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題名 | Kinetic Studies and Catalytic Activity for H[feaf]O[feaf]Disproportionation of Bis (1,1,1,5,5,5- hexafluoropentane-2,4-dionate) Manganese (Ⅱ) Complexes with Diazine Ligands=六氟乙醯丙酮及雙氮嗪配位基錳錯化合物對過氧化氫不均化催化反應之活性與動力學研究 |
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作者 | 洪當明; Hong, Dang-ming; |
期刊 | 慈濟技術學院學報 |
出版日期 | 19990800 |
卷期 | 1 1999.08[民88.08] |
頁次 | 頁127-147 |
分類號 | 346.2 |
語文 | eng |
關鍵詞 | 六氟乙醯丙酮; 雙氮嗪配位基錳錯化合物; 過氧化氫; 動力學; Disproportionation; Turnover number; Michaelis-menten constant; |
中文摘要 | 雙核〔Mn2(hfac)4(pyz)(H2O)2 2H2O〕(1)和單核〔Mn(hfac)2(pym)(H2O)〕(2)兩個錳錯化合物對過氧化氫的分解成氧氣和水,非常有效率的催化作用。由錯化合物分解過氧化氫反應的氧氣釋出結果,證明此兩錯化合物對於過氧化氫在砒碇中不均化分解具有催化的活性。兩錯化合物催化活性的更換值分別為每秒 0.215 及 0.119 ,顯示錯化合物(1)的活性比錯化合物(2)的活性強。 錯化合物催化過氧化氫分解的反應速率定律式為:-d〔H2O2〕/dt=k〔H2O 2〕x〔complex〕y ,指數x、y分別代表過氧化氫、錯化合物的反應級數,k為反應速率常數。實驗結果:錯化合物(1)之x、y和k值分別為1.0192、1.0005和2.6405升/莫耳.秒;錯化合物(2) 之x、y和k值分別為0.9884、1.0069和2.1959升/莫耳.秒。 錯化合物催化過氧化氫分解的最大速率(Vmax)和米氏常數(Km)實驗結果為:錯化合物(1)之Vmax和Km值分別為0.1087mM/sec和0.1256M;錯化合物(2)之Vmax和Km值分別為13.1mM/sec和18.83M。 |
英文摘要 | Binuclear complex 〔Mn2(hfac)4(pyz)(HO2)2. 2HO2〕 (1)and mononuclear complex 〔Mn(hfac)2(pym)(H2O)〕 (2)(hfac=1,1,1,5,5,5-hexafluoropentane-2, 4-dionate, pyz=pyrazine and pym=pyrimidine) catalyze hydrogen peroxide decomposing to dioxygen and water very efficiently. The evolution of O2 by decomposing of H2O2 shows that all the complexes are catalytic activity towards disproportionation of H2O2 in pyridine at 10℃. The turnover number of complex 1, 2 are 0.215 sec-1, 0.119 sec-1, respectively, reveals that the complex 1 is more active than that of complex 2. The decomposition of H2O 2 by complex 1 and 2 has reaction rate law of the form - d〔H2O2〕/dt =k〔H2O 2〕X〔complex〕Y, the exponents x, y represent the order of the reaction and K is rate constant. The values of x, y and k are obtained as 1.0192, 1.0005 and 2.6405 dm3 mol-1 sec-1 for complex 1; 0.9884, 1.0069 and 2.1959 dm3 mol-1 sec-1 for complex 2, respectively. The maximal rate, Vmax, of the catalase-like reaction is 0.1087 mM/sec per mg for complex 1, 13.1 mM/sec per mg for complex 2. The Michaelis-Menten constant, Km, of complex 1, 2 are 0.1256 M and 18.83 M for hydrogen peroxide. |
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