Probing the balance of attraction and repulsion in binary mixtures of dimethyl sulfoxide and n-alcohols

Ellis, Andrew M.; Zehentbauer, Florian M.; Kiefer, Johannes

doi:10.1039/c2cp42902k

Cited by 12 publications

(10 citation statements)

References 25 publications

(33 reference statements)

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“…www.chemphyschem.org phase IR spectra of simple alcohols. [23] The calculated IR and Raman intensities are in good agreement with the main features of the experimental spectra.T he infrared spectra of the four cyanohydrins are characterized by very low intensities of the stretching bands and medium to high intensities of the other deformations bands. Fore xample, the stretching vibrations of the CH, OH, and CN bonds in different groups absorb weakly in almost all the studied compounds whereas their corresponding movementso fd eformation and bending are much more intense.…”

supporting

confidence: 72%

The Electronic Structure of Some Cyanohydrins—A Spectroscopically Under‐Investigated Family of Compounds

et al. 2015

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Cyanohydrins are usually formed by addition of hydrogen cyanide to aldehydes or ketones while the elimination of HCN from cyanohydrins is easily observed upon heating. The low thermal stability of these highly boiling compounds leads to difficult studies in the gas phase where partial or complete decomposition is usually observed. Consequently, the reported physicochemical properties of such compounds in the gas phase are still scarce. Keeping with this, four simple cyanohydrins, the glycolonitrile and methyl, vinyl and ethynyl derivatives, have been selected. These are possible candidates for the Interstellar Medium, where the corresponding aldehydes and HCN have been detected, and could have played an important role in prebiotic chemistry, as already proposed for some of them. Three well-suited spectroscopic techniques, namely, UV photoelectron, infrared, and Raman spectroscopies, in tandem with quantum calculations, have been chosen for the structure analysis. Photoelectron spectroscopy, successfully performed with gaseous compounds, provides the first comparative study on cyanohydrins in the gas phase.

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confidence: 72%

The Electronic Structure of Some Cyanohydrins—A Spectroscopically Under‐Investigated Family of Compounds

et al. 2015

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“…[18][19][20] It can be used to enhance the spectral resolution of the IR bands under study and look at changes in the dipole moment, reflecting changes in the charge distribution of the vibrating system. The procedure of calculating excess IR spectra was introduced by Li et al 18 lending the concept of thermodynamic excess properties.…”

Section: Excess Absorbance Spectramentioning

confidence: 99%

Characterization of gasoline/ethanol blends by infrared and excess infrared spectroscopy

Corsetti

Zehentbauer

McGloin

et al. 2015

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Fuels for automotive propulsion are frequently blends of conventional gasoline and ethanol.However, the effects of adding an alcohol to a petrochemical fuel are yet to be fully understood. We report Fourier-transform infrared spectroscopy (FTIR) of ethanol/gasoline mixtures with systematically varied composition. Frequencies shifts and excess infrared absorbance are analyzed in order to investigate the mixture behavior at the molecular level.The spectroscopic data suggest that the hydrogen bonding between ethanol molecules is weakened upon gasoline addition, but the hydrogen bonds do not disappear. This can be explained by a formation of small ethanol clusters that interact via Van der Waals forces with the surrounding gasoline molecules. Furthermore, approaches for measuring the chemical composition of ethanol/gasoline blends by FTIR are discussed. For a simplistic approach based on the Beer-Lambert relation, an optimized set of parameters for quantitative measurements are determined. The best compromise between measurement sensitivity and accuracy is found for the CO stretching mode of the alcohol. For the traditional method of calibrating the ratio of integrated band intensities of the CH and OH stretching regions it is found that narrowing the spectral window of the CH stretch can significantly improve the measurement sensitivity.

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“…While there is extensive information available on the macroscopic mixture behaviour of binary acetone/alcohol solutions, the ternary ABE system has not been studied in detail. The excess molar enthalpies for binary mixtures of acetone with primary aliphatic alcohols were found similar, which indicates a general similarity of the prevalent hydrogen bonding in the different mixtures . In contrast, the corresponding excess molar volumes show a rather different behaviour ––.…”

Section: Introductionmentioning

confidence: 84%

“…The excessm olare nthalpies for binary mixtures of acetonew ith primary aliphatic alcohols were found similar, [7a, c, f, g, i] which indicates ag eneral similarity of the prevalent hydrogen bondingi n the different mixtures. [8] In contrast, the corresponding excess molar volumes show ar ather different behaviour. [7b-d, j-r] While binary mixtures of acetone with methanol, ethanol and 1-propanol show negative excessm olar volumes, positive values have been reported for binary acetone/1-butanol and acetone/ Mixtures of acetone, butanol, and ethanol( ABE) are common intermediate productsi nt he production of biofuelsv ia biomass fermentation.…”

Section: Introductionmentioning

confidence: 99%

Molecular Solution Behaviour of an Intermediate Biofuel Feedstock: Acetone–Butanol–Ethanol (ABE)

Zehentbauer

Kiefer

2015

ChemPhysChem

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Mixtures of acetone, butanol, and ethanol (ABE) are common intermediate products in the production of biofuels via biomass fermentation. Their separation to yield, for example, bio-butanol, is still difficult due to the lack of a fundamental understanding of these mixtures at the molecular level. In order to bridge this gap, a detailed analysis of characteristic features of the vibrational spectrum is carried out. A systematic study of the binary solutions of acetone with ethanol and butanol does not only reveal a universal behaviour at the molecular level when acetone is mixed with short-chain alcohols, it also shows that the phenomena at a length scale between the molecules and in the macroscopic solution need to be taken into account to understand the structure-property relationships. The size of self-associated molecule clusters seems to determine whether or not a system exhibits an azeotrope. When a second alcohol is added to an acetone/alcohol solution, no additional non-idealities are induced, which is advantageous for modelling ternary ABE mixtures and for improving their processing in the production of biofuels.

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Probing the balance of attraction and repulsion in binary mixtures of dimethyl sulfoxide and n-alcohols

Cited by 12 publications

References 25 publications

The Electronic Structure of Some Cyanohydrins—A Spectroscopically Under‐Investigated Family of Compounds

The Electronic Structure of Some Cyanohydrins—A Spectroscopically Under‐Investigated Family of Compounds

Characterization of gasoline/ethanol blends by infrared and excess infrared spectroscopy

Molecular Solution Behaviour of an Intermediate Biofuel Feedstock: Acetone–Butanol–Ethanol (ABE)

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