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Nickel double salts

Nickel can form various double salts.

Tutton's salts

Nickel is one of the metals that can form Tutton's salts. The singly charged ion can be any of the full range of potassium, rubidium, cesium, ammonium (NH<sub>4</sub>), or thallium.

Mineral forms

As a mineral the ammonium nickel salt, (NH<sub>4</sub>)<sub>2</sub>Ni(SO<sub>4</sub>)<sub>2</sub>, can be called nickelboussingaultite. With sodium, the double sulfate is nickelblödite Na<sub>2</sub>Ni(SO<sub>4</sub>)<sub>2</sub> from the blödite family. Nickel can be substituted by other divalent metals of similar sized to make mixtures that crystallise in the same form.

Langbeinites

Anhydrous salts of the formula M<sub>2</sub>Ni<sub>2</sub>(SO<sub>4</sub>)<sub>3</sub>, which can be termed metal nickel trisulfates, belong to the family of langbeinites. The known salts include (NH<sub>4</sub>)<sub>2</sub>Ni<sub>2</sub>(SO<sub>4</sub>)<sub>3</sub>, K<sub>2</sub>Ni<sub>2</sub>(SO<sub>4</sub>)<sub>3</sub> and Rb<sub>2</sub>Ni<sub>2</sub>(SO<sub>4</sub>)<sub>3</sub>, and those of Tl and Cs are predicted to exist.

Double halides

Fluorides

Double fluorides include the fluoroanion salts, and those fluoronickelates such as NiF<sub>4</sub> and NiF<sub>6</sub>:

  • KNiF<sub>3</sub>·H<sub>2</sub>O and NaNiF<sub>3</sub>·H<sub>2</sub>O – apple green coloured
  • aluminium nickel pentafluoride (AlNiF<sub>5</sub>·7H<sub>2</sub>O)
  • ceric nickelous decafluoride (Ce<sub>2</sub>NiF<sub>10</sub>·7H<sub>2</sub>O)
  • niobium nickel fluoride (Ni<sub>3</sub>H<sub>4</sub>Nb<sub>2</sub>F<sub>20</sub>·19H<sub>2</sub>O)
  • vanadium nickel pentafluoride (VNiF<sub>5</sub>·7H<sub>2</sub>O)
  • vanadyl nickel tetrafluoride (VONiF<sub>4</sub>·7H<sub>2</sub>O)
  • chromic nickelous pentafluoride (CrNiF<sub>5</sub>·7H<sub>2</sub>O)
  • molybdenum nickel dioxytetrafluoride (NiMoO<sub>2</sub>F<sub>4</sub>·6H<sub>2</sub>O)
  • tungsten nickel dioxytetrafluoride hexahydrate (NiWO<sub>2</sub>F<sub>4</sub>·6H<sub>2</sub>O) and decahydrate (NiWO<sub>2</sub>F<sub>4</sub>·10H<sub>2</sub>O)
  • manganic nickel pentafluoride (MnNiF<sub>4</sub>·7H<sub>2</sub>O)
  • nickelous ferric fluoride (FeNiF<sub>5</sub>·7H<sub>2</sub>O)

Chlorides

Trichlorides

Nickel trichloride double salts exist which are polymers. Nickel is in octahedral coordination, with double halogen bridges. Examples of this include RbNiCl<sub>3</sub>, pinkish tan coloured H<sub>2</sub>NN(CH<sub>3</sub>)<sub>3</sub>NiCl<sub>3</sub>.

Other double trichlorides include:

  • potassium nickel trichloride (KNiCl<sub>3</sub>·5H<sub>2</sub>O)
  • yellow cesium nickel trichloride (CsNiCl<sub>3</sub>)
  • lithium nickel trichloride (LiNiCl<sub>3</sub>·3H<sub>2</sub>O)
  • nickel ammonium chloride hexahydrate (NH<sub>4</sub>NiCl<sub>3</sub>·6H<sub>2</sub>O)

Tetrachlorides

The tetrachloronickelates contain a tetrahedral NiCl<sub>4</sub><sup>2−</sup> and are dark blue. Some salts of organic bases are ionic liquids at standard conditions. Tetramethylammonium nickel trichloride is pink and very insoluble.

Other tetrachlorides include:

  • hyrdrazinium nickel tetrachloride
  • lithium nickel tetrachloride (Li<sub>2</sub>NiCl<sub>4</sub>·4H<sub>2</sub>O) – stable from 23 to 60°
  • rubidium nickel tetrachloride
  • stannous nickel tetrachloride (SnCl<sub>2</sub>·NiCl<sub>2</sub>·6H<sub>2</sub>O)

Hexachlorides

Double hexachlorides include:

  • cadmium dinickel hexachloride (CdCl<sub>2</sub>•2NiCl<sub>2</sub>•12H<sub>2</sub>O) – crystallises in hexagonal system
  • dicadmium dinickel hexachloride (2CdCl<sub>2</sub>•NiCl<sub>2</sub>•12H<sub>2</sub>O) – rhombic crystals, pleochroic varying from light to dark green.
  • lithium nickel hexachloride Li<sub>4</sub>NiCl<sub>6</sub>·10H<sub>2</sub>O – stable from 0 to 23°
  • stannic nickel hexachloride (SnCl<sub>4</sub>·NiCl<sub>2</sub>·6H<sub>2</sub>O) – tetragonal

Octochlorides

Thallic nickel octochloride 2TlCl<sub>3</sub>·NiCl<sub>2</sub>·8H<sub>2</sub>O is bright green.

Oxychlorides

Copper nickel dioxychloride 2CuO·NiCl<sub>2</sub>·6H<sub>2</sub>O and copper nickel trioxychloride 3CuO·NiCl<sub>2</sub>·4H<sub>2</sub>O exist.

Bromides

Double bromides include the tetrabromonickelates. Other salts include:

  • caesium nickel tribromide (CsNiBr<sub>3</sub>)
  • copper nickel trioxybromide (3CuO·NiBr<sub>2</sub>·4H<sub>2</sub>O)
  • didymium nickel bromide (2(Pr,Nd)Br<sub>3</sub>·3NiBr<sub>2</sub>·18H<sub>2</sub>O) – reddish brown, mixture of praseodymium and neodymium
  • lanthanum nickel bromide (2LaBr3·3NiBr2·18H2O)
  • mercuric nickel bromides (Hg<sub>2</sub>NiBr6) and (HgNiBr<sub>4</sub>)
  • mercuric nickel oxybromide (6NiO·NiBr<sub>2</sub>•HgBr<sub>2</sub>•20H<sub>2</sub>O) – prepared by reacting nickel bromide with mercuric oxide
  • nickel stannic bromide or nickel bromostannate (NiSnBr<sub>6</sub>·8H<sub>2</sub>O) – apple green

Iodides

The tetraiodonickelates are blood-red coloured salts of the NiI<sub>4</sub> ion with large cations. The diperiodatonickelates of nickel(IV) are strong oxidisers, and akali monoperiodatonickelates also are known.

Double iodides include:

  • mercuric nickel hexaiodide (2HgI<sub>2</sub>·NiI<sub>2</sub>)
  • mercuric nickel tetraiodide (HgI<sub>2</sub>·NiI<sub>2</sub>)
  • lead nickel hexaiodide (I<sub>2</sub>·2NiI<sub>2</sub>)

Double nitrates

Lanthanides

Nickel forms double nitrates with the lighter rare-earth elements. The solid crystals have the formula Ni<sub>3</sub>Me<sub>2</sub>(NO<sub>3</sub>)<sub>12</sub>•24H<sub>2</sub>O. The metals include La, Ce, Pr, Nd, Sm, Gd and the non rare earth Bi. Nickel can also be replaced by similar divalent ions Mg, Mn, Co, and Zn. For the nickel salts melting temperatures range from 110.5° for La, 108.5° for Ce, 108° for Pr, 105.6° for Nd, 92.2° for Sm and down to 72.5° for Gd, the Bi salt melting at 69°. Crystal structure is hexagonal with Z=3. Ni<sub>3</sub>La<sub>2</sub>(NO<sub>3</sub>)<sub>12</sub>•24H<sub>2</sub>O becomes ferromagnetic below 0.393&nbsp;K. These double nickel nitrates have been used to separate the rare earth elements by fractional crystallization.

Actinides

Nickel thorium nitrate has formula NiTh(NO<sub>3</sub>)<sub>6</sub>. Nickel atoms can be substituted by other ions with radius 0.69 to 0.83&nbsp;Å. The nitrates are coordinated on the thorium atom and the water to the nickel. Enthalpy of solution of the octahydrate is 7 kJ/mol. Enthalpy of formation is -4360 kJ/mol. At 109° the octahydrate becomes NiTh(NO<sub>3</sub>)<sub>6</sub>•6H<sub>2</sub>O, and at 190° NiTh(NO<sub>3</sub>)<sub>6</sub>•3H<sub>2</sub>O and anhydrous at 215°. The hexahydrate has Pa cubic structure.

Double nitrites

Double amides

Various double amides containing nickel clusters have been made using liquid ammonia as a solvent. These are called amidonickel compounds.

These include:

  • Li<sub>3</sub>Ni<sub>4</sub>(NH<sub>2</sub>)<sub>11</sub>·NH<sub>3</sub> (Pna21; Z = 4; a = 16.344(3) Å; b = 12.310(2) Å; c = 8.113(2) Å v=1631 D=1.942) – red
  • Li<sub>4</sub>Ni<sub>4</sub>(NH<sub>2</sub>)<sub>12</sub>·NH<sub>3</sub>, Na<sub>2</sub>Ni(NH<sub>2</sub>)<sub>4</sub>
  • Na<sub>2</sub>Ni(NH<sub>2</sub>)<sub>4</sub>•NH<sub>3</sub>
  • Na<sub>2</sub>Ni(NH<sub>2</sub>)<sub>4</sub>•2NH<sub>3</sub> – orange red
  • K<sub>2</sub>Ni(NH<sub>2</sub>)<sub>4</sub>•0.23KNH<sub>2</sub>
  • Rb<sub>2</sub>Ni(NH<sub>2</sub>)<sub>4</sub>•0.23RbNH<sub>2</sub>
  • Cs<sub>2</sub>Ni(NH<sub>2</sub>)<sub>4</sub>•NH<sub>3</sub> (P21/c; Z = 4; a =9.553(3) Å; b = 8.734(3) Å; c = 14.243(3) Å; β = 129.96(3)° V=910 D=2.960)

Double hydrides

Double hydrides of nickel exist, such as Mg<sub>2</sub>NiH<sub>4</sub>.

Double dihydrogen phosphides

Nickel dihydrogen phosphide (Ni(PH<sub>2</sub>)<sub>2</sub>) can form orange, green or black double salts KNi(PH<sub>2</sub>)<sub>3</sub>) that crystallise from liquid ammonia. They are unstable above -78&nbsp;°C, giving off ammonia, phosphine and hydrogen.

Double tetrafluoroberyllates

Nickel forms double salts with Tutton's salt structure with tetrafluoroberyllate and a range of cations including ammonia, potassium, rubidium, cesium, and thallium.

Other minerals

Some minerals are double salts, for example nickelzippeite Ni<sub>2</sub>(UO<sub>2</sub>)<sub>6</sub>(SO<sub>4</sub>)<sub>3</sub>(OH)<sub>10</sub> · 16H<sub>2</sub>O which is isomorphic to cobaltzippeite, magnesiozippeite and zinczippeite, part of the zippeite group.

Table of nickel double salts

References