By M. Liler
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Additional info for Reaction Mechanisms in Sulphuric Acid and other Strong Acid Solutions
The symbol Hc was suggested for this measured function, based on carbon bases (Reagan, 1969). The discrepancy between H^ and Hc is due to the inadequacy of the 2. /R+ =/>ιβπη/Λ+> from which it follows that/ R O H =foienn- This is not strictly true, probably owing to the hydrogen-bonding ability of the carbinol. 1 gives a plot of most acidity functions discussed in this Section against weight per cent of sulphuric acid in sulphuric acid/water mixtures. The acidity function for oleum solutions is not shown.
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).
2. In plotting curve (b) an average activity coefficient for primary anilines was used, since values for iV,iV-dimethylaniline are not available. Bearing in mind a possible uncertainty here, it can be seen from Fig.