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 at which that transformation takes place.
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 \( T_r \) \( {\displaystyle {}\ll 1} \). The heat of vaporization diminishes with increasing temperature and it vanishes completely at a certain point called the critical temperature ( \( {\displaystyle T_{r}=1} \) ). Above the critical temperature, the liquid and vapor phases are indistinguishable, and the substance is called a supercritical fluid.
Units
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
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
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
\( {\displaystyle \Delta H_{\text{vap}}=\Delta U_{\text{vap}}+p\Delta \,V} \)
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 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:
\( {\displaystyle \Delta _{\text{v}}S=S_{\text{gas}}-S_{\text{liquid}}={\frac {\Delta _{\text{v}}H}{T_{\text{b}}}}} \)
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 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 ( \( {\displaystyle \Delta _{\text{v}}S} \) 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
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
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Elements
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Enthalpies of vaporization of the elements
Enthalpies of vaporization of the elements
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---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | |||
Group → | ||||||||||||||||||||
↓ Period | ||||||||||||||||||||
1 | H0.44936 | He0.0845 | ||||||||||||||||||
2 | Li145.92 | Be292.40 | B489.7 | C355.8 | N2.7928 | O3.4099 | F3.2698 | Ne1.7326 | ||||||||||||
3 | Na96.96 | Mg127.4 | Al293.4 | Si300 | P12.129 | S1.7175 | Cl10.2 | Ar6.447 | ||||||||||||
4 | K79.87 | Ca153.6 | Sc314.2 | Ti421 | V452 | Cr344.3 | Mn226 | Fe349.6 | Co376.5 | Ni370.4 | Cu300.3 | Zn115.3 | Ga258.7 | Ge330.9 | As34.76 | Se26.3 | Br15.438 | Kr9.029 | ||
5 | Rb72.216 | Sr144 | Y363 | Zr581.6 | Nb696.6 | Mo598 | Tc660 | Ru595 | Rh493 | Pd357 | Ag250.58 | Cd100 | In231.5 | Sn295.8 | Sb77.14 | Te52.55 | I20.752 | Xe12.636 | ||
6 | Cs67.74 | Ba142 | La414 | Hf575 | Ta743 | W824 | Re715 | Os627.6 | Ir604 | Pt510 | Au334.4 | Hg59.229 | Tl164.1 | Pb177.7 | Bi104.8 | Po60.1 | At27.2 | Rn16.4 | ||
7 | Frn/a | Ra37 | Acn/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 | ||
Ce414 | Prn/a | Ndn/a | Pmn/a | Smn/a | Eun/a | Gdn/a | Tbn/a | Dyn/a | Hon/a | Ern/a | Tmn/a | Ybn/a | Lun/a | |||||||
Th514.4 | Pan/a | Un/a | Npn/a | Pun/a | Amn/a | Cmn/a | Bkn/a | Cfn/a | Esn/a | Fmn/a | Mdn/a | Non/a | Lrn/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
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) | (J/mol) | (J/g) | |
Acetone | 329g | 56 | 133 | 31300 | 538.9 |
Aluminium | 2792 | 2519 | 4566 | 294000 | 10500 |
Ammonia | 240 | −33.34 | −28 | 23350 | 1371 |
Butane | 272–274 | −1 | 30–34 | 21000 | 320 |
Diethyl ether | 307.8 | 34.6 | 94.3 | 26170 | 353.1 |
Ethanol | 352 | 78.37 | 173 | 38600 | 841 |
Hydrogen (parahydrogen) | 20.271 | −252.879 | −423.182 | 899.2 | 446.1 |
Iron | 3134 | 2862 | 5182 | 340000 | 6090 |
Isopropyl alcohol | 356 | 82.6 | 181 | 44000 | 732.2 |
Methane | 112 | −161 | −259 | 8170 | 480.6 |
Methanol | 338 | 64.7 | 148 | 35200[3] | 1104 |
Propane | 231 | −42 | −44 | 15700 | 356 |
Phosphine | 185 | −87.7 | −126 | 14600 | 429.4 |
Water | 373.15 | 100 | 212 | 40660 | 2257 |
See also
Enthalpy of fusion, specific heat of melting
Enthalpy of sublimation
Joback method, estimation of the heat of vaporization at the normal boiling point from molecular structures)
Clausius-Clapeyron equation
References
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.
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.
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.
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States of matter (list)
State
Solid Liquid Gas / Vapor Plasma
Phase change - en.svg
Low energy
Bose–Einstein condensate Fermionic condensate Degenerate matter Quantum Hall Rydberg matter Rydberg polaron Strange matter Superfluid Supersolid Photonic matter
High energy
QCD matter Lattice QCD Quark–gluon plasma Color-glass condensate Supercritical fluid
Other states
Colloid Glass Crystal Liquid crystal Time crystal Quantum spin liquid Exotic matter Programmable matter Dark matter Antimatter Magnetically ordered
Antiferromagnet Ferrimagnet Ferromagnet String-net liquid Superglass
Transitions
Boiling Boiling point Condensation Critical line Critical point Crystallization Deposition Evaporation Flash evaporation Freezing Chemical ionization Ionization Lambda point Melting Melting point Recombination Regelation Saturated fluid Sublimation Supercooling Triple point Vaporization Vitrification
Quantities
Enthalpy of fusion Enthalpy of sublimation Enthalpy of vaporization Latent heat Latent internal energy Trouton's ratio Volatility
Concepts
Baryonic matter Binodal Compressed fluid Cooling curve Equation of state Leidenfrost effect Macroscopic quantum phenomena Mpemba effect Order and disorder (physics) Spinodal Superconductivity Superheated vapor Superheating Thermo-dielectric effect
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