Thallium(I) iodate solubility product and iodic acid dissociation constant from 2 to 75�C

Ramette, Richard W.; Palmer, Donald A.

doi:10.1007/bf00650371

Cited by 14 publications

(7 citation statements)

References 13 publications

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“…Step is the acid dissociation process of iodic acid. K a = 0.156 ± 0.002 M was established independently by Ramette and Palmer, as well as by Strong and Pethybridge at zero ionic strength. Considering that the ionic strength is set to 1.0 M in our experiments, K a = 0.32 M is used throughout the entire calculation process.…”

Section: Discussionmentioning

confidence: 76%

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On the Kinetics and Mechanism of the Thiourea Dioxide–Periodate Autocatalysis-Driven Iodine-Clock Reaction

et al. 2019

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The thiourea dioxide−periodate reaction has been investigated under acidic conditions using phosphate buffer within the pH range of 1.1−2.0 at 1.0 M ionic strength adjusted by sodium perchlorate. Absorbance−time series are monitored as a function of time at 468 nm, the isosbestic point of the I 2 −I 3 − system. The profile of these kinetic runs follows either sigmoidal-shaped or rise-and-fall traces depending on the initial concentration ratio of the reactants. The clock species iodine appears after a well-defined but reproducible time lag even in substrate excess, meaning that the system may be classified as an autocatalysis-driven clock reaction. It is also demonstrated that the age of the thiourea dioxide solution markedly shortens the Landolt time, suggesting that the original form of thiourea dioxide (TDO) rearranges into a more reactive form and reacts faster than the original one. The behavior found is consistent with that recently observed in other oxidation reactions of TDO. To characterize the system quantitatively, a 22-step kinetic model is constructed from adapting the kinetic model of the TDO−iodate reaction published recently by supplementing it with six different reactions of periodate. By the help of seven fitted rate coefficients a sound agreement between the measured and calculated absorbance− time traces is obtained.

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Section: Discussionmentioning

confidence: 76%

“…Step R2 is the acid dissociation process of iodic acid. K a = 0.156 ± 0.002 M was established independently by Ramette and Palmer, 27 as well as by Strong and Pethybridge 28…”

Section: ■ Discussionmentioning

confidence: 80%

On the Kinetics and Mechanism of the Thiourea Dioxide–Periodate Autocatalysis-Driven Iodine-Clock Reaction

et al. 2019

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“…Reaction is the well-established acid dissociation process of iodic acid. K a = 0.156 ± 0.002 M was established independently by Ramette and Palmer as well as by Strong and Pethybridge at zero ionic strength. Considering that it is 1.0 M in our experiments, we used K a = 0.32 M throughout the whole calculation process.…”

Section: Discussionmentioning

confidence: 82%

Autocatalysis-Driven Clock Reaction III: Clarifying the Kinetics and Mechanism of the Thiourea Dioxide–Iodate Reaction in an Acidic Medium

Csekõ

Gao

et al. 2019

J. Phys. Chem. A

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The thiourea dioxide−iodate reaction has been reinvestigated spectrophotometrically under acidic conditions using phosphoric acid−dihydrogen phosphate buffer within the pH range of 1.1−1.8 at 1.0 M ionic strength adjusted by sodium perchlorate and at 25 °C. The system was found to exhibit clock behavior, having a well-defined and reproducible time lag called Landolt time, though elementary iodine may even be detected in substrate excess; hence, under these conditions, the reaction can be classified as an autocatalysis-driven clock reaction. It is clearly demonstrated that the previously proposed kinetic model suffers from serious drawbacks from both theoretical and experimental points of view. The reaction may be characterized by either sigmoidal-shaped or rise-and-fall kinetic traces, depending on the initial concentration ratio of the reactants. Iodide significantly accelerates the appearance of the clock species iodine acting therefore as an autocatalyst. The age of stock TDO solution also has a great, so far completely overlooked impact on the Landolt time. On the basis of evaluating simultaneously the kinetic curves, a 16 step kinetic model including 5 well-known rapidly established equilibria is proposed with 7 fitted rate coefficients in which the rate coefficients of both forms of TDO were determined.

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“…Reaction (E) is the combination (A) – 5 × (D) – (F) + 5 × (G). The above values of K A and K D with 1/ K F = 0.156 M 50,51 and K G = 0.5 M −1 37 give The activity of the proton a

_{H^{+}}

is given by the Hammett acidity function 52,53 where γ B /γ

_{BH^{+}}

is the ratio of the activity coefficients of the nonprotonated and protonated forms of an indicator with the assumption that this ratio is the same for all indicators of the same charge type. We assume that it is also the ratio γ IOH /γ

_{IOH_{+}^{2}}

.…”

Section: Iodine(i) and Iodine(iii) In Concentrated Sulfuric Acid Solumentioning

confidence: 86%

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

Schmitz

2008

Int J of Chemical Kinetics

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Thallium(I) iodate solubility product and iodic acid dissociation constant from 2 to 75�C

Cited by 14 publications

References 13 publications

On the Kinetics and Mechanism of the Thiourea Dioxide–Periodate Autocatalysis-Driven Iodine-Clock Reaction

On the Kinetics and Mechanism of the Thiourea Dioxide–Periodate Autocatalysis-Driven Iodine-Clock Reaction

Autocatalysis-Driven Clock Reaction III: Clarifying the Kinetics and Mechanism of the Thiourea Dioxide–Iodate Reaction in an Acidic Medium

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

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