The enthalpy of vaporization can be written as \Delta H_\text{vap} = \Delta U_\text{vap} + p\,\Delta V. It is equal to the increased
internal energy of the vapor phase compared with the liquid phase, plus the work done against ambient pressure. The increase in the internal energy can be viewed as the energy required to overcome the
intermolecular interactions in the liquid (or solid, in the case of
sublimation). Hence
helium has a particularly low enthalpy of vaporization, 0.0845 kJ/mol, as the
van der Waals forces between helium
atoms are particularly weak. On the other hand, the
molecules in liquid
water are held together by relatively strong
hydrogen bonds, and its enthalpy of vaporization, 40.65 kJ/mol, is more than five times the energy required to heat the same quantity of water from 0 °C to 100 °C (
cp = 75.3 J/(K·mol)). Care must be taken, however, when using enthalpies of vaporization to
measure the strength of intermolecular forces, as these forces may persist to an extent in the gas phase (as is the case with
hydrogen fluoride), and so the calculated value of the
bond strength will be too low. This is particularly true for metals, which often form
covalently bonded molecules in the gas phase: in these cases, the
enthalpy of atomization must be used to obtain a true value of the
bond energy. An alternative description is to view the enthalpy of condensation as the heat which must be released to the surroundings to compensate for the drop in
entropy when a gas condenses to a liquid. As the liquid and gas are in
equilibrium at the boiling point (
Tb),
ΔvG = 0, which leads to \Delta_\text{v} S = S_\text{gas} - S_\text{liquid} = \frac{\Delta_\text{v} H}{T_\text{b}}. As neither entropy nor
enthalpy vary greatly with temperature, it is normal to use the tabulated standard values without any correction for the difference in temperature from 298 K. A correction must be made if the
pressure is different from 100
kPa, as the entropy of an
ideal gas is proportional to the logarithm of its pressure. The entropies of liquids vary little with pressure, as the
coefficient of thermal expansion of a liquid is small. These two definitions are equivalent: the boiling point is the temperature at which the increased entropy of the gas phase overcomes the intermolecular forces. As a given quantity of matter always has a higher entropy in the gas phase than in a condensed phase (\Delta_\text{v} S is always positive), and from \Delta G = \Delta H - T\Delta S, the
Gibbs free energy change falls with increasing temperature: gases are favored at higher temperatures, as is observed in practice. ==Vaporization enthalpy of electrolyte solutions==