Production Of OH Radicals Research Articles

Single crystal structure feature of a new 0D Cr(III) complex, a catalyst for mild peroxidative oxidation of toluene

[Cr(dipic)(2,2'-bipyridine).H 2 O] 2 .4H 2 O. 2 NO 3 (complex 1 ) • A new water-soluble inorganic complex of Cr(III) has been synthesized. • The complex presents a the triclinic system with the space group P 1 ¯ . • The complex was used for mild peroxidative oxidation of toluene. • The complex shows the maximum catalytic activity of 43.4% • The reactions to this complex appear to follow a radical mechanism. A novel water-soluble inorganic complex of Cr(III), formulated as [Cr(dipic)(2,2'-bipyridine).H 2 O] 2 .4H 2 O. 2(NO 3 ) (complex 1 ) where dipic 2- = pyridine 2,6-dicarboxylate was synthesized. Complex 1 has been characterized by elemental analysis, Fourier transformed-infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), differential thermal analysis (DTA), and single-crystal X-Ray diffraction (SC-XRD). SC-XRD results revealed a triclinic system with space group P 1 ¯ for the expected composition. Each metal center is six-coordinates, and Cr(III) ions are in a distorted octahedral geometry. 1 is a zero-dimensional mononuclear complex that is expanded to a 3D supramolecular network by extensive hydrogen bonds between adjacent layers. The catalytic activity of complex 1 was evaluated towards the peroxidative oxidation (with hydrogen peroxide as a green oxidant) of toluene to the corresponding product (benzyl alcohol and benzaldehyde) in a homogenous medium under mild conditions. The influence of various parameters such as temperature, time, amounts of nitric acid, acetonitrile, catalyst, and n(H 2 O 2 )/n(catalyst) was evaluated to optimize the catalytic system. Complex 1 exhibited high efficiency in the homogeneous oxidation system without requiring the presence of an acid promoter. In this reaction, under optimized conditions, toluene was oxidized to benzyl alcohol and benzaldehyde with a maximum total yield of 43.4%. The study of the mechanism of reaction showed that this process is carried out through both carbon-centered and oxygen-centered radicals. Also, the reaction is promoted by the production of OH radicals that act as active oxidizing agents.

An experimental and modeling study on auto-ignition of ammonia in an RCM with N2O and H2 addition

Deep insights into the combustion kinetics of ammonia (NH3) can facilitate its application as a promising carbon-free fuel. Due to the low reactivity of NH3, experimental data of NH3 combustion can only be obtained within a limited range. In this work, nitrous oxide (N2O) and hydrogen (H2) were used as additives to investigate NH3 auto-ignition in a rapid compression machine (RCM). Ignition delay times for NH3, NH3/N2O blends, and NH3/H2 blends were measured at 30 bar, temperatures from 950 to 1437 K. The addition of N2O and H2 ranged from 0 to 50% and 0 to 25% of NH3 mole fraction, respectively. Time-resolved species profiles were recorded during the auto-ignition process using a fast sampling system combined with a gas chromatograph (GC). An NH3 combustion model was developed, in which the rate constants of key reactions were constrained by current experimental data. The addition of N2O affected the ignition of NH3 primarily through the decomposition of N2O (N2O (+M) = N2 + O (+M), R1) and direct reaction between N2O and NH2 (N2H2 + NO = NH2 + N2O, R2). The rate constant of R2 was constrained effectively by experimental data of NH3/N2O mixtures. Two-stage ignition behaviors were observed for NH3/H2 mixtures, and the corresponding first-stage ignition delay times were reported for the first time. Experimental species profiles suggested the first-stage ignition resulted from the consumption of H2. The oxidation of H2 provided extra HO2 radicals, which promoted the production of OH radicals and initiated first-stage ignition. Reactions between HO2 radicals and NH3/NH2 dominated the first-ignition delay times of NH3/H2 mixtures. Moreover, the first-stage ignition led to the fast production of NO2, which acted as a key intermediate and affected the following total ignition. Consequently, the reaction NH2 + NO2 = H2NO + NO (R3) was constrained by total ignition delay times.

Photo-Fenton Catalyzed by Cu2O/Al2O3: Bisphenol (BPA) Mineralization Driven by UV and Visible Light

This work aimed to demonstrate Cu2O/Al2O3 as a catalyst of the photo-Fenton process in the UV and visible spectra. Cu2O nanoparticles were synthesized by laser ablation in liquid and supported on Al2O3. The catalytic activity of the resulting solid was assessed in the mineralization of bisphenol A (BPA). The studied variables were type of Al2O3α and γ, Cu content (0.5 and 1%), and H2O2 concentration (1, 5, and 10 times the stoichiometric amount). The response variables were BPA concentration and total organic carbon (TOC) removal percentage. The presence of Cu2O nanoparticles (11 nm) with an irregular sphere-like shape was confirmed by transmission electron microscopy (TEM) and their dispersion over the catalytic surface was verified by energy-dispersed spectroscopy (EDS). These particles improve ·OH radical production, and thus a 100% removal of BPA is achieved along with ca. 91% mineralization in 60 min. The BPA oxidation rate is increased one order of magnitude compared to photolysis and doubles that for H2O2 + UV. An increase of 40% in the initial oxidation rate of BPA was observed when switching from α-Al2O3 to γ-Al2O3. 4-hydroxybenzaldehyde, 4-hydroxybenzoic acid, acetaldehyde, and acetic acid are the BPA oxidation by-products identified using LC/MS and based on this a reaction pathway was proposed. Finally, it was also concluded that the synthesized catalyst exhibits catalytic activity not only in the UV spectrum but also in the visible one under circumneutral pH. Therefore, Cu2O/Al2O3 can be recommended to conduct a solar photo-Fenton reaction that can degrade other types of molecules.

A kinetic investigation on low-temperature ignition of propane with ozone addition in an RCM

To extend the temperature for propane ignition to a lower region (< 680 K), ozone (O3) was used as an ignition promoter to investigate the low-temperature chemistry of propane. Ignition delay times for propane containing varying concentrations of O3 (0, 100, and 1000 ppm) were measured at 25 bar, 654–882 K, and equivalence ratios of 0.5 and 1.0 in a rapid compression machine (RCM). Species profiles during propane ignition with varying O3 concentrations were recorded using a fast sampling system combined with a gas chromatograph (GC). A kinetic model for propane ignition with O3 was developed. O3 shortened ignition delay times of propane significantly, and the NTC behavior was weakened. O atoms released from O3 reacted with propane through hydrogen abstraction reactions, which led to the fast production of OH radicals. The following oxidation of fuel radicals generated additional OH radicals. Consequently, the inhibition caused by the slow chemistry of hydrogen peroxide (H2O2) in the NTC region was weakened in the presence of O3. Experimental results with O3 addition can provide extra constraints on the low-temperature chemistry of propane. Species profiles during propane ignition at 730 K with 1000 ppm O3 addition showed the production of propanal (C2H5CHO), acetone (CH3COCH3), and acetaldehyde (CH3CHO) was promoted significantly. Model analyses indicated that O3 shifted the oxidation temperature of propane to a lower region, in which reactions of ROO radicals (NC3H7O2 and IC3H7O2) tend to generate RO radicals (NC3H7O and IC3H7O). The promotion of RO radicals led to the fast production of C2H5CHO, CH3COCH3, and CH3CHO. The corresponding species profile highlighted the reaction relevant to ROO and RO radicals (NC3H7O + O2 = C2H5CHO + HO2 and 2 IC3H7O2 = 2 IC3H7O + O2). Rate constants of these reactions were updated, which can potentially improve the performance of the core mechanism under lower temperatures and provide references for model development of larger hydrocarbons.

Vertical distributions of atmospheric HONO and the corresponding OH radical production by photolysis at the suburb area of Shanghai, China

Nitrous acid (HONO) is considered as one of the main sources of the hydroxyl radical (OH), the most relevant oxidant in the atmosphere. Multi-AXis-Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements were conducted to obtain the vertical profiles of aerosol and HONO from November 1, 2020 to January 31, 2021 at a suburb site of Shanghai, China. HONO was mainly distributed near the surface, but high values HONO occasionally occurred around 0.7 km, indicating an unaccounted source of daytime HONO at high altitudes. The positive correlation between HONO and aerosols suggested that the photo-enhanced heterogeneous reactions on the aerosol surface were an important source of daytime HONO at high altitudes. To obtain the vertical distribution of OH production by HONO photolysis (P(OH)HONO), the vertical profiles of photolysis rate of HONO (JHONO) were calculated by establishing a method of combining observations with empirical relationship based on heterogeneous atmospheric and radiative transfer models. The JHONO increased approximately linearly with increasing altitudes and the noontime averages value of JHONO near the ground were 6.68 × 10−4 s−1, which was strongly negatively affected by aerosols in the morning and afternoon. The P(OH)HONO profile varied in different months (November, December, January) that the changes were mainly affected by HONO and JHONO. P(OH)HONO was more positively affected by JHONO at high altitude and noon but greatly influenced by HONO concentrations in the morning and afternoon.

Comparison of Simultaneous Measurements of Indoor Nitrous Acid: Implications for the Spatial Distribution of Indoor HONO Emissions.

Despite its importance as a radical precursor and a hazardous pollutant, the chemistry of nitrous acid (HONO) in the indoor environment is not fully understood. We present results from a comparison of HONO measurements from a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) and a laser photofragmentation/laser-induced fluorescence (LP/LIF) instrument during the House Observations of Microbial and Environmental Chemistry (HOMEChem) campaign. Experiments during HOMEChem simulated typical household activities and provided a dynamic range of HONO mixing ratios. The instruments measured HONO at different locations in a house featuring a typical air change rate (ACR) (0.5 h–1) and an enhanced mixing rate (∼8 h–1). Despite the distance between the instruments, measurements from the two instruments agreed to within their respective uncertainties (slope = 0.85, R2 = 0.92), indicating that the lifetime of HONO is long enough for it to be quickly distributed indoors, although spatial gradients occurred during ventilation periods. This suggests that emissions of HONO from any source can mix throughout the house and can contribute to OH radical production in sunlit regions, enhancing the oxidative capacity indoors. Measurement discrepancies were likely due to interferences with the LP/LIF instrument as well as calibration uncertainties associated with both instruments.

An Atomic Insight into the Confusion on the Activity of Fe3O4 Nanoparticles as Peroxidase Mimetics and Their Comparison with Horseradish Peroxidase.

Although Fe3O4 nanoparticles were early reported to outperform horseradish peroxidase (HRP), recent studies suggested that this material bears a very poor activity instead. Here, we resolve this disagreement by reviewing the definition of descriptors used and provide an atomic view into the origin of Fe3O4 nanoparticles as peroxidase mimetics. The redox between H2O2 and Fe(II) sites on the Fe3O4 surface was identified as the key step to producing OH radicals for the oxidation of colorimetric substrates. This mechanism involving free radicals is distinct from that of HRP oxidizing substrates with a radical retained on its Fe-porphyrin ring. Surprisingly, the distribution and chemical state of Fe species were found to be very different on single- and polycrystalline Fe3O4 nanoparticles with the latter bearing not only a higher Fe(II)/Fe(III) ratio but also a more reactive Fe(II) species at surface grain boundaries. This accounts for the unexpected gap in the catalytic constant (kcat) observed for this material in the literature.

Nanosecond pulsed plasma assisted combustion of ammonia-air mixtures: Effects on ignition delays and [formula omitted] emission

Computational investigation of plasma assisted combustion of ammonia-air mixtures in constant volume and constant pressure reactors are conducted, to determine the impact of operating conditions on ignition delays and NOx emissions. Due to the lack of a chemical kinetic mechanism for plasma discharge of ammonia (NH3)/air mixtures, a mechanism has been assembled in this work using well-validated plasma reactions of NH3 with O2 and N2, alongside plasma kinetics of air from the literature. The impact of the reduced electric field (E/N), equivalence ratio, pressure, pulse frequency and the energy density on the ignition delays and NO/NO2 emission is discussed. At lower E/N, vibrational-to-translational (VT) relaxation of the vibrational states of NH3 and N2 is observed to play a dominant role in the gas heating process on account of the higher vibrational energy contribution. The ignition event is observed to be faster for fuel-lean mixture (ϕ = 0.5) compared to stoichiometric and fuel-rich (ϕ = 1.2) conditions owing to the lower consumption of OH radicals through the reactivity-inhibiting reaction NH3+OH→NH2+H2O between plasma pulses for leaner mixtures. Nevertheless, the fuel-lean mixture is observed to exhibit higher production of NOx than stoichiometric and fuel-rich mixtures, resulting from plasma chemistry involving oxygen radical and electronic excited states of N2. At the higher pressure of 3 atm, the pressure dependent recombination reaction H+O2+M→HO2+M is found to delay the ignition by limiting the reactive radicals compared to the corresponding 1 atm case. Higher rates of collisional quenching at higher pressures during the inter-pulse gaps resulted in lesser amount of electronically excited states of N2 and O2, which resulted in lower production of air-bound NOx during the pulses. Pulse frequency and energy density per pulse are seen to exhibit an inversely proportional effect on the ignition delay times. Most importantly, a faster ignition and lower production of NOx is observed in the case of plasma discharges compared to thermal energy deposition, owing to the enhanced production of OH radicals and the reforming of NH3 to produce N2 with plasma, respectively. Interesting roles of fuel-radicals such as NH2 and NH in both producing and reducing NO at different instants have also been discussed.

An experimental and modeling study of acetylene-dimethyl ether mixtures oxidation at high-pressure

The oxidation of acetylene (as soot precursor) and dimethyl ether (DME, as a promising fuel additive) mixtures has been analyzed in a tubular flow reactor, under high-pressure conditions (20, 40 and 60 bar), in the 450–1050 K temperature range. The effect of varying the air excess ratio (λ≈0.7, 1 and 20) and the percentage of DME with respect to acetylene (10 and 40%) has been analyzed from both experimental and modeling points of view. The addition of DME modifies the composition of the radical pool, increasing the production of OH radicals which cause a shift in the onset temperature for C2H2 conversion to lower temperatures; the higher the amount of DME, the lower the temperature. The presence of DME favors the oxidation of C2H2 towards products such as CO and CO2, eliminating carbon from the paths that lead to the formation of soot. On the other hand, in the presence of C2H2, DME begins to be consumed at temperatures higher than those required for the high-pressure oxidation of neat DME, around 175–200 K more. Consequently, the negative temperature coefficient (NTC) region characteristic of this compound at low temperatures is not observed under those conditions. However, an additional analysis of the influence of DME inlet concentration (at 20 bar and λ=1) indicates that, if the amount of DME in the mixture is increased to 500 ppm and more (700 or 1000 ppm), the reaction pathways responsible for this high DME reactivity at low temperatures become more relevant and the NTC region can now be observed.

Study on Chemical Kinetics Mechanism of Ignition Characteristics of Dimethyl Ether Blended with Small Molecular Alkanes

Dimethyl ether (DME)/C1-C4 alkane mixtures are ideal fuel for homogeneous charge compression ignition (HCCI) engines. The comparison of ignition delay and multi-stage ignition for DME/C1-C4 alkane mixtures can provide theoretical guidance for expanding the load range and controlling the ignition time of DME HCCI engines. However, the interaction mechanism between DME and C1-C4 alkane under engine relevant high-pressure and low-temperature conditions remains to be revealed, especially the comprehensive comparison of the negative temperature coefficient (NTC) and multi-stage ignition characteristic. Therefore, the CHEMKIN-PRO software is used to calculate the ignition delay process of DME/C1-C4 alkane mixtures (50%/50%) at different compressed temperatures (600–2000 K), pressures (20–50 bar), and equivalence ratios (0.5–2.0) and the multi-stage ignition process of DME/C1-C4 alkane mixtures (50%/50%) over the temperature of 650 K, pressure of 20 bar, and equivalence ratio range of 0.3–0.5. The results show that the ignition delay of the mixtures exhibits a typical NTC characteristic, which is more prominent at a low equivalence ratio and pressure range. The initial temperature of DME/CH4 mixtures of the NTC region is the highest. In the NTC region, the ignition delay DME/CH4 mixtures are the shortest, whereas DME/C3H8 mixtures are the longest. At low-temperature and lean-burn conditions, DME/C1-C4 alkane mixtures exhibit a distinct three-stage ignition characteristic. The time corresponding to heat release rate and pressure peak is the shortest for DME/CH4 mixtures, and it is the longest for DME/C3H8 mixtures. Kinetic analysis indicates that small molecular alkane competes with the OH radical produced in the oxidation process of DME, which inhibits the oxidation of DME and promotes the oxidation of small molecular alkane. The concentration of active radicals and the OH radical production rate of elementary reactions are the highest for DME/CH4 mixtures, and they are the lowest for DME/C3H8 mixtures.

Enhancement of Fenton Performance at Near-Neutral pH by Using Ethylene Diamine Tetra Acetic Acid for Anionic Surfactant Removal from a Laundry Wastewater

Fenton process involving Fe2+ ions and H2O2 produces OH radicals, that act as a strong oxidizing agent for degradation of a variety of organic pollutants. However the process is poor performance at neutral pH limiting its application for industrial wastewater treatment. The short coming problem, in the current study, is solved by introducing ethylene diamine tetra acetic acid (EDTA) as a complexing compound. The degradation was conducted through batch experiment, by varying EDTA concentration and pH. In addition, the Fe2+ and H2O2 concentrations, and the reaction time were optimized. The research results assign that the addition of EDTA could remarkably enhance the degradation of anionic surfactant, that was 96% at pH 6-8. The increase of the degradation was proportional to the concentrations of EDTA and 6 mg/L showed the optimum level. The highest degradation of 162 mg/L anionic surfactant in 20 mL of the laundry wastewater could be achieved within 30 mins by using Fe2+ 10 mM, H2O2 50 mM, and in the pre12sence of EDTA 6 mg/L at pH 7. Key words : Fenton, EDTA, degradation, surfactant, wastewater

Non-thermal argon plasma jets of various lengths for selective reactive oxygen and nitrogen species production

Plasma jets simultaneously create a wide range of reactive oxygen species (ROS) and reactive nitrogen species (RNS), making selective production challenging. In this study, an attempt was made to address this problem by adjusting the downstream length of the plasma jet to regulate reactive species production in an AC-driven argon plasma jet. Jets with short downstream lengths are dominated by RNS, whereas longer ones are dominated by ROS. The energy impact collision between energetic electrons and diffused ambient air is primarily responsible for the generation of RNS in argon plasma. Short plasma jets have a higher electron temperature in the plasma effluent, allowing for better excitation and ionization of N2 molecules. In contrast, in longer jets, electrons transfer most of their energy to neutrals and moisture, even before the diffusion of ambient air. Thus, the production of OH radicals and H2O2 is dominant in longer plasma jets. Further, the ratio of NO2- to H2O2 in plasma-activated water decreased from 1.8 to 0.07, as the downstream length was increased from 1 cm to 10 cm. RNS-enriched short plasma jets are appropriate for immune cell activation, jets of intermediate length are suitable for gold nanoparticle formation because of the synergistic action of ROS and electron energy, and ROS-dominated longer plasma jets are excellent for methylene blue degradation. These findings are applicable to the design of plasma devices in which the generation of ROS and RNS in practical quantities is required to realize plasma technology for a wide range of applications.

Enhanced secondary organic aerosol formation during dust episodes by photochemical reactions in the winter in Wuhan

To investigate the effect of frequently occurring mineral dust on the formation of secondary organic aerosol (SOA), 106 volatile organic compounds (VOCs), trace gas pollutants and chemical components of PM2.5 were measured continuously in January 2021 in Wuhan, Central China. The observation period was divided into two stages that included a haze period and a following dust period, based on the ratio of PM2.5 and PM10 concentrations. The average ratio of secondary organic carbon (SOC) to elemental carbon (EC) was 1.98 during the dust period, which was higher than that during the haze period (0.69). The contribution of SOA to PM2.5 also increased from 2.75% to 8.64%. The analysis of the relationships between the SOA and relative humidity (RH) and the odd oxygen (e.g., OX = O3 + NO2) levels suggested that photochemical reactions played a more important role in the enhancement of SOA production during the dust period than the aqueous-phase reactions. The heterogeneous photochemical production of OH radicals in the presence of metal oxides during the dust period was believed to be enhanced. Meanwhile, the ratios of trans-2-butene to cis-2-butene and m-/p-xylene to ethylbenzene (X/E) dropped significantly, confirming that stronger photochemical reactions occurred and SOA precursors formed efficiently. These results verified the laboratory findings that metal oxides in mineral dust could catalyse the oxidation of VOCs and induce higher SOA production.

Rapid Allylic 1,6 H-Atom Transfer in an Unsaturated Criegee Intermediate.

A novel allylic 1,6 hydrogen-atom-transfer mechanism is established through infrared activation of the 2-butenal oxide Criegee intermediate, resulting in very rapid unimolecular decay to hydroxyl (OH) radical products. A new precursor, Z/E-1,3-diiodobut-1-ene, is synthesized and photolyzed in the presence of oxygen to generate a new four-carbon Criegee intermediate with extended conjugation across the vinyl and carbonyl oxide groups that facilitates rapid allylic 1,6 H-atom transfer. A low-energy reaction pathway involving isomerization of 2-butenal oxide from a lower-energy (tZZ) conformer to a higher-energy (cZZ) conformer followed by 1,6 hydrogen transfer via a seven-membered ring transition state is predicted theoretically and shown experimentally to yield OH products. The low-lying (tZZ) conformer of 2-butenal oxide is identified based on computed anharmonic frequencies and intensities of its conformers. Experimental IR action spectra recorded in the fundamental CH stretch region with OH product detection by UV laser-induced fluorescence reveal a distinctive IR transition of the low-lying (tZZ) conformer at 2996 cm-1 that results in rapid unimolecular decay to OH products. Statistical RRKM calculations involving a combination of conformational isomerization and unimolecular decay via 1,6 H-transfer yield an effective decay rate keff(E) on the order of 108 s-1 at ca. 3000 cm-1 in good accord with the experiment. Unimolecular decay proceeds with significant enhancement due to quantum mechanical tunneling. A rapid thermal decay rate of ca. 106 s-1 is predicted by master-equation modeling of 2-butenal oxide at 298 K, 1 bar. This novel unimolecular decay pathway is expected to increase the nonphotolytic production of OH radicals upon alkene ozonolysis in the troposphere.

Generation and Release of OH Radicals from the Reaction of H2O with O2 over Soot

AbstractOH radicals in the air maintain the oxidizing power of the troposphere. A conventional view is that particulate matter (PM) in the atmosphere is a major sink of OH radicals, thereby lowering the oxidizing power of atmosphere in the event of high‐level PM. By contrary, our joint experimental/theoretical study reveals a new mechanism for the generation of gaseous OH radicals by carbonaceous soot particles. We show that water and O2 react on carbonaceous surfaces and give rise to gaseous OH radicals under irradiation. With ample delocalized π electrons, carbonaceous surfaces enable the easy desorption of hydroxyl groups to produce gaseous OH radicals, evidenced by direct observation of the steady generation of OH radicals on a carbonaceous surface. Our results reveal a new chemical mechanism for the production of OH radicals.

Generation and Release of OH Radicals from the Reaction of H2 O with O2 over Soot.

OH radicals in the air maintain the oxidizing power of the troposphere. A conventional view is that particulate matter (PM) in the atmosphere is a major sink of OH radicals, thereby lowering the oxidizing power of atmosphere in the event of high-level PM. By contrary, our joint experimental/theoretical study reveals a new mechanism for the generation of gaseous OH radicals by carbonaceous soot particles. We show that water and O2 react on carbonaceous surfaces and give rise to gaseous OH radicals under irradiation. With ample delocalized π electrons, carbonaceous surfaces enable the easy desorption of hydroxyl groups to produce gaseous OH radicals, evidenced by direct observation of the steady generation of OH radicals on a carbonaceous surface. Our results reveal a new chemical mechanism for the production of OH radicals.

Characterization of Atmospheric Processes of Brevetoxins in Sea Spray Aerosols from Red Tide Events.

Atmospheric processes can affect the longevity of harmful toxins in sea spray aerosols (SSA). This study characterized the degradation of brevetoxin (BTx) in SSA under different environmental conditions. The samples of seawater collected during a Karenia brevis bloom in Manasota, Florida, were nebulized into a large outdoor photochemical chamber to mimic the atmospheric oxidation of aerosolized toxins and then aged in the presence or absence of sunlight and/or O3. Aerosol samples were collected during the aging process using a Particle-Into-Liquid Sampler. Their BTx concentrations were measured using an enzyme-linked immuno-sorbent assay (ELISA) and high-performance liquid chromatography/tandem mass spectroscopy. The BTx ozonolysis rate constant measured by ELISA was 5.74 ± 0.21 × 103 M-1 s-1. The corresponding lifetime for decay of 87.5% BTx in the presence of 20 ppb of O3 was 7.08 ± 0.26 h, suggesting that aerosolized BTx can still travel long distances at night before SSA deposition. BTx concentrations in SSA decreased more rapidly in the presence of sunlight than in its absence due to oxidation with photochemically produced OH radicals.

Key Points of Advanced Oxidation Processes (AOPs) for Wastewater, Organic Pollutants and Pharmaceutical Waste Treatment: A Mini Review

Advanced oxidation procedures (AOPs) refer to a variety of technical procedures that produce OH radicals to sufficiently oxidize wastewater, organic pollutant streams, and toxic effluents from industrial, hospital, pharmaceutical and municipal wastes. Through the implementation of such procedures, the (post) treatment of such waste effluents leads to products that are more susceptible to bioremediation, are less toxic and possess less pollutant load. The basic mechanism produces free OH radicals and other reactive species such as superoxide anions, hydrogen peroxide, etc. A basic classification of AOPs is presented in this short review, analyzing the processes of UV/H2O2, Fenton and photo-Fenton, ozone-based (O3) processes, photocatalysis and sonolysis from chemical and equipment points of view to clarify the nature of the reactive species in each AOP and their advantages. Finally, combined AOP implementations are favored through the literature as an efficient solution in addressing the issue of global environmental waste management.

Analysis of OH Radical Injection and Production Behavior by Pulsed Flame Jet in HCCI Combustion

Analysis of OH Radical Injection and Production Behavior by Pulsed Flame Jet in HCCI Combustion

Chemical dynamics of the autoignition of near-stoichiometric and rich methanol/air mixtures

The homogeneous, isochoric and adiabatic autoignition of rich methanol mixtures is analysed using algorithmic tools of Computational Singular Perturbation. It is shown that ignition delay decreases as the equivalence ratio ϕ increases, due to the faster production of OH radicals via the reactions CHOH + HO CHOH + HO and HO (+M) OH + OH (+M). After ignition and for sufficiently rich mixtures the phenomenon of super-adiabatic temperature (SAT) is observed; i.e. the temperature after ignition decreases with time. This feature is accompanied by the appearance of an explosive mode. With increasing values of ϕ, SAT becomes more pronounced and the explosive mode becomes faster; i.e. its time scale is shortened. SAT is due to the fact that as ϕ increases the role of hydrogen chemistry diminishes and the explosive character of the process is basically generated by endothermic dissociation reactions of carbon-containing species that cause an increase in number of molecules and a temperature decrease.