[- 218 ] 



XIII. 



ON THE ACTION OF BROMINE OX SOME DERIVATIVES OF 



DIPHENYLAMINE. 



By HUGH RYAN, D.Sc, am. WILLIAM O'RIORDAN, M.Sc, 



• iy College, Dublin. 



Xovemiieh II, 191S. I'uMishea Fbbbuabt, 13, 1919. 



When diphenylamine is employed tiliser it is gradually changed, by 



the action of tin- decomposition pn the powder, intonitro derivatives 



which c rb nitrous gases, and. hence, do not act as stabilising 



It i> important, therefore, t" have a reliable method f<>v estimating 

 tin- amount of diphenylamine remaining un tltered al any time during the life 

 Further, diphenyl uitrosamine, which i- probably the first 

 luct formed by the action •>< the nitrou n diphenylamine, is itself 



aim iiphenylamine, so that a means of ascertain- 



in.' tin' amount of this product would also !"• "i" much importance. 



M. Buisson in I olumetric method, 



to M. Berji ■ - I' Ires de Vei sai les, for the 



mation of thi imount of diphenylamine, no matter whethei il 



iwder in tli' • its nitroso derivative. The 



method depends on the fact that diphenylamine, when acted upon by bromine, 



i-dipheii] ghed quantity of the 



_ iphenylamine, diphenylnitrosamine ami nitro derivatives 



enylamine) is boiled with a dilute solution inm hydroxide in 



a i' i with a condenser. Under tin- action of the alkali and the 



•.<l.-t the diphenylnitrosamine is converted, 



t | M Bergei Iiphenylamine, and, as the latter is volatile with 



mi, the di.-tiil tins all the diphenylamine contained in the powder 



free diphenylamine ami diphenylnitrosamine. The nitro derivatives of 



diphenylamii averted during this process into 



diphenylamine. The dipheuylainine in the distillate is then estimated by 



ting it into its tetrabromo derivative by ad i standard 



5 the excess of bromine volumetrically. 

 Experiments carried out at the Ardeer factory of Nobel's Exploi 



nfirm the statement that the diphenylnitrosamine in the 

 process described ia Iiphenylamine, ami in this connexion 



