Lithium aluminate

Last updated
Lithium aluminate
LiAlO2 unit cell.png
__ Li +     __ Al 3+     __ O 2−
Names
Preferred IUPAC name
Lithium aluminate
Systematic IUPAC name
Lithium(1+) aluminate
Other names
Lithium metaaluminate

Lithium aluminum oxide

Lithium aluminium double hydroxyde
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.031.291 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 234-434-9
MeSH Lithium+aluminate
PubChem CID
  • InChI=1S/Al.Li.2O/q;+1;;-1 Yes check.svgY
    Key: YQNQTEBHHUSESQ-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/Al.Li.2O/q;+1;;-1/rAlO2.Li/c2-1-3;/q-1;+1
    Key: YQNQTEBHHUSESQ-YICCBGQXAE
  • [Li+].[O-][Al]=O
Properties
AlLiO2
Molar mass 65.92 g·mol−1
Appearancewhite crystalline powder
Density 2.615 g/cm3, solid
Melting point 1,625 [1]  °C (2,957 °F; 1,898 K)
insoluble
Thermochemistry
Std molar
entropy
(S298)
53.35 J/mol·K [2]
-1188.670 kJ/mol [2]
-1126.276 kJ/mol [2]
Hazards
Safety data sheet (SDS) External MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Lithium aluminate (LiAlO
2
), 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.[ citation needed ] In nuclear technology, lithium aluminate is of interest as a solid tritium breeder material, for preparing tritium fuel for nuclear fusion.[ citation needed ] [3] Lithium aluminate is a layered double hydroxide (LDH) with a crystal structure resembling that of hydrotalcite.[ dubious ][ clarification needed ] Lithium aluminate solubility at high pH (12.5 – 13.5) 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. [4] 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. [5] This hinders the aluminium oxidation by the protons of water and reduces the hydrogen evolution rate by a factor of 10. [6]

Contents

Lithium aluminate also finds its use as an inert electrolyte support material in molten carbonate fuel cells, where the electrolyte may be a mixture of lithium carbonate, potassium carbonate, and sodium carbonate. [7]

History

In 1906 Weyberg described his newly synthesized compound, lithium hydrogen aluminate. This was the first known synthesis of this unique compound. He asserted that this new compound had the corresponding chemical formula: [8]

LiHAl
2
O
4
+ 5 H2O

In 1915 Allen and Rogers asserted that an insoluble aluminate of lithium is formed when aluminum is dissolved in a solution of lithium hydroxide. This air-dried substance had an atomic ratio of 2Li:5Al and the chemical formula: [9]

LiH(AlO
2
)
2
+ 5 H2O

In 1929 Prociv recreated Allen and Rogers experiment and through a series of conductometric measurements on the saturated solution of the substance concluded that lithium and aluminum were present in the ratio of 0.8Li:2Al, which, he says, is an atomic ratio of approximately 1Li:2Al. According to him lithium aluminate may also be precipitated by the addition of a solution of lithium hydroxide to a solution of aluminum salt or by adding a solution of lithium salt to a solution of an alkali aluminate. Thus there was disagreement between Allen/Rogers and Prociv as to the composition of lithium aluminate. This may have been attributed to variations between their precipitation conditions. [9]

In 1932 Dobbins and Sanders described the formation of lithium aluminate by the addition of dilute ammonia to a solution containing lithium and aluminum salt, in the presence of phelphtalein as an indicator. In their preparation of acid lithium aluminate they dissolved strips of amalgamated aluminum in normal and tenth normal solutions of lithium hydroxide. The lithium aluminate was precipitated by the addition of a solution of lithium hydroxide to a solution of aluminum salts, or by adding a solution of lithium salt to a solution of alkaline aluminate. In all cases the composition of the compound of lithium aluminate was expressed by the formula: [10]

Li
2
O
2
Al
2
O
2

They claimed that the formed compound contained lithium and aluminum in the atomic ratio of 2Li:5Al. Their chemical formula was simplified into the modern formulation for lithium aluminate:

LiAlO
2

Fields of interest

The fundamental compound of lithium aluminate has found attention in two different fields: nuclear physics and solid-state chemistry. At least five different phases of lithium aluminate have been found. [11] The lithium aluminate crystal structure may be found in either α, β, or γ phases. [12]

Nuclear physicists are interested in the γ-LiAlO
2
modification of lithium aluminate, because of its good performance under high neutron and electron radiation. This modification also exhibits the essential chemical, thermo physical and mechanical stability at high temperature along with the required irradiation behavior. This phase appears to be a promising lithium ceramic, suitable as an in site tritium breeding material in future fusion reactors. [11]

Solid-state chemists investigating preparational routes to lithium aluminate discovered its interesting acid-base chemistry. The α-LiAlO
2
modification (but neither β-LiAlO
2
or γ-LiAlO
2
) reacts with molten benzoic acid leading to nearly total Li+
proton exchange thus forming LiHAl
2
O
4
There is a lot of interest in the chemical reactivity among the three modifications of LiAlO
2
. The reasons for the α-LiAlO
2
modification being highly reactive and the β-LiAlO
2
or γ-LiAlO
2
modifications being totally unreactive is currently a mystery. [11]

Formation

Early methods

Lithium aluminate powder preparation was based on the solid-state reactions between Al
2
O
3
and lithium-containing compounds like Li
2
CO
3
, LiOH, Li
2
O
, LiAc, and reactions occurred at temperatures between 400Deg C to 1000 Deg C. Due to the evaporation of lithium at high temperatures and contamination from grinding operations, pure lithium aluminate with controlled particle size has been difficult to synthesize. [13]

Current methods

Synthesis of lithium aluminate has been essentially performed by several methods: in the solid state, by wet chemical, sol-gel, with the use of templates, various precursors, and combustion processes. The main product in a solid state reaction is the α-LiAlO
2
phase; in a wet chemical reaction, the main product is a solid solution of α-LiAlO
2
and γ-LiAlO
2
phases. [12] The α-LiAlO2 modification (low temperature phase), with a hexagonal structure, undergoes transformation to the γ-modification (High temperature phase), with a tetragonal structure, at about 900 °C. The metastable β-modification, with a monoclinic structure, is assumed to transform to the γ-modification at about 900 °C. [13]

Natural occurrence

The compound is unknown in the natural environment. However, a related compound, LiAl5O8, is known as the very recently discovered (as of 2020) and very rare mineral chukochenite. [14] [15]

Related Research Articles

<span class="mw-page-title-main">Bauxite</span> Sedimentary rock rich in aluminium

Bauxite is a sedimentary rock with a relatively high aluminium content. It is the world's main source of aluminium and gallium. Bauxite consists mostly of the aluminium minerals gibbsite (Al(OH)3), boehmite (γ-AlO(OH)) and diaspore (α-AlO(OH)), mixed with the two iron oxides goethite (FeO(OH)) and haematite (Fe2O3), the aluminium clay mineral kaolinite (Al2Si2O5(OH)4) and small amounts of anatase (TiO2) and ilmenite (FeTiO3 or FeO.TiO2). Bauxite appears dull in luster and is reddish-brown, white, or tan.

<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">Lithium carbonate</span> Chemical compound

Lithium carbonate is an inorganic compound, the lithium salt of carbonic acid with the formula Li
2
CO
3
. This white salt is widely used in processing metal oxides. It is on the World Health Organization's List of Essential Medicines for its efficacy in the treatment of mood disorders such as bipolar disorder.

<span class="mw-page-title-main">Sodium hydroxide</span> Chemical compound with formula NaOH

Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations Na+ and hydroxide anions OH.

<span class="mw-page-title-main">Aluminium oxide</span> Chemical compound with formula Al2O3

Aluminium oxide (or Aluminium(III) oxide) is a chemical compound of aluminium and oxygen with the chemical formula Al2O3. It is the most commonly occurring of several aluminium oxides, and specifically identified as aluminium oxide. It is commonly called alumina and may also be called aloxide, aloxite, or alundum in various forms and applications. It occurs naturally in its crystalline polymorphic phase α-Al2O3 as the mineral corundum, varieties of which form the precious gemstones ruby and sapphire. Al2O3 is significant in its use to produce aluminium metal, as an abrasive owing to its hardness, and as a refractory material owing to its high melting point.

In chemistry, a hydride is formally the anion of hydrogen (H). 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.

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

Aluminium hydroxide, Al(OH)3, is found in nature as the mineral gibbsite (also known as hydrargillite) and its three much rarer polymorphs: bayerite, doyleite, and nordstrandite. Aluminium hydroxide is amphoteric, i.e., it has both basic and acidic properties. Closely related are aluminium oxide hydroxide, AlO(OH), and aluminium oxide or alumina (Al2O3), the latter of which is also amphoteric. These compounds together are the major components of the aluminium ore bauxite. Aluminium hydroxide also forms a gelatinous precipitate in water.

The Bayer process is the principal industrial means of refining bauxite to produce alumina (aluminium oxide) and was developed by Carl Josef Bayer. Bauxite, the most important ore of aluminium, contains only 30–60% aluminium oxide (Al2O3), the rest being a mixture of silica, various iron oxides, and titanium dioxide. The aluminium oxide must be further purified before it can be refined into aluminium metal.

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

Lithium aluminium hydride, commonly abbreviated to LAH, is an inorganic compound with the chemical formula Li[AlH4] or LiAlH4. It is a white solid, discovered by Finholt, Bond and Schlesinger in 1947. This compound is used as a reducing agent in organic synthesis, especially for the reduction of esters, carboxylic acids, and amides. The solid is dangerously reactive toward water, releasing gaseous hydrogen (H2). Some related derivatives have been discussed for hydrogen storage.

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

Raney nickel, also called spongy nickel, is a fine-grained solid composed mostly of nickel derived from a nickel–aluminium alloy. Several grades are known, of which most are gray solids. Some are pyrophoric, but most are used as air-stable slurries. Raney nickel is used as a reagent and as a catalyst in organic chemistry. It was developed in 1926 by American engineer Murray Raney for the hydrogenation of vegetable oils. Raney is a registered trademark of W. R. Grace and Company. Other major producers are Evonik and Johnson Matthey.

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

Sodium aluminate is an inorganic chemical that is used as an effective source of aluminium hydroxide for many industrial and technical applications. Pure sodium aluminate (anhydrous) is a white crystalline solid having a formula variously given as NaAlO2, NaAl(OH)4 (hydrated), Na2O·Al2O3, or Na2Al2O4. Commercial sodium aluminate is available as a solution or a solid.
Other related compounds, sometimes called sodium aluminate, prepared by reaction of Na2O and Al2O3 are Na5AlO4 which contains discrete AlO45− anions, Na7Al3O8 and Na17Al5O16 which contain complex polymeric anions, and NaAl11O17, once mistakenly believed to be β-alumina, a phase of aluminium oxide.

In chemistry, an aluminate is a compound containing an oxyanion of aluminium, such as sodium aluminate. In the naming of inorganic compounds, it is a suffix that indicates a polyatomic anion with a central aluminium atom.

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

Aluminium sulfide is a chemical compound with the formula Al2S3. This colorless species has an interesting structural chemistry, existing in several forms. The material is sensitive to moisture, hydrolyzing to hydrated aluminum oxides/hydroxides. This can begin when the sulfide is exposed to the atmosphere. The hydrolysis reaction generates gaseous hydrogen sulfide (H2S).

Uranium compounds are compounds formed by the element uranium (U). Although uranium is a radioactive actinide, its compounds are well studied due to its long half-life and its applications. It usually forms in the +4 and +6 oxidation states, although it can also form in other oxidation states.

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

Aluminium hydride (also known as alane and alumane) is an inorganic compound with the formula AlH3. Alane and its derivatives are common reducing (hydride addition) reagents in organic synthesis that are used in solution at both laboratory and industrial scales. In solution—typically in etherial solvents such tetrahydrofuran or diethyl ether—aluminium hydride forms complexes with Lewis bases, and reacts selectively with particular organic functional groups (e.g., with carboxylic acids and esters over organic halides and nitro groups), and although it is not a reagent of choice, it can react with carbon-carbon multiple bonds (i.e., through hydroalumination). Given its density, and with hydrogen content on the order of 10% by weight, some forms of alane are, as of 2016, active candidates for storing hydrogen and so for power generation in fuel cell applications, including electric vehicles. As of 2006 it was noted that further research was required to identify an efficient, economical way to reverse the process, regenerating alane from spent aluminium product.

Aluminium hydroxide oxide or aluminium oxyhydroxide, AlO(OH) is found as one of two well defined crystalline phases, which are also known as the minerals boehmite and diaspore. The minerals are important constituents of the aluminium ore, bauxite.

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

Lithium titanates are chemical compounds of lithium, titanium and oxygen. They are mixed oxides and belong to the titanates. The most important lithium titanates are:

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

Lithium iridate, Li2IrO3, is a chemical compound of lithium, iridium and oxygen. It forms black crystals with three slightly different layered atomic structures, α, β, and sometimes γ. Lithium iridate exhibits metal-like, temperature-independent electrical conductivity, and changes its magnetic ordering from paramagnetic to antiferromagnetic upon cooling to 15 K.

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

Aluminium (or aluminum) 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.

Neptunium compounds are compounds containg the element neptunium (Np). Neptunium has five ionic oxidation states ranging from +3 to +7 when forming chemical compounds, which can be simultaneously observed in solutions. It is the heaviest actinide that can lose all its valence electrons in a stable compound. The most stable state in solution is +5, but the valence +4 is preferred in solid neptunium compounds. Neptunium metal is very reactive. Ions of neptunium are prone to hydrolysis and formation of coordination compounds.

References

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  2. 1 2 3 R. Robie, B. Hemingway, and J. Fisher, “Thermodynamic Properties of Minerals and Related Substances at 298.15K and 1bar Pressure and at Higher Temperatures,” US Geol. Surv., vol. 1452, 1978.
  3. "Lithium Aluminate Material Development". Pacific Northwest National Lab. Retrieved 26 July 2023.
  4. MATSUO, Toshiaki; Takashi NISHI; Masami MATSUDA; Tatsuo IZUMIDA (1995). "LiNO
    3
    addition to prevent hydrogen gas generation from cement-solidified aluminum wastes". Journal of Nuclear Science and Technology. 32 (9): 912–920. doi:10.1080/18811248.1995.9731793. ISSN   0022-3131.
  5. Fujita, M.; Tanaka H.; Muramatsu H.; Asoh H.; Ono S. (2013-10-15). Corrosion resistance improvement technology of anodic oxide films on aluminum alloy that uses a lithium hydroxide solution. Warrendale, PA: SAE International. Retrieved 2014-11-08.
  6. MATSUO, Toshiaki; Masami MATSUDA; Michihiko HIRONAGA; Yoshihiko HORIKAWA (1996-11-01). "Effect of LiNO
    3
    on corrosion prevention of aluminum wastes after their land disposal". Journal of Nuclear Science and Technology. 33 (11): 852–862. doi:10.1080/18811248.1996.9732020. ISSN   0022-3131.
  7. Molten carbonate fuel cell electrolyte Archived 2007-09-29 at the Wayback Machine , United States Patent 4079171
  8. Weyberg. Chemisches Zentralblatt (1906): 645. Print.
  9. 1 2 The Formation and Composition of Lithium Aluminate Harold A. Horan and John B. Damiano Journal of the American Chemical Society 1935 57 (12), 2434-2436
  10. Determination of Aluminum. Formation Lithium Aluminate J. T. Dobbins and J. P. Sanders Journal of the American Chemical Society 1932 54 (1), 178-180
  11. 1 2 3 Reactivity and acidity of Li in lithium aluminum oxide (LiAlO2) phases Richard Dronskowski Inorganic Chemistry 1993 32 (1), 1-9
  12. 1 2 Synthesis of lithium aluminate by thermal decomposition of a lithium dawsonite-type precursor J. Jimenez-Becerril & I. Garcia-Sosa, Journal of Ceramic Processing Research. Vol. 12, No. 1, pp. 52-56 (2011)
  13. 1 2 Chatterjee & Naskar “Novel technique for the synthesis of lithium aluminate (LiAlO2) powders from water-based sols” Journal of Materials Science Letters, Vol 22, Issue 24, pp 1747-1749
  14. "Chukochenite".
  15. "List of Minerals". 21 March 2011.