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'''VTPR''' (short for Volume-Translated Peng–Robinson)<ref>Ahlers J., "Entwicklung einer universellen Gruppenbeitragszustandsgleichung", Thesis, Carl-von-Ossietzky-Universität Oldenburg, 1-144, 2003</ref><ref>Schmid B., "Einsatz einer modernen Gruppenbeitragszustandsgleichung für die Synthese thermischer Trennprozesse", Thesis, C.v.O. Universität Oldenburg, 2011</ref>
is an estimation method for the calculation of phase equilibria of mixtures of chemical components. The original goal for the development of this method was to enable the estimation of properties of mixtures which contain supercritical components. These class of substances couldn't be predicted with established models like [[UNIFAC]].

== Principle ==
VTPR is a group contribution [[equation of state]].<ref>{{Cite journal |last1=Schmid |first1=Bastian |last2=Schedemann |first2=Andre |last3=Gmehling |first3=Jürgen |date=2014-02-26 |title=Extension of the VTPR Group Contribution Equation of State: Group Interaction Parameters for Additional 192 Group Combinations and Typical Results |url=https://pubs.acs.org/doi/10.1021/ie404118f |journal=Industrial & Engineering Chemistry Research |language=en |volume=53 |issue=8 |pages=3393–3405 |doi=10.1021/ie404118f |issn=0888-5885}}</ref> This is class of prediction methods combine equations of state (mostly cubic) with [[activity coefficient]] models based on [[Group contribution method|group contributions]] like UNIFAC.<ref>{{Citation |last1=Carreón-Calderón |first1=Bernardo |title=Cubic Equations of State |date=2021 |work=Thermophysical Properties of Heavy Petroleum Fluids |pages=41–107 |url=https://link.springer.com/10.1007/978-3-030-58831-1_3 |access-date=2024-05-10 |place=Cham |publisher=Springer International Publishing |language=en |doi=10.1007/978-3-030-58831-1_3 |isbn=978-3-030-58830-4 |last2=Uribe-Vargas |first2=Verónica |last3=Aguayo |first3=Juan Pablo}}</ref> The activity coefficient model is used to adapt the equation of state parameters for mixtures by a so-called [[mixing rule]].<ref>{{Cite book |last1=Mokhatab |first1=Saeid |title=Handbook of Natural Gas Transmission and Processing |last2=Poe |first2=William A. |last3=Mak |first3=John Y. |publisher=[[Gulf Professional Publishing]] |year=2019 |isbn=978-0-12-815817-3 |edition=4th |pages=37–101 |language=en |chapter=Chapter 2 - Phase Behavior of Natural Gas Systems |doi=10.1016/C2017-0-03889-2 |chapter-url=https://www.sciencedirect.com/science/article/abs/pii/B9780128158173000022}}</ref>

The usage of an equation of state introduces all thermodynamic relations defined for equations of state into the VTPR model. This allows the calculation of [[Density|densities]], [[Enthalpy|enthalpies]], [[Heat Capacity|heat capacities]], and more.<ref>{{Cite journal |last1=Wilhelmsen |first1=Øivind |last2=Aasen |first2=Ailo |last3=Skaugen |first3=Geir |last4=Aursand |first4=Peder |last5=Austegard |first5=Anders |last6=Aursand |first6=Eskil |last7=Gjennestad |first7=Magnus Aa. |last8=Lund |first8=Halvor |last9=Linga |first9=Gaute |last10=Hammer |first10=Morten |date=2017-04-05 |title=Thermodynamic Modeling with Equations of State: Present Challenges with Established Methods |url=https://pubs.acs.org/doi/10.1021/acs.iecr.7b00317 |journal=Industrial & Engineering Chemistry Research |language=en |volume=56 |issue=13 |pages=3503–3515 |doi=10.1021/acs.iecr.7b00317 |issn=0888-5885|hdl=11250/2482318 |hdl-access=free }}</ref>

== Equations ==
VTPR is based on a combination of the [[Equation of state#Peng–Robinson equation of state|Peng–Robinson equation of state]] with a mixing rule whose parameters are determined by UNIFAC.

=== Equation of state ===
The [[Peng–Robinson equation of state]] is defined as follows:

<math>P = \frac{ R \; T } { v - b } - \frac{ a\; \alpha(T) } { v^2 + 2bv - b^2 }</math>

The originally used α-function has been replaced by the function of Twu, Bluck, Cunningham and Coon
.<ref>Twu C.H., Bluck D., Cunningham J.R., Coon J.E., "A Cubic Equation of State with a New Alpha Funktion and a New Mixing Rule", Fluid Phase Equilib., 69, 33-50, 1991.
 {{ISSN|0378-3812}}, {{doi|10.1016/0378-3812(91)90024-2}}</ref>

<math>\alpha(T_r) = T_r^{N \left( M-1 \right)} exp \left( L \left( 1- T_r^{ M N }\right) \right)</math>

The parameters of the Twu equation are fitted to experimental vapor pressure data of pure components and guarantee therefore a better description of the vapor pressure than the original relation.

=== Mixing rule ===
The VTPR mixing rule calculate the parameter a and b of the equation of state by

<math> a(T) = b \cdot \left( \sum_i {x_i} \frac{a_{ii}(T)}{b_{ii}} + \frac{g^E_{res}} {-0.53087} \right) </math>

with

<math>P_{ref} = 1\,atm</math>

and

<math> b_{ij}^{3/4} = \frac{ b_{ii}^{3/4} + b_{jj}^{3/4} }{2}</math>

<math> b_{ii}=0.0778 \cdot \frac{R \cdot T_{c,i}}{P_{c,i}}</math>

<math> b = \sum_i \sum_j x_i \; x_j \; b_{ij}</math>

by the parameters  a<sub>i</sub> und b<sub>i</sub> of the pure substances, their mole fractions x<sub>i</sub> and the residual part of excess Gibbs energy g<sup>E</sup>. The excess Gibbs energy is calculated by a modified UNIFAC model.

== Model parameters ==
For the equation of state VTPR needs the [[critical temperature]] and [[Critical pressure|pressure]] and additionally at least the acentric factor for all pure components in the considered mixture.<ref>{{Cite journal |last1=Schmid |first1=Bastian |last2=Gmehling |first2=Jürgen |year=2012 |title=Revised parameters and typical results of the VTPR group contribution equation of state |url=https://linkinghub.elsevier.com/retrieve/pii/S0378381212000076 |journal=Fluid Phase Equilibria |language=en |volume=317 |pages=110–126 |doi=10.1016/j.fluid.2012.01.006|bibcode=2012FlPEq.317..110S }}</ref>

A better quality can be achieved if the acentric factor is replaced by Twu constants which have been fitted to experimal vapor pressure data of pure components.<ref>{{Cite journal |last1=Zhao |first1=Wenying |last2=Sun |first2=Xiaoyan |last3=Xia |first3=Li |last4=Xiang |first4=Shuguang |date=2018-09-26 |title=Research into the Polynomial Alpha Function for the Cubic Equation of State |url=https://pubs.acs.org/doi/10.1021/acs.iecr.8b02549 |journal=Industrial & Engineering Chemistry Research |language=en |volume=57 |issue=38 |pages=12602–12623 |doi=10.1021/acs.iecr.8b02549 |issn=0888-5885|doi-access=free }}</ref>

The mixing rule uses UNIFAC which needs a variety of UNIFAC-specific parameters. Beside some model constants the most important are group interaction parameters which are fitted to experimental vapor–liquid equilibria of mixtures.<ref>{{Citation |last1=Abildskov |first1=Jens |title=Models for Liquid Phase Activity Coefficients - UNIFAC |date=2004 |work=Computer Aided Chemical Engineering |volume=19 |pages=59–74 |url=https://linkinghub.elsevier.com/retrieve/pii/S1570794604800063 |access-date=2024-05-10 |publisher=Elsevier |language=en |doi=10.1016/s1570-7946(04)80006-3 |isbn=978-0-444-51153-9 |last2=Kontogeorgis |first2=Georgios M. |last3=Gani |first3=Rafiqul}}</ref>

Hence, for high-quality model parameters experimental data (pure component vapor pressures and [[vapor–liquid equilibrium]] and liquid–liquid equilibrium data, activity coefficients of mixtures, heats of mixing) are needed. These are normally provided by factual data banks like the [[Dortmund Data Bank]] which has been the base for the VTPR development.<ref>{{Cite journal |last1=Marcilla |first1=A. |last2=Olaya |first2=M.M. |last3=Reyes-Labarta |first3=J.A. |year=2016 |title=Comments on the correlation of vapor–liquid equilibrium (VLE) data in azeotropic ternary systems |url=https://linkinghub.elsevier.com/retrieve/pii/S0378381216300607 |journal=Fluid Phase Equilibria |language=en |volume=426 |pages=110–118 |doi=10.1016/j.fluid.2016.02.010|bibcode=2016FlPEq.426..110M |hdl=10045/57678 |hdl-access=free }}</ref><ref>{{Cite journal |last1=Kontogeorgis |first1=Georgios M. |last2=Dohrn |first2=Ralf |last3=Economou |first3=Ioannis G. |last4=de Hemptinne |first4=Jean-Charles |last5=ten Kate |first5=Antoon |last6=Kuitunen |first6=Susanna |last7=Mooijer |first7=Miranda |last8=Žilnik |first8=Ljudmila Fele |last9=Vesovic |first9=Velisa |date=2021-04-07 |title=Industrial Requirements for Thermodynamic and Transport Properties: 2020 |journal=Industrial & Engineering Chemistry Research |language=en |volume=60 |issue=13 |pages=4987–5013 |doi=10.1021/acs.iecr.0c05356 |issn=0888-5885 |pmc=8033561 |pmid=33840887}}</ref>

== Volume translation ==
{{Unreferenced section|date=October 2023}}
VTPR implements a correction to the pure component densities resp. volume. This volume translation corrects systematic deviations of the Peng–Robinson equation of state (PR EOS).
The translation constant is obtained by determining the difference between the calculated density at T<sub>r</sub>=0.7 and the real value of the density obtained from experimental data. T<sub>r</sub> is close to the [[normal boiling point]] for many substances. The volume translation constant c<sub>i</sub>

<math>c_i=v_{PR,i}-v_{exp,i}</math>

is therefore component specific.

This volume/density translation is then applied to the complete density/volume curve calculated by the PR EOS. This is sufficient because the calculated curve has the right slope and is only shifted.

The Peng–Robinson equation of state is then

<math>P=\frac{R \cdot T}{v+c-b} - \frac{a \cdot \alpha(T)}{(v+c) \cdot (v+c+b) + b \cdot (v+c-b)}</math>

== Modifications to the UNIFAC model ==
{{Unreferenced section|date=October 2023}}
UNIFAC use two separate parts to calculate the activity coefficients, a combinatorial part and a residual part. The combinatorial part is calculated only from group specific constants and is omitted in the VTPR model. VTPR use only the residual part calculated from interaction parameters between groups.

<math>g_{res}^E= R \cdot T \cdot \sum { x_i \cdot \ln \; \gamma_{res,i} }</math>

This has the side effect that r<sub>i</sub> values (van der Waals volumes) are not needed and only the van der Waals surfaces
q<sub>i</sub> are used.

In addition, the q<sub>i</sub> values are not constant properties of the groups, instead they are adjustable parameters and fitted to experimental data together with the interaction parameters between groups.

== Example calculation ==
The prediction of a vapor–liquid equilibrium is successful even in mixtures containing supercritical components.

[[Image:VTPR VLE Prediction Cyclohexane and Carbon Dioxide.png|350px|Vapor–liquid equlibrium of [[Cyclohexane]] and [[Carbon Dioxide]]]]

The mixture has to be subcritical though. In the given example carbon dioxide is the supercritical component with T<sub>c</sub>=304.19 K<ref>Ambrose D., ''Trans. Faraday Soc.'', 52, 772-781, 1956. {{ISSN|0014-7672}}, {{doi|10.1039/TF9565200772}}</ref> and P<sub>c</sub>=7475 kPa.<ref>Schmidt E., Thomas W., ''Forsch. Geb. Ingenieurwes. Ausg. A'', 20, 161-170, 1954</ref> The critical point of the mixture lies at T=411 K und P≈15000 kPa. The composition of the mixture is near 78 mole% carbon dioxide und 22 mole% cyclohexane.

VTPR describes this binary mixture quite well, the [[dew point]] curve as well as the bubble point curve and the critical point of the mixture.

== Electrolyte systems ==
VTPR normally cannot handle [[electrolyte]] containing mixtures because the underlying UNIFAC doesn't support salts. It is however possible to exchange the UNIFAC [[activity coefficient]] model by a model that supports electrolytes like [[LIFAC]].<ref>Eileen Collinet, [[Jürgen Gmehling]], "Prediction of phase equilibria with strong electrolytes with the help of the volume translated Peng–Robinson group contribution equation of state (VTPR)", ''Fluid Phase Equilibria'', 246(1–2), 111–118, 2006.  {{ISSN|0378-3812}}, {{doi|10.1016/j.fluid.2006.05.033}}</ref>

== See also ==
* [[PSRK]] (Predictive Soave–Redlich–Kwong), VTPRs predecessor of the same group contribution equation of state type but using a different equation of state, a different α function, and a different UNIFAC modification.

== Literature ==
<references/>

== External links==
* {{Cite web| url = http://www.ddbst.com/VTPR.html |title= Published VTPR parameters |accessdate= 18 May 2015 |publisher= DDBST GmbH }}


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[[Category:Thermodynamic models]]