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 (PageIndex{1}).
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.
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Previously, we defined the enthalpy changes associated with various chemical and physical processes. The melting points and molar enthalpies of fusion ((ΔH_{fus})), the energy required to convert from a solid to a liquid, a process known as fusion (or melting), as well as the normal boiling points and enthalpies of vaporization ((ΔH_{vap})) of selected compounds are listed in Table (PageIndex{1}).
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Table (PageIndex{1}): Melting and Boiling Points and Enthalpies of Fusion and Vaporization for Selected Substances. Values given under 1 atm. of external pressure. 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
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).
Less energy is needed to allow molecules to move past each other than to separate them totally.
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The direct conversion of a solid to a gas, without an intervening liquid phase, is called sublimation. The amount of energy required to sublime 1 mol of a pure solid is the enthalpy of sublimation (ΔHsub). Common substances that sublime at standard temperature and pressure (STP; 0°C, 1 atm) include CO2 (dry ice); iodine (Figure (PageIndex{2})); naphthalene, a substance used to protect woolen clothing against moths; and 1,4-dichlorobenzene. As shown in Figure (PageIndex{1}), 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.
[ΔH_{sub} =ΔH_{fus} +ΔH_{vap} label{Eq1} ]
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). 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.
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