MAY 15, 1937
ANALYTICAL EDITION
Cone, R. M., Hatcher, W. H., and Greenwald, W. F., Chem.
(4)
Met. Eng., 43, 128-32 (1936). (5) Darkis, F. R., Dixon, L. F., and Gross, P. M., IND.ENG.CEIEM., 27, 1152 (1935). (6) Dixon, L. F.,Darkis, F. R., et al., Ibid., 28, 180 (1936). (7) Fausz, J., and Rumm, H., Kolloid Beihefte, 39, 58-104 (1933). (8) Garner, W. W., Bacon, C. W., and Bowling, J. D., Jr., IND. E N G .CHEM.,26, 970-4 (1934). (9) Gladkov, N. G . , and Trankvilitzkaya, N. A.,TahachnaW Prom., 2, 23-6 (1934). (10) Kotnitzkii, A. I., Ibid., 4, 52 (1934).
221
(11) Lmdner, Josei, 2.anal. Chem., 86, 141-53 (1931). (12) Miloslavskii, N. M., and Palant. A. I., L'kmin. Xheni. Zhur., 5, Tech. Pt., 117-25 (19301. (13) Sadtler, S. S.,J. IND.E N G .CHEY.,2, 66-7 (1910). (14) Vladescu, I., and Zaporojanu, I., Bul. cultivarei feernientaveh T u t u n u h i , 24, 67-83 (1935). (15) Wilson, R. E., and Fuwa, Tyler, J. IXD.EKG. CHEW,14, 913-18 (1922). RECEIVED September 28, 1936. Presented before the Divlsion of . I g ~ ~ c u l tural and Food Chemistry at the 92nd Meeting of the American Chemical Society, Pittsburgh, Pa., September 7 to 11, 1936,
Separation of Beryllium in the Presence of Complex Tartrates HOKE S. MILLER, Department of Chemistry, Columbia University, New York, N. Y.
0
WING to statements in the literature (1, 4) that solu-
tions of beryllium salts in the presence of tartrate are stable to strong alkali, the idea has arisen that beryllium cannot be precipitated as the hydroxide in the presence of tartrate. The author has found, however, that beryllium may be precipitated from its complex tartrate solution by means of an optimum hydroxy Lion concentration provided by the addition of ammonium hydroxide. In this way it is possible to separate beryllium, to a fairly quantitative extent, from such elements as aluminum, iron, copper, and chromium, which form complex tartrates from which the hydroxides of the metals are not precipitable upon addition of an optimum quantity of ammonium hydroxide. Recently Jilek and Kota (9) demonstrated that beryllium could be separated quantitatively from aluminum by adding a known quantity of ammonium tartate solution to the TABLEI. PRECIPITATION .OF BERYLLIUM FROM TARTRATE Be0 Theoretical .~~.
0.5 M Potassium Tartrate
146 3a 146.3" 146.3" 146.3'" 146,3O 146.3O 146.3O 146.3'3 146,3a 146.3O
20 20 20 20 25 25 25 25 25 25
MO . I
16 M N&OH Cc. 8
cc .
salts of aluminum and beryllium; subsequent addition of an excess guanidine carbonate precipitates beryllium as the basic carbonate while the aluminum remains in solution. The method herein proposed eliminates the use of guanidine carbonate by employing ammonium hydroxide. A solution of beryllium nitrate, containing a known quantity of beryllium, was accurately pipetted into a 250-cc. beaker, to which was added a measured portion of 0.5 M potassium tartrate solution. The contents of the beaker were well mixed, after which a specified amount of 16M ammonium hydroxide was added dropwise. After standing at room temperature (25' C.) for 10 hours, the precipitate was filtered on No. 44 Whatman paper, washed with water containing a trace of ammonium nitrate (S), dissolved with dilute nitric acid, reprecipitated as many times as indicated in the Tables I and 11, washed as described above, ignited, and weighed as beryllium oxide.
Tables I and I1 are illustrative of typical results. It is significant that the amount of beryllium recovered depends, to within certain limits, on the quantity of ammonium ITSCOMPLEX hydroxide added to a given quantity of the salt solution. If the final solution is too feebly alkaline with ammonium hydroxide, all the beryllium may not be precipitated, thus Be0 Found leading to low results. Mu.
113.8 126.0 144.4 146.4 146.2 145.1 145.1 144.1 143.7 144.2
10 14 16 15 16 16 16 16 16
25 15 140.0 140,Oa 3 5 14.2 14.0b 3 5 14.0 14.Ob 5 14.0 14.0b 3 5 14.0 14.0b 3 ~- . 5 50.00 DC. of Be(N0& solution w 146.3 mg. of BeO, etc. b 5.00 cc. of Be(N0a)a solution 20 cc. HzO ci 14.0mg. of Be?. In each case the precipitate was dissolved in dilute nitric acid and reprecipitated.
+
Precipitation of Beryllium Eight determinations of beryllium were made by precipitating beryllium as beryllium hydroxide in the presence of the complex tartrates of aluminum, iron, copper, and chromium. To 50 cc. of solution containing Be(NO& = 140.0 mg. BeO, AlC13 = 11.2 mg. Al, FeC13 = 20.7 mg. Fe, CuCl? s 47.3 mg. Cu, and CrCl3 = 19.5 mg. Cr, were added 30 cc. of 0.5 M potassium tartrate, followed by the dropwise addition of 16 cc. of 16 M ammonium hydroxide. From this point on the procedure described above was followed. The precipitates were redissolved three times and reprecipitated. An average of 143.6 * 1.3 mg. Be0 (theoretical, 140.0 mg. BeO) was obtained.
TABLE11. PRECIPITATION OF BERYLLIUM FROM ITSCOMPLEX The principal disadvantage of this method of analysis is TARTRATE" the tendency of gelatinous precipitates to co-precipitate (In the presence of aluminum w 33.5 mg.) crystalloidal matter. For this reason it is not recommended 0.5 M Potassium 16 M Be0 for very precise and accurate separations and determinations. NHPOH Found Tartrate cc.
cc.
(1 For each determination 50.00 CC. of 146.3 m g . of Be0 and AlClil m.33.5 mg. solved In nitric acid and reprecipitated.
Mg.
Literature Cited (1) Aubel, C., and Rsmdohr, G., Liebigs A n n . Chem., 103, 33 (1857). (2) Jilek, A., and Kota, J., 2.anal. Chem., 87, 422 (1932) ; CoZZection CrechosZou. Chem. Commun., 4, 97 (1932). (3) Parsons, C . L., and Barnes, S. K., J. Am. Chem. SOC.,28, 1589 (1906). (4) Rosenheim, A., and Lehmann, F., Ann., 440, 153 (1924). RECBIVED January 11, 1937.
