Abstract
The hydrolysis, effected by both a simple and a polymeric alkali of the potassium ethyl monoesters of oxalic, maIonic, succinic, glutaric and adipic acids, prepared in a high state of purity, have been studied. The polymeric alkali used was the (known) poly (vinyl-benzyltrieihyl ammonium hydroxide), which was prepared as an aqueous solution from chloromethylated polystyrene by quaternisation and basification by ion exchange. Second-order rate-plots, obtained for the oxalate conductimetrieally and for the other esters by a titration technique, were found to be linear for the hydrolyses conducted in the presence of sodium hydroxide and convexly curved, in a manner indicating deceleration, for those conducted in the presence of the polymeric hydroxide. For the temperature and concentration conditions used the instantaneous rate constants in the presence of the polymeric hydroxide were found to be higher by factors ranging between 1. 78 and 7. 86 than those in sodium hydroxide. The catalytic efficiency of the polymeric hydroxide has been discussed in terms of electrostatic association of the charged monoesters near and within the polycation in which region there is also an enhanced concentration of hydroxyl counterions. The fall-off of rate with time in the presence of the polymeric hydroxide, and the effect of temperature on the reaction rate, together with the effect of the increase in molecular length of the ester anion on the rate-increase factor, have also been considered. Three condensation reactions involving compounds with active methylene groups in aqueous buffered solution alone and in the presence of three water-soluble polymers have been studied using a gravimetric technique. Small increases in rates of condensation have been observed in the presence of the polymers. This latter investigation, commenced before the work described above, was discontinued since the accelerations observed were not large and the reaction situations are complex.