Estimation of the thermodynamic parameters of hydrogen bonding in alcohol solutions by the method of infrared spectroscopy

Vedernikova, E. V.; Гафуров, М. М.; Ataev, M. B.

doi:10.1007/s11182-011-9498-2

Cited by 10 publications

(7 citation statements)

References 10 publications

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“…Probing the interaction of acetonitrile with methanol and ethanol has been a challenging topic for a long time. ,,− Most of the efforts are made in liquid phase as all three are widely used as solvents. Recently, we have reported the solid-phase interaction of acetonitrile with water at low temperatures .…”

Section: Introductionmentioning

confidence: 99%

Interaction of Acetonitrile with Alcohols at Cryogenic Temperatures

et al. 2017

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Temperature-dependent interaction of acetonitrile with methanol and ethanol, as codeposited and sequentially deposited films, was studied in the 10–130 K window, in ultra high vacuum. Films in the range of 50–100 monolayers were investigated using temperature-dependent reflection–absorption infrared spectroscopy (RAIRS), Cs+ ion scattering mass spectrometry, and temperature-programmed desorption (TPD). Acetonitrile interacts with methanol and ethanol through intermolecular hydrogen bonding. When a codeposited system was annealed, acetonitrile underwent a phase segregation at 110 K, and large changes in the infrared spectrum were observed. The OH stretching of methanol gave two peaks characteristic of the change to the α-phase of methanol, while ethanol gave three peaks at the same temperature. The surface composition of the systems probed by 40 eV Cs+ scattering showed that both the alcohols and the acetonitrile were of equal intensity below 110 K, while above 110 K the intensity of the latter went down substantially. We find that the presence of acetonitrile does not allow ethanol to undergo complete phase transition prior to desorption, while methanol could do so. This behavior is explained on the basis of the size, extent of hydrogen bonding, and phase transition temperature, of the two alcohols. Additional peaks in the hydroxyl region observed in alcohols in the 110–130 K window may be used as a signature of the presence of acetonitrile mixed with alcohol, especially ethanol, and hence this may be used in observational studies of such molecular environments.

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Section: Introductionmentioning

confidence: 99%

Interaction of Acetonitrile with Alcohols at Cryogenic Temperatures

et al. 2017

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“…While reorientational and H-bond dynamics are naturally related, their connection varies with the alcohol ( vide infra ). This role of alcohols as commonly used solvents in organic transformations along with the presence of OH groups in biological macromolecules has spurred significant interest in understanding hydroxyl reorientation and H-bond dynamics in alcohols. − …”

Section: Introductionmentioning

confidence: 99%

Reorientation of Isomeric Butanols: The Multiple Effects of Steric Bulk Arrangement on Hydrogen-Bond Dynamics

et al. 2015

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Molecular dynamics simulations are used to investigate OH reorientation in the four isomeric butanols in their bulk liquid state to examine the influence of the arrangement of the steric bulk on the alcohol reorientational and hydrogen-bond (H-bond) dynamics. The results are interpreted within the extended jump model in which the OH reorientation is decomposed into contributions due to "jumps" between H-bond partners and "frame" reorientation of the intact H-bonded pair. Reorientation is fastest in iso-butanol and slowest in tert-butanol, while sec- and n-butanol have similar reorientation times. This latter result is a fortuitous cancellation between the jump and frame reorientation in the two alcohols. The extended jump model is shown to provide a quantitative description of the OH reorientation times. A detailed analysis of the jump times shows that a combination of entropic, enthalpic, and dynamical factors, including transition state recrossing effects, all play a role. A simple model based on the liquid structure is proposed to estimate the energetic and entropic contributions to the jump time. This represents the groundwork for a predictive model of OH reorientation in alcohols, but additional studies are required to better understand the frame reorientation and transition state recrossing effects.

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“…The former feature is ∼178 cm −1 lower than the free OH stretch of cis-cyclohexane-1,3-diol in CCl 4 24 due, at least in large part, to the hydrogen bond-accepting ability of the acetonitrile cosolvent. 25 Gas-phase B3LYP/6-31+G(d,p) computations reproduce the experimental spectrum nevertheless, and the predicted bands at 3492, 3024, 2945, and 2915 cm −1 are within 5 to 59 cm −1 of the observed frequencies.…”

Section: ■ Introductionmentioning

confidence: 69%

Power of a Remote Hydrogen Bond Donor: Anion Recognition and Structural Consequences Revealed by IR Spectroscopy

et al. 2014

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Natural and synthetic anion receptors are extensively employed, but the structures of their bound complexes are difficult to determine in the liquid phase. Infrared spectroscopy is used in this work to characterize the solution structures of bound anion receptors for the first time, and surprisingly only two of three hydroxyl groups of the neutral aliphatic triols are found to directly interact with Cl(–). The binding constants of these triols with zero to three CF3 groups were measured in a polar environment, and KCD3CN(Cl(–)) = 1.1 × 10(6) M(–1) for the tris(trifluoromethyl) derivative. This is a remarkably large value, and high selectivity with respect to interfering anions such as, Br(–), NO3(–) and NCS(–) is also displayed. The effects of the third “noninteracting” hydroxyl groups on the structures and binding constants were also explored, and surprisingly they are as large or larger than the OH substituents that hydrogen bond to Cl(–). That is, a remote hydroxyl group can play a larger role in binding than two OH substituents that directly interact with an anionic center.

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Estimation of the thermodynamic parameters of hydrogen bonding in alcohol solutions by the method of infrared spectroscopy

Cited by 10 publications

References 10 publications

Interaction of Acetonitrile with Alcohols at Cryogenic Temperatures

Interaction of Acetonitrile with Alcohols at Cryogenic Temperatures

Reorientation of Isomeric Butanols: The Multiple Effects of Steric Bulk Arrangement on Hydrogen-Bond Dynamics

Power of a Remote Hydrogen Bond Donor: Anion Recognition and Structural Consequences Revealed by IR Spectroscopy

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