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) for
chelate-forming reactions and the relation
2.303RT
log
T
P
G
r
T
P
S
r
(3)
where G
r
are taken from Shock et al. (1997). Solid circles represent standard-state
entropy values. Open symbols designate the values at various ionic strengths from 0.1 to 0.5 m, some of which were
measured at 20C. The solid lines exhibit a consistent slope of 0.84.
3934 P. Prapaipong and E. Shock
1988; Sassani and Shock, 1992). These correlations vary in
their functional dependence of S
of aqueous
ions are dependent on Z and linearly proportional to crystallo-
graphic radii (r
x
). To take into account the hydration effects on
r
x
, effective electrostatic radii (r
e
) were introduced, and it was
demonstrated that values of S
and Z/r
e
.
In addition to the estimation approaches based on physical
models, S
)
1
of aqueous cations and anions in
the complexes or chelates (Charles, 1954; George, 1959;
Frausto da Silva and Candida T. Abreu Vaz, 1977; Hovey,
1988; Shock and Koretsky, 1993, 1995; Sverjensky et al., 1997;
Prapaipong et al., 1999). George (1959) proposed that S
r
for
inorganic complexes and S
h
S
h
k, (4)
where k is an empirical function of cations and anions. Linear
correlations were also found between S
r
and S
h
of cations for
metalEDTA complexes (Nancollas, 1960) and for uramildi-
acetate complexes of alkali and alkaliearth metals (Frausto da
Silva and Candida T. Abreu Vaz, 1977).
1
S
h
of aqueous metal
cations (S
M
, as
well as values of S
r
at other ionic strengths. We focused our
search on ligands that contain various numbers of functional
groups, from one carboxyl group (Appendices A1A4) to ve
carboxyl groups (Appendix A16).
In cases where more than one source of data is available, we
selected the values that are underlined, based on our critique of
the original papers and represent the values we believe are most
reliable. The original papers must dene equilibrium quotients,
describe chemicals, instruments, procedures and calculation
methods used to obtain the data, as well as identify the com-
positions, ionic strengths, pH values, and temperatures of the
solutions. If different sources meet the above criteria, the data
derived at the standard state were selected. Examples of this
include S
r
, Pb(acetate)
, and Cu(ox-
alate) in Appendices A1 and A5. In cases where values of
entropies at the standard state are not available, the data ob-
tained by direct calorimetric measurement are preferable to
those obtained from the regression of stability constants at
various temperatures. This criterion was used to selected the
data for acetate complexes of Ho
3
, Er
3
and Cm
3
, Ce(gly-
colate)
2
, as well as NTA and HEDTA complexes of alkaline
earth elements (Appendices A1, A3, A9, and A10). If the data
from different sources were all derived from calorimetry, we
considered other criteria including ionic strengths and sources
of stability constants used to calculate S
r
. For example, S
r
values for Cd(acetate)
involving
complex formation where a ligand replaces (a) one and (b) six mole-
cules (m) of water surrounding a cation for which coordination num-
bers (n) vary from 4 to 12. We propose the slope of m/n for the
correlations, i.e., the slope becomes more negative as more water
molecules are displaced and as the coordination numbers of the cation
decrease (see text).
Table 1. Slopes and intercepts from Figures 14 for estimating S
r
o
.
Slope Ligand Intercept
0.15 acetate 7
0.15 glycinate 8
0.15 glycolate 4.4
0.15 picolinate 6
0.32 oxalate 16.3
0.32 malonate 16.3
0.32 dipicolate 10
0.32 diglycolate 10
0.84 NTA 18
0.84 HEDTA 13
0.84 N-(2-Carboxyethyl) iminodiacetate 18
0.84 N-(2-Carboxyphenyl) iminodiacetate 23
0.92 EDTA 24
0.92 CDTA 45
0.92 EGTA 17
0.92 DTPA 27
3936 P. Prapaipong and E. Shock
were selected from the sources cited in Appendices A1, A6,
A8, A10, and A13 because the measurements were made at
lower ionic strengths. As another example, we selected S
r
for
alkaline earth complexes of CDTA, EGTA, and DTPA (Ap-
pendices A14, A15, A16) derived by Anderegg (1963, 1964a,
1965) because the values were calculated from enthalpy and
Gibbs free energy of complexation measured in the same study,
whereas in the other studies only enthalpies were measured and
Gibbs free energy data were adopted from other sources, which
in some cases were derived in different types of solution media
of different ionic strengths.
In cases where data from all sources were obtained by
regression of stability constants at various temperatures, we
considered temperature ranges used for the regression and
agreement with other studies where more than two sources of
data were available. For example, S
r
for Mg(acetate)
from
Shock and Koretsky (1993) was selected because a stability
constant at 75C was available for the regression in addition to
stability constants at 25C and 35C used by Nancollas (1956).
Entropy values from certain studies were not selected because
the data were consistently found to differ from other studies,
including S
r
and S
r
are plotted against S
M
in Figure 1. The
intercept is constrained by values of S
r
taken from Martell and Smith (1974, 1977, 1982) and Smith and Martell (1989).
Values of S
M
are those from Shock et al. (1997). Different symbols designate differences in ionic strengths.
3938 P. Prapaipong and E. Shock
ligand structures, and that the correlations are independent of
cation charge. The slopes and intercepts from Figures 14 are
summarized in Table 1. These correlations allow estimates of
S
r
from S
M
is m/n.
Consider the hypothetical case of a ligand for which standard
partial molal entropies of metal complexes, S
C
S
M
S
C
S
L
, (5)
a plot of S
r
vs. S
M
and S
L
and S
M
are those from Shock et al. (1997). Solid circles represent the entropy data at standard state. Open symbols designate
the values at ionic strengths of 0.1 m.
3939 Entropies of association for aqueous metalorganic complexes
chelate. In cases where the number of water molecules dis-
placed is less, the slopes would be less negative.
Depicted in Figure 5 are calculated slopes for correlations
involving complexes of ligands for which m 1 and m 6.
The calculated slopes in Figure 5a would apply to correlations
involving monodentate ligands such as acetate, glycolate, and
glycinate (m 1) forming complexes with metal cations of
various C.N.; the slopes of the correlations are 1/4, 1/6,
1/8, and 1/12 when the C.N. of metal cations or n values
are 4, 6, 8, and 12 respectively. Returning to plots for com-
plexes of monovalent ligands in Figure 1, the slope obtained by
tting experimental data is 0.15, which is close to the theo-
retical slope of 1/6 for complexes of monodentate ligands
(m 1) and metal cations with n 6, a common C.N. for
cations. Note that although the ordinate in Figure 5a represents
a smaller range than the plots in Figures 14, the slopes of
1/12 to 1/4 are barely distinguishable. In fact, for this
reason, distinctive slopes for various C.N. from experimental
data were not detected in the construction of Figure 1. It is
evident from Figure 5a that differences in the slopes of 1/12
(0.08) to 1/4 (0.25) affect the estimation of S
r
only
slightly. In cases involving complexes of divalent ligands such
Fig. 9. Prediction of the partial molal entropy of association for
citrate complexes at 25C and 1 bar from the slope of 0.84 for the
correlation of S
r
and S
M
in Figure
4. The intercept is constrained by values of S
r
, taken from Martell and Smith (1974, 1977, 1982) and Smith and Martell
(1989). Values of S
M
r
for chelate-forming reactions in cases where experimental data are limited.
Ligand
Ligand
(common name) Slope Intercept
alkylmalonate butylmalonate 0.32 16
alkylmalonate t-butylmalonate 0.32 15
alkylmalonate ethylmalonate 0.32 15
2-amino-2-deoxy-D-gluconate D-glucosaminate 0.15 12
L-2-amino-3-hydroxybutanoate threonine 0.15 12
DL-2-amino-3-(2-hydroxyphenyl) O-tyrosine 0.15 15
DL-2-amino-3-(3-hydroxyphenyl) M-tyrosine 0.15 6
L-2-amino-3-(4-hydroxyphenyl) propanoate tyrosine 0.15 14
L-2-amino-3-hydroxypropanoate serine 0.15 10
L-2-amino-3-phenylpropanoate phenylalanine 0.15 12
L-2-amino-3-(4-imidazolyl) propanoate histidine 0.15 10
DL-2-aminobutanoate 0.15 12
DL-3-aminobutanoate 0.15 9
L-2-aminopropanoate alanine 0.15 12
3-aminopropanoate -alanine 0.15 7
benzenecarboxylate benzoate 0.15 8
benzene-1,2-dicarboxylate phthalate 0.32 13
benzene-1,3-dicarboxylate isophtalate 0.32 6
cis-butenedioate maleate 0.32 16
trans-1,2-cyclopentylene CPDTA 0.92 30
D-2,3-dihydroxybutanedioate D-tartarate 0.32 6
D-2,3-dihydroxybutanedioate D-tartarate 0.32 5
DL-(1,2-dimethylethylene) dinitrilotetraacetate 0.92 36
ethylenediiminodiacetate EDDA 0.32 21
ethylenedioxydiacetate 0.32 14
glycylglycine diglycinate 0.15 2
glycylglycylglycine triglycinate 0.15 5
hexamethyleneditrilotetraacetate 0.92 17
L-hydroxybutanedioate malate 0.32 6
N-(2-hydroxymethyl) iminodiacetate HIDA 0.32 17
2-hydroxypropane-1,2,3-tricarboxylate citrate 0.84 10
2-hydroxy-2-methylpropanoate 0.15 1
3-hydroxypropanoate 0.15 11
D-2-hydroxypropanoate lactate 0.15 2
L-4-hydroxypyrrolidine-2-carboxylate hydroxyprolinate 0.15 8
mercaptoacetate thioglycolate 0.15 9
3-mercaptopropanoate 0.15 14
DL-2-mercaptopropanoate thiolactate 0.15 6
DL-(methylethylene) dinitrilotetraacetate PDTA 0.92 35
N-methyliminodiacetate MIDA 0.32 15
2-methylpropanoate isobutyrate 0.15 14
N-(6-methyl-2-pyridylmethyl) iminodiacetate 0.32 28
nitrosalicylate 0.15 45
octamethylenedinirilotetraacetate 0.92 22
2-oxopropanoate pyruvate 0.15 4
oxybis(ethylenenitrilo)tetraacetate EEDTA 0.92 22
pentamethylenedinitrilotetraacetate 0.92 23
pentane-3,3-dicarboxylate diethylmalonate 0.32 15
phenoxyacetate 0.15 5
L-phenylhydroxyacetate mandelate 0.15 0
polychloroacetate dichloroacetate 0.15 2
polychloroacetate trichloroacetate 0.15 5
pyridine-2-acetate 0.15 3
pyrrole-2-carboxylate 0.15 9
1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate DOTA 0.92 29
1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetraacetate TETA 0.92 26
1,4,7,10-tetraazacyclotridecane-1,4,7,10-tetraacetate TRITA 0.92 30
tetramethylenedinitrilotetraacetate 0.92 32
thiobis(ethylenenitrilo)tetraacetate TEDTA 0.92 21
N-thioureidoiminodiacetate 0.32 14
trimethylenedinitrilotetraacetate TMDTA 0.92 31
uramil-N,N-diacetate 0.32 21
N-uridoiminodiacetate 0.32 24
3941 Entropies of association for aqueous metalorganic complexes
as oxalate and malonate, the theoretical slopes also agree well
with those obtained from experimental data. In Figure 2, the slope
of 0.32 was obtained by tting all of the experimental data for
dicarboxylate complexes, whereas the calculated slope is 2/6
(0.33) for cations with C.N. of six.
In contrast to mono- and dicarboxylate ligands, numbers of
water molecules replaced by more complicated ligands that
form chelates with metal cations are not well identied. In fact,
the numbers of water molecules replaced by a chelating agent
are not necessarily the same as numbers of functional groups or
carboxyl groups in the chelating agent. As an example, if we
equate values of m with the number of carboxyl groups, then
for n 6, the calculated slopes would be 3/6 (0.50) and
4/6 (0.67) for complexes of ligands containing three and
four carboxyl groups respectively. In contrast, the slopes ob-
tained from tting experimental data are 0.84 (Fig. 3) and
0.92 (Fig. 4) respectively. It should be noted further that there
is a large discrepancy between the experimental slopes for
complexes of dicarboxylate (0.33) and tricarboxylate ligands
(0.84).
We believe that the source of these differences, especially
the dramatic difference in slopes between complexes of small
and large ligands, relates to the ability of large ligands to form
chelates. Because chelating agents like NTA or EDTA are large
in size and have multiple functional groups, their molecules are
exible and can surround metal cations, which allows them to
repel more water molecules than estimated from an inventory
of their carboxyl functional groups. Note that the slopes ob-
tained from experimental data of 0.84 and 0.92 for chelates
of ligands containing three and four carboxyl groups are close
to 5/6 and 6/6. This implies that after chelation most of the
water molecules surrounding metal cations are likely to be
displaced by the formation of chelates. Note also that the slope
of 0.92 for chelates of ligands containing four carboxyl
groups is also applicable to complexes of DTPA, which con-
sists of ve carboxyl groups. This suggests that steric hin-
drances may prohibit some carboxyl groups from bonding with
metal cations when the chelating agent has a relatively large
structure.
In cases of ligands with multiple functional groups such as
EDTA and DTPA, virtually no water molecules remain in the
immediate vicinity around cations after chelation. Figure 5b
shows calculated slopes for correlations involving complexes
of ligands like EDTA, for the case where m 6. The slopes
vary from 6/6 to 6/12 for complexes of metal cations with
C.N. of 6 to 12. Note that the ordinate range of the plot is twice
as large as that in Figure 5a, hence the slopes for complexes of
cations with various C.N. are more distinctive. Therefore, C.N.
of metal cations have more inuence on predicted slopes and
consequently on estimates of S
r
during chelation when com-
pared with simple complexation. Nevertheless, as shown in
Figures 3 and 4, the slopes t many experimental data for a
variety of metal complexes within 5 cal mol
1
K
1
, and the
vast majority within 10 cal mol
1
K
1
. Adopting common
slopes provides a convenient yet reliable method for predicting
S
r
for chelates and complexes of a variety of cations.
Unlike correlation schemes for estimating S
r
for inorganic
complexes developed by Sverjensky et al. (1997) and for
monocarboxylate complexes obtained by Shock and Koretsky
(1993, 1995), correlations in this study are found to be inde-
pendent of cation charge. As a result, the estimates for mono-
carboxylate complexes in this study are not consistent with
those from Shock and Koretsky (1993, 1995).
Recent experimental results allow us to test whether the
correlations for estimating S
r
proposed here represent an
improvement over those proposed previously. Predicted asso-
ciation constants as functions of temperature for acetate com-
plexes of La
3
, Gd
3
, Nd
3
, and Yb
3
using S
r
values from
this study and those from Shock and Koretsky (1993) are
shown in Figure 6, together with experimental results from
Archer and Monk (1964, 1966), Deberdt et al. (1998, 2000),
and Wood et al. (2000). None of these experimental results
were regressed to obtain values of S
r
used to construct the
correlation shown in Figure 1a. It can be seen in Figure 6 that
the new predictive methods, which are meant to provide reli-
able estimates to 100 to 150C, are an improvement over the
systematically low estimates made by Shock and Koretsky
(1993). This difference is a direct result of more positive values
of S
r
estimated with the new correlation. The solid curves in
Figure 6 were calculated with new parameters for the revised
Helgeson-Kirkham-Flowers equation of state using values of
standard partial molal heat capacity (C
p
) and volume (V
) for
the complexes taken from Shock and Koretsky (1993). The
difference between predicted values and experimental data for
Nd(acetate)
2
association above 150C suggests that improve-
ments in the estimation procedure for C
p
of acetate complexes
of trivalent cations may now be possible.
As described above, we believe that there should be a second
order effect on the slopes and intercepts of entropy correlations
that is cation-dependent, perhaps because of variations in co-
ordination number. However, distinctive slopes for complexes
of cations with different charges can not be reliably identied
with the existing experimental data. In fact, we found that
adopting a single slope produces estimates for most metal
complexes of a given ligand to within approximately 5 cal
mol
1
K
1
despite differences in cation charge. Additional
factors in complexation, including displacement or reorienta-
tion of water molecules surrounding a ligand, may contribute to
a second order effect, and may help explain different slopes
obtained for ligands of various sizes. Changes in the location
and coordination of water molecules surrounding organic acid
ligands during complexation can be modeled with molecular
orbital calculations (Kubicki et al., 1996), and this should be a
way to test and improve upon the simple suggestions made
here. Meanwhile, by adopting common slopes, correlations can
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Latimer W. M. and Bufngton R. M. (1926) The entropy of aqueous
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Latimer W. M. and Kasper C. (1929) The theoretical evaluation of the
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Latimer W. M., Pitzer K. S., and Slansky C. M. (1939) The free energy
of hydration of gaseous ions, and the absolute potential of the normal
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Levy S. C. (1962) Some properties of rare earth-nitrilotriacetate com-
plexes. Ph.D. dissertation, Iowa State University of Science and
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Lindsay W. L. (1974) Role of chelation in micronutrient availability. In
The Plant Root and Its Environment (ed. E. W. Carson), pp. 507
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Lipton W. V. and Goldin A. S. (1976) Some factors inuencing the
uptake of plutonium-239 by pea plants. Health Physics 31, 425430.
Lovley D. R. and Woodward J. C. (1996) Mechanisms for chelator
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1924.
Lovley D. R., Woodward J. C., and Chapelle F. H. (1994) Stimulated
anoxic biodegradation of aromatic hydrocarbons using Fe(III) li-
gands. Nature 370, 128131.
Lundstrom U. and O
r
Ref.
Na
0 6.7* a
K
0 2.9* a
Ag
0 6 l
Mg
2
0 0.6* b
0 0.7* k
Ca
2
0 7.2* a
0 8.7* b
0 5.4* k
Sr
2
0 7.8* b
Ba
2
0 2.5* b
Fe
2
0 3.5* k
Cu
2
3.0 NaClO
4
12.1 c
Zn
2
3.0 NaClO
4
11.2 c
0 15.0* k
Cd
2
3.0 NaClO
4
10.9 c
0.25 NaClO
4
11.5 d
Pb
2
3.0 HClO
4
10.5 c
0 11.2* k
UO
2
2
1.0 NaClO
4
19.5 e
Al
3
0 26.3* o
Cr
3
0.3 HClO
4
18* j
La
3
2.0 NaClO
4
14.6 f
Ce
3
2.0 NaClO
4
14.8 e
2.0 NaClO
4
15.2* i
Pr
3
2.0 NaClO
4
14.2 f
Nd
3
2.0 NaClO
4
14.6 f
2.0 NaClO
4
15.4* m
Sm
3
2.0 NaClO
4
14.2 f
Eu
3
2.0 NaClO
4
13.4* i
2.0 NaClO
4
13 g
Gd
3
2.0 NaClO
4
14.8 f
Dy
3
2.0 NaClO
4
17.6 f
Ho
3
2.0 NaClO
4
18.3 f
2.0 NaClO
4
16.8* n
Er
3
2.0 NaClO
4
18.5 f
2.0 NaClO
4
18.5* n
Yb
3
2.0 NaClO
4
19.5 f
Y
3
2.0 NaClO
4
18.1 f
Am
3
2.0 NaClO
4
23.4* i
Cm
3
2.0 NaClO
4
14 g
2.0 NaClO
4
23.8* i
Th
4
1.0 NaClO
4
26.7 h
a. Daniele et al. (1985a); b. Nancollas (1956); c. Gerding (1967); d.
Gerding and Johansson (1968); e. Ahrland and Kullberg (1971); f.
Grenthe (1964); g. Choppin et al. (1985); h. Portanova et al. (1975); i.
Choppin and Schneider (1970); j. Tedesco and Gonzalez Quintana
(1970); k. Shock and Koretsky (1993); l. Martell and Smith (1977); m.
Bukietynska et al. (1981a); n. Bukietynska et al. (1981b); o. Palmer and
Bell (1994).
* S
r
from regression of log at various temperatures.
Appendix A2. Entropies of association (in cal mol
1
K
1
) for
glycinate complexes obtained from the literature by calorimetric mea-
surement at 25C and various ionic strengths (I) in m, unless otherwise
indicated.
Species I Medium S
r
Ref.
Ag
0.5 1 h
Mg
2
0.5 9 h
Ca
2
0 5.3* a
Mn
2
0 13.5* b
0 14 d
0 14.1* c
Fe
2
0 7.5 d
0 17.1* c
Co
2
0 13.7 b
0 13.6 d
0 13.5* c
Ni
2
0 14.5* b
0 14.3* c
0 13.4 d
Cu
2
0 19.7 d
0 19.0 e
0 19.7* c
Zn
2
0 15.4 d
0 15.7* c
Cd
2
0 14.4 d
0 15.9* c
Pb
2
3.0 NaClO
4
16.4* f
Ce
3
2.0 NaClO
4
14* g
Eu
3
2.0 NaClO
4
11* g
Pm
3
2.0 NaClO
4
15* g
Am
3
2.0 NaClO
4
13* g
Cm
3
2.0 NaClO
4
15* g
a. Daniele et al. (1985a); b. Brannan et al. (1964); c. Shock and
Koretsky (1995); d. Izatt et al. (1972); e. Izatt et al. (1964); f. Corrie
and Williams (1976); g. Tanner and Choppin (1968); h. Smith and
Martell (1989).
* S
r
from regression of log at various temperatures.
3947 Entropies of association for aqueous metalorganic complexes
Appendix A3. Entropies of association (in cal mol
1
K
1
) for
glycolate complexes obtained from the literature by calorimetric mea-
surement at 25C and various ionic strengths (I) in m, unless otherwise
indicated.
Species I Medium S
r
Ref.
Mg
2
0 4.8* f
Ba
2
0 5.5* f
Cu
2
1.0 9 h
UO
2
2
1.0 NaClO
4
15 b
La
3
2.0 NaClO
4
7.9 a
2.0 NaClO
4
7.0 d
Ce
3
2.0 NaClO
4
8.0 a
2.0 NaClO
4
8.9* e
Nd
3
2.0 NaClO
4
7.4 a
2.0 NaClO
4
7.8 d
Sm
3
2.0 NaClO
4
8.1 a
2.0 NaClO
4
7.9 d
Eu
3
2.0 NaClO
4
9.7* c
2.0 NaClO
4
8.1 d
Gd
3
2.0 NaClO
4
9.3 a
2.0 NaClO
4
8.8 d
2.0 NaClO
4
9.9* e
Tb
3
2.0 NaClO
4
10.7 d
Dy
3
2.0 NaClO
4
11.0 a
2.0 NaClO
4
11.1 d
Ho
3
2.0 NaClO
4
10.8 d
Er
3
2.0 NaClO
4
11.3 a
2.0 NaClO
4
11.8 d
Tm
3
2.0 NaClO
4
11.1 d
Yb
3
2.0 NaClO
4
11.4 a
2.0 NaClO
4
10.6 d
Lu
3
2.0 NaClO
4
10.0 d
Y
3
2.0 NaClO
4
11.1 a
2.0 NaClO
4
10.3 d
Am
3
2.0 NaClO
4
7.3* c
Cm
3
2.0 NaClO
4
8.6* c
Th
4
1.0 NaClO
4
20.5 g
a. Grenthe (1964); b. Di Bernardo et al. (1976); c. Choppin and
Degischer (1972); d. Choppin and Friedman (1966); e. Choppin and
Chopoorian (1961); f. Shock and Koretsky (1995); g. Di Bernardo et al.
(1978); h. Smith and Martell (1989).
* S
r
from regression of log at various temperatures.
Appendix A4. Entropies of association (in cal mol
1
K
1
) for
picolinate complexes obtained from the literature by calorimetric mea-
surement at 25C and various ionic strengths (I) in m, unless otherwise
indicated.
Species I Medium S
r
Ref.
Mg
2
0.2 NaNO
3
10.8 a
Ca
2
0.2 NaNO
3
4.5 a
Sr
2
0.2 NaNO
3
6.1 a
Ba
2
0.2 NaNO
3
6.8 a
Ni
2
1.0 NaNO
3
9.6 b
Cu
2
1.0 NaNO
3
13.6 b
Zn
2
1.0 NaNO
3
9.8 b
La
3
0.5 NaClO
4
11.9 c
Ce
3
0.5 NaClO
4
10.7 c
Pr
3
0.5 NaClO
4
11.0 c
Nd
3
0.5 NaClO
4
10.3 c
Sm
3
0.5 NaClO
4
10.8 c
Eu
3
0.5 NaClO
4
11.4 c
Gd
3
0.5 NaClO
4
12.5 c
Tb
3
0.5 NaClO
4
14.9 c
Dy
3
0.5 NaClO
4
14.9 c
Ho
3
0.5 NaClO
4
15.3 c
Er
3
0.5 NaClO
4
15.5 c
Tm
3
0.5 NaClO
4
15.9 c
Yb
3
0.5 NaClO
4
16.7 c
Lu
3
0.5 NaClO
4
15.6 c
Y
3
0.5 NaClO
4
15.6 c
a. Aruga (1983); b. Aruga (1979); c. Gritmon (1968).
Appendix A5. Entropies of association (in cal mol
1
K
1
) for
oxalate complexes obtained from the literature by calorimetric mea-
surement at 25C and various ionic strengths (I) in m, unless otherwise
indicated.
Species I Medium S
r
Ref.
Na
0 7.9* a
K
0 7.0* a
Mn
2
0 23.3* b
Co
2
0 24.1* b
Ni
2
0 25.9* b
Cu
2
0 28 c
0.1 NaClO
4
28.3 d
Pb
2
0 24.9* b
Fe
3
1.0 NaClO
4
40 e
a. Daniele et al. (1983); b. Prapaipong et al. (1999); c. McAuley et
al. (1966); d. Arena et al. (1978b); e. Dellien (1977).
* S
r
from regression of log at various temperatures.
3948 P. Prapaipong and E. Shock
Appendix A6. Entropies of association (in cal mol
1
K
1
) for
malonate complexes obtained from the literature by calorimetric mea-
surement at 25C and various ionic strengths (I) in m, unless otherwise
indicated.
Species I Medium S
r
Ref.
Li
0 15.5* a
Na
0 6.7* b
0 6.2* c
K
0 7.9* b
0 7.2* c
Mg
2
0 24.2* a
Co
2
0 27 d
Cu
2
0.1 NaClO
4
28 e, f
Zn
2
0 27.4* a
Cd
2
0 21.6* a
Pb
2
0 31.0* a
UO
2
2
1.0 NaClO
4
32 g
Sc
3
1.0 NaClO
4
38 h
Al
3
0 48.9* a
Fe
3
1.0 NaClO
4
43 i
La
3
0.1 NaClO
4
30 j
1.0 NaClO
4
24 k
Ce
3
0.1 NaClO
4
31 j
1.0 NaClO
4
25 k
Pr
3
0.1 NaClO
4
32 j
1.0 NaClO
4
25 k
Nd
3
0.1 NaClO
4
33 j
1.0 NaClO
4
26 k
Sm
3
0.1 NaClO
4
32 j
1.0 NaClO
4
27 k
Eu
3
0.1 NaClO
4
32 j
1.0 NaClO
4
27 k
Gd
3
0.1 NaClO
4
32 j
1.0 NaClO
4
27 k
Tb
3
0.1 NaClO
4
32 j
1.0 NaClO
4
28 k
Dy
3
0.1 NaClO
4
34 j
1.0 NaClO
4
28 k
Ho
3
1.0 NaClO
4
28 k
Er
3
0.1 NaClO
4
32 j
1.0 NaClO
4
28 k
Tm
3
0.1 NaClO
4
32 j
1.0 NaClO
4
29 k
Yb
3
0.1 NaClO
4
32 j
1.0 NaClO
4
29 k
Lu
3
0.1 NaClO
4
33 j
1.0 NaClO
4
29 k
Th
4
1.0 NaClO
4
44 g
a. Prapaipong et al. (1999); b. Daniele et al. (1985a); c. Daniele et al.
(1983); d. McAuley and Nancollas (1963); e. Arena et al. (1978b); f.
Arena et al. (1978a); g. Di Bernado et al. (1977); h. Grenthe and
Hansson (1969); i. Dellien (1977); j. Degischer and Choppin (1972); k.
Dellien (1973).
* S
r
from regression of log at various temperatures.
Appendix A7. Entropies of association (in cal mol
1
K
1
) for
dipicolinate complexes obtained from the literature by calorimetric
measurement at 25C and various ionic strengths (I) in m, unless
otherwise indicated.
Species I Medium S
r
Ref.
Mg
2
0.2 NaNO
3
22.7 a
Ca
2
0.2 NaNO
3
9.2 a
Sr
2
0.2 NaNO
3
10.3 a
Ba
2
0.2 NaNO
3
8.4 a
Ni
2
1.0 NaNO
3
20.3 b
Cu
2
1.0 NaNO
3
27.4 b
Zn
2
1.0 NaNO
3
20.3 b
Sc
3
0.5 Na/HClO
4
37.9 c
La
3
0.5 HClO
4
25.8 d
Ce
3
0.5 HClO
4
26.1 d
Pr
3
0.5 HClO
4
26.1 d
Nd
3
0.5 HClO
4
26.5 d
Sm
3
0.5 HClO
4
25.9 d
Eu
3
0.5 HClO
4
26.6 d
Gd
3
0.5 HClO
4
27.8 d
Tb
3
0.5 HClO
4
30.5 d
Dy
3
0.5 HClO
4
32.4 d
Ho
3
0.5 HClO
4
33.2 d
Er
3
0.5 HClO
4
33.8 d
Tm
3
0.5 HClO
4
34.2 d
Yb
3
0.5 HClO
4
34.0 d
Lu
3
0.5 HClO
4
33.9 d
Y
3
0.5 HClO
4
33.8 d
a. Aruga (1983); b. Aruga (1979); c. Grenthe and Hansson (1969); d.
Grenthe (1963).
Appendix A8. Entropies of association (in cal mol
1
K
1
) for
diglycolate complexes obtained from the literature by calorimetric
measurement at 25C and various ionic strengths (I) in m, unless
otherwise indicated.
Species I Medium S
r
Ref.
Li
0 8.4* a
Na
0 11.2* a
K
0 10.0* a
Ca
2
0 11.5* a
Ni
2
1.0 NaNO
3
20.1 b
Cu
2
1.0 NaNO
3
22.8 b
0.1 NaClO
4
31.1 c
Zn
2
1.0 NaNO
3
21.5 b
Cd
2
1.0 NaNO
3
13.5 b
UO
2
2
1.0 NaClO
4
36.9 d
Sc
3
1.0 Na/HClO
4
36.3 e
La
3
1.0 HClO
4
22.3 f
Ce
3
1.0 HClO
4
22.2 f
Pr
3
1.0 HClO
4
22.1 f
Nd
3
1.0 HClO
4
22.1 f
Sm
3
1.0 HClO
4
21.8 f
Eu
3
1.0 HClO
4
22.6 f
Gd
3
1.0 HClO
4
23.5 f
Tb
3
1.0 HClO
4
27.0 f
Dy
3
1.0 HClO
4
28.8 f
Ho
3
1.0 HClO
4
29.6 f
Er
3
1.0 HClO
4
30.1 f
Tm
3
1.0 HClO
4
30.5 f
Yb
3
1.0 HClO
4
30.2 f
Lu
3
1.0 HClO
4
30.0 f
Y
3
1.0 HClO
4
30.0 f
Th
4
1.0 NaClO
4
44.0 g
a. Daniele et al. (1985a); b. Aruga (1978); c. Cal ` et al. (1979); d. Di
Bernado et al. (1980); e. Grenthe and Hansson (1969); f. Grenthe
(1963); g. Di Bernardo et al. (1983).
* S
r
from regression of log at various temperatures.
3949 Entropies of association for aqueous metalorganic complexes
Appendix A9. Entropies of association (in cal mol
1
K
1
) for NTA
complexes obtained from the literature by calorimetric measurement at
25C and various ionic strengths (I) in m, unless otherwise indicated.
Species I Medium S
r
Ref.
Li
0.25 18* a
Na
0.25 12* a
K
0.25 17* a
VO
2
1.0 Na/HClO
4
62.9* b
Be
2
0.1 KNO
3
57* c
Mg
2
0.1 KNO
3
32* d
0 44.3*, e
0.1 KNO
3
39.8 f
Ca
2
0.1 KNO
3
23* d
0 31.4*, e
0.1 KNO
3
24.7 g
0.1 KNO
3
24.2 f
Sr
2
0.1 KNO
3
15* d
0.1 KNO
3
20.9 g
0.1 KNO
3
17.5 f
Ba
2
0.1 KNO
3
18* d
0 22.8*, e
0.1 KNO
3
17.1 f
Mn
2
0 46.0*, e
0.1 KNO
3
37.9 g
0.1 KNO
3
38.9 f
Co
2
0.1 KNO
3
47.1 g
0.1 KNO
3
47.2 f
Ni
2
0.1 KNO
3
44.1 g
0.1 KNO
3
43.9 f
Cu
2
0.1 KNO
3
53.0 g
0.1 KNO
3
52.8 f
Zn
2
0.1 KNO
3
46.0 g
0.1 KNO
3
45.5 f
Cd
2
0.1 KNO
3
31.3 f
Pb
2
0.1 KNO
3
39.1 f
Fe
3
0.1 KNO
3
83.6 f
La
3
0.5 NaClO
4
41.6 h
0.1 KNO
3
73.2*, i
Ce
3
0.5 NaClO
4
43.0 h
0.1 KNO
3
65.9*, i
Pr
3
0.5 NaClO
4
42.6 h
0.1 KNO
3
61.6*, i
Nd
3
0.5 NaClO
4
43.9 h
0.1 KNO
3
64.5*, i
Sm
3
0.5 NaClO
4
45.4 h
0.1 KNO
3
67.1*, i
Eu
3
0.5 NaClO
4
45.9 h
0.1 KNO
3
69.9*, i
Gd
3
0.5 NaClO
4
47.7 h
0.1 KNO
3
75.1*, i
Tb
3
0.5 NaClO
4
50.4 h
0.1 KNO
3
80.1*, i
Dy
3
0.5 NaClO
4
53.0 h
0.1 KNO
3
77.0*, i
Ho
3
0.5 NaClO
4
54.1 h
0.1 KNO
3
75.1*, i
Er
3
0.5 NaClO
4
53.8 h
0.1 KNO
3
78.3*, i
Tm
3
0.5 NaClO
4
54.5 h
0.1 KNO
3
78.9*, i
Yb
3
0.5 NaClO
4
54.3 h
0.1 KNO
3
75.1*, i
Lu
3
0.5 NaClO
4
54.0 h
0.1 KNO
3
78.8*, i
Y
3
0.5 NaClO
4
53.2 h
0.1 KNO
3
86.5*, i
Am
3
0.1 HClO
4
56.1* j
Zr
4
0 129.8 k
Hf
4
0 124.0 k
a. Daniele et al. (1985b); b. Yamada et al. (1976); c. Frausto da Silva
and Candida T. Abreu Vaz (1977); d. Beltran et al. (1965); e. Hughes
and Martell (1956); f. Anderegg (1964b); g. Hull et al. (1964); h.
Gritmon (1968); i. Levy (1962); j. Eberle and Sabau (1972); k. Vasilev
et al. (1981).
* S
r
from regression of log at various temperatures.
S
r
at 20C.
Appendix A10. Entropies of association (in cal mol
1
K
1
) for
HEDTA complexes obtained from the literature by calorimetric mea-
surement at 25C and various ionic strengths (I) in m, unless otherwise
indicated.
Species I Medium S
r
Ref.
Mg
2
0.1 KNO
3
19* a
0.1 KNO
3
43 b
Ca
2
0.1 KNO
3
19* a
0.1 KNO
3
15 b
Sr
2
0.1 KNO
3
11* a
0.1 KNO
3
14 b
Ba
2
0.1 KNO
3
5* a
0.1 KNO
3
10 b
Mn
2
0.1 KNO
3
32 b
Fe
2
0.1 KNO
3
33 b
Co
2
0.1 KNO
3
44 b
Ni
2
0.1 KNO
3
45 b
Cu
2
0.1 KNO
3
48 b
Zn
2
0.1 KNO
3
38 b
Cd
2
0.1 KNO
3
25 b
Hg
2
0.1 KNO
3
64.8* c
0.1 KNO
3
25 b
Pb
2
0.1 KNO
3
29 b
Al
3
0.1 KNO
3
89.1* c
Y
3
0.1 KCl 58.2 d
0.5 NaClO
4
57.2 e
0.100.11 KNO
3
66.1* f
La
3
0.1 KCl 46.5 d
0.5 NaClO
4
44.8 e
0.100.11 KNO
3
54.2* f
Ce
3
0.1 KCl 47.0 d
0.5 NaClO
4
46.1 e
0.100.11 KNO
3
54.4* f
Pr
3
0.1 KCl 45.5 d
0.5 NaClO
4
43.8 e
0.100.11 KNO
3
52.0* f
Nd
3
0.1 KCl 46.7 d
0.5 NaClO
4
43.7 e
0.100.11 KNO
3
53.8* f
Sm
3
0.1 KCl 45.7 d
0.5 NaClO
4
42.5 e
0.100.11 KNO
3
54.4* f
Eu
3
0.1 KCl 46.0 d
0.5 NaClO
4
42.5 e
0.100.11 KNO
3
54.1* f
Gd
3
0.1 KCl 46.4 d
0.5 NaClO
4
44.1 e
0.100.11 KNO
3
54.1* f
Tb
3
0.1 KCl 49.2 d
0.5 NaClO
4
46.4 e
0.100.11 KNO
3
58.8* f
Dy
3
0.1 KCl 52.9 d
0.5 NaClO
4
51.8 e
0.100.11 KNO
3
62.8* f
Ho
3
0.1 KCl 57.5 d
0.5 NaClO
4
56.4 e
0.100.11 KNO
3
66.3* f
Er
3
0.1 KCl 61.4 d
0.5 NaClO
4
59.6 e
0.100.11 KNO
3
69.4* f
Tm
3
0.1 KCl 64.3 d
0.5 NaClO
4
63.3 e
0.100.11 KNO
3
74.5* f
Yb
3
0.1 KCl 64.5 d
0.5 NaClO
4
62.8 e
0.100.11 KNO
3
74.0* f
Lu
3
0.1 KCl 64.9 d
0.5 NaClO
4
62.7 e
0.100.11 KNO
3
73.4* f
a. Beltran et al. (1965); b. Wright et al. (1965); c. Moeller and Chu
(1966); d. Fuger et al. (1968); e. Gritmon (1968); f. Moeller and Ferrus
(1961).
* S
r
from regression of log at various temperatures.
3950 P. Prapaipong and E. Shock
Appendix A11. Entropies of association (in cal mol
1
K
1
) for
N-(2-carboxyethyl)iminodiacetate complexes obtained from the litera-
ture by calorimetric measurement at 25C and various ionic strengths
(I) in m, unless otherwise indicated.
Species I Medium S
r
Ref.
Mg
2
0.1 KNO
3
35.6 a
Ca
2
0.1 KNO
3
22.2 a
Sr
2
0.1 KNO
3
16.2 a
Ba
2
0.1 KNO
3
15.2 a
Mn
2
0.1 KNO
3
37.2 b
Co
2
0.1 KNO
3
40.1 b
Ni
2
0.1 KNO
3
39.9 a
0.1 KNO
3
39.9 b
Cu
2
0.1 KNO
3
46.7 b
Zn
2
0.1 KNO
3
42.1 b
a. Uhlig and Martin (1969); b. Martin and Uhlig (1970).
Appendix A12. Entropies of association (in cal mol
1
K
1
) for
N-(2-carboxyphenyl)iminodiacetate complexes obtained from the liter-
ature by calorimetric measurement at 25C and various ionic strengths
(I) in m, unless otherwise indicated.
Species I Medium S
r
Ref.
Mg
2
0.1 KNO
3
44.0 a
Ca
2
0.1 KNO
3
27.7 a
Sr
2
0.1 KNO
3
22.5 a
Ba
2
0.1 KNO
3
20.7 a
Mn
2
0.1 KNO
3
42.4 b
Co
2
0.1 KNO
3
49.6 b
Ni
2
0.1 KNO
3
48.3 a
0.1 KNO
3
48.3 b
Cu
2
0.1 KNO
3
56.1 b
Zn
2
0.1 KNO
3
48.9 b
a. Uhlig and Martin (1969); b. Martin and Uhlig (1970).
Appendix A13. Entropies of association (in cal mol
1
K
1
) for
EDTA complexes obtained from the literature by calorimetric measure-
ment at 25C and various ionic strengths (I) in m, unless otherwise
indicated.
Species I Medium S
r
Ref.
Li
1.0 (CH
3
)
4
NH
4
Cl 14.9 a
0.1 (CH
3
)
4
NH
4
Cl 14.3 a
13 b
0.25 14* c
Na
1.0 (CH
3
)
4
NH
4
Cl 1.5 a
0.1 NaCl 4 a
3 b
0.25 5.5* c
0 4.7* d
K
0.25 7.2* c
0.1 (CH
3
)
4
NNO
3
3.7* e
Ag
0.1 KNO
3
7.8 a
Tl
0.1 KNO
3
5.3 a
Be
2
0.1 KNO
3
76* f
Mg
2
0.1 KNO
3
51.0 g, h, i
0.16 (CH
3
)
4
NH
4
Cl 51* j
0.1 KNO
3
50.5 k
0.0 32* l
52 b
0.1 KNO
3
50.5 m
0 65.1* n
0 61.9* p
Appendix A13. (Continued)
Species I Medium S
r
Ref.
Ca
2
0.1 KNO
3
26.6 g,h,i
0.16 (CH
3
)
4
NH
4
Cl 29* j
0.1 KNO
3
26.9 k
0.0 42* l
31 b
0.1 KNO
3
26.9 m
0 36.6* p
Sr
2
0.1 KNO
3
25.6 g
0.1 KNO
3
25.4 k
0.0 26* l
26 b
0.1 KNO
3
25.4 m
Ba
2
0.1 KNO
3
19.0 k
0.0 22* l
18 b
0.1 KNO
3
18.7 g
0.1 KNO
3
19.0 m
0 27.75* q
0.1 KNO
3
18 r
Fe
2
0.1 KNO
3
51 r
Mn
2
0.1 KNO
3
44.5 m
0.1 KNO
3
47.6 g,i
0.1 KNO
3
46.6 h
41 b
Co
2
0.1 KNO
3
60.3 g,h,i
58 b
0.1 KNO
3
59.7 m
Ni
2
0.1 KNO
3
59.4 g,h,i
0.1 KNO
3
56.7 k
55 b
0.1 KNO
3
56.7 m
0.1 KNO
3
57 r
Cu
2
0.1 KNO
3
58.2 g,h,i
0.1 KNO
3
56.4 k
55 b
0.1 KNO
3
56.4 m
0 67.1 s
0.1 KNO
3
56 r
Zn
2
0.1 KNO
3
57.8 h
0.1 KNO
3
59.0 g,i
0.1 KNO
3
56.3 k
55 b
0.1 KNO
3
56.3 m
0.1 KNO
3
57 r
Cd
2
0.1 KNO
3
44.4 g,h,i
0.1 KNO
3
40.9 k
38 b
0.1 KNO
3
40.9 m
0.1 KNO
3
42 r
Hg
2
0.1 KNO
3
35.5 g,h,i
0.1 KNO
3
67.4* t
0.1 KNO
3
37 r
Pb
2
0.1 KNO
3
37.5 g,h,i
0.1 KNO
3
34.5 k
35 b
0.1 KNO
3
34.5 m
UO
2
2
0.1 KNO
3
45* bb
Al
3
0.1 KNO
3
117.4* t
0.1 KNO
3
116.6 m
Fe
3
0.2 75*, u
0.1 HClO
4
/NaClO
4
105 v
In
3
0.1 KNO
3
89.5 m
Y
3
0.5 NaClO
4
66.8 w
0.1 KNO
3
77.5 x
0.1 KNO
3
83.8 m
La
3
0.1 KNO
3
61.4 g,h,i
0.1 KCl 66.8* y
0.1 KCl 68.8 z
0.5 NaClO
4
53.7 w
0.1 KNO
3
59.7 x
3951 Entropies of association for aqueous metalorganic complexes
Appendix A14. Entropies of association (in cal mol
-1
K
-1
) for CDTA
complexes obtained from the literature by calorimetric measurement at
25C and various ionic strengths (1) in m, unless otherwise indicated.
Species I Medium S
r
Ref.
Mg
2
0.2 KNO
3
64.7 a
1 KCI 54.1 b
0.1 KNO
3
52 c
0.1 KNO
3
63.1 d
Ca
2
0.2 KNO
3
47.0 a
1 KCI 39.2 b
0.1 KNO
3
35 c
0.1 KNO
3
47.5 d
Sr
2
0.2 KNO
3
44.9 a
1 KCI 46.2 b
0.1 KNO
3
34 c
0.1 KNO
3
45.7 d
Ba
2
0.2 KNO
3
39.6 a
1 KCI 34.0 b
0.1 KNO
3
29 c
0.1 KNO
3
40.9 d
Mn
2
0.1 KNO
3
52 c
0.1 KNO
3
65.6 d
Fe
2
0.1 KNO
3
61 c
Co
2
0.1 KNO
3
68 c
0.1 KNO
3
80.0 d
Ni
2
0.1 KNO
3
63 c
Cu
2
0.1 KNO
3
67 c
0.1 KNO
3
79.7 d
Zn
2
0.2 KNO
3
80.4 a
0.1 KNO
3
59 c
0.1 KNO
3
81.8 d
Cd
2
0.2 KNO
3
66.1 a
0.1 KNO
3
50 c
0.1 KNO
3
65.7 d
Hg
2
0.2 KNO
3
58.4 a
0.1 KNO
3
62.19* c
0.1 KNO
3
48 c
0.1 KNO
3
59.0 d
0.1 KNO
3
60.04* g
Pb
2
0.1 KNO
3
47 c
0.1 KNO
3
54.2 d
Al
3
0.1 KNO
3
121.7* h
Fe
3
0.2 86*, f
Y
3
0.1 KNO
3
103.0* g
La
3
0.1 KNO
3
82.8 d
0.1 KNO
3
86.7* g
Ce
3
86 i
Pr
3
0.1 KNO
3
95.6* g
87 i
Nd
3
0.1 KNO
3
97.6* g
88 i
Sm
3
0.1 KNO
3
102.0* g
95 i
Eu
3
0.1 KNO
3
104.5* g
95 i
Gd
3
0.1 KNO
3
105.3* g
96 i
Tb
3
0.1 KNO
3
105.1* g
99 i
Dy
3
0.1 KNO
3
100.5* g
99 i
Ho
3
0.1 KNO
3
95.0* g
100 i
Er
3
0.1 KNO
3
92.8* g
101 i
Tm
3
0.1 KNO
3
88.3* g
101 i
Yb
3
0.1 KNO
3
80.2* g
101 i
Appendix A13. (Continued)
Species I Medium S
r
Ref.
Ce
3
0.1 KCl 69.1* y
0.5 NaClO
4
55.8 w
0.1 KNO
3
60.8 x
0.1 KNO
3
64.8 m
Pr
3
0.1 KCl 69.4* y
0.5 NaClO
4
54.0 w
0.1 KNO
3
61.4 x
Nd
3
0.1 KCl 70.7* y
0.5 NaClO
4
50.0 w
0.1 KNO
3
61.3 x
0.1 KNO
3
65.8 m
Sm
3
0.1 KCI 72.9* y
0.5 NaCIO
4
53.0 w
0.1 KNO
3
64.4 x
Eu
3
0.1 KCI 75.7* y
0.5 NaCIO
4
56.0 aa
0.5 NaCIO
4
54.3 w
0.1 KNO
3
67.6 x
Gd
3
0.1 KCl 78.4* y
0.5 NaCIO
4
56.1 w
0.1 KNO
3
71.2 x
0.1 KNO
3
75.7 m
Tb
3
0.1 KCI 84.3* y
0.5 NaCIO
4
63.2 w
0.1 KNO
3
75.5 x
Dy
3
0.1 KCl 86.3* y
0.5 NaCIO
4
63.9 w
0.1 KNO
3
77.3 x
Ho
3
0.1 KCI 86.7* y
0.5 NaCIO
4
65.2 w
0.1 KNO
3
78.0 x
Er
3
0.1 KCI 89.1* y
0.5 NaCIO
4
66.2 w
0.1 KNO
3
78.3 x
Tm
3
0.1 KCI 90.6* y
0.5 NaCIO
4
67.5 w
0.1 KNO
3
79.1 x
Yb
3
0.1 KCI 91.3* y
0.5 NaCIO
4
68.7 w
0.1 KNO
3
79.2 x
Lu
3
0.1 KCI 89.7* y
0.5 NaCIO
4
68.9 w
0.1 KNO
3
79.1 x
Pu
3
0.1 KCI 68.6 z
Am
3
0.1 KCI 67.5 z
Cm
3
0.5 NaCIO
4
53.8 aa
Zr
4
0 147.9 cc,dd
133 ee
Hf
4
0 153.5 gg
134 ee
Th
4
0.1 96 ff
a. Anderegg (1976); b. Charles (1954); c. Daniele et al. (1985b); d.
Vasilev and Belonogova (1976b); e. Hovey (1988), recalculated from
other studies; f. Frausto da Silva and Candida T. Abreu Vaz (1977); g.
Anderegg (1963); h. Anderegg (1964a); i. Anderegg (1965); j. Arena et
al. (1983); k. Care and Staveley (1956); l. Carini and Martell (1953); m.
Staveley and Randall (1958); n. Vasilev and Belonogova (1975); p.
Vasilev and Belonogova (1976a); q. Vasilev et al. (1983); r. Wright
et al. (1965); s. Vasilev and Belonogova (1977); t. Moeller and Chu
(1966); u. Borggaard (1972); v. Doi (1978); w. Gritmon (1968); x.
Mackey et al. (1962); y. Betts and Dahlinger (1959); z. Fuger and
Cunningham (1965); aa. Choppin et al. (1985); bb. Frausto da Silva and
Lourdes Sadler Simoes (1969); cc. Vasilev et al. (1978a); dd. Vasilev
et al. (1978b); ee. Martell and Smith (1982), assuming H for 1 of
0.0 H for 0.1; ff. Smith and Martell (1989); gg. Vasilev et al.
(1978c).
* S
r
from regression of log at various temperatures.
S
r
at 20C.
3952 P. Prapaipong and E. Shock
Appendix A15. Entropies of association (in cal mol
-1
K
-1
) for EGTA
complexes obtained from the literature by calorimetric measurement at
25C and various ionic strengths (I) in m, unless otherwise indicated.
Species I Medium S
r
Ref.
Mg
2
0.1 KNO
3
41.5 a
0.1 KCl or KNO
3
42.6 b
0.1 KNO
3
40 c
Ca
2
0.1 KNO
3
21.6 a
0.1 KCl or KNO
3
23.2 b
0.1 KNO
3
23 c
Sr
2
0.1 KCl or KNO
3
19.3 b
0.1 KNO
3
15 c
Ba
2
0.1 KCl or KNO
3
7.8 b
0.1 KNO
3
7.1 c
Mn
2
0.1 KNO
3
21.5 a
0.1 KNO
3
27 c
Fe
2
0.1 KNO
3
37 c
Co
2
0.1 KNO
3
46.5 a
0.1 KNO
3
45 c
Ni
2
0.1 KNO
3
41.0 a
0.1 KNO
3
45 c
Cu
2
0.1 KNO
3
43.5 a
0.1 KNO
3
46 c
Zn
2
0.1 KNO
3
44.4 a
0.1 KCl or KNO
3
42.1 b
0.1 KNO
3
53 c
Cd
2
0.1 KNO
3
23.2 a
0.1 KCl or KNO
3
25.7 b
0.1 KNO
3
29 c
Hg
2
0.1 KNO
3
25.2 a
0.1 KNO
3
63.05* d
0.1 KNO
3
37 c
Pb
2
0.1 KNO
3
9.1 a
0.1 KNO
3
25 c
La
3
0.1 KNO
3
53.6 a
UO
2
2
0.1 KNO
3
51* e
Th
4
0.1 KNO
3
105.10* d
Zr
4
0.1 KNO
3
78.82* d
a. Anderegg (1964a); b. Boyd et al. (1965); c. Wright et al. (1965);
d. Hseu and Jyi (1981); e. Frausto da Silva and Lourdes Sadler Simoes
(1969).
* S
r
from regression of log at various temperatures.
S
r
at 20C.
Appendix A16. Entropies of association (in cal mol
1
K
1
) for DTPA
complexes obtained from the literature by calorimetric measurement at
25C and various ionic strengths (I) in m, unless otherwise indicated.
Species I Medium S
r
Ref.
Mg
2
0.1 KNO
3
52.4 a
0.1 KNO
3
50 b
0.1 KNO
3
54 c
Ca
2
0.1 KNO
3
29.5 a
0.1 KNO
3
30 b
0.1 KNO
3
29 c
Sr
2
0.1 KNO
3
21 b
0.1 KNO
3
19 c
Ba
2
0.1 KNO
3
16 b
0.1 KNO
3
14 c
Mn
2
0.1 KNO
3
47.0 a
0.1 KNO
3
46 c
Fe
2
0.1 KNO
3
49 c
Co
2
0.1 KNO
3
56.2 a
0.1 KNO
3
56 c
Ni
2
0.1 KNO
3
52.7 a
0.1 KNO
3
54 c
Cu
2
0.1 KNO
3
52.2 a
0.1 KNO
3
53 c
Zn
2
0.1 KNO
3
55.0 a
0.1 KNO
3
50 c
Cd
2
0.1 KNO
3
46.4 a
0.1 KNO
3
45 c
Hg
2
0.1 KNO
3
41.3 a
0.1 KNO
3
46.1* d
0.1 KNO
3
44 c
Pb
2
0.1 KNO
3
21.8 a
0.1 KNO
3
22 c
Al
3
0.1 KNO
3
110 e
0.1 KNO
3
113* f
Sc
3
0.1 86 i
Y
3
0.1 KNO
3
79 e
0.1 KNO
3
83.4* d
La
3
0.1 KNO
3
73.5 a
0.1 KNO
3
72 e
0.1 KNO
3
71.8 g
0.1 KNO
3
70.0* d
Ce
3
0.1 67.36* h
Pr
3
0.1 KNO
3
74.8 g
0.1 KNO
3
72.0* d
Nd
3
0.1 KNO
3
75.0 g
0.1 KNO
3
79.4* d
Sm
3
0.1 KNO
3
75.7 g
0.1 KNO
3
74.7* d
Eu
3
0.1 KNO
3
76.0 g
0.1 KNO
3
75.3* d
Gd
3
0.1 KNO
3
76.7 g
0.1 KNO
3
77.6* d
Tb
3
0.1 KNO
3
78.0 g
0.1 KNO
3
78.1* d
Dy
3
0.1 KNO
3
78.0 g
0.1 KNO
3
77.6* d
Ho
3
0.1 KNO
3
79.0 g
0.1 KNO
3
78.7* d
Er
3
0.1 KNO
3
79.3 g
0.1 KNO
3
79.6* d
Tm
3
0.1 KNO
3
82.0 g
0.1 KNO
3
85.5* d
Yb
3
0.1 KNO
3
82.7 g
0.1 KNO
3
85.1* d
Lu
3
0.1 KNO
3
85.7 g
0.1 KNO
3
87.2* d
Th
4
0.1 84.66* h
a. Anderegg (1965); b. Carson et al. (1968c); c. Wright et al. (1965);
d. Moeller and Thompson (1962); e. Carson et al. (1968a); f. Moeller
and Chu (1966); g. Carson et al. (1968b); h. Hseu et al. (1983); i.
Martell and Smith (1974).
* S
r
from regression of log at various temperatures.
S
r
at 20C.
S
r
at 27C.
Appendix A14. (Continued)
Species I Medium S
r
Ref.
Lu
3
0.1 KNO
3
79.2* g
103 i
Zr
4
0.1 KNO
3
80.51* e
Th
4
0.1 KNO
3
107.08* e
a. Carson et al. (1969); b. Simeon et al. (1969); c. Wright et al.
(1965); d. Anderegg (1963); e. Hseu et al. (1965); f. Borggaard (1972);
g. Moeller and Hseu (1962); h. Moeller and Chu (1966); i. Smith and
Martell (1989); assuming H for I of 0.5 H for 0.1.
* S
r
from regression of log at various temperatures.
S
r
at 20C.
3953 Entropies of association for aqueous metalorganic complexes