Mercury-sensitized luminescence of alcohols

Rate constants for quenching 253.7 nm fluorescence, and quantum efficiencies for emission of luminescence during mercury-sensitized photolysis have been measured for methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol and tert-amyl alcohol. From the variation of luminescent efficiency with the structure of the alcohol it is concluded that the main process competing with luminescence is normally the abstraction of an α-hydrogen by a metastable Hg(³P₀) atom formed during quenching of Hg(³P₁). For tert-butanol and tert-amyl alcohol the rate constants for reaction with Hg(³P₀) are (7.5 ± 2.5)× 10^–12 and (2.2 ± 0.8)× 10^–11 cm³ molecule^–1s^–1 respectively; lower limits are given for the rates of reaction of the other alcohols with Hg(³P₀).