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Gas Chromatography (GC) is one of the most important and widely used tools in analytical chemistry. However, they are bulky, have a longer measurement cycle, and consume a high amount of power. Micro-Gas Chromatography (µGC) is portable and energy-efficient, which allows onsite, real-time biological, forensic, and environmental analyses. This thesis presents a ready-to-deploy implementation of microfabricated gas chromatography (µGC) system capable of separating complex samples. We describe robust, modular, and scalable hardware and software architecture based on Real-Time Operating System (RTOS) and Python Graphical User Interface (GUI) integrated with various microfabricated devices to realize a fully functional µGC system. A sample heater for headspace injection, microfabricated separation column (µSC), a Photoionization Detector (PI-D), and a flow controller unit are integrated with the modular hardware and software to realize a fully functional Vacuum Outlet µGC system. We have designed a novel auto-calibration method for temperature calibration of the microfabricated devices which does not require changing the electronic circuitry or reprogramming the device. The vacuum outlet µGC setup is tested with various mixture of analytes. For these experiments, an average relative standard deviation (RSD) for retention time repeatability of 2.5% is achieved. Data processing techniques for raw chromatograms, including baseline correction and peak detection, are implemented on a microcontroller board and tested extensively as a part of this work. A novel algorithm for multidimensional analysis for the identification of co-eluting compounds in complex samples is implemented with a prediction accuracy of 94%. / Master of Science / Toxic volatile organic compounds (VOCs) such as benzene and toluene found in gasoline and xylene used in ink, rubber, and leather industries are of concern as they are present at elevated concentrations due to their higher vapor pressure. Sufficient exposure to these toxicants, even at lower concentrations like 100 parts-per-billion-volume (ppbv), may cause adverse health effects. Gas Chromatography (GC) has been the established method for assessing the presence and concentration of VOCs in the environment. Traditional GC systems are bulky, power-hungry, expensive, and require expert supervision for analysis. Recent research in microelectromechanical systems (MEMS) has reduced the size of the GC components, also called micro-GC (µGC), while improving the performance. The majority of the research and development of µGC is aimed at advancing microfabricated components such as preconcentrators, separation columns, and gas detectors. However, the integration of these different components is an important topic that requires more investigation. In this thesis, we present a robust and scalable software and hardware architecture that can be used to develop a portable and modular µGC system. The thesis discusses different experiments to calibrate various microfabricated devices, which are then used to build a fully modular µGC system. We show the separation capacity of the modular µGC system by passing complex compounds like kerosene and diesel. As the chromatogram from the µGC system has noise, the second part of the thesis explores data analysis techniques such as baseline correction, peak detection. These data analysis tools are used to filter the noise, detect relevant peaks in the chromatograms, and identify the compounds in a complex sample.

If the gas chromatographic retention behavior of a compound is known under isothermal conditions at several temperatures, then it is possible to predict accurately the retention time under temperature programmed conditions. This work details the calculations required to perform such predictions. A discussion of isothermal and temperature programmed retention is presented, along with a discussion of carrier gas flow relationships. These theories are then applied to the problem of predicting temperature programmed retention times from isothermal data. It is shown that accurate and precise predictions are possible for many situations. These predicted retention times are then applied to qualitative analysis by the use of retention indices. An architecture for a retention time or index database is proposed. Finally, the use of gas chromatography for the determination of thermodynamic quantities and gas viscosities is demonstrated. / Ph. D.

A digital computer was used to measure accurate gas chromatographic peak symmetry, position and dispersion by central statistical moments. Benzene samples were chromatographed on squalane for columns of 3, 6 and 12 foot lengths and 1/8", 1/ 4" and 1/2" diameters as a function of sample size. Peak symmetry was monitored by measuring skew, γ₁ , and "excess," γ₂ two quantities derived from the higher central moments. Skew was found to increase in a positive manner for tailing peaks, pass through a maximum and approach a limiting step form for extremely overloaded columns. Skew could be used to indicate saturation of the liquid phase when it passes through a maximum. Negative skew for fronting peaks also approached a zero limiting form. Excess, γ₂ was found to decrease rapidly for all columns. A few microliters of sample were sufficient to cause significant negative values of excess. Excess provides a semi-quantitative measure of column capacity. Three general types of peak shapes were observed with increasing sample sizes: 1) gaussian behavior at very low sample sizes; 2) distorted peaks suitable characterized by central moments at normal analytical size samples; and 3) highly distorted peaks at larger sample sizes where central moments no longer reflect the step shapes observed. Moments can be used to set limits on sample sizes which will produce these highly distorted peaks. Two moment related measures of skewness were also calculated. Pearson’s skew, (Mean - Mode)/(variance)^½, along with Pearson’s β, γ measure of skewness, were found to qualitatively reflect peak shape behavior only in the region of analytical sample sizes. Pearson's skew is subject to difficult interpretation due to equivalent modal values for large samples and the β, γ measure was insensitive to fronting peaks. Third and fourth central moments were observed to have regular behavior as a function of sample size. A moment definition of resolution was derived R = 0.5 (M(1)₂ - M(1)₁) /( √M(2)₁ + √M(2)₂ ) where M(1) = mean and M(2) = variance. This definition was used to compare solvent efficiency for the separation of benzene and cyclohexane on three liquid phases, squalane, dinonalphalate and TRIS. In terms of equivalent throughput, defined as moment resolution per unit time per gram of sample, TRIS was found to be 175 times more selective than squalane. A preparative chromatograph was built with four thermal conductivity detectors at 50' intervals in a 200' x 3/8" column. Column efficiency was measured by comparison of moment parameters at the end of each 50' section. The column was operated both at normal, high pressure drop (ambient outlet pressure) and low differential pressure (constricted outlet). The condition of high pressure drop caused acceleration of samples through the last two column sections and resulted in much poorer column efficiency. The low differential pressure column, inlet 350 psi, outlet approximately 150 psi produced a more linear velocity and greater column efficiency. In fact 100 feet of the low differential pressure column generated the same resolution as 200 feet of the high pressure column. For most chromatographic peaks manual methods of peak evaluation are subject to significant operator errors due to the subjective nature of assigning base width and peak retention time. The use of moments greatly increases the accuracy of two important measurements; (1) retention time as measure from the first moment and (2) resolution for preparative scale samples as measured from the first and second moments. The method of moments provides an accurate means of measuring retention time, dispersion, resolution and preparative scale equivalent throughput. / Ph. D.

The chromatographic properties of various silicone stationary phases for capillary gas chromatography have been extensively studied, yet the properties of nonsilicone phases have not been so well investigated. The most popular nonsilicone phases are the high molecular weight polyethylene glycols (HMW PEG) which are commercially available in a wide range of molecular weights, cross-linkable and uncross-linkable (Carbowax 2OM and 4OM, the Superox series, etc.). Their most outstanding features are their unique polarity and selectivity; for this reason these phases are widely used in the analysis of aqueous solutions, essential oils, and perfumes. Unfortunately HMW-PEG's are very sensitive to slight differences in preparation and handling procedures which can cause analyses to differ with each laboratory, each column, and even each use. HMWâ PEG's also suffer from low temperature stability, a high minimum allowable operating temperature, and have lower diffusion coefficients than silicone phases. This study examines the efficiency differences of eight columns differing only in immobilization procedure and added functional groups. Comparison is made using HETP versus u and separation number (TZ) versus u curves. These curves offer important information, in particular, the effect of carrier gas, u, column operating temperature, degree of cross-linking, and cross-linking temperature on chromatographic efficiency and separation number. In addition, the contributions of the CL (resistance to mass transfer in the liquid phase) and DL (diffusion coefficient in the liquid phase) terms in the Golay equation are calculated [1]. Solids at room temperature, PEG stationary phases undergo a solid-liquid phase transition within their useful temperature range. The effect of this transition on the chromatographic properties is investigated using efficiency, separation number, capacity ratio, and retention index versus temperature curves. Four more columns, in addition to the eight mentioned above, demonstrate the influence of end-groups and the molecular weight of the stationary phase on the phase transition temperature range. / Master of Science

Wide-bore, fused-silica capillary columns can be an excellent replacement for packed columns in many cases. They can provide higher surface inertness and thermal stability, as well as higher efficiency or speed of analysis. Wide-bore, open-tubular (WBOT) columns with thick films have higher sample capacities than conventional narrow-bore capillary columns and can be used in unmodified packed-column gas chromatographs. The majority of gas chromatographic analyses are still performed using packed columns. Many chromatographers associate open-tubular columns exclusively with split injection, often perceived as less repeatable or quantitative. Also, many packed-column methods use application-specific stationary phases which are not readily available on capillary columns. WBOT columns with standard phases can often be substituted due to higher available efficiencies. While several studies have been published on qualitative differences, there is little comparative quantitative data available on O.53â mm I.D. and packed columns. / Master of Science

A ready-to-deploy implementation of microfabricated gas chromatography (microGC) system characterized for detecting hazardous air pollutants (HAPs) at parts-per-billion (ppb) concentrations in complex mixtures has been described. A microfabricated preconcentrator (microPC), a MEMS separation column with on-chip thermal conductivity detector (microSC-TCD), the flow controller unit, and all the necessary flow and thermal management as well as user interface circuitry are integrated to realize the fully functional microGC system. The work reports extensive characterization of microPC, microSC and micro]TCD for target analytes: benzene, toluene, tetrachloroethylene, chlorobenzene, ethylbenzene, and p-xylene. Limit of Detection (LOD) of ~1 ng was achieved, which corresponds to 10 min sampling time at a flow rate of 1 mL/min for analyte present at ~25 ppbv concentration. An innovative method for generating very sharp injection plugs from the microPC even in the presence of flow sensitive detectors like micro]TCD is described. A one-to-one comparison between microGC system and conventional Automated Thermal Desorption-Gas Chromatograph-Flame Ionization Detector (ATD GC-FID) system for real gasoline samples in simulated car refueling scenario is reported. / Master of Science

The experimental parameters controlling the rate and mechanism of the decomposition of compounds and the products formed, in a moving carrier gas stream were investigated. The parameters studied included the effects of pyrolysis temperature, sample size, sample weight, flow rate of the carrier gas, the method of introducing the sample into the pyrolysis unit. An apparatus for pyrolysis-gas chromatography, using tho commonly used boat and furnace technique, was developed. Commercial grade sodium dodecylbenzene sulfonate was chosen for a model compound. The optimum conditions for the pyrolysis-gas chromatographic analysis of this material were established by the careful study of the experimental parameters. The most serious limitations to this method of pyrolysis-gas chromatography appeared to be the strong dependence on the sample size and tho dependence on pyrolysis temperature, i.e., on the rate at which the sample was brought to the pyrolysis temperature. As the size of the sample was increased the amount of residue in the boat also increased. Also, although the majority of the sample was pyrolyzed at 580°C the amount of residue would decrease as the temperature was raised to a maximum of 710°C. A certain amount of residue always remained in the boat. The residue can be explained as the product of secondary reactions occurring between the initial pyrolysis intermediates (free radicals) and the unpyrolyzed portion of the sample. In an attempt to eliminate these effects of secondary reactions a new technique of pyrolysis-gas chromatography by direct injection of solutions was developed. By handling the samples in dilute solution it was shown that a much smaller sample could be pyrolyzed such that the probability or secondary reactions was greatly reduced. Also the very small samples allow an apparent instantaneous heating of the samples to a given pyrolysis temperature. This approach offers a means of obtaining the simplest possible products from the pyrolysis of a compound, therefore offering a more accurate insight into the mechanism of the pyrolysis. These products then offer a means of establishing the structure of the original compound. Using this technique a method was developed for analyzing aqueous solutions containing the alkylbenzene sulfonates. This method provides not only a measure of the total detergent present but also differentiates between the various alkyl groups found in the commercial products. The alkyl groups form the 1-alkenes which can be easily identified chromatographically. The conditions for this analysis along with curves showing the products obtained from the pyrolysis of samples with both straight and branched alkyl groups are given. While the majority of the work done here was with aqueous solutions an attempt was made to determine the stability or some of the common organic solvents under such pyrolysis conditions. Those solvents studied were methylene chloride, chloroform, carbon tetrachloride, methanol, ethanol, and acetone. All of these solvents were round to be stable up to 500°C; however, at temperatures greater than this the decomposition of the solvents limits their use. The technique of pyrolysis-gas chromatography by direct injection or solutions was also applied to certain amino acids in ethanol-water solutions. The results were again much more accurate than those found with the boat technique. This technique was also shown to be useful in determining the structure of organic chelates bound to metal atoms. Solutions of copper II and chromium III acetyl-acetonates in chloroform were pyrolyzed and the product identified as acetylacetone. This offers a means of determining both the number and type of chelates bound to a given metal atom. / Ph. D.

Ventilation in underground mines is vital to creating a safe working environment. Though there have been numerous improvements in mine ventilation, it is still difficult to ascertain data on the state of the ventilation system following a disaster in which ventilation controls have been potentially damaged. This information is important when making the decision to send rescue personnel into the mine. By utilizing tracer gas techniques, which are powerful techniques for monitoring ventilation systems, especially in remote or inaccessible areas, analysis of the ventilation system immediately following a mine emergency can be more rapidly ascertained. However, the success of this technique is largely dependent on the accuracy of release and sampling methods. Therefore, an analysis of sampling methods is crucial for rapid response and dependable results during emergencies. This research project involves evaluating and comparing four well-accepted sampling techniques currently utilized in the mining industry using sulfur hexafluoride, an industry standard, as the tracer gas. Additionally, Solid Phase Microextraction (SPME) fibers are introduced and evaluated as an alternative sampling means. Current sampling methods include plastic syringes, glass syringes, Tedlar bags, and vacutainers. SPME fibers have been successfully used in a variety of industries from forensics to environmental sampling and are a solvent-less method of sampling analytes. To analyze these sampling methods, samples were taken from a 0.01% standard mixture of SF6 in nitrogen and analyzed using electron capture gas chromatography (GC). The technical and practical issues surrounding each sampling method were also observed and discussed. Furthermore, the use of multiple tracer gases could allow for rapid assessment of the functionality of ventilation controls. This paper describes experimentation related to the determination of a novel mine tracer gas. Multiple tracer gases greatly increase the level of flexibility when conducting ventilation surveys to establish and monitor controls. A second tracer would substantially reduce the time it takes to administer multiple surveys since it is not necessary to wait for the first tracer to flush out of the mine which can take up to a few days. Additionally, it is possible to release different tracers at different points and follow their respective airflow paths, analyzing multiple or complex circuits. This would be impossible to do simultaneously with only one tracer. Three different tracer gases, carbon tetrafluoride, octofluoropropane, and perfluoromethlycyclohexane, were selected and evaluated on various GC columns through utilizing different gas chromatographic protocols. Perfluoromethylcyclohexane was selected as the novel tracer, and a final protocol was established that ensured adequate separation of a mixture of SF6 and perfluoromethylcyclohexane. Since there is limited literature comparing sampling techniques in the mining industry, the findings and conclusions gained from the sampling comparison study provide a benchmark for establishing optimal sampling practices for tracer gas techniques. Additionally, the determination of a novel tracer gas that can be used with and separated from SF6 using the same analytical method increases the practicality and robustness of multiple mine tracer gas techniques. This initial work will contribute to the larger project scope of determining a methodology for the remote characterization of mine ventilation systems through utilizing multiple mine tracer gases and computational fluid dynamics (CFD). This will be completed through several phases including initial laboratory testing of novel tracer gases in a model mine apparatus to develop a methodology for releasing, sampling, and modeling a mine ventilation plan and tracer gas dispersion in CFD and eventually completing field trials to validate and enhance the multiple tracer gas methodology. / Master of Science

This study concerns the effect of column temperature on selectivity in gas chromatography (GC). Reversal of peak elution order at different temperatures is observed when selectivity is sufficiently changed by changing the temperature. A study of homologous functional groups and the elution order of a test mixture was made at several temperatures, by keeping constant operating chromatographic parameters such as column head pressure, split ratio, sample concentration, injector and detector temperature. The homologous series studied were esters, carboxylic acids, ketones and alkanes. The stationary phases used were Carbowax (Supelcowax 10), and 5% diphenyl and 95% dimethyl silicone ( HP Ultra 2). The identification of each compound was confirmed by two methods : comparing retention times, and spiking the sample. The results of an investigation for accurately determining the dead time is also presented. The experimental results of using 10% methane in helium and the results of a theoretical model based on Poiseuille's equation were studied and compared. It is concluded that dead time calculations are a major source of error for the calculations in this work. In addition, a derived thermodynamic equation based on the Van't Hoff equation was obtained and used to calculate the molar enthalpy and entropy of compounds over a range of temperatures. The experimental thermodynamic values were compared with the theoretical values obtained from the Clausius- Clapeyron equation. From the data obtained, a graph of In k' (retention factor) versus 1/ temperature for a homologous series, known as a Van't Hoff plot, predicts a reversal of elution order where an intersection of two lines occur. Selectivity of the stationary phase has changed solely due to temperature effects. This can only occur when different solute/solvent interactions are present. This work is an attempt to predict when peak inversion should occur based on the Van Hoff's plot. Experimental result are presented that confirm the prediction. / Master of Science