Molecular Parameters of Tert-Butyl Chloride and Its Isotopologues Determined from High-Resolution Rotational Spectroscopy

A broadband chirped-pulse Fourier transform microwave spectrometer was used to detect the rotational spectra of the products of a chemical reaction in the gas phase from 1-18 GHz under the supersonic expansion condition. In natural abundance, pure rotational energy level transitions of tert-butyl chloride and its isotopologues (13C, 37Cl) were observed and assigned. The rotational spectral parameters (rotational constant, quadrupole coupling constant and centrifugal distortion constant) of these isotopologues were determined. The experimental results are in great agreement with the calculated values of quantum chemistry and the spectral parameters in the literature. The accuracy and the capability for chemical detection of our homemade rotational spectrometer were verified by this experiment.

INTERACTION OF ALUMINUM-COBALT AND ALUMINUM-NICKEL ALLOYS ACTIVATED BY LIQUID GALLIUM-INDIUM EUTECTIC WITH TERT-BUTYL CHLORIDE FOR FORMATION OF CATALYTIC METAL - ALUMO-CHLORIDE COMPLEXES

It is known that binary alloys of aluminum and metals of the iron group (cobalt, nickel) after their activation with the liquid eutectic gallium-indium by the removal of “passivating” oxide layers sharply increase the reactivity with respect to organochlorines. Corresponding reactions lead to the formation of metal – alumo - chloride complexes as inorganic products, which are active in many practically important catalytic reactions of liquid-phase conversion of hydrocarbons such as: alkylation, isomerization, oligomerization. This approach which was previously developed by the authors for the polycrystalline aluminum, is of interest in metal-complex catalysis since the formation of catalytic alumo-chloride and/or metal-alumo-chloride complexes can be carried out directly in the reaction medium, i.e. in situ. In this work, the local composition, structure and morphology of surface layers of aluminum-cobalt and aluminum-nickel alloys activated with liquid gallium-indium eutectic were studied using the methods of scanning electron microscopy and X-ray energy-dispersive spectrometry to determine the physicochemical regularities of the dynamics of their interaction with tert-butyl chloride at room temperatures. The formation of metal chloride complexes in the interphase area “activated alloy - tert-butyl chloride” was studied by ATR-FT-IR method in situ. The results obtained indicate that mono- and bi- nuclear alumo-chloride anions stabilized by cobalt and nickel cations are formed during the interaction. It is assumed that the ionic complex pairs formed are the active centers in liquid-phase reactions of hydrocarbons transformation at low temperatures. These structures are responsible for significantly change in the selectivity of catalytic processes compared to aluminum chloride catalyst. For citation: Arbuzov A.B., Drozdov V.A., Shlyapin D.A., Lavrenov A.V. Interaction of aluminum-cobalt and aluminum-nickel alloys activated by liquid gallium-indium eutectic with tert-butyl chloride for formation of catalytic metal - alumo-chloride complexes. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 64-69