480 P. 0. Ray — Mercurous Nitrite and its Derivatives. [No. 4, 



This is also the case with silver nitrite, though not in so marked a 

 degree.* 



Exp. IV. This was a control experiment in which silver nitrite 

 was digested with ethyl iodide : 90 g. of the silver salt were treated 

 with 88 g. of the alkyl haloid. The yield of ethyl nitrite was 4'2g. 



Nitro Ethane. 



After the evolution of ethyl nitrite had ceased, the contents of the 

 flask were subjected to distillation, first over a water bath, and after- 

 wards over an oil bath. The distillates were caught separately. 



It was invariably found that during distillation over an oil bath, the 

 receiver was filled witli nitrons fumes, a part of which was absorbed by 

 the distillate, imparting to it a bluish tinge. As there was not the 

 slightest trace of yellow colour either in the flask or in the condenser 

 itself, it was suspected that nitric oxide was evolved by the slow and 

 gradual decomposition of a portion of mercurous nitrite, which combined 

 with the oxygen of the air in the receiver. The suspicion was confirmed. 

 The presence of the nitrous fumes is highly objectionable, as the crude 

 nitro ethane so obstinately holds them in solution that they cannot be 

 got rid of during fractionation. Distillation in a slow current of carbon 

 dioxide was therefore resorted to for excluding air. In the control 

 experiment with silver nitrite (See ante, Exp. IV.) nitrous fumes, though 

 in a far lesser degree, were also noticed in the receiver.f 



After the distillation was over, the compact mass of mercurous 

 iodide and nitrite were removed from the flask, well powdered in a 

 mortar, and once more treated with the fraction below 100°, when a 

 further quantity of crude nitro ethane was obtained. 



A fair idea of the yield of nitro ethane may be had from the 

 details of one among several experiments. 190 g. of mercurous nitrite 

 and 95 g. of ethyl iodide yielded a distillate of 7 g. between 100°-108°, 

 of 3Jg. between 108°-] 10°, and of 4g. between 111°-1 14°. 



The fraction which came off between 113°'5-114° (uncorrected) was 

 practically pure nitro ethane. It was treated with an alcoholic solution 

 of caustic soda as recommended by Nef. (Annalen : 280, p. 267). The 



* " Es gelang uns unter keinen Umstanden das ganze Jodathyl in die Reaction 

 zu verwiekeln, sonderu stets war das bei der Rectification zuersfc iibergehende 

 Produkt stark jodhaltig. Wir haben auf jede weise versucht, das Jodathyl voll 

 standig anszubenten, doch imraer vergeblich." (Loc. cit., p. 402.) 



f The behaviour of Mercurous Nitrite in this respect also resembles that of 

 Silver Nitrite. Cf. Divers and Schimidzu " Action of heat upon Silver Nitrite, air 

 being excluded" — (Trans. Chera. Soc. Journ., 47, 634), where it is shown that nitric 

 oxide is one of the products of decomposition. 



