The development and evaluation of analytical methods for the analysis of trace levels of moisture in high purity gas samples

Hickman Mosdell, B. L.
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Three methods, for the analyses of low levels of moisture in gas samples, were developed and optimized. The analytical techniques included Fourier Transform Infrared Spectroscopy (FTIR) and Pulsed Discharge Helium Ionization/Gas Chromatography (PDHID/GC). The methods included the direct analyses of moisture in gas samples using FTIR as well as the analysis of acetylene (C2H2) by FTIR and GC/PDHID. For the latter methods, the purpose was to convert the moisture in a gas sample to C2H2 by hydrolization of the calcium carbide (CaC2) with moisture to C2H2 and then analyze the resulting C2H2 content by FTIR or GC/PDHID. The C2H2 result was then converted back to moisture to obtain the moisture content of the sample. The FTIR moisture method developed provided eleven different wavenumbers for quantitation providing a wide analytical scope, specifically in complex gas matrices, where there is often peak overlap between matrix and moisture. A heated eight meter glass long path gas cell and a mercury cadmium telluride (MCT) detector were utilized. The FTIR method required much greater volumes of sample than the GC method but allowed for direct analysis of moisture without prior conversion to acetylene. Moisture permeation standards were used for calibration and the LOD’s ranged from 0.5 to 1 ppm with quantification possible from 0.5 to 10ppm. For the FTIR C2H2 method various concentration ranges were established from 50 up to 2000 ppm. Three wavenumbers were evaluated for C2H2 and methane was introduced as an internal standard. The use of methane as an internal standard provided better r2 values on the calibration data than for the tests run without internal standard. A gas chromatographic (GC), pulsed discharge helium ionization detector (PDHID) method for the determination of moisture content in small quantities of gases, based on the conversion of the moisture to acetylene (C2H2) prior to analysis, was developed. The method developed on the GC/PDHID for C2H2, provided a quantitation range from 0.6 to 7.7 ppm. Conversion of the moisture to acetylene was achieved by hydrolysing an excess of calcium carbide (CaC2) in a closed reaction vessel with a measured volume of a sample containing a known quantity of moisture. The gaseous reaction mixture was transferred, using helium (He) carrier gas, to a GC/PDHID, set up with “sample injection and heart cut to detector” to prevent matrix disturbances on the PDHID, for analysis. The acetylene concentration values thus obtained were converted back to moisture values and percentage recoveries calculated. A similar conversion process was applied on FTIR. The conversion of moisture to C2H2 using CaC2 was tested and proven to be viable. Quantification was not possible as the available sample holder could not be adequately sealed to prevent air ingress. This led to higher C2H2 values than expected. This process can be optimized by the design and production of a sealed sample holder.
A Dissertation submitted in fulfillment of the requirements for the degree Master of Science In the Faculty of Sciences at the University of the Witwatersrand, Johannesburg Johannesburg, January 2015