Inorganic Synthesis

Nickel(II) sulfate hydrates


Nickel(II) sulfate is simple, water soluble salt of sulfuric acid. It occurs in nature as minerals retgersite (NiSO4·6H2O), morenosite (NiSO4·7H2O) and some other mixed sulfates. Crystals of Nickel(II) sulfate hexahydrate  have frequent use in optics. Some of their most  availed optical properties is optical rotatory dispersion that ranges from 200 nm to 2500 nm in the wavelength [1] and circular dichroism in the visible spectral range [2]. Their unusual bandlike absorption spectrum in the range 200–1200 nm, which contains only three trans-mission bands (peaked at 250, 490, and 880 nm) makes them one of the most effective band filters in the solar blind spectral range. At the same time, the transmission in the UV region exceeds 80% [3].

Nickel(II) sulfate forms four hydrates (mono-, di- ,hexa-, hepta-,). The hydrate with the biggest amount of crystal water – NiSO4·7H2O – crystallizes from the solutions at temperatures below 31,5°C [4,5]. Heptahydrate has two polymorhs – monoclinic and orthorombic. This hydrate loose crystal water when exposed to air even at room temperatures and decompose to nickel sulfate hexahydrate.

NiSO4 (4)

Orthorombic crystals of NiSO4·7H2[photo: Juraj Kmotorka]

At temperatures from 31,5°C to 53,3°C an α-polymorph of nickel sulfate hexahydrate  is formed. It crystallize in tetragonal crystal system[4]. It has saturated blue-green colour. aNHS crystal

α-polymorph of NiSO4·6H2O [photo: Juraj Kmotorka]

Αt temperatures above 53,3°C a monoclinic β-polymorph of NiSO4·6H2O  crystallizes from aqueous solutions. This polymorph has green colour.


β-polymorph of NiSO4·6H2[photo: Juraj Kmotorka]

The temperatures at which these hydrates crystallize from the solution  can be  changed by adding H2SO4 to a solution which is often done to increase the efficiency of growth technology [7].


Crystallization curve of NiSO4 [8]


Nickel(II) sulfate was made from nickel metal powder and sulfuric acid

Ni(s) + H2SO4(aq) → NiSO4(aq) + H2(g)

An excess of sulfuric acid (75mL 95%, 0,73mol) was poured into a beaker and 100mL of H2O was added. Then Nickel metal powder (29,35g, 0.5mol) was carefully added. The mixture was constantly stirred and gently heated to speed up the reaction. After the reaction ended up the solution was filtered and the nickel sulfate  was recrystallized 2 times and dried. Yield: 71.33 %.  The product was a mixture of hepta- and hexahydrate which has after some time fully converted to hexahydrate.

Crystallization of several forms of NiSO4:
1. Orthorombic Nickel sulfate heptahydrate: Nickel sulfate hexahydrate (44,16g, 168mmol) was dissolved in distilled water (54mL). The solution was heated to 40°C and then let to freely crystallize at room temperature.
2. Monoclinic Nickel sulfate hexahydrate: Nickel sulfate hexahydrate (63.17) was dissolved in distilled water (100mL). The solution was heated up to 85°C and slowly cooled.
3. Tetragonal Nickel sulfate hexahydrate
was crystalized out from 100 mL of 30 % sulfuric acid solution containing nickel(II) sulfate hexahydrate (40g, 152mmol) at 20°C by evaporation process.


[1] Ya. O. Dovgi œ and I. G. Man’kovskaya, Fiz. Tverd. Tela (St. Petersburg) 40 (9), 1608 (1998) [Phys. Solid State 40, 1460 (1998)].
[2] J. R. L. Moxon, A. R. Renshaw, and I. J. Tebbutt, J. Phys. D: Appl. Phys. 24, 1187 (1991).
[3] K. Stadnicka, A. M. Glazer, and M. Koralewski, Acta Crystallogr., Sect. B: Struct. Sci.43, 319 (1987)
[4] V. L. Manomenova, E. B. Rudneva, A. É. Voloshin, L. V. Soboleva, A. B. Vasil’ev,B. V. Mchedlishvili Crystallography Reports September 2005, Volume 50, Issue 5, pp 877-882
[5] A. Holden, P. Morrison Crystals and crystal growing The MIT Press; 1st MIT edition (August 17, 1982)
[6] Beevers, C. A., and C. M. Schwartz. “The Crystal Structure of Nickel Sulphate Heptahydrate NiSO4O.” Zeitschrift für Kristallographie-Crystalline Materials91.1-6 (1935): 157-169.
[7] L. V. Soboleva, E. B. Rudneva, and I. L. Smolsky, Crystallogr. Rep.43, 706 (1998).
[8] Bertram Dillon Steele, D.Sc. and F. M. G. Johnson J. Chem. Soc., Trans., Vol. 85, p. 113-120 (1904).