Capillary choice

The most common mobile phases for GC are He, Ar, and N2, which have the advantage of being chemically inert toward both the sample and the stationary phase. The choice of which carrier gas to use is often determined by the instrument s detector. With packed columns the mobile-phase velocity is usually within the range of 25-150 mF/min, whereas flow rates for capillary columns are 1-25 mF/min. Actual flow rates are determined with a flow meter placed at the column outlet. 

Viscometers may be separated into three main types capillary, rotational, and moving body. There are other kinds, usually designed for special apphcations. For any given type there usually is a choice of several different instmments. The choice depends on the particular requirements of the investigator and the price range. 

The original Ostwald viscometer has been modified in many ways, and a number of different versions are on the market (Table 4) (21). Most are available with a wide choice of capillary diameters and therefore a number of viscosity ranges. A number of viscometers are described in ASTM D445, which also Hsts detailed recommendations on dimensions and methods of use. 

The most widely used method of analysis for methyl chloride is gas chromatography. A capillary column medium that does a very good job in separating most chlorinated hydrocarbons is methyl siUcone or methyl (5% phenyl) siUcone. The detector of choice is a flame ionisation detector. Typical molar response factors for the chlorinated methanes are methyl chloride, 2.05 methylene chloride, 2.2 chloroform, 2.8 carbon tetrachloride, 3.1, where methane is defined as having a molar response factor of 2.00. Most two-carbon chlorinated hydrocarbons have a molar response factor of about 1.0 on the same basis. 

For capillary columns fused siHca is the material of choice for the column container. It has virtually no impurities (<1 ppm metal oxides) and tends to be quite inert. In addition, fused siHca is relatively easily processed and manufacture of columns from this material is reproducible. In trace analysis, inertness of tubing is an important consideration to prevent all of the tiny amounts of sample from becoming lost through interaction with the wall during an analysis. 

The patient then needs to be prepared. In the case of the heel prick, a leg of the infant is massaged or warmed so as to increase circulation to the heel where the puncture is to be made. The site from which the collection of blood is made, is determined by the size of the infant. In prematures, where the fingers are extremely tiny, one has no choice but to obtain the specimen from the heel. In older children, the large toe may be used. In using the heel, one does not use the bottom of the heel because here the capillaries lie deep. One uses instead the back of the heel, where the capillaries come near the surface. Generally, sterile scapel blades or lances are used to puncture the skin and obtain the blood flow. Figure 8 illustrates the process of obtaining the specimen. 

At present, the most promising methods for synthetic colorant analysis seem to be those based on separation approaches such as HPLC and capillary electrophoresis (CE). CE is the method of choice for the determination of synthetic dyes in biological materials while HPLC is generally a more suitable method for the identification and determination of hydrophobic natural pigments, having a better sensitivity and efficiency than CE. 

When performing catalytic reactions or reactions with immobilized reactants, a bed or support has to be fiUed into a tube or capillary. The fiUing may be a bed of powder, a bed of granules or a three-dimensional material network (e.g. a polymerized foam). By special choice of the filling, e.g. very regularly sized particles, it is attempted to improve the flow characteristics. 

Lord and Pawliszyn" developed a related technique called in-tube SPME in which analytes partition into a polymer coated on the inside of a fused-silica capillary. In automated SPME/HPLC the sample is injected directly into the SPME tube and the analyte is selectively eluted with either the mobile phase or a desorption solution of choice. A mixture of six phenylurea pesticides and eight carbamate pesticides was analyzed using this technique. Lee etal. utilized a novel technique of diazomethane gas-phase methylation post-SPE for the determination of acidic herbicides in water, and Nilsson et al. used SPME post-derivatization to extract benzyl ester herbicides. The successful analysis of volatile analytes indicates a potential for the analysis of fumigant pesticides such as formaldehyde, methyl bromide and phosphine. 

The use of SPE with porous materials such as alumina, diatomaceous earth, Horisil and silica for the cleanup of fat-soluble organochlorine pesticides in fatty foods such as meat, flsh, shellfish, milk and vegetable oils has been well documented. The choice of elution solvents is critical because relatively small amounts of lipid in the final extract can cause rapid deterioration of GC capillary columns and also contaminate the gas chromatograph. A number of workers have used a porous material in tandem with Cig to effect an improved cleanup.Di Mucchio employed a multicartridge system comprising Extrelut, silica and Cig to extract organophosphorus pesticides from oils and fatty extracts. Relatively few literature applications include the pyrethroids, but Ramesh and Balasubramanian reported a simple carbon-based SPE method for the analysis of pyrethroids in vegetable oil. 

Numerous types of GC injectors have been manufactured over the past four decades. The most commonly used injection techniques have been reviewed and described by Grob, who correctly states that analysts must fully understand the techniques before they can make the most appropriate choice for their particular application(s). For most GC capillary column applications, the split/splitless, programmed-temperature vaporization (PTV) and on-column injectors remain the most popular. However, over the last few years, technology has progressed rapidly to provide injectors that allow more of the sample extract on to the GC column without overloading it. 

The principal limitation in the use of electrophoretic techniques is the lack of availability of suitable detection systems for quantitative analysis and unequivocal identification of pesticide analytes. Traditionally, either ultraviolet/visible (UVA IS) or fluorescence detection techniques have been used. However, as with chromatographic techniques, MS should be the detection system of choice. A brief comparison of the numbers of recent papers on the application of GC/MS and LC/MS with capillary elec-trophoresis/mass spectrometery (CE/MS) demonstrates that interfaces between CE... 

Slurry packing techniques are required for the preparation of efficient columns with rigid particles of less than 20 micrometers in diameter. The same general packing apparatus. Figure 4.8, can be used to pack columns by the balanced-density slurry, liquid slurry, or the viscous slurry techniques. Down-fill slurry packing is the method of choice for small bore columns and packed capillary columns. 

An exeuaple of a nodular apparatus for capillary electrophoretic separation methods, is shown in Figure 4.43 [637-639,681-684]. It Offers a choice of automated sample introduction methods with on-column detection and has a... 

For two-dimensional TLC under capillary flow controlled. conditions it should be possible to achieve a spot capacity, in theory, on the order of 100 to 250, but difficult to reach 400 and nearly impossible to exceed 500 [52,140]. Theoretical calculations indicate that by forced-flow development it should be relatively > easy to generate spot capacities well in excess of 500 with an upper bound of several thousand, depending on the choice of operating conditions. -fE... 

---