ION PAIR EFFECTS IN THE REACTION BETWEEN POTASSIUM FERROCYANIDE AND POTASSIUM PERSULFATE

1966 ◽  
Vol 44 (4) ◽  
pp. 437-445 ◽  
Author(s):  
R. W. Chlebek ◽  
M. W. Lister
Keyword(s):  
Ionic Strength ◽  
Rate Constants ◽  
Equilibrium Constants ◽  
Ion Pairs ◽  
Ion Pair ◽  
Glass Electrode ◽  
Potassium Ferrocyanide ◽  
Potassium Persulfate ◽  
Ion Concentration ◽  
True Rate

The rate of the reaction between potassium ferrocyanide and potassium persulfate has been measured over a range of conditions. The rate is dependent on the potassium ion concentration, and it is shown that this is explained if it is assumed that KFe(CN)63− and KS2O8− are the reacting species. The equilibrium constants governing the formation of these ion pairs were measured with a cation-sensitive glass electrode. Similar constants for the products KFeCCN6)2− and KSO4−, and also for KNO3, were measured. From these equilibrium constants, the true rate constants of the reaction can be obtained, and it is shown that these vary with ionic strength in the manner predicted by Brönsted's equation.

The trans effect in cobalt(III) complexes. Kinetics and mechanism of substitution of cobalt(III) sulphito complexes

1978 ◽  
Vol 31 (3) ◽  
pp. 561 ◽  
Author(s):  
JK Yandell ◽  
LA Tomlins
Keyword(s):  
Ionic Strength ◽  
Water Molecule ◽  
Rate Constants ◽  
Equilibrium Constants ◽  
Ion Concentration ◽  
Nitrite Ion ◽  
Hydrogen Ion Concentration ◽  
Thiocyanate Ion ◽  
Order Rate ◽  
Incoming Ligand

Equilibrium constants K and rate constants kf have been measured, at 25°C and ionic strength of 1.0, for the substitution of the labile water molecule in trans-[aquabis(ethylenediamine)sulphito-cobalt(III)] ion by thiosulphate ion (K = 1.8×102 mol-1 1., kf = 1.27×103 mol-1 1. s-1), thiocyanate ion (2.5×103, 2.75×102), nitrite ion (1.0×103, 2.06×102), azide ion (2.9×102, 2.4×102) ferricyanide ion (-, 1.72×103), hydrogen azide (< 1.2,1.4×10), ammonia (3.0, 6.7) and imidazole (2.6×102, 5.2). ��� The correlation of these rate constants with charge on the incoming ligand, as well as a decrease in the apparent second-order rate constants observed at high concentrations of the anionic ligands, requires a rapid outer-sphere pre-equilibrium step followed by a rate- determining dissociative interchange of the incoming ligand with the bound water molecule. The activation energy of the thiocyanate substitution was found to be 48 kJ mol-1. Aquation of cis- [azidobis(ethylenediamine)-sulphitocobalt(III)] ion, in the range of hydrogen ion concentration between 10-2 and 0.2 M, was found to give the trans-aquasulphito complex with a first-order rate constant consistent with the equation ��������������������������� k = 4.9×10-4[H+]+1.0×10-5 s-1 at 25°C and ionic strength 1.0.

Isotope effects and activation parameters for the proton transfer reaction from 1-(4-nitrophenyl)-1-nitroethane to free anions and ion pairs of cesium n-propoxide in n-propanol solvent

1986 ◽  
Vol 64 (6) ◽  
pp. 1021-1025 ◽  
Author(s):  
Arnold Jarczewski ◽  
Grzegorz Schroeder ◽  
Przemyslaw Pruszynski ◽  
Kenneth T. Leffek
Keyword(s):  
Proton Transfer ◽  
Rate Constants ◽  
Isotope Effects ◽  
Ion Pairs ◽  
Activation Parameters ◽  
Solvation Shell ◽  
Ion Pair ◽  
Initial State ◽  
Free Ion ◽  
Deuteron Transfer

Rate constants for the proton and deuteron transfer from 1-(4-nitrophenyl)-1-nitroethane to cesium n-propoxide in n-propanol have been measured under pseudo-first-order conditions with an excess of base for four temperatures between 5 and 35 °C. Using literature values of the fraction of cesium n-propoxide ion pairs that are dissociated into free ions, separate second-order rate constants for the proton and deuteron transfer to the ion pair and to the free ion have been calculated. The cesium n-propoxide ion pair is about 2.8 times more reactive than the free n-propoxide ion. The primary kinetic isotope effects for the two reactions are the same (kH/kD = 6.1–6.3 at 25 °C) within experimental error. The enthalpy of activation is smaller for the ion-pair reaction and the entropy of activation more negative than for the free-ion reaction. For proton transfer, ΔH±ion pair = 8.3 ± 0.2 kcal mol−1, ΔH±ion = 9.6 ± 1.0 kcal mol−1, ΔS±ion pair = −12.3 ± 0.6 cal mol−1 deg−1, ΔS±ion = −10.1 ± 3.4 cal mol−1 deg−1. The greater reactivity of the ion pair relative to the free ion is interpreted in terms of the weaker solvation shell of the ion pair in the initial state.

Ionization of Water in Concentrated Potassium Halide Media

2000 ◽  
Vol 53 (5) ◽  
pp. 369 ◽  
Author(s):  
Faradj K. Samani ◽  
Stephen G. Capewell ◽  
Pal M. Sipos ◽  
Peter M. May ◽  
Glenn Hefter
Keyword(s):  
Ionic Strength ◽  
Aqueous Solutions ◽  
High Precision ◽  
Excellent Agreement ◽  
Ion Pairs ◽  
Formation Constants ◽  
Glass Electrode ◽  
Ionic Product ◽  
Ionization Of Water ◽  
Potassium Halide

The ionic product of water, pKw = –log[H+][OH–], has been determined as a function of ionic strength (I ) in concentrated aqueous solutions of KCl, KBr and KI at 25˚C by high-precision glass electrode potentiometric titrations. The pKw values obtained are in excellent agreement with, but generally more precise than, literature data. At I > 1 M the pKw values increase smoothly and show systematic differences in the order KCl < KBr < KI, consistent with the decreasing H+-acceptor ability of the medium anions. Analogous behaviour is observed in MCl solutions, with pKw values varying in the order NaCl < KCl < CsCl. Formation constants of MOH0 ion pairs derived from these data are consistent with literature values.

Kinetic evidence for the importance of solvent-separated ion pairs during the solvolyses of adamantylideneadamantyl derivatives

2004 ◽  
Vol 82 (9) ◽  
pp. 1336-1340
Author(s):  
Xicai Huang ◽  
Andrew J Bennet
Keyword(s):  
Ionic Strength ◽  
Transition State ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Ion Pairs ◽  
Kinetic Isotope Effects ◽  
Ion Pair ◽  
Salt Effects ◽  
Kinetic Isotope

The aqueous ethanolysis reactions of adamantylideneadamantyl tosylate, -bromide, and -iodide (1-OTs, 1-Br and 1-I) were monitored as a function of ionic strength. Special salt effects are observed during the solvolyses of both homoallylic halides, but not in the case of the tosylate 1-OTs. The measured α-secondary deuterium kinetic isotope effects for the solvolysis of 1-Br in 80:20 and 60:40 v/v ethanol–water mixtures at 25 °C are 1.110 ± 0.018 and 1.146 ± 0.009, respectively. The above results are consistent with the homoallylic halides reacting via a virtual transition state in which both formation and dissociation of a solvent-separated ion pair are partially rate-determining. While the corresponding transition state for adamantylideneadamantyl tosylate involves formation of the solvent-separated ion pair.Key words: salt effects, kinetic isotope effect, internal return, solvolysis, ion pairs.

Solute–solvent interactions in the association of hexacyanoferrate(III) with group II A cations. A calorimetric study

1982 ◽  
Vol 60 (14) ◽  
pp. 1828-1831 ◽  
Author(s):  
Roberto Aruga
Keyword(s):  
Equilibrium Constants ◽  
Ion Pairs ◽  
Ion Pair ◽  
Pair Formation ◽  
Calorimetric Study ◽  
Thermodynamic Quantities ◽  
Gibbs Function ◽  
Direct Calorimetry ◽  
Solvent Interactions ◽  
Enthalpy Of Association

Enthalpy of association of hexacyanoferrate(III) ion with Mg(II), Ca(II), Sr(II), and Ba(II) cations has been determined by direct calorimetry. Using the equilibrium constants, Gibbs function and entropy were also obtained. Measurements were carried out in aqueous medium at 25 °C and ionic strength I = 0.1 mol L−1. Examination of the thermodynamic quantities obtained and calculation of the distance of closest approach between cation and anion show the presence of different desolvation processes for the metals studied. More particularly, solvent-separated ion pairs in the case of magnesium and contact pairs in the case of barium seem to be present. The presence of desolvation processes is uncertain for calcium and strontium. The ΔH0 and ΔS0 values show also an important influence from solvent-destructuring processes on ion pair formation.

The retroaldol reaction of chalcone

1983 ◽  
Vol 61 (11) ◽  
pp. 2621-2626 ◽  
Author(s):  
J. Peter Guthrie ◽  
John Cossar ◽  
Patricia A. Cullimore ◽  
Nayyer Monshizadeh Kamkar ◽  
Kathleen F. Taylor
Keyword(s):  
Ionic Strength ◽  
Sodium Hydroxide ◽  
Rate Constants ◽  
Equilibrium Constants ◽  
Aqueous Sodium Hydroxide ◽  
Adduct Formation ◽  
Aqueous Sodium ◽  
Catalyzed Reactions

All four rate constants required to describe the hydration and aldolization/dealdolization reactions of chalcone (1,3-diphenyl-2-propen-1-one) have been determined in aqueous sodium hydroxide solutions. Kinetics were studied starting with chalcone, with its hydrate, 1,3-diphenyl-3-hydroxy-1-propanone, and with benzaldehyde in the presence of excess acetophenone. The rate constants for hydroxide catalyzed reactions, defined in terms of eq. [1] are: k12 = 10.5 ± 0.5 × 10−4 M−1 s−1; k21 = 0.026 ± 0.002 M−1 s−1; k23 = 0.194 ± 0.017 M−1 s−1; and k32 = 0.84 ± 0.12 M−2 s−1 (all at ionic strength 0.1). The corresponding equilibrium constants for aldol adduct formation and dehydration are 4.3 M−1 and 25.

Study of the dissociation of the products of some proton transfer reactions in acetonitrile solvent

1992 ◽  
Vol 70 (3) ◽  
pp. 935-942 ◽  
Author(s):  
Wlodzimierz Galezowski ◽  
Arnold Jarczewski
Keyword(s):  
Proton Transfer ◽  
Rate Constants ◽  
Isotope Effects ◽  
Equilibrium Constants ◽  
Ion Pair ◽  
Transfer Reactions ◽  
Side Reactions ◽  
First Order ◽  
Kinetic Isotope ◽  
Proton Transfer Reactions

The conductometric study of the products of the proton transfer reactions of C-acids (nitriles, nitroalkanes, and 2,4,6-trinitrotoluene) with the strong amine bases (1,1,3,3-tetramethylguanidine (TMG), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,8-bis(dimethylamino)naphthalene (DMAN), and piperidine) in acetonitrile shows their large degree of dissociation into free ions. The dissociation constant values have been estimated at 25 °C to be larger than 1 × 10−4 M. This weakens the formalism commonly accepted in spectrophotometric kinetic studies of these systems of reactions, based on the assumption that the product is an ion pair. Spectrophotometric equilibrium and kinetic measurements provided evidence that reverse reaction is a second-order process (pseudo-first order because cation concentration is controlled by side reactions). The influence of the common cation (TMGH+) on the equilibria of the proton abstraction from 2-methyl-1-(4-nitrophenyl)-1-nitropropane and 4-nitrophenylcyanomethane with TMG base in acetonitrile at 25 °C was examined and was found to be compatible with the assumption of large dissociation of the reaction product for free ions. "Equilibrium constants" estimated by the Benesi and Hildebrand method (which assumes an ion-pair product) decreased with increasing concentration of added TMGH+ cation, but these "equilibrium constants" multiplied by [TMGH+] are constant. The observed pseudo-first-order rate constants of the proton transfer reaction, measured at large excess of the base over C-acid, grow with the cation concentration due to the increase of the backward reaction rate. The concentration of added common cation shows a negligible influence on the observed rate constants of deuteron transfer reaction. Thus, as a result of side reactions, in which extra amounts of cation are formed, some second-order rate constants [Formula: see text] and also kinetic isotope effects (KIEs) [Formula: see text] that have been measured in acetonitrile can be substantially overestimated. Keywords: ion-pair dissociation, proton transfer reactions, kinetic isotope effects.

The Effect of Aromatic Amines on the Catalyzed Decarboxylation of 3-Oxo-glutaric Acid

1972 ◽  
Vol 50 (22) ◽  
pp. 3573-3586 ◽  
Author(s):  
K. N. Leong ◽  
M. W. Lister
Keyword(s):  
Ionic Strength ◽  
Stability Constants ◽  
Rate Constants ◽  
Aromatic Amines ◽  
Copper Complexes ◽  
Glutaric Acid ◽  
Equilibrium Constants ◽  
Nickel Compound ◽  
Ph Measurements ◽  
Cobalt Nickel

Equilibrium constants have been measured for the formation of MA species, where M is divalent manganese, cobalt, nickel, or zinc, and A2− is the 3-oxo-glutarate ion. Equilibrium constants have also been measured for the reactions [Formula: see text], where B is 2,2′-bipyridyl or 1,10-phenanthroline. These constants were obtained by pH measurements at 25 °C and an ionic strength of 0.60. The results are compared with those for similar systems, especially as regards the tendency to form ternary mixed complexes of the type MAB.The rates of decarboxylation of the various MA and MAB species have been measured. The resulting rate constants follow the Irving–Williams order for stability constants, except that in both MAB species the cobalt compound decomposed slightly faster than the nickel compound. The aromatic base, which had been found earlier to have very little effect in copper complexes, increased the rate constants appreciably with other metals, especially with manganese and zinc. Usually 1,10-phenanthroline has a larger effect than 2,2′-bipyridyl. Some possible explanations of the results are considered.

OXIDATION OF MANGANATE BY HYPOCHLORITE

1961 ◽  
Vol 39 (1) ◽  
pp. 96-101
Author(s):  
M. W. Lister ◽  
Y. Yoshino
Keyword(s):  
Activation Energy ◽  
Potassium Permanganate ◽  
Rate Constants ◽  
Effective Activation Energy ◽  
Equilibrium Constants ◽  
Intermediate Formation ◽  
Ion Concentration ◽  
Effective Activation ◽  
Text Data ◽  
Hydroxide Ion

The oxidation of potassium manganate to potassium permanganate by potassium hypochlorite has been examined. The rate of the reaction is proportional to the square of the manganate concentration and the first power of the hypochlorite, and it is inversely proportional to the permanganate concentration and to the square of the hydroxide ion concentration. It seems probable that the reaction involves the intermediate formation of hypomanganate ions from a relatively fast disproportionation of manganate, followed by a slower oxidation by hypochlorite. The following mechanism is tentatively proposed:[Formula: see text]Data on the over-all rate and effective activation energy (19.6 kcal/g-molecule) are given; but at present it is not possible to separate all the rate constants and equilibrium constants.

Ion Pairing and the Reaction of Alkali Metal Ferrocyanides and Persulfates

1971 ◽  
Vol 49 (18) ◽  
pp. 2943-2947 ◽  
Author(s):  
R. W. Chlebek ◽  
M.W. Lister
Keyword(s):  
Alkali Metal ◽  
Rate Constants ◽  
Equilibrium Constants ◽  
Ion Pairs ◽  
Activation Parameters ◽  
Ion Pairing ◽  
Similar Rate ◽  
Thermodynamic Quantities ◽  
Kinetics Of

Osmometric measurements have been made on the alkali metal persulfates, and these are interpreted in terms of formation of ion pairs, MS2O8−, by means of the method of Masterton and Berka (5). Equilibrium constants, and the derived thermodynamic quantities are deduced for the reactions [Formula: see text]. These results are applied to the interpretation of the kinetics of the reactions[Formula: see text]With M = K+, Rb+, and Cs+, the reacting species are MFe(CN)63− + MS2O8−, with very similar rate constants; with M = Li+, Na+ the species are MFe(CN)63− + S2O82−; and for lithium the reaction of Fe(CN)64− + S2O82− is also important. Rate constants and activation parameters are deduced.

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