Download PDF by M. Liler: Reaction Mechanisms in Sulphuric Acid: And other Strong Acid

By M. Liler

ISBN-10: 0124500501

ISBN-13: 9780124500501

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Additional resources for Reaction Mechanisms in Sulphuric Acid: And other Strong Acid Solutions

Sample text

The chemical shift of the ions themselves is probably sensitive to the nature of the neighbour­ ing molecules or ions (in ion pairs). Chemical shifts of oleum solutions have also been measured by Gutowsky and Saika (1953), by Gillespie and White (1960) and by Stopperka (1966b). The effect of increasing concentrations of sulphur trioxide is almost nil up to 20 per cent free S0 3 , but at higher concentrations there is a steady up-field shift, probably due to the break-up of hydrogen-bonded structure (Stopperka, 1966b).

The sulphate is separated as barium sulphate. Its conversion into 35S-labelled sulphuric acid has been described by Masters and Norris (1952). The dried barium sulphate is dissolved in 96 per cent sulphuric acid, and the solution is then equilibrated with sulphur dioxide at 350°C (Norris, 1950). Isotopic exchange takes place and 35S-labelled sulphur dioxide is obtained. This can be used to label inactive sulphuric acid by the same equilibration procedure at higher temperature. More recently two other methods of converting neutron-irradiated potas­ sium chloride into labelled sulphuric acid have been described (Nikolov and Mikhailov, 1965; Suarez, 1966).

Thus ions affect the chemical shift of the solvent molecules by the effect of their charge in the solvation shell, and outside it, by disturbing the hydrogen-bonded structure of the remaining solvent. , 1959) and the disruption of the structure therefore makes a positive contribution to the shielding of the protons. The chemical shift of the ions themselves is probably sensitive to the nature of the neighbour­ ing molecules or ions (in ion pairs). Chemical shifts of oleum solutions have also been measured by Gutowsky and Saika (1953), by Gillespie and White (1960) and by Stopperka (1966b).

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