THE INTERACTION OF METHANE AND METHANE-d4 ON NICKEL AND THE STATE OF THE CATALYST SURFACE

1949 ◽  
Vol 27b (4) ◽  
pp. 303-317 ◽  
Author(s):  
Maurice M. Wright ◽  
Hugh S. Taylor
Keyword(s):  
Kinetic Data ◽  
Surface Reaction ◽  
Catalyst Surface ◽  
Dissociative Adsorption ◽  
Fischer Tropsch ◽  
Heats Of Adsorption ◽  
First Order ◽  
First Order Kinetics ◽  
Surface Equilibrium ◽  
Adsorption Of Methane

The interaction of methane and methane-d4 on nickel has been re-examined. The data strengthen the previous concept of a dissociative adsorption of methane on the catalyst. The kinetic data indicate first-order disappearance of methane-d4 with an activation energy of 20.9 kcal. between 100° and 255 °C. Poisoning by carbonaceous residues occurs at all temperatures. First-order kinetics are indicated for the formation of methane-d3 and methane-d2 on the catalyst surface. Reaction of hydrogen with surface residues, after an exchange reaction, indicate that CX, CX2, and CX3 fragments are present on the surface where X is H or D. Higher temperatures favor an equilibrium between these fragments on the surface, equilibrium being displaced towards CX3 as temperature increases. This equilibrium will be dependent on the heats of adsorption of the fragments and of hydrogen on the surface and therefore involves also the metal used as catalyst. The data suggest a basic approach to the mechanism of the Fischer–Tropsch synthesis on metal catalysts.

scholarly journals Kinetic Modelling of Biodegradability Data of Commercial Polymers Obtained under Aerobic Composting Conditions

Eng ◽  
2021 ◽  
Vol 2 (1) ◽  
pp. 54-68
Author(s):  
Ilenia Rossetti ◽  
Francesco Conte ◽  
Gianguido Ramis
Keyword(s):  
Kinetic Data ◽  
Kinetic Modelling ◽  
Kinetic Equations ◽  
Second Order ◽  
Aerobic Biodegradation ◽  
First Order ◽  
First Order Kinetics ◽  
Plastic Materials ◽  
Partial Degradation ◽  
Commercial Polymers

Methods to treat kinetic data for the biodegradation of different plastic materials are comparatively discussed. Different samples of commercial formulates were tested for aerobic biodegradation in compost, following the standard ISO14855. Starting from the raw data, the conversion vs. time entries were elaborated using relatively simple kinetic models, such as integrated kinetic equations of zero, first and second order, through the Wilkinson model, or using a Michaelis Menten approach, which was previously reported in the literature. The results were validated against the experimental data and allowed for computation of the time for half degradation of the substrate and, by extrapolation, estimation of the final biodegradation time for all the materials tested. In particular, the Michaelis Menten approach fails in describing all the reported kinetics as well the zeroth- and second-order kinetics. The biodegradation pattern of one sample was described in detail through a simple first-order kinetics. By contrast, other substrates followed a more complex pathway, with rapid partial degradation, subsequently slowing. Therefore, a more conservative kinetic interpolation was needed. The different possible patterns are discussed, with a guide to the application of the most suitable kinetic model.

Infrared Investigation of H2S Adsorption and Decomposition on Alumina and on Alumina Supported Molybdenum Sulfide

1972 ◽  
Vol 50 (21) ◽  
pp. 3416-3423 ◽  
Author(s):  
T. L. Slager ◽  
C. H. Amberg
Keyword(s):  
Hydrogen Bonding ◽  
Rate Constants ◽  
Kinetic Data ◽  
Surface Reaction ◽  
Molybdenum Sulfide ◽  
Subsequent Reaction ◽  
Alumina Support ◽  
First Order ◽  
H2s Adsorption ◽  
Surface Bond

Adsorption and subsequent reaction of H2S on alumina gave major i.r. bands at 1341, 1568, 1625, and 3400 cm−1. Relative band intensities were used to follow the first order decomposition of adsorbed H2S and formation of H2O. Rate constants of the surface reaction at 23, 55, and 80 °C were 0.70, 1.48, and 3.42 × 10−3 s−1, respectively. A mechanism consistent with the observed spectral and kinetic data involved adsorption to an exposed Al ion forming an Al—S surface bond, and hydrogen bonding to neighboring O and OH species. It was assumed that the sulfur remained on the surface as a sulfide. The 1568 cm−1 band was discussed in terms of an Al—O species.With adsorption on MoS2–Al2O3, bands appeared at 1330 and 1575 cm−1. Behavior in all respects was similar to that observed on the alumina support alone.

Some observations on the kinetics of the Jaffé reaction for creatinine.

1977 ◽  
Vol 23 (9) ◽  
pp. 1527-1530 ◽  
Author(s):  
R M Shoucri ◽  
M Pouliot
Keyword(s):  
Rate Constants ◽  
Kinetic Data ◽  
Serum Samples ◽  
First Order ◽  
Order Rate ◽  
First Order Kinetics ◽  
Pseudo First Order ◽  
Kinetics Of

Abstract The Jaffé reaction for creatinine assay appears to follow pseudo-first-order kinetics; first-order rate constants are different for different samples. Rate constants for 10 different serum samples varied from a low value of 0.0040 +/- 0.0003 s-1 to 0.0084 +/- 0.0008 s-1. We describe an approach for determining first-order rate constants from kinetic data and discuss the effects of the above observations on the mathematical formulations required for reliable kinetic determinations of creatinine.

Photo-catalytic degradation of gaseous pollutants in paper mills of southern China

TAPPI Journal ◽  
2018 ◽  
Vol 17 (03) ◽  
pp. 167-178 ◽  
Author(s):  
Xin Tong ◽  
Jiao Li ◽  
Jun Ma ◽  
Xiaoquan Chen ◽  
Wenhao Shen
Keyword(s):  
Degradation Rate ◽  
Southern China ◽  
Catalytic Degradation ◽  
Pulp And Paper ◽  
Gaseous Pollutants ◽  
Pulp And Paper Mills ◽  
Paper Mills ◽  
Initial Concentration ◽  
First Order ◽  
First Order Kinetics

Studies were undertaken to evaluate gaseous pollutants in workplace air within pulp and paper mills and to consider the effectiveness of photo-catalytic treatment of this air. Ambient air at 30 sampling sites in five pulp and paper mills of southern China were sampled and analyzed. The results revealed that formaldehyde and various benzene-based molecules were the main gaseous pollutants at these five mills. A photo-catalytic reactor system with titanium dioxide (TiO2) was developed and evaluated for degradation of formaldehyde, benzene and their mixtures. The experimental results demonstrated that both formaldehyde and benzene in their pure forms could be completely photo-catalytic degraded, though the degradation of benzene was much more difficult than that for formaldehyde. Study of the photo-catalytic degradation kinetics revealed that the degradation rate of formaldehyde increased with initial concentration fitting a first-order kinetics reaction. In contrast, the degradation rate of benzene had no relationship with initial concentration and degradation did not conform to first-order kinetics. The photo-catalytic degradation of formaldehyde-benzene mixtures indicated that formaldehyde behaved differently than when treated in its pure form. The degradation time was two times longer and the kinetics did not reflect a first-order reaction. The degradation of benzene was similar in both pure form and when mixed with formaldehyde.

Modeling the Electrical Double Layer to Understand the Reaction Environment in a CO2 Electrocatalytic System

2019 ◽  
Author(s):  
Divya Bohra ◽  
Jehanzeb Chaudhry ◽  
Thomas Burdyny ◽  
Evgeny Pidko ◽  
wilson smith
Keyword(s):  
Electric Field ◽  
Double Layer ◽  
Electrical Double Layer ◽  
Surface Reaction ◽  
Catalyst Surface ◽  
Local Reaction ◽  
Reaction Diffusion ◽  
Alkali Metal Cations ◽  
Applied Potential ◽  
Critical Aspect

<p>The environment of a CO<sub>2</sub> electroreduction (CO<sub>2</sub>ER) catalyst is intimately coupled with the surface reaction energetics and is therefore a critical aspect of the overall system performance. The immediate reaction environment of the electrocatalyst constitutes the electrical double layer (EDL) which extends a few nanometers into the electrolyte and screens the surface charge density. In this study, we resolve the species concentrations and potential profiles in the EDL of a CO<sub>2</sub>ER system by self-consistently solving the migration, diffusion and reaction phenomena using the generalized modified Poisson-Nernst-Planck (GMPNP) equations which include the effect of volume exclusion due to the solvated size of solution species. We demonstrate that the concentration of solvated cations builds at the outer Helmholtz plane (OHP) with increasing applied potential until the steric limit is reached. The formation of the EDL is expected to have important consequences for the transport of the CO<sub>2</sub> molecule to the catalyst surface. The electric field in the EDL diminishes the pH in the first 5 nm from the OHP, with an accumulation of protons and a concomitant depletion of hydroxide ions. This is a considerable departure from the results obtained using reaction-diffusion models where migration is ignored. Finally, we use the GMPNP model to compare the nature of the EDL for different alkali metal cations to show the effect of solvated size and polarization of water on the resultant electric field. Our results establish the significance of the EDL and electrostatic forces in defining the local reaction environment of CO<sub>2</sub> electrocatalysts.</p>

Kinetic of oxidation of methyl orange by vanadium(V) under conditions VO2+ and decavanadates coexist: Catalysis by Triton X-100 micellar medium

2019 ◽  
Author(s):  
Chem Int
Keyword(s):  
Methyl Orange ◽  
Solution Ph ◽  
Vanadium Concentration ◽  
Limiting Behavior ◽  
First Order ◽  
First Order Kinetics ◽  
Ph Range ◽  
Kinetic Pattern ◽  
Triton X ◽  
Kinetics Of

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 &lt; 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.

Biodegradation rates of aromatic contaminants in biofilm reactors

1995 ◽  
Vol 31 (1) ◽  
pp. 117-128 ◽  
Author(s):  
Jean-Pierre Arcangeli ◽  
Erik Arvin
Keyword(s):  
Aromatic Hydrocarbons ◽  
Competitive Inhibition ◽  
Removal Rate ◽  
First Order ◽  
Biofilm Reactors ◽  
First Order Kinetics ◽  
Reducing Conditions ◽  
Low Concentrations ◽  
Degradation Rates ◽  
Order Surface

This study has shown that microorganisms can adapt to degrade mixtures of aromatic pollutants at relatively high rates in the μg/l concentration range. The biodegradation rates of the following compounds were investigated in biofilm systems: aromatic hydrocarbons, phenol, methylphenols, chlorophenols, nitrophenol, chlorobenzenes and aromatic nitrogen-, sulphur- or oxygen-containing heterocyclic compounds (NSO-compounds). Furthermore, a comparison with degradation rates observed for easily degradable organics is also presented. At concentrations below 20-100 μg/l the degradation of the aromatic compounds was typically controlled by first order kinetics. The first-order surface removal rate constants were surprisingly similar, ranging from 2 to 4 m/d. It appears that NSO-compounds inhibit the degradation of aromatic hydrocarbons, even at very low concentrations of NSO-compounds. Under nitrate-reducing conditions, toluene was easily biodegraded. The xylenes and ethylbenzene were degraded cometabolically if toluene was used as a primary carbon source; their removal was influenced by competitive inhibition with toluene. These interaction phenomena are discussed in this paper and a kinetic model taking into account cometabolism and competitive inhibition is proposed.

In-vitro Kinetic Hydrolysis Study of Metronidazole Derivatives with Carvacrol and Eugenol Using Validated RP-HPLC Method

2020 ◽  
Vol 16 ◽  
Author(s):  
M. Alarjah
Keyword(s):  
Half Life ◽  
Hplc Method ◽  
Hydrolysis Rate ◽  
First Order ◽  
First Order Kinetics ◽  
Rp Hplc ◽  
Pharmacokinetic Properties ◽  
Pseudo First Order ◽  
Kinetic Hydrolysis

Background: Prodrugs principle is widely used to improve the pharmacological and pharmacokinetic properties of some active drugs. Much effort was made to develop metronidazole prodrugs to enhance antibacterial activity and or to improve pharmacokinetic properties of the molecule or to lower the adverse effects of metronidazole. Objective: In this work, the pharmacokinetic properties of some of monoterpenes and eugenol pro metronidazole molecules that were developed earlier were evaluated in-vitro. The kinetic hydrolysis rate constants and half-life time estimation of the new metronidazole derivatives were calculated using the validated RP-HPLC method. Method: Chromatographic analysis was done using Zorbbax Eclipse eXtra Dense Bonding (XDB)-C18 column of dimensions (250 mm, 4.6 mm, 5 μm), at ambient column temperature. The mobile phase was a mixture of sodium dihydrogen phosphate buffer of pH 4.5 and methanol in gradient elution, at 1ml/min flow rate. The method was fully validated according to the International Council for Harmonization (ICH) guidelines. The hydrolysis process carried out in an acidic buffer pH 1.2 and in an alkaline buffer pH 7.4 in a thermostatic bath at 37ºC. Results: The results followed pseudo-first-order kinetics. All metronidazole prodrugs were stable in the acidic pH, while they were hydrolysed in the alkaline buffer within a few hours (6-8 hr). The rate constant and half-life values were calculated, and their values were found to be 0.082- 0.117 hr-1 and 5.9- 8.5 hr., respectively. Conclusion: The developed method was accurate, sensitive, and selective for the prodrugs. For most of the prodrugs, the hydrolysis followed pseudo-first-order kinetics; the method might be utilised to conduct an in-vivo study for the metronidazole derivatives with monoterpenes and eugenol.

Decomposition of 4,4'-(Diazoamino)-bis(5-methoxy-2-methylbenezenesulfonic Acid) in Solutions ofFD&C Red No. 40

1984 ◽  
Vol 67 (4) ◽  
pp. 844-845
Author(s):  
Naomi Richfield-Fratz
Keyword(s):  
Liquid Chromatography ◽  
Aqueous Solutions ◽  
Borate Buffer ◽  
Sodium Borate ◽  
First Order ◽  
First Order Kinetics ◽  
Color Additive ◽  
Sodium Borate Buffer

Abstract 4,4'-(Diazoamino)-bis(5-methoxy-2-methylbenzenesuIfonic acid), when present as a reaction by-product in FD&C Red No. 40, is shown to decompose rapidly in aqueous solutions of the color additive. The decomposition is halted by the addition of sodium borate buffer. Quantitationly liquid chromatography shows that decomposition is nonlinear with time and follows approximate first order kinetics.

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