Sulfosalts

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In chemistry, sulfo salts are the salts of thioacids (H 3 (AsS 3 ), H 3 (BiS 3 ), H 3 (SbS 3 ) etc.) and similar compounds .

In the mineral system , the structurally very heterogeneous sulfosalts form an important group in the class of sulfides .

Strunz and Nickel use the following definition for the Strunz Mineralogical Tables :

Sulphosalts are structurally characterized by complex anions with the basic building blocks [AsS 3 ] 3− , [SbS 3 ] 3− and [BiS 3 ] 3− . The ions of these anion complexes are arranged in the form of a trigonal pyramid with the three sulfur anions at the base of the pyramid and the semimetal cation at the top. The semimetal cations have another, free electron pair at the tip of the pyramid that is not involved in any bonds. The classification of the sulfosalts according to Strunz is carried out on the one hand structurally according to the concept of SnS and PbS structure types and homologous series derived from them and on the other hand according to the chemical-structural scheme of Nowacki and Edenharter.

The sulfosalt sub-committee of the IMA commission on ore mineralogy is developing a revised system of sulfosalts with a more general definition:

Sulphosalts are minerals with complex anions from semimetal or metal cations and chalcogenide anions . The criterion for differentiation from other chalcogenide compounds is the lack of bonds between the central cations in the anion complexes and the other cations in the structure. According to this definition, in addition to the classic sulfosalts of Strunz's groups 2H and 2J, numerous chalcogenides from other groups (e.g. 2E, 2F, 2G, 2K, 2L) also belong to the sulfosalts, currently around 260 minerals . For another 200, the affiliation is still unclear.

The compositions obey the general formula A m (B n X p ), wherein

  • A stands for the metal cations Pb 2+ , Ag + , Cu + , Zn 2+ , Hg 2+ , Tl + , Cd 2+ , Fe 2+ , Sn 2+ , Mn 2+ , Au + ,
  • B for the cations As 3+ , Sb 3+ , Bi 3+ , Te 4+ , Sn 4+ , Ge 4+ , As 5+ , Sb 5+ , V 5+ , Mo 6+ , W 6+ , In
  • and X for chalcogen anions S 2− , Se 2− , Te 2− , some of which can be replaced by Cl - or O 2− .

The structural formulas are sometimes complex and variable and often not stoichiometric, i.e. the number of atoms is not always in an integer ratio to one another. Sometimes different formulas are given for a mineral. Various sulfosalt minerals with similar compositions or structures often appear in submicroscopic, regular adhesions. Until recently, some of these adhesions were considered to be minerals in their own right.

Sulphosalts are opaque with mostly lead-gray metallic sheen and medium reflectivity. Their Mohs hardness is low (2–4) and their density of 4–7 g / cm³ is very high. The electrical properties of some sulfosalts ( semiconductors , solid electrolytes ) make them interesting for technical applications.

Etymology and history

The term was introduced in the 19th century by analogy with the oxy salts. The complex anions of arsenates , phosphates or silicates , for example , can be clearly identified there on the basis of the bond strengths as independent structural units in the overall structure. Strong bonds with a high covalent content occur within the oxidic anion complexes , whereas the bonds to the other cations are significantly weaker with predominantly ionic character. The introduction of the term “sulfosalt” was associated with the idea that comparable proportions prevail for the salts of sulfonic acids. However, later studies could not always confirm this. The bond conditions in sulfosalts are more complex with a clearly metallic character and the bond strengths between the cations and the sulfur ions of the anion complexes are not always weaker than the z. B. within the AsS 3 group.

Education and Locations

Sulphosalts are widespread in hydrothermal deposits, where they are deposited both at low to medium temperatures (sulfoantimotites, sulfoarsenites) and at higher temperatures (sulfobismuthites). They can also be found as waste products from undersea volcanoes , black smokers and white smokers.

structure

Structurally, minerals in this group differ from other chalcogenides such as B. Arsenopyrite (FeAsS) or Löllingite (FeAs 2 ) in that the A cations do not form any bonds with the B semimetal ions. Most of the time, the B cations form pyramidal BS 3 anion complexes with the three anions at the base and the semimetal cation at the top, which has a free pair of unbound electrons. However, other anion environments, especially Bi and Sb, occur.

use

The industrial importance of the sulfo salts is low. They are of local importance as raw materials for rare metals such as Ag, Au, Tl, Te. Some sulfosalts are currently attracting strong interest from industry because of their semiconductor properties. Synthetic sulfosalts (Sn x (Sb, Bi) y (S, Se) z , CuInSe 2 ) can be used for the production of solar cells. The use of these materials promises a higher degree of efficiency than silicon with lower production costs. Another area of ​​application is the manufacture of detectors for X-rays.

Classification

Chemical classification
Anion cation Chemical name
S 2− As 3+ Thioarsenites
Sb 3+ Thioantimonites
Bi 3+ Thiobismuthites
Te 4+ Thiotellurites
(P 5+ ) Thiophospates
As 5+ Thioarsenates
Sb 5+ Thioantimonates
Sn 4+ Thiostannates
Ge 4+ Thiogermanate
V 5+ Thiovanadate
Mon 6+ Thiomolybdates
W 6+ Thio tungstates
Se 2− As 3+ Selenioarsenite
Sb 3+ Selenioantimonite
Bi 3+ Seleniobismuthite
Sb 5+ Selenium antimonates
Te 2− Bi 3+ Tellurobismuthite

A classification based solely on the composition divides the sulfosalts according to the structure of their complex anions (see table).

The current mineralogical classification of the IMA committee for sulfosalts is shown here. For the sulfosalts with As 3+ , Sb 3+ , Bi 3+ , Te 4+ on the B position, they first give a classification according to chemically defined classes and below that purely structurally with the following levels:

The following abbreviations are used in the structural formulas of the groups and subgroups:

Sulphosalts with a cation / chalcogen ratio of 1: 1

Binary sulfosalts M + PnCh 2

Matildit series: (Strunz: 2.CD.15)

Aramayoit series: (Strunz: 2.HA.25)

Cuboargyrit type: (Strunz: 2.CD.10)

Miargyrite type: (Strunz: 2.HA.10)

Smithite type: (Strunz: 2.GC.30)

Trechmannite type: (Strunz: 2.GC.35)

Emplectit series: (Strunz: 2.HA.05)

Weissbergite homeotype:

Ternary sulfosalts (M1 + M2 2+ PnS 3 )

Free life family

  • Free life : AgPbSbS 3 (Strunz: 2.JB.15)
  • Marrit : AgPbAsS 3 (Strunz: 2.JB.15)
  • Diaphorite : Ag 3 Pb 2 Sb 3 S 3 (Strunz: 2.JB.5)
  • Quadratite : Ag (Cd, Pb) (As, Sb) S 3 (Strunz: 2.GC.25)
  • Schapbachite : Ag 0.4 Pb 0.2 Bi 0.4 S 3 (Strunz: 2.CD.10)

Bournonite series: (Strunz: 2.GA.50)

Mückeit series: (Strunz: 2.GA.25)

Christite-Type: (Strunz: 2.HD.15)

Quaternary sulfosalts (M1 + M2 2+ M3 3+ Pn 2 S 5 )

Hatchit isotype: (Strunz: 2.GC.05)

Lead sulfosalts with pronounced two-dimensional architecture (layer structures)

Sulphosalts with tetradymite-like layer structures

Aleksit series Pb (n − 1) Bi 2 Ch n + 2 : (Strunz: 2.DC.05)

Complex structural variant :: (Strunz: 2.DC.05)

Composite structures with alternating pseudo-hexagonal and PbS / SnS-like layers

Commensurable structures

Nagyaite series: (Strunz: 2.HB.20)

Related structure:

  • Museumite : [Pb 2 (Pb, Sb) 2 S 8 ] (Te, Au) 2 (Strunz: 2.HB.20)
  • Berryite : Cu 3 Ag 2 Pb 3 Bi 7 S 16 (Strunz: 2.HB.05)

provisionally assigned

Incommensurable structures

Kylindrit series: (Strunz: 2.HF.25)

Franckeit type :: (Strunz: 2.HF.25)

  • Coiraite : (Pb, Sn) 12.5 As 3 Sn 5 FeS 28
  • Franckeit : ~ Fe (Pb, Sn 2+ ) 6 Sn 4+ Sb 2 S 14

Lengenbachite type: (Strunz: 2.HF.30)

Cannizzarite type: (Strunz: 2.JB.20)

Commensurable composite structures derived from cannizzarite

Cannizzarit Plesiontye

Structures with stepped layers: (Strunz: 2.JB.25)

Structures with sheared, checkerboard-like layers: (Strunz: 2.JB.45)

Cannizarite modifications with honeycomb structures

  • Neyit : Cu 6 Ag 2 Pb 25 Bi 26 S 68 (Strunz: 2.JB.50)
  • Rouxelite : Cu 2 HgPb 22 S 64 (O, S) 2 (Strunz: 2.HF.35)

Lead sulfosalts with large 2-dimensional fragments which can be traced back to the PbS / SnS structure type

Lillianite series

All minerals in this family belong to a homologous series. Their structure is based on PbS-like layers of different thicknesses. The layer thickness is given in the number N of octahedra in the notation N L or N1, N2 L for different layers of different thicknesses.

Lillianit homeotype ( 4 L): (Strunz: 2.JB.40)

Bi-rich

Sb-rich - Andorite series:

The andorite series includes orthorhombic and pseudoorthorhombic sulfosalt minerals, the composition of which can be expressed with the formula n * (PbAgMn) 2 + x Sb 3-x S 6 .

  • Ramdohrite : (PbAgMn) 4.5 Sb 5.5 S 12 with x = 0.25 and n = 2 ((Cd, Mn, Fe) Ag 5.5 Pb 12 Sb 21.5 S 48 )
  • Fizélyit : (PbAgMn) 4.75 Sb 5.25 S 12 with x = 0.375 and n = 2 (Ag 5 Pb 14 Sb 21 S 48 )
  • Uchucchacuait : (PbAgMn) 5 Sb 5 S 12 with x = 0.5 and n = 2 (MnAgPb 3 Sb 5 S 12 )
  • Andorite IV : (PbAgMn) 8 Sb 12 S 24 with x = 0 and n = 4 (Ag 15 Pb 18 Sb 47 S 96 )
  • Andorite VI : (PbAgMn) 12 Sb 18 S 36 with x = 0 and n = 6 (AgPbSb 3 S 6 )

Lilianite dimorphic ( 4.4 L):

( 4.7 L) homologous:

( 4.8 L) homologous:

Heyrovskýit series: ( 7 L): (Strunz: 2.JB.40)

Structurally related ( 5.9 L):

Ouaryit pair ( 11.11 L): (Strunz: 2.JB.40)

Related structure? (Strunz: 2.LB.10)

Pavonit series (Strunz: 2.JA.05)

Derived structures

Cuprobismutite series (Strunz: 2.JA.10)

Related

Meneghinit series (Strunz: 2.HB.05)

Jordanite series

Jordanite type: (Strunz: 2.JB.30)

Kirkiit type: (Strunz: 2.JB.30)

Related structure (?): (Strunz: 2.LB.15)

PbS structure type (hexagonal) (Strunz: 2.JB.55)

Plagionite series (Strunz: 2.HC.10)

Sartorit series (Strunz: 2.HC.05)

Sartorite type

Baumhauerite type

Dufrénoysite type

Homologues with stacking sequences of high periodicity

Structures derived from Dufrenoysite

Pierrotite type

Unclassified

  • Mutnovskit : Pb 2 AsS 3 (I, Cl, Br) (Strunz: 2.FC.40)

Lead sulfosalts with one-dimensional, mostly rod-shaped structural units that can be traced back to the PbS / SnS structure type

Boulangerite family (rod and layer-shaped units)

Jamesonite series (Strunz: 2.HB.15)

Berthierite series (Strunz: 2.HA.20)

Zinkenite family

Zinkenit series

  • Zinkenit : Pb 9 Sb 22 S 42 (Strunz: 2.JB.35)
  • Pilait : Pb 9 Sb 10 S 23 ClO 0.5 (Strunz: 2.JB.35)
  • Scainiit : Pb 14 Sb 30 S 54 O 5 (Strunz: 2.JB.35)
  • Marrucciite : Hg 3 Pb 16 Sb 18 S 46 (Strunz: 2.JB.60)
  • Pellouxite : (Cu, Ag) 2 Pb 21 Sb 23 S 55 ClO (Strunz: 2.JB.35)
  • Vurroit : Sn 2 Pb 20 (Bi, As) 22 S 54 Cl 6 (Strunz: 2.LB.45)
  • Owyheeit : Ag 3 Pb 10 Sb 11 S 28 (Strunz: 2.HC.35)

Related structures with checkerboard-like structural units

Kobellite series (Strunz: 2.HB.10)

Geissenite type: (Strunz: 2.HB.10)

  • Giessenite : (Cu, Fe) 2 Pb 26.4 (Bi, Sb) 19.6 S 57 (monoclinic)
  • Izoklakeit : (Cu, Fe) 2 Pb 26.4 (Sb, Bi) 19.6 S 57 (orthorhombic)

Related structure: (Strunz: 2.HB.10)

  • Eclarit : (Cu, Fe) Pb 9 Bi 12 S 28

Structural relationship unclear: (Strunz: 2.HB.10)

Aikinite bismuthinite series (Strunz: 2.HB.05)

Related sulfosalts with unknown structure (January 2008) (Strunz: 2.LB.30)

Tl (Pb) and Hg sulfosalts: structures with SnS layers

Hutchinsonite series

Hutchinsonite-Bernadite pair

Ebenharterit-Jentschit pair

Other

  • Imhofit : Tl 5.8 As 15.4 S 26 (Strunz: 2.HD.30)
  • Gillulyit : Tl 2 As 7.5 Sb 0.3 S 13 (Strunz: 2.JC.10)

PbS original type

  • Gerstleyite : Na 2 (Sb, As) 8 S 13 .2H 2 O (Strunz: 2.HE.05)

Rebulit couple

  • Rebulit : Tl 5 As 8 Sb 5 S 22 (Strunz: 2.HD.25)
  • Jankovićit : Tl 5 Sb 9 (As, Sb) 4 S 22 (Strunz: 2.HD.20)

Sure type

  • Safety : Ag 2 Tl (As, Sb) 4 S 6 (Strunz: 2.HD.55)

Unclassified

  • Erniggliit : SnTl 2 As 2 S 6 (Strunz: 2.GA.45)
  • Vrbait : Hg 3 Tl 4 As 8 Sb 3 S 20 (Strunz: 2.HF.20)
  • Simonite : HgTlAs 3 S 6 (Strunz: 2.GC.20)
  • Vaughanite : HgTlSb 4 S 7 (Strunz: 2.LA.20)
  • Gabrielite : Cu 2 AgTl 2 As 3 S 7 (Strunz: 2.HD.60)

Sulphosalts with an excess of small (monovalent) cations (Ag, Cu) in relation to As, Sb, Bi

Cu (Ag) - rich sulfo salts

Wittichenite type (Strunz: 2.GA.20)

Tetrahedron series (Strunz: 2.GB.05)

Related structure type: (Strunz: 2.GB.05)

  • Galkhait : (Cs, Tl) (Hg, Cu, Zn, Tl) 6 (As, Sb) 4 S 12

Nowackiit series (Strunz: 2.GA.30)

Related structures:

Routhierite type (Struz: 2.GA.40)

Unclassified Cu sulfosalts

  • Miharait : Cu 4 FePbBiS 6 (Strunz: 2.LB.05)
  • Petrovicit : Cu 3 HgPbBiSe 5 (Strunz: 2.LB.40)
  • Mazzettiite : Ag 3 HgPbSbTe 5 (Strunz: 2.LB.40)
  • Chaméanite : (Cu, Fe) 4 As (Se, S) 4 (Strunz: 2.LA.35)
  • Mgriit : (Cu, Fe) 3 AsSe 3 (Strunz: 2.LA.45)
  • Larosite : (Cu, Ag) 21 PbBiS 13 (Strunz: 2.LB.35)
  • Arcubisit : CuAg 6 BiS 4 (Strunz: 2.LA.40)

Ag-rich sulfosalts

Samsonite type

  • Samsonite : MnAg 4 Sb 2 S 6 (Strunz: 2.GA.15)

Pyrargyrite family

Pyrostilpnit type (Strunz: 2.GA.10)

Polybasit series (Strunz: 2.GB.15)

Stephanite type

Unclassified Ag sulfosalts

Unclassified sulfosalts

Oxysulfosalts

  • Sarabauit : Sb 4 S 6 . CaSb 6 O 10 (Strunz: 2.HE.1)
  • Cetineite : NaK 5 Sb 14 S 3 O 18 (H 2 O) 6 (Strunz: 2.FD.15)
  • Ottensite : Na 3 (Sb 2 O 3 ) 3 (SbS 3 ). 3H 2 O (Strunz: 2.FD.15)

Subsulfosalts (?)

PGE sulfosalts (?)

  • Borovskit : Pd 3 SbTe 4 (Strunz: 2.LA.60)
  • Crerarit : (Pt, Pb) Bi 3 (S, Se) 4-x (Strunz: 2.CD.10)

Sulphosalts not taken into account in the current classification of the IMA

Thioarsenates

Thioantimonates

Tiostannate

Thioindate

  • Cadmoonite : CdIn 2 S 4 (Strunz: 2.DA.05)
  • Indit : FeIn 2 S 4 (Strunz: 2.DA.05)

Thiogermanate

  • Argyrodite : Ag 8 GeS 6 (Strunz: 2.BA.35)
  • Barquillite : Cu 2 (Cd, Zn) GeS 4 (Strunz: 2.KA.10)
  • Briartite : Cu 2 (Fe, Zn) GeS 4 (Strunz: 2.KA.10)
  • Calvertite : Cu 5 Ge 0.5 S 4 (Strunz: 2.CA.15)
  • Germanite : Cu 13 Fe 2 Ge 2 S 16 (Strunz: 2.CB.30)
  • Putzit : Cu 4.7 Ag 3.3 GeS 6 (Strunz: 2.BA.35)

Thiovanadate

Thiomolybdate / stannate

  • Hemusite : Cu 6 SnMoS 8 (Strunz: 2.CB.35)

Thio tungstate / stannate

Thiomolybdate / germanate

  • Maikainite : Cu 20 (Fe, Cu) 6 Mo 2 Ge 6 S 32 (Strunz: 2.CB.30)

Thio tungstate / germanate

  • Catamarcaite : Cu 6 GeWS 8 (Strunz: 2.CB.35)
  • Ovamboite : Cu 20 (Fe, Cu, Zn) 6 W 2 Ge 6 S 32 (Strunz: 2.CB.30)

Other mixed species

  • Colusite : (Cu 12 V (Sb, As, Sn) 3 ) S 16 (Strunz: 2.CB.30)
  • Germanocolusite : Cu 13 V (Ge, As) 3 S 16 (Strunz: 2.CB.30)
  • Nekrasovit : Cu 13 V (Sn, As, Sb) 3 S 16 (Strunz: 2.CB.30)
  • Renierite : (Cu, Zn) 11 Fe 4 (Ge, As) 2 S 16 (Strunz: 2.CB.35)
  • Stibiocolusite : Cu 13 V (As, Sb, Sn) 3 S 16 (Strunz: 2.CB.30)
  • Vinciennite : (Cu 10 Fe 4 SnAs) S 16 (Strunz: 2.CB.35)

Selenioantimonate

Web links

literature

  • NN Mozgova: Sulfosalt mineralogy today . (PDF; 61 MB) MSF Mini-Symposium Modern Approaches to Ore and Environmental Mineralogy , 2000, Espoo Finland, Extended Abstracts, p. 66.
  • Yves Moëlo, Emil Makovicky, Nadejda N. Mozgova, John L. Jambor, Nigel Cook, Allan Pring, Werner Paar, Ernest H. Nickel, Stephan Graeser, Sven Karup-Møller, Tonči Balic-Žunic, William G. Mumme, Filippo Vurro , Dan Topa, Luca Bindi, Klaus Bente, Masaaki Shimizu: Sulfosalt systematics: a review. Report of the sulfosalt sub-committee of the IMA Commission on Ore Mineralogy . In: European Journal of Mineralogy . tape 20 , no. 1 , 2008, p. 7–62 , doi : 10.1127 / 0935-1221 / 2008 / 0020-1778 ( PDF ).
  • Hugo Strunz , Ernest H. Nickel: Strunz Mineralogical Tables . 9th edition. E. Schweizerbart'sche Verlagbuchhandlung (Nägele and Obermiller), Stuttgart 2001, ISBN 3-510-65188-X , p. 56 .
  • Massimo Nespolo, Tohru Ozawa, Yusuke Kawasaki, Kazumasa Sugiyama: Structural relations and pseudosymmetries in the andorite homologous series . In: Journal of Mineralogical and Petrological Sciences . tape 107 , no. 6 , 2012, p. 226-243 , doi : 10.2465 / jmps.120730 ( PDF ).

Individual evidence

  1. ↑ Strunz Mineralogical Tables, 9th edition
  2. ↑ N. Makovicky. In: Jb. Min. , Abh. 1989, pp. 269–297 etc.
  3. ↑ Switzerland. Min. Petr. Mitt. , 1969, pp. 109-156
  4. ↑ Switzerland. Min. Petr. Mitt. , 1976, pp. 195-217
  5. ↑ a b Sufosalt systematics: a review .
  6. ↑ a b c d e f Nespolo et al .: Structural relations and pseudosymmetries in the andorite homologous series . 2012