13598-36-2 Usage
Description
Different sources of media describe the Description of 13598-36-2 differently. You can refer to the following data:
1. Phosphorous acid is an intermediate in the preparation of other phosphorous compounds. It is a raw material to prepare phosphonates for water treatment such as iron and manganese control, scale inhibition and removal, corrosion control and chlorine stabilization. The alkali metal salts (phosphites) of phosphorous acid are being widely marketed either as an agricultural fungicide (e.g. Downy Mildew) or as a superior source of plant phosphorous nutrition. Phosphorous acid is used in stabilizing mixtures for plastic materials. Phosphorous acid is used for inhibiting high-temperature of corrosion-prone metal surfaces and to produce lubricants and lubricant additives.
2. Phosphorous acid, H3PO3, is diprotic (readily ionizes
two protons), not triprotic as might be suggested by this
formula. Phosphorous acid is as an intermediate in the
preparation of other phosphorous compounds. Because
preparation and uses of “phosphorous acid” actually
pertain more to the major tautomer, phosphonic acid,
it is more often referred to as “phosphorous acid”. Phosphorous
acid has the chemical formula H3PO3, which is
best expressed as HPO(OH)2 to show its diprotic character.
P(OH)3 (IUPAC: phosphorous acid) has CAS
number 10294-56-1. It has been shown to be a stable
tautomer.
References
[1] Allison E. McDonald, Bruce R. Grant and William C. Plaxton, Phosphite (Phosphorous Acid): Its Relevance in The Environment and Agriculture and Influence on Plant Phosphate Starvation Response, Journal of Plant Nutrition, 2001, vol. 24, 1505-1519
[2] Sai-Shek Young, Stabilizers for plastic materials, Patent, 1993
[3] Guido Sartori, Method for inhibiting corrosion using phosphorous acid, Patent,2004
[4] John R Morris, Lubricant containing a phosphorous acid ester-aldehyde condensation product, Patent, 1956
Chemical Properties
Phosphorous acid is a white crystalline deliquescent solid that can be prepared by the action of water on phosphorus( III) oxide or phosphorus(III) chloride. It is a dibasic acid producing the anions H2PO3- and HPO3 2- in water. The acid and its salts are slow reducing agents. On warming, phosphonic acid decomposes to phosphine and phosphoric(V) acid. Phosphorus acid is used to prepare phosphite salts. It is usually sold as a 20% aqueous solution.
Physical properties
White crystalline mass; deliquescent; garlic-like odor; density 1.651 g/cm3 at 21°C; melts at 73.6°C; decomposes at 200°C to phosphine and phosphoric acid; soluble in water, about 310 g/100mL; K1 5.1x10-2 and K2 1.8x10-7; soluble in alcohol.
Uses
Phosphorous acid is used to produce the fertilizer phosphate salt like potassium phosphite, ammonium phosphite and calcium phosphite. It is actively involved in the preparation of phosphites like aminotris(methylenephosphonic acid) (ATMP), 1-hydroxyethane 1,1-diphosphonic acid (HEDP) and 2-phosphonobutane-1,2,4-tricarboxylic Acid (PBTC), which find application in water treatment as a scale or corrosive inhibitor. It is also used in chemical reactions as a reducing agent. Its salt, lead phosphite is used as PVC stabilizer. It is also used as a precursor in the preparation of phosphine and as an intermediate in the preparation of other phosphorus compounds.
Application
Phosphorous acid (H3PO3, orthophosphorous acid) may be used as one of the reaction components for the synthesis of the following:α-aminomethylphosphonic acids via Mannich-Type Multicomponent Reaction1-aminoalkanephosphonic acids via amidoalkylation followed by hydrolysisN-protected α-aminophosphonic acids (phospho-isosteres of natural amino acids) via amidoalkylation reaction
Definition
ChEBI: Phosphorous acid is a phosphorus oxoacid. It is a conjugate acid of a dihydrogenphosphite. It is a tautomer of a phosphonic acid.
Preparation
Phosphorus acid can be prepared by the reaction of phosphorus trichloride with water: PCl3 + 3H2O → H3PO4 + 3HClThe reaction is violent. Addition of PCl3 should be extremely cautious and slow. The addition can be carried out safely in the presence of concentrated HCl. Alternatively, a stream of air containing PCl3 vapor is passed into icecold water and solid crystals of H3PO4 form. Alternatively, phosphorus acid can be prepared by adding phosphorus trichloride to anhydrous oxalic acid: PCl3 + 3(COOH）2 → H3PO3 + 3CO + 3CO2 + 3HCl In this reaction, all products except H3PO3 escape as gases leaving the liquid acid. Dissolution of phosphorus sesquioxide in water also forms phosphorus acid. When shaken with ice water, phosphorus acid is the only product . P4O6 + 6H2O → 4H3PO3 However, in hot water part of the phosphorus acid disproportionates to phosphoric acid and phosphorus or phosphine.
General Description
Phosphorous acid appears as a white or yellow crystalline solid (melting point 70.1 deg C) or a solution of the solid. Density 1.651 g /cm3 . Contact may severely irritate skin, eyes, and mucous membranes. Toxic by ingestion, inhalation and skin absorption.
Air & Water Reactions
Deliquescent. Absorbs oxygen from the air very readily to form phosphoric acid [Hawley]. Soluble in water.
Reactivity Profile
Phosphorous acid decomposes when heated to form phosphine, a gas that usually ignites spontaneously in air. Absorbs oxygen from the air to form phosphoric acid [Hawley]. Forms yellow deposits in aqueous solution that are spontaneously flammable upon drying. Reacts exothermically with chemical bases (for example: amines and inorganic hydroxides) to form salts. These reactions can generate dangerously large amounts of heat in small spaces. Dissolution in water or dilution of a concentrated solution with additional water may generate significant heat. Reacts in the presence of moisture with active metals, including such structural metals as aluminum and iron, to release hydrogen, a flammable gas. Can initiate the polymerization of certain alkenes. Reacts with cyanide compounds to release gaseous hydrogen cyanide. May generate flammable and/or toxic gases in contact with dithiocarbamates, isocyanates, mercaptans, nitrides, nitriles, sulfides, and strong reducing agents. Additional gas-generating reactions occur with sulfites, nitrites, thiosulfates (to give H2S and SO3), dithionites (to give SO2), and carbonates (to give CO2).
Health Hazard
TOXIC; inhalation, ingestion or skin contact with material may cause severe injury or death. Contact with molten substance may cause severe burns to skin and eyes. Avoid any skin contact. Effects of contact or inhalation may be delayed. Fire may produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.
Fire Hazard
Non-combustible, substance itself does not burn but may decompose upon heating to produce corrosive and/or toxic fumes. Some are oxidizers and may ignite combustibles (wood, paper, oil, clothing, etc.). Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated.
Flammability and Explosibility
Nonflammable
Industrial uses
This collector was developed recently and was used primarily as specific collector for cassiterite
from ores with complex gangue composition.On the basis of the phosphonic acid, Albright and Wilson had developed a range of collectors
mainly for flotation of oxidic minerals (i.e. cassiterite, ilmenite and pyrochlore).
Very little is known about the performance of these collectors. Limited studies conducted
with cassiterite and rutile ores showed that some of these collectors produce voluminous
froth but were very selective.
Safety Profile
Moderately toxic by ingestion. When heated to decomposition at 200℃ it emits toxic fumes of POx and phosphme whch may ignite. See also PHOSPHINE.
Check Digit Verification of cas no
The CAS Registry Mumber 13598-36-2 includes 8 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 5 digits, 1,3,5,9 and 8 respectively; the second part has 2 digits, 3 and 6 respectively.
Calculate Digit Verification of CAS Registry Number 13598-36:
(7*1)+(6*3)+(5*5)+(4*9)+(3*8)+(2*3)+(1*6)=122
122 % 10 = 2
So 13598-36-2 is a valid CAS Registry Number.
InChI:InChI=1/3H2O.H3P/h3*1H2;1H3/q;;;+3/p-3
13598-36-2Relevant articles and documents
Pedler, A.
, p. 599 - 613 (1890)
Mitchell, A. D.
, p. 1624 - 1638 (1922)
Griffith, R. O.,McKeown, A.
, p. 530 - 538 (1934)
Kinetics and Mechanism of Oxidation of Phosphinic, Phenylphosphinic, and Phosphonic Acids by Pyridinium Chlorochromate
Seth, Monila,Mathur, Abha,Banerji, Kalyan K.
, p. 3640 - 3643 (1990)
Oxidation of the lower oxyacids of phosphorus by pyridinium chlorochromate (PCC) results in the formation of the corresponding higher oxyacids of phosphorus.The reaction is of first order with respect to PCC and the oxyacid.The reaction is catalyzed by hydrogen ions, kobs = a + b.The reaction exhibited a substantial primary kinetic isotope effect.The rates in 19 different organic solvents have been analyzed using Kamlet-Taft's and Swains's equations.It has been found that the cation-solvating power of the solvents plays a predominant role.It is proposed that the "inactive" tautomer of the phosphorus oxyacids is the reactiv e species.Transfer of a hydride ion from the P-H bond to PCC, in the rate-determining step, has been proposed.
Jones, R. T.,Swift, E. H.
, p. 1272 - 1274 (1953)
Griffith, R. O.,McKeown, A.,Taylor, R. P.
, p. 752 - 766 (1940)
31PNMR study on the reactions of amino acids and sugar derivatives with pyrophosphorous acid as a possible prebiotic phosphonylating agent
Seio, Kohji,Shiozawa, Takashi,Sugiyama, Daiki,Ohno, Kentaro,Tomori, Takahito,Masaki, Yoshiaki
, p. 905 - 911 (2019)
Phosphorus is an essential element in living organisms. Evaluating prebiotic processes that lead to phosphorylated biomolecules is an important step toward understanding the origin of life. Schreibersite ([Fe,Ni]3P) is a meteoritic phosphorus mineral which releases various phosphorus species reactive toward biomolecules. We studied the reactions between biomolecules and pyrophosphorus acid (H4P2O5), which is a phosphorous acid derivative released from schreibersite. The reactions between pyrophosphorous acid and molecules having hydroxy groups were carried out under mild alkaline conditions. Notably, some biologically important molecules such as L-serine, L-tyrosine, L-threonine, D-ribose, and D-glyceraldehyde reacted with pyrophosphorous acid to give corresponding phosphonates. These results suggested that if schreibersite and the biomolecules co-existed in the prebiotic earth, they formed the phosphonates which were able to play roles as surrogates or precursors of phosphorylated biomolecules.
Jenkins, W. A.,Jones, R. T.
, p. 1353 - 1354 (1952)
Oxidation of white phosphorus by peroxides in water
Abdreimova,Akbaeva,Polimbetova
, p. 1873 - 1876 (2017)
A mixture of hypophosphorous, phosphorous, and phosphoric acids is formed during the anaerobic oxidation of white phosphorus by peroxides [ROOН; R = Н, 3-ClC6H4CO, (СН3)3С] in water. The rate of reactions grows considerably upon adding nonpolar organic solvents. The activity series of peroxides and solvents are determined experimentally. NMR spectroscopy shows that the main product of the reaction is phosphorous acid, regardless of the nature of the peroxide and solvent. A radical mechanism of oxidation of white phosphorus by peroxides in water is proposed. It is initiated by the homolysis of peroxide with the formation of НO? radicals that are responsible for the homolytic opening of phosphoric tetrahedrons. Further oxidation and stages of the hydrolysis of intermediate phosphorus-containing compounds yield products of the reaction.
Electrochemical generation of P4 2- dianion from white phosphorus
Yakhvarov,Gorbachuk,Khayarov, Kh. R.,Morozov,Rizvanov, I. Kh.,Sinyashin
, p. 2423 - 2427 (2014)
Electrochemical reduction of elemental (white) phosphorus in an undivided cell equipped with a sacrificial metal anode (Al, Co, Nb, Sn) results in the formation of the reduced form of white phosphorus, P4 2- dianion, which was detected in solution by 31P NMR spectroscopy.
Bernhart, D. N.
, p. 1798 - 1799 (1954)
The first water-soluble tetraphosphorus ruthenium complex. Synthesis, characterization and kinetic study of its hydrolysis
Caporali, Maria,Gonsalvi, Luca,Kagirov, Rustam,Mirabello, Vincenzo,Peruzzini, Maurizio,Sinyashin, Oleg,Stoppioni, Piero,Yakhvarov, Dmitry
, p. 67 - 73 (2012)
Reaction of the water-soluble complex [CpRu(TPPMS)2Cl] (1) [TPPMS = sodium salt of m-monosulfonated triphenylphosphine, Ph 2P(m-C6H4SO3Na)] with 1 equiv of white phosphorus in the presence of TlPFsub
Synthesis of monophosphines directly from white phosphorus
Scott, Daniel J.,Cammarata, Jose,Schimpf, Maximilian,Wolf, Robert
, p. 458 - 464 (2021/04/09)
Monophosphorus compounds are of enormous industrial importance due to the crucial roles they play in applications such as pharmaceuticals, photoinitiators and ligands for catalysis, among many others. White phosphorus (P4) is the key starting material for the preparation of all such chemicals. However, current production depends on indirect and inefficient, multi-step procedures. Here, we report a simple, effective ‘one-pot’ synthesis of a wide range of organic and inorganic monophosphorus species directly from P4. Reduction of P4 using tri-n-butyltin hydride and subsequent treatment with various electrophiles affords compounds that are of key importance for the chemical industry, and it requires only mild conditions and inexpensive, easily handled reagents. Crucially, we also demonstrate facile and efficient recycling and ultimately catalytic use of the tributyltin reagent, thereby avoiding the formation of substantial Sn-containing waste. Accessible, industrially relevant products include the fumigant PH3, the reducing agent hypophosphorous acid and the flame-retardant precursor tetrakis(hydroxymethyl)phosphonium chloride. [Figure not available: see fulltext.]
Synthesis of H-Phosphonate Intermediates and Their Use in Preparing the Herbicide Glyphosate
-
Paragraph 0036; 0056, (2014/10/16)
The esterfication of hypophosphorous acid is followed by reaction with another molecule of alcohol under the action of a nickel catalyst to provide a green method for the preparation of H-phosphonate diesters. This method avoids the need for any stoichiometric chlorine unlike those based on phosphorous trichloride.
