0000000000117494
AUTHOR
Alessandro De Robertis
Equilibrium Studies in Natural Fluids. A Chemical Speciation Model for the Major Constituents of Seawater.
AbstractThe speciation of CI−, OH− and SO42- in synthetic sea water has been studied by Potentiometric measurements (pH-metric and ISE-Na methods) and by literature data analysis, using a well tested complex formation model. Stability constants, together with distribution of hypothesised species in synthetic sea water, as a function of temperature and salinity, are reported. The speciation model proposed in this work is discussed on the basis of chemical and statistical considerations. Comparison with some literature sea water models is given.
Thermodynamic parameters for the formation of glycine complexes with magnesium(II), calcium(II), lead(II), manganese(II), cobalt(II), nickel(II), zinc(II) and cadmium(II) at different temperatures and ionic strengths, with particular reference to natural fluid conditions
Abstract Protonation constants and Mg 2+ , Ca 2+ , Pb 2+ , Mn 2+ -, Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ and Cd 2+ glycine complex formation constants have been determined in different aqueous media at different temperatures. Salt effects are explained by a complex formation model which takes into account the formation of weak species. From the temperature dependence of the formation constants, thermodynamic parameters ΔH θ (and in some cases ΔC θ p ) have been obtained. A rigorous analysis of literature data, together with experimental findings, allows recommended formation parameters, in the ranges 0 ≤ I e ≤ 1 mol l −1 ( I e is the effective ionic strength) and 5°C ≤ T ≤ 45°C, to be obt…
Stability−Charge and Stability−Structure Relationships in the Binding of Dicarboxylic Ligands by Open-Chain Polyammonium Cations
The stability of complexes formed by 5 dicarboxylic ligands with 11 open-chain polyammonium cations (40 systems) was studied potentiometrically, in aqueous solution, at 25 °C. In all the systems ALHr species (A = amine, L = dicarboxylic ligand, r = 1 ... n; diamines n = 3, triamines n = 4, tetraamines n = 4 or 5) were found. Formation constants for the various complexes studied in this work, together with data for the analogous systems previously studied (20 systems), were examined as a function of charges involved in the formation reaction and of the structure of both the dicarboxylic ligand and the polyammonium cation. Structure generally has little effect on stability, while charges play…
Salt effects on the protonation of l-histidine and l-aspartic acid: a complex formation model
Abstract Protonation constants of l -histidine (histidinate: his − ) and l -aspartic acid (aspartate: asp 2− ) were determined potentiometrically, using the (H + ) glass electrode, in aqueous tetraethylammonium iodide (Et 4 NI), calcium chloride and sodium chloride solutions, at 0 −3 and 10 ⩽, T ⩽, 45 ° C. Differences in protonation constants determined in different salt media were explained by a complex formation model and, according to this model, the presence of the following species was hypothesized: Ca(his) + , CaH(his) 2+ , CaH 2 (his) 3+ Na(his) 0 , H 3 (his)X + , H 2 (his)X 0 , Et 4 N(his) 0 , Et 4 NH(his) + , Ca(asp) 0 , CaH(asp) + , CaH 2 (asp) 2+ , Na(asp) − , NaH(asp) 0 , H 3 (a…
Protonation constants and association of polycarboxylic ligands with the major components of seawater
Apparent protonation constants, log βjH*, of 11 carboxylic acids were determined potentiometrically ([H+]-glass electrode) in artificial seawater containing six of the major components (Na+, K+, Mg2+, Ca2+, Cl-, and SO42-) at different salinities: S (‰) = 5, 15, 25, 35, 45. Values of log βjH* were fitted by the simple polynomial equation log βjH* = log TβjH + a1S1/2 + a2S + a3S3/2 (log TβjH = protonation constants at infinite dilution; a1, a2, a3 = empirical parameters), for mono-, di-, and tricarboxylates. For carboxylic anions with charge < −3, a better fit was obtained using the equation log βjH* = log TβjH + b1I + b0z* log(1 + b2I) (b0, b1, b2 = empirical parameters, z* = square sum of…
Binding of acrylic and sulphonic polyanions by open-chain polyammonium cations
Abstract The interactions between some acrylic and sulphonic polyanions and some protonated amines (diamines NH 2 -(CH 2 ) x -NH 2 , x =2,…,10; linear tri-, tetra-, penta- and hexa-amines) were studied potentiometrically in aqueous solution, at 25°C. For both types of polyanions AL 2 H i (L − , monomer of polyanion, A, amine) species are formed, with i =1,…, n ( n =number of amino groups in the amine). The stability of these species is strictly dependent on the polyammonium cation charge, and fairly independent of the type of amine (in diamine species maximum stability is observed for x =4, 5). Acrylic and sulphonic polyanion complexes are considerably stronger than analogous species formed…
Hydrolysis of (CH3)Hg+ in Different Ionic Media: Salt Effects and Complex Formation
The hydrolysis of monomethylmercury(II) was studied potentiometrically, in NaNO3, Na2SO4, and NaCl aqueous solution, in a wide range of ionic strengths (NaNO3, 0 ≤ I ≤ 3.25; Na2SO4, 0 ≤ I ≤ 1; NaCl, 0 ≤ I ≤ 3 mol dm-3) and at t = 25 °C. For the reaction (CH3)Hg+ = (CH3)Hg(OH)° + H+, we found log K1 = −4.528 (I = 0 mol dm-3). The species [(CH3)Hg]2(OH)+ was also found, with log β2 = −2.15. Monomethylmercury(II) forms quite strong complexes with Cl- (log K = 5.45, I = 0 mol dm-3) and SO42- (log K = 2.64, I = 0 mol dm-3). The dependence on ionic strength of formation constants was considered by using a Debye−Huckel type equation. Hydrolysis and complex formation constants (at different ionic s…
Interaction of methyltin(IV) compounds with carboxylate ligands. Part 1: formation and stability of methyltin(IV)–carboxylate complexes and their relevance in speciation studies of natural waters.
Quantitative data on the stability of mono-, di- and trimethyltin(IV)-carboxylate complexes (acetate, malonate, succinate, malate, oxydiacetate, diethylenetrioxydiacetate, tricarballylate, citrate, butanetetracarboxylate and mellitate) are reported at t=25°C and I → 0 mol l - 1 . Several mononuclear, mixed proton, mixed hydroxo and polynuclear species are formed in these systems. As expected, the stability trend is mono- > di- > trimethyltin(IV) and mono < di < tri < tetra < hexa for the organotin moieties and carboxylate ligands investigated, respectively. Moreover, ligands containing, in addition to carboxylic,-O-and-OH groups show a significantly higher stability with respect to analogou…
Solubility of some calcium-carboxylic ligand complexes in aqueous solution
Insoluble species were identified in the systems Ca(2+)-hemimellitate, Ca(2+)-1,2,3,4-butanetetracarboxylate and Ca(2+)-citrate, and their solubilities were determined in aqueous solution at T = 25 degrees C. Values of pK(s0) were obtained for the species CaLH (L = benzene-1,2,3-tricarboxylate or hemimellitate), Ca(2)L (L = 1,2,3,4-butanetetracarboxylate), CaLH and Ca(3)L(2) (L = citrate), together with their dependence on ionic strength. Solid compounds were also characterized by thermogravimetry. The complex formation in solution for the system Na(+) - and Ca(2+)-hemimellitate was studied too.