Kinetics of the Cu(II) – Nitrilotriacetic Acid Reaction

1974 ◽  
Vol 52 (24) ◽  
pp. 4106-4108 ◽  
Author(s):  
James Maguire

The kinetics of the reaction between Cu(II) and nitrilotriacetic acid (NTA) to form the 1:1 complex have been studied by the stopped-flow technique over the pH range 2–6. The reaction is kinetically first order in both [Cu(II)] and [NTA]total; the rate constant has a minimum value of 1.1 × 105 l mol−1 s−1 in the pH range 3.5–5 and increases with either increasing or decreasing pH. An explanation for the observed kinetic behavior may be that in the case of the monoprotonated species HNTA2− there is a rate-limiting transfer of a proton from nitrogen before complex formation takes place, and that this transfer is facilitated with increasing acidity.


1973 ◽  
Vol 51 (11) ◽  
pp. 1721-1723 ◽  
Author(s):  
R. James Maguire ◽  
H. Brian Dunford

The kinetics of the oxidation of p-cresol by compound II of lactoperoxidase have been studied over the pH range 2.1–11.2 by the stopped-flow technique. The reaction is kinetically first-order with respect to p-cresol over the entire pH range. Use is made of the diffusion-controlled limit that can be placed on a bimolecular rate constant to show that p-cresol reacts in the unionized form. The complexity of the pH-rate profile is discussed in terms of acid dissociation constants of groups in the enzyme and the ionization of the substrate.



2019 ◽  
Author(s):  
Chem Int

The kinetics of oxidation of methyl orange by vanadium(V) {V(V)} has been investigated in the pH range 2.3-3.79. In this pH range V(V) exists both in the form of decavanadates and VO2+. The kinetic results are distinctly different from the results obtained for the same reaction in highly acidic solution (pH < 1) where V(V) exists only in the form of VO2+. The reaction obeys first order kinetics with respect to methyl orange but the rate has very little dependence on total vanadium concentration. The reaction is accelerated by H+ ion but the dependence of rate on [H+] is less than that corresponding to first order dependence. The equilibrium between decavanadates and VO2+ explains the different kinetic pattern observed in this pH range. The reaction is markedly accelerated by Triton X-100 micelles. The rate-[surfactant] profile shows a limiting behavior indicative of a unimolecular pathway in the micellar pseudophase.



1966 ◽  
Vol 19 (8) ◽  
pp. 1365 ◽  
Author(s):  
RH Smith ◽  
IR Wilson

Initial rates of reaction for the above oxidation have been measured by a stopped-flow conductance method. Between pH 2 and 3.6, the initial rate of reaction, R, is given by the expression R{[HSO5-]+[SCN-]} = {kb+kc[H+]}[HSO5-]0[SCN-]20+ka[H+]-1[HSO5]20[SCN-]0 As pH increases, there is a transition to a pH-independent rate, first order in each thiocyanate and peroxomonosulphate concentrations.



1992 ◽  
Vol 45 (12) ◽  
pp. 1943 ◽  
Author(s):  
SJ Dunne ◽  
RC Burns ◽  
GA Lawrance

Oxidation of Ni2+,aq, by S2O82- to nickel(IV) in the presence of molybdate ion, as in the analogous manganese system, involves the formation of the soluble heteropolymolybdate anion [MMogO32]2- (M = Ni, Mn ). The nickel(IV) product crystallized as (NH4)6 [NiMogO32].6H2O from the reaction mixture in the rhombohedra1 space group R3, a 15.922(1), c 12.406(1) � ; the structure was determined by X-ray diffraction methods, and refined to a residual of 0.025 for 1741 independent 'observed' reflections. The kinetics of the oxidation were examined at 80 C over the pH range 3.0-5.2; a linear dependence on [S2O82-] and a non-linear dependence on l/[H+] were observed. The influence of variation of the Ni/Mo ratio between 1:10 and 1:25 on the observed rate constant was very small at pH 4.5, a result supporting the view that the precursor exists as the known [NiMo6O24H6]4- or a close analogue in solution. The pH dependence of the observed rate constant at a fixed oxidant concentration (0.025 mol dm-3) fits dequately to the expression kobs = kH [H+]/(Ka+[H+]) where kH = 0.0013 dm3 mol-1 s-1 and Ka = 4-0x10-5. The first-order dependence on peroxodisulfate subsequently yields a second-order rate constant of 0.042 dm3 mol-1 s-1. Under analogous conditions, oxidation of manganese(II) occurs eightfold more slowly than oxidation of nickel(II), whereas oxidation of manganese(II) by peroxomonosulfuric acid is 16-fold faster than oxidation by peroxodisulfate under similar conditions.



1990 ◽  
Vol 68 (2) ◽  
pp. 476-479
Author(s):  
Donald C. Wigfield ◽  
Douglas M. Goltz

The kinetics of the reconstitution reaction of apotyrosinase with copper (II) ions are reported. The reaction is pseudo first order with respect to apoenzyme and the values of these pseudo first order rate constants are reported as a function of copper (II) concentration. Two copper ions bind to apoenzyme, and if the second one is rate limiting, the kinetically relevant copper concentration is the copper originally added minus the amount used in binding the first copper ion to enzyme. This modified copper concentration is linearly related to the magnitude of the pseudo first order rate constant, up to a copper concentration of 1.25 × 10−4 M (10-fold excess), giving a second order rate constant of 7.67 × 102 ± 0.93 × 102 M−1∙s−1.Key words: apotyrosinase, copper, tyrosinase.





2012 ◽  
Vol 554-556 ◽  
pp. 1925-1928 ◽  
Author(s):  
Ji Wu Li ◽  
Xiao Hong Zhu ◽  
Jun Ya Pan

The stain of Fusarium sp. HJ01 used in 4-chlorophenol (4-CP) degradation was isolated in our laboratory. The effects of pH, temperature, 4-CP concentration, carbon source on 4-CP degradation rate were studied. It was concluded that Fusarium sp. HJ01 could grow with 4-CP as the sole carbon and energy source. 4-CP concentration of 100mg/L in the pH range of 4~10 and temperature range of 25°C~35°C could be degraded completely. The capacity of 4-CP degradation was effectively enhanced by the addiction of sucrose. The kinetics of 4-CP degradation could well accord with the Haldane model for 4-CP as the sole carbon source and with first order equation for added other sucrose.



2009 ◽  
Vol 74 (10) ◽  
pp. 1531-1542 ◽  
Author(s):  
Vlado Cuculić ◽  
Ivanka Pižeta

The kinetics of iron(III) hydrolysis and precipitation in aqueous glycine solutions were studied by cathodic voltammetry with a mercury drop electrode. The kinetics was controlled by changing ionic strength (I), pH and glycine concentration. Voltammetric measurements clearly showed formation and dissociation of a soluble Fe(III)–glycine complex, formation of iron(III) hydroxide and its precipitation. The rate constants of iron(III) hydroxide precipitation were assessed. The precipitation is first-order with respect to dissolved inorganic iron(III). The calculated rate constants of iron(III) precipitation varied from 0.18 × 10–5 s–1 (at 0.2 M total glycine, pH 7.30, I = 0.6 mol dm–3) to 2.22 × 10–3 s–1 (at 0.1 M total glycine, pH 7.30, I = 0.2 mol dm–3). At 0.5 M total glycine and I = 0.6 mol dm–3, the iron(III) precipitation was not observed.



1975 ◽  
Vol 147 (3) ◽  
pp. 541-547 ◽  
Author(s):  
C J Dickenson ◽  
F M Dickinson

1. The kinetics of oxidation of butan-1-ol and propan-2-ol by NAD+, catalysed by yeast alcohol dehydrogenase, were studied at 25 degrees C from pH 5.5 to 10, and at pH 7.05 from 14 degrees to 44 degrees C, 2. Under all conditions studied the results are consistent with a mechanism whereby some dissociation of coenzyme from the active enzyme-NAD+-alcohol ternary complexes occurs, and the mechanism is therefore not strictly compulsory order. 3. A primary 2H isotopic effect on the maximum rates of oxidation of [1-2H2]butan-1-ol and [2H7]propan-2-ol was found at 25 degrees C over the pH range 5.5-10. Further, in stopped-flow experiments at pH 7.05 and 25 degrees C, there was no transient formation of NADH in the oxidation of butan-1-ol and propan-2-ol. The principal rate-limiting step in the oxidation of dependence on pH of the maximum rates of oxidation of butan-1-ol and propan-2-ol is consisten with the possibility that histidine and cysteine residues may affect or control catalysis.



1990 ◽  
Vol 55 (6) ◽  
pp. 1535-1540 ◽  
Author(s):  
Prerepa Manikyamba

Kinetics of oxidation of 1- and 2-acetylnaphthalenes by iodate in the presence of sulphuric acid in aqueous methanol has been studied. The reaction is first order with respect to both [iodate] and [acetylnaphthalene]. Solvent effect indicates a cation-dipole type of interaction in the rate limiting step. A mechanism is proposed with a slow attack of IO2+ on enol form of acetylnaphthalene forming an intermediate carbonium ion, which ultimately gives corresponding ω-hydroxyacetylnaphthalene. The higher reactivity of 2-acetyl isomer is attributed to the greater stability of the corresponding carbonium ion than that of 1-acetyl isomer.



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