Kinetics of ozone reactions with 1-naphthalene, 1,5-naphthalene and 3-nitrobenzene sulphonic acids in aqueous solutions

2001 ◽  
Vol 44 (5) ◽  
pp. 7-13 ◽  
Author(s):  
V. Calderara ◽  
M. Jekel ◽  
C. Zaror

This paper describes the ozone oxidation kinetics of 1-naphthalene (1NS), 1,5-naphthalene (1,5NDS), and 3-nitrobenzene (3NBS) sulphonic acid. The presence of hydroxyl radicals and their effect on the overall rate of reaction was studied. Second order kinetic constants of direct reactions were estimated at around 252 M-1s-1, 41 M-1s-1 and 22 M-1s-1, for 1NS, 1,5NDS, and 3NBS sulphonic acids, respectively. At pH 3, the indirect reaction accounted for 2%, 15% and 4% of total primary oxidation of 1NS, 1,5NBS, and 3NBS sulphonic acids, respectively. At pH 9, indirect reaction contribution increased to 73%, 84% and 48%, respectively. C4 compounds (maleic and fumaric acids), C2 (oxalic), C1 (formic) and sulphate were identified as oxidation by-products in all cases. TOC slowly decreased throughout ozonation, reaching around 40-60% and 60-70% reduction over 90 minutes at pH 7 and 3, respectively.

Author(s):  
Aigul A. Maksyutova ◽  
Elvina R. Khaynasova ◽  
Yuriy S. Zimin

The ultraviolet spectroscopy method has been applied to study the kinetics of the ozone reactions with nitrogenous bases (NB), namely adenine and cytosine in aqueous solutions. At the first research stage, the range of NB working concentrations has been determined. It was found that linear dependences between optical densities and concentrations of nitrogenous bases aqueous solutions are quite reliable, with correlation coefficients r ≥ 0.998, are satisfied up to [NB] = 2.3 ∙ 10–4 mol/l. According to the Bouguer-Lambert-Beer law, adenine and cytosine extinction coefficients in aqueous solutions were determined and subsequently used to calculate their residual concentrations. At the next stage, the kinetics of nitrogenous bases ozonized oxidation was studied with equal initial concentrations of the starting substances ([NB]0 = [О3]0). The results revealed that the kinetic consumption curves of the starting reagents are fairly well linearized (r ≥ 0.996) in the second-order reaction equation coordinates. As found with the bubbling installation, 1 mol of the absorbed ozone falls on 1 mol of the used NB. Thus, the reactions of ozone with adenine and cytosine explicitly proceed according to the second-order kinetic laws (the first – according to О3 and the first – according to NB). The rate constants were calculated by the integral reaction equations, the values of which indicate a higher ozone reactivity in relation to nitrogen bases. The temperature dependences of the second-order rate constants was studied ranging 285-309 K, and the activation parameters (pre-exponential factors and activation energies) of the ozone reactions with adenine and cytosine in aqueous solutions were determined.


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.


2012 ◽  
Vol 65 (12) ◽  
pp. 2175-2182
Author(s):  
Abeer S. Elsherbiny ◽  
Sahar H. El-Khalafy ◽  
Michael P. Doyle

The kinetics of the oxidative degradation of an azo dye Metanil Yellow (MY) was investigated in aqueous solution using dirhodium(II) caprolactamate, Rh2(cap)4, as a catalyst in the presence of H2O2 as oxidizing agent. The reaction process was followed by UV/Vis spectrophotometer. The decolorization and degradation kinetics were investigated and both followed a pseudo-first-order kinetic with respect to the [MY]. The effects of various parameters such as H2O2 and dye concentrations, the amount of catalyst and temperature have been studied. The studies show that Rh2(cap)4 is a very effective catalyst for the formation of hydroxyl radicals HO• which oxidized and degraded about 92% of MY into CO2 and H2O after 24 h as measured by total carbon analyzer.


2021 ◽  
Vol 11 (21) ◽  
pp. 10142
Author(s):  
Małgorzata Matusiak ◽  
Sławomir Kadłubowski ◽  
Piotr Ulański

Carbon-centered radicals have been randomly generated on the chains of poly(acrylic acid), PAA, the simplest synthetic anionic polyelectrolyte, by pulse-irradiating its dilute, oxygen-free aqueous solutions by 6 MeV electron beam. In some experiments, oligo(acrylic acid), OAA, and propionic acid, PA, were used as PAA models. Recombination kinetics of PAA radicals has been followed by fast spectrophotometry. A strong pH dependence of radical lifetime on pH, and thus on the linear charge density due to deprotonated carboxylate groups, has been confirmed, while a weaker amplitude of pH dependence was observed for OAA and PA. Decay kinetics of PAA radicals in the protonated state, at pH 2, have been studied in some detail. At moderate doses of ionizing radiation, resulting in a moderate average initial number of radicals per chain, ZR0, the decay can be satisfactorily described by a second-order kinetic model, but a somewhat better fit is obtained by using a dispersive kinetics approach. While for a constant polymer concentration the reciprocal half-lives are proportional to the initial radical concentrations, such a data series for different PAA concentrations do not overlap, indicating that the overall radical concentration is not the decisive factor controlling the kinetics. Arranging all data, in the form of second-order rate constants, as a function of the average initial number of radicals per chain allows one to obtain a common dependence. The latter seems to consist of two parts: a horizontal one at low ZR0 and another one of positive slope at higher ZR0. This is interpreted as two kinetic regimes where two distinct reactions dominate, intermolecular and intramolecular recombination, respectively. Comparison of the low ZR0 data with calculations based on the translational diffusion model indicate that the latter is not the rate-controlling process in intermolecular recombination of polymer radicals; segmental diffusion is the more likely candidate.


Author(s):  
Chen-Yan Hu ◽  
Si-Cheng Ren ◽  
Yi-Li Lin ◽  
Ji-Chen Zhang ◽  
Ye-Ye Zhu ◽  
...  

Abstract In this study, we studied the degradation kinetics of a common iodine contrast agent, diatrizoate, by ozone and the formation of disinfection by-products (DBPs) in the sequential chlorination. Effects of ozone concentration, solution pH, and bromide concentration on diatrizoate degradation were evaluated. The results indicate that diatrizoate can be effectively degraded (over 80% within 1 h) by ozone, and the degradation kinetics can be well described using the pseudo-first-order kinetic model. The pseudo-first-order rate constant (kobs) of diatrizoate degradation significantly increased with increasing ozone concentration and decreasing bromide concentration. The kobs kept increasing with the increase of pH value and reached a maximum of 6.5 (±0.05) × 10−2 min−1 at pH 9. As the ozone concentration gradually increased from 0.342 to 1.316 mg/L, the corresponding kobs of diatrizoate degradation increased from 1.76 (±0.20) × 10−3 to 4.22 (±0.3) × 10−2 min−1. The bromide concentration exhibited a strong inhibitory effect on diatrizoate degradation because of the competition for ozone with diatrizoate. Trichloromethane was the only detected DBP in the subsequent chlorination in the absence of bromide. However, in the presence of bromide, six other DBPs were detected, and bromochloroiodomethane and tribromomethane became the major products with concentrations 1–2 orders higher than those of the other DBPs. In order to provide safe drinking water to the public, water should be maintained at circumneutral pH values and low bromine concentrations (<5 μM) before reaching the chlorine disinfection process to effectively control the formation of DBPs.


2012 ◽  
Vol 441 ◽  
pp. 598-602 ◽  
Author(s):  
Bo Yu ◽  
Zai Sheng Cai ◽  
Wei Ming Wang ◽  
Chun Chun Lu

The photocatalyst of Ag doped TiO2 in liquid state was applied to decolorize the Reactive Red 3BS under UV irradiation. The rate of photocatalytic degradation of the dye was improved with increasing the concentration of catalyst from 1 g/L to 8 g/L. But as a result of light attenuation for the rising catalyst concentration, the rate of reaction was constant at 8-12 g/L of the catalyst concentration. The rate of dye photocatalytic degradation decreased with increasing initial concentration of dye. The kinetics of photocatalytic reaction was also studied. The results showed that degradation reaction is congruent with an apparent first-order kinetic equation, and the relationship between apparent reaction rate and initial dye concentration fits approximately a negative second-order kinetic relationship.


2013 ◽  
Vol 78 (6) ◽  
pp. 897-905 ◽  
Author(s):  
Shweta Sharma ◽  
Rakshit Ameta ◽  
R.K. Malkani ◽  
Suresh Ameta

Various semiconductors have been used as photocatalysts for removal of different dyes from their aqueous solutions. Zinc sulphide semiconductor is used in the present investigation as a photocatalyst for the removal of rose Bengal dye. Effect of different parameters, which affect the rate of reaction; like pH, concentration of dye, amount of semiconductor and light intensity have been studied. A mechanism has also been proposed in which hydroxyl radicals are shown as an active oxidizing species.


2020 ◽  
Author(s):  
Camilo A. Mesa ◽  
Ludmilla Steier ◽  
Benjamin Moss ◽  
Laia Francàs ◽  
James E. Thorne ◽  
...  

<p><i>Operando</i> spectroelectrochemical analysis is used to determine the water oxidation reaction kinetics for hematite photoanodes prepared using four different synthetic procedures. Whilst these photoanodes exhibit very different current / voltage performance, their underlying water oxidation kinetics are found to be almost invariant. Lower photoanode performance was found to correlate with the observation of optical signals indicative of charge accumulation in mid-gap oxygen vacancy states, indicating these states do not contribute directly to water oxidation.</p>


2018 ◽  
Vol 69 (9) ◽  
pp. 2323-2330 ◽  
Author(s):  
Daniela C. Culita ◽  
Claudia Maria Simonescu ◽  
Rodica Elena Patescu ◽  
Nicolae Stanica

A series of three chitosan-based magnetic composites was prepared through a simple coprecipitation method. It was investigated the influence of mass ratio between chitosan and magnetite on the physical and chemical properties of the composites in order to establish the optimum conditions for obtaining a composite with good adsorption capacity for Pb(II) and Cu(II) from mono and bicomponent aqueous solutions. It was found that the microspheres prepared using mass ratio chitosan / magnetite 1.25/1, having a saturation magnetization of 15 emu g--1, are the best to be used as adsorbent for the metal ions. The influence of different parameters such as initial pH values, contact time, initial concentration of metal ions, on the adsorption of Pb(II) and Cu(II) onto the chitosan-based magnetic adsorbent was investigated in details. The adsorption process fits the pseudo-second-order kinetic model in both mono and bicomponent systems, and the maximum adsorption capacities calculated on the basis of the Langmuir model were 79.4 mg g--1 for Pb(II) and 48.5 mg g--1 for Cu(II) in monocomponent systems, while in bicomponent systems were 88.3 and 49.5 mg g--1, respectively. The results revealed that the as prepared chitosan-based magnetic adsorbent can be an effective and promising adsorbent for Pb(II) and Cu(II) from mono and bicomponent aqueous solutions.


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