Search results for "Rate equation"
showing 10 items of 38 documents
Photochemical generation of E′ centres from Si–H in amorphous SiO2under pulsed ultraviolet laser radiation
2006
In situ optical absorption spectroscopy was used to study the generation of E' centres () in amorphous SiO2 occurring by photo-induced breaking of Si–H groups under 4.7 eV pulsed laser radiation. The dependence on laser intensity of the defect generation rate is consistent with a two-photon mechanism for Si–H rupture, while the growth and saturation of the defects are conditioned by their concurrent annealing due to a reaction with mobile hydrogen arising from the same precursor. A rate equation is proposed to model the kinetics of the defects and is tested on experimental data.
Nonresonant dielectric hole burning spectroscopy of supercooled liquids
1997
The nonexponential response of propylene carbonate and glycerol near their glass transitions could be selectively altered using nonresonant spectral hole burning (NSHB) experiments. This observation provides evidence of the existence of a distribution of relaxation times in these supercooled liquids. NSHB is based on a pump, wait, and probe scheme and uses low-frequency large amplitude electrical fields to modify the dielectric relaxation. The temporal evolution of the polarization of the sample is then measured subsequent to a small voltage step. By variation of a recovery time inserted between pump and probe, the refilling of the spectral features could be monitored and was found to take …
Kinetics of the permanganate oxidation of formic acid in aqueous solution
1987
The kinetics of the permanganate oxidation of formic acid in aqueous perchloric acid at 30°C were examined by the spectrophotometric method. The chemical reaction 2MnO + 3HCOOH + 2H+ 2MnO2 + 3CO2 + 4H2O, appears to proceed via several parallel reactions. The overall rate equation has been obtained by using statistical multilinear regression analysis of the 660 cases studied, and the presence in the rate equation of two new terms in relation to previous studies shows that both permanganate autocatalytic effects and acid media inhibition must be taken into account when the reaction proceeds at constant ionic strength.
Rate Theory for Electrocatalytic Systems: Fixed Potential Formulation for General, Electron Transfer, and Proton-Coupled Electron Transfer Reactions
2019
Atomistic modeling of electrocatalytic reactions is most naturally conducted within the grand canonical ensemble (GCE) which enables fixed chemical potential calculations. While GCE has been widely adopted for modeling electrochemical and electrocatalytic thermodynamics, the electrochemical reaction rate theory within GCE is lacking. Molecular and condensed phase rate theories are formulated within microcanonical and canonical ensembles, respectively, but electrocatalytic systems described within the GCE require extension of the conventionally used rate theories for computation reaction rates at fixed electrode potentials. In this work, rate theories from (micro) canonical ensemble are gene…
Unified Rate Theory of Electrochemistry and Electrocatalysis: Fixed Potential Formulation for General, Electron Transfer, and Proton-Coupled Electron…
2019
Atomistic modeling of electrocatalytic reactions is most naturally conducted within the grand canonical ensemble (GCE) which enables fixed chemical potential calculations. While GCE has been widely adopted for modeling electrochemical and electrocatalytic thermodynamics, the electrochemical reaction rate theory within GCE is lacking. Molecular and condensed phase rate theories are formulated within microcanonical and canonical ensembles, respectively, but electrocatalytic systems described within the GCE require extension of the conventionally used rate theories for computation reaction rates at fixed electrode potentials. In this work, rate theories from (micro)canonical ensemble are gener…
Data Treatment in Kinetics
2000
Chemical kinetics is an important part of chemistry devoted to study how reactions proceed and quantify the rate of the process. The reaction mechanism is the chemical model that describes how the chemical change occurs. From the proposed mechanism, a mathematical model can be obtained to explain the evolution of the chemical species with time. In many cases, the mechanism can be simplified to a single rate law that relates the reaction rate with concentrations. In the last decades, the study of kinetic systems has benefited from the development of instrumentation, the increasing availability of specialized computer software, and the advances in data treatment techniques. A comprehensive re…
Determination of kinetic parameters of redox reactions using CE‐ICP‐MS: A case study for the reduction of Np(V) by hydroxylamine hydrochloride
2018
The rate constants k of the reduction of 5 × 10-5 M Np(V) to Np(IV) by hydroxylamine hydrochloride (HAHCl) in 1 M HCl have been determined by CE-ICP-MS in the temperature range of ϑ = 30-70°C and with varying concentrations of HAHCl from 1 to 7.2 M. The reaction was found to have (pseudo)first order kinetics with respect to HAHCl. The experimental results for k ranged from 0.0029(1) min-1 (ϑ = 40°C, c(HAHCl) = 3 M) to 0.039(7) min-1 (ϑ = 60°C, c(HAHCl) = 7.2 M). The activation energy of the reaction was determined as EA = (72 ± 10) kJ/mol. These results and a comparison with literature data show that the coupling of CE to ICP-MS provides a powerful analytical tool for the investigation of…
Size dependent carrier thermal escape and transfer in bimodally distributed self assembled InAs/GaAs quantum dots
2012
We have investigated the temperature dependent recombination dynamics in two bimodally distributed InAs self assembled quantum dots samples. A rate equations model has been implemented to investigate the thermally activated carrier escape mechanism which changes from exciton-like to uncorrelated electron and hole pairs as the quantum dot size varies. For the smaller dots, we find a hot exciton thermal escape process. We evaluated the thermal transfer process between quantum dots by the quantum dot density and carrier escape properties of both samples. © 2012 American Institute of Physics.
Simulation of mid-IR amplification in Er3+-doped chalcogenide microstructured optical fiber
2009
International audience; This paper deals with the design of an erbium doped microstructured optical fiber (MOF) amplifier operating in the mid-infrared (mid-IR) wavelength range, more precisely around 4.5 µm wavelength. A homemade numerical code which solves the rate equations and the power propagation equations has been ad hoc developed to theoretically investigate the feasibility of mid-IR MOF amplifier. On the basis of the measured energy level transition parameters of a Er3+-doped Ga5Ge20Sb10S65 chalcogenide glass, the amplifier feasibility is demonstrated exhibiting high gain and low noise figure.
Implementation of a double-scanning technique for studies of the Hanle effect in rubidium vapor
2007
We have studied the resonance fluorescence of a room-temperature rubidium vapor exited to the atomic 5P3/2 state (D2 line) by powerful single-frequency cw laser radiation (1.25 W/cm^2) in the presence of a magnetic field. In these studies, the slow, linear scanning of the laser frequency across the hyperfine transitions of the D2 line is combined with a fast linear scanning of the applied magnetic field, which allows us to record frequency-dependent Hanle resonances from all the groups of hyperfine transitions including V- and Lambda - type systems. Rate equations were used to simulate fluorescence signals for 85Rb due to circularly polarized exciting laser radiation with different mean fre…