The Effect of Surface Area on mp. and bp.

 n-Pentane vs. 2,2-Dimethylpropane (Neopentane)


Pentane

mp. -130 oC

bp. 36 oC

Surface Area = 118 Å2



Neopentane

mp. -16.6 oC

bp. 9.5 oC

Surface Area = 112 Å2

(How to manipulate JSmol structures)

London Dispersion Forces are the weakest intermolecular forces. They apply to both polar and non-polar molecules but are a smaller contributor in polar compounds. When non-polar molecules near one another their electrons are temporarily polarized (think formation of a tiny bar magnets). They are attracted to one another. The more electrons available, the greater the attraction. While the two alkanes in question have the same formula, mass and number of electrons, the exposure of the electrons differs owing to the shapes of the two alkanes. The difference in behavior reduces to a question of surface area. The greater the surface area; the greater the attraction between molecules. Greater attractive forces favor the liquid state over the gaseous state. Neopentane is spheroid, molecular contact is "tangential". Hence, its boiling point is lower than n-pentane, which has a larger surface area. However, the spheroid shape of neopentane favors the solid state over the liquid state. In the solid, crystalline state, efficient packing of molecules -- or atoms for that matter -- is essential (Think of the stacking of cannon balls in a pyramid). On the other hand, n-pentane has many more conformations available to it than neopentane and, therefore, more difficult to organize into crystals. Consequently, n-pentane has a much lower melting point (freezing point) than neopentane. The more spherical of two isomers will tend to have a smaller gap between its melting and boiling point.