Coulometric studies of the reduction of nitric oxide,nitrous acid and nitrogen dioxide in acidic halide media with a platinum flow-through electrode

The apparent values of n for the reduction of NO, HNO₂ and NO₂ in acidic halide solutions of intermediate concentration have been determined coulometrically. The value of n_app for HNO₂ is 1.0 in HCl solutions for intermediate flow rates at potential values in the range of the first two cathodic waves observed in voltammetric data. The value of n_app exceeds 1.0 at low flow rate. The values of n_app for reductions of NO in 5 M HC1 and NO₂ in 3.0 M HClO₄ containing 0.1 M bromide are 0.5. These results are explained on the basis of chemical reactions coupled to the electrode processes.     

Chemical Effects of Air Plasma Species on Aqueous Solutes in Direct and Delayed Exposure Modes: Discharge,Post-discharge and Plasma Activated Water

The chemical interaction between non-thermal plasma species and aqueous solutions is considered in the case of discharges in humid air burning over aqueous solutions with emphasis on the oxidizing and acidic effects resulting from formed peroxynitrite ONOO^? and derived species, such as transient nitrite and stable HNO₃. The oxidizing properties are mainly attributed to the systems ONOO^?/ONOOH [E°(ONOOH/NO₂) = 2.05 V/SHE], ^·OH/H₂O [E°(^·OH/H₂O) = 2.38 V/SHE] and to the matching dimer system H₂O₂/H₂O [E°(H₂O₂/H₂O) = 1.68 V/SHE]. ONOOH tentatively splits into reactive species, e.g., nitronium NO⁺ and nitrosonium NO ₂ ⁺ cations. NO⁺ which also results from both ionization of ^·NO and the presence of HNO₂ in acidic medium, is involved in the amine diazotation/nitrosation degradation processes. NO ₂ ⁺ requires a sensibly higher energy than NO⁺ to form and is considered with the nitration and the degradation of aromatic molecules. Such chemical properties are especially important for organic waste degradation and bacterial inactivation. The kinetic aspect is also considered as an immediate consequence of exposing an aqueous container to the discharge. The relevant chemical effects in the liquid result from direct and delayed exposure conditions. The so called delayed conditions involve both post-discharge (after switching off the discharge) and plasma activated water. An electrochemical model is proposed with special interest devoted to the chemical mechanism of bacterial inactivation under direct or delayed plasma conditions.     

Gaseous Nitrogen Oxides Catholyte for Rechargeable Redox Flow Batteries

There is a strong interest in finding highly soluble redox compounds to improve the energy density of redox flow batteries (RFBs). However, the performance of electrolytes is often negatively influenced by high solute concentration. Herein, we designed a high-potential (0.5 V vs. Ag/Ag⁺) catholyte for RFBs, where the charged and discharged species are both gaseous nitrogen oxides (NO_x). These species can be liberated from the liquid electrolyte and stored in a separate gas container, allowing scale-up of storage capacity without increasing the concentration and volume of the electrolyte. The oxidation of NO in the presence of NO₃⁻ affords N₂O₃, and the reduction of N₂O₃ regenerates NO and NO₃⁻, together affording the electrochemical reaction: NO₃⁻+3 NO⇌2 N₂O₃+e⁻ with a low mass/charge ratio of 152 grams per mole of stored electron. A proof-of-concept NO_x symmetric H-cell shows 200 stable cycles over 400 hours with >97 % Coulombic efficiency and negligible capacity decay.     

Identification of Thermal Decomposition Products and Reactions for Liquid Ammonium Nitrate on the Basis of Ab Initio Calculation

This work analyzed the thermal decomposition of ammonium nitrate (AN) in the liquid phase, using computations based on quantum mechanics to confirm the identity of the products observed in past experimental studies. During these ab initio calculations, the CBS‐QB3//ωB97XD/6–311++G(d,p) method was employed. It was found that one of the most reasonable reaction pathways is HNO₃ + NH₄⁺ → NH₃NO₂⁺ + H₂O followed by NH₃NO₂⁺ + NO₃^– → NH₂NO₂ + HNO₃. In the case in which HNO₃ accumulates in the molten AN, alternate reactions producing NH₂NO₂ are HNO₃ + HNO₃ → N₂O₅ + H₂O and subsequently N₂O₅ + NH₄⁺ → NH₂NO₂ + H₂O. In both scenarios, HNO₃ plays the role of a catalyst and the overall reaction can be written as NH₄⁺ + NO₃^– (AN) → NH₂NO₂ + H₂O. Although the unimolecular decomposition of NH₂NO₂ is thermodynamically unfavorable, water and bases both promote the decomposition of this molecule to N₂O and H₂O. Thus AN thermal decomposition in the liquid phase can be summarized as NH₄⁺ + NO₃^– (AN) → N₂O + 2H₂O.     

Low-temperature activation of nitrogen oxide on Cu-ZSM-5 catalysts

The adsorption and activation of NO molecules on Cu-ZSM-5 catalysts with different Cu/Al and Si/Al ratios (from 0.05 to 1.4 and from 17 to 45, respectively) subjected to different pretreatment was studied by ultraviolet-visible diffuse reflectance (UV-Vis DR). It was found that the amount of chemisorbed NO and the catalyst activity in NO decomposition increased with an increase in the Cu/Al ratio to 0.35–0.40. The intensity of absorption bands at 18400 and 25600 cm⁻¹ in the UV-Vis DR spectra increased symbatically. It was hypothesized that the adsorption of NO occurs at Cu⁺ ions localized in chain copper oxide structures with the formation of mono- and dinitrosyl Cu(I) complexes, and this process is accompanied by the Cu²⁺...Cu⁺ intervalence transfer band in the region of 18400 cm⁻¹. The low-temperature activation of NO occurs through the conversion of the dinitrosyl Cu(I) complex into the π-radical anion (N₂O₂)⁻ stabilized at the Cu²⁺ ion of the chain structure, [Cu²⁺-cis-(N₂O₂)⁻], by electron transfer from the Cu⁺ ion to the cis dimer (NO)₂. This complex corresponds to the L → M charge transfer band in the region of 25600 cm⁻¹. The subsequent destruction of the complex [Cu²⁺-cis-(N₂O₂)⁻] at temperatures of 150–300°C leads to the release of N₂O and the formation of the complex [Cu²⁺O⁻], which further participates in the formation of the nitrite-nitrate complexes [Cu²⁺(NO₂)⁻], [Cu²⁺(NO)(NO₂)⁻], and [Cu²⁺(NO₃)⁻] and NO decomposition products.     

Transient Spark Discharge Generated in Various N2/O2 Gas Mixtures: Reactive Species in the Gas and Water and Their Antibacterial Effects

Reactive species generated in the gas and in water by cold air plasma of the transient spark discharge in various N₂/O₂ gas mixtures (including pure N₂ and pure O₂) have been examined. The discharge was operated without/with circulated water driven down the inclined grounded electrode. Without water, NO and NO₂ are typically produced with maximum concentrations at 50% O₂. N₂O was also present for low O₂ contents (up to 20%), while O₃ was generated only in pure O₂. With water, gaseous NO and NO₂ concentrations were lower, N₂O was completely suppressed and HNO₂ increased; and O₃ was lowered in O₂ gas. All species production decreased with the gas flow rate increasing from 0.5 to 2.2 L/min. Liquid phase species (H₂O₂, NO₂￣, NO₃￣, ^·OH) were detected in plasma treated water. H₂O₂ reached the highest concentrations in pure N₂ and O₂. On the other hand, nitrites NO₂￣ and nitrates NO₃￣ peaked between 20 and 80% O₂ and were associated with pH reduction. The concentrations of all species increased with the plasma treatment time. Aqueous ^·OH radicals were analyzed by terephthalic acid fluorescence and their concentration correlated with H₂O₂. The antibacterial efficacy of the transient spark on bacteria in water increased with water treatment time and was found the strongest in the air-like mixture thanks to the peroxynitrite formation. Yet, significant antibacterial effects were found even in pure N₂ and in pure O₂ most likely due to high ^·OH radical concentrations. Controlling the N₂/O₂ ratio in the gas mixture, gas flow rate, and water treatment time enables tuning the antibacterial efficacy.

     

The Effect of Oxygen and Water Vapor on Nitric Oxide Conversion with a Dielectric Barrier Discharge Reactor

The effect of O₂ and H₂O vapor on the Nitric oxide (NO) removal rate, the NO₂ generation rate and the discharge characteristics were investigated using the dielectric barrier discharge (DBD) reactor at 1 atm pressure and at room temperature (20°). The results showed that the O₂ present in the flue gas always hampered the removal of NO and the generation of N₂O, but that the O₂ could enhance the generation of NO₂ in the NO/N₂/O₂ mixtures. Furthermore, with the increase of oxygen, the average discharge current gradually decreases in the reactor. The H₂O present in N₂/NO hindered the removal of NO and the generation of NO₂ but had no impact on the average discharge current in the reactor in the NO/N₂/H₂O mixtures in which the HNO₂ and HNO₃ was detected. The energy efficiency of the DBD used to remove the NO from the flue gas was also estimated.     

Hemoglobin as a nitrite anhydrase: modeling methemoglobin-mediated N2O3 formation

Nitrite has recently been recognized as a storage form of NO in blood and as playing a key role in hypoxic vasodilation. The nitrite ion is readily reduced to NO by hemoglobin in red blood cells, which, as it happens, also presents a conundrum. Given NO’s enormous affinity for ferrous heme, a key question concerns how it escapes capture by hemoglobin as it diffuses out of the red cells and to the endothelium, where vasodilation takes place. Dinitrogen trioxide (N₂O₃) has been proposed as a vehicle that transports NO to the endothelium, where it dissociates to NO and NO₂. Although N₂O₃ formation might be readily explained by the reaction Hb‐Fe³⁺+NO₂^?+NO?Hb‐Fe²⁺+N₂O₃, the exact manner in which methemoglobin (Hb‐Fe³⁺), nitrite and NO interact with one another is unclear. Both an “Hb‐Fe³⁺‐NO₂^?+NO” pathway and an “Hb‐Fe³⁺‐NO+NO₂^?” pathway have been proposed. Neither pathway has been established experimentally. Nor has there been any attempt until now to theoretically model N₂O₃ formation, the so‐called nitrite anhydrase reaction. Both pathways have been examined here in a detailed density functional theory (DFT, B3LYP/TZP) study and both have been found to be feasible based on energetics criteria. Modeling the “Hb‐Fe³⁺‐NO₂^?+NO” pathway proved complex. Not only are multiple linkage‐isomeric (N‐ and O‐coordinated) structures conceivable for methemoglobin–nitrite, multiple isomeric forms are also possible for N₂O₃ (the lowest‐energy state has an N? N‐bonded nitronitrosyl structure, O₂N? NO). We considered multiple spin states of methemoglobin–nitrite as well as ferromagnetic and antiferromagnetic coupling of the Fe³⁺ and NO spins. Together, the isomerism and spin variables result in a diabolically complex combinatorial space of reaction pathways. Fortunately, transition states could be successfully calculated for the vast majority of these reaction channels, both M_S=0 and M_S=1. For a six‐coordinate Fe³⁺‐O‐nitrito starting geometry, which is plausible for methemoglobin–nitrite, we found that N₂O₃ formation entails barriers of about 17–20 kcal mol^?1, which is reasonable for a physiologically relevant reaction. For the “Hb‐Fe³⁺‐NO+NO₂^?” pathway, which was also found to be energetically reasonable, our calculations indicate a two‐step mechanism. The first step involves transfer of an electron from NO₂^? to the Fe³⁺–heme–NO center ({FeNO}⁶) , resulting in formation of nitrogen dioxide and an Fe²⁺–heme–NO center ({FeNO}⁷). Subsequent formation of N₂O₃ entails a barrier of only 8.1 kcal mol^?1. From an energetics point of view, the nitrite anhydrase reaction thus is a reasonable proposition. Although it is tempting to interpret our results as favoring the “{FeNO}⁶+NO₂^?” pathway over the “Fe³⁺‐nitrite+NO” pathway, both pathways should be considered energetically reasonable for a biological reaction and it seems inadvisable to favor a unique reaction channel based solely on quantum chemical modeling.     

On the structure and photodissociation of cluster ions in the gas phase. (N2) (O2+) and (NO)2+

Results are presented for two experiments on N₂O₂⁺ cluster ions formed via the reactions O₂⁺ + N₂ + M → (N₂) (O₂⁺) + M (i), and NO⁺ + NO + M → (NO)₂⁺ + M (ii). In the first experiment the N₂O₂⁺ clusters are collisionally dissociated. The resulting collision-induced dissociation (CID) spectra show almost exclusively O₂⁺ and N₂⁺ products from N₂ O₂⁺ formed via the first reaction, and almost exclusively NO⁺ products from N₂O₂⁺ formed via the second reaction. In the second experiment, single-photon photodissociation of N₂O₂⁺ ions produced by both reactions (i) and (ii) was investigate using 514.5 and 634 nm radiation. The results indicate that the N₂O₂⁺ cluster from reaction (i) cannot be photodissociated while the N₂O₂⁺ cluster from reaction (ii) undergoes photodissociation at both wavelengths. These experiments indicate that two distinct N₂O₂⁺ cluster ions exist and that reactions (i) and (ii) selectively produce the two ions.     

Airborne gaseous 13N species and noxious gases produced at the 12 GeV proton synchrotron

The irradiation of atmospheric air with high-energy protons has been performed at the 12 GeV proton synchrotron. The specific activity of ¹³N, one of the principal airborne radioactivities, was measured as a function of the irradiation time at a dose rate of about 6·10¹⁶ eV/g/s, and compared with the calculated values. The predominant chemical species of ¹³N produced were found to be ¹³N₂and ¹³NO₂. Their proportions were approximately 55% for ¹³N₂ and 45% for¹³NO₂, being almost independent of the irradiation time. Smaller quantities of ¹³NO and H¹³NO₂ were also observed. Measurements of radiolytic products showed that ozone is a main product and that NO₂predominates among the products of nitrogen compounds, including HNO₂ and HNO₃. The G-value for ozone formation in air was estimated from the experimental data as 6.4 molecules/100 eV.     

Catalytic reduction of nitrogen monoxide with propene over Nb/TiO2 mixed mechanically with Mn2O3

Selective catalytic reduction of nitrogen monoxide (NO) over a catalyst of mechanically mixed Nb/TiO₂ and Mn₂O₃ (Mn₂O₃+Nb/TiO₂) in an oxidizing atmosphere with propene (C₃H₆) was studied. The Mn₂O₃+Nb/TiO₂ catalyst showed high activity for the reduction of NO to N₂. The maximum conversion of NO to N₂ was observed at 200∼300°C, with about 80% reduction of NO to N₂. Mn₂O₃ enhanced the formation of NO₂ from NO and the activation of propene to react with NO₂ for reduction to N₂.     

Solvent and deuterium isotope effects on the decomposition of ammonium nitrite solutions

The rate of decomposition of NH₄NO₂ solutions, at pH 5–7, equals k[NH₃] [HNO₂]² or k[NH ₄ ⁺ ] [NO ₂ ^– ][HNO₂]. A plausible mechanism involves a ratedetermining attack of N₂O₃, derived from HNO₂, on NH₃. H⁺⁺ and S⁺⁺ are 82 kJ-mol^–1 and –27 J-mol^–1-K^–1, respectively. On partially replacing the solvent water by methanol or ethanol, the change G⁺⁺, coupled with the calculated standard Gibbs energy of transfer of the reactants from water to the mixed solvent indicated that, in the latter, there is a greater destabilization of the transition state compared to that of the reactants. This can be explained by assuming two hydrogen bonds from the same water molecule to the transition state and hence a loss of hydrogen bond energy in the mixed solvent compared to the aqueous solution. The rate constant for the reaction of ND₄NO₂ in D₂O compared to the reaction of NH₄NO₂ in water, gave a composite isotope effect involving two acid-base equilibria, suggested in the proposed mechanism; in addition to primary isotope effects in the equilibrium: 2 HNO₂N₂O₃+H₂O.     

High‐Performance Chemically Regenerative Redox Fuel Cells Using a NO3−/NO Regeneration Reaction

In this study, we proposed high‐performance chemically regenerative redox fuel cells (CRRFCs) using NO₃⁻/NO with a nitrogen‐doped carbon‐felt electrode and a chemical regeneration reaction of NO to NO₃⁻ via O₂. The electrochemical cell using the nitrate reduction to NO at the cathode on the carbon felt and oxidation of H₂ as a fuel at the anode showed a maximal power density of 730 mW cm⁻² at 80 °C and twofold higher power density of 512 mW cm⁻² at 0.8 V, than the target power density of 250 mW cm⁻² at 0.8 V in the H₂/O₂ proton exchange membrane fuel cells (PEMFCs). During the operation of the CRRFCs with the chemical regeneration reactor for 30 days, the CRRFCs maintained 60 % of the initial performance with a regeneration efficiency of about 92.9 % and immediately returned to the initial value when supplied with fresh HNO₃.     

Electron-transfer transitions during the collision of O2, N2, NO and CO with their respective ions

An improved theory of electron transfer absorption is proposed. The possibility of such absorption during the collision of ion-molecule pairs is discussed and frequencies for the O₂O₂⁺, O₂O₂^?, NONO^?, COCO⁺ and N₂N₂⁺ pairs are estimated. Oscillator strengths are also estimated for the O₂O₂⁺ pair.     

An NO+ reactant ion source for ion mobility spectrometry

The major reactant ion in conventional ion mobility spectrometry (IMS) is the hydronium ion, H₃O⁺ which is produced in the usual ionization sources such as corona discharge or radioactive sources. Using the hydronium reactant ion, mostly the analytes with proton affinity higher than that of water are ionized. A broader range of compounds can be detected by IMS if other alternative ionization channels, such as charge transfer from NO⁺, are employed. In this work we introduce a simple and novel method for producing NO⁺ as the major reactant ion in IMS. This was achieved by adding neutral NO to the corona discharge ionization source. The neutral NO was prepared via an additional discharge in an air stream, flowing into the corona discharge source. A curtain plate was mounted in front of the corona discharge to prevent the influence of the analyte on the production of NO⁺. Using this technique, the reactant ion could easily and quickly switch between the H₃O⁺ and NO⁺. The performance of the new source was evaluated by recording ion mobility spectra of test compounds with both H₃O⁺ and NO⁺ reactant ions.     

Anhydrous Nitrates and Nitrosonium Nitratometallates of Manganese and Cobalt,M(NO3)2, NO[Mn(NO3)3], and (NO)2[Co(NO3)4]: Synthesis and Crystal Structure

Crystalline NO[Mn(NO₃)₃] ( I ) and (NO)₂[Co(NO₃)₄] ( II ) were synthesized by reaction of the corresponding metal and a liquid N₂O₄/ethylacetate mixture. I is orthorhombic, Pca2₁, a = 9.414(2), b = 15.929(3), c = 10.180(2) Å, Z = 4, R₁ = 0.0286. II is monoclinic, C2/c, a = 14.463(3), b = 19.154(4), c = 13.724(3) Å, β = 120.90(3), Z = 12, R₁ = 0.0890. Structure I consists of [Mn(NO₃)₃]^– sheets with NO⁺ cations between them. Two types of Mn atoms have CN_Mn = 7 and 8. Structure II is ionic containing isolated [Co(NO₃)₄]‐anions and NO⁺ cations with CN_Co = 8. Crystals of Mn(NO₃)₂ ( III ) and Co(NO₃)₂ ( IV ) were obtained by concentration of metal nitrate hydrate solutions in 100% HNO₃ in a desiccator with P₂O₅. III is cubic, Pa 3, a = 7.527(2) Å, Z = 4, R₁ = 0.0987. IV is trigonal, R 3, a = 10.500(2), c = 12.837(3) Å, Z = 12, R₁ = 0.0354. The three dimensional structure III is isotypic to the strontium and barium dinitrates. Structure IV contains a three dimensional network of interconnected Co(NO₃)_6/3 units with a distorted octahedral coordination environment of Co atoms. General correlations between central atom coordination and coordination modes of NO₃ groups are discussed.     

The electronic structure of N4O62+ and the bonding interaction of NO+ and NO3−

The results are reported of an MO-SCF-CNDO/2 study of the experimental and optimal geometries of the N₄O₆²⁺ion cluster. The calculations are shown to support the stable existence of the N₄O₆²⁺ complex and the suggestion of its discoverers [1] on the role of NO⁺ in the N₂O₄ solutions. The proposed interpretation of the bonding interaction explains why the shortest N β O distances are found with the NO⁺ ions which have their nitrogen atoms displaced out of the NO₃^? plane.     

Optical detection of NO3 and NO2 in “pure” HNO3 vapor,the liquid-phase decomposition of HNO3

Flowing and static gas-phase samples of HNO₃ in O₂ and N₂ were analyzed by long-path ultraviolet/visible (UV/VIS) spectroscopy to reveal the presence of both NO₂ and NO₃, the concentrations of which were calculated using differential absorption cross sections. NO₂ is produced predominantly by the heterogeneous decomposition of HNO₃, whereas NO₃ is generated in the gas phase by the thermal decomposition of N₂O₅, a product of the self-disproportionation of liquid HNO₃. © 1993 John Wiley & Sons, Inc.     

Positive electron impact and chemical ionization mass spectra of some nitramine nitrates

The positive electron impact (EI) and isobutane chemical ionization (CI) mass spectra of six nitramine nitrates were studied with the aid of some accurate mass measurements. In the EI spectra, β fission relative to both the nitramine and nitrate ester is important. In the CI spectra a major ion occurs at [MH – 45]⁺ and was found to be mainly due to [M + 2H ? NO₂]⁺. All of the compounds except N-(2 hydroxyethyl)-N-(2′,4′,6′-trinitrophenyl)nitramine nitrate gave an [MH]⁺ ion. The [MH – 45]⁺ ion in the isobutane CI mass spectra of tetryl is also due to [M + 2H ? NO₂]⁺.     

Reaction mechanism of simultaneous catalytic removal of NOx and diesel soot particulates

Reactions of diesel soot and NOx with and without O₂ were carried out over CuFe₂O₄ catalyst. The ignition temperature of soot with the NO+O₂ feed was lower than that in O₂ or NO but close to those in NO₂ and NO₂+O₂, indicating the implication of NO₂ especially in decreasing the ignition temperature. On the other hand, the reduction of NOx into N₂ was enhanced by coexisting O₂. Based on these results and mechanisms of O₂-soot and NO-soot reactions, the possible reaction mechanism of the simultaneous NOx-soot removal with the NO+O₂ feed has been proposed.