London Dispersion Forces

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Two pairs of molecules are shown where each molecule has one larger blue side labeled “delta sign, negative sign” and a smaller red side labeled “delta sign, positive sign.” Toward the middle of the both molecules, but still on each distinct side, is a black dot. Between the two images is a dotted line labeled, “Attractive force.” In the first image, the red and blue sides are labeled, “Unequal distribution of electrons.” Below both images are brackets. The brackets are labeled, “Temporary dipoles.”
Figure 1. Dispersion forces result from the formation of temporary dipoles, as illustrated here for two nonpolar diatomic molecules. Source: OpenStax Chemistry 2e

London Dispersion Forces (OpenStax Chemistry 2e)

One of the three van der Waals forces is present in all condensed phases, regardless of the nature of the atoms or molecules composing the substance. This attractive force is called the London dispersion force in honor of German-born American physicist Fritz London who, in 1928, first explained it. This force is often referred to as simply the dispersion force. Because the electrons of an atom or molecule are in constant motion (or, alternatively, the electron’s location is subject to quantum-mechanical variability), at any moment in time, an atom or molecule can develop a temporary, instantaneous dipole if its electrons are distributed asymmetrically. The presence of this dipole can, in turn, distort the electrons of a neighboring atom or molecule, producing an induced dipole. These two rapidly fluctuating, temporary dipoles thus result in a relatively weak electrostatic attraction between the species—a so-called dispersion force like that illustrated in Figure 1.

Dispersion forces that develop between atoms in different molecules can attract the two molecules to each other. The forces are relatively weak, however, and become significant only when the molecules are very close. Larger and heavier atoms and molecules exhibit stronger dispersion forces than do smaller and lighter atoms and molecules. F2 and Cl2 are gases at room temperature (reflecting weaker attractive forces); Br2 is a liquid, and I2 is a solid (reflecting stronger attractive forces). Trends in observed melting and boiling points for the halogens clearly demonstrate this effect, as seen in Table 1.

Melting and Boiling Points of the Halogens

HalogenMolar MassAtomic RadiusMelting PointBoiling Point
fluorine, F238 g/mol72 pm53 K85 K
chlorine, Cl271 g/mol99 pm172 K238 K
bromine, Br2160 g/mol114 pm266 K332 K
iodine, I2254 g/mol133 pm387 K457 K
astatine, At2420 g/mol150 pm575 K610 K
Table 1 Source: OpenStax Chemistry 2e

The increase in melting and boiling points with increasing atomic/molecular size may be rationalized by considering how the strength of dispersion forces is affected by the electronic structure of the atoms or molecules in the substance. In a larger atom, the valence electrons are, on average, farther from the nuclei than in a smaller atom. Thus, they are less tightly held and can more easily form the temporary dipoles that produce the attraction. The measure of how easy or difficult it is for another electrostatic charge (for example, a nearby ion or polar molecule) to distort a molecule’s charge distribution (its electron cloud) is known as polarizability. A molecule that has a charge cloud that is easily distorted is said to be very polarizable and will have large dispersion forces; one with a charge cloud that is difficult to distort is not very polarizable and will have small dispersion forces.

The shapes of molecules also affect the magnitudes of the dispersion forces between them. For example, boiling points for the isomers n-pentane, isopentane, and neopentane (shown in Figure 2) are 36 °C, 27 °C, and 9.5 °C, respectively. Even though these compounds are composed of molecules with the same chemical formula, C5H12, the difference in boiling points suggests that dispersion forces in the liquid phase are different, being greatest for n-pentane and least for neopentane. The elongated shape of n-pentane provides a greater surface area available for contact between molecules, resulting in correspondingly stronger dispersion forces. The more compact shape of isopentane offers a smaller surface area available for intermolecular contact and, therefore, weaker dispersion forces. Neopentane molecules are the most compact of the three, offering the least available surface area for intermolecular contact and, hence, the weakest dispersion forces. This behavior is analogous to the connections that may be formed between strips of VELCRO brand fasteners: the greater the area of the strip’s contact, the stronger the connection.

Three images of molecules are shown. The first shows a cluster of large, gray spheres each bonded together and to several smaller, white spheres. There is a gray, jagged line and then the mirror image of the first cluster of spheres is shown. Above these two clusters is the label, “Small contact area, weakest attraction,” and below is the label, “neopentane boiling point: 9.5 degrees C.” The second shows a chain of three gray spheres bonded by the middle sphere to a fourth gray sphere. Each gray sphere is bonded to several smaller, white spheres. There is a jagged, gray line and then the mirror image of the first chain appears. Above these two chains is the label, “Less surface area, less attraction,” and below is the label, “isopentane boiling point: 27 degrees C.” The third image shows a chain of five gray spheres bonded together and to several smaller, white spheres. There is a jagged gray line and then the mirror image of the first chain appears. Above these chains is the label, “Large contact area, strong attraction,” and below is the label, “n-pentane boiling point 36 degrees C.”
Figure 2. The strength of the dispersion forces increases with the contact area between molecules, as demonstrated by the boiling points of these pentane isomers. Source: OpenStax Chemistry 2e

Source:

Flowers, P., Theopold, K., Langley, R., & Robinson, W. R. (2019, February 14). Chemistry 2e. Houston, Texas: OpenStax. Access for free at: https://openstax.org/books/chemistry-2e

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Related External Links

On the role of London dispersion forces in biomolecular structure determination