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1.
Dubey Sapna Sharma Neetu Khandelwal Chandra L. Sharma Prem D. 《Transition Metal Chemistry》2003,28(2):176-181
The kinetics of osmium(VIII)-catalyzed oxidation of hypophosphite with hexacyanoferrate(III) in alkaline medium has been studied. The rate is independent of the concentration of the oxidant. The order with respect to hydroxide ion is variable. Rate law (1) conforms with the experimental observations.
The equilibrium constant 'K
1' for step (2)
has been evaluated kinetically to be (21 ± 5.0), (23 ± 5.0), (26 ± 6) and (32 ± 6) at 25, 30, 32 and 35 °C and I = 1.0 mol dm–3 respectively. The energy and entropy of activation were calculated to be (42 ± 2.0) kJ mol–1 and (82 ± 6.0) J K–1 mol–1 respectively. A plausible reaction mechanism has been suggested. 相似文献
2.
The oxidation of H2NOH is first-order both in [NH3OH+] and [AuCl4
–]. The rate is increased by the increase in [Cl–] and decreased with increase in [H+]. The stoichiometry ratio, [NH3OH+]/[AuCl4
–], is 1. The mechanism consists of the following reactions.
The rate law deduced from the reactions (i)–(iv) is given by Equation (v) considering that [H+] K
a.
The reaction (iii) is a combination of the following reactions:
The activation parameters for the reactions (ii) and (iii) are consistent with an outer-sphere electron transfer mechanism. 相似文献
3.
Summary The oxidation of H2O2 by [W(CN)8]3– has been studied in aqueous media between pH 7.87 and 12.10 using both conventional and stopped-flow spectrophotometry. The reaction proceeds without generation of free radicals. The experimental overall rate law,
, strongly suggests two types of mechanisms. The first pathway, characterized by the pH-dependent rate constant k
s, given by
, involves the formation of [W(CN)8· H2O2]3–, [W(CN)8· H2O2·W(CN)8]6– and [W(CN)8· HO]3– intermediates in rapid pre-equilibria steps, and is followed by a one-electron transfer step involving [W(CN)8·HO]3– (k
a) and its conjugate base [W(CN)8·O]4– (k
b). At 25 °C, I = 0.20 m (NaCl), the rate constant
with H
a
=40±6kJmol–1 and S
a
=–151±22JK–1mol–1; the rate constant
with H
b
=36±1kJmol–1 and S
b
=–136±2JK–1mol–1 at 25 °C, I = 0.20 m (NaCl); the acid dissociation constant of [W(CN)8·HO]3–, K
5
=(5.9±1.7)×10–10
m, with
and
is the first acid dissociation constant of H2O2. The second pathway, with rate constant, k
f, involves the formation of [W(CN)8· HO2]4– and is followed by a formal two-electron redox process with [W(CN)8]3–. The pH-dependent rate constant, k
f, is given by
. The rate constant k
7
=23±6m
–1
s
–1 with
and
at 25°C, I = 0.20 m (NaCl). 相似文献
4.
The oxidation of a ternary complex of chromium(III), [CrIII(DPA)(Mal)(H2O)2]?, involving dipicolinic acid (DPA) as primary ligand and malonic acid (Mal) as co-ligand, was investigated in aqueous acidic medium. The periodate oxidation kinetics of [CrIII(DPA)(Mal)(H2O)2]? to give Cr(VI) under pseudo-first-order conditions were studied at various pH, ionic strength and temperature values. The kinetic equation was found to be as follows: \( {\text{Rate}} = {{\left[ {{\text{IO}}_{4}^{ - } } \right]\left[ {{\text{Cr}}^{\text{III}} } \right]_{\text{T}} \left( {{{k_{5} K_{5} + k_{6} K_{4} K_{6} } \mathord{\left/ {\vphantom {{k_{5} K_{5} + k_{6} K_{4} K_{6} } {\left[ {{\text{H}}^{ + } } \right]}}} \right. \kern-0pt} {\left[ {{\text{H}}^{ + } } \right]}}} \right)} \mathord{\left/ {\vphantom {{\left[ {{\text{IO}}_{4}^{ - } } \right]\left[ {{\text{Cr}}^{\text{III}} } \right]_{\text{T}} \left( {{{k_{5} K_{5} + k_{6} K_{4} K_{6} } \mathord{\left/ {\vphantom {{k_{5} K_{5} + k_{6} K_{4} K_{6} } {\left[ {{\text{H}}^{ + } } \right]}}} \right. \kern-0pt} {\left[ {{\text{H}}^{ + } } \right]}}} \right)} {\left\{ {\left( {\left[ {{\text{H}}^{ + } } \right] + K_{4} } \right) + \left( {K_{5} \left[ {{\text{H}}^{ + } } \right] + K_{6} K_{4} } \right)\left[ {{\text{IO}}_{4}^{ - } } \right]} \right\}}}} \right. \kern-0pt} {\left\{ {\left( {\left[ {{\text{H}}^{ + } } \right] + K_{4} } \right) + \left( {K_{5} \left[ {{\text{H}}^{ + } } \right] + K_{6} K_{4} } \right)\left[ {{\text{IO}}_{4}^{ - } } \right]} \right\}}} \) where k 6 (3.65 × 10?3 s?1) represents the electron transfer reaction rate constant and K 4 (4.60 × 10?4 mol dm?3) represents the dissociation constant for the reaction \( \left[ {{\text{Cr}}^{\text{III}} \left( {\text{DPA}} \right)\left( {\text{Mal}} \right)\left( {{\text{H}}_{2} {\text{O}}} \right)_{2} } \right]^{ - } \rightleftharpoons \left[ {{\text{Cr}}^{\text{III}} \left( {\text{DPA}} \right)\left( {\text{Mal}} \right)\left( {{\text{H}}_{2} {\text{O}}} \right)\left( {\text{OH}} \right)} \right]^{2 - } + {\text{H}}^{ + } \) and K 5 (1.87 mol?1 dm3) and K 6 (22.83 mol?1 dm3) represent the pre-equilibrium formation constants at 30 °C and I = 0.2 mol dm?3. Hexadecyltrimethylammonium bromide (CTAB) was found to enhance the reaction rate, whereas sodium dodecyl sulfate (SDS) had no effect. The thermodynamic activation parameters were estimated, and the oxidation is proposed to proceed via an inner-sphere mechanism involving the coordination of IO4 ? to Cr(III). 相似文献
5.
The kinetics and mechanism of the reduction of enneamolybdonickelate(IV) by iodide in acid aqueous solution was studied by spectrophotometry. The reaction rate increases, as the concentration of H+ increases and with temperature. It shows that the reaction rate law is
The reaction rate constants and activation parameters of the rate-determining steps were evaluated. A mechanism related to the reaction is proposed. 相似文献
6.
Balesh A. Deganatti Nagaraj P. Shetti Sharanappa T. Nandibewoor 《Transition Metal Chemistry》2009,34(2):143-152
The oxidation of l-valine (l-val) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium at a constant ionic strength of 3.0 × 10−3 mol dm−3 was studied spectrophotometrically at 298 K and follows the rate law;
where K
4, K
5 and K
6 are the equilibrium constants for the different steps involved in the mechanism, k is the rate constant for the slow step of the reaction. The appearance of [l-val] term in both numerator and denominator explains the observed less than unit order in [l-val]. Similarly the appearances of [H3IO6
2−] and [OH−] in the denominator obey the experimental negative less than unit order in [H3IO6
2−] and [OH−], respectively. The oxidation reaction in alkaline medium proceeds via a DPC-l-valine complex, which decomposes slowly in a rate determining step followed by other fast steps to give the products. The
main products were identified by spot test and spectroscopic studies. 相似文献
7.
The kinetics and mechanism of the reduction of enneamolybdonickelate(IV) by arsenite in aqueous acid solution was studied by spectrophotometry. The reaction rate increases with increasing concentrations of H+ and with temperature. The associated rate law is:
. The rate constants and activation parameters of the rate-determining step were evaluated. A mechanism related to this reaction was proposed. 相似文献
8.
The equilibrium constant for the hydrolytic disproportionation of I2
has been determined at 25°C and at ionic strength 0.2 M(NaClO4) in buffered solution. The reaction was followed in the pH range where the equilibrium concentration of I2, I–, and IO3
–are commensurable, i.e., the fast equilibrium
is also established. The equilibrium concentrations of I2and I3
–were determined spectrophotometrically, and the concentrations of all the other species participating in process (1) were calculated from the stoichiometric constraints. The constants determined are \log K_1 = -47.61\pm 0.07 and \log K_2 = 2.86 \pm 0.01. 相似文献
9.
Reinaldo F. Teófilo Helder J. Ceragioli Alfredo C. Peterlevitz Leonardo M. Da Silva Flavio S. Damos Márcia M. C. Ferreira Vitor Baranauskas Lauro T. Kubota 《Journal of Solid State Electrochemistry》2007,11(10):1449-1457
The electrochemical properties of boron-doped diamond (BDD) polycrystalline films grown on tungsten wire substrates using
ethanol as a precursor are described. The results obtained show that the use of ethanol improves the electrochemistry properties
of “as-grown” BDD, as it minimizes the graphitic phase upon the surface of BDD, during the growth process. The BDD electrodes
were characterized by Raman spectroscopy, scanning electronic microscopy, cyclic voltammetry (CV), and electrochemical impedance
spectroscopy (EIS). The boron-doping levels of the films were estimated to be ∼1020 B/cm3. The electrochemical behavior was evaluated using the and redox couples and dopamine. Apparent heterogeneous electro-transfer rate constants were determined for these redox systems using the CV and EIS techniques. values in the range of 0.01–0.1 cm s−1 were observed for the and redox couples, while in the special case of dopamine, a lower value of 10−5 cm s−1 was found. The obtained results showed that the use of CH3CH2OH (ethanol) as a carbon source constitutes a promising alternative for manufacturing BDD electrodes for electroanalytical
applications. 相似文献
10.
Khan Zaheer Rafiquee Mohammad Z. A. Niaz Mohammad A. Khan Abdul Aziz Kabir-ud-Din 《Transition Metal Chemistry》1998,23(5):537-540
The kinetics of alkaline hydrolysis of Co(Asn)2, yielding Co(OH)2, NH3 and aspartic acid, have been studied spectrophotometrically, and the effects of CoII and NaOH concentrations on the reaction rate determined. The rate increases with increasing [NaOH], whereas variation of [CoII] has no significant effect. The kinetics of NH3 evolution conform to the rate law:
It is proposed that the reaction proceeds through formation of a dianionic tetrahedral intermediate. 相似文献
11.
M. Y. El-Sheikh A. M. Habib A. K. Abou-Seif A. B. Zaki 《Journal of inclusion phenomena and macrocyclic chemistry》1986,4(4):359-367
The kinetics of the decomposition of hydrogen peroxide was studied in aqueous medium in the temperature range 25–40°C in the presence of Wofatit KPS-resin in the form of Cu(II)-ammine complex ions. The rate constant was deduced at various degrees of resin cross-linkage and different concentrations of hydrogen peroxide. The order of the decomposition reaction varied from first order to half order, i.e., the order of the reaction decreased with increasing the concentration of H2O2. The decomposition process was found to be a catalytic reaction which was controlled by the chemical reaction of H2O2 molecules with the active species inside the resin particles. The mechanism of the reaction can be summarized by the equation
in which the subsequent reactions of the probable active complex are discussed. 相似文献
12.
The kinetics of oxidation of cis-[CrIII(gly)2(H2O)2]+ (gly = glycinate) by $ {\text{IO}}_{ 4}^{ - } $ has been studied in aqueous solutions. The reaction is first order in the chromium(III) complex concentration. The pseudo-first-order rate constant, k obs, showed a small change with increasing $ \left[ {{\text{IO}}_{ 4}^{ - } } \right] $ . The pseudo-first-order rate constant, k obs, increased with increasing pH, indicating that the hydroxo form of the chromium(III) complex is the reactive species. The reaction has been found to obey the following rate law: $ {\text{Rate}} = 2k^{\text{et}} K_{ 3} K_{ 4} \left[ {{\text{Cr}}\left( {\text{III}} \right)} \right]_{t} \left[ {{\text{IO}}_{ 4}^{ - } } \right]/\left\{ {\left[ {{\text{H}}^{ + } } \right] + K_{ 3} + K_{ 3} K_{ 4} \left[ {{\text{IO}}_{ 4}^{ - } } \right]} \right\} $ . Values of the intramolecular electron transfer constant, k et, the first deprotonation constant of cis-[CrIII(gly)2(H2O)2]+, K 3 and the equilibrium formation constant between cis-[CrIII(gly)2(H2O)(OH)] and $ {\text{IO}}_{ 4}^{ - } $ , K 4, have been determined. An inner-sphere mechanism has been proposed for the oxidation process. The thermodynamic activation parameters of the processes involved are reported. 相似文献
13.
Abdel-Khalek Ahmed A. Mohamed Adel A. Ewais Hassan A. 《Transition Metal Chemistry》1999,24(2):233-238
The kinetics of oxidation of the chromium(III)-DL- aspartic acid complex, [CrIIIHL]+ by periodate have been investigated in aqueous medium. In the presence of FeII as a catalyst, the following rate law is obeyed:
Catalysis is believed to be due to the oxidation of iron(II) to iron(III), which acts as the oxidizing agent. Thermodynamic activation parameters were calculated. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO
4
-
to CrIII. 相似文献
14.
Luminescence Behavior of Polynuclear Alkynylcopper(I) Phosphines 总被引:1,自引:0,他引:1
A series of soluble trinuclear and tetranuclear copper(I) complexes containing 3-l acetylides
, and
have been synthesized and shown to exhibit rich photoluminescent behavior at room temperature. The electrochemistry of the trinuclear Cu(I) acetylide complexes and the excited-state redox properties of
have been investigated. The X-ray crystal structures of
and
have been determined. 相似文献
15.
Oxidation of 3-(4-methoxyphenoxy)-1,2-propanediol (MPPD) by bis(hydrogenperiodato) argentate(III) complex anion, [Ag(HIO6)2]5− has been studied in aqueous alkaline medium by use of conventional spectrophotometry. The major oxidation product of MPPD
has been identified as 3-(4-methoxyphenoxy)-2-ketone-1-propanol by mass spectrometry. The reaction shows overall second-order
kinetics, being first-order in both [Ag(III)] and [MPPD]. The effects of [OH−] and periodate concentration on the observed second-order rate constants k′ have been analyzed, and accordingly an empirical expression has been deduced:
where [IO4
−]tot denotes the total concentration of periodate and k
a = (0.19 ± 0.04) M−1 s−1, k
b = (10.5 ± 0.3) M−2 s−1, and K
1 = (5.0 ± 0.8) × 10−4 M at 25.0 °C and ionic strength of 0.30 M. Activation parameters associated with k
a and k
b have been calculated. A mechanism is proposed, involving two pre-equilibria, leading to formation of a periodato–Ag(III)–MPPD
complex. In the subsequent rate-determining steps, this complex undergoes inner-sphere electron-transfer from the coordinated
MPPD molecule to the metal center by two paths: one path is independent of OH−, while the other is facilitated by a hydroxide ion. 相似文献
16.
Rosso Janina A. Villata Laura S. Mártire Daniel O. Capparelli Alberto L. 《Transition Metal Chemistry》1998,23(5):645-648
The molecular oxygen-mediated decomposition of the binuclear complex, prepared from oxomolybdate(V) and L-(+)-cysteine, was studied spectrophotometrically at pH 3.5–5.6. The formation of MoVI was detected. The effects of pH and [O2] on the decomposition kinetics are given by the equation:
with the apparent first order rate constant, kobs, expressed in s–1 and the concentrations in molar units. 相似文献
17.
The oxidation of aquaethylenediaminetetraacetatocobaltate(II) [Co(EDTA)(H2O)]−2 by N-bromosuccinimide (NBS) in aqueous solution has been studied spectrophotometrically over the pH 6.10–7.02 range at 25 °C.
The reaction is first-order with respect to complex and the oxidant, and it obeys the following rate law:
\textRate = k\textet K 2 K 3 [ \textCo\textII ( \textEDTA )( \textH 2 \textO ) - 2 ]\textT [\textNBS] \mathord | / |
\vphantom [\textNBS] ( [ \textH + ] + K 2 ) ( [ \textH + ] + K 2 ) {\text{Rate}} = k^{\text{et} } K_{ 2} K_{ 3} \left[ {{\text{Co}}^{\text{II}} \left( {\text{EDTA}} \right)\left( {{\text{H}}_{ 2} {\text{O}}} \right)^{ - 2} } \right]_{\text{T}} {{[{\text{NBS}}]} \mathord{\left/ {\vphantom {{[{\text{NBS}}]} {\left( {\left[ {{\text{H}}^{ + } } \right]{ + }K_{ 2} } \right)}}} \right. \kern-\nulldelimiterspace} {\left( {\left[ {{\text{H}}^{ + } } \right]{ + }K_{ 2} } \right)}} 相似文献
18.
K. Juodkazis J. Juodkazytė V. Šukienė A. Grigucevičienė A. Selskis 《Journal of Solid State Electrochemistry》2008,12(11):1399-1404
Comparative study of capacitative properties of RuO2/0.5 M H2SO4 and Ru/0.5 M H2SO4 interfaces has been performed with a view to find out the nature of electrochemical processes involved in the charge storage
mechanism of ruthenium (IV) oxide. The methods of cyclic voltammetry and scanning electron microscopy (SEM) were employed
for the investigation of electrochemical behavior and surface morphology of RuO2 electrodes. It has been suggested that supercapacitor behavior of RuO2 phase in the potential E range between 0.4 and 1.4 V vs reference hydrogen electrode (RHE) should be attributed to double-layer-type capacitance,
related to non-faradaic highly reversible process of ionic pair formation and annihilation at RuO2/electrolyte interface as described by following summary equation:
19.
The solubility of rhodochrosite (MnCO3) at 25°C under constant carbon dioxide partial pressure p(CO2) was determined in NaCl solutions as a function of ionic strength I. The dissolution of MnCO3(s) for the reaction
20.
Reena Singh Atanu Banerjee Yee Gordon Kajal Krishna Rajak 《Transition Metal Chemistry》2009,34(6):689-694
Abstract The title complexes and have been synthesized in excellent yields by reacting Co(OAc)2·4H2O with H2L1 and H2L2, respectively, in acetonitrile solution. Here, [L1]2− and [L2]2− are the deprotonated forms of N,N-bis(2-hydroxybenzyl)-N′,N′-dimethylethylenediamine and N,N-bis(2-hydroxybenzyl)-2-picolylamine, respectively. The crystal structures of and were determined by x-ray crystallography. In , each cobalt atom has distorted trigonal bipyramid geometry, while in , each cobalt atom has distorted octahedral geometry. Variable temperature magnetic moment measurements show weak antiferromagnetic
interaction in . The magnetic characterization for is in agreement with the presence of Co(II) and Co(III) centers.
Graphical Abstract The title complexes and have been synthesized in excellent yields by reacting Co(OAc)2·4H2O with dianionic N2O2 coordinating ligands. In complex 1, each cobalt atom has distorted trigonal bipyramid geometry, while in complex 2, each
cobalt atom has distorted octahedral geometry. Variable temperature magnetic moment measurements show weak antiferromagnetic
interaction in complex 1. The magnetic characterization for complex 2 is in agreement with the presence of Co(II) and Co(III)
centers.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
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