Hydrogen-bonded species of acetic acid in inert solvents

Goldman, Mark A.; Emerson, Merle T.

doi:10.1021/j100638a008

Cited by 27 publications

(21 citation statements)

References 8 publications

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“…This has been found to be true of the self-association behavior of carboxylic acids as well, which can also form hydrogen bonded cyclic dimers. 10 A study of a lactam in a variety of nonpolar solvents should indicate if the tendency to form trimers, tetramers, or other higher oligomers is a general phenomenon of these compounds or if their behavior is strongly dependent upon specific solute-solvent interactions. In view of our finding that the system of 2-pyrrolidinone in CCI4 is best described by a monomer-dimer-trimer model7 it was decided to reinvestigate the dielectric polarization of this lactam in benzene and, in addition, to examine the infrared and Raman spectra for the presence of oligomers higher than the dimer.…”

Section: Introductionmentioning

confidence: 99%

Self-association of 2-pyrrolidinone. 2. Spectral and dielectric polarization studies of benzene solutions

Walmsley¹

1978

J. Phys. Chem.

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The self-association of 2-pyrrolidinone in benzene has been investigated using infrared and Raman spectroscopy and dielectric polarization measurements. For solutions up to 0.5 M this system is best described as an equilibrium between monomer and cyclic dimer solute species. No evidence for the presence of trimers or other higher n-mers was found. Using a computer fit of the dielectric polarization data a dimerization constant of 33 ± 5 M"1 and dipole moments of 3.91 ± 0.20 D for the monomer and 2.06 ± 0.23 D for the dimer were determined. The Raman spectra confirm that the major associated species is a cyclic dimer. The presence of acyclic dimers cannot be ruled out, but on the basis of all the experimental measurements it is concluded that the concentration must be small, if it exists at all in this solvent.

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Section: Introductionmentioning

confidence: 99%

Self-association of 2-pyrrolidinone. 2. Spectral and dielectric polarization studies of benzene solutions

Walmsley¹

1978

J. Phys. Chem.

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“…[1][2][3] It is well known that carboxylic acids form in the gas phase and solution cyclic structure with two very strong O-H … O=C hydrogen bonds. Several experimental studies such as IR spectroscopy, 4,5 NMR spectroscopy, [6][7][8] X-ray crystallography, [9][10][11] microwave spectroscopy 12 vapor-density measurements 13 and thermal conductivity measurements 14 indicate that carboxylic acids form hydrogen-bonded cyclic dimers. In addition the characterization of the hydrogen bonding interaction between carboxylic acids has been studied by a lot of theoretical calculations.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Studies of Hydrogen Bond Interactions in Fluoroacetic Acid Dimer

Chermahini¹,

Mahdavian²,

Teimouri³

2010

Bulletin of the Korean Chemical Society

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Ab initio and density functional theory methods have been employed to study all theoretically possible conformers of fluoroacetic acid. Molecular geometries and energetic of cis and trans monomers and cis dimers in gaseous phase have been obtained using HF, B3LYP and MP2 levels of theory, implementing 6-311++G(d,p) basis set. It was found that cis rotamers are more stable. In addition, it was found that in comparison with acetic acid the strength of hydrogen bonding in fluoroacetic acid decreased. The infrared spectrum frequencies and the vibrational frequency shifts are reported. Natural population and atom in molecule analysis performed to predict electrostatic interactions in the cyclic H-bonded complexes and charges. The proton transfer reaction is studied and activation energy is compared with acetic acid proton transfer reaction.

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“…[5][6][7][8][9][10][11][12] Many qualitative and quantitative studies have been carried out using different experimental techniques to understand acetic acid structural forms as well as their compositions in nonpolar media. 7,10,11,13,14 One of the most utilized techniques to reveal the structure of a molecule is through dielectric measurement. Indeed, some dielectric measurements of acetic acid solutions in some nonpolar solvents have been performed in order to determine the dipole moment of acetic acid monomer and cyclic dimer.…”

Section: Introductionmentioning

confidence: 99%

Experimental Dipole Moments for Nonisolatable Acetic Acid Structures in a Nonpolar Medium. A Combined Spectroscopic, Dielectric, and DFT Study for Self-Association in Solution

2008

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Acetic acid can exist in many possible structural forms depending on its surrounding medium. A recently developed inverse problem methodology (J. Phys. Chem. B 2007, 111, 13064-13074) was utilized in order to elucidate acetic acid structures in a dilute nonpolar medium. In this regard, simultaneous and stopped-flow measurements of the bulk solution densities, refractive indices, relative permittivities, and IR spectra of acetic acid in toluene were performed at several different concentrations in a semibatch closed-loop experimental setup at 298.15 K and 0.1013 MPa. This combined IR spectroscopic and dielectric, density, and refractive index analysis was employed in order to distinguish acetic acid structures and to further determine the dipole moments of the monomer, cyclic dimer, and "lumped-sum" open dimers. The infrared spectra were first analyzed to provide qualitative understanding as well as quantitative estimates for each acetic acid species. Subsequently, the dipole moments of these species were calculated using a direct approach which was primarily based on response surface models. The present method allows the determination of individual dipole moments not only for the monomer but also for the cyclic dimer and the open dimer. The results obtained from this study experimentally show that the cyclic dimer with centrosymmetric structure has a dipole moment approximately 0 D. The results also suggest that the linear dimers are present as mixtures of linear dimers structures. The existence of the linear dimers mixture was also indicated by the experimental infrared analysis of the OH-stretching region (particularly for measurements in n-hexane as solvent) and comparison of these spectra with DFT predictions. Finally, the present methodology which incorporates simultaneous physicochemical and spectroscopic analysis is undoubtedly useful for physicochemical characterization for other nonisolatable solute species and self-associated structures in solution.

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Hydrogen-bonded species of acetic acid in inert solvents

Cited by 27 publications

References 8 publications

Self-association of 2-pyrrolidinone. 2. Spectral and dielectric polarization studies of benzene solutions

Self-association of 2-pyrrolidinone. 2. Spectral and dielectric polarization studies of benzene solutions

Theoretical Studies of Hydrogen Bond Interactions in Fluoroacetic Acid Dimer

Experimental Dipole Moments for Nonisolatable Acetic Acid Structures in a Nonpolar Medium. A Combined Spectroscopic, Dielectric, and DFT Study for Self-Association in Solution

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