Precision trace gas analysis by FT-IR spectroscopy. 1. Simultaneous analysis of CO2, CH4, N2O, and CO in air

We report the development of a method of trace gas analysis based on 1-cm-1 resolution Fourier transform infrared (FT-IR) spectroscopy, deployable in both laboratory and field applications. Carbon dioxide, methane, nitrous oxide, and carbon monoxide may be analyzed simultaneously in a single air sample using this method. We have demonstrated that the method can provide analytical precision of the order of +/- 0.15 mumol mol-1 for CO2, +/- 0.9 nmol mol-1 for CH4, +/- 0.3 nmol mol-1 for N2O, and +/- 0.3 nmol mol-1 for CO, expressed as mole fractions in dry air. The analytical precision is in all cases competitive with or superior to that of the more usual methods of analysis for these trace gases, namely, nondispersive infrared spectroscopy for CO2 and gas chromatography-based techniques for CH4, N2O, and CO. The novel FT-IR method relies on calibration using synthetically calculated absorbance spectra and a chemometric multivariate calibration algorithm, classical least squares.     

Quantitative CARS spectroscopy of CO2 and N2O

Experimental and theoretical investigations of the CARS spectroscopy of CO2(2v2) and N2O(v3) were carried out. The experimental spectra were measured in a heated test cell, and excellent agreement with the observed temperature dependences was obtained from numerical simulations. Assignments were made for all hot bands, and the role of collisional narrowing was quantified. Observed nonresonant susceptibility effects in pure N2O have made it possible to estimate the nonresonant background susceptibility for this molecule by using the resonant contribution as a reference calibration.     

N2 and CO vibrational CARS and H2 rotational CARS spectroscopy of CH4/N2O flames

Broadband CARS spectra of N2 and CO have been obtained from the postflame gases of rich CH4/N2O flames using the nonplanar BOXCARS technique. The temperature and concentration of both N2 and CO in these flames were estimated from CARS spectra with the aid of model calculations and agreed with standard thermochemical predictions. In addition, several pure rotational H2 CARS transitions, certain of which had been previously unobserved, were seen in several spectral regions, most notably in both the CO and NO CARS regions. These observations are important in future modeling of CARS data.     

氮气(空气)中一氧化碳、丙烷混合气体标准样品的研制

通过大量实验,以称量法制备氮气（空气）中一氧化碳、丙烷混合气体标准样品,以气相色谱法对其各项性能进行考核,确保汽车污染物检测仪器数据准确可靠。     

Synthesis,crystal structure and solubility of C6H14N4O2,C4H4O4,2H2O

Synthesis, crystal structure and solubility of a new non-linear optical material l-arginine maleate dihydrate have been reported here. From the solubility studies with different solvents, water was found to be the most suitable one. Title compound crystallized in the triclinic space group P1 with Z=1 and unit cell dimensions a=5.264(3) Å, b=8.039(3) Å, c=9.784(3) Å, α=106.19(3)°, β=97.24(3)°, γ=101.66(2)°. The present complex of l-arginine contains a positively charged zwitterionic arginine molecule and a negatively charged semi-maleate ion. The molecules are held together by a three-dimensional network of hydrogen bonds.     

Pure rotational coherent anti-Stokes Raman spectroscopy in mixtures of CO and N2

We present a model for quantitative measurements in binary mixtures of nitrogen and carbon monoxide by the use of dual-broadband rotational coherent anti-Stokes Raman spectroscopy. The model has been compared with experimental rotational coherent anti-Stokes Raman scattering spectra recorded within the temperature range of 294-702 K. Temperatures and concentrations were evaluated by spectral fits using libraries of theoretically calculated spectra. The relative error of the temperature measurements was 1-2%, and the absolute error of the CO concentration measurements was <0.5% for temperatures < or =600 K. For higher temperatures, the gas composition was not chemically stable, and we observed a conversion of CO to CO2. The influence of important spectroscopic parameters such as the anisotropic polarizability and Raman line-broadening coefficients are discussed in terms of concentration measurements. In particular, it is shown that the CO concentration measurement was more accurate if N2-CO and CO-N2 line-broadening coefficients were included in the calculation. The applicability of the model for quantitative flame measurements is demonstrated by measuring CO concentrations in ethylene/air flames.     

Refractive index of air: 3. The roles of CO2, H2O,and refractivity virials

The author's recent studies of the refractive index of air are extended, and several assumptions made therein are further examined. It is shown that the alternative dispersion equations for CO2, which are due to Edlen [Metrologia 2, 71 (1966)] and Old et al. [J. Opt. Soc. Am. 61, 89 (1971)] result in differences of less than 2 x 10(-9) in the phase refractive index and less than 3 x 10(-9) in the group refractive index for current and predicted concentrations of CO2. However, because the dispersion equation given by Old et al. is consistent with experimental data in the near infrared, it is preferable to the equation used by Edlen, which is valid only in the ultraviolet and the visible. The classical measurement by Barrell and Sears [Philos. Trans. R. Soc. London Ser. A 238, 1 (1939)] on the refractivity of moist air is shown to have some procedural errors in addition to the one discussed by Birch and Downs [Metrologia 30, 155 (1993)]. It is shown that for normal atmospheric conditions the higher refractivity virial coefficients related to the Lorentz-Lorenz relation are adequately incorporated into the empirically determined first refractivity virial. As a guide to users the practical limits to the calculation of the refractive index of the atmosphere that result from the uncertainties in the measurement of the various atmospheric parameters are summarized.     

Laser-induced breakdown spectroscopy for ambient air particulate monitoring: correlation of total and speciated aerosol particle counts

A statistical analysis of ambient air particle monitoring, namely PM2.5, is presented to elucidate the correlations between laser-induced breakdown spectroscopy (LIBS)-based speciated aerosol monitoring and non-speciated aerosol monitoring (i.e., total particle counts). LIBS was used in a real-time, conditional-processing mode to identify individual aerosol particles containing detectable quantities of either calcium or sodium, as based on the resulting atomic emission signals. Using this technique, real-time measurements of speciated aerosol particle concentrations and analyte mass concentrations were evaluated for a total of 60 1-hour sampling periods spread over a 5-week period. For each 1-hour sampling period, total aerosol counts were simultaneously monitored using a commercial light scattering-based instrument. Over the 30 sampling periods, aerosol counts (both total and LIBS-based) were found to vary by more than one order of magnitude. For aerosol particles in the 500 nm to 2.5 microm size range, significant correlations were found between the two sampling methods, resulting in correlation coefficients (r2) ranging from 0.22 to 0.93. In addition, transient fluctuations in aerosol counts on a timescale of 5 to 10 minutes were successfully observed simultaneously with the two monitoring techniques, thereby demonstrating the temporal resolution of LIBS.     

Crystal structure of a new organic dihydrogenomonophosphate (C6H8N3O)2(H2PO4)2

Chemical preparation, X-ray single-crystal, thermal behavior, and IR spectroscopy investigations are given for a new organic cation dihydrogenomonophosphate (C₆H₈N₃O)₂(H₂PO₄)₂ (denoted IAHP) in the solid state. This compound crystallizes in the orthorhombic space group P2₁2₁2₁. The unit cell dimensions are: a = 7.422(3) Å, b = 12.568(5) Å, c = 20.059(8) Å with V = 1871.1(13) Å³ and Z = 4. The structure has been solved using direct method and refined to a reliability R factor of 0.029. The atomic arrangement can be described as inorganic layers of H₂PO₄⁻ anions between which are located the organic groups (C₆H₈N₃O)⁺ through multiple hydrogen bonds.     

Mn(C_2Cl_3O_2)Cl(C_(12)H_8N_2)_2的合成、表征及其纳米晶体参数计算

以Cl3CCOOH、1,10-菲罗啉为配体,以MnCl2·4H2O为金属离子盐,通过溶液蒸发法合成了具有纳米级金属骨架的三元配合物Mn(C2Cl3O2)Cl(C12H8N2)2。通过元素分析、红外光谱、X单晶衍射测得配合物属于单斜晶系,其空间群为P21/c,a=1.8155nm,b=1.0638nm,c=1.4685nm,β=112.9°,z=4,V=2.6110nm3。通过纳米化计算的方法,计算出总晶胞数、总原子数、及表面参数随粒径变化的关系,得出Mn(C2Cl3O2)Cl(C12H8N2)2最佳纳米化尺度为115nm。     

Preparation of SiC ultrafine particles from SiH2Cl2 and C2H4 gas mixtures by a CO2 laser

Preparation of SiC ultrafine particles from SiH₂Cl₂-C₂H₄ mixtures by a CO₂ laser was investigated. The powders with specific surface area in the 8–150 m² g^–1 range were obtained by irradiating SiH₂Cl₂-C₂H₄ gas mixtures with a CO₂ laser at atmospheric pressure. X-ray diffraction of the products showed that silicon, SiC and free carbon were produced and the composition of the powders depended on the C₂H₄/SiH₂Cl₂ ratio. The reaction flame temperature changed from less than 1273 K to more than 3073 K with the laser power density and C₂H₄/SiH₂Cl₂ ratio. When SiH₂Cl₂ was irradiated with the CO₂ laser, the reaction temperature was less than 1273 K and silicon particles were formed. When the SiH₂Cl₂-C₂H₄ mixture was irradiated with a CO₂ laser, the reaction temperature was low (<1273 K) at low power density and low C₂H₄/SiH₂Cl₂ ratio, but it increased rapidly to around 3000 K at high laser power density and high C₂H₄/SiH₂Cl₂ ratio (>0.3). SiC was formed at both high and low reaction flame temperatures. It was considered that the rapid increase in the reaction flame temperature was caused by the initiation of exothermic reactions and the increase in laser absorption which was caused mainly by carbon particle formation. Hysteresis was observed between the reaction flame temperature and the power density of the laser beam. It was found that SiH₂Cl₂ underwent a disproportionation reaction on irradiation with the CO₂ laser, and silicon and SiC particles were formed through the various products of the disproportionation reaction. In particular, at low reaction flame temperature, the reactive species, such as SiH₄ and SiH₃Cl, produced by the disproportionation of SiH₂Cl₂ were considered to play an important role in the formation of silicon and SiC particles.     

Neutron and X-ray powder diffraction studies of the oxynitrides SrW(O,N)3, Ba3W2(O,N)8 and Ba3Mo2(O,N)8

Oxynitrides of composition SrW(O,N)₃, Ba₃W₂(O,N)₈ and Ba₃Mo₂(O,N)₈ have been prepared by the ammonolysis of stoichiometric mixtures of oxides and carbonates. Combined Rietveld refinements of powder neutron and powder X-ray diffraction data have allowed the structure of each to be determined. SrW(O,N)₃ was found to have a cubic Perovskite structure whereas Ba₃W₂(O,N)₈ and Ba₃Mo₂(O,N)₈ have a layered hexagonal structure. In the hexagonal structures the oxygen and nitrogen atoms are distributed almost randomly over two sites in the unit cell producing 4-fold co-ordination to tungsten and molybdenum, a distorted octahedral co-ordination to one barium site and a 10-fold co-ordination to the other.     

Concentration dependence of thermodiffusion constant of H2-He and N2-N2O mixtures

Experimental data on the thermodiffusion constants of H₂-He and N₂-N₂O mixtures obtained on a two-tank instrument are presented. The experimental results are compared with theoretical results based on the allowance for elastic and inelastic collisions.     

Characterization of pH in liquid mixtures of methanol/H2O/CO2

The presence of H2O and CO2 in enhanced-fluidity liquids changes the pH in these mixtures due to the formation of carbonic acid. The acid-base equilibria in enhanced-fluidity liquids will also be affected by the reduction in the dielectric constant with the addition of CO2. The pH of enhanced-fluidity liquid mixtures at room temperature was determined from the UV/visible absorption spectra of several pH indicators. pH values of methanol/H2O/CO2 mixtures with CO2 proportions as high as 19.2 mol% are reported. The effect of adding buffer to methanol/H2O/CO2 mixtures on pH was also studied. It was also shown that pressure variation did not significantly influence the pH of enhanced-fluidity liquids.     

Precision refractive index measurements of air, N2, O2, Ar, and CO2 with a frequency comb

We report precision measurements of the refractive indices of dry air, N(2), O(2), Ar, and CO(2), performed by using a frequency comb as the light source in a Mach-Zehnder interferometer setup. Improved dispersion formulas for all gases are derived with a sensitivity level of 10(-9). These results are valid for a wavelength range from 740 to 860 nm and are in good agreement with measurements from other groups.     

Simultaneous in situ measurement of CO,H2O,and gas temperatures in a full-sized coal-fired power plant by near-infrared diode lasers

We present what is to our knowledge the first near-infrared diode-laser-based absorption spectrometer that is suitable for simultaneous in situ measurement of carbon monoxide, water vapor, and temperature in the combustion chamber (20-m diameter, 13-m path length) of a 600-MW lignite-fired power plant. A fiber-coupled distributed-feedback diode-laser module at 1.56 microm served for CO detection, and a Fabry-Perot diode laser at 813 nm was used to determine H2O concentrations and temperature from multiline water spectra. Despite severe light losses (transmission, <10(-8)) and strong background radiation we achieved a resolution of 1.9 x 10(-4) (1sigma) fractional absorption, equivalent to 200 parts in 10(6) by volume of CO (at 1450 K, 10(5) Pa) with 30-s averaging time.     

Carbon-thermal reduction and nitridation of mixtures of SiO2 and Al2O3 · 2H2O

Sialon powders have been prepared by heating mixtures of SiO₂, Al₂O₃ 2H₂O and carbon in flowing nitrogen at 1470° C. The nitrogen content in the product powder increased with increasing added carbon, and was independent of both the flow rate of nitrogen gas and the surface area of pellet. The amount of SiO lost increased with an increase in the flow rate of nitrogen gas and surface area of the pellet and with a decrease in the amount of added carbon. A major part of the SiO evolved by the carbon reduction was trapped by carbon then consumed by carbon reduction and nitridation to form the sialon powder. The rest of the SiO was carried out of the system by the nitrogen gas. The amount of SiO lost and the nitrogen content can be estimated using the residual carbon content.     

Solid Ar, N2, CO, and O2 in Nanopores

Molecular solids enclosed in pores with diameters in the nm-range are a research field which attracts growing interest. The major questions asked in this context are: what is the structure and the dynamics? How are phase and glass transitions modified by the geometrical constraint? In this contribution we present structural information, by x-ray diffraction measurements, as well as thermodynamic characterization, by vapor pressure and heat capacity measurements, on Ar, which is usually considered the simplest of all condensates, and on the small diatomic molecules N₂, C0, O₂ in porous glasses with average pore diameters from 50 to 130Å.     

Laser-induced breakdown spectroscopy for the environmental determination of total carbon and nitrogen in soils

Soils from various sites have been analysed with the laser-induced breakdown spectroscopy (LIBS) technique for total elemental determination of carbon and nitrogen. Results from LIBS have been correlated to a standard laboratory-based technique (sample combustion), and strong linear correlations were obtained for determination of carbon concentrations. The LIBES technique was used on soils before and after acid washing, and the technique appears to be useful for the determination of both organic and inorganic soil carbon. The LIBS technique has the potential to be packaged into a field-deployable instrument.