Investigation of Properties of Electrolytes in Propylene Carbonate and Thermodynamic Studies of Certain High-Energy Electrochemical Reactions

• Main Author: Boden, David P
• Format: Dissertation
• Language: English
• Published: ProQuest Dissertations & Theses 01-01-1970
• Subjects: Electromagnetics; Molecular chemistry; Organic chemistry; Physical chemistry
• ISBN: 9798363541261

Equilibria of a series of 1:1 salts have been studied in propylene carbonate using conductance and viscosity measurements, In this respect, the salts LiCIO, KI, KCIO,, (Et), NCI, (Et), NCIO (n-Bu) NBr, (n-Bu), CIO, (1-Am), Ni and (1-Am), N(I-Am) B were found to be completely dissociated whereas LICI(K557), LiBr (K 18,5) and (CH) NCI(K 7.0) showed association, Single a ion conductances were determined on the basis of the assumption that the ions (i-Am) and (i-Am) B have identical conductivity and, additionally, through measurements of the transference numbers of LA and CIO" using suitable concentration cells. These single ion conductances reveal that small ions are extensively solvated in propylene carbonate: for example, the equivalent conductivity of Li at infinite dilution is 7.30 ohm³ cm³ mole" whereas that of (Am) N is B. 18 ohmcm³ mole" at 25°C. This indicates that the effective (solvated) size of the Lit lon is greater than that of the (i-Am), Nt lon. In the case of the alkali metal salta the a parameters obtained from analysis of the data by the Fuoss-Onsager equation are in general agreement with the sums of the crystallographic radil; however, this is not true in the case of the quaternary ammonium salts.