Electron spin resonance studies of ion pair formation in solutions of Fremy's salt

Abstract

It is shown that Fremy's salt ((KS03)2N0) is ion paired under a variety of experimental conditions. When dissolved in dioxane-water solutions in the presence of CsC104, two superimposed spectra are observed. One spectrum is that normally observed. The other has an additional splitting by a single cesium ion. An estimate of the dissociation constant has been made. Solutions of (KS03)2N0 when in the presence of such salts as RbCl and CsCl show g value shifts which are interpreted in terms of the formation of ion pairs with the added alkali metal ions. Analysis of the shifts yields estimates of the dissociation constants of 1.7(±0.4) and 1.4(±0.4) for the RbCl and CsCl salts, respectively, for a single dissociation/association process. Finally, the ESR line shapes for dilute solutions of (KS03)2N0 as a function of added alkali metal ions have been studied. It is shown that in previous work some of the reported distortion was the result of magnetic field modulation at too large a frequency. However, when lower frequencies are used there still remains a small distortion which can be interpreted in terms of a small unresolved metal hfs in the range of 5-20 mG depending upon the salt.

ESR studies of ion pair formation in solutions of the triphenylene anion radical

“…It is well established that acoustic cavitation decomposes water to produce hydrogen and hydroxyl radicals. 1,8,10,19 While the formation of hydrated electrons has also been proposed, direct evidence for their existence in an ultrasonic field (US) has not yet been obtained. In any event, in the acidic medium in which the present experiments were conducted, hydrated electrons would readily react with protons to form hydrogen atoms.…”

EPR studies of spin-spin exchange processes: A physical chemistry experiment

“…A careful study of this system leads to the conclusion that all of the above effects are potentially significant (2,10,11).…”

Intramolecular hydrogen bonding in hydroxylated semiquinones inhibits semiquinone–Mg2+ complex formation

“…Differences in the magnetic field positions of the semiquinones' first derivative EPR central peak between a sample without MgCl 2 and those corresponding to samples with increasing concentrations of this salt were measured using the dual-cavity technique, 19,20 where field/frequency lock was applied. For this purpose, the cavity was tuned with the presence of samples contained in septa-stoppered EPR quartz flat cells (60 × 10 × 0.25 mm).…”