A chemiluminescence study of the kinetics of reactions of Cr(III) with carboxylate ligands: oxalate, salicylate, and humic acid

1990 ◽  
Vol 68 (6) ◽  
pp. 881-885 ◽  
Author(s):  
Douglas L. Huizenga ◽  
Howard H. Patterson
Keyword(s):  
Humic Acid ◽  
Reaction Kinetics ◽  
Rate Constants ◽  
Natural Waters ◽  
Ligand Concentration ◽  
Reaction Pathways ◽  
Carboxylate Ligands ◽  
Kinetics Of ◽  
Insight Into

The reaction of Cr(III) with chelate-forming carboxylate ligands can be monitored at the low ligand concentrations typical of natural waters by chemiluminescence analysis of unreacted Cr(III). This technique is utilized here for the measurement of Cr(III) reaction kinetics with oxalate, salicylate, and humic acid over a wider ligand concentration range than previously reported. Variation of the pH and ligand concentrations allowd the determination of rates of reaction by three pathways with different pH dependencies. The magnitude of rate constants of these pathways for Cr(III) with inorganic (Cl−, SCN−) and carboxylate ligands gives insight into the reaction pathways for the environmentally important ligand humic acid. Keywords: Cr(III), oxalate, salicylate, humic acid.

Hydrogen Passivation Kinetics of Si Nanocrystals in SiO2

2003 ◽  
Vol 770 ◽  
Author(s):  
Andrew R. Wilkinson ◽  
Robert G. Elliman
Keyword(s):  
Reaction Kinetics ◽  
Activation Energies ◽  
Hydrogen Passivation ◽  
Time Resolved ◽  
Luminescence Efficiency ◽  
Si Nanocrystals ◽  
Preliminary Study ◽  
Kinetics Of ◽  
Insight Into

AbstractHydrogen passivation of non-radiative defects increases the luminescence intensity from silicon nanocrystals. In this study, photoluminescence (PL) and time-resolved PL were used to investigate the chemical kinetics of the hydrogen passivation process. Isochronal and isothermal annealing sequences were used to determine the reaction kinetics for the absorption and desorption of hydrogen, using the generalised consistent simple thermal (GST) model proposed by Stesmans for Pb defects at planar Si/SiO2 interfaces. This included determination of the activation energies and rate constants for the forward and reverse reactions as well as the associated spread in activation energies. The reaction kinetics determined from such measurements were found to be in excellent agreement with those for the passivation of Pb defects at planar Si/SiO2 interfaces, suggesting the nanocrystal emission process is also limited by such defects. These results provide useful model data as well as insight into the processing conditions needed to achieve optimum passivation in H2. As an extension to the work, a preliminary study into passivation by atomic hydrogen was pursued via a post-metallization Al anneal (alneal). A considerable gain in luminescence efficiency was achieved over the previously optimised passivation in H2.

Determination of the Nucleophilicity of Tricarbonyliron Coordinated Cyclohepta-1,3,5-triene

1999 ◽  
Vol 64 (11) ◽  
pp. 1770-1779 ◽  
Author(s):  
Herbert Mayr ◽  
Karl-Heinz Müller
Keyword(s):  
Gibbs Energy ◽  
Ambient Temperature ◽  
Rate Constants ◽  
Second Order ◽  
Order Rate ◽  
Electrophilic Additions ◽  
Kinetics Of

The kinetics of the electrophilic additions of four diarylcarbenium ions (4a-4d) to tricarbonyl(η4-cyclohepta-1,3,5-triene)iron (1) have been studied photometrically. The second-order rate constants match the linear Gibbs energy relationship log k20 °C = s(E + N) and yield the nucleophilicity parameter N(1) = 3.69. It is concluded that electrophiles with E ≥ -9 will react with complex 1 at ambient temperature.

scholarly journals Determination of the steady-state turnover rates of the metabolically active pools of phosphatidylinositol 4-phosphate and phosphatidylinositol 4,5-bisphosphate in human erythrocytes

1989 ◽  
Vol 259 (3) ◽  
pp. 893-896 ◽  
Author(s):  
C E King ◽  
P T Hawkins ◽  
L R Stephens ◽  
R H Michell
Keyword(s):  
Steady State ◽  
Rate Constants ◽  
Human Erythrocytes ◽  
Turnover Rates ◽  
Metabolic Fluxes ◽  
Metabolic Pool ◽  
Phosphatidylinositol 4 ◽  
Kinetics Of ◽  
Phosphate Groups

When intact human erythrocytes are incubated at metabolic steady state in a chloride-free medium containing [32P]Pi, there is rapid labelling of the gamma-phosphate of ATP, followed by a slower labelling of the monoester phosphate groups of phosphatidylinositol 4-phosphate (PtdIns4P) and phosphatidylinositol 4,5-bisphosphate [PtdIns(4,5)P2] [King, Stephens, Hawkins, Guy & Michell (1987) Biochem. J. 244, 209-217]. We have analysed the early kinetics of the labelling of these phosphate groups, in order to determine: (a) the steady-state rates of the interconversions of phosphatidylinositol, PtdIns4P and PtdIns(4,5)P2; and (b) the fractions of the total cellular complement of PtdIns4P and PtdIns(4,5)P2 that participate in this steady-state turnover. The experimental data most closely fit a pattern of PtdIns4P and PtdIns(4,5)P2 turnover in which one-quarter of the total cellular complement of each lipid is in the metabolic pool that participates in rapid metabolic turnover, with rate constants of 0.028 min-1 for the interconversion of PtdIns and PtdIns4P, and of 0.010 min-1 for the PtdIns4P/PtdIns(4,5)P2 cycle. These rate constants represent metabolic fluxes of approx. 2.1 nmol of lipid/h per ml of packed erythrocytes between PtdIns and PtdIns4P and of approx. 5.7 nmol/h per ml of cells between PtdIns4P and PtdIns(4,5)P2.

Annealing experiments on CO2-bearing jadeite glass: an insight into the true temperature dependence of CO2 speciation in silicate melts

2001 ◽  
Vol 65 (6) ◽  
pp. 701-707 ◽  
Author(s):  
Y. Morizet ◽  
S. C. Kohn ◽  
R. A. Brooker
Keyword(s):  
Temperature Dependence ◽  
Rate Constants ◽  
Negative Charge ◽  
Silicate Melts ◽  
True Temperature ◽  
Carbonate Group ◽  
Image Position ◽  
Kinetics Of ◽  
Annealing Experiments ◽  
Insight Into

AbstractThe thermodynamics and kinetics of CO2 speciation in silicate melts have been studied by measuring the concentration of CO2mol and carbonate in jadeite glass annealed at 575, 450 and 400°C. Assuming that the reaction is1where CO2mol..Obr represents a CO2 molecule weakly bonded to a bridging oxygen in the network and CO3 represents a bridging carbonate group with no net negative charge, ΔH for the reaction is –17 (+4/–8) kJ mol−1 and ΔS is –24 (+6/–9) J K−1 mol−1. The rate of equilibration of the species was measured at each temperature and the rate constants were deduced. The temperature dependence of the rate constants was used to determine the activation energy of the forward and reverse reactions which are 68 (+3/–31) kJ mol−1 and 86 (+1/–69) kJ mol−1 respectively. The data suggest that CO2mol may be much more abundant in silicate melts than previously assumed on the basis of studies of CO2-bearing glasses. Models of solubility, diffusion, and isotope fractionation should take this into account.

Reaction kinetics of humic acid with sodium hypochlorite

1993 ◽  
Vol 27 (5) ◽  
pp. 815-820 ◽  
Author(s):  
M.C. Sánchez Jimenez ◽  
A. Pedraza Domínguez ◽  
J.M. Cachaza Silverio
Keyword(s):  
Humic Acid ◽  
Reaction Kinetics ◽  
Sodium Hypochlorite ◽  
Kinetics Of

scholarly journals Application of a multiphase microreactor chemostat for the determination of reaction kinetics of Staphylococcus carnosus

2019 ◽  
Vol 42 (6) ◽  
pp. 953-961 ◽  
Author(s):  
S. Lladó Maldonado ◽  
J. Krull ◽  
D. Rasch ◽  
P. Panjan ◽  
A. M. Sesay ◽  
...  
Keyword(s):  
Reaction Kinetics ◽  
Staphylococcus Carnosus ◽  
Kinetics Of
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