Noble metal
A noble metal is ordinarily regarded as a metallic
In more specialized fields of study and applications the number of elements counted as noble metals can be smaller or larger. In
Meaning and history
While lists of noble metals can differ, they tend to cluster around the six
In addition to this term's function as a compound noun, there are circumstances where noble is used as an adjective for the noun metal. A galvanic series is a hierarchy of metals (or other electrically conductive materials, including composites and semimetals) that runs from noble to active, and allows one to predict how materials will interact in the environment used to generate the series. In this sense of the word, graphite is more noble than silver and the relative nobility of many materials is highly dependent upon context, as for aluminium and stainless steel in conditions of varying pH.[5]
The term noble metal can be traced back to at least the late 14th century[6] and has slightly different meanings in different fields of study and application.
Prior to Mendeleev's publication in 1869 of the first (eventually) widely accepted periodic table, Odling published a table in 1864, in which the "noble metals" rhodium, ruthenium, palladium; and platinum, iridium, and osmium were grouped together,[7] and adjacent to silver and gold.
-
Chalcopyrite, which is copper iron sulfide (CuFeS2), is the most abundant copper ore mineral
-
One half of a ruthenium bar.
Size ~ 40 × 15 × 10 mm
Weight ~44 g -
Rhodium: 1 g powder, 1g pressed cylinder, 1 g pellet.
-
Palladium
-
Acanthite, or silver sulfide (Ag2S)
-
Osmium crystals, 2.2 g
-
Pieces of pure iridium, 1 g, size: 1–3 mm each
-
Crystals of pure platinum
-
Gold nugget from Australia, nearly 9,000 g or 317 oz
-
Cinnabar or mercury sulfide (HgS) is the most common source ore for refining elemental mercury
Properties
Geochemical
The noble metals are
Copper, silver, gold, and the six
Corrosion resistance
Noble metals tend to be highly resistant to oxidation and other forms of corrosion, and this corrosion resistance is often considered to be a defining characteristic. Some exceptions are described below.
Copper is dissolved by nitric acid and aqueous potassium cyanide.
Ruthenium can be dissolved in aqua regia, a highly concentrated mixture of hydrochloric acid and nitric acid, only when in the presence of oxygen, while rhodium must be in a fine pulverized form. Palladium and silver are soluble in nitric acid, while silver's solubility in aqua regia is limited by the formation of silver chloride precipitate.[8]
Rhenium reacts with oxidizing acids, and hydrogen peroxide, and is said to be tarnished by moist air. Osmium and iridium are chemically inert in ambient conditions.[9] Platinum and gold can be dissolved in aqua regia.[10] Mercury reacts with oxidising acids.[9]
In 2010, US researchers discovered that an organic "aqua regia" in the form of a mixture of thionyl chloride SOCl2 and the organic solvent pyridine C5H5N achieved "high dissolution rates of noble metals under mild conditions, with the added benefit of being tunable to a specific metal" for example, gold but not palladium or platinum.[11]
Electronic
In physics, the expression noble metal is sometimes confined to copper, silver, and gold,[n 1] since their full d-subshells contribute to what noble character they have. In contrast, the other noble metals, especially the platinum group metals, have notable catalytic applications, arising from their partially filled d-subshells. This is the case with palladium which has a full d-subshell in the atomic state but in condensed form has a partially filled sp band at the expense of d-band occupancy.[12]
The difference in reactivity can be seen during the preparation of clean metal surfaces in an ultra-high vacuum: surfaces of "physically defined" noble metals (e.g., gold) are easy to clean and keep clean for a long time, while those of platinum or palladium, for example, are covered by carbon monoxide very quickly.[13]
Electrochemical
Element | Z | G | P | Reaction | SRP(V) | EN | EA |
---|---|---|---|---|---|---|---|
Gold ✣ | 79 | 11 | 6 | Au3+ + 3 e− → Au |
1.5 | 2.54 | 223 |
Platinum ✣ | 78 | 10 | 6 | Pt2+ + 2 e− → Pt |
1.2 | 2.28 | 205 |
Iridium ✣ | 77 | 9 | 6 | Ir3+ + 3 e− → Ir |
1.16 | 2.2 | 151 |
Palladium ✣ | 46 | 10 | 5 | Pd2+ + 2 e− → Pd |
0.915 | 2.2 | 54 |
Osmium ✣ | 76 | 8 | 6 | OsO 2 + 4 H+ + 4 e− → Os + 2 H 2O |
0.85 | 2.2 | 104 |
Mercury | 80 | 12 | 6 | Hg2+ + 2 e− → Hg |
0.85 | 2.0 | −50 |
Rhodium ✣ | 45 | 9 | 5 | Rh3+ + 3 e− → Rh |
0.8 | 2.28 | 110 |
Silver ✣ | 47 | 11 | 5 | Ag+ + e− → Ag |
0.7993 | 1.93 | 126 |
Ruthenium ✣ | 44 | 8 | 5 | Ru3+ + 3 e− → Ru |
0.6 | 2.2 | 101 |
Polonium ☢ | 84 | 16 | 6 | Po2+ + 2 e− → Po |
0.6 | 2.0 | 136 |
Water | 2 H 2O + 4 e− +O 2 → 4 OH− |
0.4 | |||||
Copper | 29 | 11 | 4 | Cu2+ + 2 e− → Cu |
0.339 | 2.0 | 119 |
Bismuth | 83 | 15 | 6 | Bi3+ + 3 e− → Bi |
0.308 | 2.02 | 91 |
Technetium ☢ | 43 | 7 | 6 | TcO 2 + 4 H+ + 4 e− → Tc + 2 H 2O |
0.28 | 1.9 | 53 |
Rhenium | 75 | 7 | 6 | ReO 2 + 4 H+ + 4 e− → Re + 2 H 2O |
0.251 | 1.9 | 6 |
ArsenicMD | 33 | 15 | 4 | As 4O 6 + 12 H+ + 12 e− → 4 As + 6 H 2O |
0.24 | 2.18 | 78 |
AntimonyMD | 51 | 15 | 5 | Sb 2O 3 + 6 H+ + 6 e− → 2 Sb + 3 H 2O |
0.147 | 2.05 | 101 |
Z atomic number; G group; P period; SRP standard reduction potential; EN electronegativity; EA electron affinity | |||||||
✣ traditionally recognized as a noble metal; MD metalloid; ☢ radioactive |
The adjacent table lists
The simplified entries in the reaction column can be read in detail from the Pourbaix diagrams of the considered element in water. Noble metals have large positive potentials;[16] elements not in this table have a negative standard potential or are not metals.
Electronegativity is included since it is reckoned to be, "a major driver of metal nobleness and reactivity".[3]
On account of their high electron affinity values,
Arsenic and antimony are usually considered to be metalloids rather than noble metals. However, physically speaking their most stable allotropes are metallic. Semiconductors, such as selenium and tellurium, have been excluded.
The black tarnish commonly seen on silver arises from its sensitivity to hydrogen sulfide:
- 2 Ag + H2S + 1/2O2 → Ag2S + H2O.
Rayner-Canham[4] contends that, "silver is so much more chemically-reactive and has such a different chemistry, that it should not be considered as a 'noble metal'." In dentistry, silver is not regarded as a noble metal due to its tendency to corrode in the oral environment.[19]
The relevance of the entry for water is addressed by Li et al.[20] in the context of galvanic corrosion. Such a process will only occur when:
- "(1) two metals which have different electrochemical potentials are...connected, (2) an aqueous phase with electrolyte exists, and (3) one of the two metals has...potential lower than the potential of the reaction (H
2O + 4e + O
2 = 4 OH•) which is 0.4 V...The...metal with...a potential less than 0.4 V acts as an anode...loses electrons...and dissolves in the aqueous medium. The noble metal (with higher electrochemical potential) acts as a cathode and, under many conditions, the reaction on this electrode is generally H
2O − 4 e• − O
2 = 4 OH•)."
The superheavy elements from hassium (element 108) to livermorium (116) inclusive are expected to be "partially very noble metals"; chemical investigations of hassium has established that it behaves like its lighter congener osmium, and preliminary investigations of nihonium and flerovium have suggested but not definitively established noble behavior.[21] Copernicium's behaviour seems to partly resemble both its lighter congener mercury and the noble gas radon.[22]
Oxides
Element | I | II | III | IV | VI | VII | VIII |
---|---|---|---|---|---|---|---|
Copper | 1232 | 1326 | |||||
Ruthenium | d1300 d75+ |
25 | |||||
Rhodium | d1100 | d1050 | |||||
Palladium | d750[n 2] | ||||||
Silver | d200 | d100[n 3] ? |
|||||
Rhenium | d1000 | d400 | 327 | ||||
Osmium | d500 | 40 | |||||
Iridium | d1100 | ||||||
Platinum | 450 d100 |
||||||
Gold | d150 | ||||||
Mercury | d500 | ||||||
Strontium‡ | 2430 | ||||||
Molybdenum‡ | 801 d70 |
||||||
AntimonyMD | 655 | ||||||
Lanthanum‡ | 2320 | ||||||
Bismuth‡ | 817 | ||||||
d = decomposes; if there are two figures, the 2nd is for the hydrated form; ‡ = not a noble metal; MD = metalloid |
As long ago as 1890, Hiorns observed as follows:
- "Noble Metals. Gold, Platinum, Silver, and a few rare metals. The members of this class have little or no tendency to unite with oxygen in the free state, and when placed in water at a red heat do not alter its composition. The oxides are readily decomposed by heat in consequence of the feeble affinity between the metal and oxygen."[23]
Smith, writing in 1946, continued the theme:
- "There is no sharp dividing line [between 'noble metals' and 'base metals'] but perhaps the best definition of a noble metal is a metal whose oxide is easily decomposed at a temperature below a red heat."[n 4][25]
- "It follows from this that noble metals...have little attraction for oxygen and are consequently not oxidised or discoloured at moderate temperatures."
Such nobility is mainly associated with the relatively high electronegativity values of the noble metals, resulting in only weakly polar covalent bonding with oxygen.[3] The table lists the melting points of the oxides of the noble metals, and for some of those of the non-noble metals, for the elements in their most stable oxidation states.
Catalytic properties
Many of the noble metals can act as catalysts. For example, platinum is used in catalytic converters, devices which convert toxic gases produced in car engines, such as the oxides of nitrogen, into non-polluting substances.
Gold has many industrial applications; it is used as a catalyst in hydrogenation and the water gas shift reaction.
See also
Notes
- ^ See, for example: Harrison WA 1989, Electronic structure and the properties of solids: The physics of the chemical bond, Dover Publications, p. 520
- ^ Palladium oxide PdO can be reduced to palladium metal by exposing it to hydrogen in ambient conditions[10]
- ^ Ag4O4 is a mixed oxidation state compound silver in the oxidation state of 1 and 3.
- ^ Incipient red heat corresponds to 525 °C[24]
References
- ISBN 9780471976707.
- ISBN 978-3-319-69741-3.
- ^ S2CID 210087180.
- ^ ISBN 978-0-190-668532.
- ^ Everett Collier, "The Boatowner's Guide to Corrosion", International Marine Publishing, 2001, p. 21
- ^ "the definition of noble metal". Dictionary.com. Retrieved April 6, 2018.
- ^ W. Xing, M. Lee, Geosys. Eng. 20, 216, 2017
- ^ a b Parish RV 1977, The metallic elements, Longman, London, p. 53, 115
- ^ a b A. Holleman, N. Wiberg, "Inorganic Chemistry", Academic Press, 2001
- ^ Urquhart J 2010, "Challenging aqua regia's throne", Chemistry World, 24 September
- S2CID 250786579.
- ^ S. Fuchs, T.Hahn, H.G. Lintz, "The oxidation of carbon monoxide by oxygen over platinum, palladium and rhodium catalysts from 10−10 to 1 bar", Chemical engineering and processing, 1994, V 33(5), pp. 363–369 [1]
- ^ G. Wulfsberg 2000, "Inorganic Chemistry", University Science Books, Sausalito, CA, pp. 270, 937.
- ^ G. Wulfsberg, "Inorganic Chemistry", University Science Books, 2000, pp. 247–249 ✦ Bratsch S. G., "Standard Electrode Potentials and Temperature Coefficients in Water at 298.15 K", Journal of Physical Chemical Reference Data, vol. 18, no. 1, 1989, pp. 1–21 ✦ B. Douglas, D. McDaniel, J. Alexander, "Concepts and Models of Inorganic Chemistry", John Wiley & Sons, 1994, p. E-3
- ISBN 9780080480336.
- ^ Viswanathan, B (2002). Catalysis: Principles and Applications. Boca Raton: CRC Press. p. 291.
- doi:10.1063/1.89262.
- ^
Powers, JM; Wataha, JE (2013). Dental materials: Properties and manipulation (10th ed.). St Louis: Elsevier Health Sciences. p. 134. ISBN 9780323291507.
- ISBN 978-0-387-88782-1.
- .
- PMID 31596013.
- ^ Hiorns AH 1890, Mixed metals or metallic alloys, p. 7
- ^ Hiorns RH 1890, Mixed metals or metallic alloys, MacMillian, New York, p. 5
- ^ Smith, JC (1946). The chemistry and metallurgy of dental materials. Oxford: Blackwell. p. 40.
Further reading
- Balshaw L 2020, "Noble metals dissolved without aqua regia", Chemistry World, 1 September
- Beamish FE 2012, The analytical chemistry of the noble metals, Elsevier Science, Burlington
- Brasser R, Mojzsis SJ 2017, "A colossal impact enriched Mars' mantle with noble metals", Geophys. Res. Lett., vol. 44, pp. 5978–5985,
- Brooks RR (ed.) 1992, Noble metals and biological systems: Their role in medicine, mineral exploration, and the environment, CRC Press, Boca Raton
- Brubaker PE, Moran JP, Bridbord K, Hueter FG 1975, "Noble metals: a toxicological appraisal of potential new environmental contaminants", Environmental Health Perspectives, vol. 10, pp. 39–56,
- Du R et al. 2019, "Emerging noble metal aerogels: State of the art and a look forward", Matter, vol. 1, pp. 39–56
- Hämäläinen J, Ritala M, Leskelä M 2013, "Atomic layer deposition of noble metals and their oxides", Chemistry of Materials, vol. 26, no. 1, pp. 786–801, doi:10.1021/cm402221
- Kepp K 2020, "Chemical causes of metal nobleness", ChemPhysChem, vol. 21 no. 5. pp. 360−369,
- Lal H, Bhagat SN 1985, "Gradation of the metallic character of noble metals on the basis of thermoelectric properties", Indian Journal of Pure and Applied Physics, vol. 23, no. 11, pp. 551–554
- Lyon SB 2010, "3.21 - Corrosion of noble metals", in B Cottis et al. (eds.), Shreir's Corrosion, Elsevier, pp. 2205–2223,
- Medici S, Peana MF, Zoroddu MA 2018, "Noble metals in pharmaceuticals: Applications and limitations", in M Rai M, Ingle, S Medici (eds.), Biomedical applications of metals, Springer,
- Pan S et al. 2019, "Noble-noble strong union: Gold at its best to make a bond with a noble gas atom", ChemistryOpen, vol. 8, p. 173,
- Russel A 1931, "Simple deposition of reactive metals on noble metals", Nature, vol. 127, pp. 273–274, doi:10.1038/127273b0
- St. John J et al. 1984, Noble metals, Time-Life Books, Alexandria, VA
- Wang H 2017, "Chapter 9 - Noble Metals", in LY Jiang, N Li (eds.), Membrane-based separations in metallurgy, Elsevier, pp. 249–272,
External links
- Noble metal – chemistry Encyclopædia Britannica, online edition