24%
VOL. 7, NO. 4
INDUSTRIAL AND ENGINEERING CHEMISTRY
The data presented in Table I11 show that the water content of synthetic sulfur mixtures b y the distillation method agreed closely with the amount of water originally added. The accuracy of the distillation method was 1.0.2 ml. water. There was no interfering action between sulfur, gas oil, and light oil mixtures, upon the determination of moisture.
Summary
A rapid distillation method for the determination of water in by-product sulfur has been presented. The accuracy of the distillation method has been established from two angles.by the use of synthetic moisture-sulfur mixtures of known moisture content, and by the study of an air-drying method. Data are presented as to the accuracy of the new method. Drying the sulfur cake for 1 hour at 100’ C. for moisture content gives inaccurate results.
Acknowled,oment The author wishes to acknowledge the cooperation of members of the laboratory staff, and in particular E. N. Button, Jr., in carrying out this work.
Liteiature Cited
,
Materials, Proc., Vol. 25, Pt. I, p. 416, 1925. Am. Soc. T&ing Materials Standards, Pt. 11, D 95-30, p. 556, g
1930; p. 891+,1933. 8 , Colbert, F. D., Gas Agepecord, 65, 783 (1930). Cooper, J. F., Ibid., 65, 506 (1930). Fresenius, C. R., “Quantithtive Chemical Analysis,” Vol. 2, p. 704, New York, John Wiley & Sons Co., 1915. Geiger, C. W., Gus Age-Record, 60, 41 (1927) Gollmar, H. A., IND.ENQ.CHEM.,26, 130 (1934). Griffin, R. C., “Technical Methods of Analysis,” 2nd ed., p. 23, New York, McGraw-Hill Book Co., 1927. Jacobson, D. L., Gus Age-Record, 63, 895 (1929). Lunge, G., “Technical Methods of Chemical Analysis,” Vol. 1, p. 266, New York, D. Van Nostrand Co., 1908. Sauohelli, V., IND.ENO.CHEM.,25, 363 (1933). “Standard Methods of Chemical Analysis,” 4th ed., p. 519, New York, D. Van Nostrand Co., 1927. Seil, G. E., and Heiligman, H. A., Am. Gas J., 131, 36 (1929). Sperr, F. Proc. Am. Gus Assoc., 3, 282 (1921). Ibid., 5, 1900 (1923). Sperr, F. W., Proc. Canadian Gas Assoc., July, 1926. (16)
w.,
RECE~IVHID March 18, 1935. 1
Detection and Estimation of Orthophenylphenol WILLIAM 0. EMERY AND HENRY C. FULLER, 1835 I St., N. W., Washington, D. C.
B
Y VIRTUE of its relatively high phenol coefficient and
other physical properties, orthophenylphenol has acquired a position of considerable importance in bacteriological investigations, and the question arose as to the possibility of detecting and estimating i t if and when recovered from the body eliminations, notably the urine. Having in mind the peculiar behavior of phenol and salicylic acid when treated with iodized potassium iodide in the presence of hot aqueous alkaline carbonates (to which one of us has already given some attention, 1-4), it appeared not improbable that orthophenylphenol might under like circumstances develop a similar characteristic reaction. I n the case of phenol and of salicylic acid (orthocarboxyphenol), the above-mentioned reagents on continued addition finally bring about the precipitation of a reddish iodine derivative, CeHz120, variously designated by its earlier investigators “Lautemann’s Korper,” diiodophenylene oxide, tetraiodophenylene oxide, and tetraiodophenylene quinone, a substance insoluble in aqueous alkaline media and the more common organic solvents, but readily lending itself to quantitative determination. Similar tests with orthophenylphenol under conditions parallel t o those observed with phenol and salicylic acid yielded immediately a characteristic purplish red precipitate, analysis of which disclosed the composition, simply expressed, CI2H,IO, and as readily susceptible of estimation as the corresponding phenol, or salicylic acid derivative. The procedure f o l l o ~ ~ eisdsubstantially that indicated below. In a 0.5-liter Erlenmeyer flask containing a little water dissolve 200 mg. of ortho henylphenol by means of a few drops of 10
per cent sodium Rydroxide solution, place on a steam bath, and add 200 ml. of distilled water, 2 grams of anhydrous sodium carbonate, and 0.2 gram of sodium bicarbonate (the latter to neutralize any free sodium hydroxide), heat for some minutes, then add 0.2 N iodine solution (iodized potassium iodide) in about 10-cc. portions, until after heating 15 to 20 minutes the reaction mixture retains a permanent yellow coloration, due to excess iodine. Now add just sufficient sulfur dioxide solution, if available (otherwise a small crystal of sodium sulfite), to discharge the yellow coloration, remove from bath, allow the purplish red precipitate to subside, then decant the supernatant
liquid into a tared Gooch crucible, add hot water to the flask, mix thoroughly, and gradually transfer the entire precipitate quantitatively to the crucible, washing with not less than 200 ml. of hot distilled water. During the operation of washing, care should be taken that the precipitate on the filter remains somewhat moist until the final suction, otherwise cracks develop, thereby rendering a uantitative elimination of accompanying salts more difficult. i f t e r the final washing, however, the precipitate is by adequate suction almost completely freed of moisture. Finally dry in an oven at 100’ C. to constant weight. When pure, 200 mg. of orthophenylphenol should yield approximately 0.3459 gram of the iodine derivative, C12H,I0. In a series of controls the following recoveries were obtained: 0.3467, 0.3479, and 0.3466 gram of the iodine derivative, while determination of the iodine content (by fusion with anhydrous sodium and potassium carbonates) yielded the values 43.39 and 43.50 per cent; theoretical, 43.20 per cent. No allowance was made for traces of chlorides present, hence the relatively high percentages of iodine found.
For purposes of comparison, the corresponding iodine derivative of orthomethylphenol (orthocresol) was obtained in exactly the same manner, as a muddy light green substance, having the composition CsHJO, 200 mg. of the phenol yielding 0.4270 gram of the iodine derivative; theoretical, 0.4296 gram. For the above iodine derivatives the following structural formulas are suggested as representing their simplest molecular arrangement: 0
I
0
~
H H Phenol derivative
0
1 I 0 1Q-c” H H Orthophenylphenol derivative
Orthomethylphenol derivative
Literature Cited (1) (2) (3) (4)
Bougault, J. pharm. chim.,[e] 28, 147. Knmmerer and Benzinger, Ber., 11, 557 (1878). Kekul6, Ann., 131, 221 (1864). Lautemann, Ibid., 120, 309 (1861).
RECEIVED April 12, 1935.
