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Kinetics and thermodynamics of sulfuric acid‐mediated cleavage of substituted diaryl sulfones
Author(s) -
Ward Robert S.,
Diaper Richard L.,
Roberts David W.
Publication year - 2001
Publication title -
journal of surfactants and detergents
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.349
H-Index - 48
eISSN - 1558-9293
pISSN - 1097-3958
DOI - 10.1007/s11743-001-0173-5
Subject(s) - chemistry , sulfuric acid , arrhenius equation , activation energy , sulfonic acid , reaction rate constant , titration , kinetics , cleavage (geology) , sulfonate , order of reaction , inorganic chemistry , organic chemistry , physics , geotechnical engineering , quantum mechanics , fracture (geology) , engineering , sodium
The cleavage of di‐ p ‐tolyl sulfone with concentrated sulfuric acid has been shown to occur at elevated temperatures (>120°C). The products were confirmed as the corresponding sulfonic acids by gas chromatography‐mass spectrometry analysis of the sulfonate ester derivatives. The cleavage reactions of a series of di‐ p ‐substituted diaryl sulfones with sulfuric acid have been studied. A method using a double end‐point titration has been used to quantify the amounts of sulfonic acid formed as the reactions proceed. These data have been used to construct second‐order rate plots over a range of temperatures and to determine rate constants for the cleavage reactions. The second‐order rate plots showed good linearity. Activation energies were determined from Arrhenius plots of the second‐order rate constants over a range of temperatures. The presence of electron‐donating groups decreases the activation energy of the reaction, whereas the presence of electron‐with‐drawing groups increases the activation energy of the reaction.