LITERATURE CITED
Furfural Furfuryl alcohol 5-Hydroxymethylfurfural
I. Column and Paper Chromatographic Data Column Paper developer Fraction developer RJ Indicator Toluene 5-12 Toluene ... Aniline acetate Toluene 13-23 Toluene 0.79 Aniline acetate Chloroform 42-56 Methanol0.81 Aniline acetate acetone
Fumaric acid
95%, EtOH
Table
60-69
development with toluene, furfural appeared in fractions 5-12, fractions 13 and 14 contained a mixture of furfural and furfuryl alcohol, fractions 15-23 contained pure furfuryl alcohol. Following this, the 5-hydroxymethylfurfural n-a. eluted with chloroform as a yellow-orange band. The eluent was monitored for 5-hydroxymethylfurfural with 2-thiobarbituric acid. When the color test showed that the compound had been eluted, 957, ethanol was added to the column. The presence of colorless fumaric acid in the in-
(8: 1) Methanolacetone (8: 1)
0.61
Methyl red
dividual fractions was detected by measuring p H change. The results are summarized in Table I. The identification of the pure individual compounds was made from the Rf values on paper chromatograms and by ultraviolet and infrared analyses. Furfural and furfuryl alcohol were chromatographed in the toluene system, using aniline acetate as an indicator. A methanol-acetone system (8 : 1 v,/v.) n-as used to develop 5-hydroxymethylfurfural and fumaric acid. Aniline acetate and methyl red were used as indicator..
( 1 ) Aeschlimann, F., Bethge, P., Eggers, J., 2. Anal. Chem. 161, 3 (1958). (2) Barker, S. A., Murray, K., Stacey, M., Nature 186,469 (1960). (3) Bethge, P. O., Perssen, R. W., Suensk Papperstid 59, 535 (1956).
(4) de la Burde, R., Crayton, F., Bavley, A., Nature 196, 166 (1962). ( 5 ) Cier, A., Nofre, C., Drevon, B., Lefier, A., Bull. SOC.Chim. France 74, (1959). (6) Furlani, A. P., Univ. Stud. Trieste, Fac. Econ. Corn. Ist. Merceol 12, 13 (1959). (7) Lindermann, Erich, Die Starke 7 , 280 (1935). (8) Mudshoyan, E. L., Biokhirn Binodeliya Sbornik 4, 142 (1953). (9) Newth, F. H., Adzan. Carbohydrate Chem. 6 , 83 (1954). (IO) Schade, J., Marsch, G., Eckert, J., Food Res. 23, 446 (1958). (11) Weidenhagen, R., Stelzig. C., Zucher, 12, 244 (1959).
Philip Morris Inc. Research Center Richmond 6, Va.
R. DE L A BURDE J . E. JARRELL A. B A ~ L E Y
RECEIVED for review May 6, 1963. Accepted July 8, 1963.
Separation of Oxygen and Nitrogen by Packed Column Chromatography at Room Temperature SIR: I n the course of the development of gas chromatographic methods for the assay of various chlorofluoromethanes and ethanes, we have found that the 6-foot and 12-foot columns of Dow Corning 200 Silicone oil on Chromasorb P operating a t various temperatures are extremely useful in this work and remarkably stable. A rerious limitation of these columns was the poor resolution of the low boiling fraction a t ordinary temperatures. R e have found, however, that a 50foot column of D C 200 oil on Chromosorb P. operating at about 30' C., is an excellent column for separating these low boilers and in particular will separate oxygen from nitrogen. Since w c h separations are normally performed at low temperatures or on absorption columns, we feel the unique ability of this column operating a t room temperature worth describing.
posited on water washed Chromosorb P (30/60 mesh). Loadings of 570, 15%, and 20% D C oil gave no separation of nitrogen and oxygen. Benzene was used as the solvent for the substrate. The column material was added to a 50-foot length of '/4 inch 0.d. copper tubing and packed by tapping continuously along tJhe length during filling. Each end was plugged with glass wool. The packed column was coiled around a 3-inch diameter mandrel and then conditioned for 8 t o 12 hours directly in the instrument under operating conditions. Instrument and Operation. A Perkin-Elmer 154D Vapor Fractometer was used for these analyses. T h e column temperature was maintained a t 30" C. and the flow rate
Table I.
Tabulation of Retention Values
Compound EXPERIMENTAL
Column Preparation. I n preparing this column, i t is important t h a t the correct amount of substrate be used; otherwise, the separation of oxygen from nitrogen will not take place. T h e successful packing consisted of 331/2% by weight of the Dow Corning Silicone oil 200 (50 centistoke) de1536
ANALYTICAL CHEMISTRY
S? 0 2
CHFI CFaC1 COa CHz=CFz CHF~HF CHClF? CClzFz
Retention time, Min. 7.30 7.60 10.0 11.0 11.1
12.4 16.4 25.4 35.3
of carrier gas (Helium) was 44 cc. per minute. Both 1/4-cc. and 1-cc. gas sample loops were used. RESULTS AND DISCUSSION
The retention times for oxygen, nitrogen, and some common halocompounds on this column are presented in Table I. The separation betlveen the oxygen and nitrogen peaks, while not complete, is adequate for identification and a reasonable estimation of quantitative content is possible. The identity of the eluted components was established by comparing standard know-n mixtures and by the use of infrared spectrophotometry and mass spectrometry for the identification of the trapped components. Over a period of t r o years thiq column exhibited exceptionally good .tability with practically no aging. As a practical result, we have found such columns ideal for process chromatograph. n-hen applicable. HARRY T. REIX MAERICEE. MIVILLE ARNOLD H FAIKBERG Pennsalt Chemical Corp. Technological Center King of Prussia, Pa. RECEIVEDfor review May 3, 1963. Accepted June 28, 1963.
