Lithium aluminium hydride

Lithium aluminium hydride, commonly abbreviated to LAH, is an inorganic compound with the chemical formula LiAlH4. It is a grey solid. It was discovered by Finholt, Bond and Schlesinger in 1947.[4] 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.

Lithium aluminium hydride
Wireframe model of lithium aluminium hydride
Unit cell ball and stick model of lithium aluminium hydride
Names
Preferred IUPAC name
Lithium tetrahydridoaluminate(III)
Systematic IUPAC name
Lithium alumanuide
Other names
Lithium aluminium hydride

Lithal
Lithium alanate
Lithium aluminohydride

Lithium tetrahydridoaluminate
Identifiers
3D model (JSmol)
Abbreviations LAH
ChEBI
ChemSpider
ECHA InfoCard 100.037.146
EC Number
  • 240-877-9
13167
RTECS number
  • BD0100000
UNII
Properties
LiAlH4
Molar mass 37.95 g/mol
Appearance white crystals (pure samples)
grey powder (commercial material)
hygroscopic
Odor odorless
Density 0.917 g/cm3, solid
Melting point 150 °C (302 °F; 423 K) (decomposes)
Reacts
Solubility in tetrahydrofuran 112.332 g/L
Solubility in diethyl ether 39.5 g/100 mL
Structure
monoclinic
P21/c
Thermochemistry
86.4 J/mol K
87.9 J/mol K
-117 kJ/mol
-48.4 kJ/mol
Hazards[1]
Safety data sheet Lithium aluminium hydride
GHS pictograms
GHS Signal word Danger
H260, H314
P223, P231+232, P280, P305+351+338, P370+378, P422[2]
NFPA 704 (fire diamond)
Flash point 125 °C (257 °F; 398 K)
Related compounds
Related hydride
 aluminium hydride
sodium borohydride
sodium hydride
Sodium aluminium hydride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)
Infobox references

Properties, structure, preparation
SEM image of LAH powder

LAH is a colourless solid but commercial samples are usually gray due to contamination.[5] This material can be purified by recrystallization from diethyl ether. Large-scale purifications employ a Soxhlet extractor. Commonly, the impure gray material is used in synthesis, since the impurities are innocuous and can be easily separated from the organic products. The pure powdered material is pyrophoric, but not its large crystals.[6] Some commercial materials contain mineral oil to inhibit reactions with atmospheric moisture, but more commonly it is packed in moisture-proof plastic sacks.[7]

LAH violently reacts with water, including atmospheric moisture to liberate dihydrogen gas. The reaction proceeds according to the following idealized equation:[5]

LiAlH4 + 4 H2O → LiOH + Al(OH)3 + 4 H2

This reaction provides a useful method to generate hydrogen in the laboratory. Aged, air-exposed samples often appear white because they have absorbed enough moisture to generate a mixture of the white compounds lithium hydroxide and aluminium hydroxide.[8]

Structure
The crystal structure of LAH; Li atoms are purple and AlH4 tetrahedra are tan.

LAH crystallizes in the monoclinic space group P21/c. The unit cell has the dimensions: a = 4.82, b = 7.81, and c = 7.92 Å, α = γ = 90° and β = 112°. In the structure, Li+ centers are surrounded by five AlH−
4 tetrahedra. The Li+ centers are bonded to one hydrogen atom from each of the surrounding tetrahedra creating a bipyramid arrangement. At high pressures (>2.2 GPa) a phase transition may occur to give β-LAH.[9]

X-ray powder diffraction pattern of as-received LiAlH4. The asterisk designates an impurity, possibly LiCl.

Preparation

LiAlH4 was first prepared from the reaction between lithium hydride (LiH) and aluminium chloride:[4][5]

4 LiH + AlCl3 → LiAlH4 + 3 LiCl

In addition to this method, the industrial synthesis entails the initial preparation of sodium aluminium hydride from the elements under high pressure and temperature:[10]

Na + Al + 2 H2 → NaAlH4

LiAlH4 is then prepared by a salt metathesis reaction according to:

NaAlH4 + LiCl → LiAlH4 + NaCl

which proceeds in a high yield. LiCl is removed by filtration from an ethereal solution of LAH, with subsequent precipitation of LiAlH4 to yield a product containing around 1% w/w LiCl.[10]

An alternative preparation starts from LiH, and metallic Al instead of AlCl3. Catalyzed by a small quantity of TiCl3 (0.2%), the reaction proceeds well using dimethylether as solvent. This method avoids the cogeneration of salt.[11]

Solubility data
Solubility of LiAlH4 (mol/L)[12]
Solvent Temperature (°C)
0255075100
Diethyl ether –5.92–––
THF –2.96–––
Monoglyme 1.291.802.573.093.34
Diglyme 0.261.291.542.062.06
Triglyme 0.560.771.291.802.06
Tetraglyme 0.771.542.062.061.54
Dioxane –0.03–––
Dibutyl ether –0.56–––

LAH is soluble in many ethereal solutions. However, it may spontaneously decompose due to the presence of catalytic impurities, though, it appears to be more stable in tetrahydrofuran (THF). Thus, THF is preferred over, e.g., diethyl ether, despite the lower solubility.[12]

Thermodynamic data

The table summarizes thermodynamic data for LAH and reactions involving LAH,[13][14] in the form of standard enthalpy, entropy, and Gibbs free energy change, respectively.

Thermodynamic data for reactions involving LiAlH4
ReactionΔH°
(kJ/mol)		ΔS°
(J/(mol·K))		ΔG°
(kJ/mol)		Comment
Li (s) + Al (s) + 2 H2(g) → LiAlH4 (s)−116.3−240.1−44.7Standard formation from the elements.
LiH (s) + Al (s) + ​3⁄2 H2 (g) → LiAlH4 (s)−95.6−180.2237.6Using ΔH°f(LiH) = −90.579865, ΔS°f(LiH) = −679.9, and ΔG°f(LiH) = −67.31235744.
LiAlH4 (s) → LiAlH4 (l)22––Heat of fusion. Value might be unreliable.
LiAlH4 (l) → ​1⁄3 Li3AlH6 (s) + ​2⁄3 Al (s) + H2 (g)3.46104.5−27.68ΔS° calculated from reported values of ΔH° and ΔG°.

Thermal decomposition

LAH is metastable at room temperature. During prolonged storage it slowly decomposes to Li3AlH6 and LiH.[15] This process can be accelerated by the presence of catalytic elements, such as titanium, iron or vanadium.

Differential scanning calorimetry of as-received LiAlH4.

When heated LAH decomposes in a three-step reaction mechanism:[15][16][17]

3 LiAlH4 → Li3AlH6 + 2 Al + 3 H2

 

 

 

 

(R1)

2 Li3AlH6 → 6 LiH + 2 Al + 3 H2

 

 

 

 

(R2)

2 LiH + 2 Al → 2 LiAl + H2

 

 

 

 

(R3)

R1 is usually initiated by the melting of LAH in the temperature range 150–170 °C,[18][19][20] immediately followed by decomposition into solid Li3AlH6, although R1 is known to proceed below the melting point of LiAlH4 as well.[21] At about 200 °C, Li3AlH6 decomposes into LiH (R2)[15][17][20] and Al which subsequently convert into LiAl above 400 °C (R3).[17] Reaction R1 is effectively irreversible. R3 is reversible with an equilibrium pressure of about 0.25 bar at 500 °C. R1 and R2 can occur at room temperature with suitable catalysts.[22]

Applications

Use in organic chemistry

Lithium aluminium hydride (LiAlH4) is widely used in organic chemistry as a reducing agent.[5] It is more powerful than the related reagent sodium borohydride owing to the weaker Al-H bond compared to the B-H bond.[23] Often as a solution in diethyl ether and followed by an acid workup, it will convert esters, carboxylic acids, acyl chlorides, aldehydes, and ketones into the corresponding alcohols (see: carbonyl reduction). Similarly, it converts amide,[24][25] nitro, nitrile, imine, oxime,[26] and azide compounds into the amines (see: amide reduction). It reduces quaternary ammonium cations into the corresponding tertiary amines. Reactivity can be tuned by replacing hydride groups by alkoxy groups. Due to its pyrophoric nature, instability, toxicity, low shelf life and handling problems associated with its reactivity, it has been replaced in the last decade, both at the small-industrial scale and for large-scale reductions by the more convenient related reagent sodium bis (2-methoxyethoxy)aluminium hydride, which exhibits similar reactivity but with higher safety, easier handling and better economics.[27]

LAH is most commonly used for the reduction of esters[28][29] and carboxylic acids[30] to primary alcohols; prior to the advent of LiAlH4 this was a difficult conversion involving sodium metal in boiling ethanol (the Bouveault-Blanc reduction). Aldehydes and ketones[31] can also be reduced to alcohols by LAH, but this is usually done using milder reagents such as NaBH4; α, β-unsaturated ketones are reduced to allylic alcohols.[32] When epoxides are reduced using LAH, the reagent attacks the less hindered end of the epoxide, usually producing a secondary or tertiary alcohol. Epoxycyclohexanes are reduced to give axial alcohols preferentially.[33]

Partial reduction of acid chlorides to give the corresponding aldehyde product cannot proceed via LAH, since the latter reduces all the way to the primary alcohol. Instead, the milder lithium aluminium tri(t-butoxy)hydride, which reacts significantly faster with the acid chloride than with the aldehyde, must be used. For example, when isovaleric acid is treated with thionyl chloride to give isovaleroyl chloride, it can then be reduced via lithium aluminium tri(t-butoxy)hydride to give isovaleraldehyde in 65% yield.[34]

Error: imagemap_invalid_image

Lithium aluminium hydride also reduces alkyl halides to alkanes.[35][36] Alkyl iodides react the fastest, followed by alkyl bromides and then alkyl chlorides. Primary halides are the most reactive followed by secondary halides. Tertiary halides react only in certain cases.[37]

Lithium aluminium hydride does not reduce simple alkenes or arenes. Alkynes are reduced only if an alcohol group is nearby.[38]It was observed that the LiAlH4 reduces the double bond in the N-allylamides.[39]

Inorganic chemistry

LAH is widely used to prepare main group and transition metal hydrides from the corresponding metal halides. For example, sodium hydride (NaH) can be prepared from sodium chloride (NaCl) through the following reaction:[13]

LiAlH4 + 4 NaCl → 4 NaH + LiCl + AlCl3

LAH also reacts with many inorganic ligands to form coordinated alumina complexes associated with lithium ions.[13]

LiAlH4 + 4NH3 → Li[Al(NH2)4] + 4H2

Hydrogen storage
Volumetric and gravimetric hydrogen storage densities of different hydrogen storage methods. Metal hydrides are represented with squares and complex hydrides with triangles (including LiAlH4). Reported values for hydrides are excluding tank weight. DOE FreedomCAR targets are including tank weight.

LiAlH4 contains 10.6 wt% hydrogen, thereby making LAH a potential hydrogen storage medium for future fuel cell-powered vehicles. The high hydrogen content, as well as the discovery of reversible hydrogen storage in Ti-doped NaAlH4,[40] have sparked renewed research into LiAlH4 during the last decade. A substantial research effort has been devoted to accelerating the decomposition kinetics by catalytic doping and by ball milling.[41] In order to take advantage of the total hydrogen capacity, the intermediate compound LiH must be dehydrogenated as well. Due to its high thermodynamic stability this requires temperatures in excess of 400 °C, which is not considered feasible for transportation purposes. Accepting LiH + Al as the final product, the hydrogen storage capacity is reduced to 7.96 wt%. Another problem related to hydrogen storage is the recycling back to LiAlH4 which, owing to its relatively low stability, requires an extremely high hydrogen pressure in excess of 10000 bar.[41] Cycling only reaction R2 — that is, using Li3AlH6 as starting material — would store 5.6 wt% hydrogen in a single step (vs. two steps for NaAlH4 which stores about the same amount of hydrogen). However, attempts at this process have not been successful so far.

Other tetrahydridoaluminiumates

A variety of salts analogous to LAH are known. NaH can be used to efficiently produce sodium aluminium hydride (NaAlH4) by metathesis in THF:

LiAlH4 + NaH → NaAlH4 + LiH

Potassium aluminium hydride (KAlH4) can be produced similarly in diglyme as a solvent:[42]

LiAlH4 + KH → KAlH4 + LiH

The reverse, i.e., production of LAH from either sodium aluminium hydride or potassium aluminium hydride can be achieved by reaction with LiCl or lithium hydride in diethyl ether or THF:[42]

NaAlH4 + LiCl → LiAlH4 + NaCl
KAlH4 + LiCl → LiAlH4 + KCl

"Magnesium alanate" (Mg(AlH4)2) arises similarly using MgBr2:[43]

2 LiAlH4 + MgBr2 → Mg(AlH4)2 + 2 LiBr

Red-Al (or SMEAH, NaAlH2(OC2H4OCH3)2) is synthesized by reacting sodium aluminum tetrahydride (NaAlH4) and 2-methoxyethanol:[44]

See also

References
  1. Index no. 001-002-00-4 of Annex VI, Part 3, to Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December 2008 on classification, labelling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006. OJEU L353, 31.12.2008, pp 1–1355 at p 472.
  2. Sigma-Aldrich Co., Lithium aluminium hydride. Retrieved on 2018-06-1.
  3. Lithium aluminium hydride
  4. Finholt, A. E.; Bond, A. C.; Schlesinger, H. I. (1947). "Lithium Aluminum Hydride, Aluminum Hydride and Lithium Gallium Hydride, and Some of their Applications in Organic and Inorganic Chemistry". Journal of the American Chemical Society. 69 (5): 1199–1203. doi:10.1021/ja01197a061.
  5. Gerrans, G. C.; Hartmann-Petersen, P. (2007). "Lithium Aluminium Hydride". Sasol Encyclopaedia of Science and Technology. New Africa Books. p. 143. ISBN 978-1-86928-384-1.
  6. Keese, R.; Brändle, M.; Toube, T. P. (2006). Practical Organic Synthesis: A Student's Guide. John Wiley and Sons. p. 134. ISBN 0-470-02966-8.
  7. Andreasen, A.; Vegge, T.; Pedersen, A. S. (2005). "Dehydrogenation Kinetics of as-Received and Ball-Milled LiAlH4" (PDF). Journal of Solid State Chemistry. 178 (12): 3672–3678. Bibcode:2005JSSCh.178.3672A. doi:10.1016/j.jssc.2005.09.027. Archived from the original (PDF) on 2016-03-03. Retrieved 2010-05-07.
  8. Pohanish, R. P. (2008). Sittig's Handbook of Toxic and Hazardous Chemicals and Carcinogens (5th ed.). William Andrew Publishing. p. 1540. ISBN 978-0-8155-1553-1.
  9. Løvvik, O. M.; Opalka, S. M.; Brinks, H. W.; Hauback, B. C. (2004). "Crystal Structure and Thermodynamic Stability of the Lithium Alanates LiAlH4 and Li3AlH6". Physical Review B. 69 (13): 134117. Bibcode:2004PhRvB..69m4117L. doi:10.1103/PhysRevB.69.134117.
  10. Holleman, A. F., Wiberg, E., Wiberg, N. (2007). Lehrbuch der Anorganischen Chemie (102nd ed.). de Gruyter. ISBN 978-3-11-017770-1.CS1 maint: multiple names: authors list (link)
  11. Xiangfeng, Liu; Langmi, Henrietta W.; McGrady, G. Sean; Craig, M. Jensen; Beattie, Shane D.; Azenwi, Felix F. (2011). "Ti-Doped LiAlH4 for Hydrogen Storage: Synthesis, Catalyst Loading and Cycling Performance". J. Am. Chem. Soc. 133 (39): 15593–15597. doi:10.1021/ja204976z. PMID 21863886.
  12. Mikheeva, V. I.; Troyanovskaya, E. A. (1971). "Solubility of Lithium Aluminum Hydride and Lithium Borohydride in Diethyl Ether". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 20 (12): 2497–2500. doi:10.1007/BF00853610.
  13. Patnaik, P. (2003). Handbook of Inorganic Chemicals. McGraw-Hill. p. 492. ISBN 978-0-07-049439-8.
  14. Smith, M. B.; Bass, G. E. (1963). "Heats and Free Energies of Formation of the Alkali Aluminum Hydrides and of Cesium Hydride". Journal of Chemical & Engineering Data. 8 (3): 342–346. doi:10.1021/je60018a020.
  15. Dymova T. N.; Aleksandrov, D. P.; Konoplev, V. N.; Silina, T. A.; Sizareva; A. S. (1994). Russian Journal of Coordination Chemistry. 20: 279. Missing or empty |title= (help)
  16. Dilts, J. A.; Ashby, E. C. (1972). "Thermal Decomposition of Complex Metal Hydrides". Inorganic Chemistry. 11 (6): 1230–1236. doi:10.1021/ic50112a015.
  17. Blanchard, D.; Brinks, H.; Hauback, B.; Norby, P. (2004). "Desorption of LiAlH4 with Ti- and V-Based Additives". Materials Science and Engineering B. 108 (1–2): 54–59. doi:10.1016/j.mseb.2003.10.114.
  18. Chen, J.; Kuriyama, N.; Xu, Q.; Takeshita, H. T.; Sakai, T. (2001). "Reversible Hydrogen Storage via Titanium-Catalyzed LiAlH4 and Li3AlH6". The Journal of Physical Chemistry B. 105 (45): 11214–11220. doi:10.1021/jp012127w.
  19. Balema, V.; Pecharsky, V. K.; Dennis, K. W. (2000). "Solid State Phase Transformations in LiAlH4 during High-Energy Ball-Milling". Journal of Alloys and Compounds. 313 (1–2): 69–74. doi:10.1016/S0925-8388(00)01201-9.
  20. Andreasen, A. (2006). "Effect of Ti-Doping on the Dehydrogenation Kinetic Parameters of Lithium Aluminum Hydride". Journal of Alloys and Compounds. 419 (1–2): 40–44. doi:10.1016/j.jallcom.2005.09.067.
  21. Andreasen, A.; Pedersen, A. S.; Vegge, T. (2005). "Dehydrogenation Kinetics of as-Received and Ball-Milled LiAlH4". Journal of Solid State Chemistry. 178 (12): 3672–3678. Bibcode:2005JSSCh.178.3672A. doi:10.1016/j.jssc.2005.09.027.
  22. Balema, V.; Wiench, J. W.; Dennis, K. W.; Pruski, M.; Pecharsky, V. K. (2001). "Titanium Catalyzed Solid-State Transformations in LiAlH4 During High-Energy Ball-Milling". Journal of Alloys and Compounds. 329 (1–2): 108–114. doi:10.1016/S0925-8388(01)01570-5.
  23. Brown, H. C. (1951). "Reductions by Lithium Aluminum Hydride". Organic Reactions. 6: 469. doi:10.1002/0471264180.or006.10. ISBN 0471264180.
  24. Seebach, D.; Kalinowski, H.-O.; Langer, W.; Crass, G.; Wilka, E.-M. (1991). "Chiral Media for Asymmetric Solvent Inductions. (S,S)-( + )-1,4-bis(Dimethylamino)-2,3-Dimethoxybutane from (R,R)-( + )-Diethyl Tartrate". Organic Syntheses.; Collective Volume, 7, p. 41
  25. Park, C. H.; Simmons, H. E. (1974). "Macrocyclic Diimines: 1,10-Diazacyclooctadecane". Organic Syntheses. 54: 88.; Collective Volume, 6, p. 382
  26. Chen, Y. K.; Jeon, S.-J.; Walsh, P. J.; Nugent, W. A. (2005). "(2S)-(−)-3-exo-(Morpholino)Isoborneol". Organic Syntheses. 82: 87.
  27. "Red-Al, Sodium bis(2-methoxyethoxy)aluminumhydride". Organic Chemistry Portal.
  28. Reetz, M. T.; Drewes, M. W.; Schwickardi, R. (1999). "Preparation of Enantiomerically Pure α-N,N-Dibenzylamino Aldehydes: S-2-(N,N-Dibenzylamino)-3-Phenylpropanal". Organic Syntheses. 76: 110.; Collective Volume, 10, p. 256
  29. Oi, R.; Sharpless, K. B. (1996). "3-[(1S)-1,2-Dihydroxyethyl]-1,5-Dihydro-3H-2,4-Benzodioxepine". Organic Syntheses. 73: 1.; Collective Volume, 9, p. 251
  30. Koppenhoefer, B.; Schurig, V. (1988). "(R)-Alkyloxiranes of High Enantiomeric Purity from (S)-2-Chloroalkanoic Acids via (S)-2-Chloro-1-Alkanols: (R)-Methyloxirane". Organic Syntheses. 66: 160.; Collective Volume, 8, p. 434
  31. Barnier, J. P.; Champion, J.; Conia, J. M. (1981). "Cyclopropanecarboxaldehyde". Organic Syntheses. 60: 25.; Collective Volume, 7, p. 129
  32. Elphimoff-Felkin, I.; Sarda, P. (1977). "Reductive Cleavage of Allylic Alcohols, Ethers, or Acetates to Olefins: 3-Methylcyclohexene". Organic Syntheses. 56: 101.; Collective Volume, 6, p. 769
  33. Rickborn, B.; Quartucci, J. (1964). "Stereochemistry and Mechanism of Lithium Aluminum Hydride and Mixed Hydride Reduction of 4-t-Butylcyclohexene Oxide". The Journal of Organic Chemistry. 29 (11): 3185–3188. doi:10.1021/jo01034a015.
  34. Wade, L. G. Jr. (2006). Organic Chemistry (6th ed.). Pearson Prentice Hall. ISBN 0-13-147871-0.
  35. Johnson, J. E.; Blizzard, R. H.; Carhart, H. W. (1948). "Hydrogenolysis of Alkyl Halides by Lithium Aluminum Hydride". Journal of the American Chemical Society. 70 (11): 3664–3665. doi:10.1021/ja01191a035. PMID 18121883.
  36. Krishnamurthy, S.; Brown, H. C. (1982). "Selective Reductions. 28. The Fast Reaction of Lithium Aluminum Hydride with Alkyl Halides in THF. A Reappraisal of the Scope of the Reaction". The Journal of Organic Chemistry. 47 (2): 276–280. doi:10.1021/jo00341a018.
  37. Carruthers, W. (2004). Some Modern Methods of Organic Synthesis. Cambridge University Press. p. 470. ISBN 0-521-31117-9.
  38. Wender, P. A.; Holt, D. A.; Sieburth, S. Mc N. (1986). "2-Alkenyl Carbinols from 2-Halo Ketones: 2-E-Propenylcyclohexanol". Organic Syntheses. 64: 10.; Collective Volume, 7, p. 456
  39. Thiedemann, B.; Schmitz, C. M.; Staubitz, A. (2014). "Reduction of N-allylamides by LiAlH4: Unexpected Attack of the Double Bond With Mechanistic Studies of Product and Byproduct Formation". The Journal of Organic Chemistry. 79 (21): 10284–95. doi:10.1021/jo501907v. PMID 25347383.
  40. Bogdanovic, B.; Schwickardi, M. (1997). "Ti-Doped Alkali Metal Aluminium Hydrides as Potential Novel Reversible Hydrogen Storage Materials". Journal of Alloys and Compounds. 253–254: 1–9. doi:10.1016/S0925-8388(96)03049-6.
  41. Varin, R. A.; Czujko, T.; Wronski, Z. S. (2009). Nanomaterials for Solid State Hydrogen Storage (5th ed.). Springer. p. 338. ISBN 978-0-387-77711-5.
  42. Santhanam, R.; McGrady, G. S. (2008). "Synthesis of Alkali Metal Hexahydroaluminate Complexes Using Dimethyl Ether as a Reaction Medium". Inorganica Chimica Acta. 361 (2): 473–478. doi:10.1016/j.ica.2007.04.044.
  43. Wiberg, E.; Wiberg, N.; Holleman, A. F. (2001). Inorganic Chemistry. Academic Press. p. 1056. ISBN 0-12-352651-5.
  44. Casensky, B.; Machacek, J.; Abraham, K. (1971). "The chemistry of sodium alkoxyaluminium hydrides. I. Synthesis of sodium bis(2-methoxyethoxy)aluminium hydride". Collection of Czechoslovak Chemical Communications. 36 (7): 2648–2657. doi:10.1135/cccc19712648.

Further reading
This article is issued from Wikipedia. The text is licensed under Creative Commons - Attribution - Sharealike. Additional terms may apply for the media files.