Fluid Phase Equilibria 313 (2012) 9196

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Estimation of the vaporization heat

Jing Fan, Xiaoming Zhao , Zhigang Liu
MOE Key Laboratory of Thermo-Fluid Science and Engineering, Xian Jiaotong University, Xian, Shaanxi 710049, China

a r t i c l e

i n f o

Article history:
Received 9 May 2011
Received in revised form
20 September 2011
Accepted 23 September 2011
Available online 1 October 2011

a b s t r a c t
In the present work, a new equation for estimating vaporization heat was developed by applying wagner
vapor pressure equation and using the ClausiusClapeyron equation. The new proposed equation was
valid over the entire range from the triple point to the critical point for most of the substances. The
vaporization heat of 76 pure liquids was calculated to verify the new equation, with the average absolute
deviation 0.80%, compared with the literature values.
2011 Elsevier B.V. All rights reserved.

Keywords:
Vaporization heat
Vapor pressure equation
Estimate

1. Introduction

2. Estimation equation

The vaporization heat of liquid, one of the most important

thermophysical properties, is the amount of heat absorbed in
the process where liquid changes to its vapor at constant pressure or constant temperature. It is widely used in energy and
power, chemistry, new materials and other phase transition elds.
Moreover, this property is sometimes used in the prediction or
correlation of other thermodynamic properties. Values of the
vaporization heat can be obtained by means of calorimetry directly,
or by means of difference between the enthalpy of the saturated vapor and that of the saturated liquid indirectly. Majer
and Svoboda summarized the experimental data of the vaporization heat for a lot of uid [13]. But they still cannot meet the
requirements of chemical engineering process design. Therefore,
estimating becomes an important way. Many equations for estimating the vaporization heat have been reported, which based
on group-contribution method, corresponding-states principle or
residual function [47]. This paper, we estimate the vaporization heat by another method. We proposed a new equation that
is derived from the slope of vapor pressure equations according to the ClausiusClapeyron equation. Seventy-six pure uids
whose average absolute deviation was 0.80% were calculated. The
results demonstrate the accuracy and effectiveness of the new
equation.

2.1. Formula of vaporization heat

Corresponding author. Tel.: +86 29 82668727; fax: +86 29 82668789.

E-mail address: xmzhao@mail.xjtu.edu.cn (X. Zhao).
0378-3812/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2011.09.024

The ClausiusClapeyron equation was established in the phase

equilibria where the pressure and the temperature are identical
between the two phases [1]. The equation is shown as follows
h
dp
=
T (vv vl )
dT

(1)

It relates vaporization heat with vapor pressure. Eq. (1) can be

expressed as
T
dp
h
=
(vv vi )
RTc
RTc
dT

(2)

h
d ln pr
= (Zv Zl )Tr2
RTc
dTr

(3)

d ln pr
h
= ZTr2
RTc
dTr

(4)

pr =

p
,
pc

Tr =

T
Tc

where h is vaporization heat, R is the mol gas constant, Tc is the

critical temperature, pc is the critical
pressure, Tr is the reduced temperature, pr is the reduced pressure, and Zv and
Zl are the compressibility factors of the saturated vapor and the
saturated liquid respectively. If there are a precise vapor pressure
equation and an expression of Z(Zv Zl ), the vaporization heat h
can be calculated. It is easy to measure the saturated pressure and

92

J. Fan et al. / Fluid Phase Equilibria 313 (2012) 9196

Table 1
Parameters of wagner vapor pressure expression.
Substances

Tc (K)

Pc (Mpa)

Parameters
a1

a2

a3

a4

Water
Oxygen
Nitrogen
Carbon dioxide
Benzene
Toluene
Methanol
Methane
Ethane
Propane
Butane
Pentane
Normalhexane
Cyclohexane
Octane
Heptane
Decane
Ethene
Propylene
Propyne
Dodecane
2-Methylpentane
Iso-butane
2, 2-Dimethylpropane
2-Methylbutane
R11
R12
R13
R14
R21
R22
R113
R114
R115
R116
R123
R125
R134a
R141b
R142b
R143a
R152a
R227ea
R236ea
R245fa
R236fa
R245ca
R23
R32
R41
Cyclopropane
Cyclobutane
Cyclopentane
Methylcyclopentane
Methylcyclohexane
Ethylcyclopentane
Ethylcyclohexane
Propylcyclopentane
Propylcyclohexane
Fluoromethane
Trichloromethane
Tetrachloromethane
Chloroethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1,1-Trichloroethane
Pentachloroethane
Hexachloroethane
1-Chloropropane
1,2-Dichloropropane
1,4-Dichlorobutane
1-Butylene
Iso-butylene
1-Pentene
1,2-Dimethylbenzene
1,3-Dimethylbenzene
1,4-Dimethylbenzene

647.14
154.58
126.2
430.8
562.05
591.75
512.64
190.56
305.32
369.83
425.12
469.7
507.82
553.64
569.32
540.13
617.7
282.34
365.57
402.38
658.1
497.7
407.81
433.74
460.35
471.1
385.1
302
227.51
451.48
369.28
487.21
418.83
353.1
293.03
456.831
339.173
374.26
477.5
410.26
345.857
386.41
375.95
412.44
427.2
398.07
447.57
299.293
351.255
317.28
397.8
459.9
511.6
532.7
572.1
569.5
609
603
639
317.8
536.4
561.4
460.4
523
561
550.2
661.3
697.2
503
577
641.2
419.55
417.85
464.65
631.15
618.05
617.15

22.064
5.043
3.398
78.84
4.894
4.1263
8.097
4.599
4.872
4.248
3.796
3.37
3.034
4.075
2.497
2.736
2.103
5.041
4.6646
5.626
1.817
3.04
3.629
3.196
3.3957
4.472
4.13
3.879
3.75
5.1812
4.986
3.3922
3.257
3.12
3.048
3.6618
3.6177
4.059
4.212
4.055
3.761
4.516
2.999
3.50198
3.64
3.2
3.925
4.832
5.782
5.897
5.49
4.99
4.51
3.79
3.47
3.39
3.03
3
2.81
5.88
5.47
4.56
5.27
5.07
5.37
4.41
3.68
3.34
4.58
4.46
3.61
4.022
4
4.052
3.689
3.546
3.475

7.76843
6.04938
6.11542
6.97563
7.01711
7.41301
8.5408
6.01393
6.45394
6.75956
7.02545
7.26189
7.46006
6.95451
7.90803
7.7194
8.47885
6.76934
6.69614
6.87152
8.85962
7.38609
6.88687
6.92955
7.22697
7.21499
6.85423
6.84317
6.75473
7.01314
7.00931
7.18948
7.16923
6.9779
7.28627
7.36373
7.42778
7.53371
7.03256
7.16222
7.30167
7.36004
7.75688
8.92926
7.76621
7.90664
7.74421
7.31305
7.4092
7.08123
6.42838
6.9985
6.82574
7.03781
6.97621
7.09841
7.13994
7.34394
7.09342
6.82469
7.30737
6.15502
6.82361
7.44178
7.56474
6.75539
7.17467
7.02517
6.93145
7.51737
7.47723
6.79812
6.81442
7.09263
6.73572
7.20237
6.66518

1.459811
1.18958
1.184232
1.250583
1.444109
1.656843
0.724622
1.202489
1.272749
1.423091
1.478153
1.47843
1.441315
1.284642
1.472804
1.499644
1.788442
2.085485
1.428189
0.81216
1.766895
1.469137
1.394569
1.387105
1.608814
1.96948
1.341224
1.408728
1.075813
1.501468
1.255321
1.332907
1.265836
0.758421
1.525868
1.427438
1.318671
1.304033
1.344248
1.484617
1.413673
1.397174
1.54117
4.416984
1.453368
1.700685
1.515179
1.437662
1.444616
1.537786
1.020027
1.086578
1.172589
1.215227
1.01435
0.897328
1.29938
1.508954
0.777609
1.080839
1.843019
0.087358
1.24332
1.924502
1.766062
1.069411
1.261155
1.080453
0.938156
2.082238
1.098552
1.108619
1.059918
0.547032
0.30302
0.608242
0.65996

2.75676
1.00523
1.135
3.31423
2.94363
3.21159
2.87279
0.84191
1.6093
2.27656
2.56501
2.96038
3.37085
2.65882
4.28428
3.84525
5.45598
2.5086
2.31897
0.4243
6.19907
3.21134
2.54961
2.83456
2.85694
3.09836
2.32729
2.46701
1.79524
3.1974
2.55239
2.92114
2.72261
1.72974
3.33647
3.3242
3.34822
3.32341
2.77363
2.9458
2.71771
2.78135
3.94557
10.7577
4.42418
4.67942
3.82843
2.83192
2.63985
2.36843
1.87942
1.59153
2.55917
2.61134
2.32206
2.25748
2.99901
3.69161
0.42362
1.76451
2.82835
1.15599
2.80628
3.12967
3.26824
2.46835
3.08146
2.84295
1.95676
3.56075
2.99869
2.42766
1.97556
1.00555
0.76356
2.35902
0.383

1.32923
1.36549
1.64156
4.112915
2.25572
2.07493
0.273389
1.29752
1.38115
1.26995
1.56226
1.75459
1.65146
2.7266
2.34063
2.13472
2.00793
0.83961
1.12759
0.83072
2.89958
1.89419
1.41781
0.50428
1.82485
1.14584
1.90672
1.68664
2.66395
0.43032
2.04292
2.71278
2.98747
4.49472
0.14017
2.25104
2.18906
2.59457
2.41787
1.80308
2.14522
2.0902
2.80846
28.491
1.86836
1.35599
2.54325
1.77213
1.81491
0.52565
0.89001
1.93706
0.74597
2.45231
3.39796
4.17562
6.32522
4.23476
35.1815
2.22873
2.55498
4.65721
0.0829
1.90942
0.1933
1.66793
1.65775
2.34233
3.43752
2.40133
2.06573
1.12454
2.94155
2.55111
7.2609
2.74432
6.30718

J. Fan et al. / Fluid Phase Equilibria 313 (2012) 9196

93

Table 2
Heat of vaporization calculation results of different estimated models compared with literature values.
Substances

Tr

Number of Points

R12
R32
R113
R152a
R142b
R143a
R123
R22
R134a
R227ea
R115
R245fa
Methane
Propane
Pentane
Normalhexane
Cyclohexane
Octane
Decane
Propylene
Oxygen
Benzene
Toluene
Carbon dioxide
Nitrogen
Ethane
Butane
R23
Water
Methanol
R245ca
R116
R114
R21
R14
R13
R11
Ethene
Propyne
Iso-butane
2,2-Dimethylpropane
2-Methylbutane
2-Methylpentane
Heptane
Cyclopropane
Cyclobutane
Cyclopentane
Methylcyclopentane
Methylcyclohexane
Ethylcyclopentane
Ethylcyclohexane
Propylcyclopentane
Propylcyclohexane
Fluoromethane
Trichloromethane
Tetrachloromethane
Chloroethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1,1-Trichloroethane
Pentachloroethane
Hexachloroethane
1-Chloropropane
1,2-Dichloropropane
1,4-Dichlorobutane
1-Butylene
Iso-butylene
1,2-Dimethylbenzene
1,3-Dimethylbenzene
1,4-Dimethylbenzene
Average absolute deviations

0.340.98
0.390.97
0.500.97
0.410.98
0.350.98
0.480.97
0.370.96
0.350.98
0.460.96
0.400.97
0.510.98
0.470.95
0.500.97
0.270.97
0.310.98
0.350.98
0.510.96
0.380.97
0.400.97
0.310.97
0.390.97
0.500.97
0.310.97
0.720.99
0.510.95
0.310.97
0.320.98
0.400.97
0.420.97
0.350.98
0.450.95
0.600.97
0.660.99
0.440.99
0.440.99
0.310.98
0.360.96
0.370.53
0.680.97
0.280.98
0.600.98
0.260.92
0.250.96
0.340.97
0.530.98
0.460.99
0.410.96
0.400.96
0.470.97
0.480.97
0.510.97
0.520.98
0.640.93
0.670.98
0.540.84
0.450.81
0.460.85
0.480.94
0.480.99
0.460.93
0.470.90
0.470.97
0.500.94
0.470.96
0.480.86
0.460.98
0.460.99
0.430.88
0.400.96
0.470.86
2.09

50
41
46
23
52
35
55
24
38
44
34
42
19
27
64
64
50
67
72
49
19
52
79
16
13
21
29
34
72
33
46
23
29
50
26
42
29
10
24
59
34
69
72
69
9
13
15
16
15
15
15
15
10
6
9
11
11
13
15
14
15
18
14
15
13
11
12
13
18
13
1.76

Note: Dev . % = 100(hliterature hestimation )/hliterature .

Dev.%
Haggenmacher [13]

Pitzer [1]

Morgan [15]

This work

2.5
0.8
2.5
0.84
1.56
0.73
1.25
1.8
0.69
0.47
3.47
1.01
5.68
2.9
1.76
1.26
0.85
0.32
0.95
2.41
4.69
2.91
0.55
4.6
5.5
3.04
2.03
0.6
0.63
3.96
0.67
2.96
4.52
2.36
4.19
2.41
1.36
0.14
2.36
2.23
3.52
1.26
0.75
1.01
5.16
2.58
1.84
1.41
2.76
1.93
3.24
1.99
2.09
4.37
1.84
2.49
1.36
0.87
1.68
2.28
1.39
1.1
1.65
1.94
1.08
2.67
3.08
1.32
1.27
0.74
2.13

1.18
2
2.44
0.48
1.38
0.47
2.03
1.19
1.32
2.4
1.2
1.93
1.41
0.75
1.3
1.4
9.88
2.41
2.85
0.9
1.59
1.76
1.79
1.55
0.75
1.1
0.8
0.58
1.75
5.78
1.6
1.74
2.12
1.23
1.51
1.29
1.22
0.16
1.1
1.17
1.6
1.32
2.19
2.27
0.51
2.56
1.19
1.24
1.82
1.72
3.61
4.48
2.91
0.86
1.63
0.75
5.96
1.17
0.83
1.06
2.42
1.77
0.25
1.89
2.21
1.17
1.32
1.06
1.64
0.41
0.80

0.8
4.54
0.48
2.89
1.03
2.61
1.15
1.28
1.88
1.85
1.53
1.69
1.96
1.21
0.91
1.43
7.1
1.99
2.51
1.4
2.24
0.9
1.86
1.94
1.01
1.89
1.24
2.93
4.7
11.27
2.56
0.75
0.73
1.06
1.41
0.56
0.86
0.88
2.32
0.83
0.87
1.19
1.35
0.13
1.24
4.37
1.52
2.9
0.39
2.63
2.53
7.65
2.02
2.47
0.69
0.95
8.39
3.51
3.11
0.79
0.26
2.43
2.44
0.35
0.64
1.51
1.45
2.36
3.89
3.2

0.25
1.78
0.9
0.79
0.19
0.88
0.42
0.21
0.23
0.58
0.87
1.64
0.46
0.22
0.31
0.37
1.15
1.44
1.51
0.43
0.19
0.5
0.6
0.5
0.41
0.33
0.23
1.04
0.6
0.93
0.4
0.96
1.41
0.3
0.92
0.32
0.71
0.33
0.99
0.25
0.46
0.32
0.31
0.55
0.56
2
0.63
1.07
1.03
0.9
1.18
1.03
1.26
1.43
0.94
1.38
0.78
1.21
1.07
0.96
0.69
1.18
1.17
0.56
1.17
1.44
1.01
1.23
1.06
0.75

94

J. Fan et al. / Fluid Phase Equilibria 313 (2012) 9196

1.1

1.1
Literature
This work
Haggenmacher

1.0
0.9

0.9

0.8

0.8

0.7

0.7

0.6

Literature
This work
Haggenmacher

1.0

0.5

0.6
0.5

0.4

0.4

0.3

0.3

0.2
0.3

0.4

0.5

0.6

0.7

0.8

0.9

Tr
Fig. 1. Plot of Z of R12 versus the reduced temperature Tr .

1.0

0.2

0.3

0.4

0.5

0.6

Tr

0.7

0.8

0.9

1.0

Fig. 2. Plot of Z of butane versus the reduced temperature Tr .

Fig. 3. The uniformity of the calculation results and literature values (from 76 substances). h: vaporization heat; Tr : reduced temperature; () NIST; (

) this work.

J. Fan et al. / Fluid Phase Equilibria 313 (2012) 9196

95

Fig. 4. The comparison of the absolute deviation between this work and previous models. Dev.%: absolute deviation; Tr : reduced temperature; () this work; (
( ) Pitzer.

temperature in the research of thermophysical properties [812],

and the expression of vapor pressure can be gained according to
the saturated pressure and temperature. This work, we choose a
familiar wagner vapor pressure equation. It is as
a1  + a2 1.5 + a3 3 + a4 6
ln pr =
1

(5)

one we proposed for estimating vaporization heat. Table 1 shows

the parameters of some substances.
2.2. Function of Z(Zv Zl )
There is a published empirical formula by Haggenmacher in
1946 [13]. The form is

We derivate Eq. (5), which results in the following equation

a1 + 1.5a2
d ln pr
=
dTr

0.5

+ 3a3
1

2

+ 6a4

vv vl =

5

a1  + a2 1.5 + a3 3 + a4 6
( 1)2

RT
Mp


Z =

( 1)

(7)

h
= Z[( 1)(a1 + 1.5a2 0.5 + 3a3 2 + 6a4 5 )
RTc
(a1  + a2 1.5 + a3 3 + a4 6 )]

pr
Tr3

(9)

Pr

0.5
(10)

Tr3

We found that the exponent of Tr in Eq. (10) was not a constant

but a function of the temperature in our study. Therefore, we made
the improvement to Haggenmachers expression as follows

a1 + 1.5a2 0.5 + 3a3 2 + 6a4 5

1

a1  + a2 1.5 + a3 3 + a4 6

Introduce the equation of state pv = ZRT to Eq. (9), and it becomes

(6)

Introducing Eq. (6) to Eq. (4) yields

h
= ZTr2
RTc

) Morgan;


Z =

pr

0.5
(11)

TrA

According to Eq. (11), A is given by

(8)

Here  = 1 Tr ; a1 , a2 , a3 , and a4 are constants which can be tted

from values of the saturated temperature and pressure. Eq. (8) is the

A = f (Tr ) = B + C

Tr
ln Tr

(12)

Respectively, each liquid was corresponding with a set of values

of parameters B and C. By comparing the values, we noticed that C

96

J. Fan et al. / Fluid Phase Equilibria 313 (2012) 9196

did not vary with the liquid obviously, so we regarded C as a constant. Then, we observed that B varied with the substances acentric
factor, which is shown in the following expression
B = exp(0 + 1 2 )

(13)

Here is the acentric factor; C = 0.023,  0 = 0.8426,  1 = 1.4227, and

 2 = 1.4207. Figs. 1 and 2 show the curves of Z Tr of the two
representative substances R12 and Butane.
3. Calculation of vaporization heat
Vaporization heat can be calculated when introducing Eqs.
(11)(13) into Eq. (8). To test the performance of the new equation,
2190 points of 76 pure uids were estimated. The average absolute
deviation was 0.80%, which compared with the literature values
[14]. Most of the deviations of calculated points were between 0 and
1 percent. The calculation results of 76 pure uids in comparison
with some previous models have been shown in Table 2.
The uniformity of the calculation results and literature values
[14] is reected further in Fig. 3. There are four curves of four pure
substances chosen from the 76 pure substances.
The results calculated by the new function of Z, in contrast
with the ones calculated by Haggenmachers formula, were owning
higher accuracy. The absolute deviations of Morgans and Pitzers
method are larger than 1 percent. On the contrary, the new equation
was valid over the entire range, and most of the absolute deviations
ranged from 0 to 1 percent. The absolute deviation curves of this
works method and some previous models are shown in Fig. 4.
4. Conclusion
This paper has proposed a new expression of the difference of
compressibility factors between the saturated vapor and the saturated liquid, and on such a basis, a simple accurate new equation
was constructed to estimate vaporization heat. Some uids have
been estimated, and their average absolute deviation was less than
1 percent which meet the engineering design. The results suggest
that it is available and precise to apply the developed equation to
the calculation of vaporization heat of pure uid.

List of symbols
h
vaporization heat
R
mol gas constant
critical temperature
Tc
pc
critical pressure
Tr
reduced temperature
reduced pressure
pr
Z
compressibility factor
a0 a4
tting parameters
A
exponent
variable quantity
B
C
constant
Greek letters
 0  3
constants

acentric factor
Acknowledgment
We acknowledge the support of the National Natural Science
Foundation of China (Grant No. 50836004 and Grant No. 50776072).
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