Table Of ContentC R C H A N D B O O K O F
T
HERMODYNAMIC
D
of
ATA
A
QUEOUS
P
OLYMER
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OLUTIONS
Christian Wohlfarth
CRC Press
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Foreword
The knowledge of thermodynamic data of aqueous polymer solutions is important for basic and
applied chemistry and chemical engineering, computational modelling and thermodynamic research. It has
many applications in the fields of biotechnology, membrane science and membrane technology,
environmental and green chemistry, food chemistry and food industry.
Among the existing publications in this field are C. Wohlfarth’s own book Vapor-Liquid
Equilibria of Binary Polymer Solutions (Elsevier, 1994) and his recent CRC Handbook of Thermo-
dynamic Data of Copolymer Solutions (CRC Press, 2001). Liquid-liquid equilibrium data can be found in
Albertson’s book Partition of Cell Particles and Macromolecules (Wiley, 1986), and more recently in
Zaslavsky’s book Aqueous Two-Phase Partitioning. Physical Chemistry and Bioanalytical Applications
(Dekker, 1995). All these data are fairly old and cover a limited number of properties and chemical
systems that represent only a minor portion in comparison with this new book. Commercial electronic
databases do not provide such data. This Handbook offers a new and complete collection on
thermodynamic data of aqueous polymer solutions.
This new book contains low- and high-pressure equilibrium data, vapor-liquid equilibria, liquid-
liquid equilibria, enthalpic and volumetric data, as well as second virial coefficients. This covers all the
necessary areas for researchers and engineers who work in this field. It will help users to retrieve quickly
all the relevant information from the original literature and also help researchers to plan new
measurements where data are missing.
The structure and the contents of this book are organized in a similar way as in the CRC
Handbook of Thermodynamic Data of Copolymer Solutions and this will facilitate the extraction of the
desired new data.
Last but not least, author C. Wohlfarth has been known for his experience in thermodynamics of
polymer solutions for more than 20 years.
I am sure that readers interested in the field of thermodynamic properties of polymer solutions
will benefit from this Handbook and will identify the work that has to be done in the future.
Dr. Henry V. Kehiaian
IUPAC Representative on ICSU Committee on
Data for Science and Technology (CODATA)
PREFACE
Knowledge of thermodynamic data of polymer solutions is a necessity for industrial and
laboratory processes. Such data serve as essential tools for understanding the physical behavior of
polymer solutions, for studying intermolecular interactions, and for gaining insights into the molecular
nature of mixtures. They also provide the necessary basis for any developments of theoretical
thermodynamic models. Scientists and engineers in academic and industrial research need such data and
will benefit from a careful collection of existing data. The CRC Handbook of Thermodynamic Data of
Aqueous Polymer Solutions provides a reliable collection of such data for such polymer solutions from the
original literature.
The Handbook is divided into seven chapters: (1) Introduction, (2) Vapor-Liquid Equilibrium
(VLE) Data of Aqueous Polymer Solutions, (3) Liquid-Liquid Equilibrium (LLE) Data of Aqueous
Polymer Solutions, (4) High-Pressure Phase Equilibrium (HPPE) Data of Aqueous Polymer Solutions, (5)
Enthalpy Changes for Aqueous Polymer Solutions, (6) PVT Data of Polymers and Solutions, and (7)
Second Virial Coefficients (A ) of Aqueous Polymer Solutions. Finally, appendices quickly route the user
2
to the desired data sets. Thus, the book covers all the necessary areas for researchers and engineers who
work in this field.
In comparison with low-molecular systems, the amount of data for aqueous polymer solutions is
still rather small. About 800 literature sources were perused for the purpose of this handbook, including
some dissertations and diploma papers. About 1000 data sets, i.e., 165 vapor-pressure isotherms, a
number of Henry’s constants, 500 LLE and a small number of HPPE data sets, a number of volumetric
and enthalpic data and some second osmotic virial coefficients, are reported. Additionally, tables of
systems are provided where results were published only in graphical form in the original literature to lead
the reader to further sources. Data are included only if numerical values were published or authors
provided their numerical results by personal communication (and I wish to thank all those who did so). No
digitized data have been included in this data collection. The Handbook is the first complete overview
about this subject in the world’s literature. The closing day for the data collection was May 31, 2003. The
Handbook results from parts of a more general database, Thermodynamic Properties of Polymer Systems,
which is continuously updated by the author. Thus, the user who is in need of new additional data sets is
kindly invited to ask for new information beyond this book via e-mail at [email protected].
Additionally, the author will be grateful to users who call his attention to mistakes and make suggestions
for improvements.
The CRC Handbook of Thermodynamic Data of Aqueous Polymer Solutions will be useful to
researchers, specialists, and engineers working in the fields of polymer science, physical chemistry,
chemical engineering, material science, biological science and technology, and those developing
computerized predictive packages. The Handbook should also be of use as a data source to Ph.D. students
and faculty in Chemistry, Physics, Chemical Engineering, Biotechnology, and Materials Science
Departments at universities.
Christian Wohlfarth
Merseburg, August 2003
About the Author
Christian Wohlfarth is Associate Professor for Physical Chemistry at Martin Luther University
Halle-Wittenberg, Germany. He earned his degree in Chemistry in 1974 and wrote his Ph.D. thesis on
investigations on the second dielectric virial coefficient and the intermolecular pair potential in 1977, both
at Carl Schorlemmer Technical University Merseburg. In 1985, he wrote his habilitation thesis, Phase
Equilibria in Systems with Polymers and Copolymers, at Technical University Merseburg.
Since then, Dr. Wohlfarth’s main research has been related to polymer systems. Currently, his
research topics are molecular thermodynamics, continuous thermodynamics, phase equilibria in polymer
mixtures and solutions, polymers in supercritical fluids, PVT-behavior and equations of state, and sorption
properties of polymers, about which he has published approximately 100 original papers. He has also built
a database, Thermodynamic Properties of Polymer Systems, and has written the books Vapor-Liquid
Equilibria of Binary Polymer Solutions and CRC Handbook of Thermodynamic Data of Copolymer
Solutions.
He is working on the evaluation, correlation, and calculation of thermophysical properties of pure
compounds and binary mixtures resulting in six volumes of the Landolt-Börnstein New Series. He is a
respected contributor to the CRC Handbook of Chemistry and Physics.
CONTENTS
1. INTRODUCTION
1.1. Objectives of the handbook...............................................................................................1
1.2. Experimental methods involved........................................................................................2
1.3. Guide to the data tables...................................................................................................20
1.4. List of symbols................................................................................................................24
1.5. References.......................................................................................................................26
2. VAPOR-LIQUID EQUILIBRIUM (VLE) DATA
OF AQUEOUS POLYMER SOLUTIONS
2.1. Partial water vapor pressures or water activities
for binary polymer solutions..............................................................................................29
2.2. Partial solvent vapor pressures or solvent activities
for ternary aqueous polymer solutions...............................................................................58
2.3. Classical mass-fraction Henry’s constants of water vapor
in molten polymers............................................................................................................74
2.4. References.........................................................................................................................78
3. LIQUID-LIQUID EQUILIBRIUM (LLE) DATA
OF AQUEOUS POLYMER SOLUTIONS
3.1. Cloud-point and/or coexistence curves of quasibinary solutions.......................................81
3.2. Table of systems where binary LLE data were published only in
graphical form as phase diagrams or related figures..........................................................97
3.3. Cloud-point and/or coexistence curves of quasiternary solutions
containing water and at least one polymer.......................................................................105
3.3.1. Nonelectrolyte solutions............ ....................................................................105
3.3.2. Electrolyte solutions.......................................................................................167
3.4. Table of systems where ternary LLE data were published only in
graphical form as phase diagrams or related figures........................................................283
3.5. Cloud-point and/or coexistence curves of quasiquaternary solutions
containing water and at least one polymer.......................................................................301
3.5.1. Nonelectrolyte solutions........... .....................................................................301
3.5.2. Electrolyte solutions.......................................................................................315
3.6. Table of systems where quaternary LLE data were published only in
graphical form as phase diagrams or related figures.......................................................328
3.7. Lower critical (LCST) and/or upper critical (UCST) solution temperatures
of aqueous polymer solutions..........................................................................................331
3.8. References.......................................................................................................................339
4. HIGH-PRESSURE PHASE EQUILIBRIUM (HPPE) DATA
OF AQUEOUS POLYMER SOLUTIONS
4.1. Experimental data of quasibinary polymer solutions.......................................................365
4.2. Table of systems where binary HPPE data were published only
in graphical form as phase diagrams or related figures....................................................369
4.3. Experimental data of quasiternary solutions containing water
and at least one polymer..................................................................................................370
4.4. Table of systems where ternary HPPE data were published only
in graphical form as phase diagrams or related figures....................................................374
4.5. References.......................................................................................................................375
5. ENTHALPY CHANGES FOR AQUEOUS POLYMER SOLUTIONS
5.1. Enthalpies of mixing or intermediary enthalpies of dilution,
and partial enthalpies of mixing (at infinite dilution),
or polymer (first) integral enthalpies of solution ............................................................377
5.2. Partial molar enthalpies of mixing at infinite dilution of water
and enthalpies of solution of water vapor in molten polymers
from inverse gas-liquid chromatography (IGC)...............................................................413
5.3. Table of systems where additional information on enthalpy effects
in aqueous polymer solutions can be found.....................................................................416
5.4. References.......................................................................................................................424
6. PVT DATA OF POLYMERS AND SOLUTIONS
6.1. PVT data of some polymers and their aqueous solutions................................................431
6.2. Excess volumes and/or densities of aqueous polymer solutions......................................448
6.3. Table of systems where additional information on volume effects
in aqueous polymer solutions can be found.....................................................................471
6.4. References.......................................................................................................................473
7. SECOND VIRIAL COEFFICIENTS (A )
2
OF AQUEOUS POLYMER SOLUTIONS
7.1. Experimental A data.......................................................................................................477
2
7.2. References.......................................................................................................................485
APPENDICES
Appendix 1 List of systems and properties in order of the polymers......................................487
Appendix 2 List of solvents in alphabetical order...................................................................505
Appendix 3 List of solvents in order of their molecular formulas...........................................507
INDEX.....................................................................................................................................................509
