Phosphorus oxoacid

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Phosphorus oxoacid (or phosphorus acid) is a generic name for any acid whose molecule consists of atoms of phosphorus, oxygen, and hydrogen. [1] There is a potentially infinite number of such compounds. Some of them are unstable and have not been isolated, but the derived anions and organic groups are present in stable salts and esters. The most important ones—in biology, geology, industry, and chemical research—are the phosphoric acids, whose esters and salts are the phosphates.

Contents

In general, any hydrogen atom bonded to an oxygen atom is acidic, meaning that the –OH group can lose a proton H+
leaving a negatively charged –O
group and thus turning the acid into a phosphorus oxoanion. Each additional proton lost has an associated acid dissociation constant Ka1, Ka2 Ka3, ..., often expressed by its cologarithm (pKa1, pKa2, pKa3, ...). Hydrogen atoms bonded directly to phosphorus are generally not acidic.

Classification

The phosphorus oxoacids can be classified by the oxidation state(s) of the phosphorus atom(s), which may vary from +1 to +5. The oxygen atoms are usually in oxidation state -2, but may be in state -1 if the molecule includes peroxide groups.

Oxidation state +1

Hypophosphorous acid Hypophosphorous-acid-2D.png
Hypophosphorous acid

Oxidation state +3

Phosphorous acid Acido fosforoso.png
Phosphorous acid

Oxidation state +4

Hypophosphoric acid Hypophosphoric acid.svg
Hypophosphoric acid

Oxidation state +5

The most important members of this group are the phosphoric acids, where each phosphorus atom bonded to four oxygen atoms, one of them through a double bond, arranged as the corners of a tetrahedron. Two or more of these PO
4
tetrahedra may be connected by shared single-bonded oxygens, forming linear or branched chains, cycles, or more complex structures. The single-bonded oxygen atoms that are not shared are completed with acidic hydrogen atoms. Their generic formula is Hnx+2PnO3nx+1, where n is the number of phosphorus atoms and x is the number of fundamental cycles in the molecule's structure.

These acids, and their esters and salts ("phosphates") include some of the best-known and most important compounds of phosphorus.

Orthophosphoric acid, H
3PO
4. Phosphoric-acid-3D-vdW.png
Orthophosphoric acid, H
3
PO
4
.

The simplest member of this class is:

The smallest compounds of this class with two or more phosphorus atoms are called "oligophosphoric acids", and the larger ones, with linear –P–O– backbones, are "polyphosphoric acids"; with no definite separation between the two. Some of the most important members are:

The backbone may be branched, as in:

The PO
4
tetrahedra may be connected to form closed –P–O– chains, as in:

Metaphosphoric acid is a general term for phosphoric acids with a single cycle, (–P(O)(OH)–O–)n, whose elemental formula is HPO
3
.

Another compound that may be included in this class is

Mixed oxidation states

Some phosphorus oxoacids have two or more P atoms in different oxidation states. One example is

Phosphoric anhydride
P4O10 Phosphorus-pentoxide-3D-vdW.png
Phosphoric anhydride
P4O10
Some phosphoric acids Various Phosphoric Acids.PNG
Some phosphoric acids

See also

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An acid is a molecule or ion capable of either donating a proton (i.e. hydrogen ion, H+), known as a Brønsted–Lowry acid, or forming a covalent bond with an electron pair, known as a Lewis acid.

<span class="mw-page-title-main">Acid–base reaction</span> Chemical reaction

An acid–base reaction is a chemical reaction that occurs between an acid and a base. It can be used to determine pH via titration. Several theoretical frameworks provide alternative conceptions of the reaction mechanisms and their application in solving related problems; these are called the acid–base theories, for example, Brønsted–Lowry acid–base theory.

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

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

Hydroxide is a diatomic anion with chemical formula OH. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It functions as a base, a ligand, a nucleophile, and a catalyst. The hydroxide ion forms salts, some of which dissociate in aqueous solution, liberating solvated hydroxide ions. Sodium hydroxide is a multi-million-ton per annum commodity chemical. The corresponding electrically neutral compound HO is the hydroxyl radical. The corresponding covalently bound group –OH of atoms is the hydroxy group. Both the hydroxide ion and hydroxy group are nucleophiles and can act as catalysts in organic chemistry.

<span class="mw-page-title-main">Phosphorus</span> Chemical element, symbol P and atomic number 15

Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Earth. It has a concentration in the Earth's crust of about one gram per kilogram. In minerals, phosphorus generally occurs as phosphate.

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

In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthophosphoric acid, AKA phosphoric acid H3PO4.

An oxyanion, or oxoanion, is an ion with the generic formula A
x
Oz
y
. Oxyanions are formed by a large majority of the chemical elements. The formulae of simple oxyanions are determined by the octet rule. The corresponding oxyacid of an oxyanion is the compound H
z
A
x
O
y
. The structures of condensed oxyanions can be rationalized in terms of AOn polyhedral units with sharing of corners or edges between polyhedra. The oxyanions adenosine monophosphate (AMP), adenosine diphosphate (ADP) and adenosine triphosphate (ATP) are important in biology.

<span class="mw-page-title-main">Phosphodiester bond</span> –O– linkage between phosphoric acid and two other compounds

In chemistry, a phosphodiester bond occurs when exactly two of the hydroxyl groups in phosphoric acid react with hydroxyl groups on other molecules to form two ester bonds. The "bond" involves this linkage C−O−PO−2O−C. Discussion of phosphodiesters is dominated by their prevalence in DNA and RNA, but phosphodiesters occur in other biomolecules, e.g. acyl carrier proteins.

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

Pyrophosphoric acid, also known as diphosphoric acid, is the inorganic compound with the formula H4P2O7 or, more descriptively, [(HO)2P(O)]2O. Colorless and odorless, it is soluble in water, diethyl ether, and ethyl alcohol. The anhydrous acid crystallizes in two polymorphs, which melt at 54.3 and 71.5 °C. The compound is a component of polyphosphoric acid, an important source of phosphoric acid. Anions, salts, and esters of pyrophosphoric acid are called pyrophosphates.

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

Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts readily with water to release hydrogen chloride.

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

Phosphorous acid (or phosphonic acid) is the compound described by the formula H3PO3. This acid is diprotic (readily ionizes two protons), not triprotic as might be suggested by this formula. Phosphorous acid is an intermediate in the preparation of other phosphorus compounds. Organic derivatives of phosphorous acid, compounds with the formula RPO3H2, are called phosphonic acids.

<span class="mw-page-title-main">Phosphoric acids and phosphates</span>

A phosphoric acid, in the general sense, is a phosphorus oxoacid in which each phosphorus (P) atom is in the oxidation state +5, and is bonded to four oxygen (O) atoms, one of them through a double bond, arranged as the corners of a tetrahedron. Two or more of these PO
4
tetrahedra may be connected by shared single-bonded oxygens, forming linear or branched chains, cycles, or more complex structures. The single-bonded oxygen atoms that are not shared are completed with acidic hydrogen atoms. The general formula of a phosphoric acid is H
n+2−2x
P
n
O
3n+1−x
, where n is the number of phosphorus atoms and x is the number of fundamental cycles in the molecule's structure, between 0 and (n+2)/2.

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

Phosphorus pentoxide is a chemical compound with molecular formula P4O10 (with its common name derived from its empirical formula, P2O5). This white crystalline solid is the anhydride of phosphoric acid. It is a powerful desiccant and dehydrating agent.

The arsenate is an ion with the chemical formula AsO3−4. Bonding in arsenate consists of a central arsenic atom, with oxidation state +5, double bonded to one oxygen atom and single bonded to a further three oxygen atoms. The four oxygen atoms orient around the arsenic atom in a tetrahedral geometry. Resonance disperses the ion's −3 charge across all four oxygen atoms.

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

Phosphoryl chloride is a colourless liquid with the formula POCl3. It hydrolyses in moist air releasing phosphoric acid and fumes of hydrogen chloride. It is manufactured industrially on a large scale from phosphorus trichloride and oxygen or phosphorus pentoxide. It is mainly used to make phosphate esters such as tricresyl phosphate.

An oxyacid, oxoacid, or ternary acid is an acid that contains oxygen. Specifically, it is a compound that contains hydrogen, oxygen, and at least one other element, with at least one hydrogen atom bonded to oxygen that can dissociate to produce the H+ cation and the anion of the acid.

<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.

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

Hydrogen phosphate or monohydrogen phosphate(systematic name) is the inorganic ion with the formula [HPO4]2-. Its formula can also be written as [PO3(OH)]2-. Together with dihydrogen phosphate, hydrogenphosphate occurs widely in natural systems. Their salts are used in fertilizers and in cooking. Most hydrogenphosphate salts are colorless, water soluble, and nontoxic.

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

Hypophosphoric acid is a mineral acid with the formula H4P2O6, with phosphorus in a formal oxidation state of +4. In the solid state it is present as the dihydrate, H4P2O6·2H2O. In hypophosphoric acid the phosphorus atoms are identical and joined directly with a P−P bond. Isohypophosphoric acid is a structural isomer of hypophosphoric acid in which one phosphorus has a hydrogen directedly bonded to it and that phosphorus atom is linked to the other one by an oxygen bridge to give a phosphorous acid/phosphoric acid mixed anhydride. The two phosphorus atoms are in the +3 and +5 oxidation states, respectively.

<span class="mw-page-title-main">Peroxymonophosphoric acid</span> Oxyacid of phosphorus

Peroxymonophosphoric acid is an oxyacid of phosphorus. It is a colorless viscous oil. Its salts are called peroxymonophosphates. Another peroxyphosphoric acid is peroxydiphosphoric acid, H4P2O8.

References

  1. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.

Further reading