Atomic Number - History

History

Loosely speaking, the existence of a periodic table creates an ordering for the elements. Such an ordering is not necessarily a numbering, but can be used to construct a numbering by fiat. Dmitri Mendeleev claimed he arranged his tables in order of atomic weight ("Atomgewicht") However, in deference to the observed chemical properties, he violated his own rule and placed tellurium (atomic weight 127.6) ahead of iodine (atomic weight 126.9). This placement is consistent with the modern practice of ordering the elements by proton number, Z, but this number was not known or suspected at the time.

A simple numbering based on periodic table position was never entirely satisfactory. Besides iodine and tellurium, later several other pairs of elements (such as argon and potassium, cobalt and nickel) were known to have nearly identical or reversed atomic weights, leaving their placement in the periodic table by chemical properties to be in violation of known physical properties. Another problem was that the gradual identification of more and more chemically similar and indistinguishable lanthanides, which were of an uncertain number, led to inconsistency and uncertainty in the numbering of elements at least from lutetium (element 71) onwards (hafnium was not known at this time).

In 1911, Ernest Rutherford gave a model of the atom in which a central core held most of the atom's mass and a positive charge which, in units of the electron's charge, was to be approximately equal to half of the atom's atomic weight, expressed in numbers of hydrogen atoms. This central charge would thus be approximately half the atomic weight (though it was almost 25% off the figure for the atomic number in gold (Z = 79, A = 197), the single element from which Rutherford made his guess). Nevertheless, in spite of Rutherford's estimation that gold had a central charge of about 100 (but was element Z = 79 on the periodic table), a month after Rutherford's paper appeared, Antonius van den Broek first formally suggested that the central charge and number of electrons in an atom was exactly equal to its place in the periodic table (also known as element number, atomic number, and symbolized Z). This proved eventually to be the case.

The experimental situation improved dramatically after research by Henry Moseley in 1913. Moseley, after discussions with Bohr who was at the same lab (and who had used Van den Broek's hypothesis in his Bohr model of the atom), decided to test Van den Broek and Bohr's hypothesis directly, by seeing if spectral lines emitted from excited atoms fit the Bohr theory's demand that the frequency of the spectral lines be proportional to a measure of the square of Z.

To do this, Moseley measured the wavelengths of the innermost photon transitions (K and L lines) produced by the elements from aluminum (Z = 13) to gold (Z = 79) used as a series of movable anodic targets inside an x-ray tube. The square root of the frequency of these photons (x-rays) increased from one target to the next in a linear fashion. This led to the conclusion (Moseley's law) that the atomic number does closely correspond (with an offset of one unit for K-lines, in Moseley's work) to the calculated electric charge of the nucleus, i.e. the proton number Z. Among other things, Moseley demonstrated that the lanthanide series (from lanthanum to lutetium inclusive) must have 15 members—no fewer and no more—which was far from obvious from the chemistry at that time.

The conventional symbol Z possibly comes from the German word Atomzahl (atomic number). However, prior to 1915, the word Zahl (simply number) was used for an element's assigned number in the periodic table.