Journal of Solution Chemistry

, Volume 32, Issue 6, pp 473–487

Solubility of Oxygen in Some 1-1, 2-1, 1-2, and 2-2 Electrolytes as a Function of Concentration at 25°C

Authors

  • Frank J. Millero
    • Rosenstiel School of Marine and Atmospheric ScienceUniversity of Miami
  • Fen Huang
  • Taylor B. Graham
Article

DOI: 10.1023/A:1025301314462

Cite this article as:
Millero, F.J., Huang, F. & Graham, T.B. Journal of Solution Chemistry (2003) 32: 473. doi:10.1023/A:1025301314462

Abstract

The solubility of oxygen has been measured in a number of electrolytes [(LiCl, KCl, RbCl, CsCl, NaF, NaBr, NaI, NaNO3, KBr, KI, KNO3, CaCl2, SrCl2, BaCl2, Li2SO4, K2SO4, Mn(NO3)3)] as a function of concentration at 25°C. The solubilities, μmol (kg-H2O)−1, have been fitted to a function of the molality m (standard deviation σ < 3μmol-kg−1)
$$\ln \left( {\left[ {{\text{O}}_{\text{2}} } \right]^0 /\left[ {{\text{O}}_{\text{2}} } \right]} \right) = \ln \gamma \left( {{\text{O}}_2 } \right) = Am + Bm^2 $$
where A and B are adjustable parameters and the activity coefficient of oxygen γ)O2) = [O2]0/[O2]. The limiting salting coefficient, kS = (∂ln γ/∂ m)m=0 = A, was determined for all salts. The salting coefficients for the chlorides and sodium salts showed a near linear correlation with the crystal molar volume Vcryst = 2.52 r3. The salting coefficients determined from the Scaled Particle Theory were in reasonable agreement with the measured values. The activity coefficients of oxygen in the solutions have been interpreted using the Pitzer equation
$$\ln \gamma _{{\text{O}}_{\text{2}} } = 2\sum\limits_{\text{c}} {\lambda _{{\text{O}}_{\text{2}} {\text{c}}} m_{\text{c}} /m^{\text{0}} + 2\sum\limits_{\text{a}} {\lambda _{{\text{O}}_{\text{2}} {\text{a}}} m_{\text{a}} + } \sum\limits_{\text{c}} {\sum\limits_{\text{a}} {m_{\text{c}} m_{\text{a}} } } \zeta _{{\text{O}}_{\text{2}} {\text{ca}}} }$$
where \(\lambda _{{\text{O}}_{\text{2}} {\text{i}}} \) is a parameter that accounts for the interaction of O2 with cations (c) and anions (a) with molalities ma and mc, and \(\zeta _{{\text{O}}_{\text{2}} {\text{ca}}}\) accounts for interactions for O2 with the cation and anion pair (c-a). The \(\lambda _{{\text{O}}_{\text{2}} {\text{i}}}\) and \(\zeta _{{\text{O}}_{\text{2}} {\text{ca}}}\) coefficients determined for the most of the ions are in reasonable agreement with the tabulations of Clegg and Brimblecombe. The values of \(\lambda _{{\text{O}}_{\text{2}} {\text{i}}}\) for most of the ions are a linear function of the electrostriction molar volume (Velect = V0Vcryst).
OxygenSolubilityactivity coefficientsaltsalkali and alkaline earth chlorides

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© Plenum Publishing Corporation 2003