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{{Redirect|AgF}} |
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| ImageFile = silverIfluoride.jpg |
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| ImageFile1 = Silver(I)-fluoride-3D-ionic.png |
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| ImageFile1 = Silver(I) fluoride.jpg |
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| ImageFile = Silver(I)-fluoride-3D-ionic.png |
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| IUPACName = Silver(I) fluoride |
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| OtherNames = Argentous fluoride <br/> Silver monofluoride |
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| Section1 = {{Chembox Identifiers |
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| Abbreviations = |
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| CASNo_Ref = {{cascite|correct|??}} |
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| CASNo = 7775-41-9 |
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| CASNo = 7775-41-9 |
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| UNII = 1Z00ZK3E66 |
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| PubChem = 62656 |
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| SMILES = AgF |
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| SMILES = . |
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| RTECS = VW4250000 |
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| Ag=1 | F=1 |
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| Formula = AgF |
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| MolarMass = 126.866 g/mol |
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| Appearance = yellow-brown solid |
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| Appearance = yellow-brown solid |
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| Density = 5.852 g/cm<sup>3</sup>, solid |
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| Density = 5.852 g/cm<sup>3</sup> (15 °C) |
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| MeltingPtC = 435 |
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| MeltingPtC = 435 |
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| BoilingPtC = 1159 |
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| BoilingPtC = 1159 |
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| Solubility = 85.78 g/100 mL (0 °C)<br> 119.8 g/100 mL (10 °C)<br> 179.1 g/100 mL (25 °C)<br> 213.4 g/100 mL (50 °C)<ref name=chemister>Chemister Chemical Database, Kiper Ruslan Anatolievich, 2002-15. URL: http://chemister.ru/Database/properties-en.php?dbid=1&id=1067</ref> |
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| Solubility = 1.8 kg/L (20 °C) |
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| SolubleOther = 83g/100 g (11.9 °C) in ]<br> 1.5g/100 mL in ](25 °C)<ref name = "Stoner">{{cite journal|last1=Busse|first1=Juliette K.|last2=Stoner|first2=Eric J.|title=Silver (I) fluoride|journal=E-EROS Encyclopedia of Reagents for Organic Synthesis|date=2001|doi=10.1002/047084289X.rs016|isbn=0471936235}}</ref> |
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| MagSus = −36.5·10<sup>−6</sup> cm<sup>3</sup>/mol}} |
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| CrystalStruct = cubic |
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| DeltaGf = -187.9 kJ/mol<ref name=chemister /> |
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| DeltaHf = -206 kJ/mol<ref name=chemister /> |
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| Entropy = 83.7 J/mol·K<ref name=chemister /> |
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| GHSPictograms = {{GHS05}} |
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| GHS_ref = <ref name="sigma">{{Sigma-Aldrich|id=226858|name=Silver(I) fluoride|accessdate=2014-05-08}}</ref> |
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| HPhrases = {{H-phrases|314}} |
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| PPhrases = {{P-phrases|260|280|303+361+353|304+340|305+351+338|310}}<ref>{{cite web|title = Silver Fluoride|url = https://www.americanelements.com/silver-fluoride-7775-41-9|publisher = ]|access-date = 2018-09-07}}</ref> |
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'''Silver(I) fluoride''' is the ] with the formula AgF. It is one of the three main ], the others being ] and ]. AgF has relatively few niche applications; it has been employed as a ] and ] ] in ] and in ] as a ] in ]. |
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'''Silver(I) fluoride''' (AgF), also known as argentous fluoride and silver monofluoride, is a compound of ] and ]. It is a ginger-coloured solid, melting point 435 °C,<ref name="greenwood">Greenwood, N. N.; Earnshaw, A. (1997). ''Chemistry of the Elements'', 2nd Edition, Oxford:Butterworth-Heinemann. ISBN 0-7506-3365-4.</ref> which blackens on exposure to moist air. Unlike other silver halides such as ] it is soluble in ] to the extent of 1.8 kg/L,<ref name="greenwood" /> and it even has some solubility in ]. AgF is made from ] and ]. |
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The ] of AgF present as colourless, while pure ] samples are yellow.<ref name ="Palmer" />{{rp|150}} |
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Silver(I) fluoride finds most application in ] for addition of ] across multiple bonds. For example, AgF adds to perfluoro]s in acetonitrile to give perfluoroalkylsilver(I) derivatives:<ref>Miller, W. T.; Burnard, R. J., ''J. Am. Chem. Soc.'' '''1968''', ''90'', 7367-7368.</ref> |
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R<sub>F</sub>CF=CF<sub>2</sub> + AgF → R<sub>F</sub>CF(CF<sub>3</sub>)Ag. |
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== Preparation == |
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] also forms a higher fluoride, ]. |
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High-purity silver(I) fluoride can be produced by the heating of ] to {{Convert|310|C|F|abbr=on}} under a ] environment, in a ] tube:<ref name="Roesky">{{cite book|last=Roesky|first=Herbert W.|title=Efficient Preparation of Fluorine Compounds|date=2012|publisher=Wiley|location=Somerset, New Jersey|isbn=9781118409428}}</ref>{{rp|9}} |
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:<chem>Ag2CO3 + 2 HF -> 2 AgF + H2O + CO2</chem> |
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Laboratory routes to the compound typically avoid the use of gaseous hydrogen fluoride. One method is the ] of ]: |
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== See also == |
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:<chem>AgBF4 -> AgF + BF3</chem> |
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*] |
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In an alternative route, ] is dissolved in concentrated aqueous ], and the silver fluoride is precipitated out of the resulting solution by ].<ref name="Roesky" />{{rp|10}} |
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==External links== |
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:<chem>Ag2O + 2 HF -> 2 AgF + H2O</chem> |
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{{Commons category|Silver(I) fluoride}} |
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* |
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== Properties == |
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=== Structure=== |
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The structure of AgF has been determined by ].<ref name ="BF">{{cite journal|last1=Ott|first1=H.|title=XI. Die Strukturen von MnO, MnS, AgF, NiS, SnJ4, SrCl2, BaF2; Präzisionsmessungen einiger Alkalihalogenide|journal=Z. Kristallogr.|date=1926|volume=63|issue=1–6|pages=222–230|doi=10.1524/zkri.1926.63.1.222|s2cid=102244646}}</ref><ref name ="BG">{{cite journal|last1=Bottger|first1=G.L.|last2=Geddes|first2=A.L.|title=Lattice Vibrations, Crystal Structure, Dielectric Properties, and Elastic Constants of AgF|journal=J. Chem. Phys.|date=1972|volume=56|issue=8|pages=3735–3739|doi=10.1063/1.1677770|bibcode=1972JChPh..56.3735B}}</ref>{{rp|3736}}<ref name ="Lozinsek-IUCRData-2023">{{cite journal|last1=Lozinšek|first1=Matic|last2=Belak Vivod|first2=Matic|last3=Dragomir|first3=Mirela|title=Crystal structure reinvestigation of silver(I) fluoride, AgF|journal=IUCrData|date=2023|volume=8|issue=Pt 1 |pages=x230018|doi=10.1107/S2414314623000184|pmid=36794053 |pmc=9912324}}</ref> At ambient temperature and pressure, silver(I) fluoride exists as the polymorph AgF-I, which adopts a ] with space group ''Fm{{overline|3}}m'' in the ]. The ] is adopted by the other silver monohalides. The lattice parameter is 4.936(1) ], significantly lower than those of AgCl and AgBr.<ref name ="BDPK">{{cite journal|last1=Birtcher|first1=R.C.|last2=Deutsch|first2=P.W.|last3=Wendelken|first3=J.F.|last4=Kunz|first4=A.B.|title = Valence band structure in silver fluoride|journal=J. Phys. C: Solid State Phys.|date=1972|volume=5|issue=5|pages=562–6|doi=10.1088/0022-3719/5/5/008|bibcode=1972JPhC....5..562B}}</ref>{{rp|562}} ] and X-ray diffraction studies have further shown that at 2.70(2) GPa, a structural transition occurs to a second polymorph (AgF-II) with the ] structure, and lattice parameter 2.945 Å.<ref name=Hull>{{cite journal|last1=Hull|first1=S.|last2=Berastegui|first2=P|title=High-pressure structural behaviour of silver(I) fluoride|journal=J. Phys.: Condens. Matter|date=1998|volume=10|issue=36|pages=7945–7955|doi=10.1088/0953-8984/10/36/005|bibcode=1998JPCM...10.7945H|s2cid=250869196 }}</ref>{{rp|7945}}<ref>{{cite journal|last1=Halleck|first1=P.M.|last2=Jamieson|first2=J.C.|title=B1 and B2 phase change of AgF at high pressure|journal=J. Phys. Chem. Solids|date=1972|volume=33|issue=4|pages=769–773|doi=10.1016/s0022-3697(72)80093-3|bibcode=1972JPCS...33..769H}}</ref>{{rp|770}} The associated decrease in volume is approximately ten percent.<ref name=Hull />{{rp|7946}} A third polymorph, AgF-III, forms on reducing the pressure to 2.59(2) GPa, and has an inverse ] structure. The lattice parameters are a = 3.244(2) Å and c = 6.24(1) Å; the rock salt structure is regained only on reduction of the pressure to 0.9(1) GPa. ] is exhibited by all three polymorphs under extreme pressures.<ref>{{cite journal|last1=Jamieson|first1=J.C.|last2=Halleck|first2=P.M.|last3=Roof|first3=R.B.|last4=Pistorius|first4=C.W.F.T.|title=Additional polymorphism and non-stoichiometry in AgF|journal=Journal of Physics and Chemistry of Solids|date=1975|volume=36|issue=9|pages=939–944|doi=10.1016/0022-3697(75)90172-9|bibcode=1975JPCS...36..939J}}</ref>{{rp|939}}<ref name=Hull />{{rp|7947}} |
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=== Spectroscopy === |
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Silver(I) fluoride exhibits unusual optical properties. Simple ] predicts that the fundamental ] ] for AgF would lie higher than that of AgCl (5.10 eV) and would correspond to a transition from an anionic valence band as for the other silver halides. Experimentally, the fundamental exciton for AgF lies at 4.63 eV.<ref>{{cite journal|last1=Marchetti|first1=A.P.|last2=Bottger|first2=G.L.|title=Optical Absorption Spectrum of AgF|journal=Physical Review B|date=1971|volume=3|issue=8|pages=2604–7|doi=10.1103/physrevb.3.2604|bibcode=1971PhRvB...3.2604M}}</ref>{{rp|2604}} This discrepancy can be explained by positing transition from a valence band with largely silver 4d-orbital character.<ref name ="BDPK"/>{{rp|563}} The high frequency ] is 1.73(2).<ref name ="BG"/>{{rp|3737}} |
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=== Photosensitivity === |
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In contrast with the other ]s, anhydrous silver(I) fluoride is not appreciably ], although the ] is.<ref>{{cite book|last1=Slayter|first1=Elizabeth|title=Light and Electron Microscopy|date=1992|publisher=Cambridge University Press|isbn=9780521339483|url=https://books.google.com/books?id=LlePVS9oq7MC}}</ref>{{rp|286}}<ref name ="Palmer">{{cite book|last1=Palmer|first1=William George|title=Experimental Inorganic Chemistry|date=1954|publisher=CUP Archive|isbn=9780521059022}}</ref>{{rp|150}} With this and the material's solubility in water considered, it is unsurprising that it has found little application in ] but may have been one of the salts used by ] in his "]",<ref>{{Cite book|url=https://archive.org/details/treatiseonhelioc00hill|title=A treatise on heliochromy : or, The production of pictures, by means of light, in natural colors. Embracing a full, plain, and unreserved description of the process known as the hillotype, including the author's newly discovered collodio-chrome, or natural colors on collodionized glass ...|last=Hill|first=Levi L.|date=1856|publisher=New York : Robinson & Caswell|others=Getty Research Institute|page=143}}</ref> although a US patent for an experimental AgF-based method was granted in 1970.<ref>{{cite patent |
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| country = US |
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| number = 3537855 |
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| status = patent |
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| title = Photosensitive silver fluoride element |
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| pubdate = 1971-11-3 |
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}}</ref> |
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=== Solubility === |
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Unlike the other silver halides, AgF is highly ] (1800 g/L), and it even has some solubility in ]. It is also unique among silver(I) compounds and the silver halides in that it forms the hydrates AgF·(H<sub>2</sub>O)<sub>2</sub> and AgF·(H<sub>2</sub>O)<sub>4</sub> on precipitation from aqueous solution.<ref name="greenwood">{{Greenwood&Earnshaw2nd|page=}}</ref>{{rp|1185}}<ref name="Tyrra">{{cite journal|last1=Tyrra|first1=Wieland|title=Silver(I) fluoride and related compounds in chemical synthesis|journal=Heteroatom Chemistry|year=2002|volume=13|issue=6|pages=561–566|doi=10.1002/hc.10102}}</ref> Like the ] fluorides, it dissolves in hydrogen fluoride to give a conducting solution.<ref name=Schwartz>{{cite book|last1=Schwartz|first1=Mel|title=Encyclopedia of Materials, Parts and Finishes|date=2002|publisher=CRC press|isbn=1420017160|page=305|edition=2nd}}</ref> |
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== Applications == |
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=== Organic synthesis === |
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Silver(I) fluoride finds application in ] for addition of ] across multiple bonds. For example, AgF adds to perfluoro]s in acetonitrile to give perfluoroalkylsilver(I) derivatives.<ref>{{cite journal | last1 = Miller | first1 = W. T. | last2 = Burnard | first2 = R. J. | year = 1968 | title = Perfluoroalkylsilver compounds" "Title | journal = J. Am. Chem. Soc. | volume = 90 | pages = 7367–7368 | doi=10.1021/ja01028a047}}</ref>{{rp|7367}} It can also be used as a desulfuration-fluorination reagent on ] derived substrates.<ref name=Tyrra />{{rp|562}} Due to its high solubility in water and organic solvents, it is a convenient source of ] ions, and can be used to fluorinate ]s under mild conditions.<ref name=Stoner /> An example is given by the following reaction:<ref name=Muller>{{cite journal|last1=Muller|first1=Paul|last2=Etienne|first2=Robert|last3=Pfyfer|first3=Jean|last4=Pinenda|first4=Nelson|last5=Schipoff|first5=Michel|title=Allylic Reactions of Benzocyclopropenes. Discrimination of Halogen Substituents in 1,l-Dihalogenobenzocyclopropenes|journal=Helvetica Chimica Acta|date=1978|volume=61|issue=7|pages=2482–8|doi=10.1002/hlca.19780610719 }}</ref> |
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:] |
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Another organic synthetic method using silver(I) fluoride is the ]-AgF complex catalyzed ] protonation of ]s:<ref>{{cite journal|last1=Yanagisawa|first1=Akira|last2=Touge|first2=Taichiro|last3=Takayoshi|first3=Arai|title=Enantioselective Protonation of Silyl Enolates Catalyzed by a Binap⋅AgF Complex|journal=Angewandte Chemie International Edition|date=2005|volume=44|issue=10|pages=1546–8|doi=10.1002/anie.200462325|pmid=15645475}}</ref>{{rp|1546}} |
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:] |
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=== Inorganic synthesis === |
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The reaction of ] with a concentrated solution of silver(I) fluoride results in the formation of a ]-like <sup>2+</sup> cluster with endohedral acetylenediide.<ref>{{cite journal|last1=Guo|first1=Guo-Cong|last2=Zhou|first2=Gong-Du|last3=Wang|first3=Qi-Guang|last4=Mak|first4=Thomas C.W.|title=A Fully Encapsulated Acetylenediide in Ag<sub>2</sub>C<sub>2</sub>.8AgF|journal=Angewandte Chemie International Edition|date=1998|volume=37|issue=5|pages=630–2|doi=10.1002/(sici)1521-3773(19980316)37:5<630::aid-anie630>3.0.co;2-k|pmid=29711066 }}</ref> |
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] fluorides can be conveniently prepared in the laboratory by the reaction of the tetralkylammonium bromide with an aqueous AgF solution.<ref>{{cite journal|last1=Clark|first1=James H.|title=Fluoride ion as a base in organic synthesis|journal=Chemical Reviews|year=1980|volume=80|issue=5|pages=429–452|doi=10.1021/cr60327a004}}</ref>{{rp|430}} |
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=== Other === |
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It is possible to coat a silicon surface with a uniform silver microlayer (0.1 to 1 μm thickness) by passing AgF vapour over it at 60–800 °C.<ref name=VM>{{cite journal|last1=Voorhoeve|first1=R. J. H.|last2=Merewether|first2=J. W.|title=Selective Deposition of Silver on Silicon by Reaction with Silver Fluoride Vapor|journal=J. Electrochem. Soc.|date=1972|volume=119|issue=3|pages=364–368|doi=10.1149/1.2404203|bibcode=1972JElS..119..364V|doi-access=free}}</ref> The relevant reaction is: |
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:<chem>4 AgF + Si -> 4 Ag + SiF4</chem> |
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Multiple studies have shown silver(I) fluoride to be an effective ] agent, although the mechanism is the subject of current research.<ref name="dental review">{{cite journal|last1=Peng|first1=J. J-Y.|last2=Botelho|first2=M.G.|last3=Matinlinna|first3=J.P.|title=Silver compounds used in dentistry for caries management: A review|journal=Journal of Dentistry|date=2012|volume=40|issue=7|pages=531–541|doi=10.1016/j.jdent.2012.03.009|pmid=22484380}}</ref> Treatment is typically by the "atraumatic" method, in which 40% by mass aqueous silver(I) fluoride solution is applied to carious leisons, followed by sealing of the dentine with ].<ref name=Got97>{{cite journal|last1=Gotjamanos|first1=Theo|last2=Afonso|first2=Fernando|title=Unacceptably high levels of fluoride in commercial preparations of silver fluoride|journal=Australian Dental Journal|date=1997|volume=42|issue=1|pages=52–3|doi=10.1111/j.1834-7819.1997.tb00097.x|pmid=9078648|doi-access=free}}</ref> Although the treatment is generally recognised to be safe, ] has been a significant clinical concern in ] applications, especially as some commercial preparations have had considerable ] contamination in the past.<ref name=Got97 /><ref>{{cite journal|last1=Gotjamanos|first1=Theo|last2=Orton|first2=Vergil|title=Abnormally high fluoride levels in commercial preparations of 40 per cent silver fluoride solution: Contraindications for use in children|journal=Australian Dental Journal|date=1998|volume=43|issue=6|pages=422–7|doi=10.1111/j.1834-7819.1998.tb00203.x|pmid=9973713}}</ref><ref name=Shah14>{{cite journal|last1=Shah|first1=Shalin|last2=Bhaskar|first2=Visjay|last3=Venkatraghavan|first3=Karthik|last4=Choudhary|first4=Prashant|last5=Trivedi|first5=Krishna|last6=M.|first6=Ganesh|title=Silver Diamine Fluoride: A Review and Current Applications|journal=Journal of Advanced Oral Research|date=2014|volume=5|issue=1|pages=25–35|doi=10.1177/2229411220140106|s2cid=56987580|doi-access=free}}</ref> Due to the instability of concentrated AgF solutions, ] (Ag(NH<sub>3</sub>)<sub>2</sub>F) is now more commonly used.<ref name=Shah14 />{{rp|26}} Preparation is by the addition of ammonia to aqueous silver fluoride solution or by the dissolution of silver fluoride in aqueous ammonia.<ref>{{cite patent |
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| number = 3567823 |
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| title = Silver ammonia fluoride solution and method of its use |
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| pubdate = 1971-2-12 |
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| invent1 = Yokomizo Ichiro |
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| invent2 = Yamaga Reiichi |
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== References == |
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== References == |
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{{reflist}} |
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{{reflist}} |
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{{Silver compounds}} |
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{{Silver compounds}} |
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{{Fluorides}} |
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{{DEFAULTSORT:Silver(I) Fluoride}} |
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{{DEFAULTSORT:Silver(I) Fluoride}} |
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