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Effect of Chloride Ions on the Hydrolysis of Trivalent

Lanthanum, Praseodymium and Lutetium in Aqueous
Solutions of 2 M Ionic Strength

Article  in  Journal of Solution Chemistry · April 2005

DOI: 10.1007/s10953-005-5193-7

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Journal of Solution Chemistry, Vol. 34, No. 4, April 2005 (

C 2005)

DOI: 10.1007/s10953-005-5193-7

Effect of Chloride Ions on the Hydrolysis

of Trivalent Lanthanum, Praseodymium
and Lutetium in Aqueous Solutions
of 2 M Ionic Strength
H. López-González,1,2 M. Solache-Rı́os,1,∗ M. Jiménez-Reyes,1
J.J. Ramı́rez-Garcı́a,1,2 and A. Rojas-Hernández2

Received July 16, 2004; revised December 15, 2004

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.

KEY WORDS: Lanthanides; hydrolysis; solubility; stability constants; chloride

complexes.

1. INTRODUCTION
The determination of equilibrium constants can be difficult when several
chemical species are simultaneously present in the solution, which can be

1 InstitutoNacional de Investigaciones Nucleares, Depto. de Quı́mica. Apdo. Postal 18-1027. 11801

México, DF; e-mail: msr@nuclear.inin.ms.
2 Universidad Autónoma Metropolitana-Iztapalapa, Área de Quı́mica Analı́tica. Apdo. Postal 55-534.

09340 México, DF.

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

mononuclear or polynuclear, and soluble or insoluble.(1) In the latter case, the

conditions under which the solutions become saturated and the solubility product
constants must be known.
Equilibrium constants have been determined by several methods. Potentio-
metric pH titration, which is frequently used, requires the use of a computer
program to calculate the constants. One such program is SUPERQUAD(2) which
considers only soluble species. However, when insoluble species are formed, a
part of the metal content escapes determination and systematic errors arise. The
magnitude of the error depends upon the nature of the particular metal being
studied and the mathematical analysis used to extract the equilibrium constants.
The influence of the data analysis can be understood and foreseen by studying the
behavior of the metal ions in solution by means of their pM(aq) -pC H diagrams.(3)
Kragten and Decnop-Weever(4−11) have applied these pM(aq) -pC H diagrams
to the trivalent cation-hydroxide systems of cerium, samarium, gadolinium, ytter-
bium, erbium, neodymium, and lanthanum. The hydrolysis and solubility product
constants were determined for each element; all of their studies were carried out
in 1 M sodium perchlorate solutions in a nitrogen atmosphere and at room tem-
perature. Stability constants for Ce(III), Sm(III) and Nd(III) polynuclear species
were also determined.
The aim of the present research was to explore the influence of chloride ions
on the solubility product of solid hydroxides and the first hydrolysis constants of
La(III), Pr(III) and Lu (III). The measurements were made at 2 M ionic strength,
imposed with NaClO4 (aq) or NaCl(aq). The temperature was controlled at 303 K
and the experimental methods used were potentiometry and determination of the
pLn(aq) − pCH diagrams. Data obtained from the former method were treated
with both the program SUPERQUAD and by fitting of the results with the mean
ligand number equation. The results from the pLn(aq) − pCH diagrams were treated
according to the appropriate solubility equation.
The fundamentals of hydrolysis and solubility of the trivalent rare-earth
elements and pLn(aq) − pCH diagrams are given elsewhere;(12) only the main def-
initions are included here. At the initial stage, the first hydrolysis constant is
calculated using

∗ [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+

Ln denotes the total rare-earth concentration, and

∗
∗
β1,H
β1,H = (7)
1 + β1,Cl [Cl− ]
Finally:
∗
β1,H
∗
β1,H
−1 [LnCl2+ ]
β1,Cl = − = (8)
[Cl ] [Ln3+ ][Cl− ]

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

The standard solutions of sodium hydroxide were prepared in a glove box

under a nitrogen atmosphere, by diluting the supernatant from a 50% w/v
sodium hydroxide aqueous solution which had been centrifuged to separate
the insoluble sodium carbonate.(13) The titration of the standard solutions with
hydrochloric acid proved that the resulting solutions were free of carbonate
ions. These solutions were used immediately, or were stored in the same glove
box under a nitrogen atmosphere. The lids of the solution bottles had a trap
containing ascarite as a CO2 absorbent. The concentration of sodium hydrox-
ide of each stock solution was determined by titration with potassium hydro-
gen phthalate, the ionic strength being adjusted with NaClO4 or
NaCl.
The pH measurements were carried out with a combined electrode sys-
tem (glass–AgCl/Ag), which has low interference coefficients for alkali ions. A
pH-meter (Radiometer TIM900 Titrilab), together with an automatic buret (Ra-
diometer ABU901), a double-walled cell, and a constant-temperature circulator
(Polyscience Circulator 12101-10), were used to measure the pH with a precision
of 0.001 pH units. All the experiments were carried out at (303.0 ± 0.1) K, and
a nitrogen flux was maintained in the reaction cell. The pC H of the NaCl(aq) and
NaClO4 (aq) stock solutions were adjusted to three with hydrochloric acid in order
to prevent the hydrolysis of rare-earth elements before the experiments began. The
solutions were centrifuged at 16,000 rpm (Hermle Labortechnik Labnet z323) to
remove solid material.
All experimental procedures for the radioactivity measurements of rare-earth
element solutions, the precipitate formation (diagrams pLn(aq) − pCH ) and the pH
titrations are described elsewhere.(14)
The isotopes 140 La, 142 Pr and 177 Lu were obtained by irradiating stan-
dard nitrate solutions of the rare-earth elements in a nuclear reactor TRIGA
MARK III with a thermal neutron flux of 1 × 1013 cm−2 s−1 . Irradiation times
of 5 min were used for La, 1 h for Pr, and 2 h for Lu. The resulting iso-
topes were identified by means of their typical gamma radiation spectra and
by measurements of their half-lives (t 1/2 = 40.3 h, 19.2 h and 6.64 days, re-
spectively). Experimental results are in agreement with the literature
values.(15)
Lanthanum was taken as a typical example for the characterization of the
fresh rare-earth element hydroxide precipitate. The solid was obtained under a
nitrogen atmosphere by adding a sodium hydroxide solution free of carbonate ions
(prepared as described above) to a lanthanum nitrate solution of initial pH value
of three, until a pH about ten was reached. The solid was then immediately filtered
and dried at 373 K. These solids were precipitated from both 2 M NaClO4 (aq)
and 2 M NaCl(aq), and were studied by X-ray diffraction, IR spectrometry and
scanning electron microscopy.
Effect of Chloride Ions on the Hydrolysis of Trivalent Rare-Earth Elements 431

Powder X-ray diffraction patterns of the samples were obtained with a

Siemens D500 diffractometer coupled to a copper-anode X-ray tube. Conventional
X-ray diffraction patterns were used to identify the compounds.
IR spectra of samples in KBr pellets were recorded in the range 4000–
450 cm−1 on a Perkin-Elmer/1600 FTIR spectrometer.
For scanning the electron microscopy, the samples were mounted directly
on the holders and then observed at 10 and 20 kV. A Philips XL 30 electron
microscope was used for determining the scanning electron micrographs. The
microanalyses were carried out with a DX-4 sonde.
Potentiometric calibration lines were obtained as described elsewhere,(14) and
all pH measurements were corrected by means of the resulting equations:

pCH = (1.03 ± 0.01) pH + (0.606 ± 0.005), (9)

where r = 0.999 for 2 M NaClO4 (aq)

pCH = (1.05 ± 0.02) pH + (0.243 ± 0.007), (10)

where r is the correlation coefficient equal to 0.999 for 2 M NaClO4 (aq)

The concentrations of the solutions used for the potentiometric titrations were
fixed at 1 × 10−4 M for the REE and 2.5 × 10−3 M for NaOH in 2 M aqueous
NaClO4 or NaCl. The initial volume in the titration cell was 20 cm3 and at
least three experiments were performed under the same conditions to yield the
reproducibility of the measurements. Data were mathematically treated with the
program SUPERQUAD in order to calculate the equilibrium constants.
The pH for the determination of the log10 β ∗1,H of the lanthanides was mea-
sured with the equipment mentioned above and independently with a pH meter
(Radiometer Tacussel TTP2) together with an automatic titration buret (EBX3),
glass and a reference electrodes, and a constant temperature water circulator (Cole
Parmer Polystat Constant Temperature Circulator, 12101-10). The pH measure-
ments were corrected by means of the equations obtained:

pCH = (1.06 ± 0.006) pH + (0.724 ± 0.044), (11)

where r = 0.998 for 2 M NaClO4 (aq);

pCH = (1.12 ± 0.01) pH + (0.037 ± 0.065), (12)

where r = 0.998 for 2 M NaCl(aq)

The concentrations of the REE solutions and sodium hydroxide in the 2 M
NaClO4 or NaCl solutions were similar to those mentioned above.
432 López-González, Solache-Rı́os, Jiménez-Reyes, Ramı́rez-Garcı́a, and Rojas-Hernández

3. RESULTS AND DISCUSSION

3.1. Lanthanum Hydroxide Characterization
The X-ray diffraction patterns of the samples were compared with those
listed on the cards of the Joint Committee on Powder Diffraction Standard: JCPDS
36-1481 (La(OH)3 ), JCPDS 5-0628 (NaCl), JCPDS 1-0606 (NaClO4 ·H2 O), and
JCPDS 25-1400 (La2 (CO3 )3 ·8H2 O). The solids were found to be composed of lan-
thanum hydroxide and sodium chloride or perchlorate, depending on the medium
in which they were prepared. The IR spectrum of the sample prepared in sodium
chloride showed the characteristic vibration bands of water (a wide and intense
band at 3445 cm−1 , and a well-defined vibration band at 1640 cm−1 ), whereas
the IR spectrum of the lanthanum hydroxide prepared in sodium perchlorate so-
lution showed characteristic vibration bands of water (a wide and intense band at
3445 cm−1 and a well-defined vibration band at 1638 cm−1 ), along with those of
sodium perchlorate (a wide band between 1050 and 1170 cm−1 , a small vibra-
tion band at 940 cm−1 and a well-defined vibration band at 630 cm−1 ). Finally,
scanning electron microscopy showed that the samples contained sodium, chlo-
rine, lanthanum and oxygen. These results indicate that regardless of the media,
NaCl or NaClO4 , the fresh precipitates obtained were predominantly lanthanum
hydroxide. Since neither carbon nor carbonate ions were found by any of these
techniques, the hydroxides may be considered to be free of hydroxycarbonate or
carbonate species.

3.2. pLn(aq) − pCH Diagrams

Figure 1 shows the pLn(aq) − pCH diagrams obtained for La(III), Pr(III) and
Lu(III) in 2 M NaCl(aq). Although the diagrams obtained in 2 M NaClO4 (aq) were
similar, a sudden increase of pLn(aq) was observed at lower pC H values.

Fig. 1. pLn(aq) − pCH diagrams for La(III), Pr(III) and

Lu(III) in aqueous 2 M NaCl at 303 K. The lines were
obtained using the polynomial solubility equation.
Effect of Chloride Ions on the Hydrolysis of Trivalent Rare-Earth Elements 433

The base-10 logarithms of the solubility products of freshly precipitated

REE(III) hydroxides and the hydrolysis constants were calculated by using the
polynomial equation for the solubility product, Eq. (3). For this purpose, a fit-
ting method was applied to the experimental data of the pLn(aq) − pCH diagrams
using an Excel program from MS Office 97 (Microsoft).Figure 1 shows the
curves fitted to the experimental points that were used to calculate both log10 K ∗ sp
∗/ ∗ ∗
and log10 β1,H in 2 M NaCl(aq). The values of K sp and β1,H obtained in 2 M
NaClO4 (aq) were similarly determined. These log10 Ksp and log10 K ∗ sp values
∗
∗
are included in Table I and the log10 β ∗ 1,H and log10 β1,H values are included in
Table II.
The solubility product (K i = [Ln3+ ](aq) /[H+ ]3 ) was calculated from each
data point. Log10 Ki is a linear function of pC H , when account is taken of the
initial concentration of the lanthanide in the pC H range where precipitation does
not take place. The corresponding equation is log10 K i = 3pCH − pLn(aq) (see
Fig. 2). However, this equation is no longer valid when pC H is high enough for
precipitation to occur. Moreover, changes of the lanthanide concentration resulting
from the addition of the NaOH solution must also be considered. Figure 2 shows
that the experimental data follow the behavior predicted by this equation up to a
certain pC H value. The inflection point indicates the limit between the unsaturated
and saturated zones.

Table I. Limits of Precipitation pC H and Solubility Product Constants (Units of

M−2 ) for the Fresh Precipitates of La(OH)3 (s), Pr(OH)3 (s), and Lu(OH)3 (s) in 2
M Aqueous NaClO4 (log10 K sp ∗ ) and in 2 M Aqueous NaCl (log K ∗ ) at 303 K,
10 sp
as Derived from the pLn(aq) − pCH Diagrams

Ln(OH)3 (s) + 3H+ (aq) 

 Ln3+ (aq) + 3H2 O(l)
Lanthanidea
La3+ Pr3+ Lu3+

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

Ln3+ (aq) + H2 O(l) 

 Ln(OH)2+ (aq) + H+ (aq)
Lanthanidea
La3+ Pr3+ Lu3+

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).

Fig. 2. Experimental data to the solubility product of La(III) as a function

of pC H in aqueous 2 M NaClO4 at 303 K. The equation of the line is
log10 K i = 3pCH − pLa(aq) .
Effect of Chloride Ions on the Hydrolysis of Trivalent Rare-Earth Elements 435

The experimental straight-line equations obtained in 2 M NaClO4 (aq) are as

follows:
log10 K i,exp = 2.98pCH − 3.88 for La(III),

log10 K i,exp = 2.97pCH − 3.91 for Pr(III),

log10 K i,exp = 2.96 pCH − 3.86 for Lu(III).

In 2 M NaCl(aq), the experimental equations obtained are as follows:

log10 K i,exp = 2.96 pCH − 3.87 for La(III),


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.

Fig. 3. Typical titration curves of Lu(III) in aqueous 2 M NaClO4

([Lu3+ ]initial = 1.8 × 10−4 M; [NaOH] = 2.9 × 10−3 M) and 2 M NaCl
([Lu3+ ]initial = 9.8 × 10−5 M; [NaOH] = 2.8 × 10−3 M). First derivative
lines are also included.
Effect of Chloride Ions on the Hydrolysis of Trivalent Rare-Earth Elements 437

Fig. 4. Mean ligand number as a function of pC H for La(III)

Pr(III) and Lu(III) in 2 M NaClO4 at 303 K. The lines correspond
to the best fits to the experimental data.

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.

∗ or log β ∗ for La(III), Pr(III) and Lu(III)

Fig. 5. Values of log10 β1,H 10 1,H
as a function of the charge density (z2 /r). Data in aqueous 1 M NaCl for
La(III), Pr(III). Eu(III), Er(III) and Lu(III), and in 2 M NaClO4 Eu(III)
were reported previously.(20,21)
438 López-González, Solache-Rı́os, Jiménez-Reyes, Ramı́rez-Garcı́a, and Rojas-Hernández

∗ ∗
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)

Ln3+ (aq) + Cl− (aq) 

 Ln(Cl)2+ (aq)
La3+ Pr3+ Lu3+
Experimental conditions Methoda β 1,Cl log10 β 1,Cl β 1,Cl log10 β 1,Cl β 1,Cl log10 β 1,Cl References

I=0M E 3.02 0.48 2.75 0.44 1.70 0.23 22

E 1.9 0.28 2.09 0.32 0.93 −0.03 23, 24
E 0.63 −0.2 — — 0.447 −0.35 25
I = 1 M NaClO4 — 0.794 −0.1 0.794 −0.01 0.398 −0.4 25
P 1.6 ± 0.03 0.2 1.58 ± 0.05 0.199 — — 28
I = 1 M HClO4 SE 0.8 −0.097 0.9 −0.046 28.2 1.45 26
SE 0.9 ± 0.3 −0.046 0.9 ± 0.3 −0.046 0.4 ± 0.2 −0.398 27
I = 2 M NaClb P 0.943 −0.0255 0.699 −0.155 0.174 −0.758 This work

a E: estimated; P: pH titration; SE: solvent extraction.

bT = 303 K.
Effect of Chloride Ions on the Hydrolysis of Trivalent Rare-Earth Elements
439
440 López-González, Solache-Rı́os, Jiménez-Reyes, Ramı́rez-Garcı́a, and Rojas-Hernández

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.

3.5. The Stability Constants of the First Chloride Species

The log10 β 1,Cl values were calculated by using the first hydrolysis constants
obtained in 2 M NaCl and 2 M NaClO4 using Eq. (8). Table IV compares the values
obtained in this research and those found in the literature.(22−28) Experimental
conditions are different again, although the values obtained here are of the same
order of magnitude as those reported by Peppard et al.(26) and Goto and Smutz.(27)
It is, however, worth noting that as expected β 1,Cl decreases with the atomic
number of the REE. The stability constant for the species EuCl2+ (0.535 M −1 )
calculated in the 2 M NaCl ionic medium using the data reported elsewhere,(17)
follows the same along the lanthanide series.

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

9. J. Kragten and L. G. Decnop-Weever, Talanta 30, 134 (1983).

10. J. Kragten and L. G. Decnop-Weever, Talanta 31, 731 (1984).
11. J. Kragten and L. G. Decnop-Weever, Talanta 34, 861 (1987).
12. C. F. Baes, Jr. and R. E. Mesmer, The Hydrolysis of Cations, (Wiley and Sons, New York, USA,
1977).
13. Daniel C. Harris, Análisis Quı́mico Cuantitativo, (Grupo Editorial Iberoamericana, S. A. de C.V.,
México 1992).
14. J. J. Ramı́rez-Garcı́a, E. Fernández-Ramı́rez, M. Jiménez-Reyes, M. Solache-Rı́os, H. López-
González, and A. Rojas-Hernández, J. Radioanal. Nucl. Chem. 257, 299 (2003).
15. C. M. Lederer, J. M. Hollander, and I. Perlman, Tables of Isotopes, (Wiley and Sons, New York,
USA, 1968).
16. T. Moeller and H. E. Kremers, Chem. Rev. 37, 97 (1945).
17. M. Jiménez-Reyes, M. Solache-Rı́os, and A. Rojas-Hernández, J. Solution Chem. 31, 131 (2002).
18. F. R. Hartley, C. Burgess, and R. M. Alcock, Solution Equilibria (Wiley and Sons, New York,
USA, 1980).
19. L. Ciavata, R. Porto, and E. Vasca, Polyhedron 8, 983 (1989).
20. J. J. Ramı́rez-Garcı́a, M. Jiménez-Reyes, M. Solache-Rı́os, and A. Rojas-Hernández, J. Solution
Chem. 32, 879 (2003).
21. M. Jiménez-Reyes, Thesis, Universidad Autónoma Metropolitana, Unidad Iztapalapa, México,
2003.
22. S. A. Wood, Chem. Geol. 82, 159 (1990).
23. J. R. Hass, E. L. Shock, and D. C. Sassani, Geochim. Cosmochim. Acta. 59, 4329 (1995).
24. F. J. Millero, Geochim. Cosmochim. Acta. 56, 3123 (1992).
25. R. M. Smith and A. E. Martell, Critical Stability Constants, Vol. 4, (Plenum Press, New York,
1981).
26. D. F. Peppard, G. W. Mason, and I. Hucher, J. Inorg. Nucl. Chem. 24, 881 (1962).
27. T. Goto, and M. Smutz, J. Inorg. Nucl. Chem. 27, 663 (1965).
28. H. M. N. H. Irving and P. K. Khopkar, J. Inorg. Nucl. Chem. 26, 1561 (1964).

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