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At least 91 records · Page 5Linked to original sources
PubMed2001

PCDD/DF formations by the heterogeneous thermal reactions of phenols and their TiO2 photocatalytic degradation by batch-recycle system.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) formation by the thermal reactions of phenols with CuCl2 under oxygen flux were carried out in relation to their formation mechanisms. To evaluate the effect of photocatalytic degradation of titanium dioxide (TiO2) thin film prepared by the sol-gel method, the photocatalysis of PCDD/DFs in acetonitrile/water solution by batch-recycle system was conducted. For the thermal reaction system of powder mixtures of 2,4,5-trichlorophenol (2,4,5-TCP) and CuCl2, the formation rates were 8.1 microg/g-2,4,5-TCP/min for total PCDD/DFs and 6.9 microg/g-2,4,5-TCP/min for PCDDs, and total PCDD/DF rate was higher by approximately 40 fold compared to phenol vapor/oxygen/CuCl2 powder system. For the system of 2,4,5-TCP, PCDDs were mainly formed via ortho-phenoxyphenols (POP) intermediate by the condensation of 2,4,5-trichlorophenate. For PCDD/DF photocatalytic degradations, most PCDD congeners photodecomposed rapidly and the rates presented more than 70% (as dechlorination rates of 76% for PCDDs) at 24 h after irradiation, using PCDD/DFs formed with 2,4,5-TCP. The rate constants were in the order of 4.8-6.1 x 10(-3) min(-1), assuming the pseudo-first-order reactions for their low levels.

Air Pollutants↗
PubMed2000

Kinetics of heterogeneous ozone reactions.

Earlier results on ozone destruction on solid surfaces gave apparent first order kinetics. Estimating the reaction kinetics from our data on ozone destruction on various powders (silica-gel, alumina, wood ash, coal ash, Saharan sand, calcite), we found that only calcite and wood ash exhibited such a behaviour. Removal of ozone by other powders used showed two straight lines in ln c-t plot with two different half-lives, t'(1/2) < t''(1/2). Comparing the kinetic constants for ozone removal on silica-gel and that of ozone reactions with polynuclear aromatic hydrocarbons (PAHs) adsorbed in submonolayer coverage on the same powder, the first reaction seems to be more likely in the case of pyrene and particularly fluoranthene. Enhanced ozone destruction on airborne aerosols could be an additional reason for fluoranthene stability in the real atmosphere.

Bioreactors↗
PubMed1998

Heterogeneous cholinergic reactions of ringed seal coronary arteries.

Coronary blood flow of some seal species is unusual in that it is highly variable in both non-diving and diving conditions and shows intermittent fluctuations, especially during dives when it frequently ceases for brief periods. We sought regulatory mechanisms governing these reactions by studying isometric tension recordings of isolated left circumflex (LC) and left anterior descending (LAD) coronary arteries of ringed seals, Phoca hispida, during reactions to a variety of agents for stimulating or blocking autonomic responses of the vascular smooth muscle. Micromolar acetylcholine (ACh) produced constriction of the small diameter segments of the LAD, but relaxation of the LC and larger segments of LAD. Both constrictions and dilations were prevented by atropine. Small vessel constriction by ACh was prevented by micromolar indomethacin and by a thromboxane receptor antagonist. Large vessel ACh dilations were prevented or reduced by rubbing off the endothelium and by the L-arginine analog, L-NG-nitro-arginine, an inhibitor of nitric oxide synthesis. We conclude that cholinergic, muscarinic, dilation of ringed seal large coronary arteries is mediated by endothelial-derived relaxing factor (EDRF), whereas ACh constriction of small arteries is mediated by a prostaglandin.

Acetylcholine↗
PubMed1999

Homogeneous and heterogeneous asymmetric reactions: Part 11. Sonochemical enantioselective hydrogenation of trifluoromethyl ketones over platinum catalysts.

Enantioselective sonochemical hydrogenation of alpha,alpha,alpha-trifluoromethyl ketones, namely, 1,1,1-trifluoroacetophenone and 1,1,1-trifluoro-phenylacetone was carried out over various platinum catalysts modified by cinchonidine in different solvents. Both compounds yielded the (R)-alcohol as major product. The reaction rates and the enantiomeric excesses were determined over Pt/C, Pt/SiO2, Pt/K-10 and Pt/Al2O3 catalysts under conventional conditions. Since Pt/Al2O3 exhibited the best catalytic performance the effect of ultrasound on the catalytic activity and enantioselectivity was tested using this catalyst applying different sonochemical pretreatments. These methods included a pretreatment before the reaction in hydrogen and oxygen or both. The ultrasonic irradiation was found to be highly advantageous in the case of trifluoroacetophenone, whereas only moderate changes were observed using trifluoro-phenylacetone. After insonation of the catalyst, the enantioselectivity was considerably improved. Both the aerobic and anaerobic sonochemical pretreatments resulted in significant improvement in optical yield (up to 49% and 17% ee, at room temperature under 10 bar in 1,2-dichlorobenzene). In parallel, the hydrogenation rates increased to a small extent (1.1-1.2-fold increase) after hydrogenative ultrasonic pretreatment, whereas the rates decreased by a factor of 1.5-2 after aerobic insonation. To obtain more insight into the process, the effect of insonation time on the activity and enantioselectivity and actual changes of the catalyst were also studied.

Journal Article↗
PubMedDate not supplied

Development and validation of a kinetic model for enzymatic saccharification of lignocellulosic biomass.

A multireaction kinetic model was developed for closed-system enzymatic hydrolysis of lignocellulosic biomass such as corn stover. Three hydrolysis reactions were modeled, two heterogeneous reactions for cellulose breakdown to cellobiose and glucose and one homogeneous reaction for hydrolyzing cellobiose to glucose. Cellulase adsorption onto pretreated lignocellulose was modeled via a Langmuir-type isotherm. The sugar products of cellulose hydrolysis, cellobiose and glucose, as well as xylose, the dominant sugar prevalent in most hemicellulose hydrolyzates, were assumed to competitively inhibit the enzymatic hydrolysis reactions. Model parameters were estimated from experimental data generated using dilute acid pretreated corn stover as the substrate. The model performed well in predicting cellulose hydrolysis trends at experimental conditions both inside and outside the design space used for parameter estimation and can be used for in silico process optimization.

Carbohydrates↗
PubMed2000

Consequences of affinity in heterogeneous catalytic reactions: highly chemoselective hydrogenolysis of iodoarenes

The catalytic hydrodeiodination reaction using molecular hydrogen and Pd/C has been revisited. It is shown, for the first time, that the chemoselectivity of this reaction is controlled by the high affinity of the iodinated compound for the catalyst. This reaction is compatible with most easily reducible functional groups (nitro, aldehyde, olefin, etc.). Using this reaction, the first general method for tritium labeling of 3-(trifluoromethyl)-3-phenyldiazirine is described.

Journal Article↗
PubMed2005

In situ 13C DEPT-MRI as a tool to spatially resolve chemical conversion and selectivity of a heterogeneous catalytic reaction occurring in a fixed-bed reactor.

The distortionless enhancement by polarisation transfer (DEPT) nuclear magnetic resonance (NMR) technique, combined with magnetic resonance imaging (MRI), has been used to provide the first in situ spatially-resolved and quantitative measurement of chemical conversion and selectivity within a fixed-bed reactor using natural abundance 13C NMR.

Journal Article↗
PubMed1999

Surface restructuring, kinetic oscillations, and chaos in heterogeneous catalytic reactions.

We present comprehensive Monte Carlo simulations of isothermal kinetic oscillations and chaos in catalytic reactions accompanied by adsorbate-induced surface restructuring. Our analysis is based on the lattice-gas model describing surface restructuring in terms of the statistical theory of first-order phase transitions. As an example, we treat the kinetics of the NO-H2 reaction on the Pt(100) surface. A proposed reduced mechanism of this reaction includes NO adsorption, desorption, and decomposition occurring on the restructured patches of the surface (the decomposition products are rapidly removed from the surface via N2 desorption and H2O formation and desorption). Calculations are performed with a qualitatively realistic ratio between the rates of different elementary steps. In particular, NO diffusion is several orders of magnitude faster compared to the other steps. On the nm scale, the model predicts formation of restructured islands with atomically sharp boundaries. The shape of the islands is found to change dramatically with varying reaction conditions. Despite phase separation on the surface, the transition from almost harmonic oscillations (with relatively small separate islands) to chaos (with merging islands) is demonstrated to occur via the standard Feigenbaum scenario. Near the critical point, the dependence of the amplitude of oscillations on the governing parameter is shown to be close to that predicted for the Hopf supercritical bifurcation.

Journal Article↗
PubMed1999

Surface restructuring and kinetic oscillations in heterogeneous catalytic reactions.

We extend our earlier Monte Carlo simulations of isothermal kinetic oscillations in the NO-H(2)/Pt(100) system [V. P. Zhdanov, Phys. Rev. E 59, 6292 (1999)]. The analysis, based on a lattice-gas model describing surface restructuring in terms of the statistical theory of first-order phase transitions, is primarily focused on adsorbate-diffusion-mediated synchronization of oscillations. The conventional condition for synchronization, (D tau)(1/2)>L (D is the diffusion coefficient, tau the oscillation period, and L the lattice size), is proved to considerably underestimate the role of surface diffusion. Due to the formation of mesoscopic islands, well developed oscillations are found to be possible in the cases when the left part of this condition is much lower than the right part.

Journal Article↗
PubMed2001

Reply to "Comment on 'Surface restructuring, kinetic oscillations, and chaos in heterogeneous catalytic reactions' ".

In my numeration, the criticism of my simulations of kinetic oscillations in NO reduction by H2 on Pt(100) [V. P. Zhdanov, Phys. Rev. E 59, 6292 (1999)] by Kuzovkov, Kortlüke, and von Niessen [preceding paper, Phys. Rev. 63, 023101 (2001)] contains 19 comments. I show that four comments are irrelevant. The other 15 comments are wrong, because they either contradict the basic principles of the theory of phase transitions, Monte Carlo simulations, and catalytic chemistry or ignore numerous experimental data on adsorbate-induced restructuring of the Pt(100) surface.

Comment↗