296 



Phelps and Eddy — Ester Formation. 



Art. XXXIII. — Researches on the Influence of Catalytic 

 Agents in Ester Formation. The Esterification of Benzoic 

 Acid with Certain Chlorides / by I. K. and M. A. Phelps 

 and E. A. Eddy. 



[Contributions from the Kent Chemical Laboratory of Yale Univ. — clxxxix.] 



Irc this Journal* in earlier work under the direction of one 

 of as, the efficiency of zinc chloride with hydrochloric acid as a 

 catalytic agent in the formation of the ethyl esters of benzoic, 

 succinic, malonic, and cyanacetic acids has been shown. The 

 esterification was carried on at a temperature of 100°-110° in 

 an apparatus arranged for the purpose. 



In the work given in this paper, in the specially arranged 

 flasks illustrated in the work on succinic ester referred to, the 

 catalytic action of certain chlorides in presence of hydrochloric 

 acid in small amount in the esterification of benzoic acid with 

 ethyl alcohol is brought into comparison with the similar action 

 of zinc chloride with hydrochloric or of hydrochloric acid 

 alone as catalytic agent. The esterification of this acid with- 

 out a catalytic agent is shown to be almost none at all. 



Table I. 



Ben- 

 zoic 

 No. acid 

 grm. 



( 1) 50 

 ( 2) 50 

 ( 3) 50 

 ( 4) 50 

 ( 5) 50 

 ( 6) 50 

 ( ?) 50 

 ( 8) 50 

 ( 9) 50 



(10) 50 



(11) 50 



(12) 50 



(13) 50 



(14) 50 



(15) 50 



(16) 50 



(17) 50 



(18) 50 



(19) 50 



(20) 50 

 \ 



Catalyzer 



grm. 



(21) 50 



ZnCl 2 



1 



1 



1 



10 



10 







8 



1 



10 







6 



NHC1 



4 



7 



CuCl 2 1 



" 9 



CuCL. 



a 

 a 

 a 



NaCl 



a 



KC1 



a 



LiCl 



a 



2HO 



12 



50 

 00 

 00 

 00 

 00 

 00 

 86 

 60 

 09 

 90 

 62 

 20 

 79 

 85 

 00 

 87 



Abs. Ale. 

 with HC1 



Benzoic ester 



Time 



cm" 

 300 

 200 

 200 

 200 

 200 

 200 

 300 

 300 

 200 

 400 

 200 

 200 

 200 

 200 

 200 

 200 

 200 

 200 

 200 

 200 



per ct. 



58 200 1-25 



25 

 25 

 25 

 25 

 25 

 25 

 25 

 25 

 25 

 25 

 25 

 25 

 25 

 25 

 25 

 25 

 25 

 25 

 25 



hr. 

 3 



2 

 3 

 4 



2 

 2 

 2 

 3 

 2 

 4 

 2 

 2 

 2 

 2 

 2 

 2 

 2 

 2 

 2 

 3 



20 



20 

 20 



Theory Found 



grm. 



_. 61 



.. 61 



30 61 



_. 61 



._ 61 



.. 61 



48 

 48 

 48 

 48 

 48 

 48 

 48 

 48 

 48 

 48 

 48 

 48 

 48 

 48 

 48 

 48 

 48 

 48 

 48 

 48 



grm. 



trace 



44-54 



50-88 



51*53 



53-26 



52-86 



59-23 



60-27 



60-79 



61*48 



38*14 



42-00 



43-94 



37*23 



42-14 



37-80 



36-00 



32*95 



5391 



5962 



per cent 



72 

 82 

 83 

 86 

 86 

 96 

 98 

 98 

 100 

 62 

 68 

 71 

 60 

 68 

 61 

 58 

 53 

 87 

 97 



61-48 59-05 96-1 



* This Journal, xxiv, 194 ; xxv, 39 ; xxvi, 143 ; xxvi, 264. 



