Hypophosphate
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Hypophosphoric acid is a
mineral acid A mineral acid (or inorganic acid) is an acid derived from one or more inorganic compounds, as opposed to organic acids which are acidic, organic compounds. All mineral acids form hydrogen ions and the conjugate base when dissolved in water. Ch ...
with the formula H4P2O6, with phosphorus in a formal
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical Electrical charge, charge of an atom if all of its Chemical bond, bonds to other atoms are fully Ionic bond, ionic. It describes the degree of oxidation (loss of electrons ...
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 In chemistry, a structural isomer (or constitutional isomer in the IUPAC nomenclature) of a compound is a compound that contains the same number and type of atoms, but with a different connectivity (i.e. arrangement of bonds) between them. The ...
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 Phosphorous acid (or phosphonic acid) is the Compound (chemistry), compound described by the chemical formula, formula . It is diprotic (readily ionizes two protons), not triprotic as might be suggested by its formula. Phosphorous acid is an in ...
/
phosphoric acid Phosphoric acid (orthophosphoric acid, monophosphoric acid or phosphoric(V) acid) is a colorless, odorless phosphorus-containing solid, and inorganic compound with the chemical formula . It is commonly encountered as an 85% aqueous solution, ...
mixed
anhydride An acid anhydride is a type of chemical compound derived by the removal of water molecules from an acid (chemistry), acid. In organic chemistry, organic acid anhydrides contain the functional group . Organic acid anhydrides often form when one ...
. The two phosphorus atoms are in the +3 and +5 oxidation states, respectively.


Preparation and reactions

Hypophosphoric acid can be prepared by the reaction of red phosphorus with
sodium chlorite Sodium chlorite (NaClO2) is a chemical compound used in the manufacturing of paper and as a disinfectant. Use The main application of sodium chlorite is the generation of chlorine dioxide for bleaching and stripping of textiles, pulp, and pa ...
at room temperature.Phosphorus: Chemistry, Biochemistry and Technology, Sixth Edition, 2013, D.E.C. Corbridge, CRC Pres, Taylor Francis Group, :2 P + 2 NaClO2 + 2 H2O → Na2H2P2O6 + 2 HCl A mixture of hypophosphoric acid,
phosphorous acid Phosphorous acid (or phosphonic acid) is the Compound (chemistry), compound described by the chemical formula, formula . It is diprotic (readily ionizes two protons), not triprotic as might be suggested by its formula. Phosphorous acid is an in ...
(H3PO3) and
phosphoric acid Phosphoric acid (orthophosphoric acid, monophosphoric acid or phosphoric(V) acid) is a colorless, odorless phosphorus-containing solid, and inorganic compound with the chemical formula . It is commonly encountered as an 85% aqueous solution, ...
(H3PO4) is produced when white phosphorus oxidises in air when partially immersed in water. The tetrasodium salt Na4P2O6·10H2O crystallises at pH 10 and the disodium salt, Na2H2PO6·6H2O at pH 5.2. The disodium salt can be passed through an ion exchange column to form the acid dihydrate, H4P2O6·2H2O. The anhydrous acid can be formed by vacuum dehydration over P4O10 or by the reaction of H2S on lead hypophosphate, Pb2P2O6. Hypophosphoric acid is tetraprotic with dissociation constants p''K''a1 = 2.2, p''K''a2 = 2.8, p''K''a3 = 7.3 and p''K''a4 = 10.0. On standing the anhydrous acid undergoes rearrangement and disproportionation to form a mixture of isohypophosphoric acid, HPO(OH)-O-PO2(OH); pyrophosphoric acid H2P2O7 and pyrophosphorous acid. Hypophosphoric acid is unstable in hot
hydrochloric acid Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...
, in 4 M HCl it hydrolyses to give H3PO3 + H3PO4.


Structure

Hypophosphorus acid contains oxonium ions and is best formulated 3O+sub>2 2P2O6sup>2−. The acid is isostructural with the diammonium salt which contains the OPO2PO2OHsup>2− anion with a P−P bond length of 219 pm. The HOPO2PO2OH2− anion in Na2H2P2O6·6H2O has a symmetric, staggered
ethane Ethane ( , ) is a naturally occurring Organic compound, organic chemical compound with chemical formula . At standard temperature and pressure, ethane is a colorless, odorless gas. Like many hydrocarbons, ethane is List of purification methods ...
-like structure with a P−P bond of length 219 pm. Each phosphorus atom has two P−O bonds with length 151 pm, and a P−OH bond length of 159 pm.


Hypophosphate salts

Many hypophosphate salts are known, for example, K4P2O6·8H2O, Ca2P2O6·2H2O, K3HP2O6·3H2O, K2H2P2O6·2H2O, KH3P2O6. On standing in air, hypophosphates tend to oxidise to
pyrophosphate In chemistry, pyrophosphates are phosphorus oxyanions that contain two phosphorus atoms in a linkage. A number of pyrophosphate salts exist, such as disodium pyrophosphate () and tetrasodium pyrophosphate (), among others. Often pyrophosphates a ...
s containing the ion where P has a formal oxidation state of +5. Hypophosphates are stable to alkali hydroxides. In fused
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive base (chemistry), ...
they convert rapidly to the orthophosphate containing .


Polyhypophosphates

Polyhypophosphates are known containing linear anions, for example Na5P3O8 containing )3O5− with a P−P−P chain and Na6P4O10·2H2O containing )4O6−, with a P−P−P−P chain. The cyclic anion , (hypohexametaphosphate) where each phosphorus atom has an oxidation state of +3 is formed when a suspension of red phosphorus in KOH is oxidised with bromine.


See also

* Dithionic acid, the sulfur equivalent.


References

{{Reflist Mineral acids Phosphorus oxoacids