Solvation enthalpies and rates of nucleophilic displacement of alkali halides in dimethyl sulfoxide

1968 ◽  
Vol 90 (24) ◽  
pp. 6698-6700 ◽  
Author(s):  
R. F. Rodewald ◽  
K. Mahendran ◽  
John L. Bear ◽  
Richard. Fuchs
Keyword(s):  
Dimethyl Sulfoxide ◽  
Alkali Halides ◽  
Nucleophilic Displacement

Mechanisms of Nucleophilic Displacement in Aqueous Dimethyl Sulfoxide Solutions

1961 ◽  
Vol 83 (20) ◽  
pp. 4281-4284 ◽  
Author(s):  
Richard Fuchs ◽  
Gloria E. McCrary ◽  
Jordan J. Bloomfield
Keyword(s):  
Dimethyl Sulfoxide ◽  
Nucleophilic Displacement

Ion Pair Formation and Solvation Energies in Solutions of Alkali Halides in Dimethyl Sulfoxide. II. Model Calculations

1975 ◽  
Vol 53 (7) ◽  
pp. 1007-1018 ◽  
Author(s):  
Merrill S. Goldenberg ◽  
Peeter Kruus ◽  
Stephen K. F. Luk
Keyword(s):  
Dimethyl Sulfoxide ◽  
Electrostatic Interactions ◽  
Minimum Energy ◽  
Alkali Halides ◽  
Dmso Molecule ◽  
Ion Pair ◽  
Model Calculations ◽  
Energy Calculations ◽  
Solvation Energies ◽  
Repulsive Forces

Energy calculations were carried out on models of molecular-level structures likely to be present in solutions of alkali halides in dimethyl sulfoxide (DMSO). Classical electrostatic interactions were assumed, and polarization of a DMSO molecule was assumed due to the fields of the ions only. The validity of this assumption was tested. DMSO molecules were represented by increasingly detailed models, with most calculations carried out with each molecule represented by 10 point charges and 9 polarizable bonds. A program including up to 14 such molecules and two ions was used for energy and distance calculations, and is made available. Polarization effects are as important as interactions between permanent charges for energy calculations. The configurations of minimum energy determined by classical electrostatics often do not involve overlap of the "hard-sphere radii" of neighboring species, so that the neglect of quantum mechanical repulsive forces seems justified. Energy cycles using the calculated energies for ion–solvent complexes predicted experimental cation enthalpies with some success. The form of the potential for vibration of a cation in a solvent shell was investigated and found in cases not to have an energy minimum at the shell center. Calculations including next-nearest solvating DMSO's indicate a rather loose structure. An energy profile for an anion moving from a solvent-separated ion pair position to a contact-ion pair position is presented.

Ion Pair Formation in Solutions of Alkali Halides in Dimethyl Sulfoxide: Ultrasonic Absorption Studies

1971 ◽  
Vol 49 (19) ◽  
pp. 3107-3113 ◽  
Author(s):  
D. R. Dickson ◽  
P. Kruus
Keyword(s):  
Dimethyl Sulfoxide ◽  
Solvent Molecule ◽  
Alkali Halides ◽  
Ion Pair ◽  
Ultrasonic Absorption ◽  
Absorption Studies ◽  
System Water ◽  
Excess Absorption ◽  
Stepwise Formation ◽  
Rate Of Movement

The ultrasonic absorption of dimethyl sulfoxide solutions of several alkali halides has been studied in the frequency range 1.5 to 52 MHz. An excess absorption, relaxing between 3 and 8 MHz, was observed. The relaxation was assigned to the final step in the stepwise formation of a contact ion pair, with the relaxation frequency controlled by the rate of movement of a solvent molecule rather than an ion. Data on the system water – dimethyl sulfoxide are also presented and the effect of water on the relaxation discussed.

DIFFUSION AND MOBILITY IN ALKALI HALIDES IN THE EXTRINSIC REGION

1973 ◽  
Vol 34 (C9) ◽  
pp. C9-425-C9-430 ◽  
Author(s):  
L. B. HARRIS ◽  
J. L. SCHLEDERER
Keyword(s):  
Alkali Halides
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