Oxygen evolution is the process of generating molecular

oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...

(O₂) by a

chemical reaction A chemical reaction is a process that leads to the IUPAC nomenclature for organic transformations, chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the pos ...

, usually from water. Oxygen evolution from

water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a ...

is effected by oxygenic

photosynthesis Photosynthesis is a process used by plants and other organisms to convert light energy into chemical energy that, through cellular respiration, can later be released to fuel the organism's activities. Some of this chemical energy is stored i ...

electrolysis 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 n ...

of water, and thermal decomposition of various oxides. The biological process supports aerobic life. When relatively pure oxygen is required industrially, it is isolated by distillation of liquified air.

Oxygen evolution in nature

Photosynthetic oxygen evolution is the fundamental process by which oxygen is generated in earth's

biosphere The biosphere (from Greek βίος ''bíos'' "life" and σφαῖρα ''sphaira'' "sphere"), also known as the ecosphere (from Greek οἶκος ''oîkos'' "environment" and σφαῖρα), is the worldwide sum of all ecosystems. It can also be ...

. The reaction is part of the

light-dependent reaction Light-dependent reactions is jargon for certain photochemical reactions that are involved in photosynthesis, the main process by which plants acquire energy. There are two light dependent reactions, the first occurs at photosystem II (PSII) and ...

s of photosynthesis in

cyanobacteria Cyanobacteria (), also known as Cyanophyta, are a phylum of gram-negative bacteria that obtain energy via photosynthesis. The name ''cyanobacteria'' refers to their color (), which similarly forms the basis of cyanobacteria's common name, blu ...

and the

chloroplast A chloroplast () is a type of membrane-bound organelle known as a plastid that conducts photosynthesis mostly in plant and algal cells. The photosynthetic pigment chlorophyll captures the energy from sunlight, converts it, and stores it in ...

s of

green algae The green algae (singular: green alga) are a group consisting of the Prasinodermophyta and its unnamed sister which contains the Chlorophyta and Charophyta/Streptophyta. The land plants (Embryophytes) have emerged deep in the Charophyte alga as ...

and

plant Plants are predominantly photosynthetic eukaryotes of the kingdom Plantae. Historically, the plant kingdom encompassed all living things that were not animals, and included algae and fungi; however, all current definitions of Plantae exclud ...

s. It utilizes the energy of

light Light or visible light is electromagnetic radiation that can be perceived by the human eye. Visible light is usually defined as having wavelengths in the range of 400–700 nanometres (nm), corresponding to frequencies of 750–420 tera ...

to split a water molecule into its

proton A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...

s and

electron The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have no kn ...

s for photosynthesis. Free oxygen, generated as a by-product of this reaction, is released into the

atmosphere An atmosphere () is a layer of gas or layers of gases that envelop a planet, and is held in place by the gravity of the planetary body. A planet retains an atmosphere when the gravity is great and the temperature of the atmosphere is low. A s ...

. Water oxidation is catalyzed by a

manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...

-containing cofactor contained in

photosystem II Photosystem II (or water-plastoquinone oxidoreductase) is the first protein complex in the light-dependent reactions of oxygenic photosynthesis. It is located in the thylakoid membrane of plants, algae, and cyanobacteria. Within the photosystem ...

known as the

oxygen-evolving complex The oxygen-evolving complex (OEC), also known as the water-splitting complex, is the portion of photosystem II where photo-oxidation of water occurs during the light reactions of photosynthesis. The OEC is surrounded by four core protein subunits ...

(OEC) or water-splitting complex. Manganese is an important cofactor, and

calcium Calcium is a chemical element with the symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to ...

and

chloride The chloride ion is the anion (negatively charged ion) Cl−. It is formed when the element chlorine (a halogen) gains an electron or when a compound such as hydrogen chloride is dissolved in water or other polar solvents. Chloride salts ...

are also required for the reaction to occur. The stoichiometry this reaction follows: : 2H₂O ⟶ 4e⁻ + 4H⁺ + O₂ The protons are released into the

thylakoid lumen Thylakoids are membrane-bound compartments inside chloroplasts and cyanobacteria. They are the site of the light-dependent reactions of photosynthesis. Thylakoids consist of a thylakoid membrane surrounding a thylakoid lumen. Chloroplast thyl ...

, thus contributing to the generation of a proton gradient across the thylakoid membrane. This proton gradient is the driving force for ATP synthesis via

photophosphorylation In the process of photosynthesis, the phosphorylation of ADP to form ATP using the energy of sunlight is called photophosphorylation. Cyclic photophosphorylation occurs in both aerobic and anaerobic conditions, driven by the main primary source of ...

and coupling the absorption of light energy and oxidation of water to the creation of chemical energy during photosynthesis.

History of discovery

It was not until the end of the 18th century that

Joseph Priestley Joseph Priestley (; 24 March 1733 – 6 February 1804) was an English chemist, natural philosopher, separatist theologian, grammarian, multi-subject educator, and liberal political theorist. He published over 150 works, and conducted exp ...

discovered by accident the ability of plants to "restore" air that had been "injured" by the burning of a candle. He followed up on the experiment by showing that air "restored" by

vegetation Vegetation is an assemblage of plant species and the ground cover they provide. It is a general term, without specific reference to particular taxa, life forms, structure, spatial extent, or any other specific botanical or geographic character ...

was ''"not at all inconvenient to a

mouse A mouse ( : mice) is a small rodent. Characteristically, mice are known to have a pointed snout, small rounded ears, a body-length scaly tail, and a high breeding rate. The best known mouse species is the common house mouse (''Mus musculus' ...

."'' He was later awarded a medal for his discoveries that: ''"...no vegetable grows in vain... but cleanses and purifies our atmosphere."'' Priestley's experiments were followed up by

Jan Ingenhousz Jan (or John) Ingenhousz or Ingen-Housz FRS (8 December 1730 – 7 September 1799) was a Dutch-born British physiologist, biologist and chemist. He is best known for discovering photosynthesis by showing that light is essential to the process ...

, a Dutch physician, who showed that "restoration" of air only worked in the presence of light and green plant parts. Ingenhousz suggested in 1796 that CO₂ (

carbon dioxide Carbon dioxide (chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is transpar ...

) is split during photosynthesis to release oxygen, while the

carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...

combined with water to form

carbohydrate In organic chemistry, a carbohydrate () is a biomolecule consisting of carbon (C), hydrogen (H) and oxygen (O) atoms, usually with a hydrogen–oxygen atom ratio of 2:1 (as in water) and thus with the empirical formula (where ''m'' may or ma ...

s. While this hypothesis was attractive and reasonable and thus widely accepted for a long time, it was later proven incorrect. Graduate student C.B. Van Niel at

Stanford University Stanford University, officially Leland Stanford Junior University, is a private research university in Stanford, California. The campus occupies , among the largest in the United States, and enrolls over 17,000 students. Stanford is consider ...

found that

purple sulfur bacteria The purple sulfur bacteria (PSB) are part of a group of Pseudomonadota capable of photosynthesis, collectively referred to as purple bacteria. They are anaerobic or microaerophilic, and are often found in stratified water environments including ...

reduce carbon to carbohydrates, but accumulate

sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...

instead of releasing oxygen. He boldly proposed that, in analogy to the sulfur bacteria's forming elemental sulfur from H₂S (

hydrogen sulfide Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. The unde ...

), plants would form oxygen from H₂O (water). In 1937, this hypothesis was corroborated by the discovery that plants are capable of producing oxygen in the absence of CO₂. This discovery was made by Robin Hill, and subsequently the light-driven release of oxygen in the absence of CO₂ was called the ''Hill reaction''. Our current knowledge of the mechanism of oxygen evolution during photosynthesis was further established in experiments tracing

isotopes of oxygen There are three known stable isotopes of oxygen (8O): , , and . Radioactive isotopes ranging from to have also been characterized, all short-lived. The longest-lived radioisotope is with a half-life of , while the shortest-lived isotope is ...

from water to oxygen gas.

Water electrolysis

Together with

hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...

(H₂), oxygen is evolved by

electrolysis of water Electrolysis of water, also known as electrochemical water splitting, is the process of using electricity to decompose water into oxygen and hydrogen gas by electrolysis. Hydrogen gas released in this way can be used as hydrogen fuel, or remi ...

Electrons (e⁻) are transferred from the cathode to protons to form hydrogen gas. The

half reaction A half reaction (or half-cell 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. ...

, balanced with acid, is: :2 H⁺ + 2e⁻ → H₂ At the positively charged anode, an

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

reaction occurs, generating oxygen gas and releasing electrons to the anode to complete the circuit: :2 H₂O → O₂ + 4 H⁺ + 4e⁻ Combining either half reaction pair yields the same overall decomposition of water into oxygen and hydrogen: :Overall reaction: :2 H₂O → 2 H₂ + O₂

Chemical oxygen generation

Chemical oxygen generator A chemical oxygen generator is a device that releases oxygen via a chemical reaction. The oxygen source is usually an inorganic superoxide, chlorate, or perchlorate; ozonides are a promising group of oxygen sources. The generators are usually ig ...

s consist of chemical compounds that release O₂ upon some stimulation, usually heat. They are used in submarines and commercial aircraft, providing emergency oxygen. Oxygen is generated by high-temperature decomposition of sodium chlorate: :2 NaClO₃ → 2 NaCl + 3 O₂ Potassium permanganate also releases oxygen upon heating, but the yield is modest. :2 KMnO₄ → MnO₂ + K₂MnO₄ + O₂

References

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External links