Boiling Points

For general purposes it is useful to consider temperature to be a measure of the kinetic energy of all the atoms and molecules in a given system. As temperature is increased, there is a corresponding increase in the vigor of translational and rotation motions of all molecules, as well as the vibrations of atoms and groups of atoms within molecules. Experience shows that many compounds exist normally as liquids and solids; and that even low-density gases, such as hydrogen and helium, can be liquified at sufficiently low temperature and high pressure. A clear conclusion to be drawn from this fact is that intermolecular attractive forces vary considerably, and that the boiling point of a compound is a measure of the strength of these forces. Thus, in order to break the intermolecular attractions that hold the molecules of a compound in the condensed liquid state, it is necessary to increase their kinetic energy by raising the sample temperature to the characteristic boiling point of the compound.

The following table illustrates some of the factors that influence the strength of intermolecular attractions. The formula of each entry is followed by its formula weight in parentheses and the boiling point in degrees Celsius. First there is molecular size. Large molecules have more electrons and nuclei that create van der Waals attractive forces, so their compounds usually have higher boiling points than similar compounds made up of smaller molecules. It is very important to apply this rule only to like compounds. The examples given in the first two rows are similar in that the molecules or atoms are spherical in shape and do not have permanent dipoles. Molecular shape is also important, as the second group of compounds illustrate. The upper row consists of roughly spherical molecules, whereas the isomers in the lower row have cylindrical or linear shaped molecules. The attractive forces between the latter group are generally greater. Finally, permanent molecular dipoles generated by polar covalent bonds result in even greater attractive forces between molecules, provided they have the mobility to line up in appropriate orientations. The last entries in the table compare non-polar hydrocarbons with equal-sized compounds having polar bonds to oxygen and nitrogen. Halogens also form polar bonds to carbon, but they also increase the molecular mass, making it difficult to distinguish among these factors.

Table 1: Boiling Points (ºC) of Selected Elements and Compounds

Increasing Size
Atomic	Ar (40) -186	Kr (83) -153	Xe (131) -109
Molecular	CH4 (16) -161	(CH3)4C (72) 9.5	(CH3)4Si (88) 27	CCl4 (154) 77
Molecular Shape
Spherical:	(CH3)4C (72) 9.5	(CH3)2CCl2 (113) 69	(CH3)3CC(CH3)3 (114) 106
Linear:	CH3(CH2)3CH3 (72) 36	Cl(CH2)3Cl (113) 121	CH3(CH2)6CH3 (114) 126
Molecular Polarity
Non-polar:	H2C=CH2 (28) -104	F2 (38) -188	CH3C≡CCH3 (54) -32	CF4 (88) -130
Polar:	H2C=O (30) -21	CH3CH=O (44) 20	(CH3)3N (59) 3.5	(CH3)2C=O (58) 56
	HC≡N (27) 26	CH3C≡N (41) 82	(CH2)3O (58) 50	CH3NO2 (61) 101

The melting points of crystalline solids cannot be categorized in as simple a fashion as boiling points. The distance between molecules in a crystal lattice is small and regular, with intermolecular forces serving to constrain the motion of the molecules more severely than in the liquid state. Molecular size is important, but shape is also critical, since individual molecules need to fit together cooperatively for the attractive lattice forces to be large. Spherically shaped molecules generally have relatively high melting points, which in some cases approach the boiling point. This reflects the fact that spheres can pack together more closely than other shapes. This structure or shape sensitivity is one of the reasons that melting points are widely used to identify specific compounds.

Table 2: Melting and Boiling points of Select Compounds

Compound	Formula	Boiling Point	Melting Point
pentane	CH3(CH2)3CH3	36ºC	–130ºC
hexane	CH3(CH2)4CH3	69ºC	–95ºC
heptane	CH3(CH2)5CH3	98ºC	–91ºC
octane	CH3(CH2)6CH3	126ºC	–57ºC
nonane	CH3(CH2)7CH3	151ºC	–54ºC
decane	CH3(CH2)8CH3	174ºC	–30ºC
tetramethylbutane	(CH3)3C-C(CH3)3	106ºC	+100ºC

Notice that the boiling points of the unbranched alkanes (pentane through decane) increase rather smoothly with molecular weight, but the melting points of the even-carbon chains increase more than those of the odd-carbon chains. Even-membered chains pack together in a uniform fashion more compactly than do odd-membered chains. The last compound, an isomer of octane, is nearly spherical and has an exceptionally high melting point (only 6º below the boiling point).

Contributors

• William Reusch, Professor Emeritus (Michigan State U.), Virtual Textbook of Organic Chemistry