A Raman Spectral Study of the Kinetics of Hydrolysis of Acetonitrile Catalyzed by Hg(II)

Sze, Yu-Keung; Irish, D. E.

doi:10.1139/v75-059

Cited by 20 publications

(11 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Further support for a surface hydrolysis reaction may be given by the results reported for the hydrolysis of acetonitrile . A slow hydrolysis was measured under mild conditions at room temperature catalyzed by Hg 2+ with the conversion of acetonitrile to acetamide in a high yield and purity as determined by Raman spectroscopic measurements.…”

Section: Resultsmentioning

confidence: 86%

Electrochemical and Fourier Transform Infrared Spectroscopy Studies of Benzonitrile Adsorption at the Au(111) Electrode

et al. 1997

View full text Add to dashboard Cite

The subtractively normalized interfacial Fourier transform infrared technique has been employed to study the adsorption of benzonitrile (BN) at the Au(111) electrode surface. The vibrational spectra have been used to study (i) the dependence of the band intensity on the surface coverage, (ii) the character of surface coordination, and (iii) the stability of adsorbed BN molecules at positive potentials. Our studies show that BN molecules are totally desorbed from the Au(111) surface at potentials more negative than -0.6 V (SCE) and they adsorb at the gold surface at more positive potentials. At potentials more negative than 0.05 V (SCE), the adsorption has an associative character. The BN molecules are initially oriented flat (π-bonded) on the electrode surface and progressively reorient from the flat to a vertical (N-bonded) state when the electrode potential approaches the potential of zero charge. This change of the surface coordination is gradual and apparently involves a progressive change of the tilt angle. When the potential is greater than 0.05 V (SCE), the character of BN adsorption becomes dissociative and the adsorbed molecules partially hydrolyze to form benzamide (BA). The adsorbed layer becomes a mixture of BN and BA molecules. The ratio of BN to BA molecules decreases as the electrode potential increases. The optical properties of CaF 2 prisms and flat windows have also been investigated. Our results show that flat windows should not be used to study physical features such as orientation and coordination of adsorbates. However, they are useful to extract quantitative information about the surface concentration of adsorbed species and to determine the composition of the interfacial region.

show abstract

Section: Resultsmentioning

confidence: 86%

Electrochemical and Fourier Transform Infrared Spectroscopy Studies of Benzonitrile Adsorption at the Au(111) Electrode

et al. 1997

View full text Add to dashboard Cite

show abstract

“…It is interesting that the properties of Br^nsted acids in these two solvents show a parallel behavior. For example, Kolthoff and Chantooni (30) concluded that in such systems the behavior of 2-PrOH is closer to that of -BuOH than to that of 1-PrOH, even though the dielectric constant of t-BuOH (12) is much lower than those of 2-PrOH (18) and 1-PrOH (20).…”

Section: Resultsmentioning

confidence: 99%

“…All potential measurements were made within 3 h after preparation of copper(II) solutions. In the case of water-acetonitrile and water-dimethylformamide mixtures, measurements were made immediately after preparation of solutions because it is conceivable that hydrolysis of acetonitrile and dimethylformamide will be catalyzed by copper(II) ion, as it is by mercury(II) (18).…”

mentioning

confidence: 99%

Copper ion-selective electrode for evaluation of free energies of transfer of copper(II) ion from water to other solvents

Coetzee¹,

Istone²

1980

Anal. Chem.

View full text Add to dashboard Cite

“…Hydrolysis of acetonitrile (to form acetic acid) occurs under acidic conditions but is very slow. 32 Furthermore, in this system only trace amounts of water and few protons are present. Reactions between formic acid and acetonitrile might reasonably be expected to lead to a product exhibiting an NH stretching mode.…”

Section: Formic Acid-acetonitrilementioning

confidence: 95%

Raman spectral study of ‘neat’ formic acid and aqueous and organic solutions of formic acid

Bartholomew¹,

Irish²

1999

J. Raman Spectrosc.

View full text Add to dashboard Cite

The Raman spectra of 'neat' formic acid and formic acid in several solvents (water, acetonitrile, 1,4dioxane and dichloromethane) were measured. In aqueous solution a very clear non-coincidence effect (NCE) indicative of resonance energy transfer was observed. The size of the NCE (ca 64 cm −1 ) indicates that strong intermolecular forces exist between the formic acid molecules, no doubt augmented by hydrogen bonding. In acetonitrile and 1,4-dioxane, two bands (at 1735 and 1765 cm −1 ) develop with dilution. The 1735 cm −1 band was assigned to 'free' formic acid monomer and the band at 1765 cm −1 to formic acid 'complexed' to the solvent. Liquid formic acid is unlike acetic acid in that it does not arrange itself into discrete, longlived dimers or polymers. It is viewed as a collection of monomeric units which interact through hydrogen bonding, thereby imposing local, short-term order in the liquid. This allows the resonance energy transfer to occur and results in a large non-coincidence effect.

show abstract

A Raman Spectral Study of the Kinetics of Hydrolysis of Acetonitrile Catalyzed by Hg(II)

Cited by 20 publications

References 10 publications

Electrochemical and Fourier Transform Infrared Spectroscopy Studies of Benzonitrile Adsorption at the Au(111) Electrode

Electrochemical and Fourier Transform Infrared Spectroscopy Studies of Benzonitrile Adsorption at the Au(111) Electrode

Copper ion-selective electrode for evaluation of free energies of transfer of copper(II) ion from water to other solvents

Raman spectral study of ‘neat’ formic acid and aqueous and organic solutions of formic acid

Contact Info

Product

Resources

About