Gibbs energies of formation of chlorinated benzoic acids and benzoates and application to their reductive dechlorination

Tang, Aili; Wang, Lingyu; Zhou, Ruiheng

doi:10.1016/j.theochem.2010.08.021

Cited by 9 publications

(16 citation statements)

References 23 publications

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“…Chlorinated benzoates are the compounds with which Tiedje and co-workers made their seminal observations on microbial dehalogenation (Suflita et al 1982 ). (Tang et al 2010 ) recently used quantum chemical methods (at the G3XMP2 level) plus a polarizable conductor model to estimate Gibbs free energy of formation values of chlorinated benzoic acids for both the gas and the aqueous phase. At pH 7 chlorinated benzoic acids are essentially fully deprotonated: their p K a values range between −3.3 and 3.6 (Tang et al 2010 ).…”

Section: Resultsmentioning

confidence: 99%

“…(Tang et al 2010 ) recently used quantum chemical methods (at the G3XMP2 level) plus a polarizable conductor model to estimate Gibbs free energy of formation values of chlorinated benzoic acids for both the gas and the aqueous phase. At pH 7 chlorinated benzoic acids are essentially fully deprotonated: their p K a values range between −3.3 and 3.6 (Tang et al 2010 ). Table 5 lists the Gibbs free energy values of all 19 chlorobenzoate congeners.…”

Section: Resultsmentioning

confidence: 99%

“…Thus, our third objective is to outline the effect of pH on the change in Gibbs free energy for the reductive dehalogenation of halogenated phenols and on the redox potentials for the corresponding redox couples. In recent years Tang et al ( 2010 ) and Sadowsky et al ( 2013 ) have updated the existing database of thermochemical properties for halogenated aromatics with state-of-the-art quantum chemical information on chlorobenzoates and halobenzenes. The fourth objective of the present paper is to integrate these data into a consistent set of redox potentials for various classes of halogenated aromatics.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

The Gibbs free energy of formation of halogenated benzenes, benzoates and phenols and their potential role as electron acceptors in anaerobic environments

Dolfing

Novak

2014

Biodegradation

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The sequence of redox reactions in the natural environment generally follows the electron affinity of the electron acceptors present and can be rationalized by the redox potentials of the appropriate half-reactions. Answering the question how halogenated aromatics fit into this sequence requires information on their Gibbs free energy of formation values. In 1992 Gibbs free energy data for various classes of halogenated aromatic compounds were systematically explored for the first time based on Benson’s group contribution method. Since then more accurate quantum chemical calculation methods have become available. Here we use these methods to estimate enthalpy and Gibbs free energy of formation values of all chlorinated and brominated phenols. These data and similar state-of-the-art datasets for halogenated benzenes and benzoates were then used to calculate two-electron redox potentials of halogenated aromatics for standard conditions and for pH 7. The results underline the need to take speciation into consideration when evaluating redox potentials at pH 7 and highlight the fact that halogenated aromatics are excellent electron acceptors in aqueous environments.Electronic supplementary materialThe online version of this article (doi:10.1007/s10532-014-9710-5) contains supplementary material, which is available to authorized users.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The Gibbs free energy of formation of halogenated benzenes, benzoates and phenols and their potential role as electron acceptors in anaerobic environments

Dolfing

Novak

2014

Biodegradation

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“…85 Other contributing factors include the significant difference in the experimental and/or theoretical values of proton solvation energies in the range between -1083.6 and -1114.6 kJ mol -1 . 80,85 Nevertheless, the present method yields relatively accurate pK a values for a wide variety of organic systems. [86][87][88] In the case of mixed halogenated phenols, we find that pK a values depend strongly on the 81 While obtaining values of ∆ R8 G° based on the CBS-QB3as in the study by Liptak et al 81 -might be computationally unfeasible for high-molecularweight halogenated phenols, we have shown in this study a more computationally affordable approach for estimating pK a .…”

Section: Acid Dissociation Constants (Pk a )mentioning

confidence: 93%

“…, we compare the calculated values of pK a for phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, and obromophenol with the measurements available in literature 80,[90][91][92][93][94]. as well as with estimates from the Marvin software95 which deploys a neural network algorithm.…”

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confidence: 99%

Thermodynamic Parameters Including Acid Dissociation Constants for Bromochlorophenols (BCPs)

et al. 2015

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This contribution reports standard gas-phase enthalpies of formation (∆ f H°2 98), entropies (Sº 298) and heat capacities (C p º(T)) for all plausible 64 bromochlorophenols (BCPs) at the M062X meta hybrid level using a polarised basis set of 6-311+G(d,p). Isodesmic work reactions served to calculate the standard enthalpies of formation for all bromochlorophenol molecules and several bromochlorophenoxy radicals. Standard entropies and heat capacities comprise correction terms due to the treatment of O˗H bonds as hindered rotors. Values of the bond dissociation enthalpies (BDHs) of O-H bonds, calculated for a selected series of bromochlorophenols, vary slightly with the change in the pattern and degree of halogenation of the phenyl ring. A thermodynamic cycle facilitated the estimation of pK a values, based on the calculated solvation and gas-phase deprotonation energies. We estimated the solvation energies of 19 out of 64 BCPs and their respective anions based on the integral equation formalism polarisable continuum model using optimised structures in the aqueous phase. Values of pK a decrease significantly from around 9 for monohalogenated to around 3 for pentahalogenated phenols.

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Integrating density functional theory into reductive dechlorination research

Das Schober,

Kurwadkar,

Harper

2023

Remediation Journal

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Chlorinated organics have been frequently detected in groundwaters, threatening the quality of drinking water supplies worldwide. A promising method for groundwater remediation involves reductive dechlorination (RD), in which chlorine atoms are sequentially removed and substituted by hydrogen, producing less harmful byproducts. In this paper, for the first time, RD research is reviewed in light of the growing incorporation of density functional theory (DFT) as a research tool. DFT has been used to uncover a variety of reaction properties for a range of relevant groundwater pollutants, including 1,2,3‐trichloropropane, hexachlorobenzene, and various dioxins. DFT models have revealed the role of surface interactions in driving the kinetics of catalytically driven RD. Mechanisms involved with biologically mediated RD have also been elucidated with insights gleaned from DFT. Issues and challenges for future research are also discussed.

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Gibbs energies of formation of chlorinated benzoic acids and benzoates and application to their reductive dechlorination

Cited by 9 publications

References 23 publications

The Gibbs free energy of formation of halogenated benzenes, benzoates and phenols and their potential role as electron acceptors in anaerobic environments

The Gibbs free energy of formation of halogenated benzenes, benzoates and phenols and their potential role as electron acceptors in anaerobic environments

Thermodynamic Parameters Including Acid Dissociation Constants for Bromochlorophenols (BCPs)

Integrating density functional theory into reductive dechlorination research

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