Journal of Advanced Research (2014) 5, 261269

Cairo University

Journal of Advanced Research

ORIGINAL ARTICLE

An ecient reliable method to estimate the

vaporization enthalpy of pure substances according
to the normal boiling temperature and critical
properties
Babak Mehmandoust, Ehsan Sanjari *, Mostafa Vatani
Mechanical Engineering Department, Khomeinishahr Branch, Islamic Azad University, P.O. Box 119-84175, Isfahan, Iran

A R T I C L E

I N F O

Article history:
Received 24 December 2012
Received in revised form 21 March
2013
Accepted 26 March 2013
Available online 31 March 2013
Keywords:
Enthalpy
Vaporization
Correlation
Pure substances
Normal boiling temperature

A B S T R A C T
The heat of vaporization of a pure substance at its normal boiling temperature is a very important property in many chemical processes. In this work, a new empirical method was developed
to predict vaporization enthalpy of pure substances. This equation is a function of normal boiling temperature, critical temperature, and critical pressure. The presented model is simple to use
and provides an improvement over the existing equations for 452 pure substances in wide boiling range. The results showed that the proposed correlation is more accurate than the literature
methods for pure substances in a wide boiling range (20.3722 K).
2013 Cairo University. Production and hosting by Elsevier B.V. All rights reserved.

Introduction
Vaporization enthalpies are used frequently in adjusting
enthalpies of formation of liquids to the standard state and
in evaluating environmental transport properties. Accurate
thermodynamic correlations are required to enhance the reli* Corresponding author. Tel.: +98 311 366 00 11.
E-mail addresses: sanjary@gmail.com, sanjari@iaukhsh.ac.ir (E.
Sanjari).
Peer review under responsibility of Cairo University.

Production and hosting by Elsevier

ability of such simulations. Of the thermodynamic properties,

heat of vaporization is one of the most important parameters
for a multi-component multistage vaporliquid equilibrium
process as it is the one which controls the temperature as well
as liquid and vapor proles in a column [1]. Moreover, this
property is sometimes used in the prediction or correlation
of other thermodynamic properties. There is thus engineering
and theoretical interest in the measurement and correlation
of values of this property [212].
The normal boiling enthalpy can be calculated using either
equations of state applied to the liquid and vapor phases or
more simply by means of empirical correlations that allow calculating the enthalpy of vaporization of pure uids [622].
Some of them are general analytical expressions that only require as input parameters certain properties of the uid, such

2090-1232 2013 Cairo University. Production and hosting by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jare.2013.03.007

262

B. Mehmandoust et al.

as the critical temperature, critical pressure, normal boiling

point temperature, and molecular weight [6,23].
In this study, an accurate empirical correlation was presented by incorporating the normal boiling temperature and
critical points of the pure substances. This equation can predict
the heat of vaporizations for pure substances over the entire
range of normal boiling point temperatures of practical interest.

Table 1 Tuned coefcients of new

proposed model.

Methodology
In this research, we considered some of well known analytical
models that do not require specic adjustable coefcients for
each substance, but rather are based on a knowledge of some
properties of the liquidvapor equilibrium (critical properties
mainly) or on molecular properties. In particular, we selected
seven specic expressions that are valid only for the calculation
of the vaporization enthalpy. These are including the correlation of Riedel [13], Chen [15], and Zhao et al. (ZNY) [17], the
simplest method dened as Trouton rule [19], two models presented by Vetere [20,21] and a more recent proposal of Liu [22].
Riedel model [13]
DHmb 1:093 RTb

lnPc  1:013
0:93  Tb =Tc

Coecients

Values

A
b1
b2
b3
c1
c2
c3
d1
d2
d3

0.01290
0.00086
0.00206
0.01150
0.01983
0.00632
0.04279
0.02086
0.00459
0.03544


DHmb RTb


0:0627
Tb
220

1  Tb =Tc 0:38 lnPc =Pa

1  Tb =Tc 0:38Tb =Tc lnTb =Tc

where Pa is atmospheric pressure in bar.

1
New proposed vaporization enthalpy correlation
1

where DHvb is vaporization enthalpy (J mol ), R is universal gas

constant (8.3145 J mol1 K1), Tb is normal boiling point (K),
Tc is critical temperature (K), and Pc is critical pressure (bar).
Chen model [15]
DHmb RTb

3:978Tb =Tc  3:958 1:555lnPc

1:07  Tb =Tc

Trouton rule [19]

DHmb 88 Tb J mol1

Zhao et al. model (ZNY) [17]

DHmb Tb 36:6 8:314lnTb

Vetere model (V-79) [21]

DHmb RTb A BTbr CT2br DT3br

DHmb RTb


In this study, we tried to nd a more accurate and rapid model

to calculate vaporization enthalpies of pure substances based
on experimental data [14,2426]. Thermophysical properties
of compounds are obtained from the literatures [6,23]. By
investigation of more than 452 data points vaporization enthalpy of pure substances and using 352 points of them in multiple regression analysis, a new empirical correlation is
suggested to accurately prediction of vaporization enthalpy
with the wide ranges of normal boiling temperatures (20.3
722 K).
The new presented model has three dependent variables
(Pc, Tc, and Tb) and 10 independent variables as follows:

1  Tb =Tc 0:38 lnPc  0:513 0:5066T2c =Pc T2b 

B b1 b2 Pc b3 lnPc

10

1  Tb =Tc 1  1  Tb =Tc 0:38 lnTb =Tc

5

90

Vetere model (V-95) [20]

For hydrocarbons:


0:0068Tb 0:0009T2b
DHmb 4:1868Tb 9:08 4:36log10 Tb

M
M
6
For alcohols:

6:37Tb
DHmb 4:1868Tb 18:82 3:34log10 Tb 
M

0:036T2b 5:2  105 T3b


M
M
where M is molecular weight (kg/kmol).
Liu [22]

Calculated Enthalpy (kJ/mol)

80
70
60
50
40
30
20
10
0

10

20

30

40

50

60

70

80

90

Measured Enthalpy (kJ/mol)

Fig. 1 Accuracy of presented model versus experimental data

points from the literatures.

Estimation of the boiling vaporization enthalpy of pure substances

Table 2
models.

263

Average absolute relative deviation of the values obtained by presented correlation in comparison with other empirical

Hydrocarbon type

C10H12
C10H14
C10H18
C10H20O2
C10H22
C10H22O
C10H7Br
C10H7Cl
C10H8
C11H10
C11H24
C12H10O
C12H26
C12H27N
C13H28
C14H12O2
C15H32
C2H2Br4
C2H2Cl2
C2H2Cl4
C2H3Br
C2H3Cl
C2H3Cl2F
C2H3Cl3
C2H3F3
C2H3N
C2H4
C2H4Br2
C2H4Cl2
C2H4F2
C2H4O
C2H4O2
C2H5Br
C2H5Cl
C2H5ClO
C2H5I
C2H5NO2
C2H6
C2H6O
C2H6O2
C2H6OS
C2H6S
C2H6S2
C2H7N
C2H7NO
C2H8N2
C2HBrClF3
C2HCl3
C2HCl5
C2HF3O2
C2N2
C3Cl2F6
C3H3N
C3H4O
C3H5Br
C3H5Cl
C3H5Cl3
C3H5ClO2
C3H5N

Number of isomers

1
2
2
2
5
1
1
1
1
1
8
1
2
1
1
1
1
1
3
1
1
1
1
2
1
1
1
1
2
1
2
2
1
1
1
1
1
1
2
1
1
2
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1

AARD%
Liu [22]

V-95 [20]

V-79 [21]

Riedel [13]

Chen [15]

ZNY [17]

Trouton [19]

This study

2.29
1.79
1.34
6.28
1.10
7.35
2.74
7.88
1.70
2.38
2.69
0.12
4.12
3.18
3.74
3.12
2.86
7.86
3.86
2.49
11.40
3.60
0.82
1.71
2.19
8.11
2.22
2.21
0.33
2.33
1.04
6.18
2.74
1.19
2.40
3.76
5.03
1.92
3.39
7.87
0.99
0.84
0.36
5.01
0.56
1.83
1.50
0.04
0.25
3.73
3.50
4.78
3.50
3.11
0.78
8.62
2.47
3.37
3.22

2.58
8.68
6.09
4.00
5.36
15.77
5.40
3.54
7.24
7.87
4.43
3.70
2.69
3.87
2.16
0.24
1.29
3.99
1.98
0.25
6.14
7.80
1.22
1.33
0.85
14.94
3.57
3.55
0.63
1.74
1.65
29.70
0.25
1.59
9.51
2.51
5.32
5.32
6.98
6.41
4.16
2.87
3.09
5.14
12.00
2.35
1.12
1.56
5.24
8.09
6.45
0.54
0.39
4.96
0.05
2.54
5.40
6.29
9.99

3.87
1.88
3.04
5.07
0.69
7.45
0.49
9.64
0.34
0.38
1.98
1.20

10.73
4.20
3.74
12.69
4.58
0.48
2.35
0.09
8.41
1.02
0.77
0.32
0.52
2.28
31.86
3.31
0.49
0.82
3.47
5.00
0.74
1.21
8.47
2.59
0.61
1.47
3.46
3.34
2.62
1.20
0.53
1.50
1.40
1.39
3.89
3.17
3.75
0.81
8.92
1.29
3.06
3.06

1.95
2.62
1.96
5.06
2.21
9.52
3.06
7.47
1.39
2.56
1.94
1.88

10.41
4.28
2.51
14.66
4.53
0.23
1.39
0.73
11.06
0.19
1.62
1.92
0.58
4.21
34.98
4.90
0.22
5.24
4.69
2.10
0.21
2.63
4.69
0.56
0.18
0.33
1.28
13.01
7.34
0.07
0.52
0.91
3.56
0.69
3.42
0.90
5.94
2.47
8.96
3.03
0.64
5.08

2.86
2.26
2.61
4.60
0.63
8.06
1.85
8.56
0.65
1.51
1.62
0.22

10.61
4.26
3.07
14.45
4.50
0.11
1.80
0.32
10.11
0.17
1.41
1.45
0.15
3.84
33.48
4.61
0.01
2.38
4.46
3.11
0.24
0.96
5.95
1.11
0.04
0.52
1.95
8.03
5.69
0.61
0.17
1.31
0.82
0.19
3.92
1.78
5.22
1.96
9.08
2.24
0.94
4.24

3.69
2.89
0.33
8.10
0.96
10.86
0.18
9.31
0.16
0.79
1.04
2.18
2.20
8.03
2.67
5.40
3.39
6.07
4.66
3.21
3.37
3.47
1.45
2.58
2.86
1.87
0.76
0.71
3.75
5.09
5.87
25.19
2.80
3.18
16.11
0.03
12.24
0.48
13.51
18.24
6.05
3.06
3.25
11.48
22.20
11.45
2.53
1.82
2.16
11.42
10.79
1.54
8.29
2.50
3.36
7.26
0.89
11.25
0.16

3.63
4.75
3.53
1.36
0.72
2.20
7.81
5.59
1.60
1.57
11.73
1.23
1.08
1.23
10.12
0.96
0.03
1.19
0.16
0.75
1.18
1.10
3.03
2.93
2.31
1.21
8.13
3.34
3.12
1.49
7.23
6.58
4.44
1.76
6.64
10.44
2.49
4.25
1.89
4.00
8.66
10.66
9.94
3.59
3.04
0.28
2.27
2.49
4.68
0.91
4.95
6.42
10.17
1.46
2.44
0.07
1.34
0.78
1.31
0.90
1.21
0.85
24.56
2.73
1.42
1.81
1.91
1.08
14.60
1.46
3.32
2.13
10.34
7.23
10.55
1.61
10.70
0.85
18.02
10.75
5.64
4.05
1.22
1.45
1.48
2.46
6.66
5.03
21.56
3.22
9.60
0.18
1.33
1.21
0.99
1.09
3.25
0.56
8.52
5.81
4.93
2.86
2.88
0.73
5.40
4.83
1.29
2.17
0.11
0.34
3.43
8.42
2.03
0.56
9.68
6.39
2.44
1.82
(continued on next page)

264
Table 2

B. Mehmandoust et al.
(continued)

Hydrocarbon type

Number of isomers

AARD%
Liu [22]

V-95 [20]

V-79 [21]

Riedel [13]

Chen [15]

ZNY [17]

Trouton [19]

This study
1.03
6.55
2.63
1.96
3.44
2.52
2.14
0.41
1.04
4.86
3.71
2.14
3.22
0.82
1.56
0.72
3.32
1.95
2.58
4.43
2.08
1.56
3.48
0.03
0.96
0.36
1.93
0.49

C3H6
C3H6Br2
C3H6Cl2
C3H6O
C3H6O2
C3H6S
C3H7Br
C3H7Cl
C3H7I
C3H7NO2
C3H8
C4H10
C5H12
C5H12S
C5H13N
C6H10
C6H10O
C6H10O2
C6H10O3
C6H10O4
C6H12
C6H12O
C6H12O2
C6H12S
C6H13Cl
C6H13N
C6H14
C6H14O

2
1
1
4
2
1
2
2
2
2
1
2
3
6
2
1
1
1
1
1
21
7
7
1
1
1
5
10

1.22
9.48
1.12
3.09
2.53
0.49
3.29
0.57
2.36
2.29
1.34
0.67
1.08
1.17
0.73
0.35
2.34
6.51
1.76
11.47
4.29
1.21
3.55
1.61
0.69
2.00
0.23
6.30

4.47
3.25
1.57
5.03
2.19
4.67
2.17
3.96
3.50
2.16
4.40
6.46
7.44
5.56
1.91
5.86
2.67
0.49
2.11
0.65
5.32
3.21
1.07
7.59
4.10
3.73
7.28
9.85

0.35
9.14
1.80
2.66
1.95
1.36
3.33
0.52
1.54
2.29
3.55
0.27
1.51
1.71
0.77
1.03
2.85
9.14
3.17
15.69
3.59
1.21
3.75
0.07
0.99
1.55
0.17
5.15

0.18
12.64
0.15
2.21
1.01
0.61
4.91
1.30
2.45
0.75
4.39
0.46
2.20
1.85
2.00
0.44
1.06
16.55
9.27
27.19
3.50
1.93
4.31
1.20
0.95
4.09
0.48
4.11

0.13
11.46
0.84
2.32
0.89
0.75
4.49
0.96
2.14
0.51
3.99
0.42
1.84
1.69
1.17
0.75
1.97
12.16
5.78
19.52
3.63
1.45
3.86
0.66
0.15
3.03
0.17
4.23

0.78
0.54
3.35
8.46
7.44
2.35
1.04
0.81
0.89
8.48
0.50
1.55
2.59
0.90
3.59
0.10
3.42
4.70
7.26
4.35
2.74
2.31
4.25
1.49
0.93
2.48
2.29
12.37

6.60
2.07
1.43
5.01
3.92
0.24
2.43
3.42
3.55
6.77
6.97
7.60
7.54
2.48
1.54
2.89
1.73
3.15
6.48
3.86
4.33
1.20
2.22
2.59
0.69
0.86
6.04
12.19

C6H14O2
C6H14O3
C6H14S
C6H15N
C6H4Cl2
C6H4F2
C6H5Cl
C6H5F
C6H6
C6H6ClN
C6H6O
C6H6S
C6H7N
C7H12
C7H14
C7H14O
C7H14O2
C7H16
C7H16O
C7H5F3
C7H5N
C7H6O
C7H6O2
C7H7Cl
C7H7F
C7H8
C7H8O
C7H9N
C8H10

4
3
4
6
3
3
1
1
1
1
1
1
4
1
17
6
6
9
5
1
1
1
1
2
2
1
5
9
4

8.26
11.75
1.99
1.62
1.71
1.79
0.95
2.49
0.16
3.02
1.53
3.83
0.96
7.96
3.07
4.59
3.08
0.53
2.43
2.01
2.35
1.13
6.25
1.03
2.38
0.60
3.34
1.49
11.85

2.21
10.20
3.68
3.49
5.45
1.72
4.93
3.00
5.09
2.00
5.42
3.13
3.26
6.31
9.37
7.05
1.06
7.15
4.49
2.02
4.21
0.13
15.36
4.62
2.18
5.75
4.83
3.03
17.47

8.79
13.29
2.76
2.28
1.34
1.98
0.24
2.55
0.39
2.05
1.90
3.16
0.86
9.77
1.93
3.99
3.65
0.43
4.19
2.36
3.77
2.04
27.39
1.02
2.86
0.19
3.92
1.39
11.22

7.81
19.22
4.00
4.99
2.11
3.17
0.96
4.67
0.44
5.73
2.26
6.49
2.29
11.53
2.04
1.81
5.78
0.41
9.48
1.21
11.00
0.85
35.79
1.45
2.57
1.02
3.43
3.67
12.76

8.45
15.70
2.94
3.46
1.79
2.71
0.50
3.87
0.14
4.21
0.84
5.20
1.47
11.47
1.94
3.06
4.28
0.27
6.28
1.89
7.11
0.28
31.69
1.00
2.51
0.48
3.07
2.30
11.85

6.67
4.80
1.72
1.81
0.55
2.34
0.46
1.91
1.05
4.52
12.88
3.37
3.92
1.00
3.85
8.81
3.55
2.19
3.83
1.23
11.35
6.98
8.01
1.14
3.47
0.34
11.07
3.85
10.92

4.78
7.60
5.87
8.81
1.19
1.41
1.94
1.15
1.22
1.09
0.43
1.00
1.25
0.72
0.97
1.08
1.99
0.75
4.48
1.18
12.36
2.13
2.53
0.39
2.68
1.64
3.73
5.34
6.49
1.66
8.17
2.14
2.08
2.42
5.11
1.64
3.42
1.84
1.20
1.63
10.99
3.81
6.38
4.40
8.31
2.15
1.19
1.10
2.08
3.27
1.89
0.41
10.69
3.04
3.13
1.52
12.45
0.82
(continued on next page)

Estimation of the boiling vaporization enthalpy of pure substances

(continued)

Hydrocarbon type

C8H10O
C8H11N
C8H14
C8H14O3
C8H16
C8H16O
C8H16O2
C8H17F
C8H18
C8H18O
C8H18S
C8H19N
C8H8
C8H8O
C8H8O3
C9H10
C9H10O2
C9H18
C9H20
C9H7N
CH2Br2
CH2Cl2
CH2I2
CH2O2
CH3Br
CH3Cl
CH3I
CH3NO2
CH4
CH4O
CH5N
CHBr3
CHCl3

Number of isomers

1
2
4
1
11
1
1
1
19
4
1
2
1
1
1
1
1
1
5
2
1
1
1
1
1
1
1
1
1
1
1
1
1

AARD%
Liu [22]

V-95 [20]

V-79 [21]

Riedel [13]

Chen [15]

ZNY [17]

Trouton [19]

This study

3.95
0.75
5.31
9.31
1.79
10.84
4.07
10.27
1.47
3.83
4.73
3.96
5.39
0.70
5.88
1.21
9.63
2.51
1.76
3.36
1.85
2.08
7.26
7.60
2.52
0.51
3.08
3.72
1.71
0.15
3.56
6.31
0.18

2.55
3.07
1.42
12.69
8.29
3.86
0.11
6.64
6.89
4.59
15.05
2.56
0.26
1.64
0.78
5.95
8.39
8.98
8.05
1.43
1.13
1.76
4.15
59.43
0.83
0.71
0.29
3.33
7.08
6.09
4.94
5.62
0.27

4.19
1.46
5.90
7.23
1.62
12.90
4.00
9.42
0.64
4.82
7.70
6.10
6.43
1.84
6.45
0.24
10.05
2.02
1.73
5.34
1.28
1.77
9.51
51.90
3.73
1.04
3.46
3.81
3.65
2.55
1.57
7.96
0.11

10.20
0.98
4.70
0.47
1.84
14.67
1.65
6.49
1.02
7.13
10.80
12.52
5.07
0.98
13.06
1.53
6.71
3.94
2.30
3.07
2.73
0.68
9.30
55.57
4.93
1.68
4.77
6.79
1.39
8.59
0.95
7.35
1.25

7.40
0.28
5.45
4.86
1.85
14.45
3.06
8.34
0.61
5.27
10.39
8.43
5.71
0.27
9.59
0.75
8.50
2.77
1.93
3.85
2.62
0.87
9.38
54.58
4.99
1.67
4.72
6.02
1.31
6.51
0.54
7.43
0.96

9.14
2.84
3.93
16.91
2.91
0.82
4.11
10.86
1.95
3.60
10.28
2.75
6.23
5.09
6.31
0.50
13.36
3.41
3.17
7.95
3.56
5.83
6.31
41.58
3.56
4.01
2.49
5.44
3.36
18.46
13.44
7.52
2.90

9.14
2.04
2.29
16.73
4.84
0.80
2.84
9.55
4.13
4.12
11.72
1.81
4.92
4.93
6.53
0.17
13.40
4.59
4.85
8.45
1.05
1.79
5.76
45.11
1.82
2.42
1.62
3.08
19.99
15.59
8.28
6.31
0.62

1.18
2.70
4.87
0.96
0.77
6.54
3.69
9.17
1.62
2.91
1.62
1.72
6.78
4.08
0.38
1.08
0.65
2.80
2.72
7.05
0.81
3.12
10.09
1.87
0.20
1.25
0.98
2.05
6.06
1.80
2.87
9.29
0.85

C c1 c2 Pc c3 lnPc

11

D d1 d2 Pc d3 lnPc

12
1

In this equation, DHvb is vaporization enthalpy (kJ mol ), R

is universal gas constant and equals to 8.3145 J mol1 K1,
Tb (K) is normal boiling temperature, Tc (K) is critical temperature, Tbr is reduced temperature dened as Tb/Tc, and Pc (bar)
is critical pressure. Also, tuned coefcients that have been
determined by minimizing the sum of square errors of the
model are presented in Table 1.

Table 3 Statistical parameters of this study compared with

other methods.
Liu [22]
V-95 [20]
V-79 [21]
Riedel [13]
Chen [15]
ZNY [17]
Trouton [19]
This Study

AARD%

ARD%

RMSD

3.05
5.44
3.28
3.95
3.47
4.49
4.91
2.28

0.090
3.091
0.046
2.121
0.982
2.298
0.033
0.025

4.28
7.79
7.21
8.63
7.87
7.56
7.67
3.61

Results and discussions

We carried out regression analysis for 352 pure substances and
also for 100 other substances which are not participate in
1
0.9

Cumulative frequency %

Table 2

265

0.8
0.7
0.6
0.5
0.4

Liu [22]
V-95 [20]

0.3

V-79 [21]
Riedel [13]

0.2

Chen [15]
ZNY [17]

0.1

Trouton [19]
This study

10

12

14

AARD%

Fig. 2 AARD% of various methods in calculating vaporization

enthalpies as function of cumulative frequency.

266

B. Mehmandoust et al.

Table 4 Average absolute relative deviation of the values obtained by presented correlation in comparison with other empirical
models for 100 new data.
Hydrocarbon type

CH6N2
C2Br2ClF3
C2Cl2F4
C2Cl3F3
C2Cl4
C2ClF5
C2F6
C4F10
C4F8
C4H10O
C4H10O2
C4H10S
C4H11N
C4H4N2
C4H4O
C4H4S
C4H5N
C4H6
C4H6O2
C4H6O3
C4H7N
C4H8
C4H8O
C4H8O2
C4H9Br
C4H9Cl
C4H9N
C4H9NO
C5H10
C5H12
C5H5N
C5H6S
C5H8O
C5H9N
C6H12
C16H34
C17H36
C18H34O2
C18H38
C19H40
C20H42
C21H44
C22H46
C23H48
C24H50
C25H52
C26H54
C27H56
C28H58
C29H60
C30H62
CCl2F2
CCl3F
CCl4
CClF3
CO
CS2
H2O

Number of isomers

1
1
1
1
1
1
1
1
1
4
1
2
5
1
1
1
1
3
3
1
2
5
2
5
2
3
1
1
7
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1

AARD%
This study

Liu [22]

V-95 [20]

V-79 [21]

Riedel [13]

Chen [15]

ZNY [17]

Trouton [19]

0.56
0.43
0.44
0.55
1.63
3.05
1.60
2.69
0.69
4.77
3.05
3.17
2.92
1.80
2.81
2.51
5.09
1.21
7.93
2.28
1.90
1.64
4.30
5.21
2.50
1.51
3.36
0.85
1.54
3.32
0.95
1.77
2.69
1.41
0.43
1.92
2.01
8.19
2.24
1.96
1.99
3.14
2.57
2.14
1.54
0.05
0.46
0.16
0.73
1.36
1.85
1.35
4.05
5.10
0.65
7.46
2.33
2.37

0.23
0.76
2.37
0.91
0.02
0.57
4.30
1.80
3.82
5.14
1.84
2.38
2.55
19.16
2.34
0.87
3.00
1.15
9.37
1.06
3.55
2.77
6.96
6.50
4.00
2.16
1.86
1.63
1.09
0.48
1.15
0.27
0.71
3.76
0.10

15.67
16.20
16.70
17.09

17.92
18.06
18.52
18.64
19.03

5.56
3.19
1.28

4.59
1.82
0.25
1.91
1.24
0.21
0.00
0.00
3.58
11.46
0.45
3.41
0.68
11.78
0.37
2.62
1.36
3.60
8.44
0.44
8.53
4.86
4.77
4.54
3.68
3.93
0.10
0.16
5.20
8.22
2.50
3.56
3.32
7.63
6.52
0.98
0.56
11.16
0.20
0.49
0.90
10.22
10.74
11.26
11.75
12.21
12.69
13.09
13.57
13.97
14.38
1.07
1.32
2.65
1.62
0.10
6.09
5.26

0.75
1.43
1.28
0.69
1.02
1.80
1.12
0.85
1.57
3.16
1.56
2.16
2.19
30.98
1.89
1.50
3.60
0.95
9.45
1.44
3.45
2.51
7.76
7.02
3.88
2.47
2.05
1.43
1.11
0.01
0.51
1.19
1.55
3.63
0.51

9.71
9.54
9.40
8.98

8.22
7.45
6.95
6.00
5.48

1.49
3.13
0.26

4.91
0.83
0.82
0.08
0.19
2.65
0.98
2.70
0.08
3.80
0.69
1.81
0.99
0.00
0.85
0.64
1.28
1.64
7.07
5.47
5.84
3.02
11.31
9.09
6.01
2.78
0.27
4.55
1.15
0.47
2.45
0.30
0.23
6.68
0.02

0.08
1.23
2.34
4.07

7.58
10.24
12.67
16.10
18.78

0.99
3.47
3.48

3.92
1.24
1.23
0.53
0.23
2.07
1.32
1.49
0.93
2.14
0.30
1.97
1.27
37.12
1.11
0.83
1.81
1.25
7.99
3.58
4.76
3.05
9.47
7.91
5.15
2.74
0.74
3.53
1.06
0.61
2.02
0.43
0.43
5.20
0.35

8.66
8.58
8.52
8.21

7.73
7.11
6.82
6.10
5.81

0.91
3.63
4.07

14.58
0.64
0.92
0.36
1.85
0.64
2.85
1.47
4.32
13.75
5.55
4.78
5.06
20.86
5.40
3.03
10.08
2.01
14.42
6.37
0.03
0.86
5.21
6.72
1.22
0.69
6.80
6.54
1.48
3.84
4.63
2.10
3.94
0.43
1.06
3.63
3.97
15.24
4.26
4.85
5.19
14.06
14.50
14.95
15.37
15.76
16.17
16.51
16.92
17.26
17.60
0.38
0.69
0.05
2.55
1.04
0.90
21.21
(continued

12.13
3.37
4.60
4.42
0.09
6.63
6.28
4.24
1.37
13.48
2.78
3.37
1.62
20.81
1.07
0.16
8.49
3.41
12.53
4.94
2.27
5.06
3.79
5.20
2.83
2.78
4.11
4.85
4.43
9.40
2.60
0.12
2.26
1.06
4.40
4.94
5.51
17.33
6.02
6.78
7.30
16.14
16.72
17.29
17.82
18.33
18.83
19.27
19.76
20.19
20.61
6.55
4.12
3.22
6.80
18.96
5.03
19.22
on next page)

Estimation of the boiling vaporization enthalpy of pure substances

Table 4

(continued)

Hydrocarbon type

H3N
Kr
N2
N2O
N2O4
Ne
NO
O2
O2S
Xe
Average

267

Number of isomers

AARD%
This study

Liu [22]

V-95 [20]

V-79 [21]

Riedel [13]

Chen [15]

ZNY [17]

Trouton [19]

1
1
1
1
1
1
1
1
1
1

2.41
1.28
6.73
4.04
4.96
2.46
9.85
3.29
2.93
0.37

2.86
2.59
30.65
4.81
11.05
5.88
14.28
4.15
3.26
0.45

2.77
1.24
1.91
7.91
33.05
1.85
31.50
1.14
8.87
4.14

0.07
2.50
27.41
1.34
6.37
7.34
5.93
2.64
1.34
2.78

2.41
0.69
38.31
0.42
2.24
1.77
0.37
0.86
0.84
1.13

2.54
0.61
37.71
0.41
1.60
1.94
2.33
0.80
0.61
1.08

15.54
0.91
1.04
10.64
35.26
1.35
32.84
2.09
12.51
3.79

9.54
16.23
22.22
1.69
32.06
39.31
22.75
16.39
7.17
15.54

100

2.74

5.17

5.49

3.93

3.87

3.97

6.52

8.15

tting procedure. It showed that presented model can be used

for many types of pure substances. The values of the critical
pressure, critical temperature, normal boiling temperature,
and molecular weight (for comparison with other models) were
taken from the literatures [14,2426].
To compare the accuracy of presented empirical model, calculated enthalpies of vaporizations for 352 pure substances
versus experimental measured enthalpies have been presented
in Fig. 1.
In Table 2, the AARD% of enthalpies calculated from proposed and other models for each substance include one or
more isomers with respect to the values given by experimental
measurements were presented. It showed that presented model
was more accurate than other empirical correlations for all
types of compounds considered in this study.
Data points with AARD of more than 40% were not participated in statistical parameters calculations. These data were
marked with dash.
Table 3 presents the statistical parameters including average absolute relative deviation percentage (AARD%), average
relative deviation, (ARD%), and root mean square deviation
(RMSD) of the considered models and new proposed
correlation.
Fig. 2 shows the cumulative frequency of different empirical
correlations versus average absolute relative deviations. Fig. 2
also shows the accuracy of different empirical methods in prediction of vaporization enthalpies of 352 pure substances. As
shown in Fig. 2, the new proposed model is more accurate than
the seven commonly used correlations.
The new method has successfully predicted 75% of the all
measurements with AARD less than 3% and 84% of the data
with AARD less than 4%. Only 2% of the enthalpy measurements were predicted with AARD of more than 10% by the
new method. Liu model, that is the second accurate empirical
method, predicted 65% of the enthalpies measurements with
AARD less than 3% and 75% of the measurements with
AARD less than 4%.
For real comparison and estimate the applicability of presented method to calculate vaporization enthalpy of pure substances, some independent data for more than 100 pure
substances which are not employed in regression analysis of
new proposed correlation were studied [2426]. Finally,
AARD of the new method and other mentioned models for
these substances are presented in Table 4.

Table 5 presents the statistical parameters including average absolute percentage relative deviation percentage
(AARD%), average relative deviation, (ARD%), and root
mean square deviation (RMSD) of the considered models
and new proposed correlation for 100 new data points.
Consequently, Fig. 3 shows calculated enthalpies of vaporizations versus experimental measured enthalpies and Fig. 4
indicates cumulative frequency of different empirical correlations versus average absolute relative deviations for new 100
substances. As shown in Fig. 4, the new presented model estimated 85% of all 100 measurements with AARD less than 4,
while Riedel model, that is the second accurate empirical method in this comparison, predicts 77% of 100 measurements with
AARD less than 4%.
Hence, the superiority of this new empirical method over
the other empirical methods has been veried for all experimental data.
All considered models were obtained by using some experimental data points for vaporization enthalpies. But our presented correlation was tted with more experimental data for
more constant parameters than other models which can helps
to generalize the equation to calculate tting data and other
independent data which are not employed in regression analysis with lower deviations. The new correlation has a potential
validation for calculation of vaporization enthalpy for acetates, alcohols, aldehyds, alkans, alkenes, alkyl and multi-alkyl
benzene, alkynes, amines, anhydrides, anilines, carboxylic
acids, cetones, cyclo alkanes, dimethyl alkanes, esters, halo alkanes, halo alkenes, halo benzene, methyl alkans, naphthalenes, nitriles, nitro alkanes, pyridynes, suld and sulfoxids,
xylene, and some other hydrocarbons.
Table 5 Statistical parameters of this study compared with
other methods for 100 new substances.
Liu [22]
V-95 [20]
V-79 [21]
Riedel [13]
Chen [15]
ZNY [17]
Trouton [19]
This Study

AARD%

ARD%

RMSD

5.17
5.49
3.93
3.87
3.97
6.52
8.15
2.74

0.14
3.95
0.85
1.14
0.59
3.01
0.98
0.07

3.76
8.06
8.04
6.43
6.93
7.31
9.88
11.25

268

B. Mehmandoust et al.
90

Acknowledgements

Calculated Enthalpy (kJ/mol)

80
70

The supports of Khomeinishahr branch of Islamic Azad University for supporting this work are gratefully acknowledged.

60

References

50
40
30
20
10
0

10

20

30

40

50

60

70

80

90

Measured Enthalpy (kJ/mol)

Fig. 3 Accuracy of presented model versus experimental data

points for 100 new substances.
1

Cumulative frequency %

0.9
0.8
0.7
0.6
0.5
0.4

Liu [22]
V-95 [20]

0.3

V-79 [21]
Riedel [13]

0.2

Chen [15]
ZNY [17]

0.1

Trouton [19]
This study

10

12

14

AARD%

Fig. 4 AARD% of various methods in calculating vaporization

enthalpies as function of cumulative frequency for 100 new
substances.

Conclusions
In this study, the new empirical method was presented to estimate the vaporization enthalpy of pure substances at their normal boiling temperature. To estimate accuracy of this
correlation, the comparisons were done for presented model
and seven commonly used empirical methods include Vetere
(V-95), Vetere (V-79), Riedel, Chen, Zhao et al. (ZNY), Liu,
and Tourton rule. Results indicate the superiority of the new
presented correlation over all other methods used to calculate
vaporization enthalpies with average absolute relative deviation percent (AARD%) of 2.28. Also to estimate the applicability of the new method, some data for more than 100 pure
substances which are not participate in regression analysis
are examined, and the results showed again the superiority
of presented correlation with lower deviation.
Conict of interest
The authors have declared no conict of interest.

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