Redox

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Sodium and fluorine bonding ionically to form sodium fluoride. Sodium loses its outer electron to give it a stable electron configuration, and this electron enters the fluorine atom exothermically. The oppositely charged ions are then attracted to each other. The sodium is oxidized; and the fluorine is reduced. NaF.gif
Sodium and fluorine bonding ionically to form sodium fluoride. Sodium loses its outer electron to give it a stable electron configuration, and this electron enters the fluorine atom exothermically. The oppositely charged ions are then attracted to each other. The sodium is oxidized; and the fluorine is reduced.
Demonstration of the reaction between a strong oxidizing and a reducing agent. When a few drops of glycerol (mild reducing agent) are added to powdered potassium permanganate (strong oxidizing agent), a violent redox reaction accompanied by self-ignition starts.
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

Redox (reduction–oxidation, /ˈrɛdɒks/ RED-oks, /ˈrdɒks/ REE-doks [2] ) is a type of chemical reaction in which the oxidation states of substrate change. [3]

Contents

There are two classes of redox reactions:

Terminology

"Redox" is a combination of the words "reduction" and "oxidation". The term "redox" was first used in 1928. [5] The processes of oxidation and reduction occur simultaneously and cannot occur independently. [4] In redox processes, the reductant transfers electrons to the oxidant. Thus, in the reaction, the reductant or reducing agent loses electrons and is oxidized, and the oxidant or oxidizing agent gains electrons and is reduced. The pair of an oxidizing and reducing agent that is involved in a particular reaction is called a redox pair. A redox couple is a reducing species and its corresponding oxidizing form, [6] e.g., Fe2+
/ Fe3+
.The oxidation alone and the reduction alone are each called a half-reaction because two half-reactions always occur together to form a whole reaction.

Oxidants

Oxidation originally implied reaction with oxygen to form an oxide. Later, the term was expanded to encompass oxygen-like substances that accomplished parallel chemical reactions. Ultimately, the meaning was generalized to include all processes involving the loss of electrons. Substances that have the ability to oxidize other substances (cause them to lose electrons) are said to be oxidative or oxidizing, and are known as oxidizing agents, oxidants, or oxidizers. The oxidant (oxidizing agent) removes electrons from another substance, and is thus itself reduced. And, because it "accepts" electrons, the oxidizing agent is also called an electron acceptor. Oxidants are usually chemical substances with elements in high oxidation states (e.g., H
2
O
2
, MnO
4
, CrO
3
, Cr
2
O2−
7
, OsO
4
), or else highly electronegative elements (O2, F2, Cl2, Br2) that can gain extra electrons by oxidizing another substance.[ citation needed ]

Oxidizers are oxidants but the term is mainly reserved for sources of oxygen, particularly in the context of explosions. Nitric acid is an oxidizer.

The international pictogram for oxidizing chemicals GHS-pictogram-rondflam.svg
The international pictogram for oxidizing chemicals

Oxygen is the quintessential oxidizer.

Reducers

Substances that have the ability to reduce other substances (cause them to gain electrons) are said to be reductive or reducing and are known as reducing agents, reductants, or reducers. The reductant (reducing agent) transfers electrons to another substance and is thus itself oxidized. And, because it donates electrons, the reducing agent is also called an electron donor. Electron donors can also form charge transfer complexes with electron acceptors. The word reduction originally referred to the loss in weight upon heating a metallic ore such as a metal oxide to extract the metal. In other words, ore was "reduced" to metal. Antoine Lavoisier demonstrated that this loss of weight was due to the loss of oxygen as a gas. Later, scientists realized that the metal atom gains electrons in this process. The meaning of reduction then became generalized to include all processes involving a gain of electrons. Reducing equivalent refers to chemical species which transfer the equivalent of one electron in redox reactions. The term is common in biochemistry. [7] A reducing equivalent can be an electron, a hydrogen atom, as a hydride ion. [8]

Reductants in chemistry are very diverse. Electropositive elemental metals, such as lithium, sodium, magnesium, iron, zinc, and aluminium, are good reducing agents. These metals donate or give away electrons relatively readily. They transfer electrons.

Hydride transfer reagents, such as NaBH4 and LiAlH4, reduce by atom transfer: they transfer the equivalent of hydride or H. These reagents widely used in [the reduction of carbonyl compounds to alcohols. [9] [10] A related method of reduction involves the use of hydrogen gas (H2) as sources of H atoms.

Electronation and deelectronation

The electrochemist John Bockris proposed the words electronation and deelectronation to describe reduction and oxidation processes, respectively, when they occur at electrodes. [11] These words are analogous to protonation and deprotonation. [12] They have not been widely adopted by chemists worldwide, although IUPAC has recognized the term electronation. [13]

Rates, mechanisms, and energies

Redox reactions can occur slowly, as in the formation of rust, or rapidly, as in the case of burning fuel. Electron transfer reactions are generally fast, occurring within the time of mixing.

The mechanisms of atom-transfer reactions are highly variable because many kinds of atoms can be transferred. Such reactions can also be quite complex, i.e. involve many steps. The mechanisms of electron-transfer reactions occur by two distinct pathways, inner sphere electron transfer and outer sphere electron transfer.

Analysis of bond energies and ionization energies in water allow calculation of the thermodynamic aspects of redox reactions.

Standard electrode potentials (reduction potentials)

Each half-reaction has a standard electrode potential (Eo
cell
), which is equal to the potential difference or voltage at equilibrium under standard conditions of an electrochemical cell in which the cathode reaction is the half-reaction considered, and the anode is a standard hydrogen electrode where hydrogen is oxidized:

12 H2 → H+ + e

The electrode potential of each half-reaction is also known as its reduction potentialEo
red
, or potential when the half-reaction takes place at a cathode. The reduction potential is a measure of the tendency of the oxidizing agent to be reduced. Its value is zero for H+ + e12 H2 by definition, positive for oxidizing agents stronger than H+ (e.g., +2.866 V for F2) and negative for oxidizing agents that are weaker than H+ (e.g., −0.763 V for Zn2+). [14]

For a redox reaction that takes place in a cell, the potential difference is:

Eo
cell
= Eo
cathode
Eo
anode

However, the potential of the reaction at the anode is sometimes expressed as an oxidation potential:

Eo
ox
 = Eo
red

The oxidation potential is a measure of the tendency of the reducing agent to be oxidized but does not represent the physical potential at an electrode. With this notation, the cell voltage equation is written with a plus sign

Eo
cell
= Eo
red(cathode)
+ Eo
ox(anode)

Examples of redox reactions

Illustration of a redox reaction Redox reaction.png
Illustration of a redox reaction

In the reaction between hydrogen and fluorine, hydrogen is being oxidized and fluorine is being reduced:

H2 + F2 → 2 HF

This reaction is spontaneous and releases 542 kJ per 2 g of hydrogen because the H-F bond is much stronger than the F-F bond. This reaction can be analyzed as two half-reactions. The oxidation reaction converts hydrogen to protons:

H2 → 2 H+ + 2 e

The reduction reaction converts fluorine to the fluoride anion:

F2 + 2 e → 2 F

The half reactions are combined so that the electrons cancel:

H
2
2 H+ + 2 e
F
2
+ 2 e
2 F

H2 + F22 H+ + 2 F

The protons and fluoride combine to form hydrogen fluoride in a non-redox reaction:

2 H+ + 2 F → 2 HF

The overall reaction is:

H2 + F2 → 2 HF

Metal displacement

A redox reaction is the force behind an electrochemical cell like the Galvanic cell pictured. The battery is made out of a zinc electrode in a ZnSO4 solution connected with a wire and a porous disk to a copper electrode in a CuSO4 solution. Galvanic cell with no cation flow.svg
A redox reaction is the force behind an electrochemical cell like the Galvanic cell pictured. The battery is made out of a zinc electrode in a ZnSO4 solution connected with a wire and a porous disk to a copper electrode in a CuSO4 solution.

In this type of reaction, a metal atom in a compound (or in a solution) is replaced by an atom of another metal. For example, copper is deposited when zinc metal is placed in a copper(II) sulfate solution:

Zn (s) + CuSO4 (aq) → ZnSO4 (aq) + Cu (s)

In the above reaction, zinc metal displaces the copper(II) ion from copper sulfate solution and thus liberates free copper metal. The reaction is spontaneous and releases 213 kJ per 65 g of zinc.

The ionic equation for this reaction is:

Zn + Cu2+ → Zn2+ + Cu

As two half-reactions, it is seen that the zinc is oxidized:

Zn → Zn2+ + 2 e

And the copper is reduced:

Cu2+ + 2 e → Cu

Other examples

2 NO3 + 10 e + 12 H+ → N2 + 6 H2O

Corrosion and rusting

Oxides, such as iron(III) oxide or rust, which consists of hydrated iron(III) oxides Fe2O3*nH2O and iron(III) oxide-hydroxide (FeO(OH), Fe(OH)3), form when oxygen combines with other elements Rust screw.jpg
Oxides, such as iron(III) oxide or rust, which consists of hydrated iron(III) oxides Fe2O3·nH2O and iron(III) oxide-hydroxide (FeO(OH), Fe(OH)3), form when oxygen combines with other elements
Iron rusting in pyrite cubes PyOx.JPG
Iron rusting in pyrite cubes
4 Fe + 3 O2 → 2 Fe2O3
Fe2+ → Fe3+ + e
H2O2 + 2 e → 2 OH
Here the overall equation involves adding the reduction equation to twice the oxidation equation, so that the electrons cancel:
2 Fe2+ + H2O2 + 2 H+ → 2 Fe3+ + 2 H2O

Disproportionation

A disproportionation reaction is one in which a single substance is both oxidized and reduced. For example, thiosulfate ion with sulfur in oxidation state +2 can react in the presence of acid to form elemental sulfur (oxidation state 0) and sulfur dioxide (oxidation state +4).

S2O2−3 + 2 H+ → S + SO2 + H2O

Thus one sulfur atom is reduced from +2 to 0, while the other is oxidized from +2 to +4. [15]

Redox reactions in industry

Cathodic protection is a technique used to control the corrosion of a metal surface by making it the cathode of an electrochemical cell. A simple method of protection connects protected metal to a more easily corroded "sacrificial anode" to act as the anode. The sacrificial metal instead of the protected metal, then, corrodes. A common application of cathodic protection is in galvanized steel, in which a sacrificial coating of zinc on steel parts protects them from rust.[ citation needed ]

Oxidation is used in a wide variety of industries such as in the production of cleaning products and oxidizing ammonia to produce nitric acid.

Redox reactions are the foundation of electrochemical cells, which can generate electrical energy or support electrosynthesis. Metal ores often contain metals in oxidized states such as oxides or sulfides, from which the pure metals are extracted by smelting at high temperature in the presence of a reducing agent. The process of electroplating uses redox reactions to coat objects with a thin layer of a material, as in chrome-plated automotive parts, silver plating cutlery, galvanization and gold-plated jewelry.[ citation needed ]

Redox reactions in biology

Ascorbic acid structure.svg
Dehydroascorbic acid 2.svg
Enzymatic browning is an example of a redox reaction that takes place in most fruits and vegetables. Extremely overripe banana.jpg
Enzymatic browning is an example of a redox reaction that takes place in most fruits and vegetables.

Many important biological processes involve redox reactions. Before some of these processes can begin iron must be assimilated from the environment. [16]

Cellular respiration, for instance, is the oxidation of glucose (C6H12O6) to CO2 and the reduction of oxygen to water. The summary equation for cell respiration is:

C6H12O6 + 6 O2 → 6 CO2 + 6 H2O

The process of cell respiration also depends heavily on the reduction of NAD+ to NADH and the reverse reaction (the oxidation of NADH to NAD+). Photosynthesis and cellular respiration are complementary, but photosynthesis is not the reverse of the redox reaction in cell respiration:

6 CO2 + 6 H2O + light energy → C6H12O6 + 6 O2

Biological energy is frequently stored and released by means of redox reactions. Photosynthesis involves the reduction of carbon dioxide into sugars and the oxidation of water into molecular oxygen. The reverse reaction, respiration, oxidizes sugars to produce carbon dioxide and water. As intermediate steps, the reduced carbon compounds are used to reduce nicotinamide adenine dinucleotide (NAD+) to NADH, which then contributes to the creation of a proton gradient, which drives the synthesis of adenosine triphosphate (ATP) and is maintained by the reduction of oxygen. In animal cells, mitochondria perform similar functions. See the Membrane potential article.

Free radical reactions are redox reactions that occur as a part of homeostasis and killing microorganisms, where an electron detaches from a molecule and then reattaches almost instantaneously. Free radicals are a part of redox molecules and can become harmful to the human body if they do not reattach to the redox molecule or an antioxidant. Unsatisfied free radicals can spur the mutation of cells they encounter and are, thus, causes of cancer.

The term redox state is often used to describe the balance of GSH/GSSG, NAD+/NADH and NADP+/NADPH in a biological system such as a cell or organ. The redox state is reflected in the balance of several sets of metabolites (e.g., lactate and pyruvate, beta-hydroxybutyrate, and acetoacetate), whose interconversion is dependent on these ratios. An abnormal redox state can develop in a variety of deleterious situations, such as hypoxia, shock, and sepsis. Redox mechanism also control some cellular processes. Redox proteins and their genes must be co-located for redox regulation according to the CoRR hypothesis for the function of DNA in mitochondria and chloroplasts.

Redox cycling

Wide varieties of aromatic compounds are enzymatically reduced to form free radicals that contain one more electron than their parent compounds. In general, the electron donor is any of a wide variety of flavoenzymes and their coenzymes. Once formed, these anion free radicals reduce molecular oxygen to superoxide and regenerate the unchanged parent compound. The net reaction is the oxidation of the flavoenzyme's coenzymes and the reduction of molecular oxygen to form superoxide. This catalytic behavior has been described as a futile cycle or redox cycling.

Redox reactions in geology

Blast furnaces of Trinec Iron and Steel Works, Czech Republic VysokePece1.jpg
Blast furnaces of Třinec Iron and Steel Works, Czech Republic

Minerals are generally oxidized derivatives of metals. Iron is mined as its magnetite (Fe3O4). Titanium is mined as its dioxide, usually in the form of rutile (TiO2). To obtain the corresponding metals, these oxides must be reduced, which is often achieved by heating these oxides with carbon or carbon monoxide as reducing agents. Blast furnaces are the reactors where iron oxides and coke (a form of carbon) are combined to produce molten iron.The main chemical reaction producing the molten iron is: [17]

Fe2O3 + 3 CO → 2 Fe + 3 CO2

Redox reactions in soils

Electron transfer reactions are central to myriad processes and properties in soils, and electron "activity", quantified as Eh (platinum electrode potential (voltage) relative to the standard hydrogen electrode) or pe (analogous to pH as -log electron activity), is a master variable, along with pH, that controls and is governed by chemical reactions and biological processes. Early theoretical research with applications to flooded soils and paddy rice production was seminal for subsequent work on thermodynamic aspects of redox and plant root growth in soils. [18] Later work built on this foundation, and expanded it for understanding redox reactions related to heavy metal oxidation state changes, pedogenesis and morphology, organic compound degradation and formation, free radical chemistry, wetland delineation, soil remediation, and various methodological approaches for characterizing the redox status of soils. [19] [20]


Mnemonics

The key terms involved in redox can be confusing. [21] [22] For example, a reagent that is oxidized loses electrons; however, that reagent is referred to as the reducing agent. Likewise, a reagent that is reduced gains electrons and is referred to as the oxidizing agent. [23] These mnemonics are commonly used by students to help memorise the terminology: [24]

See also

Related Research Articles

<span class="mw-page-title-main">Electrochemistry</span> Branch of chemistry

Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outcome of a particular chemical change, or vice versa. These reactions involve electrons moving via an electronically-conducting phase between electrodes separated by an ionically conducting and electronically insulating electrolyte.

<span class="mw-page-title-main">Electrochemical cell</span> Electro-chemical device

An electrochemical cell is a device capable of either generating electrical energy from chemical reactions or using electrical energy to cause chemical reactions. The electrochemical cells which generate an electric current are called voltaic or galvanic cells and those that generate chemical reactions, via electrolysis for example, are called electrolytic cells. A common example of a galvanic cell is a standard 1.5 volt cell meant for consumer use. A battery consists of one or more cells, connected in parallel, series or series-and-parallel pattern.

Electrolysis Technique in chemistry and manufacturing

In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from naturally occurring sources such as ores using an electrolytic cell. The voltage that is needed for electrolysis to occur is called the decomposition potential. The word "lysis" means to separate or break, so in terms, electrolysis would mean "breakdown via electricity".

A half reaction is either the oxidation or reduction reaction component of a redox reaction. A half reaction is obtained by considering the change in oxidation states of individual substances involved in the redox reaction. Often, the concept of half reactions is used to describe what occurs in an electrochemical cell, such as a Galvanic cell battery. Half reactions can be written to describe both the metal undergoing oxidation and the metal undergoing reduction.

In electrochemistry, the Nernst equation is a chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction from the standard electrode potential, absolute temperature, the number of electrons involved in the oxydo-reduction reaction, and activities of the chemical species undergoing reduction and oxidation respectively. It was named after Walther Nernst, a German physical chemist who formulated the equation.

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

Oxidizing agent Chemical compound used to oxidize another substance in a chemical reaction

An oxidizing agent is a substance in a redox chemical reaction that gains or "accepts"/"receives" an electron from a reducing agent. 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.

<span class="mw-page-title-main">Galvanic cell</span> Electrochemical device

A galvanic cell or voltaic cell, named after the scientists Luigi Galvani and Alessandro Volta, respectively, is an electrochemical cell in which an electric current is generated from spontaneous Oxidation-Reduction reactions. A common apparatus generally consists of two different metals, each immersed in separate beakers containing their respective metal ions in solution that are connected by a salt bridge or separated by a porous membrane.

Manganese dioxide 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
is 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.

Electrolytic cell Cell that uses electrical energy to drive a non-spontaneous redox reaction

An electrolytic cell is an electrochemical cell that utilizes an external source of electrical energy to drive a chemical reaction that would not otherwise occur. This is in contrast to a galvanic cell, which itself is a source of electrical energy and the foundation of a battery. The net reaction taking place in a galvanic cell is a spontaneous reaction, i.e, the Gibbs free energy remains negative, while the net reaction taking place in an electrolytic cell is the reverse of this spontaneous reaction, i.e, the Gibbs free energy is positive.

In electrochemistry, standard electrode potential, or , is a measure of the reducing power of any element or compound. The IUPAC "Gold Book" defines it as: "the value of the standard emf of a cell in which molecular hydrogen under standard pressure is oxidized to solvated protons at the left-hand electrode".

Alkaline fuel cell Type of fuel cell

The alkaline fuel cell (AFC), also known as the Bacon fuel cell after its British inventor, Francis Thomas Bacon, is one of the most developed fuel cell technologies. Alkaline fuel cells consume hydrogen and pure oxygen, to produce potable water, heat, and electricity. They are among the most efficient fuel cells, having the potential to reach 70%.

Organic redox reaction 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 in the electrochemical sense of the word. Instead the relevant criterion for organic oxidation is gain of oxygen and/or loss of hydrogen, respectively.

Redox potential is a measure of the tendency of a chemical species to acquire electrons from or lose electrons to an electrode and thereby be reduced or oxidised respectively. Redox potential is expressed in volts (V). Each species has its own intrinsic redox potential; for example, the more positive the reduction potential, the greater the species' affinity for electrons and tendency to be reduced.

Electrolysis of water Electricity-induced chemical reaction

Electrolysis of water, also known as electrochemical water splitting, is the process of using electricity to decompose water into oxygen and hydrogen gas by a process called electrolysis. Hydrogen gas released in this way can be used as hydrogen fuel, or remixed with the oxygen to create oxyhydrogen gas, which is used in welding and other applications.

In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly related to a cell's voltage efficiency. In an electrolytic cell the existence of overpotential implies that the cell requires more energy than thermodynamically expected to drive a reaction. In a galvanic cell the existence of overpotential means less energy is recovered than thermodynamics predicts. In each case the extra/missing energy is lost as heat. The quantity of overpotential is specific to each cell design and varies across cells and operational conditions, even for the same reaction. Overpotential is experimentally determined by measuring the potential at which a given current density is achieved.

Electrosynthesis in chemistry is the synthesis of chemical compounds in an electrochemical cell. Compared to ordinary redox reaction, electrosynthesis sometimes offers improved selectivity and yields. Electrosynthesis is actively studied as a science and also has industrial applications. Electrooxidation has potential for wastewater treatment as well.

An enzymatic biofuel cell is a specific type of fuel cell that uses enzymes as a catalyst to oxidize its fuel, rather than precious metals. Enzymatic biofuel cells, while currently confined to research facilities, are widely prized for the promise they hold in terms of their relatively inexpensive components and fuels, as well as a potential power source for bionic implants.

Biological photovoltaics, also called biophotovoltaics or BPV, is an energy-generating technology which uses oxygenic photoautotrophic organisms, or fractions thereof, to harvest light energy and produce electrical power. Biological photovoltaic devices are a type of biological electrochemical system, or microbial fuel cell, and are sometimes also called photo-microbial fuel cells or “living solar cells”. In a biological photovoltaic system, electrons generated by photolysis of water are transferred to an anode. A relatively high-potential reaction takes place at the cathode, and the resulting potential difference drives current through an external circuit to do useful work. It is hoped that using a living organism as the light harvesting material, will make biological photovoltaics a cost-effective alternative to synthetic light-energy-transduction technologies such as silicon-based photovoltaics.

A sugar battery is an emerging type of biobattery that is fueled by maltodextrin and facilitated by the enzymatic catalysts.

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Further reading