Rotational CARS for simultaneous measurements of temperature and concentrations of N2, O2, CO, and CO2 demonstrated in a CO/air diffusion flame

Rotational coherent anti-Stokes Raman spectroscopy (CARS) has over the years demonstrated its strong potential to measure temperature and relative concentrations of major species in combustion. A recent work is the development and experimental validation of a CO₂ model for thermometry, in addition to our previous rotational CARS models for other molecules. In the present work, additional calibration measurements for relative CO₂/N₂ concentrations have been made in the temperature range 294-1246 K in standardized CO₂/N₂ mixtures. Following these calibration measurements, rotational CARS measurements were performed in a laminar CO/air diffusion flame stabilized on a Wolfhard-Parker burner. High-quality spectra were recorded from the fuel-rich region to the surrounding hot air in a lateral cross section of the flame. The spectra were evaluated to obtain simultaneous profiles of temperature and concentrations of all major species; N₂, O₂, CO, and CO₂. The potential for rotational CARS as a multi-species detection technique is discussed in relation to corresponding strategies for vibrational CARS.     

Measurement of nanoparticle temperature in a (CO2) N cluster beam using SF6 molecules as tiny probe thermometers

A temperature measurement technique using SF₆ molecules as tiny probe thermometers is described, and results are presented, for large (CO₂) _N van der Waals clusters (with N ≥ 10²) in a cluster beam. The SF₆ molecules captured by (CO₂) _N clusters in crossed cluster and molecular beams sublimate (evaporate) after a certain time, carrying information about the cluster velocity and internal temperature. Experiments are performed using detection of these molecules with an uncooled pyroelectric detector and infrared multiphoton excitation. The multiphoton absorption spectra of molecules sublimating from clusters are compared with the IR multiphoton absorption spectra of SF₆ in the incoming beam. As a result, the nanoparticle temperature in the (CO₂) _N cluster beam is estimated as T _cl < 150 K. Time-of-flight measurements using a pyroelectric detector and a pulsed CO₂ laser are performed to determine the velocity (kinetic energy) of SF₆ molecules sublimating from clusters, and the cluster temperature is found to be T _cl = 105 ± 15 K. The effects of various factors on the results of nanoparticle temperature measurements are analyzed. The potential use of the proposed technique for vibrational cooling of molecules to low temperatures is discussed.     

In-cylinder gas temperature and water concentration measurements in HCCI engines using a multiplexed-wavelength diode-laser system: Sensor development and initial demonstration

A wavelength-multiplexed, fiber-optic-based, line-of-sight, diode-laser absorption sensor is developed for crank-angle-resolved measurements of temperature and water concentration in a homogeneous-charge-compression-ignition (HCCI) engine. An initial demonstration of its use on two optical HCCI engines at Sandia National Laboratories is reported. The measurements encompassed both motored- and fired-engine operation for temperatures between 300 and 1700 K and pressures between 1 and 55 bar. A spectroscopic line selection process identifies the most appropriate water absorption linepair for thermometry under these conditions. Key solutions to suppress crank-angle-dependent noise in the transmitted laser signals are reported, including careful spectroscopic design and optical engineering to accommodate beam-steering, engine vibration and polarization-related interference. Data obtained through this sensor can provide critical engine characteristics such as combustion efficiency, peak combustion temperature, and autoignition temperature. The flexibility of the wavelength-multiplexed architecture allows the straightforward addition of other wavelengths to potentially enable the simultaneous measurement of other important engine parameters such as temperature non-uniformity, and fuel, CO, and CO₂ concentrations.     

Determination of binary diffusion coefficients of gases using photothermal deflection technique

A photothermal deflection (PD) technique was applied to measure the binary diffusion coefficients of various gases (CO₂–N₂, CO₂–O₂, N₂–He, O₂–He, and CO₂–He). With an in-house-made Loschmidt diffusion cell, a transverse PD system was employed to measure the time-resolved PD signal associated with the variation of the thermal diffusivity and the temperature coefficient of the refractive index of the gas mixture during the diffusion. The concentration evolution of the gas mixture was deduced from the PD amplitude and phase signals based on our diffraction PD model and was processed using two mass-diffusion models explored in this work for both short- and long-time diffusions to find the diffusion coefficient. An optical fiber oxygen sensor was also used to measure the concentration changes of the mixtures with oxygen. Experimental results demonstrated that the binary diffusion coefficients precisely measured with the PD technique were in agreement with the literature values. Moreover, the PD technique can measure the diffusion coefficients of various gas mixtures with both short- and long-time diffusions. In contrast, the oxygen sensor is only suitable for the long-time diffusion measurements of the gas mixtures with oxygen. PACS 78.20.Nv; 51.20.+d     

Effects of O2–CO2 polarization beating on femtosecond coherent anti-Stokes Raman scattering (fs-CARS) spectroscopy of O2

Femtosecond coherent anti-Stokes Raman scattering (fs-CARS) spectroscopy has recently emerged as a promising laser-based temperature-measurement technique in flames. In fs-CARS, the broad spectral bandwidths of the pump and Stokes lasers permit the coupling of each ro-vibrational Raman transition via a large number of pump-Stokes photon pairs, creating a strong Raman coherence. However, the broad-bandwidth fs pulses also excite other molecular transitions that are in resonance. The polarization beating between these closely spaced Raman transitions can affect the coherence dephasing rate of the target molecule, making it difficult to extract accurate medium temperature. In a previous study our group investigated N₂/CO polarization beating in N₂ fs-CARS; in the present work we study O₂/CO₂ polarization beating in O₂ fs-CARS. O₂ fs-CARS can be particularly important for thermometry in non-air-breathing combustion in the absence of N₂. The effects of O₂/CO₂ polarization beating are investigated in the temperature range 300–900 K at atmospheric pressure and also at 300 K for pressures up to 10 bar. Unlike in the N₂/CO system, it was observed in the O₂/CO₂ system that the presence of CO₂ can significantly alter the time evolution of the Raman coherence and, hence, affect the measured temperature.     

Application of time-resolved spectroscopy to concentration measurements in gas mixtures

Concentration measurements using femtosecond Raman Induced Polarization Spectroscopy (RIPS) are performed in binary gas mixtures CO₂–N₂ and CO₂–N₂O at room temperature. The principle of these measurements is based on the nonlinear rotational time response of each molecular component of the mixture. The general form of this molecular response is a series of periodic transients with a period related to the rotational constant B_e. The relative strength of the individual responses allows an accurate determination of the concentration. Two techniques are presented using either two pulses (one pump and one probe) or three pulses (two pumps and one probe).     

Measurements and simulation of in-cylinder UV-absorption in spark ignition and Diesel engines

Spatially and spectrally resolved in-cylinder absorption measurements were performed in spark-ignited internal combustion engines and in Diesel engines. With UV-broadband illumination it was shown that the UV attenuation occurs throughout the burned gas area with roughly homogeneous absorption cross-sections. Model calculations based on the absorption properties of CO₂ at elevated temperatures show that this species gives the main contribution to in-cylinder UV absorption. A previously suggested technique of assessing UV absorption using O₂ laser-induced fluorescence (LIF) as probe light is successfully applied to in-cylinder measurements of the light absorption inside a fired heavy-duty Diesel engine. Even in this environment, the comparison with model calculations shows that CO₂ is the main contributor to UV light absorption. Since the O₂-LIF absorption technique is based on the identical geometry used for LIF concentration measurements, the results can directly be used for correcting LIF signal data such as that obtained from NO imaging. Received: 20 April 2001 / Published online: 18 July 2001     

The viscosity and diffusion coefficients of eighteen binary gaseous systems

The paper reports accurate measurements of the viscosity of the eighteen binary gaseous systems: CF₄ with He, Ne, Ar, N₂, CO₂, CH₄; SF₆ with He, Ne, Ar, N₂, CO₂, CH₄, CF₄ and O₂ with He, Ne, CO₂, CF₄, SF₆. The measurements were performed in a high-precision oscillating-disk viscometer at atmospheric pressure and in the temperature range 25–200°C for the systems containing CH₄ or SF₆ and in the temperature range 25–400°C for the remainder. The reported viscosities are believed to be accurate to within ±0.1% at room temperature and to within ±0.2% at 400°C.It is shown that the data conform to the extended law of corresponding states developed by Kestin, Ro and Wakeham despite the complexity of some of the component gases. The standard deviation between the experimental values and those calculated from the law of corresponding states is only 0.3% which is commensurate with the uncertainty in the experimental results.Binary diffusion coefficients derived from the mixture viscosity data are also presented; they have an estimated uncertainty of ±2%.     

Temperatures in a hollow-catmode discharge

Rotational and vibrational temperatures of He, O₂. and CO₂have been examined in carbon and molybdenum cathodes as functions of pressure and discharge current. The rotational temperature is strongly dependent on the conditions. The rotational temperatures of CO⁺, N ₂ ⁺ , C₂, CN, and OH are identical in simultaneous measurements.     

Carbon dioxide concentration and temperature in flames by raman spectroscopy

The interpretation and prediction of high temperature Raman spectra for CO₂ in flames requires a more detailed treatment of the upper vibrational states than is required for room-temperature spectra. A method for calculating these upper state contributions is presented and is used to evaluate the results of a series of experiments. Laser Raman CO₂ spectra have been obtained for CH₄-air, CO₂ seeded CH₄-air, and CO-air flames. The results indicate that both the high and low temperature CO₂ spectra agree with the theoretical predictions. Comparison of the CO₂ temperature to the N₂ temperature, both measured at the same position in the flames, indicates a better prediction of temperature from the N₂ spectrum than from the CO₂ spectrum. Accurate values for the CO₂ concentrations, however, can be determined from a comparison of the CO₂ spectrum with the N₂ spectrum.     

Raman and fluorescence lidar measurements of aircraft engine emissions

Laser induced Raman and fluorescent measurements were made in the exhaust of a gas turbine engine with a new field portable instrument devised specifically for gas turbine exhaust measurements. The gas turbine exhaust was analyzed by conventional instruments for CO, CO₂, NO, NO_x, total hydrocarbons, smoke and temperature, and these data were used as a ‘calibration’ standard for the evaluation of the laser Raman instrument. Results thus far indicate good correlations for CO₂, O₂, smoke, hydrocarbons and temperature. The instrument was not sensitive enough for NO detection but the data analysis indicates that 100 ppm may be detectable with instrument improvements. CO analysis was not attempted, but it is expected that CO could be detected with further research. NO₂ (or NO_x) was not attempted because theoretical and experimental laboratory analysis indicated severe interference with CO₂. The conclusion was that laser Raman shows a good potential for aircraft gas turbine emission analysis.     

Sensitive detection of CO2 concentration and temperature for hot gases using quantum-cascade laser absorption spectroscopy near 4.2 μm

Mid-infrared quantum-cascade laser (QCL) absorption spectroscopy of CO₂ near 4.2 μm has been developed for measurement of temperature and concentration in hot gases. With stronger absorption line-strengths than transitions near 1.5, 2.0, and 2.7 μm used previously, the fundamental band (00⁰1–00⁰0) of CO₂ near 4.2 μm provides greatly enhanced sensitivity and accuracy to sense CO₂ in high-temperature gases. Line R(74) and line R(96) are chosen as optimum pair for sensitive temperature measurements due to their high-temperature sensitivity, equal signal-to-noise ratio (SNR), weak interference of H₂O transitions, as well as relatively strong line-strengths in high temperature and weak absorption in room temperature. The high-resolution absorption spectrum of the far wings of the R-branch (R56–R100) in the fundamental vibrational band of CO₂ is measured in a heated cell over the range 2,384–2,396 cm^?1 at different temperatures from 700 to 1,200 K. Taking three factors into consideration, including SNR, concentration detectability, and uncertainty sensitivity, the absorption line R(74) is selected to calculate CO₂ concentration. The tunable QCL absorption sensor is validated in mixtures of CO₂ and N₂ in a static cell for temperature range of 700–1,200 K, achieving an accuracy of ±6 K for temperature and ±5 % for concentration measurements.     

Combined raman elastic-backscatter LIDAR for vertical profiling of moisture,aerosol extinction,backscatter, and LIDAR ratio

A combined Raman elastic-backscatter lidar has been developed. A XeCl excimer laser is used as the radiation source. Inelastic Raman backscatter signals are spectrally separated from the elastic signal with a filter or grating polychromator. Raman channels can be chosen to register signals from CO₂, O₂, N₂, and H₂O. Algorithms for the calculation of the water-vapor mixing ratio from the Raman signals and the particle extinction and backscatter coefficients from both elastic and inelastic backscatter signals are given. Nighttime measurements of the vertical humidity distribution up to the tropopause and of particle extinction, backscatter, and lidar ratio profiles in the boundary layer, in high-altitude water and ice clouds, and in the stratospheric aerosol layer are presented. Daytime boundary-layer measurements of moisture and particle extinction are made possible by the improved daylight suppression of the grating polychromator. Test measurements of the CO₂ mixing ratio indicate the problems for the Raman lidar technique in monitoring other trace gases than water vapor.     

Sims studies of the adsorption of O2, CO and CO2 on titanium using low primary energies

The influence of the adsorption of O₂, CO and CO₂ on secondary ion yields from titanium has been examined using 500 eV primary argon ions. Secondary ion energy distributions were also measured. Electron-induced desorption was used as an auxiliary technique. For oxygen adsorption there is agreement with measurements using other techniques and the adsorption process is shown to occur in two stages, an initial rapid chemisorption regime followed by an oxide regime. For carbon monoxide adsorption, the measurements suggest that dissociation does not occur significantly at room temperature. For CO₂, the results are more complex. Complete dissociation seems unlikely but there may be partial dissociation. Some tentative generalizations are made concenrning the influence of adsorption on secondary ion yields.     

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.     

Cross-interference correction and simultaneous multi-gas analysis based on infrared absorption

In this paper, we present simultaneous multiple pollutant gases (CO 2 , CO, and NO) measurements by using the non-dispersive infrared (NDIR) technique. A cross-correlation correction method is proposed and used to correct the cross-interferences among the target gases. The calculation of calibration curves is based on least-square fittings with third-order polynomials, and the interference functions are approximated by linear curves. The pure absorbance of each gas is obtained by solving three simultaneous equations using the fitted interference functions. Through the interference correction, the signal created at each filter channel only depends on the absorption of the intended gas. Gas mixture samples with different concentrations of CO 2 , CO, and NO are pumped into the sample cell for analysis. The results show that the measurement error of each gas is less than 4.5%.     

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.     

Reactions of molybdenum atoms with NO,O<Subscript>2</Subscript>, N<Subscript>2</Subscript>O,and CO<Subscript>2</Subscript> molecules behind shock waves

Experimental results on the interaction of Mo atoms with various oxygen-containing molecules (NO, O₂, N₂O, and CO₂) at high temperatures (>1200 K) are presented, which are in close agreement with measurements at moderate and low temperatures. It is demonstrated that the height of the activation barrier is additionally increased for spin-forbidden reactions and that an increase in the heat of reaction causes an increase in the rate constant for a given type of reaction. For the reactions of Mo atoms with O₂ and N₂O, interpolated temperature dependences of the rate constants, based on the high-temperature measurements conducted in the present work and the published low-temperature data, are proposed.     

High resolution polarization spectroscopy and laser induced fluorescence of CO<Subscript>2</Subscript> around 2μm

High resolution Infrared Polarisation Spectroscopy (IRPS) and Infrared Laser Induced Fluorescence (IRLIF) techniques were used to probe CO₂/N₂ binary gas mixture at atmospheric pressure and ambient temperature. The probed CO₂ molecules were prepared by laser excitation to an overtone and combination ro-vibrational state (12⁰1, J=15) of CO₂, centred at 4988.6612 cm^-1. IRPS and IRLIF line profiles were recorded for several CO₂/N₂ binary mixtures. The observed IRLIF line shapes have the expected Lorentzian form while the observed IRPS line shapes are narrower by a factor of two than those recorded with the IRLIF and appear to have a Lorentzian-cubed profile. The recorded line profiles provide measurements of the pressure-broadening coefficient directly at atmospheric pressure. The Full-Width-Half-Maxima (FWHM) pressure broadening coefficients are measured, based on IRLIF, to be 0.2174±0.0092 cm^-1atm^-1 and 0.1327 ±0.0077 cm^-1atm^-1 for self- and N₂ collision broadening, respectively. The broadening coefficients obtained based on IRPS were measured to be ~8% larger than those obtained with IRLIF.     

Determination of temperature by stimulated raman scattering of molecular nitrogen,oxygen, and carbon dioxide

We have determined the temperature from SRS spectra of N₂-N₂, N₂-CO₂, O₂-O₂, and CO₂-CO₂ recorded in wide pressure and temperature ranges. The fitting procedure takes simultaneously into account the Dicke effect and motional narrowing. We have quantified the accuracy of the MEG and ECS-P models for rotational relaxation. The temperature extracted from each model is compared with thermocouple measurements. The influence of vibrational broadening and shifting is discussed in detail.