.PNG)
'Molar heat content of zinc' above 298.15 K and at 1 atm pressure, showing discontinuities at the melting and boiling points. The enthalpy of melting (Δ''H''°m) of zinc is 7323 J/mol, and the enthalpy of vaporization (Δ''H''°v) is 115 330 J/mol.
The 'enthalpy of vaporization', (symbol
), also known as the 'heat of vaporization' or 'heat of evaporation', is the
energy required to transform a given quantity of a substance into a gas. It is measured at the
boiling point of the substance, although tabulated values are usually corrected to 298
K: the correction is small, and is often smaller than the
uncertainty in the measured value. Values are usually quoted in
kJ/
mol, although kJ/
kg,
kcal/mol, cal/g and
Btu/
lb are also possible, among others.
The 'enthalpy of condensation' (or 'heat of condensation') is numerically exactly equal to the enthalpy of vaporization, but has the opposite sign: enthalpy changes of vaporization are always positive (
heat is absorbed by the substance), whereas enthalpy changes of condensation are always negative (heat is released by the substance).
The enthalpy of vaporization 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, 40.8 kJ/mol, is more than five times the energy required to heat the same quantity of water from 0 °C to 100 °C (
''c''p = 75.3 J K
−1 mol
−1). 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 of 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 (''T''
b),
Δv''G'' = 0, which leads to:
:
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 a gas is proportional to its pressure (or, more precisely, to its
fugacity): the entropies of liquids vary little with pressure, as the
compressibility 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 (
is always positive), and from
:
,
the
Gibbs free energy change falls with increasing temperature: gases are favored at higher temperatures, as is observed in practice.
Selected values
Elements
'Enthalpies of vaporization of the elements in kJ/mol'
| 0–10 kJ/mol | 10–100 kJ/mol | 100–300 kJ/mol | >300 kJ/mol |
Other common substances
Common substances sorted by heat of vaporization:
See also
★
Enthalpy of fusion
References
Sears, Zemansky et al., University Physics, Addison-Wessley Publishing Company, Sixth ed., 1982, ISBN 0-201-07199-1