Chemistry:Nickel oxyacid salts

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bright green crystals in two clusters on a white and grey rock
Mint green Annabergite, a nickel arsenite

The Nickel oxyacid salts are a class of chemical compounds of nickel with an oxyacid. The compounds include a number of minerals and industrially important nickel compounds.

Nickel(II) sulfate can crystallise with six water molecules yielding Retgersite or with seven making Morenosite which is isomorphic to Epsom salts. These contain the hexaquanickel(II) ion.[1] There is also an anhydrous form, a dihydrate and a tetrahydrate, the last two crystallised from sulfuric acid. The hexahydrate has two forms, a blue tetragonal form, and a green monoclinic form, with a transition temperature around 53 °C.[2] The heptahydrate crystallises from water below 31.5 above this blue hexhydrate forms, and above 53.3 the green form.[3] Heating nickel sulfate dehydrates it, and then 700° it loses sulfur trioxide, sulfur dioxide and oxygen.

Nickel sulfite can be formed by bubbling sulfur dioxide through nickel carbonate suspended in water. A solution is formed that slowly loses sulfur dioxide, and which crystallises nickel sulfite hexahydrate. Crystals are frequently in the shape of stars, caused by the two opposite triangular enantiomorphs growing base to base. nickel sulfite hexahydrate is highly piezoelectric. Optically it is uniaxial negative with refractive indexes ω=1.552 ε=1.509.[4] When heated it dehydrates and then ends up producing nickel oxide and nickel sulfate.[5]

Nickel thiosulfate NiS2O3 has the same structure as the magnesium salt. It has alternating layers of octahedral shaped nickel2+ hexahydrate, and tetrahedral shaped S2O32− perpendicular to the β direction.[6] When heated to 90 °C it decomposes to form NiS. NiS2O3 can be made from BaS2O3 and NiSO4.[7] Nickel sulfamate can be used for nickel or mixed nickel-tungsten plating.[8] It can be formed by the action of sulfamic acid on nickel carbonate.[9]

Nickel selenite NiSeO3 has many different hydrates, anhydrous NiSeO3 • ​13H2O, NiSeO3 • H2O, NiSeO3 • 2H2O (which is also a mineral called ahlfeldite), and NiSeO3 • 4H2O.[10]

Nickel nitrate commonly crystallises with six water molecules,[1] but can also be anhydrous, or with two, four or nine waters.[11] triphenylphosphine oxide nickel nitrate [(C6H6)3PO]2Ni(NO3)2 is non ionic, with nitrato as a ligand. It can be made from nickel perchlorate. It is yellow and melts at 266 °C.[12]

Nickel carbonate NiCO3 • 6H2O, hellyerite,[13] crystallising with six water molecules, precipitates when an alkali bicarbonate is added to a Ni aqueous solution.[1] Basic nickel carbonate, zaratite, with the formula Ni4CO3(OH)6(H2O)4, is produced when alkali carbonates are added to a nickel solution. Nickel phosphate, Ni3(PO4)2 • 7H2O is also insoluble.[1] A number of other phosphates have been made, including nanoporous substances resembling zeolites named with "Versailles Santa Barbara" or VSB.[14] The nanoporous nickel phosphates can accommodate sufficiently small molecules and selectively catalyze reactions on them.[15] A nickel arsenate, Ni3(AsO4)2·8H2O occurs as the mineral annabergite.[16][17]

Nickel perchlorate, Ni(ClO4)2 • 6H2O,[1] nickel chlorate, Ni(ClO3)2 • 6H2O,[18] nickel chromate (NiCrO4), nickel chromite (NiCr2O4), nickel(II) titanate, nickel bromate Ni(BrO3)2 • 6H2O,[19] nickel iodate (Ni(IO3)2 • 4H2O), nickel stannate (NiSnO3 • 2H2O)[20] are some other oxy-salts.

The uranates include NiU2O6,[21] NiUO4 α and β forms (orthorhombic a=6.415 Å; b=6.435 Å; c=6.835 Å),[22] and NiU3O10.[22]

List

formula name mol struct cell Å ° V Z density colour refs
wt a b c β Å3 g/cm3
NiSO3 • 6H2O nickel(II) sulfite hexahydrate hexagonal 8.794 9.002 603 2.04 emerald green [4][23]
NiSO3 • 3H2O nickel(II) sulfite trihydrate light green [24]
NiSO3•3N2H4 • H2O nickel(II) sulfite trihydrazine hydrate rose [5]
NiSO3•2N2H4 • H2O nickel(II) sulfite dihydrazine hydrate blue [5]
NiS2O3•6H2O Nickel(II) thiosulfate hexahydrate 463.03 orthorhombic 9.282 14.44 6.803 912.1 4 2.03 green [6]
diaqua (4,4´-dimethylbipyridine- N,N´)(methanol) thiosulfato(S) nickel(II) triclinic 8.157 9.685 11.714 α=76.73 β=73.56 γ=78.23 854.2 2 [25]
aqua terpyridine(N,N´,N´´) thiosulfato(S,O) nickel(II) hemihydrate monoclinic,C2/c 27.866 9.274 14.216 114.24˚ 3350. 8 [25]
bis(dipyridylamine) thiosulfato(S,O) nickel(II) hemihydrate orthorhombic, Iba2 12.986 16.821 19.479 4254.9 8 [25]
NiS2O3(2,9-dimethyl-1,10-phenanthroline)(H2O)·H2O·CH3OH monoclinic, C2/c 26.269 7.641 18.381 97.00 3662 8 [26]
NiS2O3(2,9-dimethyl-1,10-phenanthroline) monoclinic, P21/n 11.108 10.955 11.666 103.32˚ 1381.4 4 [26]
Ni(NH2SO3)2 • 4H2O Nickel(II) sulfamate tetrahydrate 322.95 triclinic P1 6.33 6.73 6.78 α= 88.9 β=67.87 γ=67.76 245.27 1 2.19 green [9]
Ni(SO3F)2 nickel(II) fluorosulfate yellow [27]
NiSeO3 anhydrous nickel(II) selenite 742.68 C2/c 15.4915 9.9355 14.8416 111.173 2130.15 32 4.630 yellow brown [10]
NiSeO3 anhydrous nickel(II) selenite 742.68 Orthorhombic 5.8803 7.5235 4.9394 218.52 yellow green high pressure [28]
NiSeO3 • ​13H2O alpha nickel(II) selenite one third hydrate triclinic P1 8.1383 8.4034 8.5724 α=123.713 β=90.174 γ=111.823 435.83 2 1.429 citron yellow [10]
NiSeO3 • ​13H2O beta nickel(II) selenite one third hydrate triclinic P1 8.0222 8.2133 8.4364 α=68.654 β=61.782 γ=66.363 438.11 2 1.422 citron yellow [10]
NiSeO3 • 2H2O nickel(II) selenite dihydrate monoclinic 6.3782 8.7734 7.5467 81.451 417.61 4 3.524 yellow brown [10]
NiSeO3 • 4H2O nickel(II) selenite tetrahydrate light green [10]
NiSe2O5 anhydrous nickel(II) pyroselenite Pnab Orthorhombic 60754 10.3662 6.7913 427.71 4 4.605 light yellow [10]
Ni12F2(SeO3)8(OH)6 nickel hydroxo fluoro selenite, Dumortierite structure hexagonal P63mc 12.702 4.922 1 [29]
Ni12(SeO3)8(OH)8 nickel hydroxy selenite, Dumortierite structure (basic nickel(II) selenite) hexagonal P63mc 12.7004 4.9201 687.28 1 pale green [29]
NiTeO3 anhydrous nickel(II) tellurite Orthorhombic 5.9564 7.4986 5.2128 232.83 yellow green high pressure [28]
Ni3TeO6 trinickel tellurate (nickel(II) orthotellurate) Hexagonal 5.103 5.103 13.781 4.272 [30]
NiTe2O5 nickel pyrotellurite Orthorhombic 8.869 8.441 12.126 5.042 [30]
Ni2Te3O8 Monoclinic 12.392 5.207 11.496 98.6 5.702 [30]
Ni6(TeO3)4(OH)4 nickel hydroxy tellurite hexagonal 12.993 4.958 2 light green [31]
Ni5Te4O12Cl2 nickel tellurium oxychloride 1066.585 Monoclinic 19.5674 5.2457 16.3084 125.289 1366.38 4 5.186 orange [32]
Ni5Te4O12Br2 nickel tellurium oxybromide 1155.77 Monoclinic 20.255 5.2498 16.3005 124.937 1421.0 4 5.403 orange [32]
Ni5Te4O12I2 nickel tellurium oxyiodide Monoclinic 20.766 5.230 16.464 125.79 1451.1 4 brown [32]
Ni11(HPO3)8(OH)6 nickel hydroxyphosphite (basic nickel(II) phosphite) hexagonal 12.6329 4.9040 677.77 1 light green [33]
NiMoO4•xH2O nickel(II) molybdate (hydrate) monoclinic 11.923 8.220 14.007 113.01 1264 [34]
Ni(NO3)2 • 2H2O nickel(II) nitrate dihydrate triclinic 5.09465 7.10410 8.42881 γ=78.698 β=102.7640 α=83.1985 287.5 [34]
Ni(NO3)2 • 4H2O nickel(II) nitrate tetrahydrate triclinic 7.5710 6.623 16.26 γ=97.26 β= 90.015 α=82.57 802.3 [34]
NiN2O2 nickel(II) hyponitrite light green [35]
NiP2O6 • 12H2O nickel(II) hypophosphate orthorhombic Pnmm 11.2418 18.5245 7.3188 1523.1 4 2.142 [36]
Ni3(PO4)2 nickel(II) phosphate monoclinic 10.1059 4.6964 5.8273 91.138 276.52 2 4.396 greenish yellow title=Standard X-Ray Diffraction Powder Patterns from The JCPDS Research Associateship journal=Powder Diffraction volume=2 |issue=1 |pages=41–52 |doi=10.1017/S0885715600012239|bibcode=1987PDiff...2...41M |s2cid=251057066 }}</ref>
α-Ni2P2O7 alpha nickel(II) pyrophosphate monoclinic 6.9177 8.275 8.974 113.879 469.7 4 4.12 ∃ α',β and δ forms [37]
NiHPO4 nickel(II) hydrophosphate beige yellow [38]
[Ni(PO3)2]3•xH2O nickel trimetaphosphate [38]
[Ni(PO3)2]4•xH2O nickel tetrametaphosphate [38]
Ni2P4O12 nickel cyclotetraphosphate monoclinic C12/c1 11.611 8.218 9.826 118.41 824.7 4 green [39]
Ni12H6(PO4)8(OH)6 nickel hydroxy phosphate (basic nickel(II) phosphate) hexagonal 12.4697 4.9531 1 light green [31]
(H3O+NH4+)4[Ni18(HPO4)14(OH)3F9]•12H2O Nanoporous nickel phosphate VSB-1 hexagonal 19.834 5.0379 1710 [15]
Ni20[(OH)12(H2O)6][(HPO4)8(PO4)4]•12H2O Nanoporous nickel phosphate VSB-5 hexagonal 18.153 6.387 1827 [15]
Ni3P6O18 • 17H2O nickel hexametaphosphate triclinic 9.109 9.267 10.75113 α=84.885 β=102.44 γ=101.64 867.4 pale green [40]
Ni3(AsO4)2·8H2O annabergite Monoclinic 10.179 13.309 4.725 105 2 light green [17]
Ni12H6(AsO4)8(OH)6 nickel hydroxy arsenate (basic nickel(II) arsenate) hexagonal 12.678 5.0259 1 light green [31]
NiAs2O4 Nickel arsenite [41]
Ni3(AsO4)2 o-nickel orthoarsenate 454.01 orthorhombic 5.943 11.263 8.164 546.5 4 5.517 [42]
Ni3(AsO4)2 m-nickel orthoarsenate xanthiosite 453.91 monoclinic 5.764 9.559 10.194 92.95 560.9 4 5.394 golden yellow [42]
Ni8.5As3O16 Aerugite 979.8 trigonal 5.9511 27.567 281.9 1 5.772 dark green [43]
NiSb2O4 Nickel metantimonite tetragonal 8.6388 5.9052 413.58 (at 240K) [44]
NiSb2O6 Nickel metantimonate
(nickel antimony oxide)
P42/mnm 4.62957 9.1981 2 [45]
Ni(H2O)6[Sb(OH)6]2 bottinoite Nickel hexahydroantimonate(V) P3 16.060 9.792 2187.2 6 pale blue [46]
NiTa2O6 Nickel metatantalate P42/mnm 4.71581 9.1163 2 [45]
NiSn(SO3F)6 nickel tin fluorosulfate light yellow [27]
Ni(SO3CF3)2 nickel trifluoromethanesulfonate [47]
NiSn(SO3CF3)6 nickel tin triflate light yellow [27]
(Ni,Mg)10Ge3O16 871.7 trigonal R3 5.8850 28.6135 286.1 1 5.060 [48]
NiCO3 anhydrous nickel(II) carbonate 118.72 rhombohedral 4.6117 14.735 271.39 6 4.358 [49]
Ni2SiO4 nickel(II) orthosilicate
liebenbergite
nickel silicate olivine
orthorhombic Pbnm 4.727 10.120 5.911 285.0 4 [50]
Ni2GeO4 nickel orthogermanate cubic Fd3m 8.221 8 [51]
Ni(CN)2 anhydrous nickel(II) cyanide tetragonal quad layer 4.8570 12.801 4 [52]
NiB4O7 γ-nickel(II) metadiborate P6522 4.256 34.905 547.5 6 [53]
Ni(BrO4)2•6H2O nickel(II) perbromate hexahydrate 454.61 trigonal P3 7.817 5.235 277.9 1 2.725 [54]

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