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Estimation of standard-state entropies of association for aqueous metalorganic


complexes and chelates at 25C and 1 bar
PANJAI PRAPAIPONG and EVERETT L. SHOCK*
GEOPIG, Department of Earth and Planetary Sciences, Washington University, St. Louis, MO 63130, USA
(Received October 16, 2000; accepted in revised form May 31, 2001)
AbstractLinear correlations between entropies of association for metalorganic complexes and chelates
(S
r
) and standard partial molal entropies of aqueous cations (S
M

) at 25C and 1 bar are identied to estimate


the temperature dependence for association constants of aqueous metalorganic complexes and chelates. The
correlations are systematically dependent on ligand structure and cation coordination number as revealed by
common slopes of 0.15, 0.32, 0.84, and 0.92 for complexes of monocarboxylate ligands, dicarboxy-
late ligands, and ligands consisting of three and four carboxyl groups, respectively. The grouping of different
types of ligands allows the use of structural considerations in the correlation methods, which provide rapid
estimation of the temperature dependence of association constants. These developments expand the number
and variety of metalorganic complexes and chelates that can be included in theoretical models of the
distribution, transport, and bioavailability of metals in geochemical and environmental processes. Copyright
2001 Elsevier Science Ltd
1. INTRODUCTION
Despite the fact that the majority of organic acids in natural
waters are not well-identied, complexes between organic ac-
ids and metal cations appear to be ubiquitous in natural waters.
In fact, in some aquatic environments, the speciation of metal
cations is dominated by organic complexes. For example, over
99% of Cu in seawater, over 60% of Zn in estuarine water, 50
to 70% of Pb in seawater, and 40% of Al in freshwater are
present as organic complexes (Morel and Hering, 1993). Metal
organic complexes are also found in other environments where
organic acids are abundant, including soil solutions in root
zones, swamps, marshes, and some oil-eld brines. Addition-
ally, human activities have dramatically increased the abun-
dance of aquatic organic compounds, some of which are strong
complexing and chelating agents. As a consequence, the effects
of organic compounds in geochemical and biogeochemical
processes such as mobility, toxicity, and bioavailability of
metals can be enhanced even in river water or groundwater
where organic acids are believed to be relatively dilute.
Quantitative models of these processes require association
constants of all complexes that these ligands are likely to form.
Ample data at 25C and 1 bar are available for these com-
plexes, but less is known about how association constants
change with temperature over the range of 0 to 150C where
natural or anthropogenic compounds are present. Efforts have
been made to predict thermodynamic data at high temperature
and pressure for organic acids, metalacetate, metalmonocar-
boxylate, and metaldicarboxylate complexes (Shock, 1995;
Shock and Koretsky, 1993, 1995; Prapaipong et al., 1999). The
present study builds upon these efforts to estimate the temper-
ature dependence for association constants of metal chelates
containing up to ve carboxyl groups. Examples of these li-
gands include benzoate, an aromatic monocarboxylate; lactate,
a monocarboxylate with three carbon atoms and one hydroxyl
group; phthalate, an aromatic dicarboxylate; and citrate, a tri-
carboxylate consisting of six carbon atoms and one hydroxyl
group. It is also the purpose of this study to investigate ther-
modynamic properties of larger carboxylate chelates such as
nitrilotriacetate (NTA), consisting of one tertiary amine with
three carboxyl groups; ethylenedinitrilotetraacetate (EDTA),
made up of four carboxyl groups branching off two tertiary
amines which connect to each other by an alkane chain; trans-
1,2-cyclohexylenedinitrilotetraacetate (CDTA), similar to
EDTA, but with the two tertiary amines connected to each other
by a cycloalkane group; and diethylenetrinitrilopentaacetate
(DTPA), composed of ve carboxyl groups branching off three
tertiary amines which bond to each other by an alkane chain.
The sources of mono-, di-, and some tricarboxylic acids in
aquatic systems can be biotic, but most well-dened chelating
agents are anthropogenic. Biotic origins of organic acids are
thought to include the decomposition of plant and animal
residues and diagenesis of kerogen, as well as direct secretions
from plants, fungi, and microorganisms (Prapaipong et al.,
1999). Owing to their ability to sequester and reduce metals,
chelating agents are widely used to remove unwanted metals in
industrial, pharmaceutical, medical, and agricultural applica-
tions, including nuclear power plants, all of which have become
major contributors of organic compounds in some aquatic
environments (Ayres, 1970; Wallace, 1972; Lindsay, 1974;
Bell, 1977; Rubin and Martell, 1980; Means et al., 1980;
Martell et al., 1985; Cleveland and Rees, 1981; Raymond,
1985; Morel and Hering, 1993; Martell and Hancock, 1996;
Brooks et al., 1998; Read et al., 1998).
These industrial and medical applications, as well as natural
sources, introduce chelating agents and metalorganic chelates
into the environment, where they can affect various geochemi-
cal and biogeochemical processes including mineral dissolu-
tion, secondary porosity enhancement, trace element mobility,
and trace element bioavailability and toxicity. As the environ-
* Author to whom correspondence should be addressed (shock@
zonvark.wustl.edu).
Pergamon
Geochimica et Cosmochimica Acta, Vol. 65, No. 21, pp. 39313953, 2001
Copyright 2001 Elsevier Science Ltd
Printed in the USA. All rights reserved
0016-7037/01 $20.00 .00
3931
mental input of synthetic organic chelates rises, these effects
can be further enhanced and complicated. For example, as
organic acids or chelating agents migrate in subsurface waters
or sediments, they can form complexes with metal ions on the
surfaces of oxide or silicate minerals, or directly adsorb on the
mineral surfaces and alter the adsorption of metal cations
(Stone and Morgan, 1984; Lundstrom and O

hman, 1990; Man-


ning et al., 1991; Huang and Longo, 1992; Luther et al., 1992;
Ullman et al., 1996). Mechanisms of coadsorption of trace
metals such as Pb
2
, Co
2
, Ni
2
, Zn
2
, Cu
2
, Cd
2
, As
3
,
Se
4
and actinides with NTA, N-(2-hydroxyethyl)ethylene di-
nitrilotriacetate (HEDTA), and EDTA on the surface of min-
erals, such as Fe-, Mn-, and Al oxides and hydroxides have
been proposed by several investigators (Means et al., 1978;
Bowers and Huang, 1986; Arnold et al., 1988; Girvin et al.,
1993; Jardine et al., 1993; Scott and Morgan, 1995, 1996;
Zachara et al., 1995; Bargar et al., 1996; Brooks et al., 1996;
Nowack and Sigg, 1996, 1997; Bargar et al., 1997a, b;
McArdell et al., 1998; Bargar et al., 1999; Collins et al., 1999;
Klewicki and Morgan, 1999). Furthermore, the dissolution of
minerals by chelating agents can complicate biogeochemical
processes. Lovley and Woodward (1996) found that microbial
ferric reduction in sediments can be induced by the enhanced
dissolution of ferric oxides by NTA. This study has also led to
possible uses of synthetic chelators in bioremediation. For
instance, microbial reduction of ferric chelators can be used to
clean up petroleum-contaminated aquifers (Lovley et al., 1994).
In phytoextraction, EDTA can be applied to Pb-contaminated
soil to increase bioavailable Pb, which is then removed from
soil by Pb-accumulating plants (Lipton and Goldin, 1976; Jr-
gensen, 1993; Blaylock et al., 1997; Huang et al., 1997). Efforts
to develop remediation and detoxication methods, as well as
efforts to understand the roles of organic complexes and che-
lates in aquatic environments that occur in a wide range of
temperatures, would benet from consistent sets of association
constants for the complexes and chelates involved in the sys-
tems, and their temperature dependence.
Thermodynamic properties of metal complexes and chelates
predicted in the present study allow quantitative models of
processes such as those described above in a variety of settings,
including sedimentary basins, hot springs, aquatic systems im-
pacted by industry, landlls, waste depositories, and soil envi-
ronments in the vicinity of microorganisms and plant roots. In
addition to the direct applications of the estimated thermody-
Fig. 1. Plots of the partial molal entropy of association at 25C and 1 bar for monocarboxylate complexes, (a) acetate,
(b) glycinate, (c) glycolate, and (d) picolinate, as a function of the standard partial molal entropy of the aqueous cations at
25C and 1 bar. Literature values of S
r
are taken from Appendices A1A4, and values of S
M

are taken from Shock et al.


(1997). Solid circles represent entropy data at standard state. Open symbols designate those measured at various ionic
strengths from 0.2 to 3 m. The solid lines exhibit a consistent slope of 0.15.
3932 P. Prapaipong and E. Shock
namic data to the systems enriched with organic chelates and
complexes, these data can be used as models for more compli-
cated organic molecules such as proteins, carbohydrates, and
humic substances. Although the size and structure of these
molecules are large and complex, the chemical functional groups
in the molecules can be categorized into a few classes including
carboxyl, hydroxyl, phenol, and amine, which are essentially
the same as those in organic compounds in this study. Further
investigation of thermodynamic additivity correlations will al-
low approximates of thermodynamic properties of the wide
varieties of large organic molecules that appear to be abundant
in most natural aquatic and terrestrial environments. In the
present study, the temperature dependence for stability con-
stants of metalorganic complexes and chelates was estimated
by identifying ligand-dependent correlations of partial molal
entropy of association (S
r
) of the complexes and chelates with
the standard-state entropies (S

) of the aqueous cations at 25C


and 1 bar.
2. TEMPERATURE DEPENDENCE OF ASSOCIATION
CONSTANTS FOR METALORGANIC COMPLEXES
AND CHELATES
Association constants for metal-chelate formation are equi-
librium constants for reactions of the type
M
Z
xL
y
ML
x
z-xy
(1)
where M
z
represents a metal cation of charge z, L
y
stands
for an organic chelating agent (or ligand) of charge y,
ML
zxy
designates the complex or chelate, and x refers to the
number of ligands in the complex. Therefore, the association
constant () for reaction (1) refers to the equilibrium activity
(a) ratio given by

a
ML
x
z-xy
(a
M
z)(a
L
y)
x
(2)
Note that the complexes considered in this study are those
formed by the coordination of one ligand (x 1). In many
Fig. 2. Plots of the partial molal entropy of association at 25C and 1 bar for dicarboxylate complexes, (a) oxalate, (b)
malonate, (c) dipicolinate, and (d) diglycolate, as a function of the standard partial molal entropy of the aqueous cations at
25C and 1 bar. Literature values of S
r
are compiled in Appendices A5A8, and values of S
M

are taken from Shock et al.


(1997). Solid circles represent standard-state entropy data. Open symbols designate the values at various ionic strengths
from 0.1 to 1 m. The solid lines exhibit a consistent slope of 0.32.
3933 Entropies of association for aqueous metalorganic complexes
cases, equilibrium activities of the chelate are many times
greater than the activities of the cation and ligand, resulting in
large positive values for log . There are literally thousands of
experimental log values for chelate-forming reactions at
25C and 1 bar, but fewer data at other temperatures and
pressures. In the present study we are interested in estimating
the temperature dependence of log , which we accomplish by
evaluating the standard partial molal entropy change (S
r

) for
chelate-forming reactions and the relation
2.303RT

log
T

P

G
r

T

P
S
r

(3)
where G
r

stands for the standard partial molal Gibbs free


energy of the chelate-forming reaction. We provide correlations
for estimating S
r

that can be used to predict log with


reasonable accuracy at temperatures up to 100 to 150C. Pre-
dictions at higher temperatures require estimates of the stan-
dard partial molal heat capacity of chelate formation. Experi-
mental data of this type are very limited, and we have not
achieved estimation methods of this type for chelates.
3. REVIEW OF METHODS FOR ESTIMATING
STANDARD PARTIAL MOLAL ENTROPIES OF AQUEOUS
IONS AND COMPLEXES
Standard partial molal entropy data are available for hun-
dreds of aqueous ions, complexes, and chelates. These data
show considerable systematic behavior. Because entropy mea-
surements are time-consuming, several empirical and semiem-
pirical equations for estimating standard partial molal entropies
of aqueous ions and complexes (S

) have been developed that


take advantage of the systematic behavior. Various correlations
for predicting S

from charges (Z) and radii (r) of ions have


been investigated (Latimer and Bufngton, 1926; Latimer and
Kasper, 1929; Latimer et al., 1939; Powell and Latimer, 1951;
Latimer, 1955; Cobble, 1953a, b; Laidler, 1956; Glueckauf,
1964; Helgeson and Kirkham, 1976; Shock and Helgeson,
Fig. 3. Plots of the partial molal entropy of association at 20 and 25C and 1 bar for complexes consisting of three
carboxyl groups, (a) NTA, (b) HEDTA, (c) N-(2-carboxyethyl) iminodiacetate, and (d) N-(2-carboxyphenyl)iminodiacetate,
as a function of the standard partial molal entropy of the aqueous cations at 25C and 1 bar. Values of S
r
are from the
literature (Appendices A9A12), and values of S
M

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

on Z and r and by factors


added to account for the nature of different ions and complexes.
Latimer and Bufngton (1926) proposed that 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

of aqueous ions are proportional


to Z
2
and inversely proportional to r
e
(Latimer and Kasper,
1929; Latimer et al., 1939; Powell and Latimer, 1951; Latimer,
1955; Cobble, 1953a, b; Glueckauf, 1964; Helgeson and
Kirkham, 1976; Shock and Helgeson, 1988; Sassani and Shock,
1992). Laidler (1956) suggested similar correlations, but using
univalent radii (r
u
) instead of r
e
, where r
u
values were calcu-
lated as if Coulombic attractive and repulsive forces between
ions were equivalent to those between monovalent ions. Powell
and Latimer (1951) showed that values of S

for ions are


proportional to Z and inversely proportional to r
e
2
. Cobble
(1953a, b) and Latimer (1955) demonstrated linear correlations
between S

and Z/r
e
.
In addition to the estimation approaches based on physical
models, S

for aqueous complexes and chelates can be calcu-


lated from values of S
r

, which have linear relations with S

and hydration entropies (S


h

)
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

of corresponding aqueous anions


in the complexes are correlated by the general equation
S
r

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

refers to the entropy change during the hydration process and is


equivalent to the difference between the standard entropies of an ion in
the gas phase and aqueous phase.
Fig. 4. Plots of the partial molal entropy of association for complexes consisting of four and ve carboxyl groups, (a)
EDTA, (b) CDTA, (c) EGTA, and (d) DTPA, as a function of the standard partial molal entropy of the aqueous cations at
25C and 1 bar. Values of S
r
are from the literature (Appendices A13A16), and values of S
M

are taken from Shock et


al. (1997). The S
r
data were obtained at 0.1 m and 20, 25, and 25C. The solid lines exhibit a consistent slope of 0.92.
3935 Entropies of association for aqueous metalorganic complexes
Values of S
r

are also linearly related to S

of aqueous metal
cations (S
M

). Sverjensky et al. (1997) found linear correlations


between stepwise S
r
of inorganic ligand and acetate complex
formation with S

of the cation or complex to which the ligand


is added. The slopes and intercepts of the correlations depend
systematically on charges of the cations or complexes, as well
as on S

of the aqueous anions. Shock and Koretsky (1993,


1995) and Prapaipong et al. (1999) modied this estimation
scheme for metal complexes of monovalent and divalent or-
ganic acid anions. The latter authors found that the slope was
independent of cation charge. Similar correlations have been
found to apply to chelates as well. For example, Charles (1954)
discovered that a plot of the S
r

for metal complexes of EDTA


and corresponding values of S
M

exhibits a straight line with a


slope of one. Hovey (1988) plotted S
r

for metalEDTA com-


plexes against values of the absolute standard partial molal
entropy of metal ions, S
M
abs
, and also found a straight line, but
the slope was not equal to one. In the present study, we have
developed a new set of correlations between S
r
for metal
organic complexes and chelates and S
M

that permits reliable


estimates of S
r

and prediction of log to elevated tempera-


ture.
4. CORRELATIONS FOR ESTIMATING ENTROPIES OF
ASSOCIATION OF METALORGANIC COMPLEXES AND
CHELATES AT 25C AND 1 BAR
The results of a literature search for values of entropies of
association for metalorganic complexes and chelates obtained
by calorimetric measurement or by regression of stability con-
stants at various temperatures are compiled in Appendices
A1A16. These tables contain standard-state values of S
r

, 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

values for Zn(acetate)

, 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)

and Cu(diglycolate), as well as mal-


onate, HEDTA, and EDTA complexes of rare earth elements
Fig. 5. Hypothetical correlations between S
r
and S
M

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

for EDTA complexes determined by Vasilev


and Belonogova (1975), Vasilev and Belonogova (1976a,
1977), and Vasilev et al. (1983), as well as S
r
for HEDTA,
CDTA, and DTPA complexes of rare earth elements, and the
HgEGTA complex evaluated by Moeller and Ferrus (1961),
Moeller and Hseu (1962), Moeller and Thompson (1962), and
Hseu and Jyi (1981), respectively.
The selected values of S
r

and S
r
are plotted against S
M

taken from Shock et al. (1997), as shown in Figures 14.


Estimated values of S
r

need to have uncertainties of only a


few entropy units to maintain the accuracy of predicted values
of log . To illustrate whether our correlations are within 5
cal mol
1
K
1
of the experimental data, we have placed error
bars on the symbols in Figures 14.
As mentioned above, some of the entropy of association
values plotted in Figures 14 are not at the standard state. As
reported in the Appendices, these values of S
r
were measured
in various media of ionic strengths up to 3 m, and some data
were measured at 20 and 27C. However, these variables
appear to have a minor effect on the correlations between S
r
and S
M

. We have conrmed that the data at 20 and 27C do not


Fig. 6. Comparison of equilibrium association constants as functions of temperature for acetate complexes of La
3
, Nd
3
,
Gd
3
, and Yb
3
using S
r
values from this study (solid curves), and those from Shock and Koretsky (1993) (dashed
curves), together with experimental data (symbols). The solid curves are predictions and are strictly independent of the
experimental data.
3937 Entropies of association for aqueous metalorganic complexes
signicantly differ from those at 25C such that they would
affect the slopes of the correlation lines. In Figures 3 and 4, all
of the data were obtained at a relatively low ionic strength of
0.1 m, which has a minimal effect on the correlations. In
contrast, data for mono- and dicarboxylate complexes in Fig-
ures 1 and 2 refer to a variety of ionic strengths. Whereas most
values of the entropy of association for mono- and divalent
metal cations are standard-state data, those for rare earth ele-
ments refer to higher ionic strengths ranging from 0.1 to 2 m.
Considering these plots individually, despite the differences in
ionic strengths for complexes of various metal cations, we
found linear correlations in every case. Furthermore, compar-
ison of the plots of monocarboxylate complexes (Fig. 1ad)
shows that although the ionic strengths differ among the data
for complexes of rare earth elements in these plots, a unique
slope of 0.15 is applicable to all. This is also the case for
dicarboxylate complexes in Figure 2ad, all of which are
consistent with a slope of 0.32. Therefore, all available data
were used in plots presented here despite the differences in
ionic strengths. Unlike association constants, which depend
strongly on ionic strength, the ionic strength dependence of S
r
tends to be on the order of a few entropy units. This reects the
fact that the temperature dependence of association constants is
not a strong function of concentration.
Plots like those in Figures 14 for dozens of complexes and
chelates were generated to identify the effect of ligand structure
on the correlation of S
r
and S
M

. Linear ts were applied to all


plots. Note that the data for rare earth element complexes were
treated as one data point during the tting, so that they do not
disproportionately affect the linear ts. In some cases, a few
data were omitted in the linear ts due to the ambiguity in the
original literature using our criteria described above. Examples
of these include Th
4
, Zr
4
, and Hf
4
complexes of NTA,
CDTA, EGTA, and DTPA determined by Vasilev et al.
(1981), Hseu et al. (1965), Hseu and Jyi (1981), and Hseu et al.
(1983). The slopes of the correlations appear to correspond
systematically to ligand structures. In fact, the slopes of 0.15,
0.32, 0.84, and 0.92 are consistently applicable to com-
plexes of ligands containing one, two, three, and four carboxyl
groups respectively. The slope of 0.92 is also valid for
complexes of ligands with ve carboxyl groups. Note that
unlike the slopes, the intercepts do not appear to correlate with
Fig. 7. Prediction of the partial molal entropy of association for selected monocarboxylate complexes at 25C and 1 bar
where experimental data are limited. The slope of 0.15 is obtained from the correlations of S
r
and 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

for complexes for which experimental data are not


available.
5. DISCUSSION
The plots in Figures 14 demonstrate that the slopes of the
correlations are related to ligand structure, and become steeper
as the ligands become larger and contain more functional
groups. As described in this section, the slope values can be
explained by accounting for the number of water molecules
surrounding a cation before and after complexation or chela-
tion, which is governed by the number of functional groups in
the ligand that forms the complex or chelate, as well as the
coordination numbers (C.N.) of the cation in aqueous solution.
Specically, we propose that during complex formation where
a ligand replaces mmolecules of water surrounding a cation for
which C.N. equals n, the slope of the correlation between S
r
and S
M

is m/n.
Consider the hypothetical case of a ligand for which standard
partial molal entropies of metal complexes, S
C

, are all the same


regardless of the values of S
M

of the corresponding cations.


Because
S
r

S
M

S
C

S
L

, (5)
a plot of S
r

vs. S
M

would have a slope of 1. Furthermore,


both S
C

and S
L

would be constants and would dene the


intercept. In most cases values of S
L

are not available. How-


ever, values of S
r

and S
M

are available and correlations like


those shown in Figures 14 can be constructed. The correla-
tions in Figure 4 have slopes that approach 1, implying that
chelates involving ligands with four or ve carboxyl groups
approach the case where S
C

is constant. We believe that this


corresponds to a case where most of the water molecules
surrounding the cation are displaced by the formation of the
Fig. 8. Prediction of the partial molal entropy of association for selected dicarboxylate complexes at 25C and 1 bar where
measurements are limited. The slope of 0.32 is obtained from the correlations of S
r
and S
M

in Figure 2. 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). 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 3. 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). Solid circles represent standard-state entropy data. Open sym-
bols designate the values at ionic strengths of 0.1 m.
Fig. 10. Prediction of the partial molal entropy of association for complexes consisting of four carboxyl groups at 25C
and 1 bar where measurements are limited. The slope of 0.92 is obtained from the correlations 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

are those from Shock et al. (1997). The S


r
data were measured at 0.1 m.
3940 P. Prapaipong and E. Shock
Table 2. Slopes and intercepts for estimating S

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
be generalized that allow estimates of S
r

for numerous com-


plexes, including those of Al
3
, Fe
3
, rare earth and actinide
cations, which are important in environmental and biogeo-
chemical systems.
6. PREDICTED CORRELATIONS FOR STANDARD-STATE
ENTROPIES OF METALORGANIC COMPLEXES AND
CHELATES
We have adopted and applied the slopes from Figures 14 to
complexes and chelates of other ligands such as pyruvate,
benzoate, lactate, phthalate, citrate, and several others that are
common in geochemical and biogeochemical environments,
but for which thermodynamic data are limited. The correlations
between S
r
and S
M

for these complexes are depicted in Fig-


3942 P. Prapaipong and E. Shock
ures 710. It can be seen that the estimated slopes agree well
with the experimental data. Moreover, it is apparent that only a
few data values are needed to constrain the intercepts. Encour-
aged by these results, we have expanded the estimates to
include dozens of other complexes and chelates. Their slopes
and intercepts, together with those obtained from Figures 710
are summarized in Table 2. These estimates can be used with
values of log at 25C and 1 bar to estimate the temperature
dependence of log for thousands of metalorganic complexes
and chelates
2
that may be present in natural environments or
those impacted by human activities. It is our hope that these
estimates will enable new quantitative models of biogeochemi-
cal processes that involve metalorganic complexes and chelates
including trace element mobility, bioavailability, and toxicity.
AcknowledgmentsThis paper is dedicated to Harold Helgeson on the
occasion of his 70th birthday. We are encouraged by his example to be
bold in our efforts to push predictive methods into new areas. The
authors thank Andrey Plyasunov and Carla Koretsky for helpful dis-
cussions, and Jacques Schott for a constructive review. This is
GEOPIG contribution #221.
Associate editor: D. J. Wesolowski
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Appendix A1. Entropies of association (in cal mol
1
K
1
) for
acetate 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 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