平衡に支配された昇温脱離スペクトルから吸着熱を算出する方法
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(2) 24. ↰⋥િਤ⠀ ᐙ㧦ᐔⴧߦᡰ㈩ߐࠇߚ᷷⣕㔌ࠬࡍࠢ࠻࡞߆ࠄๆ⌕ᾲࠍ▚ߔࠆᣇᴺ. ߚߛߒ㧘 0* ߪๆ⌕ߒߚࠕࡦࡕ࠾ࠕࠍ␜ߒ㧘. ߪⓨߩๆ⌕ὐࠍ␜ߔ㧚. ᑼߩᐔⴧቯᢙ K ߪߟ߉ߩࠃ߁ߦᦠߌࠆ㧚 . ࠕࡦࡕ࠾ࠕๆ⌕ᾲߪ㉄ᒝᐲߩᜰᮡߢࠆ㧚߹ߚๆ ⌕ᾲߪ⏕ߥቯ⟵ࠍᜬߟࡄࡔ࠲ߢࠆ߆ࠄ㧘 ઁߩ‛ℂൻቇ⊛ᜰᮡ㧘߃߫ * ᜰᢙߣ㑐ㅪߠߌࠆ ߎߣ߽ߢ߈ࠆ㧚. . Cg / mol m. -3. 0.015. K=. 1 − θ Cg RT θ P°. 0.005. 400. 500. 600. 700 T/K. 800. 900 . ࿑ 1 ࠕࡦࡕ࠾ࠕTPDࠬࡍࠢ࠻࡞ߩ৻㧚⹜ᢱߪ ࠝࠗ࠻ߩ৻⒳ࡕ࡞࠺࠽ࠗ࠻㧚 ߚߛߒ㧘ๆ⌕ᾲߩ⸘▚ߪන⚐ߢߪߥߊ㧘ᾲജቇ ߦၮߠߊ⸃ᨆࠍᔅⷐߣߔࠆ㧚╩⠪ࠄߪࠕࡦࡕ࠾ࠕ 62& ߩታ㛎ᴺߩ㐿⊒ߣਗⴕߒߡ㧘ๆ⌕ᾲߩౕ⊛ ߥ⸘▚ᚻ㗅ࠍឭ᩺ߒ㧘ߎࠇ߇ౝᄖߢᐢߊࠊࠇߡ ߈ߚ㧚ᧄⓂߢߪ 62& ࠬࡍࠢ࠻࡞ߦ㑐ߔࠆᾲജቇ⊛ ⠨ኤ㧘ๆ⌕ᾲߩ▚ᴺ߅ࠃ߮ߘߩㅴᱠߦߟߡ⸃ ⺑ߔࠆ㧚ߎߩᣇᴺߪࠕࡦࡕ࠾ࠕ 62& ߦ㒢ࠄߕ㧘ᐔ ⴧᡰ㈩ߩ 62& ㆊ⒟ߦኻߒߡ৻⥸⊛ߦ߃ࠆߪߕߢ ࠆ㧚 ߥ ߅ 㧘 ㄭ ᐕ ╩ ⠪ ࠄ ߪ ⿒ ᄖ ಽ శ +4 ߣ ⾰ ㊂ ಽ ᨆ. /5 ࠍ⚵ߺวࠊߖߚࠕࡦࡕ࠾ࠕ +4/562& ᴺߦࠃ ߞߡ㧘62& ࠬࡍࠢ࠻࡞ߦኻߔࠆ․ቯߩ⒳㘃ߩ㉄ὐ ߩነਈࠍᛮ߈ߒߡ᷹ቯߔࠆᣇᴺ߽㐿⊒ߒߚ=?㧚 ࠬࡍࠢ࠻࡞߇ᓧࠄࠇߚᓟߩᢙቇ⊛⸃ᨆᴺߪหߓߥ ߩߢ㧘ᧄⓂߢߪߒߥߢ⼏⺰ߔࠆ㧚 㧞㧚ℂ⺰ᑼߩዉ ╩⠪ࠄߪ㧘ㅢᏱߩࠕࡦࡕ࠾ࠕ 62& ᷹ቯߢߪ㧘ᄙ ߊߩ࿕㉄⸅ᇦߢᐔⴧ ߇ᚑ┙ߒ㧘ౣๆ⌕߇⥄ ↱ߦ߈ߡࠆߎߣࠍߒߚ=?㧚 . 0* . 0* I . . ∆H °. ∆S °. . K = e RT e R ߚߛߒ㧘ǻHº㧘ǻSº ߪߘࠇߙࠇ ᑼ ࠕࡦࡕ࠾ࠕ ߩ⣕㔌 ߦ߁ᮡḰࠛࡦ࠲࡞ࡇ ,OQN ߅ࠃ߮ ࠛࡦ࠻ࡠࡇᄌൻ ,-OQN ߢࠆ㧚ǻHº ߪๆ ⌕ᾲߣ߽߫ࠇࠆ㧚. ᑼ߆ࠄ ᑼ߇ዉ߆ࠇࠆ㧚 −. . . ߚߛߒ㧘ș, Cg, R, T, Pº ߪߘࠇߙࠇⵍⷒ₸ ㉄ὐߩ ߁ߜࠕࡦࡕ࠾ࠕ߇ๆ⌕ߒߚ߽ߩߩഀว 㧘᳇⋧ࠕࡦ ࡕ࠾ࠕỚᐲ OQNO 㧘᳇ቯᢙ ,-OQN 㧘 ᷷ᐲ - 㧘ᮡḰ⁁ᘒߩജ 2C ߢࠆ㧚 ߎߩᐔⴧቯᢙߪᾲജቇ⊛ࡄࡔ࠲ߣ ᑼߩࠃ ߁ߦ㑐ㅪߠߌࠄࠇࠆ㧚 . 0.01. 0. . ∆H °. . θ P° − RT Cg = e e 1 − θ RT. ∆S ° R. . . . ᑼߪ᳇⋧ࠕࡦࡕ࠾ࠕỚᐲߩ᷷ᐲଐሽᕈࠍ␜ ߒߡࠆ㧚ߔߥࠊߜ 62& ࠬࡍࠢ࠻࡞ߩᢙቇ⊛ߥ⸥ ㅀߢࠆ㧚 ৻ᣇ㧘ࠕࡦࡕ࠾ࠕߩ⣕㔌ㅦᐲߪⵍⷒ₸ߩᷫዋㅦ ᐲߦ㉄ὐߩᢙࠍਸ਼ߓߚ߽ߩߢࠅ㧘ߎࠇ߇᳇⋧ߩ ࠕࡦࡕ࠾ࠕߩឃㅦᐲߦ╬ߒ߆ࠄ㧘 ᑼ߇ዉ߆ ࠇࠆ㧚 . FC g = − βA0W. dθ dT. . . ߚߛߒ㧘ȕ㧘F, A0, W ߪߘࠇߙࠇ᷷ㅦᐲ -U 㧘 ࠠࡖࠕࠟࠬߩᵹㅦ OU 㧘࿕⹜ᢱߩන㊀㊂ ߚࠅߩ㉄㊂ OQNMI 㧘⹜ᢱ㊂ MI ߢࠆ㧚ᓟ ߩෳ⠨ߩߚߦ␜ߔߣ㧘ታߦࠃߊ᷹ⷰߐࠇࠆ A0 ߪ 㨪OQNMI ⒟ᐲߢ㧘 ࠃߊ↪ࠄࠇࠆ ȕF, W ߪߘࠇߙࠇ -U㧘㨪OU㧘 㨪MI ⒟ᐲߢࠆ㧚. ᑼ߆ࠄߪ ߩ㑐ଥ߇ᓧࠄࠇࠆ㧚.
(3) 25. 㠽 ข ᄢ ቇ ᄢ ቇ 㒮 Ꮏ ቇ ⎇ ⓥ ⑼㧛Ꮏ ቇ ㇱ ⎇ ⓥ ႎ ๔ ╙㧠㧜ภ. ∆H °. dθ F P° − RT θ e e = dT 1 − θ βA0W RT. −. ∆S ° R. . . . ߅ࠃ߮ ᑼ߇ࠕࡦࡕ࠾ࠕ 62& ࠬࡍࠢ࠻࡞ࠍ ⸥ㅀߔࠆℂ⺰ᑼߢࠆ㧚 㧟㧚ᄙὐᴺ=? . ᑼࠍ᷷ᐲߢᓸಽߔࠆߣ ᑼ߇ᓧࠄࠇࠆ㧚 dC g dT. ∆H °. =. P° − RT e e R. ∆S ° R. 1. 1. (1 − θ )T 1 − θ. dθ θ (∆H ° − RT ) + dT RT 2 . . . ᑼߦ ᑼࠍઍߔࠆߣ ᑼ߇ᓧࠄࠇࠆ㧚 dC ∆H ° − RT P° F θ 1 g. dT. =. R. e. −. ∆H ° RT. e. ∆S ° R. −. (1 − θ )RT (1 − θ )2. β A0W. P°e. −. ∆H ° RT. e. ∆S ° R. +. T. . . ⣕㔌ࡇࠢߩ㗂ὐߢߪ dCg/dT ߇ࡠߥߩߢ㧘. ᑼ߇ᚑ┙ߔࠆ㧚 ∆H °. 2. β (1 − θ m ) (∆H ° − RTm ) F Tm = e RTm ∆S ° A0W P°e R. ߣ߁ߎߣߢࠆ㧚 ߎߩߎߣߪ㧘ࠕࡦࡕ࠾ࠕ 62& ᴺߩ⍴ᚲࠍ␜ߒߡ ࠆࠃ߁ߦ߃ࠆ㧚62& ࠬࡍࠢ࠻࡞ߩ⣕㔌᷷ᐲߪ ࿕ߩ㉄ᒝᐲࠍ⋥ធߦߪ␜ߐߥߒ㧘ታ㛎᧦ઙߩ ⇣ߥࠆࠬࡍࠢ࠻࡞ߩ⣕㔌᷷ᐲࠍᲧセߒߡ߽ᗧ߇ ߥ㧚ߦታ㛎᧦ઙࠍឥ߃ߡⴕߞߚߣߒߡ߽㧘 ᑼߦࠃࠇ߫㧘࿕ߩ․ᕈߢࠆ A0 ߦࠃߞߡ Tm ߇ Ꮐฝߐࠇࠆ A0 ߇ߤࠇ߶ߤᄢ߈ߊ Tm ߦᓇ㗀ߔࠆ߆ ࠍᓟߢ␜ߔ 㧚ߔߥࠊߜ㧘ᧂ⍮ߩ⹜ᢱߩ㉄ᒝᐲࠍಽ ᨆߔࠆߎߣߪਇน⢻ߦ߃ࠆ㧚 ߒ߆ߒߥ߇ࠄ㧘 ᑼࠍၮߦߔࠇ߫㧘ߒ⸃ ᨆࠍ⚻ߡ㧘㉄ὐߣࠕࡦࡕ࠾ࠕߩ㑆ߩᔕߩᕈ⾰ࠍ ␜ߔࡄࡔ࠲ ǻHº㧘ǻSº ࠍ᳞ࠆߎߣ߇ߢ߈ࠆ㧚 ᐔⴧ߇ᚑ┙ߒߡࠆߎߣߪ㧘⍴ᚲߢߪߥߊ㐳ᚲߥ ߩߢࠆ㧚 2. ᑼ ߩ ln β (1 − θ m ) (∆H ° − RTm ) ߦ ታ ߦ ࠃ ߊ ∆S °. P°e R ᓧࠄࠇࠆࡄࡔ࠲ࠍᒰߡߪࠆߣ ⒟ᐲߢ߶ ߷৻ቯߣߥࠆ㧚ߎߩ㗄ࠍቯᢙߣߥߔߣ㧘. ln Tm − ln. A0W ߪ 1/T ߩ৻ᰴ㑐ᢙߣߥࠆ㧚 m F. ᑼߩਛߢ㧘R, Pº ߪቯᢙW, F, ȕ ߪታ㛎᧦ ઙTm, A0, șm ߪታ㛎ߦࠃߞߡᓧࠄࠇࠆታ᷹୯ߢ ࠆ㧚ᱷࠅߩᧂ⍮ߩᄌᢙ ǻHº㧘ǻSº ߪ㧘㉄ὐߣࠕࡦ ࡕ࠾ࠕߩ㑆ߩᔕߩᕈ⾰ࠍ␜ߔࡄࡔ࠲ߢࠆ㧚 ᧂ⍮ߩᄌᢙߪߎࠇࠄ ߟߒ߆ߥߩߢ㧘 ߟߩ⹜ ᢱ ߦ ኻ ߒ ߡ ⇣ ߥ ࠆ W/F ߢ ᢙ ࿁ ߩ ᷹ ቯ ࠍ ⴕ 㧘. AW ln Tm − ln 0 ࠍ 1/T m ߦኻߒߡࡊࡠ࠶࠻ߒ㧘ᓧࠄࠇ ߚߛߒ㧘Tmșm ߪߘࠇߙࠇࡇࠢ㗂ὐߢߩ᷷ᐲ F. - ߣⵍⷒ₸ߢࠆ㧚. ᑼߩਔㄝߩኻᢙࠍขߞߡ ᑼ߇ᓧࠄࠇࠆ㧚 ߚ⋥✢ߩ߈ߣಾ ߆ࠄߎࠇࠄ ߟߩࡄࡔ࠲ ǻHº㧘ǻSº ࠍ᳞ࠆߎߣ߇ߢ߈ࠆ㧚ߎߩᣇᴺߪ෩ኒ 2 ߦታ᷹୯ߩߺ߆ࠄࠕࡦࡕ࠾ࠕๆ⌕ߩᾲജቇ⊛ࡄ A W ∆H ° β (1 − θ m ) (∆H ° − RTm ) + ln ln Tm − ln 0 = ࡔ࠲ࠍ᳞ࠆᣇᴺߢ㧘ᢙ࿁ߩታ㛎ࠍⷐߔࠆߩߢ ∆S ° F RTm P°e R ᄙὐᴺߣࠎߢࠆ㧚 ᄙὐᴺߩࡊࡠ࠶࠻ߩࠍ࿑ߦ␜ߔ㧚ߎߩࡊࡠ ࠶࠻ߩ߈߇ ǻHº/R ߥߩߢ㧘߈ߦ R ࠍਸ਼ߓߡ ǻHº ࠍᓧࠆ㧚ߟ߉ߦ㧘ߎߩࡊࡠ࠶࠻ߩಾ ߇ ߎߩᑼߪ㧘62& ࠬࡍࠢ࠻࡞ߦ߅ߌࠆࡇࠢ⟎ 2 Tm ߇ታ㛎᧦ઙ W/F ߦᏀฝߐࠇࠆߎߣࠍ␜ߒߡ β (1 − θ m ) (∆H ° − RTm ) ߢࠆߩߢ㧘ࡄࡔ࠲ࠍ ln ࠆ㧚ታ㓙ߦ ߟߩ⹜ᢱߢ W/F ࠍ ᩴ߶ߤᄌ߃ߡ᷹ ∆S ° R P ° e ቯߔࠆߣ㧘ࡇ᷷ࠢᐲߪ - એᄌൻߔࠆ㧚ߎ ࠇࠍ⇣ߥࠆᦠ߈ᣇߢ⺑ߔࠆߣ㧘᷹ቯਛߦ♽ౝߢ ోㇱઍߒߡ ǻSº ࠍᓧࠆ㧚ǻHº ߣߒߡߪ 㨪M, ࠕࡦࡕ࠾ࠕߩౣๆ⌕߇⥄↱ߦ߈ࠆߚ㧘ࠠࡖ OQN ⒟ᐲ߇ᓧࠄࠇࠆߎߣ߇ᄙ㧚߹ࠇߦ ǻHº ࠕࠟࠬᵹㅦߦኻߒߡ⹜ᢱ㊂߇ᄙߣߞߚࠎ⣕㔌 M,OQN ߩ㕖Ᏹߦ㜞୯߇ⷰኤߐࠇࠆ=?㧚 ߒߚࠕࡦࡕ࠾ࠕߩౣๆ⌕߇ᄙߊ➅ࠅߐࠇ㧘㜞 ᷷ᐲߦߥࠆ߹ߢࠕࡦࡕ࠾ࠕ߇♽ᄖߦឃߐࠇߥ.
(4) 26. ↰⋥િਤ⠀ ᐙ㧦ᐔⴧߦᡰ㈩ߐࠇߚ᷷⣕㔌ࠬࡍࠢ࠻࡞߆ࠄๆ⌕ᾲࠍ▚ߔࠆᣇᴺ. ൻߐߖ㧘 . 10 2-. ln Tm - lnA 0 W/ F. SO4 /ZrO2. 5. -2. WO3 (5.1 nm ) / ZrO2. -2. WO3 (5.8 nm ) / ZrO2. 0. 0.0012. 0.0014. 0.0016 -1. (1/ Tm ) / K. 2. A0W ∆H ° β (1 − θ m ) (∆H ° − RTm ) − − ln ∆S ° F RTm P°e R . ln Tm − ln. 0.0018. 0.002. ࿑ 2 ᄙὐᴺߩߚߩࡊࡠ࠶࠻ߩ㧚ߎߩࡊࡠ࠶ ࠻߆ࠄߪ㧘SO42-/ZrO2ߢߪ200 kJ mol-1㧘WO3/ZrO2 ߢߪ130 kJ mol-1ߩǻHº߇ᓧࠄࠇߚ㧚 㧠㧚৻ὐᴺ=? ᄙὐᴺߢᄙߊߩࠝࠗ࠻߅ࠃ߮ⶄว㉄ൻ‛ ⸅ᇦߩ ǻHº㧘ǻSº ࠍቯߒߚߣߎࠈ㧘ǻSº ߪ᷹ቯߒ ߚߤߩ࿕㉄ߦߟߡ߽߶߷৻ቯߢࠆߎߣ߇ࠊ ߆ߞߚ㧚ǻSº ߆ࠄ᳇ߩᷙวߦࠃࠆࠛࡦ࠻ࡠࡇ ჇടࠍᏅߒᒁߊߣ㧘ࠕࡦࡕ࠾ࠕ⣕㔌ߩࠛࡦ࠻ࡠࡇ ߪߤߩ࿕㉄ߢ߽⚂ ,-OQN ߢ৻ቯߢ ࠆ㧚6TQWVQP ߩᴺೣߦࠃࠆߣ㧘ᄙߊߩᶧߩ⫳ ⊒ࠛࡦ࠻ࡠࡇߪ ,-OQN ⒟ᐲߢ৻ቯߢ㧘 ߎࠇߪ⫳⊒ߦࠃߞߡ₪ᓧߐࠇࠆਗㅴߩ⥄↱ᐲߦ⋧ ᒰߔࠆ=?㧚᷹ቯߐࠇߚ⣕㔌ࠛࡦ࠻ࡠࡇߪߎߩ୯ ߣㄭߣ⠨߃ߡ߽ࠃ㧚ߐࠄߦߪ㧘ࠕࡦࡕ࠾ࠕߩ ⫳⊒ࠛࡦ࠻ࡠࡇ,-OQN ߦ߶ߣࠎߤ৻⥌ߒ ߡࠆ㧚ߎߩߎߣߪ㧘⒳ߩޘ࿕㉄ߢߩࠕࡦࡕ ࠾ࠕߩ⥄↱ᐲ߇ㅢߢࠆߎߣ㧘⣕㔌ߦࠃߞߡਗ ㅴߩ⥄↱ᐲࠍ₪ᓧߔࠆߎߣࠍ␜ߒߡ߅ࠅ㧘᷹ቯߩ ᅷᒰᕈࠍᡰᜬߒߡ߅ࠅ㧘߹ߚᄙߊߩ࿕㉄߇ㅢ ߩ ǻSº ୯ࠍᜬߟߎߣࠍ␜ໂߒߡࠆ㧚 ߘߎߢ ǻSº ߇৻ቯߣቯߔࠆߣ㧘 ᑼߦ߅ߌ ࠆᧂ⍮ߩࡄࡔ࠲ߪ ǻHº ߛߌߣߥࠆ㧚ߒߚ߇ߞ ߡ ࿁ߩ᷹ቯ߆ࠄ ᑼࠍ↪ߡ ǻHº ࠍ▚ߔࠆ ߎߣ߇น⢻ߢࠆ㧚ߎߩ ǻHº ߎߘ߇㧘㉄ὐߣࠕࡦ ࡕ࠾ࠕߩ⚿วߩ⾰⊛ߥᒝߐ㧘ߔߥࠊߜ㉄ᒝᐲࠍ␜ ߔࠕࡦࡕ࠾ࠕๆ⌕ᾲߢࠆ㧚 ߚߛߒ㧘ǻHº એᄖߩࡄࡔ࠲߇ోߡࠊ߆ߞߚ ߣߒߡ߽㧘 ᑼࠍ ǻHº ߦ㑐ߔࠆᣇ⒟ᑼߣߒߡ⸃ ߊߩߪ࿎㔍ߢࠆ㧚ߘߎߢ㧘ǻHº ࠍ⹜ⴕ㍲⺋ߢᄌ. ߇ᚑ┙ߔࠆ ǻHº ࠍㆬ߱ߩ߇ታ⊛ߥᣇᴺߢࠆ㧚 ߎߩᣇᴺߦࠃߞߡ㧘 ࿁ߩ᷹ቯ߆ࠄ㉄㊂㉄ᒝᐲ. ࠕࡦࡕ࠾ࠕๆ⌕ᾲ ࠍቯߢ߈ࠆ㧚 㧡㧚TPD ࠬࡍࠢ࠻࡞ࠍ␜ߔ㑐ᢙߩᕈ⾰ A0 ߣ ǻHº ߩ 62& ࠬࡍࠢ࠻࡞߳ߩᓇ㗀ߪ ᑼߦ␜ߐࠇߡࠆ߇㧘ߎߎߢࠪࡒࡘ࡚ࠪࡦࠍ ↪ߡౕ⊛ߥᓇ㗀ࠍ⺑ߔࠆ㧚. ᑼฝㄝߩࡄࡔ࠲ߩ߁ߜ㧘R, Pº, W, F, ȕ, ǻSº ߪߎߎ߹ߢㅀߴߚࠃ߁ߦᣢ⍮ߢࠆ㧚ߒߚ߇ ߞߡ㧘ࠆ᷷ᐲ T ߦ߅ߌࠆ ș ߇ࠊ߆ߞߡࠆߣ߈㧘 A0 ߣ ǻHº ࠍቯߔࠆߣ㧘ࠊߕ߆ߥ᷷ᐲ dT ߩ 㑆ߩⵍⷒ₸ߩᷫዋㅦᐲ-dș/dT ࠍ ᑼߢ⸘▚ߔࠆ ߎߣ߇ߢ߈ࠆ㧚᷹ቯ㐿ᆎᤨߩ ș ࠍ ߦㄭߣߒ ߚ ߛߒ ߦࠃࠆ㒰▚ߩ࿁ㆱߩߚߦ߃߫ ߣߔࠆᔅⷐ߇ࠆ 㧘ࠊߕ߆ߥ᷷ᐲ ߃߫ - ߩ ߩ㑆ߩ-dș/dT ࠍ ᑼߢ⸘▚ߔࠆ㧚ߎࠇࠍ ߦઍߔࠆߣ㧘ߘߩ᷷ᐲߦ߅ߌࠆ Cg ࠍ▚ߢ߈ࠆ㧚 ৻ᣇ㧘ᓧࠄࠇߚ-dș/dT ߦ dT ࠍਸ਼ߓࠆߣ-dș ߇ᓧࠄ ࠇ㧘ߎࠇࠍᦨೋߩ ș ߆ࠄᒁߊߣ㧘dT ߛߌ᷷ᐲ߇ ߇ߞߚᓟߩ ș ࠍ⸘▚ߢ߈ࠆ㧚ߎࠇࠄࠍ➅ࠅߔߣ ș-dș/dT, Cg ࠍ T ߩ㑐ᢙߣߒߡᓧࠆߎߣ߇ߢ߈ࠆ㧚 ߟ߹ࠅ㧘A0 ߣ ǻHº ࠍቯߔࠆߣ TPD ࠬࡍࠢ࠻࡞. T ߩ㑐ᢙߣߒߡߩ Cg ࠍࠪࡒࡘ࠻ߔࠆߎߣ߇ ߢ߈ࠆ㧚ࠪࡒࡘ࠻ߐࠇߚࠬࡍࠢ࠻࡞ߩࠍ࿑ ߣ࿑ߦ␜ߔ㧚ߎࠇࠄߩߢߪታ㛎᧦ઙ߇ታ⊛ ߥ᧦ઙߢ⛔৻ߐࠇ㧘A0 ߣ ǻHº ߩߺࠍᄌൻߐߖߡࠬ ࡍࠢ࠻࡞߇ឬ߆ࠇߡࠆ㧚 ࿑ߢߪ A0 ࠍ৻ቯߣߒߡ ǻHº ߩᓇ㗀߇␜ߐࠇ ߡࠆ㧚⥄ߩߎߣߢࠆ߇㧘A0 ߇৻ቯߥߩߢࡇ ࠢߩ㕙Ⓧߪ৻ቯߢ㧘ǻHº ߔߥࠊߜๆ⌕ߩᒝߐ߇ ᄢ߈߶ߤࡇࠢߪ㜞᷷ߦࠇࠆ㧚ߎߩ᧦ઙߢߪ㧘 ǻHº ߇ M,OQN Ⴧߔߣࡇ᷷ࠢᐲ߇ - ߶ߤ Ⴧߔߎߣ߇ࠊ߆ࠆ㧚.
(5) 27. 㠽 ข ᄢ ቇ ᄢ ቇ 㒮 Ꮏ ቇ ⎇ ⓥ ⑼㧛Ꮏ ቇ ㇱ ⎇ ⓥ ႎ ๔ ╙㧠㧜ภ. ∆H0 = 120 kJ mol-1. 0.015 150. Cg / mol m. Cg / mol m. A0 = 1 mol kg -1. 0.9 0.8 0.7. 160 -3. 140. -3. 0.01. 130. 0.005. 0.6 0.5 0.4. 0.01. 0.3. 0.005. 0.2 0.1. 0. 400. 500. 600 700 T/K. 800. ࿑ 3 A0ࠍ৻ቯߣߒ㧘ǻHºࠍ╬㑆㓒ߢᄌൻߐߖߚߣ߈ ߩ(5), (6)ᑼߦࠃࠆCgߩ⸘▚୯㧚ȕ = 0.17 K s-1, W = 10-4 kg, A0 = 0.6 mol kg-1, F = 7.610-6 m3 s-1, ǻSº = 95 J K-1 mol-1 + ᷙวߩࠛࡦ࠻ࡠࡇߣቯߒ㧘࿑ਛߦ⸥ߒߚ ǻHºࠍቯߒߚ㧚. 0. 400. 500. 600 700 T/K. 800. ࿑ 4 ǻHºࠍ৻ቯߣߒ㧘A0ࠍ╬㑆㓒ߢᄌൻߐߖߚߣ߈ ߩ(5), (6)ᑼߦࠃࠆCgߩ⸘▚୯㧚ǻHº = 140 kJ mol-1ߣ ቯߒ㧘࿑ਛߦ⸥ߒߚA0ࠍቯߒߚ㧚ઁߩ᧦ઙߪ࿑ 3 ߣหߓߣߒߚ㧚 㧢㧚ࠞࡉࡈࠖ࠶࠹ࠖࡦࠣᴺ=? ৻ᣇ㧘࿑ߢߪ ǻHº ࠍ৻ቯߣߒߡ A0 ߩᓇ㗀߇ ␜ߐࠇߡࠆ㧚A0 ߇ᄢ߈߶ߤࡇࠢ㕙Ⓧ߇ᄢ߈ ߐߡ㧘ࠪࡒࡘ࡚ࠪࡦߦࠃߞߡᓧࠄࠇߚ࿑ ߩߪᒰὼߛ߇㧘ǻHº ߇৻ቯߢࠆߦ߽߆߆ࠊࠄ ߿࿑ߩࠬࡍࠢ࠻࡞ߩᒻ⁁ߪ㧘࿑ߩࠃ߁ߥౖဳ ߕ㧘A0 ߇ᄢ߈߶ߤࡇࠢ߇㜞᷷ߦࠇߡࠆ㧚 ⊛ߥࠝࠗ࠻ߢታ᷹ߐࠇࠆࠬࡍࠢ࠻࡞ߦࠃߊ ߎࠇߪ㧘 ᑼߦ␜ߐࠇߚࠃ߁ߦ㧘ࡇ᷷ࠢᐲߦ ૃߡࠆ㧚 ኻߒߡ A0 ߇ᓇ㗀ߔࠆߚߢࠆ㧚ࠍᄌ߃ࠆߣ㧘 ߘߎߢ㧘⹜ⴕ㍲⺋ߢ A0 ߣ ǻHº ࠍᄌൻߐߖߡࠬ A0 ߇ᄢ߈߶ߤ♽ౝߩࠕࡦࡕ࠾ࠕߩ㊂߇ᄙߩ ࡍࠢ࠻࡞ࠍឬߊ㧚ࠬࡍࠢ࠻࡞߇ታ᷹୯ߣࡈࠖ࠶࠻ ߢ㧘ߞߚࠎ⣕㔌ߒߚࠕࡦࡕ࠾ࠕߩౣๆ⌕߇߈ ߔࠆߣ߈㧘ቯߒߚ A0 ߣ ǻHº ߇࿕ߩ㉄㊂ߣ㉄ ߿ߔߊ㧘ౣๆ⌕ߦࠃߞߡࡇࠢ߇㜞᷷ߦࠪࡈ࠻ߒ ᒝᐲ ࠕࡦࡕ࠾ࠕๆ⌕ᾲ ࠍ␜ߔߪߕߢࠆ㧚ߎߩ ߚߎߣࠍ␜ߒߡࠆ㧚ߎߩࠪࡈ࠻ߪήⷞߢ߈ࠆᄢ ࠃ߁ߦߒߡ A0 ߣ ǻHº ࠍ᳞ࠆᣇᴺࠍࠞࡉࡈࠖ ߈ߐߢߪߥߊ㧘ߎߩ᧦ઙߢߪ A0 ߇ ߆ࠄ OQN ࠶࠹ࠖࡦࠣᴺߣࠎߢࠆ㧚 MI ߹ߢჇടߔࠆߣ - ߶ߤࠪࡈ࠻ߒߡࠆ㧚 ᄙὐᴺ߅ࠃ߮৻ὐᴺߢᓧࠄࠇࠆ㉄ᒝᐲߪࡇ ߎߩࠪࡈ࠻ߩ⒟ᐲߪ࿑ߦ߅ߡ ǻHº ߇ M, ᷷ࠢᐲߣ߁ ߟߩᖱႎ߆ࠄᓧࠄࠇࠆઍ୯ߢ OQN Ⴧߒߚ႐วߣห╬ߢࠆ㧚A0 ߩᓇ㗀ࠍ⠨ᘦߖ ࠆ㧚࿕ߩ㉄ᒝᐲߦߪಽᏓ߇ࠆ߆߽⍮ࠇߥ㧚 ߕ㧘නߦࡇ᷷ࠢᐲߛߌ߆ࠄ㉄ᒝᐲࠍ⹏ଔߒߚ႐ ࠞࡉࡈࠖ࠶࠹ࠖࡦࠣᴺߢߪ㧘એਅߦㅀߴࠆࠃ߁ ว㧘ߎࠇࠄߩ㉄㊂ߣ㉄ᒝᐲߩ㆑ࠍᷙหߒߡߒ߹ ߦࡇࠢߩᒻࠍ↪ߒߡ㉄ᒝᐲߩಽᏓࠍ᳞ࠆߎ ߁ߎߣߦߥࠆ㧚 ߣ߇ߢ߈ࠆ㧚 ታ㓙ߩ⎇ⓥߢࠕࡦࡕ࠾ࠕ 62& ߇↪ࠄࠇࠆ႐ว㧘 ࿑ ߩ ࠬ ࡍ ࠢ ࠻ ࡞ ታ ᷹ ୯ ࠍ ࿑ ߩ ᄥ ✢ ߣ ߒ ߡ ߃߫ࠆ⒳ߩࠝࠗ࠻ߩ⚿᥏᭴ㅧࠍߞߚ߹ ౣឝߔࠆ㧚ࡇࠢ㕙Ⓧ߆ࠄ A0 OQNMI ߢ ߹ Al ㊂ࠍߒߛߦჇ߿ߒߚࠅᷫࠄߒߚࠅߒߚߣ ࠆߎߣߪࠊ߆ߞߡࠆ㧚 ᑼߦߎߩ A0 ߈㧘㉄ᒝᐲ߇ᄌൻߔࠆ߆ߤ߁߆ࠍ⼏⺰ߔࠆࠃ߁ߥ ߅ࠃ᷹߮ቯ᧦ઙࠍઍߒߡࠬࡍࠢ࠻࡞ࠍࠪࡒࡘ ߎߣ߇ᄙ㧚ේೣߣߒߡ A0 ߪ Al ේሶᢙߣหߓߢ ࠻ߒ㧘ታ᷹୯ߣࡈࠖ࠶࠻ߔࠆࠬࡍࠢ࠻࡞ࠍਈ߃ ࠆ߆ࠄ㧘A0 ߽߹ߚჇᷫߔࠆ㧚ߎߩࠃ߁ߥߣ߈㧘 ࠆ ǻHº ࠍត⚝ߔࠆ㧚ǻHº M,OQN ߩߣ߈࿑ A0 ߦࠃࠆࡇ᷷ࠢᐲߩࠪࡈ࠻ࠍ㉄ᒝᐲߩᄌൻߣ ߩ⚦✢߇ᓧࠄࠇ㧘⣕㔌᷷ᐲ߇߶߷╬ߒ㧚ߎߩߎ ᷙหߔࠆߣ㧘ቢోߦ㑆㆑ߞߚ⚿⺰ࠍᓧߡߒ߹߁ߎ ߣߪ㧘᷹ቯߐࠇߚ ǻHº ߩᐔဋ୯߇ M,OQN ߦ ߣߦߥࠆ㧚 ㄭߎߣࠍ␜ߒߡࠆ㧚ታ㓙ߦߎߩࠬࡍࠢ࠻࡞߆.
(6) 28. ↰⋥િਤ⠀ ᐙ㧦ᐔⴧߦᡰ㈩ߐࠇߚ᷷⣕㔌ࠬࡍࠢ࠻࡞߆ࠄๆ⌕ᾲࠍ▚ߔࠆᣇᴺ. ࠇߪᗐቯߒߚߣ߅ࠅߛ߇㧘# ߣᲧߴߡૐ᷷ߩߺ ߦ߇ᐢ߇ߞߡ߅ࠅ㧘ࡇࠢ㗂ὐ᷷ᐲ߽ ' ߩᣇ߇ # ࠃࠅૐ㧚㉄ᒝᐲߩᐔဋ୯ߪหߓߪߕߥߩߢ㧘 ߎࠇߪวℂ⊛ߢߥ㧚. 0.02. A E. Cg / mol m. -3. ࠄߪ৻ὐᴺߢ߶߷หߓ୯߇ᓧࠄࠇࠆ㧚 ߒ߆ߒ㧘࿑ߩታ᷹୯ߩࡇࠢߪ⸘▚୯ࠃࠅ ዋߒᐢ㧚⸘▚ߢߪ ǻHº ࠍන৻ߩ୯ߣቯߣߒߡ ࠆ߇㧘ታߦߪ ǻHº ߦ⧯ᐓߩಽᏓ߇ࠆߚߣ ⠨߃ࠄࠇࠆ㧚ߘߎߢ㧘ዋߒ⇣ߥࠆ ǻHº ࠍᜬߟⶄᢙ ߩ⒳㘃ߩ㉄ὐࠍቯߒ㧘ߎࠇࠄ߆ࠄߩ⣕㔌ࡇࠢ ߩว⸘ࠍឬߊߎߣߦߔࠆ㧚ߚߛߒ㧘ⶄᢙߩࡇࠢ ࠍว⸘ߔࠆ㓙㧘A0 ߩࡇ᷷ࠢᐲ߳ߩᓇ㗀ࠍߟ߉ߩ ࠃ߁ߦ⠨ᘦߔࠆᔅⷐ߇ࠆ㧚. 0.02. C 0.01 B. Cg / mol m. -3. D. 0.01. 0. 0. 400. 500. 600. 700 T/K. 800. 900. ࿑ 5 ࿑ 1ߩTPDࠬࡍࠢ࠻࡞ታ᷹୯(ᄥ✢)ߣ㧘A0 = 1.25 mol kg-1, ǻHº = 148 kJ mol-1ࠍቯߒߚࠪࡒࡘ ࡚ࠪࡦ(⚦✢)㧚 ߹ߕ㧘ᓇ㗀ࠍ⠨ᘦߒߥߣߤ߁ߥࠆ߆ࠍ␜ߔ㧚 ࿑ߩࠪࡒࡘ࡚ࠪࡦ ⚦✢ ࠍ࿑ߩ A ߣߒߡ ౣឝߔࠆ㧚A ߢߪోߡߩ㉄ὐ߇ M,OQN ߩ ǻHº ࠍᜬߟߣቯߒߚ߇㧘ቯࠍᄌ߃㧘㉄ὐߩ߁ߜ ߇ M,OQN ߩ ǻHº㧘 ߇ M,OQN ૐ ǻHº㧘 ߇ M,OQN 㜞 ǻHº ࠍᜬߟߣߔࠆ㧚ߟ߹ࠅ㧘 ㉄ᒝᐲߩᐔဋ୯ߪหߓߢࠆ߇㧘㉄ᒝᐲߦಽᏓ߇ ࠆߣቯߔࠆ㧚ߘߎߢ㧘A0 OQNMIǻHº M,OQN $ 㧘A0 OQNMIǻHº M,OQN % 㧘A0 OQNMIǻHº M,OQN & ߩ ߟߩࠬࡍࠢ࠻࡞ᚑಽࠍ▚ߒ㧘 ࿑ߦ␜ߔ㧚ᵈ⋡ߔߴ߈ߎߣߪ㧘% ߩࠬࡍࠢ࠻࡞ ߪ # ߣหߓ㉄ᒝᐲࠍᜬߟߦ߽߆߆ࠊࠄߕ㧘㉄㊂߇ ዊߐߩߢ߿߿ૐ᷷ߦࡇࠢࠍᜬߟߎߣߢࠆ. ࿑ߦ␜ߒߚߣ߅ࠅ㧘ǻHº ߪ৻ቯߢߞߡ߽ A0 ߇ዊߐ߶ߤࡇ᷷ࠢᐲߪૐ 㧚$㨪& ߩ ᚑಽ ࠍว⸘ߒߚ ' ߢߪ㧘# ࠃࠅࡇࠢߩ߇ᐢߊ㧘㉄ ᒝᐲߦಽᏓࠍᜬߚߖߚߎߣ߇ᤋߐࠇߡࠆ㧚ߘ. 400. 500. 600. 700 T/K. 800. 900. ࿑ 6 A0 = 1.25 mol kg-1, ǻHº = 148 kJ mol-1 (A)㧘A0 = 0.3125 mol kg-1, ǻHº = 138 kJ mol-1 (B)㧘A0 = 0.625 mol kg-1, ǻHº = 148 kJ mol-1 (C)㧘A0 = 0.3125 mol kg-1, ǻHº = 158 kJ mol-1 (D)ࠍቯߒߚࠪࡒࡘ࡚ࠪࡦ߅ࠃ߮㧘 B, C, Dߩว⸘(E)㧚ǻSºߩ߁ߜᷙวࠛࡦ࠻ࡠࡇߪ࿑ 1ߩታ᷹୯ߩ᳇⋧⚵ᚑ߆ࠄ᳞ߚ㧚ઁߩ᧦ઙߪ࿑ 3 ߣหߓߢࠆ㧚 ߎߩࠃ߁ߥߎߣ߇߈ࠆߩߪ㧘 ᑼ߇␜ߔࠃ ߁ߦ ǻHº ߇৻ቯߩߣ߈ A0 ߇ዊߐ߶ߤࡇ᷷ࠢ ᐲ߇ૐߊߥࠆߚߢࠆ㧚㉄ὐߩ⒳㘃ࠍಽഀߒߡ ߘࠇߙࠇߦߟߡዊߐߥ A0 ࠍቯߔࠆߣ㧘ࡇࠢ ߪૐ᷷ߦឬ߆ࠇࠆߎߣߦߥࠆ㧚㉄ὐߩ⒳㘃ࠍ⚦߆ ߊಽߌ㧘A0 ࠍዊߐߊߔࠆ߶ߤࡇࠢߪૐ᷷ߦ⒖േ ߔࠆ㧚ߒߚ߇ߞߡ㧘หߓ⣕㔌᷷ᐲࠍࠪࡒࡘ࠻ ߔࠆߚߦߪ㜞 ǻHº ࠍቯߔࠆߎߣ߇ᔅⷐߦߥ ߞߡߒ߹߁㧚ࡇࠢߩ߇ᐢ߶ߤ㉄ᒝᐲ߇ᒝߊ ▚ߐࠇࠆߎߣߦߥࠅ㧘วℂ⊛ߢߥ㧚 ߹ߚ㧘ߎࠇࠍ⇣ߥࠆߢ⺑ߔࠆߣ㧘߃߫ $ ߩࠬࡍࠢ࠻࡞ࠍ⸘▚ߔࠆ㓙ߦߪหߓ⒳㘃ߩ㉄ὐ ߆ࠄ⣕㔌ߒߚࠕࡦࡕ࠾ࠕߩౣๆ⌕ߒ߆⠨ᘦߐࠇߕ㧘 ♽ౝߦሽߔࠆ % ߿ & ࠍ␜ߔ㉄ὐ߆ࠄߩࠕࡦࡕ࠾ ࠕߩౣๆ⌕߇ήⷞߐࠇߡࠆ߆ࠄߢࠆ㧚ߎߩࠃ ߁ߦ⇣ߥࠆ⒳㘃ߩ㉄ὐ߆ࠄߩౣๆ⌕ࠍήⷞߔࠇ߫㧘 ౣๆ⌕ߩᓇ㗀߇ㆊዊ⹏ଔߐࠇ㧘ࡇࠢߪૐ᷷ߦឬ ߆ࠇࠆ㧚 ߎࠇࠍ⸃ߔࠆߚߦߪోߡߩᐔⴧࠍ⸃ᨆߔ ߴ߈ߢࠆ߇㧘ᭂߡⶄ㔀ߦߥࠆߩߢߟ߉ߩࠃ߁.
(7) 29. 㠽 ข ᄢ ቇ ᄢ ቇ 㒮 Ꮏ ቇ ⎇ ⓥ ⑼㧛Ꮏ ቇ ㇱ ⎇ ⓥ ႎ ๔ ╙㧠㧜ภ. ߦㄭૃߔࠆ㧚A0 ࠍᄌ߃ߕߦ ǻHº ߩ⇣ߥࠆ㉄ὐࠍ ቯߒߡⶄᢙߩࡇࠢࠍឬ߈㧘ߎࠇࠄߦߘߩ㉄ὐߩ ሽᲧࠍਸ਼ߓߡࠬࡍࠢ࠻࡞ࠍวᚑߔࠆ㧚ߎߎߦ ߍߚߢߪ㧘$%& ߩઍࠊࠅߦߘࠇߙࠇ A0 OQNMIǻHº M,OQN ( 㧘A0 OQN MIǻHº M,OQN ) 㧘A0 OQNMI ǻHº M,OQN * ߩ ߟߩࠬࡍࠢ࠻࡞ᚑಽ ࠍ▚ߒ㧘( ) * ࠍోߩࠬࡍࠢ࠻࡞ ߣߒߡᓧࠆ㧚ߎࠇࠄߩᦛ✢ࠍ࿑ߦ␜ߔ㧚ߎߩࠃ ߁ߦߒߡᓧࠄࠇߚࠬࡍࠢ࠻࡞ . ߪ㧘ࡇࠢߩ᷷ᐲ ߇߶߷ # ߣหߓߢ㧘ࡇࠢߩ߇ᐢ㧚ߎߩࠃ߁ ߦߒߡ㧘㉄㊂ߣᐔဋ㉄ᒝᐲ߇หߓߢ㉄ᒝᐲߦಽᏓ ߇ࠆߎߣࠍߢ߈ࠆ㧚 A=G 0.02. L=I+J+K F. J = G/2. -3. 0.015. K = H/4 0.01. I = F/4. 0. 400. 500. 600 700 T/K. 800. ࿑ 7 A0 = 1.25 mol kg , ǻHº = 148 kJ mol (A)㧘A0 = 1.25 mol kg-1, ǻHº = 138 kJ mol-1 (F)㧘A0 = 1.25 mol kg-1, ǻHº = 148 kJ mol-1 (G, Aߣหߓ)㧘A0 = 1.25 mol kg-1, ǻHº = 158 kJ mol-1 (H)ࠍቯߒߚࠪࡒࡘ࡚ࠪࡦ ߅ࠃ߮㧘F/4 (I), G/2 (J), H/4 (K), I, J, Kߩว⸘(L)㧚ઁ ߩࡄࡔ࠲ߪ࿑ 6ߣหߓߢࠆ㧚 -1. Cg / mol m. -3. Cg / mol m. H. ߎߩᣇᴺߢ㧘 ࿁ߩ᷹ቯ߆ࠄ㉄㊂㧘㉄ᒝᐲ㧘ߘ ߩಽᏓࠍ᳞ࠆߎߣ߇ߢ߈ࠆ㧚࿑ߩࠬࡍࠢ࠻࡞ ߦㆡ↪ߒߚࠍ࿑ߦ␜ߔ㧚࿕㉄⸅ᇦߩ㊀ⷐߥ ৻⟲ߢࠆࠝࠗ࠻ߢߪ㧘ᄙߊߩ⹜ᢱߢࠕࡦࡕ ࠾ࠕๆ⌕ᾲߦᢙ M,OQN ߩಽᏓࠍቯߔࠆߣߎߩ ࠃ߁ߥ⦟ࡈࠖ࠶࠹ࠖࡦࠣ߇ᓧࠄࠇࠆ㧚 1 ǻHºߩᐔဋ୯߇ǻHºavgߢᮡḰᏅ߇ıߩࠟ࠙ࠬ ಽᏓࠍቯߒߚߣ߈ߩ㧘7⒳㘃ߩ㉄ὐߩ㊂(ో㉄㊂ߦ ኻߔࠆഀวf)ߣᒝᐲ(ǻHº) f ǻHº 0.0059 ∆Hºavg -3σ 0.060 ∆Hºavg -2σ 0.24 ∆Hºavg -σ 0.38 ∆Hºavg 0.24 ∆Hºavg +σ 0.060 ∆Hºavg +2σ 0.0059 ∆Hºavg +3σ. 0.01. 0.005. -1. ߟ߉ߦ㧘㉄ᒝᐲߩಽᏓࠍቯߔࠆ㧚ઁߦᖱႎ߇ ߥߩߢ㧘ߎߎߢߪ ǻHº ߇ࠟ࠙ࠬ㑐ᢙߦߒߚ߇ߞ ߡಽᏓࠍᜬߟߣቯߔࠆ ߚߛߒߎߩቯߦߪ‛ ℂ⊛ᗧߪߥ 㧚ߔࠆߣ㧘ቯߔߴ߈ᄌᢙߪ ǻHº ߩᐔဋ୯ߣᮡḰᏅߩ ߟߢࠆ㧚߹ߚ㧘Ṗࠄ߆ ߥಽᏓࠍᜬߟᄙᢙߩ᭴ᚑⷐ⚛ࠍቯߔࠆߣ⸘▚ᤨ 㑆߇㐳ߊߥࠆߩߢ㧘ǻHº ߩಽᏓࠍ 㗔ၞߦಽߌ㧘 ⇣ߥࠆ ǻHº ࠍᜬߟ ⒳㘃ߩ㉄ὐࠍߩࠃ߁ߦ ቯߔࠆ㧚ߎࠇࠄߩ㉄ὐ߆ࠄߩ⣕㔌ࠬࡍࠢ࠻࡞ࠍ࿑ ߣหߓේℂߢว⸘ߔࠆ㧚ታ᷹୯ߣࠃߊࡈࠖ࠶࠻ߔ ࠆࠬࡍࠢ࠻࡞ࠍਈ߃ࠆ A0㧘ǻHº avg㧘ı ߇᷹ቯߒߚ ⹜ᢱߩ㉄㊂㧘ᐔဋ㉄ᒝᐲ㧘㉄ᒝᐲಽᏓࠍߘࠇߙࠇ ␜ߔ㧚. 0. 400. 500. 600. 700 T/K. 800. 900 . ࿑ 8 ࿑ 1ߩࠕࡦࡕ࠾ࠕTPDࠬࡍࠢ࠻࡞ታ᷹୯(ᄥ ✢)ߣ㧘ࠞࡉࡈࠖ࠶࠹ࠖࡦࠣᴺߦࠃࠆᦨㆡࠪࡒࡘ ࡚ࠪࡦ(⚦✢)ߩᲧセ㧚A0 = 1.25 mol kg-1㧘ǻHºavg = 148 kJ mol-1㧘ı = 8 kJ mol-1ߣቯߒߚ㧚ߘߩઁߩࡄࡔ ࠲ߪ࿑ 3ߣหߓ㧚 㧣㧚࠰࡞ࡃߦࠃࠆࠞࡉࡈࠖ࠶࠹ࠖࡦࠣᴺ=? ࠞࡉࡈࠖ࠶࠹ࠖࡦࠣᴺߢߪ㉄ᒝᐲߩಽᏓࠍ ࠆ⒟ᐲ᳞ࠆߎߣ߇ߢ߈ࠆ߇㧘ታ᷹ߐࠇߚࠬࡍ ࠢ࠻࡞߇න৻ߩ㉄ᒝᐲࠍቯߒߚࠪࡒࡘ࡚ࠪ ࡦߦૃߚᒻ⁁ߢࠆߣ߈㧘ߔߥࠊߜ㉄ᒝᐲಽᏓ߇ ⁜႐วߦߒ߆ㆡ↪ߢ߈ߥ㧚㕖ࠝࠗ࠻ߩᄙ.
(8) 30. ↰⋥િਤ⠀ ᐙ㧦ᐔⴧߦᡰ㈩ߐࠇߚ᷷⣕㔌ࠬࡍࠢ࠻࡞߆ࠄๆ⌕ᾲࠍ▚ߔࠆᣇᴺ. ࠍᜬߜ㧘ǻHº M,OQN ⒟ᐲߩ㉄ὐ߇ᄙ߇㧘 ߎࠇࠃࠅᒝ㉄ὐ߽ሽߒ㧘ǻHº ߪ M,OQN ⒟ᐲ߹ߢㅪ⛯⊛ߦಽᏓߒߡࠆߣ⸒߃ࠆ㧚ߎߩࠃ ߁ߦߒߡ㧘㉄㊂ߣ㉄ᒝᐲߩಽᏓࠍ⚦ߦ᳞ࠆߎ ߣ߇ߢ߈ࠆ㧚 ߎߩᣇᴺߦࠃߞߡᓧࠄࠇࠆ 62& ࠬࡍࠢ࠻࡞ߩࠪ ࡒࡘ࡚ࠪࡦߪలಽߦṖࠄ߆ߢࠆ߇ ࿑ 㧘 ㉄ᒝᐲಽᏓߪ ǻHº ߦߒߡ M,OQN ೞߺߩ☻ᦛ ✢ ࿑ ߣߒߡᓧࠄࠇࠆ㧚㉄ὐߩಽഀᢙࠍჇ߿ߔ ߣ♖ኒߦߥࠆߪߕߛ߇㧘/KETQUQHV'ZEGN ߩ⸘▚ น⢻ኈ㊂߿ㅦᐲ߆ࠄߪ㉄ὐߩ⒳㘃ࠍߎࠇએჇ߿ ߔߎߣߪ࿎㔍ߢ㧘ኾ↪ߩ࠰ࡈ࠻࠙ࠚࠕߩ㐿⊒߇ᔅ ⷐߢࠆ㧚 0.003 (dCw/d∆H) / (mol kg-1 / kJ mol-1). Concentration of ammonia in gas phase / mol m. -3. ߊߩ࿕㉄߇㧘࿑ 1DUGTXGF ߩࠃ߁ߦᐢ 62& ࠬࡍࠢ࠻࡞ࠍ␜ߒ㧘ߎࠇߪᐢ㧘ࠆߪⶄ 㔀ߥ㉄ᒝᐲಽᏓࠍᤋߒߡࠆ㧚ߎߩࠃ߁ߥ႐ว ߦߪ㧘㉄ᒝᐲಽᏓߩቯߩᣇᴺߦᎿᄦ߇ᔅⷐߢ ࠆ㧚 ߘߎߢࠞࡉࡈࠖ࠶࠹ࠖࡦࠣᴺࠍ⊒ዷߐߖ㧘 㨪M,OQN ߹ߢ M,OQN ೞߺߩ ǻHº ࠍᜬߟ ⒳ߩ㉄ὐࠍቯߒ㧘ߎࠇࠄ ⒳ߩ㉄㊂ࠍᄌൻ ߐߖߡ 62& ࠬࡍࠢ࠻࡞ࠍࠪࡒࡘ࠻ߒ㧘ታ᷹ߐ ࠇߚࠬࡍࠢ࠻࡞ߣ৻⥌ߔࠆࠃ߁ߦ ⒳ߩ㉄㊂ߩ ⚵ߺวࠊߖࠍㆬ߱ᣇᴺࠍ⠨᩺ߒߚ㧚ߚߛߒᄌᢙ߇ ᄙߔ߉ߡ⥄↱ᐲ߇ᄢ߈ߊ㧘ቴⷰ⊛ߦᦨㆡߥ⚵ߺว ࠊߖࠍㆬ߱ߎߣߪᚻᬺߢߪ࿎㔍ߢࠆ㧚ߘߎߢ /KETQUQHV'ZEGN ߩ࠰࡞ࡃᯏ⢻ࠍ↪ࠆᣇᴺࠍ 㐿⊒ߒߚ㧚 0.00002 Simulated Observed 0.00001. 0. 0.002. 0.001. 0 0. 400. 500 600 Temperature / K. 700. ࿑ 9 SO42-/ZrO2 ߩࡉࡦࠬ࠹࠶࠼㉄ߩࠕࡦࡕ࠾ࠕ TPDࠬࡍࠢ࠻࡞(ᄥ⎕✢)ߣ㧘ቯߒߚฦ⒳ߩ㉄ὐ߆ࠄ ߩࠬࡍࠢ࠻࡞ᚑಽߩࠪࡒࡘ࡚ࠪࡦ(⚦ታ✢)㧘ߘߩ ว⸘(ᄥታ✢)ߩᲧセ㧚ȕ = 0.17 K s-1, W = 8.6×10-6 kg, A0 = 0.074 mol kg-1, F = 6.8×10-5 m3 s-1, ǻSº = 95 J K-1 mol-1 + ᷙวߩࠛࡦ࠻ࡠࡇߣቯߒ㧘࿑ 10ߦ␜ߔ ಽᏓࠍᜬߟǻHºࠍቯߒߚ㧚ᚑಽ(⚦ታ✢)ߪ࿑ 7ߩI, J, Kߣหߓේℂߢ▚ߒߚ㧚 ࿑ 1DUGTXGF ߩࠬࡍࠢ࠻࡞ߦኻߒߡ⸃ᨆࠍ ⴕߞߚߣߎࠈ㧘࿑ߩࠃ߁ߥ ǻHº ߩಽᏓ߇ឭ᩺ ߐࠇߚ㧚࿑ߦߪߘࠇߙࠇߩ ǻHº ࠍᜬߟ㉄ὐߩ ሽ㗫ᐲ߇㧘ǻHº ߦࠃࠆᓸಽᦛ✢ߩᒻᑼߢߐࠇ ߡࠆ㧚ߎߩಽᏓߦၮߠߡ 62& ࠬࡍࠢ࠻࡞ࠍࠪ ࡒࡘ࠻ߒߚߣߎࠈ㧘࿑ 5KOWNCVGF ߩࠃ߁ ߥࠬࡍࠢ࠻࡞߇ᓧࠄࠇ㧘ታ᷹୯ߣ߶߷৻⥌ߒߚ㧚 ߒߚ߇ߞߡߎߩ⹜ᢱߩ ǻHº ߪ࿑ߩࠃ߁ߥಽᏓ. 100. 150 200 -1 ∆H / kJ mol. 250. ࿑ 10 ࿑ 9ߩTPDࠬࡍࠢ࠻࡞߆ࠄᓧࠄࠇߚ㉄ᒝᐲ ಽᏓ㧚 㧤㧚▚ߐࠇߚๆ⌕ᾲߩ⹏ଔߣᗧ⟵ એߩࠃ߁ߦ㧘ࠕࡦࡕ࠾ࠕ 62& ࠬࡍࠢ࠻࡞ࠍ⸃ ᨆߒ㧘㉄ᒝᐲࠍ␜ߔࠕࡦࡕ࠾ࠕๆ⌕ᾲ ǻHº ࠍ᳞ ࠆᣇᴺࠍ㐿⊒ߒߚ㧚ᄙὐᴺߦࠃࠆߣⶄᢙߩ᷹ቯ߆ ࠄ ǻHº㧘ǻSº ઍ୯ ࠍ᳞ࠆߎߣ߇ߢ߈ࠆ㧚৻ ὐᴺߢߪ ࿁ߩ᷹ቯ߆ࠄ ǻHº ઍ୯ ࠍ᳞ࠆߎ ߣ߇ߢ߈ࠆ㧚ࠞࡉࡈࠖ࠶࠹ࠖࡦࠣᴺߢߪ ǻHº ߩ ಽᏓ߇⁜႐วߦߘߩಽᏓࠍ᳞ࠆߎߣ߇ߢ߈ࠆ㧚 ࠰࡞ࡃߦࠃࠆࠞࡉࡈࠖ࠶࠹ࠖࡦࠣᴺߢߪ ǻHº ߩಽᏓ߇ᐢ႐วߦ߽ಽᏓࠍ᳞ࠆߎߣ߇ߢ߈㧘 ǻHº ߩಽᏓᦛ✢߇ᓧࠄࠇࠆ㧚 ߊߟ߆ߩ᷹ቯߦߟߡ㧘ᓧࠄࠇߚࠕࡦࡕ࠾ࠕ ๆ⌕ᾲࠍᓸዊᾲ㊂⸘ߦࠃࠆ⋥ធ᷹ቯ୯ߣᲧセߒߚ ߣߎࠈ㧘߅߅ߨ৻⥌ߒߚ=?㧚ߎࠇߪࠕࡦࡕ࠾ࠕ 62& ߩታ㛎⸃ᨆᴺਔᣇߩᱜ⏕ߐࠍታ⸽ߒߡࠆ㧚.
(9) 31. 㠽 ข ᄢ ቇ ᄢ ቇ 㒮 Ꮏ ቇ ⎇ ⓥ ⑼㧛Ꮏ ቇ ㇱ ⎇ ⓥ ႎ ๔ ╙㧠㧜ภ. ߹ߚ㧘ᓧࠄࠇߚࠕࡦࡕ࠾ࠕๆ⌕ᾲ߇㉄ᒝᐲߩᜰᮡ ߢࠆ 1* િ❗ᝄേߩᵄᢙߣኻᔕߒߡࠆߎߣ=? ߽㧘ᧄᚻᴺߩᅷᒰᕈࠍᡰᜬߒߡࠆ㧚 ࠕࡦࡕ࠾ࠕๆ⌕ᾲߪ‛ℂൻቇ⊛ߦቯ⟵ߩ⏕ ߥࡄࡔ࠲ߥߩߢ㧘ᓥ᧪ߩ㉄ᒝᐲߩዤᐲߢࠆ * ᜰᢙߦᄌ឵߽ߢ߈ࠆ=?㧚߹ߚ㧘ࠕ࡞ࠞࡦಽ⸃ߥ ߤߩ⸅ᇦᔕߩㅦᐲ߿㧘ߐࠄߦ♖ኒߦߪᵴᕈൻࠛ ࡀ࡞ࠡߣࠃߊኻᔕߒߡ߅ࠅ㧘⸅ᇦ↪ࠍวℂ⊛ ߦ⺑ߢ߈㧘㜞ᵴᕈࠍᜬߟ⸅ᇦߩ⸳⸘ᜰ㊎ࠍਈ ߃ߡࠆ=?㧚߹ߚ㧘ᧄ⸃ᨆᣇᴺߪ࿕㉄ߩ ࠕࡦࡕ࠾ࠕ 62& ߦ㒢ࠄߕᐔⴧᡰ㈩ߩ 62& ߦᐢߊㆡ ↪ߢ߈㧘0C ࠝࠗ࠻ߩ࠻࡞ࠛࡦߩๆ⌕ᕈ⾰ߩ ⸃ᨆߦ߽ᔕ↪ߐࠇࠆ=?ߥߤ㧘ᵄലᨐ߽ᄢ߈㧚 ߐࠄߦ㧘࿕㉄⸅ᇦߩ㊀ⷐߥ৻⟲ߢࠆࠝ ࠗ࠻ߦ߅ߡߪ㧘᷹ቯߐࠇߚࠕࡦࡕ࠾ࠕๆ⌕ᾲ߇ ኒ ᐲ ᳢ 㑐 ᢙ ℂ ⺰ FGPUKV[ HWPEVKQPCN VJGQT[ &(6 ߦࠃࠆ⸘▚୯ߣࠃߊ৻⥌ߔࠆ=?㧚ߎ ߩߎߣߪ⸃ᨆᴺߩᅷᒰᕈࠍ␜ߒߡࠆߩߺߥࠄߕ㧘 ታ㛎ߣℂ⺰ࠍ৻ߣߒߡ⎇ⓥߔࠆߎߣߦࠃߞߡ㧘 ࿕㉄ߩේℂࠍ⸃ߔࠆၮ␆⊛ߥ⍮ࠍ߽ߚࠄߒ ߡࠆ㧚ࠍߍࠆߣ㧘; ဳࠝࠗ࠻ߩ⚦ሹߦ ⓭߈ߒߚ㉄ὐߩⵣ ოߩਛ ߦ %C ߥߤᄙଔࠞ ࠴ࠝࡦࠍ㈩⟎ߔࠆߣ㔚ሶ߇ๆᒁߐࠇ㧘㉄ὐ߇ᒝ ࠄࠇࠆߎߣ=?㧘ߎߩࠃ߁ߥઁ⒳ߩࠞ࠴ࠝࡦߩᓇ 㗀ߩߥ႐วߦߪ㧘⚿᥏᭴ㅧߦ↱᧪ߔࠆ᭴ㅧ⊛ߥ ߭ߕߺߦࠃߞߡ㉄ᒝᐲ߇߹ࠆߎߣ=?ߥߤ㧘࿕ ㉄ᕈ⾰߇ߤߩࠃ߁ߦ߹ߞߡࠆߩ߆ߦ㑐ߔࠆ ㊀ⷐߥ⊒߇ߥߐࠇߡࠆ㧚 ෳ⠨ᢥ₂ =? Niwa, M., Suzuki, K., Katada, N., Kanougi, T., and Atoguchi, T. : Ammonia IRMS-TPD study on the distribution of acid sites in mordenite, J. Phys. Chem., B, 109, pp. 18749-18757, 2005. =?Niwa, M., Katada, N., Sawa M., and Murakami, Y. : Temperature-Programmed Desorption of Ammonia with Readsorption Based on the Derived Theoretical Equation, J. Phys. Chem., 99, pp. 8812-8816, 1995. =?Naito, N., Katada, N., and Niwa, M. : Tungsten Oxide Monolayer Loaded on Zirconia: Determination of Acidity Generated on the Monolayer, J. Phys. Chem., B, 103, pp. 7206-7213, 1999. =? ↰⋥િ㧘ਤ⠀ ᐙ ࿕㉄ᕈ⾰᷹ቯߦ߅ ߌࠆᦨㄭߩㅴᱠ⸅ᇦRR =?ᄢ㐷 ኡ㧘ၴ৻ᚑ⸶ ࡃࡠ‛ℂൻቇ ╙ 㧘R㧘᧲੩ൻቇหੱ㧘㧚 =?Katada, N., Igi, H., Kim, J.-H., and Niwa, M. : Determination of the Acidic Properties of Zeolite. by Theoretical Analysis of Temperature-Programmed Desorption of Ammonia Based on Adsorption Equilibrium, J. Phys. Chem., B, 101, pp. 5969-5977, 1997. =?Katada, N., Tsubaki, T., and Niwa, M : Measurements of Number and Strength Distribution of Brønsted and Lewis Acid Sites on Sulfated Zirconia by Ammonia IRMS-TPD Method, Appl. Catal., A: Gen., 340, pp. 76-86, 2008. =?Suzuki, K., Noda, T., Katada, N., and Niwa, M. : IRMS-TPD of ammonia: Direct and Individual Measurement of Brønsted Acidity in Zeolites and its Relationship with the Catalytic Cracking Activity, J. Catal., 250, pp. 151-160, 2007. =?Katada, N., Endo, J., Notsu, K., Yasunobu, N., Naito, N., and Niwa, M. : Superacidity and Catalytic Activity of Sulfated Zirconia, J. Phys. Chem., B, 104, pp. 10321-10328, 2000. =?Noda, T., Suzuki, K., Katada, N., and Niwa, M. : Combined Study of IRMS-TPD Measurement and DFT Calculation on Brønsted Acidity and Catalytic Cracking Activity of Cation Exchanged Y Zeolites, J. Catal., 259, pp. 203-210, 2008. =?Yoshimoto, R., Hara, K., Okumura, K., Katada, N., and Niwa, M. : Analysis of Toluene Adsorption on Na-form Zeolite Using Temperature-Programmed Desorption Method, J. Phys. Chem., C, 111, pp. 1474-1479, 2007. =?Suzuki, K., Sastre, G., Katada, N., and Niwa, M. : Quantitative Measurements of Brønsted Acidity of Zeolites by Ammonia IRMS-TPD Method and Density Functional Calculation, Chem. Lett., 36, pp. 1034-1035, 2007. =?Suzuki, K., Sastre, G., Katada, N., and Niwa, M. : Ammonia IRMS-TPD Measurements and DFT Calculation on Acidic Hydroxyl Groups in CHA-type Zeolite, Phys. Chem. Chem. Phys., 9, pp. 5980-5987, 2007. =?Suzuki, K., Noda, T., Sastre, G., Katada, N., and Niwa, M. : Periodic Density Functional Calculation on Brønsted Acidity of Modified Y-type Zeolite, J. Phys. Chem., C, 113, pp. 5672-5680, 2009. =? Suzuki, K., Sastre, G., Katada, N., and Niwa, M. : Periodic DFT Calculation of the Energy of Ammonia Adsorption on Zeolite Brønsted Acid Sites to Support the Ammonia IRMS-TPD Experiment, Chem. Lett., 38, pp. 354-355, 2009. =?Katada, N., Suzuki, K., Noda, T., Sastre, G., and Niwa, M. : Correlation between Brønsted Acid Strength and Local Structure in Zeolites, J. Phys. Chem., C, doi: 10.1021/jp903788n. . ฃℂ ᐔᚑ 21 ᐕ 10 28 ᣣ .
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