Electrolyte concentration effects in the formation of pentaaquochlorochromium(III) ion in aqueous perchloric acid solution

Hale, C. F.; King, Edward L.

doi:10.1021/j100865a035

Cited by 6 publications

(2 citation statements)

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“…The values for the stability constant of FeCl + have been reported in the range 0.13 ×10 −3 M −1 to 2.29 ×10 −3 M −1 , [17][18][19][20][21][22] while highly variable values have been reported for Cr complexes. [23][24][25][26] For instance, the stability constant of CrCl 2+ is found to be 0.22 M −1 in 1.0 M perchloric acid while it is reported to be 6 M −1 at 6.7 M perchloric acid at 40°C. 23,24 Although future quantitative analysis on the local chemistry of the pit is needed to justify the coordination num- ber as well as the stability constant of chloro-complexes, the K value for FeCl + will be obtained from the literature as mentioned above, while that of chromium complexes will be varied in a wider range with some values estimated from OLI Analyzer Studio and assuming all dissolved chromium can make complexes in some cases.…”

Section: Mass Transport Model In a One-dimensional Corrosion Pit-inmentioning

confidence: 99%

The Effect of Cation Complexation on the Predicted “B” Value in Galvele's Pit Model

Nguyen

Carcea

Ghaznavi

et al. 2019

J. Electrochem. Soc.

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A reaction-transport model in a one-dimensional pit geometry is constructed to study the effect of both cation complexation and concentration-dependent diffusivity on the IR potential drop at steady state and with an anodic limiting current density. When there is no cation complexation, the B value from Galvele's pitting potential equation remains at 59 mV, even when the ionic diffusivities are functions of chloride concentration. However, the B value is found to depend on the anionic charge and the formation of cation complexes. When doubly charged anions are assumed, the B value decreases to 30 mV as predicted from both numerical and analytical results. For the pit dissolution of Fe-17Cr alloy in chloride solution, the B value increases up to 100 mV, in agreement with experiments, assuming dissolved chromium can make cationic chloro-complexes. Such results can be rationalized via the distribution of potential and ionic fluxes at the pit mouth which not only maintain the critical chemistry for pit stability but also sustain the complexation reaction inside the pit.

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Section: Mass Transport Model In a One-dimensional Corrosion Pit-inmentioning

confidence: 99%

The Effect of Cation Complexation on the Predicted “B” Value in Galvele's Pit Model

Nguyen

Carcea

Ghaznavi

et al. 2019

J. Electrochem. Soc.

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show abstract

“…A reaction scheme embodying these concepts is given in eq [19][20], in which hydroxide ion was arbitrarily assigned the role of a bridging ligand on the trivalent ion. The rate constants in the mechanism are related to the empirical rate parameters by the equations / = f'K and h = h'Qa.…”

Section: Crcl2+mentioning

confidence: 99%

Oxidation-reduction catalysis of chromium(III) substitution. Kinetics of the reaction of vanadium(II) and chlorochromium(III) ions and its reverse. An example of nonsteady-state kinetics

Espenson¹,

Parker²

1968

J. Am. Chem. Soc.

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Studies have been carried out on the kinetics of three of the individual processes in the two-step sequence of reactions relating V(II), V(III), Cr(II), and Cr(III) in solutions containing chloride and/or perchlorate ions. The ions V2+ and CrCl2+ react in a second-order process, with a rate constant fa = e + //[H+]. In chloride solution the third-order rate constant for the reaction V3+ + Cr2+ + Cl" in which (H20)5CrCl2+ is formed is given by fa = g + /[ +], In perchlorate solution, the reaction of V3+ + Cr2+ follows a second-order rate expression, with the rate constant fa = qfr + [H+]). At 25.00 and ionic strength 2.50 M, values (units M and sec) are: e = 0.0384,/ = 0.0025, g = 4.3, h = 0.27, q = 1.09, and r = 0.12. The reaction of V2+ and CrCl2+ did not follow steady-state kinetics unless either V3+ or Cr2+ was added, since the latter ions were formed as intermediates but reacted only relatively slowly. From the steady-state data (V3+ or Cr2+ added) the best values of fa were derived. Known rate constants were used to find numerical solutions for the nonsteady-state situation by a Runge-Kutta iteration process on a computer. The interrelations of the various rate steps are demonstrated. The detailed mechanism, particularly the question of inneror outer-sphere electron transfer, is discussed with special emphasis on comparisons with reactions of established mechanism.

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Mechanisms of Electron Transfer Reactions: The Bridged Activated Complex

Haim¹

1983

Progress in Inorganic Chemistry

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Electrolyte concentration effects in the formation of pentaaquochlorochromium(III) ion in aqueous perchloric acid solution

Cited by 6 publications

References 0 publications

The Effect of Cation Complexation on the Predicted “B” Value in Galvele's Pit Model

The Effect of Cation Complexation on the Predicted “B” Value in Galvele's Pit Model

Oxidation-reduction catalysis of chromium(III) substitution. Kinetics of the reaction of vanadium(II) and chlorochromium(III) ions and its reverse. An example of nonsteady-state kinetics

Mechanisms of Electron Transfer Reactions: The Bridged Activated Complex

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