Oxidizing agent

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The international pictogram for oxidizing chemicals. GHS-pictogram-rondflam.svg
The international pictogram for oxidizing chemicals.
Dangerous goods label for oxidizing agents DOT hazmat class 5.1.svg
Dangerous goods label for oxidizing agents

An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor ) is a substance in a redox chemical reaction that gains or "accepts"/"receives" an electron from a reducing agent (called the reductant, reducer, or electron donor ). In other words, an oxidizer is any substance that oxidizes another substance. The oxidation state, which describes the degree of loss of electrons, of the oxidizer decreases while that of the reductant increases; this is expressed by saying that oxidizers "undergo reduction" and "are reduced" while reducers "undergo oxidation" and "are oxidized". Common oxidizing agents are oxygen, hydrogen peroxide, and the halogens.

Contents

In one sense, an oxidizing agent is a chemical species that undergoes a chemical reaction in which it gains one or more electrons. 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

Example of a reduction-oxidation reaction between sodium and chlorine, with the OIL RIG mnemonic Redox example.svg
Example of a reduction–oxidation reaction between sodium and chlorine, with the OIL RIG mnemonic
Tetracyanoquinodimethane is an organic electron-acceptor. Tetracyanoquinodimethane Formula V.1.svg
Tetracyanoquinodimethane is an organic electron-acceptor.

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
5
H
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. [2]

Extensive tabulations of ranking the electron accepting properties of various reagents (redox potentials) are available, see Standard electrode potential (data page).

Atom-transfer reagents

In more common usage, an oxidizing agent transfers oxygen atoms to a substrate. In this context, the oxidizing agent can be called an oxygenation reagent or oxygen-atom transfer (OAT) agent. [3] 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
,ie permanganate to manganate.

Common oxidizing agents

Dangerous materials definition

The dangerous goods definition of an oxidizing agent is a substance that can cause or contribute to the combustion of other material. [4] By this definition some materials that are classified as oxidizing agents by analytical chemists are not classified as oxidizing agents in a dangerous materials sense. An example is potassium dichromate, which does not pass the dangerous goods test of an oxidizing 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(a)1 and Class 5; Division 5.1(a)2. Division 5.1 "means a material that may, generally by yielding oxygen, cause or enhance the combustion of other materials." Division 5.(a)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(a)2 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." [5]

Common oxidizing agents and their products

AgentProduct(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 sulfur dioxide S sulfur
(Claus process, ultramarine production, more commonly reducing agent)
Hexavalent chromium
CrO3 chromium trioxide
CrO2−
4
chromate
Cr
2
O2−
7
dichromate
Cr3+, H2O
MnO
4
permanganate
MnO2−
4
manganate
Mn2+ (acidic) or
MnO2 (basic)
SbF5 antimony pentafluoride SbF6- hexafluoroantimonate or SbF3 antimony trifluoride
PtF6 platinum hexafluoride PtF6- hexafluoroplatinate
RuO
4
ruthenium tetroxide
OsO
4
osmium tetroxide
in organic lab scale synthesis
H2O2, other peroxides Various, including oxides and H2O
Tl(III) thallic compoundsTl(I) thallous compounds, in organic lab scale synthesis

See also

Related Research Articles

<span class="mw-page-title-main">Chemical reaction</span> Process that results in the interconversion of chemical species

A chemical reaction is a process that leads to the chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the positions of electrons in the forming and breaking of chemical bonds between atoms, with no change to the nuclei, and can often be described by a chemical equation. Nuclear chemistry is a sub-discipline of chemistry that involves the chemical reactions of unstable and radioactive elements where both electronic and nuclear changes can occur.

<span class="mw-page-title-main">Redox</span> Chemical reaction in which oxidation states of atoms are changed

Redox is a type of chemical reaction in which the oxidation states of a substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a decrease in the oxidation state.

In chemistry, a reducing agent is a chemical species that "donates" an electron to an electron recipient. Examples of substances that are common reducing agents include the alkali metals, formic acid, oxalic acid, and sulfite compounds.

<span class="mw-page-title-main">Manganese dioxide</span> Chemical compound

Manganese dioxide is the inorganic compound with the formula MnO
2
. This blackish or brown solid occurs naturally as the mineral pyrolusite, which is the main ore of manganese and a component of manganese nodules. The principal use for MnO
2
is for dry-cell batteries, such as the alkaline battery and the zinc–carbon battery. MnO
2
is also used as a pigment and as a precursor to other manganese compounds, such as KMnO
4
. It is used as a reagent in organic synthesis, for example, for the oxidation of allylic alcohols. MnO
2
has an α-polymorph that can incorporate a variety of atoms in the "tunnels" or "channels" between the manganese oxide octahedra. There is considerable interest in α-MnO
2
as a possible cathode for lithium-ion batteries.

<span class="mw-page-title-main">Potassium permanganate</span> Chemical compound

Potassium permanganate is an inorganic compound with the chemical formula KMnO4. It is a purplish-black crystalline salt, that dissolves in water as K+ and MnO
4
, an intensely pink to purple solution.

In environmental chemistry, the chemical oxygen demand (COD) is an indicative measure of the amount of oxygen that can be consumed by reactions in a measured solution. It is commonly expressed in mass of oxygen consumed over volume of solution which in SI units is milligrams per litre (mg/L). A COD test can be used to easily quantify the amount of organics in water. The most common application of COD is in quantifying the amount of oxidizable pollutants found in surface water or wastewater. COD is useful in terms of water quality by providing a metric to determine the effect an effluent will have on the receiving body, much like biochemical oxygen demand (BOD).

<span class="mw-page-title-main">Chromate and dichromate</span> Chromium(VI) anions

Chromate salts contain the chromate anion, CrO2−
4
. Dichromate salts contain the dichromate anion, Cr
2
O2−
7
. They are oxyanions of chromium in the +6 oxidation state and are moderately strong oxidizing agents. In an aqueous solution, chromate and dichromate ions can be interconvertible.

<span class="mw-page-title-main">Potassium dichromate</span> Chemical compound

Potassium dichromate, K2Cr2O7, is a common inorganic chemical reagent, most commonly used as an oxidizing agent in various laboratory and industrial applications. As with all hexavalent chromium compounds, it is acutely and chronically harmful to health. It is a crystalline ionic solid with a very bright, red-orange color. The salt is popular in laboratories because it is not deliquescent, in contrast to the more industrially relevant salt sodium dichromate.

<span class="mw-page-title-main">Permanganate</span> Chemical compound

A permanganate is a chemical compound with the manganate(VII) ion, MnO
4
, the conjugate base of permanganic acid. Because the manganese atom has a +7 oxidation state, the permanganate(VII) ion is a strong oxidising agent. The ion is a transition metal ion with a tetrahedral structure. Permanganate solutions are purple in colour and are stable in neutral or slightly alkaline media. The exact chemical reaction depends on the carbon-containing reactants present and the oxidant used. For example, trichloroethane (C2H3Cl3) is oxidised by permanganate ions to form carbon dioxide (CO2), manganese dioxide (MnO2), hydrogen ions (H+), and chloride ions (Cl).

<span class="mw-page-title-main">Organic redox reaction</span> Redox reaction that takes place with organic compounds

Organic reductions or organic oxidations or organic redox reactions are redox reactions that take place with organic compounds. In organic chemistry oxidations and reductions are different from ordinary redox reactions, because many reactions carry the name but do not actually involve electron transfer. Instead the relevant criterion for organic oxidation is gain of oxygen and/or loss of hydrogen.

<span class="mw-page-title-main">Potassium manganate</span> Chemical compound

Potassium manganate is the inorganic compound with the formula K2MnO4. This green-colored salt is an intermediate in the industrial synthesis of potassium permanganate, a common chemical. Occasionally, potassium manganate and potassium permanganate are confused, but these compounds's properties are distinct.

Potassium hypomanganate is the inorganic compound with the formula K3MnO4. Also known as potassium manganate(V), this bright blue solid is a rare example of a salt with the hypomanganate or manganate(V) anion, where the manganese atom is in the +5 oxidation state. It is an intermediate in the production of potassium permanganate and the industrially most important Mn(V) compound.

<span class="mw-page-title-main">Chromium compounds</span> Chemical compounds containing chromium

Chromium is a member of group 6, of the transition metals. The +3 and +6 states occur most commonly within chromium compounds, followed by +2; charges of +1, +4 and +5 for chromium are rare, but do nevertheless occasionally exist.

A pyrotechnic composition is a substance or mixture of substances designed to produce an effect by heat, light, sound, gas/smoke or a combination of these, as a result of non-detonative self-sustaining exothermic chemical reactions. Pyrotechnic substances do not rely on oxygen from external sources to sustain the reaction.

The mercury beating heart is an electrochemical redox reaction between the elements mercury, iron and chromium. The reaction causes a blob of mercury in water to oscillate.

<span class="mw-page-title-main">Oxygen compounds</span>

The oxidation state of oxygen is −2 in almost all known compounds of oxygen. The oxidation state −1 is found in a few compounds such as peroxides. Compounds containing oxygen in other oxidation states are very uncommon: −12 (superoxides), −13 (ozonides), 0, +12 (dioxygenyl), +1, and +2.

Permanganometry is one of the techniques used in chemical quantitative analysis. It is a redox titration that involves the use of permanganates to measure the amount of analyte present in unknown chemical samples. It involves two steps, namely the titration of the analyte with potassium permanganate solution and then the standardization of potassium permanganate solution with standard sodium oxalate solution. The titration involves volumetric manipulations to prepare the analyte solutions.

The Pinnick oxidation is an organic reaction by which aldehydes can be oxidized into their corresponding carboxylic acids using sodium chlorite (NaClO2) under mild acidic conditions. It was originally developed by Lindgren and Nilsson. The typical reaction conditions used today were developed by G. A. Kraus. H.W. Pinnick later demonstrated that these conditions could be applied to oxidize α,β-unsaturated aldehydes. There exist many different reactions to oxidize aldehydes, but only a few are amenable to a broad range of functional groups. The Pinnick oxidation has proven to be both tolerant of sensitive functionalities and capable of reacting with sterically hindered groups. This reaction is especially useful for oxidizing α,β-unsaturated aldehydes, and another one of its advantages is its relatively low cost.

In situ chemical oxidation (ISCO), a form of advanced oxidation process, is an environmental remediation technique used for soil and/or groundwater remediation to lower the concentrations of targeted environmental contaminants to acceptable levels. ISCO is accomplished by introducing strong chemical oxidizers into the contaminated medium to destroy chemical contaminants in place. It can be used to remediate a variety of organic compounds, including some that are resistant to natural degradation. The in situ in ISCO is just Latin for "in place", signifying that ISCO is a chemical oxidation reaction that occurs at the site of the contamination.

In chemistry, molecular oxohalides (oxyhalides) are a group of chemical compounds in which both oxygen and halogen atoms are attached to another chemical element A in a single molecule. They have the general formula AOmXn, where X is a halogen. Known oxohalides have fluorine (F), chlorine (Cl), bromine (Br), and/or iodine (I) in their molecules. The element A may be a main group element, a transition element, a rare earth element or an actinide. The term oxohalide, or oxyhalide, may also refer to minerals and other crystalline substances with the same overall chemical formula, but having an ionic structure.

References

  1. "Metals". Bitesize. BBC. Archived from the original on November 3, 2022.
  2. 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.
  3. Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, ISBN   978-0-471-72091-1
  4. Australian Dangerous Goods Code, 6th Edition
  5. 49 CFR 172.127 General Requirements for Shipments and Packagings; Subpart D