Dispersion Forces 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 electrons 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 speciesa so-called dispersion force. 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. Table 1. Melting and Boiling Points of the Halogens Halogen Molar Mass Atomic Radius Melting Point Boiling Point fluorine, F2 38 g/mol 72 pm 53 K 85 K chlorine, Cl2 71 g/mol 99 pm 172 K 238 K bromine, Br2 160 g/mol 114 pm 266 K 332 K iodine, I2 254 g/mol 133 pm 387 K 457 K astatine, At2 420 g/mol 150 pm 575 K 610 K 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 molecules 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.
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