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研究生:連明惠
研究生(外文):MingHuiLien
論文名稱:維他命C與五氰鐵(III)錯合物之氧化還原反應探討
論文名稱(外文):The Investigation of the Redox Reactions between Ascorbic Acid and Pentacyanoferrate(III) Complexes
指導教授:葉玉堂
學位類別:碩士
校院名稱:東海大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2004
畢業學年度:92
語文別:中文
中文關鍵詞:維他命C
外文關鍵詞:Ascorbic Acid
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維他命C還原[Fe(CN)5L]2-(L=py, isn)的反應屬外圈電子轉移反應機構,反應速率受溶液pH影響,主要乃由於維他命C為雙質子酸,在不同pH條件下分別以H2A,HA‾及A2‾型態出現,從pH=1~7.5,μ=0.10M HClO4/LiClO4條件下動力學探討結果分別得k0(H2A)= 1.8 ( L=py ),7.0 (L=isn);k1(HA‾)=1.6×103 ( L=py ),4.5×103 (L=isn);k2(A2‾)=6.5×108 ( L=py ),8.8×108 (L=isn) M-1s-1,根據Marcus理論分析,發現在不同pH條件下之所以有如此大的還原速率差異k0:k1:k2~1:103:108,與反應物之電荷效應無多大關聯,主要乃由維他命C在不同型態中反應活性(kex)及反應能障之差異所引起。
以計量化學的方式用quercetin來還原 [Ru(NH3)5isn]3+錯合物,確定quercetin為3個電子的還原劑。在pH=5.0條件下,於μ=0.1M LiCl,T=25℃的條件下進行測量反應速率常數為(1.57±0.02)×104 M-1s-1。
The oxidation of ascorbic acid by [Fe(CN)5L]2‾(L=py, isn) complexes undergoes outer-sphere electron transfer mechanism. The rate of the reduction depends on the pH of the solution for the reason that ascorbic acid exists in different forms, namely H2A, HA‾ and A2‾, at various pH values. The kinetic studies of the reactions at [H+]= 0.01~0.10 M and pH=4~7.5 yield specific rate constants of reduction as k0(H2A)= 1.8 ( L=py ),7.0 (L=isn);k1(HA-)=1.6×103 ( L=py ),4.5×103 (L=isn);k2(A2-)=6.5×108 ( L=py ),8.8×108 (L=isn)M-1s-1,respectively at m=0.10 M HClO4/LiClO4 and T=25℃. Our kinetic results conform with Marcus theory for outer-sphere electron transfer. Moreover, the detailed theoretical analysis indicates that, the tremendously large rate difference with k0:k1:k2~1:103:108, arises predominantly from the equilibrium barrier and the intrinsic reactivities of the different acid forms of the ascorbic acid, and is rather insensitive to the charge effect of the reactants.
The stoichiometry for the reduction of [Ru(NH3)5isn]3+ complexes by the quercetin, shows that sure the quercetin is a three electron reductant. The kinetic studies of the reactions at pH=5.0 yield specific rate constant of reduction k = (1.57±0.02)×104 M-1s-1 at m =0.10 M LiCl and T=25℃.
第一章 序 論………………………………………………….1
第二章 實 驗…………………………………………………12
一、 主要的藥品來源……………………………………..12
二、 藥品的純化與溶液配製……………………………..14
三、 合成…………………………………………………..16
四、 去氧系統……………………………………………..18
五、 分析儀器及方法……………………………………..20
第三章 結 果………………………………………………….26
一、 光譜鑑定……………………………………………..26
二、 計量化學……………………………………………..30
三、 還原反應動力學……………………………………..32
第四章 討 論………………………………………………...53
一、 還原反應動力學……………………………………..53
二、 Marcus理論…………………………………………..58
第五章 槲皮素氧化探討………………………………………65
第六章 結論……………………………………………………77
參考文獻………………………………………………………….78
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