Nickel(II) sulfate

Last updated
Nickel(II) sulfate
Nickel sulfate anh.jpg
Anhydrous
Nickel sulfate hydrate.jpg
Hexahydrate
N9(H2O)6SO4.png
Names
IUPAC name
Nickel(II) sulfate
Other names
Nickelous sulfate
Nickel (II) sulphate
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.029.186 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 232-104-9
PubChem CID
RTECS number
  • QR9600000
UNII
  • InChI=1S/Ni.H2O4S/c;1-5(2,3)4/h;(H2,1,2,3,4)/q+2;/p-2 Yes check.svgY
    Key: LGQLOGILCSXPEA-UHFFFAOYSA-L Yes check.svgY
  • InChI=1/Ni.H2O4S/c;1-5(2,3)4/h;(H2,1,2,3,4)/q+2;/p-2
    Key: LGQLOGILCSXPEA-NUQVWONBAG
  • anhydrous:[Ni+2].[O-]S([O-])(=O)=O
  • hexahydrate:[OH2+][Ni-4]([OH2+])([OH2+])([OH2+])([OH2+])[OH2+].[O-]S(=O)(=O)[O-]
Properties
NiSO4
Molar mass 154.75 g/mol (anhydrous)
262.85 g/mol (hexahydrate)
280.86 g/mol (heptahydrate)
Appearanceyellow-green solid (anhydrous)
turquoise crystals (hexahydrate)
turquoise crystals (heptahydrate)
Odor odorless
Density 4.01 g/cm3 (anhydrous)
2.07 g/cm3 (hexahydrate)
1.948 g/cm3 (heptahydrate)
Melting point 1210 °C (anhydrous, at high pressure)
53 °C (hexahydrate)
Boiling point > 640 °C (anhydrous, decomposes)
100 °C (hexahydrate, decomposes)
65 g/100 mL (20 °C)
77.5 g/100 mL (30 °C) (heptahydrate)
Solubility anhydrous
insoluble in ethanol, ether, acetone
hexahydrate
insoluble in ethanol, ammonia
heptahydrate
soluble in alcohol
Acidity (pKa)4.5 (hexahydrate)
+4005.0·10−6 cm3/mol
1.511 (hexahydrate)
1.467 (heptahydrate)
Structure
orthorombic (anhydrous)
tetragonal (hexahydrate)
rhombohedral (heptahydrate)
Hazards
GHS labelling:
GHS-pictogram-silhouette.svg GHS-pictogram-exclam.svg GHS-pictogram-pollu.svg
Danger
H302+H332, H315, H317, H334, H341, H350, H360D, H372, H410
P201, P261, P273, P280, P308+P313, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
0
0
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
264 mg/kg
Safety data sheet (SDS) External MSDS
Related compounds
Other cations
Cobalt(II) sulfate
Copper(II) sulfate
Iron(II) sulfate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Nickel(II) sulfate, or just nickel sulfate, usually refers to the inorganic compound with the formula NiSO4(H2O)6. This highly soluble turquoise coloured salt is a common source of the Ni2+ ion for electroplating. Approximately 40,000 tonnes were produced in 2005. [1]

Contents

Structures

Nickel sulfate hexahydrate under a microscope. Nickel sulfate hexahydrate (microscope).jpg
Nickel sulfate hexahydrate under a microscope.

At least seven sulfate salts of nickel(II) are known. These salts differ in terms of their hydration or crystal habit.

The common tetragonal hexahydrate crystallizes from aqueous solution between 30.7 and 53.8 °C. Below these temperatures, a heptahydrate crystallises, and above these temperatures an orthorhombic hexahydrate forms. The yellow anhydrous form, NiSO4, crystallizes in orthorhombic crystal system [2] and in standard pressure decomposes to NiO in temperatures above 640 °C, before reaching the melting point. [3] It melts only at high system pressure, using a constant volume method the melting point was found to be 1210 °C. [4] The anhydrous sulfate is produced by heating the hydrates above 330 °C.

X-ray crystallography measurements show that NiSO4·6H2O consists of the octahedral [Ni(H2O)6]2+ ions. These ions in turn are hydrogen bonded to sulfate ions. [5] Dissolution of the salt in water gives solutions containing the aquo complex [Ni(H2O)6]2+.

All nickel sulfates are paramagnetic.

Production, applications, and coordination chemistry

The salt is usually obtained as a by-product of copper refining. It can also be produced by dissolution of nickel metal or nickel oxides in sulfuric acid.

Aqueous solutions of nickel sulfate react with sodium carbonate to precipitate nickel carbonate, a precursor to nickel-based catalysts and pigments. [6] Addition of ammonium sulfate to concentrated aqueous solutions of nickel sulfate precipitates Ni(NH4)2(SO4)2·6H2O. This blue-coloured solid is analogous to Mohr's salt, Fe(NH4)2(SO4)2·6H2O. [1]

Nickel sulfate has some uses in the laboratory. Columns used in polyhistidine-tagging, useful in biochemistry and molecular biology, are regenerated with nickel sulfate. Aqueous solutions of NiSO4·6H2O and related hydrates react with ammonia to give [Ni(NH3)6]SO4 and with ethylenediamine to give the complex [Ni(H2NCH2CH2NH2)3]SO4. The latter is occasionally used as a calibrant for magnetic susceptibility measurements because it has no tendency to hydrate.

Natural occurrence

Nickel sulfate occurs as the rare mineral retgersite, [7] which is a hexahydrate. The second hexahydrate is known as nickelhexahydrite (Ni,Mg,Fe)SO4·6H2O, which is the monoclinic dimorph of retgersite. The heptahydrate, which is relatively unstable in air, occurs as morenosite. The monohydrate occurs as the very rare mineral dwornikite (Ni,Fe)SO4·H2O.

Safety

Patch test Epikutanni-test.jpg
Patch test

In 2005–2006, nickel sulfate was the top allergen in patch tests (19.0%). [8] Nickel sulfate is classified as a human carcinogen [9] [10] based on increased respiratory cancer risks observed in epidemiological studies of sulfidic ore refinery workers. [11] In a 2-year inhalation study in F344 rats and B6C3F1 mice, there was no evidence of carcinogenic activity, although increased lung inflammations and bronchial lymph node hyperplasia were observed. [12] These results strongly suggest that there is a threshold for the carcinogenicity of nickel sulfate via inhalation. In a 2-year study with daily oral administration of nickel sulfate hexahydrate to F344 rats, no evidence for increased carcinogenic activity was observed. [13] The human and animal data consistently indicate a lack of carcinogenicity via the oral route of exposure and limit the carcinogenicity of nickel compounds to respiratory tumours after inhalation. [14] Whether these effects are relevant to humans is unclear as epidemiological studies of highly exposed female workers have not shown adverse developmental toxicity effects. [15]

Related Research Articles

<span class="mw-page-title-main">Nickel</span> Chemical element with atomic number 28 (Ni)

Nickel is a chemical element; it has symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive, but large pieces are slow to react with air under standard conditions because a passivation layer of nickel oxide forms on the surface that prevents further corrosion. Even so, pure native nickel is found in Earth's crust only in tiny amounts, usually in ultramafic rocks, and in the interiors of larger nickel–iron meteorites that were not exposed to oxygen when outside Earth's atmosphere.

<span class="mw-page-title-main">Iron(II) sulfate</span> Chemical compound

Iron(II) sulfate (British English: iron(II) sulphate) or ferrous sulfate denotes a range of salts with the formula FeSO4·xH2O. These compounds exist most commonly as the heptahydrate (x = 7) but several values for x are known. The hydrated form is used medically to treat or prevent iron deficiency, and also for industrial applications. Known since ancient times as copperas and as green vitriol (vitriol is an archaic name for hydrated sulfate minerals), the blue-green heptahydrate (hydrate with 7 molecules of water) is the most common form of this material. All the iron(II) sulfates dissolve in water to give the same aquo complex [Fe(H2O)6]2+, which has octahedral molecular geometry and is paramagnetic. The name copperas dates from times when the copper(II) sulfate was known as blue copperas, and perhaps in analogy, iron(II) and zinc sulfate were known respectively as green and white copperas.

<span class="mw-page-title-main">Magnesium sulfate</span> Chemical compound with formula MgSO4

Magnesium sulfate or magnesium sulphate is a chemical compound, a salt with the formula MgSO4, consisting of magnesium cations Mg2+ (20.19% by mass) and sulfate anions SO2−4. It is a white crystalline solid, soluble in water but not in ethanol.

<span class="mw-page-title-main">Zinc sulfate</span> Chemical compound

Zinc sulfate describes a family of inorganic compounds with the formula ZnSO4(H2O)x. All are colorless solids. The most common form includes water of crystallization as the heptahydrate, with the formula ZnSO4·7H2O. As early as the 16th century it was prepared on the large scale, and was historically known as "white vitriol" (the name was used, for example, in 1620s by the collective writing under the pseudonym of Basil Valentine). Zinc sulfate and its hydrates are colourless solids.

In chemistry, water(s) of crystallization or water(s) of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions. In some contexts, water of crystallization is the total mass of water in a substance at a given temperature and is mostly present in a definite (stoichiometric) ratio. Classically, "water of crystallization" refers to water that is found in the crystalline framework of a metal complex or a salt, which is not directly bonded to the metal cation.

<span class="mw-page-title-main">Chromium(III) chloride</span> Chemical compound

Chromium(III) chloride (also called chromic chloride) is an inorganic chemical compound with the chemical formula CrCl3. It forms several hydrates with the formula CrCl3·nH2O, among which are hydrates where n can be 5 (chromium(III) chloride pentahydrate CrCl3·5H2O) or 6 (chromium(III) chloride hexahydrate CrCl3·6H2O). The anhydrous compound with the formula CrCl3 are violet crystals, while the most common form of the chromium(III) chloride are the dark green crystals of hexahydrate, CrCl3·6H2O. Chromium chlorides find use as catalysts and as precursors to dyes for wool.

<span class="mw-page-title-main">Nickel(II) chloride</span> Chemical compound

Nickel(II) chloride (or just nickel chloride) is the chemical compound NiCl2. The anhydrous salt is yellow, but the more familiar hydrate NiCl2·6H2O is green. Nickel(II) chloride, in various forms, is the most important source of nickel for chemical synthesis. The nickel chlorides are deliquescent, absorbing moisture from the air to form a solution. Nickel salts have been shown to be carcinogenic to the lungs and nasal passages in cases of long-term inhalation exposure.

<span class="mw-page-title-main">Vanadyl sulfate</span> Chemical compound

Vanadyl(IV) sulfate describes a collection of inorganic compounds of vanadium with the formula, VOSO4(H2O)x where 0 ≤ x ≤ 6. The pentahydrate is common. This hygroscopic blue solid is one of the most common sources of vanadium in the laboratory, reflecting its high stability. It features the vanadyl ion, VO2+, which has been called the "most stable diatomic ion".

<span class="mw-page-title-main">Nickel(II) carbonate</span> Chemical compound

Nickel(II) carbonate describes one or a mixture of inorganic compounds containing nickel and carbonate. From the industrial perspective, an important nickel carbonate is basic nickel carbonate with the formula Ni4CO3(OH)6(H2O)4. Simpler carbonates, ones more likely encountered in the laboratory, are NiCO3 and its hexahydrate. All are paramagnetic green solids containing Ni2+ cations. The basic carbonate is an intermediate in the hydrometallurgical purification of nickel from its ores and is used in electroplating of nickel.

<span class="mw-page-title-main">Nickel(II) oxide</span> Chemical compound

Nickel(II) oxide is the chemical compound with the formula NiO. It is the principal oxide of nickel. It is classified as a basic metal oxide. Several million kilograms are produced annually of varying quality, mainly as an intermediate in the production of nickel alloys. The mineralogical form of NiO, bunsenite, is very rare. Other nickel(III) oxides have been claimed, for example: Ni
2
O
3
and NiO
2
, but remain unproven.

<span class="mw-page-title-main">Manganese(II) sulfate</span> Chemical compound

Manganese(II) sulfate usually refers to the inorganic compound with the formula MnSO4·H2O. This pale pink deliquescent solid is a commercially significant manganese(II) salt. Approximately 260,000 tonnes of manganese(II) sulfate were produced worldwide in 2005. It is the precursor to manganese metal and many other chemical compounds. Manganese-deficient soil is remediated with this salt.

<span class="mw-page-title-main">Iron(III) sulfate</span> Chemical compound

Iron(III) sulfate (or ferric sulfate), is a family of inorganic compounds with the formula Fe2(SO4)3(H2O)n. A variety of hydrates are known, including the most commonly encountered form of "ferric sulfate". Solutions are used in dyeing as a mordant, and as a coagulant for industrial wastes. Solutions of ferric sulfate are also used in the processing of aluminum and steel.

<span class="mw-page-title-main">Chromium(III) sulfate</span> Chemical compound

Chromium(III) sulfate usually refers to the inorganic compounds with the formula Cr2(SO4)3.x(H2O), where x can range from 0 to 18. Additionally, ill-defined but commercially important "basic chromium sulfates" are known. These salts are usually either violet or green solids that are soluble in water. It is commonly used in tanning leather.

<span class="mw-page-title-main">Cobalt(II) sulfate</span> Inorganic compound

Cobalt(II) sulfate is any of the inorganic compounds with the formula CoSO4(H2O)x. Usually cobalt sulfate refers to the hexa- or heptahydrates CoSO4.6H2O or CoSO4.7H2O, respectively. The heptahydrate is a red solid that is soluble in water and methanol. Since cobalt(II) has an odd number of electrons, its salts are paramagnetic.

<span class="mw-page-title-main">Nickel(II) bromide</span> Chemical compound

Nickel(II) bromide is the name for the inorganic compounds with the chemical formula NiBr2(H2O)x. The value of x can be 0 for the anhydrous material, as well as 2, 3, or 6 for the three known hydrate forms. The anhydrous material is a yellow-brown solid which dissolves in water to give blue-green hexahydrate (see picture).

<span class="mw-page-title-main">Beryllium sulfate</span> Chemical compound

Beryllium sulfate normally encountered as the tetrahydrate, [Be(H2O)4]SO4 is a white crystalline solid. It was first isolated in 1815 by Jons Jakob Berzelius. Beryllium sulfate may be prepared by treating an aqueous solution of many beryllium salts with sulfuric acid, followed by evaporation of the solution and crystallization. The hydrated product may be converted to anhydrous salt by heating at 400 °C.

Nickel compounds are chemical compounds containing the element nickel which is a member of the group 10 of the periodic table. Most compounds in the group have an oxidation state of +2. Nickel is classified as a transition metal with nickel(II) having much chemical behaviour in common with iron(II) and cobalt(II). Many salts of nickel(II) are isomorphous with salts of magnesium due to the ionic radii of the cations being almost the same. Nickel forms many coordination complexes. Nickel tetracarbonyl was the first pure metal carbonyl produced, and is unusual in its volatility. Metalloproteins containing nickel are found in biological systems.

<span class="mw-page-title-main">Vanadium(II) sulfate</span> Chemical compound

Vanadium(II) sulfate describes a family of inorganic compounds with the formula VSO4(H2O)x where 0 ≤ x ≤ 7. The hexahydrate is most commonly encountered. It is a violet solid that dissolves in water to give air-sensitive solutions of the aquo complex. The salt is isomorphous with [Mg(H2O)6]SO4. Compared to the V–O bond length of 191 pm in [V(H2O)6]3+, the V–O distance is 212 pm in the [V(H2O)6]SO4. This nearly 10% elongation reflects the effect of the lower charge, hence weakened electrostatic attraction.

<span class="mw-page-title-main">Nickel oxyacid salts</span>

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.

Gallium(III) sulfate refers to the chemical compound, a salt, with the formula Ga2(SO4)3, or its hydrates Ga2(SO4)3·xH2O. Gallium metal dissolves in sulfuric acid to form solutions containing [Ga(OH2)6]3+ and SO42− ions. The octadecahydrate Ga2(SO4)3·18H2O crystallises from these solutions at room temperature. This hydrate loses water in stages when heated, forming the anhydrate Ga2(SO4)3 above 150 °C and completely above 310 °C. Anhydrous Ga2(SO4)3 is isostructural with iron(III) sulfate, crystallizing in the rhombohedral space group R3.

References

  1. 1 2 K. Lascelles, L. G. Morgan, D. Nicholls, D. Beyersmann “Nickel Compounds” in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. Vol. A17 p. 235 doi : 10.1002/14356007.a17_235.pub2.
  2. Dimaras, P. I. (1957-04-10). "Morphology and structure of anhydrous nickel sulphate". Acta Crystallographica. 10 (4): 313–315. doi:10.1107/S0365110X57000900. S2CID   98635639.
  3. Tagawa, Hiroaki (October 1984). "Thermal decomposition temperatures of metal sulfates". Thermochimica Acta. 80 (1): 23–33. doi:10.1016/0040-6031(84)87181-6.
  4. Kobertz, Dietmar; Müller, Michael (June 2014). "Experimental studies on NiSO4 by thermal analysis and calorimetry". Calphad. 45: 55–61. doi:10.1016/j.calphad.2013.10.008.
  5. Wells, A. F. (1984). Structural Inorganic Chemistry, Oxford: Clarendon Press. ISBN   0-19-855370-6.
  6. H. B. W. Patterson, "Catalysts" in Hydrogenation of Fats and Oils G. R. List and J. W. King, Eds., 1994, AOCS Press, Urbana.
  7. "Retgersite". mindat.org.
  8. Zug KA, Warshaw EM, Fowler JF Jr, Maibach HI, Belsito DL, Pratt MD, Sasseville D, Storrs FJ, Taylor JS, Mathias CG, Deleo VA, Rietschel RL, Marks J. Patch-test results of the North American Contact Dermatitis Group 2005–2006. Dermatitis. 2009 May–Jun;20(3):149-60.
  9. IARC (2012). “Nickel and nickel compounds” IARC Monogr Eval Carcinog Risks Hum, Volume 100C: 169-218.
  10. NTP (National Toxicology Program). 2016. “Report on Carcinogens”, 14th Edition.; Research Triangle Park, NC: U.S. Department of Health and Human Services, Public Health Service. https://ntp.niehs.nih.gov/pubhealth/roc/index-1.html Accessed July 13, 2017.
  11. International Committee on Nickel Carcinogenesis in Man (ICNCM). (1990). Report of the International Committee on Nickel Carcinogenesis in Man. Scan. J. Work Environ. Health.16(1): 1-82.
  12. National Toxicology Program (NTP). (1996). Toxicology and Carcinogenesis Studies of Nickel Sulfate Hexahydrate (CAS NO. 10101-97-0) in F344/N Rats and B6CF1 Mice (Inhalation Studies). US DHHS. NTP TR 454. NIH Publication No. 96-3370.
  13. Heim, K. E.; Bates, H. K.; Rush, R. E.; Oller, A. R. (2007). “Oral Carcinogenicity Study with Nickel Sulfate Hexahydrate in Fischer 344 Rats.” Toxicol. Appl. Pharmacol.224(2): 126-137.
  14. Cogliano, V. J.; Baan, R.; Straif, K.; Grosse, Y.; Lauby-Secretan, B.; Ghissassi, F. E.; Bouvard, V.; Benbrahim-Tallaa, L.; Guha, N.; Freeman, C.; Galichet, L.; Wild, C. P. (2011). “Preventable Exposures Associated With Human Cancers”. J Natl Cancer Inst103: 1827-1839.
  15. Vaktskjold, A.; Talykova, L. V.; Chashchin, V. P.; Odland, J. O.; Nieboer, E. (2008). “Spontaneous abortions among nickel-exposed female refinery workers.” Int J Environ Health Res.18(2): 99-115.