Substituted Aliphatic Acids. 



295 



Procedure. — The hydrolysis experiments were carried on in 

 the thermostat described in the first paper* of the series. The 

 temperature was regulated so that variations were never more 

 than a tenth of a degree. The esters were hydrolyzed in 250 cm3 

 flasks, which were filled to the mark with decinormal hydro- 

 chloric acid and warmed to the temperature of the thermostat 

 before starting the reaction. The esters were measured out in 

 quantities of about 2-5 cm3 from a graduated pipette. At regular 

 intervals 25 cn ' 3 portions of the reaction mixture were removed 

 by means of a pipette, run into cold water, and immediately 

 titrated with decinormal barium hydroxide solution. Phenol- 

 phthalein was used as an indicator. 



Experiments were carried on at 25 , 2°, 35°, and 45°, duplicates 

 being obtained in all the cases. Calculations were made by 

 using the titration formula for reactions of the first order. 

 Figures are given below for the series which gave, the most 

 regular constants. Averages of duplicate series are also 

 recorded. 



Table I. 



N/10 HC1. 

 Ethyl 

 Glycollate 

 10 5 K 



Hydrolysis at 25'2° 

 Ethyl 

 Acetate 

 10 5 K 



Time 

 (minutes) 



120 63-6 



240 67-0 



360 64-9 



600 64-2 



840 64-9 



1380 65-6 



2040 65-0 



3180 



Averages... 64*7 



Averages 64*9 



(duplicate) 



Hydrolysis at 35° 



Ethyl Alkyloxy Acetates 

 Methyloxy Ethyloxy Propyloxy 



90 

 180 

 360 

 600 

 900 

 1440 

 2160 



(155-5) 

 158-8 

 163-7 

 162-1 

 162-8 

 16G-4 



(174-0) 



. 162-7 

 . 162-6 



71-0 

 69-5 

 69-6 

 (79-8) 

 71-9 

 69 9 

 70-6 



70-4 

 68-5 



171-1 

 184-0 

 183-1 

 176-1 

 168-0 

 166-9 

 160-5 



172-8 

 166-2 



10 5 K 



36-3 

 39-9 

 41-8 

 36-7 

 38-2 

 37-7 

 36-0 



38-1 

 38-9 



89-5 



89-5 



88-4 



90-9} 



90 4 



90-5 



92-3 



90-2 

 90-0 



10 5 Kf 

 37-4 

 36-4 

 36-5 

 35-4 

 36-3 

 36-5 

 35-2 



36-2 

 36-1 



(80-5) 

 85-3 

 87-2 

 88-3J 

 87-2 

 87-5 

 87-9 



87-2 



87-5 



10 5 Kf 



34-1 



36-0 



35-6 



35-7 



36-3 



36-9 



35-9 



35-8 

 35-8 



(71 



(78 

 82 

 85 

 85 

 86 

 86 



85 

 84 



8) 



4t 



Averages.. 162-7 172-8 90-2 87-2 85-3 



Averages.. 162-6 166-2 90"0 87-5 84-0 



(duplicate) 



* Loc. cit. 



f These constants for 25'2° are calculated from series run at 25'0°. Time 

 intervals are slightly different. \ Time interval, 700 minutes. 



