Analytical Reaction Gas Chromatography, 1968

The most universal and effective method for the analysis of complex multicomponent mixtures of volatile substances is gas chromatography. However, there are a number of limitations asso­ ciated with the classical variation of this technique which retard its development and the further expansion of its application: 1) the identification of the components of a complex mix­ ture of unknown composition is in itself a complex and difficult problem, unless the homologous series of the component to be identified is known; 2) the overlapping of chromatographic peaks for several compounds makes it difficult, and in a number of cases impossible, to carry out qualitative and quantitative analysis of these components, and leads to the necessity of using several columns of different polarities or to the use of columns with very high efficiency; 3) the direct analysis of unstable and nonvolatile compounds is impossible; 4) the difficulty of quantitative chromatographic analysis using thermal conductivity detectors increases with the necessity of determining individual response (calibration) factors; the insensitivity of the flame ionization detector to a number of substances (inorganic gases) leads to the necessity of introducing additional operations (prelimi­ nary concentration of trace components) in connection with thermal conductivity detectors. vii viii FOREWORD The directed use of chemical conversion of the compounds analyzed usually makes it possible to remove the limitations cited above.

I. Main Directions in the Development of Analytical Reaction Gas Chromatography.- New Applications of Gas Chromatography.- Improvement in the Separation and Identification of Sample Components.- The Use of Chemical Reactions to Detect the Compounds Being Analyzed.- Literature Cited.- II. Some Problems in the Theory of Analytical Reaction Gas Chromatography.- Chemical Reactions in Chromatographic Reactors.- Analytical Application of the Kinetic Method in Gas Chromatography.- Effect of the Reactor on the Chromatographic Characteristics of the Compounds Being Analyzed.- Literature Cited.- III. Chromatographic Systems in Analytical Reaction Gas Chromatography.- Literature Cited.- IV. The Analysis of Complex Mixtures.- Hydrogenation and Dehydrogenation.- Ester Preparation and Hydrolysis.- Pyrolysis of Volatile Substances.- Dehydration and Decarboxylation.- Reactions for the Formation of Nonvolatile Compounds.- Oxidation.- Literature Cited.- V. Analysis of Impurities.- Use of Specific Chemical Reactions for the Retardation of the Main Component (Formation of Nonvolatile Compounds).- Conversion of the Impurity into a Volatile Compound.- Chemical Concentration of the Impurities.- Chemical Conversion of Impurities and the Main Component in Order to Change the Sensitivity of Detection.- Literature Cited.- VI. Analysis of Polymers and Other Nonvolatile Compounds.- Identification of Polymers.- Analysis of Copolymers.- Prospects for the Development of Destruction Chromatographic Methods.- Literature Cited.- VII. Elemental Analysis.- Determination of Carbon and Hydrogen.- Determination of Nitrogen.- Determination of Oxygen.- Determination of Sulfur.- Literature Cited.- VIII. Qualitative Analysis and Change in Detector Sensitivity.- Qualitative Chemical Reactions and Detectors.- Use of Chemical Reactions in Front of the Detector.- Literature Cited.- IX. Selective, Chemically-Active Sorbents in Gas Chromatography.- Literature Cited.