PEROXYLAMINESULPHONATES Ä.ND HYDROXYLAMINETRISULPHOMATES. L9 



lead peroxide, silver oxide, or ozone should raise the valency of the 

 nitrogen to only quadrivalency and not to quinquevalency, and 

 that it should raise it at all without converting the sulphonate to 

 sulphate radicals. Neither Clans nor Raschig assumes thai it does, 

 for according to them the nitrogen of the hydroxylaminedisulphonate 

 is itself quinque valent. But there arc two strong reasons for 

 rejecting the assumption that the valency <>f the nitrogen is raised by 

 the oxidation of hydroxylaminedisulphonates to peroxylaminesul- 

 phonates. One of these is the nature of the products of the 

 spontaneous decomposition of a peroxylaminesulphonate. These 

 products, in so far as they contain nitrogen, are all trivalent nitrogen 

 compounds, namely and in the main, hydroxylaminetrisulphonate, 

 hydroxylaminedisulphonate, and nitrite ; if nitrous oxide is also recog- 

 nised, that will not affect the argument. No nitrate can be found 

 among these products (p. 36). It is, of course, the establishment of the 

 tri valency of the nitrogen of the first-named product which has really set- 

 tled the matter. But as it is only as yet on the chemical work of Divers 

 and the author (this Journ., 7, 3-1), that the adoption of the trivalency of 

 the nitrogen in hydroxylaminedisulphonates can be based, the result 

 of a determination by a cryoscopic method (p. 33) of the molecular 

 magnitude of the normal sodium hydroxylaminedisulphonate may 

 be adduced in support of it. This result shows that the molecule 

 of the salt contains but one atom of nitrogen (necessarily therefore 

 trivalent), and not two atoms as had been represented by 

 Clans and by Raschig. Now, the spontaneous decomposition of 

 a peroxylaminesulphonate can only be hydrolytic and, is therefore 

 one not affecting the valency of the nitrogen ; or, should this be 

 contested, it can still be asserted that at least this decomposition 

 cannot be interpreted as a change involving a fall of the valency of 

 the nitrogen. 



