Temperature dependent near-UV molar absorptivities of aliphatic aldehydes and ketones in aqueous solution

Xu, Huan; Wentworth, Pamela J.; Howell, Noel W.; Joens, Jeffrey A.

doi:10.1016/0584-8539(93)80076-m

Cited by 33 publications

(42 citation statements)

References 32 publications

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“…We note that \documentclass{article}\pagestyle{empty}\begin{document}$\widetilde A\,^{1}A_{2}\leftarrow\widetilde X\,^{1}A_{2}$\end{document} is an electric dipole forbidden transition which is made weakly allowed by vibronic interaction. We also note that, in certain respects, acetone is the simplest carbonyl compound that is well suited for a study such as the present one because aldehyde spectra are complicated by gem ‐diol (acetal) formation 55, and formaldehyde spectra are additionally complicated by polymerization to paraformaldehyde 56.…”

Section: Applicationsmentioning

confidence: 95%

“…The solvatochromic shifts of acetone have been examined in several solvents, and we have chosen for study nine solvents for each of which we have two to six references 15, 55, 63–67. In all cases the various experimental references for a given solvent agree within ∼200–300 cm −1 .…”

Section: Applicationsmentioning

confidence: 99%

“…Table I gives VEM42 results for acetone from calculations in which all solvent molecules are represented by the continuum. Experimental results 15, 55, 63–67 are given for comparison.…”

Section: Applicationsmentioning

confidence: 99%

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Two-response-time model based on CM2/INDO/S2 electrostatic potentials for the dielectric polarization component of solvatochromic shifts on vertical excitation energies

Cramer

Truhlar

2000

Int. J. Quant. Chem.

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ABSTRACT:A model is presented for the electrostatic component of solvatochromic shifts on vertical electronic excitation energies. The model, called vertical electrostatic model 42 (VEM42), is based on representing the solute by a set of distributed atomic monopoles obtained by charge model 2 (CM2) and representing the solvent by its static and optical dielectric constants. The theory is applied here with intermediate neglect of differential overlap for spectroscopy-parameterization 2 (INDO/S2) configuration interaction wave functions. The model is implemented in the ZINDO electronic structure code package. We present illustrative applications to the singlet n → π * excitation of acetone in nine solvents. When the electrostatics are augmented by one-parameter estimates of dispersion and hydrogen-bonding contributions, the experimental solvatochromic shifts in the nine solvents are reproduced with a mean unsigned error of 65 cm −1 (0.2 kcal/mol). These calculations present a compelling picture of the quantitative origin of the solvatochromic red and blue shifts in this prototype n → π * excitation.

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Section: Applicationsmentioning

confidence: 95%

Section: Applicationsmentioning

confidence: 99%

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Two-response-time model based on CM2/INDO/S2 electrostatic potentials for the dielectric polarization component of solvatochromic shifts on vertical excitation energies

Cramer

Truhlar

2000

Int. J. Quant. Chem.

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“…Table 2 gives the most probable data for K hy = [hydrate]/[aldehyde] available in the literature. [31][32][33][34][35][36][37][38][39][40][41][42][43] Hydration in acidic solution is rapid compared with oxidation (k H = 500-800 dm 3 mol Ϫ 1 s Ϫ 1 for acetaldehyde 31,32,36,38,41 and 450-490 dm 3 mol Ϫ 1 s Ϫ 1 for propionaldehyde 32,36,41 ), i.e. the kinetic equation does not show whether the aldehyde or the hydrate is the reactive form.…”

Section: Kinetics In Acidic Solutionmentioning

confidence: 99%

“…For K hy we applied literature data [31][32][33][34][35][36][37][38][39][40][41][42][43] (given in Table 2); k 0 is the rate constant measured in neutral media, and therefore the two-parameter fitting of…”

Section: Kinetics In Alkaline Solutionmentioning

confidence: 99%

Oxidation of Aldehydes With Permanganate in Acidic and Alkaline Media

JÁKY¹,

SZAMMER²

1997

J. Phys. Org. Chem.

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The oxidation mechanism of aldehydes with permanganate was studied in acidic and alkaline media on acetaldehyde, propionaldehyde, pivalaldehyde (2,2Ј-dimethylpropanal) and chloral substrates. On addition of water to acetaldehyde dissolved in organic solvents the rate increased, and therefore it may be stated that the hydrate form is more reactive than the aldehyde form. Acid-catalysed nucleophilic addition of permanganate is suggested. In alkaline medium a mechanism based on electron abstraction from the alkoxy anion of the hydrate is proposed. Deprotonation constants of hydrate could be calculated..

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Oxidation of Aldehydes With Permanganate in Acidic and Alkaline Media

Jáky

Szammer

1997

J. Phys. Org. Chem.

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The oxidation mechanism of aldehydes with permanganate was studied in acidic and alkaline media on acetaldehyde, propionaldehyde, pivalaldehyde (2,2′‐dimethylpropanal) and chloral substrates. On addition of water to acetaldehyde dissolved in organic solvents the rate increased, and therefore it may be stated that the hydrate form is more reactive than the aldehyde form. Acid‐catalysed nucleophilic addition of permanganate is suggested. In alkaline medium a mechanism based on electron abstraction from the alkoxy anion of the hydrate is proposed. Deprotonation constants of hydrate could be calculated. © 1997 John Wiley & Sons, Ltd.

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Temperature dependent near-UV molar absorptivities of aliphatic aldehydes and ketones in aqueous solution

Cited by 33 publications

References 32 publications

Two-response-time model based on CM2/INDO/S2 electrostatic potentials for the dielectric polarization component of solvatochromic shifts on vertical excitation energies

Two-response-time model based on CM2/INDO/S2 electrostatic potentials for the dielectric polarization component of solvatochromic shifts on vertical excitation energies

Oxidation of Aldehydes With Permanganate in Acidic and Alkaline Media

Oxidation of Aldehydes With Permanganate in Acidic and Alkaline Media

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