Fluoruro d'argento

Fluoruro d'argento
Fluoruro di argento
Fluoruro di argento
Fluoruro di argento
Fluoruro di argento
Nome IUPAC
Fluoruro di argento
Caratteristiche generali
Formula bruta o molecolareAgF
Massa molecolare (u)126,867 u
AspettoPolvere gialla
Numero CAS7775-41-9
Numero EINECS231-895-8
PubChem62656 e 165912
SMILES
F[Ag]
Proprietà chimico-fisiche
Solubilità in acqua1800 g/L (T=25 °C)
Temperatura di fusione435 °C (708,15 K)
Indicazioni di sicurezza
Simboli di rischio chimico
corrosivo
pericolo
Frasi H314
Consigli P280 - 305+351+338 - 310 [1]

Il fluoruro d'argento, o anche monofluoruro di argento, è un composto binario di argento e fluoro ed è anche il sale di argento(I) dell'acido fluoridrico, avente formula AgF. Cristallizza nella stessa struttura cubica del cloruro di sodio,[2][3] come pure fanno AgCl e AgBr (non AgI).[4]

Tra i fluoruri di argento AgF è intermedio, per stato di ossidazione, tra il subfluoruro di argento Ag2F (Ag) e il difluoruro AgF2 (Ag+2).[4]

Viene utilmente impiegato come blando fluorurante[5] e come desililante.[6]

Proprietà

A temperatura ambiente, appena preparato, si presenta in forma di fiocchi cristallini di color bianco,[7] tendenti al giallo via via più scuro quando esposto all'aria e/o luce, o in campioni commerciali; è inodore, molto igroscopico,[8] meno fotosensibile degli altri alogenuri di argento (non è usato in fotografia chimica[9]) ma, esposto alla luce solare, tende rapidamente a scurirsi o anche annerirsi;[10] è sensibile all'umidità e andrebbe conservato in atmosfera inerte e al riparo dalla luce.[11]

A marcata differenza dagli altri alogenuri di argento, che sono praticamente insolubili in acqua, AgF forma idrati (AgF·2 H2O e AgF·4 H2O) e soprattutto è solubilissimo in acqua: ~1800 g/L a 25 °C, che corrisponde a una soluzione ~14,2 m.[4] È anche molto solubile in HF anidro (832 g/kg, ~6,55 m a 12 °C)[12] dando soluzioni che conducono la corrente elettrica;[13] mostra una certa solubilità in soluzioni acquose di ammoniaca, in metanolo, acido acetico e acetonitrile.[7] Data la pratica insolubilità degli altri alogenuri di argento, una soluzione acquosa di AgF, trattata con soluzione di cloruri, bromuri o ioduri, si intorbida immediatamente e dà i corrispondenti precipitati; con cloruri, ad esempio, si ha:

AgF (sol) + Cl (sol)  →  AgCl + F(sol)

Reazioni di questo tipo possono essere usate in chimica organica per trasformare i cloruri di tetraalchilammonio nei corrispondenti fluoruri, che hanno spiccate proprietà basiche e nucleofile, specie in solventi polari aprotici:[14]

R4NCl + AgF  →  AgCl + R4NF

A differenza degli altri alogenuri d'argento, prevalentemente covalenti,[15] AgF è un composto essenzialmente ionico, in cui figura lo ione Ag+, in configurazione elettronica d10, diamagnetico, e lo ione fluoruro (ottetto completo). In fase gassosa la molecola AgF mostra un potenziale di ionizzazione di 11,0 eV.[16]

Sintesi

Si può preparare per reazione diretta tra ossido di argento (Ag2O),[4] o anche carbonato di argento (Ag2CO3),[7] e acido fluoridrico secondo le reazioni:

Ag2O + 2 HF → 2 AgF + H2O
Ag2CO3 + 2 HF → 2 AgF + H2O + CO2

Si può anche preparare per decomposizione termica del tetrafluoroborato di argento:[17]

AgBF4 → AgF + BF3

Può essere altresì ottenuto molto puro, e con ottima resa, elettrolizzando una soluzione di fluoruro di potassio in acido acetico glaciale con un anodo di argento e una garza di platino come catodo. Il fluoruro di argento che si va formando sulla superficie dell'anodo cade poi sul fondo e si può recuperare per filtrazione, lavandolo sul filtro con acido acetico e poi con benzene, ponendolo poi in essiccatore per far evaporare il benzene che aderisce.[7]

Note

  1. ^ Sigma Aldrich; rev. del 21.02.2014
  2. ^ (EN) H. Ott, XI. Die Strukturen von MnO, MnS, AgF, NiS, SnJ 4 , SrCl 2 , BaF 2 ; Präzisionsmessungen einiger Alkalihalogenide, in Zeitschrift für Kristallographie - Crystalline Materials, vol. 63, n. 1-6, 1º novembre 1926, pp. 222–230, DOI:10.1524/zkri.1926.63.1.222. URL consultato il 26 luglio 2022.
  3. ^ (EN) G. L. Bottger e A. L. Geddes, Lattice Vibrations, Crystal Structure, Dielectric Properties, and Elastic Constants of AgF, in The Journal of Chemical Physics, vol. 56, n. 8, 15 aprile 1972, pp. 3735–3739, DOI:10.1063/1.1677770. URL consultato il 26 luglio 2022.
  4. ^ a b c d N. N. Greenwood e A. Earnshaw, Chemistry of the Elements, 2ª ed., Butterworth - Heinemann, 1997, p. 1185, ISBN 0-7506-3365-4.
  5. ^ (EN) Paul Müller, Robert Etienne e Jean Pfyffer, Allylic Reactions of Benzocyclopropenes. Discrimination of halogen substituents in 1, 1-Dihalogenobenzocyclopropenes, in Helvetica Chimica Acta, vol. 61, n. 7, 1º novembre 1978, pp. 2482–2487, DOI:10.1002/hlca.19780610719. URL consultato il 26 luglio 2022.
  6. ^ (EN) Akira Yanagisawa, Taichiro Touge e Takayoshi Arai, Enantioselective Protonation of Silyl Enolates Catalyzed by a Binap?AgF Complex, in Angewandte Chemie International Edition, vol. 44, n. 10, 25 febbraio 2005, pp. 1546–1548, DOI:10.1002/anie.200462325. URL consultato il 26 luglio 2022.
  7. ^ a b c d (EN) Georg Brauer, HANDBOOK OF PREPARATIVE INORGANIC CHEMISTRY, traduzione di Reed F. Riley, vol. 1, 2ª ed., Academic Press, 1963 [1960], pp. 240-241.
  8. ^ CRC Handbook of Chemistry and Physics, 97ª ed., CRC Press, 31 luglio 2016, p. 367, DOI:10.1201/9781315380476, ISBN 978-1-315-38047-6. URL consultato l'8 luglio 2023.
  9. ^ editor, La Fotografia Chimica, su Agenzia Luce. URL consultato l'8 settembre 2024.
  10. ^ (EN) PubChem, Silver fluoride, su pubchem.ncbi.nlm.nih.gov. URL consultato il 26 luglio 2022.
  11. ^ (EN) Silver fluoride | 7775-41-9, su ChemicalBook. URL consultato il 26 luglio 2022.
  12. ^ N. N. Greenwood e A. Earnshaw, Chemistry of the Elements, 2ª ed., Butterworth - Heinemann, 1997, p. 817, ISBN 0-7506-3365-4.
  13. ^ Mel M. Schwartz, Encyclopedia of materials, parts, and finishes, 2nd ed, CRC Press, 2002, ISBN 1-56676-661-3, OCLC 50329912. URL consultato il 26 luglio 2022.
  14. ^ (EN) D. Phillip Cox, Jacek Terpinski e Witold Lawrynowicz, "Anhydrous" tetrabutylammonium fluoride: a mild but highly efficient source of nucleophilic fluoride ion, in The Journal of Organic Chemistry, vol. 49, n. 17, 1984-08, pp. 3216–3219, DOI:10.1021/jo00191a035. URL consultato l'8 luglio 2023.
  15. ^ F. A. Cotton e G. Wilkinson, ADVANCED INORGANIC CHEMISTRY, 5ª ed., Wiley Interscience, 1988, p. 942, ISBN 0-471-84997-9.
  16. ^ (EN) silver fluoride, su webbook.nist.gov. URL consultato l'8 luglio 2023.
  17. ^ A.G. Sharpe, The preparation of silver tetrafluoroborate and silver(I)fluoride, in J. Chem. Soc., 1952, pp. 4538–4539.

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