The people of the Caral culture traded for sodalite from the Collao altiplano.[6] First discovered by Europeans in 1811 in the Ilimaussaq intrusive complex in Greenland, sodalite did not become widely important as an ornamental stone until 1891 when vast deposits of fine material were discovered in Ontario, Canada.
Structure
The structure of sodalite was first studied by Linus Pauling in 1930.[7] It is a cubic mineral of space group P43n (space group 218) which consists of an aluminosilicate cage network with Na+ cations and chloride anions in the interframework. (There may be small amounts of other cations and anions instead.) This framework forms a zeolite cage structure. Each unit cell has two cavities, which have almost the same structure as the borate cage (B 24O 48)24− found in the zinc borateZn 4O(BO 2) 6,[8] the beryllosilicate cage (Be 12Si 12O 48)24− ,[7] and the aluminate cage (Al 24O 48)24− in Ca 8(Al 12O 24)(WO 4) 2,[9] and as in the similar mineral tugtupite (Na 4AlBeSi 4O 12Cl) (see Haüyne#Sodalite group). There is one cavity around each chloride ion. One chloride is located at the corners of the unit cell, and the other at the centre. Each cavity has chiral tetrahedral symmetry, and the cavities around these two chloride locations are mirror images one of the other (a glide plane or a four-fold improper rotation takes one into the other). There are four sodium ions around each chloride ion (at one distance, and four more at a greater distance), surrounded by twelve SiO 4 tetrahedra and twelve AlO 4 tetrahedra. The silicon and aluminum atoms are located at the corners of a truncated octahedron with the chloride and four sodium atoms inside.[8] (A similar structure called "carbon sodalite" may occur as a very high pressure form of carbon — see illustration in reference.[10]) Each oxygen atom links between an SiO 4 tetrahedron and an AlO 4 tetrahedron. All the oxygen atoms are equivalent, but one half are in environments that are enantiomorphic to the environments of the other half. The silicon atoms are at the location and symmetry-equivalent positions, and the aluminum ions at the location and symmetry-equivalent positions. The three silicon atoms and the three aluminum atoms listed above closest to a given corner of the unit cell form a six-membered ring of tetrahedra, and the four in any face of the unit cell form a four-membered ring of tetrahedra. The six-membered rings can serve as channels in which ions can diffuse through the crystal.[11]
The structure is a crumpled form of a structure in which the three-fold axes of each tetrahedron lie in planes parallel to the faces of the unit cell, thus putting half the oxygen atoms in the faces. As the temperature is raised the sodalite structure expands and uncrumples, becoming more like this structure. In this structure the two cavities are still chiral, because no indirect isometry centred on the cavity (i.e. a reflexion, inversion, or improper rotation) can superimpose the silicon atoms onto silicon atoms and the aluminum atoms onto aluminum atoms, while also superimposing the sodium atoms on other sodium atoms. A discontinuity of the thermal expansion coefficient occurs at a certain temperature when chloride is replaced by sulfate or iodide, and this is thought to happen when the framework becomes fully expanded or when the cation (sodium in natural sodalite) reaches the coordinates (et cetera).[11] This adds symmetry (such as mirror planes in the faces of the unit cell) so that the space group becomes Pm3n (space group 223), and the cavities cease to be chiral and take on pyritohedral symmetry.
Natural sodalite holds primarily chloride anions in the cages, but they can be substituted by other anions such as sulfate, sulfide, hydroxide, trisulfur with other minerals in the sodalite group representing end member compositions. The sodium can be replaced by other alkali group elements, and the chloride by other halides. Many of these have been synthesized.[11]
The characteristic blue color arises mainly from caged S−3 and S4 clusters.[12]
Properties
A sample of sodalite-carbonate pegmatite from Bolivia, with a polished rock surface.
A light, relatively hard yet fragile mineral, sodalite is named after its sodium content; in mineralogy it may be classed as a feldspathoid. Well known for its blue color, sodalite may also be grey, yellow, green, or pink and is often mottled with white veins or patches. The more uniformly blue material is used in jewellery, where it is fashioned into cabochons and beads. Lesser material is more often seen as facing or inlay in various applications.
Although somewhat similar to lazurite and lapis lazuli, sodalite rarely contains pyrite (a common inclusion in lapis) and its blue color is more like traditional royal blue rather than ultramarine. It is further distinguished from similar minerals by its white (rather than blue) streak. Sodalite's six directions of poor cleavage may be seen as incipient cracks running through the stone.
Hackmanite dodecahedron from the Koksha Valley, Afghanistan
Hackmanite is a variety of sodalite exhibiting tenebrescence.[14] When hackmanite from Mont Saint-Hilaire (Quebec) or Ilímaussaq (Greenland) is freshly quarried, it is generally pale to deep violet but the color fades quickly to greyish or greenish white. Conversely, hackmanite from Afghanistan and the Myanmar Republic (Burma) starts off creamy white but develops a violet to pink-red color in sunlight. If left in a dark environment for some time, the violet will fade again. Tenebrescence is accelerated by the use of longwave or, particularly, shortwave ultraviolet light. Much sodalite will also fluoresce a patchy orange under UV light.
^ abcHassan, I.; Grundy, H. D. (1984). "The crystal structures of sodalite-group minerals". Acta Crystallographica Section B. 40: 6–13. doi:10.1107/S0108768184001683.
^ abLe Maitre, R.W., ed. (2002). Igneous Rocks — A Classification and Glossary of Terms (2nd ed.). Cambridge: Cambridge University Press. p. 143. ISBN0-521-66215-X.
^Buhl, Josef-Christian; Löns, Jürgen (1996). "Synthesis and crystal structure of nitrate enclathrated sodalite Na8[AlSiO4]6(NO3)2". Journal of Alloys and Compounds. 235: 41–47. doi:10.1016/0925-8388(95)02148-5.
^Buhl, Josef-Christian (1996). "The properties of salt-filled sodalites. Part 4. Synthesis and heterogeneous reactions of iodate-enclathrated sodalite Na8[AlSiO4]6(IO3)2−x(OH·H2O)x; 0.7 < x < 1.3". Thermochimica Acta. 286 (2): 251–262. doi:10.1016/0040-6031(96)02971-1.
^Brenchley, Matthew E.; Weller, Mark T. (1994). "Synthesis and structures of M8[ALSiO4]6·(XO4)2, M = Na, Li, K; X = Cl, Mn Sodalites". Zeolites. 14 (8): 682–686. doi:10.1016/0144-2449(94)90125-2.
^Veit, Th.; Buhl, J.-Ch.; Hoffmann, W. (1991). "Hydrothermal synthesis, characterization and structure refinement of chlorate- and perchlorate-sodalite". Catalysis Today. 8 (4): 405–413. doi:10.1016/0920-5861(91)87019-J.
