Russian Journal of Coordination Chemistry, Vol. 30, No. 7, 2004, pp. 496–504. Translated from Koordinatsionnaya Khimiya, Vol.

30, No. 7, 2004, pp. 530–539.

Original Russian Text Copyright © 2004 by Vinokurov, Kuznetsov, Bondar’.

Aqueous Solutions of Cr(III) Sulfate: Modeling of Equilibrium

Composition and Physicochemical Properties
E. G. Vinokurov*, V. V. Kuznetsov*, and V. V. Bondar’**
*Mendeleev University of Chemical Engineering, Miusskaya pl. 9, Moscow, 125190 Russia
**All-Russian Research Institute of Scientific and Technical Information, Russian Academy of Sciences, Moscow, Russia
Received June 3, 2003

Abstract—Chemical equilibria in aqueous solutions of chromium sulfate are studied and the mathematical
model of chromium complexation is developed in a wide range of concentrations (0.001–1.2 mol/l). The results
of calculations satisfactorily agree with the experimental data, which confirms the adequacy of the suggested
mathematical model of the equilibrium composition of an aqueous chromium sulfate solution. The nature of
“green” modification of Cr2(SO4)3 is established. This modification occurs in its diluted solutions (c < 0.1
mol/l) due to predominant polynuclear chromium hydroxo complexes, whereas in the concentrated solutions (c
> 0.1 mol/l), it forms due to prevailing chromium sulfate complexes. The diagram was plotted that shows the
regions with different prevailing forms of the complexes in the equilibrium system H2O–Cr2(SO4)3 at different
concentrations and pH and explains the experimental data on the basis of some physicochemical properties
(electric conductivity, viscosity, light absorption) of chromium sulfate solutions within a wide range of concen-
trations.

The solution of many scientific and practical prob- tions of the complexes in the diffusion layer can differ
lems requires data on the equilibrium composition of a significantly from those in the bulk of the solution.
solution, which makes it possible to identify what spe- The determination of the chemical state of the Cr3+
cies occur as the real kinetic units and thus participate ions in the sulfate solutions is essential due to their
in a reaction. wide use in many technological processes. Chromium
In the case with the aqueous electrolyte solutions, sulfate, as many other salts of trivalent chromium,
the equilibrium composition cannot be adequately forms “green” and “violet” solutions. Today, several
established due to the interaction of the dissolved com- viewpoints have been suggested that explained the dif-
pound with water and the formation of the hydrolysis ference between the solutions of the “green” and “vio-
products, namely, hydroxo complexes. As far as in let” modifications capable of the mutual transforma-
1908, N. Bjerrum studied the hydrolysis of Cr3+ ions tions.
and was the first to discover the formation of polynu- Most of the researchers believe that in the aqueous
clear hydroxo compounds in a solution. It was found fur- solutions of the “violet” modification, the Cr3+ ions
ther that most of the metals form polynuclear hydroxo occur as the kinetically inert hexaaqua complexes
complexes at the concentration 10–3–10–2 mol/l, [Cr(H2O)6]3+. They retain this structure also in the aque-
while many give multicharge ions at the concentrations ous concentrated solutions (up to 2.2 mol/l), with the
~10–5 mol/l [1]. The fact that the concentrated electro- secondary hydration sheath containing 15–18 water
lyte solutions, which are used in many technological molecules [2]. When the “violet” modification solu-
process, only form mononuclear complexes is an tions are heated, the anions or hydroxide ions migrate
exception rather than a rule. to the inner coordination sphere of the Cr3+ ion, and the
The mechanism of electrochemical reactions occur- violet color of the solutions change to the green color.
ring during the metal (including chromium) elec- The “green” modification of the Cr(III) salts has very
trodeposition cannot be studied without consideration composite stoichiometric composition. According to
of the equilibrium composition of the solutions. The lit- data in [3], such solutions contain the bridging tet-
erature data indicate that the efficient electrodeposition raaqua-µ-dioxydichromium(III) ion. The dependence
of chromium from electrolytes on the basis of Cr(III) of the formation of polynuclear complexes on the total
compounds can be achieved only at the specific pH val- concentration of the Cr3+ ions in the Cr(NO3)3 solutions
ues. At the same time, many recommendations are con- (0.0002–0.32 mol/l) is reported in [4] and is repre-
tradictory, which requires additional investigations of sented as a multiple system of simultaneously occur-
the pH effect on the composition of chromium com- ring equilibria.
plexes. Moreover, during electrolysis of the solutions The review of the literature data showed that the
on the basis of Cr(III) compounds, pH and concentra- composition and structure of the complexes in the

1070-3284/04/3007-0496 © 2004 åÄIä “Nauka /Interperiodica”

 AQUEOUS SOLUTIONS OF Cr(III) SULFATE 497

aqueous chromium sulfate solutions of the “green” MATHEMATICAL MODEL

modification and the equilibrium therein cannot be con- The mathematical modeling of the equilibrium
sidered as unambiguously established. Many authors compositions with the use of the calculation experiment
provide contradictory data, which can be explained by can be of a significant help and can substantially reduce
the application of different methods and by different the expenses for the experimental and technological
concentration ranges they used. work while developing the composite electrolytes for
Many authors believe that the solution of chromium the metal electroplating.
sulfate of the “green” modification has very involved The calculation of the equilibrium compositions of
composition with the predominant polynuclear hydrox- the electrolyte solutions, particularly of the multicharge
osulfate complexes. metals, is noticeably complicated by the need to take
into consideration the ion activity coefficients when
The aim of this work was to develop the mathemat- going from the thermodynamic to the concentration
ical model of the equilibrium composition of an aque- constants. The concentration equilibrium constants
ous chromium sulfate solution in a wide concentration used in the calculations can have the estimate values,
range (0.001–1.2 mol/l) and to establish the nature of its since these constants are determined with the minimum
“green” modification depending on its concentration error of 0.1 in the logarithmic scale. In order to estimate
and pH of the solution. the accuracy of the calculations, let us analyze the error
in determining the fraction of the complex as the result
of inaccurate stability constants used.
EXPERIMENTAL
If the complexes formed in the system have the com-
The reagent grade Cr2(SO4)3 · 6H2O and distilled position [MLn] (n = 1, 2, … , N) and the concentration
water were used in the experiment. In order to speed up stability constants (βn), then the fraction of the nth com-
the exchange of the ligands in the kinetically inert plex (αn) will be
Cr(III) complexes, the chromium sulfate was dissolved n
at 80–90°ë. The obtained concentrated solution was βn [ L ]
α n = ----------------------------------
-. (1)
stored for 2 weeks and then the precise Cr3+ concentra- n=N

∑ β [L]
n
tion in its colored complex with EDTA was determined 1+ n
by the photometric method. n=1

The working solutions were prepared by diluting the The absolute error in the αn values due to an error in
initial concentrated solution and were used to record the stability constants can be determined by differenti-
the electronic absorption spectra and to determine pH, ating Eq. (1) on condition d[L] = 0:
the electric conductivity (κ), and viscosity (η). All n
working solutions were preliminarily kept on a water βn [ L ] dβ
- --------n
dα n = ----------------------------------
bath for 1 h. n=N
βn
∑
n
The electronic absorption spectra were taken in 1, 3, 1+ βn [ L ]
and 16 days after preparation of the working solutions n=1
(2)
using a SF-46 spectrophotometer with the digital read- βn [ L ]
n n=N
βn [ L ]
n
dβ n
out. An error in the determination of optical density in
the range of 0.1–1 was ±0.001 and ±0.005 at the higher
– ----------------------------------
n=N
- ∑
----------------------------------
n=N
- --------.
βn
∑ ∑
n n
values. The measurements were carried out at 20°ë in 1+ βn [ L ] n = 1 1 + βn [ L ]
the glass cells with l = 0.1 cm and water used as a ref- n=1 n=1
erence solution. The relative error (ε(αn)) for αn can be found by
The electric conductivity of solutions was deter- dβ
dividing Eq. (2) by Eq. (1) and by replacing ------ by
mined at 20°ë using a LF41 conductometer with the β
platinum electrodes. The cell was calibrated with the 2.3d log β :
0.1 M and 1 M solutions of KCl.
n=N
The viscosity of the solutions was found by the
method of the liquid outflow from the capillary using ε ( α n ) = 2.3 d log β n – ∑ α d log β
n n . (3)
viscometer calibrated against water. The dynamic vis- n=1
cosity was calculated from the densities of the aqueous If the errors in determination of the stability con-
chromium sulfate solutions converted to the tempera- stants are identical, i.e., ∆ log β 1 = ∆ log β 2 = … =
ture of 20°ë [6].
∆ log β , then Eq. (3) will acquire a simple form
After aging the solutions for 16 days, all the physic-
n=N
ochemical properties under study showed constant val-
ues, which made it possible to assume that the system ε ( α n ) = 2.3∆ log β 1 – ∑α n = 2.3α 0 ∆ log β , (4)
attained the equilibrium state. n=1

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 7 2004

498 VINOKUROV et al.

αn equivalent to the introduction of errors to the stability

1.0 (a) constants.
0.8 The application of the mathematical modeling to the
1 2 3 4 ionic equilibria of the aqueous solutions of Cr2(SO4)3
0.6 makes it possible to calculate the fraction of a specific
complex that occurs in the electrolyte, i.e., to establish
0.4
the state of the Cr3+ ions in the solution. Such calcula-
0.2 tions were performed for the first time for the Cr2(SO4)3
solutions at different concentration ratios of Cr3+ and
0 2–
–6 –5 –4 –3 –2 –1 0 1 SO 4 [7]. However, the authors of this work only took
log[L] into consideration the formation of five mononuclear
1.0 (b) Cr complexes due to the lacking data on the stability
0.8 1 4 constants for another Cr complexes.
2
3 The mathematical analysis of interdependent homo-
0.6 geneous chemical equilibria in chromium sulfate solu-
0.4 tions and the construction of the mathematical model
were performed as described in [8]. Some equilibrium
0.2 constants used in the calculations have estimate values:
the statistical values for the mixed complexes, the val-
0 ues of the constants were determined with an error of
–5 –4 –3 –2 –1 0 1
logcL 0.1 in the logarithmic scale.
The following assumptions were made in the math-
Fig. 1. The distribution of complexes in the M–L model sys- ematical model of estimation of the equilibrium con-
tem depending on (a) equilibrium [L] and (b) analytical cL centrations of species in the Cr2(SO4)3 solution: the
concentration of a ligand (solid lines correspond to a set of qualitative composition of a solution is known before-
constants log β 1 = 3.0, log β 2 = 5.0, log β 3 = 6.0, while hand and remains constant for a specific model; the
the dotted lines correspond to log β 1 = 3.5, log β 2 = 5.5, oxolated chromium complexes are absent from the
solution; all reactions occurring in the solution attain
log β 3 = 6.5).
the dynamic equilibrium; the concentration equilibrium
constants are equal to the thermodynamic constants.
where α0 is the fraction of aqua complex. The generalization of the literature data made it pos-
sible to describe the chemical equilibrium in the H2O–
It follows from Eq. (4) that when the metal ions Cr2(SO4)3 system by a general equation of formation of
mainly occur in a solution as the complexes, i.e., when chromium hydroxosulfate complexes:
the concentration of the hydrated ions is insignificant 3+ 2– – 3 p – 2r – q
(α0 0), the relative error in determination of αn will pCr + rSO 4 + qOH [ Cr p ( SO 4 ) r ( OH ) q ]
,
be insignificant, though the errors in the stability con- (5)
stants are noticeable. If α0 = 0.1, ∆ log β = 0.5, then characterized by the concentration stability constants
ε(αn) = 0.115 (11.5%), which is admissible for the most βprq:
estimate and technical calculations used for the deter- [ Cr p ( SO 4 ) r ( OH ) q ]
mination of compositions of solutions of the complexes β prq = ---------------------------------------------.
p r q
(6)
and for plotting the diagrams showing the prevalence of [ Cr ] [ SO 4 ] [ OH ]
a specific complex. Figure 1 shows the diagrams of the
complex distribution in the model system (M–L) with Given in Table 1 are the chemical reactions (for sim-
plicity, water in the inner coordination sphere of ions is
log β = 3.0, 5.0, and 6.0 and with increasing these val-
omitted, and the hydroxonium ion is written as H+) and
ues by 0.5. An error introduced to log β brings about an the thermodynamic stability constants of the respective
error in the calculations of α0 and α1, but almost does complexes for the equilibrium concentrations. Since
not affect the values of α2 and α3 and the concentration some of the constants were determined at the ionic
boundary lines ( log c L ) separating the areas with a spe- strength different from zero, the thermodynamic stabil-
cific prevailing complex (Fig. 1b). ity constants of the chromium complexes were calcu-
lated with the use of the literature data and of the aver-
Thus, the results obtained confirm that in the esti- age ionic activity coefficients of the supporting electro-
mates and technical calculations of the equilibrium lyte indicated in the corresponding paper or from the
concentrations, the concentration constants can be Devis equation.
replaced by the thermodynamic or concentration con- The equilibrium concentrations of the hydrogen,
stants determined at different ionic strengths, which is chromium, and sulfate ions formed upon dissolution of

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 7 2004

 AQUEOUS SOLUTIONS OF Cr(III) SULFATE 499

Cr2(SO4)3 were found from a system of equations of the Table 1. Chemical reactions, logarithmic thermodynamic
2– stability constants in the system H2O–Cr2(SO4)3
material balance for the Cr3+ and SO 4 ions and the
proton balance equation: Refe-
Chemical reaction logβprq
rences
2c = β Cr ( HSO4 ) x 1 x 4 x 100
 H+ + OH– H2O 14.00 [9]
 P = 4R = 3Q = 7 q
 r  K w
∑∑∑
2– –
+ pβ x
p
x ------ - , H+ + SO 4 HSO 4 1.92 [10]
 prq 100 4 
x1 
 p=1r=0q=0 2–
 Cr3+ + H+ + SO 4 [Cr(HSO4)]2+ 2.1 [11]
 3c = x 4 + β HSO4 x 1 x 4 + β Cr ( HSO4 ) x 1 x 4 x 100
 P = 4R = 3Q = 7 Cr3+ + SO 4
2–
[Cr(SO4)]+ 1.3 [12]
 r K
q (7)
∑∑∑ rβ prq x 100 x 4  ------w- ,
p
+  x1  Cr3+ + 2 SO 4
2–
[Cr(SO4)2]– 2.0 [12]
 p=1r=0q=0
 2–
 x 1 + β HSO4 x 1 x 4 + β Cr ( HSO4 ) x 1 x 4 x 100 Cr3+ + 3 SO 4 [Cr(SO4)3]3– 2.5 [12]

 Kw P = 4 R = 3 Q = 7 r K
q 2Cr3+ + 3 SO 4
2–
[Cr2(SO4)3]0 3.5* [13]
∑∑∑ qβ prq x 100 x 4  ------w- ,
p
 = ------- +
 x1 p = 1 r = 0 q = 0  x1  2–
Cr3+ + OH– + SO 4 [Cr(OH)(SO4)]0 11.1** [14]
where Ò is the total concentration of Cr2(SO4)3 in the Cr3+ + OH– [Cr(OH)]2+ 10.1*** [4]
solution (mol/l); x1 = [H+], x4 = [OH–], x100 = [Cr3+]. Cr3+ + 2OH– [Cr(OH)2]+ 18.2 [4]
Then, the equilibrium concentrations of the remaining
species were found from Eq. (6). Cr3+ + 3OH– [Cr(OH)3]0 24.0 [4]
The mathematical model of pH effect on the distri- 2Cr3+ + OH– [Cr2(OH)]2+ 11.6 [4]
bution of chromium complexes was based on the solu- 2Cr3+ + 2OH– [Cr2(OH)2]2+ 24.2 [4]
tion of the above system of equations less the proton 3Cr3+ + 2OH– [Cr3(OH)2]7+ 24.8 [4]
balance equation, whereas the hydrogen ion concentra- 3Cr3+ + 3OH– [Cr3(OH)3]6+ 37.5 [4]
tion was preset.
3Cr3+ + 4OH– [Cr3(OH)4]5+ 48.7 [4]
3Cr3+ + 5OH– [Cr3(OH)5]4+ 59.6 [4]
COMPARISON OF CALCULATION MODELING 3Cr3+ + 6OH– [Cr3(OH)6]3+ 69.7 [4]
DATA WITH EXPERIMENTAL DATA
3Cr3+ + 7OH– [Cr3(OH)7]2+ 80.8 [4]
The pH values of Cr2(SO4)3 solutions with different
concentrations, the fraction of the “violet” modifica- 4Cr3+ + 4OH– [Cr4(OH)4]8+ 52.4 [15]
tion, and that of the complexes of the different charge 4Cr3+ + 6OH– [Cr4(OH)6]6+ 73.6 [15]
can be easily measured. The obtained data can be used 0
to verify the validity of the mathematical model for * The stability constant is calculated from the values of ∆G f
estimating the equilibrium concentration of the species 2–
[13] for Cr2(SO4)3 and Cr3+, SO 4 ions in aqueous solutions.
occurring in the solution. Table 2 presents the calcu-
lated and experimental data of the above-mentioned ** The calculated statistical value of the formation constant for
complexes with mixed ligands.
parameters at different Cr2(SO4)3 concentrations and *** The stability constants were determined in [4] with a 0.2 M
the absolute and relative errors of calculations. The NaNO3 supporting electrolyte.
“violet” modification fraction in a 0.385 M solution of
chromium sulfate at pH 2 was found experimentally to
be 0.115 [17]. The corresponding value calculated from in the anionic and neutral complexes was 0.28 and 0.27,
the considered mathematical model was 0.085, which respectively.
agrees satisfactorily with the experimental data. Taking into account the above assumptions one can
According to the results of calculations, an increase conclude that the calculated data agree well with the
in the Cr2(SO4)3 concentration brings about a signifi- experimental results and the mathematical model
cant increase in the fraction of chromium contained in makes it possible to estimate the equilibrium concen-
neutral complexes (from 0.05 to 0.40) and a decrease in trations of species in chromium sulfate solution.
the fraction of the positively charged complexes (from
0.75 to 0.35). The chromium fraction in the negatively CALCULATION EXPERIMENT
charged complexes remains almost unchanged (0.2–
0.25). The ionic exchange experiment (with CU-2 cat- The Effect of Chromium Sulfate Concentration
ion exchanger and AN-1 anion exchanger) revealed that on the Complex Distributions
in a 0.48 M chromium sulfate solution, the chromium As follows from the calculation data in Fig. 2, an
fraction in the cationic complexes was 0.45, while that increase in the Cr2(SO4)3 concentration in electrolyte

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 7 2004

500 VINOKUROV et al.

Table 2. The calculated and experimental pH values of Cr2(SO4)3 solutions of different concentration, the fraction of “violet”
modification and of chromium in complexes with different charges

Characteristics of chromium sulfate solution c, mol/l Calculation Experiment |∆|* |ε|, %*

pH 0.23 1.96 1.69 0.27 16

0.35 1.90 1.58 0.32 20
0.47 1.86 1.42 0.44 31
0.58 1.83 1.35 0.48 35
0.70 1.81 1.29 0.52 40
0.80 1.78 1.25 0.53 42
0.93 1.76 1.20 0.56 46
1.20 1.72 1.09 0.59 52
The fraction of the “violet” 0.385 (pH 2) 0.085 0.115 [17] 0.03 26
modification of chromium sulfate
The fraction of chromium in:
negatively charged complexes 0.48 0.29 0.28 0.01 3.6
positively charged complexes 0.48 0.50 0.45 0.05 11
neutral complexes 0.48 0.22 0.27 0.05 18
Average 28
* |∆| and |ε| are the absolute and relative errors, respectively.

from 0.001 to 1.5 mol/l leads to a decrease of the chro- Let us analyze the distribution of chromium in dif-
mium fraction in aqua complexes from 0.69 to 0.1 and ferent complexes in more detail, depending on chro-
in hydroxo complexes, from 0.28 to 0.1, and to an mium sulfate concentration. All plots of the chromium
increase in the chromium fraction in the sulfate com- distribution refer to the complexes with the minimum
plexes from 0.03 to 0.85. The results of calculations chromium fraction 5%.
showed that in the diluted solutions of chromium sul- Distribution of hydroxo complexes. The results of
fate (Ò < 0.1 mol/l), the “green” modification is speci- calculation (Fig. 3) revealed that the total fraction of
fied by chromium hydroxo complexes in the solution, chromium in hydroxo complexes in the range of chro-
whereas in the concentrated solutions (Ò > 1 mol/l), it mium sulfate concentration 0.001–0.1 mol/l was 0.28–
occurs due the prevailing chromium sulfate complexes. 0.25. As the Cr2(SO4)3 concentration was further
increased, the Cr3+ fraction in hydroxo complexes was
decreased to reach 0.11 at 1.5 mol/l.
α
1.0 It was found that even at low Cr2(SO4)3 concentra-
tions (0.001 mol/l), the prevailing species in the solu-
3 tion were the polynuclear hydroxo complexes (with a
0.8
0.20 fraction of chromium); in the mononuclear com-
plexes, this fraction did not exceed 0.08 (as the
0.6 [Cr(OH)]2+ form), while it reduced almost to zero when
the chromium sulfate concentration was increased to
0.4 0.1 mol/l.
0.2 2
The polynuclear complexes mainly occur as
[Cr4(OH)4]8+ with the chromium fraction in this form
1 being increased from 0.05 to 0.2 as the Cr2(SO4)3 con-
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 centration was increased from 0.001 to 0.1 mol/l. With
cCr (SO4)3, mol/l the further increase in concentration to 1.5 mol/l, the
2
fraction of chromium in this complex decreased to 0.1.
Fig. 2. Chromium distribution in (1) aqua, (2) hydroxo, and In the other polynuclear hydroxo complexes
(3) sulfato complexes in equilibrium system H2O– ([Cr2(OH)]5+, [Cr2(OH)2]4+, [Cr3(OH)3]6+, [Cr3(OH)4]5+,
Cr2(SO4)3. [Cr3(OH)5]4+), the fraction of chromium did not exceed

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 7 2004

 AQUEOUS SOLUTIONS OF Cr(III) SULFATE 501

α α
0.3 5 0.8
6
0.6 5
0.2 4
0.4
3 2
1
0.2
0.1 3 4
0
2 10–3 10–2 10–1 100 101
1 cCr (SO4)3, mol/l
0 2
10–3 10–2 10–1 100 101
cCr , mol/l
2(SO4)3

Fig. 3. The distribution of hydroxo complexes in H2O– Fig. 4. The distribution of chromium sulfate complexes in
Cr2(SO4)3 equilibrium system: (1) [CrOH]2+, (2) H2O–Cr2(SO4)3 equilibrium system: (1) [CrSO4]+, (2)
[Cr2(OH)2]4+, (3) [Cr2(OH)4]8+, (4) polynuclear hydroxo [Cr2(SO4)3]0, (3) [Cr(SO4)2]–, (4) [Cr(SO4)3]3–, (5) mono-
complexes, and (5) total fraction of chromium in hydroxo nuclear complexes, and (6) the total fraction of chromium in
complexes. sulfate complexes.

0.1 and decreased almost to zero as the chromium sul- When pH of an electrolyte (Fig. 5b) increases from
fate concentration increased to 0.2. 0 to 3.8, the fraction of chromium in aqua complexes
reduces from 0.45 to 0. In hydroxo complexes, the frac-
Sulfate complexes. As was shown by the results of tion of chromium grows in this case to 0.8, but it
calculations (Fig. 4), the total fraction of chromium in sharply increases when pH is higher than 1.4. The
the sulfate complexes in the range of Cr2(SO4)3 concen- change in the fraction of chromium in sulfate com-
trations from 0.001 to 1.5 mol/l increased from 0.03 to plexes exhibits the extreme nature with the maximum
0.8. Chromium was mainly found in the mononuclear (0.75) at pH 1.5.
sulfate complexes, where its fraction is maximum
(0.52) at the chromium sulfate concentration in the Thus, one can suggest that in concentrated
solution 0.3 mol/l. The maximum fraction (0.25) of Cr2(SO4)3 solutions (Ò = 0.5 mol/l) at pH < 1.5, the Cr3+
[Cr(SO4)]+ was found at the concentration of 0.1 mol/l; ions mainly occur in aqua and sulfato complexes; at
the maximum fraction (0.2) of [Cr(SO4)2]– was formed 1.8 < pH < 2.8, they occur in hydroxo and sulfato com-
plexes; at pH > 2.8, the polynuclear hydroxo complexes
at the concentration of 0.4 mol/l; the maximum fraction predominate in the solution. The results obtained also
(0.092) of [Cr(SO4)3]3– occurred at the concentration of show that the “green” modification occurs in the con-
0.7 mol/l. The polynuclear complexes are presented by centrated chromium sulfate solutions due to the prevail-
the form [Cr2(SO4)3]0 where the chromium fraction ing sulfate complexes.
sharply increases at c Cr2 ( SO4 )3 higher than 0.1 mol/l, and Now, we shall consider the chromium distribution in
at c Cr2 ( SO4 )3 = 1.5 mol/l, it reaches 0.4. In addition to the different complexes depending on pH of the chromium
sulfate solution.
above complexes, at the concentration exceeding
0.2 mol/l, the solution also contains the protonated Distribution of hydroxo complexes. It follows
complex [Cr(HSO4)]2+, whose fraction is 0.02. The from the results of calculations (Fig. 6) that the total
fraction of chromium in hydrosylfate complexes is less fraction of chromium in hydroxo complexes in the pH
than 0.01. range 0–1.2 is almost zero. As pH of a solution is fur-
ther increased, the fraction of chromium in hydroxo
complexes sharply increases and at pH 3.8, it equals
Effect of pH of Chromium Sulfate Solution 0.75. At pH values up to 3.6, the solution mainly con-
on the Distribution of Complexes in the Equilibrium tains [Cr4(OH)4]8+ with the maximum fraction of chro-
System H2O–Cr2(SO4)3 mium (0.45) being reached at pH 2.8. The further
increase in pH leads to a significant decrease in the con-
The data in Fig. 5a indicate that in the range of pH centration of this complex and in the formation of
values from 0 to 0.5, the fraction of chromium in poly- [Cr4(OH)6]6+, [Cr3(OH)4]5+, [Cr3(OH)5]4+, [Cr3(OH)6]3+,
nuclear complexes is insignificant. As pH increases [Cr3(OH)7]2+ with the maximum fraction of chromium
from 0.5 to 3.8, the chromium fraction in mononuclear in each of these complexes being less than 0.1. At pH
complexes decreases from 1 to 0.2, while in polynu- higher than 3.6, the [Cr3(OH)7]2+ complex prevails in
clear complexes, it increases respectively from 0 to 0.8. the solution that is transformed later to Cr(OH)3.

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 7 2004

502 VINOKUROV et al.

α fraction (0.25) of [Cr(SO4)]+ is attained at pH 1.2, while

1.0
1 (a)
the maximum fraction (0.2) of [Cr(SO4)2]– is reached at
0.8 pH 2.2 and that of [Cr(SO4)3]3– (0.25) is found at pH
3.2. The fraction of chromium in hydroxo sulfate com-
0.6 plexes is negligible at all pH values under consider-
0.4 ation. In polynuclear complexes represented by
[Cr2(SO4)3]0, the chromium fraction increases sharply at
0.2 2 pH values exceeding 0.5 and becomes maximum (0.25)
0 at pH 1.6. At pH > 3.6, the solution almost contains nei-
(b) ther polynuclear sulfate complexes nor [Cr(SO4)]+.
1.0
3
0.8
RESULTS AND DISCUSSION
0.6 2
1 The pattern of the equilibrium system H2O–
0.4
Cr2(SO4)3 at different c Cr2 ( SO4 )3 and pH values can be
0.2
obtained in detail from the diagram of regions with the
0 1 2 3 4 prevailing fraction of a complex [8] (vertical cross sec-
pH tion of a three-dimensional diagram αi–ç–c), which
makes it possible to establish the predominant species
Fig. 5. The distribution of chromium in complexes of H2O– in a solution (Fig. 8).
Cr2(SO4)3 equilibrium system vs. pH: (a) in (1) mononu-
clear and (2) polynuclear; (b) in (1) aqua, (2) hydroxo, and Some experimental data were presented above that
(3) sulfato complexes. agree with the calculation results. The diagram shows
the experimental dependence of pH (Fig. 8, 1) and of
light absorption A (Fig. 8, 2) of the chromium sulfate
Sulfate complexes. The calculations revealed solutions of different concentrations. The plot ç–c
(Fig. 7) that the total fraction of chromium in sulfate intersects two interfaces in the diagram and crosses
complexes in the pH range from 0 to 1.5 grows from three regions of existence of different complexes,
0.55 to 0.75. When pH is increased to 3.8, the chro- namely, [Cr(H2O)6]3+, [CrSO4]+, [Cr2(SO4)3].
mium fraction in sulfate complexes reduces to 0.25. The number of compounds prevailing in the equilib-
Chromium is mainly contained in mononuclear sul- rium system can be determined from the photometric
fate complexes where its fraction in the pH range 0–3.8 data (Aij is the absorption of the ith solution with the
varies from 0.55 to 0.25. At pH 0–1, the predominant total concentration of the metal ions ci at the jth wave
complex is [Cr(HSO)4)]2+ whose fraction is nearly 0.5 length), by calculating the rank (R) of a matrix built up
at pH 0 and 0.2 at pH 1. At pH 2, the solution does not of the absorption elements Aij [14]. The electronic
almost contain the protonated complex. The maximum absorption spectra of chromium sulfate solutions were

α α
1.0 0.8
7
0.8
0.6 6
0.6 5 1
0.4
3
0.4 5
1 2
4 0.2
0.2 4
2
3 0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 pH
pH
Fig. 6. The distribution of chromium in hydroxo complexes Fig. 7. The distribution of chromium in sulfate complexes
of H2O–Cr2(SO4)3 equilibrium system vs. pH: (1) of H2O–Cr2(SO4)3 system vs. pH: (1) [Cr(HSO)4]2+, (2)
[Cr4(OH)4]8+, (2) [Cr4(OH)6]6+, (3) [Cr3(OH)5]4+, (4) [CrSO4]+, (3) [Cr2(SO4)3]0, (4) [Cr(SO4)2]–, (5)
[Cr3(OH)7]2+, and (5) the total fraction of chromium in [Cr(SO4)3]3–, (6) mononuclear complexes, and (7) the total
polynuclear complexes (dotted line corresponds to the for- fraction of chromium in sulfate complexes (dotted line cor-
mation of chromium hydroxide). responds to the formation of chromium hydroxide).

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 7 2004

 AQUEOUS SOLUTIONS OF Cr(III) SULFATE 503

A pH pH κ, mCm/m
4 4 6 6 20
[Cr3(OH)7]2+
[Cr(SO4)3]3–

2
2 18
3 3 [Cr3(OH)7]2+
[Cr4(OH)4]8+ 4 4
[Cr(SO4)3]3–

η, mPa s
[Cr4(OH)4]8+ 16
2 2 3
[CrSO4]+
[Cr2(SO4)3]
2 2 [CrSO4]+ [Cr2(SO4)3]
[Cr(H2O)6 ]3+ pH 1.25 14
1 1 1 1
[Cr(H2O)6]3+ [Cr(HSO4)]2+
[Cr(HSO4)]2+ 0 12
0 0.5 1.0 1.5
0 0 cCr (SO4)3, mol/l
2
0.5 1.0 1.5
cCr2(SO4)3, mol/l
Fig. 9. The diagram of regions with prevailing complexes in
H2O–Cr2(SO4)3 equilibrium system and the experimental
Fig. 8. The diagram of regions with prevailing complexes in plots of (1) pH, (2) viscosity, and (3) specific conductivity
H2O–Cr2(SO4)3 equilibrium system and the experimental of chromium sulfate solutions vs. c Cr ( SO ) .
2 4 3
plots of (1) pH and (2) light absoprtion of chromium sulfate
vs. c Cr ( SO ) .
2 4 3

Particularly in this concentration interval, the pH vs.c

plot only crosses the region of the [CrSO4]+ prevalence.
recorded at eight values of Cr2(SO4)3 concentrations
(0.233, 0.349, 0.465, 0.582, 0.698, 0.814, 0.93, and The deviations from the Bouguer–Lambert–Beer
1.163 mol/l). The 8 × 8 matrix was made of the absorp- law are observed in the domain where the ç–Ò curve
tion elements of these solutions at eight wave lengths intersects the region of prevalence of a specific com-
(400, 419, 492, 530, 560, 581, 600, and 716 nm). The plex (Fig. 8). When the ç–Ò curve crosses the region
results of calculating R for chromium sulfate solutions with the predominant complex, the plot of the optical
stored for different time (t) after heating are given density vs. concentration has the linear sections. Thus,
below: the deviations from the Bouguer–Lambert–Beer law
with the increasing concentration of Cr2(SO4)3 are only
τ, day 1 3 16 apparent and explained by transition to the region
where another type of the absorbing species prevails.
R 5 3 3
The changes in viscosity and specific conductivity
of chromium sulfate solution within a wide range of
The above data indicate that as the solution is aged, c Cr2 ( SO4 )3 can be also interpreted within the framework
i.e., as the system approaches equilibrium, the number of
complexes in the whole range of the studied concentra- of the mathematical model (Fig. 9). Thus, in the region
tions of chromium sulfate decreases and reduces to 3. with a specific prevailing chromium complex (with the
ç–c curve crossing over this region), the η vs. c plot
A similar conclusion can be made for the plot of the has a specific slope, which changes on transition to the
optical density vs. chromium sulfate concentration other region and depends on the nature of the species
(Fig. 8, 2). The Bouguer–Lambert–Beer law does not that prevails in this region (Fig. 9, 1, 2). The compari-
hold over the entire range of concentrations under son of the experimental data on viscosity of chromium
study. However, in the ranges of Cr2(SO4)3 concentra- sulfate solutions with the diagram of the regions with
tions ~0–0.2, 0.45–0.8, and 0.95–1.15 mol/l, this plot predominant complexes makes it possible to derive the
has linear sections passing through the origin of coordi- following order of the changing viscosity: [Cr(H2O)6]3+
nates and having different slopes (1.1, 2.1, and 2.7,
respectively). One can suggest that only one complex < [CrSO4]+ < [Cr2(SO4)3]. When going from hexaaqua
species predominates within each of the indicated complexes to sulfate and, particularly, to polynuclear
regions. This is confirmed by the determination of the sulfate complexes, the viscosity of solutions sharply
rank of the 4 × 4 matrix built up of the Aij elements for increases.
the concentration range 0.45–0.8 mol/l at four wave The specific conductivity measurements for chro-
lengths. Such a matrix has the rank equal to 1, which mium sulfate solutions at constant pH value of 1.25 and
suggests the prevalence of only one complex species. the comparison of the results obtained with the diagram

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 7 2004

504 VINOKUROV et al.

of prevailing complexes show that the maximum of the Chemical Engineering for valuable advice and remarks
specific conductivity corresponds to the boundary line of during discussion of the results.
transition to the region with the prevailing [Cr2(SO4)3]
complex (Fig. 9, 3). In the domain of the transition bound-
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Prof. S. Solov’ev from the Mendeleev University of Elektrokhimiya, 1993, vol. 29, no. 7, p. 651.

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 7 2004