Dissociation equilibrium of dinitrogen tetroxide in organic solvents: An electron paramagnetic resonance measurement

The dissociation equilibrium of N₂O₄−NO₂ has been measured in hexane, carbon tetrachloride and chloroform at different temperatures. The equilibrium constants at 298.15 K (25°C),K _m (molality basis), are 3.5·10⁻⁵ in hexane, 5.9·10⁻⁶ in carbon tetrachloride and 5.3·10⁻⁶ in chloroform. The EPR technique has been used to quantify the NO₂ radical. These data are compared with gas-phase and solution data of previous reports. The applicability of Hildebrand and Scatchard theory of solutions is also discussed and some thermodynamic properties are deduced, such as Henry’s N₂O₄ and NO₂ constants in different solvents.     

Adsorption of pairs of NOx molecules on single-walled carbon nanotubes and formation of NO + NO3 from NO2

The adsorption of NO_x(x = 1, 2, 3) molecules on single-walled carbon nanotubes (SWCNTs) is investigated using first-principle calculations. Single NO, NO₂ and NO₃ molecules are found to physisorb on SWCNTs, but molecules can be chemisorbed in pairs on the top of carbon atoms at close sites of SWCNTs. The adsorption energy for pairs of NO or NO₃ molecules is larger than for pairs of NO₂ molecules. The local curvature is found to have a sizable effect on adsorption energies. The possibility of a surface reaction NO₂ + NO₂ → NO + NO₃ is examined and the relative pathway and barrier is calculated. The results are discussed with reference to available experimental results.     

A first-principles study of gas molecule adsorption on hydrogen-substituted graphdiyne

Hydrogen-substituted graphdiyne (HsGDY) is a novel alkynyl carbon material with a structure similar to that of graphene. In this paper, the adsorption of four gas molecules (NO, NO₂, NH₃, and N₂) on HsGDY and B-doped HsGDY (B-HsGDY) was studied using density functional theory. The results show that the adsorption of NO and NO₂ on HsGDY and B-HsGDY is characterized by a larger charge transfer, stronger interaction, and higher adsorption energy compared with that of NH₃ and N₂. Based on the doping with B atoms, the adsorption energies of the gas molecules on HsGDY significantly improve, especially that of NO and NO₂. The gas molecule adsorption on both HsGDY and B-HsGDY is physical adsorption and the adsorption selectivity is good and thus may be applied for gas-sensitive NO and NO₂ materials.     

The Conversion of NOx in a Corona Discharge with an Electrode Material Variation

The spatial and surface chemical products and effectiveness of NO_x removal (abbreviated deNO_x) under the corona discharge action at atmospheric pressure were investigated. The influence of high-voltage electrode material on a discharge character and the heterogeneous influence of the electrode surface are also reported in the article. The qualitative analysis was performed using infrared absorption spectrometry. Special attention was paid to NO and NO₂ calibration measurements.     

The reactions of NO with diesel soot, fullerene, carbon nanotubes and activated carbons doped with transition metals

This work investigates the reactions of NO with eight different types of carbon particles: activated pinewood charcoal, activated charcoals doped with iron, nickel, copper or platinum nitrates, fullerene, carbon nanotubes and soot produced from a heavy duty diesel engine. For this mixtures of NO and argon were passed through a fixed bed of carbonaceous particles mixed with quartz sand, held at a temperature between 25 and 850 °C. The concentrations of CO, CO₂, NO, NO₂ and N₂O in the off-gases were measured; the concentration of N₂ was inferred by atomic balance. The balance on atomic oxygen closed well for all the materials studied. The results are discussed in terms of an elementary reaction mechanism; estimates are made of apparent activation energies for the overall reactions forming CO and CO₂.     

(TPP)NO3的合成、表征与分子识别NO

在氯仿与无水乙醇的混合溶剂(体积比为1:1)中,四苯基卟啉(TPP)与Ce(NO₃)·6H₂O混合反应后,得产物Ce(TPP)NO₃. 通过紫外-可见光谱、红外光谱、荧光光谱、质谱、核磁共振氢谱的分析与表征,四苯基卟啉与铈原子以四齿方式进行配位,在同一个铈原子上还有一个硝酸根配位. 向Ce(TPP)NO₃的二氯甲烷溶液中通入NO气体,NO可以配位在同一个铈原子上,得到新的配合物Ce(TPP)(NO)NO₃,向此溶液中通入N₂,金属卟啉配合物可以恢复为配合物Ce(TPP)NO₃.     

Carbon tetrachloride as a liquid matrix for ortho-para diagnostics of water. Capabilities of IR and NMR spectroscopy

A version of ortho-para diagnostics of water at room temperature, based on the combined use of optical and NMR spectroscopy of water dissolved in carbon tetrachloride in a monomeric form, is proposed. Within this study, the capabilities of spectral diagnostics of water with natural ortho-para composition (ortho/para = 3/1) were fully realized. An experimental technique for preparing large amounts of carbon tetrachloride dried to a high degree (water: CCl₄ < 1: 10⁵) was worked out. The results of successful NMR measurements of the ortho-isomer concentration will be published later.     

SERS and XPS observation of the adsorption behavior of NO and NO2 on a silver powder surface

The influence of H₂O on the adsorption behavior of NO or NO₂ on a silver powder surface was studied by SERS and XPS at room temperature. Water vapor was found to be responsible for the adsorption of NO on the silver powder surface. When surface species such as Ag₂O are present on the surface, some of the NO₂ molecules are adsorbed on the surface species to produce NO^-₃, whereas NO molecules are adsorbed on a different site to produce NO^-₂.     

High-temperature NO or NO2 sensor using stabilized zirconia and tungsten oxide electrode

Stabilized zirconia-based electrochemical devices for which the sensing electrode was provided with a single-metal oxide were tested for NO and NO₂ sensing properties at high temperature. Among the many single-metal oxides examined, WO₃ was found to give the best sensing properties to NO and NO₂ at 500–700°C. The EMF response of the WO₃-attached device was linear to the logarithm of NO or NO₂ concentration. The response and recovery kinetics were speedy. The device gave very small cross-sensitivities to H₂, CO, CH₄, CO₂ and water vapor. The sensing mechanism involving mixed-potential was confirmed from the measurements of polarization curves.     

Reduction of nitric oxide on the carbon pretreated Rh{331} single crystal surface; evidence for molecular CN− formation

The chemisorption of NO on the carbon pretreated Rh{331} single crystal surface has been investigated by XPS, LEED and SIMS. The carbon overlayer was prepared by dehydrogenation of chemisorbed C₂H₄. Results of NO adsorption at room temperature show that surface carbon blocks adsorption sites that normally coordinate molecular NO_ADS and its dissociated products, N_Ads and O_Ads, as determined by comparing to experiments performed on clean Rh{331}. Heating the surface which contains NO_Ads, n_Ads, O_Ads and C_Ads, induces a series of chemical reactions starting with the dissociation of molecular NO_Ads. Above 400 K, the C_Ads and N_Ads atoms combine to form CN^?. The formation of the latter species is confirmed by the temperature evolution of the Rh₂CN⁺ and CN^? SIMS ion yields. The C_Ads species also reacts with O_Ads to produce CO and/or CO₂. These processes occur preferentially over the desorption of N₂ and O₂. In general, it is demonstrated that by using the XPS and SIMS methods, it is possible to identify the reaction species present on the surface at any given temperature and to unravel rather complex reaction pathways.     

Chemical kinetic interactions of NO with a multi-component gasoline surrogate: Experiments and modeling

This work reports an experimental and modeling study on the chemical kinetic interactions of NO with a multi-component gasoline surrogate, namely PACE-20, using a twin-piston rapid compression machine at a stochiometric fuel loading with 20% EGR (exhaust gas recirculation) by mass, pressures of 20 and 40 bar, and temperatures from 700 to 930 K. Five NO concentrations are investigated, namely 0, 20, 50, 70 and 150 ppm, where NO addition effects are characterized through changes in PACE-20 ignition reactivity and heat release characteristics. Experiments indicate that within the low-temperature regime, NO promotes low-temperature heat release rate and main ignition reactivity at low addition levels, with saturation or even inhibiting effects observed at >50 ppm NO addition, while within the NTC/intermediate-temperature regime, adding NO only promotes reactivity. A recently updated, detailed chemical kinetic model with chemistry specific to NOx/hydrocarbons interaction incorporated is used to simulate the experiments, and reasonable agreement is obtained. In-depth sensitivity and rate of production analyses are further performed. The results indicate that NO interacts with PACE-20 via two types of interaction: (a) direct interactions between NO and PACE-20 derivatives, primarily through NO+HO₂↔NO₂+OH and RO₂+NO↔RO+NO₂, and (b) indirect interactions between PACE-20 derivatives and NO₂ produced from the direct interactions, primarily through R+NO₂↔RO+NO. The observed NO inhibiting effect at low temperatures and 150 ppm NO addition is attributed to the lack of HO₂ radicals to sustain NO consumption via NO+HO₂↔NO₂+OH, and the take-up of inhibiting pathways via RO₂+NO↔RO+NO₂. The results also indicate that even with the presence of multiple fuel components, NOx/hydrocarbons interactions are highly selective, and are mainly initiated by the interactions between NO and RO₂ radicals from cyclopentane and ethanol, as well as between NO₂ and R radicals from toluene, 1,2,4-trimethylbenzene and 1-hexene. Further studies on these interactive reactions are therefore highly recommended.     

Pulsed cavity ring-down spectroscopy of NO and NO2 in the exhaust of a diesel engine

The application of pulsed cavity ring-down spectroscopy has been demonstrated for the in situ quantitative determination of NO and NO₂ in the exhaust of a diesel engine. NO absorption has been monitored at the transition from the Χ²Π ground state to the A²Σ⁺ state at 226 nm. For NO₂, absorption bands in the spectral region from 438 nm to 450 nm were used. At the selected engine conditions, concentrations of 212±22 ppm and 29±4 ppm have been measured for NO and NO₂, respectively, in good agreement with separate chemical exhaust gas analysis. The method is sensitive enough to meet the European Euro V standard directive on NO_x emissions. This communication discusses the relatively simple setup needed for this type of measurement, the problems encountered, as well as the prospects for single-stroke, simultaneous measurements of both NO and NO₂ at the sub-ppm level. Received: 30 November 2001 / Revised version: 18 February 2002 / Published online: 14 March 2002     

In situ sensor for cycle-resolved measurement of temperature and mole fractions in IC engine exhaust gases

We present a multi-species mole fraction and temperature sensor for in situ exhaust gas diagnostic of internal combustion (IC) engines. The sensor is based on Tunable Diode Laser Absorption Spectroscopy (TDLAS) and incorporates four optical channels - two miniature White cells and two double-traversal cells - with base lengths of 6?cm. It has been demonstrated at a hot air test stand and in the exhaust manifold of a single-cylinder research engine, with measured temperatures of up to 1000?K. Stable operation was achieved with absorption lengths of up to 192?cm (test stand) and 97?cm (engine). Employing time-division multiplexed detection, six species were measured simultaneously in the engine exhaust, at wavelengths ranging from 1.4?µm to 5.2 µm: water vapor (H₂O), carbon dioxide (CO₂), carbon monoxide (CO), methane (CH₄), nitrogen dioxide (NO₂) and nitric oxide (NO). The effective measurement rate was as high as 1?kHz, and cycle-to-cycle variations were clearly detected. We show the correlation of the air-fuel equivalence ratio with the spectroscopically measured mole fraction of each species. At a cycle-resolved rate, detection limits for the legally regulated species NO and NO₂ were 1?ppm and 4?ppm, respectively. The sensor is intended to help improve the understanding of IC engine emission behavior during fast transients.     

FEM study of NOW and NO2W adsorption system

Nitric oxide adsorption on tungsten and nitric dioxide adsorption on tungsten have been investigated by the FEM method. When NO or NO₂ adsorbs gradually on W at 300 K and at 80 K, the FEM patterns which appear at first are found to be similar to those which appear in N₂ adsorption on W. In the case of NO adsorption on W at 80 K, with further exposure, no further change of the FEM patterns is observed. However, in the cases of NO adsorption on W at 300 K, NO₂ adsorption on W at 300 K, and NO₂ adsorption on W at 80 K, further changes of the FEM patterns are observed with further exposure, and the FEM pattern which is obtained at the saturated state is found to be similar to the FEM pattern which appears at the saturated state of O₂ adsorption on W. From the above results it is suggested that NO and NO₂ dissociate on W at 300 and at 80 K.     

B-, N-doped and BN codoped C60 heterofullerenes for environmental monitoring of NO and NO2: a DFT study

ABSTRACT

Using density functional theory calculations, we investigate the gas sensing performance of B-, N-doped and BN-codoped C₆₀ fullerenes towards NO and NO₂ molecules. The calculated adsorption energies and net charge-transfer values indicate that NO and NO₂ molecules have a stronger interaction with the BN-codoped fullerenes compared to the B- or N-doped ones. It is also found that the electronic properties of the BN-codoped C₆₀ exhibit a larger sensitivity towards NO and NO₂ molecules. An increase in the concentration of doped/co-doped B and N atoms tends to weaken the gas sensing ability of these systems.     

Simultaneous catalytic ozonation of NO and dichloromethane on Mn/H-ZSM-5 catalysts: Interaction effect and mechanism

Catalytic ozonation is a promising method for simultaneous removal of NO_x and Cl-VOCs, but needs to clarify their interaction mechanism and the influence of catalyst acidity. In this paper, the simultaneous catalytic ozonation of NO and dichloromethane (DCM) on Mn/H-ZSM-5 molecular sieve catalysts were investigated experimentally. Results show that the overall acidity, acid sites type and intensity have a significant impact on the degradation efficiency, the conversion path of Cl element, and the interaction of NO/DCM adsorption-degradation. Nevertheless, regardless of catalysts, NO could be preferentially oxidized by ozone to generate NO₂ in co-ozonation process, which inhibited and even shielded DCM ozonation at O₃/DCM ratio <1.7. In addition, the highly active oxidizing species such as NO₃/N₂O₅, produced by the deep ozonation of NO₂, exhibited a synergistic effect on the conversion of DCM and intermediates, which in turn weakened NO₂ deep oxidation. Specifically, NO addition caused a general decrease in the HCl selectivity, and a slight increase in the CHCl₃ selectivity of all samples, while the Cl₂ selectivity was determined by the overall catalyst acidity. The samples with higher overall acidity exhibited lower activity for DCM degradation. In particular, for samples with the weak overall acidity but strong acid sites, the sum selectivity of HCl, Cl₂, and CHCl₃ was significantly improved under the interplay effect of NO, indicating that strong acidic sites were beneficial to the complete degradation of DCM. In-situ DRIFTS revealed that aldehydes and carboxylates were the key intermediates of DCM ozonation. In the co-ozonation, NO and its oxidation products (such as nitrates) could promote the formation and conversion of these intermediates, and further converted into CO and CO₂ by the active oxidant from ozone. Finally, the interference of H₂O and SO₂ on the NO/DCM co-ozonation were revealed.     

Decomposition of NO2 in Oxygen-free NO2: N2 Gas Mixture by Back-Corona Generated Plasma

The back-corona discharge has been successfully applied as a plasma source for decomposition of NO₂ in the oxygen-free gas mixture of N₂:NO₂. The paper reports a first attempt to use back-corona discharge for noxious gas conversion. The preliminary results of laboratory experiments in a needle-to-plate reactor show that the De-NO_x processes in back-corona discharge are similar to the dc streamer corona discharges generated in the same geometry. Both types of discharges convert NO₂ to nitrogen, oxygen and also to N₂O and NO. However, back-corona discharge produces less NO, and is more efficient energetically in NO_x decomposition than the dc streamer corona discharge.     

Application of photocatalytic technology for NO<Subscript>x</Subscript> removal

Materials that contain a photocatalyst have a semi-permanent capacity for removing harmful gases from the ambient air. It is the purpose of this study to investigate the photocatalytic activity of commercial paints containing TiO₂ nanoparticles towards NO and NO₂. Experiments were carried out in a stainless steel (30 m^-3) walk-in type environmental chamber (Indoortron), under “real world setting” conditions of temperature, relative humidity, irradiation and pollutant concentrations. Two types of nanoparticle TiO₂-containing paints were tested for their depolluting properties: a mineral silicate paint and a water-based styrene acrylic paint. The results showed a significant effect of TiO₂-materials in reducing NO_x. It was found that up to 74% of NO and 27% of NO₂ were photo-catalytically degraded by the mineral silicate paint, while degradation percentage using the styrene acrylic paint reached 91% and 71% for NO and NO₂, respectively. The photo-catalytic rate of NO on the mineral and styrene acrylic paint was calculated to 0.11 μg m^-2 s and 0.18 μg m^-2 s, respectively, indicating higher photocatalytic performance of the organic based material. The effect of relative humidity (RH) was also investigated. An increase of RH from 20% to 50% inhibited the NO_x photocatalysis on the surface of the samples. PACS 81.16.Hc; 81.65.Mq; 82.33.Tb; 82.50.Hp; 82.65.+r     

Effects of residence time on the NOx emissions of premixed ammonia-methane-air swirling flames at elevated pressure

In this study, a bespoke single-stage swirl burner was used to experimentally investigate the effects of residence time on emissions from premixed ammonia-methane-air flames. The residence time was altered in two ways: by modifying the combustion chamber's length or by modifying the swirl number. Exhaust emissions of O₂, CO₂, CO, NO, NO₂, and N₂O were measured at an absolute pressure of 2 bar for equivalence ratios between 0.50 and 0.95 and ammonia fractions in the fuel blend between 0 and 100%. Spatial distributions of NO and OH radicals were also imaged using PLIF inside the combustion chamber at different heights above the nozzle. Data shows that increasing residence time can further advance chemical reactions, as evidenced by a reduction in O₂ concentration in the exhaust. Increasing the swirl number reduces emissions of NO, NO₂, and N₂O more efficiently than tripling the chamber's length. However, a decrease in the combustion efficiency may be responsible for a fraction of this NOx reduction when the swirl number is increased for some equivalence ratios. NO emissions are not modified when the chamber's length is increased, which is consistent with the fact that the NO-LIF signal does not decay when the distance from the nozzle increases. Therefore, NO formation is somehow restricted to within the main reaction zone of the swirling flame, that is, the zone whose height does not exceed 60 mm for this burner. Conversely, tripling the chamber's length reduces the concentrations of NO₂ and N₂O. This reduction is not reflected in a measurable increase in NO concentration because NO is present in much larger quantities than NO₂ and N₂O in flames examined here. Consistent with the fact that OH promotes NO formation via fuel-NOx pathways, a positive correlation is found between NO- and OH-LIF intensities.     

Kinetics and thermodynamics of reversible disproportionation–comproportionation in redox triad oxoammonium cations – nitroxyl radicals – hydroxylamines

Kinetics and equilibrium of the acid‐catalyzed disproportionation of cyclic nitroxyl radicals R₂NO^? to oxoammonium cations R₂NO⁺ and hydroxylamines R₂NOH is defined by redox and acid–base properties of these compounds. In a recent work (J. Phys. Org. Chem. 2014, 27, 114‐120), we showed that the kinetic stability of R₂NO^? in acidic media depends on the basicity of the nitroxyl group. Here, we examined the kinetics of the reverse comproportionation reaction of R₂NO⁺ and R₂NOH to R₂NO^? and found that increasing in –I‐effects of substituents greatly reduces the overall equilibrium constant of the reaction K₄. This occurs because of both the increase of acidity constants of hydroxyammonium cations K_3H+ and the difference between the reduction potentials of oxoammonium cations E_R2NO+/R2NO? and nitroxyl radicals E_R2NO?/R2NOH. pH dependences of reduction potentials of nitroxyl radicals to hydroxylamines E_1/3Σ and bond dissociation energies D(O–H) for hydroxylamines R₂NOH in water were determined. For a wide variety of piperidine‐ and pyrrolidine‐1‐oxyls values of pK_3H+ and E_R2NO+/R2NO? correlate with each other, as well as with the equilibrium constants K₄ and the inductive substituent constants σ_I. The correlations obtained allow prediction of the acid–base and redox characteristics of redox triads R₂NO^?–R₂NO⁺–R₂NOH. Copyright © 2014 John Wiley & Sons, Ltd.