2.3.3: Covalent and Ionic Radii

Measurement of Radius

There are several methods that can be used to determine radii of atoms and ions:

• Nonpolar atomic radii: The radius of an atom is derived from the bond lengths within nonpolar molecules; one-half the distance between the nuclei of two atoms within a covalent bond.
• van der Waals radius: The radius of an atom is determined by collision with other atoms.
• Crystal radii: The atomic or ionic radius is determined using electron density maps from X-ray data.

The measurement of atomic or ionic size will depend on a number of factors, including the covalent character of bonding in any particular molecule, coordination number, physical state (liquid, solid, gas), the identity of nearby atoms/ions, variation in crystal structure, and distortions within regular crystal structures. You should keep in mind that the size of an atom or ion is a "fuzzy" measure, and the radius under a different set of conditions will probably change slightly.

Regardless, measured atomic and ionic radii reveal obvious trends across the periodic table and between atoms and ions. The relative atomic sizes shown in Figure \(\PageIndex{1}\) were derived from crystallographic data.¹

Trends in Atomic Radius

Atomic size generally decreases gradually from left to right across a period of elements. As nuclear charge (Z) increases, we expect the effective nuclear charge (Z*) of the valence electrons to also increase. Increasing Z pulls electrons closer to the nucleus. However, with each additional unit of Z, there is also an additional electron. The change in size is a balance of a compression caused by increasing Z and an expansion in the number of electrons. As a result, the atomic radius decreases gradually across a period.

Atomic size generally increases going down a group. As valence electrons occupy higher level shells due to the increasing quantum number (n), size increases despite the fact that Z and Z* are increasing going down the group.

Figure \(\PageIndex{1}\). Atomic Radii Calculated from Crystalographic Data. Data from Cordero, Beatriz, Veronica Gomez, Ana E. Platero-Prats, Marc Reves, Jorge Echeverria, Eduard Cremades, Flavia Barragan, and Santiago Alvarez. “Covalent Radii Revisited.” Dalton Transactions, no. 21 (2008): 2832–38. doi:10.1039/b801115j. (Kathryn Haas; CC-NC-BY-SA)

Trends in Ionic Radius

Trends in ionic radius follow general trends in atomic radius for ions of the same charge. Ionic radius varies with the charge of the ion (and number of electrons) and the electron configuration (e.g. high spin or low spin).

Cations

Compared to their atoms, cations have the same Z but fewer electrons. Removal of electrons from an atom to form a cation results in a significant increase in effective nuclear charge, resulting in all other electrons being more strongly attracted to the nucleus, and having a lower energy level. The result is a contraction in size from the atom to cation. Figure \(\PageIndex{2}\) visually illustrates the relative size of atoms and some cations of the first four periods; the data is available in tabular format in Figure \(\PageIndex{3}\).

Anions

Compared to their atoms, anions have the same Z but more electrons. Addition of electrons to an atom to form an anion results in a decrease in effective nuclear charge, which corresponds to a decrease in attractive force between the nucleus and electrons. Lower attractive force leads to expansion, where the size of the atom becomes larger in the formation of an anion. Figure \(\PageIndex{2}\) visually illustrates the relative size of atoms and some anions of the first four periods, while the data is available in tabular format in Figure \(\PageIndex{3}\).

Figure \(\PageIndex{2}\). This figure illustrates relative size of atoms and ions of the first four periods of the periodic table. Atomic radius is indicated by grey circles. Radius of cations is shown in green (+1), lime (+2), and yellow (+3) circles. Radius of anions are shown as aqua (-1), blue (-2), and purple (-3) circles. Data from sources 1-3. (Kathryn Haas; CC-NC-BY-SA)

Figure \(\PageIndex{3}\). This figure shows radii (in Angstroms) of atoms and ions of the first four periods of the periodic table. Radii from each element are listed from largest to smallest, ionic charge indicated in parentheses (); hs = high spin, ls = low spin, cn6 = coordination number is 6. Data from sources 1-3. (Kathryn Haas; CC-NC-BY-SA)

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References

1. Cordero, Beatriz, Veronica Gomez, Ana E. Platero-Prats, Marc Reves, Jorge Echeverria, Eduard Cremades, Flavia Barragan, and Santiago Alvarez. “Covalent Radii Revisited.” Dalton Transactions, no. 21 (2008): 2832–38. doi:10.1039/b801115j.
2. R. D. Shannon (1976). "Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides". Acta Crystallogr A. 32 (5): 751–767. Bibcode:1976AcCrA..32..751S. doi:10.1107/S0567739476001551.
3. Wikipedia articles on Atomic Radius and Ionic Radius.