The standard Gibbs energies of formation, ΔfG°, of intermediate compounds of Cr3B4, CrB2, and CrB4 in the boron-rich side of the Cr–B binary system were determined by measuring electromotive forces of the galvanic cells using ZrO2–Y2O3 solid electrolyte. The phase equilibria for the Cr–B binary system were clarified to construct the cells using the solid electrolyte. The measured electromotive forces of the cells were evaluated as linear temperature functions under the conditions that the transport numbers of oxide ion in solid electrolyte were regarded as 1.0. The ΔfG° functions determined from the electromotive forces via the Nernst equation were as follows:
ΔfG°(Cr3B4)/J (mol of compd)−1 = −264540 − 26.697 T ± 970 (1256–1322 K),
ΔfG°(CrB2)/J (mol of compd)−1 = −84572 − 32.442 T ± 790 (1253–1350 K),
ΔfG°(CrB4)/J (mol of compd)−1 = −105120 − 57.921 T ± 2200 (1280–1352 K).
The present ΔfG° values satisfied the phase equilibria in the Cr–B binary system. Using the ΔfG° values determined in the present study, the composition-oxygen partial pressure diagram of the Cr–B–O ternary system was constructed under the conditions of 1300 K and a total pressure of 1 bar (100 kPa). It is useful to understand the oxidation path of the boron-rich side of Cr–B binary alloys.
Fig. 4 Δ
fG°(Cr
3B
4), Δ
fG°(CrB
2), and Δ
fG°(CrB
4) values expressed for the formulation of one mole of atoms at 1300 K compared with those in the references.
11,12)
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