Index

A ac

frequency effect on dendrite growth, 287, 289

method for double-layer capacity, 177-179

Acetone, heats of solvation in, 7 Acetonitrile, heats of solvation in, 7 Activation, volume of, in kinetics, 98 Activity

coefficients, solvation numbers from tabulated, 36

method, for solvation numbers, 34 of solvent, in ion-pairing equilibria,

72 Addition agents, leveling, 259 Additive consumption, in nickel

deposition, 261 Adsorbed

intermediates, in electrode reactions, 121, 129, 156

molecules, and incorporation in whiskers, 247

reactants, reactions of, 155 Adsorption

air-water and air-solution, 145 and double-layer capacity, 176 and experimental phenomena, 152 and inhibition of reactions, 153 and ring size with aromatics, 149 and solubility, 147, 148 and solvent orientation, 150 at electrodes, methods for study of,

143 definition of, 147 diffusion

control in, 145

Adsorption (cont'd) effects in, 185

direct methods for determination of, 157

energy of H, and kinetics, 132, 133 from capacity measurements, 175 in Faradaic processes, 185 isotht]rms

tests for, 182 measurement of

extraction of characteristic values from, 184

in situ, 158 near redox potential, 156

mechanism of orientation in, 146 methods for, problems in, 157 or inorganic species, 154 of pyridine and acid derivatives,

148 optical measurements on, 159 polarographic studies of, 186 potential range of, 156 processes, and electron transfer,

144 radioisotope method for studies of,

158 studies, summary of methods and

problems in, 187 Air - solution and air - water,

adsorption at interfaces, 145 Air-water interface, Gibbs equation

for, 170

399

Alkaline halides

heats of solvation in nonaqueous solvents,S, 6,7

solvation entropies in nonaqueous

400

Alkaline (cont'd) solvents, 17

metals, and solvated electrons, 121 Amalgams

bismuth, processes at, 375 copper, processes at, 375 indium, 341 solvated electrons in dissolution of,

335 use of in studies of metal reactions,

315 variation of metal concentration in,

315 zinc, 341, 382

Amplification effects, and concentration in metal

deposition, 219 of surface irregularities, 197, 203

Anodic and cathodic limiting currents, and exchange currents, 344

Appearance of dendrites, 222 Aqueous mixtures, Jones-Dole

coefficients for, 57 Areas, molecular, in adsorption, 170 Aromatic hydrocarbons, ring size and

adsorption of, 149 Association

B

ion pairs in equilibrium, 69 ionic, in conductance, 69 of ions, references for, 72

Barker, photo-effect, work of, 102, 103

Birch reaction, 83, 119 Bismuth

amalgams polarization diagram for, 375, 377 processes at, 375

solid, polarization diagram for, 375, 377

Bjerrum, theory of, 69 Born equation

applications of, 20 application to mixed solvents, 40 corrections in, 6 in calculations of transfer energies,

40 ionic contributions from, 12 treatment for ion solvation, 6

Born-Haber cycle, for electrode calculations, 87

Break criterion condition for, 365 for stepwise mechanisms, 332

Butanol, heats of solvation in, 5

C

Index

Capacitance, in copper dissolution, 271

Capacity double-layer, measurement of, 173 frequency dispersion of, 178 measurement of, 160

Cathodes, experimental photo-effect at, 103

Cathodic injection chemical evidence for, 117 of solvated electrons, 10 1

Cation reduction, steps in, 187 Cavity model, in solutions, 29 Charge

determination of surface-, 174 electrode, measurement of, 160

Chemical reactions, of solvated electrons, 118 shift

in perchlorate solution, 48 in solvation studies, 48

Chemisorbed films, 154 Chemisorption, 154 Component reactions, in mixed

processes, 93 Compressibility

measurements, tabulated solvation numbers from, 33

method, for solvation numbers, 32 Concentration

effects, and leveling, 259 of metal in amalgams, 315

Conductance and Stokes' law, 63 and Walden's rule, 63 ionic,61

association effects in, 69 tabulated, 61, 62

in mixed solvents, 66 theory of, and solvation, 56

Contact angle, at solid electrodes, 172 Continuum

dielectric, solvation in, 23 thermodynamic calculations for, 23

Copper amalgam

Index

Copper (cont'd) , polarization diagram for, 381

processes at, 375 deposit, on rough surface, 200 deposition

and diffusion effects, 218 and surface roughness, 216

dissolution capacitance in, 271 resistance in, 271

electropolishing of, time constants for, 281

Corresponding states, in solvation, 14 Corrosion reactions, hydrated electrons

in, 124 Coupled process, isolation of step in,

333 Criteria for stepwise mechanisms, 332

summary, 371 Critical current density

for powder formation, 251 for whisker growth, 244

Crystal habit, of dendrites, 242 structure and metal deposition, 238

Current density, and leveling, 260 distribution, 197 transients, in deposition, 215

D

Dendrite appearance of, 220 crystal habits of, 242 growth

ac frequency effect on, 289 and crystal structure, 238 and Kelvin effect, 214 comparison with experiment, 231 initiation of, 223 morphology of, with pulsating

potential, 292 - 293 of, and kinetics, 220

of zinc, 232 - 235 temperature dependence of, 237 prevention of, 202 time of appearance of with

pUlsating currents, 290 under superimposed ac, 288

of silver, illustrated, 201 of zinc, illustrated, 239, 240 propagation, 225

Dendrite (cont'd) rate of growth of, 221 tip, paraboloidal shape, 226

Deposition time and sinusoidal irregularities, 207

Desorption, in polarography, 173 Dielectric

constant and ionic association, 77 differential, for methanol, 26

continuum calculations for, 23 model,23 thermodynamics of, 24

relaxation and Stokes' law, 64, 65

saturation at ions, 26

401

radii for nonaqueous solvents, 27 theory, of ionic volumes, 25

Differential dielectric constant, 26 Diffusion

and electropolishing, 273 at paraboloidal growing tip, 228 conditions, at growing dendrites,

226 control

conditions in powder formation, 252

on irregularity, 208 theory, in powder deposition,

252-253 controlled processes

computer calculations in, 306 Kelvin effect in, 305 quantitative aspects of, 302 quantitative solutions for special

cases, 305 controlled smoothing, theory of, 277 distance, of solvated electrons, 116 effects

in adsorption, 185 in copper deposition, 218 in scavenger behavior, 110, 111

flux and leveling, 265 in electropolishing, 282

in adsorption processes, 145 layer

development of, 301 development of, at an irregularity,

307,309

402

Diffusion (cont'd) steady state, 302

Dimethylsulfoxide heats of solvation in, 7 ionic heats of solvation in, 9

Dioxane-water mixtures Jones - Dole coefficients, 59 NMR of, 48 radii for, 68 transfer functions for, 42

Disproportionation, in stepwise reactions, 367

Double layer capacity

ac measurement of, 177- 179 and roughness effects, 178 and surface fIlms measurement of, 160, 176

effects in kinetics, 319 suppression of, 323

equivalent circuit for, 177 frequency effects on, 178 in electrochemical photoeffect, 107

Drop time measurements, 171 accuracy of, 171

E

in relation to capillary electrometer results, 171

Effective work function, Frumkin calculation of, 85

Electroactive species, 144 Electrochemical

engineering, uses of solvated electrons in, 83

photoeffect, 83, 102 experimental relations for, 104,

105 reactions

general aspects, 314 hydrated electrons in, 122 of adsorbed species, 155 stepwise, classification of, 314

studies, combined with radioisotope measurements, 336

Electrochemical adsorbed hydrogen, 129

Electrochemisorption role of, for hydrogen and oxygen,

155 theories of, 155

Index

Electrode application of Gibbs equation to,

162 charge

determination of, 174 measurement of, 160

ideally polarizable, 169 potential, in a practical cell, 90 reactions, intermediates, in, 156

Electrolytes, historical significance of, 1

Electron injection, and ion electrode

processes, 87 transfer

and adsorption processes, 144 Gurney condition for, 95, 97 multi-,316 radiationless, 85 tunneling, 13 2

Electronic work function and solvated electrons, 85 in electrode processes, 87-90

Electropolishing and flow rate, 269 and passivation, 273 and polarization curves, 270 copper, time constants for, 281 defined, 202 diffusion effect, treatment of, 277 diffusion flux in, 273 experimental facts, 268 models of, 273 of steel, illustrated, 203 photoeffect in, 270 radius of curvature of irregularities

in, 279 steady-state rates, 277 time dependence of recess depths,

273 Electrostatic theory

of selective solvation, 44 of solvation, 20

Electrostriction and dielectric properties, 25 circuit for, 91 components in measured, 91 method, for free energies of

solvation, 10 pressure dependence of, 125 theory of, 25

Index

Energetics, of solvated electron production, 87, 91

Energy levels, for solvated electrons, 100

Enthalpies ionic, of solvation - see Heats of solvation

tabulated,S theoretical, 24

of transfer water-glycerol, 37 water-mixed solvents, tabulated,

38 Entropies of solvation, 16

standard ionic, 18 theoretical, 24, 28

Equations for partial anodic currents, 360

Equilibria, successive solvation, 4 Equivalent circuit

for copper dissolution, 271 for double layer, 177

Ethanol, heats of solvation in,S Ethylene glycol, heats of solvation in,

6 Exchange current

and anodic and cathodic limiting currents, 344

and solvated electrons, 333 apparent, from polarization data,

333 determination of by radioisotope

exchange, 333 direct determination of, 315 extrapolated, 360 for hydrogen evolution, and the

metal, 133 for partial electrochemical processes,

360 from cathodic and anodic

polarization curves, 389 pressure dependence of, significance,

125 relation between true and

extrapolated values, 360 true, 360

Exchange rates, direct measurements of, 339

Experimental arrangements, problems in, 179 behavior in electropolishing, 268 phenomena and adsorption, 152

Experiments, relation to dendrite growth, 231

F Faradaic

processes

403

adsorption effects in, 185 diffusion in and adsorption, 185

reactions, inhibition of, 153 Ferrocene, redox equilibrium, 153 Film formation and reaction products,

284 Flash photoeffect, 115 Flow rate and electropolishing, 269 Formamide

ionic enthalpies in, 30 ionic heats of solvation in, 9 heats of solvation in, 7

Formic acid, heats of solvation in, 6 Free energies

of ions, real, in nonaqueous solvents, tabulated, 21

of solvation, 9 ionic, in liquid ammonia, 22, 23 ionic contributions in, 12

of transfer theoretical, 28 water-mixed solvents, 39 water to methanol, 16

Frequency dispersion, of capacity, 178

Frumkin, review on capacity work, 177

Fuoss and Zwanzig, theory of ionic motion, 64

G

Gallium electrode

in electrochemical studies, 385 reactions at, 386

surface tension of, 171 Geometry of cell, effects of, 179 Gibbs

adsorption equation, 143 and reference conditions, 168

equation and surface excess, 151 application to electrodes, 162 derivation of, 161 for air-water interface, 170 Guggenheim treatment of, 163

404

Gibbs (cont'd) Parsons' treatment of, 163

own treatment of the adsorption equation, 161, 162

Grahame, wOFk of, 161 Growth

geometry of metal crystal, 210 of dendrites, 200, 220

and crystal structure, 238 conditions of appearance for, 221 frequency of instance of, 221 theory of, 222 tip, paraboloidal, 226

of powers, 200 of whiskers, 200, 242

Guggenheim, treatment of Gibbs equation, 163

Gurney

H

condition, for solvated electron production, 95, 97

criteria, for electron transfer, 95, 97 theory, 132

applied to electron transfer into solu tion, 85

Hardness, surface, in adsorption, 172 Heats

of solvation, 3 from Born equation, 6 ionic in water, 8 ta bula ted, 5

of transfer, water-glycerol, 37 water-mixed solvents, tabulated,

38 Heyrovsky

photo-effect work of, 102, 103 theory of electron transfer, 317

Higher order reactions, 366 Historical survey, of stepwise electro­

chemical reactions, 316 Hydrated electrons

and volume of activation, 124 as intermediate, 84 energy conditions for production of,

95 illumination effects in production of,

136 in electrochemical reactions, 122 in hydrogen evolution, problems of

dependence of metal, 132 production, microscopic reversibility

Hydrated electrons (cont'd) problems, 128

production, thermodynamic problems, 126

Index

standard potential for, problems, 134

Hydrocarbons, aromatic, adsorption of, 149

Hydrogen atomic, adsorption of, 132, 133 bonding

and association, 47 and NMR, 47 in mixed solvents, 47

electrochemically adsorbed, 129, 130,133

electrochemisorption of, 155 evolution

in metal deposition, 387 reaction

adsorbed H in, 132, 133 hydrated electrons in, 123 solvated electrons in, 84

Ideally polarized electrode, 169 Indium amalgams, 341 Inhibition of Faradaic reactions, 153 Initiation of dendrite growth, 223 Inorganic species, and adsorption, 154 Interactions, in solvent mixtures, 2 Intermediates,

adsorbed, in electrode reactions, 156

in cation reduction, 187 Ion

association and dielectric constant, 72 and solvent activity, 72 Denison and Ramsey theory, 70

electrode and electron injection, 87 pairs, types of, 69 pairing

and dielectric constant, 72 theories of, 70

Ionic association

Gilkerson theory, 70 references for, 72

conductance, 60 in mixed solvents, 66 relation to viscosity, 66

Index

Ionic (cont'd) tabulated, 61, 62

contributions additivity of, in solvation, 53 in enthalpies of solvation, 8, 9 in free energies of solvation, 12 in transfer free energies, 16

enthalpies of solvation, in fonnamide,30

free energies of solvation, tabulated, 8

in nonaqueous solvents, 9 intermediates

accumulation of, 334 and ring-disc studies, 335

radii for dioxane-water mixtures, 68 from Zwanzig's equation, 66

radius, dependence of solvation energy on, 13

solvation effects, in slowness of last charge transfer step, 347

standard entropies of solvation, 13 volume, 3

and specific solvation in mixed solvents, 43

dielectric theory of, 25 formal relations in, 3 solvation numbers from, 35

IrregUlarity, height of, with time, 214 Irreversible process, under pUlsating

potential conditions, 299 Iron, stepwise processes in oxidation

of, 317 Isotherms, adsorption, 182 Isotope dilution technique, 31

J lones-Dole coefficients, 54

for aqueous mixtures, 57

K

in dioxane-water mixtures, 59 tabulated, 55

for aqueous mixtures, 57

Kelvin effect and radius of curvature, 212 in electropolishing, 273 in growth of irregularities, 214

Kinetics activation volume in, 98 double-layer effects in, 319

405

Kinetics (cont'd) equations, with double-layer

effects, 319, 323 of dendrite growth, 221 of higher order reactions, 366 of hydrogen evolution, and adsorbed

H, 132, 133 parameters, tabulated, for various

mechanisms, 372 with excess of supporting electrolyte,

319, 323 Krichmar, work of, 248, 249, 271

L

Large ions, use in determination of ionic contributions, 3

Last charge transfer step, slowness of, in a series, 347

Lead oxidation of, 391 valence states in oxidation of,

391,392 Leveling

agent, and nickel deposition illustrated, 202

and current density, 260 and diffusion fluxes, 265 and polarization curves, 259 basic facts, 256 defined, 200 dependence on additive

concentration, 257 in nickel deposition, polarization

curves for, 258 model for, 261 theory of, 263

Limiting current density of metal deposition,

and powder formation, 251 step, single, 318

Lippmann electrometer, 171 Liquid ammonia

electrons in, 83 ionic free energies of solvation in,

22,23 standard electrode potential for

solvated electrons in, 91 Low valence

intermediates, 335 metal ions, 84

M Mass spectrometer, studies with, 3

406

Measurement, of surface tension, 171 Mechanisms of metal deposition, and

energy diagrams, 209 Medium effect method, for free

energies of solvation, 9 Mercury, surface tension of, 171 Metal

deposition at a periodically changing rate,

285 reactions

consecutive steps in, 209 potential energy diagrams for,

209 under reversing current conditions,

286 univalent intermediates in, 316 with hydrogen evolution, 386 with pulsating currents, 290 with superimposed ac, 288

ions, low valence, 84, 335 reactions, use of amalgams in, 315

Methanol dielectric saturation in, 26 differential dielectric constant for,

26 heats of solvation in, 5 -water, transfer free energies, 16

Methods for free energies of solvation, 9, 10 for measuring adsorption directly,

157 Microscopic reversibility, problems in

hydrated electron production, 128

Mixed processes, 93

corrosion, 96 solvated electrons in (criticisms),

96 solvents, 37

Born equation, for, 40 enthalpies and free energies of

transfer to, 37, 38, 39 ionic conductance behavior in, 66 ionic volumes and specificity, 43 NMR studies in, 48 selective solvation in, 44 specific solvation in, 43 structural effects in, 38, 67

Mobility measurements, solvation numbers

Mobility (cont'd) from, 35

Index

method, for solvation numbers, 34 Model

cavity, for ion in solvent, 29 for solvation and structure, 29 of surface irregularities, 204

Molecular areas, 170 Mole fraction, surface, 165 Morphology

of deposits and theory of pulsating electrolysis,

294 under pulsating conditions,

illustrated, 292-293 of metal deposit, experimental and

theoretical, under pulsating electrolysis conditions, 309

Multi-electron transfer, 314-330, 328

N Nickel deposition

consumption of additive in, 261 polarization in, 258 with leveling agent, 202

Nitrous oxide, reactions of, 139 NMR

and hydrogen bonding, 47 and water exchange, 50 applications to solvation, 47 broadening effect, and preferential

solvation, 50 chemical shift, 48 of dioxane-water mixtures, 48 relaxation times, 50 studies, tabulated results for, 51 technique, for solvation numbers, 31

N-Methyl acetamide heats of solvation in, 7 ionic heats of solvation in, 9

N-Methyl Formamide heats of solvation, 7 ionic heats of solvation in, 9

N-N-Dimethyl formamide, heats of solvation in, 7

Nonaqueous solvents - see under names of solvents for tabulated data

and solvated electrons, 119 dielectric saturation radii, 27 entropies of solvation in, 17 real free energies of ions in, 21 solvation numbers in, 35

Index

Nonaqueous solvents (cant 'd) standard ionic entropies in, 18

Nonelectrolyte correction, in solvation energies, 15

Numbers, solvation, for ions, 30

o One-electron transfer processes, 317 Optical measurements, on adsorption,

159 Organic

compounds, in electrochemical photoeffects, 105

electrochemical reactions, and solvated electrons, 138

ions, solvation of, 15 salts, solvation of, 15 substances, and solvated electron

reactions, 118 Orientation of solvent, in adsorption

processes, 150 Oxygen, electrochemisorption of, 155

P

Paraboloidal diffusion, 228 tip, growth of, 226

Parsons' treatment, of electrochemical adsorption, 163

Partial anodic

and cathodic current relations, 362

currents, equations for, 360 process, direct measurement by

radioisotope studies, 333 Periodic effects, in metal deposition,

285 Tr -electrons, in adsorption, 170 Photoeffect

at cathodes, 103 double layer in, 107 electrochemical, 83

experimental relations for, 104, 105

flash, 115 in electropolishing, 270 scavenger behavior in, 109

Photoelectric effect, quantal, 102 Photoelectrochemical emission

characterization of, 103 conditions for, 101

407

Photoproduction of solvated electrons, 101

Platinum, adsorption at, by optical methods, 159

Polarization and exchange currents, 333 curves

and electropolishing, 270 calculated

for stepwise reactions, 368 for three-step mechanism, 357

for copper deposition, 345 for indium amalgam, 343 for metal deposition, and leveling,

259 for nickel deposition, 258 for zinc amalgams, 342

diagram for bismuth, 380

amalgam, 375, 377 for copper amalgam, 381 for partial anodic and cathodic

currents, 362, 363 for solid bismuth, 380 for thallium redox reactions, 386

Polar media, state of electrons in, 99 Polarographic

effects, of adsorption, 173 results, for solvated electrons, 92 studies of adsorption, 186

Positive charge, primitive, hydration energy of, 85

Potential energy diagrams, for metal

deposition reactions, 209 of zero charge, 144 range, of adsorption, 156

Potentiostatic transients, in deposition, 213

Powder deposits

critical current density for formation of, 251

features of, 250 formation of, 250

formation and diffusion control conditions,

252 and limiting current density of

metal deposition, 251 transport control in, 254

growth, 200

408

Preferential solvation NMR broadening effect in, 50 parameters for, tabulated, 46

Pressure dependence of exchange current,

significance of, 98 effects, L-, in kinetics, 98

Primitive positive charge, hydration energy of, 85

Process of adsorption and orientation, schematic, 146

Propagation of dendrites, 225

n-Propanol, heats of solvation in, 5

Propylene carbonate heats of solvation in, 7 ionic heats of solvation in, 9

Proton exchange, and NMR, 50 1/! potential, effects in kinetics, 319

Pulsating currents and metal deposition, 290 electrolysis, at reversible electrodes,

295 for irreversible process, 299 in a reversible process, 295 morphology of deposits in, 309 theory of, 294 with irreversible metal deposition,

299 Pyridine and acid derivatives,

adsorption of, 148

Q

Quasiequilibrium, in stepwise reactions, 321

R

Radiationless electron transfer, 85

Radical reactions, in solvated electron processes, 113

Radii, for dielectric saturation in nonaqueous solvents, 27

Radioisotope and electrochemical measurements,

comparison of, 338 exchange studies, in stepwise

reactions, 333 measurements, combined with

electrochemical studies, 336

Index

Radioisotope (cont'd) method, for adsorption, 158 studies, advantages of, 337

Radiotracer and electrochemical measurements, simultaneous, 364

Radius of curvature

and amplification factor, 213 in dissolu tion rate, 270 of irregularity, and Kelvin effect,

212 of whiskers and growth rate, 243

Rate constants, comparable for successive

steps, 349 equations, for steps with comparable

rate constants, 349, 353 Real energy of solvation, 20 Reaction

higher order, 366 order, in stepwise processes, 328 products, and film formation, 284

Recess depth, time dependence in

deposition, 273 passivation at, 274

Redox reactions solvated electrons in (criticisms), 34 stepwise mechanisms in, 391 thermodynamics of, 94

Reentrant groove growth at, 241 maintenance of, 241

Reference conditions, in Gibbs adsorption theory, 168

Reflectance effects, in solvated electron production, 136

Relaxation times, NMR, 50 Resistance, in copper dissolution, 271 Reversible process, under pulsating

potential conditions, 295 Reversing currents

and metal deposition, 286 sinusoidal, 287

Ring -disc electrodes, and ionic

intermediates, 335 size, and adsorption of aromatic

hydrocarbons, 149 Rough surface, copper deposition on,

200

Index

Roughness effects, in double-layer capacity measurements, 178

S

Salting-out, and selection solvation, 44,49

Salts heats of solvation for,S organic, solvation of, 15

Samoilov theory, of solvation, 53 Scavenger behavior

diffusion effects in, 11 0, 111 with solvated electrons, 108

Scavenging reactions and standard potential for hydrated

electrons, 134 kinetics of, 135 with solvated electrons, 84

Selective solvation organic components and, 49 theory of, 44

Sessile drops, and surface tension, 172 Shape of dendrites and crystal

structure, 238 Shielded anode, smoothing efficiency

at, 272 Silver

dendrite, illustrated, 201 deposition, at dendrites, relation to

tip radius, 230 whisker illustrated, 201

Single interface processes, 87 limiting step, in stepwise processes,

318 Sinusoidal

irregularities, and metal deposition time, 207

model of surface irregularity, 205 theory of, 205

reversing currents, 287 Slowness, in last charge transfer step,

347 Solid

electrodes, adsorption at, 172 metals, reactions at, 386

Solubility and adsorption, 147, 148 method, for free energies of

solvation, 9

409

Solutions of ions, 1, et seq. of solvated electrons, nature of, 119

and low-valence intermediates, 335 and organic electrochemical

reactions, 138 and polarography 92 and radical reactions, 113 and standard potential scale, 92 and surface potential, 86 and transition state, 138 cathodic injection of, 101, 117 energy levels for, 100 Gurney condition for production

of, 95,97 in dissolution of amalgams, 335 photoproduction of, 101 possible uses for electrochemical

engineering processes, 83 scavenger behavior, 108 scavenging reactions with, 84 solutions, nature of, 119 standard electrode potential for,

in water, 91 standard potentials for, in liquid

ammonia and water, 91 state of, 99

Solvation and conductance, 56 and lones-Dole coefficients, 54 and Stokes' law, 63 and Walden's rule, 63 applications of viscosity measure-

ments in, 52 energy nonelectrolyte correction in,

15 entropies, tabulated for salts, 17 entropy of, 16

tabulated for salts, 16 free energies

of, 9 real, 20

gas phase studies of, 3 heats of, 3 ionic

contribu tions in, for large ions, 54 enthalpies in formamide (see also

under names of other solvents), 30

NMR aspects of, 47 numbers, 30

410

Solvation (cont'd) activity method for, 32 compressibility method for, definitions of, 30 from compressibility measure­

ments, tabulated, 33 in nonaqueous solvent mixtures

NMR methods, 51 in sulfuric acid, 36 isotope dilution method for, 31 methods for, 31 mobility method for, 34 NMR method for, 31 tabulated

from activity coefficients, from mobility measurements, 35 from NMR studies, 51 from viscosity and volumes, 35

viscosity method for, 33 volume difference method for, 32

selective, in mixed solvents, 44 specific, in mixed solvents, 43 structural effects in, 29 theories of, 20 thermodynamics ofl 2

Solvents distinction between, 2 mixed, 37 mixtures

excess functions for, 2 types of interaction in, 2

orientation and adsorption, 150 protic and aprotic, 2

Standard ionic entropies of solvation, 18 potential, for solvated electrons, 92

scale, for solvated electrons, 92 criticized, 92

Steel, electropolishing of, illustrated, 203

Step growth and incorporation of adsorbed molecules, 247

Stepwise electrochemical reactions

classification of, 314 historical survey on, 316

mechanisms, break criterion for, 332 criteria for, 332

summary, 371 tabulated, 374

features of, 328 in redox reactions, 388

Index

Stepwise (cont'd) kinetic parameters, tabulated, 371

processes in oxidation of iron, 317 involving disproportionation, 366 polarization curves for, 327 relation between transfer

coefficients in, 329 with a single limiting step, 318

reactions ionic intermediates in, 334

quasiequilibria in, 321 radioisotope exchange studies in,

333 Stoichiometry of solvation shell, 3 Stokes'law

and conductance, 63 dielectric relaxation and, 64, 65

Structural effects in mixed solvents, 38, 67 in solvation, 29 in transfer functions, 41

Successive steps with comparable rate constants, 349

Sulfuric acid, solvation number in, 36 Superimposed ac

effects on dendrite growth, 288 in metal deposition, 288

Supporting electrolyte, excess, 323 Surface

coverage, and molecular size, 170 excess

and adsorption, Grahame's discussion, 167

and Gibbs equation, 151 definitions, 151 negative, 166 general significance of, 165 theoretical significance of, 160

films and frequency dependence of

double-layer capacity, 180 optical measurements on, 159

hardness and adsorption, 172 irregularities

amplification of, 197, 203 effect of radius of curvature in

deposition, 213 models of, 204 sinusoidal model for, 205 time dependence in deposition,

214

Index

Surface (cont'd) mole fraction, 165 potential, and solvated electrons, 86 roughness

definition, 197 time dependence in copper

deposition, 214, 216 tension

measurement of, 160, 171 thermodynamic theory of, 160

Surfactants and whisker growth, 244 incorporation in deposits, 247 traces of, and frequency effect, 180

Symmetry coefficient, 321

T

Tafel slopes for stepwise mechanisms, tabulated, 356

Tensametric processes, 181 waves, 181

Tetraalkylammonium ions, 67 salts, solvated electrons in solutions

of, 118, 119 Thallium

reactions, electrochemistry of, 389,390

redox reactions, polarization diagram for, 389

Theory electrostatic, of solvation, 20 of conductance, 56 of dielectric continuum, 23 of leveling, 263 of pulsating electrolysis, 296-297 of Samoilov, 53 of selective solvation, 44 of solvation, 20

Thermodynamic calculations for dielectric continuum,

23 of a dielectric continuum, 24 of solvation, 2 theory, of surface tension, 160

Tip radius, and deposition of silver and zinc dendrites, 230

Transfer coefficient, 321

for stepwise mechanisms, tabulated, 356

Transfer (cont'd) relation between

in stepwise processes, 329 tabulated, 330

sum, criterion of, 360 energies

calculation of, 40 structure effects in, 41

enthalpies water-glycerol

411

water-mixed solvents, tabulated, 38

free energies water-mixed solvents, 39 water to methanol, 16

fUnctions, water-dioxane mixtures, 42

Transients, in metal deposition, 215 Transition state, and solvated electron

injection, 138 Transport

control, in powder formation, 254 controlled processes

computer calculations for, 306 generalized model, 300

processes, 52 Triangular elevations

equivalent circuits for reaction at, 275

potential field at, 274 True exchange current, 360 Two-electron transfer processes, 317

U

Univalent intermediates, in metal deposition, 316

V

Viscosity applications to solvation, 52 J ones-Dole coefficients, 54

tabulated, 55 method, for solvation numbers, 33 properties, solvation numbers from,

35 relation to ionic conductance, 66

Volume difference method, for solvation

numbers, 32 of activation, 98

and hydrated electrons, 124

412

W

Walden's rule and conductance, 63 Walden's rule, deviation from, 63 Water-methanol, transfer free energies

in, 16 Water molecule exchange, and NMR,

50 Waves, tensametric, 181 Whiskers

growth, 200, 242 and surfactants, 244 and tip contamination, 245 critical current density and radius,

243 of silver, illustrated, 201

Work function effective, for solvated electron

production, 84

Index

Work function (cont'd)

Z

in electrode reactions, 85, 87 - 89, 90

Zero charge potentials, 144 Zinc

amalgams, 341, 382 dendrite

growth, temperature dependence of of, 237

illustrated, 239, 240 tip current density at, 236, 237

deposition and dendrite growth, 232-235

Zwanzig's equation, and ionic radii, 66 theory, and Stokes' law, 64