GAS SAMPLING AT INFRARED ANALYSIS, INC.
Infrared Analysis, Inc. seeks to make gas sampling as simple and inexpensive as possible. We wish for the analyst to do his quantitative analysis at normal conditions of temperature and pressure. We wish to minimize the use of pumps in sample gathering and to avoid the use of heated sample lines and heated absorption cells.
Simplification of sampling and simplification of the analytical method go hand in hand. Our quantitative analysis program, QASoft, uses reference spectra that were recorded and calibrated at normal temperature and pressure. When the sample is then studied under the same normal conditions, a correct quantitative analysis is obtained.
Flue gases, engine exhausts, incinerator effluents and other products of combustion are hot, wet, and laced with toxic gases. There is a widespread impression that to do a spectroscopic analysis of such gas mixtures, one needs to maintain the high sample temperature. There is concern that if the gas sample is cooled, the water will condense and alter the sample by dissolving some of the toxic pollutants. It is the experience of Infrared Analysis, Inc. that such concern can be avoided by proper sample handling. Working at room temperature is feasible in almost all cases.
Mistaken efforts to maintain a high temperature in the combustion gases cause difficulties in the handling of the sample. Heated sampling lines and a heated absorption cell are then needed.. Furthermore, these efforts cause complications in the spectroscopic analysis by maintaining a large amount of high temperature water vapor in the optical path. To allow a good infrared analysis, the heavy pattern of water vapor lines must be subtracted out of the spectrum. This must be done with a water reference spectrum made at the same temperature at which the sample spectrum was made and with nearly the same pathlength-concentration product as applied to the sample spectrum.. At high temperature, this matching is difficult to do because you must control the temperature and monitor the temperature during recording of both the sample spectrum and the reference spectrum.
Another difficulty arising from the high temperature is that you do not usually have available calibration and reference spectra made at the high temperature. Most available digitized reference spectra have been recorded only at room temperature.
Furthermore, one must consider the reaction of the gases with the internal components of the cell. Many of the gases to be measured are acidic and toxic. Such vapors will attack and degrade the mirrors, windows and hardware of the cell. This degradation proceeds much faster when a cell is at high temperature than when it is at room temperature. Chemists say that reaction rates double for every 10 degrees increase in temperature. How much easier things are if one is able to do the analyses at room temperature! The heated lines and heating jackets are gone! The temperature controller and temperature monitor are gone! The reference spectra for subtraction of water and CO2 interference are available! The calibration spectra for the quantitative analysis are available!
What are the obstacles to doing the analysis at room temperature? None! It is an easy thing to dilute the sample. The dilution gas may be instrument air, ambient air, or tank nitrogen. As the sample is diluted, it is cooled down. The dilution must be great enough that the water does not condense. A hot combustion gas may contain up to 10% water vapor. However, at room temperature, a gas mixture cannot hold more than 3% water vapor. The dilution factor in sampling must then be at least 3-to-1.
One may ask: isn't the 3-to-1 dilution going to reduce the measurement sensitivity by a factor of 3? The answer is no. The dilution will reduce all absorbances by a factor of 3, but this includes the interfering water lines. Measuring compounds like NO, NO2 and SO2, whose bands are badly mixed in with the water, will be made easier by the dilution. For these compounds, the dilution may even increase the measurement sensitivity.
Water and CO2 Line Subtraction
One of the principal difficulties in measuring trace gases in air or in combustion effluents is the interference by the spectral lines of water vapor. To enable a complete, fully sensitive analysis, water lines should be removed from the spectrum before the other lines are measured. The water lines are removed by means of a water subtraction spectrum. Each user needs to prepare his own water subtraction spectrum as well as his own CO2 subtraction spectrum. The reason for this is that a good subtraction requires the sample spectrum and the subtraction spectrum to have an exact match of line positions, line widths and line shapes. Since each spectrometer has its own “spectrum signature” with a unique combination of line positions, widths and shapes, the water and CO2 subtraction spectra must be made on the same instrument as the sample spectra. Many of the water and CO2 lines will have a high degree of absorbance, and therefore absorption saturation effects will distort the lines. Absorbances will not be proportional to concentration. It is therefore necessary that the spectra used for water and CO2 subtraction should have nearly the same absorbance values as the values in the sample spectrum.
Detailed instructions for preparing water and CO2 subtraction spectra are given in the Analysis System Manuals.
Infrared Analysis, Inc. offers five components of hardware that permit quantitative, room temperature gas handling:
(1) Gas sampling syringes.
(2) An Easy-capture gas container.
(3) Gas sampling bags.
(4) Humidification Device (Wet-dry tube)
(5) A CO2 dispensing tube.
Return to Table of Contents