A General Equation of the Polarographic Wave Applicable to Solvents of Low Dielectric Constant; Effect of Ion-pair Formation on Half-wave Potentials

1960 ◽  
Vol 82 (8) ◽  
pp. 1837-1841 ◽  
Author(s):  
Ward B. Schaap
Keyword(s):  
Dielectric Constant ◽  
General Equation ◽  
Ion Pair ◽  
Pair Formation ◽  
Low Dielectric Constant ◽  
Polarographic Wave ◽  
Ion Pair Formation ◽  
Low Dielectric ◽  
Half Wave

SULPHONIUM SALT SOLVOLYSIS: PART I. EFFECT OF CONCENTRATION, ANION TYPE, AND SOLVENT VARIATION ON RATE OF REACTION

1961 ◽  
Vol 39 (6) ◽  
pp. 1207-1213 ◽  
Author(s):  
J. B. Hyne
Keyword(s):  
Dielectric Constant ◽  
Ion Pair ◽  
Pair Formation ◽  
Rate Dependence ◽  
Rate Data ◽  
Independent Evidence ◽  
Ion Pair Formation ◽  
Rate Of Reaction ◽  
Anion Type

Previous work on the mechanism of sulphonium salt solvolysis is reviewed briefly. Rate data, determined by two independent methods, is presented for the solvolysis of dimethyl-t-butyl sulphonium iodide, bromide, and chloride in water and various ethanol–water mixtures. Rate dependence on the anion character and concentration of salt is shown to develop as the dielectric constant of the medium is lowered. The results are interpreted in terms of the increasing importance of an ion-pair mechanism as the composition of the medium is changed. The interpretation is substantiated by independent evidence for ion-pair formation.

Tropolone-triethylamine equilibria in various solvents

1980 ◽  
Vol 33 (3) ◽  
pp. 491 ◽  
Author(s):  
B Poh ◽  
H Siow
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Dielectric Constant ◽  
Aprotic Solvent ◽  
Ion Pair ◽  
Pair Formation ◽  
Spectroscopic Methods ◽  
Aprotic Solvents ◽  
Ion Pair Formation ◽  
No Formation ◽  
Hydrogen Bonded

Infrared and nuclear magnetic resonance spectroscopic methods were used to study the tropolonetriethylamine equilibria. In aprotic solvents tropolone transfers its proton to triethylamine to form an ion pair which is in equilibrium with the intramolecularly hydrogen-bonded tropolone. The extent of ion pair formation increases with the dielectric constant of the aprotic solvent. Unlike the case of the p- nitrophenol-triethylamine system, there is no formation of a hydrogen bonded complex between tropolone and triethylamine. In the case of the tropolone-dibutylamine system in aprotic solvents, only ion pair formation is observed.

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