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Pressure and solvent effects on the kinetics of a Menshutkin reaction in aliphatic alcohols
Author(s) -
Viana César A. N.,
Calado António R. T.,
Pinheiro Lídia M. V.
Publication year - 1995
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610080202
Subject(s) - chemistry , kinetics , triethylamine , solvent , reaction rate constant , thermodynamics , intermolecular force , volume (thermodynamics) , reaction rate , isothermal process , organic chemistry , computational chemistry , catalysis , molecule , physics , quantum mechanics
The kinetics of the Menshutkin reaction between triethylamine and iodoethane was studied at 313 K in seven primary and secondary alkanols. An accurate conductimetric method was employed to obtain second‐order rate constants at pressures of 0·1–200 MPa. Volumes and isothermal compressions of activation were calculated by different model‐based equations which are compared. Activation volumes at 0·1 MPa are in the range −26 to −33 cm 3 mol −1 . Procedures for dissecting intra‐ and intermolecular contributions to the volume of activation are discussed. A clear dependence of model parameters on the solvent volumetric properties was found.