Accepted Manuscript

Vapor pressures and enthalpies of vaporization of a series of γ and δ-lactonesby correlation gas chromatography

Mikhail Kozlovskiy Chase Gobble James Chickos

PII S0021-9614(14)00021-4DOI httpdxdoiorg101016jjct201401016Reference YJCHT 3828

To appear in J Chem Thermodynamics

Please cite this article as M Kozlovskiy C Gobble J Chickos Vapor pressures and enthalpies of vaporization ofa series of γ and δ-lactones by correlation gas chromatography J Chem Thermodynamics (2014) doi httpdxdoiorg101016jjct201401016

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1

Vapor pressures and enthalpies of vaporization of a series of γ and δ-lactones by

correlation gas chromatography

Mikhail Kozlovskiy Chase Gobble and James Chickosa

Department of Chemistry and Biochemistry

University of Missouri-St Louis

St Louis MO 63121

Dedicated to the memory of the late Professor Manuel Ribeiro da Silva

ABSTRACT

The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and γ and δ-

dodecanolactone used commercially as flavor ingredients are reported as are their vapor

pressures over the temperature range T = (29815 to 350) K Vaporization enthalpies at T

= 29815 K of (660plusmn39) (794plusmn44) (801plusmn45) (839plusmn46) and (8461plusmn47) kJsdotmol-1

and vapor pressures also at T = 29815 K of (28plusmn09) (012plusmn005) (009plusmn004)

(004plusmn002) and (003plusmn002) Pa respectively have been evaluated by correlation gas

chromatography experiments The vaporization enthalpies of the lactones studied are

reproduced within plusmn05 kJsdotmol-1

using a group additivity scheme reported previously for

γ- and δ-lactones The vaporization enthalpies of the γ- and δ-lactones are compared to a

similar series of ω-lactones

Keywords γ- and δ-Lactones Vapor pressure Enthalpy of vaporization Correlation Gas

chromatography

This article is dedicated to the memory of the late Professor Manuel Ribeiro da Silva

2

e-mail jscumsledu

PhFax 314 516 53775342

1 Introduction

A number of γ and δ-lactones of hydroxylated fatty acids are important components in

flavors For example γ-dodecanolactone is described as having a waxy fatty sweet aroma

with green rind-like notes whereas δ- dodecanolactone is described as having fruity

peach-like and buttery notes [1] Nearly all the γ and δ-lactones from C6 to C14 are GRAS

chemicals (Generally Recognized As Safe) as recognized by the US Federal Food Drug

and Cosmetic Act [2] and are used as components in flavors

Recently the vapor pressures and vaporization enthalpies of a series of γ and δ-lactones

have been reported [34] The vapor pressures and vaporization enthalpies of a number of

the materials reported in these two articles have been used to evaluate these properties for

γ-octanolactone both γ and δ-undecanolactone and γ and δ-dodecanolactone by

correlation gas chromatography Vapor pressures and vaporization enthalpies do not

appear to have been previously reported for these lactones Vapor pressures are available

on MSDS sheets but it is not clear whether these are experimental or estimated

properties The structures of both the γ and δ-lactones as well as the corresponding ω-

lactones to which they are compared to are illustrated in figure 1

2 Experimental methods

21 Compounds and purity controls

Table 1 lists the origin and purity of both the standards and targets All γ-lactones greater

than C4 and all δ-lactones greater than C5 are chiral and yet the olfactory properties of

individual enantiomers are not generally discussed The commercial samples are all

assumed to be racemic Several of the materials used in this study are also reported as

mixtures of isomers All materials were analyzed by gas chromatography to evaluate their

chemical composition The results are reported in table 1 While our analyses differ

slightly from the values reported by the suppliers in a few instances some of our samples

were acquired some time ago The isomers which were present in some of the samples

3

were not identified All were present in minor amounts Their analyses are given in the

footnotes of table 1 Figure 2 provides a copy of the gas chromatograph of the mixture

The ability to generate reliable thermochemical data with less than pure samples is one of

the advantages of the correlation gas chromatography method

22 Methods

The measurements were performed on an HP 5890 gas chromatograph running HP

Chemstation Isothermal chromatograms were obtained over a T = 30 K temperature

range at intervals of T = 5 K on a Supelco 15 m 032 mm 10 microm film thickness SPB-5

capillary column at a split ratio of approximately 1001 using helium as the carrier The

column temperature was monitored continuously using a Vernier stainless steel

temperature probe with a GoLink USB interface running Logger Lite software The

column temperature was maintained by the instrument at plusmn01 K The solvent used was

methanol which also served as the non-retained reference at the temperatures of the

experiments

Residence time of each analyte on the column was calculated by difference between the

retention time of each analyte and the non retained reference The experimental retention

times are provided in the supplementary material The residence time ta is inversely

proportional to an analytersquos vapor pressure off the column Plots of ln(tota) against 1T

for each analyte where to refers to the reference time 60 s resulted in straight lines with

slopes equal to the enthalpy of transfer of the analyte from the column to the gas phase

divided by the gas constant -∆Htrn(Tm)R The correlation coefficient of the fit for each

analyte r2 exceeded 099 The enthalpy of transfer ∆Htrn(Tm) is related to the

vaporization enthalpy ∆lgHm(Tm) by equation 1[6]

The ∆Hintr(Tm) term represents the

enthalpy of interaction of the analyte with the column and is generally small in magnitude

in comparison to ∆lgHm(Tm) [7] Additional details of the correlation gas chromatography

method have been provided previously [78] The results of a second plot of ∆Htrn(Tm)

versus ∆lgH(29815) is described below as are the results of correlating ln(ppo) against

ln(tota) to evaluate vapor pressures

4

∆Htrn(Tm) = ∆lgHm (Tm) + ∆Hintr(Tm) (1)

23 Literature vaporization enthalpies and vapor pressures

The vaporization enthalpies of all the standards are available at T = 29815 K [34] The

temperature range of available vapor pressures varies some but generally data are

available from T = (29815 to 350) K All literature vapor pressure data have been fit to

equation 3 [34] Vaporization enthalpies and the A B and C constants of equation 2 are

reported in table 2

ln(pPa) = [A ndash BT(K) ndashCsdotln(T(K)29815)]R (2)

24 Temperature adjustments

The vapor pressures of all the standards are available roughly from T = (29815 to 350)

K As a means of evaluating how well the vapor pressures evaluated from correlations of

ln(ppo) with ln(tota) as described below reproduced their temperature dependence the

vaporization enthalpies calculated from the vapor pressures evaluated by correlation of

both the standards and targets were calculated at their mean temperature Tm = 324 K

They were then adjusted back to T = 29815 K for comparison with the values of the

standards and those of the targets as obtained by correlation Equation 3 was used for this

temperature adjustment [9] The term Cp(298 K)(l) refers to the heat capacity of the liquid

at T = 29815 k and was estimated by group additivity [10] The vaporization enthalpy

values obtained are provided and discussed below

∆lgHm(29815 K)(kJmol

-1) = ∆l

gHm(Tm)kJmol

-1 +

[(1058 + 026Cp(298 K)(l)(Jmol-1K

-1))( TmK - 29815 K)]1000 (3)

25 Uncertainties

The uncertainty associated with equation 3 is given by 16( TmK - 29815 K)1000

kJmol-1

[9] Uncertainties associated with the correlations were calculated as (u12 + u2

2)

05

where u represents the uncertainty associated with both the slope and intercept A similar

5

protocol was used in evaluating vaporization enthalpies adjusted to 29815 K from the

mean temperature

3 Experimental results and discussion

31 Vaporization enthalpies

If appropriate standards are used in the correlation between ∆Htrn(Tm) and ∆lgHm (29815

K) a good linear relationship is obtained despite the fact that the two enthalpies are

referenced to different temperature Figure 3 illustrates this correlation for the lactones

used as standards in run 1 The details of two correlations are summarized in tables 3A

and B and equations 4 and 5 listed below each respective table The results of both runs

are summarized in table 4 and compared to the literature values Despite the uncertainty

of approximately 4 kJmol-1

calculated from the correlation equations the vaporization

enthalpies of the standards are reproduced with an uncertainty of plusmn13 kJmol-1

(2 σ)

32 Vapor pressures

Vapor pressures generated from equation 2 at T = 29815 K were first converted to values

of ppo where po = 101325 Pa and then correlated as ln(ppo) with the corresponding

values of ln(tota) calculated from the slopes and intercepts listed in table 3 for both runs 1

and 2 The results of plotting ln(ppo) against ln(tota) at T = 29815 K for run 1 are

summarized in table 5 by equation 6 and illustrated in figure 4 The square symbols and

their associated uncertainties in the figure represent the values of ln(ppo) of the targets

calculated using equation 6 Results for run 2 are summarized by equation 7 and a table

similar to table 5 is provided in the supplementary material These correlation were then

repeated from T = (29815 to 350) K at 10 K intervals (not shown) The correlation

coefficients for each temperature evaluated r 2 gt 099 The vapor pressures obtained over

this 50 K temperature range were then fit to equation 8 The slopes and intercepts of the

fits are provided in table 6 for run 1 The vapor pressures calculated over this temperature

range for run 2 were virtually identical in most cases to those of run 1 after rounding off

and are not reported here Vapor pressure data for run 2 are provided in the

supplementary material All fits of ln(ppo) evaluated by correlation as a function of

temperature as 1T were characterized by correlation coefficients r2 gt 099

6

ln(ppo) = Arsquo+ Brsquo(TK) (8)

As an independent means of determining the overall quality of these correlations as a

function of temperature vaporization enthalpies were calculated from the product of the

slope of line of equation 8 and the gas constant (R) for each compound These values are

reported in the third column of table 6 These values were then adjusted back to T =

29815 K using equation 2 and the heat capacities listed in the table column 5 These

vaporization enthalpies adjusted to T = 29815 K are included in column 6 of table 6 and

compared to the values used as standards or to the values reported in table 4 in the last

column of the table The vaporization enthalpies of both standards and targets are all

reproduced with a standard deviation of plusmn15 kJsdotmol-1

(2 σ)

The vapor pressures at T = 29815 K in the last column of table 5 calculated using

equation 6 and reproduced in column 3 of table 7 are compared with available

experimental and estimated values in table 7 columns 2 and 5 respectively The

uncertainties associated with equation 6 were calculated from the corresponding

uncertainties in the slope and intercept of the equation as described above Vapor

pressures calculated using equation 8 and the constants of table 6 column 4 of table 7

differ slightly but also reproduce both literature values and those calculated using

equation 6 well within the uncertainties cited The vapor pressures of the standards are

reproduced using both equation 6 and by equation 8 and the constants of table 6 within 9

of their value The last two columns of the table compare vapor pressures calculated at

T = 29315 K using equation 8 and the constants of table 6 The vapor pressures reported

in column 6 are from MSDS sheets made available by the supplier [5] It is not known if

they represent experimental or estimated values The vapor pressures calculated in this

work are consistently smaller than the MSDS values by roughly a factor of 4 Equation 8

and the constants of table 6 can be used to provide vapor pressures of the materials

evaluated in this work from T = (29815 to 350) K

33 Vaporization enthalpy estimates

7

Emelrsquoyanenko et al[4] reported a group additivity procedure for predicting the

vaporization enthalpies of γ and δ-lactones Table 8 summarizes the group values they

reported and table 9 compares the predicted values with the experimental vaporization

enthalpies reported previously and those evaluated in this work Agreement with the

results reported here are well within the experimental uncertainties All values in column

4 are slightly over predicted but are reproduced with a standard deviation of plusmn10 kJsdotmol-1

(2 σ)

34 Vaporization enthalpy comparisons

In addition to the γ and δ-lactones studied Wiberg and Waldron [13] reported the

vaporization enthalpies of a corresponding series of ω-lactones These results are

compared in table 10 It should be noted that ω and γ-butanolactone and ω and δ-

pentanolactone refer to the same material and are included to illustrate the reproducibility

of literature values As the ring size increases and becomes more flexible the

vaporization enthalpies appear to attenuate Consistent with this interpretation an

alternative estimation equation eq 9 generated from the vaporization enthalpies of

acyclic esters [14] greatly underestimates the vaporization enthalpies of both the smaller

γ and δ-lactones but appears to provide an improved estimation of the larger ones as

indicated in the last column of table 10 The cyclic ethers oxetane tetrahydrofuran and

pyran are also under-estimated by eq 9 [15] The nC nQ and b terms in equation 9 refer to

the total number of carbons the number of quaternary sp3 hybridized carbons (0) and the

contribution of the functional group (105 kJsdotmol-1

) respectively

∆lgHm(298 K) kJsdotmol

-1 = 469(nC - nQ) 13nQ +30 + b (9)

33 Summary

The vaporization enthalpies at T = 29815 K and vapor pressures from T = (29815 to

350) K of three γ and two δ-lactones are evaluated by correlation gas chromatography

using a series of closely related standards The vaporization enthalpies are believed

known with an uncertainty somewhat less than plusmn4 kJsdotmol-1

and vapor pressures within an

uncertainty of approximately 40 of their value

8

Appendix A Supplementary data

Supplementary data associated with this article can be found in the online version at

http

References

(1) httpwwwbedoukiancomproductsproductaspid=463 accessed 82813

(2) httpwwwfdagovFoodIngredientsPackagingLabelingGRAS accessed

82813

(3) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 39 (2007) 10-15

(4) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 40 (2008) 911-16

(5) httpbedoukiancomproductssearchflavorasp accessed 82913

(6) L A Peacock R Fuchs J Am Chem Soc 99 (1977) 5524-5

(7) D Lipkind J S Chickos J Chem Eng Data 55 (2010) 698-707

(8) J A Wilson J S Chickos J Chem Eng Data 57 (2012) 2281-2285

(9) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-940

(10) J S Chickos D G Hesse J F Liebman Struct Chem 4 (1993) 261-269

(11) The EPI Suite is available as a download from

httpwwwepagovopptexposurepubsepisuitedlhtm accessed 61013

(12) M Covarrubias-Cervantes I Mokbel D Campion J Jose A Voilley Food

Chem 85 (2004) 221-229

(13) K B Wiberg R F Waldron J Am Chem Soc 113 (1991) 7697-7705

(14) J S Chickos W E Acree Jr J F Liebman Estimating Phase Change

Enthalpies and Entropies In Computational Thermochemistry Symposiun Series

677 K K IrikuraD J Frurip Ed ACS Washington DC 1998 Chapter 4

(15) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-942

9

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

O

O

(CH2)n

Figure 1 The structures of the γ and δ-lactone standards and targets and the ω-lactones

Time min

0 5 10 15 20

Inte

nsi

tyc

ou

nts

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

22000

Figure 2 GC chromatograph of a γ and δ-lactone mixture at T = 418 K 1 methanol 2 γ-

hexanolactone 3 γ-octanolactone 4 δ-octanolactone 5 γ-nonanolactone 6 δ-

nonanolactone 7 γ-decanolactone 8 δ-decanolactone 9 γ-undecanolactone 10 δ-

undecanolactone 11 γ-dodecanolactone 12 δ-dodecanolactone

12

11

10

9

8

6 7

1 2 3 5

4

10

∆Htrn

(Tm)kJmol

-1

30 35 40 45 50 55 60

∆lgH

(29

81

5 K

)kJ

mol-1

40

50

60

70

80

90

100

Figure 3 The correlation observed between the vaporization enthalpy ∆lgHm(Tm) and the

enthalpy of transfer ∆Htrn(Tm) for run 1 The line represents the results of a linear

regression analysis of the standards (circles) The squares (and their associated

uncertainties) are the vaporization enthalpies calculated for the targets

11

ln(tot

a)

-10 -9 -8 -7 -6 -5 -4 -3

ln(p

po)

-16

-15

-14

-13

-12

-11

-10

-9

-8

Figure 4 The correlation observed between ln(ppo) and ln(tota) for run 1 The line

represents the results of a linear regression analysis of the standards (circles) The squares

(and their associated uncertainties) are the vapor pressures calculated for the targets

12

TABLE 1

Origin of the standards and targets and their analysis

Compound

FEMA

CAS

registry no

Supplier

Mass

fraction

purity

(supplier)

Mass

fraction

purity

(GC)

γ-hexanolactone FCC 2556 695-06-7 Bedoukian gt098 0993

γ-octanolactone FCC 2796 104-50-7 Bedoukian gt097 0996

δ-octanolactone FCC 3214 698-76-0 Bedoukian 098a 0989

ab

γ-nonanolactone FCC 2781 104-61-0 Bedoukian 098 0982

δ-nonanolactone FCC

3356

3301-94-8

Citrus and

Allied

Essences 098 086

γ-decanolactone FCC 2360 706-14-9 Bedoukian 097 0984

δ-decanolactone FCC 2361 705-86-2 Bedoukian 098a 0975

ac

γ-undecanolactone FCC 3091 104-67-6 SAFC gt098 0984

δ-undecanolactone FCC 3294 710-04-3 Bedoukian 098a 0948

ad

γ-dodecanolactone FCC 2400 2305-05-7 Bedoukian 097 0930

δ-dodecanolactone FCC 2401 713-95-1 Bedoukian 098a 0983

ae

a Sum of isomers reference [5]

b Two isomers 0977023 the minor isomer separated but was not identified

c Two isomers 0788 0212 the minor isomer separated but was not identified

d Two isomers 0928 0072 the minor isomer separated but was not identified

e Two isomers 0985 0015 the minor isomer separated but was not identified

13

TABLE 2

Thermochemical properties of the γ and δ lactones used as standardsa

∆lgHm(298 K)

kJsdotmol-1

A

B

C

TK(range)

γ-hexanolactone3 572plusmn03 2887 796414 627 283-353

δ-octanolactone3 670plusmn02 3107 906819 792 288-353

γ-nonanolactone4 703plusmn03 3251 968999 892 296-363

δ-nonanolactone3 707plusmn04 3236 968266 876 293-348

γ-decanolactone4 756plusmn03 3420 1046661 975 298-365

δ-decanolactone3 742plusmn03 3326 1027922 959 309-358

a A B and C are constants of equation 2

TABLE 3

A The correlation of enthalpies of transfer with vaporization enthalpies

Run 1

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42544 10338 3537 572plusmn03 575plusmn36

γ-octanolactone -51151 11381 4252 659plusmn39

δ-octanolactone -51695 11362 4298 670plusmn02 665plusmn39

γ-nonanolactone -55556 11927 4619 703plusmn03 703plusmn40

δ-nonanolactone -56242 11941 4676 707plusmn04 709plusmn41

γ-decanolactone -60035 1249 4991 756plusmn03 747plusmn42

δ-decanolactone -60638 12495 5041 742plusmn03 752plusmn42

γ-undecanolactone -64508 13057 5363 791plusmn44

δ-undecanolactone -65139 1307 5415 797plusmn44

γ-dodecanolactone -68966 13622 5734 834plusmn46

δ-dodecanolactone -69615 13641 5788 841plusmn46

∆lgHm(29815 K)kJsdotmol

-1 = (118plusmn0062)∆Htrn(434 K) + (1562plusmn28) r

2 = 09890 (4)

B The correlation of enthalpies of transfer with vaporization enthalpies

Run 2

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42798 10387 3558 572plusmn03 572plusmn37

γ-octanolactone -51374 11424 4271 661plusmn39

δ-octanolactone -51926 11407 4317 670plusmn02 666plusmn40

γ-nonanolactone -55748 11962 4635 703plusmn03 706plusmn41

δ-nonanolactone -56418 11974 469 707plusmn04 713plusmn41

γ-decanolactone -60181 12513 5003 756plusmn03 752plusmn43

δ-decanolactone -60804 12526 5055 742plusmn03 758plusmn43

γ-undecanolactone -64622 13075 5372 797plusmn44

δ-undecanolactone -65275 13094 5427 804plusmn45

γ-dodecanolactone -69059 1364 5741 843plusmn46

δ-dodecanolactone -69695 13655 5794 850plusmn47

∆lgHm(29815 K)kJsdotmol

-1 = (119plusmn0063)∆Htrn(434 K) + (1512plusmn29) r

2 = 09889 (5)

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

2

e-mail jscumsledu

PhFax 314 516 53775342

1 Introduction

A number of γ and δ-lactones of hydroxylated fatty acids are important components in

flavors For example γ-dodecanolactone is described as having a waxy fatty sweet aroma

with green rind-like notes whereas δ- dodecanolactone is described as having fruity

peach-like and buttery notes [1] Nearly all the γ and δ-lactones from C6 to C14 are GRAS

chemicals (Generally Recognized As Safe) as recognized by the US Federal Food Drug

and Cosmetic Act [2] and are used as components in flavors

Recently the vapor pressures and vaporization enthalpies of a series of γ and δ-lactones

have been reported [34] The vapor pressures and vaporization enthalpies of a number of

the materials reported in these two articles have been used to evaluate these properties for

γ-octanolactone both γ and δ-undecanolactone and γ and δ-dodecanolactone by

correlation gas chromatography Vapor pressures and vaporization enthalpies do not

appear to have been previously reported for these lactones Vapor pressures are available

on MSDS sheets but it is not clear whether these are experimental or estimated

properties The structures of both the γ and δ-lactones as well as the corresponding ω-

lactones to which they are compared to are illustrated in figure 1

2 Experimental methods

21 Compounds and purity controls

Table 1 lists the origin and purity of both the standards and targets All γ-lactones greater

than C4 and all δ-lactones greater than C5 are chiral and yet the olfactory properties of

individual enantiomers are not generally discussed The commercial samples are all

assumed to be racemic Several of the materials used in this study are also reported as

mixtures of isomers All materials were analyzed by gas chromatography to evaluate their

chemical composition The results are reported in table 1 While our analyses differ

slightly from the values reported by the suppliers in a few instances some of our samples

were acquired some time ago The isomers which were present in some of the samples

3

were not identified All were present in minor amounts Their analyses are given in the

footnotes of table 1 Figure 2 provides a copy of the gas chromatograph of the mixture

The ability to generate reliable thermochemical data with less than pure samples is one of

the advantages of the correlation gas chromatography method

22 Methods

The measurements were performed on an HP 5890 gas chromatograph running HP

Chemstation Isothermal chromatograms were obtained over a T = 30 K temperature

range at intervals of T = 5 K on a Supelco 15 m 032 mm 10 microm film thickness SPB-5

capillary column at a split ratio of approximately 1001 using helium as the carrier The

column temperature was monitored continuously using a Vernier stainless steel

temperature probe with a GoLink USB interface running Logger Lite software The

column temperature was maintained by the instrument at plusmn01 K The solvent used was

methanol which also served as the non-retained reference at the temperatures of the

experiments

Residence time of each analyte on the column was calculated by difference between the

retention time of each analyte and the non retained reference The experimental retention

times are provided in the supplementary material The residence time ta is inversely

proportional to an analytersquos vapor pressure off the column Plots of ln(tota) against 1T

for each analyte where to refers to the reference time 60 s resulted in straight lines with

slopes equal to the enthalpy of transfer of the analyte from the column to the gas phase

divided by the gas constant -∆Htrn(Tm)R The correlation coefficient of the fit for each

analyte r2 exceeded 099 The enthalpy of transfer ∆Htrn(Tm) is related to the

vaporization enthalpy ∆lgHm(Tm) by equation 1[6]

The ∆Hintr(Tm) term represents the

enthalpy of interaction of the analyte with the column and is generally small in magnitude

in comparison to ∆lgHm(Tm) [7] Additional details of the correlation gas chromatography

method have been provided previously [78] The results of a second plot of ∆Htrn(Tm)

versus ∆lgH(29815) is described below as are the results of correlating ln(ppo) against

ln(tota) to evaluate vapor pressures

4

∆Htrn(Tm) = ∆lgHm (Tm) + ∆Hintr(Tm) (1)

23 Literature vaporization enthalpies and vapor pressures

The vaporization enthalpies of all the standards are available at T = 29815 K [34] The

temperature range of available vapor pressures varies some but generally data are

available from T = (29815 to 350) K All literature vapor pressure data have been fit to

equation 3 [34] Vaporization enthalpies and the A B and C constants of equation 2 are

reported in table 2

ln(pPa) = [A ndash BT(K) ndashCsdotln(T(K)29815)]R (2)

24 Temperature adjustments

The vapor pressures of all the standards are available roughly from T = (29815 to 350)

K As a means of evaluating how well the vapor pressures evaluated from correlations of

ln(ppo) with ln(tota) as described below reproduced their temperature dependence the

vaporization enthalpies calculated from the vapor pressures evaluated by correlation of

both the standards and targets were calculated at their mean temperature Tm = 324 K

They were then adjusted back to T = 29815 K for comparison with the values of the

standards and those of the targets as obtained by correlation Equation 3 was used for this

temperature adjustment [9] The term Cp(298 K)(l) refers to the heat capacity of the liquid

at T = 29815 k and was estimated by group additivity [10] The vaporization enthalpy

values obtained are provided and discussed below

∆lgHm(29815 K)(kJmol

-1) = ∆l

gHm(Tm)kJmol

-1 +

[(1058 + 026Cp(298 K)(l)(Jmol-1K

-1))( TmK - 29815 K)]1000 (3)

25 Uncertainties

The uncertainty associated with equation 3 is given by 16( TmK - 29815 K)1000

kJmol-1

[9] Uncertainties associated with the correlations were calculated as (u12 + u2

2)

05

where u represents the uncertainty associated with both the slope and intercept A similar

5

protocol was used in evaluating vaporization enthalpies adjusted to 29815 K from the

mean temperature

3 Experimental results and discussion

31 Vaporization enthalpies

If appropriate standards are used in the correlation between ∆Htrn(Tm) and ∆lgHm (29815

K) a good linear relationship is obtained despite the fact that the two enthalpies are

referenced to different temperature Figure 3 illustrates this correlation for the lactones

used as standards in run 1 The details of two correlations are summarized in tables 3A

and B and equations 4 and 5 listed below each respective table The results of both runs

are summarized in table 4 and compared to the literature values Despite the uncertainty

of approximately 4 kJmol-1

calculated from the correlation equations the vaporization

enthalpies of the standards are reproduced with an uncertainty of plusmn13 kJmol-1

(2 σ)

32 Vapor pressures

Vapor pressures generated from equation 2 at T = 29815 K were first converted to values

of ppo where po = 101325 Pa and then correlated as ln(ppo) with the corresponding

values of ln(tota) calculated from the slopes and intercepts listed in table 3 for both runs 1

and 2 The results of plotting ln(ppo) against ln(tota) at T = 29815 K for run 1 are

summarized in table 5 by equation 6 and illustrated in figure 4 The square symbols and

their associated uncertainties in the figure represent the values of ln(ppo) of the targets

calculated using equation 6 Results for run 2 are summarized by equation 7 and a table

similar to table 5 is provided in the supplementary material These correlation were then

repeated from T = (29815 to 350) K at 10 K intervals (not shown) The correlation

coefficients for each temperature evaluated r 2 gt 099 The vapor pressures obtained over

this 50 K temperature range were then fit to equation 8 The slopes and intercepts of the

fits are provided in table 6 for run 1 The vapor pressures calculated over this temperature

range for run 2 were virtually identical in most cases to those of run 1 after rounding off

and are not reported here Vapor pressure data for run 2 are provided in the

supplementary material All fits of ln(ppo) evaluated by correlation as a function of

temperature as 1T were characterized by correlation coefficients r2 gt 099

6

ln(ppo) = Arsquo+ Brsquo(TK) (8)

As an independent means of determining the overall quality of these correlations as a

function of temperature vaporization enthalpies were calculated from the product of the

slope of line of equation 8 and the gas constant (R) for each compound These values are

reported in the third column of table 6 These values were then adjusted back to T =

29815 K using equation 2 and the heat capacities listed in the table column 5 These

vaporization enthalpies adjusted to T = 29815 K are included in column 6 of table 6 and

compared to the values used as standards or to the values reported in table 4 in the last

column of the table The vaporization enthalpies of both standards and targets are all

reproduced with a standard deviation of plusmn15 kJsdotmol-1

(2 σ)

The vapor pressures at T = 29815 K in the last column of table 5 calculated using

equation 6 and reproduced in column 3 of table 7 are compared with available

experimental and estimated values in table 7 columns 2 and 5 respectively The

uncertainties associated with equation 6 were calculated from the corresponding

uncertainties in the slope and intercept of the equation as described above Vapor

pressures calculated using equation 8 and the constants of table 6 column 4 of table 7

differ slightly but also reproduce both literature values and those calculated using

equation 6 well within the uncertainties cited The vapor pressures of the standards are

reproduced using both equation 6 and by equation 8 and the constants of table 6 within 9

of their value The last two columns of the table compare vapor pressures calculated at

T = 29315 K using equation 8 and the constants of table 6 The vapor pressures reported

in column 6 are from MSDS sheets made available by the supplier [5] It is not known if

they represent experimental or estimated values The vapor pressures calculated in this

work are consistently smaller than the MSDS values by roughly a factor of 4 Equation 8

and the constants of table 6 can be used to provide vapor pressures of the materials

evaluated in this work from T = (29815 to 350) K

33 Vaporization enthalpy estimates

7

Emelrsquoyanenko et al[4] reported a group additivity procedure for predicting the

vaporization enthalpies of γ and δ-lactones Table 8 summarizes the group values they

reported and table 9 compares the predicted values with the experimental vaporization

enthalpies reported previously and those evaluated in this work Agreement with the

results reported here are well within the experimental uncertainties All values in column

4 are slightly over predicted but are reproduced with a standard deviation of plusmn10 kJsdotmol-1

(2 σ)

34 Vaporization enthalpy comparisons

In addition to the γ and δ-lactones studied Wiberg and Waldron [13] reported the

vaporization enthalpies of a corresponding series of ω-lactones These results are

compared in table 10 It should be noted that ω and γ-butanolactone and ω and δ-

pentanolactone refer to the same material and are included to illustrate the reproducibility

of literature values As the ring size increases and becomes more flexible the

vaporization enthalpies appear to attenuate Consistent with this interpretation an

alternative estimation equation eq 9 generated from the vaporization enthalpies of

acyclic esters [14] greatly underestimates the vaporization enthalpies of both the smaller

γ and δ-lactones but appears to provide an improved estimation of the larger ones as

indicated in the last column of table 10 The cyclic ethers oxetane tetrahydrofuran and

pyran are also under-estimated by eq 9 [15] The nC nQ and b terms in equation 9 refer to

the total number of carbons the number of quaternary sp3 hybridized carbons (0) and the

contribution of the functional group (105 kJsdotmol-1

) respectively

∆lgHm(298 K) kJsdotmol

-1 = 469(nC - nQ) 13nQ +30 + b (9)

33 Summary

The vaporization enthalpies at T = 29815 K and vapor pressures from T = (29815 to

350) K of three γ and two δ-lactones are evaluated by correlation gas chromatography

using a series of closely related standards The vaporization enthalpies are believed

known with an uncertainty somewhat less than plusmn4 kJsdotmol-1

and vapor pressures within an

uncertainty of approximately 40 of their value

8

Appendix A Supplementary data

Supplementary data associated with this article can be found in the online version at

http

References

(1) httpwwwbedoukiancomproductsproductaspid=463 accessed 82813

(2) httpwwwfdagovFoodIngredientsPackagingLabelingGRAS accessed

82813

(3) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 39 (2007) 10-15

(4) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 40 (2008) 911-16

(5) httpbedoukiancomproductssearchflavorasp accessed 82913

(6) L A Peacock R Fuchs J Am Chem Soc 99 (1977) 5524-5

(7) D Lipkind J S Chickos J Chem Eng Data 55 (2010) 698-707

(8) J A Wilson J S Chickos J Chem Eng Data 57 (2012) 2281-2285

(9) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-940

(10) J S Chickos D G Hesse J F Liebman Struct Chem 4 (1993) 261-269

(11) The EPI Suite is available as a download from

httpwwwepagovopptexposurepubsepisuitedlhtm accessed 61013

(12) M Covarrubias-Cervantes I Mokbel D Campion J Jose A Voilley Food

Chem 85 (2004) 221-229

(13) K B Wiberg R F Waldron J Am Chem Soc 113 (1991) 7697-7705

(14) J S Chickos W E Acree Jr J F Liebman Estimating Phase Change

Enthalpies and Entropies In Computational Thermochemistry Symposiun Series

677 K K IrikuraD J Frurip Ed ACS Washington DC 1998 Chapter 4

(15) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-942

9

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

O

O

(CH2)n

Figure 1 The structures of the γ and δ-lactone standards and targets and the ω-lactones

Time min

0 5 10 15 20

Inte

nsi

tyc

ou

nts

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

22000

Figure 2 GC chromatograph of a γ and δ-lactone mixture at T = 418 K 1 methanol 2 γ-

hexanolactone 3 γ-octanolactone 4 δ-octanolactone 5 γ-nonanolactone 6 δ-

nonanolactone 7 γ-decanolactone 8 δ-decanolactone 9 γ-undecanolactone 10 δ-

undecanolactone 11 γ-dodecanolactone 12 δ-dodecanolactone

12

11

10

9

8

6 7

1 2 3 5

4

10

∆Htrn

(Tm)kJmol

-1

30 35 40 45 50 55 60

∆lgH

(29

81

5 K

)kJ

mol-1

40

50

60

70

80

90

100

Figure 3 The correlation observed between the vaporization enthalpy ∆lgHm(Tm) and the

enthalpy of transfer ∆Htrn(Tm) for run 1 The line represents the results of a linear

regression analysis of the standards (circles) The squares (and their associated

uncertainties) are the vaporization enthalpies calculated for the targets

11

ln(tot

a)

-10 -9 -8 -7 -6 -5 -4 -3

ln(p

po)

-16

-15

-14

-13

-12

-11

-10

-9

-8

Figure 4 The correlation observed between ln(ppo) and ln(tota) for run 1 The line

represents the results of a linear regression analysis of the standards (circles) The squares

(and their associated uncertainties) are the vapor pressures calculated for the targets

12

TABLE 1

Origin of the standards and targets and their analysis

Compound

FEMA

CAS

registry no

Supplier

Mass

fraction

purity

(supplier)

Mass

fraction

purity

(GC)

γ-hexanolactone FCC 2556 695-06-7 Bedoukian gt098 0993

γ-octanolactone FCC 2796 104-50-7 Bedoukian gt097 0996

δ-octanolactone FCC 3214 698-76-0 Bedoukian 098a 0989

ab

γ-nonanolactone FCC 2781 104-61-0 Bedoukian 098 0982

δ-nonanolactone FCC

3356

3301-94-8

Citrus and

Allied

Essences 098 086

γ-decanolactone FCC 2360 706-14-9 Bedoukian 097 0984

δ-decanolactone FCC 2361 705-86-2 Bedoukian 098a 0975

ac

γ-undecanolactone FCC 3091 104-67-6 SAFC gt098 0984

δ-undecanolactone FCC 3294 710-04-3 Bedoukian 098a 0948

ad

γ-dodecanolactone FCC 2400 2305-05-7 Bedoukian 097 0930

δ-dodecanolactone FCC 2401 713-95-1 Bedoukian 098a 0983

ae

a Sum of isomers reference [5]

b Two isomers 0977023 the minor isomer separated but was not identified

c Two isomers 0788 0212 the minor isomer separated but was not identified

d Two isomers 0928 0072 the minor isomer separated but was not identified

e Two isomers 0985 0015 the minor isomer separated but was not identified

13

TABLE 2

Thermochemical properties of the γ and δ lactones used as standardsa

∆lgHm(298 K)

kJsdotmol-1

A

B

C

TK(range)

γ-hexanolactone3 572plusmn03 2887 796414 627 283-353

δ-octanolactone3 670plusmn02 3107 906819 792 288-353

γ-nonanolactone4 703plusmn03 3251 968999 892 296-363

δ-nonanolactone3 707plusmn04 3236 968266 876 293-348

γ-decanolactone4 756plusmn03 3420 1046661 975 298-365

δ-decanolactone3 742plusmn03 3326 1027922 959 309-358

a A B and C are constants of equation 2

TABLE 3

A The correlation of enthalpies of transfer with vaporization enthalpies

Run 1

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42544 10338 3537 572plusmn03 575plusmn36

γ-octanolactone -51151 11381 4252 659plusmn39

δ-octanolactone -51695 11362 4298 670plusmn02 665plusmn39

γ-nonanolactone -55556 11927 4619 703plusmn03 703plusmn40

δ-nonanolactone -56242 11941 4676 707plusmn04 709plusmn41

γ-decanolactone -60035 1249 4991 756plusmn03 747plusmn42

δ-decanolactone -60638 12495 5041 742plusmn03 752plusmn42

γ-undecanolactone -64508 13057 5363 791plusmn44

δ-undecanolactone -65139 1307 5415 797plusmn44

γ-dodecanolactone -68966 13622 5734 834plusmn46

δ-dodecanolactone -69615 13641 5788 841plusmn46

∆lgHm(29815 K)kJsdotmol

-1 = (118plusmn0062)∆Htrn(434 K) + (1562plusmn28) r

2 = 09890 (4)

B The correlation of enthalpies of transfer with vaporization enthalpies

Run 2

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42798 10387 3558 572plusmn03 572plusmn37

γ-octanolactone -51374 11424 4271 661plusmn39

δ-octanolactone -51926 11407 4317 670plusmn02 666plusmn40

γ-nonanolactone -55748 11962 4635 703plusmn03 706plusmn41

δ-nonanolactone -56418 11974 469 707plusmn04 713plusmn41

γ-decanolactone -60181 12513 5003 756plusmn03 752plusmn43

δ-decanolactone -60804 12526 5055 742plusmn03 758plusmn43

γ-undecanolactone -64622 13075 5372 797plusmn44

δ-undecanolactone -65275 13094 5427 804plusmn45

γ-dodecanolactone -69059 1364 5741 843plusmn46

δ-dodecanolactone -69695 13655 5794 850plusmn47

∆lgHm(29815 K)kJsdotmol

-1 = (119plusmn0063)∆Htrn(434 K) + (1512plusmn29) r

2 = 09889 (5)

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

3

were not identified All were present in minor amounts Their analyses are given in the

footnotes of table 1 Figure 2 provides a copy of the gas chromatograph of the mixture

The ability to generate reliable thermochemical data with less than pure samples is one of

the advantages of the correlation gas chromatography method

22 Methods

The measurements were performed on an HP 5890 gas chromatograph running HP

Chemstation Isothermal chromatograms were obtained over a T = 30 K temperature

range at intervals of T = 5 K on a Supelco 15 m 032 mm 10 microm film thickness SPB-5

capillary column at a split ratio of approximately 1001 using helium as the carrier The

column temperature was monitored continuously using a Vernier stainless steel

temperature probe with a GoLink USB interface running Logger Lite software The

column temperature was maintained by the instrument at plusmn01 K The solvent used was

methanol which also served as the non-retained reference at the temperatures of the

experiments

Residence time of each analyte on the column was calculated by difference between the

retention time of each analyte and the non retained reference The experimental retention

times are provided in the supplementary material The residence time ta is inversely

proportional to an analytersquos vapor pressure off the column Plots of ln(tota) against 1T

for each analyte where to refers to the reference time 60 s resulted in straight lines with

slopes equal to the enthalpy of transfer of the analyte from the column to the gas phase

divided by the gas constant -∆Htrn(Tm)R The correlation coefficient of the fit for each

analyte r2 exceeded 099 The enthalpy of transfer ∆Htrn(Tm) is related to the

vaporization enthalpy ∆lgHm(Tm) by equation 1[6]

The ∆Hintr(Tm) term represents the

enthalpy of interaction of the analyte with the column and is generally small in magnitude

in comparison to ∆lgHm(Tm) [7] Additional details of the correlation gas chromatography

method have been provided previously [78] The results of a second plot of ∆Htrn(Tm)

versus ∆lgH(29815) is described below as are the results of correlating ln(ppo) against

ln(tota) to evaluate vapor pressures

4

∆Htrn(Tm) = ∆lgHm (Tm) + ∆Hintr(Tm) (1)

23 Literature vaporization enthalpies and vapor pressures

The vaporization enthalpies of all the standards are available at T = 29815 K [34] The

temperature range of available vapor pressures varies some but generally data are

available from T = (29815 to 350) K All literature vapor pressure data have been fit to

equation 3 [34] Vaporization enthalpies and the A B and C constants of equation 2 are

reported in table 2

ln(pPa) = [A ndash BT(K) ndashCsdotln(T(K)29815)]R (2)

24 Temperature adjustments

The vapor pressures of all the standards are available roughly from T = (29815 to 350)

K As a means of evaluating how well the vapor pressures evaluated from correlations of

ln(ppo) with ln(tota) as described below reproduced their temperature dependence the

vaporization enthalpies calculated from the vapor pressures evaluated by correlation of

both the standards and targets were calculated at their mean temperature Tm = 324 K

They were then adjusted back to T = 29815 K for comparison with the values of the

standards and those of the targets as obtained by correlation Equation 3 was used for this

temperature adjustment [9] The term Cp(298 K)(l) refers to the heat capacity of the liquid

at T = 29815 k and was estimated by group additivity [10] The vaporization enthalpy

values obtained are provided and discussed below

∆lgHm(29815 K)(kJmol

-1) = ∆l

gHm(Tm)kJmol

-1 +

[(1058 + 026Cp(298 K)(l)(Jmol-1K

-1))( TmK - 29815 K)]1000 (3)

25 Uncertainties

The uncertainty associated with equation 3 is given by 16( TmK - 29815 K)1000

kJmol-1

[9] Uncertainties associated with the correlations were calculated as (u12 + u2

2)

05

where u represents the uncertainty associated with both the slope and intercept A similar

5

protocol was used in evaluating vaporization enthalpies adjusted to 29815 K from the

mean temperature

3 Experimental results and discussion

31 Vaporization enthalpies

If appropriate standards are used in the correlation between ∆Htrn(Tm) and ∆lgHm (29815

K) a good linear relationship is obtained despite the fact that the two enthalpies are

referenced to different temperature Figure 3 illustrates this correlation for the lactones

used as standards in run 1 The details of two correlations are summarized in tables 3A

and B and equations 4 and 5 listed below each respective table The results of both runs

are summarized in table 4 and compared to the literature values Despite the uncertainty

of approximately 4 kJmol-1

calculated from the correlation equations the vaporization

enthalpies of the standards are reproduced with an uncertainty of plusmn13 kJmol-1

(2 σ)

32 Vapor pressures

Vapor pressures generated from equation 2 at T = 29815 K were first converted to values

of ppo where po = 101325 Pa and then correlated as ln(ppo) with the corresponding

values of ln(tota) calculated from the slopes and intercepts listed in table 3 for both runs 1

and 2 The results of plotting ln(ppo) against ln(tota) at T = 29815 K for run 1 are

summarized in table 5 by equation 6 and illustrated in figure 4 The square symbols and

their associated uncertainties in the figure represent the values of ln(ppo) of the targets

calculated using equation 6 Results for run 2 are summarized by equation 7 and a table

similar to table 5 is provided in the supplementary material These correlation were then

repeated from T = (29815 to 350) K at 10 K intervals (not shown) The correlation

coefficients for each temperature evaluated r 2 gt 099 The vapor pressures obtained over

this 50 K temperature range were then fit to equation 8 The slopes and intercepts of the

fits are provided in table 6 for run 1 The vapor pressures calculated over this temperature

range for run 2 were virtually identical in most cases to those of run 1 after rounding off

and are not reported here Vapor pressure data for run 2 are provided in the

supplementary material All fits of ln(ppo) evaluated by correlation as a function of

temperature as 1T were characterized by correlation coefficients r2 gt 099

6

ln(ppo) = Arsquo+ Brsquo(TK) (8)

As an independent means of determining the overall quality of these correlations as a

function of temperature vaporization enthalpies were calculated from the product of the

slope of line of equation 8 and the gas constant (R) for each compound These values are

reported in the third column of table 6 These values were then adjusted back to T =

29815 K using equation 2 and the heat capacities listed in the table column 5 These

vaporization enthalpies adjusted to T = 29815 K are included in column 6 of table 6 and

compared to the values used as standards or to the values reported in table 4 in the last

column of the table The vaporization enthalpies of both standards and targets are all

reproduced with a standard deviation of plusmn15 kJsdotmol-1

(2 σ)

The vapor pressures at T = 29815 K in the last column of table 5 calculated using

equation 6 and reproduced in column 3 of table 7 are compared with available

experimental and estimated values in table 7 columns 2 and 5 respectively The

uncertainties associated with equation 6 were calculated from the corresponding

uncertainties in the slope and intercept of the equation as described above Vapor

pressures calculated using equation 8 and the constants of table 6 column 4 of table 7

differ slightly but also reproduce both literature values and those calculated using

equation 6 well within the uncertainties cited The vapor pressures of the standards are

reproduced using both equation 6 and by equation 8 and the constants of table 6 within 9

of their value The last two columns of the table compare vapor pressures calculated at

T = 29315 K using equation 8 and the constants of table 6 The vapor pressures reported

in column 6 are from MSDS sheets made available by the supplier [5] It is not known if

they represent experimental or estimated values The vapor pressures calculated in this

work are consistently smaller than the MSDS values by roughly a factor of 4 Equation 8

and the constants of table 6 can be used to provide vapor pressures of the materials

evaluated in this work from T = (29815 to 350) K

33 Vaporization enthalpy estimates

7

Emelrsquoyanenko et al[4] reported a group additivity procedure for predicting the

vaporization enthalpies of γ and δ-lactones Table 8 summarizes the group values they

reported and table 9 compares the predicted values with the experimental vaporization

enthalpies reported previously and those evaluated in this work Agreement with the

results reported here are well within the experimental uncertainties All values in column

4 are slightly over predicted but are reproduced with a standard deviation of plusmn10 kJsdotmol-1

(2 σ)

34 Vaporization enthalpy comparisons

In addition to the γ and δ-lactones studied Wiberg and Waldron [13] reported the

vaporization enthalpies of a corresponding series of ω-lactones These results are

compared in table 10 It should be noted that ω and γ-butanolactone and ω and δ-

pentanolactone refer to the same material and are included to illustrate the reproducibility

of literature values As the ring size increases and becomes more flexible the

vaporization enthalpies appear to attenuate Consistent with this interpretation an

alternative estimation equation eq 9 generated from the vaporization enthalpies of

acyclic esters [14] greatly underestimates the vaporization enthalpies of both the smaller

γ and δ-lactones but appears to provide an improved estimation of the larger ones as

indicated in the last column of table 10 The cyclic ethers oxetane tetrahydrofuran and

pyran are also under-estimated by eq 9 [15] The nC nQ and b terms in equation 9 refer to

the total number of carbons the number of quaternary sp3 hybridized carbons (0) and the

contribution of the functional group (105 kJsdotmol-1

) respectively

∆lgHm(298 K) kJsdotmol

-1 = 469(nC - nQ) 13nQ +30 + b (9)

33 Summary

The vaporization enthalpies at T = 29815 K and vapor pressures from T = (29815 to

350) K of three γ and two δ-lactones are evaluated by correlation gas chromatography

using a series of closely related standards The vaporization enthalpies are believed

known with an uncertainty somewhat less than plusmn4 kJsdotmol-1

and vapor pressures within an

uncertainty of approximately 40 of their value

8

Appendix A Supplementary data

Supplementary data associated with this article can be found in the online version at

http

References

(1) httpwwwbedoukiancomproductsproductaspid=463 accessed 82813

(2) httpwwwfdagovFoodIngredientsPackagingLabelingGRAS accessed

82813

(3) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 39 (2007) 10-15

(4) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 40 (2008) 911-16

(5) httpbedoukiancomproductssearchflavorasp accessed 82913

(6) L A Peacock R Fuchs J Am Chem Soc 99 (1977) 5524-5

(7) D Lipkind J S Chickos J Chem Eng Data 55 (2010) 698-707

(8) J A Wilson J S Chickos J Chem Eng Data 57 (2012) 2281-2285

(9) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-940

(10) J S Chickos D G Hesse J F Liebman Struct Chem 4 (1993) 261-269

(11) The EPI Suite is available as a download from

httpwwwepagovopptexposurepubsepisuitedlhtm accessed 61013

(12) M Covarrubias-Cervantes I Mokbel D Campion J Jose A Voilley Food

Chem 85 (2004) 221-229

(13) K B Wiberg R F Waldron J Am Chem Soc 113 (1991) 7697-7705

(14) J S Chickos W E Acree Jr J F Liebman Estimating Phase Change

Enthalpies and Entropies In Computational Thermochemistry Symposiun Series

677 K K IrikuraD J Frurip Ed ACS Washington DC 1998 Chapter 4

(15) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-942

9

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

O

O

(CH2)n

Figure 1 The structures of the γ and δ-lactone standards and targets and the ω-lactones

Time min

0 5 10 15 20

Inte

nsi

tyc

ou

nts

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

22000

Figure 2 GC chromatograph of a γ and δ-lactone mixture at T = 418 K 1 methanol 2 γ-

hexanolactone 3 γ-octanolactone 4 δ-octanolactone 5 γ-nonanolactone 6 δ-

nonanolactone 7 γ-decanolactone 8 δ-decanolactone 9 γ-undecanolactone 10 δ-

undecanolactone 11 γ-dodecanolactone 12 δ-dodecanolactone

12

11

10

9

8

6 7

1 2 3 5

4

10

∆Htrn

(Tm)kJmol

-1

30 35 40 45 50 55 60

∆lgH

(29

81

5 K

)kJ

mol-1

40

50

60

70

80

90

100

Figure 3 The correlation observed between the vaporization enthalpy ∆lgHm(Tm) and the

enthalpy of transfer ∆Htrn(Tm) for run 1 The line represents the results of a linear

regression analysis of the standards (circles) The squares (and their associated

uncertainties) are the vaporization enthalpies calculated for the targets

11

ln(tot

a)

-10 -9 -8 -7 -6 -5 -4 -3

ln(p

po)

-16

-15

-14

-13

-12

-11

-10

-9

-8

Figure 4 The correlation observed between ln(ppo) and ln(tota) for run 1 The line

represents the results of a linear regression analysis of the standards (circles) The squares

(and their associated uncertainties) are the vapor pressures calculated for the targets

12

TABLE 1

Origin of the standards and targets and their analysis

Compound

FEMA

CAS

registry no

Supplier

Mass

fraction

purity

(supplier)

Mass

fraction

purity

(GC)

γ-hexanolactone FCC 2556 695-06-7 Bedoukian gt098 0993

γ-octanolactone FCC 2796 104-50-7 Bedoukian gt097 0996

δ-octanolactone FCC 3214 698-76-0 Bedoukian 098a 0989

ab

γ-nonanolactone FCC 2781 104-61-0 Bedoukian 098 0982

δ-nonanolactone FCC

3356

3301-94-8

Citrus and

Allied

Essences 098 086

γ-decanolactone FCC 2360 706-14-9 Bedoukian 097 0984

δ-decanolactone FCC 2361 705-86-2 Bedoukian 098a 0975

ac

γ-undecanolactone FCC 3091 104-67-6 SAFC gt098 0984

δ-undecanolactone FCC 3294 710-04-3 Bedoukian 098a 0948

ad

γ-dodecanolactone FCC 2400 2305-05-7 Bedoukian 097 0930

δ-dodecanolactone FCC 2401 713-95-1 Bedoukian 098a 0983

ae

a Sum of isomers reference [5]

b Two isomers 0977023 the minor isomer separated but was not identified

c Two isomers 0788 0212 the minor isomer separated but was not identified

d Two isomers 0928 0072 the minor isomer separated but was not identified

e Two isomers 0985 0015 the minor isomer separated but was not identified

13

TABLE 2

Thermochemical properties of the γ and δ lactones used as standardsa

∆lgHm(298 K)

kJsdotmol-1

A

B

C

TK(range)

γ-hexanolactone3 572plusmn03 2887 796414 627 283-353

δ-octanolactone3 670plusmn02 3107 906819 792 288-353

γ-nonanolactone4 703plusmn03 3251 968999 892 296-363

δ-nonanolactone3 707plusmn04 3236 968266 876 293-348

γ-decanolactone4 756plusmn03 3420 1046661 975 298-365

δ-decanolactone3 742plusmn03 3326 1027922 959 309-358

a A B and C are constants of equation 2

TABLE 3

A The correlation of enthalpies of transfer with vaporization enthalpies

Run 1

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42544 10338 3537 572plusmn03 575plusmn36

γ-octanolactone -51151 11381 4252 659plusmn39

δ-octanolactone -51695 11362 4298 670plusmn02 665plusmn39

γ-nonanolactone -55556 11927 4619 703plusmn03 703plusmn40

δ-nonanolactone -56242 11941 4676 707plusmn04 709plusmn41

γ-decanolactone -60035 1249 4991 756plusmn03 747plusmn42

δ-decanolactone -60638 12495 5041 742plusmn03 752plusmn42

γ-undecanolactone -64508 13057 5363 791plusmn44

δ-undecanolactone -65139 1307 5415 797plusmn44

γ-dodecanolactone -68966 13622 5734 834plusmn46

δ-dodecanolactone -69615 13641 5788 841plusmn46

∆lgHm(29815 K)kJsdotmol

-1 = (118plusmn0062)∆Htrn(434 K) + (1562plusmn28) r

2 = 09890 (4)

B The correlation of enthalpies of transfer with vaporization enthalpies

Run 2

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42798 10387 3558 572plusmn03 572plusmn37

γ-octanolactone -51374 11424 4271 661plusmn39

δ-octanolactone -51926 11407 4317 670plusmn02 666plusmn40

γ-nonanolactone -55748 11962 4635 703plusmn03 706plusmn41

δ-nonanolactone -56418 11974 469 707plusmn04 713plusmn41

γ-decanolactone -60181 12513 5003 756plusmn03 752plusmn43

δ-decanolactone -60804 12526 5055 742plusmn03 758plusmn43

γ-undecanolactone -64622 13075 5372 797plusmn44

δ-undecanolactone -65275 13094 5427 804plusmn45

γ-dodecanolactone -69059 1364 5741 843plusmn46

δ-dodecanolactone -69695 13655 5794 850plusmn47

∆lgHm(29815 K)kJsdotmol

-1 = (119plusmn0063)∆Htrn(434 K) + (1512plusmn29) r

2 = 09889 (5)

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

4

∆Htrn(Tm) = ∆lgHm (Tm) + ∆Hintr(Tm) (1)

23 Literature vaporization enthalpies and vapor pressures

The vaporization enthalpies of all the standards are available at T = 29815 K [34] The

temperature range of available vapor pressures varies some but generally data are

available from T = (29815 to 350) K All literature vapor pressure data have been fit to

equation 3 [34] Vaporization enthalpies and the A B and C constants of equation 2 are

reported in table 2

ln(pPa) = [A ndash BT(K) ndashCsdotln(T(K)29815)]R (2)

24 Temperature adjustments

The vapor pressures of all the standards are available roughly from T = (29815 to 350)

K As a means of evaluating how well the vapor pressures evaluated from correlations of

ln(ppo) with ln(tota) as described below reproduced their temperature dependence the

vaporization enthalpies calculated from the vapor pressures evaluated by correlation of

both the standards and targets were calculated at their mean temperature Tm = 324 K

They were then adjusted back to T = 29815 K for comparison with the values of the

standards and those of the targets as obtained by correlation Equation 3 was used for this

temperature adjustment [9] The term Cp(298 K)(l) refers to the heat capacity of the liquid

at T = 29815 k and was estimated by group additivity [10] The vaporization enthalpy

values obtained are provided and discussed below

∆lgHm(29815 K)(kJmol

-1) = ∆l

gHm(Tm)kJmol

-1 +

[(1058 + 026Cp(298 K)(l)(Jmol-1K

-1))( TmK - 29815 K)]1000 (3)

25 Uncertainties

The uncertainty associated with equation 3 is given by 16( TmK - 29815 K)1000

kJmol-1

[9] Uncertainties associated with the correlations were calculated as (u12 + u2

2)

05

where u represents the uncertainty associated with both the slope and intercept A similar

5

protocol was used in evaluating vaporization enthalpies adjusted to 29815 K from the

mean temperature

3 Experimental results and discussion

31 Vaporization enthalpies

If appropriate standards are used in the correlation between ∆Htrn(Tm) and ∆lgHm (29815

K) a good linear relationship is obtained despite the fact that the two enthalpies are

referenced to different temperature Figure 3 illustrates this correlation for the lactones

used as standards in run 1 The details of two correlations are summarized in tables 3A

and B and equations 4 and 5 listed below each respective table The results of both runs

are summarized in table 4 and compared to the literature values Despite the uncertainty

of approximately 4 kJmol-1

calculated from the correlation equations the vaporization

enthalpies of the standards are reproduced with an uncertainty of plusmn13 kJmol-1

(2 σ)

32 Vapor pressures

Vapor pressures generated from equation 2 at T = 29815 K were first converted to values

of ppo where po = 101325 Pa and then correlated as ln(ppo) with the corresponding

values of ln(tota) calculated from the slopes and intercepts listed in table 3 for both runs 1

and 2 The results of plotting ln(ppo) against ln(tota) at T = 29815 K for run 1 are

summarized in table 5 by equation 6 and illustrated in figure 4 The square symbols and

their associated uncertainties in the figure represent the values of ln(ppo) of the targets

calculated using equation 6 Results for run 2 are summarized by equation 7 and a table

similar to table 5 is provided in the supplementary material These correlation were then

repeated from T = (29815 to 350) K at 10 K intervals (not shown) The correlation

coefficients for each temperature evaluated r 2 gt 099 The vapor pressures obtained over

this 50 K temperature range were then fit to equation 8 The slopes and intercepts of the

fits are provided in table 6 for run 1 The vapor pressures calculated over this temperature

range for run 2 were virtually identical in most cases to those of run 1 after rounding off

and are not reported here Vapor pressure data for run 2 are provided in the

supplementary material All fits of ln(ppo) evaluated by correlation as a function of

temperature as 1T were characterized by correlation coefficients r2 gt 099

6

ln(ppo) = Arsquo+ Brsquo(TK) (8)

As an independent means of determining the overall quality of these correlations as a

function of temperature vaporization enthalpies were calculated from the product of the

slope of line of equation 8 and the gas constant (R) for each compound These values are

reported in the third column of table 6 These values were then adjusted back to T =

29815 K using equation 2 and the heat capacities listed in the table column 5 These

vaporization enthalpies adjusted to T = 29815 K are included in column 6 of table 6 and

compared to the values used as standards or to the values reported in table 4 in the last

column of the table The vaporization enthalpies of both standards and targets are all

reproduced with a standard deviation of plusmn15 kJsdotmol-1

(2 σ)

The vapor pressures at T = 29815 K in the last column of table 5 calculated using

equation 6 and reproduced in column 3 of table 7 are compared with available

experimental and estimated values in table 7 columns 2 and 5 respectively The

uncertainties associated with equation 6 were calculated from the corresponding

uncertainties in the slope and intercept of the equation as described above Vapor

pressures calculated using equation 8 and the constants of table 6 column 4 of table 7

differ slightly but also reproduce both literature values and those calculated using

equation 6 well within the uncertainties cited The vapor pressures of the standards are

reproduced using both equation 6 and by equation 8 and the constants of table 6 within 9

of their value The last two columns of the table compare vapor pressures calculated at

T = 29315 K using equation 8 and the constants of table 6 The vapor pressures reported

in column 6 are from MSDS sheets made available by the supplier [5] It is not known if

they represent experimental or estimated values The vapor pressures calculated in this

work are consistently smaller than the MSDS values by roughly a factor of 4 Equation 8

and the constants of table 6 can be used to provide vapor pressures of the materials

evaluated in this work from T = (29815 to 350) K

33 Vaporization enthalpy estimates

7

Emelrsquoyanenko et al[4] reported a group additivity procedure for predicting the

vaporization enthalpies of γ and δ-lactones Table 8 summarizes the group values they

reported and table 9 compares the predicted values with the experimental vaporization

enthalpies reported previously and those evaluated in this work Agreement with the

results reported here are well within the experimental uncertainties All values in column

4 are slightly over predicted but are reproduced with a standard deviation of plusmn10 kJsdotmol-1

(2 σ)

34 Vaporization enthalpy comparisons

In addition to the γ and δ-lactones studied Wiberg and Waldron [13] reported the

vaporization enthalpies of a corresponding series of ω-lactones These results are

compared in table 10 It should be noted that ω and γ-butanolactone and ω and δ-

pentanolactone refer to the same material and are included to illustrate the reproducibility

of literature values As the ring size increases and becomes more flexible the

vaporization enthalpies appear to attenuate Consistent with this interpretation an

alternative estimation equation eq 9 generated from the vaporization enthalpies of

acyclic esters [14] greatly underestimates the vaporization enthalpies of both the smaller

γ and δ-lactones but appears to provide an improved estimation of the larger ones as

indicated in the last column of table 10 The cyclic ethers oxetane tetrahydrofuran and

pyran are also under-estimated by eq 9 [15] The nC nQ and b terms in equation 9 refer to

the total number of carbons the number of quaternary sp3 hybridized carbons (0) and the

contribution of the functional group (105 kJsdotmol-1

) respectively

∆lgHm(298 K) kJsdotmol

-1 = 469(nC - nQ) 13nQ +30 + b (9)

33 Summary

The vaporization enthalpies at T = 29815 K and vapor pressures from T = (29815 to

350) K of three γ and two δ-lactones are evaluated by correlation gas chromatography

using a series of closely related standards The vaporization enthalpies are believed

known with an uncertainty somewhat less than plusmn4 kJsdotmol-1

and vapor pressures within an

uncertainty of approximately 40 of their value

8

Appendix A Supplementary data

Supplementary data associated with this article can be found in the online version at

http

References

(1) httpwwwbedoukiancomproductsproductaspid=463 accessed 82813

(2) httpwwwfdagovFoodIngredientsPackagingLabelingGRAS accessed

82813

(3) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 39 (2007) 10-15

(4) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 40 (2008) 911-16

(5) httpbedoukiancomproductssearchflavorasp accessed 82913

(6) L A Peacock R Fuchs J Am Chem Soc 99 (1977) 5524-5

(7) D Lipkind J S Chickos J Chem Eng Data 55 (2010) 698-707

(8) J A Wilson J S Chickos J Chem Eng Data 57 (2012) 2281-2285

(9) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-940

(10) J S Chickos D G Hesse J F Liebman Struct Chem 4 (1993) 261-269

(11) The EPI Suite is available as a download from

httpwwwepagovopptexposurepubsepisuitedlhtm accessed 61013

(12) M Covarrubias-Cervantes I Mokbel D Campion J Jose A Voilley Food

Chem 85 (2004) 221-229

(13) K B Wiberg R F Waldron J Am Chem Soc 113 (1991) 7697-7705

(14) J S Chickos W E Acree Jr J F Liebman Estimating Phase Change

Enthalpies and Entropies In Computational Thermochemistry Symposiun Series

677 K K IrikuraD J Frurip Ed ACS Washington DC 1998 Chapter 4

(15) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-942

9

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

O

O

(CH2)n

Figure 1 The structures of the γ and δ-lactone standards and targets and the ω-lactones

Time min

0 5 10 15 20

Inte

nsi

tyc

ou

nts

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

22000

Figure 2 GC chromatograph of a γ and δ-lactone mixture at T = 418 K 1 methanol 2 γ-

hexanolactone 3 γ-octanolactone 4 δ-octanolactone 5 γ-nonanolactone 6 δ-

nonanolactone 7 γ-decanolactone 8 δ-decanolactone 9 γ-undecanolactone 10 δ-

undecanolactone 11 γ-dodecanolactone 12 δ-dodecanolactone

12

11

10

9

8

6 7

1 2 3 5

4

10

∆Htrn

(Tm)kJmol

-1

30 35 40 45 50 55 60

∆lgH

(29

81

5 K

)kJ

mol-1

40

50

60

70

80

90

100

Figure 3 The correlation observed between the vaporization enthalpy ∆lgHm(Tm) and the

enthalpy of transfer ∆Htrn(Tm) for run 1 The line represents the results of a linear

regression analysis of the standards (circles) The squares (and their associated

uncertainties) are the vaporization enthalpies calculated for the targets

11

ln(tot

a)

-10 -9 -8 -7 -6 -5 -4 -3

ln(p

po)

-16

-15

-14

-13

-12

-11

-10

-9

-8

Figure 4 The correlation observed between ln(ppo) and ln(tota) for run 1 The line

represents the results of a linear regression analysis of the standards (circles) The squares

(and their associated uncertainties) are the vapor pressures calculated for the targets

12

TABLE 1

Origin of the standards and targets and their analysis

Compound

FEMA

CAS

registry no

Supplier

Mass

fraction

purity

(supplier)

Mass

fraction

purity

(GC)

γ-hexanolactone FCC 2556 695-06-7 Bedoukian gt098 0993

γ-octanolactone FCC 2796 104-50-7 Bedoukian gt097 0996

δ-octanolactone FCC 3214 698-76-0 Bedoukian 098a 0989

ab

γ-nonanolactone FCC 2781 104-61-0 Bedoukian 098 0982

δ-nonanolactone FCC

3356

3301-94-8

Citrus and

Allied

Essences 098 086

γ-decanolactone FCC 2360 706-14-9 Bedoukian 097 0984

δ-decanolactone FCC 2361 705-86-2 Bedoukian 098a 0975

ac

γ-undecanolactone FCC 3091 104-67-6 SAFC gt098 0984

δ-undecanolactone FCC 3294 710-04-3 Bedoukian 098a 0948

ad

γ-dodecanolactone FCC 2400 2305-05-7 Bedoukian 097 0930

δ-dodecanolactone FCC 2401 713-95-1 Bedoukian 098a 0983

ae

a Sum of isomers reference [5]

b Two isomers 0977023 the minor isomer separated but was not identified

c Two isomers 0788 0212 the minor isomer separated but was not identified

d Two isomers 0928 0072 the minor isomer separated but was not identified

e Two isomers 0985 0015 the minor isomer separated but was not identified

13

TABLE 2

Thermochemical properties of the γ and δ lactones used as standardsa

∆lgHm(298 K)

kJsdotmol-1

A

B

C

TK(range)

γ-hexanolactone3 572plusmn03 2887 796414 627 283-353

δ-octanolactone3 670plusmn02 3107 906819 792 288-353

γ-nonanolactone4 703plusmn03 3251 968999 892 296-363

δ-nonanolactone3 707plusmn04 3236 968266 876 293-348

γ-decanolactone4 756plusmn03 3420 1046661 975 298-365

δ-decanolactone3 742plusmn03 3326 1027922 959 309-358

a A B and C are constants of equation 2

TABLE 3

A The correlation of enthalpies of transfer with vaporization enthalpies

Run 1

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42544 10338 3537 572plusmn03 575plusmn36

γ-octanolactone -51151 11381 4252 659plusmn39

δ-octanolactone -51695 11362 4298 670plusmn02 665plusmn39

γ-nonanolactone -55556 11927 4619 703plusmn03 703plusmn40

δ-nonanolactone -56242 11941 4676 707plusmn04 709plusmn41

γ-decanolactone -60035 1249 4991 756plusmn03 747plusmn42

δ-decanolactone -60638 12495 5041 742plusmn03 752plusmn42

γ-undecanolactone -64508 13057 5363 791plusmn44

δ-undecanolactone -65139 1307 5415 797plusmn44

γ-dodecanolactone -68966 13622 5734 834plusmn46

δ-dodecanolactone -69615 13641 5788 841plusmn46

∆lgHm(29815 K)kJsdotmol

-1 = (118plusmn0062)∆Htrn(434 K) + (1562plusmn28) r

2 = 09890 (4)

B The correlation of enthalpies of transfer with vaporization enthalpies

Run 2

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42798 10387 3558 572plusmn03 572plusmn37

γ-octanolactone -51374 11424 4271 661plusmn39

δ-octanolactone -51926 11407 4317 670plusmn02 666plusmn40

γ-nonanolactone -55748 11962 4635 703plusmn03 706plusmn41

δ-nonanolactone -56418 11974 469 707plusmn04 713plusmn41

γ-decanolactone -60181 12513 5003 756plusmn03 752plusmn43

δ-decanolactone -60804 12526 5055 742plusmn03 758plusmn43

γ-undecanolactone -64622 13075 5372 797plusmn44

δ-undecanolactone -65275 13094 5427 804plusmn45

γ-dodecanolactone -69059 1364 5741 843plusmn46

δ-dodecanolactone -69695 13655 5794 850plusmn47

∆lgHm(29815 K)kJsdotmol

-1 = (119plusmn0063)∆Htrn(434 K) + (1512plusmn29) r

2 = 09889 (5)

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

5

protocol was used in evaluating vaporization enthalpies adjusted to 29815 K from the

mean temperature

3 Experimental results and discussion

31 Vaporization enthalpies

If appropriate standards are used in the correlation between ∆Htrn(Tm) and ∆lgHm (29815

K) a good linear relationship is obtained despite the fact that the two enthalpies are

referenced to different temperature Figure 3 illustrates this correlation for the lactones

used as standards in run 1 The details of two correlations are summarized in tables 3A

and B and equations 4 and 5 listed below each respective table The results of both runs

are summarized in table 4 and compared to the literature values Despite the uncertainty

of approximately 4 kJmol-1

calculated from the correlation equations the vaporization

enthalpies of the standards are reproduced with an uncertainty of plusmn13 kJmol-1

(2 σ)

32 Vapor pressures

Vapor pressures generated from equation 2 at T = 29815 K were first converted to values

of ppo where po = 101325 Pa and then correlated as ln(ppo) with the corresponding

values of ln(tota) calculated from the slopes and intercepts listed in table 3 for both runs 1

and 2 The results of plotting ln(ppo) against ln(tota) at T = 29815 K for run 1 are

summarized in table 5 by equation 6 and illustrated in figure 4 The square symbols and

their associated uncertainties in the figure represent the values of ln(ppo) of the targets

calculated using equation 6 Results for run 2 are summarized by equation 7 and a table

similar to table 5 is provided in the supplementary material These correlation were then

repeated from T = (29815 to 350) K at 10 K intervals (not shown) The correlation

coefficients for each temperature evaluated r 2 gt 099 The vapor pressures obtained over

this 50 K temperature range were then fit to equation 8 The slopes and intercepts of the

fits are provided in table 6 for run 1 The vapor pressures calculated over this temperature

range for run 2 were virtually identical in most cases to those of run 1 after rounding off

and are not reported here Vapor pressure data for run 2 are provided in the

supplementary material All fits of ln(ppo) evaluated by correlation as a function of

temperature as 1T were characterized by correlation coefficients r2 gt 099

6

ln(ppo) = Arsquo+ Brsquo(TK) (8)

As an independent means of determining the overall quality of these correlations as a

function of temperature vaporization enthalpies were calculated from the product of the

slope of line of equation 8 and the gas constant (R) for each compound These values are

reported in the third column of table 6 These values were then adjusted back to T =

29815 K using equation 2 and the heat capacities listed in the table column 5 These

vaporization enthalpies adjusted to T = 29815 K are included in column 6 of table 6 and

compared to the values used as standards or to the values reported in table 4 in the last

column of the table The vaporization enthalpies of both standards and targets are all

reproduced with a standard deviation of plusmn15 kJsdotmol-1

(2 σ)

The vapor pressures at T = 29815 K in the last column of table 5 calculated using

equation 6 and reproduced in column 3 of table 7 are compared with available

experimental and estimated values in table 7 columns 2 and 5 respectively The

uncertainties associated with equation 6 were calculated from the corresponding

uncertainties in the slope and intercept of the equation as described above Vapor

pressures calculated using equation 8 and the constants of table 6 column 4 of table 7

differ slightly but also reproduce both literature values and those calculated using

equation 6 well within the uncertainties cited The vapor pressures of the standards are

reproduced using both equation 6 and by equation 8 and the constants of table 6 within 9

of their value The last two columns of the table compare vapor pressures calculated at

T = 29315 K using equation 8 and the constants of table 6 The vapor pressures reported

in column 6 are from MSDS sheets made available by the supplier [5] It is not known if

they represent experimental or estimated values The vapor pressures calculated in this

work are consistently smaller than the MSDS values by roughly a factor of 4 Equation 8

and the constants of table 6 can be used to provide vapor pressures of the materials

evaluated in this work from T = (29815 to 350) K

33 Vaporization enthalpy estimates

7

Emelrsquoyanenko et al[4] reported a group additivity procedure for predicting the

vaporization enthalpies of γ and δ-lactones Table 8 summarizes the group values they

reported and table 9 compares the predicted values with the experimental vaporization

enthalpies reported previously and those evaluated in this work Agreement with the

results reported here are well within the experimental uncertainties All values in column

4 are slightly over predicted but are reproduced with a standard deviation of plusmn10 kJsdotmol-1

(2 σ)

34 Vaporization enthalpy comparisons

In addition to the γ and δ-lactones studied Wiberg and Waldron [13] reported the

vaporization enthalpies of a corresponding series of ω-lactones These results are

compared in table 10 It should be noted that ω and γ-butanolactone and ω and δ-

pentanolactone refer to the same material and are included to illustrate the reproducibility

of literature values As the ring size increases and becomes more flexible the

vaporization enthalpies appear to attenuate Consistent with this interpretation an

alternative estimation equation eq 9 generated from the vaporization enthalpies of

acyclic esters [14] greatly underestimates the vaporization enthalpies of both the smaller

γ and δ-lactones but appears to provide an improved estimation of the larger ones as

indicated in the last column of table 10 The cyclic ethers oxetane tetrahydrofuran and

pyran are also under-estimated by eq 9 [15] The nC nQ and b terms in equation 9 refer to

the total number of carbons the number of quaternary sp3 hybridized carbons (0) and the

contribution of the functional group (105 kJsdotmol-1

) respectively

∆lgHm(298 K) kJsdotmol

-1 = 469(nC - nQ) 13nQ +30 + b (9)

33 Summary

The vaporization enthalpies at T = 29815 K and vapor pressures from T = (29815 to

350) K of three γ and two δ-lactones are evaluated by correlation gas chromatography

using a series of closely related standards The vaporization enthalpies are believed

known with an uncertainty somewhat less than plusmn4 kJsdotmol-1

and vapor pressures within an

uncertainty of approximately 40 of their value

8

Appendix A Supplementary data

Supplementary data associated with this article can be found in the online version at

http

References

(1) httpwwwbedoukiancomproductsproductaspid=463 accessed 82813

(2) httpwwwfdagovFoodIngredientsPackagingLabelingGRAS accessed

82813

(3) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 39 (2007) 10-15

(4) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 40 (2008) 911-16

(5) httpbedoukiancomproductssearchflavorasp accessed 82913

(6) L A Peacock R Fuchs J Am Chem Soc 99 (1977) 5524-5

(7) D Lipkind J S Chickos J Chem Eng Data 55 (2010) 698-707

(8) J A Wilson J S Chickos J Chem Eng Data 57 (2012) 2281-2285

(9) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-940

(10) J S Chickos D G Hesse J F Liebman Struct Chem 4 (1993) 261-269

(11) The EPI Suite is available as a download from

httpwwwepagovopptexposurepubsepisuitedlhtm accessed 61013

(12) M Covarrubias-Cervantes I Mokbel D Campion J Jose A Voilley Food

Chem 85 (2004) 221-229

(13) K B Wiberg R F Waldron J Am Chem Soc 113 (1991) 7697-7705

(14) J S Chickos W E Acree Jr J F Liebman Estimating Phase Change

Enthalpies and Entropies In Computational Thermochemistry Symposiun Series

677 K K IrikuraD J Frurip Ed ACS Washington DC 1998 Chapter 4

(15) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-942

9

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

O

O

(CH2)n

Figure 1 The structures of the γ and δ-lactone standards and targets and the ω-lactones

Time min

0 5 10 15 20

Inte

nsi

tyc

ou

nts

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

22000

Figure 2 GC chromatograph of a γ and δ-lactone mixture at T = 418 K 1 methanol 2 γ-

hexanolactone 3 γ-octanolactone 4 δ-octanolactone 5 γ-nonanolactone 6 δ-

nonanolactone 7 γ-decanolactone 8 δ-decanolactone 9 γ-undecanolactone 10 δ-

undecanolactone 11 γ-dodecanolactone 12 δ-dodecanolactone

12

11

10

9

8

6 7

1 2 3 5

4

10

∆Htrn

(Tm)kJmol

-1

30 35 40 45 50 55 60

∆lgH

(29

81

5 K

)kJ

mol-1

40

50

60

70

80

90

100

Figure 3 The correlation observed between the vaporization enthalpy ∆lgHm(Tm) and the

enthalpy of transfer ∆Htrn(Tm) for run 1 The line represents the results of a linear

regression analysis of the standards (circles) The squares (and their associated

uncertainties) are the vaporization enthalpies calculated for the targets

11

ln(tot

a)

-10 -9 -8 -7 -6 -5 -4 -3

ln(p

po)

-16

-15

-14

-13

-12

-11

-10

-9

-8

Figure 4 The correlation observed between ln(ppo) and ln(tota) for run 1 The line

represents the results of a linear regression analysis of the standards (circles) The squares

(and their associated uncertainties) are the vapor pressures calculated for the targets

12

TABLE 1

Origin of the standards and targets and their analysis

Compound

FEMA

CAS

registry no

Supplier

Mass

fraction

purity

(supplier)

Mass

fraction

purity

(GC)

γ-hexanolactone FCC 2556 695-06-7 Bedoukian gt098 0993

γ-octanolactone FCC 2796 104-50-7 Bedoukian gt097 0996

δ-octanolactone FCC 3214 698-76-0 Bedoukian 098a 0989

ab

γ-nonanolactone FCC 2781 104-61-0 Bedoukian 098 0982

δ-nonanolactone FCC

3356

3301-94-8

Citrus and

Allied

Essences 098 086

γ-decanolactone FCC 2360 706-14-9 Bedoukian 097 0984

δ-decanolactone FCC 2361 705-86-2 Bedoukian 098a 0975

ac

γ-undecanolactone FCC 3091 104-67-6 SAFC gt098 0984

δ-undecanolactone FCC 3294 710-04-3 Bedoukian 098a 0948

ad

γ-dodecanolactone FCC 2400 2305-05-7 Bedoukian 097 0930

δ-dodecanolactone FCC 2401 713-95-1 Bedoukian 098a 0983

ae

a Sum of isomers reference [5]

b Two isomers 0977023 the minor isomer separated but was not identified

c Two isomers 0788 0212 the minor isomer separated but was not identified

d Two isomers 0928 0072 the minor isomer separated but was not identified

e Two isomers 0985 0015 the minor isomer separated but was not identified

13

TABLE 2

Thermochemical properties of the γ and δ lactones used as standardsa

∆lgHm(298 K)

kJsdotmol-1

A

B

C

TK(range)

γ-hexanolactone3 572plusmn03 2887 796414 627 283-353

δ-octanolactone3 670plusmn02 3107 906819 792 288-353

γ-nonanolactone4 703plusmn03 3251 968999 892 296-363

δ-nonanolactone3 707plusmn04 3236 968266 876 293-348

γ-decanolactone4 756plusmn03 3420 1046661 975 298-365

δ-decanolactone3 742plusmn03 3326 1027922 959 309-358

a A B and C are constants of equation 2

TABLE 3

A The correlation of enthalpies of transfer with vaporization enthalpies

Run 1

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42544 10338 3537 572plusmn03 575plusmn36

γ-octanolactone -51151 11381 4252 659plusmn39

δ-octanolactone -51695 11362 4298 670plusmn02 665plusmn39

γ-nonanolactone -55556 11927 4619 703plusmn03 703plusmn40

δ-nonanolactone -56242 11941 4676 707plusmn04 709plusmn41

γ-decanolactone -60035 1249 4991 756plusmn03 747plusmn42

δ-decanolactone -60638 12495 5041 742plusmn03 752plusmn42

γ-undecanolactone -64508 13057 5363 791plusmn44

δ-undecanolactone -65139 1307 5415 797plusmn44

γ-dodecanolactone -68966 13622 5734 834plusmn46

δ-dodecanolactone -69615 13641 5788 841plusmn46

∆lgHm(29815 K)kJsdotmol

-1 = (118plusmn0062)∆Htrn(434 K) + (1562plusmn28) r

2 = 09890 (4)

B The correlation of enthalpies of transfer with vaporization enthalpies

Run 2

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42798 10387 3558 572plusmn03 572plusmn37

γ-octanolactone -51374 11424 4271 661plusmn39

δ-octanolactone -51926 11407 4317 670plusmn02 666plusmn40

γ-nonanolactone -55748 11962 4635 703plusmn03 706plusmn41

δ-nonanolactone -56418 11974 469 707plusmn04 713plusmn41

γ-decanolactone -60181 12513 5003 756plusmn03 752plusmn43

δ-decanolactone -60804 12526 5055 742plusmn03 758plusmn43

γ-undecanolactone -64622 13075 5372 797plusmn44

δ-undecanolactone -65275 13094 5427 804plusmn45

γ-dodecanolactone -69059 1364 5741 843plusmn46

δ-dodecanolactone -69695 13655 5794 850plusmn47

∆lgHm(29815 K)kJsdotmol

-1 = (119plusmn0063)∆Htrn(434 K) + (1512plusmn29) r

2 = 09889 (5)

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

6

ln(ppo) = Arsquo+ Brsquo(TK) (8)

As an independent means of determining the overall quality of these correlations as a

function of temperature vaporization enthalpies were calculated from the product of the

slope of line of equation 8 and the gas constant (R) for each compound These values are

reported in the third column of table 6 These values were then adjusted back to T =

29815 K using equation 2 and the heat capacities listed in the table column 5 These

vaporization enthalpies adjusted to T = 29815 K are included in column 6 of table 6 and

compared to the values used as standards or to the values reported in table 4 in the last

column of the table The vaporization enthalpies of both standards and targets are all

reproduced with a standard deviation of plusmn15 kJsdotmol-1

(2 σ)

The vapor pressures at T = 29815 K in the last column of table 5 calculated using

equation 6 and reproduced in column 3 of table 7 are compared with available

experimental and estimated values in table 7 columns 2 and 5 respectively The

uncertainties associated with equation 6 were calculated from the corresponding

uncertainties in the slope and intercept of the equation as described above Vapor

pressures calculated using equation 8 and the constants of table 6 column 4 of table 7

differ slightly but also reproduce both literature values and those calculated using

equation 6 well within the uncertainties cited The vapor pressures of the standards are

reproduced using both equation 6 and by equation 8 and the constants of table 6 within 9

of their value The last two columns of the table compare vapor pressures calculated at

T = 29315 K using equation 8 and the constants of table 6 The vapor pressures reported

in column 6 are from MSDS sheets made available by the supplier [5] It is not known if

they represent experimental or estimated values The vapor pressures calculated in this

work are consistently smaller than the MSDS values by roughly a factor of 4 Equation 8

and the constants of table 6 can be used to provide vapor pressures of the materials

evaluated in this work from T = (29815 to 350) K

33 Vaporization enthalpy estimates

7

Emelrsquoyanenko et al[4] reported a group additivity procedure for predicting the

vaporization enthalpies of γ and δ-lactones Table 8 summarizes the group values they

reported and table 9 compares the predicted values with the experimental vaporization

enthalpies reported previously and those evaluated in this work Agreement with the

results reported here are well within the experimental uncertainties All values in column

4 are slightly over predicted but are reproduced with a standard deviation of plusmn10 kJsdotmol-1

(2 σ)

34 Vaporization enthalpy comparisons

In addition to the γ and δ-lactones studied Wiberg and Waldron [13] reported the

vaporization enthalpies of a corresponding series of ω-lactones These results are

compared in table 10 It should be noted that ω and γ-butanolactone and ω and δ-

pentanolactone refer to the same material and are included to illustrate the reproducibility

of literature values As the ring size increases and becomes more flexible the

vaporization enthalpies appear to attenuate Consistent with this interpretation an

alternative estimation equation eq 9 generated from the vaporization enthalpies of

acyclic esters [14] greatly underestimates the vaporization enthalpies of both the smaller

γ and δ-lactones but appears to provide an improved estimation of the larger ones as

indicated in the last column of table 10 The cyclic ethers oxetane tetrahydrofuran and

pyran are also under-estimated by eq 9 [15] The nC nQ and b terms in equation 9 refer to

the total number of carbons the number of quaternary sp3 hybridized carbons (0) and the

contribution of the functional group (105 kJsdotmol-1

) respectively

∆lgHm(298 K) kJsdotmol

-1 = 469(nC - nQ) 13nQ +30 + b (9)

33 Summary

The vaporization enthalpies at T = 29815 K and vapor pressures from T = (29815 to

350) K of three γ and two δ-lactones are evaluated by correlation gas chromatography

using a series of closely related standards The vaporization enthalpies are believed

known with an uncertainty somewhat less than plusmn4 kJsdotmol-1

and vapor pressures within an

uncertainty of approximately 40 of their value

8

Appendix A Supplementary data

Supplementary data associated with this article can be found in the online version at

http

References

(1) httpwwwbedoukiancomproductsproductaspid=463 accessed 82813

(2) httpwwwfdagovFoodIngredientsPackagingLabelingGRAS accessed

82813

(3) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 39 (2007) 10-15

(4) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 40 (2008) 911-16

(5) httpbedoukiancomproductssearchflavorasp accessed 82913

(6) L A Peacock R Fuchs J Am Chem Soc 99 (1977) 5524-5

(7) D Lipkind J S Chickos J Chem Eng Data 55 (2010) 698-707

(8) J A Wilson J S Chickos J Chem Eng Data 57 (2012) 2281-2285

(9) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-940

(10) J S Chickos D G Hesse J F Liebman Struct Chem 4 (1993) 261-269

(11) The EPI Suite is available as a download from

httpwwwepagovopptexposurepubsepisuitedlhtm accessed 61013

(12) M Covarrubias-Cervantes I Mokbel D Campion J Jose A Voilley Food

Chem 85 (2004) 221-229

(13) K B Wiberg R F Waldron J Am Chem Soc 113 (1991) 7697-7705

(14) J S Chickos W E Acree Jr J F Liebman Estimating Phase Change

Enthalpies and Entropies In Computational Thermochemistry Symposiun Series

677 K K IrikuraD J Frurip Ed ACS Washington DC 1998 Chapter 4

(15) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-942

9

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

O

O

(CH2)n

Figure 1 The structures of the γ and δ-lactone standards and targets and the ω-lactones

Time min

0 5 10 15 20

Inte

nsi

tyc

ou

nts

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

22000

Figure 2 GC chromatograph of a γ and δ-lactone mixture at T = 418 K 1 methanol 2 γ-

hexanolactone 3 γ-octanolactone 4 δ-octanolactone 5 γ-nonanolactone 6 δ-

nonanolactone 7 γ-decanolactone 8 δ-decanolactone 9 γ-undecanolactone 10 δ-

undecanolactone 11 γ-dodecanolactone 12 δ-dodecanolactone

12

11

10

9

8

6 7

1 2 3 5

4

10

∆Htrn

(Tm)kJmol

-1

30 35 40 45 50 55 60

∆lgH

(29

81

5 K

)kJ

mol-1

40

50

60

70

80

90

100

Figure 3 The correlation observed between the vaporization enthalpy ∆lgHm(Tm) and the

enthalpy of transfer ∆Htrn(Tm) for run 1 The line represents the results of a linear

regression analysis of the standards (circles) The squares (and their associated

uncertainties) are the vaporization enthalpies calculated for the targets

11

ln(tot

a)

-10 -9 -8 -7 -6 -5 -4 -3

ln(p

po)

-16

-15

-14

-13

-12

-11

-10

-9

-8

Figure 4 The correlation observed between ln(ppo) and ln(tota) for run 1 The line

represents the results of a linear regression analysis of the standards (circles) The squares

(and their associated uncertainties) are the vapor pressures calculated for the targets

12

TABLE 1

Origin of the standards and targets and their analysis

Compound

FEMA

CAS

registry no

Supplier

Mass

fraction

purity

(supplier)

Mass

fraction

purity

(GC)

γ-hexanolactone FCC 2556 695-06-7 Bedoukian gt098 0993

γ-octanolactone FCC 2796 104-50-7 Bedoukian gt097 0996

δ-octanolactone FCC 3214 698-76-0 Bedoukian 098a 0989

ab

γ-nonanolactone FCC 2781 104-61-0 Bedoukian 098 0982

δ-nonanolactone FCC

3356

3301-94-8

Citrus and

Allied

Essences 098 086

γ-decanolactone FCC 2360 706-14-9 Bedoukian 097 0984

δ-decanolactone FCC 2361 705-86-2 Bedoukian 098a 0975

ac

γ-undecanolactone FCC 3091 104-67-6 SAFC gt098 0984

δ-undecanolactone FCC 3294 710-04-3 Bedoukian 098a 0948

ad

γ-dodecanolactone FCC 2400 2305-05-7 Bedoukian 097 0930

δ-dodecanolactone FCC 2401 713-95-1 Bedoukian 098a 0983

ae

a Sum of isomers reference [5]

b Two isomers 0977023 the minor isomer separated but was not identified

c Two isomers 0788 0212 the minor isomer separated but was not identified

d Two isomers 0928 0072 the minor isomer separated but was not identified

e Two isomers 0985 0015 the minor isomer separated but was not identified

13

TABLE 2

Thermochemical properties of the γ and δ lactones used as standardsa

∆lgHm(298 K)

kJsdotmol-1

A

B

C

TK(range)

γ-hexanolactone3 572plusmn03 2887 796414 627 283-353

δ-octanolactone3 670plusmn02 3107 906819 792 288-353

γ-nonanolactone4 703plusmn03 3251 968999 892 296-363

δ-nonanolactone3 707plusmn04 3236 968266 876 293-348

γ-decanolactone4 756plusmn03 3420 1046661 975 298-365

δ-decanolactone3 742plusmn03 3326 1027922 959 309-358

a A B and C are constants of equation 2

TABLE 3

A The correlation of enthalpies of transfer with vaporization enthalpies

Run 1

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42544 10338 3537 572plusmn03 575plusmn36

γ-octanolactone -51151 11381 4252 659plusmn39

δ-octanolactone -51695 11362 4298 670plusmn02 665plusmn39

γ-nonanolactone -55556 11927 4619 703plusmn03 703plusmn40

δ-nonanolactone -56242 11941 4676 707plusmn04 709plusmn41

γ-decanolactone -60035 1249 4991 756plusmn03 747plusmn42

δ-decanolactone -60638 12495 5041 742plusmn03 752plusmn42

γ-undecanolactone -64508 13057 5363 791plusmn44

δ-undecanolactone -65139 1307 5415 797plusmn44

γ-dodecanolactone -68966 13622 5734 834plusmn46

δ-dodecanolactone -69615 13641 5788 841plusmn46

∆lgHm(29815 K)kJsdotmol

-1 = (118plusmn0062)∆Htrn(434 K) + (1562plusmn28) r

2 = 09890 (4)

B The correlation of enthalpies of transfer with vaporization enthalpies

Run 2

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42798 10387 3558 572plusmn03 572plusmn37

γ-octanolactone -51374 11424 4271 661plusmn39

δ-octanolactone -51926 11407 4317 670plusmn02 666plusmn40

γ-nonanolactone -55748 11962 4635 703plusmn03 706plusmn41

δ-nonanolactone -56418 11974 469 707plusmn04 713plusmn41

γ-decanolactone -60181 12513 5003 756plusmn03 752plusmn43

δ-decanolactone -60804 12526 5055 742plusmn03 758plusmn43

γ-undecanolactone -64622 13075 5372 797plusmn44

δ-undecanolactone -65275 13094 5427 804plusmn45

γ-dodecanolactone -69059 1364 5741 843plusmn46

δ-dodecanolactone -69695 13655 5794 850plusmn47

∆lgHm(29815 K)kJsdotmol

-1 = (119plusmn0063)∆Htrn(434 K) + (1512plusmn29) r

2 = 09889 (5)

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

7

Emelrsquoyanenko et al[4] reported a group additivity procedure for predicting the

vaporization enthalpies of γ and δ-lactones Table 8 summarizes the group values they

reported and table 9 compares the predicted values with the experimental vaporization

enthalpies reported previously and those evaluated in this work Agreement with the

results reported here are well within the experimental uncertainties All values in column

4 are slightly over predicted but are reproduced with a standard deviation of plusmn10 kJsdotmol-1

(2 σ)

34 Vaporization enthalpy comparisons

In addition to the γ and δ-lactones studied Wiberg and Waldron [13] reported the

vaporization enthalpies of a corresponding series of ω-lactones These results are

compared in table 10 It should be noted that ω and γ-butanolactone and ω and δ-

pentanolactone refer to the same material and are included to illustrate the reproducibility

of literature values As the ring size increases and becomes more flexible the

vaporization enthalpies appear to attenuate Consistent with this interpretation an

alternative estimation equation eq 9 generated from the vaporization enthalpies of

acyclic esters [14] greatly underestimates the vaporization enthalpies of both the smaller

γ and δ-lactones but appears to provide an improved estimation of the larger ones as

indicated in the last column of table 10 The cyclic ethers oxetane tetrahydrofuran and

pyran are also under-estimated by eq 9 [15] The nC nQ and b terms in equation 9 refer to

the total number of carbons the number of quaternary sp3 hybridized carbons (0) and the

contribution of the functional group (105 kJsdotmol-1

) respectively

∆lgHm(298 K) kJsdotmol

-1 = 469(nC - nQ) 13nQ +30 + b (9)

33 Summary

The vaporization enthalpies at T = 29815 K and vapor pressures from T = (29815 to

350) K of three γ and two δ-lactones are evaluated by correlation gas chromatography

using a series of closely related standards The vaporization enthalpies are believed

known with an uncertainty somewhat less than plusmn4 kJsdotmol-1

and vapor pressures within an

uncertainty of approximately 40 of their value

8

Appendix A Supplementary data

Supplementary data associated with this article can be found in the online version at

http

References

(1) httpwwwbedoukiancomproductsproductaspid=463 accessed 82813

(2) httpwwwfdagovFoodIngredientsPackagingLabelingGRAS accessed

82813

(3) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 39 (2007) 10-15

(4) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 40 (2008) 911-16

(5) httpbedoukiancomproductssearchflavorasp accessed 82913

(6) L A Peacock R Fuchs J Am Chem Soc 99 (1977) 5524-5

(7) D Lipkind J S Chickos J Chem Eng Data 55 (2010) 698-707

(8) J A Wilson J S Chickos J Chem Eng Data 57 (2012) 2281-2285

(9) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-940

(10) J S Chickos D G Hesse J F Liebman Struct Chem 4 (1993) 261-269

(11) The EPI Suite is available as a download from

httpwwwepagovopptexposurepubsepisuitedlhtm accessed 61013

(12) M Covarrubias-Cervantes I Mokbel D Campion J Jose A Voilley Food

Chem 85 (2004) 221-229

(13) K B Wiberg R F Waldron J Am Chem Soc 113 (1991) 7697-7705

(14) J S Chickos W E Acree Jr J F Liebman Estimating Phase Change

Enthalpies and Entropies In Computational Thermochemistry Symposiun Series

677 K K IrikuraD J Frurip Ed ACS Washington DC 1998 Chapter 4

(15) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-942

9

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

O

O

(CH2)n

Figure 1 The structures of the γ and δ-lactone standards and targets and the ω-lactones

Time min

0 5 10 15 20

Inte

nsi

tyc

ou

nts

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

22000

Figure 2 GC chromatograph of a γ and δ-lactone mixture at T = 418 K 1 methanol 2 γ-

hexanolactone 3 γ-octanolactone 4 δ-octanolactone 5 γ-nonanolactone 6 δ-

nonanolactone 7 γ-decanolactone 8 δ-decanolactone 9 γ-undecanolactone 10 δ-

undecanolactone 11 γ-dodecanolactone 12 δ-dodecanolactone

12

11

10

9

8

6 7

1 2 3 5

4

10

∆Htrn

(Tm)kJmol

-1

30 35 40 45 50 55 60

∆lgH

(29

81

5 K

)kJ

mol-1

40

50

60

70

80

90

100

Figure 3 The correlation observed between the vaporization enthalpy ∆lgHm(Tm) and the

enthalpy of transfer ∆Htrn(Tm) for run 1 The line represents the results of a linear

regression analysis of the standards (circles) The squares (and their associated

uncertainties) are the vaporization enthalpies calculated for the targets

11

ln(tot

a)

-10 -9 -8 -7 -6 -5 -4 -3

ln(p

po)

-16

-15

-14

-13

-12

-11

-10

-9

-8

Figure 4 The correlation observed between ln(ppo) and ln(tota) for run 1 The line

represents the results of a linear regression analysis of the standards (circles) The squares

(and their associated uncertainties) are the vapor pressures calculated for the targets

12

TABLE 1

Origin of the standards and targets and their analysis

Compound

FEMA

CAS

registry no

Supplier

Mass

fraction

purity

(supplier)

Mass

fraction

purity

(GC)

γ-hexanolactone FCC 2556 695-06-7 Bedoukian gt098 0993

γ-octanolactone FCC 2796 104-50-7 Bedoukian gt097 0996

δ-octanolactone FCC 3214 698-76-0 Bedoukian 098a 0989

ab

γ-nonanolactone FCC 2781 104-61-0 Bedoukian 098 0982

δ-nonanolactone FCC

3356

3301-94-8

Citrus and

Allied

Essences 098 086

γ-decanolactone FCC 2360 706-14-9 Bedoukian 097 0984

δ-decanolactone FCC 2361 705-86-2 Bedoukian 098a 0975

ac

γ-undecanolactone FCC 3091 104-67-6 SAFC gt098 0984

δ-undecanolactone FCC 3294 710-04-3 Bedoukian 098a 0948

ad

γ-dodecanolactone FCC 2400 2305-05-7 Bedoukian 097 0930

δ-dodecanolactone FCC 2401 713-95-1 Bedoukian 098a 0983

ae

a Sum of isomers reference [5]

b Two isomers 0977023 the minor isomer separated but was not identified

c Two isomers 0788 0212 the minor isomer separated but was not identified

d Two isomers 0928 0072 the minor isomer separated but was not identified

e Two isomers 0985 0015 the minor isomer separated but was not identified

13

TABLE 2

Thermochemical properties of the γ and δ lactones used as standardsa

∆lgHm(298 K)

kJsdotmol-1

A

B

C

TK(range)

γ-hexanolactone3 572plusmn03 2887 796414 627 283-353

δ-octanolactone3 670plusmn02 3107 906819 792 288-353

γ-nonanolactone4 703plusmn03 3251 968999 892 296-363

δ-nonanolactone3 707plusmn04 3236 968266 876 293-348

γ-decanolactone4 756plusmn03 3420 1046661 975 298-365

δ-decanolactone3 742plusmn03 3326 1027922 959 309-358

a A B and C are constants of equation 2

TABLE 3

A The correlation of enthalpies of transfer with vaporization enthalpies

Run 1

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42544 10338 3537 572plusmn03 575plusmn36

γ-octanolactone -51151 11381 4252 659plusmn39

δ-octanolactone -51695 11362 4298 670plusmn02 665plusmn39

γ-nonanolactone -55556 11927 4619 703plusmn03 703plusmn40

δ-nonanolactone -56242 11941 4676 707plusmn04 709plusmn41

γ-decanolactone -60035 1249 4991 756plusmn03 747plusmn42

δ-decanolactone -60638 12495 5041 742plusmn03 752plusmn42

γ-undecanolactone -64508 13057 5363 791plusmn44

δ-undecanolactone -65139 1307 5415 797plusmn44

γ-dodecanolactone -68966 13622 5734 834plusmn46

δ-dodecanolactone -69615 13641 5788 841plusmn46

∆lgHm(29815 K)kJsdotmol

-1 = (118plusmn0062)∆Htrn(434 K) + (1562plusmn28) r

2 = 09890 (4)

B The correlation of enthalpies of transfer with vaporization enthalpies

Run 2

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42798 10387 3558 572plusmn03 572plusmn37

γ-octanolactone -51374 11424 4271 661plusmn39

δ-octanolactone -51926 11407 4317 670plusmn02 666plusmn40

γ-nonanolactone -55748 11962 4635 703plusmn03 706plusmn41

δ-nonanolactone -56418 11974 469 707plusmn04 713plusmn41

γ-decanolactone -60181 12513 5003 756plusmn03 752plusmn43

δ-decanolactone -60804 12526 5055 742plusmn03 758plusmn43

γ-undecanolactone -64622 13075 5372 797plusmn44

δ-undecanolactone -65275 13094 5427 804plusmn45

γ-dodecanolactone -69059 1364 5741 843plusmn46

δ-dodecanolactone -69695 13655 5794 850plusmn47

∆lgHm(29815 K)kJsdotmol

-1 = (119plusmn0063)∆Htrn(434 K) + (1512plusmn29) r

2 = 09889 (5)

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

8

Appendix A Supplementary data

Supplementary data associated with this article can be found in the online version at

http

References

(1) httpwwwbedoukiancomproductsproductaspid=463 accessed 82813

(2) httpwwwfdagovFoodIngredientsPackagingLabelingGRAS accessed

82813

(3) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 39 (2007) 10-15

(4) V N Emelrsquoyanenko S A Kozlova S P Verevkin G N Roganov J Chem

Thermodyn 40 (2008) 911-16

(5) httpbedoukiancomproductssearchflavorasp accessed 82913

(6) L A Peacock R Fuchs J Am Chem Soc 99 (1977) 5524-5

(7) D Lipkind J S Chickos J Chem Eng Data 55 (2010) 698-707

(8) J A Wilson J S Chickos J Chem Eng Data 57 (2012) 2281-2285

(9) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-940

(10) J S Chickos D G Hesse J F Liebman Struct Chem 4 (1993) 261-269

(11) The EPI Suite is available as a download from

httpwwwepagovopptexposurepubsepisuitedlhtm accessed 61013

(12) M Covarrubias-Cervantes I Mokbel D Campion J Jose A Voilley Food

Chem 85 (2004) 221-229

(13) K B Wiberg R F Waldron J Am Chem Soc 113 (1991) 7697-7705

(14) J S Chickos W E Acree Jr J F Liebman Estimating Phase Change

Enthalpies and Entropies In Computational Thermochemistry Symposiun Series

677 K K IrikuraD J Frurip Ed ACS Washington DC 1998 Chapter 4

(15) W Acree Jr J S Chickos J Phys Chem Ref Data 39 (2010) 1-942

9

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

O

O

(CH2)n

Figure 1 The structures of the γ and δ-lactone standards and targets and the ω-lactones

Time min

0 5 10 15 20

Inte

nsi

tyc

ou

nts

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

22000

Figure 2 GC chromatograph of a γ and δ-lactone mixture at T = 418 K 1 methanol 2 γ-

hexanolactone 3 γ-octanolactone 4 δ-octanolactone 5 γ-nonanolactone 6 δ-

nonanolactone 7 γ-decanolactone 8 δ-decanolactone 9 γ-undecanolactone 10 δ-

undecanolactone 11 γ-dodecanolactone 12 δ-dodecanolactone

12

11

10

9

8

6 7

1 2 3 5

4

10

∆Htrn

(Tm)kJmol

-1

30 35 40 45 50 55 60

∆lgH

(29

81

5 K

)kJ

mol-1

40

50

60

70

80

90

100

Figure 3 The correlation observed between the vaporization enthalpy ∆lgHm(Tm) and the

enthalpy of transfer ∆Htrn(Tm) for run 1 The line represents the results of a linear

regression analysis of the standards (circles) The squares (and their associated

uncertainties) are the vaporization enthalpies calculated for the targets

11

ln(tot

a)

-10 -9 -8 -7 -6 -5 -4 -3

ln(p

po)

-16

-15

-14

-13

-12

-11

-10

-9

-8

Figure 4 The correlation observed between ln(ppo) and ln(tota) for run 1 The line

represents the results of a linear regression analysis of the standards (circles) The squares

(and their associated uncertainties) are the vapor pressures calculated for the targets

12

TABLE 1

Origin of the standards and targets and their analysis

Compound

FEMA

CAS

registry no

Supplier

Mass

fraction

purity

(supplier)

Mass

fraction

purity

(GC)

γ-hexanolactone FCC 2556 695-06-7 Bedoukian gt098 0993

γ-octanolactone FCC 2796 104-50-7 Bedoukian gt097 0996

δ-octanolactone FCC 3214 698-76-0 Bedoukian 098a 0989

ab

γ-nonanolactone FCC 2781 104-61-0 Bedoukian 098 0982

δ-nonanolactone FCC

3356

3301-94-8

Citrus and

Allied

Essences 098 086

γ-decanolactone FCC 2360 706-14-9 Bedoukian 097 0984

δ-decanolactone FCC 2361 705-86-2 Bedoukian 098a 0975

ac

γ-undecanolactone FCC 3091 104-67-6 SAFC gt098 0984

δ-undecanolactone FCC 3294 710-04-3 Bedoukian 098a 0948

ad

γ-dodecanolactone FCC 2400 2305-05-7 Bedoukian 097 0930

δ-dodecanolactone FCC 2401 713-95-1 Bedoukian 098a 0983

ae

a Sum of isomers reference [5]

b Two isomers 0977023 the minor isomer separated but was not identified

c Two isomers 0788 0212 the minor isomer separated but was not identified

d Two isomers 0928 0072 the minor isomer separated but was not identified

e Two isomers 0985 0015 the minor isomer separated but was not identified

13

TABLE 2

Thermochemical properties of the γ and δ lactones used as standardsa

∆lgHm(298 K)

kJsdotmol-1

A

B

C

TK(range)

γ-hexanolactone3 572plusmn03 2887 796414 627 283-353

δ-octanolactone3 670plusmn02 3107 906819 792 288-353

γ-nonanolactone4 703plusmn03 3251 968999 892 296-363

δ-nonanolactone3 707plusmn04 3236 968266 876 293-348

γ-decanolactone4 756plusmn03 3420 1046661 975 298-365

δ-decanolactone3 742plusmn03 3326 1027922 959 309-358

a A B and C are constants of equation 2

TABLE 3

A The correlation of enthalpies of transfer with vaporization enthalpies

Run 1

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42544 10338 3537 572plusmn03 575plusmn36

γ-octanolactone -51151 11381 4252 659plusmn39

δ-octanolactone -51695 11362 4298 670plusmn02 665plusmn39

γ-nonanolactone -55556 11927 4619 703plusmn03 703plusmn40

δ-nonanolactone -56242 11941 4676 707plusmn04 709plusmn41

γ-decanolactone -60035 1249 4991 756plusmn03 747plusmn42

δ-decanolactone -60638 12495 5041 742plusmn03 752plusmn42

γ-undecanolactone -64508 13057 5363 791plusmn44

δ-undecanolactone -65139 1307 5415 797plusmn44

γ-dodecanolactone -68966 13622 5734 834plusmn46

δ-dodecanolactone -69615 13641 5788 841plusmn46

∆lgHm(29815 K)kJsdotmol

-1 = (118plusmn0062)∆Htrn(434 K) + (1562plusmn28) r

2 = 09890 (4)

B The correlation of enthalpies of transfer with vaporization enthalpies

Run 2

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42798 10387 3558 572plusmn03 572plusmn37

γ-octanolactone -51374 11424 4271 661plusmn39

δ-octanolactone -51926 11407 4317 670plusmn02 666plusmn40

γ-nonanolactone -55748 11962 4635 703plusmn03 706plusmn41

δ-nonanolactone -56418 11974 469 707plusmn04 713plusmn41

γ-decanolactone -60181 12513 5003 756plusmn03 752plusmn43

δ-decanolactone -60804 12526 5055 742plusmn03 758plusmn43

γ-undecanolactone -64622 13075 5372 797plusmn44

δ-undecanolactone -65275 13094 5427 804plusmn45

γ-dodecanolactone -69059 1364 5741 843plusmn46

δ-dodecanolactone -69695 13655 5794 850plusmn47

∆lgHm(29815 K)kJsdotmol

-1 = (119plusmn0063)∆Htrn(434 K) + (1512plusmn29) r

2 = 09889 (5)

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

9

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

O

O

(CH2)n

Figure 1 The structures of the γ and δ-lactone standards and targets and the ω-lactones

Time min

0 5 10 15 20

Inte

nsi

tyc

ou

nts

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

22000

Figure 2 GC chromatograph of a γ and δ-lactone mixture at T = 418 K 1 methanol 2 γ-

hexanolactone 3 γ-octanolactone 4 δ-octanolactone 5 γ-nonanolactone 6 δ-

nonanolactone 7 γ-decanolactone 8 δ-decanolactone 9 γ-undecanolactone 10 δ-

undecanolactone 11 γ-dodecanolactone 12 δ-dodecanolactone

12

11

10

9

8

6 7

1 2 3 5

4

10

∆Htrn

(Tm)kJmol

-1

30 35 40 45 50 55 60

∆lgH

(29

81

5 K

)kJ

mol-1

40

50

60

70

80

90

100

Figure 3 The correlation observed between the vaporization enthalpy ∆lgHm(Tm) and the

enthalpy of transfer ∆Htrn(Tm) for run 1 The line represents the results of a linear

regression analysis of the standards (circles) The squares (and their associated

uncertainties) are the vaporization enthalpies calculated for the targets

11

ln(tot

a)

-10 -9 -8 -7 -6 -5 -4 -3

ln(p

po)

-16

-15

-14

-13

-12

-11

-10

-9

-8

Figure 4 The correlation observed between ln(ppo) and ln(tota) for run 1 The line

represents the results of a linear regression analysis of the standards (circles) The squares

(and their associated uncertainties) are the vapor pressures calculated for the targets

12

TABLE 1

Origin of the standards and targets and their analysis

Compound

FEMA

CAS

registry no

Supplier

Mass

fraction

purity

(supplier)

Mass

fraction

purity

(GC)

γ-hexanolactone FCC 2556 695-06-7 Bedoukian gt098 0993

γ-octanolactone FCC 2796 104-50-7 Bedoukian gt097 0996

δ-octanolactone FCC 3214 698-76-0 Bedoukian 098a 0989

ab

γ-nonanolactone FCC 2781 104-61-0 Bedoukian 098 0982

δ-nonanolactone FCC

3356

3301-94-8

Citrus and

Allied

Essences 098 086

γ-decanolactone FCC 2360 706-14-9 Bedoukian 097 0984

δ-decanolactone FCC 2361 705-86-2 Bedoukian 098a 0975

ac

γ-undecanolactone FCC 3091 104-67-6 SAFC gt098 0984

δ-undecanolactone FCC 3294 710-04-3 Bedoukian 098a 0948

ad

γ-dodecanolactone FCC 2400 2305-05-7 Bedoukian 097 0930

δ-dodecanolactone FCC 2401 713-95-1 Bedoukian 098a 0983

ae

a Sum of isomers reference [5]

b Two isomers 0977023 the minor isomer separated but was not identified

c Two isomers 0788 0212 the minor isomer separated but was not identified

d Two isomers 0928 0072 the minor isomer separated but was not identified

e Two isomers 0985 0015 the minor isomer separated but was not identified

13

TABLE 2

Thermochemical properties of the γ and δ lactones used as standardsa

∆lgHm(298 K)

kJsdotmol-1

A

B

C

TK(range)

γ-hexanolactone3 572plusmn03 2887 796414 627 283-353

δ-octanolactone3 670plusmn02 3107 906819 792 288-353

γ-nonanolactone4 703plusmn03 3251 968999 892 296-363

δ-nonanolactone3 707plusmn04 3236 968266 876 293-348

γ-decanolactone4 756plusmn03 3420 1046661 975 298-365

δ-decanolactone3 742plusmn03 3326 1027922 959 309-358

a A B and C are constants of equation 2

TABLE 3

A The correlation of enthalpies of transfer with vaporization enthalpies

Run 1

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42544 10338 3537 572plusmn03 575plusmn36

γ-octanolactone -51151 11381 4252 659plusmn39

δ-octanolactone -51695 11362 4298 670plusmn02 665plusmn39

γ-nonanolactone -55556 11927 4619 703plusmn03 703plusmn40

δ-nonanolactone -56242 11941 4676 707plusmn04 709plusmn41

γ-decanolactone -60035 1249 4991 756plusmn03 747plusmn42

δ-decanolactone -60638 12495 5041 742plusmn03 752plusmn42

γ-undecanolactone -64508 13057 5363 791plusmn44

δ-undecanolactone -65139 1307 5415 797plusmn44

γ-dodecanolactone -68966 13622 5734 834plusmn46

δ-dodecanolactone -69615 13641 5788 841plusmn46

∆lgHm(29815 K)kJsdotmol

-1 = (118plusmn0062)∆Htrn(434 K) + (1562plusmn28) r

2 = 09890 (4)

B The correlation of enthalpies of transfer with vaporization enthalpies

Run 2

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42798 10387 3558 572plusmn03 572plusmn37

γ-octanolactone -51374 11424 4271 661plusmn39

δ-octanolactone -51926 11407 4317 670plusmn02 666plusmn40

γ-nonanolactone -55748 11962 4635 703plusmn03 706plusmn41

δ-nonanolactone -56418 11974 469 707plusmn04 713plusmn41

γ-decanolactone -60181 12513 5003 756plusmn03 752plusmn43

δ-decanolactone -60804 12526 5055 742plusmn03 758plusmn43

γ-undecanolactone -64622 13075 5372 797plusmn44

δ-undecanolactone -65275 13094 5427 804plusmn45

γ-dodecanolactone -69059 1364 5741 843plusmn46

δ-dodecanolactone -69695 13655 5794 850plusmn47

∆lgHm(29815 K)kJsdotmol

-1 = (119plusmn0063)∆Htrn(434 K) + (1512plusmn29) r

2 = 09889 (5)

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

10

∆Htrn

(Tm)kJmol

-1

30 35 40 45 50 55 60

∆lgH

(29

81

5 K

)kJ

mol-1

40

50

60

70

80

90

100

Figure 3 The correlation observed between the vaporization enthalpy ∆lgHm(Tm) and the

enthalpy of transfer ∆Htrn(Tm) for run 1 The line represents the results of a linear

regression analysis of the standards (circles) The squares (and their associated

uncertainties) are the vaporization enthalpies calculated for the targets

11

ln(tot

a)

-10 -9 -8 -7 -6 -5 -4 -3

ln(p

po)

-16

-15

-14

-13

-12

-11

-10

-9

-8

Figure 4 The correlation observed between ln(ppo) and ln(tota) for run 1 The line

represents the results of a linear regression analysis of the standards (circles) The squares

(and their associated uncertainties) are the vapor pressures calculated for the targets

12

TABLE 1

Origin of the standards and targets and their analysis

Compound

FEMA

CAS

registry no

Supplier

Mass

fraction

purity

(supplier)

Mass

fraction

purity

(GC)

γ-hexanolactone FCC 2556 695-06-7 Bedoukian gt098 0993

γ-octanolactone FCC 2796 104-50-7 Bedoukian gt097 0996

δ-octanolactone FCC 3214 698-76-0 Bedoukian 098a 0989

ab

γ-nonanolactone FCC 2781 104-61-0 Bedoukian 098 0982

δ-nonanolactone FCC

3356

3301-94-8

Citrus and

Allied

Essences 098 086

γ-decanolactone FCC 2360 706-14-9 Bedoukian 097 0984

δ-decanolactone FCC 2361 705-86-2 Bedoukian 098a 0975

ac

γ-undecanolactone FCC 3091 104-67-6 SAFC gt098 0984

δ-undecanolactone FCC 3294 710-04-3 Bedoukian 098a 0948

ad

γ-dodecanolactone FCC 2400 2305-05-7 Bedoukian 097 0930

δ-dodecanolactone FCC 2401 713-95-1 Bedoukian 098a 0983

ae

a Sum of isomers reference [5]

b Two isomers 0977023 the minor isomer separated but was not identified

c Two isomers 0788 0212 the minor isomer separated but was not identified

d Two isomers 0928 0072 the minor isomer separated but was not identified

e Two isomers 0985 0015 the minor isomer separated but was not identified

13

TABLE 2

Thermochemical properties of the γ and δ lactones used as standardsa

∆lgHm(298 K)

kJsdotmol-1

A

B

C

TK(range)

γ-hexanolactone3 572plusmn03 2887 796414 627 283-353

δ-octanolactone3 670plusmn02 3107 906819 792 288-353

γ-nonanolactone4 703plusmn03 3251 968999 892 296-363

δ-nonanolactone3 707plusmn04 3236 968266 876 293-348

γ-decanolactone4 756plusmn03 3420 1046661 975 298-365

δ-decanolactone3 742plusmn03 3326 1027922 959 309-358

a A B and C are constants of equation 2

TABLE 3

A The correlation of enthalpies of transfer with vaporization enthalpies

Run 1

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42544 10338 3537 572plusmn03 575plusmn36

γ-octanolactone -51151 11381 4252 659plusmn39

δ-octanolactone -51695 11362 4298 670plusmn02 665plusmn39

γ-nonanolactone -55556 11927 4619 703plusmn03 703plusmn40

δ-nonanolactone -56242 11941 4676 707plusmn04 709plusmn41

γ-decanolactone -60035 1249 4991 756plusmn03 747plusmn42

δ-decanolactone -60638 12495 5041 742plusmn03 752plusmn42

γ-undecanolactone -64508 13057 5363 791plusmn44

δ-undecanolactone -65139 1307 5415 797plusmn44

γ-dodecanolactone -68966 13622 5734 834plusmn46

δ-dodecanolactone -69615 13641 5788 841plusmn46

∆lgHm(29815 K)kJsdotmol

-1 = (118plusmn0062)∆Htrn(434 K) + (1562plusmn28) r

2 = 09890 (4)

B The correlation of enthalpies of transfer with vaporization enthalpies

Run 2

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42798 10387 3558 572plusmn03 572plusmn37

γ-octanolactone -51374 11424 4271 661plusmn39

δ-octanolactone -51926 11407 4317 670plusmn02 666plusmn40

γ-nonanolactone -55748 11962 4635 703plusmn03 706plusmn41

δ-nonanolactone -56418 11974 469 707plusmn04 713plusmn41

γ-decanolactone -60181 12513 5003 756plusmn03 752plusmn43

δ-decanolactone -60804 12526 5055 742plusmn03 758plusmn43

γ-undecanolactone -64622 13075 5372 797plusmn44

δ-undecanolactone -65275 13094 5427 804plusmn45

γ-dodecanolactone -69059 1364 5741 843plusmn46

δ-dodecanolactone -69695 13655 5794 850plusmn47

∆lgHm(29815 K)kJsdotmol

-1 = (119plusmn0063)∆Htrn(434 K) + (1512plusmn29) r

2 = 09889 (5)

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

11

ln(tot

a)

-10 -9 -8 -7 -6 -5 -4 -3

ln(p

po)

-16

-15

-14

-13

-12

-11

-10

-9

-8

Figure 4 The correlation observed between ln(ppo) and ln(tota) for run 1 The line

represents the results of a linear regression analysis of the standards (circles) The squares

(and their associated uncertainties) are the vapor pressures calculated for the targets

12

TABLE 1

Origin of the standards and targets and their analysis

Compound

FEMA

CAS

registry no

Supplier

Mass

fraction

purity

(supplier)

Mass

fraction

purity

(GC)

γ-hexanolactone FCC 2556 695-06-7 Bedoukian gt098 0993

γ-octanolactone FCC 2796 104-50-7 Bedoukian gt097 0996

δ-octanolactone FCC 3214 698-76-0 Bedoukian 098a 0989

ab

γ-nonanolactone FCC 2781 104-61-0 Bedoukian 098 0982

δ-nonanolactone FCC

3356

3301-94-8

Citrus and

Allied

Essences 098 086

γ-decanolactone FCC 2360 706-14-9 Bedoukian 097 0984

δ-decanolactone FCC 2361 705-86-2 Bedoukian 098a 0975

ac

γ-undecanolactone FCC 3091 104-67-6 SAFC gt098 0984

δ-undecanolactone FCC 3294 710-04-3 Bedoukian 098a 0948

ad

γ-dodecanolactone FCC 2400 2305-05-7 Bedoukian 097 0930

δ-dodecanolactone FCC 2401 713-95-1 Bedoukian 098a 0983

ae

a Sum of isomers reference [5]

b Two isomers 0977023 the minor isomer separated but was not identified

c Two isomers 0788 0212 the minor isomer separated but was not identified

d Two isomers 0928 0072 the minor isomer separated but was not identified

e Two isomers 0985 0015 the minor isomer separated but was not identified

13

TABLE 2

Thermochemical properties of the γ and δ lactones used as standardsa

∆lgHm(298 K)

kJsdotmol-1

A

B

C

TK(range)

γ-hexanolactone3 572plusmn03 2887 796414 627 283-353

δ-octanolactone3 670plusmn02 3107 906819 792 288-353

γ-nonanolactone4 703plusmn03 3251 968999 892 296-363

δ-nonanolactone3 707plusmn04 3236 968266 876 293-348

γ-decanolactone4 756plusmn03 3420 1046661 975 298-365

δ-decanolactone3 742plusmn03 3326 1027922 959 309-358

a A B and C are constants of equation 2

TABLE 3

A The correlation of enthalpies of transfer with vaporization enthalpies

Run 1

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42544 10338 3537 572plusmn03 575plusmn36

γ-octanolactone -51151 11381 4252 659plusmn39

δ-octanolactone -51695 11362 4298 670plusmn02 665plusmn39

γ-nonanolactone -55556 11927 4619 703plusmn03 703plusmn40

δ-nonanolactone -56242 11941 4676 707plusmn04 709plusmn41

γ-decanolactone -60035 1249 4991 756plusmn03 747plusmn42

δ-decanolactone -60638 12495 5041 742plusmn03 752plusmn42

γ-undecanolactone -64508 13057 5363 791plusmn44

δ-undecanolactone -65139 1307 5415 797plusmn44

γ-dodecanolactone -68966 13622 5734 834plusmn46

δ-dodecanolactone -69615 13641 5788 841plusmn46

∆lgHm(29815 K)kJsdotmol

-1 = (118plusmn0062)∆Htrn(434 K) + (1562plusmn28) r

2 = 09890 (4)

B The correlation of enthalpies of transfer with vaporization enthalpies

Run 2

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42798 10387 3558 572plusmn03 572plusmn37

γ-octanolactone -51374 11424 4271 661plusmn39

δ-octanolactone -51926 11407 4317 670plusmn02 666plusmn40

γ-nonanolactone -55748 11962 4635 703plusmn03 706plusmn41

δ-nonanolactone -56418 11974 469 707plusmn04 713plusmn41

γ-decanolactone -60181 12513 5003 756plusmn03 752plusmn43

δ-decanolactone -60804 12526 5055 742plusmn03 758plusmn43

γ-undecanolactone -64622 13075 5372 797plusmn44

δ-undecanolactone -65275 13094 5427 804plusmn45

γ-dodecanolactone -69059 1364 5741 843plusmn46

δ-dodecanolactone -69695 13655 5794 850plusmn47

∆lgHm(29815 K)kJsdotmol

-1 = (119plusmn0063)∆Htrn(434 K) + (1512plusmn29) r

2 = 09889 (5)

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

12

TABLE 1

Origin of the standards and targets and their analysis

Compound

FEMA

CAS

registry no

Supplier

Mass

fraction

purity

(supplier)

Mass

fraction

purity

(GC)

γ-hexanolactone FCC 2556 695-06-7 Bedoukian gt098 0993

γ-octanolactone FCC 2796 104-50-7 Bedoukian gt097 0996

δ-octanolactone FCC 3214 698-76-0 Bedoukian 098a 0989

ab

γ-nonanolactone FCC 2781 104-61-0 Bedoukian 098 0982

δ-nonanolactone FCC

3356

3301-94-8

Citrus and

Allied

Essences 098 086

γ-decanolactone FCC 2360 706-14-9 Bedoukian 097 0984

δ-decanolactone FCC 2361 705-86-2 Bedoukian 098a 0975

ac

γ-undecanolactone FCC 3091 104-67-6 SAFC gt098 0984

δ-undecanolactone FCC 3294 710-04-3 Bedoukian 098a 0948

ad

γ-dodecanolactone FCC 2400 2305-05-7 Bedoukian 097 0930

δ-dodecanolactone FCC 2401 713-95-1 Bedoukian 098a 0983

ae

a Sum of isomers reference [5]

b Two isomers 0977023 the minor isomer separated but was not identified

c Two isomers 0788 0212 the minor isomer separated but was not identified

d Two isomers 0928 0072 the minor isomer separated but was not identified

e Two isomers 0985 0015 the minor isomer separated but was not identified

13

TABLE 2

Thermochemical properties of the γ and δ lactones used as standardsa

∆lgHm(298 K)

kJsdotmol-1

A

B

C

TK(range)

γ-hexanolactone3 572plusmn03 2887 796414 627 283-353

δ-octanolactone3 670plusmn02 3107 906819 792 288-353

γ-nonanolactone4 703plusmn03 3251 968999 892 296-363

δ-nonanolactone3 707plusmn04 3236 968266 876 293-348

γ-decanolactone4 756plusmn03 3420 1046661 975 298-365

δ-decanolactone3 742plusmn03 3326 1027922 959 309-358

a A B and C are constants of equation 2

TABLE 3

A The correlation of enthalpies of transfer with vaporization enthalpies

Run 1

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42544 10338 3537 572plusmn03 575plusmn36

γ-octanolactone -51151 11381 4252 659plusmn39

δ-octanolactone -51695 11362 4298 670plusmn02 665plusmn39

γ-nonanolactone -55556 11927 4619 703plusmn03 703plusmn40

δ-nonanolactone -56242 11941 4676 707plusmn04 709plusmn41

γ-decanolactone -60035 1249 4991 756plusmn03 747plusmn42

δ-decanolactone -60638 12495 5041 742plusmn03 752plusmn42

γ-undecanolactone -64508 13057 5363 791plusmn44

δ-undecanolactone -65139 1307 5415 797plusmn44

γ-dodecanolactone -68966 13622 5734 834plusmn46

δ-dodecanolactone -69615 13641 5788 841plusmn46

∆lgHm(29815 K)kJsdotmol

-1 = (118plusmn0062)∆Htrn(434 K) + (1562plusmn28) r

2 = 09890 (4)

B The correlation of enthalpies of transfer with vaporization enthalpies

Run 2

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42798 10387 3558 572plusmn03 572plusmn37

γ-octanolactone -51374 11424 4271 661plusmn39

δ-octanolactone -51926 11407 4317 670plusmn02 666plusmn40

γ-nonanolactone -55748 11962 4635 703plusmn03 706plusmn41

δ-nonanolactone -56418 11974 469 707plusmn04 713plusmn41

γ-decanolactone -60181 12513 5003 756plusmn03 752plusmn43

δ-decanolactone -60804 12526 5055 742plusmn03 758plusmn43

γ-undecanolactone -64622 13075 5372 797plusmn44

δ-undecanolactone -65275 13094 5427 804plusmn45

γ-dodecanolactone -69059 1364 5741 843plusmn46

δ-dodecanolactone -69695 13655 5794 850plusmn47

∆lgHm(29815 K)kJsdotmol

-1 = (119plusmn0063)∆Htrn(434 K) + (1512plusmn29) r

2 = 09889 (5)

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

13

TABLE 2

Thermochemical properties of the γ and δ lactones used as standardsa

∆lgHm(298 K)

kJsdotmol-1

A

B

C

TK(range)

γ-hexanolactone3 572plusmn03 2887 796414 627 283-353

δ-octanolactone3 670plusmn02 3107 906819 792 288-353

γ-nonanolactone4 703plusmn03 3251 968999 892 296-363

δ-nonanolactone3 707plusmn04 3236 968266 876 293-348

γ-decanolactone4 756plusmn03 3420 1046661 975 298-365

δ-decanolactone3 742plusmn03 3326 1027922 959 309-358

a A B and C are constants of equation 2

TABLE 3

A The correlation of enthalpies of transfer with vaporization enthalpies

Run 1

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42544 10338 3537 572plusmn03 575plusmn36

γ-octanolactone -51151 11381 4252 659plusmn39

δ-octanolactone -51695 11362 4298 670plusmn02 665plusmn39

γ-nonanolactone -55556 11927 4619 703plusmn03 703plusmn40

δ-nonanolactone -56242 11941 4676 707plusmn04 709plusmn41

γ-decanolactone -60035 1249 4991 756plusmn03 747plusmn42

δ-decanolactone -60638 12495 5041 742plusmn03 752plusmn42

γ-undecanolactone -64508 13057 5363 791plusmn44

δ-undecanolactone -65139 1307 5415 797plusmn44

γ-dodecanolactone -68966 13622 5734 834plusmn46

δ-dodecanolactone -69615 13641 5788 841plusmn46

∆lgHm(29815 K)kJsdotmol

-1 = (118plusmn0062)∆Htrn(434 K) + (1562plusmn28) r

2 = 09890 (4)

B The correlation of enthalpies of transfer with vaporization enthalpies

Run 2

- slope

TK

intercept

∆Htrn(434 K)

kJsdotmol-1

∆lgHm(298 K)

kJsdotmol-1

(lit)

∆lgHm(298 K)

kJsdotmol-1

(calc)

γ-hexanolactone -42798 10387 3558 572plusmn03 572plusmn37

γ-octanolactone -51374 11424 4271 661plusmn39

δ-octanolactone -51926 11407 4317 670plusmn02 666plusmn40

γ-nonanolactone -55748 11962 4635 703plusmn03 706plusmn41

δ-nonanolactone -56418 11974 469 707plusmn04 713plusmn41

γ-decanolactone -60181 12513 5003 756plusmn03 752plusmn43

δ-decanolactone -60804 12526 5055 742plusmn03 758plusmn43

γ-undecanolactone -64622 13075 5372 797plusmn44

δ-undecanolactone -65275 13094 5427 804plusmn45

γ-dodecanolactone -69059 1364 5741 843plusmn46

δ-dodecanolactone -69695 13655 5794 850plusmn47

∆lgHm(29815 K)kJsdotmol

-1 = (119plusmn0063)∆Htrn(434 K) + (1512plusmn29) r

2 = 09889 (5)

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

14

TABLE 4

A Summary of the vaporization enthalpies in kJsdotmol-1

of both standards and targets

∆vapHm(298 K)

kJsdotmol-1

Run 1 Run 2 Avg Lit

γ-hexanolactone 575plusmn36 572plusmn37 574plusmn37 572plusmn03

γ-octanolactone 659plusmn39 661plusmn39 660plusmn39

δ-octanolactone 665plusmn39 666plusmn40 666plusmn40 670plusmn02

γ-nonanolactone 703plusmn40 706plusmn41 705plusmn41 703plusmn03

δ-nonanolactone 709plusmn41 713plusmn41 711plusmn41 707plusmn04

γ-decanolactone 747plusmn42 752plusmn43 750plusmn43 756plusmn03

δ-decanolactone 752plusmn42 758plusmn43 755plusmn43 742plusmn03

γ-undecanolactone 791plusmn44 797plusmn44 794plusmn44

δ-undecanolactone 797plusmn44 804plusmn45 801plusmn45

γ-dodecanolactone 834plusmn46 843plusmn46 839plusmn46

δ-dodecanolactone 841plusmn46 850plusmn47 846plusmn47

TABLE 5

Correlation of ln(tota) with ln(ppo)exp at T = 29815 K for run 1

ln(tota) ln(ppo)exp ln(ppo)calc pPalit pPacalc

γ-hexanolactone -393 -846 -841plusmn025 216 225plusmn64

γ-octanolactone -578 -105plusmn029 278plusmn09

δ-octanolactone -598 -1074 -1073plusmn029 22 221plusmn08

γ-nonanolactone -671 -1151 -1156plusmn031 101 097plusmn04

δ-nonanolactone -692 -1167 -1180plusmn031 087 076plusmn03

γ-decanolactone -765 -1261 -1262plusmn033 034 033plusmn01

δ-decanolactone -784 -1299 -1285plusmn033 023 027plusmn01

γ-undecanolactone -858 -1368plusmn035 012plusmn005

δ-undecanolactone -878 -1391plusmn036 009plusmn004

γ-dodecanolactone -951 -1474plusmn038 004plusmn002

δ-dodecanolactone -971 -1496plusmn038 003plusmn002 a A vapor pressure of pPa = 213 also reported for γ-hexanolactone was not used

reference [12]

Run 1

ln(ppo)calc = (1134plusmn0033) ln(ppo)exp - (395plusmn022) r 2 = 09967 (6)

Run 2

ln(ppo)calc = (1137plusmn0033) ln(ppo)exp - (390plusmn022) r 2 = 09967 (7)

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

15

TABLE 6

The slopes and intercepts of equation 8 and the vaporization enthalpy at T = 29815 K

calculated from correlations of ln(tota) with ln(ppo)exp for run 1 from T = (29815 to 350)

K

Arsquo Brsquo

∆lgHm(Tm)

a

kJsdotmol-1

Cp(298 K)(l)

JsdotK-1

sdotmol-1

∆lgHm(29815 K)

kJsdotmol-1

calc lit

γ-hexanolactone 1414 -67205 559plusmn02 2066 575plusmn05 572plusmn03b

γ-octanolactone 1532 -76939 640plusmn03 2704 661plusmn05 660plusmn39c

δ-octanolactone 1530 -77554 645plusmn03 2644 665plusmn05 670plusmn02b

γ-nonanolactone 1594 -81922 681plusmn03 3023 704plusmn05 703plusmn03b

δ-nonanolactone 1595 -82697 688plusmn03 2963 710plusmn05 707plusmn04b

γ-decanolactone 1657 -86988 723plusmn04 3342 748plusmn06 756plusmn03b

δ-decanolactone 1658 -87669 729plusmn04 3282 754plusmn06 742plusmn03b

γ-undecanolactone 1721 -92047 765plusmn04 3661 793plusmn06 794plusmn44c

δ-undecanolactone 1723 -92760 771plusmn04 3601 798plusmn06 801plusmn45c

γ-dodecanolactone 1785 -97090 807plusmn04 398 837plusmn06 843plusmn46c

δ-dodecanolactone 1787 -97823 813plusmn04 392 842plusmn06 856plusmn47c

a Tm = 324 K

b Refences [34]

c This work

TABLE 7

A comparison of the literature vapor pressures with this work using equations 6 and 8

(run 1)

pPa

29815 K

lita

pPa (29815 K)

this work

eq 6 eq 8

pPa

29815 K

EPIestb

pPa

29315 K

litc

pPa

29315 K

this workd

γ-hexanolactone 216 225plusmn64 228plusmn33 22 800 155plusmn23

γ-octanolactone 28plusmn09 28plusmn05 846 547 18plusmn03

δ-octanolactone 22 22plusmn08 23plusmn04 363 229 15plusmn03

γ-nonanolactone 101 10plusmn04 10plusmn02 157 097 062plusmn01

δ-nonanolactone 087 08plusmn04 08plusmn02 145 089 048plusmn01

γ-decanolactone 034 033plusmn01 034plusmn01 0683 042 021plusmn005

δ-decanolactone 023 027plusmn01 027plusmn01 0633 039 017plusmn004

γ-undecanolactone 012plusmn005 012plusmn003 0545 034 0070plusmn002

δ-undecanolactone 009plusmn004 095plusmn002 0261 014 0056plusmn001

γ-dodecanolactone 004plusmn002 041plusmn001 0141 008 0024plusmn0006

δ-dodecanolactone 003plusmn002 0033plusmn001 0132 008 0019plusmn0005 a From references [34] unless noted otherwise

b Calculated using the EPI Suite reference [11]

c MSDS sheets reference [5]

d Using equation 8 and the constants of table 6

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

16

TABLE 8

Group additivity values for vaporization enthalpy calculation of γ and δ-lactonesa

Group Increment GroupValue kJsdotmol-1

C γlactone five membered lactone ring 539

C δlactone six membered lactone ring 587

C-(H)3(Clactone) methyl ring substitient 111

C-(H)2(Clactone) methylene ring substitient -067

C-(H)3(C) methyl group 633

C-(H)2(C)2 methylene group 452

(C-C)1-4 14-carbon-carbon interaction 026

(C-O)1-4 14-carbon-oxygen interaction -326 a From reference [4]

TABLE 9

A comparison of estimated vaporization enthalpies with experimental values

∆lgHm(29815 K)

kJsdotmol-1

Estimation

∆lgHm(29815 K)

kJsdotmol-1

Literature [34]

∆lgHm(29815 K)

kJsdotmol-1

This Work

γ-butanolactone 539 544

γ-pentanolactone 551 539

γ-hexanolactone 566 572

γ-heptanolactone 614 623

γ-octanolactone 661 660plusmn39

γ-nonanolactone 709 703

γ-decanolactone 757 756

γ-undecanolactone 805 794plusmn44

γ-dodecanolactone 852 839plusmn46

δ-pentanolactone 587 582

δ-hexanolactone 598 610

δ-octanolactone 661 670

δ-nonanolactone 709 707

δ-decanolactone 757 742

δ-undecanolactone 805 801plusmn45

δ-dodecanolactone 853 846plusmn47

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

17

TABLE 10

A comparison of the vaporization enthalpies of a series of γ δ and ω-lactones

∆lgHm(298 K)

kJsdotmol-1

γa δ

b ω

c

∆lgHm(298 K)

kJsdotmol-1

Est (Eq 9)

butanolactone 544plusmn04 556plusmn14d 323

pentanolactone 539plusmn02 582plusmn03e 602plusmn13

f 370

hexanolactone 572plusmn03 610plusmn01e 620plusmn13 416

octanolactone 660plusmn39b 670plusmn02

e 528plusmn13 510

nonanolactone 703plusmn02 711plusmn41 590plusmn13 557

decanolactone 756plusmn03 755plusmn43 630plusmn15 604

undecanolactone 794plusmn44b

801plusmn45 662plusmn13 651

dodecanolactone 839plusmn46b 846plusmn47 705plusmn17 698

a From reference [4] unless noted otherwise

b This work unless noted otherwise

c From reference [13]

d Same as γ-butanolactone

e From reference [3]

f Same as δ-pentanolactone

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

18

O

O

(CH2)nCH3

O

O

(CH2)nCH3

n = 1 4 5 n = 2 3 4Standards

Targets

n = 3 6 7 n = 5 6

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values

19

Highlights The vaporization enthalpies of γ-octanolactone γ- and δ-undecanolactone and

γ and δ-dodecanolactone are reported

Equations for predicting the vapor pressures over the temperature range T = (29815 to

350) K are provided

Vaporization Enthalpies are compared to predicted values