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DISCUSSION The experimental values for the partial molal volume of zinc chloride in water is about 40ml/mole for concentrations greater than 2 molar. The experimental data yields poor values in dilute solutions due to the large concentration interval. In constructing Figure 30-5 from the handbook values, concentration intervals of 0.1 to 0.2 molar were used as previously described. At high concentrations, the experimental molal volumes for zinc chloride are in good agreement with the calcu lated values. The partial molal volumes of zinc chloride in potassium chloride have considerable variance. These are believed to be experimental scatter of data due to the tech nique used, rather than real variations. It would appear that the partial molal volume of zinc chloride in potassium chloride is about 45ml/mole, and essentially independent of the zinc chloride concentration. This value is observed to be about 5ml/mole higher than the value of zinc chloride in water. The partial molal volumes of potassium chloride and sodium chloride in zinc chlo- r de medium are also observed to be 5ml/mole larger than their respective aqueous values. This increase in molal volume may be due, in part, to the formation of chloro-zinc complexes. The formation of such complexes would free the water of hydration from the chloride ion and zinc ion as well. Also, the tetra-chloro zinc ion is larger than a tetra-aquo zinc ion (30-6) (30-7). The combination of free ing bound water, formation of the tetra-chloro zinc complex with its low affinity for water, and interionic repulsions in concentrated solutions may account for the constant changes in molal volumes observed in this work. In summary, the electrolyte pH will change by 0.5 - 0.8 pH units during a battery cycle due to changes in the zinc chloride concentration. Also, the electrolyte volume will contract by about 10% as the battery goes from fully discharged to fully charged. This volume contraction is due to the removal of zinc chloride from the electrolyte. REFERENCES 30-1 H.H. Willard, L.L. Merritt, Jr., and J.A. Dean. Instrumental Methods of Analysis. 4th ed. New York: D. Van Nostrand Co., Inc., 1965, pp. 568-577. 30-11PDF Image | Development of the Zinc-Chlorine Battery for Utility
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