A chemical equilibrium model for natural waters

Frank J Millero, Denis Pierrot

Research output: Contribution to journalArticle

125 Citations (Scopus)

Abstract

This paper reviews the present status of the Pitzer chemical equilibrium model, which can be used to characterize the one-atmosphere activity coefficients of ionic and non-ionic solutes in natural waters as a function of temperature and ionic strength. The model considers the ionic interactions of the major seasalt ions (H, Na, K, Mg, Ca, Sr, Cl, Br, OH, HCO3, B(OH)4, HSO4, SO4, CO3, CO2, B(OH)3, H2O) and is based on the 25 °C model of Weare and co-workers. The model has been extended by a number of workers so that reasonable estimates can be made of the activity coefficients of most of the major seasalt ions from 0 to 250 °C. Recently coefficients for a number of solutes that are needed to determine the dissociation constants of the acids from 0 to 50 °C (H3CO3, B(OH)3, H2O, HF, HSO4-, H3PO4, H2S, NH4+ etc.) have been added to the model. These results have been used to examine the carbonate system in natural waters and determine the activity of inorganic anions that can complex trace metals. The activity and osmotic coefficients determined from the model are shown to be in good agreement with measured values in seawater. This model can serve as the foundation for future expansions that can examine the activity coefficient and speciation of trace metals in natural waters. At present this is only possible from 0 to 50 °C over a limited range of ionic strengths (<1.0) due to the limited stability constants for the formation of the metal complexes. The future work needed to extend the Pitzer model to trace metals is discussed.

Original languageEnglish (US)
Pages (from-to)153-199
Number of pages47
JournalAquatic Geochemistry
Volume4
Issue number1
DOIs
StatePublished - 1998

Fingerprint

chemical equilibrium
Water
water
activity coefficient
Activity coefficients
trace metal
coefficients
Ionic strength
metals
solute
solutes
Ions
carbonate system
chemical
ion
Carbonates
Coordination Complexes
Seawater
Anions
anion

Keywords

  • Activity
  • Activity coefficients
  • Aquatic environment
  • Ions
  • Water chemistry

ASJC Scopus subject areas

  • Geochemistry and Petrology
  • Geophysics

Cite this

A chemical equilibrium model for natural waters. / Millero, Frank J; Pierrot, Denis.

In: Aquatic Geochemistry, Vol. 4, No. 1, 1998, p. 153-199.

Research output: Contribution to journalArticle

Millero, Frank J ; Pierrot, Denis. / A chemical equilibrium model for natural waters. In: Aquatic Geochemistry. 1998 ; Vol. 4, No. 1. pp. 153-199.
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