Rate constant, base hydrolysis pesticides

Base hydrolysis kinetic data are reported for ppb solutions of carbofuran,3-OH carbofuran, methomyl and oxamyl. The results are compared with those reported previously for aldicarb, aldlcarb sulfoxide, and aldicarb sulfone. Second order reaction rate constants, k, have been calculated and range from 169 liter mln mole for oxamyl to 1.15 liter mln mole for aldicarb. The order for rate of base hydrolysis is as follows oxamyl >3-hydroxycarbofuran >aldicarb sulfone v- carbofuran >aldicarb sulfoxide > methomyl -v aldicarb. The activation energy for the base hydrolysis of carbofuran was measured to be 15.1 +0.1 kcal mole , and is similar to the value previously reported for aldicarb sulfone. Rapid detoxification of aldicarb, a representative oxime carbamate pesticide, by in situ hydrolysis on reactive ion exchange beds is reported. 

Table VI. Base Hydrolysis Rate Constants of Carbamate Pesticides and Metabolites at 15°C...

The hydrolysis of pesticides which are sorbed to sterilized natural sediments has been investigated in aqueous systems at acid, neutral and alkaline pH s. The results show that the rate constants of pH independent ("neutral") hydrolyses are the same within experimental uncertainties as the corresponding rate constants for dissolved aqueous phase pesticides. Base-catalyzed rates, on the other hand, are substantially retarded by sorption and acid-catalyzed rates are substantially enhanced. A large body of evidence will be presented which substantiates these conclusions for a variety of pesticide types sorbed to several well-characterized sediments. The significance of our results for the evaluation of the effects of sorption on the degradation of pesticides in waste treatment systems and natural water bodies will also be discussed. 

Both the automatic coulometric titration of petroleum streams and the continuous monitoring of pesticides and sulfur-halogen compounds indicate that the coulometric titrator method is amenable to the automatic maintenance of the concentration of a component in a solution system. A manual version of this approach has been used to study the kinetics of hydrogenation of olefins as well as to determine the rate of hydrolysis of esters.12 The latter system is a pH-stat that is based on the principles of coulometric titrations. Equations (4.9)-(4.11) indicate how this approach is applied to the evaluation of the rate constants for ester hydrolysis. A similar approach could be used to develop procedures for kinetic studies that involve most of the electrochemical intermediates summarized in Table 4.1. The coulometric titration method provides a convenient means to extend the range of systems that can be subjected to kinetic study in solution. 

---