Ionic Complexes of Xe and C2H2 Produced by the Radiolysis of These Gases

Abstract

Binaqr mixt?re~ of. acetylene and the noble gases were irradiated by 90 ev electrons at pressures up to 1.3 mm III the IOruzation chamber of a research mass spectrometer. Various proportions of the mixtures and ~ range of pressures were emp~oyed ~n this study. Ionic complexes, [XeC2H]+ and [XeC~2J+, were observed In the C2J:I2-~e system. The intenSIty ratio [XeC~2]+ /[XeC2H]+ increased linearly with increasing pressure. No 10ruC complexes were observed in the other mixtures. A series of reactions involving Xe+ is presented.

Xenon as a Nucleophile in Gas-Phase Displacement Reactions: Formation of the Methyl Xenonium Ion

“…Several groups of investigators have reported the formation by ion-molecule reactions in a mass spectrometer of molecular ions containing rare gas atoms (1)(2)(3)(4)(5)(6)(7)(8). Such ions have included ZH+ (1)(2)(3)(4) and small amounts (less than 1 percent of the total ionization) of ZCmHn+ (m = 1, 2; n = 0 to 4) (1-3, 5,6), ZY+ (Y = Cl, Br, I, 0) (5), ZC2N2+ (7), Z2+ (1,2,8,9), ZN2+ (9), and ZCO+ (9), where Z is a rare gas atom, usually xenon.…”

“…Such ions have included ZH+ (1)(2)(3)(4) and small amounts (less than 1 percent of the total ionization) of ZCmHn+ (m = 1, 2; n = 0 to 4) (1-3, 5,6), ZY+ (Y = Cl, Br, I, 0) (5), ZC2N2+ (7), Z2+ (1,2,8,9), ZN2+ (9), and ZCO+ (9), where Z is a rare gas atom, usually xenon. In a different series of studies the production of rare gas-alkyl ions resulting from the /3--decay of the corresponding isoelectronic radioactive alkyl halides has been observed (10)(11)(12).…”

Studies of the initial steps in the polymerization of C2N2 induced by Xe+

“…This increase in rate has been explained in terms of an initial charge transfer reaction involving the rare gas ion for those noble gases which have a higher ionization energy than CzNz (2). Xenon has been viewed as an exception because of its relatively low ionization energy and it has been argued that the simple charge transfer theory cannot explain the observations with xenon additive (3). An alternative mechanism has been proposed in which a complex of the type [XeCIN?lf is invoked as an intermediate in a sequence of steps [ I ] to [3] [I] Xe -+ Xe' + e- [2] Xe' + C2N2 + [XCCZNZ*] ' where n and m equal 1 to 4 but 12 is not necessarily equal to tn.…”

“…An alternative mechanism has been proposed in which a complex of the type [XeCIN?lf is invoked as an intermediate in a sequence of steps [ I ] to [3] [I] Xe -+ Xe' + e- [2] Xe' + C2N2 + [XCCZNZ*] ' where n and m equal 1 to 4 but 12 is not necessarily equal to tn. p = 4 -tz and q = 4 -m (1,3). Neutral cyanogen can continue to react with the ionic species produced in step [3] to form polymeric ions which ultimately can lead to neutral products by ion-ion or ion-electron recombination.…”

“…p = 4 -tz and q = 4 -m (1,3). Neutral cyanogen can continue to react with the ionic species produced in step [3] to form polymeric ions which ultimately can lead to neutral products by ion-ion or ion-electron recombination. The addition complex [XeC2N21C has actually been observed with a mass spectrometer to be formed in a 3.5 : 1 mixture of cyanogen and xenon at a total pressure of 1 Torr (1).…”