Hypophosphorous acid (HPA), or phosphinic acid, is a

phosphorus 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 Ear ...

oxyacid 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 ...

and a powerful

reducing agent In chemistry, a reducing agent (also known as a reductant, reducer, or electron donor) is a chemical species that "donates" an electron to an (called the , , , or ). Examples of substances that are commonly reducing agents include the Earth meta ...

with

molecular formula In chemistry, a chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, ...

H₃PO₂. It is a colorless low-melting compound, which is soluble in water,

dioxane 1,4-Dioxane () is a heterocyclic organic compound, classified as an ether. It is a colorless liquid with a faint sweet odor similar to that of diethyl ether. The compound is often called simply dioxane because the other dioxane isomers ( 1,2- ...

and alcohols. The formula for this acid is generally written H₃PO₂, but a more descriptive presentation is HOP(O)H₂, which highlights its monoprotic character. Salts derived from this acid are called

hypophosphite Phosphinates or hypophosphites are a class of phosphorus compounds conceptually based on the structure of hypophosphorous acid. IUPAC prefers the term phosphinate in all cases, however in practice hypophosphite is usually used to describe inorganic ...

s. HOP(O)H₂ exists in equilibrium with the minor

tautomer Tautomers () are structural isomers (constitutional isomers) of chemical compounds that readily interconvert. The chemical reaction interconverting the two is called tautomerization. This conversion commonly results from the relocation of a hydr ...

HP(OH)₂. Sometimes the minor tautomer is called hypophosphorous acid and the major tautomer is called phosphinic acid.

Preparation and availability

Hypophosphorous acid was first prepared in 1816 by the French chemist

Pierre Louis Dulong Pierre Louis Dulong FRS FRSE (; ; 12 February 1785 – 19 July 1838) was a French physicist and chemist. He is remembered today largely for the law of Dulong and Petit, although he was much-lauded by his contemporaries for his studies into ...

(1785–1838). The acid is prepared industrially via a two step process: Firstly, elemental

white phosphorus Elemental phosphorus can exist in several allotropes, the most common of which are white and red solids. Solid violet and black allotropes are also known. Gaseous phosphorus exists as diphosphorus and atomic phosphorus. White phosphorus White ...

reacts with

alkali In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a basic, ionic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a ...

and

alkaline earth The alkaline earth metals are six chemical elements in group 2 of the periodic table. They are beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).. The elements have very similar properties: they are al ...

hydroxide 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. I ...

s to give an aqueous solution of hypophosphites: :P₄ + 4 OH⁻ + 4 H₂O → 4 + 2 H₂ Any

phosphite The general structure of a phosphite ester showing the lone pairs on the P In organic chemistry, a phosphite ester or organophosphite usually refers to an organophosphorous compound with the formula P(OR)3. They can be considered as esters of a ...

s produced in this step can be selectively precipitated out by treatment with

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 ...

salts. The purified material is then treated with a strong, non-oxidizing acid (often

sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...

) to give the free hypophosphorous acid: : + H⁺ → H₃PO₂ HPA is usually supplied as a 50% aqueous solution. Anhydrous acid cannot be obtained by simple evaporation of the water, as the acid readily oxidises to

phosphorous acid Phosphorous acid (or phosphonic acid (singular)) 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 th ...

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, w ...

and also

disproportionates In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. More generally, the term can ...

to phosphorous acid and

phosphine Phosphine (IUPAC name: phosphane) is a colorless, flammable, highly toxic compound with the chemical formula , classed as a pnictogen hydride. Pure phosphine is odorless, but technical grade samples have a highly unpleasant odor like rotting ...

. Pure anhydrous hypophosphorous acid can be formed by the continuous extraction of aqueous solutions with

diethyl ether Diethyl ether, or simply ether, is an organic compound in the ether class with the formula , sometimes abbreviated as (see Pseudoelement symbols). It is a colourless, highly volatile, sweet-smelling ("ethereal odour"), extremely flammable liq ...

Properties

When heated hypophosphorous acid undergoes

disproportionation In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. More generally, the term can b ...

to give

and

Reactions

Inorganic

Hypophosphorous acid can reduce chromium(III) oxide to chromium(II) oxide: :H₃PO₂ + 2 Cr₂O₃ → 4 CrO + H₃PO₄

Inorganic derivatives

Most metal-hypophosphite complexes are unstable, owing to the tendency of hypophosphites to reduce metal cations back into the bulk metal. Some examples have been characterised, including the important nickel salt i(H₂O)₆H₂PO₂)₂.

DEA List I chemical status

Because hypophosphorous acid can reduce elemental

iodine Iodine is a chemical element with the symbol I and atomic number 53. The heaviest of the stable halogens, it exists as a semi-lustrous, non-metallic solid at standard conditions that melts to form a deep violet liquid at , and boils to a vi ...

to form

hydroiodic acid Hydroiodic acid (or hydriodic acid) is an aqueous solution of hydrogen iodide (HI). It is a strong acid, one that is ionized completely in an aqueous solution. It is colorless. Concentrated solutions are usually 48% to 57% HI. Reactions Hyd ...

, which is a reagent effective for reducing

ephedrine Ephedrine is a central nervous system (CNS) stimulant that is often used to prevent low blood pressure during anesthesia. It has also been used for asthma, narcolepsy, and obesity but is not the preferred treatment. It is of unclear benefit in ...

pseudoephedrine Pseudoephedrine (PSE) is a sympathomimetic drug of the phenethylamine and amphetamine chemical classes. It may be used as a nasal/sinus decongestant, as a stimulant, or as a wakefulness-promoting agent in higher doses. It was first characteri ...

methamphetamine Methamphetamine (contracted from ) is a potent central nervous system (CNS) stimulant that is mainly used as a recreational drug and less commonly as a second-line treatment for attention deficit hyperactivity disorder and obesity. Methamph ...

, the

United States Drug Enforcement Administration The Drug Enforcement Administration (DEA; ) is a United States federal law enforcement agency under the U.S. Department of Justice tasked with combating drug trafficking and distribution within the U.S. It is the lead agency for domestic en ...

designated hypophosphorous acid (and its salts) as a List I precursor chemical effective November 16, 2001.66 FR 52670—52675.
17 October 2001. Accordingly, handlers of hypophosphorous acid or its salts in the

United States The United States of America (U.S.A. or USA), commonly known as the United States (U.S. or US) or America, is a country primarily located in North America. It consists of 50 states, a federal district, five major unincorporated territorie ...

are subject to stringent regulatory controls including registration, recordkeeping, reporting, and import/export requirements pursuant to the

Controlled Substances Act The Controlled Substances Act (CSA) is the statute establishing federal government of the United States, federal drug policy of the United States, U.S. drug policy under which the manufacture, importation, possession, use, and distribution of ...

and 21 CFR §§ 1309 and 1310.21 USC, Chapter 13 (Controlled Substances Act)
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Organic

In organic chemistry, H₃PO₂ can be used for the reduction of arenediazonium salts, converting to Ar–H. When diazotized in a concentrated solution of hypophosphorous acid, an

amine In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituen ...

substituent can be removed from arenes. Owing to its ability to function as a mild reducing agent and oxygen scavenger it is sometimes used as an additive in Fischer esterification reactions, where it prevents the formation of colored impurities. It is used to prepare phosphinic acid derivatives.

Applications

Hypophosphorous acid (and its salts) are used to reduce metal salts back into bulk metals. It is effective for various

transition metals In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that ca ...

ions (i.e. those of: Co, Cu, Ag, Mn, Pt) but is most commonly used to reduce

nickel Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow to ...

. This forms the basis of

electroless nickel plating Electroless nickel-phosphorus plating is a chemical process that deposits an even layer of nickel-phosphorus alloy on the surface of a solid substrate, like metal or plastic. The process involves dipping the substrate in a water solution containi ...

(Ni–P), which is the single largest industrial application of hypophosphites. For this application it is principally used as a salt (

sodium hypophosphite Sodium hypophosphite (NaPO2H2, also known as sodium phosphinate) is the sodium salt of hypophosphorous acid and is often encountered as the monohydrate, NaPO2H2·H2O. It is a solid at room temperature, appearing as odorless white crystals. It is so ...

Sources

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ChemicalLand21 Listing
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References

{{Hydrogen compounds Hydrogen compounds Phosphorus oxoacids * Reagents for organic chemistry Reducing agents