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IR and UV–Vis Spectroscopy of Aldehydes and Ketones01:29

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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...
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Oxidation of aldehydes and ketones results in the formation of carboxylic acids. Aldehydes, bearing hydrogen next to the carbonyl group, are easily oxidized compared to ketones. This is because an aldehydic proton can easily be abstracted during oxidation.
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NMR Spectroscopy and Mass Spectrometry of Aldehydes and Ketones01:15

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In aldehydes, the hydrogen atom connected to the carbonyl carbon helps distinguish aldehydes from other carbonyl compounds using ¹H NMR spectroscopy. The closeness of aldehydic hydrogen to the electrophilic carbonyl carbon highly deshields the hydrogen atom causing its signal to appear around 10 ppm in the ¹H NMR spectra. α hydrogens split the aldehydic proton signal, which helps identify the number of α hydrogens in the molecule. For instance, one α hydrogen creates a...
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Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
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Preparation of Aldehydes and Ketones from Alcohols, Alkenes, and Alkynes01:33

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Aldehydes and ketones are prepared from alcohols, alkenes, and alkynes via different reaction pathways. Alcohols are the most commonly used substrates for synthesizing aldehydes and ketones. The conversion of alcohol to aldehyde, which involves the oxidation process, depends on the class of the alcohol used and the strength of the oxidizing agent. For instance, primary alcohol will form an aldehyde when treated with a weak oxidizing agent; however, it gets over-oxidized to a carboxylic acid in...
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Calculated Absorption Cross Sections and Photolysis Rates of Hydroperoxyaldehydes.

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The Journal of Physical Chemistry. A
|December 19, 2025
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Summary
This summary is machine-generated.

Photolysis is a minor atmospheric loss path for hydroperoxymethyl thioformate (HPMTF) and other hydroperoxyaldehydes. Structure-activity relationships for predicting photolysis rates are unreliable due to unconsidered heteroatom effects.

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Area of Science:

  • Atmospheric chemistry
  • Computational chemistry
  • Environmental science

Background:

  • Hydroperoxyaldehydes are atmospheric oxidation products of volatile organic compounds.
  • Hydroperoxymethyl thioformate (HPMTF) is a significant hydroperoxyaldehyde formed from dimethyl sulfide.
  • Understanding HPMTF's atmospheric fate is vital for assessing its impact on sulfate production.

Purpose of the Study:

  • To calculate electronic absorption cross sections for HPMTF and related hydroperoxyaldehydes.
  • To estimate atmospheric photolysis rates for these compounds.
  • To evaluate the reliability of structure-activity relationships for predicting photolysis.

Main Methods:

  • Nuclear ensemble approach to compute electronic absorption cross sections.
  • Calculation of atmospheric photolysis rates using spectral data.
  • Implementation of HPMTF's absorption cross section in a global atmospheric model.

Main Results:

  • Photolysis is a minor loss pathway for HPMTF in the atmosphere.
  • Structure-activity relationship predictions for photolysis rates are unreliable, particularly when ignoring heteroatom effects.
  • Hydroperoxyaldehydes with α-heteroatoms (O or N) exhibit insignificant photolysis.

Conclusions:

  • Photolysis plays a limited role in the atmospheric removal of HPMTF.
  • Accurate photolysis rate calculations require considering heteroatom effects, not just functional groups.
  • The presence of α-heteroatoms significantly reduces the photolytic degradation of hydroperoxyaldehydes.