Abstract
Existing thermodynamic functions for the equilibrium vapor species over liquid KCl and KOH are based largely on an extrapolation of data for the lower temperature solid systems together with estimated spectroscopic constants. The degree of importance of dimeric or more complex vapor species is especially uncertain, with a wide disparity indicated for the various literature studies. Using a transpiration mass spectrometric method, we have determined the equilibrium vapor composition in the presence of liquid over a wide range of temperature and pressure. The results for KCl are in very good agreement with the JANAF evaluation of previous work. In addition, thermodynamic data are given for the (KCl)3 trimer species for the first time. For the KOH system, the dimer species (KOH)2 is much more important than suggested by the JANAF evaluation of previous work. Second law thermodynamic data, at 1000 K, with current JANAF values given in parentheses are: for vaporization to yield KOH(g), ΔH v = 164 ± 4 (159 ± 17) kJ/mol, ΔS v = 109 ± 4 (102 ± 4) J/K mol; for vaporization to yield (KOH)2(g), ΔH v = 159 ± 5 (123 ± 17) kJ/mol, and ΔS v = 95.0 ± 4 (50.0 ± 13) J/K mol. Thermochemical data are also reported for the KO2 species produced by the reaction:
from which we derive at 1000 K, ΔG f (KO2) = − 169 ± 12 kJ/mol and ΔH f (KO2) = − 73.6 ± 13 kJ/mol.
Bond dissociation energies and entropies for the various potassium halide and hydroxide species are found to correlate well with other alkali halide systems. Evidence of temperature dependent electron impact ionization is also indicated in these studies.
Author to whom all correspondence and reprint requests should be addressed.
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Hastie, J.W., Zmbov, K.F., Bonnell, D.W. (1984). Transpiration Mass Spectrometric Analysis of Liquid KCl and KOH Vaporization. In: Margrave, J.L. (eds) Modern High Temperature Science. Humana Press. https://doi.org/10.1007/978-1-4612-5180-4_19
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DOI: https://doi.org/10.1007/978-1-4612-5180-4_19
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