The Photolysis of Carbon Disulfide and Carbon Disulfide – Oxygen Mixtures

Abstract

These data show that I from the second method has two NMe proton peaks in a ratio of 1:2 a t 6 = 4.28 and 4.90 upfield from benzene. All the other spectra contain these two peaks in the same ratio, but other peaks are also present. In the spectra of crude products and in the 90 and 100 OC sublimate from both methods, another pair of peaks is located a t approxiinately 6 = 4.25 and 4.78 upfield from benzene and in the ratio of 1:2. These two closely spaced pairs suggest the presence of two forms of Be(NNIe2)2 of similar structure.If Be(N&11e~)~ were a cyclic trimer as suggested by Coates ( I ) , there should be two types of NhIe protons in a ratio of 1:1, that is, there should be 18 methyl protons bonded to terminal NMez groups and 18 protons on the bridging NA' Ie2 groups. Since the ratio of the two types of NMe protons is 1:2, a trimeric structure of the type is indicated to achieve a maxiinuin coordination for beryllium. The other form of Be(NMez)z may be another configuration of this trimer; for example, there may exist cis and trans forms for the terminal NMez groups.Only I of the second method appears to be a pure compound; hence, the molecular weight of this substance was the only one measured. The values 308 and 311 (calcd. 291.3 for Be(NMe2)z trirner) indicate this material is trimeric in freezing benzene; therefore, the form of Be(NMe2)2 obtained by sublimation a t 65 OC is more accurately represented by the structure shown above than by the cyclic form.

The long‐wavelength photochemistry of carbon disulfide

“…Theoretical precision of the concentration measurements was much higher (in the FTIR experiments) than the reproducibility of the quantran yields, especially those at high PCS2. Although the quantum yields at PCS2 > 3 tort cannot be considered primary quantum yields for photopolymerization, they provide a link to the previous studies [de Sorgo et al, 1965;tVood and Heicklen, 1971b]. It is also possible that the size of the growing (CS2)x cluster affects its reaction efficiency with CS2".…”

Direct Observation of the C + S2 Channel in CS2 Photodissociation

“…There have been several reports of CS 2 photochemistry that have tried to illustrate the formation mechanism of S 2 fragments. In one study, de Sorgo et al observed transient absorption spectra of S 2 ( v = 0), but no S atoms were observed by that method. They concluded that S 2 must be formed by the reaction CS 2 * + CS 2 → 2CS + S 2 .…”

Experimental Analysis of Characterization of Aerosol Sediments Formed by Plasma-Induced CS2 Destruction Processes

“…In previous studies, high pressure polymerization (Whalley, 1960;Chan and Jonscher, 1969), photolysis (de Sorgo et al, 1965), chemical polymerization (Tsukamoto and Takahashi, 1986), laser-induced polymerization (Ernst and Hoffman, 1979;Matsuzaki et al, 1992;Desai et al, 1995), and plasma polymerization (Hirotsu, 1981;Asano, 1983;Sadhir and Schoch, 1996;Denisov et al, 1997) of CS 2 usually led to the formation of dark brown to black depositions or polymers. The structures of the polymers have been described as linearor crosslinked (CS 2 ) n for the 45 kilobar products or thermal decomposition of photopolymerization products (Whalley, 1960;Chan and Jonscher, 1969;Colman et al, 1996), as (CS) n for plasmalysis (Denisov et al, 1997), laser-induced aerosol (Ernst and Hoffman, 1979;Desai et al, 1995) or combustion (Cullis, 1972), and as [CS(S) m ] n (m ϭ 0, 1, 2 .…”