气相室温检测 - - 丁氧化消极剂的气相室温检测
Casper Vindahl Jensen1, Henrik G Kjaergaard1
1Department of Chemistry, University of Copenhagen, 2100 Copenhagen-Ø, Denmark.
The journal of physical chemistry. A
|August 1, 2023
概括
研究人员使用FTIR在气相中检测到三甲基氧化物二次体. 这项研究确定了二分体.
科学领域:
- 物理化学 物理化学
- 频谱学是一种光谱学.
- 化学物理 化学物理
背景情况:
- 特-丁氧化 (TBHP) 是一种有机过氧化物,具有各种工业应用.
- 了解TBHP在气相中的自我结合对于其化学行为至关重要.
- 之前的研究没有最终确定气相中的TBHP二聚体.
研究的目的:
- 在气相中检测和表征三丁氧化二聚物.
- 为了确定二次体的结构和光谱特性.
- 为了估计TBHP的二分化常数.
主要方法:
- 气相里埃变换红外光谱 (FTIR) 在室温下.
- 阿贡矩阵隔离FTIR光谱在12K.
- 计算化学 (密度函数理论) 用于结构分析.
- 对与结合的OH伸展带的分析.
主要成果:
- 在气相中直接检测三-基氧化物二聚物 (BuOOH) 的直接检测.
- 对二次体的结O-H延伸的特征红移吸收带 (∼3452cm-1) 的识别.
- 确定最低能量的二次体结构,作为一个具有双键的六个成员环.
- 估计气相二分化常数 (K) 在1 bar时为0.4.
结论:
- 这项研究提供了第一个直接的光谱证据,证明了 tert-butyl氧化二元体在气相中的存在.
- 二元体存在于一个双结合的六个成员的环.
- 二元化常数为TBHP的自我关联倾向提供了洞察力.
更多相关视频
相关概念视频
Autoxidation of Ethers to Peroxides and Hydroperoxides
7.7K
Ethers represent a class of chemical compounds that become more dangerous with prolonged storage because they tend to form explosive peroxides when standing in the air. Autoxidation is the spontaneous oxidation of a compound in air. In the presence of oxygen, ethers slowly oxidize to form hydroperoxides and dialkyl peroxides.
7.7K
Hydroboration-Oxidation of Alkenes
8.4K
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
8.4K
Regioselectivity of Electrophilic Additions-Peroxide Effect
8.7K
In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.
8.7K
Hydrolysis of Chlorobenzene to Phenol: Dow Process
2.9K
Simple aryl halides do not react with nucleophiles under normal conditions. However, the reaction can proceed under drastic conditions involving high temperatures and high pressure to give the substituted products. For example, chlorobenzene is converted to phenol using aqueous sodium hydroxide at 350 °C under high pressure by the Dow process. The reaction follows an elimination-addition mechanism involving a benzyne intermediate. Here, the chloride ion is...
2.9K
Gas Chromatography: Types of Detectors-II
418
In gas chromatography, different detectors are employed to meet specific analytical needs. These detectors are often categorized based on their detection mechanisms and the types of compounds they are best suited to analyze. Thermal Conductivity Detectors (TCD), Flame Ionization Detectors (FID), and Electron Capture Detectors (ECD) represent common categories, each with unique operating principles and applications. However, beyond these, several other detectors are designed for more specialized...
418
¹H NMR of Labile Protons: Deuterium (²H) Substitution
925
This lesson illustrates the role of deuterium substitution in simplifying the NMR spectrum of compounds comprising labile protons. One method employed is the use of deuterium. Amongst the three isotopes of hydrogen, deuterium (2H) has a nucleus composed of one proton and one neutron. When the D2O solvent is added to a pure dry ethanol solution, its labile proton is substituted with deuterium.
925


