A Selected Thermodynamic Database For REE To Be Us

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A selected thermodynamic database for REE to be used in HLNW performance

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SE9700007
TECHNICAL
REPORT 95-35
SKB
A selected thermodynamic database for

REE to be used in HLNW performance
assessment exercises
Kastriot Spahiu, Jordi Bruno
MBT Tecnologia Ambiental, Cerdanyola. Spain
January 1995
SVENSK KARNBRANSJ.EHANTERING AB
SWEDISH NUCLEAR FUEL AND WASTE MANAGEMENT CO
P.O.BOX 5864 S-102 40 STOCKHOLM SWEDEN
PHONE + 46 8 665 28 00 ThLEX 13108 SKB
FAX+46 8 661 57 19
-u5
A SELECTED THERMODYNAMIC
DATABASE FOR REE TO BE
USED IN HLNW PERFORMANCE
ASSESSMENT EXERCISES
Kastriot Spahiu, Jordi Bruno
MBT Tecnologia Ambiental, Cerdanyola, Spain
January 1995
This report concerns a study which was conducted for SKB. The conclusions
and viewpoints presented in the report are those of the author(s) and do not
necessarily coincide with those of the client.
Information on SKB technical reports from 1977-1978 (TR 121), 1979

(TR 79-28), 1980 (TR 80-26), 1981 (TR 81-17), 1982 (TR 82-28), 1983
(TR 83-77), 1984 (TR 85-01), 1985 (TR 85-20), 1986 (TR 86-31), 1987
(TR 87-33), 1988 (TR 88-32), 1989 (TR 89-40), 1990 (TR 90-46), 1991
(TR 91-64), 1992 (TR 92-46), 1993 (TR 93-34) and 1994 (TR 94-33) is
available through SKB.
A SELECTED THERMODYNAMIC DATABASE FOR REE
TO BE USED IN HLNW PERFORMANCE ASSESSMENT
EXERCISES
Kastriot Spahiu and Jordi Bruno1
MBT Tecnologia Ambiental, Pare Tecnologic del Valles

C. Argenters 2, 08290 Cerdanyola, Spain.
1
Present adress, Intera (Spain), Pare Tecnologic del Valles, 08290 Cerdanyola, Spain.
ABSTRACT
A selected thermodynamic database for the Rare Earth Elements (REE) to
be used in the safety assessment of high-level nuclear waste has been
compiled. Thermodynamic data for the aqueous species of the REE with the
most important ligands relevant for granitic groundwater conditions have
been selected and validated. The dominant soluble species under repository
conditions are the carbonate complexes of REE. The solubilities of the
oxides, hydroxides, carbonates, hydroxycarbonates, phosphates and other
important solids have been selected and validated. Solubilities and solubility
limiting solids in repository conditions have been estimated with the selected
database. At the initial stages of fuel dissolution, the UO2(s) matrix
dissolution will determine the concentrations of REE. Later on, solid
phosphates, hydroxycarbonates and carbonates may limit their solubility.
Recommendations for further studies on important systems in repository
conditions have been presented.
11
ABSTRACT (Swedish)
En utvald termodynamisk databas för de sällsynta jordartsmetallerna
(lantaniderna), för användning i säkerhetsanalyser av förvaring av högaktivt
radioaktivt avfall, har kompilerats. Termodynamiska data för vattenlösliga
specier av lantaniderna med de viktigaste liganderna i granitiska grundvatten
har valts ut och validerats. Den dominerande specien under förvarsförhål-
landen är lantanidemas karbonatkomplex. Löslighetsprodukterna av oxider,
hydroxider, karbonater, hydroxykarbonater, fosfater och andra viktiga mineral
har valts och validerats. Lösligheter och löslighetsbegränsande faser under
förvarsförhållanden har bestämts med den utvalda databasen. I den tidiga
skedena av bränsleupplösningen kommer UO2 - matrisens upplösning att
bestämma koncentrationen av lantanider. I senare skeden kommer fosfater,
hydroxykarbonater och karbonater att bestämma lösligheten. Rekomenda-
tioner för fortsatta studier av, under förvarsförhållanden, viktiga system har
gjorts.
m
TABLE OF CONTENTS
ABSTRACT i
INTRODUCTION 1
1. DATA SELECTION 2
1.1. Simple lanthanide ions 2

1.2. Solution species 3
1.2.1. Hydrolytic solution species 6
1.2.2. Carbonate complexes 7
1.2.3. Phosphate complexes 8
1.2.4. Sulfate and fluoride complexes 11
1.2.5. Chloride, nitrate and other solution species 12
1.3. Solid phases 13

1.3.1 Solubility of the oxides and hydroxides 14
1.3.2 Solubility of the carbonates and hydroxycarbonates 15
1.3.3 Solubility of phosphates 21
1.3.4. Other solids 22
1.4. Data tables 24
2. TEST CASES 57
3. SOLUBILITIES OF REE IN REPOSITORY CONDITIONS 61
4. CONCLUSIONS AND RECOMMENDATIONS 66
REFERENCES 67
IV
INTRODUCTION
The cycling of the rare earth elements (REE) in Nature has been
largely increased in the past 30 years due to their anthropogenic
usage. Particularly, in the electronic industry with the developement
of semi- and supraconductor materials. The production of significant
amounts of REE during the fission of uranium and piutonium nuclear
reactor fuels constitutes another potential anthropogenic source.
The geochemistry of REE has been thoroughly studied, mainly as
indicator of selective water rock interactions where the REE have
been used to differentiate between various alteration processes. The
study of the low temperature geochemistry of the REE has increased
steadily in the last decades and several compilations have been
produced concerning particular aspects of the REE coordination
chemistry and thermodynamics( e.g. 1-13, 17-21). However, no
attempt has been made so far to produce a selected thermodynamic
database of REE to be used in the safety assessment of high-level
nuclear waste.
Our objective is therefore to produce an up to date thermodynamic

data base that includes the aqueous and solid phases specificly
relevant for granitic groundwater conditions.
1. DATA SELECTION
The thermodynamic databases associated to the geochemical modelling

computer codes, normally used in performance assessment exercises (i. e.
Harphreeqe (134) and EQ 3/6 (135) ) contain very few data on REE and their
compounds. This is also true for working data bases that have been produced in
international efforts like Chemval (136). Only data on europium, based on the
selection by Rard (5) and some sporadic data for La and Sm species and solids
are available in the databases associated to the Phreeqe and EQ 3/6 code
packages. The main sources of information for our compilation of soluble
species have been a review paper by Wood (1) and the later ones by Millero (2)
and Lee and Byrne (3). In addition, we have derived most of the solubility
constants from primary literature data. The details of the data compilation and
selection are given in the appropriate sections.
1.1. Simple lanthanide ions.
The dominant oxidation state of the REE in aqueous solution at 25 °C is the +3

state. However under oxidizing conditions Ce4* and under extremely reducing
conditions Eu2+, Sm2+ and Yb2+ are formed. The values chosen in the database
for the redox potentials are those reported in the review of Morss (21),
compared whenever possible with experimental determinations and with the
spectroscopic estimations of Nuggent et al.(23). The standard state
thermodynamic properties at 25 °C of Morss (21) are in good agreement with
NBS Technical Notes 270-5(18) and 270-7(19). The standard reduction
potentials of the reaction (in EQ 3/6 format):
Ln 3+ +0.5 H2O ^ Ln2+ + H+ + 0.25 O2(g)
for ytrium, lanthanum and the lanthanides reported in the tables were calculated
from the AGf°(Ln3+) and AGf°(Ln2+) of reference (21) and the equilibrium:
+
2 H20 ^ 4 H + 0 2 (g) + 4e~ log K = - 83.106
The only lanthanide(ll) ion which can exist in water for an appreciable period of
time at 25 °C is Eu(ll). Wood (4) calculates an increase of the stability of the two
valent state with temperature, to the point of its domination above 250 °C. Even
though temperatures other than 25 °C are not considered in this work, the
values of the constants for this equilibrium have been included in the database
for all REE.
For europium, Rard (5) uses a slightly different value from (21), based on new
experimental determinations (26), which has been accepted in this work. For the
other REE, the accuracy of the estimated redox(ll)-(lll) values is of the order of
0.1 V (21), which we consider quite acceptable for our pourposes.
The redox potential for the Ce(lll)-Ce(IV) couple
C e ^ + H+ + 0.25 O2(g) ^ Ce4+ + 0.5 H2O
is the only one of significance for performance assessment calculations. Since

the estimations of these potentials are more uncertain (21) and the importance
of the four valent state is reduced with the increase of the temperature (4), the
rest of the REE(III)-REE(IV) redox potentials were not included in the database.
1.2. Solution species
As mentioned above, at 25 °C the main oxidation state of lanthanum, the

lanthanides and yttrium is the +3 state. Since very few data are available for
complexes of only Eu(ll) and Ce(IV), and no recent data on the complexation
and solubility of the REE in oxidation state other than +3 were found, in the
following the discussion is centered on the complexation of trivalent REE.
Several reviews on the aqueus chemistry of the REE have been published (1, 7
-11) and the short summary given in this paragraph is based on this work.
The REE(III) ions are hard acceptors in the Pearson-Ahrland sense and form
strong complexes with hard ligands containing highly electronegative donor
atoms such as carbonate, phosphate, hydroxide, fluoride, and sulfate. The
bonds between REE3+ ions and hard ligands such as CO 3 ' 2 or F" are mainly
electrostatic in character and the 4f electrons do not seem to participate to a
large extent in the bonding. An approximately linear dependence of the log Pi
on the inverse of the sum of anionic and cationic radii has been reported (11) .
The deviations from this general behavior, with a break in the slope most often
occurring at Gd (named "tetrad" or "nephelauxetic" effect), are often very small
to be detected for most geochemically important ligands. Another consequence
of the dominantly electrostatic nature of bonding is that the coordination number
and the geometry of REE ions are less constrained than those of transition
metal ions. The coordination number of the REE in solid compounds ranges
from 3 to 12, while in solution it is generally accepted that for heavy REE(HREE)
it is mainly 8 and for LREE 8 or 9.
The stabilities of the solution species of the lanthanides are mainly based on the
recent reviews of Wood (1), Millero (2) and Lee and Byrne (3). It should be
pointed out that the primary experimental data used in these works to calculate
thermodynamic values of the constants are in some cases the same, as e. g. for
carbonate or phosphate complexes, but the calculation of activity coefficients to
extract thermodynamic values differs. In the process of selecting the values in
this work the following was considered:
Wood (1) uses a modified extended Debye - Huckel expression and assumes
the log K values to be linear with Vl/(1+Vl). While this is quite acceptable for low
ionic strengths and for complex formation reactions of the REE3* ions with high
charge ligands, the same can not be expected at high ionic strengths and for
monovalent ligands, since the Debye-Huckel contribution to the activity
coefficient expression is not as dominant.
Millero (6) has proposed a mixture of the ion association approach and specific
ion interaction approach of Pitzer. The main assumptions of the ion association
approach, such as the use of the mean salt method, based on the dependence
of the activity coefficients only on the ionic strength, are not true within the
frame of the Pitzer or any ion interaction approach. Byrne and coworkers
(3,64,65,66) use the ion association approach modified by Millero which for the
lanthanides gives in general slightly higher values of the constants than the
values obtained by the method used by Wood.
In another work (2) Millero modifies Pitzer's equations to functions of only ionic
strength. From the equations thus obtained, values of the thermodynamic
constants of lanthanide complexes with the most important ligands in natural
waters are calculated. This form of Pitzer equations is correctly applied in
calculating activity coefficients of trace species in ionic media, but the lack of
parameter values makes necessary other simplifications. For example, the
calculation of the thermodynamic constants for various lanthanide ion pairs is
carried out considering only the P(0) parameter for ion pairs, while all Pitzer
parameters are considered for the other ions. The neglection of the P(1)
parameter for the ion pairs leaves without compensation the respective large (3(1)
values for the lanthanide ions. This results in values at l=0 smaller than the ones
obtained with any one of the other methods. Also the unsymetricai mixing terms
for highly charged ions should influence appreciably the results obtained by using
the Pitzer method, and in Millero's treatement these terms are considered for
univalent ions, but have not been taken into account for the much higher same
sign and triple interactions of the lanthanide ions.
The selected values were extracted from the data of Lee and Byrne, Wood and
Millero, taking into account the above effects for each reaction. In cases when
recent and reliable experimental determinations were available, they were
included in the analysis.
1.2.1. Hydrolvtic solution species
The hydrolysis of the lanthanides has been reviewed in the competent work of
Baes and Mesmer (29) and their values have been accepted by Wood (1). A
linear free energy relationship was used to evaluate the hydrolysis constants of
several elements for which no sufficient good quality data were available. In the
cases when new data have been published after this compilation, they have
been included in the tables. In general, there is agreement between the values
reported by Baes and Mesmer and the most reliable recent measurements, as
discussed shortly in the following.
Kragten and Dencop-Weever (30-37) have studied the hydrolysis of La, Ce, Nd,
Sm, Gd, Tb and Yb measuring the solubility of their freshly precipitated (5 min.
aged) hydroxides. Their values measured at 1M NaCIO4 agree reasonably well
with the values selected by Baes and Mesmer, after accounting for the
difference in the ionic strength.
Davidov and Voronik (43) have used ion-exchange and spectrophotometry and
obtain -6.4 for the first hydrolysis constant of yttrium, in good agreement with
the value accepted in this work.
M'Halla et al. (40) have measured conductometrically the first hydrolysis

constants of La, Eu, Gd and Lu. Their values for the first hydrolysis constant
(-7.6 for La, -7.3 for Eu, -9.3 for Gd and < - 5 for Lu) are too high compared to
the ones proposed by Baes and Mesmer (29) (respectively -5.5, -6.2, -6.0, -6.4).
One possible explanation may be carbonate complexation due to carbon
dioxide contamination of the solution. Schmidt et al. (42) find weaker hydrolysis
for Eu and Yb using measurements of transient conductivity changes after pulse
radiation (-5.3±0.2 for both Eu and Yb, compared with -6.2 for Eu and -6.3 for
Yb). Bilal and Koss(44) have determined very large first hydrolysis constants for
Ce, Eu, Tb and Yb at 1 M NaCIO4 (-log p ^ -6.6, < -5, -7.4, -8.4, and for p2,
-11.8, -13.7, -14.30, -15.9 respectively). According to Bingler and Byrne (85) this
overestimation is due to the use of phosphate buffers, which complex the
lanthanide ions. The value -log p., = -6.43 of the first hydrolysis constant for Eu
at 0.7 M CI" reported by Caceci and Choppin (41) was calculated from
competitive reactions with oxalate complexing and assuming no hydrolysis at
pH=5.9. Lundqvist (52) estimates -5.7 for the same constant at 1 M NaCIO4,
while Nair et al.(44) report -5.71 for Eu and -5.0 for Sm at the same conditions
and -logp2 = -11.9 and -12.2 for their respective second hydrolysis constants.
These values are in fair agreement with the values selected here, after
accounting for the ionic strength difference. As a conclusion, the data reported
in ref.(29) for the hydrolysis of the REE have been accepted in this work. They
are changed only slightly in some cases when reliable new measurements have
been reported.
Ciavatta and coworkers (38, 39) have shown that at higher temperatures (50 or
60 °C) the polynuclear hydrolytic complexes predominant in lanthanide systems
may be different from those at 25 °C. For this reason, and because polynuclear
complexes are seldom formed in natural waters, owing to the low concentrations
of the lanthanide ions, the corresponding constants have been included only in
the cases reported in ref. (29).
1.2.2 Carbonate complexes.
In most natural waters, the carbonate complexes are accepted as the dominant
soluble species of the rare earths (1, 3, 11, 12, 16, 64). There seems to be
agreement about the speciation and the stability constants for the carbonate
complexation of the lanthanides. The bicarbonate complex and the various
carbonate complexes REE(CO3)n , n = 1 - 4, have been reported. The values
chosen in the database mainly rely on the measurements of Byrne and
coworkers (3, 58, 60, 61, 64), Lundqvist (52), Ciavatta et al. (50), Ferri et al. (53)
and Spahiu (56, 57). Since the position of yttrium in the lanthanide series varies
with the ligand, the experimental values of Spahiu (56, 57) for YHCO 3 2+ and
YCO 3 + were used to interpolate the value for Y(CO3)2' from data of Lee and
Byrne (64). The values reported by Chat (62) are in good agreement with the
accepted values.
Dumenceau and coworkers (54, 55) have reported constants for the
tetracarbonate complexes of the lanthanides, while Ferri (53) reports the tri and
tetracarbonate complex of Ce. The values given by Ferri (53) for the first and
second carbonate complex are higher than the values we have selected for Ce
and the neighbouring elements, even after accounting for the ionic strength
difference, while Wood (1) indicates shortcomings in the work of Dumenceau et
al. (55, 56). Thus the higher carbonate complexes (tri - and tetracarbonate)
were not considered, untill new experimental evidence becomes available. On
the other hand their importance would be limited in carbonate concentration and
pH ranges of most groundwaters.
Bernkopf (94) and Bidoglio and Marcandalli (130) propose mixed

hydroxocarbonate complexes of Eu, but the speciation schemes used in these
works seem problematic (1), and have not been confirmed in later studies.
Further experimental evidence is needed to confirm the existence of the mixed
complexes.
1.2.3 Phosphate complexes
The phosphate complexation of the REE has recently been studied by Byrne
and coworkers (85,86) and the species REEH2PO42+, REEHPO4 and
REE(HPO4)2 have been proposed. The species REEH2PO42+ seems to be well
established also in other works. Thus Rao et al. (83) report -log p1 = -1.61 for La
at 0.5 M NaCIO4, while Afonin and Pechurova (84) report -1.24 for Nd at * 0.7 M
(Na, H)CI. Borisov et al. (82) report for the same constant (at zero ionic
strength) -2.33 for Ce, -2.51 for Pm and -2.65 for Y.
8
The other species, GdHPO4+ and Gd(HPO4)2', have been directly measured
only for Gd (85), while the values for the other REE have been estimated by us
using linear free energy relationships and parameters reported in refs. (3) and
(86), in order to compare them with the values reported by Millero (2).
In a recent work on phosphate complexation of Gd and Ce (86), Byrne and
coworkers report stability constants for the complexes of GdPO4° and CePO4°
and linear free energy estimates for all LnPO4° and Ln(PO4)2"3 complexes. The
outcome of this work indicates that in previous works the stability of these
species have been overestimated by several orders of magnitude (87, 88)
[Mayer and Schwartz (81) propose a CePO4 constant of -18.5 instead of -11.35
estimated by Byrne et al.]. These species become more important for the heavy
lanthanides, as shown in the figures 1a, 1b. and 1c. In these figures the
speciation of La, Eu and Lu has been calculated with the present database for
soluble species (the precipitation of solids was suppressed) in a typical granitic
ground water. The total concentration of the various REE and of the ligands in
the granitic ground water [Allard (96)] were as given below:
2 REE 3 ** 2 10"7 M, I C O 3 2 ' = 1.8 10"3M, Z CI" = 1 10"3 M, Z SO4"2 = 1 10"4 M,

Z P = 5 10"5 M, S PO 4 3 = 2 10"6 M,
As seen from the diagrams, the carbonate complexation dominates the

speciation of REE in granitic groundwaters. This is in agreement with geological
information (14, 15) which link the REE mobility in uranium mineralisations to
the carbonate and exclude the importance of phosphate in this process.
Anyhow, for ratios of total carbonate/total phosphate lower than 100, the
phosphate complexes become dominant, especially for heavy REE. These
species have been included in the database, but since they are obtained from
only one measurement for Gd (the value for the Ce complex is estimated from
linear free energy relationships, the measured one is considered unreliable by
the authors), the values of these phosphate complexes are given in italics in the
tables 1-16.
1.0 r . La(QH) 3
0. 0
Fig 1a. Aqueous speciation of lanthanum in granitic ground water
calculated with the data selected in the present work.
i.O Eu(DH)3
o.o L
Fig 1b. Speciation of europium calculated with data from this work.
10
[C03-2]TOT= 1 . 8 0 mM [Cl-]TOr= l . D O mM
[l_u + 3 ] T Q T = D . Q 2M M [F-]T0T= 5Q.DD pM
Lu(0H) 3
Lu(C0 3 .' " —
0.0
Fig. 1c. Speciation of lutetium in groundwater, calculated with the present
database.
1.2.4. Sulfate and fluoride complexes.
Considerable effort has been devoted to the study of the sulfate complexation of
the REE [e. g. 108-112; more complete reference list in (1)]. Wood (1) selects
the values of Powell (112), while most of Millero's (2) primary data are those of
Choppin and coworkers (110), and the values from different sources seem to be
in reasonable agreement. No recent measurements were considered and the
values in the tables were extracted from the reports mentioned above.
Fluoride complexes also seem to be well determined and their importance
increases in the acidic range, especially for natural waters with high fluoride
11
content. The values of the higher fluoride complexes are less certain and were
included only for some elements, mostly as reported by Wood (1).
1.2.5 Chloride, nitrate and other solution species
The complexes of REE with chloride and nitrate are weak (114-120), generally
outer sphere complexes and the studies on these systems are in fair
agreement. Wood accepts the values of Mironov (117), which are in fair
agreement with the values reported in the two other sources (2,3). The same
holds for the nitrate complexes. No recent measurements were considered for
these complexes and the values were selected based on the reports already
mentioned (1,2,3).
There are indications that the complexation of the REE with geochemically
important organic ligands is strong (131, 132, 12,13), but very few reliable data
are available. Thus only the values of fulvic and humic acid complexes for Eu
have been included in this work as tentative ones.
12
1.3. Solid phases.
A number of sparingly soluble solid phases are formed by the REE. The most
important as potential solubility limiting solids in many natural systems include
hydroxides, carbonates, hydroxycarbonates, fluorocarbonates, fluorides and
phosphates. In spite of their importance, very few data exist in literature and for
important systems as hydroxydes, carbonates and fluorides the agreement
between the results of different researchers is poor, often spanning several
orders of magnitude. In this context, we agree with the statement by Wood(1)
"The major missing piece of information which prevents the modeling of such
chemical dispersion processes at the present time is accurate solubility products
for the most common primary and secondary REE-bearing phases such as
bastnaesite, monazite, allanite etc."
The REE form amorphus hydroxides which may incorporate substantial

quantities of anions present in the system as in the case of hydroxychlorides,
but with aging the solubility often drops several orders of magnitude and the
solid phase is transformed to normal hydroxide (48). The same holds for
carbonates, which can form hydroxyl carbonates or fluorocarbonates,
accompanied with changes in the solubility. On the other hand for solid
phosphates (89) or fluorides (5, 10) of REE, slow hydration equilibria influence
the solubility. These possible phase changes during the measurements,
together with other factors discussed in the following paragraphs, may explain
the scatter in the reported solubility products.
Only in a few recent studies a careful characterisation of the solid phase before
and after the experiment has been performed. On the other hand the
importance of americium in nuclear waste management has resulted in a
considerable effort in the study of its chemistry in the last years. In many cases
recent results on americium show much lower solubilities than accepted
13
previously, thus the comparison of e. g. Nd solubilities with recent data on Am
has been taken into account in selecting the solid phase data.
1.3.1 Solubility of the oxides and hydroxides
The oxides of REE are easily hydrated and quite soluble in water to be the
solubility limiting solids. The data for the solubility of the oxides, that is for the
reaction:
REE2O3(s) + 6 H+ ^ 2 REE3* + 3H2O

were calculated from AG{0(Ln203) values as reported in ref.(19) and based in
ref.(17,18), considered the most reliable ones and from AGf°(REE3+) for aqua
ions of Morss(21), using CODATA values for water.
The values of the solubilities for the amorphous hydroxides are based on data
of Kragten and Denkop-Weever (30-37) for freshly precipitated hydroxides, after
extrapolation to zero ionic strength.
The data of Baes and Mesmer for the solubility of the hydroxides have been
reported as a summary of the previous work in the tables. They based their
estimations in the data of Akselrud (48) for aged precipitates (more than 150
days). Anyhow, recent measurements on well characterized crystalline
neodymium hydroxide (46) or on europium hydroxide (94) and americium
hydroxide (47, 49) report lower solubilities. The correlation of the a parameter of
the unit cell and the solubility product, used by Baes and Mesmer(29), does not
seem reliable in the case of Eu, when the experimental value (48) seems to be
in better agreement with more recent results (94) than the estimated one.
Furthermore, a common feature of the few validations of REE thermodynamic
databases are the larger solubilities calculated e.g. in Nd-glass dissolution tests
(74) than the ones measured. Thus Rai and coworkers (74) propose that the
solubility of Nd(OH)3(s) glass) of the same magnitude as that reported by
Bernkopf (94) for Am (-28.9) to explain their solubility data. This value is even
14
lower than the one measured by Silva (46) for the corresponding crystalline
solid (-26.2).
28 -
26 -
24
x" /
o
LLT 22 - ^
LU
a:
20 -
-^-Selected
a Baes and Mesmer(29)
18 - o Axdrud(48)
T Silva(46) for Nd(OH)3(c), Bemkopf(94) for Eu
16 1 1 f 1 1 1 1 I 1 1 1 1 1 1 t
LaCePrNdPmSmEuGdTbDyHo&TmYbLu Y
Fig. 2. Solubility products of REE hydroxides.
The solubilities reported by Baes and Mesmer (29) are recomended for the
other REE solid hydroxides (fig. 2). It is difficult to predict the solubility products
of the crystalline hydroxides without having new experimental evidence, so only
the value of Silva (46) for Nd has been selected.
1.3.2 Solubility of the carbonates and hydroxycarbonates.
Solid REE carbonates and hydroxocarbonates have been proposed (11,12) to

be solubility limiting in natural waters. However, the experimental data
concerning the solubility of REE carbonates and hydroxycarbonates are quite
scattered. There are several reasons for this scattering.
As already mentioned, a carefull characterization of the solid phase before and
after the solubility measurements is very important because of the possible
15
phase transformations. It is not straightforward to predict which solid phase is
stable at 25 °C and a given set of conditions in the REE3* - CO2(g) - H2O
system. In the following, a summary of the chemical and geochemical literature
concerning this problem is given.
Caro and coworkers (67,122) have measured solubilities and identified solid
phases in the REE2O3(s)-CO2(g)-H2O system. Normal carbonates of the type
REE2(CO3)3 nH2O with n=8 for La through Nd, n=3 for Sm through Tm and Y,
n=6 for Yb and Lu were identified by equilibrating the corresponding hydroxides
with 1 atm. CO2(g). The reaction kinetics is slow for oxides and oxycarbonates
obtained through thermal decomposition of oxalates, but rapid and complete for
hydroxydes. This is expected following the discussion of the reaction kinetics of
the CO 2 attachment to hydroxides as given in ref. (133). The difficulties caused
by the influence of very fine particles(under 1 |im), especially for the amorphous
carbonates (Yb, Lu), in the solubility measurements have been stressed.
In another work of Caro et al. (68), the phases formed at lower partial pressures
of CO2(g) and room temperature have been studied. The results are that the
hydroxides transform to normal carbonates for P C 0 2 > 0.1 atm., while at the
P CO2 of air (3 10"4 atm.) the hydroxides of La through Eu give well crystallized
phases with ratios C0 2 /Ln 2 0 3 near 2, that is hydroxycarbonates. For Gd
through Lu this ratio is between 1 and 1.5, the solids are amorphous and the
results hardly reproducible. The normal carbonates are stable for P CO2 > 0.01
atm., but in air hydrolyze rapidly for Pr and Nd (24 hours) or slowly for Sm and
Eu (8 days) to form hydroxycarbonates Ln(OH)CO3, similar to those obtained
from the hydroxides at the P C 0 2 of air. The carbonates of Gd through Lu and
also of La are very resistant to the hydrolysis and after several weeks the X-ray
spectra are only slightly altered (enlargement of lines), while the ratio
CO 2 /Ln 2 O 3 is near 2.8. The prolonged hydrolysis of the carbonates of Pr
through Eu in argon atmosphere permits to lower the ratio C0 2 /Ln 2 0 3 to 2.3 till
1, but the hydrolysis product has essentially the same X-ray diffraction pattern,
16
This is explained by the authors by the formation of a nonstoichiometric phase
of the composition Ln2(CO3)x(OH)2(3.X) nH2O. In argon atmosphere the
carbonates of Gd through Lu, including that of La, behave like in air.
Even though no solubility products of the hydroxycarbonates are reported in this
study, we have given the results in some detail to show the complexity of the
system.
In the geochemical literature, the interest in the hydroxycarbonates is connected

with the importance of the mineral bastnaesite, LnCO3F(s), which is analogous
to the hydroxycarbonate (the corresponding mineral is named hydroxyl-
bastnaesite). Minerals with high coordination numbers (10-12) are LREE
selective, while those with low coordination number (6) are HREE selective. The
coordination number of REE in bastnaesite is 11. Thus Williams-Jones and
Wood (80) conclude that apparently high contents of HREE and Y in
bastnaesite represent intergrowths and inclusions of other minerals.
Furthermore, attempts to synthesize bastnaesite analogues containing HREE's
have not been successful. This agrees with the results of Caro and coworkers
(68), that the hydroxycarbonates are formed easier for the light REE.
The most studied hydroxyl-bastnaesite has been Nd(OH)CO3, while limited
hydrothermal synthesis studies have been carried out on those of La, Gd, Pr, Er
and Y (78, 79, 124, 125). From these studies it follows that the T-XCO2 stability
field of hydroxyl-bastnaesite decreases with decreasing ionic radius of the REE
and Y. From the study of Wakita and Kinoshita (88) it follows that the hydroxyl-
bastnaesite of La is synthesized at atmospheric pressure in air over 65 °C, while
normal carbonate (lanthanite) forms at lower temperatures. Tareen and
Kutty(87) find that for X CO2 =0.01 and below 250 °C Gd2(CO3)3. 2H2O is
synthesized in the Gd-CO2-H2O system at 1.5 kbar, while the hydroxycarbonate
is stable over this temperature.
Owing to the similarity with americium, the Eu and Nd solid carbonates and
hydroxy carbonates have been extensively studied in the last years. Thus the
17
hydroxy carbonate solubility products have been reported only for these
systems for which direct experimental data exist, while for the rest of the REE
only the values for the normal carbonate have been reported. Very possibly in
repository conditions the hydroxycarbonates of Ce, Pr and Pm form and as a
crude approximation the values given for Nd and Eu can be used, while for the
rest of the REE further experimental evidence is preferred. The values reported
for Nd and Eu are based on the measurements of Kim and coworkers (71, 72),
accompanied by a complete characterization of the solid phases using X-ray,
FTIR and DTA. The data of Bernkopf (94) for Eu those of Rai et al. (74) for Nd
have also been considered, while data of Silva and Nitsche (127), Felmy et al.
(70) on Am have been used for comparison with Nd. Runde et al. (72) report for
both Nd and Eu the formation of normal carbonate for PCO2 = 1 atm and 0.01
atm., while the Ln(OH)CO3(s) forms at P c 0 2 of air (0.0003 atm.). Carroll (77)
claims the formation of the hydroxycarbonate of Nd at 0.1 and 1 atm. CO2(g) for
long equilibration times, which seems in discordance with all previous
information.
The solubility products of the normal carbonates are reported for the reaction:
REE2(CO3)3(s) ^ 2 REE3* + 3 CO 3 2
which involves high charge ions and depends strongly on activity coefficient
estimation. Thus already the pure electrostatic contribution accounted for by the
Debye-Huckel term gives around 3 logarithmic units difference between the
constant measured at 0.1 M and the value at zero ionic strength. The carbonic
acid dissociation equilibria also influence in the values of the reported
constants, since the dissolution equilibrium which is measured experimentally in
the presence of carbon dioxide is
REE2(CO3)3(s) + 6 H+ ^ 2 REE3* + 3 CO2(g)+ 3 H2O
and has to be combined with the constants of the carbonic acid dissociation to
derive the constant for the solubility.
18
The most complete set of measurements of the REE normal carbonates are
those of Firshing and Mohammadzadel (69) and Jordanov and Havezov (66). In
both these studies no characterization of the solid phase after equilibration has
been performed and the carbonate complexes at equilibrium pH 4.8-6.15 in
(69), and 4.76-5.75 in solutions saturated with CO2(g) or 7.55-8.16 in presence
of bicarbonate in (66), have been neglected. This would result in both cases in
higher solubility products than the true ones. Thus Choppin (12) recalculates a
value of -35.3 for Nd carbonate accounting for carbonate complexation from
data in (69) instead of -34.1 reported by the authors. While in (66) a regular
increase of solubility is observed from La to Yb and Y, in (69) the behaviour is
much different (see fig. 3). It is evident that higher solubilities in (69) are
observed in the cases of the higher equilibrium pH (for La and Er) showing the
influence of carbonate complexes. On the other hand the partial dissolution of
solid carbonates with 10 mM perchloric acid may cause losses of CO2(g) at the
initial stages of the experiment, while latter, CO2(g) from air may have been
absorbed (Pco2 ' s substantially lower than that of air in their equilibrium
solutions, even assuming no losses of CO2). This is most possible during the
manipulations in the three months period of equilibration. Another point which
makes difficult recalculations in this case is the possibility of phase changes due
to the low partial pressure of CO2(g) and the long equilibration time.
In the studies of Grenthe et al. (73) for Y and Gamsjager (76) for La, the Pitzer
approach has been used with excellent results to describe the ionic strength
influence on the solubility product of REE carbonates. Since proper
characterization of the solid phase together with controlled conditions as Pco2
pressure and carbonate complexation were used in the studies of Ferri et al.(53)
for Ce, Ciavatta et al. (50) for La, Meinrath and Kim for Nd (71) and Runde et al.
(72) for Nd and Eu, we have used the Pitzer approach to obtain the
thermodynamic solubility products of these carbonates (fig. 3). These values
19
were used as reference ones to estimate the solubility products of the other
lanthanide carbonates.
For the REE Gd through Lu, the values of the solubility products were selected
on the basis of the recalculated values of Jordanov and Havezov (66)
potentiometric data in the presence of 1 atm. CO2(g). From the results of Caro
et al. (68) this should assure the stability of the normal carbonates. The data
were recalculated using mixed activity-concentration constants for the carbonic
acid and assuming a liquid junction potential of 0.08 pH units for 0.1 M NaCIO4,
then were extrapolated to zero ionic strength using the same method as for La
andY.
—o—-Selected
O Rrshing, Moharrmadzadel(69)
38- • Jonianov, Havezov(66)
o T Pitzer cala of (76,53,71,72,73)
• Recalculated data from (66)
O Chopping), Bemkopf(94)
36-
9 B •
34- o
o o
o
32- o
D o o o
•
J Q.
30- o
28- o
i i 1 1 1 i t I 1 1 1 1 1 1 1 1 I
LaCePr NdPmSmEuGdTbDyHo&TmYbLu Y
Fig 3. Solubility products of REE normal carbonates
Besides much higher solubilities of carbonates of REE, (e. g. in Rard (5) for Eu
from old values which the same author (51) has corrected later), also some
much lower ones have been reported. Bernkopf (94), measured the solubility of
Eu carbonate in a pH region where complexes form, assuming mixed
20
hydroxocarbonate complexes. As discussed above, this speciation scheme is
not confirmed in later studies, and this may explain the low solubility product
deduced together with the constants for the complexes. In Chemval 5 database
a value of -41.6 is calculated from data of Shiloh et al. (127) for americium
carbonate, measured at variable moderate ionic strengths and high carbonate
concentrations, together with improper speciation (128). Choppin (12) recently
reports -37.9 for Nd carbonate in sea water, but this is probably a sign error in
the activity coefficient calculations, since all experimental studies show an
increase of the solubility with ionic strength.
Double solid carbonates as NaCe(CO3)2(s), which are reported (53) to form at

high sodium concentrations, were not considered relevant for the present
applications.
It is clear that owing to the importance of carbonates and hydroxy carbonates as

potential solubility limiting solids, more experimental data are highly needed for
these systems. The solubilities of at least two HREE carbonates from over and
undersaturation, at well controlled ionic strengths, with a careful characterization
of the solid phases before and after equilibration and known partial pressure of
CO 2 should be performed to fully understand these systems.
1.3. 3 Solubility of phosphates
In nature the LREE commonly occur as the phosphate mineral monazite, while
the HREE and yttrium form the phosphate mineral xenotime, with similar
composition, but different coordination of the cation. Monazite type minerals are
usually formed under hydrothermal conditions. However, recent studies in
Belgium indicate the formation of monazites at low temperatures. Rare earth
phosphate phases are very insoluble, therefore it is likely that one or more such
phases control the concentrations of the REE in natural systems.
21
The data in the tables are based mainly in the work of Jonasson et al. (89) on
the solubilities of the hydrated phosphate phase of La, Pr, Nd and Er, measured
at 25 and 100 °C. The solid phase LnPO4 xH2O was produced in reflux for 24
hours and may have a better crystallinity than the corresponding amorphous
phases (see discussion in test cases). There seems to be a reasonable
agreement between their data and other measurements reported (74, 90, 91).
The change in the logarithm of the solubility product from La (log Ks0= - 24.5) to
Er (-24.18) seems to be small. Rai et al. (74) report log Ks0= -24.45 for Nd,
which compares well with our estimates of log Ks0= -24.6 for Nd and log Ks0=
-24.7 for Pr. These estimates have been made from data at 100 °C in (89),
assuming the same temperature dependence in solubility as for Er (log Ks0(100)
- log Ks0(25) s -1.3). Jonasson et al. (89) compare their measurements with
those of Tananaev and coworkers (90, 91), accounting for the ionic strength
differences and estimate log Ks0= -25.3 for La and log Ks0= -25.1 for Gd. A
regular linear increase of the cell parameters of the monazite type phosphates
of La through Gd with the ionic radius of the REE has been reported (93). This
may explain the small and regular increase in the solubility products noted in
(89). This allowed us to assume a linear correlation to interpolate the values of
the solubility products for all REE phosphates reported in the tables.
1.3.4. Other solids.
There are data on the solubilities of chlorides and bromides(10), sulfates (113),
nitrates (121) and iodates of the REE, but we considered them not relevant for
safety assessment reasons, due to their high solubility.
Rare earth fluorides are quite insoluble and precipitate from aqueous media as the
hemihydrates, REEF 3 0.5 H2O(s). The data on the solubility of REE fluorides are
quite spread, with solubility products ranging from log Ks0 = -14 to -29. Even in the
same study (106) the solubility product for the same element, measured with three
22
different methods differs more than two orders of magnitude. The values of the
solubility product of LaF3(s) obtained with fluoride ion-selective electrodes,
constructed from lanthanum trifluoride result extremely low (-24 to -29) and
scattered. This is due to aging and hydration effects in the electrode monocrystal
(5), and these data were not considered in the selection. The available literature
data, together with the selected values are shown in fig. 4. From the selected
values and the typical fluoride concentrations in ground waters, it follows that the
importance of fluorides as potential solubility limiting solids is small as compared to
other solids (e.g. phosphates or hydroxycarbonates).
25
20 a g D
-B-
o
15
uT —•—- Selected
UJ a Ref(101), stoichiometric
B 10 o Ref(101), therrrocherrical
A Ref(102)
V Ref(103)
Q. o Ref. (104)
5 + Ref. (9) for Ce,Y; Ref. [105] for La, Eu
X Ref. [106] for Eu, [107] for Tb
UCePrNdPrnSmEuGdlbDyHoErTmYbLu Y
Fig. 4. Literature data and selected values for the solubility product
of REE fluorides.
William-Jones and Wood (80) mention a variety of low solubility mineral phases
such as bastnaesite and its solid solutions with calcite as parisite, synchisite,
roentgenite or oxycarbonates etc, but no solubility data were found for them in the
literature.
23
1.4 Data tables
All data correspond to 25 °C and data from all sources have been converted in EQ 3/6
format using CODATA key values. The values of the constants as reported in literature
are shown with the reference number followed by a star, when this value does not
correspond to the standard state (l*0). When the value of the constant for a given
reaction has been estimated by us from literature values, it is included in square brackets.
The values of some of the selected constants are given in italics when we consider that
they need further confirmation. In all this work the values of the constants correspond to
the reaction as written in the tables. Tables for Eu and Sm are given before, since there
are some data (given in the first column) for these elements in the EQ 3/6 and in the
Hatches (HARPHRQ) databases .
Table 1. Europium solution species.
logK logK logK logK Selec-

Reaction EQ3/6 Millero Wood L i t > (ref) ted.
Hat.(H)
EuOH2+- E u ^ + OH" -7.10 -5.83 -6.2 - 6 . 1 ( 3 ) , -6.2 < 2 9 ) , -6.4 (94 > -6.2
(H)
-6.2 -7.3 ( 3 3 ) ,-5.3 ( 3 4 > ,-5.7 ( 4 4 - s r )
Eu(OH) 2 + ^ Eu 3+ + 2OH" -13.12 - - -11.63 (3) ,-11.9 (M ' ) ) -11.6
-11.4 t29) ,11.9 (44 ' 1
Eu(OH) 3 - E u ^ + SOH" - - - -16.6^,-16.6lZ9) -16.8
17.1(94">
EuCCV^ Eu^ + CCV2 -8.13 -7.37 -8.00 - 8 . 0 ( 3 6 4 ) , -8.08 1 6 2 ', -7.9
-5.93(5r)
Eu(CO3)2" ^ Eu3* + 2CO 3 2 -13.52 -12.24 -12.96 -13.52 ( 3 ) ,-12.8 ( 6 2 ) -12.9
-13.4 ( 6 1 ' 6 4 ) , -10.7(52">
EuHCO 3 2 + - E u ^ + HCOg" - -1.60 -2.08 [-2.54] l64) -2.1
EuH2PO42+ - Eu3* + H2PO4- - -2.21 - [-2.82] l d ^ J -2.4
EuHPO4+ ^ Eu3* + HPO42" - -5.42 - [-5.95] lJ ' 00 ' -5.7
Eu(HPO4)2' ^ Eu3* + 2 HPO42" - -9.10 - [-10.0]lJ>BOJ -9.6
EuPO4 ^ Eu3+ + PC^3" - - -12.22 <3) -12.2
Eu(PO4)23- ~ Eu3* + 2 P O / - - -20.66 (3) -20.66
24
Table 1. Europium solution species, (continued)

Reaction EQ3/6 Millero Wood L i t .(ref) ted.
Hat.<H-)
E u S O 4 + ^ E u ^ +S O / 2 -3.58 -3.37 -3.67 -3.5
-3.67 ( H )
Eu(SO4)2 ^ Eu3+ + 2SO4-2 -5.13 - -5.42 -5.2
EuF+2 ^ Eu3+ + F" -3.35 -3.63 -4.24 -3.9
E u F 2 + ^ Eu3+ + 2F" -5.80 - -7.96 -6.9
E u F 3 - Eu3+ + 3F" -10.60 - - -10.6
E u C I + 2 ^ Eu3+ + CI" -0.38 -0.28 -0.34 -0.34
E u C I 2 + ^ Eu3+ + 2CI" 0.05 - - 0.05
EuBr2* - Eu 3+ + Br" -0.25 - - -0.25
EuBr 2 + ^ Eu 3+ + 2Br" 0.09 - - 0.09
EuNO 3 + 2 ^ E u ^ + NCV -0.65 -0.83 -1.23 -0.8
EuBrO3+2 ^ Eu 3 * + Br" + 1.5 O2(g) 17.21 - - 17.21
EulO3+2 ^ Eu 3+ + I" + 1.5 O2(g) -15.18 - - -15.18
Eu(HumAc)2+ ^ Eu 3+ + HumAc" - - -13.3

-13.3 (H)
Eu(HumAc)2+ ^ Eu 3 * + 2 HumAc" - - -14.6
(H)
-14.6
Eu(FulAc)2+ ^ Eu 3+ + FulAc" - - -6.49
-6.49 (H)
Eu(FulAc)2+ ^ Eu3+ + 2FulAc" - - -10.5
-10.5 (H)
Eu(ll)
Eu +3 + 0.5 H2O ^ Eu2+ + H + + 0.25O2(g) 26.68 - - 26.69126', 25.56(21) 26.68
25
Table 1.2. Europium solids.
Reaction logK logK logK Selec-

EQ36 Hatch. Lit.(ref.) ted.
Eu(s)
Eu(s) + 3H + + 0.75 O2(g) - Eu3+ + 1.5 H2O 163.27 163.23 162.96(26) 163.2
162.88(21)
Eu(lll)
E u ( O H ) 3 ( s ) ^ E u - + 3OH- -26.39 -24.5 -24.5 ( 2 9 ) -26.9

-26.54 (48) , -27.2 ( 9 4 )
Eu2O3(cubic) + 6H + ^ 2 Eu3* + 3 H2O 52.39 52.4 52.4
Eu2O3(monoclinic) + 6H + ^ 2 Eu3* + 3 H2O 54.00 54.01 54.08 (1S) 54.0
Eu2(CO3)3-3H2O(s) ^ 2Eu3+ + 3CO32" + 3H2O -26.59 -26.58 -35.03 (69) ,-34.64 (9< ' ) -35.0
(51) (7:! >
-32.46 ,-31.78 '
Eu(OH)CO3(s) ^ Eu 3+ + OH+CO32- - - -20.49-V20.18-> -21.8
EuPO4xH2O(s) ^ Eu3+ + PO42" + x H2O - - [-24.4] (B9 -' 4) -24.4
Eu2(SO4)3-8H2O(s) ^ 2Eu3+ + 3SO42" + 8H2O -10.20 -10.18 -10.2
EuF30.5H2O(s) - Eu3* + 3F" + 0.5H2O -16.21 -16.21 -17.2

-18.9 (102) ! -15.4 (103)
-21.9(1O4),-16.7(1D5)
EuCI3-6H2O(s) ^ Eu3* + 3CI" 5.21 5.22 5.2
EuOCI (s) + 2H + ^ Eu3+ + H2O + CI" 15.81 15.82 15.81
Eu(OH)2CI (s) ^ Eu3* + 2OH" + Cl" -18.87 -18.87 -18.87
Eu(OH)2.5CI05 (s) ^ Eu3* + 2.5 OH' + 0.5 CI" -22.11 -22.11 -22.11
EuBr3 (s) ^ Eu3* + 3Br" 30.19 30.19 30.19
Eu(NO3 )3-6H2O(s) ^ Eu3* + 3NO3-+ 6H2O 1.84 1.85 1.84
Eu(IO3)3-2H2O(s) ^ Eu3++ 3r+2H2O+4.5O2(g) -51.39 -51.11 -51.4
Eu(ll)
Eu3O4(s) + 9H + + 0.25O2(g) - Eu3* + 4.5H2O 114.74 114.73 114.74
EuO(s) + 3H + + 0.25O2(g) ^ Eu3* + 1.5H2O 64.57 -64.56 64.57
EuSO4(s)+H++0.25O2(gFEu3++SO42-+0.5H2O 18.26 -18.25 18.26
EuS(s) +2H++0.25O2(g) ^ E u ^ HS>0.5H2O 41.99 41.97 41.98
EuCI2(s)+ H++0.25O2(g) - Eu3++2CI> 0.5H2O 31.99 -31.98 31.99
26
Table 2. Lanthanum solution species.

Reaction EQ3or Wood Mill. Lit .(ref.) ted.
Hatch.< H '
L a O H 2 ^ ^ La 3+ + O H ' -5.5^ P) -5.5 -5.10 -5.34 (3) -5.4
-5.2 ( 3 r ) ,
-7.6 (40)
L a ( O H ) 2 + ^ La 3+ + 2OH" - - - -9.86(J) -9.8
-9.7<37*'
L a ( O H ) 3 ^ La 3+ + 3OH" - - -14.1(3) -14.0
-14.04 137 "'
La 2 (OH) 2 4 + - 2 La 3 * + 2 OH" -5.0< H) - - >-10.5(29) -5.0
LasCOH)^ ^ 5La 3+ + 9 O H ' -54.8 lH) - - -54.8129' -54.8
L a C O 3 + ^ La 3+ + C O 3 2 [-7.42] -6.82 -7.1213'64' -7.3

-7.78 (50)
-7.74120'
La(CO 3 ) 2 ' ^ La 3+ + 2CO 3 ' 2 - [-12.0] -11.31 -11.59' J ' -11.8
-12.0 (64)
LaHCO 3 2 + ^ La 3 * + HCOg" - [-2.5] -2.02 -2.5150' -2.3
[-2.46](64)
LaH 2 PO 4 2 + ^ La 3 * + H2PO4" - - -2.50 [-2.42]!B63) -2.5
-1.61' 83 " 1
LaHPO 4 + ^ La 3+ + HPO 4 " 2 - - -4.87 [-5.27] 1863 ' -5.1
La(HPO 4 ) 2 " ^ La 3+ + 2 HPO 4 ' 2 - - -8.17 [-8.61 ] ( 8 6 3 ' -8.4
LaPO 4 ^ La 3+ + PO4"3 - - - -10.96 lJ ' -10.96
La(PO 4 ) 2 3 " ^ La 3+ + 2 P O 4 3 - - - -17.63^ -17.6
L a S O 4 + ^ L a ^ + SO 4 " 2 - -3.62 -3.21 -0.8 (20> -3.4
La(SO 4 ) 2 ^ L a ^ + 2SO 4 " 2 - -5.29 - -1.0 ( 2 0 ) -5.1
L a F 2 + ^ La 3+ + F~ - •3.72 ^3.12 -2.02 ( 2 0 ) -3.4
LaF 2 + ^ L a ^ + 2 F" - -6.84 - -6.2
LaF 3 ^ La 3 * + 3 F" - •10.20 - -10.2
L a C l 2 + ^ L a ^ + CI" - -0.48 •0.29 -0.64 ( 2 0 ) -0.38
LaNO 3 + ^ La 3 * + NO 3 " - [-1.1] -0.58 -0.8
La(ll)
La+3 + 0.5 H2O ^ La2+ + H+ + 0.25O2(g) - 73.2 (21) 73.2

23
8 4.0( )
27
Table 2.1. Lanthanum solids.
logK logK Selec-

Reaction EQ36 Literature*"*) ted.
Hat.' H)
La(s)
La(s) + 3H + + 0.75 O2(g) - La3* + 1.5 H2O - 182.5< 21 > 182.5
La(lll)
La(OH)3(am) ^ La3+ + 3OH" - -22.48' 20 ', [-18.5]<37> -18.5
La(OH)3(s) ^ La3+ + 3OH' -20.7' H ) -21.7 ( 2 9 ) ,-21.05' 2 0 ' -21.7
La2O3(c, hex.) + 6H + - 2 La3* + 3 H2O - 66.23 ( 2 0 ) , 66.13 ( 1 9 ) 66.2
La2(CO3)3-8H2O(s) ^ 2La3+ + 3CO32- + 8H2O -33.4' H ) -35.25 l ' 0 \[-35.45] V0O ' /Jl " >J -35.3
-29.91 ( 6 9 ) , -32.6 ( 2 0 ) ,
-33.4 (66) , [-35.2] (66)
La(OH)CO3(s) ^ La 3+ + OH+CO32- - - -
LaPO4 x H2O(s) ^ La3* + P O / + x H2O - -24.5âj -24.7

.25.3(90.89)
LaF3 0.5 H2O(s) ^ L a ^ 3 F" + 0.5 H2O -is.g^'.ô.^101', -18.7

-20.5 (102 ),-17.1 (l03) ,
-18.7(104),-18.5(105)
LaCI3(s) ^ La 3 + +3CI" - 14.43120' 14.4
LaCI3-7H2O(s) ^ La3+ + 3CI" + 7H2O - 4.73120' 4.7
28
Table 3. Cerium solution species.
Reaction logK logK logK logK Selec-

Lee&By. ref
Wood Mill. Lit.< > ted.
+ 3+
CeOH2 ^ Ce + OH" -5.59 -5.7 -5.60 -5.7 ( 2 9 ) -5.65
_5.7(3o-)
+ 3+
Ce(OH)2 ^ Ce + 2OH" -10.40 - - -lO^29' -10.4
-11.3(30-)
Ce(OH)3 ^ Ce3+ + 3OH" -14.77 - - -14.8<29> -14.8

-14.9(30')
Ce3(OH)54+ ~ ZCe^ + 5OH" - - - -36.5< 29 > -36.5
CeCO3+ - Ce3* + CO 3 2 -7.40 -7.56 -6.95 -8 4(53) -7.5

_7.4<«>
Ce(CO3)2' ^ Ce3* + 2CO 3 2 -12.18 -12.19 -11.50 -13.7^' -12.5

-12.63 (64)
CeHCO32+ ^ Ce3* + HCCV - -2.42 -1.95 -1.49 1 * 8 '' -2.2
[-2.461(64)
CeH2PO42+ ^ Ce3* + H2PO4' - - -2.43 [-2.56r'3) -2.5
.233,82,
CeHPO4+ ^ Ce3+ + HPO 4 2 - - -4.98 [-5.5] (86 ' 3> -5.2
Ce(HPO4)2" ^ Ce3+ + 2 HPO 4 2 - - -8.34 [-9.1] l863) -8.7
CePO4 ^ Ce3+ + PO4"3 -11.35 - - -11.73 iab) •11.35

-18.53 (81)
CeCPOJg3" ^ Ce3+ + 2 PO4"3 -18.48 - - -15.7186'* -18.5
CeSO4+ ^ Ce3+ + SO4"2 - [-3.62] -3.29 -3.4
CeF2+ ^ C e ^ + F" - -3.86 -3.28 -3.6
CeF2+ ^ Ce3+ + 2 F' -7.30 - [-6.4] 11 -"' -6.4
CeCI2+ ^ Ce3* + CI" - -0.47 -0.31 -0.4
CeNO3+ ^ Ce3+ + NO 3 ' - -1.13 -0.69 -0.9
Ce(IV)
Ce3+ + H + + 0.25 O2(g) ^ C e ^ 0.5 H2O - - - -8.64< 25 > -8.64

-8.97< 2 1 )
CeOH3* ^ C e ^ OH" -15.2(29'f -17.2
-14.5 ( 9 5 )
-19.2 ( 2 1 )
Ce(OH)22+ ^ Ce4+ + 2OH" - - - -28.5 1 2 9 "' -30.0
-30 ( 9 5 )
Ce2(OH)26+ ^ 2Ce4+ + 2OH- - - - -31.8 1 2 9 "' -31.0
-31(95)
Ce(ll)
Ce+3 + 0.5 H2O ^ Ce 2+ + H+ + 0.25 O2(g) - 76.6(23) 84.4

84.4(2D
29
Table 3.1. Cerium solids.
Reaction logK Selec-

Literature<ref) ted.
Ce(s)
Ce(s) + 3H + + 0.75 O2(g) ^ Ce3* + 1.5 H2O 180.7 (21) 180.7
Ce(lll)
Ce(OH)3(am) ~ Ce3* + 3OH" -21.24(30'>, -20.8
Ce(OH) 3 (s)^ Ce 3+ + 3OH' -22.1<29>, -22.1
Ce2O3(c, hex., a) + 6H + ^ 2 Ce3+ + 3 H2O 62.3 (19) 62.3
Ce2(CO3)3-8H2O(s) ^ 2Ce3+ + 3CO32" + 8H2O -35.55 (53) , -35.24 (53 - 73 - 76) -35.1
Ce(OH)CO3(s) ^ Ce 3+ + OH+ CO32- - -
CePO4 x H2O ^ Ce3* + PO43- + x H2O -21.3< 92 ->,[-24.6f 9 - 74 ' -24.6
CeF3 0.5 H2O ^ Ce3+ + 3 F + 0.5 H2O -18.8
Ce(IV)
CeO 2 (c) + 4 H + ^ C e ^ + 2 H 2 O -8.16 (17>29) -8.16
Ce 3 (PO 4 ) 4 (s) ^ Ce 4 * + 3 PO4*" -90.1<92*> -90.1
30
Table 4. Samarium solution species.

Hatches Wood Mill. Lit .(ref.) ted.
SmOH2+^ Srcv^ + OH" -6.1 -6.1 -5.81 -6.04 ( 3 ) , -6.1
-6 4 ( 3 n
-4.97'45"1
Sm(OH) 2 + ^ Sm3+ + 2OH" [-11.51" -11.5 13 ',- -11.5
12.8 ( 3 r )
-11.9< <r)
Sm(OH) 3 ^ Sm 3+ + 3OH" - [•16.1] m - -16.09 (3) -16.1
-18.6l3n
Sm(OH)4 ^ Sm3+ + 4OH" - - - -19.0 135 "' -19.1
[-19.11(29)
S m C C V ^ Sm3+ + CO 3 2 - [-7.92] -7.30 -7.93 ? 3 ) -7.8
-7.88 ( 6 4 )
Sm(CO3)2" - Sm3+ + 2CO 3 2 - [-12.81] -12.11 . , 3.37(3. 64) -12.8
SmHCO32+ ^ Sm3* + HCO3" - [-2.12] -1.75 [-2.52] (64 > -2.1
SmH2PO42+ ^ Sm3+ + H2PO4" - - -2.23 f.2.79](3.86) -2.35
SmHPO4+ - Sm3+ + HPO 4 2 - - -5.35 [-5.9]<3-86' -5.6
Sm(HPO4)2- ^ Sm3* + 2 HPO 4 2 - - -8.96 [-g.gp86) -9.4
S m P O 4 ^ Sm3* + PO 4 3 - - - -12.11 ( 3 ) -12.1
Sm(PO4)23" - Sm3* + 2 PO4"3 - - - -20.42 (3) -20.4
S m S O 4 + ^ Sm3+ + SO4~2 -3.54 -3.66 -3.28 -3.5
Sm(SO 4 ) 2 - Sm3* + 2SO4"2 - -5.24 - -5.2
SmF2+ ^ Sm3+ + F' - -4.17 -3.58 -3.8
S m C I 2 + - Sm3+ + CI" - -0.48 -0.30 -0.4
SmNO3+ ^ Sm3+ + N0 3 " - [-1.2] -0.78 -0.9
Sm(ll)
S m ^ + 0.5 H2O ^ Sm2++ H+ + 0.25O2(g) - ~ — 47.0(23) 47.2

47.2<21'
31
Table 4.1. Samarium solids.
Reaction logK logK Selec-

Hatches Literature(ref) ted.
Sm(s)
Sm(s) + 3H + + 0.75 O2(g) ^ Sm3+ + 1.5 H2O - 178.8 ( 2 1 ) 178.8
Sm(lll)
Sm(OH) 3 (am)^ S m ^ + 301-r - -23.84< 3r >, -23.4
Sm(OH)3(s) ^ Sm3+ + 3OH" -25.5 -25.5 ( 2 9 ) , -25.5
Sm2O3(c, mon.) + 6H + ^ 2 Sm3+ + 3 H2O - 42.9(19>, 42.9
Sm2(CO3)3 ^ 2 Sm3+ + 3 CO32' -26.75 -34.4 (69) , -32.5 l66) -34.5
Sm(OH)CO3(s) ^ Sm3+ + OH+ CO32" - - -
SmPO4 x H2O (s) ^ Sm3* + PO43" + x H2O - [-24.5] ( 8 9 ' 9 1 ' 9 2 J 4 ) -24.5
SmF3 0.5 H2O (s) ^ Sm3+ + 3 P + 0.5 H2O - -17 9 (101) -19 3 (101) -17.5
-19.0 002) !-16.0 (103)
Sm2(SO4)3(s) ^ 2 Sm3* + 3 SO42' -9.8 -9.8
32
Table 5. Praseodymium solution species.

ref
Lee&By. Wood Mill. Lit.< -> ted.
P r O H 2 + ^ Pr^ + OH" -5.73 -5.9 -5.60 -5.9 (29) -5.8
Pr(OH) 2 + - Pr3+ + 2OH" -10.73 - - [-11.0f9) -10.8
Pr(OH) 3 ^ Pr^ + SOH" -15.37 - - [-15.6f9) -15.4
PrCO 3 + ^ P ^ + COa2 -7.57 [-7.65] -7.03 -7.56 (M) -7.55
Pr(CO3)2" ^ Pr3* + 2CO3"2 -12.54 [-12.35] -11.65 -12.91(64) -12.55
PrHCO32+ - Pr^ + HCO3" - [-2.24] -1.89 [-2A8]m -2.15
PrH 2 PO 4 2 + ^ Pr^ + HgPO^ - - -2.37 [-2.63]' 3 - 861 -2.45
PrHPO4+ ^ P\3+ + HPO 4 2 - - -5.08 [-5.63f'86) -5.4
Pr(HPO4)2- ^ Pr*+ + 2 HPO 4 2 - - -8.50 [-9.3f'86) -8.9
PrPO4 ^ Pf^+ + PO4'3 -11.60 - - -11.60
Pr(PO4)23" ^ Pr3* + 2 PO4"3 -19.08 - - -19.08
P r S O / ^ Pr3+ + SO4"2 - -3.62 -3.27 -3.4
Pr(SO 4 ) 2 ^ Pr3+ + 2SO4"2 - -4.92 - -4.9
PrF2+ ^ Pr^ + F" - -4.06 -3.48 -3.7
P r C I 2 + ^ Pr^ + CI" - -0.44 -0.32 -0.3
PrNO 3 + ^ Pr3+ + NO3" - -1.2 -0.69 -0.9
Pr(ll)
Pr+3 + 0.5 H2O ^ P^+ + H+ + 0.25 O2(g) - - - 66.4 ( 2 3 ) 80.7

80.7<21>
33
Table 5.1 Praseodymium solids.

Literature(re( •) ted.
Pr(s)
Pr(s) + 3H + + 0.75 O2(g) - Pr3* + 1.5 H2O 181.4!21) 181.4
Pr(lll)
Pr(OH)3(am) ^ Pr^ + SOH" [-20.9] (3 °- 37) , -20.9
Pr(OH) 3 (s)^ Pr^ + SOH" -22.5 ( 2 9 ) , -22.08<48> -22.4
Pr2O3(c, hex.) + 6H + ^ 2 Pr3* + 3 H2O 61.4 t l 9 ) , 61.4
Pr2(CO3)3(s) ^ 2 Pr3* + 3 COg* -33.2 ( 6 9 ) , -27.0(65*», -34.8
Pr(OH)CO3(s) ^ Pr3* + OH+CO 3 2 " - -
PrPO4 x H2O (s) - Pr3* + P O / + x H2O -26.0 ( 8 9 *\[-24.6] ( 8 9 ' 7 4 ) -24.6
PrF3 0.5 H2O (s) ~ Pr3* + F + 0.5 H2O -18.9 (101) ,-20.2 (101) , -18.7
-18.8 (102) ,-17.0 (103)
34
Table 6. Neodymium solution species.

Lee&Byr. Wood Mill. Lit.(ref.) ted.
N d O H 2 + ^ N d ^ + OH" -5.84 -6.0 -5.67 -6.0(29) -5.9
-5.7 (36 *>
N d ( O H ) 2 + - Nd 3 + + 2OH" -10.96 - - -11.4 <36 "' -11.1
-11.1s91
Nd(OH)3^ N d ^+ S O H ' -15.60 - - -17.0 ( 3 6 '> -15.6
-15.5 ( 2 9 )
N d ( O H ) 4 " ^ Nd 3 + + 4 O H " - - - -18.9 ( 2 9 > -18.9
N d ^ O H ) ^ ^ 2Nd 3 + + 2 O H ' - - - -15.9 (36 *> -14.1

-14.14 ( 2 9 )
N d C O 3 + ^ Nd 3 + + C O 3 2 -7.69 [-7.75] -7.13 -7.67 ( 6 4 > -7.6
Nd(CO 3 ) 2 " - N d ^ + 2003- 2 -12.79 [-12.5] -11.80 -13.09 lM) -12.6
NdHCO 3 2 + - Nd 3 + + HCO3- - [-2.14] -1.83 [-2.51] 164 ' -2.12
NdH 2 PO 4 2 + ^ Nd 3 + + H2PO4- - - -2.31 [-2.68f' 86)

-1.28184"'
-2.4
3+ 2
N d H P O / ^ Nd + HPO 4 - - - -5.18 [-5.72]13-86' -5.4
Nd(HPO 4 ) 2 - ^ Nd 3 + + 2 H P O 4 2 - - -8.66 [-9.47] (386) -9.1
NdPO 4 ^ Nd 3 + + PO 4 " 3 -11.78 - - - -11.8
Nd(PO 4 ) 2 3 - - Nd 3 * + 2 P O 4 3 -19.50 - - - -19.5
N d S O 4 + ^ Nd3+ + SO 4 " 2 - -3.65 -3.26 -3.5
Nd(SO 4 ) 2 ^ Nd3+ + 2SO 4 - 2 - -5.15 - -5.1
N d F 2 + ^ N d ^ + F" - -4.14 -3.56 -3.8
N d C I 2 + ^ N d ^ + CI" - -0.40 -0.32 -0.35
NdNO 3 + ^ Nd3+ + NO 3 " -1.25 -0.79 -1.0
Nd(ll)
Nd +3 + 0.5 H 2 O ^ Nd 2+ + H + + 0.25 O2(g) 64.7(23) 65.1

(21
65.1 >
35
Table 6.1. Neodymium solids.

Literature^') ted.
Nd(s)
Nd(s) + 3H + + 0.75 O2(g) ^ Nd 3+ + 1.5 H 2 O 180.0 (21) 180.0
Nd(lll)
Nd(OH) 3 (am) ^ Nd 3+ + 3OH" -22.4*36*>, -21.5
N d ( O H ) 3 ( s ) ^ Nd 3 + + 3OH" -23.4 (29) , -23.9^48), -23.9

[-28.7] (74 * )
N d ( O H ) 3 ( c ) ^ Nd 3 + + 3OH" -26.2 ( 4 ^ -26.2
Nd 2 O 3 (c, hex.) + 6H + - Nd 3 * + 3 H 2 O 58.6 ( 1 9 ) 58.6
Nd 2 (CO 3 ) 3 ^ 2 Nd 3 * + 3 CO 3 2 ' -33.0 {66) , -34.1 ( 6 9 ) , -34.65
[-Z4.6r™6™, [-34.7](66)
Nd(OH)CO 3 (s) ^ N d ^ + OH+CO 3 2 - -ig.94^ 2 *),-21.74 ( 7 7 ) -21.5
-19.19<71*>, - 2 2 . 5 4 ^
NdPO 4 x H2O (s) ^ Nd 3 * + P O ^ + x H 2 O -25.9 (89 \ -24.45™ -24.5
[-24.6](89)
NdF 3 0.5 H 2 O (s) - Nd 3 + + 3 F + 0.5 H 2 O -18.6 <101) ,-19.9 (101) , -18.6
-19.3 ( 1 0 2 )
-17 1 ( 1 0 3 ) - 2 0 3 ( 1 0 4 )
36
Table 7. Prometium solution species.

Lee&By. Wood Mill. Lit.< ref > ted.
PmOH2+^ Prn^+ OH' -5.94 -6.05 -5.77 [-6.05f 9) -6.0
P m ( O H ) 2 + ^ Pm 3 + + 2OH" -11.22 - - -11.2
P m ( O H ) 3 ^ Prrv^ + SOH" -15.85 - - -15.8
P m C O 3 + ^ Pm 3 + + CO 3 - 2 -7.81 [-7.84] -7.22 7.78 (64) -7.7
Pm(CO 3 ) 2 " ^ Pm3++ 2CO32 -13.08 [-12.65] -11.96 -13.23 ( 6 4 ) -12.7
PmHCO 3 2+ ^ Pm 3 + + HCO3- - [-2.11] -1.79 [-2.52] (64> -2.1
PmH 2 PO 4 2+ - P m ^ + H2PO4- - - -2.27 [-2.74] 13861 -2.4
PmHPO 4 + ^ Pm 3 + + HPO 4 " 2 - - -5.27 [-5.8f 66) -5.5

-4.05' 8 2 '' 8 5 '
Pm(HPO 4 ) 2 - ^ Pm 3 * + 2 H P O 4 2 - - -8.81 [-9.6] 13 - 86 ' -9.2
P m P O 4 ^ P m ^ + PO^3 -11.95 - - -11.95
Pm(PO4)23' ^ Pm3* + 2 P < V -19.96 - - -19.96
P m S O / ^ Pm3+ + SO 4 ' 2 - [-3.66] -3.34 -3.5
P m ( S O 4 ) 2 ^ Pm3+ + 2SO 4 " 2 - [-5.33] - -5.2
PmF 2+ ^ Pm3+ + F" - [-4.16] -3.63 -3.8
P m C I 2 + ^ P m ^ + CI" - [-0.38 -0.31 -0.34
P m N O 3 + ^ P m ^ + NOg" - -1.31 -0.88 -1.1
Pm(ll)
Pm + 3 + 0.5 H 2 O ^ Pm 2+ + H + + 0.25O 2 (g) 64.7< 23) 66.0

66.0 ( 2 1 )
37
Table 7.1. Prometium solids.

Literature(ref) ted.
Pm(s)
Pm(s) + 3H + + 0.75 O2(g) ^ Pm3+ + 1.5 H2O 178.5< 21) 178.5
Pm(lll)
Pm(OH) 3 (am)^ Pm3+ + 3OH" [-24.1]<3°-37*> -23.7
Pm(OH)3 (s) - Pm3+ + 3OH" -24.5 (29) -24.5
Pm2O3 (c, hex.) + 6H + ^ Pm3+ + 3 H2O [48.8] (19) 48.8
Pm2(CO3)3 (s) - 2 Pm3+ + 3 CO32" [-34.3] (69) , t-34.55]^76-73) -34.55
Pm(OH)CO3 (s) ^ Pm 3+ + OH+CO 3 2 ' - -
PmPO4 x H2O (s) ^ Pm3* + PO43' + x H2O [-24.5](89'74> -24.5
PmF3 0.5 H2O (s) ^ Pm3+ + 3 P + 0.5 H2O -18.3< 101J ,-19.5t 101 >, -18.1
-16.5 ( 1 0 3 )
38
Table 8. Gadolinium solution species.

Lee&By. Wood Miller. Ljt .(ref.) ted.
GdOH 2+ ^ Gd 3+ + OH" -6.07 -6.0 -5.79 -6 0129> -6.0
-9.3(V
-6.0 ( 3 r )
+ 3+
Gd(OH) 2 ^ Gd + 2OH" -11.63 - - -11.6 ( 2 9 > -11.8
-12.4<3r)
Gd(OH) 3 ^ Gd J + + 3OH" -16.72 - - -16.8(29) -17.5
-19.0<3r)
Gd(OH)4" ^ Gd J + + 4OH" - - - -21.6(29) -22.1
GdCO 3 + ^ Gd 3+ + CO3-2 -7.97 [-8.05] -7.44 .7.82^ -7.8
Gd(CO 3 ) 2 " ^ Gd 3 + + 2CO3-Z -13.52 1-13.08] -12.39 -13.35 ( 6 4 ) -13.1
GdHCO 3 2+ - Gd 3+ + HCO3- - [-2.1] -1.72 _2.57<f*86> -2.1
GdH 2 PO 4 2+ ^ Gd 3+ + H2PO4- - - -2.20 - 2 . 8 1 <85> -2.4

-2.74< 86 >
GdHPO/^ Gd3++HPO4'2 - - -5.49 -5.70( 85 ' -5.7
.5.9-1(86)
Gd(HPO 4 ) 2 - ^ Gd 3 + + 2 HPO4"2 - - -9.24 .9.5(85) -9.6
.9.97(86)
GdPO 4 ^ Gd 3 + + POA'3 -12.20 - - 12.19 ( 8 6 ) -12.2
Gd(PO 4 ) 2 3 " ^ Gd 3 + + 2 PO4"3 -20.71 - - - -20.7
GdSO 4 + ^ Gd 3 + + SO 4 ' 2 - -3.66 -3.25 -3.4
Gd(SO 4 ) 2 ^ Gd3+ + 2SO 4 ' 2 - -5.20 - -5.1
GdF 2+ ^ Gd3+ + F" - -4.36 -3.75 -4.1
G d F 2 2 + ^ Gd 3 + + 2F" - -8.27 - -7.2
GdCI 2+ ^ Gd 3+ + CI" - -0.33 -0.28 -0.3
GdNO 3 + ^ Gd 3+ + NO 3 " - -1.1 -0.47 -0.8
Gd(ll)
Gd + 3 + 0.5 H2O ^ Gd 2 + + H + + 0.25O2(g) — — - 8 6 J(23) 85.4

85.4(21)
39
Table 8.1. Gadolinium solids.

Literature^-) ted.
Gd(s)
Gd(s) + 3H + + 0.75 O2(g) ^ Gd d+ + 1.5 H 2 O 178.6(21) 178.6
Gd(lll)
Gd(OH) 3 (am) ^ Gd 3 + + 3OH" -24.34(32') -24.0
Gd(OH) 3 (s) ^ Gdi+ + 3OH" -26.4(29), -26.9(48) -26.4
Gd 2 O 3 (c, monocl.) + 6H + ^ Gd J + + 3 H2O 53.8(19> 53.8
Gd(OH)CO 3 (s) ^ Gd J + + OH" + CO 3 2 " - -
Gd 2 (CO 3 ) 3 (S) ^ 2 Gd 3 + + 3 CO 3 2 - -35.45 (69) ,-32.2 (66) , -34.7

[_34.4](66)
GdPO 4 x H 2 O (s) ^ Gd 3 + + P O ^ + x H2O -25.1 ( 9 1 8 9 ) ,[-24.3F 9 ' 7 4 ) -24.3
GdF 3 0.5 H 2 O (s) ^ Gd J + + 3 F + 0.5 H2O -16.8 ( 1 0 1 > ,-18.1 ( 1 0 1 ) , -16.9

-18.6 ( 1 0 2 ) , -15.3 < 1 0 3 ) ,
40
Table 9. Terbium solution species.

Ut (ref.)
Lee&By. Wood Mill. ted.
TbOH 2 + ^ T V * + OH" -6.14 -6.1 -5.98 -6.1 1 ^ -6.1
-8.4 W
Tb(OH) 2 + ^ Tb 3+ + 2OH" -11.82 - - I-11.7T" -11.7
_14.3<«o
Tb(OH) 3 ^ Tb 3+ + 3OH" -16.92 - - t-16.95f9) -16.9
TbCO 3 + ^ Tb 3+ + CO3"2 -8.08 [-8.1] -7.50 -7.93 ( 6 4 ) -7.9
Tb(CO3)2" ^ Tb 3+ + 2 C < V -13.73 [-13.2] -12.52 -13.53' M) -13.1
TbHCO 3 2 + - Tb 3 + + HCO3- - [-2.13] -1.71 [-2.55](M) -2.1
TbH 2 PO 4 2+ ^ Tb 3 + + H2PO4" - - -2.19 [-2.77p-3> -2.4
T b H P O / ~ Tb 3 + + HPO4"2 - - -5.54 [-5.97]' 8631 -5.8
Tb(HPO 4 ) 2 - ^ Tb 3 + + 2 HPO4"2 - - -9.37 [-10.1] (863) -9.7
TbPO 4 ^ Tb 3+ + PO 4 " 3 -12.39 - - - -12.4
Tb(PO 4 ) 2 3 " ^ Tb 3 + + 2 PO 4 " J -21.02 - - - -21.0
TbSO 4 + ^ Tb 3+ + SO 4 '^ - -3.63 -3.20 -3.4
Tb(SO4)2 ^ Tb3+ + 2 S O / 2 - -5.13 - -5.0
TbF 2 + ^ Tb3+ + F" - -4.47 -3.85 -4.2
TbCI 2+ ^ Tb 3+ + CI" - -0.32 -0.27 -0.3
TbNO 3 + ^ Tb 3+ + NO 3 " - -0.97 -0.51 -0.7
Tb(ll)
Tb +3 + 0.5 H2O ^ Tb 2+ + H + + 0.25 O2(g) — ™ 83.3 (23) 79.5

79.5<21>
41
Table 9.1. Terbium solids.

Tb(s)
Tb(s) + 3H + + 0.75 O2(g) - Tb3+ + 1.5 H2O 179.2 (21)
Tb(lll)
Tb(OH)3(am) ^ Tb3+ + 3OHT [-23.2P"30, -23.2
Tb(OH)3(s) ^ Tb 3+ + 3OH" -25.5 ( 2 9 ) , - 2 6 . 3 1 ( 4 B ) -26.3
Tb2O3(c, cub.) + 6H + ^ Tb3+ + 3 H2O 47.1(19), 47.1
Tb(OH)CO3(s) ^ Tb3+ + OH" + CO32' - -
Tb2(CO3)3 (s) ^ 2 Tb3+ + 3 CO32- -34.86(68\ -34.2

TbPO4 x H2O (s) ^ Tb3+ + P O ^ + x H2O [- 24.3] ( B a ' / A ) -24.3
TbF 3 0.5 H2O (s) ^ Tb3+ + 3 P + 0.5 H2O -16.7 (101) ,-18.0 (101) ,-18.5 (102) -16.7
-14.9 (103) , -16.44 (107)
42
Table 10. Dysprosium solution species.

Lit (ref)
Lee&Byr Wood Mill. ted.
D y O H 2 + ^ Dy 3+ + O H " -6.19 -6.0 -6.04 -6.0 ( Z 9 ) -6.05
D y ( O H ) 2 + ^ Dy 3+ + 2OH" -11.90 - - -11.8(29) -11.8
Dy(OH) 3 ^ Dy 3+ + 3OH" -17.17 - - -17.3(29) -17.3
Dy(OH)4'^ Dy^ + ÔH" -22.5<29> -22.5
D y C O 3 + ^ Dy 3+ + CO 3 - 2 -8.14 [-8.13] -7.55 -8.0 ( b 4 ) -7.95
Dy(CO 3 ) 2 - ^ Dy J+ + 2CO 3 ^ -13.83 [-13.3] -12.65 -13.66<M> -13.2
DyHCO 3 2 + ^ Dy 3+ + HCO 3 " - [-2.15] -1.72 [-2.48]^' -2.15
DyH 2 PO 4 2 + ^ Dy 3+ + H 2 PO 4 ' - - -2.20 [-2.76J'8€3> -2.4
D y H P O 4 + ^ Dy 3+ + HPO 4 " 2 - - -5.60 [-6.0F6'3' -5.8
Dy(HPO 4 ) 2 " ^ Dy 3+ + 2 HPO 4 " 2 - - -9.49 [-10.2] c863) -9.8
DyPO 4 ^ Dy 3+ + PO 4 " 3 -12.52 - - -12.5
Dy(PO 4 ) 2 3 - ^ Dy J+ + 2 P < V -21.22 - - -21.2
D y S O 4 + ^ Dy 3+ + SO 4 - 2 - -3.83 -3.15 -3.5
Dy(SO 4 ) 2 ^ Dy3+ + 2SO 4 " 2 - -5.03 - -5.0
DyF 2 + ^ Dy 3+ + F - - -4.51 -3.89 -4.2
D y C I 2 + ^ Dy 3+ + CI" - -0.31 -0.27 -0.3
DyNO 3 + ^ Dy3+ + NO 3 " - [-1.05] -0.15 -0.6
Dy(ll)
Dy+3 + 0.5 H2O ^ Dy2* + H+ + 0.25 O2(g) - - 64.7(23) 61.8

21
61.8< >
43
Table 10.1. Dysprosium solids.

Literature<ref) ted.
Dy(s)
Dy(s) + 3H + + 0.75 O2(g) ^ DyJ+ + 1.5 H2O 178.6 (21) 178.6
Dy(lll)
Dy(OH) 3 (am) ^ Dy J+ + 3OH" [-24.5](30-3^, -24.5
Dy(OH) 3 (s) ^ Dy 3+ + 3OH" .26.1^ -26.1
Dy 2 O 3 (c, cub.) + 6H + ^ Dy 3+ + 3 H 2 O 47.0 (19) , 47.0
Dy(OH)CO 3 (s) ^ D y 3 + + O H ' + CO 3 2 ' - -
Dy 2 (CO 3 ) 3 (s) ^ 2 Dy J+ + 3 CO 3 ^ -31.5lM>\-33.97los', [-34.0P -34.0
DyPO 4 x H 2 O (s) - Dy J+ + POf + x H2O [-24.3] ( 8 9 ' 7 4 ) -24.3
DyF 3 0.5 H 2 O (s) - Dy J+ + 3 P + 0.5 H2O -16.3 ( 1 0 1 ) ,-17.6 ( 1 0 1 ) , -16.5

-18.2 ( 1 0 2 ) ,-14.6 ( 1 0 3 )
44
Table 11. Holmium solution species.
Reactron logK logK logK logK Selec-

Lee&Byr Wood Mill. Lit (ref.) ted.
HoOH2+ ^ HoJ+ + OH" -6.22 -6.0 -6.01 -6.0 ( 2 9 ) -6.1
Ho(OH) 2 + - Ho<J+ + 2OH" -11.93 - - -11.95 (29) -11.9
Ho(OH)3 ^ Ho3+ + 3OH" -17.44 - - -17.55 <29) -17.5
H o C O 3 + - HoJ+ + CO3^ -8.18 [-8.17] -7.59 -8.04 l M J -8.0
Ho(CO 3 ) 2 " ^ Ho 3+ + 2 C < V -13.86 [-13.5] -Mil -13.71^' -13.3
HoHCO 3 2+ ^ Ho 3+ + HCO3" - [-2.2] -1.73 [-2.44]'641 -2.17
H o H 2 P 0 4 2 + ^ Ho 3+ + H2PO4" - - -2.21 [-2.75] (B63) -2.3
H o H P O / ^ Ho 3+ + HPO 4 2 - - -5.64 [-6.03]*86'3' -5.8
Ho(HP0 4 ) 2 " ^ Ho 3+ + 2 HPO4"2 - - -9.62 [-10.2] 1863 ' -9.9
HoPO 4 ^ Ho 3+ + PO4"3 -12.59 - - - -12.6
Ho(PO 4 ) 2 3 ' ^ Ho 3+ + 2 PO4"3 -21.27 - - - -21.3
HoSO 4 + ^ Ho 3+ + SO 4 ' 2 - -3.60 -3.16 -3.4
H o ( S O 4 ) 2 ^ Ho3+ + 2SO 4 ' 2 - -4.90 - -4.9
HoF 2+ ^ Ho 3+ + F" - -4.57 -3.95 -4.3
H o C I 2 + ^ Ho 3+ + CI" - -0.30 -0.27 -0.3
HoNO 3 + ^ Ho 3+ + NO 3 ' - [-0.8] -0.25 -0.5
Ho(ll)
Ho +3 + 0.5 H2O - Ho 2+ + H + + 0.25 O2(g) — 69 8 (23) 68.1

68.1<21>
45
Table 11.1. Holmium solids.

Literature^) ted.
Ho(s)
Ho(s) + 3H + + 0.75 O2(g) ^ Ho3+ + 1.5 H2O 180.6(21) 180.6
Ho(lll)
Ho(OH)3(am) ^ Ho 3 + + 3OH" | _ 2 4 2](30-37) -24.2
Ho(OH) 3 (s)- Ho3+ + 3OH" -26.6 ( 2 9 ) , -26.6 ( 4 8 ) -26.6
Ho2O3(c, cub.) + 6H + ~ Ho3+ + 3 H2O 47.3 C19) , 47.3
Ho(OH)CO3(s) ^ Ho 3+ + OH" + CO3Z- - -
Ho2(CO3)3 (s) ^ 2 Ho3+ + 3 CO32" -32.8 ( 6 9 ) , [-33.8] (66> 73i/b) -33.8
HoPO 4 x H2O (s) ^ Ho3+ + P O ^ + x H2O [-24.2] ( 8 9 7 4 ) -24.2
HoF 3 0.5 H2O (s) ^ Ho 3+ + 3 P + 0.5 H2O -15.8 (101) ,-17.2 (101) , -16.4
-18.0<102), -14.6 (103)
46
Table 12. Erbium solution species.
Reaction log* logK logK logK Selec-

Lee&By. Wood Mill. Ut .(ref.) ted.
ErOH 2 + ^ Er>+ + OH" -6.27 -6.1 -6.15 _6.<|i») -6.13
-7.0™
E r ( O H ) 2 + ^ Er 3+ + 2Of-T -12.04 - - -12.1< 29 > -12.1
-12.5(34">
Er(OH) 3 ^ Er>+ + 3OH" -17.65 - - -17.8(29) -17.8
.17.8W
Er(OH)4-^ E ^ + ^ H - - - - -23.4t/aj -23.4
ErCO3+^ E ^ +CO^2 -8.24 [-8.2] -7.63 -8.11tb4) -8.05
Er(CO3)2- ^ Er3* + 2C<V -13.98 [-13.6] -12.88 -13.89< M) -13.4
ErHCO 3 2+ ^ Er3* + HCO 3 ' - [-2.26] -1.76 [-2.38]' 8631 -2.2
ErH 2 PO 4 2+ - Er>+ + H 2 PCV - - -2.24 [-2.77J'66'3) -2.4
ErHPO 4 + ^ Er3* + H P O 4 2 - - -5.68 [-6.07]*863' -5.9
Er(HPO4)2" ^ Er3* + 2 HP<V - - -9.73 [-10.3] (863) -10.0
ErPO 4 ^ Er 3 * + PO 4 " 3 -12.69 - - - -12.7
Er(PO 4 ) 2 3 - ^ Er 3 * + 2 P O 4 3 -21.41 - - - -21.4
ErSO 4 + ^ Er3+ + SO 4 - 2 - -3.59 -3.15 -3.4
Er(SO 4 ) 2 ^ Er3+ + 2SO 4 " 2 - -5.05 - -5.0
ErF 2+ - Er3+ + F - - -4.59 -3.98 -4.3
ErCr ^ Er3+ + CI" - -0.26 -0.28 -0.27
ErNO 3 + ^ Er3+ + NO 3 " - [-0.74] -0.15 -0.4
Er(ll)
Er+3 + 0.5 H 2 O ^ Er2* + H + + 0.25 O2(g) 70.9 (21) 70.9
47
Table 12.1. Erbium solids.

Literature<ref> ted.
Er(s)
Er(s) + 3H+ + 0.75 O2(g) ^ Er3* + 1.5 H2O 179.5(21) 179.5
Er(lll)
Er(OH)3(am) ~ Er3* + 3OH' -23.7*»'\ -23.0
Er(OH) 3 (s)^ Er^ + SOH" -27.0 ( 2 9 ) , -26.6 { 4 B ) -27.0
Er2O3(c, cub.) + 6H + ^ Er3* + 3 H2O 42.109) 42.1
Er(OH)CO3(s) ^ Er3* + OH" + CO3Z" - -
Er2(CO3)3 (s) - 2 Er3* + 3 CO 3 A -28.25 (69) , -22.9 (65 * ) , -33.6

[-32.2] ( 6 9 ) ,[-33.6] ( 6 6 ' 7 3 7 6 )
ErPO4 x H2O (s) ^ Er3* + P O / + x H2O -24.18 (89) -24.2
ErF3 0.5 H2O (s) - Er3* + 3 P + 0.5 H2O -15.5 ( n 0 1 J ,-16.8 ( a 0 1 ) , -16.3
-17.8 ( l 0 2 ) ,-15.5 ( 1 0 3 ) ,
48
Table 13. Thulium solution species.

Lee&By. Wood Mill. L|t(ref.) ted.
TmOH2+ ^ Tm 3 + + OH" -6.32 -6.3 -6.19
( a)
-6.3 * -6.25
Tm(OH) 2 + ^ Tm J + + 2OH" -12.12 - - -12.15'^ -12.1
Tm(OH) 3 ~ Tm 3 + + 3 0 H " -17.82 - - -17.85^J -17.8
TmCO 3 + - Tm 3+ + CO 3 ' 2 -8.32 [-8.27] -7.66 -8.19 ( M ) -8.1
Tm(CO 3 ) 2 " ^ Tm 3+ + 2CO 3 2 -14.07 [-13.7] -13.0 -14.03<M> -13.5
TmHCO 3 2+ - Tm 3+ + HCO{ - [-2.29] -1.79 [-2.33]<M> -2.25
TmH 2 PO 4 2+ ^ Tm 3+ + H2PCV - - -2.27 [-2.78](863» -2.5
TmHPO 4 + ^ Tm 3+ + HPO 4 ' 2 - - -5.71 [-6.11](86'3> -5.9
Tm(HPO 4 ) 2 - ^ Tm 3+ + 2 HPO4"2 - - -9.84 [-10.3]' 86 ' 3 ' -10.1
TmPO 4 ^ Tm 3+ + P < V -12.82 - - - -72.5
Tm(PO 4 ) 2 3 - ^ Tm 3+ + 2 PO 4 ' 3 -21.57 - - - -21.6
TmSO 4 + ^ Tm 3+ + SO 4 '^ - -3.60 -3.07 -3.3
Tm(SO 4 ) 2 ^ Tm 3+ + 2 S O / 2 - -5.15 - -5.1
TmF 2+ ^ Tm 3+ + F" - -4.61 -3.99 -4.3
TmCI 2+ - Tm3+ + Cl" - -0.25 -0.27 -0.26
TmNO 3 + - Tm 3 + + NO 3 ' - -0.67 -0.20 -0.4
Tm(ll)
Tm + 3 + 0.5 H2O ^ Tm 2+ + H + + 0.25O2(g) — 59 6 (23) 59.1

59.1(21>
49
Table 13.1. Thulium solids.

Literature^"*) ted.
Tm(s)
Tm(s) + 3H + + 0.75 O2(g) - Tm J+ + 1.5 H2O 179.5(21) 179.5
Tm(IH)
Tm(0H) 3 (am) - Tm 3 + + 3OH" [-24.7]t3U-3'"\ -24.7
Tm(OH) 3 (s) ^ Tm 3+ + 3OH" -27.0 (29) -27.0
Tm 2 O 3 (c) + 6H + ^ Tm 3+ + 3 H2O 447(19) 44.7
Tm(OH)CO 3 (s) - Tm 3+ + OH" + CO32- - -
Tm 2 (CO 3 ) 3 (s) - 2 Tm 3+ + 3 CO32" -31.67 ( 6 9 \[-33.4] ( b 6 - 7 3 ' 7 6 ) -33.4
TmPO 4 x H2O (s) - Tm 3+ + P O / + x H2O [-24 2l ( 8 9 > 9 1 i 9 2 i 7 4 ) -24.2
TmF 3 0.5 H2O (s) ^ Tm 3+ + 3 F + 0.5 H2O -15.8 (1U1) , - 1 7 . 1 I 1 U 1 \ -16.2

-17.6 ( 1 0 2 ) ,-14.6 ( 1 0 3 )
50
Table 14. Ytterbium solution species.

Lit (ref.)
Lee&Byr Wood Mill. ted.
YbOH2+ ^ Yb3+ + OH" -6.40 -6.3 -6.22 - 6 3(29> -6.35
-5.6<33*>
-5.3(42>
-8.4("">
Yb(OH)2+ ^ Yb3+ + 2OH" -12.26 -12.2I 29 ', -12.3
-15.9 (4V)
Yb(OH)3 ^ Yb3+ + 3OH" -18.15 - - -17.9^ -18.0

-17.8<33'>
Yb(OH)4" - Yb3+ + 4OH" - - - -23.3<29> -23.3
YbCO3+ ^ Yb3+ + CO3"2 -8.40 -8.31 -7.67 -8.28 ( 6 4 ) -8.15
Yb(CO3)2" ^ Yb3+ + 2 C < V -14.22 -13.81 -13.08 -14.21 «•*•» -13.6
YbHCO 3 2 + ^ Yb J + + HCO 3 ' - -2.33 -1.84 [-2.27](M> -2.25
YbH 2 PO 4 2 + - Yb 3 + + H2PO4" - - -2.32 [-2.8] t86 ' 3) -2.4
YbHPO4+ ^ Yb3+ + H P < V - - -5.73 [-6.2J< 86 ^ -6.0
Yb(HPO4)2" ^ Yb 3+ + 2 HP<V - - -9.95 [-10.4]^863) -10.2
YbPO4 ^ Yb3+ + P < V -12.94 - - - -72.9
Yb(PO4)23" ^ Yb 3+ + 2 PO/ 3 -21.79 - - - -21.9
YbSO4+ ^ Yb3+ + SO 4 -Z - -3.59 -3.06 -3.3
Yb(SO4)2 ^ Yb3+ + 2SO/ 2 - -5.18 - -5.1
YbF2+ - Yb3+ + F" - -4.63 -4.02 -4.3
YbCI2+ ^ Yb3+ + CI" - -0.24 -0.16 -0.2
YbNO3+ ^ Yb3+ + NO3" [-0.6] -0.25 -0.4
Yb(ll)
Yb +3 + 0.5 H2O - Yb2+ + H+ + 0.25 O2(g) - • 40.2(23) 38.3

38.3(21)
51
Table 9.1. Ytterbium solids.

Yb(s)
Yb(s) + 3H + + 0.75 O2(g) ^ YbJ+ + 1.5 H2O 1751(21)

175.1
Yb(lll)
Yb(OH)3(am) ^ Yb 3+ + 30hT -22.94 (33 ">, -23.0
Yb(OH)3(s) ^ Yb 3+ + 3OH- -27.3 ( 2 9 ) , -26.64 ( 4 B ) -27.3
Yb2O3(c, cub.) + 6H + ^ Yb3+ + 3 H2O 47.8 ( 1 S ) 47.8
Yb(OH)CO3(s) ^ Yb3+ + OH" + CO 3 ^ - -
Yb2(CO3)3 (s) ^ 2 Yb3+ + 3 CO32" -31.67 ( 6 9 ) ,-31.1 ( 6 6 ) , -33.3

[-33.6] (66)
YbPO4 x H2O (s) ^ Yb3+ + P O ^ + x H2O [-24.1] (B9 - /4 > -24.1
YbF3 0.5 H2O (s) ^ Yb J+ + 3 P + 0.5 H2O -15.0 l l u i ; ,-16.3 l l u ", -16.0
-17.2 (102) ,-14.6 (103)
52
Table 15. Lutetium solution species.

Ljt (ref)
Lee&By. Wood Mill. ted.
3+
LuOH2+ ^ Lu + OH" -6.41 -6.4 -6.24 _6.4^ -6.4
>-5.0<40>
L u ( O H ) 2 + ^ Lu 3+ + 2OHT -12.33 - - [-12.3H -12.3
Lu(OH) 3 ^ Lu 3+ + 3 O H ' -18.15 - - [-18.0fSJ -18.1
LuCO 3 + ^ Lu 3+ + C O 3 2 -8.43 [-8.35] -7.70 -8.29<b4) -8.2
Lu(CO 3 ) 2 - ^ Lu 3+ + 2CO 3 ' 2 -14.29 [-13.9] -13.20 -14.2'64' -13.8
LuHCO 3 2+ ^ Lu 3 + + HCO3" - [-2.35] -1.90 [-2.22](b4') -2.3
LuH 2 PO 4 2+ ^ Lu 3+ + H2PO4" - - -2.38 [-2.82](B6i3) -2.5
LuHPO 4 + ^ Lu 3+ + HPO4"2 - - -5.75 [-6.2](86'3) -6.0
Lu(HPO 4 ) 2 - ^ Lu 3 + + 2 HPO4"2 - - -10.05 [-10.5](86'3> -10.3
LuPO 4 ^ Lu 3+ + PO 4 ' 3 -12.99 - - -13.0
Lu(PO4)23" ^ Lu3+ + 2 P < V -21.90 - - -21.9
LuSO 4 + ^ Lu3+ + S O / ^ - -3.60 -3.01 -3.3
L u ( S O 4 ) 2 ^ Lu3+ + 2SO 4 " 2 - -5.39 - -5.3
LuF 2+ ^ Lu^ + + F - -4.66 -4.05 -4.3
LuCI 2+ ^ Lu3+ + CI" - -0.23 0.03 -0.1
LuNO 3 + - Lu 3 + + NO 3 " - [-0.6] -0.56 -0.6
53
Table 15.1. Lutetium solids.

Literature( ref ) ted.
Lu(s)
Lu(s) + 3H + + 0.75 O2(g) ^ Lu3+ + 1.5 H2O 179.2 (21) 179.2
Lu(HI)
Lu(OH) 3 (am) - L u 3 + + 3OH" [-23.0f°*r), -23.0
L u ( O H ) 3 ( s ) - Lu 3 + + 3OhT - 2 7 . 5 ( 2 9 \ -27.0 ( 4 8 ) -27.5
Lu 2 O 3 (c, hex.) + 6H + ^ Lu 3 + + 3 H 2 O 45.0 ( 1 9 ) 45.0
Lu(OH)CO 3 (s) ^ Lu 3+ + OH" + CO 3 2 ' - -
Lu 2 (CO 3 ) 3 (s) ^ 2 Lu 3 + + 3 CO3Z- -32.16 ( B 9 ) , [33.0] ( b b - / 3 ) -33.0
LuPO 4 x H2O (s) - Lu 3 + + P O ^ + x H2O [-24.0] ( 8 9 ' 7 4 ) -24.0
LuF 3 0.5 H2O (s) ^ Lu 3 + + 3 P + 0.5 H2O -15.0 l1ul) , -16.4<1U1J -15.9
-16.9 (102) , -14.6 (103) ,
54
Table 16. Yttrium solution species.

Lit (ref.)
ted.
YOH 2 + ^ Y 3+ + OH" -6.3 (29) , - e . 4 ^ 3 ^ -6.3
Y(OH) 2 + ^ Y J + + 2OH" -11.6^ -11.6
Y(OH) 3 ^ Y J + + 3OH" -16.0 ( " a; -16.0
Y(OH) 4 " ^ Y 3+ + 4OH" -19.5 (2a) -19.5
Y 2 (OH) 2 4 + - 2 Y 3+ + 2 OH" -13.8^ -13.8
Y 3 (OH) 5 4+ ;=: 3 Y 3 + + 5 O H " -38.4
YCO 3 + - Y 3+ + CO 3 - 2 -8.07 (t>b) , -8.05
Y(CO 3 ) 2 " ^ Y 3+ + 2CO 3 - 2 [-13.3](56M» -13.3
YHCO 3 2 + ^ Y 3+ + HCO 3 - -2.36 li)b) , [-2.38]^-^ -2.3
YH 2 PO 4 2 + ^ Y 3+ + H2PO4" [-2.4r-^\ -2.65(W), -2.4
YHPO 4 + ^ Y 3+ + H P O 4 2 [-6.0] (8b3) , [-5.7] M -5.9
Y(HPO 4 ) 2 " ^ Y 3+ + 2 HPO 4 ' 2 [-10.2f bJJ , [-9.6] w -9.9
Y P O 4 ^ Y 3+ + P O 4 3 [-12.6] ia) -72.6
Y(PO 4 ) 2 3 " ^ Y 3+ + 2 PO4"3 [-21.4]13' -27.4
YSO 4 + ^ Y3+ + SO 4 " 2 [-3.4](1'2) -3.4
Y(SO 4 ) 2 ^ Y3+ + 2SO 4 " 2 [-4.9] ll) -4.9
YF 2 + ^ Y3+ + F' -4.3 (1 ^ -4.3
YF 2 2 + ^ Y3+ + 2F" -8.58(1) [-7.8] ll ^' s ' -7.8
YF 3 2 + - Y3+ + 3F" -12.49 ll) [-11.2] 111 ^ -11.2
YCI 2+ ^ Y 3+ + CI" [-0.3]11^ -0.3
YNO 3 + ^ Y 3+ + NO 3 " [-0Af2) -0.4
55
Table 16.1. Yttrium solids.

Literature<rcf) ted.
Y(s)
Y(s) + 3H + + 0.75 O2(g) ^ Y 3+ + 1.5 H2O 182.3 (21) 182.3
Y(lll)
Y(OH) 3 (am) ^ Y 3+ + 3OH" [-22.6](30-37"\ -23.2 (48) -23.0
Y(OH) 3 (s) =± Y 3+ + 3OH" -24.S™, -24.5 (40) -24.5
Y 2 O 3 (c, cub.) + 6H + ^ Y 3+ + 3 H2O 4 6 .4d9) 46.4
Y(OH)CO 3 (s) ^ Y a + + OH" + CO 3 2 " - -
Y 2 (CO 3 ) 3 3H 2 O (s) - 2 Y 3+ + 3 CO 3 2 " + 3H2O -32.77 ( ' 3 \ -30.6(b6^ -32.8

-31.52 ( 6 9 ) ,[-32.8] ( 6 6 )
YPO 4 x H 2 O (s) ^ Y J + + P O ^ + x H2O [-24.2](89-74) -24.2
YF 3 0.5 H 2 O (s) ^ Y J + + 3 P + 0.5 H2O -17.3w,-17.3(l01),-18.4(10i!) -16.9

-14.8(103),-18.3(104)
56
2. TEST CASES.
A rigorous validation of the selected data base is difficult, owing to the lack of
independent solubility data as a function of the different master variables. As an
example, most of the carbonate solubility studies used to derive the solubility
products (fig. 3) have been performed at one particular set of conditions.
Neodymium and europium, as chemical analogs of Am, have received special
attention in the last years and there are some data concerning the solubility of
Nd, Eu or Am hydroxide, carbonate, hydroxycarbonate, and phosphate at
various conditions. These data have been reported mainly by Kim and
coworkers (71, 72, 94) and Rai and coworkers (70,74, 129).
•A
-5
A
-6
J(lll
LU -7 \
s o
-8
y
Q
O O
-9 -
1 1 . 1
10
Fig. 5. Solubility of Eu(OH)3(s) from ref. (94). The theoretical curve was
calculated by using the constants selected in the present work.
57
In fig. 5 the experimental data by Bernkopf (94) for the solubility of Eu(OH)3(s)
until pH =10.5 are represented, together with the prediction from this work.
In fig. 6 the data of Ferri et al. (53) for the solubility of Ce2(CO3)3(s) are
represented, together with the theoretical curve calculated with the constants
selected in this work. As seen the agreement is good, except for the part of the
lower solubilities. We have recalculated the carbonate constants at 3 M NaCIO4
using e(Na+, CO3"2)= -0.08 and s(Na+, HCO3")= -0.002
4.0 5.0 5.5 6.0 6.5 7.0 7.5

-log[Hi
Fig 6. Solubility data for cerium carbonate from ref.(53) calculated with
the constants selected in this work.
The data of Runde, Meinrath and Kim(72) for the solubility of europium
carbonate and hydroxycarbonate were digitized as represented in fig. 7,
together with the model calculations using the constants selected this work. As
seen the agreement is good and in the same work reference is made to similar
solubilities for Nd and Am carbonates and hydroxycarbonates.
58
-2.0
-2.5-
=, -3-<H
UJ
8?
-3.5-
-4.0
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5
PH
Fig. 7. Solubilities of Eu2(CO3)3(s) and EuOHCO3(s) from ref. (72).
In fig. 8 the data on the solubility of neodymium carbonate and

hydroxycarbonate as reported by Meinrath and Kim (71) are represented
together with the model calculations using the solubility products from this work.
59
-2
-3
• Ref(71). N t y C O ^ s ) . 1 atm. COj(g)

A Ref(71). NrtjfCO^s), 0.01 atm. CO^g)
V Ref(71). NdOHCO^s). CCfc (g) ar
• Ref(77). NdOHCOj (s), 1 atm. CCyg)
O Ref(77). N0OHCO3 (s). 0.1atm. CO^g)
-7
4,0 4,5 5,0 5,5 6,0 6,5
-log{aH+}
Fig. 8. Solubilities of Nd(CO3)3(s) and Nd(OH)CO3(s) from ref. (71) and

(77) and model calculations with the constants selected in this work.
In the same figure are represented the data of Caroll (77) which claims to have
determined only the hydroxycarbonate of Nd at all partial pressures of CO2(g).
Even though phase transformations at prolonged equilibration times in this
system are an open question, it seems that some data of Carroll fit well with the
solubility of the normal carbonate as calculated from the constants selected in
this work.
60
3. SOLUBILITIES OF REE IN REPOSITORY CONDITIONS.
The REE in the fuel are present as oxides in solid solution with uranium dioxide.
Hence their solubility in the first period will be limited by matrix dissolution and
very low concentrations are to be expected. Anyhow, after some time the
saturation with respect to various secondary solid phases should be reached
and their solubility will be further governed by these phases. We have used as
example our Eu database and the groundwater with the composition given in
paragraph 1. 2. 3. to calculate solubilities and solubility limiting solids in
repository conditions. From the reported solubilities, the normal phosphates
seem the most insoluble (fig 9) and should limit the solubility of the REE in the
interval 10~10 -10" 12 in typical pH values for most groundwaters.
EuP0 4 .xH ? 0(s) Eu(OH) 3 (s)

1.0 r
0.0
6 8 ID 12
pH
Fig 9. Distribution of Eu at the 2 10"7 M level among solids and solute
species in groundwater.
61
-5
O
tn
CO
-10
o
-15
ID 12
PH
Fig. 10. Solubility of EuPO4.x H2O(s) in ground water.
Anyhow, in a validation of the Nd database (74) for the solubility of neodymium

doped glass, solubilities several orders of magnitude higher than the one
predicted assuming formation of NdPO4 xH2O(s) were observed in the presence
of phosphate. The authors suppose the formation of a much more soluble than
NdPO4 x H2O(s) phosphate phase in the Nd - PO 4 - H2O system. This is also a
very important point to be clarified by further experimental work.
As the next less soluble phase most studies indicate the hydroxycarbonates, but
only data for Eu and Nd are available. In fig. 11 is shown the solubility of
EuOHCO3(s) in the granitic ground water given above, calculated with the
values of the constants from this work. As seen, solubilities of the order of
lO^-IO" 9 M are to be expected in the presence of this solid phase.
62
0
Eu(DH)C03( s )
-5 -
o
to
m -10 -
o
-15
• i i I I r i i i i
6 a ID 12
PH
Fig. 11. Solubility of EuOHCO3(s) in granitic ground water as calculated
with values of the constants selected in this work.
On the other hand the solubilities in the case of the carbonate as the solubility
limiting phase would be of the order 10"7 - 10' 75 M, as shown in fig 11 for
Eu2(CO3)3(s).
Eu 2 (C0 3 ) 3 (s)
-5
O
in
-id
-15 I I I
6 a ID 12
PH
Fig.12. Solubility of Eu2(CO3)3 3H2O(s) in granitic ground water as

calculated with values of the constants selected here.
63
In this work it is considered that these two phases, i. e. carbonate and
hydroxycarbonate form at different P c 0 2 pressures as reported in most studies

(67, 68, 71, 72, 75) and their stability fields can be calculated from the constants
reported in the database and the known constants of the carbon dioxide-water
system.
Thus for Eu(lll) the constant of the reaction:
Eu(OH)3(s) + CO2(g) = Eu(OH)CO3(s) + H2O

can be calculated from the solubility constants of Eu(OH)3(s), Eu(OH)CO3(s),
1^°= -14 and the constant KHK1K2 = -18.15 for the reaction CO2(g) + H2O ^ ^
CO 3 2 ' + 2H + as K= -4.85. This corresponds to a CO2(g) partial pressure for the
equilibrium between these two solids of 0.14-10"4 bar. In the same way may be
obtained the constants for the equilibrium:
Eu(OH)3(s) + 1.5 CO2(g) ^ 0.5 Eu2(CO3)3 (s) + 1.5 H2O K= 5.48
corresponding to an equilibrium P C02 = 0.033 10"4 bar, and for the reaction:
Eu(OH)CO3(s) + 0.5 CO2(g) ^ 0.5 Eu2(CO3)3 (s) + 0.5 H2O K= 0.63
which gives an equilibrium PCo2 = ° - 2 3 bar

-
A typical predominance diagram for Eu at the 2 10"7 M level in ground water,
calculated with the constants selected in this work, but excluding phosphate for
the above mentioned reasons, is presented in fig. 13.
64
[PD4d"]TQr= 2.00 [ci-]Tar= 1 . 0 0 mm
[Eu3*]TQT= D.20 5 D . 0 0 j-im
Q_
V)
D
t= 25°C
Fig. 13. Predominance area diagram for the Eu -CO2(g)-H2O system
As seen for P C 0 2 typical for air, the hydroxy carbonate is the dominant phase,
while at higher carbonate contents the normal carbonate forms. As discussed
above, more work is needed to fully understand this system for all the REE,
since it is difficult to make predictions when neither the existence nor the
solubility of the hydroxycarbonates of the heavy REE is known.
65
3. CONCLUSIONS AND RECOMMENDATIONS.
1. We have compiled a selected thermodynamic database for the REE under

repository conditions.
1. The solution speciation of the REE is known with an acceptable degree of
accuracy for most important ligands, especially as compared to the known
solubilities of the most important solids.
2. Carbonate complexes of the REE are the dominant soluble species under
3. More reliable data on the stability of inorganic aqueous complexes like

hydroxide, phosphate, higher carbonate, are of particular importance in the
speciation of REE in hyperalkaline(cement) environments. Additionally, the
increase of the stability of the two valent state with temperature and its
complexation represent areas where more future studies are needed.
4. At the initial stages of fuel dissolution, UO2(s) matrix dissolution will determine
the concentrations of REE. Later, solid phosphates, hydroxycarbonates and
carbonates may limit their solubility, probably under 10"7 M.
5. Neither the solids formed, nor their solubilities are known with any degree of
reliability in many important systems as Ln-H2O-CO3, Ln-CO3-F, Ln-H2O-PO4.
There is a need for accurate studies on these systems, with good control of the
solid phase and solution parameters, to model the behaviour of the REE in
66
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80
List of SKB reports
Annual Reports
1977-78 1986
TR 121 TR 86-31
KBS Technical Reports 1 - 1 2 0 SKB Annual Report 1986
Summaries Including Summaries of Technical Reports Issued
Stockholm, May 1979 during 1986
Stockholm, May 1987
1979
TR 79-28 1987
The KBS Annual Report 1979 TR 87-33
KBS Technical Reports 79-01 - 79-27 SKB Annual Report 1987
Summaries Including Summaries of Technical Reports Issued
Stockholm, March 1980 during 1987
Stockholm, May 1988
1980
TR 80-26
The KBS Annual Report 1980 1988
TR 88-32
KBS Technical Reports 80-01 - 80-25
Summaries
SKB Annual Report 1988
Including Summaries of Technical Reports Issued
Stockholm, March 1981
during 1988
Stockholm, May 1989
1981
TR 81-17
KBS Technical Reports 81-01 - 81-16 TR 89-40
Summaries SKB Annual Report 1989
Stockholm, ApriM 982 Including Summaries of Technical Reports Issued
during 1989
Stockholm, May 1990
1982
TR 82-28
Stockholm, July 1983 Including Summaries of Technical Reports Issued
during 1990
Stockholm, May 1991
1983
TR 83-77
Stockholm, June 1984 Including Summaries of Technical Reports Issued
during 1991
1984 Stockholm, April 1992
TR 85-01
Annual Research and Development 1992
Report 1984 TR 92-46
Including Summaries of Technical Reports Issued SKB Annual Report 1992
during 1984. (Technical Reports 84-01 -84-19) Including Summaries of Technical Reports Issued
Stockholm, June 1985 during 1992
Stockholm, May 1993
1985
TR 85-20 1993
Annual Research and Development TR 93-34
Report 1985 SKB Annual Report 1993
Including Summaries of Technical Reports Issued Including Summaries of Technical Reports Issued
during 1985. (Technical Reports 85-01 -85-19) during 1993
Stockholm, May 1986 Stockholm, May 1994
1994 TR 95-05
TR 94-33 Groundwater sampling and chemical
SKB Annual Report 1994 characterisation of the Laxemar deep
Including Summaries of Technical Reports Issued borehole KLX02
during 1994. Marcus Laaksoharju', John Smellie2
Stockholm, May 1995 Ann-Chatrin Nilsson3, Christina Skarman1
1
GeoPointAB, Sollentuna, Sweden
2
Conterra AB, Uppsala, Sweden
3
KTH, Stockholm, Sweden
February 1995
List of SKB Technical Reports 1995 TR 95-06

Palaeohydrological implications in
TR 95-01 the Baltic area and its relation to the
Biotite and chlorite weathering at 25°C. groundwater at Aspo, south-eastern
The dependence of pH and (bi) carbonate Sweden - A literature study
on weathering kinetics, dissolution Bill Wallin
stoichiometry, and solubility; and the Geokema AB, Lidingo, Sweden
relation to redox conditions in granitic March, 1995
aquifers
TR 95-07
Maria Malmstrom1, Steven Banwart1, Lara Duro2,
Paul Wersin3, Jordi Bruno3
Aspo Hard Rock Laboratory
' Royal Institute of Technology, Department of Annual Report 1994
Inorganic Chemistry, Stockholm, Sweden SKB
2
Universidad Politecnica de Catalufia, Departmento April 1995
de Inginen'a Qufmica, Barcelona, Spain
3
MBT Tecnologi'a Ambiental, Cerdanyola, Spain TR 95-08
January 1995 Feasibility study for siting of a deep
repository within the Storuman
municipality
TR 95-02 Swedish Nuclear Fuel and Waste
Copper canister with cast inner Management Co., Stockholm
component. Amendment to project on January 1995
Alternative Systems Study (PASS),
SKB TR 93-04 TR 95-09
Lars Werme, Joachim Eriksson
A thermodynamic data base for Tc
Swedish Nuclear Fuel and Waste Management Co, to calculate equilibrium solubilities
Stockholm, Sweden at temperatures up to 300°C
March 1995 Ignasi Puigdomenech1, Jordi Bruno2
1
Studsvik AB, Nykoping, Sweden
2
Intera Information Technologies SL,
TR 95-03 Cerdanyola, Spain
Prestudy of final disposal of long-lived April 1995
low and intermediate level waste
Marie Wiborgh (ed.) TR 95-10
Kemakta Konsult AB, Stockholm, Sweden Investigations of subterranean
January 1995 microorganisms.
Their importance for performance
assessment of radioactive waste
TR 95-04 disposal
Spent nuclear fuel corrosion: Karsten Pedersen1, Fred Karlsson2
The application of ICP-MS to direct 1
Goteborg University, General and Marine
actinide analysis Microbiology, The Lundberg Institute,
RSForsyth 1 ,U-BEklund 2 Goteborg, Sweden
1 2
Caledon-Consult AB, Nykoping, Sweden Swedish Nuclear Fuel and Waste
2
Studsvik Nuclear AB, Nykoping, Sweden Management Co., Stockholm, Sweden
March 1995 June 1995
TR 95-11 TR 95-17
Solute transport in fractured media - Measurements of colloid concentra-
The important mechanisms for tions in the fracture zone, Aspo Hard
performance assessment Rock Laboratory, Sweden
Luis Moreno, Bjorn Gylling, Ivars Neretnieks Anna Ledin, Anders Diiker, Stefan Karlsson,
Department of Chemical Engineering and Bert Allard
Technology, Royal Institute of Technology, Department of Water and Environmental
Stockholm, Sweden Studies, Linkoping University, Linkdping, Sweden
June 1995 June 1995
TR 95-12
Literature survey of matrix diffusion TR 95-18
theory and of experiments and data Thermal evidence of caledonide fore-
including natural analogues land, molasse sedimentation in
Yvonne Ohlsson, Ivars Neretnieks Fennoscandia
Department of Chemical Engineering and Eva-Lena Tullborg1, Sven Ake Larsson1, Lennart
Technology, Royal Institute of Technology, Bjorklund1, Lennart Samuelsson2, Jimmy Stigh1
1
Stockholm, Sweden Department of Geology, Earth Sciences Centre,
August 1995 Goteborg University, Goteborg, Sweden
2
Geological Survey of Sweden, Earth Sciences
TR 95-13 Centre, Goteborg, Sweden
Interactions of trace elements with November 1995
fracture filling minerals from the Aspo
Hard Rock Laboratory
Ove Landstrom1, Eva-Lena Tullborg2 TR 95-19
1
Studsvik Eco & Safety AB Compaction of bentonite blocks.
2
Terralogica AB Development of technique for industrial
June 1995
production of blocks which are
manageable by man
TR 95-14 Lars-Erik Johannesson, Lennart Borgesson,
Consequences of using crushed Torbjorn Sanden
crystalline rock as ballast in KBS-3 Clay Technology AB, Lund, Sweden
tunnels instead of rounded quartz April 1995
particles
Roland Pusch
Clay Technology AB TR 95-20
February 1995 Modelling of the physical behaviour of
water saturated clay barriers.
TR 95-15 Laboratory tests, material models and
Estimation of effective block finite element application
conductivities based on discrete Lennart Borgesson1, Lars-Erik Johannesson1,
network analyses using data from the Torbjorn Sanden1, Jan Hernelind2
1
Aspo site Clay Technology AB, Lund, Sweden
2
Paul R La Pointe1, Peter Wallmann1, Sven Follin2 FEM-Tech AB, Vasteras, Sweden
1
Golder Associates Inc., Seattle, WA, USA September 1995
2
Golder Associates AB, Lund, Sweden
September 1995
TR 95-16 TR 95-21
Temperature conditions in the SKB Conceptual model for concrete long
study sites time degradation in a deep nuclear
Kaj Ahlbom', Olle Olsson', Stefan Sehlstedt2 waste repository
1
Conterra AB Bjorn Lagerblad, Jan Tragardh
2
MRM Konsult AB Swedish Cement and Concrete Research Institute
June 1995 February 1994
TR 95-22 TR 95-28
The use of interaction matrices for DECOVALEX I -Test Case 2:
identification, structuring and ranking Calculation of the Fanay-Augeres THM
of FEPs in a repository system. Test-Thermomechanical modelling of
Application on the far-field of a deep a fractured rock volume
geological repository for spent fuel Lennart Borgesson1, Jan Hernelind2
1 2 1 1
Kristina Skagius , Anders Strom , Marie Wiborgh Clay Technology AB, Lund, Sweden
1 2
Kemakta, Stockholm, Sweden Fern-Tech AB, Vasteras, Sweden
2
Swedish Nuclear Fuel and Waste Management December 1995
Co, Stockholm, Sweden
November 1995 TR 95-29
DECOVALEX I -Test Case 3:
TR 95-23 Calculation of the Big Ben Experiment
Spent nuclear fuel. A review of - Coupled modelling of the thermal,
properties of possible relevance mechanical and hydraulic behaviour of
to corrosion processes water-unsaturated buffer material in a
Roy Forsyth simulated deposition hole
Caledon Consult AB Lennart Borgesson1, Jan Hernelind2
April 1995 1
Clay Technology AB, Lund, Sweden
2
Fern-Tech AB, Vasteras, Sweden
TR 95-24 December 1995
Studies of colloids and their
importance for repository TR 95-30
performance assessment DECOVALEX I - Bench-Mark Test 3:
Marcus Laaksoharju1, Claude Degueldre2, Thermo-hydro-mechanical modelling
Christina Skarman1 Jan Israelsson
1
GeoPoint AB, Sollentuna, Sweden Itasca Geomekanik AB
2
University of Geneva, Switzerland December 1995
December 1995
TR 95-31
TR 95-25
DECOVALEX I -Test Case 1: Coupled
Sulphate reduction in the Aspo stress-flow model
HRL tunnel Lars Rosengren1, Mark Christianson2
Marcus Laaksoharju (ed.) 1
1tasca Geomekanik AB
GeoPoint AB, Sollentuna, Sweden 2
Itasca Consulting Group Inc.
December 1995
December 1995
TR 95-26
The Aspo redox investigations in TR 95-32
block scale. Project summary and Partitioning and transmutation (P&T)
implications for repository 1995. A review of the current state of
performance assessment the art
Steven Banwart (ed.) Mats Skalberg1, Anders Landgren1, Lena Spjuth1,
Dept. of Civil and Environmental Engineering, Jan-Olov Liljenzin1, Waclaw Gudowski2
1
University of Bradford, UK Department of Nuclear Chemistry, Chalmers
November 1995 University of Technology, Gothenburg, Sweden
2
Department of Neutron and Reactor Physics,
TR 95-27 Royal Institute of Technology, Stockholm,
Survival of bacteria in nuclear waste Sweden
buffer materials. The influence of December 1995
nutrients, temperature and water
activity TR 95-33
1
Karsten Pedersen , Mehrdad Motamedi , 1 Geohydrological simulation of a deep
Ola Karnland2 coastal repository
1
Department of General and Marine Microbiology, Sven Follin
the Lundberg Institute, Goteborg University, Golder Associates AB, Stockholm, Sweden
Goteborg, Sweden December 1995
2
Clay Technology AB, Lund, Sweden
December 1995
TR 95-34
General Siting Study 95 - Siting of a
deep repository for spent nuclear fuel
Swedish Nuclear Fuel and Waste Management Co
October 1995
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A selected thermodynamic database for REE to be used in HLNW performance

The user has requested enhancement of the downloaded file.

A selected thermodynamic database for

Kastriot Spahiu, Jordi Bruno

MBT Tecnologia Ambiental, Cerdanyola. Spain

Kastriot Spahiu, Jordi Bruno

MBT Tecnologia Ambiental, Cerdanyola, Spain

Information on SKB technical reports from 1977-1978 (TR 121), 1979

TO BE USED IN HLNW PERFORMANCE ASSESSMENT

Kastriot Spahiu and Jordi Bruno1

MBT Tecnologia Ambiental, Pare Tecnologic del Valles

A selected thermodynamic database for the Rare Earth Elements (REE) to

be used in the safety assessment of high-level nuclear waste has been

most important ligands relevant for granitic groundwater conditions have

conditions are the carbonate complexes of REE. The solubilities of the

oxides, hydroxides, carbonates, hydroxycarbonates, phosphates and other

database. At the initial stages of fuel dissolution, the UO2(s) matrix

dissolution will determine the concentrations of REE. Later on, solid

phosphates, hydroxycarbonates and carbonates may limit their solubility.

Recommendations for further studies on important systems in repository

conditions have been presented.

En utvald termodynamisk databas för de sällsynta jordartsmetallerna

(lantaniderna), för användning i säkerhetsanalyser av förvaring av högaktivt

radioaktivt avfall, har kompilerats. Termodynamiska data för vattenlösliga

specier av lantaniderna med de viktigaste liganderna i granitiska grundvatten

har valts ut och validerats. Den dominerande specien under förvarsförhål-

landen är lantanidemas karbonatkomplex. Löslighetsprodukterna av oxider,

hydroxider, karbonater, hydroxykarbonater, fosfater och andra viktiga mineral

har valts och validerats. Lösligheter och löslighetsbegränsande faser under

förvarsförhållanden har bestämts med den utvalda databasen. I den tidiga

skedena av bränsleupplösningen kommer UO2 - matrisens upplösning att

bestämma koncentrationen av lantanider. I senare skeden kommer fosfater,

hydroxykarbonater och karbonater att bestämma lösligheten. Rekomenda-

1.1. Simple lanthanide ions 2

1.3. Solid phases 13

1.4. Data tables 24

3. SOLUBILITIES OF REE IN REPOSITORY CONDITIONS 61

4. CONCLUSIONS AND RECOMMENDATIONS 66

Our objective is therefore to produce an up to date thermodynamic

The thermodynamic databases associated to the geochemical modelling

1.1. Simple lanthanide ions.

The dominant oxidation state of the REE in aqueous solution at 25 °C is the +3

Ln 3+ +0.5 H2O ^ Ln2+ + H+ + 0.25 O2(g)

C e ^ + H+ + 0.25 O2(g) ^ Ce4+ + 0.5 H2O

is the only one of significance for performance assessment calculations. Since

1.2. Solution species

As mentioned above, at 25 °C the main oxidation state of lanthanum, the

M'Halla et al. (40) have measured conductometrically the first hydrolysis

1.2.2 Carbonate complexes.

Bernkopf (94) and Bidoglio and Marcandalli (130) propose mixed

1.2.3 Phosphate complexes

2 REE 3 ** 2 10"7 M, I C O 3 2 ' = 1.8 10"3M, Z CI" = 1 10"3 M, Z SO4"2 = 1 10"4 M,

As seen from the diagrams, the carbonate complexation dominates the

Fig 1a. Aqueous speciation of lanthanum in granitic ground water

calculated with the data selected in the present work.

Fig. 1c. Speciation of lutetium in groundwater, calculated with the present

1.2.4. Sulfate and fluoride complexes.

1.2.5 Chloride, nitrate and other solution species