Linhart — Hydrolysis of Alkyl Metallic Sulphates. 289 





JBaSO, 



I = X 







t 



, *■ 



\ 



K* 



Kf 



in hours 



in grams 



in grm. 

 equiv. 



1st order 



2d order 



44-2 



0-1550 



0-0664 



0-00520 



0-0200 



65-5 



0-2110 



0904 



0-00488 



0-0193 



135-2 



0-3717 



0-1593 



0-00446 



0-0193 



231-7 



0-5188 



0-2223 



0-00390 



0-0189 



00 



0-6435 



0-2757 







Methyl 

 Barium 



barium sulphate 0-3 grm. 

 hydroxide 0*4441 " 



equiv. per 1. 

 " 1. 



= B 

 = A 





BaS0 4 



— X 







t 



, v 



» 



K* 



Kf 



in hours 



in grams 



in grm. 

 equiv. 



1st order 



2d order 



16-5 



0-0954 



0-0409 



0-00856 



0-0197 



29*0 



0-1614 



0-0692 



0-00842 



0-0198 



44*5 



0-2352 



0-1008 



0-00828 



0-0198 



64*7 



0-3174 



0-1360 



0-00796 



0-0195 



94-5 



0-4288 



0-1846 



0-00777 



0-0198 



136*0 



0-5494 



0-2354 



0-00736 



0-0193 



205-0 



0-7046 



0-3019 



0-00681 



0-0191 



257-0 



0-8004 



0-3429 



0-00658 



0-0194 



354-0 



0-9326 



0-3991 



0*00616 



0-0195 



689-0 



1-2000 



0-5014 



0-00524 



0*0195 



00 



1-4004 



0-6000 







Summary. — The experimental results lead to the following 

 conclusions : 



1. Kremann's theory that the decomposition of ethyl barium 

 sulphate in alkaline solution is a reaction of the first order is 

 necessarily wrong, since it is based on his observation that the 

 sodium ethyl sulphate does not undergo any transformation to 

 sodium sulphate during the entire course of the reaction, and 

 on his assumption that the OH ions have no appreciable effect 

 on the rate of the reaction, except to a very small degree 

 according to the following equation : 



" Ba(C 2 H 6 S0 4 ) 2 + 4NaOH = BaS0 4 + Na 2 S0 4 +3C 2 H 5 OH + 2H 2 0." 



2. In order to verify the assumption that the reaction is of 

 the second order, experiments were carried out with bases 

 having the metallic element similar to or the same as the one 

 contained in the ester. From these experiments concordant 

 constants are obtained if the experimental results are substi- 

 tuted in a formula representing a reaction of the second order, 

 while if substituted in a formula representing a reaction of the 

 first order, which according to Kremann should give fairly con- 

 cordant constants, a gradual decrease of about 40 per cent is 

 observed. 



* See page 285. f See page 287. 



X Since strontium sulphate is somewhat soluble in water, it is instantane- 

 ously and quantitatively removed from the reacting system, by combining 

 with barium hydroxide present to form barium sulphate. It is the weights of 

 this barium sulphate equivalent to the strontium sulphate expressed in gram 

 equivalents per liter which are given in the table under grams and gram 

 equivalents. 



