Boiling Point - Boiling Point As A Reference Property of A Pure Compound

Boiling Point As A Reference Property of A Pure Compound

As can be seen from the above plot of the logarithm of the vapor pressure vs. the temperature for any given pure chemical compound, its normal boiling point can serve as an indication of that compound's overall volatility. A given pure compound has only one normal boiling point, if any, and a compound's normal boiling point and melting point can serve as characteristic physical properties for that compound, listed in reference books. The higher a compound's normal boiling point, the less volatile that compound is overall, and conversely, the lower a compound's normal boiling point, the more volatile that compound is overall. Some compounds decompose at higher temperatures before reaching their normal boiling point, or sometimes even their melting point. For a stable compound, the boiling point ranges from its triple point to its critical point, depending on the external pressure. Beyond its triple point, a compound's normal boiling point, if any, is higher than its melting point. Beyond the critical point, a compound's liquid and vapor phases merge into one phase, which may be called a superheated gas. At any given temperature, if a compound's normal boiling point is lower, then that compound will generally exist as a gas at atmospheric external pressure. If the compound's normal boiling point is higher, then that compound can exist as a liquid or solid at that given temperature at atmospheric external pressure, and will so exist in equilibrium with its vapor (if volatile) if its vapors are contained. If a compound's vapors are not contained, then some volatile compounds can eventually evaporate away in spite of their higher boiling points.

In general, compounds with ionic bonds have high normal boiling points, if they do not not decompose before reaching such high temperatures. Many metals have high boiling points, but not all. Very generally—with other factors being equal—in compounds with covalently bonded molecules, as the size of the molecule (or molecular mass) increases, the normal boiling point increases. When the molecular size becomes that of a macromolecule, polymer, or otherwise very large, the compound often decomposes at high temperature before the boiling point is reached. Another factor that affects the normal boiling point of a compound is the polarity of its molecules. As the polarity of a compound's molecules increases, its normal boiling point increases, other factors being equal. Closely related is the ability of a molecule to form hydrogen bonds (in the liquid state), which makes it harder for molecules to leave the liquid state and thus increases the normal boiling point of the compound. Simple carboxylic acids dimerize by forming hydrogen bonds between molecules. A minor factor affecting boiling points is the shape of a molecule. Making the shape of a molecule more compact tends to lower the normal boiling point slightly compared to an equivalent molecule with more surface area.

Most volatile compounds (anywhere near ambient temperatures) go through an intermediate liquid phase while warming up from a solid phase to eventually transform to a vapor phase. By comparison to boiling, a sublimation is a physical transformation in which a solid turns directly into vapor, which happens in a few select cases such as with carbon dioxide at atmospheric pressure. For such compounds, a sublimation point is a temperature at which a solid turning directly into vapor has a vapor pressure equal to the external pressure.