Chemistry:Sulfate carbonate

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Short description: Class of chemical compounds
Hanksite

The sulfate carbonates are a compound carbonates, or mixed anion compounds that contain sulfate and carbonate ions. Sulfate carbonate minerals are in the 7.DG and 5.BF Nickel-Strunz groupings.[1]

They may be formed by crystallization from a water solution, or by melting a carbonate and sulfate together.

In some structures carbonate and sulfate can substitute for each other. For example a range from 1.4 to 2.2 Na2SO4•Na2CO3 is stable as a solid solution.[2] Silvialite can substitute about half its sulfate with carbonate[3] and the high temperature hexagonal form of sodium sulfate (I) Na2SO4 can substitute unlimited proportions of carbonate instead of sulfate.[4]

Minerals

name formula system space group unit cell volume

Å3

density optical ref
Brianyoungite Zn12(CO3)3(SO4)(OH)16 Monoclinic P21/m a = 15.724 b = 6.256 c = 5.427 β = 90° 533.8 4.09 Biaxial nα = 1.635 nβ = 1.650 [5]
Burkeite Na6(CO3)(SO4)2 orthorhombic a = 7.05 b = 9.21 c = 5.16 335.04 2.57 Biaxial (-) nα = 1.448 nβ = 1.489 nγ = 1.493

2V: measured: 34° , calculated: 32°

Max birefringence: δ = 0.045

[6]
Caledonite Pb5Cu2(SO4)3(CO3)(OH)6 Orthorhombic Pmn21 a = 20.089 b = 7.146 c = 6.56 941.7 5.77 Biaxial (-) nα = 1.818(3) nβ = 1.866(3) nγ = 1.909(3)

2V: measured: 85° , calculated: 84°

Max birefringence: δ = 0.091

bluish green

[7]
Carraraite Ca3(SO4)[Ge(OH)6](CO3) · 12H2O hexagonal P63/m? a = 11.056 c = 10.629 1125.17 Uniaxial (+) nω = 1.479(1) nε = 1.509(1)

Max birefringence: δ = 0.030

[8]
Carbonatecyanotrichite Cu4Al2(CO3,SO4)(OH)12 · 2H2O Orthorhombic Biaxial (+) nα = 1.616 nβ = 1.630 nγ = 1.677

2V: measured: 55° to 60°, calculated: 60°

Max birefringence: δ = 0.061

pale blue

[9]
Claraite (Cu,Zn)15(AsO4)2(CO3)4(SO4)(OH)14·7H2O triclinic P1 a = 10.3343 b = 12.8212 c = 14.7889 α = 113.196°, β = 90.811°, γ = 89.818° 1800.9 [10]
Ferrotychite Na6(Fe,Mn,Mg)2(CO3)4(SO4)[1] Isometric Fd3 a = 13.962 2,721.7 2.79 Isotropic n = 1.550 [11]
Hanksite Na22K(SO4)9(CO3)2Cl hexagonal P 63/m a = 10.4896 c = 21.2415 2024.1 2.562 Uniaxial (-) nω = 1.481 nε = 1.461

Max birefringence: δ = 0.020

[12]
Hauckite Fe3+3(Mg,Mn2+)24Zn18(SO4)4(CO3)2(OH)81 hexagonal P6/mmm a = 9.17 c = 30.21 2200 3.02 Uniaxial (+) nω = 1.630 nε = 1.638

Max birefringence: δ = 0.008

[13]
Jouravskite Ca3Mn4+(SO4)(CO3)(OH)6 · 12H2O Hexagonal P63 a = 11.0713 c = 10.6265 Z=3 1128.02 Uniaxial (-) nω = 1.556 nε = 1.540

Max birefringence: δ = 0.016

[14]
Korkinoite Ca4(SO4)2(CO3)2 · 9H2O Orthorhombic Pmmm Biaxial (+) [15]
Latiumite (Ca,K)4(Si,Al)5O11(SO4,CO3) Monoclinic a = 12.06 Å, b = 5.08 Å, c = 10.81 Å

β = 106°

636.6 Biaxial (+/-) nα = 1.600 - 1.603 nβ = 1.606 - 1.609 nγ = 1.614 - 1.615

2V: measured: 83° to 90°, calculated: 84° to 88°

Max Birefringence: δ = 0.014

[16]
Leadhillite Pb4(SO4)(CO3)2(OH)2 Monoclinic P21/b a = 9.11 b = 20.82 c = 11.59

β = 90.46°

2198 6.55 Biaxial (-) nα = 1.870 nβ = 2.009 nγ = 2.010

2V: 10°

Max birefringence: δ = 0.140

[17][18]
Macphersonite Pb4(SO4)(CO3)2(OH)2[17] Orthorhombic a = 10.38 b = 23.05 c = 9.242 2211.8 Biaxial (-) nα = 1.870 nβ = 2.000 nγ = 2.010

2V: measured: 35° calculated: 28°

Max birefringence: δ = 0.140

[19]
Manganotychite Na6(Mn,Fe,Mg)2(SO4)(CO3)4[17] Isometric Fd3 a = 13.9951 2,741.12 2.7 n = 1.544 pink [20]
Mineevite-Y Na25BaY2(SO4)11(HCO3)4(CO3)2F2Cl[17] Hexagonal P63/m a = 8.811 c = 37.03 Z=2 2489.6 Uniaxial (-) nω = 1.536 nε = 1.510

Max birefringence: δ = 0.026

pale green

[21]
Nakauriite Cu8(SO4)4(CO3)(OH)6•48H2O orthorhombic a = 14.58 b = 11.47 c = 16.22 2,712.5 2.39 blue

Biaxial (-) nα = 1.585 nβ = 1.604 nγ = 1.612

2V: measured: 65° , calculated: 64°

Max birefringence: δ = 0.027

[22]
Nasledovite PbMn3Al4(CO3)4(SO4)O5 · 5H2O 3.069 Biaxial [23]
Paraotwayite Ni(OH)2-x(SO4,CO3)0.5x monoclinic a = 7.89 b = 2.96 c = 13.63 β = 91.1° 318 3.30 Biaxial nα = 1.655 nγ = 1.705

Max birefringence: δ = 0.050

emerald-green

[24]
Philolithite Pb12Mn2+(Mg,Mn2+)2(Mn2+,Mg)4(CO3)4(SO4)O6(OH)12Cl4[1] Tetragonal a = 12.627 c = 12.595 2008.2 Biaxial (+) nα = 1.920 nβ = 1.940 nγ = 1.950

Max birefringence: δ = 0.030

apple green

[25]
Putnisite SrCa4Cr83+(CO3)8(SO4)(OH)16·25 H2O Orthorhombic Pnma a = 15.351 b = 20.421 c = 18.270 Z = 4 5727.3 Biaxial(-); α = 1.552 nβ = 1.583 nγ = 1.599

Max birefringence: δ =0.047

violet

[26]
Pyroaurite Mg6Fe2(SO4,CO3)(OH)16·4H2O Trigonal R3_m a = 3.1094 c = 23.4117 196.03 2.1 Uniaxial (-) nω = 1.564 nε = 1.543

Max birefringence: δ = 0.021

[27]
Hexagonal P63/mmc a = 3.113 c = 15.61 131.01
Rapidcreekite Ca2(SO4)(CO3)•4H2O orthorhombic a = 15.49 b = 19.18 c = 6.15 1827.15 Biaxial (+) nα = 1.516 nβ = 1.518 nγ = 1.531

2V: measured: 45° , calculated: 44°

Max birefringence: δ = 0.015

[28]
Schröckingerite NaCa3(UO2)(SO4)(CO3)3F•10(H2O)[17] triclinic P1 a = 9.634 b = 9.635 c = 14.391

α = 91.41(1)°, β = 92.33(1)°, γ = 120.26(1)°

Biaxial (-) nα = 1.495 nβ = 1.543 nγ = 1.544

Max birefringence: δ = 0.049

[29]
Susannite Pb4(SO4)(CO3)2(OH)2[1] trigonal P3 a = 9.07 Å, c = 11.57 Å Z=3 824.62 6.52 clear [30]
Tatarskite Ca6Mg2(SO4)2(CO3)2(OH)4Cl4•7H2O[31] Orthorhombic 2.341 nα = 1.567(2) nβ = 1.654(2) nγ = 1.722 biaxial(-) 2V=83 [32]
Thaumasite Ca3(SO4)[Si(OH)6](CO3) · 12H2O hexagonal P63 a = 11.030 c = 10.396 1095.3 Uniaxial (-) nω = 1.507 nε = 1.468

Max birefringence: δ = 0.039

[33]
Tychite Na6Mg2(SO4)(CO3)4 Isometric Fd3 a = 13.9038 Z=8 2687.82 2.456 isotropic [34]
Alloriite Na19K6Ca5[Al22Si26O96](SO4)5Cl(CO3)x(H2O) trigonal P31c a = 12.892 c = 21.340 [35]
Potassium-Schröckingerite KCa3(UO2)(CO3)3(SO4)F•10H2O triclinic yellow [36]

Artificial

name formula formula weight crystal system space group unit cell volume density refractive index comment CAS reference
Na4CO3SO4 Hexagonal P3m1 a=5.2284 c=6.8808 Z=1 2.538 uniaxial (-) n=~1.45 [37][38]
Mg4(OH)2(CO3)2SO4·6H2O [39]
LDH-SO4-CO3 Mg6Al2SO4CO3(OH)14·4H2O P3m a=3.070 c=22.3 layered [40]
Co6Al2SO4CO3(OH)14·4H2O [40]
Cu6Al2SO4CO3(OH)14·4H2O [40]
Complexes
Tetrammine carbonatocobalt(III) sulfate trihydrate [Co(NH3)4CO3]2SO4·3H2O Monoclinic P21/c a=7.455 b=10.609 c=23.627 β =98.346 Z=4 1849 1.88 dark red [41]
μ-Carbonato-bis(pentaamminecobalt(III)) sulfate tetrahydrate [Co(NH3)5]2CO3SO4·4H2O dark red 49731-04-6 [42]
μ-Carbonato-μ-dihydroxo-bis(triamminecobalt(III)) sulfate pentahydrate [(NH3)3Co(μ-OH)2(μ-CO3)Co(NH3)3]SO4 . 5H2O 500.21 Triclinic a= 6.6914 b= 11.2847 c= 11.825, α = 92.766 β= 99.096 γ= 101.496 861.1 1.929 dark red 75476-69-6 [43]

References

  1. ↑ 1.0 1.1 1.2 1.3 "Susannite: Mineral information, data and localities.". https://www.mindat.org/min-3833.html. 
  2. ↑ Green, Stanley J.; Frattali, Francis J. (September 1946). "The System Sodium Carbonate-Sodium Sulfate-Sodium Hydroxide-Water at 100°". Journal of the American Chemical Society 68 (9): 1789–1794. doi:10.1021/ja01213a033. 
  3. ↑ Teertstra, D. K.; Schindler, M.; Sherriff, B. L.; Hawthorne, F. C. (June 1999). "Silvialite, a new sulfate-dominant member of the scapolite group with an Al-Si composition near the 14/ m – P 4 2 / n phase transition" (in en). Mineralogical Magazine 63 (3): 321–329. doi:10.1180/002646199548547. ISSN 0026-461X. Bibcode: 1999MinM...63..321T. https://www.cambridge.org/core/product/identifier/S0026461X00009142/type/journal_article. 
  4. ↑ Eysel, W.; Höfer, H. H.; Keester, K. L.; Hahn, Th. (1985-02-01). "Crystal chemistry and structure of Na 2 SO 4 (I) and its solid solutions". Acta Crystallographica Section B: Structural Science 41 (1): 5–11. doi:10.1107/S0108768185001501. ISSN 0108-7681. Bibcode: 1985AcCrB..41....5E. http://scripts.iucr.org/cgi-bin/paper?S0108768185001501. 
  5. ↑ "Brianyoungite: Mineral information, data and localities.". https://www.mindat.org/min-772.html. 
  6. ↑ "Burkeite: Mineral information, data and localities.". https://www.mindat.org/min-805.html. 
  7. ↑ "Caledonite: Mineral information, data and localities.". https://www.mindat.org/min-865.html. 
  8. ↑ "Carraraite: Mineral information, data and localities.". https://www.mindat.org/min-7038.html. 
  9. ↑ "Carbonatecyanotrichite: Mineral information, data and localities.". https://www.mindat.org/min-894.html. 
  10. ↑ Biagioni, Cristian; Orlandi, Paolo (2017-12-01). "Claraite, (Cu,Zn)15(AsO4)2(CO3)4(SO4)(OH)14·7H2O: redefinition and crystal structure" (in en). European Journal of Mineralogy 29 (6): 1031–1044. doi:10.1127/ejm/2017/0029-2669. ISSN 0935-1221. Bibcode: 2017EJMin..29.1031B. http://www.schweizerbart.de/papers/ejm/detail/29/88530/Claraite_Cu_Zn_15_AsO4_2_CO3_4_SO4_OH_14_7H2O_rede?af=crossref. 
  11. ↑ "Ferrotychite: Mineral information, data and localities.". https://www.mindat.org/min-1533.html. 
  12. ↑ Callegari, Athos Maria; Boiocchi, Massimo; Zema, Michele; Tarantino, Serena Chiara (2018-08-01). "The crystal structure of hanksite, Na 22 K(CO 3 ) 2 (SO 4 ) 9 Cl, refined from high-resolution X-ray diffraction data" (in en). Neues Jahrbuch für Mineralogie - Abhandlungen 195 (2): 115–122. doi:10.1127/njma/2018/0113. ISSN 0077-7757. 
  13. ↑ "Hauckite: Mineral information, data and localities.". https://www.mindat.org/min-1830.html. 
  14. ↑ "Jouravskite: Mineral information, data and localities.". https://www.mindat.org/min-2118.html. 
  15. ↑ "Korkinoite: Mineral information, data and localities.". https://www.mindat.org/min-32154.html. 
  16. ↑ "Latiumite: Mineral information, data and localities.". https://www.mindat.org/min-2336.html. 
  17. ↑ 17.0 17.1 17.2 17.3 17.4 Jones, G. C.; Jackson, B. (2012) (in en). Infrared Transmission Spectra of Carbonate Minerals. Springer Science & Business Media. p. 18. ISBN 978-94-011-2120-0. https://books.google.com/books?id=SCUrBgAAQBAJ&pg=PT18. 
  18. ↑ "Leadhillite: Mineral information, data and localities.". https://www.mindat.org/min-2361.html. 
  19. ↑ "Macphersonite: Mineral information, data and localities.". https://www.mindat.org/min-2513.html. 
  20. ↑ "Manganotychite: Mineral information, data and localities.". https://www.mindat.org/min-2529.html. 
  21. ↑ "Mineevite-(Y): Mineral information, data and localities.". https://www.mindat.org/min-2718.html. 
  22. ↑ "Nakauriite: Mineral information, data and localities.". https://www.mindat.org/min-2948.html. 
  23. ↑ "Nasledovite: Mineral information, data and localities.". https://www.mindat.org/min-2843.html. 
  24. ↑ "Paraotwayite: Mineral information, data and localities.". https://www.mindat.org/min-3104.html. 
  25. ↑ "Philolithite: Mineral information, data and localities.". https://www.mindat.org/min-7230.html. 
  26. ↑ "Mineralienatlas - Fossilienatlas" (in de). https://www.mineralienatlas.de/lexikon/index.php/MineralData?lang=de&mineral=Putnisite. 
  27. ↑ "Pyroaurite: Mineral information, data and localities.". https://www.mindat.org/min-3330.html. 
  28. ↑ "Rapidcreekite: Mineral information, data and localities.". https://www.mindat.org/min-3366.html. 
  29. ↑ "Schröckingerite: Mineral information, data and localities.". https://www.mindat.org/min-3584.html. 
  30. ↑ "Susannite: Mineral information, data and localities.". https://www.mindat.org/min-3833.html. 
  31. ↑ "Tatarskite: Mineral information, data and localities.". https://www.mindat.org/min-3894.html. 
  32. ↑ "Tatarskite: Mineral information, data and localities.". https://www.mindat.org/min-3894.html. 
  33. ↑ "Thaumasite: Mineral information, data and localities.". https://www.mindat.org/min-3933.html. 
  34. ↑ "Tychite: Mineral information, data and localities.". https://www.mindat.org/min-4068.html. 
  35. ↑ Kaneva, Ekaterina (2015-09-01). Investigation of the sulfur speciation in cancrinite group minerals using Single crystal X-ray diffraction analysis [in Russian]. https://www.researchgate.net/publication/284486224. 
  36. ↑ "UM1997-27-CO:CaHKSU: Mineral information, data and localities.". https://www.mindat.org/min-7652.html. 
  37. ↑ Swanson, Howard E.; McMurdie, Howard F.; Morris, Marlene C.; Evans, Eloise H.; Paretzkin, Boris (February 1974). "Standard X-ray Diffraction Powder Patterns: Section 11. Data for 70 Substances" (in en). p. 51. https://digital.library.unt.edu/ark:/67531/metadc13203/m1/57/. 
  38. ↑ Wang, Jinsheng; Wu, Yinghai; Anthony, Edward J. (July 2007). "Reactions of solid CaSO4 and Na2CO3 and formation of sodium carbonate sulfate double salts". Thermochimica Acta 459 (1–2): 121–124. doi:10.1016/j.tca.2007.04.014. 
  39. ↑ Livingstone, A. (September 1987). "A basic magnesium carbonate, a possible dimorph of artinite, from Unst, Shetland" (in en). Mineralogical Magazine 51 (361): 459–462. doi:10.1180/minmag.1987.051.361.13. ISSN 0026-461X. Bibcode: 1987MinM...51..459L. https://www.cambridge.org/core/product/identifier/S0026461X00021794/type/journal_article. 
  40. ↑ 40.0 40.1 40.2 Wu, Jiansong; Yang, Yifeng (October 2019). "Synthesis and Structural Analysis of LDH-SO4-CO3 Whisker" (in en). Journal of Wuhan University of Technology-Mater. Sci. Ed. 34 (5): 1085–1088. doi:10.1007/s11595-019-2163-2. ISSN 1000-2413. 
  41. ↑ Macikenas, Dainius; Hazell, R. G.; Christensen, A. Nørlund; Balashev, Konstantin P.; Songstad, Jon; Mo, Frode; Bartfai, Tamas; Langel, Ülo (1995). "X-Ray Crystallographic Study of Tetrammine-Carbonatocobalt(III) Sulfate Trihydrate, [Co(NH3)4CO3]2SO4.3H2O." (in en). Acta Chemica Scandinavica 49: 636–639. doi:10.3891/acta.chem.scand.49-0636. ISSN 0904-213X. 
  42. ↑ Kremer, Eduardo; Piriz Mac-Coll, Carlos R. (October 1971). ".mu.-Carbonato-bis(pentaamminecobalt(III)) salts" (in en). Inorganic Chemistry 10 (10): 2182–2186. doi:10.1021/ic50104a018. ISSN 0020-1669. 
  43. ↑ Churchill, Melvyn Rowen.; Lashewycz, Romana A.; Koshy, Kanayuthu.; Dasgupta, Tara P. (February 1981). "Synthesis, properties, and crystallographic characterization of a dinuclear .mu.-carbonato complex of cobalt(III): [(NH3)3Co(.mu.-OH)2(.mu.-CO3)Co(NH3)3]SO4.5H2O" (in en). Inorganic Chemistry 20 (2): 376–381. doi:10.1021/ic50216a012. ISSN 0020-1669. 



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