VMG Packages

This document is intended to assist iPRSM users in selecting the VMG Thermo vapor & liquid
property packages which best suit their compound stream composition and flashing conditions.
The information in the following pages has been provided by the Virtual Materials Group. The source
of the information is as follows.
Pages Section Content From Manual

2-5 VMG Thermo 8.0 Release Notes VMG Thermo v. 9.5
6-10 Property Packages Introduction VMG Sim v. 9.0
11-12 Choosing Thermodynamic N/A
Models
13-17 Introducing Equations of State VMG Sim v. 9.0
18-33 Property Package Equations N/A
Copyright (c) 2002-2015Virtual Materials Group, Inc. All Rights Reserved
VMG has given permission to Curtiss Wright to publish this VMG documentation in electronic format
in connection with the iPRSM software product.
For further questions or consultation please contact support@virtualmaterials.com.

VMGThermo v. 9.5 Manual 2
Welcome to VMGThermo
Version 8.0
Released November 2013.
The new features, changes, and bug fixes for VMGThermo 8.0 are summarized below.
Thermodynamics
New Features
1. Support for VMGThermo in 64 bit including the C, COM and Matlab interface. Both, 32 bit and 64 bit files are
included in the same installer.
2. Added the Expanded Fluid Model, developed by Marco Satyro and Harvey Yarranton, to the list of available
viscosity models in VMGSim.
This model was developed and tested for light hydrocarbons, conventional crude oil, heavy oils and
their mixtures as a function of temperature and pressure and can be extended to natural gas processing applic-
ations
4. NHV calculations have been enhanced to take into account metals that could be present in the formula of an
oil pseudo component
5. Added interaction parameters for TTEG/H2O in APR
6. SARA Regular Solution property package. This property package will allow for enhanced modelling of
asphaltene precipitation, enabling estimation of asphaltene yield, asphaltene precipitation onset and
asphaltene properties.
7. New "Water-Oil Residue" flash option for difficult heavy oil and water phase separation process conditions
when a maximum of 2 liquid phases is desired.
8. Added liquid density and CASN to database for component 1-butyl-3-methylimidazolium bis[(tri-
fluoromethyl)sulfonyl]imide and 1-ethyl-3-
9. Added and re-regressed the hydrate calculation package to include the most up to date published data:
nitrogen
carbon dioxide
hydrogen sulfide
methane
ethane
propane
isobutane
n-butane
Copyright (c) 1999-2011 Virtual Materials Group, Inc. All Rights Reserved support@virtualmaterials.com
cyclopentane
cyclohexane
neopentane
benzene
isopentane
2,2-dimethylbutane
2,3-dimethylbutane
2,2,3-trimethylbutane
3,3-dimethylpentane
methylcyclopentane
methylcyclohexane
cis 12 dimethylcyclohexane
ethylcyclopentane
1,1-dimethylcyclopentane
cycloheptane
cyclooctane
ethylene
acetylene
propylene
3,3-dimethyl-1-butene
xenon
2,3-dimethyl-1-butene
2,2-dimethyl-pentane
ethylene oxide
cyclopropane
carbonylsulfide
sulfur dioxide
methyl mercaptan
Inhibitors
Methanol
Ethylene Glycol
Triethylene Glycol
Ethanol
Glycerol
Changes
1. Improved solubility of mercaptans in natural gas based on GPA Research Report 113, GPA Research
Report 135
2. Use Steam 97 as the default for steam calculations in APR/APRNG (changed from slower Steam 95)
3. Update TEG/Water interaction parameters in APR for Natural Gas property package to match correlations
developed by Parrish et (1986)
4. Improved property estimation of EG/Water, DEG/Water and TEG/Water in APR to match predictions from
APR for Natural Gas.
( based off the GPSA Thermal Conductivity, Viscosity, Heat Capacity)
Bug Fixes
1. Hydrate - Enhanced overall convergence of hydrate calculations
2. Liquid density @ 298 K is now estimated for pure compounds that are missing this property in the database
Oil Characterization
New Features
1. Added a new extrapolation method for heavy oil’s normal boiling point curves when asphaltene information
is available
2. Oil pseudo component Chemical Formulas can contain metals (V, Ni, Fe) in their formulas if the metals
content curves are provided
3. Improved the Cn Compositional Analysis option in the Oil Characterization by allowing the use of oil’s bulk
Molecular Weight or Liquid Density at 60 F to perform the characterization when Plus Fraction Molecular
Weight or Liquid Density at 60 F are missing
4. Added the Beggs-Robinson correlation to the list of viscosity estimation methods in the Oil Characterization
ranges.
The data set for which this relationship was obtained included an API gravity range between 16 and 58 and a
temperature range of 70 to 295 F.
This correlation is recommended for light to medium oils
Changes
1. Improved the calculation of oil bulk ABP when a D86 distillation curve is added as Experimental Information.
In this case, the bulk ABP will be obtained directly from the available D86 curve. The different definitions for
bulk oil ABP’s were also added and shown in the Report form of the Oil Characterization
2. The default Chemical Formula estimation method in the Oil Characterization changed from API (Auto) to
API/Content Curves (Auto / Content Curves) in order to always take into account any user elemental
distribution in the calculation of the pseudo components Chemical Formula
Bug Fixes
1. Avoided the calculation of non-monotonic distillation curves by automatically changing the interpolation
method to Linear when local minima or maxima are found
2. The API-VMG viscosity estimation method is not reliable for very light hydrocarbons (API > 70 and KW <
12).
This estimation method is replaced with the Letsou Stiel method when the wrong slope of viscosity vs. tem-
perature is obtained for light oil pseudo components
3. Fixed the interpolation of the D86 Distillation Curve when experimental data is available below 10% or above
95% distillation
VMGSim v. 9.0 Manual 3
Property Package
Basic Property Package Skills
No matter how complex or how simple your simulation is, the quality of the results will depend on the quality of
the underlining thermodynamic methods used to estimate the state of ports as well as the methods used to
estimate transport and physical properties such as densities and viscosities.
A property package is an aggregation of methods that define how thermodynamic equilibrium (and consequent
number of phases and phase amounts) and physical properties of interest are to be calculated. VMGSim uses
the VMGThermo property package system to power all of its thermodynamic calculations.
Consult the VMGThermo manual for detailed descriptions on all property packages available in VMGSim. If you
are unsure about how to best use the available property packages for your specific applications contact the
VMG office nearest to you.
One important concept to keep in mind is that no property package will be able to solve all problems of interest.
In a nutshell, available thermodynamic models are too simplistic to solve all problems. Therefore, property pack-
ages are implemented in such a way as to solve classes of problems. For certain classes of problems we can
craft specialized equations of state or activity coefficient methods, and thanks to careful and extensive fitting of
experimental data reliable thermodynamic models can be created.
VMGThermo has some of the most extensive and well documented thermodynamic model interaction para-
meter libraries in the world. Virtual Materials Group is a sponsor of the Thermodynamics Research Center at
the National Institute of Standards and Technology in Boulder, Colorado. Therefore we have the most up-to-
date and comprehensive data collection in the world.
Consult us for any specific needs you may have related to physical properties and applied thermodynamics.
A property package, no matter how sophisticated it is, is kind of useless without a robust multiphase flash
algorithm. VMGSim uses the industry proven VMGThermo multiphase flash for all thermodynamic equilibrium
calculations.
From a certain point of view, a property package is a collection of equations that describe the behavior of
nature, and a property package system such as VMGThermo contains a multiphase flash to solve the ther-
modynamic equilibrium calculations and carefully orchestrate the solution and calculation of required physical
properties.
Since VMGSim is completely interactive and it tries to use all information supplied by the user, the flash system
also has to be very flexible and capable to accept many different specifications of intensive variables, such as
pressure, temperature, enthalpy, etc.
Choosing Property Packages

Property packages can be broadly divided into three groups based on the way fugacity calculations are per-
formed. After you understand how property packages are classified then you can look at them from your own
mixture and process perspective and choose an appropriate property package.
From a process modeling point of view property packages can be divided in the following categories:
• Equations of State
• Activity Coefficient Models
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• Specialty Packages
Property Package Model Types

The basic problem we face when creating thermodynamic models for process simulation is how to determine
the thermodynamic state of a fluid. In another words, given two intensive variables (let’s say pressure and tem-
perature) and a bulk composition, how many phases and what are their compositions and amounts exist in ther-
modynamic equilibrium.
Thermodynamic equilibrium is a very useful boundary condition. In a nutshell, phases are said to be at ther-
modynamic equilibrium if their pressures, temperatures and chemical potentials are the same. The equality of
pressure and temperature across the phases guarantee that there’s no heat flow or mechanical work done by
the system. The equality of chemical potentials amongst all components in all phases ensures that there’s no
mass transfer across the phases.
Thus a system at thermodynamic equilibrium represents an abstraction where all the transformations that we
would like to have made on a fluid are made and no macroscopic changes are happening. For example, dis-
tillation tower trays and separators approximate a state of thermodynamic equilibrium.
Systems that are NOT at equilibrium are systems that experience changes with time.
The facet of chemical engineering thermodynamics that’s of greatest interest for us is the framework used to
express the equality of chemical potentials for all components across all phases. This is conveniently done
using fugacities as shown in equation 1.
1
The quantity f is the fugacity, the index “i” represents a component in the mixture and the superscript in Roman
numbers represent the phase of interest. For example, I could represent a vapor, II a liquid and so on. Finally
“np” stands for number of phases. Note that equation 1 is applied to all components in the mixture.
Equations of State Models
Equations of state models start from equation 1 and use pressure-temperature-volume-composition rela-
tionships anchored by rigid thermodynamic relationships to create expressions for the fugacity of individual com-
ponents. These relationships are usually expressed in terms of a fugacity coefficient and equation 2 is the
workhorse for equations of state models.
2
Equations of state are widely used for hydrocarbon processing.
Equations of State Models

Ideal Areas
l Simple and fast, pure component and mixture parameters easily generalized for hydrocarbons
l Consistent across the mixture critical point
l High and low pressure sections of a plant can be modeled using a consistent model.
l Good results for certain classes of problems (e.g. natural gas modeling, refinery modeling)
l Can be used with minimal amount of experimental data

l Can provide other derived physical properties in a consistent manner such as densities, entropies, enthal-
pies and heat capacities.
Drawback Areas
l By default are not accurate enough for modeling polar compounds (more advanced equations of state
such as GE-PR can nevertheless be used for the modeling of polar systems).
l Usually default liquid density predictions are not accurate enough for process design work. More
advanced equations of state such as Advanced_Peng-Robinson have methods designed to correct this
inaccuracy.
l Need critical properties and acentric factor for pure components.
l Require good experimentally based interaction parameter database and special generalizations for spe-
cial classes of compounds such as hydrocarbon/hydrocarbon, hydrocarbon/light gases, hydro-
carbon/water, etc.
l Pure component vapor pressures, unless specially fitted, are estimated using critical properties and
acentric factor. This can be inaccurate for heavy oils and polar compounds.
Avoidable Areas
l Unless heavily modified they can not be used out of the box for calculations related to environmental prob-
lems. Usually equations of state are tuned to provide a good estimate of water in the hydrocarbon phase,
but the amount of hydrocarbon in the water phase is usually poorly predicted.
l Sometimes they may predict incorrect phase split.
l Good liquid densities are obtained by using volume translation. Sometimes in extreme conditions neg-
ative liquid volumes can be calculated.
l Some implementations in the literature are plagued by discontinuities, inconsistencies and sometimes
plain mistakes. Love and tender care are required to move what’s published to what is of sufficient quality
for industrial use.
l Most improvements reported over the last decade in cubic equations of state are truly marginal.
Activity Coefficient Models

Activity coefficient models start from equation 1 but instead of using a consistent model for the vapor and liquid
phases the problem is split into having a model for the vapor phase and a separate model for the liquid phase.
This approach buys flexibility at the expense of consistency, and for many years it was the method of choice for
the modeling of aqueous, polar systems.
3
The term f0 is the standard state fugacity of a component “i” at the system pressure and temperature. Although
it is possible to develop a comprehensive framework using equation 3, the use of activity coefficients for the
vapor phase is not aesthetically pleasant and usually equation 3 is cast into its more familiar form, equation 4.
The superscript is used to denote a vapor phase.

In turn, the activity coefficient can be expressed as in equation 5, and the standard state fugacity can be
expressed as in equation 6.
6
One common snag with the use of equations of 5 and 6 is related to light gases. Usually these gases are
present in a system at a temperature well beyond their critical temperatures and therefore the use of a vapor
pressure Pv is not appropriate. In these cases it is common to express the fugacity of these compounds in liquid
phases by the use of a Henry constant as shown in equation 7.
7
Activity coefficient models are commonly used for the modeling of systems where the liquid phase non-idealities
are important, such as aqueous systems.
Ideal Areas
l Activity coefficient models can be quite flexible and able to fit complicated VLE and LLE behavior
l Coupled with a virial equation of state they can be used to model associating systems such as systems
containing formic and acetic acid.
l Pure component vapor pressure accuracy is limited only by the accuracy of experimental data and fitting
function.
l VMGThermo has extensive libraries of fitted interaction parameters for many systems of interest.
l First approximations for activity coefficient values can be determined using UNIFAC.
Drawback Areas
l Property packages using activity coefficients can not be consistent across the critical point.
l Sometimes temperature dependent interaction parameters are required, and those may extrapolate
poorly.
l Only excess enthalpies and Gibbs free energies can be derived from the model. A separate enthalpy,
entropy and heat capacity models are required, as well as a separated model for the density.
Avoidable Areas
l If no interaction parameters are available some methods default to ideal solution (Margules, van Laar,
NRTL) while others have a leftover part coming from pure component molecular parameters (Wilson,
TK-Wilson, UNIQUAC). Thus without interaction parameters no qualitative predictions are available.
Sometimes simple cubic equations of state will still provide a qualitative correct picture of thermodynamic
equilibrium even without interaction parameters.
l Some activity coefficient models can not predict the existence of multiple liquid phases such as Wilson.

Specialty Property Packages

Specialty property packages are used to model specific processes for which the general framework provided by
activity coefficient and equation of state models is not adequate. Usually specialty property packages are
designed to solve specific processes, some of which have chemical reactions happening throughout, such as
urea, sour water, sulfuric acid and amine processes. Please consult the VMGThermo for detailed information
on specialty property packages.
Rough screening of property packages

The figure below is a suggestion on how to choose property packages. Since property packages are based on
empirical and semi-empirical methods and your system and system conditions can vary significantly from the
conditions and systems used to create a given property package it is recommended that you carefully examine
the answers from the simulation. In doubt contact the Virtual Materials Group representative closest to you.

Choosing Thermodynamic Models Page 1 of2
Choosing Thermodynamic Models
The proper choice of thermodynamic models is the most important step you will take for the correct modeling your system. The treediagram below shows some basic
decisions basedongeneric information about the system you are modeling.
Get used to ask yourself questions about the process your are going to model. For example, are you looking at a hydrocarbonsystem? Do you have polar substances in the
process? What are the pressures and temperatures of interest? Do I have carboxylic acids present?
More:
Hydrocarbon Processing
Chemicals

Hydrocarbon Processing
Hydrocarbon processing covers a wide range of process conditions from near vacuum up to pressures well above 20000 kPa. Also, hydrocarbon processing may involve
highly polar substances such as water, methanol and glycols.
Processes without polar substances
Some hydrocarbon processesdonot involve polar substances, such as Styrene purification and ethane/ethylene or propane/propylene separations. In those cases, vapor
pressures andrelative volatilities are of fundamental importance for proper modeling, and the decision on using a property package over another is dependent on pressure and
vapor pressure prediction.Usually simple cubic equations of state (REFINERYSRK, SRK, PR, APR) will not be adequate for vacuum distillation of chemicals such as
Copyright(c)2002-2015VirtualMaterialsGroup,Inc.AllRightsReserved support@virtualmaterials.com
Choosing Thermodynamic Models Page 2 of2
styrene because the low temperature vapor prediction from these models is not accurate enough. Many times this inadequacy manifests itself as badly predicted reflux rates in
distillation towers, which have specifications in composition. For processes at 1 atm and above usually APR will provide reasonable vapor pressure predictions. Please note
that forhighpressure superfractionation such as propane/propylene splitting results are sensitive to interaction parameters used.
Note that isomerseparations are usually problematic, and it is recommended that a check on Virtual Materials vapor pressure prediction be performed on each isomer
(Agarwal et al, 2000).
Natural Gas Processing
Natural gasprocesses are conveniently modeled using APR. APR incorporates special correlations for water and polar compounds normally found in natural gas processing as
well as estimates for water solubility in hydrocarbons. Also, APR has consistent densities for the gas and liquid phases andallows smooth property calculations across the
mixture critical point.
Refinery
Refinery processes are conveniently modeled using APR or REFINERYSRK. Both models include special correlations for modeling hydrogen. APR will provide more
accuratedensity predictions than REFINERYSRK.
Environmental Alert: If you areperforming calculations for environmental impact studies or related applications, you should be aware that, while the prediction of water in
the hydrocarbon phase using APR or REFINERYSRK is reasonable, the prediction of hydrocarbon in the water phase is poor and should not be used for process calculations.

Chemicals
The basic questiononchemical processing is the pressure you are interested at, as it will determine if anequation of state or activity coefficient model will be necessary.
High Pressure
If vaporliquid equilibrium is important, GEPR is usually the best choice.
Association Alert: If your system contain carboxylic acids at high pressure then GEPR is not adequate and youshoulduse an activity coefficient model with Hayden
O'Connell for the vapor phase. This should be adequate for pressures corresponding toupto 50% of the mixture critical density.
If your model haslow pressure distillation and high pressure intermediate equipment (for example compressorsand reactors), a good model can be created by using SRK,
REFINERYSRK, PR, APR for the gas phase andWilson, NRTLor UNIQUAC for the liquid phase. The RK model is provided for compatibility with older calculations, and
should not be used for new calculationsas it is significantly less accurate than the more modern SRK and PR equations. See the methods AddAggregatePkgFromId and
AddAggregatePkgFromName for more details.
If you are performing initial design work, and you have little or no information about the mixture of interest, a useful method is PSRK (predictive SRK). It combines a
modification of the SRK equation of state designed to accurately model the vapor pressure of polar and nonpolar substances andthe UNIFAC method, with specially
determined atomic groups for common industrial gases. It can be used for low and highpressure conditions.
Low Pressure
Lowpressure equilibriumcalculations are usually complex due to large polar interactions between chemicalsin theliquid phase and sometimes we will find truly anomalous
behavior in the gas phase when carboxylic acids are present
Carboxylic Acids Are Present
InthiscasetheuseoftheHaydenO'Connellmodelforthegasphaseisessential.Failureofdoingsowillresultinwrongphaseequilibriumandphysicalpropertiessuchas
gas density. Usually activity coefficient models such as Wilson, NRTL or UNIQUAC will work well.
Systems That may phase split
If your mixture can phase split (for example, it contains water and hydrocarbons or heavy alcohols) and no carboxylic acids usually NRTL and UNIQUAC will be adequate
with ideal gas law for the gas phase. Ifyou have carboxylic acids make sure you use HaydenO'Connell forthe gas phase
Systems that do not phase split
Usually thebest model for theliquid phase for systems which do not phase split is Wilson, with ideal gas for the gas phase (or HaydenO'Connell if the system has carboxylic
acids).

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Thermodynamic Models
Equations of State
Advanced_Peng-Robinson (APR)
The Advanced Peng-Robinson model has all the characteristics of the Peng-Robinson model plus volume
translation for accurate liquid phase density estimation using the Peneloux (1980) idea as modified by Mathias
et al. (1991). It deals with polar components that are seen in these areas in a more appropriate way than the
Peng Robinson (PR) equation of state does. It also has a large set of interaction parameters for temperature
dependent situations, as well as volume translation to improve liquid density calculations.
Advanced Peng Robinson for Natural Gas

Much like the APR property package, the Advanced Peng Robinson for Natural Gas (APRNG) modifies the ori-
ginal Peng Robinson equation of state. It is more specialized than the APR property package. The APR for Nat-
ural Gas package is best suited for the solubility of hydrocarbons in water, as well as mercury. The APRNG
package is specifically designed for calculating water content in acid gas, hydrate inhibition, glycols and hydro-
carbon solubility. It is also good with polar components, which is similar to the APR property package.
Benedict-Webb-Rubin and Benedict-Webb-Rubin-Starling (BWR and

BWRS)
One of the oldest equations of state used in technical calculations, the BWR equation of state was originally
developed to fix problems encountered in the older Beattie_Bridgeman equation of state around the critical
point. This was accomplished by adding an exponential term to the equation which effective captures the resid-
uals one would have from a purely virial based equation of state as BB. There are very many versions of BWR
and VMGSim uses the form defined by Starling. We use Starling’s formulation since it was extensively tested
for natural gas mixtures. BWRS is an extension to BWR where the BWR parameters were generalized as func-
tions of the acentric factor, thus allowing the equation to be used for components for which experimentally
determined parameters are nor available. Avoid using BWR and BWRS for aqueous systems.
Gibbs Excess Peng-Robinson (GEPR)

GEPR is Virtual Materials Group implementation of Huron-Vidal mixing rules. The PR equation of state is mod-
ified to use the Mathias-Copeman approach to model pure component vapor pressures. The Gibbs excess
model used in GEPR is NRTL and the model is a powerful and flexible framework to model complex chemical
systems. GEPR is an advantageous model to use when dealing with polar systems which are processed at
high and low pressures since a consistent model can be created. GEPR also uses volume translation for
increased accuracy on liquid density predictions.
HaydenOConnell
The Hayden-O’Connell equation of state is used ONLY in conjunction with activity coefficient models. Since it is
a second virial coefficient based equation of state only gas phase physical properties are calculated. Use Hay-
denOConnell with an activity coefficient method when modeling dimerizing systems such as systems containing

acetic acid. The Hayden-O’Connell model will also estimate implicit enthalpies, entropies and dimerization heat
capacities.
NGL-PR
NGL-PR is Virtual Materials Group implementation of the Peng-Robinson equation of state as specified by the
GPA. NGL-PR also implements the necessary pure component physical property estimation methods and
default interaction parameters for Peng-Robinson as specified in the GPA research reports. NGL-PR also uses
volume translation to increase the accuracy of liquid density predictions. Volume translation is NOT specified by
the GPA’s research reports.
PRSK
The predictive SRK model combines the predictive capabilities of the UNIFAC activity coefficient estimation
method with the flexibility and convenience of a cubic equation of state. PSRK matches the UNIFAC model
with the equation of state model at low pressure and therefore the large UNIFAC atomic group interaction para-
meter matrix can be reused. PRSK also defines a series of new atomic groups for light gases such as nitrogen
and methane. Virtual Materials Group implementation also includes volume translation for increased accuracy
in the prediction of liquid phase densities.
Redlich-Kwong (RK)
The RK equation of state is included in VMGThermo to provide compatibility with other property packages. Usu-
ally RK is used in combination with activity coefficients to provide a model for the gas phase. RK is also the
vapor phase model used in the Chao-Seader and Grayson-Streed correlations.
Refinery-SRK
Refinery-SRK is Virtual Materials Group of the SRK equation of state as specified in the API handbook. This
implementation of SRK handles hydrogen and helium, and it uses a slightly different acentric factor gen-
eralization as compared to Soave’s original work. Interaction parameters are implemented as specified in the
API manual.
SARA Regular Solution
SARA Regular Solution is designed specifically to support SARA (saturates, aromatics, resins, asphaltenes)
characterization and asphaltene washing using hydrocarbon solvents. The SARA Regular Solution property
package allows for more accurate modeling of asphaltene precipitation processes through the estimation of
asphaltene yield, asphaltene precipitation onset and asphaltene physical properties.
In order to make use of this new package in VMGSim a SARA characterization of the oil is needed. Depending
on the information available, the saturates, aromatics, resins and asphaltenes will all be characterized sep-
arately either as hypothetical compounds or through the oil characterization environment. Commonly, the sat-
urates and aromatics will be characterized as hypothetical components and the resins and asphaltenes will be
characterized using the Gamma Characterization in the oil characterization environment. When the resins and
asphaltenes are characterized the appropriate chemical families are assigned to the pseudo-components and
the appropriate physical properties for pure components and mixtures are automatically calculated.

Steam95
The steam package is Virtual Materials Group implementation of the 1995 standard for water and steam.
Steam97
The steam package is Virtual Materials Group implementation of the 1997 standard for water and steam.
Soave-Redlich-Kwong (SRK)
SRK is a standard implementation of the SRK equation of state. Liquid densities from SRK are not reliable.
Unless you need to use a standard SRK for some special reason please consider using Refinery-SRK.
For detailed description of property packages please consult the VMGThermo Methods manual.
If you are developing solutions based on VMGThermo you may also find the VMGThermo Programmer’s
manual useful.

Activity Coefficient Methods

Ideal
Assume that all activity coefficients are equal to zero. Gas phase is assumed ideal.
Chao-Seader
Use the Chao-Seader method for the calculation of gas and liquid fugacity coefficients. RK is used for the gas
phase and regular solution is used for the liquid phase together with a specially fitted function for hydrocarbons
standard state fugacity. Water decantation is provided, and a pure water phase is assumed while water sat-
urated hydrocarbon phase is calculated when appropriate. Unless needed, the Grayson-Streed method should
be used instead of Chao-Seader.
Grayson-Streed
Use the Grayson-Streed method for the calculation of gas and liquid fugacity coefficients. RK is used for the gas
phase and regular solution is used for the liquid phase together with a specially fitted function for hydrocarbons
standard state fugacity. Water decantation is provided, and a pure water phase is assumed while water sat-
urated hydrocarbon phase is calculated when appropriate. The method also provides better estimates of hydro-
gen and hydrogen sulfide solubilities in hydrocarbons than Chao-Seader.
Margules
Use the Margules three suffix activity coefficient equation to model the liquid phase activity coefficients. Gas
phase is assumed ideal.
Margules4
Use the Margules four suffix activity coefficient equation to model the liquid phase activity coefficients. Gas
NRTL
Use the Non Random Two Liquids (NRTL) equation to model the liquid phase activity coefficients. Gas phase is
assumed ideal by default, but will be set to Virial if you choose Associating System from the property package
selection menu.
UNIFAC
Use the UNIFAC atomic group contribution method to model the liquid phase activity coefficients. Gas phase is
assumed ideal.
UNIQUAC
Use the Universal Quasi Chemical Activity Coefficient theory to model the liquid phase activity coefficients. Gas

Van Laar
Use the Monsanto definition of van Laar as described in the open literature to model the liquid phase activity
coefficients. Gas phase is assumed ideal.
Wilson
Use the Wilson activity coefficient equation to model the liquid phase activity coefficients. Note that this property
package can not predict the existence of two or more liquid phases. Gas phase is assumed ideal.
For detailed description of property packages please consult the VMGThermo Methods manual.
If you are developing solutions based on VMGThermo you may also find the VMGThermo Programmer’s
manual useful.

Summary of Virtual Materials Group Property Packages
Cubic Equations of state
Introduction
Cubic equations of state are presented in many different ways. Nevertheless, for simple cubics with covolume
independent of temperature a simple set of equations suffices to describe all different cubic equations of state.
RT a
P= − 2 1
V − b V + ubV + wb 2
a = acα (T ) 2
( ) ( )
Z 3 − 1 + B − uB 2 Z 2 + A + wB 2 − uB − uB 2 Z − AB − wB 2 − wB 3 = 0 3
aP
A= 4
(RT )2
bP
B= 5
RT
Basic Model u w ac b
RK 1 0 Ω A R 2Tci2.5 Ω B RTci
Pci Pci
SRK Family 1 0 Ω A R 2Tci2 Ω B RTci
Pci Pci
PR Family 2 -1 Ω A R 2Tci2 Ω B RTci
Pci Pci
∆A =
a
ln
(
2Z + B u − u 2 − 4w ) − RT ln(Z − B ) 6
b u − 4w2
2Z + B (u + u − 4w )
2
1 da 2Z + B (u − u − 4 w )
2
∆S = R ln (Z − B ) − ln 7
b 2 u − 4 w dT 2Z + B (u + u − 4w )
2
∆H = ∆A + T∆S + RT (Z − 1) 8
∂ P
∆Cv = T ∫  2 dV − R
V 2
∞
∂T 
9
 ∂P 
 
2
 ∂T V
 ∂P 
∆C p = ∆Cv − T
 
10
 ∂V T
__________________________________________________________________________________________
 ∂P 
  =
RT da 1
 ∂T V V − b dT V + ubV + wb
− 2 2
11
 ∂P 
  =−
RT 2a (V + b )
 ∂V T
+ 2 12
2
(
(V − b ) V + ubV + wb 2 ) 2
 ∂2P 
∫  ∂T 2  dT 2 b u 2 − 4w 2Z + B u + u 2 − 4w
 
V
d 2a 1 (
2Z + B u − u 2 − 4w )
∞
= − ln 13
( )
1 1  ∂Z 
Iso = −  
P Z  ∂P T
(Isothermal Compressibility) 14
1  ∂V 
 
V  ∂T  P
β= (coefficient of thermal expansion) 15
As long as we have available ideal gas heat capacities, enthalpies, entropies and heat capacities can be computed
from the equation of state, and therefore a complete, consistent and simple model for fluids can be constructed. The
different cubic equations of state address the issues of accuracy with respect to vapor-liquid equilibrium and density
in different ways. We will examine each of the available equations of state in VMGThermo in the next section.
__________________________________________________________________________________________
Advanced Peng-Robinson – VMG’s Recommended Default Method for
Hydrocarbon Systems
The Advanced Peng-Robinson model has all the characteristics of the Peng-Robinson model plus volume translation
for accurate liquid phase density estimation using the Peneloux (1980) idea as modified by Mathias et al. (1991).
Equation Settings
Omega A Omega B Alpha (T) Mechanical Zc

0.457235 0.0777969
(1 + f (1 −
wi Tri ))
2 0..307
f wi = 0.37464 + 1.54226wi − 0.26992wi2 if wi < 0.5 16

2 3
f wi = 0.3796 + 1.4850wi − 0.1644w + 0.01666w otherwise
i i 17
Special Treatment for Pure Compounds

Specially fitted alpha functions for water, ammonia, hydrogen sulfide, urea, hydrogen, helium, methanol, ethylene
glycol, diethylene glycol and triethylene glycol
a = ∑∑ (1 − kij ) ai a j xi x j
Mixing Rules
b = ∑ xibi 18
kij1
kij = kijo + + kij2 ln T
T
Volume translation
The Peng-Robinson model does not provide an accurate enough model for liquid densities, especially for polar
compounds. Therefore, a volume translation as suggested by Peneloux (1980) and further modifications suggested
by Mathias et al. (1991) is used in APR In addition, as special mixing rule for the calculation of excess volume
translations is used, thus allowing the calculation of accurate mixture densities. The Mathias modification for the
calculation of liquid densities is given by the following equations:
 0.41 
V corr = V + s + f c  
 0.41 + δ 
19
 ∂P 
 
V2
 ∂V T
δ =− 20
RT
f c = Vc − (3.946b + s ) 21
Where s is an adjustable parameter determined for each pure component. For mixtures the parameter s is defined by
the equation below:
__________________________________________________________________________________________
smix = ∑ si xi + s Excess (T , x )
r
22
i
Default Interaction Parameters - VLE

Hydrocarbon/Hydrocarbon, Carbon Dioxide/Hydrocarbon, Nitrogen/Hydrocarbon and Hydrogen
Sulfide/Hydrocarbon interaction parameters are estimated using the Nishiumi et al. (1988) method.
Interaction parameters between water and hydrocarbons are calculated using a modification of Tsonopolous and
Heidman method (1986)
The default PR database has all the interaction parameters for the binaries reported by Knapp et al. (1982) with
modifications for hydrogen and helium.
Proprietary interaction parameters for Triethylene Glycol and Carbon Dioxide, Hydrogen Sulfide, Methane, Ethane,
Propane, Benzene, Ethyl Benzene, Xylenes and Water.
Proprietary interaction parameters for Ethylene Glycol / Water, Diethylene Glycol / Water and Tetraethyelene
Glycol / Water
Environmental Alert: The interaction parameter between water and hydrocarbons will provide a reasonable
estimate of the solubility of water in hydrocarbons but the estimated solubility of hydrocarbons in water will not be
reliable. Do not use this model if you are performing environmental impact studies.
Default Interaction Parameters – Liquid Density

Parameters for the binary Urea/Water are provided.
Unknown binary parameters are set to zero.
__________________________________________________________________________________________
Peng-Robinson
The Peng-Robinson (Peng and Robinson, 1976) equation of state was designed to provide better liquid densities
than the SRK equation of state as well as better vapor pressures for hydrocarbons in the gasoline range.
Equation Settings
0.457235 0.0777969
(1 + f (1 −
wi Tri ))
2 0..307
f wi = 0.37464 + 1.54226wi − 0.26992wi2 if wi < 0.5 23

2 3
f wi = 0.3796 + 1.4850wi − 0.1644w + 0.01666w otherwise
i i 24

a = ∑∑ (1 − kij ) ai a j xi x j
Mixing Rules
b = ∑ xibi 25
kij1
T
Default Interaction Parameters

Hydrocarbon/Hydrocarbon, Carbon Dioxide/Hydrocarbon, Nitrogen/Hydrocarbon and Hydrogen
Sulfide/Hydrocarbon interaction parameters are estimated using the Nishiumi et al. (1988) method.
Interaction parameters between water and hydrocarbons are calculated using a modification of Tsonopolous and
Heidman method (1986)
The default PR database has all the interaction parameters for the binaries reported by Knapp et al. (1982) with
modifications for hydrogen and helium.
Proprietary interaction parameters for Triethylene Glycol and Carbon Dioxide, Hydrogen Sulfide, Methane, Ethane,
Propane, Benzene, Ethyl Benzene, Xylenes and Water.
Proprietary interaction parameters for Ethylene Glycol / Water, Diethylene Glycol / Water and Tetraethyelene
Glycol / Water
__________________________________________________________________________________________
NGL Peng-Robinson
The Peng-Robinson (Peng and Robinson, 1976) equation of state was designed to provide better liquid densities
than the SRK equation of state as well as better vapor pressures for hydrocarbons in the gasoline range. The GPA-
PR model implements the exact definition of the Peng-Robinson equation of state as specified by the GPA RR-28
(Robinson and Peng, 1978) , including the GPA recommended methods for the estimation of pure component
physical properties for oil fractions.
Equation Settings
0.457235 0.0777969
(1 + f (1 −
wi Tri ))
2 0..307
f wi = 0.37464 + 1.54226wi − 0.26992wi2 if wi < 0.5 26

f wi = 0.3796 + 1.4850wi − 0.1644wi2 + 0.01666wi3 otherwise 27

a = ∑∑ (1 − kij ) ai a j xi x j
Mixing Rules
b = ∑ xibi 28
kij1
T

Same as Advanced Peng-Robinson
For binary pairs without interaction parameters, estimated values are provided depending on the compounds making
up the binary pair according to the GPA recommended methods:
Nitrogen / Paraffins
Nitrogen / Naphthenes
Nitrogen / Aromatics
Carbon Dioxide / Paraffins
Carbon Dioxide / Naphthenes
Carbon Dioxide / Aromatics
Hydrogen Sulfide / Paraffins
Hydrogen Sulfide / Naphthenes
Hydrogen Sulfide / Aromatics
Methane / Aromatics
Methane / Naphthenes
Ethane / Aromatics
Ethane / Naphthenes
Propane / Aromatics
Propane / Naphthenes
Hydrocarbons / Water
__________________________________________________________________________________________
If no interaction parameters are available after all the estimations as defined by GPA were performed then the
estimation methods used by Advanced Peng-Robinson are used.
reliable. Do not use this model if you are performing environmental studies.
__________________________________________________________________________________________
Huron-Vidal-Peng-Robinson (GEPR)
The Huron-Vidal Peng-Robinson model has a different mixing rule designed to incorporate a Gibbs Excess model
into the equation of state as described by Huron and Vidal (1979) and in principle model mixtures with strong non-
idealities in the liquid phase. It also incorporates the volume translation from Advanced Peng-Robinson as
discussed in the Advanced Peng-Robinson section.
Equation Settings
0.457235 0.0777969 (1 + f (T )) 2 0..307
( ) (
f (T ) = 1 + Ai 1 − Tri + Bi 1 − Tri ) + C (1 −
2
i Tri )
3
29
The constants A, B and C are determined for each individual compound by fitting the vapor pressure over the range
defined by the vapor pressure correlation. Extrapolation beyond the critical point is done using the method
suggested by Mathias (1980).
Mixing Rules
a = b ∑ i xi − σG∞E 
 nc a 
 i=1 bi 
b = ∑ xi bi
30
Where GE is given by the NRTL model and σ is a numerical constant for Peng-Robinson.
Volume translation
Same as in Advanced Peng-Robinson
Default Interaction Parameters – VLE

Unknown interaction parameters are set to zero
Environmental Alert: GEPR can provide accurate LLE predictions for water and hydrocarbon rich phase as long
as interaction parameters are provided. If you are making environmental impact studies make sure the appropriate
interaction parameters are used
Default Interaction Parameters – Liquid Density

Unknown binary parameters are set to zero.
__________________________________________________________________________________________
Soave-Redlich-Kwong (SRK)
The Soave-Redlich-Kwong (Soave, 1972) equation of state accurately models the vapor pressures of light
hydrocarbons and light gases at pressures at or above atmospheric.
Equation Settings
0.42748 0.08664
(1 + f (1 −
wi Tri ))
2 1
3
f wi = 0.48 + 1.574wi − 0.176 wi2 31

Specially fitted alpha functions for water, ammonia, hydrogen, helium, methanol, ethylene glycol, diethylene glycol
and triethylene glycol
a = ∑∑ (1 − k ij ) ai a j xi x j
Mixing Rules
b = ∑ xi bi 32
o
k ij1
k ij = k +
ij + k ij2 ln T
T

Interaction parameters for hydrocarbons and hydrogen sulfide, methyl mercaptan and carbon disulfide are calculated
using the Won et al. (1981) method.
Interaction parameters between water and hydrocarbons are set to 0.5.
The default SRK database has all the interaction parameters for the binaries reported by Knapp et al. (1982)
__________________________________________________________________________________________
Refinery-SRK
The SRK implementation suggested by the API (API, 1992) uses the basic structure defined by the original SRK
equation of state (Soave, 1972) with the modifications described below.
Equation Settings
0.42747 0.08664
(1 + f (1 −
wi Tri ))
2 1
3
f wi = 0.48508 + 1.55171wi − 0.15613wi2 33

Specially fitted alpha functions for water, ammonia, hydrogen, helium, methanol, ethylene glycol, diethylene glycol
and triethylene glycol. The hydrogen alpha function is modified to avoid minimum predicted by Soave's original
equation according to the values published by Graboski and Daubert (Graboski and Daubert, 1978c).
Hydrogen Handling
API used a specific set of critical temperature and pressure for hydrogen. In order to access these specific constants
use the component API-HYDROGEN defined in VMG pure component database. If you use VMG's standard
HYDROGEN component the results will differ from the results expected based on API's procedure.
a = ∑∑ (1 − kij ) ai a j xi x j
Mixing Rules
b = ∑ xibi 34
kij1
T

Interaction parameters for hydrocarbons and methyl mercaptan and carbon disulfide are calculated using the Won et
al. (1981) method.
Interaction parameters between water and hydrocarbons are set to 0.5.
Generalized functions for estimating interaction parameters between H2S / hydrocarbons, CO2 / Hydrocarbons and
Nitrogen / hydrocarbons as defined by the API.
All binary interaction parameters between hydrocarbons set to zero
All hydrogen / all other components interaction parameters set to zero
Interaction parameters between H2S, CO2, N2 and CO from API table 8D1.3
__________________________________________________________________________________________
Viscosity Calculations
The viscosity models are different depending on the property package being used and are defined below.
Advanced Peng-Robinson, Huron-Vidal-Peng-Robinson, NGL-Peng-

Robinson.
Gas Phase
The pure component viscosities are calculated based regressed experimental data stored in the VMG pure
component database, or estimated using Chung’s method (Reid et al., 1987). With low pressure pure component
viscosities available, the values are correctd for pressure using Reichenberg’s method (Reid et al., 1987) and finally
mixture viscosities are calculated using Wilke’s method.
Special Component
Water viscosities are calculated using the 1995 Steam Tables.
Liquid Phase
The pure component viscosities are calculated based regressed experimental data stored in the VMG pure
ln µ m = ∑ xi ln µ i
component database, or estimated using the Letsou-Stiel method (1973). Liquid viscosities are calculated using the
logarithmic average shown in equation 38.
35
i
Special Component
Peng-Robinson, SRK, Refinery-SRK
Gas and Liquid Phases

The viscosites are calculate using the Lohrenz et al. correlation (1964). 40
Special Component
__________________________________________________________________________________________
Thermal Conductivity Calculations

Robinson.
Gas Phase
The pure component thermal conductivities are calculated based regressed experimental data stored in the VMG
pure component database, or estimated using Chung’s method (Reid et al., 1987). With low pressure pure
component viscosities available, the mixture thermal conductivity at low pressure is computed and corrected for
pressure effects using the Stiel and Thodos method method (Reid et al., 1987).
Special Component
Liquid Phase
The pure component thermal conductivities are calculated based regressed experimental data stored in the VMG
ln µ m = ∑ xi ln µ i
pure component database, or estimated using the API method 12A1.2 (API, 1992). Liquid thermal conductivities are
calculated using Li’s method (Reid et al., 1987).
38
i
Special Component
Water thermal conductivities are calculated using the 1995 Steam Tables.
Gas Phase
Gas phase thermal conductivities are calculated using API method 12B1.5 (API, 1992).
Special Component
The mixture surface tension is calculated using a molar average.
Liquid Phase
Gas phase thermal conductivities are calculated using API method 12A1.2 (API, 1992).
Special Component
Water thermal conductivities are calculated using the 1995 Steam Tables.
__________________________________________________________________________________________
Surface Tension Calculations

Robinson.
The pure component surface tensions are calculated based regressed experimental data stored in the VMG pure
component database, or estimated using Brock and Bird’s method (Reid et al., 1987). The mixture surface tension is
calculated using a molar average.
Special Component
Water surface tensions are calculated using the 1995 Steam Tables.

The pure component surface tensions are calculated using Hadden’s method (Reid et al., 1987). The mixture surface
tension is calculated using a molar average.
Special Component
Water surface tensions are calculated using the 1995 Steam Tables.
__________________________________________________________________________________________
Bibliography
Reid, R.C.; Prausnitz, J.M. and Poling, B.E.; "The Properties of Gases and Liquids", 4th Edition, McGraw-Hill
(1987)
American Petroleum Institute; "Technical Data Book – Petroleum Refining"; Fifth Edition, May 1992
__________________________________________________________________________________________
Property Package Process Notes
Property packages are developed to address specific process conditions and types of mixtures. In this section we
examine a few characteristics of VMG’s cubic equations of state based property packages.
Advanced Peng-Robinson / APRD

- very good for natural gases and for hydrocarbon mixtures with or without polar substances and
water and for refinery work.
- accurate and consistent liquid densities using volume translation
- includes specially fitted alpha functions for water, ammonia, hydrogen sulfide, urea, hydrogen,
helium, methanol, ethylene glycol, diethylene glycol and triethylene glycol plus polar compounds
used in natural gas processing and refinery applications
- models water solubility in hydrocarbons
- has consistent density for gas and liquid phases for smooth property calculations across the
critical point
- accurate water transport properties using the 1995 steam tables (APR)
- should be used with caution for isomer separation calculations
- not suitable for determining the solubility of hydrocarbons in water for environmental studies
Peng-Robinson
- good for natural gases and for hydrocarbon mixtures with or without polar substances and water
and for refinery work
helium, methanol, ethylene glycol, diethylene glycol and triethylene glycol plus polar compounds
used in natural gas processing and refinery applications
- models water solubility in hydrocarbons
- has consistent density for gas and liquid phases for smooth property calculations across the
critical point
- accurate water transport properties using the 1995 steam tables (APR)
- should be used with caution for isomer separation calculations
NGL-Peng-Robinson
- exact definition of Peng-Robinson from GPA RR-28 (1978) including GPA recommendations for
estimation of pure component physical properties from oil fractions. Uses RR-28 specifications
for C7+ characterization and estimation of interaction parameters
- good for natural gases and for hydrocarbon mixtures with or without polar substances and water
- same special treatment of water as Peng-Robinson
helium, methanol, ethylene glycol, diethylene glycol and triethylene glycol
Huron-Vidal-Peng-Robinson
- Huron-Vidal-Peng-Robinson equation of state is good for modeling polar and non-polar mixtures
at low and high pressures.
- can model vapor pressures with high accuracy ove large temperature ranges
- accurate and consistent liquid densities using volume translation
__________________________________________________________________________________________
- uses a different mixing rule designed to incorporate Gibbs Excess model into the equation of
state, as described by Huron and Vidal (1979) and in can model mixtures with strong non-
idealities in the liquid phase
- not suitable if carboxylic acids are present
- for environmental impact studies, it is necessary to manually supply the interaction parameters;
however, the Neotec software does not allow manual entry of the interaction parameters
Refinery-SRK
- good for refinery work
- is the SRK equation of state with the addition of the API (1992) recommended built-in binary
interaction coefficient database and interaction parameter estimations
- includes special correlation for hydrogen
- liquid densities are computed using the API recommended methid (Rackett). Densities are not
consistent across the critical point.
- includes specially fitted alpha functions for water, ammonia, hydrogen, helium, methanol,
ethylene glycol, diethylene glycol and triethylene glycol
SRK
- good for light gases and for hydrocarbon mixtures with/without polar substances
- equation of state which accurately models vapour pressures of light hydrocarbons and light gases
at pressures at or above atmospheric pressure
- includes specially fitted alpha functions for water, ammonia, hydrogen, helium, methanol,
ethylene glycol, diethylene glycol and triethylene glycol
__________________________________________________________________________________________

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This document is intended to assist iPRSM users in selecting the VMG Thermo vapor & liquid

Pages Section Content From Manual

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For further questions or consultation please contact support@virtualmaterials.com.

distribution in the calculation of the pseudo components Chemical Formula

Choosing Property Packages

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• Specialty Packages

Property Package Model Types

Equations of State Models

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Activity Coefficient Models

The superscript is used to denote a vapor phase.

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Specialty Property Packages

Rough screening of property packages

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Advanced Peng Robinson for Natural Gas

Benedict-Webb-Rubin and Benedict-Webb-Rubin-Starling (BWR and

Gibbs Excess Peng-Robinson (GEPR)

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Activity Coefficient Methods

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Omega A Omega B Alpha (T) Mechanical Zc

f wi = 0.37464 + 1.54226wi − 0.26992wi2 if wi < 0.5 16

Special Treatment for Pure Compounds

Default Interaction Parameters - VLE

Default Interaction Parameters – Liquid Density

f wi = 0.37464 + 1.54226wi − 0.26992wi2 if wi < 0.5 23

Special Treatment for Pure Compounds

Default Interaction Parameters

f wi = 0.37464 + 1.54226wi − 0.26992wi2 if wi < 0.5 26

Special Treatment for Pure Compounds

Default Interaction Parameters

Default Interaction Parameters – VLE

Default Interaction Parameters – Liquid Density

Special Treatment for Pure Compounds

Default Interaction Parameters

Special Treatment for Pure Compounds

Default Interaction Parameters

Advanced Peng-Robinson, Huron-Vidal-Peng-Robinson, NGL-Peng-

Peng-Robinson, SRK, Refinery-SRK

Gas and Liquid Phases

Advanced Peng-Robinson, Huron-Vidal-Peng-Robinson, NGL-Peng-

Peng-Robinson, SRK, Refinery-SRK

Advanced Peng-Robinson, Huron-Vidal-Peng-Robinson, NGL-Peng-

Peng-Robinson, SRK, Refinery-SRK

Advanced Peng-Robinson / APRD

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