CHARLES A. -us
2384
[CONTRIBUTION FaOM THE
AND
ELLISF. PARMENTER
BAKERLABORATORY OF CHEMISTRY AT
Vol. 56
CORNELL UNIVERSITY]
Preparation of Ammonium Trinitride from Dry Mixtures of Sodium Trinitride and an Ammonium Salt BY W. J. FRIERSON AND A. W. BROWNE was adjudged most satisfactory, in view of the lower temperature and the shorter time required. The white, crystalline sublimate was shown by the standard qualitative tests,l &d by quantitative analysis involving repeated determinations NaNa (NH&SOa +NH4Na 4-NaHS04 NH3 (1) of both ammonia and the trinitride ion, to be NaN3 NH4NOs-+ NH4N3 f NaNOa (11) ammonium trinitride of a high degree of purity. Equimolecular mixtures of the dry reagents Experiments with mixtures of the reagents in were heated either statically in a sealed tube, other than equimolecular proportions led to no in VUCZLO, or dynamically in a simple sublimation improvement in the yields of ammonium tri apparatus through which was passed a continuous nitride. current of dry air. Failure to obtain strictly quantitative yields is Mixtures containing 1 g. of ammonium sulfate in no case attributable to loss of the hT3 radical and 0.4924 g. of sodium trinitride repeatedly were by decomposition, but rather to the difficulty of found to yield 87% of the theoretical amount of securing satisfactory contact between the reammonium trinitride when heated to 300' for agents. In a number of experiments the amounts forty-five minutes in the current of air. The of N) left in the reacting mass have been deteramounts of free ammonia were found to corre- mined, with the result that it was found possible spond closely to the theory based upon Equation to account for over 99% of the tririitride origiI. Because of the relatively low melting point nally taken. of ammonium nitrate, mixtures containing one In the opinion of the authors the reaction gram of this reagent with 0.8125 g. of sodium between sodium trinitride and an ammonium salt, trinitride gave consistent yields of over 93% of the or a suitable eutectic mixture of two or more volatile salt when heated to 190' for thirty min- ammonium salts, might readily be adapted for use utes. In a series of experiments with the nitrate on a larger scale, with certain precautions to mixtures in T I ~ C U aO maximum yield of 95.7740 minimize danger of detonation. was obtained after a five-hour period at 190'. (1) Browne, THIS JOURNAL, 27, 551 (1905). The dvnamic method with ammonium nitrate ITHACA, N. Y . RECEIVED SEPTEMBER 5, 1934
Ammonium trinitride may be prepared in the pure state by the metathetical reaction between sodium trinitride and an ammonium salt such as the sulfate or the nitrate
+
+ +
[CONTRIBUTION FROM THE CHEMICAL LABORATORY OF BROWN UNIVERSITY]
Further Studies of the Oxides of Potassium
BY CHARLES A. KRAUSAND ELLISF. PARMENTER~ Of the various oxides of potassium reported in They also report a yellow product whose oxygen the literature, only KzO, K202, KaOs and KzO4 content corresponded roughly to that of Kz02, but seem actually to exist. Of these, K204 has been Kraus and Whyte report KtOa as white. Rengade6 reports an oxide, KZO, but its beestablished definitely by Vernon-Harcourt2 and havior toward liquid ammonia indicates that it Holt and Sims3and has been confirmed by Kraus may have been impure. While Kraus and Whyte and W h ~ t e . Holt ~ and Sims report a buff-colored obtained KZOs and K204 by oxidation of potassium oxide, KzOa, but without analytical details. in liquid ammonia, they could obtain no evidence (1) Du Pont Fellow in Chemistry at Brown University. of the formation of an intermediate oxide, K203. (2) Vernon-Harcourt, J . Chem. Soc., 14, 267 (1861). (3) Holt and Sims, ibid., 66, 432 (1894). In the present investigation KzOz and Kz04 (4) Kraus and Whyte, THISJOU~NAL, 48, 1781 (1926). The earlier literature is reviewed by these authors.
(5) Rengade, Ann. d i m . fihys., [SI 11, 348 (1907).
