The Foundations of Chemistry

Dispersion Forces

Dispersion forcesare weak attractive forces that are important only over extremelyshort
distances because they vary as 1/d^7. They are present between all types of molecules in con-
densed phases but are weak for small molecules. Dispersion forces are the only kind of
intermolecular forces present among symmetrical nonpolar substances such as SO 3 , CO 2 ,
O 2 , N 2 , Br 2 , H 2 , and monatomic species such as the noble gases. Without dispersion
forces, such substances could not condense to form liquids or solidify to form solids. Con-
densation of some substances occurs only at very low temperatures and/or high pressures.
Dispersion forces result from the attraction of the positively charged nucleus of one
atom for the electron cloud of an atom in nearby molecules. This induces temporarydipoles
in neighboring atoms or molecules. As electron clouds become larger and more diffuse,
they are attracted less strongly by their own (positively charged) nuclei. Thus, they are
more easily distorted, or polarized,by adjacent nuclei.

Polarizability increases with increasing numbers of electrons and therefore with

increasing sizes of molecules. Therefore, dispersion forces are generally stronger for

molecules that have more electrons or are larger.

Dispersion forces are depicted in Figure 13-6. They exist in all substances.
Figure 13-5 shows that polar covalent compounds with hydrogen bonding (H 2 O, HF,
NH 3 ) boil at higher temperatures than analogous polar compounds without hydrogen
bonding (H 2 S, HCl, PH 3 ). Symmetrical, nonpolar compounds (CH 4 , SiH 4 ) of compa-

Dispersion forces are often called

London forces, after the German-born

physicist Fritz London (1900–1954).

He initially postulated their existence

in 1930, on the basis of quantum

theory.

Although the term “van der

Waals forces” usually refers to all

intermolecular attractions, it is also

often used interchangeably with

“dispersion forces,” as are the terms

“London forces” and “dipole-induced

dipole forces.”

13-2 Intermolecular Attractions and Phase Changes 491

Figure 13-6 An illustration of how a temporary dipole can be induced in an atom. (a) An
isolated argon atom, with spherical charge distribution (no dipole). (b) When a cation
approaches the argon atom, the outer portion of the electron cloud is weakly attracted by
the ion’s positive charge. This induces a weak temporarydipole in the argon atom. (c) A
temporary dipole can also be induced if the argon atom is approached by an anion. (d) The
approach of a molecule with a permanent dipole (for instance, HF) could also temporarily
polarize the argon atom. (e) Even in pure argon, the close approach of one argon atom to
another results in temporary dipole formation in both atoms as each atom’s electron cloud is
attracted by the nucleus of the other atom or is repelled by the other atom’s electron cloud.
The resulting temporary dipoles cause weak attractions among the argon atoms. Molecules
are even more easily polarized than isolated atoms.

(a) (b) (c)

(d) (e)

δ+ δ– A +–A

A

A

A

A

δ– δ+

δ– δ+

δ–

δ+ δ– δ+

δ–

δ δ+

δ– + δ–

δ+

See the Saunders Interactive

General Chemistry CD-ROM,

Screen 13.5, Intermolecular Forces (3).