132 CHEMICAL PROPERTIES AND COMPOSITION 



with by the gradual production of water. Both these dis- 

 advantages were avoided by Menschutkin in his comparison 

 of the velocities of esterification of the alcohols, because, on 

 the one hand, instead of acetic acid he used acetic anhy- 

 dride, thus preventing formation of water and the result- 

 ing saponification, and, on the other, reduced the concen- 

 trations by employing acetone as solvent. Under these 

 circumstances the normal bimolecular process was observed, 

 following the equation (Part I, p. 193), 



dC -kCC 



~di- ^*> 



in which C^C^ are the concentrations of the alcohol and 

 acetic anhydrides, k the velocity constant, which had at 

 1 00 the following values (methyl alcohol, the highest, 

 being taken as 100) : 



I. Methyl alcohol (CH 3 OH) ... 100 



III. Secondary alcohols (XYCHOH) 



Dimethyl carbinol ..... 14-1 



Methyl ethyl carbinol ... n-6 



Methyl hexyl carbinol ... 8-7 



IV. Tertiary alcohols (XYZCOH) 



Trimethyl carbinol ..... 0-8 



The influence of hydrogen is even more clearly indicated 

 by these numbers than by those already quoted on the 

 initial velocity, and, e.g., the ratio between methyl and 

 ethyl alcohol, formerly 56:47 = 1-2 is here 100:48 = 2. 



1 The calculated value is here somewhat too small, perhaps on account 

 of the great molecular volume of C 30 H 62 O, which increases the velocity 

 of reaction. 



