Inorganic reactions of iodine(III) in acidic solutions and free energy of iodous acid formation

Schmitz, Guy

doi:10.1002/kin.20344

Cited by 24 publications

(17 citation statements)

References 49 publications

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“…The value of k À1 in Table 2 is the mean value of the results of Furrow 23 and Noszticzius et al 41 The value k1 2 = 1.9 Â 10 10 M À2 s À1 at zero ionic strength was obtained from other known kinetic and thermodynamic constants. 47 With g B 0.75 it gives k 2 = k1 2 g 2 = 1.0 Â 10 10 M À2 s À1 .…”

Section: Proposed Model For the Bray-liebhafsky Reactionmentioning

confidence: 98%

Iodine oxidation by hydrogen peroxide in acidic solutions, Bray-Liebhafsky reaction and other related reactions

Schmitz

2010

Phys. Chem. Chem. Phys.

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The kinetics of the iodine oxidation by hydrogen peroxide is a complicated function of the concentrations of iodine, hydrogen peroxide, perchloric acid and iodate. A proposed model in eight steps explains the new experimental results. It explains also the effect of the concentrations at the steady state of the hydrogen peroxide decomposition catalyzed by iodine and iodate. Without iodate added initially, the iodine oxidation by hydrogen peroxide is preceded by an induction period that depends on the oxygen concentration. A simple extension of the proposed model gives a semi-quantitative explanation of the oxygen effect and allows simulations of the Bray-Liebhafsky oscillations at 25 degrees C.

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Section: Proposed Model For the Bray-liebhafsky Reactionmentioning

confidence: 98%

Iodine oxidation by hydrogen peroxide in acidic solutions, Bray-Liebhafsky reaction and other related reactions

Schmitz

2010

Phys. Chem. Chem. Phys.

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“…k –5 was calculated using log K 5 = 12.9 in agreement with the accepted value

Δ G_{normalf}^{\circ}

(HgI + ) = 39.7 kJ/mol but very different from the negative value that Marković claims to have deduced from her measurements . Note also that the value

Δ G_{normalf}^{\circ}

(IO 2 H)) = –75 kJ/mol she used (with an error in the reference) for the calculation of K 1 is much too high and that a more likely estimate is –96 kJ/mol . The reaction

Hg (II) + {normalI}_{2} + {normalH}_{2} O ⇌ {HgI}^{+} + IOH + H^{+}

was included in the model, but, even diffusion controlled, it had no effect under our experimental conditions.…”

Section: Numerical Integrationsmentioning

confidence: 60%

“…The acidity constant of IO 2 H was never measured, but its order of magnitude is probably

K_{normala} {(IO}_{2} H ⇌ {IO}_{2}^{-} + H^{+}) = 10^{- 5}

to 10 −6 M .…”

Section: Discussionmentioning

confidence: 99%

“…However, as already mentioned by Noszticzius et al , the I(+3) solutions prepared in concentrated sulfuric acid contain always a small amount of I(+1) so that some HgI + is quickly produced at the beginning of the experiments by reactions (R2) and (R5). This initial I(+1) concentration depends critically on the concentration and purity of the sulfuric acid used to prepare the initial I(+3) solution . Third, k Mark is not equal to k 1 because the global reaction (S1) consumes 3 moles of IO 2 H so that – d[IO 2 H]/d t = 3 k 1 [IO 2 H] 2 .…”

Section: Introductionmentioning

confidence: 99%

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Kinetics of Iodous Acid Disproportionation

Schmitz

Furrow

2013

Int J of Chemical Kinetics

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The iodous acid disproportionation is autocatalytic, and it is not easy to measure the rate constant of the step 2IO 2 H → IO 3 − + IOH + H + separately. Hg(II) was used previously to suppress the autocatalytic pathway, but this method presents difficulties discussed in this work. A more effective method is the use of crotonic acid, an effective IOH scavenger. It suppresses side reactions, and a purely second-order rate law is obtained. The rate constant decreases from 5 to 0.2 M −1 s −1 when the sulfuric acid concentration increases from 0.08 to 0.60 M. The observed decrease could be explained if IO 2 − reacts faster than IO 2 H. This may have consequences for the mechanism of the oscillating Bray-Liebhafsky reaction. C 2013

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“…E 0 (Cl − /HOCl) is −1.49 V; 34 E 0 (HIO 2 /HOI) = 1.25 V, which is calculated from ΔG f 0 (HIO 2 )35 = −95 kJ M −1 and ΔG f 0 (HOI) 36 = −23.67 kcal M −1 . Potential data suggest that…”

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confidence: 99%

Chloride Ion Inhibition, Stirring, and Temperature Effects in an Ethylacetoacetate Briggs–Rauscher Oscillator in Phosphoric and Hydrochloric Acids in a Batch Reactor

Dutt

2019

J. Phys. Chem. B

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Briggs−Rauscher oscillating reaction has been investigated in hydrochloric acid media and in the presence of added chloride ions in phosphoric acid media in a batch reactor using ethylacetoacetate as the organic substrate. The changes in key oscillation parameters, namely, induction period, oscillation period, amplitude, and so forth, have been explained in terms of the steps of the skeleton mechanism proposed by Furrow and Noyes and by de Kepper and Epstein. In spite of several shortcomings as outlined in section 2 in the text, the same mechanistic steps are good enough to explain qualitatively most of the changes in oscillation parameters under different stirring rates and temperatures in phosphoric acid and hydrochloric acid media, particularly stirring effects explained well by the theory of imperfect mixing. Potential data indicate that 0.018 M HCl medium has the ability to exhibit near-zero/zero amplitudes before cessation of oscillations. Inhibition reactions from a low Cl − concentration in the 0.018 M HCl media appear to be responsible for this interesting dynamical transformation, as toward the end of oscillations, the difference between [I − ] and [I − ] crit [see eq J in the text] becomes very small because of depleted component chemicals due to chemical reactions.

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Inorganic reactions of iodine(III) in acidic solutions and free energy of iodous acid formation

Cited by 24 publications

References 49 publications

Iodine oxidation by hydrogen peroxide in acidic solutions, Bray-Liebhafsky reaction and other related reactions

Iodine oxidation by hydrogen peroxide in acidic solutions, Bray-Liebhafsky reaction and other related reactions

Kinetics of Iodous Acid Disproportionation

Chloride Ion Inhibition, Stirring, and Temperature Effects in an Ethylacetoacetate Briggs–Rauscher Oscillator in Phosphoric and Hydrochloric Acids in a Batch Reactor

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