Cinnabar
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| Cinnabar | |
|---|---|
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| General | |
| Category | Mineral |
| Chemical formula | mercury(II) sulfide, HgS |
| Identification | |
| Color | Brownish-red |
| Crystal habit | Rhombohedral to tabular. Granular to massive |
| Crystal system | Hexagonal |
| Cleavage | Prismatic, perfect |
| Fracture | Uneven to subconchoidal |
| Mohs Scale hardness | 2-2.5 |
| Luster | Adamantine to dull |
| Refractive index | 2.940-3.220[1] |
| Streak | Scarlet |
| Specific gravity | 8 - 8.2 g/cm³ |
| Solubility | 3×10-26 g per 100 ml water[citation needed] |
Cinnabar, sometimes written cinnabarite, is a name applied to red mercury(II) sulfide (HgS), or native vermilion, the common ore of mercury. The name comes from the Greek - "kinnabari" - used by Theophrastus, and was probably applied to several distinct substances. Other sources say the word comes from the Persian zinjifrah, a word of uncertain origin. In Latin it was known as minium, meaning also "red lead" - a word probably borrowed from Iberian[2] (cf. Basque armineá "cinnabar").
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[edit] Structure
HgS adopts two structures, i.e. it is dimorphous.[3] The more stable form is cinnabar, which has a structure akin to that for HgO: each Hg center has two short Hg-S bonds (2.36 Å), and four longer Hg---S contacts (3.10, 3.10, 3.30, 3.30 Å). The black form of HgS has the zinc blende structure.
[edit] Properties
Cinnabar is generally found in a massive, granular or earthy form and is bright scarlet to brick-red in color. It occasionally occurs, however, in crystals with a non-metallic adamantine luster. Cinnabar has a rombohedral bravais lattice, and belongs to the hexagonal crystal system, trigonal division. Its crystals grow usually in a massive habit, though they are sometimes twinned. The twinning in cinnabar is distinctive and forms a penetration twin that is ridged with six ridges surrounding the point of a pyramid. It could be thought of as two scalahedral crystals grown together with one crystal going the opposite way of the other crystal. The hardness of cinnabar is 2 - 2.5, and its specific gravity 8.998.
Cinnabar resembles quartz in its symmetry and certain of its optical characteristics. Like quartz, it exhibits birefringence. It has the highest refractive power of any mineral. Its mean index for sodium light is 3.08[1], whereas the index for diamond—a substance of remarkable refraction— is 2.42 and that for GaAs is 3.93.
See List of indices of refraction.
[edit] Occurrence
Generally cinnabar occurs as a vein-filling mineral associated with recent volcanic activity and alkaline hot springs.
Cinnabar is found in all localities that yield mercury, notably Almadén (Spain); New Almaden (California); Hastings Mine and St. John's Mine, Vallejo, California;[4] Idrija (Slovenia); New Idria (California); Landsberg, near Obermoschel in the Palatinate; Ripa, at the foot of the Apuan Alps (Tuscany); the mountain Avala (Serbia); Huancavelica (Peru); Terlingua (Texas); and the province of Guizhou in China, where fine crystals have been obtained.
Cinnabar is still being deposited at the present day from the hot waters of Sulphur Bank, in California, and Steamboat Springs, Nevada.
[edit] Mining and extraction of mercury
Cinnabar was mined by the Roman Empire both as a pigment (Vitruvius, DA VII; IV-V) (Pliny, HN; XXXIII, XXXVI-XLII) and for its mercury content (Pliny HN; XXXIII, XLI), and it has been the main source of mercury throughout the centuries. Some mines used by the Romans remain active today.[citation needed]
To produce liquid (quicksilver) mercury, crushed cinnabar ore is roasted in rotary furnaces. Pure mercury separates from sulfur in this process and easily evaporates. A condensing column is used to collect the liquid mercury, which is most often shipped in iron flasks.
Because of the high toxicity of mercury, both the mining of cinnabar and refining for mercury are hazardous and historic causes of mercury poisoning. In particular, the Romans used convict labor in their mines as a form of death sentence. The Spanish also used shorter term convict labor at the Almadén mines, with a 24% overall fatality rate in one 30 year period.
Abandoned mercury mine processing sites often contain very hazardous waste piles of roasted cinnabar calcines. Water runoff from such sites is a recognized source of ecological damage.
[edit] Medicinal use
Much fuss is made about medicinal use of Cinnabar, however Cinnabar has been used over the ages medicinally in the East and the West and its side effects are long known.
It is known to be highly toxic[2] - perhaps the first record of this is in the Thoroughly Revised Materia Medica (1751) and later in the work Harm and Benefit in the Materia Medica (1893). It is nevertheless used today (as is arsenic) to treat certain types of conditions with Western Medical Science translations approximating somewhere between "insomnia" and "depression". It is not "using poison to cure poison", as some claim - such images should be viewed as curious observation, not an offering for a mechanism of operation.
Modern herbal extracts that contain cinnabar (zhū shā / 朱沙) should be that obtained after aqueous tituration to refine the Cinnabar (HgS) away from any Mercury Oxide (HgO), as it is the water- and gastric-soluble forms of Mercury which are responsible for its toxicity[5]. The result is called "Floating Cinnabar" (shuǐ fēi zhū shā / 水飛朱沙), as opposed to líng shā (靈沙 / lit. "divine sand") or the highly toxic chén shā (辰沙 or 陳沙; lit "Chen sand"). The Harm and Benefit in the Materia Medica notes:
"...should be used unprepared. ... If refined with fire it is toxic, and taking it has often been fatal."
In Bensky, Clavey & Stöger's Materia Medica's entry for it, conveniently located at the beginning of the "Obsolete Substances" section, you will see this expressed in the modern language of chemistry:
"...completely pure cinnabar (HgS), when heated in the presence of oxygen, turns into mercury oxide (HgO), which is soluble in diluted acids such as gastric acid."
[edit] Decorative use
Cinnabar has been used for its color in the new world since the Olmec culture[6]. Cinnabar was often used in royal burial chambers during the peak of Mayan civilization. The red stone was inserted into limestone sarcophagi, both as a decoration and, more importantly, to deter vandals and thieves with its well-known toxicity.[citation needed]
The most popularly known use of cinnabar is in Chinese carved lacquerware, a technique that apparently originated in the Song Dynasty[3]. The danger of mercury poisoning may be reduced in ancient lacquerware by entraining the powdered pigment in lacquer[4], but could still pose an environmental hazard if the pieces were accidentally destroyed. In the modern jewelry industry, the toxic pigment is replaced by a resin-based polymer[5] that approximates the appearance of pigmented lacquer.
In the Byzantine Empire, the Emperor and certain privileged bishops (such as the Ecumenical Patriarch and the Archbishop of Cyprus) were allowed the exclusive right of signing their names with ink colored vermilion by the addition of cinnabar.
[edit] Other forms of cinnabar
- Hepatic cinnabar is an impure variety from the mines of Idrija in the Carniola region of Slovenia, in which the cinnabar is mixed with bituminous and earthy matter.
- Metacinnabarite is a black-colored form of HgS, which crystallizes in the cubic form.
- Synthetic cinnabar is produced by treatment of Hg(II) salts with hydrogen sulfide to precipitate black, synthetic metacinnabarite, which is then heated in water. This conversion is promoted by the presence of sodium sulfide.[7]
- Hypercinnabar, crystallise in the hexagonal form.
[edit] References
- ^ a b Schumann, Walter (1997). Gemstones of the World. Sterling. ISBN 0806994614.
- ^ OED "minium".
- ^ Wells, A.F. (1984). Structural Inorganic Chemistry, Oxford: Clarendon Press. ISBN 0-19-855370-6.
- ^ C.Michael Hogan, Marc Papineau et al., Environmental Assessment of the columbus Parkway Widening between Ascot Parkway and the Northgate Development, Vallejo, Earth Metrics Inc. Report 7853, California State Clearinghouse, Sept, 1989
- ^ Bensky, Dan; Clavey, Steven & Stöger, Erich (2004), Materia Medica: 3rd Edition, Eastland Press, pp. 1045-1047, ISBN 0-939616-4-24
- ^ New World's Oldest, in Time Magazine, Monday, Jul. 29, 1957[1]
- ^ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
