Capillary peak shape

The effects of pH on electrokinetic velocities in micellar electrokinetic chromatography was studied by using sodium dodecyl sulfate solutions [179]. Micellar electrokinetic capillary chromatography with a sodium dodecyl sulfate pseudostationary phase has been used to determine the partition constants for nitrophenols, thiazolylazo dyes, and metal chelate compounds [180]. A similar technique was used to separate hydroquinone and some of its ether derivatives. This analysis is suitable for the determination of hydroquinone in skin-toning creams [181]. The ingredients of antipyretic analgesic preparations have also been determined by this technique [182], The addition of sodium dodecyl sulfate improves the peak shapes and resolution in chiral separations by micellar electrokinetic chromatography [183]. 

P. Kuban and P.C. Hauser, Effects of the cell geometry and operating parameters on the performance of an external contactless conductivity detector for microchip electrophoresis, Lab Chip, 5 (2005) 407-415. J.G.A. Brito-Neto, J.A.F. da Silva, L. Blanes and C.L. do Lago, Understanding capacitively coupled contactless conductivity detection in capillary and microchip electrophoresis. Part 2. Peak shape, stray capacitance, noise, and actual electronics, Electroanalysis, 17 (2005) 1207-1214. 

Sample introduction is a major hardware problem for SFC. The sample solvent composition and the injection pressure and temperature can all affect sample introduction. The high solute diffusion and lower viscosity which favor supercritical fluids over liquid mobile phases can cause problems in injection. Back-diffusion can occur, causing broad solvent peaks and poor solute peak shape. There can also be a complex phase behavior as well as a solubility phenomenon taking place due to the fact that one may have combinations of supercritical fluid (neat or mixed with sample solvent), a subcritical liquified gas, sample solvents, and solute present simultaneously in the injector and column head [2]. All of these can contribute individually to reproducibility problems in SFC. Both dynamic and timed split modes are used for sample introduction in capillary SFC. Dynamic split injectors have a microvalve and splitter assembly. The amount of injection is based on the size of a fused silica restrictor. In the timed split mode, the SFC column is directly connected to the injection valve. Highspeed pneumatics and electronics are used along with a standard injection valve and actuator. Rapid actuation of the valve from the load to the inject position and back occurs in milliseconds. In this mode, one can program the time of injection on a computer and thus control the amount of injection. In packed-column SFC, an injector similar to HPLC is used and whole loop is injected on the column. The valve is switched either manually or automatically through a remote injector port. The injection is done under pressure. 

Despite the several detailed procedures reported for the fabrication of packed columns for CEC [14,17,20,27,30,47-50], column fabrication may still be regarded as an art. A reliable and reproducible performance of a column depends on the column fabrication. Poorly packed columns can lead to low efficiency, poor resolution, and asymmetric peak shapes. The capillary tubes typically used to fabricate CEC columns are fused silica tubes with inner diameters of 100 pm or less, with 50 and 75 pm I.D. being the most popular. The small inner diameter allows for heat dissipation, which is generated by the applied electric field. Packing such columns is an elaborated process and a skill that requires experience. 

In the SCX systems no amine additives are necessary to improve peak shape, so this raises the possibility of MS detection. A mixture of TCAs was analyzed by Spikmans et al. [129] using an automated capillary electrochroma-... 

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