研究目的
To measure the high-temperature mid-infrared absorption spectra of methanol and ethanol in the C-O stretching band between 930 and 1170 cm-1 using a rapid-scan external-cavity quantum-cascade-laser and shock tube facilities, and to compare these measurements with existing empirical models to highlight the need for a high-temperature spectroscopic database.
研究成果
An experimental cross section database for methanol and ethanol at high temperatures was established, showing temperature-broadening effects and negligible pressure dependence. Discrepancies with HITRAN 2016 indicate the need to include high-J transitions and hotbands in models. The methodology provides validation data for spectroscopic model development and supports applications in combustion science and other fields.
研究不足
The maximum temperature was limited by the rate of laser tuning relative to the rate of target species thermal decomposition. Under-sampling due to the spectral interval of the laser may miss narrow absorption features. Uncertainties arise from temperature and pressure fluctuations, especially during thermal decomposition.
1:Experimental Design and Method Selection:
A methodology using a broad-tuning, rapid-scan external-cavity quantum-cascade-laser (EC-QCL) with shock tube facilities was employed to measure absorption spectra. The Beer-Lambert relation was used to define absorption cross sections.
2:Sample Selection and Data Sources:
Methanol (CH3OH) and ethanol (C2H5OH) were selected as target species. Test gases were prepared by diluting vapor from anhydrous alcohol liquids with argon gas.
3:List of Experimental Equipment and Materials:
Equipment includes a shock tube (Stanford Kinetics Shock Tube), EC-QCL (MIRcat-QT TM), MCT detectors (Vigo System TM PVM-2TE-
4:6), CO2 gas laser (Access Laser Company TM), spectrum analyzer (Bristol Instruments TM 771B-XIR), ZnSe beam splitters and windows, filters (Edmund Optics TM 3 μm long-pass filter, Spectrogon TM 85-5 μm band-pass filter), and gas handling systems. Materials include helium, nitrogen, argon gases (Praxair TM), methanol (Sigma-Aldrich TM, 8% purity), and ethanol (Sigma-Aldrich TM, 5% purity). Experimental Procedures and Operational Workflow:
Test gases were prepared manometrically in a heated mixing tank, introduced into the shock tube, and shocked to create high-temperature conditions. The EC-QCL was tuned rapidly to scan the spectral range, with triggers from pressure transducers. Absorption spectra were collected using detectors, with corrections for wavelength drifts and thermal emissions.
5:Data Analysis Methods:
Absorption cross sections were calculated using the Beer-Lambert law. Uncertainties were assessed for temperature, pressure, and absorbance levels. Spectra were compared with models like HITRAN 2016.
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spectrum analyzer
771B-XIR
Bristol Instruments TM
Monitoring the wavelength of the CO2 gas laser before and after tests.
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long-pass filter
7.3 μm
Edmund Optics TM
Reducing thermal emissions from hot gas by filtering wavelengths.
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band-pass filter
9.85-11.5 μm
Spectrogon TM
Spectral filtering for the CO2 laser path to reduce interference.
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external-cavity quantum-cascade-laser
MIRcat-QT TM
Probing the mid-infrared absorption spectra with rapid tuning and broad scanning capabilities.
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MCT detector
PVM-2TE-10.6
Vigo System TM
Detecting laser intensity for absorption measurements, used for common-mode rejection and wavelength reference.
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CO2 gas laser
Access Laser Company TM
Monitoring concentration of methanol during high-temperature tests with fixed wavelength operation.
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shock tube
Stanford Kinetics Shock Tube
Creating high-temperature and high-pressure environments for spectroscopic measurements using shock waves.
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pressure transducer
Measuring pressure rise to trigger data acquisition and calculate shock conditions.
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ZnSe beam splitters
Splitting the laser beam for multiple detection paths.
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ZnSe windows
AR-coated, flat or 30 minute wedged
Providing optical access to the shock tube with anti-reflection coating to minimize losses.
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gas cell
Holding reference gases for wavelength calibration.
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iris
Spatial filtering to reduce beam size and improve signal quality.
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neutral density filter
Attenuating laser intensity to prevent detector saturation.
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