ChemInform Abstract: SOLVOLYSIS RATES IN AQUEOUS-ORGANIC MIXED SOLVENTS. III. KINETICS OF THE ALKALINE SOLVOLYSIS OF MONOCHLOROACETATE ION IN WATER-TERT-BUTYL ALCOHOL SOLUTIONS

1976 ◽  
Vol 7 (39) ◽  
pp. no-no
Author(s):  
EL-HUSSIENY M. DIEFALLAH
Keyword(s):  
Mixed Solvents ◽  
Butyl Alcohol ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Aqueous Organic Mixed Solvents ◽  
Kinetics Of

Solvolysis rates in aqueous–organic mixed solvents. III. Kinetics of the alkaline solvolysis of monochloroacetate ion in water – tert-butyl alcohol solutions

1976 ◽  
Vol 54 (11) ◽  
pp. 1687-1691 ◽  
Author(s):  
El-Hussieny M. Diefallah
Keyword(s):  
Mole Fraction ◽  
Mixed Solvents ◽  
Activation Parameters ◽  
Butyl Alcohol ◽  
Solvent Mixtures ◽  
First Order ◽  
Tert Butyl Alcohol ◽  
Rate Of Reaction ◽  
Aqueous Organic Mixed Solvents ◽  
Kinetics Of

The temperature dependence of the rate of alkaline solvolysis of monochloroacetate ion in water – tert-bulyl alcohol solutions has been determined. The rates of reaction were first order with respect to both the chloroacetate ion and to the total solvoxide ion concentrations. The reactivity is enhanced, first slowly, and then more rapidly, by increasing the concentration of tert-bulyl alcohol in the solvent mixtures. The rate of reaction increases with the reciprocal of the dielectric constant of the medium and the plot of log kvs. 1/D can best be represented by two lines intersecting at a point corresponding to 0.9 water mole fraction. The activation parameters ΔH*and ΔS* for the solvolysis reaction showed a minimum at about 0.9 water mole fraction. The significance of these results from the viewpoint of the electrostatic theory and the changing of solvent structure in such mixtures is discussed.

Thermodynamic and Kinetic Investigation of the Solvent Effect on the Oxidation of [Co(en)2SCH2COO]+ with S2O82- In Water-Methanol and Water-tert-Butyl Alcohol Mixtures

1993 ◽  
Vol 58 (5) ◽  
pp. 1001-1006 ◽  
Author(s):  
Oľga Vollárová ◽  
Ján Benko
Keyword(s):  
Transfer Functions ◽  
Activation Parameters ◽  
Butyl Alcohol ◽  
Oxidation Of Co ◽  
Kinetics Of Oxidation ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Alcohol Mixtures ◽  
Kinetics Of

The kinetics of oxidation of [Co(en)2SCH2COO]+ with S2O82- was studied in water-methanol and water-tert-butyl alcohol mixtures. Changes in the reaction activation parameters ∆H≠ and ∆S≠ with varying concentration of the co-solvent depend on the kind of the latter, which points to a significant role of salvation effects. The solvation effect on the reaction is discussed based on a comparison of the transfer functions ∆Ht0, ∆St0 and ∆Gt0 for the initial and transition states with the changes in the activation parameters accompanying changes in the CO-solvent concentration. The transfer enthalpies of the reactant were obtained from calorimetric measurements.

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