Diatomic Molecule - Historical Significance

Historical Significance

Diatomic elements played an important role in the elucidation of the concepts of element, atom, and molecule in the 19th century, because some of the most common elements, such as hydrogen, oxygen, and nitrogen, occur as diatomic molecules. John Dalton's original atomic hypothesis assumed that all elements were monatomic and that the atoms in compounds would normally have the simplest atomic ratios with respect to one another. For example, Dalton assumed that water's formula was HO, giving the atomic weight of oxygen as eight times that of hydrogen, instead of the modern value of about 16. As a consequence, confusion existed regarding atomic weights and molecular formulas for about half a century.

As early as 1805, Gay-Lussac and von Humboldt showed that water is formed of two volumes of hydrogen and one volume of oxygen, and by 1811 Amedeo Avogadro had arrived at the correct interpretation of water's composition, based on what is now called Avogadro's law and the assumption of diatomic elemental molecules. However, these results were mostly ignored until 1860. Part of this rejection was due to the belief that atoms of one element would have no chemical affinity towards atoms of the same element, and part was due to apparent exceptions to Avogadro's law that were not explained until later in terms of dissociating molecules.

At the 1860 Karlsruhe Congress on atomic weights, Cannizzaro resurrected Avogadro's ideas and used them to produce a consistent table of atomic weights, which mostly agree with modern values. These weights were an important pre-requisite for the discovery of the periodic law by Dmitri Mendeleev and Lothar Meyer.