CHEMISTRY. 329 



CHEMISTRY. 



Noyes, Arthur A., California Institute of Technology, Pasadena, California. 

 Researches upon (1) the properties of solutions in relation to the ionic theory; 

 {2) a system of qualitative analysis including the rare elements; (3) the deter- 

 mination of the structure of crystalline substances by X-rays; (4) the chemistry 

 of substances at very high temperatures; (5) the effect of radiations and electric 

 discharges on the rate and equilibrium of chemical reactions. (For previous 

 reports, see Year Books Nos. 2-20.) 



In November 1921, the Trustees of the Carnegie Corporation of New- 

 York appropriated funds to the Carnegie Institution of Washington to be 

 applied for a period of five years in the support of fundamental researches in 

 physics and chemistry at the California Institute of Technology. A portion 

 of this appropriation for the year 1922 was allotted by the Institution to Dr. 

 A. A. Noyes for his researches in chemistry relating especially to the nature of 

 matter. Reports relative to the additional investigations undertaken with 

 such assistance will be found principally under the fourth and fifth sections 

 which follow. 



1. Properties of Solutions in Relation to the Ionic Theory. 



A research on the electrode-potential of bismuth has been carried out by 

 Dr. David F. Smith. This consisted in measurements of the conductivity 

 of solutions containing varying quantitities of bismuth oxide dissolved in 

 perchloric acid at a series of concentrations, made with a view of determining 

 the state in which bismuth exists in these solutions, and in measurements of 

 the electromotive force of cells of the type 



^^'PHClot}' HCI ° 4 ' Ha(1 atm ° 

 The molal electrode-potential of bismuth, the constant determining its reduc- 

 ing power in the electromotive series of elements, was found to have the values 

 — 0.30 ±0.01 volt against a solution 1 formal in total bismuth and 1 molal in 

 hydrogen ion. It is therefore somewhat more reducing than copper, whose 

 potential against 1 molal cupric ion is —0.345 volt. 



The molal electrode-potential of bismuth has also been derived by Mr. 

 E. H. Swift by an entirely independent method — that of determining the 

 equilibrium conditions at 25° of the reaction between metallic bismuth and 

 copper and their perchlorates in aqueous solution. This research leads to 

 nearly the same value of the bismuth electrode- potential. 



With the assistance of Mr. Laurence E. Weymouth, the free energy of 

 formation of solid sodium hydroxide, NaOH(s), from its elements has been 

 determined by an indirect method, which has some interest because of the 

 principles involved. This constant was derived, namely, by combining the 

 results of measurements of the electromotive forces of the two cells 

 Na in Hg, NaOH(s) under C 5 H u OH.nH 2 0,H 2 (g) 

 Hg+HgO(s), NaOH(s) under C 5 HuOH.nH 2 0, H 2 (g) 



This value is of significance as being the free-energy of formation of an 

 important alkali-element hydroxide — the first that has been determined; but 

 it was studied especially in order to enable an estimate to be made of the extent 

 to which it dissociates in flames — information needed in interpreting the 

 results of an investigation referred to below. 



