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

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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 (S T and S 0, 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 β BpLHi) 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 β Hi , log β BpLHi, ΔH/kJ mol−1 of protonation, S T and S 0) 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.

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Abbreviations

Ac:

Acetic acid

Adip:

Adipic acid

Aze:

Azelaic acid

1,2,4-Benz:

1,2,4-Benzenetricarboxylic acid

Btc:

1,2,3,4-Butantetracarboxylic acid

Cit:

Citric acid

Glu:

Glutaric acid

Mal:

Malonic acid

Mala:

Malic acid

Mlt:

1,2,3,4,5,6-Benzenehexacarboxylic acid

Oda:

Diglycolic acid

Pht:

Phthalic acid

Pim:

Pimelic acid

Tar:

Tartaric acid

Tca:

1,2,3-Propanetricarboxylic acid

Toda:

Diethylenetrioxydiacetic acid

Seb:

Sebacic acid

Sub:

Suberic acid

Succ:

Succinic acid

A:

Debye-Hückel coefficient

A ϕ :

Debye-Hückel coefficient of the Pitzer model

BA:

Single salt

c :

Concentration expressed in mol dm−3

c ∞, c 0 :

Parameters for the dependence of protonation constants on ionic strength valid for I → ∞ and I → 0

C.I.:

Confidence interval

C L :

Ligand concentration (mol dm−3)

C L → 0:

Ligand concentration extrapolated at infinite dilution

E 0 :

Standard electrode potential

E j :

Junction potential

EDTA:

Ethylenediaminetetraacetic acid

e.m.f.:

Electromotive force

HPLC:

High Performance Liquid Chromatography

I :

Ionic strength (mol dm−3 or mol kg−1)

ISE-[H+]:

Ion Selective Electrode (ISE) for hydrogen ion (H+)

ja :

Junction potential coefficient

k m :

Setschenow coefficient

k ∞, k 0 :

Parameters that account for the nonlinear variation of k with (c, m) BA and valid for (c, m) BA → ∞ and (c, m) BA→ 0

K w :

Ionic product of water

log β Hi :

Overall protonation constants of the ith step

log t K H :

Protonation constant at infinite dilution

m :

Concentration expressed in mol kg−1

m BA :

Concentration of the supporting electrolyte (single salt in this case) in mol kg−1

m s :

Desired molality value

m 35 :

Molality value of the SSW at S = 35

MX:

Generic single binary electrolyte

\(n_{{\left( { - {\text{CH}}_{ 2} - } \right)}}\) :

Number of methylene groups

p i :

Empirical parameters

Q:

Accuracy of calorimetric apparatus

S :

Salinity expressed in ‰ (g/kg gram of salts/kg sea water)

s, s ∞, and s 0 :

Parameters that account for the nonlinear variation of log S T with (c, m) BA s ∞ and s 0 are valid for (c, m) BA → ∞ and (c, m) BA→ 0

SIT:

Specific ion Interaction Theory

S 0 :

Intrinsic solubility or solubility of the neutral species

SSW:

Synthetic Sea Water

S T :

Total solubility

S 00 :

Intrinsic solubility or solubility of the neutral species at infinite dilution

S T0 :

Total solubility at infinite dilution (pure water)

Std. dev.:

Standard deviation

TRIS:

Tris(hydroxymethyl)aminomethane

z M and z X :

Charges of the M and X ions

β(0), β(1), C (ϕ) :

Interaction parameters between two ions of opposite sign

γ:

Activity coefficient

γ, γ 0 :

Activity coefficients of the neutral species in the salt solution and in pure water, respectively

\(\Delta \varepsilon_{i}^{\prime }\) :

Parameter proportional to the temperature gradient of the ion-interaction coefficient

∆H :

Enthalpy change value (kJ mol−1)

Δ\(H_{\text{i}}^{\text{H0}}\) :

Enthalpy of protonation at infinite dilution

ΔG :

Free Gibbs energy change

ΔS :

Entropy change

ε:

Specific interaction coefficient

θ:

Interaction coefficient of ions of the same charge

λ:

Coefficient of the Pitzer model

ν:

Sum of the number of M and X ions

νM, νX :

Number of M and X ions

σ :

Standard deviation in the fit

ψ :

Interaction coefficient for triple interactions

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Acknowledgments

We thank University of Messina for the partial financial support.

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Authors and Affiliations

  1. Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, University of Messina, Messina, Italy

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

  2. Dipartimento di Chimica “Stanislao Cannizzaro”, University of Palermo, Palermo, Italy

    Alberto Pettignano

Authors
  1. Clemente Bretti
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  2. Rosalia Maria Cigala
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  3. Francesco Crea
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  4. Concetta De Stefano
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  5. Claudia Foti
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  6. Alberto Pettignano
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  7. Silvio Sammartano
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Correspondence to Concetta De Stefano.

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Bretti, C., Cigala, R.M., Crea, F. et al. Polycarboxylic acids in sea water: acid–base properties, solubilities, activity coefficients, and complex formation constants at different salinities. Monatsh Chem 147, 1481–1505 (2016). https://doi.org/10.1007/s00706-016-1758-y

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