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- W3025071777 abstract "Abstract Standard potentials ( E° ) of Li, K and Tl electrodes in propylene carbonate ( PC ) have been determined, at 25°, on the basis of the “solvent-independent” half-reaction: Ferricinium + + e ⇌Ferrocene. In addition, estimates of Δ G °, Δ H °, and Δ S ° for the formation of Li + , K + , and Tl + in PC have been obtained from temperature-dependence studies. The observed values of E ° are in the order Tl > Li > K as compared to the order Tl > K > Li in water. The decrease in entropy, which would serve as a measure of the order-promoting ability of an ion, follows the sequence Li > K > Tl. From a consideration of the crystallographic radii of the cations involved this trend would suggest that such ordering is primarily a result of electrostatic solvation in the immediate vicinity of the ions. The somewhat large decrease in entropy observed in the case of Li + reflects very extensive solvation of this particular cation. The free energies of transfer for the three cations from water ( D = 78·54) to PC ( D = 64·4) are calculated to be +1·81 (Li + ), −2·42 (K + ), and −2·88 (Tl + ) kcal/mole. Although an approximately linear relationship exists between these free energies of transfer and the reciprocals of crystallographic radii of the ions, both the magnitudes and the signs of these free energies are not readily understood in terms of the Born equation. The relatively large free energy decrease associated with the transfer of Tl + might be attributed to a fairly strong solvation encountered by this cation due to its empty 5 f orbital, aided by the possibility that the solvating carbonyl oxygen of PC is more accessible to the cations in general." @default.
- W3025071777 created "2020-05-21" @default.
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- W3025071777 date "1974-01-15" @default.
- W3025071777 modified "2023-09-24" @default.
- W3025071777 title "ChemInform Abstract: THERMODYNAMICS OF LITHIUM, POTASSIUM AND THALLIUM ELECTRODE IN PROPYLENE CARBONATE" @default.
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- W3025071777 doi "https://doi.org/10.1002/chin.197402014" @default.
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