Oxidizing agent
In chemistry, an oxidizing agent (oxidant, oxidizer) is a substance that has the ability to oxidize other substances (cause them to lose electrons). Common oxidizing agents are oxygen, hydrogen peroxide and the halogens.
In one sense, an oxidizing agent is a chemical species that undergoes a chemical reaction that removes one or more electrons from another atom. In that sense, it is one component in an oxidation–reduction (redox) reaction. In the second sense, an oxidizing agent is a chemical species that transfers electronegative atoms, usually oxygen, to a substrate. Combustion, many explosives, and organic redox reactions involve atom-transfer reactions.
Electron acceptors
Electron acceptors participate in electron-transfer reactions. In this context, the oxidizing agent is called an electron acceptor and the reducing agent is called an electron donor. A classic oxidizing agent is the ferrocenium ion Fe(C
5H
5)+
2, which accepts an electron to form Fe(C5H5)2. One of the strongest acceptors commercially available is "Magic blue", the radical cation derived from N(C6H4-4-Br)3.[1]
Tetracyanoquinodimethane is an organic electron-acceptor.
Extensive tabulations of ranking the electron accepting properties of various reagents (redox potentials) are available, see Standard electrode potential (data page).
Mechanism
Of great interest to chemists are the details of the electron transfer event, which can be described as inner sphere or outer sphere.
Atom-transfer reagents
In more common usage, an oxidising agent transfers oxygen atoms to a substrate. In this context, the oxidising agent can be called an oxygenation reagent or oxygen-atom transfer (OAT) agent.[2] Examples include MnO−
4 (permanganate), CrO2−
4 (chromate), OsO4 (osmium tetroxide), and especially ClO−
4 (perchlorate). Notice that these species are all oxides.
In some cases, these oxides can also serve as electron acceptors, as illustrated by the conversion of MnO−
4 to MnO2−
4, manganate.
Common oxidizing agents (O-atom transfer agents)
- Oxygen (O2)
- Ozone (O3)
- Hydrogen peroxide (H2O2) and other inorganic peroxides, Fenton's reagent
- Fluorine (F2), chlorine (Cl2), and other halogens
- Nitric acid (HNO3) and nitrate compounds
- Sulfuric acid (H2SO4)
- Peroxydisulfuric acid (H2S2O8)
- Peroxymonosulfuric acid (H2SO5)
- Chlorite, chlorate, perchlorate, and other analogous halogen compounds
- Hypochlorite and other hypohalite compounds, including household bleach (NaClO)
- Hexavalent chromium compounds such as chromic and dichromic acids and chromium trioxide, pyridinium chlorochromate (PCC), and chromate/dichromate compounds
- Permanganate compounds such as potassium permanganate
- Sodium perborate
- Nitrous oxide (N2O)
- Potassium nitrate (KNO3), the oxidizer in black powder
- Sodium bismuthate
Dangerous materials definition
The dangerous materials definition of an oxidizing agent is a substance that can cause or contribute to the combustion of other material.[3] By this definition some materials that are classified as oxidising agents by analytical chemists are not classified as oxidising agents in a dangerous materials sense. An example is potassium dichromate, which does not pass the dangerous goods test of an oxidising agent.
The U.S. Department of Transportation defines oxidizing agents specifically. There are two definitions for oxidizing agents governed under DOT regulations. These two are Class 5; Division 5.1 and Class 5; Division 5.2. Division 5.1 "means a material that may, generally by yielding oxygen, cause or enhance the combustion of other materials." Division 5.1 of the DOT code applies to solid oxidizers "if, when tested in accordance with the UN Manual of Tests and Criteria (IBR, see § 171.7 of this subchapter), its mean burning time is less than or equal to the burning time of a 3:7 potassium bromate/cellulose mixture." 5.1 of the DOT code applies to liquid oxidizers "if, when tested in accordance with the UN Manual of Tests and Criteria, it spontaneously ignites or its mean time for a pressure rise from 690 kPa to 2070 kPa gauge is less than the time of a 1:1 nitric acid (65 percent)/cellulose mixture."[4]
Common oxidizing agents and their products
| Agent | Product(s) |
|---|---|
| O2 oxygen | Various, including the oxides H2O and CO2 |
| O3 ozone | Various, including ketones, aldehydes, and H2O; see ozonolysis |
| F2 fluorine | F− |
| Cl2 chlorine | Cl− |
| Br2 bromine | Br− |
| I2 iodine | I−, I− 3 |
| ClO− hypochlorite | Cl−, H2O |
| ClO− 3 chlorate |
Cl−, H2O |
| HNO3 nitric acid | NO nitric oxide NO2 nitrogen dioxide |
| SO2 sulphur dioxide | S sulphur (Claus process, ultramarine production, more commonly reducing agent |
| Hexavalent chromium CrO3 chromium trioxide CrO2− 4 chromate Cr 2O2− 7 dichromate |
Cr3+, H2O |
| MnO− 4 permanganate MnO2− 4 manganate |
Mn2+ (acidic) or MnO2 (basic) |
| H2O2, other peroxides | Various, including oxides and H2O |
See also
References
- ↑ N. G. Connelly, W. E. Geiger (1996). "Chemical Redox Agents for Organometallic Chemistry". Chemical Reviews. 96 (2): 877–910. doi:10.1021/cr940053x. PMID 11848774.
- ↑ Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, ISBN 0-471-72091-7
- ↑ Australian Dangerous Goods Code, 6th Edition
- ↑ 49 CFR 172.127 General Requirements for Shipments and Packagings; Subpart D