Sodium Monofluorophosphate
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Sodium monofluorophosphate, commonly abbreviated SMFP, is an
inorganic compound In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemist ...
with the
chemical 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, ...
Na2PO3F. Typical for a
salt Salt is a mineral composed primarily of sodium chloride (NaCl), a chemical compound belonging to the larger class of salts; salt in the form of a natural crystalline mineral is known as rock salt or halite. Salt is present in vast quantitie ...
, MFP is odourless, colourless, and water-soluble. This salt is an ingredient in some
toothpaste Toothpaste is a paste or gel dentifrice used with a toothbrush to clean and maintain the aesthetics and health of teeth. Toothpaste is used to promote oral hygiene: it is an abrasive that aids in removing dental plaque and food from the teeth, a ...
s.Klaus Schrödter, Gerhard Bettermann, Thomas Staffel, Friedrich Wahl, Thomas Klein, Thomas Hofmann "Phosphoric Acid and Phosphates" in ''Ullmann’s Encyclopedia of Industrial Chemistry'' 2008, Wiley-VCH, Weinheim.


Uses

MFP is best known as an ingredient in some
toothpaste Toothpaste is a paste or gel dentifrice used with a toothbrush to clean and maintain the aesthetics and health of teeth. Toothpaste is used to promote oral hygiene: it is an abrasive that aids in removing dental plaque and food from the teeth, a ...
s.Wolfgang Weinert "Oral Hygiene Products" in ''Ullmann’s Encyclopedia of Industrial Chemistry'' 2000, Wiley-VCH, Weinheim. It functions as a source of
fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an inorganic, monatomic anion of fluorine, with the chemical formula (also written ), whose salts are typically white or colorless. Fluoride salts typ ...
via the following
hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water ...
reaction: :PO3F2− + OH → HPO42− + F Fluoride protects tooth enamel from attack by bacteria that cause
dental caries Tooth decay, also known as cavities or caries, is the breakdown of teeth due to acids produced by bacteria. The cavities may be a number of different colors from yellow to black. Symptoms may include pain and difficulty with eating. Complicatio ...
(cavities). Although developed by a chemist at
Procter and Gamble The Procter & Gamble Company (P&G) is an American multinational Final good, consumer goods corporation headquartered in Cincinnati, Cincinnati, Ohio, founded in 1837 by William Procter (industrialist), William Procter and James Gamble (industr ...
, its use in toothpaste (
Colgate toothpaste Colgate is an American brand principally used for oral hygiene products such as toothpastes, toothbrushes, mouthwashes and dental floss. Manufactured by Colgate-Palmolive, Colgate's oral hygiene products were first sold by the company in 1873, ...
and
Ultra Brite Ultra Brite is an American brand of toothpaste and tooth-whitener marketed by Colgate-Palmolive in the United States. Marketed as a tooth whitening, whitening toothpaste, its active ingredients are sodium bicarbonate, baking soda, hydrogen peroxide ...
) was patented by
Colgate-Palmolive Colgate-Palmolive Company is an American multinational consumer products company headquartered on Park Avenue in Midtown Manhattan, New York City. The company specializes in the production, distribution, and provision of household, health car ...
, as Procter and Gamble was engaged in the marketing of
Crest toothpaste Crest is an American brand of toothpaste and other oral hygiene products made by American multinational Procter & Gamble (P&G) and sold worldwide. In many countries in Europe, such as Germany, Bulgaria, Serbia, Ukraine, Belarus, Russia, Poland, ...
(containing
stannous fluoride Tin(II) fluoride, commonly referred to commercially as stannous fluoride (from Latin ', 'tin'), is a chemical compound with the formula SnF2. It is a colourless solid used as an ingredient in toothpastes. Oral health benefits Stannous fluoride wa ...
, marketed as "Fluoristan"). In the early 1980s, Crest was reformulated to use MFP, under the trademark "Fluoristat"; today Crest toothpastes use
sodium fluoride Sodium fluoride (NaF) is an inorganic compound with the formula . It is used in trace amounts in the fluoridation of drinking water, in toothpaste, in metallurgy, and as a flux. It is a colorless or white solid that is readily soluble in water. I ...
or
stannous fluoride Tin(II) fluoride, commonly referred to commercially as stannous fluoride (from Latin ', 'tin'), is a chemical compound with the formula SnF2. It is a colourless solid used as an ingredient in toothpastes. Oral health benefits Stannous fluoride wa ...
. Compared to straight fluorides, sodium monofluorophosphate has slightly less aftertaste. MFP is also used in some medications for the treatment of
osteoporosis Osteoporosis is a systemic skeletal disorder characterized by low bone mass, micro-architectural deterioration of bone tissue leading to bone fragility, and consequent increase in fracture risk. It is the most common reason for a broken bone ...
. In 1991, sodium monofluorophosphate was found by
Calgon Calgon is an American brand of bath and beauty products, owned by PDC Brands. Early history The original product consisted of powdered sodium hexametaphosphate (amorphous sodium polyphosphate), which in water would complex with ambient calci ...
to inhibit the dissolution of
lead Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cu ...
in drinking water when used in concentrations between 0.1 mg/L and 500 mg/L.Peter Meier
Monofluorophosphate History
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Tooth decay

Tooth decay is caused by bacteria naturally present in one's mouth. These bacteria form a sticky, colorless soft film on the teeth called
plaque Plaque may refer to: Commemorations or awards * Commemorative plaque, a plate or tablet fixed to a wall to mark an event, person, etc. * Memorial Plaque (medallion), issued to next-of-kin of dead British military personnel after World War I * Pla ...
. When foods containing
carbohydrate In organic chemistry, a carbohydrate () is a biomolecule consisting of carbon (C), hydrogen (H) and oxygen (O) atoms, usually with a hydrogen–oxygen atom ratio of 2:1 (as in water) and thus with the empirical formula (where ''m'' may or ma ...
s (
starch Starch or amylum is a polymeric carbohydrate consisting of numerous glucose units joined by glycosidic bonds. This polysaccharide is produced by most green plants for energy storage. Worldwide, it is the most common carbohydrate in human diets ...
es and
sugar Sugar is the generic name for sweet-tasting, soluble carbohydrates, many of which are used in food. Simple sugars, also called monosaccharides, include glucose, fructose, and galactose. Compound sugars, also called disaccharides or double ...
s) are eaten, the bacteria that form plaque use the sugar as a form of energy. They also turn it into a glue-like substance that helps them stick to the surface of the tooth. The plaque produces
acid In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a sequ ...
, which attacks the enamel.


Chemistry of decay

Tooth enamel consists mostly of calcium hydroxyphosphate, Ca5(PO4)3OH, also known as the mineral
hydroxyapatite Hydroxyapatite, also called hydroxylapatite (HA), is a naturally occurring mineral form of calcium apatite with the formula Ca5(PO4)3(OH), but it is usually written Ca10(PO4)6(OH)2 to denote that the crystal unit cell comprises two entities. ...
. Apatite is a hard, insoluble compound. Acid (H+), produced especially after a high-sugar meal, attacks the apatite: :Ca5(PO4)3OH(s) + H+(aq) → Ca5(PO4)3+(aq) + H2O(ℓ)


Chemistry of enamel fluoridation

The degradation of apatite by loss of OH causes the enamel to dissolve. The process is reversible as saliva supplies back OH to reform apatite. If fluoride, F, ions are present in saliva,
fluorapatite Fluorapatite, often with the alternate spelling of fluoroapatite, is a phosphate mineral with the formula Ca5(PO4)3F (calcium fluorophosphate). Fluorapatite is a hard crystalline solid. Although samples can have various color (green, brown, bl ...
, Ca5(PO4)3F, also forms. :Ca5(PO4)3+(aq) + F(aq) → Ca5(PO4)3F(s) Fluorapatite resists attacks by acids better than apatite itself, so the tooth enamel resists decay better than enamel containing no fluoride.


Preparation and structure

Sodium monofluorophosphate is produced industrially by the reaction of sodium fluoride with sodium
metaphosphate A metaphosphate ion is an oxyanion that has the empirical formula . It was first postulated in 1955 but was not observed until 1979, when it was detected by mass spectrometry. Metaphosphate is an intermediate in the hydrolysis of phosphate esters b ...
: :NaPO3 + NaF → Na2PO3F The process involves scission of a pyrophosphate bond, analogous to hydrolysis. NaMFP can also be prepared by treating
tetrasodium pyrophosphate Tetrasodium pyrophosphate, also called sodium pyrophosphate, tetrasodium phosphate or TSPP, is an inorganic compound with the chemical formula, formula Na4P2O7. As a salt, it is a white, water-soluble solid. It is composed of pyrophosphate anion an ...
or
disodium phosphate Disodium phosphate (DSP), or disodium hydrogen phosphate, or sodium phosphate dibasic, is the inorganic compound with the formula Na2HPO4. It is one of several sodium phosphates. The salt is known in anhydrous form as well as forms with 2, 7, 8, ...
with hydrogen fluoride. In the laboratory, MFP can be prepared by
hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water ...
of difluorophosphate ions with dilute
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly caustic base and alkali ...
: :PO2F2 + 2 NaOH → Na2PO3F + H2O + F


Structure

The structure of the fluorophosphate anion consists of
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 ...
at the center of a tetrahedron defined by three
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
atoms and one
fluorine Fluorine is a chemical element with the symbol F and atomic number 9. It is the lightest halogen and exists at standard conditions as a highly toxic, pale yellow diatomic gas. As the most electronegative reactive element, it is extremely reacti ...
. Formal representations depict a double bond between one oxygen atom and phosphorus, with single bonds for the other two oxygen atoms and the fluorine. In this very formal depiction, negative charge is localized on the O atoms of the single P-O bonds. MFP is similar to and
isoelectronic Isoelectronicity is a phenomenon observed when two or more molecules have the same structure (positions and connectivities among atoms) and the same electronic configurations, but differ by what specific elements are at certain locations in the ...
with Na2 SO4. The anion has C3v
symmetry Symmetry (from grc, συμμετρία "agreement in dimensions, due proportion, arrangement") in everyday language refers to a sense of harmonious and beautiful proportion and balance. In mathematics, "symmetry" has a more precise definit ...
.


Discovery and development

Sodium monofluorophosphate was first described in 1929 by the German chemist Willy Lange, who was then with the University of Berlin. His fruitless attempts to prepare the free monofluorophosphoric acid led him to check the stability of its esters. Together with Gerda von Krüger, one of his students, Lange thus synthesized diethyl fluorophosphate and some analogs, which proved to be quite toxic, being related to
nerve agent Nerve agents, sometimes also called nerve gases, are a class of organic chemicals that disrupt the mechanisms by which nerves transfer messages to organs. The disruption is caused by the blocking of acetylcholinesterase (AChE), an enzyme that ...
s. In the 1930s,
Gerhard Schrader Gerhard Schrader (25 February 1903 – 10 April 1990) was a German chemist specializing in the discovery of new insecticides, hoping to make progress in the fight against hunger in the world. Schrader is best known for his accidental discovery of ...
, working for the German company
IG Farben Interessengemeinschaft Farbenindustrie AG (), commonly known as IG Farben (German for 'IG Dyestuffs'), was a German chemical and pharmaceutical conglomerate (company), conglomerate. Formed in 1925 from a merger of six chemical companies—BASF, ...
, tried to develop synthetic
insecticide Insecticides are substances used to kill insects. They include ovicides and larvicides used against insect eggs and larvae, respectively. Insecticides are used in agriculture, medicine, industry and by consumers. Insecticides are claimed to b ...
. His work focused on esters of phosphoric acid and resulted in an accidental discovery of some other nerve agents such as DFP (
diisopropyl fluorophosphate Diisopropyl fluorophosphate (DFP) or Isoflurophate is an oily, colorless liquid with the chemical formula C6H14FO3P. It is used in medicine and as an organophosphorus insecticide. It is stable, but undergoes hydrolysis when subjected to moisture ...
), Tabun,
Soman Soman (or GD, EA 1210, Zoman, PFMP, A-255, systematic name: ''O''-pinacolyl methylphosphonofluoridate) is an extremely toxic chemical substance. It is a nerve agent, interfering with normal functioning of the mammalian nervous system by inhibiti ...
, and
Sarin Sarin (NATO designation GB G-series, "B"">Nerve_agent#G-series.html" ;"title="hort for Nerve agent#G-series">G-series, "B" is an extremely toxic synthetic organophosphorus compound.Procter and Gamble The Procter & Gamble Company (P&G) is an American multinational Final good, consumer goods corporation headquartered in Cincinnati, Cincinnati, Ohio, founded in 1837 by William Procter (industrialist), William Procter and James Gamble (industr ...
Company. In 1947, he and Ralph Livingston of
Monsanto Company The Monsanto Company () was an American agrochemical and agricultural biotechnology corporation founded in 1901 and headquartered in Creve Coeur, Missouri. Monsanto's best known product is Roundup (herbicide), Roundup, a glyphosate-based herbic ...
published the preparation of the free fluorophosphoric acids and mentioned the use of some toxic esters of monofluorophosphoric acid (like DFP) in the treatment of
glaucoma Glaucoma is a group of eye diseases that result in damage to the optic nerve (or retina) and cause vision loss. The most common type is open-angle (wide angle, chronic simple) glaucoma, in which the drainage angle for fluid within the eye rem ...
and
myasthenia gravis Myasthenia gravis (MG) is a long-term neuromuscular junction disease that leads to varying degrees of skeletal muscle weakness. The most commonly affected muscles are those of the eyes, face, and swallowing. It can result in double vision, dro ...
. The well known toxicity of these esters led to fears that the simple salts might also be toxic, and such fears precluded any large scale commercial use of the salts. In 1950, under sponsorship of the manufacturer of the compounds,
Ozark Chemical Company The Ozarks, also known as the Ozark Mountains, Ozark Highlands or Ozark Plateau, is a physiographic region in the U.S. states of Missouri, Arkansas, Oklahoma and the extreme southeastern corner of Kansas. The Ozarks cover a significant porti ...
, the toxicity of sodium monofluorophosphate was studied by Harold Hodge at the
University of Rochester The University of Rochester (U of R, UR, or U of Rochester) is a private research university in Rochester, New York. The university grants undergraduate and graduate degrees, including doctoral and professional degrees. The University of Roc ...
who included anti-cavity testing. In 1967
Colgate-Palmolive Colgate-Palmolive Company is an American multinational consumer products company headquartered on Park Avenue in Midtown Manhattan, New York City. The company specializes in the production, distribution, and provision of household, health car ...
filed several patents on the use of sodium monofluorophosphate in toothpaste.


Safety

The usual content of MFP in toothpaste is 0.76%. The compound is used in place of sodium fluoride, particularly in children's toothpastes, because it is less acutely toxic, although both have modest toxicities. The in rats is 0.9 g/kg.


References

{{DEFAULTSORT:Sodium Monofluorophosphate Phosphates Fluoro complexes Sodium compounds