finery waste waters studied is o-cresol; when its standard absorbance curve is used, a ratio of 0.89 is obtained. Figure 2 indicates that the magnitude of error involved in using the wrong calibration curve in the 4-aminoantipyrine method is considerable and increases with phenolic compound concentration. The approximately 10% phenolic compounds unaccounted for in the last ratio are probably para-substituted phenols not determined by the 4-aminoantipyrine method, nieta-substituted phenols, or xylenols. The fairly constant ratios obtained here were not experienced by Schmauch and Grubb in their analysis of 12 waste water samples; this indicates the difficult problem of analyzing waste waters which may contain a wide variety of phenolic compounds in varying concentrations. The summary in Table I shows that the 4-aminoantipyrine method is the fastest, most precise, and accurate colorimetric method, even in the low parts per billion range. The infrared absorption method, although not investigated to its fullest extent, has the decided disadvantage of cost of equipment. The ultraviolet absorption method appears to offer considerable
promise for determining all the phenolictype compounds found in refinery waste waters in both the parts per million and parts per billion ranges. It is currently believed that the ultraviolet absorption method is the best because it overcomes the serious deficiency of the other methods of becoming insensitive if the coupling position is blocked. LITERATURE CITED
American Petroleum Institute, Ken, York, “Manual on Disposal of Refinery Wastes,” Vol. IV, 1st ed., 1953. Am. Public Health Assoc., Ken. York, “Standard Method for Examination of Water and SeFage,” 10th ed., 1955. Am. Soc. Testing Materials, Philadelphia, Pa., “ASTM Standards on Petroleum Products and Lubricants-Proposed Recommended Practices for Applying Precision Data,” p. 896, 1954. Emerson, E. I., J . Ora. Chern. 3, 153 (1938): (5) Ettinger, M. B., Ruchhoft, C. C., ASAL. CHEW.20, 1191-6 (1948). (6) Ettinger, 124. B., Ruchhoft, C. C., Lishka, R. J., Zbid., 23, 1783 (1951). (7) Gibbs, H. D., J . B i d . Chem. 71, 44559 (1927). .
I
JAGDISH SHANKAR, P. G. KHUBCHANDANI, and V. M. PADMANABHAN Chemistry Division, Atomic Energy Establishment (Trombay), Bombay, India tetrafluoride has recently been prepared in this laboratory by a dry method ( I ) , which gives a pure crystalline product. RANIUM
Although the single-crystal x-ray data have been published by Zachariasen ( 2 ) , so far no powder data have been reported.
X-Ray Powder Diffraction Data for Uranium Tetrafluoride d, A. d, A. d, A. d , A. hkl (Obsd.) (Calcd.) hkl (Obsd.) (Calcd.) Illa 151 1.95 1.95 4.17 4.18 60 111 1.85 1.85 440 3.91 3.92 30 22i 1.83 1.82 350 3.69 3.68 80 220 1.80 1.80 060 3.53 3.51 10 130 1.78 1.78 530 3.34 3.33 5 222 1.72 1.72 600 3.26 3.25 40 310 1.69 1.69 2 004 2.75 2.75 33i 1.64 1.63 10 402,351 2.70 040 2.69 1.62 1.62 2.56 2 620 2.55 400 202,420 2.29 2.31 2 062 1.60 1.60 150 2.10 2.11 6 531 1.53 1.53 023 2.07 2.06 10 550 1.48 1.48 510,205 2.02 2.02 100 640 1.45 1.45 531 1.99 1.99 25 044 1.43 1.43 Eighteen more indexable lines were recorded.
1374
ANALYTICAL CHEMISTRY
RECEIVED for review October 25, 1956. Accepted .Ipril 11, 1957. Division of Kater, Sen-age, and Sanitation Chemietry, Symposium on iinalytical Methods for Kater and Waste Water, 130th Meeting, ACS, Atlantic City. N. J., September 1956.
CRYSTALMORPHOLOGY Crystal System. Monoclinic. Form and Habit. Needles elongated parallel to c. Axial Ratios. a:b:c = 1.184:1:0.784 (x-ray).
Uranium Tetrafluoride, UF,
161.
(8) Gottlieb, S., Marsh, P. B., IND.ESG. CHEM., ANAL.E D . 18, 16 (1946). (9) Hablitzel, C. P., Jacob, L. N., unpublished data, Toledo Refinery Laboratory, Sun Oil Co., Toledo, Ohio. (10) International Joint Commission, Board of Technical Advisers, Washington, D. C.-Ottawa, Canada, “Analytical Methods for Boundary Waters Quality Control,” 1949. 11) Lykkon, L., Treseder, R. S., Zahn, Y,, IND.EXG.CHEM.,ANAL.ED., 18, 103-9 (1946). 12) llurray, M ,J., ANAL.CHEIII.21, 941 (1949). 13) Rosenbaum, E. J., Bostwick, L. G., unpublished data, Sun Oil Co . Sorn-ood, Pa. 14) Rosenblatt, D. H., Demek, M. 31, Epstein, tJ., ANAL.CHEW2 6 , 1655 b (1954). 15) Schmauch, L. J.,Grubb, H. %I.,Zbid., 26, 308-11 (1954). (16) Simard, R. G., Hmegawa, I., Bandaruk, W., Headington, C. E., Ibid., 23, 1384-7 (1951). (17) Theriault,,E. J., Ind. Eng. Chem. 21, 243-6 (1929).
I/ZO 5 40 5 3 2 10 10 30 30 1 10 30
10 10
X-RAYDIFFRACTION DATA a = 12.73 A , ; b = 10.75 A.; c A, p = 126’20’.
=
8.43
Formula Weights per Cell. 12. Density. 6.72 grams per cc. (calculated). Space Group. C;i, - C 2/c. OPTICALPROPERTIES Refractive Indices. a = 1.500 0.004; p = 1.584 f: 0.004; y = 1.596 ~t0.004. Optic Axial Angle. 271 = (-) 40’ (calculated). Pleochroic between pale green and dark emerald green. The x-ray powder diffraction data were obtained using a camera 143.2 mm. in diameter and copper K radiation with nickel filter. LITERATURE CITED
(1) Prasad, N. S. K. and Dadape, V. V.,
Current Science 26, 210 (1957.) (2) Zachariasen, IV. H., Acta Cryst. 2, 388 (1949).
