Arsenate arsenite

An arsenate arsenite is a chemical compound or salt that contains arsenate and arsenite anions (AsO33- and AsO43-). These are mixed anion compounds or mixed valence compounds. Some have third anions. Most known substances are minerals, but a few artificial arsenate arsenite compounds have been made. Many of the minerals are in the Hematolite Group.

Yellow spherules of halilsarpite, an arsenate arsenite mineral, on orange-brown smolyaninovite

An arsenate arsenite compound may also be called an arsenite arsenate.

Properties

Some members of this group of materials like mcgovernite has an extremely high unit cell dimension of 204 Å.[1]

Mixed valence pnictide compounds related to the arsenate arsenites include the nitrite nitrates, and phosphate phosphites.

List
name formula ratio

AsO4:AsO3

 system space group unit cell Å volume density properties references
Arsenic dioxide AsO2 1:1 orthorhomnic Pnma a=8.597 b=5.235 c=7.269 Z=8 327.1 4.382 [2]
Arsenic(III) Arsenic(V) Oxide Hydroxide As3O5(OH) 1:2 monoclinic P21/c a = 12.504 b = 4.593 c = 10.976 β = 118.08° Z = 4 556.2 3.84 [3]
H6As3+7As5+7O31 1:1 hexagonal P63 a = 12.0525 c = 4.7344 Z = 2 595.6 [4]
Segerstromite Ca3(As5+O4)2[As3+(OH)3]2 2:1 cubic I213 a = 10.7627 Z = 4 1246.71 3.46 colourless; refract index: n = 1.731 [5]
Synadelphite Mn2+9(As5+O4)2(As3+O3)(OH)9 · 2H2O 2:1 Orthorhombic Pnma a = 10.75 b = 18.86c = 9.88 Z=4 2005 3.58 red; Biaxial (+); refract index: nα = 1.750 - 1.870 nβ = 1.751 - 1.880 nγ = 1.761 - 1.930 [6]
Hematolite (Mn,Mg,Al,Fe3+)15(As5+O4)2(As3+O3)(OH)23 2:1 trigonal R3 a = 8.275 Å, c = 36.60 Å Z=3 2,170.4 3.49 deep red; Uniaxial (-) refractive index nω = 1.733 nε = 1.714; Birefringence: 0.019 [7][8]
Turtmannite (Mn,Mg)22.5Mg3-3x((V5+,As5+)O4)3(As3+O3)x(SiO4)3O5-5x(OH)20+x trigonal a = 8.259 c = 204.3 Z=12 12,068 3.8 light yellow; Uniaxial (-); refractive index: nε = 1.787 [9]
Carlfrancisite Mn2+3(Mn2+,Mg,Fe3+,Al)42[As3+O3]2(As5+O4)4[(Si,As5+)O4]6[(As5+,Si)O4]2(OH)42 trigonal R3c a = 8.2238 c = 205.113 Z=6 12,013.5 3.620 yellow-orange; Uniaxial (+) refractive index: nω = 1.756(2) nε = 1.758 Birefringence: δ = 0.002 [10]
K2Cu3(As2O6)2 1:1 monoclinic C2m a=10.359 b=5.388 c=11.234 β=110.48° [As(V)As(III)O6]4− [11]
Dixenite CuMn2+14Fe2+(SiO4)2(As5+O4)(As3+O3)5(OH)6 1:5 trigonal R3 a = 8.233 c = 37.499 Z=3 2201 4.35 deep red-brown; Uniaxial (+) refractive index nω = 1.970 nε = 1.730 [12]
Arakiite (Zn,Mn2+)(Mn2+,Mg)12(Fe3+,Al)2(As5+O4)2(As3+O3)(OH)23 2:1 monoclinic Cc a = 14.248 b = 8.228 c = 24.23 β = 93.62° Z=4 2843 3.41 orange-red brown; Biaxial (-); refract index: nα = 1.723 nβ = 1.744 nγ = 1.750

Birefringence: 0.027

 [13]
Kraisslite Zn3(Mn,Mg)25(Fe3+,Al)(As3+O3)2[(Si,As5+)O4]10(OH)16 5:1 Orthorhombic C2221 a = 8.1821 b = 14.1946 c = 43.9103 Z=4 5099.8 3.876 pale red; Uniaxial (+) Refractive index: nε = 1.805 [14]
Mcgovernite Mn19Zn3(AsO4)3(AsO3)(SiO4)3(OH)21 3:1 trigonal R3m or R3m a = 8.22 c = 203.1 Z=6 11,887.52 3.719 brown; Uniaxial (+) Refractive index: nω = 1.757 nε = 1.760

Birefringence: δ = 0.003

 [15]
Halilsarpite [Mg(H2O)6][CaAs3+2(Fe3+2.67Mo6+0.33)(AsO4)2O7] orthorhomnic Imma a = 26.489 b = 7.4205 c = 10.4378 2051.7 lemon yellow; Biaxial (-) refractive index: nα = 1.646 nβ = 1.765(5) nγ = 1.815(5) 2V: 62° Max Birefringence: δ = 0.169 [16]
Wiklundite Pb2(Mn2+,Zn)3(Fe3+,Mn2+)2(Mn2+,Mg)19(As3+O3)2[(Si,As5+)O4]6(OH)18Cl6 hexagonal ? R3c a = 8.257 c = 126.59 Z = 6 7474 4.072 dark reddish brown [17]
Bi8O6(AsO3)2(AsO4)2 monoclinic I2/a a=24.372 b=5.528 c=29.90 β=99.058 Z=8 3978 7.652 colourless [18]
Th(AsIII4AsV4O18) 1:1 monoclinic C2/c a=18.2148 b 5.19792 c=17.3588 β=99.1298 Z=4 1622.70 4.582 colourless [19]

References
  1. Moore, P. B.; Araki, T (1 February 1978). "Hematolite; a complex dense-packed sheet structure" (PDF). American Mineralogist. 63 (1–2): 150–159.
  2. Jones, P. G.; Beesk, W.; Sheldrick, G. M.; Sharman, E. (1980-02-01). "Arsenic dioxide". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 36 (2): 439–440. doi:10.1107/S0567740880003433. ISSN 0567-7408.
  3. Bodenstein, Doris; Brehm, Axel; Jones, Peter G.; Schwarzmann, Einhard; Sheldrick, George M. (1982-02-01). "Darstellung und Kristallstruktur vom Arsen(III)arsen(V)oxidhydroxid As 3 O 5 (0H) / Preparation and Crystal Structure of the Arsenic(III) Arsenic(V) Oxide Hydroxide As 3 O 5 (OH)". Zeitschrift für Naturforschung B. 37 (2): 138–140. doi:10.1515/znb-1982-0204. ISSN 1865-7117. S2CID 96596612.
  4. Orosel, Denis; Dinnebier, Robert E.; Balog, Paul; Jansen, Martin (July 2007). "The crystal structure of a new mixed valence arsenic(III,V)oxoacid H 6 As 3+ 7 As 5+ 7 O 31". Zeitschrift für Kristallographie. 222 (7): 321–325. Bibcode:2007ZK....222..321O. doi:10.1524/zkri.2007.222.7.321. ISSN 0044-2968. S2CID 95624012.
  5. Yang, Hexiong; Downs, Robert T.; Jenkins, Robert A.; Evans, Stanley H. (2018-09-01). "Segerstromite, Ca3(As5+O4)2[As3+(OH)3]2, the first mineral containing As3+(OH)3, the arsenite molecule, from the Cobriza mine in the Atacama Region, Chile". American Mineralogist. 103 (9): 1497–1501. Bibcode:2018AmMin.103.1497Y. doi:10.2138/am-2018-6329. ISSN 0003-004X. S2CID 106199868.
  6. "Synadelphite". Mindat.
  7. "Hematolite". Mindat.
  8. Dunn, Pete J.; Peacor, Donald R. (September 1983). "A ferric iron equivalent of hematolite from Sterling Hill, New Jersey and Långban, Sweden". Mineralogical Magazine. 47 (344): 381–385. Bibcode:1983MinM...47..381D. doi:10.1180/minmag.1983.047.344.15. ISSN 0026-461X. S2CID 129662981.
  9. "Turtmannite". Mindat.
  10. "Carlfrancisite". Mindat.
  11. Effenberger, H.; Pertlik, F. (October 1987). "[As(V)As(III)O6]4−: An uncommon anion group in the crystal structure of K2Cu3(As2O6)2". Journal of Solid State Chemistry. 70 (2): 219–224. Bibcode:1987JSSCh..70..219E. doi:10.1016/0022-4596(87)90059-4.
  12. "Dixenite". Mindat.
  13. "Arakiite". Mindat.
  14. "Kraisslite". Mindat.
  15. "Mcgovernite". Mindat.
  16. Husdal, Tomas; Grey, Ian E.; Friis, Henrik; Dal Bo, Fabrice; Kampf, Anthony R.; MacRae, Colin M.; Mumme, W. Gus; Ljøstad, Ole-Thorstein; Shanks, Finlay (2020-01-23). "Halilsarpite, a new arsenate analogue of walentaite, from the Oumlil mine, Bou Azzer district, Morocco". European Journal of Mineralogy. 32 (1): 89–98. Bibcode:2020EJMin..32...89H. doi:10.5194/ejm-32-89-2020. hdl:10852/76149. ISSN 1617-4011. S2CID 211082062.
  17. Cooper, Mark A.; Hawthorne, Frank C.; Langhof, Jörgen; Hålenius, Ulf; Holtstam, Dan (August 2017). "Wiklundite, ideally Pb 2 [4] (Mn 2+ ,Zn) 3 (Fe 3+ ,Mn 2+ ) 2 (Mn 2+ ,Mg) 19 (As 3+ O 3 ) 2 [(Si,As 5+ )O 4 ] 6 (OH) 18 Cl 6 , a new mineral from Långban, Filipstad, Värmland, Sweden: Description and crystal structure". Mineralogical Magazine. 81 (4): 841–855. Bibcode:2017MinM...81..841C. doi:10.1180/minmag.2016.080.136. ISSN 0026-461X. S2CID 103754064.
  18. Liu, Jun-Hui; Kong, Fang; Gai, Yan-Li; Mao, Jiang-Gao (January 2013). "Syntheses, crystal structures and characterizations of two new bismuth(III) arsenites". Journal of Solid State Chemistry. 197: 228–235. doi:10.1016/j.jssc.2012.08.019.
  19. Yu, Na; Klepov, Vladislav V.; Kegler, Philip; Bosbach, Dirk; Albrecht-Schmitt, Thomas E.; Alekseev, Evgeny V. (2014-08-18). "Th(As III 4 As V 4 O 18 ): a Mixed-Valent Oxoarsenic(III)/arsenic(V) Actinide Compound Obtained under Extreme Conditions". Inorganic Chemistry. 53 (16): 8194–8196. doi:10.1021/ic5013704. ISSN 0020-1669. PMID 25075555.
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