Investigations into the kinetics and stoichiometry of bacterial oxidation of covellite (CuS) using a polarographic oxygen probe

1978 ◽  
Vol 24 (8) ◽  
pp. 998-1003 ◽  
Author(s):  
Pamela A. D. Rickard ◽  
Donald G. Vanselow

"Oxygraph" apparatus was used to measure quantitatively the kinetics of oxidation of synthetic covellite (CuS) in the presence and absence of Thiobacillus species. The expected stoichiometric relationship between oxygen consumed and cupric sulphate produced was verified by atomic absorption assays of cupric ion and sulphate ion. Thiobacillus cultures markedly increased the oxidation rate.The dependence of each oxygen-uptake rate on oxygen concentration was also measured. Sterile controls and some bacterial cultures showed first-order kinetics while other cultures showed zero-order kinetics.Addition of biological inhibitors to reacting slurries revealed that cultures showing first-order kinetics did not oxidize CuS itself but merely oxidized elemental sulphur formed by non-enzymic oxidation of CuS. Cultures showing zero-order kinetics oxidized CuS in a way that resulted in all oxygen reduction being enzymic. This mechanism possibly involves the cyclic oxidation and reduction of soluble iron.

2013 ◽  
Vol 779-780 ◽  
pp. 1658-1665
Author(s):  
Rong Shu Zhu ◽  
Fei Tian ◽  
Ling Ling Zhang ◽  
Ling Min Yu

This paper studied the photocatalytic reduction kinetics of bromate in aqueous dispersion of TiO2 and investigated the effects of experimental parameters, including initial concentration of BrO3-, pH, TiO2 dosage, anion and cation. The results indicate that the process of photocatalytic reduction of bromate follows a zero-order kinetics. In all the investigated experimental parameters, the initial bromate concentration, pH and anion have great effect on the photocatalytic reduction kinetics. The processes of photocatalytic reduction of bromate show the pseudo first-order kinetics at initial bromate concentration of 0.39 μmolL-1, pH=5.0, or in presence of HCO3-/CO32-, NO3-, SO42-, respectively.


2008 ◽  
Vol 55-57 ◽  
pp. 757-760 ◽  
Author(s):  
A. Kleawkla ◽  
Robert Molloy ◽  
W. Naksata ◽  
Winita Punyodom

Two novel tin(II) alkoxides, namely: tin(II) hexoxide, Sn(OC6H13)2, and tin(II) octoxide, Sn(OC8H17)2, have been synthesized for use as coordination-insertion initiators in the bulk ring-opening polymerization of ε-caprolactone. The kinetics of the polymerization reactions were studied at 140 °C by dilatometry. It was found that both alkoxides were slow to dissolve in the ε-caprolactone monomer due to their molecular aggregation in the solid state. As a result, the slow solubilization of the initiators gave rise to deviations from the expected first-order kinetics. Instead, the kinetic results adhered more closely to zero-order kinetics with apparent zero-order rate constants k0 of 6.58 x 10-2 and 4.63 x 10-2 mol l-1 min-1 for the hexoxide and octoxide respectively


1997 ◽  
Vol 3 (3) ◽  
pp. 213-218 ◽  
Author(s):  
A. Ibarz ◽  
O. Martín ◽  
G.V. Barbosa-Cánovas

Non-enzymatic browning kinetics of concentrated juice for three pear varieties (Alexandrine Douillard, Flor de Invierno and Blanquilla) was evaluated at three temperatures (90, 80 and 70 °C) and different soluble solid contents (52, 62 and 72 °Brix). The evolution of absorbance at 420 nm is described by zero order kinetics, but the formation of 5-hydroxymethyl-2 furfuraldehyde (HMF) and the reduction in formol index followed first order kinetics. The Alexandrine Douillard juices showed non-enzymatic browning which was less pronounced than in Flor de Invierno and Blanquilla juices.


2003 ◽  
Vol 58 (8) ◽  
pp. 787-794 ◽  
Author(s):  
B.Thimme Gowda ◽  
K. L. Jayalakshmi ◽  
K. Jyothi

In an effort to introduce N,N-dichloroarylsulphonamides of different oxidising strengths, four mono- and five di-substituted N,N-dichlorobenzenesulphonamides are prepared, characterised and employed as oxidants for studying the kinetics of oxidation of dimethyl sulphoxide (DMSO) in 50% aqueous acetic acid. The reactions show first order kinetics in [oxidant], fractional to first order in [DMSO] and nearly zero order in [H+]. Increase in ionic strength of the medium slightly increases the rates, while decrease in dielectric constant of the medium decreases the rates. The results along with those of the oxidation of DMSO by N,N-dichlorobenzenesulphonamide and N,N-dichloro-4- methylbenzenesulphonamide have been analysed. Effective oxidising species of the oxidants employed in the present oxidations is Cl+ in different forms, released from the oxidants. Therefore the introduction of different substituent groups into the benzene ring of the oxidant is expected to affect the ability of the reagent to release Cl+ and hence its capacity to oxidise the substrate. Significant changes in the kinetic and thermodynamic data are observed in the present investigations with change of substituent in the benzene ring. The electron releasing groups such as CH3 inhibit the ease with which Cl+ is released from the oxidant, while electron-withdrawing groups such as Cl enhance this ability. The Hammett equation, log kobs = −3.19 + 1.05 σ , is found to be valid for oxidations by all the p-substituted N,N-dichlorobenzenesulphonamides. The substituent effect on the energy of activation, Ea and log A for the oxidations is also analysed. The enthalpies and free energies of activation correlate with an isokinetic temperature of 320 K.


1986 ◽  
Vol 32 (5) ◽  
pp. 758-762 ◽  
Author(s):  
D A Smith ◽  
G C Moses ◽  
A R Henderson

Abstract We examined the stability of human lactate dehydrogenase (EC 1.1.1.27; LD) isoenzymes 1, 2, and 3--purified to specific activities of about 200 kU/g--when lyophilized in a buffered stabilized matrix of bovine albumin. Each isoenzyme was prepared at two activity concentrations and stored at -20, 4, 20, 37, and 56 degrees C for as long as six months. LD-1 activity decayed with zero-order kinetics, LD-2 and LD-3 with first-order kinetics. The extrapolated half-lives of these preparations at -20 degrees C varied between 80 and 530 years. Stability of reconstituted samples stored at 4 degrees C was excellent for LD-1 but poor for LD-2 and LD-3. We suggest that preparations of human LD-1 be further investigated as a possible reference material.


1978 ◽  
Vol 33 (6) ◽  
pp. 657-659 ◽  
Author(s):  
M. P. Singh ◽  
A. K. Singh ◽  
Mandhir Kumar

Abstract The present paper deals with the kinetics of oxidation of D-galactose by Nessler's reagent in alkaline medium. The reaction is zero order with respect to Hg(II) and first order with respect to reducing sugar. The direct proportionality of the reaction rate at low hydroxide ion concentrations shows retarding trend at higher concentrations. The reaction rate is inversely proportional to iodide ion concentration. A mechanism has been proposed taking HgI3- as the reacting species


2008 ◽  
Vol 5 (1) ◽  
pp. 43-51 ◽  
Author(s):  
Mansur Ahmed ◽  
K. Subramani

Hydrogen peroxide oxidation of pentaamminecobalt(III) complexes ofα-hydroxy acids at 35°C in micellar medium has been attempted. In this reaction the rate of oxidation shows first order kinetics each in [cobalt(III)] and [H2O2]. Hydrogen peroxide induced electron transfer in [(NH3)5CoIII-L]2+complexes ofα-hydroxy acids readily yields 100% of cobalt(II) with nearly 100% of C-C bond cleavage products suggesting that it behaves mainly as one equivalent oxidant in micellar medium. With unbound ligand also it behaves only as C-C cleavage agent rather than C-H cleavage agent. With increasing micellar concentration an increase in the rate is observed.


1986 ◽  
Vol 64 (5) ◽  
pp. 969-972 ◽  
Author(s):  
Donald C. Wigfield ◽  
Season Tse

The kinetics of oxidation of the mercurous ion by peroxidase have been measured by following the disappearance of mercurous ion using cold-vapour atomic absorption spectroscopy. Pseudo-first-order kinetics are observed with respect to mercurous ion, and the pseudo-first-order rate constants are linearly related to peroxidase concentration, showing first-order dependence on peroxidase. This behaviour is identical to oxidation of elemental mercury, and the second-order rate constant, 1.44 × 104 M−1 s−1 at 23 °C, is also, within experimental error, the same as that for elemental mercury oxidation. The data are interpreted in terms of peroxidase-induced disproportionation of the mercurous dimer, followed by two-electron oxidation of zero-valent mercury.


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