Electrochemical methods in soil and water research|RISS 상세보기

목차 (Table of Contents)

CONTENTS
Preface = ⅴ
Acknowledgements = ⅶ
Chapter 1 : Electrode Potential = 1
1.1 Origin of Electrode Potential = 1

CONTENTS
Preface = ⅴ
Acknowledgements = ⅶ
Chapter 1 : Electrode Potential = 1
1.1 Origin of Electrode Potential = 1
1.1.1 Interface reaction = 1
1.1.2 Interface potential difference = 4
1.1.3 Distribution of potential at electrode-solution interface = 6
1.1.4 Electrode potential = 6
1.2 Nernst Equation = 7
1.2.1 Thermodynamic derivation = 8
1.2.2 Some applications = 9
1.2.3 Meaning of parameters of the Nernst equation = 14
1.2.4 Membrane potential = 19
1.3 Electromotive Force = 19
1.3.1 Electrode potential and electromotive force = 19
1.3.2 Signs of electrode potential and electromotive force = 20
1.3.3 Electrochemical (Galvanic) cell and electrolytic cell = 21
1.3.4 Reversible cell and irreversible cell = 23
1.3.5 Analysis of a practical measuring cell = 24
1.3.6 Effect of temperature on electromotive force = 25
1.4 Electrode Polarization = 29
1.4.1 Causes of electrode polarization = 30
1.4.2 Butler-Volmer equation = 31
1.4.3 Some special cases in Butler-Volmer equation = 32
1.4.4 Polarizable electrode and unpolarizable electrode = 35
1.4.5 Factors affecting overpotential = 35
1.4.6 Some practical implications = 38
Chapter 2 : Principles of Potentiometric Methods = 45
2.1 Ion Activity = 45
2.1.1 Activity and activity coefficient = 45
2.1.2 Ionic strength = 48
2.1.3 Calculation of activity coefficient = 49
2.1.4 Activity standard = 50
2.1.5 pH buffer solution = 52
2.1.6 pM buffer solution = 54
2.2 Potentiometry = 56
2.2.1 Calibration curve method = 56
2.2.2 Direct indication of pX = 57
2.2.3 Known addition method = 58
2.2.4 Known subtraction method = 60
2.2.5 Known addition-dilution method = 60
2.3 Potentiometric Titration = 61
2.3.1 Titration curve method = 61
2.3.2 Gran plot method = 65
2.3.3 Null-point method = 67
Chapter 3 : Reference Electrodes = 71
3.1 Requirements for a Reference Electrode = 71
3.2 Calomel Electrodes = 73
3.2.1 Principles = 73
3.2.2 Preparation = 75
3.2.3 Properties = 79
3.2.4 Some remarks on usage = 81
3.3 Silver-silver Chloride Electrodes = 81
3.3.1 Principles = 82
3.3.2 Preparation = 84
3.3.3 Properties = 87
3.4 Mercury-mercurous Sulfate Electrode = 88
3.5 Oxidation-reduction Electrodes = 89
3.6 Reference Electrodes for Field Use = 92
3.6.1 Requirements for field use = 92
3.6.2 Copper-copper sulfate electrode = 93
3.6.3 Solid-state reference electrode = 93
3.6.4 R$$\mathop u\limits ^\circ $$$$\breve z$$i$$\breve c$$ka reference selectrode = 94
Chapter 4 : Liquid-junction Potential = 96
4.1 Introduction = 96
4.2 Principles = 96
4.2.1 Types of liquid-junction = 96
4.2.2 Origin of liquid-junction potential = 99
4.2.3 General equation for liquid-junction potential = 101
4.2.4 Calculation of liquid-junction potential = 102
4.3 Liquid-junction Potential Involving Colloidal Systems = 107
4.4 Liquid-junction Potential in Relation to Salt Bridge = 108
4.4.1 Functions of salt bridge = 108
4.4.2 Patterns of liquid-junction with commonly used reference electrodes = 110
4.4.3 Factors affecting liquid-junction potential = 111
4.4.4 Comparison among liquid-junction patterns = 112
4.5 Effect of Experimental Conditions on Liquid-junction Potential = 113
4.5.1 Ionic strength of the test solution = 113
4.5.2 pH of test solution = 113
4.5.3 Temperature = 114
4.5.4 Stirring = 114
4.5.5 Considerations in continuous measurements = 115
4.6 Residual Liquid-junction Potential = 115
4.7 Reduction and Elimination of Liquid-junction Potential = 116
4.7.1 Use of reference electrodes without liquid-junction = 117
4.7.2 Proper selection of salt bridge solution = 117
4.7.3 Proper setup of liquid-junction = 117
4.7.4 Separation from colloids and avoidance of clogging = 118
Chapter 5 : Characteristics of Ion-selective Electrodes = 121
5.1 Introduction = 121
5.2 Potential Response = 121
5.3 Detection Limit = 124
5.3.1 Definition = 124
5.3.2 Effect of solubility of membrane material = 124
5.3.3 Effect of surface condition of electrode membrane = 125
5.3.4 Effect of solution composition = 125
5.3.5 Effect of other factors = 125
5.4 Selectivity = 126
5.4.1 Definition = 126
5.4.2 Determination of $$K^{pot}_{A,B}$$ = 126
5.4.3 Comments on potentiometric selectivity coefficient = 130
5.5 Resistance = 131
5.5.1 Significance = 132
5.5.2 Methods of measurement = 132
5.5.3 Factors affecting electrode resistance = 134
5.5.4 Insulation resistance (leakage resistance) = 135
5.6 Response Time = 136
5.6.1 Definition = 136
5.6.2 Method of determination = 137
5.6.3 Models for describing dynamic response = 138
5.6.4 Factors affecting response time = 140
5.6.5 Hysteresis = 142
5.7 Other Properties = 142
5.7.1 Effect of temperature, light and radiation = 142
5.7.2 Potential drift = 143
5.7.3 Life-time = 143
Chapter 6 : Glass Electrodes and Their Applications = 147
6.1 Composition and Structure of Electrode Glass = 147
6.1.1 Elementary composition = 148
6.1.2 Structure of glass = 150
6.1.3 Types of oxides constructing electrode glass = 151
6.1.4 Function of constitutional oxides of elements in electrode glass = 152
6.2 Properties of Electrode Glass = 156
6.2.1 Sorption of water = 157
6.2.2 Gel layer = 157
6.2.3 exchange and distribution of ions at glass surface = 158
6.2.4 Chemical durability = 159
6.2.5 Electrical resistance = 161
6.3 Mechanisms of Electrode Potential = 162
6.3.1 Origin of membrane potential = 162
6.3.2 Selectivity = 164
6.3.3 Effect of structure of glass on selectivity = 165
6.3.4 Acid error and alkaline error = 166
6.3.5 Asymmetry potential = 167
6.4 Fabrication = 168
6.4.1 General consideration = 168
6.4.2 Making of sensitive glass = 169
6.4.3 Working of glass = 170
6.4.4 Inner reference electrodes = 173
6.4.5 Assembling = 174
6.5 Applications = 174
6.5.1 Determination of soil pH in the laboratory = 174
6.5.2 Determination of pH of water = 178
6.5.3 Use of cation-selective electrodes = 178
6.5.4 Determination of pH and pNa of soils in situ = 179
Chapter 7 : Solid-state Membrane Electrodes and Their Applications = 183
7.1 Principles = 183
7.1.1 Electrode potential = 183
7.1.2 Selectivity = 187
7.1.3 Sensitivity = 191
7.2 Types = 193
7.3 Construction and Fabrication = 195
7.3.1 Configuration = 195
7.3.2 Preparation of electro-active material = 196
7.3.3 Making of membrane by pressing or pressing-sintering = 198
7.3.4 Inner conducting element = 199
7.3.5 Miniature and micro-electrodes = 200
7.4 Properties and Applications of Some Electrodes = 200
7.4.1 Chloride ion-selective electrode = 200
7.4.2 Fluoride ion-selective electrode = 205
7.4.3 Sulfide ion-selective electrode = 208
7.4.4 Lead ion-selective electrode = 211
7.4.5 Cyanide ion-selective electrode = 213
Chapter 8 : Liquid-state Membrane Electrodes and Their Applications = 217
8.1 Principles = 217
8.1.1 Electrodes of the ion-exchanger type = 217
8.1.2 Electrodes of the neutral carrier type = 221
8.2 Basic Properties = 225
8.2.1 Stability of electrode potential = 225
8.2.2 Selectivity = 226
8.2.3 Detection limit = 232
8.2.4 Response time = 234
8.2.5 Life-time = 236
8.3 Construction = 237
8.3.1 Requirements for various components = 237
8.3.2 Liquid membrane type = 238
8.3.3 Polymer membrane type = 239
8.3.4 Other constructions = 239
8.4 Applications of Some Important Electrodes = 242
8.4.1 Nitrate ion-selective electrode = 242
8.4.2 Potassium ion-selective electorde = 245
8.4.3 Calcium in-selective electorde = 252
8.4.4 barium ion-selective electrode = 261
Chapter 9 : Gas Sensors and Their Applications = 267
9.1 Principles = 267
9.1.1 electrode potential = 267
9.1.2 Requirements for the production of gas = 271
9.1.3 Measuring range in relation to electrolyte concentration = 273
9.2 Construction = 276
9.2.1 Gas-permeable membrane = 277
9.2.2 Inner electrolyte solution = 280
9.2.3 Indicator electrode = 282
9.2.4 Reference electrode = 284
9.2.5 Air-gap sensor = 285
9.3 Handling = 285
9.3.1 Adjustment of pH of test solution = 285
9.3.2 Stirring and closing of test solution = 296
9.3.3 Time of reading = 287
9.3.4 Effect of temperature = 288
9.3.5 Conditioning and storage = 288
9.3.6 Some remarks = 289
9.4 Uses of Some Sensors = 289
9.4.1 Ammonia sensor = 289
9.4.2 Hydrogen sulfide sensor = 291
9.4.3 Carbon dioxide sensor = 294
Chapter 10 : Oxidation-reduction Potential and Its Measurement = 297
10.1 Principles = 297
10.1.1 Oxidation-reduction reaction and its basic equations = 297
10.1.2 Influence of pH on Eh = 300
10.1.3 Oxidation-reduction electrode = 302
10.2 Fabrication and Treatment of Oxidation-reduction Electrodes = 305
10.2.1 Electrode material = 305
10.2.2 Fabrication of platinum electrode = 305
10.2.3 Selection of platinum electrode = 306
10.2.4 Treatment of electrode surface = 307
10.3 Measurement of Oxidation-reduction Potential = 308
10.3.1 Conventional method for soils = 308
10.3.2 Depolarization method for soils = 310
10.3.3 Conventional method for water = 312
Chapter 11 : Common problems and Their Causes in Potentiometric Measurements = 314
11.1 General Examination = 314
11.1.1 Instrument = 315
11.1.2 Electrodes = 315
11.1.3 Solution = 316
11.2 Problems with the Reading = 316
11.2.1 No reading = 316
11.2.2 Pointer beyond the scale = 317
11.2.3 Pointer vibration enhanced by external induction = 319
11.2.4 Slow attainment of steady reading = 321
11.2.5 Very slow attainment of steady reading = 321
11.2.6 Parallel shifts in reading = 323
11.3 Problems with the S Value = 323
11.3.1 No potential response = 324
11.3.2 S smaller than theoretical value = 325
11.3.3 S smaller than theoretical value at low concentrations = 326
11.3.4 S deviates from theoretical value at high concentrations = 327
11.3.5 Irregular S = 328
11.4 Problems with the Solution = 328
11.5 Problems with the Liquid-junction = 329
Chapter 12 : Conductometric Methods = 332
12.1 Principles = 333
12.1.1 Electrical conductance and specific conductance = 333
12.1.2 Equivalent conductance and limiting equivalent conductance = 333
12.1.3 Ionic mobility = 336
12.1.4 Debye-H$$\ddot u$$ckel-Onsager theory = 337
12.1.5 Conductance at high frequencies and in strong electric field = 339
12.1.6 Electrical conductance of soils = 340
12.2 AC Method of Measurement = 340
12.2.1 Conductance cell and electrodes = 341
12.2.2 Factors affecting precision of measurement = 345
12.2.3 Calculation of results = 348
12.3 DC Method of Measurement = 350
12.3.1 Comparison between AC method and DC method = 350
12.3.2 Principle = 351
12.3.3 Apparatus = 352
12.3.4 Measurement = 354
12.4 Conductometric Titration = 355
12.4.1 Titration of strong acid = 355
12.4.2 Titration of a mixture of strong acid and weak acid = 356
12.4.3 Replacement titration = 357
12.4.4 Precipitation titration = 357
12.5 Applications = 359
12.5.1 Evaluation of water quality = 359
12.5.2 Measurement of electrical conductivity of soils in situ = 359
12.5.3 Estimation of salinity of soils = 362
12.5.4 Evaluation of nutrient status of soils = 363
12.5.5 Determination of cation-exchange capacity of soils = 363
12.5.6 Other applications = 363
Chapter 13 : Voltammetric Methods = 366
13.1 General Principles = 367
13.1.1 Current-voltage curve = 367
13.1.2 Diffusion current = 368
13.1.3 Half-wave potential = 376
13.2 Apparatus = 380
13.2.1 Working electrode = 380
13.2.2 Reference electrode = 387
13.2.3 Electrolytic cell = 389
13.3 Determination of Reducing Substances in Soils = 389
13.3.1 General = 389
13.3.2 Characterization = 391
13.3.3 Determination in situ = 392
13.3.4 Calibration = 392
13.4 Determination of COD of Water = 392
13.4.1 Theoretical consideration = 392
13.4.2 Determination = 344
13.4.3 Some remarks = 394
13.5 Determination of Oxygen in Soils and Water = 395
13.5.1 Principles = 395
13.5.2 Factors affecting determination = 396
13.5.3 Determination = 401
13.6 Determination of Manganous and Ferrous Ions and Stability Constants of Their Complexes = 403
13.6.1 General consideration = 403
13.6.2 Determination of manganese = 404
13.6.3 Determination of ferrous iron = 404
13.6.4 Determination of stability constant of complexes = 404
13.7 Amperometric Titration = 406
13.7.1 Principles = 406
13.7.2 Characteristics = 407
13.7.3 Determination of chloride = 407
13.7.4 Determination of sulfate = 408
Chapter 14 : Electrochemical Instruments = 413
14.1 Potentiometric Instruments = 413
14.1.1 Historical development = 413
14.1.2 Requirements for the potentiometric instruments when using ion-selective electrodes = 414
14.1.3 Components of potentiometric instruments = 422
14.1.4 Computerized potentiometric instruments = 430
14.2 Conductometric Instruments = 432
14.2.1 General consideration = 433
14.2.2 Measuring voltage source = 433
14.2.3 Measuring circuits = 435
14.2.4 Amplifier = 440
14.2.5 Indicator = 440
14.2.6 Direct-current conductometric instruments = 442
14.2.7 Computerized conductometers = 442
14.3 Voltammetric Instruments = 443
14.3.1 Basic components = 443
14.3.2 Voltage generator = 443
14.3.3 Potentiostat = 444
14.3.4 Current-voltage converter = 446
14.3.5 Instruments with constant polarization voltage = 448
14.4 Pocket Electrochemical Multimeter = 449
14.4.1 General consideration = 449
14.4.2 Measuring circuits = 449
14.4.3 High-input impedance DC amplifier = 452
14.4.4 Digital voltmeter = 452
Index = 454

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