What Is The Redox Reaction Between Hydrogen Sulphide And Chlorine?

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H2S⋯Cl2 characterised in a pre-reactive gas mixture of hydrogen sulfide and chlorine through rotational spectroscopy: the nature of the interaction

The ground-state rotational spectra of five isotopomers (H2S⋯35Cl2, H2S⋯35Cl37Cl, H2S⋯37Cl35Cl, HDS⋯35Cl2 and D2S⋯35Cl2) of a complex formed by hydrogen sulfide and chlorine have been observed with a pulsed-nozzle, Fourier-transform microwave spectrometer. The reaction of H2S and Cl2 was precluded by employing a fast-mixing nozzle. The rotational constant ½(B0+C0), the centrifugal distortion constant DJ and the Cl-nuclear quadrupole coupling constants χaa(Cli) and χaa(Cl0)(i = inner Cl atom, o = outer Cl atom) were determined in each case. The rotational constants were interpreted, under the assumption of unperturbed monomer geometries, to establish that H2S⋯Cl2 has a geometry in which the SClCl nuclei are collinear or almost collinear, with the Cl2 subunit nearly perpendicular to the plane of the H2S nuclei. The observed angular geometry is rationalised in terms of a set of rules previously used to discuss hydrogen-bonded complexes B⋯HX. The strength of the interaction, as measured by the force constant kσ(determined from DJ), and the electric charge redistribution within Cl2 on formation of H2S⋯Cl2χaa(Clx)> both indicate that the complex is of the weak, outer type described by Mulliken. A comparison of the properties of H2S⋯Cl2 and H2S⋯HCl reveals that the complexes are similar in several respects and explanations for these similarities are given in terms of the electric charge distributions of Cl2 and HCl. In particular, the reason why the angular geometries of both can be predicted by some electrostatically based rules is discussed.

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