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1446370 
Journal Article 
KINETICS OF ALKALINE HYDROLYSIS OF QUATERNARY PHOSPHONIUM SALTS. THE INFLUENCE OF PROTIC AND APROTIC SOLVENTS ON THE HYDROLYSIS OF ALKYL PHENYLPHOSPHONIUM SALTS 
Dawber, JG; Skerratt, RG; Tebby, JC; Waite, AAC 
2012 
1 
Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507
EISSN: 1563-5325 
187 
10 
1261-1268 
WOS:000306711300014 
Third order rate constants have been determined for the
alkaline hydrolysis of four series of alkylphenylphosphonium salts and
alkylphenylbenzylphosphonium salts at various temperatures in 50%-70% v/v aqueous tetrahydrofuran
and 70% v/v aqueous methanol. Thermodynamic activation parameters have been calculated for the
reactions of each substrate and the effects of varying the ratio of alkyl to phenyl groups have
been compared, as well as the effects of changes in the nature of the alkyl group. Solvation, as
revealed by trends in entropy of activation, plays a largely counter-balancing role with respect
to enthalpy and energy of activation. The role of the isokinetic effect is discussed. In aqueous
tetrahydrofuran, solvation effects on the hydrolyses of phosphonium salts change as the mole
fraction of water changes, and for aqueous methanol the trends in the thermodynamic activation
parameters actually reverse. 
Quaternary alkyphosphonium salts; kinetics; solvation; hydrolysis; activation energy; entropy; enthalpy 
IRIS
• Methanol (Non-Cancer)
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