Phelps and Tillotson, Jr. — Malonic Acid. 249 



observed. There was also some decomposition, as evidenced 

 by the odor of ethyl acetate in the distillate of experiment 

 (2) of series B, when the solution was heated immediately to 

 105° in the esterilication apparatus, but if the temperature was 

 kept at 90° for fifteen minutes, as in experiment (3) of series 

 B, the ethyl acetate was not detected by its odor in the distil- 

 late in the presence of the large amount of alcohol. For the 

 purpose of examining the distillates more closely for the pres- 

 ence of ethyl acetate, blank tests were made by mixing in a 

 side-necked flask, connected with a condenser, a solution of 

 alcohol and ethyl acetate with an equal volume of concen- 

 trated sulphuric acid, and heating the liquid to a temperature 

 of 80°, at the same time passing a current of air through the 

 liquid. About 3 cm3 of the distillate was collected in a gradu- 

 ated pipette, containing an aqueous solution of sodium chloride, 

 and thoroughly shaken. When 50 cm3 of alcohol and l/8 cm3 of 

 ethyl acetate, which was calculated as the least amount to be 

 found in any of the distillates, if all of the malonic acid not 

 found as ester had been decomposed, was treated in this man- 

 ner, 0'4 cm3 of liquid separated out, easily recognized by its 

 characteristic odor as ethyl acetate. In treating by the process 

 outlined above the first 50 cm3 of the alcoholic distillates of 

 experiments (5) and (6) of series B and (1) and (2) of series C, 

 no ethyl acetate could be detected. 



In order to learn, if possible, whether the loss of malonic 

 acid in the process of esterification was due entirely to decom- 

 position, or whether part of the malonic acid was incompletely 

 esterified, experiments were made to discover if malonic acid 

 could be recovered from water solution. Shaking out a water 

 solution containing sodium chloride and 2 grm. of malonic acid 

 three times with ether gave 0*05 grm. of malonic acid, but when 

 5 grm. of malonic acid, in a similar solution, were treated 

 eighteen hours in an ether extractor, and the ethereal solution 

 evaporated under diminished pressure at 60° until the manom- 

 eter registered 15 mm , 4*97 grm. were recovered. A blank 

 test on 5 grm. of pure malonic acid showed no loss in drying 

 from an aqueous ether solution at 60° in vacuo. The sodium 

 carbonate wash waters were acidified with hydrochloric acid 

 and treated for eighteen hours in an extractor similar to that 

 described by Van Rijn*, except that an ordinary test tube 

 of about 100 cm3 capacity was used instead of the constricted 

 and perforated tube employed by him. The amounts of 

 malonic acid so recovered are shown in Table II. The amount 

 of malonic ester taken up by the sodium carbonate wash 

 waters was determined by a blank test on 75 grm. of pure malonic 

 ester, which was treated with a sodium carbonate solution, as 



* Berichte, xxviii, 2387. 

 Am. Jour. Sci. — Fourth Series, Vol. XXVI, No. 153.— September, 1908. 

 18 



