Progress in water vapour spectroscopy at RAL Dr Robert McPheat CAVIAR Annual Meeting Imperial...
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Transcript of Progress in water vapour spectroscopy at RAL Dr Robert McPheat CAVIAR Annual Meeting Imperial...
Progress in water vapour spectroscopy at RAL
Dr Robert McPheat
CAVIAR Annual Meeting
Imperial College, 16/12/2008
MSF Measurements
• Measurements so far in the mid- and near-IR.
• These measurements are intended to target the weak water vapour continuum.– Long path lengths and / or high vapour pressures.
• Measurements carried out at moderate (0.01cm-1) & high resolution (0.002cm-1) using the Bruker IFS125 HR.
• Initial measurements revealed a need for better line data too.
LPAC & SPAC
• Long path lengths and / or high vapour pressures.– Use Long pathlength absorption cell (LPAC) / Short pathlength
absorption cell (SPAC).• LPAC
– 32 to 640 metres in IR, over 1 km in visible– Multi-pass reflective optics (White)– Room temperature to 190K– 0 to 1 bar pressure
• SPAC– 1.2 to 20 metres – Multi-pass reflective optics (White)– Existing temperature range 200 to 350K– 0 to 5 bar pressure
LPAC Measurements
• Measurement conditions– Room temperature, ~ 290 K– Water pressures up to 0.75 SVP (< 20 hPa)– Resolution up to 0.002cm-1 but mainly at 0.01cm-1
– Water/air mixtures at total pressures of 150, 500 & 1000 hPa– Pathlengths of 32, 128 & 512m
• Made measurements in 3 spectral ranges covering mid/near-IR – 650 to 2000 cm-1
• MCT detector / KBr beamsplitter / Globar– 1800 to 5500 cm-1
• InSb detector / CaF2 beamsplitter / Globar– 2000 to 11000 cm-1
• InSb detector / CaF2 beamsplitter / Quartz tungsten halogen source
Example LPAC Spectra
17hPa H2O + air to 1000hPa
SPAC redesign
• Water vapour partial pressure limited by vapour pressure at room temperature – Increase temperature to observe weak lines & continuum
• Desired upper temperature for water vapour measurements 450K– All parts of the cell & filling lines need to be at same temperature to avoid
condensation in cold spots.– Need 200ºC, 5 bar pressure gauge
• Other measurements using SPAC require lower temperatures therefore SPAC redesigned for -200 to 200ºC temperature range
• Other requirements– 5 bar maximum pressure– Mirrors adjustable from outside– Accurate temperature & humidity measurement– Corrosion resistant
Insulating Vacuum
Helium
Electrical heaters
Liquid Nitrogen
Sample Gas & White Optics
SPAC upgrade
Optics Inner Cooling Jacket
High temperature pressure gauge & filling line
Temperature & pressure logging
Temperature control
Outer vacuum jacket
Transfer optics vacuum tank
Detector box
SPAC upgrade modifications
• Additional base heaters added• Problems with thermal expansion
– Can be used for hot measurements without cooling jacket but modifications required
SPAC upgrade problems
• Heating capacity limited by rating of spectrometer room ring main.– Use several extension leads from elsewhere
• Original window seals (Indium) melted.– Initially replaced with gold wire which failed on
temperature cycling.– PTFE seals have been installed successfully.
• Long delays getting a working pressure gauge suitable for 5 bar & 200 °C
• Ready to begin measurements beginning of new year
Water line parameter measurements
• Although CAVIAR is targeted at improving the water vapour continuum, errors in line parameters contribute to the measured continuum
• First measurements with upgraded Bruker IFS120 HR– Upgraded electronics / moving
mirror to same specification as IFS125
• High resolution measurements 0.002 cm-1
– Long integration times (~ 12 hours) in mid-IR
Water line parameter measurements
• 5 cm cell to avoid saturation of strong lines
• Required sample pressures <0.5 hPa
• Absorption of water on cell walls causes difficulty in maintaining stable sample pressures
• Large variation of sample pressure with room temperature
• Filling line all stainless steel and as short as possible
• Measurements completed 1000 to 2000 cm-1, 2000 cm-1 to 9000 cm-1 next.
Example Spectra
Wavenumber /cm-1
Tra
nsm
issi
on