Phosphorous acid
Phosphorous 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.
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Names | |||
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IUPAC name
phosphonic acid | |||
Other names
Dihydroxyphosphine oxide Dihydroxy(oxo)-λ5-phosphane | |||
Identifiers | |||
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ChemSpider | |||
ECHA InfoCard | 100.033.682 | ||
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Properties | |||
H3PO3 | |||
Molar mass | 81.99 g/mol | ||
Appearance | white solid deliquescent | ||
Density | 1.651 g/cm3 (21 °C) | ||
Melting point | 73.6 °C (164.5 °F; 346.8 K) | ||
Boiling point | 200 °C (392 °F; 473 K) (decomposes) | ||
310 g/100 mL | |||
Solubility | soluble in ethanol | ||
Acidity (pKa) | 1.1, 6.7 | ||
−42.5·10−6 cm3/mol | |||
Structure | |||
pseudo-tetrahedral | |||
Hazards | |||
Main hazards | skin irritant | ||
Safety data sheet | http://www.sigmaaldrich.com/MSDS/[1] | ||
R-phrases (outdated) | 22-35 | ||
S-phrases (outdated) | 26-36/37/39-45 | ||
NFPA 704 (fire diamond) | |||
Related compounds | |||
Related compounds |
H3PO4 (i.e., PO(OH)3) H3PO2 (i.e., H2PO(OH)) | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |||
Infobox references | |||
Nomenclature and tautomerism
H3PO3 is more clearly described with the structural formula HPO(OH)2. In the solid state, HP(O)(OH)2 is tetrahedral with one shorter P=O bond of 148 pm and two longer P–O(H) bonds of 154 pm. This species exists in equilibrium with an extremely minor tautomer P(OH)3. IUPAC recommends that the latter be called phosphorous acid, whereas the dihydroxy form is called phosphonic acid.[2] Only the reduced phosphorus compounds are spelled with an "ous" ending.
Other important oxyacids of phosphorus are phosphoric acid (H3PO4) and hypophosphorous acid (H3PO2). The reduced phosphorus acids are subject to similar tautomerism involving shifts of H between O and P.
Preparation
HPO(OH)2 is the product of the hydrolysis of its acid anhydride:
- P4O6 + 6 H2O → 4 HPO(OH)2
(An analogous relationship connects H3PO4 and P4O10).
On an industrial scale, the acid is prepared by hydrolysis of phosphorus trichloride with water or steam:[3]
- PCl3 + 3 H2O → HPO(OH)2 + 3 HCl
Potassium phosphite is also a convenient precursor to phosphorous acid:
- K2HPO3 + 2 HCl → 2 KCl + H3PO3
In practice aqueous potassium phosphite is treated with excess hydrochloric acid. By concentrating the solution and precipitations with alcohols, the pure acid can be separated from the salt.
Reactions
Acid–base properties
Phosphorous acid has a pKa in the range 1.26–1.3.[4][5]
- HP(O)(OH)2 → HP(O)2(OH)− + H+ pKa = 1.3
It is a diprotic acid, the hydrogenphosphite ion, HP(O)2(OH)− is a weak acid:
- HP(O)2(OH)− → HPO2−
3 + H+ pKa = 6.7
The conjugate base HP(O)2(OH)− is called hydrogen phosphite, and the second conjugate base, HPO2−
3, is the phosphite ion.[6] (Note that the IUPAC recommendations are hydrogen phosphonate and phosphonate respectively).
The hydrogen atom bonded directly to the phosphorus atom is not readily ionizable. Chemistry examinations often test students' appreciation of the fact that not all three hydrogen atoms are acidic under aqueous conditions, in contrast with H3PO4.
Disproportionation
On heating at 200 °C, phosphorous acid disproportionates to phosphoric acid and phosphine:[7]
- 4 H3PO3 → 3 H3PO4 + PH3
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
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]
It Used in the production of basic lead phosphonate PVC stabilizer, aminomethylene phosphonic acid and hydroxyethane diphosphonic acid. Also Used as a strong reducing agent and in the production of raw materials of phosphorous acid, synthetic fibres and organophosphorus pesticides etc. It used in the production of high efficient water treatment agent amino trimethylene phosphonic acid.
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
- "MSDS - 215112". www.sigmaaldrich.com. Retrieved 12 April 2018.
- 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..
- 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.
- 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.
- CRC Handbook of Chemistry and Physics (87th ed.). p. 8–42.
- Novosad, Josef (1994). Encyclopedia of Inorganic Chemistry. John Wiley and Sons. ISBN 0-471-93620-0.
- Gokhale, S. D.; Jolly, W. L. (1967). "Phosphine". Inorganic Syntheses. 9: 56–58. doi:10.1002/9780470132401.ch17.
- 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.CS1 maint: uses authors parameter (link)
- 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.
- 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: 1202–1204. doi:10.1016/j.inoche.2004.09.012.
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.