Abstract
Several gaseous reaction equilibria involving the lower-valent Zr–F species were studied by mass spectrometry over parts of the range 1400 – 2400 K, and the derived reaction thermodynamics were used to evaluate the bond dissociation energies, BDE, and standard enthalpies of formation, ΔfH°298, of the gaseous species ZrF, ZrF2, and ZrF3. Emphasis was placed on correlation of the second and third law results as an aid in selecting the proper thermal functions. BDE values at 298 K, measured by reference to the molecule BaF, were found to be D(Zr–F)=149.9±2.5;D(FZr–F)=161.2±2.5;D(F2Zr–F=149.6±4.5; and D(F3Zr–F)=157.9±2.5 kcal mol−1. Corresponding values of ΔfH°298 for the gaseous species were calculated to be ZrF, 12.3±2.8;ZrF2,−129.9±3.7 and ZrF3,−260.5±2.8 kcal mol-1. The results are discussed in terms of other information in the literature. When all results are evaluated with consistent thermal functions and auxiliary data, there is reasonable agreement among derived thermochemical values.alues.
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