Theoretical plates capillary

Used in virtually all organic chemistry analytical laboratories, gas chromatography has a powerful separation capacity. Using distillation as an analogy, the number of theoretical plates would vary from 100 for packed columns to 10 for 100-meter capillary columns as shown in Figure 2.1. 

To minimize the multiple path and mass transfer contributions to plate height (equations 12.23 and 12.26), the packing material should be of as small a diameter as is practical and loaded with a thin film of stationary phase (equation 12.25). Compared with capillary columns, which are discussed in the next section, packed columns can handle larger amounts of sample. Samples of 0.1-10 )J,L are routinely analyzed with a packed column. Column efficiencies are typically several hundred to 2000 plates/m, providing columns with 3000-10,000 theoretical plates. Assuming Wiax/Wiin is approximately 50, a packed column with 10,000 theoretical plates has a peak capacity (equation 12.18) of... 

Microcolumns use less solvent and, because the sample is diluted to a lesser extent, produce larger signals at the detector. These columns are made from fused silica capillaries with internal diameters of 44—200 pm and lengths of up to several meters. Microcolumns packed with 3-5-pm particles have been prepared with column efficiencies of up to 250,000 theoretical plates. 

Efficiency The efficiency of capillary electrophoresis is characterized by the number of theoretical plates, N, just as it is in GC or ITPLC. In capillary electrophoresis, the number of theoretic plates is determined by... 

First, solutes with larger electrophoretic mobilities (in the same direction as the electroosmotic flow) have greater efficiencies thus, smaller, more highly charged solutes are not only the first solutes to elute, but do so with greater efficiency. Second, efficiency in capillary electrophoresis is independent of the capillary s length. Typical theoretical plate counts are approximately 100,000-200,000 for capillary electrophoresis. 

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 experimental setup for high-speed CZE can be seen in Figure 9.8. Highspeed CZE, or fast CZE (FCZE), yielded 70 000 to 90 000 theoretical plates for the separation of amino acid mixtures. Complete separation was achieved in under 11s, using a capillary length of 4 cm (24). 

Early work relied on the use of packed columns, but all modern GC analyses are accomplished using capillary columns with their higher theoretical plate counts and resolution and improved sensitivity. Although a variety of analytical columns have been employed for the GC of triazine compounds, the columns most often used are fused-silica capillary columns coated with 5% phenyl-95% methylpolysiloxane. These nonpolar columns in conjunction with the appropriate temperature and pressure programming and pressure pulse spiking techniques provide excellent separation and sensitivity for the triazine compounds. Typically, columns of 30 m x 0.25-mm i.d. and 0.25-qm film thickness are used of which numerous versions are commercially available (e.g., DB-5, HP-5, SP-5, CP-Sil 8 CB, etc.). Of course, the column selected must be considered in conjunction with the overall design and goals of the particular study. 

Figure 1.17 Separation of large ring polycyclic aroaatic hydrocarbons extracted from carbon black on a 1.8 x 0.2 n I.D. fused silica capillary column packed with 3 micrometer spherical octadecylsllanized silica gel eluted with a stepwise solvent gradient at a flow rate of 1.1 mlcroliters/min with an inlet pressure of about 360 atmospheres. Under isocratic conditions this column yielded ca. 225,000 theoretical plates. (Reproduced with permission from ref. 238. Copyright Friedr. Vieweg t Sohn).

The selection of the column type is mainly determined by the composition of the sample. In general open-tubular (capillary) columns are preferred for low-density (gas-like) SFC, whereas packed columns are most useful for high-density (liquid-like) SFC. Open-tubular columns can provide a much larger number of theoretical plates than packed columns for the same pressure drop. Volumetric flow-rates are much higher in packed column SFC (pSFC) than in open-tubular column SFC (cSFC), which makes injection and flow control less problematic. 

The main interest in cSFC comes from the high efficiency that can be obtained for involatile samples. The capillary column has the advantage of being able to chromatograph many analytes without additional solvent modifiers. cSFC generates two to three orders of magnitude more theoretical plates for a given separation than a typical packed column of 5 xm particles. 

In TLC the stationary phase is pre-wet by volatile components in the mobile phase present in the vapour phase of the chromatographic chamber. The mobile phase is at the bottom of the developing chamber and advances on the stationary phase its movement depends on capillary forces. The stationary phase is equilibrated by the mobile phase front during its movement. Separations obtained under capillary flow controlled conditions are limited to a maximum of about 5000 theoretical plates. Forced-flow development requires an external force to move the mobile phase through the layer. 

Because HPLC and HPCE are based on different physico-chemical principles, HPCE may be expected to address areas in which HPLC has shortcomings [884]. One such area is time of separation. In terms of speed of analysis, selectivity, quantitation, methods to control separation mechanism, orthogonality, CE performs better than conventional electrophoresis and varies from HPLC (Table 4.49). CE has very high efficiency compared to HPLC (up to two orders of magnitude) or GC. For typical capillary dimensions 105—106 theoretical plates are common in CE compared to 20 000 for a conventional HPLC column and... 

Correlation was found between domain size and attainable column efficiency. Column efficiency increases with the decrease in domain size, just like the efficiency of a particle-packed column is determined by particle size. Chromolith columns having ca. 2 pm through-pores and ca. 1pm skeletons show H= 10 (N= 10,000 for 10 cm column) at around optimum linear velocity of 1 mm/s, whereas a 15-cm column packed with 5 pm particles commonly shows 10,GOO-15,000 theoretical plates (7 = 10—15) (Ikegami et al., 2004). The pressure drop of a Chromolith column is typically half of the column packed with 5 pm particles. The performance of a Chromolith column was described to be similar to 7-15 pm particles in terms of pressure drop and to 3.5 1 pm particles in terms of column efficiency (Leinweber and Tallarek, 2003 Miyabe et al., 2003). Figure 7.4 shows the pressure drop and column efficiency of monolithic silica columns. A short column produces 500 (1cm column) to 2500 plates (5 cm) at high linear velocity of 10 mm/s. Small columns, especially capillary type, are sensitive to extra-column band... 

The unrestricted flow of carrier gas through the centre of capillary columns results in a much smaller pressure drop per metre than for packed columns. They can therefore be made very much longer and will generate many more theoretical plates, i.e. up to about 150,000 plates per 25 metres compared with a few thousand for a 2-metre packed column. A narrow bore and thin layer of stationary phase are essential to promote rapid mass... 

If 10,000 theoretical plates can be generated on a packed column and 250,000 theoretical plates can be generated on a capillary column assuming k = 5, what selectivity is required on each column to obtain a resolution greater than 1.5 Use this to explain why 10 times more different liquid phases have been used for packed column GC versus capillary GC. 

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