Search results for " rate constant"
showing 10 items of 220 documents
Electro- and photo-electrooxidation of 2,4,5-trichlorophenoxiacetic acid (2,4,5-T) in aqueous media with PbO2, Sb-doped SnO2, BDD and TiO2-NTs anodes…
2020
Abstract In this work, the 2,4,5-T degradation in aqueous media was studied by electro- (EC) and photoelectrochemical (PEC) oxidation methods, which are two of the most important advanced oxidation processes (AOPs) for wastewater treatment. Both EC and PEC experiments were carried out in a single compartment cell under galvanostatic conditions (30 mA cm−2) at 298 K by using 0.05 M Na2SO4 + 200 ppm 2,4,5-T at pH 3 and pH 9, as model solutions. EC oxidation was performed using Sb-doped SnO2, PbO2 and boron doped diamond (BDD) as anodic materials. Besides these anodes, TiO2 in a nanotubular structure (TiO2 NTs) with or without PbO2 dispersed nanoparticles (TiO2::PbO2) were also used for PEC ox…
Charge-Separation and Charge-Recombination Rate Constants in a Donor–Acceptor Buckybowl-Based Supramolecular Complex: Multistate and Solvent Effects
2021
The kinetics of the nonradiative photoinduced processes (charge-separation and charge-recombination) experimented in solution by a supramolecular complex formed by an electron-donating bowl-shaped truxene-tetrathiafulvalene (truxTTF) derivative and an electron-accepting fullerene fragment (hemifullerene, C30H12) has been theoretically investigated. The truxTTF·C30H12 heterodimer shows a complex decay mechanism after photoexcitation with the participation of several low-lying excited states of different nature (local and charge-transfer excitations) all close in energy. In this scenario, the absolute rate constants for all of the plausible charge-separation (CS) and charge-recombination (CR)…
Validation of a two-dimensional modeling of an externally irradiated slurry photoreactor
2015
Abstract A two-dimensional model describing the behavior of a batch cylindrical photoreactor has been validated through a series of photocatalytic reactivity runs. The light intensity radiation field produced by 1–6 external UV fluorescent lamps was modeled together with Langmuir–Hinshelwood kinetics and 4-nitrophenol (NP) and Degussa P25 TiO 2 were used as the probe molecule and the catalyst, respectively. The experiments were carried out under different conditions of light intensity, photocatalyst amount and substrate concentration. The model parameters were the kinetic constant of substrate adsorption, desorption and degradation and the exponent of the power law expressing the kinetics d…
Picosecond time-resolved study on the nature of high-energy-state quenching in isolated pea thylakoids different localization of zeaxanthin dependent…
1996
Abstract The influence of the transthylakoid proton gradient on the kinetics of picosecond fluorescence decay was examined using isolated pea thylakoids having high or low zeaxanthin contents. Fluorescence lifetime measurements were performed with open (Fo) and closed (Fm) PS II reaction centers. Zeaxanthin formation in membrane energized isolated thylakoids led to a marked decrease of the average fluorescence lifetime at both Fm and Fo. In contrast, when zeaxanthin synthesis was blocked by the inhibitor DTT, the fluorescence lifetime decrease was less pronounced in the Fm state and totally missing in the Fo state. Samples containing the uncoupler ammonium chloride did not exhinit any zeaxa…
First-Principles Computed Rate Constant for the O + O 2 Isotopic Exchange Reaction Now Matches Experiment
2018
We show, by performing exact time-independent quantum molecular scattering calculations, that the quality of the ground electronic state global potential energy surface appears to be of utmost importance in accurately obtaining even as strongly averaged quantities as kinetic rate constants. The oxygen isotope exchange reaction, 18O + 32O2, motivated by the understanding of a complex long-standing problem of isotopic ozone anomalies in the stratosphere and laboratory experiments, is explored in this context. The thermal rate constant for this key reaction is now in quantitative agreement with all experimental data available to date. A significant recent progress at the frontier of three rese…
The influence of the solvent's mass on the location of the dividing surface for a model Hamiltonian
2019
The Transition State dividing surface is a key concept, not only for the precise calculation of the rate constant of a reaction, but also for the proper prediction of product ratios. The correct location of this surface is defined by the requirement that reactive trajectories do not recross it. In the case of reactions in solution the solvent plays an important role in the location of the dividing surface. In this paper we show with the aid of a model Hamiltonian that the effective mass of the solvent can dramatically change the location of the dividing surface. Keywords: Dynamical systems, Dividing surface, Reactions in solution, 2019 MSC: 00-01, 99-00
Quantum mechanical study of the 16O + 18O18O → 16O18O + 18O exchange reaction: Integral cross sections and rate constants
2018
The isotopic exchange reaction, 16O + 18O18O → 16O18O + 18O, involving excited ozone, O3*, as intermediate complex, was investigated by means of a time independent quantum mechanical approach using the TKTHS potential energy surface (PES) [V. G. Tyuterev et al., J. Chem. Phys. 139, 134307 (2013)] of ozone. State-to-state integral cross sections were calculated for collision energies lower than 0.4 eV. Then specific and thermal rate constants were computed between 10 K and 350 K using these cross sections. The full quantum thermal rate constant is found to be in better agreement with the most recent experimental data than with previous studies where other O3 PESs were employed, confirming th…
Collisional de-excitation of the metastableD-states of Ba+ by He, Ne, N2 and H2
1989
The rate constants 〈σ · υ〉 for collisional de-excitation of the metastable 5D states of Ba+ ions have been determined in an ion trap experiment. TheD-states are selectively populated by pulsed laser excitation of the 6P1/2 or 6P3/2 state and the decay at different background pressures is monitored by the change in fluorescence intensity of the excited ions. From the pressure dependence of the decay constants we calculate the de-excitation rate constants for different collision partners, averaged over the velocity distribution of the trapped ion cloud. For He, Ne, H2 and N2 we obtain in the c.m. energy range of 0.1–0.5 eV: 〈σ·υ〉 (He)=3.0±0.2·10−13cm3/s, 〈σ·υ〉 (Ne)=5.1±0.4·10−13cm3/s, 〈σ·υ〉 (…
Model-independent determination of dissociation energies: method and applications
2003
A number of methods are available for the purpose of extracting dissociation energies of polyatomic particles. Many of these techniques relate the rate of disintegration at a known excitation energy to the value of the dissociation energy. However, such a determination is susceptible to systematic uncertainties, mainly due to the unknown thermal properties of the particles and the potential existence of 'dark' channels, such as radiative cooling. These problems can be avoided with a recently developed procedure, which applies energy-dependent reactions of the decay products as an uncalibrated thermometer. Thus, it allows a direct measurement of dissociation energies, without any assumption …
Temperature dependence of dynamic, tunnelling and kinetic isotope effects in formate dehydrogenase
2018
The origin of the catalytic power of enzymes has been a question of debate for a long time. In this regard, the possible contribution of protein dynamics in enzymatic catalysis has become one of the most controversial topics. In the present work, the hydride transfer step in the formate dehydrogenase (FDH EC 1.2.1.2) enzyme is studied by means of molecular dynamic (MD) simulations with quantum mechanics/molecular mechanics (QM/MM) potentials in order to explore any correlation between dynamics, tunnelling effects and the rate constant. The temperature dependence of the kinetic isotope effects (KIEs), which is one of the few tests that can be studied by experiments and simulations to shed li…