Buffers for pH and Metal Ion Control

This book is intended as a practical manual for chemists, biologists and others whose work requires the use of pH or metal-ion buffers. Much information on buffers is scattered throughout the literature and it has been our endeavour to select data and ins

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Buffers for pH and Metal Ion Control D. D. Perrin

John Curtin School of Medical Research Australian National University Canberra Boyd Dempsey

Faculty of Military Studies University of New South Wales Royal Military College Duntroon

London CHAPMAN AND HALL

First published in 1974 by Chapman and Hall Ltd 11 New Fetter Lane, London EC4P 4EE First issued as a Science Paperback 1979 © 1974 D.D. Perrin and Boyd Dempsey Typeset by Santype Ltd (Coldtype Division) Salisbury, Wiltshire

ISBN-J3: 978-0-412-21890-3 DOl: /0./007/978-94-009-5874-6

e-ISBN-13: 978-94-009-5874-6

This paperback edition is sold subject to the condition that it shall not, by way of trade or otherwise, be lent, re-sold, hired out, or otherwise circulated without the publisher's prior consent in any form of binding or cover other than that in which it is published and without a similar condition including this condition being imposed on the subsequent purchaser All rights reserved. No part of this book may be reprinted, or reproduced or utilized in any form or by any electronic, mechanical or other means, now known or hereafter invented, including photocopying and recording, or in any information storage or retrieval system, without the permission in writing from the publisher.

Distributed in the US.A. by Halsted Press, a Division of John Wiley & Sons, Inc, New York

Contents 1. 1.1 1.2 1.3

2.

2.1 2.2 2.3 2.4 2.5 2.6 2.6.1 2.7 2.8 2.9 2.10 2.11 2.12

3.

3.1 3.2 3.3 3.4 3.5 3.5.1 3.5.2 3.5.3 3.5.4

Preface Introduction The concept of buffer action Why are buffers needed? Some naturally occurring buffers The Theory of Buffer Action Equilibrium aspects Activity effects Effect of dilution Salt effects Ampholytes and zwitterions Buffer capacity Buffer capacity of a polybasic acid Pseudo buffers Self buffers Mixtures of buffers Temperature dependence Effect of pressure on buffers Further reading Applications of pH Buffers Factors governing the choice of a buffer Measurement of pH Biochemistry and biology Spectroscopy Buffers for special applications Volatile buffers Buffers for electrophoresis Buffers for complexometric titrations Buffers for chromatography

page viii 1 1

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vi . Contents

Buffers for polarography Buffers for proton magnetic resonance studies Buffers for solvent extraction Isotonic phannaceutical buffers Miscellaneous 4. Practical Limitations in the Use of Buffers 4.1 Chemical problems 4.2 Biological effects 4.3 Influence on chemical reactions 5. New pH-Buffer Tables and Systems 5.1 On calculating buffer composition tables 5.1.1 Buffers of constant ionic strength. No added electrolyte 5.1.2 Constant ionic strength buffers with added electrolyte 5.1.2.1 Preparation of amine buffers of constant ionic strength 5.1.3 Buffers by direct titration of weak bases or acids with strong acids or bases 5.2 On designing a new pH-buffer system 6. Buffers for use in Partially Aqueous and Non-Aqueous Solvents and Heavy Water 6.1 pH* Scales 6.2 pH* Buffers 6.3 The measur