Narrow-band BoxCARS applied to CO2 laser discharges

Summary CARS (Coherent Anti-Stokes Raman Scattering) has developed into a powerful tool for studying molecular systems. One of its possibilities is to derive vibrational and rotational temperatures as well as concentrations of molecules from measurements of the energy level population differences. A very good spatial resolution of CARS technique is one of its important advantages. This feature has been utilized for making spatially resolved measurements of the vibrational and rotational temperatures of N₂ in a d.c.-excited transverse-flow CO₂ laser discharge. Apart from that also spectra of CO₂, CO and O₂ in the discharge have been taken, which allowed us to evaluate the spatial distributions of those components in the discharge. Additionally first investigations of a microwave-excited CO₂ laser module have been performed for comparison. Paper presented at the ?XI European CARS Workshop?, Florence, Italy, 23–25 March, 1992.     

AP/(N2 + C2H2 + C2H4) gaseous fuel diffusion flame studies

Counterflow diffusion flame experiments and modeling results are presented for a fuel mixture consisting of N₂, C₂H₂, and C₂H₄ flowing against decomposition products from a solid AP pellet. The flame zone simulates the diffusion flame structure that is expected to exist between reaction products from AP crystals and a hydrocarbon binder. Quantitative species and temperature profiles have been measured for one strain rate, given by a separation of 5 mm, between the fuel exit and the AP surface. Species measured include C₂H₂, C₂H₄, N₂, CN, NH, OH, CH, C₂, NO, NO₂, O₂, CO₂, H₂, CO, HCl, H₂O, and soot volume fraction. Temperature was measured using a combination of a thermocouple at the fuel exit and other selected locations, spontaneous Raman scattering measurements throughout the flame, NO vibrational populations, and OH rotational population distributions. The burning rate of the AP was also measured for this flame’s strain rate. The measured eighteen scalars are compared with predictions from a detailed gas-phase kinetics model consisting of 105 species and 660 reactions. Model predictions are found to be in good agreement with experiment and illustrate the type of kinetic features that may be expected to occur in propellants when AP particles burn with the decomposition products of a polymeric binder.     

H2 CARS thermometry in a fuel-rich,premixed, laminar CH4/air flame in the pressure range between 5 and 40 bar

To establish H₂ CARS thermometry at high pressure, accumulated H₂ Q-branch CARS spectra were recorded in the exhaust of a fuel-rich CH₄/air flame at pressures between 5 and 40 bar. Temperatures were deduced by fitting theoretical spectra to experimental data points. The Energy-Corrected Sudden (ECS) scaling law was employed to set up an empirical model for the calculation of H₂ linewidths in high-pressure hydrocarbon flames with H₂ as a minority species. Experimental H₂ CARS spectra could be simulated very accurately with this model. The evaluated temperatures agreed well with reference temperatures obtained by spontaneous rotational Raman scattering of N₂.     

Multiplex rotational CARS of N2, O2, and CO with excimer pumped dye lasers: Species identification and thermometry in the intermediate temperature range with high temporal and spatial resolution

Pure rotational CARS spectra of N₂, O₂, air, and CO have been obtained using excimer laser pumped dye-lasers. The combination of the folded BOXCARS phase matching geometry with the broad-band laser multiplex method allowed high spatial and temporal resolution. Species and concentration analysis as well as thermometry up to 700 K is demonstrated, and possible applications are discussed.     

K-shell excitation spectra of CO,N2 and O2

Electron energy loss spectra of CO, N₂ and O₂ have been recorded in the regions of carbon, nitrogen and oxygen K-shell excitation and ionisation. These results are compared to previous energy loss, photoabsorption and theoretical studies of the same spectral regions. Several inconsistencies in the published spectra are clarified in the present work. Comparisons with recent calculations of the K-shell continua of these molecules are presented. Vibrational structure in the K → π * transitions of CO (C 1s) and N₂ (N 1s) has been resolved in high-resolution studies (< 0.1 eV FWHM) of these species.     

The chemisorption of CO,CO2, C2H2, C2H4, H2 and NH3 on the clean Fe(100) and (111) crystal surfaces

The chemisorption of small molecules (CO, CO₂, C₂H₂, C₂H₄, H₂ and NH₃) has been studied on the clean Fe(110) and (111) crystal faces by low-energy electron diffraction (LEED) and thermal desorption. C₂H₄ and C₂H₂ yield the same sequence of surface structures that change with temperature and crystal orientation. CO and CO₂ chemisorption similarly results in the formation of the same types of surface structures that change with surface temperature and crystal orientation. Ammonia forms several ordered surface structures on both iron crystal faces. All of the molecules decompose as a function of temperature on the iron surfaces as indicated by the Auger and thermal desorption spectra.     

Prediction of the thermal properties of CO2, CO, and Xe laser media

Approximation functions describing the experimental data of thermal conductivity and viscosity of chosen gases (CO₂, N₂, He, Xe, CO, O₂, Ar) are given in the paper. Introduced formulas allow to predict thermal conductivity and temperature distribution of typical high-power laser gas mixture. Examples of temperature distribution in RF excited CO₂, CO, and Xe laser media are shown. Knowledge of the temperature distribution in the laser cavity can be useful for predicting the general properties of laser.     

Determination of temperature and concentrations of main components in flames by fitting measured Raman spectra

The procedure of deriving flame temperature and major species concentrations by fitting measured Raman spectra in hydrocarbon flames is described. The approach simplifies the calibration procedure to determine temperature and major species concentrations from the measured Raman spectra. The calculations of the Raman spectra are performed using data online positions and cross sections from the current literature. Utilizing all spectral information for deriving temperature and major species concentrations substantially increases accuracy, while interferences can easily be detected and filtered out of the measured spectrum. Temperatures from the separate Raman spectra of N₂, H₂O, O₂, CO₂ and CO are systematically compared with each other over the span of more than 1,700 K. The agreement between them is generally better than 100 K. The developed procedure also allows us to determine the mole fractions of the major species with absolute accuracy of ±10 %.     

Raman spectroscopic study of a laminar hydrogen diffusion flame in air

Spontaneous Raman spectroscopy has been employed for time-averaged, spatially-resolved measurements of temperature and species concentration in an axisymmetric, laminar hydrogen diffusion flame in quiescent air. Temperatures were obtained from vibrational Q-branch raman spectra of N₂, O₂, and H₂ and the rotational Raman spectra of N₂ and H₂, and concentrations of H₂, and N₂ were determined. The results are compared to existing numerical nonequilibrium calculations for the conditions of this experiment. Significant differences between experimental and predicted temperature and concentration profiles are observed. In particular, the flame is larger in both diameter and length and the flame zone is thicker than predicted. Some possible sources of the discrepancies are discussed.     

Absolute radical concentration measurements in low-pressure H2/O2 flames during the combustion of graphite

Absolute CN and CH radical concentrations were determined in situ during the combustion of a graphite substrate in premixed, laminar, low-pressure, H₂/O₂ flames for two different equivalence ratios, = 1.0 and = 1.5. For CN measurements, a small amount of NO (1.8%) was added. The concentration of CN was measured by cavity ring-down spectroscopy (CRDS) probing the absorption of the P_1,2 (13) in the B–X (0, 0) band at 388.1 nm, and the concentration of CH was measured by linear unsaturated laser-induced fluorescence (LIF) exciting the fluorescence of the R₁ (4) in the B–X (0, 0) band at 387.4 nm. Temperature measurements were done based on LIF excitation spectra of OH in the A–X (0, 0) band. It was found that the graphite substrate reduces the flame temperature in the vicinity of its surface. The CN concentrations were found to be three times higher for the rich flame than for the stoichiometric flame. CH concentrations were slightly higher for the stoichiometric flame than for the rich flame. The observed CH/CN concentration ratio is substantially lower compared to NO-doped low-pressure CH₄/O₂ flames. The obtained quantitative information can serve as a first calibration point for detailed numerical simulations of the burning solid graphite, which are based on the concept of surface elementary reactions.     

Interaction of O2, CO2, CO,C2H4 and C2H4O with Ag(110)

The interaction of O₂, CO₂, CO, C₂H₄ AND C₂H₄O with Ag(110) has been studied by low energy electron diffraction (LEED), temperature programmed desorption (TPD) and electron energy loss spectroscopy (EELS). For adsorbed oxygen the EELS and TPD signals are measured as a function of coverage (θ). Up to θ = 0.25 the EELS signal is proportional to coverage; above 0.25 evidence is found for dipole-dipole interaction as the EELS signal is no longer proportional to coverage. The TPD signal is not directly proportional to the oxygen coverage, which is explained by diffusion of part of the adsorbed oxygen into the bulk. Oxygen has been adsorbed both at pressures of less than 10^-4 Pa in an ultrahigh vacuum chamber and at pressures up to 10³ Pa in a preparation chamber. After desorption at 10³ Pa a new type of weakly bound subsurface oxygen is identified, which can be transferred to the surface by heating the crystal to 470 K. CO₂ is not adsorbed as such on clean silver at 300 K. However, it is adsorbed in the form of a carbonate ion if the surface is first exposed to oxygen. If the crystal is heated this complex decomposes into O_ad and CO₂ with an activation energy of 27 kcal/mol(1 kcal = 4.187 kJ). Up to an oxygen coverage of 0.25 one CO₂ molecule is adsorbed per two oxygen atoms on the surface. At higher oxygen coverages the amount of CO₂ adsorbed becomes smaller. CO readily reacts with O_ad at room temperature to form CO₂. This reaction has been used to measure the number of O atoms present on the surface at 300 K relative to the amount of CO₂ that is adsorbed at 300 K by the formation of a carbonate ion. Weakly bound subsurface oxygen does not react with CO at 300 K. Adsorption of C₂H₄O at 110 K is promoted by the presence of atomic oxygen. The activation energy for desorption of C₂H₄O from clean silver is ～ 9 kcal/mol, whereas on the oxygen-precovered surface two states are found with activation energies of 8.5 and 12.5 kcal/mol. The results are discussed in terms of the mechanism of ethylene epoxidation over unpromoted and unmoderated silver.     

Detecting annual and seasonal variations of CO2, CO and N2O from a multi-year collocated satellite-radiosonde data-set using the new Rapid Radiance Reconstruction (3R-N) model

The NOAA polar meteorological satellites have embarked the TIROS-N operational vertical sounder (TOVS) since 1979. Using radiosondes and NOAA-10 TOVS measurements which are collocated within a narrow space and time window, we have studied the differences between the TOVS measurements and simulated measurements from a new fast, Rapid Radiance Reconstruction Network (3R-N), non-linear radiative transfer model with up to date spectroscopy. Simulations use radiosonde temperature and humidity measurements as the prime input. The radiative transfer model also uses fixed greenhouse gas absorber amounts (CO₂,CO,N₂O) and reasonable estimates of O₃ and of surface temperature. The 3R-N model is first presented and validated. Then, a study of the differences between the simulated and measured radiances shows annual trends and seasonal variations consistent with independent measurements of variations in CO₂ and other greenhouse gases atmospheric concentrations. The improved accuracy of 3R-N and a better handling of its deviations with respect to observations allow most of difficulties met in a previous study (J. Climate 15 (2002) 95) to be resolved.     

Dilution effects analysis of opposed-jet H2/CO syngas diffusion flames

This paper reported the analysis of dilution effects on the opposed-jet H₂/CO syngas diffusion flames. A computational model, OPPDIF coupled with narrowband radiation calculation, was used to study one-dimensional counterflow syngas diffusion flames with fuel side dilution from CO₂, H₂O and N₂. To distinguish the contributing effects from inert, thermal/diffusion, chemical, and radiation effects, five artificial and chemically inert species XH₂, XCO, XCO₂, XH₂O and XN₂ with the same physical properties as their counterparts were assumed. By comparing the realistic and hypothetical flames, the individual dilution effects on the syngas flames were revealed. Results show, for equal-molar syngas (H₂/CO = 1) at strain rate of 10 s^?1, the maximum flame temperature decreases the most by CO₂ dilution, followed by H₂O and N₂. The inert effect, which reduces the chemical reaction rates by behaving as the inert part of mixtures, drops flame temperature the most. The thermal/diffusion effect of N₂ and the chemical effect of H₂O actually contribute the increase of flame temperature. However, the chemical effect of CO₂ and the radiation effect always decreases flame temperature. For flame extinction by adding diluents, CO₂ dilution favours flame extinction from all contributing effects, while thermal/diffusion effects of H₂O and N₂ extend the flammability. Therefore, extinction dilution percentage is the least for CO₂. The dilution effects on chemical kinetics are also examined. Due to the inert effect, the reaction rate of R84 (OH+H₂ = H+H₂O) is decreasing greatly with increasing dilution percentage while R99 (CO+OH→CO₂+H) is less affected. When the diluents participate chemically, reaction R99 is promoted and R84 is inhibited with H₂O addition, but the trend reverses with CO₂ dilution. Besides, the main chain-branching reaction of R38 (H+O₂→O+OH) is enhanced by the chemical effect of H₂O dilution, but suppressed by CO₂ dilution. Relatively, the influences of thermal/diffusion and radiation effects on the reaction kinetics are then small.     

K-Shell energy loss spectra of 2.5 keV electrons in CO2 and N2O

Energy loss spectra of 2.5 keV electrons, scattered by CO₂ and N₂O through small angles, have been studied in the regions around the carbon, nitrogen and oxygen K-edges. With the exception of the oxygen K-shell spectrum of nitrous oxide, the spectra are similar to those observed¹ for the diatomic molecules, N₂ and CO, in that the spectra are dominated by one very intense discrete transition while above the K-edge considerable structure is observed in addition to the normal K-continuum. This structure represents the simultaneous transitions of K-shell and valence shell electrons. The oxygen K-shell spectrum of nitrous oxide is unique in that the higher energy discrete peaks are more intense relative to the first discrete peak compared with the other spectra, while additional continuum structures are very weak. The observed spectra for the carbon K-shell of carbon dioxide and the terminal nitrogen K-shell of nitrous oxide are not in agreement with predictions based on the core analogy model which has previously been shown¹ to apply in the case of N₂ and CO.     

DC discharge experiment in an Ar/N2/CO2 ternary mixture: A laboratory simulation of the Martian ionosphere's plasma environment

A low-pressure DC plasma discharge sustained in a 1.6%Ar–2.7%N₂–95.3%CO₂ ternary mixture is studied. This plasma was generated in a total pressure range from 1.0 to 4.0 Torr, a power of 6.3 W and a 12 l/min flow rate of gases. The electron temperature was found to be 8.41 eV and the ion density, in the order of 10⁹ cm⁻³. The species observed in the plasma mixture were CO₂, CO₂⁺, CN, CO, CO⁺, O₂, O₂⁺, N₂, N₂⁺, NO, C⁺, Ar and Ar⁺. At the pressure range in the present study, the species observed do not change their intensity due to an increase in the pressure and they separate in two groups according to their emission intensity: the band of the first group (CO₂, CO₂⁺ and CN) is approximately a factor of 3 more intense than that of the second group (CO, CO⁺, O₂, O₂⁺, N₂, N₂⁺, NO, C⁺, Ar and Ar⁺). The behavior of the emission intensities may be correlated to the constant ion density and electron temperature measured. Also, we observed the same constant behavior in the ratios of the neutral and positive species intensities to that of the N₂ intensity, as a function of pressure. This may suggest that the different rate coefficients and cross sections of elastic collision, excitation and de-excitation of electronic or vibrational levels, inelastic and superelastic collisions of electrons with the gas phase and products, neutral–neutral interactions, resonant charged transfer processes, recombination, to mention some, to produce these species change in the same proportion, as a function of the pressure to keep the relative ratios of the species almost constant.     

The adsorption of CO,H2, H2, CO2 and H2O on carburized and graphitized Ni(110)

A study of the adsorption/desorption behavior of CO, H₂O, CO₂ and H₂ on Ni(110)(4 × 5)-C and Ni(110)-graphite was made in order to assess the importance of desorption as a rate-limiting step for the decomposition of formic acid and to identify available reaction channels for the decomposition. The carbide surface adsorbed CO and H₂O in amounts comparable to the clean surface, whereas this surface, unlike clean Ni(110), did not appreciably adsorb H₂. The binding energy of CO on the carbide was coverage sensitive, decreasing from 21 to 12 $\text{kcal}\text{mol}$ as the CO coverage approached 1.1 × 10¹⁵ molecules cm^?2 at 200K. The initial sticking probability and maximum coverage of CO on the carbide surface were close to that observed for clean Ni(110). The amount of H₂, CO, CO₂ and H₂O adsorbed on the graphitized surface was insignificant relative to the clean surface. The kinetics of adsorption/desorption of the states observed are discussed.     

Interactions of D2O with CO and CO2 molecules at cryogenic temperatures

On the basis of the matrix effect of secondary-ion mass spectrometry (SIMS), the intermolecular interactions between D₂O and hydrophobic molecules have been investigated at temperature of 15 K. The D⁺ yield is found to be enhanced markedly relative to the D₃O⁺ yield when the D₂O molecule forms a complex with the CO or CO₂ molecules on the surface. The CO molecules are incorporated in the inner pores of amorphous solid water and then cover the outermost surface facing to the vacuum, which is followed by the 3D-island growth on it. A similar result is obtained for the adsorption of the CO₂ molecule but the filling of the inner pores is not complete due to the lower mobility of the CO₂ molecule. The D₂O film grows on the CO₂ layer, but a pure D₂O film is hardly formed on the CO layer due to the occurrence of intermixing.     

CARS spectral fitting with multiple resonant species using sparse libraries

The coherent anti‐Stokes Raman spectroscopy (CARS) technique is often used in the study of turbulent flames. Fast and accurate algorithms are needed for fitting CARS spectra for temperature and multiple chemical species. This paper describes the development of such an algorithm. The algorithm employs sparse libraries whose size grows more slowly with number of species than a regular library. It was demonstrated by fitting synthetic ‘experimental’ dual‐pump CARS spectra containing four resonant species (N₂, O₂, H₂ and CO₂), both with added noise and without it, and by fitting experimental spectra from a H₂ air flat flame produced by a Hencken burner. In the four‐species example, the library was nearly an order of magnitude smaller than the equivalent regular library (fitting times are correspondingly faster), and the fitting errors in the absence of added noise were negligible compared to the random errors associated with fitting noisy spectra. When fitting noisy spectra, weighted least squares fitting to signal intensity, as opposed to least squares fitting or least squares fitting to square root of intensity, minimized random and bias errors in fit parameters. Copyright © 2011 John Wiley & Sons, Ltd.     

Microwave spectrum of the heterodimers: CH3OH-CO2 and CH3OH-H2CO

Molecular complexes, dimers and heterodimers often show interesting structures, large amplitude internal motions and orientations for reaction coordinates. These properties were the motivations for the current study of the rotational spectra of the heterodimers, CH₃OH-CO₂ and CH₃OH-H₂CO, in a pulsed nozzle Fourier-transform microwave (FTMW) spectrometer. In addition to studying the normal isotopic forms, several isotopologues containing ¹³C or deuterium substituted atoms of each heterodimer were analyzed in order to obtain structural data of the complexes. All species showed splittings from internal rotation of the methyl group and splittings on the b-type transitions of the CH₃OH-H₂CO species suggesting rotation of the H₂CO group between equivalent structural forms. Stark effect measurements on each of the parent species provided dipole moment components. Theoretical ab initio results are compared to the experimentally determined molecular parameters.     

Linewidths of HCl broadened by CO2 and N2 and CO broadened by CO2

High resolution measurement of the linewidths of HCl broadened by CO₂ and N₂ and CO broadened by CO₂ have been performed in both the 1-0 and 2-0 bands of HCl and the 2-0 band of CO. The data were analyzed by the direct and the peak absorption methods. Values of the linewidths obtained by the two methods are in good agreement. For |m| ≤ 3, for the case of HCl + CO₂, the agreement is good for the values obtained in both bands of HCl. However for |m| > 3, the HCl + CO₂ linewidths in the 1-0 band are smaller than the corresponding lines in the 2-0 band by as much as 11% for |m| = 9. Lines (|m| ≤ 3) of the 1-0 and 2-0 bands of HCl broadened by CO₂ were also analyzed in terms of the super-Lorentzian line profile proposed by Varanasi, S. K. Sarangi, and G. D. T. Tejwani (J. Quan. Spectr. Radiative Transfer12, 857 (1972)) and the Lorentzian profile. The results indicate that near the line center (within 3γ), the shape of HCl + CO₂ lines are Lorentzian.