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The Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin By
Correlation Gas Chromatography
Jessica Spencer and James Chickos
Department of Chemistry and Biochemistry
University of Missouri-St Louis
Louis MO 63121
E-mail jscumsledu
A portion of the Science Complex at UMSL
Outline of the Presentation
Properties of the targets
Introduction to the fundamentals of correlation gas chromatography
Demonstration of the method as applied to Muscalure
Application to evaluate the vaporization enthalpy and vapor pressure of empenthrin
Comparison of the results on empenthrin with those obtained by another gas chromatographic retention time method that has been criticized recently1
1 Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas-Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Muscalure Z 9-Tricosene is a sex pheromone produce by female house flies (Musca domestica) Muscalure in combination with other fecal odors provides maximum attraction for male flies It is used as a pesticide is in combination with fly paper or other traps Z 9-Tricosene also serves as a communication pheromone in the waggle dance of bees The synthetic sample also contains a small amount of E 9-Tricosene
Empenthrin (E)-(RS)-1-ethynyl-2-methylpent-2-enyl (1RS)-cis-trans-22-dimethyl-3-(2-methylprop-1-enyl)-cyclopropane-carboxylate is a synthetic pyrethrin used as a pesticide It has a broad spectrum of activity on various flying insects but relatively low mammalian toxicity It consists of a racemic mixture of up to 4 possible diasteriomers At least three of the diasteriomers were detected in the commercial product
Information on the Compounds Investigated
Tmin
0 5 10 15 20
Inte
nsit
ya
rbit
rary
unit
s
10000
20000
30000
40000
Tmin
120 125 130 135 140
Intens
ity
2000
2500
3000
3500
4000
4500
5000
5500
FIGURE 1 Gas chromatograph From left to right hexane nonadecane eicosane henicosane docosane Z-9-tricosene (muscalure) E-9-tricosene tetracosene
13C NMR
Z
E
Tmin
0 5 10 15 20 25
Inte
nsit
yar
bitr
ary
unit
s
10000
20000
30000
40000
Tmin
42 44 46 48 50 52
Inte
nsit
y
2000
2500
3000
3500
4000
4500
5000
5500
FIGURE 2 Gas chromatograph From Left to right CH2Cl2 methyl dodecanoate empenthrin 1 and 2 methyl tetradecanoate methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate on a 5 phenylmethyl silicone column
1H NMR245 ppm
Fundamentals of Correlation Gas Chromatography- Vaporization Enthalpy
1 The residence time of a compound on the column ta is inversely proportional the compounds vapor pressure (ta = retention time of a solute ndash retention time of a non-retained reference ta = t ndash tnrr (often the solvent)
2 A plot of ln(tota) where to is the reference time 1 min versus 1T over a 30 K temperature range results in a straight line
3 The slope of the line -∆Htrn(Tm)R is the enthalpy of transfer of the analyte from the column to the gas phase
4 The enthalpy of transfer is related to the vaporization enthalpy (∆l
gH(T) by the following equation where ∆Hsln represents the enthalpy of interaction of the solute with the column ∆Htrn(Tm) = ∆l
gH (Tm) + ∆Hsln
(Tm)
5 If a series of standards are properly selected a second plot of ∆lgH(29815 K)
versus ∆Htrn(Tm) of the standards is also linear and the equation of the line can be used to evaluate the vaporization enthalpy of any additional targets included in the mixture
6 Appropriate standards with known vaporization enthalpies generally include compounds with the same number and type of functionality as the targets The structure of the hydrocabon portion of the molecule may vary
Use of appropriate standards with known vapor pressures also results in linear plots between ln(ppo) and ln(tota)
The equation of the line plus values of ln(tota) of the targets results in their vapor pressures
Performed over a range of temperatures can provide the vapor pressure temperature profile of the targets
Fundamentals of Correlation Gas Chromatography - Vapor Pressure
Vaporization Enthalpies and Vapor Pressure Equations of the Standards (po = 101325 Pa)
ln (ppo) = (1-TnbT)exp(Ao +A1T + A2T2) Cox equationln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial Rln(ppo) = - cd
gGdeg() + lgHdeg()[1 - 1T] + cd
gCpm()[T -1 + ln(T)] Equation of Clark and Glew
1(TK)
000192 000194 000196 000198 000200 000202 000204 000206 000208
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
FIGURE 3 A plot of ln(tota) where to = 1 min and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
2TABLE 2Experimental Retention Times of Muscalure and Various Alkanes
Htrn(Tm) kJmole-1
62 64 66 68 70 72 74 76 78
lg H
(298
K)
kJ
mol
-1
100
105
110
115
120
125
TABLE 3 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Muscalure
FIGURE 4 Vaporization enthalpy of muscalure and standards From left to right eicosane heneicosane docosane Z 9-tricosene E 9-tricosene tetracosane
lgHm(29815 K)kJmol-1 = (164001)Htrn(500 K) - (34607) r 2 = 09999
TABLE 4 A Summary of the Vaporization Enthalpies of Muscalure
Values in italics are estimated using the following equation for hydrocarbons
∆lgH(29815 K) = 469(n-nQ) + 13 nQ +30
+ b + C
n = number of carbon atoms 23
nQ = number of quaternary sp3 carbon atoms 0
b = contribution of a functional group 0
branching correction 0
2
ln(tota)
-155 -150 -145 -140 -135 -130 -125 -120 -115
ln(p
po)
-23
-22
-21
-20
-19
-18
-17
FIGURE 5 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa for muscalure at T = 29815 K From left to right tetracosane Z-9-tricosene E 9-tricosene docosane heneicosane and eicosane
ln(ppo) = (137 0003) ln(tota) - (1608 0044) r 2 = 09999
TABLE 5 Correlation Between ln(tota) and Literature ln(ppo) for Muscalure at T = 29815 K
pPa(29815) = 12middot10-4 (Z)
pPa(29815) = 11middot10-4 (E)
The correlation between ln(tota) and literature values of ln(ppo) for Muscalure and the standards was repeated from T = (29815 to 500) K at 10 K intervals resulting in the following (r 2 for all correlations gt099)
ln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Outline of the Presentation
Properties of the targets
Introduction to the fundamentals of correlation gas chromatography
Demonstration of the method as applied to Muscalure
Application to evaluate the vaporization enthalpy and vapor pressure of empenthrin
Comparison of the results on empenthrin with those obtained by another gas chromatographic retention time method that has been criticized recently1
1 Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas-Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Muscalure Z 9-Tricosene is a sex pheromone produce by female house flies (Musca domestica) Muscalure in combination with other fecal odors provides maximum attraction for male flies It is used as a pesticide is in combination with fly paper or other traps Z 9-Tricosene also serves as a communication pheromone in the waggle dance of bees The synthetic sample also contains a small amount of E 9-Tricosene
Empenthrin (E)-(RS)-1-ethynyl-2-methylpent-2-enyl (1RS)-cis-trans-22-dimethyl-3-(2-methylprop-1-enyl)-cyclopropane-carboxylate is a synthetic pyrethrin used as a pesticide It has a broad spectrum of activity on various flying insects but relatively low mammalian toxicity It consists of a racemic mixture of up to 4 possible diasteriomers At least three of the diasteriomers were detected in the commercial product
Information on the Compounds Investigated
Tmin
0 5 10 15 20
Inte
nsit
ya
rbit
rary
unit
s
10000
20000
30000
40000
Tmin
120 125 130 135 140
Intens
ity
2000
2500
3000
3500
4000
4500
5000
5500
FIGURE 1 Gas chromatograph From left to right hexane nonadecane eicosane henicosane docosane Z-9-tricosene (muscalure) E-9-tricosene tetracosene
13C NMR
Z
E
Tmin
0 5 10 15 20 25
Inte
nsit
yar
bitr
ary
unit
s
10000
20000
30000
40000
Tmin
42 44 46 48 50 52
Inte
nsit
y
2000
2500
3000
3500
4000
4500
5000
5500
FIGURE 2 Gas chromatograph From Left to right CH2Cl2 methyl dodecanoate empenthrin 1 and 2 methyl tetradecanoate methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate on a 5 phenylmethyl silicone column
1H NMR245 ppm
Fundamentals of Correlation Gas Chromatography- Vaporization Enthalpy
1 The residence time of a compound on the column ta is inversely proportional the compounds vapor pressure (ta = retention time of a solute ndash retention time of a non-retained reference ta = t ndash tnrr (often the solvent)
2 A plot of ln(tota) where to is the reference time 1 min versus 1T over a 30 K temperature range results in a straight line
3 The slope of the line -∆Htrn(Tm)R is the enthalpy of transfer of the analyte from the column to the gas phase
4 The enthalpy of transfer is related to the vaporization enthalpy (∆l
gH(T) by the following equation where ∆Hsln represents the enthalpy of interaction of the solute with the column ∆Htrn(Tm) = ∆l
gH (Tm) + ∆Hsln
(Tm)
5 If a series of standards are properly selected a second plot of ∆lgH(29815 K)
versus ∆Htrn(Tm) of the standards is also linear and the equation of the line can be used to evaluate the vaporization enthalpy of any additional targets included in the mixture
6 Appropriate standards with known vaporization enthalpies generally include compounds with the same number and type of functionality as the targets The structure of the hydrocabon portion of the molecule may vary
Use of appropriate standards with known vapor pressures also results in linear plots between ln(ppo) and ln(tota)
The equation of the line plus values of ln(tota) of the targets results in their vapor pressures
Performed over a range of temperatures can provide the vapor pressure temperature profile of the targets
Fundamentals of Correlation Gas Chromatography - Vapor Pressure
Vaporization Enthalpies and Vapor Pressure Equations of the Standards (po = 101325 Pa)
ln (ppo) = (1-TnbT)exp(Ao +A1T + A2T2) Cox equationln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial Rln(ppo) = - cd
gGdeg() + lgHdeg()[1 - 1T] + cd
gCpm()[T -1 + ln(T)] Equation of Clark and Glew
1(TK)
000192 000194 000196 000198 000200 000202 000204 000206 000208
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
FIGURE 3 A plot of ln(tota) where to = 1 min and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
2TABLE 2Experimental Retention Times of Muscalure and Various Alkanes
Htrn(Tm) kJmole-1
62 64 66 68 70 72 74 76 78
lg H
(298
K)
kJ
mol
-1
100
105
110
115
120
125
TABLE 3 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Muscalure
FIGURE 4 Vaporization enthalpy of muscalure and standards From left to right eicosane heneicosane docosane Z 9-tricosene E 9-tricosene tetracosane
lgHm(29815 K)kJmol-1 = (164001)Htrn(500 K) - (34607) r 2 = 09999
TABLE 4 A Summary of the Vaporization Enthalpies of Muscalure
Values in italics are estimated using the following equation for hydrocarbons
∆lgH(29815 K) = 469(n-nQ) + 13 nQ +30
+ b + C
n = number of carbon atoms 23
nQ = number of quaternary sp3 carbon atoms 0
b = contribution of a functional group 0
branching correction 0
2
ln(tota)
-155 -150 -145 -140 -135 -130 -125 -120 -115
ln(p
po)
-23
-22
-21
-20
-19
-18
-17
FIGURE 5 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa for muscalure at T = 29815 K From left to right tetracosane Z-9-tricosene E 9-tricosene docosane heneicosane and eicosane
ln(ppo) = (137 0003) ln(tota) - (1608 0044) r 2 = 09999
TABLE 5 Correlation Between ln(tota) and Literature ln(ppo) for Muscalure at T = 29815 K
pPa(29815) = 12middot10-4 (Z)
pPa(29815) = 11middot10-4 (E)
The correlation between ln(tota) and literature values of ln(ppo) for Muscalure and the standards was repeated from T = (29815 to 500) K at 10 K intervals resulting in the following (r 2 for all correlations gt099)
ln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Muscalure Z 9-Tricosene is a sex pheromone produce by female house flies (Musca domestica) Muscalure in combination with other fecal odors provides maximum attraction for male flies It is used as a pesticide is in combination with fly paper or other traps Z 9-Tricosene also serves as a communication pheromone in the waggle dance of bees The synthetic sample also contains a small amount of E 9-Tricosene
Empenthrin (E)-(RS)-1-ethynyl-2-methylpent-2-enyl (1RS)-cis-trans-22-dimethyl-3-(2-methylprop-1-enyl)-cyclopropane-carboxylate is a synthetic pyrethrin used as a pesticide It has a broad spectrum of activity on various flying insects but relatively low mammalian toxicity It consists of a racemic mixture of up to 4 possible diasteriomers At least three of the diasteriomers were detected in the commercial product
Information on the Compounds Investigated
Tmin
0 5 10 15 20
Inte
nsit
ya
rbit
rary
unit
s
10000
20000
30000
40000
Tmin
120 125 130 135 140
Intens
ity
2000
2500
3000
3500
4000
4500
5000
5500
FIGURE 1 Gas chromatograph From left to right hexane nonadecane eicosane henicosane docosane Z-9-tricosene (muscalure) E-9-tricosene tetracosene
13C NMR
Z
E
Tmin
0 5 10 15 20 25
Inte
nsit
yar
bitr
ary
unit
s
10000
20000
30000
40000
Tmin
42 44 46 48 50 52
Inte
nsit
y
2000
2500
3000
3500
4000
4500
5000
5500
FIGURE 2 Gas chromatograph From Left to right CH2Cl2 methyl dodecanoate empenthrin 1 and 2 methyl tetradecanoate methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate on a 5 phenylmethyl silicone column
1H NMR245 ppm
Fundamentals of Correlation Gas Chromatography- Vaporization Enthalpy
1 The residence time of a compound on the column ta is inversely proportional the compounds vapor pressure (ta = retention time of a solute ndash retention time of a non-retained reference ta = t ndash tnrr (often the solvent)
2 A plot of ln(tota) where to is the reference time 1 min versus 1T over a 30 K temperature range results in a straight line
3 The slope of the line -∆Htrn(Tm)R is the enthalpy of transfer of the analyte from the column to the gas phase
4 The enthalpy of transfer is related to the vaporization enthalpy (∆l
gH(T) by the following equation where ∆Hsln represents the enthalpy of interaction of the solute with the column ∆Htrn(Tm) = ∆l
gH (Tm) + ∆Hsln
(Tm)
5 If a series of standards are properly selected a second plot of ∆lgH(29815 K)
versus ∆Htrn(Tm) of the standards is also linear and the equation of the line can be used to evaluate the vaporization enthalpy of any additional targets included in the mixture
6 Appropriate standards with known vaporization enthalpies generally include compounds with the same number and type of functionality as the targets The structure of the hydrocabon portion of the molecule may vary
Use of appropriate standards with known vapor pressures also results in linear plots between ln(ppo) and ln(tota)
The equation of the line plus values of ln(tota) of the targets results in their vapor pressures
Performed over a range of temperatures can provide the vapor pressure temperature profile of the targets
Fundamentals of Correlation Gas Chromatography - Vapor Pressure
Vaporization Enthalpies and Vapor Pressure Equations of the Standards (po = 101325 Pa)
ln (ppo) = (1-TnbT)exp(Ao +A1T + A2T2) Cox equationln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial Rln(ppo) = - cd
gGdeg() + lgHdeg()[1 - 1T] + cd
gCpm()[T -1 + ln(T)] Equation of Clark and Glew
1(TK)
000192 000194 000196 000198 000200 000202 000204 000206 000208
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
FIGURE 3 A plot of ln(tota) where to = 1 min and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
2TABLE 2Experimental Retention Times of Muscalure and Various Alkanes
Htrn(Tm) kJmole-1
62 64 66 68 70 72 74 76 78
lg H
(298
K)
kJ
mol
-1
100
105
110
115
120
125
TABLE 3 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Muscalure
FIGURE 4 Vaporization enthalpy of muscalure and standards From left to right eicosane heneicosane docosane Z 9-tricosene E 9-tricosene tetracosane
lgHm(29815 K)kJmol-1 = (164001)Htrn(500 K) - (34607) r 2 = 09999
TABLE 4 A Summary of the Vaporization Enthalpies of Muscalure
Values in italics are estimated using the following equation for hydrocarbons
∆lgH(29815 K) = 469(n-nQ) + 13 nQ +30
+ b + C
n = number of carbon atoms 23
nQ = number of quaternary sp3 carbon atoms 0
b = contribution of a functional group 0
branching correction 0
2
ln(tota)
-155 -150 -145 -140 -135 -130 -125 -120 -115
ln(p
po)
-23
-22
-21
-20
-19
-18
-17
FIGURE 5 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa for muscalure at T = 29815 K From left to right tetracosane Z-9-tricosene E 9-tricosene docosane heneicosane and eicosane
ln(ppo) = (137 0003) ln(tota) - (1608 0044) r 2 = 09999
TABLE 5 Correlation Between ln(tota) and Literature ln(ppo) for Muscalure at T = 29815 K
pPa(29815) = 12middot10-4 (Z)
pPa(29815) = 11middot10-4 (E)
The correlation between ln(tota) and literature values of ln(ppo) for Muscalure and the standards was repeated from T = (29815 to 500) K at 10 K intervals resulting in the following (r 2 for all correlations gt099)
ln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Tmin
0 5 10 15 20
Inte
nsit
ya
rbit
rary
unit
s
10000
20000
30000
40000
Tmin
120 125 130 135 140
Intens
ity
2000
2500
3000
3500
4000
4500
5000
5500
FIGURE 1 Gas chromatograph From left to right hexane nonadecane eicosane henicosane docosane Z-9-tricosene (muscalure) E-9-tricosene tetracosene
13C NMR
Z
E
Tmin
0 5 10 15 20 25
Inte
nsit
yar
bitr
ary
unit
s
10000
20000
30000
40000
Tmin
42 44 46 48 50 52
Inte
nsit
y
2000
2500
3000
3500
4000
4500
5000
5500
FIGURE 2 Gas chromatograph From Left to right CH2Cl2 methyl dodecanoate empenthrin 1 and 2 methyl tetradecanoate methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate on a 5 phenylmethyl silicone column
1H NMR245 ppm
Fundamentals of Correlation Gas Chromatography- Vaporization Enthalpy
1 The residence time of a compound on the column ta is inversely proportional the compounds vapor pressure (ta = retention time of a solute ndash retention time of a non-retained reference ta = t ndash tnrr (often the solvent)
2 A plot of ln(tota) where to is the reference time 1 min versus 1T over a 30 K temperature range results in a straight line
3 The slope of the line -∆Htrn(Tm)R is the enthalpy of transfer of the analyte from the column to the gas phase
4 The enthalpy of transfer is related to the vaporization enthalpy (∆l
gH(T) by the following equation where ∆Hsln represents the enthalpy of interaction of the solute with the column ∆Htrn(Tm) = ∆l
gH (Tm) + ∆Hsln
(Tm)
5 If a series of standards are properly selected a second plot of ∆lgH(29815 K)
versus ∆Htrn(Tm) of the standards is also linear and the equation of the line can be used to evaluate the vaporization enthalpy of any additional targets included in the mixture
6 Appropriate standards with known vaporization enthalpies generally include compounds with the same number and type of functionality as the targets The structure of the hydrocabon portion of the molecule may vary
Use of appropriate standards with known vapor pressures also results in linear plots between ln(ppo) and ln(tota)
The equation of the line plus values of ln(tota) of the targets results in their vapor pressures
Performed over a range of temperatures can provide the vapor pressure temperature profile of the targets
Fundamentals of Correlation Gas Chromatography - Vapor Pressure
Vaporization Enthalpies and Vapor Pressure Equations of the Standards (po = 101325 Pa)
ln (ppo) = (1-TnbT)exp(Ao +A1T + A2T2) Cox equationln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial Rln(ppo) = - cd
gGdeg() + lgHdeg()[1 - 1T] + cd
gCpm()[T -1 + ln(T)] Equation of Clark and Glew
1(TK)
000192 000194 000196 000198 000200 000202 000204 000206 000208
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
FIGURE 3 A plot of ln(tota) where to = 1 min and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
2TABLE 2Experimental Retention Times of Muscalure and Various Alkanes
Htrn(Tm) kJmole-1
62 64 66 68 70 72 74 76 78
lg H
(298
K)
kJ
mol
-1
100
105
110
115
120
125
TABLE 3 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Muscalure
FIGURE 4 Vaporization enthalpy of muscalure and standards From left to right eicosane heneicosane docosane Z 9-tricosene E 9-tricosene tetracosane
lgHm(29815 K)kJmol-1 = (164001)Htrn(500 K) - (34607) r 2 = 09999
TABLE 4 A Summary of the Vaporization Enthalpies of Muscalure
Values in italics are estimated using the following equation for hydrocarbons
∆lgH(29815 K) = 469(n-nQ) + 13 nQ +30
+ b + C
n = number of carbon atoms 23
nQ = number of quaternary sp3 carbon atoms 0
b = contribution of a functional group 0
branching correction 0
2
ln(tota)
-155 -150 -145 -140 -135 -130 -125 -120 -115
ln(p
po)
-23
-22
-21
-20
-19
-18
-17
FIGURE 5 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa for muscalure at T = 29815 K From left to right tetracosane Z-9-tricosene E 9-tricosene docosane heneicosane and eicosane
ln(ppo) = (137 0003) ln(tota) - (1608 0044) r 2 = 09999
TABLE 5 Correlation Between ln(tota) and Literature ln(ppo) for Muscalure at T = 29815 K
pPa(29815) = 12middot10-4 (Z)
pPa(29815) = 11middot10-4 (E)
The correlation between ln(tota) and literature values of ln(ppo) for Muscalure and the standards was repeated from T = (29815 to 500) K at 10 K intervals resulting in the following (r 2 for all correlations gt099)
ln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Tmin
0 5 10 15 20 25
Inte
nsit
yar
bitr
ary
unit
s
10000
20000
30000
40000
Tmin
42 44 46 48 50 52
Inte
nsit
y
2000
2500
3000
3500
4000
4500
5000
5500
FIGURE 2 Gas chromatograph From Left to right CH2Cl2 methyl dodecanoate empenthrin 1 and 2 methyl tetradecanoate methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate on a 5 phenylmethyl silicone column
1H NMR245 ppm
Fundamentals of Correlation Gas Chromatography- Vaporization Enthalpy
1 The residence time of a compound on the column ta is inversely proportional the compounds vapor pressure (ta = retention time of a solute ndash retention time of a non-retained reference ta = t ndash tnrr (often the solvent)
2 A plot of ln(tota) where to is the reference time 1 min versus 1T over a 30 K temperature range results in a straight line
3 The slope of the line -∆Htrn(Tm)R is the enthalpy of transfer of the analyte from the column to the gas phase
4 The enthalpy of transfer is related to the vaporization enthalpy (∆l
gH(T) by the following equation where ∆Hsln represents the enthalpy of interaction of the solute with the column ∆Htrn(Tm) = ∆l
gH (Tm) + ∆Hsln
(Tm)
5 If a series of standards are properly selected a second plot of ∆lgH(29815 K)
versus ∆Htrn(Tm) of the standards is also linear and the equation of the line can be used to evaluate the vaporization enthalpy of any additional targets included in the mixture
6 Appropriate standards with known vaporization enthalpies generally include compounds with the same number and type of functionality as the targets The structure of the hydrocabon portion of the molecule may vary
Use of appropriate standards with known vapor pressures also results in linear plots between ln(ppo) and ln(tota)
The equation of the line plus values of ln(tota) of the targets results in their vapor pressures
Performed over a range of temperatures can provide the vapor pressure temperature profile of the targets
Fundamentals of Correlation Gas Chromatography - Vapor Pressure
Vaporization Enthalpies and Vapor Pressure Equations of the Standards (po = 101325 Pa)
ln (ppo) = (1-TnbT)exp(Ao +A1T + A2T2) Cox equationln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial Rln(ppo) = - cd
gGdeg() + lgHdeg()[1 - 1T] + cd
gCpm()[T -1 + ln(T)] Equation of Clark and Glew
1(TK)
000192 000194 000196 000198 000200 000202 000204 000206 000208
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
FIGURE 3 A plot of ln(tota) where to = 1 min and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
2TABLE 2Experimental Retention Times of Muscalure and Various Alkanes
Htrn(Tm) kJmole-1
62 64 66 68 70 72 74 76 78
lg H
(298
K)
kJ
mol
-1
100
105
110
115
120
125
TABLE 3 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Muscalure
FIGURE 4 Vaporization enthalpy of muscalure and standards From left to right eicosane heneicosane docosane Z 9-tricosene E 9-tricosene tetracosane
lgHm(29815 K)kJmol-1 = (164001)Htrn(500 K) - (34607) r 2 = 09999
TABLE 4 A Summary of the Vaporization Enthalpies of Muscalure
Values in italics are estimated using the following equation for hydrocarbons
∆lgH(29815 K) = 469(n-nQ) + 13 nQ +30
+ b + C
n = number of carbon atoms 23
nQ = number of quaternary sp3 carbon atoms 0
b = contribution of a functional group 0
branching correction 0
2
ln(tota)
-155 -150 -145 -140 -135 -130 -125 -120 -115
ln(p
po)
-23
-22
-21
-20
-19
-18
-17
FIGURE 5 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa for muscalure at T = 29815 K From left to right tetracosane Z-9-tricosene E 9-tricosene docosane heneicosane and eicosane
ln(ppo) = (137 0003) ln(tota) - (1608 0044) r 2 = 09999
TABLE 5 Correlation Between ln(tota) and Literature ln(ppo) for Muscalure at T = 29815 K
pPa(29815) = 12middot10-4 (Z)
pPa(29815) = 11middot10-4 (E)
The correlation between ln(tota) and literature values of ln(ppo) for Muscalure and the standards was repeated from T = (29815 to 500) K at 10 K intervals resulting in the following (r 2 for all correlations gt099)
ln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Fundamentals of Correlation Gas Chromatography- Vaporization Enthalpy
1 The residence time of a compound on the column ta is inversely proportional the compounds vapor pressure (ta = retention time of a solute ndash retention time of a non-retained reference ta = t ndash tnrr (often the solvent)
2 A plot of ln(tota) where to is the reference time 1 min versus 1T over a 30 K temperature range results in a straight line
3 The slope of the line -∆Htrn(Tm)R is the enthalpy of transfer of the analyte from the column to the gas phase
4 The enthalpy of transfer is related to the vaporization enthalpy (∆l
gH(T) by the following equation where ∆Hsln represents the enthalpy of interaction of the solute with the column ∆Htrn(Tm) = ∆l
gH (Tm) + ∆Hsln
(Tm)
5 If a series of standards are properly selected a second plot of ∆lgH(29815 K)
versus ∆Htrn(Tm) of the standards is also linear and the equation of the line can be used to evaluate the vaporization enthalpy of any additional targets included in the mixture
6 Appropriate standards with known vaporization enthalpies generally include compounds with the same number and type of functionality as the targets The structure of the hydrocabon portion of the molecule may vary
Use of appropriate standards with known vapor pressures also results in linear plots between ln(ppo) and ln(tota)
The equation of the line plus values of ln(tota) of the targets results in their vapor pressures
Performed over a range of temperatures can provide the vapor pressure temperature profile of the targets
Fundamentals of Correlation Gas Chromatography - Vapor Pressure
Vaporization Enthalpies and Vapor Pressure Equations of the Standards (po = 101325 Pa)
ln (ppo) = (1-TnbT)exp(Ao +A1T + A2T2) Cox equationln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial Rln(ppo) = - cd
gGdeg() + lgHdeg()[1 - 1T] + cd
gCpm()[T -1 + ln(T)] Equation of Clark and Glew
1(TK)
000192 000194 000196 000198 000200 000202 000204 000206 000208
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
FIGURE 3 A plot of ln(tota) where to = 1 min and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
2TABLE 2Experimental Retention Times of Muscalure and Various Alkanes
Htrn(Tm) kJmole-1
62 64 66 68 70 72 74 76 78
lg H
(298
K)
kJ
mol
-1
100
105
110
115
120
125
TABLE 3 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Muscalure
FIGURE 4 Vaporization enthalpy of muscalure and standards From left to right eicosane heneicosane docosane Z 9-tricosene E 9-tricosene tetracosane
lgHm(29815 K)kJmol-1 = (164001)Htrn(500 K) - (34607) r 2 = 09999
TABLE 4 A Summary of the Vaporization Enthalpies of Muscalure
Values in italics are estimated using the following equation for hydrocarbons
∆lgH(29815 K) = 469(n-nQ) + 13 nQ +30
+ b + C
n = number of carbon atoms 23
nQ = number of quaternary sp3 carbon atoms 0
b = contribution of a functional group 0
branching correction 0
2
ln(tota)
-155 -150 -145 -140 -135 -130 -125 -120 -115
ln(p
po)
-23
-22
-21
-20
-19
-18
-17
FIGURE 5 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa for muscalure at T = 29815 K From left to right tetracosane Z-9-tricosene E 9-tricosene docosane heneicosane and eicosane
ln(ppo) = (137 0003) ln(tota) - (1608 0044) r 2 = 09999
TABLE 5 Correlation Between ln(tota) and Literature ln(ppo) for Muscalure at T = 29815 K
pPa(29815) = 12middot10-4 (Z)
pPa(29815) = 11middot10-4 (E)
The correlation between ln(tota) and literature values of ln(ppo) for Muscalure and the standards was repeated from T = (29815 to 500) K at 10 K intervals resulting in the following (r 2 for all correlations gt099)
ln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Use of appropriate standards with known vapor pressures also results in linear plots between ln(ppo) and ln(tota)
The equation of the line plus values of ln(tota) of the targets results in their vapor pressures
Performed over a range of temperatures can provide the vapor pressure temperature profile of the targets
Fundamentals of Correlation Gas Chromatography - Vapor Pressure
Vaporization Enthalpies and Vapor Pressure Equations of the Standards (po = 101325 Pa)
ln (ppo) = (1-TnbT)exp(Ao +A1T + A2T2) Cox equationln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial Rln(ppo) = - cd
gGdeg() + lgHdeg()[1 - 1T] + cd
gCpm()[T -1 + ln(T)] Equation of Clark and Glew
1(TK)
000192 000194 000196 000198 000200 000202 000204 000206 000208
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
FIGURE 3 A plot of ln(tota) where to = 1 min and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
2TABLE 2Experimental Retention Times of Muscalure and Various Alkanes
Htrn(Tm) kJmole-1
62 64 66 68 70 72 74 76 78
lg H
(298
K)
kJ
mol
-1
100
105
110
115
120
125
TABLE 3 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Muscalure
FIGURE 4 Vaporization enthalpy of muscalure and standards From left to right eicosane heneicosane docosane Z 9-tricosene E 9-tricosene tetracosane
lgHm(29815 K)kJmol-1 = (164001)Htrn(500 K) - (34607) r 2 = 09999
TABLE 4 A Summary of the Vaporization Enthalpies of Muscalure
Values in italics are estimated using the following equation for hydrocarbons
∆lgH(29815 K) = 469(n-nQ) + 13 nQ +30
+ b + C
n = number of carbon atoms 23
nQ = number of quaternary sp3 carbon atoms 0
b = contribution of a functional group 0
branching correction 0
2
ln(tota)
-155 -150 -145 -140 -135 -130 -125 -120 -115
ln(p
po)
-23
-22
-21
-20
-19
-18
-17
FIGURE 5 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa for muscalure at T = 29815 K From left to right tetracosane Z-9-tricosene E 9-tricosene docosane heneicosane and eicosane
ln(ppo) = (137 0003) ln(tota) - (1608 0044) r 2 = 09999
TABLE 5 Correlation Between ln(tota) and Literature ln(ppo) for Muscalure at T = 29815 K
pPa(29815) = 12middot10-4 (Z)
pPa(29815) = 11middot10-4 (E)
The correlation between ln(tota) and literature values of ln(ppo) for Muscalure and the standards was repeated from T = (29815 to 500) K at 10 K intervals resulting in the following (r 2 for all correlations gt099)
ln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Vaporization Enthalpies and Vapor Pressure Equations of the Standards (po = 101325 Pa)
ln (ppo) = (1-TnbT)exp(Ao +A1T + A2T2) Cox equationln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial Rln(ppo) = - cd
gGdeg() + lgHdeg()[1 - 1T] + cd
gCpm()[T -1 + ln(T)] Equation of Clark and Glew
1(TK)
000192 000194 000196 000198 000200 000202 000204 000206 000208
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
FIGURE 3 A plot of ln(tota) where to = 1 min and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
2TABLE 2Experimental Retention Times of Muscalure and Various Alkanes
Htrn(Tm) kJmole-1
62 64 66 68 70 72 74 76 78
lg H
(298
K)
kJ
mol
-1
100
105
110
115
120
125
TABLE 3 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Muscalure
FIGURE 4 Vaporization enthalpy of muscalure and standards From left to right eicosane heneicosane docosane Z 9-tricosene E 9-tricosene tetracosane
lgHm(29815 K)kJmol-1 = (164001)Htrn(500 K) - (34607) r 2 = 09999
TABLE 4 A Summary of the Vaporization Enthalpies of Muscalure
Values in italics are estimated using the following equation for hydrocarbons
∆lgH(29815 K) = 469(n-nQ) + 13 nQ +30
+ b + C
n = number of carbon atoms 23
nQ = number of quaternary sp3 carbon atoms 0
b = contribution of a functional group 0
branching correction 0
2
ln(tota)
-155 -150 -145 -140 -135 -130 -125 -120 -115
ln(p
po)
-23
-22
-21
-20
-19
-18
-17
FIGURE 5 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa for muscalure at T = 29815 K From left to right tetracosane Z-9-tricosene E 9-tricosene docosane heneicosane and eicosane
ln(ppo) = (137 0003) ln(tota) - (1608 0044) r 2 = 09999
TABLE 5 Correlation Between ln(tota) and Literature ln(ppo) for Muscalure at T = 29815 K
pPa(29815) = 12middot10-4 (Z)
pPa(29815) = 11middot10-4 (E)
The correlation between ln(tota) and literature values of ln(ppo) for Muscalure and the standards was repeated from T = (29815 to 500) K at 10 K intervals resulting in the following (r 2 for all correlations gt099)
ln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
1(TK)
000192 000194 000196 000198 000200 000202 000204 000206 000208
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
FIGURE 3 A plot of ln(tota) where to = 1 min and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
2TABLE 2Experimental Retention Times of Muscalure and Various Alkanes
Htrn(Tm) kJmole-1
62 64 66 68 70 72 74 76 78
lg H
(298
K)
kJ
mol
-1
100
105
110
115
120
125
TABLE 3 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Muscalure
FIGURE 4 Vaporization enthalpy of muscalure and standards From left to right eicosane heneicosane docosane Z 9-tricosene E 9-tricosene tetracosane
lgHm(29815 K)kJmol-1 = (164001)Htrn(500 K) - (34607) r 2 = 09999
TABLE 4 A Summary of the Vaporization Enthalpies of Muscalure
Values in italics are estimated using the following equation for hydrocarbons
∆lgH(29815 K) = 469(n-nQ) + 13 nQ +30
+ b + C
n = number of carbon atoms 23
nQ = number of quaternary sp3 carbon atoms 0
b = contribution of a functional group 0
branching correction 0
2
ln(tota)
-155 -150 -145 -140 -135 -130 -125 -120 -115
ln(p
po)
-23
-22
-21
-20
-19
-18
-17
FIGURE 5 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa for muscalure at T = 29815 K From left to right tetracosane Z-9-tricosene E 9-tricosene docosane heneicosane and eicosane
ln(ppo) = (137 0003) ln(tota) - (1608 0044) r 2 = 09999
TABLE 5 Correlation Between ln(tota) and Literature ln(ppo) for Muscalure at T = 29815 K
pPa(29815) = 12middot10-4 (Z)
pPa(29815) = 11middot10-4 (E)
The correlation between ln(tota) and literature values of ln(ppo) for Muscalure and the standards was repeated from T = (29815 to 500) K at 10 K intervals resulting in the following (r 2 for all correlations gt099)
ln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Htrn(Tm) kJmole-1
62 64 66 68 70 72 74 76 78
lg H
(298
K)
kJ
mol
-1
100
105
110
115
120
125
TABLE 3 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Muscalure
FIGURE 4 Vaporization enthalpy of muscalure and standards From left to right eicosane heneicosane docosane Z 9-tricosene E 9-tricosene tetracosane
lgHm(29815 K)kJmol-1 = (164001)Htrn(500 K) - (34607) r 2 = 09999
TABLE 4 A Summary of the Vaporization Enthalpies of Muscalure
Values in italics are estimated using the following equation for hydrocarbons
∆lgH(29815 K) = 469(n-nQ) + 13 nQ +30
+ b + C
n = number of carbon atoms 23
nQ = number of quaternary sp3 carbon atoms 0
b = contribution of a functional group 0
branching correction 0
2
ln(tota)
-155 -150 -145 -140 -135 -130 -125 -120 -115
ln(p
po)
-23
-22
-21
-20
-19
-18
-17
FIGURE 5 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa for muscalure at T = 29815 K From left to right tetracosane Z-9-tricosene E 9-tricosene docosane heneicosane and eicosane
ln(ppo) = (137 0003) ln(tota) - (1608 0044) r 2 = 09999
TABLE 5 Correlation Between ln(tota) and Literature ln(ppo) for Muscalure at T = 29815 K
pPa(29815) = 12middot10-4 (Z)
pPa(29815) = 11middot10-4 (E)
The correlation between ln(tota) and literature values of ln(ppo) for Muscalure and the standards was repeated from T = (29815 to 500) K at 10 K intervals resulting in the following (r 2 for all correlations gt099)
ln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
TABLE 4 A Summary of the Vaporization Enthalpies of Muscalure
Values in italics are estimated using the following equation for hydrocarbons
∆lgH(29815 K) = 469(n-nQ) + 13 nQ +30
+ b + C
n = number of carbon atoms 23
nQ = number of quaternary sp3 carbon atoms 0
b = contribution of a functional group 0
branching correction 0
2
ln(tota)
-155 -150 -145 -140 -135 -130 -125 -120 -115
ln(p
po)
-23
-22
-21
-20
-19
-18
-17
FIGURE 5 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa for muscalure at T = 29815 K From left to right tetracosane Z-9-tricosene E 9-tricosene docosane heneicosane and eicosane
ln(ppo) = (137 0003) ln(tota) - (1608 0044) r 2 = 09999
TABLE 5 Correlation Between ln(tota) and Literature ln(ppo) for Muscalure at T = 29815 K
pPa(29815) = 12middot10-4 (Z)
pPa(29815) = 11middot10-4 (E)
The correlation between ln(tota) and literature values of ln(ppo) for Muscalure and the standards was repeated from T = (29815 to 500) K at 10 K intervals resulting in the following (r 2 for all correlations gt099)
ln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
ln(tota)
-155 -150 -145 -140 -135 -130 -125 -120 -115
ln(p
po)
-23
-22
-21
-20
-19
-18
-17
FIGURE 5 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa for muscalure at T = 29815 K From left to right tetracosane Z-9-tricosene E 9-tricosene docosane heneicosane and eicosane
ln(ppo) = (137 0003) ln(tota) - (1608 0044) r 2 = 09999
TABLE 5 Correlation Between ln(tota) and Literature ln(ppo) for Muscalure at T = 29815 K
pPa(29815) = 12middot10-4 (Z)
pPa(29815) = 11middot10-4 (E)
The correlation between ln(tota) and literature values of ln(ppo) for Muscalure and the standards was repeated from T = (29815 to 500) K at 10 K intervals resulting in the following (r 2 for all correlations gt099)
ln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
The correlation between ln(tota) and literature values of ln(ppo) for Muscalure and the standards was repeated from T = (29815 to 500) K at 10 K intervals resulting in the following (r 2 for all correlations gt099)
ln(ppo) = AT -3 + BT -2 + C T -1 + D Third order polynomial
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
TABLE 7 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental or Estimated Values (in italics)
a Estimation from US EPA Estimation Program Interface EPI Suite Version 411
b SciFinder Scholar Estimated using Advanced Chemistry Development (ACDLabs) Software V1102
c Khanal O Schooter D Chemical analysis of organics in atmospheric particulates by headspace analysis Atmos Environ 2004 38(40) 6917-6925
d Boiling temperature at p = 133 Pa Yadav J S Ready P S Joshi BV A convenient reduction of alkylated tosylmethyl isocyanides Applications for the synthesis of natural products Tetrahedron 1988 44 7243-54
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
The vapor pressure of numerous substances have been measured by the gas chromatography - retention time method 1 which differs from the method just discussed
Vapor pressure Gas Chromatography - Retention Time Method
The vapor pressure - retention time method consists in ploting ln[(tr)tar(tr)ref ]T against ln(prefT) at different temperatures resulting in the following linear relationship
ln[(tr)tar(tr)ref ]T = [1- (lgH)tar(l
gH)ref] ln(p ref T) - C
(tr)tar and lgH)tar are the relative retention time and vaporization enthalpy of the target
(tr)ref and lgH)ref refer to the corresponding properties of the reference materials
The slope and intercept of the line obtained is given by [1- (lgH)tar(l
gH)ref] and - C
The vapor pressure of the target at T = 29815 K is obtained from
ln(ptar 29815 KPa) = [(lgH)tar(l
gH)ref] ln(p ref 29815 KPa) + C
1 Hamilton D J Gas Chromatographic Measurement of Volatility of Herbicide Esters J Chromatography 1980 195 75-83
Evaluation of Empenthrin
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
1 Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-36
Tsuzuki1 using an modification of the gas chromatographic method just described used dibutyl phthalate and bis 2-ethylhexyl phthalate as standards and measured a number of other esters including empenthrin and the following
O
O
OCl
Cl
permethrin
ON
OCF3
CF3
fluvalinate
ClO
N
O
fenvalerate
Cl
O
OCF3
bifenthrin
It is not clear well phthalate diesters can serve as standards to these pyrethrinoids which in addition to being single esters have a variety of other functional groups
CO2CH2(CH2)2CH3
CO2CH2(CH2)2CH3
CO2CH2CHCH2(CH)2CH3
CO2CH2CH(CH2(CH2)CH
CH2CH3
CH2CH3
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
TABLE 8 ∆trnH(Tm) versus ∆lgH(29815
K)
FIGURE 6 Vaporization enthalpy at T = 29815 K versus the enthalpy of transfer of fatty acid methyl esters (FAMES) and dialkyl phthalates evaluated simultaneously
FAMES
Diesters
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Evaluation of the Vapor Pressure and Vaporization Enthalpy of Empenthrin Using FAMES
CCH3(CH2)nCH2
O
OCH3
n = 9 12 13 15 16
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
1(TK)
000200 000202 000204 000206 000208 000210 000212 000214 000216 000218
ln(t
ot a)
-35
-30
-25
-20
-15
-10
-05
00
05
FIGURE 7 A plot of ln(tota) where to = 60 s and ta is equal to the difference in retention time between each analyte and a non-retained reference (the solvent) against 1T
TABLE 9 Experimental Retention Times of Empenthrin with Various Esters
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Htrn(Tm) kJmol-1
45 50 55 60 65 70 75
lg H (
298
15)
kJ
mol
-1
70
80
90
100
110
120
FIGURE 8 Vaporization enthalpy of empenthrin and standards From left to right methyl dodecanoate empenthrin I empenthrin 2 methyl hexadecanoate methyl octadecanoate ethyl octadecanoate methyl nonadecanoate
lgHm(29815 K)kJmol-1 = (1480055)Htrn(480 K) - (25936) r2 = 09944
TABLE 10 Correlation of Enthalpies of Transfer With Vaporization Enthalpies Empenthrin
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
TABLE 11 A Comparison of Vaporization Enthalpies at TK = 29815 of Empenthrin and Standards With Literature and Estimated Values (in italics)
aValues in italics are estimated using the following equation for hydrocarbons∆l
gH(29815 K) = 469(n-nQ) + 13 nQ +30 + b + Cn = number of carbon atoms 18nQ = number of quaternary sp3 carbon atoms 1b = contribution of a functional group 105branching correction -2
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
ln(tota)
-15 -14 -13 -12 -11 -10 -9 -8 -7
ln(p
po)
-22
-20
-18
-16
-14
-12
-10
TABLE 12 Correlation Between ln(tota) and Literature ln(ppo) for Empenthrin at T =29815 K
ln(ppo) = (125 0032) ln(tota) avg - (224 038 ) r 2 = 09979
FIGURE 9 A plot of ln(ppo) vs ln(tota) where po = 101325 Pa at T = 29815 K for empenthrin From left to right methyl nonadecanoate ethyl octadecanoate methyl octadecanoate methyl hexadecanoate methyl pentadecanoate empenthrin 2 empenthrin 1 methyl dodecanoate
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Repeating this process at 10 K intervals from T = (29815 to 480) K resulted in the following vapor pressure ndash temperature profile the data were fit to the following equation ln(ppo) = AT -3 + BT -2 + C T -1 + D All r 2 gt 099
TABLE 13 A Summary of LiquidSubcooled Liquid Vapor Pressures and Normal Boiling Temperatures and Comparison with Experimental Values
1Tsuzuki M Vapor pressures of carboxylic esters including pyrethroids measurement and estimation from molecular structure Chemosphere 2001 45 729-362 SciFinder Scholar obtained from Syracuse Research Corporation of Syracuse New York 3 SciFinder Scholar estimate
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
TABLE 14 Application of the Gas Chromatographic ndash Retention Time Method Using Fatty Acid Methyl Esters as Standards
lgHm(29815 K)(kJmol-1) = l
gHm(Tm) + [(1058 + 026Cp(l)(Jmol-1K-1))( TmK - 29815 K)]1000
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Acknowledgements Jessica Spencer and FKS Inc for financial support
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68
Vaporization Enthalpies and Vapor Pressures of Two Insecticide Components Muscalure and Empenthrin by Correlation Gas Chromatography Spencer J Chickos J Chem Eng Data 2013 59 3513-20
Ruzicka K Koutek B Fulem M Hoskovec M Indirect Determination of Vapor Pressures by Capillary Gas- Liquid Chromatography Analysis of the Reference Vapor ndashPressure Data and Their Treatment J Chem Eng Data 2011 57 1349-68