Numerical solution of the coefficient inverse problems on nonstationary filtration to a well intersected by a hydraulic fracture

A computational algorithm is proposed to determine the reservoir and hydraulic fracture properties from the results of nonstationary hydrodynamic studies of vertical wells. The problem of oil flow to a well intersected by a fracture is solved numerically. Averaged permeabilities are used for cells through which the fracture propagates.     

Problems of the stereoselectivity in the norbornadiene [2+2]-cyclodimerization reactions catalyzed by hydride nickel(i) complexes. Theoretical aspects

Cyclodimerization of norbornadiene (NBD) yielding pentacyclic products of exo-trans(cis)endo-structure in the presence of the model catalytically active complex Ni(H)(η⁴-NBD) has been studied using the DFT/PBE method. The rate-limiting reaction step is the reductive elimination of the metallacycle, the decomposition of the latter yields the norbornadiene dimer.     

Catalytic activity of bimetallic nanoparticles M@Pd (M = Ni,Cu, Ag,Pt, Au) in deoxygenation of carboxylic acids: a quantum chemical evaluation

Russian Chemical Bulletin - The key intermediates and transition states of the mechanisms of propionic acid decarbonylation and decarboxylation on icosahedral monometallic nanoclusters Pd55 and...     

Quantum-chemical study on the mechanism of catalytic dimerization of norbornadiene in the presence of hydride nickel(I) complex

[2+2]-Cyclodimerization of norbornadiene to pentacyclic products with exo-trans(cis)-exo structure in the presence of model catalytically active η⁴-norbornadiene nickel hydride complex was simulated at the DFT/PBE level of theory. According to the calculations, the rate-determining step in the cyclodimerization process is reductive elimination of the metallacycle whose decomposition yields norbornadiene dimer. The formation of cis-dimer is unfavorable for both kinetic and thermodynamic reasons.     

Kinetics and mechanism of the production of higher olefins from stearic acid in the presence of an alumina-supported nickel sulfide catalyst

A nickel sulfide catalyst which efficient in the decarbonylation of fatty acids to olefins and dienes has been obtained for the first time by treating alumina-supported nickel sulfate with hydrogen, and its properties have been studied. In its presence, the olefin selectivity of the reaction can exceed 90%. The kinetics of stearic acid deoxygenation to heptadecenes has been investigated, a kinetic model has been constructed, and a mechanism has been proposed for the reaction over this catalyst. Olefin oligomerization is the dominant side reaction. Kinetic evidence for the catalytic inhibition of oligomerization by nickel hydrides formed on the catalyst has been obtained. The compositions of active site–reactant adsorption complexes have been discussed.     

Kinetics and Mechanism of Thermal Decomposition of Bis(η3-Allyl)Nickel Complexes

Kinetics and Catalysis - The kinetics of thermal decomposition of bis(η3-allyl) nickel complexes in various media is studied. The specific features of the mechanism are determined, including...     

Mechanism of CO oxidation by oxygen in the presence of palladium(ii) bromide complexes: a quantum chemical modeling

Russian Chemical Bulletin - Mechanisms of CO oxidation by oxygen in the PdBr2-LiBr-MeCN-H2O system in the absence and in the presence of iron(ii) phthalocyaninate (PcFe) as co-catalyst were studied...     

Quantum chemical analysis of mechanisms of phenylacetylene and styrene hydrogenation to ethylbenzene on the Pd{111} surface

The mechanisms of the hydrogenation of phenylacetylene and styrene to ethylbenzene on the Pd{111} surface, which are secondary reactions of the selective hydrogenation of phenylacetylene, were studied by the DFT-PBE method. The position of the Ph group of the styrene molecule with respect to the Pd surface is shown to exert a noticeable effect on the mechanism of the process. If the Ph group is adsorbed on the Pd surface, then the addition of the first H atom to the terminal C atom of the styrene molecule is most probable. If Ph does not contact the surface, then the most substituted C atom of the styrene molecule is first hydrogenated. On the whole, the interaction of the Ph group with the Pd{111} surface results in stable adsorption structures, the hydrogenation of which on the Pd{111} surface is strongly hindered. The Gibbs activation energy (ΔG^≠₂₉₈) is 22.9 and 27.1 kcal mol^–1 in the most probable reaction routes of styrene hydrogenation to ethylbenzene and direct hydrogenation of phenylacetylene to ethylbenzene, respectively.     

Allylation of norbornadiene in the presence of Pd0 phosphine complexes: a DFT modeling

Russian Chemical Bulletin - The formation of products of oxidative and reductive allylation of norbornadiene by allyl formate (AF) in the presence of Pd0 triphenylphosphine complexes was modeled by...     

Study of the effect of the solvent nature on cis-trans isomerization in Bis(allyl)nickel by the density functional theory method

The cis-trans isomerization of the bis(η³-allyl)nickel complex in different solvents (n-hexane, benzene, toluene, THF) has been modeled by the DFT-PBE method. According to calculations, in all cases, isomerization occurs in three stages by the η³-η¹-η³ mechanism. The rate-limiting stage is the stage of rotation of the vinyl moiety in the η¹-allyl intermediate.