Ethane-deuteroethanes

Ethane-Deuteroethanes. Chromatographic separation of ethane and perdeuteroethane was first reported by Van Hook and Kelly (32) using packed columns loaded with methylcyclopentane at subambient temperatures. These authors also reported the partial resolution of protio-ethane from mono and di-deuteroethanes. The chromatographic properties of the perdeutero-ordinary system were further investigated on a variety of liquid substrates using packed column GLC techniques by Van Hook and Phillips (34) and on an open tubular etched glass column with a wetted wall (subsequently called wet glass in this paper) by Bruner, Cartoni, and Liberti (8). 

Table III. Initial Deuteroethane Yields in TD/D2 Ethane Systems...

Somewhat different but not necessarily discordant results were obtained by Bell and Kistiakowsky9 in the photolysis of CH2N2 in the presence of excess D2. The < > ethane was the major deuteroethane found, but unlike the results of Chanmugan and Burton the do, di, da, dt, and do (trace) ethanes were also present. Since the abstraction mechanism... 

There is evidence for a species in which a -CH2-CH2- group acts as a bridge between two Cl(Cp)2Zr moieties. The reaction of triethyl aluminum with (7T-Cp)2ZrCl2 proceeds with the evolution of ethane, and the formation of an adduct containing one mole of aluminum for every mole of zirconium. The aluminum moiety can be substantially removed by treatment with THF. When tris(l,2-deuteroethyl)aluminum was used as the reagent, one mole of 1,2-deuteroethane was evolved per two moles of (i7--Cp)2ZrCl2 used in the reaction. When the product (I), which is formulated as... 

Deuteroethane distributions have been interpreted in terms of a parameter P, which is the quotient of the rate constants for ethyl to ethene and ethyl reverting to ethane. For molybdenum, tantalum, rhodium and palladium films, a single value of P (respectively 0.25, 0.25, 18 and 28) sufficed to reproduce the observed distribution, assuming that a further deuterium atom is acquired at every opportunity. With other metals, however, two simultaneous values of P appeared to operate, one contributing 30 to 50% of the reaction having a high P value (13.5-18) and another having a much lower P value (0.36-2). This analysis has not however been accorded an interpretation in terms of the metals physical properties or of ensemble sizes and structures responsible for each participant. 

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