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J. Am. Chem. SOC.the calculations for temperature rise. Corrections were made graphically for heat leak where appropriate; since the heat leak for the calorimeter was about 5 X s-l (half-time for cooling of about 200 min) reactions with half-lives of as much as 20 min could conveniently be followed. Since the response lag of all the various components of the calorimeter was only a few seconds, rates could be measured for reactions with half-lives of only a fraction of a minute. Acknowledgment.Abstract: A systematic study of the quaternary ammonium catalyzed solid-liquid esterification of alkyl chlorides by alkali formate has been undertaken. The maximum conversion and the kinetics of the reaction were found to be strongly dependent on the type of formate salt used. The reaction rate was highest when a definite amount of water was added. The optimal water content varied strongly when the inorganic cation, the reaction temperature, or the catalyst concentration was changed. When the amount of water was limited, most of it was found surprisingly in the organic phase as water of hydration of the quaternary ammonium ion pair, reducing the rate of the homogeneous reaction step. At very low water concentrations the overall rate was limited by slow mass transfer, which could be enhanced by application of ultrasound.

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