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Tutton's salt

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(Redirected from Tutton salt) Class of chemical compounds

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' crystallized in the same regular ionic lattice. 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 (CrO4), tetrafluoroberyllate (BeF4), hydrogenphosphate (HPO4) or monofluorophosphate (PO3F). Tutton's salts crystallize in the monoclinic space group P21/a. 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 .

Examples and related compounds

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

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".

  • Unit cell of ferrous ammonium sulfate (N is violet, O is red, S is orange, Fe is large red). Unit cell of ferrous ammonium sulfate (N is violet, O is red, S is orange, Fe is large red).
  • The same structure with hydrogen bonding network highlighted. The same structure with hydrogen bonding network highlighted.

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.
Such salts were of historical importance because they were obtainable in high purity and served as reliable reagents and spectroscopic standards.

Table of salts

M M formula name a Å b Å c Å β° V Å colour Biaxial 2V other
K Cd K2(SO4)2 Potassium cadmium sulfate hexahydrate
Cs Cd Cs2(SO4)2 caesium cadmium sulphate hexahydrate
NH4 Cd (NH4)2(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 density=2.05

Slowly loses water in dry air.

K Co K2(SO4)2 Potassium cobaltous sulfate 6.151 9.061 12.207 104.8° 657.78 red density=2.21
Rb Co Rb2(SO4)2 Rubidium hexaaquacobalt(II) sulphate 6.24 9.19 12.453 105.99° 686.5 ruby-red desnsity=2.56
Cs Co Cs2(SO4)2 Caesium hexaaquacobalt(II) sulphate 9.318(1) 12.826(3) 6.3650(9) 107.13(1)° 727.0 dark red
NH4 Co (NH4)2(SO4)2 Cobaltous ammonium sulfate hexahydrate 6.242 9.255 12.549 106.98° 693.3 purple density=1.89
Tl Co Tl2(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
Tl Co Tl2(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 density=4.180 g/cm
Rb Cr Rb2(SO4)2 dirubidium chromium sulfate hexahydrate
Cs Cr Cs2(SO4)2 dicaesium chromium sulfate hexahydrate
ND4 Cr (ND4)2Cr(SO4)2 · 6 H2O dideuterated ammonium chromium sulfate hexahydrate bright blue, formed from CrSO 4 3 H 2 O {\displaystyle {\ce {CrSO4.3H2O}}} with ammonium sulfate in minimal water under nitrogen gas. Stable in air from oxidation, but may dehydrate.
K Cu K2(SO4)2 cyanochroite 9.27 12.44 6.30 104.47 663.0 pale green blue density=2.21 within unit cell 7.76 between two Cu atoms
Rb Cu Rb2(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 (+) medium density=2.580g/cm3 Cu-O 2.098 Å Rb-O 3.055 Å.
Cs Cu Cs2(SO4)2 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
NH4 Cu (NH4)2(SO4)2 ammonium hexaaquacopper(II) sulfate 6.31 12.38 9.22 106.16° 691.25 density=1.921; heat of formation=-777.9 kcal/mol 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%.
Tl Cu Tl2(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 density=3.740 g/cm3
K Fe K2(SO4)2 dipotassium iron sulfate hexahydrate
Rb Fe Rb2(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
Cs Fe Cs2(SO4)2 Caesium hexaaquairon(II) sulphate 9.357(2) 12.886(2) 6.381(1) 106.94(1)° 736.0 dark yellow very pale green 1.501 1.504 1.516 biaxial (+) medium density=2.805
NH4 Fe (NH4)2(SO4)2 mohrite 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
Tl Fe Tl2(SO4)2 Thallium hexaaquairon(II) sulfate 9.262(2) 12.497(1) 6.235(2) 106.15(1)° 693.2 light green 1.590 1.605 =1.616 biaxial (-) large density=3.662g/cm3
K Mg K2(SO4)2 picromerite 9.04 12.24 6.095 104° 48' colourless or white 1.460 1.462 1.472 biaxial (+) medium density=2.025g/cm3; expanded second coordination sphere around Mg.
Rb Mg Rb2(SO4)2 rubidium magnesium sulphate hexahydrate 9.235 12.486 6.224 105°59' colourless 1.467 1.469 1.476 biaxial
Cs Mg Cs2(SO4)2 Caesium hexaaquamagnesium sulphate 9.338(2) 12.849(4) 6.361(2) 107.07(2)° 729.6 colourless 1.481 1.485 1.492 biaxial(+) medium density=2.689
NH4 Mg (NH4)2(SO4)2 boussingaultite 9.28 12.57 6.2 107°6'
NH4 Mg (NH4)2(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
Tl Mg Tl2(SO4)2 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 density=3.532 g/cm
Rb Mn Rb2(SO4)2 Dirubidium hexaaquamanganese sulfate(VI) 9.282(2) 12.600(2) 6.254(2) 105.94(2) 703.3Å
Cs Mn Cs2(SO4)2 Caesium hexaaquamanganese(II) sulphate 9.418(3) 12.963(2) 6.386(3) 107.17(4)° 744.9 pale pink purplish white 1.495 1.497 1.502 biaxial(+) large density=2.763
NH4 Mn (NH4)2(SO4)2 manganese ammonium sulfate hexahydrate 9.40 12.74 6.26 107.0° pale pink 1.482 1.456 1.492 biaxial(+) large density=1.827
Tl Mn Tl2(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)° 106.29(2)°, 700.8 light pink
K Ni K2Ni(SO4)2 · 6 H2O Potassium Nickel Sulfate Hexahydrate used as UV filter
Rb Ni Rb2(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 nm density 2.596 g cm. stable to 100.5 °C solubility in g/100ml=0.178t + 4.735 MW=529.87
Cs Ni Cs2(SO4)2 Caesium hexaaquanickel(II) sulphate, Caesium Nickel Sulfate Hexahydrate 9.259(2) 12.767(2) 6.358(1) 107.00(2)° 718.7 greenish blue 1.507 1.512 1.516 biaxial(-) very large density=2.883 used as UV filter
NH4 Ni (NH4)2(SO4)2 nickel-boussingaultite 9.186 12.468 6.424 684.0 blueish green. density=1.918 cas=51287-85-5
Tl Ni Tl2(SO4)2 Thallium hexaaquanickel(II) sulfate 9.161(2) 12.389(2) 6.210(2) 106.35(2)° 676.3 greenish blue 1.602 1.615 1.620 biaxial(-) large density=3.763
K Ru K2(SO4)2 8.950 12.268 6.135 105.27 644
Rb Ru Rb2(SO4)2 9.132 12.527 6.351 106.30
K V K2(SO4)2 Vanadium(II) potassium sulfate hexahydrate
Rb V Rb2(SO4)2 Rubidium vanadium(II) sulfate
NH4 V (NH4)2(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
K Zn K2(SO4)2 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 Thermal decomposition at 252K.
Rb Zn Rb2(SO4)2 Rubidium Zinc Sulphate Hexahydrate 9.185 12.450 6.242 105°54' colourless 1.483 1.489 1.497 biaxial large
Cs Zn Cs2(SO4)2 zinc caesium sulphate hexahydrate 9.314(2) 12.817(2) 6.369(2) 106.94(2)° 727.3 colourless 1.507 1.610 1.615 biaxial(-) large density=2.881
NH4 Zn (NH4)2(SO4)2 9.205 12.475 6.225 106°52' 684.1 heat of fusion 285 J/g
Tl Zn Tl2(SO4)2 Thallium hexaaquazinc(II) sulfate 9.219(2) 12.426(2) 6.226(1) 106.29(2)° 684.6 colourless
selenates
Cs Ni Cs2(SeO4)2 Dicaesium nickel selenate hexahydrate 7.4674 7.9152 11.7972 106.363 669.04 light green
Rb Cu Rb2(SeO4)2 Dirubidium copper selenate hexahydrate 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 Å colour Biaxial 2V other
(C4H12N2)(SO4)2 piperazinediium hexaaquazinc(II) bis(sulfate) 12.9562 10.6502 13.3251 114.032 1679.30 Colourless
cadmium creatininium sulfate 6.5584 27.871 7.1955 110.371 1232.99 colourless

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