T
r
>1: ( ) ( )
( ) exp ( ) T c T
r r
d
= 1
2

c
m
p = + + 1
2
0 3
1
.
d
c
c
=
1

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)
Mathias (1983)


- 122 -
32 (SRK-VT, Schwartzentruber-Renon):
m = + 0 48508 155171 015613
2
, , ,
if Tr<1:
( )
( ) ( ) ( )( ) T m T p T p T p T
r r r r r
= + + + 1 1 1 1
1 2 3
2
2

if Tr>1: ( ) exp ( )( ) T
d
T
r r
d
=
|
\
|
.
|
|
\
|
.
|
1
1
1
2

d
m
p p p = + + + 1
2
1
1 2 3
( )
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)
Watanasiri and Gallier (1988)
Schwartzentruber, Renon (1989)
Schwartzentruber, Renon, and Watanasiri (1990)
Aspen Plus 9.3 Handbook, model: SR-polar


- 123 -
33 (SRK-VT, Thorwart-Daubert):
m = + 0 48508 155171 015613
2
, , ,
( ) ( )
( )
T m T n
T
T
r r
r
r
= + +

|
\
|
.
|
|
1 1
1
2

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)
Thorwart and Daubert (1993)

34 (SRK-VT, Peneloux-3P):
m = + 0 48 1574 0176
2
, , ,
( ) ( ) ( ) T m T
r r
= + 1 1
2

c
RT
P
c
c
= + 040768 000385 008775 . ( . . )
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


- 124 -
35 (SRK-VT, Boston-Mathias):
m = + 0 48 1574 0176
2
, , ,
if T
r
<1: ( ) ( ) ( ) ( )( . ) T m T p T T
r r r r
= + 1 1 1 0 7
1
2

if T
r
>1: ( ) exp ( )( ) T
d
T
r r
d
=
|
\
|
.
|
|
\
|
.
| 1
1
1
2

d
m
p = + + 1
2
0 3
1
.
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)
Boston and Mathias (1980)

MIXTURE PARAMETERS:
Appendix A2. In order to avoid inconsistencies, the parameters l
ij
are set to 0. The
parameter c is the arithmetic mean of the c
i
.

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 T
c
, P
c
and 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:
P
RT
v b
a
v v c b v c
=

+ + + ( ) ( ) 3


- 125 -
a a T
c r
= ( , )

a
R T
P
c
c
c
= + ( , , , ) 0 46863 0 0378304 0 00751969
2
2 2

if T
r
<1: log ( ) ( ) ( )( )
, 10 0 1 2
2
1 T M A AT A T T
r r r r
= + +
if T
r
1: log ( ) ( ) ( )( )
, 10 0 1 2
1 T M A A A T
r r
= + +

if 0,49 M( ) , , , , = + + 0 406846 187907 0 792636 0 737519
2 3

A
0
= 0,536843
A
1
= -0,39244
A
2
= 0,26507
if 0,49<1 M( ) , , , , = + 0 581981 0171416 184441 119047
2 3

A
0
= 0,79355
A
1
= -0,53409
A
2
= 0,37273

b
RT
P
c
c
= ( , , , ) 0 0892828 0 0340903 0 00518289
2

c
b
= + + 1 29917 0 648463 0 895926
2
, , ,

3 0 40 3P1T
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omega 0.000000 0.000000

MIXTURE PARAMETERS
Appendix A2.

LITERATURE:
Yu and Lu (1987)
Yu, Adachi, and Lu (1986)


- 126 -
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 T
c
and P
c
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 T
c
, P
c
, and by Anderko in order to
prevent confusion.
In addition to these three pure-component parameters, the input of H
0
, S
0
, and C
p
0

which characterise hydrogen bonds is required for each associating component.

EOS:

P P T v T T P P
RT
v RT
v
K
P T EOS
c c c c
i
ij j
j
N
i
N
= = = = +
+ +
=
=
3 1
1
1
2
1 1 4
( , , , , , )
' ' '
r
r r r r
r r


a) compare 3P1T EOS in section 40 with
r r
T T
c c
=
'
,
r r
P P
c c
=
'
, and
r r
=
'
.

b) ) ln ( ) (
ln
0
0 0 0 0 0
T
T
C S T T T C H K RT
p p i
+ + =
Note (also true for PE V1.0):
In order to be compatible with Anderko (1989-1992), the unit of K
is [atm], so
that K K
01323 . 1 = , because the unit of K is [bar].


- 127 -
6 0 41 Anderko, linear
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omga 0.000000 0.000000
**
H 0.000000 0.000000 [kJ/mol]
S 0.000000 0.000000 [J/mol/K]
CP 0.000000 0.000000 [J/mol/K]

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
K
ij
are zero if either i or j is an inert compound, otherwise:

K K K k
ij i j ij
= ( ) 1
c
c c
i j
i j
j
N
i
N
=
+

= =

2 1 1

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 a
0
, b,
c
1
, and T
c
EXP
, whereof T
c
EXP
is set equal to the experimentally determined critical
temperature of the pure component.

**
omga is no spelling mistake. No identifier may exceed 5 characters.

- 128 -
Instead of using the radial distribution function for pure compounds for mixtures like
Tassios et al. did, the version implemented in PE uses the g
ij
for mixtures by Boublik
(1970) and Mansoori et al. (1971).

EOS:
P
RT
v b
a T
v v b
RT
v
a
asso
=

+
+
|
\
|
.
|
( )
( )
~

~
ln
( )
a
a
RT
X X
X
asso
asso
i
A
A
A
sites i
i
N
i
i
i
= = +

(
= =

1
2
1 1

a T a c T T
i i i c i
EXP
( ) ( ( / ))
,
= +
0 1 2
1 1

b N
d
i A
i
= 4
6
3

i
i
Av
b
N
=
|
\
|
.
|
1 3 /
Note:
i i
d

7 1 50 CPA-SRK-Tassios
a0 0.000000 0.000000
b 0.000000 0.000000
c1 0.000000 0.000000
TcEXP 0.000000 0.000000
eps/k 0.000000 0.000000 [K]
beta 0.000000 0.000000
Sites 0 0 0 0 0 0


- 129 -
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.

X
N X X
A
i
A j
B
j
A
i
B
j
B
j
sites j
j
N
=
+
= =
1
1
1 1

( )

A
i
B
j
ij
A
i
B
j
ij
A
i
B
j
g
kT
=
|
\
|
.
|
|

(
(
exp

1
3

with

ij
i j
=
+
2

A
i
B
j A
i
B
j
ij
k = ( ) 1

A
i
B
j A
i
B
j
ij
k = ( ) 1

g
d d
d d
d d
d d
ij
i j
i j
i j
i j
=
+
+
+
+
|
\
|
.
|
|
1
1
3
1
2
1
3
2
3
2
2
2
3
3
2
( ) ( )

k A i i
k
i
N
N X d =
= 6 1

LITERATURE:
Kontogeorgis, Voutsas, Yakoumis, Tassios (1996)
Yakoumis, Kontogeorgis, Voutsas, Tassios (1997)
Voutsas, Kontogeorgis, Yakoumis, Tassios (1997)
Soave (1972)
Pfohl (1998)


- 130 -
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 T
c
,
P
c
and , here. The prime () indicates that the critical temperature (T
c
), critical
pressure (P
c
), and acentric factor () 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 T
c
<<T
c
and thus easier to T
c
<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>T
c
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.

6 1 51 CPA-SRK
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omga 0.000000 0.000000
eps/k 0.000000 0.000000
beta 0.000000 0.000000
Sites 0 0 0 0 0 0


- 131 -
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.

6 1 52 CPA-PR
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omga 0.000000 0.000000
eps/k 0.000000 0.000000
beta 0.000000 0.000000
Sites 0 0 0 0 0 0

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(T
c
)) and b are used as first two parameters instead of T
c
and P
c
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.

6 1 53 CPA-PR (a,b,om)
a0 0.000000 0.000000
b 0.000000 0.000000
omga 0.000000 0.000000
eps/k 0.000000 0.000000
beta 0.000000 0.000000
Sites 0 0 0 0 0 0


- 132 -
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.

6 1 54 CPA-3P1T
Tc 0.000000 0.000000
Pc 0.000000 0.000000
omga 0.000000 0.000000
eps/k 0.000000 0.000000
beta 0.000000 0.000000
Sites 0 0 0 0 0 0
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.

7 1 90 SAFT-HR/vdW
u0/k 0.000000 0.000000
v00 0.000000 0.000000
m 0.000000 0.000000
eta/k 0.000000 0.000000 [/k]
kap 0.000000 0.000000 [
A
]
eps/k 0.000000 0.000000 [
A
]
Sites 0 0 0 0 0 0


- 133 -
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 l
ij
used here, is used to modify m and not
used to modify u:

m m
i j ij
j
N
i
N
=
= =

1 1
with m
m m
l
ij
i j
ij
=
+
2
1 ( )

= =
= =
=
N
i
N
j
ij j i j i
N
i
N
j
ij ij j i j i
v m m
v u m m
u
1 1
0
1 1
0

with
3
3
0
3
0
0
2 |
|
|
.
|
\
|
+
=
j i
ij
v v
v and u u u k
ij i j ij
= ( ) 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.

7 1 91 SAFT-HR/vf
u0/k 0.000000 0.000000
v00 0.000000 0.000000
m 0.000000 0.000000
eta/k 0.000000 0.000000 [/k]
kap 0.000000 0.000000 [
A
]
eps/k 0.000000 0.000000 [
A
]
Sites 0 0 0 0 0 0

MIXTURE PARAMETERS:
m m
i j ij
j
N
i
N
=
= =

1 1
with m
m m
l
ij
i j
ij
=
+
2
1 ( )

= =
=
N
i
N
j
ij j i
u f f u
1 1
with
=
=
N
j
j j j
i i i
i
v m
v m
f
1
0
0
and u u u k
ij i j ij
= ( ) 1

That means = 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.

- 134 -
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
F
t
is implemented in PE. The three pure-component parameters needed for the Deiters
EOS are: a, b, and c.

EOS:
( ) Z cc
ab
c T
h T F
i
= +

+
+
1
4 2
1
0
2
3 2 0
2
1

( )
(
~
)

with F p c T b t
t ijk
k j i
i j k
=

= = =
( )
~
( ) 1
0
10
0
6
0
3

where p
ijk
= constants obtained from Deiters.

(
~
)
~
(exp(
~
) ) T T T =
1
1
= 1 0 697816 1
2
. ( ) c
h
0
7 0794046 = . , c
0
0 6887 = . ,
~
T
ckT
=
,

=
2
6
b


k
a =

The EOS implemented in PE is for pure compounds, only.

MIXTURE PARAMETERS

LITERATURE:
Deiters (1981, 1981b, 1983)
Pfohl et al. (1998)

- 135 -
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:
Z c
mA
v T
nm
m n
m n
= +

+
|
\
|
.
|
= =
1
4 2
1
2
3
1
9
1
4

( )
~
~


~
*
v rv
=
1

~
/
T
cT
q k
=


MIXTURE PARAMETERS

LITERATURE:
Beret and Prausnitz (1975)
Donohue and Prausnitz (1978)
Carnahan and Starling (1969)
Prigogine (1957)


- 136 -
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.
Appendix A2: Mixing Rules for Cubic EOS
- 137 -
Appendix A2: Mixing Rules for Simple EOS
PE offers several mixing rules for the following simple EOS, which are mostly cubic
EOS or based on a cubic EOS:
- van der Waals (EOS 0)
- Peng-Robinson (EOS 1) and modifications (EOS 10-15)
- Hederer-Peter-Wenzel (EOS 2)
- Soave-Redlich-Kwong (EOS 3) and modifications (EOS 30-35)
- Redlich-Kwong (EOS 4)
- Dohrn-Prausnitz, nonpolar (EOS 5)
- Sako-Wu-Prausnitz (EOS 8)
- 3P1T (EOS 40)
- Anderko (EOS 41)
- CPA EOS (EOS 50-55)
Most of the mixing rules for these EOS calculate the mixture parameters a and b for
the EOS according to the one-fluid mixing rules (Eq. A2.1 and A2.2) and the only
difference between them is the combining rule that determines how the cross
coefficients a
ij
and b
ij
are calculated. However, the Mathias-Klotz-Prausnitz mixing
rule and the MKP-WS mixing rule can not be written in terms of equations A2.1 and
A2.2. In order to minimise confusion, the term mixing rule will be used instead of
combining rule, also.

a x x a
i j ij
j
N
i
N
=
= = 1 1
(A2.1)

b x x b
i j ij
j
N
i
N
=
= = 1 1
(A2.2)

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
0 and the mole fraction x
i
of one component is arbitrarily split into two mole
fractions x
i
and x
i
with x
i
+x
i
=x
i
. 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
- 138 -
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.

A2.1 Quadratic mixing rule
The quadratic mixing rule is the only mixing rule described here which only offers a
maximum of two binary interaction parameters per binary system, whereof only one is
used to adjust the parameter a. All other mixing rules described hereafter offer a
maximum of three adjustable binary parameters, whereof two are used to adjust the
parameter a. These mixing rules exactly reduce to quadratic mixing rule, if the third
parameter is not used, i.e. set to zero. Often, the quadratic mixing rule is sufficient
for the correlation of equilibria in systems that do not contain specific interactions.
Mostly, the use of the second adjustable parameter l
ij
is avoided, by setting all l = 0 .

a a a k
ij i j ij
= ( ) 1 with k k
ji ij
= (A2.3)

b
b b
ij
i j
ij
=
+
2
1 ( ) l with l l
ji ij
= (A2.4)

A2.2 Panagiotopoulos-Reid Mixing Rule (1985)
The quadratic mixing rule (A2.1) is often only sufficient for the correlation of
equilibria in systems where no specific interactions are involved. Panagiotopoulos and
Reid (1985) have been the first to use two binary interaction parameters per binary
system in order to fine-tune the parameter a (Eq. A2.5 and A2.6). In most cases, the
parameters l
ij
are set to zero, because the use of k
ij
and
ij
already allows excellent
representations of many highly non-ideal binary phase equilibria. The use of the two
parameters k
ij
and
ij
is much more powerful than the use of the two parameters k
ij
and
l
ij
of the quadratic mixing rule (compare: Schwartzentruber and Renon, 1989). If all
are set to zero, the quadratic mixing rule is obtained again.

a a a k x
ij i j ij
PR
ij
PR
i
= + ( ) 1 with
ij
PR
ij
PR
ji
PR
ji
PR
k k = = (A2.5)

b
b b
ij
i j
ij
=
+
2
1 ( ) l with l l
ji ij
= (A2.6)

- 139 -
The original formula for the calculation of parameter a proposed by Panagiotopoulos
and Reid (1985) is shown in Eq. A2.7.

a a a k k k x
ij i j ij ij ji i
= + ( ( ) ) 1 with k k
ij ji
(A2.7)

A2.3 Adachi-Sugie Mixing Rule (1986)
Adachi and Sugie (1986, A new Mixing Rule) proposed their mixing rule (Eq.
A2.8)
1
slightly later than Panagiotopoulos and Reid (1985) and claimed that this
mixing rule is identical with the Panagiotopoulos-Reid mixing rule for binary systems
but not identical with it for multicomponent mixtures. However, Pfohl (1998) showed
that both mixing rules are absolutely identical. The incorporation of both mixing rules
in PE can be stated as superfluous, therefore.

a a a k x x
ij i j ij
AS
ij
AS
i j
= ( ( )) 1 with k k
ji
AS
ij
AS
= and
ji
AS
ij
AS
= (A2.8)

b
b b
ij
i j
ij
=
+
2
1 ( ) l with l l
ji ij
= (A2.9)

The original formula for the calculation of parameter a proposed by Adachi and Sugie
(1986) is shown in Eq. (A2.10).

a a a l m x x
ij i j ij ij i j
= ( ( )) 1 with l l
ij ji
= and m m
ij ji
= (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
ij
AS
ji
AS
= + and therefore to a complete elimination of this parameter in
calculations, i.e. calculation results independent of the value of
ij
AS
.
- 140 -
A2.4 Stryjek-Vera Mixing Rule (1986)
Stryjek and Vera (1986) claimed that their Van Laar-Type mixing rule (A2.11)
2

gives better correlation results than their Margules-Type mixing rule
3
which is
identical to the Panagiotopoulos-Reid mixing rule programmed in PE.

a a a
k k
x k x k
ij i j
ij
SV
ji
SV
i
ij
SV
j
ji
SV
=
+
( ) 1 with
ij
SV
ij
SV
ji
SV
ji
SV
k k : = = (A2.11)

b
b b
ij
i j
ij
=
+
2
1 ( ) l with l l
ji ij
= (A2.12)

A2.5 Melhem Mixing Rule (1991)
Melhem et al. (1991) proposed a new mixing rule (A2.13)
4
which does not suffer of
what they call a dilution problem, i.e. that the concentration dependency of the mixing
rule decreases as the number of components increases. But, this mixing rule still
suffers of the Michelsen-Kistenmacher Syndrome detected by Michelsen and
Kistenmacher (1990), before (see above).

a a a k
x
x x
ij i j
ij
M
ij
M i
i j
= +
+
( ) 1 with
ij
M
ij
M
ji
M
ji
M
k k = = (A2.13)

b
b b
ij
i j
ij
=
+
2
1 ( ) l with l l
ji ij
= (A2.14)

A2.6 Mathias-Klotz-Prausnitz Mixing Rule (1991)
Mathias et al. (1991) proposed a new mixing rule (A2.15)
5
which does not suffer of the
Michelsen-Kistenmacher Syndrome (Michelsen and Kistenmacher, 1990). Using this
mixing rule yields the same calculation results if the mole fraction x
i
of a component is
arbitrarily split into two mole fractions x
i
and x
i
with x
i
+x
i
=x
i
. This theoretical
advantage is strongly correlated to the ability to model real systems with similar
compounds as shown by Mathias et al. (1991) for benzene + cyclohexane and Pfohl
(1998) for two cresol isomers. It is noteworthy that this mixing rule is identical with
the above mixing rules by Panagiotopoulos-Reid (= Adachi + Sugie) and Melhem for

2
Equation (13) in this publication.
3
4
5
Equations (4), (5), (6), (12), and (13) in this publication.
- 141 -
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).

( )
a x x a a k x x a a
i j i j
ij
MKP
j
N
i
N
i j i j ji
MKP
j
N
i
N
= +

= = = =
( )
/
1
1 1 1
1 3
3
1

with k k
ji
MKP
ij
MKP
= and
ji
MKP
ij
MKP
= (A2.15)

b
b b
ij
i j
ij
=
+
2
1 ( ) l with l l
ji ij
= (A2.16)

Mathias et al. (1991) used the abbreviation l
ij
instead of
ij
in Eq. A2.15.

A2.7 MKP-WS Mixing Rule
Bnz (1995) modified the above Panagiotopoulos-Reid mixing rule in order to retrieve
a mixing rule which correctly reproduces the quadratic dependence of the second virial
coefficient enforced by theory (Eq. A2.17), according to the ideas of Wong and
Sandler (1992).

b
a
RT
B x x B x x b
a
RT
i
j
N
i
N
j ij i
j
N
i
N
j
ij
= = =
= = = = 1 1 1 1
(A2.17)

Since the Panagiotopoulos-Reid mixing rule suffers the Michelsen-Kistenmacher
Syndrome, the implementation in PE by Pfohl (Eq. A2.18 and A2.19) is based on the
Mathias-Klotz-Prausnitz mixing rule.

( )
a x x a a k x x a a
i j i j
ij
BP
j
N
i
N
i j i j ji
BP
j
N
i
N
= +

= = = =
( )
/
1
1 1 1
1 3
3
1
(A2.18)

( )
b x x
b b
RT
x x a a
i j
i j
j
N
i
N
ij i j i j ji
BP
j
N
i
N
=
+
+

= = = = 2
1
1
1 1 1
1 3
3
1
( )
/
l (A2.19)

with k k
ji
BP
ij
BP
= ,
ji
BP
ij
BP
= , and l l
ji ij
=

The influence of a volume translation by introducing parameter c0 in EOS 10-19/30-
39 and using Eq. A2.19 has not been investigated. A usage of a combination of both is
not recommended therefore - although the usage is possible.
- 142 -
A2.8 Conversion of Interaction Parameters
The Panagiotopoulos-Reid mixing rule ( = Adachi-Sugie mixing rule), the Melhem
mixing rule, and the Mathias-Klotz-Prausnitz mixing rule are identical if applied to
binary systems but yield different results if applied to systems with more than two
components. If optimum binary interaction parameters have been determined by fitting
binary data, these parameters are also the optimum parameters for the other above
mixing rules, therefore.
The following table contains the conversion formulas between the binary parameters of
the different mixing rules in order to obtain identical calculation results in binary
systems.
The Melhem mixing rule is not included, because it obviously gives the same
calculation results in binary systems as the Panagiotopoulos-Reid mixing rule, if
k k
ij
M
ij
PR
= and
ij
M
ij
PR
= (compare Eq. (A2.5) and (A2.13), if x
i
+ x
j
= 1).

Table A2.1: Conversion of binary interaction parameters between different mixing
rules

Panagiotopoulos-
Reid
Adachi-Sugie Mathias-Klotz-
Prausnitz
Panagiotopoulos-
Reid
- k k
ij
PR
ij
AS
ij
AS
ij
PR
ij
AS
=
=
2

k k
ij
PR
ij
MKP
ij
MKP
ij
PR
ij
MKP
= +
=
0 5 ,

Adachi-Sugie k k
ij
AS
ij
PR
ij
PR
ij
AS
ij
PR
=
=
05
05
.
.

-
k k
ij
AS
ij
MKP
ij
AS
ij
MKP
=
= 0 5 ,

Mathias-Klotz-
Prausnitz
k k
ij
MKP
ij
PR
ij
PR
ij
MKP
ij
PR
=
=
0 5 ,

k k
ij
MKP
ij
AS
ij
MKP
ij
AS
=
= 2

-

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Preface, Contents, Survey, and Introduction

01323 . 1 = , because the unit of K is [bar].

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