研究生: |
古冠軒 Kuan-Hsuan Ku |
---|---|
論文名稱: |
DNPH與Cu(II)反應的動力學及反應機制探討 Kinetics and Mechanism of 2,4-Dinitrophenylhydrazine (DNPH) with Copper(II) |
指導教授: |
吳劍侯
Chien-Hou Wu |
口試委員: | |
學位類別: |
碩士 Master |
系所名稱: |
原子科學院 - 生醫工程與環境科學系 Department of Biomedical Engineering and Environmental Sciences |
論文出版年: | 2007 |
畢業學年度: | 95 |
語文別: | 中文 |
論文頁數: | 71 |
中文關鍵詞: | 2,4-dinitrophenylhydrazine 、銅錯合物 、動力學 、反應機制 |
外文關鍵詞: | 2,4-dinitrophenylhydrazine, copper complexes, kinetics, mechansism |
相關次數: | 點閱:3 下載:0 |
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本研究利用紫外可見光譜儀於25℃下偵測反應中2,4-dinitrophenylhydrazine (DNPH)的初始衰退速率以探討水相系統中DNPH與Cu(II)的動力學反應。DNPH為分析醛類廣泛使用的衍生試劑,由於DNPH結構中的hydrazine group容易被二價銅離子所氧化,因此造成在二價銅離子存在於系統中時,分析醛類會有嚴重的干擾。為了解此反應,實驗中探討了許多參數諸如:DNPH濃度、Cu(II)濃度、pH值、離子強度及溫度。DNPH衰退的反應速率分別隨DNPH濃度及Cu(II)濃度成一級反應,且DNPH會被質子化而形成HDNPH+,這兩個物種之間維持著平衡存在。利用Arrhenius equation和Eyring equation分別求得反應活化能為45.0 kJ/mol及反應的△H□為42.2 kJ/mol。整個系統的反應速率式可以用下列的方程式去描述:
本研究利用紫外可見光譜儀、離子層析儀、電子順磁共振儀、高效率液相層析儀以及液相層析質譜儀等的儀器來進行中間產物與產物的分析。在氧化過程中,發現當消耗1莫耳的DNPH,會產生3–4莫耳的一價銅;藉著形成中間產物aryl自由基,進一步生成2,4-dinitrophenol為主要的最終產物。最後綜合以上實驗結果提出合理的反應機制。
The kinetics and mechanism of oxidation of 2,4-dinitrophenylhydrazine (DNPH), a widely used derivatization reagent for analysis of aldehydes, with copper(II) in aqueous solution have been studied spectrophotometrically as a function of Cu(II) and DNPH concentrations at ionic strength (I = 1M) of NaCl. Since the hydrazine group of DNPH would be easily oxidized by Cu(II), serious interference for determination of aldehydes with Cu(II) was needed to be examined. The rate of the reaction was followed by monitoring the disappearance of the DNPH at 360 nm. System parameters such as pH, ionic strength, temperature and concentrations of Cu(II) and DNPH are examined. The rate of oxidation of DNPH is first order with respect to Cu(II) and DNPH concentrations. The oxidation of DNPH was studied at different temperatures (T = 293 – 313 K), and the active parameters Ea, △H□ and △S□ were evaluated. And the rate law of the whole system was followed as:
The oxidation occur via aryl radical intermediate, to produce 2,4-dinitrophenol as final product. In the oxidation 3-4 mol of Cu(I) are produced by each mol of DNPH.
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