THE FORMATION OF ALCOHOLATES BY CERTAIN SALTS IN SOLUTION IN 



METHYL AND ETHYL ALCOHOLS. 



WORK OF McMASTER. 



It has been shown by the work recorded in the earlier part of this mono- 

 graph, that a large number of salts have the power to combine with water 

 when dissolved in that solvent. Indeed, we have seen that this property 

 is possessed by salts in general, although in very different degrees. Those 

 salts that have the greatest power to combine with water as water of crystal- 

 lization, have, as a rule, the greatest power to combine with water in aqueous 

 solution. 



Having established this fact in aqueous solutions, the question naturally 

 arose, Do salts have the power to combine with any solvent other than water 

 when dissolved in the solvent in question? 



To throw light on this question some work was carried out by Jones and 

 Getman,* using ethyl alcohol as the solvent, and lithium chloride and nitrate 

 and calcium nitrate as the dissolved substances. In still earlier work, Jones 

 and Getmanf used ethyl alcohol as the solvent, and potassium iodide, sodium 

 iodide, ammonium iodide, cadmium iodide, and sodium bromide as the 

 dissolved substances. The molecular rise of the boiling-point is not only 

 greater than the theoretical rise at nearly all of the concentrations em- 

 ployed, taking into account, of course, the dissociation; but the molecular 

 rise increases rapidly with the concentration of the solution. Thus, from 

 0.07 N to 2.07 N, the molecular rise of the boiling-point produced by lithium 

 chloride increases, with a fair degree of regularity, from 1.28 to 2.43. As the 

 concentration of the solution increases, the dissociation, of course, decreases, 

 and this would tend to cause the molecular rise to decrease with increasing 

 concentration. Notwithstanding this influence, we have just seen that the 

 molecular rise increases rapidly with increase in the concentration of the solu- 

 tion. The results show, in general, that the molecular rise of the boiling- 

 point of the solvent produced by the dissolved substance is greater than the 

 theoretical molecular rise for ethyl alcohol, either as found by direct experi- 

 ment in dilute solutions of non-electrolytes in the solvent in question, or as 

 calculated from the equation 



27 12 

 = 100L ' 



In a number of the above cases very marked differences manifest them- 

 selves differences that are far too large to be accounted for on the basis 

 of the dissociation of the dissolved substance. Take the case of lithium 



*Amer. Chem. Journ., 32, 338 (1904). f Ibid., 31, 338 (1904). 



147 



