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Reactivity of Cyclanols Towards Quinaldinium Fluorochromate Oxidation.

Sekar KG, Sakthivel RV - J Solution Chem (2013)

Bottom Line: The order of reaction was found to be one with respect to oxidant and fractional with respect to the substrate and hydrogen ion concentrations.From the observed kinetic results a suitable mechanism was proposed.The relative reactivity order was found to be cyclohexanol < cyclopentanol < cycloheptanol < cyclooctanol.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, National College, Tiruchirappalli, 620001 Tamil Nadu India.

ABSTRACT
The kinetics of oxidation of cyclanols, viz., cyclohexanol, cyclopentanol, cycloheptanol and cyclooctanol by quinaldinium fluorochromate has been studied in aqueous acid medium at 313 K (±0.1 K). The cyclanols were converted to the corresponding cyclic ketones. The order of reaction was found to be one with respect to oxidant and fractional with respect to the substrate and hydrogen ion concentrations. Increase in the percentage of acetic acid increases the rate of reaction. The reaction mixture shows the absence of any free radicals in the reaction, which has ruled out the possibility of a one-electron transfer during the addition of acrylonitrile. The reaction has been studied at four different temperatures and the activation parameters were calculated. From the observed kinetic results a suitable mechanism was proposed. The relative reactivity order was found to be cyclohexanol < cyclopentanol < cycloheptanol < cyclooctanol. This was explained on the basis of I-strain theory.

No MeSH data available.


Related in: MedlinePlus

Plot of log10 k versus 1/D
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Fig3: Plot of log10 k versus 1/D

Mentions: An increase in the ionic strength of the medium from adding sodium perchlorate had no effect on the reaction rate indicating the involvement of a neutral molecule in the rate determining step. The rates were found to increase with increase in the percentage of acetic acid. A plot of log10 k versus D−1 is linear with a positive slope (Fig. 3). This suggests an interaction between a positive ion and neutral molecule. It also confirms the involvement of protonated Cr(VI) species in the rate determining step (Table 2).Fig. 3


Reactivity of Cyclanols Towards Quinaldinium Fluorochromate Oxidation.

Sekar KG, Sakthivel RV - J Solution Chem (2013)

Plot of log10 k versus 1/D
© Copyright Policy - OpenAccess
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC3824580&req=5

Fig3: Plot of log10 k versus 1/D
Mentions: An increase in the ionic strength of the medium from adding sodium perchlorate had no effect on the reaction rate indicating the involvement of a neutral molecule in the rate determining step. The rates were found to increase with increase in the percentage of acetic acid. A plot of log10 k versus D−1 is linear with a positive slope (Fig. 3). This suggests an interaction between a positive ion and neutral molecule. It also confirms the involvement of protonated Cr(VI) species in the rate determining step (Table 2).Fig. 3

Bottom Line: The order of reaction was found to be one with respect to oxidant and fractional with respect to the substrate and hydrogen ion concentrations.From the observed kinetic results a suitable mechanism was proposed.The relative reactivity order was found to be cyclohexanol < cyclopentanol < cycloheptanol < cyclooctanol.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, National College, Tiruchirappalli, 620001 Tamil Nadu India.

ABSTRACT
The kinetics of oxidation of cyclanols, viz., cyclohexanol, cyclopentanol, cycloheptanol and cyclooctanol by quinaldinium fluorochromate has been studied in aqueous acid medium at 313 K (±0.1 K). The cyclanols were converted to the corresponding cyclic ketones. The order of reaction was found to be one with respect to oxidant and fractional with respect to the substrate and hydrogen ion concentrations. Increase in the percentage of acetic acid increases the rate of reaction. The reaction mixture shows the absence of any free radicals in the reaction, which has ruled out the possibility of a one-electron transfer during the addition of acrylonitrile. The reaction has been studied at four different temperatures and the activation parameters were calculated. From the observed kinetic results a suitable mechanism was proposed. The relative reactivity order was found to be cyclohexanol < cyclopentanol < cycloheptanol < cyclooctanol. This was explained on the basis of I-strain theory.

No MeSH data available.


Related in: MedlinePlus