Phenol photonitration

This paper presents some new data on nitrophenol formation from phenol under illumination, and reviews the studies performed on phenol photonitration, from its discovery in 1988 to the very recent elucidation of its reaction pathway by the authors. Recent experimental results account for the pH effect on phenol photonitration. The nitrogen sources so far investigated are nitrate and nitrite, which undergo photolysis upon absorption of near-UV light. These studies have given a relevant information on the role of both nitrate and nitrite as environmental factors. Such processes can take place both in natural waters and in atmospheric hydrometeors.     

Study of the Photodegradation Kinetics and Pathways of Hexaflumuron in Liquid Media

Hexaflumuron, one of the benzoylphenylurea insect growth regulators, can be leached into surface water and thus having a potential impact on aquatic organisms. In this study, the photodegradation processes of hexaflumuron under high‐pressure mercury lamp irradiation were assessed. The photodegradation kinetics were studied, as were the effects of pH, different light sources, organic solvents and environmental substances, including nitrate ions (NO₃^?), nitrite ions (NO₂^?), ferrous ions (Fe²⁺), ferric ions (Fe³⁺), humic acid, sodium dodecyl sulfate (SDS) and hydrogen peroxide (H₂O₂). Three photodegradation products in methanol were identified by gas chromatography‐mass spectrometry (GC‐MS). In general, the degradation of hexaflumuron followed first‐order kinetics. In the four media studied, the photodegradation rate order was n‐hexane > methanol > ultrapure water > acetone. Faster degradation was observed under high‐pressure mercury lamp irradiation than under xenon lamp irradiation. The pH had a considerable effect, with the most rapid degradation occurring at pH 5.0. The photodegradation rate of hexaflumuron was promoted in the presence of NO₃^?, NO₂^?, Fe²⁺, humic acid, SDS and H₂O₂, but inhibited by Fe³⁺. Moreover, the presumed photodegradation pathway was proposed to be the cleavage of the urea linkage.     

Ag/TiO2光催化还原硝酸氮

利用化学还原法制备不同Ag掺杂量TiO₂纳米催化剂,采用TEM、XRD、XRF和UV-Vis对催化剂进行表征。考察了催化剂在紫外光(254 nm)和可见光照射下还原初始浓度100 mgN·L^-1水相硝酸氮的活性和效果。重点考察了紫外光照射下Ag掺杂量、不同空穴捕获剂(甲酸、甲醇、乙酸、乙醇、草酸、草酸钠等)及甲酸浓度对硝酸氮还原的影响;对硝酸氮转化率和总氮去除率、形成亚硝酸氮、氨氮浓度及氮气选择性的影响。甲酸浓度为0.030 mol·L^-1、Ag掺杂量为1.0wt%时催化剂效果最佳。此时,硝酸氮、总氮的转化率分别为98.43%、78.13%;亚硝酸氮浓度为零,转化的硝酸氮中只有20.76%转化为氨氮,氮气选择性为79.24%。可见光下进行光催化还原反应时,硝酸氮转化率仅37.98%,但氮气的选择性较高。     

VUV photolysis of aqueous solutions of nitrate and nitrite

Water homolyses upon vacuum-uv excitation into HO^* radicals, hydrogen atoms and with lower efficiency, hydrated electrons. These primary species induce a series of reactions partially depleting nitrate and nitrite from aqueous solutions. Depletion rates depend on the presence of dissolved oxygen and temperature. Nitrate, nitrite, peroxynitrite and N₂O were identified as reaction products after irradiation of, either, nitrite and nitrate in aqueous solutions. A reaction mechanism is proposed in accord with the experimental facts and with the evidence given in the literature, where NO₂ ^* and NO^* are key intermediates. NO₃ ^?, NO₂ ^?, NO₂ ^*, NO^* O₂NO₂ ^?, ONO₂ ^? and N₂O, seem to be interrelated by many redox reactions and reaction equilibria where pH and the availability of electrons determine their occurrence. The proposed mechanism is supported by a computer program with which the observed experimental behavior could be simulated.     

Quantification of nitrite and nitrate in seawater by triethyloxonium tetrafluoroborate derivatization-headspace SPME GC-MS

Triethyloxonium tetrafluoroborate derivatization combined with direct headspace (HS) or SPME-gas chromatography-mass spectrometry (GC-MS) is proposed here for the simultaneous determination of nitrite and nitrate in seawater at micromolar level after conversion to their corresponding volatile ethyl-esters (EtO-NO and EtO-NO₂). Isotopically enriched nitrite [¹⁵N] and nitrate [¹⁵N] are employed as internal standards and for quantification purposes. HS-GC-MS provided instrumental detection limits of 0.07 μM NO₂⁻ and 2 μM NO₃⁻. Validation of the methodology was achieved by determination of nitrite and nitrate in MOOS-1 (Seawater Certified Reference Material for Nutrients, NRC Canada), yielding results in excellent agreement with certified values. All critical aspects connected with the potential inter-conversion between nitrite and nitrate (less than 10%) were evaluated and corrected for by the use of the isotopically enriched internal standard.     

GC-MS Analysis of Biological Nitrate and Nitrite Using Pentafluorobenzyl Bromide in Aqueous Acetone: A Dual Role of Carbonate/Bicarbonate as an Enhancer and Inhibitor of Derivatization

Carbon dioxide (CO₂) and carbonates, which are widely distributed in nature, are constituents of inorganic and organic matter and are essential in vegetable and animal organisms. CO₂ is the principal greenhouse gas in the atmosphere. In human blood, CO₂/HCO₃⁻ is an important buffering system. Inorganic nitrate (ONO₂⁻) and nitrite (ONO⁻) are major metabolites and abundant reservoirs of nitric oxide (NO), an endogenous multifunctional signaling molecule. Carbonic anhydrase (CA) is involved in the reabsorption of nitrite and nitrate from the primary urine. The measurement of nitrate and nitrite in biological samples is of particular importance. The derivatization of nitrate and nitrite in biological samples alongside their ¹⁵N-labeled analogs, which serve as internal standards, is a prerequisite for their analysis by gas chromatography–mass spectrometry (GC-MS). A suitable derivatization reagent is pentafluorobenzyl bromide (PFB-Br). Nitrate and nitrite are converted in aqueous acetone to PFB-ONO₂ and PFB-NO₂, respectively. PFB-Br is also useful for the GC-MS analysis of carbonate/bicarbonate. This is of particular importance in conditions of pharmacological CA inhibition, for instance by acetazolamide, which is accompanied by elevated concomitant excretion of nitrate, nitrite and bicarbonate, as well as by urine alkalization. We performed a series of experiments with exogenous bicarbonate (NaHCO₃) added to human urine samples (range, 0 to 100 mM), as well as with endogenous bicarbonate resulting from the inhibition of CA activity in healthy subjects before and after ingestion of pharmacological acetazolamide. Our results indicate that bicarbonate enhances the derivatization of nitrate with PFB-Br. In contrast, bicarbonate decreases the derivatization of nitrite with PFB-Br. Bicarbonate is not a catalyst, but it enhances PFB-ONO₂ formation and inhibits PFB-NO₂ formation in a concentration-dependent manner. The effects of bicarbonate are likely to result from its reaction with PFB-Br to generate PFB-OCOOH. Nitrate reacts with concomitantly produced PFB-OCOOH to form PFB-ONO₂ in addition to the direct reaction of nitrate with PFB-Br. By contrast, nitrite does not react with PFB-OCOOH to form PFB-NO₂. Sample acidification by small volumes of 20 wt.% aqueous acetic acid abolishes the effects of exogenous and endogenous bicarbonate on nitrite measurement.     

Sequential Spectrophotometric Determination of Microgram Amounts of Nitrate and Nitrite in Mixtures

This paper describes three new methods: the first may be used for the determination of nitrite; the second is applicable to determination of nitrate; and the third permits sequential determination of both nitrite and nitrate in mixtures with no prior separation. For the determination of nitrite and nitrate in synthetic mixtures containing 1:5 to 5:1 ratios of the ions, in tap water, and in river water, mean recoveries (for 3 to 22 μg of added NO⁻₃and NO⁻₂) are 96.1 and 98.1% (n= 15) and coefficients of variation are 2.2 and 2.5% for NO⁻₃and NO⁻₂(n= 5), respectively.     

Steam distillation methods for determination of ammonium,nitrate and nitrite

Steam distillation methods of determining ammonium, nitrate, and nitrite in the presence of alkali-labile organic nitrogen compounds are described. They involve the use of magnesium oxide for distillation of ammonium, ball-milled Devarda alloy for reduction of nitrate and nitrite to ammonium, and sulfamic acid for destruction of nitrite. The methods are rapid, accurate, and precise, and they permit nitrogen isotope-ratio analysis of ammonium, nitrate, and nitrite in tracer studies using ¹⁵N-enriched compounds. They give quantitative recovery of ammonium, nitrate and nitrite added to soil and plant extracts, and appear suitable for analysis of biological materials.     

Enhanced Electrochemical Detection of Nitrite and Nitrite at a Cu-30Ni Alloy Electrode

ABSTRACT

Significant catalytic activity towards the reduction of nitrite at unmodified Cu - 30% Ni alloy electrodes was found within the concentration ranges 16 – 200 μM nitrite. The reduction of nitrite was found to occur at potentials significantly less negative than the reduction of nitrate thereby providing clear resolution and the possibility of reliable nitrite / nitrate speciation. The results are contrasted with those found at a bare copper electrode where the spatial resolution of the nitrate and nitrite reduction processes is severely limited with significant overlap of the reduction processes. The procedure represents an inexpensive and facile method for nitrite determination in a number of applications.     

The Reactivity of the Nitrate Radical (•NO3) in Aqueous and Organic Solutions

Rate constants for the nitrate (^•NO₃) radical reaction with alcohols, alkanes, alkenes, and several aromatic compounds were measured in aqueous and tert‐butanol solution for comparison to aqueous and acetonitrile values from the literature. The measured trends provide insight into the reactions of the ^•NO₃ radical in various media. The reaction with alcohols primarily consists of hydrogen‐atom abstraction from the alpha‐hydroxy position and is faster in solvents of lower polarity where the diffusivity of the radical is greater. Alkenes react faster than alkanes, and their rate constants are also faster in nonpolar solution. The situation is reversed for the nitrate radical reaction with the aromatic compounds, where the rate constants in tert‐butanol are slower. This is attributed to the need to solvate the NO₃⁻ anion and corresponding tropylium cation produced by the ^•NO₃ radical electron transfer reaction. A linear correlation was found between measured rate constants in water and acetonitrile, which can be used to estimate aqueous nitrate radical rate constants for compounds having low water solubility.     

An Addition Method for the Direct Ultraviolet Spectrophotometric Determination of Nitrite in the Presence of a Large Excess of Nitrate

Abstract

The ultraviolet spectra of aqueous nitrite and nitrate solutions and of binary mixtures were obtained. By using an addition technique and a reference nitrate/nitrite solution it was possible to compensate for the interference caused by the overlapping of the nitrate and nitrite bands, which is normally a limiting factor in the analysis of mixtures of nitrite with large excesses of nitrate. The detection limit was 5 × 10^?5 M NO₂ ^? which corresponded to a minimum detectable amount of 2.3 ppm NO₂ ^? in the presence of up to 20,000 times greater amount of NO₃ ^?. The accuracy was ± 0.6% and the standard deviation ± 0. 002.     

Determination of nitrite and nitrate in Venice lagoon water by ion interaction reversed-phase liquid chromatography

Ion interaction reversed-phase liquid chromatography with octylammonium orthophosphate as the interacting reagent and a reversed-phase C₁₈ column was applied to the identification and determination of nitrite and nitrate in Venice lagoon water. Interference by the high chloride concentration was systematically studied and the results obtained with different column packings were compared. With spectrophotometric detection at 230 nm, nitrite at 0.005 mg 1^?1 can be detected and determined even in the presence of 0.70 M chloride. The dependence of the retention time of nitrite on the chloride concentration was studied for two reversed-phase columns with different packings. Concentrations of 0.30 ± 0.05 mg 1^?1 of nitrite and 0.20 ± 0.05 mg 1^?1 of nitrate were found in Venice lagoon water.     

Effect of Ammonium Ions on the Radiation Degradation of Potassium Nitrate

The formation and thermal conversion of paramagnetic centers in -irradiated single crystals of potassium nitrate with an ammonium nitrate impurity was studied by EPR spectroscopy. It was found that the presence of ammonium nitrate decreased the radiation-chemical yield of nitrite ions, which are one of the final radiolysis products of nitrate-containing compounds. An analysis of the results of a study on NO₂ orientation in the KNO₃ crystal lattice with an impurity of NH⁺ ₄ allowed us to propose a mechanism for selective N–O bond rupture in the radiation-stimulated dissociation of the nitrate ion in a potassium nitrate matrix.     

The Synthesis and Application of Novel Nitrating and Nitrosating Agents

Alcohols and phenols are efficiently nitrated with thionyl chloride nitrate or thionyl nitrate, even in the presence of an aromatic moiety. While thionyl chloride nitrate is suitable for nitration of primary OH-groups in carbohydrates, thionyl nitrate is reactive enough to react with secondary OH-groups as well. These reagents permit the highly selective nitration of the 5′-,2′5′- and 3′, 5′-OH-groups of ribonucleosides to produce either mono-or diprotected nitro derivatives in high yields. Carbon acids and the enol form of some ketones are efficiently nitrated with trifluoromethanesulfonyl nitrate/potassium tert-butoxide. Lutidine N-oxide (2,6-(CH₃)₂C₅H₃N O) was found to have a marked effect on nitration reactions. Similarly, thionyl chloride nitrite and thionyl nitrite exhibit an excellent capacity for nitrosation of the aforementioned substrates.     

On the reaction of 4-substituted trimethyltin aromatics with perchlorylfluoride

To evaluate the suitability of [¹⁸F]perchorylfluoride [¹⁸F]FClO₃ as an electrophilic fluorination agent for the preparation of radiopharmaceuticals, the reactivity non-radioactive FClO₃ towards 4-substituted trimethyltin aromatic compounds was studied. Contrary to the expectation, an electrophilic fluorination of the aromatic nucleus did not occur. The reaction of perchlorylfluoride with aromatic trimethylstannyl compounds resulted in the formation of trimethyltin fluoride and the respective destannylated aromatics in variable yields.     

A mechanism for the photochemical transformation of nitrate in snow

Photochemical reactions of trace compounds in snow have important implications for the composition of the atmospheric boundary layer in snow-covered regions and for the interpretation of concentration profiles in snow and ice regarding the composition of the past atmosphere. One of the prominent reactions is the photolysis of nitrate, which leads to the formation of OH radicals in the snow and to the release of reactive nitrogen compounds, like nitrogen oxides (NO and NO₂) and nitrous acid (HONO) to the atmosphere. We performed photolysis experiments using artificial snow, containing variable initial concentrations of nitrate and nitrite, to investigate the reaction mechanism responsible for the formation of the reactive nitrogen compounds. Increasing the initial nitrite concentrations resulted in the formation of significant amounts of nitrate in the snow. A possible precursor of nitrate is NO₂, which can be transformed into nitrate either by the attack of a hydroxy radical or the hydrolysis of the dimer (N₂O₄). A mechanism for the transformation of the nitrogen-containing compounds in snow was developed, assuming that all reactions took place in a quasi-liquid layer (QLL) at the surface of the ice crystals. The unknown photolysis rates of nitrate and nitrite and the rates of NO and NO₂ transfer from the snow to the gas phase, respectively, were adjusted to give an optimum fit of the calculated time series of nitrate, nitrite, and gas phase NO_x with respect to the experimental data. Best agreement was obtained with a ∼25 times faster photolysis rate of nitrite compared to nitrate. The formation of NO₂ is probably the dominant channel for the nitrate photolysis. We used the reaction mechanism further to investigate the release of NO_x and HONO under natural conditions. We found that NO_x emissions are by far dominated by the release of NO₂. The release of HONO to the gas phase depends on the pH of the snow and the HONO transfer rate to the gas phase. However, due to the small amounts of nitrite produced under natural conditions, the formation of HONO in the QLL is probably negligible. We suggest that observed emissions of HONO from the surface snow are dominated by the heterogeneous formation of HONO in the firn air. The reaction of NO₂ on the surfaces of the ice crystals is the most likely HONO source to the gas phase.     

Chemical effects induced by γ-irradiated Na2SO4 in aqueous ammonium nitrate

It is well known that paramagnetic centers are formed when Na₂SO₄ crystals are exposed to -radiation. The dissolution of such crystals in aqueous ammonium nitrate results in reduction of nitrate to nitrite. Various factors which influence the yield of nitrite are investigated. The yield of nitrite is found to vary with the amount of irradiated Na₂SO₄ added, the dose absorbed by Na₂SO₄ crystals, the storing period of the irradiated salt, photoannealing time, concentration of aqueous ammonium nitrate and particle size of the Na₂SO₄ crystals. The G(NO ₂ ^– ) value under optimum conditions of the conversion of nitrate to nitrite by irradiated Na₂SO₄ in aqueous ammonium nitrate is 0.009. The efficiency of energy transfer is 1.5%. The mechanism of reduction is based on the reactions of paramagnetic centers with nitrate ions.     

Photolysis of alkaline-earth nitrates

Peroxynitrite and nitrite ions are the diamagnetic products of photolysis (with light at a wavelength of 253.7 nm) of alkaline-earth nitrates; the paramagnetic products and hydrogen peroxide were not found. The structural water in alkaline-earth nitrate crystals did not affect the qualitative composition of the photodecomposition products. The quantum yield of nitrite ions was 0.0012, 0.0038, 0.0078, and 0.0091 quanta^?1 and that of peroxynitrite ions was 0.0070, 0.0107, 0.0286, and 0.0407 quanta^?1 for Sr(NO₃)₂, Ba(NO₃)₂, Ca(NO₃)₂ · 4H₂O, and Mg(NO₃)₂ · 6H₂O, respectively.     

Interaction between NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> and the surface of supported heteropoly compounds: In situ IR spectroscopic data

The mechanism of activation of nitrogen oxides on unsupported heteropoly compounds and the composition, location, stability, and interconversion mechanisms of adsorption complexes on supported heteropoly compounds have been investigated by in situ IR spectroscopy under thermal desorption conditions. Supporting a small amount of a heteropoly compounds (1% or below) increases NO _x adsorption relative to the adsorption observed for the pure support. This effect is most pronounced for CeO₂ and least pronounced for ZrO₂. The increase in NO _x adsorption is due to NO oxidation to NO₂ on the supported heteropoly compound. The main adsorption species are nitrite and nitrate complexes, which are located on the support. As the temperature is raised, the nitrite complexes turn into the nitrate complexes. The presence of variable-valence ions in the Keggin anion reduces the nitrate complex-surface binding strength. The ions that are not components of the Keggin anion increase the binding strength. The changes in the nitrate complex-support surface binding strength are due to the support modification taking place via the destruction of part of the supported heteropoly compound.     

Spektroskopische Untersuchungen über die Rolle des Käfig-Effektes bei der Prädissoziation aromatischer Nitroverbindungen

Photolysis of the bond R_ar–NO₂ contributes to quenching of the fluorescence of aromatic nitro compounds. Since no nitro compound is known which fluoresces above 20,000 cm^?1 photolysis must occur via a predissociation process. Either a fluorine-substituted nitro compound or fluorobenzene as the solvent was used for the irradiation experiments so that ¹⁹F-NMR. spectroscopy could be used to analyse the reaction products. Cage effects play an important role. With a large distance between the radicals R _ar and NO ₂, the phenyl radical forms a diphenyl compound with a benzenetype solvent molecule, and with small distance recombination will occur. For medium to long distances geminal recombination will also occur, not to the initial nitro compound, but to the corresponding nitrite, which in the presence of oxygen forms o-nitrophenol. Mass spectrometry showed that the added oxygen atom is located in the nitro group.