Annotated Author Index

Transcription

1 Annotated Author Index Anderson, H., Statistical mechanical methods in the double layer, 179 Anderson, Anderson, and Eyring, and partial charge transfer, 186 Anderson and Bockris breakdown of contributions to specific adsorption, 187 and partial charge transfer, 186 and specific absorption of halide ions, 180 and the theory of specific adsorption, 140 Annianson, and the radiotracer method, 155 Antropov, and his treatment of adsorption or organic compound, 262 Argade and Gileadi, their deduction of the relation of pzc to the cell potential, 270 Balashova, and radiotracer work, 140 Baron, Delahay, and Kelsh, simultaneous approach to specific adsorption, 209 Baugh and Parsons, absorption of guanidium ion from solution, 212 BDM (Bockris-Devanathan-Muller), their model of the double layer, 127 Beck, and the ribbon extension method, 161 Bickerman, and corrections of diffuse layer theory, 118 Biefer and Mason, their apparatus, 409 Billiter potential, abnormal, 230 Blomgren and Bockris and their isotherms, 191 and the radiotracer method, 140, ISS, 156 Bockris and contact adsorption, 138 and the dependence of the potential of maximum on ph for organic adsorption, 266 and the determination of pzc by the use of organic compound desorption, 264 and the interpretation of the bell-shaped curve for adsorption, with organic molecules, 265 and mechanism of AEC effects, 166 second model involving birners, and organic adsorption, 380 and specific adsorption, 138 Bockris, Devanathan, and Muller their isotherm, 191 and partial chargc transfer, 186 Bockris and Habib development of isotherm, 191 and the dimer model for water in the double layer, 129 an interpretation of entropy maximum, 129 treatment of multiple-imaging isotherm, 191 Bockris model, as basis for Parsons' macromodel, 377 Bockris and Reddy deduction of relationships between pzc and maximum of adsorption, 265 and the lack of identity of maximum adsorption with the pzc, 265 and semiconductor electrochemistry, 293 Boddy and Brattain, introduction to heavy metal ions,

2 440 Bode and application of Anderson-Bockris theory, 187 his calculations of specific adsorption, 188 and partial charge transfer, 186 Bolt, and corrections to the diffuse double layer, 120 Booth and electrophoretic mobility, 412 and electroviscous effects, 418 Bordowsky and Strehlow, diffuse double layer corrections, 120 Brattain and Boddy, and germanium electrodes, 315 Brattain and Garrett, the rust paper on semiconductor electrochemistry, 291 Butler, and the pzc of india mamalgoms, 229 Carroll, and plane of shear, 416 Chapman, and the diffuse layer theory, 105 Chiu and Genshaw explanation of discrepancies in ellipsometric method, 174 and the radiotracer method, 157 their work on specific adsorption, 173 Clausius-Clapeyron equation, in the double layer, 18 Conway and associated solvent system effects in the double layer, 132 counterions in the Helmholtz layer, and their influence, 130 Conway and Barradas, and adsorption of organic compounds, 140 Conway and Bockrls, the first suggestion of partial charge transfer, 180 Conway and Dobry-Duclaux, and various effects around colloidal particles, 417 Couchman and Davidson, and the Gibbs equation, and electrostrictional effects, 21 Curie, F. Jolliot, and the electrodeposition of radioelements, 155 Damaskin and Frumkin and clusters of water in double layer, 128 inner layer water, diagramed, 129 and the pzc, maximum of adsorption relationship, 265 Davies and Rideal, and electrophoresis, 416 ANNOTATED AUTHOR INDEX Debye length, 113 Defay, and the definition of surface tension, 20 Delahay, his approach to simultaneous adsorption, 206 Deryaguin and interaction between double layers, 423 and measurement of interaction between the thin plates, 432 and repulsion, 425 Devanathan, and his data on the double layer, 164 Devanathan and Peries capacitance in electrocapillary methods are the same, 164 Deryaguin-Landau-Verwey-Overbeek (DLVO) theory and colloidal stability, 423 tests of, 428 Devereaux and de Bruyn, and colliodal interactions, 427 Dogonadze and Chizmadjev, and double layer structure in nonaqueous solution, 278 Dukhin and Deryaguin, and the measurement of electrokinetic potentials, 409 Dupre equation, 102 Dutkiewiez and Parsons, thermodynamic approach to specific adsorption, 209 Dewald, and the flatband potential, 317 Esin-Markov plot, 94 Euler, and the investigation of absorption, 140 Everett, his contribution to the thermodynamic potentials, 13 Eyring, and work on the pzc, 271 Fawcett, and treatment of clusters in double layer, 129 Fermi level and calculation of flatband potential, 322 and electrode potential, 49 Flory-Huggins, isotherm, 191 Flory-Huggins statistics and adsorption isotherms, 195 in double layer, 129 Fomenko, and work function for tellurium, 280

3 ANNOTATED AUTHOR INDEX 441 Fredlein, Damjanovic, and Bockris, and the measurements of surface tension, on solids, 161 Frens, and repulsion during rapid shearing, 426 Friedel, and electron density calculations, 51 Frumkin and comparison of potentials of charge of different metals, 222 and the concentration-polarization theory, 153 and double layer effects in electrode kinetics, 282 and double layer effects in kinetics, 117 and early electrocapillary curves in nonaqueous solution, 274 and electrocapillary curves, 223 and electrocapillary equations, 222 and "formal charge transfer coefficient," 43 his interpretation of the bell-shaped curve for organic adsorption, 266 and isoelectric change, 40 and the pzc, 270 the relation of cell between work function and potential of zero charge, 272 and specific adsorption, 138 and surface on the solid metals, 160 and the thermodynamics of irreversible adsorption, 381 and the thermodynamics of platinum metals, 39 and two-dimensional isotherms, 364 his work on the thermodynamics of platinum electrodes, 4 Frumkin's equation, for organic adsorption, 370 Frumkin's model, for organic adsorption, 370 Frumkin, Evanova, and Damaskin, Graham's method becomes inapplicable, 163 Fuchs, and repulsion theory in colloids, 430 Galvani, and potential difference, at interface, 64 Garrett and Brattain, and surface excess with semiconductors, 298 Gauss' theorem, and diffuse double-layer theory, 108 Gerischer and dependence of flatband potential on the ph, 320 Gerischer (cont.) sensitization of redox transformations, 329 Gerischer and Willig, and photosensitization, 330 Gerovich, and 1r-electron interactions, 366 Gibbs his adsorption equation, 14, 16 and the concentration-polarization theory, 153 free energy in the double layer, 6 the original paper, 2 Gibbs surface excess, 146 definition, 13 7 exemplified, 23 Gileadi, and the radiotracer method, 156 Gillespie, and viscous energy dissipation, 420 Gokhstein and specific surface work, 22 and surface stress, and the piezoelectric method,21 Goodeve, and viscous energy dissipation, 420 Gouy, G., and the diffuse layer theory, 139 early work on organic adsorption, 354 and electrocapillary curves, 355 and the first electrocapillary curves, 274 Gouy, P.M., and definition of specific adsorption, 139 Gouy-Chapman-Stern, a model, 109 Gouy theory limitations, summarized, 117 at semiconductors, 295 Grahame and his basic idea, 140 his choice for specific adsorption, 152 his data for sodium fluoride, 176 his development of Stone's theory, 140 and the distance of closeness approach, 140 and his Essin-Markov plot, 94 his extension of Malsch's theory, 118 and an integrated capacitance relationship, 25 and ions bound to surface, 186 and the streaming electrode, for the pzc, 229 his test for diffuse double layer theory, 177 Grahame's capacitance method, for specific adsorption, 149

4 442 Grahame and Parsons, and the evaluation of 'Y, 185 Grahame and Soderberg their determination of specific adsorption, 149 and their method for obtaining Gibbs surface excess, 95 and the zero charge potential, 150 Grahame and Whitney, and electrocapillary thermodynamics, 153 Green and the fust paper on semiconductor electrochemistry, 292 and the qualitative difference in potential dissolution at the interface between semiconductors and insulators, 330 Gregory, and coagulation, 431 Grahame and Whitney, and electrocapillary thermodynamics, 223 Hale and Mehl, and anthracene crystals, 347 Hamaker constant, 431 Hansen, and organic adsorption, 377 Hasted, innovation of dielectric constant to concentration, 119 Haydon, and shear planes, 405 Haydon and Taylor, and corrections of the diffuse double layer theory, 118 Heavens, and ellipsometry, 157 Helmholtz layer at semiconductor-solution interface, 319 in solution, in semiconductor-solution interface, 303 Henry, his isotherm, 189 Honig and Mul, repulsion when zeta potential is small, 427 Huckel, and electrophoretic mobility, 412 Hunter description of repulsion theories, 430 and the literature, 412 Hurwitz calculation of simultaneous adsorption, 209 thermodynamic approach to simultaneous adsorption, 209 Israelachvili and Adams, measurement of exfoliated mica of repulsion, in exfoliated mica systems, 432 ANNOTATED AUTHOR INDEX Jakuszewski and Kozlowski, and the immersion method, 229 Jhering and the book with electrocapi11ary curves, 355 his table on differential capacity measurements, 357 Joshi, and double layer theory tests, 115 Joshi and Parsons, their examination of the diffuse double layer, 177 Kafalos and Gatos, and the radio tracer method, 155, 156 Kallman and Pope, pioneering work on insulator-electrode surfaces, 329 Kazarinov, and the radiotracer method, 156 Kingston and Neustadter, and charge in semiconductor, 297 Klein and Lange, and the dipole potential at the interface, 269 Koenig and electrocapillary thermodynamics, 153 his work on thermodynamics, 3 Kovac her results for the thiocyanate on mercury, 158 her work on specific adsorption, 173 Krasny-Ergen, and the primary viscous effect, 418 Kroichkoll, and the stretching of wires in 1809,229 Landau, and interaction between double layers, 423 Langmuir, and repulsive forces, 425 Lawrance, his work on specific adsorption, 173 Lawrance and Mohilner, and surface tension vs. capacity as a method of obtaining data in the double layer, 169 Lawrance, Parsons, and Payne and the double layer effects, 169 a fmite contact angle?, 164 Levine attempt to overcome sharp boundary difficulty,203 and corrections to the double layer theory, 120 and diffuse double layer corrections, 122 his isotherm, 202

5 ANNOTATED AUTHOR INDEX Levine, BeD, and Calvert, and multiple imaging,201 Levine, BeD, and Smith, dipoles in the double layer, 128 Unford, and specific surface work, 20 Uppmann.and electrode charge, 222 his original work, 2 Uppman equation, 16,85 Loeb, and self-atmosphere effects, 120 Lohman, Gerischer, and Memming, the solvent reorganization, 329 Longsworth, and theory of electrophoresis,414 Lorentz-Lorenz equation, and specific adsorption, 158 Lorenz bonding to mercury surface, 180 and determination of partial charge, 182 and partial charge transfer, 43, 181, 224 Lorenz's method, determination of partial charge, 182 Lyklema and ph near interfaces, involving silver iodide, 403 and surface potential for silver iodide, 416 Lyklema and Overbeek and analysis of electrophoretic mobility, 416 and charge-potential plots, Mohilner and electrocapillary thermodynamics for redox electrodes, 223 and expansion of equations in the double layer, 179 Mott-Schottky their layer, 300 their plot, and the tlatband potential, 316 Myamlin and Pleskov, and semiconductor electrochemistry, 293 Novakovsky, Ukshe, and Levin, and relation between pzc and cell potential, 270 Nernst, his equation, 3 Nernst-Planck, their equation, 413 Ninham and Parsegian, and repulsion theory for colloids, 430 Norrish, and the force-distance relationship, 432 O'Brien and White, and numerical solutions, 413 Ottewill and Rowell, monographs on colloidal systems, 433 Overbeck and coagulation, 431 and electrophoretic mobility, 412 MacDonald, and qualitative theory of inner layer, 126 MacDonald and Barlow, and multiple energies, 201 Malsch, and dielectric constant depending upon fuel strength, 118 Many, and semiconductor electrochemistry, 293 Matijevic, and coagulation, 431 McCrakin, ellipsometry in homogeneous film, 159 McCrakin and Colson, and ellipsometry, 157 Mehl' exchange currents of redox reactions on anthracene, 333 limiting currents at insulating electrodes, 329 Mehl and Buchner, and anthracenc electrodes, 343 Mehl, Hale, and Lohman, charge transfer and the solvent reorganization, 329 Paik, Genshaw, and Bockris, and the ellipsometric method for specific adsorption, 158 Palm, and adsorption on bismuth, 358 Palm and Tenno, and pzc effects on electrode kinetics, 283 Parsons calculation of simultaneous adsorption, 209 and claimed invalidity of his model, 377 and tests of diffuse double layer theory, 115 Parsons' method, for specific adsorption, 149 Parsons and Davanathan, and electrocapillary thermodynamics, 153 Parsons and Trasatti, their examination of the diffuse double layer, 177 Parsons and Zolbel, interfacial tension measurements lower than those obtained from capalitance data, 164 Pauli principle, and Fermi level, 48

6 444 Payne, and his work on capadtance-surfacetension effects, 168 Planck, and the completely polarizable electrode, 222 Pleskov, and early equations for semiconductor electrochemistry, 291 Poirier, and extension of the diffuse layer theory, 122 Proskurnin and Frumkin and the effect of octyl alcohol on the capacitance-potential curve, 357 and silver surfaces, 140 ANNOTATED AUTHOR INDEX Trasatti (cont.) relation to electronegativity, 271 and the relation of spedfic adsorption to water desorption, 189 and sticking on the glass capi1lary, 171 Tverdovskii and Frumkin, adsorption on solid metals, 161 Ukshe, capadtance in nonaqueous solution, 277 Ukshe and Bukun, potentials of zero charge, 279 Randles, and the dipole potential at the interface, 269 Randles and White, their work on capacitance in nonaqueous solution, 277 Russel, analysis of electroviscosity effects, 419 Schulze-Hardy rule, and explanation of colloid theory in electrochemical terms, 431 Seiwatz and Green, and the charge in semiconductor, 297 Smith, and his work on silver iodide, 416 Sparnaay and Hurwitz, energy in the double layer, 120 Stern, his model, 109 Stern's isotherm, 187 Stigter his apparatus, 409 and plane of shear, 416 Stillinger and Kirkwood, and double layer corrections, 122 Stone-Masui and Wati1lon, and the electroviscous effect, 418 Swinkels, Green, and Bockris, and the radiotraeer method, 156 Tamm states, 303 Trasatti his approach to water orientation, 131 and cell-potential relations, 270 and dipole potential difference, 273 and double-layer thcory tests, lis and the pzc related to the work function, 271 Vasenin and relations in cells, 268 and relationship to the dipole potential, 272 Vetter and Schulze, and partial charge transfer, 43, 183 Verwey and Niessen, entry into oil-water interface, 400 Verwey and Overbeck and interaction between double layers, 423 and oil-water interfaces, 400 and repulsive forces, 425 Vijh, and demetallization of the surface, 205 Volta potential and cell potential, 267 and potential of zero charge Volta potentials, tabulated, 270 Vulca potential difference, 65 Watts-Tobin, and water dipoles in the double layer, 126 Wieckowski, and the radiotracer method, 156 Wiersema, Loeb, and Overbeck, electrophoretic mobility, 412 Wiese and Healy, and repulsion under constant charge conditions, 426 Williams, and self-atmosphere effects, 120 Wroblowa and Green, and the radiotracer method, 155 Yakushevsky and Antropov, and relations deduced for cells, 269

7 Subject Index For some named effects, equations, etc. (e.g., Nernst equation), see the Annotated Author Index. Absolute electrode potential, 72 Absolute potential, some values, 76 Absorption in anthracene crystals, 347 of methanol on platinum, 86 ac effects and double layer, mechanism of, 166 in double layer, suggested mechanism, 165 Activity coefficient, and specific adsorption, 213 Adsorbed oxygen, and organic adsorption, 382 Adsorption energy, of organic compounds, at bismuth-solution interface, 367 Adsorption isotherms, tabulated, 189 Adsorption isothermics with 2-butanol, 364 of methanol, as a function of potential, 387 on methanol, 383 of organic compounds, and molecular model,377 of organic compounds, on ideally polarizable electrodes, 354 of organic compounds, reversible, 354 of organic compounds, thermodynamics, 360 of organic molecules, 353 of organic molecules, the potential dependence, 266 on platinum, of organic compounds, 388 Alloys, in contact with two electrolytes, their thermodynamics, 35 Ambiguity, and fundamental concept in electrochemistry, 225 Amyl alcohol, adsorption of, 359 Anthracene and the adsorption ofiodine, 335 and exchange current density, 333 Approach, microscopic, to colloidal stability, 428 Bands, unbending of, 310 BDM (Bockris-Devanathan-Muller) model, of the double layer, 127 Billiter potential, abnormal, 230 Binary alloy, and electrocapillary thermodynamics, 33 Bockris model, as basis for Parson's macromodel,377 Boundaries of conduction and valence band for various semiconductors, 323 Butyl alcohol, adsorption on different electrodes, 374 Camphor, desorption, from mercury electrodes and the pzc, 262 Capacitance of inner layer, diagramed, 125 and surface tension,

8 446 Capacitance-concentration-potential plots, various, for organic compound adsorption, 361 Capacitance curves associated with organic adsorption, 356 as a function of potential, 356, 359 and wide-gap semiconductors, 316 Capacitance hump and disappearance with rise in temperature, 201 theory, 201 Capacitance humps, predicted, 199 Capacitance minima, tabulated, 198 Capacitance-surface-tension method in the double layer, concluding discussion, 172 Capacity, from the diffuse double layer theory, 109 Carrier concentration, and the surface states, 325 Cathodic current densities from Teflon to solution, 341 Cations, their surface excess, 90 Cell, diagramed, for electro-osmosis, 409 Cell potential and electronegativity, 271 Volta potential and dipole potential, 268 Cell potentials, related to the pzc and work function, 270 Cells consisting of insulators and semiconductors, 336 Charge and potential measurements, for colloids, 401 Charge, as the variable, eliminates differences between capacitance and surface-tension measurements in double layer, 165 Charge carriers, and injection, 339 Charge dissolution, and surface states, 305 Charge distribution, at interface, 10 Charge due to specifically adsorbed hexafluorophosphate as a function of charge, 99 Charge injection, at anthracene cathodes, 341 Charge on semiconductor-solution interface, 297 Charge-potential curves, diagramed, 88 Charge-potential relationships, diagramed, 92 Charge related to the integral of capacity, 26 Charge related to specific surface excess, 93 SUBJECT INDEX Charge transfer, and thermodynamics, 9 Charging curves of bismuth electrodes, with organic compounds, 364 Chloride adsorption on platinum, various techniques, 174 Clausius-Clapeyron equation, in the double layer, 18 Clusters, in the double layer, 128 Coagulation kinetics of, 430 tabulated,422 theory of, 420 Colloidal stability, and double layers, 420 Colloidal systems, 397 Components of electrode potential, 47 Constant charge, and colloidal repulsion, 426 Contact, metal-metal, 56 Continuity equation, 413 Corrected Tafel plot (CTP), 284 Corrections due to neglect of absorption of water, 180 Crystal orientation, 52 Crystalline surfaces, and work function, 53 Current-potential and nonaqueous systems, 338 Debye length, 113 Definitions used in double layer, 89 Determination of partial charge, Lorenz's method, 182 Dielectric discontinuity, in double layer, 193 Dielectric slabs, energy across, 195 Difference of surface tension between capacitance and electro capillary methods, as a function of concentration, 171 Differential capacitance on bismuth electrodes, 358 for colloids, 402 as a function of potential, 176 of germanium electrode, with the deposition of copper, 323 of germanium electrodes, 315 in nonaqueous solution, as a function of potential, 277 Differential capacities of mercury, calculated and observed, 113 Differential capacity, 373 and Frumkin's theory, 375 of Helmholtz layer for various solid metals, 262

9 SUBJECT INDEX Differential capacity (cont.) for KPF;; in nonaqueous solution, diagramed, 104 and potential, 305 at semiconductor-solution interface, 301 with sodium fluoride, diagramed, 98 Diffuse double layer, various tests, 177 Diffuse double layer theory and calculation of specific surface excess, 98 extensions, 114 limitations, 114 and surface excesses, 179 proofs, 114 validity, 175 Diffuse layer, for colloids, 400 Diffuse layer theory presented, 107 validity, 105 Diffusion equations associated with anthracene crystals, 347 Dimensionless mobility, in electrophoresis, 414 Dimer model, in the double layer, 129 Dipole interactions, in the double layer, 126 Dipole model of the double layer, 127 Dipole potential at the interface, and cell potential, 272 at the interface, determined 269 Dipole potential difference, 64 Direct determination of surface chargc, 227 Discrepancies between capacitance and surface-tension measurements in double layer, 165 Dispersion energy, and adsorption isotherms, 196 Distinction of capacitance, and surface tension, 164 Distribution of concentration of electrons, in holes, at semiconductor-solution interface, 299 Distribution of potential charge in charge at insulator-solution interfaces, 331 DLVO (Deryaguin-Landau-Verwey Overbeek) theory, and colloidal stability, 423 Double layer around a sphere, 399 capacity, in amide solvents, tabulated, 104 flat, 398 Gibbs work, 2 on semiconductor electrodes, Double layer (cont.) at the semiconductor-solution interface, 294 depth of, 296 and theory, 293 some applications of simple theory, 110 structure, 312 thermodynamics methods, I thermodynamics and temperature, 27 without specific adsorption, 83 Double layer theory, and associated solvent systems, 132 Double layers, and colloidal stability, 420 Dupre equation, 102 Effect of potential distribution, at semiconductors, 302 Effect of specific adsorption, and concentration, 143 Electrical work function, as a function of temperature, diagramed, 53 Electrocapillary and capacitance methods, different or the same?, 162 Electrocapillary curves, 171 exemplified, 87 fust determined by Gouy, 274 and Frumkin-Damaskin theory, 370 in nonaqueous solution, 278 shapes characteristic of organic compounds, 355 Electrocapillary equations, 5 deduction, 144 Electrocapillary method, for specific adsorption, 144 Electrocapillary thermodynamies and binary alloys, 33 discussion, 152 and the double layer theory, 140 of partial dissociation, 42 Electrochemical kinetics, and potential of zero charge, 281 Electrochemical systems, interfacial regions, 2 Electrode, surface species in equilibrium with, but not present in, a bolt phase, 41 Electrode bending, a method for adsorption measurements in solid, 161 Electrode kinetic phenomena, 404 Electrode potential, 45 and the crystal orientation, 52 and Galvani potential difference, 71

10 448 SUBJECT INDEX Electrode potential (cont.) of numerous situations, and absolute values, 75 origin, 60 relative, 70 and the work function, 47 Electrode potentials, in practical situations, 74 Electrode reactions, and potential, 77 Electromagnetic retardation, 428 Electron density and diffuse layer theory, 108 and potential energy at metal-metal interfaces, tabulated, 58 and potential energy proijies, tabulated, 59 Electron levels, at surface of semiconductors, occupation, 308 Electron overlap potential, 51 Electron work function as function of centering, tabulated, 54 of liquids, 54 of metals in polar liquids, 65 Electronically nonpolarizable interfaces, 72 Electro-osmosis, 405 in porous plug, 408 Electrophoresis, 412 Electrophoretic mobility measurement of, 413 theory of, 412 Electrosorption valency, 185 Electrosorption valency methods, evaluation, 185 Electrostatic interaction during adsorption process, 197 Electroviscosity, 417 secondary, 418 theory of, 419 tertiary, 419 Electroviscous effects, 417 primary, 418 Ellipsometry, and roughness, 160 Ellipsometry and electrocapillary methods on mercury, compared, 173 Ellipsometry method, for specific adsorption, 157 Energies, in specific adsorption, 187 Energy across iive dielectric slabs, 195 across four dielectric slabs, 194 across smoothly varying dielectric slabs, 195 across three dielectric slabs, 193 Energy (cont.) across two dielectric slabs, 192 diagramed, for electrons and polar liquids, and work function, 61 Energy diagrams, involving photoactivation, 346 Enthalpy, of oxide formation and water in the double layer, 131 Enthalpy and energy, temperature dependence in the double layer, 17 Equations, for thermodynamics in interfaces, basic, 12 Equilibrium, between two metals in contact, 57 Equilibrium concentration, at mercurysolution interface, tabulated, 3 Equivalent circuit, involving polarizable semiconductors, 302 Errors, due to neglect of activity coefficients, 363 Esin-Markov plot, 94 Evaluation of specific adsorption, 148 Excitons, and the insulator-solution interface, 347 Experimental techniques, for semiconductor-solution interface, 312 Expressions for double layer, compared, 130 Extensions, of diffuse double layer theory, 114 Fermi level and calculation of flatband potential, 322 and electrode potential, 49 Flatband potential and calculation of Fermi level, 321 and concentration of electrons, 318 and dependence on ph, mechanism, 320 and diffusion layer, 316 and germanium electrodes, 319 Mott-Schottky, 300 and ph, 320 and semiconductor-solution and semiconductor electrodes, 321 Flat plates and repulslon, 427 repulsion between, theorized, 423 Flory-Huggins statistics and adsorptions isotherms, 195 in double layer, 129 Fluid velocity, and distance from surface, 406

11 SUBJECT INDEX Forces, in specific adsorption, 186 Forees of interaction, between colloids, 432 Free charge. defined, 227 Free energies of adsorption, tabulated, 188 Frumkin, and tw<hlimensional isotherms, 364 Frumkin's equation, for organic adsorption, 370 Frumkin's model, for organic adsorption, 370 Gallium, adsorption on, 359 Gauss' theorem, and diffuse double-layer theory,108 Geriseher, sensitization of redox transformations, 329 Germanium electrodes and the capacitance-potential plot, 315 and tlatband potential, 319 Gibbs adsorption equation, its applications, 16 Gibbs-Duhem equation for bulk phases, 15 for separate phases, 8 Gibbs equation, and organic compound adsorption, 361 Gibbs surface excess, 146 defmition, 137 exemplified, 23 Gouy theory limitations, summarized, 117 at semiconductors, 295 Grahame's capacitance method, for specific adsorption, 149 Green, and the qualitative difference in potential dissolution at the interface between semiconductors and insulators, 330 Hale and MeW, and anthracene crystals, 347 Hamaker constant, 431 Helmholtz layer at semiconductor-solution interface, 319 in solution, in semiconductor-solution interface, 303 Hexyl alcohol, adsorption of, 359 Hump, predicted from capacitance-charge curve, 202 Ideal nonpoiarizable interface, and its thermodynamics, 28, Ideally polarizable electrode, n-solvent interaction energy, for various anions, 143 Ionic adsorption, isotherms for, 189 Inflection, on coverage-charge curve with multiple imaging, 201 Inflection points and capacitance hump, 201 in coverage-charge curves, 197 calculated, 200 Injections, and exchange currents on insulator electrodes, 339 Inner layer capacity in the presence of ethylene carbonate, 130 involving silver iodide, and the interface, 403 structure, 124 Insulator-electrode interface, 329 Insulator electrodes, and injection of charge carriers, 339 Insulator-electrolyte thermodynamics, 332 Interface blocked, 2 for metal-nonaqueous solution, 274 Interfaces, actual, 67 Interfacial tension as a function of concentration, diagramed, 163 at a gold electrode, 162 in mercury, 137 several other names proposed for it, 20 Intrinsic semiconductor, capacity as a function of potential, 301 Invalidity, of diffuse double layer theory, 175 Inversion layer, and space charge, 307 Iodide, adsorbed on anthracene electrodes, 335 Ion exchange, and electrocapillary thermodynamics, 38 Ionic crystals, with interphases, their thermodynamics, 38 Isodynamic curves, diagramed, 428 Isoelectric change, 40 Isotherm deduction of, 195 properties due to Blomgren and Bockris. 191 Isotherms multiple-energy, 20 I two-dimensional, 366

12 450 Jellium,50 Kinetics, of slow coagulation, 431 Latex suspensions, theory for, 433 Laser illumination, in electrophoresis, 414 Limitations, of diffuse double layer theory, 114 Limiting currents, at Teflon electrodes, 343 Linear sweep voltammogram, and electrocapillary thermodynamics, 40 Lippmann equation, 16, 85 Liquids, and polar surfaces, 55 Literature, for colloids, 433 Logarithmic isotherms, 142 Lorentz-Lorenz equation, and specific adsorption, IS 8 Luminescence, electrochemical, 344 Measured potentials, their meaning, 69 Measurement, of electro-osmosis, 408 Metal, in contact with solution of a single salt, thermodynamics, 22 Metal-electrolyte-melt interface, 277 Metal-nonaqueous solution interface, 274 Metal overlayers, a special case of metalmetal contacts, 60 Metal-polar-liquid contact, its thermodynamics, 61 Metallization of semiconductor-solution interface, 304 Methanol, adsorbed on platinum, 383 Methanol adsorption, irreversible, 386 Methods, for specific adsorption, 151 Microelectrophoresis, 414 Microscopic approach, to colloidal stability, 428 Microscopic sheets, interaction between, measured,433 Mobility, reduced, and the theory of electrophoresis, 414 Model, of series capacitor, 112 Models, of double layer, 100 Molecular model for adsorption, frrst presented by Butler, 377 Multiple-energy isotherms, 201 Multiple-imaging isotherm, 191 Observed and calculated values for de.ide, 97 SUBJECT INDEX Oil-water interface at colloids, 400 Operative electrode potential, 71 Organic adsorption, and hydrogen-oxygen adsorption, 383 Organic compounds, adsorption of, in Frumkin's theory, 372 Organic isotherm, a generalization, 377 Organic molecules, their adsorption, as intcrpreted by Bockris, 265 Organic substances, irreversible adsorption, 381 Origin of electode potentials, 60 Oxide systems, their capacitance, 404 Parsons' method, for specific adsorption, 149 Partial charge transfer and electrocapillary thermodynamics, 42 enunciated by Lorenz, 1961, 4 and Lorenz, 43,181,224 a summary of viewpoint, 186 and Vetter and Schultze, 183 Pauli principle, and Fermi level, 48 ph and flatband potential, 320 Phenol, adsorbed on mercury, 367 Photoelectrochemica1 measurements, and electrode potential, 74 Photoelectrochemical processes, 345 Photoelectromotive force, and current density, 347 Photoinjection, and current density, 347 Photopotential, 309 and flatband potential, 310 in semiconductors, 318 Photopotentials, and semiconductorsolution interface, 311 Photosensitized reactions, and excited molecules, 349 Pits, and condensed films, 375 Platinum, and methanol adsorption, 383 Platinum group metals, and specific adsorption, 224 Polarizable electrode, completely defmed by Planck,222 Polarizable interface, 67 Polarization curves, as a function of double layer structure, 283 Polishing, of semiconductors, 312 Poly crystalline surfaces, and work function, 53 Polymer mms, and electrodes, 341

13 SUBJECT INDEX Potential between plane of closest approach and bulk of solution, 110 and electrode reactions, 77 at interface, effective metal ions, 68 penetration into the semiconductor, 294 Potential differences, involved in semiconductor-solution interface, 296 Potential dissolution in double layer, ph dependence,320 Potential distribution in double layer, at semiconductors, 314 at flatband potential, 319 at the semiconductor-solution interface, 293 Potential drop in Helmholtz layer, diagramed, 303 of semiconductor-solution interface, calcula ted, 3 14 Potential energy of attraction, between colloidal particles, 428 as a function of separation, 423 of interaction between particles, 422 and repulsion, in colloid systems, 426 Potential energy prome, for metal-polarliquid-vacuum system, diagramed, 65 Potentials how one measures them, 69 at the pzc, tabulated, 272 Potential of zero charge (pzc), 137, 221 and electrochemical kinetics, 281 as a function of the solvent, 275 methods of determination, 227 in molten salts, 279 and nature of medium, 267 in nonaqueous solution, 280 recommended, tabulated, 228 related to work function, 101 tabulated,76 and the work function, 272 Practical situations, and electrode potential, 74 Pressure, and double layer relations, 26 Pressure, electro-osmotic, theory of, 407 Proofs, of diffuse double layer theory, 114 Pure metal in contact with nonelectrolyte in the solvent, thermodynamics, 32 and two salts in a solvent, thermodynamics, 28 Pzc, related to cell potential, 270 pzc's and relations in,-'clls; 269 in various solvents, Quasithermodynamic methods, for specific adsorption, 144 Quantum efficiency, as a function of wavelength,347 Radiotracer measurements, and double layer work,i40 Radiotracer method, 156 and specific adsorption, 154, ISS, 156 Real potential of iron and water, tabulated, 56 and work function, 61 Reciprocal capacitance, versus reciprocal diffuse layer capacitance, diagramed, 96 Redox reactions at insulator electrodes, equations for, 340 and insulators, 334 Relation of cell potential to electronegativity, 271 Relative electrode potential, 70 Relaxation, in space charge with semiconductors, 306 Relaxation time, at semiconductor-solution interface, 309 RepUlsion between dissimilar surfaccs, 427 bctwccn flat platcs, 423 bctwcen sphcrical particles, 425 Rctardation, elcctromagnctic, 428 Ribbon extcnsion mcthod, for diffcrcntial surfacc tensions, 161 Roughncss, and specific adsorption, 160 Schulze-Hardy rule, and explanation of colloid thcory in elcctrochcmical terms, 431 Seal capillaries, and electro-osmosis, 405 Semiconducting phases, and electrocapillary thermodynamics, 36 Semiconductor electrochemistry, and rcvicws, 292 Semiconductor clcctrodes, and industrial application, 326 Semiconductor-clectrolytc intcrfacc, 306

14 452 Semiconductor-solution interface, 312 experimental study, 311 and Helmholtz layer, 304 and metallization, 304 Semiconductors and the boundaries of valency and induction vacuum, 323 polishing of, 312 and insulators, cells of,337 Series capacity model, 112 Series model, for the inner double layer, 126 Shear plane, its position, 416 Shear stress, and surfaces, 21 Silicon electrodes, in coating of oxide, 314 Silver iodide, and surface potential, 416 Simultaneous adsorption, 213 of cations and anions, Delahay's approach,206 methods compared and discussed, 211 results compared, 210 Single-electrode potential, 71 Single-imaging isotherm, 191 Space charge and inversion layer, 307 and relaxation time, 309 at semiconductor-solution interface, 312 Sparnaay, and oil-water interfaces, 400 Specific adsorbability, and ionic radius, 142 Specific adsorption detection, 100 determination, 144 equations for, 147 evaluation, 148 as a function of charge, diagramed, 140 on the gold electrode, 160 history, 139 method based on adsorbated concentration in solution, 154 of nitrate ions, 208 in presence of thallous ions, 208 and partial charge transfer, 180, 341 and radio tracer method, 154 and results obtained by electrocapiuary, ellipsometry, and radio tracer methods, compared, 172 simultaneous, 207 of cations and anions, 205 and solvation sheath, 203 and temperature, 143 Specific surface excess, in terms of diffuse layer theory, III SUBJECT INDEX Spectroscopic and optical methods, for semiconductors, 312 Spreading effect, 51 Solid phases, their interfacial thermodynamics, 19 Solvation sheath, and specific adsorption, 203 "Squeezing out" effects, 365 Standard chemical potential, of iron and water, tabulated, 56 Standard model, for colloids, 400 Standard potentials, tabulated, 76 Standard state and adsorption isotherms, 189 for electrons, in electrochemical calculations, 49 Stern's isotherm, 187 Streaming potential, 409 Superequivalent adsorption, its defmition, 138 Surfa<..'C charge on different faces of single crystals, 264 of nonaqueous solution, 275 Surface concentration, of magnesium, diagramed, 115 Surface conductivity, and semiconductorsolution interface, 293, 313 Surface coverage, from ellipsometry and capacitance, compared, 173 Surface dipole potential difference, 101 Surface excess of anions, 90 as a function of charge density, 148 as a function of potential, 145 of organic compounds, 361 in simple solutions, 91 Surface of metals, described, 50 Surface potential, and silver iodide, 416 Surface states, 302 and cathodic polarization, 325 and deposition of metals, 325 elucidation of their nature, 326 and hole lifetime, 325 at semiconductors, 303 Shockley levels, 303 theory, 303 Surface tension and capacitance, 24 decreased by sodium acetate, 265 on solid metals, 160 Surfaces, with shear stresses, 21 Tamm states, 303

15 SUBJECT INDEX Technique for measurement with colloidal interfaces, 402 Techniques, and double-layer investigations, 84 Temperature, and double-layer relationships, 26, 27 Temperature dependence, of specific adsorption, diagramed, 143 Terylene electrodes, and the iodine-iodide system, 343. Test, of capacitance-surface-tension difference in double-layer determinations, 164 Tests, of DLVO theory, 428 TetraaIkylammonium halides, and adsorption at mercury surfaces, 266 Tetracene-water surface, 347 Thermodynamic potentials, in the double layer, 14 Thermodynamic treatment consistent of absorption processes, 225 Thermodynamics of adsorption of organic compounds, 360 for charged interfaces, 7 of insulator-solution interface, 332 for interfacial region, 15 of ion exchange membranes, 38 of ionic crystals, in the interphasiai region, 37 of a metal in contact with a solution containing a single associating salt, 22 of a pure metal, in contact with a solution of an electrolyte and nonelectrolyte in a solvent, 32 of pure metal, in contact with two salts, 28 of single bulk phase, 4 of three-phase electrodes, with gaseous component in equilibrium with solution, Thomas-Fermi statistics, and scmiconductor-solution interfaces, 301 Three-part model, for double layer, 130 Three-phase electrode, its electrocapillary thermodynamics, 38 Two-capacitor model, 370 Two-position model, for double-layer water, 128 Validity of diffuse double-layer theory, 175 Velocity, and streaming potential, 410 Viscosity, and double layer, 416 Volta potential and cell potential, 267 and potential of zero charge, 267 Volta potentials, tabulated, 270 VuIca potential difference, 65 Water, surface excess, and its neglect, 179 Water orientation, Trasatti's approach, 131 Ways of obtaining surface excess, 89 Wide-gap semiconductors, 292 Work function and centering, 53 and crystal orientation, 52 and crystal phase, 53 and metal equilibrium, diagramed, 67 of metal in solution, diagramed, 67 of metals made for solutions, tabulated, 76 and potential of zero charge (pzc), 271, 272. and real potential, 61 and temperature coefficient, 280 Work function difference, and cell potential, 273 Work functions differences among various metals, 281 tabulated, 50 Work of adhesion, tabulated,103