Chloroauric acid

Chloroauric acid is an inorganic compound with the chemical formula H[AuCl4]. It forms hydrates H[AuCl4]·nH2O. Both the trihydrate and tetrahydrate are known. Both are orange-yellow solids consisting of the planar [AuCl4]− anion. Often chloroauric acid is handled as a solution, such as those obtained by dissolution of gold in aqua regia. These solutions can be converted to other gold complexes or reduced to metallic gold or gold nanoparticles.

Chloroauric acid
Names
Other names
  • Hydrogen tetrachloroaurate
  • Hydrogen tetrachloroaurate(III)
  • Chlorauric acid
  • Tetrachloroauric(III) acid
  • Aurochloric acid
  • Aurate(1−), tetrachloro-, hydrogen, (SP-4-1)-
  • Hydrogen aurichloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.037.211
EC Number
  • 240-948-4
UNII
  • InChI=1S/Au.4ClH/h;4*1H/q+3;;;;/p-3 checkY
    Key: VDLSFRRYNGEBEJ-UHFFFAOYSA-K checkY
  • InChI=1/Au.4ClH.Na/h;4*1H;/q+3;;;;;+1/p-4/rAuCl4.Na/c2-1(3,4)5;/q-1;+1
    Key: IXPWAPCEBHEFOV-ACHCXQQJAP
  • InChI=1/Au.4ClH/h;4*1H/q+3;;;;/p-3/rAuCl4/c2-1(3,4)5/q-1/p+1
    Key: VDLSFRRYNGEBEJ-ZXMCYSOYAI
  • [H+].Cl[Au-](Cl)(Cl)Cl
Properties
H[AuCl4]
Molar mass
  • 339.785 g/mol (anhydrous)
  • 393.833 g/mol (trihydrate)
  • 411.85 g/mol (tetrahydrate)
Appearance orange-yellow needle-like hygroscopic crystals
Density 3.9 g/cm3 (anhydrous)
2.89 g/cm3 (tetrahydrate)
Melting point 254 °C (489 °F; 527 K) (decomposes)
350 g of H[AuCl4] in 100 g of H2O
Solubility soluble in alcohol, ester, ether, ketone
log P 2.67510 [1]
Conjugate base Tetrachloroaurate(III)
Structure
monoclinic
Hazards
GHS labelling:
GHS05: CorrosiveGHS07: Exclamation markGHS08: Health hazardGHS09: Environmental hazard
Danger
H302, H314, H317, H373, H411
P260, P261, P264, P272, P280, P301+P330+P331, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P333+P313, P363, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamond
3
0
1
Safety data sheet (SDS) JT Baker
Related compounds
Other anions
 Tetrabromoauric acid
Related compounds
 Gold(III) chloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)
Infobox references

Properties

Structure

The tetrahydrate crystallizes as [H5O2]+[AuCl4]− and two water molecules.[2] The oxidation state of gold in H[AuCl4] and [AuCl4]− anion is +3. The salts of H[AuCl4] (tetrachloroauric(III) acid) are tetrachloroaurates(III), containing [AuCl4]− anions (tetrachloroaurate(III) anions), which have square planar molecular geometry. The Au–Cl distances are around 2.28 Å. Other d8 complexes adopt similar structures, e.g. tetrachloroplatinate(II) [PtCl4]2−.

Solute properties

Solid chloroauric acid is a hydrophilic (ionic) protic solute. It is soluble in water and other oxygen-containing solvents, such as alcohols, esters, ethers, and ketones. For example, in dry dibutyl ether or diethylene glycol, the solubility exceeds 1 M.[3][4][5] Saturated solutions in the organic solvents often are the liquid solvates of specific stoichiometry. Chloroauric acid is a strong monoprotic acid.

When heated in air, solid H[AuCl4]·nH2O melts in the water of crystallization, quickly darkens and becomes dark brown.

Chemical reactions

Since [AuCl4]− is prone to hydrolyze,[6] upon treatment with an alkali metal base, chloroauric acid converts to gold(III) hydroxide.[7] The related thallium salt(Tl+[AuCl4]−) is poorly soluble in all nonreacting solvents. Salts of quaternary ammonium cations are known.[8] Other complex salts include [Au(bipy)Cl2]+[AuCl4]−[9] and [Co(NH3)6]3+[AuCl4]−(Cl−)2.

Partial reduction of chloroauric acid gives oxonium dichloridoaurate(1−).[10] Reduction may also yield other gold(I) complexes, especially with organic ligands. Often the ligand serves as reducing agent as illustrated with thiourea, CS(NH2)2:

[AuCl4]− + 3 CS(NH2)2 + H2O → [Au(CS(NH2)2)2]+ + CO(NH2)2 + S + 2 Cl− + 2 HCl

Chloroauric acid is the precursor to gold nanoparticles by precipitation onto mineral supports.[11] Heating of H[AuCl4]·nH2O in a stream of chlorine gives gold(III) chloride (Au2Cl6).[12] Gold nanostructures can be made from chloroauric acid in a two-phase redox reaction whereby metallic clusters are amassed through the simultaneous attachment of self-assembled thiol monolayers on the growing nuclei. [AuCl4]− is transferred from aqueous solution to toluene using tetraoctylammonium bromide where it is then reduced with aqueous sodium borohydride in the presence of a thiol.[13]

Production

Chloroauric acid is produced by dissolving gold in aqua regia (a mixture of concentrated nitric and hydrochloric acids) followed by careful evaporation of the solution:[14][15]

Au(s) + HNO3(aq) + 4 HCl(aq) → H[AuCl4](aq) + NO(g) + 2 H2O(l)

Under some conditions, oxygen can be used as an oxidant.[16] For higher efficiency, these processes are conducted in autoclaves, which allows greater control of temperature and pressure. Alternatively, a solution of H[AuCl4] can be produced by electrolysis of gold metal in hydrochloric acid:

2 Au(s) + 8 HCl(aq) → 2 H[AuCl4](aq) + 3 H2(g)

To prevent the deposition of gold on the cathode, the electrolysis is carried out in a cell equipped with a membrane. This method is used for refining gold. Some gold remains in solution in the form of [AuCl2]−.[17]

Uses

Chloroauric acid is the precursor used in the purification of gold by electrolysis.

Liquid–liquid extraction of chloroauric acid is used for the recovery, concentrating, purification, and analytical determinations of gold. Of great importance is the extraction of H[AuCl4] from hydrochloric medium by oxygen-containing extractants, such as alcohols, ketones, ethers and esters. The concentration of gold(III) in the extracts may exceed 1 mol/L.[3][4][5] Frequently used extractants for this purpose are dibutyl glycol, methyl isobutyl ketone, tributyl phosphate, dichlorodiethyl ether (chlorex).[18]

In histology, chlorauric acid is known as "brown gold chloride", and its sodium salt Na[AuCl4] (sodium tetrachloroaurate(III)) as "gold chloride", "sodium gold chloride" or "yellow gold chloride". The sodium salt is used in a process called "toning" to improve the optical definition of tissue sections stained with silver.[19]

Health effects and safety

Chloroauric acid is a strong eye, skin, and mucous membrane irritant. Prolonged skin contact with chloroauric acid may result in tissue destruction. Concentrated chloroauric acid is corrosive to skin and must, therefore, be handled with appropriate care, since it can cause skin burns, permanent eye damage, and irritation to mucous membranes. Gloves are worn when handling the compound.

References
  1. "hydrogen tetrachloroaurate(iii)_msds".
  2. Williams, Jack Marvin; Peterson, Selmer Wiefred (1969). "Example of the [H5O2]+ ion. Neutron diffraction study of tetrachloroauric acid tetrahydrate". Journal of the American Chemical Society. 91 (3): 776–777. doi:10.1021/ja01031a062. ISSN 0002-7863.
  3. Mironov, I. V.; Natorkhina, K. I. (2012). "On the selection of extractant for the preparation of high-purity gold". Russian Journal of Inorganic Chemistry. 57 (4): 610. doi:10.1134/S0036023612040195. S2CID 98015888.
  4. Feather, A.; Sole, K. C.; Bryson, L. J. (July 1997). "Gold refining by solvent extraction—the minataur process" (PDF). Journal of the Southern African Institute of Mining and Metallurgy: 169–173. Retrieved 2013-03-17.
  5. Morris, D. F. C.; Khan, M. A. (1968). "Application of solvent extraction to the refining of precious metals, Part 3: purification of gold". Talanta. 15 (11): 1301–1305. doi:10.1016/0039-9140(68)80053-0. PMID 18960433.
  6. Đurović, Mirjana D.; Puchta, Ralph; Bugarčić, Živadin D.; Eldik, Rudi van (1999-02-22). "Studies on the reactions of [AuCl4]− with different nucleophiles in aqueous solution". Dalton Transactions. 43 (23): 8620–8632. doi:10.1039/C4DT00247D. PMID 24760299.
  7. Kawamoto, Daisuke; Ando, Hiroaki; Ohashi, Hironori; Kobayashi, Yasuhiro; Honma, Tetsuo; Ishida, Tamao; Tokunaga, Makoto; Okaue, Yoshihiro; Utsunomiya, Satoshi; Yokoyama, Takushi (2016-11-15). "Structure of a Gold(III) Hydroxide and Determination of Its Solubility". Bulletin of the Chemical Society of Japan. The Chemical Society of Japan. 89 (11): 1385–1390. doi:10.1246/bcsj.20160228. ISSN 0009-2673.
  8. Makotchenko, E. V.; Kokovkin, V. V. (2010). "Solid contact [AuCl4]−-selective electrode and its application for evaluation of gold(III) in solutions". Russian Journal of General Chemistry. 80 (9): 1733. doi:10.1134/S1070363210090021. S2CID 95581984.
  9. Mironov, I. V.; Tsvelodub, L. D. (2001). "Equilibria of the substitution of pyridine, 2,2′-bipyridyl, and 1,10-phenanthroline for Cl− in AuCl4− in aqueous solution". Russian Journal of Inorganic Chemistry. 46: 143–148.
  10. Huang, Xiaohua; Peng, Xianghong; Wang, Yiqing; Wang, Yuxiang; Shin, Dong M.; El-Sayed, Mostafa A.; Nie, Shuming (26 October 2010). "A reexamination of active and passive tumor targeting by using rod-shaped gold nanocrystals and covalently conjugated peptide ligands". ACS Nano. ACS Publications. 4 (10): 5887–5896. doi:10.1021/nn102055s. PMC 2964428. PMID 20863096.
  11. Gunanathan, C.; Ben-David, Y.; Milstein, D. (2007). "Direct Synthesis of Amides from Alcohols and Amines with Liberation of H2". Science. 317 (5839): 790–792. Bibcode:2007Sci...317..790G. doi:10.1126/science.1145295. PMID 17690291. S2CID 43671648.
  12. Mellor, J. W. (1946). A Comprehensive Treatise on Inorganic and Theoretical Chemistry. vol. 3, p. 593.
  13. Brust, Mathias; Walker, Merryl; Bethell, Donald; Schiffrin, David J.; Whyman, Robin (1994). "Synthesis of Thiol-derivatised Gold Nanoparticles in a Two-phase Liquid-Liquid System". J. Chem. Soc., Chem. Commun. Royal Society of Chemistry (7): 801–802. doi:10.1039/C39940000801.
  14. Brauer, G., ed. (1963). Handbook of Preparative Inorganic Chemistry (2nd ed.). New York: Academic Press.
  15. Block, B. P. (1953). "Gold Powder and Potassium Tetrabromoaurate(III)". Inorganic Syntheses. Inorganic Syntheses. Vol. 4. pp. 14–17. doi:10.1002/9780470132357.ch4. ISBN 9780470132357.
  16. Novoselov, R. I.; Makotchenko, E. V. (1999). "Application of oxygen as ecologically pure reagent for the oxidizing of non-ferrous and precious metals, sulphide minerals". Chemistry for Sustainable Development. 7: 321–330.
  17. Belevantsev, V. I.; Peschevitskii, B. I.; Zemskov, S. V. (1976). "New data on chemistry of gold compounds in solutions". Izvestiya Sibirskogo Otdeleniya AN SSSR, Ser. Khim. Nauk. 4 (2): 24–45.
  18. Hill JW, Lear TA (September 1988). "Recovery of gold from electronic scrap". J. Chem. Educ. 65 (9): 802. Bibcode:1988JChEd..65..802H. doi:10.1021/ed065p802.
  19. "Silver Impregnation". Archived from the original on April 21, 2016. Retrieved April 14, 2016.
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