Application of the Retention Index Concept in Micellar Electrokinetic Capillary Chromatography. [Erratum to document cited in CA120:123851]

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The separation of herbicides by micellar electrokinetic capillary chromatography

A method for the sepn. of a no. of herbicides consisting of chlorophenoxy acids by micellar electrokinetic capillary chromatog. (MECC) was developed. SDS, Brij 35, cetyltrimethylammonium bromide (CTAB) and MeOH were introduced into the buffers to investigate their effects on the sepn. of the herbicides. SDS combined with Brij 35 as the micellar agent was found to provide the best overall sepn. of these component

Quantitative aspects of directly coupled supercritical fluid extraction-capillary gas chromatography with a conventional split/splitless injector as interface

The quant. aspects of online supercrit. fluid extn.-capillary gas chromatog. (SFE-GC) with a split/splitless injector as interface were studied. Special attention was paid to the discrimination behavior and the reproducibility of the split/splitless interface. A simple exptl. set-up is proposed that allows accurate quantitation in online SFE-split GC. The results obtained in online SFE-GC compare favorably with those from conventional GC with split injection. Discrimination is absent when working at sufficiently high interface temps. Finally, the effects of the CO2 flow rate, interface temp. and split ratio on both discrimination and reproducibility were studie

Compressibility effects in packed and open tubular gas and supercritical fluid chromatography

The influence of the pressure drop on the efficiency and speed of anal. in packed and open tubular supercrit. fluid chromatog. (SFC) is described: methods previously developed to describe the effects of mobile phase compressibility on the performance of open tubular columns in SFC have been extended to packed columns. The Horvath and Lin equation has been used to elucidate the influence of variations in velocity, diffusivity, and capacity factor along the column on the overall efficiency of packed column SFC. In packed columns, in contrast with the situation in open tubular columns, because the diffusion coeffs., the increase in both linear velocity and capacity factor which result from a significant pressure drop cause the plate height to increase along the column. The effect of liq. decompression along the length of the column on the speed of anal. in SFC has been studied and numerical expressions derived which enable calcn. of compressibility correction factors for the plate height. Both the f1 and f2 correction factors remain very close to unity for acceptable pressure drops, which means that the pressure drop has virtually no effect on the no. of plates generated per unit time for an unretained component. For retained species, the decompression of the mobile phase across the column causes the capacity factor to increase and hence leads to increased anal. time

Application of the Retention Index Concept in Micellar Electrokinetic Capillary Chromatography

The application of the retention index concept in micellar electrokinetic capillary chromatog. (MECC) was evaluated for the identification of neutral species. Homologous series of alkylbenzenes and alkylaryl ketones were applied as retention index stds. and also for the calcn. of the micelle migration time by an iteration procedure. The relation between retention indexes, I, and octanol-H2O partition coeffs. is discussed, and DI values were calcd. from retention indexes, obtained with both anionic and cationic surfactant systems, to study the sepn. mechanism for solutes with different functionalities in MECC. The influence of the phase ratio is treated theor., and the capacity factor is linearly related to the surfactant concn., whereas the retention index is independent of the surfactant concn. The temp. dependence of the retention index was studied and the std. enthalpy, entropy, and Gibbs free energy for micellar solubilization of the sample compds. were detd., showing that the hydrophobic interaction plays a significant role in MECC ana

Use of an open-tubular trapping column as phase-switching interface in on-line coupled reversed-phase liquid chromatography-capillary gas chromatography

The applicability of open-tubular traps for phase switching in coupled RPLC—GC was studied. The phase-switching process involves sorption of the analytes of interest from a methanol—water mobile phase into the stationary phase of an open-tubular column, removal of the aqueous phase by purging the trap with nitrogen and desorption of the analytes with hexane. Water elimination carried out in this manner appears to be highly efficient. In the sorption step the sampling flow-rate and the capacity factors of the analytes in the trap are critical parameters. Using a 2 m × 0.32 mm I.D. trap with a swollen 5-μm stationary phase at flow-rates not exceeding 100 μl/min, polycyclic aromatic hydrocarbons are trapped quantitatively from 300 μl of aqueous phases containing up to 65% (v/v) of methanol. For desorption 70–125 μl of hexane are needed. These volumes are easy to handle in solvent elimination carried out using a PTV injector prior to transfer of the analytes to a GC column

29Si NMR Model Dissolution Study of the Degradation of Reversed Phases for High-Performance Liquid Chromatography

To simulate aging under chromatog. conditions, mono-, di-, and trifunctional octyl and octadecyl derivatized reversed-phase high-performance liq. chromatog. silicas were exposed to very aggressive mobile phases like the medium of 6 M NaOH in MeOH/H2O (50/50 vol./vol.). 29Si NMR was used to study the dissoln. characteristics of these phases by monitoring the concns. of the dissolving silane and silica structures. Dissoln. products of alkylchlorosilanes were used as model compds. for assignment purposes. Octadecyl phases appeared to degrade by dissoln. of the silica substrate; octadecylsilane structures were insol. under the exptl. conditions. Monofunctional octyl phases were shown to deteriorate through initial dissoln. of monomeric ligand silane particles, wheres for difunctional octyl phases, the silica backbone appeared to dissolve with the silane ligands still attached. The latter mechanism was also obsd. for the trifunctional octyl phases, but these phases resemble octadecyl phases, probably because the free ligand silane particles are almost insol. and the major cause of phase degrdn. is dissoln. of the silica substrat