Calcium hydride
Calcium hydride is the chemical compound with the formula CaH2, an alkaline earth hydride. This grey powder (white if pure, which is rare) reacts vigorously with water, liberating hydrogen gas. CaH2 is thus used as a drying agent, i.e. a desiccant. CaH2 is a saline hydride, meaning that its structure is salt-like. The alkali metals and the alkaline earth metals heavier than beryllium all form saline hydrides. A well-known example is sodium hydride, which crystallizes in the NaCl motif. These species are insoluble in all solvents with which they do not react. CaH2 crystallizes in the PbCl2 (cotunnite) structure.
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| Names | |
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| IUPAC name
Calcium hydride
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| Other names
Calcium(II) hydride
Calcium dihydride Hydrolith | |
| Identifiers | |
3D model (JSmol)
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| ChemSpider | |
| ECHA InfoCard | 100.029.263 |
| EC Number |
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PubChem CID
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| UNII | |
CompTox Dashboard (EPA)
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| Properties | |
| CaH2 | |
| Molar mass | 42.094 g/mol |
| Appearance | gray powder (white when pure) |
| Density | 1.70 g/cm3, solid |
| Melting point | 816 °C (1,501 °F; 1,089 K) |
| reacts violently | |
| Solubility | reacts in alcohol |
| Structure | |
| Orthorhombic, oP12 | |
| Pnma, No. 62 | |
| Thermochemistry | |
Std molar
entropy (S⦵298) |
41.4 J/(mol·K)[1] |
Std enthalpy of
formation (ΔfH⦵298) |
−181.5 kJ/mol |
Gibbs free energy (ΔfG⦵)
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−142.5 kJ/mol |
| Hazards | |
| GHS labelling: | |
   
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| Danger | |
| H260 | |
| NFPA 704 (fire diamond) | |
| Related compounds | |
Other cations
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Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Calcium hydride is the chemical compound with the formula CaH2, an alkaline earth hydride. This grey powder (white if pure, which is rare) reacts vigorously with water, liberating hydrogen gas. CaH2 is thus used as a drying agent, i.e. a desiccant.[2]
CaH2 is a saline hydride, meaning that its structure is salt-like. The alkali metals and the alkaline earth metals heavier than beryllium all form saline hydrides. A well-known example is sodium hydride, which crystallizes in the NaCl motif. These species are insoluble in all solvents with which they do not react. CaH2 crystallizes in the PbCl2 (cotunnite) structure.[3]
Preparation
[edit]Calcium hydride is prepared from its elements by direct combination of calcium and hydrogen at 300 to 400 °C.[4][5]
Uses
[edit]Reduction of metal oxides
[edit]CaH2 is a reducing agent for the production of metal from the metal oxides of Ti, V, Nb, Ta, and U. It is proposed to operate via its decomposition to Ca metal:[4]
- TiO2 + 2 CaH2 → Ti + 2 CaO + 2 H2
Hydrogen source
[edit]CaH2 has been used for hydrogen production. In the 1940s, it was available under the trade name "Hydrolith" as a source of hydrogen:
The trade name for this compound is "hydrolith"; in cases of emergency, it can be used as a portable source of hydrogen, for filling airships. It is rather expensive for this use.[6]
The reference to "emergency" probably refers to wartime use. The compound has, however, been widely used for decades as a safe and convenient means to inflate weather balloons. Likewise, it is regularly used in laboratories to produce small quantities of highly pure hydrogen for experiments. The moisture content of diesel fuel is estimated by the hydrogen evolved upon treatment with CaH2.[4]
Desiccant
[edit]The reaction of CaH2 with water can be represented as follows:
- CaH2 + 2 H2O → Ca(OH)2 + 2 H2
The two hydrolysis products, gaseous H2 and Ca(OH)2, are readily separated from the dried solvent.
Calcium hydride is a relatively mild desiccant and, compared to molecular sieves, probably inefficient.[7] Its use is safer than more reactive agents such as sodium metal or sodium-potassium alloy. Calcium hydride is widely used as a desiccant for basic solvents such as amines and pyridine. It is also used to dry alcohols.[2]
Despite its convenience, CaH2 has a few drawbacks:
- It is insoluble in all solvents with which it does not react vigorously, in contrast to LiAlH4, thus the speed of its drying action can be slow.
- Because CaH2 and Ca(OH)2 are almost indistinguishable in appearance, the quality of a sample of CaH2 is not obvious visually.
History
[edit]During the Battle of the Atlantic, German submarines used calcium hydride as a sonar decoy called bold.[8]
Other calcium hydrides
[edit]Although the term calcium hydride almost always refers to CaH2, a number of molecular hydrides of calcium are known. One example is (Ca(μ-H)(thf)(nacnac))2.[9] Dimeric calcium hydrides arise through the reaction of a calcium amide with phenylsilane.[10] Subsequent studies have expanded the library of stabilizing ligands, but all are multidentate ligands that coordinate through nitrogen sites.[11]
See also
[edit]References
[edit]- ^ Zumdahl, Steven S. (2009). Chemical Principles (6th ed.). Houghton Mifflin Company. p. A21. ISBN 978-0-618-94690-7.
- ^ a b Gawley, Robert E.; Davis, Arnold (2001). "Calcium Hydride". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rc005. ISBN 0471936235.
- ^ Wells, A. F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. ISBN 0-19-855370-6.
- ^ a b c Rittmeyer, Peter; Wietelmann, Ulrich (2000). "Hydrides". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a13_199. ISBN 978-3-527-30673-2.
- ^ P. Ehrlich (1963). "Calcium Strontium and Barium Hydrides". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1. NY, NY: Academic Press. p. 929.
- ^ Adlam G. H. J. and Price L. S., A Higher School Certificate Inorganic Chemistry, John Murray, London, 1940.
- ^ Williams, D. Bradley G.; Lawton, Michelle (2010). "Drying of Organic Solvents: Quantitative Evaluation of the Efficiency of Several Desiccants". The Journal of Organic Chemistry. 75 (24): 8351–8354. doi:10.1021/jo101589h. PMID 20945830. S2CID 17801540.
- ^ McNeil, Ian (2002-06-01). An Encyclopedia of the History of Technology. Routledge. ISBN 9781134981649.
- ^ Mukherjee, Debabrata; Schuhknecht, Danny; Okuda, Jun (2018). "Hydrido Complexes of Calcium: A New Family of Molecular Alkaline-Earth-Metal Compounds". Angewandte Chemie International Edition. 57 (31): 9590–9602. doi:10.1002/anie.201801869. PMID 29575506. S2CID 4355887.
- ^ Harder, Sjoerd; Brettar, Julie (2006-05-19). "Rational Design of a Well-Defined Soluble Calcium Hydride Complex". Angewandte Chemie International Edition. 45 (21): 3474–3478. doi:10.1002/anie.200601013. ISSN 1433-7851. PMID 16637088.
- ^ Mukherjee, Debabrata; Schuhknecht, Danny; Okuda, Jun (2018-07-26). "Hydrido Complexes of Calcium: A New Family of Molecular Alkaline-Earth-Metal Compounds". Angewandte Chemie International Edition. 57 (31): 9590–9602. doi:10.1002/anie.201801869. ISSN 1433-7851. PMID 29575506.