Periodic Table, The: Past, Present, And Future

is a smooth progression in formulas (except for the halides), this hides sudden breaks in phase and behavior at room temperature. These changes can be related to the progression of bonding types from ionic to covalent, with the network covalent region marking the borderline between the two bonding categories [59].

The location of the network covalent species shifts diagonally from the 2nd to the 3rd Period. The common explanation is that the location is reflective of the electronegativity, which itself crosses the Periodic Table on a diagonal. The corresponding network covalent molecule in the 4th Period is beneath that in the 3rd, perhaps a reflection of the similarity resulting from the d-block contraction.

As is not uncommon in inorganic chemistry, things do not always fit neat patterns. Specifically, at room temperature, “N₂O₅” has an ionic structure: [NO₂]⁺[NO₃]⁻. The two lower members of Group 16 do not form simple XO₃ molecules, instead, “sulfur trioxide” is a trimer, S₃O₉, containing alternating sulfur and oxygen atoms to form a six-membered ring while “selenium trioxide” is an analogous tetramer, Se₄O₁₂. As another “breakdown” of pure periodicity, though chlorine forms a heptaoxide, bromine only forms a pentaoxide, a fact which might be ascribed to the 4th Period anomaly.

Table 7.4 Bonding categories for the 2nd, 3rd, and 4th Period highest oxidation-state oxides

Commentary

Periodic patterns and trends are the fundamental basis of the Periodic Table. And it is not all about Groups and Periods, as Rogers has pointed out [60]. However, in this Author’s view, sometimes periodicity is raised to almost mythical status in which patterns and trends are “cherry-picked” to illustrate near-perfect sequences. As shown in this chapter, there are many species that “stubbornly” refuse to fit how they “should.” As chemists, we should not be afraid to teach the limitations of periodicity and sometimes revel in the uniqueness of each element and its compounds.

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