14 Faraday Halides

The capacitance determined from the initial slopes of the charging curve is about 10/a F/cm2. Taking the dielectric permittivity as 9.0, one could calculate that initially (at the OCP) an oxide layer of the barrier type existed, which was about 0.6 nm thick. A Tafelian dependence of the extrapolated initial potential on current density, with slopes of the order of 700-1000 mV/decade, indicates transport control in the oxide film. The subsequent rise of potential resembles that of barrier-layer formation. Indeed, the inverse field, calculated as the ratio between the change of oxide film thickness (calculated from Faraday s law) and the change of potential, was found to be about 1.3 nm/V, which is in the usual range. The maximum and the subsequent decay to a steady state resemble the behavior associated with pore nucleation and growth. Hence, one could conclude that the same inhomogeneity which leads to pore formation results in the localized attack in halide solutions. 

Davey, E. P. Optical sensitization and adsorption of dyes on silver halide The state of the adsorbed dye. Trans. Faraday Soc. 35, 323 (1940). 

Glew, D.N. and Moelwyn-Hughes, E.A. Chemical studies of the methyl halides in water. Disc. Faraday Soc., 15 150-161, 1953. 

Yapp. C.J. (2000) Climatic implications of surface domains in arrays of 5D and 5180 from hydroxyl minerals Goethite as an example. Geochim. Cosmochim. Acta 64 2009-2025 Yariv, S. Mendelovid, E. Villalba, R. (1980) Thermal transformation of goethite into hematite in alkali halide discs. J. Chem. Soc. Faraday Trans. I. 76 1442-1454 Yariv, S. Mendelovid, E. Villalba, R. Cohen, M. (1979) Transformation of goethite to maghemite in Csl discs. Nature 279 519-520... 

In a lecture presented to the Faraday Society,332 Norrish commented on why the higher vibrational levels of NO were observed in the nitrosyl halide experiments but not by absorption in NO irradiation experiments. He reasoned that, as the emission of NO from the AZH + state populates the first five vibrational levels of NO almost equally,341 the fast-exchange reaction (4) can quickly eliminate all the vibrational levels above the first. However, in the nitrosyl halide experiments, the NO may be formed preferentially in very high levels, such as v — 10 or 11, almost exclusively. Thus, reaction (4) cannot occur initially, and depopulation must be by reaction (2). Reaction (2) is considerably slower than reaction (4), because of the increased difference in vibrational energy between the reactants and products resulting from an-harmonic effects. 

L.G. Harrison. Influence of dislocations on diffusion kinetics in solids with particular reference to the alkali halides. Trans. Faraday Soc., 57(7) 1191—1199, 1961. 

Evans, A. G., et al. The effect od solvents on the ionization of organic halides. Part I. Ionization in nitrobenzene and m-nitrotoluene. Trans. Faraday Soc. 50, 568 (1954) and the following papers by A. G. Evans. 

W.B. Miller, S.A. Safron, D.R. Herschbach, Exchange reactions of alkali atoms with alkali halides—A collision complex mechanism, Discuss. Faraday Soc. 44 (1967) 108. 

For a study of heats of formation of solid solutions of CsCl with other alkali halides, see A.K. Shukla, J.C. Ahluwalia and C.N.R. Rao, 3CS Faraday 1 72, 1288 (1976)... 

Treiner, C. and Chattopadhyay, A.K. The Setchenov constant of benzene in non-aqueous electrolyte solutions alkali-metal halides and aliphatic and aromatic salts in methanol at 298.15 K. 7. Chem Soc. Faraday Trans. 1 1983,79, 2915-2927. 

Ogg and Polanyi, Trans. Faraday Soc., 1935, 31, 1375. Further developed by Evans and Polanyi, ibid., 1938, 34, 11. Calculations based on this theory were carried out for the Na - - Methyl halide reaction by Evans and Warhurst. ibid., 1939. 35. 593-... 

This value is the sum of the CH3 radius i 40A as used by Evans and Warhurst and the Cl- radius of i 6a estimated from electron-diffraction data of gaseous alkyl-halides by Maxwell, Hendricks and Mosley, Physic. Rev., 1937, 53, 968 (see Baugham and Polanyi, Trans. Faraday Soc., 1941, 37, 648). 

J. G. McGoubrey. Trans. Faraday Soc. 51, 743-7 (1955). Acid strength of hydrogen halides in aqueous solutions. 

Electrical conductivity of molten alkali and earth alkali metal halides increase by 2 orders at melting. The electrical conductivity of these melts is purely ionic and their electrolysis follows Faraday s law. Deviations from this law are caused by secondary processes during the electrolysis, as for example dissolution or the back reaction of the electrolysis products. Electrical conductivity and thus also the mobility of ions is, in general, given by quantities like ionic charge, ionic mass, radius, polarizability, and the coordination number. 

R. Mukhopadhyay, B. A. Dasannacharya, J. Tomkinson, C. J. Carlile J. Gilchrist (1994). J. Chem. Soc. Faraday Trans., 90, 1149-1152. Rotational excitations of NH/ ions in dilute solutions in alkali-metal halide lattices. 

K.P. Brierley, J. Howard, K. Robson, T.C. Waddington C.I. Ratcliffe (1982). J. Chem. Soc. Faraday Trans. II, 78, 1101-1119. Inelastic neutron-scattering studies of the torsional and librational modes of the anilinium halides, C6H5NH3X. 

Figure 17.1.11 Reflectance changes caused by halide adsorption on gold in 0.2 M HCIO4. [From T. Takamura, K. Takamura, and E. Yeager, Symp. Faraday Soc., 4, 91 (1970), with permission.]...

GRO/HAY] Gross, P., Hayman, C., Levi, D. L., Heats of formation of metal halides. Zirconium tetrachloride, Trans. Faraday Soc., 53, (1957), 1285-1288. Cited on page 160. 

WEI/MUL] WeingSrtner, H., Muller, C., Hertz, H. G., Composition of the first coordination sphere of Ni in concentrated aqueous NiCl2 and NiBr2 solutions. Part 2 - Application of halide nuclear magnetic relaxation, J. Chem. Soc. Faraday Trans. 1, 75, (1979), 2712-2734. Cited on page 141. 

H. W. Cruse, P.J. Dagdigian, R.N. Zare, Crossed beam reactions of btirium with hydrogen halides. Faraday Discuss. Chem. Soc. 55, 277 (1973)... 

In Eqs. (122) and (123), M(Hg) is an alkali metal amalgam electrode, MX the solvated halide of the alkali metal M at concentration c in a solvent S, and AgX(s)/Ag(s) a silver halide-silver electrode. Equation (124) is the general expression for the electromotive force " of a galvanic cell without liquid junction in which an arbitrary cell reaction 0)1 Yi + 0)2Y2 + coiYi + , takes place between k components in v phases. In Eq. (124) n is the number of moles of electrons transported during this process from the anode to the cathode through the outer circuit, F the Faraday number, and the chemical potential of component Yi in phase p. Cells with liquid junctions require the electromotive force E in Eq. (124) to be replaced by the quantity E — Ej), where Ey> is the diffusion potential due to the liquid junction. The standard potential E° for the cell investigated by Eq. (122) is given by the relationship... 

Cruse HW, Dagdigian PJ, Zare RN. 1973. Crossed-beam reactions ofbariumwithhydrogen halides. Measurement of internal state distributions by laser-induced fluorescence . Faraday Discuss. Chem. Soc. 55 277-292. 

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