Mochalin V. Thermodynamics of dissolution of non electrolytes in systems water - acetic and water - sulfuric acid

Українська версія

Thesis for the degree of Candidate of Sciences (CSc)

State registration number

0401U000783

Thesis Registration Form

0401U000783.pdf

Applicant for

Specialization

  • 02.00.04 - Фізична хімія

08-02-2001

Specialized Academic Board

Д 11.216.01

Essay

New data on solubilities of various non electrolytes in systems water - acetic and water - sulfuric acid at the acid concentrations 0 - 100 % were obtained for the first time at temperatures 283 - 343 K. An equation (lga)Е = lga - xWlgaW - xAlgaA = L(VЕ/V) previously proposed by E. S. Rudakov and coworkers for non electrolytes solubilities calculations in systems water - mineral acid at the room temperatures was found to be invalid in the wide range of temperatures. The modified equation which involves appropriate volume fractions of the mixed solvent components rather then their mole fractions was found to be much more exact correlation of solubilities compared to the equation mentioned above. The unusual case of compensation effect in the H2O - H2SO4 system was found for the first time. The capacities of well known Pierotti approach for prediction of solubility of non electrolytes in pure sulfuric, nitric and acetic acid as well as in the systems water - acid in the whole composition range at 298 K h ave been discussed. New data on kinetics of isobutene hydration in aqueous sulfuric and phosphoric acids at the room temperatures have been obtained. In case of isobutene hydration correct account of non electrolyte solubility by the equation proposed here led us to elimination of contradictions between the data of various authors concerning dependency of the rate constants of this reaction vs. media acidity reported in literature. At the correct solubility account all literature data together with our experimental values are described by the one common straight line lgk = -(1,24 ± 0,02)H0 - (3,30 ± 0,03). Non unity slope in this equation was referred to salt effects of media on k and H0. Thus the result obtained is in good agreement with traditional mechanism of olefins hydration reactions developed by R. W. Jr. Taft.

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