Adventures in Thermochemistry

James S Chickos

Department of Chemistry and Biochemistry

University of Missouri-St Louis

Louis MO 63121

E-mail jscumsledu

10

Confluence of the Missouri and Mississippi Rivers

Applications of the The Correlation-Gas Chromatographic Method

Objectives To go where no one else has gone

1 Evaluation of the vaporization enthalpies of large molecules

2 Application of Correlation-Gas Chromatography to a Tautomeric Mixture - Acetylacetone

3 The Vaporization Enthalpies of Drugs and Related Substances

4 Evaluation of the Vaporization Enthalpies and Vapor Pressures of Plasticizers

Dialkyl phthalates and related isomers are important industrial products and many have been produced in large quantities for a considerable period of time Their importance ranges from their use in polymers as plasticizers to applications in cosmetics

Some plastics become brittle with time simply due to the evaporation of the plasticizer

Phthalate esters have been in use for a considerable amount of time Due to thenature of their properties and longevity of use they are ubiquitous in the environment The vapor pressures and vaporization measured repeatedly over the years This has led to large discrepancies in their thermodynamic properties

Dibutyl phthalate and bis (2-ethylhexyl) phthalate have been selected as reference compounds for vapor pressure measurements by the US EPA

We decided to examine if it were possible to establish a set of self consistent experimental values in an area that has been characterized by numerous discordant values We are not aware of any other method capable of this

As an example of the problems associated with these compounds we purchased diocyl phthalate and terephthalate from Aldrich only to discover that both materials were actually the 2-ethylhexyl derivatives Di-n-octyl phthalate is also referred to as dioctyl phthalate

Estimation of compounds containing multiple functional groups

lgH(298 K) kJmol-1 = 469(nC - nQ) + 13nQ + ΣFibi + 30 + C where the value if Fi depends

on the hybridization and substitution pattern of the carbon to which the functional group is attached

b (ester) = 105 kJmol-1 C(H3)- F = 162 -C(C)(H2)- F = 108 =C(C3)- F = 085

C(C2)(H)- = 06 C = -2 kJmol-1C branch on an sp3 hybridized carbon average deviation ~ plusmn 8

No references to the original work are provided Therefore we did not use the vapor pressure values as standards

ln(ppo) = Arsquo ndash BrsquoRT (1)

Vapor pressures reported as

ln (ppo) = (1-ToT)exp[Ao +A1(TK) +A2(TK)2] Cox Eq

Vapor pressures reported as ln(ppo) = a + b(TK)-1 + c(TK)-2

(f) Small P A Small K W Cowley P The Vapor Pressure of Some High Boiling Esters Trans Faraday Soc 1948 44 810-6

Measurements by Sergey Verevkin

lgH( 29815 K) =

(950 11) kJmol-1

Average value from Hales et al Verevkin and this work

TK

250 300 350 400 450 500 550 600 650

ln(p

po)

-20

-18

-16

-14

-12

-10

-8

-6

-4

-2

0

2

Figure Bottom curve A plot of ln(ppo) versus TK for vapor pressures reported for dibutyl phthalate by Small et al (line)17 Hales et al ( )18 and this work transpiration ()

ln(ppo) = Ardquo(TK)-3 + Brdquo(TK)-2 + Crdquo(TK)-1 + Drdquo (9)

This process was repeated at T = 10 K intervals from (29815 to 550) K and the

resulting vapor pressures fit to the following third order polynomial (r 2 gt 099)

A duplicate run resulted in the same value for bis (2-ethylhexyl) phthalate Since this value is within experimental error of the EPA value the EPA value was used of 1167plusmn05 kJ mol-1 was used in subsequent runs

bis 2-ethylhexyl phthalate1167plusmn05 EPA value

Using vapor pressures for

(9)

vapor pressures were evaluated from correlations between ln(tota) and ln(ppo) as a function of temperature from T = 29815 to 550 K

Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

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• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22

Dialkyl phthalates and related isomers are important industrial products and many have been produced in large quantities for a considerable period of time Their importance ranges from their use in polymers as plasticizers to applications in cosmetics

Some plastics become brittle with time simply due to the evaporation of the plasticizer

Phthalate esters have been in use for a considerable amount of time Due to thenature of their properties and longevity of use they are ubiquitous in the environment The vapor pressures and vaporization measured repeatedly over the years This has led to large discrepancies in their thermodynamic properties

Dibutyl phthalate and bis (2-ethylhexyl) phthalate have been selected as reference compounds for vapor pressure measurements by the US EPA

We decided to examine if it were possible to establish a set of self consistent experimental values in an area that has been characterized by numerous discordant values We are not aware of any other method capable of this

As an example of the problems associated with these compounds we purchased diocyl phthalate and terephthalate from Aldrich only to discover that both materials were actually the 2-ethylhexyl derivatives Di-n-octyl phthalate is also referred to as dioctyl phthalate

Estimation of compounds containing multiple functional groups

lgH(298 K) kJmol-1 = 469(nC - nQ) + 13nQ + ΣFibi + 30 + C where the value if Fi depends

on the hybridization and substitution pattern of the carbon to which the functional group is attached

b (ester) = 105 kJmol-1 C(H3)- F = 162 -C(C)(H2)- F = 108 =C(C3)- F = 085

C(C2)(H)- = 06 C = -2 kJmol-1C branch on an sp3 hybridized carbon average deviation ~ plusmn 8

No references to the original work are provided Therefore we did not use the vapor pressure values as standards

ln(ppo) = Arsquo ndash BrsquoRT (1)

Vapor pressures reported as

ln (ppo) = (1-ToT)exp[Ao +A1(TK) +A2(TK)2] Cox Eq

Vapor pressures reported as ln(ppo) = a + b(TK)-1 + c(TK)-2

(f) Small P A Small K W Cowley P The Vapor Pressure of Some High Boiling Esters Trans Faraday Soc 1948 44 810-6

Measurements by Sergey Verevkin

lgH( 29815 K) =

(950 11) kJmol-1

Average value from Hales et al Verevkin and this work

TK

250 300 350 400 450 500 550 600 650

ln(p

po)

-20

-18

-16

-14

-12

-10

-8

-6

-4

-2

0

2

Figure Bottom curve A plot of ln(ppo) versus TK for vapor pressures reported for dibutyl phthalate by Small et al (line)17 Hales et al ( )18 and this work transpiration ()

ln(ppo) = Ardquo(TK)-3 + Brdquo(TK)-2 + Crdquo(TK)-1 + Drdquo (9)

This process was repeated at T = 10 K intervals from (29815 to 550) K and the

resulting vapor pressures fit to the following third order polynomial (r 2 gt 099)

A duplicate run resulted in the same value for bis (2-ethylhexyl) phthalate Since this value is within experimental error of the EPA value the EPA value was used of 1167plusmn05 kJ mol-1 was used in subsequent runs

bis 2-ethylhexyl phthalate1167plusmn05 EPA value

Using vapor pressures for

(9)

vapor pressures were evaluated from correlations between ln(tota) and ln(ppo) as a function of temperature from T = 29815 to 550 K

Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

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• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22

Phthalate esters have been in use for a considerable amount of time Due to thenature of their properties and longevity of use they are ubiquitous in the environment The vapor pressures and vaporization measured repeatedly over the years This has led to large discrepancies in their thermodynamic properties

Dibutyl phthalate and bis (2-ethylhexyl) phthalate have been selected as reference compounds for vapor pressure measurements by the US EPA

We decided to examine if it were possible to establish a set of self consistent experimental values in an area that has been characterized by numerous discordant values We are not aware of any other method capable of this

As an example of the problems associated with these compounds we purchased diocyl phthalate and terephthalate from Aldrich only to discover that both materials were actually the 2-ethylhexyl derivatives Di-n-octyl phthalate is also referred to as dioctyl phthalate

Estimation of compounds containing multiple functional groups

lgH(298 K) kJmol-1 = 469(nC - nQ) + 13nQ + ΣFibi + 30 + C where the value if Fi depends

on the hybridization and substitution pattern of the carbon to which the functional group is attached

b (ester) = 105 kJmol-1 C(H3)- F = 162 -C(C)(H2)- F = 108 =C(C3)- F = 085

C(C2)(H)- = 06 C = -2 kJmol-1C branch on an sp3 hybridized carbon average deviation ~ plusmn 8

No references to the original work are provided Therefore we did not use the vapor pressure values as standards

ln(ppo) = Arsquo ndash BrsquoRT (1)

Vapor pressures reported as

ln (ppo) = (1-ToT)exp[Ao +A1(TK) +A2(TK)2] Cox Eq

Vapor pressures reported as ln(ppo) = a + b(TK)-1 + c(TK)-2

(f) Small P A Small K W Cowley P The Vapor Pressure of Some High Boiling Esters Trans Faraday Soc 1948 44 810-6

Measurements by Sergey Verevkin

lgH( 29815 K) =

(950 11) kJmol-1

Average value from Hales et al Verevkin and this work

TK

250 300 350 400 450 500 550 600 650

ln(p

po)

-20

-18

-16

-14

-12

-10

-8

-6

-4

-2

0

2

Figure Bottom curve A plot of ln(ppo) versus TK for vapor pressures reported for dibutyl phthalate by Small et al (line)17 Hales et al ( )18 and this work transpiration ()

ln(ppo) = Ardquo(TK)-3 + Brdquo(TK)-2 + Crdquo(TK)-1 + Drdquo (9)

This process was repeated at T = 10 K intervals from (29815 to 550) K and the

resulting vapor pressures fit to the following third order polynomial (r 2 gt 099)

A duplicate run resulted in the same value for bis (2-ethylhexyl) phthalate Since this value is within experimental error of the EPA value the EPA value was used of 1167plusmn05 kJ mol-1 was used in subsequent runs

bis 2-ethylhexyl phthalate1167plusmn05 EPA value

Using vapor pressures for

(9)

vapor pressures were evaluated from correlations between ln(tota) and ln(ppo) as a function of temperature from T = 29815 to 550 K

Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

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• Slide 22

Estimation of compounds containing multiple functional groups

lgH(298 K) kJmol-1 = 469(nC - nQ) + 13nQ + ΣFibi + 30 + C where the value if Fi depends

on the hybridization and substitution pattern of the carbon to which the functional group is attached

b (ester) = 105 kJmol-1 C(H3)- F = 162 -C(C)(H2)- F = 108 =C(C3)- F = 085

C(C2)(H)- = 06 C = -2 kJmol-1C branch on an sp3 hybridized carbon average deviation ~ plusmn 8

No references to the original work are provided Therefore we did not use the vapor pressure values as standards

ln(ppo) = Arsquo ndash BrsquoRT (1)

Vapor pressures reported as

ln (ppo) = (1-ToT)exp[Ao +A1(TK) +A2(TK)2] Cox Eq

Vapor pressures reported as ln(ppo) = a + b(TK)-1 + c(TK)-2

(f) Small P A Small K W Cowley P The Vapor Pressure of Some High Boiling Esters Trans Faraday Soc 1948 44 810-6

Measurements by Sergey Verevkin

lgH( 29815 K) =

(950 11) kJmol-1

Average value from Hales et al Verevkin and this work

TK

250 300 350 400 450 500 550 600 650

ln(p

po)

-20

-18

-16

-14

-12

-10

-8

-6

-4

-2

0

2

Figure Bottom curve A plot of ln(ppo) versus TK for vapor pressures reported for dibutyl phthalate by Small et al (line)17 Hales et al ( )18 and this work transpiration ()

ln(ppo) = Ardquo(TK)-3 + Brdquo(TK)-2 + Crdquo(TK)-1 + Drdquo (9)

This process was repeated at T = 10 K intervals from (29815 to 550) K and the

resulting vapor pressures fit to the following third order polynomial (r 2 gt 099)

A duplicate run resulted in the same value for bis (2-ethylhexyl) phthalate Since this value is within experimental error of the EPA value the EPA value was used of 1167plusmn05 kJ mol-1 was used in subsequent runs

bis 2-ethylhexyl phthalate1167plusmn05 EPA value

Using vapor pressures for

(9)

vapor pressures were evaluated from correlations between ln(tota) and ln(ppo) as a function of temperature from T = 29815 to 550 K

Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

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• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22

No references to the original work are provided Therefore we did not use the vapor pressure values as standards

ln(ppo) = Arsquo ndash BrsquoRT (1)

Vapor pressures reported as

ln (ppo) = (1-ToT)exp[Ao +A1(TK) +A2(TK)2] Cox Eq

Vapor pressures reported as ln(ppo) = a + b(TK)-1 + c(TK)-2

(f) Small P A Small K W Cowley P The Vapor Pressure of Some High Boiling Esters Trans Faraday Soc 1948 44 810-6

Measurements by Sergey Verevkin

lgH( 29815 K) =

(950 11) kJmol-1

Average value from Hales et al Verevkin and this work

TK

250 300 350 400 450 500 550 600 650

ln(p

po)

-20

-18

-16

-14

-12

-10

-8

-6

-4

-2

0

2

Figure Bottom curve A plot of ln(ppo) versus TK for vapor pressures reported for dibutyl phthalate by Small et al (line)17 Hales et al ( )18 and this work transpiration ()

ln(ppo) = Ardquo(TK)-3 + Brdquo(TK)-2 + Crdquo(TK)-1 + Drdquo (9)

This process was repeated at T = 10 K intervals from (29815 to 550) K and the

resulting vapor pressures fit to the following third order polynomial (r 2 gt 099)

A duplicate run resulted in the same value for bis (2-ethylhexyl) phthalate Since this value is within experimental error of the EPA value the EPA value was used of 1167plusmn05 kJ mol-1 was used in subsequent runs

bis 2-ethylhexyl phthalate1167plusmn05 EPA value

Using vapor pressures for

(9)

vapor pressures were evaluated from correlations between ln(tota) and ln(ppo) as a function of temperature from T = 29815 to 550 K

Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
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• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22

Vapor pressures reported as

ln (ppo) = (1-ToT)exp[Ao +A1(TK) +A2(TK)2] Cox Eq

Vapor pressures reported as ln(ppo) = a + b(TK)-1 + c(TK)-2

(f) Small P A Small K W Cowley P The Vapor Pressure of Some High Boiling Esters Trans Faraday Soc 1948 44 810-6

Measurements by Sergey Verevkin

lgH( 29815 K) =

(950 11) kJmol-1

Average value from Hales et al Verevkin and this work

TK

250 300 350 400 450 500 550 600 650

ln(p

po)

-20

-18

-16

-14

-12

-10

-8

-6

-4

-2

0

2

Figure Bottom curve A plot of ln(ppo) versus TK for vapor pressures reported for dibutyl phthalate by Small et al (line)17 Hales et al ( )18 and this work transpiration ()

ln(ppo) = Ardquo(TK)-3 + Brdquo(TK)-2 + Crdquo(TK)-1 + Drdquo (9)

This process was repeated at T = 10 K intervals from (29815 to 550) K and the

resulting vapor pressures fit to the following third order polynomial (r 2 gt 099)

A duplicate run resulted in the same value for bis (2-ethylhexyl) phthalate Since this value is within experimental error of the EPA value the EPA value was used of 1167plusmn05 kJ mol-1 was used in subsequent runs

bis 2-ethylhexyl phthalate1167plusmn05 EPA value

Using vapor pressures for

(9)

vapor pressures were evaluated from correlations between ln(tota) and ln(ppo) as a function of temperature from T = 29815 to 550 K

Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
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• Slide 9
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• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22

Vapor pressures reported as ln(ppo) = a + b(TK)-1 + c(TK)-2

(f) Small P A Small K W Cowley P The Vapor Pressure of Some High Boiling Esters Trans Faraday Soc 1948 44 810-6

Measurements by Sergey Verevkin

lgH( 29815 K) =

(950 11) kJmol-1

Average value from Hales et al Verevkin and this work

TK

250 300 350 400 450 500 550 600 650

ln(p

po)

-20

-18

-16

-14

-12

-10

-8

-6

-4

-2

0

2

Figure Bottom curve A plot of ln(ppo) versus TK for vapor pressures reported for dibutyl phthalate by Small et al (line)17 Hales et al ( )18 and this work transpiration ()

ln(ppo) = Ardquo(TK)-3 + Brdquo(TK)-2 + Crdquo(TK)-1 + Drdquo (9)

This process was repeated at T = 10 K intervals from (29815 to 550) K and the

resulting vapor pressures fit to the following third order polynomial (r 2 gt 099)

A duplicate run resulted in the same value for bis (2-ethylhexyl) phthalate Since this value is within experimental error of the EPA value the EPA value was used of 1167plusmn05 kJ mol-1 was used in subsequent runs

bis 2-ethylhexyl phthalate1167plusmn05 EPA value

Using vapor pressures for

(9)

vapor pressures were evaluated from correlations between ln(tota) and ln(ppo) as a function of temperature from T = 29815 to 550 K

Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
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• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22

Measurements by Sergey Verevkin

lgH( 29815 K) =

(950 11) kJmol-1

Average value from Hales et al Verevkin and this work

TK

250 300 350 400 450 500 550 600 650

ln(p

po)

-20

-18

-16

-14

-12

-10

-8

-6

-4

-2

0

2

Figure Bottom curve A plot of ln(ppo) versus TK for vapor pressures reported for dibutyl phthalate by Small et al (line)17 Hales et al ( )18 and this work transpiration ()

ln(ppo) = Ardquo(TK)-3 + Brdquo(TK)-2 + Crdquo(TK)-1 + Drdquo (9)

This process was repeated at T = 10 K intervals from (29815 to 550) K and the

resulting vapor pressures fit to the following third order polynomial (r 2 gt 099)

A duplicate run resulted in the same value for bis (2-ethylhexyl) phthalate Since this value is within experimental error of the EPA value the EPA value was used of 1167plusmn05 kJ mol-1 was used in subsequent runs

bis 2-ethylhexyl phthalate1167plusmn05 EPA value

Using vapor pressures for

(9)

vapor pressures were evaluated from correlations between ln(tota) and ln(ppo) as a function of temperature from T = 29815 to 550 K

Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
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• Slide 22

TK

250 300 350 400 450 500 550 600 650

ln(p

po)

-20

-18

-16

-14

-12

-10

-8

-6

-4

-2

0

2

Figure Bottom curve A plot of ln(ppo) versus TK for vapor pressures reported for dibutyl phthalate by Small et al (line)17 Hales et al ( )18 and this work transpiration ()

ln(ppo) = Ardquo(TK)-3 + Brdquo(TK)-2 + Crdquo(TK)-1 + Drdquo (9)

This process was repeated at T = 10 K intervals from (29815 to 550) K and the

resulting vapor pressures fit to the following third order polynomial (r 2 gt 099)

A duplicate run resulted in the same value for bis (2-ethylhexyl) phthalate Since this value is within experimental error of the EPA value the EPA value was used of 1167plusmn05 kJ mol-1 was used in subsequent runs

bis 2-ethylhexyl phthalate1167plusmn05 EPA value

Using vapor pressures for

(9)

vapor pressures were evaluated from correlations between ln(tota) and ln(ppo) as a function of temperature from T = 29815 to 550 K

Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

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ln(ppo) = Ardquo(TK)-3 + Brdquo(TK)-2 + Crdquo(TK)-1 + Drdquo (9)

This process was repeated at T = 10 K intervals from (29815 to 550) K and the

resulting vapor pressures fit to the following third order polynomial (r 2 gt 099)

A duplicate run resulted in the same value for bis (2-ethylhexyl) phthalate Since this value is within experimental error of the EPA value the EPA value was used of 1167plusmn05 kJ mol-1 was used in subsequent runs

bis 2-ethylhexyl phthalate1167plusmn05 EPA value

Using vapor pressures for

(9)

vapor pressures were evaluated from correlations between ln(tota) and ln(ppo) as a function of temperature from T = 29815 to 550 K

Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

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A duplicate run resulted in the same value for bis (2-ethylhexyl) phthalate Since this value is within experimental error of the EPA value the EPA value was used of 1167plusmn05 kJ mol-1 was used in subsequent runs

bis 2-ethylhexyl phthalate1167plusmn05 EPA value

Using vapor pressures for

(9)

vapor pressures were evaluated from correlations between ln(tota) and ln(ppo) as a function of temperature from T = 29815 to 550 K

Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

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bis 2-ethylhexyl phthalate1167plusmn05 EPA value

Using vapor pressures for

(9)

vapor pressures were evaluated from correlations between ln(tota) and ln(ppo) as a function of temperature from T = 29815 to 550 K

Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

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Using vapor pressures for

(9)

vapor pressures were evaluated from correlations between ln(tota) and ln(ppo) as a function of temperature from T = 29815 to 550 K

Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

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Dimethyl terephthalate and isophthalate and dicyclohexyl phthalate are crystalline solids at room temperature Since vapor pressures of the liquid as a function of temperature vaporization and fusion enthalpies at and T = (Tfus and 29815 K) are available it is also possivle to calculate both sublimation vapor pressures and enthalpies

ln(pcrPa) = [crgH (Tfus) + cr

gCpT] [ 1TfusK ndash 129815]R + ln(p(TfusPa))

where crgCpT = [075 + 015Cp(cr)][(Tfus K -29815)2]

Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

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Visitng Undergraduate StudentMikhail Kozlovskiy from Moscow Massiel Mori from South America

High School StudentJohn Vikman

Undergraduate StudentsJessica SpencerChristian Koebel

Graduate StudentChase GobbleJoe Wilson

Faculty CollaboratorSergey Verevkin University of Rostock Rostock Germany

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