Page:Popular Science Monthly Volume 65.djvu/394

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very great. But an inspection of the numbers of Kohlrausch and others for the conductivity of the acids and bases, compared with the measurements of Berthelot and Thomsen on their relative strength with regard to their chemical effect, showed me that the best conducting acids and bases are also the strongest. I was thereby led to suppose that the electrically active molecules are also chemically active. On the other hand, the electrically inactive molecules are also chemically inactive. In this connection I would mention the remarkable experiments of Gore, which were easily explained by the new point of view. Concentrated hydrochloric acid, free from water, has no action on oxides or carbonates. Now this hydrochloric acid is almost incapable of conducting the electric current, whereas its aqueous solutions conduct very well. The pure hydrochloric acid contains, therefore, no (or extremely few) active molecules, and this agrees very well with the experiments of Gore. In the same way we explain the fact that concentrated sulphuric acid may be preserved in vessels of iron plates without destroying them, whereas this is impossible with the diluted acid.

An unexpected conclusion may be deduced from this idea. As all electrolytes in extreme dilution are completely active, then the weak acids must increase in strength with the dilution, and approach to the strength of the strongest acids. This was soon afterwards shown by Ostwald to agree with experiments.

The Norwegian natural philosophers, Guldberg and Waage, had developed a theory according to which the strength of different acids might be measured as well by their power of displacing another acid in solutions as by their faculty to increase the velocity of chemical reactions. Therefore, we may conclude that the velocity of reaction, induced by an acid, would be proportional to the quantity of active molecules in it. I had only a few experiments by Berthelot to demonstrate this proposition, but in 1884, Ostwald published a great number of observations that showed this conclusion to be true.

The most far-reaching conclusion of the conception of active molecules was the explanation of the heat of neutralization. As this is much more easily understood by means of the theory of electrolytic dissociation, I anticipate this for a moment. According to this theory strong acids and bases, as well as salts, are at great dilution (nearly) completely dissociated in their ions, e. g., ${\displaystyle \mathrm {HCl} }$ in ${\displaystyle {\overset {\scriptstyle {+}}{\mathrm {H} }}+{\overset {\scriptstyle {-}}{\mathrm {Cl} }}}$, ${\displaystyle \mathrm {NaOH} }$ in ${\displaystyle {\overset {\scriptstyle {+~~}}{\mathrm {Na} }}+{\overset {\scriptstyle {-~~}}{\mathrm {OH} }}}$ and ${\displaystyle \mathrm {NaCl} }$ in ${\displaystyle {\overset {\scriptstyle {+~}}{\mathrm {Na} }}+{\overset {\scriptstyle {-~}}{\mathrm {Cl} }}}$. But water is (nearly) not dissociated at all. Therefore the reaction of neutralization at mixing a strong acid, e. g., ${\displaystyle \mathrm {HCl} }$ with a strong base, e. g., ${\displaystyle \mathrm {NaOH} }$, both in great dilution, may be represented by the following equation:

${\displaystyle ({\overset {\scriptstyle {+}}{\mathrm {H} }}+{\overset {\scriptstyle {-}}{\mathrm {Cl} }})+({\overset {\scriptstyle {+}}{\mathrm {Na} }}+{\overset {\scriptstyle {-}}{\mathrm {OH} }})=({\overset {\scriptstyle {+}}{\mathrm {Na} }}+{\overset {\scriptstyle {-}}{\mathrm {Cl} }})+\mathrm {HOH} }$;

or,