Transpiration and Mass Spectrometric Studies of Equilibria Involving BOF(g) and (BOF)3(g)

Abstract
The reaction of BF3(g) with B2O3(l) was studied by the transpiration method in the temperature range 600° to 1100°K. Results indicate the reaction to be BF 3 ( g )+ B 2 O 3 ( l )=( BOF ) 3 ( g ). ΔH 298° was found to be 4.2 kcal, and leads to ΔHf 298°=—566.8±1 kcal/mole for (BOF)3(g). The vapor above mixtures of MgF2 and B2O3 contained in a Knudsen cell was analyzed with a mass spectrometer and was found to contain BF3(g), (BOF)3(g), and BOF(g) in the range 980° to 1230°K. From studies of the temperature dependence of appropriate ion intensities the heat of the reaction ( BOF ) 3 ( g )=3 BOF ( g ) was derived as 131 kcal at 1125°K. Use of low ionizing electron energies was required to avoid fragmentation effects. The heat of formation of BOF(g) at 298°K was calculated to be —144±3 kcal/mole.

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