Search results for "Chemical kinetics"
showing 10 items of 60 documents
Time scale of protein aggregation dictated by liquid-liquid demixing
2003
The growing impact of protein aggregation pathologies, together with the current high need for extensive information on protein structures are focusing much interest on the physics underlying the nucleation and growth of protein aggregates and crystals. Sickle Cell Hemoglobin (HbS), a point-mutant form of normal human Hemoglobin (HbA), is the first recognized and best-studied case of pathologically aggregating protein. Here we reanalyze kinetic data on nucleation of deoxy-HbS aggregates by referring them to the (concentration-dependent) temperature Ts characterizing the occurrence of the phase transition of liquid-liquid demixing (LLD) of the solution. In this way, and by appropriate scalin…
O2(a1Δg) + Mg, Fe, and Ca: experimental kinetics and formulation of a weak collision, multiwell master equation with spin-hopping
2012
The first excited electronic state of molecular oxygen, O(2)(a(1)Δ(g)), is formed in the upper atmosphere by the photolysis of O(3). Its lifetime is over 70 min above 75 km, so that during the day its concentration is about 30 times greater than that of O(3). In order to explore its potential reactivity with atmospheric constituents produced by meteoric ablation, the reactions of Mg, Fe, and Ca with O(2)(a) were studied in a fast flow tube, where the metal atoms were produced either by thermal evaporation (Ca and Mg) or by pulsed laser ablation of a metal target (Fe), and detected by laser induced fluorescence spectroscopy. O(2)(a) was produced by bubbling a flow of Cl(2) through chilled al…
Synthesis ofN=127isotones through (p,n) charge-exchange reactions induced by relativistic208Pb projectiles
2011
The production cross sections of four N=127 isotones ({sup 207}Hg, {sup 206}Au, {sup 205}Pt, and {sup 204}Ir) have been measured using (p,n) charge-exchange reactions, induced in collisions of a {sup 208}Pb primary beam at 1 A GeV with a Be target. These data allow one to investigate the use of a reaction mechanism to extend the limits of the chart of nuclides toward the important r-process nuclei in the region of the third peak of elemental abundance distribution.
Effect of nonequilibrium charge screening in A + B ? 0 bimolecular reactions in condensed matter
1993
The formalism of many-particle densities developed earlier by the present authors is applied to the study of the cooperative effects in the kinetics of bimolecular A +B--*0 reactions between oppositely charged particles (reactants). It is shown that unlike the Debye-Hiickel theory in statistical physics, here charge screening has essentially a nonequilibrium character. For the asymmetric mobility of reactants (DA=0, D~4:0) the joint spatial distribution of similar immobile reactants A reveals at short distances a singular character associated with their aggregation. The relevant reaction rate does not approach a steady state (as it does in the symmetric case, DA=DB), but increases infinitel…
Kinetic Study of the Oxidation of n-Butane on Vanadium Oxide Supported on Al/Mg Mixed Oxide
1997
The reaction kinetics of the oxidative dehydrogenation (ODH) of n-butane over vanadia supported on a heat-treated Mg/Al hydrotalcite (37.3 wt % of V2O5) was investigated by both linear and nonlinear regression techniques. A reaction network including the formation of butenes (1-, 2-cis-, and 2-trans-butene), butadiene, and carbon oxides by parallel and consecutive reactions, at low and high n-butane conversions, has been proposed. Langmuir−Hinshelwood (LH) models can be used as suitable models which allows reproduction of the global kinetic behavior, although differences between oxydehydrogenation and deep oxidation reactions have been observed. Thus, the formation of oxydehydrogenation pro…
Initial reaction steps in the condensed-phase decomposition of propellants
2002
Understanding the reaction mechanisms for the decomposition of NO2-containing energetic materialsin the condensed phase is critical to our development of detailed kinetic models of these energetic materials in propellant combustion. To date, the reaction mechanisms in the condensed phase have been represented by global reactions. The detailed elementary reactions subsequent to the initial NO2 bond scissioning are not known. Using quantum chemical calculations, we have investigated the possible early steps in the decomposition of energetic materials that can occur in the condensed phase. We have used methylnitrate, methylnitramine, and nitroethane as prototypes for O−NO2, N−NO2 and C−NO2 nit…
Approach Matters : The Kinetics of Interfacial Inverse-Electron Demand Diels-Alder Reactions
2017
Rapid and quantitative click functionalization of surfaces remains an interesting challenge in surface chemistry. In this regard, inverse electron demand Diels Alder (IEDDA) reactions represent a promising metal-free candidate. Herein, we reveal quantitative surface functionalization within 15 min. Furthermore, we report the comprehensive effects of substrate stereochemistry, surrounding microenvironment and substrate order on the reaction kinetics as obtained via a combination of XPS and surface-bound mass spectrometry (DART-MS).
Coadsorption of NRR and HER Intermediates Determines the Performance of Ru-N4 toward Electrocatalytic N2 Reduction
2021
Efficiency of the electrochemical N2 reduction reaction (NRR) to ammonia is seriously limited by the competing hydrogen evolution reaction (HER) but our current atomic-scale insight on the factors controlling HER/NRR competition are unknown. Herein we unveil the elementary mechanism, thermodynamics, and kinetics determining the HER/NRR selectivity on the state-of-the-art NRR electrocatalyst, Ru-N4 using constant potential density functional theory calculations (DFT). The calculations show that NRR and HER intermediates coadsorb on the catalyst where HER is greatly suppressed by the NRR intermediates. The first reaction step leading to either *NNH or *H determines the selectivity towards NRR…
The influence of the “hot”-dimer adsorption mechanism on the kinetics of a monomer-dimer surface reaction
1993
“Hot” dimers are molecules which after adsorption dissociate and each of the remaining “hot” monomers fly apart up to a maximum distance R from the original adsorption site. The influence of the “hot”-dimer adsorption mechanism on relevant aspects of the bimolecular catalyzed reaction of the type A − (1/2)B2(“hot”) → AB is studied by means of the Monte-Carlo simulation technique. The temporal evolution of both the reactant's coverages as well as the rate of AB-production is evaluated and discussed. Due to the enhanced probability of “hot” species for encounters with other adsorbed particles, the rate of AB-production becomes faster when increasing R. This behavior may be relevant in the dyn…
Modeling of the catalytic effects of potassium and calcium on spruce wood gasification in CO2
2016
Abstract Using previously reported thermogravimetric analysis measurements, the effects of calcium and potassium on the char gasification rate of spruce wood were modeled. Spruce wood was leached of inorganic ash elements and doped with measured amounts of potassium and calcium. The wood was gasified in an isothermal thermogravimetric analysis device in CO 2 where the devolatilization of the wood, char formation and char gasification all occurred inside the preheated reactor. A new method for separating the effects of devolatilization and char gasification is presented. Kinetic models were evaluated for their ability to describe the observed catalytic effects of potassium and calcium on the…