TEXTBOOK OF aT CHEMICAL ANALYSIS J MENDHAM | R C DENNEY JD BARNES | M THOMAS B SIVASANKARAuthorized adaptation from the United Kingdom edition, entitled Vogel's Textbook of Quantitative Chemical Analysis, 6th Edition, ISBN: 9780582226289 by Mendham, J.; Denney, R.C.; Bames, J. D.; Thomas, M., published by Pearson Education, Ltd., Copyright © 2000 Indian Subcontinent Adaptati Copyright © 2009 Dorling Kindersley (India) Pvt. Ltd, This book is sold subject to the condition that it shall net, by way of trade or otherwise, be lent, resold, hired out or othenwise circulated without the publisher's prior written consent in any form of binding or cover other than that in which itis published without a similar condition including this condition being imposed on subsequent purchaser and without limiting the rights under copyright reserved above, no part of this publication may be reproduced, stored in or introduced into a retrieval system, or transmitted in any form or by any means (electronic, mechanical, photocopying, recording or otherwise), without the prior written permission of both the copyright owner and above-mentioned publisher of this book ISBN 978-81-317-2325-8 First Impression This edition is manufactured in India and is authorized for sale only in India, Bangladesh, Bhutan, Pakistan, Nepal, Sri Lanka and the Maldives. Published by Dorling Kindersley (India) Pvt. Ltd., licensees of Pearson Education in South Asia. Head Office: 7th Floor, Knowledge Boulevard, A-8(A), Sector-62, NOIDA 201309, UP, India. Registered Office: 14 Local Shopping Centre, Panchsheel Park, New Delhi 110 017, India. Printed in India at Tara Art Printers,Contents Detailed contents y Preface to the sixth edition xxiii Preface to first edition xxvi Safety in the laboratory xxviii Units and reagent purity XxiN 4__Chemical analysis 3 Common apparatus and basie techniques 58 4 Statistical treatment of analyt data and introduction ‘is bi 0 5 Sampling 158 6 ___ Separation techniques 7 Thin-layer chromatography 4 9 Gas chromatography 10 Titrimetric analysis 14__Gravimetric anal 12__ Thermal analysis 13 _ Electroanalytical methods 14 Nuclear magnetic resonance spectroscopy 549 15 Atomic absorption spectroscopy 562 16 Atomic emission spectroscopy 595 17 Molecular electronic spectroscopy 608 18 Vibrational spectroscopy 675 19 Mass spectromeuy 701 Appendices 749 Index 720Detailed contents 1 Chemical analysis 1 Lt Introduction 1 1.2 Applications 2 13 Stages of analysis, 3 14 Selecting the method 3 LS Searching the literature. 4 1.6 Quantitative analysis by classical methods 3 1.7 Quantitative analysis by instrumental methods 3 18 Special techniques 6 1.9 Factors affecting the choice of analytical method 8 interferences S 111 Data handling 10 1.12 Robotics 10 113° Summary n 114 Reference n 2 Solution reactions: fundamental theory 12 2.2 Activity and setivity oneficient 13 23 Chemical equilibrium 14 2.4 Factors affecting chemical reactions in solution Is 2.5 The ionic product of water 16 2.6 Electrolytic dissociation 7 2.7 __Acid-base equilibria in water 0 2.8 Dissociation of polyprotic acids 21 2.9 The hydrogen ion exponent 2 241 The hydrolysis of salts 2 2.12 Degree of hydrolysis 29 213. Solubility product 3 214 Common ion effect 38 2.15 Common ion: quantitative effects 37 2.16 Fractional precipitation 39, 2.17 _ Precipitate solubility: effect of acids 40, viiDetailed contents vil 2.18 Precipitate solubility: effect of temperature 40 219 Precipitate solubility: effect of solvent 41 220 Complex ions 4 221 Complexation al 222 Stability of complexes 42 223 Complexones 4B 224 Stability constants of EDTA complexes 45 225 Electrode potentials 47 226 — Concentration cells 50 227 Calculating the emf. of a voltaic cell 31 228 — Oxidation-reduction cells 51 229 Calculating the standard reduction potential 52 230 Equilibrium constants of redox reactions 34 232 Bibliography 37 3 Common apparatus and basie techniques 68 3.1 Introduction 38 Balances 59 32 The analytical balance 39 3.3 Care and use of analytical balances 61 34 Errors in weighing 2 Graduated glassware 63 35 Units of volume 8 36 Graduated apparatus 63 3.7 Graduated flasks 64 38 Pipettes 65 3.9 Burettes 67 3.10 Weight bureties 68 3.11 Piston burettes 69 3.12 Graduated (measuring) cylinders 69 3.13 Calibration of graduated apparatus, 69 Water for laboratory use 4 3.14 Purified water n 3.15 Wash bottles 2B General apparatus 74 3.16 Glassware, ceramics, plastic ware 1" 3.17 Metal apparatus 16 3.18 Heating apparatus B 3.19 Desiccators and dry boxes 80 3.20 Stirring apparatus 83 3.21 Filtration apparatus 83 3.22 Weighing bottles 86 Reagents and standard solutions 87 3.23 Reagents 87 324 Purification of substances 87 3.25 Standard solutions 89Detailed contents ‘Some basic techniques a 3.26 Preparing substances for analysis, a1 3.27 Weighing the sample 1 3.28 Discolving the sample a 3.29 Decomposing organic compounds 94 3.30. Precipitation 98 3.31 Filtration 96 3.32 Filter papers 96 3.33 Crucibles with permanent porous plates 98 3.34 Washing precipitates 99 3.35. Drying and igniting precipitates 100 3.36 References 102 3.37 Bibliography 103 4 Statistical treatment of analytical data and introduction to chemometrics 104 4.1 Limitations of analytical methods 104 42 Classification of errors 10a 43 Accuracy 105 44 Precision 106 4.5 How to reduce systematic errors 107 4.6 Significant figures 109 4.7 Calculators and computers 110 4.8 Mean and standard deviation 10 4.9 Distribution of random errors 112 4.10 Reliability of results 13 4.11 Confidence interval 14 4.12 Comparison of results 1s 4.13 Comparing the means of two samples 17 414 Hest 18 4.15 The number of replicate determinations 119 4.16 Conrelation and regression 120 4.17 Linear regression 122 4.18 Errors in the slope and the intercept 123 4.20 Standard additions 125 4.21 Nonlinear regression 127 4.22, Comparison of more than two means 127 4.23 Experimental design 130 4.24 Two-way analysis of variance 131 4.25 Chemometries and experimental design 133 4.26 Factorial design 134 4.27 Yates" method 4.28 Interaction effect: alternative calculation 130 4.29 Factorial design: critical appraisal 139 4.30 Optimisation methods 141 4.31 Sequential simplex optimisation 141 4.32. Simplex optimisation: critical appraisal 146 4.33 Treatment of multivariate data 147 ixDetailed contents 4.34 Factor analysis 152 4.35 Quick statisties 153 4.36 The value of chemometries 156 4.37 References 156 4.38 Bibliography 156 5 Sampling 158 5.1 Introduction 158 5.2 Gases and vapours 161 5.3 Liquids 4179 $4 Solids 35 References 197 5.6 Bibliography 197 € Separation techniques 198 6.1 Introduction 198 6.2 Separation techniques 199 63 Solvent extraction at 64 Solid phase exiraction 212 6.5. Crystallisation and precipitation 212 66 Ton exchange separations 213 6.7 Dialysis and lyophilisation 223 6.8 Instrumental separations based on chromatography 223 6.9 Comparing separation efficiencies 225 6.10 Kinetic factors: rate theory 226 6.11 Separations by electrophoresis, 229 6.12 The theory of electrophoresis, 229 6.13 Instrumentation for CE 230 6.14 Capillaries 231 6.15 The applied field 231 6.16 The detector 231 6.17 __ Applications 232 6.19 Bibliography 233 7 ‘Thin-layer chromatography 234 7.1 Introduction 234 7.2 The technique of TLC 235 7.3, Stationary phases 238 7.4 Mobile phases 238 7.5 Two-dimensional TLC 238 7.6 High-performance thin-layer chromatography (HPTLC) 239 yerimental section 240 1 Separation and recovery of dyes 240 7.8 Separation of carbohydrates 241 7.9 Separation of artificial colourants in confectionery 242 7.10 References 242 7M Bibliography 243Detailed contents 8 Liquid chromatography 244 S&L Intyeductign a 8.2. ‘Types of liquid chromatography 244 8.3 Mobile phase, sample injection, column design 251 &4 Choosing a detector 260) 8.5 Column efficiency 265 8.6 Chiral chromatography 267 8.7 Derivatisation 267 8.8 Quantitative analysis 269 Experimental section 268 8.9 Aspirin, phenacetin and caffeine in a mixture 268 8.10 References 270 8.11 Bibliography 71 9 Gas chromatography 272 intmduction. 2 9.2 Apparatus 272 93 Programmed temperature 284 94 Quantitative analysis 285 9.5 Quantitative procedures 285 9.6 Elemental analysis 286 Experimental section —___ 288 97 Intemal normalisation method for the analysis of solvents 288 38 ¢-as is timethyisilyl derivative 8 99 of alumi as its tris(acetylacetonato) complex 289 9.10 Derivatisation and quantitation of sugar alcohols 290 9.11 References 291 9.12 Bibliography 291 10 Titrimetric analysis 292 ‘Thacrbiidal eeedaartlarae 202 introduction 292 Titrimetric analysis Classification of reactions in titrimetric analysis 294 ‘Standard solutions (294 Preparation of standard solutions 295 Primary and secondary standards 295 isation trations x 10.8 Preparaion of indicator soluions 300 10.9 Mixed indicators 301 10.10 Neutralisation curves 302 10.11 Strong ecid neutralised by strong base 302 10.12 Weak acid neutralised by strong base 305 10.13. Weak base neutralised by strong acid 307Detailed contents 10.14 Weak acid neutralised by weak base 308 10.15 Polyprotic acid neutralised by strong base 309 10.15 Anions of weak acids titrated with strong acids 310 as : 4 10.18 Tivations in non-aqueous solvents 314 10.19 Solvents for non-aqueous titrations 35 10.20 Indicators for non-zqueous titrations 316 Neutralisation: fitmatric determinations a 10.22 _A mixture of carbonate and hydrogencarbonatc 317 > Z 10.25 Organic nitrogen: the Kjeldahl procedure 320 26 Nit 0 10.27 _ Phosphate: precipitation as quinoline molybdophosphate 32 10.28 Relative molecular mass of an organic acid 323 10.29 Hydroxyl groups in carbohydrates 323 10,30 Saponification value of oils and fats 325 10.31 Purity of acetylsalicylic acid (aspirin) 325 10.32 Amines using 2 non-aqueous titration 325 Complexation titrations 326 10.33__Introdwetign 32 034 Titmation. aa (10.35 Types of EDTA titration 327 (0.36 Titration of mixtures 8D ae ane 10.38 Standard EDT solutions 10.39 Some practical considerations 334 Complexation: determining individual cations 335 10.44 Iron(Til): direct titration 338 ee = 10.46 __A selection of metals by EDTA 338 10.47 Calcium in the presence of magnesium using EGTA 339 10.4% ‘Total hardness of water. permanent and temporary 340 10.49 Calcium in the presence of barium using CDTA 34 10.52__ Manganese in the presence of iron: ferromanganese 342 10.53 Nickel in the presence of iron: nickel steel 343 ‘Complexation: determining individual anions: 34g 10.55 Phosphates 344 10.55 Sulphates 343 xi opyrighted materialDetailed contents Precipitation titrations 345 10.57 Precipitation reactions 345 10.58 Determining end points in precipitation reactions 347 10.59 Standardising silver nitrate solution 350 10.60 Chlorides and bromides 352 10.61 —_Iodides 353 10.62 Preparing thiocyanate solutions: Volhard’s method 353 10.63 Silver ina silver alloy 354 10.64 Chlorides by Volhard’s method 354 10.65 Fluoride: Volhard titration of lead chlorofluoride 356 10.66 Potassium 357 Oxidation-reduction titrations 358 10.67 Change of electrode potential 358 10.68 Formal potentials 361 10.69 Detecting the end point in oxidation-reduction titrations 362 ‘Oxidations with potassium permanganate 364 10.70 Discussion 364 10.71 Preparing 0.02 M potassium permanganate 365 10.72 Standardising permanganate solutions 365 10.73 Hydrogen peroxide 366 10.74 — Nitrites 366 10.75 Persulphates 367 Oxidations with potassium dichromate 368 10.77 Preparing 0.02 M potassium dichromate 369 10.78 Iron in an ore 369 10.79 Chromium in a chromiur({Il) salt 369 10.80 Chemical oxygen demand 370 Oxidations with cerium(Iv) sulphate solution 371 10.81 General discussion 371 10.82 Preparing 0.1.4/ cerium({V) sulphate 372 10.83 Standardising cerium(IV) sulphate solutions 372 10.84 Copper 372 10.85 Molybdate 373 lodometric titrations 373 10.86 General discussion 373 10.87 Detecting the end point 375 10.88 Preparing 0.05 M iodine solution a7 10.89 Standardising iodine solutions 377 10.90 Preparing 0.1. sodium taiosulphate 378 10.91 Standardising sodium thiosulphate solutions 379 10.92.__ Copper in crystallised copper sulphate 380 10.93 Chlomres ago 1094 Hydrogen peroxide 381 10.95 Dissolved oxygen 381 10.96 Available chlorine in hypochlorites 382 10.97 — Hexacyanoferrates({Il) 383 xiDetailed contents xiv 98 Vitamin ¢ tables 84 Oxidations with potassium iodate 84 99: — ‘Geer dimen fd 10.100 Preparing 0.025 M potassium iodate 385 10.101 Arsenic or antimony 386 10,102 Hydrazine 386 10.103 Other ions 386 Oxidations with potassium bromate 387 10.104 General discussion 387 10.105 Prepering 0.02 M potassium bromate 389 10.106 Metals: using 8-hydroxyquinoline (oxine) 389 10.107 _Hydroxylamit 390 LOLORPhenof 500 Reduction of higher oxidation states 391 10,109 General discussion 391 10.110 Reduction with amalgamated zine: Jones reductor 391 10.111 The silver reductor 394 10.112 Other methods of reduction 395 10.113 References 396 10.114 _ Bibliography 397 11 Gravimetric analysis 398 11.1 Introduction 398 112 Precipitation methods 399 113 Colloidal precipitates 399 114 Contamination of preci 400 115 Practical aspects of precipitation 401 11.6 Precipitation reagents 403 Detemination of chioride, sulphate and metal ions 405 11.7 Gravimetric experiments 405 11.8 Aluminium as the 8-hydroxyquinolate (oxinate) 406 11.9 Chloride as silver chloride 406 11.10 Lead as chromate 408 HLL Nickel as the dimethylglyoximate 408 11.12 Sulphate as barium sulphate 409 11.14 Volatilization methods 413 ALIS References 1.16 Bibliography 414 12 Thermal analysis. 415 12.1 Introduction 415 122 Thermogravimetry 415 12.3 Instruments for thermogravimetry 418 124 Applications of thermogravimetry 420 Experimental section 423Detailed contents 125 Thermogravimetric experiments 423 126 Differential techniques 425 127 Instruments for DTA and DSC 426 128 Experimental and instrumental factors 228 129 Applications of DTA and DSC 4 Experimental section 430 12.10 DTA studies of hydrated copper sulphate and sodium tungstate 430 12.11 DSC determination of calcium sulphate hydrates in cement 431 12.12 Determining the purity of pharmaceuticals by DSC 432 12.13 References 433 12.14 Bibliography 434 13 _Electroanalytical methods 435 13.4 Introduction 435 Electogravimetric analysis 435 13.2 Electrogravimetry: theory 435 133 Electrogravimetry: apsaratus 436 134 Cell processes 437 13.5 Deposition and separation 440 136 Electrolytic separation of metals 40 13.7 Some metals which can be determined 441 Coulometry 4a 138 General discussion 442 129 Coufometry at controlled potential 449 13.10 Apparatus and general technique a4 Experimental section 446 13.411 Separation of nickel and cobalt 446 13.12 Flowing stream coulometry 447 13.13 Evaluation of direct coulometry 448 Coulometry at constant current 448 13.44 General 448 13.15 Principles 449 13.16 Instrumentation 450 13.17 External generation of titrant 452 13.18 Advantages 453 1419 Applications 453 1320 Neutralization titrations 455 1321 Complexation titrations 456 1322 Precipitation titrations 487 1323 Oxidation-reduction titrations 459 13.24 — Cyclohexene by coulometry 459 1325 &Hydroxyquinotine (oxine) 460, Potentiometry 461 1326 Fundamentals of potentiometry 461 xvDetailed contents Refernce electiodes a 13.27 The hydrogen electrode 462 3.28 The calomel elect 3 13.29 The silver-silver chloride electrode 465 Indicator and ion selective electrodes 465 13.30 General discussion 465 13.31 The glass electrode 466, 332 z ion selective 7. aa e Serine 13.34 Using pl metors and selective ion meters 415 13.35 Determination of pH 477 13.36__Determining fluoride 480 13.37 Potentiometry in an oscillating reaction 482 13.38 Principles of potentiometric titrations 484 13.49 General consideratiems JS 13.40 Location of end points 485 1341 Automatic titavors 486 1342 Advantages of potentiometric titrations 487 43__Neutralisation titrations ____487 13.44 Potentiometric titration of ethanoic (acetic) acid with sodium hydroxide 487 13.45 __ Potentiometric titrations in non-aqueous solvents 88 13.47 Complexation titrations 490 13.48 Precipitation titrations 492 13.49 Mixtures of halides by potentiomeity 492 30 Cheisanion- tevin dieatlan 493 13.51 Manganese by potentiometry 493 13.52 Copper by potentiometry 494 Voltammetry 494 13.53. Fundamentals of voltammetry 494 13.54 Conventional or de. polarography 494 13.55 Theoretical principles 497 13.56 Complex ions 50 13.57 Quantitative techniques 502 13.58 The effect of oxygen 504 13.59 Simple polarography end classical d.c. polarography 505 13.60 The three-electrode polarograph: potentiostatic control 307 13.61 Modified voltammetry 510 13.62 Quaniitative applications of polarosra SISDetailed contents Polarography experiments 519 13.63 Polarography experiments: introduction s19 13.64 — Half-wave potential of the cadmium ion in 1M KCI 520 13.65 Investigating the influence of dissolved oxygen 52 13.66 Copper and zinc in tap water using DPP 522 13.67 Copper and zinc in tap water using square wave polarography 524 13.68 Ascorbic acid (vitamin C) in fruit juice 524 13.69 Indirect determination of nitrate via o-nitrophenol 525 Amperometric titrations 526 13.70 Principles 526 13.71 Amperometric titration with a dropping mereury electrode (DME) 528 13.72 Apparatus 530 13.73 Biamperometric titrations 331 13.74 Advantages 332 13.75 Applications 532 13.26 EDTA titrations 1327 Zine 8 3.28 Bismuth 533 13.79 Lead by amperometry using potassium dichromate 534 13.80 Sulphate by amperometry using lead nitrate 534 13.81 Iodide by amperometry using mercury({l) nitrate 535 13.82 Thiosulphate by amperometry with iodine 536 13.83 Antimony by amperometry with potassium bromate 536 13.84 —Thiosalphate with iodine: dead-stop end point 337 13.85 Glucose by amperometry with an enzyme electrode 5337 13.86 The Clark cell for oxygen determinations 38 13.87 Water by ampsrometry using the Karl Fischer reagent 538 Stripping analysis 540 13.88 Stripping voltammetry: basic principles 540 13.89 Electrodes used for stripping analysis, 343 13.90 Apparatus for stripping analysis 343 13.91 Determination of lead in tap water 545 13.92 References 546 13.93 Bibliography 547 14 Nuclear magnetic resonance spectroscopy 549 14.1 Introduction 549 142 Theory 549 144 Coupling of magnetic nuclei 553 145 Instrumentation 554 14.6 Sample preparation SST Experimental determinations 558 147 Ethanol content of an alcoholic liquor S58 14.8 Ethanol content of a beer by standard addition, 559 149 Aspirin, phenacetin and caffeine in an analgesic tablet 560 14.10 Keto-enol tautomerism in pentan-2,4-dione (avetylacetone) 561Detailed contents xviii 14.11 References 561 14.12 Bibliography 561 45____Atomic absorption spoctroscopy 562 15.1 Introduction to etomic spectroscopy 562 15.2 Elementary theory 563 15,3. Instrumentation 366 154 Flames 5617 15.5 The nebuliser-burner system 567 15.6 Graphite fumace technique 569 15.7 Cold vapour technique and hydride generation S71 15.8 Resonance line sources 573 15.9 Monochromators 374 15.10 Detectors 374 15.11 Interferences 575 15.12 Chemical interferences 576 15.13 Background correction methods 578 15.14 Atomic absorption spectrophotometers 581 Experimental preliminaries 582 15.15 Calibration curve procedure 582 15.16 Preparation of sample solutions 583 15.17 Preparation of standard solutions 584 15.18 Safety practices 585 15.19 Detection limits 586 Selected determinations by atomic absorption spectroscopy 589 15.20 Magnesium and calcium in tap water 589 15.21 Vanadium in lubricsting oil 591 15.22 Trace elements in contaminated soil 591 15.23 Tin in canned fruit juice 593 15.24 References 594 15.25 Bibliography 594 16 Atomic emission spectroscopy 595 16.1 Introduetion 595 16.2 Emission spectra 595 16.3 Flame emission spectroscopy (FES) 397 16.4 Evaluation methods 809 16.5 Evaluating flame emission spectroscopy 599 16.6 Plasma emission spectroscopy 399 16.7 Direct current plasma (DCP) 600 16.8 Inductively coupled plasma (ICP) 600 16.9 Sample introduction 601 16.10 ICP instrumentation 602 16.11 Evaluating ICP AES 605 16.12 Determining alkali metals by flame photometry 605 16.13 References 606 16.14 Bibliography 606Detailed contents 17 171 172 173 174 173 176 177 178 179 17.10 17. 17.12 17.13 17.14 1715 17.16 17.17 17.18 17.19 17.20 1721 17.22 17.23, 1724 17.25 17.26 17.27 17.28 17.29 1730 1731 1732 1733 1734 1735 1736 1737 1738 Molecular electronic spectroscopy General discussion The origins of absorption spectra Theory of spectrophotometry and colorimeiry Methods of *colour’ measurement Photodetectors Wavelength selection Radiation sources Standard cells Data presentation Instrumental layout Derivative spectrophotometry Colormetry General remarks Choice of solvent Colorimetric determinations: general procedure Enzymatic analysis Spectrophotometric titrations General Apparatus Technique Advantages Applications Organic compounds by spectrophotometric titrations Inorganic ions by spectrophotometric titrations Copper(tt) Tron(II1) Fluorimetry (theory) Instruments for fluorimetry Some applications of fluorimeiry Flow injection anelysis Experimental section Cations Ammonia Arsenic Boron Chromium Titanium Tungsten Anions Chloride Phosphate Sulphate Organic compounds Primary amines Anionic detergents 608 608 610 él 615 616 618 623 623 623 624 626 628 628 630 61 633 634 635 635 636 636 636 636 636 637 638 61 642 63 646 646 647 ay 651 652 653 654 654 655 656 657 657 658 xixDetailed contents UVAisible spectrophotometry 659 17.39 Absorption curve and concentration of potassium nitrate 659 17.40 How substituents affect the absorption spectrum of benzoic acid 661 17.41 Simuttaneous determinations (chromium and manganese) 662 17.42 Aromatic hydrocarbons and binary mixtures 665 17.43 Phenols in water, 666 17.44 Active constituents in a medicine by derivative spectroscopy 667 1745 Glycerol in fruit juice 668 17.46 Cholesterol in mayonnaise 670 Flucrimetry 671 17.47 Quinine in tonic water 671 1748 Codeine and morphine in a mixture 6n2 17.49 References 673 17.50 Bibliography 614 18 Vibrational spectroscopy 675 18.1 Infrared spectroscopy 675 18.2 Infrared instruments 679 183 Dedicated process analysers 682 184 Infrared cells for liquid samples 684 18.5 Measuring cell path length 685 18.6 Measuring IR absorption bands 685 18.7 Beer's law: quantitative IR spectra 687 18.8 Measurements using compressed discs 689 189 Reflectance methods 690 18.10 GC-FTIR systems 691 18.11 Near-infrared spectroscopy 692 18.12 Raman spectroscopy 693 18.13 The Raman effect 694 18.14 Conelation between IR and Raman 695 18.15 Raman instruments 696 Experimental determinations 098 18.16 Purity of commercial benzoic acid by compressed dises 698 18.17 A calibration curve for cyclohexane 699 18.18 2-, 3-, 4-Methylphenols (cresols) in a mixture 699 18.19 Propanone (acetone) in propan-2-ol 699 18.20 References 700 18.21 Bibliography 700 19 Mass spectrometry 701 19.1 Introduction 701 19.2 Vacuum systems 703 19.3 Sample inlet systems 705 194 The ion source 706 19.5 Mass analysers n4 19.6 Detectors ni 19.7 Data handling mm 19.8 Inorganic mass spectrometry 23Detailed contents 19.9 Isotope ratio measurements ns 19.10 Interpretation of spectra 728 19,11 Hyphenated systems: 737 19.12 Future developments 745 19.13 References 745 19.14__ Bibliography 746 Appendices 747 Appendix | Relative atomic masses 1994 749 Appendix 2 Aqueous concentrations: common acids and ammonia 750 ‘Appendix 3. Saturated solutions of some reagents at 20°C 750 ‘Appendix 4 Sources of analysed samples. 751 Appendix 5 Buffer solutions and secondary pH standards 751 Appendix 6a Dissociation constants of some acids in water at 25°C 753 Appendix 6b Acidic dissociation constants of bases in water at 25°C 754 ‘Appendix 7 — Polarographic half-wave potentials 158 Appendix 8 Resonance lines for atomic absorption 758 ‘Appendix 9 Common chromophores: electronic absorption characteristics 759 ‘Appendix 10 Characteristic infrared absorption bands 760 Appendix 11 Percentage points of the ¢-distrbution 761 Appendix 12. F-distribution 762 Appendix 13 Critical values of @ (P= 0.05) 163 Appendix 14 Critical values of the correlation coefficient p (P = 0.05) 163 “Appendix 15 Wilcoxon signed rank test: critical values (P = 0.05) 763 Appendix 16 Critical values for 7, (P = 0.05) 164 Appendix 17 Critical F, values for one- and two-tailed tests (P = 0.05) 164 Appendix 18 Equivalents and normalities 764 Index TOaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Preface to the sixth edition in this edition and that it will continue to serve as a valuable source for teaching and the practical application of analytical chemistry for many years to come. J. Mendham, R. C. Denney, J. D. Barnes, M. Thomas September 1998 This book has been modified to ensure that its contents are in keeping with the general evolution of the topics, as followed in the course plans of instructors handling the subject in India, Discussions on quantitative chemical analysis presented in the book have been reviewed and adapted to cater to the needs of undergraduate and postgraduate students. New material has been added, and the arrangement of text have been changed at some places to ensure that the book conforms to most of the syllabi covered by Indian universities. B. Sivasankaraa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Units and reagent purity Units SI units have been used throughout this book, but as the litre (L) has been accepted as a special name for the cubic decimetre (dm'), although this is not strictly speaking an SI term, we have considered it appropriate to use the litre throughout this book. Similarly we have chosen to use millilitres (mL) instead of cubic centimetres (em’). In accordance with established practice, the following prefixes are used for decimal multiples of units. Mass is the only exception: the prefixes are used with the gram (g) but the kilogram (kg) is the base unit. Mutnpie Pretix symbol ‘Mutipie Prefix Symbol 10° ¢ 10 deca de 10? © 10° ecto h 10° m 10° kilo k 10° u 10° mega M 10° n 10° sige S 10" P 10" tera T 10" 1 10° peta Pp 10% a 10" xa E Concentrations of solutions are usually expressed as moles per litre; a molar solution (M) ‘has one mole of solute per litre. In some instances the terms parts per million (ppm) and parts per billion (ppb) are still used for indicating trace levels of analytes. This is a dimensionless unit that can be subject to misinterpretation, and where it is employed it is essential that itis established if the levels indicate a weight/volume relationship, a volumne/ volume relationship or some other basis. Other units used in special cases are explained in the text, Reagent purity Unless otherwise stated, ell reagents employed in the analytical procedures should be of appropriate analytical grade or spectroscopic grade. Similarly, where solutions are prepared in water this automatically means distilled or deionised water, from which all but very ‘minor impurities will have been removed. xxiK,aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Textbook of Quantitative Chemical Analysis 15 arisc, and find ways to circumyent any problems, Analysts will also be concerned with accuracy and precision, time and costing. The most accurate method for a certain deter- mination may prove to be lengthy or it may require expensive reagents, and in the interests of economy it may be necessary to choose a method which, although somewhat less exact, yields results of sufficient accuracy in a reasonable time. Important factors which must be taken into account when selecting an appropriate method of analysis include (a) the nature of the information which is sought, (b) the size of sample available and the proportion of the constituent to be determined, and (c) the purpose for which the analytical data is required. ‘The information sought may require very detailed data, or perhaps more general results. Chemical analyses may be classified into four types according to the data they generate: Proximate analysis determines the amount of each element in a sample but not the com- pounds that are present. Partial analysis determines selected constituents in the sample. ‘Trace constituent analysis is a type of partial analysis that determines specified compon- cents present in very minute quantity. Complete analysis determines the proportion of each component in the sample. On the basis of sample size, analytical methods are often classified as follows: Macro for quantities of 0.1 g or more Meso (semimicro) for quantities ranging fiom 107g to 10"g Micro for quantities in the range 10”'g to 10g Submicro for samples in the range 10g to 10° g Ultramicro for quantities below 10“ g Trace for 10° to 10' ugg"! (10010000 parts per million)* Microtrace for 10 ' to 10° pgg' (10 to 10 *ppm) Nanotrace for 10" to 10° fgg’ (10 to 10” ppm) The term *semimicro’ given as an alternative name for ‘meso’ is not very apt, referring as it does to samples larger than micro. ‘A major constituent accounts for 1% to 100% of the sample under investigation; a minor constituent is present in the range 0.01% to 1%; a trace constituent is present at a concentration of less than 0.01%. When the sample weight is small (0.t~1.0mg), the determination of a trace component at the 0.01% level may be called subtrace analysis. If the trace component is at the micro- trace level, the analysis is called submicrotrace. With a still smaller sample (not larger than 0.1 mg) the determination of a component at the trace level is called ultratrace analysis, and with a component at the microtrace level, the analysis is called ultramicrotrace. Searching the literature The analytical chemist will often have to design a completely novel analysis and will have to seck information from previously published data, This may involve consulting multi- volume reference works such as Kolthoff and Elving, Treatise on analytical chemistry, Wilson and Wilson, Comprehensive analytical chemistry, Fresenius and Jander, Handbuch * Concentrations are commonly quoted in parts pet million (ppm, but this should be avoided as ppm is a dimensionless quantity.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Textbook of Quantitative Chemical Analysis 28 Very small concentrations of hydrogen ions and hydroxide ions, originating from the small but finite ionisation of water, will initially be present. HA is a weak acid, i.e. itis dissoci- ated only to 2 small degree; the concentration of A” ions which can exist in equilibrium with H” ions is therefore small. In order to maintain the equilibrium, the large initial concentration of A ions must be reduced by combination with H” ions to form undissoci ated HA: H'+A =HA 27 The hydrogen ions required for this reaction can be obtained only from the further disso- ciation of the water; this dissociation simultaneously produces an equivalent quantity of hydroxyl ions. The hydrogen ions are used in the formation of HA; consequently, the hydroxide ion concentration of the solution will increase and the solution will react alkaline. It is usual in writing equations involving equilibria between completely dissociated and slightly dissociated or sparingly soluble substances to employ the ions of the completely dissociated substance and the molecules of the slightly dissociated substance. The reaction. is therefore written A +H0 = OH +HA [28] This equation can also be obtained by combining reactions [2.5] and [2.7] since both equilibria must coexist. This interaction between the ion (or ions) of a salt and water is called hydrolysis Consider now the salt of a strong acid and a weak base (class 3). Here the initial high concentration of cations M’ will be reduced by combination with the hydroxide ions of ‘water to form the slightly dissociated base MOH until the equilibrium M’ +OH = MOH is attained. The hydrogen ion concentration of the solution will thus be increased, and the solution will react acid. The hydrolysis is here represented by M+ = MOH +H" For salts of class 4, in which both the acid and the base are weak, two reactions will occur simultaneously M'+H,O=MOH+H’ A +H,O = HA +0" The reaction of the solution will clearly depend upon the relative dissociation constants of the acid and the base. If they are equal in strength the solution will be neutral; if K, > Ky it will be acid; and if K, > K, it will be alkaline. Having considered all the possible cases, we are now in a position to give a more general definition of ydrolysis. Hydrolysis is the interaction between an ion (or ions) of a salt and water with the production of (a) a weak acid or a weak bese, or (b) a week acid and a weak base. The phenomenon of salt hydrolysis may be regarded as a simple application of the general Bronsted-Lowry equation Ay + By A+B, ‘Thus the equation for the hydrolysis of mmonium salts NH; +H,0 = NH, + H,0°aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Solution Reactions: Fundamental Theory 213 ic. the solution is approximately neutral, On the other hand, fora dilute solution of ammonium methanoste pH = 7.0 + 1.88 - 2.37 =6.51 since K, = 1.77 x 10“ molL"' (pX, = 3.75) for methanoic acid, i.e. the solution has a slightly acid reaction. Solubility product For sparingly soluble salts (i,¢. those for which the solubility is less than 0.01 mol L”') it is an experimental fact that the mass action product of the concentrations of the ions is a constant at constant temperature. This product K, is called the solubility product. For a binary electrolyte ABS A+B Kyaw = (AYB] And for an electrolyte A,B,, which ionises into pA” and gB” ions, then A,B, = PAT + qBP Kaan TVR Here is a plausible deduction of the solubility product relation, When excess of a sparingly soluble electroly'e, say silver chloride, is shaken up with water some of it passes into solu- tion to form a saturated solution of the salt and the process appears to cease. The following equilibrium is actually present (the silver chloride is completely ionised in solution): AgCl (s) = Ag’ + Cr The rate of the forward reaction depends only upon the temperature, and at any given temperature nak where k, is a constant. The rate of the reverse reaction is proportional to the activity of each of the reactants; hence at any given temperature 1 = kadyyithes where &, is another constant, At equilibrium the two rates are equal, Ky = hadypagy OF agra = kyla = Kargcn, In the very dilute solutions with which we are concemed, the activities may be taken as practically equal to the concentrations, so [Ag’ [CI] = a constant. Note that the solubility product relation applies with sufficient accuracy for purposes of quantitative analysis only ta saturated solutions of slightly soluble electrolytes and with small additions of other salts, In the presence of moderate concentrations of salts, the ionic concentration, and therefore the ionic strength of the solution, will increase. In general, this will lower the activity coefficients of both ions, hence the ionic concentrations (and there- fore the solubility) must inctease in order to maintain the solubility product constant. This effect is called the salt effect; it is most marked when the added electrolyte does not possess an ion in common with the sparingly soluble salt. 33aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Textbook of Quantitative Chemical Analysis 36 The value 0.25 M has been chosen since it is the concentration at which the sulphides of certain heavy metels are precipitated. The total concentration of hydrogen sulphide may be assumed to be approximately the same as in aqueous solution, i.e. 0.1 M; [H"] will equal the concentration of the completely dissociated HCl, ie. 0.25 M, but [S”] will be reduced below 1 x 10° (see Example 2.1). Using the equilibria [2.4] and [2.5], we find K\[H,S] _ 1.0% 107 x01 ihe 025 =4.0x 10*molL! {s? a -Ux Jor yan 10") = 1.65 102! mol L"! Thus, by changing the acidity from 1.0 10M (present in saturated H,S water) to 0.25 M, the sulphide ion concentration is reduced from 1 x 10 to 1.6 x 107 mol L™ Example 2.9 What effect has the addition of 0.1 mol of anhydrous sodium ethanoate to 1 L of 0.1 Af etbanoic acid upon the degree of dissociation of the acid’ The dissociation constant of ethanoic acid at 25°C is 1.75 x 10 mol L” and the degree of ionisation a. in 0.1 Mf solution may be computed by solving the quadratic equation [H'J[CH,COO)}] __ ae _ s TCH;COOH] ~ (i = a) 71-7510 For our purpose it is sufficiently accurate to neglect a in (1 - a) since otis small, so a= fKle = [UT5x10" = 00132 Hence in 0.1 M ethanoic acid, [H'} = 0.001 32, (CH,COO’] = 0.001 32, and [CH,COOH] = 0.0987 mol L The concentrations of sodium and ethanoate ions produced by the addition of the com- pletely dissociated sodium ethanoate are [Na] =0.1 [CH,COO] = 6.1 mol L* ‘The ethanoate ions from the salt will tend to decrease the ionisation of the ethanoic acid, and consequently the ethanoate ion concentration derived from it. Hence we may write [CH,COO ] = 0.1 for the solution; and if a’ is the new degree of ionisation then [H"] = fe = 0.1o¢ and {CH,COOH] = (1 - @’Je = 0.1, since or” is negligibly small Substituting in the mass action equation: H°|[CH,COO™ [CH;COOH] ~~ 0.1 or a’ = 1.75 x10" [HJ = o’e = 1.75 x 10% mol L* The addition of a 0.1 mol of sodium ethanoate to a 0.1 M solution of ethanoic acid has decreased the degree of ionisation from 1.32% to 0.018%, and the hydrogen ion concen- tration trom 0,001 32 to 0.000018mol L '. 20:1 = 1.75 x 10°aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Textbook of Quantitative Chemical Analysis 40 247 2.18 Pre te solubility: effect of acids For sparingly soluble salts of a strong acid, the effect of the addition of an acid will be similar to that of any other indifferent electrolyte; but if the sparingly soluble salt MA is the salt of a weak acid HA, then acids will generally have a solvent effect upon it, If hydrochloric acid is added to an aqueous suspension of such a salt, the following equi- librium will be established: M’+A +H’ = HA + M* If the dissociation constant of the acid HA is very small, the anion A’ will be removed from the solution to form the undissociated acid HA. Consequently, more of the salt will pass into solution to replace the anions removed in this way, and this process will continue until equilibrium is established (i.e. until [M"][A] has become equal to the solubility product of MA), or if sufficient hydrochloric acid is present, until the sparingly soluble salt has dis- solved completely. Similar reasoning may be applied to salts of acids, such as phosphoric(V) acid (K, = 7.5 x 10° molL |, Ky = 6.2 x 10*mol L', K; = 5 x 10° mol L'), oxalic acid (K, = 5.9 10 * molL '; K, = 6.4 x 10 ‘moi L ') and arsenic(V) acid. Thus the solubility of, say, silver phosphate(V) in dilute nitric acid is due to the removal of the PO} ion as HPO; and/or H,PO; POY +H’ = HPO: ; HPOF +H With the salts of certain weak acids, such as carbonic, sulphurous and nitrous acids, an additional factor contributing to the increased solubility is the actual disappearance of the acid from solution, either spontaneously or on gentle warming. An explanation is thus pro- vided for the well-known solubility of the sparingly soluble sulphites, carbonates, oxalates, phosphates(V), arsenites(III), arsenates(V), cyanides (with the exception of silver cyanide, which is actually a salt of the strong acid H[Ag(CN)s}), fluorides, ethanoates and salts of other organic acids in strong acids. The sparingly soluble sulphates (e.g. those of barium, strontium, and lead) also exhibit increased solubility in acids as a consequence of the weakness of the second-stage ionisa- tion of sulphuric acid (K, = 1.2 x 10* mol L'): HPO; SO} +H' == HSO, But since K; is comparatively large, the solvent effect is relatively small; this is why in the quantitative separation of barium sulphate, precipitation may be carried out in slightly acid solution in order to obtain a more easily filterable precipitate and to reduce coprecipitation Precipitate solubility: effect of temperature The solubility of the precipitates encountered in quantitative analysis increases with increasing temperature. With some substances the influence of temperature is smell, but with others itis quite appreciable. Thus the solubilities of silver chloride at 10 and 100°C are respectively 1,72 and 21.1 mg L, whereas the solubilities of barium sulphate at these two temperatures are respectively 2.2 and 3.9mgL”. In many instances the common ion effect reduces the solubility to a value so small that the temperature effect, which is other- wise appreciable, becomes very small. Wherever possible it is advantageous to filter while the solution is hot; the rate of filtration is increased, as is the solubility of foreign sub- stances, thus rendering their removal from the precipitate more complete, The double phos- phates of ammonium with magnesium, manganese or zinc, as well as lead sulphate and silver chloride, are usually filtered at the laboratory temperature to avoid solubility losses.