The apparent chemical kinetics of surface reactions in external flow systems: Diffusional falsification of activation energy and reaction order

AIChE Journal ◽  
1963 ◽  
Vol 9 (3) ◽  
pp. 321-331 ◽  
Author(s):  
Daniel E. Rosner
Keyword(s):  
Activation Energy ◽  
Chemical Kinetics ◽  
Reaction Order ◽  
Surface Reactions ◽  
External Flow ◽  
Flow Systems ◽  
Kinetics Of

Vulcanization of Elastomers. 23. The Chemical Kinetics of Vulcanization Reactions and The Physical Properties of The Vulcanizates. I

1960 ◽  
Vol 33 (2) ◽  
pp. 335-341
Author(s):  
Walter Scheele ◽  
Karl-Heinz Hillmer
Keyword(s):  
Activation Energy ◽  
Physical Properties ◽  
Chemical Kinetics ◽  
Kcal Mole ◽  
First Order ◽  
Equilibrium Swelling ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization ◽  
Limiting Value ◽  
Good Agreement

Abstract As a complement to earlier investigations, and in order to examine more closely the connection between the chemical kinetics and the changes with vulcanization time of the physical properties in the case of vulcanization reactions, we used thiuram vulcanizations as an example, and concerned ourselves with the dependence of stress values (moduli) at different degrees of elongation and different vulcanization temperatures. We found: 1. Stress values attain a limiting value, dependent on the degree of elongation, but independent of the vulcanization temperature at constant elongation. 2. The rise in stress values with the vulcanization time is characterized by an initial delay, which, however, is practically nonexistent at higher temperatures. 3. The kinetics of the increase in stress values with vulcanization time are both qualitatively and quantitatively in accord with the dependence of the reciprocal equilibrium swelling on the vulcanization time; both processes, after a retardation, go according to the first order law and at the same rate. 4. From the temperature dependence of the rate constants of reciprocal equilibrium swelling, as well as of the increase in stress, an activation energy of 22 kcal/mole can be calculated, in good agreement with the activation energy of dithiocarbamate formation in thiuram vulcanizations.

scholarly journals Kinetic study of wood pyrolysis in presence of metal halides

2014 ◽  
Vol 12 (12) ◽  
pp. 1294-1303 ◽  
Author(s):  
Vladimir Beliy ◽  
Elena Udoratina
Keyword(s):  
Activation Energy ◽  
Lewis Acids ◽  
Alkaline Earth ◽  
Reaction Order ◽  
Earth Metal ◽  
Inorganic Salts ◽  
Alkaline Earth Metal ◽  
Metal Halides ◽  
Wood Pyrolysis ◽  
Kinetics Of

AbstractThe purpose of this work was to study the kinetics of wood pyrolysis in the presence of inorganic salts, representatives of classes of alkali and alkaline earth metal halides (NaCl, KCl, KBr, CaCl2, BaCl2·2H2O) and Lewis acids (AlCl3·6H2O, FeCl3·6H2O, CuCl2, CuBr2, ZnCl2·1.5H2O, NiCl2·6H2O, SnCl2·2H2O) using TG-DSC. The activity of these catalysts was estimated by the temperature of the beginning of pyrolysis, charcoal yield and kinetic parameters, such as energy of activation and reaction order. Using the Lewis acids as catalysts for pyrolysis leads to a decrease in the temperature of the process beginning and the activation energy. In the presence of other catalysts activation energy does not significantly change. The increase of a seeming reaction order in the presence of Lewis acids possibly is a consequence of complication of the thermodestruction mechanism, with the appearance of new parallel competing stages.

Synthesis and Determination of the Kinetic Parameters for Non-Isothermal Decomposition of Complexes Ln(thd)3phen

2006 ◽  
Vol 530-531 ◽  
pp. 506-512 ◽  
Author(s):  
Wilton Silva Lopes ◽  
Crislene Rodrigues da Silva Morais ◽  
A.G. de Souza
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Lanthanide Complexes ◽  
Reaction Order ◽  
Decomposition Reaction ◽  
Cylindrical Symmetry ◽  
Boundary Reaction ◽  
Phase Boundary Reaction ◽  
Kinetics Of

In this work the kinetics of the thermal decomposition of two ß-diketone lanthanide complexes of the general formula Ln(thd)3phen (where Ln = Nd+3 or Tm+3, thd = 2,2,6,6- tetramethyl-3,5-heptanodione and phen = 1,10-phenantroline) has been studied. The powders were characterized by several techniques. Thermal decomposition of the complexes was studied by non-isothermal thermogravimetry techniques. The kinetic model that best describes the process of the thermal decomposition of the complexes it was determined through the method proposed by Coats-Redfern. The average values the activation energy obtained were 136 and 114 kJ.mol-1 for the complexes Nd(thd)3phen and Tm(thd)3phen, respectively. The kinetic models that best described the thermal decomposition reaction the both complexes were R2. The model R2 indicating that the mechanism is controlled by phase-boundary reaction (cylindrical symmetry) and is defined by the function g(α) = 2[1-(1-a)1/2], indicating a mean reaction order. The values of activation energy suggests the following decreasing order of stability: Nd(thd)3phen > Tm(thd)3phen.

scholarly journals Kinetics of the Carbon Monoxide Oxidation Reaction Under Microwave Heating

1996 ◽  
Vol 430 ◽  
Author(s):  
W. Lee Perry ◽  
Joel D. Katz ◽  
Daniel Rees ◽  
Mark T. Paffett ◽  
Abhaya Datye
Keyword(s):  
Activation Energy ◽  
Carbon Monoxide ◽  
Co Oxidation ◽  
Microwave Heating ◽  
Oxidation Reaction ◽  
Reaction Order ◽  
Thermal Gradients ◽  
Exponential Factor ◽  
Co Oxidation Reaction ◽  
Kinetics Of

Abstract915 MHz microwave heating has been used to drive the CO oxidation reaction over Pd/Al2O3 without significantly affecting the reaction kinetics. As compared to an identical conventionally heated system, the activation energy, pre-exponential factor, and reaction order with respect to CO were unchanged. Temperature was measured using a thermocouple extrapolation technique. Microwave-induced thermal gradients were found to play a significant role in kinetic observations.

THE CIS-TRANS ISOMERIZATION OF AZOBENZENE IN SOLUTION

1950 ◽  
Vol 28b (4) ◽  
pp. 140-155 ◽  
Author(s):  
C. A. Winkler ◽  
J. Halpern ◽  
G. W. Brady
Keyword(s):  
Activation Energy ◽  
Internal Pressure ◽  
Solvent Effect ◽  
Chemical Kinetics ◽  
Linear Relation ◽  
Mixed Solvents ◽  
Square Root ◽  
Polar Solvents ◽  
Trans Isomerization ◽  
Kinetics Of

Relations for the solvent effect on the rate of a unimolecular, nonionic reaction are derived, using existing theories of solutions and of chemical kinetics. The kinetics of the cis-trans isomerization of azobenzene were investigated in 16 pure solvents. A linear relation between the activation energy, E, and the square root of the internal pressure of the solvent, (P′S)1/2 was found, in agreement with the theory. Linear relations between log A and E, and between log k and (P′S)1/2 were also found, but the results for the reaction in highly polar solvents deviated significantly from these relations. The kinetics of the reaction in mixed solvents indicate that the azobenzene is preferentially surrounded by the component in which it is more readily soluble.

Gas Phase and Surface Reactions of Organometallic Arsenic Sources

1989 ◽  
Vol 145 ◽  
Author(s):  
T.R. Omstead ◽  
S. Brandon ◽  
M. Hoveland ◽  
K.F. Jensen ◽  
D.A. Bohling ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Growth Rate ◽  
Gas Phase ◽  
Chemical Kinetics ◽  
Molecular Beam ◽  
Surface Reactions ◽  
Molecular Beam Mass Spectrometry ◽  
The Common ◽  
Kinetics Of

AbstractThe chemical kinetics of two new organometallic arsenic substitutes, tris-trifluoromethylarsenic (As(CF3)3) and phenylarsine (PhAsH2), for use in the MOCVD of GaAs have been characterized through the use of microbalance gravimetry and molecular beam mass spectrometry. Both growth rate and gas-phase cracking studies demonstrate that phenylarsine interacts only slightly with the common gallium precursors, which may make it a useful alternative to arsine. Growth with tris-trifluoromethylarsenic is achieved only at low V/III ratios and with pressures above 250 Torr. The compound etches GaAs under most conditions.

The Kinetics of Oxygen Delignification of Reed Kraft Pulp (I)-Kinetics of Delignification

2011 ◽  
Vol 236-238 ◽  
pp. 1420-1424
Author(s):  
Xiao Feng Pan ◽  
Le Fan Ma ◽  
Qin Qin Qu ◽  
Jia Liang Lan ◽  
Li Hong Tan
Keyword(s):  
Activation Energy ◽  
Reaction Time ◽  
Oxygen Pressure ◽  
Kraft Pulp ◽  
Reaction Order ◽  
Frequency Factor ◽  
Kappa Number ◽  
Alkali Concentration ◽  
Oxygen Delignification ◽  
Kinetics Of

The kinetics of reed kraft pulp oxygen delignification process is studied, suitable kinetics model determined is -dk/dt=Aexp(-E/RT) [OH-]b[PO2]cKa, and the parameters in the model is calculated. The function for estimation of the kappa number at different reaction time is established for the reed kraft pulp oxygen delignification process. The reaction order fitted is 6.72 for delignification (a), 0.87 for alkali concentration (b), and 0.62 for oxygen pressure(c), respectively. The activation energy E is 80.96KJ/mol and frequency factor A 1.5×104.

Curing Kinetics of Phenol Formaldehyde Resin Modified with Sodium Silicate

2012 ◽  
Vol 184-185 ◽  
pp. 1471-1479
Author(s):  
Jin Sun ◽  
Xiao Feng Zhu ◽  
Xiao Bo Wang ◽  
Rui Hang Lin ◽  
Zhen Zhong Gao
Keyword(s):  
Activation Energy ◽  
Sodium Silicate ◽  
Reaction Order ◽  
Phenol Formaldehyde ◽  
Curing Kinetics ◽  
Curing Temperature ◽  
Formaldehyde Resin ◽  
Exponential Factor ◽  
Curing Reaction ◽  
Kinetics Of

The curing kinetics of PF resin modified with sodium silicate had been investigated by differential scanning calorimetry (DSC). The kinetic analysis was performed at heating rates of 5, 10, 15, and 20°C/min，respectively. The kinetic parameters such as reaction order and activation energy were solved by Kissinger and Crane equation. The relationship between curing temperature and heating rate was also investigated. The activation energy and the curing reaction order，which were obtained by kinetic calculation, are 83.00kJ/mol and 0.917, respectively. The curing reaction kinetics equations were built by the obtained best curing temperature, reaction order, pre-exponential factor and reaction rate constant.

Kinetics of Rubber-Modified Nylon 6

2014 ◽  
Vol 887-888 ◽  
pp. 951-954
Author(s):  
Hong Kai Zhao ◽  
Hong Li Wang
Keyword(s):  
Activation Energy ◽  
Reaction Order ◽  
Styrene Butadiene Rubber ◽  
Butadiene Rubber ◽  
Exponential Factor ◽  
First Order ◽  
Adiabatic Approach ◽  
Research Findings ◽  
Styrene Butadiene ◽  
Kinetics Of

Kinetic parameters are calculated based on the reactive temperature rise curve measured by adiabatic approach at the temperature of 145 to 160 °C with the catalytic system of NaOH and acyl caprolactam End-capped butadiene-acrylonitrile rubber (CHTBN) or styrene-butadiene rubber (CHTBS). The reaction order is first order, the activation energy is between 72.91−73.16 kJ∙mol−1 and the pre-exponential factor is between 3.22×1011− 3.38×1011 mol1−n∙s−1 in the system of CHTBN/NaOH. While in CHTBS/NaOH, the reaction order is between 1.23-1.34, the activation energy is between 85.55－86.88 kJ∙mol−1 and the pre-exponential factor is between 4.52×1011−5.0 9×1011 mol1−n∙s−1. The adiabatic reaction kinetic model of caprolactam anion was constructed based on the existing research findings, by which the polymerizing reaction is simulated. The coincidence between the simulation results and the experimental data revealed that the model is reasonable and correct.

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