Bjerrum defect explained

A Bjerrum defect is a crystallographic defect which is specific to ice, and which is partly responsible for the electrical properties of ice.[1] It was first proposed by Niels Bjerrum in 1952 in order to explain the electrical polarization of ice in an electric field.[2] A hydrogen bond normally has one proton, but a hydrogen bond with a Bjerrum defect will have either two protons (D defect, from "doppel" in German, meaning "double"[3]) or no proton (L defect, from "leer" in German, meaning "empty"). D-defects are more energetically favorable than L-defects.[4] The unfavorable defect strain is resolved when a water molecule pivots about an oxygen atom to produce hydrogen bonds with single protons. Dislocations of ice Ih along a slip plane create pairs of Bjerrum defects, one D defect and one L defect.[5]

Nonpolar molecules such as methane can form clathrate hydrates with water, especially under high pressure. Although there is no hydrogen bonding of water molecules when methane is the guest molecule of the clathrate, guest-host hydrogen bonding often forms with guest molecules in clathrates of many larger organic molecules, such as pinacolone and tetrahydrofuran. In such cases the guest-host hydrogen bonds result in the formation of L-type Bjerrum defect in the clathrate lattice.[6] Oxygen atoms (in alcohol or carbonyl functional groups) and nitrogen atoms (in amine functional groups) in the guest molecules lead to transient hydrogen bonds and misoriented water molecules in the hydrate lattice.[7]

See also

Notes and References

  1. Web site: David E. Stillman . Robert E. Grimm . amp . Electrical properties of ice and implications for solar system exploration. . XXXIX . Lunar and Planetary Science . 2008 . 2010-09-09 .
  2. Bjerrum. N.. Structure and Properties of Ice. Science. 11 April 1952. 115. 2989. 385–390. 10.1126/science.115.2989.385. 17741864. 1952Sci...115..385B .
  3. Sugimoto Y . Seeing how ice breaks the rule . . 377 . 6603 . 264–265 . 2022 . 10.1126/science.add0841 . 35857600 .
  4. Watkins M, VandeVondele J, Slater B . Point defects at the ice (0001) surface . . 107 . 28 . 12429-31244 . 2010 . 10.1073/pnas.1001087107 . 2906571 . 20615938.
  5. Web site: Head, School of Earth Sciences . Dislocations . School of Earth Sciences - The University of Melbourne - Australia . March 15, 2004 . 2010-09-09 . dead . https://web.archive.org/web/20100710132411/http://web.earthsci.unimelb.edu.au/wilson/ice1/dislocation.html . July 10, 2010 .
  6. Alavi S, Susilo R, Ripmeester JA . Linking microscopic guest properties to macroscopic observables in clathrate hydrates: guest-host hydrogen bonding . Journal of Chemical Physics . 130 . 17 . 2009 . 174501 . . 10.1063/1.3124187 . 19425784. 2009JChPh.130q4501A .
  7. Alavi S, Udachin K, Ripmeester JA . Effect of guest-host hydrogen bonding on the structures and properties of clathrate hydrates . Chemistry: A European Journal . 16 . 3 . 2010 . 1017–1025 . 10.1002/chem.200902351 . 19946907.