VIII, A, 1 



Gibbs and Pratt: Hydroxyl and Carboxyl 

 Table II. — Methyl ether of salicylic acid. « 00= 387. 



37 



0/1000. 



A. 



100 cc. 



K=100k. 



32 



18.35 



4.74 



0.0073 



64 



26.30 



6.79 



0. 0077 



128 



36.81 



9.51 



0. 0078 



256 



50.77 



13.12 



0.0077 



512 



69.46 



17.95 



0.0078 



1,024 



95.00 



24.55 



0.0078 





K=0. 0077 





This value agrees with that found by Ostwald 7 when his 

 figures are calculated with the Kohlrausch units. If the above 

 values are correctly given, it is evident that the affinity constants 

 of acids are not necessarily measures of the rates of saponifica- 

 tion of similar esters of the acids. At the present time suf- 

 ficient data are not available to explain these anomalies. 



Our method of approaching this problem has included a study 

 of the hydroxyl group of phenol and its conversion in part and 

 almost wholly into its sodium salt, a study of benzoic acid and 

 of benzyl derivatives in which the >C=0 has been replaced by 

 > CH 2 , and finally of various ortho combinations of these groups, 

 as found in o-cresol, o-hydroxybenzyl alcohol, o-hydroxybenzoic 

 acid, its sodium salts, methyl ether, and the methyl ester of this 

 ether. 



PHENOL. FIG. 1 



The absorption spectrum of phenol has been investigated 

 by Hartley and Huntington; 8 Hartley, Dobie and Lauder; 9 and 

 by Baly and Ewbank. 10 The last authors observed a shift in the 

 absorption band in the presence of 4 equivalents of alkali, a 

 condition which Baly and Desh 1X found in other compounds to 

 be indicative of enol-keto tautomerism. 



We have photographed this compound in neutral and acid al- 

 cohol solution and in the presence of 0.1, 1, 5, and 500 equivalents 

 of sodium ethoxide, and have found that with the increase in 

 the concentration of the sodium salt of phenol and corresponding 

 decrease of free phenol, the absorption band becomes more 



7 Zeitschr. f. physik. Chem. (1889), 3, 266. 

 'Phil. Trans. Roy. Soc. London (1879), 170, 270. 

 'Journ. Chem. Soc. London (1902), 81, 929. 

 "Ibid. (1905), 87, 1347. 

 "Ibid. (1904), 85, 1029; (1905), 87, 766. 



