Chemistry:Aluminium hydroxide

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Aluminium hydroxide
Unit cell ball and stick model of aluminium hydroxide
Sample of aluminium hydroxide in a vial
Names
Preferred IUPAC name
Aluminium hydroxide
Systematic IUPAC name
Trihydroxidoaluminium
Other names
Aluminic acid

Aluminic hydroxide
Aluminium(III) hydroxide
Aluminium hydroxide
Aluminum trihydroxide
Hydrated alumina

Orthoaluminic acid
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
DrugBank
KEGG
RTECS number
  • BD0940000
UNII
Properties[1][2]
Al(OH)3
Molar mass 78.00 g/mol
Appearance White amorphous powder
Density 2.42 g/cm3, solid
Melting point 300 °C (572 °F; 573 K)
0.0001 g/100 mL
3×10−34
Solubility soluble in acids and alkalis
Acidity (pKa) >7
Isoelectric point 7.7
Thermochemistry[3]
−1277 kJ·mol−1
Pharmacology[4]
1=ATC code }} A02AB01 (WHO)
Hazards
Safety data sheet External MSDS
GHS pictograms GHS07: Harmful
H319, H335
P264, P261, P280, P271, P312, P304+340, P305+351+338, P337+313
NFPA 704 (fire diamond)
Flammability code 0: Will not burn. E.g. waterHealth code 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no codeNFPA 704 four-colored diamond
0
1
0
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
>5000 mg/kg (rat, oral)
Related compounds
Other anions
None
Related compounds
Sodium oxide,
aluminium oxide hydroxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is ☑Y☒N ?)
Infobox references

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.

Structure

Al(OH)3 is built up of double layers of hydroxyl groups with aluminium ions occupying two-thirds of the octahedral holes between the two layers.[5][6] Four polymorphs are recognized.[7] All feature layers of octahedral aluminium hydroxide units, with hydrogen bonds between the layers. The polymorphs differ in terms of the stacking of the layers. All forms of Al(OH)3 crystals are hexagonal :

  • gibbsite is also known as γ-Al(OH)3 [8] or α-Al(OH)3
  • bayerite is also known as α-Al(OH)3 [8] or β-alumina trihydrate
  • nordstrandite is also known as Al(OH)3[8]
  • doyleite

Hydrargillite, once thought to be aluminium hydroxide, is an aluminium phosphate. Nonetheless, both gibbsite and hydrargillite refer to the same polymorphism of aluminium hydroxide, with gibbsite used most commonly in the United States and hydrargillite used more often in Europe. Hydrargillite is named after the Greek words for water (hydra) and clay (argylles).

Properties

Aluminium hydroxide is amphoteric. In acid, it acts as a Brønsted–Lowry base. It neutralizes the acid, yielding a salt:[9]

3 HCl + Al(OH)3 → AlCl3 + 3 H2O

In bases, it acts as a Lewis acid by binding hydroxide ions:[9]

Al(OH)3 + OH → Al(OH)4

Production

Red mud reservoirs (this one in Stade, Germany) contain the corrosive residues from the production of aluminum hydroxide.

Virtually all the aluminium hydroxide used commercially is manufactured by the Bayer process[10] which involves dissolving bauxite in sodium hydroxide at temperatures up to 270 °C (518 °F). The waste solid, bauxite tailings, is removed and aluminium hydroxide is precipitated from the remaining solution of sodium aluminate. This aluminium hydroxide can be converted to aluminium oxide or alumina by calcination.

The residue or bauxite tailings, which is mostly iron oxide, is highly caustic due to residual sodium hydroxide. It was historically stored in lagoons; this led to the Ajka alumina plant accident in 2010 in Hungary, where a dam bursting led to the drowning of nine people. An additional 122 sought treatment for chemical burns. The mud contaminated 40 square kilometres (15 sq mi) of land and reached the Danube. While the mud was considered non-toxic due to low levels of heavy metals, the associated slurry had a pH of 13.[11]

Uses

Fire retardant filler

Aluminium hydroxide also finds use as a fire retardant filler for polymer applications. It is selected for these applications because it is colorless (like most polymers), inexpensive, and has good fire retardant properties.[12] Magnesium hydroxide and mixtures of huntite and hydromagnesite are used similarly.[13][14][15][16][17] It decomposes at about 180 °C (356 °F), absorbing a considerable amount of heat in the process and giving off water vapour. In addition to behaving as a fire retardant, it is very effective as a smoke suppressant in a wide range of polymers, most especially in polyesters, acrylics, ethylene vinyl acetate, epoxies, polyvinyl chloride (PVC) and rubber.[18]

Precursor to Al compounds

Aluminium hydroxide is a feedstock for the manufacture of other aluminium compounds: calcined aluminas, aluminium sulfate, polyaluminium chloride, aluminium chloride, zeolites, sodium aluminate, activated alumina, and aluminium nitrate.[6]

Freshly precipitated aluminium hydroxide forms gels, which are the basis for the application of aluminium salts as flocculants in water purification. This gel crystallizes with time. Aluminium hydroxide gels can be dehydrated (e.g. using water-miscible non-aqueous solvents like ethanol) to form an amorphous aluminium hydroxide powder, which is readily soluble in acids. Heating converts it to activated aluminas, which are used as desiccants, adsorbent in gas purification, and catalyst supports.[12]

Pharmaceutical

Under the generic name "algeldrate", aluminium hydroxide is used as an antacid in humans and animals (mainly cats and dogs). It is preferred over other alternatives such as sodium bicarbonate because Al(OH)3, being insoluble, does not increase the pH of stomach above 7 and hence, does not trigger secretion of excess acid by the stomach. Brand names include Alu-Cap, Aludrox, Gaviscon or Pepsamar. It reacts with excess acid in the stomach, reducing the acidity of the stomach content,[19][20] which may relieve the symptoms of ulcers, heartburn or dyspepsia. Such products can cause constipation, because the aluminium ions inhibit the contractions of smooth muscle cells in the gastrointestinal tract, slowing peristalsis and lengthening the time needed for stool to pass through the colon.[21] Some such products are formulated to minimize such effects through the inclusion of equal concentrations of magnesium hydroxide or magnesium carbonate, which have counterbalancing laxative effects.[22]

This compound is also used to control hyperphosphatemia (elevated phosphate, or phosphorus, levels in the blood) in people and animals suffering from kidney failure. Normally, the kidneys filter excess phosphate out from the blood, but kidney failure can cause phosphate to accumulate. The aluminium salt, when ingested, binds to phosphate in the intestines and reduce the amount of phosphorus that can be absorbed.[23][24]

Precipitated aluminium hydroxide is included as an adjuvant in some vaccines (e.g. anthrax vaccine). One of the well-known brands of aluminium hydroxide adjuvant is Alhydrogel, made by Brenntag Biosector.[25] Since it absorbs protein well, it also functions to stabilize vaccines by preventing the proteins in the vaccine from precipitating or sticking to the walls of the container during storage. Aluminium hydroxide is sometimes called "alum", a term generally reserved for one of several sulfates.

Vaccine formulations containing aluminium hydroxide stimulate the immune system by inducing the release of uric acid, an immunological danger signal. This strongly attracts certain types of monocytes which differentiate into dendritic cells. The dendritic cells pick up the antigen, carry it to lymph nodes, and stimulate T cells and B cells.[26] It appears to contribute to induction of a good Th2 response, so is useful for immunizing against pathogens that are blocked by antibodies. However, it has little capacity to stimulate cellular (Th1) immune responses, important for protection against many pathogens,[27] nor is it useful when the antigen is peptide-based.[28]

Safety

In the 1960s and 1970s it was speculated that aluminium was related to various neurological disorders, including Alzheimer's disease.[29][30] Since then, multiple epidemiological studies have found no connection between exposure to environmental or swallowed aluminium and neurological disorders, though injected aluminium was not looked at in these studies.[31][32][33]

Neural disorders were found in experiments on mice motivated by Gulf War illness (GWI). Aluminum hydroxide injected in doses equivalent to those administered to the United States military, showed increased reactive astrocytes, increased apoptosis of motor neurons and microglial proliferation within the spinal cord and cortex.[34]

References

  1. For solubility product: "Archived copy". http://www.ktf-split.hr/periodni/en/abc/kpt.html. 
  2. For isoelectric point: Gayer, K. H.; Thompson, L. C.; Zajicek, O. T. (September 1958). "The solubility of aluminum hydroxide in acidic and basic media at 25 ?c". Canadian Journal of Chemistry 36 (9): 1268–1271. doi:10.1139/v58-184. ISSN 0008-4042. 
  3. Zumdahl, Steven S. (2009). Chemical Principles (6th ed.). Houghton Mifflin Company. ISBN 978-0-618-94690-7. 
  4. Black, Ronald A.; Hill, D. Ashley (2003-06-15). "Over-the-Counter Medications in Pregnancy". American Family Physician 67 (12): 2517–2524. ISSN 0002-838X. PMID 12825840. http://www.aafp.org/afp/2003/0615/p2517.html. Retrieved 2017-07-01. 
  5. Template:Wells4th
  6. 6.0 6.1 Evans, K. A. (1993). "Properties and uses of aluminium oxides and aluminium hydroxides". in A. J. Downs. Chemistry of aluminium, gallium, indium, and thallium (1st ed.). London; New York: Blackie Academic & Professional. ISBN 9780751401035. 
  7. Karamalidis, A. K.; Dzombak D. A. (2010). Surface Complexation Modeling: Gibbsite. John Wiley & Sons. pp. 15–17. ISBN 978-0-470-58768-3. https://books.google.com/books?id=XULsOFSipsgC&pg=PA15. 
  8. 8.0 8.1 8.2 Wefers, Karl; Misra, Chanakya (1987). Oxides and hydroxides of aluminum. Alcoa Research Laboratories. pp. 2. OCLC 894928306. http://worldcat.org/oclc/894928306. 
  9. 9.0 9.1 Boundless (2016-07-26). "Basic and Amphoteric Hydroxides". Boundless Chemistry. https://www.boundless.com/chemistry/textbooks/boundless-chemistry-textbook/acids-and-bases-15/acid-base-properties-of-oxides-114/basic-and-amphoteric-hydroxides-469-6403/. 
  10. Hind, AR; Bhargava SK; Grocott SC (1999). "The Surface Chemistry of Bayer Process Solids: A Review". Colloids Surf Physiochem Eng Aspects 146 (1–3): 359–74. doi:10.1016/S0927-7757(98)00798-5. 
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  14. Hollingbery, LA; Hull TR (2010). "The Thermal Decomposition of Huntite and Hydromagnesite - A Review". Thermochimica Acta 509 (1–2): 1–11. doi:10.1016/j.tca.2010.06.012. http://clok.uclan.ac.uk/1139/1/1._The_thermal_decomposition_of_huntite_and_hydromagnesite_-_A_review.pdf. 
  15. Hollingbery, LA; Hull TR (2012). "The Fire Retardant Effects of Huntite in Natural Mixtures with Hydromagnesite". Polymer Degradation and Stability 97 (4): 504–512. doi:10.1016/j.polymdegradstab.2012.01.024. http://clok.uclan.ac.uk/3420/1/Fire%20retardant%20effect%20of%20huntite%20and%20hydromagnesite.pdf. 
  16. Hollingbery, LA; Hull TR (2012). "The Thermal Decomposition of Natural Mixtures of Huntite and Hydromagnesite". Thermochimica Acta 528: 45–52. doi:10.1016/j.tca.2011.11.002. http://clok.uclan.ac.uk/3414/1/The%20Thermal%20Decomposition%20of%20Natural%20Turkish%20Huntite%20and%20Hydromagnesite.pdf. 
  17. Hull, TR; Witkowski A; Hollingbery LA (2011). "Fire Retardant Action of Mineral Fillers". Polymer Degradation and Stability 96 (8): 1462–1469. doi:10.1016/j.polymdegradstab.2011.05.006. http://clok.uclan.ac.uk/2963/1/Hull_MineralFillersPDSAcceptedManuscript.pdf. 
  18. Huber Engineered Materials. "Huber Non-Halogen Fire Retardant Additives". https://www.hubermaterials.com/userfiles/files/PFDocs/Huber%20Non-Halogen%20Fire%20Retardant%20Additives.pdf. 
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  20. Papich, Mark G. (2007). "Aluminum Hydroxide and Aluminum Carbonate". Saunders Handbook of Veterinary Drugs (2nd ed.). St. Louis, Mo: Saunders/Elsevier. pp. 15–16. ISBN 9781416028888. 
  21. Washington, Neena (2 August 1991). Antacids and Anti Reflux Agents. Boca Raton, FL: CRC Press. p. 10. ISBN 978-0-8493-5444-1. 
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  25. "About Brenntag Biosector - Brenntag". http://www.brenntag.com/biosector/en/biosector/about-brenntag-biosector/index.jsp. 
  26. Kool, M; Soullié T; van Nimwegen M; Willart MA; Muskens F; Jung S; Hoogsteden HC; Hammad H et al. (2008-03-24). "Alum adjuvant boosts adaptive immunity by inducing uric acid and activating inflammatory dendritic cells". J Exp Med 205 (4): 869–82. doi:10.1084/jem.20071087. PMID 18362170. 
  27. "Vaccine adjuvants: current state and future trends". Immunology & Cell Biology 82 (5): 488–96. 2004. doi:10.1111/j.0818-9641.2004.01272.x. PMID 15479434. 
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  29. "Alzheimer's Myth's". Alzheimer's Association. http://www.alz.org/alzheimers_disease_myths_about_alzheimers.asp. 
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  34. Shaw, Christopher A.; Petrik, Michael S. (November 2009). "Aluminum hydroxide injections lead to motor deficits and motor neuron degeneration". Journal of Inorganic Biochemistry 103 (11): 1555–1562. doi:10.1016/j.jinorgbio.2009.05.019. ISSN 1873-3344. PMID 19740540. 

External links