Chemistry:Calcium hypochlorite

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Calcium hypochlorite
Calcium oxychloride
Names
Other names
Hypochlorous acid calcium salt, bleaching powder, chloride of lime
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
EC Number
  • 231-908-7
KEGG
RTECS number
  • NH3485000
UNII
UN number 1748 2208
Properties
Ca(ClO)2
Molar mass 142.98 g/mol
Appearance white/gray powder
Density 2.35 g/cm3 (20 °C)
Melting point 100 °C (212 °F; 373 K)
Boiling point 175 °C (347 °F; 448 K) decomposes
21 g/100 mL at 25 °C
Solubility reacts in alcohol
Hazards
Safety data sheet ICSC 0638
GHS pictograms GHS03: OxidizingGHS05: CorrosiveGHS07: HarmfulGHS09: Environmental hazard
GHS Signal word Danger
H272, H302, H314, H400
P210, P220, P221, P260, P264, P270, P273, P280, P301+312, P301+330+331, P303+361+353, P304+340, P305+351+338, P310, P321, P330, P363, P370+378, P391, P405, P501
NFPA 704 (fire diamond)
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
850 mg/kg (oral, rat)
Related compounds
Other anions
Calcium chloride
Other cations
Sodium hypochlorite
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

Calcium hypochlorite is an inorganic compound with formula Ca(ClO)2. It is a white solid, although commercial samples appear yellow. It strongly smells of chlorine, owing to its slow decomposition in moist air. This compound is relatively stable as a solid and solution and has greater available chlorine than sodium hypochlorite.[1] "Pure" samples have 99.2% active chlorine. Given common industrial purity, an active chlorine content of 65-70% is typical.[2] It is the main active ingredient of commercial products called bleaching powder,[lower-alpha 1] used for water treatment and as a bleaching agent.[3]

History

Charles Tennant and Charles Macintosh developed an industrial process in the late 18th century for the manufacture of chloride of lime.[4] It was patented in 1799 and used heavily during World War I for disinfecting the trenches and wounds.[citation needed]

Uses

Sanitation

Calcium hypochlorite is commonly used to sanitize public swimming pools and disinfect drinking water. Generally the commercial substances are sold with a purity of 65% to 73% with other chemicals present, such as calcium chloride and calcium carbonate, resulting from the manufacturing process. In solution, calcium hypochlorite could be used as a general purpose sanitizer,[5] but due to calcium residue (making the water harder), sodium hypochlorite (bleach) is usually preferred.

Organic chemistry

Calcium hypochlorite is a general oxidizing agent and therefore finds some use in organic chemistry.[6] For instance the compound is used to cleave glycols, α-hydroxy carboxylic acids and keto acids to yield fragmented aldehydes or carboxylic acids.[7] Calcium hypochlorite can also be used in the haloform reaction to manufacture chloroform.[8] Calcium hypochlorite can be used to oxidize thiol and sulfide byproducts in organic synthesis and thereby reduce their odour and make them safe to dispose of.[9] The reagent used in organic chemistry is similar to the sanitizer at ~70% purity.[10]

Production

Calcium hypochlorite is produced industrially by treating moist slaked lime (Ca(OH)2) with chlorine. The one-step reaction is shown below:[3]

2 Cl
2
+ 2 Ca(OH)
2
→ Ca(ClO)
2
+ CaCl
2
+ 2 H
2
O

Industrial setups allow for the reaction to be conducted in stages to give various compositions, each producing different ratios of calcium hypochlorite, unconverted lime, and calcium chloride.[3] In one process, the chloride-rich first stage water is discarded, while the solid precipitate is dissolved in a mixture of water and lye for another round of chlorination to reach the target purity.[2] Commercial calcium hypochlorite consists of anhydrous Ca(ClO)2, dibasic calcium hypochlorite Ca3(ClO)2(OH)4 (also written as Ca(ClO)2·2Ca(OH)2), and dibasic calcium chloride Ca3Cl2(OH)4 (also written as CaCl2·2Ca(OH)2).[11][12]

Reactions

Calcium hypochlorite reacts rapidly with acids producing calcium chloride, chlorine gas, and water:[citation needed]

Ca(ClO)
2
+ 4HCl → CaCl
2
+ 2Cl
2
+ 2H
2
O

Safety

It is a strong oxidizing agent, as it contains a hypochlorite ion at the valence +1 (redox state: Cl+1).[citation needed]

Calcium hypochlorite should not be stored wet and hot, or near any acid, organic materials, or metals. The unhydrated form is safer to handle.[citation needed]

See also

References

  1. also chlorine powder, chloride of lime, chlorinated lime, "dry chlorine"
  1. "Key operating strategies for chlorine disinfection operating systems". http://www.environmental-expert.com/Files%5C5306%5Carticles%5C13866%5C500.pdf. 
  2. 2.0 2.1 "Calcium Hypochlorite - 3V Tech" (in en). https://www.3v-tech.com/en/technologies-and-solutions/13/calcium-hypochlorite. 
  3. 3.0 3.1 3.2 Vogt, H.; Balej, J; Bennett, J. E.; Wintzer, P.; Sheikh, S. A.; Gallone, P.; Vasudevan, S.; Pelin, K. (2010). Ullmann's Encyclopedia of Industrial Chemistry. Wiley-VCH. doi:10.1002/14356007.a06_483.pub2. ISBN 978-3527306732. 
  4. "Calcium hypochlorite". Chemistry World. https://www.chemistryworld.com/podcasts/calcium-hypochlorite/3008985.article. 
  5. Template:Cite tech report
  6. Nwaukwa, Stephen; Keehn, Philip (1982). "The oxidation of aldehydes to acids with calcium hypochlorite [Ca(ClO)2]". Tetrahedron Letters 23 (31): 3131–3134. doi:10.1016/S0040-4039(00)88577-9. 
  7. Nwaukwa, Stephen; Keehn, Philip (1982). "Oxidative cleavage of α-diols, α-diones, α-hydroxy-ketones and α-hydroxy- and α-keto acids with calcium hypochlorite [Ca(ClO)2]". Tetrahedron Letters 23 (31): 3135–3138. doi:10.1016/S0040-4039(00)88578-0. 
  8. Cohen, Julius (1900). Practical Organic Chemistry for Advanced Students. New York: Macmillan & Co.. p. 63. https://books.google.com/books?id=0xRIAAAAIAAJ. 
  9. National Research Council (1995). Prudent Practices in the Laboratory: Handling and Disposal of Chemicals. Washington, DC: The National Academies Press. p. 161. doi:10.17226/4911. ISBN 978-0-309-05229-0. 
  10. "8.41799 Calcium hypochlorite for synthesis". https://www.sigmaaldrich.com/BE/en/product/mm/841799. "Assay (iodometric): 67.0 - 75.0 %" 
  11. W.L Smith, Inorganic Bleaches, Production of Hypochlorite in Handbook of Detergents,Part F, (2009) Ed. U Zoller and Paul Sosis, CRC Press, ISBN:978-0-8247-0349-3
  12. Aleksandrova, M.M.; Dmitriev, G.A.; Avojan, R.L. (1968). "The probable model of the crystal structure of the twobase calcium hypochlorite". Armyanskii Khimicheskii Zhurnal 21: 380-386. 

External links