Energy transfer from cis- and trans-decalin to benzene and toluene in their irradiated mixtures |
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| Affiliation: | 1. School of Materials Science and Engineering, Tianjin Chengjian University, 300384 Tianjin, China;2. Tianjin Key Laboratory of Building Green Functional Materials, 300384 Tianjin, China;3. School of Mechanical Engineering, Beijing Institute of Petrochemical Technology, 102617 Beijing, China;1. Department of Chemistry and Center of Excellence for Innovation in Chemistry (PERCH-CIC), Ministry of Higher Education, Science, Research and Innovation, Faculty of Science, Kasetsart University, Bangkok, 10900, Thailand;2. Department of Chemical Engineering, Tatung University, Taipei, 104, Taiwan;3. Synchrotron Light Research Institute, Nakhon Ratchasima, 30000, Thailand;4. Department of Chemistry, Faculty of Liberal Arts and Science, Kasetsart University, Kamphaeng Saen Campus, Nakhon Pathom, 73140, Thailand;1. Materials Science & Electrochemistry, Via Mantova 11, 00042 Anzio, Rome, Italy;2. ENEA, Technical Unit on Material Technologies, Faenza Laboratories, Via Ravegnana 186, 48018 Faenza, RA, Italy;3. ENEA, Technical Unit on Material Technologies, Casaccia Research Centre, Via Anguillarese 301, 00123 S. Maria di Galeria, Rome, Italy;4. ENEA, Technical Unit for Renewable Energy Sources, Casaccia Research Centre, Via Anguillarese 301, 00123 S. Maria di Galeria, Rome, Italy |
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| Abstract: | The fluorescence from β- particle irradiation of cis- and trans-decalin containing benzene or toluene has been studied as a function of aromatic concentration from ⋍ 0.002 to 0.1 M and over a spectral range that encompasses both the solvent and aromatic fluorescence. By comparisons with the fluorescence obtained using sub-ionization excitation of the decalin, the effect of benzene and toluene to intrude into the geminate ion-pair decay process has been extracted and rate constants for their scavenging action obtained via fitting to the standard diffusion model. The rate constants are compared to those reported from microwave conductivity studies on the “escaped” mobile hole in these liquids. For the reaction between trans-decalin+ + toluene, the rates are in good agreement. However, for the reactions of either cis- or trans-decalin+ with benzene, the rate constants extracted from the fluorescence analysis are about an order of magnitude larger. The discrepancies suggest the existence of differences in the internal energies and structures of the decalin positive ions when observed on the very short time scale of geminate recombination (probed in the fluorescence measurements) and that which is observed on the much longer time scales that are probed in the microwave experiments.An analysis of the development of aromatic fluorescence permits extraction of the fraction of aromatic fluorescence that derives from ionic recombination (as opposed to energy transfer) and the averaged efficiency of this recombination. In all of the systems studied here the ionic fraction remains high (i.e. >;20%) even at millimolar concentrations of the aromatic. |
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