NE DITTO TEXTBOOK OF QUANTITATIVE CHEMICAL ANALYSIS FIFTH EDITION G.H. JEFFERY * J.BASSETT © J.MENDHAM + R.C. DENNEYVOGEL’s TEXTBOOK OF QUANTITATIVE CHEMICAL ANALYSIS FIFTH EDITION Revised by the following members of The School of Chemistry, Thames Polytechnic, London GH Jeffery, BSc, PhD, C Chem, FRSC Former Principal Lecturer and Deputy Head of the School of Chemistry J Bassett, MSc, C Chem, FRSC Former Senior Lecturer in Inorganic Chemistry J Mendham, M Sc, C Chem, MRSC Principal Lecturer in Analytical Chemistry RC Denney, BSc, PhD, C Chem, FRSC, MBIM Principal Lecturer in Organic Chemistry >m>/Longman Scientific & = Technical Copublished in the United States with John Wiley & Sons, Inc., New YorkLongman Scientific & Technical Longman Group UK Limited Longman House, Burnt Mill, Harlow Essex CM20 2JE, England and Associated Companies throughout the world Copublished in the United States with John Wiley and Sons Inc, 605 Third Avenue, New York NY 10158 © Longman Group UK Limited 1978, 1989 All rights reserved; no part of the publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior written permission of the Publishers, or a licence permitting restricted copying in the United Kingdom issued by the Copyright Licensing Agency Ltd, 33-34 Alfred Place, London WC1E 7DP. First published in 1939 New impressions 1941, 1942, 1943, 1944, 1945, 1946, 1947, 1948 Second edition 1951 New impressions 1953, 1955, 1957, 1958, 1959, 1960 Third edition 1961 (published under the title A Text-book of Quantitative Inorganic Analysis Including Elementary Instrumental Analysis) New impressions 1962, 1964, 1968, 1969, 1971, 1974, 1975, Fourth edition 1978 New impressions 1979, 1981, 1983, 1985, 1986, 1987 Fifth edition 1989 British Library Cataloguing in Publication Data Vogel, Arthur Israel Vogel's textbook of quantitative chemical analysis. ~ Sth ed. 1. Quantitative analysis L Title IL Jeffery, G. H. S45 ISBN O-S82-44b93-? Library of Congress Cataloguing in Publi Vogel, Arthur Israel [Textbook of quantitative chemical analysis] Vogel's textbook of quantitative chemical analysis. ~ Sth ed./ revised by ... G. H. Jeffery ... [et al.] Pp. cm. Rev. ed. of: Vogel’s textbook of quantitative inorganic analysis. 4th ed. 1978. Includes bibliographies and index. ISBN 0-470-21517-8 1. Chemistry, Analytic- Quantitative. 2. Chemistry, Inorganic. I Jeffery, G.H. 1909 I. Vogel, Arthur Israel, Vogels textbook of quantitative inorganic analysis. III. Title. QD101.2.V63 1989 $45-de20 89-12296 CIP ion Data Set in 10/11pt Lasercomp Times New Roman Printed in Great Britain by Bath Press, Avon‘OETERMINATION OF BORIC ACIO 10.34 Procedure B. The experimental details for the preparation of the initial solution are similar to those given under Procedure A. Titrate 25 or 50 mL of the cold solution with standard 0.1M hydrochloric acid and methyl orange, methyl orange-indigo carmine, or bromophenol blue as indicator. Titrate another 25 or 50 mL of the cold solution, diluted with an equal volume of water, slowly with the standard acid using phenolphthalein or, better, the thymol—blue cresol red mixed indicator; in the latter case, the colour at the end point is rose. Calculate the result as described in the Discussion above. 10.33 DETERMINATION OF A MIXTURE OF CARBONATE AND HYDROGENCARBONATE The two methods available for this determination are modifications of those described in Section 10.32 for hydroxide/carbonate mixtures. In the first procedure, which is particularly valuable when the sample contains relatively large amounts of carbonate and small amounts of hydrogencarbonate, the total alkali is first determined in one portion of the solution by titration with standard 0.1M hydrochloric acid using methyl orange, methyl orange—indigo carmine, or bromophenol blue as indicator: CO?" +2H* = HCO, HCO; +H* = H,CO, H,CO,=H,0+C0, Let this volume correspond to VmL 1M HCL. To another sample, a measured excess of standard 0.1M sodium hydroxide (free from carbonate) over that required to transform the hydrogencarbonate to carbonate is added: HCO; +OH~ = CO}- +H,0 A slight excess of 10 per cent barium chloride solution is added to the hot solution to precipitate the carbonate as barium carbonate, and the excess of sodium hydroxide solution immediately determined, without filtering off the precipitate, by titration with the same standard acid; phenolphthalein or thymol blue is used as indicator. If the volume of excess of sodium hydroxide solution added corresponds to vmL of 1M sodium hydroxide and v’mL 1M acid corresponds to the excess of the latter, then v — v’ = hydrogencarbonate, and V —(v—v’) = carbonate. In the second procedure a portion of the cold solution is slowly titrated with standard 0.1M hydrochloric acid, using phenolphthalein, or better, the thymol blue—cresol red mixed indicator. This (say, Y mL) corresponds to half the carbonate (compare Section 10.32): co}- +H* =HCOs Another sample of equal volume is then titrated with the same standard acid using methyl orange, methyl orange—indigo carmine or bromophenol blue as indicator. The volume of acid used (say, ymL) corresponds to carbonate + hydrogencarbonate. Hence 2¥ = carbonate, and y — 2Y = hydrogencarbonate. 10.34 DETERMINATION OF BORIC ACID Discussion. Boric acid acts as a weak monoprotic acid (K, = 6.4 x 107"); it 29910 TITRIMETRIC ANALYSIS cannot therefore be titrated accurately with 0.1M standard alkali (compare Section 10.13), However, by the addition of certain organic polyhydroxy compounds, such as mannitol, glucose, sorbitol, or glycerol, it acts as a much stronger acid (for mannitol K,=1.5x 10~*) and can be titrated to a phenolphthalein end point. The effect of polyhydroxy compounds has been explained on the basis of the formation of 1:1 and 1:2-mole ratio complexes between the hydrated borate ion and 1,2- or 1,3-diols: >C(OH) >C—Q O—-C<]> \/ : 7 +H,BO; /\ Ht +3H,0 >C(OH) _>C—O O—-C< Glycerol has been widely employed for this purpose but mannitol and sorbitol are more effective, and have the advantage that being solids they do not materially increase the volume of the solution being titrated: 0.5-0.7g of mannitol or sorbitol in 10 mL of solution is a convenient quantity. The method may be applied to commercial boric acid, but as this material may contain ammonium salts it is necessary to add a slight excess of sodium carbonate solution and then to boil down to half-bulk to expel ammonia. Any precipitate which separates is filtered off and washed thoroughly, then the filtrate is neutralised to methyl red, and after boiling, mannitol is added, and the solution titrated with standard 0.1M sodium hydroxide solution: H[boric acid complex] + NaOH = Na[boric acid complex] + HO imL 1M NaOH = 0.06184g H,BO, ‘A mixture of boric acid and a strong acid can be analysed by first titrating the strong acid using methyl red indicator, and then after adding mannitol or sorbitol, the titration is continued using phenolphthalein as indicator. Mixtures of sodium tetraborate and boric acid can be similarly analysed by titrating the salt with standard hydrochloric acid (Section 10.25, B), and then adding mannitol and continuing the titration with standard sodium hydroxide solution: it must of course be borne in mind that in this second titration the boric acid liberated in the first titration will also react. Procedure. To determine the purity of a sample of boric acid, weigh accurately about 0.8 g of the acid, transfer quantitatively to a 250 mL graduated flask and make up to the mark. Pipette 25 mL of the solution into a 250 mL conical flask, add an equal volume of distilled water, 2.5—3 g of mannitol or sorbitol, and titrate with standard 0.1M sodium hydroxide solution using phenolphthalein as indicator. It is advisable to check whether any blank correction must be made: dissolve a similar weight of mannitol (sorbitol) in 50 mL of distilled water, add phenolphthalein, and ascertain how much sodium hydroxide solution must be added to produce the characteristic end point colour. 10.35 DETERMINATION OF AMMONIA IN AN AMMONIUM SALT Discussion. Two methods, the direct and indirect, may be used for this determination. 300