Browsing by Author "Fox, Malcolm F."

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Component Interactions in Aqueous Acetone
(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (7), 1972) Fox, Malcolm F.
νmax and Îµmax for the n–π* transition of acetone in aqueous solution do not vary monotonically with acetone concentration. The Klotz-Worley R parameter for these solutions shows a maximum at 0.05 x2 whereas carbonyl infrared intensities are a linear function of acetone concentration. Hydrophobic hydration of acetone is proposed in the initial region with direct molecular interaction at approximately 0.20 and 0.45 x2.
Far-Ultraviolet Solution Spectroscopy of Chloride Ion
(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (07), 1978) Fox, Malcolm F.; Barker, Barry E.; Hayon, Elie
The far-ultraviolet absorption spectra of chloride ion have been studied in a large variety of solvents and over a large range of temperatures. Solvents used include both blue- and red-shifting solvents for charge-transfer-to-solvent transitions, relative to water. New absorption bands have been observed, in addition to characterising those regarded as having been observed previously. For some solvents, measurements have been made down to 59 600 cm–1. In contrast to the iodide and bromide spectra, only one band is found for each of the several states observed because of the small 2P doublet splitting. These bands, and also higher intensity electronic bands observed at higher energies, are correlated on the basis of solvent shifts, temperature sensitivities and oscillator strengths. The nature of the bands is discussed and tentative assignments suggested. Comparisons with bromide and iodide spectra are drawn.
Far-ultraviolet solution spectroscopy of the bromide ion
(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1977, 73 (06), 1977) Fox, Malcolm F.; Hayon, Elie
The far ultraviolet absorption spectra of the bromide ion have been studied in a large variety of solvents and over a wide range of temperatures. The solvents used include those which are strongly red-shifting or blue-shifting, relative to water, for charge-transfer-to-solvent (c.t.t.s.) transitions. For some solvents measurements could be made down to ∼165 nm (60 600 cm–1). A number of new absorption bands have been observed in addition to characterising the previously observed spectra. The experimentally determined spectra are shown to be envelopes composed of overlapping absorption bands which have been deconvoluted using log-normal band shapes, whenever possible. Sets of band pairs have been identified from the spectral resolution and labelled A1/A2, B1/B2. There is some evidence for further members of the series. The first characteristic doublet, A1/A2, has a band separation very close to the doublet splitting of the bromine 2P½2P[fraction three-over-two] atomic states in the gas phase. The B1/B2 band pair has a lower doublet separation. These band pairs have strong c.t.t.s. character as shown by their temperature and solvent sensitivities. Further bands are observed at higher energies. These band systems have been correlated on the basis of solvent shifts, doublet band splittings and temperature coefficients. The nature of the bands is discussed and tentative assignments suggested.