Journal of Solution Chemistry

, Volume 25, Issue 8, pp 711–729 | Cite as

Ion association of dilute aqueous sodium hydroxide solutions to 600°C and 300 MPa by conductance measurements

  • Patience C. Ho
  • Donald A. Palmer


The limiting molar conductances Λ0 and ion association constants of dilute aqueous NaOH solutions (<0.01 mol-kg−1) were determined by electrical conductance measurements at temperatures from 100 to 600°C and pressures up to 300 MPa. The limiting molar conductances of NaOH(aq) were found to increase with increasing temperature up to 300°C and with decreasing water density ρw. At temperatures ≥400°C, and densities between 0.6 to 0.8 g-cm−3, Λ0 is nearly temperature-independent but increases linearly with decreasing density, and then decreases at densities <0.6 g-cm−3. This phenomenon is largely due to the breakdown of the hydrogen-bonded, structure of water. The molal association constants K Am for NaOH( aq ) increase with increasing temperature and decreasing density. The logarithm of the molal association constant can be represented as a function of temperature (Kelvin) and the logarithm of the density of water by
$$\begin{gathered} log K_{Am} = 2.477 - 951.53/T - (9.307 \hfill \\ - 3482.8/T)log \rho _{w } (25 - 600^\circ C) \hfill \\ \end{gathered} $$
which includes selected data taken from the literature, or by
$$\begin{gathered} log K_{Am} = 1.648 - 370.31/T - (13.215 \hfill \\ - 6300.5/T)log \rho _{w } (400 - 600^\circ C) \hfill \\ \end{gathered} $$
which is based solely on results from the present study over this temperature range (and to 300 MPa) where the measurements are most precise.

Key Words

Conductivity aqueous sodium hydroxide ion association temperature pressure 


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Copyright information

© Plenum Publishing Corporation 1996

Authors and Affiliations

  • Patience C. Ho
    • 1
  • Donald A. Palmer
    • 1
  1. 1.Chemical and Analytical Sciences DivisionOak Ridge National LaboratoryOak Ridge

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