J Solution Chem (2007) 36:81–95

DOI 10.1007/s10953-006-9094-1
ORIGINAL PAPER

Development of Accurate Chemical Equilibrium Models

for Oxalate Species to High Ionic Strength in the System:
Na ---- Ba ---- Ca ---- Mn ---- Sr ---- Cl ---- NO3 ---- PO4 ---- SO4 ---- H2 O
at 25 ◦ C

Odeta Qafoku · Andrew R. Felmy

Received: 22 March, 2006 / Accepted: 17 July, 2006 /

Published online: 21 December 2006


C Springer Science+Business Media, LLC 2006

Abstract The development of an accurate aqueous thermodynamic model is described

for oxalate species in the Na ---- Ba ---- Ca ---- Mn ---- Sr ---- Cl ---- NO3 ---- PO4 ---- SO4 ---- H2 O system at
25 ◦ C. The model is valid to high ionic strength (as high as 10 mol·kg−1 ) and from very
acid (10 mol·kg−1 H2 SO4 ) to neutral and basic conditions. The model is based upon the
equations of Pitzer and co-workers. The necessary ion-interaction parameters are determined
by comparison with experimental data taken from the literature or determined in this study.
The proposed aqueous activity and solubility model is valid for a range of applications from
interpretation of studies on mineral dissolution at circumneutral pH to the dissolution of
high-level waste tank sludges under acidic conditions.

Keywords Oxalate · Solubility · Pitzer interaction parameters

1 Introduction

Oxalate is a nearly ubiquitous dicarboxylate ligand that occurs in significant concentrations

in soils, surface waters, sedimentary basins and chemical processing solutions [1–7]. Oxalate,
which is a strong ligand for many metal ions [6–10], can bind directly to important adsorbing
surfaces for metal ions [5, 11] and can enhance the dissolution rate of minerals and other
solid phases [12, 13]. Recently, oxalic acid has also been used at U.S. Department of Energy
(DOE) waste storage sites to remove the sludges and sediments from the bottom of high-
level waste (HLW) storage tanks [1]. Unfortunately, developing an accurate thermodynamic
model for predicting the efficiency of the oxalic acid treatments of these sludges has proven
difficult owing to the high ionic strength of these solutions and the wide range in chemical
compositions of the waste sludges.
In this manuscript we present the development of an accurate aqueous thermodynamic
model for the principal cationic (Na, Ca, Mn, Sr, Ba) and anionic components (Cl, NO3 ,

O. Qafoku · A. R. Felmy (
)

Pacific Northwest National Laboratory, P.O. Box 999, MSIN K8-96, Richland, WA 99352
e-mail: ar.felmy@pnl.gov
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82 J Solution Chem (2007) 36:81–95

SO4 , PO4 ) important in both HLW tanks and environmental subsurface applications. The
model is parameterized over a broad pH range, from very acidic (pH < 1) to basic (pH >10)
and across a wide range of ionic strengths (I ∼ 10 mol·kg−1 ). The majority of the data for
model parameterization was taken from literature sources. However, as part of this study, the
solubilities for important solid phases were redetermined if the results were either unknown
in the literature or the experimental data too uncertain.

2 Experimental methods

The solubility of solid phases in three different chemical systems; oxalic acid, calcium
oxalate and strontium oxalate was experimentally investigated in this study.
The solubility of oxalic acid (H2 C2 O4 ·2H2 O) was determined from the undersaturation
direction over a range of NaCl concentrations (0.4 to 1.02 mol·kg−1 ) at a fixed concen-
tration of HCl (1.02 mol·kg−1 ) according to the following procedure. A weighed amount
of H2 C2 O4 ·2H2 O representing 2.04 mol·kg−1 oxalate if dissolved, was added to 50 mL
Oakridge centrifuge tubes. Known volumes of de-ionized (DI) water, concentrated HCl and
2.0 mol·kg−1 NaCl were added to the centrifuge tubes to reach the desired sample concentra-
tion and 30 mL final volume. The samples were placed in a rotating shaker for equilibration
(14 days). At the end of the equilibration period samples were centrifuged for 20 min at
2000 g and 5 mL of supernatant was taken for analysis. Liquid samples were analyzed for Cl
with liquid chromatography, Dionex DX-500 IC, and total acidity with a VIT90 Titrator. Di-
luted and acidified (100 µL, 2.08 mol·kg−1 HCl) supernatant was analyzed with a Shimadzu
TOC-5000A for non-purgable organic carbon (NPOC).
An oversaturation experiment containing various H2 C2 O4 concentrations (0.001 to
0.73 mol·kg−1 ) in the presence of NaCl (0.51 mol·kg−1 ) was conducted to check for possible
solid formation. The solid phase that precipitated during the oversaturation experiment was
separated by centrifugation, washed with 1 mL DI water, and air dried. The dried solid was
analyzed by XRD with a Phillips X’pert MPD X-ray diffractometer with Cu Kα radiation.
The liquid supernatants were analyzed for Cl− and total acidity as described above.
The solubility of CaC2 O4 ·H2 O and SrC2 O4 ·H2 O from undersaturation was studied in
H2 C2 O4 and Na2 C2 O4 solutions in both the presence and absence of NaCl (0.51 mol·kg−1 ).
The oxalate salts (30 mg CaC2 O4 ·H2 O and 150 mg SrC2 O4 ) were added into centrifuge
tubes followed by addition of 0.8766 g NaCl for these mixed electrolyte experiments. The
centrifuge tubes were transferred into an environmentally controlled chamber to prevent
contamination with the ambient CO2 . Known volumes of 0.94 mol·kg−1 H2 C2 O4 , 0.21
mol·kg−1 Na2 C2 O4 and DI water were mixed to reach the desired sample concentration and
a 30 mL final volume. Samples were agitated in a rotating shaker for the duration of the
experiment.
After 14 and 28 days equilibration the suspension pH’s were measured and samples


R
were centrifuged. Approximately 4 mL of supernatant was filtered through Centriplus
centrifugal filter devices with pore size 0.0036 µm (prewashed with 30mL DI water and
with 1 mL sample). The filtrates were analyzed for Ca by an inductively coupled plasma-
optical unit (ICP-OES) with a Perkin Elmer Optima 3000 and Sr by inductively coupled
plasma-mass spectrometry (ICP-MS), Hewlett Packard 4500 Series.
Analyzing the aqueous samples for Ca with ICP-OES proved difficult due to the presence
of organic carbon in the sample matrix. To overcome the matrix interference the samples
were diluted both in 2% HNO3 and DI water. The dilution in water improved the detection
limit for Ca analysis. Since the concentrations of the diluted samples were close to the
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J Solution Chem (2007) 36:81–95 83

instrument detection limit (6×10−7 mol·kg−1 ), a series of known additions for every sample
was performed to improve the accuracy of analysis.
Measurement of Ca and Sr at 14 and 28 days indicated that equilibrium was reached in
both systems. At the end of the equilibration period, non-filtered samples were analyzed for
NPOC. In addition to NPOC, a Na2 C2 O4 stock solution was also analyzed for inorganic
carbon (IC). Solids, at the beginning and the end of the solubility studies, were analyzed by
XRD.
All samples and stock solutions were prepared in degassed DI water (18 M·cm−1 ). All
chemicals used in the experiment with the exception of NaCl (GFC chemical) were Sigma-
Aldrich reagent-grade chemicals. Sample pHs were measured with an Orion combination
glass electrode calibrated at pH 4.0, 7.0 and 10.0 with standardized solutions.

3 Thermodynamic modeling

The aqueous thermodynamic model used in this study was the ion-interaction model of Pitzer
and coworkers [14, 15]. This model emphasizes a detailed description of the specific ion
interactions in the solution. The effects of the specific ion interactions on the excess solution
Gibbs energy are contained within the expressions for the activity coefficients. The activity
coefficients can be expressed in a virial-type expansion as:




ln γi = ln γiDH + βi j (I )m j + Ci jk m j m k + · · · (1)
j j k

where m is the molality and γiDH is a modified Debye-Hückel activity coefficient that is a
universal function of ionic strength. βi j (I) and Ci jk are specific for each ion interaction and
are functions of the ionic strength. Pitzer gives explicit phenomenological expressions for
the ionic-strength dependence of β. The third virial coefficient, C, is taken to be independent
of ionic strength. The form of β is different for like, unlike and neutral ion interactions.
A detailed description of the exact form of Eq. (1) is given elsewhere [16–18]. The Pitzer
thermodynamic model was used because it is applicable from zero to high electrolyte con-
centration and our experimental data extend to high ionic strength (I ∼ 10 mol·kg−1 ).

4 Model parameterization

4.1 H2 C2 O4 (aq) interactions

Under acidic conditions the principal oxalate species present is the fully protonated oxalic
acid, H2 C2 O4 (aq). Ion interactions between this neutral species and the bulk cations and
anions in solution are therefore the principal interactions responsible for the changes in
solution Gibbs energy under acid conditions. Owing to electroneutrality constraints one of
the aqueous ion-interactions must be set based upon convention. We have chosen to set
λH2 C2 O4 ,H+ to zero similar to previous work with CO2 (aq) [18] and B(OH)3 (aq) [17]. The
solubility product of H2 C2 O4 ·2H2 O(s) (Table 1) and the neutral ion-interaction parameter
λH2 C2 O4 ,Cl− (Table 2) were then adjusted to fit the oxalic acid solubility data in HCl (see
Fig. 1a). With the solubility product determined, the other anion-neutral ion-interaction
parameters λH2 C2 O4 ,NO−3 ; λH2 C2 O4 ,H3 PO4 ; λH2 C2 O4 ,HSO−4 (Table 2) were calculated from the ox-
alic acid solubility data in HNO3 , H3 PO4 , and H2 SO4 up to 10.3, 6.3 and 10.6 mol·kg−1 ,
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84 J Solution Chem (2007) 36:81–95

Table 1 Solubility products of solid phases used in this study

Equilibrium reaction log10 K Reference

H2 C2 O4 ·2H2 O(s)
2H+ + C2 O2− 4 + 2H2 O −5.53 This Study

Na2 C2 O4 (s)
2Na+ + C2 O2− 4 −2.44 This Study
NaHC2 O4 ·H2 O(s)
Na+ + HC2 O− 4 + H2 O −1.63 This Study
MnC2 O4 ·2H2 O(s)
Mn2+ + C2 O2− 4 + 2H2 O −6.54 This Study
BaC2 O4 ·2H2 O(s)
Ba2+ + C2 O2− 4 + 2H2 O −6.61 This Study
CaC2 O4 ·H2 O(s)
Ca2+ + C2 O2− 4 + H2 O −8.65 [10]
SrC2 O4 ·H2 O(s)
Sr2+ + C2 O2−4 + H2 O −6.92 This study
Sr(HC2 O4 )2 ·H2 O(s)
Sr2+ + 2HC2 O− 4 + H2 O −5.47 This study
Na2 Sr5 (C2 O4 )6 ·12H2 O(s)
2Na+ + 5Sr2+ + 6 C2 O2−
4 + 12H2 O −33.9 This study

respectively (Fig. 1). In the H2 SO4 system, the model calculations predicted HSO− 4 as the
predominant species. To better fit the oxalic acid solubility in this system, the addition of
a higher-order parameter ζH2 C2 O4 ,HSO−4 ,H+ was required. Although the experimental obser-
vations for this system extend to 14 mol·kg−1 , the model was unable to predict accurately
above 10.6 mol·kg−1 . It is possible that the activity of water is reduced significantly at
>10.6 mol·kg−1 . Indeed in the H2 C2 O4 ---- HNO3 ---- H2 O system [19] at HNO3 concentrations
>30 mol·kg−1 it was found that the solid phase changed to anhydrous H2 C2 O4 . Model-
ing the H2 SO4 experimental data with anhydrous H2 C2 O4 instead of H2 C2 O4 ·2H2 O im-
proved the prediction significantly at H2 SO4 concentrations >10.6 mol·kg−1 (dashed line in
Fig. 1b).

Table 2 Ion-interaction Pitzer parameters calculated in this study

Cij
(0) (1) (2)
Species i Species j βi j βi j βi j

Binary parameters
Na+ HC2 O−4 −0.206 0.468 0 0.074
Na+ C2 O2−
4 −0.172 1.991 0 0.131
Na+ Mn(C2 O2 )2−
2 0.200 0 0 0
Na+ Co(C2 O2 )2−
2 −0.511 1.734 0 0.253
Na+ Ni(C2 O2 )2−
2 −0.043 1.501 0 0.014
Neutral-ion parameters

Species i Species j λi j

H2 C2 O4 (aq) Cl− 0.122

H2 C2 O4 (aq) Na+ −0.061
H2 C2 O4 (aq) NO−
3 0.069
H2 C2 O4 (aq) HSO−
4 0.247
H2 C2 O4 (aq) H3 PO4 (aq) 0.059
CoC2 O4 (aq) Cl− −0.096
NiC2 O4 (aq) Cl− −0.105
Higher-order neutral-ion parameters
Species i Species j Species k µi jk
H2 C2 O4 (aq) H+ HSO−4 −0.024

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J Solution Chem (2007) 36:81–95 85

2.0 2.0
HCl
a) H2SO4 b)
HNO3 H3PO4
(19)
Linke & Seidell (19) Linke & Seidell
w/anhydrous H2C2O4
1.5 1.5
Oxalic Acid (m)

Oxalic Acid (m)

1.0 1.0

0.5 0.5

0.0 0.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
Total Acidity (m) Total Acidity (m)

Fig. 1 The solubility of H2 C2 O4 ·2H2 O under acidic conditions a) HCl and HNO3 , and b) H2 SO4 and H3 PO4

In order to complete the set of ion-interaction parameters for the neutral H2 C2 O4 (aq)
species it is also required to determine the Na+ interaction parameter (i.e., λH2 C2 O−4 Na+ ).
Theoretically, knowing λH2 C2 O4 ,Cl− , the λH2 C2 O−4 , Na+ parameter can be calculated from oxalic
acid solubility data in NaCl that are available in the literature [21]. However, in our initial
examination of these data it appeared that several data points could be oversaturated with
respect to sodium bioxalate (NaHC2 O4 ·H2 O). Therefore, we re-examined the solubility of
oxalic acid in the presence of NaCl to check for possible solid formation. The first of these
studies was performed at a fixed NaCl concentration (0.51 mol·kg−1 ) and variable oxalic acid

0.55

experimental data - this study

0.50
Pitzer model

0.45
Na+ (m)

0.40

0.35

0.30

0.25
0.1 0.2 0.3 0.4 0.5 0.6

H2C2O4 (m)

Fig. 2 The solubility of NaHC2 O4 ·H2 O at fixed NaCl concentration (0.51 mol·kg−1 ) and variable oxalic
acid concentration
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86 J Solution Chem (2007) 36:81–95

1.0

experimental data - this study

Pitzer model with Na-H2C2O4(aq) interactions

0.9
Oxalic acid (m)

0.8

0.7

0.6
0.3 0.4 0.5 0.6 0.7 0.8

NaCl (m)

Fig. 3 The solubility data of H2 C2 O4 ·2H2 O in 1.02 mol·kg−1 HCl and variable NaCl concentration, used to
determine Na ---- H2 C2 O4 (aq) interaction

concentrations (Fig. 2). The results clearly show that at oxalic acid concentrations greater
than 0.15 mol·kg−1 , sodium bioxalate precipitation occurs, lowering the total dissolved Na
in solution to below the initial 0.51 mol·kg−1 value. Therefore, the solubility data determined
by Herz and Hiebenthal [20] were oversaturated with respect to sodium bioxalate and were
not used in the model parameterization. The solubility data determined in this study at higher
acidity (1.01 mol·kg−1 HCl) were used to determine λH2 C2 O−4 , Na+ (Fig. 3).
As a note, Herz and Hiebenthal [20] calculated the aqueous oxalic acid concentration from
the total acidity measurements. They measured the Cl concentration but did not measure
organic carbon in the solution phase and did not characterize the solid after equilibration.
During bioxalate solid formation H+ is released from oxalic acid through the reaction:

NaCl(aq) + H2 C2 O4 (aq)
NaHC2 O4 · H2 O + HCl(aq) (2)

Thus, the aqueous oxalic acid concentration cannot be calculated by measuring only acidity
and the Cl− concentration. Interestingly, the total acidity measurements of Herz and Hieben-
thal [20] are in agreement with our acidity data, where sodium bioxalate was identified as
the precipitate.
With the neutral ion-interaction parameters defined, the next step is to determine the
parameters for the bioxalate (HC2 O− 2−
4 ) and oxalate (C2 O4 ) species. The ion-interaction
+
parameters for these anionic species with Na have been previously determined by Mizera
et al. [21] with the parameters for the neutral oxalic acid species set to zero; an assumption
which is not valid at high acidity. Therefore, the apparent equilibrium constant data for the
dissociation of oxalic acid and bioxalate in NaCl reported in Mizera et al. [21] were re-fit
with our new values for the neutral ion-interaction parameters (Fig. 4).
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J Solution Chem (2007) 36:81–95 87

4.5

4.0

3.5

3.0

Mizera et al. (21)

pKai

2.5
Kettler et al. (9)
Kettler et al. (10)
2.0 Pitzer model

1.5

1.0

0.5
0 1 2 3 4 5
NaCl (m)

Fig. 4 Ionic strength dependence of dissociation constants for H2 C2 O4 (aq) and HC2 O−
4 in NaCl, re-fit with
new values for neutral ion-interaction parameters. The equilibrium reactions were calculated as reported in
Mizera et al. [21]: H+ + HC2 O− 4
H2 C2 O4 ; H + C2 O4
HC2 O4
0 + 2− −

4.2 Na2 C2 O4 ---- NaHC2 O4 ---- Cl ---- H2 O system

The solubility product of sodium bioxalate (NaHC2 O4 ·H2 O) was calculated from the solubil-
ity data in Linke and Seidell [19] at 25 ◦ C. The abrupt decrease in NaHC2 O4 ·H2 O solubility
at H2 C2 O4 > 0.13 mol·kg−1 (Fig. 5) is predicted very well by the model as being due to
changes in aqueous speciation. The oxalate, C2 O2− 4 , species is the predominant aqueous
species at H2 C2 O4 < 0.13 mol·kg−1 , whereas HC2 O− 4 predominates the solution speciation
at H2 C2 O4 > 0.13 mol·kg−1 . The model also satisfactory predicts the NaHC2 O4 ·H2 O(s)
solubility data in the mixed electrolyte H2 C2 O4 ---- NaCl from the oversaturation conditions
(Fig. 2) without adjusting any parameters.
The solubility product of Na2 C2 O4 (s) was then calculated by fitting the experimental data
collected at 25 ◦ C and zero ionic strength (I) [19] and tested on the Na2 C2 O4 (s) solubility
data to 1.74 mol·kg−1 Na2 SO4 [19] (Fig. 6) with no parameters adjusted.

4.3 MnC2 O4 ---- H2 O system

Mn2+ is a divalent cation that is known to strongly interact with oxalate, possibly to form
aqueous complexes such as MnC2 O4 (aq) and Mn(C2 O4 )2− 2 [10]. Therefore, we tested dif-
ferent models that allowed or did not allow the formation of MnC2 O4 (aq) and Mn(C2 O4 )2−
2
species. The standard state equilibrium constants for the aqueous species were taken from
the NIST database [10] (Table 3). The solubility data for MnC2 O4 ·2H2 O in the presence
of H2 C2 O4 [19] was the first experimental system tested. The speciation calculations indi-
cated that the neutral complex, MnC2 O4 (aq), was the predominant aqueous species at oxalic
acid concentrations up to 0.05 mol·kg−1 . The solubility product of MnC2 O4 ·2H2 O was then
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88 J Solution Chem (2007) 36:81–95

0.30

Linke & Seidell (19)

0.25 Pitzer model

0.20
NaHC2O4 (m)

0.15

0.10

0.05

0.00
0.0 0.2 0.4 0.6 0.8 1.0 1.2

H2C2O4 (m)

Fig. 5 Prediction of the NaHC2 O4 ·H2 O solubility as function of oxalic acid concentration. The abrupt
−
decrease observed in the bioxalate solubility is due to changes in aqueous speciation C2 O2−
4 vs. HC2 O4

0.30

Linke & Seidell (19)

0.25 Pitzer model

0.20
Na2C2O4 (m)

0.15

0.10

0.05

0.00
0.0 0.4 0.8 1.2 1.6 2.0
Na2SO4 (m)

Fig. 6 The solubility of Na2 C2 O4 in Na2 SO4 with established ion-interaction parameters (no new parameters
adjusted)

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J Solution Chem (2007) 36:81–95 89

Table 3 Aqueous species and

their standard state equilibrium Species log10 K(p,q,r) Reference
∗
constants used in this study
H2 C2 O4 (aq) 5.653 (2,0,1) [21]
HC2 O−4 4.259 (1,0,1) [21]
MnC2 O4 (aq) 3.950 (0,1,1) [10]
Mn(C2 O4 )2−2 5.249 (0,1,2) [10]
CoC2 O4 (aq) 4.900 (0,1,1) [22]
2−
Co(C2 O4 )2 7.150 (0,1,2) [22]
∗ NiC2 O4 (aq) 5.242 (0,1,1) [23]
Equilibrium reaction: Ni(C2 O4 )2− 8.213 (0,1,2) [23]
pH+ + qMe2+ + r L2−
2
p+2q−2r CaC2 O4 (aq) 3.190 (0,1,1) [10]
H p Meq Lr .

determined from solubility data in aqueous oxalic acid (Fig. 7a) and was used throughout
the analysis.
The second aqueous species Mn(C2 O4 )2− 2 becomes predominant at high oxalate con-
centrations and therefore interpretation of the experimental data on manganese oxalate
solubility in aqueous Na2 C2 O4 (Fig. 7b) required inclusion of this species along with a
Na+ ---- Mn(C2 O4 )2−
2 ion-interaction parameter.
The experimental data on manganese oxalate solubility in various electrolytes MnCl2 ,
H2 SO4, Na2 SO4 and NaCl (Fig. 7c–f) were used as independent tests of the accuracy of our
model. The predictions were good in Na2 SO4 , MnCl2 and NaCl electrolytes, but initially
over-predicted the data in H2 SO4 (Fig. 7d). The over-prediction was due to the lack of an
ion-interaction parameter for Mn2+ ---- HSO− −
4 . The bisulfate, HSO4 , species is important in
2+ ---- −
H2 SO4 solutions. Since a literature value for Mn HSO4 interaction was unavailable,
the interaction parameters for Fe2+ ---- HSO−
4 and Mg 2+ ----
HSO−4 [14] were used as analogs.
Model predictions with both analogs worked equally well; with the Fe2+ analog having a
slightly better prediction (Fig. 7d).

4.4 Co(Ni)C2 O4 ---- H2 O-system

Accurate models for the Co(Ni)C2 O4 ---- H2 O-system in NaCl solutions have been previously
published [22, 23] with the neutral ion interaction parameters for H2 C2 O4 (aq) again set to
zero. Therefore, we re-fit the original apparent equilibrium constant data of Borokowski et al.
[22, 23] with our new values for the ion-interaction parameters for H2 C2 O4 (aq). The standard
state equilibrium constants for the formation of the aqueous Co and Ni-oxalate complexes
(Table 3) remained unchanged from those proposed by Borokowski et al. [22, 23]. The new
model accurately describes the apparent equilibrium constant data after adjustment of the
necessary interaction parameters (Fig. 8a and b).

4.5 BaC2 O4 ---- H2 O-system

Solubility data for BaC2 O4 ·2H2 O are available only in KCl solutions to high concentrations.
The solubility product of BaC2 O4 ·2H2 O was determined from the most dilute data points at
KCl [19] and then used to predict the solubility data at higher concentrations (Fig. 9). The
model calculations with no K+ ion-interaction parameters over-predicted the experimental
data at KCl > 0.3 mol·kg−1 (dashed line). In order to improve the model predictions to
0.6 mol·kg−1 KCl we added previously calculated Na-anion interaction parameters (i.e.,
λH2 C2 O−4 , Na+ ) as analogs for K+ , resulting in better fit to the experimental data (Fig. 9).
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90 J Solution Chem (2007) 36:81–95

1.0e-2 1.6e-2

a) 1.4e-2 b)
8.0e-3
1.2e-2
MnC2O4 (m)

MnC2O4 (m)
1.0e-2
6.0e-3

8.0e-3

4.0e-3
6.0e-3

4.0e-3
2.0e-3
2.0e-3

0.0 0.0
0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.00 0.06 0.12 0.18 0.24 0.30

H 2C 2 O 4 (m) Na2C 2O 4 (m)

0.80
2.4e-3 c) d)
0.60
2.2e-3
MnC2O4 (m)

MnC2O4 (m)

2.0e-3 0.40

1.8e-3
0.20

1.6e-3
0.00

1.4e-3
0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.0 0.3 0.6 0.9 1.2 1.5

MnCl2 (m) H 2 SO 4 (m)

1.6e-2 9.0e-3
e) f)
1.4e-2 8.0e-3

1.2e-2 7.0e-3
MnC2O4 (m)
MnC2O4 (m)

1.0e-2 6.0e-3

8.0e-3 5.0e-3

6.0e-3 4.0e-3

4.0e-3 3.0e-3

2.0e-3 2.0e-3
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 1.0 2.0 3.0 4.0

Na2SO 4 (m) NaCl (m)

Fig. 7 The solubility of MnC2 O4 ·2H2 O in different electrolytes. Experimental data from Linke and Seidell
[19] (open circles); Pitzer model with MnC2 O4 (aq) (dashed line), with MnC2 O4 (aq) and Mn(C2 O4 )2−
2 (solid
line), with Mn ---- HSO− ---- 2−
4 interaction (dash-dotted line), and with Na Mn(C2 O4 )2 interaction (dotted line)

4.6 CaC2 O4 ---- H2 O-system

The solubility data for calcium oxalate at 25 ◦ C and zero I can be highly variable ranging from
4 × 10−5 to 7 × 10−5 mol·kg−1 with a coefficient of variability (CV = 20.2%). Therefore,
we accepted the solubility product for CaC2 O4 ·H2 O from the NIST data base [10] (Table 1).
The formation constant for the neutral CaC2 O4 (aq) complex calculated from the NIST data
base [10] and for the CaHC2 O+ 4 complex [10, 24] were also initially accepted.
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J Solution Chem (2007) 36:81–95 91

8 8
a) b)
7 7

6 6
CoC2O4 pkai

NiC2O4 pkai
5 5

4 4

3 3
pka1 Borkowski et al.
(22)
pka1 Borkowski et al. (23)
pka2 Borkowski et al. (22)
pka2 Borkowski et al. (23)
2 2
0 1 2 3 4 5 6 0 1 2 3 4 5 6
NaCl (m) NaCl (m)

Fig. 8 The new Pitzer model (solid line) accurately describes the dependence of the dissociation constants
of a) CoC2 O4 and b) NiC2 O4 at various ionic strengths

The solubility data for calcium oxalate in oxalic acid [19] could not be predicted by this
initial model at > 0.15 mol·kg−1 H2 C2 O4 . The data from Linke and Seidell [19] indicated
that the solubility of calcium oxalate decreases at H2 C2 O4 > 0.3 mol·kg−1 (Fig. 10a) whereas
our initial model predicted slowly increasing concentrations. Therefore, the solubility data
for CaC2 O4 ·H2 O in H2 C2 O4 were re-determined. Our new experimental data are in better
agreement with the model predictions based upon the equilibrium constant data in the
literature for CaC2 O4 (aq) to 0.73 mol·kg−1 (Fig. 10a). The XRD patterns of the solid at the
end of equilibration indicated the presence of only CaC2 O4 ·H2 O.

1.4e-2

1.2e-2
Linke & Seidell (19)

1.0e-2
BaC2O4 (m)

8.0e-3

6.0e-3

4.0e-3

2.0e-3

0.0

0.0 0.2 0.4 0.6 0.8 1.0 1.2

KCl (m)

Fig. 9 The solubility of BaC2 O4 ·H2 O in KCl without ion interaction parameters (dashed lines) and with
K+ ---- H2 C2 O4 (aq) interaction (solid line)
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1.0e-3 5.0e-2
a) b)
8.0e-4 4.0e-2

6.0e-4 3.0e-2
CaC2O4 (m)

CaC2O4 (m)
4.0e-4 2.0e-2

2.0e-4 1.0e-2

0.0 0.0

0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2
H2C2O4 (m) HCl (m)
4.0e-4 4.0e-4

3.5e-4
c) 3.5e-4
d)

3.0e-4 3.0e-4
CaC2O4 (m)

CaC2O4 (m)

2.5e-4 2.5e-4

2.0e-4 2.0e-4

1.5e-4 1.5e-4

1.0e-4 1.0e-4

5.0e-5 5.0e-5

0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.00 0.05 0.10 0.15 0.20 0.25

NaCl m Na2SO4 m

Fig. 10 The CaC2 O4 ·H2 O solubility in different electrolytes. Experimental data from Linke and Seidell
[19] (circles), from Streit [25] (diamonds), and from this study (triangles); Pitzer model without CaC2 O4 (aq)
(dashed line); with CaHC2 O+ 4 (dotted line); with CaC2 O4 (aq) (solid line)

However, inclusion of the CaHC2 O+ 4 complex resulted in a rapid increase in the predicted
solubility (Fig. 10a). Therefore, this complex was not included in our database.
This simple model without any ion-interaction parameters for the neutral CaC2 O4 (aq)
complex also accurately predicted the CaC2 O4 ·H2 O solubility in solutions as concentrated
as 1 mol·kg−1 HCl, 1 mol·kg−1 NaCl and 0.21 mol·kg−1 Na2 SO4 (Fig. 10b, c, d) [19, 25].
Finally, we attempted to determine the solubility of calcium oxalate at various concentra-
tion of Na2 C2 O4 (from 0.001 to 0.21 mol·kg−1 Na2 C2 O4 ), but were unsuccessful since the
Ca sample concentrations were below the instrument detection limit indicating the absence
of a strong Ca(C2 O4 )2−
2 complex.

4.7 SrC2 O4 ---- H2 O-system

The solubility data for strontium oxalate in oxalic acid solution [19] showed an unusual
trend of rapidly increasing concentration to about 0.1 mol·kg−1 oxalic acid followed by a
rapid decrease (Fig. 11a). Therefore, we repeated the solubility studies of strontium oxalate
in oxalic acid solution. Although our final measured concentrations followed similar trends,
we observed a phase transition in the solubility controlling solid, from SrC2 O4 ·H2 O below
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J Solution Chem (2007) 36:81–95 93

5.0e-3 8.0e-4
a) b)
4.0e-3 6.0e-4
SrC2O4 (m)

SrC2O4 (m)
3.0e-3 4.0e-4

2.0e-3 2.0e-4

1.0e-3 0.0

0.0
0.0 0.2 0.4 0.6 0.8 0.00 0.05 0.10 0.15 0.20 0.25
H2C2O4 (m) Na2C2O4 (m)

5.0e-3

c)
4.0e-3

3.0e-3
SrC2O4 (m)

2.0e-3

1.0e-3

0.0

0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14

Na2C2O4 (m), and NaCl (0.51m )

Fig. 11 The solubility of Sr-oxalate solid phases in a) H2 C2 O4 , b) Na2 C2 O4 , and c) Na2 C2 O4 + NaCl.
Experimental data from Linke and Seidell [19] (circles) and from this study (triangles); Pitzer model with
SrC2 O4 ·H2 O(s) (solid line), with Sr(HC2 O4 )2 ·H2 O(s) (dashed line), and with Na2 Sr5 (C2 O4 )6 ·12H2 O(s)
(dotted line)

0.05 mol·kg−1 oxalic acid to Sr(HC2 O4 )2 ·H2 O at higher concentrations. So the previously
observed rapid decrease in concentration was a result of a transition in the stable phase. The
solubility products for both phases were calculated from our solubility data in oxalic acid
(Fig. 11a). This model was tested against the solubility data in Na2 C2 O4 solutions (Fig. 11b).
The modeling results indicated that inclusion of a SrC2 O4 (aq) species was not required.
The presence of a third strontium oxalate solid, namely sodium strontium oxalate hy-
drate Na2 Sr5 (C2 O4 )6 ·12H2 O was identified by XRD patterns at Na2 C2 O4 concentration
>0.21 mol·kg−1 . The strontium oxalate experimental data at a Na2 C2 O4 concentration equal
to 0.21 mol·kg−1 was used to calculate the solubility product for the Na2 Sr5 (C2 O4 )6 ·12H2 O
phase. Solubility data for this phase in mixed Na2 C2 O4 plus NaCl solutions was then used
to test the final model (Fig. 11c).

5 Summary

This paper describes the development of an accurate aqueous thermodynamic model for
oxalate species in the Na ---- Ba ---- Ca ---- Mn ---- Sr ---- Cl ---- NO3 ---- PO4 ---- SO4 ---- H2 O at 25 ◦ C. The
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model is based upon an extensive comparison with experimental data and is tested in systems
more complex than those used in model parameterization. The final model is accurate across
a broad range of ionic strengths and acidities. As a result, the model is useful for a wide
range of applications from using oxalic acid in acid leaching solutions to environmental
applications where oxalate is known to enhance mineral solubilities and dissolution rates.

Acknowledgments

This research was conducted at Pacific Northwest National Laboratory, operated by Battelle
for the U.S Department of Energy and was supported by the Environmental Management
Sciences Program (EMSP) under a project entitled “Chemical Speciation of Strontium,
Americium, and Curium in High Level Waste,” Project No. 26753.
The research described in this manuscript was performed at the W. R. Wiley Environmental
Molecular Sciences Laboratory, a National Scientific User Facility sponsored by the U.S.
Department of Energy’s Office of Biological and Environmental Research and located at
Pacific Northwest National Laboratory. PNNL is operated for the Department of Energy by
Battelle.

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