Covalent Radius

Covalent bond radius refers to half of the distance between two singly bonded atoms of the same element
( homonuclear X-X bond) and is denoted rcov. In other words, it is defined as half the covalent bond length when the
two atoms bonded are homonuclear. rcov is typically measured by X-ray diffraction. When multiple allotropes exist for
a given element, rcov is determined by averaging the bond distances found in each allotrope. Covalent radius is
measured in picometers (pm) or ngstrms () and represents one measurement that is used in determining atomic
radius.

Van der Waals Radius

van der Waals radius is defined as half of the internuclear separation of two non-bonded atoms of the same element
on their closest possible approach and is denoted rv. As shown in the following figure, the red line indicates the van
der Waals radius as the blue line is the diameter. In addition to not being covalently bonded, the atoms must also not
be of the same molecule. The term incorporates the intermolecular forces (dipole-dipole, dispersion) and is therefore
useful in determining how molecules pack in solid. rv is measured for two non-bonded atoms in the crystal of a
molecule. The name for the term comes from its relationship to van der Waals Interactions. rv is generally greater
than rcov for a given element. rv is also measured in terms of picometers (pm) and ngstrms ().

Table of Sample Values for rcov and

rv

rcov (pm) rv (pm)

Element
H

37

120

88

208

77

185

75

154

73

140

71

135

Cl

99

180

Br

114

195

133

215

He

n/a

99

Values: Housecroft, Inorganic Chemistry, 2008

Van der Waals equation was originated from the ideal gas law:

pV = nRT (p: gas pressure, V: volume, n: amount of substance, R: ideal gas constant, T: absolute temperature).
Based on the ideal gas law above, van der Waals equation takes the molecular size and the molecular force into
account. As a result, the attractive force (a/V2) is added into the pressure part. Likewise, the volume is subtracted by
the molecular volume (b), which is determined by the van der Waals radius.
Therefore, the equation for one mole is written as

(p+aV2)(Vb)=RT
And the equation for multiple moles is written as
(p + a(n/V)2)(V - nb) = nRT (n: the number of moles).

The following figure illustrates the difference between the Covalent radius and the van der Waals radius for better
understanding of two terms.

ionic radius Half the distance between the centres of

two ions of the same element. Although no precise measurement
can be made of the size of individual ions, in practice various
techniques (e.g. X-ray diffraction) can be used to estimate ionic
radii in particular crystal structures. Generally, it is found that: (a)

within the same group of the periodic table ionic radius increases
with increasing atomic number; (b) for elements of the same
period (i.e. same horizontal row) that form positive ions, ionic
radius decreases with increasing positive charge (reflecting the
greater nuclear attraction on the same number of
extranuclear electrons), for example, Na+ = 1.02, Mg2+ = 0.72,
Al3+ = 0.53, Si4+ = 0.40; (c) for the same reasons, if an element
can exist in different valence states, the higher the positive
charge the smaller the ion, for example, Mn = 0.82, Mn = 0.65; (d) for
2+

3+

elements of the same period forming negative ions, the ionic radius increases with
increasing negative charge (due to electronic repulsion).

A metallic radius is the measurement of an atom's size with regards to metal

elements only. Metallic elements are most easily measured because of even
distribution and distance between adjacent atoms, according to Purdue University.
Scientists assume the radius of an atom is half the distance between an adjacent atom
in a solid.
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