Kevin B. Thurbide

Reactive-flow luminescence detector for gas chromatography

Abstract A stable, several centimeters-long luminescent column is easily formed by a hydrogen-air mixture ascending through a glass capillary toward a glow-sustaining flame on top (which combusts the excess hydrogen with auxiliary air as a flame ionization detector). This encased glow can be used for the photometric determination of gas Chromatographic effluents of sulfur and phosphorus, in what may be termed a “reactive-flow detector” (RFD). The RFD behaves in many -though not in all- respects similar to the well-known flame photometric detector (FPD). This manuscript reports analytical figures-of-merit for an RFD prototype that are as good as, or better than, those of a typical FPD.

Characterization of low-temperature cofired ceramic tiles as platforms for gas chromatographic separations.

A gas chromatography (GC) column is fabricated within a low-temperature cofired ceramic (LTCC) tile, and its analytical properties are characterized. By using a dual-spiral design, a 100 μm wide square channel up to 15 m in length is produced within an 11 cm × 5.5 cm LTCC tile. The channel is dynamically coated with an OV-101 stationary phase that is cross-linked with dicumyl peroxide. While the uncoated LTCC tiles were able to separate a mixture of n-alkanes, the peak shapes were broad (base width of ~2 min) and tailing. In contrast to this, the coated LTCC tiles produced sharp (base width of ~8-10 s), symmetrical, well-resolved peaks for the same analytes. By using a 7.5 m long channel, about 15,000 plates were obtained for a dodecane test analyte. Further, the coated LTCC tiles were found to produce plate heights that were about 3-fold smaller than those obtained from a conventional capillary GC column of similar length, dimension, and coating operated under the same conditions. As a result, test analyte separations were slightly improved in the LTCC tiles, and their overall performance fared well. In terms of temperature programming, it was found that a series of n-alkanes separated on the LTCC tile provided a cumulative peak capacity of around 54 peaks when using C₈ to C₁₃ as analyte markers. Results indicate that LTCC tiles provide a viable and useful alternative platform for performing good quality GC separations.

Chromatography Using a Water Stationary Phase and a Carbon Dioxide Mobile Phase

A novel chromatographic separation method is introduced which employs water (saturated with CO(2)) as a stationary phase and CO(2) (saturated with water) as a mobile phase. Since water and CO(2) have little miscibility, conditions can be attained that create a stationary phase of water lining the inside of an uncoated stainless steel capillary. Because altering temperature and pressure can change both the density of the mobile phase and the polarity of the stationary phase, these experimental parameters offer good flexibility for optimizing separations and allow for different gradient programmed separation options. Further, since this method is free of organic stationary and mobile phase components, it is environmentally compatible and allows the use of universal flame ionization detection. This system offers very good sample capacity, peak symmetry, and retention time reproducibility (∼1% RSD run-to-run, ∼4% RSD day-to-day). Analytes such as alcohols, carboxylic acids, phenols, and tocopherols are employed to investigate this relatively inexpensive and robust method. As an application, the system is used to quantify ethanol in alcoholic beverages and biofuel and to analyze caffeine levels in drinks. In all cases, quantitative results are obtained with quick throughput times and often little need for sample preparation.

Quenching-resistant multiple micro-flame photometric detector for gas chromatography.

A multiple flame photometric detector (mFPD) based on many flames operated in series is introduced for the detection of sulfur and phosphorus compounds. The method employs attributes of a previously developed micro counter-current flame technique to readily establish any number of very small compact flames inside a narrow quartz tube. Results show for the first time that a five flame mFPD mode can improve hydrocarbon quenching resistance nearly 20-fold relative to a single flame (i.e., conventional FPD) mode, and nearly 10-fold relative to a two flame (i.e., dual FPD) mode. Under these conditions, the five flame mFPD mode is shown to maintain about 60% of its original analyte chemiluminescence even in the presence of over 100 mL/min of methane flow into the detector. In contrast to a conventional dual FPD device, the five flame mFPD mode also provides analyte sensitivity that is similar to a conventional FPD. Of note, the mFPD yields minimum detectable limits for sulfur and phosphorus of 4 x 10(-11) g S/s and 3 x 10(-12) g P/s respectively. Analyte selectivity over hydrocarbons, signal reproducibility, and response equimolarity are also improved in the mFPD, making it a potentially useful detector for applications in gas chromatography.

Quenching-free reactive-flow photometry☆

The reactive-flow detector (RFD) behaves in many aspects like the typical flame photometric detector (FPD) for gas chromatography, thereby strongly suggesting that it, too, may be subject to severe, analytically deleterious quenching effects by hydrocarbons. However, tests carried out with compounds of the prominent FPD analytes sulfur, phosphorus, tin and manganese demonstrate —for all their emitting species— that the quenching of chemiluminescence by hydrocarbons does not occur in the RFD. A mechanistic hypothesis involving the oxygen atom is put forth in an attempt to rationalize this important difference between conventional flame and reactive flow.

Acoustic flame detector for gas chromatography

A novel gas chromatography detector is described that uses acoustic signals from a partly premixed hydrogen-air flame burning on top of a capillary. The device, referred to as the acoustic flame detector (AFD), is based on the measurement of the frequency of acoustic transients generated at the burner under a range of operating conditions. The presence of trace amounts of analyte in the flame was found to increase the frequency of these sonic bursts from the baseline level of ∼100 Hz. The response of the AFD for n-dodecane, measured as the shift in frequency, was determined to be linear over ∼3 orders of magnitude, with a minimum detectable level of about 1-5 ng C/s using the current system. The sensitivity correlates roughly with carbon content, except for certain organometallics (Sn, Mn), which gave substantially enhanced signals. Some tailing was observed but became serious only for particular types of organometallics. The noise of the system was predominantly of the 1/f type. The effects of flow conditions, burner geometry, and flame gas constituents were investigated. The oscillations could be followed by acoustic, visual, electrical, and optical means. The AFD mechanism is shown to involve oscillatory chemical kinetics, in which the flame front (the inner cone) temporarily enters a few millimeters into the capillary during each cycle, thereby creating the acoustic signal.

Analysis of organotin compounds by gas chromatography–reactive-flow detection

The gas chromatographic (GC) reactive-flow detector (RFD) responds strongly to organotin compounds. The system yields over four orders of linearity with a minimum detectable amount of 8 x 10(-16) g Sn/s (at S/N = 2). The RFDs selectivity towards tin over carbon is approximately 2.5 x 10(5) g C/g Sn. The spectral emission includes a surface luminescence centered at 390 nm and a gas-phase luminescence centered at 470 nm. These findings suggest that the GC-RFD could serve as a sensitive and selective tool for the analysis of organotin compounds.

Packed Column Supercritical Fluid Chromatography Using Stainless Steel Particles and Water As a Stationary Phase

Stainless steel (SS) particles were demonstrated as a novel useful support for a water stationary phase in packed column supercritical fluid chromatography using a CO2 mobile phase. Separations employed flame ionization detection, and the system was operated over a range of temperatures and pressures. Retention times reproduced well with RSD values of 2.6% or less. Compared to analogous separations employing a water stationary phase coated onto a SS capillary column, the packed column method provided separations that were about 10× faster, with nearly 8-fold larger analyte retention factors, while maintaining good peak shape and comparable column efficiency. Under normal operating conditions, the packed column contains about 131 ± 4 μL/m of water phase (around a 5% m/m coating), which is over 25× greater than the capillary column and also affords it a 20-fold larger sample capacity. Several applications of the packed column system are examined, and the results indicate that it is a useful alternative to the capillary column mode, particularly where analyte loads or sample matrix interference is a concern. Given its high sample capacity, this packed column method may also be useful to explore on a more preparative scale in the future.