The relative stabilities of tungsten hexacarbonyl,silver neodecanoate some metal acetyl- and hexafluoroacetylacetonates and the thermal properties of the palladium(II) acetonates

The relative stabilities of silver neodecanoate, tungsten hexacarbonyl, and a seriesof metal acetyl- and hexafluoroacetyl- acetonates, were determined using differential ther-mal analysis (DTA) and weight loss analysis. In general, the acetylacetonates decom-pose in the solid state at relatively low temperatures (100-200° C), with several of them exhibiting appreciable vapor pressures at temperatures below which their decomposi-tion rate is significant. Hexaf luoro derivatives of these compounds are, in general, more volatile and decompose at higher temperatures. The thermal decomposition behavior of palladium(II) acetylacetonate and palladium(II) hexafluoroacetylacetonate were each investigated using DTA at atmospheric pressure and under each compound’s equilib-rium or decomposition product(s) vapor pressure in conjunction with weight loss and residue composition analysis. At the heating rates employed, ≤2° C/min, palladium(II) acetylacetonate tends to decompose upon heating in either an inert or oxidizing atmo-sphere before significant quantities volatilize. On the other hand, palladium(II) hex-afluoroacetylacetonate tends to volatilize completely before any signs of decomposition are observed under the same conditions. Heating palladium(II) acetylacetonate in ar-gon, at ≤2° C/min, shows the onset of an endotherm at approximately 196° C, at the conclusion of which a product containing 75% palladium was found, the remainder com-prised of carbon, hydrogen and oxygen. In an oxidizing atmosphere at the above men-tioned heating rate, Palladium(II) acetylacetonate decomposes exothermically at 180° C yielding essentially pure palladium. Continued heating in oxygen, to 800° C results in pure PdO. At 900° C, the PdO decomposes yielding pure palladium. Depending upon the heating rates applied, one or two endotherms may be observed during the heating of palladium(II) hexafluoroacetylacetonate. Heating at 2° C/min in either an argon or ox-ygen atmosphere, results in an endothermic transition due to fusion at 105° C in argon (101° C in oxygen), followed by a second endothermic transition at 231° C in argon (223° C in oxygen), due to the normal boiling point being achieved. If heating rates are slow enough,e.g. 0.1° C/min, complete volatilization may occur before the normal boiling point is reached.