1 • Chemistry and electricity
The connection between chemistry and electricity is a very old one, going back to A
discovery, in 1793, that electricity could be produced by placing two dissimilarmetals on opposite sides of a moistened paper. In 1800, Nicholson and Carlisle, using Volta'sprimitive battery as a source, showed that an electric current could decompose water intooxygen and hydrogen. This was surely one of the most significant experiments in the historyof chemistry, for it implied that the atoms of hydrogen and oxygen were associated with pos-itive and negative electric charges, which must be the source of the bonding forces betweenthem. By 1812, the Swedish chemist B
could propose that all atoms are electrified,hydrogen and the metals being positive, the nonmetals negative. In electrolysis, the appliedvoltage was thought to overpower the attraction between these opposite charges, pulling theelectrified atoms apart in the form of
(named by Berzelius from the Greek for “travel-ers”). It would be almost exactly a hundred years later before the shared electron pair theoryof G.N. L
could offer a significant improvement over this view of chemical bonding.Meanwhile the use of electricity as a means of bringing about chemical change continued toplay a central role in the development of chemistry. H
prepared the first ele-mental sodium by electrolysis of a sodium hydroxide melt. It was left to Davey's formerassistant, M
, to show that there is a direct relation between the amount of electric charge passed through the solution and the quantity of electrolysis products. J
immediately saw this as evidence for the “molecule of electricity”, but theworld would not be receptive to the concept of the electron until the end of the century.
Nature seems to strongly discourage any process that would lead to an excess of positive ornegative charge in matter. Suppose, for example, that we immerse a piece of zinc metal inpure water. A small number of zinc atoms go into solution as Zn ions, leaving their electronsbehind in the metal:
As this process goes on, the electrons which remain in the zinc cause a negative charge tobuild up within the metal which makes it increasingly difficult for additional positive ions toleave the metallic phase. A similar buildup of positive charge in the liquid phase adds to thisinhibition. Very soon, therefore, the process comes to a halt, resulting in a solution in whichthe concentration of Zn
is still too low (around 10
) to be detected by ordinary chemi-cal means.
Fig. 1: Oxidation of metallic zinc in contact with water