Platinum fluorides

V, A. Further experimental work on dissociation energies in fluoride series underlines the warning given on the variability of high-temperature data. A new AHf(BF,) is 79 kJ different from the old value (6), and a maximum difference of 79 kJ appears in the dissociation energies of the sulfur fluorides (9). Values for tantalum (17) and platinum fluorides (14) are also now available. 

The reaction is probably more complex than this, and the platinum of the electrodes plays a part in the secondary reactions. Possibly the fluorine first forms platinum fluoride, PtF4, which produces a double compound with the potassium fluoride. 

This compound is considered to be the electrolyte which on decomposition forms the two gases and a double potassium platinum fluoride which is deposited as a black mud. This hypothesis has been devised to explain why the initial stage of the electrolysis is irregular and jerky, and only after the lapse of an hour, when the substances in soln. are in sufficient quantities to make the passage of the current regular, is the evolution of fluorine regular. 0. Ruff 1 has shown that ammonium fluoride can be used in place of the potassium salt. 

REDOX REACTIONS IN THE XeF2/PlATINUM FLUORIDE AND XeF2/PALLADIUM FLUORIDE SYSTEMS AND THE CONVERSION OF XeF2 TO XeF4 AND Xe... 

Fig. 1. Conversion of XeF2 to XeF4 + Xe using platinum fluorides...

N. Bartlett, B. Zemva and L. Graham, Redox Reactions in the XeF2/Platinum Fluoride and XeF2/Palladium Fluoride Systems and the Conversion of XeF2 to XeF4 and Xe, J. Fluorine Chem. 7 (1976) 301-320. 

The reaction of bis(trifluoromethyl)diazomethane with (stilbene)bis-(triphenylphosphine)platinum unexpectedly gave the platinum fluorides [237] and [238], with the parameters shown, as minor products, (94) the... 

The M(VI) and M(V) states are conhned to platinum fluorides (reactions 22.125 and 22.126) Ptp5 readily dispro-portionates to Ptp4 and PtFg. 

Gore investigated anhydrous hydrofluoric acid, determined its vapour density, etc., and its action on many elements and salts. He attempted to electrolyse it (and verified Faraday s result), and also fused silverfluoride. He heated silver fluoride in a platinum boat in a platinum vessel filled with chlorine, when the boat was corroded to a reddish-brown substance (platinum fluoride). With a graphite boat a gas (CF4 ) was formed. No fluorine was obtained. Such was the state of knowledge when Moissan began his research. 

Handler KG, Harris RA, O Brien LC, O Brien JJ (2011) Intracavity laser absorption spectroscopy of platinum fluoride, PtF. J Mol Spectr 265 39- 6... 

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