Heats of Mixing and Solution

Transcription

1 Landolt-Börnstein Numerical Data and Functional Relationships in Science and Technology New Series / Editor in Chief: W. Martienssen Group IV: Physical Chemistry Volume 10 Heats of Mixing and Solution Subvolume B Binary Gaseous, Liquid, Near-Critical, and Supercritical Fluid Systems of Nonelectrolytes C.J. Wormald, J.-P.E. Grolier, J.-C. Fontaine K. Sosnkowska-Kehiaian, H.V. Kehiaian Edited by H.V. Kehiaian

2 ISSN (Physical Chemistry) ISBN-10 ISBN Springer Berlin Heidelberg New York Springer Berlin Heidelberg New York Library of Congress Cataloging in Publication Data Zahlenwerte und Funktionen aus Naturwissenschaften und Technik, Neue Serie Editor in Chief: W. Martienssen Vol. IV/10B: Editor: H.V. Kehiaian At head of title: Landolt-Börnstein. Added t.p.: Numerical data and functional relationships in science and technology. Tables chiefly in English. Intended to supersede the Physikalisch-chemische Tabellen by H. Landolt and R. Börnstein of which the 6th ed. began publication in 1950 under title: Zahlenwerte und Funktionen aus Physik, Chemie, Astronomie, Geophysik und Technik. Vols. published after v. 1 of group I have imprint: Berlin, New York, Springer-Verlag Includes bibliographies. 1. Physics--Tables. 2. Chemistry--Tables. 3. Engineering--Tables. I. Börnstein, R. (Richard), II. Landolt, H. (Hans), III. Physikalisch-chemische Tabellen. IV. Title: Numerical data and functional relationships in science and technology. QC ' This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in other ways, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution act under German Copyright Law. Springer is a part of Springer Science+Business Media springeronline.com Springer-Verlag Berlin Heidelberg 2005 Printed in Germany The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Product Liability: The data and other information in this handbook have been carefully extracted and evaluated by experts from the original literature. Furthermore, they have been checked for correctness by authors and the editorial staff before printing. Nevertheless, the publisher can give no guarantee for the correctness of the data and information provided. In any individual case of application, the respective user must check the correctness by consulting other relevant sources of information. Cover layout: Erich Kirchner, Heidelberg Typesetting: Authors and Redaktion Landolt-Börnstein, Darmstadt Printing and Binding: AZ Druck, Kempten SPIN: / Printed on acid-free paper

3 Editor H.V. Kehiaian University of Paris VII, France Contributors C.J. Wormald University of Bristol, UK J.-P.E. Grolier Blaise Pascal University, Aubière, France J.-C. Fontaine CNRS, Paris, France K. Sosnkowska-Kehiaian University of Paris VII, France H. V. Kehiaian University of Paris VII, France Landolt-Börnstein Editorial Office Gagernstr. 8, D Darmstadt, Germany fax: +49 (6151) Internet

4 Preface The volumes in this series are compilations of data on the change of energy which accompanies the formation of a multi-component gas, liquid, or supercritical fluid system from its pure components. The first volume, published in 2004, dealt with the heat of mixing of two pure liquid components to form a binary homogeneous (single-phase) liquid system or a heterogeneous (two-phase) liquid-liquid system. The present second volume in this series deals with: a) the heat of mixing of two pure gases, or two near-critical fluids, or two supercritical fluids to form a binary homogeneous (single-phase) or a heterogeneous (two-phase) liquid-liquid or fluid-fluid system and b) the heat of solution of a pure gas in a pure liquid solvent to form a binary homogeneous (single-phase) liquid system (solution). All the components are well-defined pure substances which are organic or inorganic nonelectrolytes, including water. Only heats of mixing and solution data obtained by direct calorimetric measurements are considered. Heat of mixing and solution data are important in the design of industrial processes, as they enter into energy balance and phase equilibrium calculations, and in the design of process equipment, such as refrigerators, compressors, distillation apparatus, evaporators, condensers, heaters and heat exchangers, and equipment for supercritical fluid technology. Since heats of mixing and solution are related to the structure and the energy of interaction of the molecules they are important from the theoretical point of view. While great advances have been made in the development of thermodynamic equations of state, in statistical mechanical models, and in computer simulation techniques, it is still far from easy to accurately predict the complex phase behavior of many binary mixtures. The success of the calculations is judged by agreement with experimental measurements, and it is often the case that the parameters used in the calculations are adjusted to give good agreement with measured values. It is therefore of fundamental importance to have a large database of accurate measurements of heats of mixing and solution. Using this database theorists can further develop their models, and engineers can with confidence design efficient industrial process equipment. The measurement of heats of mixing and solution is difficult, it takes many years of experience to develop the requisite skills, and a relatively small number of laboratories have specialized in this activity. Notable in this field is the work of Wormald et al. at Bristol University, UK. This group has pioneered the development of accurate flow-mixing calorimeters for the measurement of the heat of mixing of fluids from the gaseous state at atmospheric pressure, in the liquid region, and up to the supercritical region at high pressures and temperatures. They published over 100 papers in the field. Similar work has been done by the group at Brigham Young University, Provo, Utah, USA, under the leadership of Christensen, Ott, Izatt et al. ; this group has also developed calorimeters of new design. Excellent measurements have been made by Grolier et al., University of Clermont Ferrand, France, on liquid mixtures at high temperatures and pressures, and by Mather et al., University of Alberta, Canada, on mixtures of compressed gases. Wadsö et al., University of Lund, Sweden, and Gill et al., University of Colorado, Boulder, USA, pioneered the use of flow calorimeters for the measurement of the heat of solution of gases in liquids, and made many accurate measurements of these small quantities. It would be impossible to cover in a printed volume the numerical values of all the isotherms, isobars, and isopleths of all the 448 investigated systems. The book reproduces in tables and graphs the numerical

5 Preface VII values for only 314 mixtures and solutions, chosen to be representative of all the compound classes and property types. When the number of data points for a given system reported in the original source is very large, only a part of the data appears in the printed tables, but the full set is given on the CD-ROM accompanying the book. Most data files contain unsmoothed experimental calorimetric data compiled from the original literature published from 1957 to The ELBT.EXE program on the CD-ROM allows the fast search of data according to property type, chemical system (substances, mixtures, and solutions), and reference (authors, original source of data, and year of publication). The program displays the data tables for all the 448 systems as PDF files, in the same format as in the book. The totality of numerical data points is also displayed by the program in two computer readable standard ASCII file formats, SELF and ELDATA. Estimated uncertainties are reported in these files for each measured physical quantity. The concept of the SELF (Standard ELectronic File) format was developed in by the Task Group on Standard Physico-Chemical Data Formats (IUCOSPED) of the International Union of Pure and Applied Chemistry (IUPAC) and the Committee on Data for Science and Technology (CODATA) in cooperation with the International Council of Scientific and Technical Information (ICSTI). A data portal, called DataExplorer (Fachinformationszentrum, Karlsruhe, Germany), implemented SELFs for a variety of physico-chemical properties. The structure of the SELFs in this volume, as well as in the previous volume in this series, follows the general format of IUCOSPED SELFs. Each SELF file is characterized by three Digital Object Identifiers (DOI), the objects being the property type, the chemical system (mixture components), and the full reference to the original source of data. The descriptors of the DOIs are listed in three files on the CD-ROM. The purpose of SELFs and of the associated descriptor files is to allow the exporting of data files to data banks and application programs and the exchange of data between data centers. The SELFs can be easily reformatted into other formats, and the DOIs translated into other languages (nomenclature, etc.), which may be more suitable for various specific applications or professional communities. The ELDATA format is an electronic file, similar to, but more explicit than SELF, incorporating the DOI descriptors of the printed volume. In order to facilitate the storage, exchange and use of the data, the ELBT.EXE program of this volume allows importation of the information of SELF and ELDATA files, as well as of the files containing the results of correlations into Spreadsheet ML documents. Another new feature of the ELBT.EXE program on the CD is the inclusion of a comprehensive, though not exhaustive, bibliographical database on heats of mixing and solution giving 3444 references to experimental (calorimetric) heat of mixing and solution measurements published in the period for two- to six-component systems. These components are organic or inorganic electrolytes and nonelectrolytes, ionic liquids, alloys, fused salts, polymers and other materials. Eight indexes are included in the book. These are: Formula Index of Substances with main names and relative molar masses Name Index of Substances with Chemical Abstract Service Registry Numbers, synonyms, and acronyms Class Indexes of Organic Substances, Organic Systems, Carbon Dioxide-Organic Systems, and Aqueous-Organic Systems Index of Systems Containing Inorganic Substances. Formula Index of Systems The full-text electronic version of the book is also available on the CD-ROM with hypertext links to all the data files in PDF format. In a compilation of this scope it is impossible to avoid errors in reproducing correctly the data from the original literature, and assigning the uncertainties, even after careful checking. The authors will be grateful to users who call our attention to mistakes and make suggestions for improvements.

6 VIII Preface I want to thank the authors, Dr. C. J. Wormald and Prof. J.-P. E. Grolier, for writing the Introduction of these volumes and for their advice in the selection and presentation of the data, to Dr. K. Sosnkowska- Kehiaian for the entry and correlation of the data, and to Eng. J. C. Fontaine for the development of the database management system, computational programs and layout of the printed version. I am deeply grateful to Prof. V. P. Belousov (University of St. Petersburg, Russia), Prof. A. E. Mather (University of Alberta, Canada), Prof. W. A. Van Hook (University of Tennessee, USA), and to Prof. E. Wilhelm (University of Vienna, Austria) who made important contributions to this work, Finally, I wish to express my appreciation to the editorial office in Darmstadt, Germany, with special thanks to Dr. Wolfgang Finger, for their masterful job in preparing the volumes for the publisher. Paris, August 2005 The Editor

7 Contents 1 Introduction Fundamental principles and basic relations Basic thermodynamic equations Residual functions Excess functions Experimentally accessible thermodynamic quantities Calorimetric measurements of the heat of mixing Enthalpies of solution of gases in liquids Calorimetric measurement of the enthalpy of solution of gases in liquids Batch solution calorimeters Isothermal solution calorimeters Flow mixing calorimeters Injection calorimeters Principles of heat of mixing calorimetry and types of calorimeter Low pressure gas mixing flow calorimetry High pressure gas mixing flow calorimetry Calorimeters for mixing fluids in the two-phase and supercritical regions Coiled tube high pressure flow calorimetry Analysis of excess enthalpies of gas mixtures at low pressures Weakly polar gases Second virial coefficients from excess enthalpies Associated gas mixtures at low pressures Analysis of enthalpies of mixing of fluids at high pressures The virial equation of state at high pressures A two-fluid model for high pressure calculations Cubic equations of state Heats of mixing in the liquid and supercritical regions Heats of mixing across a two-phase region Binary mixture for which the critical temperatures are almost equal Binary mixture for which the critical pressures are almost equal Correlation of experimental data Tables on heats of mixing and solution Introduction Property types Organic systems Carbon dioxide organic systems Aqueous-organic systems Systems containing inorganic substances

8 X Contents 3 Instructions on using the computer program ELBT Introduction System requirements Installing the program To start Visualization of numerical data PDF display SELF (Standard Electronic File) display SELF structure. Identifiers Physical quantities and physico-chemical properties Independent variables and dependent variables Parameters Symbols, units and scales of physical quantities Numerical data and estimated uncertainties Two-phase fluid-fluid systems Linked data files ELDATA display Selection of units Graphical display Correlating experimental data Output of correlated experimental data Creating SpreadsheetML documents Indexes Formula index of substances Name index of substances Class index of organic substances Class index of organic systems Class index of carbon dioxide-organic systems Class index of aqueous-organic systems Index of systems containing inorganic substances Formula index of systems General references