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Item Theory of Electrolytes: Part 2.—Tests of the Model of Polarisable Spheres, with some Implications for “ Structure ” in Solutions(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1977, 73 (07), 1977) Bennetto, H. P.; Spitzer, Jan J.Predictions of the polarised-sphere theory of electrolytes are compared with experimental results for 1:1, 1:2 and 1:3 electrolytes in water. The theory gives a good account of activity coefficients for a large number of electrolytes in dilute solution (κa < 0.5), and the partial molal enthalpies for 1:1 electrolytes are also accommodated. A limited survey of the results for hydrochloric acid in a number of solvents shows the applicability of the theory for a wide range of the dielectric constant. The significance of ion-size parameters is discussed in relation to the polarisation of solvated ions, and further developments of the electrostatic model are considered in the light of present limitations. An outline is given of a new approach to the phenomenon of “structure” in solutions.Item Diffusion in Binary Liquid Mixtures of non Electrolytes(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (02), 1978) Barrie, James A.; Dawson, Ray B.; Sheppard, Richard N.Self diffusion coefficients at 25 'C for octamethylcyclotetrasiloxanc in binary mixtures with benzene and carbon tetrachloride have been measured by pulsed field gradient pulsed n.m.r. A comparison is made of the diffusion data for these systems with the predictions of the Darken equation and of simple hard sphere theory expressions; neither approach gives a satisfactory representation to the data. Friction coefficients, Li, for octamethylcyclotetrasiloxanc have been evaluated for part of the composition range.Item Heats of Solution of Electrolytes in Ethanol and Derived Enthalpies of Transfer from Water(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (02), 1978) Abraham, Michael H.; Ah-Sing, Eric; Namor, Angela F. Danil De; Hill, Tony; Nasehzadeh, Asadollah; Schulz, Ronald A.Heats of solution of 12 1:1 electrolytes in ethanol have been determined calorimetrically, and have been extrapolated to zero electrolyte concentration to give iXH° values for these electrolytes. Together with literature data for 9 other 1:1 electrolytes, these measurements yield a set of single ion enthalpies of transfer from water to ethanol for 11 univalent cations and 6 univalent anions. Using the assumption that A/7t‘?(Ph4As+) = A//°(Ph4B~), it is shown that small univalent cations are enthalpically more stable in ethanol than in water, but that the larger tctra-alkylammonium ions are less stable in ethanol. With the same assumption, it is also shown that all the univalent cations and anions studied are of almost the same enthalpy (within about ±0.5 kcal mol-1) in the three alcohols methanol, ethanol and 1-propanol.Item Proton and Deuteron Mobility in Normal and Heavy Water Solutions of Electrolytes(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1974, 70 (1-6), 1974) Roberts, Noel K.; Northey, Helen L.Proton and deuteron mobility in normal and heavy water solutions of some alkali halides (NaCl, KCI, KBr and KI) and tetra-alkylammonium bromides (where alkyl is Me, Et, Pr or Bu) is measured polarographically and the diffusion coefficients calculated from a corrected Ilkovic equation. The results are analysed in terms of the effect of electrolyte concentration on the excess or Grotthuss mobility of the hydrogen and deuterium ion. The results raise some questions about the accepted mechanism for the transport of the proton and deuteron in solution.Item Desorption of Electrolytes at Liquid-Vapour and Liquid-Liquid Interfaces(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1977, 73 (1), 1977) Aveyard, Robert; Saleem, Syed M.; Heselden, RoyThe desorption of various simple inorganic salts at the decanol-water interface has been studied, and analysed together with previously obtained results for the air-electrolyte and dodecane-electrolyte interfaces. The desorption of the salts is much more dependent on the nature of the anion, at all three interface types, than it is on the cation and the results are discussed in terms of the possible interaction between anions and hydration layers at the interfaces. The dependence of free energies of adsorption of alkanols, both from alkane and from electrolyte, on the alkane-electrolyte interface has also been investigated and it is concluded that the chemical potential of the alkanol at the surface is not much affected by the salts, but the influence is greater the less the desorption of the salt.Item Apparent Molar Volumes of Multiply Charged Electrolytes(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (10), 1972) Indelli, A.; Zamboni, R.The apparent molar volumes of K4Mo(CN)8, K3Cr(C2O4)3, Ca2Fe(CN)6, LaFe(CN)6 and K4Zr(C2O4)4 were measured using a pycnometric and dilatometric methods at 25 and 3.39°C. At 25°C K4Mo(CN)8 follows accurately, K3Cr(C2O4)3 and LaFe(CN)6 follow approximately the Debye-Huckel limiting law at high dilution. K4Zr(C204)4 shows very large deviations, probably due to chemical equilibria. At 3.39°C all the salts show positive deviations from the Debye-Huckel limiting law even at the lowest concentrations and have Vo values considerably smaller than at 25°C. This is considered as evidence that solute-solvent interactions are important in determining both Po and the change of v with the concentration.