Dead column

Fig. 6.3 A dissection of the frontal chromatogram [31]. The breakthrough curve is represented by the thick line. The two gray/hatched surfaces on the left side (Ai, A2) represent the mass of compound in the extra- and dead-column volumes. Area A3 represents the mass of the compound adsorbed to the stationary phase. Adapted with permission from Elsevier.

You observe that you are going through a lot more reversed-phase columns than you used to and your columns die earlier. Your supplier is not too unhappy, but you would like to know the cause. What does it mean to have a dead column If we exclude higher back pressure, decreased quality means a decrease in the number of theoretical plates (broad peaks, the packing is not OK) and/or a change in retention time (chemical change of the stationary phase). What possible causes should be considered ... 

At first we tried to explain the phenomenon on the base of the existence of the difference between the saturated vapor pressures above two menisci in dead-end capillary [12]. It results in the evaporation of a liquid from the meniscus of smaller curvature ( classical capillary imbibition) and the condensation of its vapor upon the meniscus of larger curvature originally existed due to capillary condensation. We worked out the mathematical description of both gas-vapor diffusion and evaporation-condensation processes in cone s channel. Solving the system of differential equations for evaporation-condensation processes, we ve derived the formula for the dependence of top s (or inner) liquid column growth on time. But the calculated curves for the kinetics of inner column s length are 1-2 orders of magnitude smaller than the experimental ones [12]. 

Fig. 4 illustrates the time-dependence of the length of top s water column in conical capillary of the dimensions R = 15 pm and lo =310 pm at temperature T = 22°C. Experimental data for the top s column are approximated by the formula (11). The value of A is selected under the requirement to ensure optimum correlation between experimental and theoretical data. It gives Ae =3,810 J. One can see that there is satisfactory correlation between experimental and theoretical dependencies. Moreover, the value Ae has the same order of magnitude as Hamaker constant Ah. But just Ah describes one of the main components of disjoining pressure IT [13]. It confirms the rightness of our physical arguments, described above, to explain the mechanism of two-side liquid penetration into dead-end capillaries. 

The chromatogram in Problem 4 was obtained on a 2-m column with a column dead time of 50 s. How long a column is needed to achieve a resolution of 1.5 What height of a theoretical plate is needed to achieve a resolution of 1.5 without increasing the length of the column ... 

The peripheral stiffening zone (tray ring) is generally 25 to 50 mm (1 to 2 in) wide and occupies 2 to 5 percent of the cross section, the fraction decreasing with increase in plate diameter. Peripheiy waste (Fig. 14-28) occurs primarily with bubble-cap trays and results from the inabihty to fit the cap layout to the circular form of the plate. Valves and perforations can be located close to the wall and little dead area results. Typical values of the fraction of the total cross-sectional area available for vapor dispersion and contact with the liquid for cross-flow plates with a chord weir equal to 75 percent of the column diameter are given in Table 14-6. 

Here is a tip for possible capacity increase for towers with sloped downcomers. Usually, the tray vendor doesn t use the dead area next to the bottom part of the sloped downcomer as active area if the trays are multipass, since he would require a different design for alternate trays. This area could be used for additional vapor capacity in an existing column. 

The dead volume (Vq) is the volume of mobile phase passed through the column between the injection point and the dead point. 

In practice, the retention volume of an unretained peak eluted at the dead volume (Vo), will be made up of the volume of mobile phase in the column (Vm) and extracolumn volumes, from sample valves, connecting tubes, unions, etc. (Ve)-... 

Again it is seen that only when second order effects need to be considered does the relationship become more complicated. The dead volume is made up of many components, and they need not be identified and understood, particularly if the thermodynamic properties of a distribution system are to be examined. As a consequence, the subject of the column dead volume and its measurement in chromatography systems will need to be extensively investigated. Initially, however, the retention volume equation will be examined in more detail. 

It is clear that the separation ratio is simply the ratio of the distribution coefficients of the two solutes, which only depend on the operating temperature and the nature of the two phases. More importantly, they are independent of the mobile phase flow rate and the phase ratio of the column. This means, for example, that the same separation ratios will be obtained for two solutes chromatographed on either a packed column or a capillary column, providing the temperature is the same and the same phase system is employed. This does, however, assume that there are no exclusion effects from the support or stationary phase. If the support or stationary phase is porous, as, for example, silica gel or silica gel based materials, and a pair of solutes differ in size, then the stationary phase available to one solute may not be available to the other. In which case, unless both stationary phases have exactly the same pore distribution, if separated on another column, the separation ratios may not be the same, even if the same phase system and temperature are employed. This will become more evident when the measurement of dead volume is discussed and the importance of pore distribution is considered. 

The silica dispersion showed the smallest retention volume. It should be noted, however, that the authors reported that the silica dispersion required sonicating for 5 hours before the silica was sufficiently dispersed to be used as "pseudo-solute". The retention volume of the silica dispersion gave the value of the kinetic dead volume, /.e., the volume of the moving portion of the mobile phase. It is clear that the difference between the retention volume of sodium nitroprusside and that of the silica dispersion is very small, and so the sodium nitroprusside can be used to measure the kinetic dead volume of a packed column. From such data, the mean kinetic linear velocity and the kinetic capacity ratio can be calculated for use with the Van Deemter equation [12] or the Golay equation [13]. 

It is seen that there is a good correlation between experimental and calculated values. The scatter that does exist may be due to the dead volume of the column not being precisely independent of the solvent composition. The dead volume will depend, to a small extent, on the relative proportion of the different solvents adsorbed on the stationary phase surface, which will differ as the solvent composition changes. A constant value for the dead volume was assumed in the computer program that derived the equation. 

The idea of the effective plate number was introduced and employed by Purnell [4], Desty [5] and others in the late 1950s. Its conception was evoked as a direct result of the introduction of the capillary column or open tubular column. Even in 1960, the open tubular column could be constructed to produce efficiencies of up to a million theoretical plates [6]. However, it became immediately apparent that these high efficiencies were only obtained for solutes eluted at very low (k ) values and, consequently, very close to the column dead volume. More importantly, on the basis of the performance realized from packed columns, the high efficiencies did not... 

The peak capacity of a column has been defined as the number of peaks that can be fitted into a chromatogram between the dead point and the last peak, with each peak being separated from its neighbor by 4a. The last peak of chromatogram is rather a... 

Equation (33) shows that the maximum capacity ratio of the last eluted solute is inversely proportional to the detector sensitivity or minimum detectable concentration. Consequently, it is the detector sensitivity that determines the maximum peak capacity attainable from the column. Using equation (33), the peak capacity was calculated for three different detector sensitivities for a column having an efficiency of 10,000 theoretical plates, a dead volume of 6.7 ml and a sample concentration of l%v/v. The results are shown in Table 1, and it is seen that the limiting peak capacity is fairly large. 

It is seen that a linear curve is not obtained with the use of (k ) values derived from the fully permeating dead volume and, thus, (k ) can not be used in the kinetic studies of columns. In contrast, the linear curve shown when using (k"), obtained from the use of the dynamic dead volume, confirms that (k e) values based on the excluded... 

An explosive decomposition in an ethylene oxide (EO) distillation column, similar in its results to that described in Section 7.3.2, may have been set off by polymerization of EO in a dead-end spot in the column base where rust, a polymerization catalyst, had accumulated. Such deadends should be avoided. However, it is more likely that a flange leaked the leaking gas ignited and heated an area of the column above the temperature at which spontaneous decomposition occurs. The source of ignition of the leak may have been reaction with the insulation, as described... 

Water can be trapped behind heat exchanger baffles and then suddenly vaporized by circulation of hot oil. It can also be trapped in dead-ends and U-bends in pipework (see Section 9.1.1). Such U-bends can form when one end of a horizontal pipe is raised by thermal expansion. The trays in a distillation column were damaged during startup when hot gas met water, from previous steaming, dripping down the column [3J. Section 17.12 describes an incident somewhat similar to a foamover. 

The XK column system is a medium-pressure jacketed glass column system designed for operating pressures up to 5 bar (0.5 MPa). Column dead volumes are less than 0.1% of the total column volume. Wetted materials include EPDM, TEFZEL, superpolyoxymethylene, and flurorubber. Columns use nylon nets of 10-)Lim mesh size and may be used with most SEC media with particle diameters >20 /xm. Columns are intended for use with aqueous solutions and... 

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