Open tubular columns limitations

Open tubular microcolumns also have been developed, with internal diameters of 1-50 pm and lengths of approximately 1 m. These columns, which contain no packing material, may be capable of obtaining column efficiencies of up to 1 million theoretical plates.The development of open tubular columns, however, has been limited by the difficulty of preparing columns with internal diameters less than 10 pm. 

Having established that a finite volume of sample causes peak dispersion and that it is highly desirable to limit that dispersion to a level that does not impair the performance of the column, the maximum sample volume that can be tolerated can be evaluated by employing the principle of the summation of variances. Let a volume (Vi) be injected onto a column. This sample volume (Vi) will be dispersed on the front of the column in the form of a rectangular distribution. The eluted peak will have an overall variance that consists of that produced by the column and other parts of the mobile phase conduit system plus that due to the dispersion from the finite sample volume. For convenience, the dispersion contributed by parts of the mobile phase system, other than the column (except for that from the finite sample volume), will be considered negligible. In most well-designed chromatographic systems, this will be true, particularly for well-packed GC and LC columns. However, for open tubular columns in GC, and possibly microbore columns in LC, where peak volumes can be extremely small, this may not necessarily be true, and other extra-column dispersion sources may need to be taken into account. It is now possible to apply the principle of the summation of variances to the effect of sample volume. 

The limited sample capacity and low carrier gas flow rates characteristic of open tubular column gas chromatography give rise to certain difl icultles in sample introduction. Direct sample... 

Upon substitution of the reduced parameters given above the separation time for a packed column and an open tubular column would be Identical if d 1.73 dp given the current limitations of open tubular column technology the column diameter cannot be reduced to the point %diere these columns can compete with packed columns for fast separations. This is illustrated by the practical txanple in Figure 6.3 (57). Ihe separation speed cannot be Increased for an open tubular column by increasing the reduced velocity since the reduced plate height is increased... 

Onuska and Terry [14] have described a method for the determination of chlorinated benzenes in bottom sediment deposits. Sample preparation methods using Soxhlet extraction, ultrasonic extraction or steam distillation were compared. The chlorinated benzenes were characterized by open tubular column gas chromatography with electron capture detection. In recovery studies using sediments with different organic matter contents, the steam distillation method was the most efficient. Detection limits were in the range 0.4-10pg kgy1. 

Figure 3 shows that, there might indeed, be a limited practical range of column dimensions and operating conditions tnat would make tne open tubular column a possible alternative to the packed column in LC. To separate a solute mixture with the separation ratio for the critical pair of 1.01 and an inlet pressure of 1 p.s.i would require an analysis time of 6,5... 

The curves in figure (5) show the relationship between maximum sample volume and the separation ratio of the critical pair for a fully optimized column and were obtained using equation (20) The curves give the first, indication of the limitations of open tubular columns in LC and the reason why they have not achieved the popularity and success of the packed column... 

From the curves shown in figure (5) it would appear that the very small permissible sample volume would limit the use of the open tubular column... 

The properties of open tubular columns shown in figures (I) to (6) indicate that the areas where such columns would have practical use is very restricted. At pressures in excess of 10 ps.i., and whatever the nature of the separation, whether simple or difficult, the optimum column diameters are so small that they would be exceedingly difficult to fabricate or coat with stationary phase. The maximum sample volumes and extra column dispersion that couid be tolerated would also be well below that physically possible at this time. At relatively low pressures, that Is at pressures less than 10 p.s.l. the diameter of the optimum column is large enough to fabricate and coat with stationary phase providing the separations required are difficult i.c. the separation ratio of the critical pair must be less than 1.03. However, even under these conditions the sample volume will be extremely small, the extra column dispersion restricted to an almost impossibly low limit and the analysis time would be very long Nevertheless, open tubular columns used for very difficult separations... 

Response to organic compounds is proportional to solute mass over seven orders of magnitude. The detection limit is 100 times smaller than that of the thermal conductivity detector (Table 24-5) and is reduced by 50% when N2 carrier gas is used instead of He. For open tubular columns, N2 makeup gas is added to the H2 or He eluate before it enters the detector. The flame ionization detector is sensitive enough for narrow-bore columns. It responds to most hydrocarbons and is insensitive to nonhydrocarbons such as H2, He, N2, 02, CO, C02, H2Q, NH NO, H2S, and SiF4. 

The United States Pharmacopeia (USP) test (467) describes three different approaches to measuring organic volatile impurities in pharmaceuticals. Method I uses a wide-bore coated open tubular column (G-27, 5% phenyl-95 % methylpolysiloxane) with a silica guard column deactivated with phe-nylmethyl siloxane and a flame-ionization detector. The samples are dissolved in water and about 1 p is injected. Limits are set for benzene, chloroform, 1,4-dioxane, methylene chloride, and trichloroethylene. Methods V and VI are nearly identical to method I except for varying the chromatographic conditions. For the measurement of methylene chloride in coated tablets, the headspace techniques described above are recommended. 

Despite many advantages, CEC columns packed with microparticulate sorbents do have some limitations such as the relatively large void volume between the packed particles and the slow diffusional mass transfer of solutes into the stagnant mobile phase present in the pores of the separation medium [83,84]. Alternative approaches to alleviate the problem of mass transfer and intraparticular void volume are the concepts of monolithic chromatographic beds and open-tubular columns. In mono-... 

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