The Chemical Elements

How would one find out what types of atoms there were? Today, it doesn't seem like it should have been very difficult to work out an experimental program to classify the types of atoms. For each type of atom, there should be a corresponding element, i.e. a pure substance made out of nothing but that type of atom. Atoms are supposed to be unsplittable, so a substance like milk could not possibly be elemental, since churning it vigorously causes it to split up into two separate substances: butter and whey. Similarly, rust could not be an element, because it can be made by combining two substances: iron and oxygen. Despite its apparent reasonableness, no such program was carried out until the eighteenth century. The ancients presumably did not do it because observation was not universally agreed on as the right way to answer questions about nature, and also because they lacked the necessary techniques or the techniques were the province of laborers with low social status, such as smiths and miners. Alchemists were hindered by atomism's reputation for subversiveness, and by a tendency toward mysticism and secrecy. (The most celebrated challenge facing the alchemists, that of converting lead into gold, is one we now know to be impossible, since lead and gold are both elements.)

Examples of masses of atoms compared to that of hydrogen. Note how some, but not all, are close to integers.

By 1900, however, chemists had done a reasonably good job of finding out what the elements were. They also had determined the ratios of the different atoms' masses fairly accurately. A typical technique would be to measure how many grams of sodium (Na) would combine with one gram of chlorine (Cl) to make salt (NaCl). (This assumes you've already decided based on other evidence that salt consisted of equal numbers of Na and Cl atoms.) The masses of individual atoms, as opposed to the mass ratios, were known only to within a few orders of magnitude based on indirect evidence, and plenty of physicists and chemists denied that individual atoms were anything more than convenient symbols.

Making sense of the elements

As the information accumulated, the challenge was to find a way of systematizing it; the modern scientist's aesthetic sense rebels against complication. This hodgepodge of elements was an embarrassment. One contemporary observer, William Crookes, described the elements as extending "before us as stretched the wide Atlantic before the gaze of Columbus, mocking, taunting and murmuring strange riddles, which no man has yet been able to solve." It wasn't long before people started recognizing that many atoms' masses were nearly integer multiples of the mass of hydrogen, the lightest element. A few excitable types began speculating that hydrogen was the basic building block, and that the heavier elements were made of clusters of hydrogen. It wasn't long, however, before their parade was rained on by more accurate measurements, which showed that not all of the elements had atomic masses that were near integer multiples of hydrogen, and even the ones that were close to being integer multiples were off by one percent or so.

Chemistry professor Dmitri Mendeleev, preparing his lectures in 1869, wanted to find some way to organize his knowledge for his students to make it more understandable. He wrote the names of all the elements on cards and began arranging them in different ways on his desk, trying to find an arrangement that would make sense of the muddle. The row-and-column scheme he came up with is essentially our modern periodic table. The columns of the modern version represent groups of elements with similar chemical properties, and each row is more massive than the one above it. Going across each row, this almost always resulted in placing the atoms in sequence by weight as well. What made the system significant was its predictive value. There were three places where Mendeleev had to leave gaps in his checkerboard to keep chemically similar elements in the same column. He predicted that elements would exist to fill these gaps, and extrapolated or interpolated from other elements in the same column to predict their numerical properties, such as masses, boiling points, and densities. Mendeleev's professional stock skyrocketed when his three elements (later named gallium, scandium and germanium) were discovered and found to have very nearly the properties he had predicted.

A modern periodic table. Elements in the same column have similar chemical properties. The modern atomic numbers, discussed in ch. 2, were not known in Mendeleev's time, since the table could be flipped in various ways.

One thing that Mendeleev's table made clear was that mass was not the basic property that distinguished atoms of different elements. To make his table work, he had to deviate from ordering the elements strictly by mass. For instance, iodine atoms are lighter than tellurium, but Mendeleev had to put iodine after tellurium so that it would lie in a column with chemically similar elements.