Aluminium amalgam

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Aluminium can form an amalgam in solution with mercury. Aluminium amalgam may be prepared by either grinding aluminium pellets or wire in mercury, or by allowing aluminium wire to react with a solution of mercury(II) chloride in water.[1][2]

This amalgam is used as a chemical reagent to reduce compounds, such as the reduction of imines to amines. The aluminium is the ultimate electron donor, and the mercury serves to mediate the electron transfer.

The reaction itself and the waste from it contain mercury, so special safety precautions and disposal methods are needed. As an environmentally friendlier alternative, hydrides or other reducing agents can often be used to accomplish the same synthetic result. Another environmentally friendly alternative is an alloy of aluminium and gallium which similarly renders the aluminium more reactive by preventing it from forming an oxide layer.[3]

Reactivity[edit]

Aluminium in air is ordinarily protected by a molecule-thin layer of its own oxide. This aluminium oxide layer serves as a protective barrier to the underlying aluminium itself and preventing chemical reactions with the metal. Mercury coming into contact with it does no harm. However, if any elemental aluminium is exposed (even by a recent scratch), the mercury may combine with it to form the amalgam. This process can continue well beyond the immediately exposed metal surface, potentially reacting with a large part of the bulk aluminium before it finally ends.[4]

The net result is similar to the mercury electrodes often used in electrochemistry, except instead of providing electrons from an electrical supply they are provided by the aluminium which becomes oxidized in the process. The reaction that occurs at the surface of the amalgam may actually be a hydrogenation rather than a reduction.

The presence of water in the solution is reportedly helpful—even necessary; the electron rich amalgam will oxidize aluminium and reduce H+ from water, creating aluminium hydroxide (Al(OH)3) and hydrogen gas (H2). The electrons from the aluminium reduce mercuric Hg2+ ion to metallic mercury. The metallic mercury can then form an amalgam with the exposed aluminium metal. The amalgamated aluminium then is oxidized by water, converting the aluminium to aluminium hydroxide and releasing free metallic mercury. The generated mercury then cycles through these last two steps until the aluminium metal supply is exhausted.[4]

The three reaction steps of the aluminium amalgam reaction. The first step reduces mercury ions to mercury metal. While the bottom two reactions continuously cycle until the aluminium supply is exhausted.

Due to the reactivity of aluminium amalgam, restrictions are placed on the use and handling of mercury in proximity with aluminium. In particular, large amounts of mercury are not allowed aboard aircraft under most circumstances because of the risk of it forming amalgam with exposed aluminium parts in the aircraft.[5] In the Second World War, mercury may have been used to sabotage aircraft.[6][dubious ] Accidental mercury spills in aircraft do sometimes result in insurance write-offs,[7] and is why there are severe restrictions on the transport of mercury-containing thermometers or barometers on commercial aircraft.[8]

References[edit]

  1. ^ Ward Chesworth (1971). "Use of aluminum-amalgam in mineral synthesis at low temperatures and 1 atmosphere total pressure". Clays and Clay Minerals 19 (5): 337–339. Bibcode:1971CCM....19..337C. doi:10.1346/CCMN.1971.0190510. 
  2. ^ Lourdes Muñoz, Esmeralda Rosa, Ma Pilar Bosch and Angel Guerrero (2005). "A new, practical and efficient sulfone-mediated synthesis of trifluoromethyl ketones from alkyl and alkenyl bromides". Tetrahedron Letters 46 (19): 3311–3313. doi:10.1016/j.tetlet.2005.03.106. 
  3. ^ http://news.uns.purdue.edu/x/2007a/070515WoodallHydrogen.html
  4. ^ a b Bessone, J (2006). "The activation of aluminium by mercury ions in non-aggressive media". Corrosion Science 12: 4243–4256. doi:10.1016/j.corsci.2006.03.013. 
  5. ^ 49 C.F.R. 175.10
  6. ^ Gray, Theodore (2004-09-22). "The Amazing Rusting Aluminum". Popular Science. 
  7. ^ "List of incidents where aircraft have had mercury spills in them". Archived from the original on 21 March 2009. Retrieved 2009-03-17. 
  8. ^ See for example United States Department of Transportation regulation 49 CFR 175.10(a)(13)

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