A Stirred-Flow Reactor for Investigating the Kinetics of Gaseous Reactions: Application to the Decomposition of Di-t-butyl Peroxide

1961 ◽  
Vol 14 (4) ◽  
pp. 534 ◽  
Author(s):  
MFR Mulcahy ◽  
DJ Williams
Keyword(s):  
Excellent Agreement ◽  
Rate Constant ◽  
Flow Reactor ◽  
Reaction Times ◽  
Static Method ◽  
Flow Conditions ◽  
Gaseous Reaction ◽  
Flow Method ◽  
Butyl Peroxide ◽  
Kinetics Of

The uncertainty regarding temperature and flow conditions which attaches to the conventional flow method of determining the rate of a gaseous reaction can be substantially reduced by using a stirred-flow reactor. The reagents, products, and carrier-gas (if any) are mixed sufficiently vigorously for the composition of the gas in the reactor to be virtually uniform. A reactor designed to achieve the required degree of mixing at pressures of about 1 cmHg and reaction times of the order of 1 sec to 1 min is described. The rate constant of the decomposition of di-t-butyl peroxide was determined over the temperature range 430-550 �K. The values derived on the assumption of complete mixing in the reactor were independent of the degree of conversion and in excellent agreement with those obtained by previous authors using the static method.

Kinetics of reactions involving CN emission IV. Study of the reactions of CN by electronic absorption spectroscopy

1968 ◽  
Vol 305 (1480) ◽  
pp. 107-123 ◽  
Keyword(s):  
Absorption Spectroscopy ◽  
Rate Constant ◽  
Electronic Absorption ◽  
Flow Reactor ◽  
Initial Step ◽  
Electronic Absorption Spectroscopy ◽  
Kinetics Of ◽  
Cn Radicals ◽  
Limiting Values ◽  
Oxygen Atoms

The kinetics of the reaction between oxygen atoms and cyanogen have been studied in a capacity flow reactor at temperatures between 570 and 687 °K. The concentration of CN radicals was measured by electronic absorption spectroscopy. This work confirms the previously proposed mechanism (part II). The initial step has a rate constant of k 1 = 2∙5 (± 0∙3) x 10 13 exp ( – 11000±2000/ RT ) cm 3 mole –1 s –1 . CN radicals are removed mainly by reactions (4) and (2) for which k 4 = 6∙3 (±3∙5) x 10 13 exp (–2400±700/ RT ) cm 3 mole –1 s –1 and k 2 = 4∙4 (±2∙0) x 10 12 cm 3 mole –1 s –1 . CN+O = CO+N, (4) CN+O 2 = NCO+O. (2) The rates of reaction of CN with NO and NH 3 were also measured; for CH 4 and H 2 limiting values were obtained.

Etude du système acridine orange – poly(C) et de son interaction avec les complexes du palladium(II)

1984 ◽  
Vol 62 (9) ◽  
pp. 1681-1686 ◽  
Author(s):  
Robert Ménard ◽  
Miklos Zador
Keyword(s):  
Acridine Orange ◽  
Thermodynamic Parameters ◽  
Rate Constant ◽  
Kinetic Studies ◽  
Stopped Flow ◽  
Flow Method ◽  
Polycytidylic Acid ◽  
Low Concentrations ◽  
C Complex ◽  
Kinetics Of

The complex formed between acridine orange (AO) and polycytidylic acid (poly(C)) was studied by spectrophotometry and spectrofluorometry. The complex was characterized by its stoichiometry, structure, and the thermodynamic parameters of its formation. The results are in agreement with an external aggregation of the protonated dye along the negatively charged poly(C) chain and indicate that approximately two AO molecules are bound per nucleotide unit of poly(C). The kinetics of the reaction between this complex and a Pd(II) complex was studied by the stopped-flow method. The addition of (dien)Pd(II) to the AO–poly(C) complex leads to the dissociation of the latter, due to fixation of the Pd(II) complex to the N3 site of the cytosine base of poly(C). The rate constant for the AO liberation, extrapolated at zero AO concentration, corresponds to the rate constant of Pd(II) fixation on poly(C). This indicates that AO can be used as an indicator for this reaction and allows kinetic studies at very low concentrations (≤ 5 × 10−6 M).

Errors in Determining the Rate Constant of a First-order Gaseous Reaction by the Flow Method

1963 ◽  
Vol 16 (4) ◽  
pp. 527 ◽  
Author(s):  
MFR Mulcahy ◽  
MR Pethard
Keyword(s):  
Rate Constant ◽  
Thermal Equilibrium ◽  
Contact Time ◽  
Experimental Conditions ◽  
Gaseous Reaction ◽  
Flow Method ◽  
First Order ◽  
Upper Limit ◽  
Piston Flow ◽  
Organic Vapour

The rate constant of a gaseous reaction calculated from data obtained by the conventional flow method is subject to errors arising from departures from piston flow and thermal equilibrium in the reaction tube. An approximate theoretical analysis of the errors is given for the first-order pyrolysis or isomerization of an organic vapour. In the case of a reaction occurring near 1000�K in a tube 2 cm in diameter, it is shown that for the measured value of the rate constant to be accurate within about 10% the experimental conditions should be such that z > tc/p > 0.5, where p cmHg is the total pressure and tc sec the average contact time. The upper limit (z) of tc/p increases from 3 under conditions of 50% conversion to 10 at 25% and ∞ at 0%. The analysis is applied to measurements of the rate of pyrolysis of toluene. Lack of thermal equilibrium could be at least partly responsible for the observed effect of contact time on the rate constant but does not account for the effect of pressure. The error incurred by assuming piston flow in an isothermal reactor when in fact viscous flow is occurring is discussed in the Appendix.

scholarly journals Stopped-Flow Spectrophotometric Studies of the Kinetics of Interaction of Dihydroxyfumaric Acid with the DPPH Free Radical

2010 ◽  
Vol 5 (2) ◽  
pp. 83-87
Author(s):  
Natalia Secara
Keyword(s):  
Free Radical ◽  
Reaction Kinetics ◽  
Rate Constant ◽  
Stopped Flow ◽  
Flow Method ◽  
Reaction Proceeds ◽  
Reaction Orders ◽  
Stoichiometric Reaction ◽  
Two Stages ◽  
Kinetics Of

The reaction of dihydroxyfumaric acid with the free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) was studied using the stopped-flow method, in order to describe the reaction kinetics. Dihydroxyfumaric acid reacts very rapidly with DPPH, the reaction being completed in several minutes. This 2-stoichiometric reaction proceeds in two stages, with reaction orders of 1 and 0.76 with respect to DPPH, and 0.5 and 0.3 with respect to DHF, respectively. The rate constant of the two stages of the reaction were found to be 39.1 (L/mol•s) and 0.0012 (s-1) at 20º C and pH 4.0.

Kinetics of the Fully Inhibited Thermal Decomposition of Bistrifluoromethyl Peroxide, CF3OOCF3

1975 ◽  
Vol 53 (10) ◽  
pp. 1442-1448 ◽  
Author(s):  
Bernard Descamps ◽  
Wendell Forst
Keyword(s):  
Thermal Decomposition ◽  
Gas Phase ◽  
Rate Constant ◽  
Chromatographic Analysis ◽  
Static Method ◽  
Experimental Conditions ◽  
Experimental Expression ◽  
Kinetics Of ◽  
Rate Of Accumulation

The pyrolyosis of CF3OOCF3 (BTMP) was studied in the gas phase from 5 to 100 Torr BTMP pressure and between 197 and 244 °C in a clean nickel reactor by the static method. CF3O radicals, due to the initial split[Formula: see text] were scavenged by SO3F radicals produced in situ by the thermal decomposition of their dimer S2O6F2. Under these conditions, CF3OOSO2F is the only product of BTMP pyrolysis, as shown by gas chromatographic analysis. Thus the BTMP pyrolysis becomes fully inhibited and the rate of accumulation of CF3OOSO2F is a measure of k1. The rate constant k1 turns out to be pressure-insensitive under the experimental conditions, from which it is inferred that k1 is actually k1∞, the limiting high-pressure unimolecular rate constant for reaction 1. Its temperature dependence yields the result[Formula: see text]This result is compared with other values of the O—O bond dissociation energy in BTMP. The experimental expression for k1 ∞ is used to construct the pressure falloff of k1 following the procedure of Forst. The calculation confirms that falloff begins only below 10 Torr.

Particle Destabilization in Turbulent Pipe Flow

1989 ◽  
Vol 21 (6-7) ◽  
pp. 435-442 ◽  
Author(s):  
B. Döll
Keyword(s):  
Pipe Flow ◽  
Reaction Rate ◽  
Turbulent Pipe Flow ◽  
Cationic Polymers ◽  
Flow Conditions ◽  
Polyelectrolyte Adsorption ◽  
Charge Neutralization ◽  
Silica Suspensions ◽  
Kinetics Of ◽  
Turbulent Flow Conditions

Silica suspensions (pH = 6.8) and three different cationic polymers were used to study the kinetics of charge neutralization by polyelectrolyte adsorption. The experiments were performed in a continuous flow pipe reactor under steady state turbulent flow conditions. The charge neutralization was monitored by electrophoretic mobility (EPM) measurements of the suspended particles as a function of time after polyelectrolyte audition. The results show the dependency of the destabilization reaction rate on flow and polymer characteristics.

Kinetics of the catalytic hydrodesulphurization reaction system; hydrogenolysis of thiophene

1980 ◽  
Vol 45 (10) ◽  
pp. 2728-2741 ◽  
Author(s):  
Pavel Fott ◽  
Petr Schneider
Keyword(s):  
Atmospheric Pressure ◽  
Active Sites ◽  
Flow Reactor ◽  
Kinetic Equations ◽  
Reaction System ◽  
Reaction Products ◽  
Molybdenum Catalyst ◽  
Cobalt Molybdenum Catalyst ◽  
Kinetics Of ◽  
Reaction Schemes

Kinetics have been studied of the reaction system taking place during the reaction of thiophene on the cobalt-molybdenum catalyst in a gradientless circulation flow reactor at 360 °C and atmospheric pressure. Butane has been found present in a small amount in the reaction products even at very low conversion. In view of this, consecutive and parallel-consecutive (triangular) reaction schemes have been proposed. In the former scheme the appearance of butane is accounted for by rate of desorption of butene being comparable with the rate of its hydrogenation. According to the latter scheme part of the butane originates from thiophene via a different route than through hydrogenation of butene. Analysis of the kinetic data has revealed that the reaction of thiophene should be considered to take place on other active sites than that of butene. Kinetic equations derived on this assumption for the consecutive and the triangular reaction schemes correlate experimental data with acceptable accuracy.

Kinetics of Substitution of 4-Methoxyphenylazo Groups of 2,6-Dioxo-5(3)-(4-methoxyphenylazo)-3(5)-(4-methoxyphenylhydrazono)-1,2,3,6-tetrahydropyridine-4-carboxylic Acid by Reaction with 4-Nitrobenzenediazonium Cation

1994 ◽  
Vol 59 (7) ◽  
pp. 1665-1672 ◽  
Author(s):  
Jaroslava Horáčková ◽  
Vojeslav Štěrba
Keyword(s):  
Carboxylic Acid ◽  
Rate Constant ◽  
Kinetics Of

Kinetics have been studied of gradual replacement of 4-methoxyphenylazo groups in 2,6-dioxo-5(3)-(4-methoxyphenylazo)-3(5)-(4-methoxyphenylhydrazono)-1,2,3,6-tetrahydropyridine-4-carboxylic acid (IIIa) by 4-nitrophenylazo groups using the reaction with 4-nitrobenzenediazonium cation (IIc) in acetate and phosphate buffers. The rate constant of replacement of the second methoxyphenylazo group is lower by a factor of ca 60. From the experimentally found pKa values of the corresponding azohydrazone compounds with methoxy, chloro, or nitro substituent at 4-position (IIIa - IIIf) it has been concluded that the 5(3)-(4-methoxyphenylazo)-3(5)-(4-nitrophenylhydrazono) derivative is formed in the first step.

scholarly journals Simultaneous Kinetics of Selenite Oxidation and Sorption on δ-MnO2 in Stirred-Flow Reactors

2021 ◽  
Vol 18 (6) ◽  
pp. 2902
Author(s):  
Zheyong Li ◽  
Yajun Yuan ◽  
Lin Ma ◽  
Yihui Zhang ◽  
Hongwei Jiang ◽  
...  
Keyword(s):  
Rate Constant ◽  
Photoelectron Spectroscopy ◽  
Oxide Surfaces ◽  
Kinetic Rate Constant ◽  
Flow Reactors ◽  
Mn Oxide ◽  
Remediation Strategies ◽  
Process Of Se ◽  
Kinetics Of

Selenium (Se) is an essential and crucial micronutrient for humans and animals, but excessive Se brings negativity and toxicity. The adsorption and oxidation of Se(IV) on Mn-oxide surfaces are important processes for understanding the geochemical fate of Se and developing engineered remediation strategies. In this study, the characterization of simultaneous adsorption, oxidation, and desorption of Se(IV) on δ-MnO2 mineral was carried out using stirred-flow reactors. About 9.5% to 25.3% of Se(IV) was oxidized to Se(VI) in the stirred-flow system in a continuous and slow process, with the kinetic rate constant k of 0.032 h−1, which was significantly higher than the apparent rate constant of 0.0014 h−1 obtained by the quasi-level kinetic fit of the batch method. The oxidation reaction was driven by proton concentration, and its rate also depended on the Se(IV) influent concentration, flow rate, and δ-MnO2 dosage. During the reaction of Se(IV) and δ-MnO2, Mn(II) was produced and adsorbed strongly on Mn oxide surfaces, which was evidenced by the total reflectance Fourier transform infrared (ATR-FTIR) results. The X-ray photoelectron spectroscopy (XPS) data indicated that the reaction of Se(VI) on δ-MnO2 produced Mn(III) as the main product. These results contribute to a deeper understanding of the interface chemical process of Se(IV) with δ-MnO2 in the environment.

scholarly journals Physical properties and water absorption kinetics of three varieties of Mucuna beans

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Ajibola B. Oyedeji ◽  
Olajide P. Sobukola ◽  
Ezekiel Green ◽  
Oluwafemi A. Adebo
Keyword(s):  
Physical Properties ◽  
Water Absorption ◽  
Rate Constant ◽  
Geometric Mean ◽  
Seed Mass ◽  
Activation Energies ◽  
Mucuna Pruriens ◽  
Absorption Kinetics ◽  
Kinetics Of ◽  
Soaking Temperature

AbstractThe physical properties and water absorption kinetics of three varieties of Mucuna beans (Mucuna pruriens, Mucuna rajada and Mucuna veracruz) were determined in this study. Physical properties including length, width, thickness, geometric mean diameter, sphericity, porosity, bulk density, area, volume and one thousand seed mass were calculated while hydration kinetics was studied by soaking Mucuna beans in water at 30 °C, 40 °C and 50 °C and measuring water uptake at 9 h interval. Peleg’s equation was used to model the hydration characteristics and Arrhenius equation was used to describe the effect of temperature on Peleg’s rate constant k1 and to obtain the activation energies for soaking. Significant variations were observed in almost all the physical properties of the different varieties, however, there were no significant differences (p < 0.05) in their thicknesses and bulk densities. The effectiveness of fit of Peleg’s model (R2) increased with increase in soaking temperature. Peleg’s rate constant k1 decreased with increase in soaking temperature while k2 increased with temperature increase. Activation energies of Mucuna pruriens, Mucuna rajada and Mucuna veracruz were 1613.24 kJ/mol, 747.95 kJ/mol and 2743.64 kJ/mol, respectively. This study provides useful information about the properties of three varieties of Mucuna beans that could be of importance to processors and engineers for process design and optimization.

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