11.5 Changes Of State

Energy Changes That Accompany Phase Changes

Phase changes are always accompanied by a change in the energy of a system. For example, converting a liquid, in which the molecules are close together, to a gas, in which the molecules are, on average, far apart, requires an input of energy (heat) to give the molecules enough kinetic energy to allow them to overcome the intermolecular attractive forces. The stronger the attractive forces, the more energy is needed to overcome them. Solids, which are highly ordered, have the strongest intermolecular interactions, whereas gases, which are very disordered, have the weakest. Thus any transition from a more ordered to a less ordered state (solid to liquid, liquid to gas, or solid to gas) requires an input of energy; it is endothermic. Conversely, any transition from a less ordered to a more ordered state (liquid to solid, gas to liquid, or gas to solid) releases energy; it is exothermic. The energy change associated with each common phase change is shown in Figure 11.17 "The Three Phases of Matter and the Processes That Interconvert Them When the Temperature Is Changed".

In Chapter 5 "Energy Changes in Chemical Reactions", we defined the enthalpy changes associated with various chemical and physical processes. The melting points and molar enthalpies of fusion (ΔHfus), the energy required to convert from a solid to a liquid, a process known as fusion (or melting)The conversion of a solid to a liquid., as well as the normal boiling points and enthalpies of vaporization (ΔHvap) of selected compounds are listed in Table 11.6 "Melting and Boiling Points and Enthalpies of Fusion and Vaporization for Selected Substances". The substances with the highest melting points usually have the highest enthalpies of fusion; they tend to be ionic compounds that are held together by very strong electrostatic interactions. Substances with high boiling points are those with strong intermolecular interactions that must be overcome to convert a liquid to a gas, resulting in high enthalpies of vaporization. The enthalpy of vaporization of a given substance is much greater than its enthalpy of fusion because it takes more energy to completely separate molecules (conversion from a liquid to a gas) than to enable them only to move past one another freely (conversion from a solid to a liquid).

Table 11.6 Melting and Boiling Points and Enthalpies of Fusion and Vaporization for Selected Substances

Substance	Melting Point (°C)	ΔHfus (kJ/mol)	Boiling Point (°C)	ΔHvap (kJ/mol)
N2	−210.0	0.71	−195.8	5.6
HCl	−114.2	2.00	−85.1	16.2
Br2	−7.2	10.6	58.8	30.0
CCl4	−22.6	2.56	76.8	29.8
CH3CH2OH (ethanol)	−114.1	4.93	78.3	38.6
CH3(CH2)4CH3 (n-hexane)	−95.4	13.1	68.7	28.9
H2O	0	6.01	100	40.7
Na	97.8	2.6	883	97.4
NaF	996	33.4	1704	176.1

Note the Pattern

ΔH is positive for any transition from a more ordered to a less ordered state and negative for a transition from a less ordered to a more ordered state.

The direct conversion of a solid to a gas, without an intervening liquid phase, is called sublimationThe conversion of a solid directly to a gas (without an intervening liquid phase).. The amount of energy required to sublime 1 mol of a pure solid is the enthalpy of sublimation (ΔHsub)The enthalpy change that accompanies the conversion of a solid directly to a gas.. Common substances that sublime at standard temperature and pressure (STP; 0°C, 1 atm) include CO2 (dry ice); iodine (Figure 11.18 "The Sublimation of Solid Iodine"); naphthalene, a substance used to protect woolen clothing against moths; and 1,4-dichlorobenzene. As shown in Figure 11.17 "The Three Phases of Matter and the Processes That Interconvert Them When the Temperature Is Changed", the enthalpy of sublimation of a substance is the sum of its enthalpies of fusion and vaporization provided all values are at the same T; this is an application of Hess’s law. (For more information about Hess’s law, see Chapter 5 "Energy Changes in Chemical Reactions", Section 5.2 "Enthalpy").

Equation 11.3

ΔHsub = ΔHfus + ΔHvap

Figure 11.18 The Sublimation of Solid Iodine

When solid iodine is heated at ordinary atmospheric pressure, it sublimes. When the I2 vapor comes in contact with a cold surface, it deposits I2 crystals.

Fusion, vaporization, and sublimation are endothermic processes; they occur only with the absorption of heat. Anyone who has ever stepped out of a swimming pool on a cool, breezy day has felt the heat loss that accompanies the evaporation of water from the skin. Our bodies use this same phenomenon to maintain a constant temperature: we perspire continuously, even when at rest, losing about 600 mL of water daily by evaporation from the skin. We also lose about 400 mL of water as water vapor in the air we exhale, which also contributes to cooling. Refrigerators and air-conditioners operate on a similar principle: heat is absorbed from the object or area to be cooled and used to vaporize a low-boiling-point liquid, such as ammonia or the chlorofluorocarbons (CFCs) and the hydrofluorocarbons (HCFCs) discussed in Chapter 3 "Chemical Reactions" in connection with the ozone layer. The vapor is then transported to a different location and compressed, thus releasing and dissipating the heat. Likewise, ice cubes efficiently cool a drink not because of their low temperature but because heat is required to convert ice at 0°C to liquid water at 0°C, as demonstrated later in Example 8.