J. Chem. Eng.

Data 2004, 49, 77-85 77

Vapor Pressures and Vaporization Enthalpies of the n-Alkanes from

C21 to C30 at T ) 298.15 K by Correlation Gas Chromatography

James S. Chickos* and William Hanshaw

Department of Chemistry and Biochemistry, University of MissourisSt. Louis, St. Louis, Missouri 63121

The temperature dependence of gas chromatographic retention times for n-heptadecane to n-triacontane
is reported. These data are used to evaluate the vaporization enthalpies of these compounds at T ) 298.15
K, and a protocol is described that provides vapor pressures of these n-alkanes from T ) 298.15 to 575
K. The vapor pressure and vaporization enthalpy results obtained are compared with existing literature
data where possible and found to be internally consistent. Sublimation enthalpies for n-C17 to n-C30 are
calculated by combining vaporization enthalpies with fusion enthalpies and are compared when possible
to direct measurements.

Introduction
The n-alkanes serve as excellent standards for the
measurement of vaporization enthalpies of hydrocarbons.1,2
Recently, the vaporization enthalpies of the n-alkanes
reported in the literature were examined and experimental
values were selected on the basis of how well their
vaporization enthalpies correlated with their enthalpies of
transfer from solution to the gas phase as measured by gas
chromatography.3 A plot of the vaporization enthalpies of
the n-alkanes as a function of the number of carbon atoms
is given in Figure 1. The plot is remarkably linear from C5
to C20 but does show some curvature above C20. This
curvature was explained on the basis of a systematic error
in adjusting the vaporization enthalpies of the n-alkanes,
C21 to C28 and C30, found in the literature, from the
temperature of measurement to T ) 298.15 K.3 Since these
n-alkanes exhibit very low vapor pressures at ambient
temperatures, vapor pressure measurement for most of
these materials were conducted at temperatures that
required a significant temperature adjustment to T )
Figure 1. Vaporization enthalpies of the n-alkanes; the straight
298.15 K. This temperature adjustment ranged from 9.3
line represents the results obtained by a linear regression analysis
to 51.9 kJ‚mol-1.3 In view of this curvature and our of the recommended vaporization enthalpies of n-C5 to C20.11
continuing interest in using the larger n-alkanes as stan-
dards for correlation gas chromatography measurements standards have usually been chosen at T ) 298.15 K, but
(c-gc), we have reexamined these values and would like to the correlation works for other temperatures as well. The
report the results of our measurements of both vaporization linear correlation that is observed between ∆slngHm and
enthalpy and vapor pressure at T ) 298.15 K. The results ∆lgHm is empirical and can be criticized as lacking a
of our c-gc experiments of the n-alkanes from C21 to C30 theoretical basis. In this article we would like to provide a
were obtained using a method best described as a steplad- simple mathematical basis for the linear correlation ob-
der extrapolation. The results of this stepladder approach served. The correlation is applied to the evaluation of vapor
are tested by comparison of ∆lgHm(Tm) values and vapor pressures and enthalpies of vaporization of the n-alkanes
pressures obtained by c-gc to those measured by other from C21 to C30 at T ) 298.15 K.
methods at temperatures where experimental data are
available. Discussion
Correlation gas chromatography has proven to be quite
Enthalpies of transfer from solution to the vapor,
successful in providing vaporization enthalpies of both
∆slngHm, are measured by gas chromatography by measur-
liquids and solids. The technique relies on the linear
ing the retention times of a mixture consisting of both
correlation observed between enthalpies of transfer from
standards and target solutes as a function of temperature.
solution to the vapor, ∆slngHm, as measured by gas chro-
The retention times, t, are adjusted for the dead volume of
matography and the vaporization enthalpy (∆lgHm) of a
the column by measuring the retention time of an unre-
series of standards. The vaporization enthalpies of the
tained solute, usually the solvent. Since the retention time
* To whom correspondence should be addressed. E-mail: jsc@umsl.edu. of the unretained solute is governed by the flow rate of the
Phone: 314 516 5377. carrier, its retention time as a function of temperature
10.1021/je0301747 CCC: $27.50 © 2004 American Chemical Society
Published on Web 10/31/2003
78 Journal of Chemical and Engineering Data, Vol. 49, No. 1, 2004

behaves differently from those of the other solutes. The In this equation, nc refers to the number of carbon atoms.
viscosity of the carrier gas, usually He in our experiments, This equation takes the general form mnc + b. Although
increases with temperature. Thus, the retention time of this equation was derived for vaporization enthalpies at
the nonretained reference, tnrr, increases while that for the T ) 298.15 K, the temperature selection is arbitrary and
other solutes decreases with temperature. This observation it is reasonable to assume that a similar equation of the
is useful in ensuring a reliable measurement of the time same type, m′nc + b′, could also be derived for vaporization
needed to traverse the column at each temperature. The enthalpies at T ) Tm, where m′ and b′ are appropriate
adjusted retention time, ta ) t - tnrr, measures the amount constants.6,7 Vaporization enthalpies at T ) 298.15 K differ
of time the solute spends on the stationary phase, and this from those at T ) Tm by differences in the heat capacities
time is inversely proportional to the compound’s vapor of the liquid and gas phases, and both properties are known
pressure above the condensed phase. A plot of ln(1/ta) to be modeled by group additivity.8,9 In addition, vaporiza-
versus 1/T (K-1) results in a linear plot with a slope equal tion enthalpies at both T ) 298.15 K and T ) Tm could be
to -∆gslnHm(Tm)/R. This technique has been used by others, modeled exactly by these equations by simply allowing the
notably the work of Fuchs et al.,4 who pioneered the use of intercepts, b and b′, to vary. Enthalpies of solution are
enthalpies of transfer in conjunction with enthalpies of small in comparison to vaporization enthalpies10 and also
solution to evaluate vaporization enthalpies. can be modeled by group additivity, m′′nc + b′′. This
The term ∆gslnHm(Tm) can be equated in a thermody- modeling can also be exact if b′′ is allowed to vary.
namic cycle to the sum of the vaporization enthalpy Substituting these linear functions into eq 3 and combining
measured at T ) Tm and the enthalpy of solution or similar terms results in eq 5, where msln ) (m′ + m′′) and
adsorption (∆slnHm) of each solute on the stationary phase bsln ) (b′ + b′′).
of the column as shown below. The sensitivity of the flame
ionization detector ensures dilute concentrations of solute, slope ) [mslnnc + bsln]/[mnc + b] (5)
and since the solute dissolves in the stationary phase, the
same thermodynamic cycle applies to both solids and
As long as bsln and b are small in comparison to mslnnc and
liquids.
mnc, respectively, the correlation of ∆slngHm(Tm) with
∆lgHm(298.15 K) will be linear because the ratio [mslnnc +
∆gslnHm(Tm) ) ∆glHm(Tm) + ∆slnHm(Tm) (1) bsln]tranfer/[mnc + b]vap is a hyperbolic function approaching
its asymptote, msln/m. Similar arguments can also be made
Peacock and Fuchs measured ∆gslnHm(Tm) values of a for hydrocarbon derivatives containing a single functional
series of compounds by gas chromatography and adjusted group or multiple functional groups provided the number
the results for temperature. They combined enthalpies of and type of functional groups in the correlation are kept
vaporization and solution in the liquid stationary phase constant. Alternatively, the hydrocarbon portion can be
of the column, DC 200, and compared their results to kept constant and the number of identical functional
∆gslnHm(Tm) values adjusted for temperature to T ) 298.15 groups varied. In either of these instances, it would be
K. The thermochemical cycle yielded results that were not necessary to define nc differently.
exactly identical but were very similar and were linearly
correlated.4 Experimental Section
In correlation gas chromatography, ∆gslnHm(Tm) values
All n-alkanes were purchased from the Aldrich Chemical
are correlated directly with the vaporization enthalpies of
Co. and were used without any further purification. Each
the standards at the temperature of interest, usually at
was analyzed by gas chromatography and found to be at
T ) 298.15 K. Provided the standards are appropriately
least 99 mol % pure. Correlation gas chromatography
chosen in relation to each other and to the target solutes,
experiments were performed on an HP 5890A series II gas
a linear correlation is obtained between ∆gslnHm(Tm) and
chromatograph equipped with a split/splitless capillary
∆glHm(Tm). The correlation equation derived from known
injection port and a flame ionization detector run at a split
vaporization enthalpies is then used to evaluate the
ratio of 100/1. Retention times were recorded to three
vaporization enthalpies of the target solutes.5 The following
significant figures following the decimal point on a HP
narrative describes the origin of this correlation.
3989A integrator. The instrument was run isothermally
In the thermodynamic cycle outlined by eq 1, all of the
using a 30 m SPB-5 capillary column. Helium was used as
enthalpies are referenced to the same temperature. In
the carrier gas. At the temperatures of the experiments,
c-gc, ∆gslnHm(Tm) measured at T ) Tm is correlated to
the retention time of the solvent, CH2Cl2, increased with
∆glHm(298.15 K); the correlation results in the following
increasing temperature. This is a consequence of the
slope:
increase in viscosity of the carrier gas with temperature;
it is the criterion used to confirm that the solvent is not
slope ) ∆gslnHm(Tm)/∆glHm(298.15 K) (2) being retained on the column. The retention times of the
solvent were used to determine the dead volume of the
Appropriate substitution of eq 1 into eq 2 results in the column. Adjusted retention times, ta, were calculated by
following: subtracting the measured retention time of the solvent
from the retention time of each analyte as a function of
slope ) [∆glHm(Tm) + ∆slnHm(Tm)]/∆glHm(298.15 K) (3) temperature over a 30 K range. Column temperatures were
controlled by the gas chromatograph and were monitored
Vaporization enthalpies of hydrocarbons are known to independently by using a Fluke 51 K/J thermometer.
exhibit excellent group properties. Hydrocarbons can be Temperature was maintained constant by the gas chro-
estimated quite accurately by a variety of simple relation- matograph to (0.1 K.
ships, including the following:6
Results
∆glHm(298.15 K) ) (4.64 ( 0.13)nc + (2.93 ( 0.8); Experimental retention times are presented in Table 1
r ) 0.965 (4) for a series of mixtures. A plot of ln(1/ta) versus 1/T (K-1)
 Journal of Chemical and Engineering Data, Vol. 49, No. 1, 2004 79

Table 1. Retention Times

retention times, t/min, for C14 to C20
T/K ) 434.3 T/K ) 439.3 T/K ) 444.2 T/K ) 449.1 T/K ) 454.1 T/K ) 459 T/K ) 463.8
methylene chloride 1.251 1.215 1.246 1.216 1.222 1.228 1.249
tetradecane 3.039 2.695 2.485 2.29 2.145 2.022 1.942
pentadecane 4.107 3.558 3.205 2.887 2.643 2.451 2.288
hexadecane 5.827 4.933 4.344 3.807 3.409 3.084 2.805
heptadecane 8.329 6.907 5.939 5.097 4.47 3.959 3.54
octadecane 12.283 9.994 8.403 7.065 6.071 5.265 4.624
nonadecane 18.549 14.836 12.2 10.075 8.487 7.219 6.211
eicosane 28.345 22.305 17.935 14.57 12.04 10.076 8.522

retention times, t/min, for C17 to C23

T/K ) 493.8 T/K ) 498.9 T/K ) 503.8 T/K ) 508.9 T/K ) 513.9 T/K ) 518.9 T/K ) 523.9
methylene chloride 1.721 1.747 1.746 1.765 1.779 1.792 1.816
heptadecane 2.974 2.849 2.722 2.624 2.556 2.472 2.435
octadecane 3.477 3.276 3.093 2.941 2.83 2.712 2.645
nonadecane 4.182 3.88 3.61 3.375 3.202 3.035 2.926
eicosane 5.144 4.685 4.295 3.952 3.695 3.459 3.294
heneicosane 6.496 5.826 5.255 4.743 4.368 4.034 3.787
docosane 8.37 7.392 6.56 5.811 5.275 4.799 4.44
tricosane 10.923 9.498 8.295 7.232 6.468 5.798 5.288

retention times, t/min, for C19 to C25

T/K ) 524.05 T/K ) 529 T/K ) 534.1 T/K ) 539.25 T/K ) 544.25 T/K ) 549.25 T/K ) 553.25
methylene chloride 1.822 1.82 1.847 1.858 1.888 1.935 1.981
nonadecane 2.912 2.785 2.698 2.621 2.579 2.565 2.565
eicosane 3.271 3.096 2.965 2.856 2.785 2.75 2.733
heneicosane 3.77 3.52 3.327 3.17 3.06 2.993 2.95
docosane 4.421 4.072 3.797 3.577 3.412 3.303 3.225
tricosane 5.262 4.78 4.397 4.09 3.856 3.69 3.567
tetracosane 6.365 5.701 5.174 4.751 4.425 4.182 4.001
pentacosane 7.79 6.887 6.167 5.588 5.139 4.8 4.543

retention times, t/min, for C21 to C27

T/K ) 508.7 T/K ) 513.8 T/K ) 518.9 T/K ) 523.9 T/K ) 528.9 T/K ) 534 T/K ) 539
methylene chloride 1.162 1.155 1.141 1.119 1.127 1.115 1.115
heneicosane 3.201 2.898 2.595 2.379 2.188 2.04 1.919
docosane 3.972 3.54 3.12 2.827 2.551 2.344 2.174
tricosane 4.917 4.319 3.76 3.354 2.987 2.708 2.483
tetracosane 6.258 5.412 4.645 4.088 3.581 3.201 2.9
pentacosane 7.92 6.734 5.735 4.962 4.297 3.791 3.395
hexacosane 10.197 8.514 7.192 6.132 5.244 4.574 4.04
heptacosane 13.07 10.71 9.055 7.573 6.425 5.555 4.843

retention times, t/min, for C23 to C30

T/K ) 528.9 T/K ) 533.9 T/K ) 539 T/K ) 544.1 T/K ) 549.1 T/K ) 554.1 T/K ) 559
methylene chloride 1.516 1.49 1.455 1.48 1.416 1.451 1.483
tricosane 4.027 3.611 3.235 2.979 2.726 2.605 2.53
tetracosane 4.817 4.254 3.762 3.42 3.092 2.929 2.812
pentacosane 5.818 5.064 4.422 3.972 3.548 3.327 3.158
hexacosane 7.105 6.1 5.264 4.67 4.121 3.82 3.586
heptacosane 8.795 7.455 6.349 5.565 4.852 4.447 4.126
octacosane 11.099 9.277 7.802 6.753 5.82 5.254 4.83
nonacosane 14.068 11.609 9.649 8.255 7.04 6.264 5.706
tricontane 17.922 14.64 12.041 10.183 8.594 7.547 6.81
resulted in linear plots whose slopes and intercepts are thalpies of tetracosane and pentacosane, evaluated in Table
provided in Table 2. The first mixture in Table 3 lists the 3 under C19 to C25, were used as knowns in the remaining
enthalpies of transfer from solution to the gas phase mixtures in Table 3. The vaporization enthalpies of the
measured for the series tetradecane to eicosane (column n-alkanes heneicosane through tricosane at T ) 298.15 K
2) along with recommended vaporization enthalpies (col- were evaluated in this fashion. Uncertainties reported in
umn 3).11 As can be seen from column 4, the vaporization vaporization enthalpies were calculated from the uncer-
enthalpy obtained from the correlation equation, given at tainty associated with the slope of the line obtained in each
the bottom of the series in Table 3, is in excellent agree- correlation.
ment with the experimental values. Under C17 to C23 in Figure 2 provides some idea of the quality of the
Table 3, heptadecane through eicosane were used to correlations represented by the data in Table 3. Experi-
evaluate the vaporization enthalpies of henicosane, docosane, mental data for comparison of the results reported in Table
and tricosane. Once these vaporization enthalpy values 3 at T ) 298.15 K are not available for the C21 to C30
were evaluated, they were then used as needed in subse- n-alkanes without substantial temperature adjustments.
quent mixtures to evaluate the vaporization enthalpies of Figure 3 illustrates the vaporization enthalpies of the
the remaining n-alkanes. Similarly, the vaporization en- n-alkanes from pentane through tricosane as a function of
80 Journal of Chemical and Engineering Data, Vol. 49, No. 1, 2004

Table 2. Equations for the Temperature Dependence of Table 3. Vaporization Enthalpies (in kJ‚mol-1) of the
ln(1/ta)a n-Alkanes
∆slngHm/R intercept r2 C14 to C20
C14 to C20 at Tm ) 449 K ∆lgHm(298.15 K)
tetradecane -6393.8 ( 95 14.161 ( 0.01 0.9989
pentadecane -6787.9 ( 73 14.597 ( 0.01 0.9994 ∆slngHm(449 K) lit. calc
hexadecane -7251.5 ( 62 15.190 ( 0.01 0.9996 tetradecane 53.2 71.7 71.8 ( 1.0
heptadecane -7612.6 ( 65 15.587 ( 0.01 0.9996 pentadecane 56.4 76.8 76.5 ( 1.0
octadecane -8014.8 ( 71 16.070 ( 0.01 0.9996 hexadecane 60.3 81.4 82 ( 1.1
nonadecane -8457.4 ( 74 16.640 ( 0.01 0.9996 heptadecane 63.3 86.5 86.3 ( 1.2
eicosane -8919.6 ( 85 17.257 ( 0.01 0.9995 octadecane 66.6 91.4 91.1 ( 1.3
C17 to C23 at Tm ) 508.8 K nonadecane 70.3 96.4 96.4 ( 1.4
heptadecane -6108.2 ( 78.2 12.148 ( 0.008 0.9992 eicosane 74.2 101.8 101.9 ( 1.4
octadecane -6489.9 ( 63.8 12.584 ( 0.006 0.9995 ∆lgHm(298.15 K) ) (1.436 ( 0.019)∆slngHm(Tm) -
nonadecane -6901.0 ( 58.7 13.077 ( 0.006 0.9996 (4.54 ( 0.35); r2 ) 0.9991
eicosane -7270.0 ( 60.5 13.496 ( 0.006 0.9996
heneicosane -7670.9 ( 65.3 13.974 ( 0.006 0.9996
docosane -8064.5 ( 71.6 14.439 ( 0.007 0.9996 C17 to C23
tricosane -8451.1 ( 73.9 14.897 ( 0.008 0.9996 ∆lgHm(298.15 K)
C19 to C25 at Tm ) 538.7 K ∆slngH
m(508.5 K) lit. calc
nonadecane -6165.3 ( 125.9 11.692 ( 0.01 0.9979
eicosane -6483.0 ( 127.6 12.013 ( 0.01 0.9980 heptadecane 50.8 86.5 86.4 ( 2.0
heneicosane -6888.5 ( 127.9 12.487 ( 0.01 0.9983 octadecane 54.0 91.4 91.4 ( 2.2
docosane -7256.5 ( 121.1 12.906 ( 0.01 0.9986 nonadecane 57.4 96.4 96.7 ( 2.3
tricosane -7619.9 ( 116.3 13.318 ( 0.01 0.9988 eicosane 60.4 101.8 101.6 ( 2.4
tetracosane -7972.5 ( 112.6 13.713 ( 0.01 0.9990 heneicosane 63.8 106.8 ( 2.5
pentacosane -8320.7 ( 111.6 14.105 ( 0.01 0.9991 docosane 67.0 111.9 ( 2.7
tricosane 70.3 117.0 ( 2.8
C21 to C27 at Tm ) 523.8 K
heneicosane -8494.5 ( 115.7 15.987 ( 0.01 0.9991 ∆lgHm(298.15 K) ) (1.57 ( 0.04)∆slngHm(Tm) -
docosane -8898.7 ( 106 16.459 ( 0.01 0.9993 (6.66 ( 0.30); r2 ) 0.9985
tricosane -9211.7 ( 98.3 16.784 ( 0.01 0.9994
tetracosane -9573.1 ( 102.1 17.190 ( 0.01 0.9994 C19 to C25
pentacosane -9903.7 ( 95.7 17.560 ( 0.01 0.9995
hexacosane -10250.6 ( 92.9 17.954 ( 0.01 0.9996 ∆lgHm(298.15 K)
heptacosane -10522.2 ( 106.3 18.216 ( 0.01 0.9995 ∆slngHm(538.7 K) lit. calc
C23 to C30 at Tm ) 544 K nonadecane 51.3 96.4 96.8 ( 2.2
tricosane -8729.1 ( 288.3 15.607 ( 0.03 0.9946 eicosane 53.9 101.8 101.2 ( 2.3
tetracosane -9050.3 ( 285.3 15.942 ( 0.03 0.9951 heneicosane 57.2 106.8 106.8 ( 2.5
pentacosane -9362.2 ( 280.4 16.268 ( 0.03 0.9955 docosane 60.3 111.9 112.0 ( 2.5
hexacosane -9691.1 ( 273.3 16.628 ( 0.02 0.996 tricosane 63.3 117.0 117.0 ( 2.7
heptacosane -10035.9 ( 271.9 17.016 ( 0.02 0.9963 tetracosane 66.3 121.9 ( 2.8
octacosane -10423.3 ( 273.1 17.474 ( 0.02 0.9966 pentacosane 69.2 126.8 ( 2.9
nonacosane -10792.9 ( 274.5 17.904 ( 0.02 0.9968
triacontane -11150 ( 271.3 18.311 ( 0.02 0.997 ∆lgHm(298.15 K) ) (1.67 ( 0.042)∆slngHm(Tm) -
(11.04 ( 0.41); r2 ) 0.9981
a ln(1/ta) ) ∆slngHm/R + intercept.
C21 to C27
the number of carbon atoms. The line in the figure was ∆lgHm(298.15 K)
drawn using the values of the n-alkanes from n-pentane ∆slngHm(523.8 K) lit. calc
through to n-eicosane; it represents the results of a linear
heneicosane 70.6 106.3 106.5 ( 2.7
regression analysis. As is illustrated by Figure 3, the
docosane 74.0 111.9 112.4 ( 2.8
correlation through to C30 remains quite linear in com- tricosane 76.6 117.0 116.8 ( 2.9
parison to Figure 1. A further evaluation of the quality of tetracosane 79.6 121.9 122.0 ( 3.0
the data generated for n-C21 to n-C30 is provided below. pentacosane 82.3 126.8 126.7 ( 3.1
One of the advantages of using correlation gas chroma- hexacosane 85.2 131.7 ( 3.2
tography to evaluate vaporization enthalpies is that the heptacosane 87.5 135.6 ( 3.3
choice of reference temperature is arbitrary. Consequently, ∆lgHm(298.15 K) ) (1.721 ( 0.038)∆slngHm(Tm) -
it is possible to use the retention time data provided in (15.02 ( 0.34); r2 ) 0.9985
Table 1 to evaluate vaporization enthalpies of the n-alkanes
at any temperature where experimental data for the C23 to C30
standards are available. However, before testing the equa- ∆lgHm(298.15 K)
tions provided in Table 2 for accuracy in evaluating
∆slngHm(544 K) lit. calc
vaporization enthalpies at other temperatures, we would
like to demonstrate the usefulness of these equations in tricosane 72.6 117.0 117.3 ( 4.1
tetracosane 75.2 121.9 121.9 ( 4.3
providing vapor pressure data as well. pentacosane 77.8 126.8 127.2 ( 4.4
The use of the correlation equations in providing vapor hexacosane 80.6 131.7 131.2 ( 4.6
pressure data has been briefly described previously.4 These heptacosane 83.4 135.6 136.1 ( 4.8
equations relate the temperature dependence of the vapor octacosane 86.7 141.9 ( 4.9
pressure of the solute (1/ta) above the stationary phase of nonacosane 89.7 147.1 ( 5.1
the column over a narrow temperature range. Although triacontane 92.7 152.3 ( 5.3
these equations would not be expected to be accurate in ∆lgHm(298.15 K) ) (1.738 ( 0.057)∆slngHm(Tm) -
predicting vapor pressures by themselves, when used with (-8.82 ( 0.49); r2 ) 0.9968
 Journal of Chemical and Engineering Data, Vol. 49, No. 1, 2004 81

Figure 2. Correlations obtained by plotting vaporization enthalpy Figure 4. Correlation observed between ln(1/ta) calculated by
at T )298.15 K against the enthalpy of transfer measured at the extrapolation to 298.15 K using the equations given in Table 2A
mean temperature indicated: triangles, n-C14 to C20 (449 K); solid and ln(p/p0) at 298.15 K calculated from the Cox equation for n-C14
triangles, n-C17 to C23 (508.8 K); hexagons, n-C19 to C25 (538.7 K); to n-C20. The term p0 represents the vapor pressure (101.325 kPa)
squares, n-C21 to C27 (523.8 K); circles, n-C23 to C30 (544 K). at the reference temperature, Tb, the normal boiling point of the
n-alkane; the equation of the line obtained by a linear regression
is given by ln(p/p0) ) (1.26 ( 0.01) ln(1/ta) - (1.718 ( 0.048);
r2 ) 0.9997.

Table 4. Parameters of the Cox Equation Used in the

Calculationsa
Tb A0 103A1 106A2
tetradecane 526.691 3.136 24 -2.063 853 1.541 51
pentadecane 543.797 3.167 74 -2.062 348 1.487 26
hexadecane 559.978 3.182 71 -2.002 545 1.384 48
heptadecane 575.375 3.218 26 -2.04 1.38
octadecane 590.023 3.247 41 -2.048 039 1.362 45
nonadecane 603.989 3.276 26 -2.06 1.35
eicosane 617.415 3.311 81 -2.102 218 1.348 78
octacosaneb 705 3.413 04 -1.889 4 1.045 75
a All data are from ref 11 unless otherwise noted. b Reference
12.

ln(p/p0) ) (1 - Tb/T) exp(A0 + A1T + A2T 2) (6)

The linearity observed between ln(p/p0) and ln(1/ta) for

n-C14 through C20 suggests a mechanism by which vapor
Figure 3. Vaporization enthalpies of n-C5 to C30 as a function of pressure data for the larger n-alkanes can be obtained.
the number of carbon atoms using the data from this study; the Using experimental ln(p/p0) data at T ) 298.15 K (calcu-
straight line represents the results obtained by a linear regression lated from the Cox equation) and extrapolated ln(1/ta)
analysis of the recommended vaporization enthalpies of n-C5 to values for n-C17 to n-C23 (using the appropriate equations
C20.11 given in Table 2 at T ) 298.15 K), values of ln(p/p0) for
n-C21 to n-C23 can be obtained by correlation (the top
a series of standards with known vapor pressures at the ln(p/p0)calc column in Table 5). The ln(p/p0) terms for n-C21
temperature of interest, the results obtained through a to n-C23 can then be used as needed with other ln(p/p0)
process of correlation are quite satisfactory. This is il- values and appropriate ln(1/ta) values to derived ln(p/p0)
lustrated in Figure 4 by the results obtained for n-C14 to values for other n-alkanes. For example, using the calcu-
n-C20. In this instance, the equations in Table 2 have been lated ln(p/p0) values for n-C21 to n-C23 (top of Table 5,
used to provide ln(1/ta) data at T ) 298.15 K by extrapola- column 4), the corresponding experimental values for n-C19
tion from Tm ) 449 K. Correlation of the extrapolated and n-C20, and ln(1/ta) values calculated from the appropri-
ln(1/ta) values with experimental vapor pressure data ate correlation equations (Table 2, C19 to C25), ln(p/p0)
calculated from the Cox equation, eq 6,11,12 results in the values for n-C24 and n-C25 can be calculated (see the top of
linear relationship illustrated by Figure 4. The reference Table 5, last column). Once a value of ln(p/p0) was evalu-
pressure in the Cox equation, p0 (101.325 kPa), refers to ated, it was used in subsequent correlations with appropri-
the vapor pressure at the normal boiling point, Tb. The Tb ate ln(1/ta) values to provide ln(p/p0) values for the remain-
and A terms in eq 6 for the n-alkanes in question are given ing n-alkanes. This is the protocol that was followed in
in Table 4. Table 5.
82 Journal of Chemical and Engineering Data, Vol. 49, No. 1, 2004

Table 5. Calculation of ln(p/p0) at T ) 298.15 K for the n-Alkanes C21 to C30 by Correlation with the ln(p/p0) Values of
n-C17 to n-C20 Generated from the Cox Equation11
C21 to C25
ln(1/ta)a ln(p/p0)exptb ln(p/p0)calcc ln(1/ta)d ln(p/p0)calc ln(p/p0)calce
heptadecane -8.34 -14.30 -14.2
octadecane -9.18 -15.43 -15.4
nonadecane -10.07 -16.57 -16.60 -8.99 -16.57b -16.61
eicosane -10.89 -17.70 -17.68 -9.73 -17.70b -17.64
heneicosane -11.75 -18.84 -10.61 -18.84c -18.84
docosane -12.61 -19.97 -11.43 -19.97c -19.98
tricosane -13.45 -21.09 -12.24 -21.09c -21.09
tetracosane -13.03 -22.17
pentacosane -13.80 -23.24
ln(p/p0)calc ) (1.329 ( 0.012) ln(1/ta) - (3.216 ( 0.024); r2 ) 0.9998 (7)
ln(p/p0)calc ) (1.377 ( 0.017) ln(1/ta) - (4.233 ( 0.043); r2 ) 0.9995 (8)

C26 to C30
ln(1/ta)f ln(p/p0) ln(p/p0)calcg ln(1/ta)h ln(p/p0)calc ln(p/p0)calci
heneicosane -12.50 -18.84c -18.80
docosane -13.39 -19.97c -20.04
tricosane -14.11 -21.09c -21.06 -13.67 -21.09c -21.13
tetracosane -14.92 -22.17e -22.19 -14.41 -22.17e -22.18
pentacosane -15.66 -23.24e -23.23 -15.13 -23.24e -23.19
hexacosane -16.43 -24.31 -15.88 -24.31g -24.23
heptacosane -17.08 -25.22 -16.64 -25.22g -25.31
octacosane -17.49 -26.49
nonacosane -18.30 -27.63
tricontane -19.09 -28.74
ln(p/p0)calc ) (1.405 ( 0.020) ln(1/ta) - (1.230 ( 0.050); r2 ) 0.9994 (9)
ln(p/p0)calc ) (1.404 ( 0.034) ln(1/ta) - (1.944 ( 0.080); r2 ) 0.9982 (10)
a Calculated at T ) 298.15 K using the equations in Table 2 for C
17 to C23. Calculated at T ) 298.15 K using the parameters of the
b

Cox equation given in Table 4. c Calculated using eq 7 generated from the data in columns 2 and 3 (under C21 to C25). d Calculated at
T ) 298.15 K using the equations in Table 2 for C19 to C25. e Calculated using eq 8 generated from the data in columns 5 and 6 (under
C21 to C25). f Calculated at T ) 298.15 K using the equations in Table 2 for C21 to C27. g Calculated using eq 9 generated from the data
in columns 2 and 3 (under C26 to C30). h Calculated at T ) 298.15 K using the equations in Table 2 for C23 to C30. i Calculated using
eq 10 generated from the data in columns 5 and 6 (under C26 to C30).

The calculated ln(1/ta) terms in Table 5 have footnotes Table 6. Comparison of the Vapor Pressure and
Vaporization Enthalpy of Octacosane Obtained by
to identify which equations in Table 2 were used in their Correlation Gas Chromatography with Literature Values
generation. The ln(p/p0)calc values are also footnoted to
identify their origins; eqs 7-10 were used to generate ln(p/p0) from
T/K ln(1/ta)a ln(p/p0)b ln(p/p0)c
calculated values.
The use of such an extrapolation is risky, since any errors 298.15 -26.49 -25.88 -26.52d
inherent in the first correlation can be amplified in 453.15 -8.92 -8.88 -8.91d
463.15 -8.30 -8.27 -8.28d
subsequent ones. Consequently, both the vaporization 483.1 -7.16 -7.14 -7.12e
enthalpy and the vapor pressure results obtained as 518.1 -5.45 -5.43e
described above need independent confirmation. The linear 553.1 -4.04 -4.01e
behavior of vaporization enthalpy as a function of the 588.1 -2.86 -2.83e
number of carbon atoms from n-C5 to n-C30 has already ∆lgHm(468.15 K)/kJ‚mol-1 106.7a 105.6b 107.2d
been mentioned, suggesting that the vaporization enthal-
pies obtained for n-C21 to n-C30 at T ) 298.15 K are a This work. b From ref 12. c From ref 13. d “Conformal” fit to

consistent with previous measurements made on the the Wagner equation. e Experimental values.
smaller homologues. Experimental vaporization enthalpies
and vapor pressures for n-C21 to n-C30 at T ) 298.15 K are the parameters of the Cox equation, Table 4, the equations
not available for comparison, at least without significant in Table 2, and the stepladder approach just described for
temperature adjustments. However, reliable values are obtaining ln(p/p0) at T ) 298.15 K for n-C21 to n-C30, vapor
available at elevated temperatures. As noted above, the pressures at a series of different temperatures were
equations in Table 2 can be used for correlations at any calculated. These are listed in Table 6 along with the
temperature. The range of temperatures for which the Cox experimental vapor pressures reported by Chirico et al.12
equation is applicable for the n-alkanes C17 to C20 is from from T ) 453 to T ) 483 K and by Morgan and Kobayashi13
T ) 298.15 K to the boiling point of heptadecane, T ) 575 from T ) 483.1 to T ) 588.1 K. Chirico et al. provide
K.11 Chirico et al.12 and Morgan and Kobayashi13 have parameters of the Cox equation for octacosane which are
reported high precision data for octacosane within this listed in Table 4. The Cox equation extrapolates with
temperature range. Since both the vaporization enthalpy reasonable precision over a 50-70 K range. The use of this
and vapor pressure of octacosane are evaluated last in the equation to calculate the vapor pressure of octacosane at
series of correlations described in Table 5, it seemed that T ) 298.15 K exceeds the range of its applicability.
these experimental data would provide a good test of the Nevertheless, the value calculated at this temperature for
quality of the data generated by the equations in Table 2. octacosane is compared in Table 6 to the results obtained
Using the vapor pressures of n-C17 to n-C20 generated from in this study; the two values compare favorably. The
 Journal of Chemical and Engineering Data, Vol. 49, No. 1, 2004 83

Table 7. Comparison of the Vapor Pressures and Vaporization Enthalpies (in kJ‚mol-1) of Several n-Alkanes at Various
Temperatures
ln(p/p0)
T/K from ln(1/ta)a ln(p/p0)b ln(p/p0)c ln(p/p0)d ln(p/p0)e ∆lgHm(T)a ∆lgHm(T)
docosane 463 -5.6 -5.5 85.8 85.2c
docosane 417.8 -8.1 -8.0 92.6 92.7e
docosane 417.8 -8.1 -8.0 92.6 91.7d
tetracosane 463 -6.5 -6.5 93.1 93.3c
tetracosane 417.8 -9.2 -9.0 100.2 121.4e
tetracosane 417.8 -9.2 -9.2 100.2 102.2d
hexacosane 417.8 -10.3 -10.3 108.6 109.2e
octacosane 417.8 -11.5 -11.4 116.7 114.3b
octacosane 417.8 -11.5 -11.4 116.7 116.6c
octacosane 417.8 -11.5 -11.5 116.7 128.9e
a This work. b Reference 12. c “Conformal” fits to the Wagner equation.13 d Reference 16. e Reference 17.

Table 8. Comparison of Absolute Vapor Pressures of C16

experimental measurements on octacosane by Morgan and to C18, C20 to C22, and C25 to C30 Reported in This Study
Kobayashi are at higher temperatures.13 Their data were with Other Literature Values at T ) 298.15 K
also fit to a form of the Wagner vapor pressure equation.
ln(p/Pa)
Results of their “conformal fit” are included as the fourth
this work ln(p/Pa)a ln(p/Pa)b ln(p/Pa)c ln(p/Pa)d
column of the table at temperatures T ) 453 and 463.15
K, and experimental values are provided from T ) 483.1 hexadecane -1.66 -1.68 -1.66
heptadecane -2.77 -3.52 -2.77
to T ) 553 K. The “conformal” fit of both vapor pressure
octadecane -3.91 -3.59 -3.91
and vaporization enthalpy at the lower temperatures is in eicosane -6.17 -5.8 -6.17 -6.17
good agreement with the results of this work; this work heneicosane -7.31 -7.1
also compares well with their experimental data. The vapor docosane -8.45 -8.27 -8.53
pressures reported in Table 6 also allow a determination tetracosane -10.65 -10.32 -10.7
of the vaporization enthalpy of octacosane at T ) 468.15 pentacosane -11.72 -11.35
hexacosane -12.78 -12.2
K using the different approaches. The last entry in the heptacosane -13.70 -13.38
table compares values; they appear to be in very good octacosane -14.96 -15.38 -14.36 -15.0
agreement. nonacosane -16.10 -16.22
As noted above, vaporization enthalpies and vapor triacontane -17.22 -18.58
pressures are available for all the n-alkanes examined in
a References 18 and 19. b Reference 11. c Reference 12 by ex-
this study at temperatures above T ) 298.15 K. As a
trapolation of the Cox equation. d “Conformal” fits to the Wagner
further test of the use of the equations in Table 2, we have equation, ref 13].
examined both vapor pressure and vaporization enthalpy
of a selected number of n-alkanes. As noted by Lemmon reported by Morgan and Kobayashi13 are their “conformal”
and Goodwin14 and others,3 vapor pressures and vaporiza- fits. A comparison of the results obtained from this study
tion enthalpies reported by Piacente and co-workers15 are using the recommended data of Ruzicka and Majer11 for
not generally consistent with values from other sources; n-C17 to n-C20 with those from Goss and Schwarzenbach18,19
these data as well as data reported prior to 1980 were not is quite good for most compounds.
included in this comparison. Of all the n-C17 to n-C20 alkanes used as standards,
Table 7 lists the vapor pressures and vaporization heptadecane is the alkane that exhibits the smallest
enthalpies calculated using the equations in Table 2 for temperature range for which recommended vapor pressures
some other n-alkanes using the same protocol. The results are available;11 the range extends from T ) 298.15 K to
from these calculations are compared to experimental T ) 575.4 K. Using the equations in Table 2 and the vapor
values from the literature.16,17 The literature vapor pres- pressures calculated from the Cox equations for n-C17 to
sures and vaporization enthalpies listed in Table 7 were n-C20, vapor pressures for n-C21 to n-C30 were calculated
either calculated from vapor pressures derived from the over 30 K intervals from T ) 298.15 K to T ) 575 K using
Cox,13 Wagner,17 or Antoine equations or used directly as the stepladder approach described above. The plots of
reported. The agreement with literature values is generally ln(p/p0) versus 1/T for these n-alkanes are illustrated in
very good. The vaporization enthalpies calculated from the Figure 5. The curves were fitted to a third-order polyno-
temperature dependence of vapor pressure are listed in the mial, eq 11, whose coefficients are provided in Table 9; T
last two columns. Column 7 lists the values obtained in in eq 11 refers to the absolute temperature.
this study while the last column reports literature values.
Most of the values compare quite favorably. Two of the ln(p/p0) ) AT -3 + BT -2 + CT -1 + D (11)
three vaporization enthalpies calculated from the limited
data reported by Grenier-Loustalot et al.17 appear out of The quality of the fit using eq 11 is quite good. The largest
line with other literature values and the results obtained fractional error between the vapor pressures calculated
in this work. using the equations in Table 2 and those in Table 8 was
Subcooled liquid vapor pressures of a number of n- obtained for triacontane. The fractional error ranged from
alkanes between n-C16 and n-C30 at T ) 298.15 K have been 0.011 at T ) 298.15 K to 0.003 at T ) 568 K. The fractional
cited by Goss and Schwarzenbach18 using data from Daub- errors associated with the remaining n-alkanes were
ert and Danner.19 The vapor pressure data in Table 8, considerably smaller. These equations can now be used to
reported as ln(p/Pa), include vapor pressures obtained in calculate the vapor pressures of n-C21 to n-C30 and at any
this study, data from Daubert and Danner,19 recommended temperature between T ) 298.15 K and T ) 575 K.
data from Ruzicka and Majer,11 and extrapolated data from Subcooled liquid vapor pressures and vaporization en-
the Cox equation reported by Chirico et al.12 Values thalpies are useful thermodynamic properties. Subcooled
84 Journal of Chemical and Engineering Data, Vol. 49, No. 1, 2004

liquid vapor pressures of polyaromatic hydrocarbons have

been used in a wide range of environmental applications;18-20
the vapor pressures of the n-alkanes should serve as
excellent standards for their evaluation.2,5 All the n-alkanes
C21 to C30 are solids at T ) 298.15 K; the vaporization
enthalpies reported in Table 3 represent values for the
subcooled liquid state. Sublimation enthalpies for these
compounds have not been measured directly. Table 10 lists
the values calculated by adding ∆lgHm(298.15 K) to fusion
enthalpies and any additional phase transitions occurring
between T ) 298.15 K and T ) Tfus.21 All of the n-alkanes
from C21 to C30 have at least one additional phase transition
occurring between T ) 298.15 K and T ) Tfus. The sum of
these two terms, ∆tpceHm, was adjusted to T ) 298.15 K
using the following equation:22

∆tpceHm(298.15 K)/kJ‚mol-1 )
∆crlHm(Tfus) + ∆cr2crHm(Tt) +
(0.15Cpc - 0.26Cpl - 9.83)(Tfus - 298.15)/1000 (12)
Figure 5. Plot of ln(p/p0) versus 1/T for the n-alkanes: (from top
to bottom) O, n-heneicosane; 0, docosane; 4, n-tricosane; 3, The Cpl and Cpc terms in eq 12 represent the heat capacities
tetracosane; ], pentacosane; b, hexacosane; 9, heptacosane; 2, of the solid and liquid states and were estimated using
octacosane; 1, nonacosane; [, triacontane. group values of 34.9 and 36.6 J‚mol-1‚K-1 for each methyl
group and 31.9 and 26.9 J‚mol-1‚K-1 for each methylene
Table 9. Coefficients for Calculating ln(p/p0) for n-C21 to
C30 from T ) 298.15 K to T ) 568 K According to Eq 11 group, respectively.23 The sublimation enthalpy calculated
for each alkane is listed in the last column of the table.
10-8A 10-6B C D The uncertainty in sublimation enthalpy reported in this
heneicosane 1.9989 -2.9075 -98.135 6.6591 column represents the combined uncertainty associated
docosane 2.1713 -3.1176 110.72 6.5353 with the vaporization enthalpy and the temperature ad-
tricosane 2.3386 -3.322 310.77 6.4198 justment. An uncertainty of 15% in the temperature
tetracosane 2.5072 -3.5286 530.15 6.2817
pentacosane 2.6738 -3.7307 741.19 6.1496 adjustment ((σ) was arbitrarily assigned.
hexacosane 2.8244 -3.9193 910.53 6.0704 Piacente et al.15 have also combined vaporization en-
heptacosane 3.0092 -4.1253 1198.8 5.8109 thalpies with fusion enthalpies for a number of n-alkanes,
octacosane 3.1389 -4.312 1279.4 5.8835 but as noted above, the results of their vaporization
nonacosane 3.2871 -4.5043 1431.2 5.8413 enthalpy measurements have been questioned.14 Of the
triacontane 3.4404 -4.6998 1601.6 5.7696 n-alkanes listed in Table 10, sublimation enthalpies for
Table 10. Sublimation Enthalpies Obtained by Combining ∆lgHm(298.15 K) with Total Phase Change Fusion Enthalpies
Adjusted to T ) 298.15 Ka
∆cr2crHm(Tt) +
∆crlHm(Tfus)b Tfus/K Cpl(298.15 K) Cpc(298.15 K) ∆tpceHm(298.15 K) ∆lgHm(298.15 K) ∆crgHm(298.15 K)
octadecane 61.5 301.3 580.2 503.6 61.2 91.4 152.6c
nonadecane 47.4 304 612.1 530.5 46.9 96.4 143.3c
eicosane 67.8 308.8 644 557.4 66.8 101.8 168.6c
heneicosane 63.18 313.7 675.9 584.3 61.66 106.8 169.1 ( 2.6
docosane 77.35 316.1 707.8 611.2 75.52 111.9 187.7 ( 2.7
tricosane 75.35 320.7 739.7 638.1 73.33 117 190.7 ( 2.8
tetracosane 86.19 324.1 771.6 665 83.32 121.9 205.6 ( 2.8
pentacosane 83.81 326.7 803.5 691.9 80.53 126.8 207.8 ( 2.9
hexacosane 91.7 329.5 835.4 718.8 87.96 131.7 220.2 ( 3.3
heptacosane 87.59 332.1 867.3 638.1 83.4 135.6 219.6 ( 3.4
octacosane 100.08 334.5 899.2 665 95.44 141.9 238.0 ( 5.0
nonacosane 95.82 336.6 931.1 691.9 90.74 147.1 238.6 ( 5.2
triacontane 106.32 338.7 963 718.8 100.8 152.3 253.9 ( 5.3
a Heat capacities are in J‚mol-1.K-1. Enthalpies are in kJ‚mol-1. b T g 298.15 K; see ref 21 for literature values. c Literature values:
t
C18, 152.7; C19, 143.6; C20, 170.4 kJ‚mol-1; ref 24.

Table 11. List of Symbols and Their Definitions

∆lgHm(Tm) enthalpy of vaporization at the mean temperature, Tm
∆slngHm enthalpy of transfer from solution (gc column) to the vapor
∆slnHm enthalpy of solution or adsorption on a gc column
ta the time an analyte spends on a gc column
p, p0 vapor pressure, 101.325 kPa
Cpc, Cpl heat capacity of the solid, heat capacity of the liquid
nc number of carbon atoms
Tfus melting temperature
∆cr2crHm(Tt) solid to solid transition occurring at temperature Tt
∆crlHm(Tfus) enthalpy of fusion at the melting temperature
∆tpceHm(298.15 K) total phase change enthalpy of the solid from T ) 298.15 K to Tfus adjusted to T ) 298.15 K
 Journal of Chemical and Engineering Data, Vol. 49, No. 1, 2004 85

n-C18 to n-C20 have been measured directly; values of 152.7, of solute polarizability and molar volume in solvation. Can. J.
143.6, and 170.4 kJ‚mol-1, respectively, have been re- Chem. 1987, 65, 2624-7. Fuchs, R.; Stephenson, W. K. Enthalpies
of transfer of alkane solutes from the vapor state to organic
ported.24 These results can be compared with the values solvents. Can. J. Chem. 1985, 63, 349-352. Saluja, P. P. S.;
of 152.6, 143.3, and 169.1 kJ‚mol-1 calculated by adding Young, T. M.; Rodewald, R. F.; Fuchs, F. H.; Kohli, D.; Fuchs, R.
∆tpceHm(298.15 K) to ∆lgHm(298.15 K). The results for n-C18 Enthalpies of interaction of alkanes and alkenes with polar and
nonpolar solvents. J. Am. Chem. Soc. 1977, 99, 2949-53 and
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enthalpies measured directly are compared to the sum of and related thermal data between the triple point and normal
boiling temperatures for n-alkanes C5-C20. J. Phys. Chem. Ref.
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(9) Chickos, J. S.; Hesse, D. G.; Liebman, J. F. A group additivity Received for review May 1, 2003. Accepted September 16, 2003. The
approach for the estimation of heat capacities of organic liquids authors gratefully acknowledge the University of Missouri Research
and solids at 298 K. Struct. Chem. 1993, 4, 261-269. Board for financial support.
(10) Fuchs, R.; Chambers, E. J.; Stephenson, K. W. Enthalpies of
interaction of nonpolar solutes with nonpolar solvents. The role JE0301747