Abstract
The hydrolysis of dinitrophenyl phosphate dianions was studied in the presence of cationic polyelectrolytes. The polyelectrolytes used were dimethyldiallylammonium chloride–SO2 copolymer (DM), diethyldiallylammonium chloride–SO2 copolymer (DE), methylbenzyldiallylammonium chloride–SO2 copolymer (MBZ) and methyl-p-nitrobenzyldiallylammonium chloride–SO2 copolymer (MNBZ). The hydrolysis was a first-order reaction both in the presence and in the absence of the polyelectrolytes and was largely accelerated thereby as a consequence of the electrostatic interactions, even more appreciably than by low molecular weight electrolytes. For both 2,4-dinitro-and 2,6-dinitrophenylphosphates, the acceleration factor was in the order MNBZ>MBZ>DE>DM, the largest factors being about 60 and 20 for 2,4-and 2,6-phosphates, respectively. The acceleration was found to be again due to the enthalpy decrease; the activation entropy was shown to decrease by polyelectrolyte addition.
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Ueda, T., Harada, S. & Ise, N. Catalysis by Cationic Polyelectrolytes in Hydrolysis of Dinitrophenyl Phosphate Dianions. Polym J 3, 476–481 (1972). https://doi.org/10.1295/polymj.3.476
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DOI: https://doi.org/10.1295/polymj.3.476