Rare gas sensitized radiolysis of hydrogen sulfide in the presence of butadiene. [Gamma rays]

Journal Article · Thu Aug 11 04:00:00 EDT 1977 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100531a002· OSTI ID:7305343

Jowko, A; Szamrej, I; Forys, M

Hydrogen and sulfur yields have been measured from the argon, krypton, and xenon sensitized radiolysis of hydrogen sulfide in the presence of butadiene. A sharp decrease in the yield of elemental sulfur from 5-7 molecules/100 eV down to a very low value (ca. 0.1 atoms/100 eV) has been discovered even at the lowest added amounts of butadiene. Unlike the sulfur yields, the hydrogen yields diminished smoothly with (C/sub 4/H/sub 6/)/(H/sub 2/S) ratio. A mechanism for the observed decrease in the sulfur and hydrogen yield has been discussed. It has been shown that elemental sulfur is produced via the HS/sup +/ ions and SH radicals and/or S atoms as intermediate products, each of them being scavenged by butadiene. The change in G(H/sub 2/) with the (C/sub 4/H/sub 6/)/(H/sub 2/S) ratio was ascribed to a competition between butadiene and hydrogen sulfide in an excitation transfer from the rare gas metastables, and hydrogen atom scavenging. The rate constant ratio k/sub H+H/sub 2/S//k/sub H+C/sub 4/H/sub 6// has been calculated to be in the range of 0.22-0.28, 0.18-0.22, and 0.14-0.16 for Kr, Xe, and Ar, respectively. The observed increase in the rate constant ratio as compared to that for thermal H atoms (0.11) has been accounted for by a higher kinetic energy of hydrogen atoms produced in the system. The maximum values of G/sub Xe*/, G/sub Kr*/, and G/sub Ar*/ have been found from energetic calculations to be equal to 3.1, 2.5, and 2.1, respectively. These have been compared with experimental results found under the supposition that primary radiolysis can be neglected. The discrepancy has been observed which has been ascribed to the significant decomposition of hydrogen sulfide by electrons subexcited with respect to rare gas atoms. The hydrogen yield due to the last process has been estimated to be ca. 1.4 for Ar and Xe.

• Research Organization: University Teachers Coll., Siedlce, Poland
• OSTI ID: 7305343
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 81:16; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ARGON
BUTADIENE
CHALCOGENIDES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
CRYOGENIC FLUIDS
DECOMPOSITION
DIENES
ELECTROMAGNETIC RADIATION
ELEMENTS
FLUIDS
G VALUE
GAMMA RADIATION
HYDROCARBONS
HYDROGEN
HYDROGEN COMPOUNDS
HYDROGEN SULFIDES
IONIZING RADIATIONS
KRYPTON
NONMETALS
ORGANIC COMPOUNDS
POLYENES
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADIOLYSIS
RARE GASES
SULFIDES
SULFUR
SULFUR COMPOUNDS
XENON