The extrapolation of EMF data to infinite dilution in non-aqueous and mixed solvents

Abstract

Abstract

Thermodynamics of the cell { Li- Amalgam | LiX (m)| AgX | Ag }(X=Cl,Br) and medium effects upon LiX in (acetonitrile + water), (1,4-dioxane + water), and (methanol + water) solvent mixtures with related solvation parameters

“…According to a classical scheme of the electrochemical thermodynamics, (21) analysis of the E values is performed in terms of the following function: (4) …”

Extraction of Carboxylic Acids by Amine-Based Extractants: Apparent Extractant Basicity According to the pH of Half-Neutralization

“…Moreover, calculating the activity coefficients of ions is much more complicated in an organic phase than in water, where calculations can be done according to the Debye-Hu ¨ckel equations. Marcus et al 8 proposed a method that uses the dielectric constants of the components to determine the standard potential of a nonaqueous solution. They noted that other scientists have used at least 10 terms to calculate the standard potential of an ion.…”

Ionization constants ofo-phthalic acid in (propylene carbonate + water) and (ethylene carbonate + water), and thermodynamics of the cellPt|H2|HCl(m)| Hg2Cl2|Hg

“…For cell (II) working in (EC + W) and comprising the Hg 2 Cl 2 electrode, the required E o values had to be newly obtained from our measurements of E III on the ad hoc cell (III), and are collected in table 2. According to a classical scheme of electrochemical thermodynamics, (18) combining the E III expression with the extended Debye-Hückel equation for the mean molal activity coefficients γ ± of HCl at molalities m, and rearranging, the functional equation becomes: (4) where M Z is the molar mass of the solvent mixture Z = (EC + W) at mass fraction w s of EC. The intercept of the against m straight line at m = 0 gives values of E o at the relevant mass fraction of EC, which are quoted at the bottom of table 2.…”