Inorganic greywater matrix impact on photocatalytic oxidation: does flocculation of TiO2 nanoparticles impair process efficiency?

2011 ◽  
Vol 63 (12) ◽  
pp. 2808-2813 ◽  
Author(s):  
A. Armanious ◽  
A. Özkan ◽  
U. Sohmen ◽  
H. Gulyas
Keyword(s):  
Rate Constants ◽  
Electric Double Layer ◽  
Photocatalytic Oxidation ◽  
Process Efficiency ◽  
Point Of Zero Charge ◽  
Inorganic Salts ◽  
Co2 Absorption ◽  
Oh Radical ◽  
Radical Scavengers ◽  
Subsequent Formation

This study was conducted in order to clarify whether photocatalyst flocculation – as observed in biologically pretreated greywater – contributes to photocatalytic oxidation (PCO) efficiency impairment. Aqueous solutions of tetraethyleneglycol dimethylether spiked with different inorganic salts in concentrations as found in biologically treated greywater were investigated with respect to TiO2 flocculation and PCO mineralisation kinetics. Flocculation of the photocatalyst primarily depended on pH (which was affected by the salts) and how close pH was to the point of zero charge (PZC). Photocatalyst agglomeration was maximum at pH 5.5. With salt concentrations >7 mmol L−1, flocculation was strong even at pH far above PZC due to electric double layer compression. PCO rate constants were not unequivocally related to flocculation. Increasing pH was observed as the clearest factor deteriorating PCO efficiency. This was interpreted to result from impaired adsorbability of negatively charged oxidation intermediates as well as from enhanced CO2 absorption with increasing pH and subsequent formation of HCO3− anions which are OH radical scavengers.

OH-RADICAL SCAVENGERS AND IRON CHELATOR IMPROVE POSTHYPOXIC CELLULAR INTEGRETY IN GLYCINE-PRESERVED RENAL TUBULUES

2008 ◽  
Vol 86 (Supplement) ◽  
pp. 390-391
Author(s):  
M K. Schilling ◽  
M R. Moussavian ◽  
J E. Slotta ◽  
O Kollmar ◽  
M D. Menger
Keyword(s):  
Iron Chelator ◽  
Oh Radical ◽  
Radical Scavengers

Wavelength controlled production of SO4- radicals in the ultraviolet photolysis of ceric sulfate solutions

1984 ◽  
Vol 37 (3) ◽  
pp. 475 ◽  
Author(s):  
RW Matthews
Keyword(s):  
Rate Constants ◽  
Photochemical Reaction ◽  
Transfer Reaction ◽  
Quantum Yields ◽  
Oh Radical ◽  
Transfer Energy ◽  
Fluorescence Measurements ◽  
Sulfate Solutions ◽  
Ultraviolet Photolysis ◽  
Primary Photochemical Reaction

Solutions of cerium(III)/(IV) and formic acid in 0.4 M sulfuric acid have been photolysed under 254 nm and 365 nm light. Marked differences in the reaction kinetics and quantum yields are observed at the two different wavelengths. At 365 nm, the reactions leading to cerium(IV) reduction are caused almost exclusively by the SO4- radical. The ratio of rate constants, k(SO4- + CeIII)/ k(SO4- + HCOOH), is 116 � 11 and the quantum yield of sulfate radicals, ф(SO4-), is 0.023 � 0.002. At 254 nm, the reactions leading to cerium(IV) reduction are caused mainly by the OH radical, but approximately 35% of the oxidizing radicals formed in the primary photochemical reaction are SO4-. Cerium(III) species, excited at 254 nm, transfer energy to cerium(IV) and this results in an additional yield of OH and SO4- radicals. Fluorescence measurements confirmed the efficiency of the energy transfer reaction. The ratio of rate constants, k(OH+CeIII)/k(OH+HCOOH), is 2.22 � 0.18 and ф(CeIV*) and ф(CelIII*) giving oxidizing radicals are 0.116 � 0.010 and 0.0083 � 0.0008 respectively. Thus about 5 times more total oxidizing radicals are produced from excited cerium(IV) species at 254 nm than at 365 nm.

Reaction kinetics of OH radicals with glutaric acid and adipic acid in the aqueous phase

2021 ◽  
Author(s):  
Liang Wen ◽  
Thomas Schaefer ◽  
Hartmut Herrmann
Keyword(s):  
Aqueous Phase ◽  
Adipic Acid ◽  
Rate Constants ◽  
Density Functional ◽  
Glutaric Acid ◽  
Radical Reaction ◽  
Basis Set ◽  
Oh Radicals ◽  
Oh Radical ◽  
Energy Barriers

<p>Dicarboxylic acids (DCAs) are widely distributed in atmospheric aerosols and cloud droplets and are mainly formed by the oxidation of volatile organic compounds (VOCs). For example, glutaric acid and adipic acid are two kinds of the DCAs that can be oxidized by hydroxyl radical (‧OH) reactions in the aqueous phase of aerosols and droplets. In the present study, the temperature- and pH-dependent rate constants of the aqueous OH radical reactions of the two DCAs were investigated by a laser flash photolysis-long path absorption setup using the competition kinetics method. Based on speciation calculations, the OH radical reaction rate constants of the fully protonated (H<sub>2</sub>A), deprotonated (HA<sup>-</sup>) and fully deprotonated (A<sup>2-</sup>) forms of the two DCAs were determined. The following Arrhenius expressions for the T-dependency of the OH radical reaction of glutaric acid, k(T, H<sub>2</sub>A) = (3.9 ± 0.1) × 10<sup>10</sup> × exp[(-1270 ± 200 K)/T], k(T, HA<sup>-</sup>) = (2.3 ± 0.1) × 10<sup>11</sup> × exp[(-1660 ± 190 K)/T], k(T, A<sup>2-</sup>) = (1.4 ± 0.1) × 10<sup>11</sup> × exp[(-1400 ± 170 K)/T] and adipic acid, k(T, H<sub>2</sub>A) = (7.5 ± 0.2) × 10<sup>10</sup> × exp[(-1210 ± 170 K)/T], k(T, HA<sup>-</sup>) = (9.5 ± 0.3) × 10<sup>10</sup> × exp[(-1200 ± 200 K)/T], k(T, A<sup>2-</sup>) = (8.7 ± 0.2) × 10<sup>10</sup> × exp[(-1100 ± 170 K)/T] (in unit of L mol<sup>-1</sup> s<sup>-1</sup>) were derived.</p><p>The energy barriers of the H-atom abstractions were simulated by the Density Functional Theory calculations run with the GAUSSIAN package using the M06-2X method and the basis set m062x/6-311++g(3df,2p). The results showed that the energy barriers were lower at the C<sub>β</sub>-atoms and are higher at the C<sub>α</sub>-atoms of the two DCAs, clearly suggesting that the H-atom abstractions occurred predominately at the C<sub>β</sub>-atoms. In addition, the ionizations can enhance the electrostatic effects of the carboxyl groups, significantly reducing the energy barriers, leading to the order of OH radical reactivity as  <  < . This study intends to better characterize the losing processes of glutaric acid and adipic acid in atmospheres.</p>

UV and Solar Light Induced Natural Iron Oxide Activation: Characterization and Photocatalytic Degradation of Organic Compounds

2018 ◽  
Vol 17 (1) ◽  
Author(s):  
S. Belaidi ◽  
L. Mammeri ◽  
H. Mechakra ◽  
W. Remache ◽  
K. Benhamouda ◽  
...  
Keyword(s):  
Iron Oxide ◽  
Oxalic Acid ◽  
Photocatalytic Oxidation ◽  
Diffuse Reflectance Spectroscopy ◽  
Solar Irradiation ◽  
Point Of Zero Charge ◽  
Natural Mineral ◽  
X Ray ◽  
North East ◽  
Natural Iron

Abstract In this study we demonstrate the efficiency of a natural mineral as a photocalyst. This natural mineral was provided from the iron ore deposit from Chaabet-El-Ballout which is located in North-East of Algeria. The characterization analysis of the mineral by the Energy-dispersive X-ray spectroscopy (EDX) revealed that the natural powder has a mixed elemental composition and consist mainly of iron oxide with 50 % of iron. In order to determine the crystal phase composition of the natural iron oxide (NIO), X-ray diffraction (DRX) measurement and infrared absorption spectroscopy (FTIR) were carried out. The results showed that the NIO has a mixed crystal structure composed mainly of hematite and lesser extent of goethite. The specific surface area and the total pore volume of the NIO were 79.015 m2g−1 and 0.0892 cm3g−1 respectively, measured by the Brunauer Emmett–Teller method (BET). The Raman spectrum of the NIO confirmed that the sample has seven characteristic peaks attributable to hematite. The optical properties of soil powder were examined by UV-vis diffuse reflectance spectroscopy (DRS). The pH of point of zero charge (pHpzc) of the adsorbent was determined, a value of 8.3 was found. The photocatalytic activity of the NIO particles was tested by the decomposition of aqueous solution of different class of compounds; phenolic compounds, pesticides and dyes due to their presence in many types of wastewaters. The sorption on the surface of the NIO with photocatalytic oxidation using oxalic acid and hydrogen peroxide would be an effective oxidation process for the removal of contaminants under UV and solar irradiation. High percentages of degradation of 1- Naphtol (1-NP) and Linuron were found about, 94.6 %, 97.2 % respectively, in presence of NIO and H2O2 under UV irradiation. The presence of oxalic acid with NIO enhanced the photodegradation of 2,6-dimethylphenol (2,6-DMP), 2-chlorophenol (2-CP) and Methylene blue (MB) with 72 %, 92 % and 100 % percentages of degradation respectively.

Atmospheric oxidation mechanism of polyfluorinated sulfonamides — A quantum chemical and kinetic study

2013 ◽  
Vol 91 (6) ◽  
pp. 472-478 ◽  
Author(s):  
Xiaoyan Sun ◽  
Lei Ding ◽  
Qingzhu Zhang ◽  
Wenxing Wang
Keyword(s):  
Rate Constants ◽  
Density Functional ◽  
Single Point ◽  
Oxidation Mechanism ◽  
Basis Set ◽  
Atmospheric Oxidation ◽  
Oh Radicals ◽  
Oh Radical ◽  
Orbital Theory ◽  
Point Energy

Polyfluorinated sulfonamides (FSAs, F(CF2)nSO2NR1R2) are present in the atmosphere and may serve as the source of perfluorocarboxylates (PFCAs, CF3(CF2)nCOO–) in remote locations through long-range atmospheric transport and oxidation. Density functional theory (DFT) molecular orbital theory calculations were carried out to investigate OH radical-initiated atmospheric oxidation of a series of sulfonamides, F(CF2)nSO2NR1R2 (n = 4, 6, 8). Geometry optimizations of the reactants as well as the intermediates, transition states, and products were performed at the MPWB1K level with the 6-31G+(d,p) basis set. Single-point energy calculations were carried out at the MPWB1K/6-311+G(3df,2p) level of theory. The OH radical-initiated reaction mechanism is given and confirms that the OH addition to the sulfone double bond producing perfluoroalkanesulfonic acid directly cannot occur in the general atmosphere. Canonical variational transition-state (CVT) theory with small curvature tunneling (SCT) contribution was used to predict the rate constants. The overall rate constants were determined, k(T) (N-EtFBSA + OH) = (3.21 × 10−12) exp(–584.19/T), k(T) (N-EtFHxSA + OH) = (3.21 × 10−12) exp(–543.24/T), and k(T) (N-EtFOSA + OH) = (2.17 × 10−12) exp(–504.96/T) cm3 molecule−1 s−1, over the possible atmospheric temperature range of 180–370 K, indicating that the length of the F(CF2)n group has no large effect on the reactivity of FSAs. Results show that the atmospheric lifetime of FSAs determined by OH radicals will be 20–40 days, which agrees well with the experimental values (20–50 days), 20 thus they may contribute to the burden of perfluorinated pollution in remote regions.

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