Vapor pressures and vaporization enthalpy of codlemone by correlation gas chromatography

J. Chem. Thermodynamics 89 (2015) 306–311

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Vapor pressures and vaporization enthalpy of codlemone by correlation gas chromatography Shannon M. Schultz, Harold H. Harris, James S. Chickos ⇑ Department of Chemistry and Biochemistry, University of Missouri-St. Louis, St. Louis, MO 63121, USA

a r t i c l e

i n f o

Article history: Received 20 February 2015 Received in revised form 26 May 2015 Accepted 4 June 2015 Available online 12 June 2015 Keywords: Codlemone Vapor pressure vaporization enthalpy Correlation gas chromatography Boiling temperature trans, trans 8,10-Dodecadien-1-ol

a b s t r a c t The vapor pressure and vaporization enthalpy of codlemone (trans, trans 8,10-dodecadien-1-ol), the female sex hormone of the codling moth is evaluated by correlation gas chromatography using a series of saturated primary alcohols as standards. A vaporization enthalpy of (92.3 ± 2.6) kJ  mol1 and a vapor pressure, p/Pa = (0.083 ± 0.012) were evaluated at T = 298.15 K. An equation for the evaluation of vapor pressure from ambient temperature to boiling has been derived by correlation for codlemone. The calculated boiling temperature of TB = 389 K at p = 267 Pa is within the temperature range reported in the literature. A normal boiling temperature of TB= (549.1 ± 0.1) K is also estimated by extrapolation. Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction Codlemone is the female sex hormone of the codling moth (Cydia pomonella), a small moth whose caterpillars bore into the fruits of apple and pear trees and occasionally walnuts and quinces in mid- to late-summer [1]. Various methods are used to control the moths which includes both biological and chemical control as well as by using pheromone traps. The structure of codlemone shown in figure 1, is trans, trans 8,10-dodecadien-1-ol. This work reports the vaporization enthalpy at T = 298.15 K and vapor pressures of trans, trans 8,10-dodecadien-1-ol from ambient temperature to the boiling temperature, T = TB. 2. Experimental 2.1. Compounds and purity controls Table 1 lists the origin and purity of both the standards and trans, trans 8,10-dodecadien-1-ol. The sample (PESTANAL Ò) purchased from Sigma Aldrich at the time of analysis by gas chromatography was evaluated as having a mass fraction of 0.78. The gas chromatograph of codlemone is shown in the insert of figure 2. The impurities were not identified. Purity is generally not an issue in these experiments since the analysis is performed on mixtures; the chromatography separates the different components as ⇑ Corresponding author. Tel./fax: +1 314 516 5377/5342. E-mail address: [email protected] (J.S. Chickos). http://dx.doi.org/10.1016/j.jct.2015.06.002 0021-9614/Ó 2015 Elsevier Ltd. All rights reserved.

illustrated in figure 2 [2]. This is one of the advantages of this technique. When analyzing impure components, small concentrations of the component are used in the event of an impurity overlap with a standard. Compounds are arranged according to their elution off the column. 2.2. Methods The GC correlation experiments were run on an HP 5890 gas chromatograph running HP Chemstation on a Supelco 15 m 0.32 mm, 1.0 lm thick SPB-5 capillary column using helium as the carrier gas at a split ratio of approximately 100/1. The temperature was controlled by the instrument to T = ±0.1 K and was monitored by a Fluke 50S K/J digital thermometer. Methylene chloride was used as the solvent. At the temperatures of the experiments, the solvent also served as the non-retained reference. Column residence times, ta, were determined as the difference between an analyte’s retention time and the retention time of the solvent. Experimental retention times are provided in the supplementary material (Tables S1A and S2A). Enthalpies of transfer (DtrnHm(Tm)) were calculated as the product of the gas constant (8.3145 J  K1  mol1) and the absolute value of the slope of the line obtained from plots of ln(to/ta), vs 1/T, where the reference time, to = 60 s. The term Tm refers to the mean temperature of measurement. All plots were characterized by correlation coefficients, r2 > 0.99, obtained from a linear least squares treatment of the data. The enthalpy of transfer is related to the vaporization enthalpy, Dgl Hm (Tm), by equation (1) where DintrHm(Tm) refers to

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discussed below were calculated from the uncertainties associated with each coefficient according to standard methods. Details are provided in the supplementary data.

FIGURE 1. Codlemone, trans, trans 8,10-dodecadien-1-ol.

2.5. Literature vaporization enthalpies the enthalpy associated with the interaction of each analyte with the column [3].

Dtrn Hm ðT m Þ ¼ Dgl Hm ðT m Þ þ Dintr Hm ðT m Þ

The following vaporization enthalpies summarized in table 2 have been used as standards. For 1-decanol, a value of (81.2 ± 0.4) kJ  mol1 was used which is an average of (81.5 ± 0.8) kJ  mol1 reported by Mansson et al. [6] and (80.9 ± 0.3) kJ  mol1 reported by Kulikov et al. [7]. For 1-undecanol, the value (85.8 ± 1.5) kJ  mol1, an average of (84.7 ± 0.3) and (86.8 ± 0.3) kJ  mol1 reported by Kulikov et al. [7] and N’Guimbi et al. [8], respectively, was used. The result reported by N’Guimbi et al. was adjusted to T = 298.15 K using equation (2). 1-Dodecanol has been evaluated numerous times. An average of three values reported by Mansson et al. [6], Kulikov et al. [7] and Svensson [9] of (90.8 ± 1.1) kJ  mol1 was selected. For 1-tetradecanol, the value of (99.5 ± 2.4) kJ  mol1, also represents an average of four values [10] reported by Mansson et al. [6], Kulikov et al. [7], N’Guimbi et al. [8] and Kemme and Kreps [11]. Finally the vaporization enthalpy of 1-pentadecanol, (103.5 ± 1.4) kJ  mol1, was derived as the average of two values [7,8]. Vaporization enthalpies in some cases were calculated from the experimental vapor pressures reported in the literature at the mean temperature stated in the table.

ð1Þ

Dgl Hm (T)

A second plot of DtrnHm(Tm) vs where T – Tm is also linear provided all standards are appropriately selected and their vaporization enthalpies are all referenced to the same temperature. The equation of this second line can be used to evaluate the vaporization enthalpy of the target(s) at temperature T. Bracketing the vaporization enthalpy of the targets provides the best results since heat capacity differences between the target and references are generally minimized. Vapor pressures can also be evaluated by these experiments provided the vapor pressures of the standards are available and reliable. In this case a plot of ln(p/po) against ln(to/ta) of the standards is also linear. This linearity is usually reproduced as a function of temperature up to the boiling temperature of the most volatile component. The equation of the line at a given temperature, T, is then used to evaluate the vapor pressures of the target substances at that temperature. The term po refers to a reference pressure; in this work, po = 101,325 Pa.

2.6. Vaporization enthalpy estimates

2.3. Temperature adjustments

Vaporization enthalpies of both the standards and codlemone were estimated using a simple three parameter model, equation

Vaporization enthalpies of the standards were adjusted for temperature if necessary using equation (2) [4]. The Cp(l) represents the heat capacity of the liquid and was estimated using a group additivity approach [5]. 1

1

Dlg Hm ð298:15 KÞ=ðkJ  mol Þ ¼ Dlg Hm ðT m Þ=ðkJ  mol Þ 1

þ ½ð10:58 þ 0:26  C p ðlÞ=ðJ  K1  mol ÞÞðT m =K  298:15Þ=1000 ð2Þ 2.4. Uncertainties All uncertainties refer to one standard deviation unless noted otherwise. The slopes and intercepts reported below were calculated by linear regression. Uncertainties associated with the correlations between DHtrs(Tm) and Dgl Hm (Tm) were calculated from the uncertainties in the slope and intercept as (u21 + u22)0.5; similarly for combined results. Vapor pressures fit as a function of temperature were fit by non-linear least squares. The uncertainties reported for values evaluated from logarithmic terms are reported as an average value of the two uncertainties evaluated. The standard deviation in the term Cp(l) has been evaluated as ±16 J  K1  mol1 [4]. Uncertainties in TB calculated from the third order polynomial

FIGURE 2. Codlemone with a series of 1-alkanol standards at T = 423 K. From left to right: 1-decanol (1.8), 1-undecanol (2.7), 1-dodecanol (4.1), codlemone (5.3), 1tetradecanol (10.1), 1-pentadecanol (16.2 min). Peaks less than one minute are not shown. Insert: The gas chromatograph of commercial codlemone at T = 423 K.

TABLE 1 Provenance and mass fraction purity of the materials studied.a

1-Decanol 1-Undecanol trans, trans 8,10-Dodecadien-1-ol 1-Dodecanol 1-Tetradecanol 1-Pentadecanol a b

C10H22O C11H24O C12H22O C12H26O C14H30O C15H32O

CAS No.

Supplier

Mass fraction purity

112-30-1 112-42-5 33956-49-9 112-53-8 112-72-1 629-76-5

Sigma Aldrich Fluka Sigma Aldrich Sigma Aldrich Sigma Aldrich

0.98 0.96 0.78 b 0.98 0.97 >0.99

Mass fractions reported by the suppliers except for trans, trans 8,10-dodecadien-1-ol. PESTANAL Ò, analytical standard; analysis by gas chromatography.

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TABLE 2 Experimental enthalpies of vaporization of the alcohols.

Dgl Hm (Tm)

Compound

kJ  mol

81.5 ± 0.8 80.9 ± 0.3

298 298

1-Undecanol

84.7 ± 0.3 85.7 ± 0.3

298 308

92.0 ± 0.6 90.0 ± 0.3 84.7 ± 0.5

298 298 343

102.2 ± 2.3 98.7 ± 0.6 88.1 ± 0.5 77.3 ± 2.5

298 298 353 449

102.5 ± 0.6 95.5 ± 1.7

298 358.1

1-Tetradecanol

1-Pentadecanol

Cp(l)/ JK

1-Decanol

1-Dodecanol

a

Tm/K

1

1

Dgl Hm (298 K)/kJ  mol1

DCpDT  mol

1

kJ  mol

1

References a

Value

Mean value

81.5 ± 0.8 80.9 ± 0.3

81.2 ± 0.4

[6] [7]

84.7 ± 0.3 86.8 ± 0.3

85.8 ± 1.5

1.2 ± 0.1

[7] [8]

90.8 ± 1.1

5.6 ± 0.7

92.0 ± 0.6 90.0 ± 0.3 90.3 ± 0.9

[6] [7] [9]

502.7 502.7

7.8 ± 0.9 21.2 ± 2.4

102.2 ± 2.3 98.7 ± 0.6 95.9 ± 1.0 98.5 ± 3.5

534.6

9.0 ± 1.0

102.5 ± 0.6 104.5 ± 2.0

407

438.9

[6] [7] [8] [11]

98.9 ± 2.6

103.5 ± 1.4

[7] [8]

Uncertainties are one standard deviation of the mean.

2

TABLE 3 Coefficients of Chebyshev polynomial, equation (4).

0

Tmin/K

Tmax/K

ao

a1

a2

a3

1-Decanol 1-Dodecanol

400 425

529 550

1387.15 1366.542

512.274 496.253

13.792 11.973

1.418 1.221

428 439

Correlated values [13] 652 1801.32 877.22 667 1837.30 897.45

22.81 20.84

7.47 7.82

1-Tetradecanol 1-Pentadecanol

-2 -4

ln(p/po)

Experimental

-6 -8 -10

(3) [12]. The term nC refers to the total number of carbon atoms, nQ to the number of quaternary sp3 hybridized carbons, and b refers to the contribution of the functional group. For alcohols, the contribution of the hydroxyl group is 29.4 kJ  mol1 [12]. 1

Dgl Hm ð298:15Þ=kJ  mol

¼ 4:69ðnC  nQ Þ þ 1:3nQ þ b þ 3:0

ð3Þ

2.7. Vapor pressures The vapor pressures of the standards used were obtained as follows: For 1-decanol, experimental vapor pressures from T = (281.5 to 333) K reported by Kulikov et al. [7] were combined with experimental values from T = (349.4 to 406.2) K reported by Ambrose et al. [13]. Additionally, extrapolated values from T = (416.2 to 504) K at 10 K intervals were included as calculated using equation (4) where Es(x) is the Chebyshev polynomial in x of degree s, also reported by Ambrose et al. [13]. For purposes of convenience and uniformity, vapor pressures for all the standards were then fit to equation (5). Similarly for 1-undecanol, experimental vapor pressures from T = (313.2 to 354.3) K reported by Kulikov et al. [7] and values from T = (293.2 to 403.1) K reported by N’Guimbi et al. [8] were combined with extrapolated values using equation

-12 -14 -16 0.0015

0.0020

0.0025

0.0030

0.0035

0.0040

1/T/K FIGURE 3. Experimental (h) and extrapolated (s) vapor pressures (from left to right) of 1-pentadecanol, 1-tetradecanol, 1-dodecanol, 1-undecanol and 1-decanol. The circles represent values calculated from the Chebyshev polynomial and the line represents the fit using the third order polynomial, equation (5) and the constants of table 4, po = 101,325 Pa.

(4) from T = (413.1 to 521.3) K at 10 K intervals and fit to equation (5). The coefficients of the Chebyshev polynomial for 1-undecanol were not derived from experimental data but rather through correlation by Ambrose et al. [13]. For 1-dodecanol, experimental vapor pressures from T = (303.6 to 348.3) K [7], from T = (312.9 to 413.1) K [8], and from T = (376.6 to 437.6) K [13] were combined with extrapolated values calculated from the Chebyshev polynomial from T = (437.6 to 537.6) K also at 10 K intervals [13]. Similarly for 1-tetradecanol, experimental values from T = (312.3

TABLE 4 Coefficients of the third order polynomial of the standards, equation (5).

1-Decanol 1-Undecanol 1-Dodecanol 1-Tetradecanol 1-Pentadecanol a b

A  106/K3

B  104/K2

C  102/K

D

TB calc/Ka

TB/Ka,b

257.8230 147.2111 305.9974 17.4612 354.5315

334.445 260.353 386.482 165.405 433.368

40.0282 19.6533 47.5983 10.1613 47.4067

3.201 4.768 2.531 6.985 2.802

504.3 ± 7.4 521.4 ± 5.1 538.4 ± 14.7 569.2 ± 12.1 584.3 ± 10.9

504.26 521.3 537.79 568.8 583.4

Boiling temperatures at po = 101,325 Pa. Ref. [13].

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to 346.6) K [7] and values from T = (333.2 to 438.2) K [8] were combined with extrapolated values obtained from equation (4) also derived by correlation from T = (438.2 to 568.2) K at 10 K intervals [13]. Finally for 1-pentadecanol, experimental vapor pressures from T = (319.4 to 357.9) K [7] and from T = (343.1 to 453.2) K [8] were combined with extrapolated values obtained by correlation from equation (4) from T = (453.2 to 583.2) K [13] at 10 K intervals. The coefficients of the Chebyshev polynomial used for the standards are given in table 3 and the resulting coefficients for equation (5), fit from the combined data are given in table 4. Note that po in equation (4) refers to 1 kPa and po in equation (5) refers

to 101,325 Pa. Both equations are known to extrapolate well with temperature. The last two columns of table 4 compare the boiling temperatures calculated using the constants evaluated for equation (5) with those reported by Ambrose et al. using equation (4) [13]. Figure 3 illustrates the results of combining the data. The solid circles represent experimental values while the empty circles are the extrapolated values calculated using the Chebyshev polynomial. The lines in the figure represent the resulting values calculated using equation (5). Despite the good fit, the uncertainties in some TB are significant. This is due to the scatter associated with some of the experimental data.

TABLE 5 Correlations between DtrsH(Tm) and Dgl Hm (298 K). slope/K

Intercept

1-Decanol 1-Undecanol 1-Dodecanol Codlemone 1-Tetradecanol 1-Pentadecanol

5627.00 6078.87 6534.52 6749.17 7446.81 7899.39

12.958 13.523 14.103 14.331 15.28 15.864

1-Decanol 1-Undecanol 1-Dodecanol Codlemone 1-Tetradecanol 1-Pentadecanol

5455.28 6039.58 6393.48 6597.78 7293.54 7731.58

12.517 13.411 13.737 13.941 14.885 15.434

Dgl Hm (298 K) (kJ  mol1) lit

DtrsH (409 K) (kJ  mol1)

Dgl Hm (298 K) (kJ  mol1) calca

Run 1 46.78 50.54 54.33 56.11 61.91 65.67

81.2 ± 0.4 85.8 ± 1.5 90.8 ± 1.1 98.9 ± 2.6 103.5 ± 1.4

81.4 ± 1.7 85.8 ± 1.8 90.3 ± 1.8 92.3 ± 1.9 99.1 ± 2.0 103.5 ± 2.0

Run 2 45.35 50.21 53.15 54.85 60.64 64.28

81.2 ± 0.4 85.8 ± 1.2 90.8 ± 1.1 98.9 ± 2.6 103.5 ± 1.4

80.9 ± 3.0 86.7 ± 3.2 90.2 ± 3.3 92.2 ± 3.3 99.1 ± 3.5 103.4 ± 3.6

Run 1: Dgl Hm (298.15 K)/kJ  mol1 = (1.17 ± 0.02)DtrsH (409 K) + (26.78 ± 1.3); r2 = 0.9988 (6). Run 2: Dgl Hm (298.15 K)/kJ  mol1 = (1.19 ± 0.04)DtrsH (409 K) + (26.95 ± 2.35); r2 = 0.9962 (7). a Uncertainties represent 1 standard deviation.

TABLE 6 A summary of the vaporization enthalpies in kJ  mol1 at T = 298.15 K of runs 1 and 2 Dgl Hm (298 K)/kJ  mol1. Run 1 Codlemone

Run 2

92.3 ± 1.9

Average

92.2 ± 3.3

a

Lit

b

Estimate (Equation (3))

92.3 ± 2.6

88.7 ± 4.4

Standards 1-Decanol 1-Undecanol 1-Dodecanol 1-Tetradecanol 1-Pentadecanol a b

81.4 ± 1.7 85.8 ± 1.8 90.3 ± 1.8 99.1 ± 2.0 103.5 ± 2.0

80.9 ± 3.0 86.7 ± 3.2 90.2 ± 3.3 99.1 ± 3.5 103.4 ± 3.6

81.2 ± 2.4 86.3 ± 2.5 90.3 ± 2.6 99.1 ± 2.8 103.5 ± 2.8

81.2 ± 0.4 85.8 ± 1.5 90.8 ± 1.1 98.9 ± 2.6 103.5 ± 1.4

79.3 ± 4.0 84.0 ± 4.2 88.7 ± 4.4 98.1 ± 4.9 102.8 ± 5.1

Uncertanties are standard deviations averaged over the two runs. See table 2 for references.

TABLE 7 Correlation results between liquid ln(p/po)lit and ln(to/ta)avg values at T = 298.15 K; po = 101,325 Pa. Run 1/Run 2

slope/K

Intercept

104  to/ta

1-Decanol

5627.00 5455.28

12.958 12.517

1-Undecanol

6078.87 6039.58

1-dodecanol

ln(to/ta)avg

ln(p/po)lit

ln(p/po)calca

26.989 30.893

5.845

11.269

11.22 ± 0.17

13.523 13.411

10.435 10.643

6.855

12.374

12.39 ± 0.19

6534.52 6393.48

14.103 13.737

4.04 4.497

7.759

13.363

13.44 ± 0.20

Codlemone

6749.17 6597.78

14.331 13.941

2.470 2.778

8.246

1-Tetradecanol

7446.81 7293.54

15.28 14.885

0.615 0.692

9.636

15.689

15.52 ± 0.22

1-Pentadecanol

7899.39 7731.58

15.864 15.434

0.242 0.276

10.562

16.672

16.69 ± 0.23

ln(p/po) = (1.160 ± 0.017) ln(to/ta)  (4.440 ± 0.147), r Uncertanties described in section 2.4.

a

2

= 0.9993 (8).

14.01 ± 0.21

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experimental error of the vaporization enthalpy of 1-dodecanol, the relative difference between the two is probably fairly accurate. The vaporization enthalpies of unsaturated materials are generally slightly larger than their saturated counterparts [14]. Included in the last column of the table are the values estimated using equation (3). These are also within experimental error of the values obtained by correlation.

0 -2

ln(p/po)

-4 -6 -8

3.2. Vapor pressures

-10 -12 -14 -16 0.0015

0.0020

0.0025

0.0030

0.0035

0.0040

1/T/K FIGURE 4. Experimental (h) and extrapolated (s) vapor pressures (from left to right) of 1-pentadecanol, 1-tetradecanol, 1-dodecanol, 1-undecanol and 1-decanol. The circles represent values calculated from the Chebyshev polynomial and the line represents the fit using the third order polynomial, equation (5) and the constants obtained by correlation of ln(p/po) with ln(to/ta), table 8; po = 101,325 Pa.

T=K log10 ðp=po Þ ¼ ao =2 þ

3 X

as Es ðxÞ

ð4Þ

s¼1

where Es(x) = a1(x) + a2(2x2  1) + a3  (4x2  3x); x = [2T/K  (Tmax + Tmin)]/(Tmax  Tmin); and po = 1 kPa.

lnðp=po Þ ¼ A  ðT=KÞ3 þ B  ðT=KÞ2 þ C  ðT=KÞ þ D where po ¼ 101; 325 Pa

ð5Þ

3. Experimental results 3.1. Vaporization enthalpies The slopes and intercepts obtained from plots of ln(to/ta) vs 1/T are provided in table 5 which also summarizes the results of correlations between Dgl Hm (298.15) and DHtrs(Tm). Equations (6) and (7) summarize the quality of the correlations. Both sets of plots were characterized by a correlation coefficient, r2 > 0.99. Table 6 summarizes the results of both runs. A vaporization enthalpy of (92.3 ± 2.6) kJ  mol1 is obtained for trans, trans 8,10-dodecadien-1-ol (codlemone). The uncertainty reported is also an average value of the standard deviation associated with each run. While the vaporization enthalpy of codlemone is within

Since both runs contained the same standards and were run at approximately the same temperatures, values of to/ta calculated from the slopes and intercepts of both were averaged. Values of ln(to/ta)avg of the standards were correlated with the corresponding values of ln(p/po) calculated according to equation (5) and the constants from table 4. Table 7 illustrates the correlation results obtained at T = 298.15 K. Equation (8) summarizes the relationship found between ln(p/po) and ln(to/ta)avg at this temperature while the correlation coefficient, r2 = 0.9993, provides a measure of the linearity between the two independent variables. These correlations were then repeated from T = (298.15 to 500) K at 10 K intervals. Values of ln(p/po) for both the standards and codlemone were collated and the resulting values fit to equation (5). Table 8 summarizes the resulting coefficients of equation (5) for both codlemone and the standards and compares the calculated boiling temperatures obtained by extrapolation to those reported by Ambrose et al. [13]. The boiling temperatures are reproduced within ±0.8 K. Figure 4 also provides a pictorial representation of the fit of the vapor pressures calculate by correlation using the constants provided in table 8 with the experimental, correlated and extrapolated vapor pressures of figure 3. The two figures are virtually indistinguishable. The vapor pressure of codlemone at T = 298.15 K is found to be p = (0.083 ± 0.012) Pa and its boiling temperature, TB = (389 ± 0.1) K at p = 267 Pa, is within the boiling point range of TB = (383–393) K reported in the MSDS sheet supplied by Sigma Aldrich at this pressure [15]. A boiling temperature, TB = (549.2 ± 0.2) K at p = 101,325 Pa was also evaluated. The vapor pressures of the standards at T = 298.15 K obtained by correlation are also all within experimental error of the values calculated using equation (5)and the constants from table 4. The uncertainties (1r) in TB obtained by correlation and just discussed or reported in table 8 are significantly smaller than those reported in table 4. It is important to point out that these uncertainties simply reflect how well equation (5) is capable of reproducing the analytical expressions described in columns 2 and 3 of table 5 and are not a statistically significant measurement of the uncertainty in TB.

TABLE 8 Coefficients of equation (5) resulting from correlations between ln(p/po) and ln(to/ta), of the standards, boiling temperatures and liquid vapor pressures at T = 298.15 K; po = 101,325 Pa. Target

A  106/K3

B  104/K2

C  102/K

D

TB calc/Ka

TB lit/Kb

Codlemone

217.4047

323.6394

31.0824

3.759

389.0 ± 0.1d,e

383–393d

1-Decanol 1-Undecanol 1-Dodecanol 1-Tetradecanol 1-Pentadecanol

221.7108 208.9309 212.9935 204.1518 200.3147

309.8517 306.3749 316.2683 322.1227 325.4350

35.0990 30.3080 30.3479 25.5104 23.2600

3.480 4.007 3.906 4.347 4.547

504.8 ± 0.1 520.3 ± 0.1 538.5 ± 0.1 569.6 ± 0.1 584.3 ± 0.2

504.3 521.3 537.8 568.8 583.4

102  p298 K/Pa b c Calc /lit (8.3 ± 1.2)/11.8

f

Standards

a b c d e f

Boiling temperature at po = 101,325 unless noted otherwise. Ref. [13] unless noted otherwise. Uncertainties calculated from the correlation at T = 298.15 K as described in section 2.4. TB/K at p/Pa = 267, Sigma Aldrich MSDS sheet. Boiling temperature at p = 101,325 Pa, TB = (549.1 ± 0.1) K; predicted value TB = 543.9 ± 9 K, ref. [16]. Predicted value, ref. [16].

(133 ± 17)/129 (41 ± 6)/42.8 (14.5 ± 2.0)/15.9 (1.6 ± 0.2)/1.6 (0.56 ± 0.12)/0.58

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S.M. Schultz et al. / J. Chem. Thermodynamics 89 (2015) 306–311 TABLE 9 A comparison of the vaporization enthalpies calculated by correlation between enthalpies of transfer and vaporization enthalpies and between ln plots of vapor pressures and adjusted retention times reciprocals.

Dgl Hm (298 K) kJ  mol1 from Dgl Hm (298 K) vs DtrsH(Tm)a Codlemone

92.3 ± 2.6

Dgl Hm (298 K) b kJ  mol1 fromln(p/po) vs ln(to/ta) 93.3

Standards 1-Decanol 1-Undecanol 1-Dodecanol 1-Tetradecanol 1-Pentadecanol

81.2 ± 2.4 86.3 ± 2.5 90.3 ± 2.6 99.1 ± 2.8 103.5 ± 2.8

80.7 86.5 90.9 100.8 105.7

a

From table 6. Calculated from the slope of line from a plot of ln(p/po)corr vs 1/T at Tm = 298.15 K where (p/po)corr represents the ratio calculated using equation (5) and the constants of table 8.

b

The average uncertainty associated with the standards of table 4 is ±10 K. This is probably a more reasonable estimate of the uncertainty in the boiling temperature of codlemone. As an independent check on the quality of the correlations between ln(p/po) and ln(to/ta)avg,vaporization enthalpies at T = 298.15 K were calculated from the slope of the line from plots of ln(p/po) vs 1/T using equation (5) and the constants from table 8. The results obtained are compared in table 9 to the average values obtained from correlations between enthalpies of vaporization and enthalpies of transfer, table 6. The two sets values are in agreement within the uncertainties stated. Of the two values cited in the table, the values obtained from correlations between DtrnHm(Tm) and Dgl Hm (298.15 K) are considered to be the more reliable. Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.jct.2015.06.002.

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JCT 15-105 References [1] Royal Horticultural Society at: (accessed 2.1.15).