Gas chromatography injection

Procedure After having maintained the above mentioned experimental conditions for gas chromatography inject 2p/ of solutions (1) through (4) sequentially. 

Procedure After having set the above experimental conditions for gas chromatography, inject 1 pi of the solutions (1) and (2) sequentially into the column. Repeat the determinations so as the ensure a consistent response. Determine the peak areas. ... 

Procedure After having maintained the aforesaid experimental parameter for gas chromatography, inject 1 g/ each of solutions (1), (2), (3) and (4) in a sequential manner. 

The object of the transfer system is to dilute the sample and provide adequate mixing to form a representative mixture for the gas chromatography injection vessel. 

Figure 24-16 Split and splitless injections of a solution containing 1 vol% methyl isobutyl ketone (b.p. 118°C) and 1 vol% p-xylene (b.p. 138°C) in dichloromethane (b.p. 40°C) on a BP-10 moderately polar cyanopropyl phenyl methyl silicone open tubular column (0.22 mm diameter x 10 m long, film thickness = 0.25 m, column temperature = 75°C). Vertical scale is the same for A-C. In D, signal heights should be multiplied by 2.33 to be on the same scale as A-C. [From R J. Marriott and P. D. Carpenter, Copillory Gas Chromatography Injection," J. Chem. Ed. 1996, 73, 96.]...

Internal standard calibration allows compensating for any variation due to matrix effects and gas chromatography injection. Prior to the extraction, a known additional analyte is added to each sample and standard. This compound is the internal standard. 

In gas chromatography (GC) the sample, which may be a gas or liquid, is injected into a stream of an inert gaseous mobile phase (often called the carrier gas). The sample is carried through a packed or capillary column where the sample s components separate based on their ability to distribute themselves between the mobile and stationary phases. A schematic diagram of a typical gas chromatograph is shown in Figure 12.16. 

Preparing a Volatile Sample Gas chromatography can be used to separate analytes in complex matrices. Not every sample that can potentially be analyzed by GG, however, can be injected directly into the instrument. To move through the column, the sample s constituents must be volatile. Solutes of low volatility may be retained by the column and continue to elute during the analysis of subsequent samples. Nonvolatile solutes condense on the column, degrading the column s performance. 

Time, Cost, and Equipment Analysis time can vary from several minutes for samples containing only a few constituents to more than an hour for more complex samples. Preliminary sample preparation may substantially increase the analysis time. Instrumentation for gas chromatography ranges in price from inexpensive (a few thousand dollars) to expensive (more than 50,000). The more expensive models are equipped for capillary columns and include a variety of injection options and more sophisticated detectors, such as a mass spectrometer. Packed columns typically cost 50- 200, and the cost of a capillary column is typically 200- 1000. 

Gas Chromatography Analysis. From a sensitivity standpoint, a comparable technique is a gas chromatographic (gc) technique using flame ioni2ation detection. This method has been used to quantify the trimethylsilyl ester derivative of biotin in agricultural premixes and pharmaceutical injectable preparations at detection limits of approximately 0.3 pg (94,95). 

The identification of benzene is most easily carried out by gas chromatography (83). Gas chromatographic analysis of benzene is the method of choice for determining benzene concentrations in many diverse media such as petroleum products or reformate, water, sod, air, or blood. Benzene in air can be measured by injection of a sample obtained from a syringe directiy into a gas chromatograph (84). 

The purity of a dicyclopentadiene stream may be expressed in terms of DCPD itself or in terms of available CPD monomer. Both analyses are deterrnined by gas chromatography (gc). The first analysis is capillary gc on a nonpolar column. The data from the analysis can be used to calculate the available CPD, assuming that all the DCPD and CPD codimers crack completely. In the second analysis the sample is charged to the gc equipment under temperature conditions (injection port 400°C) that cause essentially complete reaction of the dimers to monomers. 

K. Grob, On-Column Injection in Capillary Gas Chromatography, W. Beitsch, W. G. Jennings and P. Sandra (Series Eds), Hiithig, Heidelberg, Gemiany (1991). 

Figure 12.8 Mia ocolumn size exclusion chromatogram of a styrene-aaylonitrile copolymer sample fractions ti ansfeired to the pyrolysis system are indicated 1-6. Conditions fused-silica column (50 cm X 250 p.m i.d.) packed with Zorbax PSM-1000 (7p.m 4f) eluent, THF flow rate, 2.0 p.L/min detector, Jasco Uvidec V at 220 nm injection size, 20 nL. Reprinted from Analytical Chemistry, 61, H. J. Cortes et al, Multidimensional chromatography using on-line microcolumn liquid chromatography and pyrolysis gas chromatography for polymer characterization , pp. 961 -965, copyright 1989, with peimission from the American Chemical Society.

An on-line supercritical fluid chromatography-capillary gas chromatography (SFC-GC) technique has been demonstrated for the direct transfer of SFC fractions from a packed column SFC system to a GC system. This technique has been applied in the analysis of industrial samples such as aviation fuel (24). This type of coupled technique is sometimes more advantageous than the traditional LC-GC coupled technique since SFC is compatible with GC, because most supercritical fluids decompress into gases at GC conditions and are not detected by flame-ionization detection. The use of solvent evaporation techniques are not necessary. SFC, in the same way as LC, can be used to preseparate a sample into classes of compounds where the individual components can then be analyzed and quantified by GC. The supercritical fluid sample effluent is decompressed through a restrictor directly into a capillary GC injection port. In addition, this technique allows selective or multi-step heart-cutting of various sample peaks as they elute from the supercritical fluid... 

These small columns,(usually 10 mm X 1-4.6 mm i.d.) are normally packed with 10-40 p.m sorbents such as Cig-bonded silica, Cg-bonded silica or styrene-divinylbenzene copolymer. These sorbents are not very selective and more selective sorbents, such as the immunosorbent (94), have also been used with good results. Coupling of SPE-gas chromatography is in fact the one most often used in environmental analysis because it reaches a high level of trace enrichment, eliminates water and elutes retained compounds easily with an organic solvent that can be injected into the gas chromatograph. 

Figure 15.8 Multidimensional GC-MS separation of urinary acids after derivatization with methyl chloroformate (a) pre-column cliromatogram after splitless injection (h) Main-column selected ion monitoring cliromatogram (mass 84) of pyroglutamic acid methyl ester. Adapted from Journal of Chromatography, B 714, M. Heil et ai, Enantioselective multidimensional gas chromatography-mass spectrometry in the analysis of urinary organic acids , pp. 119-126, copyright 1998, with permission from Elsevier Science.

Figure 15.11 (a) Total ion clnomatogram of a Grob test mixture obtained on an Rtx-1701 column, and (b) re-injection of the entire clnomatogram on to an Rtx-5 column. Peak identification is as follows a, 2,3-butanediol b, decane c, undecane d, 1-octanol e, nonanal f, 2,6-dimethylphenol g, 2-ethylhexanoic acid h, 2,6-dimethylaniline i, decanoic acid methyl ester ], dicyclohexylamine k, undecanoic acid, methyl ester 1, dodecanoic acid, methyl ester. Adapted from Journal of High Resolution Chromatography, 21, M. J. Tomlinson and C. L. Wilkins, Evaluation of a semi-automated multidimensional gas chromatography-infrared-mass specti ometry system for initant analysis , pp. 347-354, 1998, with permission from Wiley-VCH. 

It should be noted here that the difficulty of accurately injecting small quantities of liquids imposes a significant limitation on quantitative gas chromatography. For this reason, it is essential in quantitative GLC to use a procedure, such as the use of an internal standard, which allows for any variation in size of the sample and the effectiveness with which it is applied to the column (see Sections 9.4(5) and 9.7). 

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