Tutton's salt

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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, caesium, 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+.

Contents

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 Alfred Edwin Howard 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
KCdK2[Cd(H2O)6](SO4)2Potassium cadmium sulfate hexahydrate [8]
CsCdCs2[Cd(H2O)6](SO4)2caesium cadmium sulphate hexahydrate [9]
NH4Cd(NH4)2[Cd(H2O)6](SO4)2Ammonium 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]

KCoK2[Co(H2O)6](SO4)2 [13] Potassium cobaltous sulfate [14] 6.1519.06112.207104.8°657.78 [15] reddensity=2.21
RbCoRb2[Co(H2O)6](SO4)2Rubidium hexaaquacobalt(II) sulphate6.249.1912.453105.99°686.5 [12] ruby-red [16] 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 [17] dark red
NH4Co(NH4)2[Co(H2O)6](SO4)2 [18] Cobaltous ammonium sulfate hexahydrate6.2429.25512.549106.98°693.3 [19] purple [20] 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 [21]
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 [22] density=4.180 g/cm3
RbCrRb2[Cr(H2O)6](SO4)2 [23] dirubidium chromium sulfate hexahydrate
CsCrCs2[Cr(H2O)6](SO4)2 [23] dicaesium chromium sulfate hexahydrate
ND4Cr(ND4)2Cr(SO4)2 · 6 H2O [23] dideuterated ammonium chromium sulfate hexahydratebright blue,formed from with ammonium sulfate in minimal water under nitrogen gas. Stable in air from oxidation, but may dehydrate. [24]
KCuK2[Cu(H2O)6](SO4)2 cyanochroite [14] 9.2712.446.30104.47 [25] 663.0 [25] pale green bluedensity=2.21 [25] within unit cell 7.76 between two Cu atoms [26]
RbCuRb2[Cu(H2O)6](SO4)2Dirubidium hexaaquacopper sulfate9.26712.3666.228105°19'686.8brilliant greenish blue1.4881.4911.506biaxial (+) [27] mediumdensity=2.580g/cm3 [10] Cu-O 2.098 Å Rb-O 3.055 Å. [27]
CsCuCs2[Cu(H2O)6](SO4)2 [28] dicaesium hexaaquacopper sulfate9.43912.7626.310106°11'718.5brilliant greenish blue,1.5041.5061.514biaxial (+)density=2.864g/cm3 [29]
NH4Cu(NH4)2[Cu(H2O)6](SO4)2ammonium hexaaquacopper(II) sulfate [30] 6.3112.389.22106.16°691.25 [31] density=1.921; [31] heat of formation=-777.9 kcal/mol [31] 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%. [30]
TlCuTl2[Cu(H2O)6](SO4)2Thallium copper sulfate hydrate9.26812.3646.216105°33'brilliant greenish blue1.6001.6101.620biaxialvery large [32] density=3.740 g/cm3
KFeK2[Fe(H2O)6](SO4)2dipotassium iron sulfate hexahydrate [14]
RbFeRb2[Fe(H2O)6](SO4)2Rubidium iron sulfate hydrate9.21812.4976.256105°45'pale green1.4801.4891.501biaxial (+)large,density=2.523g/cm3 [33]
CsFeCs2[Fe(H2O)6](SO4)2Caesium hexaaquairon(II) sulphate9.357(2)12.886(2)6.381(1)106.94(1)°736.0dark yellow [17] very pale green1.5011.5041.516biaxial (+)medium [34] density=2.805
NH4Fe(NH4)2[Fe(H2O)6](SO4)2 mohrite [14] 6.24(1)12.65(2)9.32(2)106.8(1)704.28vitreous pale greendensity=1.85 named after Karl Friedrich Mohr [35]
TlFeTl2[Fe(H2O)6](SO4)2Thallium hexaaquairon(II) sulfate9.262(2)12.497(1)6.235(2)106.15(1)°693.2 [21] light green1.5901.605=1.616biaxial (-)largedensity=3.662g/cm3 [36]
KMgK2[Mg(H2O)6](SO4)2 picromerite 9.0412.246.095104° 48' [14] colourless or white1.4601.4621.472biaxial (+)mediumdensity=2.025g/cm3; [37] expanded second coordination sphere around Mg. [14]
RbMgRb2[Mg(H2O)6](SO4)2rubidium magnesium sulphate hexahydrate [38] 9.23512.4866.224105°59'colourless1.4671.4691.476 [39] biaxial
CsMgCs2[Mg(H2O)6](SO4)2Caesium hexaaquamagnesium sulphate9.338(2)12.849(4)6.361(2)107.07(2)°729.6colourless [17] 1.4811.4851.492biaxial(+)mediumdensity=2.689 [40]
NH4Mg(NH4)2[Mg(H2O)6](SO4)2 boussingaultite 9.2812.576.2107°6' [14] [18]
NH4Mg(NH4)2[Mg(H2O)6](SO4)2Ammonium Magnesium Chromium Oxide Hydrate9.508±.00112.6746.246106°14'bright yellow1.6371.6381.653biaxial(+)smalldensity=1.840 g/cm 3 [10]
TlMgTl2[Mg(H2O)6](SO4)2 [41] 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 [21] 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 [42] [43]
CsMnCs2[Mn(H2O)6](SO4)2Caesium hexaaquamanganese(II) sulphate9.418(3)12.963(2)6.386(3)107.17(4)°744.9pale pink [17] purplish white [44] 1.4951.4971.502biaxial(+)largedensity=2.763 [44]
NH4Mn(NH4)2[Mn(H2O)6](SO4)2manganese ammonium sulfate hexahydrate9.4012.746.26107.0° [45] pale pink1.4821.4561.492biaxial(+)largedensity=1.827 [46]
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)° [47] 106.29(2)°,700.8 [21] light pink
KNiK2Ni(SO4)2 · 6 H2O [13] Potassium Nickel Sulfate Hexahydrate [14] used as UV filter [48]
RbNiRb2[Ni(H2O)6](SO4)2Rubidium 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. [48] 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, Caesium Nickel Sulfate Hexahydrate9.259(2)12.767(2)6.358(1)107.00(2)°718.7 [17] greenish blue1.5071.5121.516biaxial(-)very largedensity=2.883 [49] used as UV filter [48]
NH4Ni(NH4)2[Ni(H2O)6](SO4)2 nickel-boussingaultite [14] [50] 9.18612.4686.424684.0blueish green. [51] [52] density=1.918 cas=51287-85-5
TlNiTl2[Ni(H2O)6](SO4)2Thallium hexaaquanickel(II) sulfate9.161(2)12.389(2)6.210(2)106.35(2)°676.3greenish blue [21] 1.6021.6151.620biaxial(-)largedensity=3.763 [53]
KRuK2[Ru(H2O)6](SO4)2 [54] 8.95012.2686.135105.27644
RbRuRb2[Ru(H2O)6](SO4)2 [54] 9.13212.5276.351106.30
KVK2[V(H2O)6](SO4)2Vanadium(II) potassium sulfate hexahydrate [55]
RbVRb2[V(H2O)6](SO4)2Rubidium vanadium(II) sulfate
NH4V(NH4)2[V(H2O)6](SO4)2Vanadium(II) ammonium sulfate hexahydrate9.4212.766.22107.2°714.2amethystdensity=1.8 V-O length 2.15Å [56]
KZnK2[Zn(H2O)6](SO4)2 [13] [14] dipotassium zinc sulphate hexahydrate9.04112.3106.182104.777°colourless1.4781.4811.496biaxiallargedensity=2.242g/cm3 [57] Thermal decomposition at 252K. [58]
RbZnRb2[Zn(H2O)6](SO4)2Rubidium Zinc Sulphate Hexahydrate [59] 9.18512.4506.242105°54'colourless1.4831.4891.497biaxiallarge [60]
CsZnCs2[Zn(H2O)6](SO4)2zinc caesium sulphate hexahydrate [61] 9.314(2)12.817(2)6.369(2)106.94(2)°727.3colourless [17] 1.5071.6101.615biaxial(-)largedensity=2.881 [62]
NH4Zn(NH4)2[Zn(H2O)6](SO4)29.20512.4756.225106°52' [18] 684.1heat of fusion 285 J/g [63]
TlZnTl2[Zn(H2O)6](SO4)2Thallium hexaaquazinc(II) sulfate [64] 9.219(2)12.426(2)6.226(1)106.29(2)°684.6colourless [21]
selenates
CsNiCs2[Zn(H2O)6](SeO4)2Dicaesium nickel selenate hexahydrate [65] 7.46747.915211.7972106.363669.04light green
RbCuRb2[Cu(H2O)6](SeO4)2Dirubidium copper selenate hexahydrate [66] 6.36312.4319.373104.33718.3

Organic salts

Some organic bases can also form salts that crystallise like Tutton's salts.

formulanamea Åb Åc Åβ°V Å3colourNαNβNγBiaxial2Vother
(C4H12N2)[Zn(H2O)6](SO4)2piperazinediium hexaaquazinc(II) bis(sulfate) [67] 12.956210.650213.3251114.0321679.30Colourless
cadmium creatininium sulfate [68] 6.558427.8717.1955110.3711232.99colourless

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References

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  2. ↑ Ettoumi, Houda; Bulou, Alain; Suñol, Joan Josep; Mhiri, Tahar (November 2015). "Synthesis, crystal structure, and vibrational study of : A new metal hydrogenphosphate compound". Journal of Molecular Structure. 1099: 181–188. Bibcode:2015JMoSt1099..181E. doi:10.1016/j.molstruc.2015.06.060.
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  14. 1 2 3 4 5 6 7 8 9 10 Bosi, F.; G. Belardi; P. Ballirano (2009). "Structural features in Tutton's salts , with ". American Mineralogist. 94 (1): 74–82. Bibcode:2009AmMin..94...74B. doi:10.2138/am.2009.2898. ISSN   0003-004X. S2CID   97302855.
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  27. 1 2 Ballirano, Paolo; Girolamo Belardi (2007). "Rietveld refinement of the Tutton's salt from parallel-beam X-ray powder diffraction data". Acta Crystallographica Section E. 63 (2): i56–i58. doi:10.1107/S1600536807002656. ISSN   1600-5368.
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  29. ↑ Swanson, H. E.; McMurdie, H. F.; Morris, M. C.; Evans, E. H.. (September 1969). Standard X-ray Diffraction Powder Patterns: Section 7. Data for 81 Substances. Washington D.C: UNT Digital Library. p. 14. Retrieved June 17, 2013.
  30. 1 2 Simmons, Charles J.; Michael A. Hitchman; Horst Stratemeier; Arthur J. Schultz (1993). "High-pressure, low-temperature, single-crystal neutron diffraction study of deuterated and hydrogenous ammonium hexaaquacopper(II) sulfate (Tutton's salt): a pressure-switchable Jahn-Teller distortion". Journal of the American Chemical Society. 115 (24): 11304–11311. Bibcode:1993JAChS.11511304S. doi:10.1021/ja00077a032. ISSN   0002-7863.
  31. 1 2 3 "976 Diammonium hexaquacopper(ii) sulfate () (ICSD 62991)". openmopac. Retrieved 2 July 2015.
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  33. ↑ Swanson, H. E.; H. F. McMurdie; M. C. Morris; E. H. Evans (September 1970). "Standard X-ray Diffraction Powder Patterns" (PDF). National Bureau of Standards Monograph 25 Section 8. National Bureau of Standards. p. 64. Retrieved 16 June 2013.
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  38. ↑ Somasekharam, V.; Y.P. Reddy (1985). "Spectroscopic studies on vanadyl ion in rubidium magnesium sulphate hexahydrate". Solid State Communications. 53 (8): 695–697. Bibcode:1985SSCom..53..695S. doi:10.1016/0038-1098(85)90380-1. ISSN   0038-1098.
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  40. ↑ Swanson, H. E.; McMurdie, H. F.; Morris, M. C.; Evans, E. H. (September 1969). Standard X-ray Diffraction Powder Patterns: Section 7. Data for 81 Substances. Washington D.C: UNT Digital Library. p. 18. Retrieved June 17, 2013.
  41. ↑ Chand, Prem; R. Murali Krishna; J. Lakshmana Rao; S. V. J. Lakshman (1993). "EPR and optical studies of vanadyl complexes in two host-crystals of Tutton salts of thallium". Radiation Effects and Defects in Solids. 127 (2): 245–254. Bibcode:1993REDS..127..245C. doi:10.1080/10420159308220322. ISSN   1042-0150.
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  47. ↑ Nalbandyan, V. B. (29 February 2012). "Thallium manganese sulfate hexahydrate, a missing Tutton's salt, and a brief review of the entire family". Powder Diffraction. 23 (1): 52–55. Bibcode:2008PDiff..23...52N. doi:10.1154/1.2840634. S2CID   97043497.
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  58. ↑ Lim, Ae Ran; Kim, Sun Ha (23 July 2015). "Structural and thermodynamic properties of Tutton salt K2Zn(SO4)2·6H2O". Journal of Thermal Analysis and Calorimetry. 123 (1): 371–376. doi:10.1007/s10973-015-4865-9. S2CID   93389171.
  59. ↑ Somasekharam, V; Prasad, P Siva; Ramesh, K; Reddy, Y P (1 February 1986). "Electronic Spectra of VO and Cu Ions in Rubidium Zinc Sulphate Hexahydrate". Physica Scripta. 33 (2): 169–172. Bibcode:1986PhyS...33..169S. doi:10.1088/0031-8949/33/2/014. S2CID   250762626.
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  63. ↑ Voigt, W.; S. Göring (1994). "Melting of Tutton's salts studied by DSC". Thermochimica Acta. 237 (1): 13–26. Bibcode:1994TcAc..237...13V. doi:10.1016/0040-6031(94)85179-4. ISSN   0040-6031.
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  65. ↑ Yankova, Rumyana; Genieva, Svetlana (June 2019). "Crystal structure and IR investigation of double salt Cs2Ni(SeO4)2·4H2O". Chemical Data Collections. 21: 100234. doi:10.1016/j.cdc.2019.100234. S2CID   181399910.
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  67. ↑ Rekik, Walid; Naïli, Houcine; Mhiri, Tahar; Bataille, Thierry (April 2005). "Piperazinediium hexaaquazinc(II) bis(sulfate): A structural analogue of Tutton's salts". Acta Crystallographica Section E. 61 (4): m629. Bibcode:2005AcCrE..61M.629R. doi:10.1107/s1600536805005982.
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