Standard Enthalpies of Phase Transition

The enthalpies of phase transition, such as fusion (Aa,s/f), vaporization (AvapH), sublimation (Asut,//), and solution (As n//), are usually regarded as thermophysical properties, because they referto processes where no intramolecular bonds are cleaved or formed. As such, a detailed discussion of the experimental methods (or the estimation procedures) to determine them is outside the scope of the present book. Nevertheless, some of the techniques addressed in part II can be used for that purpose. For instance, differential scanning calorimetry is often applied to measure A us// and, less frequently, AmpH and AsubH. Many of the reported Asu, // data have been determined with Calvet microcalorimeters (see chapter 9) and from vapor pressure against temperature data obtained with Knudsen cells [35-38]. Reaction-solution calorimetry is the main source of AsinH values. All these auxiliary values are very important because they are frequently required to calculate gas-phase reaction enthalpies and to derive information on the strengths of chemical bonds (see chapter 5)—one of the main goals of molecular energetics. It is thus appropriate to make a brief review of the subject in this introduction. 

The standard enthalpy of transition of a substance A from a phase a to a phase P (AtrsH°) is the enthalpy associated with the process  

We have already illustrated equation 2.32 for a solution enthalpy (of liquid ethanol see section 2.5). We now apply it to another phase transition the vaporization of a pure substance. 

Although calorimetric methods are usually regarded as yielding the most accurate enthalpies of vaporization [39], the measurement of the saturation vapor pressures of a liquid as a function of temperature is also widely used for the same purpose and may afford good quality data. Among these so-called vapor pressure methods [35], differential ebulliometry is probably one of the most reliable. Briefly, the ebulliometric method consists in measuring the boiling temperatures of a liquid at different pressures. In the differential set-up, the pressure over the 

One of the critical issues in vapor pressure methods is the choice of the procedure to calculate the vaporization enthalpy. For instance, consider the vapor pressures of ethanol at several temperatures in the range 309-343 K, obtained with a differential ebulliometer [40]. The simplest way of deriving an enthalpy of vaporization from the curve shown in figure 2.4 is by fitting those data with the integrated form of the Clausius-Clapeyron equation [1]  

---

The types of values reported in the database standard enthalpies of formation at 298.15 K and 0 K, bond dissociation energies or enthalpies (D) at any temperature, standard enthalpy of phase transition—fusion, vaporization, or sublimation—at 298.15 K, standard entropy at 298.15 K, standard heat capacity at 298.15 K, standard enthalpy differences between T and 298.15 K, proton affinity, ionization energy, appearance energy, and electron affinity. The absence of a check mark indicates that the data are not provided. However, that does not necessarily mean that they cannot be calculated from other quantities tabulated in the database. 

---