Fluid Phase Equilibria 480 (2019) 41e52

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Characterization of the thermodynamic properties of some

benzenepolycarboxylic acids: Acid-base properties, weak complexes,
total and neutral species solubility, solubility products in NaClaq,
(CH3)4NClaq and Synthetic Sea Water (SSW)
Paola Cardiano, Rosalia Maria Cigala*, Francesco Crea, Concetta De Stefano,
Demetrio Milea, Silvio Sammartano
 di Messina, Viale F. Stagno D’Alcontres 31, 98166, Messina, Italy
Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche Ed Ambientali, Universita

a r t i c l e i n f o a b s t r a c t

Article history: The acid-base properties and solubilities of 1,2,3-, 1,3,5-, 1,2,4-benzenetricarboxylic and 1,2,4,5-
Received 16 July 2018 benzenetetracarboxylic acids at T ¼ (298.15 ± 0.15) K in NaClaq, (CH3)4NClaq and in Synthetic Sea Wa-
Received in revised form ter are reported. In synthetic sea water, the data were analyzed by means of the single salt approximation
25 September 2018
(BA). For each ligand, the total solubility (ST) was determined and only in some cases it was possible to
Accepted 29 September 2018
Available online 1 October 2018
calculate the neutral species solubility (S0) and the Setschenow coefficients, because the formation of
sparingly soluble species formed with the cation of the supporting electrolytes was often observed.
Different stoichiometry were proposed for the precipitates and their corresponding solubility products
Keywords:
Protonation constants
were calculated at the different experimental conditions. The dependence of the protonation constants
Solubility and solubility products on ionic strength was analyzed by Debye-Hückel type equations. The formation
Setschenow coefficients constants of the complexes formed by the different deprotonated species of the ligands with the cation of
Solubility product the supporting electrolytes were also determined.
Complexation © 2018 Elsevier B.V. All rights reserved.

1. Introduction present in natural waters as intermediate products of the

The benzenepolycarboxylic acids are commonly used in the
synthesis of new materials [1]; these ligands exhibit a variety of
coordination mode with the ability to form coordination architec-
tures of different size and shapes. Symmetric benzenepolycarbox-
ylic acids as 1,3,5-benzenetricarboxylic acid (trimesic acid) and
1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), are inten-
sively employed for the polymers construction, owing to their
bridging abilities [1]. Pyromellitic acid was found to be a potent
inhibitor of hemorrhage, with an IC(50) value of 0.035 mM [2]. The
asymmetric ligands such as 1,2,4- and 1,2,3-benzenetricarboxylic
acids (trimellitic and hemimellitic acid, respectively) can form
interesting structures by reason of the special orientation of
carboxylate groups; for example, in the 1,2,3-benzenetricarboxylic
acid molecule, none of carboxylate groups is coplanar with the
aromatic ring. Generally, benzenepolycarboxylates are often
* Corresponding author.
E-mail address: rmcigala@unime.it (R.M. Cigala).
biochemical processes of living organisms or from the degradation
of the humic substances [3]. For these reasons benzenepoly-
carboxylic acids are used as model molecules for the simulation of
the behavior of the natural organic matter and to study the role of
humic and fulvic fractions on the speciation of natural waters. To
better understand the behavior of such a class of ligands in natural
systems, it is important to investigate their chemical and physical
properties in different experimental conditions of ionic strength,
temperature and ionic medium. Concerning this last point, the
choice of (CH3)4NCl, NaCl and SSW as ionic media, is due to their
very different interacting ability towards O-donor ligands, since
generally, the first of them is considered, for O-donor ligands, a no
or weakly interacting medium; the second is the main inorganic
component of the natural waters and biological fluids and has a
significant interacting ability towards O-donor ligands, whilst the
last one is a multicomponent solution simulating from an acid-base
and complexing point of view the natural sea water. The weak in-
teractions of alkali and alkaline earth cations play a very important
role in multicomponent solutions such as sea water. As well known,

https://doi.org/10.1016/j.fluid.2018.09.027
0378-3812/© 2018 Elsevier B.V. All rights reserved.
42 P. Cardiano et al. / Fluid Phase Equilibria 480 (2019) 41e52
the highest contribution (>99.5%) to the sea water salinity is given
by the following cations and anions: Naþ, Kþ, Ca2þ, Mg2þ, Cl and
SO24 , whose concentrations (mol/kg of sea water) or salinity are
listed in Table S1 of the Supplementary Information section.
For this aim, a comprehensive picture of the acid-base, com-
plexing properties and solubility of 1,2,3-, 1,3,5-, 1,2,4-
benzenetricarboxylic acids and 1,2,4,5-benzenetetracarboxylic
acid, in NaClaq, (CH3)4NClaq and Synthetic Sea Water (SSW) at
different ionic strengths or salinities, is reported at T ¼
(298.15 ± 0.15) K.
The dependence of the log KH i on the ionic strength and medium
was investigated by means of a simple Debye-Hückel type equation
and SIT (Specific ion Interaction Theory) approach.
The total solubility and its dependence on the ionic strength was
investigated in the three ionic media; a significant variation of the
total solubility with the ionic strength was observed in dependence
on the different interacting nature of the background salts used.
The solubility of the ligand neutral species was determined only
for 1,2,3- (only in (CH3)4NCl) and 1,2,4-benzenetricarboxylic (in the
three ionic media) acids, since in the other cases the formation of
NapHiL or ((CH3)4N)pHiL sparingly soluble species was observed.
This experimental evidence was also confirmed by High Pressure
Ionic Chromatography (HPLC) analysis and calculating the total
molar Hþ and ligand concentration and their [Hþ/CL (L ¼ ligand)]
molar ratios in the saturated solutions, that resulted to be higher
than 3 for the tricarboxylic acids or four for the 1,2,4,5-
benzenetetracarboxylic acid.
The formation constants of the complexes formed by the
different deprotonated forms of the ligands and the cation (i.e.: Naþ
for NaCl, (CH3)4Nþ for (CH3)4NCl or Bþ1.117 for SSW) of the sup-
porting electrolytes were also determined.
The solubility product of the sparingly soluble species was
determined at different ionic strengths and modeled in order to
calculate the value at infinite dilution.
A comparison with some literature data was made too.
2. Experimental section
2.1. Chemicals
The solutions of 1,2,3-, 1,3,5-, 1,2,4-benzenetricarboxylic (1,2,3-
benz; 1,2,4-benz; 1,3,5-benz, respectively) acids and 1,2,4,5-
benzenetetracarboxylic (1,2,4,5-benz) acid purchased from Fluka,
were prepared by weighing the pure ligands in acid form and used
without further purification; the purity checked alkalimetrically
Table 1
Chemicals used in this work, purchased from Fluka.
Chemical Name
1,2,3-benzenetricarboxylic acid
1,3,5-benzenetricarboxylic acid
1,2,4- benzenetricarboxylic acid
1,2,4,5-benzenetetracarboxylic acid
Calcium chloride dihydrate
2,20 ,200 ,2000 -(Ethane-1,2-diyldinitrilo)tetraacetic acid
Hydrochloric acid
Magnesium chloride hexahydrate
Methanol
Potassium chloride
Potassium phthalate monobasic
Sodium carbonate
Sodium chloride
Sodium hydroxide
Sodium sulphate
Tetramethylammonium chloride
a
Recrystallized salt from methanol, as reported in Ref. [48].
resulted to be >99%. The synthetic sea water was prepared at
different salinities (S ¼ 15, 25, 35 and 45‰, see Table S1 of the
Supplementary Information) following the procedures reported in
some previous papers [4,5]. The sodium chloride, sodium sulphate
and potassium chloride solutions were prepared by weighing the
pure salts, previously dried in an oven at T ¼ (383.15 ± 0.15) K,
whilst magnesium and calcium chloride solutions were prepared
by weighing the solid products (Fluka) and then standardized by
complexometric titration, using EDTA standard solution. Tetrame-
thylammonium chloride ((CH3)4NCl or Me4NCl) solutions were
prepared after re-crystallization from methanol. Sodium and tet-
ramethylammonium hydroxide and hydrochloric acid solutions
were prepared from concentrated ampoules and standardized
against potassium phthalate and sodium carbonate, respectively.
All solutions were prepared with twice-distilled water previously
boiled. Grade A glassware was used and all the solutions were
protected from atmospheric CO2 using soda lime traps. More details
on the chemicals employed in this study are reported in Table 1.
2.2. Procedure and apparatus
Saturated solutions of 1,2,3-, 1,3,5-, 1,2,4-benzenetricarboxylic
and 1,2,4,5-benzenetetracarboxylic acids were prepared, in a ther-
mostatic room, by the addition of an amount of ligand to solutions
of NaClaq, (CH3)4NClaq and SSW at pre-established ionic strength
and salinity values (0 < I/mol$dm3  5.0; 0 < I/mol$dm3  3.0
and 0 < I/mol$dm3  0.929, respectively) to reach saturation. So-
lutions were stirred at T ¼ (298.15 ± 0.15) K for at least 24 h; pre-
liminary tests established that longer stirring times were
unnecessary. The pH value of each solution was measured when the
solubility equilibrium was reached. The excess of solid product in
the saturated solution was removed by centrifugation and filtration
by using cellulose membrane filters (Ø ¼ 0.45 mm). A volume of
25 cm3 of the filtered solution was titrated with standard NaOH or
(CH3)4NOH solution in a thermostated cell at T ¼ (298.15 ± 0.15) K,
by means a thermocryostat (model D1-G Haake). Independent ti-
trations of HCl at the same ionic strength or salinity as the sample
under study were carried out to determine the standard electrode
potential E0 and the junction potential coefficient ja (Ej ¼ ja$[Hþ]).
All the potentiometric titrations were carried out under magnetic
stirring and bubbling purified presaturated N2 through the solu-
tion, in order to exclude O2 and CO2 inside the solution.
To avoid and minimize systematic errors, the potentiometric
measurements were performed with two different and indepen-
dent apparatus; the first consisted of an 809 Metrohm Titrando
Purification Purity (% wt.)
NO >99%
NO >99%
NO >99%
NO >99%
NO 99%
NO 99%
NO 99%
NO 99%
NO 99%
NO 99%
NO 99.5%
NO 99.5%
NO 99%
NO 99%
NO 99%
YESa 99%
 P. Cardiano et al. / Fluid Phase Equilibria 480 (2019) 41e52
controlled by Metrohm TiAMO software equipped with a combined
glass electrode. The second apparatus is a 713 Metrohm potenti-
ometer equipped with a half cell glass coupled with a standard Agþ/
AgCl electrode; the potentiometer was connect to a Metrohm
motorized burette and to a pc. The automatic titrations were per-
formed using a suitable homemade computer program to control
titrant delivery, data acquisition and to check for e.m.f. stability. The
estimated precision was ±0.15 mV and ±0.003 cm3 for the e.m.f.
and titrant volume, respectively, for both potentiometric apparatus.
For each titration, 60e80 data points were collected.
To verify the composition of the precipitate in equilibrium with
the saturated solution, a small amount of precipitate was washed
with a mixture of ultrapure water/ethanol. The precipitate was then
dried under vacuum for at least 48 h and dissolved in pure water
(HPLC grade) and then analyzed by a Dionex DXLAN 500 ion-
exchange chromatographer (Sunnyvale, U.S.A.) equipped with a
pre-column (Dionex Ion-Pac CG12, 4  50 mm) and an analytical
column (Dionex Ion-Pac CS12, 4  250 mm). The HPLC was coupled
to a quaternary gradient pump (Dionex GP40) and a conductivity
detector (CD20) coupled with an electrolytic self-regenerating
suppressor (Dionex CSRS-Ultra II 4 mm). The elution solvent was
HCl (Fluka) 25 mmol dm3, pumped at 1.3 cm3/min; injection sys-
tem was a 25 mm3 Loop.
Chromatographic results confirmed in many cases the presence
in the precipitate of different cations, namely Naþ, for the NaCl ionic
medium, (CH3)4Nþ for the tetramethylammonium salt and the
simultaneously presence of Mg2þ and/or Ca2þ and trace of Naþ and
Kþ in SSW.
2.3. Calculations
The non-linear least squares computer program ESAB2M [6] and
BSTAC [7] were used to refine all the parameters of the acidebase
titration, standard electrode potential E0, liquid junction potential
coefficient, ja, ionic product of the water Kw, purity and total sol-
ubility of the ligands. The LIANA computer program, which mini-
mizes the error squares sum in y of an equation y ¼ f (xi) (a generic
function given by the user), was used to study the dependence of
protonation constants, solubility and solubility products on the
ionic strength and to calculate the Setschenow parameters. The
ES2WC computer program was used for the calculation of the weak
complexes formed by the ligands and the cations of the supporting
electrolytes.
More details on the computer programs are reported by De
Stefano et al. [8].
The procedures used to convert the ionic strength and the
protonation constants from the molar (c) to the molal (m) con-
centration scale, in the different supporting electrolytes, were
already described in previous papers [9]. The ratio c/m is given by:
c/m ¼ d0 þ a1c þ a2c2 (1)
where d0 is the water density at T ¼ 273.15 K, d0 ¼ 0.99987 g/cm3;
by using the density values at different temperatures Ref. [10] and
the procedure reported in Ref. [5] the following values were
calculated, a1 ¼ 0.017765 for NaCl and 0.107951 for (CH3)4NCl,
whilst a2 ¼ 6.525  104 for NaCl and 4.833  104 for (CH3)4NCl.
The validity range is: 0  I (NaCl)/mol kg1  6 and 0  I
((CH3)4NCl)/mol kg1  4.3.
For SSW ionic medium, the conversion of the thermodynamic
quantities from the molar to the molal concentration scale was
carried out following the procedures reported in previous papers
[5,11,12].
The calculation of the different salinity values of the solutions
was carried out by the equation:
43
ms ¼ m35 ∙ 27.56572 S/(1000e1.005714 S) (2)
where m35 is the salt concentration at the salinity 35‰ and it is
taken as reference value, ms is the desired concentration value; S is
the conventional salinity value. Moreover, in Ref. [5], two computer
programs useful to calculate and convert all the thermodynamic
parameters and concentrations regarding the equilibrium studies
on natural fluids are also reported.
3. Results and discussion
3.1. Protonation constants
The acid-base properties of 1,2,3-, 1,3,5-, 1,2,4-
benzenetricarboxylic and 1,2,4,5-benzenetetracarboxylic acids
were determined in different experimental conditions, namely, in
NaClaq (0 < I/mol$dm3  5.0), (CH3)4NClaq (0 < I/mol$dm3  3.0)
and SSW (0 < I/mol$dm3  0.929), by potentiometric technique.
The protonation constants refer to the following equilibria:
Hþ þL3 ¼ HL2 KH
1
(3)
Hþ þHL2 ¼ H2 L KH
2
(4)
Hþ þH2 L ¼ H3 L0 KH
3
(5)
In the case of 1,2,4,5-benzenetetracarboxylic acid, the charge is
z ¼ 4, therefore the further following equilibrium must be take
into account:
Hþ þH3 L ¼ H4 L0 KH
4
(6)
Similar equilibria can be expressed by means of the overall
protonation constants:
n Hþ þLz ¼ Hn LðznÞ bH (7)
Tables S2-S5 of the Supporting Information report the proton-
ation constants of the ligands here investigated at different ionic
strengths and in the different ionic media. It is possible to observe,
independent of the ligand, a very significant medium effect, espe-
cially on the most acidic protonation constants. The values in tet-
ramethylammonium salt are higher than those in NaCl that in turn
are fairly similar to the protonation constants in SSW. An opposite
trend is observed with the increase of the ionic strength; generally
data in (CH3)4Nþ tend to increase increasing the salt concentration,
whilst both in NaCl and SSW they tend to decrease up
to ~ 1.0 mol dm3. In particular, we can see that the behavior of the
protonation constants differ for the different acids; in fact, in NaClaq
the log KH i values of 1,2,4- and 1,3,5-benzenetricarboxylic acids
decrease increasing the ionic strength, up to I ¼ 0.5e1.0 mol dm3,
then they increase with increasing the NaCl concentration.
The trend of logK H1 vs. I, in NaClaq at T ¼ (298.15 ± 0.15) K, of
1,2,3-, 1,2,4- and 1,3,5-benzenetricarboxylic acids is showed in
Fig. 1. The protonation constant of 1,2,3-benzenetricarboxylic acid is
always higher than to the log KH 1 of the 1,2,4-benzenetricarboxylic
acid and in turn with respect to the 1,3,5- one.
Figure S1of the Supporting Information reports, as an example,
the titration curve of 1,3,5-benzentricarboxylic acid in NaCl
aqueous solution at I ¼ 1.0 mol dm3 and T ¼ 298.15 K; the experi-
mental potentiometric data (e.m.f./mV) are reported with the
square symbol (,), whilst the corresponding calculated values
determined by means of non-linear least squares calculation by
using the ESAB2M program are reported by as a straight line. It is
possible to observe a fairly good agreement between the
44 P. Cardiano et al. / Fluid Phase Equilibria 480 (2019) 41e52
Fig. 1. First protonation constants of 1,2,3-, 1,2,4- and 1,3,5-bezenetricarboxylic acids
vs. ionic strength in NaCl aqueous solution a T ¼ 298.15 K and p ¼ 0.1 MPa. Standard
uncertainties u are: u (T) ¼ 0.15 K, u (p) ¼ 1 KPa, u (I) ¼ 0.001 mol dm3.Legend:
, ¼ 1,2,4.benz; D ¼ 1,2,3-benz; B ¼ 1,3,5-benz.
experimental and calculated data, with a DVMax ~6 mV at the in-
flection points. This trend was also obtained for the other ligands
investigated at the different ionic strength values.
The different behavior of each ligand in the ionic media is simply
explained taking into account the interacting ability of NaCl, SSW
and (CH3)4NCl, in particular the promoting nature of NaCl and SSW
with respect to (CH3)4Nþ, that can be considered a breaking water
structure [11,13,14]. This behavior can be better observed in Fig. 2
where the first protonation constants of 1,2,4-benzenetricarboxylic
acid is reported in three ionic media and at different ionic
strengths. It is possible to observe as data in NaCl and SSW up to
~0.95 mol dm3 are fairly similar, and those in (CH3)4NCl are signif-
icantly higher than at each ionic strength values.
Moreover from a comparison between the log KH i values of the
tricarboxylic acids in the same ionic medium, seems that the values
of the 1,2,3-benzenetricarboxylic acid are higher than to those of
1,2,4- and 1,3,5-benzenetricarboxylic acids, respectively, and data
Fig. 2. First protonation constants of 1,2,4-benzenetricarboxylic acids vs. ionic strength
in NaCl, SSW and (CH3)4NCl aqueous solutions a T ¼ 298.15 K and p ¼ 0.1 MPa. Standard
uncertainties u are: u (T) ¼ 0.15 K, u (p) ¼ 1 KPa, u (I) ¼ 0.001 mol dm3. Legend: , ¼
(CH3)4NCl; D ¼ SSW; B ¼ NaCl.
of the 1,2,4,5-benzenetetracarboxylic acid are fairly similar than
those of 1,2,3-benzenetricarboxylic acid.
3.2. Dependence of the protonation constants on the ionic strength
3.2.1. Debye-Hückel type equation
The dependence on ionic strength of the protonation constants,
of 1,2,3-, 1,3,5-, 1,2,4-benzenetricarboxylic acids and 1,2,4,5-
benzenetetracarboxylic acid was analyzed by the Debye-Hückel
type equation [15e17]:
pffiffi
I
log K H ¼ log K H0  z* ,0:51 , pffiffi þ C,I þ D,I 1:5
1 þ 1:5 I
(8)
where K H0 is the protonation constant at infinite dilution, z* ¼
P 2 P 2
zreagent  zproduct ; C and D are empirical parameters for the
dependence of the formation constants on the ionic strength.
Concerning the SSW supporting electrolyte, being a multicom-
ponent solution, the modeling of the stability constants with the
ionic strength is more difficult, owing to the high number of in-
teractions that must be considered [4,5]. Taking into account an
approach already proposed [18] and widely tested on many
different classes of ligands, the SSW was considered a “single salt”
BA, where the cation B and the anion A represent all the major
cations (Naþ, Kþ, Mg2þ, Ca2þ) and anions (Cl, SO2 4 ) components in
natural sea water, respectively. By using the single salt approxi-
mation, the complexity of the system is considerably reduced, since
only three species, namely HA, BOH and BA must be considered and
a simple equation, as eq. (8), can be used to model the dependence
of the stability constants on the ionic strength. This approach gives
a general picture of the cumulative binding ability of the inorganic
components of sea water towards the ligands or metal ions,
without a significant loss of accuracy [11,12,19e22]. Table S6 of the
Supplementary Information section reports the stability constants
at infinite dilution and the parameters for the dependence on the
ionic strength of the HA, BOH and BA species.
The protonation constant values at infinite dilution, the C and D
values that account for the variation of the log KH i of the different
ligands investigated with the ionic strength are reported in Table 2.
The D parameter is useful in NaCl supporting electrolytes when
high ionic strength values were investigated. In tetramethy-
lammoniun salt, owing to the significant variation also at low ionic
strength values of the protonation constants with the increase of
the salt concentration, it is necessary to use this parameter. In SSW,
the use of D is useless.
3.2.2. Specific ion interaction theory
The dependence of the protonation constants on the ionic
strength can be modeled by means of the Specific ion Interaction
Theory (SIT) [23e27]. In this case, the activity coefficients of a
cation or an anion can be expressed by:
pffiffi
0:51 I X
log g ¼ z2 , pffiffi þ ε , mi (9)
1 þ 1:5 I
where ε is the interaction coefficient of a generic ionic species,
whilst for the neutral species we have:
log g ¼ km$I (10)
where km is the Setschenow coefficient [28] that takes into account
the change of the activity coefficient of the neutral species when
the ionic strength of the aqueous solution varies.
 P. Cardiano et al. / Fluid Phase Equilibria 480 (2019) 41e52 45

Table 2
Protonation constants of polycarboxylic ligands at infinite dilution at T ¼ 298.15 Ka.

1,2,3-benzenetricarboxylic acid

Cd Dd Cd Dd Cd

(CH3)4NCl NaCl SSW

logKH1b 6.17c 0.81 ± 0.04e 0.27 ± 0.02 0.51 ± 0.17 0.36 ± 0.18 0.20 ± 0.02
logKH2 4.24c 0.55 ± 0.03 0.18 ± 0.02 0.13 ± 0.12 0.24 ± 0.12 0.48 ± 0.01
logKH3 2.77c 0.37 ± 0.02 0.09 ± 0.01 0.18 ± 0.06 0.12 ± 0.06 0.56 ± 0.03

1,3,5-benzenetricarboxylic acid

logKH1 5.01 ± 0.02 0.47 ± 0.04 0.68 ± 0.06 0.23 ± 0.04 0.64 ± 0.03
logKH2 4.00 ± 0.03 0.31 ± 0.03 1.60 ± 0.14 1.04 ± 0.09 0.45 ± 0.01
logKH3 3.17 ± 0.01 0.16 ± 0.03 0.83 ± 0.08 0.44 ± 0.05 0.40 ± 0.03

1,2,4-benzenetricarboxylic acid

logKH1 5.54f 0.53 ± 0.04 0.14 ± 0.02 0.22 ± 0.01 0.024 ± 0.006 0.24 ± 0.01
logKH2 4.00f 0.40 ± 0.03 0.09 ± 0.02 0.26 ± 0.01 0.016 ± 0.004 0.45 ± 0.02
logKH3 2.48f 0.33 ± 0.01 0.05 ± 0.01 0.25 ± 0.01 0.008 ± 0.002 0.42 ± 0.01

1,2,4,5-benzenetetracarboxylic acid
C D C
(CH3)4NCl NaClg

logKH1 6.02 ± 0.01 1.14 ± 0.01 0.43 ± 0.01 2.03

logKH2 4.71 ± 0.01 1.194 ± 0.008 0.32 ± 0.01 1.49
logKH3 3.03 ± 0.02 1.200 ± 0.004 0.22 ± 0.02 1.13
logKH4 1.92 ± 0.02 0.664 ± 0.004 0.11 ± 0.01 0.65
a
Standard uncertainties u are: u (T) ¼ 0.15 K, u (p) ¼ 1 KPa.
b
Protonation constant expressed in mol dm3.
c
Ref. [30].
d
Empirical parameter of eq. (8).
e
95% C.I. (confidence interval).
f
Ref. [11].
g
Ref. [38].

By using the simple formulation and the molal concentration
scale (mol kg1 (H2O)), the SIT approach is identical to the one used
in eq. (10), except for the D parameter:
pffiffi
I (see next section).
log K H ¼ log K H0  z* , 0:51 , pffiffi þ ,ε ,I
1 þ 1:5 I
A modified version of the SIT equation was already proposed
[13], in which the specific interaction coefficients ε are not constant
but dependent on the ionic strength, according to the simple
relationship:
Dε0  Dε∞
Dε ¼ Dε∞ þ
I þ 1
where Dε ¼ Dεreactants  Dεproducts; if the specific interaction of the
ligand with a cation is taken into account, we can calculate the
single specific interaction coefficient ε, by means of eq. (12) or (13):
ε0  ε∞
ε ¼ ε∞ þ
I þ 1
The ε∞ and ε0 values state the dependence of SIT parameters on
ionic strength, valid for I / ∞ and I / 0, respectively.
Generally, tetraalkylammoniun salts are considered not or weakly
interacting towards O-donor ligands [9,13,19]. However, in the case
of benzenepolycarboxylic acids here investigated, we observed a
significant interaction among these components, so the SIT approach
was applied to the 1,2,3- and 1,2,4-benzenetricarboxylic acids in
(CH3)4NClaq and NaClaq (only for 1,2,4-benzenetricarboxylic acid)
since only for these ligands and in those ionic media it was possible
to determine the Setschenow parameter for the neutral species. For
1,2,4-benzenetricarboxylic acid in tetramethylammonium chloride
salt, the calculated specific interaction parameters are valid up to
I ¼ 0.5 mol dm3, since over this ionic strength value the precipita-
tion of a 1,2,4-benzenetricarboxylate-(CH3)4Nþ species was observed
(11) The interactions that have been take into account are:
Dε1 ¼ ε(Mþ,L3) þ ε(Hþ,Cl) - ε(Mþ,HL2) for log KH
1 (14)
Dε2 ¼ ε(Mþ,HL2) þ ε(Hþ,Cl) - ε(Mþ,H2L) for log KH
2 (15)
Dε3 ¼ ε(Mþ,H2L) þ ε(Hþ,Cl) e km for log KH
3 (16)
(12)
where Mþ ¼ Naþ in NaClaq and (CH3)4Nþ in (CH3)4NClaq. For
ε(Hþ,Cl), we used at T ¼ (298.15 ± 0.15) K, the values: ε ¼ 0.11,
ε∞ ¼ 0.136 and ε0 ¼ 0.0848 already reported in Ref. [29]. As regards
the single salt BA, the specific coefficients are: ε(Hþ,A1.117) ¼ 0.114
and ε(Bþ1.117,HA0.117) ¼ 0.016 [11].
The calculated specific interaction parameters of the ionic spe-
cies in the ionic media are reported in Table 3.
(13)
3.3. Solubility
In the past, our research group has been involved in the deter-
mination of the solubility of many different classes of organic li-
gands such as carboxylic ligands [11,30e35]. As a further
contribution to this kind of investigation, the total solubility (ST) of
1,2,3-, 1,3,5- and 1,2,4-benzenetricarboxylic and 1,2,4,5-
benzenetetracarboxylic acids, in different ionic media, NaClaq,
(CH3)4NClaq and SSW, at different ionic strengths was determined.
The total solubility takes into account all the species (protonated,
46 P. Cardiano et al. / Fluid Phase Equilibria 480 (2019) 41e52

Table 3
Specific interaction parameters for the ionic species of 1,2,3- and 1,2,4-benzenetricarboxylic acids in (CH3)4NClaq and 1,2,4-benzentricarboxylic acid in NaClaq and SSW at
T ¼ 298.15 Ka.

Species 1,2,3-benzenetricarboxylic acid

(CH3)4NCl

Dε b
sfit εc
sfit ε∞d ε0d sfit
þ 3 e
((CH3)4N ,L ) 0.32 ± 0.03 0.13 0.24 ± 0.06 0.13 0.20 ± 0.06 1.24 ± 0.10 0.05
((CH3)4Nþ,HL2) 0.20 ± 0.04 0.12 0.03 ± 0.04 0.12 0.17 ± 0.02 0.50 ± 0.08 0.04
((CH3)4Nþ,H2L) 0.14 ± 0.02 0.08 0.06 ± 0.02 0.09 0.05 ± 0.02 0.09 ± 0.06 0.06

1,2,4-benzenetricarboxylic acid

(CH3)4NCl

Dε sfit ε sfit ε∞ ε0 sfit

((CH3)4Nþ,L3) 0.22 ± 0.01 0.09 0.58 ± 0.02 0.09 0.08 ± 0.02 0.30 ± 0.12 0.06
((CH3)4Nþ,HL2) 0.16 ± 0.02 0.11 0.47 ± 0.02 0.11 0.10 ± 0.02 0.12 ± 0.12 0.05
((CH3)4Nþ,H2L) 0.15 ± 0.02 0.09 0.42 ± 0.01 0.09 0.20 ± 0.02 0.60 ± 0.08 0.06

NaCl

Dε sfit ε sfit
þ 3
(Na ,L ) 0.04 ± 0.02 0.07 0.45 ± 0.03 0.07
(Naþ,HL2) 0.13 ± 0.02 0.07 0.30 ± 0.02 0.07
(Naþ,H2L) 0.12 ± 0.02 0.07 0.32 ± 0.02 0.08

SSW

ε∞f ε0f

(Bþ1.117,L3) 0.567 1.643

(Bþ1.117,HL2) 0.016 1.756
(Bþ1.117,H2L) 0.069 0.884
a
Standard uncertainties u are: u (T) ¼ 0.15 K, u (p) ¼ 1 KPa.
b
Interaction parameter of eq. (11).
c
Interaction parameters of eqs.14e16.
d
Interaction parameters of eq. (13).
e
95% C.I. (confidence interval).
f
Ref. [11].

partially protonated and unprotonated) that a ligand forms in or (20) as in the case of the total solubility. In those equations both
aqueous solution; for an O-donor ligand, the total solubility can be the molar and the molal concentration scale can be used, by
expressed according to the general equation: substituting cMX with mMX.
h i h i h i If the solubility of the neutral species and the molal concen-
ST ¼ Hn L0 þ Hn1 Lzn1 þ … þ Lz (17) tration scale is used, the activity coefficient of HnL0 can be calcu-
lated by following equation:
 
where Hn L0 is the concentration of the neutral species (S0 Þ.
Considering the protonation equilibria associated to the species of g S0
log ¼ log 00 ¼ kc;m , c; mMX (21)
the ligand, it is possible to rearrange equation (17) in: g0 S
!
X
n h ii where g and g0 are the activity coefficients of the neutral species in
þ
T
S ¼ S 0
1þ bHi H (18) a given ionic medium and in pure water, respectively, and kc;m is the
1 Setschenow coefficient (in molar c or molal m concentration scale).
In dilute solutions we can assume g0 ¼ 1.
The dependence of the total solubility ST on ionic medium
concentration was modeled by a linear and not linear equation, (19) The Setschenow coefficient can be considered dependent on the
concentration of the supporting electrolyte [31e33]:
and (20):

logST ¼ log ST0 þ a, cMX (19) k0  k∞

kc;m ¼ k∞ þ (22)
c; mMX þ 1
  
a0  a∞ where k∞ and k0 are valid for c,mMX / ∞ and c,mMX /
logST ¼ logST0 þ a∞ þ , cMX (20)
1 þ cMX 0 (MX ¼ NaCl; (CH3)4NCl or SSW), respectively.
The experimental total solubility of 1,2,3-, 1,3,5-, 1,2,4-
where ST0 is the total solubility in pure water, a (eq. (19)), a∞ and a0 benzenetricarboxylic and 1,2,4,5-benzenetetracarboxylic acids in
(eq. (20)) are empirical parameters for the dependence of the total (CH3)4NClaq, NaClaq and SSW at different ionic strengths, is reported in
solubility on ionic medium concentration; for eq. (20), a∞ and a0 Tables S7-S10 of the Supporting Information. Along the manuscript,
are valid for I / ∞ and I / 0, respectively, and cMX is the molar the solubilities (total and neutral species) are given in the mol dm3
concentration of the ionic medium. scale and are also reported as logarithm values. From the analysis of
According to Long and McDevit [36], the solubility of the neutral the experimental data, we can observe that, generally, the total sol-
species ( S0 ) can be fitted with an equation similar to equation (19) ubility (ST) of the ligands follows the trend:
 P. Cardiano et al. / Fluid Phase Equilibria 480 (2019) 41e52 47

The determination of the solubility of the neutral species (S0 )

Fig. 3. Experimental total solubility in mol dm3 of 1,2,3-benzenetricarboxylic acid in
SSW at different ionic strengths and T ¼ 298.15 K and p ¼ 0.1 MPa. Standard un-
certainties u are: u (T) ¼ 0.15 K, u (p) ¼ 1 KPa, u (I) ¼ 0.001 mol dm3.
(CH3)4NClaq > NaClaq > SSW. Taking into account a given ionic
strength value, as an example I ¼ 0.5 mol dm3, the trend of the total
solubility is: 1,2,3- > 1,2,4- > 1,2,4,5e~1,3,5-, that is valid in
(CH3)4NClaq and NaClaq, whereas, in SSW, we have: 1,2,3- > 1,2,4-
> 1,3,5-.
The total solubility decreases with increasing the concentration
or the salinity of NaCl or SSW, respectively, therefore a Salting-Out
effect was found.
Fig. 3 reports the trend of the total solubility of 1,2,3-
benzenetricarboxylic acid with respect to the ionic strength in
SSW; it is possible to observe a significant Salting-out effect with
the increase of the salt concentration and a reduction of the total
solubility of about 50%.
The dependence on salt concentration of the total solubility of
the ligands was analyzed by linear and no linear equations 19 and
20; the total solubility in pure water (ST0 ) together with the
empirical parameters, a, a∞ and a0 are reported in Table 4.
was not possible for all the benzenepolycarboxylic acids investi-
gated, since in many cases we observed in the determination of the
total proton and ligand concentration a [Hþ]/[Lz] molar ratio (R)
higher than three for the tricarboxylic acids or four in the case of
the 1,2,4,5-benzenetetracarboxylic acid.
This suggested that the sparingly soluble species formed in the
solutions at the different experimental conditions (solubility
measurements) is not the ligand neutral species, namely H3L0 or
H4L0, but is formed by the interaction of different unprotonated
ligand species with the cation of the supporting electrolytes (i.e.
Naþ, (CH3)4Nþ and B1.117þ for SSW). This allows the possible for-
mation of “mixed” species of different stoichiometry (i.e. NaH2L,
Na2HL, Na2H2L, (CH3)4NH3L or BHiL (i ¼ 0e2), etc.).
The solubility of the neutral species was determined only for
1,2,3-benzenetricarboxylic acid in (CH3)4NClaq and for 1,2,4-
benzenetricarboxylic acid in (CH3)4NClaq and in NaClaq at T ¼
(298.15 ± 0.15) K. The solubility values of the neutral species are
listed in Table S11 of the Supporting Information. The total and
neutral species solubility of 1,2,4-benzenetricarboxylic acid in SSW
was already reported in a previous paper [11].
The logS00 values, in the molar concentration scale, together
with k, k∞ and k0 coefficients for 1,2,3- and 1,2,4-
benzenetricarboxylic acid are reported in Table 5.
A singular behavior was observed for the 1,2,4-
benzentricarboxylic acid in NaClaq and (CH3)4NClaq, where the
proton/ligand molar ratio results equal to three up to 0.504 and
1.019 mol dm3, respectively; at higher ionic strength values this
molar ratio is higher than three indicating the ligand interaction
with Naþ and (CH3)4Nþ to form the sparingly soluble species.
3.4. Solubility product
In all the other cases where the [Hþ]/[Lz] molar ratio (R)
resulted higher than three or four, a possible stoichiometry of the
sparingly soluble species was proposed and the corresponding
solubility product was calculated at the different ionic strengths
and in the different ionic media.

Table 4
Total solubility of the ligands at infinite dilution ( ST0 Þ and parameters a (eq. (19)), a∞ and a0 (eq. (20)) for the dependence on the ionic strength in the different ionic media at
T ¼ 298.15 Ka.

1,2,3-benzenetricarboxylic acid

(CH3)4NCl sfitb NaCl sfit SSW sfit

log ST0 ¼ 0.91 ± 0.07 c
ad
0.16 ± 0.04 e
0.17 1.62 ± 0.19 0.38 1.81 ± 0.12 0.36
ST0 ¼ 0.123 ± 0.003c a∞f 0.15 ± 0.13 0.11
a0f 0.89 ± 0.26
1,3,5-benzenetricarboxylic acid
log ST0 ¼ 1.99 ± 0.02 a 0.31 ± 0.05 0.08 0.20 ± 0.01 0.06 0.61 ± 0.04 0.10
ST0 ¼ 0.0101 ± 0.001 a∞ 0.55 ± 0.16 0.03 0.13 ± 0.03 0.05 0.12 ± 0.15 0.09
a0 1.08 ± 0.16 0.40 ± 0.08 1.18 ± 0.12
1,2,4-benzenetricarboxylic acid
log ST0 ¼ 1.160g a 0.11 ± 0.01 0.16 0.25 ± 0.01 0.18 0.056 0.08
ST0 ¼ 0.069g a∞ 0.18 ± 0.03 0.09 0.31 ± 0.03 0.09 0.523 0.07
a0 0.88 ± 0.07 0.02 ± 0.01 0.545
1,2,4,5-benzenetetracarboxylic acid
log ST0 ¼ 1.52 ± 0.04 a 0.31 ± 0.02 0.23 0.34 ± 0.08 0.11
ST0 ¼ 0.031 ± 0.002 a∞ 0.034 ± 0.008 0.16 0.70 ± 0.03 0.04
a0 1.22 ± 0.20 1.28 ± 0.04
a
Standard uncertainties u are: u (T) ¼ 0.15 K, u (p) ¼ 1 KPa.
b
Standard deviation on fit.
c
Total solubility expressed in mol dm3, (moles ligand/dm3 of solution).
d
Empirical parameter of eq. (19).
e
95% C.I. (confidence interval).
f
Empirical parameter of eq. (20).
g
Ref. [11].
48 P. Cardiano et al. / Fluid Phase Equilibria 480 (2019) 41e52

Table 5
Solubility of the neutral species H3L at infinite dilution ( S00 ) and Setschenow parameters k (eq. (21)), k∞ and k0 (eq. (22)) at T ¼ 298.15 Ka.

1,2,3-benzenetricarboxylic acid 1,2,4-benzenetricarboxylic acid

(CH3)4NCl sfitb (CH3)4NCl sfit NaCl sfit SSWf sfit

log S00 c,d
¼ 0.81 ± 0.02 log S00 ¼ 1.167 c,f

S00 ¼ 0.155 ± 0.001 S00 ¼ 0.068c,f

kg 0.09 ± 0.01 0.09 k 0.38 ± 0.04 0.12 0.33 ± 0.07 0.06 0.011 0.02
kh∞ 0.01 ± 0.06 0.08 k∞ 0.27 ± 0.03 0.09 e 0.021 0.01
kh0 0.32 ± 0.16 k0 0.97 ± 0.18 e 0.003
f
Ref. [11].
g
Setschenow parameter of eq. (21).
h
Setschenow parameters of eq. (22).
a
Standard uncertainties u are: u (T) ¼ 0.15 K, u (p) ¼ 1 KPa.
b
Standard deviation on fit.
c
Solubility of the neutral species H3L at infinite dilution expressed in mol dm3, (moles ligand/dm3 of solution).
d
95% C.I. (confidence interval).

An attempt to determine a possible stoichiometry of the spar- [Mþ]p,[Hþ]i,[Lz] ¼ Ks0 (23)

ingly soluble species was made by the determination of the metal
(Mþ ¼ Naþ or (CH3)4Nþ) concentration by HPLC (see experimental
section). Taking also into account the ligand concentration in the
solution at equilibrium with the precipitate, for NaCl medium a not
clear molar ratio was observed, indicating the possible formation of
Naþ/ligand species with different stoichiometry. On the basis of
previous investigation carried out on different classes of ligands,
two possible stoichiometry, namely NaH2L and Na2HL were pro-
posed for the benzenetricarboxylic acids and Na2H2L for the 1,2,4,5-
benzenetetracrboxylic acid [30,37e39].
In the case of (CH3)4NCl a 1:1 metal:ligand molar ratio was
observed, and the solubility product of the (CH3)4NH2L species was
determined for the 1,3,5- or 1,2,4-benzenetricarboxylic acids,
whilst for 1,2,4,5-benzenetetracarboxylic acid, the solubility prod-
uct of the (CH3)4NH3L species was calculated.
The solubility product can be expressed by the following
equation.
Concentrations in equation (23) refer to the free component
concentrations at the pH of solubility.
The free component concentrations at the different experi-
mental conditions were calculated taking into account the different
mass balance equations of the ligand and of the proton, whilst for
the metal concentration (Naþ or (CH3)4Nþ), owing to its large
excess with respect to the ligand, it was assumed that free metal
concentration ¼ total metal concentration.
The experimental solubility product of each metal-ligand spe-
cies at different ionic strengths are reported in Tables 6e8.
As for the protonation constants and the total and neutral spe-
cies solubility, also for the solubility product an equation to model
its variation with the ionic strength was proposed:

Table 6
Experimental and calculated solubility products of 1,3,5-benzenetricarboxylate/(CH3)4Nþ and 1,3,5-benzenetricarboxylate/Naþ species at different ionic strengths and at
T ¼ 298.15 Ka.

Experimental

Species Me4NH2L NaH2L Na2HL

Ib log KS0b,c Ib log KS0 log KS0

(CH3)4NCl NaCl

0.100 12.33 0.104 12.06 11.13

0.100 12.39 0.104 12.20 11.31
0.502 11.27 0.504 11.52 10.60
0.502 11.20 0.510 11.83 10.82
1.000 10.94 1.002 11.37 9.97
1.000 10.88 2.000 10.75 9.04
2.000 10.60 8.65
3.004 10.11 8.14
3.004 10.18 8.21

Calculated
Species Me4NH2L NaH2L Na2HL
Ib log KS0 Ib log KS0 log KS0

0.100 12.31 ± 0.12d 0.104 12.37 ± 0.12 11.48 ± 0.20

0.502 11.38 ± 0.08 0.504 11.52 ± 0.08 10.47 ± 0.18
1.000 10.87 ± 0.10 0.510 11.52 ± 0.08 10.46 ± 0.18
1.002 11.09 ± 0.06 9.84 ± 0.14
2.000 10.59 ± 0.06 8.94 ± 0.10
3.004 10.24 ± 0.10 8.18 ± 0.12
a
Standard uncertainties u are: u (T) ¼ 0.15 K, u (p) ¼ 1 KPa, u (I) ¼ 0.001 mol dm3.
b
Ionic strength and solubility product expressed in mol$dm3.
c
Calculated on the basis of eq. (23).
d
95% C.I. (confidence interval).
 P. Cardiano et al. / Fluid Phase Equilibria 480 (2019) 41e52 49

Table 7 for the variation of the log Ks0 values with the ionic strength
Experimental and calculated solubility products of 1,2,4-benzenetricarboxylate/
and logKsT0 is the solubility product at infinite dilution.
(CH3)4Nþ and 1,2,4-benzenetricarboxylate/Naþ species at different ionic strengths
and at T ¼ 298.15 Ka. Concerning SSW, also in this case we observed proton/ligand
molar ratios higher than the theoretical value, but we do not pro-
Experimental
pose a possible stoichiometry for the sparingly soluble species,
species Me4NH2L NaH2L Na2HL owing to the presence of different metal ions (i.e. Naþ, Kþ, Ca2þ,
Ib log KS0b,c Ib log KS0 log KS0 Mg2þ).
(CH3)4NCl NaCl Table 9 reports the log Ks0 values of each species at infinite
dilution and the parameter C for the dependence on ionic strength.
0.500 10.27 1.002 10.29 8.96
0.500 10.22 1.002 9.87 8.23
The calculated log Ks0 values at different ionic strengths are also
1.019 9.97 1.007 10.37 9.05 reported in Tables 6e8.
1.019 9.91 1.049 9.82 8.20
1.765 10.12 1.999 10.77 9.17 3.5. Complex formation with metal ions
2.091 10.36 1.999 10.82 9.20
2.014 10.64 3.008 10.76 9.10
3.034 10.53 5.002 12.52 10.48 The different trends of the protonation constants with respect to
3.034 10.68 5.002 12.16 10.12 the salt (supporting electrolyte) concentration can also be
3.039 10.83 explained in terms of complex formation between the different
Calculated deprotonated acid species and the metal cations (i.e. Naþ, Kþ, Mg2þ
species Me4NH2L NaH2L Na2HL and Ca2þ) [12,20,22,30,40e43]. Generally, it is assumed that tet-
Ib log KS0 Ib log KS0 log KS0
ralkylammoniun salts are not interacting towards O-donor ligands
0.500 9.92 ± 0.15d 1.002 10.48 ± 0.16 9.09 ± 0.21 [13,14]. For the benzenepolycarboxylic acids here investigated, we
1.019 10.24 ± 0.12 1.049 10.51 ± 0.16 9.11 ± 0.21 observed, except for 1,2,3-benzenetricarboxylic acid, that in-
1.765 10.44 ± 0.08 1.999 10.99 ± 0.15 9.43 ± 0.19
teractions occur at high tetramethylammoniun salt concentration,
2.091 10.50 ± 0.07 3.008 11.36 ± 0.20 9.62 ± 0.25
3.034 10.59 ± 0.09 5.002 11.93 ± 0.37 9.84 ± 0.45 with the formation of sparingly soluble (CH3)4NHiL species. For this
a reason, an attempt to calculate the formation constants of weak
Standard uncertainties u are: u (T) ¼ 0.15 K, u (p) ¼ 1 KPa, u
(I) ¼ 0.001 mol dm3. complexes also in this ionic medium were carried out.
b
Ionic strength and solubility product expressed in mol$dm3. In SSW medium, the contemporary presence of different metal
c
Calculated on the basis of eq. (23). cations (i.e. Naþ, Kþ, Mg2þ and Ca2þ) makes the determination of
d
95% C.I. (confidence interval). the complex formation constants particularly complicated. The use
of the single salt (BA) approximation simplify this kind of study
pffiffi since the interactions that must considered are between the
I different deprotonated acid species and the cation B1.117þ of the
log Ks0 ¼ logKsT0  z* ,0:51 , pffiffi þ C,I (24)
1 þ 1:5 I synthetic sea water, and the interaction of the anion of the single
salt A1.117 with Hþ. The complex formation constants can be
where as in equation (8), C is an empirical parameter that account expressed by means of the equilibrium:

Table 8
Experimental and calculated solubility products of 1,2,4,5-benzenetetracarboxylate/CH3)4Nþ and 1,2,4,5-benzenetetracarboxylate/Naþ species at different ionic strengths and
at T ¼ 298.15 Ka.

Experimental

species (Me)4NH3L Na2H2L

Ib log KS0b,c Ib log KS0

(CH3)4NCl NaCl

0.100 15.490 0.100 13.112

0.100 15.561 0.100 13.070
0.500 15.185 0.502 10.860
0.500 15.200 0.502 10.802
1.019 15.965 1.007 12.478
1.019 15.937 1.034 14.274
2.091 17.120
2.091 17.031
3.034 18.752
3.034 18.856

Calculated
species (Me)4NH3L Na2H2L
Ib log KS0 Ib log KS0

0.100 15.70 ± 0.06d 0.100 13.47 ± 0.22

0.500 15.19 ± 0.04 0.220 12.96 ± 0.18
1.019 15.62 ± 0.04 0.500 12.52 ± 0.12
2.091 17.20 ± 0.08 0.540 12.50 ± 0.12
3.034 18.81 ± 0.12 1.000 12.40 ± 0.20
1.040 12.41 ± 0.20
a
Standard uncertainties u are: u (T) ¼ 0.15 K, u (p) ¼ 1 KPa, u (I) ¼ 0.001 mol dm3.
b
Ionic strength and solubility product expressed in mol dm3.
c
Calculated on the basis of eq. (23).
d
95% C.I. (confidence interval).
50 P. Cardiano et al. / Fluid Phase Equilibria 480 (2019) 41e52

Table 9
Solubility products at infinite dilution and parameters for the dependence on the ionic strength at T ¼ 298.15 Ka (eq. (24)).

1,2,4-benzenetricarboxylic acid
bÞ
Species log KsT0 C
c)
NaH2L 7.84 ± 0.22 0.18 ± 0.10
Na2HL 7.10 ± 0.45 0.12 ± 0.09
Me4NH2L 7.85 ± 0.18 0.07 ± 0.05
1,3,5-benzenetricarboxylic acid
NaH2L 13.72 ± 0.06 0.18 ± 0.03
Na2HL 12.87 ± 0.11 0.58 ± 0.04
Me4NH2L 13.65 ± 0.06 0.33 ± 0.09
1,2,4,5-benzenetetracarboxylic acid
Na2H2L 15.57 ± 0.12 0.91 ± 0.18
Me4NH3L 17.69 ± 0.03 1.99 ± 0.02

Solubility product expressed in mol dm3.

b
a
Standard uncertainties u are: u (T) ¼ 0.15 K, u (p) ¼ 1 KPa.
c
95% C.I. (confidence interval).

pMnþ þ rLz þ iHþ ¼ MpLrH(p$nþi

i
e r$z)
(25)
where the charge of the cation is þ1 for Naþ and (CH3)4Nþ, þ1.117
for B (cation of the single salt).
Table 10 Reports the complex stability constants of the different
benzenepolycarboxylic acids here investigated in the different ionic
media.
Formation constant values of the NapHiL species are fairly
similar to the ones already reported in previous papers [30,37,38],
especially for 1,2,3-benzenetricarboxylic acid. For the formation of
the weak complexes in SSW a most simple speciation model was
obtained for all the systems; this model includes only the BL and
BHL species, as already obtained in Bretti et al. [11]. In tetrame-
thylammonium chloride, the speciation of the metal-ligand system
is fairly similar to the one observed in NaCl, with log bpri values
comparable between the two ionic media.
4. Literature comparison
Literature reports some data on the protonation constants of the
benzenepolycarboxylic acids here investigated in NaCl ionic me-
dium or in tetraalkylammonium salts [11,30,37e39,44,45], whilst
no information on the behavior of these ligands in SSW is present.
The dependence on ionic strength of the protonation constants of
1,2,4-benzenetricarboxylic in the different ionic media was
modeled by using at infinite dilution literature data [11]. For 1,2,4,5-
benzenetetracarboxylic acid, Curini et al. [37,38] report at infinite
dilution: log KH1 ¼ 6.09, log KH2 ¼ 4.77, log KH3 ¼ 3.00 and log
KH4 ¼ 1.95. De Robertis et al. published a paper [44] where the
thermodynamic parameters (i.e. log KH, DH and DCp of protonation)
and the parameter for the dependence on the ionic strength are
reported in tetraethylammoniun iodide solutions for different
classes of carboxylic ligands; for example, for 1,2,3-
benzenetricarboxylic acid: log KH1 ¼ 6.27, log KH2 ¼ 4.33 and log
KH3 ¼ 2.85.
As concerns the solubility of the benzenepolycarboxylic acids
here investigated, Apelblat [46] studied their total solubility only in
pure water at different temperatures, whilst no information on the
solubility in ionic media solution and the dependence on the ionic
strength is reported. The total solubility determined by Apelblat
et al. are: log ST0 ¼ 1.116 (T ¼ 295.65 K) for the 1,2,4-
benzenetricarboxylic acid (log ST0 ¼ 1.160, this work); log ST0
¼ 1.968 (T ¼ 298.15 K) for 1,3,5-benzenetricarboxylic acid (log ST0
¼ 1.990, this work). An attempt comparison can be made with the
literature data reported by Zhang and Xu [47] on the solubility of

Table 10
Formation constantsa of the weak Naþ, B1.117þ and (CH3)4Nþ complexes with the benzenepolycarboxylate anions at infinite dilution and T ¼ 298.15 Kb.

log bpric

Ligand NaL NaHL NaH2L Na2L Na2HL

d
1,2,3-benz 1.537 ± 0.002 7.061 ± 0.002 10.712 ± 0.001 2.479 ± 0.001 7.052 ± 0.003
1,2,4-benz 1.16 ± 0.20 5.77 ± 0.30 9.50 ± 0.27
1,3,5-benz 0.89 ± 0.33 6.12 ± 0.12 9.67 ± 0.12 1.56 ± 0.15 5.87 ± 0.14

NaH3L Na2L Na2HL Na2H2L

1,2,4,5-benz 14.22e 3.5 8.7 12.6
BL BHL

1,2,3-benz 1.64 ± 0.03d 6.14 ± 0.12

1,2,4-benz 1.33f 5.63f
1,3,5-benz 1.16 ± 0.14 5.79 ± 0.11
(CH3)4NL (CH3)4NHL (CH3)4NH2L ((CH3)4N)2L ((CH3)4N)2LH
d
1,2,3-benz 0.71 ± 0.11 6.14 ± 0.13 9.41 ± 0.43
1,2,4-benz 0.82 ± 0.08 5.42 ± 0.11 8.21 ± 0.55
1,3,5-benz 1.06 ± 0.07 5.66 ± 0.03 8.95 ± 0.09 1.35 ± 0.10
1,2,4,5-benz 1.44 ± 0.05 6.27 ± 0.08
a
Expressed in mol dm3.
b
Standard uncertainties u are: u (T) ¼ 0.15 K, u (p) ¼ 1 KPa.
c
Refers to equilibrium (25).
d
95% C.I. (confidence interval).
e
Ref. [37].
f
Ref. [11].
 P. Cardiano et al. / Fluid Phase Equilibria 480 (2019) 41e52
1,3,5-benzenetricarboxylic acid in water. These authors report at
T ¼ 301.05 K a total solubility value of log ST0 ¼ 2.083 that how-
ever is similar to the value above reported, extrapolated at infinite
dilution and at T ¼ 298.15 K.
In our knowledge, no information about the neutral species
solubility (log S00 ) and the Setschenow coefficients are reported in
the literature.
As regards the solubility product of the benzenepolycarboxylate
salt formed with the cation of the supporting electrolytes, we can
cite the data reported by Curini and D'Ascenzo [37], that report for
the solubility product of the 1,2,4,5-benzenetetracarboxate/Naþ
salt a stoichiometry similar to the one here obtained, namely
Na2H2L (L ¼ 1,2,4,5-benzenetetracarboxylic acid) and a solubility
product of log Ks0 ¼ 15.84, with respect to the value of log
Ks0 ¼ 15.57 ± 0.12 here determined.
In the past, our research group investigated the solubility of
the benzenetricarboxylic acids and the effect of different ionic
media on the acid-base properties [30,39,44]. In those papers, the
weak complex formation constants with Naþ were calculated and
were reported at infinite dilution. These data are in fairly good
agreement with those here determined whilst similar data for
1,2,4,5-benzenetetracarboxylic acid are reported by Daniele et al.,
1990.
5. Conclusion
The results of an investigation carried out on the acid base
properties and solubility of three isomer benzenetricarboxylic
acids, 1,2,3-, 1,2,4- and 1,3,5- and one tetracarboxylate, 1,2,4,5-
benzenetetracarboxylic acid are reported. The total solubility
and the protonation constants of the ligands were experimen-
tally determined by potentiometry in NaClaq, (CH3)4NClaq and
SSW at different ionic strengths and salinities and at T ¼
(298.15 ± 0.15) K. The trend of the protonation constants and
solubility highlight a significant medium effect on these param-
eters, with a salting-out effect in NaClaq and SSW and a salting-in
effect in (CH3)4NClaq. The dependence on salt concentration of
the solubility of the neutral species was modeled and the Set-
schenow coefficients were calculated for 1,2,3-
benzenetricarboxylic acid only in tetralkylammonium salt and
for 1,2,4-benzenetricarboxylic acid in the three ionic media, at
different supporting electrolytes concentrations.
For the other ligands, the formation of sparingly soluble species
was observed, in some case only at high supporting electrolyte
concentration. As an example, for 1,2,4-benzenetricarboxylic acid
in (CH3)4NClaq and up to I ¼ 1.019 mol dm3, the presence of the
H3L0 (ligand neutral species) was observed in the saturated solu-
tion. Over this value, the formation of the MH2L (M ¼ (CH3)4Nþ)
species was obtained. Similar behavior was observed in NaCl
aqueous solutions. In the cases of formation of sparingly soluble
species formed by the cation of the ionic medium and the depro-
tonated ligand species, different stoichiometry of the salts were
proposed on the basis of the ionic medium and of some previous
investigations on similar ligands. The solubility products of the
species were calculated at the different experimental conditions
(i.e. ionic strength and ionic medium).
The dependence on ionic strength of the protonation constants,
total and neutral species solubility, solubility product was analyzed
by a Debye-Hückel type equation, and the Specific ion Interaction
parameters were determined by SIT approach.
The stability constants of the weak complexes (NapHL; NaHiL;
NapHiL, ((CH3)4N)HiL, ((CH3)4N)pHiL or BHiL) in solution was also
determined by means of the ES2WC computer program.
51
Acknowledgement
 e della
We thank MIUR (Ministero dell’Istruzione, dell’Universita
Ricerca) for financial support (co-founded PRIN project with Prot.
2015 MP34H3).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.fluid.2018.09.027.
References
[1] Q.A. Acton, Aromatic Hydrocarbon - Advances in Research and Treatment,
Scholarly Editons, Atlanta, 2013.
[2] H.T. Aung, T. Nikai, M. Niwa, Y. Takaya, Benzenepolycarboxylic acids with
potential anti-hemorrhagic properties and structure-activity relationships,
Bioorg. Med. Chem. 19 (2011) 7000e7002.
[3] S.B. Clark, G.R. Choppin, Humic and Fulvic Acids Isolation, Structure, and
Environmental Role, American Chemical Society, Washington, DC, 1996.
[4] A. De Robertis, C. De Stefano, S. Sammartano, A. Gianguzza, Equilibrium
studies in natural fluids. A chemical speciation model for the major constit-
uents of seawater, Chem. Speciat. Bioavailab. 6 (1994) 65e84.
[5] C. De Stefano, C. Foti, S. Sammartano, A. Gianguzza, C. Rigano, Equilibrium
studies in natural fluids. Use of synthetic seawater and other media as
background salts, Ann. Chim. 84 (1994) 159e175.
[6] C. De Stefano, P. Princi, C. Rigano, S. Sammartano, Computer analysis of
equilibrium data in solution. ESAB2M: an improved version of the ESAB
program, Ann. Chim. 77 (1987) 643e675.
[7] C. De Stefano, P. Mineo, C. Rigano, S. Sammartano, Ionic strength dependence
of formation constants. XVII. The calculation of equilibrium concentrations
and formation constants, Ann. Chim. 83 (1993) 243e277.
[8] C. De Stefano, S. Sammartano, P. Mineo, C. Rigano, Computer tools for the
speciation of natural fluids, in: A. Gianguzza, E. Pelizzetti, S. Sammartano
(Eds.), Marine Chemistry - an Environmental Analytical Chemistry Approach,
Kluwer Academic Publishers, Amsterdam, 1997, pp. 71e83.
[9] F. Crea, C. De Stefano, A. Gianguzza, D. Piazzese, S. Sammartano, Protonation of
carbonate in aqueous tetraalkylammonium salts at 25 C, Talanta 68 (2006)
1102e1112.
[10] S.C. McCutcheon, J.J. Martin, T.O. Barnwell, Water quality, in: D.R. Maidment
(Ed.), Handbook of Hydrology, McGraw-Hill, New York, 1993.
[11] C. Bretti, R.M. Cigala, F. Crea, C. De Stefano, C. Foti, A. Pettignano,
S. Sammartano, Polycarboxylic acids in sea water: acidebase properties, sol-
ubilities, activity coefficients, and complex formation constants at different
salinities, Monatsh. Chem. 147 (2016) 1481e1505.
[12] C. De Stefano, C. Foti, A. Gianguzza, D. Piazzese, S. Sammartano, Binding ability
of inorganic major components of seawater towards some classes of ligands,
metals and organometallic cations, in: A. Gianguzza, E. Pelizzetti,
S. Sammartano (Eds.), Chemistry of Marine Waters and Sediments, Springer-
Verlag, Berlin, 2002, pp. 221e261.
[13] F. Crea, A. De Robertis, S. Sammartano, Medium and alkyl chain effects on the
protonation of dicarboxylates in NaCl(aq) and Et4NI(aq) at 25  C, J. Solut. Chem.
33 (2004) 499e526.
[14] P.L. Huyskens, W.A.P. Luck, Intermolecular Forces. An Introduction to Modern
Methods and Results, Springer-Verlag Berlin Heidelberg, 1991.
[15] P.G. Daniele, A. De Robertis, C. De Stefano, S. Sammartano, C. Rigano, On the
possibility of determining the thermodynamic parameters for the formation
of weak complexes using a simple model for the dependence on ionic
strength of activity coefficients. Naþ, Kþ and Ca2þ complexes of low molecular
weight ligands in aqueous solution, J. Chem. Soc. Dalton Trans. (1985)
2353e2361.
[16] P.G. Daniele, C. Rigano, S. Sammartano, Ionic strength dependence of forma-
tion constants. (Part 9). Alkali metal complexes of ethylenediaminetetraace-
tate, nitrilotriacetate, diphosphate, and tripolyphosphate in aqueous solution,
Anal. Chem. 57 (1985) 2956e2960.
, S. Sammartano, Ionic strength dependence of
[17] F. Crea, C. De Stefano, O. Giuffre
protonation constants of N-Alkylsubstituted open chain diamines in NaClaq,
J. Chem. Eng. Data 49 (2004) 109e115.
[18] C. De Stefano, C. Foti, A. Gianguzza, S. Sammartano, The single salt approxi-
mation for the major components of seawater: association and acid-base
properties, Chem. Speciat. Bioavailab. 10 (1998) 27e29.
[19] F. Crea, A. Giacalone, A. Gianguzza, D. Piazzese, S. Sammartano, Modelling of
natural synthetic polyelectrolyte interactions in natural waters by using SIT,
Pitzer and Ion Pairing approaches, Mar. Chem. 99 (2006) 93e105.
[20] C. De Stefano, S. Sammartano, A. Gianguzza, D. Piazzese, Speciation of poly-
electrolytes in natural fluids. Protonation and interaction of polymetacrylates
with major components of seawater, Talanta 58 (2002) 405e417.
[21] C. De Stefano, C. Foti, A. Gianguzza, S. Sammartano, The interaction of amino
acids with the major constituents of natural waters at different ionic
strengths, Mar. Chem. 72 (2000) 61e76.
[22] C. De Stefano, A. Gianguzza, D. Piazzese, S. Sammartano, Speciation of low
52 P. Cardiano et al. / Fluid Phase Equilibria 480 (2019) 41e52
molecular weight carboxylic ligands in natural fluids: protonation constants
and association with major components of seawater of oxydiacetic and citric
acids, Anal. Chim. Acta 398 (1999) 103e110.
[23] F. Crea, A. De Robertis, S. Sammartano, Dioxouranium carboxylate complexes.
Formation and stability of acetate species at different ionic strengths in
NaClaq, Ann. Chim. 93 (2003) 1027e1035.
[24] L. Ciavatta, The specific interaction theory in evaluating ionic equilibria, Ann.
Chim. 70 (1980) 551e567.
[25] E.A. Guggenheim, J.C. Turgeon, Specific interaction of ions, Trans. Faraday Soc.
51 (1955) 747e761.
[26] G. Scatchard, Concentrated solutions of strong electrolytes, Chem. Rev. 19
(1936) 309e327.
[27] J.N. Brønsted, Studies on solubility. IV. The principle of the specific interaction
of ions, J. Am. Chem. Soc. 44 (1922) 877e898.
[28] J.Z. Setschenow, Uber die konstitution der salzlosungenauf grund ihres ver-
haltens zu kohlensaure, Z. Phys. Chem. 4 (1889) 117e125.
[29] F. Crea, C. De Stefano, C. Foti, S. Sammartano, SIT parameters for the depen-
dence of (poly)carboxylate activity coefficients on ionic strength in (C2H4)
4NIaq (0 < I < 1.2 mol kg-1) and (CH3)4NClaq (0 < I < 3.9 mol kg-1) in the
temperature range 278 < T < 328 K, and correlation with Pitzer parameters,
J. Chem. Eng. Data 52 (2007) 2195e2203.
[30] F. Crea, G. D'Ascenzo, A. De Robertis, S. Materazzi, S. Sammartano, The for-
mation of sparingly soluble species of Ca2þ with carboxylic ligands: speciation
and thermoanalysis, Talanta 61 (2003) 611e620.
[31] C. Bretti, F. Crea, C. Foti, S. Sammartano, Solubility and activity coefficients of
o-phthalic acid and cystine in NaClaq, (CH3)4NClaq and (C2H5)4NIaq at different
ionic strengths, at t ¼ 25  C, J. Chem. Eng. Data 50 (2005) 1761e1767.
[32] C. Bretti, F. Crea, C. Foti, S. Sammartano, Solubility and activity coefficients of
acidic and basic nonelectrolytes in aqueous salt solutions. 2. Solubility and
activity coefficients of suberic, azelaic and sebacic acids in NaCl(aq),
(CH3)4NCl(aq) and (C2H5)4NI(aq) at different ionic strengths and at t ¼ 25  C,
J. Chem. Eng. Data 51 (2006) 1660e1667.
[33] C. Bretti, R.M. Cigala, F. Crea, C. Foti, S. Sammartano, Solubility and activity
coefficients of acidic and basic nonelectrolytes in aqueous salt solutions. 3.
Solubility and acitivity coefficients of adipic and pimelic acids in NaCl(aq),
(CH4)4NCl(aq) and (C2H5)4NI(aq) at different ionci strengths and at t ¼ 25  C,
Fluid Phase Equil. 263 (2008) 43e54.
[34] G. Battaglia, R.M. Cigala, F. Crea, S. Sammartano, Solubility and acid-base
properties of ethylenediaminetetraacetic acid in aqueous NaCl solution at
0 < I < 6 mol kg-1 and T ¼ 298.15 K, J. Chem. Eng. Data 53 (2008) 363e367.
[35] S. Cataldo, F. Crea, A. Gianguzza, A. Pettignano, D. Piazzese, Solubility and acid-
base properties and activity coefficients of chitosan in different ionic media
and at different ionic strengths, at T ¼ 25  C, J. Mol. Liquids 148 (2009)
120e126.
[36] F.A. Long, W.F. McDevit, Activity coefficients of nonelectrolyte solutes in
aqueous salt solutions, Chem. Rev. 51 (1952) 119e169.
[37] R. Curini, G. D'Ascenzo, A. De Robertis, C. De Stefano, S. Sammartano, Studies
on polyfunctional O-ligands. Solubility and thermal stability of 1,2,4,5-
Benzentetra-carboxylate with alkali and alkaline-earth metal ions, Thermo-
chim. Acta 173 (1990) 25e41.
[38] P.G. Daniele, A. De Robertis, C. De Stefano, S. Sammartano, Studies on poly-
functional O-ligands. Formation and stability of alkali metal-1,2,4,5-
benzenetetracarboxylate complexes at different ionic strengths in aqueous
solution, Ann. Chim. 80 (1990) 177e186.
[39] A. De Robertis, A. Gianguzza, S. Sammartano, Solubility of some calcium-
carboxylic ligand complexes in aqueous solution, Talanta 42 (1995)
1651e1662.
[40] J. Buffle, Complexation Reactions in Aquatic Systems; Analytical Approach, J.
Wiley & Sons Ltd./Ellis Horwood Ltd, Chichester, 1988.
[41] C. De Stefano, A. Gianguzza, D. Piazzese, S. Sammartano, Mar. Chem. 86 (2004)
33e44.
[42] A. De Robertis, C. De Stefano, C. Foti, A. Gianguzza, D. Piazzese, S. Sammartano,
Protonation constants and association of polycarboxylic ligands with the
major components of seawater, J. Chem. Eng. Data 45 (2000) 996e1000.
[43] P.G. Daniele, C. Foti, A. Gianguzza, E. Prenesti, S. Sammartano, Weak alkali and
alkaline earth metal complexes of low molecular weight ligands in aqueous
solution, Coord. Chem. Rev. 252 (2008) 1093e1107.
[44] A. De Robertis, C. De Stefano, C. Rigano, S. Sammartano, Thermodynamic
parameters for the protonation of carboxylic acids in aqueous tetraethy-
lammonium iodide solutions, J. Solut. Chem. 19 (1990) 569e587.
[45] L.D. Pettit, K.J. Powell, IUPAC stability constants database, in: Academic Soft-
ware, IUPAC, 2001.
[46] A. Apelblat, E. Manzurola, N. Abo Balal, The solubilities of benzene poly-
carboxylic acids in water, J. Chem. Thermodyn. 38 (2006) 565e571.
[47] D. Zhang, Q. Xu, Solubility of 1,3,5-benzenetricarboxylic acid in different
solvents, J. Chem. Eng. Data 61 (2016) 1003e1006.
[48] D.D. Perrin, W.L.F. Armarego, D.R. Perrin, Purification of Laboratory Chemicals,
1 ed., Pergamon Press, 1966.