Mercury sensitized photolysis rates

Cohen and Heicklen 46 investigated the mercury-sensitized photolysis of C2F4 and were able to determine the rate constant for the reaction... 

Birse and Melville55 measured the disappearance of N2H4 in the presence of hydrogen atoms generated by mercury-sensitized photolysis of H255. They could not discriminate between reactions (4) and (5) and assumed that the H atoms were removed by reaction (4). In view of the more recent experiments with D atoms it is, however, more likely that they determined the rate of reaction (5). They report a rate coefficient... 

The influence of mercury sensitization on the exchange rate was checked by Nadler and Turbini using a Vycor filter to eliminate light absorbed by borazine. In both cases the effect of mercury-sensitized photolysis was small compared to the effect of direct photolysis. 

The possibility of mercury-photosensitized reactions was first predicted in 1922 by Franck (45) and experimentally verified in the sensitized decomposition of H2 by Cario and Franck (46). They found that free H atoms were produced when a mixture of Hg vapor and H2 was irradiated with the 254 nm Hg resonance line at room temperature. Bates and Taylor (23) studied the Hg-sensitized decomposition of methanol, ethanol, and ethylamine, and showed that with these compounds the rate of the sensitized reaction was faster than the direct photolysis by about two orders of magnitude. Again hydrogen was the major product. Aldehydes were formed from the alcohols. 

Recent photolysis studies considered the effect of the wavelength on the rate curve [207,212,213]. Specifically, photolysis of alkali and alkaline-earth azides using a low-pressure mercury lamp gave curves (Figure 26) whose characteristic shape was sensitive to the spectral content of the photolyzing light [198,207]. If the 180-nm line was filtered from the output spectrum of a low-pressure... 

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