Products, gas-chromatographic

The high temperatures in the MHD combustion system mean that no complex organic compounds should be present in the combustion products. Gas chromatograph/mass spectrometer analysis of radiant furnace slag and ESP/baghouse composite, down to the part per biUion level, confirms this behef (53). With respect to inorganic priority pollutants, except for mercury, concentrations in MHD-derived fly-ash are expected to be lower than from conventional coal-fired plants. More complete discussion of this topic can be found in References 53 and 63. 

SHINGARI, M. K., Conder, J. R. and Fruitwala, N. A. J. Chromatog. 285 (1984) 409. Construction and operation of a pilot scale production gas chromatograph for separating heat-sensitive materials. 

Another relevant example is the pyrolysis of cnt/ -2,7,7-trimethylbicyclo[3.1.1]hept-2-en-6-ol (21) at 430 =C, which produces a mixture of several products. Gas chromatographic separation gives, among many other compounds, 3,7-dimethylocta-3,6-dienal (23) and 3,7-dimethylocta-2,6-dienal (24) in 13 and 6% yield, respectively.107 As can be seen in the diradical 22, the C — C double bond is able to offer 71-stabilization to the secondary radical. For this reason, the 1,4-diradical is generated exclusively.107... 

This study was undertaken to develop techniques for direct monitoring of organic hydrothermal synthesis reactions in DACs combined with direct microscopic and spectroscopic observations. Such direct observation provided additional insight into the mechanism, kinetics and phase behavior (miscibility characteristics) of the fluid-rich system. Described below are some results on the direct monitoring of citric acid-HaO system at high P and T with DAC Raman spectroscopy combined with quench product gas chromatographic analysis. 

Addition of dichlorocarbene, produced by treatment of ethyl tri-chloroacetate with sodium methoxide, to 3,4,6-tri-O-methyl-D-glucal gave, apparently, one product (gas-chromatographic analysis) in 82% yield. By stereochemical analogy with epoxidations, the product was considered to be l,5-anhydro-2-deoxy-l,2-C-(dichloromethylene)-3,4,6-tri-O-methyl-D-g/j/cero-D-ido-hexitol (21). Demethylation was brought about with boron trichloride at—70°, to give atriol from which a crystalline tribenzoate was obtained and reaction with lithium aluminum hydride caused reductive cleavage of the carbon-chlorine bonds.36 A similar addition was applied to 3,4-unsaturated furanosyl compound (see p. 247). 

The reaction product is cooled to room temperature, is washed with 10 ml of H2O to the purpose of removing lithium iodide and is then dehydrated over NaiS04. 3.57 g is obtained of dimethoxy-phenylacetone (III), as determined by gas-chromatographic analysis with an inner standard of 4,4 -dimethoxybeniophenone. The yield of ketone (III) relative to the olefin ( ) used as the starting material is of 87.1%. 

In current industrial practice gas chromatographic analysis (glc) is used for quahty control. The impurities, mainly a small amount of water (by Kad-Fischer) and some organic trace constituents (by glc), are deterrnined quantitatively, and the balance to 100% is taken as the acetone content. Compliance to specified ranges of individual impurities can also be assured by this analysis. The gas chromatographic method is accurately correlated to any other tests specified for the assay of acetone in the product. Contract specification tests are performed on product to be shipped. Typical wet methods for the deterrnination of acetone are acidimetry (49), titration of the Hberated hydrochloric acid after treating the acetone with hydroxylamine hydrochloride and iodimetry (50), titrating the excess of iodine after treating the acetone with iodine and base (iodoform reaction). 

Monobasic acids are determined by gas chromatographic analysis of the free acids dibasic acids usually are derivatized by one of several methods prior to chromatographing (176,177). Methyl esters are prepared by treatment of the sample with BF.—methanol, H2SO4—methanol, or tetramethylammonium hydroxide. Gas chromatographic analysis of silylation products also has been used extensively. Liquid chromatographic analysis of free acids or of derivatives also has been used (178). More sophisticated hplc methods have been developed recentiy to meet the needs for trace analyses ia the environment, ia biological fluids, and other sources (179,180). Mass spectral identification of both dibasic and monobasic acids usually is done on gas chromatographicaHy resolved derivatives. 

Concretes and absolutes, both obtained by total extraction of the plant material and not subject to any form of distillation other than solvent removal, are complex mixtures containing many chemical types over wide molecular weight ranges. In some cases, gas chromatographic analysis shows httle volatile material. Yet these products have powerful odors and contribute in important ways to the perfumes in which they are used. 

Chromatographic methods, notably hplc, are available for the simultaneous deterrnination of ascorbic acid as weU as dehydroascorbic acid. Some of these methods result in the separation of ascorbic acid from its isomers, eg, erythorbic acid and oxidation products such as diketogulonic acid. Detection has been by fluorescence, uv absorption, or electrochemical methods (83—85). Polarographic methods have been used because of their accuracy and their ease of operation. Ion exclusion (86) and ion suppression (87) chromatography methods have recently been reported. Other methods for ascorbic acid deterrnination include enzymatic, spectroscopic, paper, thin layer, and gas chromatographic methods. ExceUent reviews of these methods have been pubHshed (73,88,89). 

The levels of trace impurities in the product benzaldehyde are often more important than the product assay. Gas chromatographic methods for the deterrnination of those trace impurities are widely used. 

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). 

Operational temperatures of 4—27°C are maintained. In this process the flavor components are concentrated in the retentate. A reduced alcohol product is obtained by adding back water to give the desired flavor impact. Typical gas chromatographic results, comparing unprocessed 80° proof whiskey with reverse osmosis processed 54° proof whiskey and diluted 54° proof whiskey, indicate good congener retention in the alcohol-reduced (RO) processed whiskey (Table 7). 

All known methods of identification of authenticity products of cognac demand presence of such difficult and expensive devices as gas chromatographs, weights - spectrometers application crystallization, extractions, etc. methods of division increases time of carrying out of the analysis. 

Disappearance of benzalacetone and appearance of product can be readily monitored by thin layer or gas chromatographic analysis on a 1-m column packed with 20% Silicone SE-30 at 180°C. The reaction should be stopped as soon as disappearance of benzalacetone is confirmed. 

The aldehyde is separated from the lower aqueous layer as a colorless liquid and dried over 10 g. of anhydrous sodium sulfate. The drying agent is removed by filtration, and the product is distilled under reduced pressure using a Claisen distillation apparatus to give 92-94 g. (82-84%) of cyclohexanecarboxaldehyde, b.p. 52-63° (18 mm.), 1.4484 (Notes 10, 11). A purity of about 98% was established by gas chromatographic analysis (Note 12) the product is suitable for synthetic use without further purification (Note 13). 

Gas chromatographic analysis of the crude mixture (SE-30 on Chromosorb W, 1 m., 150°) showed the presence of some low-boiling materials (including unreacted methyl nitroacetate) and a significant amount of the doubly alkylated by-product, trimethyl 2-nitro-l,2,3-propanetricarboxylate. 

The distilled product was determined by the checkers to be 85-90% pure (gas chromatographic analysis), the major impurity being... 

At this point the submitters reported 7.07 g. of crude product which by gas chromatographic analysis on an SE 30 column at 200° showed 1-3% of 10-methyl-A < -2-octalone and 85% of the desired alkylated product. 

---