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• W2016117865 abstract "The integral enthalpies of mixing in the six binary systems formed by MgCl2, CaCl2, SrCl2, and BaCl2 have been determined calorimetrically. The results are discussed in terms of the theories of Reiss, Katz, and Kleppa and of Davis and Rice, each suitably modified to take into account the higher charge on the cation. The molar enthalpies of mixing for the systems CaCl2–SrCl2, CaCl2–BaCl2, and SrCl2–BaCl2 can be represented by the following approximate expression which is simply related to the corresponding expression for the binary alkali halides, previously derived by Hersh and Kleppa: ΔHM=X1X2(U0++−Z2340δ122) kcal/mole. Here X1 and X2 are the mole fractions of the two components; δ12=(d1—d2)/d1d2, where d1 and d2 are the sums of the ionic radii of anion and cation in the two salts, while Z=Z1Z2, the product of the charges of the anion and cation in the component salts (here Z=2). The term U0++ represents an estimate of the contribution to the enthalpy of mixing arising from the London dispersion interaction between next-nearest-neighbor cations. The quoted expression does not hold for the three binary systems involving MgCl2, which are all much less exothermic and which exhibit considerable energetic asymmetry. In all cases the enthalpy of solution of MCl2in MgCl2 is more endothermic than the opposite process. The results for these three systems are interpreted to support the view, originally advanced by Førland, that pure MgCl2 has a certain tendency to form covalently bonded Mg–Cl–Mg bridges. The breaking of these bridges gives rise to a significant endothermic contribution to the enthalpy of mixing, over and above the contributions arising from Coulombic and dispersion forces." @default.
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• W2016117865 date "1967-09-15" @default.
• W2016117865 modified "2023-09-24" @default.
• W2016117865 title "Enthalpies of Mixing in Some Binary Alkaline-Earth Chlorides" @default.
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• W2016117865 doi "https://doi.org/10.1063/1.1712231" @default.
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