Chemistry:Lithium aluminate

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Lithium aluminate
LiAlO2 unit cell.png
__ Li+     __ Al3+     __ O2−
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
EC Number
  • 234-434-9
MeSH Lithium+aluminate
Properties
AlLiO2
Molar mass 65.92 g·mol−1
Appearance white crystalline powder
Density 2.615 g/cm3, solid
Melting point 1,625[1] °C (2,957 °F; 1,898 K)
insoluble
Thermochemistry
53.35 J/mol·K [2]
-1188.670 kJ/mol [2]
-1126.276 kJ/mol [2]
Hazards
Safety data sheet External MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Lithium aluminate (LiAlO2), 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 – discuss][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(AlO2)2 · 5 H2O 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]

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]

LiHAl2O4 + 5 H
2O

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(AlO2)2 + 5 H
2O

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]

Li2O2Al2O2

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:

LiAlO2

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-LiAlO2 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-LiAlO2 modification (but neither β-LiAlO2 or γ-LiAlO2) reacts with molten benzoic acid leading to nearly total Li+ proton exchange thus forming LiHAl2O4 There is a lot of interest in the chemical reactivity among the three modifications of LiAlO2. The reasons for the α-LiAlO2 modification being highly reactive and the β-LiAlO2 or γ-LiAlO2 modifications being totally unreactive is currently a mystery.[11]

Formation

Early methods

Lithium aluminate powder preparation was based on the solid-state reactions between Al2O3 and lithium-containing compounds like Li2CO3, LiOH, Li2O, 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-LiAlO2 phase; in a wet chemical reaction, the main product is a solid solution of α-LiAlO2 and γ-LiAlO2 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]

References

  1. ↑ "Lithium Aluminate". https://www.americanelements.com/lithium-aluminate-12003-67-7. 
  2. ↑ 2.0 2.1 2.2 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.[1]
  3. ↑ "Lithium Aluminate Material Development". https://energyenvironment.pnnl.gov/projects/project_description.asp?id=383. 
  4. ↑ MATSUO, Toshiaki; Takashi NISHI; Masami MATSUDA; Tatsuo IZUMIDA (1995). "LiNO3 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. http://papers.sae.org/2013-32-9049/. Retrieved 2014-11-08. 
  6. ↑ MATSUO, Toshiaki; Masami MATSUDA; Michihiko HIRONAGA; Yoshihiko HORIKAWA (1996-11-01). "Effect of LiNO3 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 , United States Patent 4079171
  8. ↑ Weyberg. Chemisches Zentralblatt (1906): 645. Print.
  9. ↑ 9.0 9.1 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. ↑ 11.0 11.1 11.2 Reactivity and acidity of Li in lithium aluminum oxide (LiAlO2) phases Richard Dronskowski Inorganic Chemistry 1993 32 (1), 1-9
  12. ↑ 12.0 12.1 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. ↑ 13.0 13.1 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". https://www.mindat.org/min-54350.html. 
  15. ↑ "List of Minerals". 21 March 2011. https://www.ima-mineralogy.org/Minlist.htm. 



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