Octachloropropane Explained

Octachloropropane or perchloropropane is the chemical compound with elemental formula and structural formula . Its molecule has a simple chain of three carbon atoms connected by single bonds, with chlorine atoms filling their remaining bonds. It is a chlorocarbon, specifically the third simplest perchloroalkane (after carbon tetrachloride and hexachloroethane). It can be described as a derivative of propane, with all hydrogen atoms replaced by chlorine.

Octachloropropane is a clear white crystalline solid at room temperature, with hexagonal crystal structure. It is easily deformed by mechanical stress, without losing its crystal structure, like a metal.

History

Synthesis and characterization of octachloropropane was reported in 1875 by Krafft and Merz. Its remarkable crystal growth and deformation properties were noted by McCrone in 1949. Its use as a model for crystal deformation of minerals was pioneered by Win D. Means, Marc W. Jessel and others in the 1980s.

Production

Octachloropropane can be obtained by reacting partially chlorinated propane with iodine trichloride (as in the original synthesis by Krafft and Merz), or with chlorine at high pressure or with activation by light. The temperature must be close to but below 200 °C, since at higher temperatures further reaction with chlorine gives carbon tetrachloride and hexachloroethane instead.

Chemistry

Octachloropropane treated with aluminium in diethyl ether affords several unsaturated perchlorocarbons, by way of hexachloropropene . For instance,

+ 2/3 2/3 +

2 + 4/3 4/3 + (three isomers)

2 + 2 2 + (two isomers)The products were identified as

α-: colorless, m. p. 148 °C.

β-: red, m. p. 155 °Cwith conjectured structures or, and

α-: b. p. 105-110 °C at 0.1 torr.

β-: m. p. 71 °C.

γ-: m. p. 183 °C.which were claimed to be cis/trans isomers and atropisomers of (octachloro(1,3,5)hexatriene).

Applications

Crystalline plasticity model

Octacholopropane is used by geologists and metallurgists as a model to study the plastic deformation of crystalline minerals and rocks under stress. The large individual crystalline grains (0.1-1.0 mm diameter) are distinguishable with a polarized light microscope at moderate magnification, and generally retain their size and approximate aspect ratio as the material undergoes shear strain. The grains will spontaneously arise from the quenched solid, in minutes or hours, even at room temperature.

The material's flow driven by stress can be followed by embedding in it small amounts of fine inert particles, such as grit 1000 abrasives; the particles apparently do not affect the grain evolution and deformation. Camphor (with rhombohedral crystal structure) was previously proposed for this use.

Metal separation

Octachlorpropane reacts with niobium pentoxide and tantalum pentoxide at atmospheric pressure yielding the corresponding chlorides. It also reacts with titanium dioxide, if the other two oxides are present. This reaction, followed with distillation of the titanium tetrachloride at about 225 °C, could be an effective way to remove from mixtures of those oxides.

Pesticide

Octachloropropane has been commercialized as a snail killer with the brand name HRS-1622, although it was not found to be very effective.

Octachloropropane was found to be highly toxic to larvae of the housefly, with an efficiency comparable to decachlorobutane and hexachlorobenzene (BHC). Unlike the latter, it is somewhat volatile and thus effective even without physical contact with the solid.

Environmental concerns

Octachloropropane was detected as a relatively minor item among dozens of highly chlorinated and perchlorinated hydrocarbons present as contaminants in the carbon tetrachloride produced from methanol by a plant in China, and also in the condensed waste from etching aluminium films in an integrated circuit factory.

See also

References

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Notes and References

  1. F. Asinger (196662): Paraffins: Chemistry and Technology. Revised English edition of German original published in 1956. 920 pages.
  2. Mark W. Jessell and G. S. Lister (1991): "Strain localization behaviour in experimental shear zones". Pure and Applied Geophysics, volume 137, page 421–438.
  3. A. Roedig (1948): "Über die Synthese einiger Polychlorpolyene und die Atropisomerie der Oktachlorhexatriene". Experientia, volume 4, pages 305–307
  4. Win D. Means and Jin-Han Ree (1988): "Seven types of subgrain boundaries in octachloropropane". Journal of Structural Geology, volume 10, issue 7, pages 765-770.
  5. Mark Jessel (1996): "Analogue Modelling at the University at Albany, State University of New York" (1996): Online collection of videos created by Youngdo Park, Jin-Han Ree, and Win D. Means. Accessed on 2020-07-03.
  6. Paul D. Bons, Mark W. Jessel, Lynn Evans, Terence Barr, and Karl Stüwe (2001) "Modeling of anisotropic grain growth in minerals" Tectonic Modeling: A Volume in Honor of Hans Ramberg; Geological Society of America Memoir, volume 193. 276 pages.
  7. Win D. Means (1983): "Microstructure and micromotion in recrystallization flow of octachloropropane: A first look". Geologische Rundschau, volume 71, pages 511-528.
  8. W. C. McCrone (1949): "Boundary migration and grain growth". Discussions of the Faraday Society, volume 5, pages 158-166.
  9. W. C. McCrone and P. T. Cheng (1949): "Grain growth in octachloropropane". Journal of Applied Physics, volume 20, pages 230–231
  10. P. A. Beck (1949): "Comments on grain growth in octachloropropane". Journal of Applied Physics, volume 20, page 231.
  11. J. L. Urai, F. J. Humphreys, and S. E. Burrows (1980): "In-situ studies of the deformation and dynamic recrystallization of rhombohedral camphor". Journal of Materials Science, volume 15, pages 1231–1240.
  12. K. R. S. Ascher and Z. H. Levinsox (1954): "Chemicals affecting the preimaginal stages of the housefly. III. Contact toxicity for third stage larvae of some chlorinated hydrocarbons deposited on adsorbent surfaces.". Rivista di Parassitologia, Volume 15, issue 1, pages 57-61.
  13. E. A. Seiffer and H. F. Schoof (197): "Tests of 15 experimental molluscicides against Australorbis glabratus". Public Health Reports, volume 82, issue 9, pages 833–839.
  14. Lifei Zhang, Wenlong Yang, Linli Zhang, Xiaoxiu Li (2015): "Highly chlorinated unintentionally produced persistent organic pollutants generated during the methanol-based production of chlorinated methanes: A case study in China". Chemosphere, volume 133, pages 1-5.
  15. Peggy Müller, Thomas Stock, Siegfried Bauer, and Ilona Wolff (2002): "Genotoxicological characterisation of complex mixtures: Genotoxic effects of a complex mixture of perhalogenated hydrocarbons". Mutation Research/Genetic Toxicology and Environmental Mutagenesis, volume 515, issues 1–2, pages 99-109
  16. Stephen W. Tobey and Robert. West (1964): "Hexachlorocyclopropane". Journal of the American Chemical Society, volume 86, issue 1, pages 56–61.
  17. R. H. Atkinson, Joseph Steigman, and C. F. Hiskey (1952): "Analytical chemistry of niobium and tantalum. Chlorination of titania and distillation separation from niobium and tantalum". Analytical Chemistry, volume 24, issue 3, pages 484–488.