Chemical Equilibrium A Practical Introduction for the Physical and L
* The present work is designed to provide a practical introduction to aqueous equilibrium phenomena for both students and research workers in chemistry, biochemistry, geochemistry, and interdisciplin ary environmental fields. The pedagogical strategy I h
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CHEMICAL EQUILIBRIUM A PRACTICAL INTRODUCTION FOR THE PHYSICAL AND LI FE SCI ENCES
William B. Guenther
Department of Chemistry The University of the South Sewanee, Tennessee
PLENUM PRESS, NEW YORK AND LONDON
Library of Congress Cataloging in Publication Data Guenther, William B Chemical equilibrium. Bibliography: p. Includes index. 1. Chemical equilibrium. I. Title. 75-28028 QD503.G8 541 '.392 ISBN-13: 978-1-4684-2165-1 e-ISBN-13: 978-14684-2163-7 001: 10.1007/978-1-4684-2163-7
© 1975 Plenum Press, New York Softcover reprint of the hardcover 1st edition 1975 A Division of Plenum Publishing Corporation 227 West 17th Street, New York, N. Y. 10011 United Kingdom edition published by Plenum Press, London A Division of Plenum Publishing Company, Ltd. Davis House (4th Floor), 8 Scrubs Lane, Harlesden, London, NW10 6SE, England All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher
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Preface
The present work is designed to provide a practical introduction to aqueous equilibrium phenomena for both students and research workers in chemistry, biochemistry, geochemistry, and interdisciplinary environmental fields. The pedagogical strategy I have adopted makes heavy use of detailed examples of problem solving from real cases arising both in laboratory research and in the study of systems occurring in nature. The procedure starts with mathematically complete equations that will provide valid solutions of equilibrium problems, instead of the traditional approach through approximate concentrations and idealized, infinite-dilution assumptions. There is repeated emphasis on the use of corrected, conditional equilibrium constants and on the checking of numerical results by substitution in complete equations and/or against graphs of species distributions. Graphical methods of calculation and display are used extensively because of their value in clarifying equilibria and in leading one quickly to valid numerical approximations. The coverage of solution equilibrium phenomena is not, however, exhaustively comprehensive. Rather, I have chosen to offer fundamental and rigorous examinations of homogeneous step-equilibria and their interactions with solubility and redox equilibria. Many examples are worked out in detail to demonstrate the use of equilibrium calculations and diagrams in various fields of investigation. Over 100 other exercises are included, most with answers and hints for solution. I have tried to bridge the gap between the oversimplified treatment in general and analytical chemistry texts and the complexities of the advanced presentations of multiple competing equilibria in real systems found in the books by Butler, Garrels and Christ, v
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Preface
and Stumm and Morgan (see the Bibliography, Appendix A-6). Students and workers in modern biology and geology as well as in chemistry need more help than these wor
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