Aluminium amalgam

Last updated

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]

Contents

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 and the waste from it contains 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. An alloy of aluminium and gallium was proposed as a method of hydrogen generation, as the gallium renders the aluminium more reactive by preventing it from forming an oxide layer. [3] Mercury has this same effect on aluminium, but also serves additional functions related to electron transfer that make aluminium amalgams useful for some reactions that would not be possible with gallium.

Reactivity

Aluminium exposed to 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 unoxidized aluminium and prevents amalgamation from occurring. No reaction takes place when oxidized aluminium is exposed to mercury. However, if any elemental aluminium is exposed (even by a recent scratch), the mercury may combine with it to form the amalgam. This amalgamation can continue well beyond the vulnerable aluminium that was exposed, potentially reacting with a large amount of the raw aluminium before it finally ends. [4]

The net result is similar to the mercury electrodes often used in electrochemistry, however 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 necessary; the electron rich amalgam will oxidize aluminium and generate hydrogen gas from water, creating aluminium hydroxide (Al(OH)3) and free mercury. The electrons from the aluminium reduce mercuric Hg2+ ion[ clarification needed ] 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]

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] Even the transportation and packaging of mercury-containing thermometers and barometers is severely restricted. [6] Accidental mercury spills in aircraft do sometimes result in insurance write-offs. [7]

See also

Related Research Articles

<span class="mw-page-title-main">Gallium</span> Chemical element, symbol Ga and atomic number 31

Gallium is a chemical element; it has symbol Ga and atomic number 31. Discovered by the French chemist Paul-Émile Lecoq de Boisbaudran in 1875, gallium is in group 13 of the periodic table and is similar to the other metals of the group.

<span class="mw-page-title-main">Hydroxide</span> Chemical compound

Hydroxide is a diatomic anion with chemical formula OH. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It functions as a base, a ligand, a nucleophile, and a catalyst. The hydroxide ion forms salts, some of which dissociate in aqueous solution, liberating solvated hydroxide ions. Sodium hydroxide is a multi-million-ton per annum commodity chemical. The corresponding electrically neutral compound HO is the hydroxyl radical. The corresponding covalently bound group –OH of atoms is the hydroxy group. Both the hydroxide ion and hydroxy group are nucleophiles and can act as catalysts in organic chemistry.

<span class="mw-page-title-main">Rust</span> Type of iron oxide

Rust is an iron oxide, a usually reddish-brown oxide formed by the reaction of iron and oxygen in the catalytic presence of water or air moisture. Rust consists of hydrous iron(III) oxides (Fe2O3·nH2O) and iron(III) oxide-hydroxide (FeO(OH), Fe(OH)3), and is typically associated with the corrosion of refined iron.

<span class="mw-page-title-main">Electrolysis</span> Technique in chemistry and manufacturing

In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from naturally occurring sources such as ores using an electrolytic cell. The voltage that is needed for electrolysis to occur is called the decomposition potential. The word "lysis" means to separate or break, so in terms, electrolysis would mean "breakdown via electricity".

<span class="mw-page-title-main">Base (chemistry)</span> Type of chemical substance

In chemistry, there are three definitions in common use of the word "base": Arrhenius bases, Brønsted bases, and Lewis bases. All definitions agree that bases are substances that react with acids, as originally proposed by G.-F. Rouelle in the mid-18th century.

<span class="mw-page-title-main">Hydride</span> Molecule with a hydrogen bound to a more electropositive element or group

In chemistry, a hydride is formally the anion of hydrogen (H), a hydrogen atom with two electrons. The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. For inorganic chemists, hydrides refer to compounds and ions in which hydrogen is covalently attached to a less electronegative element. In such cases, the H centre has nucleophilic character, which contrasts with the protic character of acids. The hydride anion is very rarely observed.

In chemistry, an amphoteric compound is a molecule or ion that can react both as an acid and as a base. What exactly this can mean depends on which definitions of acids and bases are being used.

In chemistry, a reactivity series (or reactivity series of elements) is an empirical, calculated, and structurally analytical progression of a series of metals, arranged by their "reactivity" from highest to lowest. It is used to summarize information about the reactions of metals with acids and water, single displacement reactions and the extraction of metals from their ores.

The Brønsted–Lowry theory (also called proton theory of acids and bases) is an acid–base reaction theory which was first developed by Johannes Nicolaus Brønsted and Thomas Martin Lowry independently in 1923. The basic concept of this theory is that when an acid and a base react with each other, the acid forms its conjugate base, and the base forms its conjugate acid by exchange of a proton (the hydrogen cation, or H+). This theory generalises the Arrhenius theory.

The chloralkali process is an industrial process for the electrolysis of sodium chloride (NaCl) solutions. It is the technology used to produce chlorine and sodium hydroxide, which are commodity chemicals required by industry. Thirty five million tons of chlorine were prepared by this process in 1987. The chlorine and sodium hydroxide produced in this process are widely used in the chemical industry.

<span class="mw-page-title-main">Single displacement reaction</span> Type of chemical reaction

A single-displacement reaction, also known as single replacement reaction or exchange reaction, is a chemical reaction in which one element is replaced by another in a compound.

In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. The reverse of disproportionation, such as when a compound in an intermediate oxidation state is formed from precursors of lower and higher oxidation states, is called comproportionation, also known as synproportionation.

<span class="mw-page-title-main">Mercury battery</span>

A mercury battery is a non-rechargeable electrochemical battery, a primary cell. Mercury batteries use a reaction between mercuric oxide and zinc electrodes in an alkaline electrolyte. The voltage during discharge remains practically constant at 1.35 volts, and the capacity is much greater than that of a similarly sized zinc-carbon battery. Mercury batteries were used in the shape of button cells for watches, hearing aids, cameras and calculators, and in larger forms for other applications.

<span class="mw-page-title-main">Aluminium iodide</span> Chemical compound

Aluminium iodide is a chemical compound containing aluminium and iodine. Invariably, the name refers to a compound of the composition AlI
3
, formed by the reaction of aluminium and iodine or the action of HI on Al metal. The hexahydrate is obtained from a reaction between metallic aluminum or aluminum hydroxide with hydrogen iodide or hydroiodic acid. Like the related chloride and bromide, AlI
3
is a strong Lewis acid and will absorb water from the atmosphere. It is employed as a reagent for the scission of certain kinds of C-O and N-O bonds. It cleaves aryl ethers and deoxygenates epoxides.

<span class="mw-page-title-main">Lithium aluminate</span> Chemical compound

Lithium aluminate, also called lithium aluminium oxide, is an inorganic chemical compound, an aluminate of lithium. In microelectronics, lithium aluminate is considered as a lattice matching substrate for gallium nitride. In nuclear technology, lithium aluminate is of interest as a solid tritium breeder material, for preparing tritium fuel for nuclear fusion. Lithium aluminate is a layered double hydroxide (LDH) with a crystal structure resembling that of hydrotalcite. Lithium aluminate solubility at high pH is much lower than that of aluminium oxides. In the conditioning of low- and intermediate level radioactive waste (LILW), lithium nitrate is sometimes used as additive to cement to minimise aluminium corrosion at high pH and subsequent hydrogen production. Indeed, upon addition of lithium nitrate to cement, a passive layer of LiH(AlO
2
)
2
· 5 H
2
O
is formed onto the surface of metallic aluminium waste immobilised in mortar. The lithium aluminate layer is insoluble in cement pore water and protects the underlying aluminium oxide covering the metallic aluminium from dissolution at high pH. It is also a pore filler. This hinders the aluminium oxidation by the protons of water and reduces the hydrogen evolution rate by a factor of 10.

<span class="mw-page-title-main">Amalgam (chemistry)</span> Alloy of mercury with another metal

An amalgam is an alloy of mercury with another metal. It may be a liquid, a soft paste or a solid, depending upon the proportion of mercury. These alloys are formed through metallic bonding, with the electrostatic attractive force of the conduction electrons working to bind all the positively charged metal ions together into a crystal lattice structure. Almost all metals can form amalgams with mercury, the notable exceptions being iron, platinum, tungsten, and tantalum. Silver-mercury amalgams are important in dentistry, and gold-mercury amalgam is used in the extraction of gold from ore. Dentistry has used alloys of mercury with metals such as silver, copper, indium, tin and zinc.

<span class="mw-page-title-main">Post-transition metal</span> Category of metallic elements

The metallic elements in the periodic table located between the transition metals to their left and the chemically weak nonmetallic metalloids to their right have received many names in the literature, such as post-transition metals, poor metals, other metals, p-block metals and chemically weak metals. The most common name, post-transition metals, is generally used in this article.

AlGa (Aluminum-Gallium) is a degenerate alloy that results from liquid gallium infiltrating the crystal structure of aluminium metal. The resulting alloy is very weak and brittle, being broken under the most minute pressure. The alloy is also chemically weaker, as the gallium inhibits the aluminum from forming a protective oxide layer. A video of gallium metal causing intergrain corrosion and breaking of aluminum can be found here.

<span class="mw-page-title-main">Aluminium compounds</span>

Aluminium (British and IUPAC spellings) or aluminum (North American spelling) combines characteristics of pre- and post-transition metals. Since it has few available electrons for metallic bonding, like its heavier group 13 congeners, it has the characteristic physical properties of a post-transition metal, with longer-than-expected interatomic distances. Furthermore, as Al3+ is a small and highly charged cation, it is strongly polarizing and aluminium compounds tend towards covalency; this behaviour is similar to that of beryllium (Be2+), an example of a diagonal relationship. However, unlike all other post-transition metals, the underlying core under aluminium's valence shell is that of the preceding noble gas, whereas for gallium and indium it is that of the preceding noble gas plus a filled d-subshell, and for thallium and nihonium it is that of the preceding noble gas plus filled d- and f-subshells. Hence, aluminium does not suffer the effects of incomplete shielding of valence electrons by inner electrons from the nucleus that its heavier congeners do. Aluminium's electropositive behavior, high affinity for oxygen, and highly negative standard electrode potential are all more similar to those of scandium, yttrium, lanthanum, and actinium, which have ds2 configurations of three valence electrons outside a noble gas core: aluminium is the most electropositive metal in its group. Aluminium also bears minor similarities to the metalloid boron in the same group; AlX3 compounds are valence isoelectronic to BX3 compounds (they have the same valence electronic structure), and both behave as Lewis acids and readily form adducts. Additionally, one of the main motifs of boron chemistry is regular icosahedral structures, and aluminium forms an important part of many icosahedral quasicrystal alloys, including the Al–Zn–Mg class.

Gallium compounds are compounds containing the element gallium. These compounds are found primarily in the +3 oxidation state. The +1 oxidation state is also found in some compounds, although it is less common than it is for gallium's heavier congeners indium and thallium. For example, the very stable GaCl2 contains both gallium(I) and gallium(III) and can be formulated as GaIGaIIICl4; in contrast, the monochloride is unstable above 0 °C, disproportionating into elemental gallium and gallium(III) chloride. Compounds containing Ga–Ga bonds are true gallium(II) compounds, such as GaS (which can be formulated as Ga24+(S2−)2) and the dioxan complex Ga2Cl4(C4H8O2)2. There are also compounds of gallium with negative oxidation states, ranging from -5 to -1, most of these compounds being magnesium gallides (MgxGay).

References

  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; 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. "New process generates hydrogen from aluminum alloy to run engines, fuel cells". news.uns.purdue.edu. Archived from the original on 2008-02-01. Retrieved 2012-06-05.
  4. 1 2 Bessone, J (2006). "The activation of aluminium by mercury ions in non-aggressive media". Corrosion Science. 48 (12): 4243–4256. doi:10.1016/j.corsci.2006.03.013.
  5. "49 C.F.R. 175.10". gpoaccess.gov. Archived from the original on 2008-10-15. Retrieved 2009-03-17.
  6. See for example United States Department of Transportation regulation 49 CFR 175.10(a)(13)
  7. "List of incidents where aircraft have had mercury spills in them". Archived from the original on 21 March 2009. Retrieved 2009-03-17.