scholarly journals Don't Be Tricked by Your Integrated Rate Plot: Reaction Order Ambiguity

2004 ◽  
Vol 81 (1) ◽  
pp. 32 ◽  
Author(s):  
Sue Le Vent
Keyword(s):  
1980 ◽  
Vol 45 (12) ◽  
pp. 3338-3346
Author(s):  
Miroslav Kašpar ◽  
Jiří Trekoval

The effect of small additions of 1-octene, butyl ethyl ether and triethylamine on the polymerization kinetics of isoprene (2-methyl-1,3-butadiene) in benzene initiated with butyllithium was investigated by employing the GLC analysis. The addition of 1-octane was reflected only in a shorter induction period of the reaction; the effect on the propagation rate was insignificant. With the increasing amount of butyl ethyl ether, the polymerization rate increases linearly, while the reaction order with respect to the concentration of triethylamine is variable and increases from 0.33 to 0.66 with the increasing concentration of the initiator. For a constant concentration of triethylamine, the reaction order with respect to the initial concentration of the initiator was found to vary considerably, reaching even negative values. A reaction scheme was suggested, taking into account the competition between two different solvates of alkyllithium.


1998 ◽  
Vol 63 (11) ◽  
pp. 1945-1953 ◽  
Author(s):  
Jiří Hanika ◽  
Karel Sporka ◽  
Petr Macoun ◽  
Vladimír Kysilka

The activity of ruthenium, palladium, and nickel catalysts for the hydrogenation of 1,2-dihydroacenaphthylene in cyclohexane solution was studied at temperatures up to 180 °C and pressures up to 8 MPa. The GC-MS technique was used to identify most of the perhydroacenaphthylene stereoisomers, whose fractions in the product were found dependent on the nature of the active component of the catalyst. The hydrogenation was fastest on the palladium catalyst (3% Pd/C). The nickel catalyst Ni-NiO/Al2O3, which is sufficiently active also after repeated use, can be recommended for practical application. The activation energy of 1,2-dihydroacenaphthylene hydrogenation using this catalyst is 17 kJ/mol, the reaction order with respect to hydrogen is unity.


Minerals ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 36
Author(s):  
Jiangyan Yuan ◽  
Hongwen Ma ◽  
Zheng Luo ◽  
Xi Ma ◽  
Qian Guo

To make potassium from K-bearing rocks accessible to agriculture, processing on biotite syenite powder under mild alkaline hydrothermal conditions was carried out, in which two types of KAlSiO4 were obtained successfully. The dissolution-precipitation process of silicate rocks is a significant process in lithospheric evolution. Its effective utilization will be of importance for realizing the comprehensiveness of aluminosilicate minerals in nature. Two kinds of KAlSiO4 were precipitated in sequence during the dissolution process of biotite syenite. The crystal structures of two kinds of KAlSiO4 were compared by Rietveld structure refinements. The kinetics model derived from geochemical research was adopted to describe the dissolution behavior. The reaction order and apparent activation energy at the temperature range of 240–300 °C were 2.992 and 97.41 kJ/mol, respectively. The higher dissolution reaction rate of K-feldspar mainly relies on the alkaline solution, which gives rise to higher reaction order. During the dissolution-precipitation process of K-feldspar, two types of KAlSiO4 with different crystal structure were precipitated. This study provides novel green chemical routes for the comprehensive utilization of potassium-rich silicates.


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Ali Kuliaei ◽  
Iraj Amiri Amraei ◽  
Seyed Rasoul Mousavi

Abstract The purpose behind this research was to determine the optimum formulation and investigate the cure kinetics of a diglycidyl ether of bisphenol-A (DGEBA)-based epoxy resin cured by dicyandiamide and diuron for use in prepregs. First, all formulations were examined by the tensile test, and then, the specimens with higher mechanical properties were further investigated by viscometry and tack tests. The cure kinetics of the best formulation (based on tack test) in nonisothermal mode was investigated using differential scanning calorimetry at different heating rates. Kissinger and Ozawa method was used for determining the kinetic parameters of the curing process. The activation energy obtained by this method was 71.43 kJ/mol. The heating rate had no significant effect on the reaction order and the total reaction order was approximately constant ( m + n ≅ 2.1 $m+n\cong 2.1$ ). By comparing the experimental data and the theoretical data obtained by Kissinger and Ozawa method, a good agreement was seen between them. By increasing the degree of conversion, the viscosity decreased; as the degree of conversion increased, so did the slope of viscosity. The results of the tack test also indicated that the highest tack could be obtained with 25% progress of curing.


2013 ◽  
Vol 78 (12) ◽  
pp. 2115-2130 ◽  
Author(s):  
Martinez Gonzalez ◽  
Tanja Vidakovic-Koch ◽  
Rafael Kuwertz ◽  
Ulrich Kunz ◽  
Thomas Turek ◽  
...  

Hydrogen chloride (HCl) oxidation has been investigated on technical membrane electrode assemblies in a cyclone flow cell. Influence of Nafion loading, temperature and hydrogen chloride mole fraction in the gas phase has been studied. The apparent kinetic parameters like reaction order with respect to HCl, Tafel slope and activation energy have been determined from polarization data. The apparent kinetic parameters suggest that the recombination of adsorbed Cl intermediate is the rate determining step.


2013 ◽  
Vol 49 (2) ◽  
pp. 275-283 ◽  
Author(s):  
André Luis Máximo Daneluti ◽  
Jivaldo do Rosário Matos

Phytic acid is a natural compound widely used as depigmenting agent in galenic cosmetic emulsions. However, we have observed experimentally that phytic acid, when heated to 150 ºC for around one hour, shows evidence of thermal decomposition. Few studies investigating this substance alone with regard to its stability are available in the literature. This fact prompted the present study to characterize this species and its thermal behavior using thermal analysis (TG/DTG and DSC) and to associate the results of these techniques with those obtained by elemental analysis (EA) and absorption spectroscopy in the infrared region. The TG/DTG and DSC curves allowed evaluation of the thermal behavior of the sample of phytic acid and enabled use of the non-isothermal thermogravimetric method to study the kinetics of the three main mass-loss events: dehydration I, dehydration II and thermal decomposition. The combination of infrared absorption spectroscopy and elemental analysis techniques allowed evaluation of the intermediate products of the thermal decomposition of phytic acid. The infrared spectra of samples taken during the heating process revealed a reduction in the intensity of the absorption band related to O-H stretching as a result of the dehydration process. Furthermore, elemental analysis results showed an increase in the carbon content and a decrease in the hydrogen content at temperatures of 95, 150, 263 and 380 °C. Visually, darkening of the material was observed at 150 °C, indicating that the thermal decomposition of the material started at this temperature. At a temperature of 380 °C, thermal decomposition progressed, leading to a decrease in carbon and hydrogen. The results of thermogravimetry coupled with those of elemental analysis allow us to conclude that there was agreement between the percentages of phytic acid found in aqueous solution. The kinetic study by the non-isothermal thermogravimetric method showed that the dehydration process occurred in two stages. Dehydration step I promoted a process of vaporization of water (reaction order of zero), whereas dehydration step II showed an order of reaction equal to five. This change in reaction order was attributed to loss of chemically bonded water molecules of phytic acid or to the presence of volatile substances. Finally, the thermal decomposition step revealed an order of reaction equal to one. It was not possible to perform the kinetic study for other stages of mass loss.


1985 ◽  
Vol 107 (3) ◽  
pp. 739-743 ◽  
Author(s):  
J. A. Mulholland ◽  
W. S. Lanier

A 730 kW (2.5 × 106 Btu/hr) firetube package boiler was used to demonstrate the application of reburning for NOx emission control. An overall reduction of 50 percent from an uncontrolled NOx emission of 200 ppm was realized by diverting 15 percent of the total boiler load to a natural-gas-fired second stage burner. Tests indicate that the overall reaction order of destruction with respect to initial NOx is greater than one; thus, larger reductions can be expected from reburning applications to systems with higher initial NOx. Rich zone stoichiometry has been identified as the dominant process variable. Primary zone stoichiometry and rich zone residence time are parameters that can be adjusted to maximize NOx reduction. Reburning applied to firetube package boilers requires minimal facility modification. Natural gas would appear to be an ideal reburning fuel as nitrogen in the reburning fuel has been shown to inhibit NOx reduction.


2013 ◽  
Vol 860-863 ◽  
pp. 510-513 ◽  
Author(s):  
Yi Zhe Li ◽  
Hua Wang ◽  
Gui Rong Bao

Experiments of Rapeseed Oil Hydrolysis Reaction in Sub-Critical Water (250-300°C, 5-60min) are Conducted in this Paper. Results Show that the Best Conditions for Rapeseed Oil Hydrolysis are Reaction Temperature 290°C, Oil-Water Volume Ratio 1:3, Reaction Time 40min, and Conversion Rate 98.9%. Meanwhile, Kinetic Analysis of this Hydrolysis Reaction is Presented. we Learn that Hydrolysis Reaction Order is 0.7778, Activation Energy is 55.34kJ/mol and the Dynamic Model is .


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