Chemical Rate Constants Research Articles

Suppressed atmospheric chemical aging of cooking organic aerosol particles in wintertime conditions

Abstract. Cooking organic aerosol (COA) is one of the major constituents of particulate matter in urban areas. COA is oxidized by atmospheric oxidants such as ozone, changing its physical, chemical and toxicological properties. However, atmospheric chemical lifetimes of COA and its tracers such as oleic acid are typically longer than those that have been estimated by laboratory studies. We tackled the issue by considering temperature. Namely, we hypothesize that increased viscosity of COA at ambient temperature accounts for its prolonged atmospheric chemical lifetimes in wintertime. Laboratory-generated COA particles from cooking oil were exposed to ozone in an aerosol flow tube reactor for the temperature range of −20 to 35 °C. The pseudo-second-order chemical reaction rate constants (k2) were estimated from the experimental data by assuming a constant ozone concentration in the flow tube. The estimated values of k2 decreased by orders of magnitude for lower temperatures. The temperature dependence in k2 was fit well by considering the diffusion-limited chemical reaction mechanism. The result suggested that increased viscosity was likely the key factor to account for the decrease in chemical reactivity at the reduced temperature range, though the idea will still need to be verified by temperature-dependent viscosity data in the future. In combination with the observed global surface temperature, the atmospheric chemical lifetimes of COA were estimated to be much longer in wintertime (> 1 h) than in summertime (a few minutes) for temperate and boreal regions. Our present study demonstrates that the oxidation lifetimes of COA particles will need to be parameterized as a function of temperature in the future for estimating environmental impacts and fates of this category of particulate matter.

Improved prediction of reaction kinetics for amine absorbent-based carbon capture using reactive site-based transition state conformer search method

There is no doubt that carbon emissions are one of the greatest challenges facing humanity today. Carbon capture, utilization, and storage is an effective way to achieve carbon neutrality. However, the commonly used commercial absorbents for post-combustion captures still have some limitations such as low chemical absorption rate constants. In this paper, a universal reaction kinetic model is developed for amine-based carbon capture based on the transition state theory, density functional theory, and hybrid solvation model. The developed reaction kinetic model is applicable to a wide range of amine-solvent solutions involving primary/secondary/tertiary amines and aqueous/nonaqueous solvents. The key contribution of this work is developing a reactive site-based search method for the GENeration of Conformers for Transition States (GENConf-TS). GENConf-TS has greatly improved the prediction accuracy of the reaction kinetic model from R2 = 0.882 to R2 = 0.950 based on a dataset of 23 various amine-solvent solutions. The results highlight the critical impacts of the transition state conformational isomers on amine-based CO2 chemical absorption rate constants.

Roles of temperature and ventilation in oxygen consumption: A chemical kinetics view from the van't Hoff-based formulation

In this study, we successfully estimated the apparent activation energy of a microbially driven oxygen-consuming reaction (microbial-driven) based on tracer data. The concept of the apparent chemical reaction rate constant was employed to estimate various thermodynamic parameters associated with the oxygen consumption rate in conjunction with Arrhenius/Eyring equations. Normal Ea values of 80–90 kJ mol−1 were found in the upper layers of the South China Sea and Sulu Sea, while higher Ea values (300–1000 kJ mol−1) were observed in the rapidly ventilated Mediterranean Sea, the Sea of Japan, and the Bering Sea with lower temperatures. We classified the characteristics of typical sea basins into four categories. The temperature-dependent oxygen consumption rate relationship in each marine region was systematically calculated to derive the respective thermodynamic characteristic values. This allowed us to parameterize the rate-temperature relationship into thermodynamic quantities, enabling more effective integration of distinct basin characteristics within different sea areas into the marine biochemical model. Parameterization facilitates relatively accurate prediction of changes such as temperature, oxygen consumption rate.

Investigating the magneto-transport and thermal properties of 2D electron systems under the influence of the Aharonov–Bohm field and Eckart potential interaction

The Eckart potential is a well-known potential model with applications cutting across chemical physics and related areas. It is often used to evaluate quantum mechanical tunneling corrections in order to obtain chemical rate constants. To this end, this study focused on extensively examining the effects of perturbations on the magnetic and thermal properties of the Eckart potential. In the presence of magnetic and Aharonov–Bohm fields with Eckart potential, the Schrödinger equation is solved using the functional analysis approach (FAA). The energy equation and wave function are obtained analytically. The energy equation is used to derive expressions for the thermo-magnetic properties of the Eckart potential. An extensive analysis of the effect of these fields and potential parameters on the wave function is presented. In several configurations of the analysis, we observe that the system exhibits a diamagnetic behavior,and the specific heat capacity agree with the Dulong–Petit law. The results of this study are valuable in areas such as molecular physics and condensed matter physics, amongst others.

Novel 3D analysis of reduction behavior of single iron-oxide particle in CO-CO2 gas atmosphere

The production of steel, which is achieved by the reduction of iron ores mainly through indirect reduction reactions in a blast furnace, is gradually increasing worldwide. Because the reducing gas diffuses three-dimensionally, irregular particle shapes influence the reduction through differences in the diffusion length. The analysis of actual irregularly shaped iron-ore particles using existing models is difficult because they are primarily effective for 1D systems. Therefore, a novel reduction model based on the 3D diffusion equation that accommodates irregular particle shapes and 3D systems was developed in this study. The established model was validated by reproducing experimental conditions and comparing the quantified effective diffusivity and chemical reaction rate constant using the shrinking core model. In addition, the model was used to investigate the reducing behavior of an actual sintered-ore particle and the effects of particle sphericity and macro pore content. The sintered-ore particle had a higher reduction rate than that of a spherical equivalent with the same volume because sections of the surface with shorter diffusion lengths facilitated the gas diffusion. Additionally, the particle sphericity was determined to be inversely proportional to the reduction rate because the rate of gas diffusion into the particle depended on the diffusion length. With respect to porous particles, the gas was found to readily diffuse into the particles through pores, leading to a higher reduction rate for higher pore numbers. Overall, the gas diffusion was confirmed to drive the reduction reaction.

A chemical credit framework to predict the removal performance of organic chemicals of concern from water through an ozonation process

Ozonation is an effective barrier for removing a wide spectrum of organic Chemicals of Concern (CoC) in a water treatment process. In this study, bench- and full-scale tests were conducted on a secondary treated effluent at the Eastern Treatment Plant (ETP) of Melbourne Water to probe the performance of ozonation in removing CoC in a wastewater discharge. From the secondary treated effluent as the feed to the ozone process, 58 organic chemicals were measured out of a possible 949 compounds by using the AIQS-DB analytical method. A chemical credit framework for the ozonation process has been established according to the bench-scale results. Chemical classifications based on the chemical structures (aromatics, aliphatic and halogenated aliphatic compounds) and reaction rate constants with O3 (KO3) and the ∙OH radical (K∙OH) and a combined O3/TOC ratio and O3 CT value as operating parameters were confirmed to be useful and important in determining whether a chemical would be removed by ozone. It is shown that an O3/TOC ratio of >0.404 was shown to be necessary to overcome the instantaneous ozone demand (IOD) to guarantee enough ozone to oxidise CoC. For CoC with KO3 >105M − 1s − 1 and K∙OH >109M − 1s − 1, an O3/TOC ratio of ≥0.461 or a measurable O3 CT of ≥0.063 mg min/L can achieve log reduction values (LRVs) of ≥1, these are chemicals with aromatic structures; For CoC with low KO3 and high KOH, a combined O3/TOC ratio and O3 CT value inclusive of a chemical structure classification is indicated as necessary criteria to evaluate the removal. UV254 and TOC were demonstrated to be good online surrogates of ozone barrier performance in the absence of continuous O3/TOC ratio and O3 CT value measurements. Full-scale operational results confirm the effective predictions of the chemical credit framework, which highlights the necessity and importance of monitoring both the O3/TOC ratio and O3 CT values to predict the removal efficiency of a given chemical with a known response to O3 or a known chemical structure.

Resilience of parity-violation-induced chiral selectivity to nonequilibrium temperature fluctuations in open systems

We consider the sensitivity of chemical reactions, able to undergo spontaneous mirror symmetry breaking, to chiral bias in the presence of nonequilibrium temperature fluctuations and derive a selectivity criterion. For this, we estimate the magnitude of fluctuations $\ensuremath{\delta}k$ in chemical reaction rate constants $k$ arising from the nonequilibrium temperature fluctuations $\ensuremath{\delta}T$ about a mean value $T$. To leading order, the relative rate constant fluctuations $\ensuremath{\delta}{k}_{i}/{k}_{i}$ for each reaction $i$ are given by the product of the activation enthalpy $\mathrm{\ensuremath{\Delta}}{H}_{i}^{\ifmmode\ddagger\else\textdaggerdbl\fi{}}/RT$ for the $i\mathrm{th}$ reaction multiplied by the relative rms temperature fluctuations $\ensuremath{\delta}{T}_{\mathrm{rms}}/T$. The latter are determined by the system's specific heat at constant volume: ${C}_{V}$. We test this criterion with simulations carried out for an open-flow fully reversible Frank model, and for a range of parity-violating energy differences (PVED) within the theoretically estimated upper and lower bounds. Depending on the relative magnitudes of the deterministic PVED bias and the temperature fluctuations, the PVED bias can either (i) select the final stable chiral outcome deterministically or (ii) select one of two possible stable chiral outcomes with an asymmetric statistical weighting. For larger temperature fluctuations, the PVED bias loses its selectivity, and the final stable chiral outcomes are stochastic and equally probable. This paper points towards the possible design of small volume chemical flow reactors capable of detecting the elusive PVED bias in bulk systems, provided other sources of fluctuations can be sufficiently controlled and attenuated.

HeapSim2D – A 2D axisymmetric model of heap leaching under drip emitters I. Hydrology and solute transport

Most modern heap leaching processes involve drip irrigation, which induces certain flow and dispersion patterns within the heap. However, this important aspect of heap leaching is overlooked in most mathematical models.This is the first in a planned series of papers presenting a two-dimensional comprehensive model of heap leaching under drip emitters, called HeapSim2D. In this paper, the fundamentals of heap leach modelling are discussed, with particular attention paid to the effect of drip irrigation on the flow of water and the dispersion of solutes within heaps. The mathematical and numerical foundations of a 2D axisymmetric model of heap irrigation under a single point source are developed in detail, and a sensitivity study is presented for the simple case of a first-order gangue acid dissolution reaction in a column under a single drip emitter, using hydrological parameters based on experimental work presented in a previous paper.Simulations show that the capillary head parameter hc,0 is the master parameter which determines the degree of solution spreading under drip emitters. Ores with high capillarity (such as agglomerated ores with significant fines) will spread the solution effectively, whereas ores with low capillarity (such as pebbles without fines) will confine the flow mostly to a channel below the drip emitter. Also, even ores with high capillarity will have a largely unwetted zone at the top of the heap or column.Simulations also show that solute dispersion has a relatively subtle effect on the rate of chemical reactions within heaps and columns, but that, presuming the solution is spread out, the chemical rate constant is the most important parameter in determining the degree of reaction within heaps and columns.In future papers, models for gas flow, gas species transport, heat transport, and various case studies involving custom networks of chemical and biological reactions with kinetics will be presented.

Theory of vibrational polariton chemistry in the collective coupling regime.

We theoretically demonstrate that the chemical reaction rate constant can be significantly suppressed by coupling molecular vibrations with an optical cavity, exhibiting both the collective coupling effect and the cavity frequency modification of the rate constant. When a reaction coordinate is strongly coupled to the solvent molecules, the reaction rate constant is reduced due to the dynamical caging effect. We demonstrate that collectively coupling the solvent to the cavity can further enhance this dynamical caging effect, leading to additional suppression of the chemical kinetics. This effect is further amplified when cavity loss is considered.

Absolute determination of chemical kinetic rate constants by optical tracking the reaction on the second timescale using cavity-enhanced absorption spectroscopy.

We report a new spectroscopic platform coupled to an atmospheric simulation chamber for the direct determination of chemical rate constants with high accuracy at a second time-scale resolution. These developed analytical instruments consist of an incoherent broadband cavity enhanced absorption spectrometer using a red light emitting diode (LED) emitting at ∼662 nm (LED-IBBCEAS) associated with a multipass cell direct absorption spectrometer (MPC-DAS) coupled to an external cavity quantum cascade laser (EC-QCL) operating in the mid-infrared region at approximately 8 μm (EC-QCL-MPC-DAS). Spectrometers were employed to investigate the NO3-initiated oxidation of four selected volatile organic compounds (VOCs) for the determination of the corresponding rate constants with a dynamic range of 5 orders of magnitude (from 10-11 to 10-16 cm3 molecule-1 s-1). Rate constants of (6.5 ± 0.5) × 10-15, (7.0 ± 0.4) × 10-13, and (5.8 ± 0.5) × 10-16 cm3 molecule-1 s-1 for propanal, isoprene and formaldehyde, respectively, were directly determined by fitting the measured concentration-time profiles of NO3 and VOCs (measured using a proton transfer reaction time-of-flight mass spectrometer, PTR-ToF-MS) to chemical models based on the FACSIMILE simulation software (version 4.2.50) at 760 torr and 293 ± 2 K. The obtained rate constants are in good agreement with the most recent recommendations of the IUPAC (International Union of Pure and Applied Chemistry). In addition, a rate constant of (2.60 ± 0.30) × 10-11 cm3 molecule-1 s-1 for the oxidation of 2-methoxyphenol by NO3 radicals was first determined using the absolute kinetic method. Compared to the mostly used indirect relative rate method, the rate constant uncertainty is reduced from ∼20% to ∼12%. The results demonstrated the high potential of using modern spectroscopic techniques to directly determine the chemical reaction rate constants.

Progress towards machine learning reaction rate constants.

Quantum and classical reaction rate constant calculations come at the cost of exploring potential energy surfaces. Due to the "curse of dimensionality", their evaluation quickly becomes unfeasible as the system size grows. Machine learning algorithms can accelerate the calculation of reaction rate constants by predicting them using low cost input features. In this perspective, we briefly introduce supervised machine learning algorithms in the context of reaction rate constant prediction. We discuss existing and recently created kinetic datasets and input feature representations as well as the use and design of machine learning algorithms to predict reaction rate constants or quantities required for their computation. Amongst these, we first describe the use of machine learning to predict activation, reaction, solvation and dissociation energies. We then look at the use of machine learning to predict reactive force field parameters, reaction rate constants as well as to help accelerate the search for minimum energy paths. Lastly, we provide an outlook on areas which have yet to be explored so as to improve and evaluate the use of machine learning algorithms for chemical reaction rate constants.

Assessing and rationalizing the performance of Hessian update schemes for reaction path Hamiltonian rate calculations.

The reaction path Hamiltonian (RPH) can be used to calculate chemical reaction rate constants, going beyond transition-state theory in taking account of recrossing by providing an approximation to the dynamic transmission coefficient. However, the RPH necessitates the calculation of the Hessian matrix at a number of points along the minimum energy path; the associated computational cost stands as a bottleneck in RPH calculations, especially if one is interested in using high-accuracy electronic structure methods. In this work, four different Hessian update schemes (symmetric rank-1, Powell-symmetric Broyden, Bofill, and TS-BFGS updates) are assessed to see whether or not they reliably reproduce calculated transmission coefficients for three different chemical reactions. Based on the reactions investigated, the symmetric rank-1 Hessian update was the least appropriate for RPH construction, giving different transmission coefficients from the standard analytical Hessian approach, as well as inconsistent frequencies and coupling properties. The Bofill scheme, the Powell-symmetric Broyden scheme, and the TS-BFGS scheme were the most reliable Hessian update methods, with transmission coefficients that were in good agreement with those calculated by the standard RPH calculations. The relative accuracy of the different Hessian update schemes is further rationalized by investigating the approximated Coriolis and curvature coupling terms along the reaction-path, providing insight into when these schemes would be expected to work well. Furthermore, the associated computational cost associated with the RPH calculations was substantially reduced by the tested update schemes. Together, these results provide useful rules-of-thumb for using Hessian update schemes in RPH simulations.

Cyclic voltammetry to study kinetics of blast furnace slag and cerium dioxide modified electrode

Abstract The use of a voltammetric sensor to measure hazardous elements has gotten a lot of coverage. The electrochemical sensor in this study was modified with cerium dioxide (CeO2) and blast furnace slag (BFS), which opens up new possibilities for improving the electrocatalytic properties of the fabricated sensor. In general chemical kinetics or mass transport can restrict the reactions involved in electrochemical detection. The prepared electrodes were tested against potassium ferricyanide, K3Fe(CN)6 solution by cyclic voltammetry. Cyclic voltammetry was used to investigate the chemical reactions involve during redox process. The electron transfer kinetics, chemical rate constant, and diffusion characteristics of reactions can all be extracted using this method. Further this sensor was applied in the detection of lead and copper ions in aqueous solution. The results show that the redox reaction is a one-electron transfer mechanism with high selectivity and sensitivity. The value of transfer coefficient (α) for the electrode reaction was calculated as 0.61. Also the calculated heterogeneous electron transfer rate constant (Ks) of the modified electrode was 2.41.

Dynamical Models of Chemical Exchange in Nuclear Magnetic Resonance Spectroscopy.

Chemical exchange line-broadening is an important phenomenon in nuclear magnetic resonance (NMR) spectroscopy, in which a nuclear spin experiences more than one magnetic environment as a result of chemical or conformational changes of a molecule. The dynamic process of chemical exchange strongly affects the sensitivity and resolution of NMR experiments, and increasingly provides a powerful probe of the inter-conversion between chemical and conformational states of proteins, nucleic acids, and other biological macromolecules. A simple and often used theoretical description of chemical exchange in NMR spectroscopy is based on an idealized two-state jump model (the random-phase or telegraph signal). However, chemical exchange can also be represented as a barrier-crossing event that can be modeled using chemical reaction rate theory. The time scale of crossing is determined by the barrier height, the temperature, and the dissipation modeled as collisional or frictional damping. This tutorial explores the connection between the NMR theory of chemical exchange line-broadening and strong-collision models for chemical kinetics in statistical mechanics. Theoretical modeling and numerical simulation are used to map the rate of barrier-crossing dynamics of a particle on a potential energy surface to the chemical exchange relaxation rate constant. By developing explicit models for the exchange dynamics, the tutorial aims to elucidate the underlying dynamical processes that give rise to the rich phenomenology of chemical exchange observed in NMR spectroscopy. Software for generating and analyzing the numerical simulations is provided in the form of Python and Fortran source codes.

Measurement of Interpeptidic CuII Exchange Rate Constants of CuII-Amyloid-β Complexes to Small Peptide Motifs by Tryptophan Fluorescence Quenching.

The interpeptidic CuII exchange rate constants were measured for two Cu amyloid-β complexes, Cu(Aβ1-16) and Cu(Aβ1-28), to fluorescent peptides GHW and DAHW using a quantitative tryptophan fluorescence quenching methodology. The second-order rate constants were determined at three pH values (6.8, 7.4, and 8.7) important to the two Cu(Aβ) coordination complexes, components Cu(Aβ)I and Cu(Aβ)II. The interpeptidic CuII exchange rate constant is approximately 104 M-1 s-1 but varies in magnitude depending on many variables. These include pH, length of the Aβ peptide, location of the anchoring histidine ligand in the fluorescent peptide, number of amide deprotonations required in the tryptophan peptide to coordinate CuII, and interconversion between Cu(Aβ)I and Cu(Aβ)II. We also present EPR data probing the CuII exchange between peptides and the formation of ternary species between Cu(Aβ) and GHW. As the nonfluorescent GHK and DAHK peptides are important motifs found in the blood and serum, their ability to sequester CuII ions from Cu(Aβ) complexes may be relevant for the metal homeostasis and its implication in Alzheimer's disease. Thus, their kinetic CuII interpeptidic exchange rate constants are important chemical rate constants that can help elucidate the complex CuII trafficking puzzle in the synaptic cleft.

Intermolecular dynamics and paramagnetic properties of Tm-Na heterometallic complex with macrocyclic ligand by 23Na dynamic NMR

The temperature dependence of lanthanide-induced shifts (LIS) and chemical exchange rate constants are studied. The analysis of chemical exchange rate constants was carried out using the method of analysis of the bandshape taking into account the temperature change in the LIS. The value of Gibbs free energy for the activation of intermolecular dynamics is ΔG≠(298 K) = 55 ± 2 kJ/mol. Method of analysis of the bandshape taking into account the temperature change in the paramagnetic lanthanide-induced shifts used for estimation the activation energy of intermolecular dynamics ΔG≠(298 K) = 55 ± 2 kJ/mol.

Determining chemical exchange rate constants in nanoemulsions using nuclear magnetic resonance.

In this work, the second-order kinetics of molecules exchanging between chemically distinct microenvironments, such as those found in nanoemulsions, is studied using nuclear magnetic resonance (NMR). A unique aspect of NMR exchange studies in nanoemulsions is that the difference in molecular resonance frequencies between the two phases, which determines whether the exchange is fast, intermediate, or slow on the NMR timescale, can depend upon the emulsion droplet composition, which is also determined by the kinetic exchange constants themselves. Within the fast-exchange regime, changes in resonance frequencies and line widths with dilution were used to extract the exchange rate constants from the NMR spectra in a manner analogous to determining the kinetic parameters in NMR ligand binding experiments. As a demonstration, the kinetic exchange parameters of isoflurane release from an emulsification of isoflurane and perflurotributylamine (FC43) were determined using NMR dilution and diffusion studies.

Comparison of acoustic and hydrodynamic cavitation based hybrid AOPs for COD reduction of commercial effluent from CETP

The present work investigates the treatment of commercial effluent obtained from Common Effluent Treatment Plants (CETP) using acoustic cavitation (AC) and hydrodynamic cavitation (HC) based hybrid AOPs. Comparison of different hybrid AOPs viz. H2O2, Fe2+/H2O2, Fe2+/H2O2/Air, Fe2+/H2O2/S2O82− and Fe2+/H2O2/S2O82−/Air in combination with both AC and HC has been performed in terms of extent of chemical oxygen demand (COD) reduction and kinetic rate constants. The best results of COD reduction as 95.2% and 97.28% were obtained for AC/Fe2+/H2O2/Air and HC/Fe2+/H2O2/Air systems respectively at Fe2+/H2O2 ratio of 0.1 and pH of 2 within 60 min of treatment under conditions of ultrasonic power dissipation as 150 W, inlet pressure for HC as 4 bar (as applicable depending on process) and temperature of 30 ± 2 °C. Slightly lower efficacy was established for the combination approach involving AC or HC coupled with Fe2+-activated S2O82− and H2O2 yielding COD reduction of 82.9% and 86.93% for the AC/Fe2+/H2O2/S2O82−/Air and HC/Fe2+/H2O2/S2O82−/Air systems respectively at Fe2+/H2O2/S2O82− ratio of 1:40:17.5. Cost estimation on the basis of cavitational yield performed on the AC and HC based treatment systems revealed economical nature of HC based treatment. Kinetic studies were also performed by fitting the experimental data with pseudo first order kinetic model (PFOKM), generalized kinetic model (GKM) and Behnajady-Modirshahla-Ghanbery kinetic model (BMGKM). It was demonstrated that GKM provided best fitting for all the experiments whereas BMGKM was most suitable for Fenton based reactions. It was clearly established that complex CETP effluent can be effectively treated using the combined approaches based on HC with potential for larger scale operation.

Modeling the Mineralization Kinetics of Visible Led Graphene Oxide/Titania Photocatalytic Ozonation of an Urban Wastewater Containing Pharmaceutical Compounds

In a water ozonation process, dissolved organics undergo two reactions at least: direct ozone attack and oxidation with hydroxyl radicals generated from the ozone decomposition. In the particular case of urban wastewater contaminated with pharmaceuticals, competition between these two reactions can be studied through application of gas–liquid reaction kinetics. However, there is a lack in literature about kinetic modeling of ozone processes in water specially in photocatalytic ozonation. In this work, lumped reactions of ozone and hydroxyl radicals with total organic carbon have been proposed. Urban wastewater containing a mixture of eight pharmaceutical compounds has been used to establish the kinetic model that simulates the mineralization process. The kinetic model is based on a mechanism of free radical and molecular reactions and the knowledge of mass transfer, chemical reaction rate constants, and radiation transfer data. According to the model, both single ozonation and photocatalytic ozonation present two distinct reaction periods characterized by the absence and presence of dissolved ozone. In the first period (less than 10 min), pharmaceuticals mainly disappear by direct ozone reactions and TOC variation due to these compounds has been modeled according to gas–liquid reaction kinetics through a lumped ozone-pharmaceutical TOC fast second order reaction. The corresponding rate constant of this reaction was found to change with time from 3 × 105 to 200 M−1 s−1 with Hatta values higher than 0.3. In the second period (nearly 5 h), competition between direct and hydroxyl radical reactions takes place and a kinetic model based on a direct and free radical reaction mechanism is proposed. Main influencing parameters to be known were: Direct ozone reaction rate constant, catalyst quantum yield, and hydroxyl radical scavengers. The first two take values of 0.5 M−1 s−1 and 5 × 10−4 mol·photon−1, respectively, while a fraction of TOC between 10% and 90% that changes with time was found to possess hydroxyl radical scavenger nature.

Mass transport and dynamical instabilities in a model electrocatalytic process with a preceding chemical reaction

The influence of mass transport on the occurrence of periodic current oscillations and bistability in a model electrocatalytic process with a preceding homogeneous first-order chemical reaction in the Nernst diffusion layer for different diffusion coefficients of species involved in the chemical reaction is shown. The impacts of the diffusion coefficients of electrochemically active and inactive species, as well as the preceding chemical reaction rate constants on the emergence of these dynamical instabilities are uncovered. The effect of the aforementioned parameters on frequency of oscillations is determined. The peculiarities of the system behavior at the bifurcation points are demonstrated in the Nyquist and Bode plots. For the first time, the role of diffusion coefficient of inactive species in these nonlinear processes is presented theoretically.