List of Experiments |
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xvii | |
Preface |
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xix | |
Acknowledgments |
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xxi | |
Author |
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xxiii | |
Introduction to Laboratory Work |
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xxv | |
Chapter 1 Introduction to Analytical Science |
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1 | (18) |
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1.1 Analytical Science Defined |
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1 | (1) |
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1.2 Classifications of Analysis |
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2 | (1) |
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3 | (1) |
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1.4 The Analytical Process |
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3 | (1) |
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1.5 Analytical Technique and Skills |
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4 | (1) |
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1.6 Elementary Statistics |
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5 | (8) |
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5 | (1) |
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6 | (2) |
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1.6.3 Distribution of Measurements |
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8 | (2) |
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10 | (2) |
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12 | (1) |
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1.6.6 Final Comments on Statistics |
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13 | (1) |
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1.7 Precision, Accuracy, and Calibration |
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13 | (6) |
Chapter 2 Sampling and Sample Preparation |
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19 | (30) |
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19 | (1) |
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19 | (1) |
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2.3 Statistics of Sampling |
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20 | (1) |
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21 | (2) |
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21 | (1) |
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2.4.2 Maintaining Sample Integrity |
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22 | (1) |
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2.5 Sample Preparation-Solid Materials |
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23 | (2) |
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2.5.1 Particle Size Reduction |
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23 | (1) |
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2.5.2 Sample Homogenization and Division |
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23 | (1) |
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2.5.3 Solid-Liquid Extraction |
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24 | (1) |
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2.5.4 Other Extractions from Solids |
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24 | (1) |
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2.6 Water Purification and Use |
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25 | (1) |
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2.6.1 Purifying Water by Distillation |
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25 | (1) |
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2.6.2 Purifying Water by Deionization |
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26 | (1) |
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2.7 Total Sample Dissolution and Other Considerations |
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26 | (4) |
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27 | (1) |
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27 | (1) |
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28 | (1) |
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28 | (1) |
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28 | (1) |
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28 | (1) |
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28 | (1) |
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29 | (1) |
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30 | (1) |
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2.9 Sample Preparation: Liquid Samples, Extracts, and Solutions of Solids |
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30 | (2) |
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2.9.1 Extraction from Liquid Solutions |
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30 | (2) |
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2.9.2 Dilution, Concentration, and Solvent Exchange |
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32 | (1) |
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32 | (1) |
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2.10 Liquid-Liquid Extraction |
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32 | (6) |
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32 | (1) |
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2.10.2 The Separatory Funnel |
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33 | (1) |
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34 | (1) |
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2.10.4 Calculations Involving Equation 2.2 |
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35 | (1) |
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2.10.5 Calculations Involving Equation 2.3 |
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36 | (1) |
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2.10.6 Calculations Involving a Combination of Equations 2.3 (or 2.7) and 2.4 |
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37 | (1) |
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2.10.7 Calculation of Percent Extracted (Equation 2.5) |
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37 | (1) |
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38 | (1) |
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2.11 Solid-Liquid Extraction |
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38 | (1) |
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2.12 Distillation of a Mixture of Liquids |
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39 | (2) |
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2.13 Reagents Used in Sample Preparation |
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41 | (1) |
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2.14 Labeling and Record Keeping |
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41 | (8) |
Chapter 3 Gravimetric Analysis |
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49 | (24) |
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49 | (1) |
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49 | (1) |
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49 | (2) |
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51 | (1) |
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3.5 Calibration and Care of Balances |
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52 | (1) |
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3.6 When to Use Which Balance |
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52 | (1) |
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3.7 Details of Gravimetric Methods |
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53 | (10) |
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3.7.1 Physical Separation Methods and Calculations |
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53 | (5) |
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55 | (1) |
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55 | (1) |
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3.7.1.3 Residue on Ignition |
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56 | (1) |
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3.7.1.4 Insoluble Matter in Reagents |
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56 | (1) |
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3.7.1.5 Solids in Water and Wastewater |
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56 | (1) |
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3.7.1.6 Particle Size by Analytical Sieving |
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57 | (1) |
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3.7.2 Chemical Alteration/Separation of the Analyte |
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58 | (1) |
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3.7.3 Gravimetric Factors |
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59 | (2) |
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3.7.4 Using Gravimetric Factors |
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61 | (2) |
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3.8 Experimental Considerations |
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63 | (10) |
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63 | (1) |
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3.8.2 Weighing by Difference |
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63 | (1) |
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3.8.3 Isolating and Weighing Precipitates |
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64 | (9) |
Chapter 4 Introduction to Titrimetric Analysis |
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73 | (40) |
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73 | (1) |
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73 | (2) |
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4.3 Review of Solution Concentration |
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75 | (4) |
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75 | (2) |
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77 | (2) |
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4.4 Review of Solution Preparation |
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79 | (3) |
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4.4.1 Solid Solute and Molarity |
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80 | (1) |
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4.4.2 Solid Solute and Normality |
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81 | (1) |
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4.4.3 Solution Preparation by Dilution |
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82 | (1) |
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4.5 Stoichiometry of Titration Reactions |
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82 | (2) |
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84 | (4) |
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4.6.1 Standardization Using a Standard Solution |
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84 | (2) |
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4.6.2 Standardization Using a Primary Standard |
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86 | (2) |
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88 | (1) |
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4.7 Percentage Analyte Calculations |
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88 | (3) |
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91 | (9) |
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91 | (3) |
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94 | (4) |
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98 | (2) |
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4.8.4 Cleaning and Storing Procedures |
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100 | (1) |
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4.9 Pipetters, Automatic Titrators, and Other Devices |
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100 | (3) |
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100 | (2) |
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4.9.2 Bottle-Top Dispensers |
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102 | (1) |
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4.9.3 Digital Burets and Automatic Titrators |
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102 | (1) |
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4.10 Calibration of Glassware and Devices |
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103 | (1) |
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4.11 Analytical Technique |
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103 | (10) |
Chapter 5 Applications of Titrimetric Analysis |
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113 | (52) |
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113 | (1) |
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5.2 AcidBase Titrations and Titration Curves |
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113 | (10) |
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5.2.1 Titration of Hydrochloric Acid |
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113 | (2) |
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5.2.2 Titration of Weak Monoprotic Acids |
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115 | (1) |
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5.2.3 Titration of Monobasic Strong and Weak Bases |
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116 | (1) |
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5.2.4 Equivalence Point Detection |
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116 | (2) |
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5.2.5 Titration of Polyprotic Acids: Sulfuric Acid and Phosphoric Acid |
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118 | (3) |
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5.2.6 Titration of Potassium Biphthalate |
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121 | (1) |
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5.2.7 Titration of Tris-(Hydroxymethyl)Amino Methane |
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122 | (1) |
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5.2.8 Titration of Sodium Carbonate |
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122 | (1) |
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5.3 Examples of Acid/Base Determinations |
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123 | (4) |
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5.3.1 Alkalinity of Water or Wastewater |
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124 | (1) |
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5.3.2 Back Titration Applications |
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124 | (2) |
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5.3.3 Indirect Titration Applications |
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126 | (1) |
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5.4 Other Acid/Base Applications |
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127 | (1) |
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5.5 Buffer Solution Applications |
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127 | (6) |
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5.5.1 Conjugate Acids and Bases |
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128 | (1) |
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5.5.2 HendersonHasselbalch Equation |
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129 | (4) |
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5.6 Complex Ion Formation Reactions |
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133 | (11) |
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133 | (1) |
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5.6.2 Complex Ion Terminology |
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133 | (2) |
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5.6.3 EDTA and Water Hardness |
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135 | (3) |
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5.6.4 Expressing Concentration Using Parts per Million |
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138 | (3) |
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5.6.4.1 Solution Preparation |
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139 | (2) |
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5.6.5 Water Hardness Calculations |
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141 | (2) |
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5.6.6 Other Uses of EDTA Titrations |
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143 | (1) |
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5.7 OxidationReduction Reactions |
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144 | (8) |
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5.7.1 Review of Basic Concepts and Terminology |
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144 | (3) |
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5.7.2 The Ion-Electron Method for Balancing Equations |
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147 | (1) |
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5.7.3 Analytical Calculations |
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148 | (2) |
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150 | (17) |
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5.7.4.1 Potassium Permanganate |
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150 | (1) |
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5.7.4.2 Iodometry: An Indirect Method |
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150 | (2) |
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5.7.4.3 Prereduction and Preoxidation |
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152 | (1) |
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152 | (13) |
Chapter 6 Introduction to Instrumental Analysis |
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165 | (20) |
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6.1 Review of the Analytical Process |
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165 | (1) |
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6.2 Instrumental Analysis Methods |
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166 | (1) |
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6.3 Basics of Instrumental Measurement |
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167 | (5) |
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6.3.1 Sensors, Signal Processors, Readouts, and Power Supplies |
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168 | (1) |
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6.3.2 Calibration of an Analytical Instrument |
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168 | (2) |
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6.3.3 Mathematics of Linear Relationships |
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170 | (1) |
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6.3.4 Method of Least Squares |
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171 | (1) |
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6.3.5 The Correlation Coefficient |
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172 | (1) |
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6.4 Preparation of Standards |
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172 | (1) |
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173 | (1) |
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173 | (1) |
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174 | (1) |
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174 | (1) |
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6.6 Post-Run Calculations in Instrumental Analysis |
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174 | (4) |
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6.6.1 Calculation of ppm Analyte in a Solution Given Mass and Volume Data |
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175 | (1) |
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6.6.2 Calculation of ppm Analyte in a Solid Sample Given Mass Data |
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175 | (1) |
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6.6.3 Calculation of the Mass of Analyte Found in an Extract |
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175 | (1) |
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6.6.4 Calculation of ppm Analyte in a Liquid or Solid That Was Extracted |
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176 | (1) |
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6.6.5 Calculation When a Dilution Is Involved |
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176 | (2) |
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6.7 Laboratory Data Acquisition and Information Management |
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178 | (7) |
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178 | (1) |
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6.7.2 Laboratory Information Management |
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179 | (6) |
Chapter 7 Introduction to Spectrochemical Methods |
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185 | (30) |
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185 | (1) |
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185 | (4) |
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7.2.1 Wavelength, Speed, Frequency, Energy, and Wavenumber |
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186 | (3) |
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7.3 The Electromagnetic Spectrum |
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189 | (1) |
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190 | (3) |
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7.5 Absorption and Emission of Light |
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193 | (9) |
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193 | (3) |
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7.5.2 Atoms vs. Molecules and Complex Ions |
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196 | (1) |
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197 | (4) |
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201 | (1) |
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7.6 Absorbance, Transmittance, and Beer's Law |
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202 | (5) |
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7.7 Effect of Concentration on Spectra |
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207 | (8) |
Chapter 8 UV-Vis and IR Molecular Spectrometry |
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215 | (44) |
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215 | (1) |
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8.2 UV-Vis Instrumentation |
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215 | (13) |
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215 | (1) |
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8.2.1.1 Tungsten Filament Lamp |
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215 | (1) |
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216 | (1) |
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216 | (1) |
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8.2.2 Wavelength Selection |
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216 | (4) |
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8.2.2.1 Absorption Filters |
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217 | (1) |
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217 | (3) |
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220 | (6) |
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8.2.3.1 Single-Beam Spectrophotometer |
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220 | (1) |
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8.2.3.2 Beam Splitting and Chopping |
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221 | (1) |
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8.2.3.3 Double-Beam Designs |
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222 | (1) |
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8.2.3.4 Diode Array Design |
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223 | (2) |
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225 | (1) |
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226 | (3) |
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8.2.4.1 Photomultiplier Tube |
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226 | (2) |
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228 | (1) |
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8.3 Cuvette Selection and Handling |
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228 | (1) |
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8.4 Interferences, Deviations, Maintenance, and Troubleshooting |
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229 | (2) |
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229 | (1) |
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229 | (1) |
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230 | (1) |
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230 | (1) |
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231 | (2) |
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8.6 Introduction to IR Spectrometry |
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233 | (1) |
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234 | (1) |
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235 | (5) |
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235 | (5) |
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240 | (4) |
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8.9.1 Solution Prepared and Placed in a Liquid Sampling Cell |
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240 | (1) |
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8.9.2 Thin Film Formed by Solvent Evaporation |
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240 | (1) |
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240 | (2) |
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242 | (1) |
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8.9.5 Reflectance Methods |
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242 | (2) |
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8.9.5.1 Specular Reflectance |
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242 | (1) |
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8.9.5.2 Internal Reflectance |
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242 | (2) |
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8.9.5.3 Diffuse Reflectance |
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244 | (1) |
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244 | (1) |
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8.10 Basic IR Spectra Interpretation |
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244 | (3) |
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8.11 Quantitative Analysis |
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247 | (12) |
Chapter 9 Atomic Spectroscopy |
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259 | (32) |
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9.1 Review and Comparisons |
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259 | (1) |
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9.2 Brief Summary of Techniques and Instrument Designs |
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260 | (2) |
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9.3 Flame Atomic Absorption |
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262 | (13) |
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9.3.1 Flames and Flame Processes |
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262 | (1) |
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9.3.2 Spectral Line Sources |
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263 | (2) |
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9.3.2.1 Hollow Cathode Lamp |
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264 | (1) |
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9.3.2.2 Electrodeless Discharge Lamp |
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265 | (1) |
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265 | (2) |
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267 | (1) |
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9.3.5 Practical Matters and Applications |
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268 | (3) |
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9.3.5.1 Slits and Spectral Lines |
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268 | (1) |
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9.3.5.2 Linear and Nonlinear Standard Curves |
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269 | (2) |
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9.3.5.3 Hollow Cathode Lamp Current |
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271 | (1) |
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271 | (1) |
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271 | (1) |
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9.3.5.6 Burner Head Position |
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271 | (1) |
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9.3.5.7 Fuel and Oxidant Sources and Flow Rates |
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271 | (1) |
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271 | (3) |
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9.3.6.1 Chemical Interferences |
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272 | (1) |
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9.3.6.2 Spectral Interferences |
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273 | (1) |
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9.3.7 Safety and Maintenance |
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274 | (1) |
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9.4 Graphite Furnace Atomic Absorption |
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275 | (3) |
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9.4.1 General Description |
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275 | (2) |
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9.4.2 Advantages and Disadvantages |
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277 | (1) |
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9.5 Inductively Coupled Plasma |
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278 | (3) |
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9.6 Miscellaneous Atomic Techniques |
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281 | (1) |
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281 | (1) |
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282 | (1) |
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282 | (1) |
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282 | (1) |
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9.6.5 Atomic Fluorescence |
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282 | (1) |
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9.7 Summary of Atomic Techniques |
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282 | (9) |
Chapter 10 Introduction to Chromatography |
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291 | (20) |
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291 | (1) |
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291 | (1) |
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10.3 "Types" of Chromatography |
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292 | (3) |
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10.3.1 Partition Chromatography |
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292 | (1) |
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10.3.2 Adsorption Chromatography |
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293 | (1) |
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10.3.3 Ion-Exchange Chromatography |
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294 | (1) |
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10.3.4 Size Exclusion Chromatography |
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295 | (1) |
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10.4 Chromatography Configurations |
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295 | (11) |
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10.4.1 Paper and Thin-Layer Chromatography |
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296 | (2) |
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10.4.2 Classical Open-Column Chromatography |
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298 | (3) |
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10.4.3 Instrumental Chromatography |
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301 | (1) |
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10.4.4 Instrumental Chromatogram |
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301 | (4) |
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10.4.5 Quantitative Analysis with GC and HPLC |
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305 | (1) |
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306 | (5) |
Chapter 11 Gas Chromatography |
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311 | (30) |
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311 | (1) |
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11.2 Vapor Pressure and Solubility |
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311 | (1) |
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11.3 Instrument Components |
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312 | (2) |
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314 | (2) |
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316 | (5) |
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11.5.1 Instrument Logistics |
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316 | (1) |
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11.5.2 Packed, Open Tubular, and Preparative Columns |
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317 | (1) |
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11.5.3 The Nature and Selection of the Stationary Phase |
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318 | (1) |
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11.5.4 Column Temperature |
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319 | (1) |
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11.5.5 Carrier Gas Flow Rate |
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320 | (1) |
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321 | (4) |
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11.6.1 Flame Ionization Detector (FID) |
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321 | (1) |
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11.6.2 Thermal Conductivity Detector (TCD) |
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322 | (1) |
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11.6.3 Electron Capture Detector (ECD) |
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323 | (1) |
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11.6.4 Nitrogen/Phosphorus Detector (NPD) |
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324 | (1) |
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11.6.5 Flame Photometric Detector (FPD) |
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324 | (1) |
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11.6.6 Electrolytic Conductivity (Hall Detector) |
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324 | (1) |
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11.6.7 Gas ChromatographyMass Spectrometry (GC-MS) |
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324 | (1) |
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11.6.8 Photoionization Detector (PID) |
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325 | (1) |
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11.7 Qualitative Analysis |
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325 | (1) |
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11.8 Quantitative Analysis |
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326 | (3) |
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11.8.1 Quantitation Methods |
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326 | (1) |
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11.8.2 Response Factor Method |
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326 | (1) |
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11.8.3 Internal Standard Method |
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327 | (1) |
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11.8.4 Standard Additions Method |
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328 | (1) |
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329 | (12) |
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11.9.1 Diminished Peak Size |
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329 | (1) |
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11.9.2 Unsymmetrical Peak Shapes |
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329 | (1) |
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11.9.3 Altered Retention Times |
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330 | (1) |
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330 | (1) |
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11.9.5 Baseline Perturbations |
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330 | (1) |
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11.9.6 Appearance of Unexpected Peaks |
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330 | (11) |
Chapter 12 High-Performance Liquid Chromatography and Electrophoresis |
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341 | (30) |
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341 | (1) |
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341 | (1) |
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12.1.2 Comparisons with GC |
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341 | (1) |
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12.2 Mobile Phase Considerations |
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342 | (2) |
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344 | (2) |
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344 | (1) |
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12.3.2 Gradient vs. Isocratic Elution |
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345 | (1) |
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346 | (2) |
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348 | (2) |
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12.5.1 Normal Phase Columns |
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348 | (1) |
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12.5.2 Reverse-Phase Columns |
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348 | (1) |
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12.5.3 Adsorption Columns |
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349 | (1) |
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12.5.4 Ion Exchange and Size Exclusion Columns |
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349 | (1) |
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12.5.5 The Size of the Stationary Phase Particles |
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349 | (1) |
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349 | (1) |
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350 | (5) |
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350 | (1) |
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351 | (1) |
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351 | (2) |
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353 | (1) |
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354 | (2) |
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|
354 | (1) |
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|
354 | (1) |
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12.7 Qualitative and Quantitative Analysis |
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|
355 | (1) |
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|
356 | (1) |
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12.8.1 Unusually High Pressure |
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|
356 | (1) |
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12.8.2 Unusually Low Pressure |
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|
356 | (1) |
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|
356 | (1) |
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|
357 | (1) |
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12.8.2.3 Column "Channeling" |
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|
357 | (1) |
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12.8.2.4 Decreased Retention Time |
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|
357 | (1) |
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|
357 | (1) |
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|
357 | (14) |
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|
357 | (2) |
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12.9.2 Capillary Electrophoresis |
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|
359 | (37) |
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12.9.2.1 Electroosmotic Flow |
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|
361 | (1) |
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12.9.2.2 Sample Introduction |
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|
361 | (1) |
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12.9.2.3 Analyte Detection |
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|
361 | (10) |
Chapter 13 Mass Spectrometry |
|
371 | (16) |
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|
371 | (1) |
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13.2 Sample Inlet Systems and Ion Sources |
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|
372 | (1) |
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373 | (3) |
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|
376 | (1) |
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|
377 | (1) |
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|
378 | (1) |
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|
378 | (2) |
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|
380 | (1) |
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13.9 Tandem Mass Spectrometry |
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|
381 | (6) |
Chapter 14 Electroanalytical Methods |
|
387 | (30) |
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|
387 | (4) |
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14.2 Transfer Tendencies: Standard Reduction Potentials |
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|
391 | (2) |
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14.3 Determination of Overall Redox Reaction Tendency: E°cell |
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|
393 | (1) |
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|
394 | (2) |
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|
396 | (9) |
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14.5.1 Reference Electrodes |
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|
396 | (3) |
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14.5.1.1 The Saturated Calomel Reference Electrode (SCE) |
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|
396 | (2) |
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14.5.1.2 The SilverSilver Chloride Electrode |
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|
398 | (1) |
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14.5.2 Indicator Electrodes |
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|
399 | (1) |
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14.5.2.1 The pH Electrode |
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|
399 | (1) |
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14.5.3 Combination Electrodes |
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|
400 | (3) |
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14.5.3.1 The Combination pH Electrode |
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|
400 | (1) |
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14.5.3.2 Ion-Selective Electrodes |
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|
401 | (2) |
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14.5.4 Other Details of Electrode Design |
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|
403 | (1) |
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14.5.5 Care and Maintenance of Electrodes |
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|
403 | (1) |
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14.5.6 Potentiometric Titrations |
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|
404 | (1) |
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14.6 Voltammetry and Amperometry |
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|
405 | (1) |
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|
405 | (1) |
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|
406 | (1) |
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14.7 Karl Fischer Titration |
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|
406 | (11) |
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14.7.1 End Point Detection |
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|
406 | (1) |
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14.7.2 Elimination of Extraneous Water |
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|
407 | (1) |
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14.7.3 The Volumetric Method |
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|
407 | (2) |
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14.7.4 The Coulometric Method |
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|
409 | (8) |
Chapter 15 Miscellaneous Instrumental Techniques |
|
417 | (26) |
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|
417 | (5) |
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|
417 | (1) |
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15.1.2 X-Ray Diffraction Spectroscopy |
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|
418 | (3) |
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15.1.3 X-Ray Fluorescence Spectroscopy |
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|
421 | (1) |
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|
421 | (1) |
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15.1.5 Safety Issues Concerning X-Rays |
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|
422 | (1) |
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15.2 Nuclear Magnetic Resonance Spectroscopy |
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|
422 | (6) |
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|
422 | (1) |
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|
423 | (2) |
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|
425 | (3) |
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|
425 | (2) |
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15.2.3.2 Peak Splitting and Integration |
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|
427 | (1) |
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15.2.4 Solvents and Solution Concentration |
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|
428 | (1) |
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|
428 | (1) |
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|
428 | (6) |
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|
428 | (1) |
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|
429 | (1) |
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15.3.3 Temperature Dependence |
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|
430 | (1) |
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15.3.4 Capillary Viscometry |
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|
430 | (3) |
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15.3.5 Rotational Viscometry |
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|
433 | (1) |
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|
434 | (3) |
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|
434 | (1) |
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|
434 | (2) |
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15.4.3 DSC Instrumentation |
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|
436 | (1) |
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15.4.4 Applications of DSC |
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|
437 | (1) |
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|
437 | (6) |
Appendix 1: Formulas for Solution Concentration and Preparation Calculations |
|
443 | (4) |
Appendix 2: The Language of Quality Assurance and Good Laboratory Practice (GLP) Laws: A Glossary |
|
447 | (4) |
Appendix 3: Significant Figure Rules |
|
451 | (2) |
Appendix 4: Answers to Questions and Problems |
|
453 | (48) |
Index |
|
501 | |