An introduction to aqueous electrolyte solutions:
"An Introduction to Aqueous Electrolyte Solutions is a comprehensive coverage of the subject including the development of key concepts and theory that focus on the physical rather than the mathematical aspects. Important links are made between the study of electrolyte solutions and other branch...
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| Main Author: | |
|---|---|
| Format: | Book |
| Language: | English |
| Published: |
Chichester
Wiley
2007
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| Subjects: | |
| Online Access: | Table of contents only Inhaltsverzeichnis |
| Summary: | "An Introduction to Aqueous Electrolyte Solutions is a comprehensive coverage of the subject including the development of key concepts and theory that focus on the physical rather than the mathematical aspects. Important links are made between the study of electrolyte solutions and other branches of chemistry, biology and biochemistry, making it a useful cross-reference tool for students studying this important area of electrochemistry." "An invaluable text for students taking courses in chemistry and chemical engineering, this book will also be useful for biology, biochemistry and biophysics students required to study electrochemistry."--BOOK JACKET. |
| Item Description: | Includes index. |
| Physical Description: | XXVIII, 574 S. graph. Darst. |
| ISBN: | 9780470842942 9780470842935 |
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MARC
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| 100 | 1 | |a Wright, Margaret Robson |e Verfasser |4 aut | |
| 245 | 1 | 0 | |a An introduction to aqueous electrolyte solutions |c Margaret Robson Wright |
| 264 | 1 | |a Chichester |b Wiley |c 2007 | |
| 300 | |a XXVIII, 574 S. |b graph. Darst. | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 500 | |a Includes index. | ||
| 520 | 1 | |a "An Introduction to Aqueous Electrolyte Solutions is a comprehensive coverage of the subject including the development of key concepts and theory that focus on the physical rather than the mathematical aspects. Important links are made between the study of electrolyte solutions and other branches of chemistry, biology and biochemistry, making it a useful cross-reference tool for students studying this important area of electrochemistry." "An invaluable text for students taking courses in chemistry and chemical engineering, this book will also be useful for biology, biochemistry and biophysics students required to study electrochemistry."--BOOK JACKET. | |
| 650 | 7 | |a Equilíbrio químico |2 larpcal | |
| 650 | 7 | |a Solutions (chimie) |2 ram | |
| 650 | 7 | |a Solutions d'électrolyte |2 ram | |
| 650 | 7 | |a Soluções eletrolíticas |2 larpcal | |
| 650 | 7 | |a Équilibre chimique |2 ram | |
| 650 | 4 | |a Electrolyte solutions | |
| 650 | 4 | |a Chemical equilibrium | |
| 650 | 4 | |a Solution (Chemistry) | |
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| _version_ | 1804136592011427840 |
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| adam_text | AN INTRODUCTION TO AQUEOUS ELECTROLYTE SOLUTIONS MARGARET ROBSON WRIGHT
FORMERLY OF ST ANDREWS UNIVERSITY, UK BICHTIHHIAU BICENTENNIAL JOHN
WILEY & SONS, LTD CONTENTS PREFACE PRELIMINARY CHAPTER GUIDANCE TO
STUDENT LIST OF SYMBOLS 1 CONCEPTS AND IDEAS: SETTING THE STAGE 1.1
ELECTROLYTE SOLUTIONS - WHAT ARE THEY? 1.2 IONS - SIMPLE CHARGED
PARTICLES OR NOT? 1.2.1 SIMPLE PROPERTIES OF IONS 1.2.2 MODIFICATIONS
NEEDED TO THESE SIMPLE IDEAS: A SUMMARY 1.3 THE SOLVENT: STRUCTURELESS
OR NOT? 1.4 THE MEDIUM: ITS STRUCTURE AND THE EFFECT OF IONS ON THIS
STRUCTURE 1.5 HOW CAN THESE IDEAS HELP IN UNDERSTANDING WHAT MIGHT
HAPPEN WHEN AN ION IS PUT INTO A SOLVENT? 1.6 ELECTROSTRICTION 1.7 IDEAL
AND NON-IDEAL SOLUTIONS - WHAT ARE THEY? 1.7.1 SOLUTE-SOLUTE
INTERACTIONS, I.E. ION-ION INTERACTIONS 1.7.2 SOLUTE-SOLVENT
INTERACTIONS, I.E. ION-SOLVENT INTERACTIONS-COLLECTIVELY KNOWN AS
SOLVATION 1.7.3 SOLVENT-SOLVENT INTERACTIONS 1.8 THE IDEAL ELECTROLYTE
SOLUTION 1.9 THE NON-IDEAL ELECTROLYTE SOLUTION 1.10 MACROSCOPIC
MANIFESTATION OF NON-IDEALITY 1.11 SPECIES PRESENT IN SOLUTION 1.12
FORMATION OF ION PAIRS FROM FREE IONS 1.12.1 CHARGE DISTRIBUTION ON THE
FREE ION AND THE ION PAIR 1.12.2 SIZE OF AN ION AND AN ION PAIR IN
SOLUTION 1.13 COMPLEXES FROM FREE IONS 1.14 COMPLEXES FROM IONS AND
UNCHARGED LIGANDS 1.15 CHELATES FROM FREE IONS 1.16 MICELLE FORMATION
FROM FREE IONS 1.17 MEASURING THE EQUILIBRIUM CONSTANT: GENERAL
CONSIDERATIONS 1.18 BASE-LINES FOR THEORETICAL PREDICTIONS ABOUT THE
BEHAVIOUR EXPECTED FOR A SOLUTION CONSISTING OF FREE IONS ONLY,
DEBYE-HUECKEL AND FUOSS-ONSAGER THEORIES AND THE USE OF BEER S LAW 1.18.1
DEBYE-HUECKEL AND FUOSS-ONSAGER EQUATIONS 1.18.2 BEER S LAW EQUATION VIII
CONTENTS 1.19 ULTRASONICS 26 1.20 POSSIBILITY THAT SPECIFIC EXPERIMENTAL
METHODS COULD DISTINGUISH BETWEEN THE VARIOUS TYPES OF ASSOCIATED
SPECIES 29 1.21 SOME EXAMPLES OF HOW CHEMISTS COULD GO ABOUT INFERRING
THE NATURE OF THE SPECIES PRESENT 29 2 THE CONCEPT OF CHEMICAL
EQUILIBRIUM: AN INTRODUCTION 33 2.1 IRREVERSIBLE AND REVERSIBLE
REACTIONS 34 2.2 COMPOSITION OF EQUILIBRIUM MIXTURES, AND THE APPROACH
TO EQUILIBRIUM 34 2.3 MEANING OF THE TERM POSITION OF EQUILIBRIUM AND
FORMULATION OF THE EQUILIBRIUM CONSTANT 35 2.3.1 IDEAL AND NON-IDEAL
EQUILIBRIUM EXPRESSIONS 37 2.3.2 PREDICTION OF THE IDEAL ALGEBRAIC FORM
OF THE EQUILIBRIUM CONSTANT FROM THE STOICHIOMETRIC EQUATION 38 2.4
EQUILIBRIUM AND THE DIRECTION OF REACTION 39 2.5 A SEARCHING PROBLEM 44
2.6 THE POSITION OF EQUILIBRIUM 45 2.7 OTHER GENERALISATIONS ABOUT
EQUILIBRIUM 46 2.8 K AND PK 46 2.9 QUALITATIVE EXPERIMENTAL OBSERVATIONS
ON THE EFFECT OF TEMPERATURE ON THE EQUILIBRIUM CONSTANT, K 47 2.10
QUALITATIVE EXPERIMENTAL OBSERVATIONS ON THE EFFECT OF PRESSURE ON THE
EQUILIBRIUM CONSTANT, K 49 2.11 STOICHIOMETRIC RELATIONS 49 2.12 A
FURTHER RELATION ESSENTIAL TO THE DESCRIPTION OF ELECTROLYTE SOLUTIONS -
ELECTRICAL NEUTRALITY 50 3 ACIDS AND BASES: A FIRST APPROACH 53 3.1 A
QUALITATIVE DESCRIPTION OF ACID-BASE EQUILIBRIA 54 3.1.1 ACIDIC
BEHAVIOUR 54 3.1.2 BASIC BEHAVIOUR 55 3.2 THE SEIF IONISATION OF WATER
56 3.3 STRENG AND WEAK ACIDS AND BASES 56 3.4 A MORE DETAILED
DESCRIPTION OF ACID-BASE BEHAVIOUR 57 3.4.1 THE WEAK ACID, E.G. BENZOIC
ACID 57 3.4.2 THE WEAK BASE, E.G. METHYLAMINE 58 3.4.3 THE AMPHOTERIC
SOLVENT WATER 59 3.5 AMPHOLYTES 60 3.6 OTHER SITUATIONS WHERE ACID/BASE
BEHAVIOUR APPEARS 62 3.6.1 SALTS AND BUFFERS 62 3.7 FORMULATION OF
EQUILIBRIUM CONSTANTS IN ACID-BASE EQUILIBRIA 66 3.8 MAGNITUDES OF
EQUILIBRIUM CONSTANTS 67 3.9 THE SEIF IONISATION OF WATER 67 3.10
RELATIONS BETWEEN K A AND K B : EXPRESSIONS FOR AN ACID AND ITS
CONJUGATE BASE AND FOR A BASE AND ITS CONJUGATE ACID 68 3.11
STOICHIOMETRIC ARGUMENTS IN EQUILIBRIA CALCULATIONS 70 3.12 PROCEDURE
FOR CALCULATIONS ON EQUILIBRIA 71 CONTENTS IX 4 EQUILIBRIUM CALCULATIONS
FOR ACIDS AND BASES 73 4.1 CALCULATIONS ON EQUILIBRIA: WEAK ACIDS 74
4.1.1 POSSIBLE APPROXIMATIONS FOR THE WEAK ACID 75 4.1.2 THE WEAK ACID
WHERE BOTH APPROXIMATIONS CAN BE MADE 76 4.1.3 THE WEAK ACID WHERE THERE
IS EXTENSIVE IONISATION AND APPROXIMATION 1 IS INVALID 77 4.1.4 THE WEAK
ACID IS SUFFICIENTLY WEAK SO THAT THE SEIF IONISATION OF WATER CANNOT BE
IGNORED AND APPROXIMATION 2 IS INVALID 78 4.1.5 ELECTRICAL NEUTRALITY 80
4.2 SOME WORKED EXAMPLES 80 4.3 CALCULATIONS ON EQUILIBRIA: WEAK BASES
85 4.3.1 POSSIBLE APPROXIMATIONS FOR THE WEAK BASE 86 4.3.2 THE WEAK
BASE WHERE BOTH APPROXIMATIONS CAN BE MADE 88 4.3.3 THE WEAK BASE WHERE
THERE IS EXTENSIVE PROTONATION AND APPROXIMATION 1 IS INVALID 88 4.3.4
THE WEAK BASE IS SUFFICIENTLY WEAK SO THAT THE SEIF IONISATION OF WATER
CANNOT BE IGNORED AND APPROXIMATION 2 IS INVALID 89 4.4 SOME
ILLUSTRATIVE PROBLEMS 90 4.5 FRACTION IONISED AND FRACTION NOT IONISED
FOR A WEAK ACID; FRACTION PROTONATED AND FRACTION NOT PROTONATED FOR A
WEAK BASE 97 4.6 DEPENDENCE OF THE FRACTION IONISED ON PK A AND PH 98
4.6.1 MAXIMUM % IONISED FOR A WEAK ACID AND MAXIMUM % PROTONATED FOR A
WEAK BASE 100 4.7. THE EFFECT OF DILUTION ON THE FRACTION IONISED FOR
WEAK ACIDS LYING ROUGHLY IN THE RAENGE: P/F A = 4.0 TO 10.0 101 4.8
REASSESSMENT OF THE TWO APPROXIMATIONS: A RIGOROUS EXPRESSION FOR A WEAK
ACID 103 4.9 CONJUGATE ACIDS OF WEAK BASES 104 4.10 WEAK BASES 105 4.11
EFFECT OF NON-IDEALITY 105 5 EQUILIBRIUM CALCULATIONS FOR SALTS AND
BUFFERS 107 5.1 AQUEOUS SOLUTIONS OF SALTS 108 5.2 SALTS OF STRONG
ACIDS/STRONG BASES 108 5.3 SALTS OF WEAK ACIDS/STRONG BASES 108 5.4
SALTS OF WEAK BASES/STRONG ACIDS 109 5.4.1 A MORE RIGOROUS TREATMENT OF
WORKED PROBLEM 5.1 112 5.5 SALTS OF WEAK ACIDS/WEAK BASES 117 5.6 BUFFER
SOLUTIONS 119 5.6.1 BUFFER: WEAK ACID PLUS ITS SALT WITH A STRONG BASE
120 5.6.2 THE RIGOROUS CALCULATION FOR THE BUFFER OF A WEAK ACID PLUS
ITS SALT WITH A STRONG BASE 122 5.6.3 BUFFER: WEAK BASE PLUS ITS SALT
WITH A STRONG ACID 129 5.6.4 THE RIGOROUS CALCULATION FOR THE BUFFER OF
A WEAK BASE PLUS ITS SALT WITH A STRONG ACID 131 5.6.5 EFFECT OF
DILUTION ON BUFFERING CAPACITY 134 5.6.6 EFFECT OF ADDITION OF H 3 0 +
(AQ) OR OH~(AQ) ON THE PH OF A BUFFER 134 5.6.7 EFFECT OF ADDITION OF H
3 0 + (AQ) OR OH (AQ) ON THE PH OF A WEAK ACID ON ITS OWN 135 5.6.8
BUFFER CAPACITY 135 X CONTENTS 6 NEUTRALISATION AND PH TITRATION CURVES
139 6.1 NEUTRALISATION 140 6.2 PH TITRATION CURVES 141 6.2.1
NEUTRALISATION OF A STRONG ACID BY A STRONG BASE, E.G. HCL(AQ) WITH
NAOH(AQ) 141 6.2.2 NEUTRALISATION OF A STRONG BASE BY A STRONG ACID,
E.G. NAOH(AQ) WITH HCL(AQ) 145 6.2.3 NEUTRALISATION OF A WEAK ACID BY A
STRONG BASE, E.G. CH 3 COOH(AQ) WITH NAOH(AQ) 145 6.2.4 NEUTRALISATION
OF A WEAK BASE BY A STRONG ACID, E.G. NH 3 (AQ) WITH HCL(AQ) 148 6.3
INTERPRETATION OF PH TITRATION CURVES 149 6.4 POLYBASIC ACIDS 153 6.4.1
ANALYSIS OF POLYBASIC PH TITRATION CURVES 156 6.4.2 A DIBASIC ACID WITH
TWO APPARENTLY SEPARATED PA VALUES, E.G. MALONIC ACID 157 6.5 PH
TITRATIONS OF DIBASIC ACIDS: THE CALCULATIONS 161 6.5.1 THE BEGINNING OF
THE TITRATION 162 6.5.2 THE FIRST EQUIVALENCE POINT 162 6.5.3 THE FIRST
BUFFER REGION 164 6.5.4 ANALYSIS OF THE FIRST BUFFER REGION 164 6.5.5
THE SECOND EQUIVALENCE POINT 165 6.5.6 THE SECOND BUFFER REGION 166 6.6
TRIBASIC ACIDS 166 6.6.1 ANALYSIS OF THE TITRATION CURVE 168 6.6.2 AN
IMPORTANT THOUGHT 168 6.7 AMPHOLYTES 168 6.7.1 ANALYSIS OF THE TITRATION
CURVES FOR ALIPHATIC AND AROMATIC AMINO ACIDS, AND AMINO PHENOLS 173 7
ION PAIRING, COMPLEX FORMATION AND SOLUBILITIES 177 7.1 ION PAIR
FORMATION 178 7.2 COMPLEX FORMATION 184 7.2.1 FRACTIONS ASSOCIATED 186
7.2.2 MEAN NUMBER OF LIGANDS BOUND 187 7.2.3 EQUILIBRIA CALCULATIONS 187
7.2.4 DETERMINATION OF SS L , SS 2 , FROM THE DEPENDENCE OF ACTUAL 188
7.2.5 DETERMINATION OF SS L , SS 2 , FROM THE DEPENDENCE OF N ON [L]
ACTUAL 188 7.3 SOLUBILITIES OF SPANNGLY SOLUBLE SALTS 195 7.3.1
FORMULATION OF THE SOLUBILITY PRODUCT IN TERMS OF THE SOLUBILITY 195
7.3.2 SOLUBILITY RELATIONS WHEN A SPARINGLY SOLUBLE SALT IS DISSOLVED IN
A SOLUTION CONTAINING ONE OF THE IONS OF THE SOLID: THE COMMON ION
EFFECT 196 7.3.3 POSSIBILITY OR OTHERWISE OF PRECIPITATION OF A
SPARINGLY SOLUBLE SALT WHEN TWO SOLUTIONS CONTAINING THE RELEVANT IONS
ARE MIXED 198 7.3.4 THE EFFECT OF COMPLEXING ON SOLUBILITY EQUILIBRIA
203 7.3.5 ANOTHER INTERESTING EXAMPLE 205 7.3.6 FURTHER EXAMPLES OF THE
EFFECT OF COMPLEXING ON SOLUBILITY 208 8 PRACTICAL APPLICATIONS OF
THERMODYNAMICS FOR ELECTROLYTE SOLUTIONS 215 8.1 THE FIRST LAW OF
THERMODYNAMICS 8.2 THE ENTHALPY, H 216 217 CONTENTS XI 8.3 THE
REVERSIBLE PROCESS 217 8.4 THE SECOND LAW OF THERMODYNAMICS 217 8.5
RELATIONS BETWEEN Q, W AND FHERMODYNAMIC QUANTITIES 218 8.6 SOME OTHER
DEFINITIONS OF IMPORTANT THERMODYNAMIC FUNCTIONS 218 8.7 A VERY
IMPORTANT EQUATION WHICH CAN NOW BE DERIVED 218 8.8 RELATION OF EMFS TO
THERMODYNAMIC QUANTITIES 219 8.9 THE THERMODYNAMIC CRITERION OF
EQUILIBRIUM 220 8.10 SOME FURTHER DEFINITIONS: STANDARD STATES AND
STANDARD VALUES 221 8.11 THE CHEMICAL POTENTIAL OF A SUBSTANCE 221 8.12
CRITERION OF EQUILIBRIUM IN TERMS OF CHEMICAL POTENTIALS 222 8.13
CHEMICAL POTENTIALS FOR SOLIDS, LIQUIDS, GASES AND SOLUTES 223 8.14 USE
OF THE THERMODYNAMIC CRITERION OF EQUILIBRIUM IN THE DERIVATION OF THE
ALGEBRAIC FORM OF THE EQUILIBRIUM CONSTANT 224 8.15 THE TEMPERATURE
DEPENDENCE OF AEFF 9 230 8.16 THE DEPENDENCE OF THE EQUILIBRIUM CONSTANT,
K, ON TEMPERATURE 231 8.16.1 CALCULATION OF AH 9 FROM TWO VALUES OF K
231 8.16.2 DETERMINATION OF AH E FROM VALUES OF K OVER A RAENGE OF
TEMPERATURES 231 8.17 THE MICROSCOPIC STATISTICAL INTERPRETATION OF
ENTROPY 236 8.17.1 THE STATISTICAL MECHANICAL INTERPRETATION OF ENTROPY
236 8.17.2 THE ORDER/DISORDER INTERPRETATION OF ENTROPY 236 8.18
DEPENDENCE OF K ON PRESSURE 237 8.19 DEPENDENCE OF AG ON TEMPERATURE
242 8.20 DEPENDENCE OF AS* ON TEMPERATURE 242 8.21 THE NON-IDEAL CASE
244 8.21.1 NON-IDEALITY IN ELECTROLYTE SOLUTIONS 244 8.21.2 THE IONIC
STRENGTH AND NON-IDEALITY 244 8.22 CHEMICAL POTENTIALS AND MEAN ACTIVITY
COEFFICIENTS 247 8.23 A GENERALISATION 251 8.24 CORRECTIONS FOR
NON-IDEALITY FOR EXPERIMENTAL EQUILIBRIUM CONSTANTS 258 8.24.1
DEPENDENCE OF EQUILIBRIUM CONSTANTS ON IONIC STRENGTH 258 8.25 SOME
SPECIFIC EXAMPLES OF THE DEPENDENCE OF THE EQUILIBRIUM CONSTANT ON IONIC
STRENGTH 263 8.25.1 THE CASE OF ACID/BASE EQUILIBRIA 263 8.25.2 THE WEAK
ACID WHERE BOTH APPROXIMATIONS ARE VALID 263 8.25.3 THE WEAK ACID WHERE
THERE IS EXTENSIVE IONISATION 266 8.26 GRAPHICAL CORRECTIONS FOR
NON-IDEALITY 270 8.27 COMPARISON OF NON-GRAPHICAL AND GRAPHICAL METHODS
OF CORRECTING FOR NON-IDEALITY 270 8.28 DEPENDENCE OF FRACTION IONISED
AND FRACTIION PROTONATED ON IONIC STRENGTH 271 8.29 THERMODYNAMIC
QUANTITIES AND THE EFFECT OF NON-IDEALITY 271 9 ELECTROCHEMICAL CELLS
AND EMFS 273 9.1 CHEMICAL ASPECTS OF THE PASSAGE OF AN ELECTRIC CURRENT
THROUGH A CONDUCTING MEDIUM 274 9.2 ELECTROLYSIS 275 9.2.1 QUANTITATIVE
ASPECTS OF ELECTROLYSIS 278 9.2.2 A SUMMARY OF ELECTROLYSIS 279 9.3
ELECTROCHEMICAL CELLS 280 9.3.1 THE ELECTROCHEMICAL CELL OPERATING
IRREVERSIBLY OR REVERSIBLY 280 9.3.2 POSSIBLE SOURCES OF CONFUSION 280
9.3.3 CELLS USED AS BATTERIES AS A SOURCE OF CURRENT, I.E. OPERATING
IRREVERSIBLY 280 9.3.4 CELLS OPERATING REVERSIBLY AND IRREVERSIBLY 284
9.3.5 CONDITIONS FOR REVERSIBILITY OF CELLS 285 XII CONTENTS 9.4 SOME
EXAMPLES OF ELECTRODES USED IN ELECTROCHEMICAL CELLS 285 9.4.1 GAS
ELECTRODES 285 9.4.2 METAL ELECTRODE DIPPING INTO AN AQUEOUS SOLUTION OF
ITS IONS 286 9.4.3 METAL COATED WITH A SPARINGLY SOLUBLE COMPOUND OF THE
METAL DIPPING INTO AN AQUEOUS SOLUTION CONTAINING THE ANION OF THE
SPARINGLY SOLUBLE COMPOUND 287 9.4.4 THE REDOX ELECTRODE 288 9.4.5
REACTIONS OCCURRING AT THE ELECTRODES IN A REDOX CELL 288 9.4.6 THE
AMALGAM ELECTRODE 290 9.4.7 GLASS ELECTRODES 292 9.5 COMBINATION OF
ELECTRODES TO MAKE AN ELECTROCHEMICAL CELL 292 9.6 CONVENTIONS FOR
WRITING DOWN THE ELECTROCHEMICAL CELL 293 9.6.1 USE OF A VOLTMETER TO
DETERMINE THE POLARITY OF THE ELECTRODES 294 9.7 ONE VERY IMPORTANT
POINT: CELLS CORRESPONDING TO A NET CHEMICAL REACTION 298 9.8 LIQUID
JUNCTIONS IN ELECTROCHEMICAL CELLS 298 9.8.1 CELLS WITHOUT LIQUID
JUNCTION 298 9.8.2 CELLS WITH LIQUID JUNCTION 299 9.8.3 TYPES OF LIQUID
JUNCTIONS 299 9.8.4 CELLS WITH A LIQUID JUNCTION CONSISTING OF A NARROW
TUBE: A CELL WITH TRANSFERENCE 299 9.8.5 CELLS WITH A POROUS POT
SEPARATING TWO SOLUTIONS: A CELL WITH TRANSFERENCE 301 9.8.6 CELLS WITH
A SALT BRIDGE: CELLS WITHOUT TRANSFERENCE 302 9.9 EXPERIMENTAL
DETERMINATION OF THE DIRECTION OF FLOW OF THE ELECTRONS, AND MEASUREMENT
OF THE POTENTIAL DIFFERENCE 305 9.10 ELECTRODE POTENTIALS 305 9.10.1
REDOX POTENTIALS 305 9.10.2 ELECTRODE POTENTIALS FOR STANDARD AND
NON-STANDARD CONDITIONS 306 9.11 STANDARD ELECTRODE POTENTIALS 306
9.11.1 STANDARD REDOX POTENTIALS 307 9.12 POTENTIAL DIFFERENCE,
ELECTRICAL WORK DONE AND AG FOR THE CELL REACTION 308 9.12.1
THERMODYNAMIC QUANTITIES IN ELECTROCHEMISTRY: RELATION OF AG TO E 309
9.12.2 THERMODYNAMIC QUANTITIES IN ELECTROCHEMISTRY: EFFECT OF
TEMPERATURE ON EMF 310 9.13 AG FOR THE CELL PROCESS: THE NERNST EQUATION
312 9.13.1 CORRECTIONS FOR NON-IDEALITY 313 9.13.2 A FURTHER EXAMPLE
DEDUCING THE NERNST EQUATION AND THE DEPENDENCE OF EMF ON IONIC STRENGTH
314 9.14 METHODS OF EXPRESSING CONCENTRATION 315 9.15 CALCULATION OF
STANDARD EMFS VALUES FOR CELLS AND AG E VALUES FOR REACTIONS 317 9.16
DETERMINATION OF PH 320 9.17 DETERMINATION OF EQUILIBNUM CONSTANTS FOR
REACTIONS WHERE K IS EITHER VERY LARGE OR VERY SMALL 322 9.18 USE OF
CONCENTRATION CELLS 324 9.19 CONCEALED CONCENTRATION CELLS AND SIMILAR
CELLS 326 9.20 DETERMINATION OF EQUILIBRIUM CONSTANTS AND PK VALUES FOR
REACTIONS WHICH ARE NOT DIRECTLY THAT FOR THE CELL REACTION 328 9.20.1
DETERMINATION OF PK VALUES FOR THE IONISATION OF WEAK ACIDS AND WEAK
BASES, AND FOR THE SEIF IONISATION OF H 2 0(1) 328 9.20.2 SOLUBILITY
PRODUCTS 333 9.20.3 A FURTHER USE OF CELLS TO GAIN INSIGHT INTO WHAT IS
OCCURRING IN AN ELECTRODE COMPARTMENT - ION PAIR FORMATION 334 CONTENTS
XIII 9.20.4 COMPLEX FORMATION 336 9.20.5 USE OF CELLS TO DETERMINE MEAN
ACTIVITY COEFFICIENTS AND THEIR DEPENDENCE ON IONIC STRENGTH 337 9.21
USE OF CONCENTRATION CELLS WITH AND WITHOUT LIQUID JUNCTIONS IN THE
DETERMINATION OF TRANSPORT NUMBERS 343 9.21.1 USE OF CELLS WITH AND
WITHOUT TRANSFERENCE IN DETERMINATION OF THE TRANSPORT NUMBERS OF LARGE
IONS 347 10 CONCEPTS AND THEORY OF NON-IDEALITY 349 10.1 EVIDENCE FOR
NON-IDEALITY IN ELECTROLYTE SOLUTIONS 350 10.2 THE PROBLEM THEORETICALLY
351 10.3 FEATURES OF THE SIMPLE DEBYE-HUECKEL MODEL 351 10.3.1 NAIVETY OF
THE DEBYE-HUECKEL THEORY 353 10.4 ASPECTS OF ELECTROSTATICS WHICH ARE
NECESSARY FOR AN UNDERSTANDING OF THE PROCEDURES USED IN THE
DEBYE-HUECKEL THEORY AND CONDUCTANCE THEORY 353 10.4.1 THE ELECTRIC
FIELD, FORCE OF INTERACTION AND WORK DONE 353 10.4.2 COULOMB S LAW 355
10.4.3 WORK DONE AND POTENTIAL ENERGY OF ELECTROSTATIC INTERACTIONS 355
10.4.4 THE RELATION BETWEEN THE FORCES OF INTERACTION BETWEEN TWO
CHARGES AND THE ELECTRIC FIELDS ASSOCIATED WITH EACH OF THEM 358 10.4.5
THE RELATION BETWEEN THE ELECTROSTATIC POTENTIAL ENERGY AND THE
ELECTROSTATIC POTENTIAL 359 10.4.6 RELATION BETWEEN THE ELECTRIC FIELD
AND THE ELECTROSTATIC POTENTIAL 359 10.5 THE IONIC ATMOSPHERE IN MORE
DETAIL 360 10.5.1 A SUMMARY 362 10.6 DERIVATION OF THE DEBYE-HUECKEL
THEORY FROM THE SIMPLE DEBYE-HUECKEL MODEL 363 10.6.1 STEP 1 STATING THE
PROBLEM 363 10.6.2 STEP 2 THE PROBLEM IS TO CALCULATE V,* IN TERMS OF
OTHER CALCULABLE POTENTIALS, BUT WHAT ARE THESE? 364 10.6.3 STEP 3 THE
QUESTION NOW IS: IS THERE ANYTHING IN PHYSICS, THAT IS, IN ELECTROSTATIC
THEORY, WHICH WOULD ENABLE THIS TO BE DONE? 365 10.6.4 TRANSLATING THE
POISSON EQUATION DIRECTLY TO THE CASE OF AN ELECTROLYTE IN SOLUTION 365
10.6.5 STEP 4 HOW CAN THE DISTRIBUTION OF THE DISCRETE IONS IN THE IONIC
ATMOSPHERE OF THE /-ION BE DESCRIBED? 366 10.6.6 THE TWO BASIC EQUATIONS
367 10.6.7 STEP 5 THE PROBLEM IS TO COMBINE THE POISSON EQUATION WITH
THE MAXWELL-BOLTZMANN EQUATION - HOW CAN THIS BE DONE? 368 10.6.8 STEP 6
COMBINING THE POISSON AND MAXWELL-BOLTZMANN EQUATIONS 370 10.6.9 STEP 7
SOLVING THE POISSON-BOLTZMANN EQUATION 370 10.6.10 EXPANSION AND
APPROXIMATION OF THE POISSON-BOLTZMANN EQUATION TO ONE NON-ZERO TERM
ONLY 371 10.6.11 THE IONIC STRENGTH 372 10.6.12 THE NEXT STEP IS TO
SOLVE THE TRUNCATED POISSON-BOLTZMANN EQUATION 372 10.6.13 STEP 8
CALCULATION OF THE POTENTIAL AT THE SURFACE OF THE CENTRAL J- ION DUE TO
THE IONIC ATMOSPHERE, AND THENCE FINDING THE ELECTROSTATIC ENERGY OF
INTERACTION BETWEEN AN ION AND ITS IONIC ATMOSPHERE 373 10.6.14
CALCULATION OF IJRJ BY SUBSTITUTION OF R = A IN EQUATION (10.48) 374
10.6.15 STEP 9 THE PROBLEM IS TO CALCULATE THE MEAN IONIC ACTIVITY
COEFFICIENT, Y 375 10.6.16 CONSTANTS APPEARING IN THE DEBYE-HUECKEL
EXPRESSION 377 10.6.17 THE PHYSICAL SIGNIFICANCE OF K~ 1 AND PJ 377 10.7
THE DEBYE-HUECKEL LIMITING LAW 380 10.8 SHORTCOMINGS OF THE DEBYE-HUECKEL
MODEL 382 XIV CONTENTS 10.8.1 STRENG ELECTROLYTES ARE COMPLETELY
DISSOCIATED 382 10.8.2 RANDOM MOTION IS NOT ATTAINED 382 10.8.3
NON-IDEALITY RESULTS FROM COULOMBIC INTERACTIONS BETWEEN IONS 382 10.8.4
IONS ARE SPHERICALLY SYMMETRICAL AND ARE UNPOLARISABLE 383 10.8.5 THE
SOLVENT IS A STRUCTURELESS DIELECTRIC 383 10.8.6 ELECTROSTRICTION IS
IGNORED 383 10.8.7 CONCEPT OF A SMEARED OUT SPHERICALLY SYMMETRICAL
CHARGE DENSITY 384 10.9 SHORTCOMINGS IN THE MATHEMATICAL DERIVATION OF
THE THEORY 384 10.10 MODIFICATIONS AND FURTHER DEVELOPMENTS OF THE
THEORY 385 10.10.1 EMPIRICAL METHODS 385 10.10.2 EMPIRICAL EXTENSION
USING A TERM. LINEAR IN IONIC STRENGTH 388 10.11 EVIDENCE FOR ION
ASSOCIATION FROM DEBYE-HUECKEL PLOTS 391 10.11.1 AN EXPLANATION OF THE
STATEMENT THAT IF AN ELECTROLYTE IS ASSOCIATED THEN THE GRAPH OF LOG 10
Y S.Y/L/L + BAY/L WILL APPROACH THE DEBYE-HUECKEL SLOPE FROM BELOW 391
10.11.2 UNKNOWN PARAMETERS IN THE DEBYE-HUECKEL EXTENDED EQUATION WHEN
ASSOCIATION OCCURS 393 10.12 THE BJERRUM THEORY OF ION ASSOCIATION 393
10.12.1 THE GRAPH AT THE HEART OF THE BJERRUM THEORY 394 10.12.2 THE
THEORETICAL EXPRESSION FOR THE ASSOCIATION CONSTANT FOR SYMMETRICAL
ELECTROLYTES 396 10.12.3 CALCULATION OF SS FROM THE BJERRUM THEORY 396
10.12.4 EXTENSION TO ACCOUNT FOR NON-IDEALITY 399 10.12.5 CRITIQUE OF
BJERRUM S THEORY 400 10.12.6 FUOSS ION PAIRS AND OTHERS 400 10.13
EXTENSIONS TO HIGHER CONCENTRATIONS 401 10.13.1 GUGGENHEIM^ NUMERICAL
INTEGRATION 401 10.13.2 EXTENSIONS TO HIGHER CONCENTRATIONS:
DAVIES EQUATION 402 10.14 MODERN DEVELOPMENTS IN ELECTROLYTE THEORY 402
10.15 COMPUTER SIMULATIONS 402 10.15.1 MONTE CARLO CALCULATIONS 403
10.15.2 MOLECULAR DYNAMICS 404 10.16 FURTHER DEVELOPMENTS TO THE
DEBYE-HUECKEL THEORY 404 10.16.1 DEVELOPMENTS FROM THE GURNEY CONCEPT OF
THE CO-SPHERE: A NEW MODEL 405 10.16.2 THE UNMODIFIED DEBYE-HUECKEL
THEORY 406 10.16.3 A FIRST MODIFICATION TO THE SIMPLE DEBYE-HUECKEL MODEL
406 10.16.4 A LESS SIMPLE GURNEY MODEL: A SECOND MODIFICATION TO THE
DEBYE-HUECKEL MODEL 407 10.16.5 A LESS SIMPLE GURNEY MODEL: A THIRD
MODIFICATION TO THE DEBYE-HUECKEL MODEL 408 10.16.6 A FURTHER
MODIFICATION INVOLVING A CAVITY TERM 408 10.16.7 USE OF THESE IDEAS IN
PRODUCING A NEW TREATMENT 409 10.17 STATISTICAL MECHANICS AND
DISTRIBUTION FUNCTIONS 409 10.17.1 THE SIMPLEST SITUATION: THE RADIAL
DISTRIBUTION FUNCTION OF THE DEBYE-HUECKEL THEORY 410 10.17.2 MORE
COMPLEX DISTRIBUTION FUNCTIONS 411 10.17.3 CONTRIBUTIONS TO THE TOTAL
POTENTIAL ENERGY OF THE ELECTROLYTE SOLUTION 413 10.18 APPLICATION OF
DISTRIBUTION FUNCTIONS TO THE DETERMINATION OF ACTIVITY COEFSSCIENTS DUE
TO KIRKWOOD; YVON; BORN AND GREEN; AND BOGOLYUBOV 414 10.18.1 USING
DISTRIBUTION FUNCTIONS TO FORMULATE A NEW QUANTITY G 415 10.19 A FEW
EXAMPLES OF RESULTS FROM DISTRIBUTION FUNCTIONS 417 10.20
BORN-OPPENHEIMER LEVEL MODEIS 419 10.21 LATTICE CALCULATIONS FOR
CONCENTRATED SOLUTIONS 419 CONTENTS XV 11 CONDUCTANCE: THE IDEAL CASE
421 11.1 ASPECTS OF PHYSICS RELEVANT TO THE EXPERIMENTAL STUDY OF
CONDUCTANCE IN SOLUTION 422 11.1.1 OHM SLAW 422 11.1.2 THE ELECTRIC
FLELD 424 11.2 EXPERIMENTAL MEASUREMENT OF THE CONDUCTIVITY OF A
SOLUTION 425 11.3 CORRECTIONS TO THE OBSERVED CONDUCTIVITY TO ACCOUNT
FOR THE SEIF IONISATION OF WATER 427 11.4 CONDUCTIVITIES AND MOLAR
CONDUCTIVITIES: THE IDEAL CASE 428 11.5 THE PHYSICAL SIGNIFICANCE OF THE
MOLAR CONDUCTIVITY, A 431 11.6 DEPENDENCE OF MOLAR CONDUCTIVITY ON
CONCENTRATION FOR A STRENG ELECTROLYTE: THE IDEAL CASE 432 11.7
DEPENDENCE OF MOLAR CONDUCTIVITY ON CONCENTRATION FOR A WEAK
ELECTROLYTE: THE IDEAL CASE 433 11.8 DETERMINATION OF A 436 11.9
SIMULTANEOUS DETERMINATION OF K AND A 438 11.10 PROBLEMS WHEN AN ACID
OR BASE IS SO WEAK THAT IT IS NEVER 100% IONISED, EVEN IN VERY, VERY
DILUTE SOLUTION 441 11.11 CONTRIBUTIONS TO THE CONDUCTIVITY OF AN
ELECTROLYTE SOLUTION FROM THE CATION AND THE ANION OF THE ELECTROLYTE
441 11.12 CONTRIBUTIONS TO THE MOLAR CONDUCTIVITY FROM THE INDIVIDUAL
IONS 442 11.13 KOHLRAUSCH S LAW OF INDEPENDENT IONIC MOBILITIES 443
11.14 ANALYSIS OF THE USE OF CONDUCTANCE MEASUREMENTS FOR DETERMINATION
OF PAF A S FOR VERY WEAK ACIDS AND PAET B S FOR VERY WEAK BASES: THE
BASIC QUANTITIES INVOLVED 447 11.14.1 ANALYSIS OF THE USE OF CONDUCTANCE
MEASUREMENTS FOR DETERMINATION OF PJF A S FOR VERY WEAK ACIDS AND P# B S
FOR VERY WEAK BASES: THE ARGUMENT 449 11.14.2 APPLICATION OF THE ABOVE
ANALYSIS TO THE CASES OF WEAK ACIDS AND WEAK BASES FOR WHICH THE
RELATION A = A/A IS TAKEN TO BE VALID AND A * 1 AS C * 0 450 11.15
USE OF CONDUCTANCE MEASUREMENTS IN DETERMINING SOLUBILITY PRODUCTS FOR
SPARINGLY SOLUBLE SALTS 451 11.16 TRANSPORT NUMBERS 453 11.17 IONIC
MOBILITIES 457 11.18 ABNORMAL MOBILITY AND IONIC MOLAR CONDUCTIVITY OF H
3 0 + (AQ) 463 11.19 MEASUREMENT OF TRANSPORT NUMBERS 464 11.19.1 THE
HITTORF METHOD FOR DETERMINING TRANSPORT NUMBERS 465 11.19.2 THE MOVING
BOUNDARY METHOD 468 11.19.3 THE ARGUMENT FOR THE UNSYMMETRICAL
ELECTROLYTE 470 11.19.4 THE FUNDAMENTAL BASIS OF THE MOVING BOUNDARY
METHOD 470 11.19.5 SUMMARY OF THE USE MADE OF TRANSPORT NUMBERS AND
MOBILITIES 473 12 THEORIES OF CONDUCTANCE: THE NON-IDEAL CASE FOR
SYMMETRICAL ELECTROLYTES 475 12.1 THE RELAXATION EFFECT 476 12.1.1
APPROXIMATE ESTIMATE OF THE RELAXATION TIME FOR THE IONIC ATMOSPHERE 477
12.1.2 CONFIRMATION OF THE EXISTENCE OF THE IONIC ATMOSPHERE 478 12.1.3
THE RELAXATION TIME AND THE DEBYE-FALKENHAGEN EFFECT, I.E. THE EFFECT OF
HIGH FREQUENCIES 478 12.1.4 THE RELAXATION TIME AND THE WIEN EFFECT,
I.E. THE EFFECT OF VERY LARGE FIELDS 479 12.2 THE ELECTROPHORETIC EFFECT
480 XVI CONTENTS 12.3 CONDUCTANCE EQUATIONS FOR STRONG ELECTROLYTES
TAKING NON-IDEALITY INTO CONSIDERATION: EARLY CONDUCTANCE THEORY 480
12.3.1 QUALITATIVE ASPECTS OF THE DERIVATION OF THE DEBYE-HUECKEL-ONSAGER
1927 EQUATION 481 12.4 A SIMPLE TREATMENT OF THE DERIVATION OF THE
DEBYE-HUECKEL-ONSAGER EQUATION 1927 FOR SYMMETNCAL ELECTROLYTES 483
12.4.1 STEP 1 STATING THE PROBLEM 483 12.4.2 STEP 2 THE CONTRIBUTION AT
INFINITE DILUTION RESULTING FROM A BALANCE OF THE EFFECTS OF THE FIELD
AND THE FRICTIONAL FORCE ON THE MOVING ION 483 12.4.3 STEP 3 THE
CONTRIBUTION FROM THE ELECTROPHORETIC EFFECT 484 12.4.4 STEP 4 THE
CONTRIBUTION FROM THE RELAXATION EFFECT 485 12.4.5 STEP 5 THE FINAL STEP
IN ARRIVING AT THE CONDUCTANCE EQUATION FOR SYMMETNCAL ELECTROLYTES 486
12.5 THE FUOSS-ONSAGER EQUATION 1932 488 12.6 USE OF THE
DEBYE-HUECKEL-ONSAGER EQUATION FOR SYMMETNCAL STRONG ELECTROLYTES WHICH
ARE FULLY DISSOCIATED 488 12.6.1 ASSESSMENT OF EXPERIMENTAL RESULTS FOR
1-1, 1-2 AND 1-3 ELECTROLYTES IN CONCENTRATION RANGES WHERE THEY ARE
EXPECTED TO BE FULLY DISSOCIATED 489 12.7 ELECTROLYTES SHOWING ION
PAIRING AND WEAK ELECTROLYTES WHICH ARE NOT FULLY DISSOCIATED 490 12.7.1
CALCULATION OF A , A AND K ISSOC FOR WEAK ELECTROLYTES AND ION PAIRS
USING THE DEBYE-HUECKEL-ONSAGER EQUATION 492 12.8 EMPIRICAL EXTENSIONS TO
THE DEBYE-HUECKEL-ONSAGER 1927 EQUATION 492 12.9 MODERN CONDUCTANCE
THEORIES FOR SYMMETRICAL ELECTROLYTES - POST 1950 493 12.10
FUOSS-ONSAGER 1957: CONDUCTANCE EQUATION FOR SYMMETRICAL ELECTROLYTES
493 12.10.1 USE OF THE FUOSS-ONSAGER EQUATION TO DETERMINE A AND A 498
12.10.2 IMPLICATIONS OF THE FUOSS-ONSAGER EQUATION FOR UNASSOCIATED
SYMMETRICAL ELECTROLYTES 498 12.11 A SIMPLE ILLUSTRATION OF THE EFFECTS
OF ION ASSOCIATION ON EXPERIMENTAL CONDUCTANCE CURVES 500 12.12 THE
FUOSS-ONSAGER EQUATION FOR ASSOCIATED ELECTROLYTES 500 12.12.1
DETERMINATION OF A , ^ASSOCIATION AND A USIN G THE FUOSS-ONSAGER
EQUATION FOR ASSOCIATED ELECTROLYTES 503 12.13 RANGE OF APPLICABILITY OF
FUOSS-ONSAGER 1957 CONDUCTANCE EQUATION FOR SYMMETRICAL ELECTROLYTES 503
12.14 LIMITATIONS OF THE TREATMENT GIVEN BY THE 1957 FUOSS-ONSAGER
CONDUCTANCE EQUATION FOR SYMMETRICAL ELECTROLYTES 504 12.15 MANIPULATION
OF THE 1957 FUOSS-ONSAGER EQUATION, AND LATER MODIFICATIONS BY FUOSS AND
OTHER WORKERS 505 12.16 CONDUCTANCE STUDIES OVER A RAENGE OF RELATIVE
PERMITTIVITIES 506 12.17 FUOSS ET AL. 1978 AND LATER 506 12.17.1 THE
FRACTION OF IONS WHICH ARE FREE TO CONDUCT THE CURRENT 511 12.17.2 THE
FUOSS 1978 EQUATION FOR ASSOCIATED SYMMETRICAL ELECTROLYTES 512 APPENDIX
1 . 5 1 2 APPENDEX 2 515 13 SOLVATION 517 13.1 CLASSIFICATION OF
SOLUTES: A RESUME 518 13.2 CLASSIFICATION OF SOLVENTS 518 13.3 SOLVENT
STRUCTURE 519 13.3.1 LIQUID WATER AS A SOLVENT 519 CONTENTS XVII 13.3.2
H-BONDING IN WATER 519 13.4 THE EXPERIMENTAL STUDY OF THE STRUCTURE OF
WATER 522 13.5 DIFFRACTION STUDIES 522 13.5.1 DETERMINATION OF THE
NUMBER OF H 2 0 MOLECULES CORRESPONDING TO EACH PEAK AND THE
THREE-DIMENSIONAL ARRANGEMENT CORRESPONDING TO EACH PEAK 524 13.5.2
RESULTS OF DIFFRACTION STUDIES: THE STRUCTURE OF LIQUID WATER 525 13.6
THE THEORETICAL APPROACH TO THE RADIAL DISTRIBUTION FUNCTION FOR A
LIQUID 526 13.7 AQUEOUS SOLUTIONS OF ELECTROLYTES 526 13.7.1 EFFECT OF
IONS ON THE RELATIVE PERMITTIVITY OF WATER 528 13.8 TERMS USED IN
DESCRIBING HYDRATION 528 13.8.1 SOLVATION SHELL 529 13.8.2 BOUND AND
NON-BOUND WATER 529 13.8.3 FURTHER TERMS: PRIMARY AND SECONDARY
SOLVATION 530 13.9 TRADITIONAL METHODS FOR MEASURING SOLVATION NUMBERS
530 13.9.1 VIBRATIONAL SPECTRA (IR AND RAMAN) AND ELECTRONIC SPECTRA
(UV, VISIBLE AND IN SOME CASES IR) 530 13.9.2 TRANSPORT PHENOMENA 531
13.9.3 RELATIVE PERMITTIVITY OF THE SOLUTION 532 13.9.4 ACTIVITY
MEASUREMENTS 532 13.10 MODERN TECHNIQUES FOR STUDYING HYDRATION: NMR 533
13.10.1 LIMITATIONS OF NMR 534 13.10.2 SLOW EXCHANGES OF WATER MOLECULES
534 13.10.3 FAST EXCHANGES OF WATER MOLECULES 535 13.10.4 RESULTS OF NMR
STUDIES OF HYDRATION 536 13.10.5 RESIDENCE TIMES FROM NMR AND ULTRASONIC
RELAXATION 536 13.11. MODERN TECHNIQUES OF STUDYING HYDRATION: NEUTRON
AND X-RAY DIFFRACTION 538 13.11.1 NEUTRON DIFFRACTION WITH ISOTOPE
SUBSTITUTION 539 13.12 MODERN TECHNIQUES OF STUDYING SOLVATION: AXD
DIFFRACTION AND EXAFS 541 13.13 MODERN TECHNIQUES OF STUDYING SOLVATION:
COMPUTER SIMULATIONS 542 13.14 CAUTIONARY REMARKS ON THE SIGNIFICANCE OF
THE NUMERICAL VALUES OF SOLVATION NUMBERS 543 13.15 SIZESOFIONS 544
13.16 A FIRST MODEL OF SOLVATION - THE THREE REGION MODEL FOR AQUEOUS
ELECTROLYTE SOLUTIONS 544 13.16.1 STRUCTURE MAKING AND STRUCTURE
BREAKING IONS 545 13.16.2 EVIDENCE FOR STRUCTURE MAKING/STRUCTURE
BREAKING 545 13.16.3 A FIRST ATTEMPT AT CLASSIFICATION 545 13.16.4
THERMODYNAMIC EVIDENCE 546 13.16.5 DETERMINATION OF PARTIAL MOLAR
ENTROPIES FOR INDIVIDUAL IONS 547 13.16.6 STANDARD ENTROPIES OF
HYDRATION 548 13.16.7 SIGNIFICANCE OF ENTROPIES OF HYDRATION FOR
STRUCTURE MAKING/BREAKING 549 13.17 VOLUME CHANGES ON SOLVATION 551
13.18 VISCOSITY DATA 552 13.19 CONCLUDING COMMENT 552 13.20
DETERMINATION OF AGT, DRATION 552 13 21 DETERMINATION OF AH^ YD[ALION
553 13.22 COMPILATION OF ENTROPIES OF HYDRATION FROM AGFJ YDRATION AND
AH^ YDRATION 554 13.23 THERMODYNAMIC TRANSFER FUNCTIONS 554 13.24
SOLVATION OF NON-POLAR AND APOLAR MOLECULES - HYDROPHOBIC EFFECTS 554
13.25 EXPERIMENTAL TECHNIQUES FOR STUDYING HYDROPHOBIC HYDRATION 556
13.25.1 RESULTS OF METHODS (I) AND (II) 556 13.25.2 RESULTS OF
THERMODYNAMIC STUDIES 557 13.25.3 ENTROPIES OF HYDRATION AT INFINITE
DILUTION, AS 9 557 XVIII CONTENTS 13.25.4 AEV E OF SOLVATION AT INFINITE
DILUTION 557 13.25.5 THERMODYNAMIC TRANSFER FUNCTIONS 557 13.26
HYDROPHOBIC HYDRATION FOR LARGE CHARGED IONS 559 13.27 HYDROPHOBIC
INTERACTION 560 13.28 COMPUTER SIMULATIONS OF THE HYDROPHOBIC EFFECT 560
SUBJECT MATTER OF WORKED PROBLEMS 561 INDEX 563
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AN INTRODUCTION TO AQUEOUS ELECTROLYTE SOLUTIONS MARGARET ROBSON WRIGHT
FORMERLY OF ST ANDREWS UNIVERSITY, UK BICHTIHHIAU BICENTENNIAL JOHN
WILEY & SONS, LTD CONTENTS PREFACE PRELIMINARY CHAPTER GUIDANCE TO
STUDENT LIST OF SYMBOLS 1 CONCEPTS AND IDEAS: SETTING THE STAGE 1.1
ELECTROLYTE SOLUTIONS - WHAT ARE THEY? 1.2 IONS - SIMPLE CHARGED
PARTICLES OR NOT? 1.2.1 SIMPLE PROPERTIES OF IONS 1.2.2 MODIFICATIONS
NEEDED TO THESE SIMPLE IDEAS: A SUMMARY 1.3 THE SOLVENT: STRUCTURELESS
OR NOT? 1.4 THE MEDIUM: ITS STRUCTURE AND THE EFFECT OF IONS ON THIS
STRUCTURE 1.5 HOW CAN THESE IDEAS HELP IN UNDERSTANDING WHAT MIGHT
HAPPEN WHEN AN ION IS PUT INTO A SOLVENT? 1.6 ELECTROSTRICTION 1.7 IDEAL
AND NON-IDEAL SOLUTIONS - WHAT ARE THEY? 1.7.1 SOLUTE-SOLUTE
INTERACTIONS, I.E. ION-ION INTERACTIONS 1.7.2 SOLUTE-SOLVENT
INTERACTIONS, I.E. ION-SOLVENT INTERACTIONS-COLLECTIVELY KNOWN AS
SOLVATION 1.7.3 SOLVENT-SOLVENT INTERACTIONS 1.8 THE IDEAL ELECTROLYTE
SOLUTION 1.9 THE NON-IDEAL ELECTROLYTE SOLUTION 1.10 MACROSCOPIC
MANIFESTATION OF NON-IDEALITY 1.11 SPECIES PRESENT IN SOLUTION 1.12
FORMATION OF ION PAIRS FROM FREE IONS 1.12.1 CHARGE DISTRIBUTION ON THE
FREE ION AND THE ION PAIR 1.12.2 SIZE OF AN ION AND AN ION PAIR IN
SOLUTION 1.13 COMPLEXES FROM FREE IONS 1.14 COMPLEXES FROM IONS AND
UNCHARGED LIGANDS 1.15 CHELATES FROM FREE IONS 1.16 MICELLE FORMATION
FROM FREE IONS 1.17 MEASURING THE EQUILIBRIUM CONSTANT: GENERAL
CONSIDERATIONS 1.18 BASE-LINES FOR THEORETICAL PREDICTIONS ABOUT THE
BEHAVIOUR EXPECTED FOR A SOLUTION CONSISTING OF FREE IONS ONLY,
DEBYE-HUECKEL AND FUOSS-ONSAGER THEORIES AND THE USE OF BEER'S LAW 1.18.1
DEBYE-HUECKEL AND FUOSS-ONSAGER EQUATIONS 1.18.2 BEER'S LAW EQUATION VIII
CONTENTS 1.19 ULTRASONICS 26 1.20 POSSIBILITY THAT SPECIFIC EXPERIMENTAL
METHODS COULD DISTINGUISH BETWEEN THE VARIOUS TYPES OF ASSOCIATED
SPECIES 29 1.21 SOME EXAMPLES OF HOW CHEMISTS COULD GO ABOUT INFERRING
THE NATURE OF THE SPECIES PRESENT 29 2 THE CONCEPT OF CHEMICAL
EQUILIBRIUM: AN INTRODUCTION 33 2.1 IRREVERSIBLE AND REVERSIBLE
REACTIONS 34 2.2 COMPOSITION OF EQUILIBRIUM MIXTURES, AND THE APPROACH
TO EQUILIBRIUM 34 2.3 MEANING OF THE TERM 'POSITION OF EQUILIBRIUM' AND
FORMULATION OF THE EQUILIBRIUM CONSTANT 35 2.3.1 IDEAL AND NON-IDEAL
EQUILIBRIUM EXPRESSIONS 37 2.3.2 PREDICTION OF THE IDEAL ALGEBRAIC FORM
OF THE EQUILIBRIUM CONSTANT FROM THE STOICHIOMETRIC EQUATION 38 2.4
EQUILIBRIUM AND THE DIRECTION OF REACTION 39 2.5 A SEARCHING PROBLEM 44
2.6 THE POSITION OF EQUILIBRIUM 45 2.7 OTHER GENERALISATIONS ABOUT
EQUILIBRIUM 46 2.8 K AND PK 46 2.9 QUALITATIVE EXPERIMENTAL OBSERVATIONS
ON THE EFFECT OF TEMPERATURE ON THE EQUILIBRIUM CONSTANT, K 47 2.10
QUALITATIVE EXPERIMENTAL OBSERVATIONS ON THE EFFECT OF PRESSURE ON THE
EQUILIBRIUM CONSTANT, K 49 2.11 STOICHIOMETRIC RELATIONS 49 2.12 A
FURTHER RELATION ESSENTIAL TO THE DESCRIPTION OF ELECTROLYTE SOLUTIONS -
ELECTRICAL NEUTRALITY 50 3 ACIDS AND BASES: A FIRST APPROACH 53 3.1 A
QUALITATIVE DESCRIPTION OF ACID-BASE EQUILIBRIA 54 3.1.1 ACIDIC
BEHAVIOUR 54 3.1.2 BASIC BEHAVIOUR 55 3.2 THE SEIF IONISATION OF WATER
56 3.3 STRENG AND WEAK ACIDS AND BASES 56 3.4 A MORE DETAILED
DESCRIPTION OF ACID-BASE BEHAVIOUR 57 3.4.1 THE WEAK ACID, E.G. BENZOIC
ACID 57 3.4.2 THE WEAK BASE, E.G. METHYLAMINE 58 3.4.3 THE AMPHOTERIC
SOLVENT WATER 59 3.5 AMPHOLYTES 60 3.6 OTHER SITUATIONS WHERE ACID/BASE
BEHAVIOUR APPEARS 62 3.6.1 SALTS AND BUFFERS 62 3.7 FORMULATION OF
EQUILIBRIUM CONSTANTS IN ACID-BASE EQUILIBRIA 66 3.8 MAGNITUDES OF
EQUILIBRIUM CONSTANTS 67 3.9 THE SEIF IONISATION OF WATER 67 3.10
RELATIONS BETWEEN K A AND K B : EXPRESSIONS FOR AN ACID AND ITS
CONJUGATE BASE AND FOR A BASE AND ITS CONJUGATE ACID 68 3.11
STOICHIOMETRIC ARGUMENTS IN EQUILIBRIA CALCULATIONS 70 3.12 PROCEDURE
FOR CALCULATIONS ON EQUILIBRIA 71 CONTENTS IX 4 EQUILIBRIUM CALCULATIONS
FOR ACIDS AND BASES 73 4.1 CALCULATIONS ON EQUILIBRIA: WEAK ACIDS 74
4.1.1 POSSIBLE APPROXIMATIONS FOR THE WEAK ACID 75 4.1.2 THE WEAK ACID
WHERE BOTH APPROXIMATIONS CAN BE MADE 76 4.1.3 THE WEAK ACID WHERE THERE
IS EXTENSIVE IONISATION AND APPROXIMATION 1 IS INVALID 77 4.1.4 THE WEAK
ACID IS SUFFICIENTLY WEAK SO THAT THE SEIF IONISATION OF WATER CANNOT BE
IGNORED AND APPROXIMATION 2 IS INVALID 78 4.1.5 ELECTRICAL NEUTRALITY 80
4.2 SOME WORKED EXAMPLES 80 4.3 CALCULATIONS ON EQUILIBRIA: WEAK BASES
85 4.3.1 POSSIBLE APPROXIMATIONS FOR THE WEAK BASE 86 4.3.2 THE WEAK
BASE WHERE BOTH APPROXIMATIONS CAN BE MADE 88 4.3.3 THE WEAK BASE WHERE
THERE IS EXTENSIVE PROTONATION AND APPROXIMATION 1 IS INVALID 88 4.3.4
THE WEAK BASE IS SUFFICIENTLY WEAK SO THAT THE SEIF IONISATION OF WATER
CANNOT BE IGNORED AND APPROXIMATION 2 IS INVALID 89 4.4 SOME
ILLUSTRATIVE PROBLEMS 90 4.5 FRACTION IONISED AND FRACTION NOT IONISED
FOR A WEAK ACID; FRACTION PROTONATED AND FRACTION NOT PROTONATED FOR A
WEAK BASE 97 4.6 DEPENDENCE OF THE FRACTION IONISED ON PK A AND PH 98
4.6.1 MAXIMUM % IONISED FOR A WEAK ACID AND MAXIMUM % PROTONATED FOR A
WEAK BASE 100 4.7. THE EFFECT OF DILUTION ON THE FRACTION IONISED FOR
WEAK ACIDS LYING ROUGHLY IN THE RAENGE: P/F A = 4.0 TO 10.0 101 4.8
REASSESSMENT OF THE TWO APPROXIMATIONS: A RIGOROUS EXPRESSION FOR A WEAK
ACID 103 4.9 CONJUGATE ACIDS OF WEAK BASES 104 4.10 WEAK BASES 105 4.11
EFFECT OF NON-IDEALITY 105 5 EQUILIBRIUM CALCULATIONS FOR SALTS AND
BUFFERS 107 5.1 AQUEOUS SOLUTIONS OF SALTS 108 5.2 SALTS OF STRONG
ACIDS/STRONG BASES 108 5.3 SALTS OF WEAK ACIDS/STRONG BASES 108 5.4
SALTS OF WEAK BASES/STRONG ACIDS 109 5.4.1 A MORE RIGOROUS TREATMENT OF
WORKED PROBLEM 5.1 112 5.5 SALTS OF WEAK ACIDS/WEAK BASES 117 5.6 BUFFER
SOLUTIONS 119 5.6.1 BUFFER: WEAK ACID PLUS ITS SALT WITH A STRONG BASE
120 5.6.2 THE RIGOROUS CALCULATION FOR THE BUFFER OF A WEAK ACID PLUS
ITS SALT WITH A STRONG BASE 122 5.6.3 BUFFER: WEAK BASE PLUS ITS SALT
WITH A STRONG ACID 129 5.6.4 THE RIGOROUS CALCULATION FOR THE BUFFER OF
A WEAK BASE PLUS ITS SALT WITH A STRONG ACID 131 5.6.5 EFFECT OF
DILUTION ON BUFFERING CAPACITY 134 5.6.6 EFFECT OF ADDITION OF H 3 0 +
(AQ) OR OH~(AQ) ON THE PH OF A BUFFER 134 5.6.7 EFFECT OF ADDITION OF H
3 0 + (AQ) OR OH"(AQ) ON THE PH OF A WEAK ACID ON ITS OWN 135 5.6.8
BUFFER CAPACITY 135 X CONTENTS 6 NEUTRALISATION AND PH TITRATION CURVES
139 6.1 NEUTRALISATION 140 6.2 PH TITRATION CURVES 141 6.2.1
NEUTRALISATION OF A STRONG ACID BY A STRONG BASE, E.G. HCL(AQ) WITH
NAOH(AQ) 141 6.2.2 NEUTRALISATION OF A STRONG BASE BY A STRONG ACID,
E.G. NAOH(AQ) WITH HCL(AQ) 145 6.2.3 NEUTRALISATION OF A WEAK ACID BY A
STRONG BASE, E.G. CH 3 COOH(AQ) WITH NAOH(AQ) 145 6.2.4 NEUTRALISATION
OF A WEAK BASE BY A STRONG ACID, E.G. NH 3 (AQ) WITH HCL(AQ) 148 6.3
INTERPRETATION OF PH TITRATION CURVES 149 6.4 POLYBASIC ACIDS 153 6.4.1
ANALYSIS OF POLYBASIC PH TITRATION CURVES 156 6.4.2 A DIBASIC ACID WITH
TWO APPARENTLY SEPARATED PA" VALUES, E.G. MALONIC ACID 157 6.5 PH
TITRATIONS OF DIBASIC ACIDS: THE CALCULATIONS 161 6.5.1 THE BEGINNING OF
THE TITRATION 162 6.5.2 THE FIRST EQUIVALENCE POINT 162 6.5.3 THE FIRST
BUFFER REGION 164 6.5.4 ANALYSIS OF THE FIRST BUFFER REGION 164 6.5.5
THE SECOND EQUIVALENCE POINT 165 6.5.6 THE SECOND BUFFER REGION 166 6.6
TRIBASIC ACIDS 166 6.6.1 ANALYSIS OF THE TITRATION CURVE 168 6.6.2 AN
IMPORTANT THOUGHT 168 6.7 AMPHOLYTES 168 6.7.1 ANALYSIS OF THE TITRATION
CURVES FOR ALIPHATIC AND AROMATIC AMINO ACIDS, AND AMINO PHENOLS 173 7
ION PAIRING, COMPLEX FORMATION AND SOLUBILITIES 177 7.1 ION PAIR
FORMATION 178 7.2 COMPLEX FORMATION 184 7.2.1 FRACTIONS ASSOCIATED 186
7.2.2 MEAN NUMBER OF LIGANDS BOUND 187 7.2.3 EQUILIBRIA CALCULATIONS 187
7.2.4 DETERMINATION OF SS L , SS 2 , FROM THE DEPENDENCE OF ACTUAL 188
7.2.5 DETERMINATION OF SS L , SS 2 , FROM THE DEPENDENCE OF N ON [L]
ACTUAL 188 7.3 SOLUBILITIES OF SPANNGLY SOLUBLE SALTS 195 7.3.1
FORMULATION OF THE SOLUBILITY PRODUCT IN TERMS OF THE SOLUBILITY 195
7.3.2 SOLUBILITY RELATIONS WHEN A SPARINGLY SOLUBLE SALT IS DISSOLVED IN
A SOLUTION CONTAINING ONE OF THE IONS OF THE SOLID: THE COMMON ION
EFFECT 196 7.3.3 POSSIBILITY OR OTHERWISE OF PRECIPITATION OF A
SPARINGLY SOLUBLE SALT WHEN TWO SOLUTIONS CONTAINING THE RELEVANT IONS
ARE MIXED 198 7.3.4 THE EFFECT OF COMPLEXING ON SOLUBILITY EQUILIBRIA
203 7.3.5 ANOTHER INTERESTING EXAMPLE 205 7.3.6 FURTHER EXAMPLES OF THE
EFFECT OF COMPLEXING ON SOLUBILITY 208 8 PRACTICAL APPLICATIONS OF
THERMODYNAMICS FOR ELECTROLYTE SOLUTIONS 215 8.1 THE FIRST LAW OF
THERMODYNAMICS 8.2 THE ENTHALPY, H 216 217 CONTENTS XI 8.3 THE
REVERSIBLE PROCESS 217 8.4 THE SECOND LAW OF THERMODYNAMICS 217 8.5
RELATIONS BETWEEN Q, W AND FHERMODYNAMIC QUANTITIES 218 8.6 SOME OTHER
DEFINITIONS OF IMPORTANT THERMODYNAMIC FUNCTIONS 218 8.7 A VERY
IMPORTANT EQUATION WHICH CAN NOW BE DERIVED 218 8.8 RELATION OF EMFS TO
THERMODYNAMIC QUANTITIES 219 8.9 THE THERMODYNAMIC CRITERION OF
EQUILIBRIUM 220 8.10 SOME FURTHER DEFINITIONS: STANDARD STATES AND
STANDARD VALUES 221 8.11 THE CHEMICAL POTENTIAL OF A SUBSTANCE 221 8.12
CRITERION OF EQUILIBRIUM IN TERMS OF CHEMICAL POTENTIALS 222 8.13
CHEMICAL POTENTIALS FOR SOLIDS, LIQUIDS, GASES AND SOLUTES 223 8.14 USE
OF THE THERMODYNAMIC CRITERION OF EQUILIBRIUM IN THE DERIVATION OF THE
ALGEBRAIC FORM OF THE EQUILIBRIUM CONSTANT 224 8.15 THE TEMPERATURE
DEPENDENCE OF AEFF 9 230 8.16 THE DEPENDENCE OF THE EQUILIBRIUM CONSTANT,
K, ON TEMPERATURE 231 8.16.1 CALCULATION OF AH 9 FROM TWO VALUES OF K
231 8.16.2 DETERMINATION OF AH E FROM VALUES OF K OVER A RAENGE OF
TEMPERATURES 231 8.17 THE MICROSCOPIC STATISTICAL INTERPRETATION OF
ENTROPY 236 8.17.1 THE STATISTICAL MECHANICAL INTERPRETATION OF ENTROPY
236 8.17.2 THE ORDER/DISORDER INTERPRETATION OF ENTROPY 236 8.18
DEPENDENCE OF K ON PRESSURE 237 8.19 DEPENDENCE OF AG" ON TEMPERATURE
242 8.20 DEPENDENCE OF AS* ON TEMPERATURE 242 8.21 THE NON-IDEAL CASE
244 8.21.1 NON-IDEALITY IN ELECTROLYTE SOLUTIONS 244 8.21.2 THE IONIC
STRENGTH AND NON-IDEALITY 244 8.22 CHEMICAL POTENTIALS AND MEAN ACTIVITY
COEFFICIENTS 247 8.23 A GENERALISATION 251 8.24 CORRECTIONS FOR
NON-IDEALITY FOR EXPERIMENTAL EQUILIBRIUM CONSTANTS 258 8.24.1
DEPENDENCE OF EQUILIBRIUM CONSTANTS ON IONIC STRENGTH 258 8.25 SOME
SPECIFIC EXAMPLES OF THE DEPENDENCE OF THE EQUILIBRIUM CONSTANT ON IONIC
STRENGTH 263 8.25.1 THE CASE OF ACID/BASE EQUILIBRIA 263 8.25.2 THE WEAK
ACID WHERE BOTH APPROXIMATIONS ARE VALID 263 8.25.3 THE WEAK ACID WHERE
THERE IS EXTENSIVE IONISATION 266 8.26 GRAPHICAL CORRECTIONS FOR
NON-IDEALITY 270 8.27 COMPARISON OF NON-GRAPHICAL AND GRAPHICAL METHODS
OF CORRECTING FOR NON-IDEALITY 270 8.28 DEPENDENCE OF FRACTION IONISED
AND FRACTIION PROTONATED ON IONIC STRENGTH 271 8.29 THERMODYNAMIC
QUANTITIES AND THE EFFECT OF NON-IDEALITY 271 9 ELECTROCHEMICAL CELLS
AND EMFS 273 9.1 CHEMICAL ASPECTS OF THE PASSAGE OF AN ELECTRIC CURRENT
THROUGH A CONDUCTING MEDIUM 274 9.2 ELECTROLYSIS 275 9.2.1 QUANTITATIVE
ASPECTS OF ELECTROLYSIS 278 9.2.2 A SUMMARY OF ELECTROLYSIS 279 9.3
ELECTROCHEMICAL CELLS 280 9.3.1 THE ELECTROCHEMICAL CELL OPERATING
IRREVERSIBLY OR REVERSIBLY 280 9.3.2 POSSIBLE SOURCES OF CONFUSION 280
9.3.3 CELLS USED AS BATTERIES AS A SOURCE OF CURRENT, I.E. OPERATING
IRREVERSIBLY 280 9.3.4 CELLS OPERATING REVERSIBLY AND IRREVERSIBLY 284
9.3.5 CONDITIONS FOR REVERSIBILITY OF CELLS 285 XII CONTENTS 9.4 SOME
EXAMPLES OF ELECTRODES USED IN ELECTROCHEMICAL CELLS 285 9.4.1 GAS
ELECTRODES 285 9.4.2 METAL ELECTRODE DIPPING INTO AN AQUEOUS SOLUTION OF
ITS IONS 286 9.4.3 METAL COATED WITH A SPARINGLY SOLUBLE COMPOUND OF THE
METAL DIPPING INTO AN AQUEOUS SOLUTION CONTAINING THE ANION OF THE
SPARINGLY SOLUBLE COMPOUND 287 9.4.4 THE REDOX ELECTRODE 288 9.4.5
REACTIONS OCCURRING AT THE ELECTRODES IN A REDOX CELL 288 9.4.6 THE
AMALGAM ELECTRODE 290 9.4.7 GLASS ELECTRODES 292 9.5 COMBINATION OF
ELECTRODES TO MAKE AN ELECTROCHEMICAL CELL 292 9.6 CONVENTIONS FOR
WRITING DOWN THE ELECTROCHEMICAL CELL 293 9.6.1 USE OF A VOLTMETER TO
DETERMINE THE POLARITY OF THE ELECTRODES 294 9.7 ONE VERY IMPORTANT
POINT: CELLS CORRESPONDING TO A 'NET CHEMICAL REACTION' 298 9.8 LIQUID
JUNCTIONS IN ELECTROCHEMICAL CELLS 298 9.8.1 CELLS WITHOUT LIQUID
JUNCTION 298 9.8.2 CELLS WITH LIQUID JUNCTION 299 9.8.3 TYPES OF LIQUID
JUNCTIONS 299 9.8.4 CELLS WITH A LIQUID JUNCTION CONSISTING OF A NARROW
TUBE: A CELL WITH TRANSFERENCE 299 9.8.5 CELLS WITH A POROUS POT
SEPARATING TWO SOLUTIONS: A CELL WITH TRANSFERENCE 301 9.8.6 CELLS WITH
A SALT BRIDGE: CELLS WITHOUT TRANSFERENCE 302 9.9 EXPERIMENTAL
DETERMINATION OF THE DIRECTION OF FLOW OF THE ELECTRONS, AND MEASUREMENT
OF THE POTENTIAL DIFFERENCE 305 9.10 ELECTRODE POTENTIALS 305 9.10.1
REDOX POTENTIALS 305 9.10.2 ELECTRODE POTENTIALS FOR STANDARD AND
NON-STANDARD CONDITIONS 306 9.11 STANDARD ELECTRODE POTENTIALS 306
9.11.1 STANDARD REDOX POTENTIALS 307 9.12 POTENTIAL DIFFERENCE,
ELECTRICAL WORK DONE AND AG FOR THE CELL REACTION 308 9.12.1
THERMODYNAMIC QUANTITIES IN ELECTROCHEMISTRY: RELATION OF AG TO E 309
9.12.2 THERMODYNAMIC QUANTITIES IN ELECTROCHEMISTRY: EFFECT OF
TEMPERATURE ON EMF 310 9.13 AG FOR THE CELL PROCESS: THE NERNST EQUATION
312 9.13.1 CORRECTIONS FOR NON-IDEALITY 313 9.13.2 A FURTHER EXAMPLE
DEDUCING THE NERNST EQUATION AND THE DEPENDENCE OF EMF ON IONIC STRENGTH
314 9.14 METHODS OF EXPRESSING CONCENTRATION 315 9.15 CALCULATION OF
STANDARD EMFS VALUES FOR CELLS AND AG E VALUES FOR REACTIONS 317 9.16
DETERMINATION OF PH 320 9.17 DETERMINATION OF EQUILIBNUM CONSTANTS FOR
REACTIONS WHERE K IS EITHER VERY LARGE OR VERY SMALL 322 9.18 USE OF
CONCENTRATION CELLS 324 9.19 'CONCEALED' CONCENTRATION CELLS AND SIMILAR
CELLS 326 9.20 DETERMINATION OF EQUILIBRIUM CONSTANTS AND PK VALUES FOR
REACTIONS WHICH ARE NOT DIRECTLY THAT FOR THE CELL REACTION 328 9.20.1
DETERMINATION OF PK VALUES FOR THE IONISATION OF WEAK ACIDS AND WEAK
BASES, AND FOR THE SEIF IONISATION OF H 2 0(1) 328 9.20.2 SOLUBILITY
PRODUCTS 333 9.20.3 A FURTHER USE OF CELLS TO GAIN INSIGHT INTO WHAT IS
OCCURRING IN AN ELECTRODE COMPARTMENT - ION PAIR FORMATION 334 CONTENTS
XIII 9.20.4 COMPLEX FORMATION 336 9.20.5 USE OF CELLS TO DETERMINE MEAN
ACTIVITY COEFFICIENTS AND THEIR DEPENDENCE ON IONIC STRENGTH 337 9.21
USE OF CONCENTRATION CELLS WITH AND WITHOUT LIQUID JUNCTIONS IN THE
DETERMINATION OF TRANSPORT NUMBERS 343 9.21.1 USE OF CELLS WITH AND
WITHOUT TRANSFERENCE IN DETERMINATION OF THE TRANSPORT NUMBERS OF LARGE
IONS 347 10 CONCEPTS AND THEORY OF NON-IDEALITY 349 10.1 EVIDENCE FOR
NON-IDEALITY IN ELECTROLYTE SOLUTIONS 350 10.2 THE PROBLEM THEORETICALLY
351 10.3 FEATURES OF THE SIMPLE DEBYE-HUECKEL MODEL 351 10.3.1 NAIVETY OF
THE DEBYE-HUECKEL THEORY 353 10.4 ASPECTS OF ELECTROSTATICS WHICH ARE
NECESSARY FOR AN UNDERSTANDING OF THE PROCEDURES USED IN THE
DEBYE-HUECKEL THEORY AND CONDUCTANCE THEORY 353 10.4.1 THE ELECTRIC
FIELD, FORCE OF INTERACTION AND WORK DONE 353 10.4.2 COULOMB'S LAW 355
10.4.3 WORK DONE AND POTENTIAL ENERGY OF ELECTROSTATIC INTERACTIONS 355
10.4.4 THE RELATION BETWEEN THE FORCES OF INTERACTION BETWEEN TWO
CHARGES AND THE ELECTRIC FIELDS ASSOCIATED WITH EACH OF THEM 358 10.4.5
THE RELATION BETWEEN THE ELECTROSTATIC POTENTIAL ENERGY AND THE
ELECTROSTATIC POTENTIAL 359 10.4.6 RELATION BETWEEN THE ELECTRIC FIELD
AND THE ELECTROSTATIC POTENTIAL 359 10.5 THE IONIC ATMOSPHERE IN MORE
DETAIL 360 10.5.1 A SUMMARY 362 10.6 DERIVATION OF THE DEBYE-HUECKEL
THEORY FROM THE SIMPLE DEBYE-HUECKEL MODEL 363 10.6.1 STEP 1 STATING THE
PROBLEM 363 10.6.2 STEP 2 THE PROBLEM IS TO CALCULATE V,* IN TERMS OF
OTHER CALCULABLE POTENTIALS, BUT WHAT ARE THESE? 364 10.6.3 STEP 3 THE
QUESTION NOW IS: IS THERE ANYTHING IN PHYSICS, THAT IS, IN ELECTROSTATIC
THEORY, WHICH WOULD ENABLE THIS TO BE DONE? 365 10.6.4 TRANSLATING THE
POISSON EQUATION DIRECTLY TO THE CASE OF AN ELECTROLYTE IN SOLUTION 365
10.6.5 STEP 4 HOW CAN THE DISTRIBUTION OF THE DISCRETE IONS IN THE IONIC
ATMOSPHERE OF THE /-ION BE DESCRIBED? 366 10.6.6 THE TWO BASIC EQUATIONS
367 10.6.7 STEP 5 THE PROBLEM IS TO COMBINE THE POISSON EQUATION WITH
THE MAXWELL-BOLTZMANN EQUATION - HOW CAN THIS BE DONE? 368 10.6.8 STEP 6
COMBINING THE POISSON AND MAXWELL-BOLTZMANN EQUATIONS 370 10.6.9 STEP 7
SOLVING THE POISSON-BOLTZMANN EQUATION 370 10.6.10 EXPANSION AND
APPROXIMATION OF THE POISSON-BOLTZMANN EQUATION TO ONE NON-ZERO TERM
ONLY 371 10.6.11 THE IONIC STRENGTH 372 10.6.12 THE NEXT STEP IS TO
SOLVE THE TRUNCATED POISSON-BOLTZMANN EQUATION 372 10.6.13 STEP 8
CALCULATION OF THE POTENTIAL AT THE SURFACE OF THE CENTRAL J-'ION DUE TO
THE IONIC ATMOSPHERE, AND THENCE FINDING THE ELECTROSTATIC ENERGY OF
INTERACTION BETWEEN AN ION AND ITS IONIC ATMOSPHERE 373 10.6.14
CALCULATION OF IJRJ BY SUBSTITUTION OF R = A IN EQUATION (10.48) 374
10.6.15 STEP 9 THE PROBLEM IS TO CALCULATE THE MEAN IONIC ACTIVITY
COEFFICIENT, Y 375 10.6.16 CONSTANTS APPEARING IN THE DEBYE-HUECKEL
EXPRESSION 377 10.6.17 THE PHYSICAL SIGNIFICANCE OF K~ 1 AND PJ 377 10.7
THE DEBYE-HUECKEL LIMITING LAW 380 10.8 SHORTCOMINGS OF THE DEBYE-HUECKEL
MODEL 382 XIV CONTENTS 10.8.1 STRENG ELECTROLYTES ARE COMPLETELY
DISSOCIATED 382 10.8.2 RANDOM MOTION IS NOT ATTAINED 382 10.8.3
NON-IDEALITY RESULTS FROM COULOMBIC INTERACTIONS BETWEEN IONS 382 10.8.4
IONS ARE SPHERICALLY SYMMETRICAL AND ARE UNPOLARISABLE 383 10.8.5 THE
SOLVENT IS A STRUCTURELESS DIELECTRIC 383 10.8.6 ELECTROSTRICTION IS
IGNORED 383 10.8.7 CONCEPT OF A SMEARED OUT SPHERICALLY SYMMETRICAL
CHARGE DENSITY 384 10.9 SHORTCOMINGS IN THE MATHEMATICAL DERIVATION OF
THE THEORY 384 10.10 MODIFICATIONS AND FURTHER DEVELOPMENTS OF THE
THEORY 385 10.10.1 EMPIRICAL METHODS 385 10.10.2 EMPIRICAL EXTENSION
USING A TERM. LINEAR IN IONIC STRENGTH 388 10.11 EVIDENCE FOR ION
ASSOCIATION FROM DEBYE-HUECKEL PLOTS 391 10.11.1 AN EXPLANATION OF THE
STATEMENT THAT IF AN ELECTROLYTE IS ASSOCIATED THEN THE GRAPH OF LOG 10
Y\S.Y/L/L + BAY/L WILL APPROACH THE DEBYE-HUECKEL SLOPE FROM BELOW 391
10.11.2 UNKNOWN PARAMETERS IN THE DEBYE-HUECKEL EXTENDED EQUATION WHEN
ASSOCIATION OCCURS 393 10.12 THE BJERRUM THEORY OF ION ASSOCIATION 393
10.12.1 THE GRAPH AT THE HEART OF THE BJERRUM THEORY 394 10.12.2 THE
THEORETICAL EXPRESSION FOR THE ASSOCIATION CONSTANT FOR SYMMETRICAL
ELECTROLYTES 396 10.12.3 CALCULATION OF SS FROM THE BJERRUM THEORY 396
10.12.4 EXTENSION TO ACCOUNT FOR NON-IDEALITY 399 10.12.5 CRITIQUE OF
BJERRUM'S THEORY 400 10.12.6 FUOSS ION PAIRS AND OTHERS 400 10.13
EXTENSIONS TO HIGHER CONCENTRATIONS 401 10.13.1 GUGGENHEIM^ NUMERICAL
INTEGRATION 401 10.13.2 EXTENSIONS TO HIGHER CONCENTRATIONS:
DAVIES'EQUATION 402 10.14 MODERN DEVELOPMENTS IN ELECTROLYTE THEORY 402
10.15 COMPUTER SIMULATIONS 402 10.15.1 MONTE CARLO CALCULATIONS 403
10.15.2 MOLECULAR DYNAMICS 404 10.16 FURTHER DEVELOPMENTS TO THE
DEBYE-HUECKEL THEORY 404 10.16.1 DEVELOPMENTS FROM THE GURNEY CONCEPT OF
THE CO-SPHERE: A NEW MODEL 405 10.16.2 THE UNMODIFIED DEBYE-HUECKEL
THEORY 406 10.16.3 A FIRST MODIFICATION TO THE SIMPLE DEBYE-HUECKEL MODEL
406 10.16.4 A LESS SIMPLE GURNEY MODEL: A SECOND MODIFICATION TO THE
DEBYE-HUECKEL MODEL 407 10.16.5 A LESS SIMPLE GURNEY MODEL: A THIRD
MODIFICATION TO THE DEBYE-HUECKEL MODEL 408 10.16.6 A FURTHER
MODIFICATION INVOLVING A 'CAVITY' TERM 408 10.16.7 USE OF THESE IDEAS IN
PRODUCING A NEW TREATMENT 409 10.17 STATISTICAL MECHANICS AND
DISTRIBUTION FUNCTIONS 409 10.17.1 THE SIMPLEST SITUATION: THE RADIAL
DISTRIBUTION FUNCTION OF THE DEBYE-HUECKEL THEORY 410 10.17.2 MORE
COMPLEX DISTRIBUTION FUNCTIONS 411 10.17.3 CONTRIBUTIONS TO THE TOTAL
POTENTIAL ENERGY OF THE ELECTROLYTE SOLUTION 413 10.18 APPLICATION OF
DISTRIBUTION FUNCTIONS TO THE DETERMINATION OF ACTIVITY COEFSSCIENTS DUE
TO KIRKWOOD; YVON; BORN AND GREEN; AND BOGOLYUBOV 414 10.18.1 USING
DISTRIBUTION FUNCTIONS TO FORMULATE A NEW QUANTITY G 415 10.19 A FEW
EXAMPLES OF RESULTS FROM DISTRIBUTION FUNCTIONS 417 10.20
'BORN-OPPENHEIMER LEVEL' MODEIS 419 10.21 LATTICE CALCULATIONS FOR
CONCENTRATED SOLUTIONS 419 CONTENTS XV 11 CONDUCTANCE: THE IDEAL CASE
421 11.1 ASPECTS OF PHYSICS RELEVANT TO THE EXPERIMENTAL STUDY OF
CONDUCTANCE IN SOLUTION 422 11.1.1 OHM'SLAW 422 11.1.2 THE ELECTRIC
FLELD 424 11.2 EXPERIMENTAL MEASUREMENT OF THE CONDUCTIVITY OF A
SOLUTION 425 11.3 CORRECTIONS TO THE OBSERVED CONDUCTIVITY TO ACCOUNT
FOR THE SEIF IONISATION OF WATER 427 11.4 CONDUCTIVITIES AND MOLAR
CONDUCTIVITIES: THE IDEAL CASE 428 11.5 THE PHYSICAL SIGNIFICANCE OF THE
MOLAR CONDUCTIVITY, A 431 11.6 DEPENDENCE OF MOLAR CONDUCTIVITY ON
CONCENTRATION FOR A STRENG ELECTROLYTE: THE IDEAL CASE 432 11.7
DEPENDENCE OF MOLAR CONDUCTIVITY ON CONCENTRATION FOR A WEAK
ELECTROLYTE: THE IDEAL CASE 433 11.8 DETERMINATION OF A 436 11.9
SIMULTANEOUS DETERMINATION OF K AND A 438 11.10 PROBLEMS WHEN AN ACID
OR BASE IS SO WEAK THAT IT IS NEVER 100% IONISED, EVEN IN VERY, VERY
DILUTE SOLUTION 441 11.11 CONTRIBUTIONS TO THE CONDUCTIVITY OF AN
ELECTROLYTE SOLUTION FROM THE CATION AND THE ANION OF THE ELECTROLYTE
441 11.12 CONTRIBUTIONS TO THE MOLAR CONDUCTIVITY FROM THE INDIVIDUAL
IONS 442 11.13 KOHLRAUSCH'S LAW OF INDEPENDENT IONIC MOBILITIES 443
11.14 ANALYSIS OF THE USE OF CONDUCTANCE MEASUREMENTS FOR DETERMINATION
OF PAF A S FOR VERY WEAK ACIDS AND PAET B S FOR VERY WEAK BASES: THE
BASIC QUANTITIES INVOLVED 447 11.14.1 ANALYSIS OF THE USE OF CONDUCTANCE
MEASUREMENTS FOR DETERMINATION OF PJF A S FOR VERY WEAK ACIDS AND P# B S
FOR VERY WEAK BASES: THE ARGUMENT 449 11.14.2 APPLICATION OF THE ABOVE
ANALYSIS TO THE CASES OF WEAK ACIDS AND WEAK BASES FOR WHICH THE
RELATION A = A/A IS TAKEN TO BE VALID AND A * 1 AS C * 0 450 11.15
USE OF CONDUCTANCE MEASUREMENTS IN DETERMINING SOLUBILITY PRODUCTS FOR
SPARINGLY SOLUBLE SALTS 451 11.16 TRANSPORT NUMBERS 453 11.17 IONIC
MOBILITIES 457 11.18 ABNORMAL MOBILITY AND IONIC MOLAR CONDUCTIVITY OF H
3 0 + (AQ) 463 11.19 MEASUREMENT OF TRANSPORT NUMBERS 464 11.19.1 THE
HITTORF METHOD FOR DETERMINING TRANSPORT NUMBERS 465 11.19.2 THE MOVING
BOUNDARY METHOD 468 11.19.3 THE ARGUMENT FOR THE UNSYMMETRICAL
ELECTROLYTE 470 11.19.4 THE FUNDAMENTAL BASIS OF THE MOVING BOUNDARY
METHOD 470 11.19.5 SUMMARY OF THE USE MADE OF TRANSPORT NUMBERS AND
MOBILITIES 473 12 THEORIES OF CONDUCTANCE: THE NON-IDEAL CASE FOR
SYMMETRICAL ELECTROLYTES 475 12.1 THE RELAXATION EFFECT 476 12.1.1
APPROXIMATE ESTIMATE OF THE RELAXATION TIME FOR THE IONIC ATMOSPHERE 477
12.1.2 CONFIRMATION OF THE EXISTENCE OF THE IONIC ATMOSPHERE 478 12.1.3
THE RELAXATION TIME AND THE DEBYE-FALKENHAGEN EFFECT, I.E. THE EFFECT OF
HIGH FREQUENCIES 478 12.1.4 THE RELAXATION TIME AND THE WIEN EFFECT,
I.E. THE EFFECT OF VERY LARGE FIELDS 479 12.2 THE ELECTROPHORETIC EFFECT
480 XVI CONTENTS 12.3 CONDUCTANCE EQUATIONS FOR STRONG ELECTROLYTES
TAKING NON-IDEALITY INTO CONSIDERATION: EARLY CONDUCTANCE THEORY 480
12.3.1 QUALITATIVE ASPECTS OF THE DERIVATION OF THE DEBYE-HUECKEL-ONSAGER
1927 EQUATION 481 12.4 A SIMPLE TREATMENT OF THE DERIVATION OF THE
DEBYE-HUECKEL-ONSAGER EQUATION 1927 FOR SYMMETNCAL ELECTROLYTES 483
12.4.1 STEP 1 STATING THE PROBLEM 483 12.4.2 STEP 2 THE CONTRIBUTION AT
INFINITE DILUTION RESULTING FROM A BALANCE OF THE EFFECTS OF THE FIELD
AND THE FRICTIONAL FORCE ON THE MOVING ION 483 12.4.3 STEP 3 THE
CONTRIBUTION FROM THE ELECTROPHORETIC EFFECT 484 12.4.4 STEP 4 THE
CONTRIBUTION FROM THE RELAXATION EFFECT 485 12.4.5 STEP 5 THE FINAL STEP
IN ARRIVING AT THE CONDUCTANCE EQUATION FOR SYMMETNCAL ELECTROLYTES 486
12.5 THE FUOSS-ONSAGER EQUATION 1932 488 12.6 USE OF THE
DEBYE-HUECKEL-ONSAGER EQUATION FOR SYMMETNCAL STRONG ELECTROLYTES WHICH
ARE FULLY DISSOCIATED 488 12.6.1 ASSESSMENT OF EXPERIMENTAL RESULTS FOR
1-1, 1-2 AND 1-3 ELECTROLYTES IN CONCENTRATION RANGES WHERE THEY ARE
EXPECTED TO BE FULLY DISSOCIATED 489 12.7 ELECTROLYTES SHOWING ION
PAIRING AND WEAK ELECTROLYTES WHICH ARE NOT FULLY DISSOCIATED 490 12.7.1
CALCULATION OF A , A AND K ISSOC FOR WEAK ELECTROLYTES AND ION PAIRS
USING THE DEBYE-HUECKEL-ONSAGER EQUATION 492 12.8 EMPIRICAL EXTENSIONS TO
THE DEBYE-HUECKEL-ONSAGER 1927 EQUATION 492 12.9 MODERN CONDUCTANCE
THEORIES FOR SYMMETRICAL ELECTROLYTES - POST 1950 493 12.10
FUOSS-ONSAGER 1957: CONDUCTANCE EQUATION FOR SYMMETRICAL ELECTROLYTES
493 12.10.1 USE OF THE FUOSS-ONSAGER EQUATION TO DETERMINE A AND A 498
12.10.2 IMPLICATIONS OF THE FUOSS-ONSAGER EQUATION FOR UNASSOCIATED
SYMMETRICAL ELECTROLYTES 498 12.11 A SIMPLE ILLUSTRATION OF THE EFFECTS
OF ION ASSOCIATION ON EXPERIMENTAL CONDUCTANCE CURVES 500 12.12 THE
FUOSS-ONSAGER EQUATION FOR ASSOCIATED ELECTROLYTES 500 12.12.1
DETERMINATION OF A , ^ASSOCIATION AND A USIN G THE FUOSS-ONSAGER
EQUATION FOR ASSOCIATED ELECTROLYTES 503 12.13 RANGE OF APPLICABILITY OF
FUOSS-ONSAGER 1957 CONDUCTANCE EQUATION FOR SYMMETRICAL ELECTROLYTES 503
12.14 LIMITATIONS OF THE TREATMENT GIVEN BY THE 1957 FUOSS-ONSAGER
CONDUCTANCE EQUATION FOR SYMMETRICAL ELECTROLYTES 504 12.15 MANIPULATION
OF THE 1957 FUOSS-ONSAGER EQUATION, AND LATER MODIFICATIONS BY FUOSS AND
OTHER WORKERS 505 12.16 CONDUCTANCE STUDIES OVER A RAENGE OF RELATIVE
PERMITTIVITIES 506 12.17 FUOSS ET AL. 1978 AND LATER 506 12.17.1 THE
FRACTION OF IONS WHICH ARE FREE TO CONDUCT THE CURRENT 511 12.17.2 THE
FUOSS 1978 EQUATION FOR ASSOCIATED SYMMETRICAL ELECTROLYTES 512 APPENDIX
1 . 5 1 2 APPENDEX 2 515 13 SOLVATION 517 13.1 CLASSIFICATION OF
SOLUTES: A RESUME 518 13.2 CLASSIFICATION OF SOLVENTS 518 13.3 SOLVENT
STRUCTURE 519 13.3.1 LIQUID WATER AS A SOLVENT 519 CONTENTS XVII 13.3.2
H-BONDING IN WATER 519 13.4 THE EXPERIMENTAL STUDY OF THE STRUCTURE OF
WATER 522 13.5 DIFFRACTION STUDIES 522 13.5.1 DETERMINATION OF THE
NUMBER OF H 2 0 MOLECULES CORRESPONDING TO EACH PEAK AND THE
THREE-DIMENSIONAL ARRANGEMENT CORRESPONDING TO EACH PEAK 524 13.5.2
RESULTS OF DIFFRACTION STUDIES: THE STRUCTURE OF LIQUID WATER 525 13.6
THE THEORETICAL APPROACH TO THE RADIAL DISTRIBUTION FUNCTION FOR A
LIQUID 526 13.7 AQUEOUS SOLUTIONS OF ELECTROLYTES 526 13.7.1 EFFECT OF
IONS ON THE RELATIVE PERMITTIVITY OF WATER 528 13.8 TERMS USED IN
DESCRIBING HYDRATION 528 13.8.1 SOLVATION SHELL 529 13.8.2 BOUND AND
NON-BOUND WATER 529 13.8.3 FURTHER TERMS: PRIMARY AND SECONDARY
SOLVATION 530 13.9 TRADITIONAL METHODS FOR MEASURING SOLVATION NUMBERS
530 13.9.1 VIBRATIONAL SPECTRA (IR AND RAMAN) AND ELECTRONIC SPECTRA
(UV, VISIBLE AND IN SOME CASES IR) 530 13.9.2 TRANSPORT PHENOMENA 531
13.9.3 RELATIVE PERMITTIVITY OF THE SOLUTION 532 13.9.4 ACTIVITY
MEASUREMENTS 532 13.10 MODERN TECHNIQUES FOR STUDYING HYDRATION: NMR 533
13.10.1 LIMITATIONS OF NMR 534 13.10.2 SLOW EXCHANGES OF WATER MOLECULES
534 13.10.3 FAST EXCHANGES OF WATER MOLECULES 535 13.10.4 RESULTS OF NMR
STUDIES OF HYDRATION 536 13.10.5 RESIDENCE TIMES FROM NMR AND ULTRASONIC
RELAXATION 536 13.11. MODERN TECHNIQUES OF STUDYING HYDRATION: NEUTRON
AND X-RAY DIFFRACTION 538 13.11.1 NEUTRON DIFFRACTION WITH ISOTOPE
SUBSTITUTION 539 13.12 MODERN TECHNIQUES OF STUDYING SOLVATION: AXD
DIFFRACTION AND EXAFS 541 13.13 MODERN TECHNIQUES OF STUDYING SOLVATION:
COMPUTER SIMULATIONS 542 13.14 CAUTIONARY REMARKS ON THE SIGNIFICANCE OF
THE NUMERICAL VALUES OF SOLVATION NUMBERS 543 13.15 SIZESOFIONS 544
13.16 A FIRST MODEL OF SOLVATION - THE THREE REGION MODEL FOR AQUEOUS
ELECTROLYTE SOLUTIONS 544 13.16.1 STRUCTURE MAKING AND STRUCTURE
BREAKING IONS 545 13.16.2 EVIDENCE FOR STRUCTURE MAKING/STRUCTURE
BREAKING 545 13.16.3 A FIRST ATTEMPT AT CLASSIFICATION 545 13.16.4
THERMODYNAMIC EVIDENCE 546 13.16.5 DETERMINATION OF PARTIAL MOLAR
ENTROPIES FOR INDIVIDUAL IONS 547 13.16.6 STANDARD ENTROPIES OF
HYDRATION 548 13.16.7 SIGNIFICANCE OF ENTROPIES OF HYDRATION FOR
STRUCTURE MAKING/BREAKING 549 13.17 VOLUME CHANGES ON SOLVATION 551
13.18 VISCOSITY DATA 552 13.19 CONCLUDING COMMENT 552 13.20
DETERMINATION OF AGT, DRATION 552 13 21 DETERMINATION OF AH^ YD[ALION
553 13.22 COMPILATION OF ENTROPIES OF HYDRATION FROM AGFJ YDRATION AND
AH^ YDRATION 554 13.23 THERMODYNAMIC TRANSFER FUNCTIONS 554 13.24
SOLVATION OF NON-POLAR AND APOLAR MOLECULES - HYDROPHOBIC EFFECTS 554
13.25 EXPERIMENTAL TECHNIQUES FOR STUDYING HYDROPHOBIC HYDRATION 556
13.25.1 RESULTS OF METHODS (I) AND (II) 556 13.25.2 RESULTS OF
THERMODYNAMIC STUDIES 557 13.25.3 ENTROPIES OF HYDRATION AT INFINITE
DILUTION, AS 9 557 XVIII CONTENTS 13.25.4 AEV E OF SOLVATION AT INFINITE
DILUTION 557 13.25.5 THERMODYNAMIC TRANSFER FUNCTIONS 557 13.26
HYDROPHOBIC HYDRATION FOR LARGE CHARGED IONS 559 13.27 HYDROPHOBIC
INTERACTION 560 13.28 COMPUTER SIMULATIONS OF THE HYDROPHOBIC EFFECT 560
SUBJECT MATTER OF WORKED PROBLEMS 561 INDEX 563 |
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| id | DE-604.BV022495267 |
| illustrated | Illustrated |
| index_date | 2024-07-02T17:53:19Z |
| indexdate | 2024-07-09T20:58:51Z |
| institution | BVB |
| isbn | 9780470842942 9780470842935 |
| language | English |
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| spelling | Wright, Margaret Robson Verfasser aut An introduction to aqueous electrolyte solutions Margaret Robson Wright Chichester Wiley 2007 XXVIII, 574 S. graph. Darst. txt rdacontent n rdamedia nc rdacarrier Includes index. "An Introduction to Aqueous Electrolyte Solutions is a comprehensive coverage of the subject including the development of key concepts and theory that focus on the physical rather than the mathematical aspects. Important links are made between the study of electrolyte solutions and other branches of chemistry, biology and biochemistry, making it a useful cross-reference tool for students studying this important area of electrochemistry." "An invaluable text for students taking courses in chemistry and chemical engineering, this book will also be useful for biology, biochemistry and biophysics students required to study electrochemistry."--BOOK JACKET. Equilíbrio químico larpcal Solutions (chimie) ram Solutions d'électrolyte ram Soluções eletrolíticas larpcal Équilibre chimique ram Electrolyte solutions Chemical equilibrium Solution (Chemistry) Wässrige Lösung (DE-588)4124928-8 gnd rswk-swf Elektrolytlösung (DE-588)4133913-7 gnd rswk-swf SoluÇÕes (QuÍmica) larpcal Elektrolytlösung (DE-588)4133913-7 s Wässrige Lösung (DE-588)4124928-8 s DE-604 http://www.loc.gov/catdir/toc/ecip0713/2007011329.html Table of contents only GBV Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=015702412&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Wright, Margaret Robson An introduction to aqueous electrolyte solutions Equilíbrio químico larpcal Solutions (chimie) ram Solutions d'électrolyte ram Soluções eletrolíticas larpcal Équilibre chimique ram Electrolyte solutions Chemical equilibrium Solution (Chemistry) Wässrige Lösung (DE-588)4124928-8 gnd Elektrolytlösung (DE-588)4133913-7 gnd |
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| title | An introduction to aqueous electrolyte solutions |
| title_auth | An introduction to aqueous electrolyte solutions |
| title_exact_search | An introduction to aqueous electrolyte solutions |
| title_exact_search_txtP | An introduction to aqueous electrolyte solutions |
| title_full | An introduction to aqueous electrolyte solutions Margaret Robson Wright |
| title_fullStr | An introduction to aqueous electrolyte solutions Margaret Robson Wright |
| title_full_unstemmed | An introduction to aqueous electrolyte solutions Margaret Robson Wright |
| title_short | An introduction to aqueous electrolyte solutions |
| title_sort | an introduction to aqueous electrolyte solutions |
| topic | Equilíbrio químico larpcal Solutions (chimie) ram Solutions d'électrolyte ram Soluções eletrolíticas larpcal Équilibre chimique ram Electrolyte solutions Chemical equilibrium Solution (Chemistry) Wässrige Lösung (DE-588)4124928-8 gnd Elektrolytlösung (DE-588)4133913-7 gnd |
| topic_facet | Equilíbrio químico Solutions (chimie) Solutions d'électrolyte Soluções eletrolíticas Équilibre chimique Electrolyte solutions Chemical equilibrium Solution (Chemistry) Wässrige Lösung Elektrolytlösung SoluÇÕes (QuÍmica) |
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