Professional Documents
Culture Documents
2005JSolChem 34 04 427 - 441 PDF
2005JSolChem 34 04 427 - 441 PDF
net/publication/226142372
CITATIONS READS
11 158
5 authors, including:
Some of the authors of this publication are also working on these related projects:
All content following this page was uploaded by Melania Jiménez-Reyes on 14 December 2015.
DOI: 10.1007/s10953-005-5193-7
The solubility product of the solid hydroxides and the first hydrolysis constants of
trivalent ions of lanthanum, praseodymium and lutetium, were determined in 2 M
NaClO4 (aq) and 2 M NaCl(aq) at 303 K, where M denotes the concentration in mol-
L−1 . Solubility diagrams (pLn(aq) − pCH ) were measured by means of a radiochemical
method. The pC H borderlines of precipitation and the solubility products were deter-
mined from these diagrams. The fitting of the solubility equation with the experimental
values from the pLn(aq) − pCH diagrams also allowed the calculation of the first hy-
drolysis constants and the solubility products. In separate experiments, the stability
constants for the first monohydroxide species were determined by means of potentio-
metric pH titrations, where the data were treated with both the program SUPERQUAD
and by fitting of the results to the mean ligand number equation. Values of the log10 β 1,Cl
constants for the LnCl2+ species were also calculated at 2 M ionic strength and 303
K, using the hydrolysis constants obtained in both perchlorate and chloride media. The
quantitative effects of chloride ions on the hydrolysis reactions and solubilities were
determined for these three rare-earths spanning the lanthanide series.
1. INTRODUCTION
The determination of equilibrium constants can be difficult when several
chemical species are simultaneously present in the solution, which can be
427
0095-9782/05/0400-0427/0
C 2005 Springer Science+Business Media, Inc.
428 López-González, Solache-Rı́os, Jiménez-Reyes, Ramı́rez-Garcı́a, and Rojas-Hernández
∗ [Ln(OH)2+ ][H+ ]
β1,H = (1)
[Ln3+ ]
and the solubility product constant of the solid hydroxide in a saturated solution
is calculated using
∗
[Ln3+
(aq) ]
K sp = (2)
[H+ ]3
Effect of Chloride Ions on the Hydrolysis of Trivalent Rare-Earth Elements 429
The solubility of the rare-earth hydroxides, taking into account the first
hydrolysis species, is
s∼ ∗
= [Ln3+ ](aq) + [Ln(OH)2+ ](aq) = K sp [H+ ]3 + β1,H
∗ ∗
K sp [H+ ]2 (3)
Finally, the experimental and calculated mean hydroxide numbers, respec-
tively, are given by:
COH− − [OH− ] + [H+ ]
n̄ exp = (4)
CLn
and
∗
β1,H /[H+ ]
n̄ calc = ∗ (5)
1 + β1,H /[H+ ]
Considering the influence of a 2 M NaCl medium on the hydrolysis equi-
librium, the log10 β 1,Cl values may be calculated from the hydrolysis constant
values obtained in both the absence and the presence of chloride ions at the same
ionic strength and temperature. In a solution of chloride ions as high as 2 M, the
following equilibrium must be considered:
[Ln(OH)2+ ]
Ln + OH− →
← Ln(OH)
2+ ∗
β1,H = (6)
[Ln ][OH− ]
where
Ln = Ln3+ + LnCl2+
2. EXPERIMENTAL
All reagents were of analytical grade and boiled deionized water was used to
prepare the solutions. All studied aqueous solutions contained either 2 M NaCl or
NaClO4 .
430 López-González, Solache-Rı́os, Jiménez-Reyes, Ramı́rez-Garcı́a, and Rojas-Hernández
2 M NaClO4
pC H 8.44 ± 0.05 7.99 ± 0.05 7.45 ± 0.05
log10 K∗sp (A) 21.22 19.98 18.13
log10 K∗sp (B) 21.18 ± 0.09 19.81 ± 0.11 18.01 ± 0.01
log10 K∗sp (C) 21.20 ± 0.09 19.90 ± 0.11 18.07 ± 0.01
2 M NaCl
pC H 8.82 ± 0.14 8.55 ± 0.12 7.64 ± 0.18
∗ (A)
log10 K sp 22.39 21.74 18.8
∗ (B)
log10 K sp 22.15 ± 0.32 21.35 ± 0.26 18.52 ± 0.29
∗ (C)
log10 K sp 22.27 ± 0.32 21.54 ± 0.26 18.66 ± 0.29
a Values obtained by (A) fitting to the solubility equation, (B) limiting value of the
solubility product equation, and (C) mean values of the A and B calculations.
434 López-González, Solache-Rı́os, Jiménez-Reyes, Ramı́rez-Garcı́a, and Rojas-Hernández
Table II. First Hydrolysis Constants in Molarity Units for La(III), Pr(III) and
∗ ) and 2 M Aqueous NaCl (log β ∗ )
Lu(III), in 2 M Aqueous NaClO4 (log10 β1,H 10 1,H
at 303 K
2 M NaClO4
log10 β ∗ 1,H (A) −8.62 −8.37 −7.85
log10 β ∗1,H (B) −(8.65 ± 0.02) −(8.38 ± 0.02) −(8.01 ± 0.02)
log10 β ∗1,H (C) −(8.63 ± 0.05) −(8.36 ± 0.01) −(8.00 ± 0.07)
log10 β ∗1,H (D) −(8.63 ± 0.05) −(8.37 ± 0.02) −(7.95 ± 0.07)
2 M NaCl
∗ (A)
log10 β1,H −8.9 −8.75 −8.09
∗ (B)
log10 β1,H −(9.11± 0.04) −(8.76 ± 0.02) −(8.14 ± 0.02)
∗ (C)
log10 β1,H −(9.04 ± 0.01) −(8.75 ± 0.03) −(8.13 ± 0.01)
∗ (D)
log10 β1,H −(9.02 ± 0.04) −(8.75 ± 0.04) −(8.12 ± 0.02)
a From (A) pLn(aq) − pCH diagrams fitted to the solubility equation, (B) pH titration
and using the SUPERQUAD program, (C) pH titration data fitted to the ligand number
equation and mean values of these calculations are also included (D).
log10 K i,exp = 2.96pCH − 3.89 for Pr(III),
log10 K i,exp = 2.97pCH − 3.93 for Lu(III).
The values of the slopes of all these equations are around three, and their
intersections with the ordinate axis correspond to the initial concentration of
each lanthanide, regardless of the experimental medium. The correlation coeffi-
cients for the experimental data used to determine these equation parameters were
∗
>0.9999 when pC H was lower than the precipitation limit. Values of log10 K sp
∗
and log10 K sp were calculated from the average of two points, the first one being
the last point when r > 0.9999 and the following one (r ≤ 0.9999) (see Table I).
The averages of the corresponding pC H values (the borderlines of precipitation)
are also given in Table I.
It is observed (Table I) that as the atomic number increases, both the pC H
limits of precipitation and the solubility product values of the freshly precipitated
REE(III) hydroxides decrease. Moeller and Kremers(16) have explained this be-
havior according to the REE basicity properties; as the atomic number of the REE
increases, the cations bind hydroxyl ions more strongly, thereby decreasing the
solubility product values.
The same table shows that, in general, the pC H borderlines of precipitation are
lower in aqueous NaClO4 than in NaCl solutions. This behavior can be explained
by the formation of the soluble LnCl2+ species in the system that can be detected
under the experimental conditions of this research, due to the high concentration
of chloride ions present in 2 M NaCl(aq). According to the stability constant
values of the LnCl2+ species,(17) chloride ions compete with hydroxyl ions for the
complex formation with REE(III) and the pC H of precipitation are thus higher in
the presence of chloride ions than in their absence. Similarly, the solubility product
constants of freshly precipitated REE(III) hydroxides are higher in 2 M NaCl(aq)
than in 2 M NaClO4 (aq); the smallest difference was found for lutetium. Then, the
stability constants for LnCl2+ should decrease with atomic number as well.
436 López-González, Solache-Rı́os, Jiménez-Reyes, Ramı́rez-Garcı́a, and Rojas-Hernández
∗
A comparison of the log10 K sp values determined in this research with those
reported in the literature is difficult, because the experimental conditions such as
ionic strength, rare-earth concentration, temperature, along with other factors, are
different. Actually, data are found in the literature for “aged” and “fresh” precipi-
tates, where the solubility products for freshly precipitated active solids are higher
than for aged solids in which the particles are larger. In this research, pLn(aq) − pCH
diagrams were obtained from data corresponding to freshly precipitated REE(III)
∗
hydroxides. The log10 K sp for freshly precipitated La(III) hydroxide determined
here is different from the value reported (22.8) by Kragten and Decnop-Weever(11)
that was obtained by means of pLn(aq) − pCH diagrams as well, under CO2 -free
conditions, but in 1 M NaClO4 ionic strength and at (294.5 ± 0.5) K. As far as we
∗
know, there are no reported values of log10 K sp for freshly precipitated Pr(III) and
Lu(III) hydroxides determined under similar conditions.
3.3. pH Titration
Figure 3 shows typical curves of pH titrations for Lu(III) carried out in 2 M
aqueous NaClO4 and 2 M NaCl; the corresponding curves for La(III) and Pr(III)
are similar. The data range used as input for the program SUPERQUAD was
selected as follows: The initial point was taken immediately after the excess acid
was neutralized, i.e., where the first inflection point of the titration curve occurs.
On the other hand, the end point was selected just before Ln(OH)3 (s) precipitation
started, according to the pLn(aq) − pCH diagrams. As mentioned above, all these
determinations were carried out using two separate experimental procedures and
the results obtained from both of them are statistically similar.
Table II lists the Brönsted first hydrolysis constants for La(III), Pr(III), and
Lu(III) in aqueous 2 M NaClO4 and 2 M NaCl that were calculated by taking Kw
as a constant (log10 K w = −13.72 for 2 M NaClO4 and log10 K w = −13.68 for 2
M NaCl). The statistical parameters obtained from the SUPERQUAD program
were σ total between 1.4 and 3.6, and χ 2 was between 8.8 and 42.6.
The first hydrolysis constants were also calculated by means of the mean
hydroxide number equations (n̄).(12,18) Calculations were done using Eqs. (4) and
(5) given above and using the data over the same pC H range described for the
SUPERQUAD program calculations. Figure 4 compares the typical fitted curves
∗
obtained and the experimental data. The log10 β1,H values obtained are included
in Table II as well.
∗ ∗
As expected, the values of both log10 β1,H and log10 β1,H increase with atomic
number, because of the basicity properties of the rare-earth series. Besides, the
∗ ∗
results reported in Table II show that for a given element, β1,H > β1,H with the
largest difference being for La(III). As discussed above, this behavior can be
explained by the high concentration of chloride ions present in these solutions.
For a comparison of the values obtained in the present research with those
from previous studies, the constants should be referred to the same experimental
∗
conditions. Ciavatta et al.(19) reported a value of log10 β1,H = −8.75 for Pr(III) in
∗
3 M LiClO4 and at 333 K, and Kragten and Decnop-Weever(11) reported log10 β1,H
=−8.6 in 1 M sodium perchlorate at (294.65 ± 0.5) K for La(III). These values
are of the same order of magnitude as those reported in this paper, although ionic
strengths and temperatures are different.
Figure 5 shows the influence of charge density (z2 /r) on the hydrolysis con-
∗ ∗
stants. The log10 β1,H and log10 β1,H values of the present research, together with
those reported previously in 1 M NaCl(20) and 2 M NaClO4 ,(21) are plotted versus
∗
z2 /r in this figure. As charge density increases, the log10 β1,H values measured in 2
M NaClO4 increase as well, in good agreement with the basicity properties of the
REE(III) series with change of the ionic radius. As observed, the presence of chlo-
ride ions and their concentrations are important parameters for the determination
of the hydrolysis constants. The differences in the obtained hydrolysis constants,
in the presence and absence of chloride ions, are higher for La(III) than they are for
Lu(III), as noted above for the solubility product constants. This behavior can be
also explained by the basicity properties of the REE(III). Chloride ions compete
Table III. Solubility (in Molarity Units) of Ln3+ (s1,0 and s1,0 ),
), and the Total Solubility (s and s )
Ln(OH)2+ (s1,1 and s1,1
Lanthanide
La3+ Pr3+ Lu3+
2 M NaClO4
s = 4 K sp /27 a 4.5 × 10−6 2.1 × 10−6 7.4 × 10−7
s1,0 2.4 × 10−6 1.2 × 10−6 4.4 × 10−7
s1,1 4.7 × 10−6 2.0 × 10−6 6.6 × 10−7
s = s1,0 + s1,1 7.1 × 10−6 3.2 × 10−6 1.1 × 10−6
2 M NaCl
s = 4 K sp /27 a 8.9 × 10−6 5.9 × 10−6 1.1 × 10−6
s1,0 5.5 × 10−6 3.3 × 10−6 6.7 × 10−7
s1,1 7.5 × 10−6 5.8 × 10−6 9.7 × 10−7
+ s
s = s1,0 1.3 × 10−5 9.1 × 10−6 1.6 × 10−6
1,1
a The solubility calculated with the usual formula is also included, where
K sp = [Ln3+ ][OH− ]3 .
Table IV. Comparison of Stability Constants of LnCl2+ (Units of M−1 ) Taken from the Literature and Those Obtained in the Present
Research (T = 298 K)
with hydroxyl ions more strongly for complex formation with La(III) than for
Lu(III); Lu(III) hydrolyzes easier than La(III) because of its lower ionic radii and
higher charge density.
3.4. Solubility
Table III shows the solubility (in molarity units) of La(III) Pr(III) and Lu(III)
hydroxides in aqueous 2 M NaClO4 and 2 M NaCl. The solubilities of Ln3+
(s1,0 ) and Ln(OH)2+ (s1,1 ) were calculated according to the method of Jiménez–
Reyes.(21) In both media, the solubility decreases as the atomic number increases,
on account of the chemical properties of the lanthanide series discussed above. The
values calculated considering only the Ln3+ species (K ps = [Ln3+ ][OH− ]3 ) are
always lower than when both the solubility of Ln3+ plus Ln(OH)2+ are considered.
Moreover, the solubility of these rare-earth hydroxides is higher in NaCl(aq)
solution than in NaClO4 solution, by reason of the formation of the first chloride
species.
ACKNOWLEDGMENT
We are grateful to the Consejo Nacional de Ciencia y Tecnologı́a (CONACYT)
for financial support through the research project 32124E.
REFERENCES
1. A. Ringbom, Complexation in Analytical Chemistry, (Wiley and Sons, New York, USA, 1963).
2. P. Gans, A. Sabatini, and A. Vacca, J. Chem. Soc. Dalton Trans. 1195 (1985).
3. J. Kragten, Talanta 24, 483 (1977).
4. J. Kragten and L. G. Decnop-Weever, Talanta 25, 147 (1978).
5. J. Kragten and L. G. Decnop-Weever, Talanta 26, 1105 (1979).
6. J. Kragten and L. G. Decnop-Weever, Talanta 27, 1047 (1980).
7. J. Kragten and L. G. Decnop-Weever, Talanta 29, 219 (1982).
8. J. Kragten and L. G. Decnop-Weever, Talanta 30, 131 (1983).
Effect of Chloride Ions on the Hydrolysis of Trivalent Rare-Earth Elements 441