Aluminium amalgam

Last updated

Aluminium amalgam is a solution of aluminium in mercury. In practice the term refers to particles or pieces of aluminium with a surface coating of the amalgam. A gray solid, it is typically used for organic reductions. It is written as Al(Hg) in reactions. [1]

Contents

Al(Hg) 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. [2] [3] [1]

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

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. [4] 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. [5]

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. 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 supply is exhausted. [5]

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. [6] Even the transportation and packaging of mercury-containing thermometers and barometers is severely restricted. [7] Accidental mercury spills in aircraft do sometimes result in insurance write-offs. [8]

See also

Related Research Articles

<span class="mw-page-title-main">Aluminium</span> Chemical element with atomic number 13 (Al)

Aluminium is a chemical element; it has symbol Al and atomic number 13. Aluminium has a density lower than that of other common metals, about one-third that of steel. It has a great affinity towards oxygen, forming a protective layer of oxide on the surface when exposed to air. Aluminium visually resembles silver, both in its color and in its great ability to reflect light. It is soft, nonmagnetic, and ductile. It has one stable isotope, 27Al, which is highly abundant, making aluminium the twelfth-most common element in the universe. The radioactivity of 26Al leads to it being used in radiometric dating.

<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 ion with two electrons. In modern usage, this is typically only used for ionic bonds, but it is sometimes (and more frequently in the past) been applied to all compounds containing covalently bound H atoms. In this broad and potentially archaic sense, water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. In covalent compounds, it implies hydrogen is 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, a reducing agent is a chemical species that "donates" an electron to an electron recipient.

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.

<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 an archaic concept in chemistry. It describes the stoichiometry of some chemical reactions in which one element or ligand is replaced by atom or group.

<span class="mw-page-title-main">Organic redox reaction</span> Redox reaction that takes place with organic compounds

Organic reductions or organic oxidations or organic redox reactions are redox reactions that take place with organic compounds. In organic chemistry oxidations and reductions are different from ordinary redox reactions, because many reactions carry the name but do not actually involve electron transfer. Instead the relevant criterion for organic oxidation is gain of oxygen and/or loss of hydrogen. Simple functional groups can be arranged in order of increasing oxidation state. The oxidation numbers are only an approximation:

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

Aluminium isopropoxide is the chemical compound usually described with the formula Al(O-i-Pr)3, where i-Pr is the isopropyl group (–CH(CH3)2). This colourless solid is a useful reagent in organic synthesis.

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

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">Gallium(III) chloride</span> Chemical compound

Gallium(III) chloride is an inorganic chemical compound with the formula GaCl3 which forms a monohydrate, GaCl3·H2O. Solid gallium(III) chloride is a deliquescent white solid and exists as a dimer with the formula Ga2Cl6. It is colourless and soluble in virtually all solvents, even alkanes, which is truly unusual for a metal halide. It is the main precursor to most derivatives of gallium and a reagent in organic synthesis.

<span class="mw-page-title-main">Organoaluminium chemistry</span>

Organoaluminium chemistry is the study of compounds containing bonds between carbon and aluminium. It is one of the major themes within organometallic chemistry. Illustrative organoaluminium compounds are the dimer trimethylaluminium, the monomer triisobutylaluminium, and the titanium-aluminium compound called Tebbe's reagent. The behavior of organoaluminium compounds can be understood in terms of the polarity of the C−Al bond and the high Lewis acidity of the three-coordinated species. Industrially, these compounds are mainly used for the production of polyolefins.

<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, basic metals, and chemically weak metals. The most common name, post-transition metals, is generally used in this article.

In organic chemistry, the Ziegler process is a method for producing fatty alcohols from ethylene using an organoaluminium compound. The reaction produces linear primary alcohols with an even numbered carbon chain. The process uses an aluminum compound to oligomerize ethylene and allow the resulting alkyl group to be oxygenated. The usually targeted products are fatty alcohols, which are otherwise derived from natural fats and oils. Fatty alcohols are used in food and chemical processing. They are useful due to their amphipathic nature. The synthesis route is named after Karl Ziegler, who described the process in 1955.

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.

In chemistry, aluminium(I) refers to monovalent aluminium (+1 oxidation state) in both ionic and covalent bonds. Along with aluminium(II), it is an extremely unstable form of aluminium.

<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. 1 2 Troyansky, Emmanuil I.; Baker, Meghan (2016). "Aluminum Amalgam". Encyclopedia of Reagents for Organic Synthesis. pp. 1–6. doi:10.1002/047084289X.ra076.pub2. ISBN   978-0-470-84289-8.
  2. 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 .
  3. 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.
  4. "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.
  5. 1 2 Bessone, J (2006). "The activation of aluminium by mercury ions in non-aggressive media". Corrosion Science. 48 (12): 4243–4256. Bibcode:2006Corro..48.4243B. doi:10.1016/j.corsci.2006.03.013.
  6. "49 C.F.R. 175.10". gpoaccess.gov. Archived from the original on 2008-10-15. Retrieved 2009-03-17.
  7. See for example United States Department of Transportation regulation 49 CFR 175.10(a)(13)
  8. "List of incidents where aircraft have had mercury spills in them". Archived from the original on 21 March 2009. Retrieved 2009-03-17.