356 



Integration of the equations of velocity yields for the relative 

 concentrations of free glycerine and free fatty acid after the very- 

 short time t: 



g z= e—iP+^)k-i^ (17) 



and : 



T = \\2e-pht J^ e-k-^i] (18) 



from which: 



T = {\.,^,^^^,\ (19) 



Equation (19) gives for: 



i? = 1 T — g'k or g — T' 



P = 2 7'z.zlj 2//. + ^/Bj „ g = l^\V^\T^AY-l]* 



When now the values found experimentally are compared with 

 the values of column 8 of table 3 and with the curve g= T^ of 

 the figure, it appears that the experiment can be explained by the 

 above reaction, if the initial value of />is/;^l. 



The above should strictly speaking be completed with the deter- 

 mination of the quantity of "sulphate of glycerine mono sulphuric 

 acid" formed when glycerine and sulphuric acid are mixed, which, 

 however, will be exceedingly difficult to accomplish. 



It is, therefore, only our intention to give a plausible explanation 

 of the experimentally found curve B of the figure. Whether this 

 explanation is perfectly correct may perhaps be decided by later 

 experiments. 



We see, therefore, that in the esterification of glycerine with fatty 

 acid dissolved in strong sulphuric acid, complications are again met 

 with, which cause a deviation from the ideal case. 



Probably others than glycei-ine esters will be better adapted to 

 realise this ideal case. It appears, however, from the above that it 

 is exactly the deviations that often furnish valuable data about the 

 mechanism of a reaction that takes place in stages. 



In conclusion a few words about the second phase of the sulphuric 

 acid saponification, viz. the boiling with water. When the reaction 

 product of the first phase is made to flow into boiling water, a very 

 fine emulsion is formed, the dispersity of which rapidly diminishes. 

 The temporary fineness is caused by the presence of monolaurine, 

 which greatly lowers the surface tension between water and fat.') 

 This is attended with adsorption of monolaurine at the surface of 

 contact between fat and water (the place of reaction in saponification 

 in emulsion), which causes it to be quickly saponified, and the dis- 



1) Treub 1. c. 



