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Examples with tetrafluroberyllate include dipotassium dimanganese tetrafluoroberyllate K<sub>2</sub>Mn<sub>2</sub>(BeF<sub>4</sub>)<sub>3</sub>,<ref name="Guelylah1996">{{cite journal|last=Guelylah|first=A.|coauthors=T. Breczewski, G. Madariaga|year=1996|title=A New Langbeinite: Dipotassium Dimanganese Tetrafluoroberyllate|journal=Acta Crystallographica Section C Crystal Structure Communications|volume=52|issue=12|pages=2951–2954|issn=01082701|doi=10.1107/S0108270196008827}}</ref>
Examples with tetrafluroberyllate include dipotassium dimanganese tetrafluoroberyllate K<sub>2</sub>Mn<sub>2</sub>(BeF<sub>4</sub>)<sub>3</sub>,<ref name="Guelylah1996">{{cite journal|last=Guelylah|first=A.|coauthors=T. Breczewski, G. Madariaga|year=1996|title=A New Langbeinite: Dipotassium Dimanganese Tetrafluoroberyllate|journal=Acta Crystallographica Section C Crystal Structure Communications|volume=52|issue=12|pages=2951–2954|issn=01082701|doi=10.1107/S0108270196008827}}</ref>

sodium barium diiron tris-(phosphate) NaBaFe<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> is yet another variation with the same structure but differently charged ions.<ref name="Hidouri2008">{{cite journal|last=Hidouri|first=Mourad|coauthors=Hasna Jerbi, Mongi Ben Amara|year=2008|title=The iron phosphate NaBaFe2(PO4)3|journal=Acta Crystallographica Section E Structure Reports Online|volume=64|issue=8|pages=i51–i51|issn=1600-5368|doi=10.1107/S1600536808023040|pmid=21202994}}</ref>
Other tetrafluoroberyllates may include Rb2Mg2(BeF4)3 Tl2Mg2(BeF4)3 Rb2Mn2(BeF4)3 Tl2Mn2(BeF4)3 Rb2Ni2(BeF4)3 Tl2Ni2(BeF4)3 Rb2Zn2(BeF4)3 Tl2Zn2(BeF4)3 Cs2Ca2(BeF4)3 Rb2Ca2(BeF4)3 RbCsMnCd(BeF4)3 Cs2MnCd(BeF4)3 RbCsCd2(BeF4)3 Cs2Cd2(BeF4)3. Tl2Cd2(BeF4)3 (NH4)2Cd2(BeF4)3 KRbMnCd(BeF4)3 K2MnCd(BeF4)3 Rb2MnCd(BeF4)3 Rb2Cd2(BeF4)3 RbCsCo2(BeF4)3 (NH4)2Co2(BeF4)3 K2Co2(BeF4)3 Rb2Co2(BeF4)3 Tl2Co2(BeF4)3 RbCsMn2(BeF4)3 Cs2Mn2(BeF4)3 RbCsZn2(BeF4)3 (NH4)2Mg2(BeF4)3 (NH4)2Mn2(BeF4)3 (NH4)2Ni2(BeF4)3 (NH4)2Zn2(BeF4)3 KRbMg2(BeF4)3 K2Mg2(BeF4)3. KRbMn2(BeF4)3 K2Mn2(BeF4)3 K2Ni2(BeF4)3 K2Zn2(BeF4)3<ref name="Pies1973">{{cite journal|last=Pies|first=W.|coauthors=A. Weiss|year=1973|title=a458, I.1.3 Complex fluorides and fluorine double salts|volume=7a|pages=91–103|doi=10.1007/10201462_9}}</ref>


The phosphate containing langbeinites were found in 1972 with the discovery of KTi<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, and since then a few more phosphates that also contain titanium have been found such as Na<sub>2</sub>FeTi(PO<sub>4</sub>), Na<sub>2</sub>CrTi(PO<sub>4</sub>)<sub>3</sub>. By substituting metals in A<sub>2</sub>MTi(PO<sub>4</sub>)<sub>3</sub>, A from K, Rb, Cs, and M from Cr, Fe or V other langbeinites are made. The nasicon-type structure competes for these kind of phosphates, so not all possibilities are langbeinites.<ref name="Norberg"/>
The phosphate containing langbeinites were found in 1972 with the discovery of KTi<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, and since then a few more phosphates that also contain titanium have been found such as Na<sub>2</sub>FeTi(PO<sub>4</sub>), Na<sub>2</sub>CrTi(PO<sub>4</sub>)<sub>3</sub>. By substituting metals in A<sub>2</sub>MTi(PO<sub>4</sub>)<sub>3</sub>, A from K, Rb, Cs, and M from Cr, Fe or V other langbeinites are made. The nasicon-type structure competes for these kind of phosphates, so not all possibilities are langbeinites.<ref name="Norberg"/>
Other phosphate based substances include K2YTi(PO<sub>4</sub>)<sub>3</sub> K2ErTi(PO<sub>4</sub>)<sub>3</sub> K2YbTi(PO<sub>4</sub>)<sub>3</sub>, K2CrTi(PO<sub>4</sub>)<sub>3</sub><ref name="Norberg">{{cite journal|last=Norberg|first=Stefan T.|year=2002|title=New phosphate langbeinites, K2MTi(PO4)3 (M = Er, Yb or Y), and an alternative description of the langbeinite framework|journal=Acta Crystallographica B|volume=58|issue=5|pages=743–749|pmid=12324686|doi=10.1107/S0108270104030525}}</ref> K2AlSn(PO<sub>4</sub>)<sub>3</sub><ref name="Li2011">{{cite journal|last=Li|first=Hai-Yan|coauthors=Dan Zhao|year=2011|title=A new langbeinite-type phosphate: K2AlSn(PO4)3|journal=Acta Crystallographica Section E Structure Reports Online|volume=67|issue=10|pages=i56–i56|issn=1600-5368|doi=10.1107/S1600536811037263|pmid=22058680}}</ref> Rb<sub>2</sub>YbTi(PO<sub>4</sub>)<sub>3</sub>.<ref name="Gustafsson2006">{{cite journal|last=Gustafsson|first=Joacim C. M.|coauthors=Stefan T. Norberg, Göran Svensson|year=2006|title=The langbeinite type Rb2TiY(PO4)3|journal=Acta Crystallographica Section E Structure Reports Online|volume=62|issue=7|pages=i160–i162|issn=1600-5368|doi=10.1107/S1600536806021635}}</ref>
Other phosphate based substances include K2YTi(PO<sub>4</sub>)<sub>3</sub> K2ErTi(PO<sub>4</sub>)<sub>3</sub> K2YbTi(PO<sub>4</sub>)<sub>3</sub>, K2CrTi(PO<sub>4</sub>)<sub>3</sub><ref name="Norberg">{{cite journal|last=Norberg|first=Stefan T.|year=2002|title=New phosphate langbeinites, K2MTi(PO4)3 (M = Er, Yb or Y), and an alternative description of the langbeinite framework|journal=Acta Crystallographica B|volume=58|issue=5|pages=743–749|pmid=12324686|doi=10.1107/S0108270104030525}}</ref> K2AlSn(PO<sub>4</sub>)<sub>3</sub><ref name="Li2011">{{cite journal|last=Li|first=Hai-Yan|coauthors=Dan Zhao|year=2011|title=A new langbeinite-type phosphate: K2AlSn(PO4)3|journal=Acta Crystallographica Section E Structure Reports Online|volume=67|issue=10|pages=i56–i56|issn=1600-5368|doi=10.1107/S1600536811037263|pmid=22058680}}</ref> Rb<sub>2</sub>YbTi(PO<sub>4</sub>)<sub>3</sub>.<ref name="Gustafsson2006">{{cite journal|last=Gustafsson|first=Joacim C. M.|coauthors=Stefan T. Norberg, Göran Svensson|year=2006|title=The langbeinite type Rb2TiY(PO4)3|journal=Acta Crystallographica Section E Structure Reports Online|volume=62|issue=7|pages=i160–i162|issn=1600-5368|doi=10.1107/S1600536806021635}}</ref> Sodium barium diiron tris-(phosphate) NaBaFe<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> is yet another variation with the same structure but differently charged ions.<ref name="Hidouri2008">{{cite journal|last=Hidouri|first=Mourad|coauthors=Hasna Jerbi, Mongi Ben Amara|year=2008|title=The iron phosphate NaBaFe2(PO4)3|journal=Acta Crystallographica Section E Structure Reports Online|volume=64|issue=8|pages=i51–i51|issn=1600-5368|doi=10.1107/S1600536808023040|pmid=21202994}}</ref>


A langbeinite with [[arsenate]] is known to exist by way of K<sub>2</sub>ScSn(AsO<sub>4</sub>)<sub>3</sub>.<ref name="Harrison2010">{{cite journal|last=Harrison|first=William T. A.|year=2010|title=K2ScSn(AsO4)3: an arsenate-containing langbeinite|journal=Acta Crystallographica Section C Crystal Structure Communications|volume=66|issue=7|pages=i82–i84|issn=0108-2701|doi=10.1107/S0108270110021670}}</ref>
A langbeinite with [[arsenate]] is known to exist by way of K<sub>2</sub>ScSn(AsO<sub>4</sub>)<sub>3</sub>.<ref name="Harrison2010">{{cite journal|last=Harrison|first=William T. A.|year=2010|title=K2ScSn(AsO4)3: an arsenate-containing langbeinite|journal=Acta Crystallographica Section C Crystal Structure Communications|volume=66|issue=7|pages=i82–i84|issn=0108-2701|doi=10.1107/S0108270110021670}}</ref>

Revision as of 12:13, 25 June 2013


Langbeinites are a family of crystalline substances with basic formula M2M'2(SO4)3. M is a large univalent cation such as potassium, rubidium, cesium, or ammonium). M' is a small divalent cation for example (magnesium calcium, manganese, iron, cobalt, nickel, copper, zinc or cadmium). The sulfate group SO42- can be substituted by other tetrahedral anions with a double negative charge such as tetrafluoroberyllate BeF42-, or selenate (SeO42-).

At higher temperatures the crystal structure is cubic P213.[1] However the crystal; structure may change at lower temperatures, for example P21 P1 P212121.[1]

Examples

Sulfates include dithallium dicadmium sulfate,[2] Dirubidium dicadmium sulfate[3] dipotassium dicadmium sulfate,[4] dithallium manganese sulfate.[5] dirubidium dicalcium trisulfate.[6]

Selenates include diammonium dimanganese selenate.[1]

Chromate based langbeinites include dicesium dimanganese chromate.[1]

Molybdates include Rb2Co2(MoO4)3.[1]

Examples with tetrafluroberyllate include dipotassium dimanganese tetrafluoroberyllate K2Mn2(BeF4)3,[4]

Other tetrafluoroberyllates may include Rb2Mg2(BeF4)3 Tl2Mg2(BeF4)3 Rb2Mn2(BeF4)3 Tl2Mn2(BeF4)3 Rb2Ni2(BeF4)3 Tl2Ni2(BeF4)3 Rb2Zn2(BeF4)3 Tl2Zn2(BeF4)3 Cs2Ca2(BeF4)3 Rb2Ca2(BeF4)3 RbCsMnCd(BeF4)3 Cs2MnCd(BeF4)3 RbCsCd2(BeF4)3 Cs2Cd2(BeF4)3. Tl2Cd2(BeF4)3 (NH4)2Cd2(BeF4)3 KRbMnCd(BeF4)3 K2MnCd(BeF4)3 Rb2MnCd(BeF4)3 Rb2Cd2(BeF4)3 RbCsCo2(BeF4)3 (NH4)2Co2(BeF4)3 K2Co2(BeF4)3 Rb2Co2(BeF4)3 Tl2Co2(BeF4)3 RbCsMn2(BeF4)3 Cs2Mn2(BeF4)3 RbCsZn2(BeF4)3 (NH4)2Mg2(BeF4)3 (NH4)2Mn2(BeF4)3 (NH4)2Ni2(BeF4)3 (NH4)2Zn2(BeF4)3 KRbMg2(BeF4)3 K2Mg2(BeF4)3. KRbMn2(BeF4)3 K2Mn2(BeF4)3 K2Ni2(BeF4)3 K2Zn2(BeF4)3[7]

The phosphate containing langbeinites were found in 1972 with the discovery of KTi2(PO4)3, and since then a few more phosphates that also contain titanium have been found such as Na2FeTi(PO4), Na2CrTi(PO4)3. By substituting metals in A2MTi(PO4)3, A from K, Rb, Cs, and M from Cr, Fe or V other langbeinites are made. The nasicon-type structure competes for these kind of phosphates, so not all possibilities are langbeinites.[1] Other phosphate based substances include K2YTi(PO4)3 K2ErTi(PO4)3 K2YbTi(PO4)3, K2CrTi(PO4)3[1] K2AlSn(PO4)3[8] Rb2YbTi(PO4)3.[9] Sodium barium diiron tris-(phosphate) NaBaFe2(PO4)3 is yet another variation with the same structure but differently charged ions.[10]

A langbeinite with arsenate is known to exist by way of K2ScSn(AsO4)3.[11]

Properties

The lanbeinite crystals can show ferroelectric or ferroelastic properties.[1] For example K2Cd(SO4)3. Diammonium dicadmium sulfate identified by Jona and Pepinsky[12] with a unit cell size of 10.35Å becomes ferroelectric when the temperature drops below 95K.[13] The phase transition temperature is not fixed and can vary depending on the crystal. So the phase transition in diammonium dicadmium sulfate can occur between 89 and 95K.[14]

Preparation

Diammonium dicadmium sulfate can be made by evaporating a solution of ammonium sulfate and cadmium sulfate.[14]

References

  1. ^ a b c d e f g h Norberg, Stefan T. (2002). "New phosphate langbeinites, K2MTi(PO4)3 (M = Er, Yb or Y), and an alternative description of the langbeinite framework". Acta Crystallographica B. 58 (5): 743–749. doi:10.1107/S0108270104030525. PMID 12324686.
  2. ^ Guelylah, A. (2000). "X-ray structure determination of the monoclinic (121 K) and orthorhombic (85 K) phases of langbeinite-type dithallium dicadmium sulfate". Acta Crystallographica Section B Structural Science. 56 (6): 921–935. doi:10.1107/S0108768100009514. ISSN 0108-7681. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
  3. ^ Guelylah, Abderrahim (2003). "Dirubidium dicadmium sulfate at 293 K". Acta Crystallographica Section C Crystal Structure Communications. 59 (5): i32–i34. doi:10.1107/S0108270103007479. ISSN 0108-2701. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
  4. ^ a b Guelylah, A. (1996). "Microscopic distortion and order parameter in langbeinite K2Cd2(SO4)3". Phase Transitions. 59 (1–3): 155–179. doi:10.1080/01411599608220042. ISSN 0141-1594. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help) Cite error: The named reference "Guelylah1996" was defined multiple times with different content (see the help page).
  5. ^ Zemann, Anna (1957). "Die Kristallstruktur von Langbeinit, K2Mg2(SO4)3". Acta Crystallographica. 10 (6): 409–413. doi:10.1107/S0365110X57001346. ISSN 0365-110X. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
  6. ^ Boujelben, Mohamed (2007). "Langbeinite-type Rb2Ca2(SO4)3". Acta Crystallographica Section E Structure Reports Online. 63 (7): i157–i157. doi:10.1107/S1600536807027043. ISSN 1600-5368. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
  7. ^ Pies, W. (1973). "a458, I.1.3 Complex fluorides and fluorine double salts". 7a: 91–103. doi:10.1007/10201462_9. {{cite journal}}: Cite journal requires |journal= (help); Unknown parameter |coauthors= ignored (|author= suggested) (help)
  8. ^ Li, Hai-Yan (2011). "A new langbeinite-type phosphate: K2AlSn(PO4)3". Acta Crystallographica Section E Structure Reports Online. 67 (10): i56–i56. doi:10.1107/S1600536811037263. ISSN 1600-5368. PMID 22058680. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
  9. ^ Gustafsson, Joacim C. M. (2006). "The langbeinite type Rb2TiY(PO4)3". Acta Crystallographica Section E Structure Reports Online. 62 (7): i160–i162. doi:10.1107/S1600536806021635. ISSN 1600-5368. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
  10. ^ Hidouri, Mourad (2008). "The iron phosphate NaBaFe2(PO4)3". Acta Crystallographica Section E Structure Reports Online. 64 (8): i51–i51. doi:10.1107/S1600536808023040. ISSN 1600-5368. PMID 21202994. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
  11. ^ Harrison, William T. A. (2010). "K2ScSn(AsO4)3: an arsenate-containing langbeinite". Acta Crystallographica Section C Crystal Structure Communications. 66 (7): i82–i84. doi:10.1107/S0108270110021670. ISSN 0108-2701.
  12. ^ Jona, F. (1956). "Ferroelectricity in the Langbeinite System". Physical Review. 103 (4): 1126–1126. doi:10.1103/PhysRev.103.1126. ISSN 0031-899X. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
  13. ^ McDowell, C.A. (1975). "Proton N.M.R. study of the dynamics of the ammonium ion in ferroelectric langbeinite, (NH4)2Cd2(SO4)3". Molecular Physics. 29 (3): 815–824. doi:10.1080/00268977500100721. ISSN 0026-8976. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
  14. ^ a b Moriyoshi, C. (28 March 2007). "Structural Study of Langbeinite-type (NH4)2Cd(SO4)3) Crystal in the High Temperature Phase" (PDF). IMF-11. Retrieved 24 June 2013. {{cite web}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)

External links

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