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The pK 2 * for the dissociation of H2SO3 in NaCl solutions with added Ni2+, Co2+, Mn2+, and Cd2+ at 25°C

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Abstract

The pK 2 * for the dissociation of sulfurous acid from I=0.5 to 6.0 molal at 25°C has been determined from emf measurements in NaCl solutions with added concentrations of NiCl2, CoCl2, McCl2 and CdCl2 (m=0.1). These experimental results have been treated using both the ion pairing and Pitzer's specific ion-interaction models. The Pitzer parameters for the interaction of M2+ with SO 3 2− yielded

$$\begin{gathered} \beta _{NiSO_3 }^{(0)} = - 5.5, \beta _{NiSO_3 }^{(1)} = 5.8, and \beta _{NiSO_3 }^{(2)} = - 138 \hfill \\ \beta _{CoSO_3 }^{(0)} = - 12.3, \beta _{CoSO_3 }^{(1)} = 31.6, and \beta _{CoSO_3 }^{(2)} = - 562 \hfill \\ \beta _{MnSO_3 }^{(0)} = - 8.9, \beta _{MnSO_3 }^{(1)} = 18.7, and \beta _{MnSO_3 }^{(2)} = - 353 \hfill \\ \beta _{CdSO_3 }^{(0)} = - 7.2, \beta _{CdSO_3 }^{(1)} = 13.8, and \beta _{CdSO_3 }^{(2)} = - 489 \hfill \\ \end{gathered} $$

The calculated values of pK 2 * using Pitzer's equations reproduce the measured values to within ±0.01 pK units. The ion pairing model yielded

$$\begin{gathered} logK_{NiSO_3 } = 2.88 and log\gamma _{NiSO_3 } = 0.111 \hfill \\ logK_{CoSO_3 } = 3.08 and log\gamma _{CoSO_3 } = 0.051 \hfill \\ logK_{MnSO_3 } = 3.00 and log\gamma _{MnSO_3 } = 0.041 \hfill \\ logK_{CdSO_3 } = 3.29 and log\gamma _{CdSO_3 } = 0.171 \hfill \\ \end{gathered} $$

for the formation of the complex MSO3. The stability constants for the formation of MSO3 complexes were found to correlate with the literature values for the formation of MSO4 complexes.

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Correspondence to Frank J. Millero.

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Roy, R.N., Zhang, J., Sibblies, M.A. et al. The pK 2 * for the dissociation of H2SO3 in NaCl solutions with added Ni2+, Co2+, Mn2+, and Cd2+ at 25°C. J Solution Chem 20, 467–478 (1991). https://doi.org/10.1007/BF00650803

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Key words

  • Dissociation constant
  • sulfurous acid
  • NaCl solution
  • transition metal
  • potentiometric titration
  • Pitzer parameter
  • ion pairing model