In order to study the hehaviour of the individual metallic oxide in molten slags, the electrical conductivity of the systems sodium-silicate-metallic oxide was measured. The concentration of the fundamental sodium-silicate was Na
2O 32.45mol%, SiO
2 67.55mol%, and the content of additional metallic oxides SiO
2, Al
2O
3, CaO, MgO, MnO, FeO and NiO were 10mol% and 20mol%. Samples wree melted in an alundum-crucible Elema-furnace being used. Measurement was done by the conventional alternating-current-bridge method.
Generally when additinal oxides are acidic, the electrical conductivity was smaller than that of the fundamental system; and when basic, it was larger (except for CaO). This was explained to be owing to the modern acid-base definition.
When acid oxides were added, the number of mobile Na
+ decreased, lowering the conductivity, while by addition of basic oxides, the number of mobile cations increased, enhancing the conductivity.
In case the basic oxides were added, the specific electrical conductivity decreased in the order of NiO, FeO, MgO, MnO, CaO. This order corresponded to the increase of radii of cations of the added oxides (except for Mg
++), and to the decrease of εM (thermal energy per g-mol evolved when a solid oxide was formed from 1g-atom metallic ion and O
-- of the corresponding number both in the gas state) obtained by Huggins and Sum εM was by definition the strength of the bond between metallic ion and oxygen ion-that was the basicity of a metallic oxide.
Accordingly the weaker was the strength of the basic oxides added, the larger became the electrical conductivity.
The number of the mobile ions being same, only the mobility of ions was the controlling factor.
The smaller were the radii of cations, the more easily they moved; and the larger was εM, the more appreciably decreased the stability of bonds Si-O, and so again the more easily cations could move.
When CaO was added, the electrical conductivity decreased, being due to the fact that the mobility of Ca
++ was small.
The radius of cation and εM determined the form of the SiO
4-tetrahedron, and controllled the strength of bonds between cations and SiO
4-tetrahedron. This related to the activity of constituents.
In fact the order of activities of SiO
2 in several binary silicate melts corresponded to that of εM and so of the electrical conductivity.
View full abstract