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Some properties of aqueous solutions of α-NiSO4 · 6H2O

Article  in  Crystallography Reports · July 2012

DOI: 10.1134/S1063774512010099

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ISSN 10637745, Crystallography Reports, 2012, Vol. 57, No. 4, pp. 579–584. © Pleiades Publishing, Inc., 2012.
Original Russian Text © E.V. Petrova, M.A. Vorontsova, V.L. Manomenova, L.N. Rashkovich, 2012, published in Kristallografiya, 2012, Vol. 57, No. 4, pp. 648–653.

CRYSTAL
GROWTH

Some Properties of Aqueous Solutions of αNiSO4 · 6H2O

E. V. Petrovaa, M. A. Vorontsovaa, V. L. Manomenovab, and L. N. Rashkovicha
a
Moscow State University, Moscow, 119991 Russia
email: petrova@polly.phys.msu.ru
b
Shubnikov Institute of Crystallography, Russian Academy of Sciences, Leninskii pr. 59, Moscow, 119333 Russia
Received November 15, 2010

Abstract—The concentration dependences of the properties of solutions of αNiSO4 · 6H2O (mineral ret
gersite) in H2O and 20% H2SO4 have been measured in a wide range of concentrations (up to ~20 solvent
molecules per dissolvedsalt molecule). It is shown that the solution density, the light absorption coefficient
at a wavelength of 394 nm, and the intensity of the Raman scattering peak characteristic of the sulfate ion
depend linearly on the bulk salt concentration in the solutions. No shift of the Raman peak as a result of a
change in the concentration was observed. These facts indicate that the type of dissolved particles and the
character of interactions between them and with the solvent remain the same with an increase in the salt con
centration. The data in the literature on the formation of ion pairs in retgersite solutions are discussed.
DOI: 10.1134/S1063774512010099

INTRODUCTION tions are also used to grow retgersite crystals of higher

Synthetic retgersite crystals are used as optical fil
ters in the UV spectral region [1]. Their growth is met
by a number of difficulties which are caused, on the
one hand, by the presence of nickel sulfates with a dif
ferent content of crystallization water [2, 3] and, on
the other hand, the tendency to narrow the light trans
mission band.
The properties of NiSO4 solutions were studied by
many researchers. The interest in these solutions is
due to the fact that half of the world’s production of
nickel is based on the electrolysis of its salts [4]. For
our purposes, the question of primary importance was
the presence of ion pairs in solutions [5]. Calculations
[6] based on the data on the electric conductivity and
the relaxation dielectric spectroscopy data (frequen
cies 1–100 GHz) showed that the total content of con
tact and waterseparated pairs reaches 15% of the Ni
content in a solution at its concentration of 1.5 mol/l.
However, the existence of different environments of
sulfate ions has not been directly proven (as was done
for MgSO4 solutions based on their Raman spectra [7, 8]).
The crystal structure of NiSO4 has been studied in
detail [9]. Its unit cell contains four formula units:
weakly distorted Ni(6H2O)2+ octahedra, which are
bound by hydrogen bonds with each other and with
almost undistorted tetrahedra.
αNiSO4 · 6H2O is crystallized from aqueous solu
tions at temperatures t > 31.5°С, while heptahydrate
crystals are formed at t < 31.5°С [10, 11]. This critical
temperature can be changed by adding H2SO4 to the
solution, which is often done to increase the efficiency
of growth technology [12]. H2SO4containing solu
quality [1]. The crystals grown from these solutions
have better stability to surface dehydration under
atmospheric conditions than the samples obtained
from aqueous solutions. In addition, such crystals are
easier to process mechanically in the commercial pro
duction of optical filters [13].
The determination of the type of particles in solu
tion and the nature of crystal building units should
help in the development of the optimal technique for
crystal growth [14–16]. This is the purpose of our
study.
EXPERIMENTAL
We used the αNiSO4 · 6H2O agent (Scharlau) in
the form of crystals 2–5 mm in size with faceting typ
ical of retgersite and characteristic bluegreen color.
Distilled water was passed through a MilliQ ion
exchange column and had a resistivity of 16 MΘ cm.
The solution concentration was determined by
weighing the ingredients with an error of 0.1 mg. The
solution density was determined by areometers with a
scale unit of 0.001 g/cm3. Raman scattering was stud
ied on a Ramanor U1000 spectrometer (Jobin Yvon)
with a resolution of 0.05Å. Spectra were recorded with
a step of 0.2 nm. The light source was a tunable Stabi
lite 2017 argon laser (Spectra Physics) operating at a
wavelength of 514.5 nm with a focusedbeam diameter
of about 5 μm. The рН value was determined with an
error of 0.01. The absorption spectra were recorded on
a НР 8452 spectrophotometer in 10 and 0.5mm
thick cells; the solutions were not diluted in this case.

579
580 PETROVA et al.

d, g/cm3 J
150
983
1.4 (a)

100
1.3

1.2 1091
611
50

1.1

0
1.0 550 650 750 850 950 1050
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
C*, g/cm3 70
Fig. 1. Dependence of the density of retgersite aqueous 983
solutions on the bulk salt concentration for temperatures (b)
of (䊏) 35.5, (䊉) 22.8, and (䉱) 18.0°С [17].
60
RESULTS
Solution Density
The density of aqueous solutions was measured at 50 616
temperatures of 22.8 and 35.5°С. The data obtained 1090
are shown in Fig. 1 as a dependence of the density d on
the bulk solution concentration (С* = Сd, where C is 40
the mass concentration in grams of αNiSO4 · 6H2O 550 650 750 850 950 1050
per gram of solution). This representation allows one
to determine the partial densities of the solvent (dsolv) 650 1052
and dissolved salt (dsalt):
d = dsolv + (1 – dsolv/dsalt)C*. 600 983
(c)
The linearity of this dependence (Fig. 1) with 550
approximation errors of 0.003 and 0.007 g/cm3 for
22.8 and 35.5°С, respectively, indicates the constancy 500
of partial densities in the entire concentration range
under study. The partial values were found to be 450
at 22.8°С dsolv = 1.001 ± 0.003 g/cm3 400
dsalt = 2.31 ± 0.03 g/cm3 350
at 35.5°С dsolv = 1.001 ± 0.007 g/cm3
300
dsalt = 2.24 ± 0.06 g/cm3. 850 900 950 1000 1050 1100
Similar results were obtained for retgersite solu Raman shift, cm–1
tions in 20% H2SO4 at 27°С. In this case, the partial
densities were (with a linear approximation error of Fig. 2. Raman spectra of (a) a retgersite crystal at 25оС, (b)
its aqueous solution (С = 0.57 g/cm3), and (c) 11% H2SO4
0.002 g/cm3) as follows: solution.
dsolv = 1.125 ± 0.002 g/cm3 dsalt = 2.31 ± 0.03 g/cm3.
Note that the Xray crystal density is Dx = strange that the partial densities remain constant in
2.07 g/cm3 [17]. such highly concentrated solutions.
One kilogram of H2SO4free solution, saturated at
33.5°С, contains 519 g αNiSO4 · 6H2O and 481 g Raman Spectra
water or 1.975 mols salt and 26.69 mols water. Hence
there are 13.5 water molecules per retgersite molecule Figure 2 shows the Raman spectra of retgersite and
or 19.5 water molecules per NiSO4 molecule. It looks its aqueous and H2SO4 solutions. The spectrum of our

CRYSTALLOGRAPHY REPORTS Vol. 57 No. 4 2012

 SOME PROPERTIES OF AQUEOUS SOLUTIONS OF αNiSO4 · 6H2O 581

crystals is identical to that described [18]. Note that J 1

the solution and crystal spectra are identical. The 200
peaks at 983 and 1052 cm–1 are known to correspond 180 (a)
to SO 24− and HSO 4− ions. The absence of a peak at 160 2
1 – 0.566 g/cm3
1052 cm–1 in the spectrum of retgersite solution indi 140 2 – 0.416 3
cates the absence of HSO 4− ions in it. Lowfrequency 120 3 – 0.293
peaks were not identified. 4 – 0.186 4
100
Figure 3 shows the spectra of solutions with differ 5 – 0.083
ent concentrations and the concentration dependence 80 5
of the intensity of the peaks at 983 cm–1. The linear 60
approximation of the latter dependence does not 40
cause any doubts: its standard error is 5. 940 960 980 1000 1020
The solution spectrum recorded at a temperature Raman shift, cm–1
of about 35°С does not differ from the roomtemper J
ature spectrum. 180
The shape of the peaks is ideally approximated by 160
the Lorentz formula. The peak maximum is not (b)
140
shifted and cannot be expanded in several components
120
corresponding to different environments of SO 24− ions.
100
80
Absorption Spectra 60
Figure 4 shows the absorption spectra of solutions 40
with five different concentrations which were mea 20
sured at room temperature. The solutions were not
diluted. The dependence of the absorption coefficient 0 0.1 0.2 0.3 0.4 0.5 0.6
at a wavelength of 394 nm on the bulk solution con C*, g/cm3
centration is shown in Fig. 5.
The concentration dependences of the absorption Fig. 3. (a) Raman spectra of retgersite solutions with dif
coefficient are approximated well by a straight line ferent concentrations (indicated in the figure) near the
with a standard deviation of 0.1 cm–1. The slope of the peak, which is characteristic of the sulfate ion (983 cm–1),
curve (Fig. 5) is α/C* = 20 ± 0.2 cm2/g. and (b) the concentration dependence of this peak inten
sity.

pH Measurements of Solutions
The pH values were measured for αNiSO4 · 6H2O
aqueous solutions with different concentrations at
25°С (table). Triple distilled water (quartz distiller)
was used. These data are presented in Fig. 6 in the
form of the dependence of the activity of hydrogen
ions, aH, on the molar salt concentration.
It can be seen that the solution acidity increases
with an increase in the salt concentration. For the
solution saturated at 34°С (С* = 0.742 g/cm3 =
2.82 mol/l), pH = 2.7.
DISCUSSION
The constancy of partial densities and the linearity
of the concentration dependences of the light absorp
tion coefficient and the intensity of the Raman peak
that is characteristic of the sulfate ion suggest a con
stancy of the environment (H2O molecules and
Ni ions) of this ion. At the same time, there are data in
the literature on the formation of contact and water
separated ion pairs in the solution. Let us consider this
contradiction in more detail.
The above data on the solution pH does not allow
one to confidently estimate the degree of salt dissocia
tion (α = [Ni]/C*) or the degree of its hydrolysis into
hydrogen ions and NiOH+ β = [aH]/[Ni]; the square
brackets are used for molar concentrations). These
values are related by the expression αβ = [аH]/C*,
which yields (8–15) × 10–4 at closetosaturation
concentrations. Under the assumption that α is close
to unity, the hydrolysis constant appears to be too
small.
Dependence of pH on the αNiSO4 ⋅ 6H2O concentration
in solution
C, wt % 0 0.01 0.1 1 10 20 30 40
pH 7.0 6.15 6.10 4.70 4.10 3.35 3.07 2.81

CRYSTALLOGRAPHY REPORTS Vol. 57 No. 4 2012

582 PETROVA et al.

lnI0 /I [cm–1]
2.0

1 – 0.5687 g/cm3
1.5
2 – 0.4179
3 – 0.2927
4 – 0.1984
1.0 5 – 0.0816

1
0.5
2
3
4

0 5

100 200 300 400 500 600 700 800 λ, nm

Fig. 4. Absorption spectra of retgersite solutions in a 0.5mmthick cell.

The electric conductivity of NiSO4 solutions was
precisely measured in [4, 20]. The equivalent conduc
tivity of infinitely diluted solutions is also known: Λ0 ≈
80 cm2/Θ geq. An approximation of these data by the
Robinson–Stokes equation [19]
Λ = Λ0 – ((2be + brΛ0)C1/2)/(1 + aBC1/2),
where С is the concentration (mol/l); be and br are,
respectively, the electrophoretic and relaxation coeffi
cients; а is the minimum distance between the electric
centers of cations and anions in the solution; and В =
χ/I1/2 (χ is the main parameter of the Debye–Huckel
limiting law and I is the ionic force), yields poor agree
ment with the experimental data (Fig. 7). This is espe
cially evident from the obtained value Λ0 ≈ 41 ±
2 cm2/Θ geq. Approximation by the Onsager equa
tion [19] leads to a similar situation.

a, cm–1 aн, geq l–1

10–2
12

10 10–3

8
10–4
6
10–5
4
10–6
2

10–7
0 0.1 0.2 0.3 0.4 0.5 0.6 0 0.4 0.8 1.2 1.6 2.0
C*, g/cm3 C*, mol l–1

Fig. 5. Dependence of the absorption coefficient of retger

site solutions at a wavelength of 394 nm on the bulk salt Fig. 6. Dependence of the activity of hydrogen ions on the
concentration. NiSO4 molar concentration at 25°С.

CRYSTALLOGRAPHY REPORTS Vol. 57 No. 4 2012

 SOME PROPERTIES OF AQUEOUS SOLUTIONS OF αNiSO4 · 6H2O 583

Ion pairs, mol l–1

Λ, cm2/Θ geq 1.4

35 1.2
30 1.0
25
0.8
20
0.6
15
0.4
10
5 0.2

0
0 0.5 1.0 1.5 2.0 2.5 0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
C*, mol l–1 C*, mol l–1

Fig. 8. Dependence of the total concentration of neutral

Fig. 7. Approximation of the data of [20] on the conduc contact and waterseparated ion pairs on the concentra
tivity of solutions by the Robinson–Stokes equation. tion of NiSO4 solution at 25°С, according to [20].

There are two reasons for this. On the one hand, the pairs. However, the Onsager equation is applicable
approximating equations were derived for solutions only at concentrations not higher than 0.05–
with “moderate” concentrations and, on the other 0.1 mol/l; these values are for 1–1 valence electro
hand, ions can partially be bound into neutral pairs, lytes, whereas for the 2–2 valence the limiting con
which do not conduct electric current. centrations are even lower.
The real (ε') and complex (ε'') parts of the permit
tivity of NiSO4 solutions were measured in [6] at fre
CONCLUSIONS
quencies of 0.1–100 GHz. The relaxation times (fre
quencies) that (as was believed in [6]) are responsible The densities, absorption spectra, Raman spectra,
for the existence of contact and separated (by one or and pH of αNiSO4 · 6H2O solutions were measured in
two water molecules) neutral pairs of NiSO4 ions were a wide concentration range up to saturation.
calculated. This approach made it possible to expand The linearity of the concentration dependences
the frequency dependence ε'' in Gaussian components apparently indicates that the type and number of par
and calculate the concentration of different ion pairs.
Figure 8 shows the results. Here, the total fraction of
ion pairs can be approximated by a quadratic depen Λ, cm2/Θ geq
dence with two constants: y = (68.0 ± 0.2)x + (0.135 ±
0.014)x2 ± 0.008. Using the Onsager equation, one 70
obtains
60
Λ = Λ0 – {(B1Λ0 + B2)/(1 + BaC1/2)}C1/2,
50
where В = 0.3291 × 2 = 0.6582, В1 = 0.23 × 8 = 1.84,
and В2 = 60.65 × 4 = 242.60 Å–1 are the Debye– 40
Huckel constants for symmetric divalent electrolytes 30
and а is the ion size in Å. Having substituted the salt
concentration with the subtracted total number of ion 20
pairs as the concentration С1 = αС*, we obtained good
agreement with the experiment (Fig. 9). This approx 10
imation gives Λ0 = 78 ± 2 cm2/Θ geq and a reasonable 0
ion size: а = 6.9 ± 0.2 Å. 0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
The result in Fig. 9 suggests that one can always C 1, mol l–1
reach agreement with the approximating equation by
varying three parameters: the ion size a and the two Fig. 9. Approximation of the data of [20] by the Onsager
parameters characterizing the relative number of ion equation with allowance for conducting particles only.

CRYSTALLOGRAPHY REPORTS Vol. 57 No. 4 2012

584 PETROVA et al.
ticles in these solutions are independent of the salt
concentration and the solution temperature and that
the distance between dissolved particles only slightly
affects their interaction.
The Raman spectra did not confirm the presence of
ion pairs in solutions. Nevertheless, this question
remains open: the existence of these pairs requires
direct proofs.
ACKNOWLEDGMENTS
We are grateful to A.V. Turnina for her help in mea
suring Raman spectra.
This study was supported by the Russian Founda
tion for Basic Research, project no. 09.0200314a.
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Translated by A. Grudtsov
Vol. 57 No. 4 2012