PPEPPD 2016 Oporto Abstract Book

BOOK OF ABSTRACTS
14th International Conference on Properties and

Phase Equilibria for Product and Process Design
PPEPPD 2016
22-26 May 2016, Porto, Portugal
Edited by:
Maria Eugénia Rebello de Almeida Macedo
José Nuno Canongia Lopes
Faculdade de Engenharia da Universidade do Porto

Porto, Portugal
This volume contains the book of abstracts of the 14th International Conference on
Properties and Phase Equilibria for Product and Process Design – PPEPPD 2016, held in
Porto, Portugal, 22-26 May 2016.
Title: Book of Abstracts - 14th International Conference on Properties and

Author: Maria Eugénia Rebello de Almeida Macedo
Co-author: José Nuno Canongia Lopes
First Edition: May 2016
ISBN: 978-989-20-6695-0
Publisher:
Faculdade de Engenharia da Universidade do Porto
Printed by:
Titulo Genuíno
Credits to: Emília Casaca

Karina Shimizu
Oscar Rodriguez
© Faculdade de Engenharia da Universidade do Porto

PPEPPD 2016
May 22-26 | Porto | Portugal Phase Equilibria for Product and Process Design
TABLE OF CONTENTS
Welcome 4
Committees 5
Sponsors 8
About PPEPPD 9
General Information 10
Scientific Program 14
May 22-26 | Porto | Portugal
WELCOME
Dear Friend and Participant,
It is our great pleasure to welcome you to the 14th International Conference on

Properties and Phase Equilibria for Product and Process Design, PPEPPD 2016, held
for the first time in Portugal.
We chose Espinho, in the beautiful coast of northern Portugal, facing the Atlantic
Ocean and very near to the historical city of Porto (World Heritage Site by UNESCO,
1996). A coast and an Ocean where many famous Portuguese discoveries had their
beginning more than 500 years ago.
The fact that we were able to join 311 registered participants from 36 different
countries all over the world, gives us enormous satisfaction and pride, as this is the
largest PPEPPD conference ever.
As in past editions, the program prepared by the International Organizing Committee
(IOC), has focused on the current needs and challenges of our society, and at the same
time tried to keep the balance between traditional and emerging fields, fundamentals
and applications, modeling and experiment, academic interests and industry needs.
We hope that this program meets your expectations.
We will enjoy three interesting and exciting moments during PPEPPD: besides the
usual John M. Prausnitz award, the distinguished lecture of the European Working
Party on Thermodynamics and Transport Properties, and the new book “The History of
the PPEPPD Conferences 1977-2013”, by John O’Connell, will be presented.
We would like to express our gratitude to our sponsors, who made this conference
possible. Our acknowledgements are also due to the International Organizing
Committee (IOC) for their support and excellent spirit; to the Local Organizing
Committee (LOC), and particularly Oscar Rodriguez for his tireless efforts and
friendship during this long journey; to the International Advisory Board (IAB) for their
valuable input; to the young scientists of our research groups who have helped in
this organization with their enthusiasm and team spirit; to our workshop organizers
and panel members for sharing their expertise with us; to our distinguished invited
speakers, for accepting our invitation; to all speakers and poster presenters and to you
all for your interest and active participation.
And now, it is our hope that when you return to your own homes with the happiest
of memories and you remember the great Portuguese discoveries of another age,
you will have made, in this age, some important discoveries of your own as regards
Properties and Phase Equilibria for Product and Process Design.
4
Maria Eugénia Rebello de A. Macedo José Nuno Canongia Lopes
Chair Co-chair
PPEPPD 2016
COMMITTEES
International Organizing Committee
Maria Eugénia Rebello de A. Macedo (Chair) University of Porto, Portugal
José Nuno Canongia Lopes (Co-Chair) University of Lisbon, Portugal
Susana Bottini Universidad Nacional del Sur,

Bahia Blanca, Argentina
Joan Brennecke University of Notre Dame, USA
Ioannis G. Economou Texas A&M University, Qatar
João F. Fugas CUF, Portugal
Xiaohua Lu Nanjing University of Technology,

China
John O’Connell University of Virginia, USA
Athanassios Z. Panagiotopoulos Princeton University, USA
Cor Peters Delft University of Technology,

The Netherlands
The Petroleum Institute,

Abu Dhabi, UAE
Gabriele Sadowski Technical University of Dortmund,

Germany
John Shaw University of Alberta, Canada
5
Local Organizing Committee

Oscar Rodriguez (Coordinator) University of Santiago Compostela, Spain
Maria Emília Casaca University of Porto, Portugal
Karina Shimizu University of Lisbon, Portugal
Irene Dominguez Fernandez University of Porto, Portugal
Kamila Wysoczanska University of Porto, Portugal
Begoña Gonzalez de Prado University of Vigo, Spain
International Advisory Board PPEPPD 2016

Karel Aim Academy of Sciences, Czech Republic
Peter Cummings Vanderbilt University, USA
Walter Chapman Rice University, USA
Chau-Chyun Chen Texas Tech University, USA
Juan de Pablo University of Wisconsin Madison, USA
Jean-Charles de Hemptinne IFP Énergies Nouvelles, France
Sebastião Feyo de Azevedo University of Porto, Portugal
Keith Gubbins North Carolina State University, USA
Carol Hall North Carolina State University, USA
Manfred Heilig BASF, Germany
Eric Hendricks Shell Technology Centre, The Netherlands
George Jackson Imperial College London, UK
Georgios Kontogeorgis Technical University of Denmark, Denmark
Theo de Loos Delft University of Technology, The Netherlands
Manuel Nunes da Ponte New University of Lisbon, Portugal
John Prausnitz University of California, Berkeley, USA
Stan Sandler University of Delaware, USA
Ali Shariati Shiraz University, Iran
Mark Shiflett Du Pont, USA
Richard Smith Tohoku University, Japan
Frederico Tavares Universidade Federal do Rio de Janeiro, Brazil
Doros Theodorou National Technical University of Athens, Greece
Lourdes Vega Petroleum Institute, UAE
6 Juan Vera McGill University , Canada
Hu Ying East China University of Science and Technology, China
PPEPPD 2016
pubs.acs.org/jced
THERMOPHYSICAL PROPERTIES AND

PHASE EQUILIBRIA FROM EXPERIMENT
AND COMPUTATION
NEW TOPIC EXPERTS JOIN JCED AS ASSOCIATE EDITORS
David Kofke J. Ilja Siepmann

SUNY, University at Buffalo University of Minnesota
The Journal of Chemical & Engineering Data (JCED) publishes data

obtained from both experiment and computation, with a focus on
phase behavior and physical, thermodynamic, and transport
properties of well-defined materials. With over 17,000 citations, JCED
is the most cited journal among others serving the field.* JCED has
expanded its focus to emphasize molecular modeling and simulation.
* The 2014 Journal Citation Reports® (JCR) from Thomson Reuters
Submit your best papers

on Molecular Modeling 7
and Simulation
SPONSORS
Grand Sponsors
Sponsors
8
PPEPPD 2016
ABOUT PPEPPD
The origin of the PPEPPD Conferences can be traced back to the recognition in the
early 1970’s that a severe communication gap existed between fundamental and
applied aspects of product and process design, namely in the area of properties and
phase equilibrium.
The motivation and spirit of these first PPEPPD conferences have been kept for more
than 30 years of uninterrupted triennial editions:
1977: Asilomar, California, USA

1980: Berlin, Germany
1983: Callaway Gardens, Georgia, USA
1986: Elsinore, Denmark
1989: Banff, Alberta, Canada
1992: Cortina d’Ampezzo, Italy
1995: Aspen, Colorado, USA
1998: Noordwijkerhout, The Netherlands
2001: Kurashiki, Japan
2004: Snowbird, Utah, USA
2007: Hersonissos, Crete, Greece
2010: Suzhou, China
2013: Iguazu Falls, Argentina and Brazil
PPEPPD 2016
Close to the city of Porto, Espinho welcomes the 14th International Conference on
Properties and Phase Equilibria for Product and Process Design (PPEPPD 2016).
This city is modern, cosmopolitan and full of innovation. We would like to invite you to
enjoy this wonderful place where emotion and rhythms happen.
9
GENERAL INFORMATION
Registration Desk
The registration desk is located in the Main Lobby or the Foyer Area of the hotel. It will
be open:
Sunday, 22 of May – from 15.00h to 21.00h
Monday, 23 of May – from 08.00h to 18.00h
Tuesday, 24 of May – from 08.00h to 16.00h
Wednesday, 25 of May – from 08.00h to 18.30h
Thursday, 26 of May – from 08.00h to 13.00h
Oral Sessions / Speakers Preparation Room and Slide Desk

Keynote and Invited Lectures will take place in Costa Verde Room. Oral presentations
will be either in Costa Verde or Nova Iorque rooms.
Speakers are kindly asked to deliver their presentation to the Speakers Preparation
Room, located in Monaco Room, two hours before the start of the corresponding
session. For oral presentations included in a morning first session, the presentation
should be uploaded during the previous day.
Poster Sessions
Posters should be placed on their corresponding stands in their designated day of
presentation (Monday, Tuesday or Wednesday from 12h30 to 15h00). Posters can be
set-up as early as 8h00 of a given day and should be removed in the same day by
17h00 on Monday and Wednesday and by 16h00 on Tuesday.
Social Program
Welcome Reception - Sunday, 22 May
The Welcome Reception will take place in Hotel Solverde from 20.00h to 22.00h.
Excursion and dinner at Taylor’s Portwine Cellars – Tuesday, 24 May
The coaches will depart from Hotel Solverde at 16.15h.
Coaches will take participants back to the hotels at the end of dinner.
Conference Dinner – Wednesday, 25 May
The Conference Dinner will take place in Salão Atlântico at Casino de Espinho.
10
PPEPPD 2016
Internet Access
Participants will have free WIFI access within most of the conference venue area.
Scope and Topics

Fundamentals
• Thermodynamics and transport properties (experimental & modeling)
• Phase equilibria (experimental & modeling)
• Surfaces, interfaces and confinement effects
• Molecular and multiscale simulation
• Quantum mechanical calculations and force fields
Processing and Applications

• Gas and oil downstream and upstream, hydrofracking
• Product and process engineering
• Alternative energy resources and storage
• Environment, sustainability and risk management
• Carbon capture and storage
• Reaction and separation technologies (e.g., ionic liquids, electrolyte systems,
membranes, gas hydrates)
• Pharmaceuticals and cosmetics
• Food processing
• Agrochemicals and biomass
• Marine and saline systems and processes
• Materials (e.g., polymers, metals, inorganic solids, liquid crystals)
• Nanoscience and nanotechnology
11
John M. Prausnitz Award

This will be the seventh award in the John M. Prausnitz series initiated in 1998. The
seventh John M. Prausnitz award for outstanding achievements in Applied Chemical
Thermodynamics will be awarded to Professor Doros N. Theodorou, from the
Department of Materials Science and Engineering, School of Chemical Engineering,
National Technical University of Athens, Greece.
Professor Theodorou is honored for his research accomplishments in paradigm-
shifting modeling and computer simulation methods for understanding and
predicting properties of materials from their chemical constitution, with particular
emphasis on amorphous polymers and zeolites, which are used widely in academia
and industries.
List of previous awardees:

PPEPPD 1998: Prof. Athanassios Panagiotopoulos, University of Maryland, USA
PPEPPD 2001:Prof. Pablo Debenedetti, Princeton University, USA
PPEPPD 2004: Prof. David Kofke, University at Buffalo, USA
PPEPPD 2007: Prof. Joan Brennecke, University of Notre Dame, USA
PPEPPD 2010: Prof. Theodore Randolph, University of Colorado, USA
PPEPPD 2013: Prof. Peter Cummings, Vanderbilt University, USA
Distinguished Lecture of Working Party on TTP - EFCE

The third Distinguished Lecture of the Working Party on Thermodynamics and
Transport Properties of the European Federation of Chemical Engineering will be
delivered by Professor Cornelis Peters during PPEPPD 2016. Professor Peters is
recognized for his 40 years of contributions to the fundamental understanding of
phase theory. He has been a pioneer in the design, development and optimization
of new experimental methods to measure accurate thermodynamic and phase
equilibrium properties, and in the application of theoretical models for complex fluids
and molecular simulation methods to explain physical phenomena at different length
and time scales.
12
PPEPPD 2016
The PPEPPD Conferences 1977-2013

During PPEPPD 2016, a special moment will be the presentation of the book “The
PPEPPD Conferences 1977-2013”, written by Professor John P. O’Connell, Professor
Emeritus, University of Virginia, USA.
“The first Triennial Conference on Properties and Phase Equilibria for Product and Process
Design was held in 1977. Through 2013, the meetings of 100-300 fundamental and
applied workers in the area have been held in 10 different countries. This book describes
the developments and outcomes of the Conferences by the only person to have attended
every gathering and helped in their organization for over 30 years.”
The presentation will introduce the book format and contents.
Special Issue of Journal of Chemical & Engineering Data

The Editors of the Journal of Chemical & Engineering Data (JCED) have arranged for
publication of the PPEPPD 2016 Conference Proceedings as a Special Issue of JCED. All
submissions must have been presented at the Conference.
JCED requires submission through its online submission system ACS Paragon Plus.
If you do not already have a User ID, you will need to create one and log in. NOTE:
A Special Issue has been created for the Proceedings. After logging in, please choose
“Article” and then select “Proceedings of PPEPPD 2016” from the pull-down list under
Special Issue Selection.
Formatting must follow the JCED Author Guidelines. All submissions will be
subjected to the normal peer-review process. JCED welcomes data obtained from
both experiment and computation, which are viewed as complementary. Any work
concerning thermophysical properties obtained from quantum chemistry, molecular
simulation, or molecular mechanics calculations, as well as reviews of experimental
techniques, is welcome.
To be considered for this Special Issue, all manuscripts must be submitted by July 1,
2016. Manuscripts submitted after this time may be considered for other issues of
JCED. Please contact Tammy Hanna (t_hanna@acs.org) with further questions.
13
SCIENTIFIC PROGRAM
Sunday Evening – May, 22
Sunday Evening – May, 22
18:45 Opening Session (Costa Verde)

Joaquim J. Pinto Moreira (Mayor of Espinho), Eugénia A. Macedo (Chair PPEPPD),
João Falcão e Cunha (Dean of FEUP) and SebasWão Feyo de Azevedo (Rector of UP)
19:15
Opening Lecture (Costa Verde)
Chair: John O’Connell
19:15
Nanopar5cles in liquid crystals, and liquid crystals in nanopar5cles
Keynote Address
20:00 Juan de Pablo KA
14
7
PPEPPD 2016
Monday Morning – May, 23

Monday Morning – May, 23
Invited Lecture 1 (Costa Verde)

Chairs: Gabriele Sadowski and David A. Koè
8:30
Thermodynamic modeling of fluids confined in porous media: an overview of selected approaches
Marcelo CasCer IL1
9:15
Chairs: Gabriele Sadowski and David A. Koè
9:15
Coarse-graining with the rela5ve entropy: recent theory and algorithms
Sco. Shell IL2
10:00
Oral Session 1: Molecular Modeling and SimulaWon 1 (Costa Verde)

Chairs: Richard J. Sadus and Alexey Victorov
10:30
Molecular simula5on study of the mechanical proper5es of semi-crystalline polyethylene
Germain Clavier, Nadège Brusselle-Dupend, Véronique Lachet and Bernard Rousseau O1-1
11:00
Fluid–fluid coexistence in an athermal colloid–polymer mixture: thermodynamic perturba5on
theory and con5nuum molecular-dynamics simula5on
Julio Jover, Amparo Galindo, George Jackson, Erich A. Müller and Andrew J. Haslam O1-2
11:30
Understanding and predic5ng the interfacial structure and dynamics in capacita5ve energy
systems u5lizing model-integrated synthesis, characteriza5on and experiment
Mafhew W. Thompson, Yu Zhang and Peter T. Cummings O1-3
12:00
Polarizable versus non-polarizable force fields of electrolytes:
simula5on methodologies, chemical poten5als, and solubility
Ivo Nezbeda and William R. Smith O1-4
12:30
Oral Session 2: Carbon Capture and Storage (Nova Iorque)

Chairs: Sabine Enders and Frederico W. Tavares
10:30
CO2 pre-combus5on capture and CO2 storage through hydrate crystalliza5on
Duo Sun and Peter Englezos O2-1
11:00
A molecular model to characterize the effect of impuri5es on the thermophysical
proper5es on CO2 transport
Fèlix Llovell and Lourdes F. Vega O2-2
11:30
CO2 solubility in aqueous solu5ons of linear and branched polyamines
Jian Chen, Ruilei Zhang, Zhongjie Du, Yanmei Yu and Jianguo Mi O2-3
12:00
Molecular modeling studies of CH4 storage using nanoporous carbons
Di Wu, Linghong Lu, Shanshan Wang and Wei Cao O2-4
12:30
15
8
Monday Lunchtime – May, 23
12:30 – 15:00
Poster Sessions Foyer

Room
Prediction of safety-relevant properties for multicomponent PU raw-material

mixtures: flash point, auto ignition temperature and initial normal point 1 – P01
Stephanie Peper, Ralf Dohrn and Klaus Konejung
The spreading behavior of surfactant-laden aqueous droplets on textured surface

1 – P02
Zhi Li, Bei Liu, Bo Jing, Guangjin Chen and Xianren Zhang
Predicting asphaltene precipitation in petroleum fluids via NRTL-SAC

1 – P03
Md Rashedul Islam and Chau-Chyun Chen
Modeling phase equilibria of semiclathrate hydrates of CH4, CO2, N2 and gas

mixtures in aqueous solutions of TBAB and TBAF 1 – P04
Qing-Lan Ma, Jun-Li Qi, Chang-Yu Sun and Guang-Jin Chen
Development of a comprehensive molecular thermodynamic model for high

salinity produced water in oil and gas productions 1 – P05
Chau-Chyun Chen and Huan Zhou
Influence of PEG’s molecular weight on different polymer/salt ATPS phase

diagrams 1 – P06
Kamila Wysoczanska and Eugénia A. Macedo
Application of PPR78 thermodynamic framework as fill method for semi-empirical

mixing rule for hydrocarbon-water-glycol mixtures
1 – P07
Francisco J. Braña-Mulero, Seiya Hirohama, Prasanna Lakshmi Lingampally, Masakazu
Sasaki and Jean-Noël Jaubert
Prediction of solvent effects on reaction kinetics

1 – P08
Max Lemberg, Gabriele Sadowski
Common features shared by a pure substance and a binary azeotrope

1 – P09
Jean-Noël Jaubert and Romain Privat
COSMO-CAMD: A framework for computer-aided molecular design with COSMO-RS

1 – P10
Jan Scheffczyk, Lorenz Fleitmann, Annett Schwarz, André Bardow and Kai Leonhard
16
PPEPPD 2016
12:30 – 15:00

Room
The role of ionic liquids as hydrotropes on the enhanced solubilization of

antioxidants extracted from biomass
1 – P11
Ana Filipa M. Cláudio, Márcia C. Neves, Karina Shimizu, José N. Canongia Lopes, Mara G.
Freire and João A.P. Coutinho
Measurement and modeling of the phase behavior of n-alkane diluted bitumen

Kim A. Johnston, Marco A. Satyro, Shawn D. Taylor, Harvey W. Yarranton and Florian F. 1 – P12
Schoegg
All-atom force-fields for short hydrofluoroalkanes

1 – P13
Jiri Janecek, Patrice Paricaud, Celine Houriez and J. Deschamps
Rapid characterization of multicomponent vapor-liquid equilibria using Raman

spectroscopy
1 – P14
Bastian Liebergesell, Carsten Flake, Thorsten Brands, Hans-Jürgen Koß and André Bardow
Critical analysis of liquidus curves in concentrated aqueous solutions of borates

MBO2 (M = Na, K) 1 – P15
Goutaudier Christelle, Richard Tenu and Jean-Jacques Counioux
Anion effects on the solubility of R1234yf in ionic liquid

1 – P16
Xiangyang Liu, Maogang He and Lihang Bai
A review on diffusivities of gases and liquids with ionic liquids

1 – P17
Maogang He, Sanguo Peng and Xiangyang Liu
Evaluation of ionic liquid-based technology for biogas upgrading

1 – P18
Yujiao Xie, Chunyan Ma, Xiaohua Lu and Xiaoyan Ji
Solvent activity in electrolyte solutions from molecular simulations of the osmotic

pressure 1 – P19
Maximilian Kohns, Steffen Reiser, Martin Horsch and Hans Hasse
Critical point prediction using CPA for pure and multicomponent systems
1 – P20
André P. C. M. Vinhal, Georgios M. Kontogeorgis and Wei Yan
17
12:30 – 15:00

Room
Experimental and theoretical study of liquid-liquid equilibrium of water +

1-butanol + inorganic salt systems 1 – P21
Kanungnit Chawong, Vattanavongs Ratanavaraha and Panarat Rattanaphanee
Thermodynamic and transport properties for the H2O+CO2+NaCl system from

polarizable force fields 1 – P22
Hao Jiang, Othonas A. Moultos, Ioannis G. Economou and Athanassios Z. Panagiotopoulos
Calculation of vapor-liquid equilibria for Lennard-Jones fluids by molecular

dynamics simulation with large number of molecules 1 – P23
Yoshio Iwai, Issei Taniguchi and Yasuhiro Tada
Ab Initio values of the gas transport properties of helium, hydrogen isotopologues,

and their binary mixtures at low density 1 – P24
Zhuo Zhang, Kai Kang, Bo Song, Xiaopo Wang and Zhigang Liu
Measurement and modeling of the phase behaviour of (CO2 + CO) at temperatures

between (218.15 and 303.15) K and pressures up to 14 MPa 1 – P25
Lorena F. S. Souza, Saif Z. S. Al Ghafri and J. P. Martin Trusler
Thermodynamic properties prediction of big molecules wih equation of state

1 – P26
Hideo Nishiumi
Estimation of the standard molar enthalpy of formation of low-valued biomasses

and their biogas residue 1 – P27
Hongliang Qian, Chang Liu, Xin Feng and Xiaohua Lu
Evaluation of new inhibitors of hydrate clathrate formation

María Esther Rebolledo-Libreros, Joel Reza, Arturo Trejo and Diego Javier Guzmán- 1 – P28
Lucero
Thermodynamic analysis of fluoride removal using an aluminum-doped adsorbent

1 – P29
Didilia I. Mendoza-Castillo, H. Elizabeth Reynel-Ávila and Adrián Bonilla-Petriciolet
Discrete modeling: the concept of Shannon entropy used for thermodynamic

model developoment 1 – P30
Thomas Wallek, Martin Pfleger and Andreas Pfennig
18
PPEPPD 2016
12:30 – 15:00

Room
Liquid-liquid equilibria of water + 1-propanol + 1-butyl-1-methylpyrrolidinium

bis(trifluoromethanesulfonyl)imide ternary system 1 – P31
Amparo Cháfer, Javier de la Torre, Estela Lladosa and Jordi Pla-Franco
Simple equipment for measurement of total pressure of polymer + solvent mixtures

1 – P32
Jan Pavlíček, Grozdana Bogdanić and Ivan Wichterle
Prediction of interfacial properties of ternary, sulfur containing mixtures

1 – P33
Christian Bühl and Sabine Enders
A thermodynamic approach for analysis and prediction of pharmaceutical

dissolution 1 – P34
Yuanhui Ji and Raphael Paus
Surrogate design for complex hydrocarbon mixtures:

property prediction by the real-component approach 1 – P35
Kathrin Kos and Thomas Wallek
Integrated design of ORC processes and working fluids based on equilibrium and
transport properties from PCP-SAFT 1 – P36
Johannes Schilling, Matthias Lampe, Madlen Hopp, Joachim Groß and André Bardow
Modelling of phase- and interfacial behavior of branched alkanes

1 – P37
Christoph Walowski and Sabine Enders
Modeling the viscosity of gases, hydrocarbons and refrigerants with a cubic EoS
coupled to the free volume theory or the friction theory 1 – P38
Luis A. Forero G, Nicolas Ramirez V. and Daniel Muñoz L.
A simple model to represent the vapor pressure, the liquid density and the
viscosity of imidazolium-based ionic liquids 1 – P39
Luis A. Forero G., Daniela López R. and Paula Rhenals M.
A simple and generalized model to represent the vapor-liquid equilibria and the
liquid-densities of alkane-alkane, alcohol-alcohol and ether-alkane mixtures 1 – P40
Luis A. Forero G., Elizabeth Rincón P. and Jorge A. Velásquez J.
19
12:30 – 15:00

Room
Experimental study of refrigerants and their mixtures

1 – P41
Martin Doubek and Vaclav Vacek
Molecular structure characterization for hydrocarbon process simulation

1 – P42
Herbert Loria, Glen Hay and Marco A. Satyro
Molecular simulation of adsorption of polar and non-polar gases from natural gas
using FPYEu MOF 1 – P43
Flor R. Siperstein and Thaer M. Al-Jadir
Deep eutectic solvents as azeotrope breakers

1 – P44
Nerea R. Rodriguez and Maaike C. Kroon
Analytic continuation of the virial series through the critical point using parametric
approximants 1 – P45
Nathaniel S. Barlow, Andrew J. Schultz, Steven J. Weinstein and David A. Kofke
Modeling of adsorption isotherms using density-functional theory

1 – P46
Patrick Zimmermann, Thomas Goetsch, Tim Zeiner and Sabine Enders
Reactant-ratio and pH influence on the thermodynamics of enzyme-catalyzed

reactions 1 – P47
Matthias Voges, Gabriele Sadowski and Christoph Held
Permeation of supercritical fluids through microporous constrictions by molecular

simulations 1 – P48
Fouad Oulebsir, Romain Vermorel and Guillaume Galliero
Dynamic simulation of a polymer process using the PC-SAFT equation of state

1 – P49
Gang (Gary) Xu, Nevin Gerek Ince, Seiya Hirohama, Prasad Narasimhan and David Bluck
Extended distillation and property correlations for heavy oils

1 – P50
Harvey Yarranton, Catalina Sanchez Lemus, Florain Schoeggl and Shawn Taylor
Influence of solvent composition and temperature on the binding strength of

supramolecular complexes formed by perylene derivatives 1 – P51
Jörg Baz and Niels Hansen
20
PPEPPD 2016
12:30 – 15:00

Room
Ionic liquids in gas separation processes: influence of metal salts and water
contents on the viscosity 1 – P52
Gabriel Zarca, Inmaculada Ortiz and Ane Urtiaga
Group-contribution modelling of polystyrene using SAFT-γ force fields:

molecular simulations of polystyrene melts and polystyrene solutions in alkanes
1 – P53
Guadalupe Jiménez-Serratos, Carmelo Herdes, Andrew J. Haslam, George Jackson and
Erich A. Müller
Classical density functional theory for liquid-fluid interfaces and confined systems
using PC-SAFT equation of state 1 – P54
Elmar Sauer and Joachim Groß
Bubble point measurements of n-propane + n-decane binary mixtures with

comparisons of binary mixture interaction parameters for linear alkanes 1 – P55
Elisabeth Mansfield, Ian H. Bell and Stephanie L. Outcalt
Non-equilibrium hydrate phase transitions from aqueous CO2 and CO2 gas
1 – P56
Khadijeh Qorbani, Bjørn Kvamme and Richard Olsen
A new method for accurate measurement of solubility of sparingly soluble gases in

liquids 1 – P57
Amir Hossein Jalili, Ali Pourbashiri and Cyrus Ghotbi
Predicting solid-liquid equilibria of ternary semicrystalline polymer solvent

mixtures by means of lattice cluster theory 1 – P58
Michael Fischlschweiger and Sabine Enders
Atomistic simulations of the formation of perylene-based supramolecular

complexes in aqueous solution 1 – P59
Jörg Baz and Niels Hansen
Corresponding state behaviour of vapour-liquid phase equilibria of confined

square-well fluid 1 – P60
Sudhir K. Singh
21
12:30 – 15:00

Room
Separation of BTEX compounds from natural gas streams using ionic liquids
1 – P61
Mamoun Althuluth, Nerea R. Rodriguez, Cor J. Peters and Maaike C. Kroon
Understanding the interfacial behavior in isopycnic Lennard-Jones fluid mixtures

by computer simulations 1 – P62
José Matías Garrido, Manuel M. Piñeiro, Andrés Mejía and Felipe J. Blas
Extraction of lignin from biomass using deep eutectic solvents

1 – P63
Laura J.B.M. Kollau and Maaike C. Kroon
A new algorithm for simultaneous chemical and phase equilibrium calculation

1 – P64
Christos Tsanas, Wei Yan and Erling H. Stenby
A study on associative groups behaviour: effect of chain growth and hydroxyl

groups positioning into CPA EoS parameters 1 – P65
André M. Palma, Mariana B. Oliveira, António J. Queimada and João A. P. Coutinho
Phase equilibria of butanol isomers in surpercritical carbon dioxide

1 – P66
Sergiu Sima, Adrian Crişciu, Catinca Secuianu, Viorel Feroiu and Dan Geană
Monte Carlo simulations of vapor liquid equilibria of complex polar systems

1 – P67
Eliseo MarinRimoldi and Edward Maginn
Molecular simulation of phase equilibria for mixtures of species with partial

charges and polarizable molecules using Wolf summation 1 – P68
Christian Waibel and Joachim Groß
Fine-tuning of phase and self-aggregation behaviour of fluorinated ionic liquids

in aqueous solutions
1 – P69
Ana B. Pereiro, Fèlix Llovell, João M. M. Araújo, Luis Paulo N. Rebelo, Manuel M. Piñeiro
and Lourdes F. Vega
22
PPEPPD 2016
Monday ARernoon – May, 23

Monday Afternoon – May, 23

Chair: Cor Peters
15:00
Phase equilibria in ionic liquid + carbon dioxide mixtures:
implica5ons for carbon dioxide u5lisa5on
Manuel Nunes da Ponte IL3
15:45
DisWnguished Lecture of Working Party on TTP - EFCE (Costa Verde)
Chairs: Rafiqul Gani and Jean-Charles de HempWnne
15:45
Phase equilibria: from fundamentals to new industrial applica5ons
Cor Peters EFCE
16:30
History of PPEPPD (Costa Verde)

Chairs: Keith Gubbins and Carol Hall
17:00 The PPEPPD conferences 1977 – 2013
John O’Connell HPPEPPD
17:45
15th PPEPPD 2019 (Costa Verde)
Chairs: Keith Gubbins and Carol Hall
17:45
John M. Shaw 15PPEPPD
18:00
23
14
24
Sunday – May 22 Monday – May 23 Tuesday – May 24 Wednsday – May 25 Thursday – May 26
8:30 Room Costa Verde Room Costa Verde Room Costa Verde Room Costa Verde
IL: M. Cas?er IL: H. Hasse IL: M. Elimelech IL: R. Dohrn
9:15
IL: S. Shell IL: X. Zhang IL: C. Koh IL: L. Vega
10:00
Coffee break Coffee break Coffee break Coffee break
10:30 Room Nova Iorque Room Nova Iorque Room Costa Verde Room Nova Iorque
Room Costa Verde Room Costa Verde Room Nova Iorque Room Costa Verde
Rousseau Englezos Sadus Kroon Huang Enders Gani Tavares

11:00
Haslam Llovell McCabe Holzer Palmer Errington Paricaud Jaubert
Cummings Chen Victorov Siperstein Kontogeorgis Gubbins Hemp?nne S-Bartkowiak
Nezbeda Lu Collell Araújo Fraaije Muller Kroenlein Filipe
12:30
13:00
Closing
Lunch Lunch Lunch
14:00 Lunch
Poster Session I Poster Session II Poster Session III
Room Costa Verde Room Costa Verde Room Nova Iorque Room Costa Verde 15:00
IL: M. N. da Ponte KoVe Marrucho IL: M. Thommes
16:00
Mathias Held
EFCEDL: C. Peters JPA: D. Theodorou
Registra?on 16:30
Coffee break Coffee break
17:00
HPPEPPD: J. O’Connell Room Costa Room Nova Room
Verde Iorque Roma
PPEPPD 2019: J. Shaw Excursion Work- Work- Work-

Opening shop 1 shop 2 shop 3 18:40
18:45
Room Costa Verde 19:15
KA: J. de Pablo
20:00
Welcome Recep?on Dinner

Dinner at Taylor’s Conference Dinner
22:00
23:00 -23:30
KA: Keynote Address; IL: Invited Lecture; EFCEDL: European Federa?on of Chemical Engineering Dis?nguished Lecture;
JPA: John M. Prausnitz Award Lecture; HPPEPPD: History of PPEPPD Lecture
Sunday – May 22 Monday – May 23 Tuesday – May 24 Wednsday – May 25 Thursday – May 26
8:30 Room Costa Verde Room Costa Verde Room Costa Verde Room Costa Verde
IL: M. Cas?er IL: H. Hasse IL: M. Elimelech IL: R. Dohrn
9:15
IL: S. Shell IL: X. Zhang IL: C. Koh IL: L. Vega
10:00
Coffee break Coffee break Coffee break Coffee break
10:30
Room Costa Verde Room Nova York Room Costa Verde Room Nova York Room Costa Verde Room Nova York Room Costa Verde Room Nova York
11:00
MMS1 CCS MMS2 RST1 PHE1 SIC1 PHE2 SIC2
12:30
13:00
Closing
Lunch Lunch Lunch
14:00 Lunch
Poster Session I Poster Session II Poster Session III
Room Costa Verde Room Costa Verde Room Nova Iorque Room Costa Verde 15:00
IL: M. N. da Ponte KoVe Marrucho IL: M. Thommes
Held 16:00
Mathias
EFCEDL: C. Peters JPA: D. Theodorou
Registra?on 16:30
Coffee break Coffee break
17:00
HPPEPPD: J. O’Connell Room Costa Room Nova Room
Verde Iorque Roma
PPEPPD 2019: J. Shaw Excursion Work- Work- Work-

Opening shop 1 shop 2 shop 3 18:40
18:45
Room Costa Verde 19:15
KA: J. de Pablo
20:00
Welcome Recep?on Dinner

Dinner at Taylor’s Conference Dinner
22:00
23:00 -23:30
PPEPPD 2016
MMS: Molecular Modeling and Simula?on; CCS: Carbon Capture and Storage; RST: Reac?on and Separa?on Techniques;
PHE: Phase Equilibria; SIC: Surfaces, Interfaces and Confinement; TTP: Thermodynamics and Transport Proper?es
25
Tuesday Morning – May, 24


Chairs: Ioannis Economou and George Jackson
8:30 Chairs: Ioannis Economou and George Jackson
Measuring the unmeasurable by molecular simula5ons
8:30 Measuring the unmeasurable by molecular simula5ons
8:30 Hans Hasse
Measuring the unmeasurable by molecular simula5ons IL4
Hans Hasse
Measuring the unmeasurable by molecular simula5ons IL4
9:15 Hans Hasse IL4
9:15 Hans Hasse
Invited Lecture 5

IL4
(Costa Verde)
9:15 Invited Lecture 5 (Costa Verde)
Mul5scale simula5on and process analysis of ionic liquid systems
9:15 Mul5scale simula5on and process analysis of ionic liquid systems
9:15 Xiangping Zhang
Mul5scale simula5on and process analysis of ionic liquid systems IL5
Xiangping Zhang
Mul5scale simula5on and process analysis of ionic liquid systems IL5
10:00 Xiangping Zhang IL5
10:00 Xiangping Zhang IL5
10:00
10:00

Chairs: Ivo Nezbeda and Georgios M. Kontogeorgis
Chairs: Ivo Nezbeda and Georgios M. Kontogeorgis
10:30 Chairs: Ivo Nezbeda and Georgios M. Kontogeorgis
10:30 Chairs: Ivo Nezbeda and Georgios M. Kontogeorgis
Predic5ng the proper5es of aqueous systems: the role of polariza5on
10:30 Predic5ng the proper5es of aqueous systems: the role of polariza5on
10:30 I. Shvab and Richard J. Sadus
Predic5ng the proper5es of aqueous systems: the role of polariza5on O3-1
I. Shvab and Richard J. Sadus
Predic5ng the proper5es of aqueous systems: the role of polariza5on O3-1
11:00 I. Shvab and Richard J. Sadus O3-1
11:00 I. Shvab and Richard J. Sadus
Understanding the self-assembly and phase behavior of skin lipids O3-1
11:00 Understanding the self-assembly and phase behavior of skin lipids
11:00 Tim C. Moore, Shan Guo, Christopher R. Iacovella, Clare McCabe
Tim C. Moore, Shan Guo, Christopher R. Iacovella, Clare McCabe
11:30 Tim C. Moore, Shan Guo, Christopher R. Iacovella, Clare McCabe O3-2
11:30 Molecular thermodynamic modeling of self-assembly into branches and spa5al
Tim C. Moore, Shan Guo, Christopher R. Iacovella, Clare McCabe O3-2
11:30 Molecular thermodynamic modeling of self-assembly into branches and spa5al
11:30 networks in solu5on
Molecular thermodynamic modeling of self-assembly into branches and spa5al
networks in solu5on
Molecular thermodynamic modeling of self-assembly into branches and spa5al
Igor Gotlib, Michail Voznesenskiy, Ksenia Emelyanova and Alexey Victorov
networks in solu5on O3-3
12:00 Igor Gotlib, Michail Voznesenskiy, Ksenia Emelyanova and Alexey Victorov
networks in solu5on O3-3
Transport of mul5component hydrocarbon mixtures in shale organic maZer O3-3
Transport of mul5component hydrocarbon mixtures in shale organic maZer O3-3
12:00 by molecular simula5ons
Transport of mul5component hydrocarbon mixtures in shale organic maZer
by molecular simula5ons
Transport of mul5component hydrocarbon mixtures in shale organic maZer
Julien Collell, Guillaume Galliero, Romain Vermorel, Philippe Ungerer, Marianna Yiannourakou,
Julien Collell, Guillaume Galliero, Romain Vermorel, Philippe Ungerer, Marianna Yiannourakou,
François Montel and Magali Pujol
Julien Collell, Guillaume Galliero, Romain Vermorel, Philippe Ungerer, Marianna Yiannourakou, O3-4
12:30 François Montel and Magali Pujol
Julien Collell, Guillaume Galliero, Romain Vermorel, Philippe Ungerer, Marianna Yiannourakou, O3-4
12:30 François Montel and Magali Pujol O3-4
12:30 François Montel and Magali Pujol O3-4
12:30
Oral Session 4: ReacWon and SeparaWon Techniques 1 (Nova Iorque)

Chairs: Yoshio Iwai and Jean-Noël Jaubert
Chairs: Yoshio Iwai and Jean-Noël Jaubert
10:30 Chairs: Yoshio Iwai and Jean-Noël Jaubert
10:30 Chairs: Yoshio Iwai and Jean-Noël Jaubert
Hydrophobic deep eutec5c solvents: a new genera5on of water-immiscible extractants
10:30 Hydrophobic deep eutec5c solvents: a new genera5on of water-immiscible extractants
10:30 Dannie J.G.P. van Osch, Lawien F. Zubeir, Adriaan van den Bruinhorst, Marisa A.A. Rocha and
Dannie J.G.P. van Osch, Lawien F. Zubeir, Adriaan van den Bruinhorst, Marisa A.A. Rocha and
Maaike C. Kroon
Dannie J.G.P. van Osch, Lawien F. Zubeir, Adriaan van den Bruinhorst, Marisa A.A. Rocha and O4-1
11:00 Maaike C. Kroon
Dannie J.G.P. van Osch, Lawien F. Zubeir, Adriaan van den Bruinhorst, Marisa A.A. Rocha and O4-1
11:00 Maaike C. Kroon O4-1
11:00 Maaike C. Kroon
Dynamic online process op5miza5on based on rigorous thermodynamics O4-1
11:00 Dynamic online process op5miza5on based on rigorous thermodynamics
Günther Holzer and Thomas Wallek
Günther Holzer and Thomas Wallek
11:30 Günther Holzer and Thomas Wallek O4-2
11:30 From atomis5c simula5ons to process modelling: dehydra5on of gas streams using
Günther Holzer and Thomas Wallek O4-2
11:30 From atomis5c simula5ons to process modelling: dehydra5on of gas streams using
11:30 water stable metal organic frameworks as adsorbents
From atomis5c simula5ons to process modelling: dehydra5on of gas streams using
water stable metal organic frameworks as adsorbents
From atomis5c simula5ons to process modelling: dehydra5on of gas streams using
Flor R. Siperstein and Chung L. Chia
water stable metal organic frameworks as adsorbents O4-3
12:00 Flor R. Siperstein and Chung L. Chia
water stable metal organic frameworks as adsorbents O4-3
The different faces of poly(alkylene glycol)s + nature-inspired ionic fluids aqueous O4-3
The different faces of poly(alkylene glycol)s + nature-inspired ionic fluids aqueous O4-3
12:00 biphasic systems: impact of the hydrophilic-hydrophobic balance on the
The different faces of poly(alkylene glycol)s + nature-inspired ionic fluids aqueous
biphasic systems: impact of the hydrophilic-hydrophobic balance on the
The different faces of poly(alkylene glycol)s + nature-inspired ionic fluids aqueous
phase behavior and the extrac5on of proteins
Sara F. Carvalho, Nicole S. M. Vieira, Márcia Alves, Ana B. Pereiro, Margarida Archer,
Luís Paulo N. Rebelo and João M. M. Araújo
Sara F. Carvalho, Nicole S. M. Vieira, Márcia Alves, Ana B. Pereiro, Margarida Archer, O4-4
26 12:30 Luís Paulo N. Rebelo and João M. M. Araújo
Sara F. Carvalho, Nicole S. M. Vieira, Márcia Alves, Ana B. Pereiro, Margarida Archer, O4-4
12:30 Luís Paulo N. Rebelo and João M. M. Araújo 15
O4-4
12:30 Luís Paulo N. Rebelo and João M. M. Araújo 15
O4-4
12:30 15
15
PPEPPD 2016
Tuesday Lunchtime – May, 24
12:30 – 15:00

Room
Application of e-KT-UNIFAC model for improved and innovative design of biphasic
reacting systems 2 – P01
Amata Anantpinijwatna, Sun Hyung Kim, Mauricio Sales-Cruz and Rafiqul Gani
Solubility of flavonoids in natural deep eutectic solvents

2 – P02
Ning Tang and Weidong Yan
Solubilities of naringin dihydrochalcone in pure solvents and mixed solvents at

different temperatures 2 – P03
Ning Tang and Weidong Yan
Classical density functional theory for liquid-fluid interfaces using modified iSAFT
and the heterosegmented GC-PC-SAFT equation of state 2 – P04
Jonas Mairhofer and Joachim Groß
Enhanced leaching stability of protein adsorbed onto mesoporous materials with

large pore size: a case in mesoporous titania fibers
2 – P05
Chang Liu, Yanhua Guo, Qiliang Hong, Haijuan Zhang, Yihui Dong, Liangliang Huang
and Xiaohua Lu
Transport properties in ternary liquid-liquid systems

2 – P06
Marius Krapoth, Andres Kulaguin Chicaroux and Tim Zeiner
Vapour-liquid equilibria of the binary system (cyclohexanone +2-heptanone) at

different temperatures 2 – P07
Jorge Rubio, M. Carmen Martín, Rosa M. Villamañán, César R. Chamorro and Jose J. Segovia
Improved property packages for process simulation: case studies using the CPA
EoS for simulating the production of petrochemicals 2 – P08
Nuno M. Pedrosa, António J. Queimada, Xiaohong Zhang and Tim Shire
Molecular simulation study of the barrier properties of semi-crystalline

polyethylene 2 – P09
Germain Clavier, Nadège Brusselle-Dupend, Véronique Lachet and Bernard Rousseau
Self-assembly of spherical caps under gravity

2 – P10
John McBride and Carlos Avendaño
27
12:30 – 15:00

Room
Modeling polyester polyol resins and resulting extended chain structures with a
SAFT-γ Mie approach 2 – P11
Amulya Pervaje and Erik Santiso
Effects of electrostatic correlations on micelle formation

2 – P12
Mirella Simões Santos, Evaristo Chaulbaud Biscaia Jr. and Frederico Wanderley Tavares
Modeling of CO2 solubility in electrolyte solutions and brines using statistical

associating fluid theory 2 – P13
Hao Jiang, Athanassios Z. Panagiotopoulos and Ioannis G. Economou
Mutually immiscible ionic liquids for the fractional extraction of mixtures of water
and ethanol
2 – P14
Oussama Bacha, Abdelmalek Hasseine, Manuel N. Lugilde, María C. Castro, Alberto Arce,
Héctor Rodríguez and Ana Soto
The role of structural characteristics of hydroxyapatite-based sorbents for Hg0

removal: a molecular dynamics approach
2 – P15
Carla L. M. Camargo, Amanda G. Oliveira, Neuman S. Resende, Vera M. M. Salim and
Frederico W. Tavares
Confinement effect on chemical reaction yield: the nitric oxide dimer reaction
2 – P16
Deepti Srivastava, C. Heath Turner and Keith E. Gubbins
Investigation of performance of different methods for measuring equilibrium

solubility of carbon dioxide in aqueous alkanolamine solutions in low loading range 2 – P17
Ali T. Zoghi, Azam Najafloo and Farzaneh Feyzi
Improvement of transport properties in osmotic processes by nanocomposite

membranes 2 – P18
Anderson L. Ohland, Neuman S. Resende, Vera M. M. Salim and Cristiano P. Borges
Excess molar enthalpies of deep eutectic solvents (DESs) composed of quaternary

ammonium salts and glycerol or ethylene glycol 2 – P19
Pablo López, Maria Gonzalez-Miquel and Joan F. Brennecke
28
PPEPPD 2016
12:30 – 15:00

Room
High-pressure vapor + liquid equilibria for binary systems CO2 + hexanal and CO2
+ ethyl 2-methylbutyrate
2 – P20
Pablo I. López, Vasco A. Peréz, Rafael A. Villablanca, Arturo Bejarano and Juan C. de la
Fuente
Synthesis and solubility measurement of menadione derivatives, 2-((4-chlorobenzyl)

amino-3-methylnaphtalene-1,4-dione and 2-((4-chlorophenethyl)amino-3-
methylnaphtalene-1,4-dione in supercritical carbon dioxide 2 – P21
Adolfo L. Cabrera, Olga N. Nuñez, Flavia C. Zacconi, José M. del Valle and Juan C. de la
Fuente
Development of a methodology for the sustainability evaluation of industrial

pharmaceutical processes 2 – P22
Andrea Mio, Paola Posocco, Erik Laurini, Sabrina Pricl and Maurizio Fermeglia
Thermodynamic characterization of aqueous mixtures of amines

Eduardo I. Concepción, Daniel Lozano, M. Carmen Martín, Miguel A. Villamañán and 2 – P23
Jose J. Segovia Puras
Group-contribution method for thermal conductivity using PC-SAFT and entropy

scaling 2 – P24
Madlen Hopp and Joachim Groß
Experimental study and modeling on the formation of gas hydrates of methane

and CO2 at high pressure
2 – P25
Maria D. Robustillo, Davi E. Sanches de Menezes, Paula Rocha Ferrador, Thiago Waldowski
Ralha, Luis Fernando Mercier Franco and Pedro de Alcântara Pessôa Filho
Self-assembly of two-dimensional non-convex platelets

2 – P26
Nikoletta Pakalidou and Carlos Avendaño
Database on ionic liquids solubilities in molecular solvents: progress and prospects

2 – P27
Johan Jacquemin, Magdalena Bendová, Zdeněk Wagner and Nan Zhao
High-pressure viscosity measurements for the hydrofluoroether fluid HFE-7500

Natalia Muñoz-Rujas, Jean-Patrick Bazile, Fernando Aguilar, Guillaume Galliero, Eduardo 2 – P28
Montero and Christian Boned
29
12:30 – 15:00

Room
Physico-chemical properties of novel oligoglyme-substituted ionic liquids –
insight into very fine structure-property tuning 2 – P29
Jan Rotrekl, Magdalena Bendová, Zdeněk Wagner, Jan Storch, Věra Pěnkavová and Karel Aim
Activity and osmotic coefficients of binary mixtures of NTf2 – ionic liquids with a
primary alcohol 2 – P30
Noelia Calvar, Ángeles Domínguez and Eugénia A. Macedo
Comparison of 15 alpha functions for the Peng-Robinson EoS applied to vapor

pressure calculation 2 – P31
André Young and Fernando Pessoa
A kinetics and thermodynamic approach on gas hydrate inhibition via

pyrrolidinum based ionic liquids and synergistic compounds 2 – P32
Tausif Altamash, Fahed Qureshi, Bahman Tohidi, Santiago Aparicio and Mert Atilhan
Transport and volumetric properties in binary systems of CO2 and

1-alkyl-3-methylimidazolium ionic liquids
2 – P33
Mitsuhiro Kanakubo, Takashi Makino, Tatsuya Umecky, Masaki Watanabe and Daisuke
Kodama
Prediction of hydrocarbons solubility in aqueous alkanolamine solutions with

CPA-PR EoS 2 – P34
Tianyuan Wang, Elise El Ahmar and Christophe Coquelet
Density, viscosity, electrical conductivity, and CO2 solubility in protonic amidium

ionic liquids 2 – P35
Masaki Watanabe, Daisuke Kodama, Takashi Makino and Mitsuhiro Kanakubo
Effect of molecular topology on hydrocarbon surfactant performance

2 – P36
Jennifer A. Clark, Mariah Ritz and Erik E. Santiso
A group-contribution method for the calculation of transport properties using

PCP-SAFT and entropy scaling 2 – P37
Oliver Loetgering-Lin, Madlen Hopp and Joachim Groß
Multiscale simulations of protein adsorption

2 – P38
Jian Zhou
30
PPEPPD 2016
12:30 – 15:00

Room
Liquid-liquid equilibriums in aqueous solutions of demixing amines loaded with
gas for CO2 capture processes 2 – P39
Yohann Coulier, Alexander R. Lowe, J-Y. Coxam and Karine Ballerat-Busserolles
CALNESIS, applied thermodynamics for industries

2 – P40
Mickaël Simond and Jean-Claude Neyt
A modified exp-6 intermolecular potential function for calculating the second

virial coefficients of pure gases 2 – P41
Hamed Peyrovedin and Alireza Shariati
Development of a transferable force field (TAMie) for phase equilibria of pure

substance and mixtures 2 – P42
Dominik Weidler and Joachim Groß
Separation of n-propanol and n-propyl acetate binary azeotropic mixture using

ionic liquids as entrainers and the isobaric VLE studies of the system 2 – P43
Ankitha Theres George and A.R.Balakrishnan
Estimation of density of ionic liquids using a simple and general group-contribution

method 2 – P44
Hamid Taherifard and Sona Raeissi
Thermodynamic model of the urea synthesis process

2 – P45
Alexey L. Voskov and Gennady F. Voronin
Thermodynamic analysis for the dehydration of n-propanol via heterogeneous

azeotropic distillation using propyl acetate as entrainer 2 – P46
Janakey Devi V. K. P, Sai P. S. T and Balakrishnan A. R
Combining predictive models: predictive PCP-SAFT & COSMO-RS

2 – P47
Sebastian Kaminski, André Bardow and Kai Leonhard
Experimental determination and modeling of volumetric properties and flash

points of (fatty acid ethyl esters + alkanes) binary mixtures
2 – P48
Kamel Khimeche, Lakhdar Sahraoui, Mokhtar Benziane, Ilham Mokbel, Abdessalem
Mohamed and Djalal Trache
31
12:30 – 15:00

Room
Density measurements under pressure for the binary system di-isopropyl ether +
1-butanol at temperatures up to 353.15 K and at pressures up to 100 MPa 2 – P49
Adil Srhiyer, José Juan Segovia, Fernando Aguilar and Eduardo Montero
Thermodynamic properties of some alkanoic acids as potential energy storage

materials for low temperature applications 2 – P50
Diana Díez-Alcalde, Natalia Muñoz-Rujas, Fernando Aguilar and Eduardo Montero
Solubility of CO2 in mixtures of ionic liquids and organic compounds: inducing a

liquid-liquid phase split 2 – P51
Michael J. Lubben and Joan F. Brennecke
Understanding the mechanism of the protein cold denaturation with fully-

atomistic molecular simulations 2 – P52
Sang Beom Kim, Jeremy C. Palmer and Pablo G. Debenedetti
Organic matter of shale: insight from atomistic simulations

2 – P53
Lukáš Michalec and Martin Lísal
Solvent effects of renewable solvent and ionic liquid as greener entrainer for the
separation of binary azeotropic mixtures by extractive distillation
2 – P54
Hiroyuki Matsuda, Koji Inaba, Keiji Nishihara, Hirofumi Sumida, Kiyofumi Kurihara, and
Katsumi Tochigi
Solubilities and diffusion coefficients of dyestuffs in supercritical carbon dioxide

by chromatographic method 2 – P55
Toshitaka Funazukuri, Taichi Yamasaki, Chang Yi Kong and Minori Taguchi
Solid–liquid phase equilibria of binary mixtures containing terpenes and long

chain alcohols 2 – P56
Marisa A. A. Rocha, Sabine Wagenfeld, Bernd Rathke and Johannes Kiefer
Correlation of the high-pressure heat of mixing of binary systems containing

carbon dioxide using the Peng-Robinson equation of state 2 – P57
Kiyofumi Kurihara, Tomohiro Kobayashi, Hiroyuki Matsuda and Katsumi Tochigi
A new equation of state based on Wertheim’s thermodynamic perturbation theory

of third order 2 – P58
Wasilios Zmpitas and Joachim Groß
32
PPEPPD 2016
12:30 – 15:00

Room
Thermophysical properties and LLE with water of [Nf2]- based ionic liquids
2 – P59
R. Fidalgo, O. G. Sas, I. Domínguez, B. González and A. Domínguez
Study of ABS systems of ionic liquids: 1-butyl-3-methyl imidazolium dicyanamide,

[bmim][dca] and 1-ethyl-3-methyl imidazolium dicyanamide, [emim][dca] 2 – P60
Lorena P. Armada, Begoña González and Andrés Moure
Phase behaviour of surfactant ionic liquids for EOR applications

Iria Rodríguez-Escontrela, Iago Rodríguez-Palmeiro, Óscar Rodríguez, Alberto Arce and 2 – P61
Ana Soto
Simulaneous description of activity coefficients and solubility with electrolyte CPA

2 – P62
Anders Schlaikjer, Kaj Thomsen and Georgios M. Kontogeorgis
Thermodynamic stability of xenon+benzene mixed hydrates

2 – P63
Takeshi Sugahara
Effects of polymer polydispersity on liquid-liquid equilibrium

2 – P64
Han Earl Yang and Young Chan Bae
Vapour-liquid equilibria and density modelling of CO2-rich systems with PC-SAFT

and SAFT-VR Mie 2 – P65
Alfonso González Pérez, Patrice Paricaud, Antonin Chapoy and Christophe Coquelet
Thermal behavior of tricyanomethanide-based ionic liquids:

experimental determination and structure-property relationship 2 – P66
Lawien F. Zubeir, Marisa A. A. Rocha and Maaike C. Kroon
Free energy calculations of capped gold nano crystals

2 – P67
Gernot Bauer and Joachim Groß
Solubility of anthraquinone and their derivatives in supercritical carbon dioxide

2 – P68
Kazuhiro Tamura, Tatsuro Tanaka, Keisuke Shimizu and Ratna Surya Alwi
Application of an equation-of-state based activity coefficient model

2 – P69
Ning-Ju Yang, Ming-Jer Lee and Ding-Yu Peng
Molecular simulation of confined fluids: pure components and mixtures

2 – P70
Luis Fernando Mercier Franco, Marcelo Castier, Ioannis G. Economou
33
Tuesday ARernoon – May, 24

Tuesday Afternoon – May, 24
Oral Session 5: Thermodynamics and Transport ProperWes (Costa Verde)

Chairs: Andrés Mejía and CaWnca Secuianu
15:00
High-precision, high-efficiency calcula5on of proper5es by molecular simula5on
Andrew J. Schultz, Sabry G. Moustafa, Weisong Lin and David A. KoXe O5-1
15:30
Effect of phase-equilibrium uncertain5es on the separa5on of heterogeneous azeotropes –
applica5on to the water/1-butanol system
Paul M. Mathias O5-2
16:00

Chairs: Maaike C. Kroon and Eduardo J. Filipe
15:00
Eutec5c solvents: designing solvents for the future
Catarina Florindo, Andreia Gouveia, Bernardo D. Ribeiro and Isabel M. Marrucho O6-1
15:30
Applica5on of thermodynamics to bioreac5ons
Christoph Held O6-2
16:00
34
22
PPEPPD 2016
Wednesday Morning – May, 25

Wednesday Morning – May, 25

Chairs: Susana Borni and Xiaohua Lu
8:30
Energy efficiency of desalina5on: role of membranes and process design
Menachem Elimelech IL6
9:15
Chairs: Susana Borni and Xiaohua Lu
9:15
Gas hydrates, desalina5on & energy applica5ons
Carolyn Koh IL7
10:00
Oral Session 7: Phase Equilibria 1 (Costa Verde)

Chairs: Clare McCabe and Karel Aim
10:30
Phase behavior of amino acids on graphene oxide, 5tanium dioxide and their nanocomposite
Liangliang Huang, Shanshan Wang, Chang Liu, Linghong Lu and Xiaohua Lu O7-1
11:00
Phase transi5ons in models of deeply supercooled of water
Jeremy C. Palmer, Fausto Martelli, Francesco Ricci, Roberto Car,
Athanassios Z. Panagiotopoulos and Pablo G. Debeneder O7-2
11:30
20 years with the CPA equa5on of state
Georgios M. Kontogeorgis O7-3
12:00
Hybrid datamining-thermodynamic method for coarse-grained phase calcula5ons in
petrochemical and biological complex fluids
Johannes G.E.M. Fraaije and Ruben Serral Gracia O7-4
12:30
Oral Session 8: Surfaces, Interfaces and Confinement 1 (Nova Iorque)

Chairs: Bernard Rousseau and Joachim Groß
10:30
Influence of molecule architecture on phase equilibria and interfacial proper5es
Christoph Walowski, Patrick Zimmermann and Sabine Enders O8-1
11:00
Molecular simula5on study of fluids in geological forma5ons
Wenjing Guo, Adam R. Rall and Jeffrey R. Errington O8-2
11:30
Confinement-induced high pressure phases in nanopores.
Can the pressure be in the megabar range?
Cody K. Addington, DeepW Srivastava, Liangliang Huang and Keith E. Gubbins O8-3
12:00
Predic5ve molecular-based theory for interfacial tensions of industrial fluids
José Mauas Garrido, Manuel M. Piñeiro, Felipe J. Blas, Erich A. Müller and Andrés Mejía O8-4
12:30
35
23
Wednesday Lunchtime – May, 25
12:30 – 15:00

Room
The phase behavior of solutions of ionic liquids
3 – P01
Wolffram Schröer and Bernd Rathke
Nitrogen and oxygen solubility measurement in styrene, and effect on radical

polymerization of styrene 3 – P02
Shigeo Oba and Tomoya Tsuji
Influence of a proposed model in the simulation of a distillation process conducted

in a packed column 3 – P03
Adriel Sosa, Raul Rios, Luis Fernández and Juan Ortega
Solid-fluid equilibria of adsorbed Yukawa mixtures

3 – P04
Lloyd L. Lee, Anele Mkanya and Giuseppe Pellicane
Phase equilibrium and surface tension of binary and ternary polymer solutions
3 – P05
Jisu Choi and Youngchan Bae
Switching the doubly thermo-sensitivity of LCST type core-shell gels in mixed

solvent 3 – P06
Chan Hee Lee , Sang Kyu Ryu and Young Chan Bae
Thermodynamic and transport properties of biodiesel and petro-diesel mixtures

at high pressures and temperatures 3 – P07
Gorica R. Ivaniš, Ivona R. Radović, Vlada B. Veljković and Mirjana Lj. Kijevčanin
Prediction of liquid-liquid partitioning of active pharmaceutical ingredients with

the SAFT-γ Mie approach
3 – P08
Panatpong Hutacharoen, Simon Dufal, Vasileios Papaioannou, Ravi M. Shanker, Claire S.
Adjiman, Amparo Galindo and George Jackson
Modeling of hydrocarbons droplets dissolution in near-critical or supercritical

water based on GCA-EoS fugacity predictions
3 – P09
Ping He, Francisco A. Sanchez, Selva Pereda and Ahmed F. Ghoniem

Modeling of the thermodynamic properties and phase equilibria in the system

water – nitric acid – tributyl phosphate – europium nitrate 3 – P10
36 Aleksey I. Maksimov and Nikita A. Kovalenko
PPEPPD 2016
12:30 – 15:00

Room
Microfluidic measurements of diffusion in liquids using confocal Raman spectroscopy
Christine Peters, Julia Thien, Sandra Haase, Carsten Flake, Ludger Wolff, Hans-Jürgen Koß 3 – P11
and André Bardow
Prediction of thermodynamic, transport and permeability properties of ionic

liquids using molecular simulation 3 – P12
Niki Vergadou and Eleni Androulaki
Phase behavior and compositional variation modeling of petroleum fluids

containing asphaltene and CO2 by CPA-EoS 3 – P13
José A. Scilipoti, Pedro H. R. Alijó, Rogério O. Espósito and Frederico W. Tavares
The effect of material flexibility on the drying transition of water between

hydrophobic objects: thermodynamics and kinetics 3 – P14
Y. Elia Altabet and Pablo G. Debenedetti
Development of a group-contribution approach for the description of molecular

ions using SAFT-γ Mie
3 – P15
Georgia Lazarou, Esther Forte, Simon Dufal, Ravi M. Shanker, Claire Adjiman, George
Jackson and Amparo Galindo
Study and prediction of mixture interaction parameters for empirical multi-

parameter mixture models 3 – P16
Ian H. Bell and Eric W. Lemmon
Thermodynamic approach to the separation of rare earth elements

Nikita A. Kovalenko, Aleksey I. Maksimov, Alexander E. Moiseev, Michail A. Zhilin, 3 – P17
Anatoly S. Arkhipin and Irina A. Uspenskaya
Extensive accuracy test of the force-field based quasi-chemical method PAC-MAC

3 – P18
Teun Sweere and Hans Fraaije
Assessment of mass transfer parameters in olefin facilitated transport through

polymer-ionic liquid composite membranes 3 – P19
Daniel Gorri, Raúl Zarca, Alfredo Ortiz, Marcos Fallanza and Inmaculada Ortiz
Modelling the contribution of ring formation within a SAFT framework

Sara A. Febra, Simon Dufal, Ravi M. Shanker, Amparo Galindo, Claire S. Adjiman and 3 – P20
George Jackson 37
12:30 – 15:00

Room
Computational assessment between different-type materials for CO2 capture
3 – P21
Daniel Bahamon and Lourdes F. Vega
Extension of the NRTL-PRA model for the modeling of mixtures containing

electrolytes 3 – P22
Evelyne Neau and Christophe Nicolas
Separation of heptane + ethanol azeotrope using choline chloride based binary

and ternary deep eutectic solvents 3 – P23
Jelena M. Vuksanović, Mirjana Lj. Kijevčanin, Nina M. Todorović and Ivona R. Radović
Electrolyte and nonelectrolyte heterosegmented PC-SAFT equation of state

applied to ionic liquids and their mixtures with molecular solvents 3 – P24
Kamil Paduszyński
Physical properties for binary systems containing deep eutectic solvent and
alcohols at different temperatures
3 – P25
Olalla G. Sás, Rubén Fidalgo, Irene Domínguez, Eugénia A. Macedo and Begoña
González
Deep eutectic solvent-based aqueous two phase system: a benign route as novel
extraction media 3 – P26
Irene Domínguez, Eugénia A. Macedo, Angeles Domínguez and Begoña González
Group-contribution approach for prediction of enthalpies of solvation of aromatic

and heterocyclic compounds in different solvents at 298.15 K 3 – P27
Mikhail Varfolomeev, Ruslan Nagrimanov and Boris Solomonov
Uncertainty quantification and propagation associated with a transferable

intermolecular potential model for n-alkanes 3 – P28
Richard A. Messerly, Thomas A. Knotts IV, Richard A. Rowley and W. Vincent Wilding
Improved phase stability testing in the single phase region

3 – P29
Dan Vladimir Nichita
Taxonomy of cocrystal ternary phase diagrams

3 – P30
Richard B. McClurg
38
PPEPPD 2016
12:30 – 15:00

Room
New measurement technique for surface tension at high-temperature/high-
pressure fluid phase equilibrium 3 – P31
Yohei Kayukawa, Masato Umehara and Katsuyuki Tanaka
A new electrolyte model for inhibited hydrate phase equilibria predictions

3 – P32
Muhammad N. Khan, Hao Qin, Pramod Warrier, Cor J. Peters and Carolyn A. Koh
Computational platform to design crystal growth inhibitors for zeolites

3 – P33
R. John Clark, Jeremy C. Palmer and Jeffrey D. Rimer
Hydration structure and dynamics of poly(2-methacryloyloxyethyl

phosphorylcholine) 3 – P34
Christoph Klein, Christopher R. Iacovella, Clare McCabe and Peter T. Cummings
A pure prediction method for binary VLE established using experimental data of
5000 binaries 3 – P35
Satoru Kato
Liquid-liquid equilibria in ethyl propanoate+heptane+[pyridinium-derived][F4B]

ionic liquids. experimental results and modeling 3 – P36
Luis Fernández, Juan Ortega and Raul Rios
Polymer-salt ATPS: phase diagrams and modeling

3 – P37
Marlen González-Amado, Eva Rodil, Alberto Arce, Ana Soto and Oscar Rodríguez
Switching solution properties using photochromic ionic liquids

Mário R.C. Soromenho, Filipa Siopa, José N. Canongia Lopes, Luís P. N. Rebelo, Carlos A. 3 – P38
M. Afonso and José M. S. S. Esperança
Adsorption behavior of metal precursors on mesoporous silica in supercritical

carbon dioxide
3 – P39
Ikuo Ushiki, Naoto Takahashi, Masaki Ota, Yoshiyuki Sato, Richard L. Smith Jr. and
Hiroshi Inomata
Theoretical analysis of ePC-SAFT equation of state for predicting infinite dilution

partition coefficients in supercritical CO2 – ionic liquid biphasic systems 3 – P40
Yuya Hiraga, Yoshiyuki Sato and Richard L. Smith, Jr.
39
12:30 – 15:00

Room
Multicriteria screening approach for solvent selection and design for CO2 capture
3 – P41
Maria Teresa Mota-Martinez, Jason P. Hallett and Niall Mac Dowell
Spontaneous multilayering in Langmuir films of ionic liquids at the air-water

interface
3 – P42
Eduardo J. M. Filipe, Nathalie Bonatout, Pedro Morgado, Miguel Teixeira, Karina Shimizu,
Michel Goldmann and José Nuno Canongia Lopes
Vapor pressure and liquid density of fluorinated alcohols: experimental,

simulation and GC-SAFT-VR predictions
3 – P43
Gonçalo M. C. Silva, Pedro Morgado, Jessica D. Haley, Víctor Manuel Trejos Montoya,
Clare McCabe, Luís F. G. Martins and Eduardo J. M. Filipe
Rheological properties of mixtures involving ionic liquids and molecular solvents

3 – P44
Luís F. G. Martins, Bruno M. S. Faria, Pedro Morgado and Eduardo J. M. Filipe
Solubility of water in alkanes, perfluoroalkanes and perfluoroalkylalkanes:

experimental results, SAFT modeling and molecular dynamics simulations
3 – P45
Pedro Morgado, Pedro Duarte, Gaurav Das, Amparo Galindo, Clare McCabe and Eduardo
J. M. Filipe
Flower pollination algorithm for LLE data modeling in food systems

3 – P46
Abdelkrim Merzougui and Adrián Bonilla-Petriciolet
Lubrication behavior of water molecules confined in TiO2 nano-slits: molecular

dynamics study
3 – P47
Yudan Zhu, Yumeng Zhang, Mingjie Wei, Luzheng Zhang, Yijun Shi, Xiaohua Lu and
Linghong Lu
Lactic acid recovery from amine extractants using temperature swing

3 – P48
Marek Blahusiak, Dion Smink and Boelo Schuur
Modeling of asphaltene onset precipitation conditions using the

cubic-plus-association equation of state 3 – P49
Alay Arya, Nicolas von Solms and Georgios Kontogeorgis
40
PPEPPD 2016
12:30 – 15:00

Room
Understanding heterogeneous gas hydrate nucleation using molecular simulations
3 – P50
Ryan DeFever and Sapna Sarupria
A novel computer-aided model-based tool for chemical product design

3 – P51
Sawitree Kalakul, Rehan Hussain, Nimir Elbashir and Rafiqul Gani
Predictive models for amphiphilic properties of sugar-based surfactants

3 – P52
Théophile Gaudin, Guillaume Fayet, Patricia Rotureau and Isabelle Pezron
Coarse-grained force fields for oligomers and polymers using SAFT-γ Mie
3 – P53
Jos Tasche and Mark R. Wilson
Process design to obtain copper sulfate crystals using solid–liquid equilibrium of

copper sulfate – sulfuric acid – seawater 3 – P54
María E. Taboada, Francisca J. Justel, Yecid P. Jiménez and Teófilo Graber
Application of regular solutions to predict water activity and applications for

freezing point 3 – P55
Marina Dupas-Langlet
Evidence of structure-function relation for anti-agglomerants at the hydrate-

hydrocarbon interface 3 – P56
Tai Bui, Anh Phan, Alberto Striolo, Pushkala Krishnamurthy and Erick Acosta
Saturating narrow pores with water enhances the selectivity of membrane

separations 3 – P57
Anh Phan and Alberto Striolo
Phase equilibria involving carbon dioxide, reactants and products of an aldol

reaction
3 – P58
Técio Santos Bastos, Rafael Cassaro, Reinaldo C. Bazito, Cláudio Dariva, Gustavo Borges,
Silvia Maria Egues Dariva and Elton Franceschi
Viscoeslatic properties of crude oil emulsions in the presence of IL

3 – P59
Douglas Alves, Everton Lourenço, Elton Franceschi, Gustavo Borges and Claudio Dariva
41
12:30 – 15:00

Room
NH3 absorption in Brønsted acidic imidazolium-based ionic liquids
3 – P60
Takashi Makino and Mitsuhiro Kanakubo
Water on TiO2 nanotubes: a molecular dynamics simulation

3 – P61
Wei Cao, Linghong Lu, Liangliang Huang and Xiaohua Lu
Modeling and simulation of CO2 capture from biogas using aqueous choline
chloride/urea 3 – P62
Chunyan Ma, Chang Liu, Yujiao Xie, Xiaoyan Ji and Xiaohua Lu
A data processing method for measurement of diffusion coefficient by digital

holographic interferometry 3 – P63
Shi Zhang, Ying Zhang, Sanguo Peng and Maogang He
Bubble nucleation in industrial fluids: A case study combining molecular

simulations and equations of state + density gradient theory
3 – P64
Kai Langenbach, Stephan Werth, Manfred Heilig, Gerd Haderlein, Martin Horsch and
Hans Hasse
Micelle formation and micro-structure of ionic liquids in aqueous solutions

3 – P65
Xiaomin Liu, Feng Huo and Suojiang Zhang
Bubble pressure measurement and prediction for n-alkane + aromatic and

naphthenic hydrocarbon binary mixtures 3 – P66
Qingchen Liu, Sourabh Ahitan, Marco Satyro and John M. Shaw
Phase diagram and saturated phase property measurement and simulation for
peace river bitumen + propane mixtures 3 – P67
Yoann Dini, Marco Satyro and John M. Shaw
Generation and thermodynamic modelling of vapour-liquid equilibrium data for

aroma compounds in hydroalcoholic mixtures – application to the simulation of
spirits distillation units 3 – P68
Cristian Puentes, Martine Esteban-Decloux and Patrice Paricaud
42
PPEPPD 2016
Wednesday ARernoon – May, 25

Wednesday Afternoon – May, 25

Chair: Joan Brennecke
15:00
Insights into the adsorp5on and phase behaviour of fluids in micro-mesoporous adsorbents
with hierarchical pore structure: towards an advanced pore structural characteriza5on
Ma.hias Thommes IL8
15:45
Jonh M. Prausnitz Award (Costa Verde)
Chairs: Athanassios Z. Panagiotopoulos and Peter T. Cummings
15:45
Mul5scale molecular simula5ons of polymer matrix nanocomposites
Doros N. Theodorou PA
16:30
Workshop 1: ApplicaWons of SAFT-type models (Costa Verde)

Chair: Gabriele Sadowski
17:00
An introduc5on to SAFT and applica5ons in the energy industry
Walter Chapman WSAFT-1
Integrated molecular and process design with the SAFT plaform

George Jackson WSAFT-2
Applica5on of PC-SAFT to pharmaceu5cal systems

Gabriele Sadowski WSAFT-3
Predic5ng interfacial proper5es and transport proper5es using SAFT equa5ons of state
Joachim Gross WSAFT-4
Panel discussion and concluding remarks

Gabriele Sadowski
18:40
43
29
Wednesday ARernoon – May, 25

Wednesday afternoon– May, 25
Workshop 2: Force fields for properWes and phase equilibria for product and process design
Chair: Ioannis G. Economou (Nova Iorque)
17:00
Transferable poten5als for phase equilibria:
development, valida5on, verifica5on, and uncertainty
J. Ilja Siepmann WFF-1
Three worked examples for developing force fields: water, hydrates and NaCl solu5ons
Carlos Vega WFF-2
Coarse grained force field development:
applica5ons within the corresponding states framework
Guillaume Galliero WFF-3
Polarizable force fields for property predic5on of CO2 – brine
mixtures related to CCS and EOR processes
Ioannis G. Economou WFF-4
Ioannis G. Economou
18:40
Workshop 3: Industry: Research and InnovaWon (Roma)

Chair: João Fugas
17:00 Galp Energia Director
Carlos MarCns Andrade WR&D-1
Solvay R&I process engineer

Mathias Brehelin WR&D-2
Perstorp Vice President Process Innova5on

Oleg Pajalic WR&D-3
CEFIC, Execu5ve Director Research and Innova5on

Pierre Barthélemy WR&D-4

João Fugas
18:40
44
30
PPEPPD 2016
Thursday Morning – May, 26

Thursday Morning – May, 26

Chairs: Walter Chapman and John Shaw
8:30
Proper5es and phase equilibria – examples from industrial applica5ons
Ralf Dohrn IL9
9:15
Chairs: Walter Chapman and John Shaw
9:15
SAFT as a tool for phase equilibria calcula5ons and process design:
advances and remaining challenges
Lourdes Vega IL10
10:00
Oral Session 9: Phase Equilibria 2 (Costa Verde)

Chairs: Ana Soto and Erich Hendriks
10:30
Modeling of phase equilibria for aqueous-organic electrolyte systems
Sun Hyung Kim, Amata Anantpinijwatna, Jeong Won Kang and Rafiqul Gani O9-1
11:00
Reop5miza5on of COSMO-SAC parameters for vapor-liquid equilibrium using
cri5cally evaluated data
Eugene Paulechka, Vladimir Diky, Andrei Kazakov, Michael Frenkel and Kenneth Kroenlein O9-2
11:30
A new model for water in GC-PPC-SAFT and subsequent modeling of LLE, VLE, VLLE of
water mixtures with hydrocarbons and oxygenates
Saifuddin Ahmed, Nicolas Ferrando and Jean-Charles de HempCnne O9-3
12:00 Experimental measurements and predic5ons of the proper5es of
refrigerant fluids using ab-ini5o, SAFT-VR Mie and COSMO calcula5ons
J. Glorian, J. El. Abbadi, J. Janecek, P. Paricaud, L. Catoire, J. Deschamps, C. Houriez, C. Coquelet,
12:30 O. Baudouin, A. Baba-Ahmed and G. Fuchs O9-4
Oral Session 10: Surfaces, Interfaces and Confinement 2 (Nova Iorque)

Chairs: Chau-Chyun Chen and Isabel M. Marrucho
10:30 Modeling of confined fluids via molecular simula5on and equa5on of state
Gabriel D. Barbosa, Leonardo Travalloni, Frederico W. Tavares and Marcelo CasWer O10-1
11:00 Op5mal design of the cohesive parameter in cubic equa5ons of state
Romain Privat, Silvia Lasala, Yohann Le Guennec and Jean-Noël Jaubert O10-2
11:30 Water confined in nanopores; the stacking-disordered ice structures
Kamila Domina, Kwong Y Chanb, Małgorzata Śliwinska-Bartkowiaka, Yun Longc and Keith E. Gubbins O10-3
12:00 Mixtures of hydrogenated and fluorinated chains: thermodynamics,
spectroscopy and simula5on
Ana Rosa Garcia, Pedro Morgado, Miguel Teixeira, Luís F. G. MarWns, Laura Ilharco
and Eduardo J. M. Filipe O10-4
12:30
Closing Session (Costa Verde)
Eugénia A. Macedo and José N. Canongia Lopes
45
31
Maria Eugénia Rebello de A. Macedo

Departamento de Engenharia Química, Faculdade de Engenharia da Universidade do Porto
E-mail: eamacedo@fe.up.pt | Tel: +351 225 081 653
José Nuno Canongia Lopes

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa
E-mail: jnlopes@tecnico.ulisboa.pt | Tel: +351 218 419 261
46 https://paginas.fe.up.pt/~ppeppd2016/PPEPPD/Home.html
SUNDAY – MAY, 22
Keynote Address
Nanoparticles in liquid crystals, and liquid crystals in nanoparticles.
Juan de Pablo*
Institute for Molecular Engineering, University of Chicago, 5747 S. Ellis Avenue, Chicago IL 60637,USA
*Corresponding author: depablo@uchicago.edu
Abstract
(Liquid crystals are remarkably sensitive to interfacial interactions. Small perturbations at a liquid crystal
interface can in fact be amplified over relative long distances, thereby providing the basis for a wide
range of applications. Our recent research efforts have focused on the reverse phenomenon; that is, we
have sought to manipulate the interfacial assembly of nanoparticles or the organization of surface active
molecules by controlling the structure of a liquid crystal. This presentation will consist of a review of the
basic principles that are responsible for liquid crystal-mediated interactions, followed by demonstrations
of those principles in the context of several examples. In the first, a liquid crystal is used to direct the
assembly of nanoparticles; through a combination of molecular and continuum models,we show how
minute changes in interfacial energy and particle size lead to liquid-crystal induced attractions that can
span multiple orders of magnitude. Theoretical predictions are confirmed by experimental observations,
which also suggest that LC-mediated assembly provides an effective means for fabrication of plasmonic
devices. In a different set of applications, the structure of a liquid crystal is controlled by confinement.
The morphology of the liquid crystal depends on a delicate balance between bulk and interfacial
contributions to the free energy, and we show how that balance can be manipulated and exploited in a
wide array of sensing devices.

PPEPPD 2016
th
14 International Conference on Properties and
MONDAY – MAY, 23
Invited Lecture 1
Thermodynamic modeling of fluids confined in porous media: an overview of

selected approaches
Marcelo Castier
Chemical Engineering Program, Texas A&M University at Qatar, Qatar
*Corresponding author: marcelo.castier@qatar.tamu.edu
Scientific topic: Thermodynamic and transport properties
Keywords: molecular dynamics, zeolitic imidazolate frameworks, adsorption, equations of state
Abstract
Modeling the behavior of oil and gas in reservoirs, designing adsorption-based separation units,
and predicting capillary condensation are among the many problems that depend on the
properties of fluids close to solid walls. The approaches to model them vary widely. Historically
important isotherms, such the Langmuir and Freundlich models, are simple to use but the
restrictive assumptions used in their derivations limit their applicability. Detailed simulations
that use either molecular dynamics or the Monte Carlo method provide much insight into the
properties and phenomena of fluids confined in small spaces at the cost of computational loads
that are still too large for routine use in chemical process design. Methods based on classical
density functional theory and on equations of state for confined fluids have intermediate
complexity and computational load, and are potentially applicable to engineering design. This
presentation will cover some of these approaches. One topic will be the application of molecular
dynamics to simulate the separation of light gases in ZIFs (zeolitic imidazolate frameworks). A
second topic will be the development and application of equations of state for confined fluids,
which will be illustrated with results of adsorption equilibrium of pure components and mixtures
and heats of adsorption, in homogeneous and heterogeneous adsorbents. The final topic will be
the deployment of a generalized framework for the calculation of thermodynamic equilibrium in
fluids subject to multiple external fields, as those imposed by the walls of a heterogeneous
adsorbent and by the solid walls and gravity in the isothermal compositional grading of confined
fluids.
Acknowledgement
This work was made possible by NPRP grants 4-1484-2-590, 5-344-2-129, and 7-042-2-021 from the Qatar
National Research Fund (a member of Qatar Foundation). The statements made herein are solely the responsibility
of the author.

PPEPPD 2016
th
Invited Lecture 2
Coarse-Graining with the Relative Entropy: Recent Theory and Algorithms
M. Scott Shell1*
1
Department of Chemical Engineering, University of California Santa Barbara, USA
*Corresponding author: shell@engineering.ucsb.edu
Scientific topic: Molecular and multiscale simulation
Keywords: relative entropy, coarse-graining, multiscale, biomolecules
Abstract
We discuss a general approach to multiscale modeling based on the idea of variational minimization of
the information loss upon coarse-graining, naturally measured by a quantity called the relative entropy.1
This formalism offers a particularly broad statistical-mechanical framework that can be used to improve
both theoretical (analytical) and computational (simulation) models of complex systems.2,3,4 We discuss
conceptual and numerical aspects of this approach and illustrate its use with several case studies,
including water, hydrophobic interactions, peptide folding, and peptide self-assembly. We also discuss
recent extensions of the relative entropy approach to address the transferability of coarse-grained
potentials, the inclusion of multibody interactions in coarse-grained models, and the determination of the
optimal number and placement of pseudoatoms.
References
[1] M. S. Shell “The relative entropy is fundamental to multiscale and inverse thermodynamic problems” J. Chem.
Phys. 2008, 129: 144108.
[2] A. Chaimovich and M. S. Shell “Coarse-graining errors and optimization using a relative entropy framework” J.
Chem. Phys. 2011, 134: 094112.
[3] S. P. Carmichael and M. S. Shell “A New Multiscale Algorithm and its Application to Coarse-Grained Peptide
Models for Self-Assembly” J. Phys. Chem. 2012, 116: 8383.
[4] S. P. Carmichael and M. S. Shell “Entropic (de)stabilization of surface-bound peptides conjugated with
polymers” J. Chem. Phys. 2015, 143: 243103.
Acknowledgements
The author gratefully acknowledges the support of the U.S. National Science Foundation (Award No. CHE-
1300770).

PPEPPD 2016
th
Invited Lecture 3
Phase equilibria in ionic liquid + carbon dioxide mixtures: implications for

carbon dioxide utilisation
Manuel Nunes da Ponte

LAQV/REQUIMTE, Department of Chemistry, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa
*Corresponding author: mnponte@fct.unl.pt
Abstract
Interest in the development of ionic liquids that may dissolve large amounts of carbon dioxide has been
increasing rapidly, due to their potential use for carbon capture from power plants and cement factories,
in the context of global warming mitigation strategies. This research has been carried out basically at
atmospheric pressure. This in contrast with a smaller cohort of studies at high pressure, which has been
steadily proposing new applications in separations and reaction, and, in particular, in carbon dioxide
utilization, where CO2 is itself a reagent. Properties, such as solubility and viscosity, of the ionic liquid
phase in these high pressure mixtures are, in general, more favourable for reaction. But the nature of the
ionic liquid and its interactions with solid surfaces that may act as catalysts are also very important.
Examples will be given of carbon dioxide reduction in ionic liquids, either with hydrogen or
electrochemically, where multiphase equilibria, involving solid catalysts in the form of nanoparticles, is
an essential element of control of the products and yields of reaction.

PPEPPD 2016
th
EFCE
Phase Equilibria: from Fundamentals to New Industrial Applications
Cor J. Peters
Department of Chemical Engineering, The Petroleum Institute, Abu Dhabi, United Arab Emirates
*Corresponding author: cpeters@pi.ac.ae
Abstract
Phase equilibria for product and process design require proper and correct knowledge of the fundamental
thermodynamic principles behind this. In that respect, for decades molecular simulations have
contributed significant knowledge, insight and understanding to develop new and / or better models for
direct application in industrial process simulators. Nevertheless, there is still a need for further
improvement of molecular-based models, as will be demonstrated by some examples, among them for
asphaltene-containing systems, the cholesterol of the oil industry.
Although there is a worldwide reduction of experimentally oriented research on phase equilibria,

experiments remain a must for several reasons, e.g., to offer data for parameter estimation for both semi-
empirical and molecular models. Based on this view, this year a thermo-physical properties lab, with
extended facilities, will be commissioned at the Petroleum Institute.
Depletion of high-quality resources of oil and gas are becoming a near-future reality, necessitating to
bring reservoirs with high concentrations of undesired components like CO2, H2S, BTX, mercury, etc. in
production. Current capturing technology for bulk-removal of, in particular, CO2 and H2S, is
underdeveloped and, consequently, industry calls for improved and / or new technology. Therefore,
research at the Petroleum Institute has a main focus on developing novel solvents like Ionic Liquids
(ILS) and Deep Eutectic Solvents (DES) and, in addition, to apply High Gravity forces to enhance the
dissolution kinetics of the absorption processes. Also the application of ILS and DES for mercury
capturing, which is a collaborative project with the University of Minnesota (USA), will be highlighted.
Collaborative research also exists between the Petroleum Institute and the Hydrate Center at Colorado
School of Mines (USA). It concerns the application of gas hydrates in desalination of seawater and
industrial production water. Furthermore, the use of gas hydrates for CO2-capturing from flue gases and
H2 / CO2 mixtures is a research objective, which will be presented.

PPEPPD 2016
th
Oral Session 1 – Molecular Modeling and Simulation 1 - O1-1
Molecular simulation study of the mechanical properties of semi-crystalline

polyethylene
Germain Clavier1,2, Nadège Brusselle-Dupend3, Véronique Lachet1 and Bernard Rousseau2*

1
Thermodynamic and Molecular Simulation Department, IFP Energies nouvelles, Rueil-Malmaison, France
2
Physical Chemistry Department, CNRS UMR8000, Université Paris-Sud, Orsay, France
3
Solids Mechanics Department, IFP Energies nouvelles, Rueil-Malmaison, France
*Corresponding author: bernard.rousseau@u-psud.fr
Keywords: Molecular simulations, Elastic constants, Semi-crystalline polyethylene
Abstract
The present work proposes, through the development of a methodology based on molecular simulation
techniques, to link the nanoscale structure of semi-crystalline polyethylene to its mechanical properties.
In a first step, the feasibility of modeling at the atomic scale a semi-crystalline polymer is demonstrated
[1]. The challenge here is to build realistic models that include explicitly the crystalline regions and the
amorphous regions of the material as well as the interface between these two regions. A particular effort
has been made towards the description of tied, loops and free chain molecules in the interfacial region.
Different “samples” have been built and equilibrated. In a second step, the influence of the local structure
onto mechanical properties is studied using molecular simulations. Mechanical properties have been
studied in the elastic limit using molecular dynamics in the canonical ensemble (imposed number of
molecules, imposed temperature and imposed volume or strain. The obtained elastic constants are
compared to available macroscopic data and a discussion on the influence of the nano-structure of the
polymer upon its macroscopic properties is proposed.
References
[1] S. Pandiyan, B. Rousseau “Factors influencing properties of interfacial regions in semicrystalline polyethylene:
a molecular dynamics simulation study” Polymer, 2013, 54(14): 3586-3593.

PPEPPD 2016
th
Fluid–fluid coexistence in an athermal colloid–polymer mixture:

thermodynamic perturbation theory and continuum molecular-dynamics
simulation
Julio Jover, Amparo Galindo, George Jackson, Erich A. Müller and Andrew J. Haslam*
Department of Chemical Engineering, Imperial College London, South Kensington Campus,
London SW7 2AZ, United Kingdom
*Corresponding author: a.haslam@imperial.ac.uk
Scientific topic: Molecular simulation; phase equilibria
Keywords: hard spheres; chains; depletion interaction; demixing; potential of mean force
Abstract
Using both Wertheim’s thermodynamic perturbation theory (TPT1) [1,2] and continuum molecular-
dynamics simulation, we examine a mixture of hard-sphere (HS) polymer chains of degree 100, and
colloids, represented by HSs of diameter 20 times that of the monomer segments comprising the polymer
chains. According to TPT1 this athermal system phase separates into colloid-rich and polymer-rich fluid
phases. Using a continuous pseudo-HS potential developed in previous work [3], molecular-dynamics
simulations are performed at a phase point indicated by TPT1 to be well within the two-phase region,
from starting configurations corresponding to completely pre-mixed and completely phase-separated
colloids and polymers. Clear evidence is seen of the stabilization of both simulations into two co-existing
fluid phases. The peaks in the probability distributions of the densities correspond to the densities
calculated using TPT1; interestingly, an analysis of the interfacial tension of the phase-separated regions
indicates ultra-low tensions in line with previous values determined with square-gradient theory [4] and
experiment [5] for colloid–polymer systems. Further simulations are carried out to examine the nature of
these co-existing phases. Reminiscent of the Asakura-Oosawa model [6], the polymer chains are seen to
be fully penetrable by other polymers however, from the point of view of the colloids, they behave (on
average) as almost-impenetrable spheres. As expected, the averaged interaction between polymer
molecules in the polymer-rich phase is found to be of soft-repulsive character. On the other hand, the
corresponding interaction in the colloid-rich phase is revealed to be of an entirely different form,
characterized by a region of effective intermolecular attraction.
References
[1] M. S. Wertheim, J. Chem. Phys., 1987, 87: 7323.
[2] W. G. Chapman, G. Jackson, K. E. Gubbins, Mol. Phys.,1988,   65: 1057.
[3] J. Jover, A. J. Haslam, A. Galindo, G. Jackson, E. A. Müller, J. Chem. Phys., 2012, 137: 144505.
[4] A. Moncho-Jordá, B. Rotenberg, A. A. Louis, J. Chem. Phys., 2003, 119: 12667.
[5] D. G. A. L. Aarts, M. Schmidt, H. N. W. Lekkerkerker, Science, 2004: 304, 847.
[6] S. Asakura, F. Oosawa, J. Chem. Phys., 1954, 22: 1255; idem, J. Polym. Sci. 1958, 33: 183.

PPEPPD 2016
th
Understanding and Predicting the Interfacial Structure and Dynamics in

Capacitative Energy Systems Utilizing Model-Integrated Synthesis,
Characterization and Experiment
Matthew W. Thompson1,2, Yu Zhang1,2, and Peter T. Cummings1,2*

1
Department of Chemical and Biomolecular Engineering, Vanderbilt University, USA
2
Multiscale Modeling and Simulation Center, Vanderbilt University, USA
*Corresponding author: peter.cummings@vanderbilt.edu
Scientific topic: Surfaces, interfaces and confinement effects; nanoscience and nanotechnology
Keywords: Ionic liquids, nanoporous carbons, supercapactors
Abstract
In the Fluid Interface Reactions Structure and Transport (FIRST) Center, an Energy Frontier Research
Center funded by the Department of Energy, we have developed a paradigm for studying fluid/solid
interfaces interfaces relevant to energy storage that we refer to as model-integrated synthesis,
characterization and experiment (MISCE). Of the almost limitless number of possible
electrolyte/electrode fluid/solid interfacial systems, the FIRST team collectively chooses systems (fluid,
solid, geometry) that are amenable to computational modeling. Frequently, the geometries chosen also
facilitate the applications of molecular probes, such as neutron and x-ray scattering and scanning probe
microscopy. Additionally, the fluids and solids chosen may require synthesis. These highly integrated
studies have led to insights into experiments as well as laying the foundation for predicting the structure
and function of energy-relevant fluid-solid interfaces (for examples, see Refs. [1]-[4]). In this
presentation, we will describe several examples of the MISCE approach.
References
[1] Feng, G., Cummings, P. T. "Supercapacitor Capacitance Exhibits Oscillatory Behavior as a Function of
Nanopore Size" Journal of Physical Chemistry Letters, 2011, 2: 2859–2864.
[2] Uysal, A., Zhou, H., Feng, G., Lee, S. S., Li, S., Fenter, P., et al. "Structural Origins of Potential Dependent
Hysteresis at the Electrified Graphene/Ionic Liquid Interface" Journal of Physical Chemistry C, 2014, 118: 569–
574.
[3] Li, S., Han, K. S., Feng, G., Hagaman, E. W., Vlcek, L., Cummings, P. T. "Dynamic and Structural Properties
of Room-Temperature Ionic Liquids near Silica and Carbon Surfaces" Langmuir, 2013, 29: 9744–9749.
[4] Black, J. M., Walters, D., Labuda, A., Feng, G., Hillesheim, P. C., Dai, S., Cummings, P. T., Kalinin, S. V.,
Proksch, R. Balke, N. "Bias-Dependent Molecular-Level Structure of Electrical Double Layer in Ionic Liquid on
Graphite," Nano Letters, 2013, 13: 5954-5960.

PPEPPD 2016
th
Polarizable versus non-polarizable force fields of electrolytes:

Simulation methodologies, chemical potentials, and solubility
Ivo Nezbeda1,2* and William R. Smith3

1
Faculty of Science, J. E. Purkinje University, Usti n. L., Czech Republic
2
Institute of Chemical Process Fundamentals, Acad. Sci., Czech Republic
3
Department of Mathematics and Statistics, University of Guelph, Guelph, ONT, Canada
*Corresponding author: IvoNez@icpf.cas.cz
Keywords: Multi-Particle-Move Monte Carlo, Osmtic Ensemble; Polarizable force fields; Non-
polarizable foece fields; Chemical potential of electrolytes; Solubility of electrolytes
Abstract
Aqueous electrolytes are ubiquitous in environmental, biological, and industrial systems. In addition to
experimental data on their properties it has become common nowadays to study and predict their
behavior by molecular simulations using various force fields (FF), i.e., intermolecular interaction models
with specific parameters obtained by fitting the selected properties to experimental data. Among the most
important properties of solutions of electrolytes are the chemical potential and electrolyte solubility.
Typically, infinite dilution electrolyte chemical potentials and the density have been used to determine
the FFs parameters. Attempts to predict chemical potentials at finite concentrations and the electrolyte
solubility have been rare for two simple reasons. First, such calculations are both very computationally
intensive and technically challenging. Second, chemical potentials are a very sensitive test of a FF, i.e.,
different FFs may produce significantly different results. Furthermore, since the electrolyte chemical
potential curve flattens at higher concentrations, the predicted solubility value is also very sensitive to the
details of the simulation procedure used.
There are two aspects associated with the chemical potential determination from simulations. Concerning
the FFs, there has been gathered enough evidence that the pairwise models have exhausted their potential
and non-additive effects, typically via polarization, must be accounted for. Concerning the technical
aspects of simulations, the Monte Carlo (MC) techniques used to calculate chemical potential are limited
to pairwise interaction models. Furthermore, the common way to determine solubility by calculating the
chemical potential over a range of concentrations is rather cumbersome.
In order to overcome the above mentioned obstacles, we have recently developed (i) a Multi-Particle-
Move MC (MPM-MC) which makes it possible to efficiently use the MC methodology even for
polarizable models, and (ii) the osmotic ensemble (OEMC) method making it possible to determine the
solubility at one MC run. Both techniques have been used to compute the chemical potential and
concentration dependence of density of the NaCl electrolyte along with the solubility for two polarizable
models, Lamoureux and Roux SWM4—DP model and Baranyai-Kiss BK3 model. In addition to a brief
account of the used methodology, results of these simulations will be reported and discussed along with
the comparison with those produced by commonly used non-polarizable models and experimental data.
Recommendations for future work will also be discussed.

PPEPPD 2016
th
Oral Session 2 – Carbon Capture and Storage – O2-1
CO2 pre-combustion capture and CO2 storage through hydrate crystallization
Duo Sun and Peter Englezos

Department of Chemical and Biological Engineering
University of British Columbia, Vancouver BC, Canada
*Corresponding author: peter.englezos@ubc.ca
Scientific topic: Carbon capture and storage
Keywords: Carbon capture and storage, gas hydrates
Abstract
Gas hydrate or clathrate hydrate crystals are non-stoichiometric inclusion compounds, which form at
suitable thermodynamic conditions, from water (host molecule) and guest molecules with suitable size
such as CO2, H2, N2, CH4, C2H6, and C3H8. The guest molecules are accommodated inside well-defined
cages of hydrogen-bonded water molecules (host lattice). Capture of CO2 from large point sources like
cement plants, oil, gas and coal burning power plants and the subsequent storage of the captured CO 2
into a subsurface porous formation of the earth (geological storage) is considered an effective strategy to
mitigate climate change until the world’s energy systems are independent of fossil fuels. Depleted oil and
gas reservoirs constitute an attractive geological formation because the fluid trapping mechanisms and
the reservoir properties are known. The Sleipner West gas field in the North Sea and the Otway project in
Australia are examples. The storage potential in the world’s oil and gas fields is estimated to be 150 Gt
of CO2 and 520 Gt of CO2 respectively. Capture of CO2 represents the largest cost associated with
carbon management, which also includes pipeline transportation and injection of the CO 2. This
presentation aims to demonstrate that the CO2 hydrate may offer technology solutions along all aspects
of carbon management. Gas hydrates may form from flue (CO2/N2) and fuel (CO2/H2) gasses for CO2
post and pre-combustion capture respectively. Hybrid conceptual processes for pre and post-combustion
capture based on hydrate crystallization are presented with emphasis on pre-combustion capture (1).
Captured CO2 may also be stored as a solid gas hydrate and this is advantageous because solid storage
reduces the mobility and migration of CO2 in the reservoir (2). An interesting variation of the idea of
storing CO2 as hydrate is the injection of CO2 in a naturally occurring natural gas hydrate reservoir.
There is an economic benefit arising for the production of natural gas that may offset some of the
capture/storage cots for CO2.
References
[1] Babu, P., P. Linga, R. Kumar, and P. Englezos ., “A Review of the Hydrate Based Gas Separation (HBGS)
Process for Carbon Dioxide Pre-Combustion Capture”, Energy, 85, 261-279, 2015.
[2] Englezos, P., and D. Sun, "Storage of CO 2 in a partially water saturated porous medium at gas hydrate
formation conditions", Int J Greenhouse Gas Control, 25, 1-8, 2014.
Acknowledgements
Financial support from CarbonManagement Canada and Natural Sciences and Engineering research Council of
canada is apprecaited.

PPEPPD 2016
th
A molecular model to characterize the effect of impurities on the

thermophysical properties on CO2 transport
Fèlix Llovell1 and Lourdes F. Vega2
1
IQS School of Engineering, Universitat Ramon Llull,. Via Augusta, 390, 08017 Barcelona, Spain
2
Alya Technology & Innovation, Centre de Promoció Empresarial, C/ Tres Creus, 236. 08203, Sabadell,
Barcelona, Spain
*Corresponding author: felix.llovell@iqs.edu
Scientific topic: Thermodynamics and Transport Properties / Carbon capture and storage
Keywords: Carbon dioxide, pipeline transport, multicomponent mixtures, soft-SAFT, Free-Volume

Theory
Abstract
Carbon dioxide (CO2) transportation by pipeline is a very important step and often looked upon as the
‘missing link’ in the process of Carbon Capture and Sequestration (CCS). Usually, the gaseous CO2-rich
stream is compressed to be transported as a dense liquid or in a supercritical phase to avoid two-phase
flow. However, as CO2 capture processes in recovery units cannot fully eliminate the presence of small
amounts of other gases and water, the resulting stream cannot be treated as pure CO2. The effect of these
impurities can dramatically modify CO2 transport conditions, producing changes on the density, the
bubble point pressure, the supercritical region limits or the viscosity. Therefore, there is a need on having
reliable equations of state (EoSs) able to provide precise information on how the thermophysical
properties of the CO2 flow are affected depending on the upstream composition. Empirical and cubic
EoSs are commonly proposed to model those mixtures, achieving a good degree of success. However,
these equations do not fully consider some important effects, such as the hydrogen-bonding interactions
of water or the quadrupole moment of CO2, leading to some inaccuracies and a lack of extrapolation
capability. In this regard, SAFT-type EoSs are an excellent alternative to account for these interactions
and provide a complete thermodynamic picture of CO2 mixtures with a high degree of accuracy.
This work is devoted to describe the effect of several common impurities (gases and water) on the
thermophysical properties of CO2 at near-critical and supercritical conditions using the crossover soft-
SAFT EoS [1]. Soft-SAFT considers different molecular effects in independent contributions and builds
coarse-grained molecular models for each molecule based on their physical properties and chemical
structures, finding a characteristic set of molecular parameters for each compound. A crossover treatment
is included to describe the density fluctuations of the critical region. The effect of the inclusion of other
gases in the density, solubility and pressure conditions of the CO2 system is checked. Particular attention
is given to the water-CO2 mixture, providing a complete description of this system. Changes on the
viscosity stream are also studied with the Free Volume Theory (FVT) coupled with soft-SAFT [2]. A
focus on multicomponent mixtures and practical applications is also provided.
References
[1] F. Llovell, J.C. Pàmies, L.F. Vega, “Thermodynamic properties of Lennard-Jones chain molecules:
Renormalization-group corrections to a modified statistical associating fluid theory.” Journal of Chemical Physics
2004, 121: 10715-10724.
[2] F. Llovell, R.M. Marcos, L.F. Vega, “Free-Volume Theory Coupled with Soft-SAFT for Viscosity Calculations:
Comparison with Molecular Simulation and Experimental Data”. Journal of Physical Chemistry B 2013, 117,
8159−8171.
Acknowledgements
Financial support from the Catalan Government (2014SGR-1582) and the Spanish Government (CTQ2014-53987-
R) are gratefully acknowledged.

PPEPPD 2016
th
CO2 Solubility in Aqueous Solutions of Linear and Branched Polyamines
1 2 2
Jian Chen *, Ruilei Zhang , Zhongjie Du , Yanmei Yu1, and Jianguo Mi2
1
State Key Laboratory of Chemical Engineering, Tsinghua University, Beijing 100084,
China
2
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical
Technology, Beijing 100029, China
*Corresponding author: cj-dce@tsinghua.edu.cn
Scientific topic: Carbon capture and Storage
Keywords: Measurement, Gas solubility, Carbon Dioxide, Amines, Absorption heat
Abstract
Absorption technology is looked as the main one for CO2 capture from flue gases. In this paper,
absorption solubility of CO2 in aqueous solutions of ten linear and branched polyamines were determined
at 313.15 K and 393.15 K using the constant-volume method combined with gas chromatography
analysis. The relationship between molecular structure of these polyamines and absorption performance
is discussed. It is found that the capture performance is affected by the number of amino groups, the
carbon number between the amino groups and the chain length of polyamines. The corresponding values
of CO2 absorption heat were also estimated using the Gibbs-Helmholtz equation and were analyzed from
the view of molecular conformation.
References
[1] J. I. Lee, F. D. Otto, A. E. Mather. “Equilibrium between carbon dioxide and aqueous monoethanolamine
solutions” J. Appl. Chem. Biotechnol, 1976, 26:541-549.
[2] P. Singh, J. P. M. Niederer, G. F. Versteeg. “Structure and activity relationships for amine-based CO2
absorbents-I” International Journal of Greenhouse Gas Control, 2007, 1:5-10.
[3] P. Singh, J. P. M. Niederer, G. F. Versteeg. “Structure and activity relationships for amine-based CO2
absorbents-II” Chemical Engineering Research and Design, 2009, 87:135-144.
[4] L. Dong, J. Chen, G. Gao. “Solubility of Carbon Dioxide in Aqueous Solutions of 3-Amino-1-propanol” Journal
of Chemical Engineering Data, 2010, 55:1030-1034.
[5] H. Li, Y. L. Moullec, J. Lu, J. Chen, J. C. V. Marcos, G. Chen, F. Chopin. “CO2 solubility measurement and
thermodynamic modeling for 1-methylpiperazine/water/CO2” Fluid Phase Equilibria, 2015, 394: 118–128.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Nos. 51134017, 21276010 and
51373019) and National Science and Technology Support Program of China (No. 2015BAC04B01).

PPEPPD 2016
th
Molecular modeling studies of CH4 storage using nanoporous carbons

Di Wu, Linghong Lu*, Shanshan Wang, and Wei Cao
College of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing
Tech University, 5 Xinmofan Road, Nanjing, 210009, PR China
*Corresponding author: linghonglu@njtech.edu.cn
Keywords: Methane; Storage; Porous carbon; Molecular modeling
Abstract
The main ingredient in natural gas is methane. Natural gas has many advantages such as low cost, high-
octane, low emission combustion, high calorific value. Many countries are beginning to develop the use
of natural gas, optimize energy structure and reduce the dependence on oil and other energy sources. The
chief drawback of the use of natural gas as a fuel is low energy density[1]. It is needed to improve
storage density of natural gas. Adsorption natural gas (ANG) has the most advantage of future storage
methods[2]. In 3.5 ~ 6MPa ANG can get the storage density close to the compressed natural gas(CNG)
under 20MPa[3]. To find suitable adsorbent for ANG is a hot problem researching currently. This study
focused on the use of microporous-rich and high specific surface nanoporous carbon (NPCs) as
adsorbent, examine the adsorption performance from five aspects: NPCs density, pore size distribution
and pore ordering, size of micro graphite unit, -OH modification, and also study its diffusion coefficient.
Grand canonical Monte Carlo (GCMC) and equilibrium molecular dynamics (EMD) simulation methods
were used to study the adsorption and diffusion of CH4 in different NPCs. Simulation results show that:,
the optimum density range of random NPCs is 0.5 ~ 0.6g / cm3 for the adsorption of CH4; Random
micro pores with size smaller than 1nm has a great contribution to adsorption and storage of CH 4, but
ordered mesopores can promote the adsorption of micropores and increase the storage capacity under
high pressure. The effects of size of tiny graphite units on the adsorption of CH4 are not very obvious. -
OH modified NPCs have higher adsorption capacity of CH4 than the unmodified NPCs. Meanwhile the
NPCs with more -OH modified have higher CH4 adsorption capacity. The diffusion coefficient increases
with decreasing density of adsorbent. Diffusion coefficient changes obviously with density change at
lower density. This study can guide the design of CH4 adsorption storage material with good
performance and low price.
References
[1] Zhou, J. Liu, W. Su, Y. Sun, Y. Zhou “Progress in Studies of Natural Gas Storage with Wet
Adsorbents” Energy & fuels, 2010, 24: 3789-3795.
[2] J.Wegrzyn, M. Gurevich “Adsorbent storage of natural gas” Applied Energy, 1996,55: 77-83.
[3] Z. Liao, H. Jiang “Adsorbed Natural Gas Technology and Application” Oil & Gas Storage and Transportation,
2005,24:19-22.
Acknowledgements
This work was supported by the National Basic Research Program of China (Grant No. 2015CB655300), the
National Natural Science Foundation of China Grants (Grant Nos. 21176113, 21206070, 91334240) and the Project
of Priority Academic Program Development of Jiangsu High Education Institution(PAPD)

PPEPPD 2016
th
Poster Session I – P01
Prediction of Safety-Relevant Properties for Multicomponent PU Raw-

Material Mixtures: Flash Point, Auto Ignition Temperature and Initial
Normal Point
Stephanie Peper1, Ralf Dohrn1, Klaus Konejung2
1
Downstream Processes, Bayer Technology Services GmbH, Leverkusen, Germany
2
Polyurethanes, Covestro AG, Leverkusen, Germany
*Corresponding author: ralf.dohrn@bayer.cm
Scientific topic: Environment, sustainability and risk management
Keywords: Flash Point, Auto Ignition Temperature, multicomponent, Polyurethanes, prediction
Abstract
Whereas the number of raw materials for the production of polyurethanes is huge the number of mixtures
and formulations is abundant. Depending on applications and their specific requirements dedicated
mixtures of polyols or isocyanates with catalysts, stabilizers, foaming agents or defoamers, crosslinkers
or chain stoppers and other components are created. This can end up with more than 20 pure components
with molecular weight range from 18 for water to 100,000 for liquid silicones. According to the world
wide safety standards every single mixture requires a classification for transport and handling. This
classification requires a bunch of thermophysical properties. Within the Globally Harmonized System of
Classification and Labeling of Chemicals (GHS), the thermophysical properties of substances and
mixtures are the basis for their classification concerning physical hazards [1]. For example, flammable
liquids of category 1 have a flash point lower than 23°C and an initial normal boiling point not higher
than 35 °C. Aside by experimental testing or literature search, GHS allows data to be calculated.
Identical physical limits are used for the classification of dangerous goods for transport. We combined
and applied methods [2] that are based on group contributions methods UNIFAC [3] and mod. UNIFAC
(Do) [4] to predict the following thermophysical properties of polyurethane raw material mixtures:
• the flash point, “the lowest temperature at which the application of an ignition source
causes the vapors of a liquid to ignite under specified test conditions” [1]
• the autoignition temperature, the lowest temperature of a hot surface at which a
combustible material / air mixture self-ignites at atmospheric pressure without any obvious
sources of ignition.
• the initial normal boiling point.
Within the last 20 years Bayer has tested physical properties for more than 1500 multicomponent
mixtures with defined compositions. This large data base has been used to evaluate the calculation
methods developed in this work.
References
[1] Globally Harmonized System of Classification and Labelling of Chemicals (GHS, Rev. 5), United Nations,
2013.
[2] S. Peper, R. Dohrn, K. Konejung, submitted to Fluid Phase Equilibria (2015).
[3] A. Fredenslund, R.L. Jones, J.M. Prausnitz, AlChE J. 21 (1975) 1086-1099.
[4] U. Weidlich, J. Gmehling, Ind. Eng. Chem. Res. 26 (1987), 1372-1381.

PPEPPD 2016
th
The Spreading Behavior of Surfactant-laden Aqueous Droplets on
Textured Surface
Zhi Li1, 2, Bei Liu1, 2*, Bo Jing1, Guangjin Chen2 and Xianren Zhang3
1
State Key Laboratory of Offshore Oil Exploitation, Beijing 100027, China
2
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, China
3
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, China
*Corresponding author: liub@cup.edu.cn
Keywords: Molecular dynamics simulation, Surfactant, Droplet, Spreading behavior
Abstract
The fluid wetting behavior is a dynamic process of replacing one fluid to another on substrate. The
exploration of improving fluid wetting rate and promoting spreading behavior on the solid surface has
become more and more important in the field of fluid dynamic wetting. Surfactant is always used in the
territory of oil exploitation and is thought to be a good candidate for facilitating droplet spread. In our
work, molecular dynamics simulation was performed to study the spreading behavior of surfactant-water
droplet on smooth and rough substrates. Our results show that addition of surfactants could promote the
spread of droplets on smooth surface. The adsorption of surfactants on the gas-liquid and liquid-solid
interface facilitates the reduction of gas-liquid and liquid-solid interfacial tension, which is in agreement
with previous studies [1-3]. When surfactant-laden aqueous droplets are put nearby the textured surface,
the droplets’ spread was governed by the combined work of surfactants and roughness of the surface. For
droplets on hydrophobic textured surface, the adsorption of surfactants into the grooves may strengthen
the pinning effect and increase the equilibrium contact angle. While for droplets on hydrophilic rough
surface, surfactants would promote the generation of precursor film which can not be seen in the whole
process of pure liquid droplets’ spread.
References
[1] H. Y. Kim, Y. Qin, K. A. Fichthorn “Molecular dynamics simulation of nanodroplet spreading enhanced by
linear surfactants” The journal of Chemical Physics, 2006, 125: 174708.
[2] Y. Shen, A. Couzis, J. Koplik, C. Maldarelli, M. S. Tomassone “Molecular dynamics study of the influence of
surfactant structure on surfactant-facilitated spreading of droplets on solid surfaces” Langmuir, 2005, 21: 12160-
12170.
[3] P. E. Theodorakis, E. A. Müller, R. V. Craster, O. K. Matar “Superspreading: mechanisms and molecular
design” Langmuir, 2015, 31: 2304-2309.
Acknowledgements
This work was supported by the open funding project from State Key Laboratory of Offshore Oil Exploitation of
China.
PPEPPD 2016
th
Predicting Asphaltene Precipitation in Petroleum Fluids via NRTL-SAC
Md Rashedul Islam* and Chau-Chyun Chen**

Department of Chemical Engineering, Texas Tech University, USA
*Presenting author: md.islam@ttu.edu
**Corresponding author: chauchyun.chen@ttu.edu
Scientific topic: Gas and oil downstream and upstream, hydrofracking
Keywords: Asphaltene precipitation, Aggregation thermodynamics, NRTL-SAC
Abstract
Modeling asphaltene precipitation in petroleum fluids is of immense interest to researchers and engineers
participating in production, distribution, and refining activities in petroleum industries. Recent advances
in petroleomics show that asphaltene precipitation involves hierarchical structures with elements:
molecules, nanoaggregates, and clusters [1]. Asphaltene molecules undergo self-associaltion to form
nanoaggregatges and nanoaggregates subsequently form clusters. Recently, a novel thermodynamic
formulation was proposed to model the onset of asphaltene nanoaggregates formation [2]. Together with
the predictive activity coefficient models including UNIFAC, NRTL-SAC, and COSMO-SAC, the
aggregation thermodynamics has been successfully applied to predict asphaltene precipitation in wide
ranges of binary organic solvents. In this work, the aggregation thermodynamics is used with NRTL-
SAC to model asphaltene precipitation from athabasca bitumen and its blend with light gas oil. NRTL-
SAC provides a minimal set of model correlation parameters as conceptual segment numbers for
asphaltenes and nanoaggregates. The petroleum fractions are modeled with selected hydrocarbon
molecules and their compositions are identified from available petroleum crude assays [3]. The proposed
thermodynamic framework should provide an effective and practical tool to correlate and predict
asphaltene precipitation in petroleum fluids.
References
[1] O. C. Mullins "The Modified Yen Model" Energy & Fuels, 2010, 24:2179-2207.
[2] M. Wang, Y. Hao, M.R. Islam, C.-C. Chen "Aggregation Thermodynamics for Asphaltene Precipitation"
AIChE Journal, Submitted.
[3] C.-C. Chen, H. Que "Method of Characterizing Chemical Composition of Crude Oil for Petroleum Processing,"
US Patent Application Publication: 2013/0185044 A1, July 18, 2013.
Acknowledgements
The authors gratefully acknowledge the financial support of the Jack Maddox Distinguished Engineering Chair
Professorship in Sustainable Energy sponsored by the J.F Maddox Foundation.

PPEPPD 2016
th
Modeling Phase Equilibria of Semiclathrate Hydrates of CH4, CO2, N2 and

Gas Mixtures in Aqueous Solutions of TBAB and TBAF
Qing-Lan Ma*, Jun-Li Qi, Chang-Yu Sun, Guang-Jin Chen
State Key Laboratory of Heavy Oil Processing, China University of Petroleum,
Fuxue Road, Changping District, Beijing 102249, China
*Corresponding author: maql@cup.edu.cn
Scientific topic: Phase equilibria
Keywords: Semiclathrate hydrates, Phase equilibria, Tetrabutyl ammonium bromide (TBAB),

Tetrabutyl ammonium fluoride (TBAF)
Abstract
Quaternary ammonium salts (QASs) such as tetrabutyl ammonium bromide (TBAB) and fluoride
(TBAF) can form semiclathrate hydrates with water molecules at atmospheric pressure. Recently, the
semiclathrate hydrates have attracted more and more attentions for their broad applications, such as the
storage and transportation of natural gas or coal bed methane, separation of low-boiling gases and carbon
dioxide sequestration at mild conditions. In this work, the modeling investigations were conducted for
the TBAB and TBAF semiclathrate hydrates with different gases such as CH4, CO2, N2, and their
mixtures. The Chen-Guo hydrate model [1] was extended to the semiclathrate hydrate systems. The
thermodynamic properties of the gas phase were described with the Patel-Teja equation of state (PT
EOS) [2]. The PT EOS combined with a Debye-Huckel electrostatic contribution term [3] was chosen to
describe the thermodynamic properties of the electrolyte solution. The parameters in EOS for TBA+
cation were determined from the activity of water in the TBAB aqueous solution proposed by
Lindenbaum and Boyd [4], and Amado and Blanco [5]. The parameters of TBAB and TBAF in the
hydrate model were obtained from correlating the equilibrium data of semiclathrate hydrates. The
extensive tests show that the proposed model results are in acceptable agreement with the experimental
data on phase equilibria of semiclathrate hydrate systems.
References
[1] G. J. Chen, T. M. Guo “A new approach to gas hydrate modelling” Chem. Eng. J., 1998, 71: 145-151.
[2] N. C. Patel, A. S. Teja “A new cubic equation of state for fluids and fluid mixtures” Chem. Eng. Sci., 1982, 37:
463−473.
[3] Y. X. Zuo, T. M. Guo “Extension of the Patel-Teja equation of state to the prediction of the solubility of natural
gas in formation water” Chem. Eng. Sci., 1991, 46: 3251-3258.
[4] S. Lindenbaum, G. E. Boyd “Osmotic and activity coefficients for the symmetrical tetra alkyl ammonium
halides in aqueous solution at 25 °C” J. Phys. Chem., 1964, 68: 911−917.
[5] G. E. Amado, L. H. Blanco “Isopiestic determination of the osmotic and activity coefficients of dilute aqueous
solutions of symmetrical and unsymmetrical quaternary ammonium bromides with a new isopiestic cell at
298.15K” Fluid Phase Equilib., 2005, 233: 230−233.
PPEPPD 2016
th
Development of a Comprehensive Molecular Thermodynamic Model for

High Salinity Produced Water in Oil and Gas Productions
Chau-Chyun Chen1,* and Huan Zhou2

1
Department of Chemical Engineering, Texas Tech University, USA
2
College of Chemical Engineering & Materials Science, Tiamjin University of Science & Technology, China
*Corresponding author: chauchyun.chen@ttu.edu
Scientific topic: Marine and saline systems and processes
Keywords: High salinity brines, electrolyte thermodynamics, electrolyte NRTL Model
Abstract
Managing produced water in the rapidly developing shale gas industry is a major challenge for protecting
the environment [1]. Desalination for reuse of high salinity produced water depends on novel material
and process innovations. We present recent advances in the development of a comprehensive
thermodynamic model aimed to support heat and mass balance calculations and process simulation of
desalination processes with produced water. The major ions of concern for produced water management
include Na+, K+, Mg2+, Ca2+, Ba2+, Sr2+, Cl−, HCO3− and SO42− ions. Based on the electrolyte Non-
Random Two Liquid theory (eNRTL) for electrolyte solutions [2], the concentration dependency of the
solution nonideality is accounted for with two binary interaction parameters for each of the
water−electrolyte interaction pairs and the electrolyte–electrolyte interaction pairs. The temperature
dependency of the binary interaction parameters is accounted for with a Gibbs-Helmholtz type
expression with three temperature coefficients representing excess Gibbs energy, excess enthalpy, and
excess heat capacity contributions. With the binary parameters regressed from thermodynamic data of
aqueous single electrolyte binary systems and aqueous two electrolyte ternary systems, the model
provides accurate representations and reliable predictions for various thermodynamic properties of
quaternary and quinary systems examined thus far for the aqueous Na+−K+−Mg2+−Ca2+−Cl−−SO42−
hexary system with temperatures from 273.15 K to 473.15 K and concentrations up to salt saturation.
The model is being extended to cover Ba2+, Sr2+ and HCO3− ions and it should become an indispensable
scientific tool in the development of novel desalination processes for high salinity produced water in oil
and gas productions.
References
[1] D.L. Shaffer, L.H. Arias Chavez, M. Ben-Sasson, S. R.-V. Castrillón, N.Y. Yip, M. Elimelech, Environ. Sci.
Technol. 2013, 47:9569-9583.
[2] Y. Song, C.-C. Chen, “Symmetric Electrolyte Nonrandom Two-Liquid Activity Coefficient Model,” Ind. Eng.
Chem. Res. 2009, 48:7788-7797.
Acknowledgements
The authors gratefully acknowledge the financial support of the Jack Maddox Distinguished Engineering Chair
Professorship in Sustainable Energy sponsored by the J.F Maddox Foundation.

PPEPPD 2016
th
Influence of PEG´s molecular weight on different polymer/salt ATPS phase

diagrams
Kamila Wysoczanska, Eugénia A. Macedo*

Laboratory of Separation and Reaction Engineering – Laboratory of Catalysis and Materials (LSRE-LCM),
Faculty of Engineering, University of Porto, Porto, Portugal.
*Corresponding author: eamacedo@fe.up.pt
Scientific topic: Phase equilibria (experimental, modeling)
Keywords: ATPS, phase diagrams, polymer, salts
Abstract
Aqueous two-phase extraction is a very adequate technique for the separation of biologically active
materials, as it offers substantial advantages, such as rare loss of biomolecular activity, low interfacial
tension, high capacity and yield, and ease of up-scale. Aqueous two-phase systems (ATPS) can be
formed by mixing two solutions of different polymers, or of a polymer and a salt. Polyethylene glycol
(PEG) is a widely used polymer that, with another polymer or salt, can establish two immiscible phases
[1]. Citrate salts combined with PEGs ensure environmentally friendly conditions, as those components
do not contribute to formation of large quantities of hazardous waste, contrary to widely studied systems
formed by phosphates and sulfates.
Physicochemical characterization and thermodynamic studies on equilibrium phase for biphasic systems
play a key role in the step of selection of appropriate components that can form ATPS. The potential
working area is described by phase diagrams and can be used to specify the range of system applications.
The main goal of this work was to study liquid-liquid equilibria of PEG + (sodium or potassium) citrate
salt aqueous two-phase systems, at 298.15 K. Binodal data for the ATPSs formed by PEGs of different
molecular weights (4000, 6000, 8000) was obtained experimentally using cloud point method. For the
modeling of binodal curves, Merchuk equation was applied [2]. Tie-lines for systems of PEG 4000 –
(sodium, potassium) citrate and PEG 6000 – (sodium, potassium) were determined and represented using
Othmer-Tobias and Bancroft equations [3]. Data was compared with previous studies reported in the
literature, and the more efficient system in terms of phase forming was identified.
References
[1] P.A. Albertsson, Partitioning of Cell Particles and Macromolecules, Wiley Interscience, New York, 1986. pp.
8–38.
[2] Merchuk, J. C., Andrews, B. A., & Asenjo, J. A. (1998). Journal of Chromatography B: Biomedical Sciences
and Applications, 711(1), 285‐ 293.
[3] Othmer, D. F., Tobias, P. E. (1942). Industrial & Engineering Chemistry, 34(6), 690‐ 692.

PPEPPD 2016
th
Application of PPR78 Thermodynamic Framework as Fill Method
for Semi-Empirical Mixing Rule for Hydrocarbon-Water-Glycol Mixtures
Francisco J. Braña-Mulero1*, Seiya Hirohama1, PrasannaLakshmi Lingampally2,

Masakazu Sasaki3, and Jean-Noël Jaubert4
1
Global Solutions/Schneider Electric Corp.,USA
2
Standard Applications/Cognizant Corp., India
3
Process Engineering Division/Toyo Engineering Corp., Japan
4
ENSIC-LRGP, Université de Lorraine, France
*Corresponding author: francisco.brana-mulero@schneider-electric.com
Scientific topic: Gas and Oil Downstream and Upstream, Hydrofracking
Keywords: PPR78, Cubic Equation of State, Mixing Rule, Binary Interaction Parameter, Slug Catcher
Abstract
Cubic equations of state (CEoS) remain popular in many process simulations. Although there are
known intrinsic and practical limitations to CEoS, practitioners have learned that through judicious
choice of equation, mixing rule, and binary interaction parameters (BIP), these equations can provide the
fidelity and performance required in a wide variety of applications including those encountered in design
of slug catchers in gas processing units. Even for mixtures containing polar components like water or
glycols, very simple and empirical mixing rules work well for many cases with significantly low cost in
computer resource consumption which is important in dynamic simulations.
These benefits aside, the lack of experimental data for many systems of interest results in gaps in the
BIPs needed to represent many important processes. This work demonstrates the successful application
of a BIP fill procedure based on a methodology recently introduced by Jaubert and co-workers [1, 2].
The BIPs so obtained for SRK and PR CEoS are combined with an empirical mixing rule developed by
Cunnigham, Coon and Twu [3] (SRKM and PRM), which works well for mixtures containing polar
components and hydrocarbons at the same time.
The software utility of two important developments is demonstrated: 1) The BIP fill procedure makes
use of formulae that converts the BIPs (kij) generated by the predictive PPR78 method to the equivalent
BIPs for a target CEoS and alpha function. 2) A companion methodology for handling petroleum
pseudo-components within the predictive framework of PPR78 is also utilized. In particular, we take
advantage of the reliability and predictive power of PPR78 to estimate missing BIPs for important
applications where SRKM and PRM CEoS are suitable choices for CEoS. We illustrate the utility of this
approach through a series of examples, including actual applications to real-life gas processing processes.
References
[1] J-N Jaubert, R. Privat “Relationship between the binary interaction parameters (kij) of the Peng–Robinson and
those of the Soave–Redlich–Kwong equations of state: Application to the definition of the PR2SRK model” Fluid
Phase Equilibria 295 (2010) 26–37
[2] X. Xu, J-N Jaubert, R. Privat, P. Duchet-Suchaux, F. Braña-Mulero “Predicting Binary-Interaction Parameters
of Cubic Equations of State for Petroleum Fluids Containing Pseudo-components” Ind. Eng. Chem. Res. 2015, 54,
2816−2824
[3] J.R. Cunningham, J.E. Coon, C.H. Twu; “Estimation of Aromatic Hydrocarbon Emissions from Glycol
Dehydration Units using Process Simulation” Presented at 72nd Annual GPA Convention, March 15-17 (1993)
PPEPPD 2016
th
Prediction of solvent effects on reaction kinetics

Max Lemberg, Gabriele Sadowski*
Laboratory of Thermodynamics, TU Dortmund University, Germany
*Corresponding author: gabriele.sadowski@bci.tu-dortmund.de
Scientific topic: Thermodynamics and transport properties (experimental, modeling)
Keywords: esterification, reaction kinetics, Raman spectroscopy, PC-SAFT
Abstract
Solvents are known to have a significant influence on both reaction equilibria and reaction kinetics.
Therefore they can affect yield and selectivity for a desired product. As the application of solvents allows
the intensification of reactions and an effective catalyst recycling, they are very important for the
development of sustainable processes. To facilitate the solvent selection process, it is desireable to apply
thermodynamic models capable of predicting solvent effects on reactions. Recently, it was shown that
PC-SAFT is able to predict solvent effects on the reaction equilibrium of the esterifications of acetic acid
and of propionic acid with ethanol [1].
This work focuses on the solvent influence on the kinetics of the esterification of acetic acid with
ethanol. The reaction was on the one hand performed in neat reaction mixtures at different reactant ratios
and on the other hand in the solvents acetonitrile, tetrahydrofurane and dimethylformamide. The progress
of the reaction was observed by in situ Raman spectroscopy.
The so-obtained equilibrium conversions were in all cases in good agreement with literature data [1]. The
effects of the varying reactant ratio and different solvents on the reaction equilibrium were similarily
observed for the reaction kinetics. Whereas acetonitrile promotes the esterification kinetics, they are
slowed-down in DMF. Describing the reaction-rate law in terms of reactant activities (obtained from PC-
SAFT) allowed for considering the different interactions between the components in the different
reaction mixtures. Based on kinetic data of the solvent-free reaction mixture and accounting for the
reactant thermodynamic activities in the different solvents, the reaction kinetics in all investigated
solvents could be predicted in almost quantitative agreement with the experiments.
References
[1] O. Riechert, M. Husham, G. Sadowski, T. Zeiner ”Solvent Effects on Esterification Equilibria” American
Institute of Chemical Engineers Journal, 2015, 61: 3000-3011.

PPEPPD 2016
th
Common features shared by a pure substance and a binary azeotrope

Jean-Noël Jaubert1* and Romain Privat1
1
*Corresponding author: jean-noel.jaubert@univ-lorraine.fr
Scientific topic: Thermodynamic and transport properties, Phase equilibria
Keywords: pure substance, azeotropic mixture, vapor-liquid equilibrium.
Abstract
It is well established that an azeotrope has many of the characteristics of a pure substance [1]:
1) the vapor pressure ( Psat ) of a pure component is a function only of temperature. In the same way, a
system of two components and two phases with the same composition is monovariant so that the
az
azeotropic pressure ( P ) of a binary system depends only on temperature.
2) The variation with temperature of the vapor pressure of a pure component obeys the rigorous
Clausius-Clapeyron equation: d ln P
sat
 
d T1   vap H(T) R   vap Z(T) . The azeotropic pressure
of a binary system varies with temperature in a very akin way:
dln Paz d  T1   azH(T) R  az Z(T) where az H and az Z are the enthalpy and the
compressibility factor of azeotropic vaporization respectively. By integration of such equations, we
sat az
can conclude that both the logarithm of P and P are at first glance linear functions of the
reciprocal of the absolute temperature.
3) By compressing isothermally a pure gas (T < Tc), the pressure rises until the first drop of liquid is
formed at the dew-point and the pressure remains constant until the last trace of gas disappears at the
bubble-point. By compressing isothermally an azeotropic binary gas mixture, it will also be observed
that the dew and bubble pressures are the same.
4) For a pure component, the equilibrium condition writes: gliq  ggas if g denotes the chemical
potential i.e. the molar Gibbs energy. For a binary azeotropic system, the equilibrium condition also
writes: gliq  ggas if g denotes the total molar Gibbs energy of the considered phase (liquid or gas).
In this study, we propose to extensively extend such a list. It will be established that:
a) the Maxwell equal area rule can be applied to a binary azeotropic mixture.
b) The sophisticated correlations used to estimate the vapor pressures can be used for azeotropic
systems.
c) The changes of az H and az Z with temperature have the same trends as for a pure component.
d) The mathematical conditions that define a pure-component critical point can be applied to define a
critical azeotrope.
az
e) The shape of a ( P ,v) plane has all the characteristics of a pure-component (P,v) plane.
f) The Rackett equation can be used to predict the molar volume of an azeotropic liquid phase …
g)
References
[1] I. Prigogine, R. Defay, Chemical Thermodynamics, 2 nd Ed. Longmans, Green & Co, London (Great Britain),
1965.

PPEPPD 2016
th
COSMO-CAMD: A framework for Computer-Aided Molecular Design with

COSMO-RS
Jan Scheffczyk1*, Lorenz Fleitmann1, Annett Schwarz1, André Bardow1 and Kai Leonhard1
1
Chair of Technical Thermodynamics, RWTH Aachen University, Germany
*Corresponding author: jan.scheffczyk@ltt.rwth-aachen.de
Scientific topic: Product and process engineering
Keywords: Computer-aided molecular design, COSMO-RS, solvent design, extraction
Abstract
Product and process design aims at tailoring chemicals to specific needs. For this purpose, computer-
aided molecular design (CAMD) methods have been developed and applied successfully [1].
The success of CAMD methods depends strongly on the underlying property prediction method. Most
CAMD methods rely on group contribution (GC) methods which are well established and easy to apply
in a design framework. However, GC methods require experimental equilibrium data for initial
parametrization and the underlying thermodynamic picture is usually strongly simplified limiting
prediction accuracy. Very accurate predictions can be achieved by quantum mechanics but these
calculations are in most cases too costly to be included in computer-aided molecular design. A well-
balanced compromise between accuracy from quantum mechanics and computational efficiency has been
achieved by the thermodynamic model COSMO-RS [2].
In this work, COSMO-RS is therefore employed as the basis for a novel CAMD framework. This novel
framework combines systematic solvent design with a quantum mechanics-based description of potential
solvent candidates. The design problem is formulated as mixed-integer nonlinear problem and solved
using a genetic algorithm. Novel solvent candidates are generated with COSMOfrag, a high-throughput
screening shortcut for COSMO-RS [3]. Successively, refined information on the moleculare structure of
the solvent is incorporated to account for molecular interactions and real solvent effects. The proposed
COSMO-CAMD method is successfully applied to design novel solvents for liquid-liquid extraction
processes.
References
[1] L. Y. Ng, F. K. Chong, N. G. Chemmangattuvalappil “Challenges and opportunities in computer-aided
molecular design” Computers & Chemical Engineering, 2015, 81: 115–129.
[2] A. Klamt, F. Eckert, W. Arlt “COSMO-RS: an alternative to simulation for calculating thermodynamic
properties of liquid mixtures” Annual review of chemical and biomolecular engineering, 2010, 1: 101–122.
[3] M. Hornig, A. Klamt “COSMOfrag: a novel tool for high-throughput ADME property prediction and similarity
screening based on quantum chemistry” Journal of chemical information and modeling, 2005, 45: 1169–1177.
Acknowledgements
This work was performed as part of the Cluster of Excellence ”Tailor-Made Fuels from Biomass”, which is funded
by the Excellence Initiative by the German federal and state governments to promote science and research at
German universities.

PPEPPD 2016
th
The role of ionic liquids as hydrotropes on the enhanced solubilization of

antioxidants extracted from biomass
Ana Filipa M. Cláudio1, Márcia C. Neves1, Karina Shimizu2, José N. Canongia Lopes2,
Mara G. Freire1, João A.P. Coutinho1*
1
CICECO - Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro,
Portugal.
2
Centro de Química Estrutural, Instituto Superior Técnico, 1049 001 Lisboa, Portugal, Instituto de Tecnologia
Química e Biológica, UNL, AV. República Ap. 127, 2780 901 Oeiras, Portugal,
*Corresponding author: jcoutinho@ua.pt
Scientific topic: Molecular Innovation Materials for a better Future: Ionic Liquids
Keywords: Hydrotropes, ionic liquids, solubility, phenolic compounds.
Abstract
Different authors have been calling the attention to the enhanced solubilization of a wide range of
compounds in aqueous solutions of ionic liquids (ILs) and proposing these solutions as potential solvents
for the extraction of target compounds from biomass.[1] Among these, vanillin and gallic acid, two
antioxidants with outstanding features such as anti-inflammatory, antibacterial, antifungal, phytotoxic
and radical scavenging[2,3], are present in high concentrations in a variety of biomass sources, such as
fruits, vegetables and wood, and also in many residues from industrial or agricultural activities. Their
extraction from natural sources is usually carried out with mildly polar solvents such as alcohols, due to
their low solubility in water. In this work, the enhanced ability of aqueous solutions of ILs to extract and
solubilize antioxidants from biomass is explained showing that the ILs act as hydrotropes. The effects of
the IL chemical structures, their concentration and temperature on the solubility of vanillin and gallic
acid were evaluated and compared with the performance of conventional hydrotropes. The solubility of
these two antioxidants was studied in the whole composition range, from pure water to pure ILs, and an
increase in the solubility of up to 40-fold was observed. Using Dynamic Light Scattering, NMR and
molecular dynamics (MD) simulations, it was possible to infer that the enhanced solubility of
biomolecules in IL aqueous solutions is related to the formation of IL-biomolecule aggregates. Finally, it
was demonstrated that the hydrotropy induced by ILs can be used to recover solutes, by precipitation,
from aqueous media, simply by using water as anti-solvent. The results gathered in this work have a
significant impact on the understanding of the role of ILs aqueous solutions in the extraction of added-
value compounds from biomass, as well as in the design of novel processes for their recovery from
aqueous media.
References
[1] H. Passos, M.G. Freire and J.A.P. Coutinho, Ionic liquid solutions as extractive solvents for value-added
compounds from biomass, Green Chem, 2014, 16, 4786-4815.
2. A.F.M. Cláudio, A.M. Ferreira, C.S.R. Freire, A.J.D. Silvestre, M.G. Freire and J.A.P. Coutinho, “Optimization
of the gallic acid extraction using ionic-liquid-based aqueous two-phase systems”, Sep. Purif. Technol., 2012, 97,
142-149.
3. A.F.M. Cláudio , M.G. Freire, C.S.R. Freire, A.J.D. Silvestre and J.A.P. Coutinho, “Extraction of vanillin using
ionic-liquid-based aqueous two-phase systems”, Sep. Purif. Technol., 2010, 75, 39-47.
Acknowledgements
This work was developed in the scope of the project CICECO-Aveiro Institute of Materials (Ref. FCT UID/CTM
/50011/2013), financed by national funds through the FCT/MEC and when applicable co-financed by FEDER
under the PT2020. This work was also financed by national funding through the projects EXPL/QEQ-
PRS/0224/2013 and PEst-C/CTM/LA0011/2013.

PPEPPD 2016
th
Measurement and Modeling of the Phase Behavior of n-Alkane Diluted

Bitumen
Kim A. Johnston1*, Marco A. Satyro2, Shawn D. Taylor3, Harvey W. Yarranton1, Florian F. Schoeggl1
1
Department of Chemical and Petroleum Engineering, University of Calgary, Canada
2
Department of Chemical Engineering, Clarkson University, USA
3
Schlumberger DBR Research Centre, Canada
*Corresponding author: johnstka@ucalgary.ca
Scientific topic: Phase Equilibria
Keywords: Asphaltene onset point, asphaltene phase composition, saturation pressure, solvent diluted
bitumen, cubic equation of state
Abstract
The prediction of the phase behavior of mixtures of bitumens and n-alkanes is required for the design and
optimization of solvent-assisted in situ recovery processes, solvent based oil sand extraction processes,
and solvent deasphalting processes. This phase behavior can include vapour-liquid equilibrium, liquid-
liquid equilibrium, asphaltene precipitation, and the coexistence of three liquid phases. Data for these
mixtures are sparse and a model capable of describing the full range of phase behavior has proven
elusive.
In this work, phase behavior data were collected for n-pentane and propane diluted bitumen at pressures
up to 14 MPa and temperatures of 20 to 280°C. Vapour-liquid equilibria and liquid (solvent-rich)-
liquid(asphaltene-rich) equibria were observed for these mixtures. Saturation pressures were measured
using both a PVT cell and a blind cell apparatus. The composition at which asphaltenes precipitate
(asphaltene onset point) was measured using a high pressure microscope apparatus. Asphaltene yield
curves were measured in the blind cells at temperatures from 20 to 180°C and pressures up to 14 MPa. A
new experimental procedure was developed to measure the phase compositions of both the solvent-rich
light phase and the asphaltene-rich heavy phase at conditions where two liquid phases form. Phase
diagrams were constructed for these mixtures.
The Advanced Peng Robinson cubic equation of state was used to model the phase equilibria.
Compositionally dependent binary interaction parameters were introduced to model the asphaltene yield
data. A set of interaction parameters is recommended that provides a good fit for both saturation
pressures and asphatene yields. The pros and cons of this modeling methodology are discussed.

PPEPPD 2016
th
All-atom force-fields for short hydrofluoroalkanes
Jiri Janecek1*, Patrice Paricaud1,2, Celine Houriez2, J. Deschamps1

1
UCP, ENSTA Paristech, 828 Boulevard des Maréchaux, 91762 Palaiseau, France
2
Mines ParisTech, PSL research University, CTP, 35 rue Saint Honoré, 77305 Fontainebleau Cedex, France.
*Corresponding author: jiri.janecek@ensta-paristech.fr
Scientific topic: Molecular simulation, phase equilibria
Keywords: HFC, molecular simulation, force field.
Abstract
Hydrofluoroalkanes and hydrofluoroolefins have almost completely replaced chlorinated haloalkanes as

working fluids in thermodynamic cycles or as propellants for medicinal as well as technical applications.
Their mixtures with other suitable fluids (other HFC's or HFO's, hydrocarbons or CO 2) are used in order
to optimize the performance of thermodynamic cycles. Molecular simulations can be used to reduce the
experimental work associated with the searching the optimal mixture composition. Several all-atom
force-fields were developed to predict the phase behaviour of perluoroalkanes [1,2], hydrofluoroolefins
[2,3] and selected hydrofluoroalkanes: R32 [3], R134a [4] and fluoromethanes [5]. The interaction
parameters of any of the first four models [1-4] cannot be transferred to hydrofluorocarbons containing
fluorine and hydrogen bonded to the same carbon atom. Only the last force-field of Potter et al. [5] was
developed for an application to a broader variety of compounds; however it requires specific (non-
Lorentz-Berthelot) parameters for H- F pairs.
The development of all atom transferable force fields for hydrofluorocarbons is not a trivial task
as the partial charges and the C-F bond length of the molecule can dramatically change depending on the
nature of the atoms (H or F) bonded to the carbon atoms and on the molecular conformation. For
instance, the C-F bond length can vary of more than 10% from -CF3 to - CFH2 groups. Several force field
parameters such as molecular geometries and partial charges can be obtained from quantum calculation.
However, the partial charges particularly depend on the quantum chemistry method (i.e. the level of
theory and the basis set).
In this work, we propose transferable all atom force fields for short hydrofluorocarbons
(fluoromethanes and selected fluoroethanes). We used two different ab initio methods and the CHELPG
procedure to predict the atomic partial charges, and we optimized the corresponding Lennard-Jones
parameters for hydrofluoroalkanes by using the methodology of Bourasseau et al. [6]. The new forced
fields are used to predict the physical properties of some pure compounds and binary mixtures.
References
[1] E. K. Watkins, W. L. Jorgensen, J. Phys. Chem. A, 2001, 105: 4118-4125.
[2] E. Paulechka, K. Kroenlein, A. Kazakov, M. Frenkel, J. Phys. Chem. B, 2012, 116: 14389-14397.
[3] G. Raabe, J. Chem. & Eng. Data, 2013, 58: 1867-1873.
[4] R. P. S. Peguin, G. Kamath, J. J. Potoff, S. R. P. da Rocha, J. Phys. Chem. B, 2009, 113: 178-187.
[5] S. C. Potter , D. J. Tildesley , A.N. Burgess, S. C. Rogers, Mol. Phys., 1997, 92: 825-833.
[6] E. Bourasseau, H. Haboudou, A. Boutin, A. H. Fuchs, P. Ungerer, 2003, J. Chem. Phys., 118, 3020-3034
Acknowledgements
The results presented in this work are part of the ongoing project "PREDIREF". We are grateful to the National
French Research Agency (ANR-13-CDII-0008) for providing financial support to this project.

PPEPPD 2016
th
Rapid characterization of multicomponent vapor-liquid equilibria
using Raman spectroscopy
Bastian Liebergesell1*, Carsten Flake1, Thorsten Brands1, Hans-Jürgen Koß1 and André Bardow1
1
*Corresponding author: bastian.liebergesell@ltt.rwth-aachen.de
Scientific topic: Phase equilibria (experimental)
Keywords: Vapor-liquid equilibrium, static, isothermal, non-invasive, Raman spectroscopy
Abstract
A novel setup for the rapid characterization of multicomponent vapor-liquid equilibria (VLE) using
Raman spectroscopy is presented. VLE data are of major importance in many chemical processes.
Despite significant progress in predictive methods for vapor-liquid phase equilibria, experimental VLE
data are still required as basis for process design.
Large databases of VLE data already exist in literature. Still, VLE data are hard to find for novel
compounds and their mixtures. The experimental characterization of multicomponent VLE is usually
time consuming and costly. Conventional experimental methods require relatively large amounts of
substance, while novel compounds are often very expensive, or only available in small amounts. In
addition, complex handling procedures are required: Static isothermal methods require thoroughly
degassed substances to be added to a fully evacuated equilibrium chamber. Analytical methods usually
withdraw samples from the equilibrium chamber, which is challenging and known to cause a significant
error in the analytical chain. After every analysis, the equilibrium chamber is cleaned and evacuated
again, before an entirely new experiment is started. These procedures are time consuming and material
intensive.
In this work, we present a novel VLE setup overcoming these issues. To avoid potential disturbances to
the phase equilibrium by sampling, non-invasive Raman spectroscopy is employed. Raman spectroscopy
provides component-specific quantitative concentration information. The spectroscopic analysis is very
fast, taking only several seconds. Small amounts of substance (<3 ml) are required for one experiment
run, that does give access to several VLE data sets. The setup avoids extensive degassing of the fluids
and the resulting inconvenient handling of the setup and the samples. Samples are degassed directly in
the equilibrium chamber. The down-scale of the systems’ dimensions increases the surface-to-volume
ratio. Consequently, heat and mass transfer, as well as mixing within the respective phases, are enhanced,
reducing equilibration times to several minutes.
The novel setup has been validated by reproduction of isothermal VLE data from the literature.
Acknowledgements
This work was performed as part of the Cluster of Excellence “Tailor-Made Fuels from Biomass”, which is funded
by the Excellence Initiative by the German federal and state governments to promote science and research at
German universities.

PPEPPD 2016
th
Critical Analysis Of Liquidus Curves In Concentrated Aqueous Solutions Of

Borates MBO2 (M = Na, K)
Goutaudier Christelle*, Richard Tenu and Jean-Jacques Counioux

Laboratoire Multimateriaux et Interfaces, CNRS 5615, Univ Lyon 1, F-69622 Villeurbanne cedex, France
*Corresponding author: christelle.goutaudier@univ-lyon1.fr
Keywords: solid-liquid equilibria, solvation, quasi-ideal model, phase diagram
Abstract
Alkali borohydrides represent attractive chemical hydrides for hydrogen generation and storage in
portable fuel cell applications. Their hydrolysis leads to the formation of borates hydrates, MBO2.xH2O
and of hydrogen, following the reaction:
MBH4 (s) + (2+x) H2O (l) → MBO2.xH2O (s) + 4 H2 (g)
Since water is a reagent in hydrolysis, higher the hydration degree of borate formed is, lower the released
hydrogen yield. As a consequence, the thermodynamic knowledge of the hydrolysis by-products via the
binary phase diagram MBO2 – H2O, is a fundamental approach in order to increase the hydrogen storage
yield by using borohydrides.
In previous works, the liquid-solid equilibria of the binary system MBO2 – H2O (M=Na, K)
were studied by solubility, TGA and DSC measurements. Then the experimental results were
the subject of a systematic critical analysis in order to produce analytical curves describing the
limit conditions and deduce molecular interactions. These objectives are more and more difficult
to reach when activity coefficients become important and the solutions models are complicated
to use with two phases in equilibrium. The quasi-ideal model developed in the team [1] is a
predictive calculation model of equilibrium based on a simple formalism for ideal solutions in
which the thermodynamic data of pure compounds are fixed. For real solutions, the model will
take into account the existence of chemical entities resulting from strong or weak molecular
interactions such as dimerization, solvation, dissociation, etc.
References
[1] R. Tenu, C. Goutaudier, B. El Goundali, M. Kaddami, JJ. Counioux, J. Therm. Anal. Calorim., 2013, 112: 263-
8.

PPEPPD 2016
th
Anion Effects on the Solubility of R1234yf in Ionic Liquid
Xiangyang Liu, Maogang He*, Lihang Bai

Key Laboratory of Thermal Fluid Science and Engineering of MOE,
Xi’an Jiaotong University, China
*Corresponding author: mghe@mail.xjtu.edu.cn
Keywords: 2,3,3,3-Tetrafluoroprop-1-ene, Ionic liquid, Phase behavior
Abstract
Ionic liquid and hydrofluorocarbon (HFC) are a potential working pair for the absorption refrigeration
cycles [1]. The solubility hehevior of HFC in ionic liquid has an important influnce on the performance
of the absorption refrigeration cycle [2]. The experimental results in literture show that solubilities of
HFCs are greater in ionic liquids whose anions consist of fluorinated groups [3]. R1234yf has zero ozone
depletion potential and excellent life cycle climate performance, which is an new alternative refrigenrant.
This work aims to investigate the effect of the anion-structure on the solubilities of 2,3,3,3-
Tetrafluoroprop-1-ene (R1234yf) in five imidazolium-based ionic liquid with different fluorine-
containing anions. Solubilities of R1234yf in these five ionic liquids at temperature from 283K to 333K
and at pressures up to 1.0 MPa were measured with an isochoric saturation method. The interaction
between R1234yf and the five ionic liquids were analyzed.
References
[1] D. X. Zheng, L. Dong, W.J. Huang “A review of imidazolium ionic liquids research and development towards
working pair of absorption cycle” Renewable and Sustainable Energy Reviews, 2014, 37: 47–68.
[2] Y. J. Kim, S. Kim, Y. K. Joshi, A. G. Fedorov, P. A. Kohl “Thermodynamic analysis of an absorption

refrigeration system with ionic-liquid refrigerant mixture as a working fluid” Energy, 2012, 44: 1005–1016.
[3] M. B. Shiflett, A. Yokozeki “Solubility and diffusivity of hydrofluorocarbons in room-temperature ionic

liquids” AIChE Journal, 2006, 52: 1205–1219.
Acknowledgements
The supports provided by the National Natural Science Foundation of China (No. 51506172) for the present work
are gratefully acknowledged.

PPEPPD 2016
th
A Review on Diffusivities of Gases and Liquids with Ionic Liquids

Maogang He*, Sanguo Peng, Xiangyang Liu
Key Laboratory of Thermo-Fluid Science and Engineering, Ministry of Education, Xi’an Jiaotong University,
Xi’an, Shaanxi province, 710049, P. R. China
Scientific topic: Thermodynamics and transport properties
Keywords: Diffusivities, Ionic liquids, Models
Abstract
Ionic liquids (ILs) are considered as promising green solvents due to their unique properties, such as high
solubility, high thermostability, low volatility and good conductivity [1]. The diffusivities of gases and
liquids with ILs strongly affect the separation processes and chemical reactions. Much work has been
conducted to investigate the diffusivities of gases and liquids with ILs using different experimental
methods [2, 3]. In this paper ,we reviewed the experimental methods for measuring the diffusion
coefficients of gases and liquids with ILs and systematically summarized the experimental data for the
first time. A model based on free-volume theory was proposed for the prediction of the diffusion
coefficient.
References
[1] H. Tokuda, S. Tsuzuki, M. A. B. H. Susan, K. Hayamizu, M. Watanabe “How ionic are room-temperature ionic
liquids? An indicator of the physicochemical properties” The Journal of Physical Chemistry B, 2006, 110: 19593-
19600.
[2] M. B. Shiflett, A. Yokozeki “Solubility and diffusivity of hydrofluorocarbons in room-temperature ionic

liquids” Aiche Journal, 2006, 52(3):1205-1219.
[3] M. H. Rausch, J. Lehmann, A. Leipertz, A. P. Fröba “Mutual diffusion in binary mixtures of ionic liquids and
molecular liquids by dynamic light scattering (DLS)” Physical Chemistry Chemical Physics, 2011, 13(20):9525-
9533.
Acknowledgements
This work was supported by National Nature Science Fund Committee(NSFC No. 51376141). The authors
gratefully acknowledge for financial support.

PPEPPD 2016
th
Evaluation of ionic liquid-based technology for biogas upgrading

Yujiao Xie1*, Chunyan Ma1,2, Xiaohua Lu2, Xiaoyan Ji1*
1
Division of Energy Science, Lulea University of Technology, 97187 Lulea, Sweden
2
Key Laboratory of Material and Chemical Engineering, Nanjing Tech University, Nanjing 210009, China
*Corresponding authors: yujiao.xie@ltu.se; xiaoyan.ji@ltu.se
Keywords: Ionic liquid, biogas upgrading, process simulation
Abstract
Biogas upgrading technology is used to concentrate methane, remove CO2 and other gases. The use of
upgraded biogas is considered as one of the most efficient methods of utilizing the renewable energy and
reducing greenhouse gas emission [1]. Nowadays, ionic liquids (ILs) have been paid much attention to be
used as green solvents to remove CO2. The property of ILs and CO2 solubility in ILs have been measured
intensively, while the thermodynamic model and process simulation are also needed in order to promote
the application of IL-based technology.
In this work, the process simulation for biogas upgrading using ILs was performed in Aspen Plus, and
[hmim][Tf2N], [bmim][Tf2N] and [bmim][PF6] were chosen as examples of ILs in order to investigate
the effect of alkyl length and anion on the performance of the biogas-upgrading process. The critical
properties of ILs were estimated by the group contribution method while the thermo-physical properties
were correlated from the available experimental data by the semi-empirical equations. The phase
equilibria of CO2 + IL and CH4 + IL were modelled with the non-random two-liquid model and Redlich-
Kwong equation [2].
The simulation results show that IL-based technology is effective for biogas upgrading with less
energy consumption comparing to the water scrubbing process. The total energy demand increases with
the increase of the alkyl-length, and the [Tf2N]-based ILs is more effective than [PF6]-based ILs. Among
the studied ILs, the process with [bmim][Tf2N] is the one with the lowest energy consumption. The
diameter of absorber and the pressure drop increase with increasing viscosity, while the density only
influences the pressure drop in the absorber. Furthermore, the effects of pressure were studied. It shows
that with the increase of pressure in absorber, the CH4 yield and CO2 removal efficiency increase, and the
CH4 loss ratio decrease. With the increase of pressure in flash, the CH4 yield, CO2 removal efficiency
and CH4 loss ratio increase.
References
[1] Bauer F, Hulteberg C, Persson T, Tamm D. “Biogas upgrading-Review of commercial technologies”. SGC
Rapport 2013:270.
[2] Xie Y, Zhang Y, Lu X, Ji X. “Energy consumption analysis for CO 2 separation using imidazolium-based ionic
liquids”. Applied Energy 2014;136:325-35.
Acknowledgements
We’d like to thank Swedish research council and Swedish Energy Agency for financial support.
PPEPPD 2016
th
Solvent Activity in Electrolyte Solutions
from Molecular Simulations of the Osmotic Pressure
Maximilian Kohns*, Steffen Reiser, Martin Horsch, Hans Hasse

Laboratory of Engineering Thermodynamics, University of Kaiserslautern, Germany
*Corresponding author: maximilian.kohns@mv.uni-kl.de
Keywords: Electrolyte solution, osmotic pressure, solvent activity, molecular dynamics
Abstract
Electrolyte solutions play an important role in a wide variety of industrial and biological processes. One
of the most important properties of an electrolyte solution is the activity of the solvent. It is directly
related to phenomena such as lowering of the vapor pressure and freezing point depression, and it is
connected to the activity coefficient of the salt, which controls the solubility limit of the salt. Describing
electrolyte solutions with molecular simulations holds promise as the structural effects of the strong
interactions are described in a self-consistent way. However, the reliable determination of the solvent
activity in electrolyte solutions by such simulations is challenging and the development of suitable
methods is the subject of several recent studies [1,2].
In this work, a novel method for determining the activity of the solvent in electrolyte solutions by
molecular dynamics simulations is presented. The electrolyte solution is simulated in contact with the
pure solvent. Between the two phases, there is a virtual membrane which is permeable only for the
solvent. In the simulation, this is realized by an external field which acts on the solutes only, and
confines the solutes to a part of the simulation volume. The osmotic pressure, i.e. the pressure difference
of both phases, is obtained with high accuracy from the force on the membrane, so that reliable data on
the solvent activity can be determined.
The new method is validated using test cases of varying complexity. It is then applied to aqueous
electrolyte solutions, for which results for the solvent activity from other recent studies [1,2] are
available. Good agreement is observed. Finally, a systematic investigation of the water activity in
aqueous alkali halide salt solutions is carried out, using models which were developed recently in our
group [3,4]. Even though these models were developed without using activity data, and are mainly based
on density data, in many cases good agreement with experimental solvent activity data is found. The
simulations are performed with an extended version of the molecular simulation program ms2 [5].
References
[1] F. Moucka, I. Nezbeda, and W. R. Smith, J. Chem. Phys. 139 (2013) 124505.
[2] Z. Mester and A. Z. Panagiotopoulos, J. Chem. Phys. 142 (2015) 044507.
[3] S. Deublein, J. Vrabec, and H. Hasse, J. Chem. Phys. 136 (2012) 084501.
[4] S. Reiser, S. Deublein, J. Vrabec, and H. Hasse. J. Chem. Phys. 140 (2014) 044504.
[5] C. W. Glass, S. Reiser, G. Rutkai, S. Deublein, A. Koester, G. Guevara-Carrion, A.Wafai, M. Horsch, M.
Bernreuther, T. Windmann, H. Hasse, and J. Vrabec, Comput. Phys. Commun., 185 (2014) 3302-3306.

PPEPPD 2016
th
Critical Point Prediction Using CPA for Pure and Multicomponent Systems
Andre P. C. M. Vinhal1*, Georgios M. Kontogeorgis1 and Wei Yan1

1
Center for Energy Resources Engineering (CERE), Department of Chemical Engineering,
Technical University of Denmark, Denmark
*Corresponding author: anpi@kt.dtu.dk
Scientific topic: Phase Equilibria; Gas and Oil upstream
Keywords: CPA EoS, Critical Point, Parametrization
Abstract
Due to the crescent demand for fossil fuel energy, unconventional hydrocarbon sources like ultra-deep
reservoirs are becoming more important each day. On the other hand, the production of fossil fuel from
these fields are challenging, not only because of the extreme conditions, such as high pressure and high
temperature, but also owing to the complexity of reservoir fluids and rock [1].
The properties of reservoir fluids are usualy predicted by cubic equations of state (EoS). The reason that
such simple models are still important to the the oil and gas industry is that they provide enough accurate
results for hydrocarbon systems and the use of complex thermodynamic models would deeply increase
the computational effort in reservoir simulators [2]. However, despite the advantages of the cubic
models, high deviations are obtained when they are applied for describing complex fluids [3].
One of the ways to precisely estimate the properties of non-ideal fluids is to use non-cubic EoS, such as
CPA. Nonetheless, one of the drawbacks of the model is that it over predicts the critical temperature and
pressure of the pure components [4]. Comparisons between SAFT and PR show large deviations for the
non-cubic model [5].
Therefore, the goal of this work is to quantify and compare to traditional EoS the deviations of the
critical points for pure and multicomponent systems using CPA. A reparametrization of the equation is
also proposed, in order to reduce these deviations.
References
[1] J. O. d. S. Pizarro, C. C. M. Branco “Challenges in Implementing an EOR Project in the Pre-Salt Province in
Deep Offshore Brasil”, SPE, 2012, SPE-155665.
[2] W. Yan, F. Varzandeh, E. H. Stenby “PVT modeling of reservoir fluids using PC-SAFT EoS and Soave-BWR
EoS”, Fluid Phase Equilib., 2015, 386: 96-124.
[3] J. O. Valderrama “The State of the Cubic Equations of State”, Ind. Eng. Chem. Res., 2003, 42: 1603-1618
[4] G. M. Kontogeorgis, G. K. Folas, “Thermodynamic Models for Industrial Applications: From Classical and
Advanced Mixing Rules to Association Theories”, 1st Wiley: Chichester, West Sussex (UK), 2010.
[5] M. F. Alfradique, M. Castier, “Critical points of hydrocarbon mixtures with the Peng–Robinson, SAFT, and PC-
SAFT equations of state", Fluid Phase Equilib., 2007, 257: 78-101.
Acknowledgements
Ciências sem Fronteiras (CsF), Ministério da Educação (MEC), Brasil.

PPEPPD 2016
th
Experimental and Theoretical Study of Liquid-Liquid Equilibrium of Water

+ 1-Butanol + Inorganic Salt Systems
Kanungnit Chawong1, Vattanavongs Ratanavaraha2 and Panarat Rattanaphanee1*
School of Chemical Engineering, Institute of Engineering, Suranaree University of Technology, Thailand
School of Transportation Engineering, Institute of Engineering, Suranaree University of Technology, Thailand
*Corresponding author: panarat@sut.ac.th
Keywords: Liquid-liquid equilibrium, 1-Butanol, Salting out
Abstract
A presence of dissolved inorganic salts or electrolytes in an aqueous-organic solution can both negatively
or positively influence solubility of the organic solute in the solution and alter the equilibrium
composition of the system. The negative influence is accounted when the solute’s solubility is
diminished upon an addition of the salts. This effect is normally called “salting out” and is often
advantangeously applied in several separation processes: for example, distillation of closed-boiling
components or extraction where the tie-lines are parallel to the solvent axis. In this research, liquid-liquid
equilibrium (LLE) data for the ternary system containing water, 1-butanol and inorganic salt were
measured at 30, 40, and 50ºC and atmospheric pressure. The salts investigated were sodium chloride
(NaCl), sodium sulfate (Na2SO4), ammonium chloride (NH4Cl) and ammonium sulfate ((NH4)2SO4).
Mutual solubility between water and 1-butanol appeared to be decreased and the two-phase region in the
ternary diagrams were notably enlarged when the salts were added into the mixture. This phenomenon
could be regarded as salting out and was more pronounced at high salt concentration. Salting out ability
were in the order of Na2SO4 > (NH4)2SO4 > NaCl > NH4Cl. Temperature in the studied range was
found to have minor effect on the LLE behavior of these systems. In the last part of this research,
experimental LLE data were correlated by a modified extended UNIQUAC model proposed by
Pirahmadi et al., [1,2]. The binary interaction parameters in the model were determined by minimizing
the differences between the experimental and caculated mass fraction for each component over all the
tie-line data. Satisfactory agreement between the experimental and calcluated phase composition were
achieved.
References
[1] F. Pirahmadi, M.R. Dehghani, B. Behzadi, S.M. Seyedi, H. Rabiee “Experimental and theoretical study on
liquid–liquid equilibrium of 1-butanol + water + NaNO3 at 25 and 35 °C” Fluid Phase Equilibria, 2010, 299: 122-
126.
[2] F. Pirahmadi, B. Behzadi, M.R. Dehghani “Experimental measurement and thermodynamic modeling of liquid–
liquid equilibrium for 1-pentanol + water + NaNO3 at 298.15 and 308.15 K” Fluid Phase Equilibria, 2011, 307: 39-
44.

PPEPPD 2016
th
Thermodynamic and Transport Properties for the H2O+CO2+NaCl System

from Polarizable Force Fields
Hao Jiang,1 Othonas A. Moultos2, Ioannis G. Economou2 and Athanassios Z. Panagiotopoulos1*

1
Department of Chemical and Biological Engineering, Princeton University, Princeton, NJ, U.S.A
2
Chemical Engineering Program, Texas A&M University at Qatar, Education City, Doha, Qatar
*Corresponding author: azp@princeton.edu
Scientific topic: Thermodynamics and Transport Properties
Keywords: polarizable force field, phase equilibrium, simulation
Abstract
Understanding the thermophysical properties of H2O+CO2+NaCl system is of great importance to the

design of CO2 geological sequestration process. A prior simulation study[1] for this system showed that
nonpolarizable force fields are inadequate to represent simultaneously the properties of H2O- and CO2-
rich phases. Thermodynamic and transport properties of H2O+NaCl, H2O+CO2, and H2O+CO2+NaCl
mixtures were studied here by Monte Carlo and molecular dynamics simulations using polarizable force
fields. A set of recently developed Drude oscillator polarizable models for H2O, Na+ and Cl-, namely
BK3 models,[2,3] was used to study the density, mean ionic activity coefficient, salt solubility, vapor
pressure, interfacial tension and viscosity for the binary H2O+NaCl mixture.[4] The BK3 set of
polarizable models, which use Gaussian charges for Coulomb interactions and Buckingham potential for
vdW interactions, give satisfactory description for most of the properties of interest, while the NaCl
solubility in H2O and temperature effect on mean activity coefficient are less accurate. A Drude oscillator
polarizable model in the same spirit as the BK3 H2O model was developed for CO2. In general, the new
polarizable model satisfactorily represents the properties of pure CO2 including saturated density, vapor
pressure, enthalpy of vaporization, fluid density, heat capacity, structure, viscosity and diffusivity. For
the binary H2O+CO2 mixture, the cross vdW interaction parameters between BK3 H2O and the
polarizable CO2 model were optimized to vapor-liquid (or liquid-liquid) equilibrium phase compositions.
With the optimized H2O-CO2 cross interaction, equilibrium phase compositions of the ternary
H2O+CO2+NaCl mixture as well as diffusivities of CO2 in H2O and brine were investigated.
References
[1] G. A. Orozco, I. G. Economou, A. Z. Panagiotopoulos. “Optimization of intermolecular potential parameters for
the CO2/H2O mixture”, J. Phys. Chem. B 2014, 118: 11504.
[2] P. T. Kiss, Baranyai A. “A systematic development of a polarizable potential of water”, J. Chem. Phys. 2013,
138: 204507.
[3] P. T. Kiss, Baranyai A. “A new polarizable force field for alkali and halide ions”, J. Chem. Phys. 2014, 141:
114501.
[4] H. Jiang, Z. Mester, O. A. Moultos, I. G. Economou, A. Z. Panagiotopoulos “Thermodynamic and transport
properties of H2O+NaCl from polarizable force field”, J. Chem. Theroy. Comput. 2015, 11: 3802-3810.
Acknowledgements
This publication was made possible by NPRP grant number 6-1157-2-471 from the Qatar National Research Fund
(a member of Qatar Foundation). Additional support was provided by the Office of Basic Energy Sciences, U.S.
Department of Energy, under Award DE-SC0002128, by the Carbon Mitigation Initiative at Princeton University.

PPEPPD 2016
th
Calculation of vapor-liquid equilibria for Lennard-Jones fluids by molecular

dynamics simulation with large number of molecules
Yoshio Iwai*, Issei Taniguchi, and Yasuhiro Tada
Department of Chemical Engineering, Faculty of Engineering, Kyushu University,
744, Motooka, Fukuoka, 819-0395, Japan
*Corresponding author: iwai@chem-eng.kyushu-u.ac.jp
Keywords: Vapor liquid equilibrium, Lennard-Jones fluid, Molecular dynamics simulation, Activity
coefficient, CDSAP mode
Abstract
Molecular dynamics simulation was applied to calculate the phase equilibria with large number of
Lennard-Jones molecules. Vapor, liquid, and vapor-liquid interface exist in a computer cell. The activity
coefficients of the Lennard-Jones binary systems with the same molecular sizes were calculated. The
authors proposed Concentration Dependent Surface Area Parameter (CDSAP) model for activity
coefficients in a previous work [Y. Iwai, Y. Yamamoto, Fluid Phase Equilib. 337(2013) 165-173]. In the
model, the surface area parameters for pure components were cited from the surface area parameters of
UNIQUAC model to reduce the number of parameters. In this work, the reliability of the assumption was
tested by molecular dynamics simulation with Lennard-Jones fluid.

PPEPPD 2016
th
Ab Initio Values of the Gas Transport Properties of Helium, Hydrogen

Isotopologues, and Their Binary Mixtures at Low Density
Zhuo Zhang, Kai Kang, Bo Song*, Xiaopo Wang, Zhigang Liu

Key Laboratory of Thermo-Fluid Science and Engineering, Ministry of Education, School of Energy and Power
Engineering, Xi'an Jiaotong University, China
*Corresponding author: song.bo@mail.xjtu.edu.cn
Keywords: Ab initio potential, Kinetic theory, Transport properties, Helium, Hydrogen isotopologues
Abstract
In principle, the transport properties of dilute gases can be evaluated from the weak interactions between
molecules. First-principles calculations represent an approach in which interaction energies are
determined without the application of experimental data. In recent years, the progress on ab initio
potentials has made it possible to theoretically determine the transport properties of simple gases with
higher and higher accuracy. The high-level ab initio potentials for helium and hydrogen were
respectively developed by Przybytek et al. [Phys. Rev. Lett. 104, 183003 (2010)] and Patkowski et al. [J.
Chem. Phys. 129, 094304 (2008)]. In previous work, we have utilized the new potentials of Przybytek et
al. as well as Patkowski et al. to compute the transport properties of 4He, 3He, 4He-3He [Cryogenics 61, 1
(2014)] and H2, D2, H2-D2 [Mol. Phys. 111, 49 (2013)]. More recently, Bakr et al. [J. Chem. Phys. 139,
144305 (2013)] determined a three-dimensional potential energy surface for the He-H2 dimer by ab initio
calculations. In this work, the study would be extended to calculate the transport properties of helium,
hydrogen isotopologues, and their binary mixtures using the isotropic potentials by Patkowski et al.,
Przybytek et al., and Bakr et al. Helium-4 and hydrogen (H2) are considerably involved in scientific
investigations and engineering applications. The other isotopologues and their mixtures are interesting
from a theoretical standpoint, but their properties are also important for the nuclear energy industry and
analytical chemistry. The systems considered here include four pure gases: T2, HD, HT, DT and 26
binary mixtures: 4He-H2, 4He-D2, 4He-T2, 4He-HD, 4He-HT, 4He-DT, 3He-H2, 3He-D2, 3He-T2, 3He-HD,
3
He-HT, 3He-DT, H2-T2, H2-HD, H2-HT, H2-DT, D2-T2, D2-HD, D2-HT, D2-DT, T2-HD, T2-HT, T2-DT,
HD-HT, HD-DT, HT-DT. The viscosity, thermal conductivity, diffusion coefficient, and thermal
diffusion factor of the considered systems were computed by the classical kinetic theory in the
temperature range of 298 to 2000 K. The calculated values of this work were in good agreement with the
limited experimental data available, and provided additional transport property data where none existed.
Finally, we discussed the effect introduced in the property calculations by neglecting the non-spherical
terms of the interaction potentials.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Grant No. 51406154; 51376149),
the China Postdoctoral Science Foundation (Grant No. 2015T81024; 2014M562407), and the Fundamental
Research Funds for the Central Universities.

PPEPPD 2016
th
Measurement and Modeling of the Phase Behaviour of (CO2 + CO) at

Temperatures between (218.15 and 303.15) K and pressures up to 14 MPa
Lorena F. S. Souza1, Saif Z. S. Al Ghafri1 and J. P. Martin Trusler1*
1
Department of Chemical Engineering, Imperial College London, South Kensington Campus, United Kingdom
*Corresponding author: m.trusler@imperial.ac.uk
Keywords: Carbon dioxide, Carbon monoxide, Vapou-liquid equilibrium, Phase equilibria, Modeling
Abstract
Knowledge of the phase behaviour of the binary mixture (CO2 + CO) is important in gas processing,
especially in connection with synthesis-gas production. Nevertheless, very few experimental data have
been reported for this system. Accordingly, in this work, vapour-liquid equilibrium (VLE) data have
been measured for (CO2 + CO) at temperatures between (218.15 and 303.15) K and at pressures ranging
from the vapour pressure of CO2 to up to 14 MPa. These measurements were performed using a state-of-
the-art computer-controlled apparatus, based on a static-analytical method with analysis by gas
chromatography, as described in detailed by Fandiño, et al. [1]. Measurements were also made along the
three-phase solid-liquid-vapour coexistence curve at pressures from just above the triple-point pressure
of carbon dioxide to approximately 15 MPa.
The experimental VLE data have been modelled with the Statistical Associating Fluid Theory for
Variable-Range potentials of the Mie form (SAFT-VR-Mie) [2] with pure-component parameters based
on vapour-pressure and saturated-liquid density data. A single temperature-independent binary
interaction parameter was regressed against the present experimental data and generally-good agreement
is observed between the experiment and the theory. We have also modelled the data using the Peng-
Robinson equation of state (PR-EoS) [3] combined with classical one-fluid mixing rules incorporating a
temperature-dependent binary interaction parameter. The results show that the PR-EoS can also describe
the experimental VLE data of (CO2 + CO) with acceptable accuracy, except in the critical region.
References
[1] Fandiño, O., J. P. M. Trusler and D. Vega-Maza "Phase behavior of (CO2+H2) and (CO2+N2) at temperatures
between (218.15 and 303.15)K at pressures up to 15MPa." International Journal of Greenhouse Gas Control, 2015,
36: 78-92.
[2] T. Lafitte, D. Bessieres, M. M. Piñeiro and J.-L. Daridon “Simultaneous estimation of phase behavior and
second-derivative properties using the statistical associating fluid theory with variable range approach.” J. Chem.
Phys., 2006, 124.
[3] Peng, D.-Y. and D. B. Robinson "A new two-constant equation of state." Ind. Eng. Chem. Fundamentals, 1976,
15: 59−64.
Acknowledgements
We gratefully acknowledge the funding provided by of Science Without Border (Ciência Sem Fronteiras) and their
permission to publish this research.

PPEPPD 2016
th
Thermodynamic Properties Prediction of Big Molecules wih Equation of

State
Hideo Nishiumi1*
1
Chemical Engineering Laboratory, Hosei University, Tokyo, apan
*Corresponding author: nishi@hosei.ac.jp
Scientific topic: Thermodynamics and transport properties (modeling)
Keywords: prediction, Joback method, big molecule, equation of state, PAG-1
Abstract
To predict thermodynamic properties of unfamiliar substance or its mixture, the group conntribution
such as the Joback method [1] is effective. However a substance is greater, the critical temperature Tc
becomes greater, because calculated standard boiling temperature Tb is proprtional to Tc. For example,
Tc of triolein is 4,019 K according to the Joback method.
Joback correlation can’t extend to a big molecule because it has a maximum point due to a quadratic
equation. First, I developed a monotonically increasing function of Tb (boiling point)/ Tc (critical
temperature) with sum of Tc contribution increments of a molecule obtained from the Joback correlation.
Second, the correlation of Tb / Tc with Tc is not based on the linear Joback correlation but the component
family correlation of experimental data such as chain hydrocarbons, or esters. Using a 15 constant BWR
EoS with prediction parameters obtained, properties of a pure substance or mixture properties are
predicted and compared with experimental data. The results are as follows;
1. Polyethylene glycol ethers (glymes) are expected to promising solvent with carbon dioxide gas in a
high-pressure absorption tower. Comparing with the experimental data by Kodama et al. [2], vapor
pressure or liquid density of glymes, and solubility of CO2 or saturated liquid or vapor density prediction
giges excellent results.
2. For oleic acid, triolein and PAG-1, vapor pressures and solubility of H2 or CO2 in them can be
calculated well.
3. For solubility calculation of CO2 in PAG-1, selection of Tc plays an important role. In this case, Tc
is a prediction parameter. If a value of Tc decreases, convergence increases. To treat Tc as a prediction
parameter seems to extend predection area of thermodynamic properties.
References
[1] K.G.Joback, S.M. Thesis in Chemical Engineering, Massacusetts Institute of Technology, Cambridge, Mass.,
June 1955
[2] D. Kodama, M. Kanakubo, M. Kokubo, S. Hashimoto, H. Nanjo, M. Kato, Fluid Phase Equilib. 302 (2011) 103-
108

PPEPPD 2016
th
Estimation of the Standard Molar Enthalpy of Formation of Low-valued

Biomasses and Their Biogas Residue
Hongliang Qian1,2, Chang Liu2, Xin Feng2, Xiaohua Lu2*

( School of Engineering, China Pharmaceutical University, China; 2State Key Laboratory of Materials-Oriented
1
Chemical Engineering, Nanjing Tech University, China)

*Corresponding author: 271924705@qq.com
Keywords: Continuous thermodynamics, Low-valued biomaterials, Biogas residue, Enthalpy of

formation
Abstract
The standard molar enthalpy of formation of low-valued biomasses and their biogas residue is an
important thermo-chemical data, which is the base of thermodynamic analysis for biomethane,
agricultural waste treatment and so on. The estimation method for the standard molar enthalpy of
formation of low-valued biomasses and their biogas residue is proximate and ultimate analyses.
However, in the both methods, the composition of low-valued biomasses and their biogas residue is
represented by chemical elements (carbon, hydrogen, nitrogen, oxygen and sulfur) or parameters
(moisture, volatile matter (VM), fixed carbon (FC) and ash of a biomass), not their real composition. In
this paper, from the opinion of continuous thermodynamics, the composition distribution function based
on molecular weight of straw and pig manure and their biogas residue is analyzed by Gel Permeation
Chromatography (GPC), and then the standard molar enthalpy of formation of straw and pig manure and
their biogas residue is calculated by thermodynamic cycle (pyrolysis), at last the model between the
standard molar enthalpy of formation and the composition distribution function is established. It can be
concluded that the relative error of the standard molar enthalpy of formation estimated by the method in
this paper is blow 0.5%.
References
[1] Battley E H. A short review and an empirical method for estimating the absorbed enthalpy of formation and the
absolute enthalpy of dried microbial biomass for use in studies on the thermodynamics of microbial growth[J].
Journal of Thermal Analysis and Calorimetry, 2011,104: 13-22.
[2] Yin C Y. Prediction of higher heating values of biomass from proximate and ultimate analyses [J]. Fuel 90
(2011) 1128-1132.
[3] Barin I. Thermochemical Data of Pure Substances (Third Edition) [M]. Weinheim: VCH, 1995.
Acknowledgements
The research is supported by the National Basic Research Program of China(2013CB733501), the National Natural
Science Foundation of China (21136004), the Scientific Research Foundation of China Pharmaceutical University,
Jiangsu Planned Projects for Postdoctoral Research Funds(1402060B) and National Natural Science Funds of China
(21406272).

PPEPPD 2016
th
Evaluation of new inhibitors of hydrate clathrate formation

María Esther Rebolledo-Libreros*, Joel Reza, Arturo Trejo, and Diego Javier Guzmán Lucero
Instituto Mexicano del Petróleo, Dirección de Investigación en Transformación de Hidrocarburos. Gerencia de
Separación de Hidrocarburos. México
*Corresponding author: mrebolle@imp.mx
Scientific topic: materials (e.g. polymers)
Keywords: Polymers, Hydrate inhibitors, Tetrahydrofuran, natural gas, Cloud point
Abstract
In order to prevent the formation of hydrate plugs in pipelines and wells, the oil and gas industries apply
different methods such as pipeline heating, system pressure reduction, water removal, and the addition of
anti-freezing agents such as methanol and diverse glycols [1]. An alternative method has aimed at
controlling the formation of hydrate plugs by using chemical compounds that inhibit or retard the
nucleation process of such plugs; the dosage of such inhibitors is much lower (0.01-5 mass %) than the
actual amount of water [2].
The present work presents the experimental results for the evaluation of new low dosage inhibitors,
synthesized at the Mexican Petroleum Institute (MPI), which could be used to inhibit or delay the
formation of clatrate hydrates of gaseous hydrocarbons by the Mexican oil industry. The evaluation was
carried out using experimental methods developed in-house at the MPI Thermophysics Research Area.
The performance evaluation of the synthesized polymeric inhibitors, obtained from different monomers,
was done by running three types of experimental tests: Capacity to inhibit the formation of type II
tetrahydrofuran hydrates, THF, at atmospheric pressure; capacity to inhibit the formation of type II
natural gas hydrates under high pressure, and low temperature conditions; and the cloud point of the
inhibitors in aqueous solutions with high concentration of electrolytes. From the obtained results, it was
possible to establish that the synthesized copolymers and terpolymers can be considered as promising
low dosage inhibitors to prevent the formation of hydrate clots.
Once the thorough physicochemical characterization of the synthesized polymeric inhibitors is achieved,
they could be considered to develop MPI formulations for inhibiting hydrocarbon clathrate hydrates in
order to scale up the evaluation results in a multiphase flow test circuit.
References
[1] Gbaruko B.C., Igwe J.C., Gbruko P.N., Nwokeoma R.C. Gas hydrates and clathrates: Flow assurance,
environmental and economic perspectives and the Nigerian liquefied natural gas project. J. Petr. Sci. Eng. 56
(2007) 192-198.
[3] Kelland M.A. Production chemicals for the oil and Gas industry. Second edition, CRC Press. Boca Raton, Fl.
2014.

PPEPPD 2016
th
Thermodynamic analysis of fluoride removal using an aluminum-doped

adsorbent
Didilia I. Mendoza-Castillo 1,2, H. Elizabeth Reynel-Ávila 1,2, Adrián Bonilla-Petriciolet 2*

1
Catedras CONACYT/ Consejo Nacional de Ciencia y Tecnologia, Mexico
2
Department of Chemical Engineering/ Instituto Tecnologico de Aguascalientes, Mexico
*Corresponding/Presenting author: petriciolet@hotmail.com / didi_men@hotmail.com
Keywords: Aluminum-doped adsorbent, Denim fiber scraps, Flouride adsorption, Thermodynamic

studies.
Abstract
In this study, the thermodynamic analysis of fluoride removal using an aluminum-doped adsorbent was
performed. This novel adsorbent was obtained from denim fiber scraps. Thermodynamic parameters of
adsorption process that include the Gibbs free energy, enthalpy, and entropy were estimated. Batch
equilibrium experiments were carried out at 25, 30 and 40 °C using the synthesized adsorbents. Results
showed a dual thermodynamic behavior for fluoride adsorption with respect to temperature. In particular,
the maximum fluoride uptake increased from 2.2 to 4.5 mg/g when temperature varied from 25 to 30 °C.
This behavior indicated that adsorption process is endothermic (∆H= 1.84 kJ/mol). However, from 30 to
40 °C, the adsorption capacity decreased 53 % showing an exothermic nature of the adsorption process
(∆H= -13.17 kJ/mol). This behavior suggested that fluoride uptake may be caused by a combination of
both physical and chemical processes. According with Aguayo-Villarreal et al. (2011), when
chemisorption is involved, the adsorption process is usually favored with temperature; while if a physical
adsorption process is involved, a decrease of solute uptake with temperature should be expected. On the
other hand, Gibbs free energy changes are in the range of -20 and 0 kJ/mol, which confirmed that the
physisorption process was the dominating adsorption mechanism [2]. This novel adsorbent is effective
for the removal of fluoride ions and it may offer a better removal performance than those reported for
other synthetic and natural adsorbents. Based on this fact, we conclude that denim fiber scraps can be
used for synthesizing novel adsorbents for water defluoridation. In particular, the reutilization of denim
wastes offers the possibility for improving the waste management and reducing waste disposal costs in
textile industrial sector.
References
[1] I.A. Aguayo-Villarreal, A. Bonilla-Petriciolet, V. Hernández-Montoya, M.A. Montes-Morán, H.E. Reynel-Avila
“Batch and column studies of Zn2+ removal from aqueous solution using chicken feathers as sorbents” Chemical
Engineering Journal, 2011, 167: 67-76.
[2] N.M. Mahmoodi, B. Hayati, M. Arami “Kinetic, equilibrium and thermodynamic studies of ternary system dye
removal using a biopolymer” Industrial Crops and Products, 2012, 35: 295-301.
Acknowledgements
Authors acknowledge the support provided by CONACYT, DGEST and Instituto Tecnológico de Aguascalientes
(Mexico).

PPEPPD 2016
th
Discrete Modeling: The Concept of Shannon Entropy Used for

Thermodynamic Model Developoment
Thomas Wallek1*, Martin Pfleger1 and Andreas Pfennig2
1
Institute of Chemical Engineering and Environmental Technology, NAWI Graz,
Graz University of Technology, Austria
2
Department of Chemical Engineering, Université de Liège - Sart-Tilman, Belgium
*Corresponding author: thomas.wallek@tugraz.at
Scientific topic: Fundamentals / Thermodynamics and Transport Properties
Keywords: discrete modeling, Shannon entropy, maximum entropy principle, lattice model, local
compositions
Abstract
Increasing use of biobased materials challenges thermodynamics by the need to describe more complex
and/or oxygenated molecules. Established models often use local compositions for representation of
molecular properties, latest developments even accounting for molecular orientations [1]. However, the
fact that local compositions represent averaged system values, limits the ability of such approaches to
describe complex mixtures. To incorporate a more detailed molecular picture into thermodynamics,
previous papers introduced ‘discrete modeling’ as a novel approach [2-3]. As a proof of concept, the
thermal and caloric equations of state, heat capacity and Maxwell-Boltzmann distribution for ideal gas
were derived on the basis of discrete states of individual molecules. In this paper, discrete modeling is
applied to lattice systems for condensed-phase mixtures in view of gE-model development. The discrete
model is based on the definition of discrete system states, where states of equal energy are combined in
discrete energy classes, represented by discrete values of local composition. In this way, the model uses
the same level of discretization as classical statistical thermodynamics in terms of partition functions.
Considering that each energy class can be realized by several system states, the possible arrangements of
the system at a given energy are characterized by degeneracy functions. The formalism of discrete
modeling then uses probabilities of discrete local compositions along with degeneracies to express the
Shannon entropy of the system together with all relevant constraints, like energy due to molecular
interactions. Using Shannon entropy equivalently to thermodynamic entropy, constrained maximation of
entropy then yields the equilibrium distribution for the probabilities of energy classes, from which all
thermodynamic functions of interest can be derived. The results of this approach are compared to the
well-known Guggenheim model as well as Monte-Carlo simulations. To conclude, the availability of a
complete distribution of energy classes, rather than averaged local compositions, allows a more detailed
consideration of molecular conditions and is a promising basis for future gE-development.
References
[1] R. Bronneberg, A. Pfennig “MOQUAC, a New Expression for the Excess Gibbs Energy Based on Molecular
Orientations” Fluid Phase Equil. 2013, 338: 63-77.
[2] M. Pfleger, T. Wallek, A. Pfennig “Constraints of Compound Systems: Prerequisites for Thermodynamic
Modeling Based on Shannon Entropy” Entropy 2014, 16: 2990-3008.
[3] M. Pfleger, T. Wallek, A. Pfennig “Discrete Modeling: Thermodynamics Based on Shannon Entropy and
Discrete States of Molecules” Ind. Eng. Chem. Res. 2015, 54: 4643-4654.

PPEPPD 2016
th
Liquid-liquid equilibria of water + 1-propanol + 1-butyl-1-

methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ternary system
Amparo Cháfer, Javier de la Torre, Estela Lladosa* and Jordi Pla-Franco
Departamento de Ingeniería Química, Universitat de València, Spain
*Corresponding author: amparo.chafer@uv.es
Keywords: liquid-liquid equilibria, 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide,

water, 1-propanol, ionic liquid
Abstract
One of the relevant problems in the chemical industry is the separation of azeotropes. Their separation by
simple distillation is basically impossible, and extractive distallation consumes much more energy than
liquid liquid extraction, so these alternative could be interesting. Resently, researches start to explore
these option using ionic liquids as solvent [1]. The remarkable azeotrope breaking capacid of ionic
liquids, their almost null volatility at room temperatures, and their recycling ease, have garanted them
recognition as posible sustainable alternatives to conventional solvents [1]. This work continues with a
study developed by our group on the use of ionic liquids as extractant solvents of alcohols + water
mixtures which form azeotropes [2], using in this case the 1-butyl-1-methylpyrrolidinium
bis(trifluoromethanesulfonyl)imide [bmp][Tf2N] as ionic liquid.
The determination of composition of the equilibrium liquid phases for water + 1-propanol + [bmp][Tf2N]
system were carried out at different temperatures (283.15, 303.15 and 323.15 K) and atmospheric
pressure. The temperature influence on the system is remarkable. The liquid-liquid phase diagrams for
the system are type I, where only one binary subsystem has partially miscibility ([bmp][Tf 2N] + water)
and two binary subsystems are miscible. The ternary systems exhibits a large two-phase region. The size
of immiscibility gap is adequate for extraction as well as the slope of tie lines. The NRTL model is
succesfully used to correlated the experimental data [3].
References
[1] A. B. Pereiro, J. M. M. Aráujo, J. M. S. S. Esperança, I. M. Marrucho, L.P.N. Rebelo “ Ionic liquids in
separations of azeotropic systems- A review” J. Chem Thermodynamics, 2012, 46: 2-28.
[2] A. Cháfer, J. de la Torre, A. Font, E. Lladosa “Liquid–Liquid Equilibria of Water + Ethanol + 1-Butyl-3-
methylimidazolium Bis(trifluoromethanesulfonyl)imide Ternary System: Measurements and Correlation at
Different Temperatures” J. Chem. Eng. Data, 2015, 60: 2426–2433.
[3] D. S. Abrams, J. M. Prausnitz “Statistical Thermodynamics of Liquid Mixtures: A New Expression for the
Excess Gibbs Energy of Partly or Completely Miscible Systems” AIChE J. (1975) 21: 116-128.
Acknowledgements
Financial support from the Ministerio de Ciencia y Tecnología of Spain, through project No. CTQ2010-18848/PPQ
and the FEDER European Program are gratefully acknowledged.

PPEPPD 2016
th
Simple equipment for measurement of total pressure of polymer + solvent

mixtures
Jan Pavlíček, Grozdana Bogdanić, and Ivan Wichterle*

Institute of Chemical Process Fundamentals, The Czech Academy of Sciences, Prague, Czech Republic
*Corresponding author: wi@icpf.cas.cz
Scientific topic: phase equilibria (experimental, modelling)
Keywords: vapor-liquid equilibrium, polymer-solvent system, total pressure
Abstract
This study belongs to a series of continuing studies of vapour–liquid equilibria (VLE) in diluted polymer
+ solvent systems. We investigated polystyrene (PS) + butan-2-one [1] or + toluene [2], poly(methyl
methacrylate) + acetone [3] or + butan-2-one [4], poly(acrylic acid) + water [3], including earlier
measurements of VLE in solutions of co- and terpolymers of octadecyl acrylate and octadecyl
methacrylate with styrene and 1-vinyl-2-pyrrolidone [5], [6].
In this work, a new equipment designed for total pressure determination in mixtures where one of
component is not volatile, such as polymer + solvent systems, is presented. It enables measurement of
pressure above solutions within the temperature interval 30 – 160 oC and in wider concentration range.
The equipment has been tested using data on known systems, and some preliminary results on VLE
measurement for systems poly(ethylene glycol) + water, and poly(styrene) + toluene are presented.
References
[1] J. Pavlíček, G. Bogdanić, I. Wichterle, Ebulliometric Measurement of Total Pressure in the Binary Polystyrene
+ Butan-2-one system, Fluid Phase Equilib., in press.
[2] J. Pavlíček, G. Bogdanić, I. Wichterle, Vapour–Liquid Equilibria in the Polystyrene + Toluene System at
Higher Concentrations of Solvent, Chem. & Biochem. Eng. Q. 29 (2015) 1–4.
[3] J. Pavlíček, G. Bogdanić, I. Wichterle, Vapour–Liquid Equilibria in the Polymer + Solvent System Containing
Lower Concentrations of Solute at Normal or Reduced Pressures, Fluid Phase Equilib. 358 (2013) 301–303.
[4] J. Pavlíček, G. Bogdanić, I. Wichterle, Vapour–Liquid Equilibria in the Poly(methyl methacrylate) + 2-
Butanone System Containing Lower Concentrations of Solute at Normal or Reduced Pressures, Chem. Biochem.
Eng. Q. 28 (2014) 447–450.
[5] J. Pavlíček, G. Bogdanić, I. Wichterle, Circulation Micro-ebulliometer for Determination of Pressure above
Mixtures Containing Solvent and Non-volatile Component, Fluid Phase Equilib. 297 (2010) 142–148.
[6] G. Bogdanić, I. Wichterle, Vapor–Liquid Equilibrium in Diluted Polymer + Solvent Systems, J. Chem. Eng.
Data 56 (2011) 1080–1083.
Acknowledgements
This study was partly supported by the Czech Science Foundation (Grant No. 15-19542S).

PPEPPD 2016
th
Prediction of Interfacial Properties of Ternary, Sulfur Containing Mixtures
Christian Bühl* and Sabine Enders

KIT, Institute of Technical Thermodynamics and Refrigeration Engineering, Germany
*Corresponding author: christian.buehl@kit.edu
Scientific topic: Surfaces, interfaces and confinement effects
Keywords: PC-SAFT, Density gradient theory, hydrogen sulfide, sulfur dioxide, Enhanced oil recovery
Abstract
Sulfur containing components, like hydrogen sulfide (H2S) and sulfur dioxide (SO2), are always present
in mixtures relevant to oil recovery or to oil treatment. Caused be the toxicity of these molecules mostly
no experimental data in terms of phase equilibra or interfacial properties are available in the public
literature. Therefore, a releable theoretical method for the prediction of phase equlibria as well as
interfacial properties is requiered.
Recently, such a theoretical method based on PC-SAFT-EOS in combination with the density gradient
theory for the investigation of binary mixtures could be established [1]. The phase equlibria and the
interfacial properties (interfacial tension, interfacial profils, relative enrichment) for mixtures containing
carbon dioxide (CO2) and H2S or SO2 were investigated in detail [1]. In this contribution, the method is
extended to ternary mixture containing additionally methane (CH4) or heptane (C7H16) representing the
natural gas and oil. The theoretical method requires the pure-component parameters of PC-SAFT-EOS
and the so-called influence parameter, i, and for mixture the binary interaction parameter, kij. The pure-
component parameters could be taken from the literature [2,3] and the binary interaction parameter were
fitted to the vapor-liquid equilibria of the corresponding binary sub-systems, if experimental data were
available. If no experimental data were avalable, this parameter were put to zero. The quadrupole of CO 2
is taken into account using the experimental qudropule momentum, whereas, the small dipol of SO 2 is
neglected. H2S is modelled as associating component using the association schema 2B. Applying the
geometrical mixing rule for the influence parameter, permits the prediction of the interfacial properties of
the binary mixtures. For ternary mixtures, the utilised theoretical framework is fully predictive.
The following ternary mixtures: CO2+H2S+CH4, CO2+H2S+C7H16, CO2+SO2+CH4, CO2+SO2+C7H16
were investigated over a large pressure and temperature range. It turns out that the presence of the sulfur
containing molecules leads to a decrease of the interfacial tension in comparison to the corresponding
binary system [4] at the same temperature and presssure. At low pressures, CO2 as well as H2S will
enriched at the interface in the CO2+H2S+C7H16 mixture, where the enrichment effect of CO2 is more
pronounced. At constant temperature, the partial density of H2S decrease with increasing pressure, and
hence, at a certain pressure only CO2 will be adsorbed in the interface. For the mixture CO2+SO2+C7H16
only a relative enrichment of CO2 could be found. The partial density profil for SO2 shows no maximum.
References
[1] C. Bühl, A. Danzer, S. Enders “Prediction of Interfacial Properties of Ternary, Sulfur Containing Mixtures”
Fluid Phase Equlibria, 2015, in press http://dx.doi.org/10.1016/j.fluid.2015.08.026.
[2] J. Gross, G. Sadowski, “Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for Chain
Molecules.” Ind. Eng. Chem. Res. 2001, 40: 1244-1260.
[3] J. Gross, “An Equation of State Contribution for Polar Components: Quadrupolar Molecules.” AIChE Journal
2005, 51: 2556-2568.

PPEPPD 2016
th
A Thermodynamic Approach for Analysis and Prediction of Pharmaceutical

Dissolution
Yuanhui Ji* and Raphael Paus

Laboratory of Thermodynamics, Department of Biochemical and Chemical Engineering, TU Dortmund, Dortmund,
Germany
*Corresponding author: Yuanhui.Ji@bci.tu-dortmund.de
Scientific topic: Pharmaceuticals and cosmetics
Keywords: Crystalline pharmaceutical, Excipient, Dissolution kinetics, Chemical potential gradient

model, PC-SAFT EoS
Abstract
Investigation of pharmaceutical dissolution is of crucial importance for characterizing the performance of

pharmacuticals and for pharmaceutical development. The dissolution process of many poorly soluble
pharmacuticals often shows complex behaviors. This complexity makes it difficult to understand the
dissolution mechanism and to accurately describe and predict the dissolution kinetics of these
pharmaceuticals. Moreover, excipients (e.g. polymers) are often introduced to prepare pharmaceutical
formulations to enhance the dissolution rate of poorly soluble pharmaceuticals. The presence of
excipients further complicates the analysis and prediction of pharmaceutical dissolution kinetics.
Therefore, it is essential to develop a theoretical model which is able to analyze the dissolution
mechanism and to predict the dissolution kinetics of pharmaceuticals.
In this work, the dissolution of the pharmaceuticals indomethacin, naproxen and trimethoprim in the
solutions consisting of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP) and mannitol was
investigated using a rotating disk system. A molecular-based chemical potential gradient model was
developed to study the dissolution mechanisms and to predict the dissolution kinetics of the
pharmaceuticals. In this model, the perturbed-chain statistical associating fluid theory (PC-SAFT) [1]
was applied to estimate the solubility and activitiy coefficient of the components. The effects of
pharmaceutical type, excipient type, temperature and pH value of the medium on pharmaceutical
dissolution kinetics and mechanism were investigated. Furthermore, the intrinsic dissolution kinetics of
pharmaceuticals was correlated and the dissolution kinetics of cylindrical pharmaceutical tablets was
predicted and verified with experimental findings.
References
[1] J. Gross and G. Sadowski “Perturbed-chain SAFT: An equation of state based on a perturbation theory for chain
molecules” Industrial & Engineering Chemistry Research, 2001, 40(4): 1244-1260.
Acknowledgements
The authors would like to acknowledge the financial support from the Alexander von Humboldt Foundation (Y. H.
Ji) and German Science Foundation (Leibniz Award to G. Sadowski).

PPEPPD 2016
th
Surrogate Design for Complex Hydrocarbon Mixtures:

Property Prediction by the Real-Component Approach
Kathrin Kos*, Thomas Wallek

Institute of Chemical Engineering and Environmental Technology, NAWI Graz, Graz University of Technology,
Austria
*Corresponding author: kathrin.kos@tugraz.at
Scientific topic: Thermodynamics and Transport Properties / Experimental, Modeling
Keywords: real-component surrogates, optimization algorithm, thermodynamic models, property

prediction
Abstract
Process simulations dealing with petroleum products and fuels are traditionally based on the pseudo-
component approach which is satisfactory for atmospheric conditions and non-polar fossil fuels. In the
future though, the share of polar biogenic energy carriers like ethanol or biodiesel contained in fuels will
increase, significantly limiting applicability of the pseudo-component approach.
An alternative method for the characterization of complex hydrocarbon blends like gasoline, diesel or
biodiesel fuel is the generation of surrogates, i.e. substitute mixtures, composed of few real chemical
components with defined composition as required for engine and combustion CFD simulations [1]. This
real-component approach allows application of rigorous thermodynamic models such as equations of
state or activity coefficient models for equilibrium calculations, property estimation and experimental
validation.
Real-component surrogates can be easily used for experimental work as they can be exactly reproduced
at any time and in simulations. Thus, inaccuracies arising from oversimplified or imperfect fuel
characterization within simulations can be avoided.
For the generation of such multi-component surrogates an algorithm has been developed and successfully
applied to various diesel fuels [2]. A comprehensive data bank containing pure-component property data
of over seventy hydrocarbon species as well as interaction parameters serves as a data basis for mixture
properties calculation. Surrogates are generated based on the simultaneous fitting of selected fuel
properties of the substitute mixture to given data of the target fuel using a least-squares approach. Design
criteria of first choice are: true boiling point curve, liquid density, cetane number, C/H ratio, lower
heating value and biodiesel content. By means of this optimization method, the optimal composition of
the respective surrogate is obtained according to the selected target properties, their wheighing and the
chosen hydrocarbon species. The selection of an appropriate set of real components is in fact an
important criterion for the successful representation of the target fuel. For this purpose, an algorithm for
automated component selection based on the ‘F-to-enter’ and ‘F-to-remove’ approach was developed and
implemented. The resulting surrogates which typically contain five to ten real chemical components
allow reliable emulation of diesel fuel both in process simulations and engine combustion simulations.
References
[1] J. T. Farrell, N. P. Cernansky, F. L. Dryer, D. G. Friend, C. A. Hergart, C. K. Law, R. M. McDavid, C. J.
Mueller, A. K. Patel, H. Pitsch “Development of an Experimental Database and Kinetic Models for Surrogate
Diesel Fuels” SAE Paper 2007: 2007-01-0201
[2] A. M. Reiter, T. Wallek, A. Pfennig, M. Zeymer “Surrogate Generation and Evaluation for Diesel Fuel” Energy
& Fuels 2015, 29: 4181-4192
PPEPPD 2016
th
Integrated design of ORC processes and working fluids based on equilibrium

and transport properties from PCP-SAFT
Johannes Schilling1*, Dominik Tillmanns1, Matthias Lampe1, Madlen Hopp2, Joachim Gross2 and André Bardow1
1
2
Institute of Thermodynamics and Thermal Process Engineering, Stuttgart University, Germany
*Corresponding author: johannes.schilling@ltt.rwth-aachen.de
Keywords: process design, working fluid selection, PCP-SAFT, CAMD, transport properties
Abstract
Organic Rankine Cycles (ORCs) are used to generate electrical power from low-temperature heat. To
exploit the full potential of a heat source, process and workind fluid need to be tailored to the specific
application. Thus, systematic computer-aided molecular design (CAMD) methods have been proposed
for the integrated design of ORC process and working fluid. However, most computer-aided molecular
design methods are limited to equilibrium properties only. For integrated solvent and process design,
Burger et al. [1] demonstrate the merits of considering transport properties in a hierarchical method. For
ORCs, transport properties are even more crucial since they largely determine the actual cost.
In this work, we extend the Continuous-Molecular Targeting framework [2] for the integrated design of
processes and working fluids by considering transport properties: constraints on the viscosity at each
state point of the process are imposed within the optimization. The perturbed-chain polar statistical
associating fluid theory (PCP-SAFT) is used as a physically-based thermodynamic model of the working
fluid [3]. Working fluid design is enabled by a computer-aided molecular design (CAMD) formulation
and a group-contribution method based on PCP-SAFT. For the calculation of the viscosity, entropy
scaling is integrated also based on PCP-SAFT [4]. Thus, we present the first CAMD approach capturing
both equilibrium and transport properties based on a single consistent thermodynamic model. Employing
a consistent thermodynamic model guides the optimization to better solutions.
In the model, the working fluid is represented by its functional groups and directly coupled with a
process model. With this approach, the viscosity can be constrained within the optimization of process
and working fluid. Constraining the viscosity reduces friction loss and enhances heat transfer.
The resulting design approach is demonstrated in a case study of a subcritical ORC process.
References
[1] J. Burger, V. Papaioannou, S. Gopinath, G. Jackson, A. Galindo and C. S. Adjiman, A hierarchical method to
integrated solvent and process design of physical CO2 absorption using the SAFT-γ Mie approach. AIChE J., 2015.
doi: 10.1002/aic.14838
[2] M. Lampe, M. Stavrou, J. Schilling, E. Sauer, J. Gross, A. Bardow, Computer-aided molecular design in the
continuous-molecular targeting framework using group-contribution PC-SAFT, Comput. Chem. Eng., Vol. 81,
2015, Pages 278-287
[3] J. Gross and G. Sadowski. “Perturbed-chain SAFT: An equation of state based on a perturbation theory for
chain molecules”. Ind. Eng. Chem. Res., 2001, 40(4):1244–1260.
[4] O. Lötgering-Lin and J. Gross. A group contribution method for viscosities based on entropy scaling using the
perturbed-chain polar statistical associating fluid theory. Ind. Eng. Chem. Res., 2015, 54 (32), 7942-7952.
Acknowledgements
We thank the Deutsche Forschungsgemeinschaft (DFG) for funding this work (BA 2884/4-1).

PPEPPD 2016
th
Modelling of Phase- and Interfacial Behavior of Branched Alkanes
Christoph Walowski* and Sabine Enders

*Corresponding author: christoph.walowski@kit.edu
Keywords: Lattice Cluster Theory, Branching effects, Density gradient theory, Vapor pressure, Heat
capacities
Abstract
Branched molecules are often present in complex mixtures, like naphtha, or these molecules will be
formed as undesirable side products during chemical reactions. The estimation of the thermodynamic
properties, like normal boiling temperature, vapour pressure, isobaric and isochoric heat capacity or
surface tension, of isomers is always very challenging, because they are often not obtainable with a high
purity for the measurement of these properties. Caused by this situation the experimental data base is
very limited and consequently, it is very hard to fit the pure-component parameters of a suitable EOS.
Recently, an EOS based on the Lattice Cluster Theory (LCT-EOS) [e.g. 1] was formulated for pure-
components [2] and multi-component mixtures [3]. The LCT-EOS allows the direct description of a
molecule’s architecture in terms of the thermodynamic potentials without any additionally adjustable
parameters. The LCT-EOS contains three parameters for a pure component.
In this contribution, the predictive power of the LCT-EOS for the prediction of thermodynamics
properties of branched alkanes will be discussed, if the three pure-component parameters are fitted only
to linear alkanes, where a large amount of experimental data are available in the literature. The
discussion include the following thermodynamic properties: the normal boiling temperature, the vapour
pressure curve, isobaric and isochoric heat capacities and speed of sound.
The LCT-EOS can also be combined with the density gradient theory [4] in order to calculate the
interfacial properties. The density gradient theory requires the so-called influence parameter, which must
be fitted to the interfacial tension at one temperature. In the case of linear alkanes this can be done,
because a lot of experimental data are available. However, this approach cannot be used for branched
molecules, because for several molecules no data are available. Therefore, we will discuss the possibility
to transform the influence parameter from the n-alkanes to the branched molecules. This procedure
allows us to the first time to model the interfacial tension related to the vapor-liquid equilibrium and the
interfacial profile of branched alkanes.
References
[1] J. Dudowicz, K.F. Freed “Effect of Monomer Structure and Compressibility on the Properties of
Multicomponent Polymer Blends and Solutions: 1. Lattice Cluster Theory of Compressible Systems”
Macromolecules, 1991, 24: 5076-5095.
[2] K. Langenbach, S. Enders “Development of an Equation of State Based on Lattice Cluster Theory for Pure
Components” Fluid Phase Equilibria, 2012, 331: 58–79.
[3] K. Langenbach, D. Browarzik, J. Sailer, S. Enders „New Formulation of the Lattice Cluster Theory Equation of
State for Multi-Component Systems.” Fluid Phase Equilibria, 2014, 363: 196-212.
[4] J.W. Cahn, J.E. Hilliard “Free Energy of a Nonuniform System: I. Interfacial Free Energy.” J. Chem. Phys.,
1958, 28: 258-267.
Acknowledgements
For financial support the authors thank the German Science Foundation (DFG) and the Excellence Cluster
UNICAT.

PPEPPD 2016
th
Modeling the viscosity of gases, hydrocarbons and refrigerants with a cubic

EoS coupled to the free volume theory or the friction theory
Luis A. Forero G1, Nicolas Ramirez V.1 and Daniel Muñoz L.1
1
Faculty of Chemical Engineering, Universidad Pontificia Bolivariana,Colombia
*Corresponding author: luis.foreroga@upb.edu.co
Keywords: Viscosity, Cubic equation of state, Free-Volume theory, Friction theory
Abstract
A single model to describe the viscosity of gases, hydrocarbons and refrigerants is developed. The
proposed model is based on a cubic EoS translated in volume [1] and the free volume or friction theories
for visocity [2]. The parameters of the two theories are estimated by fitting the NIST recommended
experimental data for two subcritical isotherms (Tr=0.5, Tr=0.75) and one supercritical isotherm
(Tr=1.3) [3]. In total, parameters are estimated for 50 pure compounds including hydrocarbons, gases
and refrigerants.
To validate the parameters, predictive calculations are performed for the saturated liquid-vapor curve in
the range from reduced temperature at 0.5 until the critical point. Also, calculations are performed in the
single phase region including pressures from the saturation pressure up to 100 Atm. In general, results
are satisfactory with both theories. For many of the substances, the average absolute relative deviation is
around 3.60 % .
References
[1] L.A. Forero, J.A. Velásquez “A Generalized Cubic Equation of State for non-polar and polar substances” Fluid
Phase Equilibria , Accepted for publication DOI:10.1016/j.fluid.2015.09.045.
[2] S. P. Tan, H. Adidharma, B. F. Towler, M. Radosz “Friction Theory and Free-Volume Theory Coupled with
Statistical Associating Fluid Theory for Estimating the Viscosity of Pure n-Alkanes; in “Industrial & Engineering
Chemistry Research", Phillip E. Savage (Editor), 2005, 44 (22), 8409-8418.
[3] E.W. Lemmon, M.L. Huber, M. O. McLinden “Reference Fluid Thermodynamic and Transport Properties”,
National Institude of Standards and Technology Standard Reference Database 23, Version 8.0, 2007.

PPEPPD 2016
th
A simple model to represent the vapor pressure, the liquid density and the
viscosity of imidazolium-based ionic liquids
Luis A. Forero G.1* Daniela López R. 1 Paula Rhenals M.1

1
Faculty of Chemical Engineering/Pulp and Paper Research Group, Universidad Pontificia Bolivariana, Colombia
*Corresponding author: luis.foreroga@up.edu.co
Scientific topic: Thermodynamics and transport transporties
Keywords: Imidazolium ionic liquids, vapor pressure, liquid density, viscosity, cubic equations of state.
Abstract
In this work, a simple model based on a modified Peng-Robinson equation of state translated in volume
[1] is developed to describe the vapor pressure and liquid densitites of the 1-alkyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide ionic liquid series [Cnmim][Ntf2]. The vapor pressure calculations are
based on the concept of zero-pressure fugacity presented in the literature [2,3]. To describe liquid
densities, a simple translation in volume is performed by fitting one data point at 25 °C and atmospheric
pressure. The parameters of the resulting model are generalized in terms of the critical temperature, the
critical pressure and the acentric factor of the ionic liquid series.
On the other hand, the free volume theory (FVT) is selected to correlate the viscosity of the
[Cnmim][Ntf2] series [4]. The liquid density require in the FVT model is calculated with the generalized
cubic EoS developed. In general, results are in good agretment with expeirmental data, for all properties
deviations are below 5.0%.
References
[1] L.A. Forero, J.A. Velásquez “A Generalized Cubic Equation of State for non-polar and polar substances” Fluid
Phase Equilibria , Accepted for publication DOI:10.1016/j.fluid.2015.09.045.
[2] J. Wisniak, A. Apelblat, H. Segura. “Application of cubic equations of state to the fit of vapor pressures of pure
components” Chemical Engineering Science, 1998, 743-751.
[3] J.O. Valderrama, L.A. Forero “An analytical expression for the vapor pressure of ionic liquids based on an
equation of state” Fluid Phase Equilibria, 2012, 77-83.
[4] A. Allal, C. Boned, A. Baylaucq. “Free-volume viscosity model for fluids in the dense and gaseous states”.
Physical Review E 2001, 64, 011203.

PPEPPD 2016
th
A Simple and Generalized Model to Represent the Vapor-Liquid Equilibria

and the Liquid-Densities of Alkane-Alkane, Alcohol-Alcohol and Ether-
Alkane mixtures
Luis A. Forero G.1* , Elizabeth Rincón P.1 and Jorge A. Velásquez J1.
1
Faculty of Chemical Engineering, Universidad Pontificia Bolivariana, Colombia
Scientific topic: Thermodynamics and transport properties (Experimental and modeling) (Poster)
Keywords: Modified Peng-Robinson EoS, Huron-Vidal mixing rules, Vapor-liquid equilibria, Liquid
densities, Generalized expressions.
Abstract
A simple model based on a modified Peng-Robinson equation of state translated in volume [ref] and the
Huron-Vidal-NRTL mixing rules [2] were developed to describe vapor-liquid equilibria and liquid
densities of alkane-alkane, alcohol-alcohol and ether-alkane mixtures. Generalized expressions in terms
of the critical pressure and the critical temperature of alkanes, alcohols and ethers were developed for the
NRTL binary interaction parameters (A12, A21, 12). The model was proposed employing the
homologous series concept by pairing a family of compounds to another. The parameters of the
generalized expressions were determined minimizing the total absolute relative deviation in bubble
pressure. In total 34 , alkane-alkane mixtures were used to develop the model and the average absolute
deviation in bubble pressure (AADP) estimated is 2.26% and the average absolute deviation in the vapor
phase molar fraction (DY) is 0.002. For alcohol-alcohol 17 mixtures were used with AADP of 2.15% and
DY of 0.005, and for ether-alkane 19 mixtures were used with AADP of 1.44% and DY of 0.004.
Additionally, to validate the models, predictive calculations were made for 15 alkane-alkane mixtures, 18
alcohol-alcohol mixtures and 15 ether-alkane mixtures that included branched compounds. In general,
predictions are adequate and results are similar to those reported in literature by associating models like
the CPA, the SAFT and the GCA equations of state. Finally, using a generalization for the translation
parameter, liquid densities predictions were performed for 39 alkane-alkane mixtures, 10 alcohol-alcohol
mixtures and 15 ether-alkane mixtures and it was found that calculated values are in good agreement
with experimental data. The average absolute relative deviations calculated in liquid density are 2.18%,
1.58% and 1.06% respectively.
References
[1] A. P. Carneiro, O. Rodríguez, E. A. Macedo “Separation of carbohydrates and sugar alcohols from ionic liquids
using antisolvents” Separation and Purification Technology, 2014, 132: 496-504.
[2] F. M. Maia, N. Calvar, E. J. González, A. P. Carneiro, O. Rodríguez, E. A. Macedo “Modeling of ionic liquids
systems: phase equilibria and physical properties” (Chapter 2, pp 31-60); in “Ionic liquids - new aspects for the
future", Jun-Ichi Kadokawa (Editor). InTech: Rijeka (Croatia), 2013.
[3] J. M. Prausnitz, R. N. Lichtenthaler, E. G. de Azevedo, Molecular thermodynamics of fluid-phase equilibria, 3rd

Ed. Prentice Hall PTR: Upper-Saddle River, New Jersey (USA), 1999.

PPEPPD 2016
th
Experimental study of refrigerants and their mixtures

Martin Doubek1* Vaclav Vacek 1
1
Faculty of Mechanical Engineering, Czech Technical University in Prague, Czech Republic
*Corresponding author: martin.doubek@cern.ch
Keywords: Fluorocarbons, Refrigerants, Speed of sound, Equations of state, Sonar analysers
Abstract
We will present our latest research results in the thermodynamic properties of fluorocarbons that are used
as unconventional refrigerants in various applications within high-tech electronics installations both in
particle detector and other electronics industry applications.
The SAFT equations of state were used to model various thermodynamic properties, vapour-liquid phase
transition and equilibrium. Two approaches were studied and compared in details: sPC-SAFT EoS and
soft-SAFT EoS. Models were finally implemented in C programming language since an additional ideal
gas model is necessary in order to calculate ideal gas contributions to the residual thermodynamic
properties. The next move towards simulation of binary mixtures of line and unlike components is
outlined and studied as well.
A new automated apparatus for velocity of sound measurements has been prepared and gathered
experimental data were used to verified and evaluate our simulation model results namely for those
region where no published fluorocarbon experimental data are available. The actual speed of sound
measurements were carried out in two fluorocarbons C3F8 and C2F6 and their mixtures and in mixtures of
C3F8 with Nitrogen. In total, more than 600 new data points along 15 isotherms and pressures up to 0.5
MPa were obtained and will also be presented.
References
[1] Lemmon E. W, Span R., 2006, Short fundamental equations of state for 20 industrial fluids. Journal of
Chemical & Engineering Data, 51(3):785–850, 2006. doi: 10.1021/je050186n.
[2] Chapman W.G.,Gubbins K.E.,Jackson G.,Radosz M. 1989, Saft: Equation-of-state solution model for
associating fluids, Fluid Phase Equilibria, 52(0):31 – 38,. ISSN 0378-3812
[3] Gross J, Sadowski G, 2001, Perturbed-chain saft: An equation of state based on a perturbation theory for chain
molecules, Industrial & Engineering Chemistry Research, 40(4): 1244–1260, doi: 10.1021/ie0003887
[4] Johnson J. K, Zollweg J. A, Gubbins K. E, 1993, The lennard-jones equation of state revisited. Molecular
Physics, 78(3):591–618, 1993. doi: 10.1080/00268979300100411.
[5] Dias A.M.A, Llovell F., Coutinho J.A.P., Marrucho I.M., Vega L.F, 2009. Thermodynamic characterization of
pure perfluoroalkanes, including interfacial and second order derivative properties, using the crossover soft-saft eos.
Fluid Phase Equilibria, 286(2):134 – 143, ISSN 0378-3812
[6] Doubek M, 2014, Thermophysical properties of fluids experiment and simulations, Master thesis, Czech
technical university in Prague, Faculty of mechanical engineering
Hallewell G.,Vacek V.,Vins V.2010, Properties of saturated fluorocarbons: Experimental data and modeling using
perturbed-chain-saft. Fluid Phase Equilibria, 292:64 – 70, ISSN 0378-3812.
Acknowledgements
Supported by grants No:LG13009/SMSM2013LG3 - Ministry of Education, Youth and Sports of the Czech
Republic and No:SGS15/185/OHK2/3T/12 of the Czech Technical University in Prague

PPEPPD 2016
th
Molecular Structure Characterization for Hydrocarbon Process Simulation

Herbert Loria1*, Glen Hay1, Marco A. Satyro2
1
Virtual Materials Group, Canada
2
Department of Chemical and Biomolecular Engineering, Clarkson University, USA
*Corresponding author: herbert@virtualmaterials.com
Scientific topic: Gas and Oil Downstream and Upstream
Keywords: Process Simulation, Oil Characterization, Molecular Structure Characterization
Abstract
The representation of hydrocarbon mixtures in simulation models is not simple due to the presence of
potentially thousands of individual chemical species and the restrictions on currently available analytical
techniques. Traditional techniques for modeling hydrocarbon materials are often based on easily
measured properties like normal boiling point. In these techniques, one pseudo-component represents a
mixture of many pure compounds that boil within a certain temperature range. This average component
also represents components that have distinct chemical characteristics with different physical properties.
Although these techniques usually work well in situations where volatility is the major property of
interest; they fail for processes that are driven by molecular characteristics such as polarity and reactivity,
due to the lack of chemical information in the average component.
This work presents an alternative approach to the traditional characterization techniques using a new
molecular structure oriented characterization [1]. This methodology consists on using constant slates of
compounds to represent carbon number ranges of interest for the refinery industry and to model
paraffinic, olefinic, aromatic and other important chemical types typically encountered in hydrocarbon
fluids. Through combinations of these component slates, a laboratory analysis either distillation based or
compositional based can be modeled in a way similar to standard oil characterization. The key advantage
of this new method is the representation of the essential chemistry of a hydrocarbon mixture that allows
the prediction of simple properties, such as molecular weight or density, as well as more complex
refinery properties, like chemical group analyses, octane numbers, heating values or vapor pressures. In
addition, there are not limitations to the amount or type of data that can be used to find the best slate
representation of the mixture. This technique has been successfully used for tracking and estimating
properties of heavy hydrocarbon mixtures before, during, and after refinery reactors [2, 3].
References
[1] G. Hay, H. Loria, M. A. Satyro “Thermodynamic Modeling and Process Simulation through PIONA
Characterization” Energy and Fuels, 2013, 27: 3578-3584.
[2] G. Hay, H. Loria, M. A. Satyro, H. Nagata “Predicting Reactive Heavy Oil Process Operation” Petroleum
Technology Quarterly, 2014, Q4: 47-53.
[3] G. Hay, G. Rasouli, T. Morishita, J. Usami “Tube Alloy Degradation ina Steam Cracking Furnace” Petroleum
Technology Quarterly, 2015, Q2: 23-27.
Acknowledgements
The authors are grateful to Virtual Materials Group, Inc. for the permission to publish this work.

PPEPPD 2016
th
Molecular simulation of adsorption of polar and non-polar gases from

natural gas using FPYEu MOF
Flor R. Siperstein1 and Thaer M. Al-Jadir1*

1
Chemical Engineering and Analytical Science, University of Manchester, U.K.
*Corresponding author: thaer.al-jadir@postgrad.manchester.ac.uk
Scientific topic: Molecular and Multiscale Simulation
Keywords: molecular simulation, adsorption, FPYEu MOF
Abstract
Metal Organic Frameworks (MOFs) are novel adsorbents that have attracted a lot of attention due to the
possibility of tailoring their structure to obtain adsorbents with large capacity and selectivity. Molecular
simulations can aid in the discovery of new materials and can also provide a detailed picture on the
molecular scale that is not easily accessible from experimental methods.
In this work, FPYEu MOF [1] was selected as a case study of a model MOF for studying adsorption of
polar gases, such as H2S and H2O, and non-polar gases, such as CH4, and C2H6. The distribution of
Yttrium and Europium in FPYEu MOF is not known, and the position of these atoms can affect the
adsorption properties.
Grand canonical Monte Carlo simulations were carried to determine adsorption isotherms of these gases
on FPYEu MOF cells containing different distributions of Y and Eu. The transferability of force fields
was tested and some recommended adjustments are presented to enable the agreement between
experiments and simulations. Non-polar probes were used to determine the pore accessibility while polar
probes were used to assess the electrostatic interactions.
Simulations are carried out using Towhee software developed at Sandia National Labs that has the
capability of performing Monte Carlo simulations in a variety of ensembles [2].
References
[1] F. N. Shi, M. L. Pinto, D. Ananias, and J. Rocha, “Structure, topology, gas adsorption and photoluminescence
of multifunctional porous RE3+-furan-2,5-dicarboxylate metal organic frameworks,” Microporous Mesoporous
Mater., vol. 188, pp. 172–181, 2014.
[2] M. G. Martin; "MCCCS Towhee: a tool for Monte Carlo molecular simulation", Mol. Simulat. 39 1212-1222
(2013).
Acknowledgements
The HCED Iraq for financial support.

PPEPPD 2016
th
Deep Eutectic Solvents as Azeotrope Breakers
Nerea R. Rodriguez*1 and Maaike C. Kroon1,2

1
Separation Technology Group, Department of Chemical Engineering and Chemistry, Eindhoven University of
Technology, The Netherlands
2
The Petroleum Institut,Chemical Engineering Department, Abu Dhabi, United Arab Emirates
*Corresponding author: n.rodriguez@tue.nl
Scientific topic:Reaction and separation technologies
Keywords: Azeotrope, Deep Eutectic Solvent, Liquid-liquid extraction, extractive distillation
Abstract
The development of efficient and evironmentally friendly separation techniques for azeotropic mixtures
is a well-known challenge for chemical engineers. Some of the most common techniques for these
separations are azeotropic/extractive distillation and liquid-liquid extraction. Organic solvents have
traditionally been used as extracting agents in the aforementioned separation processes. However, these
solvents are generally volatile, toxic and flammable.
In the last years, ionic liquids (ILs) were found to be a promising alternative to organic solvents due to
their remarkable properties [1]. However, their complicated synthesis and purification requirements are
the main reasons for their failure at industrial scale. Rencently, deep eutectic solvents (DESs) were
reported to be a much cheaper alternative to ILs [2]. Both solvent families (ILs and DESs) share
interesting properties, i.e. negligible vapor pressure, wide liquid range, non-flammability, and tunability,
but the preparation of DESs is cheap, easy, solvent-free and without purification requirements, by mixing
natural and readily available starting materials [3].
In this work we show the applicability of different DESs for the separation of azeotropic mixtures via
extractive distillation and liquid-liquid extraction. The most important families of azeotropes, e.g.
alcohol-water, alcohol-aliphatic, aliphatic-aromatic and ketone-alcohol, have been explored. We will also
consider how the modification of the DESs constituents and ratio affects the separation performance in
terms of selectivity and distribution coefficient, and we will compare our data to conventional entrainers
and extractants.
References
[1] A. Pereiro, J. Araújo, J. Esperança, I. Marrucho, and L. Rebelo, “Ionic liquids in separations of azeotropic
systems-A review,” The Journal of Chemical Thermodynamics, vol. 46, pp. 2–28, 2012.
[2] A.P. Abbott, G. Capper, D.L. Davies, R.K. Rasheed, V. Tambyrajah “Novel solvent properties of choline
chloride/urea mixtures”Chemical communications, 2003,1: 70-71.
[3]Q. Zhang, K. D. O. Vigier, S. Royer, and F. Jérôme, “Deep eutectic solvents: syntheses, properties and
applications,” Chemical Society Reviews, vol. 41, pp. 7108–7146, 2012.
Acknowledgements
The authors thank the Dutch Organization for Scientific Research (NOW) for the financial support of this work
(grant number: ECHO.11.TD.006)

PPEPPD 2016
th
Analytic Continuation of the Virial Series Through the Critical Point Using
Parametric Approximants
Nathaniel S. Barlow,1 Andrew J. Schultz,2 Steven J. Weinstein,3 and David A. Kofke2*
1
School of Mathematical Sciences, Rochester Institute of Technology, Rochester, NY 14623, USA
2
Department of Chemical and Biological Engineering, University at Buffalo – SUNY, Buffalo, NY 14260, USA
3
Department of Chemical Engineering, Rochester Institute of Technology, Rochester, NY 14623, USA
*Corresponding author: kofke@buffalo.edu
Keywords: virial equation of state, critical point
Abstract
The virial equation of state (VEOS) is a power series in density, with coefficients that can be determined
from molecular considerations. Its rigorous connection to statistical mechanics makes it an appealing
choice for many purposes, but its utility is limited to conditions where the series converges. Singular
behavior in the equation of state, such as encountered upon approach to the critical point, restricts its
range of application. We first address this problem by forming an approximant that explicitly
incorporates this singular behavior along the critical isotherm, while remaining fully consistent with the
VEOS at low density. This treatment provides several new capabilities, including improved predictions
of critical properties from the virial coefficients, refinement of critical properties given by
simulation/experimental measurements, and an estimate of a critical amplitude for several fluids. Then,
we extend the approximant by including temperature dependence via the parametric form proposed by
Schofield [2], allowing us to incorporate scaling along the critical isochore while again retaining the
correct temperature-dependent low-density behavior as expressed by the VEOS [3]. The efficacy of the
proposed equation of state is demonstrated for the square-well fluid, chosen for this initial study because
the temperature dependence of its virial coefficients can be expressed analytically. The demonstration
suggests that much of the difficulty in convergence of the VEOS, even far from the critical point, can be
ameliorated by proper handling of the critical singularity.
References
[1] N. S. Barlow, A. J. Schultz, D. A. Kofke, and S. J. Weinstein, “Critical isotherms from virial series using
asymptotically consistent approximants,” AIChE J. 60, 3336 (2014).
[2] P. Schofield, “Parametric representation of the equation of state near a critical point,” Phys Rev Lett 22, 606
(1969).
[3] N. S. Barlow, A. J. Schultz, S. J. Weinstein, and D. A. Kofke, “Communication: Analytic continuation of the
virial
series through the critical point using parametric approximants,” J. Chem. Phys. 143, 071103 (2015).
Acknowledgements
This work was supported by the U.S. National Science Foundation (CHE-1027963, CI-TraCS- 1048579).
Computational resources were provided by the University at Buffalo Center for Computational Research.

PPEPPD 2016
th
Modeling of Adsorption Isotherms using Density-Functional Theory
Patrick Zimmermann*1, Thomas Goetsch2, Tim Zeiner2 and Sabine Enders1

1
2
TU Dortmund, Laboratory of Fluid Separations, Germany
*Corresponding author: patrick.zimmermann@kit.edu
Keywords: Lattice Cluster Theory, Branching effects, Density functional theory, Adsorption isotherms,
Separation of aldehydes
Abstract
For the separation of components having very similar vapor pressures, adsorption may be a promising
separation method leading to products with a high purity. The process design and control require the
knowledge of the adsorption isotherms as well as capillary condensation phenomena. One technical
important example is the purification of aldehydes produced via hydroformylation of olefins, especially
the separation of aldehydes having the same molecular mass, but differ in the molecule architecture is
very challenging. In the case of aldehydes, no experimental information could be found in the literature.
Therefore, a theoretical approach to calculate adsorption isotherms will be very helpful.
This contribution deals with the thermodynamic fundamentals related to this problem. The adsorption
isotherms of pure components and binary mixtures are calculated with the Density Functional Theory
(DFT) [1], in which the thermodynamic properties are expressed as functionals of the spatially varying
density, in combination with an equation of state based on the Lattice Cluster Theory [2] (LCT-EOS).
The LCT-EOS can be derived from the Lattice Cluster Theory, originally developed by Freed and
coworkers [e.g. 3]. The LCT-EOS allows to take the branching of the molecules directly into account
without any additional fitting parameter. The external field, representing the interaction of the fluid with
the pore, is established using the Steele 10-4-3 potential.
This theoretical framework can be employed for the calculation of the density profiles of pure
components and partial density profiles in the case of mixtures within the narrow pores. The integration
of these profiles leads to the adsorption isotherm. Effects of temperature, wall potentials, pore width,
aldehyde chain length and degree of branching on the adsorption isotherm are investigated theoretically.
For instance, it turns out that with decreasing temperature the difference between the phase behavior in
bulk and in narrow pore increases. The obtained adsorption isotherms show that adsorption can be a
promising technology for the separation of long-chain n-aldehydes having very similar boiling
point.
References
[1] R. Evans, Fundamentals of Inhomogeneous Fluids, edited by D. Henderson (New York: Marcel Dekker) 1992.
State for Multi-Component Systems.” Fluid Phase Equilibria 2014, 363: 196-212.
Macromolecules, 1991, 24: 5076-5095.
Acknowledgements
For financial support the authors thank the German Science Foundation (DFG) and the collaborative research centre
SFB Transregio 63.
PPEPPD 2016
th
Reactant-ratio and pH influence on the thermodynamics of enzyme-catalyzed

reactions
Matthias Voges#, Gabriele Sadowski, Christoph Held*

Department of Biochemical and Chemical Engineering, Laboratory of Thermodynamics, Technische Universität
Dortmund, Germany
# Presenting author: matthias.voges@bci.tu-dortmund.de; *Corresponding author: christoph.held@bci.tu-
dortmund.de
Keywords: reaction equilibrium, biothermodynamics, activity coefficients, yield
Abstract
Enzyme-catalyzed reactions become more and more important for the development of new alternative
synthetic routes in biotechnological processes. However, the yield of many enzyme-catalyzed reactions is
limited by thermodynamic equilibrium. Aminotransferase-reactions and dehydrogenase-reactions belong
to this class of reactions. For the thermodynamic characterization of bioreactions, the knowledge about
the Gibbs energy of reaction (Δ𝑅𝑔) is required, which depends mainly on the thermodynamic (activity-
based) equilibrium constant 𝐾𝑎∗. The latter is accessible by the experimental reaction equilibrium
concentration ratio of products over reactants (𝐾𝑚) and their activity coefficient ratio 𝐾𝛾∗.
In this work the thermodynamic equilibria of the alanine aminotransferase reaction (ALAT: L-alanine +
2-oxoglutarate ↔ L-glutamate + pyruvate) as well as the hydrogenation of acetophenone catalyzed by an
alcohol dehydrogenase (ADH: acetophenone ↔ phenylethanol) in aqueous media have been
investigated. 𝐾𝑚 _values of the ALAT-reaction were measured in a temperature range between 25 and
37 °C at 5<pH<9. 𝐾𝑚 _values of the hydrogenation-reaction were measured in a temperature range
between 25 and 30 °C at pH 7.
Prior to investigations of reaction equilibria, measurements were carried out to ensure the catalytic
activity of the enzymes in the aqueous reaction media at all considered reaction conditions. Reaction
equilibrium measurements were performed for different initial molalities of reactants. Molalities of
reactants and products at reaction equilibrium were quantified by HPLC.
It was found that the reaction equilibria (and thus also the yield) is influenced by the solution’s pH, by
the reaction temperature and by the molalities of reactants and products. The 𝐾𝑚 _values of the ALAT-
reaction increased with increasing temperature, increasing pH, increasing initial molalities of reactants
(equimolal conditions) and increasing ratio of the initial molalities of reactants. The 𝐾𝑚 _value of the
hydrogenation of acetophenone increased with increasing temperatures and increasing molalities of
reactants. Finally, activity coefficients of reactants and products were predicted with ePC-SAFT. This
allowed predicting the effect of the influencing factors (temperature, pH, reactant-ratio) on 𝐾𝑚 _in
quantitative agreement with the experimental data.

PPEPPD 2016
th
Permeation of Supercritical Fluids through Microporous Constrictions by

Molecular Simulations
Fouad Oulebsir1*, Romain Vermorel1 and Guillaume Galliero1
1
Laboratory of complex Fluids and Their Reservoirs,UMR-5150 with CNRS and TOTAL,
University of Pau, 64000 Pau, France.
*Corresponding author: fouad.oulebsir@univ-pau.fr
Scientific topic: 1.1 Applied Thermodynamics, Fluid Dynamics, Heat Transfer
Keywords: Molecular diffusion, Molecular simulations, Interfaces, Confinement effects
Abstract
Fluid transport through amorphous microporous materials has several applications among which design
of microporous carbons for gas separation, production of gas from shales and coal seams or geological
CO2 sequestration. The determination of transport properties in such media is therfore of great interest.
In the context of amorphous carbon membranes, numerous experimental studies have reported the
dependence of permeance and separation properties on thermodynamic conditions (pressure,
temperature) and also on the system properties (fluid species, structural properties of the membranes,
.etc) [1]. Recently, Botan et al performed molecular simulations that reproduced some typical features of
the experimental results found in the literature [2]. More precisely these authors evidenced that steric
effects inherent to fluid permeation through molecular size constrictions drive the overall transport
properties of the membrane. By constriction, we refer to a pore throat that opposes an energy barrier to
the flow of the permeating fluid.
The present work focuses on molecular simulations of fluids permeating through a single microporous
constriction. As a first approach, our molecular model consists in a microporous slit formed in a thin
monolayered face-centered cubic (FCC)-like arranged wall which connects two fluid reservoirs. We
report how permeation rates depend on various parameters, such as the aspect ratio between the slit and
the permeating molecules, the amplitude of molecular interactions and the thermodynamic conditions.
Based on these observations, we propose simple theoretical models to describe the relevant transport
coefficients.
References
[1] Centeno and Fuertes, “Supported carbon molecular sieve membranes based on a phenolic resin”, J. Membr.
Sci., pp 201-211, Issue 2 volume 160, 1999.
[2] Botan et al., “Molecular Simulations of Supercritical Fluid Permeation through Disordered Microporous
Carbons”, Langmuir, pp 9985-9990, 29 (32), 2013.
Acknowledgements
We gratefully acknowledge CNRS and TOTAL S.A. for financial support and for a grant for one of us (Fouad
Oulebsir). Computer time for this study was provided by the computing facilities of the MCIA (Mésocentre de
Calcul Intensif Aquitain) and of the Université de Pau et des Pays de l’Adour.
PPEPPD 2016
th
Dynamic Simulation of a Polymer Process using the PC-SAFT Equation of

State
Gang (Gary) Xu*, Nevin Gerek Ince, Seiya Hirohama, Prasad Narasimhan, David Bluck
Schneider Electric Sofware LLC,USA
*Corresponding author: Gang.Xu.us@schneider-electric.com
Scientific topic: Phase equilibria, Materials, Thermodynamics and transport properties
Keywords: PC-SAFT EOS, polymer process, Dynamic simulation, DYNSIM
Abstract
Current applications of polymer plant simulation, especially for Operator Training Simulators (OTS),
dynamic analysis of safety features as well as compressor control mechanisms require both model
accuracy and simulation performance. However, this cannot be achieved without proper selection of the
thermodynamic model. Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) [1] has been
well established for the prediction of phase equilibria of a broad range of substances and mixtures
including simple fluids, associating fluids as well as dipolar components and their mixtures. An excellent
performance of the PC-SAFT model was also shown in modelling monomer solubility into polymer
solutions [2], and hence placed itself as an excellent candidate for model accuracy in polymer plant
simulation.
On the other hand, process simulations generally need a simple, generalized, and reasonably accurate
equation of state (EOS) for the many repetitive calculations required. Specifically, dynamic process
simulation involves numerous phase equilibrium or flash calculations which can be extremely
computationally intensive. Therefore, there is always a need to reduce the computational burden and
improve the robustness of flash calculations especially for non-cubic equations.
Here, we present a state of the art implementation and modification of PC-SAFT in DYNSIM®, a
dynamic simulation tool from Schneider Electric Software LLC that achieves both model accuracy and
simulation performance, which clients can apply to do various tasks in both steady state and dynamic
analysis over the entire plant. We have equipped PC-SAFT with state-of-art mathematical techniques to
increase computational speed and robustness by taking an advantage of (i) pseudo-density extrapolation
in the vicinity of the critical region [3] (ii) super-linear approach when a previous rigorous solution has
converged and (iii) the method developed for the robust phase stability. In addition, demonstration by a
DYNSIM® simulation with PC-SAFT at key regions of polyethylene plant is provided, followed by the
potential applications to asphaltenes in heavy oils which can be modeled as low molecular weight
polymers.
References
[1] J. Gross and G. Sadowski, “Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for
Chain Molecules”, Ind. Eng. Chem. Res. 2001, 40, 1244-1260.
[2] J. Gross and G. Sadowski, “Modeling Polymer Systems Using the Perturbed-Chain Statistical
Associating Fluid Theory Equation of State”, Ind. Eng. Chem. Res. 2002, 41, 1084-1093.
[3] Xu, G., Bluck D., van Peursem D.J. and Boys, I.H., “Thermodynamic process control based on pseudo-density
root for equation of state”, U.S. Patent 8 165 860 , Apr 24 2012.
Acknowledgement
We gratefully appreciate all the helps and good discussions given by Prof.Sadowski of Dortmund Technical
University.
PPEPPD 2016
th
Extended Distillation and Property Correlations for Heavy Oils
Harvey Yarranton1*, Catalina Sanchez Lemus1, Florain Schoeggl1, Shawn Taylor2

1
Department of Chemical and Petroleum Engineering, University of Calgary, Canada
2
DBR Technology Center, Schlumberger Canada Limited, Canada
*Corresponding author: hyarrant@ucalgary.ca
Keywords: heavy oil, distillation, property correlation, characterization
Abstract
A recently developed deep vacuum fractionation apparatus (DVFA) was adapted to distill heavy oils and
to collect each distillation cut [1]. An interconversion methodology was developed to produce
atmospheric equivalent boiling points which are equivalent to true boiling points as determined with
simulated distillations [2]. Seven geographically different heavy oils were distilled. The amount distilled
varied between 50 and 60 wt% of the oil and the cumulative wt% distilled was repeatable to within 2.3%
for a given boiling point range. The specific gravity (SG), molecular weight (MW), elemental analysis,
vapor pressure, and heat capacity were measured for all cuts and residues. The property data were used to
evaluate existing property correlations and to modify or develop new correlations as required.
In this submission, the extended distillation from the DVFA is presented and the evaluation of existing
correlations is summarized. Improved property correlations between NBP, SG, and MW with deviations
of less than 2.3% for each property are also presented. A general characterization methodology for heavy
oils is discussed.
References
[1] O. Castellanos-Diaz, M.C. Sánchez, F.F. Schoeggl, M.A. Satyro, S.D. Taylor, H.W. Yarranton, “Deep Vacuum
Fractionation of Heavy Oil and Bitumen: Part 1 Apparatus and Standardized Procedure”, Energy & Fuels, 2014, 28:
2857-2865.
[2] M.C. Sánchez, F.F. Schoeggl, S.D. Taylor, M. Fulem, H.W. Yarranton “Deep vacuum fractionation of heavy oil
and bitumen: part 2 interconversion method”, Energy & Fuels, 2014, 28: 2866-2873.
Acknowledgements
We are grateful to the sponsors of the NSERC Industrial Research Chair in Heavy Oil Properties and Processing:
NSERC, Nexen, Petrobras, Schlumberger, Shell, Suncor, and Virtual Materials Group.

PPEPPD 2016
th
Influence of Solvent Composition and Temperature on the Binding Strength

of Supramolecular Complexes Formed by Perylene Derivatives
Jörg Baz1* and Niels Hansen1
1
Institute of Thermodynamics and Thermal Process Engineering, University of Stuttgart, Germany
*Presenting author: baz@itt.uni-stuttgart.de
Scientific topic: 1.1 Applied Thermodynamics
Keywords: Molecular Dynamics, Free Energy, Supramolecular Complexes, Co-solutes
Abstract
π-stacked supramolecular complexes formed from derivatives of perylene bisimide dyes in water are
materials with numerous potential applications e.g. as pigments, fluorescence sensors, semiconductors,
for drug dispense and as filtration membranes for nanoparticles. Generating such molecular aggregates in
aqueous media represents a great challenge due to the role the hydrophobic effect plays. Although
several noncovalent interactions e.g. hydrogen bonding are specific and directional in the formation of
supramolecular structures, this is usually not the case for hydrophobic interactions. But not only the
intermolecular influences mentioned above, have to be considered. Also temperature, solvent
composition, molecular structure and presence of particular additives affect the formation and shape of
supramolecular complexes. Therefore, the structures of supramolecular aggregates formed in aqueous
solutions cannot be predicted as easily as in the case of organic media [1].
Nevertheless, water offers many opportunities and advantages as a solvent for supramolecular chemistry
compared with organic media. In this regard molecular dynamics simulations in explicit solvent offer the
possibility to gain insight into the various driving forces that lead to the formation of stable molecular
aggregates in aqueous media.
As a first step a water soluble di(glycyl)imide (dipotassium salt) derivative of 3,4,9,10-perylene-
tetracarboxylic dianhydride was simulated in pure water using the GROMOS force field [2]. The binding
free energy is a measure for the aggregation strength of a dimer complex. This free energy has been
obtained as function of temperature by using umbrella sampling simulations along a one dimensional
pathway in combination with the weighted histogram analysis method.
Subsequently the influence of NaCl and ethanol on the binding free energy has been investigated. While
NaCl leads to stronger association, ethanol weakens the binding in agreement with experimental data for
this system.
References
[1] D. Görl, X. Zhang, F. Würthner, Angew. Chem. Int. Ed., 2012, 51:6328-6348.
[2] C. Oostenbrink, A. Villa, A. E. Mark, W. F. van Gunsteren, J. Comput. Chem., 2004, 25:1656-1676.

PPEPPD 2016
th
Ionic Liquids in Gas Separation Processes: Influence of Metal Salts and

Water Contents on the Viscosity
Gabriel Zarca, Inmaculada Ortiz, Ane Urtiaga
Dep. Chemical and Biomolecular Engineering, University of Cantabria, Santander, Spain
*Corresponding author: zarcag@unican.es
Keywords: ionic liquids, rheology, density, water, metal salt.
Abstract
In previous works aimed at using task-specific ionic liquids tailored to selectively absorb carbon
monoxide from tail gases of the process industry [1], we observed a great influence of the concentration
of the reagents employed as well as of the water content on the viscosity of the selected ionic liquid 1-
hexyl-3-methylimidazolium chloride, [C6mim][Cl]. Therefore, we decided to assess how the viscosity of
this ionic liquid was modified by the addition of significant amounts of CuCl, which is the responsible
agent of the high selectivity towards CO compared to N2. In this work, we present shear-dependent
viscosity data obtained at several temperatures (293-343 K) and CuCl concentrations (0-2 mol L-1) that
show how these properties, specially viscosity, can be significantly decreased thus improving the mass
transport properties of the system. Moreover, this study is completed with the assessement of the ionic
liquid density in those conditions.
In addition, given the high hygroscopicity of [C6mim][Cl], we have studied the water uptake from the
atmosphere (80% RH, 20 ºC) in 16 ionic liquids with different structure combinations, which allowed us
to go deeply into the influence of anion nature ([PF6], [Ac], [Tf2N], [Cl], [dca], [BF4], [TFO]), cation
nature (ammonium, imidazolium, phosphonium, pyridinium, pyrrolidinium) and alkyl chain length
(ethyl, butyl, hexyl, octyl). Results showed that the water sensitivity of these ionic liquids is strongly
related to the ionic liquid structure and time of exposure to the environment. Finally, the effect of the
water content on the viscosity of some ionic liquids with different hygroscopicity was assessed to show
how this impurity may affect such an important mass transport property.
References
[1] O.C. David, G. Zarca, D. Gorri, A. Urtiaga, I. Ortiz “On the improved absorption of carbon monoxide in the
ionic liquid 1-hexyl-3-methylimidazolium chlorocuprate” Separation and Purification Technology, 2012, 97: 65-72.
[2] G. Zarca, M. Fernández, A. Santamaría, I. Ortiz, A. Urtiaga “Non-Newtonian shear-thinning viscosity of carbon
monoxide-selective ionic liquid 1-hexyl-3-methylimidazolium chloride doped with CuCl” Separation and
Purification Technology, 2015, doi: 10.1016/j.seppur.2015.07.032.
Acknowledgements
Financial support from the Spanish Ministry of Economy and Competitiveness to project CTQ2012-3139 is
gratefully acknowledged.

PPEPPD 2016
th
Group-Contribution Modelling of Polystyrene using SAFT-γ Force Fields:

Molecular Simulations of Polystyrene Melts and Polystyrene Solutions in
Alkanes
Guadalupe Jiménez-Serratos*, Carmelo Herdes, Andrew J. Haslam, George Jackson, and Erich A. Müller
Department of Chemical Engineering, Imperial College London, U.K.
*Presenting author: m.jimenez-serratos@imperial.ac.uk
Keywords: coarse-graining, polymers, fluid phase equilibria, equations of state, MD simulations
Abstract
The study of long polymers and their behaviour in solution using computational simulations requires
simplified models to access the relevant spatial and temporal scales. In this work, a coarse-grained (CG)
model for atactic polystyrene is presented and studied via classical molecular-dynamics simulations. The
interactions between the CG segments are described by Mie potentials, with parameters obtained from a
top-down approach using the SAFT-γ methodology [1]; the core of the modelling philosophy lies in the
transferability and robustness of parameters obtained using this approach. The model for the polymer is
developed by taking CG models for linear-chain-like backbones with parameters corresponding to those
of an alkane model, and decorating them with side branches with parameters taken from a model of
toluene, which are thus “aromatic-like” in nature. The model is validated against the properties of
monodisperse melts, including the effect of temperature and pressure on density, as well as structural
properties: radii of gyration and end-to-end distances as functions of chain length. The model is
employed to perform large-scale simulations [2] that describe the temperature-composition phase
behaviour of binary mixtures of polystyrene and aliphatic solvents, in particular, hexane and heptane. A
single temperature-independent energy cross-interaction parameter is estimated for each solvent to
reproduce the solubility behaviour reported in experiments; this is sufficient for the quantitative
prediction of both upper and lower solution critical points and the transition to “hour-glass” phase
behaviour as expected at different conditions of composition and temperature. As an ancillary result, a
methodology is presented to determine analytically the onset of liquid-liquid phase separation. The
model shows promises as an interesting candidate to test other properties and to explore more-complex
mixtures or thermodynamic conditions.
References
[1] Müller, E. A., and Jackson, G. (2014). Force-Field Parameters from the SAFT- Equation of State for Use in
Coarse-Grained Molecular Simulations. Annual Rev. Chem. Biomolec. Eng., 5(1), 405-427.
[2] “Hoomd-blue” http://codeblue.umich.edu/hoomd-blue.
Acknowledgements
The authors acknowledge funding through the UNIHEAT project. Additional funding to the MSE Group from the
EPSRC of the United Kingdom (EP/E016340, EP/I018212, and EP/J014958) is also gratefully acknowledged. The
simulations described herein were performed using the facilities of the Imperial College High Performance
Computing Service.

PPEPPD 2016
th
Classical Density Functional Theory for Liquid-Fluid Interfaces and
Confined Systems using PC-SAFT Equation of State
Elmar Sauer1, Joachim Gross1

1
Corresponding author: gross@itt.uni-stuttgart.de, Presenting author: sauer@itt.uni-stuttgart.de
Keywords: classical density functional theory, SAFT, surface tensions, confined media
Abstract
The classical density functional theory (DFT) is an efficient method to determine thermodynamic
quantities of inhomogeneous systems. A result of DFT calculations are density profiles, which give
information about the distribution of molecules in space. Density profiles of fluid phases in confined
media can be used to study fluid phase behavior or to calculate thermodynamic properties such as
adsorption isotherms.
We present a residual Helmholtz energy functional in the PC-SAFT [1] formalism: The functional is
composed of a hard-chain [2,3], a dispersive and a dipolar contribution. For the dispersive term we
propose a weighted density approximation which is numerically efficient. The dipolar term is applied
using the local density approximation and the dipole-dipole interaction contribution proposed by Gross
and Vrabec [4].
We calculate surface tensions of various pure components and mixtures and find very good agreement
with experimental data. DFT calculations of fluid phases in confined systems were carried out for
different components. The results show that density profiles obtained from molecular simulations and
DFT density profiles are in a good agreement. We present a 2-dimensional implementation that allows us
to study hysteresis phenomena known for porous materials.
References
[1] J. Gross, G. Sadowski “Perturbed-chain SAFT: An equation of state based on a perturbation theory for chain
molecules” Industrial & Engineering Chemistry Research, 2001, 40: 1244-1260.
[2] R. Roth, R. Evans, A. Lang, G. Kahl “Fundamental measure theory for hard-sphere mixtures revisited: the
White Bear version” Journal of Physics: Condensed Matter, 2002, 14: 12063-12078.
[3] S. Tripathi, W. G. Chapman “Microstructure of inhomogeneous polyatomic mixtures from a density functional
formalism for atomic mixtures” Journal of Chemical Physics, 2005, 122: 094506.
[4] J. Gross, J. Vrabec “An equation-of-state contribution for polar components: dipolar molecules” AIChE Journal,
2006, 52: 1194-1204.
Acknowledgements
Financial support of the German Research Council (Deutsche Forschungsgemeinschaft – DFG) through the
International Research Training Group “Non-linearities and upscaling in porous media” (GRK 1398) is gratefully
acknowledged.

PPEPPD 2016
th
Bubble Point Measurements of n-Propane + n-Decane Binary Mixtures with

Comparisons of Binary Mixture Interaction Parameters for Linear Alkanes
Elisabeth Mansfield1*, Ian H. Bell1, Stephanie L. Outcalt1

1
Applied Chemicals and Materials Division, National Institute of Standards and Technology, Boulder, CO USA
*Corresponding author: elisabeth.mansfield@nist.gov
Keywords: Phase equilibria, VLE, EOS, Mixture Parameters (maximum 5 keywords)
Abstract
Many of the separation processes related to the energy industry require some knowledge of the vapor-liquid
equilibria of hydrocarbon mixtures. A testament to this is the work done by the GERG (a consortium of
European gas companies) to develop an equation of state for the thermodynamic properties of natural gases
covering the gas and liquid region including the gas-liquid phase equilibrium.[1,2] In the absence of
experimental data, empirical equations of state, such as the GERG, may fail to produce accurate property
predictions. This is especially true for the predictions of mixture properties. In this work, vapor-liquid
equilibria were measured for the binary mixture of n-propane + n-decane. This data is compiled with other
experimental measurements on systems containing small linear alkanes (propane, butane) mixed with long
chain linear alkanes (octane, nonane, decane) to provide binary data on these systems for improving mixture
models. Very few bubble point measurements of n-propane + n-decane mixtures exist in the literature.
Comparisons to the GERG-2008 equation showed considerable deviations, prompting the need for additional
measurements and improved mixture modeling.
In this work, data for a n-propane + n-decane binary system, along with published data on butane + octane and
butane + nonane binary systems,[3] are utilized to fit mixture parameters. The thermodynamic properties of
the mixture are modeled by the use of a multi-parameter mixture model. This family of models has seen wide
application because it is a Helmholtz-energy based model, and therefore all other thermodynamic properties
can be obtained from derivatives of the Helmholtz energy.[1,2,4] For the ij pair, there are a total of four
adjustable parameters – βT,ij, γT,ij, βV,ij, and γV,ij. The parameters fit here (βT,ij, γT,ij) have the strongest impact on
the prediction of bubble points and can generally be fit with a relatively small dataset size. New interaction
parameters for two butane binary systems (butane + octane, butane + nonane) are also given with the support
of previous bubble-point measurements.[4] Comparisons to literature values and impact will be discussed.
References
[1] O. Kunz and W. Wagner. The GERG-2008 Wide-Range Equation of State for Natural Gases and Other
Mixtures:An Expansion of GERG-2004. J. Chem. Eng. Data, 57:3032-3091, 2012.
[2] O. Kunz, R. Klimeck, W. Wagner, and M. Jaeschke. The GERG-2004 Wide-Range Equation of State for
Natural Gases and Other Mixtures. VDI Verlag GmbH, 2007.
[3] E. Mansfield and S. L. Outcalt. Bubble-Point Measurements of n-Butane + n-Octane and n-Butane + n-Nonane
Binary Mixtures. J. Chem. Eng. Data, 2015.
[4] Johannes Gernert, Andreas Jäger, and Roland Span. Calculation of phase equilibria for multi-component
mixtures using highly accurate Helmholtz energy equations of state. Fluid Phase Equilib., 375:209.
[5] I.H. Bell. J. Chem. Eng. Data, 2015, submitted.[6] E. Mansfield, I. H. Bell, S. L. Outcalt, J. Chem. Eng. Data,
2015, submitted.
PPEPPD 2016
th
Non-equilibrium Hydrate Phase Transitions from aqueous CO2 and CO2 gas
Khadijeh Qorbani1* Bjørn Kvamme 1 Richard Olsen1

1
Department of physics & technology, University of Bergen, Norway
*Corresponding author: khadijeh.qorbani@ift.uib.no
Keywords: CO2 storage, CO2 hydrate, hydrate reservoir simulation, non-equilibrium thermodynamics
Abstract
Storage of CO2 in aquifers is one of several options for reducing the emissions of CO2 to the atmosphere.
Generally, this option requires sealing integrity through layers of clay or shale. Many reservoirs have
regions of temperature and pressure inside hydrate formation conditions. Whether hydrate formation can
provide long term addional sealing still remains unverified in view of all co-existing phases that affect
hydrate stability. Yet another storage option for CO2 is in the form of hydrate through exchange of in situ
CH4 hydrate.
Hydrates in nature come from various hydrate formers. Even when stable over the pressure and
temperature domain, hydrate can generally not reach thermodynamic equilibrium due to Gibbs' phase
rule and the combined first and second laws of thermodynamics. These thermodynamic constraints on
distribution of masses over co-existing phases are dynamically coupled to local mass- and heat-transport.
Reservoir simulations are one possible method for investigation of possible scenarios related to injection
of CO2 into underground aquifers.
In earlier work from our group, the RetrasoCodeBright (RCB) simulator package was modified to enable
formation (dissociation) of CO2 hydrate from (to) CO2 gas and water through injection of pure CO2 gas
[1]. In this work, the RCB hydrate simulator has been extended to account for hydrate formation and
dissociation toward CO2 in the aqueous phase, as well as in the water phase, using classical nucleation
theory. Phase transitions are treated as non-equilibrium processes under local constraint of mass and heat
fluxes. CO2 hydrate formation and dissociation is resolved by looking at super-saturation and under-
saturation with respect to thermodynamics variables (CO2 mole-fraction, pressure and temperature).
Competing hydrate phase transitions were determined by investigating Gibbs free energy differences
between hydrate and parent phases (origin of hydrate formers) and energy differences were calculated
from variations in chemical potentials, which were estimated using non-equilibrium thermodynamic
approach. We have used our simulations to study pressure and temperature dependencies of CO 2 hydrate
formation and dissociation inside underground aquifers.
References
[1] , M. T. Vafaei, B. Kvamme, , A. Chejara, , & K. Jemai, “A new reservoir simulator for studying hydrate
dynamics in reservoir”. International Journal of Greenhouse Gas Control, 23, 12-21, 2014.
Acknowledgements
Research Council of Norway, STATOIL

PPEPPD 2016
th
A New Method for Accurate Measurement of Solubility of Sparingly Soluble

Gases in Liquids
Amir Hossein Jalili1*, Ali Pourbashiri2, Cyrus Ghotbi2
1
Gas Refining Technol. Group, Research Institute of Petroleum Industry (RIPI), West Blvd. Azadi Sports Complex,
P.O. Box 14665-137, Tehran, Iran.
2
Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran, Iran.
*Corresponding author: jaliliah@ripi.ir
Scientific topic: Phase equilibria (experimental and modeling)
Keywords: Gas solubility, Gas-liquid equilibria, Natural gas sweetening, Gas separation
Abstract
Reliable experimental data for solubility of sparingly soluble gases, such as light hydrocarbons and
mercaptans, in pure liquids and mixtures such as water or aqueous electrolyte solutions are of high
practical importance in designing industrial natural gas sweetening, gas separation and purification
processes.
A new dynamic apparatus has been developed in our laboratory for accurate measurement of gas–liquid
equilibrium (GLE) of homogenous binary and multi-component mixtures from atmospheric to high-
pressure (10 MPa) regions. The apparatus provides recirculation and sampling of liquid phase and is
capable of yielding accurate PTx data for homogeneous mixtures. The operating temperature range of the
apparatus is from (253 to 373) K. The apparatus is simple to construct and does not need complicated
and costly instruments such as gas chromatographs for the analysis of liquid and vapor phases. The
sampling of the liquid phase is performed without producing any disturbance in equilibrium conditions.
The experimental setup and method is applicable for studying liquid systems, which absorb gases both
physically and chemically.
The accuracy of the instrument was assessed by measuring the isothermal solubility of
methane and methanethiol in water and aqueous alkanolamine solutions. Comparison of the
measured values with reliable data reported in the literature [1,2,3] and their reproducibility and
internal consistency indicates quite high accuracy and precision of the experimental setup and
measurement method.
References
[1] J. J. Carroll, F-Y. Jou, A. E. Mather, F. D. Otto “The solubility of methane in aqueous solution of
monoethanolamine, diethanolamine and triethanolamine” Canadian Journal of Chemical Engineering, 1998, 76:
945-951.
[2] F-Y. Jou, J. J. Carroll, A. E. Mather, F. D. Otto “Solubility of methane and ethane in aqueous solutions of
methyldiethanolamine” Journal of Chemical and Engineering Data 1998, 43: 781-784.
[3] J. Kilner, S. E. McBain, M. G. Roffey, “(Vapor + liquid) equilibria of (methanethiol or ethanethiol or propan-1-
thiol or butan-1-thiol + n-hexane or n-decane or toluene or water) for mole fractions x=0 to 0.2 of thiol at
temperatures between 323 and 373 K” Journal of Chemical Thermodynamics 1990, 22: 203-210.
Acknowledgements
We are thankful to the Research Council of the Research Institute of Petroleum Industry (RIPI) and the Research
and Technology of the National Iranian Gas Company (NIGC) for their support of this work.
PPEPPD 2016
th
Predicting solid-liquid equilibria of ternary semicrystalline polymer solvent

mixtures by means of Lattice Cluster Theory
Michael Fischlschweiger1* and Sabine Enders2

1
Ottronic Technology Laboratory, Ottronic GmbH, Austria
2
Institut für Technische Thermodynamik und Kältetechnik, Karlsruhe Institut für Technologie (KIT), Germany
*Corresponding author: technology.lab@ottronic.com
Scientific topic: Processing and Applications: Materials
Keywords: polymers, semicrystallinity, solid-liquid equilibria, ternary systems
Abstract
Analytical polymer separation techniques play a crucial role to gain insight into the interrelation between
molecular architecture and properties. For explaining the theoretical background of common polymer
separation techniques, a fair prediction of solid-liquid equilibria of polymer solvent systems is required.
The thermodynamic model which is typically used for describing solid-liquid equilibria of polymer
solvent systems is the Flory-Huggins theory [1]. However, in Flory-Huggins theory the structure of the
polymer, e.g., branching distribution is not taken into account. By application of Lattice Cluster Theory
(LCT), developed by Freed and coworkers [2], the molecular architecture can be considered. In the past
it could be demonstrated that LCT is a powerful theory for calculation of liquid-liquid phase equilibria
[3]. Recently, LCT was applied to calculate solid-liquid equilibria of binary semicrystalline high-
polymer solvent mixtures having an arbitrary molecular architecture of both, polymer and solvent, where
the polymer is considered to be monodisperse [4].
Besides, influences of degree of polymer crystallinity, nucleation entropy and branching numbers, in this
contribution the impact of polymer polydispersity on the solid-liquid equilibrium of high-polymer
solvent mixtures is considered. This is realized, by application of the LCT based theory for predicting the
solid-liquid equilibria of discrete ternary high-polymer solvent mixtures. Effects of semicrystallinity and
molecular architecture of the respective components are studied for ternary systems.
References
[1] C. Elicabe, J. Carella, J. Borrajo “Modeling the fractionation process in TREF systems. II. Numerical analysis”
Journal of Polymer Science Part B: Polymer Physics, 1996, 34: 527-533.
[2] J. Dudowicz, K.F. Freed “Effect of monomer structure and compressibility on the properties of multicomponent
polymer blends and solutions: 1. Lattice Cluster theory of compressible systems” Macromolecules, 1991, 24: 5076-
5095.
[3] T. Zeiner, D. Browarzik, S. Enders “Calculation of liquid-liquid equilibrium of aqueous solutions of

hyperbranched polymers” Fluid Phase Equilibrium, 2009, 286: 127-133.
[4] M. Fischlschweiger, S. Enders “A Theory for Solubility of Semicrystalline and Branched Polymers in One
Solvent” Macromolecules, 2014, 47: 7625-7636.
PPEPPD 2016
th
Atomistic Simulations of the Formation of Perylene-Based Supramolecular

Complexes in Aqueous Solution
Jörg Baz1 and Niels Hansen1*

1
*Corresponding author: hansen@itt.uni-stuttgart.de
Scientific topic: 1.1 Applied Thermodynamics
Keywords: Molecular Dynamics, Force Field, Free Energy, Supramolecular Complexes
Abstract
The design and synthesis of complex functional dye-based materials from components held together by
intermolecular noncovalent forces is of increasing importance for many high technology applications. As
a result there is growing interest in understanding dye-dye interactions and how these interactions impact
the properties of nano- or bulk solid state materials. Such understanding can be derived from
investigations on supramolecular dye assemblies that constitute the intermediate state of matter between
monomeric dyes and supramolecular materials. During the last decade, perylene bisimide dyes (PBI)
emerged as an archetype class of colorants for the elucidation of the transition from monomeric to bulk
materials via the supramolecular state [1]. The self-assembly of amphiphilic molecules into complex
structures is determined by size and shape of the monomeric unit, system composition and
thermodynamic boundary conditions [2]. Given this diversity of factors for self-assembly, a molecular-
level understanding of the various driving forces is a promising approach for the rational bottom-up
material design. In this regard atomistic simulations in explicit solvent offer the possibility to obtain such
an understanding and to probe the effect of various parameters on the formation of dye assemblies.
However, current macromolecular force fields have not been parametrized for this type of molecules. In
the present work the parametrization of a PBI derivative based on the GROMOS force field [3] was
conducted in a fragment-based fashion, i.e. the method to estimate partial charges [4] is validated on
small fragments of the PBI derivative for which a wide variety of experimental data is available and then
used for larger fragments for which only little or no experimental data exists. The results show that only
little manual adjustment was necessary. The formation of PBI dimers as well as the influence of solvent
composition on the thermodynamics of self-assembly was subsequently investigated by molecular
dynamics simulations in aqueous solution.
References
[1] F. Würthner, C. R. Saha-Möller, B. Fimmel, S. Ogi, P. Leowanawat, D. Schmidt, Chem. Rev., DOI:
10.1021/acs.chemrev.5b00188.
[2] P. Calandra, D. Caschera, V. T. Liveri, D. Lombardo, Colloids and Surfaces A: Physicochem. Eng. Aspects,
2015, 484: 164-183.
[3] C. Oostenbrink, A. Villa, A. E. Mark, W. F. van Gunsteren, J. Comput. Chem., 2004, 25:1656-1676.
[4] A. K. Malde, L. Zuo, M. Breeze, M. Stroet, D. Poger, P. C. Nair, C. Oostenbrink, A. E. Mark, J. Chem. Theory
Comput., 2011, 7:4026-4037.

PPEPPD 2016
th
Corresponding State Behaviour of Vapour-liquid Phase Equilibria of
Confined
Square-well Fluid
Sudhir K. Singh*
Department of Chemical Engineering, Thapar University Patiala, India
*Corresponding author: sksingh@thapar.edu
Scientific topic: Phase Equilibria and Molecular Simulation

Keywords: Square-well, Phase equilibria, Corresponding state, Slit-pore
Abstract
Square-well (SW) systems has long been viewed as the simplest model able to capture the main
phenomenology of real atomic fluids by complementing hard-sphere repulsion with a finite range and constant
attractive well. Variety of theoretical and molecular simulation methods have been used to study the vapour-
liquid phase equilibria [1-3]. Corresponding state behavior in the vapour-liquid equilibrium of bulk, variable
range SW fluids have been studied by earlier investigators and they concluded deviations from this behaviour
[4]. Moreover, very little studies on the corresponding state behavior of confined SW fluid have been
performed. In the current work using GC-TMMC technique, we are reporting the corresponding state behavior
of vapour-liquid phase equilibrium of a SW fluid in slit-pore modeled by hard ( wf = 0) and attractive ( wf =
2, 3, 4 & 6) SW potential with discretely varying pore width from 1 to 40 molecular diameters. We observed
that for pore width of 3 molecular diameters or less the corresponding state behavior in vapour-liquid phase
equilibrium is well followed by the studied SW fluid and slit-pore confinements. On the other hand, at pore
width of 4 to 16 molecular diameters, significant deviation from corresponding state behavior is observed for
hard and attractive slit pore confined SW fluid. Moreover, at larger pore widths ( >16 molecular diameters),
the corresponding state behaviour of vapour-liquid coexistence envelope are reasonably well followed by
higher wall-fluid interactions ( wf = 4 & 6). However, hard ( wf =0) and smaller wall-fluid interaction ( wf
=2 & 3) has shown deviation from higher wall-fluid interactions ( wf = 4 & 6) corresponding state behavior
of phase coexistence envelope. Interestingly, for pore widths more than 4 molecular diameters, shrinkage in
the corresponding state vapour-liquid coexistence envelope of the studied SW fluid increases as wall-fluid
interaction increases for a given slit width. Moreover, corresponding state vapour coexistence density
increases and liquid coexistence density decreases with increase in the wallfluid interaction strength for a
given pore width of 4 to 40 molecular diameters. To understand this corresponding state behavior of vapour-
liquid phase equilibrium for hard and attractive slit-pores we evaluated the corresponding reduced z-density
profiles of coexisting phases at a reduced temperature for a given pore width. These reduced z-density profiles
of coexisting phases validated the behavior observed in corresponding state plot of vapour-liquid coexistence
envelope. We also studied the corresponding state behaviour of spreading pressure of the SW fluid confined
in hard and attractive slit pores. We observed that the reduced spreading pressures versus reduced temperature
shows deviations from corresponding state behavior for studied hard and attractive slit-pore confinements.
References
[1] X. Zhang and W. Wang "Square-well fluids in confined space with discretely attractive wall-fluid potentials:
Critical point shift" Phys. Rev. E, 2006, 74: 062601-1 to 062601-4.
[2] S. K. Singh, A. K. Saha, J.K. Singh "Molecular Simulation Study of Vapour-Liquid Critical Properties of a
Simple
Fluid in Attractive Slit Pores: Crossover from 3D to 2D" J. Phys. Chem. B, 2010, 114: 4283-4292.
[3] H. L. Vortler "Simulation of Fluid Phase Equilibria in Square-Well Fluids: From Three to Two Dimensions"
Collect. Czech. Chem. Commun., 2008, 73: 518-532.
[4] A. G. Villegas, F. D. Rio, A.L. Benavides "Deviations from corresponding-states behaviour in the vapour-liquid
equilibrium of the square-well fluid" Fluid Phase Equilibria, 1996, 119: 97-112.
PPEPPD 2016
th
Separation of BTEX Compounds from Natural Gas Streams Using Ionic

Liquids
Mamoun Althuluth1*, Nerea R. Rodriguez2, Cor J. Peters1,2, Maaike C. Kroon2
1
Chemical Engineering Department, The Petroleum Institute, UAE
2
Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven,
Netherlands
*
Corresponding author: malthuluth@gmail.com, Phone: +97126075321.
Scientific topic: Phase Equilibria (experimental, modeling)
Keywords: Natural Gas, Separation, Ionic Liquid, Aromatic, Aliphatics.
Abstract
Natural gas mostly consists of methane (CH4), but it also includes significant quantities of other volatile
hydrocarbons including ethane (C2H6), propane (C3H8), butane (C4H10), and pentane (C5H12), as well as
traces of heavier aliphatic hydrocarbons (hexane (C6H14) and heptane (C7H16)) and aromatic
hydrocarbons (benzene, toluene, ethylbenzene and xylene, collectively called BTEX). Moreover, natural
gas can contain acid components, such as carbon dioxide (CO2) and hydrogen sulfide (H2S) [1].
The volatile hydrocarbons and the heavier aliphatic hydrocarbons may stay in the natural gas stream,
because they have heating value and can be liquefied. However, the acid compounds have to be removed
from the natural gas stream, because they can be corrosive and have low heating value. This is normally
done by amine absorption [2] The aromatic hydrocarbons (BTEX) are also undesired in the natural gas
stream, because they can cause plugging problems in downstream processing at sufficiently high
concentrations. Reason is that they will be frozen before the other hydrocarbons liquefy in the
(cryogenic) liquid extraction units. Moreover, they can cause catalyst coking in the sulfur recovery plant
[3].
Previously, we proved that the ionic liquid (IL) 1-ethyl-3-methylimidazolium
tris(pentafluoroethyl)trifluorophosphate ([emim][FAP]) is a promising candidate for natural gas
sweetening. The reason is that the absorption capacity for CO2 is high, the selectivity for CO2/CH4 is
good, and the IL shows low affinity for light hydrocarbons (CH4, C2H6, C3H8 and C4H10) [4]. In this
study, the solubilities of the liquid aliphatic hydrocarbons (hexane, heptane, octane) and the liquid
aromatics compounds (benzene, toluene, ethylbenzene, o-xylene) occurring in natural gas in
[emim][FAP] have been measured at temperatures between 293.15 and 333.15 K at atmospheric
pressure. It was shown that the solubilities of these pure compounds in [emim][FAP] decrease in the
following order: benzene > toluene > o-xylene > ethylbenzene >> heptane > hexane > octane. Therefore,
the aromatics will be absorbed in the [emim][FAP] together with the CO2, while the aliphatics will stay
in the CH4 stream. The large difference in solubility between the aliphatic and aromatic compounds in
[emim][FAP] can also be exploited for their separation.
References
[1] S. Mokhatab, W.A. Poe, Gulf Professional Publishing, Boston, 2012, pp. 1-42.
[2] A.J. Kidnay, W.R. Parrish, D.G. McCartney, CRC Press INC, 2011.
[3] A. Valtz, M. Hegarty, D. Richon, Fluid Phase Equilib., 210 (2003) 257-276.
[4] M.Althuluth, M.T. Mota-Martinez, A. Berrouk, M.C. Kroon, C.J. Peters, J. of Supercritical Fluids, 90 (2014)
65-72.
PPEPPD 2016
th
Understanding the interfacial behavior in isopycnic Lennard-Jones fluid

mixtures by computer simulations
José Matías Garrido1*, Manuel M. Piñeiro2, Andrés Mejía1 & Felipe J. Blas3
1
Departamento de Ingeniería Química, Universidad de Concepción, Chile
2
Departamento de Física Aplicada, Universidade de Vigo, Spain
3
Departamento de Física Aplicada, Universidad de Huelva, Spain
*Corresponding author: josemagarrido@udec.cl
Keywords: adsorption/desorption, density invertion, molecular simulation, global phase diagram
Abstract
The physical characterization of the singular interfacial behavior of heterogeneous fluid systems is a very
important step in preliminary process design stages, and also in the subsequent procedures as the
determination of the optimal operating conditions. Molar isopycnicity or molar density inversion is a
especial case of phase equilibrium behavior that directly affects the relative position of phases in
heterogeneous mixtures, without being affected by gravitational fields [1]. This work is dedicated to
characterize the impact of molar density inversions on the interfacial properties of the involved mixtures.
Results and specific trends of the molar density inversion phenomena on the peculiar calculated
composition profiles across the interface and interfacial tensions are exemplified by considering
Lennard-Jones binary mixtures combined with direct Molecular Dynamics Simulations [2,3]. Our results
show that the density inversion causes a drastic change in the density profile of the mixture [4]. On one
hand, our results concerning the characterization of interfacial density profiles in symmetrical and equal-
sized Lennard-Jones mixtures indicate that desorption -relative minimum at the interface- of the total
density profile increases when the the dispersive energy parameter (ε12) between unlike species decrease.
On the other hand, adsorption -relative maximum at the interface- becomes observable when the
asymmetry of the mixture changes.
References
[1] J. L. Sengers “Mean-field theories, their weaknesses and strength” Fluid Phase Equilibria 1999, 158–160: 3–
17.
[2] M. P. Allen, D. J. Tildesley, Computer Simulation of Liquids, 1 st Ed. Oxford University Press, New York
(USA), 1987.
[3] D. Frenkel, B. Smit, Understanding Molecular Simulation, 2 nd Ed. Academic Press, New York (USA), 2002.
[4] M. J. Tardón, J. M. Garrido, H. Quinteros-Lama, A. Mejía and H. Segura “Molar isopycnicity in
heterogeneous binary mixtures” Fluid Phase Equilibria 2012, 36: 84-97.
Acknowledgements
J. M. G. acknowledges the doctoral scholarship from Conicyt (Chile) and from Red Doctoral REDOC.CTA,
MINEDUC project UCO1202 at U. de Concepción. A. M acknowledges the financial support from FONDECYT
(Chile) under the Project 1150656. M. M. P. acknowledges CESGA (www.cesga.es) for providing access to
computing facilities, and Ministerio de Economía y Competitividad, (Proj. Ref. FIS2012-33621, cofinanced with
EU FEDER funds). F. J. B. also acknowledges Ministerio de Economía y Competitividad (Proj. Ref. FIS2013-
46920-C2-1-P, cofinanced with EU FEDER funds). Additional funding from Junta de Andalucía and Universidad
de Huelva is also acknowledged.

PPEPPD 2016
th
Extraction of lignin from biomass using deep eutectic solvents

Laura J.B.M. Kollau1* and Maaike C. Kroon1
1
Separation Technology, Eindhoven University of Technology, Eindhoven
*Corresponding author: L.Kollau@tue.nl
Scientific topic: Reaction and Separation Technology; Agrochemicals and Biomass

Keywords: Lignocellulosic Biomass; Delignification; Low transition temperature mixtures (LTTMs);
Deep eutectic solvents (DESs)
Abstract
Lignin is a natural occurring complex biopolymer found in the cell walls of higher plants and woody
tissue. It consist of a complex network of the phenylpropanoids p-hydroxyphenyl, guaiacyl, and syringyl
connected mainly by ether bonds and condensed C-C linkages.[1] In the paper industry, lignin prohibits
production of high quality cellulose pulp directly from biomass, since it is bonded to the cellulose, and
thus efficient delignification is required.
Currently in industry delignification takes place during the chemical pulping process by cooking with
chemicals at high temperatures and pressure and with multiple subsequent bleaching steps, often with the
usage of chlorine. A ‘greener’ and more efficient method for wood would be highly beneficial for both
environment and business. Previously, ionic liquids (ILs) have shown their ability to selectively extract
lignin from lignocellulosic biomass without disrupting the cellulose.[2] Some of the promising
characteristics of ionic liquids are shared by Deep Eutectic solvents (DESs). DESs are low transition
temperature mixtures (LTTMs) consisting of at least one hydrogen bond donor (HBD) and one hydrogen
bond acceptor (HBA) counterparts that result on a liquid mixture showing unusual low freezing point.
DESs are nature-based, renewable, biodegradable, low-volatile, cost-effective and extremely energy
efficient, particularly because they do not require high temperatures. [3]
With its exceptional properties, like high lignin solubility at low temperatures and atmospheric pressure
and the negligible solubility of cellulose, DESs offer a groundbreaking new method for the pulping of
many different lignocellulosic materials for producing chemical pulp, pure lignin and other chemicals.
So far a solubility of alkali lignin in DESs of 20 w% has been reported in literature.[4] This solubility
screening is being elaborated with more DESs and an Organosolv lignin. These results will be presented
at the conference. Furthermore, the extractability of lignin from woody tissue and pulp is investigated
with the most promising DESs.
References
[1] J. Ralph, K. Lundquist, G. Brunow, F. Lu, H. Kim, P.F. Schatz, J.M. Marita, R.D Hatfield, S.A. Ralph, J.H.
Christensen, W. Boerjan “Lignins: Natural polymers from oxidative coupling of 4-hydroxyphenylpropanoids”
Phytochem. Rev., 2004, 3, 29-60
[2] A. Brandt, J. Gräsvik, J.P. Hallett, T. Welton “Deconstruction of lignocellulosic biomass with ionic liquids”
Green Chem., 2013, 15, 550-583
[3] M. Francisco, A. van den Bruinhorst, M.C. Kroon “Low-Transition-Temperature Mixtures (LTTMs): A New
Generation of Designer Solvents” Angew. Chem. Int. Ed., 2013, 52, 3074-3085
[4] M. Francisco, A. van den Bruinhorst, M.C. Kroon “New natural and renewable low transition temperature
mixtures (LTTMs): screening as solvents for lignocellulosic biomass processing” Green Chem., 2012, 14, 2153-
2157
Acknowledgements
The authors would like to thank the ISPT cluster “Deep Eutec- tic Solvents in the pulp and paper industry” for their
financial and in kind contribution. This cluster consists of the following organisations: Altri – Celbi, Buckman,
Crown Van Gelder, CTP, DS Smith Paper, Eska Graphic Board, Holmen, ISPT, Mayr- Melnhof, Metsä Fibre,
Mondi, Omya, Parenco BV, Portucel, Sappi, Smurfit Kappa, Stora Enso, Eindhoven University of Technology,
UPM, Van Houtum, Voith Paper, VTT Technical Research Centre of Finland Ltd and Zellstoff Pöls. Further- more,
this research is supported by Paques B.V. and the Dutch Technology Foundation STW, which is part of the
Netherlands Organisation for Scientific Research (NWO) and which is partly funded by the Ministry of Economic
Affairs.

PPEPPD 2016
th
A new algorithm for simultaneous chemical and phase equilibrium

calculation
Christos Tsanas1*, Wei Yan1† and Erling H. Stenby1

1
Department of Chemistry, Technical University of Denmark, Denmark
*Presenting author: ctsa@kemi.dtu.dk
†
Corresponding author: weya@kemi.dtu.dk
Keywords: chemical equilibrium, phase equilibrium, algorithm, heterogeneous synthesis, chemical

tracers
Abstract
From reactive distillation to heterogeneous chemical synthesis, simultaneous chemical and phase
equilibrium (CPE) plays a key-role in the chemical and petroleum industry. Even when equilibrium is
not attained due to kinetics, CPE calculations can provide a thermodynamic limit for the process.
The purpose of this work is to develop a general, reliable and efficient algorithm which will be able to
deal with multiple reactions in multiphase systems. This algorithm could be applied to heterogeneous
organic synthesis, where it is desirable to optimize the conditions of a reaction scheme. Furthermore, it
could be utilized by the oil industry in the chemical tracers test. Reactive tracers are used in an oil well to
asssess an EOR method efficiency and provide information about internal flow characteristics [1].
The algorithm follows the method of Lagrange multipliers (constrained minimization of the Gibbs
energy) [2] and consists of two successive steps. First, the total mole numbers of the phases are fixed and
a subset of the equations is solved for the Lagrange multipliers. These are subsequently utilized as initial
estimates for a Newton method which solves the full set of equations. Another method that has been
widely used to solve this problem is the RAND method [3], where the working equations are linearised
around the composition estimate, satisfying the material balance constraint at all iterations.
In this work the algorithm has been successufully tested on Vapor-Liquid Equilibrium of simple reactive
systems [4]. Future work is focused on improving the robustness of the algorithm to allow calculations
for multiphase reactive systems.
References
[1] A. Salman, B. Kurtoglu, H. Kazemi “Analysis of Chemical tracer Flowback in Unconventional Reservoirs”
SPE/CSUR Unconventional Resources Conference, 2014.
[2] M. L. Michelsen “Calculation of Multiphase Ideal Solution Chemical Equilibrium” Fluid Phase Equilibria,
1989, 53: 73-80.
[3] W. B. White, S. M. Johnson, G. B. Dantzig “Chemical Equilibrium in Complex Mixtures” The Journal of
Chemical Physics, 1958, 28: 751-755.
[4] S. Ung, M. F. Doherty “Vapor-Liquid Phase Equilibrium in Systems with Multiple Chemical Reaction”
Chemical Engineering Science, 1995, 50: 23-48.
PPEPPD 2016
th
A Study on Associative Groups Behaviour: Effect of Chain Growth and

Hydroxyl Groups Positioning into CPA EoS Parameters
André M. Palma1, Mariana B. Oliveira1, António J. Queimada2, João A. P. Coutinho1*
1
CICECO, Chemistry Department, Aveiro University, 3810-193 Aveiro, Portugal.
2
Infochem, KBC Process Technology, 93 Great Suffolk Street, SE1 0BX London, United Kingdom.
*Corresponding author e-mail: jcoutinho@ua.pt
Scientific topic: Thermodynamics and transport properties (modelling)
Keywords: Association, CPA, Equation of State, Hydroxyl groups, Polyols
Abstract
Improving the description of processes containing associative mixtures is one of the most relevant topics
in the area of process simulation software.
Recent years have brought an increase in the appeal of SAFT-like equations of state (EoS) due to their
accuracy in describing associative compounds. These EoS present advanced associative terms based on
perturbation theory to cope with the description of hydrogen bonding and solvation effects. However, the
need for optimization of each set of parameters for these associative components presents an important
limitation for process simulation software.
Parameters for these terms have been studied for many different families of compounds obtaining
parameter tendencies or in some cases constant parameters with the increase in the chain-length. Despite
the large number of studies on the effect of chain-length into the Wertheim’s term, similar studies on the
influence of the positioning of associative groups are scarce.
In order to obtain a general description of associative groups a more thorough study is needed. In this
work we start with the hydroxyl group, analyzing both the influence of chain-positioning between 1-
Alcohols and 2-Alcohols and also the influence of chain-growth in both alcohol families, glycols and
diols.
Acknowledgements
This work was funded by KBC Process Technology Ltd. under project "Extension of the CPA model for
Polyfunctional Associating Mixtures”. André M. Palma Acknowledges Infochem-KBC for his PhD grant. Mariana
B. Oliveira acknowledges her post-doctoral grant SFRH/BPD/71200/2010. This work was developed in the scope
of the projects CICECO-Aveiro Institute of Materials (Ref. FCT UID/CTM/50011/2013), financed by national
funds through the FCT/MEC and when applicable co-financed by FEDER under the PT2020 Partnership
Agreement

PPEPPD 2016
th
Phase Equilibria of Butanol Isomers in Surpercritical Carbon Dioxide
Sergiu Sima1, Adrian Crişciu1, Catinca Secuianu1,2*, Viorel Feroiu1 and Dan Geană1
1
Department of Inorganic Chemistry, Physical Chemistry & Electrochemistry, University Politehnica of Bucharest,
Romania
2
Department of Chemical Engineering, Imperial College London, United Kingdom
*Corresponding author: c_secuianu@chim.upb.ro, c.secuianu@imperial.ac.uk
Keywords: 1-butanol, 2-butanol, isobutanol, t-butanol, carbon
Abstract
The phase equilibria of carbon dioxide + alcohols is of interest in different fields, such as SCF extraction,
reaction, fractionation, nanoparticles formation, separation of non-volatile mixtures, supercritical fluid
chromatography, hydrothermal crystal growing, hydrothermal destruction of hazardous waste, polymer
processing, etc, as well as in the simulation of petroleum reservoirs, enhanced oil recovery, carbon
capture and storage, the transportation and storage of natural gas, refrigeration and heat-pump cycles, and
the study of geological processes [1-2].
Continuing our extensive study on the phase equilibria of carbon dioxide + alcohols, in this paper we
present the experimental and modelling results for the carbon dioxide + butanol isomers binary systems.
We investigated both the influence of the functional group position (hydroxil) and the influence of
hydrocarbon chain branching in alkanols.
The phase behavior of the studied systems was modeled with several thermodynamic models.
References
[1] R. Dohrn, S. Peper, J. M. S. Fonseca “High-pressure fluid-phase equilibria: Experimental methods and systems
investigated (2000-2004)” Fluid Phase Equilibria, 2010, 288: 1–54.
[2] J. M. S. Fonseca, R. Dohrn, S. Peper “Review. High-pressure fluid-phase equilibria: Experimental methods and
systems investigated (2005-2008)” Fluid Phase Equilibria, 2011, 300: 1–69.
Acknowledgements
The authors acknowledge the financial support received from the University Politehnica of Bucharest.

PPEPPD 2016
th
Monte Carlo Simulations of Vapor Liquid Equilibria of Complex Polar

Systems
Eliseo MarinRimoldi and Edward Maginn

Department of Chemical and Biomolecular Engineering, University of Notre Dame, USA
Notre Dame, IN 46545 USA
*Corresponding author: emarinri@nd.edu
Scientific topic: Phase Equilibria, Thermodynamic Properties, Molecular Simulation and Force Fields
Keywords: Monte Carlo, Phase Equilibria, Solubility, Absorption, Gibbs Ensemble
Abstract
Monte Carlo molecular simulation methods have emerged as powerful tools to predict thermodynamic
properties of complex chemical systems. The quality of these predictions has increased as a result of
more available computational power and more accurate force fields. To produce accurate predictions,
force fields must faithfully represent the intraand intermolecular interactions in a system. Typically, the
parameters involved in these force fields are obtained to match a specific set of properties at particular
conditions, and consequently, force fields cannot be used in a wide variety of environments. For
example, many fixed partial charge water models were calibrated to represent the electrostatic
environment of liquid water, and thus might not perform optimally when immersed in a medium with
dissimilar dielectric constant. In this work, an assessment of the capability of classical force fields is
conducted to reproduce the experimental vapor liquid equilibrium of complex systems involving ionic
liquids (ILs) and water. Several combinations of force fields for water and ILs are used, and it is shown
that an accurate representation of the electrostatic environment is of paramount importance. Furthermore,
a more powerful approach is implemented which includes polarization effects into the force field. Two
methods of incorporating polarization are evaluated, namely, the fluctuating charges and Drude
oscillator. A discussion of the associated algorithms as well as vapor liquid equilibrium results for a
diverse set of systems is presented. In general, predictions from these models are better when compared
to force fields that do not incorporate polarization.

PPEPPD 2016
th
Molecular Simulation of Phase Equilibria for Mixtures of Species with

Partial Charges and Polarizable Molecules using Wolf Summation
Christian Waibel1*, Joachim Gross1
1Institute of Thermodynamics and Thermal Process Engineering, University of Stuttgart, Germany
*Corresponding author: waibel@itt.uni-stuttgart.de
Keywords: electrostatic interaction, polarizability, Wolf summation, phase equilibrium
Abstract
Molecular simulation is a suitable tool for predicting phase equilibrium properties. For molecules with
partial charges or induced point dipoles special algorithms are needed to solve the electrostatic
interactions, which have a slow decaying potential. Various techniques have been developed for this
purpose. The most common method is the Ewald summation. The evaluation of electrostatic interactions
is one of the most computationally demanding tasks of molecular simulations.
In this work, a Monte Carlo procedure which calculates phase equilibrium properties in a grand
canonical ensemble {μVT}, will be presented. The Wolf method [1] is a spherically truncated direct r-1
summation with a lower computational cost than the Ewald summation. This study assesses the Wolf
method for mixtures of molecules with partial charges by systematic comparison to the Ewald
summation. Furthermore, we use the Wolf method to calculate the electric field resulting from partial
charges and point dipoles, needed to solve polarizable molecules with induced point dipoles in a self-
consistent manner. We find excellent agreement for phase equilibrium properties. The Wolf summation
is thereby extended to molecules, adding a correction term for omitting the electrostatic interactions
within a molecule.
To determine liquid-vapor phase coexistence properties, the Transition Matrix method [2] is applied. We
collect multiple histograms for varying temperature and molecule numbers N to N+ΔN in order to cover
the entire phase envelope using histogram reweighting [3]. Using this procedure we get liquid-vapor
coexistence properties. The Wolf summation makes it possible to get the electrostatic energy and the
electric field only by evaluating pair interactions. In doing so, we obtain phase equilibrium properties
with a much lower computational cost than with the Ewald summation.
References
[1] D. Wolf , P. Keblinski, S. R. Phillpot, J. Eggebrecht “Exact method for the simulation of Coulombic systems by
spherically truncated, pairwise r−1 summation ” J. Chem. Phys., 1999, 110: 8254-8282.
[2] A. S. Paluch, V. K. Shen, J. R. Errington ”Comparing the Use of Gibbs Ensemble and Grand-Canonical
Transition-Matrix Monte Carlo Methods to Determine Phase Equilibria” Ind. Eng. Chem. Res., 2008, 47: 4533-
4541.
[3] A. Z. Panagiotopoulos “Monte Carlo methods for phase equilibria of fluids” J. Phys.: Condens. Matter, 2000,
12: R25-R52.
Acknowledgements
The authors thank the German Research Foundation (DFG) for financial support of the project within the Cluster of
Excellence in Simulation Technology (EXC 310/2) at the University of Stuttgart.
PPEPPD 2016
th
Fine-Tuning of Phase and Self-Aggregation Behaviour of Fluorinated Ionic

Liquids in Aqueous Solutions
Ana B. Pereiro1,*, Felix Llovell2, João M. M. Araújo1, Luis Paulo N. Rebelo1, Manuel M. Piñeiro3 and Lourdes F.
Vega4
1
Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Oeiras, Portugal
2
IQS School of Engineering, Universitat Ramon Llull,. Via Augusta, 390, 08017 Barcelona, Spain
3
Departamento de Física Aplicada, Facultade de Ciencias, Universidade de Vigo, Vigo, Spain
4
Alya Technology & Innovation, Centre de Promoció Empresarial,
C/ Tres Creus, 236. 08203, Sabadell, Barcelona, Spain
*Corresponding author: anab@itqb.unl.pt
Keywords: Fluorinated Ionic Liquids, Liquid-liquid Equilibria, Solubility in Water, Self-Aggregation

Behaviour, Multiscale Modelling
Abstract
Fluorinated ionic liquids (FILs) constitute a specific family of ILs. Generally, FILs are able to comprise most
of the best characteristics of ionic liquids combined with the unique chemical and biological inertness of
perfluorocarbons. These properties, supplemented by the different possible arrangements of their three
nanodomains (polar, nonpolar and fluorous) [1], enable the design of the best fluid for a desired application.
Therefore, their potential use in biomedical or biomaterial applications is promising and challenging. This
work demonstrates the possibility to tune the final phase equilibria and self-aggregation behaviour of FILs in
aqueous solutions through small modifications or combinations of cations and anions.
A combined theoretical-experimental approach has been used to characterize these FILs containing four
carbons in the anion fluorinated chains. The phase equilibria and the critical aggregation concentrations for
FILs in water (which present cations and anions with surfactants properties) have been experimentally
determined. The self-assembled structures of FILs in aqueous solutions have been also evaluated. A
combination of experimental data with modelling tools has been carried out aiming at revealing how the
delicate interplay between hydrophobic, electrostatic, hydrogen bonding, coulombic, and other interactions
can provide significant conformational changes of these compounds in aqueous solutions. From an applied
perspective, it is also desirable to use theoretical tools that allow a screening of the main properties of FILs in
a rapid and efficient manner. For this purpose, a molecular model within the soft-SAFT approach has been
built based on (i) their chemical structures, (ii) preliminary ab-initio calculations and (iii) several experimental
evidences. The model has been later tested to describe the phase equilibria of these FILs in aqueous solutions.
Finally, a critical study on the aggregates formation has been carried out and compared to experimental
observations.
References
[1] A. B. Pereiro, M. J. Pastoriza-Gallego, K. Shimizu, I. M. Marrucho, J. N. C. Lopes, M. M. Piñeiro, L. P. N.
Rebelo “On the formation of a third, nanostructured domain in Ionic Liquids” Journal of Physical Chemistry B,
2013, 117: 10826-18147.
Acknowledgements
Financial support provided by the Fundação para a Ciência e Tecnologia (FCT/MEC) through projects PTDC/QEQ-
EPR/5841/2014, PTDC/QEQ-FTT/3289/2014 and UID/Multi/04551/2013 and the contracts under Investigador
FCT 2014 is gratefully acknowledged. Additional support was provided by the Catalan Government (2014SGR-
1582), the Spanish Government (CTQ2014-53987-R) and a Transbio SUDOE collaborative project (TRANSBIO-
BCN-GT2-A1-03). F. Llovell acknowledges a Short Term Scientific Mission Grant (STSM-CM1206-020315-
056728), within the framework of the COST Action EXIL - Exchange on Ionic Liquids.

PPEPPD 2016
th
TUESDAY – MAY, 24
Invited Lecture 4
Measuring the unmeasurable by molecular simulations

Hans Hasse
*Corresponding author: hans.hasse@mv.uni-kl.de
Scientific topic: Molecular modeling and simulation
Keywords: Molecular modeling and simulation, force fields, philosophy of science
Abstract
Molecular simulations with force fields are widely used in many fields of science and engineering. They are often
applied for investigations of nanoscale phenomena which cannot be studied experimen-tally. If the goal of such
simulations is retrieving quantitative information, they can be considered as an attempt to “measure the
unmeasurable”.
We first set up a framework for the discussion and analyze in general terms the relation between the real (physical)
world, mathematical models, their implementation on computers, simulations carried out with them, and finally the
comparison of the simulation results with real world experiments. Then, we discuss molecular modeling. A new
approach in this field is multi-criteria optimization. It accounts for the fact that a single model, which is necessarily
a simplification, will usually not represent different types of data equally well, so that there are conflicting
objectives between which compro-mises have to be made. The result of such optimizations is not one single model
but a set of Pareto-optimal models, from which the most attractive for a particular application can be chosen [1, 2].
While the molecular model contains in principle the essential information for the simulation, the extraction of that
information by molecular simulations is among the most challenging tasks in simulation technology. Reliable and
efficient open source codes are a prerequisite for scientific work with molecular simulations [3, 4].
If the critical issues related to molecular modeling and simulation are properly addressed and carefully developed
and tested molecular models, algorithms, and codes are used, molecular simulations can indeed open a way for
“measuring the unmeasurable”. Here, the key question is the reliability of the results. How can confidence in
simulation results be created in such cases? This is discussed using several examples of practical relevance. E.g.,
molecular simulations of fluid two-phase mixtures may show an important enrichment of components at the
interface: the density of a component at the interface may exceed the highest bulk density of that component by
more than an order of magnitude. This effect is irreconcilable with the concept of Fickian diffusion and might have
important consequences for the way we describe mass transfer in fluid separations. Unfortunately, the effect cannot
be studied experimentally in a direct way, so that “measuring the unmeasurable by molecular simulations” is the
key for further developments.
References
[1] K. Stöbener, P. Klein, S. Reiser, M. Horsch, K.-H. Küfer, H. Hasse: Multicriteria Optimization of Molecular
Force Fields by Pareto Approach, Fluid Phase Equilibria 373 (2014) 100-108.
[2] K. Stöbener, P. Klein, M. Horsch, K.H. Küfer, H. Hasse: Parametrization of Two-Center Lennard-Jones Plus
Point-Quadrupole Force Field Models by Multicriteria Optimization, Fluid Phase Equilibria 411 (2016) 33-42.
[3] C. W. Glass, S. Reiser, G. Rutkai, S. Deublein, A. Köster, G. Guevara-Carrion, A. Wafai, M. Horsch, M.
Bernreuther, T. Windmann, H. Hasse, J. Vrabec: ms2: A Molecular Simulation Tool for Thermodynamic
Properties, New Version Release, Computer Physics Communications 185 (2014) 3302-3306.
[4] C. Niethammer, S. Becker, M. Bernreuther, M. Buchholz, W. Eckhardt, A. Heinecke, S. Werth, H. J. Bungartz,
C. W. Glass, H. Hasse, J. Vrabec, M. Horsch: ls1 mardyn: The Massively Parallel Molecular Dynamics Code for
Large Systems, Journal of Chemical Theory and Computation 10 (2014) 4455-4464.
PPEPPD 2016
th
Invited Lecture 5
Multiscale Simulation and Process Analysis of Ionic Liquid Systems

Xiangping Zhang*, Xiaomin Liu, Xinyan Liu, Yongsheng Zhao, Suojiang Zhang
1
Institute of Process Engineering, Chinese Academy of Sciences, China
*Corresponding author: xpzhang@ipe.ac.cn
Scientific topic: Reaction and separation technologeis
Keywords: Process analysis, Thermodynamics, Simulation, Ionic liquids, Gas separation
Abstract
Simulation and process analysis is central to chemical process design which relies on the principles of
thermodynamics, kinetics, transfer properties and so on. A more precise design requires multiscale
method to understand the reaction/separation mechanism with viewpoints from molecule to system.
Ionic liquids (ILs) have shown great potentials to be applied as solvents in gas separations due to
unique properties, such as negligible vapor pressure, tunability of molecular structure and high gas
solubility[1]. In this work, multiscale simulation and process analysis was conducted with the aim of
developing new gas separation processes involving CO2, SO2, NH3.
At first, new thermodynamic models of the ionic fragment contribution-corresponding states (FCCS)
were developed to predict the physicochemical properties of ILs[2] and phase equilibrium of mixture
systems. In order to make the models with higher accuracy and less dependent on experimental data, we
proposed the coarse-grain force field on the basis of the fragment-based classification method, in which
Quantum-chemical was performed to calculate the fragment size, interaction and charge parameters.
Molecular Dynamics was performed based on the parameters to predict properties. Then the relationship
between the structure and the properties of ILs were obtained and guide to design suitable cations and
anions of ILs to reach high solubility and selectivity. Secondly, in a unit scale, the bubble behavior and
mass transfer properties of ionic liquid-gas systems were studied using high speed photographic and
electrical resistance tomography techniques aided with computational fluid dynamic simulation[3].
Thirdly, with the rigorous thermodynamic models and transfer properties, process simulation was
performed to determine the optimal operating parameters and the flowsheet structure considering real
industrial constraints. Furthermore, the techno-economic performance as well as the environmental
impacts of new processes was evaluated and compared with traditional technologies.
References
[1] X. P. Zhang, X. C. Zhang, H. F. Dong, et al. “Carbon capture with ionic liquids: overview and progress” Energy
Environ Sci, 2012, 5: 6668-6681.
[2] Y. Huang, H. Dong, X. Zhang, et al. “A new fragment contribution-corresponding states method for
physicochemical properties prediction of ionic liquids” AIChE J, 2013, 594: 1348-1359.
[3] D. Bao, X. Zhang, H. Dong, et al. “Numerical simulations of bubble behavior and mass transfer in CO2 capture
system with ionic liquids” Chem Eng Sci, 2015, 135: 76-88.
Acknowledgements
The National Basic Research Program of China (2013CB733500) and the National Natural Science Fund for
Distinguished Young Scholars (21425625)
PPEPPD 2016
th
Oral Session 3 – Molecular Modeling and Simulation 2 – O3-1
Predicting the Properties of Aqueous Systems: The Role of Polarization
I. Shvab1 and Richard J. Sadus2*

1
School of Civil Engineering and Geosciences, Newcastle University, UK
2
Centre for Moleclar Simulation, Swinburne University of Technology, Australia
*Corresponding author: rsadus@swin.edu.au
Keywords: Water, Molecular Simulation, Polarization, Heat Capacity, Vapor-liquid Equilibria
Abstract
Water is arguably the most important substance on Earth, playing a near-ubiquitous role in chemical,
biological and industrial processes [1]. Molecular simulation [2] is the preferred theoretical method for
studying water and aqueous systems in general because of the close nexus between the nature of the
underlying model and predicted properties. An accurate intermolecular potential for the evaluation of
inter-particle forces or energies is the key to reliable predictions. Many alternative intermolecular
potentials for water [3] have been proposed, although the basis of the underlying model is often largely
semi-empirical. The most widely used models are rigid and variants of either the four-site transferable
interaction potential (TIP4P) or the three-site simple point charge (SPC, SPC/E) models. These types of
potentials are computationally easy to implement and they have provided worthwhile predictions.
Polarization [4] is a very important contribution to the intermolecular interactions in water that has been
largely missing from many intermolecular potentials. Studies [5], using an ab initio based potential
(MCYna) indicate that including polarization greatly improves the accuracy of predictions. In this work,
we report molecular simulation results for phase equilibria, and thermodynamic properties for both water
and aqueous mixtures using the MCYna potential and compare the results from the non-polarizable
TIP4P/2005, SPC and SPC/E potentials and other alternative polarization potentials such as BK3 and
iAMOEBA. A key aspect is that predictions are reported for a wide range of state points from ambient to
supercritical conditions. The results highlight the importance of accounting for polarization, which can
often result in accuracy close to experimental error.
References
[1] P. Ball, “Water as an Active Constituent in Cell Biology” Chem. Rev., 2008, 108: 74-108.
[2] R. J. Sadus, Moelcular simulation of fluids: therory, algorithms and object-orientation, Elsevier, Amderdam,
1999.
[3] C. Vega, C. and J. L. F. Abascal, “Simulating Water with Rigid Non-Polarizable Models: A General
Perspective. Phys. Chem. Chem. Phys., 2011, 13, 19663.
[4] I. Shvab and R. J. Sadus, “Atomistic Water Models: Aqueous Thermodynamic Properties from Ambient to
Supercritical Conditions” Fluid Phase Equil. (2015) http://dx.doi.org/10.1016/j.fluid.2015.07.040.
[5] T. M. Yigzawe and R. J. Sadus, “Thermodynamic Properties of Liquid water from a Polarizable Intermolecular
Potential” J. Chem. Phys. 2013, 138, 044503.

PPEPPD 2016
th
Fluid–fluid coexistence in an athermal colloid–polymer mixture:

thermodynamic perturbation theory and continuum molecular-dynamics
simulation
Julio Jover, Amparo Galindo, George Jackson, Erich A. Müller and Andrew J. Haslam*
Department of Chemical Engineering, Imperial College London, South Kensington Campus,
London SW7 2AZ, United Kingdom
*Corresponding author: a.haslam@imperial.ac.uk
Scientific topic: Molecular simulation; phase equilibria
Keywords: hard spheres; chains; depletion interaction; demixing; potential of mean force
Abstract
Using both Wertheim’s thermodynamic perturbation theory (TPT1) [1,2] and continuum molecular-
dynamics simulation, we examine a mixture of hard-sphere (HS) polymer chains of degree 100, and
colloids, represented by HSs of diameter 20 times that of the monomer segments comprising the polymer
chains. According to TPT1 this athermal system phase separates into colloid-rich and polymer-rich fluid
phases. Using a continuous pseudo-HS potential developed in previous work [3], molecular-dynamics
simulations are performed at a phase point indicated by TPT1 to be well within the two-phase region,
from starting configurations corresponding to completely pre-mixed and completely phase-separated
colloids and polymers. Clear evidence is seen of the stabilization of both simulations into two co-existing
fluid phases. The peaks in the probability distributions of the densities correspond to the densities
calculated using TPT1; interestingly, an analysis of the interfacial tension of the phase-separated regions
indicates ultra-low tensions in line with previous values determined with square-gradient theory [4] and
experiment [5] for colloid–polymer systems. Further simulations are carried out to examine the nature of
these co-existing phases. Reminiscent of the Asakura-Oosawa model [6], the polymer chains are seen to
be fully penetrable by other polymers however, from the point of view of the colloids, they behave (on
average) as almost-impenetrable spheres. As expected, the averaged interaction between polymer
molecules in the polymer-rich phase is found to be of soft-repulsive character. On the other hand, the
corresponding interaction in the colloid-rich phase is revealed to be of an entirely different form,
characterized by a region of effective intermolecular attraction.
References
[1] M. S. Wertheim, J. Chem. Phys., 1987, 87: 7323.
[2] W. G. Chapman, G. Jackson, K. E. Gubbins, Mol. Phys.,1988,   65: 1057.
[3] J. Jover, A. J. Haslam, A. Galindo, G. Jackson, E. A. Müller, J. Chem. Phys., 2012, 137: 144505.
[4] A. Moncho-Jordá, B. Rotenberg, A. A. Louis, J. Chem. Phys., 2003, 119: 12667.
[5] D. G. A. L. Aarts, M. Schmidt, H. N. W. Lekkerkerker, Science, 2004: 304, 847.
[6] S. Asakura, F. Oosawa, J. Chem. Phys., 1954, 22: 1255; idem, J. Polym. Sci. 1958, 33: 183.

PPEPPD 2016
th
Molecular Thermodynamic Modeling of Self-Assembly into Branches and

Spatial Networks in Solution
Igor Gotlib, Michail Voznesenskiy, Ksenia Emelyanova and Alexey Victorov*

St. Petersburg State University, Russia
*Corresponding author: victorov_a@yahoo.com
Keywords: Physical gel, Amphiphile, Associative polymer, Microemulsion
Abstract
Reversible spatial networks are found in a diversity of systems. Typical examples are solutions of
wormlike surfactant micelles and polymer physical gels. Because formation and breakup of the network
controls the viscoelasticity and other important properties of the system, network-forming fluids find
numerous applications ranging from tissue engineering and drug delivery to self-healing coatings and
production of oil. The basic structural unit of a spatial network is the branching part of the chain. It has
been known that formation of reversible networks in fluids of quite different microscopic nature is
governed by the same driving force: the balance between the free energies of chain’s branching portion
and its terminal part. [1] An individual microscopic “portrait” of the system is reflected in specific
models of these free energies. Molecular thermodynamic models make possible to estimate the free
energy of the branching portion for a number of systems that include fluids of sticky spheres, surfactant
solutions and mixtures of associative polymers. [2] In this work we discuss recent advances of molecular
thermodynamic models and give several illustrative examples for these systems. We model
transformation of an amphiphilic membrane into a spatial micellar network via the appearance of
perforations in a bilayer. Phase behavior of a microemulsion including formation of a sponge phase is
also described. We consider the effect of a number of important factors (acidity and salinity of the
medium and specific chemistry of added salt) on the formation of a network. Another example is the
spatial network of associative chainlike molecules in a good solvent. We develop a mean-field model and
perform MD-simulation for systems of this type. Our results show important effects of chain cyclization
and crowding on formation of a spatial network.
References
[1] A. G. Zilman, S. A. Safran “Thermodynamics and structure of self-assembled networks” Physical Review E,
2002, 66: 051107-28.
[2] A. I. Victorov, M. A. Voznesenskiy, E. A. Safonova "Spatial networks in solutions of worm-like aggregates:

universal behavior and molecular portraits" Russian Chemical Reviews, 2015, 84: 693–711.
Acknowledgements
For financial support, we thank St.Petersburg State University (grant #12.38.199.2014) and the Russian Foundation
for Basic Research (grant #15-03-04629).

PPEPPD 2016
th
Transport of Multicomponent Hydrocarbon Mixtures in Shale Organic

Matter by Molecular Simulations
Julien Collell1, Guillaume Galliéro2, Romain Vermorel2, Philippe Ungerer3, Marianna Yiannourakou3, François
Montel1 and Magali Pujol1
1
Total SA, Centre Scientifique et Technique Jean-Féger, Avenue Larribeau,, 64018 Pau, France
2
Laboratory of Complex Fluids and their Reservoirs, UMR-5150 CNRS - Total - University of Pau, 64000 Pau,
France
3
Materials Design SARL, 18 rue de Saisset, 92120 Montrouge, France
*Corresponding author: julien.collell@total.com
Scientific topic: 1.1 Applied Thermodynamics, Fluid Dynamics, Heat Transfer
Keywords: Multicomponent Transport, Nanoporous Membrane, Molecular Simulations, Modeling
Abstract
Hydrocarbon production from shales has known an important increase in the past years.
However, the recovery process remains largely unknown, which hinders the sustainability of
such resources. In particular, hydrocarbons in shales are mostly located in microporous nodules
of organic matter, the so-called kerogen, which are likely to act as selective barriers to passage
of hydrocarbons [1].
In this work, we have investigated the mechanisms of hydrocarbons transport through
microporous kerogen structures [2]. For that purpose, molecular dynamic simulations have been
performed within the MedeA environment. In addition to quantitative data, we have come up
with a clear picture of multicomponent transport in such materials. We have shown that the
transport of hydrocarbon mixtures in shales is essentially a diffusive process, and transport
coefficients can be well approximated by the self-diffusivities. Furthermore, we have examined
the influence of the thermodynamic conditions (temperature and adsorbed amount) and the
alkane chain length. Inspired by the Rouse and surface diffusion theories, we have proposed a
simple scaling law that predicts the transport coefficients of linear alkanes in the mixture in
good agreement with our simulations data [3].
References
[1] Falk, K.; Coasne, B.; Pellenq, R.; Ulm, F.; Bocquet, L. Subcontinuum mass transport of condensed
hydrocarbons in nanoporous media. Nat. Commun. 2015, 1–25.
[2] Collell, J.; Ungerer, P.; Galliero, G.; Yiannourakou, M.; Montel, F.; Pujol, M. Molecular Simulation of Bulk
Organic Matter in Type II Shales in the Middle of the Oil Formation Window. Energy & Fuels 2014, 28, 7457–
7466.
[3] Collell, J.; Galliéro, G.; Vermorel, R.; Ungerer, P.; Yiannourakou, M.; Montel, F.; Pujol, M. Transport of
Multicomponent Hydrocarbon Mixtures in Shales Organic Matter by Molecular Simulations. J. Phys. Chem. C
2015, in press.
Acknowledgements
We gratefully acknowledge TOTAL S.A. for financial support and for a grant for one of us (Julien Collell).
Computer time for this study was provided by the computing facilities of the TOTAL Research Center (CSTJF,
Pau), of the MCIA (Mésocentre de Calcul Intensif Aquitain) and of the Université de Pau et des Pays de l’Adour.

PPEPPD 2016
th
Oral Session 4 – Reaction and Separation Techniques – O4-1
Hydrophobic Deep Eutectic Solvents: A New Generation of Water-

Immiscible Extractants
Dannie J.G.P. van Osch1,*, Lawien F. Zubeir1, Adriaan van den Bruinhorst1, Marisa A.A. Rocha2 and Maaike C.
Kroon1
1
Separation Technology Group, Department of Chemical Engineering and Chemistry, Eindhoven University of
Technology, The Netherlands
2
Technische Thermodynamik, Universität Bremen, Germany
*Corresponding author: D.v.Osch@tue.nl
Scientific topic: Reaction and separation technologies
Keywords: Hydrophobic deep eutectic solvents, water-immiscible extractants, volatile fatty acids
Abstract
It is generally accepted that the first publication regarding deep eutectic solvents (DESs) emerged in
literature in 2003, when the eutectic mixture between urea and choline chloride in a 2:1 ratio was
presented.[1] Deep eutectic solvents are composed of the combination of at least one hydrogen bond
donor (HBD) and one hydrogen bond acceptor (HBA) associated with each other via hydrogen bonding
upon the formation of an eutectic mixture with a considerable lower melting point than its constituents.
DESs have shown to have similar properties as ILs, while some limitations of the ILs, such as the
production costs, can be overcome by the use of DESs.[2]
Up until now, all DESs have shown to be hydrophilic, and thus dissolve in water. However, our group
recently discovered the existence of hydrophobic DESs.[3] These hydrophobic DESs consist of a fatty
acid, decanoic acid, as HBD and quaternary ammonium salts as HBA. The quaternary ammonium salts
used in our investigation were tetrabutylammonium chloride (N4444-Cl), methyltrioctylammonium
chloride (N8881-Cl), tetraheptylammonium chloride (N7777-Cl), tetraoctylammonium chloride (N8888-Cl),
methyltrioctylammoniumbromide (N8881-Br) and tetraoctylammonium bromide (N8888-Br). The
hydrophobicity of these developed DESs was tested via measuring the uptake of water by the DESs and
the leaching of the quaternary ammonium salts into the water. Furthermore, the developed hydrophobic
DESs were used for the extraction of volatile fatty acids (VFAs) from an aqueous environment.
The results showed that an increase of the number of the carbons on the quaternary ammonium salts led
to a decrease in water uptake for the ones with a chloride anion. The leaching had the same trend.
Regarding the extraction of the VFAs, i.e. acetic, propionic and butyric acids, it was found that N 8888-Cl
had the highest extraction efficiency, which could be explained by a combination of the lower steric
hindrance induced via the methyl group and the chloride anion of the quaternary ammonium salt.
References
[1] A. P. Abbot, G. Capper, D. L. Davies, R. K Rasheed, V. Tambyrajah “Novel solvent properties of choline
chloride/urea mixtures” Chemical Communication, 2003, 70-71.
[2] M. Francisco, A. van den Bruinhorst, M.C. Kroon, Low-Transition-Temperature Mixtures (LTTMs): A New
Generation of Designer Solvents, Angewandte Chemie International Edition, 2012, 52, 3074-3085.
[3] D. J. G. P. van Osch, L. F. Zubeir, A. van den Bruinhorst, M. A. A. Rocha, M. C. Kroon, Hydrophobic deep
eutectic solvents as water-immiscible extractants, Green Chemistry, 2015, 17, 4518-4521.
PPEPPD 2016
th
Dynamic Online Process Optimization Based on Rigorous Thermodynamics
Günther Holzer1*, Thomas Wallek2

1
CEO, Prozess Optimal Holzer GmbH, Impulszentrum 1, 8250 Vorau, Austria
2
Institute of Chemical Engineering and Environmental Technology, NAWI Graz,
Graz University of Technology, Austria
*Corresponding author: holzer@prozess-optimal.at
Scientific topic: Processing and Applications / Product and Process Engineering
Keywords: process simulation, model tuning, process optimization, online optimization, simulation-
based optimization
Abstract
Process optimization in the chemical industry is very complex, particularly when it comes to alternating
feedstocks and process parameters. Hitherto, mathematically based models are state of the art for online
process optimization. One limitation of these models is the fact that any changes are included too
late/sluggishly in the process. Furthermore, although purely mathematical approaches are capable of
accounting for variation of parameters and dynamics, extrapolation of such models beyond their validity
ranges runs the risk of violating physical or thermodynamic constraints. This may result in suboptimal
results and/or considerable uncertainties when operating modes approach their limiting conditions. In
this case, the optimization potential of chemical processes is not fully exploited. To overcome such
limitations, the use of rigorous thermodynamic approaches for online optimization instead of
mathematical models should be considered. Based on thermodynamic models, dynamic real-time
optimizations can be implemented, allowing for online predestination and simultaneous optimization of
control parameters for production. A prerequisite for such an approach is the use of real-time data from
the chemical plant as an input for the dynamic optimizer based on thermodynamics.
In this paper, a successful application of dynamic online process optimization based on rigorous
thermodynamics is presented on the basis of a benzene production plant. Using online data of distillation
column profiles, product streams and conentrations as well as heat exchanger parameters as input, the
model provides online recommendations for the operator within the process control system, comprising
optimal reflux ratio, side-stream flow rates and column control parameters.
This example illustrates that the combination of rigorous thermodynamics and dynamic optimization at
present has a great potential for various kinds of production plants in the chemical industry, particularly
when it comes to alternating feedstocks and process parameters.
References
[1] Y. Chen, J. C. Eslick, I. E. Grossmann, D. C. Miller “Simultaneous Process Optimization and Heat Integration
based on Rigorous Process Simulations” Computers & Chemical Engineering, 2015, 81: 180–199.
[2] R. Anantharamana, E. L. Johnsen, T. Gundersen “Revisiting the Simultaneous Process Optimization with Heat
Integration Problem” Computer Aided Chemical Engineering, 2014, 34: 243-248
[3] J. Gmehling, M. Kleiber, “Vapor–Liquid Equilibrium and Physical Properties for Distillation” Dilstillation –
Fundamentals and Principles, 2014, 1: 45-95.

PPEPPD 2016
th
From atomistic simulations to process modelling: dehydration of gas streams

using water stable Metal Organic Frameworks as adsorbents
Flor R. Siperstein1 and Chung L. Chia1*
1
Chemical Engineering and Analytical Science, University of Manchester, U.K.
*Corresponding author: chunglim.chia@manchester.ac.uk
Keywords: Molecular simulation, Adsorption, Metal Organic Frameworks
Abstract
Zeolite 13X is a common water adsorbent that requires large amounts of energy during the regeneration
process. A potential alternative is using an adsorbent with a high capacity and selectivity for water, but a
lower heat of adsorption. Some Metal Organic Frameworks (MOFs) exhibit excellent hydrothermal
stability, decent saturation capacity and ease of regeneration, such as UiO-66, MOF-801 and CAU-10,
showing great potential as water adsorbents. [1] Nevertheless, better understanding on the performance
of these MOFs in a fixed bed column is needed to truly exploit them in realistic applications.
Nevertheless, some of the physical properties required for the process simulation have not been measured
experimentally, but can be obtained from molecular simulations.
Important properties were obtained using molecular simulations. Grand Canonical Monte Carlo (GCMC)
molecular simulations were used to estimate the water adsorption isotherms which agreed well with
experimental data [1, 2]. Particular emphasis was placed on the temperature-dependency of these
isotherms because temperature waves occur in a fixed bed column as a result of the heat released during
the physical adsorption process [3]. Furthermore, molecular dynamic simulations were employed to
predict transport properties of water within these structures. Subsequently, this information was fed into
an adiabatic adsorption column model to simulate the adsorption and regeneration steps, using empirical
correlations for the properties defined by the column hydrodynamics.
The performance of novel MOFs is compared to traditional adsorbents such as 13X to shed some light on
the question: Can these novel materials be used in industrial dehydration processes?
References
[1] J. Canivet, A. Fateeva, Y. Guo, B. Coasne, D. Farrusseng, "Water adsorption in MOFs: fundamentals and
applications". Chemical Society Reviews, 2014. 43(16): p. 5594-5617.
[2] H. Furukawa, F. Gándara, Y.B. Zhang, J. Jiang, W.L. Queen, M.R. Hudson, O.M. Yaghi, "Water adsorption in
porous metal-organic frameworks and related materials". Journal of the American Chemical Society, 2014.
136(11): p. 4369-4381.
[3] D.M. Ruthven, S. Farooq, K.S. Knaebel, "Pressure Swing Adsorption". 1994: VCH Publishers.
Acknowledgements
The Research Impact Scholarship from the University of Manchester Alumni for financial support.

PPEPPD 2016
th
The Different Faces of Poly(alkylene glycol)s + Nature-Inspired Ionic Fluids

Aqueous Biphasic Systems: Impact of the Hydrophilic-Hydrophobic Balance
on the Phase Behavior and the Extraction of Proteins
Luís Paulo N. Rebelo, João M. M. Araújo*
Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Oeiras, Portugal
*Corresponding author: jmmda@itqb.unl.pt
Keywords: Nature-Inspired Ionic Fluids, Poly(alkylene glycol)s, Aqueous Biphasic Systems, Proteins
Abstract
In the last decade, ionic liquids (ILs) have emerged as one of the most attractive solutes for aqueous
biphasic systems (ABS). Our recent review [1] on IL-based ABS addressed their phase diagrams, relative
ability to phase splitting, and highlighted their outstanding performance in the extraction of targeted
biomolecules. Moreover, we recently proposed a benign route for ABS containing cholinium-based ILs
[2]. The superior extractive performance of IL-based ABS over conventional polymer-based systems
results from the broad hydrophobic-hydrophilic range exhibited by the coexisting phases when ILs are
employed [3]. To overcome some of the limitations of ILs + inorganic salts ABS, our pioneer work [4]
on the salting-in and salting-out effects of ILs through polymers dissolved in aqueous media
demonstrated the possibility of their formation by using poly(alkylene glycol) + IL combinations.
Herein, new nature-inspired ionic fluids (NATIFs; include ILs and deep eutectic solvents) were
synthesized by natural primary metabolites (e.g. sugars, sugar alcohols, amino acids, organic acids,
choline derivatives) and it was shown that the phase behavior of the Poly(alkylene glycol)s + NATIFs
ABS can be tailored to a relevant extent by a judicious selection of the polymer molecular weight or of
the chemical structure of the constitutive ions of the ionic fluid. The extraction of proteins, such as
lysozyme (enzyme from the class of hydrolases), elastase (enzyme from the class of proteases), insulin
(peptide hormone), and monoclonal antobody (IgG1; a therapeutic protein), was studied and compared
with conventional ABS (polymer/IL + inorganic salt). Additionally, the stability and activity of the
proteins in aqueous solution of IL was studied. Moreover, the obtained results were compared with those
of cholinium chloride and sucrose (common stabilizers of proteins).
References
[1] M.G. Freire, J.M.M. Araújo, et al. Chem. Soc. Rev., 2012, 41: 4966-4995.
[2] S. Shahriari, J.M.M. Araújo, et al. RSC Adv., 2013, 3: 1835-1843.
[3] M.G. Freire, L.P.N. Rebelo, et al. J. Phys. Chem. B, 2012, 116: 7660-7668.
[4] Z. P. Visak, J. N. Canongia Lopes, L. P. N. Rebelo. Monatsh. Chem., 2007, 138: 1153-1157.
Acknowledgements
The financial support from FCT/MEC (Portugal) through projects PTDC/QEQ-FTT/3289/2014, PTDC/QEQ-
EPR/5841/2014, UID/Multi/04462/2013 and UID/Multi/04551/2013, grant SFRH/BD/100563/2014 (N. S. M. V.),
and 2014 FCT Investigador contracts (J. M. M. A. and A. B. P.) is gratefully acknowledged.

PPEPPD 2016
th
Oral Session 5 – Thermodynamics and Transport Properties – O5-1
High-Precision, High-Efficiency Calculation of Properties by Molecular

Simulation
Andrew J. Schultz, Sabry G. Moustafa, Weisong Lin, and David A. Kofke *

Department of Chemical and Biological Engineering, University at Buffalo – SUNY, Buffalo, NY, USA
*Corresponding author: kofke@buffalo.edu
Keywords: crystalline solids, heat capacity, mapped averaging
Abstract
Knowledge of approximate harmonic behavior of crystals is introduced into a new “mapped averaging”
framework to yield alternative expressions for the thermodynamic properties of crystalline systems [1].
The expressions separate the known harmonic behavior from residual averages, which thus encapsulate
anharmonic contributions to the properties. With harmonic contributions removed, direct measurement of
these anharmonic contributions by molecular simulation can be accomplished without contamination by
noise produced by the already-known harmonic behavior. An example application to the Lennard-Jones
model shows that first-derivative properties (pressure, energy) can be obtained to a given precision via
this harmonically-mapped averaging at least 10 times faster than by using conventional averaging, and
second-derivative properties (e.g., heat capacity) are obtained at least 100 times faster; in more favorable
cases, the speedup exceeds a millionfold. Free-energy calculations are accelerated by 50 to 1000 times.
Data obtained using these formulations are rigorous and not subject to any added approximation, and in
fact are less sensitive to inaccuracies relating to finite-size effects, potential truncation, equilibration, and
similar considerations. Moreover, the approach does not require any alteration in how sampling is
performed during the simulation, so it may be used with standard Monte Carlo or molecular dynamics
methods. However, the mapped averages do require evaluation of first and second derivatives of the
intermolecular potential, for evaluation of first and second thermodynamic-derivative properties,
respectively. Apart from its usefulness to simulation, the formalism developed here may constitute a
basis for new theoretical treatments of crystals. We demonstrate the effectiveness of harmonically
mapped averaging for several crystalline systems, including those that use electronic density functional
theory to model the interatomic interactions. Then, we show how the mapped averaging concept can be
generalized, allowing high-efficiency calculation of other properties, including some for non-crystalline
systems.
References
[1] S.G. Moustafa, A.J. Schultz, and D.A. Kofke “Very fast averaging of thermal properties of crystals by
molecular simulation” Physical Review E, 2015, (in press).
Acknowledgements
Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for partial
support of this research. Funding was also provided by an IMPACT grant from the University at Buffalo.

PPEPPD 2016
th
Oral Session 5 – Thermodynamics and Transport Properties – O5-2
Effect of Phase-Equilibrium Uncertainties on the Separation of

Heterogeneous Azeotropes – Application to the Water/1-Butanol System
Paul M. Mathias1
1
Fluor Corporation, Aliso Viejo, California 92698, USA
*Corresponding author: Paul.Mathias@Fluor.com
Scientific topic: Thermodynamics and transport properties (experimental and modeling)
Keywords: vapor-liquid-liquid equilibrium, property uncertainty, azeotropic separations
Abstract
Many papers have been written highlighting the need to estimate process-design uncertainties that result
from the uncertainties in correlated physical properties. The most significant source of property
uncertainties on process design is from the correlations of phase equilibrium. However, uncertainty
analysis is not a routine element of today’s industrial process-design practice, mainly because education
and awareness are lacking, and the proposed methods are difficult and cumbersome to apply.
In order to help rectify the situation, Mathias [1] developed an intuitive and easy-to-apply method based
upon treating the mixture, for the purpose of activity-coefficient perturbation, as a set of pseudobinaries
described by the Margules equation. Mathias [1] first applied his method to two case studies − (1) a
propylene-propane superfractionator for which small changes in correlated relative volatilities have a
large effect on the design of the distillation column; and (2) a dehexanizer column that separates a
mixture containing many close-boiling hydrocarbon components − and demonstrated that the proposed
approach provides quantitative insight into the effect of property uncertainties for both these diverse
process designs, and helps to quantify the safety factors that need to be imposed upon the design. In a
subsequent study, Mathias [2] applied the methodology to a distillation train that separates the acetone-
chloroform-benzene ternary mixture, which contains one maximum-boiling azeotrope, and showed that
the approach quantifies the effect of property uncertainties on utility consumption and also identifies
limits on operating variables (specifically recycle flow).
In this presentation, the Margules perturbation method is applied to the separation of the water/1-butanol
binary mixture. The application is complex because this binary mixture forms a minimum-boiling
azeotrope and also exhibits liquid-liquid equilibrium, and the typical separation scheme includes a
decanter as well as two distillation columns (Westerberg and Wahnshafft [3]). The present presentation
extends the application of the Margules activity-coefficient perturbation method to systems exhibiting
liquid-liquid equilibrium.
References
[1] Mathias, P. M., “Sensitivity of Process Design to Phase Equilibrium – A New Perturbation Method Based Upon
the Margules Equation,” J. Chem. Eng. Data, 2014, 59, 1006-1015.
[2] Mathias, P. M., “Effect of VLE Uncertainties on the Design of Separation Sequences by Distillation – Study of
the Benzene-Chloroform-Acetone System,” accepted for publication in Fluid Phase Equilibria, September 2015.
[3] Westerberg, A.W.; Wahnschafft, O., “Synthesis of Distillation-Based Separation Processes”, Adv. Chem. Eng.,
1996, 23, 63-170.

PPEPPD 2016
th
Oral Session 6 – Reaction and Separation Techniques 2 – O6-1
Eutectic Solvents: Designing Solvents for the Future

Catarina Florindo1, Andreia Gouveia1, Bernardo D. Ribeiro2 and Isabel M. Marrucho1
1
Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa, Av. da República, 2780-157, Oeiras,
Portugal
2
Universidade Federal do Rio de Janeiro, Av Athos da Silveira Ramos, Centro de Tecnologia,
Escola de Quimica, E-102, Rio de Janeiro, Brazil
*Corresponding author: imarrucho@itqb.unl.pt
Scientific topic: Reaction and Separation echnologies
Keywords: Deep Eutetic Solvents, Thermophysical Properties, Phase equilibria, Breaking Azeotropes
Abstract
One of the major challenges in modern chemistry and chemical engineering is the formulation of
new solvents, which simultaneously meet the Green Chemistry criteria and have the ability to dissolve as
large as possible spectrum of solutes [1]. Currently two major classes of solvents, ionic liquids (ILs) and
eutectic mixtures [2] are being largely developed and used by academia and industry, with new members
being proposed at a fast pace. Regarding ILs, their commercial availability promoted the production of a
large body of information concerning their thermophysical and transport properties, toxicity and phase
equilibria, and consequently, new applications can now be properly evaluated. Conversely, eutectic
mixtures, and in particular deep eutectic solvents, prepared from a salt or an ionic liquid combined with a
neutral compound, are still in the infancy, lacking organization and properties systematization. Inspired
by this novel advanced class of green ILs, the aim of this work is to prepare eutetic mixtures from cheap,
non-toxic, biodegradable compounds using cholinium chloride, acetylcholine chloride and
benzoylcholine chloride and a wide variety of naturally occurring organic acids and carbohydrates.The
use of other compounds from natural resources , such as L,D-menthol will also be evaluated in the
preparation of eutetic mixtures, where coulombic forces are absent and hydrophobic behaviour is
obtained. Thermophysical properties of the prepared DES, such as densities and viscosities, at
atmospheric pressure and in a large range of temperatures and with variable water contents will be
discussed. Finally, the use of the prepared DES in liqui-liquid extraction of azeotropic mixtures will be
presented and their efficiency discussed in terms of selectivity and distribution coefficent.
References
[1] M. Petkovic, K.R. Seddon, L.P.N. Rebelo, C. Silva Pereira, "Ionic liquids: a pathway to environmental
acceptability", Chemical Society Reviews, 40, 1383-1403, 2011
[2] A.P. Abbott, G. Capper, D.L. Davies, R.K. Rasheed, V. Tambyrajah, "Novel solvent properties of choline
chloride/urea mixtures", Chemical Communications, 70-71, 2003
Acknowledgements
Catarina Florindo is grateful to FCT (Fundação para a Ciência e a Tecnologia) for her PhD grants
(SFRH/BD/102313/2014). Isabel M. Marrucho acknowledges FCT/MCTES (Portugal) for a contract under
Investigador FCT 2012. This work was supported by FCT through the project PTDC/EQU-FTT/1686/2012 and
Research Unit GREEN-it "Bioresources for Sustainability" (UID/Multi/04551/2013).
PPEPPD 2016
th
Oral Session 6 – Reaction and Separation Techniques 2 – O6-2
Application of Thermodynamics to Bioreactions
Christoph Held*
Department of Biochemical and Chemical Engineering, Laboratory of Thermodynamics, Technische Universität
Dortmund, Germany
*Corresponding author: christoph.held@bci.tu-dortmund.de
Keywords: reaction equilibrium, Gibbs energy of reaction, biothermodynamics, activity coefficients,

solubility
Abstract
The field of industrial biotechnology is rapidly growing. This includes the use of enzymes as catalyst to
make valuable products in chemical industry, food industry, cosmetical and pharmaceutical industry. The
application of thermodynamics to enzyme-catalyzed bioreactions can give a siginificant contribution to
feasibility and yield of reactions, which is useful in industrial biotechnology. To give an example,
bioreactions are often limited by thermodynamic equilibrium, which forces the equilibrium position to
the reactant site. Thus, it is of interest to manipulate reaction conditions in a way that the reaction
equilibrium is shifted to the product site and therewith allows increased yield. Not less important,
thermodynamics can help to understand the feasibility of biological pathways. Examples from literature
show that the application of thermodynamics to bioreactions is straightforward yet difficult and requires
careful and thermodynamically correct data analysis. This includes reaction data (e.g. Gibbs energy of
reaction ∆Rg) as well as data on the thermo-physical properties of the reacting agents (e.g. activity
coefficients, solubility).
This work will show how thermodynamics can be applied to reactions, starting with a demonstration
using a chemical reaction. Second, this approach will be transferred to bioreactions (e.g., [1,2])
emphasizing their special challenges as e.g., experimental difficulties due to very low concentrations,
solubility limitation of reactants, species distribtion of reacting agents, bioreactions in non-aquoues
medium, and poor experimental data basis. Nowadays, the latter still forces researchers to use apparent
data (concentrations) instead of true thermodynamic standard data (activities). More detailed, this means
that often concentration-dependent data (i.e. apparent equilibrium constants) are used to calculate
standard Gibbs energies of reaction due to the absence of activity-coefficient data of the reacting agents.
This might cause high errors for the analysis of processes where standard data are required.
This work adresses the dependence of apparent equilibrium constants on temperature, pH, the presence
of electrolytes and solvents, and the concentrations of all reactants and products. Special attention is
given to the ability to predict bioreaction equilibria with thermodynamic models e.g., PC-SAFT,
UNIFAC, or COSMO-RS. These predictions are applied to bioreactions in aqueous and non-aquoeus
reaction medium, considering metabolic reactions as well as industrially-relevant reactions.
References
[1] P. Hoffmann, C. Held, T. Maskow, G. Sadowski “A thermodynamic investigation of the glucose-6-phosphate
isomerization” Biophysical Chemistry, 2014, 195: 22-31
[2] P. Hoffmann, M. Voges, C. Held, G. Sadowski “The role of activity coefficients in bioreaction equilibria:
Thermodynamics of methyl ferulate hydrolysis” Biophysical Chemistry, 2013, 173/174: 21-30.
PPEPPD 2016
th
Poster Session II – P01
Application of e-KT-UNIFAC Model
for Improved and Innovative Design of Biphasic Reacting Systems
Amata Anantpinijwatna1, Sun Hyung Kim1,2, Mauricio Sales-Cruz1,3, Rafiqul Gani1*

1
Department of Chemical and Biochemical Engineering, Technical University of Denmark, Denmark
2
Department of Chemical and Biological Engineering, Korea University, South Korea
3
Departamento de Procesos y Tecnología, Universidad Autónoma Metropolitana – Cuajimalpa, Mexico
*Corresponding author: rag@kt.dtu.dk
Scientific topic: Processing and Applications, Product and Process Engineering
Keywords: Biphasic Reacting Systems, Modelling, Innovative Design
Abstract
Biphasic reacting systems have a broad range of application in chemical, pharmaceutical, and agro-bio
industries. The systems contain two immiscible liquid phases, in which reactants and catalysts (including
also biocatalysts and enzymes) can exist in different liquid phases, allowing novel synthesis paths, higher
yield, and faster reaction rate, as well as, making the separation tasks easier by manipulating process
condition after reaction. A mathematical model which collectively describe reactions, mass transfer, and
equilibrium of heterogeneous species is constructed with the biphasic reacting systems modelling
framework [1]. It can be a powerful tool for an improves and innovative design of the systems.
To handle the complexity of the system, the system is devided into sub-systems of binary species which
require an appropriate thermodynamic model to predict the partition and equilibrium of the involved
species. In the earlier models, different thermodynamic models are use for each sub-systems, which
inevitably increase the complexity and uncertainty of the model. Recently, a predictive electrolyte model
based on group contribution method (e-KT-UNIFAC) [2] has been developed. This new model has been
successfully applied for alkali-halide salts in aqueous and mixed solvent systems and has the capability
to predict the partitioning and equilibrium of electrolyte and non-electrolyte systems and also has the
potential to accommodate a wide range of reaction systems and solvents.
In this work, a case study involving the production of 5-hydroxymethylfurfural (HMF) from biomass in a
biphasic system is used to show application of the framework. The implementation of the model for
improved and innovative design of system will be demonstrated.
References
[1] A. Anantpinijwatna, G. Sin, J. P. O’Connell, and R. Gani, “A Framework for the Modelling of Biphasic
Reacting Systems,” Comput. Aided Chem. Eng., vol. 34, pp. 249–254, 2014.
[2] S. H. Kim, A. Anantpinijwatna, J. W. Kang, M. Sales-Cruz, and R. Gani, “Application of New Electrolyte
Model to Phase Transfer Catalyst (PTC) Systems,” Comput. Aided Chem. Eng., vol. 37, pp. 701–706, 2015.

PPEPPD 2016
th
Solubility of Flavoniods in Natural Deep Eutectic Solvents
Ning Tang and Weidong Yan*

Department of chemistry, Zhejiang University, Hangzhou 310027, China
*Corresponding author: yanweidong@zju.edu.cn
Scientific topic: Environment, sustainability and risk management
Keywords: Solubility, Flavoniods, Natural deep eutectic solvents
Abstract
Solvens occupy a strategic status in the area of green chemistry. As is known to all, common organic
solvents have a negative influence on the environment due to their inherent toxicity and high volatility.
Over the past two decades, with highly expectation to replace common organic solvents, room
temperature ionic liquids(RTILs) have gained enormous attention particularly in the field of catalysis,
electrochemstry, drug delivery and biocatalytic process[1]. However, many reports have pointed out the
potential toxicity and very poor biodegradability of most ILs[2]. These drawbacks together with the high
price of common ILs unfortunately hamper their appplication on a real chemistry industry. A new kind of
solvents natural deep eutectic solvents (NADES) was found recently. NADES not only share the same
advantages with ionic liquids(ILs), but also fully follow green chemistry principles such as low toxity,
sustainability, biodegradability and cheap[3]. In this study, different combinations of natural ionic liquids
or deep eutectic solvents from natural products(NADES) were made through vacuum evaporating
method[4] for measuring the solubility of flavoniods. The solubilities of several flavoniods in natural
deep eutectic solvents (NADES) were determined by an analytical method using high-performance liquid
chromatography (HPLC). This study reveals the potential of NADES for applications involving
extraction of flavoniods from natural resources.
References
[1] A. Paiva, R. Craveiro, I. Aroso, M. Martins, R. L. Reis, A. R. C. Duarte “Natural deep eutectic solvents–
solvents for the 21st century” ACS Sustainable Chemistry & Engineering, 2014, 2: 1063-1071.
[2] N. V. Plechkova, K. R. Seddon “Applications of ionic liquids in the chemical industry” Chemical Society
Reviews, 2008,37: 123-150.
[3] Q. Zhang, K. D. O. Vigier, S. Royer, F. Jérôme “Deep eutectic solvents: syntheses, properties and applications”
Chemical Society Reviews, 2012, 41: 7108-7146.
[4] Y. Dai, J. van Spronsen, G. J. Witkamp, R. Verpoorte, Y. H. Choi “Natural deep eutectic solvents as new
potential media for green technology” Analytica chimica acta, 2013,766: 61-68.

PPEPPD 2016
th
Solubilities of Naringin Dihydrochalcone in Pure Solvents and Mixed

Solvents at Different Temperatures
Ning Tang and Weidong Yan *

Department of chemistry, Zhejiang University, Hangzhou 310027, China
*Corresponding author: yanweidong@zju.edu.cn
Keywords: Solubility, Naringin dihydrochalone, Solvents, UNIQUAC
Abstract
Naringin dihydrochalcone (naringin DC) is an intense sweetener and a strong antioxidant with potential
applications in many food and pharmaceutical products [1]. However, the poor solubility and stability of
naringin DC in aqueous systems at room temperature severely limits its applications in these areas [2].
The solubility of naringin dihydochalone was quantified in water, ethyl acetate, binary solvent mixtures
of metanol + water and ethanol + water by a synthetic method. The experimental data were correlated
with an Apelblat equation, UNIQUAC model and Abraham solvation equations [3].
References
[1] S. J. Surana, S. B. Gokhale, R. A. Rajmane, R. B. Jadhav “Non-saccharide natural intense sweeteners. An
overview of current status” Natural Product Radiance,2006, 5: 270-278.
[2] L. Chebil, C. Humeau, J. Anthoni, F. Dehez, J. M. Engasser, M. Ghoul “Solubility of flavonoids in organic
solvents” Journal of Chemical & Engineering Data, 2007, 52: 1552-1556.
[3] M. H. Abraham, R. E. Smith, R. Luchtefeld, A. J. Boorem, R. Luo, W. E. Acree “Prediction of solubility of

drugs and other compounds in organic solvents” Journal of Pharmaceutical Sciences, 2010, 99: 1500-1515.

PPEPPD 2016
th
Classical Density Functional Theory for Liquid-Fluid Interfaces using

modified iSAFT and the heterosegmented GC-PC-SAFT Equation of State
Jonas Mairhofer*, Joachim Gross

*Corresponding author: mhofer@itt.uni-stuttgart.de
Keywords: classical density functional theory, statistical associating fluid theory (SAFT), interfacial
tension, surfactants
Abstract
Liquid-fluid interfaces play a determining role in many technical applications. The properties of these
inhomogeneous systems are strongly influenced by surfactants. Surface-active substances consist of
distinct functional groups with opposing chemical properties. In order to study the effect of such
substances on interfacial properties, detailed knowledge of the distribution and orientation of these
molecules at the interface is necessary.
Classical density functional theory (DFT) has proven to be a suitable framework to predict the
thermodynamic properties such as density profiles and interfacial tensions of inhomogeneous systems.
We present a DFT based on modified interfacial SAFT [1] and the heterosegmented group contribution
(GC) PC-SAFT equation of state [2]. The Helmholtz energy functional comprises a hard-sphere
contribution [3], chain formation [1], dispersion [2] and association [4]. With this DFT formalism we are
able to determine the density profiles of single functional groups of real components across liquid-fluid
interfaces and, therefore, study the local assembly of molecules like surfactants at the interface. The DFT
approach predicts interfacial tensions of pure components and multicomponent mixtures in good
agreement with experimental values.
References
[1] S. Jain, A. Dominik, W. G. Chapman “Modified interfacial statistical associating fluid theory: A perturbation
density functional theory for inhomogeneous complex fluids” The Journal of Chemical Physics, 127: 244904, 2007.
[2] J. Gross, O. Spuhl, F. Tumakaka, G. Sadowski “Modeling Copolymer Systems Using the Perturbed-Chain
SAFT Equation of State” Industrial & Engineering Chemical Research, 42: 1266-1274, 2003.
[3] R. Roth, R. Evans, A. Lang, G. Kahl “Fundamental measure theory for hard-sphere mixtures revisited: the
White bear version” Journal of Physics: Condensed Matter, 14: 12063-12078, 2002.
[4] A. Bymaster, W. G. Chapman, “An iSAFT Density Functional Theory for Associating Polyatomic Molecules”
The Journal of Physical Chemistry B, 114: 12298-12307, 2010.
Acknowledgements
Financial support of EU project NMP4-SL-2013-604271 “MODENA” is gratefully acknowledged.

PPEPPD 2016
th
Enhanced Leaching Stability of Protein Adsorbed onto Mesoporous materials

with Large Pore Size: a Case in Mesoporous Titania Fibers
Chang Liu*1,2, Yanhua Guo1, Qiliang Hong1, Haijuan Zhang1, Yihui Dong1, Liangliang Huang2, Xiaohua Lu1
1
College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, China
2
School of Chemical, Biological & Materials Engineering, University of Oklahoma, Norman, 73019, United States
*Corresponding author: ChangLiu@njtech.edu.cn
Scientific topic: According to the Conference topics list
Keywords: Mesoporous titania fibers; Bovine serum albumin; Leaching stability; Pore size effect;
Microcalorimetry
Abstract
Mesoporous titania fibers with different pore size were synthesized from layered potassium titanates and
used for bovine serum albumin (BSA) immobilization. It was found that the leaching stability of BSA on
mesoporous titania fibers at isoelectric point increased with pore size in range of 7-30nm. SEM, XRD,
FTIR and N2 Adsorption-desorption isotherm were used to characterize mesoporous titania fibers before
and after BSA adsorption. Adsorption heat of BSA on mesoporous titania fibers was determined by
isothermal microcalorimetry. It was found that BSA molecules were adsorbed onto mesoporous titania
fibers by single layer or multilayer mode, depending on pore size. With increment of heating
temperature, pore size and crystallinity of mesoporous titania fibers increased and hydroxyl group
content on them decreased. Therefore, for BSA molecules which were adsorbed onto mesopores directly,
there are stronger hydrophobic interaction between BSA and mesoporous titania fibers with larger pore
size, which results into bigger adsorption heat. In addition, for BSA molecules which were adsorbed onto
mesopores indirectly, their high adsorption stability is probably due to aggregation and nucleation of
BSA onto mesoporous titania fibers. This work supplied us a new way to enhance stability of protein
onto mesoporous materials with large pore size.
Acknowledgements
This work was supported by Chinese MOST 973 project (2013CB733501), National Natural Science Foundation
of China (21136004, 21476106) and the Priority Academic Program Development of Jiangsu Higher Education
Institutions (PAPD). We thanks Mr. Kiros Hagos to help us to revise and improve the manuscript.

PPEPPD 2016
th
Transport Properties in Ternary Liquid-Liquid systems
Marius Krapoth1, Andres Kulaguin Chicaroux1 and Tim Zeiner1*

1
Faculty of Bio-and Chemical Engineering/ Laboratory of Fluid Separations, TU Dortmund, Germany
*Corresponding author: tim.zeiner@bci.tu-dortmund.de
Keywords: Density Gradient Theory, Extraction, Interfacial Properties, Diffusion
Abstract
In chemical engineering extraction plays a crucial role for the purification of products ranging from bulk
products to biopharmaceuticals. For the extraction, the mass transfer of the target product across the
interface is essential as it determines the residence time and so the dimensions of the extraction unit. The
nature of the interface between two fluids has been the subject of science since Young, Laplace and
Gauss in the 1800 [1]. All three have the assumption of an interface between two fluids as a surface of
zero thickness. On this surface there would be unsteadiness in all physical properties. The idea of an
interface with a non-zero thickness was developed in detail by Lord Rayleigh and van der Waals
proposing gradient theories for the interface based on thermodynamic principles [1]. Based on the ideas
of the gradient theory by Van der Waals, Cahn and Hilliard developed the density gradient theory
(DGT), which can be used to calcualte interfacial properties in equilibrium and the mass transfer across
the interface in non-equilibrium [2]. In contrast to other mass transfer models, the thermodynamics can
be directly considered by the inclusion of the Helmholtz free energy in the DGT. Up to now the DGT
was used in binary system for the calculations of the mass transfer across the interface [3].
In this work this approach was expanded to ternary mixtures. Moreover, the mass transfer across the
interface is experimentally investigated by a Nitsch-Cell [4]. One investigated ternary system was the
system acetone-toluol-water. By the use of DGT to model the interfacial mass transfer of acetone across
the interface, the results were found in good agreement with experimental data. To model the mass
transfer, concentration independent diffusion coefficients were found. Next to this system, the mass
transfer of the phase forming components in an aqueous two-phase system consisting of dextran and
poylethylenglycol dissolved in water was examined. In this system an “uphill”- diffusion against the
gradient of the chemical potential could be observed and modelled by the DGT in non-equilibrium. In
this contribution the differences between classical interfacial mass transfer models and the DGT are
discussed and the results of the mass tranfer calculations by the DGT are compared to experimental data
for the first time.
References
[1] D. M. Anderson, G. B. McFadden, A. A. Wheeler “Diffuse-interface methods in fluid mechanics”, Annual
review of fluid mechanics 1998, 30, 139-165.
[2] J. W. Cahn, J. E. Hilliard “Free energy of a nonuniform system. I. Interfacial free energy”, The Journal of
chemical physics 1958, 28, 258-267.
[3] A. Kulaguin Chicaroux, A. Gorak, T. Zeiner “ Demixing of Behaviour of binary Polymer Mixtures”, Journal of
Molecular Liquids, 2015, 209, 42-49.
[4] Plucinski, P., W. Nitsch, „Mechanism of mass transfer between aqueous phase and water-in-oil microemulsion”
Langmuir, 1994, 10, 371-376.
PPEPPD 2016
th
Vapour-Liquid Equilibria of the Binary System (Cyclohexanone +2-

Heptanone) at Different Temperatures
Jorge Rubio1*, M. Carmen Martín1, Rosa M. Villamañán1, César R. Chamorro1, Jose J. Segovia1
1
TERMOCAL (Thermodynamics and Calibration) Research Group, University of Valladolid, Spain
*Corresponding author: jorge.rubio.gallego@alumnos.uva.es
Keywords: VLE, Cyclohexanone, 2-Heptanone, Separation
Abstract
Cyclohexanone is considered a key intermediate in manufacture process of caprolactam, adipic

acid and other polyamides, furthermore is an important chemical raw material and industrial
solvent. 2-Heptanone, as by-product of cyclohexanone production process, reduces quality of
cyclohexanone due to the difficulty to remove it [1].
Vapour-liquid equilibria were measured for this binary mixture at different temperatures 313.15
K, 333.15 K, 353.15 K and 393.15 K in order to determine the best conditions to separate the
mixture by distillation.
An isothermal total pressure cell was used for the measurements [2]. Experimental values of
total vapor were obtained in two overlapping runs starting from opposite ends of the
composition range. The equilibrium properties measured directly and their uncertainties are:
injected volume ± 0.03 mL, temperature ± 20 mK, and total pressure ± 2·10-4 (P/Pa )+ 5 Pa.
The composition of the liquid phase is close to the overall composition, but it is corrected taken
into account the vapor space of cell and using the virial equation of state.
VLE data were correlated using Margules equation and Wilson model, which were successfully
applied. The results show that this mixture presents an azeotrope that is broken at 393.15 K.
References
[1] Q. Zhao, Y. Huang, K. Tang, J. Li, Y. He "Adsorption of HZSM-5 zeolite on hexanal and 2-heptanone in
cyclohexanone" Journal of the Chinese Ceramic Society, 2011, 39: 1862-1866.
[2] L.M. Lozano, E.A. Montero, M.C. Martín, M.A. Villamañán "Vapor-Liquid equilibria of binary mixtures
containing methyl tert-butyl ether (MTBE) and/or substitution hidrocarbons at 298.15 K and 313.15 K" Fluid Phase
Equilibria, 1995, 110: 219-230.

PPEPPD 2016
th
Improved Property Packages for Process Simulation: Case Studies Using the
CPA EoS for Simulating the Production of Petrochemicals
Nuno M. Pedrosa1, Antonio J. Queimada1, Xiaohong Zhang1, Tim Shire2

KBC Process Technology, 93 Great Suffolk Street, SE1 0BX London, United Kingdom
KBC Process Technology, 4 Cheshire Avenue, Lostock Gralam, CW9 7UA, Northwich, United Kingdom
*Corresponding author: npedrosa@kbcat.com
Scientific topic: Gas and oil downstream and upstream
Keywords: CPA EoS, Glycols, MTBE, Process simulation, Property package
Abstract
Chemical processes must now operate with greater responsibility. Reducing the energy consumption and
providing a higher energy efficiency are the ultimate goals of the industry. To ensure such optimized
performance, the industry needs to identify opportunities for improvement. Such analysis is typically
done using software solutions (process simulators) which need to reproduce the material and energy
balances in the process as accurately as possible.
Inaccurate process simulations can lead to poor process design. One of the pillars of succesful
simulations is to have an underlying property package providing rigorous equilibrium and transport
property calculations in a broad range of temperature, pressure and composition conditions, ideally
covering the conditions used in the process.
Process simulations usually take the Peng-Robinson EoS for phase equilibrium calculations, the Lee-
Kesler model for enthalpies and some other well tested models for transport properties as the default
property package. Having been optimized and tested for decades, the Peng-Robinson EoS is surely a
reasonable choice for any phase equilibrium calculation involving simple hydrocarbons, such as is
typically the case in oil refineries. More difficult simulations involving mixtures where non-ideality is
more pronounced are usually approached by using activity coefficient models such as NRTL or
UNIQUAC, for which pre-defined sets of parameters are required.
In the last three decades a series of equations of state that can deal with more non-ideal solutions have
been proposed, such as SAFT, CPA and GCA, among others. All these contain an extra association term
that can deal with hydrogen bonding and solvation effects and are reasonably natural replacements for
Peng-Robinson for all mixtures containing hydrogen bonding species. Still, some of these models have
only recently become natively available in process simulators such as Petro-SIMTM.
In this work we will investigate two case studies were the CPA EoS is used in process simulation: 1) the
production of methyl-tert-butyl ether (MTBE, an octane enhancer) and 2) the production of glycols.
Simulation data will be compared to plant data and model parameterization and optimization will be
discussed. This work shows that major discrepancies occur when using Peng-Robinson, such as a vapour
phase being present at reactor conditions, where in fact none occurs, and an azeotrope being missed. Use
of CPA natively within simulation allows for better results, more stable simulation, and make simulation
of equipment such as liquid-liquid extraction feasible.
Acknowledgements
The authors would like to thank KBC Process Technology Ltd for supporting this work.

PPEPPD 2016
th
Molecular simulation study of the barrier properties of semi-crystalline

polyethylene
Germain Clavier1,2, Nadège Brusselle-Dupend3, Véronique Lachet1* and Bernard Rousseau2

1
Thermodynamic and Molecular Simulation Department, IFP Energies nouvelles, Rueil-Malmaison, France
2
Physical Chemistry Department, CNRS UMR8000, Université Paris-Sud, Orsay, France
3
Solids Mechanics Department, IFP Energies nouvelles, Rueil-Malmaison, France
*Corresponding author: veronique.lachet@ifpen.fr
Keywords: Molecular simulation, Permeability, Semi-crystalline polyethylene
Abstract
Polymer materials are used in numerous industrial applications where an accurate knowledge of their
barrier properties is required. In oil and gas production, polymers are used to ensure the internal and
external pipe leakproofness. For example, thermoplastic semi-crystalline polymers are located inside
pipes to prevent the penetration of carbon dioxide and hydrogen sulfide, and thus to prevent the corrosion
of the metallic structure. The permeation of these molecules through polymers depends on their solubility
and their molecular diffusivity.
The present work proposes, through the development of a methodology based on molecular simulation
techniques, to link the nanoscale structure of semi-crystalline polyethylene to its barrier properties. In a
first step, the feasibility of modeling at the atomic scale a semi-crystalline polymer is demonstrated [1].
The challenge here is to build realistic models that include explicitly the crystalline regions and the
amorphous regions of the material as well as the interface between these two regions. In a second step,
molecular dynamics and Monte Carlo simulations are performed in order to predict the barrier properties
of the polymer samples. Gas solubilities have been addressed using Monte Carlo simulations in the
osmotic ensemble (imposed number of polymer molecules, imposed penetrant chemical potentials,
imposed temperature and imposed pressure), with the polymer volume allowed to change upon penetrant
sorption. Solubility coefficients obtained for different semi-crystalline polyethylene samples with
different amorphous-crystal interfacial structures are compared with results obtained considering only the
amorphous phase of the material [2]. Penetrant diffusion coefficients have also been estimated using
canonical molecular dynamics (imposed number of molecules, imposed temperature and imposed
volume or strain). The obtained permeability coefficients are compared to available macroscopic data
and a discussion on the influence of the nano-structure of the polymer upon permeability is proposed.
References
[1] S. Pandiyan, B. Rousseau “Factors influencing properties of interfacial regions in semicrystalline polyethylene:
a molecular dynamics simulation study” Polymer, 2013, 54(14): 3586-3593.
[2] P. Memari, V. Lachet, B. Rousseau, “Molecular simulations of the solubility of gases in polyethylene below its
melting temperature”, Polymer, 2010, 51: 4978-4984.

PPEPPD 2016
th
Self-assembly of spherical caps under gravity
John McBride1, Carlos Avendaño1*

1
School of Chemical Engineering & Analytical Sciences, University of Manchester, UK
*Corresponding/Presenting author: carlos.avendano@manchester.ac.uk /
john.mcbride@postgrad.manchester.ac.uk
Scientific topic: Materials
Keywords: self-assembly, Monte Carlo, anisotropic colloids, gravity
Abstract
Self-assembly of colloidal building blocks is one of the most efficient and cost-effective methods to
produce functional materials. During this process, particles spontaneously form ordered structures when
certain conditions are met [1]. Self-assembly strategies to produce functional materials from anisotropic
particles have undergone an unprecedented growth as a result of recent advances in experimental
techniques to fabricate colloidal and nanoparticles of arbitrary shape and well-defined sizes [2,3]. In this
work, we report the self-assembly of spherical caps interacting through short-range repulsive potentials
under the influence of gravity. The particle model consists of hard spheres of diameter σ cut off by a
plane at a height χ, and their geometry is characterized by the aspect ratio χ/σ. This particle model is
based on recent experiments of particles with similar geometry, namely mushroom cap-shaped colloidal
particles, which are systems that can be used for the fabrication of photonic crystals [4-6]. Using Monte
Carlo simulations combined with free energy calculations we observe rich phase behavior as a function
of both the degree of anisotropy, ranging from spherical particles with χ/σ =1 to hemispheres with
χ/σ=1/2, and the strength of the gravitational field. In particular, at high densities we observe clear
regions where stable crystal structures are formed by highly anisotropic particles, and regions where
stable plastic crystals are formed by particles with low anisotropy.
References
[1] G. M. Whitesides and B. Grzybowski, Self-Assembly at all scales, Science, 295, 2418 (2002)
[2] S.C. Glotzer and M. J. Solomon, Anisotropic of building blocks and their assembly into complex structures, Nat.
Mater., 6, 557 (2007).
[3] S. Sacanna and D. J. Pine, Shape-anisotropic colloids: Building blocks for complex assemblies, Curr. Opin.
Colloid Interface Sci., 16, 96 (2011).
[4] E. K. Riley and C. M. Liddell Confinement-controlled self-assembly of colloids with simultaneous isotropic and
anisotropic cross-section, Langmuir, 26, 11648 (2010).
[5] C. Avendaño, C. M. Liddell-Watson, and F. A. Escobedo Directed self-assembly of spherical caps via
confinement, Soft Matter, 9, 9153 (2013).
[6] S. J. Ivell, R.P.A. Dullens, S. Sacanna, D.G.A.L. Aarts, Emerging structural disorder in a suspension of
uniformly dimpled colloidal particles, Soft Matter, 9, 9361 (2013).

PPEPPD 2016
th
Modeling Polyester Polyol Resins and Resulting Extended Chain Structures

with a SAFT-γ Mie Approach
Amulya Pervaje1* and Erik Santiso1
1
Department of Chemical and Biomolecular Engineering, North Carolina State University, USA
*Corresponding author: akpervaj@ncsu.edu
Scientific topic: Fundamentals- Thermodynamics and transport properties (experimental, modeling), Application-
Materials
Keywords: SAFT, polymers, molecular dynamics, coarse-grained, polyester polyol
Abstract
Polyester polyols are polymers containing multiple ester linkages and alcohol end groups, and they are
widely utilized in coatings, adhesives, sealants and as elastomers. The diversity of these polymers stems
from the numerous possibilities of specific acid and diol monomers as well as their wide range of
possible molecular weights. We seek to obtain a fundamental understanding of the thermodynamic
properties arising from different monomer choices and molecular weight distributions through
computational modeling by the SAFT-γ Mie approach [1] with top-down coarse-grained models [2]. We
modeled a polyester polyol resin made from neopentyl glycol (NPG) and isophthalic acid (IPA)
employing the corresponding states correlation for the SAFT-γ Mie EoS [3] to obtain Mie potential
parameters for NPG and IPA beads from relevant experimental data [4]. Molecular dynamics (MD)
simulations in the isothermal-isobaric ensemble (NPT) of NPG-IPA polyester molecules with a
molecular weight distribution comparable to an experimental resin of NPG and IPA polyester polyol
yielded agreement in the values of density and glass transition temperature between simulation and
experiment. In the interest of studying higher molecular weight thermoset structures made from the
polyester polyol resin, we simulated a system with NPG-IPA polyester polyol in a n-butyl acetate solvent
with a reactive species of hexamethylene diisocyanate (HDI) [3]. Bonds between HDI reactive ends and
NPG-IPA polymer alcohol reactive ends were added in an NPT MD simulation with a heuristic scheme
based on the reactive end to end distance. This bond forming process resulted in an extended chain
structure involving the NPG-IPA backbone with HDI incorporated. Investigation into the mechanical
behavior of just the extended chain structure was carried out by monitoring the stress as a response to
different strains. We also validate second-derivative thermodynamic properties by comparison between
simulation and experiments. These results will be useful to model multifunctional monomers effectively
and the subsequent simulation of crosslinked networks.
References
[1] A. Lymperiadis, C. S. Adjiman, A. Galindo, G. Jackson, “A group contribution method for associating chain
molecules based on the statistical associating fluid theory (SAFT-gamma)” The Journal of Chemical Physics, 2007,
127:234903.
[2] T. Lafitte, C. Avendaño, V. Papaioannou, A. Galindo, C. S. Adjiman, G. Jackson, E. A. Müller “SAFT-γ force
field for the simulation of molecular fluids: 3. Coarse-grained models of benzene and hetero-group models of n-
decylbenzene” Molecular Physics: An International Journal at the Interface Between Chemistry and Physics, 2012,
110:11-12, 1189-1203.
[3] A. Mejia, C. Herdes, E. A. Mueller, “Force Fields for Coarse-Grained Molecular Simulations from a
Corresponding States Correlation” Industrial & Engineering Chemistry Research, 2014, 53: 4131-4141.
[4]. Design Institute for Physical Properties, Sponsored by AIChE. (2012). DIPPR Project 801 - Full Version.
PPEPPD 2016
th
Effects of electrostatic correlations on micelle formation
Mirella Simões Santos1, Evaristo Chaulbaud Biscaia Jr. and Frederico Wanderley Tavares1,2*
1
Programa de Engenharia Química/ Instituto Alberto Luis Coimbra de Pó-Graduação e Pesquisa,
Federal Univerisity of Rio de Janeiro, Brazil
2
Escola de Química, Federal Univerisity of Rio de Janeiro, Brazil
*Corresponding author: tavares@eq.ufrj.br
Scientific topic: Surfaces, interfaces and confinement effects.
Keywords: micellization, electrostatic correlations, molecular thermodynamics, surfactants
Abstract
Micelles are structures formed by the self-assembly of surfactants. This phenomenon is known as
micellization and it is fundamental to countless biological and chemical processes. Ionic surfactants are
the most common kind of surfactant used in industries and laboratories. Their applications include
detergents, medicines, personal care products, coating, and lubrication. When salts are added to
surfactant solutions, the micellization can be changed dramatically depending on the kind of electrolyte
used and its concentration [1]. Traditional approaches to model and describe the micellization
phenomena do not take into account electrostatic correlation interactions between ions. It is known that
those interactions can be neglected when dealing with monovalent ions and/or low concentration
electrolyte solutions [1]. However, those interactions should be taken into account for multivalent and/or
highly concentrated electrolytes. Multivalent counterions, e.g. Al3+ and Ca2+, are great promoters of
micelle growth when compared to monovalent counterions such as Na+ with the same ionic strengh.
Therefore, the development of a theory that is able to correctly predict the behavior of surfactant
solutions with salts is key to improving the application of surfactants in industrial processes. Bazant et al.
[2] proposed a simple mean field approach to include electrostatic correlation effects, and here in this
work we coupled it with the well-established molecular thermodynamics approach to describe the
micellization phenomena. From the proposed model, we can obtain the critical micelle concentration
(CMC) of the surfactant solution and information about the size and shape of the formed micelles. The
values of CMC obtained for different ionic surfactants and salts are in good agreement with experimental
data.
References
[1] B. Lukanov; A. Firoozabadi "Specific Ion Effects on the Self-Assembly of Ionic Surfactants”: A Molecular
Thermodynamic Theory of Micellization with Dispersion Forces" Langmuir, 2014, 30:10: 6373-6383.
[2] M. Z. Bazant; B. D. Storey; A. A. Kornyshev "Double layer in ionic liquids: Overscreening vs. crowding"
Physical Review Letters, 2010, 106: 3–6.
Acknowledgements
We thank the Brazilian Agency CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico) for
providing scholarships and for supporting this work.

PPEPPD 2016
th
Modeling of CO2 Solubility in Electrolyte Solutions and Brines Using

Statistical Associating Fluid Theory
Hao Jiang1 Athanassios Z. Panagiotopoulos1 and Ioannis G. Economou2,3*
1
Department of Chemical and Biological Engineering, Princeton University, USA
2
3
National Center for Scientific Research “Demokritos”, Institute of Nanoscience and Nanotechnology, Molecular
Thermodynamics and Modeling of Materials Laboratory, Aghia Paraskeyi, Greece
*Corresponding author: ioannis.economou@qatar.tamu.edu
Scientific topic: Phase Equilibria/Modeling
Keywords: CO2 solubility, electrolyte solution, equation of state
Abstract
Modeling of CO2 solubilities in electrolyte solutions and especially in formation brines is of great
importance to the design of a CO2 geological sequestration process. Previous models [1,2], which
generally require many fitting parameters, focused on the CO2 solubility in single NaCl solution, while
CO2 solubility in mixed electrolyte solutions and brines has not been studied by advanced equation of
state. In this work, statistical associating fluid theory (SAFT) is used to study CO 2 solubilities in single
and mixed electrolyte solutions, as well as synthetic formation brines. The proposed SAFT model
implements an improved mean spherical approximation in the primitive model to handle the ion-ion
electrostatic interactions, using a parameter K to correct the excess energies (“KMSA” for short). [3]
With the KMSA, the proposed model correlates accurately the activity coefficients and liquid densities of
electrolyte solutions including Na+, K+, Ca2+, Mg2+, Cl-, Br-, and SO42- over a wide range of temperature
with only temperature-dependent parameters for the volume of anions. CO2 is modeled as a non-
associating molecule and its solubilities in H2O and single-electrolyte solutions are calculated using
temperature-dependent CO2-H2O and CO2-ion binary interaction parameters. CO2 solubilities in the
mixed electrolyte solutions and brines are calculated accurately, without any additional adjustable
parameters. The proposed SAFT-KMSA model shows great predictive power for the study of CO2
solubilities in mixed electrolyte solutions and brines.
References
[1] N. N. Akinfiev, L. W. Diamond “Thermodynamic model of aqueous CO 2–H2O–NaCl solutions from −22 to
100 °C and from 0.1 to 100 MPa” Fluid Phase Equilibria, 2010, 295: 104-124..
[2] R. Sun, J. Dubessy “Prediction of vapor–liquid equilibrium and PVTx properties of geological fluid system with
SAFT-LJ EOS including multi-polar contribution. Part II: Application to H2O–NaCl and CO2–H2O–NaCl System”
Geochimica et Cosmochimica Acta. 2012, 88: 130-145.
[3] H. Jiang, H. Adidharma. “Study of thermodynamic properties of symmetric and asymmetric electrolyte systems
in mixture with neutral components: Monte Carlo simulation results and integral equation predictions” Molecular
Simulation. 2015, 41: 727-734.
Acknowledgements
This publication was made possible by NPRP grant number 6-1157-2-471 from the Qatar National Research Fund
(a member of Qatar Foundation). The statements made herein are solely the responsibility of the authors. Additional
support was provided by the Office of Basic Energy Sciences, U.S. Department of Energy, under Award DE-
SC0002128, by the Carbon Mitigation Initiative at Princeton University, and by the 7th European Commission
Framework Program for Research and Technological Development for the project “Techno-economic Assessment
of CO2 Quality Effect on Capture, Transport and Storage” (CO2Quest, Project No.: 309102).

PPEPPD 2016
th
Mutually Immiscible Ionic Liquids for the Fractional Extraction of Mixtures

of Water and Ethanol
Oussama Bacha1,2, Abdelmalek Hasseine2, Manuel N. Lugilde1, María C. Castro1, Alberto Arce1,
Héctor Rodríguez1, Ana Soto1*
1
Departamento de Enxeñería Química, Universidade de Santiago de Compostela, E-15782,
Santiago de Compostela, Spain
2
Department of Chemical Engineering, University of Mohamed Kheider, Biskra, Algeria
*Corresponding author: ana.soto@usc.es
Keywords: Ionic liquid, liquid-liquid extraction, water-ethanol separation
Abstract
Ionic liquids, with their appealing set of properties for their utilisation as solvents, have largely
broadened the portfolio of solvents of choice for the development of potentially more sustainable liquid-
liquid extraction processes [1]. This kind of extraction with ionic liquids might represent a favourable
alternative to the energy-intensive strategies currently used for the challenging separation of ethanol and
water in the bioethanol industry [2]. The existence of mutually immiscible ionic liquids enables the
possibility of configuring a fractional extraction system with only ionic liquids acting as solvents [3]. As
a preliminary test of this idea, in this work the mutually immiscible ionic liquids
trihexyl(tetradecyl)phosphonium acetate ([P6 6 6 14][OAc]) and 1-ethyl-3-methylimidazolium acetate
([C2mim][OAc]) were selected to analyse their suitability to carry out the separation of water and
ethanol. For that purpose, the liquid-liquid equilibrium of the quaternary system water + ethanol +
[P6 6 6 14][OAc] + [C2mim][OAc] was determined at 25 ºC and atmospheric pressure. Ethanol was found
to preferentially partition to the [P6 6 6 14][OAc]-containing phase, whereas water partitioned preferentially
to the [C2mim][OAc]-containing phase, yielding good selectivity values (in a mass basis).
References
[1] M. Freemantle, An Introduction to Ionic Liquids, RSC Publishing: Cambridge (UK), 2010.
[2] C. M. S. S. Neves, J. F. O. Granjo, M. G. Freire, A. Robertson, N. M. C. Oliveira, J. A. P. Coutinho,

“Separation of ethanol-water mixtures by liquid-liquid extraction using phosphonium-based ionic liquids”, Green
Chemistry, 2011, 13: 1517-1526.
[3] A. Arce, M. J. Earle, S. P. Katdare, H. Rodríguez, K. R. Seddon, “Mutually immiscible ionic liquids”,
Chemical Communications, 2006, 2548-2550.
Acknowledgements
The authors want to thank Xunta de Galicia (Spain) for support through project GPC2014/026.

PPEPPD 2016
th
The role of structural characteristics of hydroxyapatite-based sorbents for

Hg0
removal: a molecular dynamics approach
Carla L. M. Camargo1, Amanda G. Oliveira1, Neuman S. Resende1*, Vera M. M. Salim1 and Frederico W.
Tavares1,2
1
Programa de Engenharia Química/COPPE, Universidade Federal do Rio de Janeiro, Brazil
2
Escola de Química, Universidade Federal do Rio de Janeiro, Brazil
*Corresponding author: neuman@peq.coppe.ufrj.br
Scientific topic: Processing and Applications
Keywords: hydroxyapatite, crystalline structure, molecular dynamics, mercury
Abstract
Understanding removal mechanisms is a critical point in the study of adsorption processes. Adsorption
efficiency is obviously associated with the type and the strength of adsorbent-adsorbate interactions. The
characteristics of the adsorbent surface, pore structure and crystalline matrix, however, play an important
role in the kinetic of adsorption process. In our previous works [1], transport phenomena effects inside
pores and solid matrix were taken into account in the mathematical modelling of the Hg0 adsorption
process using a hydroxyapatite-based sorbents modified with copper sulphide. Here, the molecular
simulation is used as a tool to interpret the experimental hydroxyapatite (HAp) crystalline structure.
Molecular dynamics (MD) simulations were carried out using LAMMPS code [2] and force field with
parameters proposed by Hauptmann et al. [3] to hydroxypatites. Simulation box are created by
replicating the hexagonal unit cell with 44 atoms in the three dimensions as 4 x 4 x 6 supercells. MD
simulations were performed in the microcanonical (NVE), canonical (NVT), and isothermal-isobaric
(NPT) thermodynamic ensembles. Nosé-Hoover thermostat and Raman-Parrinello barostat were used to
control the temperature and/or pressure. Simulation results to cell parameters and XRD patterns are in
good agreement with experimental XRD patterns of HAp samples. By determining Hg diffusion
coefficient, we speculate the hypothesis of Hg migration into the Hap-solid matrix.
References
[1] C. L. M. Camargo, N. S. Resende, A. G. Oliveira, V. M. M. Salim, F. W. Tavares “Investigation of adsorption-
enhanced reaction process of mercury removal from simulated natural gas by mathematical modeling” Fuel, 2014,
129: 129-137.
[2] S. Plimpton “Fast parallel algorithms for short-range molecular dynamics” Journal of Computational Physics,
1995, 117: 1-19.
[3] S. Hauptmann, H. Dufner, J. Brickmann, S. M. Kast, R. S. Berry “Potential energy function for apatites”
Physical Chemistry Chemical Physics, 2003, 5: 635-639.
Acknowledgements
The authors would like to thank CAPES, CNPq, FAPERJ and Petrobras for the financial support.
PPEPPD 2016
th
Confinement Effect on Chemical Reaction Yield: The Nitric Oxide Dimer

Reaction
Deepti Srivastava1, C. Heath Turner2 and Keith E. Gubbins1

1
Department of Chemical & Biomolecular Engineering, North Carolina State University, USA
2
Department of Chemical & Biological Engineering, University of Alabama, Tuscaloosa, USA
*Corresponding author: dsrivas@ncsu.edu
Abstract
It is well established that confinement within a nano-porous material, such as an activated carbon, carbon
nanotube, or porous oxide can affect reaction yield, reaction rate and even the mechanism of the reaction
[1,2]. These effects arise from the strong intermolecular forces between the various reacting species,
including the activated state, and the pore walls, but are poorly understood.
In this study, we report a molecular simulation study of the effects of confinement within a nanoporous
carbon material on the equilibrium yield of the nitric oxide dimerization reaction, 2NO=(NO)2. This
reaction is chosen for study both because of its importance in atmospheric chemistry and biology, and
because experimental data is available for the effect of confinement within carbon materials. Thus
Kaneko and coworkers [3] have used magnetic susceptibility measurements to determine the equilibrium
yield of the dimer in activated carbon fibers having slit-shaped pores of 0.8 nm width, while Yates and
coworkers [4] have used FTIR spectra to find the yield in single-walled carbon nanotubes of diameter
1.35 nm. At the experimental conditions the yield of dimer in the gas phase in equilibrium with the pore
phase was less than 1 mol %, whereas the yield within the pores was 100 mol % within the accuracy of
the experiment. Monte Carlo simulations reported [5] in 2001 found a large increase in the yield within
slit-shaped pores due to the confinement, but the calculated yield was well below the experimental value.
In this work, we report a Reactive Monte Carlo study of this reaction in slit-shaped carbon pores of
various widths and over a range of temperatures. We examine several approximations made in earlier
molecular simulation studies, in particular the dimensionalities of the molecular partition functions and
the force fields used, and show that the latter have a large effect on the calculated yield.
References
[1] C.H. Turner, J.K. Brennan, M. Lisal, W.R. Smith, J.K. Johnson and K.E. Gubbins, “Simulation of Chemical
Reaction Equilibria by the Reaction Ensemble Monte Carlo Method: A Review”, Molecular Simulation, 34, 119-
146 (2008).
[2] C.H. Turner, J.K. Brennan, J.K. Johnson and K.E. Gubbins, "Effect of Confinement by Porous Materials on
Chemical Reaction Kinetics", Journal of Chemical Physics, 116, 2138-2148 (2002).
[3] K. Kaneko, N. Fukuzaki, K. Kakei, T. Suzuki and S. Ozeki, Langmuir, “Enhancement of NO Dimerization by
Micropore Fields of Activated Carbon Fibers”, 5, 960-965 (1989).
[4] O. Byl, P. Kondratyuk and J. T. Yates, “Adsorption and Dimerization of NO inside Single-Walled Carbon
Nanotubes – An Infrared Spectroscopic Study”, J. Phys. Chem. B, 2003, 107, 4277-4279.
[5] C. H. Turner, J. K. Johnson and K. E. Gubbins, "Effect of Confinement on Chemical Reaction Equilibria: The
Reactions 2NO = (NO)2 and N2+3H2 = 2NH3 in Carbon Micropores", J. Chem. Phys., 114, 1851-1859 (2001).
PPEPPD 2016
th
Investigation of Performane of Different Methods for measuring Equilibruim
Solubility of Carbon Dioxide in Aqueous Alkanolamine Solutions in Low
Loading Range
Ali T. Zoghi 1* ,Azam Najafloo2 , Farzaneh Feyzi2
1
Research Institute of Petroleum Industries, Iran
2
Thermodynamics Research Laboratory, School of Chemical Engineering,
Iran University of Science and Technology, Iran
*Corresponding author: zoghiat@ripi.ir
Scientific topic: Phase Equilibria (experimental)

Keywords: equilibrium, solubility, alkanolamine, experimental, carbon dioxide
Abstract
So far, different methods have been used by researchers for mesearuing the equiriblum solubility of acid gases such
as hydrogen sulfide and carbon dioxide in aqueous alkanolamine solutions. These methods could be calssified into:
a) isochoric method [1-5], b) sampling of liquid phase and titration [6-9], c) NMR analysis of ionic spices in the
liquid phase [10-12], d) measuring pH of the liquid sample [13], d) sampling of liquid or gas pahse and anaylsis by
gas chromatography [14-19]. In the persent work, different methods of measuring solubility of carbon dioxide in
aquoeus N-methyldiethonalamine (MDEA) solutions have been compared from the accuracy and repeatability point
of veiw. The concentration of aquoues MDEA solutions has been fixed equal to 25.73 wt.%. All the mentioned
methods, except NMR and head space gas ghromatography methods, were studied in this work. The experiments
were performed at two temperatures of 313.2 and 348.2 K. All the measurments were repeated two times in order to
check the repeatability of the experimental data. The experimental data that have been already published by Sidi-
Boumedine et al. for equilibruim solubility of carbon dioxide in aqueous MDEA solution [19] is used for
comparison. The obtianed average absolute relative percent deviation (AAD%) at T=313.2 K for isochoric, gas
sample anlysis by GC, liquid sample titration and liquid sample pH measurment are:1.57, 3.06, 22.7 and 37.65,
respectively, and at T=348.2 K the corresponding AAD% values are 2.76, 10.72, 21.26 and 29.42 for loading range
of 0.02 to less than 0.8. In the isochoric method there is no need to take sample from the liquid or the gas phase and
for this reason the error of measurements is reduced. However, it should be mentioned that the effect of liquid
volume change due to absorption of carbon dioxide must be taken into account. Since withdrawal of a sample from
the gas phase change the equilibrium state, sampling from the gas phase could be the source of error when using
gas chromatography method. In titration method, the major source of error is the loss of percipated carbon dioxide
by filteraion and also liquid sample temperature change. In pH measurement, the assumption of pH behavior of
alkanolamine solution by addition of strong sulfuric acid and absorption of carbon dioxide may be the major source
of the observed error. We may conclude that based on the accuracy of equipments and instruments that have been
used in this research, the more accurtae mehod is the isochoric method.
References
[1] J.H. Jones, H.R. Froning, E.E. Claytor, Journal of Chemical & Engineering Data 4 (1959) 85-92.
[2] J.D. Lawson, A.W. Garst, Journal of Chemical & Engineering Data 21 (1976) 20-30.
[3] B. Lemoine, Y.-G. Li, R. Cadours, C. Bouallou, D. Richon, Fluid Phase Equilibria 172 (2000) 261-277.
[4] M.K. Park, O.C. Sandall, Journal of Chemical and Engineering Data 46 (2001) 166-168.
[5] M. Hosseini Jenab, M. Abedinzadegan Abdi, S.H. Najibi, M. Vahidi, N.S. Matin, Journal of Chemical & Engineering Data 50 (2004) 583-
586.
[6] J.I. Lee, F.D. Otto, A.E. Mather, Journal of Chemical & Engineering Data 21 (1976) 207-208.
[7] A. Benamor, M.K. Aroua, Fluid Phase Equilibria 231 (2005) 150-162.
[8] Y.-R. Chen, A.R. Caparanga, A.N. Soriano, M.-H. Li, The Journal of Chemical Thermodynamics 42 (2010) 518-523.
[9] C.-W. Wang, A.N. Soriano, Z.-Y. Yang, M.-H. Li, Fluid Phase Equilibria 291 (2010) 195-200.
[10] S. Bishnoi, G.T. Rochelle, Industrial & Engineering Chemistry Research 41 (2002) 604-612.
[11] W. BOttinger, M. Maiwald, H. Hasse, Fluid Phase Equilibria 263 (2008) 131-143.
[12] P.W.J. Derks, J.A. Hogendoorn, G.F. Versteeg, The Journal of Chemical Thermodynamics 42 (2010) 151-163.
[13] A. Masohan, M. Ahmed, S.K. Nirmal, A. Kumar, M.O. Garg, Indian Journal of Science and Technology 2 (2009).
[14] F.Y. Jou, A.E. Mather, F.D. Otto, Industrial & Engineering Chemistry Process Design and Development 21 (1982) 539-544.
[15] F.-Y. Jou, J.J. Carroll, A.E. Mather, F.D. Otto, The Canadian Journal of Chemical Engineering 71 (1993) 264-268.
[16] F.-Y. Jou, F.D. Otto, A.E. Mather, Journal of Chemical & Engineering Data 43 (1998) 409-412.
[17] V. Ermatchkov, Á.P.-S. Kamps, G. Maurer, Industrial & Engineering Chemistry Research 45 (2006) 6081-6091.
[18] D. Speyer, V. Ermatchkov, G. Maurer, Journal of Chemical & Engineering Data 55 (2009) 283-290.
[19] R. Sidi-Boumedine, S. Horstmann, K. Fischer, E. Provost, W. Furst, J. Gmehling, Fluid Phase Equilibria 218 (2004) 85-94.
Acknowledgements
The authors would like to thank NIGC (National Iranian GasCompany) for the financial support of this research.
PPEPPD 2016
th
Improvement of Transport Properties in Osmotic Processes by

Nanocomposite Membranes
Anderson L. Ohland*, Neuman S. Resende, Vera M. M. Salim, Cristiano P. Borges

Chemical Engineering Program/COPPE, Universidade Federal do Rio de Janeiro, Brazil
*Corresponding author: aohland@peq.coppe.ufrj.br
Scientific topic: Marine and saline systems and processes
Keywords: Cellulose acetate membrane, titanate nanowires, desalination
Abstract
Development of high-performance membranes for use in osmotic processes is thoroughly useful in

systems for water desalination by reverse osmosis and energy generation by forward osmosis, where high
water permeability and salt rejection is preferred. Mixed-matrix membranes are advanced composite
materials where an inorganic phase, usually nanostructured, is dispersed in a polymeric matrix [1] and
these membranes can combine high selectivity of inorganic materials with processability, mechanical
resistance and low cost of polymers [2]. In this study, mixed-matrix membranes were developed for use
in water desalination processes by incorporation of different amounts of titanate nanowires in a cellulose
acetate matrix. Dense membranes were synthesized by solvent evaporation method, using different
amounts of titanate nanowires dispersed by sonication in a polymeric solution of cellulose acetate and
acetone (10%wt.). These membranes were tested by reverse osmosis process, with an operated pressure
of 30 bar and a NaCl feed solution of 2000 mg/L, measuring water permeability and salt rejection.
Scanning electron microscopy presented a dense, uniform membrane formation with a highly dispersed
inorganic phase. Contact angle showed an increase from 48 to 57 (±1.1)º with the highest content of
titanate nanowires (10%wt.), showing that the addition of titanate nanoparticles increase the
hidrophilicity of the polymeric membranes. It was observed an increasing of three times in water
permeability on reverse osmosis tests, from 0.047 to 0.142 (±0.006) L.μm/(h.m..bar) with particle
content in polymer up to 10 % (wt.), while rejection of NaCl dropped from 95.6 (±1.66)% to values
around 65%. The results showed that the additional phase in membrane increase water sorption and
water permeability, but a salt permeability also enhance due to a reorganization of polymeric chains and
reducing of diffusivity resistance, addition to other factors, presenting as a promise application in
forward osmosis, where high water permeability is more needed than high rejections.
References
[1] B. Jung, G. N. B. Baroña, J. Lim, M. Choi “Interfacial polymerization of polyamide-aluminosilicate SWNT
nanocomposite membranes for reverse osmosis” Desalination, 2013, 325: 138-147.
[2] S. Hassanajili, E. Masoudi, G. Karimi, M. Khademi “Mixed matrix membranes based on polyetherurethane and
polyesterurethane containing silica nanoparticles for separation of CO2/CH4 gases” Separation and Purification
Technology, 2013, 116: 1-12.
Acknowledgements
The authors would like to thank CAPES and CNPq for the financial support.
PPEPPD 2016
th
Excess Molar Enthalpies of Deep Eutectic Solvents (DESs) Composed of

Quaternary Ammonium Salts and Glycerol or Ethylene Glycol
Pablo López1, Maria Gonzalez-Miquel2 and Joan F. Brennecke3*

1
Departamento de Ingeniería Química y Ambiental, Universidad Técnica Federico Santa María, Valparaíso, Chile.
2
School of Chemical Engineering and Analytical Science, The University of Manchester, Manchester, M13 9PL,
United Kingdom.
3
Department of Chemical and Biomolecular Engineering. University of Notre Dame, Notre Dame, USA.
*Corresponding author: jfb@nd.edu
Scientific topic: Thermodynamics and transport properties.
Keywords: Deep eutectic solvents, Excess enthalpy, Heat of mixing, Experimental data.
Abstract
Deep Eutectic Solvents (DESs) are composed mixtures of different Lewis or Brønsted acids and bases,
that form liquids at temperatures lower than 100°C. They have low vapor pressures, wide liquid ranges,
low flammability and are frequently considered as alternatives to ionic liquids. However, the main
characteristic of the DESs is the decrease of the melting point relative to the melting points of each
component of the mixture. A common class of DESs are composed of a quaternary ammonium salt and a
metal salt or other hydrogen bond donor (HBD). The mutual interactions between molecules of the
mixture promote a charge delocalization through hydrogen bonding, causing the decrease of melting
point [1]. Mixtures of choline–chloride (a quaternary ammonium salt) and glycerol (a HBD) can be used
to remove the glycerol formed as a byproduct in the production of biodiesel for improved fuel quality
[2]. Also, DESs formed from choline–chloride and glycerol or ethylene glycol (another HBD) have been
studied for removal of residual alkali metals in biodiesel to avoid engine damage [3].
Tetrabutylammonium chloride has been characterized as an alternative salt for DESs mixtures [4]. The
performance of the salt:HBD pairs can be estimated through the excess molar enthalpy of mixing (𝐻 ̃ 𝑒𝑥 ),
because it reflects the mutual interaction between the components of the DES mixture. Excess molar
enthalpies of mixing were measured for the following DESs: {choline-chloride + glycerol}, {choline-
chloride + ethylene glycol}, {tetrabutylammonium-chloride + glycerol} and {tetrabutylammonium-
chloride + ethylene glycol} at 333.15 K and molar ratios Salt:HBD of 1:4, 1:3, 1:2. The measures were
carried in a Setaram C80 calorimeter. Preliminary results show that the systems of {choline-chloride +
̃ 𝑒𝑥 of 3.5 to 5.8 kJ/mol.
ethylene glycol} and {choline-chloride + glycerol} are highly endothermic with 𝐻
References
[1] E. Smith, A. Abbott, K. Ryder “Deep eutectic solvents (DESs) and their applications” Chemical Reviews, 2014,
114: 11060−1108.
[2] A. P. Abbott, P. M. Cullis, M. J. Gibson, R. C. Harris, E. Raven “Extraction of glycerol from biodiesel into a
eutectic based ionic liquid” Green Chemistry, 2007, 9: 868–872.
[3] K. Shahbaz, F. S. Mjalli, M. A. Hashim, I. M. AlNashef “Eutectic solvents for the removal of residual palm
oilbased biodiesel catalyst” Separation and Purification Technology, 2011, 81: 216–222.
[4] F. Mjalli, J. Naser, B. Jibril “Tetrabutylammonium chloride based ionic liquid analogues and their physical
properties” J. Chem. Eng. Data, 2014, 59: 2242−2251.
PPEPPD 2016
th
High-Pressure Vapor + Liquid Equilibria for Binary Systems CO2 + Hexanal

and CO2 + Ethyl 2-Methylbutyrate
Pablo I. López1, Vasco A. Peréz1, Rafael A. Villablanca1, Arturo Bejarano2, and Juan C. de la Fuente1*
1
Laboratorio de Termodinámica de Procesos, Departamento de Ingeniería Química y Ambiental, Universidad
Técnica Federico Santa María, Valparaíso, Chile.
2
Departamento de Ingeniería Química y Bioprocesos, Pontificia Universidad Católica de Chile, Avda. Vicuña
Mackenna 4860, Macul, Santiago, Chile.
*Corresponding author: juan.delafuente@usm.cl
Keywords: Carbon dioxide, Hexanal, Ethyl 2-Methylbutyrate, Experimental data, Modeling.
Abstract
Among other compounds, hexanal and ethyl-2-methyl are relevant substances that define the nature and
quality of fruits flavors and aromas, like in apple juice flavor. Conceptualization, design and modeling of
alternative processes to concentrate fruit essences, as those that use compressed carbon dioxide (CO 2),
require reliable and accurate phase equilibria information.
Isothermal vapor + liquid equilibria was measured for binary systems CO2 + hexanal and CO2 + ethyl 2-
methylbutyrate at temperatures of 313.2, 323.2 and 333.2 K, and at pressures from 2 to 15 MPa. The
measurements were carried in a apparatus with methodology based on a static–analytic method [1]. The
composition of the vapor phase was measured with a gas chromatograph, for liquid phase a gravimetric
method with a cold trap for the phase separation and a wet test meter to measure the CO 2 content was
used. The validation of the experimental data measured was carried out verified a selected
thermodynamic consistency test, and by estimating the combined uncertainties for the reported CO 2
composition for the vapor phase < 0.005 mol/mol, and for the liquid phase < 0.001 mol/mol [2].
Information from literature for data of vapor + liquid equilibria was found for the system CO 2 + hexanal
at 323.2 K, 353.2 K and 383.2 K [3]. Differences between this work and previously reported at 323.2 K
are < 1.2 % in vapor phase, and < 13 % for liquid phase, attributed to the different experimental
methodologies used. For the system CO2 + ethyl 2-methylbutyrate there is no information in literature
about phase equilibria data at high-pressure.
Experimental data was properly correlated using the Peng-Robinson equation state, with the conventional
quadratic mixing rule and two adjustable parameters, and with Wong-Sandler mixing rule [4] with the
Non Random Two Liquid model for the calculation of the excess Gibbs free energy.
References
[1] A. Bejarano, P. I. López, J. M. del Valle, J. C. de la Fuente, “High-pressure (vapour+liquid) equilibria for
ternary systems composed by {(E)-2-hexenal or hexanal+carbon dioxide+water}: Partition coefficient
measurement”, Journal of Chemical Thermodynamics, 2015, 89: 79-88.
[2] R. D. Chirico, M. Frenkel, V. V. Diky, K. N. Marsh, R. C. Wilhoit, “ThermoMLsAn XML-Based Approach
for Storage and Exchange of Experimental and Critically Evaluated Thermophysical and Thermochemical Property
Data. 2. Uncertainties”, Journal of Chemical and Engineering Data, 2003, 48: 1344-1359.
[3] H. Orbey, S.I. Sandler, “Modeling Vapor-Liquid Equilibria, Cubic Equations of State and Their Mixing
Rules”; Cambridge University Press: Cambridge, U.K., 1998.
[4] D. Seredynska, G. Ullrich, G. Wiegand, N. Dahmen, E. Dinjus “High-Pressure Vapor-Liquid Equilibria for
CO2 + Hexanal at (323.15, 353.15, and 383.15) K”, Journal of Chemical and Engineering Data, 2007, 52: 2284-
2287.
Acknowledgements
This work was funded by Chilean agency FONDECYT (Regular project 115-0822). Ana I. González helped setting
up the gas chromatographic analysis, and experimental measurements, her help is greatly appreciated.

PPEPPD 2016
th
Synthesis and Solubility Measurement of Menadione Derivatives, 2-((4-

chlorobenzyl)amino-3-methylnaphtalene-1,4-dione and 2-((4-
chlorophenethyl)amino-3-methylnaphtalene-1,4-dione in Supercritical Carbon
Dioxide
Adolfo L. Cabrera1 , Olga N. Nuñez, Flavia C. Zacconi2, José M. del Valle3 and Juan C. de la Fuente1,*
1
Laboratorio de Termodinámica de Procesos, Departamento de Ingeniería Química y Ambiental, Universidad Técnica Federico Santa María,
Valparaíso, Chile.
2
Facultad de Química, Departamento de Química Orgánica, Pontificia Universidad Católica de Chile, Santiago, Chile.
3
Departamento de Ingeniería Química y Bioprocesos, Pontificia Universidad Católica de Chile, Avda. Vicuña Mackenna 4860, Macul,
Santiago, Chile.
*Corresponding author: juan.delafuente@usm.cl
Keywords: Menadione derivative, 2-((4-chlorobenzyl)amino-3-methylnaphtalene-1,4-dione, 2-((4-

chlorophenethyl)amino-3-methylnaphtalene-1,4-dione, synthesis, solubility, supercritical carbon dioxide
Abstract
Menadione or vitamin K3 (2-methyl-1,4-naphthoquinone) and its derivatives 2-((4-chlorobenzyl)amino-
3-methylnaphtalene-1,4-dione (DM1) and 2-((4-chlorophenethyl)amino-3-methylnaphtalene-1,4-dione
(DM2) are compound with potential biological significance for the human health as well as positive
pharmacological effects [1]. In order to use carbon dioxide (CO2) at supercritical (SC) conditions as a
solvent for insolation and purification of DM1 and DM1 from complex reaction mixtures, data about its
individual solubility in SC-CO2 (molar fraction of solute in CO2-rich phase) as a function of temperature
and pressure, is basic information required to conceptualize, design and model new separation processes
[2]. The synthesis of DM1 and DM2, solid menadione derivatives, were carried out according [3]. The
structures of both solid products were confirmed through Nuclear Magnetic Resonance (NMR) and
Infrared Resonance (IR), its purity was > 70 % molmol-1. Solubilities measurements of each pure solute
in SC-CO2 were accomplished using a dynamic-analytical methodology [4] at three isothermal
conditions, 313.2 K, 323.2 K and 333.2 K. Results indicated that the experimental pressure ranged from
9 MPa to 30 MPa, and values of solute molar fraction were lower than 450·10-6 molmol-1. For both pairs
of solubility data sets the uncertainties (specifically combined expanded uncertainties) were estimated <
150·10-6 molmol-1 [5]. The reliability of the experimental solubility data was verified by using a
thermodynamic consistency test, adapted from tools based on Gibbs-Duhem equation, and a self-
consistency test, based on the semi-empirical model of Mendes-Santiago and Teja [5].
References
[1] M. P. Brun, E. Braud, D. Anotti, O. Mondésert, M. Quaranta, M. Montes, M. Miteva, N. Gresh, B. Ducommun, C.
Garbay, “Desing, synthesis, and biological evaluation of novel naphthoquinone derivatives with CDC25 phosphatase inhibitory
activity”, Bioorganic and Medicinal Chemistry, 2005, 13: 4871-4879.
[2] J. M. del Valle, J. C. de la Fuente, “Supercritical CO2 extraction of oilseeds: Review of kinetic and equilibrium models”,
Critical Review on Food Science Nutrition, 2006, 46: 131-160.
[3] F. C. Zacconi, O. X. Nuñez, Adolfo L. Cabrera, L. M. Valenzuela, J. M. del Valle. J. C. de la Fuente, “Vitamin K
derivatives synthesis, solubility measurement and thermodynamic consistency analysis in SC-CO2”, in preparation.
[4] K. A. Araus, R. I. Canales, J. M. del Valle, J. C. de la Fuente, “Solubility of -carotene in ethanol- and triolein-modified
CO2”, Journal of Chemical Thermodynamics, 2011, 43: 1991-2001.
[5] A. L. Cabrera, A. R. Toledo, J. M. del Valle, J. C. de la Fuente, “Measuring and validation for isothermal solubility data of
solid 2-(3,4-Dimethoxyphenyl)-5,6,7,8-tetramethoxychromen-4-one (nobiletin) in supercritical carbon dioxide”, Journal of
Chemical Thermodynamics, 2015, 91: 378-383.
Acknowledgements
This work was funded by Chilean agency FONDECYT (Regular project 115-0822) and Proyecto Interdisciplina N°
20/2013 (VRI-PUC). Ana I. González helped setting up the gas chromatographic analysis and experimental
measurements, her help is greatly appreciated.
PPEPPD 2016
th
Development of a methodology for the sustainability evaluation of industrial

pharmaceutical processes
Andrea Mio, Paola Posocco, Erik Laurini, Sabrina Pricl and Maurizio Fermeglia*
MOSE Laboratory, Department of Engineering and Architecture (DEA), University of Trieste, Trieste, 34127, Italy
*Corresponding author: Maurizio.fermeglia@units.it
Scientific topic: pharmaceuticals and cosmetics
Keywords: pharmaceutical processes, sustainability, simulation, PSP
Abstract
This work extends a general framework for the prediction of industrial sustainability (Process
Sustainability Prediction –PSP - Framework proposed by Fermeglia et al. [1]) by implementing features
for treating the sustainability prediction of batch pharmaceutical processes. The resulting procedure
allows performing evaluation of different industrial batch plants alternatives using representative
indicators and metrics that cover the three aspects of sustainability: economy, environment and society.
Two kinds of sustainability indicators are used: three-dimensional indicators (3D-indicators) and one-
dimensional indicators (1D-indicators). The methodology proposed by Martins [2], containing 3D-
indicators, has been extended including the concept of time, related to discontinuous processes as
pharmaceutical ones. The methodology takes into account material intensity, energy intensity, potential
environmental impact and potential chemical risk modified by considering the cycle time of batch
reactors. The 3D-indicators are calculated using the results obtained from process simulation coupled
with the toxicological database, containing data from EPA, other sources, and an in-house procedure for
the estimation of toxicological properties based on molecular modelling.
Whenever a more sophisticated evaluation of the impact is needed, one may resort to the evaluation of
2D and 1D-indicators. One relevant 1D indicator is the Waste Reduction Algorithm (WAR) [3].
In this paper, we have modified the original framework by including the time of charge, reaction and
discharge from reactor and the introduction of new chemicals for rinsing for taking into account more
closely the industrial operation in this sector. All algorithms are implemented in a CAPE OPEN standard
methodology able to interact with most process simulation software available on the market. Process data
are extracted from process simulation software, coupled with toxicological data and with a molecular
modelling procedure based on quantum chemistry (COSMO-RS) and quantitative structure properties
relationships for the prediction of toxicological properties.
References
[1] Fermeglia M., Longo G., Toma L., Computer aided design for sustainable industrial processes: specific tools
and applications, AIChE Journal, 55: 1065-1078 (2009).
[2] Martins, A.A., Mata, T.M., Costa, C.A.V., Sikdar, S.K., 2006, Framework for Sustainability Metrics,
American Chemical Society
[3] Cabezas, H., Bare, J.C., Mallick, S.K., 1997, Pollution Prevention with Chemical Process Simulators: The
Generalized Waste Reduction (WAR) Algorithm, Computers and Chemical Engineering, 21, 305-310

PPEPPD 2016
th
Thermodynamic Characterization of Aqueous Mixtures of Amines
Eduardo I. Concepción1* , Daniel Lozano1, M. Carmen Martín1, Miguel A. Villamañán1, Jose J. Segovia Puras1
1
TERMOCAL (Thermodynamics and Calibration) Research Group, Engineering School, University of Valladolid,
Spain
*Corresponding author: eduardo.concepcion1@utp.ac.pa
Scientific topic: Thermodynamics and transport properties (experimental, modelling )
Keywords: CO2-capture, density , dynamic viscosity , heat capacity
Abstract
There is growing concern that anthropogenic carbon dioxide (CO2) emissions are contributing to global
climate change. Therefore, it is critical to develop technologies to mitigate this problem [1]. Absorption
is the most established technique to separate CO2 where amines are commonly used as solvent. Accurate
determination of physical properties of solvents, in wide ranges of pressures and temperatures, is
essential for rational design and optimization of CO2 capture units.
In the present work, thermophysical properties such as density (ρ), dynamic viscosity (η) and heat
capacity (cp), were measured at temperatures from 313.15 K to 393.15 K and pressures from 0.1 MPa to
12 MPa, for aqueous solutions of Monoethanolamine (MEA) and N -methyldiethanolamine (MDEA)
and mass fractions w = 0.30 and 0.40.
Densities were measured using an Anton Paar DMA HPM densimeter [2] with an standard uncertainty of
± 0.7 (kg·m-3) and viscosities by means of a falling body viscometer (stainless steel falling cylinder) [3]
with a relative standard uncertainty better than 2.1 %. An automated flow calorimeter was used for
isobaric heat capacity measurements whose relative standard uncertainties are 1 % [4].
In addition, the experimental data were correlated with different models and the results will be presented
and discussed.
References
[1] J. D. Figueroa, T. Fout, S. Plasynski, H. McIlvried, and R. D. Srivastava, “Advances in CO2 capture
technology-The U.S. Department of Energy’s Carbon Sequestration Program,” Int. J. Greenh. Gas Control,
vol. 2, no. 1, pp. 9–20, 2008.
[2] J. J. Segovia, O. Fandiño, E. R. López, L. Lugo, M. Carmen Martín, and J. Fernández, “Automated
densimetric system: Measurements and uncertainties for compressed fluids,” J. Chem. Thermodyn., vol. 41,
no. 5, pp. 632–638, May 2009.
[3] J. J. S. MANUEL SOBRINO, “Desarrollo de un Viscosímetro de Caída de Cuerpo para Caracterizar

Biocombustibles a alta Presión,” DYNA Ingeniería e Industria, p. Vol. 87, Núm. 4, 2012.
[4] J. J. Segovia, D. Vega-Maza, C. R. Chamorro, and M. C. Martín, “High-pressure isobaric heat capacities
using a new flow calorimeter,” J. Supercrit. Fluids, vol. 46, no. 3, pp. 258–264, 2008.

PPEPPD 2016
th
Group-contribution method for thermal conductivity

using PC-SAFT and entropy scaling
Madlen Hopp1* and Joachim Gross1

1
*Corresponding author: hopp@itt.uni-stuttgart.de
Keywords: thermal conductivity, PC-SAFT, excess-entropy
Abstract
Recent studies showed the impressive accuracy of excess entropy scaling for the calculation of transport
properties [1]. The original form of entropy scaling was proposed by Rosenfeld [2]. It is based on the
logarithmic dimensionless viscosity obtained by using the Chapman-Enskog equations [3]. The
logarithmic dimensionless viscosity shows a monovariable relationship to the excess entropy. This
relationship even holds for molecules with shape anisotropy or hydrogen-bonding interactions. Entropy
scaling enables extrapolations and even predictions of the viscosity of pure substances and mixtures [1].
In this work, we present a new group-contribution approach for the prediction of thermal conductivities
based on entropy scaling. Starting point is the dimensionless thermal conductivity. Several approaches
are evaluated and compared to obtain the dimensionless thermal conductivity since intramolecular
vibrational degrees of freedom in the low density regime cannot be neglected. The excess entropy is
calculated using the PC-SAFT equation of state [4].
The group-contribution method is shown to be in good agreement with experimental data for pure
organic fluids in a wide range of temperature and pressure, such as alkanes, alkenes, branched alkanes,
aldehydes and aromatics. This qualifies the method to be used in product and process design [5]. Finally,
we demonstrate that our method is also a promising tool for the calculation of self-diffusion coefficients.
References
[1] O. Lötgering-Lin, J. Gross, A group contribution method for viscosities based on entropy scaling using the
perturbed-chain polar statistical associating fluid theory, Ind. Eng. Chem. Res., 54 (7942-7952), 2015
[2] Y. Rosenfeld, Relation between the transport coefficients and the internal entropy of simple systems, Phys. Rev.
A, 15 (2545-2549), 1977
[3] J.O. Hirschfelder, C.F. Curtiss, R.B. Bird “Molecular Theory of Gases and Liquids”, 1954
[4] J. Gross, G. Sadowski, Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for Chain
Molecules, Ind. Eng. Chem. Res., 40 (1244-1260), 2001
[5] A. Bardow, K. Steuer, J. Gross, Continuous-Molecular Targeting fort Integrated Solvent and Process Design,
Ind. Eng. Chem. Res., 49 (2834-2840), 2010
Acknowledgements
Financial support of the German Research Councel (Deutsche Forschungsgesellschaft – DFG) through project GR
2948/2-1 is greatly acknowledged.

PPEPPD 2016
th
Experimental study and modeling on the formation of gas hydrates of

methane and CO2 at high pressure
Maria D. Robustillo*, Davi E. Sanches de Menezes, Paula Rocha Ferrador, Thiago Waldowski Ralha, Luis
Fernando Mercier Franco, Pedro de Alcântara Pessôa Filho
1
GEnBio – Bioprocess Engineering Laboratory, Department of Chemical Engineering, Engineering School,
University of São Paulo (USP), P.O. Box 61548, 05424-970, São Paulo, SP, Brazil
*Corresponding author: mrobustillof@gmail.com
Keywords: methane, CO2, gas hydrate, high-pressure calorimetry
Abstract
Low molecular weight gas molecules and water can associate under certain conditions of pressure and
temperature resulting in the formation of solid structures called gas hydrates. The interest in the study of
the mechanisms of formation and dissociation of gas hydrates is growing due to the importance of these
phenomena in various areas comprising flow assurance of gas and crude oil, water purification, capture
and sequestration of CO2, or even also in the possible use of these hydrates as an alternative energy
resource [1]. For all those applications the study of phase equilibrium of CH4, CO2 and water is of a
much concern. Although mixed hydrates of CO2 and CH4 have been extensively studied, there are few
published data on the occurrence of these phenomena in certain circumstances, such as in extreme
conditions of pressure and temperature, and the existing works do not usually provide the compositions
of the gas, hydrate and all fluid phases [2]. This creates problems of reproducibility and can affect
hydrate properties. The objective of this paper is to present new experimental equilibrium data for the
system formed by methane and CO2, the main constituents of natural gas, in different proportions and
pressures above 200 bar based on high-pressure differential scanning calorimetry. The experimental
results for this system were compared with simulations using the Multiflash 6.0 software, which uses the
Cubic Plus Association (CPA) equation of state for liquid and vapor phases and the van der Waals and
Platteeuw model for the hydrate phase [3].
References
[1] E. D. Sloan, C. A. Koh, Clathrate hydrates of natural gases, 3 rd Ed. CRC Press, Taylor and Francis Group, Boca
Raton, Florida, (USA), 2008.
[2] S. Z. S. Al Ghafri, E. Forte, G. C. Maitland, J.J. Rodriguez-Henríquez, J. P. Martin Trusler “Experimental and
Modeling Study of the Phase Behavior of (Methane + CO2 + Water) Mixtures” J. Phys. Chem. B 2014, 118:
14461−14478.
[3] Multiflash for Windows, Version 6.0, Infochem Computer Services Ltd, May 2015.
Acknowledgements
The authors thank the financial support of FAPESP (processes 2014/02140-7 and 2014/25740-0). The help from
members of the laboratories GenBio (USP) is also gratefully acknowledged.
PPEPPD 2016
th
Self-assembly of two-dimensional non-convex platelets
Nikoletta Pakalidou1* and Carlos Avendaño1

Chemical Engineering and Analytical Science1, University of Manchester, United Kingdom
*Corresponding author: nikoletta.pakalidou@manchester.ac.uk
Scientific topic: Molecular and Process Modelling
Keywords: Self-assembly, Anisotropic particles, Molecular Dynamics
Abstract
Self-assembly remains one of the most efficient techniques to fabricate functional structures [1]. It is
well known that the properties of the self-assembled structures are instrinsically dependent on the
properties of the individual particles used for the fabrication [2]. The effect of particle shape in
selfassembly has attracted considerably attention as a result of recent advances in experimental
techniques to fabricate colloidal and nanoparticles of arbitrary shape and well-defined sizes [3]. The
majority of studies have concentrated in determing the densest structures formed by colloidal particles, in
particular of those with convex shapes. However, the self-assembly of non-convex objects is a topic
scantly studied [4-5]. Non-convex particles are particularly appealing as they are in general bad packers
that can be used to fabricate low-density ordered structures. In this work, we present a computational
study of the self-assembly of non-convex platelets confined in a planar interface. Using molecular
dynamics simulations we observe that non-convex platelets exhibit the formation of a large variety of
twodimensional complex ordered structures as a function of the symmetry of the particles. In particular,
the formation of porous crystals is evident when the degree of non-convexity is large enough. We also
demonstrate how the functionalization of the platelets with ligands tethered in specific positions can be
used as a method to induce directional interactions, akin to patchy interactions, which can be used to
enhance the complexity of the phase behavior [6].
References
[1] G. M. Whitesides and M. Boncheva, “Beyond molecules- self-assembly of mesoscopic and macroscopic
components”, Proc. Natl. Acad. Sci. 99, 4769 (2002).
[2] S. C. Glotzer and M. J. Solomon, “Anisotropy of building blocks and their assembly into complex structures”,
Nat. Mater., 6, 557 (2007).
[3] S. Sacanna and D. J. Pine, “Shape-anisotropic colloids: building blocks for complex assemblies”, Curr. Opin.
Colloid Interface Sci., 16, 96 (2011).
[4] J. de Graaf, R. van Roij, and M. Dijkstra, “Dense regular packing of irregular nonconvex particles”, Phys. Rev.
Lett., 107, 155501 (2011).
[5] S. Atkinson, Y. Jiao, and S. Torquato, “Maximally dense packing of two-dimensional convex and concave
noncircular particles”, Phys. Rev. Lett., 86, 031302 (2012).
[6] Q. Chen, S. C. Bae, and S. Granick, “Directed self-assembly of a colloidal kagome lattice”, Nature, 469, 381
(2011).
Acknowledgements
Financial support for this work was been given by the Faculty of Engineering and Physical Sciences of the
University of Manchester (DTA Scholarship).

PPEPPD 2016
th
Database on ionic liquids solubilities in molecular solvents: progress and

prospects
Johan Jacquemin1*, Magdalena Bendová2, Zdeněk Wagner2, Nan Zhao1

1
QUILL Research Centre, Queen’s University of Belfast, UK
2
E. Hála Laboratory of Separation Processes, Institute of Chemical Process Fundamentals, Academy of Sciences of
the Czech Republic, Czech Republic
*Corresponding author: johan.jacquemin@qub.ac.uk
Keywords: Ionic liquids, Liquid liquid equilibrium, Database, Mathematical gnostics
Abstract
Due to an increasing interest in ionic liquids as “green” solvents, the knowledge of their physical and
chemical properties is essential for scientists and engineers designing experiments. Databases provide an
efficient way to store and retrieve data of varied properties.
In our project, a database on mutual solubility of ionic liquids with molecular solvents has been
compiled. A user-friendly web based interface is put into trial run. This online database allows end users
to get reference data with ease. Data selection and screening are carried out using a method based on
mathematical gnostics. More reliable and precise data are recommended among a large number of data
sets to scientists and engineers for free access.
Acknowledgements
The authors gratefully acknowledge the IUPAC Project # 2011-065-3-500.

PPEPPD 2016
th
High-Pressure Viscosity Measurements for the

Hydrofluoroether Fluid HFE-7500
Natalia Muñoz-Rujas1,2*, Jean-Patrick Bazile1, Fernando Aguilar2, Guillaume Galliero1, Eduardo Montero2
and Christian Boned1
1
Laboratoire des Fluides Complexes et leurs Réservoirs, CNRS-TOTAL, UMR 5051,
Université de Pau, BP 1155, 64013 Pau Cedex, France
2
Departamento de Ingeniería Electromecánica, Escuela Politécnica Superior,
Universidad de Burgos, E-09006 Burgos, Spain
*Corresponding author: nmrujas@ubu.es
Keywords: Hydrofluoroethers, Viscosity, Density.
Abstract
Hydrofluoroether fluids (HFEs) have low GWP, zero ozone depletion potential (ODP) and short
atmospheric lifetimes. HFEs are also non-flammable fluids, have very low overall toxicity [1] and have
any significant environmental hazard [2]. Since HFEs are being introduced at the end of the 20 th century,
they have been considered as a good alternative to the CFCs, HCFCs, PFCs and PFPEs replacement.
Their properties and utilities can vary widely so some of them are desirable for refrigerant applications,
others can act as working fluids in Organic Rankine Cycles (ORC), high precision for electronic
components cleaning, light-duty cleaning and heat transfer fluids, etc.
Hydrofluoroether fluid HFE-7500 shares many of the properties of the PFCs and PFPEs, being a
viable option for replace them in a wide range of applications. Their physical properties and boiling point
make it ideal to use it in heat transfer applications; semiconductor manufacturing processes, to cool
semiconductor thermal shock, in electronics cooling, and as an alternative to commonly used fluids in
chemical and pharmaceutical manufacturing processes.
In this work, high pressure viscosity measurements for the fluid HFE-7500 were carried out in
the ranges (0.1 – 100) MPa for the pressure and (293.15 – 353.15) K for the temperature. The
determination of the dynamic viscosity has been carried out with the supplementary high pressure
density measurements in the range (0.1 – 140) MPa for pressure and (293.15 – 393.15) K for the
temperature in order to calculate the high pressure dynamic viscosity data.
References
[1] 3M™ Novec™ Engineered Fluids, http://solutions.3m.com/wps/portal/3M/en_US/3M Novec/Home. (last visit:
09/18/15)
[2] M. Goto, Y. Inoue, M. Kawasaki, A. G. Guschin, L. T. Molina, M. J. Molina, T. J. Wallington, M. D. Hurley
“Atmospheric Chemistry of HFE-7500 [n-C3F7CF(OC2H5)CF(CF3)2]: Reaction with OH Radicals and Cl Atoms
and Atmospheric Fate of n-C3F7CF(OCHO∙)CF(CF3)2 and n-C3F7CF(OCH2CH2O∙)CF(CF3)2 Radicals”
Environ. Sci. Technol. 2002, 36: 2395-2402.
Acknowledgements
N. Muñoz-Rujas acknowledges support for this research to the University of Burgos, for the funding of her doctoral
grant. This work is part of the doctoral thesis of N. Muñoz-Rujas.

PPEPPD 2016
th
Physico-Chemical Properties of Novel Oligoglyme-Substituted Ionic Liquids –

Insight into Very Fine Structure-Property Tuning
Jan Rotrekl1*, Magdalena Bendová1, Zdeněk Wagner1, Jan Storch1, Věra Pěnkavová1, Karel Aim1
1
Institute of Chemical Process Fundamentals CAS, v. v. i., Rozvojová 135, 165 02 Praha 6, Czech Republic
*Corresponding author: rotrekl@icpf.cas.cz
Keywords: Ionic liquids, heat capacity, density, structure-property relationships
Abstract
Ionic liquids (ILs) represent a group of organic salts with an enormous variability in chemical structure
and physico-chemical properties and thus with a broad application potential. However, there is no
application without a proper theoretical base and that is why knowledge of structure-property relations is
needed.
Our present study focuses on a physico-chemical characterization of a new class of ILs with a
bis{(trifluoro-methyl)sulfonyl}imide anion (abbr. bistriflate). In a previous work [1] three isomeric 1-
butyl-3-alkyl-imidazolium bistriflates (where alkyl is pentyl, isopentyl, or cyclopentyl) were studied with
respect to their fine differences in chemical structure. In the present work, the butyl substituent was
replaced by 2-(2-ethoxyethoxy)ethyl and so the group of 1-(2-(2-ethoxyethoxy)ethyl)-3-alkyl-
imidazolium bistriflates was prepared.
To characterize these new chemical species, several properties of pure substances were determined. The
isobaric heat capacities as a function of temperature were measured using a differential scanning
calorimeter. The density as a function of teperature and pressure, and speed of sound as a function of
temperature were measured using vibrating tube densitometers.
Among the many possible applications of ILs, electrochemistry is one of those extensively explored.
Literature reports on some of the benefits resulting from the introduction of an (oligo)ether group, similar
to that studied in this contribution. For this reason the electrical conductivity and viscosity, which are
fundamental for any electrochemical application, were measured too in this work.
Characterization of ILs presented is this work is essential for further studies of these substances, both
from the point of view of basic research and their applications. Besides that, our data provide a fresh
insight into the influence of the very fine tuning of chemical structure on their physico-chemical
properties.
References
[1] Andresová, A.; Storch, J.; Traïkia, M.; Wagner, Z.; Bendová, M.; Husson, P. Branched and cyclic alkyl groups
in imidazolium-based ionic liquids:Molecular organization and physico-chemical properties. Fluid Phase Equilib.
2014,371, 41–49.
Acknowledgements
The authors gratefully acknowledge MEYS funding under grant No. LD141090.

PPEPPD 2016
th
Activity and osmotic coefficients of binary mixtures of NTf2- ionic liquids with
a primary alcohol
Noelia Calvar1, Ángeles Domínguez2, Eugénia A. Macedo1*
1
LSRE-Laboratory of Separation and Reaction Engineering, Associate laboratory LSRE/LCM, Department of
Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, Porto 4200-465,
Portugal
2
Advanced Separation Processes Group, Department of Chemical Engineering, University of Vigo, Campus
Lagoas-Marcosende, 36310 Vigo, Spain
*Corresponding author: eamacedo@fe.up.pt
Scientific topic: Phase Equilibria (experimental, Modeling)
Keywords: osmotic coefficients, activity coefficients, vapor pressures, mixture of ionic liquids,
modeling
Abstract
During the last decade, many studies have been carried out on ionic liquids (ILs), including the
properties of pure ionic liquids as well as of their binary mixtures mainly with organic solvents. Lately,
binary mixtures formed by two ionic liquids are drawing attention, since the combination of ionic liquids
can improve target properties and extend their applicability range. In this context, binary mixtures of ILs
have been studied for liquid-liquid extraction, as solvents for chemical synthesis and especially for
electrochemical applications. The studied properties include density, viscosity, and conductivity, where
the excess properties obtained are generally small, showing the almost ideal behavior of these properties.
Several studies on the thermal behavior of mixtures of two ILs have been also carried out.
In order to analyze the influence of the presence of mixtures of ionic liquids on the interactions present in
binary mixtures with an alcohol, in this work the vapor pressure osmometry (VPO) technique was
employed to determine osmotic and activity coefficients and vapor pressures of systems containing the
primary alcohol 1-propanol and an equimolar mixture of two ionic liquids with the same anion. The
studied mixtures are 1-propanol + EMimNTf2/HMimNTf2 or EMimNTf2/BMimNTf2 or
EMpyNTf2/BMpyNTf2 or EMpyNTf2/HMimNTf2. The results obtained are compared with the behavior
of the mixtures containing the corresponding pure ionic liquids forming the equimolar mixture;
furthermore, the selection of an equimolar mixture of ILs allows to compare the results with their
corresponding intermediate pure component.
The Extended Pitzer model [1] and the Modified Non-Random Two Liquids (MNRTL) equation [2]
were used for the correlation of the experimental osmotic coefficients. These were adopted taking into
account two cations and one anion in the mixtures.
References
[1] K. Pitzer, Activity coefficients in electrolyte solutions, 2nd Ed. CRC Press: Boca Raton, Florida (USA), 1991.
[2] A. Jaretun, G. Aly, “New local composition model for electrolyte solutions: Single solvent, single electrolyte
systems” Fluid Phase Equilib., 1999, 163: 175-193.
Acknowledgements
This work was partially supported by FCT/MEC and FEDER under Programe PT2020 (Project
UID/EQU/50020/2013), and co-financed by QREN, ON2 and FEDER (Projects NORTE-07-0162-FEDER-000050
and NORTE-07-0124-FEDER-0000011), for which the authors are thankful.
PPEPPD 2016
th
Comparison of 15 Alpha Functions for the Peng-Robinson EOS Applied to

Vapor Pressure Calculation
André Young1* and Fernando Pessoa1

1
Departamento de Engenharia Química, Universidade Federal do Rio de Janeio, Brazil
*Corresponding author: andreyoung@ufrj.br
Keywords: Alpha Function, Peng-Robinson, Vapor Pressure
Abstract
Since Peng and Robinson [1] proposed their cubic equation of state in 1976, several attempts were made
to improve its performance and to extend its application to an increasing number of substances.
Considerable part of this work were done in a pursuit for better volumetric estimations, but many authors
have focused only in the vapor pressure calculation, what in great part signifies the proposal of a new
alpha function for the attractive term. There are several works in the literature reviewing and comparing
some of these equations [2,3]. Until now, the preference for cubic equations of state in industry is
evident, due to their excellent results and simplicity. But to guarantee good results for mixtures, it is
important to have a good representation of each pure substance involved and that is why comparison
between different alpha function models are important. In this work, 15 alpha function models were
compared in the estimation of vapor pressure of a large group of compounds with the Peng-Robinson
EOS. The values calculated with the EOS were compared with values obtained with correlations from
the DIPPR 801 database [4]. With these results, it was possible to show which model is more appropriate
for each class of compounds, what is an important information for the development of new alpha
function models.
References
[1] D. Y. Peng, D. B. Robinson “A New Two-Constant Equation of State” Ind. Eng. Chem., Fundam., 1976, 15:
59-64.
[2] J. O. Valderrama “The State of the Cubic Equations of State” Ind. Eng. Chem. Res., 2003, 42: 1603-1618.
[3] L. A. Forero G., J. A. Velásquez J. “The Patel-Teja and the Peng-Robinson EoSs performance when Soave
alpha function is replaced by an exponencial funciton” Fluid Phase Equilibria, 2014, 332: 55-76.
[4] R. L. Rowley, W. V. Wilding, J. L. Oscarson, N. Giles, R. J. Rowley, T. E. Daubert, R. P. Danner, DIPPR®

Data Compilation of Pure Compound Properties, Design Institute for Physical Property Data, AIChE: New York
(USA), 2001.

PPEPPD 2016
th
A Kinetics and Thermodynamic Approach on Gas Hydrate Inhibition via

Pyrrolidinum Based Ionic Liquids and Synergistic Compounds
Tausif Altamash, Fahed Qureshi, Bahman Tohidi, Santiago Aparicio and Mert Atilhan *
Department of Chemical Engineering, Qatar University
*Corresponding author: mert.atilhan@qu.edu.qa
Keywords: Ionic liquids, Gas Hydrates, Synergistic Chemicals, Flow Assurance, Natural Gas Mixture
Abstract
This work deals with the utilization of ionic liquids (ILs) as gas hydrates inhibitors and targets both the
kinetic and thermodynamic inhibition performances when used along with specific synergistic
compounds. Use of methyl ethylene glycol (MEG) and methanol in bulk quantities is a well known
recent practice in oil and gas fields for hydrate prevention and flow assurance, however these chemicals
cause several process and environmental related issues such as chemical disposal after utilization,
corrosion, high flammability and processing cost. ILs are greatly accepted in multiple applications due to
their environmentally friendly nature and tunable properties that also provides alternatives to traditional
inhibitors. 1-Methyl-1-Propylpyrrolidinium cation with different anions (Chloride, Triflate and
dicyanamide) ILs were selected as thermodynamic and kinetic inhibitors for a synthetic quaternary gas
mixture containing: methane (85%), ethane (10%), nitrogen (2.5%) and carbon dioxide (2.5 %).
Furthermore, to enhance the inhibition performance of said ILs Tetra-pentylammonium Bromide,
Vinylcaprolactum and Poly (ethylene Oxide) added as synergants materials to enhance the inhibition
performance. All experiments were performed in hydrate rocking cell assembly from pressures ranging
in 40 to 120 bars. The pyrrolidinium based ILs were able to shift hydrate formation temperature by up to
2 °C and hydrate formation time by 1 hr. The addition of synergents with IL had little effect on the
hydrate formation temperature, but synergents were noted to have significant kinetic effect. Some
synergents were noted to shift the induction time by up to15 hrs.

PPEPPD 2016
th
Transport and Volumetric Properties in Binary Systems of CO2 and
1-Alkyl-3-methylimidazolium Ionic Liquids
Mitsuhiro Kanakubo1*, Takashi Makino1, Tatsuya Umecky1,§, Masaki Watanabe2, and Daisuke Kodama2
1
Research Institute for Chemical Process Technology, National Institute of Advanced Industrial Science and
Technology (AIST), Japan
2
Department of Chemical Biology and Applied Chemistry, College of Engineering, Nihon University, Japan
§
Present Address; Department of Chemistry and Applied Chemistry, Graduate School of Science and Engineering,
Saga University, 1 Honjo-machi, Saga 840-8502, Japan
*Corresponding author: m-kanakubo@aist.go.jp
Scientific topic: Thermodynamics and transport properties (experimental)
Keywords: Ionic liquid, Imidazolium, Carbon dioxide, Density, Viscosity, Electrical conductivity
Abstract
Ionic liquids abosorb a lot of CO2 without intensive volume expansion, which can enhance the
volume-based capacity of CO2, i.e., the molarity scaled solubility of CO2 in such media. Despite the
small volume expansion, the dissolution of CO2 can remarakably improve the transport properties in ILs
as demonstrated in our previous paper [1]. In the present study, we have investigated the effect of CO2
dissolution on electrical conductivity, viscosity, and density in a series of 1-alkyl-3-methylimidazolium
ionic liquids, [Cnmim][X], where n = 4, 6, and 8, and [X]- were [PF6]-, [BF4]- and [Tf2N]-. The partial
molar volume of CO2 was obtained as a function of CO2 mole faction. We also made the Walden plot,
the logarithmic value of molar conductivity versus fluidity (= reciprocal of viscosity), to invesitigate the
relationship between the mobility of ionic species and the macroscopic viscosity of solution. The results
are discussed in terms of interionic and intermolecular interactions between the cation, anion, and CO2 in
the binary systems.
References
[1] T. Umecky, M. Kanakubo, T. Makino, T. Aizawa, A. Suzuki, “Effect of CO2 dissolution on electrical
conductivity and self-diffusion coefficients of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid,”
Fluid Phase Equilib., 2013, 357: 76-79.
Acknowledgements
The authors would thank to Ms. Eriko Niitsuma for her assistance with the measurements. This study was
partially supported by JSPS Grant-in-Aid for Scientific Research (C), Grant No. 15K06551.

PPEPPD 2016
th
Prediction of hydrocarbons solubility in aqueous alkanolamine
solutions with CPA-PR EoS
Tianyuan Wang*, Elise El Ahmar and Christophe Coquelet

Mines Paristech –PSL Research Univercity Centre Thermodynamic des Procédés CTP, 35 Rue Saint Honoré,
77305 Fontainebleau, France
*Corresponding author: tianyuan.wang@mines-paristech.fr
Scientific topic: Thermodynamics modeling, phase equilibria modeling
Keywords: solubility, hydrocarbon, alkanolaimine, prediction, CPA-PR EoS
Abstract
Natural gas can contain acid gas (H2S, CO2) with a concentration up to 50 volume percent. Because of
the lack of heating value of CO2 and the corrosivity of H2S, acid gas is needed to be removed until
acceptable standard. Among different acid gas removal processes, absorption with aqueous alkanolamine
solution is the most established. The knowledge of the solubility of alkanes and aromatics in aqueous
alkanolamine solutions is important in acid gas capture process simulation and design.
In previous works, Cubic-Plus-Association EoS (CPA-SRK) [1] was applied to describe the phase
equilibria of alkanolamine-water [2] and hydrocarbon-water [3] binary systems. In the present work, pure
compounds parameters and binary interaction parameters of these systems were fitted with CPA-PR from
experimental data. Comparing to CPA-SRK, CPA-PR has the same performance.
However, due to the lack of experimental data concerning hydrocarbon-alkanolamine binary systems, it
is impossible to adjust directly their binary interaction parameters. In this study, it is decided to
determine the missing parameter from hydrocarbon-water-alkanolamine ternary systems experimental
data. Because a large number of Vapor-Liquid-Equilibrium, Liquid-Liquid-Equilibrium and Vapor-
Liquid-Liquid-Equilibrium experimental data of these ternary systems are available in recent research
publications (for example: [4], [5]).
Alkanes (methane, ethane, propane, n-butane and n-propane) and BTEX (benzene, toluene,
ethylbenzene, and xylenes) solubility in aqueous alkanolamine (MEA, DEA, and MDEA) have been
accurately predicted for VLE, LLE and VLLE.
References
[1] Kontogeorgis, G. M.; Voutsas, E. C.; Yakoumis, I. V.; Tassios, D. P. An Equation of State for Associating
Fluids. Ind. Eng. Chem. Res. 1996, 35 (11), 4310–4318.
[2] Avlund, A. S.; Eriksen, D. K.; Kontogeorgis, G. M.; Michelsen, M. L. Application of Association Models to
Mixtures Containing Alkanolamines. 20 Years SAFT Equ. StateRecent Adv. ChallengesSymposium 2011, 306 (1),
31–37.
[3] Kontogeorgis, G. M.; V. Yakoumis, I.; Meijer, H.; Hendriks, E.; Moorwood, T. Multicomponent Phase
Equilibrium Calculations for Water–methanol–alkane Mixtures. Fluid Phase Equilibria 1999, 158–160, 201–209.
[4] Mokraoui, S.; Valtz, A.; Coquelet, C.; Richon, D. Mutual Solubility of Hydrocarbons and Amines. GPA
research report. 021 . 2007.
[5] Valtz, A.; Guilbot, P; Richon, D. Amine BTEX Solubility. GPA research report. 971. 2002.
PPEPPD 2016
th
Density, Viscosity, Electrical Conductivity, and CO2 Solubility in Protonic

Amidium Ionic Liquids
Masaki Watanabe1, Daisuke Kodama1*, Takashi Makino2 and Mitsuhiro Kanakubo2
1
Department of Chemical Biology and Applied Chemistry, College of Engineering, Nihon University, Japan
2
Research Institute for Chemical Process Technology, National Institute of Advanced Industrial Science and
Technology (AIST), Japan
*Corresponding author: dkodama@chem.ce.nihon-u.ac.jp
Scientific topic: Thermodynamics and transport properties (experimental), Phase equilibria (experimental)
Keywords: Ionic liquid, CO2 solubility, Density, Viscosity, Electrical conductivity
Abstract
Ionic liquids generally have negligibly small vapor pressure, high thermal and chemical stability, and
show higher solubility for acidic gases such as CO2, NOx and SOx [1, 2]. Because of these characteristics,
ionic liquids can overcome the issues of conventional absorbents, i.e. emission to the atmosphere,
flammability, and high energy consumption. Therefore, ionic liquids attract much attention as a potential
absorbent for gas sweetening, in particular, CO2 capture [3]. In the previous work, we reported CO2
solubility and saturated liquid density in protonic amidium ionic liquid: [DMFH][TFSA], N,N-
dimethylformamidium bis(trifluoromethanesulfonyl)amide [4].
In the present study, we have investigated the effect of alkyl chain length on density, viscosity,
electrical conductivity, and CO2 solubility in the following protonic amidium ionic liquids:
[DMFH][TFSA]; [DMAH][TFSA], N,N-dimethylacetoamidium bis(trifluoromethanesulfonyl)amide;
[DMPH][TFSA], N,N-dimethylpropionamidium bis(trifluoromethanesulfonyl)amide. The density,
viscosity, and electrical conductivity were measured at the temperatures from 273.15 to 363.15 K and
atmospheric pressure. The CO2 solubility in the ionic liquids were measured at 313.15 K without any
analysis of phase compositions. The density and viscosity of [DMAH][TFSA] are higher than those of
the other ionic liquids. The densities were fitted to polynomials, and the viscosities and electrical
conductivities were analyzed with the Vogel-Fulcher-Tammann (VFT) and Litovitz equations. The
Walden plots (double logarithm graph of molar conductivity vs. fluidity (reciprocal viscosity)) for the
ionic liquids were obtained from the present experimental results. The solubilities of CO2 in the present
ionic liquids showed the typical pressure dependence for physical absorption. The molar volume,
volumetric concentration, and volume expansion in the ionic liquid + CO2 mixtures were discussed in
terms of the alkyl chain length on the cations.
References
[1] J. L. Anderson, J. K. Dixon, J. F. Brennecke “Solubility of CO 2, CH4, C2H6, C2H4, O2, and N2 in 1-Hexyl-3-
methylpyridinium Bis(trifluoromethylsulfonyl)imide: Comparison to Other Ionic Liquids” Acc. Chem. Res., 2007,
40: 1208-1216.
[2] J. Kumełan, A. P.-S. Kamps, D. Tuma, G. Maurer “Solubility of the Single Gases Carbon Monoxide and
Oxygen in the Ionic Liquid [hmim][Tf2N]” J. Chem. Eng. Data, 2009, 54: 966-971.
[3] M. Kanakubo “CO2 separation and recovery technology by physical absorption using ionic liquids” (Chapter 6,
pp. 125-144); in “CO2 separation, recovery, and storage technology”, NTS (Tokyo), 2009.
[4] D. Kodama, M. Kanakubo, M. Kokubo, T. Ono, H. Kawanami, T. Yokoyama, H. Nanjo, M. Kato “CO 2
absorption properties of Brønsted acid–base ionic liquid composed of N,N-dimethylformamide and
bis(trifluoromethanesulfonyl)amide” J. Supercrit. Fluids, 2010, 52: 189-192.
Acknowledgement
This study was supported by JSPS Grant-in-Aid for Scientific Research (B) 26289293.

PPEPPD 2016
th
Effect of Molecular Topology on Hydrocarbon Surfactant Performance
Jennifer A. Clark1*, Mariah Ritz1, and Erik E. Santiso1

1
Chemical and Biomolecular Engineering, North Carolina State University, United States
*Corresponding author: jaclark5@ncsu.edu
Specific topic: Surfaces, interfaces, and confinement effects
Keywords: Surfactants, Topology, Surface tension, Simulation, Coarse-graining
Abstract
In the endeavor to retrieve the remaining oil left after traditional oil extraction methods, CO2
foam has proved to be an effectual aid. Presently, some of the best-performing surfactants
known for water/CO2 systems are fluorocarbon surfactants, but they are expensive and harmful
to the environment, which limits their applicability. In an effort to find alternatives, hydrocarbon
analogues have been synthesized, but shown to be less effective than their fluorocarbon
counterparts. However, it has been shown that the topology of the tail group is a critical
parameter in determining their performance for this system.
Here, we utilize coarse-grained molecular dynamic simulations to explore a greater breadth of
tail group structures, in an attempt to gain greater insight into the topological influence of
relevant physical properties in CO2 foam. We chose a Mie potential with parameters taken from
the literature fitted to closely match the experimental surface tension and density. We assess the
performance of the surfactant based on how much it decreases the surface tension of water/CO2
interfaces, as well as the critical surface adsorption. These results will be used in later studies to
assess the effect of different tail group chemistries on surfactant performance for these systems.
Acknowledgements
ACS-PRF grant #55801-DNI6

PPEPPD 2016
th
A Group-Contribution Method for the Calculation of Transport Properties

using PCP-SAFT and Entropy Scaling
Oliver Loetgering-Lin1*, Madlen Hopp1, Joachim Gross1
1
Institute of Thermodynamics and Thermal Process Engineering, University of Stuttgart,
Pfaffenwaldring 9, 70569 Stuttgart, Germany
*Corresponding author: loetgering@itt.uni-stuttgart.de
Keywords: Viscosity, Thermal conductivity, Self-Diffusion, Entropy
Abstract
The accurate representation and prediction of transport properties is an important prerequisite for process
design. An elegant way to capture transport properties in one unified framework is the entropy scaling
approach, originally introduced by Rosenfeld in 1977 [1]. Rosenfeld showed by molecular simulations
that the viscosity, thermal conductivity as well as self-diffusion of spherical particles are directly linked
to the residual entropy. Subsequent studies showed that the entropy scaling approach is also accurate for
more complex systems. Molecular systems like Lennard-Jones chains or n-alkanes show a component
specific, though, still monovariable scaling behaviour [2, 3].
In this work we present a framework to capture the viscosity, the thermal conductivity as well as self-
diffusion of real systems applying a group contribution approach and a predictive PCP-SAFT equation of
state [4]. Predicted viscosities of various pure substances (non-polar, polar and hydrogen-bonding),
binary as well as multicomponent mixtures are in good agreement with experimental data. The thermal
conductivity has contributions from interal degrees of freedom that prevent a naive application of the
entropy scaling. We describe approaches to capture the low-density limit and assess the theory to
experimental data. Additionally first results of predicting self-diffusion coefficients are presented.
References
[1] Y. Rosenfeld “Relation between the transport coefficients and the interal entropy of simple systems” Physical
Review A, 1977, 15: 2545-2549.
[2] G. Guillaume, C. Boned “Thermal conductivity of the Lennard-Jones chain fluid model” Physical Review E,
2009, 80: 061202.
[3] T. Goel, C. N. Patra, T. Mukherjee, C. Chakravarty “Excess entropy scaling of transport properties of Lennard-
Jones chains” The Journal of Chemical Physics, 2008, 129: 164904.
[4] J. Gross, G. Sadowski “Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for Chain
Molecules” Industrial & Engineering Chemistry Research, 2001, 40: 1244-1260.

PPEPPD 2016
th
Multiscale simulations of protein adsorption
Jian Zhou*
School of Chemistry and Chemical Engineering, South China University of Technology,
Guangzhou 510640, P. R. China
*Corresponding author: jianzhou@scut.edu.cn
Keywords: protein adsorption, molecular simulation, protein orientation, multiscale
Abstract
Protein adsorption plays an important role not only in a wide range of basic biological processes but also
in many applications such as protein chromatography, drug delivery on solid substrates, biosensors,
biofuel cells and biomaterials. For these processes and applications, one key issue is the orientation of
adsorbed proteins on surfaces. Controlled antibody adsorption orientation on surfaces is necessary to
ensure that their active sites are away from the surface and accessible to bulk solution for immunoassay
applications. For biofuel cell applications, to enable fast ET, adsorbed cytochrome c should have an
orientation with the heme ring close and perpendicular to surfaces. Another key issue that determines the
activity of adsorbed proteins is their conformation (i.e., how the conformation of the adsorbed protein
resembles that of its native state). In this work, the protein orientation and conformation on charged
surfaces are investigated by a hierarchical approach, i.e., studied by colloidal, coarse-grained and all-
atom models. Parallel tempering Monte Carlo and molecular dynamics simulations are used. Effects of
surface charge density and sign, and solution ionic strength are examined in our simulations. Simulation
results show that van der Waals and electrostatic interactions codetermine the orientation of adsorbed
proteins. It is found that the electric dipole and hydrophobic dipole of adsorbed proteins play important
roles in determining the protein orientation on charged and hydrophobic surfaces.
References
[1] J. Liu, C.Y. Liao, J. Zhou. Langmuir, 2013, 29:11366-11374.
[2] Y. Xie, C.Y. Liao, J. Zhou. Biophys. Chem., 2013, 179:26-34.
[3] C.Y. Liao, Y. Xie, J. Zhou. RSC Advances, 2014, 4:15759-15769.
[4] G.B. Yu, J. Liu, J. Zhou. J. Phys. Chem. B, 2014, 118:4451-4460.
[5] C.Y. Liao, J. Zhou. J. Phys. Chem. B, 2014, 118:5843-5852.
[6] C.W. Peng, J. Liu, D.H. Zhao, J. Zhou. Langmuir, 2014, 30:11401-11411.
[7] J. Liu, G.B. Yu, J. Zhou. Chem. Eng. Sci., 2015, 121:331-339.
[8] D.H. Zhao, C.W. Peng, J. Zhou. Phys. Chem. Chem. Phys., 2015, 17:840-850.
[9] G.B Yu, J. Liu, J. Zhou. AIChE J, 2015, 61:2035-2047.
[10] C.W. Peng, J. Liu, J. Zhou. J Phys. Chem. C, 2015, 119:20773-20781.
[11] J. Liu, C.W. Peng, G.B. Yu, J. Zhou. Langmuir, 2015, 31:10751-10763.
Acknowledgements
This work is supported by National Natural Science Foundation of China (Nos. 21376089, 91334202).

PPEPPD 2016
th
Liquid-liquid equilibriums in aqueous solutions of demixing amines loaded

with gas for CO2 capture processes.
Yohann Coulier1,2, Alexander R. Lowe1,2, J-Y. Coxam1,2, Karine Ballerat-Busserolles1,2*

1
Université Clermont Auvergne, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 CLERMONT-
FERRAND, France
2
CNRS, UMR 6296, Institut de Chimie de Clermont-Ferrand, F-63171 AUBIERE, France
*Corresponding author: karine.ballerat@univ-bpclermont.fr
Scientific topic: phase equilibrium (experimental, modeling) and/or carbon capture and storage
Keywords: liquid-liquid equilibrium; piperidines; LCST; experimental measurements; modeling
Abstract
Carbon Capture and Storage (CCS) is a solid option for CO2 mitigation in the atmosphere. One option is
the CO2 capture from industrial effluents followed by storage in secured sites. Capture processes are
based on selective absorption/desorption cycles of gas in aqueous solutions of amines[1]. The cost of
CO2 treatment with classical alkanolamines is a limitation for the use of this technology. The
development of breakthrough technologies is needed to optimize the separation process. One of the
considered option is the use of a new class of amine : the demixing amines. Those amines are going
through a liquid-liquid separation phase when increasing the temperature[2]. This very interesting
property allows to treat only a part of the absorbent solution for the regeneration of the CO 2 in the
absorption/desorption cycle. The use of such new system induced the perfect knowledge of the liquid-
liquid equilibriums (LLE) in the binary mixtures water + amine, and the influence of the CO2 on such
equilibriums.
The aim of this paper is to present a method developed in the laboratory to study precisely the LLE in the
binary solutions water + amines and the ternary mixtures water+amine+CO2, as a function of the
pressure and the CO2 loading charge. A classical models are also used to correlate LLE data. The amine
chosen are based on piperidine skeleton with different substitution: methyl and ethyl groups on the
piperidine ring. These amines are well known to exhibit such phase transition[3], and a study of the
effect of CO2 on the liquid-liquid equilibrium is of high interest for the process.
References
[1] L. Raynal, P-A. Bouillon, A. Gomez, P. Broutin, Chemical Engineering Journal 171 (2011) 742– 752;
[2] Bouillon, P.-A., M. Jacquin, and L. Raynal, IFP.Energies nouvelles, Editor. (2012)
[3] Y. Coulier, K. Ballerat-Busserolles, L. Rodier, J-Y. Coxam, Fluid Phase Equilibria, 296, 206-212 (2010);
Acknowledgements
This work is realized with the financial support of ANR and NSERC through an international collaborative project
between France and Canada named DACOOTA.

PPEPPD 2016
th
A Simple and Generalized Model to Represent the Vapor-Liquid Equilibria

and the Liquid-Densities of Alkane-Alkane, Alcohol-Alcohol and Ether-
Alkane mixtures
Luis A. Forero G.1* , Elizabeth Rincón P.1 and Jorge A. Velásquez J1.
1
Faculty of Chemical Engineering, Universidad Pontificia Bolivariana, Colombia
Scientific topic: Thermodynamics and transport properties (Experimental and modeling) (Poster)
Keywords: Modified Peng-Robinson EoS, Huron-Vidal mixing rules, Vapor-liquid equilibria, Liquid
densities, Generalized expressions.
Abstract
A simple model based on a modified Peng-Robinson equation of state translated in volume [ref] and the
Huron-Vidal-NRTL mixing rules [2] were developed to describe vapor-liquid equilibria and liquid
densities of alkane-alkane, alcohol-alcohol and ether-alkane mixtures. Generalized expressions in terms
of the critical pressure and the critical temperature of alkanes, alcohols and ethers were developed for the
NRTL binary interaction parameters (A12, A21, 12). The model was proposed employing the
homologous series concept by pairing a family of compounds to another. The parameters of the
generalized expressions were determined minimizing the total absolute relative deviation in bubble
pressure. In total 34 , alkane-alkane mixtures were used to develop the model and the average absolute
deviation in bubble pressure (AADP) estimated is 2.26% and the average absolute deviation in the vapor
phase molar fraction (DY) is 0.002. For alcohol-alcohol 17 mixtures were used with AADP of 2.15% and
DY of 0.005, and for ether-alkane 19 mixtures were used with AADP of 1.44% and DY of 0.004.
Additionally, to validate the models, predictive calculations were made for 15 alkane-alkane mixtures, 18
alcohol-alcohol mixtures and 15 ether-alkane mixtures that included branched compounds. In general,
predictions are adequate and results are similar to those reported in literature by associating models like
the CPA, the SAFT and the GCA equations of state. Finally, using a generalization for the translation
parameter, liquid densities predictions were performed for 39 alkane-alkane mixtures, 10 alcohol-alcohol
mixtures and 15 ether-alkane mixtures and it was found that calculated values are in good agreement
with experimental data. The average absolute relative deviations calculated in liquid density are 2.18%,
1.58% and 1.06% respectively.
References

PPEPPD 2016
th
A Modified Exp-6 Intermolecular Potential Function for Calculating the

Second Virial Coefficients of Pure Gases
Hamed Peyrovedin, Alireza Shariati*

Natural Gas Engineering Department, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz
71345, Iran
*Corresponding author: shariati@shirazu.ac.ir
Scientific topic: Quantum Mechanical Calculations and Force Fields
Keywords: Intermolecular forces, Exp-6 potential function, Statistical thermodynamics
Abstract
In this work, we added the hard-sphere term to the Exp-6 intermolecular potential function in order to
have a more realistic model for determining the values of the second virial coefficients of nonpolar gases
[1-2]. The second virial coefficients were calculated using the proposed hard-sphere Exp-6
intermolecular potential function for 15 nonpolar gases, including alkanes from methane to octane,
benzene, tetrafluoromethane, oxygen, carbon dioxide, fluorine and ethene. The results showed that the
Exp-6 model is improved significantly by introducing the hard-sphere term as the average absolute errors
of all the 341 data points investigated [3] decreased by 52%.
References
[1] J. M. Prausnitz, R. N. Lichtenthaler, E. G. de Azevedo, Molecular Thermodynamics of Fluid-Phase Equilibria,

3rd Ed. Prentice Hall PTR: Upper-Saddle River, New Jersey (USA), 1999.
[2] T.L. Hill, An Introduction to Statistical Thermodynamics, Addison-Wesley, Reading (UK), 1986.
[3] J.H. Dymond, K.N. Marsh, R.C. Wilhoit, K.C. Wong, Virial Coefficients of Pure Gases and Mixtures;
Subvolume A: Virial Coefficients of Pure Gases, Springer-Verlag, Berlin (Germany), 2002.

PPEPPD 2016
th
Development of a transferable force field (TAMie) for phase equilibria of

pure substance and mixtures
Dominik Weidler*, Joachim Gross

Institute of Technical Thermodynamics and Thermal Process Engineering , University of Stuttgart, Germany
*Corresponding author: weidler@itt.uni-stuttgart.de
Keywords: Monte Carlo Simulations, United atom, TAMie, molecular force field, PC-SAFT EOS
Abstract
We present a transferable anisotropic united atom force field (TAMie) based on the Mie potential to
describe phase equilibria of pure substances and mixtures for several chemical groups. In order to
accelerate the optimization of force field parameters we use the PC-SAFT equation of state to locally
approximate results of the molecular simulations. The algorithm leads to swift convergence even for
multidimensional optimizations [1,2]. Our objective function covers the liquid densities and vapor
pressures of pure substances and is minimized simultaneously for several substances of one chemical
group. Our simulations are done in the grand canonical ensemble using Monte Carlo sampling. To
calculate phase equilibria, the histogram reweighting technique is applied.
In this contribution, we summarize the development and results of the TAMie force field. We cover
alkanes, olefines, ethers [2,3], ketones , aldehydes and cyclic substances. We here emphasize mixture
properties and the transferability of the binary interaction parameter kij.
Apart from phase equilibrium properties, we present transport properties and interfacial tension.
References
[1] van Westen, T., Vlugt, T. J. H. & Gross, J., Determining Force Field Parameters Using a Physically Based
Equation of State, J. Phys. Chem. B, 2011, 115, 7872-7880
[2] Hemmen, A. & Gross, J., Transferable Anisotropic United-Atom Force Field Based on the Mie Potential for
Phase Equilibrium Calculations: n-Alkanes and n-Olefins, The Journal of Physical Chemistry B, 2015, 119, 11695-
11707
[3] Hemmen, A.; Panagiotopoulos, A. Z. & Gross, J. Grand Canonical Monte Carlo Simulations Guided by an
Analytic Equation of State—Transferable Anisotropic Mie Potentials for Ethers, The Journal of Physical Chemistry
B, 2015, 119, 7087-7099
Acknowledgements
We acknowledge computational resources of the BwFor Cluster

PPEPPD 2016
th
Separation of n-Propanol and n-Propyl acetate binary azeotropic mixture

using Ionic liquids as entrainers and the Isobaric VLE studies of the system.
Ankitha Theres George, A.R.Balakrishnan*

Department of Chemical Engineering, IIT Madras,India
*Corresponding author: arbala@gmail.com
Keywords: Othmer still, n-propanol, n-propyl acetate, vapour liquid equilibrium, UNIFAC
Abstract
Distillation is a widely accepted technique for the separation of binary liquid mixtures. Separation by
simple distillation is not possible for binary mixtures that form azeotropes. One of the commonly used
methods to separate azeotropes is extractive distillation, which is the process of adding an entrainer to
break the azeotropic point. Ionic liquids on account of their physiochemical properties as well as the
recyclability have been used as a preferred replacement for the conventional entrainers.
The azeotropic system under consideration in the present study is n-propanol - n-propyl acetate mixture.
These compounds which constitute the products/reactants of esterification reaction of n-propanol form a
minimum boiling azeotrope at 94.7°C.
Vapour liquid equilibrium (VLE) measurements of n-propanol and n-propyl acetate in a modified
Othmer still are performed at atmospheric pressure [1]. The most suitable ionic liquids for shifting of
azeotropic composition of the system are selected using COSMO-RS model with suitable combinations
of anions and cations [2]. The isobaric VLE of the system with [EMIM][HSO4] is obtained and
compared with the existing data. The influence of alkyl chain length on the performance of ionic liquids
is also analysed with regard to the previous studies [3]. The effect of polarity is the most important factor
on the behaviour of ionic liquid solvation in alcohols [4]. Experimental VLE data were correlated using
modified UNIFAC model.
References
[1] J. F. Morrison, J. C. Baker, H. C. Meredith, K. E. Newman, I T. D. Waiter,J. D. Massle, R. L. Perry, and P.
Cummings "Experimental Measurement of Vapor-Liquid Equilibrium in Alcohol/Water/Salt Systems",J.Chem Eng.
Data,Vol.35,No.4, 1990
[2] Ana R. Ferreira, Mara G. Freire, Jorge C. Ribeiro, Fernando M. Lopes, Jo~ao ,G. Crespo, and Jo~ao A. P.
Coutinho, "An Overview of the Liquid_Liquid Equilibria of (Ionic Liquid þ Hydrocarbon) Binary Systems and
Their Modeling by the Conductor-like Screening Model for Real Solvents.", Ind. Eng. Chem. Res. 2011, 50, 5279–
5294
[3]J. Dhanalakshmi, P. S. T. Sai and A. R. Balakrishnan, "Study of Ionic Liquids as Entrainers for the Separation of
Methyl Acetate-Methanol and Ethyl Acetate-Ethanol Systems Using the COSMO-RS Model",Ind.Eng.Chem.Res.
2013,52, 16396-16405
[4] P. Susial, D. García-Vera, R. Susial, V. D. Castillo, E. J. Estupiñan, J. C. Apolinario and J. J. Rodríguez-
Henríquez "Experimental Determination of Vapor−Liquid Equilibria Binary Systems of Methyl Acetate, Ethyl
Acetate, and Propyl Acetate with1-Propanol at 0.6 MPa", J. Chem. Eng. Data 2013, 58, 2861−2867
PPEPPD 2016
th
Estimation of Density of Ionic liquids using a Simple and General Group

Contribution Method
Hamid Taherifard and Sona Raeissi*

School of Chemical and Petroleum Engineering, Shiraz University, Iran
*Corresponding author: raeissi@shirazu.ac.ir
Keywords: Ionic liquids, Physical property, Density, Group contribution, Prediction
Abstract
There are a number of methods that have been developed for the prediction of ionic liquid densities,
however, most of them require additional information or are developed for a small variety of ionic
liquids or small ranges of pressures and temperatures [1,2]. For example, equations of states can be used
for the prediction of ionic liquid densities. However, they require knowledge of the critical properties and
acentric factors. By considering that there are no experimental data available for the critical properties of
ionic liquids, it is necessary to rely on methods that can predict these properties, such as the method
developed by Valderama et al. [3]. However, due to the absence of experimental data, the accuracy of
these methods cannot be guaranteed. In this work, we have used 21008 density data points from a vast
variety of ionic liquid families to develop a simple and general group contribution method for the
estimation of liquid densities of various families of ionic liquids, within a wide range of pressures (0.1 to
300 MPa) and temperatures (213 to 473 K). In developing the group contribution model, the idea was to
propose a simple equational form with straight-forward groups which will be easy to use, yet be general
and predicive at the same time. Genetic algorithm was used as the optimization method to obtain a
suitable equational form and the group contribution weights. For this purpose, 9957 data points were
used for training the model and optimizing the group contributions, while the remaining 11051 data
points were used as the test dataset to validate the model. Despite the simplicity of the model and the
groups considered, and by considering that the only necessary information required to use this method is
the chemical structure of the ionic liquid, the results show very high accuracy (an AARD of 1.05% and
an average absolute error of 13.07 kg/m3).
References
[1] J. A. Lazzús, “Estimation of density as a function of temperature and pressure for imidazolium-based ionic
liquids using a multilayer net with particle swarm optimization” Int. J. Thermophys,2009, 30: 883–909.
[2] N. S. Evangelista, F. R. do Carmo, R. S. de Santiago-Aguiar, H. B. de Sant’Ana, “Development of a New

Group Contribution Method Based on GCVOL Model for the Estimation of Pure Ionic Liquid Density over a
WideRange of Temperature and Pressure” Ind. Eng. Chem. Res. 2014, 53: 9506−9512.
[3] J. O. Valderama, P. A. Robles, “criticalproperties, normal boiling tempretures, and acentric factors of fifty ionic
liquids” Ind. Eng. Chem. res, 2007, 46: 1338- 1344.

PPEPPD 2016
th
Thermodynamic model of the urea synthesis process
Alexey L. Voskov1* and Gennady F. Voronin1

1
Department of Chemistry, Lomonosov MSU, Russia
*Corresponding author: alvoskov@gmail.com
Scientific topic: phase equilibria (modelling)
Keywords: urea, synthesis, vapour pressure, chemical equilibrium, thermodynamic modelling
Abstract
Urea is widely used as a fertilizer and produced commercially from ammonia and carbon dioxide by
means of Bazarov reaction. That makes a thermodynamic modeling ot the NH3-CO2-(NH2)2CO-H2O
system an actual task that may be useful for industrial processes optimization. Existing models are often
semi-quantitative [1] or not using some of available thermodynamic data [2].
The thermodynamic model of phase and chemical equilibria in the urea synthesis process has been
developed in this work. It uses the virial equation of state for the gas phase from [3] and UNIQUAC
model for the liquid phase with the next species: NH3, CO2, H2O, urea (NH2)2CO, ammonium carbamate
NH2COONH4 and ammonium hydrocarbonate NH4HCO3.
UNIQUAC model parameters have been estimated from vapour pressure data (NH3-(NH2)2CO, NH3-H2O
and CO2-H2O binary subsystems are included) and carbon dioxide to urea conversion rates. The next
thermodynamic data have been used during this evaluation:
 Gibbs energies of vapourization of NH3 and H2O have been estimated from saturated
vapour pressure (for ammonia – with extrapolation above its critical temperature) and for
ΔfG(CO2) – from Henry constant in water at t=0-2500C
 ΔfG(NH2COONH4, liq) and ΔfG((NH2)2CO, liq) have been calculated from
thermodynamic properties of the compounds (ΔfH0, Cp(T) ΔmH, ΔmCp etc.).
The model is valid for t=140-200°C, n0(NH3)/n0(CO2)=26 and n0(H2O)/n0(CO2)=01 (n0(NH3), n0(CO2),
n0(H2O) are their initial amounts before urea, NH2COONH4 and NH4HCO3 formation). It describes
vapour-liquid equilibria (bubble point, dew point) with the saddle azeotrope and carbon dioxide to urea
equilibrium conversion ratio n((NH2)2CO)/n0(CO2) in the liquid phase (where n((NH2)2CO) is amount of
urea).
References
[1] S. M. Lemkowitz, de Cooker M., P. J. van der Berg “An empirical thermodynamic model for the ammonia –
water – carbon dioxide at urea synthesis conditions” Journal of Applied Chemistry and Biochemistry, 1973, 23(1):
63-76.
[2] M. A. Isla, H. A. Irazoqui, C. M. Genoud “Simulation of a urea synthesis reactor. 1. Thermodynamic

framework” Industrial & Engineering Chemistry Research, 1993, 32(11): 2662-2670.
[3] G. F. Voronin, M. V. Genkin, I. B. Kutsenok “Virial equations of state for gaseous ammonia, water, carbon
dioxide and their mixtures at elevated temperatures and pressures” Russian Journal of Physical Chemistry A, 2015,
89(11): 1958-1970.
PPEPPD 2016
th
Thermodynamic Analysis for the Dehydration of n-Propanol via

Heterogeneous Azeotropic Distillation using Propyl Acetate as Entrainer
Janakey Devi V. K. P, Sai P. S. T and Balakrishnan A. R*

Department of Chemical Engineering, IIT Madras, India
*Corresponding author: arbala@iitm.ac.in
Keywords: Vapor-liquid-liquid equilibrium, ultrasonic homogenizer, NRTL, UNIQUAC, UNIFAC.
Abstract
Heterogeneous azeotropic distillation is a widely popular process in chemical process industries for the
separation of binary azeotropic mixtures into their constituent pure components. It involves the addition
of an entrainer which is partially miscible and forms a heterogeneous azeotrope preferably with one of
the original components. This is a powerful technique which combines several physical phenomena such
as presence of azeotropes and liquid-liquid immiscibilities, and is used widely in industries to enhance
difficult or intractable distillation separations. For the design of heterogeneous azeotropic distillation
columns, a detailed study of the heterogeneous region is crucial to plan the distillation sequence, which
requires experimental vapor-liquid-liquid equilibrium (VLLE) data.
The present study focuses on the investigation of the heterogeneous region of the well known industrially
available azeotropic mixture n-Propanol-Water system using Propyl acetate as entrainer. The VLE data
of the system was generated by means of modified Othmer still and the still is modified using a probe
type ultrasonic homogenizer to account for the heterogeneity in a manner similar to that of Gomis et al.
[1] and Pla-Franco et al [2]. Isobaric vapor-liquid-equilibrium and vapor-liquid-liquid-equilibrium data at
atmospheric pressure have been obtained for the ternary system n-Propanol-water-propyl acetate and the
constituent binary systems. The experimental results have been used to test the accuracy of
thermodynamic models such as NRTL, UNIQUAC and UNIFAC in the calculation and prediction of the
equilibrium data.
References
[1] V. Gomis, F. Ruiz, and J. C. Asensi, “The application of ultrasound in the determination of isobaric vapour –
liquid – liquid equilibrium data,” Fluid Phase Equilib., 2000, 172: 245–259.
[2] J. Pla-franco, E. Lladosa, and S. Loras, “Isobaric Vapor−Liquid−Liquid Equilibria for the Ternary Systems
Ethanol + Water + Propyl Acetate and 1-Propanol + Water + Propyl acetate,” J. Chem. Eng. Data, 2014, 59: 2054–
2064.

PPEPPD 2016
th
Combining predictive models: predictive PCP-SAFT & COSMO-RS
Sebastian Kaminski1, André Bardow1, Kai Leonhard1*

1
*Corresponding author: sebastian.kaminski@ltt.rwth-aachen.de
Scientific topic: quantum mechanical calculations / phase equilibria (modeling)
Keywords: PCP-SAFT, COSMO-RS, property prediction, log-likelihood
Abstract
Two property prediction models are combined to increase overall accuracy. The two models are:
predictive PCP-SAFT [4] based on PCP-SAFT (perturbed-chain polar statistical associating fluid theory)
[1,2,3] and COSMO-RS (conductor-like screening model for real solvents) [5]. Both models are based on
quantum-mechanical calculations for pure components.
In the proposed approach, the properties predicted by the two methods are not just averaged, but
weighted by their respective variances. For this purpose, the predicted information is combined in the
space of PCP-SAFT parameters based on a log-likelihood-function, resulting in a new set of PCP-SAFT
parameters. These new parameters can then be used to calculate properties, even if they are not originally
accessible from COSMO-RS.
Application of the suggested approach to a test set shows that average and maximum prediction errors of
saturation pressure and enthalpy of vaporization estimation could be improved compared to both
predictive models. Density estimations, which COSMO-RS can only calculate at 25°C, stay at the same,
good accuracy of predictive PCP-SAFT throughout the temperature range on average, but maximum
errors are even lowered.
The presented combination provides a practical way to improved predictions of thermodynamic
properties based on quantum-mechanical calculations.
References
[1] J. Gross, G. Sadowski “Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for Chain
Molecules” Ind. Eng. Chem. Res., 2001, 40: 1244-1260.
[2] J. Gross “An Equation of State Contribution for Polar Components: Quadrupolar Molecules” AIChE J., 2005,
51: 2556-2568.
[3] J. Gross, J. Vrabec “An Equation of State Contribution for Polar Components: Dipolar Molecules” AIChE J.,
2006, 52: 1194-1201.
[4] N. van Nhu, M. Singh, K. Leonhard “Quantum Mechanically Based Estimation of Perturbed-Chain Polar
Statistical Associating Fluid Theory Parameters for Analyzing Their Physical Significance and Predicting
Properties” J. Phys. Chem. B, 2008, 112: 5693-5701.
[5] A. Klamt, “Conductor-Like Screening Model for Real Solvents: A New Approach to the Quantitative
Calculation of Solvation Phenomena” J. Phys. Chem., 1995, 99: 2224-2235.
Acknowledgements
This work was performed as part of the Cluster of Excellence “Tailor-Made Fuels from Biomass” funded by the
Excellence Initiative by the German federal and state governments to promote science and research at German
universities.

PPEPPD 2016
th
Experimental determination and modeling of volumetric properties and flash

points of (Fatty Acid ethyl esters + alkanes) binary mixtures.
Kamel Khimeche1, Lakhdar Sahraoui1, Mokhtar Benziane2, Ilham Mokbel3, Abdessalem Mohamed1, Djalal
Trache1
1
Ecole Militaire Polytechnique EMP, BP 17 Bordj-El-Bahri, Alger, Algérie.
2
Ecole Supérieure du Matériel ESM, BP 188 Beau-Lieu, Alger, Algérie.
3
Laboratoire des Sciences Analytiques UMR 5280, Université de Lyon-UCB Lyon 1, 43 Bd du 11 Novembre 1918,
69622 Villeurbanne, France
*Corresponding author: djalaltrache@gmail.com
Keywords: Volumetric properties; Fatty Acid Ethyl Ester (FAEE); group contribution model; flash point.
Abstract
Volumetric properties of binary systems (Fatty Acid Ethyl esters + alkanes), were measured by means of
a Electronic DMA 500 Densimeter at temperatures between 288.15 K and 353.15 K. Flash points of the
same systems mere determined by using flash point apparatus. Flash points were correlated with group
contribution model. The Redlich-Kister polynomial equation was used to fit the excess/deviation
properties. Prediction of excess molar volumes was also done using Prigogine-Flory-Patterson (PFP)
model. Partial molar volumes are in good agreement with calculated values for all the investigated
temperatures and over the whole composition range. Deviations were observed between experimental
and predicted flash points.

PPEPPD 2016
th
Density measurements under pressure for the binary system di-isopropyl

ether + 1-butanol at temperatures up to 353.15 K and at pressures up to 100
MPa.
Adil Srhiyer1,2, José Juan Segovia2, Fernando Aguilar1* and Eduardo Montero1
1
Department of Electromechanical Engineering, Universidad de Burgos, Spain
2
Grupo de Termodinámica y Calibración TERMOCAL, Universidad de Valladolid, Valladolid, Spain
*Corresponding author: faguilar@ubu.es
Scientific topic: thermodynamic and transport properties
Keywords: di-isopropylether, 1-butanol, density, bio-fuel.
Abstract
Tertiary alkyl ethers like di-isopropylether DIPE, having similar properties (e.g., vapour pressures) to
hydrocarbons and the potential to increase the octane number and to decrease the emission of carbon
monoxide, have become important additives for gasoline. The ethers increase the amount of oxygen in
gasoline in order to reduce the CO content in the exhaust gas of automobiles. DIPE, pure or mixed with
alkanols or alkanes, has been recommended as a high octane blending agent for motor gasoline.
Ether + alcohol mixtures are of interest as model mixtures for gasoline in which the ether and the alcohol
act as non-polluting, high octane number blending agents. Despite of this interest, density data of binary
mixtures containing ether + alcohol at pressures other than the atmospheric pressure are very scarce in
the literature. Density of the binary mixture DIPE + 1-butanol have been measured under pressure and
reported in this work using a vibrating tube densitometer. Though density data for pure components is
available [1, 2], no literature date on the density at high temperature and pressure for the same binary
mixture has been found.
Experimental densities for the binary system DIPE + 1-butanol have been measured at, 298.15, 313.15,
333.15 and 353.15 K and at nineteen isobars up to 100 MPa. For each composition, the experimental
values were correlated using a Tait-type equation. Furthermore, the excess molar volume and the
isothermal compressibility were calculated from the density data.
This paper is part of the Doctoral Thesis of A. Shriyer.
References
[1] M. Dakkach, F. Aguilar, F. E. M. Alaoui, E. A. Montero “Liquid density of oxygenated additive 2,4-dimethyl-
3-oxapentane at pressures up to 140 MPa and temperatures from (293.15 to 393.29) K” J. Chem. Thermodyn. 2015,
80: 135–141.
[2] F. Alaoui, E. Montero, J. P. Bazile, M. J. P. Comuñas, G. Galliero, C. Boned “Liquid density of 1-butanol at
pressures up to 140 MPa and from 293.15 K to 403.15 K”, Fluid Phase Equilib. 2011, 301: 131-136.
Acknowledgements
This paper is part of the Doctoral Thesis of A. Shriyer.

PPEPPD 2016
th
Thermodynamic properties of some alkanoic acids as potential energy storage

materials for low temperature applications
Diana Díez-Alcalde1*, Natalia Muñoz-Rujas1, Fernando Aguilar1 and Eduardo Montero1

1
Department of Electromechanical Engineering, University of Burgos, Spain
*Corresponding author: ddiezalcalde@gmail.com
Scientific topic: thermodynamic and transport properties
Keywords: alkanoic acids, heat capacity, heat of melting, viscosity.
Abstract
The linear alkanoic acids (CnH2nO2) constitute a homologous series which is of considerable importance
for industry. At present, they are considered as potential latent heat thermal energy storage compounds,
known as phase change materials (PCM), and can be obtained from underused and renewable feedstock.
This work present a study on thermodynamic and transport properties of several alkanoic acids that are
potential PCM candidates for low temperature energy storage. Nonanoic acid, decanoic acid and
dodecanoic acid show melting points ranging from 283 K to 318 K, wich make them suitable for air
conditioning applications. Heat capacity, enthalpy of melting, as well as density and viscosity of liquid
phase of nonanoic, decanoic and dodecanoic acid at atmospheric pressure are presented in this work.
Results are compared with literature data, which are rather scarce in some properties [1-3].
References
[1] R. C. F. Schaake, J. C. van Miltenburg, C. G. De Kruif, “Thermodynamic properties of the normal alkanoic
acids. I. Molar heat capacities of seven odd-numbered normal alkanoic acids” J. Chem. Thermodyn., 1982, 14: 763-
769.
[2] R. C. F. Schaake, J. C. van Miltenburg, C. G. De Kruif “Thermodynamic properties of the normal alkanoic
acids. II. Molar heat capacities of seven even-numbered normal alkanoic acids” J. Chem. Thermodyn., 1982, 14:
771-778.
[3] K. Y. Liew, C. E. Seng, E. K. Lau “Viscosities of Some Long-Chain Fatty Acids and Their Relationship with
Chainlength” J. Am. Oil Chem. Soc., 1991, 68: 488-492.
Acknowledgements
D. Diez-Alcalde acknowledges support for this research to the Fundación Villalar Castilla y León for the funding of
her doctoral grant 2015. This work is part of the Doctoral Thesis of D. Diez-Alcalde.

PPEPPD 2016
th
Solubility of CO2 in Mixtures of Ionic Liquids and Organic Compounds:

Inducing a Liquid-Liquid Phase Split
Michael J. Lubben1* and Joan F. Brennecke1

1
Department of Chemical and Biomolecular Engineering, University of Notre Dame, USA
*Corresponding author: mlubben@nd.edu
Scientific topic: Separation Techniques – Absorption/Extraction
Keywords: Ionic Liquids, Carbon Dioxide, Separations, Supercritical, Gas Antisolvent
Abstract
Ionic liquids have been shown to be effective extraction solvents for the extraction of aromatic
compounds from aliphatic compounds. The most costly step in an extraction process is typically the
regeneration of the solvent. As an alternative to energy intensive solvent regeneration methods of
distillation or stripping, it has been shown that near supercritical CO2 can be used as an antisolvent gas to
induce a liquid-liquid phase split in some mixtures of ionic liquids and organic compounds [1-6].
Previous work has shown the organic-rich liquid phase contains negligible ionic liquid, making the gas
antisolvent process a very effective separation technique, as CO2 can be removed easily by lowering
pressure.
CO2 solubility has been measured in mixtures of ionic liquids and aromatic compounds, where a
liquid+vapor to liquid+liquid+vapor phase transition is observed. To be an energy efficient process, a
low phase transition pressure with a low composition of CO2 in the liquid phases is desired. Additionally,
the ionic liquid must have high selectivity and capacity for the aromatic in the liquid-liquid extraction
process. Different ionic liquids have been tested to understand what properties are necessary to achieve
desireable phase transition conditions. Properties of excess enthalpy, excess volume, and volume
expansion upon CO2 absorption have been measured to further understand the trends in phase equilibria
that are observed.
References
[1] L. A. Blanchard, D. Hancu, E. J. Beckman, J. F. Brennecke “Green Processing Using Ionic Liquids and CO2”
Nature, 1999, 399: 28–29.
[2] L. A. Blanchard and J. F. Brennecke “Recovery of Organic Products from Ionic Liquids Using Supercritical
Carbon Dioxide,” Ind. Eng. Chem. Res., 2001, 40: 287–292.
[3] A. M. Scurto, S. N. V. K. Aki, J. F. Brennecke “CO2 as a Separation Switch for Ionic Liquid/Organic Mixtures”
J. Am. Chem. Soc., 2002, 124: 10276–10277.
[4] S. N. V. K. Aki, A. M. Scurto, J. F. Brennecke “Ternary Phase Behavior of Ionic Liquid (IL)−Organic−CO2
Systems” Ind. Eng. Chem. Res., 2006, 45: 5574–5585.
[5] B. R. Mellein and J. F. Brennecke “Characterization of the Ability of CO2 to Act as an Antisolvent for Ionic
Liquid/Organic Mixtures” J. Phys. Chem. B, 2007, 111: 4837–4843.
[6] R. I. Canales and J. F. Brennecke “Liquid-Liquid Phase Split in Ionic Liquid + Toluene Mixtures Induced by
CO2” AIChE J., 2015, 61: 2968–2976.
Acknowledgements
University of Notre Dame Incropera-Remick Endowment for Excellence

PPEPPD 2016
th
Understanding the Mechanism of the Protein Cold Denaturation with Fully-

Atomistic Molecular Simulations
Sang Beom Kim1*, Jeremy C. Palmer2 and Pablo G. Debenedetti1

1
2
Department of Chemical and Biomolecular Engineering, University of Houston, USA
*Corresponding author: sangbk@princeton.edu
Keywords: Protein Cold Denaturation, Molecular Simulation, Trp-cage Miniprotein
Abstract
Proteins maintain their unique, three-dimentional structures under their physiological conditions, which
is important for their functionalities. When these conditions are disrupted, for example by either raising
or lowering temperautres, it is well known that the proteins starts unfolding from their compact structures
[1]. The heat denaturations of proteins are well understood with both experiments and simulations, where
the disordred, denatured states are favored due to the increased entropy of the system. The mechanism of
the cold denaturations, however, is still in veil due to the difficulties of studying these systems at cold
temperatures experimentally or computationally. Theories and models have been suggested, but the
simplicities of these models have prevented us from fully understanding the atomistic details of the cold
denaturation. We present the first fully atomistic simulation of the cold denaturation of globular, helical
proteins, using the Trp-cage miniprotein. We explicitly compare the cold and heat denaturations, and our
results show that the cold denaturation occurs locally while maintaining the compact structure and alpha-
helices of the proteins. We find the denatured structures at the cold temperatures allow intrusion of water
molecules to the core of the proteins, which makes the cold denaturation as the enthalpically favorable
process. Our findings are also in agreement with the experimentals studies of cold denaturation.
References
[1] L. Smeller “Pressure–temperature phase diagrams of biomolecules” Biochimica et Biophysica Acta (BBA)-
Protein
Structure and Molecular Enzymology, 2002, 1595: 11-29.
Acknowledgements
The authors acknowledge the financial support from the National Science Foundation. The computations were
performed at the Terascale Infrastructure for Groundbreaking Research in Engineering and Science (TIGRESS) at
Princeton University and the Opuntia cluster of the Center for Advanced Computing and Data Systems at the
University of Houston.

PPEPPD 2016
th
Organic Matter of Shale: Insight from Atomistic Simulations

Lukáš Michalec1,2* and Martin Lísal1,2
1
Laboratory of Aerosols Chemistry and Physics, Institute of Chemical Process Fundamentals of the ASCR, v. v. i.,
Prague, Czech Republic
2
Department of Physics, Faculty of Science, J. E. Purkinje University, Ústí n. Lab., Czech Republic
*Corresponding author: michalec@icpf.cas.cz
Keywords: all-atom molecular dynamics, asphaltene, kerogen, porous structure, resin
Abstract
We used all-atom molecular dynamics simulations to study the structural and physical properties of bulk
organic matter present in shales under typical reservoir conditions (338 K, up to 200 bar). We first built
atomistic models of kerogen (the most abundant part of the organic matter), asphaltenes and resins using
the CVFF force field and structures proposed by Ungerer et al. [1, 2]. We explored their aggregation
behavior in organic solvents and n-alkanes by performing cluster analysis of the kerogen, asphaltene and
resin molecules to deduce their solubilities in the solvents. We then generated various dense kerogen
structures by gradual cooling and compression of initial low-density random configurations of kerogen
molecules. We systematically charecterized the porous kerogen structures by calculating the accessible
surface area and geometric pore size distribution and by analysing the structure connectivity and
percolation of the porous space [3]. Finally, we considered various porous organic matter structures
generated by an analogous way as the kerogen structures. The porous structures of the organic matter
consisted of the kerogen, asphaltene/resin, hydrocarbon, and carbon dioxide/water fractions and we
assumed the atomic balance is preserved during the maturation process [4]. Besides characterization of
the porous structures, we simulated release of light compounds from the porous structures of the organic
matter to mimic an experimental situation when a shale sample is brought to normal condition of 300 K
and 1 bar.
References
[1] J. Collell, P. Ungerer, G. Galliero, M. Yiannourakou, F. Montel, M. Pujol “Molecular Simulation of Bulk
Organic Matter in Type II Shales in the Middle of the Oil Formation Window” Energy Fuels, 2014, 28: 7457−7466.
[2] P. Ungerer, J. Collell, M. Yiannourakou “Molecular Modeling of the Volumetric and Thermodynamic
Properties of Kerogen: Influence of Organic Type and Maturity" Energy Fuels, 2015, 29: 91−105.
[3] L. Sarkisov, A. Harrison “Computational Structure Characterisation Tools in Application to Ordered and
Disordered Porous Materials” Molecular Simulations, 2011, 37: 1248-1257.
[4] B. P. Tissot, D. H. Welte, Petroleum Formation and Occurrence, Springer, Berlin (Germany), 1984.
Acknowledgements
We acknowledge funding from the European Union’s Horizon 2020 research and innovation programme under
grant agreement No 640979 and Czech Science Foundation under project No P106-13-02938S.

PPEPPD 2016
th
Solvent Effects of Renewable Solvent and Ionic Liquid as Greener Entrainer

for the Separation of Binary Azeotropic Mixtures by Extractive Distillation
Hiroyuki Matsuda*, Koji Inaba, Keiji Nishihara, Hirofumi Sumida, Kiyofumi Kurihara, and Katsumi Tochigi
Department of Materials and Applied Chemistry, Nihon University
*Corresponding author: matsuda.hiroyuki@nihon-u.ac.jp
Keywords: Vapor-liquid equilibria, Renewable solvent, Ethyl lactate, Ionic liquids, Entrainer
Abstract
Alternative solvents for green chemistry have been attracted much attention in recent years as
promising candidates to replace toxic organic solvents and VOCs. Ionic liquids (ILs) have unique
properties, such as high polarity, negligible vapor pressure, and conductive properties. Also, renewable
solvents can be easily produced from biomass feedstocks. Especially, ethyl lactate, one of renewable
solvents, has excellent properties as a solvent, such as low toxicity, relatively low volatility, low
viscosity, and good biodegradability, and recyclability [1]. Because of their features, ILs and renewable
solvents could be used as a solvent for green separation and purification.
The object of this study is to consider a solvent effect of renewable solvent and IL as an entrainer
candidate for the separation of binary azeotropic mixtures by extractive distillation. We selected ethyl
lactate and 1-hexyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl) imide ([HMIM]+[TFSI]-) as
renewable solvent and IL, respectively. Also, we selected five binary azeotropic systems, e.g., methyl
acetate + methanol, methanol + dimethyl carbonate (DMC), ethanol + ethyl acetate, ethyl acetate +
methyl ethyl ketone, and acetone + chloroform. Isobaric vapor-liquid equilibria (VLE) for binary
consituent systems containing ethyl lactae or [HMIM]+[TFSI]- were determined by an ebulliometric
method [2, 3] at pressures of (40.00 to 101.3) kPa. Experimental VLE data were represented by the
Wilson and NRTL models. The solvent effects of ethyl lactate or [HMIM]+[TFSI]- were evaluated by
two approaches, i.e., the residue curve maps and the calculation of the separation factors α12 using the
binary Wilson or NRTL parameters. Both of the calculated results for the residue curve maps and the
separation factors show that both ethyl lactate and [HMIM]+[TFSI]- can be used as entrainer for
extractive distillation of the investigated binary azeotropic systems.
References
[1] C. S. M. Pereira, V. M. T. M. Silva, A. E. Rodrigues “Ethyl lactate as a solvent: properties, applications and
production processes – a review” Green Chemistry, 2011, 13: 2658-2671.
[2] H. Matsuda, H. Yamada, R. Takahashi, A. Koda, K. Kurihara, K. Tochigi, K. Ochi “Ebulliometric

determination and prediction of vapor-liquid equilibria for binary mixture ethanol + ethyl hexanoate” J. Chem. Eng.
Data, 2011, 56: 5045-5051.
[3] H. Matsuda, M. Fukano, S. Kikkawa, D. Constantinescu, K. Kurihara, K. Tochigi, K. Ochi, J. Gmehling

“Ebulliometric determination and prediction of vapor-liquid equilibria for binary and ternary mixtures containing
alcohols (C1 – C4) and dimethyl carbonate” J. Chem. Thermodyn., 2012, 44: 84-96.

PPEPPD 2016
th
Solubilities and Diffusion Coefficients of Dyestuffs in Supercritical Carbon

Dioxide by Chromatographic Method
Toshitaka Funazukuri1*, Taichi Yamasaki1, Chang Yi Kong2 and Minori Taguchi1

1
Departmen of Applied Chemistry, Faculty of Science and Engineering, Chuo University, Japan
2
Department of Applied Chemistry and Biochemical Engineering, Graduate School of Integrated Science and
Technology, Shizuoka University, Japan
*Corresponding author: tfunazo@kc.chuo-u.ac.jp
Scientific topic: Therodynamics and Transport Properties
Keywords: Solubility, Dyestuff, Estimation, Chromatography, Diffusion coefficient
Abstract
Since physical properties of supercritical fluids can be tuned over a wide range of density from gas-like
to liquid-like by changing temperature and/or pressure, many applications with supercritical fluids have
been made to versatile chemical processes. As one of practical applications dyeing of textile fibers with
supercritical carbon dioxide (sc CO2) has been developed and applied. To design reactors solubilities of
dyestuffs were required. While many efforts on the measurements and the developments of the
correlation have been made, the solubility data are not sufficiently enough for many dye species over a
wide range of temperature and pressure. Molecular diffusion coefficients of dyestuffs in sc CO2 are also
required as well as diffusion coefficients in fibers. However, the measurements are scarce and the
accurate estimation is limited because dyestuffs are so polar that the Taylor dispersion method, which
has been mainly employed to measure diffusion coefficients in supercritical fluids, does not provide
accurate measurements due to response curve tailing. For measurements of polar compounds such as
dyestuffs the CIR (chromatographic impulse response) method [1] using a polymer coated capillary
column is suitable because adsorption of the solute dyestuffs to polymer coated on the column walls can
be taken into account. The CIR method suits to simultaneously determining diffusion coefficient and
retention factor, with which the solubilities can be correlated. In the present study, using the CIR method
both infinite dilution molecular diffusion coefficients and retention factors of disperse dyes such as
orange 11, red 60 and blue 14, in sc CO2 were measured at temperatures from 35 to 60 °C and pressures
up to 30 MPa. The diffusion coefficients and retention factors were well correlated with temperature and
solvent viscosity, and with temperature and solvent density, respectively. In addition, using the literature
data on solubilities of disperse dyes in sc CO2, the predictive correlations of the solubilities were
developed from two relationships (1) between retention factor and CO2 density and (2) between
solubility and CO2 density. The accuracies of the correlations to predict the solubilities were found to be
within deviations for experimental solubility data reported in the literature.
References
[1] T. Funazukuri, C. Y. Kong, N. Murooka, S. Kagei “Measurements of binary diffusion coefficients and partition
ratios for acetone, phenol, α-tocopherol, and β-carotene in supercritical carbon dioxide with a poly(ethylene
glycol)-coated capillary column” Ind. Eng. Chem. Res., 2000, 39: 4462-4469.
[2] C. Y. Kong, K. Sone, T. Sako, T. Funazukuri, S. Kagei “Solubility determination of organometallic complexes
in supercritical carbon dioxide by chromatographic impulse response method” Fluid Phase Equilib., 2011, 302:
347-353.
PPEPPD 2016
th
Solid–Liquid Phase Equilibria of Binary Mixtures Containing Terpenes and

Long Chain Alcohols
Marisa A. A. Rocha*, Florian M. Zehentbauer, Bernd Rathke, Johannes Kiefer

Technische Thermodynamik, Universität Bremen, Badgasteiner Str. 1,28359 Bremen, Germany
*Corresponding author: mrocha@uni-bremen.de
Keywords: Solid-liquid equilibria, molecular structure, deep eutectic solvents, terpenes, long chain
alcohols
Abstract
Research on sustainable solvents has become a hot topic initiating the development of new classes of
chemicals with desirable and less hazardous properties. Ionic liquids (ILs) and deep eutectic solvents
(DESs) have emerged as green and designable solvents with desirable properties to be applied in
numerous fields such as, synthesis, separation processes, and material science [1-3].
DESs can be prepared by simply combining a hydrogen bond donor (HBD) and a hydrogen bond
acceptor (HBA) with moderate melting points to form a liquid at room temperature. Compared to ILs,
DESs also possess the capability of tuning their physicochemical properties by the proper selection of the
components in terms of molecular structure, chemical nature, compositions and water content [2,3].
Nevertheless, DESs present the advantage of being prepared without the need of a solvent or purification
steps.
Despite of the increasing interested in these kind of systems there is a lack of experimental data to
characterize the fundamental thermodynamics of DESs.
In this work, binary mixtures containing terpenes and long chain alcohols are explored on both
macroscopic and a microscopic level. Solid-liquid (SL) phase equilibria of the binary mixtures are
investigated to determine the concentration range where a room temperature liquid mixture is formed and
to characterize the eutectic composition of the mixture. This study is complemented by a comprehensive
study of the molecular interactions and bulk structural organization of the binary mixtures by vibrational
spectroscopy (FTIR and Raman). Based on the obtained results, the effects of the chemical nature and
concentration of each component in the binary mixture on the formation of room temperature liquid
mixture are analyzed.
References
[1] F. Pena-Pereira, J. Namieśnik “Ionic liquids and deep eutectic mixtures: sustainable solvents for extraction
processes” ChemSusChem, 2014, 7: 1784-1800.
[2] E. L. Smith, A. P. Abbott, K. S. Ryder “Deep eutectic solvents (DESs) and their applications” Chemical
Reviews, 2014, 114: 11060-11082.
[3] M. Francisco, A. van den Bruinhorst, M. C. Kroon “Low-transition-temperature mixtures (LTTMs): a new
generation of designer solvents” Angewandte Chemie International Edition, 2013, 52: 3074-3085.
Acknowledgements
The authors gratefully acknowledge financial support by the Institutional Strategy funded by the Federal
Government's and the Federal States' Excellence Initiative.
PPEPPD 2016
th
Correlation of the High-pressure Heat of Mixing of Binary Systems

Containing the Carbon dioxide Using the Peng-Robinson Equation of State
Kiyofumi Kurihara*, Tomohiro Kobayashi, Hiroyuki Matsuda, Katsumi Tochigi

Department of Materials and Applied Chemistry, Nihon University, 1-8-14 Kanda Surugadai,
Chiyoda-ku, Tokyo 101-8308, Japan
*Corresponding author: kurihara.kiyofumi@nihon-u.ac.jp
Scientific topic: Thermodynamics and transport (experimental, modeling)
Keywords: Heat of mixing, Supercritical carbon dioxide, Equation of state, EOS-GE model
Abstract
Many researchers have measured the heat of mixing (ΔHM) of mixtures containing carbon dioxide
(CO2) and an organic solvent near the critical point of CO2. Our research group has also measured ΔHM
for binary systems of CO2 + alcohol (methanol, 2-propanol, 2-butanol, and 2-methyl-1-propanol) [1-4], +
ester (dimethyl carbonate (DMC) [5], diethyl carbonate (DEC) [6], ethyl acetate [7]), + ether (diisopropyl
ether (DIPE) [8], tert-butyl methyl ether (TBME) [9]). The CO2 + ester and + ether systems showed
extremely large exothermic behavior in their ΔHM data. A two-phase region in which ΔHM varies linearly
with composition was also found in the CO2-rich region of these five systems.
The objective of the present work was to correlate our experimental ΔHM data for CO2 + DMC, + DEC
+ ethyl acetate, + DIPE, and TBME usig the Peng–Robinson equation of state [10] coupled with the the
van der Waals one fluid mixing rule and the EOS-GE models (MHV1 [11], MHV2 [11], and Wong-
Sandler [12]) which combines equation of state with excess free energy model at the standard state of
zaro pressure or infinite pressre.
References
[1] W. Dai, K. Ochi, K. Kurihara, K. Kojima, and M. Hongo, Jpn. J. Thermophys. Prop., 1998, 12: 64–69.
[2] W. Dai, K. Kojima, K. Ochi, J. Chem. Eng. Data, 1999, 44: 161–164.
[3] W. Dai, K. Kojima, K. Ochi, J. Chem. Eng. Data, 2000, 45: 6–10.
[4] K. Ochi, W. Dai, Y. Wada, H. Hayashi, K. Kurihara, K.Kojima, Fluid Phase Equilib., 2002, 194-197: 919–928.
[5] H. Matsuda, S. Yoshii, A. Nagashima, K. Kurihara, K. Ochi, J. Chem. Eng. Data, 2005, 50: 1419–1424.
[6] H. Matsuda, S. Yoshii, A. Nagashima, K. Kurihara, K. Ochi, Fluid Phase Equilib., 2005, 236: 146–155.
[7] K. Kurihara, Y. Nakamura, T. Okamoto, Y. Itazu, H. Matsuda, K. Tochigi, Fluid Phase Equilib., 2014, 362:
313–317.
[8] H. Matsuda, E. Machida, Y. Yamanaka, K. Kurihara, and K. Ochi, J. Chem. Eng. Data, 2008, 53: 1612-1617.
[9] K. Kurihara, To. Kobayashi, H. Matsuda, K. Tochigi, submited to Fluid Phase Equilibria.
[10] D. Peng, D.B. Robinson, Ind. Eng. Chem. Fundam. 15(1976)59-64.
[11] M. L. Michelsen, Fluid Phase Equilib., 1990, 60: 213–219.
[12] D. S. H. Wong, S. I. Sandler, AIChE Journal, 1992, 38: 671-680.
PPEPPD 2016
th
A new equation of state based on Wertheim's thermodynamic perturbation

theory of third order
Wasilios Zmpitas, Joachim Gross*

Institute of Thermodynamics and Thermal Engineering, University of Stuttgart,
Pfaffenwaldring 9, 70569 Stuttgart, Germany
*Corresponding author: gross@itt.uni-stuttgart.de
Keywords: SAFT, TPT, perturbation theory, hard chain
Abstract
Our study concerns Wertheims' theory applied to the limit of hard-chain fluids. Wertheims' perturbation
theory of first order (TPT1[1]) is known to over-estimate the pressure of chain fluids (for segment
number m>3). The second order theory (TPT2[2]) alleviates the problem to some extent. The pressure,
however, is still over-estimated.
In this study we demostrate, that an expansion by higher order terms in the framework of Wertheims'
single-chain approximation only leads to a negligible improvement. By dividing the third-order term into
a density- and chainlength-dependent contribution and determining the chainlength-dependent
contribution by enforcing a second virial coefficient of chain fluids, we obtain an analytical equation of
state for chain fluids. An analytical expression for the second virial coefficient has been proposed by van
Westen et al. [3] based on molecular simulations. We observe a marked improvement of the model
compared to TPT1 and TPT2. The terms of second and third order are also independently evaluated with
molecular simulation data.
References
[1] M. S. Wertheim, J. Stat. Phys. 42, (1986), 459-492
[2] M. S. Wertheim, J. Chem. Phys. 87, (1987), 7323-7331
[3] T. van Westen, Mol. Phys. 112, (2014), 919-928

PPEPPD 2016
th
Thermophysical Properties and LLE with Water of [Nf2]- Based Ionic Liquids
R. Fidalgo1,*, O. G. Sas1, I. Domínguez2, B. González1, A. Domínguez1

1
Advanced Separation Processes Group, Edif. Isaac Newton, Department of Chemical Engineering, University of
Vigo, Lagoas-Marcosende, 36310 Vigo, Spain
2
Department of Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, s/n,
Porto 4200-465, Portugal
* Presenting author: rfidalgo@uvigo.es
Scientific topic: Phase equilibria.
Keywords: Liquid-Liquid Equilibria, Ionic Liquids, Thermophysical Properties,

bis(fluorosulfonyl)imide.
Abstract
Ionic Liquids (ILs) have high importance due to its implementation in many areas such as reactions
involving gases, organic and inorganic synthesis extraction processes include solid, liquid and gas [1]
among others. A wide study about a big variety of physical properties is important in the evaluation of
ILs for their potential use in industrial processes.
This work include pure component properties such as density, viscosity, speed of sound and refractive
index of commercial 1-Ethyl-3-Methylimidazolium bis(fluorosulfonil)imide ([EMim][Nf2]) as a function
of temperature and at atmospheric pressure. The density, speed of sound, and refractive index data were
properly fitted to a linear equation, while viscosity data were fitted to Arrhenius-like law [2], Vogel-
Fulcher-Tamman (VFT), [3-5] a modified VFT, Litovitz [6], and fluidity [7] equations. Besides, the
water solubility of the ionic liquid was experimentally determinate at several temperature values and
atmospheric pressure. Also, the miscibility of water are described with the Non-Random Two-Liquid
(NRTL) thermodynamic model.
References
[1] Wasserscheid, P.; Welton, T. “Ionic Liquids in Sysnthesis” Wiley-VCH Verlag GmbH & Co. KgaA, 2002.
[2] Andrade, E. N. A “Theory of the Viscosity of Liquids” Philosophical Magazine, 1934, 17: 698−732.
[3] Vogel, H. “The Law of the Relation Between the Viscosity of Liquids and the Temperature” Physikalische
Zeitschriftm, 1921, 22: 645−646.
[4] Fulcher, G. S. “Analysis of Recent Measurements of the Viscosity of Glasses” Journal of the American Ceramic
Society, 1925, 8: 339−355.
[5] Tammann, G.; Hesse, W. Z. “The Dependence of Viscosity upon the Temperature of Supercooled Liquids”
Zeitschrift für anorganische und allgemeine Chemie, 1926, 156: 245−257.
[6] Litovitz, T. A. “Temperature Dependence of the Viscosity of Associated Liquids” The Journal of Chemical
Physics, 1952, 20: 1088−1089.
[7] Ghatee, M. H.; Zare, M.; Moosavi, F.; Zolghadr, A. R. “Temperature-Dependent Density and Viscosity of the
Ionic Liquids 1-Alkyl-3-methylimidazolium Iodides: Experiment and Molecular Dynamics Simulation” Journal of
Chemical & Engineering Data, 2010, 55: 3084−3088.
Acknoledgements
O. G. Sas is grateful to the Comisión Interministerial de Ciencia y Tecnología (Spain) for her FPI grant (BES-2014-
067694). I. Domínguez is grateful to the Xunta de Galicia for her scholarship (ED481B 2014/104-O). R. Fidalgo
and B. González are grateful to the Comisión Interministerial de Ciencia y Tecnología (Spain) for the project
CTM2013- 46093-P and Xunta de Galicia (Spain) for the project EM2014/039.

PPEPPD 2016
th
Study of ABS systems of ionic liquids: 1-butyl-3-methyl imidazolium

dicyanamide, [BMim][dca] and 1-ethyl-3-methyl imidazolium dicyanamide,
[EMim][dca]
Lorena P. Armada1,*, Begoña González1, Andrés Moure2
1
2
Department of Chemical Engineering, University of Vigo, Lagoas, 32004 Ourense, Spain
*Corresponding author: loreperez@uvigo.es
Scientific topic: phase equlibria
Keywords: Ionic Liquid, ABS, [BMim][dca], [EMim][dca]
Abstract
Nowadays and due to increasing demand from industries processes more respectful of the environment,
numerous studies on the ionic-liquid-based Aqueous Biphasic Systems (ABS) are made. These
researches are looking for change the traditional solvents used, such as volatile organic compounds
(VOCs), for ABS which are more careful with the environment. ABS are based on combinations of high
concentrated solutes (polymer-polymer, polymer-salt or salt-salt) dissolved in water, that stop being
soluble to give two immiscible aqueous phases. The advantages presented by ionic liquids (ILs) versus
other solvents are negligible vapor pressure, non-flammability, high thermal stability, and high solubility
for both polar and non-polar organic and inorganic compounds and recovery.
In this work the differences of the ability to form ABS systems between two ionic liquids (1-butyl-3-
methyl imidazolium dicyanamide [BMim][dca] and 1-ethyl-3-methyl imidazolium dicyanamide
[EMim][dca]), with several inorganic salts sodium carbonate (Na2CO3), potassium hydrogen phosphate
(K2HPO4), sodium dihydrogen phosphate (NaH2PO4), potassium phosphate (K3PO4) and potassium
carbonate (K2CO3) are evaluated. The differences found between the two ionic liquids purpose of this
study can be explained for length alkyl chain because when the alkyl chain length of IL anion is
increasing, the biphasic region increasing. The results indicate that the salting-out strength of salts to
induce the formation of a second aqueous phase follows the rank: Na 2CO3 > K3PO4 > K2CO3 > K2HPO4
> NaH2PO4. Finally, it was used an empirical mathematical equation developed by Merchuck et al.[1],
where the result of the correlation shows that the above mentioned equation is appropriate to reproduce
satisfactorily the solubility curves of these systems.
References
[1] J. C. Merchuk, B. A. Andrews, J. A. Asenjo. “Aqueous two-phase systems for protein separation Studies on
phase inversion” J. Chromatogr. B 711 (1998) 285–293.
Acknowledgements
The authors are grateful to the Comisión Interministerial de Ciencia y Tecnología (Spain) for the project CTM2013-
46093-P and Xunta de Galicia (Spain) for the project EM2014/039.
PPEPPD 2016
th
Phase behaviour of surfactant ionic liquids for EOR applications
Iria Rodríguez-Escontrela, Iago Rodríguez-Palmeiro, Óscar Rodríguez, Alberto Arce, Ana Soto*
Department of Chemical Engineering, University of Santiago de Compostela, Santiago de Compostela, Spain
* Corresponding author: ana.soto@usc.es
Keywords: Phase behavior, Ionic liquid, Interfacial tension, Surfactant
Abstract
There are several methods to improve oil extraction from reservoirs. Among them, the addition of
surfactants to the extraction fluid is a promising alternative [1]. Amphiphilic compounds reduce oil/water
interfacial tension and therefore capillary forces that entrap petroleum into reservoir pores also decrease
[2]. Surface active ionic liquids (SAILs) have been proposed as suitable chemicals to be used in
surfactant flooding due to its capacity to reduce oil/water interfacial tension and solubilise oil. SAILs
show a number of advantages over typical ionic and non-ionic surfactants: their liquid character over a
wide range of temperatures (including room temperature) which makes their handling easier; their
usually high viscosity that could increase aqueous phase viscosity avoiding digitations; their design
opportunities; the possibility of avoiding the use of co-surfactants because SAILs form stable aggregates
due to their strong cohesive forces; etc [3].
The main mechanism of surfactant enhanced oil recovery (EOR) is reducing interfacial tension, which
has been linked to water and oil solubilisation and the presence of a third, immiscible, microemulsion
phase. Therefore, the determination of phase behavior and interfacial tension between phases in
equilibrium is necesary as a fundamental study to evaluate the use of SAILs in EOR.
In this work, the phase behavior of several SAILs (combining phosphonium and imidazolium cations
with different anions) in a ternary system with water or brine (as aqueous phase) and n-dodecane (as oil
phase) has been determined using analytical or visual methods. Phase diagrams are critical looking for
the splitting of the third microemulsion phase. The solubilization of the aqueous and oil phase in this
micromeulsion has also been evaluated. A screening to evaluate the influence of temperature and the
aqueous phase salinity (NaCl concentration), critical for reservoir conditions, was also studied.
Interfacial tensions between the phases in equilibrium were measured experimentally since its reduction
is the final proof for EOR applications.
References
[1] J.J. Sheng, Modern chemical enhanced oil recovery, Theory and Practice, Elsevier, Amsterdam, 2011.
[2] J. G. Speight, Enhanced recovery methods for heavy oil and tar sands, Gulf publishing company, Houston
(2009).
[3] S. Lago, H. Rodriguez, M. K. Khoshkbarchi, A. Soto, A. Arce, Enhanced oil recovery using the ionic liquid
trihexyl(tetradecyl)phosphonium chloride: phase behaviour and properties, RSC Adv. 2 (2012) 9392-9397.
Acknowledgements
The authors acknowledge the Ministry of Economy and Competitiveness of Spain for financial support through
project CQT2012-33359. I. Rodríguez -Escontrela and O. Rodriguez also acknowledge financial support (FPI grant
ref. BES-2013-062735, Ramón y Cajal fellow RYC-2012-10378).
PPEPPD 2016
th
Simulaneous description of activity coefficents and solubility
with electrolyte CPA
Anders Schlaikjer1*, Kaj Thomsen1 and Georgios M. Kontogeorgis1

1
Center for Energy Resources Engineering, Department of Chemical and Biochemical Engineering,
Technical University of Denmark, Denmark
*Corresponding author: andsh@kt.dtu.dk
Keywords: Equation of state, Electrolytes, Solubility
Abstract
While activity coefficient models have classically dominated the modelling of electrolytes, electrolyte
equations of state have gained more attention during the last decade, where several developments based
on SAFT and CPA have been presented [1-3]. Within the growing number of electrolyte equations of
state, the description of salt solubility have received little attention so far, and no research group have
systematically investigated their models ability to describe solubility simultaneously with other
properties.
In this work we have parameterized the electrolyte CPA equation of state [1] for several salts with the
goal of obtaining simultaneous description of solubility and activity/osmotic coefficients over an
extended temperature range. Description of solubility with an equaiton of state requires a model for the
solid phase. In this work the solubility index is used and it require several solid standard state properties,
e.g. the Gibbs energy and enthalpy of formation as well as the heat capacity. For many salts these
properties are available trough databases, however for most hydrated salts this is not the case, and for
these salts the solid standard state properties are treated as adjustable parameters together with the model
parameters.
The binary correlations and ternary/multicomponent predictions, with this new parameter set, is
evaluated by comparison to the orginal parameter set of the model, only fitted to osmotic and activity
coefficients, as well as the well known activity coefficient model, extended UNIQUAC.
References
[1] L.F.Cameretti, G. Sadowski, J.M. Mollerup “ Modeling of aqueous electrolyte solutions with perturbed-chain
statistical associated fluid theory”, ind. Eng. Chem. Res., 2005, 44:3355-3362.
[2] S.P. Tan, H. Adidharma, M. Radosz “Statistical associating fluid theory coupled with restricted primitive model
to represent aqueous strong electrolytes”, 2005, 44:4442-4452.
[3]B. Maribo-Mogensen, K. Thomsen, G.M. Kontogeorgis “An Electrolyte CPA equation of state for mixed solvent
electrolytes” AIChE Journal, 2015, 61:2933-2950.
Acknowledgements
The authors would like the thank the DTU CERE CHIGP constortium and DTU for financial support for this
project.

PPEPPD 2016
th
Thermodynamic Stability of Xenon+Benzene Mixed Hydrates
Takeshi Sugahara*
Division of Chemical Engineering, Department of Materials Engineering Science, Graduate School of Engineering
Science, Osaka University, Japan
*Corresponding author: sugahara@cheng.es.osaka-u.ac.jp
Keywords: Clathrate hydrate, Phase equilibria, Raman spectroscopy, Diffraction, Benzene
Abstract
It has been published that benzene forms clathrate hydrates with assistance of methane [1]. The mobility
of the benzene molecule in the aqueous phase and the cage is interesting [2, 3] and the benzene
molecules often form the dimer. In the present study, thermodynamic stability boundaries of xenon (Xe)
+ benzene (C6H6) mixed hydrate system are measured. The four-phase equilibrium curve H+Lw+LHC+G
of the Xe+C6H6 mixed hydrate system intersects at 282 K and 0.38 MPa with the three-phase equilibrium
curve H+Lw+G of the simple Xe hydarte system (H: hydrate phase, Lw: aqueous phase, LHC: benzene-rich
phase, G: gas phase). The slope (dp/dT) of H+Lw+LHC+G in the Xe+C6H6 mixed hydrate system changes
around 283 K and 0.45 MPa. At temperatures abouve 283 K, the slope of H+Lw+LHC+G is almost the
same as that of H+Lw+G of the simple Xe hydarte system. The powder XRD profile reveals that the
structure of the Xe+C6H6 mixed hydrate prepared at 277 K and 0.2 MPa is structure-II (cubic). The
lattice constant (recorded at 153 K) is 1.732 nm.
References
[1] A. Danesh, B. Tohidi, R. W. Burgass, A. C. Todd, “Benzene can Form Gas Hydrates”, Trans IChem E, 1993,
71: 457-459.
[2] M. Nakahara, C. Wakai, N. Matubayasi, “Jump in the Rotational Mobility of Benzene Induced by the Clathrate
Hydrate Formation”, The Journal of Physical Chemistry, 1995, 99: 1377-1379.
[3] M. Nakahara, C. Wakai, Y. Yoshimoto, N. Matubayasi, “Dynamic of Hydrophobic Hydration of Benzene”, The
Journal of Physical Chemistry, 1996, 100: 1345-1349.
Acknowledgements
We acknowledge the scientific supports from the “Gas-Hydrate Analyzing System (GHAS)” of Division of
Chemical Engineering, Graduate School of Engineering Science, Osaka University and Shimadzu Corporation
(only for the PXRD measurement at low temperatures)

PPEPPD 2016
th
Effects of polymer polydispersity on Liquid-Liquid Equilibrium
Han Earl Yang1 and Young Chan Bae2*

1
Department of Chemical Engineering, Hanyang University, Republic of Korea
2
Department of Chemical Engineering, Hanyang University, Republic of Korea
*Corresponding author: ycbae@hanyang.ac.kr
Keywords: polymer solution, polydispersity, liquid liquid equilibrium, continuous thermodynamics
Abstract
The polymer polydispersity effects on the liquid-liquid equilibrium (LLE) of polymer solutions are
studied. Various types of cloud point curves such as upper critical solution temperature (UCST), lower
critical solution temperature (LCST), both UCST and LCST, and closed loop miscibility are investigated
by two different approaches: discrete methods and continuous thermodynamics. For discrete approaches,
polymer solutions composed of a solvent and two monodisperse polymer homologs with different
molecular weight are studied. On the other hand, LLE of polydisperse polymer solution are considered
with molecular weight distribution of the polymer. Determination of various types of cloud points curves
for polydisperse polymer solutions are conducted from thermal optical analysis (TOA). To describe the
phase equilibrium of polydisperse polymer solutions, incompressible lattice model with chain length
contribution term is applied. The used thermodynamic model appropriately describes characteristic phase
behavior of polydisperse polymer solutions and the calculated results show good agreement with
experimental data.
References
[1] J.M. Prausnitz, R.N. Lichtenthaler, E.G. de Azevedo, Molecular Thermodynamics of Fluid-Phase Equilibria,
3rd ed., Prentice-Hall, New Jersey, 1999.
[2] H. Tompa, Trans. Faraday Soc., 45 (1949) 1142-1152.
[3] A.R. Shultz, P.J. Flory, J. Am. Chem. Soc., 74 (1952) 4760–4767.
[4] M. Tsuyumoto, Y. Einaga, H. Fujita, Polym. J., 16 (1984) 229-240.
[5] M.T. Ratzsch, H. Kehlen, Prog. Polym. Sci., 14 (1989) 1-46.
[6] S.K. Ryu, Y.C. Bae, Polymer, 53 (2012) 1339-1346.
[7] J.J.Choi, Y.C. Bae, Fluid Phase Equilibr., 157 (1999) 213-228

PPEPPD 2016
th
Vapour-liquid equilibria and density modelling of CO2-rich systems

with PC-SAFT and SAFT-VR Mie.
Alfonso González Pérez1,2, Patrice Paricaud3, Antonin Chapoy2*, Christophe Coquelet1*

1
Mines ParisTech PSL Research Universite, CTP-Centre Thermodynamic of Processes, France
2
Institute of Petroleum Engineering, Heriot Watt University, United Kingdom
3
Laboratoire Chimie et Procédé, UCP-ENSTA ParisTech, France
*Corresponding author1: christophe.coquelet@mines-paristech.fr
*Corresponding author2: antonin.chapoy@pet.hw.ac.uk
Scientific topic: Thermodynamics and transport properties. Carbon Capture Storage.
Keywords: SAFT, Density, Phase behaviour, CCS.
Abstract
Carbon capture and storage (CCS) is nowadays considered as one of the most promising methods to
counterbalance the CO2 emissions from the combustion of fossil fuels, the natural gas processing, cement
manufacturing, etc. The development and research of accurate thermodynamic models to predict
thermophisical properties are required for a safe, optimum and worthwhile transport and storage of CO 2-
rich steams. One important aspect of these thermodynamic model (equations of state) concerns the
prediction of densities and understanding of phase diagrams. The predcition of the transport properties
are strongly dependant of the accuracy of these equations of state (EoSs). Therefore, in the present work
two molecular based EoSs are compared in order to evaluate their capability to describe the density and
phase behaviour of systems relevant to CCS.
The EoSs considered herein are founded on the statistical associating fluid theory (SAFT), one based on
the perturbed-chain SAFT (PC-SAFT) [1], and another one on the variable range interaction through Mie
potentials SAFT (SAFT-VR Mie) [2]. The SAFT-EoSs were used to predict the phase diagrams (vapour-
liquid equilibria (VLE) and vapour-liquid-liquid equilibria (VLLE)) and the densities of gas, liquid and
supercritical phases. To assess and compare the adequacy of the selected models, the modelling results
were compared against experimental data of several CO2-rich systems in a wide range of conditions of
temperature, pressure and compositions from the literature. The studied systems of interest for the CCS
were compound by CO2, O2, N2, Ar, H2S and hydrocarbons.
Both SAFT-EoSs showed low absolute average deviations (below 5%) between the modelling results and
the experimental data from the literature. However, significative differences have been observed between
PC-SAFT and SAFT-VR Mie depending on the experimental conditions.
References
[1] Gross, J. and Sadowski, G., “Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for
Chain Molecules”, Ind. Eng. Chem. Res., vol. 40, no. 4, pp. 1244–1260, Feb. 2001.
[2] Lafitte, T., Apostolakou, A., Avendaño, C., Galindo, A., Adjiman, C. S., Müller, E. and Jackson, G., “Accurate
statistical associating fluid theory for chain molecules formed from Mie segments”, Journal of Chemical Physics,
139, 2013.
PPEPPD 2016
th
Thermal Behavior of Tricyanomethanide-based Ionic Liquids:

Experimental Determination and Structure-Property Relationship
Lawien F. Zubeir1*,, Marisa A. A. Rocha2, Maaike C. Kroon1,3

1
Eindhoven University of Technology, Dept. of Chemical Engineering and Chemistry, Den Dolech 2, 5612 AZ
Eindhoven, The Netherlands
2
University of Bremen, Engineering Thermodynamics, Badgasteiner Str. 1, D-28359 Bremen, Germany
3
The Petroleum Institute, Dept. Chemical Engineering, P.O. Box 2533, Abu Dhabi, United Arab Emirates
*Corresponding author: L.F.Zubeir@tue.nl
Scientific topic: Thermodynamics and transport properties (experimental)
Keywords: Ionic liquids, Heat capacities, Thermal decomposition temperature, Melting point
Abstract
The properties of ionic liquids (ILs) can be tuned by adjusting the structure and composition of the
cations and the anions. The versatility of the ILs has led to intense research in several areas. The diverse
research fields range from the potential use of ILs as heat transfer fluids for heat exchange to their use as
absorbents for carbon dioxide (CO2) capture.
Heat capacity is one of the most important thermophysical properties that characterizes the liquid phase,
and is intimately related with the temperature dependence of fundamental thermodynamic properties. For
instance, it is shown that the imidazolium-based ILs present higher heat capacities per unit of volume
than two high performance commercial thermal fluids (e.g., Parathem HE, Dowtherm MX) [1].
Therefore, the knowledge of the heat capacity is required for the evaluation of the applicability of the ILs
as heat transfer fluids. Furthermore, to establish the thermal operating range of the ILs, the thermal
decomposition temperature and the melting point have to be determined. Normally, the thermal stability
of the ILs is obtained from the dynamic results, as the so-called onset decomposition temperature (Tonset).
However, ILs usually degrade at temperatures far below Tonset. To obtain more precise values, long-term
isothermal studies at temperatures below Tonset are required, which give a better insight into the thermal
decomposition kinetics and activation energy.
In this work, the ILs 1-alkyl-3-methylimidazolium tricyanomethanide ([Cnmim][TCM], where n=2-8 and
12) were investigated. First, dynamic and isothermal thermogravimetric analyses were carried out. The
influence of the experimental conditions, such as the heating rate and the sample mass were considered.
Second, the melting and or the glass transition points were determined. Third, the molar, specific and
volumic heat capacities and their temperature dependency were measured.
Furthermore, the ILs, 1-[2-(methoxyethyl)ethyl]-3-methylimidazolium-, and 1-[2-(2-
methoxyethoxy)ethyl]-3-methylimidazolium tricyanomethanide have been studied to evaluate the effect
of the ether groups on the measured properties. The experimental results obtained were used to evaluate
the influence of the following modifications: i) alkyl chain length of the cation; ii) nature and size of the
anion and iii) ether functionalization of the anion.
References
[1] J. M. P. França, C. A. Nieto de Castro, M. M. Lopes, V. M. B. Nunes, “Influence of Thermophysical Properties
of Ionic Liquids in Chemical Process Design” Journal of Chemical & Engineering Data, 2009, 54: 2569-2575.
Acknowledgements
Financial support from the European Union FP-7-Energy project (IOLICAP) is gratefully acknowledged.
PPEPPD 2016
th
Free energy calculations of capped gold nano crystals
Gernot Bauer1* and Joachim Gross1

1
*Corresponding author: bauer@itt.uni-stuttgart.de
Keywords: Free energy calculation of solids, gold nano crystals, potential of mean force, phase
equilibrium
Abstract
For more than two decades, nano crystals (NC) are intensively studied – theoretical, experimental as well
as via molecular simulations – due to their ability to self-assemble into highly ordered structures. The
formation of these so-called superstructures depends on the shape and size of the NC as well as
parameters such as solvent and temperature. Understanding the interplay of all parameters, one can – in
theory – design a material in a custom made fashion by modifying the NC on an atomistic level. The aim
of this work is a description of how atomistic alternations affect the formation of superstructures.
The first part of this work describes an effective potential – the potential of mean force (PMF) – between
isolated pairs and triplets of icosahedral gold NC (core sizes between 1.8 nm ~ 3.7 nm) that are capped
with thiols. Capturing all atomic interactions by effective two and three body potentials enables us to
simulate large systems which would not be feasible within atomistic simulations. We perform molecular
dynamics simulations and measure the forces between pairs of NC which we then integrate to calculate
the PMF. These PMF are combined with simulations of NC triplets to isolate three body effects. This
procedure allows us to analyse how shape and size as well as temperature and solvent influences the
PMF.
The second part of this work illustrates our strategy to evaluate the phase behaviour of NC systems. We
take candidate solid structures found in experiments and perform free energy calculations based on the
two body PMF to determine phase transition curves. First, an initial phase coexistence point is found by
simulating relative Gibbs energies of candidate structures as well as of the fluid. We take the perfect
Einstein molecule[1] as reference for the solids. From the initial phase coexistence point, we then trace
the coexistence curves using multiple simulations in the isobaric-isothermal ensemble. Having
determined a coexistence curve for a specific PMF (representing a specific shaped and sized NC and
solvent) one can estimate coexistence curves for different PMF by formulating a set of generalized
Clapeyron equations. Using this technique, we outline a strategy to evaluate the influence of different
shaped NC, solvents as well as the role of three body interactions.
References
[1] Vega, Carlos, and Eva G. Noya. "Revisiting the Frenkel-Ladd method to compute the free energy of solids: The
Einstein molecule approach." The Journal of chemical physics 127.15 (2007): 154113.
Acknowledgements
Funding support from the DFG through Collaborative Research Centre 716, Project A.7 is greatly acknowledged.
PPEPPD 2016
th
Solubility of Anthraquinone and Their Derivartives
in Supercritical Carbon Dioxide
Kazuhiro Tamura,* Tatsuro Tanaka, Keisuke Shimizu and Ratna Surya Alwi
Schhol of Natural System, College of Science and Engineering, Kanazawa University, Japan
*Corresponding author: tamura@se.kanazawa-u.ac.jp
Scientific topic: Fundamentals: Phase Equilibria(experimental and modeling)
Keywords: Solubility, Anthraquinone, Dyestuff, Supercritical Carbon dioxide, Equation of State
Abstract
In the development and design of the supercritical dyeing process, the solubility of dyestuffs and the
phase behavior should be well known primarily. Among the dyestuffs used in dyeing processes, there
exist anthraquinone derivatives formed by several functional groups. As evidenced from the current
measurements, the solubility of anthraquinone derivatives changes variously with the substitutional
groups on the anthraquinone. To understand the solubility of anthraquinone dyestuffs in sc-CO2, one
needs to find out the effect of substituted groups in anthraquinone systems on the solubilities in sc-CO2.
In the present work, we measured the solubility of anthraquinone derivatives including -CH3, -NH2, -
NO2, -Cl, and -OH groups at the temperature of (323.15, 353.15 and 383.15) K and over pressure ranges
(12.5 to 25.0) MPa by a flow-type apparatus to clarify how the solubility of anthraquinone compounds in
sc-CO2 changes with the substitutional groups on the anthraquinone. The solubilities of anthraquinone
derivatives were analyzed thermodynamically by equations of state of Peng-Robinson, Peng-Robinson-
Stryjek-Vera [1]. Furthermore the experimental results were correlated and predicted by the PSRK
(Predictive-Soave-Redlich-Kwong) equation of state [2] coupled with the Gibbs energy model given by
the extended form of UNIFAC group contribution model [3]. The calculated solubilities of anthraquinone
derivatives were in satisfactory agreement with the experimental results.
References
[1] R. Stryjek and J. H. Vera “PRSV: An improved Peng—Robinson equation of state for pure compounds and
mixtures” Can. J. Chem. Eng. 323–333.
T. Holderbaum, J. Gmehling
[2] T. Holderbaum, J. Gmehling “PSRK: A group contribution equation of state based on UNIFAC” Fluid Phase
Equilibria, 1991, 70, 251–265.
[3] I. Nagata, T. Meyer, J. Gmehling “Correlation of binary liquid-liquid equilibrium data over awide range
temperature range using UNIQUAC and extended UNIQUAC models” Fluid Phase Equilibria, 1991, 65 19-
39.251–265.

PPEPPD 2016
th
Application of an Equation-of-State Based Activity Coefficient Model
Ning-Ju Yang1, Ming-Jer Lee1, and Ding-Yu Peng2*

1
Departmen of Chemical Engineering, National Taiwan University of Science & Technology,Taiwan
2
Department of Chemical & Biological Engineering, University of Saskatchewan, Canada
*Corresponding author: dingyu.peng@usask.ca
Keywords: Activity coefficient, van Laar equation, Vapor-liquid-liquid equilibria, Multicomponent

system,
Abstract
The van Laar model [1] is one of the frequently mentioned activity coefficient models in vapor-liquid
equilibrium calculations. It was based in part on the use of the van der Waals equation as an empirical
model for the fluids. However, unlike the original formulation given by van Laar, the Carlson-Colburn
formulation [2], which is the version actually appearing in modern literature, involves two adjustable
parameters that do not have any physical significance. Furthermore, this formulation cannot be used to
represent the phase behavior relations for multicomponent systems. Peng [3] has recently showed that the
deficiency of the original van Laar model can be rectified by treating the attraction energy parameter in
the van der Waals type of equation of state as a function of temperature. The resulting formulation has
been shown to be applicable to multicomponent systems as well as binary systems using only pure-
component parameters and one binary interaction parameter for each of the consitituent binary systems.
In this presentation the application of the rectified formulation to the representation of phase equilibria
for polar sytems and in particular for the water-alkanol systems involving vapor-liquid-liquid equilibria
will be depicted. New experimental phase equilibrium data for some water-alkanol systems will be
presented. The capability of the reformulated model in representing these data will be compared with
those of the Wilson model [4] and the NRTL model [5].
References
[1] J. J. van Laar, Sechs Vorträgen über das thermodynamiche Potentia, Braunschweig, Fried. Vieweg & Sohn,
1906.
[2] H. C. Carlson, A. P. Colburn “Vapor-liquid equilibria od model solutions. Utilization of theoretical methods to
extend data” Industrial and Engineering Chemistry, 1942, 34: 581-589.
[3] D.-Y. Peng “Extending the van Laar model to multicomponent systems” The Open Thermodynamics Journal,
2010, 4: 129-140.
[4] G. M. Wilson “Vapor-liquid equilibrium. XI. A new expression for the excess free energy of mixing” Journal of
the American Chemical Society, 1964, 86: 127-130.
[5] H. Renon, J. M. Prausnitz “Local compositions in thermodynamic excess functions for liquid mixtures” AIChE
Journal, 1968, 14: 135-144.
Acknowledgements
The authors are grateful for financial support provided by the Ministry of Science and Technology (MOST),
Taiwan, through MOST 104-ET-E011-002-ET.
PPEPPD 2016
th
Molecular simulation of confined fluids: pure components and mixtures
Luis Fernando Mercier Franco *, Marcelo Castier, Ioannis G. Economou

1
Chemical Engineering Program, Texas A&M University at Qatar, P.O. Box 23874, Doha, Qatar
*Corresponding author: l.mercier_franco@qatar.tamu.edu
Keywords: Molecular dynamics, confined fluids, adsorption, self-diffusion coefficient
Abstract
Fluids in confinement media are present in several chemical and biochemical processes, such as:
adsorption, membrane separation, catalysis, chromatography, and DNA purification. The interactions
between the fluid particles and the confinement material affect the macroscopic properties of the fluid.
For carbonate rocks, these effects are extremely relevant for nanopores. Calcite is the main constituent of
carbonate rocks, which form most of the world's reservoirs. In this work, we performed molecular
dynamics simulations of methane and carbon dioxide confined between two calcite crystals. For calcite,
we applied the force field developed by Xiao et al. [1]. For methane and carbon dioxide, we used TraPPE
force field [2,3]. The results for pure methane adsorption isotherms obtained by our simulations are in
excellent agreement with literature experimental data [4] of methane adsorption in shale rocks with ~ 50
wt % of calcite in their mineral composition. For mixtures of methane and carbon dioxide, the density
profiles calculated via molecular dynamics simulations show that carbon dioxide is preferentially
adsorbed on calcite surface. We also calculated the parallel self-diffusion coefficients for different
distances to the calcite surface. Near the surface, we have observed an anisotropy of the parallel self-
diffusion coefficients, that is, the self-diffusion coefficients are different in orthogonal directions parallel
to the calcite surface. This anisotropy might be explained by the anisotropic arrangement of the atoms in
calcite [5].
References
[1] S. Xiao, S. Edwards, F. Gräter “A new transferable forcefield for simulating the mechanics of CaCO 3 crystals”
J. Phys. Chem. C 2001, 115: 20067-20075.
[2] M. G. Martin, J. I. Siepmann “Transferable Potentials for Phase Equilibria. 1. United-atom description of n-
alkanes” J. Phys. Chem. B 1998, 102: 2569-2577.
[3] J. J. Potoff, J. I. Siepmann “Vapor-Liquid equilibria of mixtures containing alkanes, carbon dioxide, and
nitrogen. AIChE J. 2001, 47: 1676-1682.
[4] T. F. Rexer, E. J. Mathia, A. C. Aplin, K. M. Thomas “High-Pressure Methane Adsorption and Characterization
of Pores in Posidonia Shales and Isolated Kerogens” Energy Fuels 2014, 28: 2886-2901.
[5] L. F. M. Franco, M. Castier, I. G. Economou “Anisotropic parallel self-diffusion coefficients near calcite
surface: A molecular dynamics study” 2016 (submitted).

PPEPPD 2016
th
WEDNESDAY – MAY, 25
Invited Lecture 6
Energy Efficiency of Desalination: Role of Membranes and Process Design
Menachem Elimelech
Department of Chemical & Environmental Engineering, Yale University
*Corresponding author: menachem.elimelech@yale.edu
Abstract
Seawater and brackish water desalination has become an important pathway for increasing fresh water
supply to alleviate global water scarcity. Among available technologies, reverse osmosis (RO) has
become the gold-standard for desalination, mainly due to its process maturity and reliability. Other
emerging technologies such as forward osmosis (FO) and membrane distillation (MD) can find niche
applications in treating high salinity feed waters that cannot be desalinated by RO. In this presentation
we will discuss the energy efficiency of desalination and the possible reductions in energy demand by
advanced membranes and state-of-the art seawater desalination technologies. The energy efficiency of
reverse osmosis desalination will be discussed first, focusing on single-stage operation as well as various
approaches of multi-staged operations. It will be shown that multi-staged operations can significantly
reduce the specific energy of desalination, approaching the theoretical thermodynamic minimum energy
of desalination. The relationship between the specific energy of desalination and RO membrane
permeability and selectivity will be delineated and guidelines and novel approaches for membrane design
will be discussed. Finally, an analysis of the energy efficiency of FO and MD desalination will be
presented and the implications for process selection and design will be provided.

PPEPPD 2016
th
Invited Lecture 7
Gas Hydrates and Their Role in Energy Applications and Desalination
Carolyn A. Koh*,1, M. Naveed Khan1,2, Hongfei Xu1, Cornelis Peters2,3, E. Dendy Sloan1,
David T. Wu1, Luis Zerpa1
1
Center for Hydrate Research, Department of Chemical & Biological Engineering
Colorado School of Mines, Golden, CO 80401, U.S.A.
2
Chemical Engineering Department Petroleum Institute Abu Dhabi U.A.E
3
Department of Chemical Engineering and Chemistry, Separation Technology Group Eindhoven
University of Technology Eindhoven, The Netherlands
*Corresponding author: ckoh@mines.edu
Scientific topic: Gas & oil downstream & upstream; Marine and saline systems & proceses
Keywords: Gas Hydrate, Clathrate, Flow Assurance, Desalination
Abstract
Gas hydrates are crystalline inclusion compounds comprising hydrogen-bonded water cages that trap
small gas molecules [1]. Understanding the formation and decomposition processes of gas hydrates is
critical in a number of energy applications. These application areas include: maintaining flow in oil/gas
subsea pipelines without forming gas hydrate blockages (flow assurance); energy recovery from natural
gas hydrate deposits in oceanic sediments and sediments under the permafrost in arctic regions; energy
storage (natural gas, hydrogen) in clathrate hydrate materials. A further application of clathrate hydrates
is the process of seawater desalination, in which salt ions are excluded from the hydrate lattice. This
leads to salt ions being concentrated in the remaining water phase, while fresh water can be potentially
extracted on hydrate dissociation. The key barriers to achieving effective desalination using a hydrate-
based technology are the hydrate nucleation and growth/conversion processes, as well the effective
separation of hydrate crystallites from seawater. This paper provides an overview of the technological
advancements of hydrate science and engineering, and the strategies that have been adopted to achieve
acceptable desalination efficiencies.
References
[1] E.D. Sloan and C.A. Koh, Clathrate Hydrates of Natural Gases, 3rd Ed., CRC Press, Boca Raton, FL, 2007.
Acknowledgements
The authors would like to acknowledge the funding from the CSM Center for Hydrate Research Consortium for the
Energy Applications work, and the Petroleum Institute, Abu Dhabi for funding MNK and HX and the desalination
project.

PPEPPD 2016
th
Invited Lecture 8
Insights into the Adsorption and Phase Behaviour of Fluids in Micro-

Mesoporous Adsorbents with Hierarchical Pore Structure:
Towards an Advanced Pore Structural Characterization
Matthias Thommes* and Katie A.Cychosz
Quantachrome Instruments, Boynton Beach, FL 33426
*Corresponding author: matthias.thommes@quantachrome.com
Scientific topic: Adsorpion, Porous Materials
Keywords: adsorption, nanopores, fluid phase behavior, characterization
Abstract
Recently, much effort has been devoted to the development of materials which exhibit hierarchical pore
structure with the appropriate balance of micropores and mesopores, as well as advantageous pore
connectivity. The network of interconnected micro- and mesopores facilitates efficient transfer of fluids
to and from catalytically active sites, leading to benefits in numerous catalytic applications. With the
development of these materials, a large amount of work has been dedicated to their pore structural
characterization. Detailed insights about the pore architecture (pore size distribution, pore volume, and
pore interconnectivity) are important because they control transport phenomena, diffusional rates, and
govern selectivity.
Gas adsorption is well suited for this characterization because it assesses a wide range of pore sizes,
spanning the entire micro- and mesopore range. Within the last two decades major progress has been
achieved in understanding the adsorption and phase behavior of fluids in ordered nanoporous materials
and in the development of advanced approaches based on statistical mechanics such as molecular
simulation and density functional theory (DFT) of inhomogeneous fluids (see reviews [1,2] and
references therein). This progress, coupled with the availability of high resolution experimental
procedures for the adsorption of various subcritical fluids, has led to major advances in the structural
characterization by physical adsorption. These advances and corresponding recommendations for
physisorption characterizatoin are also sumarized in a new IUPAC technical report which has been
recently [3]. In fact, argon (87 K) adsorption coupled with methods such as non-local density functional
theory (NLDFT) allow one to obtain an accurate pore size distribution over the entire micro- and
mesopore size range using a single method [1 -3]. However, for an in-depth characterization of the pore
network (and the development of new methodologies) [4], a detailed understanding of the adsorption and
phase behaviour of fluids confined in such complex pore structures is needed. This is crucial for
advancing the application of nanoporous materials such as mesoporous zeolites in catalysis, separations,
and other industrial processes.
References
[1] Thommes, M., Cychosz, K.A. Adsorption 20, 233 (2014).
[2] Landers, J., Gor, G.Y., Neimark, A.V. Colloids Surfaces A 437, 3 (2013).
[3] M. Thommes, K. Kaneko, A.V. Neimark, J.P. Olivier, F. Rodriguez Reinoso, J. Rouquerol and K.S.W Sing,
Pure Appl. Chem. 87, 1051 (2015)
[4] Garcia-Martinez, J., Xiao, C., Cychosz, K.A., Li, K., Wan, W., Zou, X., Thommes, M. ChemCatChem 6, 3110
(2014).

PPEPPD 2016
th
Jonh M. Prausnitz Award
Multiscale Molecular Simulations of Polymer Matrix Nanocomposites
Georgios G. Vogiatzis and Doros N. Theodorou*

School of Chemical Engineering, National Technical University of Athens, Greece
*Corresponding author: doros@central.ntua.gr
Scientific topic: Molecular and multiscale simulation, nanoscience and nanotechnology
Keywords: polymers, nanocomposites, glass transition, chain conformation, multiscale modeling
Abstract
The dispersion of nanoparticles within polymer matrices can serve as a basis for developing materials
with novel properties. How these properties depend on the molecular characteristics of the constitutent
chains and nanoparticles is still not fully understood, however. Molecular modeling and simulation hold
great promise as means for elucidating and predicting structure-property relations, but face serious
challenges associated with the very broad spectra of time and length scales governing the behavior of
polymer matrix nanocomposites.
In this presentation we will outline a hierarchical strategy for predicting the structure, thermomechanical,
and rheological properties of materials consisting of spherical nanoparticles of roughly spherical shape
dispersed in amorphous polymers. This strategy encompasses (a) detailed molecular dynamics (MD)
simulations [1]; (b) coarse-grained Monte Carlo (MC) simulations, in which every repeat unit of the
polymer is represented as a single interaction site [1]; (c) Field Theory-inspired Monte Carlo (FTiMC)
simulations, in which chains are treated as sequences of Kuhn statistical segments [2,3]; (d) Brownian
Dynamics/kinetic Monte Carlo (BD/kMC) simulations, where chains are reduced to strings of beads
connected by springs, each bead encompassing 5-10 Kuhn segments, and entanglement points are
reduced to slip-springs connecting beads on different chains. Each level of model representation invokes
parameters that can be derived from more detailed levels, so that, ultimately, all predictions are based on
an atomistic force field.
Invoking these computational tools, we will explore (i) how the conformations, segmental motions, and
glass transition of atactic polystyrene are affected by dispersion of fullerenes; (ii) how the structure and
dimensions of the corona of grafted polystyrene chains on the surface of a silica nanoparticle, used to
promote dispersion in molten polystyrene, depend on molar mass and surface grafting density; (iii) how
the stress relaxation modulus, which quantifies the linear viscoelasticity of cis-1,4 polyisoprene melts, is
affected by their molecular characteristics.
References
[1] G.G. Vogiatzis, D.N. Theodorou, “Local segmental dynamics and stresses in polystyrene-C60 mixtures”
Macromolecules, 2014, 47: 387-404.
[2] G.G. Vogiatzis, D.N. Theodorou, “Structure of polymer layers grafted to nanoparticles in silica-polystyrene
nanocomposites” Macromolecules, 2013, 46: 4670-4683.
[3] D.N. Theodorou, G.G. Vogiatzis, G. Kritikos, “Self-consistent field study of adsorption and desorption kinetics
of polyethylene melts on graphite and comparison with atomistic simulations” Macromolecules, 2014, 47: 6964-
6981.

PPEPPD 2016
th
Workshop 1: Applications of SAFT-type models - WSAFT-1
An Introduction to SAFT and Applications in the Energy Industry
Walter G. Chapman
Dept. of Chemical and Biomolecular Engineering, Rice University
*Corresponding author: wgchap@rice.edu
Abstract
In this workshop, we will present the physical basis of the SAFT family of models. An advantage of
theoretically based models is that the theory can be validated versus molecular simulation and
systematically improved for more complex fluid systems. We demonstrate these points through
applications for bulk phase behavior, interfacial properties, and self-assembly in hydrocarbon energy
systems.
In the energy field, flow assurance, compositional grading, and enhanced oil recovery require accurate
modeling of phase behavior, transport properties, interfacial properties, and molecular level self-
assembly. Past approaches in the industry have required specialized models for varying conditions and
for each separate phase with sometimes unsatisfactory results. The SAFT approach is enabling engineers
to predict fluid properties in the hydrocarbon, aqueous, and gaseous phases as well as the interfacial
properties between these phases with a single unified model. Successes are shown in applications of the
SAFT approach in characterizing crude oil and describing asphaltene phase behavior, water content, and
surfactant self-assembly.

PPEPPD 2016
th
Integrated molecular and process design with the SAFT platform
A. Galindo, C. S. Adjiman, and G. Jackson
Department of Chemical Engineering, Centre for Process Systems Engineering,
Imperial College London, London SW7 2AZ, UK
*Corresponding author: g.jackson@imperial.ac.uk
Abstract
The statistical associating fluid theory (SAFT) molecular-based equation of state can now be considered
as a mature technology for the representation of the thermodynamic properties and fluid-phase equilibria
of complex fluids and mixtures. On the other hand the use of the more sophisticated SAFT equations of
state as a thermodynamic platform within the context of process modelling is relatively rare. The group
contribution formulations of SAFT offer a particular advantage in the area of integrated
molecular/mixture and process design. A key objective of this type of work is to provide a unified
systems approach and model-based platform in order to assess the potential capabilities of alternative
molecules and mixtures. In this talk the focus will be on the use of SAFT in process models to assess
solvents and solvent blends for the economics of the separation of carbon dioxide (CO2) from methane at
well-head conditions. The post-combustion capture of CO2 from flue gas at large fixed point emission
sources will also be discussed. In developing this methodology, one combines SAFT thermodynamics
with rigorous process simulation tools and techniques. To account for the non-idealities that are typical
of amines and water, the SAFT formalism can be used to represent some of the equilibrium reactions
characterising the system, thereby simplifying the description of the chemical reactions. A validated rate-
based model of an absorber/stripper system for the chemisorption of acid gas in aqueous solvent
solutions is implemented in the gPROMS software package. Our model does not consider reaction
products explicitly; these are accounted for at the level of the thermodynamic model proposed for the
fluid as reacted aggregates. Cost-optimal process and solvent-blend design can identified via a
constrained, multi-parametric optimisation approach. The objective function is the minimisation of total
process cost (both CAPEX and OPEX) per unit of CO2 captured. The design variables are the flowrate
and state of the lean solvent and inlet gas streams as well as column geometry. Key performance
indicators such as CO2 emissions, solvent losses to the environment as well as the minimisation of
energy required for solvent regeneration and also minimisation of CO2 emissions to the atmosphere are
included in the optimality criteria.

PPEPPD 2016
th
Application of PC-SAFT to pharmaceutical systems
Gabriele Sadowski
Laboratory of Thermodynamics, TU Dortmund University, Germany
*Corresponding author: gabriele.sadowski@bci.tu-dortmund.de
Scientific topic: workshop SAFT modeling
Keywords: pharmaceutical systems, amorphous dispersions, influence of humidity
Abstract
The talk discusses the application of Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT)
for modeling the phase behavior of systems containing active pharmaceutical ingredients (APIs). This
includes APIs in aqueous solutions as well as ASD formulations in polymers.
APIs often show a very low solubility in water as well as a low dissolution rate, both resulting in a very
low bioavailability. One approach to improve the API dissolution rate is the formation of amorphous
solid dispersions (ASDs) in which the API is molecularly dissolved in an amorphous polymer matrix.
The thermodynamic phase behavior of such a system determines, whether the API can be completely
dissolved in the polymer resulting in a thermodynamically-stable state or tends to recrystallize or
whether the ASD separates into two amorphous phases.
Moreover, humidity has a huge impact on the phase behavior of ASDs. Depending on the kind of API
and polymer and on temperature and humidity, ASDs absorb remarkable amounts of water. This may
lead to a tremendous change in the phase diagram compared to the water-free systems. In particular this
often causes much lower solubilites of the hydrophobic API and therewith increases the probability of
recrystallization and phase separation during storage and can be also predicted by PC-SAFT.

PPEPPD 2016
th
Predicting interfacial properties and transport properties
using SAFT equations of state
Joachim Gross
*Corresponding author: gross@itt.uni-stuttgart.de
Abstract
Analytic equations of state based on the SAFT model [1] have developed as versatile tools to predict
various thermodynamic properties. Interfacial properties and transport properties have in recent years
shifted into focus. When applied with the classical density functional theory, SAFT models provide a
powerful framework to predict interfacial properties. This workshop-contribution gives a review of
SAFT-based approaches for calculating interfacial properties [2,3]. A brief review of the density
functional theory is given. Results are presented for vapor-liquid and liquid-liquid interfacial properties,
as well as for fluids in confined space (porous materials).
As a second topic, the talk reviews entropy-scaling as a framework for predicting transport properties,
such as viscosities or thermal conductivities. Comprehensive data analysis shows a remarkable accuracy
of excess entropy scaling, as originally proposed by Rosenfeld [4], for the calculation of transport
properties. A new group-contribution approach for the prediction of shear viscosities and thermal
conductivities is described [5]. For pure organic fluids in a wide range of temperature and pressure the
approach is found in good agreement with experimental data. Additionally, first results for mixture
viscosities are shown as well as for self-diffusion coefficients. The results suggest the method is suitable
for use in product and process design [6].
References
[1] W. G. Chapman, G. Jackson, K. E. Gubbins, Phase equilibria of associating fluids: Chain molecules with
multiple bonding sites. Molec. Phys. 1988, 65, 1057.
[2] J. Gross, G. Sadowski, Perturbed-chain SAFT: An equation of state based on a perturbation theory for chain
molecules. Ind. Eng. Chem. Res. 2001, 40, 1244.
[3] J. Gross.A density functional theory for vapor-liquid interfaces using the PCP-SAFT equation of state. J. Chem.
Phys. 2009, 131, 204705.
[4] Y. Rosenfeld, Relation between the transport coefficients and the internal entropy of simple systems, Phys. Rev.
A 1977, 15, 2545-2549
[5] O. Lötgering-Lin, J. Gross, A group contribution method for viscosities based on entropy scaling using the
pertubed-chain polar statistical associating fluid theory, Ind. Eng. Chem. Res. 2015, 54, 7942-7952.
[6] A. Bardow, K. Steur, J. Gross. Continuous-Molecular Targeting for Integrated Solvent and Process Design. Ind.
Eng. Chem. Res. 2010, 49, 2834.
PPEPPD 2016
th
Workshop 2: Force fields for properties and phase equilibria for product and
process design- WFF-1
Transferable Potentials for Phase Equilibria: Development, Validation,

Verification, and Uncertainty
J. Ilja Siepmann1,2
1
Department of Chemical Engineering and Materials Science, University of Minnesota, USA
2
Department of Chemistry and Chemical Theory Center, University of Minnesota, USA
*Corresponding author: siepmann@umn.edu
Scientific topic: Thermodynamics and transport properties, Phase equilibria, Molecular and multiscale simulation,
Quantum mechanical calculations and force fields,
Keywords: Force field, potential energy function, predictive modeling
Abstract
This presentation will highlight the efforts to develop accurate and efficient molecular mechanics force
fields that allow predictive modeling for a wide range of chemical compounds, state points, and
thermophysical properties. The to some extent competing virtues of accuracy and efficiency necessitate a
family of force fields that can utilized to address problems of different degrees of complexity. The talk
will discuss the parameterization strategy used for the various members of the TraPPE force field. The
talk will also address efforts made to validate, verify, and quantify the uncertainty of the TraPPE force
fields and in developing a comprehensive cyberinfrastructure for parameter and property retrieval.
Acknowledgements
Financial support from the National Science Foundation and computer resources from the Minnesota
Supercomputing Institute are gratefully acknowledged.

PPEPPD 2016
th
Three worked examples for developing force fields:

water, hydrates and NaCl solutions
Carlos Vega
1
Departamento de Quimica Fisica, Universidad Complutense de Madrid, Spain
*Corresponding author: cvega@quim.ucm.es
Keywords: Keyword1, Keyword2, Keyword3 (maximum 5 keywords)
Abstract
When performing computer simulations, it is necessary to choose a potential model. It should be

recognized that the exact energy of the system for a certain configuration can only be obtained after
solving exactly the Schrodinger equation. The computational cost of that is huge and for this reason one
often uses an approximate expression commonly denoted as force field. Empirical force fields have
some parameters that must be determined. It is impossible that empirical force fields describe all
properties. For this reason one should select a set of target properties to be reproduced. In this
presentation we shall present the procedure we used to develop a force field around water: TIP4P/2005.
We shall also discuss an important point: the potential parameters that are good to describe the potential
energy surface may not be good to describe the dipole moment surface [1]. We shall illustrate the
limitations of non-polarizable models when describing water properties.
The cases of mixtures is even more challenging as one must describe the cross interaction between the
two components. We shall present results about how to develop a force field for hydrates[2,3] and the
current situation of force fields for ions in water [4,5,6].
References
[1] C. Vega, Mol. Phys., 113, 1145 , (2015)
[2] J.M. Míguez, M.M. Conde, J.P. Torre, F.J. Blas, M.M. Pineiro, and C. Vega, J. Chem. Phys., 142, 124505,
(2015)
[3] V.K. Michalis, J.Costandy, I.N. Tsimpanogiannis, A.K.Stubos and I.G. Economou, J. Chem. Phys., 142,
044501, (2015)
[4] A.L. Benavides, J.L. Aragones and C. Vega , J. Chem. Phys., 144 ,124504, (2016)
[5] Z. Mester and A.Z.Panagiotopoulos, J. Chem. Phys., 142, 044507, (2015)
[6] I.Nezbeda, W.R.Smith and F.Moucka, Mol.Phys., in press, (2016) DOI:10.1080/00268976.2016.1165296
PPEPPD 2016
th
Coarse grained force field development:

applications within the corresponding states framework
Guillaume Galliero*
Laboratoire des Fluides Complexes et leurs Réservoirs (UMR-5150 with CNRS and TOTAL), Université de Pau et
des Pays de l'Adour, BP 1155, F-64013 Pau Cedex, France
*Corresponding author: guillaume.galliero@univ-pau.fr
Scientific topic: Workshop on force field development
Keywords: Coarse grained models, Fluids, Transport properties, Corresponding states
Abstract
During the workshop, we will present a generic top-down strategy [1], based on an extended
corresponding states framework [2], to build force fields for some coarse grained molecular models [3].
As an example the proposed strategy will be applied to the Mie-Chain model.
It will be shown that such an approach, combined with classical molecular simulations, allows to
provide a very good estimate of thermophysical (equilibrium, interfacial and transport) properties of
some fluids typical of the oil&gas industry. In addition, it will be shown how such an approach can be
combined with modern molecular thermodynamics to yield thermophysical properties without molecular
simulations [3-5].
References
[1] A. Mejía, C. Herdes and E. A. Müller, “Force Fields for Coarse-Grained Molecular Simulations from a
Corresponding States Correlation”, Industrial& Engineering Chemistry Research, 2014, 53, 4131−4141
[2] W.G. Noid,” Perspective: Coarse-grained models for biomolecular systems”, Journal of Chemical Physics,
2013, 139, 090901.
[3] G. Galliero, “Equilibrium, interfacial and transport properties of n-alkanes: Towards the simplest coarse grained
molecular model”, Chemical Engineering Research and Design, 2014, 92, 2031-2037.
[4] G. Galliero, C. Boned, J. Fernandez, “Scaling of the viscosity of the Lennard-Jones chain fluid model, argon
and some normal alkane”, Journal of Chemical Physics, 2011, 134, 064505.
[5] T. Lafitte, A. Apostolakou, C. Avendaño, C.S. Adjiman, E.A. Müller, G. Jackson, “”Journal of Chemical
Physics, 2013, 139, 154504.
Acknowledgements
We gratefully acknowledge TOTAL S.A. for letting us publishing these results.

PPEPPD 2016
th
Polarizable force fields for property prediction of CO2 – brine mixtures

related to CCS and EOR processes
Ioannis G. Economou
Texas A&M University at Qatar, Chemical Engineering Program, Doha, Qatar
*Corresponding author: ioannis.economou@qatar.tamu.edu
Abstract
One of the greatest global problems today is the increase of CO2 concentration in the atmosphere that at
the end of March 2016 reached the value of 405 ppm, which is unprecedented for the last several
thousands of years. CO2 is the most important of the so called greenhouse gases (GHGs) which are
considered to be the main reason behind the global climate changes. Carbon capture and sequestration
(CCS) is advocated widely as the most promising technology for the generous decrease of CO2
concentration in the atmosphere. Furthermore, CO2 injection in depleted oil wells has been used since the
1980s in enhanced oil recovery (EOR) processes to increase oil recovery rates. Conceptual design,
simulation and optimization of these processes are based on the fundamental understanding of the
molecular interactions of CO2 with the reservoir rocks and the interactions of CO2 with H2O and salts
(since many CCS sites are close to aquifers), and a number of other gases in small concentrations from
the original source. Using appropriate computational methods, one can calculate a broad range of
physical properties (such as phase equilibria, diffusion coefficients, permeability, wettability, etc.) that
are critical for the process design. In this presentation, we will focus on the development and validation
of polarizable force fields for the prediction of equilibrium and transport properties of CO2 – brine
mixtures [1,2]. It will be shown that polarizable force fields are more accurate than two-body force
fields for the majority of the properties examined [3,4].
References
1. H. Jiang, Z. Mester, O.A. Moultos, I.G. Economou and A.Z. Panagiotopoulos, “Thermodynamic and Transport
Properties of H2O + NaCl from Polarizable Force Fields”, J. Chem. Theory Comput., 11(8), 3802 – 3810
(2015).
2. H. Jiang, O.A. Moultos, I.G. Economou and A.Z. Panagiotopoulos, “Gaussian-Charge Polarizable and
Nonpolarizable Models for CO2”, J. Phys. Chem. B, 120(5), 984 – 994 (2016).
3. O.A. Moultos, I.N. Tsimpanogiannis, A.Z. Panagiotopoulos and I.G. Economou, “Atomistic Molecular
Dynamics Simulations of CO2 Diffusivity in H2O for a Wide Range of Temperatures and Pressures”, J. Phys.
Chem. B, 118(20), 5532 – 5541 (2014).
4. G.A. Orozco, O.A. Moultos, H. Jiang, I.G. Economou and A.Z. Panagiotopoulos, “Molecular Simulation of
Thermodynamic and Transport Properties for the H2O + NaCl System”, J. Chem. Phys., 141(23), 234507-1 –
234507-8 (2014).
Acknowledgments
This publication was made possible by NPRP [grant number 6-1157-2-471] form the Qatar National Research Fund
(a member of Qatar Foundation). The statements made herein are solely the responsibility of the authors. We are
grateful to the High Performance Computing Center of Texas A&M University at Qatar for generous resource
allocation

PPEPPD 2016
th
Oral Session 7 – Phase Equilibria 1 – O7-1
Phase Behavior of Amino Acids on Graphene Oxide, Titanium Dioxide and

their Nanocomposite
Liangliang Huang1*, Shanshan Wang2,3, Chang Liu2,3, Linghong Lu2,3 and Xiaohua Lu2,3
1
School of Chemical, Biological and Materials Engineering, University of Oklahoma
Norman, OK 73019-1003, U.S.A.
2
School of Chemical Engineering, Nanjing Tech University, Nanjing 210009, China
3
State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009,
China
*Corresponding author: HLL@ou.edu
Scientific topic: Molecular Innovation:Materials for a better future (Catalysis)
Keywords: Surface chemistry, molecular modeling, phase behavior, reactive adsorption, graphene oxide,
titanium dioxide, nanocomposite
Abstract
It is well known that the phase behavior of near-surface molecules can be fine tuned by a combination of
surface geometry, surface chemistry and the solution effects such as pH and concentration. A knowledge
of these effects and a strategic optimization are important in many applications: examples include
biochemical sensing and separation, cell imaging, in vitro and in vivo targeted drug delivery, cancer
therapy, toxic species removal from air, remediation of soils and ground water.
As the fundamental biomolecular building blocks, amino acids are excellent simple models for
understanding the interactions of biomaterials with surfaces and interfaces. In this work, we combine
multi-scale modeling techniques to study the phase behavior of amino acids on graphene oxide (GO),
titanium dioxide (TiO2) and their nanocomposite (GO/TiO2). By ab initio density functional theory
(DFT) method and reactive molecular dynamics (RxMD) simulations, we calculate amino acid
interaction with these model systems. Specific focuses have been placed on: (a) the surface
functionalization of GO, that is, a comparison between pristine graphene and realistic atomistic GO
models1 will be discussed; (b) the facet reactivity of TiO2 and the solution effect, following our previous
results2 where water demonstrates significantly different properties on various TiO2 facets. The GO/TiO2
nanocomposite and the enhancement towards amino acid adsorption and diffusion will be also discussed.
Parallel experimental studies, such as Fourier transform infrared spectroscopy, gas chromatography and
mass spectrometry, thermal analysis, X-ray diffraction and potentiometric titration measurements, will be
discussed and compared with the theoretical results.
References
[1] Liangliang Huang, Mykola Seredych, Teresa J. Bandosz, Adri C. T. van Duin, Xiaohua Lu and Keith E.
Gubbins, “Controllable Atomistic Graphene Oxide Model and its Application in Hydrogen Sulfide Removal”, J.
Chem. Phys., 2013, 139, 194707.
[2] Liangliang Huang, Keith E. Gubbins, Licheng Li and Xiaohua Lu, “Water on Titanium Dioxide Surface: A
Revisiting by Reactive Molecular Dynamics Simulations”, Langmuir, 2014, 30, 14832.

PPEPPD 2016
th
Phase Transitions in Models of Deeply Supercooled of Water
Jeremy C. Palmer1,*, Fausto Martelli2, Francesco Ricci3, Roberto Car2,

Athanassios Z. Panagiotopoulos3 and Pablo G. Debenedetti3
1
Department of Chemical and Biomolecular Engineering, University of Houston, USA
2
Department of Chemistry, Princeton University, USA
3
*Corresponding author: jcpalmer@uh.edu
Keywords: water, supercooled, metastable phase transition
Abstract
Many of the well-known thermodynamic anomalies of water, such as its negative thermal
expansion and increased compressibility upon cooling, become more pronounced when it is
cooled below its freezing point into a metastable liquid. One thermodynamically consistent
interpretation of water’s anomalies posits that water becomes highly compressible when
cooled below its freezing point due to the presence of a second critical point associated
with a first-order phase transition between two metastable liquid phases 1. Because the
region of the phase diagram where this hypothetical critical point would occur is below the
homogenous nucleation temperature of bulk water, obtaining direct experimental evidenc e
to falsify the second critical point hypothesis has so far proved to be a significant
challenge.
We examine the phase behavior of the ST2 water model under deeply supercooled
conditions using six state of the art computation methods to compute the revers ible free
energy surface parameterized by density and bond-orientational order[1]. We find that free
energy surfaces clearly show two liquid phases in coexistence. The nature of the liquid -
liquid phase transition is also investigated by examining the finite-size scaling behavior of
the free energy barrier separating the two liquids. Our calculations show that the barrier
height obeys the N 2/3 scaling law expected for a first-order transition, suggesting the
existence of an associated second critical point in ST2 water. To our knowledge, this is the
first unambiguous computational evidence of a mestastable liquid-liquid phase transition in
a pure substance.
References
[1] J. C. Palmer, F. Martelli, Y. Liu, R. Car, A. Z. Panagiotopoulos, P. G. Debenedetti, “Metastable liquid-liquid
transition in a molecular model of water” Nature 2014, 501:385-388.

PPEPPD 2016
th
20 years with the CPA Equation of State
Georgios M. Kontogeorgis
Center for Energy Resources Engineering (CERE)
Department of Chemical and Biochemical Engineering
Technical University of Denmark, Building 229, DK-2800, Denmark
*Corresponding author: gk@kt.dtu.dk
Scientific topic: Thermodynamics, Phase Equilibria (modeling)
Keywords: Cubic-Plus-Association, Equation of State, Industrial applications
Abstract
Almost a century and a half has elapsed since van der Waals proposed his now famous equation of state
(EoS) which bears his name. For almost one century, much research and applications were dominated by
the cubic EoS, including the advanced EoS/GE mixing rules during the 80s and 90s (Huron-Vidal,
MHV2, PSRK, Wong-Sandler, LCVM,…) [1,2]. While such models have found widespread industrial
applications, especially in the petroleum and chemical industries, non-cubic equations of state are
progressively become popular. Many of these more advanced models are now presented in textbooks
[3,4]. A major breakthrough came in the late 80’s with the advent of the SAFT theory (Statistical
Associating Fluid Theory), which resulted by now in a large number of variants. In 1996 the CPA
(Cubic-Plus-Association) equation of state has been published [5], a model combining the cubic equation
of state (e.g. SRK) for the physical term Wertheim’s association term (as used in SAFT).
20 years after its publication, CPA is now a rather mature model that is widely used by many companies
and provided by several commercial vendors. Much has been accomplished and much more still needs to
be done! This presentation will provide a short overview, largely based on unpublished results and
personal experiences, on some of the major CPA applications, accomplishments and future challenges.
The applications will be related to problems of petroleum, energy (in general), and chemical industries.
Comparisons to SAFT and other models will be presented for some cases.
References
[1] G.M. Kontogeorgis, Ph. Coutsikos, 2012. Thirty years with EoS/GE models – wht have we learned? Ind. Eng.
Chem. Res., 51(11), 4119-4142.
[2] G.M. Kontogeorgis, I.G. Economou, 2010. Equations of state: From the ideas of van der Waals to association
theories. J. of Supercritical Fluids, 55, 421-437.
[3] J.M. Prausnitz, R.N. Lichtenthaler, E.G. de Azevedo. Molecular Thermodynamics of Fluid-Phase Equilibria
(3rd edition). Prentice Hall Int., 1999.
[4] G.M. Kontogeorgis, G.K. Folas. Thermodynamic models for industrial applications. From Classical and
Advanced mixing rules to association theories, Wiley, 2010.
[5] G.M. Kontogeorgis, E. Voutsas, I. Yakoumis, D.P. Tassios, 1996. An equation of state for associating fluids.
Ind. Eng. Chem. Res., 35: 4310-4318.

PPEPPD 2016
th
Hybrid Datamining-Thermodynamic Method for Coarse-Grained Phase

Calculations in Petrochemical and Biological Complex Fluids.
Johannes G.E.M. Fraaije12* and Ruben Serral Gracia2

1
Leiden Institute of Chemistry, Leiden University, The Netherlands
2
Culgi BV, Leiden, The Netherlands
*Corresponding author: hans.fraaije@culgi.com
Scientific topic: Thermodynamics, Phase Equilibria
Keywords: Thermodynamics, Database, Crude Oil. Pharmaceuticals, Complex Fluids
Abstract
With the advance in computational chemistry methods, easy database access and cheap computer power,
the quest is for calibration of 3D molecular interaction potentials using massive amounts of data. Such
potentials find immediate usage in a wide range of truly complex fluids, whether from biological or
petrochemical origin, that are quite common in an industrial context. We discuss the fundamentals of
such approach in the framework of soft potentials as they arise in coarse-grained modeling. The protocol
consists of four concerted steps: (a) the automation of finding groups of atoms as coarse-grained units
(Automated Fragmentation), followed by (b) the automated calculation of densities and mixing
thermodynamics (Gibbbs energies) using ultrafast equation-based coarse-grained Hypernetted Chain/
Reference Interaction Site Modeling, (c) the development of an extremely simple interaction model, that
is essentially based on only excluded volume interactions and COSMO-RS thermodynamics, and finally,
(d) calibration using large databases from PubChem (for fragmentation study) and NIST Thermodynamic
Data Engine (TDE, calibration on thermodynamics data). Using the automated fragmentation on sets up
to 100k molecules, we find that fragment distribution follows Zipf and Heap scaling laws. These laws are
quite common in linguistics, but new in thermodynamics. We speculate that a few ten thousands
fragments of 2-4 atoms could be enough to cover the chemical thermodynamics of vast repositories such
as the CAS registry, or for that matter any existing chemicals thermodynamics database. Most
importantly, from the automated parameterization on mixing Gibbs energies using 1092 pairs of liquids
from the NIST TDE databank, we achieve an unprecedented accuracy in mixing thermodynamics of a
few 100 kJoule per mol of fragment, which we consider is enough for many old and new applications in
both materials and life science research. The approach propels existing coarse-grained group
classification from laborious chemical intuition into rule-based automation. The approach brings
chemistry into coarse-grained modeling in a systematic and unified way and is therefore suited for
handling massive databases of extremely wide chemical diversity. CULGI is sponsored by an
international industrial consortium, from chemical industry, personal care, pharmaceutical and petroleum
industries. As proof op concept, we will demonstrate the approach on two opposing real world problems:
emulsion formation in oil reservoirs, and pharmaceutical docking calculations.

PPEPPD 2016
th
Oral Session 8 – Surfaces, Interfaces and Confinement 1 – O8-1
Influence of Molecule Architecture on Phase Equilibria and Interfacial

Properties
Christoph Walowski, Patrick Zimmermann and Sabine Enders*
*Corresponding author: sabine.enders@kit.edu
Keywords: Lattice Cluster Theory, Branching effects, Density gradient theory, Density functional
theory, Adsorption isotherms
Abstract
All occurring phase equilibria as well as the interfacial properties depend on the one side on the
interactions between the molecules present and on the other hand on the architecture of the
molecules. This contribution focuses on the influence of the molecular architecture on different
types of phase equilibria and the properties related to two different interfaces. The incorporation
of these effects in the thermodynamic equations can be realized by the Lattice Cluster Theory
(LCT) originally developed by Freed and Coworkers [e.g. 1] and applied for different substance
classes reaching from pure alkanes [2] to mixtures containing linear, branched and
hyperbranched polymers [e.g. 3,4].
Within the LCT the Helmholtz energy can be obtained by double series expansion in inverse
coordination number and in interaction energy taking into account the molecule architecture. This
situation allows us to model the liquid-liquid-equilibrium (LLE) and the solid-liquid-equilibrium (SLE).
In order to model the vapor-liquid equilibrium (VLE) empty lattices are placed on the lattice resulting in
an equation of state (LCT-EOS).
In this contribution, the LCT-EOS will be applied to two different interfaces. The first one is the
interphase established between two fluid phases related to the VLE or the LLE. In this case the LCT-
EOS will be combined with the density gradient theory. This allows the calculation of the interfacial
tension and the interfacial profile. The second one is the interphase between a bulk-fluid phase and a
porous solid. This situation requires the combination of the LCT-EOS with the density functional theory
including an external potential for the description of the interaction between the fluid and the pore [5].
This approach is used to discuss the possibilty for separation of closed-boiling mixtures of different types
of aldehydes by adsorption.
References
Macromolecules, 1991, 24: 5076-5095.
[2] K. Langenbach, S. Enders, “Development of an Equation of State Based on Lattice Cluster Theory for Pure
Components” Fluid Phase Equilibria 2012, 331: 58–79.
State for Multi-Component Systems.” Fluid Phase Equilibria 2014, 363: 196-212.
[4] T. Zeiner, S. Enders, “Phase-Behavior of Hyperbranched Polymer Solutions in Mixed Solvents.” Chem. Eng.
Sci. 2011, 66: 5244–5252.
[5] R. Evans, Fundamentals of Inhomogeneous Fluids, edited by D. Henderson (New York: Marcel Dekker) 1992.
Acknowledgements
For financial support the authors thank the German Science Foundation (DFG) and the collaborative research centre
SFB Transregio 63.
PPEPPD 2016
th
Molecular Simulation Study of Fluids in Geological Formations
Wenjing Guo1, Adam R. Rall1 , and Jeffrey R. Errington1*

1
Department of Chemical and Biological Engineering, University at Buffalo, The State University of New York,
Buffalo, NY 14260-4200, USA
*Corresponding author: jerring@buffalo.edu
Scientific topic: Surfaces, interfaces, and confinement effects; Phase equilibria; Molecular and multiscale
simulation; Carbon capture and storage
Keywords: Wetting, water/CO2, water/oil, molecular simulation
Abstract
Fluids within geological formations play an important role in many industrial processes and strategies to
protect the environment. For example, carbon dioxide storage via injection into saline aquifers is a
promising option for the reduction of greenhouse gas emissions and the potential mitigation of global
climate change. Here, the estimation of reservoir capacity relies upon knowledge of two key interfacial
properties of the CO2/water/rock system: (1) the interfacial tension between the CO2-rich and water-rich
phases and (2) the contact angle that a water-rich droplet forms at a mineral surface in a mother CO2-rich
background. A second example relates to the extraction of oil from underground reservoirs. The well
environment is characterized by porous rock surrounded by oil- and water-based liquids. Here, the
development of enhanced oil recovery strategies relies upon knowledge of the wetting behavior of
oil/water/rock systems. In this presentation, we first discuss the development of Monte Carlo simulation
methods for determining the bulk and interfacial properties of these systems. We then provide examples
of their implementation to study the properties of two model systems. We first consider the properties of
a CO2/water/silica system. Results are presented for the evolution of the contact angle and CO 2/water
interfacial tension over a range of pressures at select temperatures. We then examine the behavior of a
octane/water/silica system. We present results that show how wetting properties, such as the contact
angle of a water droplet at a silica surface in a mother octane phase, evolve with temperature, pressure,
and composition. We also discuss how contaminants (e.g., carboxylic acids) modify the wetting behavior
of this system. In all cases, we examine connections between macroscopic properties and the manner in
which particles organize within these inhomogeneous systems. Connections are also made to
experimental studies when possible.
Acknowledgements
We gratefully acknowledge the financial support of the National Science Foundation (CBET-1264323).

PPEPPD 2016
th
Confinement-Induced High Pressure Phases In Nanopores.
Can The Pressure Be In The Megabar Range?
Cody K. Addington1, Deepti Srivastava1, Liangliang Huang2 and Keith E. Gubbins1

1
Department of Chemical & Biomolecular Engineering, North Carolina State University,
Box 7905, Raleigh, NC 27695-7905, U.S.A.
2
Chemical, Biological and Materials Engineering, University of Oklahoma, Norman, OK 73019
*Corresponding author: keg@ncsu.edu
Scientific topic: Molecular Innovation: Materials for a better future
Keywords: Lignin, Platinum, Palladium, Nanoparticles, Catalysis
Abstract
There is an abundance of anecdotal evidence that nanophases adsorbed within nanoporous

materials can exhibit high pressures as a result of the confinement1,2. For example, phase changes and
chemical reactions that only occur at high pressures in the bulk phase occur in the confined phase at bulk
phase pressures that are orders of magnitude lower. The pressure in the pore is a second order tensor, and
for simple pore geometries has both a normal pressure component (normal to the walls) and one or more
tangential components (parallel to the walls).
For simple fluids in pores that are up to a few nanometers in width, molecular simulations show
that both the normal and tangential pressures can be locally very high (thousands or tens of thousands of
bars) in the pore, even though the bulk phase in equilibrium with the pore is at a pressure of one bar or
less. The cause of these high in-pore pressures will be discussed, and where possible comparison with
experimental results will be made3.
When the molecules in the confined nanophase react with each other chemically it may be
possible to achieve even higher tangential pressures, in the megabar range. Evidence for this is provided
by recent experiments on sulfur (an insulator at ambient conditions) in narrow single-walled carbon
nanotubes, carried out by Kaneko and coworkers4. They find that the sulfur atoms within the pore
covalently bond to form a one-dimensional phase that is metallic. In the bulk phase sulfur forms a
metallic phase only at pressures above 95 GPa. In our recent molecular dynamics simulations of this
system we find that the sulfur atoms are covalently bonded in the pore and that they experience
tangential pressures in excess of 100 GPa as a result of the strong confinement.
References
[1] Yun Long, Jeremy C. Palmer, Benoit Coasne, Małgorzata Śliwinska-Bartkowiak and Keith E. Gubbins,
“Pressure enhancement in carbon nanopores: A major confinement effect”, Physical Chemistry Chemical Physics,
13, 17163-17170 (2011).
[2] Yun Long, Jeremy C. Palmer, Benoit Coasne, Małgorzata Śliwinska-Bartkowiak, George Jackson, Erich A.
Müller and Keith E. Gubbins, “On the Molecular Origin of High Pressure Effects in Nanoconfinement: Effects of
Surface Chemistry and Roughness”, Journal of Chemical Physics, 139, 144701 (2013)
[3] H. Drozdowski, M. Kempinski, M. Śliwinska-Bartkowiak, M. Jazdzewska, Y. Long, J.C. Palmer and K.E.
Gubbins, „Structural Analysis of the Behavior of Water Adsorbed in Activated Carbon Fibers”, Physical Chemistry
Chemical Physics, DOI: 10.1039/C2CP22111J (2012).
[4] Y. Fujimori, A. Morelos-Gómez, Z. Zhu, et al., “Conducting Linear Chains of Sulphur Inside Carbon
Nanotubes”, Nature Comm., 4, DOI 10.1038/ncomms3162 (2013).
PPEPPD 2016
th
Predictive molecular-based theory for interfacial tensions of industrial fluids.
José Matías Garrido1*, Manuel M. Piñeiro2, Felipe J. Blas3, Erich A. Müller4 & Andrés Mejía1
1
Departamento de Ingeniería Química, Universidad de Concepción, Chile
2
Departamento de Física Aplicada, Universidade de Vigo, Spain
3
Departamento de Física Aplicada, Universidad de Huelva, Spain
4
Department of Chemical Engineering, Imperial College London, United Kingdom
*Corresponding author: josemagarrido@udec.cl
Keywords: SAFT, Coarse Grained models, square gradient theory, molecular simulations, influence
parameter
Abstract
The magnitude of interfacial (or surface) tension governs the performance of most processes in chemical,
petroleum and environmental engineering; e.g. interfacial mass transfer unit operations, emulsification of
liquids, phase wettability, gravity-drainage recovery, tertiary oil recovery and gas injection in enhanced
oil recovery processes, groundwater remediation, amongst many others. In spite of this, the available
models for predicting the interfacial tension are based on empirical correlations limited in terms of the
temperature (or pressure) ranges, nature of the chemical species and accuracy of their results. This work
provides a molecular thermodynamic theory that allows the prediction of the interfacial tensions of pure
fluids with accuracy and robustness that surpasses all existing models.
The proposed model is based on the van der Waals square gradient theory (SGT) [1] and elegantly
combines the SAFT VR – Mie EoS [2], the corresponding states principia for parameter determination
[3] and scaling arguments. There is no need for experimentally adjusted parameters, typical of other SGT
applications. The results are expressed in terms of the reduced energy, size and range of the Mie
potential; hence the application to real fluids relies on mapping these properties to critical constants. The
only input parameters needed are the critical temperature, the acentric factor and the liquid density of the
fluid at a reference temperature.
The new theory has been tested for both molecular fluids (i.e. Mie  – 6 fluids and chains, with repulsive
exponent λ = 8 to 44) and industrial fluids (i.e. hydrocarbons, fluorocarbons, polar molecules, among
others), showing a maximum average absolute deviation of 2.2 %.
References
[1] J. S. Rowlinson. “Translation of J. D. van der Waals The thermodynamic theory of capillarity under the
hypothesis of a continuous variation of density” Journal of Statistical Physics 1979, 20(2):197–200.
[2] T. Lafitte, A. Apostolakou, C. Avendaño, A. Galindo, C. S. Adjiman, E. A. Müller, G. Jackson “Accurate

statistical associating fluid theory for chain molecules formed from Mie segments” The Journal of Chemical
Physics 2013, 139(15):154504–154540.
[3] A. Mejía, C. Herdes, E. A. Müller “Force Fields for Coarse-Grained Molecular Simulations from a
Corresponding States Correlation” Industrial & Engineering Chemistry Research 2014, 53(10):4131-4141.
Acknowledgements
The authors gratefully acknowledge the financial supports from Conicyt and Fondecyt (Chile) and EPSRC (U.K.).
Ministerio de Economía y Competitividad (Spain) is also acknowledged.

PPEPPD 2016
th
Poster Session III – P01
The Phase Behavior of Solutions of Ionic Liquids
Wolffram Schröer1 and Bernd Rathke2*

1
Universität Bremen, Institut für Anorganische und Physikalische Chemie, Leobener Str., 28359 Bremen,
Germnany
2
Universität Bremen, Technische Thermodynamik, Badgasteiner Str. 1, 28359 Bremen, Germany
*Corresponding author: rathke@uni-bremen.de
Keywords: Ionic liquid, Liquid-liquid equilibrium, Criticality, Solubility
Abstract
A comprehensive review about the liquid-liquid phase behavior (LLE) of solutions of Ionic liquids of
mixtures of different ILs with alcohols and aprotic polar and non-polar liquids is given. The review
focuses on different classes of systems, where in particular the influence on the LLE by a variation of the
chain or even side chain length of the components has been examined, mainly mixtures of 1-alkyl-3-
methylimidazolium bis((trifluoro-methyl)sulfonyl)amides (CxmimNTf2; 1 ≤ x ≤ 14) with n-alkyl alcohols
(CnOH; 1 ≤ n ≤ 20) are considered. Partial miscibility with upper critical solution temperatures (UCST)
is usually observed increasing with the chain lengths of the alcohols and decreasing with the length of the
side chain of the cation. In water and diols, however, the UCSTs increase with the length of the alkyl-
chains of the ILS.
The numerical analysis of the phase diagrams is consistent with Ising criticality. Concepts for the
description of the asymmetry of the phase diagram presuming the validity of universal scaling behavior
as given by the theory of complete scaling are applied. This concept does not only allow for perfect
description of the phase diagrams with a minimum of parameters but enables predictions of phase
diagrams in regions that are not explored.
The systematic trends of the phase behavior and the results of the analysis (UCST, critical composition,
width and diameter of the phase diagrams) are discussed in detail. The underlying concept which focuses
on the near critical region of the phase diagram is successfully proofed for off critical conditions. This
allows for a significant improvement of the description of LLE data within also the off critical range. The
application of corresponding phase behavior on the systems investigated so far yields one single master-
curve. Furthermore simple empirical relationships are formulated, that allow for the description or
estimate of UCSTs of the IL-alcohol family.
References
[1] V. R. Vale, S. Will, W. Schröer, B. Rathke “The General Phase Behavior of Mixtures of 1-Alkyl-3-
Bis(trifluoromethyl)sulfonylamide Ionic Liquids with n-Alkyl Alcohols” ChemPhysChem, 2012, 13: 1860-1867.
[2] X.W. Shao, W. Schröer, B. Rathke “Liquid-Liquid Phase Behavior of Solutions of 1,3-Dimethylimidazolium-
and 1-Methyl-3-propylimidazolium Bis((trifluoromethyl)sulphonyl)amide (C(1,3)mimNTf(2)) in n-Alkyl Alcohols”
Journal of Chemical and Engineering Data 2014, 59: 225-233.

PPEPPD 2016
th
Nitrogen and Oxygen Solubility Measurement in Styrene, and Effect on

Radical Polymerization of Styrene
Shigeo Oba1* and Tomoya Tsuji2

1
Applied Thermodynamics and Physical Properties Co. Ltd., Japan
2
Colledgeof Industrial Tecnology, Nihon University, Japan
*Corresponding author: shigeo.oba@at-pp.co.jp
Keywords: Gas solubility, PC-SAFT, Polymerization, Reaction rate
Abstract
Oxygen has been well known for an inhibitor in radical polymerization, because oxygen reacts
with vinyl monomers or polymer radicals at the propagation reactions, and stabilized to be peroxide
radicals. Then, the monomer solution, saturated with gaseous nitrogen, is often used to avoid the oxygen
inhibition. On the contrary, oxygen is sometimes fed into the solution to inhibit an unexpected radical
reaction in the reservoir, and to interrupt an uncontrollable reaction. However, the precise gas solubility
data are not available in the literature. Then, in this study, nitrogen and oxygen solubility in styrene were
measured around room temperature, 298, 303, and 313 K. In the measurement, a synthetic type apparatus
was employed. The detail equipment, and the procedures have been already described [1]. The
panoramic view cell employed was made of Pyrex glass, and its inner volume about 37 cm3. The cell was
specially designed, and its safe pressure up to 7.5 MPa. To check the relability, nitrogen and oxygen
solubility in benzene were also measured, and compared with those of literatures[2][3][4][5].
Surprisingly, the nitrogen solubilities in styrene are almost the same as those in benzene. Even in the
oxygen solubility, the similar tendency was observed. Therefore, it suggested that the nitrogen or oxygen
solubility just depends on the number of aromatic rings. The experimenatal data wer correlated with PC-
SAFT equation installed in Aspen Plus. Due to missing PC-SAFT pura parameters for styrene in Aspen
plus, we regressed them from vapor pressure, liquid density, and heat of vaporization. The regressed
model have a good representation for those two gas solubilities in styrene and benzen. In this study,
effect of those gas solubilities to the polystyrene polymerization reaction will be evaluated.
References
[1] T. Tsuji, Y. Shinya, T. Hiaki, N. Itoh “Hydrogen solubility in a chemical hydrogen storage medium, aromatic
hydrocarbon, cyclic hydrocarbon, and their mixture for fuel cell systems” Fluid Phase Equilibria, 2005, Volumes
228-229, 499-503.
[2] Miller, P.; Dodge, B. F. Ind. Eng. Chem., 1940, 32, 434-438 The system benzene nitrogen. Liquid-vapor phase
equlibria at elevated pressures
[3] Llave, F. M.; Chung, T. H. J. Chem. Eng. Data, 1988, 33, 123 Vapor-Liquid Equilibria of Nitrogen-
Hydrocarbon Systems at Elevated Pressures
[4] Gao, W.; Gasem, K. A. M.; Robinson Jr., R. L. J. Chem. Eng. Data, 1999, 44, 185-9 Solubilities of nitrogen in
selected naphthenic and aromatic hydrocarbons at temperatures from 344 to 433 K and pressures to 22.8 MPa
[5] Fischer, K.; Noll, O.; Gmehling, J. J. Chem. Eng. Data, 2001, 46, 1504-1505 Experimental Determination of the
Oxygen Solubility in Benzene
PPEPPD 2016
th
Influence of a proposed model in the simulation of a

distillation process conducted in a packed column
Adriel Sosa1*, Raul Rios1, Luis Fernández1, Juan Ortega1

1
Grupo de Ingeniería Térmica, Universidad de Las Palmas de Gran Canaria, España
*Corresponding author: adrielsm10@gmail.com
Scientific topic: Reaction and Separation Technologies
Keywords: Distillation, Process simulation, Modeling.
Abstract
The design of the separation operations is based (among others) in the thermodynamic-mathematical
model used to represent the behavior of the solutions (e.g.: NRTL [1], UNIFAC [2], etc.). The influence
of the chosen model in the simulation of the equipment and processes is vital for optimal designs under
economic and environmental criteria.
Our research group has been working for years with a parametric model [3,4], which acceptably
represents several thermodynamic quantities of the specified solution, including the presence of different
phase equilibria. Once obtained the modeling for a particular system, it is adequate to use it in a
subsequent stage of simulation of separation operations, and more specifically in distillation columns.
In this Conference the results obtained in the simulation of a distillation packed column with known
dimensions are presented, using both the proposed model [3,4] as those above mentioned. In all cases,
the models used are integrated in behavior equations of the simulated device. The simulation results are
evaluated considering the experimental information obtained in a laboratory-scale packed column, whose
main characteristics are used in the simulation process. The column operates batchwise with variable
reflux; the monitoring of pressure and temperature allows the real-time analysis of the behavior of the
system.
Different solutions are used in order to check the models at different conditions, System 1: Benzene (1)
+Heptane (2), is selected because this system is considered as a reference, since exists a dense database
in the literature; System 2: Methyl ethanoate (1)+Heptane (2), is chosen to verify the effect of mixing
energies in the simulation process; System 3: Methyl ethanoate (1)+Ethyl propanoate (2)+Heptane (3),
ternary system, which is used to check the capacity of extrapolation of the results using the
corresponding models previously obtained for the binaries.
References
[1] H. Renon, J.M. Prausnitz. Local Composition in Thermodynamic Excess Function for liquid Mixtures. AIChE
Journal, 1968, 14, 135-142.
[2] A. Fredenslund, R.L. Jones, J.M. Prausnitz. Group-Contribution Estimation of Activity Coefficients in Nonideal
Liquid Mixtures. AIChE Journal, 1975, 21, 1086-1098.
[3] J. Ortega, F. Espiau, J. Wisniak. New Parametric Model to Correlate the Gibbs Excess Function and Other
Thermodynamic Properties of Multicomponent Systems. Application to Binary Systems. Industrial & Engineering
Chemistry Research, 2010, 49, 406-421.
[4] L. Fernández, E. Pérez, J. Ortega, J. Canosa, J. Wisniak. Multiproperty modeling for a set of binary systems.
Evaluation of a model to correlate simultaneously several mixing properties of methyl ethanoate + alkanes and new
experimental data. Fluid Phase Equilibria, 2013, 341, 105-123.
PPEPPD 2016
th
Solid-fluid Equilibria of Adsorbed Yukawa Mixtures
Lloyd L. Lee,1* Anele Mkanya2, and Giuseppe Pellicane2

1
Department of Chemical & Materials Engineering, California State University, California, USA
2
School of Chemistry &Physics, University of Kwazulu-Natal, 3209, Pietermaritzburg, South Africa
*Corresponding author: profllee@yahoo.com
Scientific topic: Surfaces, interfaces, and confinement effects
Key words: solid-fluid equilibrium, density functional theory, new bridge functional, Yukawa mixtures,
contact-value sum rules
Abstract
The conference language is English and the abstract should be written in English in Times New Roman
12pt. The abstract should fit on one page A4. Please do not change the page margins (use the ones of this
document) or the font size and use single spacing. The headings (abstract, references) should be Times
New Roman 12pt bold. Please format the references according to the given examples (in Times New
Roman 10pt). Please use square brackets to refer to references [1]. Figures and tables cannot be used in
the abstract.
We examine the adsorption of binary Yukawa fluids on a solid wall. One of the objectives is to aim at,
for the future, explaining the behavior of charged species on the electric double layer*. The fluid is
composed of repulsive Yukawa molecules and attractive Yukawa molecules with a hard core.
Description of the system:
•Bulk Fluid: Equal molar mixtures of species A and B molecules. The A-A and B-B pairs
interact via the repulsive Yukawa potential; while A-B pairs via the attractive Yukawa potential.
•Wall: a planar structureless hard wall occupying the entire left-half of the space z < 0.
The underlying theoretical approach is the integral equation-based density functional theory (DFT) with
a new closure theory based on the OZ3-type bridge functionals.[1] We delineate the behavior by
exhibiting the singlet density profiles, the cavity distribution functions, the indirect correlations, and the
underlying bridge functions. Special attention is paid to the contact-value sum rules at the hard wall.
Monte Carlo simulations are carried out at temperatures from T* = kTd+/B = 0.28, and 0.595 (B being
the Bjerrum length). We start with the screening parameter λ =3.0 and let it shrink to 0.01 where
Coulomb-interaction behavior begins to show up. Equal diameters (d+ = d- ) and asymmetrical species
(d- = 2.12 d+) will be examined. The small-sized species exhibits “depletion” at the wall due to
“crowding-out” by the larger “ions”. As compared to the MC data, the satisfaction of the hard-wall sum
rules can guarantee to a large extent the accuracy of the theoretical DFT results.
References
* . The Yukawa potential tends to the Coulomb interaction when the screen parameter λ approaches zero.
[1] L. L. Lee, “Constructing a new closure theory based on the third-order Ornstein-Zernike equation and a study of
the adsorption of simple fluids” Journal of Chemical Physics, 2011, 135: 204706.

PPEPPD 2016
th
Phase equilibrium and surface tension of binary and ternary polymer

solutions
Jisu Choi1 and Youngchan Bae2*

1,2
Division of Chemical Engineering and Molecular Thermodynamics Laboratory
Hanyang University, Seoul 133-791, Korea
Scientific topic: Phase equilibria (modeling)
Keywords: Vapor-liquid equilibrium, Liquid-liquid equilibrium, Surface tension
Abstract
A thermodynamic model is proposed to correlate the phase equilibrium and surface tesnsions and the
calculated results are comopared with experimental data. A new lattice fluid equations of state is
established by introducing holes into the modified double lattice model [1] to describe vapor-liquid
equilibrium and liquid-liquid equilibrium simultaneously. The propoesed model is also combined with a
density gradient theroy [2] to calculate surface tension of systems. The model parameters are obtained by
correlating experimental liquid densities and vapor pressures for simiple fluids and the model parameters
of pure polymers are fitted by experimental PVT properties. The obtained pure paramters are used to
describe phase equilibrium and surface tensions of binary and ternary polymer solutions.
References
[1] J.S. Oh, Y.C. Bae, “Liquid-liquid equilibria for binary polymer solutions from modified double-lattice model”
Polymer, 1998, 39: 1149-1154.
[2] J.W. Cahn, J. E. Hilliard, “Free energy of a nonuniform system. I. Interfacial free energy” The Journal of
Chemical Physics, 1958, 28: 258-267.
Acknowledgements
This research was supported by Basic Science Research Program through the National Research Foundation of
Korea (NRF) funded by the Ministry of Education, Science, and Technology (No. 2011- 0024330).

PPEPPD 2016
th
Switching the Doubly Thermo-sensitivity of LCST type
Core-Shell gels in mixed solvent
Chan Hee Lee1 , Sang Kyu Ryu2 and Young Chan Bae*
Department of Chemical Engineering/Molecular Thermodynamics Laboratory, Hanyang University, Korea
Keywords: PNDEAm, PNIPAm, PNVCL, Core-shell, Molecular thermodynamic model
Abstract
Switching the LCST of thermo-sensitive core-shell gel has been detected in the aqueous mixed solvent
system. Two types of core-shell gels are prepared by a precipitation polymerization, which are composed
of poly(N-isopropylacrylamide) (PNIPAm) core/poly(N-vinylcaprolactam) (PNVCL) shell and PNIPAm
core/poly(N-diethylacrylamide) (PNDEAm) shell gels [1]. Both core-shell gels represent only one LCST
volume phase transition (VPT) in aqueous solution. With adding organic solvent (Dimehtylformamide
(DMF)) to the core-shell gel in aqueous solution, the volume phase transition temperature (VPTT) of
core and shell material is varied considerably due to the characteristic of chemical group. We use the
photon correlation spectroscopy (PCS) technique to measure the switched VPTT of the core-shell gels in
mixed solvent system. A molecular thermodynamic framework [2], combined the modified double-lattice
T model (MDL-T) [3] with the Flory-Rehner (F-R) chain model, is utilized to describe the
thermosensitive swelling behaviors of homo/core-shell gels.
References
[1] C. S. Scherzinger, P. Lindner, M. Keerl, W. Richtering, “Cononsolvency of Poly(N,N-diethylacrylamide)
(PDEAAM) and Poly(N-isopropylacrylamide) (PNIPAM) Based Microgels in Water/Methanol Mixtures:
Copolymer vs Core-Shell Microgel”, Macromolecules, 2010, 43: 6829-6833.

[3] S. M. Lee, Y. C. Bae “Swelling Behaviors of Doubly Thermosensitive Core-Shell Nanoparticle Gels”,
Macromolecules, 2014, 47: 8394-8403.
Acknowledgements
This research was supported by Global PH.D Fellowship Program through the National Research Foundation of
Korea(NRF) funded by the Ministry of Education (2015H1A2A1034513)
This research was respectfully supported by Engineering Development Research Center (EDRC) funded by the
Ministry of Trade, Industry & Energy (MOTIE). (No. N0000990)
PPEPPD 2016
th
Thermodynamic and Transport Properties of Biodiesel and Petro-diesel

Mixtures at High Pressures and Temperatures
Gorica R. Ivaniš1, Ivona R. Radović1, Vlada B. Veljković2 and Mirjana Lj. Kijevčanin1*
1
Faculty of Technology and Metallurgy, University of Belgrade, Belgrade, Serbia
2
Faculty of Technology, University of Niš, Leskovac, Serbia
*Corresponding author: mirjana@tmf.bg.ac.rs
Keywords: High pressure density, Viscosity, Sunflower oil methyl esters, Isothermal compressibility,
Isobaric thermal expansivity
Abstract
Mixtures of biodiesel with petro-diesel, containing up to 20% of biodiesel, can be used as fuel in existing
diesel engines without additional corrections in engines design, which makes them very attractive as a
substitution for conventional fuels. Also, the European Union set a directive on replacing at least 10% of
the petro-diesel with biodiesel or other renewable fuels in the transport sector by 2020 [1]. Biodiesel
mixtures with petro-diesel have different properties than pure petro-diesel so the knowledge of their
thermodinamic properties is of utmost importance, especially of density and viscosity. Viscosities of pure
petro-diesel and its mixtures with sunflower oil methyl esters [2], in the ratio of 10% vol. and 20% vol.
of the biodiesel, were measured at temperatures 288.15-373.15 K and at atmospheric pressure. Densities
of the same samples were determined in temperature range 293.15-413.15 K and at pressures up to 60
MPa and the measurements were performed using an Anton Paar DMA HP digital vibrating U tube
densimeter [3]. Classical one-fluid calibration method was applied and the obtained density data were
fitted to the modified Tammann-Tait equation. Thereafter, the isothermal compressibility and the
isobaric thermal expansivity were calculated for all of the three studied samples at temperatures 293.15-
413.15 K and at pressures 0.1-60 MPa.
References
[1] J. Malca, F. Freire “Life-cycle studies of biodiesel in Europe: A review addressing the variability of results and
modeling issues” Renewable and Sustainable Energy Reviews, 2011,15:338–351.
[2] G. R. Ivaniš, I. R. Radović, V. B. Veljković, M. Lj. Kijevčanin “Biodiesel density and derived thermodynamic
properties at high pressures and moderate temperatures” Fuel, 2015, Accepted for publishing
[3] G. R. Ivaniš, A. Ž. Tasić, I. R. Radović, B. D. Djordjević, S. P. Šerbanović, M. Lj. Kijevčanin “An apparatus
proposed for density measurements in compressed liquid regions at the pressures 0.1–60 MPa and the temperatures
288.15–413.15 K” Journal of the Serbian Chemical Society, 2015, 80:1073-1085.
Acknowledgements
The authors gratefully acknowledge the financial support received from the Research Fund of Ministry of
Education and Science (projects No 172063 and partly No III45001), Serbia and the Faculty of Technology and
Metallurgy, University of Belgrade.
PPEPPD 2016
th
Prediction of Liquid-Liquid Partitioning of Active Pharmaceutical

Ingredients with the SAFT-γ Mie Approach
Panatpong Hutacharoen1, Simon Dufal1, Vasileios Papaioannou1, Ravi M. Shanker2, Claire S. Adjiman1,
Amparo Galindo1, and George Jackson1*
1
Department of Chemical Engineering, Imperial College London, London, SW7 2AZ, United Kingdom
2
Pfizer Inc., Pharmaceutical Sciences, Worldwide R&D, Groton, CT, 06340, USA
*Corresponding author: g.jackson@imperial.ac.uk
Scientific topic: Pharmaceuticals and cosmetics
Keywords: Partition coefficient, API, LLE, SAFT
Abstract
Lipophilicity is a fundamental physicochemical property in drug discovery and is usually quantified by

the partitioning equilibrium of solute molecules between water and an immiscible organic solvent. A
number of surrogate solvents are typically used to model transport and partitioning of drugs in biological
systems taking advantage of chemical similarity between the surrogate and the phospholipid bilayer. The
most popular surrogate in this context is the 1-octanol/water system. The partitioning of solutes in
alkane/water solvents (e.g., hexane/water and hexadecane/water) is also of interest for drug discovery.
We have developed a general approach to predict partition coefficients in octanol/water (logKOW) and
alkane/water (logKalk) systems solely from the chemical structure of compounds. In particular, the SAFT-
γ Mie [1, 2] approach, a group contribution version of the SAFT equation of state, is used. In SAFT-γ
Mie, molecules are described in terms of the different types of functional groups and modeled as
composed of fused spherical segments that interact via Mie (generalized Lennard-Jones) potentials of
variable repulsive and attractive range. With this approach, an accurate alkane-water model is
established, and the parameters are transferred to obtain an accurate octanol-water model. Partition
coefficients as well as infinite dilution properties of several families of organic compounds are used to
test the reliability of the model. The results are found to be in good agreement with the experimental
data. Subsequently, partition coefficients of active pharmaceutical ingredients are calculated. The
difference between logKOW and logKalk (∆logK), which is a measure of the hydrogen bonding potential of
a molecule, can also be obtained simultaneously by this approach.
References
[1] V. Papaioannou, T. Lafitte, C. Avendaño, C. S. Adjiman, G. Jackson, E. A. Müller, A. Galindo “Group
contribution methodology based on the statistical associating fluid theory for heteronuclear molecules formed from
Mie segments”, The Journal of Chemical Physics, 2014, 140: 054107-29.
[2] S. Dufal, V. Papaioannou, M. Sadeqzadeh, T. Pogiatzis, A. Chremos, C. S. Adjiman, G. Jackson, and A.

Galindo “Prediction of Thermodynamic Properties and Phase Behavior of Fluids and Mixtures with the SAFT-γ
Mie Group-Contribution Equation of State”, Journal of Chemical & Engineering Data, 2014, 59: 3272-3288
Acknowledgements
We gratefully acknowledge financial support from Pfizer Inc.
PPEPPD 2016
th
Modeling of hydrocarbons droplets dissolution in near-critical or

supercritical water based on GCA-EoS fugacity predictions
Ping He1, Francisco A. Sanchez2, Selva Pereda2*, Ahmed F. Ghoniem1

1
Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge MA 02139, USA
2
Planta Piloto de Ingeniería Química – PLAPIQUI - Universidad Nacional del Sur – CONICET, Camino La
Carrindanga Km 7 – CC: 717, Bahía Blanca, Argentina
*Corresponding author: spereda@plapiqui.eduar
Keywords: water, hydrocarbon, mixing properties, GCA-EoS, Maxwell-Stefan equations
Abstract
Upgrading heavy crude oil using near-critical or supercritical water (NCW/SCW) shows
advantages such as high yielding of light oils, removal of sulfur content and heavy metals, etc.
We study the thermodynamic and mixing process of crude oil and NCW/SCW using
representative hydrocarbons, like benzene and 1-decylnaphthalene. GCA-EoS, the first equation
of state that takes into account association using a SAFT-like group contribution term, is used to
predict the thermodynamic properties and phase equilibrium compositions. The generalized
Maxwell-Stefan equations are solved to model the multicomponent mass transfer with the
driving force expressed in terms of fugacity gradients to account for effects of non-ideality on
mass fluxes. The mixing of a hydrocarbon droplet in the bulk of supercritical water is studied
numerically at different mixing conditions in a 1-D spherical symmetric geometry. We
demonstrate here that the GCA model can play an important role in the design of supercritical
fluids reactors.

PPEPPD 2016
th
Modeling of the Thermodynamic Properties and Phase Equilibria in the

System Water – Nitric Acid – Tributyl Phosphate – Europium Nitrate
Aleksey I. Maksimov*, Nikita A. Kovalenko

Chemistry Department, Lomonosov Moscow State University, Russian Federation
*Corresponding author: ai.maksimov@td.chem.msu.ru
Keywords: Electrolytes, Mixed-solvent, Thermodynamic Model, Extraction
Abstract
Rare earth elements compounds are widely used in the manufacturing of modern high-tech products. Tri-
n-butyl phosphate extraction in water–organic solvents is one of the most popular methods of extraction
and separation of lanthanoid compounds. Usually process conditions are based on experimental data and
adjusted empirically. To optimize extraction process composition and quantities of coexisting aqueous
and organic phases are required. Thermodynamic modeling is quite efficient method for obtaining this
type of data. The aim of this work is to construct thermodynamic model of the systems containing water,
tributyl phosphate, nitric acid and europium nitrate.
Thermodynamic properties of solutions were described with the electrolyte version of generalized local
composition model. This model generalizes well-known local composition models such as UNIQUAC,
Wilson and Tsuboka – Katayama, effect of electrolytes is described by means of Debye–Huckel and
polynomial Pitzer–type terms. Temperature – concentration dependance of the dielectric constant is
taken into account.
Parameters of the model were fitted using experimental data of the water – tri-n-butyl phosphate system
(water activities, liquid–liquid equilibria, mixing enthalpies), water – nitric acid system (vapour–liquid
equilibria, solid–liquid equilibria, dilution and dissolution enthalpies), water – europium nitrate system
(water activities), water – tributyl phosphate – nitric acid system (liquid–liquid equilibria, vapour–liquid
equilibria) and water – tributyl phosphate – nitric acid - europium nitrate system (liquid–liquid
equilibria). The estimation of model parameters was performed by minimization sum of squares of
residuals. 95 % confidence intervals for parameters were calculated, only statistically significant
parameters were used.
Strict and detailed thermodynamic description of the water – tri-n-butyl phosphate, water – tributyl
phosphate – nitric acid and water – tributyl phosphate – nitric acid - europium nitrate systems was
obtained in this work. This thermodynamic model allows to calculate the distribution of europium nitrate
as a function of concentration or acidity. Suggested model is a good basis for modeling of the systems
containing different rare earth nitrates. These models can be used for the prediction of phase equilibria in
solutions of several rare earth nitrates, it would be helpful for development of effective rare earth
elements compounds separation technology.
Acknowledgements
This work was funded by RFBR according to the research project No. 16-33-01038 mol_a.
PPEPPD 2016
th
Microfluidic Measurements of Diffusion in Liquids Using Confocal Raman

Spectroscopy
Christine Peters, Julia Thien, Sandra Haase, Carsten Flake, Ludger Wolff, Hans-Jürgen Koß and André Bardow*
*Corresponding author: andre.bardow@ltt.rwth-aachen.de
Scientific topic: Fundamentals: Thermodynamics and transport properties
Keywords: diffusion, multicomponent, confocal Raman spectroscopy, microfluidics
Abstract
Diffusive transport is omnipresent in (bio-)chemical processes. As diffusion is often rate-limiting,

diffusion coefficients are required for the design of industrial processes. Still, there is a lack of diffusion
data, especially for multicomponent systems, which are most relevant in technical applications. This lack
of data is due to the fact that diffusion measurements are time consuming and complex, and that the
measurement effort scales quadratically with the number of components.
A promising approach to more efficient diffusion measurements is microfluidics. The short diffusion
distances in microfluidic devices lead to faster measurements, while sample volumes are simultaneously
reduced. So far, microfluidic setups have only been used for binary diffusion where simple analytical
methods suffice. For multicomponent mixtures, spectral techniques like Raman spectroscopy offer the
potential for simultaneous quantification of all components.
In this work, confocal Raman spectroscopy and microfluidics have therefore been combined to measure
diffusion coefficients in binary and ternary systems. This combined approach allows determining
concentration profiles of all components with high spatial resolution. The mass transport model of
Häusler et al. [1] is extended to ternary systems. Combining the concentration profiles measured by
Raman spectroscopy with the mass transport model, diffusion coefficients can be determined.
The developed measurement set-up was validated using a binary mixture. Then, the feasibility for ternary
systems was investigated. All binary and ternary experiments show a good agreement between the
measured and the calculated concentration profiles. Therefore, it can be assumed that the model
assumptions are justified. The measured diffusion coefficients agree with literature data demonstrating
that the microfluidic Raman set-up is suitable for the efficient and fast measurement of diffusion
coefficients in liquids.
References
[1] E. Häusler, P. Domagalski, M. Ottens, A. Bardow. “Microfluidic diffusion measurements: The optimal H-cell.”
Chemical Engineering Science, 2012, 72:45-50.
Acknowledgements
We acknowledge support by the German Federation of Industrial Research Associations (AiF) (IGF-Nr. 18803).
PPEPPD 2016
th
Prediction of Thermodynamic, Transport and Permeability Properties of

Ionic Liquids using Molecular Simulation
Niki Vergadou1* and Eleni Androulaki1

1
Institute of Nanoscience and Nanotechnology, National Center for Scientific Research “Demokritos”, Greece
*Corresponding author: n.vergadou@inn.demokritos.gr
Scientific topic: Molecular and multiscale simulations
Keywords: ionic liquids, molecular simulation, diffusivity, viscosity, gas separations
Abstract
Ionic liquids (ILs) [1] are organic salts with melting points usually near room temperature
(RTILs) and are usually consisted of a bulky organic cation and an organic or inorganic anion.
ILs are characterized by negligible vapor pressures, good electrolytic and solvation properties,
thermal stability, chemical tunability and in many cases by large CO2 absorption capacity. They
are identified as novel ‘green’ designer solvents as the chemical diversity in the molecular
structure of the ions affects directly the physicochemical properties of the ILs. The present work
focuses on the molecular simulation of imidazolium-based tricyanomethanide ionic liquid
family using an optimized classical atomistic force field [2]. The force field in use has been
validated against experimental data by performing molecular dynamics (MD) simulations of the
[Cnmim+][TCM-], n = 2, 4, 8 ionic liquid family at various temperatures and at atmospheric
pressure [2]. Very long molecular dynamics simulations of several tens of nanoseconds were
performed in order to calculate the thermodynamic, structural and transport properties of the
pure ILs. The microscopic and the complex dynamic behaviour [3] of the systems under study
was thoroughly investigated and the effect of the alkyl tail lengnth and the temperature on the
extracted properties was studied. Permeability and selectivity properties were estimated by
calculating gas (CO2, N2, CH4, Ar, O2, SO2, H2S) diffusivity and solubility in a wide temperature
range. The reliability of the molecular simulation predictions is confirmed by direct comparison
to experimental measurements.
References
[1] P. Wasserscheid and T. Welton, “Ionic Liquids in Synthesis”, Wiley-VCH: Weinheim, Germany, 2003.
[2] N. Vergadou, E. Androulaki, J.-R. Hill and I. G. Economou, submitted, 2015.
[3] E. Androulaki, N. Vergadou and I. G. Economou, “Analysis of the heterogeneous dynamics of imidazolium-
based [Tf2N−] ionic liquids using molecular simulation”, Molecular Physics, 2014, 112:2694-2706.
Acknowledgements
This work has received funding from the Seventh European Framework Programme for Research and
Technological Development within the project “Novel Ionic Liquid and Supported Ionic Liquid Solvents for
Reversible Capture of CO2” (IOLICAP Project 283077).
PPEPPD 2016
th
Phase Behavior and Compositional Variation Modeling of Petroleum Fluids

Containing Asphaltene and CO2 by CPA-EoS
José A. Scilipoti2, Pedro H. R. Alijó1,2, Rogério O. Espósito3, Frederico W. Tavares2,4*

1
Departamento de Físico-Química, IQ, Universidade do Estado do Rio de Janeiro, 20550-900,
Rio de Janeiro/RJ, Brasil
2
Departamento de Engenharia Química, EQ, Universidade Federal do Rio de Janeiro, 21941-909,
3
Petrobras S.A., E&P-PRESAL/CT/PP, Rio de Janeiro/RJ, Brasil.
4
Programa de Engenharia Química, COPPE, Universidade Federal do Rio de Janeiro, 21941-972,
*Corresponding author: tavares@eq.ufrj.brt
Keywords: Asphaltene precipitation, Cubic-Plus-Association EoS, PVT properties of petroleum fluids.
Abstract
Asphaltenes are recognized as the heaviest, most polar, and most complicated fraction of a crude oil. The
solubility variation of asphaltenes in paraffins and other important fluids, such as carbon dioxide (CO 2),
is a source of problems during crude oil production operations. Association effect beetwen asphaltene
molecules is crucial to predict liquid-liquid equilibria with an asphaltene-rich phase [1,2]. In addition, the
presence of CO2 introduce more challenges on phase equilibria modeling, specially due to cross
association with asphaltene fractions. Here, we study the cross- and self-associative effects on the onset
curves of asphaltene precipitation of heavy olis with high CO2 concentrations, using the Cubic-Plus-
Association equation of state (CPA EoS) [3]. We have improved and modified an algorithm for
compositional variation modeling, developed by Reservoir Engineering Research Institute (RERI)
[1,2,4], to take into account the associative effects. We have regressed CPA EoS parameters based on
PVT data for several wells with differents amounts of asphaltenes and CO2. Based on this adjustment,
compositional variation calculations show that association effects may predict phase transitions that are
not captured with traditional approaches.
References
[1] Z. Li, A. Firoozabadi, Modeling Asphaltene Precipitation by n -Alkanes from Heavy Oils and Bitumens
Using Cubic-Plus-Association Equation of State, Energy & Fuels. 24 (2010) 1106–1113.
doi:10.1021/ef9009857.
[2] Z. Li, A. Firoozabadi, Cubic-Plus-Association Equation of State for Asphaltene Precipitation in Live Oils,
Energy & Fuels. 24 (2010) 2956–2963. doi:10.1021/ef9014263.
[3] D. Peng, J. Pang, B.C., Y. Lu, An equation of state for associating systems, J. Chinese Inst. Eng. 28 (2005)
1157–1168. doi:10.1080/02533839.2005.9671092.
[4] E. W. Bolton, A. Firoozabadi, Numerical modeling of temperature and species distributions in hydrocarn
reservoirs, J. Geophys. Res. Solid Earth 119 (2014) 18–31. doi: 10.1002/2013JB010043.
Acknowledgements
We thank Petrobras, COPPETEC Fundation and National Counsel of Technological and Scientific Development
(CNPq) for supporting this project.
PPEPPD 2016
th
The Effect of Material Flexibility on the Drying Transition of Water between

Hydrophobic Objects: Thermodynamics and Kinetics
Y. Elia Altabet1* and Pablo G. Debenedetti1

*Corresponding author: altabet@princeton.edu
Keywords: Hydrophobic interactions, elasticity
Abstract
Liquid water confined between hydrophobic objects of sufficient size becomes metastable with respect to
its vapor at separations smaller than a critical drying distance. Macroscopic thermodynamic arguments
predicting this distance and nearly all molecular simulations of this phenomenon have been restricted to
the limit of perfectly rigid confining materials. However, no material is perfectly rigid, and it is of
interest to account for this fact in both theoretical and in silico analyses. First, we present a theory that
combines the current macroscopic theory with the thermodynamics of elasticity to derive an expression
for the critical drying distance for liquids confined between flexible materials [1]. Thermodynamic
arguments show that flexibility increases the critical drying distance, and additional calculations
demonstrate that this increase can be dramatic for flexibilities consistent with that of biological materials.
Second, we present calculations of the rate of evaporation of water as a function of both object separation
and flexibility. Rate calculations, obtained via forward flux sampling [2] in conjunction with molecular
dynamics simulations, show that the rate increases substantially as the material is made more flexible,
suggesting more flexible materials provide lower kinetic barriers to evaporation.
References
[1] Y.E. Altabet, P.G. Debenedetti “The role of material flexibility on the drying transition of water between
hydrophobic objects: a thermodynamics analysis” Journal of Chemical Physics, 2014, 141: 18C531.
[2] R.J. Allen, C. Valeriani, P.R. ten Wolde “Forward flux sampling for rare event simulations” Journal of Physics:
Condensed Matter, 2009, 21: 463102.
Acknowledgements
We gratefully acknowledges the support of the National Science Foundation (Grant No. CHE-1213343).

PPEPPD 2016
th
Development of a group contribution approach for the description of

molecular ions using SAFT-γ Mie
Georgia Lazarou1, Esther Forte1, Simon Dufal1, Ravi M. Shanker2, Claire Adjiman1, George Jackson1,
Amparo Galindo1*
1
Department of Chemical Engineering, Imperial College London, London, SW7 2AZ, United Kingdom
2
Pfizer Inc., Groton Laboratories, USA
*Corresponding author: a.galindo@imperial.ac.uk
Scientific topic: Phase equilibria (modelling)
Keywords: SAFT, Electrolytes, Equation of state
Abstract
Thermodynamic modelling of electrolyte solutions using an equation of state proves particularly

challenging when considering organic electrolyte molecules which give rise to similarly massive ions. As
the size and complexity of ionic species increases, a molecular-based approach becomes limiting with
respect to realistically capturing the geometry and charge density of a given ion. Therefore a group-
contribution approach can be beneficial in cases where the topology of complex ions demands a more
detailed description than the commonly adopted spherical point-charged model.
With the SAFT-γ Mie equation of state [1] a group-contribution approach is employed which allows the
implementation of heteronuclear models of molecules, composed of transferrable functional groups.
Hence it is an ideal framework for developing models of complex ionic species. The benefit of the
approach is two-fold: the structure of the molecule can be better represented via defined functional
groups, which are neutral or charged; and consequently localised charge effects can be accounted for.
The SAFT-γ Mie equation of state is extended with the incorporation of an ionic contribution and a Born
contribution to the total Helmholtz free energy. The ionic term follows from a formulation of the
primitive asymmetric Mean Spherical Approximation [2] within a group-contribution framework, and
the Born solvation free energy [3] is expressed accordingly to accompany this formulation. The
capabilities of the resulting SAFT-γ Mie equation of state to predict the physicochemical properties of
electrolyte solutions containing ions of varying complexity are here demonstrated.
References
[1] V. Papaioannou, T. Lafitte, C. Avendaño, C. S. Adjiman, G. Jackson, E. A. Müller, A. Galindo, “Group
contribution methodology based on the statistical associating fluid theory for heteronuclear molecules formed from
Mie segments” The Journal of Chemical Physics, 2014, 140: 054107.
[2] L. Blum, J. Hoye, “Mean spherical model for asymmetric electrolytes. 2. Thermodynamic properties and the
pair correlation function” The Journal of Physical Chemistry, 1977, 81: 1311-1316.
[3] M. Born, “Volumen und Hydratationswärme der Ionen” Zeitschrift für Physik, 1920, 45-48.
Acknowledgements
We gratefully acknowledge funding from Pfizer Inc.
PPEPPD 2016
th
Study and prediction of mixture interaction parameters for
empirical multi-parameter mixture models
Ian H. Bell1* and Eric W. Lemmon1

1
Applied Chemistry and Materials Division, National Institute of Standards and Technology, Boulder, CO, USA
*Corresponding author: ian.bell@nist.gov
Keywords: mixture interaction parameters, mixture modeling, vapor-liquid equilibria
Abstract
The current state-of-the-art in mixture property modeling is the so-called GERG formulation [1, 2]. In
this formulation, the reducing functions used in the non-dimensionalized Helmholtz energy contain four
adjustable parameters. In the past, these adjustable parameters were obtained through a combination of
deterministic optimization and manual iteration. In recent work [3] a minimal set of these interaction
parameters were obtained for more than 900 mixtures through an entirely automatic evolutionary
optimization paradigm.
Unfortunately, there are many binary mixtures for which no experimental data exist. In these cases, it is
still necessary to be able to yield reasonable predictions for the mixture behavior, even if only
qualitatively. In order to fill this gap in experimental measurements, simple interaction parameter
estimation schemes (linear and Lorentz-Berthelot mixing rules) have been proposed in the literature and
are investigated in this study. It is demonstrated that users should be appropriately wary when using
these estimation schemes as they are not suitable in all cases.
Furthermore, by investigating binary interaction parameters for families of binary pairs, clear trends are
seen. For instance, in the linear alkane/linear alkane binary pairs, the interaction parameters demonstrate
a striking familial trend – a nearly linear relationship. For other families, the trends are more complex;
for carbon dioxide binary mixtures, there is a clear trend with linear alkanes, but the trend becomes less
clear for other binary mixtures.
Finally, we close with a few correlations for the prediction of the binary interaction parameters for
families where sufficient experimental data exist to be able to identify familial trends. It is hoped that in
the future the knowledge gained in this process can be generalized to a simple empirical rule that can be
used to predict all mixture interaction parameters with reasonable accuracy.
References
[1] O. Kunz, R. Klimeck, W. Wagner, and M. Jaeschke. The GERG-2004 Wide-Range Equation of State for
Natural Gases and Other Mixtures. VDI Verlag GmbH, 2007.
[2] O. Kunz and W. Wagner. The GERG-2008 Wide-Range Equation of State for Natural Gases and Other
Mixtures: An Expansion of GERG-2004. J. Chem. Eng. Data, 57:3032–3091, 2012. doi:10.1021/je300655b.
[3] I. H. Bell and E. W. Lemmon “Automatic fitting of binary interaction parameters for multi-parameter mixture
models” J. Chem. Eng. Data, 2016 (to be submitted)
PPEPPD 2016
th
Thermodynamic Approach to the Separation of Rare Earth Elements
Nikita A. Kovalenko*, Aleksey I. Maksimov, Alexander E. Moiseev, Michail A. Zhilin, Anatoly S. Arkhipin,
Irina A. Uspenskaya
Chemistry Department, Lomonosov Moscow State University, Russian Federation
*Corresponding author: kovalenko@td.chem.msu.ru
Keywords: thermodynamic modeling, extraction, vapor pressure, electrolytes
Abstract
Liquid-liquid extraction is one of the most important parts of rare earth element (REE) production. The
separation technology of rare earths involves the large number of steps each of which represents a
distribution of electrolytes between aqueous and organic phases. Traditional approach to the problem of
modeling extraction stages is based on the huge amount of experimental work devoted to the
determination of distribution coefficients. After that the correlation dependencies between distribution
coeeficients and a composition of the system are obtained. Due to the large number of components in the
systems it is almost impossible to solve the problem by exhaustively searching all of the parameters. As
alternative choice the thermodynamic approach may be used which is baseded on the construction of the
strict thermodynamic model of the multicocmponent system. This method implies a description of the
Gibbs energy of the system. Modeling of solutions begins with binary systems, whereupon a number of
the components is increased gradually. Basically thermodynamic models have the ability to predict a
behaviour of the multicomponent systems based on the description of the smaller order subsystems. An
application of the thermodynamic models permits to get information about the distribution of rare earths
between two liquid phases reducing an amount of experimental work.
For the demonstration of the discussed method nitrates of medium rare earth elements were chosen as the
objects of the research. Thereby the main purpose of the work is a construction of the thermodynamic
model of the system formed by water, nitric acid, tributyl phosphate and nitrates of samarium, europium,
gadolinium. The reliable thermodynamic model has to be based on the set of varied experimental data.
Use of only liquid-liquid equilibria data is insufficient. Particular attention was given to the vapor
pressure measurement data due to the importance of thermodynamic properties of solutions for
modeling. Binary systems are sufficiently completely described in the literature. Vapor presure
measurements of the ternary solutions were conducted. The apparatus based on the transpiration method
was built for this experiments. Also liquid-liquid equilibria were determined for the multicomponent
systems. This study involved the conduction of the extraction experiments and determination of the
composition of the equilibrium phases. The content of lanthanides was determined by ICP-AES and
spectrophotometry methods. Nitric acid in the both phases and water in the organic phase were
determined by acid-base potentiometric and Fischer titration accordingly. All the experimental results
obtained in the present work and literature data concerning the system under investigation were used for
thermodynamic modeling. For this task the electrolyte version of generalized local composition model
was applied. As a result the thermodynamic model of the multicomponent system was constructed. This
model may be used for an engineering of the medium rare earth elements separation technology.
Acknowledgements
This work was funded by RFBR according to the research project No. 16-33-01038 mol_a.
PPEPPD 2016
th
Extensive Accuracy Test of the Force-Field Based
Quasi-Chemical Method PAC-MAC
Teun Sweere1*, Hans Fraaije2

1
Leiden Institute of Chemistry, Leiden University, the Netherlands
2
Leiden Institute of Chemistry, Leiden University, the Netherlands
*Corresponding author: a.j.m.sweere@chem.leidenuniv.nl
Keywords: Quasi-Chemical Method, Pair Sampling, Activity Coefficient, Vapor-Liquid Equilibrium
Abstract
Activity coefficients of multi-component fluid mixtures provide a useful source of information for the
calculation of various chemical properties, such as vapor-liquid equilibrium data and Flory-Huggins
interaction parameters. Experimental databases are one way to obtain these properties. However, for
cases where experimental data are not available, one has to find other ways to predict the thermodynamic
behavior of fluid mixtures.
We present a comprehensive evaluation of the recently developed Pair Configuration to Molecular
Activity Coefficient (PAC-MAC) method [1]. This quasi-chemical method is based on the pair sampling
technique of Blanco [2] with an extension that takes the packing of the molecules into account by a free
energy model. The intermolecular energy between neighboring pairs of molecules is calculated using
classical force-fields. PAC-MAC is able to predict activity coefficients and corresponding vapor-liquid
equilibrium diagrams at least 4 orders of magnitude faster than molecular simulations. The accuracy of
this method is tested by comparing the calculated excess mixing free energy with experimental data for
1092 binary mixtures. PAC-MAC is proven to predict miscibility properties with proper accuracy. In
addition, two modifications to the model are proposed which further reduce the root mean squared error
to 0.15 kBT.
References
[1] A. J. M. Sweere, J. G. E. M. Fraaije “Force-Field Based Quasi-Chemical Method for Rapid Evaluation of
Binary Phase Diagrams” J. Phys. Chem. B, 2015, soon to be published.
[2] C. F. Fan, B. D. Olafson, M. Blanco, S. L. Hsu “Application of Molecular Simulation to Derive Phase Diagrams
of Binary Mixtures” Macromolecules, 1992, 25: 3667-3676.

PPEPPD 2016
th
Assessment of mass transfer parameters in olefin facilitated transport

through polymer-ionic liquid composite membranes
Daniel Gorri1*, Raúl Zarca1, Alfredo Ortiz1, Marcos Fallanza1, Inmaculada Ortiz1
1
Department of Chemical & Biomolecular Engineering, University of Cantabria, Spain
* Presenting author: gorrie@unican.es
Keywords: Facilitated transport, propylene, ionic liquids, silver, membrane composite
Abstract
Separation of light gaseous olefins from paraffin’s of the refinery process off-gasses has been
traditionally performed by cryogenic distillation, which is a highly capital and energy intensive
operation. This handicap creates an incentive for the investigation of alternative olefin/paraffin
separation technologies. In this regard, membrane technology supposes a potential solution for process
intensification.
Previous works of our research group reported the use of facilitated transport composite membranes
integrating the use of PVDF-HFP polymer, BMImBF4 ionic liquid and AgBF4 silver salt. In this type of
membranes, the silver cations react selectively and reversibly with the olefin, allowing the separation via
mobile and fixed carrier mechanisms. Ionic liquids were selected as membrane additives because in
addition to their negligible vapour pressure that avoids solvent losses by evaporation, they provide
stability to the metallic cation dissolved inside, and modify the structure improving the facilitated
transport. This technology offers a commercial attractive separation alternative thanks to their modular
form of operation, high values of selectivity and permeability and low operational costs.
In the present work, continuous flow propane/propylene permeation experiments, involving the use of
different ionic liquids as well as different membrane compositions, were performed. Moreover, basing on
the transport and equilibrium parameters previously obtained, a mathematical model description of the
system has been proposed fitting the remaining parameters and allowing the design and optimization of
the propane/propylene separation process at industrial levels.
References
[1] M. Fallanza, A. Ortiz, D. Gorri, I. Ortiz, Experimental study of the separation of propane/propylene mixtures by
supported ionic liquid membranes containing Ag+–RTILs as carrier, Sep. Purif. Technol. 97 (2012) 83-89.
[2] M. Fallanza, A. Ortiz, D. Gorri, I. Ortiz, Polymer–ionic liquid composite membranes for propane/propylene
separation by facilitated transport, J. Membr. Sci. 444 (2013) 164-172.
Acknowledgements
This research was supported by the Ministry of Education and Science under the projects CTQ2012-31639
(MINECO, SPAIN-FEDER 2001-2013) and CTM2013-44081-R.

PPEPPD 2016
th
Modelling the Contribution of Ring Formation within a SAFT Framework
Sara A. Febra1*, Simon Dufal1, Ravi M. Shanker2, Amparo Galindo1, Claire S. Adjiman1 and George Jackson1
1
Department of Chemical Engineering, Centre for Process Systems Engineering,
Imperial College London, London, SW7 2AZ, United Kingdom
2
Pfizer Inc, Pharmaceutical Sciences, Worldwide R&D, Groton, CT, 06340, USA
*Corresponding author: s.febra14@imperial.ac.uk
Scientific topic: Thermodynamics (modelling)
Keywords: SAFT, inter/intramolecular association, TPT1
Abstract
The SAFT approach [1] constitutes one of the most sophisticated and successful molecular-based
approaches for industrial applications. However, most versions of the approach are based on Wertheim’s
first-order thermodynamic perturbation theory (TPT1), which neglects any type of ring formation, i.e. by
covalent bonding, inter and intramolecular association. This TPT1 approach limits SAFT applicability to
systems where these effects are relevant.
Although the dependence intramolecular association on density is less marked, its competition with
intermolecular association is not. For a pure fluid, it is expected that the intramolecular association gains
relevance with the decrease of density, due to the intermolecular distances being larger. Sear and Jackson
[2] and Ghonasgi et al. [3] developed, independently, theories to account for intramolecular in addition
to intermolecular association, following the original theory of Wertheim.
In the current work, intramolecular association is considered in an effective manner. Additionally, by
extending the theory present in literature [2] to multiple associating sites and multiple component
mixtures, a general analytical theory to account for ring formation within a SAFT framework is under
development. The results of predicted thermodynamic properties with SAFT-VR SW [1] for simple
systems accounting and neglecting ring formation are presented and compared.
References
[1] A. Gil-Villegas, A. Galindo, P. J. Whitehead, S. J. Mills, G. Jackson, A. N. Burgess “Statistical associating
fluid theory for chain molecules with attractive potentials of variable range” The Journal of Chemical Physics,
1997, 106: 4168-4186.
[2] R. P. Sear, G. Jackson “Thermodynamic perturbation theory for association into chains and rings” Physical
Review E, 1994, 50: 386-394.
[3] D. Ghonasgi, W. G. Chapman “Competition between intermolecular and intramolecular association in flexible
hard chain molecules” The Journal of Chemical Physics, 1995, 102: 2585-2592.
Acknowledgements
Funding from EPSRC, Innovate UK and Pfizer is gratefully acknowledged.

PPEPPD 2016
th
Computational assessment between different-type materials for CO2 capture
Daniel Bahamon1 and Lourdes F. Vega1*

1
ALYATECH, C/Tres Creus, 236, Centre de Promoció Empresarial, 08203, Sabadell. Barcelona, Spain
*Corresponding author: lourdes.f.vega@gmail.com
Scientific topic: Carbon capture and storage.
Keywords: CO2 Adsorption, MOFs, Zeolites, Monte Carlo Simulations.
Abstract
There is an increasing interest on CO2 capture and separation from flue gas streams, being adsorption
technology the most advantageous for these problems due to their low energy requirements compared to
other conventional using aqueous amine solvents [1]. Traditional industrial adsorbents such as zeolites
and porous carbons have been extensively studied due to their specific properties. In addition, Metal–
Organic Frameworks (MOFs) have recently appeared as a new class of crystalline nanoporous materials
with sufficient synthetic versatility to enable a “materials by design” approach [2].
An ideal adsorbent should exhibit high selectivities and adsorption capacities, as well as minimal energy
penalty for regeneration and long-term stability [3], however the investigation of the effects from
coexisting components, moisture or impurities such as SO2 and others is less explored [4]. In this regard,
molecular simulation plays an essential role since it can be used as a screening method and allows
obtaining new insights for multicomponent adsorption phenomenon [5].
In this work, we present a systematic computational comparison of several representative types of MOFs
vs. typically zeolites and materials used in industry for CO2 separation from multi-component flue gas
mixtures. GCMC simulations were used to identify features of these structures including impurities and
water traces. The main objective was to identify the most suitable adsorbent-type for different Swing
Adsorption processes. A first screening was based on pure adsorption isotherms, for a further detailed
analysis of mixtures considering a molecular understanding of changes in the adsorption location onto
the structure and isosteric heats distributions. After considering different operating conditions, and
although MOFs CuBTC and Mg-MOF-74 have great potential to become materials to be used in such
processes [6], at the moment, the zeolite 13X remains as the more suitable candidate, given the limited
applicability of the first ones to large scale today.
References
[1] C. D. Keeling, T. P. Whorf, M. Wahlen, J. Vanderplicht. Nature, 1995, 375, 666.
[2] M. O'Keeffe, O. M. Yaghi. Chem. Rev., 2012, 112 (2), 675.
[3] Y.-S. Bae, O. K. Farha, J. T. Hupp, R. Q. Snurr. J. Mater. Chem., 2009, 19, 2131.
[4] J. Yu, Y. Ma, P. B. Balbuena. Langmuir, 2012, 28, 8064.
[5] T. Duren, Y.-S. Bae, R. Q. Snurr. Chem. Soc. Rev., 2009, 38, 1237.
[6] D. Bahamon, L. F. Vega. Chemical Eng. J. 2016, in press (10.1016/j.cej.2015.08.098).
Acknowledgements:
Financial support from the Spanish Government (project CTQ2014-53987-R) and the Generalitat of Catalonia
(project 2014SGR1582) is gratefully acknowledged.

PPEPPD 2016
th
Extension of the NRTL-PRA model
for the modeling of mixtures containing electrolytes
Evelyne Neau1* and Christophe Nicolas2

1
M2P2(Mécanique et Modélisation et Procédés Propres) UMR 7340, Aix-Marseille Université, France
2
MIO (Mediterranean Institute of Oceanography), UMR 7294, Aix Marseille Université, France
* Corresponding author: evelyne.neau@univ-amu.fr
Scientific topic: Phase equilibria ( experimental, modeling)
Keywords: phase equilibria, EoS/gE model, hydrocarbons, associating compounds and electrolytes
Abstract
Petroleum fluids encountered during offshore exploitations in extreme conditions of pressure and
temperature are mainly composed of hydrocarbons and light gases (methane, carbon dioxide or hydrogen
sulfide) with salt water. Hence, gas hydrate formation is a major problem which requires injection of
inhibitors, mostly methanol.
The NRTL-PRA model was previously developed [1,2] to predict vapor-liquid and liquid-liquid
equilibria and excess enthalpies of methanol – hydrocarbon mixtures in presence of water. For this
purpose, the general formalism [3,4] of the NRTL-PR model, based on the cubic EoS/gE, was modified
by introducing an additional term characteristic of the self-association in the excess Gibbs energy gE.
In this work, the NRTL-PRA model is extended to phase equilibrium predictions of mixtures
containing electrolytes, water, methanol and light gases. As for the modeling of associated compounds,
specific terms were introduced in the excess Gibbs energy gE, in order to account for interactions
between ions and solvents (“middle range” and “long range” type contributions). Satisfactory results
were obtained for the modeling of mixtures containing sodium chloride in water, methanol and light
gases.
References
[1] E, Neau, I. Raspo,, J; Escandell, C. Nicolas, A. Khalfi, proceedings of the 28th ESAT (2015).
[2] E, Neau, I. Raspo,, J; Escandell, to be submitted to Fluid Phase Equilibria (2015).
[3] E. Neau, J. Escandell, C. Nicolas, Ind. Eng. Chem. Res., 49 (2010), 7589-7596.
[4] J. Escandell, E. Neau, C. Nicolas, Fluid Phase Equilib., 301 (2011), 80-97.
Acknowledgements
The authors gratefully acknowledge financial support from TOTAL

PPEPPD 2016
th
Separation of heptane + ethanol azeotrope using choline chloride based

binary and ternary deep eutectic solvents
Jelena M. Vuksanović1, Mirjana Lj. Kijevčanin1, Nina M. Todorović2, Ivona R. Radović1*

1
Department of Chemical Engineering/Faculty of Technology and Metallurgy, University of Belgrade, Serbia
2
ICTM – Center for Chemistry, University of Belgrade, Studentski trg 12–16, 11158 Belgrade, Serbia
*Corresponding author: ivonag@tmf.bg.ac.rs
Keywords: Deep eutectic solvents, Liquid-liquid equilibria, Choline chloride, 1,2-Propanediol, Ternary
DES
Abstract
The ability of non-toxic and biodegradable deep eutectic solvent (DES) choline chloride + 1,2-
propanediol in the molar ratio 1:3 for breaking the azeotrope heptane + ethanol by means of liquid-liquid
extraction was evaluated. Dai et al. [1] have already reported the structure of investigated DES, as well as
the influence of water on the supermolecular structure and hydrogen bonding within DES components.
Results have shown that the formed structure has been preserved as long as water content is below 50%.
Dai et al. [2] confirmed that the polarity of examined DES increases by addition of water which indicates
that the extraction efficiency of such ternary DES might be improved. Knowing this, extraction ability of
ternary DES choline chloride + 1,2-propanediol + water in the molar ratio 1:1:2 was also examined.
Liquid-liquid equilibrium experiments were performed at 298.15 K and at atmospheric pressure.
Additionally, NRTL and UNIQUAC models were applied for the correlation of the phase equilibrium
data of two investigated systems.
Based on the selectivity results and distribution ratio values, extraction ability of the investigated deep
eutectic solvents, in comparison with conventionally used solvents, promising results are obtained.
Besides a higher selectivity towards ethanol an advantage of the ternary DES is its lower viscosity which
is an important aspect for a potential industrial application.
References
[1] Y. Dai, G.-J. Witkamp, R. Verpoorte “Tailoring properties of natural deep eutectic solvents with water to
facilitate their applications” Food Chemistry, 2015, 187: 14-19.
[2] Y. Dai, J. van Spronsen, G.-J. Witkamp, R. Verpoorte, Y. H. Choi “Natural Deep Eutectic Solvents as new
potential media for green technology” Analytica Chimica Acta, 2013, 766: 61-68.
Acknowledgements
The authors gratefully acknowledge the financial support received from the Research Fund of Ministry of Science
and Environmental Protection, Serbia and the Faculty of Technology and Metallurgy, University of Belgrade
(project No 172063).

PPEPPD 2016
th
Electrolyte and Nonelectrolyte Heterosegmented PC-SAFT Equation of State

Applied to Ionic Liquids and Their Mixtures with Molecular Solvents
Kamil Paduszyński
1
Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Poland
*Corresponding author: kpaduszynski@ch.pw.edu.pl
Keywords: ionic liquids, PC-SAFT, phase equilibria
Abstract
Heteronuclear molecular models based on statistical associating fluid theory (SAFT) are viewed as
promising thermodynamic tools for modeling properties and phase equilibria. They differ from
conventional SAFT-based methodologies as they account for varying sizes and interactions of segments
constituting chain molecules. What is even more important, they pose as entirely predictive model when
applied to model mixtures since combining rules involve “group parameters” rather than classical
“molecular parameters”.
In this paper, an extension of heterosegmented version of perturbed-chain SAFT (hs-PC-SAFT)
[1] to ionic liquids (ILs) is presented and discussed. The pure-fluid parameters for ILs were determined
on the basis of fundamental pure-fluid properties of their molecular analogues (e.g. parameters for
“imidazolium core” from vapor pressure and density of alkylimidazoles, etc.) and some representative
reference binary data. In particular, an impact of inclusion of Debye-Huckel electrolyte term to residual
energy of mixture is considered. The ILs under study comprised those based on several cationic
(imidazolium, pyridinium, pyrrolidinium) and anionic families (bistriflamide, triflate, [BF 4], [PF6]). The
proposed parameterization was then applied to model binary vapor-liquid and liquid equilibria of mixture
of ILs with molecular solvents, including non-polar compounds like alkanes as well as polar and self-
associating compounds like alcohols.
References
[1] K. Paduszyński, U. Domańska “Heterosegmented Perturbed-Chain Statistical Associating Fluid Theory as a
Robust and Accurate Tool for Modeling of Various Alkanes. 1. Pure Fluids” Industrial Engineering & Chemistry
Research, 2012, 51: 12967-12983.
Acknowledgements
Funding for this research was provided by the Ministry of Science and Higher Education in the years 2015–2016
within the framework of the project “Iuventus Plus” no. 0347/IP3/2015/73.

PPEPPD 2016
th
Physical properties for binary systems containing deep eutectic solvent and
alcohols at different temperatures.
Olalla G. Sás1,*, Rubén Fidalgo1, Irene Domínguez2, Eugenia A. Macedo2, Begoña González1
1
2
Portugal
*Corresponding author: olallags83@uvigo.es
Scientific topic: thermodynamics and transport properties
Keywords: DES, density, viscosity, pure and binary systems
Abstract
Compared with the conventional ionic liquids, Deep Eutectic Solvents (DES) are more biodegradable
and biocompatible. Moreover, they are easily prepared with high purity at low cost. Because of this, an
extensive study of both properties of pure DES and of their binary mixtures with alcohols, in function of
temperature is very necessary and of considerable importance for the development and design of new
processes using these solvents.
In this work, DES are prepared using the heating method that is based on mixing the two components,
which are then heated under constant stirring until an homogeneus liquid is formed. The DES used are
based on choline chloride and combined with HBD carboxilyc acids.
Therefore, the viscosity, the density, speed of sound, and refractive index for pure and binary systems
containing DES and different alcohols have been measured in the temperature range between 293.15 and
353.15 K. The data obtained were analysed to evaluate the effect of (i) temperature, (ii) the nature of the
DES, and (iii) the nature of the alcohols used.
Acknowledgements
and NORTE-07-0124-FEDER 0000011), for which the authors are thankful.
The authors are alsograteful to the Comisión Interministerial de Ciencia y Tecnología (Spain) for the project
CTM2013- 46093-P and Xunta de Galicia (Spain) for the project EM2014/039. I. Domínguez is grateful to the
Xunta de Galicia for her scholarship (ED481B 2014/104-O).

PPEPPD 2016
th
Deep Eutectic solvent-based aqueous two phase system: a benign route as

novel extraction media.
Irene Domínguez1,*, Eugenia A. Macedo1, Angeles Domínguez2, Begoña González2

1
Portugal
2
Advanced Separation Processes Group, Edif. Isaac Newton, Department of Chemical Engineering,
University of Vigo, Lagoas-Marcosende, 36310 Vigo, Spain
*Corresponding author: irene@uvigo.es
Keywords: DES, Levulinic Acid, furfural, ABS
Abstract
Several processes have been suggested for treatment of biomass. Acid hydrolysis is one of these
processes which has shown great potential for the conversion of biomass. In this work, aqueous biphasic
systems (ABS) are proposed as alternative. Biocompatible liquid-liquid extraction techniques for the
recovery and purification of carboxilic acids, levulinic acid and furfural molecules from an aqueous
synthetic acid hydrolysis process stream are evaluated. A novel class of aqueous biphasic systems using
deep eutectic solvent (DES) is proposed instead toxic and poorly biodegradable ionic liquids that have
been explored hitherto. Nowadays, DES are considered as new green ionic liquids.
Several types of ABS, depending on their chemical composition, are known: water + polymer+ salt,
water + polymer + polymer, water + salt + salt. However, in this study, biodegradable and non toxic
organic salts, carbohydrates or aminoacidos will be used, as inorganic salts may lead to environmental
problems
In this work, the synthesis of two green deep eutectic solvent (DES) together with the liquid-liquid
equilibrium data and the phase diagrams of the aqueous biphasic systems at 25ºC are presented. In
addition, the partitioning of levulinic acid and furfural is investigated at 25ºC and atmospheric pressure.
Acknowledgements
and NORTE-07-0124-FEDER-0000011), for which the authors are thankful.
The authors are also grateful to the Comisión Interministerial de Ciencia y Tecnología (Spain) for the project
CTM2013- 46093-P and Xunta de Galicia (Spain) for the project EM2014/039. I. Domínguez is grateful to the
Xunta de Galicia for her scholarship (ED481B 2014/104-O).

PPEPPD 2016
th
Group contribution approach for prediction of enthalpies of solvation of

aromatic and heterocyclic compounds in different solvents at 298.15 K
Mikhail Varfolomeev*, Ruslan Nagrimanov, Boris Solomonov

Department of Physical Chemistry, Kazan Federal University, Russia
*Corresponding author: mikhail.varfolomeev@kpfu.ru
Keywords: Enthalpy of solvation, Enthalpy of solution, Group contributions, Calorimetry, Aromatic

compounds
Abstract
Enthalpy of solvation is important thermochemical value which gives quantitative information regarding
solute-solvent interactions in fluid solution. This value can be used for analysis of solvent effect on
different processes realized in liquid state. Also, enthalpies of solvation can be valuable tool for testing
solution models, modeling tools and quantum chemical computations. At the same time they can be
utilized to extrapolate gas-to-liquid partition coefficients to system temperatures slightly higher and/or
lower than the measurement temperature through standard thermodynamic relationships. Generally,
enthalpy of solvation can be presented as a sum of contributions of different intermolecular interactions:
enthalpy of non-specific solvation (van der Waals interactions), enthalpy of specific interaction (donor-
acceptor interactions, hydrogen bonds) and etc. Another common ratio relates the enthalpy of solvation
with the enthalpy of solution and the enthalpy of vaporization for liquid solutes or enthalpy of
sublimation for solid solutes. These two general relations can be used for evaluation of enthalpies of
intermolecular interactions or enthalpies of phase transitions directly at 298.15 K. Solvation enthalpies
can be measured only for gaseous at standard conditions solutes. Consequently, simple and rapid
methods for determination of solvation enthalpies are of great practical interest.
In this work we proposed a new approach for determination enthalpies of solvation of any solute in
studied solvent. According to this method the value of solvation enthalpy of aromatic or heterocyclic
compound in any solvent is calculated as a sum of the solvation enthalpy of the reference unit (aromatic
hydrocarbon; heteroaromatic compound without substituent, for example, pyridine) and contributions
due to the substitution of the hydrogen atoms in the reference unit by any other groups. Solvation
enthalpies of aromatic hydrocarbons and heteroaromatic compounds without substituents required for
this procedure were determined from the experimental data on solution enthalpies in the same solvent
and vaporization/sublimation enthalpies. Group contributions due to the substitution of hydrogen atom
by other groups were calculated as the difference between enthalpy of solvation of monosubstituted
benzene and benzene. Totally contributions of 17 groups (halogen, nitro, hydroxyl, alkyl, amino,
carbonyl, etc.) in different solvents were determined. Also, this procedure was adapted for heterocyclic
compounds with nitrogen, oxygen and sulfur atoms. We determined solvation enthalpies for different
solute-solvent systems using group-addivity scheme. Comparison of obtained values with available in the
literature data confirms validity of proposed approach.
Acknowledgements
This work has been supported by grant MK-7126.2015.3 and performed according to the Russian Government
Program of Competitive Growth of Kazan Federal University.

PPEPPD 2016
th
Uncertainty Quantification and Propagation Associated with a Transferable

Intermolecular Potential Model for n-Alkanes
Richard A. Messerly*, Thomas A. Knotts IV, Richard A. Rowley, and W. Vincent Wilding
Chemical Engineering, Brigham Young University, USA
*Corresponding author: r.alma.messerly@gmail.com
Scientific topic: Fundamentals: Quantum mechanical calculations and force fields
Keywords: Force Field, Uncertainty Quantification, Transferable Potential Model, Critical Constants
Abstract
The Design Institute for Physical Properties (DIPPR 801 database) is one of the premiere databases for
evaluated physical properties. An important feature of the database is the assignment of uncertainty
associated with the property values, which is essential for robust process design. However, determining
an appropriate uncertainty is normally more straightforward for experimental measurements than for
molecular simulation results. This is because molecular simulation has many layers of uncertainty that
are difficult to quantify. Since the reliability of molecular simulation is intimately connected with the
intermolecular potential model chosen and the corresponding model parameters, one of the most
important layers of uncertainty in molecular simulation is related to the optimization of the model
parameters. By quantifying this uncertainty, the DIPPR 801 database can better assess the reliability of
molecular simulation results. This is important for predicting properties that are difficult to measure
experimentally, such as the critical constants for large n-alkanes.
Historically, most studies that report molecular models neglect to perform a statistical analysis of their
optimized parameters. Occasionally, the literature provides a sensitivity analysis, where the model
parameters are varied by an arbitrary amount and the effect on the simulation results is reported.
However, a sensitivity analysis of this nature actually provides little insight because model parameters
are often strongly correlated. A more rigorous approach to assess the uncertainty is to examine which
combinations of parameters deviate from the optimized parameter set to within a given statistical
tolerance level. Historically, a rigorous analysis has been considered infeasible due to the computational
cost of molecular simulations, though recently small molecular systems have been investigated. This
study is the first attempt to rigorously quantify the intermolecular parameter uncertainties for a
compound as large as n-octane.
In this work, we have investigated the rigorous uncertainty associated with a transferable Lennard-Jones
12-6 potential model for n-alkanes by systematically exploring the parameter space of 𝜖 and 𝜎 for CH3
and CH2. This was accomplished by performing thousands of Gibbs Ensemble Monte Carlo simulations
at the same conditions used in the TraPPE parameterization for ethane and n-octane. We have
demonstrated that, due to the advances in computational speed, rigorous statistical analysis is now
possible for transferable parameter sets. We also performed a propagation of error analysis for the critical
constants of larger n-alkanes to determine the uncertainty associated with predicting these properties
from molecular simulation. By so doing, we have enhanced the ability of molecular simulation to be a
quantitative tool in physical property assessment and process design. Therefore, this study has aided the
DIPPR 801 project in predicting the long-chain-length trend for the critical constants of n-alkanes.
PPEPPD 2016
th
Improved phase stability testing in the single phase region
Dan Vladimir Nichita1*

1
CNRS UMR 5150, Laboratoire des Fluides Complexes et leurs Réservoirs,
Université de Pau et des Pays de l’Adour, 64013 Pau, France
*Corresponding author: dnichita@univ-pau.fr
Keywords: Phase stability, Stability test limit locus, Singularity, Convergence, Robustness
Abstract
Phase stability analysis is essential in process systems engineering and petroleum reservoir engineering.
The stability test limit locus (STLL) [1,2] is an important underlying property of multi-component
system phase diagrams because in its vicinity the number of iterations for phase stability testing
dramatically increases and divergence may occur. The cause of convergence problems in phase stability
calculations in the single-phase state is the topology of the TPD surface. At the STLL, the TPD surface
exhibits a saddle point and for pressures just above the STLL the Hessian matrix is ill-conditioned in a
domain of the hyperspace that must be “crossed” by iterates starting from one of the two-sided initial
guesses [3]. This makes stability testing in the vicinity of the STLL really challenging, and any algorithm
will experience difficulties in this region [3,4,5]. In this work, a new formulation of the phase stability
problem is presented, as a constrained optimization problem with specific sets of variables and
constraints, for both conventional (in the compositional space) and reduced (in the hyperspace defined by
reduction parameters [6]) variables. A hybrid gradient-Newton (with line search and bring-back
procedures as safety features) algorithm is used in the minimization. Formal links between conventional
and reduction formulations are established. The proposed method is tested and compared with previous
methods by spanning large P-T-Z domains for synthetic and natural hydrocarbon mixtures combined
with non-hydrocarbon components. Numerical experiments show a highly improved convergence
behavior, mainly for pressures above the STLL, recommending the proposed method for compositional
simulators, in which the problematic domain is crossed a very large number of times during simulations.
References
[1] C.H. Whitson, M.L. Michelsen “The negative flash” Fluid Phase Equilib. 1990, 53: 51-72.
[2] D.V. Nichita, D. Broseta, F. Montel “Calculation of convergence pressure/temperature and stability test limit
loci of mixtures with cubic equations of state” Fluid Phase Equilib. 2007, 261: 176-184.
[3] M.L. Michelsen “The isothermal flash problem. Part I. Stability” Fluid Phase Equilib., 1982, 9: 1-20.
[4] D.V. Nichita, M. Petitfrere “A reduction method for phase stability analysis”, Fluid Phase Equilib. 2013, 358:
27-39.
[5] M. Petitfrere, D.V. Nichita “A comparison of conventional and reduction approaches for phase equilibrium
calculations” Fluid Phase Equilib. 2015, 386: 30-46.
[6] E.M. Hendriks “Reduction theorem for phase equilibria problems”, Ind. Eng. Chem. Res. 1988,27: 1728-1732.

PPEPPD 2016
th
Taxonomy of Cocrystal Ternary Phase Diagrams
Richard B. McClurg*
SSCI, a division of Albany Molecular Research Inc. (AMRI), West Lafayette, IN, 47906, USA
*Corresponding author: richard.mcclurg@amriglobal.com
Scientific topics: Phase Equilibria, Pharmaceuticals
Keywords: ternary phase diagram, pharmaceutical, cocrystal
Abstract
Multi-component solids are commonly used in the pharmaceutical industry to deliver active
pharmaceutical ingredients (APIs). Solids are desirable to confer physical and chemical stability with the
convenience of solid oral dosage (tablets). For many APIs there are several solid forms available and
one must be chosen for development. Options include salts [1], hydrates [2], solvates [3], and cocrystals
[4]. For the purpose of this abstract, a cocrystal is a crystalline phase that contains an API and another
molecular species other than water or solvent, called the coformer.
Three component phase diagrams (API, coformer, and solvent) are beginning to be used to understand
cocrystal systems [5,6]. Phase coexistance loci have typically been fit using algebraic expressions
derived from idealized equilibrium models [5]. In this poster, the connection between the free energy
surface and the phase diagram is used to develop a taxonomy of cocrystal phase diagrams.
References
[1] S. M. Berge, L. D. Bighley, and D. C. Monkhouse “Pharmaceutical salts” J. Pharm. Sci., 1977, 66(1): 1-19.
[2] D. J. W. Grant and T. Higuchi, Solubility Behavior of Organic Compounds (Techniques of Chemistry) Wiley,
1990.
[3] FDA Guidance for Industry, "Q3C Impurities: Residual Solvents" accessed from FDA website:
www.fda.gov/downloads/Drugs/GuidanceComplianceRegulatoryInformation/Guidances/UCM073394.pdf on 20
October, 2015.
[4] N. Schultheiss and A. Newman “Pharmaceutical Cocrystals and Their Physicochemical Properties” Cryst.
Growth Des., 2009, 9(6): 2950-2967.
[5] A. Jayasankar, L. S. Reddy. S. J. Bethune, and N. Rodriguez-Hornedo “Understanding and Predicting the
Effect of Cocrystal Components and pH on Cocrystal Solubility” Cryst. Growth Des., 2009, 9(2): 889-897.
[6] R. Thakuria; A. Delori; W. Jones; M. P. Lipert; L. Roy; N. Rodríguez-Hornedo “Pharmaceutical cocrystals

and poorly soluble drugs” Int. J. of Pharm., 2013, 453(1):101-125.

PPEPPD 2016
th
New measurement technique for surface tension at high-temperature/high-

pressure fluid phase equilibrium
Yohei Kayukawa1* , Masato Umehara2 and Katsuyuki Tanaka2

1
National Metrology Institute of Japan/National Institute of Advanced Industrial Science and Technology, Japan
2
Department of Precison Machinery Engineering/Nihon University, Japan
*Corresponding author: kayukawa-y@aist.go.jp
Keywords: Surface tension, high pressure, magnetic suspension balance (maximum 5 keywords)
Abstract
Considering thermal efficiency of evaporators or condensors used in heat pump systems, surface tension
is very important to simulate the flow regime. Since transport properties for engineering fluid are also
important in heat-transfer engineering, thermal conductivities or viscosities for several working fluids
have been studied. For surface tensions, however, there exist not many experimental studies. One reason
is that measurement for surface tension at high-temperature/high pressure codition is difficult. For
example, to measure height of raise of meniscus in glass capillary is the most effective procedure but not
applicable at very high temperature or pressure. The Wilhelmy method is valid under ambient pressure.
In the present study, therefore, the authors have proposed and developed a novel experimental technique
to measure surface tensions under high-temperature/high-pressure condition. The core component is a
magnetic suspension balance (MSB). Commercially available MSB was employed to mesure force
change acting on a platinum ring placed on the vapor-liquid interface to order of 0.01mg. The MSB
enables the present appratus to be operated at wide range of temperature (up to 470 K) and pressure (up
to 20 MPa).

PPEPPD 2016
th
A New Electrolyte Model for Inhibited Hydrate Phase Equilibria Predictions
Muhammad N. Khan1,2, Hao Qin1, Pramod Warrier1, Cor J. Peters2,3 Carolyn A. Koh1*
1
Center for Hydrate Research, Chemical & Biological Department,
Colorado School of Mines, Golden, CO 80401, USA,
2
Chemical Engineering Department Petroleum Institute Abu Dhabi U.A.E
3
Department of Chemical Engineering and Chemistry, Separation Technology Group
Eindhoven University of Technology, Eindhoven, The Netherlands
*Corresponding author: ckoh@mines.edu
Keywords: Gas Hydrates, Phase equilibria, Electrolyte model
Abstract
Gas hydrates are crystalline inclusion compounds which form when water and gas come into
contact at high pressure and low temperature conditions. Since these conditions are prevalent in
deepwater oil/gas transmission lines, gas hydrates can form flowline blockages, which can lead to severe
safety and environmental risks. Preventing hydrate flowline blockages requires sound knowledge of
hydrate phase equilibria behavior. Current hydrate phase equilibria predictions using different models
based on statistical thermodynamics for inhibited systems (with salts, e.g. NaCl, KCl, CaCl 2, also
methanol, ethylene glycol) exhibit large errors. The current Colorado School of Mines Gibbs Energy
minimization (CSMGem) activity model is not reliable for predicting these inhibited systems, especially
when the concentrations are greater than around 30 Wt.%. Therefore, the association EoS needs to be
coupled with a reliable electrolyte activity model. In this work, various electrolyte models: Debye-
Hückel, truncated Debye-Hückel, Pitzer theory and Bromley activity models were tested in mean activity
coefficient calculations. The Debye-Hückel and truncated Debye-Hückel models give accurate
predictions at lower salt concentrations, but significant deviations were observed at a molal concentration
of higher than 1 mol/kg. The Bromley activity model and Pitzer theory were found to be good
alternatives to the Debye-Hückel models and its modifications. For 1:1 electrolytes, the Pitzer theory and
Bromley activity models give accurate predictions up to the saturation limit of salt solutions. Conversely,
mean activity coefficient calculations for 1:2 electrolytes (CaCl2, MgCl2 and BaCl2) using the Pitzer
theory, Bromley activity model, or Debye-Hückel model and its modification were not able to capture
the electrolyte contribution of these salts. A more rigorous statistical thermodynamics approach (Mean
Field Spherical Approximation) has also been developed in this work to more accurately predict the
activity of the aqueous phase and 1:2 electrolytes.
Acknowledgements
The authors would like to acknowledge the funding from the CSM Center for Hydrate Research Consortium and
the Petroleum Institute, Abu Dhabi for funding MNK.

PPEPPD 2016
th
Computational Platform to Design Crystal Growth Inhibitors for Zeolites
R. John Clark, Jeremy C. Palmer* and Jeffrey D. Rimer

Department of Chemical and Biological Engineering, University of Houston, USA
*Corresponding author: jcpalmer@uh.edu
Keywords: Zeolites, Crystal Growth, Inhibitors, Molecular Simulation
Abstract
Microporous zeolite materials find use in a variety of important industrial applications including fluid-
based separations, ion exchange, hydrocarbon cracking, and methanol reformation. Despite their
widespread use, fully optimizing zeolites for targeted technological applications remains a formidable
challenge due to the difficulty in controlling crystal morphology and structure during synthesis. It has
been recently demonstrated, however, that such control may be gained through the addition of small-
molecule structure directing agents, or zeolite growth modifiers (ZGMs), which bind to specific crystal
surfaces and inhibit growth along targeted crystallographic directions [1]. Using small amines and
polyols as ZGMs, this strategy has been successfully applied to synthesize zeolite L crystals (LTL type)
with controlled pore lengths, suggesting a novel strategy for tuning the transport properties of zeolites
[1].
Although ZGMs show tremendous promise in facilitating the development of improved zeolite materials,
the underlying molecular-level mechanisms that allow them to regulate crystal growth are not fully
understood. To elucidate such mechanisms, we employ molecular simulation techniques to investigate
the interactions between small polyol ZGMs and the different crystal faces of zeolite L. While bulk
materials have been studied extensively using computational methods, modeling the crystal faces of
zeolites poses a unique set of challenges due to the complex surface chemistry involved in terminating
the crystal. We discuss these challenges in detail and describe several different approaches for modeling
zeolite surfaces. We then demonstrate that state-of-the-art free energy techniques, such as metadynamics
and umbrella sampling, can be used to gain significant insight regarding the sorption and binding of
ZGMs on zeolites. Our findings support the hypothesis that polyols form hydrogen bonds with the
surface of zeolite L, inhibiting growth through a molecular recognition process that is sensitive to both
the structure of the polyol and zeolite [1]. Finally, we discuss the broarder implications of our findings
and the potential of computational techniques to aid in the judicious selection of ZGMs to target specific
crystal faces of zeolites.
References
[1] A. I. Lupulescu, M. Kumar, J. D. Rimer, “A facile strategy to design zeolite L crystal with tunable morphology
and surface architecture” Journal of the Americal Chemical Society, 2013, 135: 6608-6617.

PPEPPD 2016
th
Hydration structure and dynamics of poly(2-methacryloyloxyethyl

phosphorylcholine)
Christoph Klein*, Christopher R. Iacovella, Clare McCabe, and Peter T. Cummings

Department of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville,
Tennessee 37235, United States
*Corresponding author: christoph.klein@vanderbilt.edu
Keywords: Nanotribology, hydration lubrication, zwitterionic
Abstract
We explore the hydration structure and dynamics of poly(2-methacryloyloxyethyl phosphorylcholine)50,

or pMPC50, in solution using molecular dynamics simulations. Surface bound films of this biocompatible
polymer have been shown experimentally to produce tribological properties that surpass those of the
human synovial joint [1] and are being developed for use in artificial joints [2]. The mechanism by which
such materials are thought to provide ultra-low friction coefficients has been termed “hydration
lubrication” [3]. In previous work, we explored the conditions under which water favorably hydrates
surface bound MPC monomers and enables such materials to utilize the hydration lubrication mechanism
[4]. Here, we further characterize the molecular level structure and dynamics of this hydration water
around the much larger pMPC molecules that are experimentally grafted onto substrates for biomimetic
lubrication. Our results show that the charged choline groups of individual monomers tend to fold onto
neighboring monomers. This has the threefold effect of i) compacting the polymer, ii) excluding
significant volume where hydration shells could otherwise form around the choline groups and iii)
bending the monomers at the phosphate group thus preferentially exposing the two strongly negatively
charged oxygen atoms in the phosphate group to the aqueous environment. These results suggest that the
predominant contribution to hydration lubrication in pMPC based materials is derived from water
hydrating the phosphate group and that the choline group plays a lesser or perhaps negligible role.
However, the strong association of the choline groups with neighboring monomers may serve to stabilize
the overall polymer structure which would contribute to the high resistance to compression exhibited by
hydrated pMPC films. Comparisons of the steady-state residence time of water molecules in several
hydration shells around the polymer are computed and compared to our previous results for surface
bound MPC monomers to demonstrate the effect of the structural difference on hydration.
References
[1] M. Chen et al., “Lubrication at Physiological Pressures by Polyzwitterionic Brushes.” Science 2009, 323: 1698–
1701.
[2] M. Kyomoto et al., “Biomimetic hydration lubrication with various polyelectrolyte layers on cross-linked
polyethylene orthopedic bearing materials.” Biomaterials 2012, 33: 4451-9.
[3] J. Klein, “Hydration lubrication.” Friction 2013, 1: 1–23.
[4] C. Klein, C. R. Iacovella, C. McCabe, P. T. Cummings, “Tunable transition from hydration to monomer-
supported lubrication in zwitterionic monolayers revealed by molecular dynamics simulation.” Soft Matter 2015,
11: 3340-6.
PPEPPD 2016
th
A Pure Prediction Method for Binary VLE Established Using Experimental

Data of 5000 Binaries
Satoru Katoa*
a
TC Lines NZ Ltd, New Zealand
*Corresponding author: kato@tc-lines.com, webpage: http://tc-linex.com
Scientific topic: Phase equilibria ( modeling)
Keywords: Pure prediction method, VLE, TC lines
Abstract
Applications of a pure prediction method for binary VLE are presentd.

Pure Prediction Method: a universal function of temperature, T, for the infinite dilution activity
coefficient of component i, lnaiinf, has been formulated using vapor pressures, p1s and p2s, as a differential
equation:
d ln ai inf
 U (T , p1s , p2 s , ln a1inf , ln a2 inf ) 　　　　 (i  1,2) 　　　　　 (1)
dT
ln ai inf  ln ai inf 　　 at　 T　　　　　　　　　　

B.C. : 　　　　　　 (2)
Conventional activity coefficient equations satisfy the Gibbs-Duhem equation: therefore, the Margules,
van Laar, UNIQUAC, NRTL or Wilson [1] is used for the determination of activity coefficeints using
γi∞determined from Eqs. (1) and (2).
Applications: i) the pure prediction method successfully predicts P, T, x, y relationships of 5000 binaries
[2]. TC lines (thermodynamic consistency lines) [2, 3] were used to examine the accuracy of the
temperature dependency of VLE data, because the TC line is a high-precision correlation of VLE data.
ii) UNIFAC group interaction parameters are improved using the pure prediction method, because the
pure prediction method, Eqs. (1) and (2), can predict binary VLE, even if experimental VLE data is
lacking.
References
[1] B.E. Poling, J.M. Prausnitz, J.P. O’Connell, The Properties of Gases and Liquids, 5 th ed. McGraw-Hill, New
York, 2001.
[2] J. Gmehling, U. Onken, Vapor–Liquid Equilibrium Data Collection, Chemistry, Data Series, vol.1, part 1–8,
1981, Dechema.
[3] S. Kato, J. P. Schmelzer, P. Gostomski, K. N. Marsh,“Vapor-phase mole fractions determined from the P, x data
using the Margules equation for high-pressure binary vapor-liquid equilibrium systems including carbon dioxide”J.
Chem. Eng. Data, 56 (2011) 4927-4934.
[4] S. Kato, P. Gostomski, A. Oda, J. Freitag, S. Hirohama, D. Bluck,” Prediction of mutual solubility and low-
pressure VLE using high-precision correlation lines” Fluid Phase Equilib., 357 (2013) 36-42.
PPEPPD 2016
th
Liquid-liquid equilibria in ethyl propanoate+heptane+[pyridinium-

derived][F4B] Ionic Liquids. Experimental results and modeling
Luis Fernández1*, Juan Ortega1, Raul Rios1,

1
Grupo de Ingeniería Térmica, Universidad de Las Palmas de Gran Canaria, España
*Corresponding author: luis.fdz.suarez@gmail.com
Keywords: Liquid-liquid equilibrium, ionic liquids, ester, alkane
Abstrac
The presence of an azeotrope in a solution limits the possibility of obtaining products of high purity by
distillation. There are several ways to solve this problem of separation, however one of the best known is
the liquid-liquid extraction. The use of ionic liquids (ILs) as extraction agent has been studied by various
researchers [1,2], because of their particular characteristics. For years, our group is working with fluid
systems containing alkyl esters with other components such as saturated hydrocarbons [3], alkanols [4],
among others. In a matrix of binaries ESTERxALKANE the azeotropic situation of those solutions is
presented, showing the composition in a central zone xaz[0.4-0.6] of the systems: methyl
methanoate+pentane, butyl ethanoate+octane, and ethyl propanoate+heptane. Of these, the last binary is
chosen to analyze the effect as entrainer of a series of pyridinium-based ionic liquids, [bXmpy] [F4B]
(X=2,3,4), [hpy] [F4B], [opy][F4B]. At a pressure of 101.32 kPa, the system CH3(CH2)CO2C2H5 + C7H16
has the following coordinates of the singular point: xaz=0.481, Taz=367 K [3]. More specifically, it is
analyzing the influence of the position of the alkyl radical (ortho-, meta-, para-) with isomers [bXmpy]
[F4B] (X=2,3,4), and the length of the radical of the pyridinium group (butyl-, hexyl-, octyl-), in the
displacement of the azeotrope.
The experimental procedure consists in a cell where, by isothermal agitation-decantation, the resulting
phases are separated and the composition of each is determined by gas chromatography, using a
headspace-sampler. The experimental results are represented by a model developed by our group [5],
using a mathematical procedure that ensures compliance with the phase stability criteria. This model is
used to evaluate the selectivity and capacity of each of the ionic liquids in order to select the most
suitable to achieve the separation of compounds in the binary ethyl propanoate (1)+heptane(2).
References
[1] J. G. Huddleston, H. D. Willauer, R. P. Swatloski, A. E. Visser, R. D. Rogers. “Room temperature ionic liquids
as novel media for ‘clean’ liquid-liquid extraction.” Chemical Communications, 1998, 1765-1766.
[2] M. Larriba, P. Navarro, J. García, F. Rodríguez. “Liquid-liquid extraction of toluene from heptane using
[EMIM][DCA], [BMIM][DCA], and [EMIM][TCM] ionic liquids.” Industrial & Engineering Chemistry Research,
2013, 52, 2714-2720.
[3] R. Rios, J. Ortega, L. Fernández, I. de la Nuez, J. Wisniak. “Improvements in the experimentation and the
representation of thermodynamic properties (iso-p VLE and yE) of alkyl propanoate + alkane binaries.” Journal of
Chemical & Engineering Data, 2014, 59, 125-142.
[4] F. Espiau, J. Ortega, E. Penco, E. J. Wisniak. “Advances in the Correlation of Thermodynamic Properties of
Binary Systems Applied to Methanol Mixtures with Butyl Esters.” Industrial & Engineering Chemistry Research,
2010, 49, 9548-9558.
PPEPPD 2016
th
Polymer-Salt ATPS: Phase diagrams and modeling
Marlen González-Amado,1 Eva Rodil,1 Alberto Arce,1 Ana Soto1 and Oscar Rodríguez1*
1
Departamento de Enxeñería Química, Universidade de Santiago de Compostela, Spain
*Corresponding author: oscar.rodriguez@usc.es
Keywords: ATPS, protein, partitioning, polymer, electrolytes
Abstract
Aqueous two-phase systems (ATPS) are obtained upon mixing of aqueous solutions of two polymers, a
polymer and a salt, or even two salts (one being an ionic liquid). They can be used for the recovery of a
wide array of solutes in aqueous solution (metal ions, small molecules, biomolecules) but their most
prominent use is for bioseparations. The presence of a mild aqueous medium in both phases is suitable
for the recovery of proteins, antibodies and other biomolecules, organelles and even whole cells and
viruses [1]. Polymer-salt ATPS are often preferred due to the lower cost of the phase-forming
components. The knowledge of the ATPS phase diagram and the partitioning of the target solutes on its
different tie-lines is critical for the extraction process selection, design and optimization.
In this work, the phase diagram for a set of different polymer-salt ATPS has been obtained
experimentally at different temperatures using compositional analysis of the phases in equilibrium. ATPS
were formulated combining typical polymers such as polyethylene glycol (PEG), and inorganic salts like
sulfates. PEG is extensively used in ATPS due to its biocompatibility and GRAS (Generally Recognized
As Safe) status. Sulfate salts are used due to their availability and low cost. Compositional analysis was
carried out from density and refractive index measurements from each equilibrium phase. The effect of
different features such as polymer and salt nature or temperature in the phase diagram is discussed.
Differences in the ATPS phase diagram can be explained in terms of excluded volume or hydration shell.
Partitioning of some example proteins was carried out in some selecetd ATPS. Typical proteins such as
bovine serum albumin (BSA) or lactalbumin have been used for the purpose. Thermodynamic partition
coefficients of the proteins (independent of solute composition) were obtained as ratio of solute
compositions in both phases, measured experimentally [2].
References
[1] P.A. Albertson, Partition of cells particles and macromolecules, 3rd edition, New York (USA), 1971.
[2] O. Rodríguez, S.C. Silvério, P.P.Madeira, J.A. Teixeira, E.A. Macedo “Physicochemical Characterization of the
PEG8000-Na2SO4 Aqueous Two-Phase System” Industrial & Engeneering Chemistry Research, 2007, 46: 8199-
8204.
Acknowledgements
This work was funded by Xunta de Galicia (Spain) through Project EM2014/023. O. Rodriguez also acknowledge
financial support of the Ramón y Cajal fellowships RYC-2012-10378.

PPEPPD 2016
th
Switching Solution Properties using Photochromic Ionic Liquids
Mário R.C. Soromenho1, Filipa Siopa2, José N. Canongia Lopes1,

Luís P. N. Rebelo1, Carlos A. M. Afonso2, José M. S. S. Esperança1,*
1
Instituto de Tecnologia Química e Biológica, Univ. Nova Lisboa, Portugal
2
iMed UL, Faculdade de Farmácia, Univ. Lisboa, Portugal
*Corresponding author: jmesp@itqb.unl.pt
Scientific topic: Thermodynamics and Transport properties
Keywords: Photochromic, Ionic Liquids, Physical and Transport Properties, Switching Tool
Abstract
Photochromism is seen as a light-driven reversible A↔B switch leading to changes in the electronic and
structural state of matter. The photoinduced inter-conversion of one state of a photochromic compound
into another is accompanied by significant structural and electronic transformations, generating
important changes in its physical and chemical properties.
The creation of new photochromic ionic liquids (PCILs) by the incorporation of a photochromic center as
a substituent in the ionic liquid cation leads to a bifunctional material which joins together the properties
of both ionic liquids and chromophores directing to the development of a plethora of novel applications.
In this work, we synthetized a chromophore center, 1,2-bis(2-methyl-1-benzothiophene-3-
yl)perfluorocyclopentene (BTF6) which has been used to study the effect of photoinduction on its
conversion in solutions with distinct solvents and ionic liquids. The results clearly show an enhancement
of the photoinduced conversion of the chromophore by using ionic liquids as additives.[1]
In a second stage we developed completely new PCILs based on a diarylethene center. These are
dicationic ILs that use distinct IL cations, namely alkylimidazoliums or tetraalkylammoniums. The
synthesized PCILs are soluble in water which represents an extraordinary advantage over diarylethene
derivatives. Upon irradiation with UV light we have observed changes in the physical and chemical
properties of distinct solutions containing these PCILs, even at very low concentrations.
Ab-initio calculations and molecular dynamics simulations will reveal the underlying structural changes
responsible for the observed experimental results.
The use of these compounds in distinct processes is being evaluated and some recent results will be
highlighted.
References
[1] M.R.C. Soromenho, F. Siopa, C.A.M. Afonso, J.M.S.S. Esperança “Enhanced photoconversion of 1,2-bis(2-
methyl-1-benzothiophene-3-yl)perfluorocyclopentene in solution with ionic liquids” to be submitted
Acknowledgements
The authors thank Fundação para a Ciência e Tecnologia, FCT/MEC (Portugal), for financial support through
grants (M.R.C.S., F.S.), FCT Investigator contract (J.M.S.S.E) and projects PTDC/CTM-NAN/121274/2010,
PTDC/QUI-QUI/117340/2010, FCT-ANR/CTM-NAN/0135/2012 and UID/Multi/04551/2013.

PPEPPD 2016
th
Adsorption Behavior of Metal Precursors on Mesoporous Silica in

Supercritical Carbon Dioxide
Ikuo Ushiki 1*, Naoto Takahashi 2, Masaki Ota 2, Yoshiyuki Sato 2, Richard L. Smith Jr. 1, 2, Hiroshi Inomata 2
1
Graduate School of Environmental Studies, Tohoku University, Japan
2
Research Center of Supercritical Fluid Technology, Tohoku University, Japan
*Corresponding author: iushiki@scf.che.tohoku.ac.jp
Keywords: Metal precursor, Supercritical carbon dioxide, Adsorption, Mesoporous Silica
Abstract
Mesoporous silica has attracted attention as a support medium of catalyst due to its unique pore structure
and high surface area. Supercritical carbon dioxide (scCO2) impregnation of metal particles into porous
materials is used because its ability to disperse particles into medium is superior to that by conventional
methods [1][2]. For efficient design of the supported catalyst, it is important to understand quantitative
adsorption behavior of metal precursor which is considered to be an initiation process of the
impregnation [3]. In this work, adsorption behavior of metal precursors (Rh(acac)3, Co(acac)3) on various
types of mesoporous silica (MCM-41, MSU-H, and HMS) under scCO2 conditions was measured and
analyzed by using the Dubinin-Astakhov (DA) equation [4] in consideration of the adsorption equilibria.
The amount of adsorbed metal precursors was found to increase with increasing temperature and
decreasing pressure, which could be explained by CO2 density effects. The DA equation demonstrated
satisfactory correlation of the experimental results, and the fitting parameters provided quantitative
information about the adsorption phenomena of the metal precursors in scCO2.
References
[1] T. Shimizu, I. Ushiki, M. Ota, Y. Sato, N. Koizumi, H. Inomata “Preparation of Mesoporous Silica Supported
Cobalt Catalysts using Supercritical Fluids for Fischer-Tropsch Synthesis” Chemical Engineering Research and
Design, 2015, 95: 64-68.
[2] J. Morere, M.J. Tenorio, M.J. Torralvo, C. Pando, J.A.R. Renuncio, A. Cabanas “Deposition of Pd into
mesoporous silica SBA-15 using supercritical carbon dioxide” Journal of Supercritical Fluids, 2011, 56: 213-222.
[3] Y. Zhang, C. Erkey “Preparation of supported metallic nanoparticles using supercritical fluids: A review”
Journal of Supercritical Fluids, 2006, 38: 252-267.
[4] M.M. Dubinin, V.A. Astakhov “Description of adsorption equilibria of vaporson zeolites over wide ranges of
temperature and pressure” Advances in Chemistry Series, 1971, 105: 69-85.
Acknowledgements
This research was financial supported byu JSPS KAKENHI (No. 25289271 and 15J02431). I. U. is a JSPS
Research Fellow (PD) and received financial supports from JSPS Research Fellowships for Young Scientists.

PPEPPD 2016
th
Theoretical Analysis of ePC-SAFT Equation of State for Predicting

Infinite Dilution Partition Coefficients in
Supercritical CO2 – Ionic Liquid Biphasic Systems
Yuya Hiraga1*, Yoshiyuki Sato1, Richard L. Smith, Jr.2
1
Graduate School of Engineering, Tohoku University, Japan
2
Graduate School of Environmental Studies, Tohoku University, Japan
*Corresponding author: yuya-h@scf.che.tohoku.ac.jp
Keywords: Ionic liquid, ePC-SAFT, partition coefficient
Abstract
Although the ePC-SAFT equation of state has been shown to provide reliable predictions of the solubility
of CO2 in many ionic liquids [1], the equation fails to provide quantitative predictions when applied to
solute partitioning in supercritical CO2 – ionic liquid biphasic systems, even when the solute-ionic liquid
and solute-supercritical CO2 binary interactions are determined from experimental data [2]. In this work,
the contribution of the Helmholtz energy ionic term to the calculation is examined in detail through
analysis of solute partitioning in CO2 – ionic liquid biphasic systems that contain hydrophobic ionic
liquids (e.g., 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [bmim][Tf2N]) or
hydrophilic ionic liquids (e.g.,1-allyl-3-methylimidazolium chloride, [amim]Cl) using both literature and
experimental measurements [2-5]. It is found that ionic liquids for which CO2 has high solubility in the
ionic liquid phase the solute-ionic liquid interactions change as CO2 dissolves into the ionic liquid phase.
Modification of the dielectric constant in the ionic term of the ePC-SAFT equation of state is one method
for improving the description of solute partitioning in supercritical CO2 – biphasic systems.
References
[1] X. Ji, C. Held, G. Sadowski, "Modeling imidazolium-based ionic liquids with ePC-SAFT", Fluid Phase
Equilibria, 2012, 335: 64-73.
[2] Y. Hiraga, Y. Sato, R.L. Smith, "Measurement of infinite dilution partition coefficients of isomeric benzene
derivatives in [bmim][Tf2N]-CO2 biphasic system and correlation with the ePC-SAFT equation of state", Fluid
Phase Equilibria, Under review.
[3] Y. Hiraga, A. Kato, Y. Sato, T.M. Aida, M. Watanabe, R.L. Smith, "Separation factors for [amim]Cl-CO2
biphasic systems from high pressure density and partition coefficient measurement ", Separation and Purification
Technology, 2015, 155: 139-148.
[4] Y. Hiraga, A. Hayasaka, Y. Sato, M. Watanabe, R.L. Smith, "Partition coefficients of furan derivative
compounds in 1-n-butyl-3-methylimidazolium chloride ([bmim][Cl])-supercritical CO2 biphasic systems and their
correlation and prediction with the LSER-delta model", Journal of Supercritical Fluids, 2013, 79: 32-40.
[5] Y. Hiraga, W. Endo, H. Machida, Y. Sato, T.M. Aida, M. Watanabe, R.L. Smith Jr, "Infinite dilution partition
coefficients of benzene derivative compounds in supercritical carbon dioxide + ionic liquid systems: 1-butyl-3-
methylimidazolium chloride [bmim][Cl], 1-butyl-3-methylimidazolium acetate [bmim][Ac] and 1-butyl-3-
methylimidazolium octylsulfate [bmim][OcSO 4]", Journal of Supercritical Fluids, 2012, 66: 49-58.

PPEPPD 2016
th
Multicriteria screening approach for solvent selection and design for CO2
capture
Maria Teresa Mota-Martinez1,3,*, Jason P. Hallett1 and Niall Mac Dowell2,3

1
Department of Chemical Engineering, Imperial College London, UK
2
Centre for Environmental Policy, Imperial College London, UK
3
Center of Process Systems Engineering, Imperial College London, UK
* Presenting author: m.mota-martinez@imperial.ac.uk
Scientific topic: Product and Process Engineering
Keywords: Carbon capture, process modelling, physical properties, solvent desing, carbon dioxide
Abstract
Decarbonization of energy generation is essential to tackle global warming. While renewable energy
starts to penetrate into the energy mix, fossil fuels currently remain the prevailing source of energy.
Consequently, Carbon Capture and Storage (CCS) technology is going to play a crucial role in reducing
carbon dioxide (CO2) emissions from fossil fuel powered plants. CCS implementation is hampered by
the relatively high cost of the most mature technology, i.e. chemiabosroption in aqueous alkanolamines,
associated with parasitic energy penalties of the process.
Whereas the development of new solvents (e.g. ionic liquids) has primarily focused on increasing the
CO2 absorption capacity, these solvents do not neccesarily lead to cost-effective capture processes. Other
properties of the solvents, e.g. viscosity, heat capacity, surface tension, etc., have a significant effect on
process performance and the capital and operating expenditure. For example, we found that a solvent
presenting a viscosity 100 times higher than water requires an absorber twice as high as the one used
with the benchmark solvent, i.e. 30% aqueous monoethanolamine, whereas their lower heat of absorption
reduces significantly the energy requirements.
This work presents a integrated approach to screen new generations of solvents based on user defined
key performance indicators including solvent perfomance, energy requirements, and capital and
operating cost. A compromise between rigourous and tractable multiscale models enables efficient
screening of solvents. As a result, the relationship between the solvent physical properties and the
process cost of carbon capture is elucidated. We then use this to identify idealised target properties for
the solvent mixture which can, in turn, be used to specify a computer aided material design problem.
Acknowledgements
The authors would like to acknowledge the UKCCS research centre for the financial support under the grand
UKCCSRC-C2-199.

PPEPPD 2016
th
Spontaneous multilayering in Langmuir films of ionic liquids
at the air-water interface
Eduardo J. M. Filipe1*, Nathalie Bonatout2, #Pedro Morgado1, Miguel Teixeira1, Karina Shimizu1,
Michel Goldmann2,3 and José Nuno Canongia Lopes1
1
Centro de Química Estrutural, Instituto Superior Técnico, 1049-001 Lisboa, Portugal
2
Sorbonne Universités, UPMC Univ Paris 06, CNRS-UMR 7588,
Institut des NanoSciences de Paris, F-75005, Paris, France
3
Synchrotron SOLEIL L'Orme des Merisiers Saint-Aubin - BP48 91192 Gif/Yvette Cedex France
*Corresponding author: efilipe@ist.utl.pt
Keywords: Ionic Liquids, Langmuir films, Water interface, Molecular Dynamics
Abstract
Many of the potential applications of ionic liquids (IL) involve processes that take place at interfaces,
either at the liquid-vapour interface of a pure IL or solution, or at the surface of other liquids and solids.
The study of the interfacial properties of ILs, pure or in solution, is therefore of utmost importance for
the development of their technological applications, since their properties can be significantly different
from those of the bulk liquids.
Despite its obvious importance, the knowledge of the behavior of ILs at the air/water interface is still
quite poor. A better understanding of the organization of ILs at this interface can be obtained studying
the formation of thin films through the Langmuir and Langmuir-Blodgett techniques. To date, this is a
largely unexplored field. The structure and stability of the corresponding Langmuir films remains
practically unstudied.
In this work we have studied the behaviour of a number of ILs of the methyl-imidazolium family at the
air-water interface using the Langmuir and Langmuir-Blodgett techniques. The overall behavior of the
films is quite complex. Additionally, molecular dynamics simulations have been performed to obtain
molecular level insight on the structure of the films. In the case of [octadecylmim][NTf2] and
[octadecylmim][Cl] we have obtained for the first time evidence of the spontaneous formation of
multilayers of these ionic liquid at the air-water interface.
Acknowledgements
P.M. acknowledges funding from Fundação para a Ciência e Tecnologia, in the form of Grant
SFRH/BPD/81748/2011. E.J.M.F. and P.M. acknowledge support from Fundação para a Ciência e a Tecnologia
through Grant Pest-OE/QUI/UI0100/2013.

PPEPPD 2016
th
Vapor Pressure and Liquid Density of Fluorinated Alcohols: Experimental,

Simulation and GC-SAFT-VR Predictions
Gonçalo M. C. Silva1#, Pedro Morgado1, Jessica D. Haley1, Víctor Manuel Trejos Montoya1, Clare McCabe2,3,
Luís F. G. Martins4 and Eduardo J. M. Filipe1*
1
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Portugal
2
Department of Chemical and Biomolecular Engineering and 3Department of Chemistry, Vanderbilt University,
U.S.A.
4
Centro de Química de Évora, Universidade de Évora, Portugal
*Corresponding author: efilipe@ist.utl.pt ; #Presenting author: goncalo.silva20@gmail.com
Keywords: Fluorinated Substances, Alcohols, Vapor Pressure, SAFT, Molecular Dynamics
Abstract
Highly fluorinated compounds have become important substances, both from an industrial and
fundamental point of view. Fluorinated alcohols, in particular, find application in numerous commercial
products from textile protection agents and fire-fighting foams, to detergents, paints, and as precursors in
the production of fluorinated polymers.
The fluorotelomer alcohols studied in this work are linear highly fluorinated molecules
possessing a terminal OH group, with the general formula, CF3(CF2)n(CH2)mOH (n+1:m FTOH). This
molecular structure results in an enhanced amphiphilic character compared to hydrogenated alcohols, as
fluorinated chains are known to be more hydrophobic than their hydrogenated analogues.
New experimental data is presented for the vapor pressures and liquid densities of four liquid
1H,1H-perfluoroalcohols (CF3(CF2)nCH2OH, n = 1, 2, 3, 4) as a function of temperature. Molar
enthalpies of vaporization were derived from the experimental data and the results are compared with
data from the literature for other perfluoroalcohols as well as their equivalent hydrogenated alcohols.
Molecular dynamics simulations were performed in order to obtain molecular level insight into
the experimental results; the force field used was validated by comparison to the experimental molar
enthalpies of vaporization and liquid densities. The simulations show that the compounds studied have a
lower degree of hydrogen bonding in the liquid state than the analogous hydrogenated n-alcohols, and
that the molecules in the vapor phase are electrostatically stabilized by an intramolecular gauche
interaction between the positively charged hydrogen of the hydroxil group and the negative fluorine
atoms. Both effects help to explain the low enthalpies of vaporization observed, when compared to the
hydrogenated alcohols. Additionally, the GC-SAFT-VR equation was used to predict the experimental
results without any fitting to the new experimental data. Excellent agreement has been found between the
theoretical predictions and the experimental densities, vapour pressures and vaporization enthalpies.
Acknowledgements
through Grant Pest-OE/QUI/UI0100/ 2013.

PPEPPD 2016
th
Rheological properties of mixtures involving ionic liquids and molecular

solvents
Luís F. G. Martins1*, Bruno M. S. Faria2, Pedro Morgado2, Eduardo J. M. Filipe2

1
Centro de Química de Évora & Departamento de Química, Instituto de Investigação e Formação Avançada &
Escola de Ciências e Tecnologia, Universidade de Évora, Rua Romão Ramalho, 59, 7000-671 Évora, Portugal
2
*Corresponding author: lfgm@uevora.pt
Keywords: Ionic liquids, Rheological behaviour, Molecular solvents, Viscosity
Abstract
Mixtures of ionic liquids (IL) with molecular solvents have atracted the attention of the scientic
community in the last years due to their countless applications both in scientific and industrial domains,
as solvents, reaction media or carbon capture systems [1]. Their main advantadge over pure IL is that
they ally good solvency and low vapour pressure to the absence of problems related to the high viscosity
of IL [2]. On the other hand, some binary mixtures of IL with molecular solvents (mainly water) are
known to form gels with many potential applications, such as drug delivery and gas permeation [3]. The
knowledge of thermophysical properties of mixtures involving IL and molecular solvents is very useful
both for performance evaluation and proper design of industrial processes where this systems intervene.
In particular the rheological behaviour of this kind of mixtures is extremely important in industrial
processing context.
In this work the rheological behaviour of some binary mixtures of IL with molecular solvents
was studied as a function of composition and temperature. Imidazolium based ionic liquids with long
cation chains (between 8 and 16 carbon atoms) were chosen, combined with different kinds of anions,
such as chlorine, bis(trifluoromethylsulfonyl)-imide and hexafluorophosphate. Also methyl-
trioctylammonium bis(trifluoromethylsulfonyl)-imide was studied. Besides water, propylene glycol,
glycerol and triethanolamine were the molecular solvents used.
Viscosity as a function of shear stress in rotational mode, viscoelastic properties in oscillation
mode and the existence of thixotropy in time dependent mode were studied. The results were rationalized
in terms of molecular structure of IL and the molecular solvents.
References
[1] M. M. Hoffmann, E. D. Sylvester, J. W. Russo, “On the temperature dependence of several physicochemical
properties for aqueous solutions of the ionic liquid 1-butyl-3-methylimidazolium methanesulfonate
([C4mim][MeSO3])”, Journal of Molecular Liquids, 2014, 199: 175–183.
[2] Y. Huang, Y. Zhao, S. Zeng, X. Zhang, S. Zhang “Density prediction of mixtures of ionic liquids and molecular
solvents using two new generalized models”, Industrial & Engineering Chemistry Research, 2014, 53:
15270−15277.
[3] I. Goodchild, L. Collier, S. L. Millar, I. Prokeš, J. C.D. Lord, C. P. Butts, J. Bowers, J. R.P. Webster, R. K.
Heenan, “Structural studies of the phase, aggregation and surface behaviour of 1-alkyl-3-methylimidazolium halide
+ water mixtures”, Journal of Colloid and Interface Science, 2007, 307: 455–468.
Acknowledgements
The authors aknowledge to LADECA, ALENT-07-0262-FEDER-001878 for funding.

PPEPPD 2016
th
Solubility of Water in Alkanes, Perfluoroalkanes and Perfluoroalkylalkanes:

Experimental Results, SAFT Modeling and Molecular Dynamics Simulations
Pedro Morgado1, #Pedro Duarte1, Gaurav Das2, Amparo Galindo4, Clare McCabe2,3 and Eduardo J. M. Filipe1*
1
2
Department of Chemical and Biomolecular Engineering and 3Department of Chemistry, Vanderbilt University,
U.S.A.
4
Department of Chemical Engineering and Centre for Process System Engineering, Imperial College London, U.K.
*Corresponding author: efilipe@tecnico.ulisboa.pt ; #Presenting author: pedro.duarte@tecnico.ulisboa.pt
Keywords: Solubility, Karl-Fischer coulometry, SAFT, Molecular Dynamics
Abstract
The solubility of water in liquid alkanes and their mixtures is of vital importance to the gas and
petroleum industries. Preventing corrosion and hydrate crystal formation in subsea and terrestrial
pipelines are examples of operating and safety problems, which require a precise knowledge of water
content in hydrocarbons. Given the importance of the subject, a large number of results can be found in
the literature. However, significant disagreement is found between these results, surely reflecting the
difficulty of these measurements.
On the other hand, the mutual (im)miscibility between water and perfluoroalkanes or
perfluoroalkylalkanes (PFAA) has a very important role in their biomedical applications, and also in their
use in biphasic synthesis and catalysis. Moreover, it has been demonstrated that the presence of water is
fundamental for the processes of self-organization and nano-pattern formation in molecular films of
PFAA.
In this work, new experimental results for the solubility of water in liquid n-alkanes,
perfluoroalkanes, in their mixtures and in perfluoroalkylalkanes, as a function of temperature, will be
presented. The corresponding solution thermodynamic quantities are presented and discussed, and
suggest a specific interaction between water and PFAA.
A molecular-level interpretation of the results combines a theoretical approach, the hetero-
SAFT-VR equation that explicitly takes into account the presence of dipoles, and all-atom molecular
dynamics simulations (MD). Both approaches help to rationalize the observed trends in solubility and
derived thermodynamic properties, with the simulations giving particular insight on the differences in the
structuration of the solvents around the water molecules and on the associated interaction energies. The
theoretical predictions quantitatively describe the experimental results and, together with the MD results,
confirm the importance of dipolar interactions in the behavior of water-PFAA systems.
Acknowledgements
through Grant Pest-OE/QUI/UI0100/ 2013. C.M. and G.D. acknowledge support from the National Science
Foundation through Grant CBET-1067642.

PPEPPD 2016
th
Flower Pollination Algorithm for LLE data modeling in food systems
Abdelkrim Merzougui1 and Adrián Bonilla-Petriciolet2*

1
Department of Chemical Engineering, University of Biskra, Algeria
2
Department of Chemical Engineering, Instituto Tecnologico de Aguascalientes, Mexico
*Corresponding author: petriciolet@hotmail.com
Keywords: Liquid-liquid equilibrium, Flower Pollination Algorithm, Food systems, Parameter

estimation
Abstract
In this study, the liquid–liquid equilibrium of twenty two ternary and quaternary systems relevant for
food industry was modeled using the NRTL and UNIQUAC equations and the Flower Pollination
Algorithm (FPA). FPA is an emerging nature-inspired stochastic global optimization method and it has
been used for LLE parameter identification of local composition models in multicomponent mixtures.
FPA and its modified version (MFPA) were assessed for solving LLE parameter estimation problems in
several systems relevant for food industry. The numerical performance of these stochastic methods has
been analyzed at different numerical scenarios with and without the application of closure equations.
Results showed that MFPA outperformed FPA and other metaheuristics (e.g., Simulated Annealing,
Genetic Algorithm and Harmony Search) for LLE parameter identification in local compositions models.
MFPA with closure equations is a reliable approach for determining the best interaction parameter of
NRTL and UNIQUAC models in the LLE data processing of food-related thermodynamic systems.
References
[1] H. Katayama and T. Satoh, “Liquid-liquid equilibria of three ternary systems: Glycerol + Acetone +Water,
Glycerol + 1,4Dioxane + Water, Glycerol + Acetonitrile+Water”, Solvent Extr. Res. Dev. Jpn., vol. 22, pp. 1-15,
2015.
[2] J. Rydberg, M. Cox, C. Musikas and G.R. Choppin, Solvent extraction principles and practice, Second Ed.,
Marcel Dekker, New York, 2004.
[3] H. Zhang, A. Bonilla-Petriciolet and G.P. Rangaiah, “A Review on Global Optimization Methods for Phase
Equilibrium Modeling and Calculations”, Open Thermodynamics J., vol. 5, pp. 71-92, 2011.
[4] X.S. Yang, “Flower pollination algorithm for global optimization”, Lecture Notes in Computer Science, vol.
7445, pp. 240–249, 2012.
[5] S. A.Ahmad and A.Khanna, “Closure equations in the estimation of binary interaction parameters”, Korean J.
Chem. Eng., vol. 20, pp. 736-744.
[6] A. Kabouche, A. Boultif, A. Abidi and N. Gherraf, “Interaction parameter estimation in liquid-liquid phase
equilibrium modeling using stochastic and hybrid algorithms”, Fluid Phase Equilib., vol. 336, pp. 113–121, 2012.
Acknowledgements
Authors acknolewdge the financial support of University of Briska and Instituto Tecnologico de Aguascalientes.

PPEPPD 2016
th
Lubrication Behavior of Water Molecules Confined in TiO2 Nano-slits:

Molecular Dynamics Study
Yudan Zhu1*, Yumeng Zhang1, Mingjie Wei1, Luzheng Zhang2, Yijun Shi3, Xiaohua Lu1*, Linghong Lu1
1
College of Chemistry and Chemical Engineering, Key Laboratory of Materials-Oriented Chemical Engineering,
Nanjing Tech University, P. R .China
2
Illinois State Geological Survey, University of Illinois at Urbana–Champaign, USA
3
Country Division of Machine Elements, Luleå University of Technology, Sweden
*Corresponding author: ydzhu@njtech.edu.cn
Scientific topic: Surfaces, interfaces and confinement effects; Poster presentation
Keywords: Molecular simulation, nanoconfinement, friction
Abstract
Titanium (Ti) metal has been widely used in orthopedic implants such as knee replacements and
fractural fixation devices due to the nature of a passivating nanolayer of TiO2 formed on its surface,
which can responsible for the good biocompatibility and low frictional coefficient. In this work, a series
of nanofriction-based non-equilibrium molecular dynamics (NEMD) [1] have been performed to
investigate the microstructure and lubrication of water molecules confined in TiO 2 nano-slits under
shearing. The effects of slit gap width and shear velocity on the friction coefficient were evaluated to
shed light on the role of confined water molecules for lubrication. It was found that, the fluctuations in
velocity distribution became more obvious when the shear velocity of wall decreased. These results
suggest that statistical thermal motion of water molecules becomes dominant. For the 0.8 nm of slit, the
strong interactions between TiO2 and water layers results in high friction coefficient. As the width
increased, the amount of free water increased and the average H-bonds lifetime of confined water
molecules decrease accordingly, which induces reducing of friction coefficient. This understanding can
be used to explain the observation in our previous AFM experiment [2] at molecular scale.
References
[1] Y. D. Zhu , L. Z. Zhang, X. H. Lu, L. H. Lu, X. M. Wu, “Flow resistance analysis of nanoconfined water in silt
pores by molecular simulations: effect of pore wall interfacial properties”, Fluid Phase Equilibria, 2014, 362: 235-
241
[2] R. An, Q. M. Yu, L. Z. Zhang, Y. D. Zhu, X. J. Guo, S. Q. Fu, L. C. Li, C. S. Wang, X. M. Wu, C. Liu, X. H.
Lu, “Simple physical approach to reducing frictional and adhesive forces on a TiO2 surface via creating
heterogeneous nanopores”, Langmuir, 2012, 28: 15270–15277
Acknowledgements
This work was supported by the National Basic Research Program of China (2015CB655301), National Science
Foundation of China Grants (No.21206070, 21576130 and 21490584), the Natural Science Foundation of the
Jiangsu Higher Education Institutions of China (No. 14KJB530008).

PPEPPD 2016
th
Lactic acid recovery from amine extractants using temperature swing
Marek Blahusiak*, Dion Smink, Boelo Schuur

Sustainanble Process Technology Group, University of TWENTE, Netherlands
*Presenting author: m.blahusiak@utwente.nl
Scientific topic: Phase Equlibria
Keywords: extraction, lactic acid, amines, temperature swing
Abstract
Lactic acid (LA) is a very versatile chemical, with raising importance as a building block of
biobased polymers [1]. LA is produced mainly by fermentation with consequitive addition of CaO to
titrate produced acid and supress its inhibitive effect [2]. Consequitevely, H2SO4 is added to the
fermentation broth to release the undissociated form LA while the insoluble CaSO4 is obtained as a waste
in stoichiometric ratio to the produced acid.
As an alternative to CaO addition, the neutral form of LA can be extracted in situ from the
fermentation broth to keep the fermentation running. Many extractants and conditions have been studied
over the years for extraction of lactic acid, and increased acid concentrations due to large distribution
coefficients were observed. However, the problem of solvent regeneration to obtain pure acid poses a
serious chalenge for extractive separations.
Evaporation of LA from the solvent, even at deep vacuum conditions is an unlikely option, due
to its large boiling point and thermal instability of monomeric form. Some authors propose backstripping
of the extracted acid using alkali or with a small, water soluble amine. Using alkali, concentrated solution
of LA salt is obtained and the problem of waste salt formation remains. Small toxic amines may possibly
get to the fermentor due to their solubility in the solvent [3].
We present here a study on the recoverability of lactic acid from the amine containing solvent
and the focus in the presented work was on the possibility of recovery of LA from the solvent containing
various diluents using temperature-swing back extraction, instead of producing salts. In this way, reuse
of added materials is better possible, and hence, a much greener process becomes feasible. LA extraction
equilibria with different amines and diluents at two temperatures (25 and 90°C) will be presented. Based
on the equilibrium data, the potential for concentrating LA by extraction - temperature swing back-
extraction was evaluated, including an estimation of the heat duty of such processes.
References
[1] Wee, Y.J., J.N. Kim, and H.W. Ryu, Biotechnological production of lactic acid and its recent
applications. Food Technology and Biotechnology, 2006. 44(2): p. 163-172.
[2] Hofvendahl, K. and B. Hahn-Hagerdal, Factors affecting the fermentative lactic acid production from
renewable resources. Enzyme and Microbial Technology, 2000. 26(2-4): p. 87-107.
[3] Joglekar, H.G., et al., Comparative assessment of downstream processing options for lactic acid.
Separation and Purification Technology, 2006. 52(1): p. 1-17.
Acknowledgment
This is ISPT project BL-20-05 in the EEBLS cluster

PPEPPD 2016
th
Modeling of Asphaltene Onset Precipitation Conditions using the Cubic-Plus-

Association Equation of State
Alay Arya*, Nicolas von Solms, Georgios Kontogeorgis

*Corresponding author: alaya@kt.dtu.dk
Scientific topic: Phase Equilibria (Modeling)
Keywords: Asphaltene Modeling
Abstract
The Cubic-Plus-Association (CPA) equation of state (EoS) has already been proven to be a successful
model for phase equilibrium calculations for systems containing associating components and has already
been applied for asphaltene modeling by few researchers. In the present work, we apply the CPA EoS to
determine asphaltene precipitation onset conditions for various reservoir fluids but with a different
modeling approach than the literature approaches. A simple oil characterization technique is adopted
which divides the C6+ fraction of the oil into “heavy component (maltene)” and asphaltene. Self-
association between asphaltene molecules and cross-association between asphaltene and heavy
component molecules are considered. Experimental data of several reservoir fluids are compared with
model results and it is found that the three model parameters (temperature dependent cross-association
energy, self-association energy and critical pressure of heavy component) correlate asphaltene phase
envelope (APE) quite well in agreement with the experimental data. Further, number of reservoir fluids
are studied to validate whether the model is able to calculate the effect of different types (e.g. N2, CO2,
methane) and amounts (e.g. 10/20/30 mol%) of gas injections in agreement with the experimental data
from the literature. Sensitivity of the model results when we calculate either two or three model
parameters from the experimental data is also studied. Model dependency on Saturates-Aromatics-
Resins-Asphaltenes analysis or molecular weight of asphaltene is also analyzed. In addition, a unique
characteristic of the model for the given stock tank oil (STO) is identified, which does not change with
different types and amounts of gas injections, and also remains same at upper and lower onset pressure
boundaries. Based on this unique characteristic, a simple procedure to predict APE for the reservoir oil
with relatively simple and few experimental data, performed on STO with n-pentane/n-heptane as
precipitant, is proposed. This proposed procedure avoids the need of high pressure measurements of
upper onset pressure (UOP). Model reliability for the calculation of PVT properties, obtained from the
experiments like constant mass expansion, differential vaporization, and swelling test, is also validated.
Preliminary study is also done to calculate onset conditions on mixing of different STOs in different
amounts.
References
[1] Arya, Alay, Nicolas von Solms, and Georgios M. Kontogeorgis. "Determination of asphaltene onset conditions
using the cubic plus association equation of state." Fluid Phase Equilibria 400 (2015): 8-19.
[2] Arya, A., von Solms, N., & Kontogeorgis, G. M. (2015). Investigation of Gas Injection Effect on Asphaltene
Onset Precipitation using the Cubic-Plus-Association (CPA) Equation of State. Energy & Fuels.
Acknowledgements
The authors wish to thank BP International limited (UK), Statoil (Norway) and Petrobras (Brazil) for supporting the
work as part of the CHIGP (Chemical in Gas Processing) projects.

PPEPPD 2016
th
Understanding Heterogeneous Gas Hydrate Nucleation

Using Molecular Simulations
Ryan DeFever1 and Sapna Sarupria1*

1
Chemical and Biomolecular Engineering, University, Clemson, SC, USA
*Corresponding author: ssarupr@g.clemson.ed
Scientific topic: Molecular and Multiscale simulation; Surfaces, interfaces and confinement effects
Keywords: Gas Hydrates, Nucleation, Molecular dynamics, Interfaces
Abstract
Gas hydrates represent a long-standing flow assurance problem in the oil and gas industry as well as the
potential energy source for the next generation. Several other applications of gas hydrates such as water
purification and gas separation have also been proposed in recent years. In all these applications, it is
imperative to understand the process through which a solution of gas-water transforms into a crystalline
structure usually resulting in orders of magnitude increase in the solubility of the gas in water. The
relevant timescales and lengthscales are usually difficult to access through experiments, and ideally-
suited for simulations[1]. However, the long waiting times involved in capturing nucleation events
through straightforward molecular dynamics (MD) simulations has limited the sampling of this
phenomena. In our research, we have developed novel computational framework to study rare events
such as nucleation in molecular simulations efficiently and enable sampling of hundreds of such events.
Using these tools, we study the nucleation of sII hydrate former at various conditions. We will discuss
the mechanism of hydrate nucleation that emerges from our studies. Specifically, we find that while the
features of sII hydrate nucleation are similar to those observed in sI hydrate nucleation[2], the pathways
are subtely different. In addition, we have studied the influence of various surfaces and confinements on
the nucleation of gas hydrates. We find that surfaces lacking any structural templating do not directly
affect hydrate nucleation but indirect effects are observed due to their effects on the concentration of the
guest molecules in solution. There are also additional effects arising from the surface effects on
interfacial water which are difficult to discern. Comprehensively, our simulations provide insights into
hydrate nucleation in different environments and solution conditions. Our studies are relevant to
designing inhibitors or promoters for hydrate nucleation as well as in understanding how confinement
and interfaces affect hydrate nucleation.
References
[1] Debenedetti, P. G. and Sarupria, S., “Hydrate Molecular Ballet”, Science, 2009, 326: 1070-1071
[2] Sarupria S and Debenedetti PG, “Homogeneous Nucleation of Methane Hydrate in Microsecond Molecular
Dynamics Simulations”, The Journal of Physical Chemistry Letters, (2012) 3: 2942-2947
Acknowledgements
We acknowledge funding from ACS PRF DNI grant (grant number 54557-DN16) and Clemson
University Start Up Funds.We are also thankful to CITI group for providing the Palmetto
Supercomputing resources.
PPEPPD 2016
th
A Novel Computer-aided Model-based Tool for Chemical Product Design
Sawitree Kalakul1, Rehan Hussain2, Nimir Elbashir2, and Rafiqul Gani1*

1
SPEED, Department of Chemical and Biochemical Engineering, Technical University of Denmark, Denmark
2
Department of chemical Engineering, Texas A&M University at Qatar, Qatar
*Corresponding author: rag@kt.dtu.dk
Scientific topic: Product and Process Engineering
Keywords: Chemical Product Design, Computer-aided Model-based Approach, Blend Design of Jet-
fuels
Abstract
In chemical product design, the application of model-based methodologies can help to design/improve
products so as to reach the market faster by reducing costly and time-consuming experiments at the early
stages of design [1]. That is, experiments are only performed during the last stage as a verification step.
Since product candidates involve thousands of mixtures/blends of chemicals that need to be evaluated, a
huge amount of data on physico-chemical properties of chemicals and their mixtures and/or models that
can reliably predict them are needed for tailor-made design of products. This is a challenging task
requiring data acquisition, data testing, model development, model-based design method development,
etc, that needs to be integrated within a computer-aided framework so that chemicals based products can
be designed, analyzed and verified in a fast, efficient and systematic manner [2].
In this paper, the development of a systematic model-based framework for product design and
evaluation, implemented in a new product design simulator called VPPD-Lab is presented. The
framework has built-in libraries of product performance models and product-chemical property models.
The built-in knowledge base has a suit of databases containing properties of different classes of
chemicals (lipids, solvents, aroma,polymers, cosmetics, etc.) and blended products (gasoline, jet-fuels,
lubricants, hair spray, etc.). It can calculate 55 pure component properties (such as critical properties,
acentric factor and solubility parameter) and 10 functional properties (such as vapor pressure, liquid
viscosity, and surface tension) and databases covering more than 24,000 compounds. Also, it has models
for phase equilibrum prediction such as UNIQUAC, UNIFAC, NRTL and PC-SAFT. It has special
model parameters and data for lipids and ionic liquids. Transport related properties and new interaction
parameters for UNIFAC model for lipids systems have also been incorporated. These features together
allow the design of a very wide range chemical-based products. The large amount of data, models and
calculation-algorithms are managed through specially developed ontology.
The application of the software is highlighted for the case of tailor-made design of jet-fuels, which is a
blended chemicals based product as well as other single molecule and blended products.
References
[1] S. Kalakul, R. Hussain, N. Elbashir, R. Gani “VPPD Lab -The Chemical Product Simulator” Computer Aided
Chemical Engineering,2015, 37, 1415-1420.
[2] R. Gani, Ka M. Ng “Product design – Molecules, devices, functional products, and formulated products”
Computers and Chemical Engineering, 2015, 81, 70-79.

PPEPPD 2016
th
Predictive models for amphiphilic properties of sugar-based surfactants
Théophile Gaudin1,2*, Guillaume Fayet1, Patricia Rotureau1, Isabelle Pezron2

1
Direction des Risques Accidentels, INERIS, Verneuil-en-Halatte
2
Sorbonne Universités, Université de Technologie de Compiègne, EA TIMR 4297, Compiègne, France
*Corresponding author: theophile.gaudin@utc.fr
Keywords: sugar-based surfactants, amphiphilic properties, predictive models, QSPR
Abstract
This project aims to develop new predictive models of the amphiphilic properties of biomass-based
surfactants, in order to better anticipate their performance as ingredients of formulated products, such as
detergents, or cosmetics. This contribution will present the different steps towards the development of
predictive models for amphiphilic properties of sugar-based surfactants.
A large collection of available experimental data was conducted for four important [1] amphiphilic
properties for sugar-based surfactants: critical micelle concentration (CMC), surface tension at CMC
(γCMC), efficiency (pC20), and Krafft temperature (TK).
From a qualitative analysis of this database, important structural features for the targeted properties were
identified. Several molecular descriptors for sugar-based surfactants were computed and analyzed, and it
appeared that fragment descriptors (computed from the polar head or the apolar chain) have a better
ability to discriminate sugar-based surfactants with respect to these features. In order to further
understand how subtle structural changes can influence CMC, γCMC and pC20, a molecular
thermodynamic [2] approach was also used. Based on all these studies, predictive Quantitative Structure-
Property Relationship (QSPR) models [3] were developed for CMC, γCMC and pC20 that demonstrated
reasonable predictive capabilities and potential for industrial applications. Predictive modelling for TK is
currently under investigation.
References
[1] M.J. Rosen, J.T. Kunjappu, Surfactants and Interfacial Phenomena, 4th ed. 2012
[2] S. Puvvada, D. Blankschtein, “Molecular-thermodynamic approach to predict micellization, phase behavior and
phase separation of micellar solutions. I. Application to nonionic surfactants”, Journal of Chemical
Physics, 1990, 6: 3710-3724
[3] J. C. Dearden, P. Rotureau, G. Fayet, “QSPR prediction of physico-chemical properties for REACH”, SAR and
QSAR in Environmental Research, 2013, 24: 279-318
Acknowledgments
This work was performed, in partnership with the SAS PIVERT, within the framework of the French Institute for
the Energetic Transition (ITE, for “Institut pour la Transition Energétique”) PIVERT (www.institut-pivert.com). It
was supported (as PIVERT itself) by the French “Investissement d’Avenir” program under the reference ANR-001-
01.

PPEPPD 2016
th
Coarse-grained force fields for oligomers and polymers using SAFT-γ Mie
Jos Tasche1* and Mark R. Wilson1

1
Department of Chemistry, Durham University, UK
*Corresponding author: jos.tasche@durham.ac.uk
Keywords: Molecular Dynamics, SAFT, Polymers
Abstract
Reliable predictions for the compatibility of oligomer and polymer systems are of high interest, since the
experimental measurement of solubilities and other phase equilibrium properties can be very time-
consuming. Simulation approaches such as molecular dynamics (MD) using readily-available atomistic
or united-atom force fields are often too expensive for the prediction of phase equilibria of slow
processes. One way forward is to speed up molecular dynamics simulations by describing the same
molecules with fewer beads (coarse graining). Typical coarse-graining methods such as iterative
Boltzmann inversion (IBI) [1], use structural properties (e.g. radial distribution functions) of higher-
resolution reference simulations for the development of the coarse-grained potentials. Those potentials
are usually reliable for structural properties, but do not necessarily give an accurate description of
thermodynamic properties. A method connecting non-bonded potentials and a range of thermodynamic
properties is the Statistical Association Fluid Theory (SAFT). It has been shown for low molecular-
weight compounds [2] that the non-bonded Mie potentials obtained from the SAFT-γ Mie [3] equation of
state can be used in coarse-grained MD simulations to give an accurate representation of thermodynamic
properties.
In this work we investigate the combination of SAFT-γ Mie and MD to develop coarse-grained force
fields for oligomer and polymer systems. The non-bonded potentials of the force field are parameterised
using the SAFT-γ Mie equation of state, while the bonded potentials are obtained with direct or iterative
Boltzmann inversion of simulations with higher-resolution force fields.
References
[1] D. Reith, M. Pütz and F. Müller-Plathe, J. Comput. Chem., 2003, 24: 1624.
[2] T. Lafitte, C. Avendaño, V. Papaioannou, A. Galindo, C. S. Adjiman, G. Jackson and E. A. Müller, Molecular
Physics, 2012, 110: 1189-1203.
[3] V. Papaioannou, T. Lafitte, C. Avendaño, C. S. Adjiman, G. Jackson, E. A. Müller and A. Galindo, J. Chem.
Phys., 2014, 140: 054107.
Acknowledgements
Financial support by industrial collaborators is gratefully acknowledged.

PPEPPD 2016
th
Process design to obtain copper sulfate crystals using solid–liquid equilibrium

of copper sulfate – sulfuric acid – seawater
María E. Taboada*, Francisca J. Justel, Yecid P. Jiménez , Teófilo Graber.

Department of Chemical and Mineral Process Engineering, Universidad de Antofagasta,Chile.
Centro de Investigación Científico Tecnológico para la Minería, CICITEM.
*Corresponding author: mariaelisa.taboada@uantof.cl
Scientific topic: Reaction and separation thecnologies
Keywords: Copper sulfate, seawater, sulfuric acid
Abstract
With the thermodynamic representation of the phase equilibrium of the copper sulfate – sulfuric acid –
seawater system and by applying of a simple methodology reported in the literature, a process to
crystalize copper sulfate from a leaching copper solution by addition of sulfuric acid was designed. The
sulfuric acid acts like a co-solvent, because as acid concentration increases the copper sulfate solubility
decreases. Thus, this process could be consider as drowing-out crystallization process.
The solid-liquid equilibrium is represented by the Pitzer model to model the effect of the salt (copper
sulfate), and Born-type equation approach is used to model the effect of the co-solvent (sulfuric acid).
The conceptual process include four stage: a mixer, a crystallizer, a filter and a dryer.
References

Acknowledgements
The authors acknowledge CONICYT for financing this study through the Fondecyt Project No. 1140169.

PPEPPD 2016
th
Application of regular solutions to predict water activity and applications for

freezing point
Marina Dupas-Langlet*
1
Department Food Science and Technology, Nestle Research Center, Switzerland
*Corresponding author: marina.dupas-langlet@rdls.nestle.com
Keywords: Regular solution, water activity, deliquescence, freezing point
Abstract
Water activity in hygroscopic powders, has become one of the crucial parameters for the evaluation and
the control of the risk of degradation or alteration of products during their conditioning, transport,
storage, drying or industrial transformation. Food industry contains many hygroscopic substances having
different properties and developing different types of interactions with water: hydrogen bonding, Van des
Waals forces … Numerous thermodynamical models which allow calculating water activity in aqueous
solutions of solute alone, electrolyte or organic one, were proposed and checked experimentally during
those last decades. Yet, water activity prediction in aqueous solutions of multi-solutes like mixtures of
sugars, salts and amino acids has not been developed enough and is still under study.
In 1946, Scatchard and Hildebrand proposed to neglect excess entropy and excess of mixing volume and
assumed that intermolecular forces are due primarily to dispersion forces. They defined then a regular
solution. In this presentation, we will show that this model is successfully applied to the simplest
systems like sugar solutions to the most complex ones. After establishing ternary diagrams of mixtures,
the very good adequacy between experimental measurements and the calculated points will be
highlighted in the range of undersaturated and saturated solutions of deliquescent substances and at
different temperatures. Finally, the robustness of the model will be also challenged with an indirect
prediction of freezing point compared to experimental measurements.
References
[1] Mauer, L.J., Taylor, L.S. “Water Solid Interactions Deliquescence”, Annu. Rev. Food Sci. Technol., 2010,1: 41-
63.
[2] Kwok, K. “Phase behavior and moisture sorption of deliquescent powders”, Chemical Engineering Science,
2010, 65: 5639-5650.
[3] Clegg S.L. “Thermodynamic modelling of aqueous aerosols containing electrolytes and dissolved organic
compounds”, Journal of Aerosol Science, 2001,34: 667-690.
[4] Dupas-Langlet, M. et al. “Deliquescence lowering in mixtures of NaCl and sucrose powders elucidated by
modeling the water activity of corresponding solutions”, Journal of Food Engineering, 2013, 115: 391-397.

PPEPPD 2016
th
Evidence of Structure-Function Relation for Anti-Agglomerants at the

Hydrate-Hydrocarbon Interface
Tai Bui1, Anh Phan1, Alberto Striolo 1*, Pushkala Krishnamurthy and Erick Acosta 2
1
Department of Chemical Engineering, University College London, UK
2
Halliburton, TX, USA
*Corresponding author: a.striolo@ucl.ac.uk
Scientific topic: Surfaces, Interfaces and Confinement Effects & Gas and Oil Downstream and Upstream
Keywords: Molecular Simulation, Agglomeration, Performance, Transport
Abstract
The formation of hydrates plugs can cause interruptions in the flow of oil in pipelines, with a substantial
negative impact both economical and environmental. To maintain flow assurance the industry employs
three types of hydrate inhibitors: thermodynamic inhibitors such as methanol, which shift the stability
region of the hydrates, kinetic inhibitors, such as PVCAP, which are thought to both reduce the
frequency of hydrate nucleation events and delay the growth of hydrate particles once formed, and anti-
agglomerants, AAs, which are thought to prevent the assembly of hydrate particles into large
agglomerates. The molecular mechanisms responsible for the performance of AAs are at present not
completely understood. In an attempt to fill this knowledge gap we report here atomistic molecular
dynamics simulations conducted in a system composed by decane, methane, water, hydrates, and models
of anti-agglomerants. The AAs are chosen so that they represent compounds with high and low
performance. The system composition is chosen to mimic experimental conditions relevant to flow
assurance applications. The simulation results are quantified in terms of density profiles, adsorption
energies, structures of the adsorbed AAs films, energies of adsorption, and free energy profiles
experienced during the coalescence of water droplets and hydrate particles. When possible, the
simulations are compared to available experimental data. The results could be useful for understanding
the structure-function mechanisms that dictate the performance of anti-agglomerants in flow assurance
applications.

PPEPPD 2016
th
Saturating Narrow Pores with Water Enhances the Selectivity of Membrane

Separations
Anh Phan1 and Alberto Striolo 1*

1
Department of Chemical Engineering, University College London, UK
*Corresponding author: a.striolo@ucl.ac.uk
Scientific topic: Surfaces, Interfaces and Confinement Effects & Reaction and Separation Technologies
Keywords: Molecular Simulation, Transport Mechanisms, Confinement Effects
Abstract
We report atomistic molecular simulation results for the transport of various gases, including methane,
H2S, and ethane, through narrow pores saturated by liquid water. The slit-shaped pores are of width of
approximately 1 nm. This pore width is selected because the pore surface strongly affects the structure of
confined water throughout the entire pore volume. Different solid materials are chosen for the pores,
because they are known to affect differently the structure of interfacial water. While some materials are
realistic, e.g., the cristobalite mineral of silicon dioxide, others are model ones used as proof of concept
in our calculations. Equilibrium molecular dynamics simulations are used to assess the adsorption of
various gases within the confined water as a function of bulk pressure. The results show that when
confined water is characterized by relatively high fluctuations in density, the solubility of hydrophobic
gases can be significantly enhanced compared to the solubility of the same gases in bulk water at
comparable thermodynamic conditions. We analysed the free energy barriers experienced by the various
gases to enter the pores saturated with water by conducting umbrella-sampling simulations, and we find
that the density of water near the pore entrance determines such barriers. We then analysed the transport
of the various gases within the pores using a number of statistical techniques, and we compared the
selective transport of various gases through the pores filled with water. The results suggest that water
could be used to enhance selectivity in membrane separations, although the permeability is reduced
significantly compared to values achievable for the pores without water present.

PPEPPD 2016
th
Phase Equilibria Involving Carbon Dioxide, Reactants and Products of a Aldol
Reaction
Técio Santos Bastos1, Rafael Cassaro2, Reinaldo C. Bazito2, Cláudio Dariva1, Gustavo Borges1, Silvia Maria
EguesDariva1*, Elton Franceschi1
1
Núcleo de Estudos em Sistemas Coloidais – NUESC/ITP, Programa de Pós Graduação em Engenharia de
Processos,Universidade Tiradentes, Brazil
2
Departamento de Química Fundamental, Instituto de Quimica – Universidade de São Paulo
*Corresponding author: smsegues@gmail.com
Keywords: Supercritical carbon dioxide, aldol reaction, phase equilibria, green chemistry
Abstract
The knowledge of the high-pressure phase behavior of the compounds involved in the aldol condensation
in supercritical medium allows the understanding of the reaction paths, and establishesthermodynamic
conditions for the assembling of equipments [1]. In this study, phase equilibriaexperimental data for
binary and ternary systems involving reactants and products of a model aldolreaction between p-
nitrobenzaldehyde and acetone using carbon dioxide as a solvent were obtained through the visual static
synthetic method [2]. Temperature, pressure, and mass fraction of solute (p-nitrobenzaldehyde, 4-
hydroxy-4-(4-nitrophenyl)butan-2-one, (E)-4-(4-nitrophenyl)but-3-en-2-one, L-proline, terc-
butyl(dimethyl)sili-L-proline) ranges investigated were 10-70°C, 0-290 bar, and 0.0015-0.10,
respectively. The results obtained for the p-nitrobenzaldehyde-CO2 binary system suggested aremarkable
influence of the mass fraction of solute in the phase behavior. For the binary systemsinvolving products
or catalysts in compressed CO2, only the catalyst terc-butyl(dimethyl)sili-L-prolinewas completely
soluble in carbon dioxide. The effect of acetone was analyzed through the addition ofthis reactant at
distinct molar ratios (solute:acetone). For the ternary system p-nitrobenzaldehyde-CO2-acetone, the
results showed that acetone acted as a co-solvent. L-proline and the addition product (4-hydroxy-4-(4-
nitrophenyl)butan-2-one) were not completely micible in the conditions investigated. This study shows
possible experimental PTx conditions in which the aldol reaction occurs in a singlephase where, over the
course of the reaction, it is possible to obtain the addition product as a precipitatefrom the reaction
medium.
References
[1] N. Musko, J. Grunwaldt, “Heterogeneously Catalysed Aldol Reactions in Supercritical Carbon Dioxide as
Innovative and Non-Flammable Reaction Medium” Top Catal., 2011, 54: 1115–1123, 2011.
[2] E. T. Tenório Neto, M. H. Kunita, A. F. Rubira, B. M. Leite, C. Dariva, A. F. Santos, M. Fortuny, E.
Franceschi, “Phase Equilibria of the Systems CO2 + Styrene, CO2 + Safrole, and CO2 + Styrene + Safrole” J.
Chem. Eng. Data, 2013, 58: 1685-1691.
Acknowledgements
The authors thank to FAPITEC/SE for the financial support and scholarships.
PPEPPD 2016
th
Viscoeslatic properties of crude oil emulsions in the presence of IL
Douglas Alves1, Everton Lourenço1, Elton Franceschi1, Gustavo Borges1, Claudio Dariva1*
1
NUESC/ITP/UNIT, Av. Murilo Dantas, 300, Predio do NUESC, Aracaju-SE, Brazil, 49032-49, (+55)7932182157
*Corresponding author: claudio.dariva@gmail.com
Keywords: interfacial properties, crude oil, ionic liquid
Abstract
The natural crude oil surfactants, such as resin and asphaltene, form a rigid interface which tends to
prevent the coalescence between the droplets [1]. The rheological behavior of the interfacial film can be
properly monitored using dilational rheological techniques, which provide information about the kinetics
of formation and rupture of the surfactant film and adsorption mechanisms of surfactants at the interface
[2]. To increase the destabilization of emulsions, it is common the injection of chemical demulsifiers
with high interfacial activity that decreases the interfacial rigidity and increases the coalescence rate [1].
Some ionic liquids (ILs) have the ability to act as a tensoative and could be used as a desemulsifier agent
[3]. The aim of this study is to determine the interfacial properties in systems involving a brazilian crude
+ -
oil using the IL [C12min] [NTf2] as a tensoative (5, 15, 30, 50, 75, 100 ppm). Interfacial tension
measurements and viscoelastic modules were assessed by the pendant drop technique (Tracker, Teclis)
through dynamic and static tests at room temperature. Ultrapure water was used as the aqueous phase.
The results showed a high interfacial activity of IL as surfactant, since there is a clear reduction in the
interfacial tension with the enhancement of the IL concentration. It is also observed a change in elasticity
and compressibility of the interfacial film formed.The reduction of viscoelastic modulus suggests a less
rigid interfacial film for systems containing ionic liquid. The decrease of the phase angle between the
oscillations of the interfacial tension and the area indicates the production of a film with more elastic
than viscous characteristic. These results show a clear correlation between the changes in elasticity and
compressibility of the interfacial film and the stability of the crude oil emulsions.
References
[1] M. Rondón, J. C. Pereira, P. Bouriat, A. Graciaa, J. Lachise, J. L. Salager. “Beraking of Water-in-Crude-Oil
Emulsion. 2. Influence of Asphltene Concentration and Diluent Nature on Demulsifier Action” Energy & Fuels,
2008, 22: 702-707.
[2 P. M. Spiecker, P. K. Kilpatrick “Interfacial Rheology of Petroleum Asphaltenes at the Oil-Water Interface”

Langmuir, 2004, 20: 4022-4032.
[3] E. B. Silva, D. Santos, D. R. M. Alves, M. S. Barbosa, R. C. L. Guimarães, B. M. S. Ferreira, R. A. Guarnieri,

E. Franceschi, C. Dariva, A. F. Santos, M. Fortuny “Demulsification of Heavy Crude Oil Emulsions Using Ionic
Liquids” Energy & Fuel, 2013, 27:6311-6315.
Acknowledgements
The authors thank CNPq, CAPES and FAPITEC/SE (Brazilian funding agencies) and Petrobras
(Petróleo Brasileiro S.A., Brazil) for supporting this work.
PPEPPD 2016
th
NH3 absorption in Brønsted acidic imidazolium-based ionic liquids

Takashi Makino* and Mitsuhiro Kanakubo*
1
Research Institute for Chemical Process Technology,
National Institute of Advanced Industrial Science and Technology, Japan
*Corresponding author: makino.t@aist.go.jp, m-kanakubo@aist.go.jp
Keywords: Ammonia, Absorption, Ionic liquid, Brønsted acid
Abstract
NH3 is an important substance used as raw materials in chemical industry, energy storage medium,
refrigerant for freezing and refrigeration, and so on. Current NH3 production is an energy intensive
technology because NH3 is synthesized under high-temperature and high-pressure conditions, and
purified with the cryogenic separation. This purification process demands ~30 % of total energy
consumption. Thus, it is of particular importance to develop new energy saving technologies for NH 3
separation. One of the alternatives is absorption, however, conventional NH3 absorbents like acid
aqueous solutions are not applicable directly to NH3 separation at high temperatures due to their
volatility, which brings down the loss of absorbent and the contamination. Ionic liquids (ILs) can
overcome these issues, because they have negligibly small vapor pressure and high thermal stability.
Some earlier studies have reported the anion effect on NH3 physical absorption in imidazolium based ILs
[1-3]. It was pointed out that the solubilities in tetrafluoroborate and hexafluorophosphate ILs are slightly
superior to that in bis(trifluoro-methanesulfonyl)amide ILs. In the present study, for further improvement
of NH3 absorption property, we focused on the ILs with Brønsted acidic sites, which can absorb NH3
chemically. We measured the NH3 solubilities in the imidazolium-based ILs with the sulfonic and
sulfuric groups over the temperature range from 298 K to 353 K. The experimental results indicated that
1-(4-sulfonylbutyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (2.2 mol-NH3 per mole of
IL) successfully absorbed the larger amount of NH3 than1-(2-hydroxyethyl)-3-methylimidazolium
bis(trifluoro-methanesulfonyl)amide (1.3 mol-NH3 per mole of IL) and 1-ethyl-3-methylimidazolium
bis(trifluoro-methanesulfonyl)amide (0.33 mol-NH3 per mole of IL). The NMR and Raman peaks of the
sulfonic group showed pronounced shifts, revealing that the sulfonic group strongly interacted with NH3.
References
[1] A. Yokozeki, M. B. Shiflett “Ammonia Solubilities in Room-Temperature Ionic Liquids” Industrial and
Engineering Chemistry Research, 2007, 46: 1605-1610.
[2] G. Li, Q. Zhou, X. Zhang, L. Wang, S. Zhang, J. Li “Solubilities of ammonia in basic imidazolium ionic
liquids” Fluid Phase Equilibria, 2010, 297: 34-39.
[3] J. Palomar, M. Gonzalez-Miquel, J. Bedia, F. Rodriguez, J. J. Rodriguez “Task-specific ionic liquids for
efficient ammonia absorption” Separation and Purification Technology, 2011, 82: 43-52.
Acknowledgements
The authors would thank to Ms. Eriko Niitsuma and Mr. Fumihito Sato for their assistance with the
measurements in the present study. This study is supported by JSPS Grant-in-Aid for Young Scientists (B),
Grant No. 15K18260.

PPEPPD 2016
th
Water on TiO2 nanotubes: a molecular dynamics simulation
Wei Cao1, Linghong Lu1, Liangliang Huang2 and Xiaohua Lu1*

1
State Key Laboratory of Materials-Oriented Chemical Engineering,
Nanjing University of Technology, Nanjing, Jiangsu 210009,China
2
School of Chemical, Biological and Materials Engineering, University of Oklahoma,
Norman, Oklahoma 73019, United States
*Corresponding author: xhlu@njtech.edu.cn
Scientific topic: Nanoscience and Nanotechnology
Keywords: TiO2 nanotube, water, molecular simulation
Abstract
Nanotubes made from metal oxide such as titanium dioxide nanotubes is of great interest to enable
potential application as nanosize defined biocompatible coatings and drug delivery devices. Decoration
of TiO2 nanotubes with graphene showed higher photocatalytical activity than normal unmodified TiO2
nanotubes.[1] The modified surface facilitates electronic transmissions on the one hand. One the other
hand, how water behave is crucial to the splitting on TiO2 nanotubes surface, including the adsorption,
dissociation and diffusion characteristics. Detailed molecular-level understanding of water/solid
interfaces is essential.
Molecular dynamics simulation is applied to study the water structure and diffusion on TiO 2 nanotubes.
Simulation results demonstrate that “bilayer water” can form on outside wall of tubes, rather than the one
layer structure inside tubes where the orientation of water is homogeneous. The hydrogen bonds between
water and TiO2 surface (first layer) are stronger than water in the second layer, which is as same as water
on metal[2]. What’s more, water is trapped inside tubes and move faster outside tube. In order to
promote the flow of water inside tubes, a graphene modified TiO2 surface could be an alternative way.[3]
The results show that rates of water inside carbon covered TiO2 nanotubes are higher than water outside
tubes. After the modification, hydrogen bonds are weaken and the orientation becomes disordered for
water inside tubes, due to the modification. Further we would study water dissociation on TiO2
nanotubes using molecular dynamics simulations with the ReaxFF force field. Our findings interpret the
mechanisms of water on TiO2 nanotubes at molecular level and provide evidence of the usage of
graphene/TiO2 nanotubes in water splitting.
References
[1] L. Kiyoung, A. Mazare, P. Schmuki "One-dimensional titanium dioxide nanomaterials: nanotubes" Chemical
reviews, 2014, 114(19): 9385-9454.
[2] C. Javier, A. Hodgson, A. Michaelides "A molecular perspective of water at metal interfaces" Nature materials,
2012, 11(8): 667-674.
[3] M. Wei, L. Zhang, L. Lu, Y. Zhu, K. E. Gubbins, X. Lu "Molecular behavior of water in TiO2 nano-slits with
varying coverages of carbon: a molecular dynamics simulation study" Physical Chemistry Chemical Physics,
2012,14: 16536-16543.
Acknowledgements
This work was supported by the National Natural Science Foundation of China Grants (No. 21490584, 91334202).

PPEPPD 2016
th
Modeling and simulation of CO2 capture from biogas using aqueous choline
chloride/urea
Chunyan Ma1,2, Chang Liu1, Yujiao Xie2, Xiaoyan Ji2, Xiaohua Lu1*
1
Key Laboratory of Material and Chemical Engineering, Nanjing Tech University, Nanjing, P. R. China 210009
2
Division of Energy Science, Luleå University of Technology, Luleå, Sweden, 97187
*Corresponding author: xhlu@njtech.edu.cn
Keywords: Biogas upgrading, Aqueous choline chloride/urea, Process simulation, High pressure water
scrubbing
Abstract
Biogas has been considered as an alternative renewable energy, and raw biogas needs to be purified [1].
Upgraded biogas can be used as vehicle fuel or injection into nature gas grid. Besides methane (CH4),
carbon dioxide (CO2) is also the main component in the raw biogas from anaerobic digestion. CO2, as the
main impurity of biogas, has to be removed in order to increase the heating value, decrease transportation
costs and avoid the corrosion in pipelines [2].
Nowadays, Ionic liquids (ILs) have shown great potential to be used as a new solvent to capture CO2 [3].
However, the high production cost, high viscosity and potential toxicity for most of synthesized ILs limit
their industrial application. Choline-based ILs (or DESs) are considered as a type of promising solvents
to achieve large-scale applications because of their low production cost, low toxicity, biodegradability
and easily synthesis [4]. However, its viscosity is still too high. It has been observed that the addition of
water can significantly decrease the viscosity, but the CO2 solubility will also decrease. Therefore, how
the addition of water will affect the whole performance of the process is highly interesting.
In this work, the conceptual process for biogas upgrading using aqueous choline chloride (ChCl) /urea
(1:2 on a molar basis) was developed and simulated with Aspen plus. In order to carry out the process
simulation, the thermophysical properties of ChCl/Urea (1:2) were predicted or obtained from the
available experimental data and then implemented into Aspen plus; the vapor-liquid equilibrium was
modeled by the non-random two-liquid model and Redlich-Kwong equation (NRTL-RK) with the
parameters obtained from or verified by the experimental data. The equilibrium approach was used for
process simulation. The simulation results show that with the addition of ChCl/Urea (1:2) the diameters
for both absorber and desorber decreased; the total electrical power significantly decreased by 30%; and
the green degree was higher than the pure water scrubbing process.
References
[1] P. Börjesson, B. Mattiasson. Trends in Biotechnology 2008, 26: 7-13.
[2] F. Bauer, C. Hulteberg, T. Persson, D. Tamm. Biogas upgrading-Review of commercial technologies. SGC
Rapport 2013.
[3] L. A. Blanchard, D. Hancu, E. J. Beckman, J. F. Brennecke. Nature 1999, 399: 28-29.
[4] A. P. Abbott, G. Capper, D. L. Davies, R. K. Rasheed, V. Tambyrajah. Chemical Communications 2003, 1: 70-
71.
Acknowledgements
This work was supported by the National Basic Research Program of China (No. 2013CB733501), the National
Natural Science Foundation of China (No. 21136004, No. 21476106), the Project of Priority Academic Program
Development of Jiangsu Higher Education Institutions (PAPD) and the Swedish Energy Agency.

PPEPPD 2016
th
A data processing method for measurement of diffusion coefficient by digital

holographic interferometry
Shi Zhang, Ying Zhang, Sanguo Peng, Maogang He*

MOE Key Laboratory of Thermal Fluid science and Engineering, Xi’an Jiaotong University, China
Scientific topic: Thermodynamics and transport properties(experimental)
Keywords: Holographic interferometry, Digital holography, Diffusion coefficient, Refractive index
Abstract
It is found that the extreme difference of two peaks in phase difference profile between two times, which
comes from two holograms, is only determined by diffusion time and a constant parameter A. With this
characteristic, a method is put forward to calculate the initial time for diffusion and the diffusion
coefficient respectively. It needs varying diffusion coefficient in fitting for one experimental phase
difference profile, which can reduce calculation complexity compared with the method by fitting for
many experimental concentration profiles through varying both diffusion coefficient and the initial time.
Having relation with constant A, the derivative of refractive index on concentration can be also
determined. In order to certify the method, diffusion coefficient of KCl in water at 0.33 mol.L-1 and 25
ºC has been measured. Besides, the relationship between characteristics in phase difference profile and
physical quantities has been concluded.

PPEPPD 2016
th
Bubble nucleation in industrial fluids: A case study combining molecular

simulations and equations of state + density gradient theory
Kai Langenbach1*, Stephan Werth1, Manfred Heilig2, Gerd Haderlein2, Martin Horsch1, Hans Hasse1
1
2
Global Process Technology, BASF SE Ludwigshafen, Germany
*Corresponding author: kai.langenbach@mv.uni-kl.de
Keywords: molecular simulation, density gradient theory, PC-SAFT, bubble nucleation, industrial
mixtures
Abstract
The present work describes results from an academic-industrial cooperation on molecular modeling and
simulation of homogeneous bubble nucleation and related thermodynamic properties of fluids. The
system chosen for the case study is carbon dioxide + hydrogen chloride + toluene. Besides the ternary
system also the binary subsystems and pure components are considered. Two independent methods from
molecular thermodynamics are applied: molecular simulation using force fields and the PC-SAFT
equation of state in combination with density gradient theory (DGT). The two methods are used in parts
parallel and in other parts complementary. The overall goal of the investigation is to predict
homogeneous bubble nucleation for industrially relevant conditions.
Independently, both methods are used to investigate vapor-liquid equilibria, densities in the stable and
metastable region, interfacial tension and interfacial adsorption. Models are taken from prior work or
fitted to pure component and binary data. The two methods are then checked for mutual consistency and
compared to literature data, where available. Both carbon dioxide and hydrogen chloride adsorb strongly
at the vapor-liquid interface and show pronounced density maxima. This is consistently predicted both by
the molecular simulations and PC-SAFT + DGT.
On this basis, homogeneous bubble nucleation kinetics is investigated. With molecular simuations, it is
possible to predict the homogeneous bubble nucleation rates close to the spinodal. Using DGT, the
thermodynamic barrier for nucleation can be predicted in the whole metastable range, however, the
kinetic prefactor is not accessible as only stationary density profiles can be considered. However,
combining molecular simulations with PC-SAFT + DGT enables the prediction of homogeneous bubble
nucleation in the complete metastable range. Results are shown for nucleation rates, as well as cavitation
pressures.

PPEPPD 2016
th
Micelle formation and micro-structure of ionic liquids in aqueous solutions
Xiaomin Liu1, Feng Huo1, Suojiang Zhang1*

1
Beijing Key Laboratory of Ionic Liquids Clean Process, State Key Laboratory of Multiphase Complex Systems,
Key Laboratory of Green Process and Engineering. Institute of Process Engineering, Chinese Academy of
Sciences.
*Corresponding author: sjzhang@ipe.ac.cn
Keywords: Ionic Liquids, Micelle, Molecular Simulation
Abstract
Ionic liquids (ILs) have been applied to catalysis, electrochemistry, separation, and the other chemical
engineering processes [1]. Among the unique interactions and structures, aggregation or ion cluster has
been proved to make ILs different from water and the conventional organic solvents and provide a
unique environment for chemical reactions. The structure and behavior of ion cluster in IL solutions have
been investigated by spectroscopy and thermodynamics. However, the mechanism of aggregation
forming process has not been clearly understood. As ions interaction and structure in ILs are complex to
study in detail experimentally, molecular simulations are usually applied to elucidate the process.
In this work, we elucidated the entire process of spontaneous aggregation for [C12mim]Br into small
vesicle or rodlike micelle under different concentrations by molecular dynamics simulations. [C10mim]Br
and [C14mim]Br were also investigated to make comparisons with [C12mim]Br. However, only irregular
vesicles were obtained in the aqueous solution of [C10mim]Br and only spherical micelles were observed
for [C14mim]Br, although the final concentrations are higher than the experimental inflection point of
rodlike micelle to vesicle [2].
The entire spontaneous process for forming vesicle or rodlike micelle in the aqueous solutions of
[C12mim]Br were investigated. Radial distribution functions reveal that the strong spatial correlation
between cation and anion still exists in the presence of a large amount of water. For vesicle micelle, the
inner layer of vesicle is packed denser than that of the outer layer. By analyzing hydrogen bond numbers
and coordination number in the solution, it is implied that binding between counterions enhanced with
concentration increasing, and the distribution density of ions in vesicle is close to the neat system.
Moreover, the dominant mechanisms and compromise process were also studied through the energy
analyzation.
References
[1] H. Wang, L. Zhang, J. Wang, Z. Li, S. Zhang "The first evidence for unilamellar vesicle formation of ionic
liquids in aqueous solutions" Chemistry Communication, 2013, 49: 5222-5224.
[2] X. Liu, G. Zhou, H. He, X. Zhang, S. Zhang "Rodlike micelle structure and formation of ionic liquid in aqueous
solution by molecular simulation", Industrial & Engineering Chemistry Research, 2015, 54: 1681-1688.
Acknowledgements
This work was supported by National Natural Science Foundation of China (91434111, 91434203), and Center for
Mesoscience, Institute of Process Engineering, Chinese Academy of Sciences (COM2015A003).

PPEPPD 2016
th
Bubble Pressure Measurement and Prediction for n-Alkane + Aromatic and

Naphthenic Hydrocarbon Binary Mixtures
Qingchen Liu, 1 Sourabh Ahitan, 1 Marco Satyro, 2 John M. Shaw *,1
1
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta, Canada, T6G
2G6.
2
Department of Chemical & Biomolecular Engineering, Clarkson University, Potsdam, NY 13699-5705, USA.
*Corresponding author: jmshaw@ualberta.ca
Scientific topic: hydrocarbon phase behaviour measurement and prediction
Keywords: Equation of State, cubic, SAFT, phase behaviour, measurement, prediction
Abstract
N-alkane + aromatic and naphthenic hydrocarbon binary mixtures exhibit Type I phase behaviour [1]. In
a recent work [2] we showed that common cubic equations of state systematically predict the phase
behaviour Type of long chain n-alkane + aromatic and naphthenic hydrocarbon binary mixtures
incorrectly unless negative binary interaction parameter (kij) values are used. As zero or positive kij
values are normally used in hydrocarbon process calculations, expected and observed phase and transport
properties in processes are dissonant over broad ranges of temperature, pressure and composition. We
also showed that the PC-SAFT equation of state computes the correct phase behaviour Type, with binary
interaction parameters set to zero. However, it was not possible to verify the quality of predicted bubble
pressures or to define interaction parameters systematically for cubic equations of state in the absence of
experimental data. In this follow up study, high-precision bubble-pressure measurements are presented
for representative binary mixtures drawn from the calculation set comprising 150 n-alkane + aromatic
and n-alkane + naphthenic hydrocarbon binary mixtures. The focus of the reported measurements is on
n-alkanes from C20 to C40 combined with alkyl-benzene, alkyl-naphthtalene, and alkyl-phenanthrene
compounds, and their naphthenic analogues such as alkyl-cyclohexanes. Regressed interaction parameter
values applicable to the Peng-Robinson, Soave-Redlich-Kwong and the PC-SAFT equations of state are
reported and their systematic variation is discussed. Expected applications of this work include improved
phase behavior model accuracy applicable to hydrocarbon production and transport environments, and
improved corresponding state based transport property prediction, particularly for viscosity, that require
accurate phase behaviors and phase compositions as inputs.
References
[1] P. H. van Konynenburg and R. L. Scott, “Critical lines and phase-equilibria in binary van der Waals mixtures”,
Philos. Trans. R. Soc., A 1980, 298, 495-540.
[2] S. Ahitan, M. A. Satyro, J. M. Shaw, "Systematic Misprediction of n-Alkane + Aromatic and Naphthenic
Hydrocarbon Phase Behavior Using Common Equation of State", J. Chem. Eng. Data 2015.
DOI:10.1021/acs.jced.5b00539
Acknowledgements
Three of the authors (Ahitan, Liu, Shaw) gratefully acknowledge financial support from the sponsors of the NSERC
Industrial Research Chair in Petroleum Thermodynamics: the Natural Sciences and Engineering Research Council
of Canada (NSERC), Alberta Innovates Energy and Environment Solutions, BP Canada, ConocoPhillips Canada
Resources Corp., Nexen Energy ULC, Shell Canada Ltd., Total E&P Canada Ltd., and the Virtual Materials Group.

PPEPPD 2016
th
Phase Diagram and Saturated Phase Property Measurement and Simulation

for Peace River Bitumen + Propane Mixtures
Yoann Dini, 1 Marco Satyro, 2 John M. Shaw *,1

1
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta, Canada, T6G
2G6.
2
Department of Chemical & Biomolecular Engineering, Clarkson University, Potsdam, NY 13699-5705, USA.
*Corresponding author: jmshaw@ualberta.ca
Scientific topic: hydrocarbon phase behaviour measurement and prediction
Keywords: Equation of State, cubic, phase behaviour, property, measurement, prediction
Abstract
One proposed option for the development of production processes for heavy oils with lowered
environmental impacts is to inject n-alkanes into reservoirs instead of, or in combination with steam.
Such processes are complex from a phase behaviour perspective because heavy oils + n-alkane pseudo
binary mixtures exhibit Type III phase behaviour [1,2]. Peace River Bitumen + propane is no exception
[3]. Proposed processes are also complex from a phase property perspective because water, also present,
is less dense than typical heavy oils, but is more dense than heavy oils diluted with low molar mass
hydrocarbons. Operating conditions for subsurface and surface facilities must be selected carefully to
avoid or exploit phase inversions in reservoirs and in process equipment [4]. In this work, we present the
experimental phase diagram, saturated phase compositions and phase densities for the Peace River
Bitumen + propane pseudo binary mixture. We also discribe and discuss a phase behavior and phase
property model for such mixtures that builds on our prior simulation work with heavy oils [5-9].
References
[1] P. H. van Konynenburg and R. L. Scott, “Critical lines and phase-equilibria in binary van der Waals mixtures”, Philos.
Trans. R. Soc., A 1980, 298, 495-540.
[2] J. M. Shaw, M. A. Satyro and H. W. Yarranton, Chapter 7., The Phase Behaviour and Properties of Heavy Oils,
"Practical Advances in Petroleum Production and Processing", co-edited by Chang Samuel Hsu and Paul R. Robinson
(Springer: New York) in press, 2015.
[3] Y. Dini, "Phase Behavior and Thermophysical Properties of Peace River Bitumen + Propane mixtures, University of
Alberta, 2015.
[4] Stewart, Robert A., Wood, Caitlin V., Murowchuck, Steven J., Shaw, John M., "Phase Order Inversion During Heavy
Oil and Bitumen Production with Solvent Addition", Energy & Fuels, 2014, 28(7), pp 4835-4848
[5] Saber, N., Zhang,X, Zou, X-Y., Shaw, J.M., Simulation of the phase behaviour of Athabasca vacuum residue +n-
alkane mixtures. Fluid Phase Equilibria 2012,313(0), 25-31.
[6] Saber, N., Satyro, M., Yarranton, H., Shaw J.M., Multiphase Equilibrium Prediction for Ill-defined Asymmetric
Hydrocarbon Mixtures, Hydrocarbon World 2011, 6 (2), 51-57
[7] Nima Saber and John M. Shaw, On the phase behavior of Athabasca vacuum residue + n-decane, Fluid Phase
Equilibria, 302(1-2)(2011), 254-259.
[8] Richard A, McFarlane, Murray R. Gray, John M. Shaw, Evaluation of co-volume mixing rules for bitumen liquid
density and bubble pressure estimation, Fluid Phase Equilibria. 293,(1), (2010) 87-100.
[9] S. Ahitan, M. A. Satyro, J. M. Shaw, "Systematic Misprediction of n-Alkane + Aromatic and Naphthenic
Hydrocarbon Phase Behavior Using Common Equation of State", J. Chem. Eng. Data 2015.
DOI:10.1021/acs.jced.5b00539
Acknowledgements
Two of the authors (Dini and Shaw) gratefully acknowledge financial support from the sponsors of the NSERC
Industrial Research Chair in Petroleum Thermodynamics: the Natural Sciences and Engineering Research Council
of Canada (NSERC), Alberta Innovates Energy and Environment Solutions, BP Canada, ConocoPhillips Canada
Resources Corp., Nexen Energy ULC, Shell Canada Ltd., Total E&P Canada Ltd., and the Virtual Materials Group.

PPEPPD 2016
th
Generation and thermodynamic modelling of vapour-liquid equilibrium data

for aroma compounds in hydroalcoholic mixtures - Application to the
simulation of spirits distillation units
Cristian Puentes1*, Martine Esteban-Decloux1, and Patrice Paricaud2

1
Unité Mixte de Recherche Ingénierie Procédés Aliments (UMR GENIAL), AgroParisTech, INRA, Université
Paris-Saclay F-91300, Massy, France.
2
Unité de Chimie et Procédés (UCP), ENSTA ParisTech, Université Paris-Saclay, F-91120, Palaiseau, France.
*Corresponding author: cristian.puentes@agroparistech.fr
Scientific topic: Thermodynamics and Transport Properties (Applied Thermodynamics, Fluid Dynamics, Heat
Transfer - Chemical Engineering Fundamentals)
Keywords: Vapour-liquid equilibria, aroma compounds, experimental and predictive approaches, Spirits
distillation, computer simulation.
Abstract
The quality of spirits is a parameter related to the composition of volatile aroma compounds. This
composition is largely conditioned by the distillation step, a very old separation technology but whose
mastery is still limited because the units’ operation relies heavily on empirical knowledge. The aim of
our study is to contribute to a better understanding of the aroma compounds behaviour in different spirits
distillation methods through computer simulation.
For the implementation of simulation modules, it is essential to know the vapour-liquid equilibria (VLE)
of aroma compounds in hydroalcoholic solution and to make a suitable choice of thermodynamic models
with a view to achieve an accurate description of concentration profiles in the distillation units. The
comparison of the simulation using BatchColumn by ProSim® with respect to the experimental data of
Cognac distillation [1] shows that the profiles predicted by UNIFAC model are incorrect for certain
compounds with a high sensory impact, including ethyl lactate and 2-phenylethanol, and are far away
from the actual behaviour in batch distillation.
In this context, this poster presents a methodology for the generation and validation of VLE data of the
two aroma compounds at atmospheric pressure, followed by simulation results with NRTL activity
coefficient model, widely used to describe hydroalcoholic solutions at low pressures. Three
complementary approaches are described for the generation of equilibrium data : 1. Information from
literature, 2. Experimental measurements by a dynamic method using the device Labodest VLE 602 TM
[2], and 3. Predictions with COSMO quantum chemistry based models [3], [4].
References
[1] R. Cantagrel, L. Lurton, J.-P.Vidal, B. Galy. “La distillation charentaise pur l’obtention des eaux-de-vie de
Cognac”. Presented at 1er symposium international sur les eaux-de-vie traditionnelles d’origine viticole. Bordeaux
(France), 1990.
[2] V. Athès, P. Paricaud, M. Ellaite, I. Souchon, W. Fürst. “Vapour–liquid equilibria of aroma compounds in
hydroalcoholic solutions: Measurements with a recirculation method and modelling with the NRTL and COSMO-
SAC approaches”. Fluid Phase Equilibria, 2002, 265 : 139 – 154.
[3] A. Klamt. “Conductor-like Screening Model for Real Solvents : A new approach to the Quantitative Calculation
of Solvation Phenomena”. Journal of Physical Chemistry, 1995, 99 : 2224 – 2235.
[4] S.-T. Lin, Sandler S.I. “A Priori Phase Equilibrium Prediction from a Segment Contribution Solvation Model”.
Industrial and Engineering Chemistry Research, 2002, 41 : 899 – 913.
PPEPPD 2016
th
THURSDAY – MAY, 26
Invited Lecture 9
Properties and Phase Equilibria – Examples from Industrial Applications
Ralf Dohrn1*, Stephanie Peper1, José M. S. Fonseca2

1
Downstream Processes, Bayer Technology Services, Leverkusen, Germany
2
Reaction Kinetics and Thermodynamics, Covestro Deutschland AG, Leverkusen, Germany
*Corresponding author: ralf.dohrn@bayer.com
Keywords: thermophysical properties, phase equilibria, industrial applications, azeotrope
Abstract
The knowledge of the thermophysical properties and the phase equilibria of components taking part in a
chemical reaction including the dependence on temperature and pressure is essential for process
optimization. For difficult separations, small uncertainties in phase equilibrium data might have a huge
impact on the design of the separation process [1]. Furthermore, properties and phase equilibria gain
increasing importance in the Life Sciences, e.g., for the design of controlled release drug delivery
systems. In this presentation examples from industrial practice are given for cases in which Applied
Thermodynamics played an important role to optimize a process or a product:
 Process Design: Prediction and experimental verification of an azeotrope

 Process Design and Process Safety: Prediction and verification of a hydrate formation in a
decanter of a distillation column.
 Sustainability: Incorporation of CO2 into a Polyol; avoiding errors during the experimental
determination of high-pressure VLE [2, 3]; precise determination of low-pressure VLE [3]
 Avoid animal testing: Precise determination of very low vapor pressures [4]
 Safety: Prediction of the flash point, the auto ignition temperature, and the normal initial
boiling point of PU raw materials [5]
 Bee Health: Fighting the varroa tick
Companion animals: No chance for parasites
References
[1] E. Hendriks, G. Kontogeorgis, R. Dohrn, J.-C. de Hemptinne, I.G. Economou, L. Fele Zilnik, V. Vesovic,
Industrial requirements for thermodynamics and transport properties. Ind. Eng. Chem. Res. 2010, 49 (22), 11131–
11141.
[2] R. Dohrn, J.M.S. Fonseca, S. Peper, Experimental methods for phase equilibria at high pressures. Annu. Rev.
Chem. Biomol. Eng., 2012, 3:343–367
[3] J.M.S. Fonseca, B. Libório, R. Dohrn, A. Wolf, Phase equilibria in process design for the production of
polymers derived from carbon dioxide, Fluid Phase Equilibria, 2016, 409: 369-375
[4] J.M.S. Fonseca, N. Gushterov, R. Dohrn, Vapour pressures of selected organic compounds down to 1 mPa,
using mass-loss Knudsen effusion method, J. Chem. Thermodyn., 2014, 73: 148–155
[5] S. Peper, R. Dohrn, K. Konejung, Methods for the Prediction of thermphysical properties of poylurethane raw
material mixtures, Fluid Phase Equilibria, 2016, in press

PPEPPD 2016
th
Invited Lecture 10
SAFT as a tool for phase equilibria calculations and process design: advances
and remaining challenges
Lourdes F. Vega1
1
Alya Technology & Innovation, Centre de Promoció Empresarial, C/ Tres Creus, 236, 08203 Sabadell, Barcelona,
Spain.
*Corresponding author: lvega@alyatech.com
Keywords: SAFT modeling, aqueous solutions, ionic liquids, biodiesel, process design.
Abstract
25 years have passed since the first paper published on the development of the SAFT equation of state or
the SAFT approach [1] (from the Statistical Associating Fluid Theory). SAFT was developed, from the
very beginning, to describe the thermodynamic properties and phase behaviour of associating systems,
naturally extended to oligomers, polymers and other systems with highly directional and short range
attractive forces.
During these years different version of SAFT have been implemented by different authors and the
approach has been widely used to model highly non ideal systems, including including ionic liquids,
aqueous solutions, gas separation processes, electrolyte systems, surfactants and biodiesels, to mention
few of them. These works have demonstrated that the SAFT appoach is, by far, more accurate and
reliable than other modeling approaches for complex systems such as those needed in industrial
processes. However, and in spite of the successes, there are still remaining opportunities for further
development before SAFT can be truly considered a standard tool in industrial process design.
This talk will first provide an overview on how having the right physics with the adequate level of
approximations has made SAFT and its extensions a successful tool in both, academia and industry. It
will also show where some of the remaining limitations are. For this purpose we will focus on some
recent applications of soft-SAFT to associating fluids such as ionic liquids, biodiesels [2] and aqueous
solutions [3], highlighting the robutness and limitations of the approach. We will also address the
opportunities on moving SAFT from academia to industry and backwards.
References
[1] W.G. Chapman, K.E. Gubbins, G. Jackson, M. Radosz, “New reference equation of state for associating
liquids”, Ind. Eng. Chem. Res. 29 (1990) 1709-1721.
[2] M.B. Oliveira, S.V.D. Freitas, F. Llovell, L.F. Vega, J.A.P. Coutinho, “Development of simple and transferable
molecular models for biodiesel production with the soft-SAFT equation of state”. Chemical Engineering Research
and Design 92 (2014), 2898-2911.
[3] L. F. Vega, F. Llovell, F. J. Blas, “Capturing the solubility minima of n-alkanes in water by soft-SAFT”. J.
Phys. Chem. B 113 (2009) 7621-7630.
Acknowledgements
We acknowledge financial support from the Catalan Government (project 2014SGR-1582).

PPEPPD 2016
th
Modeling of Phase Equilibira for Aqueous-Organic Electrolyte Systems
Sun Hyung Kim1,2, Amata Anantpinijwatna1, Jeong Won Kang2* and Rafiqul Gani1
1
2
Department of Chemical and Biological Engineering, Korea University, Republic of Korea
*Corresponding author: jwkang@korea.ac.kr
Scientific topic: Phase equilibria (modeling)
Keywords: Electrolyte, Mixed Solvent, Debye-Hückel, UNIFAC, Temperature Dependence
Abstract
An electrolyte model developed by Kim et al. [1] has previously been used for calculating
thermodynamic properties of alkali halid aqueous solution, for which results show good agreement with
the data. The proposed model mainly consists of three terms, that is, a Debye-Hückel term, a second
virial coefficient-type term and a KT-UNIFAC term. In this work, the model is extended to mixed
solvent systems containing water, alcohols and alkali halide salts. A Born term is included in the model
for the mixed solvent system to correct the change of the reference state from infinite-dilution mixed-
solvent solution to infinite-dilution aqueous solution. Required binary interaction parameters between
solvents and ions, and cations and anions are newly estimated from experimental data of binary and
ternary systems. A linear temperature-dependent coefficient is included in the binary parameters to get
better agreement in a wide range of temperature. Calculated results are extensively compared with
available data and models. The proposed model covers various phase behaviors including mean ionic
activity coefficients and osmotic coefficients at concentartions from diluted solution to salt solubility as
well as vapor-liquid, liquie-liquid and solid-liquid equilibria with the desired accuracy.
References
[1] S. H. Kim, A. Amata, J. W. Kang, R. Gani “Analysis and Modeling of Alkali Halide Aqueous Solutions” Fluid
Phase Equilibria, 2015, submitted.

PPEPPD 2016
th
Reoptimization of COSMO-SAC Parameters for Vapor-Liquid Equilibrium

Using Critically Evaluated Data
Eugene Paulechka1, Vladimir Diky1, Andrei Kazakov1, Michael Frenkel1, and Kenneth Kroenlein1*
1
Thermodynamics Research Center, National Institute of Standards and Technology, USA
*Corresponding author: kenneth.kroenlein@nist.gov
Keywords: Thermophysical properties of liquids; activity coefficients; prediction methods; COSMO
Abstract
Quantum-chemistry-based statistical thermodynamic calculations are routinely used for reliable

prediction of thermodynamic properties of ideal gases. Prediction of thermodynamic properties of pure
liquids and liquid solutions is a more complicated problem due to multiple interactions between
molecules and non-periodic structure of these phases, which has resulted in the extensive adoption of
empirical models. A bridge between empirical models and quantum chemistry was created when Klamt
et al. proposed COSMO-RS (COnductor-like Screening Model for Real Solvents)[1, 2]. A number of
alternative formulations have been proposed, such as the widely adopted COSMO-SAC[3].
In this work, COSMO-SAC was reparameterized with use of the critically evaluated data generated by
the NIST ThermoData Engine[4] for vapor-liquid equilibria, excess enthalpies for binary mixtures, and
activity coefficients of binary mixture components. The calculated σ-profile library contained 897
individual compounds. The temperature-dependent σ-profiles included contributions of up to 40
conformers of a molecule. Splitting of the H-bonding σ-profiles into OH- and non-OH-parts decreased
the root-mean square deviation from the experimental data points by about 10 % compared to the model
using one H-bonding parameter. Predictions of the reparameterized models demonstrate comparable
performance with common empirical approaches. The challenges of uncertainty evaluation for
parameters of the model and the predicted values are discussed.
References
[1] Klamt, A. Conductor-like screening model for real solvents: a new approach to the quantitative calculation of
solvation phenomena. J. Phys. Chem. 1995, 99, 2224-2235.
[2] Klamt, A.; Jonas, V.; Burger, T.; Lohrenz, J. C. W. Refinement and Parametrization of COSMO-RS. J. Phys.
Chem. A 1998, 102, 5074-5085.
[3] Lin, S. T.; Sandler, S. I. A Priori Phase Equilibrium Prediction from a Segment Contribution Solvation Model.
Ind. Eng. Chem. Res. 2002, 41, 899-913.
[4] Frenkel, M.; Chirico, R. D.; Diky, V.; Kroenlein, K.; Muzny, C. D.; Kazakov, A. F.; Magee, J. W.;
Abdulagatov, I. M.; Lemmon, E. W. NIST ThermoData Engine, NIST Standard Reference Database 103b - Pure
Compounds, Binary Mixtures, and Chemical Reactions, version 9.0; Standard Reference Data Program; National
Institute of Standards and Technology: Gaithersburg, MD, 2014.
PPEPPD 2016
th
A new model for water in GC-PPC-SAFT and subsequent modeling of LLE,

VLE, VLLE of water mixtures with hydrocarbons and oxygenates
Saifuddin Ahmed1, Nicolas Ferrando1, Jean-Charles de Hemptinne1*

1
IFP Energies nouvelles, 1 et 4 Avenue de Bois-Préau, 92852 Rueil-Malmaison Cedex, France
* Corresponding author: jean-charles.de-hemptinne@ifpen.fr
Keywords: GC-PPC-SAFT, Water, Vapor-Liquid-Liquid Equilibrium, Hard sphere diameter
Abstract
The first generation biofuels, however promising, appear unsustainable because their feed are food
sources, which are already suffering wide shortages. This is why the use of ligno-cellulosic biomass
derived from agricultural and forest residues is now considered as an alternative for the production of so-
called second-generation biofuels through biochemical and thermochemical means. One of the
challenges in the design of processes for converting these feedstocks into valuable products is the
description of phase equilibria: due to the highly oxygenated nature of these products and the presence of
large amounts of water, both liquid-vapour and liquid-liquid equilibria can occur.
The present work is focused on improving the GC-PPC-SAFT parameterization of pure water. A
previous work with this model [1] has led to succesful modelling of the phase equilibria, but large
density deviations were observed. Here, we used the approach proposed by Held et al. [2], consisting in
modifying the temperature dependence of the hard sphere diameter of water in order to improve the
global phase behaviour of this compound in a large temperature range. The deviations in vapor pressure
and specially liquid density is now significantly reduced compared to our previous model [1], to as low
as 2.2% and 0.6% ARD respectively, over a temperature range from 0ºC to 550ºC. Four new parameters
are therefore introduced.
Mixtures of water with alkanes, aromatics, alcohols, aldehydes, ketones, ethers and ester are then
investigated using the group-contribution concept for predicting their LLE and VLE. Results in term of
mutual solubilities are found similar or better than our previous works on these mixtures [3]. The VLLE
of certain water-alcohol heteroazeotropic mixtures are also investigated. A comparison is also drawn
between our pure predictive approach vs the approach using fitted binary interaction paramters (kij). The
results so far reflect that after employing our new modifiations, the model moves closer to real behaviour
and prediction accuracy is enhanced for water mixtures.
References
[1] N. H. Dong, J.C. de-Hemptinne, R. Lugo, J. P. Passarello, P. Tobaly. “Modeling Liquid-Liquid and Vapor-
Liquid enquilbria of Binary systems containing water with an Alkane, an aromatic hydrocarbon, an alcohol or a gas,
using GC-PPC-SAFT” Industrial Engineering and Chemical Research, 2011, 50: 7467-7483.
[2] C. Held, L.F. Cameretti, G. Sadowski “Modeling of electrolyte solutions Part 1. Fully dissociated electrolytes”
Fluid Phase Equilibria, 2008, 270: 87-96.
[3] T.B. Nguyen, J.C. de Hemptinne, B. Creton, G.M. Kontogeorgis. “ Improving GC-PPC-SAFT equation of state
for LLE of hydrocarbons and oxygenated compounds with water” Fluid Phase Equilibria, 2014, 372: 113-125.

PPEPPD 2016
th
Experimental measurements and predictions of the properties of refrigerant

fluids using ab-initio, SAFT-VR Mie and COSMO calculations
J. Glorian1, J. El. Abbadi2, J. Janecek1, P. Paricaud1,2, L. Catoire1, J. Deschamps1, C. Houriez2, C. Coquelet2,
O. Baudouin3, A. Baba-Ahmed4 , G. Fuchs4
1
UCP, ENSTA Paristech, 828 Boulevard des Maréchaux, 91762 Palaiseau, France
2
Mines ParisTech, PSL research University, CTP, 35 rue Saint Honoré, 77305 Fontainebleau Cedex, France.
3
Prosim, 51 rue Ampère, Immeuble Stratège A, 31670 Labège.
4
Arkema, Chemin Henri Moissan, 69310 Pierre-Bénite, France
*Corresponding author: patrice.paricaud@ensta-paristech.fr
Scientific topic: Thermodynamics Properties and Phase Equilibria
Keywords: SAFT, ab initio calculations, VLE measurements, new refrigerants
Abstract
On account of the constraints imposed by the European and International legislations, the
refrigerant industry must constantly find alternative refrigerant fluids that have lower impacts on the
global warming of Earth and Ozone layer. The hydrofluoroolefins (HFO) have been proposed to replace
the currently used hydro fluorocarbons (HFC), as they have a much lower global warming potential. In
order to select the optimal mixture composition for the design and operation of a refrigeration process, it
is necessary to know the phase diagram and thermodynamic properties of the mixtures. In particular, the
vapor-liquid equilibria (VLE) and the location of azeotropes must be accurately known. Besides, the
design of chemical processes and heat engines requires a good knowledge of both the ideal gas and the
residual thermodynamic properties of the refrigerants. The aim of this work is to propose various
thermodynamic approaches to predict these properties.
First, we performed ab initio calculations on isolated molecules to determine the ideal gas
properties of refrigerant fluids. Ideal enthalpies of formation and heat capacities can be accurately
predicted by using either DFT [1] or some specific semi-empirical methods. We then used several
activity coefficient models based on the COSMO approach, to predict the VLE of refrigerant mixtures.
VLE and azeotropes can be well predicted by the COSMO-RS model [2]. While the first versions of
COSMO-SAC are very inaccurate for such systems, it is possible to obtain good predictions with the
COSMO-SAC-dsp model [3] by readjusting some universal parameters. New experimental
measurements of vapor-liquid equilibria on mixtures involving HFO have been performed with a static
analytic equipment, to complete the literature data for mixtures of HFO with other refrigerants.
We then propose a modified version of the SAFT-VR-Mie [4] equation of state (EoS) that
includes a polar contribution to explicitly take electrostatic interaction into account. The polar SAFT-
VR-Mie EoS is used to describe the VLE and some derivative thermodynamic properties of refrigerant
mixtures. A new association model that takes the formation of cyclic clusters is proposed for hydrogen
floride (HF), which is one major compound of the refrigerant production process. The new models can
be used in process simulation softwares, thanks to the cape-open and Simulis Thermodynamics®
interfaces.
References
[1] A. Osmont et al., Combustion and Flame, 151, 262 (2007)
[2] F. Eckert, A. Klamt, Fluid Phase Equilib., 172, 73 (2010)
[3] C.-H. Hsieh et al., Fluid Phase Equilib., 367, 709 (2014)
[4] T. Lafitte et al., J. Chem. Phys., 139,154504 (2013).
Acknowledgements
The results presented in this work are part of the ongoing project "PREDIREF". We are grateful to the National
French Research Agency (ANR-13-CDII-0008) for providing financial support to this project.
PPEPPD 2016
th
Oral Session – 10 Surfaces, Interfaces and Confinement 2 – O10-1
Modeling of Confined Fluids via Molecular Simulation and Equation of State
Gabriel D. Barbosa1, Leonardo Travalloni1, Frederico W. Tavares1*, Marcelo Castier2

1
Chemical Engineering Department, School of Chemistry, Federal University of Rio de Janeiro, Brazil
2
*Corresponding author: tavares@eq.ufrj.br
Keywords: Adsorption, Monte Carlo, Peng-Robinson
Abstract
The thermodynamic modeling of confined fluids is fundamental for several chemical engineering
applications. However, the most accurate approaches for describing these systems, such as molecular
simulations and density functional theory, have a large computational cost. Thus, the development of
equations of state for confined fluids is an attractive alternative. In previous work [1, 2], classic cubic
equations of state were extended to fluids confined in cylindrical pores, based on a purely empirical
modeling of strutctural properties of the fluid. In this work, the Peng-Robinson equation of state was
extended to fluids confined in slit pores, based on the generalized van der Waals theory and on Monte
Carlo molecular simulation data. The simulations were performed in order to evaluate geometric and
energetic effects of different confinement degrees on the fluid structure. Fluid molecules were considered
as spheres interacting with each other and with the pore walls through square-well potentials. Pairwise
additivity was assumed for both molecule-molecule and molecule-wall interactions. The obtained
equation of state relates the usual thermodynamics properties (temperature, volume, and pressure) with
the pore size and two molecule-wall interaction parameters. The model showed a high flexibility in
describing different types of adsorption isotherms. The molecule-wall interaction parameters were
estimated from pure fluid adsorption data and used for predicting the behavior of adsorbed mixtures,
without the fitting of binary interaction parameters. Good results were obtained for some of the studied
systems.
References
[1] L. Travalloni, M. Castier, F. W. Tavares, S. I. Sandler “Thermodynamic modeling of confined fluids using an
extension of the generalized van der Waals theory” Chemical Engineering Science, 2010, 65: 3088-3099.
[2] L. Travalloni, M. Castier, F. W. Tavares “Phase equilibrium of fluids confined in porous media from an
extended Peng-Robinson equation of state” Fluid Phase Equilibria, 2014, 362: 335-341.
Acknowledgements
This work was made possible by the NPRP grant 5-344-2-129 from the Qatar National Research Fund (a member
of Qatar Foundation). The statements made herein are solely the responsibility of the authors.

PPEPPD 2016
th
Optimal design of the cohesive parameter in cubic equations of state
Romain Privat1*, Silvia Lasala1, Yohann Le Guennec1 , Jean-Noël Jaubert1

1
*Corresponding author: romain.privat@univ-lorraine.fr
Scientific topic: Thermodynamic and transport properties, Phase equilibria
Keywords: cohesive parameter, alpha functions, cubic equations of state, Soave, Twu.
Abstract
Depending on the considered thermodynamic system, the modeling capability of cubic equations of state
could be strongly affected by the formulation of the alpha-function integrated in their attractive term. To
avoid non-physical negative values of the attractive term of cubic equations of state, an alpha-function
should be a continuous positive function at all temperatures. Moreover, it should approach zero for
infinite temperatures and a finite value for temperature tending to zero. Furthermore, it is possible to
establish that the residual heat capacity at constant volume is proportional to the second derivative of the
alpha function with respect to temperature. In other words, if the alpha function exhibits an inflexion

point at temperature T* characterized by: d 2 dT 2
T T*

 0 , the residual heat capacity at constant
volume vanishes and the fluid heat capacity becomes equal to that of the perfect gas. Since for a perfect
gas, cv only depends on temperature, we will get whatever the pressure:
cv,pure fluid (T* ,P)  cv,perfect gas (T* ) . As a conclusion, in a (cv,T) plane, all the isobars would intersect
at temperature T*. Such a behavior was however never experimentally observed. We can thus conclude
that the alpha function must not exhibit inflexion points. To sum up, the alpha function must be a
continuous positive - monotonically decreasing - convex function of temperature. Unfortunately none of
the many alpha-functions available in the open literature (Soave [1], Mathias-Copeman [2], Twu [3] …)
have such characteristics when used with the parameters published by their authors.
This study aims at proposing a new generalized alpha-function, the universal parameters of which were
obtained by regression over vapor pressure, enthalpy of vaporization and liquid heat capacity data for
hundreds of components. The fitting procedure was conducted in order to fulfill the characteristics
previously discussed. The third derivative of the alpha function, with respect to temperature was also
imposed positive in order to increase the accuracy in the supercritical region. The results clearly indicate
that the proposed alpha function is much more accurate than those previously published.
References
[1] G. Soave “Equilibrium constants from a modified Redlich–Kwong equation of state” Chemical Engineering
Science, 2012, 27: 1197–1203.
[2] P. M. Mathias, T. W. Copeman “Extension of the Peng–Robinson equation of state to complex mixtures:
evaluation of the various forms of the local composition concept” Fluid Phase Equilibria, 1983, 13: 91–108.
[3] C. H. Twu, D. Bluck, J. R. Cunningham, J. E. Coon “A cubic equation of state with a new alpha function and a
new mixing rule” Fluid Phase Equilib, 1991, 69: 33–50.

PPEPPD 2016
th
Water confined in nanopores; the stacking-disordered ice structures
Kamila Domina, Kwong Y Chanb, Małgorzata Śliwinska-Bartkowiaka, Yun Longc and Keith E. Gubbinsd
a
Faculty of Physics, Adam Mickiewicz University, Poznan 61-614, Poland
b
Department of Chemistry, Hong-Kong University , Pokfulam Road , Hong Kong
c
Department of Chemical& Biomolecular Engineering, National University of Singapore, Singapore
d
Department of Chemical& Biomolecular Engineering, North Carolina State University, Raleigh, NC , USA
*Corresponding author: msb@amu.edu.pl
Keywords: Nanocarbons, confined ice structures, diffraction methods
Abstract
We report X –rays diffraction studies of water and carbon tetrachloride adsorbed in nanoporous activated
carbon fibres (ACFs) and CMK-3 carbon mesopores of different pore size. The fibres are built of
turbostratic nanoparticles separated by quasi two-dimensional voids, forming narrow slit-shaped pores;
CMK-3 are the reverse carbon replica of silica SBA-15 porous matrices. We observe the significant
changes in the interlayer distance of the carbon nanoparticles under the water adsorption conditions; the
results suggest that very high pressures arise within the pores, about a few hundreds MPa, as has been
observed in molecular simulations [1,2] .Such a results are confirmed by observation of high pressure
forms of ice in cylindrical nanocarbons , using neutron and X –rays diffraction methods. [3] For water in
multiwalled carbon nanotubes (MWCN), below the pore melting point the existence of cubic ice was
observed. This kind of structure of ice can be obtained during re-crystallisation from high pressure
phases at low temperatures for the water bulk. For CMK-3 mesopores we observe the existence of a
stacking-disordered ice, Isd [4 ], This metastable ice is neither cubic nor hexagonal, and is not a simple
mixture of the two, but a combination of cubic sequences intertwined with hexagonal sequences.
Moreover, the stacking disorder may vary in complexity depending on the way the ice is formed and on
the prevailing thermal conditions during this process. The analysis of the kind of Isd formed in CMK-3
of different pore size will be presented. These crystal forms, which occur in bulk water only at
temperatures below 180 K in the case of cubic ice, and at pressures of hundreds or thousands MPa are
stabilized by the confinement.
References
[1] M.Sliwinska-Bartkowiak, M.Drozdowski, M.Jazdzewska, Y.Long, J.Palmer, K.E.Gubbins, Phys. Chem. Chem.
Phys., 14, 2012, 71454.
[2] Y. Long, J.Palmer, B.Coasne, M.Sliwinska-Bartkowiak, K.E.Gubbins, Phys. Chem. Chem. Phys , 13 ,2011,
17163.
[3] M.Jazdzewska , M. Sliwinska-Bartkowiak, A.I. Beskrovnyy, S.G. Vasilovskiy, S.W. Ting, K.Y. Chan, L.L.
Huang, K.E. Gubbins, Phys. Chem. Chem. Phys., 13 ,9008 (2011); K.Domin, M.Sliwinska-Bartkowiak,K.Y.Chan,
K.E.Gubbins-in press.
[4] Malkin, T. L., Murray, B. J., Salzmann, C., Molinero, V., Pickering, S. J., & Whale, T. F. Phys. Chem. Chem.
Phys., 2014, 17(1), 60-76; A.Haji-Akbari, P.G.Debenedetti, PNAS, 2015, 112, 10582.
Acknowledgements
We thank for financial support for National Center of Science, Grant No: DEC-2013/09/B/ST4/03711
PPEPPD 2016
th
Mixtures of Hydrogenated and Fluorinated Chains: Thermodynamics,

Spectroscopy and Simulation
Ana Rosa Garcia2, Pedro Morgado1, Miguel Teixeira1, Luís F. G. Martins3, Laura Ilharco2 and Eduardo J. M.
Filipe1*
1
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal
2
Centro de Química-Física Molecular, Instituto Superior Técnico, 1049-001 Lisboa, Portugal
3
Centro de Química de Évora, University of Évora, Rua Romão Ramalho, 59, 7000-671 Évora, Portugal
*Corresponding author: efilipe@ist.utl.pt
Keywords: Fluorinated, Surface tension, Density, IR Spectroscopy, Molecular dynamics
Abstract
Highly fluorinated compounds have become key fluids in a wide range of fields due to
their chemical inertness, biocompatibility and peculiar physical properties. Some of their most
significant applications involve its use in liquid ventilation formulations, as oxygen carriers in
blood substitutes or as solvents for biphasic synthesis and lubricants. Perfluorinated chains (-
CF2CF2CF2-) are not only highly hydrophobic, but also lyophobic, i.e. they segregate
hydrogenated chains. In fact, mixtures of alkanes and perfluoroalkanes are known to be highly
non-ideal systems, exhibiting large regions of liquid–liquid immiscibility and large positive
excess properties.
In this work bulk and interfacial properties of several mixtures of hydrogenated and
fluorinated alkanes and alcohols have been studied: surface tensions and densities as a function
of composition, temperature and pressure have been experimentally measured. Additionally,
infrared spectra of the pure alcohols and mixtures have been recorded and molecular dynamics
simulations have been performed in order to gain a better understanding of the intermolecular
interactions in these systems.
The organization of the liquids seems to be the result of a delicate balance between the
unfavourable unlike dispersion interactions.1 Important conformational changes have also been
identified in the mixtures. At the surface, geometrical constraints may play an important role in
the structure of the interface.
Understanding these phenomena at the molecular level will ultimately allow the prediction and
fine-tuning of the structure of molecular films of the long-chain hydrogenated and fluorinated alcohols,
which are known to form patterned structures at the nanometer scale.
References
[1] P. Duarte, M. Silva, D. Rodrigues, P. Morgado, L. F. G. Martins, E. J. M. Filipe, J. Phys. Chem. B, 2013, 117:
9709–9717.

PPEPPD 2016
th
AUTHOR INDEX
Author Index
Full Name Contributions
Aguilar-Romero, Fernando 2 – P28, 2 – P49, 2 – P50
Aim, Karel 2 – P29
Al-Jadir, Thaer Munem 1 – P43
Altabet, Y. Elia 3 – P14
Altamash, Tausif 2 – P32
Alves da Rocha, Marisa Alexandra O4-1, 2 – P56, 2 – P66
Anantpinijwatna, Amata O9-1, 2 – P01
Araújo, João M. M. O4-4, 1 – P69
Arce, Alberto 2 – P14, 2 – P61, 3 – P37
Arya, Alay 3 – P49
Ballerat-Busserolles, Karine 2 – P39
Barthélemy, Pierre WR&D-5
Baudouin, Olivier O9-4
Bauer, Gernot 2 – P67
Baz, Jörg 1 – P51, 1 – P59
Bell, Ian 1 – P55, 3 – P16
Blahušiak, Marek 3 – P48
Bogdanić, Grozdana 1 – P32
Bonilla-Petriciolet, Adrián 1 – P29, 3 – P46
Bottini, Susana 3 – P09
Brehelin, Mathias WR&D-2
Brennecke, Joan F. 2 – P19, 2 – P51
Bühl, Christian 1 – P33
Cabrera, Adolfo L. 2 – P21
Canongia Lopes, José Nuno 1 – P11, 3 – P38, 3 – P42
Cao, Wei O2-4, 3 – P61
Casaca, Maria Emília
Castier, Marcelo IL1, O10-1

Author Index
Chapman, Walter WSAFT-1
Chen, Chau-Chyun 1 – P03, 1 – P05
Chen, Jian O2-3
Chia, Chung Lim O4-3
Choi, Jisu 3 – P05
Clark, Jennifer 2 – P36
Clark, Robert John 3 – P33
Concepción Rodríguez, Eduardo 2 – P23
Cummings, Peter O1-3, 3 – P34
Dariva, Cláudio 3 – P58, 3 – P59
Dawass, Noura
de Hemptinne, Jean-Charles O9-3
de Loos, Theo
de Pablo, Juan OL
Díez-Alcalde, Diana 2 – P50
Dohrn, Ralf IL9, 1 – P01
Domínguez, Ángeles 2 – P30, 2 – P59, 3 – P26
Domínguez, Irene 2 – P59, 3 – P25, 3 – P26
dos Santos de Souza, Lorena Fernanda 1 – P25
Doubek, Martin 1 – P41
Duarte, Pedro 3 – P45
Dupas-Langlet, Marina 3 – P55
Economou, Ioannis G. WFF-4, 1 – P22, 2 – P13
Egues, Silvia Maria 3 – P58
Elimelech, Menachem IL6
Enders, Sabine O8-1, 1 – P33, 1 – P37, 1 – P46, 1 – P58
Englezos, Peter O2-1
Errington, Jeffrey O8-2

Author Index
Esperança, José M. S. S. 3 – P38
Febra, Sara A. 3 – P20
Fernández Suárez, Luis Jesús 3 – P03, 3 – P36
Fidalgo Blanco, Ruben 2 – P59, 3 – P25
Filipe, Eduardo J. M. O10-4, 3 – P42, 3 – P43, 3 – P44, 3 – P45
Fischlschweiger, Michael 1 – P58
Fisher, Laura
Forero Gaviria, Luis Alejandro 1 – P38, 1 – P39, 1 – P40
Fouad, Oulebsir 1 – P48
Fraaije, Johannes G. E. M. O7-4, 3 – P18
Fugas, João F.
Funazukuri, Toshitaka 2 – P55
Galindo, Amparo O1-2, 3 – P08, 3 – P15, 3 – P20, 3 – P45
Galliero, Guillaume WFF-3, O3-4, 1 – P48, 2 – P28
Gani, Rafiqul O9-1, 2 – P01, 3 – P51
Gaudin, Théophile 3 – P52
George, Ankitha Theres 2 – P43
González, Begoña 2 – P59, 2 – P60, 3 – P25, 3 – P26
Gonzalez Perez, Alfonso 2 – P65
González Sas, Olalla 2 – P59, 3 – P25
Gorri, Daniel 3 – P19
Groß, Joachim WSAFT-4, 1–P36, 1–P54, 1–P68, 2–P04, 2–P24, 2–P37, 2–P42, 2–P58, 2–P67
Goutaudier, Christelle 1 – P15
Gruetzner, Thomas
Gubbins, Keith E. O8-3, O10-3, 2 – P16
Hanna, Tamara
Hansen, Niels 1 – P51, 1 – P59
Haslam, Andrew J. O1-2, 1 – P53

Author Index
Hasse, Hans IL4, 1 – P19, 3 – P64
He, Maogang 1 – P16, 1 – P17, 3 – P63
He, Yan
Held, Christoph O6-2, 1 – P47
Hendriks, Eric
Hiraga, Yuya 3 – P40
Holzer, Günther O4-2
Hopp, Madlen 1 – P36, 2 – P24, 2 – P37
Huang, Liangliang O7-1, O8-3, 2 – P05, 3 – P61
Huo, Feng 3 – P65
Hutacharoen, Panatpong 3 – P08
Islam, Md Rashedul 1 – P03
Iwai, Yoshio 1 – P23
Jackson, George WSAFT-2, O1-2, 1 – P53, 3 – P08, 3 – P15, 3 – P20
Jalili, Amir Hossein 1 – P57
Jaubert, Jean-Noël O10-2, 1 – P07, 1 – P09
Ji, Yuanhui 1 – P34
Ji, Xiaoyan 1 – P18, 3 – P62
Jiang, Hao 1 – P22, 2 – P13
Jiménez-Serratos, Guadalupe 1 – P53
Jiri, Janecek 1 – P13
Johnston, Kimberly 1 – P12
Julien, Collell O3-4
Kalakul, Sawitree 3 – P51
Kaminski, Sebastian 2 – P47
Kanakubo, Mitsuhiro 2 – P33, 2 – P35, 3 – P60
Kato, Satoru 3 – P35
Kayukawa, Yohei 3 – P31

Author Index
Kijevčanin, Mirjana Lj. 3 – P07, 3 – P23
Kim, Sang Beom 2 – P52
Klein, Christoph 3 – P34
Kodama, Daisuke 2 – P33, 2 – P35
Kofke, David A. O5-1, 1 – P45
Koh, Carolyn IL7, 3 – P32
Kohns, Maximilian 1 – P19
Kollau, Laura J. B. M. 1 – P63
Kontogeorgis, Georgios M. O7-3, 1 – P20, 2 – P62, 3 – P49
Kos, Kathrin 1 – P35
Kovalenko, Nikita A. 3 – P10, 3 – P17
Kroenlein, Kenneth O9-2
Kroon, Maaike O4-1, 1 – P44, 1 – P61, 1 – P63, 2 – P66
Kurihara, Kiyofumi 2 – P54, 2 – P57
Kvamme, Bjørn 1 – P56
Lachet, Véronique O1-1, 2 – P09
Langenbach, Kai 3 – P64
Lazarou, Georgia 3 – P15
Lee, Chan Hee 3 – P06
Lee, Lloyd L. 3 – P04
Lemberg, Max 1 – P08
Leonhard, Kai 1 – P10, 2 – P47
Liebergesell, Bastian 1 – P14
Lindeboom, Tom
Lingampally, Prasanna Lakshmi 1 – P07
Liu, Bei 1 – P02
Liu, Chang O7-1, 1 – P27, 2 – P05, 3 – P62
Liu, Xiangyang 1 – P16, 1 – P17

Author Index
Lladosa, Estela 1 – P31
Llovell, Fèlix O2-2, 1 – P69
López, Pablo 2 – P19, 2 – P20
Lopez Rivera, Daniela 1 – P39
Lötgering-Lin, Oliver 2 – P37
Lu, Linghong O2-4, O7-1, 3 – P47, 3 – P61
Lu, Xiaohua O7-1, 1 – P18, 1 – P27, 2 – P05, 3 – P47, 3 – P61, 3 – P62
Lubben, Michael J. 2 – P51
Ma, Qing-Lan 1 – P04
Ma, Ruoxin
Mac Dowell, Niall 3 – P41
Macedo, Eugénia A. 1 – P06, 2 – P30, 3 – P25, 3 – P26
Mairhofer, Jonas 2 – P04
Makino, Takashi 2 – P33, 2 – P35, 3 – P60
Maksimov, Aleksey I. 3 – P10, 3 – P17
Małgorzata, Śliwinska-Bartkowiak O10-3
Mansfield, Elisabeth 1 – P55
Marin-Rimoldi, Eliseo 1 – P67
Marrucho, Isabel M. O6-1
Martins, Luís F. G. O10-4, 3 – P43, 3 – P44
Mascarello, Francesco
Mathias, Paul M. O5-2
Matsuda, Hiroyuki 2 – P54, 2 – P57
McBride, John 2 – P10
McCabe, Clare O3-2, 3 – P34, 3 – P43, 3 – P45
McClurg, Richard B. 3 – P30
Mejía, Andrés O8-4, 1 – P62
Mendoza-Castillo, Didilia I. 1 – P29

Author Index
Messerly, Richard A. 3 – P28
Michalec, Lukáš 2 – P53
Mio, Andrea 2 – P22
Mota-Martinez, Maria Teresa 3 – P41
Müller, Erich A. O1-2, O8-4, 1 – P53
Muñoz-Rujas, Natalia 2 – P28, 2 – P50
Naicker, Sivanna
Neau, Evelyne 3 – P22
Nezbeda, Ivo O1-4
Nichita, Dan Vladimir 3 – P29
Nicolas, Christophe 3 – P22
Nishiumi, Hideo 1 – P26
Nunes da Ponte, Manuel IL3
O’Connell, John HPPEPPD
Oba, Shigeo 3 – P02
Ohland, Anderson Luis 2 – P18
Ottiger, Stefan
Paduszyński, Kamil 3 – P24
Pajalić, Oleg WR&D-3
Pakalidou, Nikoletta 2 – P26
Palma, André M. 1 – P65
Palmer, Jeremy C. O7-2, 2 – P52, 3 – P33
Panagiotopoulos, Athanassios Z. O7-2, 1 – P22, 2 – P13
Pathayaturayil, Janakey Devi V. K. 2 – P46
Patrice, Paricaud O9-4, 1 – P13, 2 – P65, 3 – P68
Pellegrini Pessoa, Fernando Luiz 2 – P31
Peng, Ding-Yu 2 – P69
Pereiro, Ana B. O4-4, 1 – P69

Author Index
Perez Armada, Lorena 2 – P60
Pervaje, Amulya 2 – P11
Peters, Christine 3 – P11
Peters, Cor EFCE, 1 – P61, 3 – P32
Phan, Anh 3 – P56, 3 – P57
Piccolo, Chiara
Piñeiro, Manuel M. O8-4, 1 – P62, 1 – P69
Privat, Romain O10-2, 1 – P09
Puentes Mancipe, Cristian Felipe 3 – P68
Qian, Hongliang 1 – P27
Queimada, Antonio J. 1 – P65, 2 – P08
Radović, Ivona R. 3 – P07, 3 – P23
Raeissi, Sona 2 – P44
Ramírez Vélez, Nicolás 1 – P38
Ratanavaraha, Vatanavongs 1 – P21
Rathke, Bernd 2 – P56, 3 – P01
Rebolledo-Libreros, María Esther 1 – P28
Resende, Neuman S. 2 – P15, 2 – P18
Rhenals Montoya, Paula 1 – P39
Robustillo Fuentes, Maria Dolores 2 – P25
Rodriguez, Nerea R. 1 – P44, 1 – P61
Rodríguez, Óscar 2 – P61, 3 – P37
Rotrekl, Jan 2 – P29
Rousseau, Bernard O1-1, 2 – P09
Rubio Gallego, Jorge 2 – P07
Sadowski, Gabriele WSAFT-3, 1 – P08, 1 – P47
Sadus, Richard J. O3-1
Santiso, Erik 2 – P11, 2 – P36

Author Index
Sarupria, Sapna 3 – P50
Sass, Richard
Satyro, Marco A. 1 – P12, 1 – P42, 3 – P66, 3 – P67
Sauer, Elmar 1 – P54
Scheffczyk, Jan 1 – P10
Schilling, Johannes 1 – P36
Schlaikjer, Anders 2 – P62
Schultz, Andrew J. O5-1, 1 – P45
Scilipoti, José A. 3 – P13
Secuianu, Catinca 1 – P66
Selam, Muaz
Shariati, Alireza 2 – P41
Shaw, John M. 15PPEPPD, 3 – P66, 3 – P67
Shell, Scott IL2
Shimizu, Karina 1 – P11, 3 – P42
Siepmann, Ilja WFF-1
Silva, Gonçalo 3 – P43
Simões Santos, Mirella 2 – P12
Simond, Mickaël 2 – P40
Singh, Sudhir K. 1 – P60
Siperstein, Flor R. O4-3, 1 – P43
Sosa Marco, Adriel 3 – P03
Soto Campos, Ana 2 – P14, 2 – P61, 3 – P37
Srivastava, Deepti O8-3, 2 – P16
Striolo, Alberto 3 – P56, 3 – P57
Sugahara, Takeshi 2 – P63
Sweere, Teun 3 – P18
Taboada, María Elisa 3 – P54

Author Index
Taghi Zoghi, Ali 2 – P17
Tamura, Kazuhiro 2 – P68
Tang, Ning 2 – P02, 2 – P03
Tasche, Jos 3 – P53
Tavares, Frederico Wanderley O10-1, 2 – P12, 2 – P15, 3 – P13
Theodorou, Doros N. PA
Thommes, Matthias IL8
Trache, Djalal 2 – P48
Trusler, Martin 1 – P25
Tsanas, Christos 1 – P64
Tsuji, Tomoya 3 – P02
Ushiki, Ikuo 3 – P39
van Bochove, Gerard
van Osch, Dannie J. G. P. O4-1
Varfolomeev, Mikhail 3 – P27
Vega, Maria Lourdes F. IL10, O2-2, 1 – P69, 3 – P21
Vega de Las Heras, Carlos WFF-2
Vergadou, Niki 3 – P12
Vermorel, Romain O3-4, 1 – P48
Victorov, Alexey O3-3
Vinhal, Andre Pinto Coelho Muniz 1 – P20
Voges, Matthias 1 – P47
Voskov, Alexey L. 2 – P45
Waibel, Christian 1 – P68
Wallek, Thomas O4-2, 1 – P30, 1 – P35
Walowski, Christoph O8-1, 1 – P37
Wang, Tianyuan 2 – P34

Author Index
Watanabe, Masaki 2 – P33, 2 – P35
Weidler, Dominik 2 – P42
Westerholt, Antje
Wichterle, Ivan 1 – P32
Wysoczanska, Kamila 1 – P06
Xie, Yujiao 1 – P18, 3 – P62
Xu, Gang 1 – P49
Yamada, Junya
Yan, Weidong 2 – P02, 2 – P03
Yang, Han Earl 2 – P64
Yarranton, Harvey 1 – P12, 1 – P50
Zarca, Gabriel 1 – P52
Zeiner, Tim 1 – P46, 2 – P06
Zhang, Shi 3 – P63
Zhang, Xiangping IL5
Zhang, Zhuo 1 – P24
Zhao, Nan 2 – P27
Zhou, Huan 1 – P05
Zhou, Jian 2 – P38
Zhu, Yudan 3 – P47
Zhuang, Wei
Zimmermann, Patrick O8-1, 1 – P46
Zmpitas, Wasilios 2 – P58
Zou, Fengxia
Zubeir, Lawien O4-1, 2 – P66

LIST OF PARTICIPANTS
List of Participant
Algeria
Trache, Djalal
Unité d'Enseignement et de Recherche en Chimie
Appliquee, Ecole Militaire Polytechnique
BP 17, BordjBahri Alger
djalaltrache@gmail.com
Argentina
Bottini, Susana
PLAPIQUI, UNS, CONICET
Camino La Carrindanga, Km 7, 8000 Bahía Blanca
sbottini@plapiqui.edu.ar
Australia
Sadus, Richard
Centre for Moleclar Simulation,
Swinburne University of Technology
John Street, Hawthorn, Victoria 3122
rsadus@swin.edu.au
Austria
Fischlschweiger, Michael Kos, Kathrin
Ottronic Technology Laboratory, Ottronic GmbH Institute of Chemical Engineering and Environmental
Büschendorf 7, 8786 Rottenmann Technology, Graz University of Technology
michael.fischlschweiger@gmx.net Inffeldgasse 25c, 8010 Graz
kathrin.kos@tugraz.at
Holzer, Guenther Wallek, Thomas

R&D, Prozess Optimal Holzer GmbH Institute of Chemical Engineering and Environmental
Impulszentrum 1,8250 Vorau Technology, Graz University of Technology
holzer@prozess-optimal.at Inffeldgasse 25c, 8010 Graz
thomas.wallek@tugraz.at
Belgium
Barthélemy, Pierre
Executive Director-Research and Innovation, CEFIC,
Avenue E. van Nieuwenhuyse, 4 box 1, 1160 Brussels
PBA@cefic.be
Brazil
Dariva, Cláudio Ohland, Anderson Luis
Instituto de Tecnologia e Pesquisa, Tiradentes Federal University of Rio de Janeiro
University Av. Moniz Aragão, nº 360,Bloco 1, Cidade
Av. Murilo Dantas, 300, Aracaju, 49032-490 Universitária, Ilha do Fundão, 21.941-594 RJ
claudio.dariva@gmail.com aohland@peq.coppe.ufrj.br
Egues, Silvia Maria Pellegrini Pessoa, Fernando Luiz

Instituto de Tecnologia e Pesquisa, Tiradentes Tecnology Center, UFRJ
University Avenida Athos da Silveira Ramos, 149, 21949-909 RJ
Av. Murilo Dantas, 300, Aracaju, 49032-490 pessoa@eq.ufrj.br
smsegues@gmail.com
List of Participant
Resende, Neuman S. Simoes Santos, Mirella

Federal University of Rio de Janeiro Federal University of Rio de Janeiro
Av. Moniz Aragão, nº 360 - Bloco 1 Cidade Avenida Athos da Silveira Ramos, 149, 21949-909 RJ
Universitária, Ilha do Fundão, 21.941-594 ss.mirella@gmail.com
neuman@peq.coppe.ufrj.br
Robustillo Fuentes, Maria Dolores Tavares, Frederico W.

University of São Paulo Tecnology Center, UFRJ
Av. Porf. Lineu Prestes, 580, Bloco 20, Cidade Avenida Athos da Silveira Ramos, 149, 21949-909 RJ
Universitária, 05508-000 pessoa@eq.ufrj.br
mrobustillof@gmail.com tavares@eq.ufrj.br
Scilipoti, José
Federal University of Rio de Janeiro
Avenida Athos da Silveira Ramos, 149, 21949-909 RJ
jscilipoti@gmail.com
Canada
Ahitan, Sourabh Peng, Ding-Yu
University of Alberta University of Saskatchewan
Donadeo Innovation Centre for Engineering 12-361 57 Campus Drive, S7N5A9 Saskatoon
T6G 1H9 Edmonton dingyu.peng@usask.ca
ahitan@ualberta.ca
Englezos, Peter Shaw, John M.

The University of British Columbia Faculty of Engineering, University of Alberta
2360 East Mall, V6T 1Z3 Vancouver Edmonton, AB T6G 1H9
peter.englezos@ubc.ca jmshaw@ualberta.ca
Johnston, Kimberly Yarranton, Harvey

University of Calgary University of Calgary
2500 University Dr. NW, T2N 1N4 Calgary, Alberta 2500 University Dr. NW, T2N 1N4 Calgary, Alberta
johnstka@ucalgary.ca hyarrant@ucalgary.ca
Chile
Cabrera, Adolfo L. Mejia, Andres
Tecnical University of Frederico Santa Maria University of Conception
Casa Central, Av. España 1680, Valparaíso 4070386 Conception
adolfo.cabrera@usm.cl mejia@udec.cl
López, Pablo Taboada, Maria Elisa

Tecnical University of Frederico Santa Maria University of Antofagasta
Casa Central, Av. España 1680, Valparaíso Avenida Angamos 601, 1240000 Antofagasta
pablo.lopezporfiri@gmail.com mariaelisa.taboada@uantof.cl
China
Cao, Wei Chen, Jian
College of Chemical Engineering, Nanjing Tech State Key Laboratory of Chemical Engineering,
University Tsinghua University
No.5, Xin Mofan Road, Nanjing 210009 100084 Beijing
392284718@qq.com cj-dce@tsinghua.edu.cn
List of Participant
Guo, Xiaojing Ma, Ruoxin

Shanghai Institute of Applied Physics, Chinese Tianjin University of Science and Technology
Academy of Sciences No.29,13th street, TEDA, Tianjin 300457
4288 Shuangzhu Hwy, Jiading, Shanghai maruoxin@tust.edu.cn
xiaojing-8443@163.com
He, Maogang Qian, Hongliang

Xi'an Jiaotong University China Pharmaceutical University
No.28, Xianning West Road, Xi'an 710049 24 Tongjiaxiang, Gulou District, Nanjing 210009
mghe@mail.xjtu.edu.cn 271924705@qq.com
Huo, Feng Qin, Huibo

Institute of Process Engineering, Chinese Academy of China University of Petroleum
Sciences 18 Fuxue Road, Changping, Beijing 102249
1 North 2nd Street, Zhongguancun, Haidian District, 592248863@qq.com
Beijin 100190
huofeng@ipe.ac.cn
Li, Zhi Tang, Ning

China University of Petroleum-Beijing Chemistry, Zhejiang University
18 Fuxue Road, Changping, Beijing 102249 Jiao 8-320, 38 Zheda Road, 310027 Hangzhou
lz979157903@163.com tangning1001@zju.edu.cn
Liu, Chang Wu, Jiangtao

College of Chemical Engineering, Nanjing Tech Faculty of Engineering Thermophysics, Xi’an Jiaotong
University University
No. 5 Xinmofan Road, Nanjing 210009 Center of Thermal & Fluid Science, Xi’an, Shaanxi
change94@qq.com 710049
jtwu@mail.xjtu.edu.cn
Liu, Xiangyang Yan, Weidong

Xi'an Jiaotong University Chemistry, Zhejiang University
No.28, Xianning West Road, Xi'an 710049 Jiao 8-320, 38 Zheda Road, 310027 Hangzhou
lxyyang@mail.xjtu.edu.cn yanweidong@zju.edu.cn
Lu, Linghong Zhang, Shi

College of Chemical Engineering, Nanjing Tech Xi'an Jiaotong University
University No.28, Xianning West Road, Xi’an 710049
No. 5 Xinmofan Road, Nanjing 210009 zhangshi@stu.xjtu.edu.cn
linghonglu@njtech.edu.cn
Lu, Xiaohua Zhang, Xiangping

Nanjing Tech University, Nanjing Institute of Process Engineering, Chinese Academy of
No. 5 Xinmofan Road, Nanjing 210009 Sciences
xhlu@njtech.edu.cn 1 North 2nd Street, Zhongguancun, Haidian District,
Beijin 100190
xpzhang@ipe.ac.cn
List of Participant
Ma, Qinglan Zhang, Zhuo

College of Chemical Engineering, China University of School of Energy and Power Engineering, Xi'an
Petroleum Jiaotong University
18 Fuxue Road, Changping, Beijing 102249 No.28, Xianning West Road，Xi‘an, Shaanx 710049
maql@cup.edu.cn 443090803@qq.com
Zhou, Huan Zhu, Yudan
College of Chemical Engineering and Materials, College of Chemical Engineering, Nanjing Tech
Tianjin University of Science and Technology University
13th St, Binhai, Tianjin 300457 No. 5 Xinmofan Road, Nanjing, 210009
zhouhuan@tust.edu.cn yd_zhu1982@163.com
Zhou, Jian
School of Chemistry and Chemical Engineering,
South China University of Technology
No. 381, Wushan Road, Rm 302, No.16 Building,
Guangzhou 510640
jianzhou@scut.edu.cn
Colombia
Forero Gaviria, Luis Alejandro Ramírez Vélez, Nicolás
Faculty of Chemical Engineering, University of Faculty of Chemical Engineering, University of
Pontificia Bolivariana Pontificia Bolivariana
Circular 1 70-01, Medellín 56006 Circular 6 43-214, Medellín 56006
luis.foreroga@upb.edu.co nram.vel94@gmail.com
Lopez Rivera, Daniela Rhenals Montoya, Paula

Faculty of Chemical Engineering, University of Faculty of Chemical Engineering, University of
Pontificia Bolivariana Pontificia Bolivariana
Circular 83,50-86, Medellín 56006 Circular 54 77d-64, Medellín 56006
daniela.lopezriv@upb.edu.co paula.rhenalsm@gmail.com
Czech Republic
Aim, Karel Nezbeda, Ivo
Institute of Chemical Process Fundamentals of the Institute of Chemical Process Fundamentals of the
Czech Academy of Sciences Czech Academy of Sciences
Rozvojová 135, 165 02 Praha 6 Rozvojová 135, 165 02 Praha 6
kaim@icpf.cas.cz ivonez@icpf.cas.cz
Bogdanic, Grozdana Rotrekl, Jan

Institute of Chemical Process Fundamentals of the Institute of Chemical Process Fundamentals of the
Czech Academy of Sciences Czech Academy of Sciences
Rozvojová 135, 165 02 Praha 6 Rozvojová 135, 165 02 Praha 6
bogdanic@icpf.cas.cz rotrekl@icpf.cas.cz
Doubek, Martin Wichterle, Ivan

Czech technical University Institute of Chemical Process Fundamentals of the
Technicka 4, Praha 6, 16607 Praha Czech Academy of Sciences
martin.doubek@cern.ch Rozvojová 135, 165 02 Praha 6
wi@icpf.cas.cz
List of Participant
Michalec, Lukáš
Institute of Chemical Process Fundamentals of the
Czech Academy of Sciences
Rozvojová 135, 165 02 Praha 6
michalec@icpf.cas.cz
Denmark
Anantpinijwatna, Amata Kontogeorgis, Georgios
Technical University of Denmark Technical University of Denmark
Room 015 Building 239 Kolonnevej, 2800 Kgs. Building 229, Soltofts Plads, 2800 Kgs. Lyngby
Lyngby gk@kt.dtu.dk
amatana@kt.dtu.dk
Arya, Alay Vinhal, Andre Pinto Coelho Muniz

Building 229, Soltofts Plads, 2800 Kgs. Lyngby Building 229, Soltofts Plads, 2800 Kgs. Lyngby
alaya@kt.dtu.dk anpi@kt.dtu.dk
Gani, Rafiqul Schlaikjer, Anders

Building 229, Soltofts Plads, 2800 Kgs. Lyngby Building 229, Soltofts Plads, 2800 Kgs. Lyngby
rag@kt.dtu.dk andsh@kt.dtu.dk
Kalakul, Sawitree Tsanas, Christos

Anker Engelundsvej 1 Building 101A, 2800 Kgs Building 229, Soltofts Plads, 2800 Kgs. Lyngby
Lyngby ctsa@kemi.dtu.dk
sawit@kt.dtu.dk
France
Ballerat Busserolles, Karine Fouad, Oulebsir
Chemical Institute of Clermont-Ferrand University of Pau
Campus Universitaire des Cézeaux, 24 avenue Blaise UPPA, Avenue de l Universite, 64000 Pau
Pascal, TSA 60026 CS Aubiere fouad.oulebsir@univ-pau.fr
karine.ballerat@univ-bpclermont.fr
Baudouin, Olivier Galliero, Guillaume

ProSim SA University of Pau
Immeuble Stratege A, 51 Ampère Street, 31670 UPPA, Avenue de l Universite, 64000 Pau
Labege guillaume.galliero@univ-pau.fr
olivier.baudouin@prosim.net
Brehelin, Mathias Gaudin, Théophile

Research Center Lyon, SOLVAY R&I University ofTechnologie de Compiègne
85 Avenue des Frères Perret - BP 62, 69192 Saint- 60, Rue du Docteur Schweitzer, 76130 Compiègne
Fons theophile.gaudin@utc.fr
mathias.brehelin@solvay.com
Collell, Julien Gonzalez Perez, Alfonso

Total E&P Heriot-Watt/Mines ParisTech
Avenue Larribau, 64018 Pau 60 bld Saint-Michel, 75272 Paris
julien.collell@total.com alfonso.gonzalez@pet.hw.ac.uk
List of Participant
de Hemptinne, Jean-Charles Goutaudier, Christelle

IFP Energies Nouvelles University of Claude Bernard Lyon 1
1&4 avenue de Bois Preau, 92854 , Rueil Malmaison Chevreul Building, 43 bd 11 novembre, 69622
j-charles.de-hemptinne@ifpen.fr Villeurbanne cedex
christelle.goutaudier@univ-lyon1.fr
Janecek, Jiri Privat, Romain

ENSTA ParisTech University of Lorraine/ENSIC
828 Boulevard des Maréchaux, 91762 Palaiseau CNRS - SCTD 2573, TSA N° 51003, 54500 Vandoeuvre
cedex les Nancy
jiri.janecek@ensta-paristech.fr romain.privat@univ-lorraine.fr
Jaubert, Jean-Noël Puentes Mancipe, Cristian Felipe

University of Lorraine / ENSIC AgroParisTech
CNRS - SCTD 2573, TSA N° 51003, 54500 Vandoeuvre 1 Avenue des Olympiades, 91744 Massy
les Nancy cpuentestb@gmail.com
jean-noel.jaubert@univ-lorraine.fr
Lachet, Véronique Rousseau, Bernard

IFP Energies Nouvelles Physical Chemistry, University Paris-Sud, CNRS
1&4 avenue de Bois Preau, 92854 , Rueil Malmaison Laboratoire de Chimie Physique, Bâtiment 349,
veronique.lachet@ifpen.fr 91405 Orsay
bernard.rousseau@u-psud.fr
Neau, Evelyne Simond, Mickaël

Aix Marseille University CALNESIS
M2P2 - Laboratory of Physical Chemistry 20 Street Henri and Gilberte Goudier, 63200 Riom
163 Avenue de Luminy, 13000 MArseille mickael.simond@calnesis.com
evelyne.neau@univ-amu.fr
Nichita, Dan Vladimir Vermorel, Romain

University of Pau Univerty of Pau
UPPA, Avenue de l Universite, 64000 Pau UPPA, Avenue de l Universite, 64000 Pau
dan.nichita@univ-pau.fr romain.vermorel@univ-pau.fr
Nicolas, Christophe Wang, Tianyuan

Aix-Marseille University Mines Paristech
M2P2 - Laboratory of Physical Chemistry 60 bd Saint-Michel, 75272 Paris
163 Avenue de Luminy, 13000 MArseille tianyuan.wang@mines-paristech.fr
christophe.nicolas@univ-amu.fr
Paricaud, Patrice
ENSTA ParisTech, UCP
828 Boulevard des Maréchaux, 91762 Palaiseaux
cedex
patrice.paricaud@ensta-paristech.fr
Germany
Alves da Rocha, Marisa Alexandra Baz, Jörg
University of Bremen University of Stuttgart
Schinkelstraße 8, 52062 Aachen Pfaffenwaldring 9, 70569 Stuttgart
marisa.alexandra.rocha@gmail.com baz@itt.uni-stuttgart.de
List of Participant
Bauer, Gernot Bühl, Christian

University of Stuttgart ITTK, KIT
Pfaffenwaldring 9, 70569 Stuttgart Engler-Bunte Ring 21, 76131 Karlsruhe
Bauer@itt.uni-stuttgart.de christian.buehl@kit.edu
Dohrn, Ralf Langenbach, Kai

Bayer Technology Services and TU Hamburg-Harburg University of Kaiserslautern
51368 Leverkusen Erwin-Schrödinger-Str. 44, 67663 Kaiserslautern
ralf.dohrn@bayer.com Kai.Langenbach@mv.uni-kl.de
Groß, Joachim Lemberg, Max

University of Stuttgart TU Dortmund University
Pfaffenwaldring 9, 70569 Stuttgart Emil-Figge-Str. 70, 44221 Dortmund
sekretariat@itt.uni-stuttgart.de max.lemberg@bci.tu-dortmund.de
Hansen, Niels Leonhard, Kai

University of Stuttgart RWTH Aachen University
Pfaffenwaldring 9, 70569 Stuttgart Schinkelstraße 8, 52062 Aachen
hansen@itt.uni-stuttgart.de leonhard@ltt.rwth-aachen.de
Hasse, Hans Liebergesell, Bastian

Kaiserslautern University of Technology RWTH Aachen University
Erwin-Schrödinger-Straße 1, 67663 Kaiserslautern Schinkelstraße 8, 52062 Aachen
jennifer.bergmann@mv.uni-kl.de bastian.liebergesell@ltt.rwth-aachen.de
Heilig, Manfred Lötgering-Lin, Oliver

BASF SE University of Stuttgart
GCP/TD – L443, Carl-Bosch Str., 67056 Ludwigshafen Pfaffenwaldring 9, 70569 Stuttgart
romy.weinriefer@basf.com loetgering@itt.uni-stuttgart.de
Held, Christoph Mairhofer, Jonas

TU Dortmund University University of Stuttgart
Emil-Figge-Straße 72, 44221 Dortmund Pfaffenwaldring 9, 70569 Stuttgart
christoph.held@bci.tu-dortmund.de mairhofer@itt.uni-stuttgart.de
Hopp, Madlen Peters, Christine

University of Stuttgart RWTH Aachen University
Pfaffenwaldring 9, 70569 Stuttgart Schinkelstraße 8, 52062 Aachen
hopp@itt.uni-stuttgart.de christine.peters@ltt.rwth-aachen.de
Ji, Yuanhui Rathke, Bernd

TU Dortmund University University of Bremen
Emil-Figge-Str. 70, 44221 Dortmund Timmersloher Str. 16, 28215 Bremen
Yuanhui.Ji@bci.tu-dortmund.de rathke@uni-bremen.de
Kaminski, Sebastian Enders, Sabine

RWTH Aachen University ITTK, KIT
FB 4 Produktionstechnik, Badgasteiner Str. 1, 28359 Engler-Bunte Ring 21, 76131 Karlsruhe
Bremen sabine.enders@kit.edu
sebastian.kaminski@ltt.rwth-aachen.de
List of Participant
Kohns, Maximilian Sadowski, Gabriele

University of Kaiserslautern TU Dortmund University
Erwin-Schrödinger-Str. 44, 67663 Kaiserslautern Emil-Figge-Str. 70, 44221 Dortmund
maximilian.kohns@mv.uni-kl.de Gabriele.Sadowski@bci.tu-dortmund.de
Sass, Richard Walowski, Christoph

DECHEMA e.V. ITTK, KIT
Theodor-Heuss-Allee 25, 60486 Frankfurt Engler-Bunte Ring 21, 76131 Karlsruhe
sass@dechema.de christoph.walowski@kit.edu
Sauer, Elmar Weidler, Dominik

University of Stuttgart University of Stuttgart
Pfaffenwaldring 9, 70569 Stuttgart Pfaffenwaldring 9, 70569 Stuttgart
sauer@itt.uni-stuttgart.de weidler@itt.uni-stuttgart.de
Scheffczyk, Jan Zeiner, Tim

RWTH Aachen University TU Dortmund University
Schinkelstraße 8, 52062 Aachen Emil-Figge-Str. 70, 44221 Dortmund
jan.scheffczyk@ltt.rwth-aachen.de tim.zeiner@bci.tu-dortmund
Schilling, Johannes Zimmermann, Patrick

RWTH Aachen University ITTK, KIT
Schinkelstraße 8, 52062 Aachen Engler-Bunte Ring 21, 76131 Karlsruhe
johannes.schilling@ltt.rwth-aachen.de patrick.zimmermann@kit.edu
Voges, Matthias Zmpitas, Wasilios

TU Dortmund University University of Stuttgart
Emil-Figge-Str. 70, 44221 Dortmund Pfaffenwaldring 9, 70569 Stuttgart
matthias.voges@bci.tu-dortmund.de zmpitas@itt.uni-stuttgart.de
Waibel, Christian
University of Stuttgart
Pfaffenwaldring 9, 70569 Stuttgart
waibel@itt.uni-stuttgart.de
Greece
Theodorou, Doros N. Vergadou, Niki
National Technical University of Athens NCSR "Demokritos"
9, Heroon Polytechniou Str., Zographou Campos, Kolokotroni 102 Str, 13231 Petroupoli
15780 Athens n.vergadou@inn.demokritos.gr
doros@chemeng.ntua.gr
India
George, Ankitha Theres Pathayaturayil, Janakey Devi Vayavinat Kizhakkepat
Indian Institute of Technoplogy Madras, Chennai Institute of Technology Madras, Chennai
Room no:212, Chemical Engineering Laboratory, IIT Room no:212, Chemical Engineering Laboratory, IIT
Madras, 600036 Chennai Madras, 600036 Chennai
georgeankitha@gmail.com janakiparrat@gmail.com
List of Participant
Iran
Jalili, Amir Hossein Raeissi, Sona
Research Institute of Petroleum Industry Shiraz University
West side of Azadi Complex, 1485733111 Tehran Molla Sadra Street, School of Chemical and
jaliliah@ripi.ir Petroleum Engineering, 71345 Shiraz
s_raeissi@yahoo.com
Shariati, Alireza Taghi Zoghi, Ali
Shiraz University Research Institute of Petroleum Industry
Molla Sadra Street, School of Chemical and West side of Azadi Complex, 1485733111 Tehran
Petroleum Engineering, 71345 Shiraz zoghiat@ripi.ir
shariati@shirazu.ac.ir
Italy
Mio, Andrea
University of Trieste
Alfonso Valerio Street, 6/1, 34127 Trieste
andrea.mio@phd.units.it
Japan
Funazukuri, Toshitaka Makino, Takashi
Chuo University National Institute of Advanced Industrial Science and
1-13-27 Kasuga, 112-8551 Tokyo Technology
tfunazo@kc.chuo-u.ac.jp 4-2-1 Nigatake, Miyagino-ku, 983-8551 Sendai
makino.t@aist.go.jp
Hiraga, Yuya Matsuda, Hiroyuki

Tohoku University Nihon University
Aramaki Aza Aoba 6-6-11-414, Aoba-ku, 980-8579 1-8-14 Kanda Surugadai, Chiyoda-ku, 101-8308
Sendai Tokyo
yuya-h@scf.che.tohoku.ac.jp matsuda.hiroyuki@nihon-u.ac.jp
Iwai, Yoshio Nishiumi, Hideo

Kyushu University Hosei University
744 Motooka, Nishi-ku, 819-0395 Fukuoka 3-25-12 Shinmei, 191-0016 Hino-city, Tokyo
iwai@chem-eng.kyushu-u.ac.jp nishi@hosei.ac.jp
Kanakubo, Mitsuhiro Oba, Shigeo

National Institute of Advanced Industrial Science and AT-PP, Co., Ltd.
Technology 1-12-11-505 Sodegaura, 275-0021 Narashino
4-2-1 Nigatake, Miyagino-ku, 983-8551 Sendai shigeo.oba@at-pp.co.jp
m-kanakubo@aist.go.jp
Kayukawa, Yohei Sugahara, Takeshi

AIST Tsukuba Central Osaka University
AIST Tsukuba Central 3, 1-1-1, Umezono, 3058563 1-1 Yamadaoka, Suita, Osaka Prefecture 565-0871
Tsukuba sugahara@cheng.es.osaka-u.ac.jp
kayukawa-y@aist.go.jp
List of Participant
Kodama, Daisuke Tamura, Kazuhiro

College of Engineering, Nihon University Kanazawa University
1 Nakagawara, Tokusada, Tamura-machi, 963-8642 Kakuma-machi, 920-1192 Kanazawa
Koriyama, Fukushima tamura@se.kanazawa-u.ac.jp
dkodama@chem.ce.nihon-u.ac.jp
Kurihara, Kiyofumi Ushiki, Ikuo

Nihon university Tohoku University
1-8-14 Kanda Surugadai, Chiyoda-ku, 101-8308 6-6-11-403, Aoba, Aramaki, Aoba-ku, 980-8579
Tokyo Sendai
kurihara.kiyofumi@nihon-u.ac.jp iushiki@scf.che.tohoku.ac.jp
Watanabe, Masaki Yamada, Junya

College of Engineering, Nihon University Inpex Corporation
1 Nakagawara, Tokusada, Tamura-machi, 963-8642 9-23-30 Kitakarasuyama, Setagaya-ku, 157-0061
Koriyama, Fukushima Tokyo
nabe.0410@gmail.com junya.yamada@inpex.co.jp
Korea, Republic of South

Choi, Jisu Yang, Hanearl
Hanyang University Hanyang University
17 Haengdang-dong, Seongdong-gu, 4763, Seoul 17 Haengdang-dong, Seongdong-gu, 4763, Seoul
laiaa214@hanyang.ac.kr haner12@hanyang.ac.kr
Lee, Chan Hee

Hanyang University
17 Haengdang-dong, Seongdong-gu, 4763, Seoul
chyicap@hanyang.ac.kr
Malaysia
Tsuji, Tomoya
Universiti Teknologi Malaysia
Off Jalan Sultan Yahya Petra, 54100, Kuala Lumpur
t5tsuji.tomoya@gmail.com
Mexico
Bonilla-Petriciolet, Adrián Rebolledo-Libreros, María Esther
Instituto Tecnologico de Aguascalientes Instituto Mexicano del Petróleo
Av. Lopez Mateos 1801, Fracc. Bonagens Eje Central Lázaro Cárdenas Norte 152, San Bartolo
20256, Aguascalientes Atepehuacan, Gustavo A. Madero, 7730, México,
ileana.mencas@gmail.com Distrito Federal
mrebolle@imp.mx
Mendoza-Castillo, Didilia I.
Instituto Tecnologico de Aguascalientes
Av. Lopez Mateos 1801, Fracc. Bonagens
20256, Aguascalientes
didi_meca@yahoo.com.mx
List of Participant
Netherlands
Blahušiak, Marek Mattei, Michele
University of TWENTE AkzoNobel
Drienerlolaan 5, 7522 NB, Enschede Zutphenseweg 10, 7418 AJ, Deventer
m.blahusiak@utwente.nl michele.mattei@akzonobel.com
de Loos, Theo Rodriguez Rodriguez, Nerea

T.U. Delft Eindhoven University of Technology
Leeghwaterstraat 39, 2628 CB,Delft Groene Loper 5, 5612 AE, Eindhoven
t.w.deloos@tudelft.nl n.rodriguez@tue.nl
Dijk, Nicolette Sweere, Teun

Elsevier Leiden University
Radarweg 29, 1043, Amsterdam Einsteinweg 55, 2333CC, Leiden
n.vandijk@elsevier.com a.j.m.sweere@chem.leidenuniv.nl
Fraaije, Johannes van Bochove, Gerard

Leiden University Corbion
Einsteinweg 55, 2300 RA, Leiden Arkelsedijk 46, 4206AC, Gorinchem
hans@culgi.com g.van.bochove@corbion.com
Hendriks, Eric van Osch, Dannie

Shell Global Solutions Eindhoven University of Technology
Grasweg 31, 1031 HW, Amsterdam Groene Loper 5, 5612 AE, Eindhoven
eric.hendriks@shell.com D.v.Osch@tue.nl
Kollau, Laura Westerholt, Antje

Eindhoven University of Technology Shell
PO box 513, 5600MB, Eindhoven Grasweg 31, 1031 HW, Amsterdam
l.kollau@tue.nl antje.westerholt@shell.com
Lawien, Zubeir
Eindhoven University of Technology
Groene Loper 5, 5612 AZ, Eindhoven
l.f.zubeir@tue.nl
New Zealand
Kato, Satoru
TC Lines NZ Ltd.
94 Balrudry St., Avonhead, 8042, Christchurch
kato@tc-lines.com
Norway
Kvamme, Bjørn
University of Bergen
Allégaten 55, 5007, Bergen
bjorn.kvamme@ift.uib.no
List of Participant
Poland
Malgorzata, Sliwinska-Bartkowiak Paduszyński, Kamil
Adam Mickiewicz University Warsaw University of Technology
Umultowska 85, 61-614 Poznan Pl. Politechniki 1, 00-664 Warsaw
msb@amu.edu.pl kpaduszynski@ch.pw.edu.pl
Portugal
Almeida Santos, Diogo Martins, Luís
CUF-Químicos Industriais, SA Universidade de Évora
Rua do Amoníaco Português, n. 10 Av. Rovisco Pais 1, 1049-001, Lisboa
Q.ta da Indústria, Beduído, 3860-680, Estarreja lfgm@uevora.pt
diogo.santos@cuf-qi.pt
Araújo, João Martins de Andrade, Carlos

ITQB-UNL GALP
Av. da República, 2780-157, Oeiras Rua Tomás da Fonseca - Torre C, 1600-209, Lisboa
jmmda@itqb.unl.pt martins.andrade@galpenergia.com
Canongia Lopes, José Nuno Nunes da Ponte, Manuel

Instituto Superior Técnico Universidade Nova de Lisboa
Av. Rovisco Pais, 1049-001, Lisbon 2829-516, Caparica
zenunoi@me.com mnp@fct.unl.pt
Maria Emília Lopes Borges Ferreira Casaca Palma, André

FEUP Universidade de Aveiro
Rua Dr. Roberto Frias, 4200-465, Porto Campus Universitário de Santiago, 3810-193, Aveiro
mecasaca@gmail.com andre.palma@ua.pt
Duarte, Pedro Pereiro, Ana B

Instituto Superior Técnico ITQB/UNL
Av. Rovisco Pais, 1049-001, Lisbon Av. da República, 2780-157, Oeiras
pedro.duarte@tecnico.ulisboa.pt anab@itqb.unl.pt
Esperança, José Shimizu, Karina

ITQB/UNL Instituto Superior Técnico
Av. da República, 2780-157, Oeiras Av. Rovisco Pais, 1049-001, Lisbon
jmesp@itqb.unl.pt karina.shimizu@tecnico.ulisboa.pt
Filipe, Eduardo Silva, Gonçalo

Instituto Superior Técnico Instituto Superior Técnico
Av. Rovisco Pais, 1049-001, Lisbon Av. Rovisco Pais, 1049-001, Lisbon
efilipe@ist.utl.pt goncalo.silva20@gmail.com
Macedo, Maria Eugenia Marrucho, Isabel

FEUP ITQB/UNL
Rua Dr. Roberto Frias, 4200-465, Porto Av. da República, 2780-157, Oeiras
eamacedo@fe.up.pt imarrucho@itqb.unl.pt
Wysoczanska, Kamila
FEUP
Rua Dr. Roberto Frias, 4200-465, Porto
wysoczanska.kamila@gmail.com
List of Participant
Qatar
Altamash, Tausif G. Economou, Ioannis
Qatar University Texas A&M University at Qatar
2713, Doha PO Box 23874 Education City, 974, Doha
tausif.altamash@qu.edu.qa ioannis.economou@qatar.tamu.edu
Castier, Marcelo Selam, Muaz

Texas A&M University at Qatar Texas A&M University at Qatar
PO Box 23874 Education City, 974, Doha PO Box 23874 Education City, 974, Doha
marcelo.castier@qatar.tamu.edu muaz.selam@qatar.tamu.edu
Dawass, Noura
Texas A&M University at Qatar
PO Box 23874 Education City, 974, Doha
noura.dowass@qatar.tamu.edu
Romania
Secuianu, Catinca
University Politehnica of Bucharest
1-7 Gh. Polizu Street, S1, Building E, 3rd Floor, Room
E304-305, 11061, Bucharest
c_secuianu@chim.upb.ro
Russia
Kovalenko, Nikita Victorov, Alexey
Lomonosov Moscow State University St.Petersburg State University
Leninskie gory, 1-3, 119991, Moscow Universitetsky prosp., 26, 199504, St.Petersburg
kovalenko@td.chem.msu.ru victorov_a@yahoo.com
Maksimov, Aleksey Voskov, Alexey

Moscow State University Lomonosov Moscow State University
Leninskie Gory 1, b. 3, 119991, Moscow Leninskie gory, 1-3, 119991, Moscow
maksimoff@chemist.com alvoskov@gmail.com
Varfolomeev, Mikhail
Kazan Federal University
Kremlevskaya str. 18, 420008, Kazan
mikhail.varfolomeev@kpfu.ru
Serbia
Kijevcanin, Mirjana Radovic, Ivona
University of Belgrade University of Belgrade
Karnegijeva 4, 11000, Belgrade Karnegijeva 4, 11000, Belgrade
mirjana@tmf.bg.ac.rs ivonag@tmf.bg.ac.rs
Spain
Aguilar-Romero, Fernando Lladosa, Estela
Universidad de Burgos University of Valencia
Avda. Cantabria s/n, E 09006, Burgos Avda. Universitat s/n, Escuela Técnica Superior de
faguilar@ubu.es Ingeniería, 46100, Burjassot
estela.lladosa@uv.es
List of Participant
Arce, Alberto Llovell, Fèlix

Universidade de Santiago Compostela IQS School of Engineering
Rúa Lope Gómez de marzoa, s/n, E-15782, Santiago Via Augusta, 390, 8017, Barcelona
de Compostela felix.llovell@iqs.edu
alberto.arce@usc.es
Concepción Rodríguez, Eduardo Muñoz-Rujas, Natalia

Universidad de Valladolid Universidad de Burgos
Plaza Colegio Santa Cruz, 47002, Valladolid Avenida Cantabria s/n, 9006, Burgos
eduardo.concepcion1@utp.ac.pa nmrujas@ubu.es
Diez-Alcalde, Diana Perez Armada, Lorena

Universidad de Burgos University of Vigo
Hospital del Rey S/N, 9001, Burgos Lagoas Marcosende, 36310, Vigo
ddiezalcalde@gmail.com lorenaperezarmada@gmail.com
Domínguez, Ángeles Rodriguez, Oscar

University of Vigo Universidade de Santiago Compostela
Lagoas Marcosende, 36310, Vigo Rúa Lope Gómez de marzoa, s/n, E-15782, Santiago
admguez@uvigo.es de Compostela
oscar.rodriguez@usd.es
Domínguez, Irene Rubio Gallego, Jorge

University of Vigo Universidad de Valladolid
Lagoas Marcosende, 36310, Vigo Plaza Colegio Santa Cruz 8, 47002, Valladolid
irene@uvigo.es jorge.rubio.gallego@alumnos.uva.es
Fernández Suárez, Luis Jesús Sosa Marco, Adriel

Universidad de Las Palmas de Gran Canaria Universidad de Las Palmas de Gran Canaria
c/ Juan de Quesada, 30, 35001, Las Palmas de Gran c/Juan de Quesada, 30, 35001, Las Palmas de Gran
Canaria Canaria
luis.fdz.suarez@gmail.com adriel.sm10@gmail.com
Fidalgo Blanco, Ruben Soto Campos, Ana

University of Vigo Universidade de Santiago Compostela
Lagoas Marcosende, 36310, Vigo Rúa Lope Gómez de marzoa, s/n, E-15782, Santiago
rubenfidalgob@gmail.com de Compostela
ana.soto@usc.es
González, Begoña Vega de Las Heras, Carlos

University of Vigo Universidad Complutense de Madrid
Lagoas Marcosende, 36310, Vigo Madrid
bgp@uvigo.es cvega@quim.ucm.es
González Sas, Olalla Zarca, Gabriel

University of Vigo Universidad de Cantabria
Lagoas Marcosende, 36310, Vigo Av. Los Castros s/n, 39005, Santander
olallags83@uvigo.es gabriel.zarca@unican.es
List of Participant
Gorri, Daniel
Universidad de Cantabria
Avda. de los Castros s/n, 39005, Santander
gorrie@unican.es
Sweden
Ji, Xiaoyan Xie, Yujiao
Luleå Tekniska Universitet Luleå Tekniska Universitet
97187, Luleå Fakturaservice FE 227, Frösön, 83873, Lulea
xiaoyan.ji@ltu.se yujiao.xie@ltu.se
Pajalic, Oleg
Perstorp
Kärnyxvägen 2, 29166, Kristianstad
oleg.pajalic@perstorp.com
Switzerland
Dupas-Langlet, Marina Ottiger, Stefan
Nestlé Research Center Lonza AG
Route du Jorat, Vers-chez-les-blanc, 1000, Lausanne Lonzastrasse, 3930, Visp
marina.dupas-langlet@rdls.nestle.com stefan.ottiger@lonza.com
Gruetzner, Thomas Piccolo, Chiara

Lonza AG Firmenich SA
Lonzastrasse, 3930, Visp Route de la Plaine 125, 1283, La Plaine
thomas.gruetzner@lonza.com chiara.piccolo@firmenich.com
Mascarello, Francesco
DSM Nutritional Products
Wurmisweg 576, CH-4303 Kaiseraugst
francesco.mascarello@dsm.com
Thailand
Ratanavaraha, Vatanavongs
Suranaree University of Technology
111 University Ave., Suranaree, Muang, 30000,
Nakhon Ratchasima
panarat@sut.ac.th
United Arab Emirates

Kroon, Maaike Vega, Lourdes
Petroleum Institute Petroleum Institute
P.O.Box 2533, P.O.Box 2533, Abu Dhabi P.O.Box 2533, P.O.Box 2533, Abu Dhabi
mkroon@pi.ac.ae lourdes.f.vega@gmail.com
Peters, Cornelis
Petroleum Institute
P.O.Box 2533, P.O.Box 2533, Abu Dhabi
cpeters@pi.ac.ae
List of Participant
United Kingdom
Al-Jadir, Thaer Munem Mac Dowell, Niall
University of Manchester Imperial College London
Oxford Road, The Mill, M13 9PL, Manchester 14 Princes Gardens, SW7 1NA, London
thaer.al-jadir@postgrad.manchester.ac.uk nmac-dow@ic.ac.uk
Chia, Chung Lim McBride, John

University of Manchester University of Manchester
Oxford Road, The Mill, M13 9PL, Manchester Oxford Road, The Mill, M13 9PL, Manchester
chunglim.chia@manchester.ac.uk john.mcbride@postgrad.manchester.ac.uk
dos Santos de Souza, Lorena Fernanda Mota-Martinez, Maria Teresa

Imperial College London Imperial College London
South Kensington Campus, SW7 2AZ, London South Kensington Campus, SW7 2AZ, London
ld14@imperial.ac.uk m.mota-martinez@imperial.ac.uk
Febra, Sara Muller, Erich

Imperial College London Imperial College London
South Kensington Campus, SW7 2AZ, London South Kensington Campus, SW7 2AZ, London
s.febra14@imperial.ac.uk e.muller@imperial.ac.uk
Fisher, Laura Pakalidou, Nikoletta

Royal Society of Chemistry University of Manchester
Thomas Graham House, 290 Science Park, Milton Rd, Oxford Road, The Mill, M13 9PL, Manchester
CB4 0WF, Cambridge nikoletta.pakalidou@manchester.ac.uk
fisherl@rsc.org
Galindo, Amparo Phan, Anh

Imperial College London University College London
South Kensington Campus, SW7 2AZ, London Roberts Building, Torrington Place, WC1E 7JE,
a.galindo@imperial.ac.uk London
anh.phan.13@ucl.ac.uk
Haslam, Andrew Queimada, Antonio

Imperial College London KBC Process Technology
South Kensington Campus, SW7 2AZ, London 93 Great Suffolk Street, SE1 0BX, London
a.haslam@imperial.ac.uk AQueimada@kbcat.com
Hutacharoen, Panatpong Hutacharoen Siperstein, Flor

Imperial College London University of Manchester
South Kensington Campus, SW7 2AZ, London Oxford Road, The Mill, M13 9PL, Manchester
ph1812@ic.ac.uk flor.siperstein@manchester.ac.uk
Jackson, George Striolo, Alberto

Imperial College London University College London
South Kensington Campus, SW7 2AZ, London Roberts Building, Torrington Place, WC1E 7JE,
g.jackson@imperial.ac.uk London
a.striolo@ucl.ac.uk
List of Participant
Jimenez Serratos, M Guadalupe Tasche, Jos

Imperial College London University of Durham
South Kensington Campus, SW7 2AZ, London South Road, DH1 3LE, Durham
mgjimene@ic.ac.uk jos.tasche@durham.ac.uk
Lafitte, Thomas Trusler, J P Martin

Process Systems Enterprise Imperial College London
London, United Kingdom South Kensington Campus, SW7 2AZ, London
t.lafitte@psenterprise.com m.trusler@imperial.ac.uk
Lazarou, Georgia Zhao, Nan

Imperial College London Queen's University Belfast
South Kensington Campus, SW7 2AZ, London David Kier Building, Stranmillis Road, BT95AG,
georgia.lazarou12@imperial.ac.uk Belfast
nzhao01@qub.ac.uk
Lindeboom, Tom
Imperial College London
Orient House, Station Court Imperial Road, SW6 2EP,
London
trl11@ic.ac.uk
United States
Clark, Robert Marin Rimoldi, Eliseo
University of Houston University of Notre Dame
4726 Calhoun Rd, S222 Engineering Building 1, 2627 Arabian Court Apt 1B, 46628, South Bend
77204, Houston emarinri@nd.edu
cord.palmer@gmail.com
Cummings, Peter Mathias, Paul

Vanderbilt University Fluor Corporation
1727 Hillmont Dr, 37215, Nashville 3 Polaris Way, CA 92698, Aliso Viejo
peter.cummings@vanderbilt.edu Paul.Mathias@Fluor.com
de Pablo, Juan Mccabe, Clare

University of Chicago Vanderbilt University
5747 S. Ellis Avenue, Chicago IL 60637 1727 Hillmont Dr, 37215, Nashville
depablo@uchicago.edu c.mccabe@vanderbilt.edu
Elimelech, Menachem McClurg, Richard

Yale University SSCI, a division of AMRI
P.O. Box 208286 (express mail: 9 Hillhouse Avenue) 3065 Kent Ave., 47906, West Lafayette, IN
New Haven, CT 06520-8286 richard.mcclurg@amriglobal.com
meny.elimelech@gmail.com
Errington, Jeffrey Messerly, Richard A. Messerly

University at Buffalo Brigham Young University
509 Furnas Hall, 14260, Buffalo Clyde Building, Room 350, 84602, Provo
jerring@buffalo.edu ramess101@gmail.com
List of Participant
Gubbins, Keith O’Connell, John

North Carolina State University University of Virginia
911 Partners Way, 27695, Raleigh 1762 Blue Court, 93444, Nipomo, CA
keg@ncsu.edu jpo2x@eservices.virginia.edu
Hall, Carol Palmer, Jeremy

North Carolina State University University of Houston
911 Partners Way, 27695, Raleigh 4726 Calhoun Rd, S222 Engineering Building 1,
hall@ncsu.edu 77204, Houston
jpalmer2@central.uh.edu
Hanna, Tamara Panagiotopoulos, Athanassios

American Chemical Society Princeton Unversity
1155 16th St NW, 20036, Washington A317 Engineering Quadrangle, NJ 08544, Princeton
T_Hanna@acs.org azp@princeton.edu
Huang, Liangliang Pervaje, Amulya

University of Oklahoma North Carolina State University
Sarkeys Energy Center, 100 E Boyd Street, Norman, 2413 Long and Winding Rd, 27603 Raleigh, NC
OK 73019 akpervaj@ncsu.edu
hll@ou.edu
Islam, Md Santiso, Erik

Texas Tech University North Carolina State University
6th and Canton Avenue, 79409, Lubbock 911 Partners Way, Room 7905, 27695-7905, Raleigh,
md.islam@ttu.edu NC
eesantis@ncsu.edu
Jiang, Hao Sarupria, Sapna

Princeton University Clemson University
08544, Princeton 206 S Palmetto Blvd, Earle Hall, 29634, Clemson
haoj@princeton.edu ssarupr@g.clemson.edu
Kim, Sang Beom Satyro, Marco

Princeton University Clarkson University
08544, Princeton 8 Clarkson Ave., 13699, Potsdam
sangbk@princeton.edu msatyro@clarkson.edu
Klein, Christoph Schultz, Andrew

Vanderbilt University University at Buffalo
1727 HILLMONT DR, 37215, Nashville 509 Furnas Hall, 14260, Buffalo, NY
christoph.klein@vanderbilt.edu ajs42@buffalo.edu
Kofke, David Shell, M. Scott

University at Buffalo University of California, Santa Barbara
303 Furnas Hall, 14260-4200, Buffalo 93106-5080, Santa Barbara
kofke@buffalo.edu shell@engineering.ucsb.edu
Koh, Carolyn Siepmann, Ilja

Colorado School of Mines University of Minnesota
CO 80401, Golden 207 Pleasant Street SE, MN 55455, Minneapolis
ckoh@mines.edu siepmann@umn.edu
List of Participant
Kroenlein, Kenneth Srivastava, Deepti

NIST North Carolina State University
325 Broadway MS 647.01, 80305, Boulder, CO 911 Partners Way, 27606, Raleigh
kenneth.kroenlein@nist.gov dsrivas@ncsu.edu
Lee, Lloyd Sandler, Stanley I

California State University University of Delaware
3801 West Temple Avenue, CA 91768, Pomona 233 CLB, Newark, Delaware 19716
profllee@yahoo.com sandler@udel.edu
Lingampally, Prasanna Lakshmi Thommes, Matthias

Cognizant Corp., India Quantachrome Instruments
10900 Equity Dr, 77041, Houston Boynton Beach, Florida
PrasannaLakshmi.Lingampally@cognizant.com matthias.thommes@quantachrome.com
Lubben, Michael Xu, Gang

University of Notre Dame Schneider-Electric
182 Fitzpatrick Hall, 46556, Notre Dame 26561 Rancho Parkway South, suite 100, 92630, Lake
mlubben@nd.edu Forest, CA
Gang.Xu.us@schneider-electric.com
Mansfield, Elisabeth
National Institute of Standards and Technology
325 Broadway, MS 647, 80305, Boulder
elisabeth.mansfield@nist.gov

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PPEPPD 2016 Oporto Abstract Book

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BOOK OF ABSTRACTS

14th International Conference on Properties and

22-26 May 2016, Porto, Portugal

José Nuno Canongia Lopes

Faculdade de Engenharia da Universidade do Porto

Title: Book of Abstracts - 14th International Conference on Properties and

Author: Maria Eugénia Rebello de Almeida Macedo

Co-author: José Nuno Canongia Lopes

First Edition: May 2016

Credits to: Emília Casaca

© Faculdade de Engenharia da Universidade do Porto

Dear Friend and Participant,

It is our great pleasure to welcome you to the 14th International Conference on

International Organizing Committee

Maria Eugénia Rebello de A. Macedo (Chair) University of Porto, Portugal

José Nuno Canongia Lopes (Co-Chair) University of Lisbon, Portugal

Susana Bottini Universidad Nacional del Sur,

Joan Brennecke University of Notre Dame, USA

Ioannis G. Economou Texas A&M University, Qatar

João F. Fugas CUF, Portugal

Xiaohua Lu Nanjing University of Technology,

John O’Connell University of Virginia, USA

Athanassios Z. Panagiotopoulos Princeton University, USA

Cor Peters Delft University of Technology,

The Petroleum Institute,

Gabriele Sadowski Technical University of Dortmund,

John Shaw University of Alberta, Canada

Local Organizing Committee

International Advisory Board PPEPPD 2016

THERMOPHYSICAL PROPERTIES AND

NEW TOPIC EXPERTS JOIN JCED AS ASSOCIATE EDITORS

David Kofke J. Ilja Siepmann

The Journal of Chemical & Engineering Data (JCED) publishes data

* The 2014 Journal Citation Reports® (JCR) from Thomson Reuters

Submit your best papers

1977: Asilomar, California, USA

Oral Sessions / Speakers Preparation Room and Slide Desk

Scope and Topics

Processing and Applications

John M. Prausnitz Award

List of previous awardees:

Distinguished Lecture of Working Party on TTP - EFCE

The PPEPPD Conferences 1977-2013

The presentation will introduce the book format and contents.

Special Issue of Journal of Chemical & Engineering Data

Sunday Evening – May, 22

18:45 Opening Session (Costa Verde)

Monday Morning – May, 23

Invited Lecture 1 (Costa Verde)

Oral Session 1: Molecular Modeling and SimulaWon 1 (Costa Verde)

Oral Session 2: Carbon Capture and Storage (Nova Iorque)

Monday Lunchtime – May, 23

Poster Sessions Foyer

Prediction of safety-relevant properties for multicomponent PU raw-material

The spreading behavior of surfactant-laden aqueous droplets on textured surface

Predicting asphaltene precipitation in petroleum fluids via NRTL-SAC

Modeling phase equilibria of semiclathrate hydrates of CH4, CO2, N2 and gas

Development of a comprehensive molecular thermodynamic model for high

Influence of PEG’s molecular weight on different polymer/salt ATPS phase

Application of PPR78 thermodynamic framework as fill method for semi-empirical

Prediction of solvent effects on reaction kinetics

Common features shared by a pure substance and a binary azeotrope

COSMO-CAMD: A framework for computer-aided molecular design with COSMO-RS

Monday Lunchtime – May, 23

Title: Book of Abstracts - 14th International Conference on Properties and

Author: Maria Eugénia Rebello de Almeida Macedo