Calcium carbide

Calcium carbide
Names
IUPAC name
Calcium carbide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.000.772
Properties
CaC2
Molar mass 64.099 g/mol
Appearance White powder to grey/black crystals
Density 2.22 g/cm3
Melting point 2,160 °C (3,920 °F; 2,430 K)
Boiling point 2,300 °C (4,170 °F; 2,570 K)
Rapid hydrolysis
Structure
Tetragonal [1]
D174h, I4/mmm, tI6
6
Thermochemistry
70 J·mol−1·K−1
−63 kJ·mol−1
Hazards
Main hazards Reacts with water to release acetylene gas
NFPA 704
Flammability code 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g., propaneHealth code 1: Exposure would cause irritation but only minor residual injury. E.g., turpentineReactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g., phosphorusSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g., cesium, sodiumNFPA 704 four-colored diamond
4
1
2
305 °C (581 °F; 578 K) (acetylene)
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 carbide is a chemical compound with the chemical formula of CaC2. Its main use industrially is in the production of acetylene and calcium cyanamide.[2]

The pure material is colorless, however pieces of technical-grade calcium carbide are grey or brown and consist of about 80–85% of CaC2 (the rest is CaO (calcium oxide), Ca3P2 (calcium phosphide), CaS (calcium sulfide), Ca3N2 (calcium nitride), SiC (silicon carbide), etc.). In the presence of trace moisture, technical-grade calcium carbide emits an unpleasant odor reminiscent of garlic.[3]

Applications of calcium carbide include manufacture of acetylene gas, and for generation of acetylene in carbide lamps; manufacture of chemicals for fertilizer; and in steelmaking.

Production

Calcium carbide is produced industrially in an electric arc furnace from a mixture of lime and coke at approximately 2200 °C.[4] This method has not changed since its invention in 1892:

CaO + 3 C → CaC2 + CO

The high temperature required for this reaction is not practically achievable by traditional combustion, so the reaction is performed in an electric arc furnace with graphite electrodes. The carbide product produced generally contains around 80% calcium carbide by weight. The carbide is crushed to produce small lumps that can range from a few mm up to 50 mm. The impurities are concentrated in the finer fractions. The CaC2 content of the product is assayed by measuring the amount of acetylene produced on hydrolysis. As an example, the British and German standards for the content of the coarser fractions are 295 L/kg and 300 L/kg respectively (at 101 kPa pressure and 20 °C temperature). Impurities present in the carbide include phosphide, which produces phosphine when hydrolysed.[5]

This reaction was an important part of the industrial revolution in chemistry, and was made possible in the USA as a result of massive amounts of inexpensive hydroelectric power produced at Niagara Falls before the turn of the 20th century.[6]

The method for the production in an electric arc furnace was discovered in 1892 by T. L Willson and independently by H. Moissan in the same year.[7][8][9]

Crystal structure

Pure calcium carbide is a colourless solid. The common crystalline form at room temperature is a distorted rock-salt structure with the C22− units lying parallel.[10]

Applications

Production of acetylene

The reaction of calcium carbide with water, producing acetylene and calcium hydroxide,[4] was discovered by Friedrich Wöhler in 1862.

CaC2(s) + 2H2O(aq) → C2H2(g) + Ca(OH)2(aq)

This reaction was the basis of the industrial manufacture of acetylene, and is the major industrial use of calcium carbide.

At high temperatures, CaC2 reacts with water vapor to give calcium carbonate, carbon dioxide and hydrogen.

Today acetylene is mainly manufactured by the partial combustion of methane or appears as a side product in the ethylene stream from cracking of hydrocarbons. Approximately 400,000 tonnes are produced this way annually (see Acetylene Preparation).

In China, acetylene derived from calcium carbide remains a raw material for the chemical industry, in particular for the production of polyvinyl chloride. Locally produced acetylene is more economical than using imported oil.[11] Production of calcium carbide in China has been increasing. In 2005 output was 8.94 million tons, with the capacity to produce 17 million tons.[12]

In the USA, Europe, and Japan, consumption of calcium carbide is generally declining.[13] Production levels in the USA in 1990s were 236,000 tons per year.[10]

Production of calcium cyanamide

Calcium carbide reacts with nitrogen at high temperature to form calcium cyanamide:[4]

CaC2 + N2 → CaCN2 + C

Commonly known as nitrolim, calcium cyanamide is used as fertilizer. It is hydrolysed to cyanamide, H2NCN.[4]

Steelmaking

Calcium carbide is used:

Carbide lamps

Lit carbide lamp

Calcium carbide is used in carbide lamps. Water dripping on carbide produces acetylene gas, which burns and produces light. While these lamps gave steadier and brighter light than candles, they were dangerous in coal mines, where flammable methane gas made them a serious hazard. The presence of flammable gases in coal mines led to miner safety lamps such as the Davy lamp, in which a wire gauze reduces the risk of methane ignition. Carbide lamps were still used extensively in slate, copper, and tin mines where methane is not a serious hazard. Most miners' lamps have now been replaced by electric lamps.

Carbide lamps are still used for mining in some less wealthy countries, for example in the silver mines near Potosí, Bolivia. Carbide lamps are also still used by some cavers exploring caves and other underground areas,[14] although they are increasingly being replaced in this use by LED lights.

Carbide lamps were also used extensively as headlights in early automobiles, motorcycles and bicycles, but have been replaced entirely by electric lamps.[15]

Other uses

Calcium carbide is sometimes used as source of acetylene gas, which is a ripening agent similar to ethylene.[16] However, this is illegal in some countries as, in the production of acetylene from calcium carbide, contamination often leads to trace production of phosphine and arsine.[17][18] These impurities can be removed by passing the acetylene gas through acidified copper sulfate solution, but, in developing countries, this precaution is often neglected.

Calcium carbide is used in toy cannons such as the Big-Bang Cannon, as well as in bamboo cannons. In the Netherlands calcium carbide is used around new-year to shoot with milk churns.[19]

Calcium carbide, together with calcium phosphide, is used in floating, self-igniting naval signal flares, such as those produced by the Holmes' Marine Life Protection Association.

References

  1. ↑ Massalimov, I. A.; Kireeva, M. S.; Sangalov, Yu. A. (2002). "Structure and Properties of Mechanically Activated Barium Peroxide". Inorganic Materials. 38 (4): 363. doi:10.1023/A:1015105922260.
  2. ↑ Patnaik, Pradyot (2003). Handbook of Inorganic Chemical Compounds. McGraw-Hill. ISBN 0-07-049439-8.
  3. ↑ Vincoli, Jeffrey Wayne (25 November 1996). Risk Management for Hazardous Chemicals. CRC Press. p. 429. ISBN 978-1-56670-200-3.
  4. 1 2 3 4 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 298. ISBN 0-08-037941-9.
  5. 1 2 Calcium Carbide, Bernhard Langhammer, Ullmann's Encyclopedia of Industrial Chemistry, Wiley Interscience. (Subscription required)
  6. ↑ Freeman, Horace (1919). "Manufacture of Cyanamide". The Chemical News and the Journal of Physical Science. 117: 232.
  7. ↑ Morehead, J. T. and de Chalmot, G. (1896). "The Manufacture of Calcium Carbide". Journal of the American Chemical Society. 18 (4): 311–331. doi:10.1021/ja02090a001.
  8. ↑ Moissan, H. (1892). "Chimie Minérale – Description d'un nouveau four électrique". Comptes rendus hebdomadaires des séances de l'Académie des sciences. 115: 1031.
  9. ↑ Renouf, Edward (1899). "The use of Acetylene". Popular Science Monthly: 335–347.
  10. 1 2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0-08-037941-9.
  11. ↑ Dun, Ya (2006-01-23). "Troubles in the PVC industry". Hong Kong Trade Development Council. Archived from the original on 2007-12-28.
  12. ↑ "Government takes measures to curb development of calcium carbide sector". China Daily via BusyTrade.com. 2007-05-16. Archived from the original on 2007-02-11.
  13. ↑ Lacson, Jamie; Schlag, Stefan and Toki, Goro (December 2004). "Calcium Carbide". SRI Consulting.
  14. ↑ "Caving equipment and culture (from Te Ara Encyclopedia of New Zealand)".
  15. ↑ Clemmer, Gregg (1987). American Miners' Carbide Lamps: A Collectors Guide to American Carbide Mine Lighting. Westernlore Publications.
  16. ↑ Abeles, F. B. and Gahagan, H. E. III (1968). "Abscission: The Role of Ethylene, Ethylene Analogues, Carbon Dioxide, and Oxygen". Plant Physiol. 43 (8): 1255–1258. doi:10.1104/pp.43.8.1255. PMC 1087003. PMID 16656908.
  17. ↑ "Bet on it. Your mango is ripened using carbide". dna. 2013-05-18. Retrieved 2018-08-25.
  18. ↑ "Eating Artificially Ripened Fruits is Harmful".
  19. ↑ "Carbidschieten wordt feest" (in Dutch). Algemeen Dagblad. 2016-12-24.
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