The activity coefficients of non-electrolytes in seawater

Frank Millero

Research output: Contribution to journalArticle

36 Scopus citations

Abstract

The solubility of non-electrolytes in electrolyte solutions has frequently been examined using the Setschnow equation ln(S0/S) = lnγ(N) = k(s)m where S0 and S are the solubilities in water and solution, k(s) is the salting coefficient of the non-electrolyte (N), γ(N) is the activity coefficient, and m is the molality. The values of the salting coefficients are available for a number of non-electrolytes in some electrolyte solutions. Values are however not readily available for many of the major salts that make up natural waters (MgCl2, CaCl2, MgSO4, and Na2SO4). This requires the development of methods that can be used to estimate the salting coefficients of unknown salts for calculations of the solubility of non-electrolytes in natural waters. The measured values of k(s) have been shown to be in reasonable agreement with the values calculated using the Scaled Particle Model (k(s) = k(α) + k(β), where k(α) is related to the free energy of making space in the solution for the non-electrolyte and k(β) is the free energy related to the interaction of the ions and the non-electrolyte). The values of k(s) in a given electrolyte have also been determined using the semi-empirical equation k(s) = a + b(e/k) where e/k is an energy parameter related to the polarizibility of the non-electrolyte, while the values in different electrolytes have been determined using correlations of the measured values of k(s) of two non-electrolytes k(s)(N) = a' + b'k(s)(O2) (a, a', b, and b' are adjustable parameters). These semi-empirical equations yield calculated values of k(s) that are in better agreement with the measured values than the Scaled Particle Theory. The measured and estimated values of k(s) have been used to estimate the Pitzer coefficients for 21 non-electrolytes (He, H2, Ne, N2, CO, N2O, O2, Ar, NO, CH4, CF4, Kr, C2H2, SF6, C2H4, Xe, C2H6, Rn, CCl4, C6H6, H2S) in major seasalts. The Pitzer parameters for the ions (λ(Ni) which is related to the interaction of ion I with the non-electrolyte N) have been used to estimate the activity coefficients in seawater. The calculated values are in good agreement with the measured values (H2, Ne, N2, CO, N2O, O2, Ar, CH4, Kr) and are in better agreement (σ = 0.033) than the estimates made using the Scaled Particle Model (σ = 0.077). A simple correlation of lnγ(N) = 0.0938 + 0.3404 k(s) (NaCl) gives an excellent fit (σ = 0.014) of the experimental measurements in seawater (S = 35 and t = 25°C). This empirical equation can be used to determine solubilities for non-electrolytes in seawater from measurements made in NaCl solutions. (C) 2000 Elsevier Science B.V.

Original languageEnglish (US)
Pages (from-to)5-22
Number of pages18
JournalMarine Chemistry
Volume70
Issue number1-3
DOIs
StatePublished - May 1 2000

Keywords

  • Activity coefficients
  • Non-electrolytes
  • Sea water

ASJC Scopus subject areas

  • Oceanography
  • Chemistry(all)
  • Environmental Chemistry
  • Water Science and Technology

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