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

110th Anniversary: Theory of Activity Coefficients for Lithium Salts in Aqueous and Nonaqueous Solvents and in Solvent Mixtures

“…Figure shows calculated (lines) and measured (symbols) mean ion activity coefficients for LiCl in mixtures of H 2 O/MeOH (a), , /EtOH (b), , /acetonitrile (c), and /1,4-dioxane at 298.15 K with varying H 2 O bulk solvent compositions. We put into eq and in turn, in eq , where is given by the solution of eqs SI1–SI3.…”

“…We put into eq and in turn, in eq , where is given by the solution of eqs SI1–SI3. Table gives ε r and salt-free solvent mixture density for different solvent compositions determined by measurements. − To calculate of a nonaqueous component of a mixed-solvent electrolyte, we fit σ to the measured mean ion activity coefficient for LiCl in that solvent and use eq . (If salt-in-single-solvent activity coefficients are not available, we use the solvent mixture that is richest in that solvent.)…”

“…Measured (symbols) and calculated (lines) ln f ± for LiCl in mixtures of water/methanol (a, data from refs and ), water/ethanol (b, data from refs and ), water/acetonitrile (c, data from ref ), and water/1,4-dioxane (d, data from ref ) for various volume fractions of each solvent (noted in the figure) at 298.15 K. The insets show ion diameter σ as a function of bulk solvent water volume fraction, ϕ H 2 O .…”

“…This solvated diameter provides a molecular basis for calculating activity coefficient f ± in a mixed solvent with parameter ω t for each solvent t in the mixture. Figure 5 shows calculated (lines) and measured (symbols) mean ion activity coefficients for LiCl in mixtures of H 2 O/ MeOH (a), 68,69 /EtOH (b), 70,71 /acetonitrile (c), 68 and /1,4dioxane 68 at 298.15 K with varying H 2 O bulk solvent compositions. We put ω t into eq 27 and in turn, in eq 16, where φ * t is given by the solution of eqs SI1−SI3.…”

Activity coefficients of LiCl in (PEG 4000+water) at T=(288.15, 298.15, and 308.15)K

“…In an earlier work [20], we also obtained good results with selective electrodes for Na + and Cl À in obtaining the activity coefficients of LiCl in (water + ethanol). The electrode system employed in the earlier work [20] was previously checked and calibrated by measuring the activity coefficients of LiCl to w = 0, 0.2, and 0.4 (methanol + water) and comparing them with results obtained from the literature [21].…”