PER0XYLAMIXE3ULPH0NATES AND HYDROXY LAM I NLTRISULPHOXATES. 21 



h [s already known (this Journ 3, 218 ; 7, 40) that, in the presence 

 of alkali, the nitroxy- radicals of a hydroxylaminesulphonate tend to 

 separate from the sulphonate radicals. Such a tendency, exercised in 

 the presence of undecomposed peroxylaminesulphonate, will lead to 

 the production of hydroxylaminetrisulphonate and nitrite in the case 

 of hydroperoxylaminesulphonate, and of the former salt and hyponitrite 

 in the case of hydroxy laminedisulphonate, thus : 



(SO i K)Ä0 1 +(SO,K) 1 NO.OH=2(SO,K) t NO(SO i K)+HONO; 



(S0 i K) 4 N 1 1 +(S0,K) f N0H =2(S0 3 K) 2 NO(S0 3 K)+7 2 (HON) 2 . 

 When the three equations are combined, the intermediate products 

 disappear and the following equation is left, 



6(SO i K) 4 N 1 1 +H 1 0=8(SO I K) J NO+2NO i H+N' 1 (1) 



or, leaving the comparatively stable hydroxylaininedisulphonate 

 unchanged, 



2(SO I K) 4 N 1 O f +H f O=2(S0 8 K) I NO+(SO I Kj 1 NOH+NO i H....(2) 

 It is fairly -certain that the sulphate which, in greatly varying 

 although never very large quantity, is always produced, does not come 

 from the hydrolysis of the salt itself or from that of either the 

 hydroxylaminetrisulphonate or hydroxylaininedisulphonate derived 

 from it. For the trisulphonate is remarkably stable in presence of 

 alkali, and the disulphonate, although unstable in its presence, yields 

 not sulphate but sulphite. As this is also true of hydroxy laminemono- 

 sulphonate, it may be assumed to be so in the case of peroxylamine- 

 sulphonate. The sulphate should therefore have another origin, which 

 may well be taken to be the decomposition of the hydroperoxylamine- 

 sulphonate in circumstances in which it fails to interact with peroxyl- 

 aminesulphonate, perhaps because the temperature of the solutionis 

 too low. In that case, it will naturally hydrolyse, one half becoming 

 hydroxylaminedisulphonate by oxidising the other half into 

 sulphate and nitrous acid, 



