VELOCITY OF ESTERIFICATION 131 



converted into esters by heating equivalent quantities for 



an hour at 144 : 



0123456789 

 HOCH 3 .... 56 - - 



HOCH 2 X ... 39 40 47 47 ----- - 



HOCHXY ... 15 15 22 27 



HOCXYZ ... ______ 012 i 



The table shows the highest initial velocity, 56, for methyl 

 alcohol ; for the primary alcohols from 39 to 47, whilst for 

 tertiary the numbers fall to between o and 2. But the 

 numbers are arranged according to the number of hydrogen 

 atoms which are attached to the second carbon, and increase 

 from left to right. Thus, e.g. under the heading 3 for 

 HOCH 2 X the number 47 refers to H 3 CCH 2 OH; under 2 

 the mean for the alcohols XCH 2 CH 2 OH, and so on. 



Three deductions may be noted : firstly, the accelerative 

 action of the hydrogen attached to the hydroxylic carbon 

 atom, secondly, that even the more distant hydrogen pro- 

 duces a similar effect, and thirdly, that the latter influence 

 is smaller than the former ; thus three more distant atoms 

 raise the value 39 for HOCH 2 X to 47, but one directly 

 combined atom raises it to 56. 



A similarly arranged table shows that the action on 

 acids, when they are heated with a fixed alcohol, ethyl 

 alcohol, is similar : 



I 



HC^ 



0123 

 O 



62 



OH 



.0 



6 2<; 25 46 



\)H 



A second series of investigations by the same author 1 

 refer to a simpler process of esterification. In the preced- 

 ing case it is somewhat complicated by the fact that the 

 concentrations are large, and the esterification interfered 



1 Zeitschr. f. Phys. Chem. I. 610 ; see also ester formation from acid 

 chlorides, Bruner and Tolloczko, Acad. de Cracovie, 1899, 474. 



I 2 



