170 The Philippine Journal of Science wis 



are static in their meaning. The term isorropesis was proposed 

 to designate the interrelation between groups of this type. The 

 activity of a carbonyl radical is not inherent in the group itself, 

 but is produced by the action of neighboring atoms that render 

 the group nascent. 15 The causes underlying this action are more 

 easily understood by means of the partial valency theory. The 

 amount of affinity in excess of that utilized in holding the doubly 

 bound atoms together will depend upon the presence of free 

 affinity exerted by neighboring atoms. In the absence of such 

 forces, the energy of the two atoms will be mutually neutralized 

 and in equilibrium. 



When phthaloxime is converted into its salts, a marked altera- 

 tion in molecular vibration is manifested to the eye by the change 

 from a colorless compound to a colored one. The new vibration 

 may be due either to a different equilibrium of the same molecule 

 induced by the presence of a positive metal atom, or to an actual 

 alteration in molecular structure. 



COLOR DUE TO CHANGE IN EQUILIBRIUM BETWEEN PARTIAL 



VALENCIES 



If the production of color in the formation of salts of phthal- 

 oxime is due to a change in the vibration of the molecule un- 

 accompanied by atomic tautomerism, it must be dependent upon 

 a new equilibrium between the partial valencies of the unsatu- 

 rated groups. The change of equilibrium is not to be attributed 

 to the increased weight of the molecule and consequent reduc- 

 tion in the period of vibration. The replacement of the acidic 

 hydrogen by groups with high molecular weight, as in the case 

 of the benzoate, causes a change in the activity of the molecule 

 shown by a reduction in the persistence of the characteristic 

 absorption band in the spectrum. However, the type of 

 spectrum remains the same. Therefore, the activity of the 

 hydrogen is not greatly different from that of various organic 

 radicals, and the compound retains its true oxime condition in 

 every case. It is to be noted that an aqueous solution of oxime 

 shows a slightly more pronounced yellow tint than a correspond- 

 ing alcohol solution and that the color in both cases is decreased 

 by a trace of mineral acid. The ethers and esters of the oxime 

 do not behave in an analogous manner, but always give solutions 

 of equal color intensity that are unchanged by traces of acid. 

 The acidic hydrogen, therefore, influences the equilibrium to a 



15 Baly and Schaefer, ibid. (1908), 93, 1814. 



