Enthalpy of vaporization

Summary

In thermodynamics, the enthalpy of vaporization (symbol Hvap), also known as the (latent) heat of vaporization or heat of evaporation, is the amount of energy (enthalpy) that must be added to a liquid substance to transform a quantity of that substance into a gas. The enthalpy of vaporization is a function of the pressure and temperature at which the transformation (vaporization or evaporation) takes place.

Temperature-dependency of the heats of vaporization for water, methanol, benzene, and acetone

The enthalpy of vaporization is often quoted for the normal boiling temperature of the substance. Although tabulated values are usually corrected to 298 K, that correction is often smaller than the uncertainty in the measured value.

The heat of vaporization is temperature-dependent, though a constant heat of vaporization can be assumed for small temperature ranges and for Reduced temperature Tr ≪ 1. The heat of vaporization diminishes with increasing temperature and it vanishes completely at a certain point called the critical temperature (Tr = 1). Above the critical temperature, the liquid and vapor phases are indistinguishable, and the substance is called a supercritical fluid.

Units

edit

Values are usually quoted in J/mol, or kJ/mol (molar enthalpy of vaporization), although kJ/kg, or J/g (specific heat of vaporization), and older units like kcal/mol, cal/g and Btu/lb are sometimes still used among others.

Enthalpy of condensation

edit

The enthalpy of condensation (or heat of condensation) is by definition equal to the enthalpy of vaporization with 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).

Thermodynamic background

edit
 
Molar enthalpy of zinc above 298.15 K and at 1 atm pressure, showing discontinuities at the melting and boiling points. The enthalpy of melting (ΔH°m) of zinc is 7323 J/mol, and the enthalpy of vaporization (ΔH°v) is 115330 J/mol.

The enthalpy of vaporization can be written as

 

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 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 (Tb), ΔvG = 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.

Vaporization enthalpy of electrolyte solutions

edit

Estimation of the enthalpy of vaporization of electrolyte solutions can be simply carried out using equations based on the chemical thermodynamic models, such as Pitzer model[1] or TCPC model.[2]

Selected values

edit

Elements

edit
Enthalpies of vaporization of the elements
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Group →
↓ Period
1 H0.90 He0.08
2 Li136 Be292 B508 C715 N5.57 O6.82 F6.62 Ne1.71
3 Na97.4 Mg128 Al284 Si359 P12.4 S45 Cl20.4 Ar6.53
4 K76.9 Ca155 Sc333 Ti425 V444 Cr339 Mn221 Fe340 Co377 Ni379 Cu300 Zn115 Ga256 Ge334 As32.4 Se95.5 Br30.0 Kr9.08
5 Rb75.8 Sr141 Y390 Zr573 Nb690 Mo617 Tc585 Ru619 Rh494 Pd358 Ag254 Cd99.9 In232 Sn296 Sb193 Te114 I41.6 Xe12.6
6 Cs63.9 Ba140   Lu414 Hf648 Ta733 W807 Re704 Os678 Ir564 Pt510 Au342 Hg59.1 Tl165 Pb179 Bi179 Po103 At54.4 Rn18.1
7 Fr65 Ra113   Lrn/a Rfn/a Dbn/a Sgn/a Bhn/a Hsn/a Mtn/a Dsn/a Rgn/a Cnn/a Nhn/a Fln/a Mcn/a Lvn/a Tsn/a Ogn/a

  La400 Ce398 Pr331 Nd289 Pm289 Sm172 Eu176 Gd301 Tb391 Dy280 Ho251 Er280 Tm191 Yb129
  Ac400 Th514 Pa481 U417 Np336 Pu333 Amn/a Cmn/a Bkn/a Cfn/a Esn/a Fmn/a Mdn/a Non/a
 
Enthalpy in kJ/mol, measured at their respective normal boiling points
0–10 kJ/mol 10–100 kJ/mol 100–300 kJ/mol >300 kJ/mol

The vaporization of metals is a key step in metal vapor synthesis, which exploits the increased reactivity of metal atoms or small particles relative to the bulk elements.

Other common substances

edit

Enthalpies of vaporization of common substances, measured at their respective standard boiling points:

Compound Boiling point, at normal pressure Heat of vaporization
(K) (°C) (°F) (kJ/mol) (J/g)
Acetone 329 56 133 31.300 538.9
Aluminium 2792 2519 4566 294.0 10500
Ammonia 240 −33.34 −28 23.35 1371
Butane 272–274 −1 30–34 21.0 320
Diethyl ether 307.8 34.6 94.3 26.17 353.1
Ethanol 352 78.37 173 38.6 841
Hydrogen (parahydrogen) 20.271 −252.879 −423.182 0.8992 446.1
Iron 3134 2862 5182 340 6090
Isopropyl alcohol 356 82.6 181 44 732.2
Methane 112 −161 −259 8.170 480.6
Methanol 338 64.7 148 35.2[3] 1104
Propane 231 −42 −44 15.7 356
Phosphine 185 −87.7 −126 14.6 429.4
Water 373.15 100 212 40.66 2257

See also

edit

References

edit
  1. ^ Ge, Xinlei; Wang, Xidong (20 May 2009). "Estimation of Freezing Point Depression, Boiling Point Elevation, and Vaporization Enthalpies of Electrolyte Solutions". Industrial & Engineering Chemistry Research. 48 (10): 5123. doi:10.1021/ie900434h.
  2. ^ Ge, Xinlei; Wang, Xidong (2009). "Calculations of Freezing Point Depression, Boiling Point Elevation, Vapor Pressure and Enthalpies of Vaporization of Electrolyte Solutions by a Modified Three-Characteristic Parameter Correlation Model". Journal of Solution Chemistry. 38 (9): 1097–1117. doi:10.1007/s10953-009-9433-0. ISSN 0095-9782. S2CID 96186176.
  3. ^ NIST
  • CODATA Key Values for Thermodynamics
  • Gmelin, Leopold (1985). Gmelin-Handbuch der anorganischen Chemie / 08 a (8., völlig neu bearb. Aufl. ed.). Berlin [u.a.]: Springer. pp. 116–117. ISBN 978-3-540-93516-2.
  • NIST Chemistry WebBook
  • Young, Francis W. Sears, Mark W. Zemansky, Hugh D. (1982). University physics (6th ed.). Reading, Mass.: Addison-Wesley. ISBN 978-0-201-07199-3.{{cite book}}: CS1 maint: multiple names: authors list (link)