[Physics] Why does the thermal conductivity of water decrease with increasing salinity

physical-chemistrythermodynamics

Intuitively I would expect the thermal and electric conductivity to be positively related, and since electric conductivity increases with salinity, so should thermal. But according to this table (p.10) it decreases. Why is this?

Related: is there such a thing as the Wiedemann-Franz law for liquids like water?

There's a paper that has theoretical derivations about it, but it's nowhere to be found:
Predvoditelev, A. S., "Some invariant Quantities in the Theories of Heat Conductance and the Viscosity of Liquids," Russian Journal of Physical Chemistry, Vol. 22, p. 339 (1948)

Best Answer

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A short answer would be that although electric and thermal conductivity have (movement of free) electrons as their primary carriers, they operate on different ranges/frequencies/wavelengths, and as such the structure and energy zones of the material (or material compound) can have quite different factors for each type of conductance.

From the Wikipedia article on thermal conductivity:

In metals, thermal conductivity approximately tracks electrical conductivity according to the Wiedemann–Franz law, as freely moving valence electrons transfer not only electric current but also heat energy. However, the general correlation between electrical and thermal conductance does not hold for other materials, due to the increased importance of phonon carriers for heat in non-metals. Highly electrically conductive silver is less thermally conductive than diamond, which is an electrical insulator, but due to its orderly array of atoms it is conductive of heat via phonons