CRC HANDBOOK OF

THERMODYNAMIC
DATA of
COPOLYMER
SOLUTIONS

© 2001 by CRC Press LLC

CRC HANDBOOK OF

THERMODYNAMIC
DATA of
COPOLYMER
SOLUTIONS
Christian Wohlfarth

CRC Press
Boca Raton London New York Washington, D.C.
1074/Disclaimer Page 1 Tuesday, March 13, 2001 12:33 PM

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 Foreword

Practical applications of thermodynamics as well as theoretical calculations of thermodynamic

properties generally require data of real systems. In most cases these data rest on laboratory measurements
of various physical properties. The study of phase behavior and thermodynamic properties of polymers
and mixtures containing polymers has been subject of interest during the last 50 years. Investigations on
such properties for copolymer systems were emphasized during the last decade when copolymers gained
an increasing commercial interest because of their unique physical properties.

Much effort has been devoted over the years to compiling thermodynamic data for types of
systems from literature and preparing compilations and databases for both scientific and industrial use.
However, scarcely anything is found when one looks for compilations or databases that provide
thermodynamic properties of polymer, or even more specially, copolymer solutions. Experimental
information is spread over many articles and journals. There are only a small number of data books that
cover this field. The author of this handbook wrote one of them on vapor-liquid equilibria of binary
polymer solutions in 1994. He is known for his experience and his own experimental investigations on
polymer and copolymer solutions for more than 20 years. With his new Handbook of Thermodynamic
Data of Copolymer Solutions for the first time a compilation of thermodynamic data for copolymer
solutions from the original literature is available.

Taking into account vapor-liquid equilibrium (VLE) data, liquid-liquid equilibrium (LLE) data,
high-pressure phase equilibrium (HPPE) data of copolymer solutions in supercritical fluids, volumetric
property (PVT) data of copolymer melts, enthalpy data, and second osmotic virial coefficients of
copolymer solutions, the book covers all the necessary areas for researchers and engineers who work in
this field.

When dealing with copolymer systems, one encounters the special problem of copolymer
characterization since a copolymer is far from well-defined only by its chemical formula. Copolymers
vary by a number of characterization variables. Molar mass, chemical composition, and distribution
functions, tacticity, sequence distribution, branching, and end groups determine their thermodynamic
behavior in solution. It is far from clear how these parameters influence the thermodynamic properties in
detail. Unfortunately, there usually is not much information in the original papers; the available ones are
added to each system in this book.

In comparison to low-molecular systems, the amount of data for copolymer solutions is still
rather small. About 300 literature sources were perused for the purpose of this handbook, including some
dissertations and diploma papers. Several hundred vapor-pressure isotherms, Henry’s constants, LLE and
HPPE data sets, a number of PVT data and some second osmotic virial coefficients are reported.

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.

Henry V. Kehiaian
Chairman
IUPAC-CODATA Task Group on Standard Physico-Chemical Data Formats

© 2001 by CRC Press LLC

 PREFACE

Knowledge of thermodynamic data of copolymer solutions is a necessity for industrial and

laboratory processes. Such data serve as essential tools for understanding the physical behavior of
copolymer 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
Copolymer Solutions provides a reliable collection of such data for copolymer solutions from the original
literature.

The Handbook is divided into seven chapters: (1) Introduction, (2) Vapor-Liquid Equilibrium
(VLE) Data of Binary Copolymer Solutions, (3) Liquid-Liquid Equilibrium (LLE) Data of Quasibinary or
Quasiternary Copolymer Solutions, (4) High-Pressure Phase Equilibrium (HPPE) Data of Quasibinary or
Quasiternary Copolymer Solutions in Supercritical Fluids, (5) Enthalpy Changes for Binary Copolymer
Solutions, (6) PVT Data of Molten Copolymers, and (7) Second Virial Coefficients (A2) of Copolymer
Solutions. Finally, four appendices quickly route the user to the desired data sets.

Original data have been gathered from approximately 300 literature sources, including also a
number of dissertations and diploma papers. The Handbook provides about 250 vapor-pressure isotherms,
75 tables of Henry’s constants, 50 LLE data sets, 175 HPPE data sets, and 70 PVT data tables for more
than 165 copolymers and 165 solvents. 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, but some tables include systems data
published in graphical form. The Handbook is the first complete overview about this subject in the
world’s literature. The closing day for the data collection was October 1, 2000. 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 for new additional data sets is kindly
invited to ask for new information beyond this book via e-mail at wohlfarth@chemie.uni-halle.de.
Additionally, the author will be grateful to users who call his attention to mistakes and make suggestions
for improvements.

The Handbook also highlights the work still to be done − obvious, when one compares the
relatively small number of copolymer solutions for which data exist with the number of copolymers in use
today. Additionally, only a small minority of possible solutions of the copolymers covered by this book
were properly investigated (in relation to the combinatorial number of copolymer/solvent pairs, although it
is appreciated that not all make thermodynamic sense or are of practical use).

The CRC Handbook of Thermodynamic Data of Copolymer Solutions will be useful to

researchers, specialists, and engineers working in the fields of polymer science, physical chemistry,
chemical engineering, material science, 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, and Materials Science Departments at universities.

Merseburg, January 2001 Christian Wohlfarth

© 2001 by CRC Press LLC

 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, his main research is related to polymer systems. Currently, his research topics are
molecular thermodynamics, continuous thermodynamics, phase equilibria in (co)polymer mixtures and
solutions, (co)polymers in supercritical fluids, PVT-behavior and equations of state, sorption properties of
(co)polymers, about which he has published approximately 90 original papers. He has also built a
database, Thermodynamic Properties of Polymer Systems, and has written the book Vapor-Liquid
Equilibria of Binary Polymer Solutions.

He is working on the evaluation, correlation, and calculation of thermophysical properties of pure

compounds and mixtures resulting in 6 volumes of Landolt-Börnstein New Series. He is a member of the
Editorial Board of ELDATA: The International Electronic Journal of Physico-Chemical Data.

© 2001 by CRC Press LLC

 CONTENTS

1. INTRODUCTION
1.1. Objectives of the handbook
1.2. Experimental methods involved
1.3. Guide to the data tables
1.4. List of symbols
1.5. References

2. VAPOR-LIQUID EQUILIBRIUM (VLE) DATA

OF BINARY COPOLYMER SOLUTIONS
2.1. Partial solvent vapor pressures or solvent activities for copolymer solutions
2.2. Classical mass-fraction Henry's constants of solvent vapors in molten
copolymers
2.3. References

3. LIQUID-LIQUID EQUILIBRIUM (LLE) DATA

OF QUASIBINARY OR QUASITERNARY COPOLYMER SOLUTIONS
3.1. Cloud-point and/or coexistence curves of quasibinary solutions
3.2. Table of systems where binary LLE data were published only in
graphical form as phase diagrams or related figures
3.3. Cloud-point and/or coexistence curves of quasiternary solutions
containing at least one copolymer
3.4. Table of systems where ternary LLE data were published only in
graphical form as phase diagrams or related figures
3.5. Lower critical (LCST) and/or upper (UCST) critical solution temperatures
of copolymer solutions
3.6. References

4. HIGH-PRESSURE PHASE EQUILIBRIUM (HPPE) DATA

OF COPOLYMER SOLUTIONS IN SUPERCRITICAL FLUIDS
4.1. Experimental data of quasibinary copolymer solutions
4.2. Table of systems where binary HPPE data were published only in
graphical form as phase diagrams or related figures
4.3. Experimental data of quasiternary solutions containing at least
one copolymer
4.4. Table of systems where ternary HPPE data were published only in
graphical form as phase diagrams or related figures
4.5. References

© 2001 by CRC Press LLC

 5. ENTHALPY CHANGES FOR BINARY COPOLYMER SOLUTIONS
5.1. Enthalpies of mixing or intermediary enthalpies of dilution,
and copolymer partial enthalpies of mixing (at infinite dilution),
or copolymer (first) integral enthalpies of solution
5.2. Partial molar enthalpies of mixing at infinite dilution of solvents
and enthalpies of solution of gases/vapors of solvents in molten
copolymers from inverse gas-liquid chromatography (IGC)
5.3. Table of systems where additional information on enthalpy effects
in copolymer solutions can be found
5.4. References

6. PVT DATA OF MOLTEN COPOLYMERS

6.1. Experimental data and/or Tait equation parameters
6.2. References

7. SECOND VIRIAL COEFFICIENTS (A2) OF COPOLYMER SOLUTIONS

7.1. Experimental A2 data
7.2. References

8. APPENDICES
8.1. List of copolymer acronyms
8.2. List of systems and properties in order of the copolymers
8.3. List of solvents in alphabetical order
8.4. List of solvents in order of their molecular formulas

© 2001 by CRC Press LLC