Kinetic Modeling of Ozone Generation via Dielectric Barrier Discharges

A mathematical model combining chemical kinetic and reactor geometry is developed for ozone synthesis in dry O₂ streams with a wire-tube dielectric barrier discharge (DBD) reactor. Good agreement is found between the predicted ozone concentrations and experimental data. Sensitivity analysis is conducted to elucidate the relative importance of individual reactions. Results indicate that the ground-state oxygen atom is the most important species for O₃ generation; however, ozone generation will be inhibited if the O atom is overdosed. The excited species, that is, O(¹ D) and O₂(b ¹Σ), can decompose O₃ and suppress ozone synthesis. The model developed is then applied to modify the original DBD reactor design for the enhancement of ozone yield. With a thinner dielectric thickness, more than 10% increase of ozone concentration is achieved.     

Energy conversion and temperature dependence in ozone generator fed by synthetic air

A homogenous chemical kinetic model consisting of 21 species and 118 reactions is applied to investigate energy conversion and its temperature dependence in ozone generator fed by synthetic air. The portion of electric energy converted into reaction heat, gas heating and heat loss to surroundings (by convection) in terms of the total electric energy input, the conversion ratios η_reaction, η_gas, and η_loss, are obtained. The detailed reaction pathway including the degree of transformation among species for ozone production is also obtained via simulation of the reaction kinetics. In addition, sensitivity analysis and rate-of-production analysis for the three foremost species O₃, O, and N₂(A) are performed to understand quantitatively the temperature dependence of sensitivity coefficient and production rate for each individual reaction. η_reaction shows a steep rise at low specific energy, but then suffers a gradual decrease at high specific energy. η_loss has a contrary behavior. And η_gas increases steadily with the increase of specific energy. The η_reaction peak of 35.1% is achieved at specific energy of 0.17 J/cm³ at the conditions under investigation. Additionally, inlet gas temperature only has a small effect on energy conversion. Moreover, high gas temperature in discharge gap is confirmed to be not favorable for ozone formation from the view of reaction heat. The sensitivity coefficients of reactions with electron participation are sensitive to gas temperature. O+O₂+O₂→O₂+O₃ and O+O₂+N₂→N₂+O₃ account for about 70% and 30% of generated ozone respectively at the given conditions. And e+O₂→e+O+O, N₂(A)+O₂→N₂O+O, and N₂(A)+O₂→O+O+N₂ are responsible for about 51.3%, 14.7%, and 32.0% of oxygen atom, respectively.     

Energy Conversion and Temperature Dependence in Ozone Generator Using Pulsed Discharge in Oxygen

A detailed reaction kinetic model consisting of 10 species and 63 reactions is developed to investigate the energy conversion and temperature dependence in an ozone generator using oxygen pulsed discharge. The energy conversion ratios of total electric energy converted into reaction heat, heat carried by gas and heat loss to ambient, namely η_reaction, η_gas and η_loss, are obtained for the first time. The ratio of reaction heat η_reaction decreases substantially with increasing specific energy and inlet gas temperature, which represents how much energy is utilized effectively to synthesize ozone. Correspondingly, η_loss and η_gas increase gradually. η_reaction declines from 55.4% to 27.7% at inlet gas temperature of 298 K when specific energy changes from 0.06 J/cm³ to 0.78 J/cm³. The detailed reaction pathway including the degree of transformation among species for ozone formation is also obtained via kinetics simulation. Meanwhile, sensitivity analysis and rate-of-production analysis for the four most important species O₃, O, O(1D) and O₂(b¹∑) obtained from the reaction pathway are executed to understand quantitatively the temperature dependence of sensitivity coefficient and production rate for each individual reaction. The production rate of ozone via the most important ozone generation reaction O+O₂+O₂ = > O₃+O₂ increases linearly with the increase of gas temperature, as well as the destruction rates of ozone via the most important ozone decomposition reactions O₃+O₃ = > O₂+O₂+O₂ and O₃ + O = > O₂(b¹∑)+O₂.     

Reaction of Ozone with Ag(I)—Mechanistic Considerations

Ozone reacts slowly with Ag⁺ (circumneutral pH, k = (11 ± 3) × 10^?2 M^?1 s^?1). After some time, ozone decay kinetics may suddenly become faster with the concomitant formation of silver sol. As primary process, an O-transfer from O₃ to Ag(I) is suggested, whereby Ag(III) is formed [Ag⁺ + O₃ + 2 H₂O → Ag(OH)₃ + O₂ + H⁺]. This conproportionates with Ag(I), which is in large excess, leading to Ag(II) [Ag⁺ + Ag(OH)₃ ? 2 Ag(OH)⁺ + HO^?]. Further, Ag(II) reacts with ozone in a high exergonic reaction [Ag(OH)⁺ + O₃ → Ag + 2 O₂ + H⁺], where ozone acts as a reducing agent. Thereby, a single silver atom, Ag, is formed that can be oxidized by O₂ and O₃ or can aggregate to a silver sol. Aggregation slows down the rate of oxidation. When Ag⁺ is complexed by acetate ions, ozone decay and silver sol formation are speeded up by enhancing Ag(II) formation [Ag(I)acetate + O₃ → Ag(III)acetate → Ag(II) + CO₂ + ?CH₃]. In the presence of oxalate, the formed complex reacts faster with ozone than Ag⁺, and Ag(III)oxalate decarboxylates rapidly [Ag(I)oxalate + O₃ → Ag(III)oxalate → Ag⁺ + 2 CO₂]. This enhances ozone decay but prevents silver sol formation. Quantum chemical calculations have been carried out for substantiating mechanistic suggestions.     

Ozone and chlorine dioxide: Similar chemistry and measurement issues

The chemical reactions associated with ozone and chlorine dioxide can be complicated and involve numerous intermediates. When ozone is applied, the presence of reactive intermediate species (O₂ ^‐, O₃ ^‐, OH, HO₂, HO₂ ^‐, and H₂O₂) influence the extent of oxidation that takes place and determines the amount and types of by‐products formed. Similarly, when chlorine dioxide is applied the amount of intermediate (Cl₂O₂) formed determines whether chlorine dioxide producing reactions or chlorate ion forming reactions occur. Ozone and chlorine dioxide are excellent agents for inactivating Cryptosporidium and Giardia. Microbiologically, each of the agents are very reactive. In the case of ozone, typically each molecule undergoes a one‐electron change. The mechanism of chlorine dioxide inactivation involves a recycling process whereby chlorine dioxide is reduced to chlorite ion followed by the “regeneration” of chlorine dioxide that continues to react within the cell over and over again. Chlorite ion also has oxidizing power and in some cases, is a biocide. When ozone and chlorine dioxide are used in combination, it is important that the chlorine dioxide application follow the ozone treatment to prevent the formation of unwanted by‐products such as ClO₃ ^‐.     

The Reaction of Ozone with Bisulfide (HS−) in Aqueous Solution – Mechanistic Aspects

The ozone demand to oxidize HS^?/H₂S [pK_a(H₂S) = 6.9, k(HS^? + O₃) = 3 × 10⁹ M^?1 s^?1, k(H₂S + O₃) = 3 × 10⁴ M^?1 s^?1] to SO₄ ^2? is only 2.4 mol ozone per mol SO₄ ^2? formed, much lower than stoichiometric 4.0 mol/mol if a series of O-transfer reactions would occur. As primary step, the formation of an ozone adduct to HS^?, HSOOO^–, is suggested that decomposes into HSO^– and singlet oxygen (16%) or rearranges into peroxysulfinate ion, HS(O)OO^– (84%). Potential reactions of the above intermediates are discussed. Some of these can account for the low ozone demand.     

Experimental Study of Ozone Generation by Negative Corona Discharge in Mixtures of N2 and O2

Ozone generation by negative DC corona discharge in N₂-O₂ mixtures has been experimentally investigated using a coaxial wire-cylinder corona reactor operating at room temperature and atmospheric pressure. The experiments have been carried out under different gas flows (15 cm³ min^?1 to 200 cm³ min^?1) and gas compositions (5% to 90% of O₂), and the effect of these parameters on the corona current, the ozone density and the efficiency of the ozone generator have been analyzed. The global rate coefficients for ozone formation and destruction have also been evaluated, and their values compared with those reported by other authors. The maximum efficiency for ozone production was found in gas mixtures with oxygen content about 70–80%.     

First‐Principle Calculation and Assignment for Vibrational Spectra of Ba(Mg1/2W1/2)O3 Microwave Dielectric Ceramic

Ba(Mg_1/2W_1/2)O₃ ceramic was synthesized using a conventional solid‐state reaction method at 1500°C for 4 h. The face‐centered cubic crystal structure of the material was confirmed by Rietveld refinement of X‐ray diffraction (XRD) data, and vibrational modes were obtained by Raman and Fourier transform far‐infrared (FTIR) reflection spectroscopies. First‐principle calculations based on density functional theory with local density approximation were used to calculate Gamma‐point modes and dielectric properties of Ba(Mg_1/2W_1/2)O₃. The Raman spectrum with nine active modes can be fitted with Lorentzian function, and the modes were assigned as F_2g⁽¹⁾ (126 cm^?1), F_2g⁽²⁾ (441 cm^?1), E_g(O) (538 cm^?1), and A_1g(O) (812 cm^?1). Far‐infrared spectrum with 12 infrared active modes was fitted using both the Lorenz three‐parameter classical and four‐parameter semiquantum models. Consequently, the modes were assigned as F_1u⁽¹⁾ (144 cm^?1), F_1u⁽²⁾ (284 cm^?1), F_1u⁽³⁾ (330–468 cm^?1), and F_1u⁽⁴⁾ (593–678 cm^?1). The active modes were represented by linear combinations of symmetry coordinates that were obtained by group theory analyses. The Raman mode A_1g, which has the highest wave number (812 cm^?1) is dominated by the breath vibration of the MgO₆ octahedron. The infrared modes F_1u⁽²⁾, that can be described as the inverted vibrations of Mg atoms in the MgO₆ octahedron along the x_i, y_i, and z_i axes have the most contributions to the microwave permittivity and dielectric loss.     

Heterogeneous Catalytic Ozonation of Refinery Wastewater over Alumina-Supported Mn and Cu Oxides Catalyst

An economical method was proposed to develop an efficient alumina-supported manganese (Mn) and copper (Cu) oxides (Mn-Cu-O/Al₂O₃) catalyst with a high surface area, 184.06 cm² g^?1. The catalyst was utilized for degradation refinery wastewater by heterogeneous catalytic ozonation. The effects of various operating variables including pH, ozone and catalyst dosages, and temperature were systematically investigated in detail to obtain the optimized conditions for accelerated degradation of refinery wastewater. The optimum values were as follows: ozone dose 50.0 mg L^?1, catalyst dose 3.0 g L^?1, initial pH = 6.8, T = 17 °C. Refinery wastewater samples were analyzed by chemical oxygen demand (COD) and the results indicated that kinetics of COD followed a pseudo–first-order degradation. Moreover, hydroxyl radical mechanism rather than absorption was proposed, indicating that the surface hydroxyl groups were the active sites that played a significant role in catalytic ozonation.     

Kinetic Study of Ozone Decay in Homogeneous Phosphate-Buffered Medium

The ozone decomposition reaction is analyzed in a homogeneous reactor through in-situ measurement of the ozone depletion. The experiments were carried out at pHs between 1 to 11 in H₂PO₄^?/HPO₄^2– buffers at constant ionic strength (0.1 M) and between 5 and 35 °C. A kinetic model for ozone decomposition is proposed considering the existence of two chemical subsystems, one accounting for direct ozone decomposition leading to hydrogen peroxide and the second one accounting for the reaction between the hydrogen peroxide with the ozone to give different radical species. The model explains the apparent reaction order respect of the ozone for the entire pH interval. The decomposition kinetics at pH 4.5, 6.1, and 9.0 is analyzed at different ionic strength and the results suggest that the phosphate ions do not act as a hydroxyl radical scavenger in the ozone decomposition mechanism.     

The Reactions of Bromide with Ozone Towards Bromate and the Hypobromite Puzzle: A Density Functional Theory Study

Taking the solvent water into account, the energetics of the reactions of O₃ with Br^? leading to BrO₃ ^? have been calculated by Density Functional Theory at the B3LYP/6–311+G(d)/SCRF =COSMO level. Br^? reversibly forms an adduct, BrOOO^?, (ΔG?=?+6 kJ mol^?1) that decays spin allowed into BrO^? and O₂(¹Δ_g) (ΔG?=?+13 kJ mol^?1). BrO^? undergoes an oxidation to BrO₂ ^? and a reduction to Br^?. This may be accounted for if two different adducts, OBrOOO^? and BrOOOO^?, decay into BrO^? plus O₂ and Br^? plus 2 O₂. After cyclization, OBrOOO^? may also lead to Br^? plus 2 O₂.     

Effects of Ozone-Gas Bubble Size and pH on Ozone/UV Treatment

A series of ozone/UV treatment under injection of ozone with different ozone-gas bubble sizes was performed at pH 1.7 and 7.4. The increase in the bubble size and the decrease in pH enhanced the ozone utilization efficiency. The enhancement of ozone utilization efficiency was caused by the shift of the production pathway of hydroxyl radical (OH) from the OH production via O₃ ^– to the UV photolysis of H₂O₂. The lower pH caused this shift through the chemical equilibrium of H₂O₂ and HO₂ ^–, and the large bubbles caused this shift through the augmentation of H₂O₂ transport from the bubble surface to the bulk solution.     

Determination of Rate Constants for Ozonation of Ofloxacin in Aqueous Solution

The ozonation of the quinolone antibiotic ofloxacin in water has been investigated with focus on kinetic parameters determination. The apparent stoichiometric factor and the second-order rate constants of the reactions of ozone and hydroxyl radical with ofloxacin were determined at 20 °C in the pH range of 4–9. The apparent stoichiometric factor was found to be about 2.5 mol O₃/mol ofloxacin regardless of the pH. The rate constant of the reaction between ozone and ofloxacin was determined by a competitive method (pH = 6–9) and a direct ozonation method (pH = 4). It was found that this rate constant increases with pH due to the dissociation of ofloxacin in water. The direct rate constants of ofloxacin species were determined to be 1.0?×?10², 4.3?×?10⁴ and 3.7?×?10⁷ for cationic, neutral-zwitterion and anionic species, respectively. Accordingly, the attack of ozone to ofloxacin mainly takes place at the tertiary amine group of the piperazine ring, though some reactivity is also due to the quinolone structure and oxazine substituent. The rate constant of the reaction between ofloxacin and hydroxyl radical was obtained from UV/H₂O₂ photodegradation experiments. It was found that this rate constant varies with pH from 3.2?×?10⁹ at pH 4 to 5.1?×?10⁹ at pH 9.     

Sorption of Pb(II), Cd(II), and Ni(II) From Single- and Multimetal Solutions by Recycled Waste Porous Glass

Selective sorption of lead, cadmium, and nickel ions on recycled waste porous glass beads was investigated. Single-metal equilibrations were carried out in demineralized water and ternary metal equilibrations were carried out in demi- and tap water. Freundlich isotherm gave a good correlation of the experimental data. Maximum metal retention (q_max) in single-ion solutions were 18.66 mg/g_RPWG (0.090 mmol/g_RPWG), 4.83 mg/g_RPWG (0.043 mmol/g_RPWG), 4.00 mg/g_RPWG (0.068 mmol/g_RPWG), respectively, for Pb⁺², Cd⁺², and Ni⁺², and lower figures were in the case of ternary systems: 13.50 mg/g_RPWG(0.065 mmol/g_RPWG), 2.23 (0.020 mmol/g_RPWG), 2.05 mg/g_RPWG(0.034 mmol/g_RPWG), respectively, for Pb⁺², Cd⁺², and Ni⁺², with further drastic reduction in tap water. Metal exhausted beads were used as thermal insulators in cement mortars, minimizing their potential impact in the environment.     

Ozonation as a Pre-treatment for Anaerobic Digestion of Waste-Activated Sludge: Effect of the Ozone Doses

The aim of the present study was to improve the anaerobic biodegradability of waste-activated sludge by using ozonation. The effect of different ozone doses was assessed in terms of biogas production, maximum biogas production rate, and concentration of amino acids and long-chain fatty acids in the waste-activated sludge. Four different doses were used: 0.043 gO₃ g_TSS^?1, 0.063 gO₃ g_TSS^?1, 0.080 gO₃ g_TSS^?1, and 0.100 gO₃ g_TSS^?1. The lower doses resulted in biogas production increases and a higher maximum biogas production rate in the anaerobic digestion of waste-activated sludge, while the contrary occurred at higher doses. The amino acids and long-chain fatty acids concentrations decreased when the ozone dose increased. The correlation with the ozone dose was nonlinear for amino acids and linear for long-chain fatty acids. The reaction products of long-chain fatty acids (aldehydes) are proposed as the cause of inhibition observed in the anaerobic digestion of waste-activated sludge treated with higher ozone doses.     

Bactericidal Effectiveness of O3, O3/H2O2 and O3/TiO2 on Clostridium perfringens

The purpose of this research is to evaluate the bactericidal capacity of different Advanced Oxidation Treatments (AOTs) based on ozone: ozone, ozone/hydrogen peroxide and ozone/titanium dioxide on a wild strain of Clostridium perfringens, a fecal bacterial indicator in drinking water. The dose of ozone consumed ranges from 0.6 mg L^?1 min^?1 to 5.13 mg L^?1 min^?1 depending on the process and on the sample. In the treatments combined with O₃, H₂O₂ dose utilized is 0.04 mM and TiO₂ dose, 1 g L^?1. In order to evaluate the influence of natural organic matter and suspension solids over the disinfection rate, treatments are performed with two types of water – natural water from Ebro River (Zaragoza, Spain) and NaCl solution 0.9%. To achieve 4 log units of inactivation, 3.6 mg O₃ L^?1 is necessary in O₃ treatment, 4.25 mg O₃ L^?1 in O₃/TiO₂ system and 2.7 mg O₃ L^?1 in O₃/H₂O₂ after processing the natural water. In NaCl solution, to get the same inactivation, 0.42 mg O₃ L^?1 is necessary in O₃ treatment, 1.15 mg O₃ L^?1 in O₃/TiO₂ system and 0.06 mg O₃ L^?1 in O₃/H₂O₂ process. Even though the three treatments studied have a high bactericidal activity due to the number of surviving bacteria decreases to non-detectable levels, O₃/H₂O₂ is the most effective system for eliminating C. perfringens cells in a lower contact time, followed by O₃ and finally O₃/TiO₂ system.     

Effect of Chemical Reaction and Mass Transfer on Ozonation of the Azo Dyes Reactive Black 5 and Reactive Orange 96

Ozonation of wastewater containing azo dye has been studied to evaluate the enhancement of ozone mass transfer from O₂O₃ gas into water with the presence of chemical reactions in a bubble column reactor. Experiments were performed at different initial dye concentrations and at various gas flow rates. C.I. Reactive Black 5 (RB 5) and C.I. Reactive Orange 96 (RO 96) have been chosen as representative model substances being found in wastewater from textile-finishing wastewater. Results show that the rate of ozone mass transfer increases with increasing initial dye concentration and gas flow rate. Consequently, an enhancement factor E for ozone mass transfer with chemical reaction could be calculated which increases with dye concentration. The chemical reaction between ozone and dye enhanced the mass transfer within the liquid film of the gas liquid boundary. The greatest enhancement factor for wastewater containing RO 96 of 2050 mgL^?1 is E = 15.4 compared with E = 9.1 for RB 5 of 3800 mgL^?1, both for gas flow rates of 19 Lh^?1. For lower gas flow rates, higher enhancement factors were observed, particularly for RO 96.     

Hydrothermal and soft-templating synthesis of mesoporous NiCo2O4 nanomaterials for high-performance electrochemical capacitors

Mesoporous nickel cobaltite (NiCo₂O₄) nanoparticles were synthesized via a hydrothermal and soft-templating method through quasi-reverse-micelle mechanism. The physicochemical properties of the NiCo₂O₄ materials were characterized via X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectra, and nitrogen sorption isotherms measurements. The electrochemical performances of the NiCo₂O₄ electrode were investigated by cyclic voltammetry, chronopotentiometry, and electrochemical impedance spectroscopy tests. The obtained NiCo₂O₄ materials exhibit typical mesoporous structures, with an average particle size of about 200 nm, a specific surface area of 88.63 m² g^?1, and a total pore volume of 0.337 cm³ g^?1. The facile electrolytes penetration for the mesoporous structures favors high-performance of the NiCo₂O₄ electrode. The NiCo₂O₄ electrode shows a high specific capacitance (591 F g^?1 at 1 A g^?1), high-rate capability (248 F g^?1 at 20 A g^?1), and a good cycling behavior for tested 3,000 cycles, indicating a promising application for electrochemical capacitors.     

Ozone-Based Processes Applied to Municipal Secondary Effluents

This study analyzes the performances of 2 methods of oxidation based on ozone, namely ozonation and ozone combined with hydrogen peroxide (O₃/H₂O₂), on two biotreated municipal wastewater effluents. The main parameters monitored to evaluate the effectiveness of the processes were Chemical Oxygen Demand (COD), Dissolved Organic Carbon (DOC) and Biochemical Oxygen Demand (BOD₅). Ozonation and O₃/H₂O₂ treatment removed 44% and 48%, respectively, of the COD, after 90 min, of the secondary effluent of Calafell wastewater treatment plant (Spain). On the secondary effluent from the Grasse wastewater treatment plant (France), these same treatments (O₃; O₃/H₂O₂) achieved, respectively, a degradation of 52% and 100% of the COD after 60 min. The transferred ozone dose (TOD) during Calafell and Grasse effluents' ozonation were 122 mg·L^?1 and 77 mg·L^?1 after 90 min, respectively. A low removal of DOC was monitored during both O₃ or O₃/H₂O₂ treatments applied to Calafell wastewater, respectively 12% and 14%. Better DOC reductions were obtained on the water of Grasse treated with O₃ or O₃/H₂O₂, respectively, 48% and 60%. In addition, ammonia nitrogen was oxidized to nitrate nitrogen thus giving rise to an over ozone consumption. And finally, both processes proceeded with an increase of pH values. These results highlight the strong dependency of O₃ or O₃/H₂O₂ treatment effectiveness in terms of dissolved organic matter (DOM) removal and ozone consumption on wastewater composition (organic and inorganic substances).     

Experimental Aspects of Mechanistic Studies on Aqueous Ozone Decomposition in Alkaline Solution

Ozone decomposition in aqueous solution was studied by the stopped - flow method over the pH 10.4 - 13.2 range at 25 ± 0.1 °C and I = 0.5 M NaClO₄. At 260 nm the molar absorptivity of aqueous ozone was determined to be 3135 ± 22 M^?1cm^?1. It was shown that various experimental factors may significantly alter the course of the reaction. Even small amounts of H₂O₂ absorbed by the plastic parts of the stopped-flow instrumént can affect the kinetic features of the reaction for an extended period of time. Under strictly controlled experimental conditions sufficiently reproducible data could be obtained for the decomposition. The data were evaluated by comparing experimental and simulated kinetic traces. A detailed kinetic model was developed which is able to predict the decay and life-time of ozone as well as the formation and decomposition of the ozonide ion radical (O₃ ^?) over the pH 10.4 - 13.2 range.