A novel method for the conversion of hydrocarbons to alcohols using a reaction of gas-phase oxidation by oxygen in the presence of boron trichloride has been developed and described in detail. The reaction represents radical long-chain alkoxylation of boron trichloride. It proceeds at moderate temperatures of 150–180°C and atmospheric pressures of less than one atmosphere, resulting in methane conversion to (CH 3 O) 3– n BCl n ( n = 0–2) and ethane conversion to (CH 3 CH 2 O) 3– n BCl n ( n = 0–2). The hydrolysis of the reaction products generates CH 3 OH and C 2 H 5 OH, respectively. The yield of methanol reaches up to 55% at the conversion of methane of ~15% at the early stages of the reaction. The yield of ethanol is at least 65% of the reacted ethane nearly to the end of the reaction.

Using a spectroscopic complex designed for studying the kinetics of chemical reactions, the rate constant for the gas-phase reaction between a Lewis base and a Lewis acid—CH3OH + BCl3 → CH3OBCl2 + HCl—at at room temperature and pressures of 1.5–27.9 Torr has been derived for the first time. The complex comprises a reactor embedded in the optical system of a commercial AF-3 Fourier transform IR spectrometer capable of recording the spectra of reactants during the process. The reaction mechanism has been analyzed.

We present the results of a Fourier transform IR spectroscopy study of the kinetics of the gas-phase reaction between methanol and boron trichloride. From spectral data on the kinetics of the process, we determined the rate constant for the reaction of CH3OH and BCl3. The studies were conducted on a setup consisting of a chemical reactor, optically and structurally combined with a commercial AF-3 Fourier transform IR spectrometer.

It has been found that under conditions more favourable for the reaction HF*+F2→HF+2F than those used earlier/1,2/the contribution of this reaction to chain branching at the second explosion limit of a fluorine-hydrogen mixture is insignificant as compared with that of the reaction H2+F2→H+HF+F.

Qualitative and quantitative analyses have been made of the more stable reaction products of clear and leaded isooctane formed in a motored single-cylinder CFR engine. By varying the compression ratio (CR) of the engine, oxidative reactions could be followed from initial reaction to incipient autoignition. Cool flame characteristics of the fuels were followed and peak cycle pressures were measured. Techniques were developed to collect, separate, measure and identify the complex mixtures of reaction products. The combination of capillary gas-liquid chromalography (GLC) and time-of-flight mass spectrometry proved to be particularly valuable in identifying minor reaction products. Twenty compounds were identified, accounting for approximately 98% w of the products observed Isobutene, the isomers of diisobutylene, two C8 cyclic ethers, and a C8 aldehyde were the predominant reaction intermediates detected. Tetraethyllead (TEL) markedly reduced the intensity of the cool flame observed and, in general, inhibited the degradation of isooctane at all severity levels studied. At incipient autoignition, TEL reduced the concentration (per unit volume) of detected peroxides to a significantly greater extent than any other product or class of products measured. Thus, the main action of TEL appears to be the deactivation of peroxides and peroxy chain-branching intermediates.

Calculations of the probabilities of vibrational transitions P-1.0 have been made for HX molecules (X is F. Cl, Br, I) for their collisions with HX, H-2, He, Ar. The rotational anisotropy of the intermolecular potential was taken into account. A diagram of electronic density for the HF molecules was used in the calculations.