( 770 ) 



The reaction proved to l)e one of the tirst order, tlio velofity constant 

 did not change with the concentration; so it is a nionomolecnUir 

 one. At 65°, for instance /• = 0.0019 for a sohition of 2.5 grams of 

 the oxinie in 50 as well as in 100 cc. of 93. 67n sulphuric acid (time 

 in minutes; transformation of \'._, of the oxime after 160 minutes). 



The transformation velocity increases with the concentration of the 

 acid as shown from the following table: 



At 65°, a 86.57n sulphuric acid gave a constant of 0.0006 (time 

 ofVa transformation ^501 minutes). When nsing 99.2"/„ acid at 6(P, 

 practically all the oxime had been converted after 15 minutes. 



The influence of the temperature is ap[)arent from the following 

 figures : 



at 60°, 93.6V0H.3ÖO,,, /■ = 0,0011; 94 6 7„II,S(),, Z= 0,0013 

 65°, „ „ „ = 0,0019 „ „ „ = 0,0021 



The temjierature-coefficient for 10^ is lliei-efoi-e about 3. 



A solution of SO, in chloroform did nol uppeai- lo cause any trans- 

 formation of the oxime. 



The results of this research therefore contirm the view that in the 

 BECKMANN-transformation we are dealing with a real intramolecular 

 rearrangement. E\oii if (he application of sulphuric acid should cause 

 the formalion of an ijitermediate compound (which has not yet l)een 

 positi\ely proved, but \\hich is very probal)le ') ) our experiments 

 show that this formation (or the conversion 1 into II) lakes place 

 with immeasurably great \elocily. The \ ery ])erceptible development 

 of heat which occurs on luixiug the oxime willi Ihe coiiceuti'aled 

 sulj)lnu'ic acids also poiiUs to this fact. 



Addcnduiii. Of late years, Stikglitz and his coworkers (Amer. 

 Chem. J. 1896—1903) have been engaged in tiie study of the 

 BECKMANiN-rearrangemeut. In my opinion Stik(;ijtz's ideas caimot be 

 accej)ted in theii- entirety. Recently this chemist has given a sunnnary 

 of his conclusions in a separate article "on the l>K(;KMANN-i'eai'range- 



^) If to an ollioreal solnlion of llic oxiiiio is added n solution ot' sulpliiirlc arid 

 ill elliei', a precipitate is olitained llie nature of which will be investigated. 



