sts v 34s T A TEXT-BOOK OF QUANTITATIVE INORGANIC ANALYSIS INCLUDING ELEMENTARY INSTRUMENTAL ANALYSIS BY ARTHUR I. VOGEL, D.Sc. (Lonp.),. D.I.C., F.R.I.C. Heap or Cuzmistry DepantMunr, WooLwicx Poryrecuntc: Somutime Berr Screntrric Research FELLOW OF THE IuerrraL Couiar, Lonpon With Dtagrams and Illustrations THIRD EDITION LONGMANSPREFACE TO THIRD EDITION Tue kind reception accorded to the First and Second Editions has encouraged the author in the belief that his main aims have been largely achieved. Those include the provision of a text-book which will be of value: (i) to the student throughout the whole of his training and in his subsequent, career, and (ii) to practising analytical chemists and to all those workers (including industrial chemists) who bave occasion to utilise methods of quantitative inorganic analysis, During the ten years that have elapsed since the previous edition was published, inorganic analytical chemistry has developed in numerous directions, more particularly in the extended use of instrumental methods of analysis. It is generally accepted that training in at least some of the instrumental methods is highly desirable: the text now contains sufficient new matter to meet this objective. Nevertheless, it is of the greatest importance that the balance between what might be termed the classical method and the modern instrumental method of training the student in inorganic analysis be maintained; this can be achieved only if due emphasis be placed upon classical methods in the course of instruction. The task of revision has occupied several years, and much new experimental work carried out in the author’s laboratory has been included; in some cases, typical experimental results obtained under average laboratory conditions have been given. In order to incor- porate the very extensive changes and additions, the book has been entirely reset. ‘The volume is now divided into twenty-three chapters, some (¢.g., Hlectro-gravimetric Analysis, Analysis of Complea Materials) arising from sub-division of long chapters in the previous edition. ‘The following chapters are new: IV. Complezometric (largely EDTA) Titra- tions; . Coulometric Titrations; IX. Ion Exchange and Chromato- graphic Methods in Analysis; XI. Fluorimetric Analysis; XII. Nephelo- metric and Turbidimetric Analysis; XIII. Emission Spectrographie Analysis; XIV. Flame Photometric Analysis; XV. Solvent Extraction Methods of Analysis; and XVIII. High-frequency Titrations. The task of selecting, checking, and, where necessary, modifying experimental details described in the extensive literature has not been easy: in many instances, particularly where instrumental methods are used, new procedures have been devised. The author ventures to hope that he has at least succeeded in giving a reasonable account of the subjects which are of importance to the student during his period of training in inorganic analysis. ‘The Selected Bibliography at the end of each chapter will assist the reader in locating the sources where further information may be found. The insertion of references to the literature throughout the text would have increased the length (and the price) of the book considerably; this feature, although of great value to advanced students and practising analysts, has after very careful consideration not been included in the present edition. On the whole, it was decided that the volume was sufficiently large and vvi Preface to Third Edition comprehensive as a text-book, and that the inclusion of Selected Biblio- graphies might be acceptable as a reasonable compromise. ‘The text has been carefully revised and brought up-to-date in the - light of advances made during the last ten years; due consideration has been given to comments, criticisms, and Suggestions made by teachers and others throughout the world. It may be regarded as a dual work comprising classical inorganic analysis and elementary instrumental analysis as applied in the inorganic field. Owing to limitations of space, such topics as X-ray methods, mass spectrometry, Raman spectrography, ges chromatography, radiochemical methods, nuclear magnetic resonance spectroscopy, polarimetry, and refractometry have not been included in the text. It is hoped that the subjects discussed will suffice to form the basis of a course of elementary instrumental analysis utilising equipment which one would normally expect to find in an average well-equipped college laboratory. ‘The major changes in the Third Edition may now be enumerated: Chapter I. Tue TurorEriost Basis or Quantrrative INoR@aNic Anauysis. (i) Formal potentials (Section 1, 50). (i) Precipitation from homogeneous solution (I, 68). (ii) Ignition of the precipitate. Thermogravimetric method of analysis , 60). (iv) Extraction reagents (I, 63). Chapter II. Exrsrmextan Tsounique or Quanzirativa Ixoreaxio ANALYSIS. (i) Extornally controlled weight loading balances of the three-knife two- pan and two-knife single-pan types (IL, 9). , (Gi) Standardised volumetric flasks, pipettes and Burettes: tolerances of British Standards Institution (1952) and of the National Bureau of Standards (1958) (1, 20-22). (iii) Use of perchloric acid in inorganic analysis (If, 40). Chapter TI. Vorumerare (Trrsmrmrarc) Awaysts. {i) Oxidations with sodium hypochlorite (II, 145-147). Reductions with mercurous nitrate (IIT, 148-152), (iii) Phosphorus as quinoline phosphomolybdato (III, 158), silicon as quino- line silicomolybdate (MI, 156), phosphite (I, 159), and hypophosphite (Ui, 160). Chapter IV. Comprexomerrio (Larcrty EDTA) Trraations. Complexometric (largely EDTA) titrations constitute a very important development of volumetric (titrimetric) analysis and merit an independent ehapter. Of the numerous metal-ion indicators (pM indicators) that have been proposed, only those have been included which have been tested by the author and found satisfactory. A comprehensive range of experiments is provided. Chapter V. Gravimerrig ANALysIs. (i) Precipitation from homogeneous solution: bismuth as phosphate (¥, 17E); alumininm as basic succinate ond as oxinate (V, 28B and V, 28D); iron as basic formate (¥, 81A”); nickel as dimethylglyoximate (V, 2A); chtomium as lead chromate (V, 80D); thorium as tetrachlorophthalatePreface to Third Edition vii (V, 88D); zirconium as phosphate (V, 41A); calcium as oxalate (V, 484); strontium as sulphate (V, 444); barium as sulphate (V, 45A) and as chromate (V, 45B); and magnesium as oxinate (V, 46B). : (ii) Numerous new determinations, e., bismuth with dimethylglyoxime (V, 177); cadmium with 2-(o-hydroxyphenyl)benzoxazole (V, 18G) and as the thiourea-reineckate (V, 18H); tin with V-benzoylphenylhydroxylamine {V, 28D); palladium with nioxime (V, 260), 4-methylnioxime (V, 26D) and with 1,2,3-benzotriazole (V, 26E); nickel with 4-methylnioxime (V, 32D); cobalt as mercuri-thiocyanate (V, 38C); thallium with “thionalide” (V, 49B) and os tetraphenylarsonium chiorothallate (V, 42); potassium as tetraphenylborate (V, 48E); borate as nitron tetrafluchorate (V, 69); and silicon as quinoline silicomolybdate (V, 70C). Chapter VI. Exzorro-cravmerrio ANnatysis. The account of electrolytic determinations with controlled potential at the cathode has been extended (VI, 18-20). Chapter VIII. Covnommrric AnaLysts. This chapter is new. It includes: coulometry at controlled potential; coulometry at constant current; and coulomotric titrations. Titrations are described ‘with electrolytically generated iodine, bromine, ferrous ion, ceric ion, mercurous ion, silver ion, ferricyanide ion, ferrocyanide ion, hydroxide ion, and hydrogen ion. Chapter IX. Ion Exonanon anp Owromatocrapnic Merxops In ANALY- A now chapter is devoted to this important subject. ‘The determinations and separations described include: Ton exchange: zinc and magnesium {IX,8); chloride and bromide (IX, 9); cobalt and nickel (IX, 11); cadmium and zinc (IX, 12); sodium and potas- sium (IX, 16); determination of fluoride (IX, 18); sulphur in iron pyrites (0 1)3 and sodium (IX, 15). = a matography: separations on paper strips 18-20); iron ant aluminium (2/81), cobalt and nickel’ @X. 22), copper and nickel (IX, 23) on a cellulose column. Chapter X. CoLormmerric anp SPEOTROPHOTOMETEIC ANALYSIS. The sections dealing with apparatus and instruments havo beon rovised. A number of new determinations are described. These include: arsenic with silver diethyldithiocarbamate (X, 21); sulphate with barium chlorani- Jate and fluoride with thorium chloranilate (X, 29); chloride with mercuric chioranilate (X, 80); phosphate (X, 32); and borate (X, 33). A short account is given of experiments involving ultra-violet and visible spectrophotometers (X, 84-X, 86), of spectrophotomettic titrations (x, 97- X, 41), and of infra-red spectrophotometry (X, 42-X, 48). Chapter XI. Fuvortmerrio Awatysts and Chapter XEI. Nupnxto- . METRIC AND Tugsrpmerrio ANALYSIS. ‘These chapters are new and include number of simple determinations. Chapter XIII. Enossron SrnorgocraPHtc ANALYSIS. This is a new chapter. The importance of emission spectrographic analysis as part of a student’s training in analysis cannot be over-emphasised. Sufficient detail is given of the use of comparatively inexpensive apparatus to enable the student to carry out simple qualitative and quantitative analysis, aeviii Preface to Third Edition Chapter XIV. Fuame Proromerrio Anatysts. ‘This is a new chapter, and a number of simple determinations are described. Chapter XV. Sonvent Extraction MrTHops In ANALYSIS. ‘This is a new chapter and may be regarded as an extension of Chapter X on colorimetric and spectrophotometric analysis. A few simple applications are given: iron by chloride extraction (XV, 5); iron as the 8-hydroxyquino- late (XV, 8): uranium as the 8-hydroxyquinolate (XV, 7; leed with dithizone (XV, 8); nickel with dimethylglyoxime {XV, 9); copper as the diethyldithiocarbamate complex (XV, 10) and as the “neo-cuproin ” com- plex (XV, 11); beryllium as the acetyiacetone complex (XV, 12); and molyb- denum by the thiocyanate method (XV, 13). Chapter XVI. Potextiomerrio Trrrations, The main changes and additions are: modern pH scale (XVI, 1) and pH meters (KVL 2); location of end point by an analytical method (XVI, 8); automatic potentiometric titrations (KVI, 5); determination of nitrate (“‘doad-stop ” titrimetry, XVI, 14); sulphate by lead nitrate and redox system (XVI, 15); ferric iron with EDTA (XVI, 17); potassium perman- ganate solution with potassium iodide (KVI, 18); nickel and also cobalt by complexation with cyanide (XVI, 19); fluoride by null-point method (XVI, 20); and EDTA titrations with the mercury electrode (XVI, 16). Chapter XVIII. Hiau-rrequenoy Trrrations. ‘This new chapter contains » number of simple determinations using the apparatus developed by the author. Chapter XTX. Potarocrarmic ANatysts. The sections on apparatus (XIX, 6-XIX, 8) have been revised. An experiment on the determination of the formula and stability constant of a metal-ion complex has been introduced (XIX, 14). Chapter XX, Aweuzomeraio Trreazroxs. New experiments include the determination of cobalt with a-nitroso-8- naphthol (XX, 6); coppor with benzoin a-oxime (XX, '?); cadmium with B-naphthoquinoline (EX, 8); fluoride with thorium nitrate (KX, 9); zine and also bismuth with EDTA (XX, 10 and XX, 12); iodide with mercuric nitrate (XX, 12); potassiam with sodium tetraphenylborate using a graphite indicating cloctrode (KX, 18); also titrations with a rotating platinum micro-electrode (XX, 14-16); and with two indicator electrodes (‘ dead- stop end point ”, XX, 18-19). APPENDIX. A number of sections given in the Second Edition have been omitted as these are now no longer of real value; these include schemes of study, many of the details concerning buffer solutions, and lists of books (most of the latter are included in the Selected Bibliography at the end of each chapter). ‘The tables of chemical factors (A, 2) have been modified and enlarged. “Now sections include: solubility products at about room temperature (A, 16); dissociation constants of some acids in water at 25° C. (A, 17); polarographio half-wave potentials (A, 18); tables of “ raies ultimes ” and persistent for spectrographic analysis (A, 19); and tables of reciprocals (A, 22). It is impossible to make adequate acknowledgment to all who have contributed either directly or indirectly to the present volume. Com- mercial firms and organisations have always been willing to help inPreface to Third Edition ix providing diagrams, descriptive literature, and special information; the names of these firms are given in the appropriate places in the text. The author wishes to place on record the debt he owes to these firms and organisations and takes this opportunity of thanking them for their assistance. Acknowledgment is also due to the numerous books and publications which have been consulted; these are too numerous to be mentioned individually, but reference to some of the books will be found in the Selected Bibliography at the end of each chapter. Tn connexion with the experimental work, the author is indebted to a number of undergraduates and steéf (both laboratory and teaching) of the Chemistry Department of this Polytechnic, Especial thanks aro duo to: (i) J, Bassett, MSo., for chooking and developing many of tho new titri- metric procedures involving EDTA, ion oxchange and chromatographic separations as well as gravimetric procedures based upon precipitation homogeneous solution. (ii) V. Kyte for checking some of the Brogedares based upon coulometry (these were commenced by C. M. Bllis, M.Sc.), spectrophotometry, fluori- metry, nephelometry, turbidimetry, flame photometry, potentiomotry, polsoaey, amperometry, and high-frequency titrimetry. Gi) J. mm, Grad.B.1.C., for checking and/or developing the oxperi- ments on emission spectrographic analysis, various potentiometric titrations, including those with EDTA and tho mercury electrode, and the determination of the formula and stability constant of a metal ion complex by polaro- eephy. L. Blight, M.Sc. for checking the experiments involving solvent extraction methods and precipitation from homogeneous solution. (v) Dr. G. H. Jeffery for work in connexion with the spectrophotometric detormination of the pX value of an indicator (methyl red). (vi) Dr. G. H. Jollery, ‘Dr. C. W. N. Cumper, J. Bassett, M.Sc., H. A. Glastonbury, B.Sc., W. T. Cresswell, B.Sc., and Dr. D. J. Morantz for reading all tho galley proofs and making a number of helpful suggestions. (viii) Dr. G. H. Jeffery for his assistance in a supervisory capacity in numerous ways and for reading all the page © proofs is advice upon many Tnatters of detail has led to the elimination of much ambiguity and has also resulted in many improvements in the text. Tt will be noted that the symbols pH, pM, and pX are used through- out the book. ‘This conforms with the practice of the Journal of the American Chemical Society prior to about November 1960 when the manuscript of the book was almost complete. The recommendations of the International Union of Pure and Applied Chemistry (see J. A. Christiansen, ‘Manual of Physico-Chemi Symbols and Termino- logy ”, Journal of the American Chemical Society, 1960, 82, 5517) are that the quantity pH be printed in roman type: it is presumably implied, but not specifically mentioned, that the present author’s pM and pX should now be written as pM (both letters in roman type) and pK (p in roman type). The student is recommended to read also “Delinitive Rules for Nomenclature of jmonganio Chemistry ” (ibid., 1960, 82, 5523) and “‘ Definitive Rules for fomenclature of Organic Chemistry ” (ibid., 1960, 82, 5545). Current Practice of The Chemical Society, London, is incorporated in the book “ Handbook for Chemical Society Authors”, 1960 (Special Publication No. 14). ‘The author would appreciate constructive suggestions (including newx Preface to Third Edition experiments of general interest) for the improvement of the book and also to have his attention drawn to any errors which may have escaped his notice. Artuur I. Voorn Woolwich Polytechnic, London, 8.2.18. June, 1961.CONTENTS CHAPTER I THE THEORETICAL BASIS TS OF QUANTITATIVE INORGANIC I, 1. Bleotrolytic dissociation =... we wk I, 2. The law of mass action : . . . . . I, 8. Activity and coefficient | | | ft I, 4. Acid-base equilibria in water. Determination of ionisation constants : . . : . . I, 3, Strengths of acids and bases. | ||) I, 6. Ionisation of polybasic acids, 95 5 sf) I, % Common ion effect. Pot I, 8. Solubility product 1 common ion . oe 1, 10. Limitations of the solubility product principle : I, 11, Fractional precipitation — : 1,18, Complex ions. : I, 13. Effect of acids upon the solubility of a precipitate | I, 14, Effect of temperature upon the solubility of a precipitate I, 15. Effect of solvent upon the solubility of a a precipitate ¥, 16. ‘The ionie product of water . : 3,17. The hydrogen-ion exponent, pH - 5} ] 118. The hydrolysis of ealta cya ‘ Do I, 19. Hydrolysis conatant ree of hydrolysis. =| | 1,20, Baller solutions yee : VOLUMETRIC (rreamenrnto) ANALYSIS vA J, 21, Volumetric (titrimetric) analysis. ¥, 28. Classification of reactions in volumetric (analysis) titrimetric T, 28. Equivalent weights. Normal solutions . 1,24, Advantages of the uso of the equivalent oyster i for the pre- aration of standard solutions . : i, 1, 25. Preparation of standard solutions. 9. | : 126. Primary standard substances =. : THEORY OF ACID-BASE TITRATIONS 1, 27. Neutralisation indicators . to. I, 28. Preparation of indicator solutions . . . . . I, 29. Mixed indicators . . . . . 1, 80. Universal or multiple range indicators ton I, 81, Neutralisation curves . . . L 32, Neutralisation of a strong acid and a strong base . I, 83, Neutralisation of weak acid with a strong base : T, 34, Neutralisation of a weak base with a strong acid. . I, 35, Neutralisation of a weak acid with a weak base. . 1, 86, Neutralisation of a polybasic acid with a strong base. I, 87. Titration of anions of weak acids (Bronsted bases) with strong acids. “ Displacement titrations”. . 1, 88. Choice of indicators in neutralisation reactions xiii 9, Completeness of prodptaion “Quantitative effects of axiv Contents THEORY OF PRECIPITATION AND COMPLEX FORMATION PROCESSES nce 1, 39. Precipitation reactions =. . wee 1, 40, Complex formation réactions : 1” 1,41. Determination of end points in precipitation and ‘in complex formation reactions . Soe 16 THEORY OF OXIDATION-REDUCTION REACTIONS I, 42, Oxidation-reduction reactions 9.5 sw wwe 8B 1, 48. Electrode potentials...) ss I, 44. Concentration cells . . . . . 87 I, 45, Calculation of the em. ofa voltaic cel | + + | 88 I, 46. Oxidation-reduction cells 2 of 88 I, 47. Calculation of the standard (reduction) potential - | | 90 I, 48. Equilibrium constants of oxidation-reduction reactions . 91 T, 49. Change of tho clectrode potential during the titration of an oxidant and a reductant. Oxidation-reduction curve. . 94 1, 50. Formal potentials. : 97 I, 51. Detection of the end point in oxidation-reduction titrations | 99 THEORY OF GRAVIMETRIC ANALYSIS I, 52. Gravimetric analysis . . . : . . . » 104 I, 58, Precipitation methods Dot : I, 54. The colloidal state. : . . . . I, 56. Supersaturation and precipitate formation . . . I, 56. The purity of the precipitate. Co-precipitation . . . 110 I, 52. Conditions of precipitation . . I, 58, Precipitation from homogeneous solution | T, 59. Washing of the precipitate . 1 00. Ignition of the precipitate ‘Thermogravimetric method of analysis. rn ne 1, 61. Fractional precipitation 1. 1 1 LLL 80 1, 62. Organic precipitant). | |) ft te I, 63. Extraction reagents. . . . : . 14 I, 64. Volotilisation or evolution methods =. | |). 187 1,65. Selected bibliography. | sk 89 CHAPTER II EXPERIMENTAL TECHNIQUE or OE RUANTITATIVE INORGANIC Ii, 1, Balance, weights, and wghing . see. 140 IE, 2. Description of a typical analytical balance | | 0) (HAL Il, 8, The requirements of a good balance. + . . - 142 I, 4. Weights, reference masses... |] ft] ) gg, Care and use of the balance . . . . . . 144 Ti, 6. Methods of weighing». | f] Td a WW, %. Errorsinweighing =») ee Ii, 8. Calibration of weights =» |) ) La TH, 9. Other types of balances =. |) |) Sa GENERAL APPARATUS, REAGENTS, AND OPERATIONS 11,10, General apparatus... wD IE, 11, Reagents . Boe et a8 II, 12. Purification of substances . . . . . . » 181Contents MI, 18. Heating apparatus 5 ww ww, Ui, 14. Stirring of liquids . . . . . . . 15. Samplingofsolids 2 sf ff] TI, 16, Solution of the sample . . . . . If, 25. Storage and preservation of solutions for volumetric analysis. 1,2. Precipitation. =. 7 wee Il, 27. Filtration . . . . . . 28. Filter papers 2) | kt U9. Fiterpulp 5 2 5. I, 80. Filter mats. Gooch crucibles. . . U, 81. Preparation of a Gooch crucible . . . . . , 82. Munroe crucibles . . . . . TL, 98. Crucibles fitted with pormanent porous plates TT, 34. Washing of precipitates Lee I, 85, Technique oo Tt, 386. Drying and ignition of precipitates. UL, 37, Tho care and use of platinum vessels. Wi, 88, Perforated screens for crucibles . TECHNIQUE OF GRAVIMETRIC ANALYSIS filtration : MISCELLANEOUS OPERATIONS M1, 59, Reduction with metals =. swe, TL, 40. Use of perchloric acid in inorganic analysis || : IE, 41, Selected bibliography =. =... st BB m, / TL, m1, i, 1m, Im, im, I, CHAPTER It VOLUMETRIC (TITRIMETRIC) ANALYSIS AQUEOUS ACID-BASE TITRATIONS ACIDIMETRY AND ALKALIMETRY 1. Preparation of a standard acid . . . . . 2. Preparation of constant-boiling-point hydrochloric acid. | 8. Direct. preparation of 0-1N-bydrochloric acid from the constant-boiling-point acid. - . . 4, Preparation of 0-1N-hydrochloric acid and standardisation . 6. Preparation of standard alkali . + . + . . 6. Standardisation of the approximately 0-1V-sodium hydroxide. 7. Other standard substances for acidimetry and alkalimetry 8. Standard barium hydroxide (baryta) solution =... 9. D.* of the NaqCO, content of washing soda nn 10. D. of the strength of glacial acetic acid =. |]! 11. D. of sulphuric acid in the concentrated acid . . . *D, = determination. a TECHNIQUE OF VOLUMETRIC (TITRIMETRIC) ANALYSIS H,1%. Unitofvolume. 2. 2 ww TL, 18. Standard temperature | |) Ii, 19. Volumetric apparatus =| IT, 20. Volumetric flasks Do IL @1. Pipettes 2 Ii, 22. Burettes | Dol IL, 98. Weight burettes. =. 5 1, Tl, 24. Graduated cylinders xV rok 183 186 187 188. 191 191 192 196 200 207 233 234. 234 239 242 243 246 248xvi Contents Tf, 12. D. of sulphuric acid in the fuming acid (oleum) II, 18. D. of carbon dioxide in the atmosphere . . MIL, 14. D. of a mixture of carbonate and hydroxide. “Analysis of commercial caustic soda. . . I, 15. D. of a mixture of carbonate and bicarbonate . If, 16. D. of phosphoric acid in commercial ortho- hosphorie acid I, 17. D. of boric acid and borax . . TH, 18. D. of ammonia in an ammonium salt | . IM, 19. D. of nitrates (sodium nitrate in Chile salipetre) « : II, 20. D. of nitrogen by Kjeldahl’s method . Dot PRECIPITATION TITRATIONS TI, 21, General discussion. . . . . IIL, 22. Preparation of 0-1N-silver nitrate IL, 23. Standardisation of the silver nitrate solution III, 24. D. of chlorides . . . . IM, 25. D. of bromides . HI, 26, D. of chlorides and of bromides with standard merourous perchlorate solution —. rn : IIL, 27. D. of iodides. . . . . . . . Uf, 28. D. of thiocyanates | : IM, 28. D. of mixtures of halides with adsorption indicators | Uf, 30. D. of mixtures of halides by an indirect method . . . IIT, 31. Preparation and use of 0:1N-ammonium or potassium thio- cyanate. Titrations according to Volhard’s method . IH, 82. D.ofsilverinasilveralloy . . . . . IH, 38. D. of chlorides (Volhard’s method). . . . MI, 34. D. of bromides (Volhard’s method) . . . . III, 35. D. of iodides (Volhard’s method) . . . . I, 86. D. of dithionites . . . . . . . IM, 37. D. of cobalt. . . : : . . . . IMT, 88. D. of nickel. . . H, 89. D. of fluoride as lead ‘chlorofiuoride . UT, 40. D. of arsenic as silver arsenate . WT, 41. > of cyanides . 42. D. D. of chloride M44. D. of barium ond of sulphates... OXIDATION-REDUCTION TITRATIONS. OXIDIMETRY AND REDUCTIMETRY HI, 45. General discussion. . . . . . OXIDATIONS WITH POTASSIUM, PERMANGANATE IM, 46, Discussion . . IIL, 47. Preparation of O-1N-potassium permanganate | |! IIL, 48. Standardisation of potassium permanganate solutions . TIL, 49. Permanence of potassium permanganate solutions Ii, 50. D. of ferrousiron . . . . Ill, 51. Reduction of ferric to ferrous iron woe . . III, 52. D. of iron in ferric ammonium sulphate . . . I, 58. D. of the total iron in an iron ore . . . . II, 54. D. of calcium in calcium carbonate . . . . TIL, 55, Analysis of hydrogen peroxide .° . . . . . II, 56. Analysis of sodium peroxide nn II, 57. D. of manganese dioxide in pyrolasite . . . IH, 58. D. of nitrites. . . .Contents If, 59. D. of persulphatos MIL, 60. D. of manganese in atecl II, 61. D. of formates and of formic acid : MI, 62. Diofsdonium. =... OXIDATIONS WITH POTASSIUM DICHROMATE Il, 63. General disoussion . Loe HIT, 64. Preparation of 0-1N-potassium dichromate | UL, 66. Standardisation of potessfum dichromate solution against M1, 68. D. of ferrous iron UL, 67. D. of ferric iron (iron in ferric ammonium sulphate) 11, 68. D. of the total iron in an iron ore. : Il, 69. D. of ferrous and forric iron in anironore |, TH, 70. D. of chromium ina chromicsalt =. | | € chromium in chromite ft : . of chlorate . . . . . : OXIDATIONS WITH CERIC SULPHATE IM, 73. Goneral discussion. toe IY, %4. Preparation of O1N-ceric sulphate: | |! IIL, 75. Standardisation of ceric sulphate solutions | UL, 36. D. of oxalates (H,C,0, in orysallsed oxalio saci). ML, 72. D. of iron in an iron ore. . IL %8. D.ofnitrites . 6) Lt M79. Dofeoppr 2 2} fff? IM, 80. D.ofmolybdonum > FS IM, 81. D. of tellurium , . . . . . . . . TH, 82. D. of cerium - . soe . . : . . OXIDATIONS WITH MANGANIC SULPHATE IH, 88. General discussion. . i, 84, Preparation and standardisation of manganic sulphate solu- 1H, 85, Applications of manganic sulphate solutions =|} REDUCTIONS WITH TITANOUS SALTS IL, 86. General discussion coe TIL, 87. Preparation of titanous solutions TL, 88, Standerdisetion of the titanous sulphate (or ‘titendus chloride} solution . . . . . 0,89. D.ofirminanore. . } fet REDUCTIONS WITH AMALGAMATED ZINC AND WITH LIQUID AMALGAMS TIL, 90. General discussion . . . ote . . it 91. D. of uranium . . : . . . D. of titanium . . . . . . of molybdenum - . of titanium (zine amalgam method) | . of tun, nungséen (lead amalgam method) : in oe Simplified technique in the use of liquid amalgam reductors Ill, 9%, Reductions with hypovanadous salts . . . . xvii Pace 298 301 302 327 327 327 329 329 330, 331xviii Contents Pace IM, 98. Reductions with chromous salts . . . 340 OXIDATION AND REDUCTION PROCESSES INVOLVING IODINE—IODIMETRY AND TIODOMETRY Ill, 99. General discussion . Se 848 Il, 100, Detection of the end point . . . . 845 TI, 101. Preparation of 0-1N-sodium thiosulphate . . - 348 TL, 102. Standardisation of sodium thiosulphate solutions . + 349 IM, 103. Preparation of 0-1N-iodine solution . . . . - 354 TI, 104. Standardisation of iodine solutions . . . . 855 II, 105. D. of copper in crystallised copper sulphate se 858 WW, 106. D. of copper in an ore. tk B88 TIL, 107. D. of manganese dioxide in pyrolusite . | | | 360 TH, 108. D. of chlorates . . . . . . 361 UE, 109, Volumetric determination ‘of lead . . . . . 362 IM, 110. Analysis of hydrogen peroxide . : of. B68 HI, 111, D. of available chlorine in bleaching powder . . + 363 IML, 112. D. of hypochlorites. fof 365 II, 113. D. of antimony(II1) tek 865 IIL, 114, D. of antimony(V) in antimonie oxide and in“ antimonates 366 IIL, 115. D. of arsenie(¥) ) in arsenic oxide and in arsenates . . 367 TIL, 116. D. of tin(II) . ee 887 DIL, 117, D. of antimony and tin in type metal = |). 369. I1T, 118. D. of sulphurous acid and of sulphites =. . | | 370 II, 119. D. of hydrogen sulphide and of aulphides Hook 870 IHL, 120, D. of ferricyanides soo. 8d IIL, 121, D. of ferric iron (iodometrie method) =| |], 87 OXIDATIONS WITH POTASSIUM IODATE IM, 122. General discussion . . . 374 IM, 128, Preparation of 0- LN (Or 025M). -potassiam iodate . ‘ + 375 IM, 124. D. of iodides . + + . . . 875 I, 125, D. of arsenic or of antimony . : . . + . 376 IM, 126. D. of copper . Bee BIT TL, 127. D. of mercury. . . . . . : . . 317 MM, 128. D. of tin : . 378 TfL, 129. D. of dioxides (lead, barium, and manganese dioxides) + 379 TIL, 130. D. of hydrogen peroxide. |. too : 379 I,181.D.ofhydrazime . . . . . . . . 380 IIT, 182. D. of thallium . . . . . . . . 380 DY, 188. D. of iron . . . . . . . . » 380 W134. D.ofvanadium 5. we BL OXIDATIONS WITH POTASSIUM BROMATE TI, 185. General discussion . . . . . 383 TEI, 186, Preparation of O-LN~ potassium ‘bromate . . . . 385 IH, 187. D. of antimony or of arsenic. . 385 II, 188, D. of metals by means of 8- hydroxy quinoline w xine”) | 386 TIL, 139. D. of hydroxylamine 2 301 OXIDATIONS WITH CHLORAMINE-F WI, 140, Generel discussion. Preparation and standardisation of OLN-solutin . . + 392 MH, Ui. D.ofantimony =... e802 ILL, 142. D. of nitrites - : : : : . : : + 393Contents I, 143, D.oftin MI, 144. D. of ferrocyanides | OXIDATIONS WITH SODIUM HYPOCHLORITE MIL, 145, General discussion . . TL, 140. Preparation of -1N-sodium hypochlorite | : MI, 147, D. of ammonia in an ammonium salt (hypobromite method) REDUCTIONS WITH MERCUROUS NITRATE ‘HI, 148, General discussion . . II, 149, Preparation of 0-1N-mereurous nitrate | IIT, 180. D. of ferric iron (mercurous nitrate method) MHL, 151, Miscellaneous determinations with standard’ mercurous nitrate solution . TH, 162. D. of fervioyenide with’ standard mercurous “perchlorate solution". . . MISCELLANEOUS VOLUMETRIC (TITRIMETRIC) DETERMINATIONS MH, 158. D. of zine with standard potassium. ferrocyanide solution . LI, 154. D. of phosphorus as ammonium phosphomolybdate . Ii, 155. D. of phosphorus as quinoline phosphomolybdate HY, 188, D- of silicon as quinoline ‘ilicomolybdate IH, 157, D. of calcium (urea hydrolysis Soathods precipitation from ‘homogeneous solution) . + IM, 158, D. of zirconium as the normal selenite, Zr(Se0.)e : uL 159. D. of en Lo on : , 160. D. of yp! ites. : : . IH, 161. D. of sodiuen ne . . . . . . . MI, 162, D. of potassium Bo IL, 168. Selected bibliography =. . . . . . CHAPTER IV COMPLEXOMETRIC (LARGELY EDTA) TITRATIONS 1, General discussion. : . . : tability constants . | se Titration curves + . . . . . ‘Types of EDTA titrations | Vy tration of mixtures. Masking and demesking agents. IV, 6. Metal ion indicators . . . IV, 7%. Some examples of metal i ion indicators IV, 8 Detection of colour changes of metal ion indicators by an instrumental method. . . : Iv, 9. Standard EDTA solutions . + IV, 10. D. of zine using Eriochrome Black T a8 indicator. 1V, 41. D. of magnesium using Eriochrome Black T’ as indicator IV, 12. D. of manganese using Eriochrome Black T as indicator IV, 18. D. of magnesium using Solochrome Black 6B as indicator IV, 14, D. of nickel using murexide as indicator (direct titration) IV, 15. D. of nickel using Eriochrome Black T as indicator (back- titration). IV, 16, D. of aluminium sing Eriochrome Black T as indicator ‘(back- titration) woe oe xix Pace 393 394 395. 396 396 398 398 399 399 _ 400 408 409 410 All All 412 414 432 432 433. 434. 434 435 435, 435 436xx Contents IV, 17. D. of calcium using Eriochrome Black T as indicator (sub- stitution titration). IV, 18. D. of the total hardness (permanent and temporary) of water using Eriochrome Black T as indicator . /W, 19. D. of calcium and of magnesium in admixture fo IV, 20. D. of copper using Fast Sulphon Black F as indicator» - IV, 21. D. of nickel using Bromopyrogallol Red as indicator. IV, 22. D. of bismuth using Bromopyrogallol Red as indicator. IV, 28. D. of bismuth using Xylenol Orange as indicator... IV, 24. D. of thorium using Xylenol Orange as indicator. =. IV, 25. D. of lead using Xylonol Orange as indicator =. sk IV, 26. D. of cobalt using Xylenol Orange as indicator Dot AV, 27. D. of zine using Xylenol Orange as indicator 5. “WY, 28. D. of cadmium using Xylenol Orange as indicator, =. IV, 29. D. of ferric iron using Variamine Blue Bas indicator . IV, 80. D. of thorium using Pyrocatechol Violet as indicator. IV, 81. D. of bismuth using Pyrocatechol Violet as indicator. IV, 82. D. of copper using Pyrocatechol Violet as indicator =. IV, 83. D. of nickel using Hriochrome Red B as indicator : IV, 34. D. of manganese using Thymolphthalexone as indicator. IV, 85, D. of sulphate by precipitation as barium sulphate and dis- solution of the precipitate in excess of EDTA IV, 86. D. of sulphate by precipitation as lead sulphate and indirect ‘titration with EDTA IV, 87. D. of phosphate by precipitation as Mg(NH,)P0,,6H,0 and irect titration with EDTA . IV, 88, Indirect determination of halides: potassium nickelocyanide and nickel ion-indicator method IV, 89. Indirect determination of silver: potassium niokelooyanide and nickel ion-indicator method IV, 40. Analysis of manganeso-magnesium and of manganesé-mag- nesium-zine mixtures. . . . + IV, 41, Analysis of solder Bo IV, 42, D. of manganoso in fervo-manganese |). IV, 48. D. of nickel in nickel steel . fo IV, 44. Analysis of low-melting Bi-Pb-Cd-Sn alloys : IV, 45. Selected bibliography. to CHAPTER V GRAVIMETRIC ANALYSIS ¥, 1. General discussion Bo V, 2 Note-book, entries, and calculations | Do V, 8. Calculations of gravimetric analysis. Chemical factors | SIMPLE GRAVIMETRIC DETERMINATIONS ¥, 4 D. of water of hydration in enystalised barium chloride. « ¥, 5. D. of chloride as silver chloride toe V, 6, D. of sulphate as barium sulphate Bot ¥, % D. ofsulphur iniron pyrites of iron as ferric oxi to of aluminium as aluminium oxide ©) ) 1! - of ealeinin as oxalate v1 sium as the ammonium Phosphate hexahydrate ae the pyrophosphate. an Vy 1% D.ofnickel a thedimethylglyoximate =| |]! BERPDS ee 450 453 453 457 458 458 458Contents SYSTEMATIC GRAVIMETRIC ANALYSIS. Y, 15. Silver . . Vi16. Mercury . y, 17. Biemuth . . ¥, 18. Cadmium . . ¥, 19. Copper V, 20. Arsenio. . . : V,21. Antimony. 9. ss V, 22, Tin . . . . . : V.93, Molybdenum V, 24. Selenium and tellarium . . V, 25. Platinum . . . . . V, 26. Palladinm . . . : : V, 27. Gold . . . . . V, 28. Aluminium . . V, 29. Beryllium . : Y, 30. Chromium . . . Y, 31. Iron . . . . . . V, 82. Nickel . . . . . V, 88. Cobalt. . . . . V, 84. Zinc . . . . . Y, 85. Manganese . . . V, 36, Vanadium . . . . YV, 37. Uranium - . . . Y, 38. Thorium . . . ¥, 39. Cerium. . . V, 40. Titanium . . . . Y, 41. Zirconium . . . . . -» 42, Thallium . . . . . ‘Y, 43. Calcium - . + . . vy, 44, Strontium . . . . . Vv, 45, Barium. . . . . V, 46, Magnesium . : . . V, 47, Sodium : YV, 48. Potassium . . Vv, 49. Lithium . . V, 50, Ammonium . . v.51, Tungston. - V, 52, Chloride . . . . . V, 58. Bromide . . . . . V, 54, Iodide. . . . . ¥, 65. Thiocyanate - . . . V, 56, Cyanide. . . . V, 57. Fluoride - . . . . ¥, 58. Chlorate - . + . . V, 59, Perchlorate =. - . . V, 60, Iodate = - . . Viel. Sulphate» st ¥, 62. Sulphide - . . . . Y, 68, Sulphite . . . . . V_ 64. Thiosulphate ¥, 85, Phosphate - Do Y¥, 68, Phosphite - . . . . ¥, 67. Hypophosphite - : : .xxii Contents V, 68. Oxalate. . . . V, 68. Borate : . . V, 70. Silicate 2. VY, 71. Fluosilicate . . V, 72. Ferrocyanide . . V, 73. Ferricyanide : V, 74. Nitrite. . . V, 75. Nitrate 2. V, 76, Carbonate . . V, 72. Sclected bibliography. CHAPTER VI ELECTRO-GRAVIMETRIC ANALYSIS VE, 1. ‘Theory of clectro-analyts « VI, 2. Electrode reactions VI, 3. Overvoltage VE, 4. Completeness of deposition. VI, 5. Electrolytic separation of metals. Character of the deposit. potential - Hlootrolytic separation of rotals with controled cathode 588 592 593 594 595 597 598 ELECTROLYTIC DETERMINATIONS AT CONSTANT CURRENT VI, 8. Appareins fo. VL 9. . . . : VE 10. Lend fot VEL. Cadmimms 2) VI, 12. Nickel : : VI, 18. Cobalt. Do VUl4. Silver 2. we VU48. Zine swe VI, 16. Bismuth . 601 2 608 ‘VI, 17. Bleotrolytic separation and determination of copper and 611 612 613 614 614 615 615 616 ELECTROLYTIC DETERMINATIONS WITH CONTROLLED POTENTIAL AT THE CATHODE VI, 18. General considerations VE, 19. Controlled potential clectro-analysis. Apparatus for auto- matic control of potential VI, 20. D. of metals in alloys using controlled potential at tho cathode VI, 21. Internal electrolysis... VI, 28. Selected bibliography CHAPTER VIE ANALYSES OF COMPLEX MATERIALS VU, 1. General discussion . . VIL, 2. Analysis of brass. VIL, 3. Analysis of bronze . VI, 4. Analysis of nickel silver 618 620 621 625 627 628 629 635Contents VI, 5. Analysisofsolder 2. 1 wee Vil, 6. Analysis of a silver alloy . : . - VE, 7. Analysis of steel =. . WH, 8. Analysis of a limestone or dolomite WL, 9. Analysis of an insoluble silicate. Don VII, 10. Analysis of Portland cement =. . . . . . VIL 1, Selected bibliography] |] CHAPTER VIIT COULOMETRIC ANALYSIS VIM, 1. General discussion . Boe 8. Coulometry at controlled potential | VII, &. Separation of nickel and cobalt by « coulometrie analysis at controlled potential . 663, 669 674 COULOMETRY AT CONSTANT CURRENT. COULOMETRIC TITRATIONS Vul, 4. General discussion . : : . . . . . Vit, 5. Instrumentation . . . Vill, 6. Circuit and cell for coulometry. ‘at controlled current | . VII, 7. Coulometric titrations with e low-inertia integrating motor. General considerations . VII, 8 Coulometric titration using an integrating motor-counter unit. Experimental detail . VII, 9. External generation of titrant | VIM, 10. Experimental details for typical coulometric titrations ab constant current . . . + . . ELECTROLYTICALLY GENERATED IODINE VIU,l. Antimony). . . . wet VIM, 12. Thiosulphate . . . . . . . ELECTROLYTICALLY GENERATED BROMINE VIL, 18. Oxine (8-1 jhydroxy quinoline) . . . . . . Metal oxinates . . . : . . ELECTROLYTICALLY GENERATED FERROUS ION ‘VIII, 14. Potassium dichromate (dichromate ion) . . . . ELECTROLYTICALLY GENERATED CERIC ION ‘VI, 15. Ferrousiron. Be ELECTROLYTICALLY GENERATED MERCUROUS ION VIII, 16. Chloride, bromide, and iodide . . . . . . ELECTROLYTICALLY GENERATED SILVER ION VHI, 17. Bromide and iodide . . . . ELECTROLYTICALLY GENERATED FERRICYANIDE ION VIII, 18, Thallium(I) - . : : . . ELECTROLYTICALLY GENERATED FERROCYANIDE ION VID, 19. Zine. . . : . ELECTROLYTICALLY GENERATED HYDROXIDE ION VIM, 20. Titration of acids . . . . . 676 679 680 681 684 685 686 687 688 688 689 689 691 692 694 695 696 697xxiv Contents ELECTROLYTICALLY GENERATED HYDROGEN ION VIII, 21, Titration of bases . . . . . : . . VIN, 22. Selected bibliography 2) fl CHAPTER IX ION EXCHANGE AND CHROMATOGRAPHIC METHODS IN ANALYSIS ION-EXCHANGE METHODS IX, 1. General discussion . IX, 2. Action of ion-exchange resins Bt IX, 3, Columnoperation =~. 1 eke TK 4. Experimental techniques Do TE, 5. Changing the fonie form. Some widely used resins SIMPLE APPLICATIONS IN ANALYTICAL CHEMISTRY IX, 6. General remarks on the preparation of ion-exchange resins. TX, 7 Determination, of the capacity of an ion-exchange resi (column method) . IX, 8. Separation of zinc and magnesium on an anion exchanger XX, |B. Separation of chloride and bromide on an anion exchanger IX, 10. D. of the total cation concentration in water . . IX, 11. Separation of cobalt and nickel on an anion exchanger. IX, 12. Separation of cadmium and zine on an anion exchanger IX, 18. D. of fluoride with the aid of a cation exchanger . 1X, 14. D. of sulphur in iron pyrites with the aid of a eation exchanger IX, 15. D. of sodium with the aid of a cation excl 1X, 16. D. of sodium and potessium in edmixture. ‘Uso of o cation exchanger... . Lo CHROMATOGRAPHIC METHODS IX, 17. General introduction IX, 18, Soparation of nickel, manganese, cobalt, and zine on’ paper strips. Determination of Ry values IX, 19. Soparation of nickel, copper, cobalt, and zino on paper strips . 1X, 20. Semi-quantitative separation of eopper, cobalt, and nickel on slotted paper strips. 1X, 21. Separation of iron and aluminium on a cellulose column IX, 22, Separation of cobalt and nickel on a cellulose column . IX, 23. Soparation of coppor and nickel on a cellulose column IX, 24. Selected bibliography . 3 . 3 . 3 . . 1. CHAPTER X COLORIMETRIC AND SPECTROPHOTOMETRIC ANALYSIS X, 1. General discussion. X; 2 Theory of spoctrophotometry and colorimetry X 8. Cluesiication of methods of “ colour” measurement or com- X, 4, Standard series method || X, 5. Duplication method » |} st X, 6. Balancing method: Dt X, 7. Photoelectric filter photometer method” : X, 8 D. of pH of solutions by colorimetric methods. | XX, 9. Somo general remarks upon colorimetric determinations - Pao 701 702 708 710 Tl ‘714 714 ‘715 716 716 ni 718 720 T21 722 723 TRA 727 728 ‘729 730 733 ‘734 736X10. D.ofammonia. 2 1. wee, X, 11. D. of nitrites. . . . . . . . . KieDofion. 2 2 Ft X18. Manganese et Xi. Vitenum. Ft Kis. Vanadium, 6 | Kji6. Chromium, 6 sft Xi. Alminum 2 fF Ft X18. Molybdenum 2 |e, XiNikl 2 | E20. Cobalt 2 | FP Kel Arenio - 7 28. X, 29. Sulphate Fluoride . X, 80. Chloride. ‘ X, 81. Silicate. . . . . . . . . . X, 82. Phosphate Be X, 88, Borate. . . : . . : : . : EXPERIMENTS WITH ULTRA-VIOLET AND VISIBLE SPECTROPHOTOMETERS X, 84, Determination of the absorption curve of a substance (potassium nitrate). Use of a spectrophotometer for the determination of the concentration of a solution. X, 85. Spectrophotometric determination of the pK value of an indicator (the acid dissociation constant of methyl red) . X, 86. Simultaneous spectrophotometrie determination (chromium and manganese). . . . . . SPECTROPHOTOMETRIC TITRATIONS X, 87, Spectrophotometric titrations — . . . . X, 88, Apparatus for spectrophotometric titrations | . . &, 39. Spestrophotometrie determination of ferric iron with EDTA | X, 40. Spectrophotometric determination of cupric ion with EDTA . X, 41. Spectrophotometric determination of nickel ion with EDTA . INFRA-RED SPECTROPHOTOMETRY X, 42, Infra-red absorption spectrophotometry . . . . X, 48, Apparatus for infra-red spectrophotometry . . . : X, 44, Commercial instruments % AB. Some experiments with the infra-red spestrophotometer. &, 46. Sele ibliography . . . . . . CHAPTER XI FLUORIMETRIC ANALYSIS XI, 1. General discussion. Boe eee XT, 2. Instruments for fluorimetric analysis © |. lt 838 839xxvi Contents XI, 3. Some applications of fluorimetry . foe XI, 4. Fluorimetric determination of quinine |. 1) XI, 5. Fluorimetric determination of aluminum => |) XI, 6. Fluorimetric determination of zine . . XI, 7. Fluorimetric determination of cadmium Doo XI, 8. Selected bibliography. 9. st CHAPTER XII NEPHELOMETRIC AND TURBIDIMETRIC ANALYSIS ZI, 1, General discussion. to XM, 2. Instruments for nephelometry and turbidimetry - : : XI, 8. Nephelometric determination of sulphate XII, 4. Nephelometrie dotermination of phosphate « 2 ot XII, §. Selected bibliography : BG CHAPTER XIII EMISSION SPECTROGRAPHIC ANALYSIS XII, 1. General discussion . an XMI, 2. Equipment for emission spectrographio analysis « 2 XML, 8. Qualitative spectrographic analysis tot XUL, 4. Quantitative spectrographic analysi XI, 5. Qualitative spectrographic ‘onalyais of (a) a non-ferrous alloy and (b) a complex inorganic mixture... XIN, 6. Spectrographic determination of lead in brass XID, 7. Spectrographic determination of eopper and. lead in white metal . . XII, 8. Selected Bibliography | . . . : . . CHAPTER XIV FLAME PHOTOMETRIC ANALYSIS XIV, 1. General discussion . . . . . . XIV, 2. Instruments. . . XIV, 3. Use of a typical simple fame photometer | XIV, 4, Experiments with a simple flame photometer XIV, 5. Use of a typical flame spectrophotometer XIV, 6. Atomic absorption spectroscopy - . : XIV, 7. Selected bibliography =. |] : CHAPTER XV SOLVENT EXTRACTION METHODS IN ANALYSIS LIQUID-LIQUID SYSTEMS XV, 1, General discussion. So XV, 2. Factors favouring solvent extraction | : XV, 8. Quantitative treatment of solvent-extraction equilib : XV, 4. Some practical considerations . : : SOME SIMPLE APPLICATIONS XV, 5. D.ofiron by chloride extraction 9... 6. D. of iron as the 8-hydroxyquinolate. =|) |! . of uranium as the 8-hydroxyquinolate | | | xv, 854 856 867 869 872 875 878 890 891 895 897 899Contents xxvii XV, 8. D. of lead by the dithizone method . . . xv, of nickelas the dimethylglyoxime complex... xv, of copper as the giethyaithioesrbemate complex 2. ye . of copper as the “ neo-cuproin ” complex . . . . D. of beryllium asthe acetylacetone complex. | |! , 13. D. of molybdenum by the thiocyanate method - : SOLID-LIQUID SYSTEMS XV, 14. Extraction of soluble mixtures by solvents... XV, 15. Selected bibliography . . . . 1 CHAPTER XVI POTENTIOMETRIC TITRATIONS XVI, 1. General considerations. . . . : . : XVI, 2. Determination of pH Dl XVI, 8. Potentiometric titrations. Classical method . . . XVI, 4. Potentiometric titrations.—Electronic instruments. XVI, 5. Automatic potentiometric titrations . XVI, 6. Determination of water with the Karl Fischer reagent XVI, 7, Some experimental details for potentiometric titrations XVI, 8, Standardisation of sodium thiosulphate or of iodine solution with potassium permanganate or with Potassium ae chromate XVI, 9. D. of the available chlorine in Bleaching powder” . . XVI, 10. D. of copper . . . . . . . XVI, 11. D.of chromium. : . . . . . . XVL12.D.ofmanganese © sf XVI, 18. D. of cobalt . . . . . . . . . XVI, 14. D. of nitrate . . . . . . . . . XVI, 15, D.of sulphate | XVI, 16, Potentiometric EDTA titrations with the mercury electrode XVI, 17, D. of ferric iron with EDTA. XVI, 18, Standardisation of potassium pormangenate solution with potassium iodide . . XVI, 19. D. of nickel and of cobalt) by oun with ‘cyanide XVI, 20. D. of fluoride by a null-point method . . : XVI, 21. Selected bibliography . . po CHAPTER XVII CONDUCTOMETRIC TITRATIONS ‘XVII, 1. General considerations. . . . . . XVI, 2. Apparatus and measurements . to. XVIL, 3. Applications of conductometric titrations | | XVO, 4. Some experimental details for conductometric titrations XVI, 5. Applications of single determinations of conductance . . ‘XVI, 6. Sclected bibliography . . . . . . CHAPTER XVIII HIGH-FREQUENCY TITRATIONS XVIII, 1. General considerations. . XVIII, 2. Construction and use of a high-frequency titrimeter | XVIIT, 8. Determinations with the high. froquoncy titrimeter XVIII, 4. Sclected bibliography : PAGE 899 901 901 902 903, 904. 907 969 972, 978 985 987xxviii Contents CHAPTER XIX POLAROGRAPHIC ANALYSIS XIX, 1, General introduction 2... XIX, 2. Theoretical principles . 5 1 0. XIX, 3. Quantitative technique. General considerations XIX, 4. Evaluation of quantitative results . : XIX, 5. Measurement of wave heights. . | | XIX, 6, Manual non-recording polarograpbs. 2 XIX, 7. Commercial polarogra XIX, 8. Ancillary equipment for polarography x 9B. the ilteware potential of the cadmium ion in potassium chloride solution . XIX, 10. D: of the half-wave potentials of the zine and manganous ions in M-potassinum chloride solution . . 1028 XIX, 11. D. of cadmium in solution . . + 1028 XIX, 12, Investigation of the influonce of dissolved oxygen | | 1029 XIX, 18. D. of lead and copper in steel 1030 XIX, 14. Determination of the formula and the stability constant of a metal ion complex (lead oxalate complex} toe 1031 XIX, 15. Selected bibliography - . . . » 1034 CHAPTER XX AMPEROMETRIC TITRATIONS XX, 1, Theoretical considerations 1035 XX, 2. Technique of amperometric titrations with the droping mercury electrode 1038 XX, 8. D. of lead with standard Potassium dichromate solution + 1039 XX, 4. D. of sulphate with standard lead nitrate solution. . 1040 XX, 5. D. of nickel with dimethylglyoxime. . . . . 1041 XX, 6. D. of cobalt with «-nitroso-f-naphthol . : . « 1042 XX, 7. D. of copper with benzoin «oxime . 1043 XX, 8. D.of cadeaium with 6-naphthoquinoline (5, (6-1 -benzoquizoline) 1044 XX, 9,-D. of fluoride with standard thorium nitrate solution . 1044 XX, 10. D. of zine with EDTA . . : ~ 1045 XX, 11. D. of bismuth with EDTA. . 1046 XX, 12. Titration of an iodide solution with mercuric nitrate solution 1046 XX, 18. D, of potsssium with sodium tetraphenylborate (graphite jndicating electrode). 5 1047 TITRATIONS WITH THE ROTATING PLATINUM MICRKO- ELECTRODE XX, 14. Discussion and apparatus 1048 XX, 15. D. of thiosulphate with iodine (rotating platinum micro- ‘electrode) . . 1049 XX, 16. D. of arsenite with standard iodine solution (rotating platinum microelectrode) > 1050 XX, 17, D. of antimony with standard potassium’ bromiate solution (rotating platinum miero-electrodo) =. =. =. «1050 AMPEROMETRIC TITRATION WITH TWO INDICATOR ELECTRODES (“ DEAD-STOP END POINT”) XX, 18. General discussion . + 1051 XX, 19. Titration of thiosulphate with iodine « dead. stop end 1 . 1051 XX, 20. sche bibliography ae 075Contents xxix CHAPTER XXI GAS ANALYSIS Pace XXI, 1, General discussion. 2. wee XXI, 2, Sampli . + . . . . . » 1054 XXL 3. Puri cation of mercury | : 1056 XXT, 4, Correction of volume of gas for temporature and pressure | 1058 XxL 5. Calibration of gas measuring vessels =. sss «1060 XXI, Apparatus employed in gas analysis . . . + 1061 XXL ‘Absorbents for the various gases. 1079 XXI, 8. Determinations by losin, slow combustion an and fractional combustion methods. + . » 1083 XXI, 9. Exercises in gas analysis | |] ] So] ] 1088 GAS-VOLUMETRIC METHODS OF ANALYSIS FOR SOLIDS AND LIQUIDS XXI, 10, The Lunge nitrometer - 5 ss ss 1088 XXI, 11, D. of nitrates . . - . . . . 1088 XXL, 12. D. of hydrogen peroxide 9: | |}. 1000 XT, 13, Evaluation of pyrolusite {floor XXI, 14. D. of the available chlorine in bleaching powder | | 1091 XXL, 15. Evaluation of zinc dust. yee 1091 XXT, 16. D. of ammonia in ammonium salts: 1 | || 1092 XXI,17. Selected bibliography . . . . . . 1098 CHAPTER XXII MICRO-GRAVIMETRIC AND MICRO-VOLUMETRIC (TTTRIMETRIC) ANALYSIS XXL, 1, General discussion . : . : . . . » 1094 ‘XXII, 2. Micro-balances. . . - 1094 XXII, 3, Miscollancous apperatus for micro-snalysis | | «(1096 XXII, 4. Apparatus for quantitative filtration +. 1108 XXII, 5. Apparatus for micro-volumetric (micro-titrimetric) analysis 1109 6. Some simple micro-gravimetric determinations . 1116 XXIL 7. Some simple miero- volumetric (micro -titrimetric) determina- ns 1 XXII, 8 Selected bibliography on micro-gravimotrie ‘and ‘micro- volumetric (titrimetric) analysis... ~ 1120 CHAPTER XXIII ERRORS IN QUANTITATIVE ANALYSIS XML 1. Accuracy. Precision. Mean (average) deviation. Stan dard deviation. . Hat XXII, 2, Classification of errors») sss BB XXL, 8. Minimisation of errors | 1124 XXII, 4. Determination of the accuracy of methods of quantitative 8 alysis - . ul EXIM, 6, Signifisent figures and computations SLL ez XXIM, 6. Statistical methods in analysis. =. |] | || 1188 XXIU, 7. Selected bibliography. . |] tC APPENDIX A, 1, International atomic weights, 19599... 0... LIBEL A, 2. Chemical factors . : . . : . . 1132X&xX Contents A, 8, The literature of analytical chemistry . A, 4, Densities of acids at 20° C. . . A, 5. Densities of alkaline solutions at 20°C. A, 6. Data on the strength of aqueous solutions of ‘the common acids and of aqueous ammonia . : A, 7. Saturated solutions of some reagents ab20°C. | A, 8. Solubilities of some inorganic compounds in water at various gatemperatures see les and solutions for elementary analysis . iy 10. seabed samples. an 2,11, Buffer solutions and secondary pH standards | A, 12. Approximate pH values of some common. reagent solutions at out room temperature . . . A, 13. Comparison of metric and other units§ =. =. A, 14, Decimals of an inch, LS.W.G., and millimetres. . A, 15. The Greck alphabet. : ‘A, 16. Solubility products at about room temperature . oo. A, 17. Dissociation constants of some acids in water at 25° C. A, 18. Polarographio half-wave potentials A, 19. Tables of aro “ raies ultimes ” and persistent ines for spectro. A, 20, Four. logarithms =. . . . . . . A,QL, Five-figure logarithms =. 9. 5.) wt A, 22, Reciprocals =. . . . . . . . Index. . . . : . : . . Paar 1137 1142 1142 1148 1144 1146 1160 1161 1165 1165 1166 1167 1169 1170 Hm 1176 1195 1199