Polycarboxylic acids in sea water: acid–base properties, solubilities, activity coefficients, and complex formation constants at different salinities

Alberto Pettignano, Silvio Sammartano, Claudia Foti, Concetta De Stefano, Clemente Bretti, Rosalia Maria Cigala, Francesco Crea

Research output: Contribution to journalArticle

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Abstract

This paper reports the results of the investigations carried out in synthetic sea water at different salinities for different classes of polycarboxylic acids. The investigations can be summarized as follows: (a) Determination of the protonation constants in such multicomponent solution in a salinity range 15 ≤ S ≤ 45, at t = 25 °C, for the linear dicarboxylic acids HOOC-(CH2)n–COOH (0 ≤ n ≤ 8), and aromatic polycarboxylic acids (o-phthalic and 1,2,4-benzenetricarboxylic acids). For malonic, succinic, 1,2,3-benzenetricarboxylic, and 1,2,3,4-benzenetetracarboxylic acids, investigations were also carried out at t = 10 and 37 °C; (b) Determination of the total and intrinsic solubility (ST and S0, respectively) of the linear dicarboxylic acids HOOC-(CH2)n-COOH (0 ≤ n ≤ 8), o-phthalic, 1,2,4-benzenetricarboxylic acids at t = 25 °C and 15 ≤ S ≤ 45, and calculation of the corresponding Setschenow parameters and activity coefficients; (c) Modeling the dependence of the experimental and literature protonation constants of the polycarboxylic acids on salinity, acid concentration, temperature, and number of the methylene groups in the molecules by means of new empirical equations; (d) Determination of the specific interaction parameters in synthetic sea water of the ionic species of the acids by means of the specific ion interaction theory and Pitzer models; (e) Determination of the protonation constant of the anion A1.117− of the single salt BA at different salinities and temperatures; (f) Determination and modeling in dependence of the salinity of the ΔH/kJ mol−1 of protonation of the linear dicarboxylic acids and of the A1.117− anion, by means of a Debye-Hückel type equation; (g) Determination of the complex formation constants (log βBpLHi) between the cation B1.117+ and the different deprotonated species of the carboxylic acids at different salinities and temperatures. Independent of the thermodynamic aqueous properties determined, a significant dependence of these parameters (log βiH, log βBpLHi, ΔH/kJ mol−1 of protonation, ST and S0) on the ionic medium, salinity, and temperature was observed. Moreover, the huge number of data collected allowed us to propose some empirical equations to model/predict the behavior of these classes of O-donor ligands in a multicomponent solution such as synthetic sea water. Graphical abstract: [Figure not available: see fulltext.]
Original languageEnglish
Pages (from-to)1481-1505
Number of pages25
JournalMONATSHEFTE FÜR CHEMIE
Volume147
Publication statusPublished - 2016

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Protonation
Activity coefficients
Solubility
Dicarboxylic Acids
Acids
Water
Anions
Temperature
Succinic Acid
Carboxylic Acids
Carboxylic acids
Cations
Salts
Thermodynamics
Ions
Ligands
Molecules
trimellitic acid

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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Polycarboxylic acids in sea water: acid–base properties, solubilities, activity coefficients, and complex formation constants at different salinities. / Pettignano, Alberto; Sammartano, Silvio; Foti, Claudia; De Stefano, Concetta; Bretti, Clemente; Cigala, Rosalia Maria; Crea, Francesco.

In: MONATSHEFTE FÜR CHEMIE, Vol. 147, 2016, p. 1481-1505.

Research output: Contribution to journalArticle

Pettignano, Alberto ; Sammartano, Silvio ; Foti, Claudia ; De Stefano, Concetta ; Bretti, Clemente ; Cigala, Rosalia Maria ; Crea, Francesco. / Polycarboxylic acids in sea water: acid–base properties, solubilities, activity coefficients, and complex formation constants at different salinities. In: MONATSHEFTE FÜR CHEMIE. 2016 ; Vol. 147. pp. 1481-1505.
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abstract = "This paper reports the results of the investigations carried out in synthetic sea water at different salinities for different classes of polycarboxylic acids. The investigations can be summarized as follows: (a) Determination of the protonation constants in such multicomponent solution in a salinity range 15 ≤ S ≤ 45, at t = 25 °C, for the linear dicarboxylic acids HOOC-(CH2)n–COOH (0 ≤ n ≤ 8), and aromatic polycarboxylic acids (o-phthalic and 1,2,4-benzenetricarboxylic acids). For malonic, succinic, 1,2,3-benzenetricarboxylic, and 1,2,3,4-benzenetetracarboxylic acids, investigations were also carried out at t = 10 and 37 °C; (b) Determination of the total and intrinsic solubility (ST and S0, respectively) of the linear dicarboxylic acids HOOC-(CH2)n-COOH (0 ≤ n ≤ 8), o-phthalic, 1,2,4-benzenetricarboxylic acids at t = 25 °C and 15 ≤ S ≤ 45, and calculation of the corresponding Setschenow parameters and activity coefficients; (c) Modeling the dependence of the experimental and literature protonation constants of the polycarboxylic acids on salinity, acid concentration, temperature, and number of the methylene groups in the molecules by means of new empirical equations; (d) Determination of the specific interaction parameters in synthetic sea water of the ionic species of the acids by means of the specific ion interaction theory and Pitzer models; (e) Determination of the protonation constant of the anion A1.117− of the single salt BA at different salinities and temperatures; (f) Determination and modeling in dependence of the salinity of the ΔH/kJ mol−1 of protonation of the linear dicarboxylic acids and of the A1.117− anion, by means of a Debye-H{\"u}ckel type equation; (g) Determination of the complex formation constants (log βBpLHi) between the cation B1.117+ and the different deprotonated species of the carboxylic acids at different salinities and temperatures. Independent of the thermodynamic aqueous properties determined, a significant dependence of these parameters (log βiH, log βBpLHi, ΔH/kJ mol−1 of protonation, ST and S0) on the ionic medium, salinity, and temperature was observed. Moreover, the huge number of data collected allowed us to propose some empirical equations to model/predict the behavior of these classes of O-donor ligands in a multicomponent solution such as synthetic sea water. Graphical abstract: [Figure not available: see fulltext.]",
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T1 - Polycarboxylic acids in sea water: acid–base properties, solubilities, activity coefficients, and complex formation constants at different salinities

AU - Pettignano, Alberto

AU - Sammartano, Silvio

AU - Foti, Claudia

AU - De Stefano, Concetta

AU - Bretti, Clemente

AU - Cigala, Rosalia Maria

AU - Crea, Francesco

PY - 2016

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N2 - This paper reports the results of the investigations carried out in synthetic sea water at different salinities for different classes of polycarboxylic acids. The investigations can be summarized as follows: (a) Determination of the protonation constants in such multicomponent solution in a salinity range 15 ≤ S ≤ 45, at t = 25 °C, for the linear dicarboxylic acids HOOC-(CH2)n–COOH (0 ≤ n ≤ 8), and aromatic polycarboxylic acids (o-phthalic and 1,2,4-benzenetricarboxylic acids). For malonic, succinic, 1,2,3-benzenetricarboxylic, and 1,2,3,4-benzenetetracarboxylic acids, investigations were also carried out at t = 10 and 37 °C; (b) Determination of the total and intrinsic solubility (ST and S0, respectively) of the linear dicarboxylic acids HOOC-(CH2)n-COOH (0 ≤ n ≤ 8), o-phthalic, 1,2,4-benzenetricarboxylic acids at t = 25 °C and 15 ≤ S ≤ 45, and calculation of the corresponding Setschenow parameters and activity coefficients; (c) Modeling the dependence of the experimental and literature protonation constants of the polycarboxylic acids on salinity, acid concentration, temperature, and number of the methylene groups in the molecules by means of new empirical equations; (d) Determination of the specific interaction parameters in synthetic sea water of the ionic species of the acids by means of the specific ion interaction theory and Pitzer models; (e) Determination of the protonation constant of the anion A1.117− of the single salt BA at different salinities and temperatures; (f) Determination and modeling in dependence of the salinity of the ΔH/kJ mol−1 of protonation of the linear dicarboxylic acids and of the A1.117− anion, by means of a Debye-Hückel type equation; (g) Determination of the complex formation constants (log βBpLHi) between the cation B1.117+ and the different deprotonated species of the carboxylic acids at different salinities and temperatures. Independent of the thermodynamic aqueous properties determined, a significant dependence of these parameters (log βiH, log βBpLHi, ΔH/kJ mol−1 of protonation, ST and S0) on the ionic medium, salinity, and temperature was observed. Moreover, the huge number of data collected allowed us to propose some empirical equations to model/predict the behavior of these classes of O-donor ligands in a multicomponent solution such as synthetic sea water. Graphical abstract: [Figure not available: see fulltext.]

AB - This paper reports the results of the investigations carried out in synthetic sea water at different salinities for different classes of polycarboxylic acids. The investigations can be summarized as follows: (a) Determination of the protonation constants in such multicomponent solution in a salinity range 15 ≤ S ≤ 45, at t = 25 °C, for the linear dicarboxylic acids HOOC-(CH2)n–COOH (0 ≤ n ≤ 8), and aromatic polycarboxylic acids (o-phthalic and 1,2,4-benzenetricarboxylic acids). For malonic, succinic, 1,2,3-benzenetricarboxylic, and 1,2,3,4-benzenetetracarboxylic acids, investigations were also carried out at t = 10 and 37 °C; (b) Determination of the total and intrinsic solubility (ST and S0, respectively) of the linear dicarboxylic acids HOOC-(CH2)n-COOH (0 ≤ n ≤ 8), o-phthalic, 1,2,4-benzenetricarboxylic acids at t = 25 °C and 15 ≤ S ≤ 45, and calculation of the corresponding Setschenow parameters and activity coefficients; (c) Modeling the dependence of the experimental and literature protonation constants of the polycarboxylic acids on salinity, acid concentration, temperature, and number of the methylene groups in the molecules by means of new empirical equations; (d) Determination of the specific interaction parameters in synthetic sea water of the ionic species of the acids by means of the specific ion interaction theory and Pitzer models; (e) Determination of the protonation constant of the anion A1.117− of the single salt BA at different salinities and temperatures; (f) Determination and modeling in dependence of the salinity of the ΔH/kJ mol−1 of protonation of the linear dicarboxylic acids and of the A1.117− anion, by means of a Debye-Hückel type equation; (g) Determination of the complex formation constants (log βBpLHi) between the cation B1.117+ and the different deprotonated species of the carboxylic acids at different salinities and temperatures. Independent of the thermodynamic aqueous properties determined, a significant dependence of these parameters (log βiH, log βBpLHi, ΔH/kJ mol−1 of protonation, ST and S0) on the ionic medium, salinity, and temperature was observed. Moreover, the huge number of data collected allowed us to propose some empirical equations to model/predict the behavior of these classes of O-donor ligands in a multicomponent solution such as synthetic sea water. Graphical abstract: [Figure not available: see fulltext.]

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EP - 1505

JO - Monatshefte für Chemie und verwandte Teile anderer Wissenschaften

JF - Monatshefte für Chemie und verwandte Teile anderer Wissenschaften

SN - 0343-7329

ER -