The orthorhombic-tetragonal structural phase transition behaviors of Pr
2NiO
4+δ and Nd
2NiO
4+δ were investigated by DSC and TG–DTA under controlled oxygen partial pressure,
P(O
2), and their difference was discussed. Endothermic peak corresponding to the structural phase transition was observed in DSC curves. The transition temperature,
Tp, decreases with decreasing
P(O
2) both in Pr
2NiO
4+δ and Nd
2NiO
4+δ. A discrete weight variation originating from the variation of oxygen content, Δδ, was observed during the phase transition both in Pr
2NiO
4+δ and Nd
2NiO
4+δ. The Δδ of Pr
2NiO
4+δ was larger than that of Nd
2NiO
4+δ, and the Δδ of Pr
2NiO
4+δ increased with decreasing
P(O
2), while that of Nd
2NiO
4+δ was independent on
P(O
2), suggesting that not only the valence of Ni but also that of Pr changed during the phase transition in Pr
2NiO
4+δ. From the Ellingham diagram prepared using
Tp measured by DSC under various
P(O
2), Δ
H° and Δ
S° at the phase transition were evaluated. It was revealed that Δ
H° of Nd
2NiO
4+δ is larger than that of Pr
2NiO
4+δ, whereas Δ
S° shows little difference, showing agreement with higher
Tp of Nd
2NiO
4+δ that that of Pr
2NiO
4+δ.
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