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Modeling of Protonation Constants of Linear Aliphatic Dicarboxylates Containing -S-Groups in Aqueous Chloride Salt Solutions, at Different Ionic Strengths, Using the SIT and Pitzer Equations and Empirical Relationships

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Abstract

The protonation constants of ethylenedithiodiacetic, dithiodipropionic and dithiodibutyric acids were obtained from potentiometric measurements in NaCl(aq) (I≤5 mol⋅L−1) and (CH3)4NCl(aq) (I≤3 mol⋅L−1) at t=25 °C. Their dependences on ionic strength were modeled by the SIT and Pitzer approaches. The activity coefficients of the neutral species were obtained by solubility measurements. The literature values of the protonation constants of (HOOC)-(CH2) n -S-(CH2) n -(COOH) (n=1 to 3) and (HOOC)-(CH2)-S-(CH2) n -S-(CH2)-(COOH) (n=0 to 5) in NaCl(aq) and KCl(aq) (I≤3 mol⋅L−1) at 18 °C were also analyzed using the above approaches. Both the log 10 K H i and interaction parameter values follow simple linear trends as a function of certain structural characteristics of the ligands. Examples of modeling these trends are reported.

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Authors and Affiliations

  1. Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone 31, 98166, Messina, Vill. S. Agata, Italy

    Clemente Bretti, Concetta De Stefano & Silvio Sammartano

  2. Rosenstiel School of Marine and Atmospheric Sciences, University of Miami, 4600 Rickenbacker Causeway, Miami, FL, 33133, USA

    Frank J. Millero

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  1. Clemente Bretti
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  2. Concetta De Stefano
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  3. Frank J. Millero
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  4. Silvio Sammartano
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Correspondence to Silvio Sammartano.

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Bretti, C., De Stefano, C., Millero, F.J. et al. Modeling of Protonation Constants of Linear Aliphatic Dicarboxylates Containing -S-Groups in Aqueous Chloride Salt Solutions, at Different Ionic Strengths, Using the SIT and Pitzer Equations and Empirical Relationships. J Solution Chem 37, 763–784 (2008). https://doi.org/10.1007/s10953-008-9273-3

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