Salt effects on the kinetics of dissociation of the pentacyano-4-cyanopyridineferrate(II) anion

Barrios, Antonio; Graciani, Marı́a del Mar; González-Jiménez, R.; Múñoz, Ernestina; Sánchez, Francisco; Moyá, Marı́a Luisa; Alshehri, Saad M.; Burgess, John

doi:10.1007/bf02910844

Cited by 18 publications

(9 citation statements)

References 15 publications

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“…Analogous plots for the 4-phenylpyridine and 4-t-butylpyridine complexes also showed remarkably good linear correlations, as reported earlier for the 4-cyanopyridine analogue. Using the method of estimation detailed earlier (8) to obtain 'surfaces of activation', and hence activation volumes, the values of AV ~ are 15.6, 12.5 and 9.1cm3mo1-1 for the 4,4'-bipyridyl, 4-phenylpyridine and 4-t-butylpyridine complexes, respectively. Earlier treatment of the results for the 4-cyanopyridine complex indicated AV ~ = 8 cm 3 tool-1 for its dissociation.…”

Section: Resultsmentioning

confidence: 99%

“…We have recently described how activation volumes may be estimated from salt effects on reactivities for one complex of this type, viz. the 4-cyanopyridine anion [Fe(CN)5(4CNpy)] s- (8). From rate constants determined in aqueous solutions of electrolytes at concentrations up to 6 mol dm-3 it proved possible, via the estimation of a 'surface of activation' from the correlation of rate constants with surface tension of the respective salt solutions, to determine an activation volume of 8cm 3mO1-1.…”

Section: Introductionmentioning

confidence: 99%

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Volumes of activation for dissociation of pentacyanoferrates(II) through pressure and salt effects on reactivity

Al-Alousy

Alshehri

Burgess

et al. 1993

Transition Met Chem

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Dependences of rate constants on pressure (up to 1 kbar) and on added salt concentration (up to 6.0moldm -3 LiNO3, NaNO3, NaC1, Na2SO4 or KNO3) have been established for dissociative substitution of pentacyanoferrates(II), [Fe(CN)sL] 3-with L = 4-cyanopyridine, 4,4'-bipyridyl, 4-phenylpyridine and 4-t-butylpyridine. Activation volumes derived directly from pressure effects, and indirectly from salt effects via surface tension dependences and derived surfaces of activation, are reported, compared and discussed.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Volumes of activation for dissociation of pentacyanoferrates(II) through pressure and salt effects on reactivity

Al-Alousy

Alshehri

Burgess

et al. 1993

Transition Met Chem

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“…The 10 À2 mol dm À3 stock solution of Br 2 was prepared using Br 2 ampoules and the resulting solution was standardized regularly against standard solution of sodium thiosulphate (Sarabhai M Chemicals, India) using KI (Merck) and starch solution. [31] The solutions of [Ru(CN) 5 H 2 O] 3À was prepared by mixing equi-molar concentration of K 4 Ru(CN) 6 and Br 2 in presence of at least ten fold excess of NaBr using the literature method. [12] The pH of the reaction mixture was adjusted to a desired value using KCl=HCl or Potassium hydrogen phthalate (A.R Qualigens Fine Chemicals, India) and HCl=NaOH buffer solutions as reported in literature.…”

Section: Methodsmentioning

confidence: 99%

“…[1] In recent years, the influence of medium on the reactivity of pentacyanoferrate(II) complexes, has been investigated extensively. [2][3][4][5][6][7][8][9][10] The formation of various pentacyanoruthenate(II) complexes with variety of nitrogen heterocyclic ligands were prepared much earlier, utilizing, [Ru(CN) 5 H 2 O 3À ]. [11] The ligand substitution reactions on substituted pentacyanoruthenate(II), [Ru(CN) 5 L] 3À complexes have attracted the attention of several investigators with respect to kinetic and spectroscopic investigations [12][13][14][15][16][17][18][19][20] in aqueous medium.…”

Section: Introductionmentioning

confidence: 99%

The Kinetics and Mechanism of Ligand Substitution Reaction of Aquapentacyanoruthenate(II) with Nitroso-R-salt and α-Nitroso-β-Naphthol in Presence of Anionic Surfactant Micelle

Naik

Singh

Asthana

2010

Journal of Dispersion Science and Technology

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The kinetics and mechanism of ligand substitution reaction of coordinated water in complex, [Ru(CN) 5 H 2 O] 3À by two incoming naphthalene substituted ligands [L n ], that is, L n ¼ nitroso-Rsalt (NRS) and a-nitroso-b-naphthol (aNbN) have been studied spectrophotometrically by following an increase in absorbance at k max ¼ 525 nm in aqueous medium in presence of anionic surfactant micelle, sodium dodecyl sulphate (SDS) at 25.0 AE 0.1 C as a function of pH, [nitro-Rsalt], [a-nitroso-b-naphthol], [Ru(CN) 5 H 2 O 3À ], [SDS] and ionic strength(I) under pseudo-firstorder conditions by taking excess [L]. The values of pseudo-first-order rate constants (k obs ) were evaluated from the slope of ln(A 1 À A t ) versus time plots for each variation. Both systems were found to follow a dissociative mechanism (D), through the formation of an intermediate, [Ru(CN) 5 ] 3À . The activation parameters, that is, enthalpy of activation (DH 6 ¼ ) and entropy of activation (DS 6 ¼ ) were computed from the slope and intercept of ln(k f /T) versus (1/T) plot, which support the proposed mechanistic scheme.

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“…Effects of reaction media on reactivity have been established and discussed for a variety of reactions of inorganic complexes in aqueous salt solutions [1]. Various solutes and/or co-solvents can increase or decrease the distribution of hydrogen bond in water.…”

Section: Introductionmentioning

confidence: 99%

Kinetic study of the base-catalyzed hydrolysis of novel high-spin hydrophobic Fe(II)-azomethine amino acid chelates: Salt and structure effects on the reactivity

et al. 2015

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The effect of salts on reactivity of basic hydrolysis of Fe(II) chelates bis(naphthylidenealanate) (nali), bis(naphthylidenephenylalanate) (nphali), bis(naphthylideneaspartate) (nasi), (naphthylidene histidinate) (nhi), bis(naphthylidene arginate) (nari) has been studied in aqueous media containing alkali metal halides, LiBr, NaCl, KBr, tetramethylammonium bromide (TMAB), tetraethylammonium bromide (TEAB), and tetrabutylammonium bromide (TBAB). The suggested mechanism of the base hydrolysis involves the parallel attack of OHions on Fe 2+ central atom attached to a singly bonded OHligand and dissociation of the first ligand as rate-determining step. Generally, presence of a salt markedly enhances the rate of the reaction compared to that without a salt. Such tendency is in accord of anionic nature of the transient species. Upon gradual addition of NaCl and NaBr the rate of the reaction decreases. On the contrary, addition of TMAB, TEAB and TBAB salts results in the initial rate increase followed by decrease when their concentration increases further.

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Salt effects on the kinetics of dissociation of the pentacyano-4-cyanopyridineferrate(II) anion

Cited by 18 publications

References 15 publications

Volumes of activation for dissociation of pentacyanoferrates(II) through pressure and salt effects on reactivity

Volumes of activation for dissociation of pentacyanoferrates(II) through pressure and salt effects on reactivity

The Kinetics and Mechanism of Ligand Substitution Reaction of Aquapentacyanoruthenate(II) with Nitroso-R-salt and α-Nitroso-β-Naphthol in Presence of Anionic Surfactant Micelle

Kinetic study of the base-catalyzed hydrolysis of novel high-spin hydrophobic Fe(II)-azomethine amino acid chelates: Salt and structure effects on the reactivity

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