Chloroplatinic acid

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Chloroplatinic acid (also known as hexachloroplatinic acid) is an inorganic compound with the formula [H3O]2[PtCl6](H2O)x (0 ≤ x ≤ 6). A red solid, it is an important commercial source of platinum, usually as an aqueous solution. Although often written in shorthand as H2PtCl6, it is the hydronium (H3O+) salt of the hexachloroplatinate anion (PtCl2−6).[1][2][3] Hexachloroplatinic acid is highly hygroscopic.

Production

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Platinum being dissolved in hot aqua regia

Hexachloroplatinic acid may be produced via a variety of methods. The most common of these methods involves dissolution of platinum in aqua regia. Other methods include exposing an aqueous suspension of platinum particles to chlorine gas, or via electrolysis.

When produced by the aqua regia route, hexachloroplatinic acid is thought to arise by the following equation: [4][5]

Pt + 4 HNO3 + 6 HCl → H2PtCl6 + 4 NO2 + 4 H2O

The resulting orange/red solution can be evaporated to produce brownish red crystals. Some authors suggest that hexachloroplatinic acid produced using this method is contaminated with nitrosonium hexachloroplatinate. Newer literature indicates that this is not the case, and that once the nitric acid has been driven off, samples prepared via this method contain no detectable nitrogen.

Alternative methods have been investigated and described, often motivated by the avoidance of nitrogen contamination.[6]

Structure

Structure of solid hexachloroplatinic acid. Color code: green = Cl, red = O, gray = Pt. H atoms not shown.

According to X-ray crystallography, hexachloroplatinic acid consists of octahedral PtCl2−6  ions linked by hydrogen bonding. The cubic array of these octahedra encase water molecules.[7]

Reactions

When heated, hexachloroplatinic acid decomposes to platinum(IV) chloride.[1]

(H3O)2PtCl6·nH2O → PtCl4 + 2 HCl + (n + 2) H2O

Applications

Potassium determination

Chloroplatinic acid was popularized for the quantitative analysis of potassium. The potassium is selectively precipitated from solution as potassium hexachloroplatinate. Determinations were done in 85% (v/v) alcohol solutions with excess platinate ions, and the precipitated product was weighed. Potassium could be detected for solutions as dilute as 0.02 to 0.2% (m/v).[8]

This method for determination of potassium was advantageous compared to the sodium cobaltinitrite method used previously, since it required a single precipitation reaction.[8]Gravimetric analysis of precipitated products has been supplanted by modern instrumental analysis methods such as ion selective electrodes, flame photometry, ICP-AES or ICP-MS.

Purification of platinum

Upon treatment with an ammonium salt, such as ammonium chloride, chloroplatinic acid converts to ammonium hexachloroplatinate, which precipitates as a solid.[4] Upon heating in an atmosphere of hydrogen, the ammonium salt converts to elemental platinum. Platinum is often isolated from ores or recycled from residues using this method.[9]

Catalysis

Like many platinum compounds, chloroplatinic acid is a catalyst (or precatalyst) for hydrogenation and related reactions. As first reported by John Speier and colleagues from Dow Corning, it catalyzes the addition of hydrosilanes to olefins, i.e. hydrosilylation. Early demonstration reactions used isopropanol solutions of trichlorosilane (SiHCl3) with pentenes. Prior work on the addition of silanes to alkenes required radical reactions that were inefficient.[10][11] As well as with Karstedt's catalyst, Speier's catalyst enjoys widespread use for hydrosilylation, the main drawback is the deliquescent properties of the catalyst.[12]

It is generally agreed that chloroplatinic acid is a precursor to the actual catalyst. A possible role for colloidal platinum or zero-valent complexes has also been considered.[13]

Chloroplatinic acid prepared from aqua regia is proposed to contain nitrosonium hexachloroplatinate, (NO)2PtCl6. Nitrosonium hexachloroplatinate is obtained by the reaction of nitrosyl chloride (NOCl) and platinum metal.[14] Nitrosonium hexachloroplatinate has been found to react vigorously with water and hydrochloric acid, making contamination of chloroplatinic acid prepared with aqua regia with nitrosonium hexachloroplatinate unlikely.

References

  1. 12Schweizer, A. E.; Kerr, G. T. (1978). "Thermal Decomposition of Hexachloroplatinic Acid". Inorg. Chem.17 (8): 2326–2327. doi:10.1021/ic50186a067.
  2. ↑Holleman; Wiberg (2001). Inorganic Chemistry (First ed.). New York: Academic Press. ISBN 0-12-352651-5.
  3. ↑Greenwood, N. N.; Earnshaw, A. (1997). Chemistry of the Elements (Second ed.). New York: Elsevier Butterworth-Heinemann. ISBN 978-0-7506-3365-9.
  4. 12Kauffman, George B. (1967). "Ammonium Hexachloroplatinate(IV)". Inorganic Syntheses. Inorganic Syntheses. Vol. 9. pp. 182–185. doi:10.1002/9780470132401.ch51. ISBN 9780470132401.
  5. ↑Grube, H. (1963). "Hexachloroplatinic(IV) Acid". In Brauer, G. (ed.). Handbook of Preparative Inorganic Chemistry. Vol. 2 (2nd ed.). New York: Academic Press. p. 1569.
  6. ↑Rudnick, Paul; Cooke, R. D. (1917). "The Preparation of Hydrochloroplatinic Acid by Means of Hydrogen Peroxide". J. Am. Chem. Soc.39 (4): 633–635. Bibcode:1917JAChS..39..633R. doi:10.1021/ja02249a011.
  7. ^ راو، ف. كليمنت، يو. النطاق، K.-J. (1995). "التركيب البلوري لسداسي كلوروبلاتينات الأوكسونيوم (IV)، (H 3 O) 2 PtCl 6 ". Zeitschrift für Kristallographie - المواد البلورية . 210 (9): 684. بيب كود : 1995ZK....210..684R . دوى : 10.1524/zkri.1995.210.9.684 .
  8. 1 2 سميث، ج. فريدريك؛ غرينغ، ج. ل. (1933). "فصل وتحديد الفلزات القلوية باستخدام حمض البيركلوريك. 5. حمض البيركلوريك وحمض الكلوروبلاتينيك في تحديد كميات صغيرة من البوتاسيوم في وجود كميات كبيرة من الصوديوم". مجلة الجمعية الكيميائية الأمريكية 55 (10): 3957-3961 . Bibcode : 1933JAChS..55.3957S . doi : 10.1021/ja01337a007 .
  9. ↑ كوتون، إس. أ. (1997). كيمياء المعادن الثمينة . لندن: تشابمان وهول. ISBN 0-7514-0413-6.
  10. ↑ سبير، جيه إل؛ ويبستر، جيه إيه؛ بارنز، جي إتش (1957). "إضافة هيدريدات السيليكون إلى الروابط المزدوجة الأوليفينية. الجزء الثاني: استخدام محفزات فلزات المجموعة الثامنة". مجلة الجمعية الكيميائية الأمريكية 79 (4): 974-979 . Bibcode : 1957JAChS..79..974S . doi : 10.1021/ja01561a054 .
  11. ↑ سام، جون سي؛ سبير، جون إل. (1958). "إضافة هيدريدات السيليكون إلى الروابط المزدوجة الأوليفينية. الجزء الثالث: الإضافة إلى الأوليفينات غير الطرفية في وجود حمض الكلوروبلاتينيك". مجلة الجمعية الكيميائية الأمريكية 80 (15): 4104-4106 . Bibcode : 1958JAChS..80.4104S . doi : 10.1021/ja01548a073 .
  12. ↑ سيبي، موكوند ب. (2001). "سداسي كلورو البلاتينات الهيدروجيني (IV)". موسوعة الكواشف للتخليق العضوي . جون وايلي وأولاده. doi : 10.1002/047084289X.rh038 . ISBN 0471936235.
  13. ↑ لويس، إل إن؛ سي، كيه جي؛ براينت، جي إل؛ دوناهو، بي إي (1991). "هدرجة الألكاينات المحفزة بالبلاتين". مركبات عضوية فلزية . 10 (10): 3750-3759 . doi : 10.1021/om00056a055 .
  14. ↑ مورافيك، آر تي؛ كوفمان، جي بي؛ محمود، تي. (1967). "نيتروزيل سداسي كلورو البلاتينات (IV)". التخليق غير العضوي . التخليق غير العضوي . المجلد 9. الصفحات 217-220 . doi : 10.1002/9780470132555.ch63 . ISBN   9780470132555.