Identification of HGeCl by chemiluminescence from the reaction of GeH₄ with Cl₂

Abstract

Chemiluminescence from the reaction of germane with chlorine has been observed in the region 4450–5200 Å. This emission has been identified as the [Formula: see text] transition in HGeCl. From the observed transitions, approximate equations for the vibrational levels of the lower and upper electronic states were obtained. Thermodynamic considerations indicate that HGeCl is probably produced by the reaction GeH2 + Cl2 → HGeCl* + HCl which is exothermic by approximately 70 kcal/mol. A continuum centered at approximately 4300 Å and extending into the HGeCl spectrum was identified as resulting from GeCl2*.

The ground state energy levels and molecular structure of jet-cooled HGeCl and DGeCl from single vibronic level emission spectroscopy

“…Although HGeCl and DGeCl each consists of ten isotopomers with significant natural abundances, in most cases the isotope splittings were not resolved in the LIF or emission spectra, so in all calculations involving isotopic masses we have assumed that we are dealing with the most abundant species, H 74 Ge 35 Cl and D 74 Ge 35 Cl. 12 Excitation of the 3 0 1 band of HGeCl shows a strong emission transition down to 3 1 and a weaker feature which can be assigned as the 3 2 1 band, which allowed the determination of the x 33 anharmonicity constant. Pumping the p Q 1 branch of each band guaranteed that the emission down to each ground state vibrational level consisted of a single K a Ј=0−K a Љ=1 subband, yielding the simplest, most intense emission spectra.…”

Chemiluminescence from oxidation of inorganic hydrides: spectrum of TeF

“…TeH + F, --t TeF* + H F + 80 kcal/mol A reaction exoergicity of -73 kcallmol is sufficient to account for the observed TeF'hmission from vibrational levels u ' I 12; thus the combination of reactions [2] and [3] appears thermodynamically consistent with the observed spectrum.…”

“…Although it is difficult to definitively assign one of the above processes as the source of the observed TeF emission, based primarily on expected flame concentration, we favour the series of stripping reactions [2] and [3]. Future studies will be directed towards the elucidation of a reaction mechanism.…”

“…The gross features of the currently observed band system closely parallel those for the known spectrum of the S F radical. chemiluminescence which results upon the intiExperimental mate mixing of mono-or disilane with F,, CI,, or CIF ( I ) , and the production of HGeC]" from mixHydrogen telluride, HzTe, was prepared by tures of GeH, and CI, (2). As part of a continuing dropwise addition of 4 M HCI to AI2Te3 (Alfa effort to oxidation in various inorganic Products, 99.9%) and purified by trap-to-trap dismetal and nonmetal hydride systems, we report the tillation in ciacuo.…”

The microwave spectrum of HGeCl

“…Vacuum UV photolysis of H 3 GeCl in an argon matrix produced a species giving rise to an IR absorption band at 1862 cm À1 which was tentatively identified as chlorogermylene. In 1977, Patel and Stewart [6] identified HGeCl as the carrier of the blue chemiluminescence resulting from the reaction of germane and chlorine and were able to assign the vibrational structure of theÃð 1 A 00 Þ-e X ð 1 A 0 Þ transition of HGeCl and DGeCl. In 1990, Ito et al [7] produced chlorogermylene by reacting germane with the microwave discharge products of a mixture of chlorine and argon, and studied the A-X transition of HGeCl at 0.04 cm À1 resolution by laser-induced fluorescence (LIF).…”