THE KINETICS OF THE FORMATION OF THE MONO–FLUORO COMPLEX OF IRON (III) IN AQUEOUS SOLUTION

1960 ◽  
Vol 38 (4) ◽  
pp. 567-575 ◽  
Author(s):  
D. Pouli ◽  
W. MacF. Smith

The kinetics of the reactions involved in the formation of the mono–fluoro complex of iron (III) in aqueous solutions have been examined spectrophotometrically at ionic strength 0.5 and over the temperature interval 0.1 to 12.1 °C. The results are interpretable on the assumption that the following two reactions contribute significantly to the rate Fe+++ + F− = FeF++ and Fe+++ + HF = FeF++ + H+, the former having a heat of activation of 22.8 ± 2.5 kcal mole−1 and an entropy of activation of 35 ± 9 cal deg−1 mole−1, the latter having a heat of activation of 8.7 ± 0.7 kcal mole−1 and an entropy of activation of −24.5 ± 3 cal deg−1 mole−1.


1955 ◽  
Vol 33 (12) ◽  
pp. 1780-1791 ◽  
Author(s):  
R. H. Betts

The kinetics of oxidation of uranium (IV) by iron (III) in aqueous solutions of perchloric acid have been investigated at four temperatures between 3.1 °C. and 24.8 °C. The reaction was followed by measurement of the amount of ferrous ion formed. For the conditions (H+) = 0.1–1.0 M, ionic strength = 1.02, (FeIII) = 10−4–10−5 M, and (UIV) = 10−4–10−5 M, the observed rate law is d(Fe2+)/dt = −2d(UIV)/dt[Formula: see text]K1 and K2 are the first hydrolysis constants for Fe3+ and U4+, respectively, and K′ and K″ are pseudo rate constants. At 24.8 °C., K′ = 2.98 sec.−1, and K″ = 10.6 mole liter−1 sec−1. The corresponding temperature coefficients are ΔH′ = 22.5 kcal./mole and ΔH″ = 24.2 kcal./mole. The kinetics of the process are consistent with a mechanism which involves, as a rate-controlling step, electron transfer between hydrolyzed ions.



1962 ◽  
Vol 40 (9) ◽  
pp. 1836-1845 ◽  
Author(s):  
G. G. Davis ◽  
W. MacF. Smith

The kinetics of formation of the monosulphato complex of iron (III) has been examined spectrophotometrically using a continuous-flow technique over the range of temperatures 15.6 to 34.5 °C in an aqueous medium of ionic strength 0.5 and a range of concentrations of hydrogen ions 0.05 to 0.30 M. The experimental data may be interpreted on the assumption that the significant reactions are a bimolecular association opposed by a first-order dissociation [Formula: see text] For the forward reaction ΔH≠ is 18.0 kcal mole−1 and ΔS≠ is 19.4 cal mole−1 deg−1.



2003 ◽  
Vol 07 (03) ◽  
pp. 139-146 ◽  
Author(s):  
Peter Hambright ◽  
Ines Batinić-Haberle ◽  
Ivan Spasojević

The relative reactivities of the tetrakis( N -alkylpyridinium- X - yl )-porphyrins where X = 4 (alkyl = methyl, ethyl, n -propyl) , X = 3 (methyl) , and X = 2 (methyl, ethyl, n -propyl, n -butyl, n -hexyl, n -octyl) were studied in aqueous solution. From the ionic strength dependence of the metalation rate constants, the effective charge of a particular cationic porphyrin was usually larger when copper(II) rather than zinc(II) was the reactant. The kinetics of ZnOH + incorporation and the acid catalyzed removal of zinc from the porphyrins in 1.0 M HCl were also studied. In general, the more basic 4- (para-) and 3- (meta-) isomers were the most reactive, followed by the less basic 2- (ortho-) methyl to n -butyl derivatives, with the lipophilic ortho n -hexyl and n -octyl porphyrins the least reactive.



2017 ◽  
Vol 228 ◽  
pp. 98-107 ◽  
Author(s):  
Adriana Campos-Ramírez ◽  
Maripaz Márquez ◽  
Liliana Quintanar ◽  
Luis F. Rojas-Ochoa


1974 ◽  
Vol 29 (1) ◽  
pp. 141-144
Author(s):  
T. S. Rao ◽  
S. I. Mali

The kinetics of the reaction between has been studied under conditions of production of iodine at a known rate by the persulfate-iodide reaction and its consumption by S2O3-- . The effective concentration of iodine during the steady state is measured from its reduction potential at a bright platinum foil electrode. The reaction is of first order with respect to I3- and S2O3-- individually and hence of over all second order. The specific rate is 1.51 X 105 M -1 sec-1 and the frequency factor is 1.69 × 1012 M -1 sec-1 at 25 °C. The energy of activation for the reaction is 9.58 × 103 cal/mole and the entropy of activation is -2.55 cal/mole deg.



1962 ◽  
Vol 40 (3) ◽  
pp. 363-372 ◽  
Author(s):  
R. W. Burley ◽  
W. H. Cook

The effect of pH, temperature, ionic strength, and lipoprotein concentration on the reversible dissociation of α- and β-lipovitellin in aqueous solutions above pH 6 has been examined by ultracentrifugal measurements. Under otherwise similar conditions α- and β-lipovitellin are 50% dissociated at pH 10.5 and 7.8, respectively. Both lipovitellins undergo an irreversible aggregation above about pH 11; β-lipovitellin is sometimes converted to a non-dissociable form upon aging. Dissociation of both lipovitellins decreases with increasing ionic strength and increasing temperature. Although the ultracentrifugal method has limitations, provisional equilibrium constants and thermodynamic data were obtained from it that are comparable with those obtained for certain protein systems.



1982 ◽  
Vol 76 (2) ◽  
pp. 984-996 ◽  
Author(s):  
Mei Hsu Dung ◽  
John J. Kozak


1970 ◽  
Vol 48 (7) ◽  
pp. 1054-1058 ◽  
Author(s):  
T. W. Swaddle ◽  
W. E. Jones

The kinetics of the hydrogen-ion-independent pathway for the replacement of fluoride in aqueous (NH3)5CoF2+ by H2O have been reinvestigated using a specific fluoride-ion electrode, with due regard for the concomitant autocatalytic loss of the ammine ligands. In perchlorate media of ionic strength 0.1 M, the first-order rate coefficient is 1.22 × 10−6 s−1 at 45°, and the kinetics are represented by ΔH* = 24.4 kcal mole−1 and ΔS* = −9 cal deg−1 mole−1 over the range 35–75° at least. The relationship of these data to those for the aquation of other species of the type ML5Xn+ is discussed.



1986 ◽  
Vol 64 (6) ◽  
pp. 1267-1272 ◽  
Author(s):  
Oswald S. Tee ◽  
Jana Pika ◽  
M. Judith Kornblatt ◽  
Michael Trani

The kinetics of bromination of the title compound (1) have been measured in aqueous solutions of pH 0–6. The change in the order of reaction which occurs around pH 2.5 is explained by 1 reacting via its covalent hydrate, 3. Furthermore, there is sufficient 3 present at equilibrium that the kinetics of its equilibration with 1 were also measured. From these two studies the extent of covalent hydration of 1 is estimated to be 5%.Kinetic studies of the bromination of the dimethyl cation 5 and of its equilibration with the pseudobase 6 were also carried out for the purposes of comparison.The present results for 1, 3, 5, and 6 are compared to earlier results for 2-pyrimidinone and analogous derivatives.



1962 ◽  
Vol 15 (2) ◽  
pp. 211 ◽  
Author(s):  
W Kitching ◽  
RH Smith ◽  
IR Wilson

The kinetics and stoicheiometry of the decomposition of aqueous solutions of sulphur dicyanide have been studied at temperatures between 0-70 �C and in media ranging from dilute perchloric acid to pH 7. The predominant reaction is nucleophilic substitution at carbon, but in perchloric acid solutions an alternative reaction path has been revealed.



Sign in / Sign up

Export Citation Format

Share Document