scholarly journals The Kinetics of the α-Chymotrypsin-catalyzed Hydrolysis of p-Nitrophenyl Acetate in Organic Solvent-Water Mixtures

1966 ◽  
Vol 241 (21) ◽  
pp. 4825-4834
Author(s):  
Larry Faller ◽  
Julian M. Sturtevant
1974 ◽  
Vol 27 (7) ◽  
pp. 1423 ◽  
Author(s):  
DG Oakenfull

With the general aim of elucidating the role of water structure in the kinetics of hydrolysis, a comparative study has been made of the kinetics of the hydrolysis of acetic anhydride and the reaction of 4-nitrophenyl acetate with imidazole in mixtures of water with ethanol, t-butyl alcohol, dimethyl sulphoxide and dioxan. Both rate constants were always reduced by the addition of organic solvent. Transition state activity coefficients were measured for both reactions in dimethyl sulphoxide-water mixtures and compared with the activity coefficient of phenylalanine (a model zwitterionic transition state). Activation parameters were measured for the hydrolysis of aceticanhydride in t-butyl alcohol-water and dimethyl sulphoxide-water mixtures. Semilogarithmic plots of rate constant against Winstein's Y-value were non-linear for some of the solvents and this fact, coupled with the effect of dimethyl sulphoxide on the transition state activity coefficients, leads to the conclusion that specific interactions of the solvent with the reactants and with the transition state could be of major importance in controlling the reaction rate.There was no obvious relationship between the effect of an organic solvent on the kinetics of hydrolysis of acetic anhydride and its effect on the structure of water.


1980 ◽  
Vol 45 (11) ◽  
pp. 2873-2882
Author(s):  
Vladislav Holba ◽  
Ján Benko

The kinetics of alkaline hydrolysis of succinic acid monomethyl and monopropyl esters were studied in mixed aqueous-nonaqueous media at various temperatures and ionic strengths. The results of measurements are discussed in terms of electrostatic and specific interactions between the reactants and other components of the reaction mixture. The kinetic parameters in the media under study are related to the influence of the cosolvent on the solvation sphere of the reactants.


1987 ◽  
Vol 52 (10) ◽  
pp. 2375-2382 ◽  
Author(s):  
Ľubica Adamčíková ◽  
Peter Ševčík

Glycerol causes chemical oscillations in Belousov-Zhabotinskii reaction in a closed system as well as in a reaction solution bubbled with nitrogen. Since the oxidation of glycerol with bromate ions does not proceed autocatalytically and bromine in the oxidation state 0 or +1 in the absence of light does not react with glycerol, hydrolysis of bromine is the probable source of bromide ions in the studied oscillation system.


1981 ◽  
Vol 46 (5) ◽  
pp. 1229-1236 ◽  
Author(s):  
Jan Balej ◽  
Milada Thumová

The rate of hydrolysis of S2O82- ions in acidic medium to peroxomonosulphuric acid was measured at 20 and 30 °C. The composition of the starting solution corresponded to the anolyte flowing out from an electrolyser for production of this acid or its ammonium salt at various degrees of conversion and starting molar ratios of sulphuric acid to ammonium sulphate. The measured data served to calculate the rate constants at both temperatures on the basis of the earlier proposed mechanism of the hydrolysis, and their dependence on the ionic strength was studied.


1986 ◽  
Vol 51 (12) ◽  
pp. 2786-2797
Author(s):  
František Grambal ◽  
Jan Lasovský

Kinetics of formation of 1,2,4-oxadiazoles from 24 substitution derivatives of O-benzoylbenzamidoxime have been studied in sulphuric acid and aqueous ethanol media. It has been found that this medium requires introduction of the Hammett H0 function instead of the pH scale beginning as low as from 0.1% solutions of mineral acids. Effects of the acid concentration, ionic strength, and temperature on the reaction rate and on the kinetic isotope effect have been followed. From these dependences and from polar effects of substituents it was concluded that along with the cyclization to 1,2,4-oxadiazoles there proceeds hydrolysis to benzamidoxime and benzoic acid. The reaction is thermodynamically controlled by the acid-base equilibrium of the O-benzylated benzamidoximes.


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