Free energies for degradation reactions of 1,2,3-trichloropropane from ab initio electronic structure theory

Eric J. Bylaska, Kurt R. Glaesemann, Andrew R. Felmy, Monica Vasiliu, David A. Dixon, Paul Tratnyek

Research output: Contribution to journalArticle

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Abstract

Electronic structure methods were used to calculate the gas and aqueous phase reaction energies for reductive dechlorination (i.e., hydrogenolysis), reductive β-elimination, dehydrochlorination, and nucleophilic substitution by OH- of 1,2,3-trichloropropane. The thermochemical properties ΔHf°(298.15 K), S°(298.15 K, 1 bar), and ΔG S(298.15 K, 1 bar) were calculated by using ab initio electronic structure calculations, isodesmic reactions schemes, gas-phase entropy estimates, and continuum solvation models for 1,2,3-trichloropropane and several likely degradation products: CH3-CHCl-CH2Cl, CH 2Cl-CH2-CH2Cl, CH 2-CHCl-CH2Cl, CH2Cl-CH-CH 2Cl, CH2=CCl-CH2Cl, cis-CHCl=CH-CH 2Cl, trans-CHCl=CH-CH2Cl, CH2=CH-CH 2Cl, CH2Cl-CHCl-CH2OH, CH2Cl-CHOH- CH2Cl, CH2=CCl-CH2OH, CH2=COH- CH2Cl, cis-CHOH=CH-CH2Cl, trans-CHOH=CH-CH2Cl, CH(=O)-CH2-CH2Cl, and CH3-C(=O)-CH 2Cl. On the basis of these thermochemical estimates, together with a Fe(II)/Fe(III) chemical equilibrium model for natural reducing environments, all of the reactions studied were predicted to be very favorable in the standard state and under a wide range of pH conditions. The most favorable reaction was reductive β-elimination (ΔGrxn ° ≈ -32 kcal/mol), followed closely by reductive dechlorination (Δ Grxn ° ≈ -27 kcal/mol), dehydrochlorination (ΔGrxn ° ≈ -27 kcal/mol), and nucleophilic substitution by OH-Grxn ° ≈ -25 kcal/mol). For both reduction reactions studied, it was found that the first electron-transfer step, yielding the intermediate CH 2-CHCl-CH2Cl and the CH2Cl-C H-CH2Cl species, was not favorable in the standard state (ΔGrxn ° ≈ +15 kcal/mol) and was predicted to occur only at relatively high pH values. This result suggests that reduction by natural attenuation is unlikely.

Original languageEnglish (US)
Pages (from-to)12269-12282
Number of pages14
JournalJournal of Physical Chemistry A
Volume114
Issue number46
DOIs
StatePublished - Nov 25 2010

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Dechlorination
Free energy
Electronic structure
Substitution reactions
Gases
free energy
Natural attenuation
methylidyne
degradation
electronic structure
Degradation
Hydrogenolysis
Solvation
Entropy
Electrons
1,2,3-trichloropropane
hydroxide ion
elimination
substitutes
vapor phases

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Free energies for degradation reactions of 1,2,3-trichloropropane from ab initio electronic structure theory. / Bylaska, Eric J.; Glaesemann, Kurt R.; Felmy, Andrew R.; Vasiliu, Monica; Dixon, David A.; Tratnyek, Paul.

In: Journal of Physical Chemistry A, Vol. 114, No. 46, 25.11.2010, p. 12269-12282.

Research output: Contribution to journalArticle

Bylaska, Eric J. ; Glaesemann, Kurt R. ; Felmy, Andrew R. ; Vasiliu, Monica ; Dixon, David A. ; Tratnyek, Paul. / Free energies for degradation reactions of 1,2,3-trichloropropane from ab initio electronic structure theory. In: Journal of Physical Chemistry A. 2010 ; Vol. 114, No. 46. pp. 12269-12282.
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title = "Free energies for degradation reactions of 1,2,3-trichloropropane from ab initio electronic structure theory",
abstract = "Electronic structure methods were used to calculate the gas and aqueous phase reaction energies for reductive dechlorination (i.e., hydrogenolysis), reductive β-elimination, dehydrochlorination, and nucleophilic substitution by OH- of 1,2,3-trichloropropane. The thermochemical properties ΔHf°(298.15 K), S°(298.15 K, 1 bar), and ΔG S(298.15 K, 1 bar) were calculated by using ab initio electronic structure calculations, isodesmic reactions schemes, gas-phase entropy estimates, and continuum solvation models for 1,2,3-trichloropropane and several likely degradation products: CH3-CHCl-CH2Cl, CH 2Cl-CH2-CH2Cl, C•H 2-CHCl-CH2Cl, CH2Cl-C•H-CH 2Cl, CH2=CCl-CH2Cl, cis-CHCl=CH-CH 2Cl, trans-CHCl=CH-CH2Cl, CH2=CH-CH 2Cl, CH2Cl-CHCl-CH2OH, CH2Cl-CHOH- CH2Cl, CH2=CCl-CH2OH, CH2=COH- CH2Cl, cis-CHOH=CH-CH2Cl, trans-CHOH=CH-CH2Cl, CH(=O)-CH2-CH2Cl, and CH3-C(=O)-CH 2Cl. On the basis of these thermochemical estimates, together with a Fe(II)/Fe(III) chemical equilibrium model for natural reducing environments, all of the reactions studied were predicted to be very favorable in the standard state and under a wide range of pH conditions. The most favorable reaction was reductive β-elimination (ΔGrxn ° ≈ -32 kcal/mol), followed closely by reductive dechlorination (Δ Grxn ° ≈ -27 kcal/mol), dehydrochlorination (ΔGrxn ° ≈ -27 kcal/mol), and nucleophilic substitution by OH- (ΔGrxn ° ≈ -25 kcal/mol). For both reduction reactions studied, it was found that the first electron-transfer step, yielding the intermediate C•H 2-CHCl-CH2Cl and the CH2Cl-C •H-CH2Cl species, was not favorable in the standard state (ΔGrxn ° ≈ +15 kcal/mol) and was predicted to occur only at relatively high pH values. This result suggests that reduction by natural attenuation is unlikely.",
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AU - Bylaska, Eric J.

AU - Glaesemann, Kurt R.

AU - Felmy, Andrew R.

AU - Vasiliu, Monica

AU - Dixon, David A.

AU - Tratnyek, Paul

PY - 2010/11/25

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N2 - Electronic structure methods were used to calculate the gas and aqueous phase reaction energies for reductive dechlorination (i.e., hydrogenolysis), reductive β-elimination, dehydrochlorination, and nucleophilic substitution by OH- of 1,2,3-trichloropropane. The thermochemical properties ΔHf°(298.15 K), S°(298.15 K, 1 bar), and ΔG S(298.15 K, 1 bar) were calculated by using ab initio electronic structure calculations, isodesmic reactions schemes, gas-phase entropy estimates, and continuum solvation models for 1,2,3-trichloropropane and several likely degradation products: CH3-CHCl-CH2Cl, CH 2Cl-CH2-CH2Cl, C•H 2-CHCl-CH2Cl, CH2Cl-C•H-CH 2Cl, CH2=CCl-CH2Cl, cis-CHCl=CH-CH 2Cl, trans-CHCl=CH-CH2Cl, CH2=CH-CH 2Cl, CH2Cl-CHCl-CH2OH, CH2Cl-CHOH- CH2Cl, CH2=CCl-CH2OH, CH2=COH- CH2Cl, cis-CHOH=CH-CH2Cl, trans-CHOH=CH-CH2Cl, CH(=O)-CH2-CH2Cl, and CH3-C(=O)-CH 2Cl. On the basis of these thermochemical estimates, together with a Fe(II)/Fe(III) chemical equilibrium model for natural reducing environments, all of the reactions studied were predicted to be very favorable in the standard state and under a wide range of pH conditions. The most favorable reaction was reductive β-elimination (ΔGrxn ° ≈ -32 kcal/mol), followed closely by reductive dechlorination (Δ Grxn ° ≈ -27 kcal/mol), dehydrochlorination (ΔGrxn ° ≈ -27 kcal/mol), and nucleophilic substitution by OH- (ΔGrxn ° ≈ -25 kcal/mol). For both reduction reactions studied, it was found that the first electron-transfer step, yielding the intermediate C•H 2-CHCl-CH2Cl and the CH2Cl-C •H-CH2Cl species, was not favorable in the standard state (ΔGrxn ° ≈ +15 kcal/mol) and was predicted to occur only at relatively high pH values. This result suggests that reduction by natural attenuation is unlikely.

AB - Electronic structure methods were used to calculate the gas and aqueous phase reaction energies for reductive dechlorination (i.e., hydrogenolysis), reductive β-elimination, dehydrochlorination, and nucleophilic substitution by OH- of 1,2,3-trichloropropane. The thermochemical properties ΔHf°(298.15 K), S°(298.15 K, 1 bar), and ΔG S(298.15 K, 1 bar) were calculated by using ab initio electronic structure calculations, isodesmic reactions schemes, gas-phase entropy estimates, and continuum solvation models for 1,2,3-trichloropropane and several likely degradation products: CH3-CHCl-CH2Cl, CH 2Cl-CH2-CH2Cl, C•H 2-CHCl-CH2Cl, CH2Cl-C•H-CH 2Cl, CH2=CCl-CH2Cl, cis-CHCl=CH-CH 2Cl, trans-CHCl=CH-CH2Cl, CH2=CH-CH 2Cl, CH2Cl-CHCl-CH2OH, CH2Cl-CHOH- CH2Cl, CH2=CCl-CH2OH, CH2=COH- CH2Cl, cis-CHOH=CH-CH2Cl, trans-CHOH=CH-CH2Cl, CH(=O)-CH2-CH2Cl, and CH3-C(=O)-CH 2Cl. On the basis of these thermochemical estimates, together with a Fe(II)/Fe(III) chemical equilibrium model for natural reducing environments, all of the reactions studied were predicted to be very favorable in the standard state and under a wide range of pH conditions. The most favorable reaction was reductive β-elimination (ΔGrxn ° ≈ -32 kcal/mol), followed closely by reductive dechlorination (Δ Grxn ° ≈ -27 kcal/mol), dehydrochlorination (ΔGrxn ° ≈ -27 kcal/mol), and nucleophilic substitution by OH- (ΔGrxn ° ≈ -25 kcal/mol). For both reduction reactions studied, it was found that the first electron-transfer step, yielding the intermediate C•H 2-CHCl-CH2Cl and the CH2Cl-C •H-CH2Cl species, was not favorable in the standard state (ΔGrxn ° ≈ +15 kcal/mol) and was predicted to occur only at relatively high pH values. This result suggests that reduction by natural attenuation is unlikely.

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