1969 Volume 42 Issue 12 Pages 3478-3483
Influence of polyvalent metal ions on the hydrolysis of 2-, 3- and 4-pyridylmethyl phosphate was investigated at μ=0.01 in a lower pH range. The thorium ion accelerated the hydrolysis rate of all the phosphates to a remarkable extent as investigated at 40, 70 and 90°C. The primary participation of the phosphate moiety of each pyridylmethyl phosphate in the interaction with thorium(IV) was considered to be the main cause of this catalysis. Thus, the thorium catalysis was mechanistically distinguished from the copper catalysis which has been clarified previously. In addition, the vanadyl ion also demonstrated positive catalytic effect. On the other hand, iron(III) and aluminum(III) retarded the hydrolysis rate. This was ascribed to the reduced fraction of the active monoionic species as a result of metal-complex formation with the phosphates in the course of hydrolysis.
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