08/03/2018 Phosphorous acid - Wikipedia

Phosphorous acid
Phosphorous acid is the compound described by the
Phosphorous acid
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.

Contents Names
Nomenclature and tautomerism IUPAC name
Preparation phosphonic acid
Reactions Other names
Acid–base properties Dihydroxyphosphine oxide
Disproportionation
Dihydroxy(oxo)-λ5-phosphane
Reductions of metal ions
As a ligand Dihydroxy-λ5-phosphanone
Orthophosphorous acid
Uses
Oxo-λ5-phosphanediol
Organic derivatives
References Oxo-λ5-phosphonous acid
Further reading Identifiers
CAS 13598-36-2 (http://www.commonchem
Number
istry.org/ChemicalDetail.aspx?ref=135
Nomenclature and 98-36-2)
tautomerism 3D model Interactive image (https://chemapps.st
(JSmol)
H3PO3 is more clearly
olaf.edu/jmol/jmol.php?model=OP%2
described with the
8%3DO%29O)
structural formula ChEBI CHEBI:44976 (https://www.ebi.ac.uk/c
HPO(OH)2. In the solid hebi/searchId.do?chebiId=44976)
state, HP(O)(OH)2 is
ChemSpider 10449259 (http://www.chemspider.co
tetrahedral with one
m/Chemical-
shorter P=O bond of 148 pm and two longer P–O(H) bonds
Structure.10449259.html)
of 154 pm. This species exists in equilibrium with an
extremely minor tautomer P(OH)3. IUPAC recommends that 10459438 (http://www.chemspider.co
the latter be called phosphorous acid, whereas the dihydroxy m/Chemical-Structure.10459438.html)
form is called phosphonic acid.[2] Only the reduced (17O3)
phosphorus compounds are spelled with an "ous" ending. ECHA 100.033.682 (https://echa.europa.eu/s
InfoCard ubstance-information/-/substanceinfo/
Other important oxyacids of phosphorus are phosphoric acid
100.033.682)
(H3PO4) and hypophosphorous acid (H3PO2). The reduced
phosphorus acids are subject to similar tautomerism
KEGG C06701 (http://www.kegg.jp/entry/C06
involving shifts of H between O and P. 701)
RTECS SZ6400000
Preparation number
UNII 35V6A8JW8E (https://fdasis.nlm.nih.g

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08/03/2018 Phosphorous acid - Wikipedia

HPO(OH)2 is the product of the hydrolysis of its acid ov/srs/srsdirect.jsp?regno=35V6A8JW

anhydride: 8E)

P4O6 + 6 H2O → 4 HPO(OH)2 InChI

SMILES
(An analogous relationship connects H3PO4 and P4O10).
Properties
On an industrial scale, the acid is prepared by hydrolysis of Chemical H3PO3
phosphorus trichloride with water or steam:[3] formula
Molar mass 81.99 g/mol
PCl3 + 3 H2O → HPO(OH)2 + 3 HCl
Appearance white solid
Potassium phosphite is also a convenient precursor to deliquescent
phosphorous acid: Density 1.651 g/cm3 (21 °C)
Melting point 73.6 °C (164.5 °F; 346.8 K)
K2HPO3 + 2 HCl → 2 KCl + H3PO3
Boiling point 200 °C (392 °F; 473 K) (decomposes)
In practice aqueous potassium phosphite is treated with Solubility in 310 g/100 mL
excess hydrochloric acid. By concentrating the solution and water
precipitations with alcohols, the pure acid can be separated Solubility soluble in alcohol
from the salt.
Acidity (pKa) 1.1, 6.7
Magnetic −42.5·10−6 cm3/mol
Reactions susceptibility
(χ)
Structure
Acid–base properties Molecular pseudo-tetrahedral
Phosphorous acid is a strong acid with a pKa in the range shape
1.26–1.3.[4][5] Hazards
Main skin irritant
HP(O)(OH)2 → HP(O)2(OH)− + H+ hazards
pKa = 1.3
Safety data http://www.sigmaaldrich.com/MSDS/[1]
It is a diprotic acid, the hydrogenphosphite ion, HP(O)2(OH) sheet
− is a moderately strong acid: R-phrases 22-35
(outdated)
HP(O)2(OH)− → HPO32− + H+
S-phrases 26-36/37/39-45
pKa = 6.7
(outdated)

The conjugate base HP(O)2(OH)− is called hydrogen NFPA 704

phosphite, and the second conjugate base, HPO2− 0
3 , is the
phosphite ion.[6] (Note that the IUPAC recommendations are
3 1
hydrogen phosphonate and phosphonate respectively).
Related compounds
The hydrogen bonded directly to the phosphorus atom is not
readily ionizable. Chemistry examinations often test students' Related H3PO4 (i.e., PO(OH)3)
compounds H3PO2 (i.e., H2PO(OH))
appreciation of the fact that not all three hydrogen atoms are
acidic under aqueous conditions, in contrast with H3PO4. Except where otherwise noted, data are given for
materials in their standard state (at 25 °C [77 °F],
100 kPa).
Disproportionation verify (what is ?)
On heating at 200 °C, phosphorous acid disproportionates to Infobox references
phosphoric acid and phosphine:[7]

4 H3PO3 → 3 H3PO4 + PH3

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08/03/2018 Phosphorous acid - Wikipedia

This reaction is used for laboratory-scale preparations of PH3.

Reductions of metal ions

Both phosphorous acid and its deprotonated forms are good reducing agents, although not necessarily quick to react. They
are oxidized to phosphoric acid or its salts. It reduces solutions of noble metal cations to the metals. When phosphorous
acid is treated with a cold solution of mercuric chloride, a white precipitate of mercurous chloride forms:

H3PO3 + 2 HgCl2 + H2O → Hg2Cl2 + H3PO4 + 2 HCl

Mercurous chloride is reduced further by phosphorous acid to mercury on heating or on standing:

H3PO3 + Hg2Cl2 + H2O → 2 Hg + H3PO4 + 2 HCl

As a ligand
Upon treatment with metals of d6 configuration, phosphorous acid is known to coordinate as the otherwise rare P(OH)3
tautomer. Examples include Mo(CO)5(P(OH)3) and [Ru(NH3)4(H2O)(P(OH)3)]2+.[8][9]

Uses
The most important use of phosphorous acid (phosphonic acid) is the production of basic lead phosphite, which is a
stabilizer in PVC and related chlorinated polymers.[3]

Phosphites have shown effectiveness in controlling a variety of plant diseases, in particular, treatment using either trunk
injection or foliar containing phosphorous acid salts is indicated in response to infections by phytophthora and pythium-
type plant pathogens (both within class oomycetes, known as water molds), such as dieback/root rot and downy
mildew.[10] Anti-microbial products containing salts of phosphorous acid are marketed in Australia as 'Yates Anti-Rot';
and in the United States of America, for example, aluminum salts of the monoethyl ester of phosphorous acid (known
generically as 'Fosetyl-Al') are sold under the trade name 'Aliette' and potassium salts of phosphorous acid (known
generically as potassium phosphite) are sold under the trade name ProPhyt. Phosphorous acid and its salts, unlike
phosphoric acid, are somewhat toxic and should be handled carefully.[11][12]

Organic derivatives
The IUPAC (mostly organic) name is phosphonic acid. This nomenclature is commonly reserved for substituted
derivatives, that is, organic group bonded to phosphorus, not simply an ester. For example, (CH3)PO(OH)2 is
"methylphosphonic acid", which may of course form "methylphosphonate" esters.

References
1. http://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?
country=US&language=en&productNumber=215112&brand=SIAL&PageToGoToURL=http%3A%2F%2Fwww.sigmaaldr
2. International Union of Pure and Applied Chemistry (2005). Nomenclature of Inorganic Chemistry (IUPAC
Recommendations 2005). Cambridge (UK): RSC–IUPAC. ISBN 0-85404-438-8. Electronic version. (http://old.iupac.or
g/publications/books/rbook/Red_Book_2005.pdf).
3. Betterman, G.; Krause, W.; Riess, G.; Hofmann, T. “Phosphorus Compounds, Inorganic” Ullmann’s Encyclopedia of
Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi: 10.1002/14356007.a19_527 (https://doi.org/10.1002%2F1435
6007.a19_527).
4. Larson, John W.; Pippin, Margaret (1989). "Thermodynamics of ionization of hypophosphorous and phosphorous
acids. Substituent effects on second row oxy acids". Polyhedron. 8: 527–530. doi:10.1016/S0277-5387(00)80751-2 (h
ttps://doi.org/10.1016%2FS0277-5387%2800%2980751-2).
5. CRC Handbook of Chemistry and Physics (87th ed.). p. 8–42.

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08/03/2018 Phosphorous acid - Wikipedia

6. Novosad, Josef (1994). Encyclopedia of Inorganic Chemistry. John Wiley and Sons. ISBN 0-471-93620-0.
7. Gokhale, S. D.; Jolly, W. L. (1967). "Phosphine". Inorganic Syntheses. 9: 56–58. doi:10.1002/9780470132401.ch17 (h
ttps://doi.org/10.1002%2F9780470132401.ch17).
8. Sernaglia, R. L.; Franco, D. W. (2005). "The ruthenium(II) center and the phosphite-phosphonate tautomeric
equilibrium". Inorg. Chem. 28: 3485–3489. doi:10.1021/ic00317a018 (https://doi.org/10.1021%2Fic00317a018).
9. Xi, Chanjuan; Liu, Yuzhou; Lai, Chunbo; Zhou, Lishan (2004). "Synthesis of molybdenum complex with novel P(OH)3
ligand based on the one-pot reaction of Mo(CO)6 with HP(O)(OEt)2 and water". Inorganic Chemistry
Communications. 7 (11): 1202. doi:10.1016/j.inoche.2004.09.012 (https://doi.org/10.1016%2Fj.inoche.2004.09.012).
10. Organic Labs. Phosphites with approved fungicide label in the (http://organiclabs.com/images/logos/110_EXEL%20L
G%20Back%20NEW.doc) European Union countries such as France sold under the trade name 'LBG' and in the
United States of America sold under the trade name 'ProPhyt'. The Product label for 'Exel LG,' Retrieved April 9,
2007.
11. Yates, a Division of Orica Australia Pty Ltd. “MSDS ('Yates Anti Rot Phosacid Systemic Fungicide').” Version 1. SH&E
Shared Services, Orica. Homebush, NSW (Australia): April 4, 2005 (retrieved from www.orica.com April 9, 2007). (htt
p://msds.orica.com/pdf/shess-en-cds-010-000000020540.pdf)
12. [[s:Image:Fosetyl-al red-facts 1994.pdf|US EPA. “Fosetyl-Al (Aliette): Reregistration Eligibility Dh as Franceecision
(RED) Fact Sheet.” Office of Pesticide Programs, US EPA. Washington, DC (USA): 1994 (retrieved from
www.epa.gov April 9, 2007).]]

Further reading
Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 0-12-352651-5.
Corbridge., D. E. C. Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology (5th ed.). Amsterdam:
Elsevier. ISBN 0-444-89307-5.
Lee, J.D. Concise Inorganic Chemistry. Oxford University Press. ISBN 978-81-265-1554-7.

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