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Pulse radiolysis study on electrons trapped in aqueous solid clathrates

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100277a051· OSTI ID:5890207

Early concepts on the nature of the 620-nm trapped electron have now been supported by results obtained on clathrates other than tetrabutylammonium (TBA) hydroxide (TBAOH.29H/sub 2/O). In aqueous solid clathrates of trimethylamine, diethylamine, and tert-butylamine, similar e/sub t//sup -//sub (aq)/ transient spectra have been observed. These amines are protonated and OH/sup -/ ions are present in solution which produces a clathrate. In the process of clathrate crystallization from the melt or solution, typical anionic vacancies are created in which some OH/sup -/ ions are missing. Since that ion is a part of the water lattice its absence is equivalent to a vacancy of one water molecule in an aqueous surrounding. This unusual vacancy becomes an aqueous trap for electrons. The same applies to a vacancy of F/sup -/ in tetrabutylammonium fluoride clathrate (TBAF.32H/sub 2/O) which shows identical e/sub t//sup -//sub (aq)/ spectra. Aqueous solid clathrates of acetone and tetrabutylammonium oxalate (neutral pH of liquefied clathrate) do not show the typical high yield, comparatively long-lived e/sub t//sup -//sub (aq)/ spectrum, because there are no traps equivalent to those mentioned above. 25 references, 9 figures.

Research Organization:
Univ. of Notre Dame, IN
OSTI ID:
5890207
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:5; ISSN JPCHA
Country of Publication:
United States
Language:
English