EXPERIMENTAL CHEMISTRY

By C. CANII

CHAPTER 1 BASIC NOTIONS OF STATISTICS 1 11 Introduction 1 12 Distributions of Random Variables 1 121 Characterization of Distributions 1 13 Measures of Location 3 14 Measures of Dispersion 6 15 Measures of Asymmetry 8 16 Measures of Concentration 9 17 Statistical Hypothesis Testing 10 18 Statistical Tests 12 181 Confidence Interval Method 12 182 Critical Range Method 14 183 Dixon’s Q Test 15 184 Chi Square (?2) Test 16 185 Snedecor’s F Test 17 186 Hartley’s Fmax Test 18 187 Bartlett’s Test 18 188 Morgan’s Test 19 189 Student’s t Test 20 1810 Cochran-Cox C Test 22 1811 Aspin-Welch Test 23 1812 Cochran’s Test 24 1813 Grubbs’ Test 24 1814 Hampel’s Test 26 1815 Z-Score 27 1816 En-Score 27 1817 Mandel’s Test 28 1818 Kolmogorov-Smirnov Test 29 19 Linear Regression 29 110 Significant Digits Rules of Rounding 31 References 33 chAPter 2 QuALity of AnALyticAL resuLts 35 21 Definitions 35 22 Introduction 35 23 Quality Assurance System 36 24 Conclusions 42 References 42 chAPter 3 internAL QuALity controL 43 31 Definitions 43 32 Introduction 43 33 Quality Control in the Laboratory 44 34 Control Charts 46 341 Shewhart Charts 46 342 Shewhart Chart Preparation 46 343 Shewhart Chart Analysis 48 344 Types of Control Charts 55 345 Control Samples 63 35 Conclusion 65 References 66 chAPter 4 trAceAbiLity 67 41 Definitions 67 42 Introduction 68 43 The Role of Traceability in Quality Assurance/ Quality Control System 70 44 Conclusion 75 References 75 chAPter 5 uncertAinty 77 51 Definitions 77 52 Introduction 78 53 Methods of Estimating of Measurement Uncertainty 79 531 Procedure for Estimating the Measurement Uncertainty According to Guide to the Expression of Uncertainty in Measurement 80 54 Tools Used for Uncertainty Estimation 89 55 Uncertainty and Confidence Interval 89 56 Calibration Uncertainty 91 57 Conclusion 96 References 97 chAPter 6 reference MAteriALs 99 61 Definitions 99 62 Introduction 99 63 Parameters That Characterize RMs 104 631 General Information 104 632 Representativeness 104 633 Homogeneity 105 634 Stability 105 635 Certified Value 107 64 Production of CRMs – Requirements (ISO 17034) 108 65 Practical Application of CRMs 110 66 Conclusion 127 References 128 chAPter 7 interLAborAtory coMPArisons 130 71 Definitions 130 72 Introduction 130 73 Classification of Interlaboratory Studies 132 74 Characteristics and Organization of Interlaboratory Comparisons 136 75 The Presentation of Interlaboratory Comparison Results Statistical Analysis in Interlaboratory Comparisons 136 751 Comparisons of Results Obtained Using Various Procedures 154 752 Comparison of the Measurement Results Obtained in a Two-Level Study (for Two Samples with Various Analyte Concentrations) 158 76 Organization of Proficiency Testing – Requirements (ISO 17043) 165 77 Conclusions 167 References 168 chAPter 8 cALibrAtion 169 81 Introduction 169 82 Types of Calibration 170 83 Calibration Techniques 171 831 Single Standard Technique 171 832 Bracketing Solutions Technique 173 833 Calibration Curve Technique 175 834 Standard Addition Technique 179 835 Multiple Standard Addition Technique 182 836 Internal Standard Technique 184 84 Conclusions 189 References 189 chAPter 9 Method vALidAtion 190 91 Introduction 190 92 Characterization of Validation Parameters 194 921 Selectivity 194 922 Linearity 196 923 Limit of Detection and Limit of Quantitation 204 924 Range 223 925 Sensitivity 226 926 Precision 227 927 Accuracy and Trueness 237 928 Robustness and Ruggedness 260 929 Uncertainty 261 93 Conclusions 269 Bibliography 280 References 282 chAPter 10 Method eQuivALence 285 101 Introduction 285 102 Ways of Equivalence Demonstration 285 1021 Difference Testing 286 1022 Equivalence Testing 292 1023 Regression Analysis Testing 295 103 Conclusions 298 References 298