Abstract
Results of studies to determine the fluoride ion affinity in GeF/sub 4/ and BF/sub 3/ are presented herein. Thermodynamic and structural data for (SF/sub 3/)/sub 2/GeF/sub 6/, ClO/sub 2/GeF/sub 2/, and ClO/sub 2/BF/sub 4/ are tabulated. The first fluoride ion affinity of GeF/sub 4/ was found to be 4-8kcal more energetic than that of BF/sub 3/. The packing volume of the BF/sub 4//sup -/ ion was found to be 16 +/- 2 A/sup 3/ which is less than the smaller GeF/sub 5//sup -/. It is noted that in small-cation structures, with close-packed ion arrangements, the lattice energy of fluoroborates can be approximately 5kcal mol/sup -1/ more favorable than for related fluorogermanates. Thus for this type of salts, the better fluoride acceptor ability of GeF/sub 4/ is largely offset by a poorer lattice energy, with the lattice difference decreasing as the cation becomes larger.
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