The Kinetics of Formation and Aquation of Bis(oxalato)bis(dimethyl sulfoxide)chromate(III)

Ashley, Kenneth R.; Hamm, Randall E.

doi:10.1021/ic50044a003

Cited by 21 publications

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“…Equations similar to (3) were used for the determination of rate constants for biphasic reactions [10][11][12][13][14]. This analysis yielded two values for the rate constants, k 34 and k 45 , for the faster and the slower processes, respectively.…”

Section: Resultsmentioning

confidence: 99%

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Biphasic Oxidation of cis‐Diaquabis(1,10‐phenanthroline)chromium(III) by N‐Bromosuccinimide and the Formation of Chromium(IV) and Chromium(V)

Eljack

Sulfab

2016

Int J of Chemical Kinetics

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The oxidation of cis-diaquabis (1,10-phenanthroline) chromium(III) [cisCr III (phen) 2 (H 2 O) 2 ] 3+ by N -bromosuccinimide (NBS) to yield cis-dioxobis(1,10-phenanthroline)chromium(V) has been studied spectrophotometrically in the pH 1.57-3.56 and 5.68-6.68 ranges at 25.0°C. The reaction displayed biphasic kinetics at pH < 4.0 and a simple first order at the pH > 5.0. In the low pH range, the reaction proceeds by two successive steps; the first faster step corresponds to the oxidation of Cr(III) to Cr(IV), and the second slower one corresponds to the oxidation of Cr(IV) to Cr(V), the final product of the reaction. The formation of both Cr(IV) and Cr(V) has been detected by electron spin resonance (ESR). The ESR clearly showed the formation and decay of Cr(IV) as well as the formation of Cr(V). Each oxidation process exhibited a first-order dependence on the initial [Cr(III)]. The pseudo-first-order rate constants k 34 and k 45 , for the faster and slower steps, respectively, were obtained by a computer program using Origin7.0. Both rate constants showed first-order dependence on [NBS] and increased with increasing pH.

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Section: Resultsmentioning

confidence: 99%

“…From the reaction sequence shown above, the rate law for the fast step is given by Eq. (10). Since the reaction is first order, in each reactant the dependence of k 2 on [H + ] is given by Eq.…”

Section: (Ho)(o)]mentioning

confidence: 99%

Biphasic Oxidation of cis‐Diaquabis(1,10‐phenanthroline)chromium(III) by N‐Bromosuccinimide and the Formation of Chromium(IV) and Chromium(V)

Eljack

Sulfab

2016

Int J of Chemical Kinetics

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“…This type of biphasic kinetic profile has been simply described by a two‐step consecutive reaction scheme as shown in Eq. (2)

\begin{matrix} true \\ right normalA \overset{k_{1}}{\to} normalB \overset{k_{2}}{\to} normalC \end{matrix}

…”

Section: Resultsmentioning

confidence: 99%

“…(2)) is given by Eq. (3):

\begin{matrix} true \\ right A_{t} - A_{\infty} = a_{1} prefixexp (- k_{1} t) + a_{2} prefixexp (- k_{2} t) \end{matrix}

where A t and A ∞ are the absorbance values at time t and time infinity .…”

Section: Resultsmentioning

confidence: 99%

Kinetics and Mechanism of Oxidation of S₂O₃²⁻ by a Co‐Bound μ‐Amido‐μ‐Superoxo Complex

Singh

Das

Banerjee

et al. 2015

Int J of Chemical Kinetics

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In acetate buffer media (pH 4.5-5.4 2− ) and temperature (T), but it decreases with an increase in [H + ] and the ionic strength (I). Analysis of the log A t versus time data (A is the absorbance of 1 at time t) reveals that overall the reaction follows a biphasic consecutive reaction path with rate constants k 1 and k 2 and the change of absorbance is equal to {a 1 exp(-k 1 t) + a 2 exp(-k 2 t)}, where k 1 > k 2 .

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“…Krishnamuthy [1] has reviewed the substitution reactions of the oxalate complexes of chromium(III). However, very few papers have been published on the kinetics of Cr(C 2 O 4 ) 2 X 2 nmoiety; where X is any monodentate ligand other than water [2][3][4][5][6].…”

Section: Introductionmentioning

confidence: 99%

<b>Kinetics of substitution of cis-bis(malonato)diaquochromate(III) with glycine, DL-alanine and DL-phenylalanine in alkaline medium</b>

Mushini¹,

Ramam

Rao

2011

Bull. Chem. Soc. Eth.

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The kinetics of interaction among amino acids such as glycine, DL-alanine and DL-phenylalanine and cis-bis(malonato)diaquochromate(III) has been studied spectrophotometrically as a function of [glycine], [DL-alanine] and [DL-phenylalanine] in alkaline medium. The effect of pH, temperature and substrate was also studied. The substitution reaction has been found to proceed via two steps: amino acid dependent and amino acid independent path. In this process, it indicated that the substitution reaction occurs through an Ia mechanism in the amino acid dependent path and a dissociative mechanism in the independent path, showing the higher reactivity of single ended malonate complex.

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The Kinetics of Formation and Aquation of Bis(oxalato)bis(dimethyl sulfoxide)chromate(III)

Cited by 21 publications

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Biphasic Oxidation of cis‐Diaquabis(1,10‐phenanthroline)chromium(III) by N‐Bromosuccinimide and the Formation of Chromium(IV) and Chromium(V)

Biphasic Oxidation of cis‐Diaquabis(1,10‐phenanthroline)chromium(III) by N‐Bromosuccinimide and the Formation of Chromium(IV) and Chromium(V)

Kinetics and Mechanism of Oxidation of S₂O₃²⁻ by a Co‐Bound μ‐Amido‐μ‐Superoxo Complex

<b>Kinetics of substitution of cis-bis(malonato)diaquochromate(III) with glycine, DL-alanine and DL-phenylalanine in alkaline medium</b>

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The Kinetics of Formation and Aquation of Bis(oxalato)bis(dimethyl sulfoxide)chromate(III)

Cited by 21 publications

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Biphasic Oxidation of cis‐Diaquabis(1,10‐phenanthroline)chromium(III) by N‐Bromosuccinimide and the Formation of Chromium(IV) and Chromium(V)

Biphasic Oxidation of cis‐Diaquabis(1,10‐phenanthroline)chromium(III) by N‐Bromosuccinimide and the Formation of Chromium(IV) and Chromium(V)

Kinetics and Mechanism of Oxidation of S2O32− by a Co‐Bound μ‐Amido‐μ‐Superoxo Complex

<b>Kinetics of substitution of cis-bis(malonato)diaquochromate(III) with glycine, DL-alanine and DL-phenylalanine in alkaline medium</b>

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Kinetics and Mechanism of Oxidation of S₂O₃²⁻ by a Co‐Bound μ‐Amido‐μ‐Superoxo Complex