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BWR制御材の影響に着目したシビアアクシデント時のFP化学挙動評価,3; 高温質量分析法を用いた気体CsBO$$_{2}$$の熱力学研究

Evaluation of FP chemistry under sever accident conditions with focuses on the effects of BWR control material, 3; Thermodynamic study of gaseous CsBO$$_{2}$$ by Knudsen effusion mass spectrometry

中島 邦久  ; 高井 俊秀  ; 古川 智弘  ; 逢坂 正彦  

Nakajima, Kunihisa; Takai, Toshihide; Furukawa, Tomohiro; Osaka, Masahiko

軽水炉のシビアアクシデント時、B$$_{4}$$Cの影響を考慮した熱力学平衡計算によれば、温度に依存するがCsの気相中での主な化学形は、CsBO$$_{2}$$(g)と予想されている。しかし、この解析に使用されたCsBO$$_{2}$$(g)の熱力学データの信頼性は高くない(poor qualityと判定)。そのため、より信頼性の高いCsBO$$_{2}$$(g)の熱力学データを得ることを目的に、高温質量分析法によるCsBO$$_{2}$$の平衡蒸気圧測定を試みた。その結果、CsBO$$_{2}$$の平衡蒸気圧測定データを用いて、第二法則, 第三法則処理により評価した気体CsBO$$_{2}$$の標準生成エンタルピー${it $Delta$$_{f}$H$^{circ}$$_{298}$}$(CsBO$$_{2}$$,g)は、それぞれ、-700.6$$pm$$9.8kJ/mol, -698.0$$pm$$10.6kJ/molとなった。

Gaseous cesium metaborate, CsBO$$_{2}$$(g), is predicted to be the main cesium vapor species, depending on temperature, in severe light water reactor accidents according to thermodynamic analysis, which treats chemical reactions between boron and cesium. But quality of the thermodynamic data of CsBO$$_{2}$$(g) used in this thermodynamic analysis is considered to be poor. Thus, Knudsen-effusion mass-spectrometric measurement of CsBO$$_{2}$$ was performed to obtain reliable thermodynamic quantities of CsBO$$_{2}$$(g). The standard enthalpy values of formation of CsBO$$_{2}$$(g), ${it $Delta$H$^{circ}$$_{298}$}$(CsBO$$_{2}$$,g), were obtained by the 2nd law and the 3rd law treatments from measured vapor pressures and found to be -700.6 $$pm$$ 9.8kJ/mol and -698.0 $$pm$$ 10.6kJ/mol, respectively. These two values agree within the error limits and the evaluated thermodynamic data of CsBO$$_{2}$$(g) are considered to be reliable.

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