Thermodynamic properties of pyruvic acid and its methyl ester

Emel′yanenko, Vladimir N.; Туровцев, В. В.; Fedina, Yulia A.

doi:10.1016/j.tca.2018.05.009

Cited by 9 publications

(4 citation statements)

References 11 publications

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“…Calculated electron affinities at the CCSD(T)/CBS (aug-cc-pVXZ X = D,T,Q)//B3LYP/aug-cc-pVTZ level and using the G3 model chemistry (second-order Møller–Plesset perturbation theory (MP2) geometry) are in good agreement, while that calculated using the G4 model chemistry (density functional theory (DFT) geometry) is somewhat larger. The calculated energy for the trans–trans conformer, which Perkins et al estimate as a 3% contribution in ambient PA, was lower by 0.2 eV among the different calculations, in agreement with the G4 results of Emel’yaneko et al Our G4 calculations also provided the gas-phase acidity of PA at 298 K, with Δ G acid (327.3 kcal mol –1 ) and Δ H acid (335.6 kcal mol –1 ) in excellent agreement with the measurements of Graul et al, 326.5 ± 1.6 and 333.4 ± 1.6, respectively . The G3 method yielded values of 337.3 and 329.1, respectively.…”

Section: Discussionsupporting

confidence: 88%

Thermal Electron Attachment to Pyruvic Acid, Thermal Detachment from the Parent Anion, and the Electron Affinity of Pyruvic Acid

et al. 2022

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The kinetics of electron attachment to pyruvic acid (CH 3 COCOOH) and thermal detachment from the resulting parent anion were measured from 300−515 K using a flowing afterglow�Langmuir probe apparatus. An adiabatic electron affinity (EA) for pyruvic acid was derived, 0.84 ± 0.02 eV. Electron attachment rate constants to pyruvic acid of 2.1 × 10 −8 and 1.2 × 10 −8 were measured at 300 and 400 K, respectively. Rate constants at higher temperatures are less well-defined due to possible contributions from attachment to zymonic open ketone, an endemic impurity in pyruvic acid. Similarly, unimolecular detachment rates are complicated by secondary proton transfer reaction of the pyruvic acid anion with pyruvic acid to yield an 87 Da anion. The possible contributions from these chemistries are considered, and in all cases the equilibrium constant between attachment and detachment remains well-defined, allowing for determination of the EA.

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Section: Discussionsupporting

confidence: 88%

Thermal Electron Attachment to Pyruvic Acid, Thermal Detachment from the Parent Anion, and the Electron Affinity of Pyruvic Acid

et al. 2022

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“…Processes reducing the volatility of these compounds can increase the fraction of organic mass that remains in the particle phase after water evaporation. Among these is pyruvic acid, with a vapor pressure of ∼10 2 Pa at 20 °C. , Aqueous OH-radical initiated oxidation, dark acid-catalyzed accretion reactions, and salt formation of pyruvic acid (not shown) have the potential to reduce the volatility of pyruvic acid. Aqueous OH oxidation of pyruvic acid forms acetic acid, glyoxylic acid, and subsequently oxalic acid, whose vapor pressure is in the semivolatile range ( p o = 10 –2 to 10 –4 Pa). , The preference of oxalic acid for the particle phase in the atmosphere is likely due to the formation of low-volatility oxalate salts or complexes. ,, This work suggests that evaporating pyruvic acid solution droplets at aerosol-, fog-, and cloud-relevant concentrations and atmospheric temperatures (10–25 °C) in the absence of an inorganic catalyst leads to the formation of acetals and/or cyclic dimers with estimated vapor pressures of 4 × 10 –5 Pa and 10–30% volumetric yields.…”

Section: Resultsmentioning

confidence: 99%

“…Among these is pyruvic acid, with a vapor pressure of ∼10 2 Pa at 20 °C. 103,104 Aqueous OH-radical initiated oxidation, dark acidcatalyzed accretion reactions, and salt formation of pyruvic acid (not shown) have the potential to reduce the volatility of pyruvic acid. Aqueous OH oxidation of pyruvic acid forms acetic acid, glyoxylic acid, and subsequently oxalic acid, whose vapor pressure is in the semivolatile range (p o = 10 −2 to 10 −4 Pa).…”

Section: Edb Evaporation Experimentsmentioning

confidence: 99%

Volatility Change during Droplet Evaporation of Pyruvic Acid

Petters

Hilditch

Tomaz

et al. 2020

ACS Earth Space Chem.

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Atmospheric water-soluble organic gases such as pyruvic acid are produced in large quantities by 13 photochemical oxidation of biogenic and anthropogenic emissions and undergo water-mediated 14 reactions in aerosols and hydrometeors. These reactions can contribute to aerosol mass by forming 15 less volatile compounds. While progress is being made in understanding the relevant aqueous 16 chemistry, little is known about the chemistry that takes place during droplet evaporation. Here we 17 examine the evaporation of aqueous pyruvic acid droplets using both the Vibrating Orifice Aerosol 18 Generator (VOAG) and an electrodynamic balance (EDB). In some cases pyruvic acid was first 19 oxidized by OH radicals. The evaporation behavior of oxidized mixtures was consistent with 20 expectations based on known volatilities of reaction products. However, independent VOAG and 21 EDB evaporation experiments conducted without oxidation also resulted in stable residual 22 particles; the estimated volume yield was 10-30% of the initial pyruvic acid. Yields varied with 23 temperature and pyruvic acid concentration across cloud, fog, and aerosol-relevant concentrations. 24The formation of low volatility products, likely cyclic dimers, suggests that pyruvic acid accretion 25 reactions occurring during droplet evaporation could contribute to the gas-to-particle conversion 26 of carbonyls in the atmosphere. 27 mass. [4][5][6] However, the contribution of aqueous reactions to SOA mass remains uncertain due in 35 part to a limited understanding of precursors and limited laboratory results to parameterize 36 models. 1,[7][8][9][10][11] Quantifying the impacts of aqueous and multiphase chemistry on aerosol mass 37 remains challenging, and a more detailed understanding of product volatility is needed.A significant fraction of low molecular weight acids, aldehydes and carbonyls dissolve into 39 cloud or fog droplets. In the absence of additional reactions, these WSOGs largely evaporate 40 during water evaporation; the trace amounts that remain in the aerosol phase are determined by 41 their partial pressure in the gas phase and activity in the aerosol matrix. However, multiphase 42 reactions can generate low-volatility products that are retained in the equilibrated aerosol. Several 43 important criteria determine whether aqueous processing can appreciably increase SOA mass: (1) 44 the precursor must be abundant, (2) it must have a high vapor pressure before aqueous reactions, 45(3) it must have a high Henry's law coefficient and thus strongly partition into water, and (4) it 46 must react in the aqueous phase to form less volatile products. 47

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“…The Pvap(PyA) at a specific T was calculated using Eq. ( 3) with a literature value for the standard molar enthalpy of vaporization ΔH vap(PyA) at 298.15 K of 53.6 ± 2.1 kJ mol −1 (Emel'yanenko et al, 2018). The calculation used a Pvap of 289.9±7.3 Pa at a temperature of 308.2 K (Emel'yanenko et al, 2018).…”

Section: Pyruvic Acid (Pya)mentioning

confidence: 99%

A Nitrate Ion Chemical Ionization Atmospheric Pressure interface Time-of-Flight Mass Spectrometer (NO₃⁻ ToFCIMS): calibration and sensitivity study

Alage,

Michoud,

Harb

et al. 2024

Preprint

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Abstract. Volatile organic compounds (VOCs) play a key role in tropospheric chemistry, giving rise to secondary products such as highly oxygenated organic molecules (HOMs) and secondary organic aerosols (SOA). HOMs, a group of low-volatility gas-phase products, are formed through the autoxidation process of peroxy radicals (RO2) originating from the oxidation of VOCs. The measurement of HOMs is made by a NO3¯ ToFCIMS instrument, which also detects other species like small highly oxygenated VOCs (e.g. dicarboxylic acids) and sulfuric acid (H2SO4). The instrument response to HOMs is typically estimated using H2SO4, as HOMs are neither commercially available nor easily synthesized in the laboratory. The resulting calibration factor is then applied to quantify all species detected using this technique. In this study, we explore the sensitivity of the instrument to commercially available small organic compounds, primarily dicarboxylic acids, given the limitations associated with producing known amounts of HOMs for calibration. We compare these single compound calibration factors to the one obtained for H2SO4 under identical operational conditions. The study found that the sensitivity of the NO3¯ ToFCIMS varies depending on the specific type of organic compound, illustrating how a single calibration factor derived from sulfuric acid is clearly inadequate for quantifying all detected species using this technique. The results highlighted substantial variability in the calibration factors for the tested organic compounds, with 4-nitrocatechol exhibiting the highest sensitivity, and pyruvic acid the lowest. The obtained sulfuric acid calibration factor agreed well with the previous values from the literature. In summary, this research emphasized the need to develop reliable and precise calibration methods for progressively oxygenated reaction products measure with NO3¯ CIMS, for example, HOMs.

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Thermodynamic properties of pyruvic acid and its methyl ester

Cited by 9 publications

References 11 publications

Thermal Electron Attachment to Pyruvic Acid, Thermal Detachment from the Parent Anion, and the Electron Affinity of Pyruvic Acid

Thermal Electron Attachment to Pyruvic Acid, Thermal Detachment from the Parent Anion, and the Electron Affinity of Pyruvic Acid

Volatility Change during Droplet Evaporation of Pyruvic Acid

A Nitrate Ion Chemical Ionization Atmospheric Pressure interface Time-of-Flight Mass Spectrometer (NO₃⁻ ToFCIMS): calibration and sensitivity study

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Thermodynamic properties of pyruvic acid and its methyl ester

Cited by 9 publications

References 11 publications

Thermal Electron Attachment to Pyruvic Acid, Thermal Detachment from the Parent Anion, and the Electron Affinity of Pyruvic Acid

Thermal Electron Attachment to Pyruvic Acid, Thermal Detachment from the Parent Anion, and the Electron Affinity of Pyruvic Acid

Volatility Change during Droplet Evaporation of Pyruvic Acid

A Nitrate Ion Chemical Ionization Atmospheric Pressure interface Time-of-Flight Mass Spectrometer (NO3− ToFCIMS): calibration and sensitivity study

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A Nitrate Ion Chemical Ionization Atmospheric Pressure interface Time-of-Flight Mass Spectrometer (NO₃⁻ ToFCIMS): calibration and sensitivity study