Kinetics of the C2H5O2+ NOxReactions:  Temperature Dependence of the Overall Rate Constant and the C2H5ONO2Branching Channel of C2H5O2+ NO

2000 ◽  
Vol 104 (24) ◽  
pp. 5758-5765 ◽  
Author(s):  
Dana L. Ranschaert ◽  
Nicholas J. Schneider ◽  
Matthew J. Elrod

2003 ◽  
Vol 107 (17) ◽  
pp. 3040-3047 ◽  
Author(s):  
Jessica M. Chow ◽  
Angela M. Miller ◽  
Matthew J. Elrod


1999 ◽  
Vol 103 (22) ◽  
pp. 4378-4384 ◽  
Author(s):  
Kurtis W. Scholtens ◽  
Benjamin M. Messer ◽  
Christopher D. Cappa ◽  
Matthew J. Elrod


1994 ◽  
Vol 59 (7) ◽  
pp. 1665-1672 ◽  
Author(s):  
Jaroslava Horáčková ◽  
Vojeslav Štěrba

Kinetics have been studied of gradual replacement of 4-methoxyphenylazo groups in 2,6-dioxo-5(3)-(4-methoxyphenylazo)-3(5)-(4-methoxyphenylhydrazono)-1,2,3,6-tetrahydropyridine-4-carboxylic acid (IIIa) by 4-nitrophenylazo groups using the reaction with 4-nitrobenzenediazonium cation (IIc) in acetate and phosphate buffers. The rate constant of replacement of the second methoxyphenylazo group is lower by a factor of ca 60. From the experimentally found pKa values of the corresponding azohydrazone compounds with methoxy, chloro, or nitro substituent at 4-position (IIIa - IIIf) it has been concluded that the 5(3)-(4-methoxyphenylazo)-3(5)-(4-nitrophenylhydrazono) derivative is formed in the first step.



1995 ◽  
Vol 73 (12) ◽  
pp. 2137-2142 ◽  
Author(s):  
A.J. Elliot ◽  
M.P. Chenier ◽  
D.C. Ouellette

In this publication we report: (i) the rate constants for reaction of the hydrated electron with 1-hexyn-3-ol ((8.6 ± 0.3) × 108 dm3 mol−1 s−1 at 18 °C), cinnamonitrile ((2.3 ± 0.2) × 1010 dm3 mol−1 s−1 at 20 °C), and 1,3-diethyl-2-thiourea ((3.5 ± 0.3) × 108 dm3 mol−1 s−1 at 22 °C). For cinnamonitrile and diethylthiourea, the temperature dependence up to 200 °C and 150 °C, respectively, is also reported; (ii) the rate constants for the reaction of the hydroxyl radical with 1-hexyn-3-ol ((5.5 ± 0.5) × 109 dm3 mol−1 s−1 at 20 °C), cinnamonitrile ((9.2 ± 0.3) × 109 dm3 mol−1 s−1 at 21 °C), and diethylthiourea ((8.0 ± 0.8) × 108 dm3 mol−1 s−1 at 22 °C). For cinnamonitrile, the temperature dependence up to 200 °C is also reported; (iii) the rate constant for the hydrogen atom reacting with 1-hexyn-3-ol ((4.3 ± 0.4) × 109 dm3 mol−1 s−1 at 20 °C). Keywords: radiolysis, corrosion inhibitors, rate constants.



Author(s):  
Zheyong Li ◽  
Yajun Yuan ◽  
Lin Ma ◽  
Yihui Zhang ◽  
Hongwei Jiang ◽  
...  

Selenium (Se) is an essential and crucial micronutrient for humans and animals, but excessive Se brings negativity and toxicity. The adsorption and oxidation of Se(IV) on Mn-oxide surfaces are important processes for understanding the geochemical fate of Se and developing engineered remediation strategies. In this study, the characterization of simultaneous adsorption, oxidation, and desorption of Se(IV) on δ-MnO2 mineral was carried out using stirred-flow reactors. About 9.5% to 25.3% of Se(IV) was oxidized to Se(VI) in the stirred-flow system in a continuous and slow process, with the kinetic rate constant k of 0.032 h−1, which was significantly higher than the apparent rate constant of 0.0014 h−1 obtained by the quasi-level kinetic fit of the batch method. The oxidation reaction was driven by proton concentration, and its rate also depended on the Se(IV) influent concentration, flow rate, and δ-MnO2 dosage. During the reaction of Se(IV) and δ-MnO2, Mn(II) was produced and adsorbed strongly on Mn oxide surfaces, which was evidenced by the total reflectance Fourier transform infrared (ATR-FTIR) results. The X-ray photoelectron spectroscopy (XPS) data indicated that the reaction of Se(VI) on δ-MnO2 produced Mn(III) as the main product. These results contribute to a deeper understanding of the interface chemical process of Se(IV) with δ-MnO2 in the environment.



2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Ajibola B. Oyedeji ◽  
Olajide P. Sobukola ◽  
Ezekiel Green ◽  
Oluwafemi A. Adebo

AbstractThe physical properties and water absorption kinetics of three varieties of Mucuna beans (Mucuna pruriens, Mucuna rajada and Mucuna veracruz) were determined in this study. Physical properties including length, width, thickness, geometric mean diameter, sphericity, porosity, bulk density, area, volume and one thousand seed mass were calculated while hydration kinetics was studied by soaking Mucuna beans in water at 30 °C, 40 °C and 50 °C and measuring water uptake at 9 h interval. Peleg’s equation was used to model the hydration characteristics and Arrhenius equation was used to describe the effect of temperature on Peleg’s rate constant k1 and to obtain the activation energies for soaking. Significant variations were observed in almost all the physical properties of the different varieties, however, there were no significant differences (p < 0.05) in their thicknesses and bulk densities. The effectiveness of fit of Peleg’s model (R2) increased with increase in soaking temperature. Peleg’s rate constant k1 decreased with increase in soaking temperature while k2 increased with temperature increase. Activation energies of Mucuna pruriens, Mucuna rajada and Mucuna veracruz were 1613.24 kJ/mol, 747.95 kJ/mol and 2743.64 kJ/mol, respectively. This study provides useful information about the properties of three varieties of Mucuna beans that could be of importance to processors and engineers for process design and optimization.



1996 ◽  
Vol 50 (11) ◽  
pp. 1352-1359 ◽  
Author(s):  
Ping Chiang ◽  
Kuang-Pang Li ◽  
Tong-Ming Hseu

An idealized model for the kinetics of benzo[ a]pyrene (BaP) metabolism is established. As observed from experimental results, the BaP transfer from microcrystals to the cell membrane is definitely a first-order process. The rate constant of this process is signified as k1. We describe the surface–midplane exchange as reversible and use rate constants k2 and k3 to describe the inward and outward diffusions, respectively. The metabolism is identified as an irreversible reaction with a rate constant k4. If k2 and k3 are assumed to be fast and not rate determining, the effect of the metabolism rate, k4, on the number density of BaP in the midplane of the microsomal membrane, m3, can be estimated. If the metabolism rate is faster than or comparable to the distribution rates, k2 and k3, the BaP concentration in the membrane midplane, m3, will quickly be dissipated. But if k4 is extremely small, m3 will reach a plateau. Under conditions when k2 and k3 also play significant roles in determining the overall rate, more complicated patterns of m3 are expected.



1969 ◽  
Vol 113 (4) ◽  
pp. 611-615 ◽  
Author(s):  
J. Leichter ◽  
M. A. Joslyn

Results are presented on the rate of thiamin cleavage by sulphite in aqueous solutions as affected by temperature (20–70°), pH(2·5–7·0), and variation of the concentration of either thiamin (1–20μm) or sulphite (10–5000μm as sulphur dioxide). Plots of the logarithm of percentage of residual thiamin against time were found to be linear and cleavage thus was first-order with respect to thiamin. At pH5 the rate was also found to be proportional to the sulphite concentration. In the pH region 2·5–7·0 at 25° the rate constant was 50m−1hr.−1 at pH5·5–6·0, and decreased at higher or lower pH values. The rate of reaction increased between 20° and 70°, indicating a heat of activation of 13·6kcal./mole.



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