Gallium (III) Ion Hydrolysis Under Physiological Conditions: Brahim Hacht
Gallium (III) Ion Hydrolysis Under Physiological Conditions: Brahim Hacht
Gallium (III) Ion Hydrolysis Under Physiological Conditions: Brahim Hacht
2 Brahim Hacht
The hydrolysis of gallium(III) has been studied using potentiometric techniques under physiological conditions
of temperature 37 °C and ionic strength 0.15 mol·dm−3 NaCl and at different metal ion concentrations. Changes
in pH were monitored with a glass electrode calibrated daily in hydrogen ions concentrations. The titration
data within the pH range of 2.5-9.99 were analyzed to determine stability constants of hydroxide species using
the SUPERQUAD program. Several different species were considered during the calculation procedure
and the following hydroxides have been characterized: Ga(OH)3, Ga(OH)4− Ga3(OH)112−, Ga4(OH)11+ and
Ga6(OH)153+. Speciation calculations based on the determined constants were then used to simulate the species
distribution.
Key Words : Gallium(III), Hydrolysis, Stability constants, Potentiometry, Physiological conditions
calomel electrode, fitted in a thermostated Metrohm 20 cm3 the reaction for the hydrolysis can be written:
cell unit. E.m.f. variations were monitored by a Beckman
+ qH 2 O ↔ M p ( OH ) q
3+ 3p – q +
pM + qH (1)
model 4500 digital mV-meter. The temperature of the
reaction vessel was maintained at 37 ± 0.02 °C by circulating The numerical treatment of the data was performed by the
water and all titrations were carried out under a constant program SUPERQUAD. To be in agreement with the
bubbling of purified and thermostatted nitrogen. The above notations of this program, the cumulative stability constant
electrode system was calibrated in the concentration scale,20 of the equilibrium (1) is given by the equation (2) where
the ionic product of water being found equal to 10−13.24 under charges and molecules of water have been omitted for the
the present conditions. The value of Kw was estimated using sake of simplicity:
acide-base titration curves and the refined value was obtain- [ M p ( OH ) q ]
ed using the SUPERQUAD21 computer program. Accord- β pq = ----------------------------
- (2)
[M] [H]
p –q
ingly, the symbol pH used throughout actually represents
–log[H+]. The slope s from the Nernst equation, E = E0 – According to SUPERQUAD notations, the hydroxo-
s.pH was determined using acide-base titration.20 The elec- complexes are referred to as (p, −q) pairs and the hydroxide
trode slope was found equivalent to the expected theoretical ion is thus (0, −1).
one (61.54 mV·pH −1). In these conditions, the value of the The experimental hydroxylation curves were plotted using
standard electromotive force, E0 takes into account the liquid equation (3). These curves represent the average number of
junction potential and activity coefficient terms. With a view hydroxides bound to each metal ion:
to avoid the day-to-day drift of E0, the E of 0.01 mol·dm−3 C OH – C H – [ OH ] + [ H ]
− +
HCl was measured at the beginning of each titration. q = --------------------------------------------------------------
- (3)
CM
Successive aliquots of sodium hydroxide 0.1 mol·dm−3
were delivered from a Radiometer ABU 12 Autoburette with COH and CH = total concentrations of strong hydroxide
equipped with a 25 cm3 glass cylinder, both titrate and titrant and acid, respectively, as a function of pOH. From the shape
containing 0.15 mol·dm−3 NaCl. of these curves, estimates of some formation constants can
As may be noted in Table 1, where titration data are be made. They were consequently used as an input data and
summarized and whose results are given in the supple- refined with the help of the SUPERQUAD computer pro-
mentary data, metal ions concentration were varied signifi- gram. Then the final discrimination between sets displaying
cantly over the set of these experiments in view to allow the similar SUPERQUAD analyses was based on the two
formation of different metal-hydroxide stoichiometries. parameters: σ (connected with the objective function) and χ2
It is well known that hydrolytic complexation largely statistics. The critical values are assumed as σ < 3 and χ2 ≤
depends on the experiment conditions, which have a strong 12.60 at the 0.95 confidence level. Graphical comparisons
influence on the nature and relative concentrations of the between calculated curves and the corresponding simulated
formed species.22-25 The main technical difficulty arises from data were taken into account too.
the very slow reaction process. This phenomenon was
already mentioned in the case of Al(III) hydrolysis investi- Results and Discussion
gated under the same conditions of temperature and ionic
strength.26 It is worth noting that for pH values above ca. 5 and
In view of this, it was decided to select the same independently of Ga3+ concentration, a slight opacity was
operational protocol as detailed in reference.26 It consists in observed in the titration cell, indicative of the initiation of a
experiments with the smallest aliquots of hydroxide with precipitation process which can be assigned to the neutral
potentials been read every 2 min. hydroxide Ga(OH)3. Titrations were not stopped in view to
Calculation Procedures. Potentiometric data were treated collect data beyond the true equilibrium which may some-
following our usual approach27,28 involving optimization and times be useful in defining the stoichiometry of hydroxides
simulation in successive steps. predominating under such conditions.26 The study of the
For a general complex formula corresponding to Ga(III)-OH − system was thus conducted in two steps: (i) all
3p – q
M p ( OH ) q (M = Ga(III) metal ion, OH = hydroxide ion, the measurement data shown in figue 1 were first considered
for examination and (ii) when the set of stability constant
representing the best model was established with the help of
Table 1. Summary of the Titration Data Used for this Studya
SUPERQUAD program, it was then used for the interval of
System CM CH pH range Exp. n data pairs limited to pH 5.
Ga(III)-hydroxide 3.242 2.570 2.71-8.03 + 50 Figure 1 represents the experimental hydroxylation curves
4.539 3.675 2.47-9.99 × 67 as defined in equation (3) of the Ga(III)-hydroxide system
5.187 4.138 2.42-5.62 □ 44 for the reactant concentrations shown in Table 1.
6.484 5.199 2.28-7.23 △ 53 One can notice that our experimental hydroxylation curves
6.484 5.140 2.28-7.94 ▽ 44 are strikingly similar to that of aluminium hydrolysis carried
a
Initial total concentration (mmol·dm−3) of metal (CM), hydrochloric acid out in the same conditions.26 Indeed, the two sets of curves
(CH) and number of experimental observations (n). Exp.: Experiment. are superimposable with a relative shift to higher pOH in the
374 Bull. Korean Chem. Soc. 2008, Vol. 29, No. 2 Brahim Hacht
[M] [H]
p –q
obtained by means of SIMDIS program using results in Table 2 (i);
meter given by SUPERQUAD; n = number of experimental observations. key to symbols as in Table 1.
Gallium(III) Ion Hydrolysis under Physiological Conditions Bull. Korean Chem. Soc. 2008, Vol. 29, No. 2 375
Conclusion
Table 3. Logarithm of the formation constants for some selected
monomeric gallium hydroxydes in aqueous solution at different
conditions taken from the literature. The aim of this study was to make a contribution towards
the hydrolysis of Gallium(III) in aqueous medium and near
Temp. log10βpq
Medium Ref. physiological conditions. This was done using potentio-
(°C) (1, −1) (1, −2) (1, −3) (1, −4) metric techniques assisted by computer calculations.
0.15 M NaCl 37 − − −9.52 −18.06 This study From the overall presented study, it is concluded that in
0.10 M KNO3 25 −3.16 −7.07 − − 25 physiological conditions (37 °C, 0.15 mol·dm−3 NaCl) and
0.10 M NaCl 25 −2.90 −6.60 −11.00 − 31 for the range of concentrations used, gallium(III) ions gives
0.10 M NaClO4 25 −2.87 −6.55 −11.07 − 32 rise to monomeric hydroxydes M(OH)3 and M(OH)4 along
with polycationic species M3(OH)11, M4(OH)11 and M6(OH)15.
Our results are in good agreement with the prediction of
validity of the approach used. Baes and Mesmer14 who indicate the tendency of Ga(III) to
Concerning the data limited to pH range defined above engender polycationic hydroxides and the difficulty to deter-
(see figure 1), the ‘best’ model shown in Table 2 (ii) was mine mononuclear species. Indeed, our speciation calcu-
obtained according to the same procedure relative to the lations show that M6(OH)15 is formed around pH = 2.8.
whole pH interval. As may be noted, the species M(OH)4 Moreover, our results confirm the resemblance of Ga(III)
and M3(OH)11 are not formed in this restricted pH range. and Al(III) regarding aqueous hydrolysis, since the latter
Nevertheless, one may note the existence of M(OH)3 beside produces monomeric and polymeric hydroxides under the
polynuclear hydroxides M4(OH)11 and M6(OH)15. Moreover, same conditions of temperature and ionic strength.26 Never-
theless, there is a poor concordance with many literature
data obtained at different conditions,31,32 which confirm
exclusively the presence of mononuclear hydroxides.
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