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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27

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

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27