PHOTOCHEMICAL SEPARATION OF MERCURY ISOTOPES. IV. THE REACTION OF Hg$sup 202$6($sup 3$$P$$sub 1$) ATOMS, PHOTOEXCITED IN NATURAL MERCURY VAPOR, WITH METHYL CHLORIDE AND ISOPROPYL CHLORIDE

Journal Article · Sat Aug 01 04:00:00 EDT 1959 · Canadian Journal of Chemistry (Canada)

DOI:https://doi.org/10.1139/v59-195· OSTI ID:4254351

Osborn, K R; Gunning, H E

A detailed investigation has been made of the reaction of Hg/sup 202/ 6(sup 3/P/sub 1/ atoms, photoexcited in natural mercury vapor (Hg/sup N/), with methyl chloride, at room temperature. Data are also reported on the reaction with isopropyl chloride as substrate. Hg/sup 202/ enrichment in the calomel product is taken as evidence of its formation in the primary quenching reaction. Under static conditions the methyl chloride reaction was found to form calomel with the natural Hg/sup 202/ abundance (29.8%). With increasing flow rate a progressive increase in Hg/sup 202/ abundance was observed. Maximum enrichments were found at fast flow rates, low substrate pressures, and high values for the absorbed light intensity (I/sub A/). The most highly enriched calomel obtained in this study contained 50.4% Hg/sup 202/. With increasing I/sub A/ corresponding increase in flow rate was required to achieve maximum Hg/sup 202/ enrichment. The addition of propylene or butene-1 to the methyl chloride stream was found to result in a slight decrease in Hg/sup 202/ abundance over that for the pure substrate. The decrease in enrichment observed at high substrate pressures is shown to be due to Lorentzbroadening effects on the hyperfine absorption contours of Hg/sup N/. The failure to obtain enrichment under static conditions is explained by the depletion in Hg/sup 202/ of the Hg/sup N/ in the cell. The investigation shows that there are two primary processes operative in the mercury6(/sup 3/P/sub 1/ photosensitized decomposition of alkyl chlorides, in one of which calomel is formed. These proeesses presumably involve a common short-lived intermediate R --- Cl --- Hg. (auth) The polymerization of 1- octene, trans-2-octene, cyclohexene, and 2,4,4-trimethyl-2-pentene under irradiation of 500-kv electrons was studied. The monomer is consumed according to the first order relationship, log (100/x) = kD, where x is the percentage of non-transformed monomer at the time t and U is the radiation dose in watt-hours/ gm. The formation of the polymer is also of the first order. The radiochemical yields, in number of monomer molecules transformed per 100 ev, corresponding lip various doses are tabulated. The polymer composition for 0.5 and 2 w-hr/gm is also tabulated. The yields support the hypothesis of an ionic mechanism for the polymer formation. The effect of temperature on the reactions is slight. (J.S.R.)

• Research Organization: Illinois Inst. of Tech., Chicago; and Univ. of Alberta, Edmonton, Can.
• Sponsoring Organization: USDOE
• NSA Number: NSA-13-019019
• OSTI ID: 4254351
• Journal Information: Canadian Journal of Chemistry (Canada), Journal Name: Canadian Journal of Chemistry (Canada) Vol. Vol: 37; ISSN CJCHA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

ALKENES
CALOMEL
CHEMISTRY
DECOMPOSITION
ENRICHMENT
EXCITATION
ISOTOPE SEPARATION
LOW TEMPERATURE
MERCURY 202
MERCURY CHLORIDES
MERCURY ISOTOPES
METHYL RADICALS
ORGANIC CHLORINE COMPOUNDS
PHOTOCHEMISTRY
PROPYL RADICALS
PROPYLENE
QUANTITY RATIO
VAPORS