Enthalpy of Formation of C2H2O4 (Oxalic Acid) from High-Level Calculations and the Active Thermochemical Tables Approach

Feller, David; Bross, David H.; Ruscic, Branko

doi:10.1021/acs.jpca.8b12329

Title: Enthalpy of Formation of C₂H₂O₄ (Oxalic Acid) from High-Level Calculations and the Active Thermochemical Tables Approach

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Abstract

High-level coupled cluster calculations obtained with the Feller–Peterson–Dixon (FPD) approach and new data from the most recent version of the Active Thermochemical Tables (ATcT) are used to reassess the enthalpy of formation of gas-phase C₂H₂O₄ (oxalic acid). The theoretical value was further calibrated by comparing FPD and ATcT gas-phase enthalpies of formation for H₂CO (formaldehyde) and the two low-lying conformations of C₂H₄O₂ (syn and anti acetic acid). The FPD approach produces a theoretical enthalpy of formation of gas-phase oxalic acid of –732.2 ± 4.0 kJ/mol at 298.15 K (–721.8 ± 4.0 kJ/mol at 0 K). An independently obtained ATcT value, based on reassessing the existent experimental determinations and expanding the resulting thermochemical network with select mid-level composite theoretical results, disagrees with several earlier recommendations that were based solely on experimental determinations but is in excellent accord with the current FPD value. The inclusion of the latter in the most recent ATcT thermochemical network produces a further refined value for the gas-phase enthalpy of formation, –731.6 ± 1.2 kJ/mol at 298.15 K (–721.0 ± 1.2 kJ/mol at 0 K). In conclusion, the condensed-phase ATcT enthalpy of formation of oxalic acid is –829.7 ± 0.5 kJ/mol, and the resulting sublimation enthalpy ismore » 98.1 ± 1.3 kJ/mol, both at 298.15 K.« less

Authors:

^[1];

^[2];

^[3]

Washington State Univ., Pullman, WA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); The Univ. of Chicago, Chicago, IL (United States)

Publication Date:: 2019-03-22

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1530415

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Additional Journal Information:: Journal Volume: 123; Journal Issue: 16; Journal ID: ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Active Thermochemical Tables; electronic structure theory; enthalpy of formation; high-level theory

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                    Feller, David, Bross, David H., and Ruscic, Branko. Enthalpy of Formation of C2H2O4 (Oxalic Acid) from High-Level Calculations and the Active Thermochemical Tables Approach.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.jpca.8b12329.

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                    Feller, David, Bross, David H., & Ruscic, Branko. Enthalpy of Formation of C2H2O4 (Oxalic Acid) from High-Level Calculations and the Active Thermochemical Tables Approach.  United States.  https://doi.org/10.1021/acs.jpca.8b12329

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                    Feller, David, Bross, David H., and Ruscic, Branko. Fri .  
"Enthalpy of Formation of C2H2O4 (Oxalic Acid) from High-Level Calculations and the Active Thermochemical Tables Approach".  United States.  https://doi.org/10.1021/acs.jpca.8b12329.  https://www.osti.gov/servlets/purl/1530415.

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@article{osti_1530415,

  title        = {Enthalpy of Formation of C2H2O4 (Oxalic Acid) from High-Level Calculations and the Active Thermochemical Tables Approach},

  author       = {Feller, David and Bross, David H. and Ruscic, Branko},

  abstractNote = {High-level coupled cluster calculations obtained with the Feller–Peterson–Dixon (FPD) approach and new data from the most recent version of the Active Thermochemical Tables (ATcT) are used to reassess the enthalpy of formation of gas-phase C2H2O4 (oxalic acid). The theoretical value was further calibrated by comparing FPD and ATcT gas-phase enthalpies of formation for H2CO (formaldehyde) and the two low-lying conformations of C2H4O2 (syn and anti acetic acid). The FPD approach produces a theoretical enthalpy of formation of gas-phase oxalic acid of –732.2 ± 4.0 kJ/mol at 298.15 K (–721.8 ± 4.0 kJ/mol at 0 K). An independently obtained ATcT value, based on reassessing the existent experimental determinations and expanding the resulting thermochemical network with select mid-level composite theoretical results, disagrees with several earlier recommendations that were based solely on experimental determinations but is in excellent accord with the current FPD value. The inclusion of the latter in the most recent ATcT thermochemical network produces a further refined value for the gas-phase enthalpy of formation, –731.6 ± 1.2 kJ/mol at 298.15 K (–721.0 ± 1.2 kJ/mol at 0 K). In conclusion, the condensed-phase ATcT enthalpy of formation of oxalic acid is –829.7 ± 0.5 kJ/mol, and the resulting sublimation enthalpy is 98.1 ± 1.3 kJ/mol, both at 298.15 K.},

  doi          = {10.1021/acs.jpca.8b12329},

  journal      = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},

  number       = 16,

  volume       = 123,

  place        = {United States},

  year         = {2019},

  month        = {3}

}

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Title: Enthalpy of Formation of C2H2O4 (Oxalic Acid) from High-Level Calculations and the Active Thermochemical Tables Approach

Abstract

Citation Formats

Title: Enthalpy of Formation of C₂H₂O₄ (Oxalic Acid) from High-Level Calculations and the Active Thermochemical Tables Approach