α- And β Pahases of oxalic acid, H2C2O4: Vibrational spectra, normal-coordinate calculations, and intermolecular forces

Villepin, J. de; Novák, A.; Bougeard, D.

doi:10.1016/0301-0104(82)85170-7

Cited by 34 publications

(35 citation statements)

References 31 publications

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“…75). The Raman spectra of both polymorphs, including the low wavenumber region, were measured by DeVillepin and coworkers 76. The most intense Raman modes in α‐oxalic acid were found at 148, 130, 121 and 110 cm −1 at 300 K, which shifted by + 7 to + 13 cm −1 when cooling the sample to 90 K. This compares very well with the Raman spectrum of α‐carbonic acid (Fig.…”

Section: Resultssupporting

confidence: 73%

“…In addition, we report new low wavenumber Raman data for β‐H 2 CO 3 . While this type of Raman spectra has been reported between 30 and 100 years ago for other carboxylic or dicarboxylic acids such as formic acid,77, 78, oxalic acid,76, 79–81 malonic acid57, 79, 82 or acetic acid,67 the smallest organic acid, containing only one C atom, has eluded attempts of Raman characterization until 2009 14. Because of the possible astrophysical relevance of carbonic acid2–15 and the possibility of exploring astrophysical objects such as Mars using Raman spectroscopy,83–88 the data are of importance in possibly identifying α‐H 2 CO 3 in outer space.…”

Section: Discussion/conclusionmentioning

confidence: 72%

“…Data at 300 K are from Ref. 76 and are corrected by + 10 cm −1 in order to correct for the temperature change from 300 K to ∼80 K.…”

Section: Resultsmentioning

confidence: 99%

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Local structural order in carbonic acid polymorphs: Raman and FT‐IR spectroscopy

Mitterdorfer

Bernard

Klauser

et al. 2011

J Raman Spectroscopy

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Two different polymorphs of carbonic acid, α-and β-H 2 CO 3 , were identified and characterized using infrared spectroscopy (FT-IR) previously. Our attempts to determine the crystal structures of these two polymorphs using powder and thin-film X-ray diffraction techniques have failed so far. Here, we report the Raman spectrum of the α-polymorph, compare it with its FT-IR spectrum and present band assignments in line with our work on the β-polymorph [Angew. Chem. Int. Ed. 48 (2009) 2690-2694]. The Raman spectra also contain information in the wavenumber range ∼90-400 cm −1 , which was not accessible by FT-IR spectroscopy in the previous work. While the α-polymorph shows Raman and IR bands at similar positions over the whole accessible range, the rule of mutual exclusion is obeyed for the β-polymorph. This suggests that there is a center of inversion in the basic building block of β-H 2 CO 3 whereas there is none in α-H 2 CO 3 . Thus, as the basic motif in the crystal structure we suggest the cyclic carbonic acid dimer containing a center of inversion in case of β-H 2 CO 3 and a catemer chain or a sheet-like structure based on carbonic acid dimers not containing a center of inversion in case of α-H 2 CO 3 . This hypothesis is strengthened when comparing Raman active lattice modes at <400 cm −1 with the calculated Raman spectra for different dimers. In particular, the intense band at 192 cm −1 in β-H 2 CO 3 can be explained by the inter-dimer stretching mode of the centrosymmetric RC(OHO) 2 CR entity with R OH. The same entity can be found in gas-phase formic acid (R H) and in β-oxalic acid (R COOH) and produces an intense Raman active band at a very similar wavenumber. The absence of this band in α-H 2 CO 3 confirms that the difference to β-H 2 CO 3 is found in the local coordination environment and/or monomer conformation rather than on the long range.

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Section: Resultssupporting

confidence: 73%

Section: Discussion/conclusionmentioning

confidence: 72%

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Local structural order in carbonic acid polymorphs: Raman and FT‐IR spectroscopy

Mitterdorfer

Bernard

Klauser

et al. 2011

J Raman Spectroscopy

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“…32,37b,71 Oxalic acid is the shortest of the dicarboxylic acids and presents special challenges. The anhydrous solid shows polymorphism 72 and different saturation vapor pressures have been reported for the anhydrous α-orthorhombic and β-monoclinic forms. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 44 represent one standard error.…”

Section: Oxalic Acid (C 2 H 2 O 4 )mentioning

confidence: 96%

Saturation Vapor Pressures and Transition Enthalpies of Low-Volatility Organic Molecules of Atmospheric Relevance: From Dicarboxylic Acids to Complex Mixtures

Bilde

Barsanti

Booth³

et al. 2015

Chem. Rev.

212

307

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Introduction 4116 2. Theoretical Background and Framework for Atmospheric Aerosols 4117 2.1. Saturation Vapor Pressures 4117 2.2. Vapor−Liquid or Vapor−Solid Equilibria over Mixed Solutions 4118 2.3. Equilibria over Curved Surfaces 4118 2.4. Dynamic Evaporation and Condensation from and to an Aerosol Particle 4119 2.5. Ambient Partitioning 4120 3. Experimental Methods 4120 3.1. Knudsen-Cell-Based Methods 4121 3.1.1. Knudsen Mass Loss Methods 4121 3.

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“…Oxalic acid is special when compared to the higher mass dicarboxylic acids because in this case oxalic acid dihydrate forms in aqueous solutions and the solids exhibit polymorphism (de Villepin et al, 1982;Tanaka, 1984;Camus et al, 1997). Vapor pressure data of aqueous solutions are of special importance here, since they do not require any knowledge about crystalline stoichiometry nor crystalline form.…”

Section: Oxalic Acidmentioning

confidence: 99%

The vapor pressures and activities of dicarboxylic acids reconsidered: the impact of the physical state of the aerosol

et al. 2010

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Abstract. We present vapor pressure data of the C 2 to C 5 dicarboxylic acids deduced from measured evaporation rates of single levitated particles as both, aqueous droplets and solid crystals. The data of aqueous solution particles over a wide concentration range allow us to directly calculate activities of the dicarboxylic acids and comparison of these activities with parameterizations reported in the literature. The data of the pure liquid state acids, i.e. the dicarboxylic acids in their supercooled melt state, exhibit no even-odd alternation in vapor pressure, while the acids in the solid form do. This observation is consistent with the known solubilities of the acids and our measured vapor pressures of the supercooled melt. Thus, the gas/particle partitioning of the different dicarboxylic acids in the atmosphere depends strongly on the physical state of the aerosol phase, the difference being largest for the even acids.Our results show also that, in general, measurements of vapor pressures of solid dicarboxylic acids may be compromised by the presence of polymorphic forms, crystalline structures with a high defect number, and/or solvent inclusions in the solid material, yielding a higher vapor pressure than the one of the thermodynamically stable crystalline form at the same temperature.

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α- And β Pahases of oxalic acid, H2C2O4: Vibrational spectra, normal-coordinate calculations, and intermolecular forces

Cited by 34 publications

References 31 publications

Local structural order in carbonic acid polymorphs: Raman and FT‐IR spectroscopy

Local structural order in carbonic acid polymorphs: Raman and FT‐IR spectroscopy

Saturation Vapor Pressures and Transition Enthalpies of Low-Volatility Organic Molecules of Atmospheric Relevance: From Dicarboxylic Acids to Complex Mixtures

The vapor pressures and activities of dicarboxylic acids reconsidered: the impact of the physical state of the aerosol

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