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词条 Tutton's salt
释义

  1. Examples and related compounds

  2. History

  3. Table of salts

  4. References

Tutton's salts are a family of salts with the formula M2M'(SO4)2(H2O)6 (sulfates) or M2M'(SeO4)2(H2O)6 (selenates). These materials are double salts, which means that they contain two different cations, M+ and M'2+ crystallized in the same regular ionic lattice.[1] The univalent cation can be potassium, rubidium, cesium, ammonium (NH4), deuterated ammonium (ND4) or thallium. Sodium or lithium ions are too small. The divalent cation can be magnesium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc or cadmium. In addition to sulfate and selenate, the divalent anion can be chromate (CrO42−), tetrafluoroberyllate (BeF42−), hydrogenphosphate (HPO42−)[2] or monofluorophosphate (PO3F2−). Tutton's salts crystallize in the monoclinic space group P21/a.[3] The robustness is the result of the complementary hydrogen-bonding between the tetrahedral anions and cations as well their interactions with the metal aquo complex [M(H2O)6]2+.

Examples and related compounds

Perhaps the best-known is Mohr's salt, ferrous ammonium sulfate (NH4)2Fe(SO4)2.(H2O)6).[4] Other examples include the vanadous Tutton salt (NH4)2V(SO4)2(H2O)6 and the chromous Tutton salt (NH4)2Cr(SO4)2(H2O)6.[5] In solids and solutions, the M'2+ ion exists as a metal aquo complex [M'(H2O)6]2+.

Related to the Tutton's salts are the alums, which are also double salts but with the formula MM'(SO4)2(H2O)12. The Tutton's salts were once termed "false alums".[6]

History

Tutton salts are sometimes called Schönites after the naturally occurring mineral called Schönite (K2Mg(SO4)2(H2O)6). They are named for A. E. H. Tutton, who identified and characterised a large range of these salts around 1900.[7]
Such salts were of historical importance because they were obtainable in high purity and served as reliable reagents and spectroscopic standards.

Table of salts

M1M2formulanamea Åb Åc Åβ°V Å3colourNαNβNγBiaxial2Vother
KCdK2Cd(SO4)2·6H2OPotassium cadmium sulfate[8]
CsCdCs2Cd(SO4)2·6H2Ocaesium cadmium sulphate hexahydrate[9]
NH4Cd(NH4)2Cd(SO4)2.6H2OAmmonium Cadmium Sulfate Hydrate9.39512.7766.299106°43'727.63colourlessl.4861.4881.494Biaxial(-f)large[10]density=2.05[11]

Slowly loses water in dry air.[12]

KCoK2Co(SO4)2·6H2O [13]Potassium cobaltous sulfate[14]6.1519.06112.207104.8°657.78[14]reddensity=2.21
RbCoRb2[Co(H2O)6](SO4)2Rubidium hexaaquacobalt(II) sulphate6.249.1912.453105.99°686.5[12]ruby-red[15]desnsity=2.56
CsCoCs2[Co(H2O)6](SO4)2Caesium hexaaquacobalt(II) sulphate9.318(1)12.826(3)6.3650(9)107.13(1)°727.0[18]dark red
NH4Co(NH4)2Co(SO4)2·6 H2O[19]Cobaltous ammonium sulfate hexahydrate6.2429.25512.549106.98°693.3[16]purple[17]density=1.89
TlCoTl2[Co(H2O)6](SO4)2Cobaltous thallium sulfate hexahydrate, Thallium hexaaquacobalt(II) sulfate,9.227(1)12.437(2)6.220(1)106.40(1)°684.7light red[18]
TlCoTl2[Co(H2O)6](SO4)2dithallium cobalt sulfate hexahydrate9.235(1)12.442(2)6.227(1)106.40(1)°yellowish pink1.5991.6131.624biaxial(-)medium large[19]density=4.180 g/cm3
RbCrRb2Cr(SO4)2.6H2O[20]dirubidium chromium sulfate hexahydrate
CsCrCs2Cr(SO4)2.6H2O[20]dicaesium chromium sulfate hexahydrate
ND4Cr(ND4)2Cr(SO4)2.6H2O[20]dideuterated ammonium chromium sulfate hexahydratebright blue,formed from CrSO4.3H2O with ammonium sulfate in minimal water under nitrogen gas. Stable in air from oxidation, but may dehydrate.[21]
KCuK2[Cu(H2O)6](SO4)2cyanochroite[14]9.2712.446.30104.47[22]663.0[22]pale green bluedensity=2.21[22] within unit cell 7.76 between two Cu atoms[23]
RbCuRb2[Cu(H2O)6](SO4)2Dirubidium hexaaquacopper sulfate9.26712.3666.228105°19'686.8brilliant greenish blue1.4881.4911.506biaxial (+)[33]mediumdensity=2.580g/cm3[10] Cu-O 2.098 Å Rb-O 3.055 Å.[24]
CsCuCs2[ Cu(H2O)6](SO4)2[25]dicaesium hexaaquacopper sulfate9.43912.7626.310106°11'718.5brilliant greenish blue,1.5041.5061.514biaxial (+)density=2.864g/cm3[26]
NH4Cu(NH4)2[Cu(H2O)6](SO4)2ammonium hexaaquacopper(II) sulfate[38]6.3112.389.22106.16°691.25[27]density=1.921;[27] heat of formation=-777.9 kcal/mol[27] Jahn-Teller distortion axis switches under pressure of ~1500 bars, a,b axis shrinks 3.3% and 3.5% and c axis extends 4.5%.[28]
TlCuTl2[Cu(H2O)6](SO4)2Thallium copper sulfate hydrate9.26812.3646.216105°33'brilliant greenish blue1.6001.6101.620biaxialvery large[29]density=3.740 g/cm3
KFeK2Fe(SO4)2·6 H2Odipotassium iron sulfate hexahydrate[14]
RbFeRb2Fe(SO4)2.6H2ORubidium iron sulfate hydrate9.21812.4976.256105°45'pale green1.4801.4891.501biaxial (+)large,density=2.523g/cm3[30]
CsFeCs2[Fe(H2O)6](SO4)2Caesium hexaaquairon(II) sulphate9.357(2)12.886(2)6.381(1)106.94(1)°736.0dark yellow[18] very pale green1.5011.5041.516biaxial (+)medium[31]density=2.805
NH4Fe(NH4)2Fe(SO4)2·6 H2Omohrite[14]6.24(1)12.65(2)9.32(2)106.8(1)704.28vitreous pale greendensity=1.85 named after Karl Friedrich Mohr[32]
TlFeTl2Fe(SO4)2·6H2OThallium hexaaquairon(II) sulfate9.262(2)12.497(1)6.235(2)106.15(1)°693.2[18]light green1.5901.605=1.616biaxial (-)largedensity=3.662g/cm3[33]
KMgK2Mg(SO4)2·6H2Opicromerite9.0412.246.095104° 48'[14][34]colourless or white1.4601.4621.472biaxial (+)mediumdensity=2.025g/cm3;[35] expanded second coordination sphere around Mg.[34]
RbMgRb2Mg(SO4)2 · 6H2Orubidium magnesium sulphate hexahydrate[36]9.23512.4866.224105°59'colourless1.4671.4691.476[37]biaxial
CsMgCs2[Mg(H2O)6](SO4)2Cesium hexaaquamagnesium sulphate9.338(2)12.849(4)6.361(2)107.07(2)°729.6colourless[38]1.4811.4851.492biaxial(+)mediumdensity=2.689[39]
NH4Mg(NH4)2Mg(SO4)2 · 6H2Oboussingaultite9.2812.576.2107°6'[34][19]
NH4Mg(NH4)2Mg(Cr04)2.6H20Ammonium Magnesium Chromium Oxide Hydrate9.508±.00112.6746.246106°14'bright yellow1.6371.6381.653biaxial(+)smalldensity=1.840 g/cm 3[10]
TlMgTl2Mg(SO4)2·6H2O[40]dithallium magnesium sulfate hexahydrate9.22 9.262(2)12.42 12.459(2)6.185 6.207(1)106°30' 106.39(2)°687.1colourless[18]density=3.532 g/cm3
RbMnRb2[Mn(H2O)6](SO4)2Dirubidium hexaaquamanganese sulfate(VI)9.282(2)12.600(2)6.254(2)105.94(2)703.3Å3[41][42]
CsMnCs2[Mn(H2O)6](SO4)2Caesium hexaaquamanganese(II) sulphate9.418(3)12.963(2)6.386(3)107.17(4)°744.9pale pink[38] purplish white[68]1.4951.4971.502biaxial(+)largedensity=2.763[43]
NH4Mn(NH4)2[Mn(H2O)6](SO4)2manganese ammonium sulfate hexahydrate9.4012.746.26107.0°[44]pale pink1.4821.4561.492biaxial(+)largedensity=1.827 [45]
TlMnTl2[Mn(H2O)6](SO4)2Thallium manganese sulfate hexahydrate9.3276(6), 9.322(2)12.5735(8), 12.565(2)6.2407(4), and 6.233(1)106.310(3)°[46] 106.29(2)°,700.8[18]light pink
KNiK2Ni(SO4)2·6H2O[13] Potassium Nickel Sulfate Hexahydrate[34] used as UV filter[76]
RbNiRb2Ni(SO4)2·6H2ORubidium Nickel Sulfate Hexahydrate6.22112.419.131106.055°677.43001 surface has step growth of 4.6 Å, optical transmission bands at 250, 500 and 860 nm which are the same as nickel sulfate hexahydrate, but UV band transmits more. Heavy absorption 630-720 nm and 360-420 nm3 density 2.596 g cm−3.[47] stable to 100.5 °C solubility in g/100ml=0.178t + 4.735 MW=529.87
CsNiCs2[Ni(H2O)6](SO4)2Caesium hexaaquanickel(II) sulphate, Cesium Nickel Sulfate Hexahydrate9.259(2)12.767(2)6.358(1)107.00(2)°718.7[38]greenish blue1.5071.5121.516biaxial(-)very largedensity=2.883 [48] used as UV filter[47]
NH4Ni(NH4)2Ni(SO4)2·6 H2Onickel-boussingaultite[34][49]9.18612.4686.424684.0blueish green.[50][51]density=1.918 cas=51287-85-5
TlNiTl2Ni(SO4)2·6 H2OThallium hexaaquanickel(II) sulfate9.161(2)12.389(2)6.210(2)106.35(2)°676.3greenish blue[18]1.6021.6151.620biaxial(-)largedensity=3.763[52]
KRuK2Ru(SO4)2·6 H2O[53]8.95012.2686.135105.27644
RbRuRb2Ru(SO4)2·6 H2O[53]9.13212.5276.351106.30
KVK2V(SO4)2·6 H2OVanadium(II) potassium sulfate hexahydrate [54]
RbVRb2V(SO4)2·6 H2ORubidium vanadium(II) sulfate
NH4V(NH4)2V(SO4)2·6 H2OVanadium(II) ammonium sulfate hexahydrate9.4212.766.22107.2°714.2amethystdensity=1.8 V-O length 2.15Å[55]
KZnK2Zn(SO4)2 · 6H2O [13][34]dipotassium zinc sulphate hexahydrate9.04112.3106.182104.777°colourless1.4781.4811.496biaxiallargedensity=2.242g/cm3[56] Thermal decomposition at 252K.[57]
RbZnRb2[Zn(H2O)6](SO4)2 Rubidium Zinc Sulphate Hexahydrate[58]9.18512.4506.242105°54'colourless1.4831.4891.497biaxiallarge [59]
CsZnCs2[Zn(H2O)6](SO4)2zinc cesium sulphate hexahydrate [60]9.314(2)12.817(2)6.369(2)106.94(2)°727.3colourless[38]1.5071.6101.615biaxial(-)largedensity=2.881 [61]
NH4Zn(NH4)2Zn(SO4)2·6H2O9.20512.4756.225106°52'[62]684.1heat of fusion 285 J/g[63]
TlZnTl2Zn(SO4)2 · 6H2OThallium hexaaquazinc(II) sulfate [64]9.219(2)12.426(2)6.226(1)106.29(2)°684.6colourless[18]

References

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32. ^{{cite web|url=http://www.handbookofmineralogy.org/pdfs/mohrite.pdf|title=Mohrite|publisher=Mineral Data Publishing|accessdate=17 June 2013}}
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34. ^1 2 3 4 5 6 7 8 9 10 {{cite journal|last=Bosi|first=F. |author2=G. Belardi |author3=P. Ballirano|year=2009|title=Structural features in Tutton's salts K2[M2+(H2O)6](SO4)2, with M2+ = Mg, Fe, Co, Ni, Cu, and Zn|journal=American Mineralogist|volume=94|issue=1|pages=74–82|issn=0003-004X|doi=10.2138/am.2009.2898|bibcode=2009AmMin..94...74B}}
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39. ^{{cite book|last=Swanson,|first=H. E. |author2=McMurdie, H. F. |author3=Morris, M. C. |author4=Evans, E. H. |title=Standard X-ray Diffraction Powder Patterns: Section 7. Data for 81 Substances|url= https://digital.library.unt.edu/ark:/67531/metadc13215/m1/24/|page=18|accessdate=June 17, 2013|date=September 1969|publisher=UNT Digital Library|location=Washington D.C}}
40. ^{{cite journal|last=Chand|first=Prem |author2=R. Murali Krishna |author3=J. Lakshmana Rao |author4=S. V. J. Lakshman|year=1993|title=EPR and optical studies of vanadyl complexes in two host-crystals of Tutton salts of thallium|journal=Radiation Effects and Defects in Solids|volume=127|issue=2|pages=245–254|issn=1042-0150|doi=10.1080/10420159308220322|bibcode=1993REDS..127..245C}}
41. ^{{cite web|url=http://chem5.nchc.org.tw/icsd/details.php?id[]=60195|title=ICSD for WWW|accessdate=15 June 2013}}
42. ^{{cite journal|last=Euler|first=H. |author2=B. Barbier |author3=S. Klumpp |author4=A. Kirfel|year=2000|title=Crystal structure of Tutton’s salts, Rb2[MII(H2O)6](SO4)2, MII = Mg, Mn, Fe, Co, Ni, Zn|journal=Zeitschrift für Kristallographie. New crystal structures|volume=215|issue=4|pages=473–476|issn=1433-7266|url=ftp://ftp.oldenbourg.de/pub/download/frei/ncs/218-4/409737_38_39_40_41_42.pdf|accessdate=15 June 2013|doi=10.1515/ncrs-2000-0408}}
43. ^1 {{cite book|last=Swanson,|first=H. E. |author2=McMurdie, H. F. |author3=Morris, M. C. |author4=Evans, E. H. |title=Standard X-ray Diffraction Powder Patterns: Section 7. Data for 81 Substances|url= https://digital.library.unt.edu/ark:/67531/metadc13215/m1/26/|page=20|accessdate=June 17, 2013|date=September 1969|publisher=UNT Digital Library|location=Washington D.C}}
44. ^{{cite journal|last=Montgomery|first=H. |author2=R. V. Chastain |author3=E. C. Lingafelter|year=1966|title=The crystal structure of Tutton's salts. V. Manganese ammonium sulfate hexahydrate|journal=Acta Crystallographica|volume=20|issue=6|pages=731–733|issn=0365-110X|doi=10.1107/S0365110X66001762}}
45. ^{{cite book|last=Swanson,|first=H. E. |author2=McMurdie, H. F. |author3=Morris, M. C. |author4=Evans, E. H. |title=Standard X-ray Diffraction Powder Patterns: Section 8. Data for 81 Substances|url=http://digicoll.manoa.hawaii.edu/techreports/PDF/NBS25-8.pdf|page=12|accessdate=June 17, 2013|date=September 1970|location=Washington D.C}}
46. ^{{cite journal|last1=Nalbandyan|first1=V. B.|title=Thallium manganese sulfate hexahydrate, a missing Tutton's salt, and a brief review of the entire family|journal=Powder Diffraction|date=29 February 2012|volume=23|issue=1|pages=52–55|doi=10.1154/1.2840634|bibcode=2008PDiff..23...52N}}
47. ^1 2 {{cite journal|last=Wang|first=Xia |author2=Xinxin Zhuang |author3=Genbo Su |author4=Youping He|year=2008|title=A new ultraviolet filter: Rb2Ni (SO4)2·6H2O (RNSH) single crystal|journal=Optical Materials|volume=31|issue=2|pages=233–236|issn=0925-3467|doi=10.1016/j.optmat.2008.03.020|url=http://ir.fjirsm.ac.cn/bitstream/350002/5857/1/Wang-2008-A%20new%20ultraviolet%20fi.pdf|bibcode=2008OptMa..31..233W}}
48. ^{{cite book|last=Swanson,|first=H. E. |author2=McMurdie, H. F. |author3=Morris, M. C. |author4=Evans, E. H. |title=Standard X-ray Diffraction Powder Patterns: Section 7. Data for 81 Substances|url= https://digital.library.unt.edu/ark:/67531/metadc13215/m1/29/|page=23|accessdate=June 17, 2013|date=September 1969|publisher=UNT Digital Library|location=Washington D.C}}
49. ^{{cite journal|last=Montgomery|first=H. |author2=E.C. Lingafelter|date=10 November 1964|title=The crystal structure of Tutton's salts. II. Magnesium ammonium sulfate hexahydrate and nickel ammonium sulfate hexahydrate|journal=Acta Crystallographica|publisher=International Union of Crystallography|volume=17|issue=11|page=1478|doi=10.1107/s0365110x6400367x}}
50. ^{{cite book|last=Morris|first=Marlene C |author2=McMurdie, Howard F. |author3=Evans, Eloise H. |author4=Paretzkin, Boris |author5=Hubbard, Camden R. |author6=Carmel, Simon J.|title=Standard X-ray Diffraction Powder Patterns: Section 17. Data for 54 Substances|url=https://digital.library.unt.edu/ark:/67531/metadc13209/m1/15/}}
51. ^https://archive.org/stream/philtrans02006988/02006988_djvu.txt
52. ^{{cite book|last=Swanson,|first=H. E. |author2=McMurdie, H. F. |author3=Morris, M. C. |author4=Evans, E. H. |title=Standard X-ray Diffraction Powder Patterns: Section 7. Data for 81 Substances|url= https://digital.library.unt.edu/ark:/67531/metadc13215/m1/84/|page=78|accessdate=June 17, 2013|date=September 1969|publisher=UNT Digital Library|location=Washington D.C}}
53. ^1 {{cite journal|last1=Bernhard|first1=Paul|last2=Ludi|first2=Andreas|title=Infrared and Raman spectra of the hexaaquaruthenium ions: normal-coordinate analysis for Ru(H2O)62+ and Ru(H2O)63+|journal=Inorganic Chemistry|date=March 1984|volume=23|issue=7|pages=870–872|doi=10.1021/ic00175a015}}
54. ^{{cite book|last1=Mido|first1=M. Satake & Y.|last2=Satake|first2=M.|title=Chemistry Of Transition Elements|url=https://books.google.com/books?id=XwPh1_aTMrkC&pg=PA43|accessdate=17 June 2013|date=2010-01-01|publisher=Discovery Publishing House|isbn=9788171412433|page=43}}
55. ^{{cite journal|last=Montgomery|first=H. |author2=B. Morosin |author3=J. J. Natt |author4=A. M. Witkowska |author5=E. C. Lingafelter|year=1967|title=The crystal structure of Tutton's salts. VI. Vanadium(II), iron(II) and cobalt(II) ammonium sulfate hexahydrates|journal=Acta Crystallographica|volume=22|issue=6|pages=775–780|issn=0365-110X|doi=10.1107/S0365110X67001550}}
56. ^{{cite book|last=Swanson,|first=H. E. |author2=McMurdie, H. F. |author3=Morris, M. C. |author4=Evans, E. H. |title=Standard X-ray Diffraction Powder Patterns: Section 7. Data for 81 Substances|url= https://digital.library.unt.edu/ark:/67531/metadc13215/m1/49/|page=43|accessdate=June 17, 2013|date=September 1969|publisher=UNT Digital Library|location=Washington D.C}}
57. ^{{cite journal|last1=Lim|first1=Ae Ran|last2=Kim|first2=Sun Ha|title=Structural and thermodynamic properties of Tutton salt K2Zn(SO4)2·6H2O|journal=Journal of Thermal Analysis and Calorimetry|date=23 July 2015|volume=123|issue=1|pages=371–376|doi=10.1007/s10973-015-4865-9}}
58. ^{{cite journal|last1=Somasekharam|first1=V|last2=Prasad|first2=P Siva|last3=Ramesh|first3=K|last4=Reddy|first4=Y P|title=Electronic Spectra of VO and Cu Ions in Rubidium Zinc Sulphate Hexahydrate|journal=Physica Scripta|date=1 February 1986|volume=33|issue=2|pages=169–172|doi=10.1088/0031-8949/33/2/014|bibcode=1986PhyS...33..169S}}
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60. ^{{cite journal|last=Lakshmana Rao|first=J. |author2=K. Purandar|year=1980|title=Absorption spectrum of VO2+ in zinc cesium sulphate hexahydrate|journal=Solid State Communications|volume=33|issue=3|pages=363–364|issn=0038-1098|doi=10.1016/0038-1098(80)91171-0|bibcode=1980SSCom..33..363L}}
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62. ^1 2 {{cite journal|last1=Ananthanarayanan|first1=V.|title=Raman spectra of crystalline double sulphates Part II. Ammonium double sulphates|journal=Zeitschrift für Physik|date=June 1962|volume=166|issue=3|pages=318–327|doi=10.1007/BF01380779|bibcode=1962ZPhy..166..318A}}
63. ^{{cite journal|last=Voigt|first=W. |author2=S. Göring|year=1994|title=Melting of Tutton's salts studied by DSC|journal=Thermochimica Acta|volume=237|issue=1|pages=13–26|issn=0040-6031|doi=10.1016/0040-6031(94)85179-4}}
64. ^{{cite journal|last1=Chand|first1=Prem|last2=Krishna|first2=R. Murali|last3=Rao|first3=J. Lakshmana|last4=Lakshman|first4=S. V. J.|title=EPR and optical studies of vanadyl complexes in two host-crystals of Tutton salts of thallium|journal=Radiation Effects and Defects in Solids|date=November 1993|volume=127|issue=2|pages=245–254|doi=10.1080/10420159308220322|bibcode=1993REDS..127..245C}}

2 : Double salts|Sulfates
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