在振动强合下测量动力学:测试水和酒精的核友性变化
Cyprien Muller1, Robert J Mayer1,2, Maciej Piejko1
1University of Strasbourg, CNRS, ISIS UMR 7006, 67000, Strasbourg, France.
Angewandte Chemie (International ed. in English)
|August 21, 2024
概括
振动强合 (VSC) 在极性反应中没有显著改变水和酒精的核友性. 新的光腔方法可以进行精确的动力测量,这表明VSC通过未知的机制修改反应.
科学领域:
- 化学动力学 化学动力学
- 物理化学 物理化学
- 频谱学是一种光谱学.
背景情况:
- 已知振动强合 (VSC) 会影响有机反应速率.
- 对VSC的影响的机制理解受到动力测量的挑战所限制.
- 在VSC下开发可靠的动力分析方法对于该领域的进步至关重要.
研究的目的:
- 调查振动强合 (VSC) 是否改变极地物种如水和酒精的核友性.
- 在VSC条件下建立一种方便和准确的方法来测量反应动力学.
- 探索VSC对极性反应影响的潜在机制.
主要方法:
- 利用最近开发的固定宽度光学空洞进行VSC实验.
- 采用UV/Vis光谱法来获得精确的动力数据集 (±1-5%的误差).
- 用基离子作为带有和没有VSC的电友的核友性捕获的确定速率常数.
主要成果:
- 在VSC下,只观察到水和酒精反应速率常数的微小变化.
- 结果独立于通过VSC结合的特定振动.
- 发现水和酒精的核友性在很大程度上不受VSC的影响.
结论:
- 振动强度合 (VSC) 不大大改变水和酒精的核友性.
- 由VSC修饰的极地反应可能通过目前未知的机制进行.
- 固定宽度的腔提供了一个强大的平台,用于在VSC修饰化学中进行可重现的动力学研究.
相关概念视频
¹H NMR of Labile Protons: Temporal Resolution
1.1K
Protons bonded to heteroatoms such as nitrogen and oxygen exhibit a range of chemical shift values. This is due to the varying degree of hydrogen bonding between the proton and the heteroatom in other molecules. The extent of hydrogen bonding affects the electron density around the proton, thereby giving different chemical shift values for the protons in the proton NMR spectrum.
The –OH proton in alcohols typically appears in the range of δ 2 to 5 ppm but can vary depending on the specific...
The –OH proton in alcohols typically appears in the range of δ 2 to 5 ppm but can vary depending on the specific...
1.1K
Measuring Reaction Rates
24.9K
Polarimetry finds application in chemical kinetics to measure the concentration and reaction kinetics of optically active substances during a chemical reaction. Optically active substances have the capability of rotating the plane of polarization of linearly polarized light passing through them—a feature called optical rotation. Optical activity is attributed to the molecular structure of substances. Normal monochromatic light is unpolarized and possesses oscillations of the electrical...
24.9K
Physical Properties of Alcohols and Phenols
14.1K
Alcohols are organic compounds in which a hydroxy group is attached to a saturated carbon. Phenols are a class of alcohols containing a hydroxy group attached to an aromatic ring. The physical properties of the alcohols and phenols are influenced by hydrogen bonding due to the oxygen–hydrogen dipole in the hydroxy functional group and dispersion forces between alkyl or aryl regions of alcohol and phenol molecules.
Alcohols possess a higher boiling point than aliphatic hydrocarbons of...
Alcohols possess a higher boiling point than aliphatic hydrocarbons of...
14.1K
IR and UV–Vis Spectroscopy of Aldehydes and Ketones
5.4K
Infrared spectroscopy, also known as vibrational spectroscopy, is mainly used to determine the types of bonds and functional groups in molecules. In aldehydes and ketones, the carbonyl (C=O) bond shows an absorption around 1710 cm-1. The C=O bond vibration of an aldehyde occurs at lower frequencies than that of a ketone. In addition to the C=O absorption in an aldehyde, the aldehydic C–H bond also gives two peaks in the 2700–2800 cm-1 range. This absorption, coupled with the...
5.4K
Titration in Nonaqueous Solvents
769
Most acid-base titrations are performed in an aqueous medium. In aqueous titrations, water competes with weaker acids or bases for proton donation or acceptance, leading to ambiguous endpoints in the titration curve. Water also affects the partial ionization of weak acids or bases. For example, water accepts a proton from acetic acid to form hydronium and acetate ions. The hydronium ion formed is a stronger acid than acetic acid, and the acetate ion is a stronger base than water. As a result,...
769
Acidity and Basicity of Alcohols and Phenols
18.7K
Like water, alcohols are weak acids and bases. This is attributed to the polarization of the O–H bond making the hydrogen partially positive. Moreover, the electron pairs on the oxygen atom of alcohol make it both basic and nucleophilic. Protonation of an alcohol converts hydroxide, a poor leaving group, into water—a good one. The two acid–base equilibria corresponding to ethanol are depicted below.
18.7K


