Chemical transformations of methane in trifluoroacetic acid

The reaction of methane conversion in anhydrous trifluoroacetic acid (TFA) is shown to take place at room temperature and atmospheric pressure and to result in the formation of a resinous product. Signals of ions with molecular weights of 684 and 700 are observed in MALDI-TOF spectra of the dry residue of methane conversion products.     

Kinetics of Absorption of Carbon Dioxide and Sulfur Dioxide in Fluorine-Containing Media

Kinetics and Catalysis - It has been established that the reactions of sulfur dioxide oxidation and carbon dioxide conversion take place in aqueous suspensions of calcium fluoride at room...     

Oxidation of benzene on a vanadium-molybdenum catalyst in the presence of thiophene

The catalytic oxidation of benzene by air oxygen on a vanadium-molybdenum mixed oxide (1 ? x)V₂O₅ · xMoO₃ (x = 0.25) over a temperature range of 200–320°C is studied. It is shown that the introduction of small amounts of thiophene into benzene inhibits the oxidation to maleic anhydride in this temperature range. It is established that the operation of the catalyst is accompanied by significant changes in its phase composition and morphology, with a few first operation cycles being characterized by a high conversion of benzene. A possible mechanism of the process is proposed.     

Activation of molecular oxygen in trifluoroacetic acid

The interaction of molecular oxygen with aqueous trifluoroacetic acid (TFA) led to an increase in pH. This effect was explained by a decrease in the concentration of the protonated CF₃CO₂H₂⁺ and H₃O⁺ species after oxygen was fed in the reactor. Quantum-chemical calculations show that a radical pair can be formed in an activation-free exothermal reaction involving the radical residue of the acid, the CF₃CO₂H₂⁺...³O₂...CF₃CO₂⁻ peroxide radical, and the acid molecule in the CF₃C₂^·...HOO^· collision complex. It was assumed that the activation of molecular oxygen in aqueous TFA solutions, providing the activity of the system in oxidations of various organic and inorganic substrates, is related to the formation of peroxide radicals in them.     

Low-temperature oxidation of sulfur dioxide by molecular oxygen in aqueous solutions of non-transition metals trifluoroacetates

Oxidation of SO₂ was shown to occur in aqueous solutions of Li, Na, and K trifluoroacetates at room temperature. Oxidative activity of the non-transition metal trifluoroacetates increases on decreasing pH of solution and at equal pH values, it follows the sequence: Li < Na < K.     

Singlet oxygen in the heterogeneous catalytic oxidation of benzene

The partial oxidation of benzene on vanadium and molybdenum oxides and the participation of singlet oxygen in this reaction were studied. A correlation between the activity of the catalysts in the partial oxidation of benzene and their ability to generate singlet oxygen was observed. The character of the initiation of oxidative benzene transformations under the action of molecular singlet oxygen was analyzed.     

Low-temperature emission of singlet oxygen from the surface of transition metal oxides

Low-temperature emission of the singlet form of dioxygen ¹O₂ from the surface of the individual and mixed V and Mo oxides was detected by thermal desorption at 20–350°C. The amount of the desorbing ¹O₂ and the temperature range of ¹O₂ emission were found to depend on the composition of the catalyst; the low-temperature ¹O₂ form can be regenerated after its contact with oxygen.     

The catalytic oxidation of organic compounds in superacids

Transformations of aromatic and aliphatic organic substances in anhydrous trifluoroacetic acid (TFA) at room temperature were studied. TFA was found to be capable of activating molecular oxygen dissolved in it. This activated oxygen endows the acid with strong oxidizer properties. Transformations of organic substances in TFA involved the formation of peroxo compounds, and alkylaromatic molecules were only oxidized at the benzene ring, side chains remaining intact. The transformations of toluene and p-xylene in trifluoroacetic acid were similar in a way to the biochemical oxidation of these substrates by mono-and dioxygenases. Mechanisms were suggested for the oxidation of toluene, p-xylene, and propylene by active oxygen in superacids.     

Paramagnetic species on the surface of chemically activated silica

Active centers of SiO₂ formed during thermolysis of methoxylated silica surface has been studied by ESR. Several types of coordinatively unsaturated silicon atoms, which differ in location and number but show similar reactivity toward various adsorbates, have been found.

---

, . - , , , H₂, CO, O₂.

     

Transformation of organic and inorganic compounds in trifluoroacetic acid

It is established that the effectiveness of fluorine-containing acids in the transformation of organic and inorganic substrates is due to the ability of the acid to perform several functions: to accumulate relatively high concentrations of molecular oxygen, to activate it, and to serve as a hydrogen-containing medium.