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Oxidation of Alcohols02:37

Oxidation of Alcohols

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In this lesson, the oxidation of alcohols is discussed in depth. The various reagents used for oxidation of primary and secondary alcohols are detailed, and their mechanism of action is provided.
The process of oxidation in a chemical reaction is observed in any of the three forms:
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Oxidations of Aldehydes and Ketones to Carboxylic Acids01:15

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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.
Aldehydes readily undergo oxidation in strong oxidizing agents such as potassium permanganate and chromic acid. The oxidation can also be carried out using mild oxidizing agents such as silver oxide. In fact, aldehydes can be easily oxidized...
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Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation01:22

Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation

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Baeyer–Villiger oxidation converts aldehydes to carboxylic acids and ketones to esters. The reaction uses peroxy acids or peracids and is often catalyzed by acid. The reaction is named after its pioneers, Adolf von Baeyer and Victor Villiger. The reaction is achieved by a wide range of peracids such as m-chloroperoxybenzoic acid (mCPBA), perbenzoic acid (C6H5COOOH), peracetic acid (CH3COOOH), hydrogen peroxide (H2O2), and tert-butyl hydroperoxide (t-BuOOH).
The carbonyl center is activated by...
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Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids02:04

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

7.2K
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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Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide02:44

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Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
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Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate02:21

Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate

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Alkenes can be dihydroxylated using potassium permanganate.  The method encompasses the reaction of an alkene with a cold, dilute solution of potassium permanganate under basic conditions to form a cis-diol along with a brown precipitate of manganese dioxide.
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Advanced Glycerol Oxidation to Formic Acid in a Multiphasic Jet Loop Reactor Using Polyoxometalate Catalysts.

Ira Christina Wirth1, Daniel Niehaus1, Dorothea Voß1

  • 1Institute of Technical and Macromolecular Chemistry, Universität Hamburg, Bundesstrasse 45, Hamburg 20146, Germany.

ACS Sustainable Chemistry & Engineering
|January 16, 2026
PubMed
Summary

This study demonstrates a jet loop reactor (JLR) for efficient production of biogenic formic acid (FA) from glycerol. The JLR offers significant mass transfer advantages over stirred-tank reactors, enabling high yields at lower oxygen pressures.

Keywords:
formic acidglycerol oxidationjet loop reactorpolyoxometalate catalystprocess intensification

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Area of Science:

  • Chemical Engineering
  • Green Chemistry
  • Catalysis

Background:

  • Glycerol, a biodiesel byproduct, can be converted to valuable biogenic formic acid (FA).
  • Current industrial FA production (OxFA process) uses stirred-tank reactors (STRs) but is limited by low oxygen solubility, requiring high pressures (10-30 bar).
  • Efficient gas-liquid mass transfer is crucial for optimizing this oxidation reaction.

Purpose of the Study:

  • To implement and evaluate a jet loop reactor (JLR) for the multiphasic selective oxidation of glycerol to FA.
  • To compare the JLR's economic and mass transfer performance against conventional STRs.
  • To determine kinetic parameters and assess the reaction regime in the JLR.

Main Methods:

  • Utilized a homogeneous H5PV2Mo10O40 (HPA-2) polyoxometalate catalyst for glycerol oxidation.
  • Characterized the JLR to determine volumetric mass transfer coefficients (k l · a values).
  • Compared glycerol oxidation performance in JLR and STR under identical conditions.
  • Determined kinetic parameters (reaction orders, activation energy) and the Hatta number in the JLR.

Main Results:

  • The JLR exhibited efficient gas-liquid mass transfer with k l · a values from 51 to 173 h-1.
  • The JLR achieved high FA space-time-yields (STY) of up to 30.0 gFA LR -1 h-1 at only 5 bar oxygen pressure.
  • Kinetic analysis in the JLR showed reaction orders of 0.83 for glycerol and 0.54 for oxygen, with an activation energy of 78.3 kJ mol-1.
  • A Hatta number of 0.014 indicated the reaction operates in the kinetic regime at low pressures in the JLR.

Conclusions:

  • The jet loop reactor (JLR) offers significant mass transfer and economic advantages for biogenic formic acid production from glycerol compared to STRs.
  • The JLR facilitates efficient oxidation at lower oxygen pressures, demonstrating its high potential for green chemical synthesis.
  • The study highlights the JLR as a promising reactor concept for optimizing catalytic oxidation processes.