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INDUSTRIAL A N D ENGINEERING CHEMISTRY
Resorcinol was chosen as a representative dihydroxy phenol. This analysis was made before the apparatus had been developed to the stage where solid phenols could be handled easily, and as resorcinol is not very soluble in toluene a mixture of phenol and resorcinol, which would dissolve more readily than resorcinol alone, was prepared, which contained 81.12 per cent of phenol and 18.88 per cent of resorcinol. The theoretical hydroxyl number for this mixture was calculated to be 483, whereas the value actually determined was 488. A sample of freshly distilled carvacro1,t which was collected a t 236’ C. (bar. 749.3 mm.-29.50 inches) gave a sodium hydroxide equivalent of 268, the theoretical value being 266. A sample of p-dihydroxyphenylbutanet (mol. wt. 242, m. p. 136) was analyzed. As this compound is a solid and is not hygroscopic, it was packed into a small weighing tube which was open a t both ends so that the solvent could have ready access to the sample. The sodium hydroxide equivalent of the sample was found to be 165, just half of the calculated theoretical value of 331. Apparently, in this case only one hydroxyl group reacts with the sodium, which may be due to the insolubility of the monosodium salt in toluene. As soon as the sodium has reacted with one hydroxyl group this salt is precipitated and the compound is no longer available for reaction. The possibility of using the method for determining the free phenol in intermediate synthetic resin mixtures was suggested. A sample of commercial formaldehyde resin was melted together with phenol giving a mixture containing 9.15 per cent free added phenol.$ An analysis of the mixture by the sodium method showed a phenol content of 9.47 per cent, which is 0.32 per cent high. Another sample of a resin-phenol mixture was prepared. I n its analysis gasoline was used as the solvent. The total phenol content of the sample, including a blank on the resin, was 21.22 per cent, whereas the phenol content as determined by the sodium method was found to be 20.99, which is 0.23 per cent low. The results of these experiments show that the method may have important application in the examination of synthetic phenolic resins. Modified NaOH Method for Determining Phenols in Tar Oils
The method’ of determining percentage of phenols in an oil, by taking the difference in weight of the caustic solution before and after the extraction, was not sufficiently accurate for the purposes of the investigation of the caustic t By courtesy of A. W. Hixon, Columbia University. 1: The writers are indebted to H . L. Bender for the sample of 9-dihydroxyphenylbutane and the phenol-resin samples, as well as for the results of the analysis in which gasoline was used as a solvent.
Vol. 17, No. 6
soda process of extracting tar acids, as no allowance is made for the oils that are mixed with the sodium phenolate or for the sodium phenolate that adheres to the sides of the funnels. The liberation method* for tar acids gave results which were variable and high, especially with concentrated caustic solutions, due to the oils which were included in the sodium phenolate solution. It was found, however, that the liberation method could be modified so as to give satisfactory results with all concentrations of caustic solutions. In the modified method the tar acids are extracted from the oil by shaking with sodium hydroxide solution and the sodium phenolate solution is drawn off into a small Erlenmeyer flask, where it is acidified with 20 per cent sulfuric acid. After cooling to room temperature, the liberated tar acids and the sulfate solution are poured through 65 cc. of benzene in a Type 2 tar acid f ~ n n e l . ~ The sulfate solution is drawn off into the original flask and poured back through the benzene. I n this manner the flask is rinsed out and all the tar acids are absorbed by the benzene. Sufficient benzene is then added to bring the volume of the benzene solution of tar acids to 100 cc. Fifty cubic centimeters of 10 per cent sodium hydroxide are now added and the funnel is thoroughly shaken. After complete separation of the layers, the sodium phenolate is drawn off and the volume of the residual benzene is read. The benzene is shaken with another portion of 20 cc. of 10 per cent caustic to insure complete removal of the phenols. Two treatments with caustic are usually sufficient to remove the tar acids from the benzene. The decrease in volume of the benzene is taken as the volume of tar acids present. When a 100-cc. sample of oil is used, this volume represents the percentage of tar acids, by volume, in the oil. This method eliminates the errors in the liberation method, which are caused by the residual oils mechanically included or dissolved in the sodium phenolate solution, as these residual oils are left in the benzene when the tar acids are extracted from the benzene solution with the 10 per cent caustic. The per cent of tar acids as determined by the liberation method, especially with the more concentrated caustic solutions, was in certain cases 5 or 6 per cent in excess of the value obtained by the above method. Bibliography 1-HUB, Chcm. Met. Eng., 26, 113 (1922). 2-Schryver, J . SOL.Chcm Ind., 18, 553 (1899). 3-A. Heldring, Chcm. Wcckblad, 18, 96 (1921); Kolthoff, 2. anorg. allgem. Chem., 112, 87 (1920). 4--Borck, German Patent 322,242 (June 23, 1920); Chem. Zcnfr., Ql (IV), 302 (1920). &Fox and Barker, J . SOL.Chcm. I n d . , 36, 843 (1917). G P e t r i e , I b i d . , 38, 132T (1919). 7-Morgan and Soule, Chcm. Met. E m . , 26, 923 (1922). 8-Weiss, J . I n d . Eng. Chem., 10, 817 (1918). 9-Weiss, loc. c i f . ; also Empire Laboratory Supply Co., Inc , Bulletin, “Apparatus Used in the Coal-Tar Industry.”
Chemical Advisory Committee to the Department of Commerce Formed At the invitation of the Secretary of Commerce, a Chemical Advisory Committee to the Department was organized May 19. The members have been requested to serve in their individual capacities and not as representatives of particular industries or trade associations. They are: LEO H. BAEKBLAND, Bakelite Corp., 247 Park Ave., New York, N . Y. A. S. BURDICK, Abbott Laboratories, Ravenswood, Chicago, Ill. CRAS. H. HERTY, Synthetic Organic Chemical Manufacturers Assoc., 1 Madison Ave., New York, N. Y. HENRYHOWARD, Grasselli Chemical Co., Guardian Bldg., Cleveland, Ohio. H. E. HOWE, Industrial and Engineering Chemistry, 706 Mills Bldg., Washington, D. C.,secretary. A. C R ~ S SMORRISON, Y Union Carbide & Carbon Corp., 30 E. 42nd St., New York, N. Y., chairman.
G. O B ~ RG. , Ober & Sons, 110 E. Lombard St., Baltimore, Md. E. T. TRIOO, John Lucas & Co., 322 Race St., Philadelphia, Pa. S. W. WILDB-R, Merrimac Chemical Co., 148 State St., Boston, Mass.
The day was devoted to a review of the development of the Chemical Division and to a discussion of the various types of service that the several divisions of the Bureau of Foreign and Domestic Commerce can render to the chemical industry. It is understood that the committee is to serve as liaison between the industry and the Department, doing whatever it can to increase cooperation between the two, advising the Department as to work to be undertaken for industry, and obtaining within the industry the cooperation frequently desired by the Department. A stated meeting will be held annually with interim meetings at the call of the chairman or of the Department.
