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Study of solvent effects on hydrolysis of mono-m-toluidine phosphate
Abstract
The study of solvent effects on the hydrolysis of mono-m-toluidine phosphate has been carried out in 1, 4 dioxane/water and DMSO/water binary systems at various compositions. The pseudo first order rate constants have been determined. The rate of reaction increases with increase in percentage of 1, 4 dioxane and DMSO from 10 to 50% (v/v) at different temperatures. The activation parameters (ΔH≠, ΔG≠, ΔS≠) have been calculated. The results obtained have been explained on the basis of solute-solvent interaction, solvent of the transition state of the medium.
... Under this condition a relation between activation of alcohol and dielectric strength of medium was observed. Various efforts have been put forward to explain the solvent effect in last decade but here I pay a great attention on an important ester which is used as solvent for the antimony reduction of aluminum chloride phosphorus, tri chloride alkyl complex to form the corresponding alkyl phosphorus dichloride [3][4][5]. ...
The rate of base catalyzed hydrolysis of butyle salicylate has been studied in in water-DMF mixture containing up to 30-70% (v/v) has been studied over the temperature ranging from 20-400C. The specific rate constant values followed second order kinetics and decreases with increasing proportion of organic solvent. Number of water molecules associated with activated complex has also been calculated at different temperature with the help of slopes of logk against different mole % of waters. Iso-kinetic temperature was calculated and its numerical values are found to be greater than 300, is an indication of great solvent-solute interaction during the hydrolysis of ester.
The rate of acid catalyzed hydrolysis of propyle methanoate has been studied in the presence of 0.1N-HCI in water-propanol mixture containing up to 30-70% (v/v) has been studied over the temperature ranging from 20-400C. The specific rate constant values followed first order kinetics and decreases with increasing proportion of organic solvent. Number of water molecules associated with activated complex has also been calculated at different temperature with the help of slopes of logk against different mole % of waters. Iso-kinetic temperature was calculated and its numerical values are found to be greater than 300, is an indication of great solvent-solute interaction during the hydrolysis of ester.
The acid catalyzed hydrolysis of butyl formate in presence of 0.1N-HCI in water and the presence of water-DMSO mixture containing up to 30-70% (v/v) was studied over the temperature ranging from 20-400C. The rate of reaction decreases with decrease of water content of the solvent mixture and reached minima at about 70% of organic solvent. The number of water molecule associated with activated complex was showing decrease in trend with increase of temperature, is an indication of change in mechanism from unimolecular to bimolecular in reaction media. The parameters of thermodynamic activation were also calculated and discussed in terms of solvent effect with help of plots of ΔH* versus ΔS*, the isokinetic temperature was calculated and found to be greater than 300.
The kinetic result of hydrolysis of Ethyl Caprlyate has been investigated at different composition of aqueous-organic solvent with Acetone (30-70% v/v) over the temperature range of 20 to 400c. The calculated result follows second order kinetics and is observed that the rate decreases with increasing proportion of Acetone. This behavior is attributed electrostatic nature that various solvent-solute interaction in reaction media. Linear plots of Logk against water concentration shows that equilibrium shifted from dense form to bulky form. Iso-kinetic temperature has been determined with the help of slopes of (ΔH*) versus (ΔS*). Thermodynamic parameter has been calculated with the help of Wynne-Jones and Eyring equation.
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