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Concept
Rayon ionique
Résumé
Ionic radius, rion, is the radius of a monatomic ion in an ionic crystal structure. Although neither atoms nor ions have sharp boundaries, they are treated as if they were hard spheres with radii such that the sum of ionic radii of the cation and anion gives the distance between the ions in a crystal lattice. Ionic radii are typically given in units of either picometers (pm) or angstroms (Å), with 1 Å = 100 pm. Typical values range from 31 pm (0.3 Å) to over 200 pm (2 Å).
The concept can be extended to solvated ions in liquid solutions taking into consideration the solvation shell.
Ions may be larger or smaller than the neutral atom, depending on the ion's electric charge. When an atom loses an electron to form a cation, the other electrons are more attracted to the nucleus, and the radius of the ion gets smaller. Similarly, when an electron is added to an atom, forming an anion, the added electron increases the size of the electron cloud by interelectronic repulsion.
The ionic radius is not a fixed property of a given ion, but varies with coordination number, spin state and other parameters. Nevertheless, ionic radius values are sufficiently transferable to allow periodic trends to be recognized. As with other types of atomic radius, ionic radii increase on descending a group. Ionic size (for the same ion) also increases with increasing coordination number, and an ion in a high-spin state will be larger than the same ion in a low-spin state. In general, ionic radius decreases with increasing positive charge and increases with increasing negative charge.
An "anomalous" ionic radius in a crystal is often a sign of significant covalent character in the bonding. No bond is completely ionic, and some supposedly "ionic" compounds, especially of the transition metals, are particularly covalent in character. This is illustrated by the unit cell parameters for sodium and silver halides in the table. On the basis of the fluorides, one would say that Ag+ is larger than Na+, but on the basis of the chlorides and bromides the opposite appears to be true.
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