Mendeleev was one of a dozen or more chemists who aimed to create a classification of elements in the mid-19th century. Mendeleev distinguished himself among the discoverers of the periodic system in their priority disputes because he was the only one who bothered to provide a clear definition of the entities to be ordered. This paper will first outline the role of Mendeleev's conceptual distinction between "element" and "simple substance" in the process of constructing the periodic table. Symmetrically, it will emphasize how the periodic system reconfigured the notion of the element as a relational entity, defined by its relations with other elements, a notion stabilized by the invention of the concept of isotopes in the early 20th century.atom, isotopes, Mendeleev, molecule, Prout's hypothesis, simple substances Dmitri Mendeleev (1834-1907) is universally credited for being "the father" of the periodic system, which is still viewed as the icon of chemistry and the navigation chart of the material world. Mendeleev has even occasionally been described as a genius who bravely anticipated future developments in the investigation of the structure of atoms. In particular, French philosopher François Dagognet argued that, given that in 1869 only 63 of the 105 elements then known had been identified, the discovery of the periodic law was extremely improbable. 1With so few pieces of the puzzle in hands, how did Mendeleev manage to construct a whole picture that was able to accommodate later discoveries of unknown elements?For historians of chemistry, such views are largely inadequate for at least two reasons. First, Mendeleev was only one among more than a dozen chemists who attempted to classify chemical elements, and he was not alone in 1 Dagognet (1969).