Molecular Modeling of Macroscopic Phase Changes 3 - Heat and Rate of Evaporation

Vol.
8, 2023-11
Molecular Modeling of Macroscopic Phase Changes 3: Heat and Rate of

Evaporation
Hugo Hernandez
ForsChem Research, 050030 Medellin, Colombia
hugo.hernandez@forschem.org
doi: 10.13140/RG.2.2.32905.42083
Abstract
This is the third part of a series of reports presenting a molecular model of phase change, and
in this case, heat and rates of evaporation are discussed. The heat of evaporation represents
the difference in average intermolecular potential energy between the liquid and gas phases,
which is difficult to determine theoretically due to the mathematical complexity involved.
Alternatively, the heat of evaporation is determined as the difference between the average
kinetic energy of molecules overcoming an energy barrier for evaporation at the vapor/liquid
interface, and the average kinetic energy of all molecules in the liquid phase. According to this
model, the heat of evaporation at the normal boiling temperature is found to be correlated
with the cohesion temperature, which is associated to the overall energy barrier for
evaporation of a pure compound. Such correlation has been found to satisfy both the Clausius-
Clapeyron relation and Trouton’s rule. In fact, a molecular explanation of Trouton’s rule is
obtained. In addition, a molecular model for the rate of evaporation of liquids is derived and
presented.
Keywords
Clausius-Clapeyron Equation, Cohesion Temperature, Energy Barrier, Heat of Vaporization,

Kinetic Energy, Latent Heat, Rate of Evaporation, Trouton’s Rule, Vapor Pressure
1. Introduction
In the previous parts [1,2] of this report series, a general mechanistic model for describing the
vapor pressure of a pure compound was obtained based on an energy barrier for the transfer
of molecules from the liquid to the gas phase. This model employs only two parameters and
can satisfactorily replace common empirical models including Antoine equation.
Cite as: Hernandez, H. (2023). Molecular Modeling of Macroscopic Phase Changes 3: Heat and Rate of
Evaporation. ForsChem Research Reports, 8, 2023-11, 1 - 34. Publication Date: 15/08/2023.
Molecular Modeling of Macroscopic Phase
Changes 3: Heat and Rate of Evaporation
Hugo Hernandez
ForsChem Research
According to this model, the vapor pressure ( ) can be related to the system temperature ( )
using the following relation [1]:
( )
( ) ̃( ) ( )
( )
(1.1)
where is a crowding factor in the condensed phase, represents

Boltzmann constant, ̃( ) is the molecular number density of the liquid or condensed phase at
temperature (neglecting pressure effects), is the energy barrier to condensation,
is an energy barrier to evaporation, and is the error function.
Neglecting the energy barrier for condensation, model (1.1) was alternatively expressed as
follows [2]:
( ) ( ) ( )
(1.2)
where
( ) ̃( )
(1.3)
(1.4)
is the complementary error function, parameter ( ) is expressed in units of pressure per

unit of absolute temperature, and parameter , denoted as cohesion temperature, is expressed
in units of absolute temperature.
By considering the vapor pressure at any reference temperature, a single parameter model is
obtained:
( )
( )
( ) ( )
(1.5)
Cohesion temperature values for different pure chemical compounds were obtained from
available experimental data, and published in the previous part of this series [2].
In this third report of the series, theoretical derivations of the heat and rate of evaporation are
obtained based on the same principles and assumptions considered to obtain model (1.1). The
derivation of the heat of evaporation is presented in Section 2. Then in Section 3, the entropy
15/08/2023 ForsChem Research Reports Vol. 8, 2023-11

10.13140/RG.2.2.32905.42083 www.forschem.org (2 / 34)
Hugo Hernandez
ForsChem Research
of evaporation is theoretically determined from the model and compared to Trouton’s rule and
to experimental values reported in the literature. Section 4 presents a brief discussion about
the effects of temperature and pressure on the heat of evaporation, including the Clausius-
Clapeyron relation. Finally, mathematical expressions for the rate of evaporation of pure
compounds and mixtures are obtained in Section 5.
2. Theoretical Derivation of the Heat of Evaporation
The heat of evaporation, also known as heat of vaporization, enthalpy of vaporization, or latent
heat of vaporization, can be defined as “the amount of heat needed to turn 1 g of a liquid into a
vapor, without a rise in the temperature of the liquid” [3]. Of course, the heat of evaporation
can be expressed in any other unit of mass or unit of quantity of substance in general.
Particularly in this report, the heat of evaporation per molecule is considered.
The heat of evaporation is commonly determined by means of a calorimeter. In this equipment,

the heat absorbed by the vaporizing substance is compensated by heating, keeping the
temperature of the liquid in the calorimeter constant and equal to that of the surrounding
thermostat [4]. The amount of substance evaporated is determined by weight difference, and
the total heat is calculated from the voltage and electrical current supplied to a resistance, in
the case of electrical heating. Notice that the heat of evaporation, like any other measure of
energy, is calculated rather than directly measured.
From a macroscopic perspective, it is quite reasonable to assume that the energy supplied to
the liquid is absorbed by the vapor, since the liquid temperature remains constant. Now, it is
commonly accepted that the vapor is at equilibrium with the liquid, and therefore, the
temperature of the vapor must also remain constant. Thus, the energy supplied to the system
must have been used to compensate for the difference in intermolecular potential energies
between the liquid and vapor phases. This may lead to considering the heat of vaporization as
the heat needed to induce this phase change [5].
There are, however, some issues with this interpretation. First of all, evaporation also takes
place at temperatures below the corresponding boiling point of a substance. In second place,
evaporation also occurs even if no heat is supplied to the liquid, and in this case, a decrease in
temperature is observed as a result of evaporation. In addition, from a molecular perspective,
both liquid and vapor molecules can only have the exact same temperature if all molecules in
the liquid have the same probability of evaporation, which is not necessarily the case.
Let us recall that the translational relative kinetic energy ( ) of the molecules in a system can
be described by a distribution with degrees of freedom, according to the following
probability density distribution function [6]:

Hugo Hernandez
ForsChem Research
( ) √
( )
(2.1)
having an average value of:
〈 〉 ∫ √
( )
(2.2)
Now, we may assume that the energy needed to overcome intermolecular attractive forces in
the liquid state can be supplied by the own translational motion of the molecules. Then,
assuming a net energy barrier for evaporation ( ) depending on the temperature and
pressure of the system, the average translational kinetic energy of the molecules overcoming
the barrier at a system temperature will be:
∫ √ ∫
( ) ( ) ( )
〈 〉
∫ √ ∫
( ) ( ) ( )
( )
( ) ( )
( )
( ) ( )
( )
√ ( ) ( ) ( )
(√ ) (( ) √ )
( )
√ ( ) ( )
(√ ) √
( )
(2.3)
Since the average translational kinetic energy of the molecules is , then the loss of the
fastest molecules implies a decrease in the average kinetic energy of the molecules remaining
in the liquid phase. In simple words, the temperature of the system decreases as a result of the
loss of the fastest molecules in the form of vapor. Now, since the heat of evaporation has been
defined (and determined) as the heat needed to maintain a constant temperature, then we
may determine the molecular heat of evaporation ( ) as follows:
( ) 〈 〉 〈 〉
(2.4)

Hugo Hernandez
ForsChem Research
Notice that for ( ) we have evaporation without temperature change in the liquid
phase.
Using Eq. (2.2) and (2.3) in Eq. (2.4) we obtain:
( )
√ (√
( )
) ((
( )
√ ( )
)
)
( )
( )
√ (√
( )
) √ ( )
( )
( )
( )
( )
( )
√ (√
( )
) √ ( )
(2.5)
However, all translational kinetic energy is not necessarily available for overcoming the energy
barrier. In principle, only the translational kinetic energy perpendicular to the interface can be
used to overcome the interfacial energy barrier. Thus, it would be more accurate to determine
the average translational kinetic energy of the molecules overcoming the barrier as follows:
∫ √ ∫
( ) ( )
〈 〉
∫
∫ ( )
( ) √
( )
( ) ( )
( )
( ) ( )
( )
√ ( ) ( )
(√ ) √
( )
√ (√ )
( )
(2.6)
where the first term ( ) represents the average translational kinetic energy of the molecules
parallel to the interface, and the translational kinetic energy perpendicular to the interface is
given by a distribution with a single degree of freedom.

Hugo Hernandez
ForsChem Research
Then, the corresponding heat of evaporation for this case is:
( )
√ ( ) ( )
(√ ) √
( )
( )
√ (√ )
( )
( )
( )
√
( )
√ (√ )
(2.7)
Figure 1 illustrates the behavior of the heat of vaporization obtained with Eq. (2.7) as a function
of the energy barrier for evaporation.
Figure 1. Reduced heat of vaporization as a function of the reduced energy barrier for vaporization.
Green solid line: Reduced heat of evaporation according to Eq. (2.7). Gray dotted line: Reduced energy
barrier used as reference value.
In general, we can observe a clear dependence of the heat of vaporization on the energy
barrier for vaporization. Considering only translational motion perpendicular to the surface, the
heat of vaporization is found to be slightly larger than the energy barrier value. Such difference
is found to be less than . In the case where the energy barrier is negligible ( ( ) ),
we find that ( ) indicating that virtually all molecules can abandon the liquid phase.
As the energy barrier increases, the heat of vaporization also increases almost linearly.

Hugo Hernandez
ForsChem Research
According to this model, the heat of vaporization might be estimated from the energy barrier
of vaporization at the particular conditions of the system. Previously [2], the cohesion
temperature of the substance was related to an “overall” energy barrier over a wide range of
temperatures and pressures. For example, Table 4 in [2] provides a list of values of the
cohesion temperature for over 1400 pure compounds. Such cohesion temperature is a constant
parameter, but the net energy barrier for vaporization depends on environmental conditions,
since the difference in strength of intermolecular forces between gas and liquid phases are
strongly influenced by temperature and pressure. At low pressures, for example, the
intermolecular forces in the vapor phase are negligible. However, at high temperature and
pressures, the strength of intermolecular forces at both liquid and gas phases are practically
identical (supercritical conditions).
As an approximation, we may conclude that:
( ) ( ) ( ) ( ) 〈 ( )〉 〈 ( )〉
(2.8)
where 〈 ( ) 〉 and 〈 ( ) 〉 are the average intermolecular potential energy in the gas and
liquid phase, respectively. Notice that the intermolecular potential energy is negative in the
case of attractive forces, and positive in the case of repulsive forces.
3. Trouton’s Rule
One of the most interesting observations about the heat of evaporation was presented by
Frederick Trouton in the 1880’s [7]. Trouton determined the entropy of evaporation of
different compounds, using the following expression:
( )
( )
(3.1)
and found that at atmospheric (normal) pressure, the entropy of vaporization of most
compounds was almost identical, with an approximate value of [8].
Notice that the entropy of vaporization is closely related to the reduced heat of vaporization
( )
defined in the previous section as . Let us recall that entropy is not a tangible physical
property, but rather it is a mathematical concept [9], just like energy [10] and enthalpy [11].

Hugo Hernandez
ForsChem Research
In order to understand this particular behavior of chemical compounds, let us first obtain the
boiling temperature ( ) at atmospheric pressure ( ) from the vapor
pressure equation (Eq. 1.2):
( )
̃( )
(3.2)
Unfortunately, Eq. (3.2) does not provide an explicit value for . However, for most
compounds we may assume that the vapor behaves an ideal gas at atmospheric pressure, and
therefore:
̃( )
( )
̃( )
(3.3)
which can be equivalently expressed as follows:
̃( )
( )
̃( )
(3.4)
Now, replacing Eq. (3.4) in Eq. (3.1):
( ) ( ) ̃( ) ( )
( ) ( )
̃( )
̃( ) ( )
( )
̃( )
(3.5)
Thus, the almost constant entropy of vaporization observed at atmospheric pressure implies
that:
 The ratio between the molecular densities at the liquid and gas phases at the normal
boiling temperature (at atmospheric pressure), corrected by the “crowding factor” is
approximately constant for all compounds.
 The ratio between the net energy barrier of evaporation at the normal boiling
temperature and the “overall” energy barrier of evaporation is approximately constant
for all compounds.
While these two assumptions seem reasonable, deviations in the values of those ratios can also
explain experimental deviations from Trouton’s rule.

Hugo Hernandez
ForsChem Research
̃( )
First, let us consider the behavior of the term ( ̃(
). Figure 2 shows the
)
histogram of the values of this term obtained for over 1400 compounds using the vapor
pressure parameters reported earlier [2]. The data can be approximately represented by a
normal distribution with unbiased parameter estimations: and ,
corresponding to a relative variation of .
̃( )
Figure 2. Histogram of values for the term ( ) from a database of 1461 pure
̃( )
compounds. Red line: Normal distribution approximation.
On the other hand, the behavior of the ratio between experimental values of the heat of
evaporation at atmospheric pressure (used as an approximation to the energy barrier of
vaporization), and the energy barrier obtained from the cohesion temperature fitted from
experimental data [2], is illustrated in Figure 3. The data can be approximately represented by a
normal distribution with unbiased parameter estimations: and ,
The experimental data was obtained from calorimetric data reported in the literature [12-15] for
selected compounds (135 pure substances). The experimental data is summarized in Table 1,
including the calculation of entropy of vaporization and the corresponding cohesion
temperature ( ) and overall energy barrier for evaporation ( ) of the compound,
determined in a previous report [2].
Now, the behavior of the entropy of vaporization obtained from experimental data is
illustrated in Figure 4. The entropy of vaporization can be approximated by a normal
distribution with unbiased parameter estimations: and ,

Hugo Hernandez
ForsChem Research
( )
Figure 3. Histogram of values for the term from a database of 135 pure compounds. Red line:
Normal distribution approximation.
Table 1. Normal boiling temperature ( ), calorimetric heat of evaporation ( ), and entropy of

evaporation ( ) data of selected compounds.
Name Formula [K] [ ]

[ ] [ ] [ ]
Silver Ag 2485 251208 101.08 5569.99 277853
Aluminum Al 2329 290900 124.90 5416.47 270195
Argon Ar 88 6523 74.51 178.59 8909
Gold Au 3239 342400 105.71 7326.64 365482
Barium Ba 1911 177100 92.67 3619.72 180566
Bismuth Bi 1693 172078 101.63 5156.72 257238
Bromine Br2 331 30560 92.23 780.24 38921
Decyl alcohol C10H22O 504 50208 99.59 1159.91 57861
Trichlorotrifluoroethane C2Cl3F3 321 27489 85.70 706.01 35219
Ethylene C2H4 169 13544 79.93 365.51 18233
1,2-Dichloroethane C2H4Cl2 356 32008 89.86 803.31 40072
Methyl formate C2H4O2 305 27900 91.43 690.19 34429
Ethyl bromide C2H5Br 312 27000 86.66 704.07 35122
Ethyl chloride C2H5Cl 285 24800 86.88 639.41 31896
Ethane C2H6 185 14707 79.69 395.11 19710
Dimethyl ether C2H6O 249 21500 86.19 557.90 27830
Ethanol C2H6O 352 38744 110.21 883.88 44092
Dimethyl sulfide C2H6S 309 27000 87.34 684.96 34168
Dimethylamine C2H7N 281 26485 94.40 644.14 32132
Ethylamine C2H7N 290 28033 96.75 666.01 33223
Propylene C3H6 225 18410 81.66 487.78 24332
Acetone C3H6O 330 29121 88.34 757.95 37810
Ethyl formate C3H6O2 327 29800 91.01 740.85 36957
Methyl acetate C3H6O2 331 30500 92.16 757.76 37800
1-Bromopropane C3H7Br 344 29700 86.30 717.84 35809
2-Bromopropane C3H7Br 333 28400 85.25 688.22 34331
Propane C3H8 231 18774 81.26 499.09 24897

Hugo Hernandez
ForsChem Research
Table 1 (cont.). Normal boiling temperature ( ), calorimetric heat of evaporation ( ), and entropy
of evaporation ( ) data of selected compounds.

[ ] [ ] [ ]
1-Propanol C3H8O 371 41756 112.57 918.36 45812
2-Propanol C3H8O 356 39832 112.00 901.68 44980
1-Propanethiol C3H8S 341 29500 86.62 714.31 35633
Propylamine C3H9N 322 29706 92.36 731.21 36476
Trimethylamine C3H9N 276 24100 87.30 556.87 27779
2-Methylpropane C4H10 261 21297 81.46 545.83 27228
Butane C4H10 273 22393 82.13 588.43 29353
Butyl alcohol C4H10O 391 43095 110.32 967.54 48265
Diethyl ether C4H10O 308 26694 86.74 679.85 33914
Isobutyl alcohol C4H10O 381 42049 110.32 979.63 48868
sec-Butyl alcohol C4H10O 373 40794 109.47 929.79 46382
ter-Butyl alcohol C4H10O 356 39037 109.64 897.30 44761
Diethylamine C4H11N 329 27824 84.66 734.23 36626
Thiophene C4H4S 358 31500 88.10 755.53 37689
1-Butyne C4H6 282 24500 86.93 586.25 29244
1-Butene C4H8 267 21907 82.09 541.72 27023
2-Methylpropene C4H8 266 22117 83.07 541.74 27024
trans-2-Butene C4H8 274 22800 83.20 546.66 27269
2-Butanone C4H8O 353 31300 88.73 732.96 36563
Ethyl acetate C4H8O2 350 31900 91.08 794.62 39639
Methyl propionate C4H8O2 353 32100 90.95 801.35 39975
Propyl formate C4H8O2 354 33500 94.51 797.75 39795
1-Chlorobutane C4H9Cl 351 29400 83.77 731.89 36510
1-Pentene C5H10 303 25196 83.09 620.58 30957
2-Methyl-1-butene C5H10 293 25900 88.29 581.85 29025
2-Methyl-2-butene C5H10 312 26300 84.39 629.24 31389
Cyclopentane C5H10 322 27300 84.66 662.49 33048
2-Pentanone C5H10O 376 33400 88.72 914.61 45624
3-Methyl-2-butanone C5H10O 362 32300 89.21 899.29 44860
3-Pentanone C5H10O 376 33500 89.13 914.13 45600
Propyl acetate C5H10O2 375 33900 90.41 853.38 42570
2,2-Dimethylpropane C5H12 283 22753 80.50 539.14 26895
2-Methylbutane C5H12 301 24686 82.03 654.50 32649
Pentane C5H12 309 25857 83.61 675.09 33676
Amyl alcohol C5H12O 411 44350 107.92 982.36 49004
Isoamyl alcohol C5H12O 404 40585 100.52 977.85 48779
Pyridine C5H5N 389 35100 90.34 820.24 40917
Cyclohexane C6H12 354 29957 84.66 771.94 38507
2,2-Dimethylbutane C6H14 323 26305 81.48 653.77 32613
2,3-Dimethylbutane C6H14 331 27280 82.38 718.65 35849
2-Methylpentane C6H14 333 27782 83.32 688.86 34363
3-Methylpentane C6H14 336 28075 83.44 692.35 34537
Hexane C6H14 342 28853 84.40 743.91 37109
1-Hexanol C6H14O 430 48534 112.83 1035.08 51634
Fluorobenzene C6H5F 358 31200 87.19 796.96 39755
Benzene C6H6 353 30761 87.08 790.00 39408
2,2,3-Trimethylbutane C7H16 354 28949 81.77 711.84 35510
2,2-Dimethylpentane C7H16 352 28800 81.74 723.53 36093
3-Ethylpentane C7H16 367 30957 84.43 762.13 38018

Hugo Hernandez
ForsChem Research

[ ] [ ] [ ]
Heptane C7H16 372 31698 85.31 816.39 40725
1-Heptanol C7H16O 449 48116 107.17 1079.22 53836
Toluene C7H8 384 33179 86.46 856.85 42743
Anisole C7H8O 429 38900 90.75 903.48 45069
2-Xylene C8H10 418 36819 88.18 882.10 44003
3-Xylene C8H10 412 36359 88.20 870.93 43446
4-Xylene C8H10 411 35982 87.45 867.14 43256
Ethylbenzene C8H10 409 35564 86.88 919.08 45847
2,2,4-Trimethylpentane C8H18 372 31008 83.28 764.05 38114
Octane C8H18 399 34413 86.30 884.90 44143
1-Octanol C8H18O 468 50626 108.09 1113.19 55530
Calcium Ca 1760 150700 85.62 3566.59 177916
Dichlorodifluoromethane CCl2F2 243 19966 82.05 525.59 26219
Trichlorofluoromethane CCl3F 297 25200 84.89 650.37 32443
Carbon tetrachloride CCl4 350 30019 85.81 767.31 38277
Cadmium Cd 1038 99600 95.94 2142.69 106886
Nitromethane CH3NO2 374 34000 90.82 792.29 39522
Methane CH4 112 8185 73.31 231.35 11541
Methanol CH4O 338 35254 104.35 842.69 42037
Methylamine CH5N 267 25983 97.37 626.12 31234
Trichloromethane CHCl3 334 29391 87.88 756.75 37750
Chlorodifluoromethane CHClF2 232 20200 86.94 518.05 25842
Chlorine Cl2 239 20423 85.33 529.37 26407
Carbon monoxide CO 82 6046 73.86 164.58 8210
Carbon dioxide CO2 195 17154 87.99 474.30 23660
Chromium Cr 2755 342100 124.17 6656.20 332038
Cesium Cs 963 66600 69.15 1723.99 86000
Carbon disulfide CS2 320 26796 83.83 713.45 35590
Copper Cu 2868 304800 106.27 6344.81 316504
Fluorine F2 85 6527 76.56 163.01 8132
Iron Fe 3008 340400 113.16 7284.89 363400
Gallium Ga 2344 270500 115.39 5624.81 280588
Hydrogen H2 21 904 43.79 34.39 1715
Water H2O 373 40656 108.95 931.60 46472
Helium He 5 84 18.40 3.39 169
Mercury Hg 630 61127 97.00 1332.61 66476
Iodine I2 456 41900 91.86 1010.99 50432
Potassium K 1047 79500 75.92 1956.57 97602
Krypton Kr 121 9035 74.58 258.89 12914
Lithium Li 1645 147800 89.84 3226.79 160965
Magnesium Mg 1380 127700 92.53 3000.78 149691
Manganese Mn 2424 231100 95.33 5060.05 252415
Molybdenum Mo 5077 590300 116.27 11481.67 572751
Nitrogen N2 77 5581 72.15 157.16 7840
Sodium Na 1165 97971 84.08 2316.64 115563
Neon Ne 27 1841 67.81 52.56 2622
Nickel Ni 3005 374300 124.55 7335.57 365928
Oxygen O2 90 6825 75.79 187.46 9351
Phosphorous (yellow) P 553 51900 93.83 1179.68 58847

Hugo Hernandez
ForsChem Research

[ ] [ ] [ ]
Lead Pb 2017 178776 88.63 4102.09 204628
Radon Rn 211 16412 77.65 391.35 19522
Silicon Si 2560 384800 150.30 8269.41 412511
Silicon tetrachloride SiCl4 330 29308 88.82 683.20 34081
Tin Sn 2543 293076 115.24 6370.56 317789
Stannic chloride SnCl4 386 34750 89.99 851.82 42492
Tellurium Te 1360 104700 76.98 2482.37 123831
Titanium tetrachloride TiCl4 409 35169 85.96 816.89 40750
Xenon Xe 165 12648 76.59 346.69 17294
Zinc Zn 1180 114300 96.85 2553.28 127368
Figure 4. Histogram of values for the entropy of vaporization from a database of 135 pure compounds.
Red line: Normal distribution approximation.
Several important points must be discussed here. First of all, considering the sample of pure
compounds shown in Table 1, the average entropy of vaporization at atmospheric pressure is
, slightly larger than the theoretical value of Trouton’s rule ( ). Of
course, the sample average obtained in each case will be strongly influenced by the selection of
chemical compounds in the analysis.
Notice also that the relative standard deviation of experimental values evaporation entropy is
more than (for the particular data set considered). The extreme experimental values
observed in this sample correspond to about and of the value suggested by
Trouton’s rule. Thus, it seems quite reasonable to assume that such variation is the result of
deviations in the density and energy ratios, as illustrated in Figure 2 and Figure 3.

Hugo Hernandez
ForsChem Research
An evaluation of Eq. (3.5) using simply average values (which is not necessarily adequate for
variables with large variability as in this case), yields:
( )
(3.6)
quite close to the average value of obtained from the data set.
Trouton’s rule can also be illustrated by plotting the heat of vaporization with respect to the
normal boiling temperature of different compounds. Figure 5 shows this particular plot,
indicating how Trouton’s rule is a good approximation for substances with normal boiling
temperatures up to . Thus, while Trouton’s rule may work well for many compounds,
the truth is that large deviations are observed particularly for less volatile materials.
Considering materials with normal boiling temperatures up to we might conclude that
the mean entropy of evaporation is instead of .
Figure 5. Correlation between heat of vaporization and boiling temperature at atmospheric pressure for
different pure compounds. Left plot: Normal boiling temperatures up to . Right plot: Normal
boiling temperatures up to .
An alternative way to represent Trouton’s rule, and more specifically the relation between
molar densities of gases and liquids, is plotting the cohesion temperature versus the normal
boiling temperature. This is illustrated in Figure 6 for more than 1400 pure substances. A simple
linear model is proposed to approximate this relation as follows:
(3.7)
Furthermore, the cohesion temperature can be correlated with the experimental heat of
vaporization, as shown in Figure 7. The resulting linear model also indicates the following
approximate relation:
( ) [ ] [ ]
(3.8)

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ForsChem Research
Figure 6. Correlation between cohesion temperature and normal boiling temperature for different pure
compounds. Left plot: Original scale. Right plot: Logarithm scale. The green dotted lines represent a
linear regression model with no intercept obtained from the data.
Figure 7. Correlation between heat of vaporization at atmospheric pressure and cohesion temperature
for different pure compounds. Left plot: Original scale. Right plot: Logarithm scale. The green dotted
lines represent a linear regression model with no intercept obtained from the data.
Combining Eq. (3.7) and (3.8) we obtain:
( ) [ ] [ ]
(3.9)
Notice that the coefficient found in this case is , quite close to the value of
found earlier for the whole data set (see Figure 5).
4. Effect of Temperature and Pressure on the Heat of Evaporation
Eq. (2.8) illustrated that the heat of vaporization can be approximately considered as the
difference in average intermolecular potential energies between the liquid and vapor phases. It
also indicated such difference is influenced by environmental conditions such as temperature

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ForsChem Research
and pressure. It also depends on composition, but we have been considering only pure
substances so far.
The effect of temperature on the heat of vaporization of pure substances has been widely
reported in the scientific literature. There are at least about different empirical models
available for describing the influence of temperature on the heat of vaporization [16].
In order to obtain a mechanistic expression for the effect of environmental conditions on the
heat of vaporization, let us first determine the average intermolecular potential energy in a
system as follows:
〈 ( )〉 ∫ ( ) ( )
(4.1)
where ( ) is the intermolecular potential energy function, ( ) is the probability density

function for the intermolecular distance ( ), and and are physical boundaries in the
system, caused by the impenetrability of matter ( ) and the finiteness of the system ( ).
The intermolecular potential energy function can be expressed in general as follows [17]:
( ) ( ) ∑ ( )
(4.2)
where , , , and are model parameters.
The probability density function of intermolecular distances can be approximated by:
( ) ̃( ) ( )
(4.3)
where ̃( ) is the molecular density of the system, and ( ) is the pair distribution function
[18], which is also a function of the environmental conditions.
Thus, the average intermolecular potential energy becomes:
〈 ( )〉 ∫ ( ( ) ∑ ( ) ) ̃( ) ( )
(4.4)
which can be alternatively expressed as follows:

Hugo Hernandez
ForsChem Research
〈 ( )〉 ̃( ) ∑ ∫ ( )
(4.5)
where
(4.6)
Considering the mathematical complexity involved in the solution of Eq. (4.5), an alternative
simplification can be considered. In this case, the average intermolecular potential is estimated
from the average intermolecular distance 〈 ( ) 〉:
〈 ( )〉 〈 ( )〉
〈 ( )〉 ( ) ∑ ( )
(4.7)
where
̃( )
〈 ( )〉 ( )
̃( )
(4.8)
is the volume of an individual molecule, and is the molecular diameter.
Of course, a more accurate estimation of intermolecular potential energy will be obtained by

solving Eq. (4.5).
Now using Eq. (4.7) and (4.8) in Eq. (2.8) we obtain:
̃ ( ) ̃ ( )
( ) [( ) ( ) ]
̃ ( ) ̃ ( )
̃ ( ) ̃ ( )
∑ [( ) ( ) ]
̃ ( ) ̃ ( )
(4.9)
Even when Eq. (4.9) is just an approximation, it results in a highly nonlinear function which also
requires knowing the behavior of the gas and liquid phase densities as functions of
temperature and pressure, thus increasing the mathematical complexity involved.

Hugo Hernandez
ForsChem Research
Also notice that when ̃ ( ) ̃ ( ) the heat of vaporization becomes negligible, as

expected for supercritical conditions. Also, as the density difference increases for a particular
substance, the heat of vaporization increases.
Another alternative to describe the effect of temperature on the heat of vaporization is using
Kirchhoff’s approach [13]. In first place, let us assume that one mole of a pure substance in
liquid state is heated from a certain temperature , completely vaporized at the normal boiling
temperature ( ), and then heated as vapor to a temperature . The molar energy of the
vapor at the end of the process ( ) can be determined as follows:
∫ ( ) ( ) ∫ ( )
(4.10)
where is the molar energy of the system completely in liquid state at temperature , ( )
and ( ) are temperature-dependent molar isobaric heat capacities for the liquid and gas
phases, respectively, and ( ) is the normal heat of vaporization.
Now, let us assume that we vaporize all the molecules at a different temperature, in this case,
at temperature . Then, the molar energy of the vapor at temperature will be:
∫ ( ) ( ) ∫ ( )
(4.11)
By equating Eq. (4.10) and (4.11), and solving for ( ), we obtain:
( ) ( ) ∫ ( ( ) ( ))
(4.12)
The isobaric heat capacities can be represented as a function of temperature by empirical

expressions like the Shomate equation [19]:
( )
(4.13)
or the extended Shomate equation [20]:
( )
(4.14)
In general, Eq. (4.12) can be expressed as follows:

Hugo Hernandez
ForsChem Research
( ) ( ) ∑ ( )
(4.15)
where for the original Shomate equation we have with , ,

, and ; and for the extended Shomate equation we have
with , , , ( ) , ( ) , and
( ) .
Eq. (4.12) can also be expressed in terms of average heat capacities:
( ) ( ) (〈 〉 〈 〉)( )
(4.16)
where 〈 〉 and 〈 〉 are average heat capacities over the range of temperatures between
and .
Now, any temperature can be used as reference temperature and not necessarily the normal
boiling point. Considering any arbitrary reference temperature , the heat of vaporization at
temperature will be:
( ) ( ) ∫ ( ( ) ( ))
( ) (〈 〉 〈 〉)( )
( ) ∑ ( )
(4.17)
Calorimetric heats of vaporization at a standard reference temperature of ( ) are

commonly found in the literature [4,13]. Table 2 summarizes standard heat of vaporization
values for pure compounds obtained by calorimetry.
Figure 8 illustrates the relation observed between the standard heat of vaporization and the
cohesion temperature of the selected pure compounds. While the heat of vaporization at the
normal boiling temperature shows a linear relationship with respect to the cohesion
temperature (Eq. 3.8), the standard heat of vaporization approximately presents a quadratic
relationship:
( )[ ] ( [ ] ) [ ]
(4.18)

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ForsChem Research
Table 2. Calorimetric standard heat of evaporation ( ( ) ) of selected compounds.
Name Formula [ ] Name Formula [ ]

[ ] [ ]
1,1,1,2-Tetrachloroethane C2H2Cl4 45700 841.3 2-Hexanone C6H12O 43100 997.5
1,1,1-Trichloroethane C2H3Cl3 32500 718.1 2-Iodopropane C3H7I 34100 748.5
1,1,2,2-Tetrachloroethane C2H2Cl4 45800 866.8 2-Methoxyethanol C3H8O2 45200 879.6
1,1,2-Trichloroethane C2H3Cl3 40250 820.6 2-Methyl-1-butene C5H10 25900 581.9
1,1-Dichloroethane C2H4Cl2 30600 731.1 2-Methyl-1-pentanol C6H14O 54700 981.6
1,2,3,4-Tetramethylbenzene C10H14 52600 1029.4 2-Methyl-2-butene C5H10 27100 629.2
1,2,3,5-Tetramethylbenzene C10H14 52000 1020.3 2-Methylbutane C5H12 25000 654.5
1,2,3-Trichloropropane C3H5Cl3 47800 920.2 2-Methylheptane C8H18 39700 822.6
1,2,3-Trimethylbenzene C9H12 49100 955.3 2-Methylhexane C7H16 34900 756.7
1,2,4-Trimethylbenzene C9H12 47900 938.6 2-Methylpentane C6H14 29900 688.9
1,2-Dichlorobutane C4H8Cl2 40100 787.5 2-Nonanone C9H18O 56400 1024.6
1,2-Dichloroethane C2H4Cl2 35100 803.3 2-Pentanone C5H10O 38400 914.6
1,2-Dichloropropane C3H6Cl2 36100 767.4 2-Propanol C3H8O 45340 901.7
1,2-Diethoxyethane C6H14O2 43200 749.7 2-Xylene C8H10 43400 882.1
1,2-Ethanediol C2H6O2 65600 1175.5 3,3-Dimethylhexane C8H18 37500 797.6
1,3,5-Trimethylbenzene C9H12 47500 928.4 3,3-Dimethylpentane C7H16 33000 734.0
1,3-Propanediol C3H8O2 72400 1185.7 3,4-Dimethylhexane C8H18 39000 815.8
1,4-Dioxane C4H8O2 38600 800.1 3-Bromopyridine C5H4BrN 52100 962.0
1-Bromobutane C4H9Br 36650 789.9 3-Ethylhexane C8H18 39600 822.8
1-Bromopropane C3H7Br 31900 717.8 3-Ethylpentane C7H16 35100 762.1
1-Chlorobutane C4H9Cl 33500 731.9 3-Methyl-2-butanone C5H10O 36800 899.3
1-Chloropropane C3H7Cl 28500 653.2 3-Methylheptane C8H18 39800 824.8
1-Decene C10H20 50400 871.3 3-Methylhexane C7H16 35100 759.8
1-Heptanol C7H16O 66800 1079.2 3-Methylpentane C6H14 30212 692.4
1-Hexadecene C16H32 80300 1316.8 3-Pentanone C5H10O 38500 914.1
1-Hexanol C6H14O 60800 1035.1 3-Xylene C8H10 42700 870.9
1-Iodopropane C3H7I 36300 777.3 4-Methyl-2-pentanone C6H12O 42500 954.0
1-Nonanol C9H20O 76900 1160.4 4-Methylheptane C8H18 39700 822.3
1-Pentene C5H10 25500 620.6 4-tert-Butylphenol C10H14O 67900 1187.1
1-Propanol C3H8O 47450 918.4 4-Xylene C8H10 42300 867.1
2,2,3-Trimethylpentane C8H18 37700 789.1 Acrylic acid C3H4O2 53100 964.5
2,2,4-Trimethyl-3-pentanone C8H16O 43300 1033.1 Amyl alcohol C5H12O 56900 982.4
2,2,4-Trimethylpentane C8H18 34900 764.1 Anisole C7H8O 46800 903.5
2,2-Dimethylbutane C6H14 27800 653.8 Benzene C6H6 33830 790.0
2,2-Dimethylhexane C8H18 37300 790.8 Bromobenzene C6H5Br 44000 959.9
2,2-Dimethylpentane C7H16 32400 723.5 Butyl alcohol C4H10O 52100 967.5
2,2-Dimethylpropane C5H12 21800 539.1 Butyl formate C5H10O2 41300 825.0
2,3,3-Trimethylpentane C8H18 37600 795.7 Butyronitrile C4H7N 39200 816.1
2,3,4-Trimethylpentane C8H18 37700 800.2 Carbon disulfide CS2 27500 713.4
2,3-Dimethylbutane C6H14 29200 718.7 Carbon tetrachloride CCl4 32456 767.3
2,3-Dimethylhexane C8H18 38800 812.4 Chlorobenzene C6H5Cl 41000 906.8
2,3-Dimethylpentane C7H16 34300 750.0 cis-1,2-Dimethylcyclohexane C8H16 39700 830.9
2,4-Dimethylhexane C8H18 37800 797.7 cis-1,3-Dimethylcyclohexane C8H16 38200 822.1
2,4-Dimethylpentane C7H16 32700 730.4 cis-1,4-Dimethylcyclohexane C8H16 39000 820.4
2,5-Dimethylhexane C8H18 37900 798.5 Cyclohexane C6H12 33017 771.9
2-Bromopropane C3H7Br 30200 688.2 Cyclohexanol C6H12O 62000 985.8
2-Butanone C4H8O 34650 733.0 Cyclohexanone C6H10O 45100 904.1
2-Chloropyridine C5H4ClN 51000 925.0 Cyclopentane C5H10 29200 662.5
2-Heptanone C7H14O 47200 1066.1 Decane C10H22 51420 967.7

Hugo Hernandez
ForsChem Research
Table 2 (cont.). Calorimetric standard heat of evaporation ( ( )) of selected compounds.
Name Formula [ ] Name Formula [ ]

[ ] [ ]
Decyl alcohol C10H22O 81500 1159.9 Methyl chloroacetate C3H5ClO2 46700 893.8
d-Fenchone C10H16O 51400 1008.1 Methyl dichloroacetate C3H4Cl2O2 47700 937.3
Dibromomethane CH2Br2 37000 767.1 Methyl formate C2H4O2 28700 690.2
Dibutyl disufide C8H18S2 62300 891.4 Methyl myristate C15H30O2 87000 1346.0
Dichloromethane CH2Cl2 30600 655.1 Methyl propionate C4H8O2 35900 801.4
Diethoxydimethylsilane C6H16O2Si 43100 840.6 Methyl propyl ether C4H10O 27600 659.4
Diethyl carbonate C5H10O3 43600 885.3 Methylcyclohexane C7H14 35387 767.5
Diethyl ether C4H10O 27100 679.8 N,N-Dimethylaniline C8H11N 52800 1019.2
Diethyl sulfide C4H10S 35800 797.3 Naphthalene C10H8 55650 1043.3
Diethylamine C4H11N 31300 734.2 Nitromethane CH3NO2 38300 792.3
Diisopropyl ether C6H14O 32100 698.6 Nonane C9H20 46550 896.9
Dimethyl sulfide C2H6S 27900 685.0 Octadecane C18H38 91440 1334.6
Diphenylmethane C13H12 66600 1134.2 Octane C8H18 41529 884.9
Dipropyl ether C6H14O 35700 728.7 Pentadecane C15H32 75400 1201.3
d-Limonene C10H16 48900 957.8 Pentane C5H12 26420 675.1
Dodecane C12H26 61520 1078.0 Propyl acetate C5H10O2 37700 853.4
Dodecyl alcohol C12H26O 91900 1280.4 Propyl formate C4H8O2 37500 797.7
Ethanol C2H6O 42260 883.9 Propylbenzene C9H12 46200 914.7
Ethoxytrimethylsilane C5H14OSi 38400 727.4 Propylene oxide C3H6O 27900 649.9
Ethyl acetate C4H8O2 35600 794.6 Pyridine C5H5N 40200 820.2
Ethyl butyrate C6H12O2 42000 838.9 sec-Butyl alcohol C4H10O 49740 929.8
Ethyl chloride C2H5Cl 24800 639.4 ter-Butyl alcohol C4H10O 46940 897.3
Ethyl chloroacetate C4H7ClO2 49500 935.4 tert-Amyl alcohol C5H12O 50100 913.6
Ethyl dichloroacetate C4H6Cl2O2 50600 927.5 Tetradecane C14H30 71730 1153.2
Ethyl isobutyrate C6H12O2 39800 874.9 Tetraethylsilane C8H20Si 39000 896.5
Ethyl propionate C5H10O2 39300 846.7 Tetramethylsilane C4H12Si 26000 654.5
Ethyl trichloroacetate C4H5Cl3O2 51000 1004.6 Toluene C7H8 38000 856.8
Ethylbenzene C8H10 42200 919.1 trans-1,2-Dimethylcyclohexane C8H16 38400 813.2
Ethylcyclohexane C8H16 40500 839.9 trans-1,3-Dimethylcyclohexane C8H16 39200 809.3
Glycerol C3H8O2 91700 1382.2 trans-1,4-Dimethylcyclohexane C8H16 39900 805.5
Glycol diacetate C6H10O4 61000 1066.5 Tribromomethane CHBr3 46100 872.6
Heptadecane C17H36 86000 1295.5 Trichloroethylene C2HCl3 34500 750.4
Heptane C7H16 36570 816.4 Trichlorofluoromethane CCl3F 25200 650.4
Hexadecane C16H34 81350 1245.1 Trichloromethane CHCl3 31100 756.7
Hexane C6H14 31520 743.9 Tridecane C13H28 66680 1135.0
Hydrogen disulfide H2S2 33800 817.6 Triethoxymethylsilane C7H18O3Si 45100 903.0
Isoamyl alcohol C5H12O 54100 977.8 Triethylpropylsilane C9H22Si 40000 959.8
Isobutyl alcohol C4H10O 50800 979.6 Undecan-2-one C11H22O 67000 1197.4
Isobutylamine C4H11N 33900 724.4 Undecane C11H24 56580 1024.5
Methanol CH4O 37400 842.7 Water H2O 43990 931.6
Methyl acetate C3H6O2 32300 757.8 α-Pinene C10H16 44600 905.5
Methyl caprylate C9H18O2 57150 1046.7 β-Pinene C10H16 45800 926.2
Methyl chloride CH3Cl 20100 556.6
Clearly, a less noisy relation with the cohesion temperature is observed for the heat of
vaporization at the normal boiling temperature. Thus, Eq. (4.16) would be preferred for
estimating heats of vaporization using the cohesion temperature of pure compounds [2].

Hugo Hernandez
ForsChem Research
Figure 8. Correlation between standard heat of vaporization (at and ) and cohesion
temperature for different pure compounds. The green dotted line represents a quadratic regression
model with no intercept obtained from the data.
Another important equation frequently employed to determine the latent heat of phase
change is the Clausius-Clapeyron relation [21,22], which for the heat of vaporization becomes:
( )
( ) ( )
̃( ) ̃( )
(4.19)
When the heat of vaporization is assumed constant, a Magnus-type [23,24] vapor pressure
equation is obtained by integrating Eq. (4.19) assuming ̃( ) ̃( ) and ideal gas
conditions [25,26]:
( )
( ) ∫ ( )
( )
(4.20)
equivalently expressed as:
( ( ))
(4.21)
where ( ( )) and , being an arbitrary reference temperature.
However, since the heat of vaporization depends on temperature, Eq. (4.21) is clearly
inaccurate.
Now, by considering the vapor pressure model presented in Eq. (1.5) we obtain the following
derivative:

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ForsChem Research
( ( )) ( )
( ) ( ) ( )
( ( ) )
( ) ( ) √
( )
( )
( )
√ ( )
(4.22)
Replacing this expression in the Clausius-Clapeyron equation we obtain:
( )
( ̃( ) ̃( ))
( ) ( )( )
̃( ) ̃( ) √ ( )
(4.23)
Now, assuming ̃( ) ̃( ) and ideal gas conditions as before:
( )
( ) ( )
√ ( )
(4.24)
which, for atmospheric conditions become:
( )
( ) ( )
√ ( )
(4.25)
By considering Eq. (3.7) which states that , then we obtain from Eq. (4.25) that
( ) [ ] [ ]. This value of is also similar to the
values previously obtained in Section 3 ( and ).
5. Rate of Evaporation
In this Section, a mechanistic molecular model of the rate of evaporation (molar rate and heat
rate) is presented. First, let us consider an irreversible evaporation where no vaporized
molecule may return to the liquid phase. Of course, this is an unrealistic assumption, and
therefore, a rate of reversible evaporation needs to be considered. The rate of evaporation
may also increase due to the influence of additional surfaces and interfaces other than the
liquid-vapor interface, giving rise to bubble formation.

Hugo Hernandez
ForsChem Research
5.1. Irreversible Evaporation Rate
The irreversible flux of molecules from the liquid to the gas phase at temperature and
pressure ( ( ) ) can be estimated as follows [1]:
( ) ̃( )
√ ( ( ))
(5.1)
where ̃( ) is the molecular density of the liquid at temperature and pressure , is the
molecular mass of the compound, and and are parameters of the vapor pressure model,
as discussed earlier. Values of the cohesion temperature for selected compounds have been
reported [2], and the value of can be determined by the following expression:
̃( ) ( ( ))
(5.2)
where , and is the normal boiling temperature of the compound.
Thus,
̃( )
( )
( ) √ ( )
√ ̃( ) ( )
(5.3)
Therefore, the irreversible molar evaporation rate ( ( )) is:
( ) ̃( )
( )
( ) √ ( )
√ ̃( ) ( )
(5.4)
where is the liquid-vapor interface and is Avogadro constant.
Notice that for completely incompressible liquids, the external pressure has no effect on the
rate of irreversible evaporation. In addition, notice that irreversible evaporation represents a
theoretical evaporation into perfect vacuum.
On the other hand, the heat rate of irreversible evaporation ( ̇ ( ) ) is:

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ForsChem Research
( ) ̃( )
( )
̇ ( ) ( ) ( ) √ ( )
√ ̃( ) ( )
(5.5)
Considering evaporation at atmospheric pressure and using Eq. (4.16):
( ( ) (〈 〉 〈 〉)( )) ̃( )
( )
̇ ( ) √ ( )
√ ̃( ) ( )
(5.6)
Figure 9 illustrates the effect of temperature on the molecular flux and heat flux of
evaporation of pure water, for temperatures between and , at atmospheric
pressure. The following parameters were used for water: ,
, , ( ) , 〈 〉 , 〈 〉
, and ̃( ) ̃( ).
Figure 9. Effect of liquid temperature on the irreversible molar flux (solid blue, left axis) and heat flux
(dashed red, right axis) of evaporation for water. Left plot: Original scale. Right plot: Logarithm scale.
Of course, these rates are much larger than those actually observed, due to the fact that we
are considering the ideal case of irreversible evaporation. For example, kg of water placed in
a cubic recipient of in side, and open at the top, would evaporate at in just
seconds, if the external pressure were close to perfect vacuum.
5.2. Reversible Evaporation Rate
In reality, atmospheric pressure exerts an additional resistance to evaporation, which

translates into the re-condensation of most molecules exiting the liquid phase. The flux of
condensation for a single-component system can be expressed as follows [1]:

Hugo Hernandez
ForsChem Research
( )
√
(5.7)
However, if the system evaporates into the atmosphere (or any other gas involving additional
components), the pressure term needs to be corrected by a partial pressure, or equivalently:
( )
( )
√
(5.8)
where ( ) is the molecular (or mole) fraction of the -th component present in the vapor
phase at the interface at temperature , and is the corresponding molecular mass.
The molecular fraction of the vapor at the interface depends on many factors, and more
particularly, on the transfer of matter through the gas phase [27]. However, a simple
approximation considering the influence of the bulk of the gas phase and the vapor pressure of
a multicomponent liquid system is the following:
( )
( )
∑ ( )
(5.9)
where ( ) is the vapor pressure of the -th compound at temperature (e.g. Eq. 1.5), and
is the molecular fraction of the -th compound in the bulk of the gas phase.
Thus, we may state Eq. (5.8) as follows:
( )
( ) ( )
∑ ( ) √
(5.10)
The reversible molar rate of evaporation ( ( )) will be then:
( ) ( ( ) ( ))
̃( )
( )
√ ( )
√ ̃( ) ( )
( )
( )
∑ ( ) √
(5.11)

Hugo Hernandez
ForsChem Research
This molar rate can also be expressed as follows:
̃( ) ( )
( ) ( ( ) ( ) )
√ ̃( ) ∑ ( )
(5.12)
where
( )
( ) ( )
( )
(5.13)
Of course, might also change during the evaporation process.
Figure 10 illustrates the reversible molar flux and reversible heat flux of evaporation for water
at atmospheric pressure, considering a completely dry environment. These results were
obtained considering the following empirical behavior of the liquid density of pure water, fitted
from reported data [28]:
̃( )
( ) ( )
̃( )
(5.14)
Figure 10. Effect of liquid temperature on the reversible molar flux (solid blue, left axis) and heat flux
(dashed red, right axis) of evaporation for water in a dry environment. Left plot: Original scale. Right
plot: Logarithm scale.
Resuming the previous example, kg of water placed in a cubic recipient of in side, and
open at the top, would evaporate at in hours, if the external environment were
always almost completely dry. However, due to evaporation the concentration of water in the
bulk of the gas increases, resulting in a reduction in evaporation rate (and longer evaporation
times). If the bulk of the external gas phase has a non-zero fraction of water, the evaporation
rate given by Eq. (5.12) may eventually become negative (at low temperatures). In those cases,

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ForsChem Research
there is a net condensation of water from the gas to the liquid. For example, assuming a
saturation partial vapor pressure of for water [29], and a relative humidity of ,
then we obtain . According to the model considered, under these conditions
there would be approximately a zero net evaporation of water at . Of course, this is not an
exact result since many assumptions were required to obtain this model. However, it provides
a qualitative, molecular, mechanistic interpretation of evaporation.
5.3. Bubble Formation
The molecular model of evaporation so far presented still lacks an important contribution to
evaporation, which is bubble formation. When high local temperatures are reached at any
interface other than the liquid/vapor interface, nucleation of bubbles may occur.
Nucleation represents the spontaneous emergence of a new phase at the molecular scale, which
can eventually grow until it is observed at the macroscopic scale. This process also implies the
emergence and growth of new interfaces.
A detailed mathematical description of spontaneous phase emergence is the purpose of an

upcoming report of this series. For that reason, only a general qualitative description of
nucleation will be presented here.
Bubbles, which are formed at other interfaces involving the liquid phase, grow by internal
evaporation of liquid molecules through the newly formed interface. While the migration of
molecules into the bubbles is an evaporation process, those bubbles that remain contained in
the liquid may eventually condense back into the liquid phase. Only bubbles capable of
escaping into the gas phase through the vapor/liquid interface can be considered as effectively
evaporating from the liquid.
The motion of bubbles inside the liquid is influenced by macroscopic forces (gravity,
hydrostatic pressure) as well as molecular forces (Brownian motion, interfacial tension). Only
when bubbles grow and reach a certain critical size, macroscopic forces will dominate. In that
case, bubbles will move towards the vapor/liquid interface due to the difference in density
between the gas and the liquid phases, and when the bubble reaches the interface with a
macroscopic kinetic energy large enough to overcome the vapor/liquid interfacial tension, then
it will abandon the liquid phase.
In summary, the loss of bubbles from the system involves the following steps:
 Nucleation of bubbles at liquid interfaces other than the liquid/vapor interface.
 Growth of the bubbles by evaporation through the liquid/bubbles interfaces.
 Macroscopic motion of the bubbles inside the liquid after reaching a critical size.
 Transfer of bubbles from the liquid to the gas phase through the vapor/liquid interface.

Hugo Hernandez
ForsChem Research
Most heat of evaporation is probably lost by the liquid during the growth of the bubbles rather
than during the transfer of the bubbles through the vapor/liquid interface. However, in the
case of reversible condensation, such heat is recovered by the liquid, so it is only irreversibly
lost during bubble escape.
The main effect of bubble formation is the sudden increase in the rate of evaporation when the
liquid approaches a critical temperature where bubbles are spontaneously formed. Such
temperature is the boiling temperature of the liquid, when the vapor pressure overcomes the
pressure in the liquid phase. In that sense, bubbles formed at the bottom of the container
require slightly higher local temperatures due to the contribution of the hydrostatic pressure of
the liquid.
6. Conclusion
Transfer of molecules from one phase to another is possible when the translational kinetic
energy of the molecule perpendicular to the interface is larger than the corresponding
interfacial energy barrier. The heat involved in this transfer is related to the difference in
average intermolecular potential energy between the two phases ( and ):
〈 〉 〈 〉
(6.1)
In the case of evaporation, where molecules from the liquid phase are transferred to the gas
phase, the corresponding heat of evaporation can be expressed in terms of a general
intermolecular potential function as follows:
̃ ( ) ̃ ( )
( ) [( ) ( ) ]
̃ ( ) ̃ ( )
̃ ( ) ̃ ( )
∑ [( ) ( ) ]
̃ ( ) ̃ ( )
(4.9)
Since the analytical determination of average intermolecular potentials is a difficult task, the
heat of transfer can be determined by the difference between the average kinetic energy of
the molecules being transferred from a phase and the average kinetic energy of the molecules
in such phase:
〈 〉 〈 〉
(6.2)

Hugo Hernandez
ForsChem Research
In the case of evaporation we then obtain (from Eq. 2.7):
( )
( )
√
( )
( )
√ (√ )
(6.3)
The heat of vaporization can also be represented in terms of a reference temperature ( ) by

any of the following relations:
( ) ( ) ∫ ( ( ) ( ))
(6.4)
( ) ( ) ∑ ( )
(6.5)
( ) ( ) (〈 〉 〈 〉)( )
(6.6)
An interesting experimental observation about the heat of evaporation was presented by

Frederick Trouton in the 1880’s [7]. Trouton found that at atmospheric (normal) pressure, the
entropy of vaporization of most compounds was almost identical, with an approximate value
of [8]. Figure 5 shows how Trouton’s rule is a good approximation for substances
with normal boiling temperatures up to . Thus, while Trouton’s rule may work well for
many compounds, the truth is that large deviations are observed, particularly for less volatile
materials.
The almost constant entropy of vaporization observed at atmospheric pressure can be

explained by assuming that:
 The ratio between the molecular densities at the liquid and gas phases, corrected by
the “crowding factor” is approximately constant for all compounds.
 The ratio between the net energy barrier of evaporation at the normal boiling
temperature (at atmospheric pressure) and the “overall” energy barrier of evaporation
is approximately constant for all compounds.

Hugo Hernandez
ForsChem Research
While these two assumptions seem reasonable, deviations in the values of those ratios can also
explain experimental deviations from Trouton’s rule.
Considering the parameters for the vapor pressure model of more than 1400 pure substances,
the following simple linear relations are obtained:
(3.7)
( ) [ ] [ ]
(3.8)
( ) [ ] [ ]
(3.9)
The last coefficient found ( ) is quite close to the value of

obtained for compounds with normal boiling temperatures up to .
Furthermore, using the Clausius-Clapeyron equation we arrive to a similar result (for

):
( )
( )
( ) [ ]
√ ( )
(6.7)
While the heat of vaporization at the normal boiling temperature shows a linear relationship
with respect to the cohesion temperature, the standard heat of vaporization (at )
approximately presents a quadratic relationship:
( )[ ] ( [ ] ) [ ]
(4.18)
On the other hand, the irreversible molar evaporation rate ( ( ) ) can be expressed as:
̃( )
( )
( ) √ ( )
√ ̃( ) ( )
(6.8)
Whereas the reversible molar rate of evaporation ( ( ) ) is:

Hugo Hernandez
ForsChem Research
̃( ) ( )
( ) ( ( ) ( ) )
√ ̃( ) ∑ ( )
(5.12)
where
( )
( ) ( )
( )
(5.13)
Of course, might also change during the evaporation process.
In addition, we need to consider the formation of new phases in the system, and particularly
for this case, bubble formation. Since bubbles can abandon the liquid system, their
contribution is important for the rate of evaporation.
The loss of bubbles from the system involves the following steps:
 Nucleation of bubbles at liquid interfaces other than the liquid/vapor interface.
 Growth of the bubbles by evaporation through the liquid/bubbles interfaces.
 Macroscopic motion of the bubbles inside the liquid after reaching a critical size.
 Transfer of bubbles from the liquid to the gas phase through the vapor/liquid interface.
Acknowledgment and Disclaimer
The author gratefully acknowledges Prof. Jaime Aguirre (Universidad Nacional de Colombia)
for helpful discussions on the topic.
This report provides data, information and conclusions obtained by the author(s) as a result of original
scientific research, based on the best scientific knowledge available to the author(s). The main purpose
of this publication is the open sharing of scientific knowledge. Any mistake, omission, error or inaccuracy
published, if any, is completely unintentional.
This research did not receive any specific grant from funding agencies in the public, commercial, or not-
for-profit sectors.
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International (CC BY-NC
4.0). Anyone is free to share (copy and redistribute the material in any medium or format) or adapt
(remix, transform, and build upon the material) this work under the following terms:
 Attribution: Appropriate credit must be given, providing a link to the license, and indicating if
changes were made. This can be done in any reasonable manner, but not in any way that
suggests endorsement by the licensor.
 NonCommercial: This material may not be used for commercial purposes.

Hugo Hernandez
ForsChem Research
References
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ForsChem Research Reports, 7, 2022-10, 1 - 20. doi: 10.13140/RG.2.2.29272.98566.
[2] Hernandez, H. (2022). Molecular Modeling of Macroscopic Phase Changes 2: Vapor Pressure
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[3] Kirkham, M. B. (2014). Principles of Soil and Plant Water Relations. 2nd Edition. Academic Press,
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[4] Wadsö, I. (1966). A Heat of Vaporization Calorimeter for Work at 25°C and for Small Amounts of
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[13] Chickos, J. S., & Acree Jr, W. E. (2003). Enthalpies of vaporization of organic and organometallic
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[14] Kolasinska, G., & Vera, J. H. (1986). On the prediction of heats of vaporization of pure compounds.
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ForsChem Research
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Molecular Modeling of Macroscopic Phase Changes 3 - Heat and Rate of Evaporation

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Vol.

Molecular Modeling of Macroscopic Phase Changes 3: Heat and Rate of

Clausius-Clapeyron Equation, Cohesion Temperature, Energy Barrier, Heat of Vaporization,

where is a crowding factor in the condensed phase, represents

is the complementary error function, parameter ( ) is expressed in units of pressure per

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2. Theoretical Derivation of the Heat of Evaporation

The heat of evaporation is commonly determined by means of a calorimeter. In this equipment,

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Using Eq. (2.2) and (2.3) in Eq. (2.4) we obtain:

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Then, the corresponding heat of evaporation for this case is:

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As an approximation, we may conclude that:

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compounds. Red line: Normal distribution approximation.

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Table 1. Normal boiling temperature ( ), calorimetric heat of evaporation ( ), and entropy of

Name Formula [K] [ ]

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Name Formula [K] [ ]

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Name Formula [K] [ ]

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Name Formula [K] [ ]

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Combining Eq. (3.7) and (3.8) we obtain:

4. Effect of Temperature and Pressure on the Heat of Evaporation

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where ( ) is the intermolecular potential energy function, ( ) is the probability density

The probability density function of intermolecular distances can be approximated by:

Thus, the average intermolecular potential energy becomes:

which can be alternatively expressed as follows:

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Of course, a more accurate estimation of intermolecular potential energy will be obtained by

Now using Eq. (4.7) and (4.8) in Eq. (2.8) we obtain:

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Also notice that when ̃ ( ) ̃ ( ) the heat of vaporization becomes negligible, as

By equating Eq. (4.10) and (4.11), and solving for ( ), we obtain:

The isobaric heat capacities can be represented as a function of temperature by empirical

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where for the original Shomate equation we have with , ,

Eq. (4.12) can also be expressed in terms of average heat capacities:

Calorimetric heats of vaporization at a standard reference temperature of ( ) are

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Table 2. Calorimetric standard heat of evaporation ( ( ) ) of selected compounds.

Name Formula [ ] Name Formula [ ]

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Table 2 (cont.). Calorimetric standard heat of evaporation ( ( )) of selected compounds.

Name Formula [ ] Name Formula [ ]

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5.1. Irreversible Evaporation Rate

Therefore, the irreversible molar evaporation rate ( ( )) is:

On the other hand, the heat rate of irreversible evaporation ( ̇ ( ) ) is:

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5.2. Reversible Evaporation Rate

In reality, atmospheric pressure exerts an additional resistance to evaporation, which

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Thus, we may state Eq. (5.8) as follows: