Capillary gas chromatography and mass spectrometry have been used for identification of most main high-boiling components of fraction of pyrolysis oil (boiling point 250 to 350° C under normal pressure) especially those boiling above the b.p. of acenaphthene. All methyl homologues of acenaphthene, phenanthrene, some isomeric methylfluorenes, trimethyl- and methylethyl naphthenes, phenylnaphthalenes, dimethylbiphenyls, benzindans, methylbenzindans and other aromatic hydrocarbons have been prepared as standards. In connection with the preparation of some trimethyl- and methylethylnaphthalenes a discussion is presented of the course of chloromethylation and acetylation of 1- and 2-methyl- and 2-ethylnaphthalenes. Content of methyl-homologues of some hydrocarbons (acenaphthene, fluorene, phenanthrene, and anthracene) in the high-boiling fraction of pyrolysis oil has been compared with that present in similar fraction of coal tar.

Using synthetic, chromatographic and spectral methods, we studied the side reactions accompanying the preparation of di-2-ethylhexyl phthalate from phthalic anhydride and 2-ethyl-hexane-1-ol in the presence of catalytic amounts of tetra-n-butyl titanate.The catalyst proper was titanium(IV) mono-2-ethylhexyl phthalate. The possibility of a simultaneous gas-chromatographic quantitative determination of mono-2-ethylhexyl phthalate, di-2-ethylhexyl phthalate, 2-ethylhexane-1-ol and tetra-n-butyl titanate, reported in the literature, has been refuted. In the esterification catalysed by hydrated titanium dioxide homogeneous catalysis by the formed organotitanate was dominating. The dissolving of hydrated titanium dioxide in the esterification of phthalic anhydride with 2-ethylhexane-1-ol was studied polarographically.

Capillary gas-liquid chromatography with three columns impregnated with non-polar, medium and polar stationary phases has been used for determination of the Kováts indexes of methylethyl- and trimethylbiphenyls carrying the alkyl groups in the both rings. From elution data of isomeric methyl- and ethylbiphenyls the increments of methyl and ethyl groups have been determined, the theoretical Kováts indexes of the mentioned methylethyl- and trimethylbiphenyls have been calculated, and possibility of prediction and assessment of the Kováts indexes of these substances has been discussed. Parameters of the straight line given by the relation IApiez.L = k . Istat.phase(2) + q have been determined, and correlation coefficients of these relations have been estimated.

Trimethyl-, tetramethyl-, and ethylmethylbiphenyls with the alkyl groups at one aromatic ring have been prepared by the Gomberg reaction and identified by capillary gas chromatography. The products are either chemical individua or mixtures of up to three isomers depending on choice of the aromatic hydrocarbon. The ethylmethylbiphenyls have been prepared as mixed standards only. Most aromatic hydrocarbons used in the Gomberg reaction have been prepared by combination of rectification and sulphonation procedures. The HMO method has been used for calculation of the values of the radical superdelocalizabilities at individual centres of the 1,2,4- and 1,2,3-trimethylbenzene molecules which have been compared with product composition of the Gomberg reactions of these hydrocarbons. Reactivities of the aromatic substrates used in the Gomberg reaction have been compared by the competition technique. Capillary gas chromatography using three columns wetted with non-polar , medium, and polar stationary phases has been used to determine the Kovats indexes of the hydrocarbons prepared and parameters of the linear dependences IApiez.L = k.Istat.phase(2) + q (with the corresponding correlation coefficients). From the elution data of the isomeric methyl- and ethylbiphenyls the increments have been derived for methyl and ethyl groups, and possibility of prediction and assessment of the Kováts indexes of polyalkybiphenyls and dimethyldiphenylmethanes is discussed.

Composition of the low-boiling fraction of the pyrolysis oil obtained from continuous rectification has been determined by combination of capillary gas-liquid chromatography with other identification methods (catalytic hydrogenation, polymerization). In this way components have been identified which form overall 86.0 per cent (m/m) of the low-boiling fraction. The said pyrolysis oil fraction has been found to contain almost 50 per cent (m/m) of unsaturated components able of polymerization, especially methylindenes, methyl-, ethyl- and dimethylvinylbenzenes, divinylbenzenes and 1,2-dihydronaphthalene. Elution behaviour of all the identified isomeric methylindenes, divinylbenzenes and 1,2-dihydronaphthalene has been evaluated by determination of parameters of the equation Ist.phase (2) = k . Ist.phase(1) + q. The Kovats elution indices of all the identified aromatic hydrocarbons have been determined with the use of a glass capillary column wetted with Carbowax 20M at 80 °C.