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• W2127200807 abstract "A further study has been made of the reaction of Hg 202 6( 3 P 1 ) atoms, in natural mercury vapor (Hg N ), with hydrogen chloride under flow conditions at room temperature. Emphasis has been placed in this study on the effect of reaction parameters and mercury-recovery techniques on the Hg 202 content of the solid calomel formed in the reaction.For pure hydrogen chloride the Hg 202 content of the calomel was found to be 39.9 ± 0.3%, compared to the natural abundance of 29.8%. With 20–40 mole % of butadiene-1,3 in the hydrogen chloride, calomels containing 83–84% of Hg 202 were consistently obtained.The isotopically specific aspects of the reaction in pure hydrogen chloride can be adequately explained by the sequence:[Formula: see text]where M in reaction [3] is a third body or the wall. From the Hg 202 -abundance data and steady-state considerations, it has been shown that the ratio of partitioning of the absorbed radiation to [1] and [2], respectively, = Φ 1 /Φ 2 = 0.40 ± 0.02. In short, 29% of the primary reaction proceeds by the isotopically specific step [1].The Hg 202 content of the calomel product was found to increase markedly when unsaturated hydrocarbons were added to the hydrogen chloride stream. The addends studied included butadiene-1,3, benzene, isoprene, acetylene, propylene, and ethylene in order of decreasing effectiveness. In the presence of the unsaturated addend (U) two additional reactions were postulated to occur:[Formula: see text]From steady-state calculations the effectiveness of the addend can be shown to be determined by the rate ratio, k 8 /k 4 .For the maximally enriching mixture of hydrogen chloride and butadiene, the effect of variations in lamp temperature and reaction pressure was studied. At lamp temperatures exceeding approximately 35 °C, reduced enrichments were obtained owing to emission-line broadening. A progressive reduction in enrichment was also observed with substrate pressures greater than 25 mm, owing presumably to Lorentz-broadening of the hyperfine absorption contours of the Hg N in the reaction cell.The Hg 202 content of the calomel product was determined by resonance radiation absorbiometry. The apparent Hg 202 abundances of the mercury recovered from the calomel product were found to depend strongly on the method used for isolating the enriched mercury from the calomel. Evidence was obtained for the occurrence of isotopically degradative exchange reactions during the recovery process. A recovery technique was developed which appeared to eliminate this exchange degradation." @default.
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• W2127200807 date "1959-09-01" @default.
• W2127200807 modified "2023-10-14" @default.
• W2127200807 title "PHOTOCHEMICAL SEPARATION OF MERCURY ISOTOPES: V. FURTHER STUDIES ON THE REACTION OF Hg²⁰²6(³<i>P</i>₁) ATOMS, PHOTOEXCITED IN NATURAL MERCURY VAPOR, WITH HYDROGEN CHLORIDE" @default.
• W2127200807 cites W2002206487 @default.
• W2127200807 doi "https://doi.org/10.1139/v59-210" @default.
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