Isotopes

Isotopes are nuclides that have the same atomic number and are therefore the same element, but differ in the number of neutrons. Most elements have a few stable isotopes and several unstable, radioactive isotopes. For example, oxygen has three stable isotopes that can be found in nature (oxygen-16, oxygen-17, and oxygen-18) and eight radioactive isotopes. Another example is hydrogen, which has two stable -isotopes (hydrogen-1 and hydrogen-2) and a single radioactive isotope (hydrogen-3).

The isotopes of hydrogen are unique in that they are each commonly referred to by a unique name instead of the common chemical element name. Hydrogen-1 is almost always referred to as hydrogen, but the term protium is infrequently used also. Hydrogen-2 is commonly called deuterium and symbolized ²₁ D. Hydrogen-3 is commonly called tritium and symbolized ³₁ T. This text will normally use the symbology ²₁ H and ³₁ H for deuterium and tritium, respectively.

Evidence for the existence of isotopes emerged from two independent lines of research, the first being the study of radioactivity. By 1910 it had become clear that certain processes associated with radioactivity, discovered some years before by Henri Becquerel, could transform one element into another. In particular, ores of the radioactive elements uranium and thorium had been found to contain small quantities of several radioactive substances never before observed. These substances were thought to be elements and accordingly received special names. Uranium ores, for example, yielded “ionium,” and thorium ores gave “mesothorium.” Painstaking work completed soon afterward revealed, however, that ionium, once mixed with ordinary thorium, could no longer be retrieved by chemical means alone. Similarly, mesothorium was shown to be chemically indistinguishable from radium. As chemists used the criterion of chemical indistinguishability as part of the definition of an element, they were forced to conclude that ionium and mesothorium were not new elements after all, but rather new forms of old ones. Generalizing from these and other data, Frederick Soddy in 1910 observed that “elements of different atomic weights may possess identical (chemical) properties” and so belong in the same place in the periodic table. With considerable prescience, he extended the scope of his conclusion to include not only radioactive species but stable elements as well. A few years later, Soddy published a comparison of the atomic weights of the stable element lead as measured in ores rich in uranium and thorium, respectively. He expected a difference because uranium and thorium decay into different isotopes of lead. The lead from the uranium-rich ore had an average atomic weight of 206.08 compared to 207.69 for the lead from the thorium-rich ore, thus verifying Soddy's conclusion.

The unambiguous confirmation of isotopes in stable elements not associated directly with either uranium or thorium followed a few years later with the development of the mass spectrograph by Francis William Aston. His work grew out of the study of positive rays (sometimes called canal rays), first discovered in 1886 by Eugen Goldstein and soon thereafter recognized as beams of positive ions. As a student in the laboratory of J.J. Thomson, Aston had learned that the gaseous element neon produced two positive rays. The ions in the heavier ray had masses about two units, or 10 percent, greater than the ions in the lighter ray. To prove that the lighter neon had a mass very close to 20 and that the heavier ray was indeed neon and not a spurious signal of some kind, Aston had to construct an instrument that was considerably more precise than any other of the time. By 1919 he had done so and convincingly argued for the existence of neon-20 and neon-22. Information from his and other laboratories accumulated rapidly in the ensuing years and by 1935 the principal isotopes and their relative proportions were known for all but a handful of elements.