Abnormal composition of commerical waxes revealed by supercritical fluid chromatography

Summary The analysis of natural waxes is a complicated process because they occur as complex mixtures. A study using supercritical fluid chromatography with packed columns made it possible to observe the behavior of each family of hydrocarbons, fatty esters, alcohols, acids and triglycerides. The latter were then separated according to their function type and alkyl chain lengths using octadecyl silica as stationary phase. With a polar modifier added to the supercritical fluid, it was possible to analyse certain waxes. Composition anomalies were observed which related to an overabundance of certain compounds which, in excess, are harmful to the quality of waxes intended for use in cosmetics.     

Evaluation of a microHPLC system dedictaed to packed capillary column liquid chromatography

Miniaturization and optimization of the solvent delivery system, mixing device, and detection system for gradient elution at few μl/min is the most important objective of instrumental development in microHPLC using packed capillary columns. Instrumental solutions and evaluation of the performence of a dedicated system for automatic gradient elution with packed capillary columns are reported. Retention time precision shown buy the system results in an RSD of 0.20–0.52% for a PAH model mixture eluted under gradient conditions at few μl/min. Compositional accuracy of gradient profiles is also demonstrated.     

Low flow rate modifier addition in packed capillary column supercritical fluid chromatography

A new method to accurately deliver small amounts (0.5 to 20 mol%) of modifier into CO₂ was used to study the effects of three different modifiers (methanol, water, and formic acid) in packed capillary column SFC. The method allows the use of different modifiers, with minimal instrument modification. The effects of the different modifiers at different concentrations on retention and peak shape are shown by analyzing a polarity test mixture and a sample of free fatty acids.     

Rapid determination of phytanic acid in human blood serum by selectivity tuning in packed column SFC

A new packed column SFC method has been developed for the determination of phytanic acid in human blood serum. Because of the low viscosity and high diffusion coefficient of supercritical carbon dioxide, several columns can be connected in series, significantly improving separation. Series connection of columns which differ in their selectivity enables the adjustment of the total selectivity towards the individual separation problem (‘selectivity tuning’). In this instance it was possible, after transesterification into their ethyl esters, to separate all the fatty acids in human blood serum, including phytanic acid, by coupling three columns (silica, amino-propyl, and RP8) in series.     

Temperature‐Programmed Packed Capillary Liquid Chromatography Coupled to Fourier‐Transform Infrared Spectroscopy

Temperature‐programmed packed capillary liquid chromatography has been coupled off‐line to Fourier‐transform infrared spectroscopy, utilizing a commercially available interface with a pneumatic nebulizer rebuilt to handle low flow rates at elevated temperatures. The modified interface showed excellent performance with regard to non‐aqueous reversed phase separations of polymer additives, resulting in constructed Gram‐Schmidt chromatograms comparable to chromatograms obtained using UV detection. The spray of the in‐house constructed nebulizer was not influenced by temperature changes of the column effluent, and hence temperature‐programmed gradient separations could be used successfully. The relative standard deviation of peak height was 4.4% (n = 5) and the mass limit of detection was determined to be about 40 ng, using a polymer antioxidant as model compound. The present instrumental coupling has been used for characterization of the antioxidant Irgafos P‐EPQ.     

High efficiency packed column supercritical fluid chromatography of sulfonylurea herbicides and metabolites from large water samples

Summary Five sulfonylurea herbicides were separated by SFC on both a 25 cm and a 1.6 meter packed column. The former produced rapid analysis, the latter allowed high resolution of a complex mixture containing the solutes of interest. The solutes were simultaneously detected with UV, nitrogen-phosphorus (NPD), and electron capture (ECD) detectors. Peaks of breakdown products of sulfonylureas were characterized by their UV spectra and the presence or absence of nitrogen and chlorine from their NPD and ECD response. Both parent and breakdown products of sulfonylureas were on-line extracted from large water samples with detection limits as low as 50 parts per trillion.     

A correlation for yield stress fluid flow through packed beds

Relatively few correlations are available for non-Newtonian fluid flows through packed beds, even though such fluids are frequently used in industry. In this paper, a correlation is presented for yield stress fluid flow through packed beds. The correlation is developed by introducing the yield stress model in place of the Newtonian model used in deriving Erguns equation. The resulting model has three parameters that are functions of the geometry and roughness of the particle surfaces. Two of the parameters can be deduced in the limit as the yield stress becomes negligible and the model reduces to Erguns equation for Newtonian fluids. The third model parameter is determined from experimental data. The correlation relates a defined friction factor to the dimensionless Reynolds and Hedstrom numbers and can be used to predict pressure drop for flow of a yield stress fluid through a packed bed of spherical particles. Conditions for flow or no-flow are also determined in the correlation. Comparison of model calculations, between a Newtonian and a yield stress fluid for flow penetration into a packed bed of spheres, shows the yield stress fluid initially performs similar to the Newtonian fluid, at large Reynolds numbers. At lower Reynolds numbers the yield stress effect becomes important and the flow rate significantly decreases when compared to the Newtonian fluid.