acid in a sealed tube a t 200’ C. for 6 hours. After the usual workup, carboxylic acids were analyzed by GLC as methyl ester and primary amine as trifluoroacetamide. Tetradecanoic acid was found to be a major constituent in the acidic product. In the basic fraction CI3 amine was predominantly found.
1635
960
RESULTS AND DISCUSSION
Hydrocarbons. I n the investigation of the hydrocarbon components of shale oil distillate, elution adsorption chromatography using silica gel has been successfully applied for the separation of paraffin from olefin (3). Further separation of isomeric olefins by this method, however, is almost impossible. The present work has shown that silica gel impregnated with silver nitrate is a useful adsorbent for the type analysis of shale oil hydrocarbons. Paraffin, terminal olefin, and nonterminal olefins were completely separated from each other on TLC as well as by elution chromatography. Among olefins, the terminal one was most strongly adsorbed; as the double bond goes to the center of the chain, it was less strongly adsorbed. Olefin concentrates were easily characterized by infrared spectra: terminal olefins a t 910 and 990 cm.-l (deformation bands) and 1635 cm.-1 (stretching band) ; nonterminal olefins a t 960 cm.-’ (deformation band). Analytical results on CI6and C17 hydrocarbons are given in Table 11. A noticeable fact about the straight-chain olefinic components is that double bond distribution is strongly favored toward the end of the chain. The same situation would be expected in fractions of both higher and lower boiling point. Nitriles. Separation of the ketonenitrile mixture into each functional component by elution adsorption chromatography was not practical because of their close polarities against various kinds of adsorbents. However, selective reduction of ketonic compounds with sodium borohydride to the corresponding secondary alcohols made it possible to isolate nitriles by silica gel chromatography. Whether or not the shale oil distillate contains aliphatic nitrile has been questioned (14). As a matter of fact, it is impossible to find in the infrared spectrum of the distillate the characteristic stretching vibration band of nitrile. As shown in Figure 8, only strong ketone (1700 crn.-l) and double bond absorption bands (1635, 990, 960, and 910 crn.-l) are observed. The present investigation confirmed the presence of nitriles of Clzthrough CISin the distillate
910
5000
3000
2000
1000
1500
700
WAVENUMBER (=my1 Figure 8.
infrared spectrum of straight-chain neutral oil from cut 4
boiling from 280’ to 305’ C., although in small amount (0.2%). Ketones. Alkanones of C13 through Cls were identified. The Schmidt reaction method which was used for the estimation of carbonyl position distribution is not necessarily the best method. There is no definit evidence about the side of the carbonyl group to which the imino group is preferably introduced in the case of the long-chain ketone. However, degradation experiments on fractions of the same carbon number showed that one carbon less carboxylic acid and two carbon less amine were predominantly formed. This suggests that 2-alkanone is the major component in the shale oil distillate of the present investigation. ACKNOWLEDGMENT
The authors are grateful to E. Ochiai for his encouragement throughout this work, and to K. Mitsuhashi of Toyama University for his helpful suggestions. They also express their thanks to M. Ishikawa and T. Tsuchiya, Tokyo Medical and Dental Cniversity, for carrying out preparative scale gasliquid chromatography, to C. H. Prien, Denver University, and B. Guthrie, U. S. Bureau of Mines, for their kind supply of Colorado shale oil, and to Idemitsukosan Co., Ltd., for the transportation of shale oil. LITERATURE CITED
(1) Barrett, C. B., Dallas, M. S. J., Padley, F. B., Chem. Ind. (London) 1962, 1050. (2) Dinneen, G. U., Cook, G. L., Jensen, H. B., ANAL.CHEM.30 2026 (1958). (3) Dinneen, G. U., Smkh, J. R., Van Meter, R., Allbright, C. S., Anthoney, W. R.. Ibid.. 27. 185 (1955). (4) Eisen, 0.; Goryuch, S., Khim. i Tekhnol. 1961, 213.
(5)Eisen, O.,Rang, S. A,, Ibid., 1961, No.4, 200. (6) Eisen, O., Rang, S. A., Arumeel, E. K.. Kim. i Tekhnol. Tovliu i Mosel 8. 38 (1963). (7)‘Hull, W.’ Q., Guthrie, B., Sipprelle, E. M., Ind. Eng. Chem. 43, 2 (1951). (8) Iida, T., J. Pharm. SOC. Japan 82, 144, 151 (1962). (9) Iida, T., Pharm. Bull. 1, 209 (1953). (10) Iida. T.. Tanaka. M.. J. Pharm. SOC. . iapan,’64,’162(1944). ’ (11) Iida, T.,Tanaka, M., Pharm. Bull. 1, 211 (1953). (12) Klesment, I. R., Eesti NSV Teaduste Akad. Toimetised 13, 297 (1964). (13) Ruark, J. R.,Berry, K. L., Guthrie, B.. U. S. Bur. Mines Revt. Invest. 5279 (1956). (14) Van Meter, R., Bailey, C. W., Smith, J. R., Moore, R. T., Allbright, C. S., Jacobson, I. A,, Hylton, V. M., Ball,’ J. S.. ANAL. &EM. 24. 1758 (1952). (15) Wagner H.,Goetschel, J. D., Lesch, P., Helu. dhim. Acta 46, 2986 (1963). \ - - - - ,
RECEIVED for review March 10, 1966. Accepted June 10,1966. Work su ported by a grant from the Ministry of Eication of Japan.
Correction Estimation of Medium Effects for Single Ions and Their Role in the Interpretation of Nonaqueous pH I n this article by Orest Popovych
(ANAL. CHEM. 38, 558 (1966)], the e. m. f. of the cell described on page 559 below Equation 9 should be equal to (Ej- k logmYH). In the title of Table I11 on page 561, the scale should read “molal,” instead of “molar. ”
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