scholarly journals Mechanistic Model and Optimization of the Diclofenac Degradation Kinetic for Ozonation Processes Intensification

Water ◽  
2021 ◽  
Vol 13 (12) ◽  
pp. 1670
Author(s):  
Bryan Acosta-Angulo ◽  
Jose Lara-Ramos ◽  
Jennyfer Diaz-Angulo ◽  
Miguel Angel Mueses ◽  
Fiderman Machuca-Martínez
Keyword(s):  
Rate Constants ◽  
Mechanistic Model ◽  
Chemical Species ◽  
Photon Absorption ◽  
Ozone Decomposition ◽  
Kinetic Regime ◽  
Degradation Kinetic ◽  
Volumetric Rate ◽  
Optimal Values ◽  
Good Agreement

This work focused on estimating the rate constants for three ozone-based processes applied in the degradation of diclofenac. The ozonation (Oz) and its intensification with catalysis (COz) and photocatalysis (PCOz) were studied. Three mathematical models were evaluated with a genetic algorithm (GA) to find the optimal values for the kinetics constants. The Theil inequality coefficient (TIC) worked as a criterion to assess the models’ deviation. The diclofenac consumption followed a slow kinetic regime according to the Hatta number (Ha<0.3). However, it strongly contrasted with earlier studies. The obtained values for the volumetric rate of photon absorption (VRPA) corresponding to the PCOz process (1.75×10−6 & 6.54×10−7 Einstein L−1 min−1) were significantly distant from the maximum (2.59×10−5 Einstein L−1 min−1). The computed profiles of chemical species proved that no significant amount of hydroxyl radicals was produced in the Oz, whereas the PCOz achieved the highest production rate. According to this, titanium dioxide significantly contributed to ozone decomposition, especially at low ozone doses. Although the models’ prediction described a good agreement with the experimental data (TIC<0.3), the optimization algorithm was likely to have masked the rate constants as they had highly deviated from already reported values.

Computational Study on the Kinetics and Mechanisms of Unimolecular Reactions of (Z)-(Z)-N-(λ5-phosphanylidene) Formohydrazonic Formic Anhydride: Intramolecular aza-Wittig Reaction in Competition with Mumm Rearrangement

2020 ◽  
Vol 17 (11) ◽  
pp. 884-889
Author(s):  
Somayeh Mirdoraghi ◽  
Hamed Douroudgari ◽  
Farideh Piri ◽  
Morteza Vahedpour
Keyword(s):  
Rate Constants ◽  
Density Functional ◽  
Wittig Reaction ◽  
Computational Study ◽  
Single Step ◽  
Low Energy ◽  
Coupled Cluster ◽  
Unimolecular Reaction ◽  
Single Step Reaction ◽  
Good Agreement

For (Z)-(Z)-N-(λ5-phosphanylidene) formohydrazonic formic anhydride, Aza-Wittig reaction and Mumm rearrangement are studied using both density functional and coupled cluster theories. For this purpose, two different products starting from one substrate are considered that are competing with each other. The obtained products, P1 and P2, are thermodynamically favorable. The product of the aza-Wittig reaction, P1, is more stable than the product of Mumm rearrangement (P2). For the mentioned products, just one reliable pathway is separately proposed based on unimolecular reaction. Therefore, the rate constants based on RRKM theory in 300-600 K temperature range are calculated. Results show that the P1 generation pathway is a suitable path due to low energy barriers than the path P2. The first path has three steps with three transition states, TS1, TS2, and TS3. The P2 production path is a single-step reaction. In CCSD level, the computed barrier energies are 14.55, 2.196, and 10.67 kcal/mol for Aza-Wittig reaction and 42.41 kcal/mol for Mumm rearrangement in comparison with the corresponding complexes or reactants. For final products, the results of the computational study are in a good agreement with experimental predictions.

scholarly journals Global earthworm distribution and activity windows based on soil hydromechanical constraints

2021 ◽  
Vol 4 (1) ◽  
Author(s):  
Siul A. Ruiz ◽  
Samuel Bickel ◽  
Dani Or
Keyword(s):  
Soil Structure ◽  
Mechanistic Model ◽  
Biophysical Model ◽  
Ecosystem Functions ◽  
Soil Conditions ◽  
Agricultural Systems ◽  
Occurrence Patterns ◽  
Additional Constraints ◽  
Earthworm Activity ◽  
Good Agreement

AbstractEarthworm activity modifies soil structure and promotes important hydrological ecosystem functions for agricultural systems. Earthworms use their flexible hydroskeleton to burrow and expand biopores. Hence, their activity is constrained by soil hydromechanical conditions that permit deformation at earthworm’s maximal hydroskeletal pressure (≈200kPa). A mechanistic biophysical model is developed here to link the biomechanical limits of earthworm burrowing with soil moisture and texture to predict soil conditions that permit bioturbation across biomes. We include additional constraints that exclude earthworm activity such as freezing temperatures, low soil pH, and high sand content to develop the first predictive global map of earthworm habitats in good agreement with observed earthworm occurrence patterns. Earthworm activity is strongly constrained by seasonal dynamics that vary across latitudes largely due to soil hydromechanical status. The mechanistic model delineates the potential for earthworm migration via connectivity of hospitable sites and highlights regions sensitive to climate.

scholarly journals Modelling and Simulation of the Radiant Field in an Annular Heterogeneous Photoreactor Using a Four-Flux Model

2018 ◽  
Vol 2018 ◽  
pp. 1-16 ◽  
Author(s):  
O. Alvarado-Rolon ◽  
R. Natividad ◽  
R. Romero ◽  
L. Hurtado ◽  
A. Ramírez-Serrano
Keyword(s):  
Photocatalytic Oxidation ◽  
Reaction Rate ◽  
Comsol Multiphysics ◽  
Discrete Ordinate Method ◽  
Discrete Ordinate ◽  
Cylindrical Coordinates ◽  
Volumetric Rate ◽  
Flux Model ◽  
Reaction Rate Equation ◽  
Good Agreement

This work focuses on modeling and simulating the absorption and scattering of radiation in a photocatalytic annular reactor. To achieve so, a model based on four fluxes (FFM) of radiation in cylindrical coordinates to describe the radiant field is assessed. This model allows calculating the local volumetric rate energy absorption (LVREA) profiles when the reaction space of the reactors is not a thin film. The obtained results were compared to radiation experimental data from other authors and with the results obtained by discrete ordinate method (DOM) carried out with the Heat Transfer Module of Comsol Multiphysics® 4.4. The FFM showed a good agreement with the results of Monte Carlo method (MC) and the six-flux model (SFM). Through this model, the LVREA is obtained, which is an important parameter to establish the reaction rate equation. In this study, the photocatalytic oxidation of benzyl alcohol to benzaldehyde was carried out, and the kinetic equation for this process was obtained. To perform the simulation, the commercial software COMSOL Multiphysics v. 4.4 was employed.

scholarly journals Probing Protein Shelf Lives from Inverse Mean First Passage Times

2019 ◽  
Author(s):  
Vishal Singh ◽  
Parbati Biswas
Keyword(s):  
Protein Aggregation ◽  
Rate Constants ◽  
Survival Probability ◽  
First Passage Time ◽  
Passage Time ◽  
First Passage ◽  
First Order Kinetics ◽  
The Mean ◽  
Passage Times ◽  
Good Agreement

Protein aggregation is investigated theoretically via protein turnover, misfolding, aggregation and degradation. The Mean First Passage Time (MFPT) of aggregation is evaluated within the framework of Chemical Master Equation (CME) and pseudo first order kinetics with appropriate boundary conditions. The rate constants of aggregation of different proteins are calculated from the inverse MFPT, which show an excellent match with the experimentally reported rate constants and those extracted from the ThT/ThS fluorescence data. Protein aggregation is found to be practically independent of the number of contacts and the critical number of misfolded contacts. The age of appearance of aggregation-related diseases is obtained from the survival probability and the MFPT results, which matches with those reported in the literature. The calculated survival probability is in good agreement with the only available clinical data for Parkinson’s disease.<br>

Generalized Mechanistic Force System Model of Ball-End Milling for Sculpture Surface Machining

2001 ◽  
Author(s):  
Ismail Lazoglu
Keyword(s):  
End Milling ◽  
Mechanistic Model ◽  
Milling Process ◽  
Force System ◽  
Workpiece Surface ◽  
Surface Machining ◽  
Ball End Milling ◽  
End Milling Process ◽  
Validation Experiments ◽  
Good Agreement

Abstract In this paper, a new mechanistic model is developed for the prediction of cutting force system in ball-end milling process. The key feature of the model includes the ability to calculate the workpiece / cutter intersection domain automatically for a given cutter location (CL) file, cutter and workpiece geometries. Moreover, an analytical approach is used to determine the instantaneous chip load and cutting forces. The model also employs a Boolean approach for given cutter, workpiece geometries, and the CL file in order to determine the surface topography and scallop height variations along the workpiece surface which can be visualized in 3-D. Some of the typical results from the model validation experiments performed on Ti-6A1-4V are also reported in the paper. Comparisons of the predicted and measured forces as well as the surface topographies show good agreement.

Electrode kinetics of Eu3+/Eu2+ reaction by cyclic voltammetry

1982 ◽  
Vol 47 (7) ◽  
pp. 1773-1779 ◽  
Author(s):  
T. P. Radhakrishnan ◽  
A. K. Sundaram
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Outer Sphere ◽  
Electrode Reaction ◽  
Transfer Reactions ◽  
Cyclic Voltammetric ◽  
Edta Solution ◽  
Kinetics Of ◽  
Activated Complex ◽  
Good Agreement

The paper is a detailed study of the cyclic voltammetric behaviour of Eu3+ at HMDE in molar solutions of KCl, KBr, KI, KSCN and in 0.1M-EDTA solution with an indigenously built equipment. The computed values of the rate constants at various scan rates show good agreement with those reported by other electrochemical methods. In addition, the results indicate participation of a bridged activated complex in the electron-transfer step, the rate constants showing the trend SCN- > I- > Br- > Cl- usually observed for bridging order of these anions in homogeneous electron-transfer reactions. The results for Eu-EDTA system, however, indicate involvement of an outer sphere activated complex in the electrode reaction.

TWO- AND THREE-PHOTON NONLINEAR ABSORPTION IN As2Se3 CHALCOGENIDE GLASS: THEORY AND EXPERIMENT

2004 ◽  
Vol 13 (01) ◽  
pp. 7-16 ◽  
Author(s):  
F. SANCHEZ ◽  
G. BOUDEBS ◽  
S. CHERUKULAPPURATH ◽  
H. LEBLOND ◽  
J. TROLES ◽  
...  
Keyword(s):  
Photon Absorption ◽  
Nonlinear Material ◽  
Closed Form Expression ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Simulation Based ◽  
Transmission Measurements ◽  
Two Photon Absorption Coefficient ◽  
Theoretical Results ◽  
Good Agreement

The absorption of a monochromatic plane wave in a medium exhibiting linear, two- and three-photon absorption is investigated theoretically. An approximate closed-form expression is derived for the optical intensity. An effective two-photon absorption coefficient is then defined. Using the theoretical results, the absorption coefficients from transmission measurements are determined. Experiment is done in a highly absorbing nonlinear material such as As 2 Se 3 to illustrate our theoretical results. Good agreement is found between experimental data and numerical simulation based on our model. Measurements of nonlinear coefficients characterizing the two- and three-photon absorption are given.

The acid-catalyzed decomposition of nitramide

1996 ◽  
Vol 74 (10) ◽  
pp. 1779-1783 ◽  
Author(s):  
Robin A. Cox
Keyword(s):  
Rate Constants ◽  
Activation Parameters ◽  
Cyclic Process ◽  
Dilute Acid ◽  
Acid Media ◽  
Dilute Acid Solution ◽  
Acid Catalyzed ◽  
Reaction With Water ◽  
Hydrochloric And Sulfuric Acids ◽  
Good Agreement

Much attention has been paid to the base-catalyzed decomposition of nitramide, but despite this it was not certain that a corresponding acid-catalyzed reaction even existed before the work described in this paper. The excess acidity method has been applied to nitramide decomposition rate constants obtained in aqueous perchloric acid media, and to a lesser extent in aqueous hydrochloric and sulfuric acids. This analysis shows that the decomposition in dilute acid solution is actually a base-catalyzed reaction, with water acting as the base (perhaps in a cyclic process involving two water molecules), with rate constants in good agreement with previous estimates. However, in more concentrated acid media a true acid-catalyzed reaction can be dissected out. Activation parameters are given for both mechanisms, and it is shown that the acid-catalyzed process is similar to the acid-catalyzed decomposition of alkylnitramines. In sulfuric acid the reaction is slightly faster than it is in the other acids, due to the presence of a base-catalyzed process involving sulfate. Key words: nitramide, excess acidity, acid-catalyzed, base-catalyzed, kinetics.

Mechanism of bromination of a quaternary pyrimidinium cation. Change of rate determining step with acidity

1978 ◽  
Vol 56 (23) ◽  
pp. 2970-2976 ◽  
Author(s):  
Oswald S. Tee ◽  
David C. Thackray ◽  
Charles G. Berks
Keyword(s):  
Kinetic Study ◽  
Rate Constants ◽  
Aqueous Media ◽  
Stopped Flow ◽  
Flow Method ◽  
High Acidity ◽  
Rate Determining Step ◽  
Kinetics Of ◽  
Good Agreement

The kinetics of bromination of the 1,2-dihydro-1,3-dimethyl-2-oxopyrimidinium cation (Q+) in aqueous media (pH 0–5) have been studied using the stopped-flow method. At the higher acidities (pH < 2) the results are consistent with rate determining attack by bromine upon the pseudobase (QOH), whereas at low acidities (pH > 4) it appears that pseudobase formation is rate determining. The change occurs because at high acidity the reversal of the pseudobase QOH to the cation is fast relative to bromine attack, whereas at low acidity the converse is true. Results obtained at intermediate acidities (pH 2–4) are consistent with this interpretation.A separate kinetic study of pseudobase formation (and decomposition) yielded rate constants in good agreement with those derived from the bromination study.

Monitoring of Chemical Speciation of DEA – CO2 – Water System by Raman Spectroscopy

2015 ◽  
Vol 1113 ◽  
pp. 358-363 ◽  
Author(s):  
Muhammad Zubair Shahid ◽  
Humbul Suleman ◽  
Adulhalim Shah Maulud ◽  
Mohammad Azmi Bustam Khalil ◽  
Zakaria Man
Keyword(s):  
Raman Spectroscopy ◽  
Water System ◽  
Chemical Species ◽  
Principal Component Regression ◽  
Principal Component ◽  
Carbon Dioxide Separation ◽  
Key Factor ◽  
Kinetics Of ◽  
Respective Characteristic ◽  
Good Agreement

Carbon dioxide separation has gained immense importance since its detrimental effects towards our environment has been realized. Commercially, CO2has been captured by absorption in alkanolamines such as diethanolamine (DEA), since many years. The thermodynamics and kinetics of the process is a key factor towards its efficiency and significantly depends on its qualitative and quantitative speciation. In this work, the analysis of speciation for CO2loaded aqueous DEA has been performed by Raman spectroscopy. Experimentally determined CO2loading data and modified Kent Eisenberg equation was used to quantify the chemical species present. The speciation results were fitted with the respective characteristic Raman peaks of (CO3-, HCO3-, DEACOO-, DEA, DEA+, CO2) by Principal Component Regression (PCR). The fitted results showed good agreement with thermodynamically predicted chemical species.

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