CRC Handbook of Enthalpy Data of Polymer-Solvent Systems.pdf

CRC

Handbook of

Enthalpy Data of

Polymer-Solvent

Systems

Christian Wohlfarth

Boca Raton London New York

A CRC title, part of the Taylor & Francis imprint, a member of the

Taylor & Francis Group, the academic division of T&F Informa plc.

Published in 2006 by

CRC Press

Taylor & Francis Group

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Boca Raton, FL 33487-2742

CRC Press is an imprint of Taylor & Francis Group

No claim to original U.S. Government works

Printed in the United States of America on acid-free paper

10987654321

International Standard Book Number-10: 0-8493-9361-2 (Hardcover)

International Standard Book Number-13: 978-0-8493-9361-7 (Hardcover)

Library of Congress Card Number 2005056860

This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with

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Library of Congress Cataloging-in-Publication Data

Wohlfarth, C.

CRC handbook of enthalpy data of polymer-solvent systems / Christian Wohlfarth.

p. cm.

Includes bibliographical references and index.

ISBN 0-8493-9361-2 (alk.)

1. Polymer solutions--Thermal properties--Handbooks, manuals, etc. 2. Copolymers--Thermal

properties--Handbooks, manuals, etc. 3. Nonaqueous solvents--Thermal properties--Handbooks, manuals,

etc. I. Title: Enthalpy data of polymer-solvent systems. II. Title.

QD381.9.S65W632 2006

547’.70456--dc22

2005056860

Visit the Taylor & Francis Web site at

http://www.taylorandfrancis.com

and the CRC Press Web site at

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Taylor & Francis Group

is the Academic Division of Informa plc.

PREFACE

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

laboratory processes. Furthermore, 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. However, no data books or databases detailing

enthalpy changes in polymer solutions presently exist. Thus, the CRC Handbook of Enthalpy Data of

Polymer-Solvent Systems builds a completely new and reliable collection of enthalpy data for polymer

solutions from the original literature. It will be a very useful completion to the CRC Handbook of

Thermodynamic Data of Copolymer Solutions , the CRC Handbook of Thermodynamic Data of Aqueous

Polymer Solutions , and the CRC Handbook of Thermodynamic Data of Polymer Solutions at Elevated

Pressures as these contain only a small amount of enthalpic data in comparison to all available data

provided in this book.

The book is divided into six chapters: (1) Introduction, (2) Enthalpies of mixing or intermediary

enthalpies of dilution, (3) Polymer partial enthalpies of mixing at infinite dilution or polymer first integral

enthalpies of solution, (4) Solvent partial enthalpies of mixing measured by calorimetry, (5) Partial molar

enthalpies of mixing or solution of solvents in molten polymers from inverse gas-liquid chromatography

(IGC), and (6) Table of additional information on enthalpy effects. Finally, appendices quickly route the

user 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 polymer solutions is still

rather small. About 800 literature sources were perused for the purpose of this book, including some

dissertations and diploma papers. About 1770 data sets, i.e., 620 data sets on enthalpies of mixing or

intermediary enthalpies of dilution, 970 data sets for polymer partial enthalpies of mixing or solution at

infinite dilution, and 180 IGC tables are reported.

Additionally, tables of systems are provided here to lead the reader to further literature 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 book is the first complete overview about this subject in the worldÓs literature.

The closing day for the data collection was June, 30, 2005. 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

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 CRC Handbook of Enthalpy Data of Polymer-Solvent Systems 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 book 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 2005

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. WohlfarthÓs 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

written the books: Vapor-Liquid Equilibria of Binary Polymer Solutions , CRC Handbook of

Thermodynamic Data of Copolymer Solutions , CRC Handbook of Thermodynamic Data of Aqueous

Polymer Solutions , and CRC Handbook of Thermodynamic Data of Polymer Solutions at Elevated

Pressures .

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-Brnstein New Series . He is

a respected contributor to the CRC Handbook of Chemistry and Physics .

CONTENTS

1. INTRODUCTION

1.1.

Objectives of the handbook..ÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈ.È È 1

1.2.

Measurement of enthalpy changes in polymer solutionsÈÈÈÈÈÈÈÈÈÈÈÈ..2

1.3.

Guide to the data tablesÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈ.8

1.4.

List of symbolsÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈ12

1.5.

References...ÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈ14

2. ENTHALPIES OF MIXING OR INTERMEDIARY ENTHALPIES

OF DILUTION

2.1.

Experimental data ÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈ.15

2.2.

ReferencesÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈ188

3. POLYMER PARTIAL ENTHALPIES OF MIXING

(AT INFINITE DILUTION) OR POLYMER (FIRST)

INTEGRAL ENTHALPIES OF SOLUTION

3.1.

Experimental data ÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈ195

3.2.

ReferencesÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈ344

4. SOLVENT PARTIAL ENTHALPIES OF MIXING

MEASURED BY CALORIMETRY

4.1.

Experimental data ÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈ351

4.2.

ReferencesÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈ366

5. PARTIAL MOLAR ENTHALPIES OF MIXING AT INFINITE

DILUTION OF SOLVENTS AND ENTHALPIES OF SOLUTION

OF GASES/VAPORS OF SOLVENTS IN MOLTEN POLYMERS

FROM INVERSE GAS-LIQUID CHROMATOGRAPHY (IGC)

5.1.

Experimental data ÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈ..ÈÈ.È367

5.2.

ReferencesÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈÈ461

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