吸着誘起相変化―p-キシレン/ZSM-5系―Adsorption induced phase transition of ZSM-5 by p-xylene
豊橋技術科学大学Toyohashi University of Technology ◇ Toyohashi-shi, Aich 441, Japan
豊橋技術科学大学Toyohashi University of Technology ◇ Toyohashi-shi, Aich 441, Japan
パラキシレン吸着によりZSM-5の相変化が起こる。室温では,圧上昇に依り,P21/n→Pnma→P212121と変化する。相変化の機構は極めて単純である。パラキシレンの圧が上がると,圧上昇を緩めようとして,吸着容量の大きい相に移る。つまり,Le Chatelier - Braunの法則に従っている。
この観点から最近のデータを解析できる。吸着等温線はLangmuirモデルで記述出来るが,吸着hysteresisは定量的には解析できない。hysteresisは結晶のドメイン構造に由来する。ZSM-5中のAl含有量が少なければ,hysteresis曲線は比較的に単純だが,Al量が増すと複雑になる。
At room temperature, the symmetry of ZSM-5 changes from P21/n to P212121 via Pnma with increasing pressure of p-xylene. The adsorption capacities of these phases are 4,4 and 8 molecules per unit cell, respectively, and the Pnma phase strongly adsorbs p-xylene than the P21/n phase. It is interpreted that the phase transitions obey Le Chatlier-Braun's law, that is, that the phase changes so as to moderate the pressure increase by adsorbing much more molecules.
Adsorption isotherms with high-siliceous ZSM-5 (Si/Al=650) are well described by Langmuir model, and adsorption hysteresises observed are explained in terms of a domain structure of the crystal. With increasing Al-content, the hysteresis curve deviates from square form, indicating a complicated structure of domains.
Adsorption heat curves have broad wells assigned to P21/n-Pnma transition and sharp ones assigned to Pnma-P212121, in accordance with the present theory.
© 1996 ゼオライト研究会© 1996 Japan Association of Zeolite
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