Quantum-chemical investigation of the effect of solvent polarity on the direction of sulfonation of pyrrole

The relative stability of the isomeric σ-complexes formed in the sulfonation of pyrrole at the α-or β-position (the α-isomer is energetically more favorable) does not agree with the experimentally established positional selectivity of substitution (the formation of β-pyrrolesulfonic acid). However, quantum-chemical calculations of the energy parameters for the reaction of pyrrole and SO₃ with due regard to the solvation effect in the model solvent methylene chloride (ε = 8.93) lead to the conclusion that the calculated activation energy of the rearrangement to the more favorable β-pyrrolesulfonic acid for the less favorable β-isomer of the σ-complex is lower than on the path to the formation of the α-pyrrolesulfonic acid. It was shown that the significant increase in the polarity of the model medium in the transition to DMSO (ε = 46.7) does not lead to substantial change in the energy parameters of the reaction. The explanation for the positional selectivity during the sulfonation of pyrrole using Py·SO₃, according to previous data, involves the participation of the pyridine in the transformation of the σ-complexes into the products. The calculations were made by the B3LYP/6-31G(d) and HF/3-21+G methods using the model of overlapping spheres to take account of solvation. Dedicated to E. J. Lukevics on his 70th birthday __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 34–40, January, 2007.     

Quantum-chemical investigation of the mechanism of the sulfonation of pyrrole

A detailed quantum-chemical study of the sulfonation of pyrrole with regard to the effect of the solvent (the model of overlapping spheres) on the energy characteristics of the formation of the σ-complexes produced during attack on the α-and β-positions of the heterocycle and their possible transformation paths was made by density functional theory [the B3LYP/6-31G(d) method]. The possibility of mutual transformations between the isomeric σ-complexes by α/β-migration of the SO₃ is examined. The formation of pyrrolesulfonic acids was studied for the case of the intramolecular rearrangement of the complexes. Comparison of the activation energies shows that in contrast to the gas-phase reaction the formation of the β-sulfonic acid is preferred in methylene chloride: the solvation energy of the α-isomer of the σ-complex is higher than the energy for the transition state of its rearrangement and its product, α-pyrrolesulfonic acid, leading to an increase in the kinetic barrier and to a decrease of the energy gain on the path to the formation of the latter. The opposite variation of the energy characteristics on the path to the β-isomer with regard to solvation leads to agreement between the calculated data and the experimentally observed preferred formation of the β-pyrrolesulfonic acid. Dedicated to Mikhail Grigor’evich Voronkov. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1647–1654, November, 2006.     

Standard enthalpy of formation of lanthanum oxybritholites

Lanthanum-bearing silicate-oxyapatites or britholites, Ca_10–xLax(PO₄)_6–x(SiO₄)_xO with 1≤x≤6, have been synthesized by solid state reaction at high temperature. They were characterized by X-ray diffraction and IR spectroscopy. Using two microcalorimeters, the heat of solution of these compounds have been measured at 298 K in a solution of nitric and hydrofluoric acid. A strained least squares method was applied to the experimental results to obtain the solution enthalpies at infinite dilution, and the mixing enthalpy in two steps. In the first step the mixing enthalpy obtained is referenced to the britholite monosubstituted and to the oxysilicate. The mixing enthalpy referenced to the oxyapatite and to the oxysilicate is then extrapolated. In order to determine the enthalpies of formation of all the terms of the solution, thermochemical cycles were proposed and complementary experiments were performed. The results obtained show a decrease of the enthalpy of formation with the amount of Si and La introduced in the lattice. This was explained by the difference in the bond energies of (Ca–O, P–O) and (La–O, Si–O).     

Regularities of extraction of uranyl thenoyltrifluoroacetonate into a number of solvents

The extraction equilibria were investigated of the thenoyltrifluoroacetone (TTA) chelate of uranyl ion between aqueous perchlorate medium and thirteen organic solvents. The extracted species was shown to be UO₂A₂. The solubility parameter of the chelate was estimated from the partition data and it was confirmed that the relationship lgP _M=n lgP _HA+const. holds for the present system. When the extraction constant (K _ex) is considered in relation to the distribution coefficients, theK _ex values are expected to be constant under certain conditions for all of the solvents; the lgK _ex values were found to be constant (lgK _ex=−2.85±0.17).     

Thermodynamics of solution of histidine

The enthalpies of solution of l-histidine in water at 288.15-318.15 K and 0.003-0.15 mol kg⁻¹ were measured. The enthalpies of solution were found to be independent of the solute molality up to ∼0.1 mol kg⁻¹. Standard enthalpies and heat capacities of solution were computed. Free energies and entropies of solution have been estimated in the temperature range studied using literature solubility data and the results of the present study. The temperature increase was found to result in a pronounced rise of the l-histidine solubility due to the significant increase of the TΔS values. The characteristic temperatures for the thermodynamic properties of histidine aqueous solutions were estimated.     

Enthalpy characteristics of dilute solutions of acetonitrile

The enthalpies of mixing of acetonitrile with formamide,N-methylformamide,N,N-dimethylformamide, and hexamethylphosphoric triamide were measured in the temperature interval from 283.15 to 328.15 K. The enthalpy coefficients of binary and ternary interactions were calculated by the methods of the McMillan-Mayer theory. The contributions to the enthalpy of solution due to the formation of a cavity in the solvent, Δ_cav H°, and those due to the interaction of the solute with the solvent, Δ_int H°, were determined. The enthalpies of the specific and non-specific solvation of acetonitrile in the corresponding amides were calculated. Specific interactions were found to contribute the most to the solvation enthalpy of acetonitrile. The obtained values were compared with analogous values for solutions of acetonitrile in water and alcohols. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 289–293, February, 1997.     

Determination of the Rate Constant of the Reaction of CCl2 with HCl

The rate constant of the reaction between CCl₂ radicals and HCl was experimentally determined. The CCl₂ radicals were obtained by infrared multiphoton dissociation of CDCl₃. The time dependence of the CCl₂ radicals' concentration in the presence of HCl was determined by laser‐induced fluorescence. The experimental conditions allowed us to associate the decrease in the concentration of radicals to the self‐recombination reaction to form C₂Cl₄ and to the reaction with HCl to form CHCl₃. The rate constant for the self‐recombination reaction was determined to be in the high‐pressure regime. The value obtained at 300 K was (5.7 ± 0.1) × 10^?13 cm³ molecule^?1 s^?1, whereas the value of the rate constant measured for the reaction with HCl was (2.7 ± 0.1) × 10^?14 cm³ molecule^?1 s^?1.     

Comparison of methods of determination of adiabatic times to maximum rate of exothermic reactions

The prediction of time to maximum rate from kinetic parameters is very difficult. This is because thet _mr values are extremely sensitive to small errors in the measured activation energy. It is felt that the determination of kinetic parameters needs to be supplemented by further thermal tests. Alternativelyt _mr can be measured directly.     

Heat of transformation of chains in amorphous sulphur

The heatQ of transformation of the chains in amorphous sulphur was measured calorimetrically. The mean value ¯Q for samples remelted atT _f=443 K increases from 31.5 to 45.9 J g^–1 in the measurement temperature range from 288 to 303 K.For samples remelted in theT _f range from 443 to 573 K, the ¯Q values are from 30.6 to 24.0 J g^–1.The results are discussed on the basis of the theory of nucleation and growth of nuclei.     

Kinetics of biodesulfurization of a high-sulfur coal

The apparent activation and deactivation energies and the corresponding frequency factors of coal desulfurization byThiobacillus ferrooxidans have been determined to be ΔE _a = 60.9 kJ,A _a = 1.45 s^-1 and ΔE_d = 178.3 kJ,A _d = 5.65×10²⁷ s^-1, respectively. The thermo-dynamic values (AG^?, ΔH ^?, and ΔS^?) of the activated complex were calculated. Kinetic parameters of the Monod equation were determined to beV _m = 55.9 mg dm^-3 h^-1 andK = 24.1% pulp density. The maximum rate of desulfurization of coal was found to beV _m = 55.7 mg dm^-3 h^-1 for the particle size. The generalized second order regression equation relating the yield of desulfurization to the leaching parameters was shown to adequately predict coal extraction data and optimum values of process variables. Tank leaching studies using optimum conditions resulted coal desulfurization about 90%. The iron hydrolysis reactions involving the formation of mono- and poly-nuclear, hydroxo- and sulfato complexes of amorphous and crystalline precipitates were discussed.     

Preparation of superacid of ruthenium-sulfated zirconia for reaction of butane to isobutane

A highly active superacid of 2–4 wt.% Ru-sulfated ZrO₂ for the isomerization of butane to isobutane was obtained by exposing RuO_x/ZrO₂ to 1 N H₂SO₄ followed by calcining in air at 550°C. The RuO_x/ZrO₂ was prepared by impregnating zirconium hydroxide with a solution of RuCl₃ followed by drying at 300°C. The catalyst was much more active than the superacid of sulfated zirconia, the temperature difference to show the same conversion between both catalysts being more than 145°C.     

Photodifluoramination of a series of hexafluoroacetone imines

Gas phase irradiation of N₂F₄ (NF₂) in the presence of hexafluoroacetone imine (I), N-chlorohexafluoroacetone imine (II), or N-bromohexafluoroacetone imine (III) resulted in the formation of products that correspond to either perhalogenation of the unsaturation or conversion of the substrate to a saturated halocarbon. The mechanism suggested involves the formation of an imino radical that reacts with N₂F₄(NF₂) to produce N,N-difluorohydrazone, (CF₃)₂CNNF₂. A bimolecular homolytic displacement (S_H2′) by Cl and F on the hydrazone forms an intermediate diazene which leads to the observed products. N-fluorohexafluoroacetone imine is inert to F atoms and NF₂ under the reaction conditions.     

Kinetics of the thermal decomposition of dinitramide

The kinetic regularities of the heat release during the thermal decomposition of liquid NH₄N(NO₂)₂ at 102.4–138.9 °C were studied. Kinetic data for decomposition of different forms of dinitramide and the influence of water on the rate of decomposition of NH₄N(NO₂)₂ show that the contributions of the decomposition of N(NO₂)₂ ⁻ and HN(NO₂)₂ to the initial decomposition rate of the reaction at temperatures about 100 °C are approximately equal. The decomposition has an autocatalytic character. The analysis of the effect of additives of HNO₃ solutions and the dependence of the autocatalytic reaction rate constant on the gas volume in the system shows that the self-acceleration is due to an increase in the acidity of the NH₄N(NO₂)₂ melt owing to the accumulation of HNO₃ and the corresponding increase in the contribution of the HN(NO₂)₂ decomposition to the overall rate. The self-acceleration ceases due to the accumulation of NO₃ ⁻ ions decreasing the equilibrium concentration of HN(NO₂)₂ in the melt. For Part 2, see Ref. 1. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 395–401 March 1998.     

Evaluation of the effect of silicon on the carbonization process of Colombian semi-anthracites

The environmental impacts associated with the exploitation and transformation of fossil resources aggravate the planet's situation in terms of climate change. Due to this, this paper studies an alternative use of mineral coal as a precursor to obtaining new materials with different properties to the starting coals. The thermal degradation of two Colombian semi-anthracites is analyzed through the thermogravimetry (TG) technique coupled to a Fourier transform infrared spectroscopy (FTIR) equipment from room temperature (25 °C) to 900 °C, at a heating rate of 10 K min^?1 in an inert atmosphere. The catalytic effect of the addition of silicon to these samples before being subjected to a carbonization process is evaluated during this process. The results indicated that the primary reaction occurs in the temperature range between 400 and 680 °C, where the highest mass loss rate was observed. At the end of the heating process, the TG profile of the samples with silicon addition showed losses between 14.33 and 18.82% in mass, these values being slightly higher compared to the starting and demineralized samples. The release of water, light gases such as CO₂, CH₄, and species such as toluene, phenol and formic acid was identified in most of the samples. The presence of silica seems to favor the release of all these species, being more evident in one of the semi-anthracites studied. According to the results obtained, it is proved that the presence of silicon in samples subjected to carbonization processes has a catalytic effect that improves some characteristics of the new materials obtained, thus contributing to the use of carbon to get new materials.

     

The investigation of the electronic effects of polyfluoro-aryl group by means of nmr spectroscopy

The relationship between NMR ¹⁵N, ¹⁷O, ³¹P, ⁷⁷Se, ¹³C spectral parameters and electronic structure of number of polyfluoroaromatic compounds has been discussed. The increase of the nuclei shielding has been found in all classes of investigated polyfluorinated compounds in respect to the corresponding hydrocarbon analogues. That effect has been discussed in terms of decrease of the conjugation between the unshared electron density of heteroatoms and the π-system of polyfluorinated benzene ring. The conductivity of substituent electronic effects on the π-system of the polyfluoroaryl group by the heteroatom has been estimated from NMR ¹³C data. The sensitivity of nuclei shielding towards interamolecular electronic effects has been noticed to increase from oxygen to selenium and the analysis of the influence of the intramolecular electronic effects on the ¹⁷O and ⁷⁷Se shifts has been given. The influence of the substituents either in pentafluorophenyl ring or adjacent to heteroatom have been shown to correspond those in the hydrocarbon analogues.The conclusion about the influence of polyfluoroaryl group on the character of bonds between different atoms in functional group has been made from the NMR ¹⁷O and ¹⁵N data for aromatic nitro-derivatives. Polyfluorophenyl group in respect to phenyl one deshields the oxygen atom and shields the nitrogen atom. The same effect of pentafluorophenyl group has been observed by other spectral methods.The different screening of ¹⁷O, ¹⁵N, ³¹P and ⁷⁷Se nuclei due to the action of substituents adjacent to the element and variation of the coordination number of heteroatom have been used to the solvation of a number of problems in chemistry of the heteroanalogues of carbenium ions and the detail investigation of the mechanism of electrophylic substitution in the field of polyfluoroaromatic compounds.     

Correlation of thermodynamic stabilities of charge transfer complexes of anthracene and chloranil with those of tetra-cyanoethylene

The formation constants of charge-transfer complexes of a number of 9- and 9,10-substituted anthracenes with chloranil have been measured by a spectrophotometric method and the corresponding thermodynamic parameters ΔG°_c, ΔH°_c and ΔS°_c evaluated in various solvents. v_max values of the chargetransfer band for chloranil were linearly related to those for tetracyanoethylene (TCNE). Good correlations were also obtained between v_max and the corresponding ionisation potentials Ip of the donor molecules. In addition ΔG°_c varied linearly with Ip and from these correlations, values of ΔG°_c, etc. for the corresponding TCNE complexes could be calculated. These values are otherwise very difficult to obtain due to the high reactivity of TCNE.     

Determination of carbonate in the presence of hydroxide : Part I. Analysis of first-derivative potentiometric curves

Mathematical consideration of the course of neutralization of a solution containing a moles of a strong base (e.g. sodium hydroxide) and a moles of a salt of a weak dibasic acid (e.g. sodium carbonate) with a strong acid (e.g. hydrochloric acid) shows that the first derivative of the titration curve should contain three maxima. The first, corresponding to neutralization of most of the hydroxide, is small (with height proportional to a^{$\text{1}\text{2}$}), displaced slightly from the equivalence point, and disappears for a less than 0.01 mol l^-1. The second corresponds to the conversion of most of the CO₃^2- to HCO₃^- and its height is almost independent of a. The third corresponds to the conversion of HCO₃^- to H₂CO₃, with height proportional to a^{$\text{1}\text{2}$}. The two minima are independent of a and of the dissociation constants of the weak acid. These conclusions were examined experimentally and were extended to the titration of hydroxide contaminated with a small amount of carbonate.     

ESR study of the effect of fluorinated alcohols on magnetic resonance parameters of spin-adducts of phosphoryl radicals with products of cycloaddition of substituted nitriloxides to C60

Regioselectivity of the addition of phosphoryl radicals to the products of cycloaddition of substituted nitriloxides to fullerene C₆₀ was studied by ESR spectroscopy. The effect of fluorine-containing alcohols on the magnetic resonance parameters of the isomers of spinadducts of phosphoryl radicals located at different distances from the five-membered heterocycle was studied. Complexation of the obtained isomeric spin-adducts with (CF₃(₃COH leads to a 3 to 5 G increase in the constant of hyperfine interaction with the phosphorus nucleus, which makes it possible to observe additional lines in the ESR spectrum. Deceased. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1808–1811, September, 1999.