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+.

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

M1 M2 formula name a Å b Å c Å β° V Å3 colour Nα Nβ Nγ Biaxial 2V other
K Cd K2[Cd(H2O)6](SO4)2 Potassium cadmium sulfate hexahydrate[8]
Cs Cd Cs2[Cd(H2O)6](SO4)2 caesium cadmium sulphate hexahydrate[9]
NH4 Cd (NH4)2[Cd(H2O)6](SO4)2 Ammonium Cadmium Sulfate Hydrate 9.395 12.776 6.299 106°43' 727.63 colourless l.486 1.488 1.494 Biaxial(-f) large[10] density=2.05[11]

Slowly loses water in dry air.[12]

K Co K2[Co(H2O)6](SO4)2[13] Potassium cobaltous sulfate[14] 6.151 9.061 12.207 104.8° 657.78[15] red density=2.21
Rb Co Rb2[Co(H2O)6](SO4)2 Rubidium hexaaquacobalt(II) sulphate 6.24 9.19 12.453 105.99° 686.5[12] ruby-red[16] desnsity=2.56
Cs Co Cs2[Co(H2O)6](SO4)2 Caesium hexaaquacobalt(II) sulphate 9.318(1) 12.826(3) 6.3650(9) 107.13(1)° 727.0[17] dark red
NH4 Co (NH4)2[Co(H2O)6](SO4)2[18] Cobaltous ammonium sulfate hexahydrate 6.242 9.255 12.549 106.98° 693.3[19] purple[20] density=1.89
Tl Co Tl2[Co(H2O)6](SO4)2 Cobaltous thallium sulfate hexahydrate, Thallium hexaaquacobalt(II) sulfate, 9.227(1) 12.437(2) 6.220(1) 106.40(1)° 684.7 light red[21]
Tl Co Tl2[Co(H2O)6](SO4)2 dithallium cobalt sulfate hexahydrate 9.235(1) 12.442(2) 6.227(1) 106.40(1)° yellowish pink 1.599 1.613 1.624 biaxial(-) medium large[22] density=4.180 g/cm3
Rb Cr Rb2[Cr(H2O)6](SO4)2[23] dirubidium chromium sulfate hexahydrate
Cs Cr Cs2[Cr(H2O)6](SO4)2[23] dicaesium chromium sulfate hexahydrate
ND4 Cr (ND4)2Cr(SO4)2 · 6 H2O[23] dideuterated ammonium chromium sulfate hexahydrate bright blue, formed from with ammonium sulfate in minimal water under nitrogen gas. Stable in air from oxidation, but may dehydrate.[24]
K Cu K2[Cu(H2O)6](SO4)2 cyanochroite[14] 9.27 12.44 6.30 104.47[25] 663.0[25] pale green blue density=2.21[25] within unit cell 7.76 between two Cu atoms[26]
Rb Cu Rb2[Cu(H2O)6](SO4)2 Dirubidium hexaaquacopper sulfate 9.267 12.366 6.228 105°19' 686.8 brilliant greenish blue 1.488 1.491 1.506 biaxial (+)[27] medium density=2.580g/cm3[10] Cu-O 2.098 Å Rb-O 3.055 Å.[27]
Cs Cu Cs2[Cu(H2O)6](SO4)2[28] dicaesium hexaaquacopper sulfate 9.439 12.762 6.310 106°11' 718.5 brilliant greenish blue, 1.504 1.506 1.514 biaxial (+) density=2.864g/cm3[29]
NH4 Cu (NH4)2[Cu(H2O)6](SO4)2 ammonium hexaaquacopper(II) sulfate[30] 6.31 12.38 9.22 106.16° 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]
Tl Cu Tl2[Cu(H2O)6](SO4)2 Thallium copper sulfate hydrate 9.268 12.364 6.216 105°33' brilliant greenish blue 1.600 1.610 1.620 biaxial very large[32] density=3.740 g/cm3
K Fe K2[Fe(H2O)6](SO4)2 dipotassium iron sulfate hexahydrate[14]
Rb Fe Rb2[Fe(H2O)6](SO4)2 Rubidium iron sulfate hydrate 9.218 12.497 6.256 105°45' pale green 1.480 1.489 1.501 biaxial (+) large, density=2.523g/cm3[33]
Cs Fe Cs2[Fe(H2O)6](SO4)2 Caesium hexaaquairon(II) sulphate 9.357(2) 12.886(2) 6.381(1) 106.94(1)° 736.0 dark yellow[17] very pale green 1.501 1.504 1.516 biaxial (+) medium[34] density=2.805
NH4 Fe (NH4)2[Fe(H2O)6](SO4)2 mohrite[14] 6.24(1) 12.65(2) 9.32(2) 106.8(1) 704.28 vitreous pale green density=1.85 named after Karl Friedrich Mohr[35]
Tl Fe Tl2[Fe(H2O)6](SO4)2 Thallium hexaaquairon(II) sulfate 9.262(2) 12.497(1) 6.235(2) 106.15(1)° 693.2[21] light green 1.590 1.605 =1.616 biaxial (-) large density=3.662g/cm3[36]
K Mg K2[Mg(H2O)6](SO4)2 picromerite 9.04 12.24 6.095 104° 48'[14] colourless or white 1.460 1.462 1.472 biaxial (+) medium density=2.025g/cm3;[37] expanded second coordination sphere around Mg.[14]
Rb Mg Rb2[Mg(H2O)6](SO4)2 rubidium magnesium sulphate hexahydrate[38] 9.235 12.486 6.224 105°59' colourless 1.467 1.469 1.476[39] biaxial
Cs Mg Cs2[Mg(H2O)6](SO4)2 Cesium hexaaquamagnesium sulphate 9.338(2) 12.849(4) 6.361(2) 107.07(2)° 729.6 colourless[17] 1.481 1.485 1.492 biaxial(+) medium density=2.689[40]
NH4 Mg (NH4)2[Mg(H2O)6](SO4)2 boussingaultite 9.28 12.57 6.2 107°6'[14][18]
NH4 Mg (NH4)2[Mg(H2O)6](SO4)2 Ammonium Magnesium Chromium Oxide Hydrate 9.508±.001 12.674 6.246 106°14' bright yellow 1.637 1.638 1.653 biaxial(+) small density=1.840 g/cm 3[10]
Tl Mg Tl2[Mg(H2O)6](SO4)2[41] dithallium magnesium sulfate hexahydrate 9.22 9.262(2) 12.42 12.459(2) 6.185 6.207(1) 106°30' 106.39(2)° 687.1 colourless[21] density=3.532 g/cm3
Rb Mn Rb2[Mn(H2O)6](SO4)2 Dirubidium hexaaquamanganese sulfate(VI) 9.282(2) 12.600(2) 6.254(2) 105.94(2) 703.3Å3[42][43]
Cs Mn Cs2[Mn(H2O)6](SO4)2 Caesium hexaaquamanganese(II) sulphate 9.418(3) 12.963(2) 6.386(3) 107.17(4)° 744.9 pale pink[17] purplish white[44] 1.495 1.497 1.502 biaxial(+) large density=2.763[44]
NH4 Mn (NH4)2[Mn(H2O)6](SO4)2 manganese ammonium sulfate hexahydrate 9.40 12.74 6.26 107.0°[45] pale pink 1.482 1.456 1.492 biaxial(+) large density=1.827 [46]
Tl Mn Tl2[Mn(H2O)6](SO4)2 Thallium manganese sulfate hexahydrate 9.3276(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
K Ni K2Ni(SO4)2 · 6 H2O[13] Potassium Nickel Sulfate Hexahydrate[14] used as UV filter[48]
Rb Ni Rb2[Ni(H2O)6](SO4)2 Rubidium Nickel Sulfate Hexahydrate 6.221 12.41 9.131 106.055° 677.43 001 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
Cs Ni Cs2[Ni(H2O)6](SO4)2 Caesium hexaaquanickel(II) sulphate, Cesium Nickel Sulfate Hexahydrate 9.259(2) 12.767(2) 6.358(1) 107.00(2)° 718.7[17] greenish blue 1.507 1.512 1.516 biaxial(-) very large density=2.883 [49] used as UV filter[48]
NH4 Ni (NH4)2[Ni(H2O)6](SO4)2 nickel-boussingaultite[14][50] 9.186 12.468 6.424 684.0 blueish green.[51][52] density=1.918 cas=51287-85-5
Tl Ni Tl2[Ni(H2O)6](SO4)2 Thallium hexaaquanickel(II) sulfate 9.161(2) 12.389(2) 6.210(2) 106.35(2)° 676.3 greenish blue[21] 1.602 1.615 1.620 biaxial(-) large density=3.763[53]
K Ru K2[Ru(H2O)6](SO4)2 [54] 8.950 12.268 6.135 105.27 644
Rb Ru Rb2[Ru(H2O)6](SO4)2 [54] 9.132 12.527 6.351 106.30
K V K2[V(H2O)6](SO4)2 Vanadium(II) potassium sulfate hexahydrate [55]
Rb V Rb2[V(H2O)6](SO4)2 Rubidium vanadium(II) sulfate
NH4 V (NH4)2[V(H2O)6](SO4)2 Vanadium(II) ammonium sulfate hexahydrate 9.42 12.76 6.22 107.2° 714.2 amethyst density=1.8 V-O length 2.15Å[56]
K Zn K2[Zn(H2O)6](SO4)2[13][14] dipotassium zinc sulphate hexahydrate 9.041 12.310 6.182 104.777° colourless 1.478 1.481 1.496 biaxial large density=2.242g/cm3[57] Thermal decomposition at 252K.[58]
Rb Zn Rb2[Zn(H2O)6](SO4)2 Rubidium Zinc Sulphate Hexahydrate[59] 9.185 12.450 6.242 105°54' colourless 1.483 1.489 1.497 biaxial large [60]
Cs Zn Cs2[Zn(H2O)6](SO4)2 zinc cesium sulphate hexahydrate [61] 9.314(2) 12.817(2) 6.369(2) 106.94(2)° 727.3 colourless[17] 1.507 1.610 1.615 biaxial(-) large density=2.881 [62]
NH4 Zn (NH4)2[Zn(H2O)6](SO4)2 9.205 12.475 6.225 106°52'[18] 684.1 heat of fusion 285 J/g[63]
Tl Zn Tl2[Zn(H2O)6](SO4)2 Thallium hexaaquazinc(II) sulfate [64] 9.219(2) 12.426(2) 6.226(1) 106.29(2)° 684.6 colourless[21]
selenates
Cs Ni Cs2[Zn(H2O)6](SeO4)2 Dicaesium nickel selenate hexahydrate[65] 7.4674 7.9152 11.7972 106.363 669.04 light green
Rb Cu Rb2[Cu(H2O)6](SeO4)2 Dirubidium copper selenate hexahydrate[66] 6.363 12.431 9.373 104.33 718.3

Organic salts

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

formula name a Å b Å c Å β° V Å3 colour Nα Nβ Nγ Biaxial 2V other
(C4H12N2)[Zn(H2O)6](SO4)2 piperazinediium hexaaquazinc(II) bis(sulfate)[67] 12.9562 10.6502 13.3251 114.032 1679.30 Colourless
cadmium creatininium sulfate[68] 6.5584 27.871 7.1955 110.371 1232.99 colourless

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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  50. ↑ Montgomery, H.; E.C. Lingafelter (10 November 1964). "The crystal structure of Tutton's salts. II. Magnesium ammonium sulfate hexahydrate and nickel ammonium sulfate hexahydrate". Acta Crystallographica. International Union of Crystallography. 17 (11): 1478. doi:10.1107/s0365110x6400367x.
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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. doi:10.1016/0040-6031(94)85179-4. ISSN 0040-6031.
  64. ↑ Chand, Prem; Krishna, R. Murali; Rao, J. Lakshmana; Lakshman, S. V. J. (November 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.
  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.
  66. ↑ Yankova, Rumyana (May 2020). "Hirshfeld surface analysis and ir investigation for the rubidium hexaaquacopper(II) selenate". Chemical Data Collections. 27: 100379. doi:10.1016/j.cdc.2020.100379. S2CID 218940437.
  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. doi:10.1107/s1600536805005982.
  68. ↑ Colaneri, Michael J.; Teat, Simon J.; Vitali, Jacqueline (20 February 2020). "Electron Paramagnetic Resonance Characteristics and Crystal Structure of a Tutton Salt Analogue: Copper-Doped Cadmium Creatininium Sulfate". The Journal of Physical Chemistry A. 124 (11): 2242–2252. Bibcode:2020JPCA..124.2242C. doi:10.1021/acs.jpca.0c00004. OSTI 1777953. PMID 32078331. S2CID 211231042.
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