Scientific Programme
and
Book of Abstracts
COMPILED BY:
RICARDO A. E. CASTRO
& TERESA M. ROSEIRO MARIA
DEPARTMENT OF CHEMISTRY | FACULTY OF PHARMACY
UNIVERSITY OF COIMBRA, PORTUGAL
25-27 MARCH 2015
Cover and JEEP 2015 logo: © Mário Rosado
TITLE: 41st Conference on Phase Equilibria | XLIèmes Journées d’Étude
des Équilibres entre Phases | JEEP 2015
Date: 25-27 March 2015
Publisher: João Canotilho & M. Ermelinda S. Eusébio
Publisher identification: 978-989-20-5592
Printed by:
XLIÈMES Journées d’Étude des Équilibres entre Phases JEEP 2015
INDEX
Foreword
5
The Historical Course of JEEP
6
General Information
7
Social Programme
9
Practical Information
12
Committees
13
Scientific Programme
15
Scientific Contributions
23
Abstracts
Workshop for Young Scientists
41
Plenary Lectures
47
Oral Communications
53
Poster Communications
77
List of Participants
149
3
Foreword
The JEEP conferences (Journées d'Étude des Équilibres entre Phases) have a long
history. Since the first time in Marseille-Luminy, this meeting has been organized
mostly in France, notwithstanding its occasional location in other European and African
countries throughout the years.
The steering committee that met in Lyon on the occasion of the 40 th JEEP decided to
invite the University of Coimbra to organize the conference in its 40 th anniversary in
2015, for the first time in Portugal.
The year 2015 is also an important date for the University of Coimbra, since it
celebrates the venerable age of 725 years old, having being established by the royal
charter Scientiae thesaurus mirabilis, in the 1st of March 1290 by king D. Dinis. The
University has recently been added by UNESCO to the list of World Heritage Sites.
The 41st Conference on Phase Equilibria (JEEP 2015) brings together relevant scientific
contributions to this ever expanding area, which applies to such multidisciplinary fields
as chemistry, pharmaceutics, material science, process engineering, environment. The
great variety of subjects presented in this conference is a testimony to the importance
of phase equilibria applications. It will be an opportune occasion to discuss the latest
developments and challenges, confronting diverse approaches from researchers
working in different scientific environments and cultures.
This brief stay among us will surely allow the participants to take a glimpse at the
variety of experiences that Coimbra, its university and Portugal have to offer. This will
surely entice them to come back later for a lengthier stay for a period of scientific
cooperation or personal leisure in our country.
We wish you a fruitful scientific and social event, and welcome you to JEEP 2015.
On behalf of the Organizing Committee
M. Ermelinda Eusébio
João Canotilho
5
THE HISTORICAL COURSE OF JEEP
1st
2nd
3rd
4th
5th
6th
7th
8th
9th
10th
11th
12th
13th
14th
15th
16th
17th
18th
19th
20th
21th
22th
23th
24th
25th
26th
27th
28th
29th
30th
31th
32th
33th
34th
35th
36th
37th
38th
39th
40th
41th
1975
1976
1977
1978
1979
1980
1981
1982
1983
1984
1985
1986
1987
1988
1989
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010
2011
2012
2013
2014
2015
Marseille
Lyon
Montpellier
Grenoble
Chatenay-Malabry
Nancy
Genève
Orsay
Barcelona
Tours
Marseille
Bordeaux
Lyon
Montpellier
Grenoble
Marseille
Utrecht
Chatenay-Malabry
Barcelona
Bordeaux
Rouen
Toulon
Hammamet
Nancy
Annecy
Marseille
Montpellier
Agadir
Lyon
St Avold
Barcelona
Rouen
Villeurbanne
Marrakech
Annecy
Montpellier
St Avold
Rouen
Nancy
Lyon
Coimbra
L. CARBONNEL
R. COHEN-ADAD
A. POTIER
I. ANSARA
B. LEGENDRE
J. HERTZ
J.L. JORDA
M. GHELFENSTEIN
M.T. CLAVAGUERA-MORA
R. CEOLIN
M. GAMBINO, G. HATEM
Y. HAGET
J.J. COUNIOUX, M.T. COHEN-ADAD
G. MASHERPA, J.C. TEDENAC
I. ANSARA, C. COLINET
J. PASTOR, J. KALOUSTIAN
H. OONK
B. LEGENDRE
M.A. CUEVAS-DIARTE, J.L. TAMARIT, E. ESTOP
Y. HAGET, A. MARBOEUF
R. BOUAZIZ, G. COQUEREL, M.N. PETIT
J. MUSSO, P. SATRE, A. SEBAOUN
M.M. ABDELKAFI, N. ARIGUIB, N. GUERFEL
J.C. GACHON ET AL.
J.L. JORDA ET AL.
C. BERGMAN, G. HATEM
J.C. TEDENAC ET AL.
M. EL HADEK ET AL.
J.C. VIALA ET AL.
M. COCHEZ, M. FERRIOL
T. CALVET, JL. TAMARIT
G. COQUEREL, M.N. PETIT, Y. CARTIGNY
M. PERONNET, C. GOUTAUDIER
M. NADIFIYINE, M. BENCHANAA
M. LOMELLO
R.M. AYRAL, F. ROUESSAC, J.C. TEDENAC
M. AILLERIE, M. COCHEZ, M. FERRIOL
G. COQUEREL, Y. CARTIGNY, M. PETIT, N. COUVRAT
N. DAVID, J.N. JAUBERT, R. PRIVAT
C. GOUTAUDIER ET AL.
M. ERMELINDA S. EUSÉBIO, J. CANOTILHO
6
GENERAL INFORMATION
Registration / Welcome desk:
With this Book of Abstracts, you will receive your participant badge and other
conference documentation. The registration desks are located in the
Department of Chemistry on Wednesday and in the University Auditorium on
Thursday and Friday.
Location:
Department of Chemistry
and
University Auditorium
Rua Larga
3004-535 Coimbra
GPS:
40.207836, -8.423864
City buses and trams:
http://www.smtuc.pt/geral/index_mapa.php
Buses number 34 and 28 stop in front of the University Auditorium.
Taxis
http://www.politaxis.pt
(+351) 239 499 090
7
[email protected]
SOCIAL PROGRAMME
Wednesday, 25th of March
19:00 GUIDED WALKING TOUR IN COIMBRA (PLACES TO VISIT)
University of Coimbra
Old Cathedral
Via Latina
Sé Velha
Visconde da Luz/Ferreira Borges/Sofia Streets
Mosteiro de Santa Cruz
Café Santa Cruz
Sá da Bandeira Avenue
Republic Square
Jardim Sá da Bandeira
Praça da República
9
SOCIAL PROGRAMME
Thursday, 26th of March
20:15 GALA DINNER AT QUINTA DAS LÁGRIMAS
http://www.quintadaslagrimas.pt
It was at Quinta das Lágrimas that in the XIVth century Prince Pedro and Inês
de Castro lived their forbidden love affair. Legend says that it was here that
Inês cried for the last time, while being pierced by the daggers of the killers sent
by King Afonso, Pedro´s father.
Her blood still colors the stone-bed of the fountain that was born of her tears,
the tears that gave the name of this romantic estate.
10
SOCIAL PROGRAMME
Friday, 27th of March
14:15 GUIDED VISIT TO THE UNIVERSITY HISTORICAL BUILDINGS
Biblioteca Joanina
Capela de S. Miguel
Sala dos Capelos
Torre da Universidade
11
PRACTICAL INFORMATION
Internet
Wireless internet access is available in all conference venues. Your home
institution eduroam credential are valid. If needed, use the following
authentication:
SSID: eduroam
User: jeep2015wifi@uc
Password: jeep2015#Z
Working Language
The working language of the conference is English. No interpretation is
provided in any other language.
Insurance
The organizers do not accept responsibility for individual medical, revel or
personal insurance. Participants are strongly advised to take out their own
insurance policies.
Certificate of attendance
All registered participants will be delivered a certificate of attendance.
Lunch
Midday Lunch will be taken in the University Auditorium.
Telephone
The international code for Portugal is +351. Public phones accept coins or
credit cards.
Emergency phone numbers
National Emergency free number is 112. This number is valid to Medical Care
(INEM) and Police. Police of Coimbra local number (+351) 239 797 640.
Dress code
The dress code for the gala dinner is smart casual.
Tourism Office
Av. Afonso Henriques, 132
3000-009 Coimbra
Telf: (+351) 239 488 120
Email: [email protected]
http://www.turismodocentro.pt
12
COMMITTEES
SCIENTIFIC COMMITTEE
J. Canotilho (Fac. Farmácia, U. Coimbra)
G. Coquerel (Lab. Sciences et Méthodes Séparatives, U. Rouen)
J. P. Coutinho (CICECO, U. Aveiro)
M. E. Eusébio (Dep. Química, U. Coimbra)
M. Ferriol (Lab. Matériaux Optiques, Photonique et Systèmes, U. Lorraine)
C. Goutaudier (Lab. des Multimatériaux et Interfaces, Université Claude
Bernard, Lyon)
M. Lomello-Tafin (Lab. Systèmes et Matériaux pour la Mecatronique, U.
Savoie)
J-L. Tamarit (U. Politècnica de Catalunya, Barcelona)
J-C. Tedenac (Institut Charles Gerhardt, Université Montpellier 2)
ORGANIZING COMMITTEE
M. Ermelinda Eusébio (Dep. Química, U. Coimbra)
João Canotilho (Fac. Farmácia, U. Coimbra)
Ricardo Castro (Fac. Farmácia, U. Coimbra)
Mariette Pereira (Dep. Química, U. Coimbra)
Manuela Ramos Silva (Dep. Física, U. Coimbra)
Mário T.S. Rosado (Dep. Química, U. Coimbra)
Teresa Roseiro Maria (Dep. Química, U. Coimbra)
António O.L Évora (PhD student)
Sara Machado (MSc student)
Melodia Oliveira (MSc student)
13
41st Conference on Phase Equilibria
XLIèmes Journées d’Étude des Équilibres entre Phases
JEEP 2015
Scientific programme
SCIENTIFIC PROGRAMME
Wednesday, 25th March
Thursday, 26th March
08:30
09:00
09:15
Welcoming Participants
08:45
Conference Opening
SESSION 1
Chair:
G. Coquerel
and
José A. Paixão
11:00
11:15
Friday, 27th March
Coffee Break
SESSION 2
Chair:
M. Ferriol
and
Valery Vassiliev
SESSION 5
Chair:
Joop ter Horst
and
Manuel João Monte
10:30
Poster Session
and
Coffee Break
11:30
12:35
12:40
13:00
Lunch
Welcoming
Participants
14:45
15:00
14:00
SESSION 3
Chair:
Olivier Baudouin
and
Josefa Fernández
16:05
Poster Session and
Coffee Break
17:05
SESSION 4
Chair:
Luís Paulo Rebelo
and
João Coutinho
18:00
Welcome Reception
18:25
19:00
Walking Guided Tour
13:00
Lunch
Workshop Opening
Workshop for
Young Scientists
Chair:
Mário Rosado
SESSION 6
Chair:
Christelle Goutaudier
and
Yohann Cartigny
Awards Announcement and
Conference Closure
19:30
20:15
Meeting at
Santa Clara
Bridge
Gala Dinner
17
14:15
Guided Visit to the
University
Historical Buildings
SCIENTIFIC PROGRAMME
Wednesday, 25th March, Department of Chemistry
13:00 – 14:45
Welcoming Participants
14:45 – 15:00
Workshop Opening
WORKSHOP FOR YOUNG SCIENTISTS Chair: Mário Rosado
15:00 – 16:00
WYS-01
X-RAY SCATTERING TECHNIQUES IN THE STUDY OF
PHASE TRANSITIONS
José António Paixão
University of Coimbra, Portugal
16:00 – 17:00
WYS-02
PHASE EQUILIBRIA: A METHODOLOGICAL AND
THERMODYNAMIC APPROACH
Luís Belchior Santos
University of Porto, Portugal
17:00 – 18:00
WYS-03
PHASE EQUILIBRIA AND VOLUMETRIC BEHAVIOUR
OF BINARY MIXTURES CONTAINING CARBON
DIOXIDE AND MOLECULAR OR IONIC LIQUIDS
Josefa Fernández
University of Santiago de Compostela, Spain
18:00 – 19:00
Welcome Reception
19:00 – 20:00
Coimbra Walking Guided Tour
Thursday, 26th March, University Auditorium
8:30 – 9:00
Welcoming Participants
9:00 – 9:15
Conference Opening
SESSION 1 Chair: Gérard Coquerel and José A. Paixão
9:15 – 10:00
PL-01
SOLUBILITY,
SOLUTE
CRYSTAL NUCLEATION
SELF-ASSOCIATION
&
Joop ter Horst
University of Strathclyde, Glasgow, United Kingdom
10:00 – 10:15
OC-01
EFFECT OF UREA DERIVATIVES IN BLOCKING THE
METASTABLE FORM OF PYRAZINAMIDE BY COSPRAY DRYING
G. Baaklini, V. Dupray, G. Coquerel
University of Normandy, France
18
SCIENTIFIC PROGRAMME
10:20 – 10:35
OC-02
A SOLUTION CO-CRYSTALLIZATION METHOD BASED
ON USING SUPERCRITICAL CO2 AS AN ANTISOLVENT
C. Pando, I. Cuadra, A. Cabañas, J.A.R.
Cheda, J.A.R. Renuncio
University Complutense de Madrid, Spain
10:40 – 10:55
OC-03
SOLVENT EFFECTS ON THE POLAR NETWORK OF
IONIC LIQUID SOLUTIONS
C.E.S. Bernardes, K. Shimizu, J.N. Canongia
Lopes
University of Lisbon and New University of Lisbon,
Portugal
11:00
Coffee Break
SESSION 2 Chair: Michel Ferriol and Valery Vassiliev
11:15 – 11:30
OC-04
THERMODYNAMIC MODELING OF Al-Ni- Gd ALLOYS
N.I. Ilinykh, V.E. Sidorov
Ural Technical Institute of Telecommunications,
Ekaterinburg and Informatics and Ural State
Pedagogical University, Ekaterinburg, Russia
11:35 – 11:50
OC-05
USING PHASE DIAGRAMS TO GUIDE CERAMICS
PRODUCTION FROM ALTERNATIVE RAW MATERIALS
A.M. Segadães
University of Aveiro, Portugal
11:55 – 12:10
OC-06
STUDY OF SOLID-LIQUID EQUILIBRIA IN THE H2O,
2Al3+, Ca2+// O2-, SO4 SYSTEM TO CHARACTERIZE
CLOGGING PHASES OBSERVED DURING URANIUM
ORE MINING
A. Teyssier, J.M. Schmitt, C. Goutaudier
University Claude Bernard Lyon 1, France
12:15 – 12:30
OC-07
PHASE EQUILIBRIA IN THE Ag–Zr SYSTEM
A. Decreton, C. Antion, A. Janghorban, M.
Lomello-Tafin, M. Barrachin, P. Benigni, J.
Rogez, G. Mikaelian
Institut de Radioprotection et Sûreté Nucléaire,
Polytech Annecy Chambéry - University of Savoie,
and Aix-Marseille University, France
12:35
Lunch
19
SCIENTIFIC PROGRAMME
SESSION 3 Chair: Olivier Baudouin and Josefa Fernández
14:00 – 14:45
PL-02
NOT-SO-COMMON
PHASE
EQUILIBRIA
AND
UNPREDICTABLE MISCIBILITY IN IONIC LIQUIDCONTAINING SYSTEMS
Luís Paulo Rebelo
New University of Lisbon, Portugal
14:45 – 15:00
OC-08
PREDICTION OF THE VAPOR PRESSURE OF
ALCOHOL/DISTILLATE OIL BLENDS
R. Privat, J.N. Jaubert, M. Molière
University of Lorraine and University of Belfort
Montbéliard, France
15:05 – 15:20
OC-09
IONIC LIQUIDS AS EXTRACTIVE SOLVENTS OF
TERPENES AND TERPENOIDS
M.A.R. Martins, U. Domańska, B. Schröder,
S.P. Pinho, J.A.P. Coutinho
University of Aveiro, Portugal, Warsaw University of
Technology, Poland and Polytechnic Institute of
Bragança, Portugal
15:25 – 15:40
OC-10
LIQUID-LIQUID EQUILIBRIA FOR BINARY AND
TERNARY SYSTEMS OF MONO ETHYLENE GLYCOL,
WATER AND N-ALKANES IN THE TEMPERATURE
RANGE BETWEEN 280.15 K AND 333.15 K
C. Lindemann, P. Duchet-Suchaux, I. Mokbel,
J. Jose
University Claude Bernard Lyon1, TOTAL and
University of Saint Etienne Jean Monnet, France
15:45 – 16:00
OC-11
ON THE IONIC LIQUIDS STRUCTURE-PROPERTY
RELATIONSHIP
P.J. Carvalho, J.A.P. Coutinho
University of Aveiro, Portugal
16:05 – 17:05
Poster Session and Coffee Break
SESSION 4 Chair: Luís Paulo Rebelo and João Coutinho
17:05 – 17:20
OC-12
OPTIMAL DESIGN OF THE BIODIESEL PRODUCTION
AND PURIFICATION PROCESS WITH SOFT-SAFT
M.B. Oliveira, F. Llovell, S.V.D. Freitas, L.F.
Veja, J.A.P. Coutinho
University of Aveiro, Portugal, MATGAS Research
Center,
Barcelona,
Spain
and
Carburos
Metálicos/Air Products Group, Barcelona, Spain.
20
SCIENTIFIC PROGRAMME
17:25 – 17:40
OC-13
GEOMETRY OF THE RESIDUE CURVES MAPS:
RIEMANNIAN MODEL
N.N. Shcherbakova, V. Gerbaud, I. RodriguezDonis
LGC, INP-ENSIACET and LGC, CNRS, Toulouse,
France
17:45 – 18:00
OC-14
THERMODYNAMIC
AND
THERMOPHYSICAL
PROPERTIES OF BINARY SYSTEMS CONTAINING
GREEN SOLVENTS DERIVED FROM BIOMASS
L. Bendiaf, A. Negadi, Ilham Mokbel, J. Jose,
L. Negadi
University of Tlemcen, Algeria, Institute of Analytical
Sciences, Villeurbanne, France and Jean Monnet
University of Saint Etienne, France
18:05 – 18:20
OC-15
HIGH TEMPERATURE VAPOUR-LIQUID EQUILIBRIUM
OF
WATER+ALCOHOL
BINARY
MIXTURES:
EXPERIMENTAL MEASUREMENTS AND PREDICTION
USING CPA EOS
A.F. Cristino, M. B. Oliveira, A.M.F. Palavra,
C.A. Nieto de Castro
University of Lisbon and University of Aveiro,
Portugal
18:25
End of Session
19:45
Meeting at Santa Clara Bridge
20:15
Gala Dinner
Friday, 27th March, University Auditorium
SESSION 5 Chair: Joop ter Horst and Manuel João Monte
08:45 – 9:30
PL-03
9:30 – 9:45
OC-16
9:50 – 10:05
OC-17
POLYMORPHISM: IS IT ALWAYS THAT CLEAR?
G. Coquerel
University of Rouen, France
A HOLISTIC APPROACH TO POLYMORPHISM
A. Joseph, R.G. Simões, C.E.S. Bernardes,
M.F.M. Piedade, M.E. Minas da Piedade
University of Lisbon, Portugal
PHASE-RELATED
STRUCTURAL CHANGES IN
HYDROXYACETONE: FROM GAS TO CRYOGENIC
CRYSTAL
I. Reva
University of Coimbra, Portugal
21
SCIENTIFIC PROGRAMME
10:10 – 10:25
OC-18
A PHASE DIAGRAM OF A TRIMORPHIC SYSTEM
OBTAINED BY SUPERPOSITION OF DIMORPHIC
DIAGRAMS
I.B. Rietveld, B. Nicolaï
Paris Descartes University, France
10:30 – 11:30
Poster Session and Coffee Break
SESSION 6 Chair: Christelle Goutaudier and Yohann Cartigny
11:30 – 11:55
OC-19
GIANT BARO- AND MAGNETOCALORIC EFFECTS IN
MAGNETIC SHAPE MEMORY ALLOYS
P. Lloveras, J. Ll. Tamarit, M. Barrio, E. SternTaulats, A. Planes, Ll. Mañosa
Polytechnics University of Catalonia, Barcelona and
University of Barcelona, Catalonia, Spain
12:00 – 12:15
OC-20
EFFECTS OF CHROMIUM CONTENT ON THE
NITRIDED LAYER OF BINARY FE-CR ALLOYS
M.E. Djeghlal, N. Benrabia, L. Barrallier
Polytechnic National School, Algiers, Algeria,
Polytechnic National School, Algeria and MecaSurf
Laboratory ParisTech, Aix–en–Provence, France
12:20 – 12:35
OC-21
TWO TERNARY PHASE DIAGRAMS OF La2O3 - Nb2O5 (W/Mo)O3:
INVESTIGATION
AND
STRUCTURE
RESOLUTION OF THEIR TWO NEW COMPOUNDS
T.D. Vu, M. Barré, K. Adil, A. Jouanneaux,
F. Goutenoire
University of Maine, France and King Abdullah
University of Science and Technology, Saudi Arabia
12:45
13:00
14:15
Awards Announcement and Conference Closure
Lunch
Guided Visit to the University Historical
22
41st Conference on Phase Equilibria
XLIèmes Journées d’Étude des Équilibres entre Phases
JEEP 2015
Scientific contributions
WORKSHOP FOR YOUNG SCIENTISTS
WORKSHOP FOR YOUNG SCIENTISTS
WYS-01
X-RAY SCATTERING TECHNIQUES IN THE STUDY OF PHASE
TRANSITIONS
José António Paixão
University of Coimbra, Portugal
WYS-02
PHASE EQUILIBRIA: A METHODOLOGICAL AND
THERMODYNAMIC APPROACH
Luís Belchior Santos
University of Porto, Portugal
WYS-03
PHASE EQUILIBRIA AND VOLUMETRIC BEHAVIOUR OF BINARY
MIXTURES CONTAINING CARBON DIOXIDE AND MOLECULAR OR
IONIC LIQUIDS
Josefa Fernández
University of Santiago de Compostela, Spain
25
PLENARY LECTURES
PLENARY LECTURES
PL-01
SOLUBILITY, SOLUTE SELF-ASSOCIATION & CRYSTAL
NUCLEATION
Joop ter Horst
University of Strathclyde, Glasgow, United Kingdom
PL-02
NOT-SO-COMMON PHASE EQUILIBRIA AND UNPREDICTABLE
MISCIBILITY IN IONIC LIQUID-CONTAINING SYSTEMS
Luís Paulo Rebelo
New University of Lisbon, Portugal
PL-03
POLYMORPHISM: IS IT ALWAYS THAT CLEAR?
Gérard Coquerel
University of Rouen, France
27
ORAL COMMUNICATIONS
ORAL COMMUNICATIONS
OC-01
EFFECT OF UREA DERIVATIVES IN BLOCKING THE METASTABLE
FORM OF PYRAZINAMIDE BY CO-SPRAY DRYING
G. Baaklini, V. Dupray, G. Coquerel
University of Normandy, France
OC-02
A SOLUTION CO-CRYSTALLIZATION METHOD BASED ON USING
SUPERCRITICAL CO2 AS AN ANTISOLVENT
C. Pando, I. Cuadra, A. Cabañas, J.A.R. Cheda, J.A.R. Renuncio
Complutense University of Madrid, Spain
OC-03
SOLVENT EFFECTS ON THE POLAR NETWORK OF IONIC LIQUID
SOLUTIONS
C.E.S. Bernardes, K. Shimizu, J.N. Canongia Lopes
University of Lisbon and New University of Lisbon, Portugal
OC-04
THERMODYNAMIC MODELING OF Al-Ni- Gd ALLOYS
N.I. Ilinykh, V.E. Sidorov
Ural Technical Institute of Telecommunications, Ekaterinburg and
Informatics and Ural State Pedagogical University, Ekaterinburg,
Russia
OC-05
USING PHASE DIAGRAMS TO GUIDE CERAMICS PRODUCTION
FROM ALTERNATIVE RAW MATERIALS
A.M. Segadães
University of Aveiro, Portugal
OC-06
STUDY OF SOLID-LIQUID EQUILIBRIA IN THE H2O, Al3+, Ca2+// O2-,
2SO4 SYSTEM TO CHARACTERIZE CLOGGING PHASES
OBSERVED DURING URANIUM ORE MINING
A. Teyssier, J.M. Schmitt, C. Goutaudier
University Claude Bernard Lyon 1, France
OC-07
PHASE EQUILIBRIA IN THE Ag–Zr SYSTEM
A. Decreton, C. Antion, A. Janghorban, M. Lomello-Tafin, M. Barrachin,
P. Benigni, J. Rogez, G. Mikaelian
Institut de Radioprotection et Sûreté Nucléaire, Polytech Annecy
Chambéry – University of Savoie, and Aix-Marseille University, France
OC-08
PREDICTION OF THE VAPOR PRESSURE OF
ALCOHOL/DISTILLATE OIL BLENDS
R. Privat, J.N. Jaubert, M. Molière
University of Lorraine and University of Belfort Montbéliard, France
OC-09
IONIC LIQUIDS AS EXTRACTIVE SOLVENTS OF TERPENES AND
TERPENOIDS
M.A.R. Martins, U. Domańska, B. Schröder, S.P. Pinho, J.A.P.
Coutinho
University of Aveiro, Portugal, Warsaw University of Technology,
Poland and Polytechnic Institute of Bragança, Portugal
29
ORAL COMMUNICATIONS
OC-10
LIQUID-LIQUID EQUILIBRIA FOR BINARY AND TERNARY
SYSTEMS OF MONO ETHYLENE GLYCOL, WATER AND NALKANES IN THE TEMPERATURE RANGE BETWEEN 280.15 K
AND 333.15 K
C. Lindemann, P. Duchet-Suchaux, I. Mokbel, J. Jose
University Claude Bernard Lyon1, TOTAL and University of Saint
Etienne Jean Monnet, France
OC-11
ON THE IONIC LIQUIDS STRUCTURE-PROPERTY RELATIONSHIP
P.J. Carvalho, J.A.P. Coutinho
University of Aveiro, Portugal
OC-12
OPTIMAL DESIGN OF THE BIODIESEL PRODUCTION AND
PURIFICATION PROCESS WITH SOFT-SAFT
M.B. Oliveira, F. Llovell, S.V.D. Freitas, L.F. Vega, J.A.P. Coutinho
University of Aveiro, Portugal, MATGAS Research Center, Barcelona,
Spain and Carburos Metálicos/Air Products Group, Barcelona, Spain
OC-13
GEOMETRY OF THE RESIDUE CURVES MAPS: RIEMANNIAN
MODEL
N.N. Shcherbakova, V. Gerbaud, I. Rodriguez-Donis
LGC, INP-ENSIACET and LGC, CNRS, Toulouse, France
OC-14
THERMODYNAMIC AND THERMOPHYSICAL PROPERTIES OF
BINARY SYSTEMS CONTAINING GREEN SOLVENTS DERIVED
FROM BIOMASS
L. Bendiaf, A. Negadi, Ilham Mokbel, J. Jose, L. Negadi
University of Tlemcen, Algeria, Institute of Analytical Sciences,
Villeurbanne, France and University of Saint Etienne Jean Monnet,
France
OC-15
HIGH TEMPERATURE VAPOUR-LIQUID EQUILIBRIUM OF
WATER+ALCOHOL BINARY MIXTURES: EXPERIMENTAL
MEASUREMENTS AND PREDICTION USING CPA EOS
A.F. Cristino, M. B. Oliveira, A.M.F. Palavra, C.A. Nieto de Castro
University of Lisbon and University of Aveiro, Portugal
OC-16
A HOLISTIC APPROACH TO POLYMORPHISM
A. Joseph, R.G. Simões, C.E.S. Bernardes, M.F.M. Piedade, M.E.
Minas da Piedade
University of Lisbon, Portugal
OC-17
PHASE-RELATED STRUCTURAL CHANGES IN
HYDROXYACETONE: FROM GAS TO CRYOGENIC CRYSTAL
I. Reva
University of Coimbra, Portugal
OC-18
A PHASE DIAGRAM OF A TRIMORPHIC SYSTEM OBTAINED BY
SUPERPOSITION OF DIMORPHIC DIAGRAMS
I.B. Rietveld, B. Nicolaï
Paris Descartes University, France
30
ORAL COMMUNICATIONS
OC-19
GIANT BARO- AND MAGNETOCALORIC EFFECTS IN MAGNETIC
SHAPE MEMORY ALLOYS
P. Lloveras, J. Ll. Tamarit, M. Barrio, E. Stern-Taulats, A. Planes, Ll.
Mañosa
Polytechnics University of Catalonia, Barcelona and University of
Barcelona, Catalonia, Spain
OC-20
EFFECTS OF CHROMIUM CONTENT ON THE NITRIDED LAYER OF
BINARY Fe-Cr ALLOYS
M.E. Djeghlal, N. Benrabia, L. Barrallier
Polytechnic National School, Algiers, Algeria, and MecaSurf Laboratory
ParisTech, Aix –en –Provence, France
OC-21
TWO TERNARY PHASE DIAGRAMS OF La2O3 - Nb2O5 - (W/Mo)O3:
INVESTIGATION AND STRUCTURE RESOLUTION OF THEIR TWO
NEW COMPOUNDS
T.D. Vu, M. Barré, K. Adil, A. Jouanneaux, F. Goutenoire
University of Maine, France and King Abdullah University of Science
and Technology, Saudi Arabia
31
POSTER COMMUNICATIONS
POSTER COMMUNICATIONS
P-01
PHASE BEHAVIOR AT HIGH PRESSURE OF CO2 + REFERENCE OR
VEGETABLE LUBRICANT SYSTEMS DEVELOPED FOR TWO
STROKE ENGINES
T. Regueira, O. Fandiño, L. Lugo, E.R. López, J. Fernández
P-02
HIGH PRESSURE SOLUBILITY: IMPROVING THE UNCERTAINTY OF
A SYNTHETIC ISOCHORIC METHOD
E.R. López, O. Fandiño, L. Lugo, J. Fernández
P-03
THE EFFECT OF THE CATION ALKYL CHAIN BRANCHING ON THE
MUTUAL SOLUBILITIES WITH WATER, N-BUTANE AND ISOBUTANE
K. Shimizu, J.N. Canongia Lopes
P-04
APPLICATION OF HYBRID METHOD BASED ON ANN AND PSO
ALGORITHM FOR ESTIMATING OF THE SOLUBILITY OF SOLID
DRUGS IN SC-CO2
A. Abdallah El Hadj, M. Laidi, S. Hanini, C. Si-Moussa, T. Omari
P-05
WATER SOLUBILITY OF N(DIETHYLAMINOTHIOCARBONYL)BENZIMIDO DERIVATIVES
M.A.R. Martins, B. Schröder, S.P. Pinho, J.A.P. Coutinho
P-06
SOLUBILITY OF CARBON DIOXIDE IN FLUOROALKYLPHOSPHATE
IONIC LIQUIDS
M.E. Zakrzewska, M. Nunes da Ponte
P-07
UNDERSTANDING THE INTERACTIONS BETWEEN AMMONIUMBASED BISTRIFLAMIDE IONIC LIQUIDS AND MOLECULAR
SOLVENTS
A. Mão de Ferro, P.M. Reis, A.J.L. Costa, C.E.S. Bernardes, K. Shimizu,
J.N. C. Lopes, J.M.S.S. Esperança, L.P.N. Rebelo
P-08
(canceled) THERMODYNAMIC STUDY OF SOLVENTS TYPE IONIC
LIQUIDS: APPLICATION IN THE SUBSTITUTION OF POLLUTED
SOLVENTS
H. Bouafia, M. Kourichi
P-09
FLUORINATED IONIC LIQUIDS: THERMOPHYSICAL
CHARACTERIZATION AND PARTITION PROPERTIES
N.S.M. Vieira, P.M. Reis, J.M.M. Araújo, K. Shimizu, J.N.C. Lopes,
J.M.S.S. Esperança, A.B. Pereiro, L.P.N. Rebelo
P-10
(canceled) PARTITION COEFFICIENTS AIR/WATER AND
OCTANOL/WATER OF FOOD PACKAGING CONTAMINANTS
ISOMERS: DIBUTYLPHTALATE AND DIISOBUYLPHTHALATE
H. Ishak, I. Mokbel, C. Goutaudier, J. Jose, J. Stephan, J. Saab
P-11
DETECTING UNIVOLATILITY CURVES IN TERNARY ZEOTROPIC
MIXTURES BY USING BINARY DISTRIBUTION LINES
I. Rodriguez-Donis, N. Shcherbakova, V. Gerbaud
33
POSTER COMMUNICATIONS
P-12
SEPARATION OF GREENHOUSE GASES WITH IONIC LIQUIDS
WITH THE SOFT-SAFT
M.B. Oliveira, L.M.C. Pereira, P.J. Carvalho, F.Llovell, L.F. Veja,
J.A.P. Coutinho
P-13
EXCESS ENTHALPIES AND PHASE BEHAVIOR OF MIXTURES OF
HYDROGENATED AND PERFLUORINATED TERT-BUTANOL
I.C.M. Vaz, A.I.M.C.L. Ferreira, P. Morgado, E.J.M. Filipe,
J.A.P. Coutinho, M. Bastos, L.M.N.B.F. Santos
P-14
(canceled) EXCESS MOLAR GIBBS ENERGIES OF HEPTAN-2-ONE +
1,4-D ICHOROBUTANE OR + 1,6-DICHLOROHEXANE
MEASUREMENTS AND PREDICTIONS
O. Tafat-Igoudjilene, A. Ait-Kaci, J. Jose
P-15
AN EXPERIMENTAL STUDY ON THE THERMOPHYSICAL
PROPERTIES OF 2-BROMOFLUORENE
J.A.S.A. Oliveira, M.D.M.C. Ribeiro da Silva, M.J.S. Monte
P-16
PHASE DIAGRAM OF 4′-METHOXYACETOPHENONE
A.R.R.P. Almeida, M.J.S. Monte
P-17
VAPOR LIQUID EQUILIBRIUM OF 3,5- AND 2,6-DIMETHYLPYRIDINE
WITH HEXANE, CYCLOHEXANE AND TOLUENE
H. B.-Makhlouf-Hakem, A. Ait-Kaci, J. Jose
P-18
LIQUID PHASE EQUILIBRIA OF (WATER-BUTYRIC ACID-DIBUTYL
ETHER) TERNARY SYSTEM AT DIFFERENT TEMPERATURES
I. Yalin, S. Çehreli
P-19
LIQUID PHASE EQUILIBRIA OF (WATER + ACETIC ACID + DILUTED
TRIBUTYLAMINE) AT T = 298.2 K
T. Evlik, Y.S. Aşçı, S. Çehreli
P-20
THERMODYNAMIC PROPERTIES OF THIO ORGANIC COMPOUNDS
WITH ALIPHATIC HYDROCARBONS
S. Didaoui, A. Ait-Kaci
P-21
PHASE EQUILIBRIA IN THE TERNARY SYSTEM TETRACOSANE +
DIBENZOFURAN + BIPHENYL: EXPERIMENTAL DATA AND
PREDICTION WITH DISQUAC AND UNIFAC MODELS
A. Chikh Baelhadj, Ao. Dahmani, R. Mahmoud, S. Berkani
P-22
PHASE EQUILIBRIA AND VOLUMETRIC PROPERTIES OF
SOLUTIONS. APPLICATION TO METHYL
ESTERS+METHANOL+OCTANE, OR +ISOOCTANE
R. Ríos, X. Florido, L. Fernández, J. Ortega
34
POSTER COMMUNICATIONS
P-23
ACRYLONITRILE RECOVERY SYSTEM BY EXTRACTIVE
DISTILLATION: SIMULATION AND OPTIMIZATION
M.R. Souza, S.P. Pinho, P.R.B. Guimarães, R.F. Vianna
P-24
PHASE EQUILIBRIA OF BULK LIQUID MEMBRANE SYSTEMS FOR
THE SEPARATION OF FORMIC ACID FROM ITS AQUEOUS
SOLUTION
T. Kaya, M. Bilgin
P-25
INVESTIGATION OF LACTIC ACID SEPARATION BY LAYERED
DOUBLE HYDROXIDE: EQUILIBRIUM, KINETICS AND
THERMODYNAMICS
M. Lalikoglu, A. Gök, M.K. Gök, Y.S. Aşçı
P-26
THERMAL BEHAVIOR AND HEAT CAPACITIES OF BENZYL
IMIDAZOLIUM IONIC LIQUIDS
F.M.S. Ribeiro, P.B.P. Serra, M.A.A. Rocha, M. Fulem, K. Růžička,
L.M.N.B.F. Santos
P-27
THERMAL BEHAVIOR OF LOW MELTING POINT MESO-A3B LONG
ALKYL CHAIN-PYRIDYL PORPHYRINS
C.A. Henriques, M.J.F. Calvete, M. Ramos Silva, M.M. Pereira,
J. Canotilho, M.E.S. Eusébio
P-28
PHASE BEHAVIOUR OF IMIDAZOLIUM NTf2 BASED IONIC LIQUIDS
A.S.M.C. Rodrigues, L.M.N.B.F. Santos
P-29
A STRUCTURAL AND THERMODYNAMIC STUDY OF
POLYMORPHISM IN SIMVASTATIN
R.G. Simões, C.E.S. Bernardes, H.P. Diogo, M.E. Minas da Piedade
P-30
POLYMORPHIC PHASES OF TRIPHENYLGUANIDINE DERIVATIVES:
CHARGE-DENSITY STUDIES
M. Gonçalves, P.S. Pereira Silva, M.R. Silva
P-31
POLYMORPHISM AND CONFORMATIONAL ISOMORPHISM OF MANISIC ACID
P.S.P. Silva, R.A.E. Castro, E. Melro, M.R. Silva, T.M.R. Maria,
J. Canotilho, M.E.S. Eusébio
P-32
PARTIAL BLOCKAGE OF THE REVERSIBLE SOLID-SOLID
TRANSITION OF STRONTIUM SUCCINATE
N. Couvrat, M. Sanselme, P. Taulelle, J.M. Lerestif, M. Lynch,
L. Vaysse-Ludot, G. Coquerel
P-33
PHASE DIAGRAMS FOR OPTIMIZATION OF PHENANTHRENE
PURIFICATION PROCESSES: ZONE MELTING vs. COCRYSTALLIZATION
A. Burel, S. Brugman, N. Couvrat, S. Tisse, Y. Cartigny, G. Coquerel
P-34
UREA/WATER PHASE DIAGRAM DETERMINATION BY MEANS OF
TEMPERATURE-RESOLVED SECOND HARMONIC GENERATION
(TR-SHG)
L. Yuan, S. Clevers, N. Couvrat, V. Dupray, G. Coquerel
35
POSTER COMMUNICATIONS
P-35
INCIDENCE OF CONFINEMENT IN THE CRYSTALLIZATION ROUTE
FROM THE AMORPHOUS STATE OF A CHIRAL MOLECULE
Q. Viel, Y. Cartigny, G.Coquerel, E. Dargent, S. Petit
P-36
STUDY ON THE SPONTANEOUS RESOLUTION OF A SOLVATED
RACEMIC DIIRON COMPLEX VIA SOLID-VAPOR EQUILIBRIA
Y. Cartigny, M. Sanselme, M.Y. Tsang, F. Teixidor, C. Viñas, J.G.
Planas, G. Coquerel
P-37
INFLUENCE OF THE WATER CONTENT ON THE SOLID-SOLID
TRANSITION OF 1,3-DIMETHYLUREA
G. Baaklini, M. Sanselme, Y. Cartigny, G. Coquerel
P-38
A NEW POLYMORPHIC FORM OF N-METHYLUREA OBTAINED
FROM MELT-CRYSTALLIZATION
G. Baaklini, M. Sanselme, G. Coquerel
P-39
NOTEWORTHY HIGH-ENERGY-CONFORMATION SELECTION IN
CRYSTALLINE 1-BROMOFERROCENE AND 1,1’DIBROMOFERROCENE
R. Fausto, M.E.S. Eusébio, T.M.R. Maria, P.A. Silva, C.M. Nunes
P-40
SYNTHESIS AND POLYMORPHISM EVALUATION OF THE
3,5-BIS(DECYLOXY)BENZALDEHYDE
C.T. Arranja, R.A.E. Castro, M.R. Silva, M.E.S. Eusébio, A.J.F.N. Sobral
P-41
TRIS(8-HYDROXIQUINOLINATES)M(III): EXPLORING THE
MOLECULAR AND SOLID STATE PROPERTIES
R.J.S Taveira, C.F.R.A.C. Lima, J.C.S. Costa, L.M.N.B.F. Santos
P-42
INVESTIGATION OF LEVETIRACETAM ENANTIOSELECTIVE CO
CRYSTALLIZATION WITH QUIRAL CO-FORMERS, IBUPROFEN AND
NAPROXEN
S.C.T. Machado, R.A.E. Castro, T.M.R. Maria, M.T.S. Rosado, M.
Ramos Silva, J. Canotilho, M.E.S. Eusébio
P-43
SLOW MOLECULAR MOBILITY ON THE AMORPHOUS STATE OF
NONSTREOIDAL ANTI-INFLAMATORY DRUGS: KETOPROFEN AND
IBUPROFEN
E. Mora, H.P. Diogo, J.J. Moura Ramos
P-44
UNDERSTANDING THE DEHYDRATION MECHANISM OF
SOLVATES: FROM MICROSCOPY TO MOLECULAR LEVEL
A. Joseph, C.E.S. Bernardes, A.S. Viana, M.F.M. Piedade,
M.E. Minas da Piedade
P-45
POLYMORPHISM OF ADAMANTANE-1-METHANOL C11H18O
B. Ben Hassine, P. Negrier, M. Barrio, J.Ll. Tamarit, D. Mondieig
36
POSTER COMMUNICATIONS
P-46
PRESSURE-TEMPERATURE PHASE DIAGRAM AND POLYMORPHIC
BEHAVIOR OF 1,2-DIBROMO-ETHANE (C2Br2D4 AND C2Br2H4)
Ph. Negrier, M. Barrio, J.Ll. Tamarit, D. Mondieig
P-47
SOLID-STATE STUDIES ON C60 SOLVATES GROWN FROM Br2CX2
SOLVENTS (X = Cl, H)
J. Ye, M. Barrio, J.Ll. Tamarit, R. Céolin
P-48
SOLID-STATE STUDIES ON C60 SOLVATES GROWN FROM
DIBROMOPROPANE (Br2C(CH3)2)
J. YE, M. Barrio, J.Ll. Tamarit, R. Céolin
P-49
THE TCAN-C60 SOLVATE: A “DILUTE” PLASTIC CRYSTAL
E. Mitsari, M. Romanini, M. Barrio, J.Ll. Tamarit, R. Macovez
P-50
SUBTLE PHASE TRANSITION IN A FLUORINATED PRASEODYMIUM
COMPLEX
V. Pereira, J. Feldl, T.M.R. Maria, P. Martín-Ramos, D.S.N. Teixeira,
J. Martín-Gil, M. Ramos Silva
P-51
MESOPHASE ASSEMBLING BY H-BONDING IN THE
4-(OCTYLOXY)BENZOIC/4-ALKYLBENZOIC ACIDS SERIES
T.M.R. Maria, M.D. Miranda, P. Martín-Ramos, F. Vaca-Chávez,
M.E.S. Eusébio, P.J. Sebastião, J. L. Figueirinhas, M. Ramos Silva
P-52
DEVELOPMENT OF A CRYOGENIC MINIATURE ACSUSCEPTOMETER FOR MAGNETIC PHASE TRANSITION
IDENTIFICATION
F.J.P. Almeida, J.A. Paixão
P-53
PLASTIC CRYSTAL FORMING ABILITIES OF CYCLOHEXANEDIOL
ISOMERS
M.F. Oliveira, T.M.R. Maria, M.T.S. Rosado, R.A.E. Castro, J. Canotilho,
M.R. Silva, M.E.S. Eusébio
P-54
THE EXTRAORDINARY LOW PRESSURE OF THE I-II-L TRIPLE
POINT OF RITONAVIR
R. Céolin, I.B. Rietveld
P-55
EFFECT OF SUBSTITUENT SIZE ON THE MOLECULAR
STRUCTURE AND POLYMORPHISM OF CYCLOHEXANE DIOLS:
TRANS-1,4-CYCLOHEXANEDIMETHANOL
M.T.S. Rosado, T.M.R. Maria, R.A.E. Castro, J. Canotilho,
M. Ramos Silva, M.E.S. Eusébio
P-56
MOLECULAR DYNAMICS STUDIES OF CONJUGATED
ZWITTERIONIC POLYELECTROLYTE INTERACTIONS WITH
SURFACTANTS IN SOLUTION
B. Stewart, T. Costa, A.T. Marques, U. Scherf, M. Knaapila,
H.D. Burrows
37
POSTER COMMUNICATIONS
P-57
IONIC LIQUIDS FOR BIOLOGICAL APPLICATIONS
J.M.M. Araújo, A.B. Pereiro, N.S.M. Vieira, L.P.N. Rebelo
P-58
TOWARDS REALISTIC MODELING OF PF8 IN THE SOLID STATE
L.L.G. Justino, M.L. Ramos, J. Morgado, R. Fausto,
H. D. Burrows
P-59
NANOSTRUCTURING 8-HYDROXYQUINOLINE-5-SULFONATE AND
TRIVALENT METAL IONS IN THE PRESENCE OF SURFACTANTS
FOR OPTOELECTRONICS AND SENSING
M.L. Ramos, L.L.G. Justino, B. Stewart, T. Costa, H.D. Burrows
P-60
THE INFLUENCE OF MOLECULAR SYMMETRY ON THE ENTROPY
OF PURE PHASES
C.F.R.A.C. Lima, A.M.S. Silva, L.M.N.B.F. Santos
P-61
MOLECULAR CROWDING EFFECTS ON THE THERMOTROPIC
PROPERTIES OF LIPID BILAYERS
A.M. Alves, R. Cardoso, M.J. Moreno
P-62
APPROXIMATION OF THE LOW-TEMPERATURE HEAT CAPACITY
OF AIIIBV COMPOUNDS BY LINEAR COMBINATION OF DEBYE’S
FUNCTIONS
V.P. Vassiliev, V.A. Lysenko, A.F. Taldrik, N.I. Ilinykh, L.G.
Sevastyanova
P-63
STUDY OF THE PHASE DIAGRAM OF FeSe SUPERCONDUCTORS
M.S.C. Henriques, J.A. Paixão
P-64
LINEAR BEHAVIOUR OF ISOTHERMAL SOLUBILITY PHENOMENA
INVOLVING STRONG ELECTROLYTES. SPECIAL CASE OF
CONCENTRATED AQUEOUS SOLUTIONS OF COBALT AND NICKEL
NITRATES
C. Goutaudier, B. El Goundali, R. Tenu, M. Kaddami, J.J. Counioux
P-65
PECULIARITIES IN CRYSTALLIZATION KINETICS OF SOME Al-NiREM AMORPHOUS ALLOYS
V.E. Sidorov, P. Svec, D. Janickovic
P-66
THE INFLUENCE OF Ga (Zr, Sn) ADDITIONS ON CRYSTALLIZATION
OF CoFeBSiNb BULK AMORPHOUS ALLOYS
V.E. Sidorov, I. Lishchynskyy, I. Kaban
P-67
CRYSTAL FIBERS GROWTH OF THE NONLINEAR OPTICAL
CRYSTAL BaCaBO3F
F. Assi, M. Cochez, M. Ferriol, M. Aillerie, G. Maxwell
38
POSTER COMMUNICATIONS
P-68
GROWTH AND CHARACTERIZATIONS OF Bi2ZnB2O7 CRYSTAL
FIBERS
F. Assi, M. Cochez, M. Ferriol, M. Aillerie, G. Maxwell
P-69
CHARACTERIZATION AND NUMERICAL SIMULATION OF THE
MECHANICAL BEHAVIOR OF AERONAUTICAL ALLOY BASED
COMPOSITE
A. Sadki, M. Babou, M. Khattal, L. Hattali, N. Mesrati
P-70
THERMODYNAMIC MODELING OF AIII-Sb MELTS
N.I. Ilinykh, I.A. Malkova, V.P. Vassiliev, V.A.Volgarev
39
41st Conference on Phase Equilibria
XLIèmes Journées d’Étude des Équilibres entre Phases
JEEP 2015
Workshop for young
scientists
WORKSHOP FOR YOUNG SCIENTIST WYS-01
X-ray scattering techniques in the study of phase
transitions
José António Paixão
CEMDRX, Department of Physics, University of Coimbra, Portugal
The old techniques of X-Ray Scattering (XRS) are still unrivaled for the study of the
structure of materials. Most of the vast amount of accurate structural data nowadays
available has been determined by XRS from materials either in single-crystal or
polycrystalline form, but XRS can be used as well to study short-range order in liquids
and amorphous materials.
By studying the evolution of the patterns of XRS as a function of parameters such as
temperature, pressure, electric or magnetic fields, different types of phase transitions,
structural or otherwise, can be investigated in detail. Such parametric studies can be
used to follow different types of phase transitions, where the order parameter couples
directly or indirectly to the structure. XRS can be used, alone or in combination with
other techniques, to determine critical temperatures, phase boundaries, critical
exponents, etc.
More recently the scope of XRS has been enlarged to new fields, taking advantage of
the high brilliance and energy-tunability of X-ray beams available at modern
synchrotron sources. Resonant X-Ray Scattering (RXS), where the energy of the
photon beam is tuned to an absorption edge of one of the elements under study, has
been used to gather novel information on the phase transitions associated with both
charge and spin degrees of freedom, such as magnetic, orbital or multipolar ordering.13
In addition, the small cross-section of elastic scattering of X-rays by the spin and
orbital moments is now accessible using synchrotron beams, and it can be used as well
to study magnetic order and the associated phase transitions, much in the same manner
as neutron scattering, but with much higher resolution in momentum space.
In this workshop we will give an overview of the application of some of the classical
and novel techniques of XRS in the study of different types of phase transitions.
(1) J.A. Paixão, C. Detlefs, M.J. Longfield, R. Caciuffo, P. Santini, N. Bernhoeft, J. Rebizant,
G.H. Lander, Phys. Rev. Lett., 89, 2002, 187202.
(2) V.H. Rodrigues, J.A. Paixão, M.M.R. Costa, D. Mannix, A. Bombardi, J. Rebizant, G.H.
Lander, J. Phys.: Condens. Matter, 23, 2011, 26002.
(3) M.J. Longfield, J.A. Paixão, N. Bernhoeft, G.H Lander, Phys. Rev. B, 66, 2002, 54417.
43
WYS-02 WORKSHOP FOR YOUNG SCIENTISTS
Phase equilibria: A methodological and
thermodynamic approach
Luís M.N.B.F. Santos
University of Porto, Portugal
The higher or lower facility to understand and learn about phase equilibria is highly
dependent on our level of knowledge in thermodynamics, as well as on our background
and expertise concerning the methodologies used to explore the phase equilibrium
“lines of equilibrium or phase boundaries”.
In this lectures: I will recall some fundamental topics of thermodynamics related with
the interpretation and discussion of phase equilibrium and phase change; use the
interpretation of experimental results and the description of some methodologies to
understand the phase equilibrium of pure and binary systems. As a summary of this
workshop I will: give an overview about the working strategy typically followed in our
R&D group; present some fundamentals about phase stability thermodynamics;
describe some key details about experimental methodologies; explain or present some
case studies concerning how experimental data is analyzed, interpreted and related with
the phase equilibrium.
44
WORKSHOP FOR YOUNG SCIENTISTS WYS-03
Phase equilibria and volumetric behaviour of binary
mixtures containing carbon dioxide and molecular
or ionic liquids
J. Fernández
Laboratorio de Propiedades Termofísicas, Departamento de Física Aplicada, Universidad de Santiago de
Compostela, E-15782 Santiago de Compostela, Spain
The knowledge of high-pressure phase equilibria of binary systems containing CO 2 is
fundamental in several application areas, i.e., supercritical fluid extraction, gas
separation, purification and storing, absorption and compression refrigeration systems,
two stroke-engines, gas hydrates or enhanced oil recovery. 1-5
In this communication, it will presented a review of experimental measurements and
modeling performed in the Thermophysical Properties Laboratory of the University of
Santiago de Compostela on gas solubility1-3 and volumetric behaviour4,5 of binary
mixtures containing carbon dioxide and molecular and ionic liquids as well as vegetable
and reference oils.
As regards to modeling, it is interesting to point out that Martín et al. 6 have developed
open source programs of advanced equations of state (classical cubic equations, cubic
equations with excess Gibbs energy mixing rules, group contribution equations and
SAFT equations) for teaching purposes. Their work6 will be briefly described.
Acknowledgments: I am indebted with all the authors of the articles indicated below. This work was supported
by Spanish Ministry of Economy and Competitiveness through CTQ2011-2392
(1) O. Fandiño, E.R. López, L. Lugo, M. Teodorescu, A.M. Mainar, J. Fernández, J. Chem. Eng.
Data, 53, 2008, 1854-1861.
(2) O. Fandiño, E.R. López, L. Lugo, J. García, J. Fernández, J. Supercrit. Fluids, 55, 2010, 6270.
(3) T. Regueira, O. Fandiño, L. Lugo, E.R. López, J. Fernández, J. Supercrit. Fluids, 91, 2014,
90-97.
(4) O. Fandiño, L. Lugo, J.J. Segovia, E.R. López, M.J.P. Comuñas, J. Fernández, J. Supercrit.
Fluids, 58, 2011, 189-197.
(5) P.J. Carvalho, T. Regueira, J. Fernández, L. Lugo, J. Safarov, E. Hassel, J.A.P. Coutinho, J.
Supercrit. Fluids, 88, 2014, 46-55.
(6) Á. Martín, M.D. Bermejo, F.A. Mato, M.J. Cocero, Educ. Chem. Eng., 6, 2011, e114–e121.
45
41st Conference on Phase Equilibria
XLIèmes Journées d’Étude des Équilibres entre Phases
JEEP 2015
Plenary lectures
PLENARY LECTURES PL-01
Solubility, solute self-association & crystal nucleation
Joop H. ter Horst
EPSRC Centre for Innovative Manufacturing in Continuous Manufacturing and Crystallisation (CMAC),
Strathclyde Institute of Pharmacy and Biomedical Sciences, University of Strathclyde, 161 Cathedral
Street, Glasgow G4 0RE, Scotland
The trend towards more complex molecules, materials and systems will proceed into
the future bringing new crystallization challenges for particulate products such as
pharmaceuticals. The solution to these challenges lies in a fundamental understanding
of solubility, driving force and crystallization kinetics onto which we can build
innovative, integrated and intensified continuous crystallization processes.
The solubility or phase diagram is essential information for efficient and reliable
crystallization process design and operation. Different principles for solubility
measurements exist and due to commercially available equipment there is now easy
access to reliable solubility data. Solubility measurements through clear point
measurements by solvent addition at constant temperature are infrequently reported.
However, solvent addition methods are convenient for complex multicomponent
systems involving co-crystals or solvates.
One long standing and industrially important issue is the control of crystal nucleation
in terms of form and rate.1 Nucleation rates can be determined by measuring induction
time distributions.2,3. These measurements show that the kinetic pre-exponential factor
of the nucleation rate equation is lower than theoretically expected which would
indicate that either the concentration of heterogeneous particles or the attachment
frequency of building units is lower than expected. They further indicate that a single
nucleus mechanism is occurring.4,5 A general occurrence of such a mechanism would
have large implications for product quality control of industrial crystallizers.
Crystal nucleation is a stochastic process in which building units attach to and detach
from a cluster forming a nucleus, usually on a heterogeneous surface. In principle
nucleation can be controlled by the crystal building units, effective templates and
alternative energies. The building unit, for instance, can be influenced through the
solvent’s effect on the self-association of the solute in solution which can be
experimentally determined through spectroscopic techniques. 6 The impact of the
solvent is reflected in the polymorphic form crystallized. Also templates 7 and
alternative energies give additional degrees of freedom to control crystal nucleation.
(1) R.J. Davey, S.L.M. Schroeder, J.H. ter Horst, Angew. Chem., 52, 2013, 2166-2179.
(2) S. Jiang, J.H. ter Horst, Cryst. Growth Des., 11, 2011, 256-261.
(3) S.A. Kulkarni, et. al., Cryst. Growth Des., 13, 2013, 2435−2440.
(4) S.S. Kadam, H.J.M. Kramer, J.H. ter Horst, Cryst. Growth Des., 11, 2011, 1271–1277.
(5) S.A. Kulkarni, H. Meekes, J.H. ter Horst, Cryst. Growth Des., 14, 2014, 1493−1499.
(6) S.A. Kulkarni, et. al., Chem. Commun., 48, 2012, 4983−4985.
(7) S.A. Kulkarni, et. al., Langmuir, 30, 2014, 12368−12375.
49
PL-02 PLENARY LECTURES
Not-so-common phase equilibria and unpredictable
miscibility in ionic liquid-containing systems
L.P.N. Rebelo, J.M.S.S. Esperança, J.N. Canongia Lopes, A.J.L. Costa,
A.B. Pereiro, J.M.M. Araújo, M.R.C. Soromenho, K. Shimizu
Instituto de Tecnologia Química e Biológica - António Xavier, Universidade Nova de Lisboa, Av. da
República, 2780-157, Oeiras, Portugal
Recently, we embarked on a program about the formation of a third, nanostructured
domain in Ionic Liquids (ILs) by using fluorinated salts.1 For the first time, three
nanosegregated domains ̶ polar, nonpolar, and fluorous ̶ were found. Other non-toxic,
fluorous ionic liquids (FILs) were used to form aqueous solutions. Unexpectedly, we
have witnessed several cases where the aqueous FILs solutions are macroscopically
completely homogeneous in the whole concentration range.2 Several distinct selfassembled structures were identified. These perfluoroanionic amphiphilic ionic liquids
form distinct aggregated structures depending on their total concentration in aqueous
solution. The possible mechanism of the phase transitions identified in this work
corresponds to a micellar shape change from monomers to spherical micelles (first
transition), from spherical micelles to globular micelles (second transition), and from
globular micelles to cylindrical or lamellar micelles (third transition). The stable selfassembled structures found in the aqueous medium may justify the completely water
solubility of these novel fluorinated ionic liquids.
Probably, the best candidate to be a non-toxic ionic liquid and the only one which is
drinkable (at least according to my fears/braveness!) is cholinium acetate. Basically,
and using a lay terminology, it derives from choline and vinegar. Choline is the name
given to the salt containing the N,N,N-trimethyl-hydroxyethyl-ammonium cation,
[N1 1 1 2OH]+, and the chloride anion. Choline (also known as cholinium chloride) is an
essential nutrient for humans and some studies state that the presence of this salt is
crucial for several biological functions. While one replaces the anion and/or increases
the chain length of the alkyl moieties in the cation full non-toxicity may be lost. The
gain is the multiplication of the chemical and thermophysical diversity. We have found 3
the unusual LCST-type of demixing behavior (high-temperature immiscibility) in
binary mixtures of three cholinium-based ionic liquids-N-alkyl-N,N-dimethylhydroxyethylammonium bis(trifluoromethane)sulfonylimide, [N1 1 n 2OH][Ntf2]– with
nine different ethers. Auxiliary ab initio calculations and Molecular Dynamics
simulations were used to rationalize the experimental results at a molecular level.
(1) A.B. Pereiro, M.J. Pastoriza-Gallego, K. Shimizu, I.M. Marrucho, J.N.C. Canongia Lopes,
M.M. Pineiro, L.P.N. Rebelo, J. Phys. Chem. B, 117, 2013, 10826−10833.
(2) A.B. Pereiro, J.M.M. Araujo, F.S. Teixeira, I.M. Marrucho, M.M. Pineiro, L.P.N. Rebelo,
Langmuir, 31, 2015, 1283−1295.
(3) A.J.L. Costa, M.R.C. Soromenho, K. Shimizu, J.M.S.S. Esperanca, J.N.C. Canongia Lopes,
L.P.N. Rebelo, RSC Adv., 3, 2013, 10262–10271.
50
PLENARY LECTURES PL-03
Polymorphism: Is it always that clear?
G. Coquerel
Normandie Université, Université of Rouen Crystal Genesis unit EA3233 F-76821 Mont Saint Aignan
Cedex France
Recently Terry Threlfall’s group published a paper1 with the following provocative
title: ‘The same but different: isostructural polymorphs and the case of 3chloromandelic Acid’!!... The authors gave evidence that two crystal structures can be
satisfactorily resolved (P21/c with Z’ = 1 and P-1 with Z’=2). Nevertheless, these
structures differ only by a slight crystal lattice distortion and hardly at all in molecular
conformation and position. This is consistent with a single crystal to single crystal
transformation. As isotructurallity and polymorph appear contradictory, one can read
in the same article the fundamental question: ‘how little difference can a structure show
and yet will be considered to be a polymorph rather than an identity?’.
A survey of the literature reveals that this example is not unique. 2,3,4 Most of these
borderline cases are related to disorder in the crystal structures and the transitions are
associated with a weak, if not a very weak, enthalpy of transition.
A new case will be presented in which conformational order - disorder transition is
somewhat disconnected to the lattice relaxation through an intermediate phase showing
some constrains.
A discussion will follow in which the structural purity, several kinds of disorders will
be considered some related to ‘true’ polymorphism some others not.
(1).S.J. Coles, T.L. Threlfall, G.J. Tizzard, Cryst. Growth Des., 14, 2014, 1623−1628.
(2) R.K. Chandrappa, Ph. Ochsenbein, C. Martineau, M. Bonin, G. Altho, F. Engelke, H.
Malandrini, B. Castro, M. El Hajji, F. Taulelle; Cryst. Growth Des., 13, 2013, 4678−4687.
(3) J. Mol. Struct. special Issue 2014: selection of papers: Polymorphism and disorder: structural,
thermodynamic and spectroscopic aspects:
Polymorphism of cis-1,4-cyclohexanediol, a new plastic crystal former. Considerations on
isomeric cyclohexanediols plastic crystal forming abilities, S.V.S. Bebiano, M.T.S. Rosado, R.
A.E. Castro, M.R. Silva, J. Canotilho, T.M.R. Maria, M.E.S. Eusébio; Detection of orderdisorder transition in organic solids by using Temperature Resolved Second Harmonic
Generation (TR-SHG), S. Clevers, C. Rougeot, F. Simon, M. Sanselme, V. Dupray, G. Coquerel;
Polymorphism and disorder in caffeine: dielectric investigation of molecular mobilities, M.
Descamps, A.A. Decroix; False asymmetry, pseudosymmetry, disorder, polymorphism and
atomic displacement parameters, G.M. Lombardo, F. Punzo;
(4) L. Fabian, A. Kalman; Acta Crystallogr., B55, 1999, 1099−1108.
51
41st Conference on Phase Equilibria
XLIèmes Journées d’Étude des Équilibres entre Phases
JEEP 2015
Oral communications
ORAL COMMUNICATIONS OC-01
Effect of urea derivatives in blocking the
metastable form of pyrazinamide by co-spray
drying
G. Baaklini, V. Dupray, G. Coquerel
SMS Laboratory, Crystallogenesis Unit, EA 3233, Normandy University, rue Lucien Tesniére, F-76821
Mont Saint-Aignan Cedex, France
The present study focuses on the ability of excipients to induce the crystallization of a
specific polymorphic form of pyrazinamide (PZA) and to block the irreversible solid–
solid transition of the metastable forms of the PZA to the stable form at room
temperature. We outline an experimental protocol for the production of a structurally
pure γ form of PZA by means of spray drying. Without any particular treatment, phase
transition to δ form was detected after 14 days of storage under ambient conditions. In
order to prevent this irreversible phase transition, urea derivatives were co-spray dried
with PZA. By co-spray drying PZA with N-methylurea and 1,1- diethylurea, a phase
transition was detected few days after storage. However, by co-spray drying 5 % in
mass of 1,3-dimethylurea (DMU) with PZA, we noticed its ability in preventing phase
transitions and thus to maintain PZA under its γ form up to 12 months of storage at
room temperature.1
(1) G. Baaklini, V. Dupray, G. Coquerel, Int. J. Pharm., 479, 2015, 163−170.
55
OC-02 ORAL COMMUNICATIONS
A solution co-crystallization method based on
using supercritical CO2 as an antisolvent
C. Pando, I. Cuadra, A. Cabañas, J.A.R. Cheda, J.A.R. Renuncio
Physical Chemistry I Department, Facultad Ciencias Químicas, Universidad Complutense, Madrid, Spain
Co-crystals have received increasing attention in the field of pharmaceuticals because
they provide a means to improve the physicochemical and biological properties of the
original active pharmaceutical ingredient such as the solubility and chemical stability
through the interaction with a coformer. Co-crystals can be prepared by solution
methods, evaporative or cooling crystallization or solid-state grinding and mixing. In
this study, a solution method based on adding supercritical CO 2 as an antisolvent is
presented. This technique only requires that the two co-crystal components are
simultaneously soluble in a polar organic solvent and poorly soluble in the supercritical
fluid, and allows the use of different coformer concentrations and, in particular, those
corresponding to the co-crystal stoichiometric composition. The 2:1 diflunisal cocrystal with nicotinamide is obtained by this method and results are compared to those
previously reported for this co-crystal by Evora et al.1 and Wang et al.2 using liquid
assisted ball mill grinding and solution crystallization.
Supercritical CO2 (Tc = 31 °C, Pc = 7.4 MPa) is introduced in a precipitation chamber
using a high-pressure pump at constant flow rate. Then the organic solution containing
the coformers is fed through a second pump also at a constant flow rate reaching steady
state operating conditions and an adequate supercritical fluid/solvent ratio. The
chamber is heated and both T and P are controlled. When the fluid dissolves in the
solution, the mixture becomes supersaturated and precipitation starts. The co-crystal is
collected at the bottom and the walls of the precipitation chamber. Later, the chamber
is washed with the antisolvent to eliminate the liquid solvent. Solvent-free
microparticles with narrow size distributions were obtained for the anti-inflammatory
drug diflunisal alone and in combination with a biocompatible polymer.3 Other
advantages are operation at moderate T in an inert atmosphere thus avoiding the product
degradation and the possibility of tuning the fluid properties with T and P changes that
enables us to control the particle size and/or morphology.
(1) A.O.L. Évora, R.A.E. Castro, T.M.R. Maria, M.R. Silva, J.H. ter Horst, J. Canotilho, M.E.S.
Eusébio, Int. J. Pharm., 466, 2014, 68-75.
(2) L. Wang, B. Tan, H. Zhang, Z. Deng, Org. Process Res. Dev., 17, 2013, 1413-8.
(3) F. Zahran, A. Cabañas, J.A.R. Cheda, J.A.R. Renuncio, C. Pando, J. Supercrit. Fluids, 88,
2014, 56-65.
56
ORAL COMMUNICATIONS OC-03
Solvent effects on the polar network of ionic liquid
solutions
C.E.S. Bernardes,* K. Shimizu,* J.N. Canongia Lopes*†
*
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Avenida Rovisco Pais
1, 1049-001 Lisboa, Portugal
†
Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa, Av. República, 2780-157
Oeiras, Portugal
Many of the physical properties of the mixtures of ionic liquids (IL) with other solvents,
is intrinsically linked to the form how the solvent interacts with the IL polar network.
A way to investigate this interaction is by using molecular dynamic simulations. By
this method it is possible to visualize the structural changes that occur with the variation
of the concentration of the IL solutions and, thus, gain a microscopic interpretation
associated with macroscopic changes of the system physical properties (e.g. excess
enthalpy, phase separation, viscosity and conductivity).1 In this work, four types of
systems
were
investigated:
i)
1-ethyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide plus benzene, hexafluorobenzene or 1,2difluorobenzene mixtures; ii) choline-based ILs plus ether mixtures; iii) choline-based
ILs plus n-alkanol mixtures; and iv) 1-butyl-3-methylimidazolium nitrate and 1-ethyl3-methylimidazolium ethyl sulfate aqueous mixtures. The results produced a wealth of
structural and aggregation information that
highlight the resilience of the polar network of
the ionic liquids (formed by clusters of
alternating ions and counter-ions) to the
addition of different types of molecular solvent.
The analysis of the MD data also shows that the
intricate balance between different types of
interaction (electrostatic, van der Waals, Hbond-like) between the different species
present in the mixtures has a profound effect on
the morphology of the mixtures at a
mesoscopic scale.
(1) M. Leskiv, C.E.S. Bernardes, M.E. Minas da Piedade, J.N. Canongia. Lopes; J. Phys. Chem.
B, 114, 2010, 13179-13188; C.E.S. Bernardes, M.E. Minas da Piedade, J.N. Canongia. Lopes; J.
Phys. Chem. B, 115, 2011, 2067-2074; F.S. Oliveira, A.B. Pereiro, J.M.M. Araújo, C.E.S.
Bernardes, J.N. Canongia Lopes, S. Todorovic, G. Feio, P.L. Almeida, L.P.N. Rebelo, I.M.
Marrucho; Phys. Chem. Chem. Phys. 15, 2013, 18138-18147.
57
OC-04 ORAL COMMUNICATIONS
Thermodynamic modeling of Al-Ni-Gd alloys
N.I. Ilinykh*, V.E. Sidorov†
* Ural Technical Institute of Telecommunications and Informatics, 15, Repin Str., Ekaterinburg, Russia
†
Ural State Pedagogical University, 26 Cosmonavtov Ave., Ekaterinburg, Russia
Thermodynamic modeling of binary Al-Ni, Al-Gd and ternary Al-Ni-Gd alloys was
carried out. It was performed using TERRA software (created in MSTU named after
N. Bauman)1. The modeling was executed at the common pressure of P = 105 Pa in
argon atmosphere and temperature range 300 - 4000 K. The modeling system was taken
as condensed phases and gas phase above it. Initial content (at.%): Al - 86, Ni - 8, Gd 6.
According to literature data2,3, the formation of ternary compounds, such as Gd3Ni5Al19,
Gd4Ni6Al23, GdNi3Al9, GdNiAl4, GdNiAl3, Gd3Ni7Al14, GdNiAl2, GdNi2Al3, is
possible in Al-Ni-Gd system. Among them only Gd4Ni6Al23 compound is
thermodynamically stable. Information about thermodynamic properties of these
compounds is lack. Moreover, after appropriate annealing at elevated temperature only
binary compounds and pure aluminum are observed. That’s why the modeling was
executed taking into account the possibility of formation of binary compounds only.
The following condensed pure substances and compounds were taken into account: Al,
Ni, Gd, NiAl, Ni2Al3, NiAl3, Ni3Al, Ni5Al3, AlGd, Al2Gd3, Al3Gd, Al2Gd, AlGd2.
The temperature dependencies of alloys equilibrium composition, activities of the
components, the integral and partial excess thermodynamic characteristics (enthalpy,
entropy and Gibbs energy) were calculated.
Using subprogram TRIANGLE1 the phase diagrams for Al-Ni-Gd system were
constructed at 800 K and 2273 K. These temperatures correspond to solid and liquid
state, respectively.
Acknowledgments: The work is supported by RFBR (grant № 13-03-96055).
(1) B.G. Trusov. Vestnik of Bauman Moscow State Technological University, v.2 (special
Issue), 2012, 240-249 (Russian).
(2) M.C. Gao, R.E. Hackenberg, G.J. Shiflet. Journal of Alloys and Compounds, v.353, 2003,
114-123.
(3) S.Delsante, G. Borzone. Intermetallics, v.45, 2014, 71-79.
58
ORAL COMMUNICATIONS OC-05
Using phase diagrams to guide ceramics
production from alternative raw materials
A.M. Segadães
University of Aveiro, Department of Materials and Ceramics Engineering (CICECO), 3810-193 Aveiro,
Portugal
Continuous industrial activity generates increasing amounts of wastes and subproducts, whose disposal is subjected to stricter environmental legislation. At the same
time, various natural raw materials already are, or might soon become, strategic.
Therefore, industries of all kinds have already looked for alternative, less expensive,
natural raw materials and have optimized their processes in order to make the most of
what is available to them with the simultaneous benefit of producing less waste. Today,
industries are also very much aware that upgrading industrial wastes to alternative raw
materials can be interesting, both technically and economically.
Natural raw materials used in the fabrication of clay-based ceramic products show wide
compositional fluctuations and the resulting products are very heterogeneous. For this
reason, such products can easily tolerate raw material changes and the ceramic industry
is very capable of incorporating a variety of waste materials. 1-4 However, maybe
because some wastes are similar in composition to the natural raw materials
traditionally used, the “natural” tendency is to simply replace part of the original raw
material content by an equal amount of the new. By doing so, the product composition
changes, the content of liquid phase formed during firing changing with it, and that
strategy might end up suggesting a minute usage of the alternative raw material or
resulting in complete failure of the desired product.
Although in normal industrial operating conditions thermodynamic equilibrium is
usually not reached, the phase equilibrium diagram of the relevant system can still be
used to foresee the reactions tendency to completion. This work illustrates the use of
phase diagrams to make educated choices of compositions and processing parameters
in ceramics production and shows how this can save time and resources and, eventually,
lead to successful upgrade of waste materials, thus ameliorating their negative impact
on the environment.
(1) E.J.A. Perez, R. Terradas, M.R. Manent, M. Seijas, S. Martinez, Ind. Ceram., 16, 1996, 7-10.
(2) F. Andreola, L. Barbieri, A. Corradi, I. Lancellotti, T. Manfredini, J. Mater. Sci., 36, 2001,
4869-73.
(3) M. Dondi, M. Raimondo, C. Zanelli, Appl. Clay Sci., 96, 2014, 91-109.
59
OC-06 ORAL COMMUNICATIONS
Study of solid-liquid equilibria in the H2O, Al3+,
Ca2+// O2-, SO42- system to characterize clogging
phases observed during uranium ore mining
A. Teyssier,*† J.M. Schmitt,* C. Goutaudier†
†
*
AREVA, BG Mines, La Défense, France
Laboratoire des Multimatériaux et Interfaces, Université Claude Bernard Lyon 1, UMR CNRS 5615,
France
During the acid processing of uranium ores, temporary precipitation of solid phases
may be observed by AREVA. These solid phases which are often amorphous or poorly
crystallized are generally absent from current thermodynamic databases and need to be
better defined. For this purpose it was necessary to study liquid – solid equilibria in a
complex system.
First analysis showed that aluminium, calcium and sulphates composed the most part
of precipitates, as calcium sulphate and aluminium hydroxisulphate, so the quaternary
diagram, H2O – Ca2+, Al3+ // O2-, SO42-, was defined on the basis of observed
precipitates.
To represent this system and define solid-liquid equilibria, binary and ternary diagrams
were studied at 25 °C and 1 atm. Several were already described 1,2, Al2(SO4)3-CaSO4H2O was drawn and Al2O3-SO3-H2O was reconsidered as a huge number of aluminium
hydroxisulphates, which are the potential precipitates causing clogging, were found in
literature.3,4 However most of them are not or not well crystallized and hence complex
to characterise. Powder X-ray diffraction analysis highlighted the decomposition of one
phase to another after liquid removal at 25 °C, yet, comparison with the diffractograms
of the ICDD database was not satisfactory as few diffraction peaks were indexed. As a
consequence, Energy-dispersive X-ray spectroscopy and titration were used to
determine solid phase composition.
In the second step, as observed precipitates are in fact more complex and occur during
the acidification process, solubility of aluminium hydroxisulphates depending on pH
needed to be studied. Basification of aluminium sulphate with sodium, magnesium and
calcium hydroxide led to the precipitation of the same aluminium hydroxisulphates as
in the ternary system. Furthermore, magnesium and calcium sulphates were observed,
whereas sodium alum and potassium alum were found.
(1) F.K. Cameron, T.M. Bell, J. Am. Chem. Soc., 28, 1906, 1220-22.
(2) L.S. Wells, W.F. Clarke, H.F. McMurdie, J. Res. Nat'l. Bur. Stand., 30, 1943, 367-409.
(3) H. Bassett, T.H. Goodwin, J. Chem. Soc., 1949, 2239-2279.
(4) J.L. Henry, G.B. King, J. Am. Chem. Soc., 72, 1950, 1282-86.
60
ORAL COMMUNICATIONS OC-07
Phase equilibria in the Ag–Zr system
A. Decreton,* C. Antion,† A. Janghorban,† M. Lomello-Tafin,†
M. Barrachin,* P. Benigni,‡ J. Rogez,‡ G. Mikaelian‡
*
†
Institut de Radioprotection et Sûreté Nucléaire, B.P. 3, 13115 Saint Paul-lez-Durance Cedex, France.
Laboratoire SYMME, Polytech Annecy Chambéry - Université de Savoie, BP. 80439, 74944 Annecy-LeVieux Cedex, France.
‡
IM2NP, UMR7334, CNRS, Aix-Marseille Université, Campus de Saint Jérôme, Avenue Escadrille
Normandie Niémen – Case 251, 13397 Marseille Cedex 20, France.
The silver-zirconium phase diagram has been experimentally investigated in order to
clarify the controversies regarding the nature of the phase equilibria in the zirconiumrich composition range. The binary samples were melted from pure elements using an
arc furnace. The temperatures of phase transformations were measured by means of
differential thermal analysis (DTA) using non-stoichiometric yttria crucibles. Scanning
electron microscopy coupled with X-ray microanalysis (EDX) was used to study the
microstructure of as-cast and post-DTA samples.
We confirm the formation of two intermetallic compounds, AgZr and AgZr 2, as already
reported in previous works.1-4 AgZr2 was found to be formed from a peritectic reaction
between the liquid phase and high-temperature zirconium solid solution, β-Zr, at 1182
°C.
Two
eutectic
microstructures
[AgZr 2
+
AgZr]
and
[AgZr + Ag] were observed in several as-cast samples and the temperatures of the
eutectic reactions were measured at 1160 °C and 954 °C, respectively. Besides, the
eutectoid decomposition of high-temperature zirconium solid solution,
β-Zr → α-Zr + AgZr2, was found to take place at 821 °C.
(1) E. Raub, M. Engel, Z. Metallkd., 39, 1948, 172-177.
(2) J.O. Betterton Jr., D.S. Easton, T. Metall. Soc. AIME 212, 1958, 470-475.
(3) T.P. Loboda, V.N. Pyatnitskii, M.V. Raevskaya, E.M. Sokolovskaya, Vestn. Mosk. U. Khim.
19, 1978, 298-301.
(4) K. Zhang, H. Zhao, Y. Zhou, J. Less-Common Met., 138, 1988, 173-177.
61
OC-08 ORAL COMMUNICATIONS
Prediction of the vapor pressure of
alcohol/distillate oil blends
R. Privat,* J.N. Jaubert,* M. Molière†
*
†
Laboratoire Réactions et Génie des Procédés, Nancy, Université de Lorraine, France
Université de Belfort Montbéliard, Sévenans (formerly: engineer at General Electric), France
Incorporating blends of alcohols and hydrocarbons to the diet of car or gas turbine
engines raises multiple technical questions relating not only to the combustion process
but also to the physical properties of these blends.
An immediate and inescapable aspect lies in the safety of the storage of such blends as
their vapor pressure can lead to ignitable gas mixtures. Although some vapor pressure
data exist in the car engine literature for ethanol-gasoline blends, when tackling gas
turbine (GT) applications1, it is necessary to take into account some specific aspects,
namely: (i) the wider range ethanol concentration possible and (ii) the vast composition
spectrum of GT fuel oils likely to generate a much larger vapor pressure envelope as
compared to automotive applications.
In order to fulfill the safety needs of this type of alternative fuel applications, the LTMP
team of the LRGP laboratory (Nancy), has developed a thermodynamic model to
approach the vaporization equilibria of alcohol-distillate oil mixtures with variable
ethanol strength and oil composition. This model is based on a modified version of the
1978 Peng-Robinson equation of state and allows the estimation of the thermodynamic
properties of a multicomponent mixture made of alcohol and hydrocarbon molecules
by using the group contribution concept. This approach has enables predicting the
equilibrium partial pressure of such blends in the various situations of relevance for the
safety analysis of the fuel storages, providing a precious tool to engineers facing such
applications.
The presentation will report the elaboration of this model and illustrate the results
obtained when using it in different operation conditions.
(1) M. Moliere, M. Vierling , M. Aboujaib, P. Patil, A. Eranki, A. Campbell, R. Trivedi, A.
Nainani, S. Roy, N. Pandey, 2009, “Gas Turbines in Alternative Fuel Applications: Bio-Ethanol
Field Test”, Proceedings of ASME Turbo Expo, Orlando, Florida, USA, ASME paper nº GT200959047.
62
ORAL COMMUNICATIONS OC-09
Ionic liquids as extractive solvents of terpenes and
terpenoids
M.A.R. Martins,* U. Domańska,† B. Schröder,* S.P. Pinho,‡
J.A.P. Coutinho*
*
CICECO, Departamento de Química, Universidade de Aveiro, Aveiro, Portugal
Physical Chemistry Department, Warsaw University of Technology, Warsaw, Poland
‡
Associate Laboratory LSRE/LCM, Instituto Politécnico de Bragança, Bragança, Portugal
†
With the new emerging perception of terpenes and terpenoids impact on the
environment, rising to implications on a global scale, solutions for their fate in the
environment have been sought. One way forward are ionic liquids (ILs), widely
proposed as entrainers in the separation processes due their thermal and chemical
stability, and high performance extraction abilities. The combination of these two
classes of compounds is promising, not only to study the recovery of terpenes and
terpenoids from biorefineries effluents, but also for their direct production...
In this work, the interactions of selected terpenes, terpenoids and water with the ILs
composed by the 1-butyl-3-methylimidazolium cation [C4mim]+, and the anions
chloride, Cl-; dimethylphosphate, [DMP]-; methanesulfonate, [CH3SO3]-; and
trifluoromethanesulfonate, [CF3SO3]-, are measured through gas–liquid
chromatography from (398.15 to 448.15) K.
Results show a significant influence of the IL anion, and solute polarities, on the infinite
dilution activity coefficients. The highest infinite dilution activity coefficients, which
represents the weaker interactions between the solute and the IL, is observed for the
pair α-pinene–anion Cl-, whereas the lowest is observed for water–anion Cl-, where the
interactions are stronger. These data are very important to select the best ionic liquid to
capture terpenes and terpenoids from contaminated effluents, enabling also an
evaluation of the polarity of the anion.
63
OC-10 ORAL COMMUNICATIONS
Liquid-liquid equilibria for binary and ternary
systems of mono ethylene glycol, water and nalkanes in the temperature range between 280.15 K
and 333.15 K
C. Lindemann,* P. Duchet-Suchaux,† I. Mokbel,*‡ J. Jose*
*
UMR 5615, Université Claude Bernard Lyon1, 43 bd du 11 Novembre 1918, 69642 Villeurbanne, France.
†
TOTAL, 2 place Jean Millier -La Défense 6, 92400 Courbevoie, France
‡
Université de Saint Etienne, Jean Monnet, F-42023 Saint Etienne, France
In petroleum industry, mono ethylene glycol (MEG) is widely used as a gas hydrate
inhibitor for the natural gas transportation. Thus, reliable liquid-liquid equilibrium data
between hydrocarbons, mono ethylene glycol and water is important for optimizing
natural gas processing plants and their treatment units. With this aim, liquid-liquid
equilibria of binary and ternary mixtures of MEG and water with n-alkanes (C6 to C16)
were experimentally determined at three temperatures between 280.15 K and 333.15 K
and under atmospheric pressure.
To establish liquid-liquid equilibrium, a glass cell equipped with a jacket (for the
circulating fluid to keep constant temperature of the liquid mixture) and two sampling
lines to withdraw both the organic and the aqueous phases. When determining low
solubility (down to 10-9 in molar fraction) an additional apparatus is used. The principle
is based on a dynamic flow of water or water/MEG through a cell filled with an
adsorbent saturated with the studied n-alkane.
The temperature was controlled within 0.1 K. Hydrocarbons in the polar phase and
MEG in the organic phase were analyzed by gas chromatography, GC-FID and GC-MS,
and water in the organic phase by a coulometric Karl Fischer titration.
The experimental solubility, expressed in molar fraction, xparaffine, range between 10-2
and 10-9. A straight line is obtained, pledge of consistent measurements, when plotting
log10 xparaffine versus the number of carbon,
Fig.1.
The experimental data were compared with
the available literature data and
satisfactorily correlated using NRTL
equation.
64
ORAL COMMUNICATIONS OC-11
On the ionic liquids structure-property relationship
P.J. Carvalho, J.A.P. Coutinho
Departamento de Química – CICECO, Universidade de Aveiro, 3810-193 Aveiro, Portugal.
Ionic liquids (ILs) are composed of ions, and as a result there are a large number of
potential compounds to be synthesized by simple structural rearrangements. Able to be
either inert, acting only as solvents or designed to actively participate in a large range
of chemical reactions, these ionic compounds have often been considered as “green
solvents” because of their negligible vapor pressures and, in many cases, low
flammability, when compared with common organic solvents. Moreover, the ionic
nature of ILs is the main characteristic responsible for some of their most outstanding
properties, namely a high ionic conductivity, high thermal and chemical stability, and
enhanced solvation ability for a large array of compounds. At the same time, the
combination of different ions, sustained by a wide chemical diversity, allows the
tailoring of their properties, making them quasi specific fluids for a particular
application, thus “designer solvents”. Nonetheless and despite the large number of
works outing ionic liquids as “designer solvents”, the number of studies dealing with
their structural design, besides the simple combination of different cations and anions,
is, at this point, surprisingly scarce.
In this work the understanding of the structure-property relationship will be evaluated
and discussed beyond the cation-anion combination. In particular the effect of cation
isomerism or quasi-isomerism, the presence/absence of the aromaticity and the
influence of the cation's central atom in a large range of physical, chemical and
biological properties is presented.
Acknowledgments: 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 Partnership Agreement. Pedro J. Carvalho acknowledge
FCT for financial support through the Post-Doctoral (SFRH/BPD/82264/2011) scholarship.
65
OC-12 ORAL COMMUNICATIONS
Optimal design of the biodiesel production and
purification process with soft-SAFT
M.B. Oliveira,* F. Llovell,† S.V.D. Freitas,* L.F. Vega,† ‡, J.A.P. Coutinho*
*
CICECO, Chemistry Department, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal
†
MATGAS Research Center, Campus de la UAB, 09193 Bellaterra, Barcelona, Spain
‡
Carburos Metálicos/Air Products Group, C/Aragón 300, 08009 Barcelona, Spain
In the last ten years, biodiesel has become an excellent alternative to fossil fuels. 1 In
order to optimize biodiesels use for different processes, an accurate model able to
describe their main thermophysical properties in wide ranges of temperature and
pressure is needed. In this work, we apply the well-known soft-SAFT equation of state
(EoS)2, as a tool for the development, design, scale-up, and optimization of biodiesels
production and purification processes, through the description of fatty acid
esters/biodiesels thermodynamic properties, as well as the phase equilibria of systems
formed at the biodiesel production and purification industrial units. The DGT approach
coupled with soft-SAFT is used for the description of interfacial properties, while
viscosities are calculated through the Free-Volume Theory, in an integrated model.
Density, surface tension and viscosity data for fatty acid methyl and ethyl esters,
ranging from C8:0 to C24:0, with up to three unsaturated bonds, are successfully
reproduced for pressures up to 150 MPa, and in the temperature range 288.15 to 423.15
K. The high pressure densities and viscosities for 8 biodiesels are also well predicted
with the soft-SAFT EoS3.
The water solubility in 9 fatty acid esters, and the VLE of 12 fatty acid ester +
methanol/ethanol systems, formed at biodiesel production and purification industrial
units, are described through a new association scheme to explicitly take into account
the solvation phenomenon between esters and water/alcohols. Only one binary
interaction parameter is used, chain length dependent for the water systems and
constant for the methanol and ethanol mixtures, showing a high degree of
transferability. Particular attention is also given to the supercritical VLE of fatty acid +
alcohol systems description, of primary importance for the biodiesel production at
supercritical conditions.
(1) F. Ma, M. A. Hanna, Bioresour. Technol. 70, 1999, 1-15.
(2) F.J. Blas, L.F. Vega, Mol. Phys., 92, 1997, 135-50.
(3) M.B. Oliveira, S.V.D. Freitas, F. Llovell, L.F. Vega, J.A.P. Coutinho, Chem. Eng. Res. Des.,
92, 2014, 2898-2911.
66
ORAL COMMUNICATIONS OC-13
Geometry of the residue curves maps:
Riemannian model
N.N. Shcherbakova,* V. Gerbaud,† I. Rodriguez-Donis†
* LGC, INP-ENSIACET, Toulouse, France
† LGC, CNRS, Toulouse, France
The preliminary design of many separation processes for multicomponent mixtures
relies upon the analysis of residue curve maps (RCM), which is a classical tool of the
qualitative analysis in the theory of distillation of multicomponent mixtures within the
thermodynamic equilibrium model. The mathematical formalism of RCM comes back
to the works of Serafimov and Zharov1 in 1970s, and it was significantly improved by
the group of Doherty2 later. Nevertheless, until now some theoretical features of RCM
remained unclear. For instance, the structure of the residue curves differential
equations, the connection between RCM and the associated boiling temperature
surface, as well as the topological characterization of the separating boundaries. 3 We
give our explanation of these properties putting in evidence the Riemmanian structure
hidden behind the thermodynamic equilibrium condition.
We consider the open evaporation process of homogeneous multicomponent mixtures
under isobaric condition. Our main result is the following: by analyzing van der Waals
– Storonkin's equation2 we show that the thermodynamic equilibrium condition implies
the existence of the Riemmanian metric Г in the space of molar concentrations.
Consequently, the residue curves differential equations can be written as a system of
gradient type :
𝑑𝑥
= 𝑥 − 𝑦(𝑥, 𝑇) = 𝛻𝛤 𝑇𝑏 (𝑥)
𝑑𝜉
where 𝑇𝑏 (𝑥)is the boiling temperature of the mixture of composition 𝑥 and 𝛻𝛤 denotes
the gradient in the sense of the metric Г. This construction implies all known topological
properties of RCM, and yields some additional ones. For instance, residue curves and
isotherms
are
orthogonal
in
the
sense
of
metric
Г.
We illustrate our results by examples of ternary mixtures.
(1) A.M. Toikka, J.D. Jenkins, Chem. Eng. J., 89, 2003, 1-27.
(2) M.F. Doherty et al. Chem. Eng. Science, 33, 34, 39, 1978-1984.
(3) V.N. Kiva, E.K. Hilmen, S. Skogestad. Chem. Eng. Science, 58, 2003, 1903-1953.
67
OC-14 ORAL COMMUNICATIONS
Thermodynamic and thermophysical properties of
binary systems containing green solvents derived
from biomass
L. Bendiaf,* A. Negadi,* Ilham Mokbel,†‡ J. Jose,† L. Negadi,*
*
LATA2M, Laboratoire de Thermodynamique Appliquée et Modélisation Moléculaire, University of
Tlemcen, Post Office Box 119, Tlemcen 13000, Algeria.
†
UMR 5280, Institut des Sciences Analytiques, 5, rue de la Doua, 69100 Villeurbanne, France.
‡
Université de Saint Etienne, Jean Monnet, F-42023 Saint Etienne, Université de Lyon, F-42023 Saint
Etienne, France.
With the steadily increasing energy consumption contributing to the depletion of fossil
resources, the insecurity of energy supply and global warming, renewable energy
resources emitting less CO2 become popular alternatives to substitute fossil fuels,
especially in the transportation sector which is responsible for a large part of the global
CO2 emissions. Among many energy alternatives, biofuels, hydrogen, natural gas and
syngas may likely emerge as the four strategically important sustainable fuel sources in
the foreseeable future. Within these four, biofuels are the most environment friendly
energy source. They are being explored to replace fossil fuels. Biofuels are referred to
liquid, gas and solid fuels predominantly produced from biomass.
The present work is part of a research program concerning the investigation of the
thermodynamic properties of binary mixtures containing solvents derived from
biomass.
In this paper, we report the vapor pressures of the binary mixtures {furfural (x1) +
ethanol or 1-butanol or 2-butanol (x2)} measured by means of a static device at
temperatures between 273 and 363 K. The data were correlated with the Antoine
equation. From these data excess Gibbs functions were calculated for several constant
temperatures and fitted to a fourth-order Redlich–Kister equation using the Barker’s
method as two systems exhibit positive deviations in GE and one negative deviations
for all investigated temperatures over the whole composition range. The NRTL,
UNIQUAC and Modified UNIFAC (Do) models have also been used.
Additionally, the density () and sound velocity (u) of the same systems were measured
at T = 283.15 to 313.15 K and at atmospheric pressure. The sound velocity data were
tested by using sound velocity mixing rules to calculate the sound velocity of the binary
mixture from pure component data. The derived properties (V Em, s, s) were also
calculated. The Redlich–Kister polynomial equation was used to fit the
excess/deviation properties. The semi-empirical calculation with the help of
HyperChem 7 shows that furfural interacts with the alcohol through the H-bonding.
68
ORAL COMMUNICATIONS OC-15
High temperature vapour-liquid equilibrium of
water+alcohol binary mixtures:
experimental measurements and prediction using
CPA EOS
A.F. Cristino,* M. B. Oliveira,† A.M.F. Palavra,*C.A. Nieto de Castro*
†
*
Lisbon University, CQE, 1749-016 Lisbon, Portugal
CICECO, Chemistry Department, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal
The knowledge of the vapour-liquid equilibria behaviour of systems composed of water
and alcohols are crucial for the design of separation processes. For systems of this kind,
the data is scarce and some obtained many years ago. With the resources that we have
nowadays, more accurate data can be obtained. In this work we present the prediction
of such type of results using Cubic-Plus-Association equation of state (CPA EoS).1 For
this prediction we have used the binary systems water + ethanol, water + 1-propanol
and ethanol + 1-propanol from previous studies.2-4
The experimental data was obtained using a flow apparatus described in previous
work.5
(1) M.B. Oliveira, J.A.P. Coutinho, A.J. Queimada, Fluid Phase Equilib., 258, 2007, 58–66.
(2) A.F. Cristino, S. Rosa, P. Morgado, A. Galindo, E.J.M. Filipe, A.M.F. Palavra, C.A. Nieto de
Castro, Fluid Phase Equilib. 341, 2013, 48-53.
(3) A.F. Cristino, S. Rosa, P. Morgado, A. Galindo, E.J.M. Filipe, A.M.F. Palavra,
C.A. Nieto de Castro, J. Chem. Thermodyn., 60, 2013, 15-18.
(4) A.F. Cristino, S. Rosa, P. Morgado, A. Galindo, E.J.M. Filipe, A.M.F. Palavra,
C.A. Nieto de Castro, Fluid Phase Equilib., (submitted 2014).
(5) S.C.S. Rosa, C.A. Nieto de Castro, A.M.F. Palavra, Proceedings of 4th Asian Thermophysical
Properties Conference, 1995, 467-470.
69
OC-16 ORAL COMMUNICATIONS
A holistic approach to polymorphism
A. Joseph,* R.G. Simões,* C.E.S. Bernardes,* M.F.M. Piedade,*†
M.E. Minas da Piedade*
*
Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa,
1749-016 Lisboa, Portugal
†
Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016
Lisboa, Portugal and Centro de Química Estrutural, Instituto Superior Técnico, Universidade de
Lisboa,1049-001 Lisboa, Portugal
Polymorphism, the ability of a given compound to crystallize in diverse crystal forms,
is a common phenomenon in organic molecular solids. Distinct polymorphs may
exhibit significant differences in properties (e.g. color, density, fusion temperature,
solubility). Consequently, their selective and reproducible preparation allows, in
principle, the production of new materials without changing the molecule involved.
This achievement finds important practical applications, for example, in the dye and
pharmaceutical industries. The lack of control over polymorphism can, on the other
hand, wreak havoc with the end uses of a given product.
Well characterized polymorphic systems are also relevant for the assessment of
crystallization theories and for the development of force-fields that are used to
rationalize the structural and energetic properties of organic molecular solids.
An effective strategy for the investigation of
polymorphism in terms of structure and stability
domains of the different forms, and of their selective
and reproducible preparation typically requires a
holistic approach, based on a variety of methods. This
approach will be illustrated here by some recent
studies
from
our
laboratory
on
4-HOC6H4COOR (R = H, CH3) systems.1-6
(1) C.E.S. Bernardes, M.F.M. Piedade, M.E. Minas da Piedade, Cryst. Growth Des., 11, 2008,
2419-2648.
(2) C.E.S. Bernardes, M.E. Minas da Piedade, Cryst. Growth Des., 12, 2012, 2932-2941.
(3) R.G. Simões, C.E.S. Bernardes, M.E. Minas da Piedade, Cryst. Growth Des., 13, 2013, 28032814.
(4) C.E.S. Bernardes, L.M. Ilharco, M.E. Minas da Piedade, J. Mol. Struct., 1078, 2014, 181187.
(5) C.E.S. Bernardes, M.L.S. Matos Lopes, J.R. Ascenso, M.E. Minas da Piedade, Cryst. Growth
Des., 14, 2014, 5436-5441.
70
ORAL COMMUNICATIONS OC-17
Phase-related structural changes in
hydroxyacetone: from gas to cryogenic crystal
I. Reva
CQC, Department of Chemistry, University of Coimbra, 3004-535, Coimbra, Portugal
Here we address capabilities of cryogenic techniques, combined with spectroscopic,
structural, and theoretical methods, in characterization of small molecules. The case
molecule is hydroxyacetone (HA). Due to internal rotations around the single C−C and
C−O bonds, HA can be conceived to adopt several isomeric forms (Scheme 1).
H
O
O
C
H
H
H
O
C
C
CH3
H
O
H
H
C
C
CH3
O
H
H
O
C
CH3
Ct
Tt
Cc
Scheme 1.
The theoretical analysis of the potential energy surface of HA shows that for the
monomeric molecule in vacuo, some of these structures are not stable (viz., Ct).1
Experimentally, structure of HA was probed by the technique where its vapors are
trapped from the gas phase into a solid cryogenic (15 K) environment of inert gas. This
sampling technique is called matrix isolation. Due to fast freezing, matrix isolation
allows to obtain a “snapshot” of the conformational composition characteristic of the
gas-phase thermal equilibrium, and study it at leisure. For HA, the dominating form at
room temperature was shown to be Cc.1
The cryogenic matrix is not a system in thermodynamic equilibrium, and the higherenergy forms may be trapped (or generated) in matrixes also, and exist long enough, if
they are separated by high-enough barriers from the lower-energy forms. For HA, the
high-energy Tt form (+11 kJ/mol) could be generated in situ, by photochemical
methods, and characterized spectroscopically.2
By depositing the neat compound onto a cryogenic substrate at 15 K, we were also able
to create an amorphous phase of HA, which upon thermal cycling, between 15 and 180
K, was transformed into a crystal. Interestingly, the spectroscopic and structural
methods reveal that in crystals HA molecules adopt the Ct structure, which at the
monomeric level is not stable at all.3 Further details – in the presentation.
Acknowledgments: Research Project PTDC/QUI-QUI/118078/2010 (FCT).
(1) A. Sharma, I. Reva, R. Fausto, J. Phys. Chem. A, 112, 2008, 5935-5946.
(2) A. Sharma, I. Reva, R. Fausto, J. Am. Chem. Soc., 133, 2009, 8752-8753.
(3) A. Sharma, I. Reva, R. Fausto, S. Hesse, Z. Xue, M. A. Suhm, S. K. Nayak, R. Sathishkumar,
R. Pal, T. N. Guru Row, J. Am. Chem. Soc., 133, 2011, 20194-20207.
71
OC-18 ORAL COMMUNICATIONS
A phase diagram of a trimorphic system obtained
by superposition of dimorphic diagrams
I.B. Rietveld, B. Nicolaï
Caractérisation des Matériaux Moléculaires à Activité Thérapeutique (CAMMAT), Faculté de Pharmacie,
Université Paris Descartes, 4 avenue de l’observatoire, 75006 Paris, France
Many organic molecules crystallize in different crystal structures, in other words they
exhibit polymorphism. In particular for the pharmaceutical industry, it is important to
establish which of the crystalline phases is the most stable one. The stability hierarchy
can be determined with a straightforward, so-called topological, approach involving (1)
calorimetric and volumetric (by X-ray) measurements, (2) the Le Chatelier principle
and (3) the Clapeyron equation with as a final result a pressure – temperature phase
diagram of the system. For known crystalline phases, it is often not even necessary to
carry out measurements under pressure. Once a phase diagram has been constructed for
a dimorphic system, additional crystalline phases can be incorporated in the stability
hierarchy, by constructing pressure – temperature phase diagrams for each combination
of two crystalline phases. By superposition of these diagrams (and effectively of the
Gibbs energy), the complete phase diagram can be constructed with stable and
metastable solid phases.
This method will be illustrated using the case of L-tyrosine ethyl ester, which possesses
(at least) two crystalline phases occurring under ordinary conditions (I and II) and one
additional phase (III), which apparently only appears under pressure.
It will be shown that the stability hierarchy of
this case of trimorphism can be solved in a
straightforward way by first considering each
dimorphism phase diagram separately. Once
the relative stabilities have been sorted out in
those diagrams, logics, or more precisely the
Gibbs energy ranking, leads to the phase
diagram describing the complete trimorphism.
In this way, a seemingly complicated phase
diagram can be resolved by passing through a
number of relatively simple steps. This
Figure 1. Superposition of dimorphism
approach can obviously be extended to higher
phase diagrams leads to a higher order
order polymorphism.
polymorphism phase diagram.
72
ORAL COMMUNICATIONS OC-19
Giant baro- and magnetocaloric effects in magnetic
shape memory alloys
P. Lloveras,* J. Ll. Tamarit,* M. Barrio,* E. Stern-Taulats,†, A. Planes,†
Ll. Mañosa†
*
Department of Physics and Nuclear Energy, Polytechnics University of Catalonia, Av. Diagonal 647,
08028, Barcelona, Catalonia, Spain
†
Department of Structure and Constituents of Matter, University of Barcelona, Martí I Franquès 1, 08028,
Catalonia, Spain
Giant caloric effects refer to large adiabatic thermal changes or isothermal entropy
changes due to field-driven phase transitions in solid materials. These effects promise
environmentally friendly cooling technologies since they entail a significant decrease
of greenhouse gases release compared to conventional vapor-compression techniques.
The nature of the applied external field leads to name magnetocaloric (MC),
electrocaloric (EC), mechanocaloric effects, etc. The study of caloric materials has been
traditionally centered in giant MC materials1 and first MC cooling prototypes are
already developed. More recently, EC materials2 are gaining importance. However,
several factors limit their practical implementation. Caloric effects under hydrostatic
pressure3 (Barocaloric effects, BC) have been less studied, but they offer great potential
due to the volume changes associated to phase transitions.
Here we report BC effects observed during the magnetostructural phase transition in
Fe-Rh and in a set of off-stoichiometric Ni-Mn-based magnetic shape memory alloys.3
The observed magnitude of the BC effects is comparable to the best known giant MC
effects. Also, it is found that slight variations in the composition lead to significant
modifications of the BC characteristics, which opens the door to the tuning of the
properties for optimal working conditions. In addition, the multiferroic character of the
studied transitions provides these materials with both giant MC and BC effects.
Moreover, in these materials the BC effect is shown to be conventional (the pressure
favors the low-temperature phase) and MC inverse (the magnetic field favors the hightemperature phase). This is explained by the evolution of the structural and magnetic
entropy contributions respectively. The analysis of the underlying physics is crucial to
understand in detail such different thermodynamic features and anticipate good
candidates for technological applications.
(1) X. Moya, S. Kar-Narayan, N.D. Mathur, Nat. Mater., 13, 2014, 439-450.
(2) X. Moya, E. Stern-Taulats, S. Crossley, D. González-Alonso, S. Kar-Narayan, A. Planes, Ll.
Mañosa,N.D. Mathur, Adv. Mater., 25, 2013,1360-1365.
(3) S. Yuce, M. Barrio, B. Emre, E. Stern-Taulats, A. Planes, J.Ll. Tamarit, Y. Mudryk, K.A.
Gschneidner Jr., V.K. Pecharsky Ll. Mañosa., Appl. Phys. Lett., 101, 2012, 071906, Ll.
Mañosa, D. González-Alonso, A. Planes, E. Bonnot, M. Barrio, J.-Ll. Tamarit, Nat. Mater., 9,
2010,478-481, Ll. Mañosa, D. González-Alonso, A. Planes, M. Barrio, J.-Ll. Tamarit et al.,
Nat. Comm., 2, 2011, 595, E. Stern-Taulats et al., Phys. Rev. B, 89, 2014, 214105, Ll. Mañosa
et al., Phys. Stat. Sol. B, 251, 2014, 2114-2119.
73
OC-20 ORAL COMMUNICATIONS
Effects of chromium content on the nitrided layer of
binary Fe-Cr alloys
M.E. Djeghlal,* N. Benrabia,* L. Barrallier†
*
Metallurgy Department , LSGM Laboratory, Polytechnic National School,10 Avenue Pasteur B.P.182,ElHarrach,Algiers Algeria.
†
MecaSurf Laboratory ParisTech, ENSAM , 02 Cours des Arts et Métiers 13617,
Aix –en –Provence , Cédex1, France.
Binary alloys were gas-nitrided at a temperature of 520 °C for 70 h and N2/NH3
ratio of 15 to 20 %. The thickness of the nitrided layers was evaluated by
Vickers hardness testing, morphology and composition of the nitrided layers
was investigated by light and scanning electron microscopy (SEM). Profiles of
phases were calculated by comparison of peak intensities method and the
element profiles by EDS. The study has led to some advantages and
disadvantages brought to nitrided layer by chromium. Namely chromium
increases the solubility of nitrogen in ferrite matrix and increases hardness of
nitrided layer by precipitation of chromium nitride CrN in both coherent and
incoherent states; it decreases thickness of the diffusion and compound layers
and it destabilizes  nitride which causes embrittlement of the compound layer.
74
ORAL COMMUNICATIONS OC-21
Two ternary phase diagrams of
La2O3 - Nb2O5 - (W/Mo)O3:
investigation and structure resolution of their two
new compounds
T.D. Vu,* M. Barré, * K. Adil,† A. Jouanneaux, * F. Goutenoire*
*
IMMM (Institute of Materials and Molecules of Mans), UMR-CNRS 6283, University of Maine, 72085 Le
Mans Cedex 9, France
†
KAUST (King Abdullah University of Science and Technology), Thuwal, Saudi Arabia
The promising La2Mo2O9 compound with high ionic conduction properties suitable for
fuel cell and hydrogen energy technologies was discovered during the investigation of
the La2O3 - MoO3 phase diagram.1 This illustrates the strong link between the study of
phase diagrams and the discovery of new materials, which is one of the intense interests
of all solid-state chemists.
Following this concept, the two ternary phase diagrams of La 2O3 - Nb2O5 - (W/Mo)O3,
which have never been explored and mentioned in literature until now, were
investigated using solid route synthesis. The samples obtained were characterized using
powder X-ray and neutron diffraction, transmission electron microscopy and
impedance spectroscopy on sintered pellets.
Nearly all mono-, bi- and tri-phase zones of these two diagrams were established.
Above all, the crystallographic structures of two novel materials La 3NbWO10 and
La5NbMo2O16 (tetragonal and cubic lattice respectively) were solved and contributed
in the material database. The latter phase does have potential because of its good oxygen
conductivity, as compared with that of La 2Mo2O9.
(1) P. Lacorre, F. Goutenoire, O. Bohnké, Nature, 404, 2000, 856-858.
75
41st Conference on Phase Equilibria
XLIèmes Journées d’Étude des Équilibres entre Phases
JEEP 2015
Poster presentations
POSTER COMMUNICATIONS P-01
Phase behavior at high pressure of CO2 + reference
or vegetable lubricant systems developed for two
stroke engines
T. Regueira,*† O. Fandiño,*‡ L. Lugo,*♯ E.R. López,* J. Fernández*
*
Laboratorio de Propiedades Termofísicas, Departamento de Física Aplicada, Universidad de Santiago de
Compostela, E-15782 Santiago de Compostela, Spain
†
Center for Energy Resources Engineering (CERE), Department of Chemistry, Technical University of
Denmark (DTU), DK 2800 Kgs. Lyngby, Denmark
‡
Dept. Chemistry, University of Guelph, Guelph, ON N1G 2W1, Canada
♯
Departamento de Física Aplicada, Facultade de Ciencias, Universidade de Vigo, E-36310 Vigo, Spain
It is estimated that approximately 50 % of all lubricants sold worldwide end up in the
environment via total loss applications, volatility, spills or accidents. The lubricant
market is dominated by mineral oils, which have a high ecotoxicity and low
biodegradability. Having this in mind, a research project named Biovesin1,2, involving
different groups from academia and several Spanish companies from the energy sector,
was looking for reliable vegetable lubricants for windmills and agricultural machinery.
In particular, two-stroke engines are one of the applications where most of the
lubricants and their degradation products are released directly into the environment,
polluting the soil, water and atmosphere.
In this work we present the CO2 and O2 solubility in a reference semi-synthetic oil, in
vegetable oils and in developed vegetable sunflower-based oils for two stroke engines.
The experimental measurements were performed using two techniques based in
synthetic isochoric or visual methods. We have measured from 283 K to 348 K and
pressures up to 9 MPa with the isochoric apparatus and from 298 K to 363 K up to 75
MPa with the visual technique. The CO2 solubilities in the vegetable oils are higher
than those in the reference oil. At low pressures, the Carvalho and Coutinho model3
provides only good predictions for CO2 solubility in vegetable oils.
Acknowledgments: The Spanish Science and Innovation Ministry and the EU FEDER program are
acknowledged for the financial support of PSE-420000-2008-4 project.
(1) T. Regueira, L. Lugo, O. Fandiño, E.R. López, J. Fernández, Green. Chem., 13 2011, 12931302.
(2) T. Regueira, O. Fandiño, L. Lugo, E.R. López, J. Fernández, J. Supercrit. Fluids, 6, 2012,
123-130.
(3) P.J. Carvalho, J.A.P. Coutinho, J. Phys. Chem. Lett., 1, 2010, 774-780.
79
P-02 POSTER COMMUNICATIONS
High pressure solubility: Improving the uncertainty
of a synthetic isochoric method
E.R. López,* O. Fandiño,*† L. Lugo,*‡ J. Fernández*
*
Laboratorio de Propiedades Termofísicas, Departamento de Física Aplicada, Universidad de Santiago de
Compostela, E-15782 Santiago de Compostela, Spain
†
Dept. Chemistry, University of Guelph, Guelph, ON N1G 2W1, Canada
‡
Departamento de Física Aplicada, Facultade de Ciencias, Universidade de Vigo, E-36310 Vigo, Spain
For the gas solubility calculations using isochoric methods, the amount of absorbed gas
is calculated from the pressure change in the system.1 The mole fraction 𝑥1 of absorbed
gas (1) in the solvent (2) is calculated according to, 𝑥1 = 𝑛1/(𝑛1+𝑛2), where 𝑛2, the
number of moles of the solvent is calculated from the degassed mass introduced in the
equilibrium cell. The volume of the absorbed gas in the solvent, vabs gas was calculated
in our previous articles1,2 using two different estimation methods depending on whether
enthalpy of vaporization is known or not. The total uncertainty of the solubility data,
expressed as mole fraction of CO2 in the liquid phase, x1, was estimated to be close to
6 %.3 The vabs gas is the major contribution to this uncertainty.
In this work we propose an alternative estimation method which improves the
uncertainty of the solubility calculation. This method is based on the availability of the
high pressure density of the analyzed system. In particular, it is presented for the system
CO2 + dipentaerythritol hexaheptanoate.2,4 The expansion volume needed for the
calculation is compared with that of other CO2 systems as those containing ionic liquids
due to the interest in carbon dioxide capture. 5
Acknowledgments: This work was supported by Spanish Ministry of Science and Innovation through
CTQ2011-2392 project and by Xunta de Galicia in the framework of the Galician Network on ILs, ReGaLIs
(R2014/015).
(1) O. Fandiño, E.R. López, L. Lugo, M. Teodorescu, A.M. Mainar, J. Fernández, J. Chem. Eng.
Data, 53, 2008, 1854-1861.
(2) O. Fandiño, E.R. López, L. Lugo, J. Fernández, J. Chem. Eng. Data, 55, 2010, 5483-5488.
(3) O. Fandiño, PhD Thesis, Universidade de Santiago de Compostela, 2009.
(4) O. Fandiño, L. Lugo, J.J. Segovia, E.R. López, M.J.P. Comuñas, J. Fernández, J. Supercrit.
Fluids, 58, 2011, 189-197.
(5) P.J. Carvalho, T. Regueira, J. Fernández, L. Lugo, J. Safarov, E. Hassel, J.A.P. Coutinho, J.
Supercrit. Fluids, 88, 2014, 46-55.
80
POSTER COMMUNICATIONS P-03
The effect of the cation alkyl chain branching on
the mutual solubilities with water, n-butane and
isobutane
K. Shimizu,* J.N. Canongia Lopes*
*
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Portugal
In order to understand from a molecular point of view the water solubility data in the
isomeric ionic liquids (n-butyl versus i-butyl alkyl side chains), we have performed
molecular dynamics (MD) simulations. Three ILs, namely [C4C1im][NTf2] and [iC4C1im][NTf2], along with [C3C1im][NTf2], were selected as representative IL systems.
Three sets of simulations were then performed: (i) pure ILs, (ii) IL-rich mixtures with
water and (iii) aqueous solutions with the ILs at infinite dilution. When the three ILrich mixtures were considered it was noticed that all polar networks remained
practically unchanged—only slightly swelled—as water molecules started to surround
them. In the case of [C3C1im][NTf2], more water molecules can be accepted around its
polar network because it can swell more its polar network. The networks for
[C4C1im][NTf2] and [i-C4C1im][NTf2] were similar but their accessibility was not: in
the iso-butyl IL the alkyl clusters remained closer to the polar network, thus partially
hindering water interactions. On the water-rich side of the mixtures, the main point to
be noticed is that the anion–cation correlation functions show that the two ions form
ion pairs more often, and for longer times than what would be expected if they were
completely isolated and solvated by water molecules and encountered each other on a
purely random basis. This suggests the tendency of these ions to form a second IL-rich
liquid phase as soon as their concentration is raised above their solubility limit in water.1
The structural analysis of the four IL solvents ([C4C1im][NTf2], [i-C4C1im][NTf2],
[C5C1im][NTf2] and [i-C4C1im][NTf2]) obtained by MD simulation is corroborated by
the experimental solubility data of n-butane and isobutane: i) the larger nonpolar
aggregates found in the pentyl-based systems will dissolve more easily the nonpolar
butyl solutes than the butyl-based systems; ii) There are no large structural differences
between the iso- and n-pentyl systems, probably because the changes caused by the
distinct packing of the terminal atoms of the two pentyl chains are less significant in
large clusters.
(1) K.A. Kurnia, T. E. Sintra, C.M.S.S. Neves, K. Shimizu, J.N. Canongia Lopes, F. Gonçalves,
S.P.M. Ventura, M.G. Freire, L.M.N.B.F. Santos, J.A.P. Coutinho, Phys. Chem. Chem. Phys.,
16, 2014, 19952-19963.
81
P-04 POSTER COMMUNICATIONS
Application of hybrid method based on ANN and
PSO algorithm for estimating of the solubility of
solid drugs in sc-CO2
A. Abdallah El Hadj,* M. Laidi,* S. Hanini,† C. Si-Moussa,† T. Omari†
†
* Université of Blida, Algeria.
LBMPT, Universite de Médéa- LBPT -26000, Algeria.
In this work, a hybrid method based on neural network and particle swarm optimization
is applied to develop and validate a model that can predict with precision the solubility
of naproxen in supercritical carbon dioxide at high pressures. ANN was used for
modelling the non-linear process. The PSO was used for two purposes: replacing the
standard back propagation in training the ANN and optimizing the process. The training
and validation strategy has been focused on the use of a validation agreement vector,
determined from linear regression analysis of the predicted versus experimental
outputs, as an indication of the predictive ability of the neural network model. Statistical
analysis of the predictability of the optimized neural network model shows excellent
agreement with experimental data (coefficient of correlation equal to 0.998).
Furthermore, the comparison in terms of average relative deviation (AARD%) between,
the predicted results for the whole temperature and pressure range shows that the ANNPSO model can predict far better the solubility of solid drugs than cubic equations of
state.
Table 1: Structure of the optimized ANN model.
Input
Layer
OSNN
MLP
Hidden Layer
Nb of
neurons
Nb of
neurons
4
6
Output Layer
Activation
Function
Tangente
hyperbolique
TANSIG
Nb of
neurons
Activation
Function
1
Identité
Purline
Training
Algorithm
TRAINSPO
(1) J. Bourquin, H. Schmidli, P. van Hoogvest, H. Leuenberger, Pharm. Dev. Technol., 2, 1997,
95-109.
(2) S.S.T. Ting, D.L. Tomasko, N.R. Foster, S.J. Macnaughton, Ind. Eng. Chem. Res., 32, 2007,
1471-1481.
82
POSTER COMMUNICATIONS P-05
Water solubility of
N-(diethylaminothiocarbonyl)benzimido derivatives
M.A.R. Martins,* B. Schröder,* S.P. Pinho,‡ J.A.P. Coutinho*
*
‡
CICECO, Departamento de Química, Universidade de Aveiro, Aveiro, Portugal
Associate Laboratory LSRE/LCM, Instituto Politécnico de Bragança, Bragança, Portugal
N-(diethylaminothiocarbonyl)benzimido derivatives1,2 have been investigated earlier
because of their application as chelation agents, e.g. in radio pharmaceuticals ( 99mTc).
These compounds are relatively stable, multi-functional substances that may serve as
model compounds for substituted thiourea-based pesticides. Obtaining accurate water
solubilities will relieve the currently unsatisfying data availability and support our
understanding of structure-energy relationships of this type of compounds, with respect
to the varying arrangements of functional moieties.
In this work we report the water solubility of N-(diethylaminothiocarbonyl) benzamidine, PhCNH2NCSNEt2; N-(diethylaminothiocarbonyl)-N’-phenylbenzamidine,
PhCNHPhNCSNEt2;
N-(diethylaminothiocarbonyl)-N’-monoethylbenzamidine,
PhCNHEtNCSNEt2;
N-(diethylaminothiocarbonyl)N’,N’-diethylbenzamidine,
PhCNEt2NCSNEt2;
and
N-(diethylaminothiocarbonyl)benzimido
ethylester,
PhCOEtNCSNEt2, at 298.15 K.
Due the very low solubility values, a particular approach has been applied for the
solubility measurements; a saturated aqueous solution was generated within a dialysis
tubing, followed by careful sampling and dilution in methanol. UV spectroscopy was
used for quantitative analysis, and the methodology showed very good precision.
(1) L. Beyer, J. Hartung, R. Widera, Tetrahedron, 40, 1984, 405-412.
(2) B. Schröder, L.R. Gomes, J.N. Low, L.M.N.B.F. Santos, A.S.M.C. Rodrigues,
J. Mol. Struct., 1004, 2011, 257-264.
83
P-06 POSTER COMMUNICATIONS
Solubility of carbon dioxide in fluoroalkylphosphate
ionic liquids
M.E. Zakrzewska, M. Nunes da Ponte
*
REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de
Lisboa, 2829-516 Caparica, Portugal
Ionic liquids (ILs) are considered promising media for gas separation processes. 1
Solubility of various gases in ILs is high, while IL have essentially no vapour pressure.
ILs with fluorous anions (e.g., hexafluorophosphate ([PF6]-) or tetrafluoroborate ([BF4]) show particularly high CO2 solubility. However, these ILs are sensitive to moisture
and air, especially at elevated temperature. To improve the hydrolytic stability of
fluorophosphates some fluorine atoms can be replaced by hydrophobic perfluoroalkyl
groups. We measured the solubility of CO2 in such ILs, 1-ethyl-3-methylimidazolium,
1-butyl-3-methylimidazolium
and
1-hexyl-3-methylimidazolium
tris(pentafluoroethyl)trifluorophosphate, at temperatures ranging from (313 to 363) K
and pressures up to 15 MPa. Results show that, as predicted, the solubility of CO 2 is
high, increasing with the length of the cation's substituent.
The measurements of solubility were performed in an apparatus design especially for
this purpose and presented in Figure 1. The core of the apparatus was a 3.5 mL,
movable-position high-pressure cell, with a sapphire window allowing visualization of
the internal volume. The cell was placed inside an air bath but equipped with
appropriate handles allowing for an operation form outside. Such a solution eliminated
the problem of “dead volume”, as equilibration of a system and subsequent sampling
could be performed in different positions (horizontally and vertically, respectively).
CO2 was introduced to the cell by a screw injector pump and a whole content was stirred
with a magnetic stirrer. After being equilibrated, samples were collected to a closed
loop and the amount of CO2 dissolved in IL was determined by an expansion into a
previously calibrated volume balloon at sub-atmospheric pressure.
CO2
1
2
4
6
CO2
scCO2
5
3
7
Figure 1. Scheme of the apparatus for solubility measurements:
1 - CO2 supply; 2 - screw injector pump; 3 - air bath;
4 - movable high-pressure view cell; 5 - magnetic stirrer;
6 - closed sampling volume; 7 - expansion volume
(1) L. Zhigang, D. Chengna, B. Chen, Chem. Rev, 114, 2014, 1289-1326.
(2) M.E. Zakrzewska, A.A. Rosatella, S.P. Simeonov, C.A.M. Afonso, V. Najdanovic-Visak,
M. Nunes da Ponte, Fluid Phase Equilib., 354, 2013, 19-23.
84
POSTER COMMUNICATIONS P-07
Understanding the interactions between
ammonium-based bistriflamide ionic liquids and
molecular solvents
A. Mão de Ferro,* P.M. Reis,* A.J.L. Costa,* C.E.S. Bernardes,†
K. Shimizu,† J.N. C. Lopes,*† J.M.S.S. Esperança,* L.P.N. Rebelo*
*
Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, 2780-157
Oeiras, Portugal
†
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa,
Portugal
In the search for more biocompatible ionic liquids (ILs), the short chain ammonium
based ones represent a window of opportunity as an environmental-benign and lowtoxicity cation for IL design. In this work, we have synthesized distinct bistriflimide
ammonium-based ILs with different alkyl chain size and number and type of functional
groups. The aim of this study is to evaluate the impact of these changes on the ILs fluid
phase equilibrium with molecular solvents such as ethers, alcohols, diols, and water,
and on their thermophysical properties such as density, viscosity, conductivity and
refractive index. The experimental results help on the interpretation of the structural
differences between the different ionic liquids used. For example, using two
comparable cations, [N2 1 1 3OH] and [N3 1 1 2OH],1 the density is not similar, which
highlights the distinct effect of increasing an alkyl chain in the apolar group or in the
alkyl chain connected to the OH group. In respect to the liquid-liquid equilibria results,
the most relevant outcome is that the functional group attached to the cation does not
influence the type of phase diagram, while the choice of the solvent does. More
specifically, lower critical solution temperatures were observed (LCST-type phase
diagrams) for mixtures of ammonium-based ionic liquids with ethers, while upper
critical solution temperature were measured (UCST-type phase diagrams) for all the
other systems. However, the miscibility behavior of ionic liquids with different solvents
strongly depends on different factors, such as the number and position of the functional
groups and the size of the alkyl chain of the solvent, as well as the functional group of
the ionic liquid. Auxiliary Ab Initio calculations and Molecular Dynamics simulations
were used to rationalize some of the experimental findings and offer a deeper insight
into the most relevant interactions that control the structure and phase behavior of these
ILs.
Acknowledgments: This work was funded by FCT/MCTES through projects PTDC/CTMNAN/121274/2010 and PTDC/QUI-QUI/117340/2010. A.J.L.C., C.E.S.B., K.S. and J.M.S.S.E.
acknowledge FCT/MCTES for a doctoral and post-doctoral grants and a FCT Investigator contract.2013,
993-9.
(1) A.J.L. Costa, M.R.C. Soromenho, K. Shimizu, I.M. Marrucho, J.M.S.S. Esperanca, J.N.C.
Canongia Lopes, L.P.N. Rebelo, Chem. Phys. Chem., 13, 2012, 1902–1909.
85
P-08 POSTER COMMUNICATIONS
canceled
Thermodynamic study of solvents type ionic
liquids: application in the substitution of polluted
solvents
H. Bouafia, M. Kourichi
Laboratory of Dynamic, Interactions and Reactivity of Systems, Department of Process Engineering,
Faculty of Applied Sciences, University of Kasdi Merbah Ouargla, Algeria
Ionic Liquids have been classed as alternatives solvents that offer possibilities to switch
ordinaries chemical processes into clean and green technologies grace to theirs
favorable physicochemical properties, such as their non volatility in the atmosphere.
Thermodynamic modeling of the liquid-liquid equilibria is very important for the
design, optimization and control of transformations and separations operations. The
optimization of the separation process is one of the most important branches in process
design.
The objective of this work is to use the experimental liquid-liquid equilibria data of
ternary systems involving ionic liquids as solvents for the estimation of new interaction
parameters of the thermodynamic model UNIFAC. The optimal values of these
parameters have been obtained by a calculation program of FORTRAN 90 based on
Nelder-Mead's Simplex optimization method.
The examination of the results permitted to conclude that the UNIFAC model give
better predictions for the 41 studied systems, with root mean square error between
experimental and calculated compositions about 2.17 %.
86
POSTER COMMUNICATIONS P-09
Fluorinated ionic liquids: thermophysical
characterization and partition properties
N.S.M. Vieira,* P.M. Reis,* J.M.M. Araújo,* K. Shimizu,† J.N.C. Lopes,*†
J.M.S.S. Esperança,* A.B. Pereiro,* L.P.N. Rebelo*
*
Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, 2780-157,
Oeiras, Portugal
†
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa,
Av. Rovisco Pais, 1049-001 Lisboa, Portugal
Ionic liquids (ILs) are salts entirely composed of ions, usually an organic cation and an
organic or inorganic anion. Characteristics like hydrophobicity, biodegradation or
toxicity can be manipulated through the conjugation of the different composing ions
take into account the final industrial application desired. These unique properties
combined with their nonvolatile nature allow the development of new and more
economical and sustainable processes attractive for industrial applications. 1
Fluorinated Ionic Liquids (FILs) are a specific family of ILs characterized by having
fluorine tags longer than four carbons. Although the number of publications in ionic
liquids had grown tremendously, there are scarce information about this specific
family.2 The presence of a fluorinated domain in FILs enables their use in extraction
processes to separate perfluoroalkyl acid contaminants from industrial effluents. With
this aim in mind we show how the balance between the three domains (polar, nonpolar
and fluorinated)3 in this specific family influences the thermal and thermophysical
properties, namely density, viscosity, iconicity, conductivity and melting and
decomposition temperature. Also the octanol-water partition coefficient was measured
to evaluate the hydrophobic and hydrophilic nature of the compounds. This information
was also essential to determine the ecotoxicity of FILs and the impact of their use in
the environment.
In conclusion, the final aim of this study is to create knowledge that allows the design
of fluorinated ionic liquid with desired properties for a specific application.
Acknowledgments: This work has been funded by Fundação para a Ciência e Tecnologia, FCT, through
projects PTDC/EQU-FTT/118800/2010, PTDC/CTM-NAN/121274/2010 (including a post-doctoral grant of
P. Reis), and PEst-OE/EQB/LA0004/ 2013. A.B. Pereiro, J.M.M. Araújo, K. Shimizu and J.M.S.S. Esperança
gratefully acknowledge FCT for Post-Doctoral grants SFRH/BPD/84433/2012, SFRH/BPD/65981/2009 and
SFRH/BPD/94291/2013, and a contract under the Investigator FCT program, respectively.2013, 993-9.
(1) R.D. Rogers, K.R. Seddon, Science, 302, 2003, 792-793.
(2) A.B. Pereiro, J.M.M., S. Martinho, F. Alves, S. Nunes, A. Matias, C.M.M. Duarte, L.P.N.
Rebelo, I.M. Marrucho, ACS Sustain Chem. Eng., 1, 2013, 427-439.
(3) A.B. Pereiro, M.J. Pastoriza-Gallego, K. Shimizu, I.M. Marrucho, J.N.C. Canongia Lopes,
M.M. Pineiro, L.P.N. Rebel., J. Phys. Chem. B, 117, 2013, 10826-10833.
87
P-10 POSTER COMMUNICATIONS
canceled
Partition coefficients air/water and octanol/water of
food packaging contaminants isomers:
dibutylphtalate and diisobuylphthalate
H. Ishak,* I. Mokbel,† C. Goutaudier,† J. Jose,† J. Stephan,‡ J. Saab*
*
Université Saint Esprit de Kaslik, Faculty of Sciences, ThEA Group « Thermodynamic, Phases
Equilibrium, and Advanced Analysis», Dept. of Chemistry and Biochemistry, B.P. 446 Jounieh, Lebanon
† Université Claude Bernard Lyon 1, Laboratoire Multimatériaux et Interfaces, UMR 5615 CNRS, bât.
Chevreul, 43, bd 11 novembre 1918 - 69622 Villeurbanne Cedex France
‡ Université Libanaise, Faculté des Sciences, work group « Analyse des Systèmes Polyphasiques-ASP »,
Dept. Chemistry Biochemistry, Fanar, Lebanon.
In order to meet the huge demand of the food industry, there was a remarkable growth
in the development of food packaging in the past decades. Now, a large number of
additives and plastics are introduced to improve the performance in processing or using
packaging materials. Nevertheless, the concern about food safety has increased
significantly by focusing not only on food additives, but also on substances migrating
from packaging material.1 The same concern was also set out in recycled materials
where plasticizers and others contaminants were detected.2
Hauder et al.3 showed that the migration of residual contaminants into the food
packaging is largely governed by their physicochemical properties. In this work, we
present the experimental determination of solubility, vapor pressure and octanol/ water
partition coefficient of two contaminant isomers from the phthalate family: the
Dibutylphthalate (DBP) and Diisobutylphthalates (DiBP). These two isomers are
widely used as plasticizers of PVC.
The vapor pressure measurements (P) were carried out in dynamic mode by the socalled "inert gas saturation method" in the range of [353.15-448.15 K] and results
showed a relative standard deviation (% RSD) less than 5 % and consistency with
literature value for both DiBP and DBP . The octanol - water partition coefficient
(logKo/w) of both isomers, determined in static mode at 298.15 K, showed reproducible
results with % RSD less than 2 % and a relative deviation from literature less than 5 %.
DiBP and DBP aqueous solubility determined in dynamic mode in the temperature
range [293.15-328.15 K] were adjusted by Heidmann equation and showed reliable
results with % RSD less than 4 %.
Acknowledgment: Authors would like to thank the Centre Supérieur de Recherche (CSR-USEK) for the
financial support.
(1) O.-W. Lau, S.-K. Wong, J. Chromatogr. A, 882, 2000, 255-270.
(2) V.I. Triantafyllou, K. Akrida-Demertzi, P.G. Demertzis, Food Chem., 101, 2007, 1759-1768.
(3) J. Hauder, H. Benz, M. Rüter, O.G. Piringer, Food Addit. Contam. A, 30, 2013, 599-611.
88
POSTER COMMUNICATIONS P-11
Detecting univolatility curves in ternary zeotropic
mixtures by using binary distribution lines
I. Rodriguez-Donis, N. Shcherbakova, V. Gerbaud
ENSIACET- INP-LGC UMR 5503, 4 allée Emile Monso. Toulouse, France
Extractive distillation process is the most common for separating low volatility mixture.
It involves the feeding of an extra entrainer E. Howere, optimal performance is
straightly related to the entrainer choice because it determines the position of the
univolatility curve αA,B = 1 into the ternary diagram ABE.1 Detection of the curve αA,B
= 1 seems problematic in the case of ternary zeotropic mixture. Kiva et al.2 revealed
that presence of the line αA,B = 1 in zeotropic ternary mixtures is linked to the behavior
of the distribution coefficient Ki on each binary side. The line αA,B = 1 exists if
interception between any two distribution coefficient lines K i occurs at any binary side
of the ternary diagram. Our contribution deals with the application of computing of K i
lines for determining the existence of αA,B = 1 line in zeotropic ternary mixtures. Figure
1 displays residue curve map of the separation of ethyl acetate – benzene by using nhexanol. Rodriguez-Donis et al.3 demonstrated that depending on n-hexanol flow rate,
benzene can be drawn as distillate instead of the expected ethyl acetate. Critical value
of n-hexanol flow rate is determined by the interception of αA,B = 1 at the binary edge
ethyl acetate–n hexanol (xPA) and at the benzene–n hexanol edge (xPB). For our study
case, crossing of Ki lines either on AE edge or BE edge indicates the existence of the
line αA,B = 1 (Figure 2) providing the value of xPA = 0.404 and xPB = 0.86. Indeed,
Figure 2b, shows that there is a composition region where benzene becomes more
volatile than ethyl acetate (KB > KA).
Figure 1. Ternary Mixture
Figure 2. Lines of distribution coefficient Ki
(b) Edge BE
(a) Edge AE
(1) L. Laroche, N Bekiaris, H.W. Andersen, M. Morari, Can. J. Chem. Eng., 69, 1991, 1302131919.
(2) V.N. Kiva, E.K. Hilmen, S. Skogestad, Chem. Eng. Sci., 58, 2003, 1903-1953.
(3) I. Rodriguez, V. Gerbaud, X. Joulia, Ind. Eng. Chem. Res., 48, 2009, 3560–3567.
89
P-12 POSTER COMMUNICATIONS
Separation of greenhouse gases with ionic liquids
with the soft-SAFT
M.B. Oliveira,* L.M.C. Pereira,* P.J. Carvalho,*
F.Llovell,†, L.F. Veja, †‡, J.A.P. Coutinho*
*
CICECO, Chemistry Department, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal
†
MATGAS Research Center, Campus de la UAB, 09193 Bellaterra, Barcelona, Spain
‡
Carburos Metálicos/Air Products Group, C/Aragón 300, 08009 Barcelona, Spain
Limitations existing in current process control for pollutants and the need for more
economical processes for natural gas streams treatments encourage the development of
new techniques and sorbents. In this sense, ionic liquids (ILs), due to their outstanding
properties and the aptness to fine-tuning, appear as viable alternatives to replace
commonly used solvents in natural gas and post-combustion streams treatment
processes.
The development of theoretical models able to describe the gas-liquid equilibrium
(GLE) of different ILs + gas systems also stands as a vital task for the development and
implementation of new capturing processes. In this regard, the soft-SAFT EoS1, with
proven capacity to accurately describe the GLE of several ILs + gas systems 2-4, is here
used to model the solubility of several pollutants, namely carbon dioxide (CO 2), nitrous
oxide (N2O), methane (CH4) and nitrogen (N2), in ionic liquids not yet addressed with
SAFT approaches, formed by the imidazolium cation and four anions from different
families ([CH3OHPO2], [N(CN)2], [SCN] and [Ac]).
A coarse-grained molecular model is proposed for each ionic liquid based on structural
information and the guidance obtained from quantum calculations, molecular
simulations and/or previous experience. A discussion about the association molecular
parameters values and its relation with the anion nature will also be addressed.
Once the molecular models have been established, high pressure phase equilibria of
binary systems composed of the gases and ILs referred above are described with softSAFT. For a large number of systems, it is possible to predict the behavior without
using binary parameters. When good agreement with the experimental data is not
achieved, a single temperature independent binary parameter is enough to reach a good
description.
Finally, Henry’s constants are calculated in order to provide a study of the selectivity
of those ILs for the CO2/N2O, CO2/CH4 and CO2/N2 separation.
(1) F.J. Blas, L.F. Vega, Mol. Phys., 92, 1997, 135-150.
(2) J.S. Andreu, L.F. Vega, J. Phys. Chem. B, 112, 2008, 15398–15406.
(3) J.S. Andreu, L.F. Vega, J. Phys. Chem. C, 111, 2007, 16028–16034.
(4) F. Llovell, R.M. Marcos, N. MacDowell, L.F. Vega, J. Phys. Chem. B, 16 ,2012, 7709–
7718.
90
POSTER COMMUNICATIONS P-13
Excess enthalpies and phase behavior of mixtures
of hydrogenated and perfluorinated tert-butanol
I.C.M. Vaz,* A.I.M.C.L. Ferreira,* P. Morgado,† E.J.M. Filipe,†
J.A.P. Coutinho,‡ M. Bastos,* L.M.N.B.F. Santos*
*
CIQ, Departamento de Química, Faculdade de Ciências da Universidade do Porto, R. Campo Alegre 687,
4169-007 Porto, Portugal
†
Centro de Química Estrutural, Instituto Superior Técnico, Universidade Técnica de Lisboa, 1049-001
Lisboa, Portugal
‡
CICECO, Departamento de Química, Universidade de Aveiro, 3810-193 Aveiro, Portugal
There are already in the literature results concerning the effect of mixing hydrogenated
and fluorinated molecules that interact through hydrogen bonding. In particular, binary
mixtures of alkanes and perfluoro-alkanes were found to have large positive excess
properties, such as enthalpy and volume.1,2 Regarding the excess properties of mixtures
of hydrogenated and fluorinated alcohols it was found large and positive excess
volumes but large and negative excess enthalpies.3
In this work the excess enthalpies of mixing (H E) of tert-butanol with perfluoro-tertbutanol were measured by Isothermal Titration Calorimetry (ITC) and the SLE was
evaluated by DSC. The ITC experiments were performed at 298.15 K at atmospheric
pressure by addition of perfluoro-tert-butanol to solutions of different molar fraction of
the two alcohols mentioned. Using this methodology it was possible to obtain both the
excess molar enthalpies of mixing and the partial contribution of each alcohols.
From the analysis of the experimental excess enthalpy and SLE diagram it was possible
to get insights into the H-bonds strength in the mixture between hydrogenated and
perfluorinated tert-butanol. The significant differences in acidity and steric hindrance
between the two alcohols leads to a strong H-bond interaction and an “unexpected”
optimal interaction molecular proportion.
(1) P. Morgado, C. McCabe, E.J.M. Filipe, Fluid Phase Equilib., 228-229, 2005, 389-393.
(2) C. Duce, M.R. Tiné, L. Lepori, E. Matteoli, J. Chem. Thermodyn., 39, 2007, 1346-1353.
(3) P. Duarte, M. Silva, D. Rodrigues, P. Morgado, L.F.G. Martins, E.J.M. Filipe,
J. Phys. Chem. B, 117, 2013, 9709-9717.
91
P-14 POSTER COMMUNICATIONS
canceled
Excess molar Gibbs energies of heptan-2-one +
1,4-dichorobutane or + 1,6-dichlorohexane
measurements and predictions
O. Tafat-Igoudjilene,* A. Ait-Kaci, * J. Jose†.
*
Laboratoire de Thermodynamique et de modélisation moléculaire, Université des
Sciences et de la Technologie Houari Boumediene, B.P. 32, El Alia, 16111
Bab-Ezzouar, Alger, Algérie
†
Laboratoire de Chimie Analytique I, Université Claude Bernard-Lyon I, 43, Bd
du 11 Novembre 1918. Villeurbanne Cedex 69622,France
The purpose of this work is the determination of the vapour-liquid equilibria, of heptan2-one + 1,4-dichlorobutane or 1,6-dichlorohexane with view to study the effect of
specific interaction (carbonyl-chlorogroup) on the excess Gibbs energies of heptan-2one + halogenated hydrocarbons.
Halogenated hydrocarbons are manufactured in large quantities and have many
applications (as refrigerants, organics solvents, medicines).
The vapor pressure of the pure compounds and the binary mixtures were measured by
means of a static apparatus at temperatures between (263.15 and 343.15) K. The
apparatus allows measurements in the P range from 27 to 200 103 Pa and from 258 to
468 K .Vapor pressure are measured by means of pressure gauges (Rosemount, model
1151 DPE 22S2, Minneapolis, Minn, USA), protected by a differential pressure
indicator (MKS, Model615D, MKS Instruments, USA).1
The data were correlated with the Antoine equation. Molar excess Gibbs energies, GE,
were calculated for several constant temperatures and fitted using the Redlich-Kister
equation.2
The experimental data of excess molar Gibbs energies, GE, have been compared with
values using the DISQUAC group contribution Model.3,4
(1) A. Blondel-Telouk, H. Loiseleur, A. Barreau, E. Behar, J. Jose, Fluid Phase Equilib.,110,
1995, 315-339.
(2) O. Redlich, A.T. Kister, Ind. Eng. Chem., 40, 1948, 345-348.
(3) H.V. Kehiaian, J.P.E. Grolier, G.C. Benson, J. chim. Phys. Phys.-Chim. Biol., 15, 1978, 10311041.
(4) H.V. Kehiaian, Pure App. Chem., 57, 1985, 15-30.
92
POSTER COMMUNICATIONS P-15
An experimental study on the thermophysical
properties of 2-bromofluorene
J.A.S.A. Oliveira, M.D.M.C. Ribeiro da Silva, M.J.S. Monte
Centro de Investigação em Química, Department of Chemistry and Biochemistry, Faculty of Science,
University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto, Portugal
Following our previous reports on PAHs derivatives with a fluorene core 1,2, the present
work focuses on the vapor pressure study of 2-bromofluorene, using a static method
based on capacitance diaphragm manometers. The experimental (T, p) results were
represented in a phase diagram (lnp vs 1/T) (fig. 1) near the triple point, and the phase
transition properties (standard molar enthalpies, entropies and Gibbs energies) were
determined. DSC measurements were performed in order to determine the enthalpy and
temperature of fusion. These results will be confronted with results reported in the
literature3.
5.0
(liq)
ln(p/Pa)
4.0
3.0
(cr)
Figure 1. Phase diagram of 2-bromofluorene:
 - crystalline vapor pressures;  - stable
liquid vapor pressures;  - super-cooled liquid
vapor pressures; dot/dash - crystalline vapour
pressures from literature3.
2.0
(g)
1.0
0.0
2.4
2.5
2.6
2.7
1000(K/T)
2.8
2.9
Acknowledgments: QREN (FCUP-CIQ-UP-NORTE-07-0124-FEDER-000065project) and to Programa
Ciência 2008 (PEst-C/QUI/UI0081/2013), for granting the financial support to CIQ-UP. JASAO also thanks
FCT for the Ph. D. research grant (SFRH/BD/80372/2011).
(1) J.A.S.A. Oliveira, M.M. Calvinho, R. Notario, M.J.S. Monte, M.D.M.C. Ribeiro da Silva, J.
Chem. Thermodyn., 9, 2013, 222–230.
(2) J.A.S.A. Oliveira, M.J.S. Monte, R. Notario, M.D.M.C. Ribeiro da Silva,
J. Chem. Thermodyn., 76, 2014, 56–63.
(3) J. Fu, E.M. Suuberg, Environ. Toxicol. Chem., 31, 2012, 486–493.
93
P-16 POSTER COMMUNICATIONS
Phase diagram of 4′-methoxyacetophenone
A.R.R.P. Almeida, M.J.S. Monte
Centro de Investigação em Química, Department of Chemistry and Biochemistry, Faculty of Science.
University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto, Portugal
4'-Methoxyacetophenone is found in alcoholic beverages, in cranberry, tomato and
anise and is used as a flavoring ingredient. A static method based on capacitance
diaphragm gauges1 was used to measure the vapor pressures of both condensed phases
of 4′-methoxyacetophenone in the temperature range (298.2 to 355.7) K. The results
enabled the determination of the standard molar entropy, enthalpy and Gibbs energy of
sublimation and of vaporization, at T = 298.15 K, as well as a phase diagram
representation of the (p,T) experimental data near the triple point (Fig. 1). The
temperature and molar enthalpy of fusion were determined using differential scanning
calorimetry and were compared with the values derived from the vapor pressure
measurements.
6.0
liquid
ln(p/Pa)
4.0
crystal
2.0
0.0
O
O
vapor
-2.0
2.80
3.00
3.20
3.40
1000(K/T)
Figure1. Phase diagram of 4'-Methoxyacetophenone. ●, liquid vapor pressures; o, supercooled liquid vapor
pressures; ▼, crystalline vapor pressures; x, ref. 2.
Acknowledgments: Fundação para a Ciência e Tecnologia, Portugal, and to Programa Ciência 2008 (PEstC/QUI/UI0081/2013), for the financial support to CIQ-UP. A.R.R.P.A also thanks FCT, Operational Program
and European Union for the award of the postdoctoral fellowship (SFRH/BPD/97046/2013).
(1) M.J.S. Monte, L.M.N.B.F. Santos, M. Fulem, J.M.S. Fonseca, C.A.D. Sousa, J. Chem. Eng.
Data, 51, 2006, 757–766.
(2) A. Aihara, Bull. Chem. Soc. Jpn. 32, 1959, 1242–1248.
94
POSTER COMMUNICATIONS P-17
Vapor liquid equilibrium of 3,5- and 2,6dimethylpyridine with hexane, cyclohexane and
toluene
H. B.-Makhlouf-Hakem,* A. Ait-Kaci,* J. Jose†
*
Laboratoire de Thermodynamique et Modélisation Moléculaire, Faculté de Chimie, USTHB, BP, 32 ElAlia 16111 Bab Ezzouar, Algerie
†
Laboratoire de Chimie Analytique I, Université Claude Bernard (Lyon I), 43 Boulevard du 11 novembre
1918, Bât Raulin/2, 69622 Villeurbanne Cedex, France
Vapor – liquid equilibrium (VLE) data are essential for engineering design of
separation processes and unit operations. They are useful for an extension of some
thermodynamical models commonly applied for designing petrochemical related
processes. Such information can be obtained experimentally or adopted from
generalized methods to calculate properties of multi-component mixtures. Usually,
densities of vapor and liquid phases are important to give proper size in the process
design of many separation equipments.
The vapour pressures of liquid mixtures 3,5- and 2,6-dimethylpyridine (or lutidines)
with hexane, cyclohexane and toluene were measured by a static method in the range
of 283.15–353.15 K. The pure components vapour pressures data and those of the
mixtures were correlated with the Antoine equation.
(1) A. Blondel-Tellouk, H. Loiseleur, A. Barreau, E. Behar, J. Jose, Fluid Phase Equilib., 110,
1995, 315-339.
(2) H.G. Rackett, J. Chem. Eng. Data 15, 1970, 514-517.
(3) C. Tsonopoulos, AIChe J., 20, 1974, 263-272.
(4) C. Tsonopoulos, AIChe J., 20, 1975, 827-829.
(5) J.A. Barker, Aust. J. Chem., 6, 1953, 207-210.
95
P-18 POSTER COMMUNICATIONS
Liquid phase equilibria of (water-butyric aciddibutyl ether) ternary system at different
temperatures
I. Yalin, S. Çehreli
Istanbul University, Engineering Faculty, Dept. of Chemical Engineering, 34320 Avcilar, Istanbul,Turkey
Butyric acid is widely used in chemical, food and pharmaceutical industries. It is also
used directly as an additive in fibers for heat and sunlight resistance enhancement.1 The
increasing consumer demand for organic natural products in food additives,
pharmaceutical products, and preservatives has taken great interest in the production of
butyric acid through fermentation process. Thus, separation of organic acids from
fermentation medium is important for economic aspect.
Liquid-liquid equilibrium (LLE) data of the related systems are needed for the design
of an efficient extraction system. Many researchs are cited for extraction of aqueous
butyric acid solutions. 2-4 LLE data for the ternary system of (water - butyric aciddibutyl ether) was investigated at 293.15, 303.15, and 313.15 K and atmospheric
pressure. There is no experimental data in the literature for relevant system and
conditions. Tie-line data were measured experimentally. Othmer-Tobias correlation
was used to check the consistency of the experimental tie-line data. Distribution
coefficients and selectivity were calculated from experimental data.
Othmer-Tobias correlation factors being nearly 1 indicates that the experimental data
are consistent. As result, it was seen that (water - butyric acid - dibutyl ether) ternary
systems exhibit liquid phase diagrams of Type I. In all cases, butyric acid was more
soluble in organic phase than in water phase.
(1) C. Zhang, H. Yang, F. Yang, Y. Ma, Curr. Microbiol., 59, 2009, 556-663.
(2) M. Bilgin, J. Chem. Thermodyn., 38, 2006, 1634-1639.
(3) H.G. Gilani, A.G. Gilani, M. Janbaz, J. Chem. Thermodyn., 57, 2013, 152-159.
(4) A.G. Gilani, H.G. Gilani, F. Amouzadeh, J. Chem. Thermodyn., 71, 2014, 103-113.
96
POSTER COMMUNICATIONS P-19
Liquid phase equilibria of (water + acetic acid +
diluted tributylamine) at T = 298.2 K
T. Evlik, Y.S. Aşçı, S. Çehreli
Istanbul University, Engineering Faculty, Chemical Engineering Department,
34320, İstanbul, Turkey
Acetic acid is a very popular and important chemical for the chemical industry. It
extensively has been produced by fermentation processes with different methods.1 It is
well-known that the ideal way to produce carboxylic acids, and also other compounds
having sufficient acidic properties, is the fermentation processes that have already been
proven to be environmentally friendly and renewable resources.2 The most important
problem of fermentation in the production of these carboxylic acids is their low
concentration (< 10 %), and separation of the acid is difficult and expensive. 3
In this work, tributylamine (TBA) solutions in octyl acetate are used as an extractant
for the separation of acetic acid from the aqueous streams.The effects of initial acid
concentration (5 %, 10 % and 15 %), TBA concentration (at six different concentration
values, 0.2 to 1.2 mol/L), and aqueous phase to organic phase ratio (5:1, 5:3, 5:5) are
investigated on the separation efficiency at 298.2 K. Important data for the design and
analysis of different separation processes such as distribution coefficients (D), loading
factors (Z), extraction efficiency (E) have been obtained as a result of batch
experiments.
(1) O. Ozcan, Y.S. Aşçı, İ. İnci, J. Chem. Eng. Data, 58, 2013, 583-587.
(2) E. İnce, Y.S. Aşçı, J. Fluid Phase Equilib., 370, 2014, 19-23.
(3) Y.S. Aşçı, İ. İnci, J. Chem. Eng. Data, 55, 2010, 2385–2389.
97
P-20 POSTER COMMUNICATIONS
Thermodynamic properties of thio organic
compounds with aliphatic hydrocarbons
S. Didaoui, A. Ait-Kaci
Laboratoire de Thermodynamique et de Modélisation Moléculaire. Faculté de Chimie, Université des
Sciences et de la Technologie Houari Boumediène B.P.32 El-Alia Bab-Ezzouar 16111 Alger, Algérie.
Sulfur compounds are one of the common impurities present in crude oil and also found
in distillates and in products from cracking, coking and alkylation processes. Organ
sulfur impurities in gasoline cause severe environmental problems. Consequently, most
countries have applied stricter regulations to lower the sulfur content in gasoline.
The knowledge of thermodynamics' properties, such as solid-liquid equilibrium (SLE),
is important for practical applications of industrial chemistry (e.g. design of
crystallization processes, safe operation of pipelines,…). Therefore, it is essential to
dispose of models able to predict and correlate phase equilibrium.
Solid-liquid equilibrium (SLE) of thiophene or diethyl sulfide with n-heptane, n-octane,
n-decane or n-dodecane mixtures were measured by a static method, heat and volume
of mixtures are measured using a Setaram calorimeter and Anton Paar densimeter
respectively. The DISQUAC group contribution models have tested to describe the
systems at constant pressure.
98
POSTER COMMUNICATIONS P-21
Phase equilibria in the ternary system tetracosane
+ dibenzofuran + biphenyl: experimental data and
prediction with DISQUAC and UNIFAC models
A. Chikh Baelhadj,* Ao. Dahmani,† R. Mahmoud,‡ S. Berkani‡
*
Laboratoire de thermodynamique et de modélisation moléculaire, Faculté de chimie, USTHB, BP 32 ElAlia 16111 Bab-Ezzouar, Algiers, Algérie
† Ecole Militaire Polytechnique EMP, BP 17 Bordj-El-Bahri, Algiers, Algeria
‡
Ecole Nationale Polytechnique, 10, Avenue Hassen Badi El Harrach Algiers, Algeria
Solid-liquid equilibria (SLE) for ternary mixtures consisting of tetracosane +
dibenzofuran + biphenyl have been determined using differential scanning calorimetry
(DSC). The phase diagrams have been established according to the experimental
results. A polynomial equation has been used to correlate the experimental data. The
experimental results have been examined in terms of the predictive group contribution
models DISQUAC1 and UNIFAC2 and compared with ideal model.
(1) S. Delcros, E. Jimenez, L. Romani, A.H. Roux, J-P.E. Grolier, H.V. Kehiaian,
Fluid Phase Equilib., 111, 1995, 71-88.
(2) H. K. Hansen, P. Rasmussen, A. Fredenslund, M. Schiller, J.
Ind. Eng. Chem. Res., 30, 1991, 2352-55.
99
Gmehling,
P-22 POSTER COMMUNICATIONS
Phase equilibria and volumetric properties of
solutions. application to methyl
esters+methanol+octane, or +isooctane
R. Ríos, X. Florido, L. Fernández, J. Ortega
Grupo de Ingeniería Térmica e Instrumentación. Sección de Termodinámica y Fisicoquímica de Fluidos,
Parque Científico-Tecnológico, 35071-Universidad de Las Palmas de Gran Canaria. Canary Islands,
Spain.
It is necessary to know well the behavior of solutions that form part of some petroleum
derived fuels, or biofuels, or even of possible additives, to raise its proposal in the
combustion processes. In this work the results of excess volumes (vE) and liquid-liquid
equilibria (LLE) are presented for the following eight ternaries
Methanol(1)+octane(2)+methyl ethanoate(3)
Methanol(1)+isooctane(2)+methyl ethanoate(3)
Methanol(1)+octane(2)+methyl propanoate(3)
Methanol(1)+isooctane(2)+methyl propanoate(3)
Methanol(1)+octane(2)+methyl butanoate(3)
Methanol(1)+isooctane(2)+methyl butanoate(3)
Methanol(1)+octane(2)+methyl pentanoate(3)
Methanol(1)+isooctane(2)+methyl pentanoate(3)
The volumetric data have been determined, but only in the composition interval having
complete miscibility, since the solutions above mentioned presented immiscibilities.
Therefore, first it was necessary to perform the corresponding studies of the LLEs. The
study of ternaries requires the knowledge of the corresponding binaries comprising the
ternaries, of which only two show partial miscibility, that is: methanol+octane, and
methanol+isooctane. A mathematical model2 was implemented in Matlab© for
correlate the vE and LLE data. A procedure based on genetic algorithms was employed
to get a fit, checking at the same time the principle of phase stability. Figure showed is
a sample of the results corresponding to the data correlation of vE and LLE. Using the
same fit procedure, the NRTL model also was employed which gave place to acceptable
results. The UNIFAC model is not so good for estimating LLE of the solutions studied
here, giving place to immiscibility areas more extensive to those really found.
(1) L.M. Casas, B. Orge, J. Tojo, J. Chem. Eng. Data, 49, 2004, 664-667.
(2) F. Espiau, J. Ortega, L.Fernández, J. Wisniak, Ind. Eng. Chem. Res., 50, 2011, 1225912270.
100
POSTER COMMUNICATIONS P-23
Acrylonitrile recovery system by extractive
distillation: simulation and optimization
M.R. Souza,* S.P. Pinho,‡ P.R.B. Guimarães,† R.F. Vianna‡
*
Programa de Pós-graduação em Engenharia Química, Escola Politécnica, Universidade Federal da Bahia,
Rua Aristides Novis 2, Federação, CEP 40210-630 Salvador, Brazil
‡
Associate Laboratory LSRE/LCM, Instituto Politécnico de Bragança, Campus de Santa Apolónia, 5301857 Bragança, Portugal
†
UNIFACS, Rua Dr. José Peroba 251, STIEP, CEP 41770-235 Salvador, Brazil
Chemical process industries in general, and acrylonitrile units in particular, require
large amounts of energy for their operation. Therefore, the advantages of operating on
optimal conditions based on minimum energy consumption are twofold: reduction in
operating costs and protection of the environment. The ammoxidation process (Sohio)
developed in late 1950, reacts propylene, ammonia and air to produce acrylonitrile, as
well as a wide variety of compounds, such as hydrocyanic acid, acrolein, water and
large amounts of acetonitrile. In the beginning of XXI century, the original Sohio
process and its modifications, were still the main route for acrylonitrile, producing 90
% of 4 million tons produced worldwide each year. 1
This work aims at investigating the optimal operating conditions based on minimum
energy consumption of a real Sohio acrylonitrile recovery system using the Aspen Plus
(vs. 7.2) and Statistic software. A thermodynamic model for representing the VLLE
was selected and the interaction parameters estimated. The simulation considers
pressure drop along the column and stage efficiency.
Results are compared to data of a real operating unit, showing very satisfactory
agreement. Changing the operating conditions, such as the ratio between the mass flows
of the extractive agent and feed, as well as their temperatures, a saving of about 10 %
in the reboiler duty is obtained.
(1) Kirk-Othmer Encyclopedia of Chemical Technology, 4th edition, Wiley-Interscience: New York, 2001.
101
P-24 POSTER COMMUNICATIONS
Phase equilibria of bulk liquid membrane systems
for the separation of formic acid from its aqueous
solution
T. Kaya, M. Bilgin
Istanbul University, Engineering Faculty, Dept. of Chemical Engineering, 34320 Avcilar, Istanbul,Turkey
A two-compartment contactor set up for layered bulk liquid membrane (BLM) system1
was used to determine the phase equilibrium data at room temperature, for separating
formic acid from its aqueous solution (10 % w/w). In the BLM system, beside aqueous
acid solution as feed phases, tributyl phosphate (TBP) dissolved in ethyl butyrate in the
concentrations of (0.5 and 1.5 mol/L) were used as carrier membrane phases, and water
or aqueous NaOH solution (1 and 2 N) were used as stripping phases. The analysis of
the feed and stripping phases was made by the titration method after reaching totally
equilibrium (9 h). Distribution coefficients (d) of formic acid and separation efficiency
(E) were calculated and presented.
(a)
(b)
Figure 1. Phase equilibrium data in terms of (a) distribution coefficients, d, of formic acid and
(b) separation efficiency, E, for the BLM systems including TBP dissolved in ethyl butyrate: The
change with the stripping phase compositions.
It was seen that the stripping phase composition was more efficient than the TBP
concentration in the membrane phase. The presence of NaOH in the stripping phase has
increased both of distribution coefficient and separation efficiency. It will be
environmentally and economically advantageous to use less TBP (0.5 mol /L).
(1) S. Schlosser, E. Sabolova, Chem. Pap., 53, 1999, 403-411.
102
7.8POSTER COMMUNICATIONS P-25
Investigation of lactic acid separation by layered
double hydroxide: equilibrium, kinetics and
thermodynamics
M. Lalikoglu, A. Gök, M.K. Gök, Y.S. Aşçı
Istanbul University, Engineering Faculty, Chemical Engineering Department,
34320, İstanbul, Turkey
Lactic acid (2-Hydroxypropionic acid) is widely used in food, beverages, cosmetic,
pharmaceutical, leather and textile industries.1,2 It is easily produced by fermentation
method and the recovery from the fermentation broth is an important matter in industry
because it effects directly the production cost. In the recent years, many kinds of
adsorbents are developed and used for the separation of carboxylic acids from aqueous
solution. Especially polymeric adsorbents have been used for removal water pollutants
and recycle products from industrial effluents. 3 In this study, the separation of lactic
acid from its aqueous solution was examined by the adsorption onto layered double
hydroxide (LDH), alternatively.
LDH with a highly crystalline structure was synthesized and characterized by FTIR,
XRD and molecular size analyses. The effects of the amount of LDH, temperature, and
initial lactic acid concentration on the adsorption process have been investigated.
Results show that the maximum removal of lactic acid was obtained as 66.49 % in the
case of 1 g LDH at 298 K. The isothermal data were fitted to Langmuir, Freundlich,
and Temkin adsorption isotherms. Elovich and other kinetic model equations were
applied. The temperature dependence of adsorption processes is associated with the
changes in several thermodynamic parameters such as standard free energy (ΔG o),
enthalpy (ΔHo) and entropy (ΔSo).
(1) W. Bi, J. Zhou, K.H. Row, Talanta, 83, 2011, 974-979.
(2) R. Datta, S.P. Tsai, P. Bonsignore, S.H. Moon, J.R. Frank, FEMS Microbiol. Rev., 16, 1995,
221-231.
(3) B. Pan, B. Pan, W. Zhang, L. Lv, Q. Zhang, S. Zheng, Chem. Eng. J., 151, 2009 19-29.
103
P-26 POSTER COMMUNICATIONS
Thermal behavior and heat capacities of benzyl
imidazolium ionic liquids
F.M.S. Ribeiro,* P.B.P. Serra,*† M.A.A. Rocha,*♯ M. Fulem,†‡ K. Růžička,† L.M.N.B.F.
Santos*
*
CIQ, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do
Campo Alegre, 687, P-4169-007 Porto, Portugal
†
Department of Physical Chemistry, Institute of Chemical Technology, Prague, CZ-166 28 Prague 6,
Czech Republic
‡
Institute of Physics, Academy of Sciences of the Czech Republic, Cukrovarnická 10, CZ-162 53 Prague 6,
Czech Republic
♯
Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Den Dolech 2,
5612 AZ Eindhoven, The Netherlands
The thermal behavior, glass transition temperatures, crystallization, melting
temperatures, enthalpies and entropies of isotropization, of ionic liquids (ILs) of the 1benzyl-3-methylimidazolium family, [BzC1im]+, with five different anions: chlorine;
tetrafluoroborate; hexafluorophosphate; 1,1,2,2-tetrafluoroethanesulfonate and
bis(trifluoromethylsulfonyl)imide, are presented.
Heat capacities of the condensed phases were measured by continuous and step method
in the temperature interval from 258 K to 358 K by Tian-Calvet microcalorimeter and,
at T = 298.15 K, by the drop calorimeter. By comparison with the CnC1im + IL series,
the obtained results give insights into the anion character and topology and the
understanding of their contribution to the thermophysical properties of these family of
ionic liquids.
Acknowledgment : Fundação para a Ciência e Tecnologia (FCT), Lisbon, Portugal and to European Social
Fund for financial support to Centro de Investigação em Química, University of Porto (strategic project PEstC/QUI/UI0081/2011). Marisa A.A. Rocha acknowledges the finantial support from FCT and the European
Social Fund (ESF) under the Community Support Framework (CSF) for the award of a Research Grant
SFRH/BD/60513/2009. Paulo B.P. Serra acknowledges financial support from specific university research
(MSMT No. 20/2014). Filipe M.S. Ribeiro acknowledges the finantial support from FCT and the European
Social Fund (ESF) under the Community Support Framework (CSF) for the award of a Research Grant
SFRH/BD/94211/2013.
104
POSTER COMMUNICATIONS P-27
Thermal behavior of low melting point meso-A3B
long alkyl chain-pyridyl porphyrins
C.A. Henriques,* M.J.F. Calvete,* M. Ramos Silva,† M.M. Pereira,* J. Canotilho,‡
M.E.S. Eusébio*
*
†
CQC, Coimbra Chemistry Centre, University of Coimbra, Portugal
CEMDRX, Department of Physics, University of Coimbra, Portugal
‡
Faculty of Pharmacy, University of Coimbra, Portugal
The design and synthesis of tetrapyrrolic macrocycles with modulated structures,
mediated by alkyl side chains, is still a scientific challenge due to their multiple
applications, namely in areas such as catalysis, medicine, molecular devices and
optoelectronics.1 However, their high melting points may limit some of their
applications, which can be overcome by the introduction of alkyl chains in the
beta/meso positions of the porphyrin ring. It should be emphasized that porphyrins have
also received considerable attention as promising candidates to obtain liquid crystalline
materials to be used for molecular electronics, nonlinear
optics, optical data storage, sensors, electrochromic
devices and electrocatalytic systems.2,3
Pursuing our interests in the development of synthetic
methods for the preparation of low melting point nonsymmetric meso-substituted porphyrins,4 with potential
to display liquid crystal properties, in this
communication the thermal behavior of unsymmetrical
porphyrins type A3B, Fig. 1 is presented and discussed.
Figure 1. Porphyrins type A3B
investigated in this work.
Acknowledgements: This work was supported by Pest-UID/QUI/00313/2013
(1) The Porphyrin Handbook Volume 6 - Applications: Past, Present and Future, K.M. Kadish,
K.M. Smith, R. Guilard (Eds), Academic Press, San Diego, 2000.
(2) S.S. Gokakakar, A.V. Slaker, J. Therm. Anal. Calorim., 109, 2012, 1487-1492.
(3) M. Castella, F. López-Calahorra, D. Velasco, H. Finkelmann, Liq. Cryst., 29, 2002, 559-565.
(4) C.A. Henriques, N.P.F. Gonçalves, A.R. Abreu, M.J.F. Calvete, M.M. Pereira, J. Porphyrins
Phthalocyanines, 16, 2012, 291-296.
105
P-28 POSTER COMMUNICATIONS
Phase behaviour of imidazolium NTf2 based ionic
liquids
A.S.M.C. Rodrigues, L.M.N.B.F. Santos
CIQUP, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade Do Porto, Rua do
Campo Alegre, 687, Porto, P-4169-007, Portugal.
Potential application of ILs as solvents, lubricants or fuel cells requires the knowledge
and understanding of their thermal behaviour, especially for low-temperature
applications.
In this work, the thermal phase behaviour of a series of imidazolium NTf2-based ionic
liquids by means of differential scanning calorimetry (DSC) was explored, focused in
the evaluation of the subcooled liquid region, glass transition temperatures,
crystallization and melting temperatures.
The ILs samples were previously heated above the melting temperature and then
submitted to a quenching step consisting in a fast cooling (50 Kmin -1) until -100 ºC.
After that ILs were subjected to several cooling and heating cycles in the crystallization
region, exceeding the glass transition and approaching the temperature of melting to
insure complete crystallization before the melting.
The temperatures of glass transition, Tg, crystallization, Tc, melting, Tf, and the
corresponding enthalpies and entropies of the transitions were determined. These
results were rationalized based on the cation chain length, structural isomerization and
the presence of an acidic N-H in the imidazolium cation.
Acknowledgements: Ana S. M. C. Rodrigues acknowledges the financial support from Fundação para a
Ciência e a Tecnologia for the award of research grant with reference SFRH/BD/81261/2011.
106
POSTER COMMUNICATIONS P-29
A structural and thermodynamic study of
polymorphism in simvastatin
R.G. Simões,* C.E.S. Bernardes,* H.P. Diogo,† M.E. Minas da Piedade*
*
Centro de Química e Bioquímica e Departamento de Química e Bioquímica, Faculdade de Ciências,
Universidade de Lisboa, 1649-016 Lisboa, Portugal
†
Centro de Química Estrutural, Complexo Interdisciplinar, Instituto Superior Técnico,
1049-001 Lisboa, Portugal
Simvastatin (C25H38O5, CAS number [79902-63-9]) is an antilipidemic drug used in the
treatment of high plasma cholesterol concentrations, and thus, in the prevention of
cardiovascular diseases. Like most drugs, simvastatin is normally incorporated as a
solid in pharmaceutical formulations. In such cases, the identification of polymorphism
occurrence and the determination of the stability domains of the different forms
becomes very important for the effective production and safe use of a drug. Indeed,
significant changes in physical properties may result from variations in the solid state
form of a given compound.
In this work, a study of the structural and energetic characterization of simvastatin
polymorphism will be presented. Different structural characterization (XRD, DRIFT,
SEM), calorimetric (DSC, combustion calorimetry), and theoretical methods (quantum
chemistry and MD calculations) were used. The results confirmed the presence of two
low temperature phase transitions1 at TIIIII = (235.9 ± 0.1) K, (  IIIII H m = (0.95 ± 0.06)
kJ·mol-1)2 and TIII = (275.2 ± 0.2) K (  III H m = (3.3 ±0.1) kJ·mol-1),2 with no other
events observed up to fusion ( Tfus = (412.2 ± 0.2) K; fus Hm = (30.4 ± 0.2) kJ·mol-1).2
QC and MD studies supported the hypothesis that these phase transitions are mainly
related to the rotational freedom of the ester group tail of
simvastatin.
Finally, the enthalpies of formation, at 298.15 K,
of solid (form I, stable above 275.2 K), liquid
and gaseous simvastatin were obtained as: f H mo (cr I), =
(1238.4 ± 5.6) kJ·mol-1, f H mo (l) = (1226.4±5.7) kJ·mol-1,
and f H mo (g) = (1063.0 ± 7.1) kJ·mol-1.2
(1) J. Čejka, B. Kratochvíl, I. Císařová, A. Jegorov, Acta Crystallogr. C, 59, 2003, O428-O430.;
M. Hušák, B. Kratochvíl, A. Jegorov, J. Brus, J. Maixner, J. Rohlíček, Struct. Chem., 21, 2010,
511-518.
(2) R.G. Simões, C.E.S. Bernardes, H.P. Diogo, F. Agapito, M.E. Minas da Piedade,
Mol. Pharm., 10, 2013, 2713-2722.
107
P-30 POSTER COMMUNICATIONS
Polymorphic phases of triphenylguanidine
derivatives: charge-density studies
M. Gonçalves, P.S.Pereira Silva, M.R. Silva
CEMDRX, Physics Department, University of Coimbra, Portugal
Triphenylguanidine (TPG) compounds are regarded as potentially interesting for
quadratic non-linear optical (NLO) applications since it was shown experimentally that
molecules with octupolar charge distributions may have NLO properties comparing
favorably to those of their dipolar counterparts. One disadvantage of dipolar molecules
is that they tend to aggregate in centrosymmetric crystals that prevent NLO activity.
The symmetry properties of octupolar molecules could circumvent this disadvantage in
the growth of non-centrosymmetric crystals.1
We will report the crystal structures of the monoclinic polymorph of triphenylguanidine
at 30K and of triphenylguanidinium trifluoroacetate (TPGTFA) at 120K, which have
an order/disorder transition caused by the hampering of the rotation of the CF3 group
with the lowering of temperature.
The XPac program2 will be used to quantify the degree of similarity of the orthorhombic
and monoclinic polymorphs of TPG and to identify similar “supramolecular constructs”
(sub-components of complete crystal structures).
Using the crystal structures obtained with the lowtemperature X-ray diffraction experiments, it was
possible to study the topological properties of the
electron density distributions (see Figure) of TPG and
TPGTFA with the software XD2006.3 All these results
will be presented and discussed.
(1) P.S. Pereira Silva, C. Cardoso, M.R. Silva, J.A. Paixão, A.M. Beja, M.H. Garcia, N. Lopes,
J. Phys. Chem. A, 114, 2010, 2607-2617.
(2) T. Gelbrich, M.B. Hursthouse, Cryst. Eng. Comm., 7, 2005, 324-336.
(3) A. Volkov, P. Macchi, L.J. Farrugia, C. Gatti, P.R. Mallinson,T. Richter, T.S. Koritsánszky,
(2006). XD2006, Rev. 5.34. University at Buffalo, State University of New York, NY, USA.
108
POSTER COMMUNICATIONS P-31
Polymorphism and conformational isomorphism of
m-anisic acid
P.S.P. Silva,* R.A.E. Castro,† E. Melro,‡ M.R. Silva,* T.M.R. Maria,‡
J. Canotilho,† M.E.S. Eusébio,‡
*
CEMDRX, Physics Department, University of Coimbra, P-3004-516 Coimbra, Portugal
†
Faculty of Pharmacy, University of Coimbra, P-3000-548 Coimbra, Portugal
‡
CCC, Department of Chemistry, University of Coimbra, P-3004-535 Coimbra, Portugal
m-Anisic acid is generally recognized as a safe (GRAS) flavoring substance. Its GRAS
status and the functional groups present in the molecule make it an interesting candidate
in pharmaceutical co-crystallization studies. The knowledge of m-anisic acid crystalline
structure/polymorphic behavior is important information for its applications. In this
work a crystalline structure of m-anisic acid form I, Tfus =105 ºC, was solved by singlecrystal X-ray diffraction: monoclinic space group P2 1/n, with a = 13.8075(5)Å, b =
5.0221(2) Å, c = 21.4455(8) Å, β= 99.325(3)º, Mr = 331.37, V = 1467.44(10)Å3. The
molecular flexibility of m-anisic acid results in the presence of two conformers in the
unit cell, a rare case of conformational isomorphism. Using DFT calculations it was
found that these two conformers differ by 4.9 kJmol-1.
Solid samples were generated by crystallization
from solutions, and by melt cooling. From a
multidisciplinary approach involving thermal
analysis (DSC, PLTM), infrared spectroscopy, Xray powder diffraction (see Figure), a monotropic
new solid form II, Tfus = 94 ºC, was identified and
characterized. Polymorph II slowly transforms
into polymorph I at room temperature.
The XPac program1 was used to quantify the degree of similarity of the supramolecular
structure of m-anisic acid with the ortho and para isomers.
(1) T. Gelbrich, M.B. Hursthouse, Cryst. Eng. Comm, 7, 2005, 324-336.
109
P-32 POSTER COMMUNICATIONS
Partial blockage of the reversible solid-solid
transition of strontium succinate
N. Couvrat,* M. Sanselme,* P. Taulelle,† J.M. Lerestif,† M. Lynch,‡
L. Vaysse-Ludot,† G. Coquerel*
*
SMS laboratory, University of Rouen, France
†
Oril Industrie, Bolbec, France
‡
Technologie Servier, Orléans, France
The characterization of APIs polymorphism landscape (i.e. exhaustive knowledge of
every crystalline form of a given compound) is nowadays a routine survey for
pharmaceutical industries.1 In case of an enantiotropic relationship between (at least)
two polymorphs (Low Temperature LT and High Temperature HT forms), such
characterization leads to the determination of: i) their temperature domain of stability
and ii) the temperature of phase transition. Moreover, this transition could be related,
in specific cases, to order/disorder transformations, starting generally from an ordered
LT form to reach a disordered (and thus more symmetrical) HT Form. The transition
type (1st or 2nd order), the existence of a critical transition temperature and the
mechanisms of these latter transformations are still under debate. 2,3
Strontium succinate is a former API produced by Servier laboratory which exhibits a
reversible order-disorder transition from a monoclinic LT form towards a tetragonal
HT form at circa 50 °C. Surprisingly, the crystallization process revealed a partial
blockage of this phase transition upon cooling (remnants traces of HT form were still
present inside the bulk at 20 °C). This partial blockage was studied by In Situ
X-Ray diffraction analyses and thermal analyses. The impact of impurities (mainly
strontium fumarate and water) on the blockage was highlighted and finally an annealing
at 300 °C during 3 hours successfully unjammed the solid-solid transition.
In this study, the impact of chemical
impurities on the thermodynamic
equilibria is discussed and the interesting
isomorphism of strontium salts at high
temperature is presented.
(1) R. Hilfiker, Polymorphism in the pharmaceutical industry, 2006.
(2) M. Kaftory, M. Botoshansky, M. Kapon, V. Shteiman, Acta Cryst. B, 57, 2001, 791-9.
(3) S.J. Coles, T.L. Threlfall, G.J. Tizzard, Cryst. Growth Des., 14, 2014, 1623-8.
110
POSTER COMMUNICATIONS P-33
Phase diagrams for optimization of phenanthrene
purification processes: zone Melting vs.
co-crystallization
A. Burel, S. Brugman, N. Couvrat, S. Tisse, Y. Cartigny, G. Coquerel
Laboratoire SMS, Université de Rouen, 76130 MONT SAINT-AIGNAN, France
Zone Melting (ZM, also called Zone Refinement) has exhibited efficiency for polycyclic
aromatic hydrocarbons (PAH) separation.1 Based on phase segregation, the process
requires knowledge on phase equilibria between the compound to purify and its
impurities in order to predict the impurities distribution in a purified sample.
On the one hand, Phenanthrene (hereafter Phen.) purification has been attempted using
this process, with the aim of reaching ultrapurity (molar purity > 99.9 %) for fine
characterization of the solid-solid transition. The preliminary analytical identification
of commercial Phen. main impurities led to previous investigations of binary phase
diagrams.2,3 9,10-Dihydroanthracene (9,10-DHA) has been identified as one of the
major impurities of selected Phen. batch and this study aims at investigating the Phen.–
9,10-DHA system by DSC and XRDP.
On the other hand, selective co-crystallization of Phenanthrene can be a promising
alternative method to purify this compound. The strategy developed in this work was
to find a co-crystal former (CCF) able to crystallize as a stoichiometric compound with
Phen., but not with its impurities.
During preliminary tests, 3,5-dinitrobenzoic acid (3,5-DNBA) was found to be a cocrystal former with Phen. The phase diagram between both compounds was established
(DSC, XRDP) and revealed the non-miscibility between Phen. and 3,5-DNBA in the
solid state and the existence of two eutectic invariants. Because of the high solubility
of 3,5-DNBA in basic water (by contrast to Phenanthrene) it appears rather
straightforward to retrieve both components after co-crystallization.
The inability of 3,5-DNBA to give co-crystals with Phen. main impurities will be
investigated in future work. In addition, CCFs screening will be continued in order to
find other potential favorable cases in Phenanthrene purification. The target purity
could thus be reached for this molecule by combining co-crystallization and then ZM.
(1) M. Tachibana, M. Furusawa, Anal. Chim. Acta., 251, 1991, 241-246.
(2) N. Couvrat, Y. Cartigny, S. Tisse, M-N. Petit, G. Coquerel, JEEP 2011, 000006, 2011, DOI:
10.1051/jeep/201100006.
(3) A. Burel, N. Couvrat, S. Tisse, Y. Cartigny, G. Coquerel, JEEP 2014, 2014.
111
P-34 POSTER COMMUNICATIONS
Urea/water phase diagram determination by means
of temperature-resolved second harmonic
generation (TR-SHG)
L. Yuan, S. Clevers, N. Couvrat, V. Dupray, G. Coquerel
Normandie université, Crystallogenesis Unit, SMS, EA 3233 Université de Rouen, F-76821 Mont-SaintAignan Cedex, France
A high powered laser wave with a wavelength of 1064 nm can interacts with a noncentrosymmetric material and gives a new wave at twice the initial frequency (532 nm),
this process is called Second Harmonic Generation (SHG). In the case of powder
samples, the detection threshold could be as low as ppm level. So, SHG can be used as
a rapid, reliable and sensitive tool for characterization of organic compounds. 1 Indeed,
it was proposed as an efficient technique for pre-screening of conglomerate forming
compounds, quantifying crystalline phases arising from amorphous materials,
monitoring solid-solid phase transitions in combination with a computer controlled
heating-cooling stage (TR-SHG).2
In this communication, we discuss the possibility of constructing phase diagram with
TR-SHG. An experimental study of urea/water eutectic system is presented. The
reported results show that phase diagram obtained from TR-SHG results fits well with
the literature values.
140
Literature data 1
Literature data 2
SHG data(present work)
120
100
Temperature C
This study demonstrates that TR-SHG is a
promising tool for phase diagram
investigations and precise determination of
eutectic
compositions
between
noncentrosymmetric components (e.g. urea) and
water.
80
60
Liq.
40
20
0
Liq.+<urea>
Liq.+<water>
-20
<water>+<urea>
0
20
40
60
wt.% Urea
(1) L. Smilowitz, B.F. Henson, J.J. Romero, J. phys. Chem. A, 113, 2009, 9650-9657.
(2) S. Clevers, F. Simon, V. Dupray, J. therm. Anal. Calorim., 112, 2013, 271-277.
112
80
100
POSTER COMMUNICATIONS P-35
Incidence of confinement in the crystallization
route from the amorphous state of a chiral
molecule
Q. Viel,*† Y. Cartigny,* G.Coquerel,* E. Dargent,† S. Petit*
*
Unité de Cristallogenèse, EA 3233 SMS, Normandie Université, Université de Rouen,
Mont-Saint-Aignan Cedex, 76821, France.
†
AMME-LECAP, EA4528 International Laboratory, Institut des Matériaux de Rouen, Université de Rouen,
BP12 Saint Etienne du Rouvray Cedex, 76801, France.
Although two enantiomers of an active pharmaceutical ingredient (API) share the same
chemical composition, the spatial arrangement of atoms differs around the asymmetric
center, which often results in significantly different pharmacological properties. The
fundamental mechanisms related to nucleation and growth of chiral APIs from glassy
materials remain largely unexplored and the scientific and industrial communities try
to understand the factors affecting the crystallization route from the amorphous state 12
. Among them some studies are focused on the role of the confinement due to the use
of a cover slide in glass-forming materials during their crystallization process 3. The
chiral drug Diprophylline is used as a racemic solid (a 50/50 mixture of both
enantiomers) in oral dosage forms for treatment of pulmonary diseases. Our previous
study devoted to the establishment of the binary phase diagram between DPL
enantiomers revealed a complex situation which is most probably a consequence of the
molecular flexibility. For instance, we have found that annealing DPL glasses with
various enantiomeric compositions above the DPL glass transition (Tg  37 °C) can
induce the crystallization of stable or metastable enantiomeric and racemic compounds
but also metastable solid solutions 4. The aim of this study is to investigate the impact
of the confinement of the crystallization media during heating of supercooled melts of
DPL with various enantiomeric compositions. Hot Stage Microscopy (HSM) analyzes,
Calorimetric measurements (DSC), X-Ray Powder Diffraction (XRPD) and Raman
spectroscopy have been used to characterize new polymorphic forms obtained with
sample covering.
(1) L. Yu, Adv. Drug Delivery Rev., 48, 2001, 27-42.
(2) B.C. Hancock, S.L. Shamblin, G. Zografi, Pharm. Res., 12, 1995, 799-806.
(3) C. Bhugra, R. Shmeis, M. Pikal, J. Pharm. Sci., 97, 2008, 1829-1849.
(4) C. Brandel, Y. Amharar, M. Rollinger, J. Griesser, Y. Cartigny, S. Petit, G. Coquerel,
Mol. Pharm., 10, 2013, 3850-3861.
113
P-36 POSTER COMMUNICATIONS
Study on the spontaneous resolution of a solvated
racemic Diiron complex via solid-vapor equilibria
Y. Cartigny,* M. Sanselme,* M.Y. Tsang,† F. Teixidor,† C. Viñas,†
J.G. Planas,† G. Coquerel*
†
*
SMS Laboratory, Crystallogenesis Unit, Normandy University, Mont Saint-Aignan France
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus U.A.B. 08193 Bellaterra, Spain.
The diiron complex of (o-carboranyl)(2-hydroxymethyl)pyridine (Fe2Cl3(oCBhmp)3,
scheme 1) presents three chiral centers inducing that a racemic solution of this complex
can crystallize under different solid forms such as racemic compound, conglomerate or
solid solution.1 Di Salvo and coworkers2 isolated and characterized an acetone solvate
racemic compound and an ether solvate conglomerate of this molecule.
The aim of the present study was to investigate the mechanism(s) of spontaneous chiral
discrimination in the solid state between acetone solvate and ether solvate by studying
the solid/vapor equilibria in the Diiron complex/Acetone/Diethylether system.
Direct observations by using microscopes,
gravimetric vapor sorption and X-ray diffraction
measurements during the storage of each
solvated solid phase under the vapor of the
“counter” solvent provided information on the
mechanism involved during the racemic
compound/conglomerate transformation.
This study proved that the solid/vapor equilibria
played a key role in the reversible switch from
racemic compound to conglomerate even if, the
mechanism(s) involve also solid/liquid equilibria
through deliquescence.
Scheme 1: complex of (o-carboranyl)(2hydroxymethyl)pyridine Fe2Cl3(oCBhmp)3.
Stars locate chiral centers.
(1) G. Coquerel, Enantiomer, 5, 2000, 481–498.
(2) F. Di Salvo, M.Y. Tsang, F. Teixidor, C. Viñas, J.G. Planas, J. Crassous, N. Vanthuyne,
N.Aliaga-alcade, E. Ruiz, G. Coquerel, S. Clevers, V. Dupray, D. Choquesillo-Lazarte, M.E.
Light, M.B. Hursthouse, Chem. Eur. J., 20, 2014, 1081-1090.
114
POSTER COMMUNICATIONS P-37
Influence of the water content on the solid-solid
transition of 1,3-dimethylurea
G. Baaklini, M. Sanselme, Y. Cartigny, G. Coquerel
SMS Laboratory, Crystallogenesis Unit, EA 3233,Normandy University, rue Lucien Tesniére, F-76821
Mont Saint-Aignan Cedex, France
Literature review on 1,3-dimethylurea (hereafter DMU) indicates that this molecule
crystallizes into two polymorphic forms, enantropically related: Form (II) is the stable
form at low temperature, and Form (I) the stable one at room temperature, with a not
well-defined transition temperature located between 253 K and room temperature. 1
DSC measurements made in our lab indicated that this solid-solid transition can be
recorded between 298 K and 323 K. The discrepancies between these experimental
results lead us to investigate the DMU-water binary system. Indeed, it is well known
that DMU has a strong interaction with water (deliquescent character if R.H.>60%),
which can influence the temperature of solid-solid transition as in ammonium nitratewater system.2 Therefore, the binary system DMU-Water was investigated by in situ
X-ray diffraction 3 and differential scanning calorimetry (DSC) in order to determine
the nature of equilibria (metatectic or peritectic) associated to the solid-solid transition
of DMU forms with water. Furthermore, the behavior of each solid form of DMU under
variable humidity was investigated by gravimetric vapor sorption experiments.
(1) C. Näther, C. Döring, I. Jess, P.G. Jones, C. Taouss, Acta Cryst., 69, 2013, 70-76.
(2) L. Misane, S. El Allali, M. Kaddami, A. Zrineh, R. Tenu, J. Berthet, J.J. Counioux,
Thermochim. Acta, 354, 2000, 135-144.
(3) International patent PCT/FR2012/050707, G. Coquerel, M.Sanselme, A. Lafontaine,
International patent application WO 2012/136921.
115
P-38 POSTER COMMUNICATIONS
A new polymorphic form of N-methylurea obtained
from melt-crystallization
G. Baaklini, M. Sanselme, G. Coquerel
SMS Laboratory, Crystallogenesis Unit, EA 3233, Normandy University, rue Lucien Tesniére — F-76821
Mont Saint-Aignan Cedex, France
The crystal structure of N-methylurea (hereafter NMU), was first proposed in
19331, the definitive structure was solved in 1976 by Huiszoon et. al. 2 NMU
crystallizes in the orthorhombic system with the chiral space group P212121.
The present work provides the evidence of a new polymorphic form of NMU.
Melt-crystallization of commercial NMU has lead to a new crystalline phase
that exhibits an X-ray powder pattern and stability behavior different from the
commercial form (Fig.1). This new phase was analyzed by Temperature
resolved X-ray diffraction, Differential Scanning Calorimetry (DSC) and
Second Harmonic Generation (SHG).3, 4 Unlike the commercial form, no SHG
signal was detected, thereby this new form crystallizes
in a centrosymmetric
METHYLUREA COMMERCIAL
space group. Furthermore, DSC
findings
show
a
possible
monotropic relationship between
the two polymorphs. This new
polymorphic form requires further
characterization and attempts will
be carried out to determine its
structure.
8000
Lin (Counts)
7000
6000
5000
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2000
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0
12.2
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
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30
2-Theta - Scale
Y + 10.0 mm - METHYLUREA COMMERCIAL - File: METHYLUREA COMMERCIAL.raw - Type: 2Th/Th locked - Start: 3.000 ° - End: 30.028 ° - Step: 0.039 ° - Step time: 96. s - Temp.: 25 °C (Room) - Time Started: 14 s Operations: Y Scale Mul 1.400 | Y Scale Mul 1.400 | Y Scale Mul 2.000 | Y Scale Mul 1.375 | Y Scale Mul 0.125 | Y Scale Mul 0.600 | Y
Y + 20.0 mm - S782 BANCOFLEUR PLAQUE MéTALLIQUE - File: S782 BANCOFLEUR PLAQUE MéTALLIQUE.raw - Type: 2Th/Th locked - Start: 3.000 ° - End: 30.264 ° - Step: 0.039 ° - Step time: 48. s - Temp.: 25 °C (
Operations: X Offset 0.000 | X Offset 0.000 | X Offset 0.000 | X Offset 0.131 | Import
Figure 1: X-ray patterns of the commercial NMU
(blue), and the melt- crystallized NMU (red)
(1) R.B. Corey, R.W.G.Z. Wyckoff, Kristallogr, 85, 1933, 132−42.
(2) C. Huiszoon, G.W.M. Tiemessen, Acta Crystallogr., Sect. B, 2, 1976,1604−1606.
(3) J.M. Cole, P.G. Waddell, C.C. Wilson, J.A.K Howard, J. Phys. Chem., 117, 2013,
25669−25676.
(4) F. Simon, S. Clevers, G. Gbabode, N. Couvrat, V. Agasse-Peulon, M. Sanselme, V. Dupray,
G. Coquerel, Cryst. Growth Des., 2015, accepted DOI: 10.1021/cg5017565.
116
POSTER COMMUNICATIONS P-39
Noteworthy high-energy-conformation selection in
crystalline 1-bromoferrocene and
1,1’-dibromoferrocene
R. Fausto, M.E.S. Eusébio, T.M.R. Maria, P.A. Silva, C.M. Nunes
CQC, Department of Chemistry, University of Coimbra, Portugal
One of the most important factors responsible for the variety molecular aggregates may
exhibit is the similarity between the energies associated with intermolecular nonbonded
interactions and those related with intramolecular conformational flexibility (~1–40 kJ
mol–1). In the chemistry and physics of the organic solid state, conformationally flexible
molecules are then usually prone to polymorphism. In typical cases, different
conformations may lead to different polymorphs, where a less favorable conformational
arrangement might be compensated by a more stabilizing intermolecular packing.
Alternatively, different molecular conformations might be simultaneously present in
the same crystal. Nevertheless, in general the molecules that are present in the crystals
assume conformations resembling those corresponding to possible minimum energy
configurations for the isolated molecule. Profound changes in the typical
conformational order of the isolated molecule upon crystallization are much less
frequent, since they require a rather efficient packing to compensate the energetic
demand resulting from unfavorable conformational intramolecular arrangements.
In this poster, enlightening examples of conformational selection upon crystallization
of 1-bromo and 1,1’-dibromo ferrocene derivatives will be reported. First, one will
show that these two molecules exist both in the gas phase and in cryogenic inert
matrices in well-defined conformers, whose structures and infrared spectra can be
unequivocally established. Then, the conformations assumed by the molecules of the
compounds in crystalline state will be compared with those characteristic of the isolated
molecules. As it will be shown, in the studied compounds intermolecular interactions
present in the solid phases are able to induce a noteworthy high-energy-conformation
selection, leading to presence in these phases of monomeric units with conformations
far from those corresponding to minimum energy structures in the gas phase and found
also to be present for monomers of the compounds isolated in cryogenic matrices.
Acknowledgements: This study was funded by “Fundação para a Ciência e a Tecnologia” (FCT) and the
European Union COMPETE Programme. The Coimbra Chemistry Centre is supported by FCT through the
project Pest OE/ UI/UI0313/2014. The authors are also grateful to Prof. Luís M.N.B.F. Santos (University of
Porto) for having provided the purified samples of the compounds and Profs. José A. Paixão and Manuela R.
Silva (University of Coimbra) for obtaining the X-ray powder diffraction patterns of the original samples.
117
P-40 POSTER COMMUNICATIONS
Synthesis and polymorphism evaluation of the
3,5-bis(decyloxy)benzaldehyde
C.T. Arranja,* R.A.E. Castro,† M.R. Silva ‡ M.E.S. Eusébio,* A.J.F.N. Sobral*
*
Coimbra Chemistry Centre, University of Coimbra, Portugal
†
Faculty of Pharmacy, University of Coimbra, Portugal
‡
CEMDRX, Department of Physics, University of Coimbra, Portugal
Aldehydes are one of the most important classes of organic compounds. Positioned in
the middle of the redox scale of organic molecules, the use of aldehydes in organic
synthesis as precursors for several larger organic molecules is widely spread, being
classical examples its use as precursors of Schiff bases, porphyrins and BODIPYs, with
applications in medicine and materials science. Additionally, aldehydes can be used as
precursors of a number of materials applied as CO2 scavengers.
Compounds with long alkyl chains tend to give rise to some conformational flexibility.
This flexibility, together with the possibility of different intermolecular interactions,
may induce different packing, and consequently several polymorphs with different
physicochemical properties. While performing the
characterization of a set of aldehydes aiming the preparation
First heating run, 32ºC
of BODIPYs for use as sensitizers in organic solar cells,
3,5-bis(decyloxy)benzaldehyde revealed a very interesting
polymorphic behavior.
That compound was characterized by differential scanning
Second heating run, 15ºC
calorimetry, polarized light thermomicroscopy, infrared
1
spectroscopy and X-ray powder diffraction. From the
combined use of those techniques, an interesting polymorphic
behavior was observed and four polymorphs were identified.
The initial compound melts around room temperature, ca. Fig. 1 - PLTM images observed
30 C and several polymorphic forms of lower melting point
during the first and second
heating runs of 3,5–
are obtained by cooling the melt, as will be showed in this bis(decyloxy)benzaldehyde.
communication.
Acknowledgements: This work was supported by PEst-C/QUI/ UI0313/2011, PEst-OE/SAU/UI0177/2011
FCT (FEDER), PEst-C/ FIS/UI0036/2011, and FCT/QREN-COMPETE through projects PTDC/AACCLI/098308/2008, PTDC/AAC-CLI/118092/2010, and SFRH/BD/48269/2008.
(1) C. T. Arranja, M. Marcos, M.R. Silva, M.E.S. Eusébio, R.A.E. Castro, A.J.F.N. Sobral, J.
Therm. Anal. Calorim., 117, 2014, 1375–1383.
118
POSTER COMMUNICATIONS P-41
Tris(8-hydroxiquinolinates)M(III): exploring the
molecular and solid state properties
R.J.S Taveira,* C.F.R.A.C. Lima,*† J.C.S. Costa,* L.M.N.B.F. Santos*
*
Centro de Investigação em Química, Departamento de Química e Bioquímica, Faculdade de Ciências,
Universidade do Porto, P-4169-007 Porto, Portugal.
†
QOPNA, Departamento de Química, Universidade de Aveiro, P-3810-193 Aveiro, Portugal.
Tris(8-Hydroxyquinolinate)M(III) derivatives belong to the list of the most used
electroluminescent/electron transport materials in the production of Organic Light
Emitting Diodes (OLEDs). These organometallic compounds have the common
abbreviation of Mq3, where M is the tetravalent coordinated metal (e.g. Al(III), Ga(III)
and In(III)) and q is the ligand, which can be 8-hydroxyquinoline or some derivative.1
Depending on the substituents in 8-hydroxyquinoline, the Mq3 compounds may adopt
mer- or fac- molecular configurations. This work focuses on evaluating how different
substituents and metals influence the mer-/fac- isomerism in this class of compounds,
and how their preferred molecular structure affects solid phase stability (e.g. existence
of polymorphism and solid-solid transitions).
In this work, several Mq3 derivatives were synthetized using different metals and
substituted 8-hydroxyquinolines, and characterized by UV-Vis, Fluorescence and
NMR spectroscopy and DSC. We aim to explore the influence of small structural
changes at the molecular level on the solid phase properties of tris(8hidroxyquinolinato)M(III) derivatives, and contribute for understanding and improving
the applicability and efficiency of this class of compounds as organic semiconductors.2
(1) B.C. Ling, C.P. Cheng, Z.Q. You, C.P. Hsu, J. Am. Chem. Soc, 127, 2005, 66−67.
(2) J.C.S. Costa, C.F.R.A.C. Lima, L.M.N.B.F. Santos, J. Phys. Chem. C., 118, 2014, 2176221769.
119
P-42 POSTER COMMUNICATIONS
Investigation of levetiracetam enantioselective
co-crystallization with quiral co-formers, ibuprofen
and naproxen
S.C.T. Machado,* R.A.E. Castro,† T.M.R. Maria, * M.T.S. Rosado, * M. Ramos Silva, ‡
J. Canotilho, †M.E.S. Eusébio*
*
CQC, Department of Chemistry, University of Coimbra, 3000-535 Coimbra, Portugal
†
Faculty of Pharmacy, University of Coimbra, 3000-548 Coimbra, Portugal
‡
CEMDRX, Physics Department, University of Coimbra, 3000-516 Coimbra, Portugal
Active pharmaceutical ingredients (APIs) are mostly administered using solid form
dosages (tablets, capsules, etc.), due to enhanced patient compliance.
Different solid forms of the API may be used – polymorphs of the pure compound,
solvates, salts and co-crystals - which may have different physicochemical proprieties.
Therefore, to understand and, if possible to control, the solid state chemistry of APIs,
is an important goal in development of pharmaceutical formulations. 1
Pharmaceutical co-crystal is alternative API solid single crystalline phase made up of
at least two compounds in a defined stoichiometry, generally linked by intermolecular
hydrogen bonds.2 The pure components should be solid at ambient conditions. 2 Cocrystals have obvious advantages when compared to solvates and may be obtained, in
opposite to salts, even if the API does not have ionizable groups.
Chiral APIs play an important role in pharmaceutical industry. The investigation of
enantiomer tendency to co-crystallize in an enantioselective manner is a subject of
current interest.
In this work solid-liquid phase diagrams are used to investigate co-crystal formation
between Levetiracetam, a first line antiepileptic drug and (S)-Ibuprofen and
(S)-Naproxen, two structurally related non-steroidal anti-inflammatory drugs. The
ability of Levetiracetam to originated co-crystals with the racemic co-formers, racemic
compounds in both cases, is also evaluated. Results are presented and discussed.
Acknowledgements: The Coimbra Chemistry Centre, CQC, supported by FCT, through, the project Pest –
UID/QUI/00313/2013.
(1) S.L. Morissette, Ö. Almarsson, M.L. Peterson, J.F. Remenar, M.J. Reada, A.V. Lemmoa, S.
Ellis, M.J. Cimab and C.R. Gardner, Advanced Drug Delivery Reviews. 5, 2004, 275-300.
(2) J. Wouters and L. Quéré, RSC Drug D. Royal Society of Chemistry, 2011, 162-168.
120
POSTER COMMUNICATIONS P-43
Slow molecular mobility on the amorphous state of
nonstreoidal anti-inflamatory drugs: ketoprofen and
ibuprofen
E. Mora,* H.P. Diogo,* J.J. Moura Ramos†
*
Centro de Química Estrutural e †Centro de Química-Física Molecular,
Instituto Superior Técnico, Universidade de Lisboa,1049-001 Lisboa, Portugal
It is alleged that ca 40 % of pharmaceutical drugs show hydrophobic activity and
consequently, present reduced water solubility. From a clinical viewpoint this behavior
results on an incomplete absorption from the gastrointestinal track which may lead to
therapeutic failure. To enhance the solubility, and consequently the bioavailability, of
an API several strategies were developed. One of them consists obtaining the drug in
the amorphous state by quenching it from the isotropic liquid. The high internal energy,
enthalpy and specific volume (metastable state), when compared with the crystalline
counterpart is connected with the instability of the amorphous phase. The molecular
mobility present in the glass state is normally a factor considered as responsible for the
devitrification of the drug. In this context, the characterization of the molecular
mobility, in the vicinity of the glass transition temperature of an amorphous drug 1, is
important for defining the best temperature conditions for storage.
In the present work the dielectric technique of thermally stimulated currents (TSC), will
be used to investigate the slow molecular movements in two nonsteroidal antiinflammatory drugs: ketoprofen and ibuprofen. In addition, DSC measurements will
also allow characterizing the glass transformation region in these two drugs. In
particular, the fragility (or steepness) index of the glass formers will be determined
from the heating rate dependence of the temperature location of the DSC glass
transition signal. The obtained value will be compared with the value obtained by TSC,
and with other results stated in the literature.
Acknowledgement: This work was partially supported by Fundação para a Ciência e a Tecnologia (FCT),
Portugal (Projects Pest-OE/CTM/LA0024/2013 and UID/QUI/00100/2013). A grant awarded by FCT to E.
Mora (PEst-OE/QUI/UI0100/2013 - BL/CQE-2013-017) is also gratefully acknowledged.
(1) E. Mora, H.P. Diogo, J.J. Moura Ramos, Thermochim. Acta, 595, 2014, 83–8.
121
P-44 POSTER COMMUNICATIONS
Understanding the dehydration mechanism of
solvates: from microscopy to molecular level
A. Joseph,* C.E.S. Bernardes,*† A.S. Viana,* M.F.M. Piedade,*†
M.E. Minas da Piedade*
*
Centro de Química e Bioquímica e Departamento de Química e Bioquímica, Faculdade de Ciências,
Universidade de Lisboa, 1749-016 Lisboa, Portugal
†
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa,1049-001 Lisboa,
Portugal
Solvates, and in particular hydrates, commonly occur during the isolation and
processing of organic molecular solids. The evaluation of their tendency to form and to
desolvate is, therefore, of particular interest if tight control over the production and
processing of crystalline organic products is to be achieved. Also relevant, from a more
fundamental point, of view is to understand the mechanism of the desolvation process.
In spite of the important efforts made to systematize the mechanisms of solid state
desolvations, the topic remains a challenge.
A kinetic and mechanistic study of the dehydration of a 4-hydroxynicotinic acid
hemihydrate (4HNA·0.5H2O) is discussed. The hydrate, previously characterized both
from structural and thermodynamic points of view, was found to be robust towards
spontaneous dehydration, thus implying the presence of a significant activation barrier
for water loss.1 This was confirmed by a series of isothermal solid state kinetic
experiments, which indicated that the activation energy, Ea , of the process varied in
the range 85-133 kJ·mol-1, depending on the particle size. These experiments also
indicated that the dehydration reaction conformed to the Avarami Erofeev A2 model,
which assumes a nucleation and growth mechanism. In order to confirm this
assumption microscopic observations (hot stage microscopy, scanning electron
microscopy and atomic force microscopy) were combined with a packing analysis
based on single crystal X-ray diffraction data. Packing analysis suggested that the
dehydration process was not topotatic. Microscopic observations evidenced structural
motifs that are compatible with one dimensional random nucleation and growth of the
anhydrous phase.
(1) E.P. Matias, C.E.S. Bernardes, M.F.M Piedade, M.E. Minas da Piedade, Cryst. Growth Des.,
11, 2011, 2803-2810.
122
POSTER COMMUNICATIONS P-45
Polymorphism of adamantane-1-methanol C11H18O
B. Ben Hassine,* P. Negrier,* M. Barrio,† J.Ll. Tamarit,† D. Mondieig*
*
Laboratoire Ondes et Matière d’Aquitaine, UMR 5798 au CNRS-Université de Bordeaux, 351, cours de la
Libération, 33405 Talence Cedex (France).
†
Grup de Caracterització de Materials, Department de Física i Enginyeria Nuclear, ETSEIB, Diagonal
647, Universitat Politècnica de Catalunya, 08028 Barcelona, Catalonia (Spain).
The derivatives of adamantane show a rich polymorphism that is not sufficiently
investigated and requires a large number of experimental and theoretical investigations
in order to explain the dynamics of disordered phases, orientationally disordered for
many of them1 or with a statistical intrinsic disorder concerning the site occupancy of
several atoms.2 In this work, the polymorphism of Adamantane-1-Methanol (C11H18O)
has been investigated by differential thermal analysis and X-ray diffraction.
Below the melting temperature (389.5 ± 0.4) K this compound exhibits an orthorhombic
phase (Phase I, Pnnm, Z = 12, Z’ = 1.5). The melting
enthalpy is determined to be (18.80 ± 0.37) J mol -1, i.e.,
with an entropy change of 5.8R, much higher than the
quoted value from Timmermans for the melting
orientationally disordered phases (2.5R), so supporting the
ordered character of phase I. This orthorhombic phase
exhibits a statistical disorder concerning the hydrogen
atom related to the oxygen atom, due to the position of one
independent molecule on the mirror. At ca. 272 K phase I
transforms continuously through an order-disorder
transition to a monoclinic phase II (P21/n, Z = 12, Z’ = 3).
The monoclinic and orthorhombic phases present a group-subgroup relationship, which
perfectly agrees with the continuous character of the transition. Moreover, by a
convenient election of an order parameter related to the continuous tilt of the c-axis,
critical exponent for this transition matches very well with the mean field exponent (
critical exponent is ca. 0.5).
(1) M. Barrio, P. Negrier, J.Ll. Tamarit, D. Mondieig. J. Phys. Chem. B, 18, 2014, 9595-9603.
(2) P. Negrier, M. Barrio, M. Romanini, J.Ll. Tamarit, D. Mondieig, A.I. Krivchikov, L.
Kepinski, A. Jezowski, D. Szewczyk, Cryst. Growth Des., 14, 2014, 2626-2632.
123
P-46 POSTER COMMUNICATIONS
Pressure-temperature phase diagram and
polymorphic behavior of 1,2-dibromo-ethane
(C2Br2D4 and C2Br2H4)
Ph. Negrier,* M. Barrio,† J.Ll. Tamarit,† D. Mondieig*
*
Laboratoire Ondes et Matière d'Aquitaine, UMR 5798 au CNRS-Université de Bordeaux, 351, cours de la
Libération, 33405 Talence Cedex, France
†
Grup de Caracterització de Materials, Department de Física I Enginyeria Nuclear, ETSEIB, Diagonal
647, 08028 Barcelona, Universitat Politècnica de Catalunya, Catalonia
Polymorphism of 1,2-dibromo-ethane (both C2Br2D4 and C2Br2H4) was determined at
normal pressure. It consists on a fully ordered low-temperature monoclinic (P21/c, Z =
4) lattice (form II) which transforms to another monoclinic form (P21/c, Z = 2), form I,
at around 256 K and 250 K for the deuterated and for the hydrogenated samples,
respectively, for which, with four equivalent orientations corresponding to /2 rotations
around the Br-Br molecular axis exists. In addition to this stable phases, a metastable
phase III (P21/c, Z = 2), the denser phase, was obtained. In this communication we
present the pressure-temperature phase diagram from the liquid state down to 200 K.
We demonstrate that the metastable phase  appears as the low-temperature and highpressure stable phase. The concurrence of the different two-phase equilibria gives rise
to a triple point involving phases I, II and III (at ca. 90 MPa and 245 K). Volume
variations for the solid-solid transitions coherently agree with the density of the
involved phases determined at normal pressure.
For the whole phases the same kind of molecular conformer, trans, has been found.
This results is quite surprising because in several halogen ethane derivatives
polymorphs are closely related to the different molecular conformers. 1-3
(1) Ph. Negrier, M. Barrio, J.Ll. Tamarit, D. Mondieig, M. Zuriaga, S.C. Pérez. Cryst.
Growth Des., 13, 2013, 2143−2148.
(2) Ph. Negrier, M. Barrio, J.Ll. Tamarit, D. Mondieig, Cryst. Growth Des. 13, 2013,
782−791.
(3) Ph. Negrier, M. Barrio, J.Ll. Tamarit, L.C. Pardo, D. Mondieig, Cryst. Growth Des.
12, 2012,1513−1519.
124
POSTER COMMUNICATIONS P-47
Solid-state studies on C60 solvates grown from
Br2CX2 solvents (X = Cl, H)
J. Ye, M. Barrio, J.Ll. Tamarit, R. Céolin
Grup de Caracterització de Materials, Department de Física I Enginyeria Nuclear, ETSEIB, Diagonal 647,
08028 Barcelona, UniversitatPolitècnica de Catalunya, Catalonia
When C60 is mixed with organic molecules new fullerene derivatives could be formed
with the "guest" species accommodated in the space between the globular C 60
molecules so as to maximize the total density.1 When the guest molecule is small, the
case of alkali fullerides2, for low stoichiometry solvates the fcc structure of the pristine
fullerene can be preserved. Usually this does not happen when the size of the molecule
is greater3,4 although some cases with globular molecules as cubane ((C8H8):C60) and
methylene fluoride ((CF2H2):C60) have been reported.5,6 While the small size of the
methylene fluoride may justify the slight distortion of C60 fcc lattice ,this does not apply
to the cubane molecule with a bigger van der Waals volume. Two binary systems with
solvents of tetrahedral molecules ((CBr2H2), (CBr2Cl2)),van der Waals volumes
intermediate between those for the former molecules and with C2v point-group
symmetries have been characterizated by means thermal analysis and X-Ray
diffraction.
This work is performed within our pursuit on the influence of the solvent molecular
symmetry on the lattice symmetry of the solvate, a topic which has still to be addressed.
(1) I.S. Neretin, Y.L. Slovokhotov, Russ. Chem. Rev., 73, 2004, 455-486.
(2) R.M. Fleming, M.J Rosseinsky, A.P. Ramirez, D.W. Murphy, J.C. Tully, R.C. Haddon, T.
Siegrist, R.Tycko, S.H. Glarum, P. Marsh, G. Dabbagh, S.M. Zahurak, A.V. Makhija, C.
Hampton, Nature, 352, 1991,701–703.
(3) M. Barrio, D.O. López, J.Ll. Tamarit, H. Szwarc, S. Toscani, R. Céolin, Chem. Phys. Lett.,
260, 1996, 78-81.
(4) C. Collins, J. Foulkes, A.D. Bond, J. Klinowski, Phys. Chem. Chem. Phys.,1, 1999, 53235326.
(5) S. Pekker, E. Kováts, G. Oszlányi, G. Bényei, G. Klupp, G. Bortel, I. Jalsovszky, E. Jakab,
F. Borondics, K. Kamarás, M. Bokor, G. Kriza, K. Tompa, G. Faigel, Nat. Mater., 4, 2005,764–
767.
(6) Y.M. Shulga, V.M. Martynenko, S.A. Baskakov, G.V. Shilov, A.N. Trukhanenok, A.F.
Shestakov, Y.G. Morozov, T.N. Fursova, A.V. Bazhenov, V.N. Vasilets, Phys. Status Solidi RRL,
3, 2009,43-45.
125
P-48 POSTER COMMUNICATIONS
Solid-state studies on C60 solvates grown from
dibromopropane (Br2C(CH3)2)
J. Ye, M. Barrio, J.Ll. Tamarit, R. Céolin
Grup de Caracterització de Materials, Department de Física I Enginyeria Nuclear, ETSEIB, Diagonal 647,
08028 Barcelona, UniversitatPolitècnica de Catalunya, Catalonia
Solvates involving tetrahedral molecules of high symmetry (CCl 4, Cl3CH,
Cl3CBr,Br3CH) involve similar stoichiometry and symmetry1-4 solvates with their
volumes and packing monitored by the van der Waals volume of the solvent. From
these results, the question to what extent the volume of the C 60 co-crystals could be
expanded without loss of cohesion, arises. Within this framework the study of the
system C60- Br2C(CH3)2has been undertaken.
A mixture of C60 with an excess of Br2C(CH3)2, was maintained at room temperature
for months in the dark. Cubic crystals were grown after several weeks and found to be
instable in air. The stoichiometry of the solvate C60:12 Br2C(CH3)2 was determined by
TGA experiments. High- resolution X-ray powder diffraction profiles obtained from
crystals crushed in capillaries together with an excess of mother liquor were indexed as
cubic (a = 28.28 Å, Z = 8).The not air-stable solvate with mother liquor was analysed
with differential scanning calorimetry (DSC) and, on heating, a signal starting at 340 K
emerged. To elucidate the nature of this transformation a capillary was heated to 340 K
and the changes of the spectra were measured as a function of time. After ca. 3 hours,
a new X-ray profile, indexed as primitive single-hexagonal (a = 10.088 Å, c = 11.446
Å), was obtained. The former procedure, heating to 340 K and slow evaporation of the
solvent, was applied to obtain the hexagonal solvate for which TGA experiments reveal
the stoichiometry 1:2 (C60:2 Br2C(CH3)2).
Thus, similarly to other solvents formed by tetrahedral molecules, two solvates can be
obtained with the Br2C(CH3)2 solvent. Lattice solvate volumes as a function of the
solvent molecular van der Waals volumes for these kind of tetrahedral molecules
correlate perfectly, which leads to the conclusion that steric effects govern the solvate
formation.
(1) M. Barrio, D.O. López, J.Ll. Tamarit, H. Szwarc, S. Toscani, R. Céolin, Chem. Phys. Lett.,
260, 1996, 78-81.
(2) M. Barrio, D.O. López, J.Ll. Tamarit, P. Espeau, R. Ceolin, Chem. Mater,. 15, 2003, 288291.
(3) J. Jansen, G. Waidmann, Z. Anorg. Allg. Chem,. 621, 1995, 56-60.
(4) C. Collins, J. Foulkes, A.D. Bond, J. Klinowski, Phys. Chem. Chem. Phys.,1, 1999, 53235326.
126
POSTER COMMUNICATIONS P-49
The TCAN-C60 solvate: a “dilute” plastic crystal
E. Mitsari, M. Romanini, M. Barrio, J.Ll. Tamarit, R. Macovez
Grup de Caracterització de Materials, Universitat Politècnica de Catalunya (UPC), Departament de Fisica
i Enginyeria Nuclear, ETSEIB, Barcelona, Spain
Fullerene solvates are ordered binary compounds obtained by evaporation of C 60
solutions in suitable solvents.1-3 We employ dielectric spectroscopy (DS) and X-ray
diffraction (XRD) to characterize the 1:1 solvate of C60 with 1,1,2-trichloroethane
((HCl2)C-C(H2Cl), TCAN). TCAN was chosen because (i) it is polar (thus detectable
by DS) and (ii) it exhibits a plastic crystalline phase at low temperature. TCAN
occupies exclusively pseudo-octahedral interstitial sites of the orthorhombic structure
of the solvate, which can be thought to result from a slightly anisotropic distortion of
the fcc lattice of pristine solid C60.2 While in the plastic phase of pure TCAN the
molecules exist only in the trans conformation, both gauche and trans conformers are
present in the solvate with comparable abundances, as evidenced by XRD, Raman, and
attenuated total reflection IR data.
DS results show that in the solvate the TCAN molecules maintain their rotational
degrees of freedom, as they do in the solvent’s plastic phase, but their relaxation
dynamics is markedly different from the pure solvent. Although all relaxations exhibit
an Arrhenius-like behavior with similar
activation energies (see the figure), the dynamics
of TCAN in the solvate is slower than in its
plastic phase due to the high polarizability of
C60, which results in an electrostatic drag against
dipolar reorientations. This is confirmed by the
slower dynamics in the solvate of the gauche
conformer, whose dipole moment is twice that of
the trans isomer, resulting in stronger
intermolecular interactions.
The TCAN-C60 solvate can therefore be thought of as a “dilute” TCAN plastic crystal
in which intermolecular distances and interactions are substantially modified with
respect to the pure solvent. The observation of two well-separated relaxations, each
corresponding to a distinct conformer, implies that they are not truly collective
relaxations of the TCAN molecules, a fact that can be rationalized considering the
relatively large distance between solvent molecules caused by the C60 spacers.
(1) M. Barrio, D.O. López, J.Ll. Tamarit, P. Espeau, R. Céolin, H. Allouchi., Chem. Mater., 15, 2003, 288291.
(2) F. Michaud, M. Barrio, D.O. López, J.Ll. Tamarit, V. Agafonov, S. Toscani, H. Szwarc, R. Céolin, Chem.
Mater., 12, 2000, 3595-3602.
(3) S. Pekker, E.Kovats, G. Oszlanyi, G. Benyei, G. Klupp, G. Bortel, I. Jalsovszky, E. Jakab, F. Borondics,
K. Kamaras, M. Bokor, G. Kriza, K. Tompa, G. Faigel, Nat. Mater., 4, 2005, 764-767.
127
P-50 POSTER COMMUNICATIONS
Subtle phase transition in a fluorinated
praseodymium complex
V. Pereira,* J. Feldl,* T.M.R. Maria, † P. Martín-Ramos, ‡ D.S.N. Teixeira,* J. MartínGil,# M. Ramos Silva*
*
CEMDRX, Physics Department, University of Coimbra, Portugal
CCC, Department of Chemistry, Rua Larga, University of Coimbra, Portugal
‡
Escuela Politécnica Superior de Huesca, Universidad de Zaragoza, 22071 Huesca, Spain
#
Advanced Materials Laboratory, ETSIIAA, Universidad de Valladolid, Avenida de Madrid 44, 34004
Palencia, Spain
†
Lanthanide (III) complexes show extensive applications in the fields of optoelectronics,
luminescence and magnetism. Lanthanide (III) with organic ligands represent a high
potential class as emissive materials for organic light-emitting diodes (OLED's).1
Trivalent lanthanide ions exhibit long luminescence lifetimes, however, direct
excitation of these ions is difficult. One way to overcome this is to use antenna linkers.
The antenna linker absorbs incoming photons and transfers the energy to the lanthanide
ion in the complex, leading to its indirect excitation.
Within a project of testing several ligands to optimize the lanthanide luminescence, we
have studied the thermal behavior of Aqua-tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl3,5-octanedionate)praseodymium(III).
An initial calorimetric study pointed to a degradation of the compound upon
temperature increase without any previous solid-solid or solid-liquid phase transition,
but a subsequent analysis with thermo-microscopy and temperature-variable X-ray
powder diffraction showed a solid-solid
transformation. These results will be presented
and discussed.
Furthermore, the crystal structure was
determined by single-crystal X-ray diffraction,
showing the ion assembling in dimers, will be
presented (see figure). Results of the magnetic
measurements,
accounting
for
an
antiferromagnetic interaction within the dimer,
will also be shown.
(1) Lanthanide-Based Luminescent Hybrid Materials, K. Binnemans, Chem. Rev.,109, 2009,
4283-374.
128
POSTER COMMUNICATIONS P-51
Mesophase assembling by H-bonding in the
4-(octyloxy)benzoic/4-alkylbenzoic acids series
T.M.R. Maria,* M.D. Miranda,†,§ P. Martín-Ramos,†,‡ F. Vaca-Chávez,#
M.E.S. Eusébio,* P.J. Sebastião,# J. L. Figueirinhas,# M. Ramos Silva†
*
CQC, Chemistry Department, University of Coimbra, Coimbra, Portugal
CEMDRX, Physics Department, University of Coimbra, Coimbra, Portugal
§
European Space Agency, Noordwijk, The Netherlands.
‡
E.P.S. de Huesca, Universidad de Zaragoza, Carretera de Cuarte s/n, 22071 Huesca, Spain
#
Condensed Matter Physics Centre / Department of Physics at Instituto Superior Técnico, Universidade de
Lisboa, Lisbon, Portugal
†
The design of hydrogen-bonded liquid crystals (HBLCs) with non-covalent interactions
is a possibility that has drawn the attention of researchers towards the synthesis of selfassembly systems. A successful HBLC requires not only a complementarity of the
interacting components (H-bond donor and H-bond acceptor), but also a certain
magnitude and direction of the H-bonds.
In the present study, a molecular recognition process between different molecular
species has been successfully used to form new mesogenic molecular structures where
the intermolecular hydrogen bonding occurs between 4-(octyloxy)benzoic acid
(8BAO) and four different 4-alkylbenzoic acids (nBAs, where n=2, 5, 6, 7), resulting
in the formation of new HBLCs.
The synthesis of the four HBLCs under study has been attained by a Green Chemistry
method, avoiding the need for solvents: a mechanochemistry approach has been chosen,
using a ball mill system.1 The resulting series of materials has been characterized by
polarizing optical microscopy, differential scanning calorimetry, vibrational
spectroscopy, X-ray powder diffraction and 1H NMR relaxometry. These results will
be presented and discussed.
The 8BAO+nBA co-crystals under study show a good
thermal and chemical stability upon several heating/cooling
cycles. They all exhibit a mesophase at temperatures from
approximately 50ºC to 130ºC.
For one of the new materials (8BAO+7BA), electro-optical
measurements have also been conducted so as to assess its
performance vs. other well-known liquid crystals.
(1) M.C. Miranda, F.V. Chávez, T.M.R. Maria, M.E.S. Eusébio,
P.J. Sebastião, M, Ramos Silva, Liquid Crystals, 41, 2014, 1743-1751.
129
P-52 POSTER COMMUNICATIONS
Development of a cryogenic miniature
AC-susceptometer for magnetic phase transition
identification
F.J.P. Almeida, J.A. Paixão
CEMDRX, Department of Physics, University of Coimbra, Rua Larga, P-3004-516 Coimbra, Portugal
Common magnetometry uses continuous magnetic fields to measure the magnetization
of materials, whereas AC susceptibility uses sinusoidal fields. This method uses a
primary coil that applies a magnetic field and a secondary one comprising two coils
connected in series and in phase opposition, being the sample placed in the center of
one of the secondary coils and the other coil the reference. The voltage applied in the
primary coil, as well as the values read from the secondary, are both generated and
measured by a Stanford Research Systems Lock-In Amplifier SR830.
This method is sensible to the slope of M(H), making it very sensitive to small magnetic
changes, being a useful method to study spin-glass behavior, magnetic phase
transitions, superparamagnetism and superconductivity.1 Each of these transitions
exhibits characteristic features on the real and imaginary components of the AC
susceptibility.
We are developing a miniature ACsusceptometer that can fit into the cold
finger of a closed-cycle He cryostat
working in the range from 5.5K to
350K. Preliminary results obtained on
samples with ferromagnetic and
superconducting phase transitions will
be presented and discussed. An
evaluation of the instrument's
performance on the basis of these
results will be made.
(1) D. Martien, AC Magnetic Measurements, Quantum Design, 2002.
130
POSTER COMMUNICATIONS P-53
Plastic crystal forming abilities of cyclohexanediol
isomers
M.F. Oliveira,* T.M.R. Maria,* M.T.S. Rosado,* R.A.E. Castro,†
J. Canotilho,† M.R. Silva,‡ M.E.S. Eusébio*
*
CQC, Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal
†
, Faculty of Pharmacy, University of Coimbra, 3000-548 Coimbra, Portugal
‡
CEMDRX, Physics Department, University of Coimbra, 3004-516 Coimbra, Portugal
For molecular crystals, the transition from a complete ordered crystalline phase towards
the liquid phase may be achieved in several stages in such a way that each phase
transition involves a stepwise increase of disorder. When heating a crystalline solid
phase, if orientational order is lost, a plastic crystal mesophase is obtained. Plastic
crystals were described in detail by Timmermans.1 This early work on a range of
molecular plastic crystalline materials identified a number of features of plastic crystal
behaviour, such as a low entropy of melting, fS < 20 JK-1mol-1.
The thermal behavior of cyclohexanediol derivatives constitute an interesting case
study. While cis-1,2 and cis-1,4 isomers present plastic crystal mesophases, for trans1,2 and trans-1,4 isomers these phases were not identified.2-4
In this communication an investigation on the polymorphism of cis-1,3 and trans-1,3cyclohexanediol isomers is undertaken. Unlike the 1,2 and 1,4 isomers in the 1,3
derivatives it is the trans isomer that presents a plastic crystal mesophase. trans-1,3,
cis-1,2 and cis-1,4-cyclohexanediol all share a common molecular feature: one
hydroxyl group in an axial position being the other equatorial.
This investigation supplements a set of experimental data already available on the
thermal behavior and crystalline structure of isomeric cyclohexanediols. These data
will be analyzed in the framework of Hirshfeld surfaces in order to look for any possible
correlation between structure and plastic crystal formation ability.
(1) J. Timmermans, J. Phys. Chem. Solids, 18, 1961, 1-8.
(2) T.M.R. Maria, F.S. Costa, M.L.P. Leitão, J.S. Redinha, Thermochim. Acta, 269, 1995, 405413.
(3) M.L.P. Leitão, R.A.E. Castro, F.S. Costa, J.S. Redinha, Thermochim. Acta, 378, 2001, 117124.
(4) S.V.S. Bebiano, M.T.S. Rosado, R.A.E. Castro, M.R. Silva, J. Canotilho,
T.M.R. Maria, M.E.S Eusébio., J. Molec. Struct., 1078, 2014,10-19.
131
P-54 POSTER COMMUNICATIONS
The extraordinary low pressure
of the I-II-L triple point of ritonavir
R. Céolin, I.B. Rietveld
Caractérisation des Matériaux Moléculaires à Activité Thérapeutique (CAMMAT), Faculté de Pharmacie,
Université Paris Descartes, 4 avenue de l’observatoire, 75006 Paris, France
A topological pressure-temperature phase diagram involving the phase relationships of
ritonavir forms I and II has been constructed using experimental calorimetric and
volumetric data available from the literature.1 The triple point I-II-liquid is located at a
temperature of about 407 K and a pressure as extraordinarily small as 17.5 MPa (175
bar). The I-II equilibrium, approximated by the expression P = 329 – 0.771 T, has a
very shallow negative slope. Thus, the less soluble solid phase (form II) will become
metastable on increasing pressure. At room temperature, form I becomes stable at
around 100 MPa indicating that form II may
turn into form I at a relatively low pressure of
a 1000 bar, which may occur under
processing conditions such as mixing or
grinding. This case is a good example for
which a proper thermodynamic evaluation
trumps “rules of thumb” such as the density
rule, as form I is denser than form II, but not
the more stable phase under ordinary
conditions.
Thus the phase behavior of ritonavir
(Figure 1) is monotropic under ordinary
conditions and with increasing pressure it
becomes relatively quickly enantiotropic with Figure 2. The topological phase diagram
form I melting at the highest temperature.
involving form I and form II of ritonavir.
(1) R. Céolin, I.B. Rietveld, Ann. Pharm. Fr., 73, 2015, 22-30.
132
POSTER COMMUNICATIONS P-55
Effect of substituent size on the molecular
structure and polymorphism of cyclohexanediols:
trans-1,4-cyclohexanedimethanol
M.T.S. Rosado,* T.M.R. Maria,* R.A.E. Castro,† J.Canotilho,†
M. Ramos Silva,‡ M.E.S. Eusébio*
*
CQC, Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal
† Faculty of Pharmacy, University of Coimbra, P-3000-548 Coimbra, Portugal
‡ CEMDRX, Department of Physics, University of Coimbra, P-3004-516 Coimbra, Portugal
The molecular conformations of cyclohexanediols, which present rich polymorphism,
are determined by the equatorial or axial substitution and the diverse intermolecular Hbond networks in condensed phases created by the hydroxyl group torsions. Although
equatorial configurations are often preferred, the importance of axial structures was
recognized before, e.g. in trans-1,4-cyclohexanediol.
This study aims to investigate the influence of a larger and more flexible substituent on
the molecular structure and polymorphism of these materials, using trans-1,4-cyclohexanedimethanol. The full conformational space of the single molecule was explored
by MP2 calculations, showing that the optimized bi-equatorial conformers have similar
stability and the bi-axial have much higher energies. The hydroxymethyl substituents
have preference for gauche/anti or gauche+/gauche− configurations.
Polymorphic forms were generated by crystallization from solutions, and by cooling
the melt, which were characterized by a combination of techniques: DSC, PLTM and
XRD. Two polymorphs were isolated and their crystal structures were solved by single
crystal X-ray analysis. Both were found to contain two of the most stable conformers
found in the computational calculations.
The influence of H-bonding in the polymorphic structures was verified by analysis of
the structural differences between the geometries present in the polymorphs determined
by XRD, and their single molecule counterparts resulting from the theoretical
calculations. Contrary to trans-1,4-cyclohexanediol, both isolated and crystalline forms
of trans-1,4-cyclohexanedimethanol, with large and flexible substituents, the bi-axial
conformations are destabilized over the bi-equatorial.
133
P-56 POSTER COMMUNICATIONS
Molecular Dynamics studies of conjugated
zwitterionic polyelectrolyte interactions with
surfactants in solution
B. Stewart,* T. Costa,* A.T. Marques,* U. Scherf,† M. Knaapila,‡
H.D. Burrows,*
†
*
Departamento de Química, Universidade de Coimbra, Portugal
Macromolecular Chemistry Group, Bergische Universität, D-42119 Wuppertal, Germany
‡
Department of Physics, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark
The high efficiencies observed in photosynthetic light harvesting systems are a result
of their elegant self-assembled structures. In order to mimic these structures in synthetic
systems it is required to both control and understand aggregation.
Here the use of computational techniques is presented as a method by which we can
observe the behaviour of anionic and zwitterionic thiophene-based conjugated polymer
structures (PBS-PF2T) and (ZT)1,2 as well as anionic fluorene based (PBS-PFT) and
cationic (HTMA) and their observed aggregation behavior, in addition to the
significance of surfactant presence upon this
aggregation. Molecular dynamics simulations
have thus far indicated that aggregation of these
polymer species is inhibited in the presence of
non-ionic oxyethylene based surfactants,3 CmEn,
by way of separating the polymers and
encapsulating them in liquid crystalline surfactant
phases. Here the effects of CmEn, as well as
polyvinyl alcohol (PVA), sulfur dodecyl sulfonate
(SDS) and cocamidopropyl betaine (CAPB) are
investigated as aggregation inhibitors. The importance of various inter- and intramolecular interactions and of solute environments will be discussed as contributing
factors in the production of well-defined aggregated structures. Experimental findings
are also included to form an overall representation of the process.
(1) H.D. Burrows, M.J. Tapia, S.M. Fonseca, S. Pradhan, U. Scherf, C.L. Silva, A. C.C. Pais,
A.J.M. Valente, K. Schillén. V Alfredsson, M. Carnerup, M. Tomišič, A. Jamnik, Langmuir., 25,
2006, 5545-5556.
(2) M. Knaapila, S.M. Fonseca, B. Stewart, M. Torkkeli, J. Perlich, S.Pradhan, U. Scherf, R.A.E.
Castro, H. D. Burrows, Soft Matter., 10, 2014, 3103-3112.
(3) H.D. Burrows, S.M. Fonseca, C.L. Silva, A.A.C.C. Pais, M.J. Tapia, S. Pradhan, U. Scherf,
Phys. Chem. Chem. Phys.,10, 2008, 4420-4428.
134
POSTER COMMUNICATIONS P-57
Ionic liquids for biological applications
J.M.M. Araújo, A.B. Pereiro, N.S.M. Vieira, L.P.N. Rebelo
Instituto de Tecnologia Química e Biológica - António Xavier, Universidade Nova de Lisboa, Av. da
República, 2780-157, Oeiras, Portugal
Ionic liquids (ILs) are emerging as novel technology promoters and new materials. A
brief discussion on their use in different biological applications, such as
pharmaceutically active components1 and amphiphilic surfactants,2 will be presented.
As for their use in pharmaceutical applications, the dual nature of ILs has been exploited
by combining the cheap, easily available (and essential nutrient) cholinium cation with
pharmaceutically active anions, upgrading the chemical, physical and
biopharmaceutical properties, particularly lowering their melting points, increasing
their aqueous solubility, and, as well their potential to penetrate cell membranes, as
compared to their parent active pharmaceutical ingredients (APIs). In vitro cytotoxicity
levels for both cholinium-based API-ILs and parent APIs were determined using
different human cells lines, demonstrating that this approach does not impair the
cytotoxicity response of the parent APIs, prompting opportunities to obtain further
advances in nowadays pharmaceutical challenges.
The study of ILs as potential new amphiphilic surfactants in aqueous media
demonstrates that ILs can be designed to provide tunable hydrophilic-lipophilic
balances, allowing improved performances. At least, a few fluorinated ionic liquids
(FILs) surfactants are of interest for both a range of biomedical applications and as
environmentally benign selective fluorinated systems. The aggregation behaviour of
some non-toxic FILs in aqueous solution was studied by conductivity and surface
tension measurements, isothermal titration calorimetry (ITC), dynamic light scattering
(DLS), and transmission electron microscopy (TEM) as well. This information is
crucial to understand how such structures influence both the use and toxicity of these
FILs. The study of both their toxicity and biocompatibility was performed using
different types of human cell cultures.
(1) J.M.M. Araújo, C. Florindo, A.B. Pereiro, N.S.M. Vieira, A.A. Matias, C.M.M. Duarte,
L.P.N. Rebelo, I.M. Marrucho, RSC Adv., 4, 2014, 28126-28132.
(2) A.B. Pereiro, J.M.M. Araujo, F.S. Teixeira, I.M. Marrucho, M.M. Pineiro, L.P.N. Rebelo,
Langmuir, 31, 2015, 1283-1295.
135
P-58 POSTER COMMUNICATIONS
Towards realistic modeling of PF8 in the solid state
L.L.G. Justino,* M.L. Ramos,* J. Morgado,† R. Fausto,* H. D. Burrows*
*
Departmento de Química, e Centro de Química de Coimbra, Universidade de Coimbra,
3004-535 Coimbra, Portugal
†
Instituto de Telecomunicações, e Departamento de Bioengenharia, Instituto Superior Técnico,
Universidade de Lisboa, Avenida Rovisco Pais, P-1049-001 Lisboa, Portugal
Polyfluorenes are conjugated polymers which have excellent photophysical and
optoelectronic properties, allowing a wide range of applications from light emitting
diodes (LEDs), to thin-film transistors, sensors and photovoltaic cells.1 In addition, they
show good solubility in many common solvents, and possess interesting phase
behavior, which can lead to different morphologies and characteristics of deposited
films. Particularly interesting behavior is observed when films of poly(9,9dioctylfluorene) (PF8), and some other linear side chain poly(9,9-dialkylfluorenes), are
obtained from poor solvents. With certain alkyl chain lengths, the so-called beta-phase
is formed, which shows enhanced emission in light emitting devices, in addition to
increased structuring and a red shift in the photoluminescence.
We have shown that DFT-based approaches allow for reasonably accurate
optoelectronic properties on fluorene polymers and copolymers in solution. 2 In this
communication we will present results on conformation and aggregation behavior of
PF8 in different solvents and over a range of concentrations. We will see that gels are
formed in dense solutions. Studies were carried out using magic angle spinning NMR
and simulation of the aggregation behavior was carried out using DFT and
semiempirical calculations. These results constitute a first step towards the analysis of
PF8 in the solid state.
(1) R.H. Friend, R.W. Gymer, A.B. Holmes, J.H. Burroughes, C. Taliani, D.D.C. Bradley, D.A.
Dos Santos, J.L. Bredas, M. Logdlund, W.R. Salaneck, Nature, 397, 1999, 121-128.
(2) L.L.G. Justino, M.L. Ramos, P.E. Abreu, A. Charas, J. Morgado, U. Scherf, B.F. Minaev, H.
Ågren, H.D. Burrows, J. Phys. Chem. C 117, 2013, 17969-17982.
136
POSTER COMMUNICATIONS P-59
Nanostructuring 8-hydroxyquinoline-5-sulfonate
and trivalent metal ions in the presence of
surfactants for optoelectronics and sensing
M.L. Ramos, L.L.G. Justino, B. Stewart, T. Costa,
H.D. Burrows
Chemistry Department and Coimbra Chemistry Centre, University of Coimbra,
3004-535 Coimbra
Over 25 years ago, Tang and VanSlyke1 showed that efficient electroluminescence
could be obtained from a device based on tris(8-hydroxyquinoline)aluminium(III)
(Alq3). The area of organic light emitting diodes (OLEDs) based on Alq 3 for high
resolution displays has developed from this into a multibillion Euro industry. We have
been studying the luminescent complexes formed by the water soluble ligand 8hydroxyquinoline-5-sulfonate (8-HQS) with trivalent metal ions, Al(III) and Ga(III) 2,3
and various other metal ions using 1H and 13C NMR, UV/visible absorption and
fluorescence spectroscopy, and density functional theory (DFT) calculations. It has
recently been shown that these can be incorporated as water based components into
LEDs by self-assembly in appropriate matrices, such as layered double hydroxides
(LDHs).4 LDHs involve surfactants, and to obtain more information on nanostructuring
in these systems we have studied the effect of cationic tetraalkylammonium surfactants
on the complexation of 8-HQS with gallium(III) in aqueous solutions using NMR,
absorption and fluorescence spectroscopy and DFT calculations. The results will be
compared with those previously obtained with aluminium(III) 5, and potential
applications of these aggregates in both optoelecronics and sensing will be discussed.
(1) C.W. Tang, S. A. VanSlyke, Appl. Phys. Lett., 51, 1987, 913-915.
(2) M.L. Ramos, L.L.G. Justino, A.I.N. Salvador, A.R.E. de Sousa, P.E. Abreu, S.M. Fonseca,
H.D. Burrows, Dalton Trans., 41, 2012, 12478-12489.
(3) M.L. Ramos, A.R.E. de Sousa, L.L.G. Justino, S.M. Fonseca, C.F.G.C. Geraldes, H.D.
Burrows, Dalton Trans., 42, 2013, 3682-3694.
(4) S. Li, J. Lu, H. Ma, D. Yan, M. Wei, D.G. Evans, X. Duan, Langmuir, 27, 2011, 1150111507.
(5) M.L. Ramos, L.L.G. Justino, T. Costa, H.D. Burrows, “Complexation of 8-Hydroxyquinoline5-Sulfonate and Metal ions in the Presence of Surfactants for Optoelectronics and Sensing” 20th
International Symposium on Surfactants in Solution, SIS2014, June 22 nd -27th 2014, Coimbra,
Portugal.
137
P-60 POSTER COMMUNICATIONS
The influence of molecular symmetry on the
entropy of pure phases
C.F.R.A.C. Lima,*† A.M.S. Silva,† L.M.N.B.F. Santos*
*
CIQ, Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, P-4169007 Porto, Portugal.
†
Department of Chemistry & QOPNA, University of Aveiro, P-3810-193 Aveiro, Portugal.
Symmetric molecular compounds are known to generally present higher melting points
and lower volatility when compared to less symmetric analogues. 1-3 However, the
question remains if more symmetry decreases the entropy of the liquid and gas phases,
increases the entropy of the solid, or it’s a combination of both effects to varying
extents.1-3 Herein a solution to this problem is proposed, which is based on accurate
thermodynamic measurements on the fusion and sublimation equilibria of some
selected interrelated compounds. The results evidence that, when considering relatively
large polyatomic molecules, molecular symmetry chiefly influences the entropy of the
crystal phase (higher symmetry → higher entropy), while it appears to have a negligible
effect on the entropy of the liquid and gas. More symmetry increases the number of
equivalent ways to allocate the molecule in the crystal lattice and consequently
increases the residual entropy of the solid.
(1) R. Abramowitz, S.H. Yalkowsky, Pharm. Res., 7, 1990, 942-947.
(2) R. Pinal, Org. Biomol. Chem., 2, 2004, 2692-2699.
(3) C.F.R.A.C. Lima, M.A.A. Rocha, A. Melo, L.R. Gomes, J.N. Low, L.M.N.B.F. Santos, J.
Phys. Chem. A, 115, 2011, 11876-11888.
138
POSTER COMMUNICATIONS P-61
Molecular crowding effects on the thermotropic
properties of lipid bilayers
A.M. Alves, R. Cardoso, M.J. Moreno
Biological Chemistry Group, Chemistry Department FCTUC, 3004-535, Coimbra, Portugal
Membranes delimit cells and organelles controlling their aqueous content and the
communication with the external aqueous media. The cytoplasm has a high
concentration of small molecules, macromolecules and supramolecular assemblies
where a significant fraction of the water is involved in solvation and does not behave
as bulk water. The limited availability of water and distinct properties affect the
structure and dynamics of macromolecules and supramolecular structures and this is
generally described as molecular crowding effects.
One common agent of molecular crowding is trehalose, a non-reducing disaccharide.
The role of crowding agents in stabilizing the molecular structure of native proteins
are well known as well as its importance in the preservation of biomembranes in
conditions of dehydration and/or very low temperatures. However the effect on the
properties of hydrated membranes and normal temperatures has been the subject of few
studies and is not well characterized.
In this work, we have evaluated the molecular crowding effects, generated by trehalose
under excess water conditions, on the thermotropic properties of different lipid bilayers.
The lipid compositions studied where mixtures of DMPC:DSPC, SpM:Chol and
POPC:SpM (at different molar ratios) corresponding to membranes in the gel, liquid
ordered or liquid disordered phase as well as with coexistence of the distinct phases.
The effects at the membrane interface and hydrophobic core were characterized by
fluorescence anisotropy of NBD-DMPE and TMA-DPH, respectively. To complement
those results, fluorescence lifetimes of NBD-DMPE in POPC, SpM and DSPC were
also measured.
It is observed a significant increase in the width of the phase transitions indicating
stabilization of phase coexistence by 1 M trehalose in the aqueous solution. This effect
is particularly relevant for membranes with coexistence of liquid-disordered and gel
phases. This may be the result of an increase in the solubility of non-polar groups in
aqueous solutions containing high trehalose concentrations, as observed recently by
us.1
(1) G. Bai, S.C.C. Nunes, M.A.A. Rocha, L.M.N.B.F. Santos, M.E.S. Eusébio, M.J. Moreno, M.
Bastos, Pure Appl. Chem., 86, 2014, 223-231.
139
P-62 POSTER COMMUNICATIONS
Approximation of the low-temperature heat
capacity of AIIIBV compounds by linear combination
of Debye’s functions
V.P. Vassiliev,* V.A. Lysenko,* A.F. Taldrik,† N.I. Ilinykh,‡ L.G. Sevastyanova*
*
Chemistry Department, Lomonosov Moscow State University, Leninskiye Gory, Moscow 119992, Russia,
†
Institute of Superconductivity and Solid State Physics, Academician 1.Kurchatov Str., Moscow123098,
Russia
‡
Ural Technical Institute of Telecommunications and Informatics, 15, Repin Str., Yekaterinburg, 620109,
Russia
In this report, we propose an approach to describe the specific heats of the same type
structures in the low temperature region. We found that the heat capacities of
isostructural phases with the same sum of atomic numbers of constituent elements are
close to each other within the experimental measurement accuracy.
The dependence of heat capacity of the compounds vs temperature can be described by
different functions, varying from simple linear equation to polynomials. In our case,
the heat capacities below 298 K for AIIIBV compounds are presented as a linear
combination of Debye’s functions from arguments T / n :
n
Cv (T )  3  R 
 an  D( n ) ;
T
1
x
T
y3
3x
D(
)  12( x) 3
dy 
y
x
n
e 1
e 1

0
R is the gas constant, T is the absolute temperature, x  n / T . The adjustable
parameters (an > 0 and n > 0) are obtained by minimizing of the sum squares method
of the difference between the experimental and calculated heat capacities. In our case,
we took n = 3. Below 298 K the value Cv is equal to Cp within limits of experimental
errors.
140
POSTER COMMUNICATIONS P-63
Study of the phase diagram of FeSe
superconductors
M.S.C. Henriques, J.A. Paixão
CEMDRX, Departamento de Física, Universidade de Coimbra, Rua Larga 3004-516 Coimbra, Portugal
The recent discovery of superconductivity in Fe-based compounds breaks the
conventional wisdom that Fe atoms are detrimental to superconductivity. Among the
Fe-based compounds, the tetragonal PbO type β-FeSe1-x has the simplest structure and
is ideal to investigate the origin of superconductivity in these compounds.
Unfortunately, the phase diagram of FeSe is somewhat complex. Another structure, the
hexagonal δ-phase (NiAs type) exists in an intermediate temperature range, and it is
difficult to produce single-phase β-FeSe starting from the melted elements. In addition,
other ferromagnetic phases such as Fe3Se4 and Fe7Se8 can also form as minority phases.
In our work, different synthesis conditions are being tested in order to produce singlephase β-FeSe. The different phases are identified by XRD and the superconducting and
magnetic properties measured by AC resistivity and VSM magnetometry.
(1) F.-C. Hsu, J.-Y. Luo, K.-W. Yeh, T.-K. Chen, T.-W. Huang, P.M. Wu, Y.-C. Lee, Y.-L.
Huang, Y.-Y. Chu, D.-C. Yan, M.-K. Wu, Proc. Natl. Acad. Sci. 105, 2008, 14262-14264.
(2) H. Okamoto, J. Phase Equilib., 12, 1991, 383-389.
141
P-64 POSTER COMMUNICATIONS
Linear behaviour of isothermal solubility
phenomena involving strong electrolytes. Special
case of concentrated aqueous solutions of cobalt
and nickel nitrates
C. Goutaudier,* B. El Goundali,† R. Tenu,* M. Kaddami,† J.J. Counioux*
†
*
Université de Lyon, Laboratoire Multimatériaux et Interface UMR CNRS 5615, France
Faculté Sciences et Techniques Settat, Laboratoire Procédés et Valorisation Ressources Naturelles,
Morocco
Concentrated electrolyte aqueous solutions are well known to be complex media which
are characterized by very high activity coefficients values. In the ternary systems,
liquidus curve modeling is generally difficult and numerous experimental
investigations must be undertaken. In these systems isothermal ice liquidus curves often
follow linear laws as predicted by the ideal solution model. 1,2 So ice solubility curves
can be calculated by using Quasi Ideal Model3, from the both equations of ice liquidus
curves and the limit aqueous binary systems.
As an example the experimental study of isotherm – 15 °C of the ternary system H2O
– Co(NO3)2 – Ni(NO3)2 shows up the existence of two substitution solid solutions as
hexahydrated cobalt or nickel nitrates and the corresponding liquidus curves follow
linear laws. At this temperature the solubility
curves are represented by straight lines as
shown in figure hereunder. Consequently the
molar fractions of cobalt and nickel in the
liquid phase can be accurately defined from the
composition of the solid phase in equilibrium.
(1) L. Misane, S. El Allali, M. Kaddami, A. Zrineh, R. Tenu, J. Berthet, J.J. Counioux,
Thermochim. Acta, 356, 2000, 117-126.
(2) B. El Goundali, M. Kaddami, Ann. Chim. Sci. Mat., 34, 2009, 109-119.
(3) R. Tenu, C. Goutaudier, B. El Goundali, M. Kaddami, J.J. Counioux,
J. Therm. Anal. Calorim., 112, 2013, 263-270
142
POSTER COMMUNICATIONS P-65
Peculiarities in crystallization kinetics
of some Al-Ni-REM amorphous alloys
V.E. Sidorov,* P. Svec,† D. Janickovic†
*
Ural State Pedagogical University, Ekaterinburg, Russia
†
Institute of Physics SAS, Bratislava, Slovakia
Al-Ni-R amorphous alloys are a novel group of engineering materials with unique
physical properties. Nowadays they are going to be used as protecting materials for the
constructions working in corrosive medium. However their crystallization pass depends
on nature of rare-earth element and its content in the alloy. It is a common opinion that
aluminum nanoparticles appear at the first stage of crystallization; but different stable
and metastable intermetallic compounds can be formed during the following stages. In
this works we investigated crystallization of Al86Ni8R6 (R = Gd, Ho, Sm) amorphous
ribbons (6 mm width, 30-35 mm thickness) prepared by the standard planar flow
method. DSC curves were obtained at heating-cooling rates of 5, 10, 20 and 40 K/min.
The following sequence of phases was detected:
- aluminum nanoparticles appear at the first stage. After 10 min exposition at 475 K
their average sizes are 2-4 nm (the largest particles were fixed in Sm-containing ribbon;
the smallest – in ribbon with Ho). They continue to grow up with the following heating.
- the intermetallic compound Al3Ni arises at the second stage independently of the alloy
composition.
- Al3R compound comes at the third stage.
- as for the forth stage (it was fixed for the alloys with gadolinium and samarium, but
not with holmium), the eutectic reaction Al + Al3Ni + Al3R → Al23Ni6R4 takes place
here. The latest compound seems to be stable: neither annealing at 800 K for several
hours nor exposition at room temperatures for several months has destroyed it. It can
be decomposed into binary compounds by heating to rather high temperatures only.
Acknowledgments: The work is partially supported by Ministry of Education and Science RF (project N
4.1177.2014/K) and RFBR (project N 13-03-96055).
143
P-66 POSTER COMMUNICATIONS
The influence of Ga (Zr, Sn) additions on
crystallization of CoFeBSiNb bulk amorphous
alloys
V.E. Sidorov,* I. Lishchynskyy,† I. Kaban‡
*
†
Ural State Pedagogical University, Ekaterinburg, Russia
Precarpathian National University, Ivano-Frankivsk, Ukraine
‡
Institute for Complex Materials, IFW, Dresden, Germany
Co-based bulk metallic glasses are a novel group of engineering materials with unique
mechanical, magnetic and corrosion properties. However their industrial application is
limited due to low glass forming ability (GFA). In this work we investigated the
influence of gallium, tin and zirconium small additions on crystallization of
Co48Fe25B19Si4Nb4 bulk amorphous alloy. The samples in the form of rods 1.5 mm in
diameter were prepared by melt injection into a water-cooled cooper mould. DSC
curves were obtained at heating-cooling rates of 5, 10, 20 and 40 K/min.
The results are analyzed in the frames of classical JMA model; the glass transition and
crystallization temperatures as well as activation energies are determined. It is found,
in particular, that in the base composition crystallization goes in one stage with the
formation of Co(Fe)23B6 compound. Introduction of 2 at.% Ga (Zr, Sn) leads to the
appearance of the second stage of crystallization with the precipitation of MNbB (M =
Fe, Ga, Sn, Zr) metastable borides. The following heating or annealing the samples
cause the decomposition of metastable phase into stable Nb2B and Fe2B.
The existing GFA criteria are discussed and it is shown that the new criterion for melts
glass forming ability should be introduced.
Acknowledgments: The work is partially supported by Ministry of Education and Science RF (project N
4.1177.2014/K) and RFBR (project N 13-03-00598-a).
144
POSTER COMMUNICATIONS P-67
Crystal fibers growth of the nonlinear optical
crystal BaCaBO3F
F. Assi,† M. Cochez,† M. Ferriol,† M. Aillerie,† G. Maxwell‡
‡
†
University of Lorraine, LMOPS E.A. 4423, Metz, F-57070 France
Shasta Crystals, 1750 Cesar Chavez St, San Francisco, CA 94124, U.S.A.
In order to generate UV light cascade frequency conversion from an IR laser, using
non-linear optical (NLO) crystals is an effective technique. In recent years, the
fluoroborate crystals have received much attention because of their excellent properties
such as large effective second harmonic generation (SHG) coefficients, wide
transparency range from deep UV (155 nm) up to middle IR (3660 nm).
In our study, we are interested to BaCaBO3F (BCBF) crystal which is chemically stable
without any hygroscopicity. The growth of NLO BCBF crystals was reported about 20
years ago and this material was shown to have favorable lasing and self frequency
doubling properties when doped with ytterbium.
Usually, BCBF crystal was grown in air using the Kyropoulos and Czochralski methods
allowing the growth of crystals with very high optical quality without inclusions. The
results of differential thermal analysis show that BCBF crystal is congruently melting
at T = (1090-1100) °C.1,2
In this contribution, the growth of BCFB crystal fibers was performed using a micropulling down method. In order to obtain an uncolored single crystal fiber of BCBF,
several attempts were made with different pulling rates.
Some additional cautions need to be considered for this process. Indeed, the BCBF
powder cannot be directly synthesized by solid-state reaction because BaF2 at elevated
temperatures causes corrosion of the crucible and introduces impurities to the grown
crystal. Thereby, BCBF was prepared in two steps (reaction 1 and 2) and characterized
by XRD and DTA
BaCO3 + 2CaCO3 + B2O3  BaCa2(BO3)2 + 3CO2 (reaction 1)
BaCa2(BO3)2 + BaF2  2BaCaBO3F (reaction 2)
and finally characterized by XRD and DTA.
This communication aims to present our preliminary results on the growth of BCBF
crystal fibers by the micro-pulling down technique.
(1) K. Lu, P. Loiseau, G. Aka, J. Cryst. Growth, 311, 2009, 2508-2512.
(2) R.K. Li, Q.D. Zeng, J. Cryst. Growth, 382, 2013, 47-51.
145
P-68 POSTER COMMUNICATIONS
Growth and characterizations of Bi2ZnB2O7 crystal
fibers
F. Assi,† M. Cochez,† M. Ferriol,† M. Aillerie,† G. Maxwell‡
‡
†
University of Lorraine, LMOPS E.A. 4423, Metz, F-57070 France
Shasta Crystals, 1750 Cesar Chavez St, San Francisco, CA 94124, U.S.A.
The growing interest in compact all-solid state laser sources based on non-linear optical
crystals emitting in the ultraviolet range is explained by their numerous applications
such as photolithography, micromachining, cutting or surgery. The only way to
generate an ultraviolet laser light from a crystal is by frequency conversion of a nearinfrared source. In these conditions, the research works are directed towards borate
crystals as new non-linear optical materials due to their performance, transparency in a
wide frequency range down to deep UV, and resistance to laser damage. The Bi2ZnB2O7
compound (BZBO), chemically stable and non-hygroscopic, is particularly interesting.
Bulk single crystals were recently grown for the first time by Czochralski and
Kyropoulos techniques.1-4
On the other hand, a big interest has arised for fiber crystal growth techniques such as
the micro-pulling down (µ-PD) due to its unequalled specifications: high axial
temperature gradients allowing high pulling rates, high length/diameter aspect ratio
favorable to light propagation, high crystal quality.
Several BZBO crystal fibers were pulled and characterized. All were transparent with
a more or less pronounced yellow-orange/red color. The origin of this color is ascribed
to the presence of Bi-rich disordered or glassy domains. The presence of this disordered
domains may be caused by the contamination of Pt crucible.
In order to obtain colorless fibers, the growth of BZBO was studied by µ-PD technique
using a gold crucible and also by LHPG (Laser-heated pedestal growth) technique
taking advantage of the absence of crucible avoiding any contamination.
The elemental analysis of crushed BZBO fibers show a deficit in boron. To avoid this
problem, several fibers were pulled from a melt containing a boron excess and then,
characterized. The purpose of this communication is to review the various aspects of
this work.
(1) N. Li, P. Fu, Y. Wu, J. Zhang, J. Cryst. Growth, 311, 2009, 3476-3478.
(2) F. Li, X. Hou, S. Pan, X. Wang, Chem. Mater., 21, 2009, 2846-2850.
(3) F. Li, S. Pan, X. Hou, Z. Zhou, J. Cryst. Growth, 312, 2010, 2383-2385.
(4) F. Li, S. Pan, J. Cryst. Growth, 318, 2011, 629-631.
146
POSTER COMMUNICATIONS P-69
Characterization and numerical simulation of the
mechanical behavior of aeronautical alloy based
composite
A. Sadki,* M. Babou,† M. Khattal,† L. Hattali,‡ N. Mesrati*†
* Laboratoire LSGM, Ecole Nationale Polytechnique, El-Harrach-Alger, Algeria
† ESTA, Dar El Beida, Alger, Algeria.
‡ Laboratoire FAST - Bat. 502 Campus Universitaire - 91405 Orsay Cedex, France
The lightening of structures is a driving force behind current research in aeronautics. In
this context, aluminum alloys need to be competitive compared to material composites.
Also, it is clearly established that, in areas of very strong concentration of effort
aeronautical structures (landing gears, masts-reactors, shutter rails and of mouthpieces
...), light metal materials (titanium alloys, of aluminum and nickel, steel) remain
indispensable and an answer to the alleviation of aeronautical structures lies in
increasing of their mechanical performance.
The elaboration of multi-material structures will solve a number of constraints linked
with conventional processes and bring significant gains in terms of adherence
aluminum alloy/deposit (Stripping, NiAl layer bonding, diffusion ... etc).1 However,
knowledge of the processes brought into play still remains delicate since it concerns
physico-chemical and mechanical effects variable according to the nature of the
materials considered.2
Tensile tests applied have shown large changes in mechanical properties of the base
alloy after coating, which are possibly related to the very different nature of the
assembled materials and conditions of application. We note a strong decrease of the
elastic limit of AG3 coated compared to AU4G. The high ductility of this alloy is the
cause which causes during the gritting process a large penetration of the granules
particles in the substrate and creation of plastic zones. Thus, a radial compression is
exerted on the section which causes a plastification process. The decrease of the average
section of the substrate after sandblasting, the stress concentration at the cavity and / or
the compressive residual stress created when sandblasting are responsible for the
decrease in breaking strength of the AU4G compared to the AG3. The material becomes
hard and fragile.
The numerical finite element simulation allowed us to understand and manage a number
of phenomena encountered during the mechanical behavior of our composites. The
experimental results obtained during our study are consistent with
those of the simulation. Indeed, it was noted that the concentration of stresses during
the tensile tests was located at the ends of the useful length of the test specimen.
(1) A.M. Kamara, K. Davey, Int. J. Solids Struct., 44, 2007, 8532-8555.
(2) L. Haddour, M. Keddam, N. Mesrati, Appl. Mech. Mater., 625, 2014, 192-195.
147
P-70 POSTER COMMUNICATIONS
Thermodynamic modeling of AIII-Sb melts
N.I. Ilinykh,* I.A. Malkova,* V.P. Vassiliev,† V.A.Volgarev*
* Ural Technical Institute of Telecommunications and Informatics, 15, Repin Str., Ekaterinburg, 620109,
Russia
†
Chemistry Department, Lomonosov Moscow State University, Leninskiye Gory, Moscow 119992, Russia
Presented work is devoted to the investigation and reassessment of the composition and
thermodynamic characteristics of binary Ga-Sb, Al-Sb and In-Sb melts using optimized
thermodynamic functions of the AIII-Sb compounds.1
The investigation was carried out using the thermodynamic modeling method. 2 As a
software the program complex TERRA was used.3 Modeling was executed in
atmosphere of argon at the common pressure of P = 105 Pa and temperature and
concentration intervals, corresponding to regions of liquid state on the phase diagrams
of above - indicated binary systems4.
The activities of components, equilibrium composition of melts, integral excess
enthalpies, entropies, integral and partial excess Gibbs energies were obtained. It was
established, that the activities of the components have big negative deviations from
Raoult’s low. Concentration dependencies of integral excess Gibbs energies, entropies
and enthalpies are no monotonous. These facts justify, that strong interaction between
atoms of different sorts takes place.
Using subprogram RECTANGLE1 the phase diagrams for Ga-Sb, Al-Sb and In-Sb
systems were constructed. On these diagrams the temperature and concentration
regions of existence of the components of the condensed phase and the gas phase are
shown.
(1) V.P. Vassiliev, A.F. Taldrik, N.I. Ilinykh. MATEC Web of Conference, 3, 2013, № 01078.
(2) N.A. Vatolin, G.K. Moiseev, B.G. Trusov. Thermodynamic modeling in high - temperature
inorganic systems, Metallurgia, Moscow, 1994 (in Russian).
(3) B.G. Trusov. Vestnik of Bauman Moscow State Technological University,
2, 2012, 240-249 (special Issue) (Russian).
(4) Phase diagrams of binary metallic systems: Handbook. In 3 vol. Edited by N.P. Ljakishev,
Mashinostroenie, Moskow, 1997 (in Russian).
148
41st Conference on Phase Equilibria
XLIèmes Journées d’Étude des Équilibres entre Phases
JEEP 2015
List of participants
LIST OF PARTICIPANTS
Full Name
Email
Institution
[email protected]
University of Blida
Algeria
Abdelaziz Chikh
Baelhadj
[email protected]
University of Sciences
and Technology Houari
Boumediene
Algeria
Abhinav Joseph
[email protected]
University of Lisbon
Portugal
Alexandre Decreton
[email protected]
IRSN – Institute for
Radiological Protection
and Nuclear Safety
France
Ana Almeida
[email protected]
University of Porto
Portugal
Ana Cristino
[email protected]
University of Lisbon
Portugal
Ana Ferreira
[email protected]
University of Porto
Portugal
anafranciscasmgcoelho.fcup
@gmail.com
University of Porto
Portugal
[email protected]
New University of
Lisbon
Portugal
Ana Rodrigues
[email protected]
University of Porto
Portugal
Ana Segadães
[email protected]
University of Aveiro
Portugal
[email protected]
University of Aveiro
Portugal
Angélique Teyssier
angelique.teyssier
@etu.univ-lyon1.fr
University Claude
Bernard Lyon 1
AREVA - BG Mines
France
Antoine Burel
antoine.burel
@etu.univ-rouen.fr
University of Rouen
France
António Évora
[email protected]
University of Coimbra
Portugal
[email protected]
University of Coimbra
Portugal
[email protected]
University of Lisbon
Portugal
[email protected]
University of Porto
Portugal
[email protected]
University of Coimbra
Portugal
christelle.goutaudier
@univ-lyon1.fr
University Claude
Bernard Lyon 1
France
[email protected]
University of Coimbra
Portugal
A. Abdallah El Hadj
Ana Francisca Coelho
Ana Pereiro
André Palma
Beverly Stewart
Carlos Bernardes
Carlos Lima
César Henriques
Christelle Goutaudier
Cláudia Arranja
151
Country
LIST OF PARTICIPANTS
[email protected]
University Complutense
Madrid
Spain
[email protected]
University of Santiago
de Compostela
Spain
[email protected]
University of Coimbra
Portugal
[email protected]
University of Lorraine
France
[email protected]
University of Lisbon
Portugal
[email protected]
University of Porto
Portugal
Francisco Almeida
[email protected]
University of Coimbra
Portugal
Francois Goutenoire
francois.goutebnoire
@univ-lemans.fr
University of Maine
France
Gérard Coquerel
[email protected]
University of Rouen
France
Grace Baaklini
[email protected]
University of Normandy
France
Hamama Ben-MakhloufHakem
[email protected]
University of Sciences
and Technology Houari
Boumediene
Algeria
Hermínio Diogo
[email protected]
University of Lisbon
Portugal
[email protected]
University of Coimbra
Portugal
Igor Reva
[email protected]
University of Coimbra
Portugal
Ilham Mokbel
[email protected]
University Claude
Bernard Lyon1
University of Saint
Etienne
France
Inês Vaz
[email protected]
University of Porto
Portugal
[email protected]
University Paris
Descartes
France
[email protected]
University of Toulouse
France
[email protected]
University Claude
Bernard Lyon 1
France
jean-claude.tedenac
@univ-montp2.fr
University of Montpellier
2
France
[email protected]
University Claude
Bernard Lyon 1
France
[email protected]
New University of
Lisbon
Portugal
Concepción Pando
Enriqueta López
Ermelinda Eusébio
Farah Assi
Fátima Piedade
Filipe Ribeiro
Hugh Burrows
Ivo Rietveld
Ivonne Rodriguez-Donis
Jacques Jose
Jean-Claude Tedenac
Jean-Jacques Counioux
João Araújo
152
LIST OF PARTICIPANTS
João Canotilho
[email protected]
University of Coimbra
Portugal
João Coutinho
[email protected]
University of Aveiro
Portugal
[email protected]
University of Porto
Portugal
[email protected]
University of Strathclyde
United
Kingdom
[email protected]
University of Coimbra
Portugal
[email protected]
New University of
Lisbon
Portugal
[email protected]
University of Porto
Portugal
Josefa Fernández
[email protected]
University of Santiago
de Compostela
Spain
Joseph Saab
[email protected]
University Saint Esprit
de Kaslik
Lebanon
[email protected]
University Complutense
of Madrid
João Monte
Joop ter Horst
José António Paixão
José Esperança
José Ferreira
Juan Rodríguez
Renuncio
Juliana Oliveira
Spain
University of Porto
Portugal
karina.shimizu
@tecnico.ulisboa.pt
University of Lisbon
Portugal
Latifa Negadi
[email protected]
University of Tlemcen
Algeria
Licínia Justino
[email protected]
University of Coimbra
Portugal
Luciana Tomé
[email protected]
University of Coimbra
Portugal
[email protected]
University of Porto
Portugal
[email protected]
University of Las
Palmas de Gran
Canaria
Spain
Luís Paulo Rebelo
[email protected]
New University of
Lisbon
Portugal
Malgorzata Zakrzewska
ma.zakrzewska
@campus.fct.unl.pt
New University of
Lisbon
Portugal
Manuel Minas da
Piedade
[email protected]
University of Lisbon
Portugal
Manuela Ramos Silva
[email protected]
University of Coimbra
Portugal
María del Barrio
[email protected]
Polytechnics University
of Catalonia
[email protected]
University of Coimbra
Karina Shimizu
Luís Belchior Santos
Luis Fernández
Maria João Moreno
153
Spain
Portugal
LIST OF PARTICIPANTS
Maria Luísa Ramos
[email protected]
University of Coimbra
Portugal
Mariana Oliveira
[email protected]
University of Aveiro
Portugal
Marianne Cochez
marianne.cochez
@univ-lorraine.fr
University of Lorraine
France
[email protected]
University of Coimbra
Portugal
[email protected]
University of Coimbra
Portugal
Marta Henriques
[email protected]
University of Coimbra
Portugal
Mauro Gonçalves
[email protected]
University of Coimbra
Portugal
Mehmet Bilgin
[email protected]
Istanbul University
Turkey
Melisa Lalikoğlu
[email protected]
Istanbul University
Turkey
Melodia Oliveira
melodia_oliveira27
@hotmail.com
University of Coimbra
Portugal
Michel Ferriol
[email protected]
University of Lorraine
France
Michel Molière
[email protected]
University of Belfort
Montbéliard
France
Mohammed-Elamine
Djeghlal
[email protected]
Polytechnic National
School, Algiers
Algeria
Mónia Martins
[email protected]
University of Aveiro
Portugal
Nadir Mesrati
[email protected]
Ecole Nationale
Polytechnique d' Alger
Algeria
nataliya.shcherbakova
@ensiacet.fr
LGC, INP-ENSIACET,
Toulouse
France
[email protected]
Ural Technical Institute
of Telecommunications
and Informatics
Russia
Olivier Baudouin
[email protected]
ProSim SA
France
Pedro Carvalho
[email protected]
University of Aveiro
Portugal
Pedro Silva
[email protected]
University of Coimbra
Portugal
Pol Lloveras
[email protected]
Polytechnics University
of Catalonia
Ricardo Castro
[email protected]
University of Coimbra
Portugal
Ricardo Taveira
[email protected]
University of Porto
Portugal
[email protected]
University of Coimbra
Portugal
Mariette Pereira
Mário T.S. Rosado
Nataliya Shcherbakova
Nina Ilinykh
Rui Fausto
154
Spain
LIST OF PARTICIPANTS
Saéda Didaoui
[email protected]
University of Sciences
and Technology Houari
Boumediene
Algeria
Sara Machado
sara_machado27
@hotmail.com
University of Coimbra
Portugal
[email protected]
Polytechnic Institute of
Bragança
Portugal
Süheyla Çehreli
[email protected]
Istanbul University
Teresa Roseiro
[email protected]
University of Coimbra
Portugal
Tuong-Dan Vu
[email protected]
University of Maine
France
Valeriy Sidorov
[email protected]
Ural State Pedagogical
University
Russia
Valery Vassiliev
[email protected]
Lomonosov Moscow
State University
Russia
[email protected]
Istanbul University
Turkey
[email protected]
University of Rouen
France
Simão Pinho
Yavuz Aşçı
Yohann Cartigny
[email protected]
http://www.uc.pt/go/jeep2015
155
Turkey