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DOSY studies of hydrogen bond association: tetramethylsilane as a reference compound for diffusion studies
Author(s) -
Cabrita Eurico J.,
Berger Stefan
Publication year - 2001
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.917
Subject(s) - chemistry , tetramethylsilane , hydrogen bond , association (psychology) , computational chemistry , diffusion , organic chemistry , molecule , thermodynamics , physics , philosophy , epistemology
The use of tetramethylsilane (TMS) as an internal diffusion reference for DOSY measurements related to molecular association forced by H‐bond in solution is proposed. By using such a reference, it is possible to determine the extent to which the diffusion of the solutes is affected by changes in viscosity or H‐bonding, after modifications in the composition of the solution under study. Therefore, changes in hydrodynamic radii due to H‐bonding can be calculated. Three examples of the use of this reference in diffusion studies related to H‐bonding are presented: the addition of an H‐bond acceptor to a mixture of two compounds with very similar hydrodynamic radii and molecular weights, but where only one can be involved in H‐bonding, the addition of an H‐bond acceptor to a mixture of alcohols with different H‐bond acidities and the addition of an H‐bond acceptor to a mixture of two isomeric alcohols with different steric hindrances. Copyright © 2001 John Wiley & Sons, Ltd.