A Study of the Photochemical Reactions between Chlorine and Propene Gases

氯氣分子與丙烯分子經由紫外線照射後，會進行加成反應： 為了研究其反應的機制，我們架設了一套真空系統。在兩個不The chlorine and propene gases will process addition reaction under the irradiation of UV light: We have built up a vacuum system in order to study the reaction mechanism. We fill chlorine gas and propene gas individually into two different stainless steel tanks, and then fill in nitrogen gas to the ratio we want. In order to control the partial pressure of chlorine and propene gases in the reaction cell, two mass flow meters are used to control the flow rate of both of them. A mercury lamp with a band-width filter is the light source, and makes the wave length of the UV light which passes through the reaction cell be about the maximum absorption near the bond energy of a chlorine molecule. So we can generate the chlorine radical to react with propene. Then the products pass through a potassium carbonate column that can trap the hydrogen chloride molecule generated in the reaction. After that, a low-temperature trap (about –80℃) is used to collect the products. The collected products are analysised by the proton-NMR. In addition to the experiment, we use the theoretical calculation software (Gaussian 03) to calculate the probable molecules in the reaction mechanism by the density functional theory with different basis sets. And compare the results with our experiments.論文摘要 vi 英文摘要 vii 第一章 緒論 1 第二章 實驗細節 3 §2.1. 光源 5 §2.2. 流量控制儀 5 §2.3. 樣品氣體及載氣 5 §2.4. 低溫收集器 5 §2.5. 產物分析 5 §2.6. 實驗方法 5 第三章 實驗結果與討論 7 §3.1. 主要產物的光譜鑑定 7 §3.2. 反應物分壓比與產物的關係 113 第四章 理論計算 18 §4.1. 全始分子軌域理論 18 §4.2. 步驟與流程 26 第五章 理論計算結果 28 §5.1. 氯原子自由基與丙烯分子的加成途徑 43 §5.2. 2-氯丙烯自由基的1,2質子轉移途徑 44 §5.3. 氯原子自由基摘取丙烯分子二號碳上的氫原子途徑 44 §5.4. 氯原子自由基摘取丙烯分子三號碳上的氫原子途徑 48 §5.5. 氯原子自由基摘取1,2-二氯丙烷分子上的氯原子途徑50 第六章 結論 52 第七章 未來展望 5