Search results for " rate constant"
showing 10 items of 220 documents
Sol-gel auto-combustion synthesis of Ca2Fe2O5 brownmillerite nanopowders and thin films for advanced oxidation photoelectrochemical water treatment i…
2019
Abstract This study describes a straightforward Ca2Fe2O5 brownmillerite nanopowder and thin film synthesis by the water-based sol-gel auto-combustion method. The material characterization results confirmed the phase pure narrow bandgap Ca2Fe2O5 nanoparticle formation. The surface area of synthesized nanopowder was 13.55 m2/g. Powders at loading 1 g/l exhibit high visible light photocatalytic activity by degrading 10 mg/l methylene blue in water in 120 min confirmed by total organic carbon studies. The high visible light photocatalytic activity is related to Ca2Fe2O5 narrow band gap and high reduction potential of its conduction band which triggers the formation of superoxide radical ∙ O 2 -…
Ion conduction in the KcsA potassium channel analyzed with a minimal kinetic model.
2004
We use a model by Nelson to study the current-voltage and conductance-concentration curves of bacterial potassium channel KcsA without assuming rapid ion translocation. Ion association to the channel filter is rate controlling at low concentrations, but dissociation and transport in the filter can limit conduction at high concentration for ions other than ${\mathrm{K}}^{+}$. The absolute values of the effective rate constants are tentative but the relative changes in these constants needed to qualitatively explain the experiments should be of significance.
Investigation of eutectic transformation of Zn−Al alloy by DTA
1995
The paper discusses the investigation of crystallization of metals and alloys by differential thermal analysis (DTA). It was assumed that this method allows determination of the mechanism and kinetics of volumetric crystallization underiso conditions (e.g. anisothermal) on the basis of the parameters of the equation expressing an integral form of the DTA curve. From DTA, a course of eutectic transformation was determined for a technical Zn−Al alloy containing 4wt% Al. Investigations were carried out under continuous cooling at various rates and the kinetics parameters were determined with the KEKAM equation:-ln(1-x)=kln
A new approach for crystallization of copper(II) oxide hollow nanostructures with superior catalytic and magnetic response.
2015
We report the synthesis of copper(II) oxide hollow nanostructures at ambient pressure and close to room temperature by applying the soft templating effect provided by the confinement of droplets in miniemulsion systems. Particle growth can be explained by considering a mechanism that involves both diffusion and reaction control. The catalytic reduction of p-nitrophenol in aqueous media is used as a model reaction to prove the catalytic activity of the materials: the synthesized hollow structures show nearly 100 times higher rate constants than solid CuO microspheres. The kinetic behavior and the order of the reduction reaction change due to the increase of the surface area of the hollow str…
Modelling polycarbonate synthesis rates on the example of bulk heteropolyaddition of diphenyl carbonate and bisphenol A diglycidyl ether
2016
This paper investigates the effects of increased reaction mixture viscosity on the kinetics of linear polymer creation in a bulk polyaddition process of diphenyl carbonate and bisphenol A diglycidyl ether. The paper presents a method for solving a system of bulk polyaddition of diphenyl carbonate and bisphenol A diglycidyl ether process balance equations, allowing the determinatiof the process kinetic parameters. Determination of polymerisation reaction kinetic parameters was also made possible by the use of the so-called partial reaction rate constant. Such an approach enabled a significant simplification of the mathematical expressions describing the heteropolyaddition process and provide…
Polybutadiene model networks —synthesis, mechanical characterization and comparison with rubber elasticity models
1995
Model networks of defined crosslink density are prepared via nonradical statistical crosslinking of polybutadiene in bulk and concentrated solution using a masked bistriazolinedione as crosslinker. The kinetics of crosslinking is monitored by FT-IR-spectroscopy. The reaction follows pseudo-1st-order reaction kinetics. The activation parameter of the crosslinking reaction is estimated from crosslinking at various temperatures. Networks of deuterated polybutadiene are prepared by this reaction in a wide range of crosslink densities. The stress strain behavior is analyzed according to the Junction Constraint-Theory of rubber elasticity (JCT) and to the approach introduced by Graessley accounti…
Lifetime and collisional depopulation of the metastable 5D 3/2-state of Yb+
1988
The lifetime and collisional depopulation rates of the metastable 5D 3/2 state of Yb+ have been determined in a radiofrequency ion trap by observation of the fluorescence count rate after ion excitation by a short laser pulse. From measurements using He, N2 and H2 as buffer gases between 10−8 and 10−6 mbar pressure and linear extrapolation to zero pressure we obtain a lifetime of τ=52.15±1.00 ms and rate constants ofR(H2)=(1.02±0.10)×10−9 cm3/s andR(N2)=(1.78±0.19)×10−10 cm3/s. The lifetime is in fair agreement with a calculated value of 74 ms.
Blue-luminescent organic lead bromide perovskites: highly dispersible and photostable materials
2015
The preparation of a blue-luminescent and photostable organic–inorganic hybrid perovskite with an X-ray powder diffraction spectrum consistent with a two-dimensional inorganic framework is reported. This perovskite can be produced with a high reaction yield and valuable optical properties, such as luminescence quantum yield over 20%, radiative rate constant of up to 80 × 106 s−1, and high photostability under UV light. This material remains stable as a solid, is toluene-dispersible, and can be reverted reversibly into its precursors by using dimethylformamide (DMF). Moreover, the DMF dispersion can be injected into toluene to produce a nanomaterial or be used to prepare films by spin-coatin…
Critical Role of Substrate Conformational Change in the Proton Transfer Process Catalyzed by 4-Oxalocrotonate Tautomerase
2009
4-Oxalocrotonate tautomerase enzyme (4-OT) catalyzes the isomerization of 2-oxo-4-hexenedioate to 2-oxo-3-hexenedioate. The chemical process involves two proton transfers, one from a carbon of the substrate to the nitrogen of Pro1 and another from this nitrogen atom to a different carbon of the substrate. In this paper the isomerization has been studied using the combined quantum mechanical and molecular mechanical (QM/MM) method with a dual-level treatment of the quantum subsystem employing the MPW1BK density functional as the higher level. Exploration of the potential energy surface shows that the process is stepwise, with a stable intermediate state corresponding to the deprotonated subs…
Reversibility and Diffusion in Mandelythiamin Decarboxylation. Searching Dynamical Effects in Decarboxylation Reactions
2012
Decarboxylation of mandelylthiamin in aqueous solution is analyzed by means of quantum mechanics/molecular mechanics simulations including solvent effects. The free energy profile for the decarboxylation reaction was traced, assuming equilibrium solvation, while reaction trajectories allowed us to incorporate nonequilibrium effects due to the solvent degrees of freedom as well as to evaluate the rate of the diffusion process in competition with the backward reaction. Our calculations that reproduce the experimental rate constant show that decarboxylation takes place with a non-negligible free energy barrier for the backward reaction and that diffusion of carbon dioxide is very fast compared…