Covalent bond distance, covalent radius, and van der Waals radius are used to

describe the size and distance between atoms. Covalent bond distance refers to the
distance between the nuclei of two bonded atoms. Covalent radius is half of the
internuclear separation between the nuclei of two single-bonded atoms of the same
species (homonuclear). While van der Waals radius is used to define half of the
distance between the closest approach of two non-bonded atoms of a given
element.
Introduction
Covalent bond distance, covalent radius, and van der Waals radius are all
experimentally determined values that describe the distance around or between
atoms.
Covalent Bond Distance
Covalent bond distance is defined by the internuclear distance between two
covalently bonded atoms and is denoted by d. It can be used as a measure of the
strength of a bond and can be measured for bonded atoms that have any bond
order (not just singly-bonded atoms, as is the case of rcov). Values for Covalent bond
distance are determined by X-ray, electron and neutron diffraction, as well as by
microwave spectroscopy. Though d is the most commonly measured value, rcov is
more commonly used (see next section below). d is measured in picometers
(1pm=10-12m) and ngstrms (1=10-10m). Covalent bond distance can be used
as a measure of how tightly two atoms are bonded and is often used to support
calculations of bond order. Typically, the higher the bond order, the shorter the
Covalent bond distance.
It should be noted that the terms 'Covalent bond distance' and 'Bond Length' are
often used interchangeably. The two terms have essentially the same definition with
the difference only being that Covalent bond distance can only refer to covalently
bonded atoms while bond length could theoretically refer to two atoms bonded in
any way.
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 nonbonded 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
rcov (p
Values for rcov and rv m)

rv (p
m)

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/V 2) 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.

Figure: Van der Waals radius and Covalent radius (illustrated by Heesung Shim)