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Journal of Physical Chemistry, Vol.100, No.14, 5993-6002, 1996
High-Mobility Ions in the Viscous Hydrocarbon Squalane
Pulsed radiolysis, laser flash photolysis, and de photoconductivity were used to measure the rates of ion-molecule reactions in the viscous hydrocarbon squalane (2,6,10,15,19,23-hexamethyltetracosane). It was found that squalane radical cation (hole) is scavenged with a rate constant similar to(5-7) x 10(9) mol(-1) dm(3) s(-1), which is 4-10 times faster than other charge transfer reactions in squalane. In this sense, squalane is similar to cyclohexane, methycyclohexane, and decalins, yielding high-mobility ions (HMIs) on radiolysis. While in squalane the hole is more mobile than molecular ions, its mobility (estimated as 2 x 10(-4) cm(2)/(V s)) is much lower than that of the HMIs in cycloalkanes. The lifetime of the squalane hole in the absence of scavengers is 20 +/- 5 ns.
Keywords:DETECTED MAGNETIC-RESONANCE;ALKANE RADICAL-CATIONS;PULSE-RADIOLYSIS;IRRADIATED CYCLOHEXANE;ABSORPTION-SPECTRA;ELECTRON-TRANSFER;RATE CONSTANTS;EXCITED-STATE;POSITIVE-IONS;SOLVENT