Rates and activation energies of nitronium ion formation and reaction in the nitration of toluene in ∼78% sulphuric acid

1978 ◽  
Vol 56 (9) ◽  
pp. 1280-1283 ◽  
Author(s):  
George F. Sheats ◽  
Alec N. Strachan
Keyword(s):  
Activation Energy ◽  
Nitric Acid ◽  
Complex Formation ◽  
Kinetic Parameters ◽  
Sulphuric Acid ◽  
Activation Energies ◽  
Reverse Reaction ◽  
Stopped Flow ◽  
Ion Formation ◽  
Encounter Complex

A stopped-flow spectrometer has been used to investigate the mechanism of the nitration of toluene, and to determine kinetic parameters for the formation and reaction of nitronium ion, in 77.3 and 78.45 wt.% sulphuric acid. The protonation of nitric acid to form nitronium ion and water is found to occur at similar rates at both acid concentrations and to have an activation energy of 18.3 ± 4.0 kcal mol−1. The activation energy of the reverse reaction, the heat of the reaction, and the activation energy of encounter complex formation between nitronium ion and toluene are estimated to be respectively 10.5 ± 4.0, 7.8 ± 0.5, and 5.9 ± 0.1 kcal mol−1 in 77.3% H2SO4 and 12.0 ± 4.0, 6.3 ± 0.5, and 6.0 ± 0.1 kcal mol−1 in 78.45% H2SO4.

The Determination of Kinetic Parameters of Transformer Oil and its Blends by Thermal Analysis

2012 ◽  
Vol 13 (4) ◽  
Author(s):  
Veresha Dukhi ◽  
Ajay Bissessur ◽  
Catherine Jane Ngila ◽  
Nelson Mutatina Ijumba
Keyword(s):  
Activation Energy ◽  
Weight Loss ◽  
Kinetic Parameters ◽  
Breakdown Voltage ◽  
Activation Energies ◽  
Transformer Oil ◽  
Dielectric Fluid ◽  
Differential Scanning Calorimetric ◽  
Significant Difference

Abstract The insulation of transformer oil comprise of two practices: paper and dielectric fluid (such as mineral transformer oil). Ageing of these oils occur mainly by thermal, electrical and oxidative stresses. This paper describes the determination of kinetic parameters of a naphthenic based transformer oil and its blends based on the Ozawa, Flynn and Wall (OFW) and Kissinger models using data obtained from thermogravimetric analysis (TGA) and differential scanning calorimetric (DSC), plots. Virgin oil and its blends were analysed from an initial temperature range of 20-25 ºC to 300 ºC at temperature ramps of 1, 2, 4, 6, 8 and 10 ºC min-1. The OFW method in conjunction with TGA data was used to calculate the apparent decomposition activation energies at each of the selected weight loss (% conversion or α) values. The activation energies at 10% weight loss were found to be 57.0, 63.7 and 69.3 kJ mol-1 for BHT-B (virgin oil-2,6-di-tert-butyl-4-methylphenol blends), DBP-B (virgin oil-2,6-di-tert-butylphenol blends) and VO (virgin transformer oil), respectively. However using this method the activation energy (Ea) of the oils showed no significant difference between virgin oil and its blends. DSC curves revealed that the decomposition reaction was exothermic in nature. From DSC data the activation energy was determined using two separate models: OFW and Kissinger models. Decomposition activation energy obtained from DSC data showed no significant difference when applied to these two models. Dissipation factor tests showed superior results for the blends when compared to those of virgin transformer oil. However, the blends showed substantial reductions in their dielectric breakdown voltage. The implication of the reduced breakdown voltage is that the blends show poorer dielectric strength in comparison to virgin transformer oil.

scholarly journals Comparative Kinetic Analysis of CaCO3/CaO Reaction System for Energy Storage and Carbon Capture

2019 ◽  
Vol 9 (21) ◽  
pp. 4601 ◽  
Author(s):  
Fedunik-Hofman ◽  
Bayon ◽  
Donne
Keyword(s):  
Activation Energy ◽  
Energy Storage ◽  
Kinetic Analysis ◽  
Kinetic Parameters ◽  
Carbon Capture ◽  
Model Fitting ◽  
Reaction System ◽  
Reaction Model ◽  
Activation Energies ◽  
Exponential Factor

The calcium carbonate looping cycle is an important reaction system for processes such as thermochemical energy storage and carbon capture technologies, which can be used to lower greenhouse gas emissions associated with the energy industry. Kinetic analysis of the reactions involved (calcination and carbonation) can be used to determine kinetic parameters (activation energy, pre-exponential factor, and the reaction model), which is useful to translate laboratory-scale studies to large-scale reactor conditions. A variety of methods are available and there is a lack of consensus on the kinetic parameters in published literature. In this paper, the calcination of synthesized CaCO3 is modeled using model-fitting methods under two different experimental atmospheres, including 100% CO2, which realistically reflects reactor conditions and is relatively unstudied kinetically. Results are compared with similar studies and model-free methods using a detailed, comparative methodology that has not been carried out previously. Under N2, an activation energy of 204 kJ mol-1 is obtained with the R2 (contracting area) geometric model, which is consistent with various model-fitting and isoconversional analyses. For experiments under CO2, much higher activation energies (up to 1220 kJ mol-1 with a first-order reaction model) are obtained, which has also been observed previously. The carbonation of synthesized CaO is modeled using an intrinsic chemical reaction rate model and an apparent model. Activation energies of 17.45 kJ mol-1 and 59.95 kJ mol-1 are obtained for the kinetic and diffusion control regions, respectively, which are on the lower bounds of literature results. The experimental conditions, material properties, and the kinetic method are found to strongly influence the kinetic parameters, and recommendations are provided for the analysis of both reactions.

Thermal degradation kinetics of a lignin particle-reinforced phenolic foam

2020 ◽  
pp. 0021955X2093288
Author(s):  
Juan Carlos Domínguez ◽  
Belén Del Saz-Orozco ◽  
Mercedes Oliet ◽  
M Virginia Alonso ◽  
Francisco Rodriguez
Keyword(s):  
Activation Energy ◽  
Thermal Degradation ◽  
Kinetic Parameters ◽  
Degradation Kinetics ◽  
Degradation Process ◽  
Activation Energies ◽  
Thermal Degradation Kinetics ◽  
Model Free ◽  
Predicted Values ◽  
Kinetics Of

In the present work, the thermal degradation kinetics of a phenolic (PF) and lignin particle-reinforced phenolic (LRPF) foam and the lignin used as the reinforcement (LR) were studied. The activation energies of the degradation processes were obtained using a discrete distributed activation energy model (discrete DAEM) and the Vyazovkin model-free kinetic (MFK) method. The discrete DAEM was validated by comparing the predicted values with the data obtained at 8 °C min−1. Heating ramps of 6 and 12 °C min−1 were used to calculate the kinetic parameters through the model. The effect of the reinforcement on the kinetics of the LRPF was studied by comparison with the results obtained for the PF. For reactions with non-zero mass fractions, the activation energies of the PF were in the range between 79.9 and 177.6 kJ mol−1, and the activation energy for the LRPF ranged from 91 to 187 kJ mol−1. For the LR, the activation energy values were in a narrower range than for the foams: 150–187 kJ mol−1. The degradation process of the LRPF was modified due to the use of LR: the range of activation energy for LRPF was between the ranges for the PF and LR. The activation energy dependence on conversion was also calculated using the Vyazovkin method and compared with the DAEM results; no compensation effect for the kinetic parameters was found.

scholarly journals High-Temperature Deformation of Naturally Aged 7010 Aluminum Alloy

Metals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 581
Author(s):  
Abdulhakim A. Almajid
Keyword(s):  
Activation Energy ◽  
Aluminum Alloy ◽  
High Temperature ◽  
Threshold Stress ◽  
Activation Energies ◽  
Temperature Deformation ◽  
High Temperature Range ◽  
Temperature Range ◽  
True Activation Energy ◽  
Two Temperatures

This study is focused on the deformation mechanism and behavior of naturally aged 7010 aluminum alloy at elevated temperatures. The specimens were naturally aged for 60 days to reach a saturated hardness state. High-temperature tensile tests for the naturally aged sample were conducted at different temperatures of 573, 623, 673, and 723 K at various strain rates ranging from 5 × 10−5 to 10−2 s−1. The dependency of stress on the strain rate showed a stress exponent, n, of ~6.5 for the low two temperatures and ~4.5 for the high two temperatures. The apparent activation energies of 290 and 165 kJ/mol are observed at the low, and high-temperature range, respectively. These values of activation energies are greater than those of solute/solvent self-diffusion. The stress exponents, n, and activation energy observed are rather high and this indicates the presence of threshold stress. This behavior occurred as a result of the dislocation interaction with the second phase particles that are existed in the alloy at the testing temperatures. The threshold stress decreases in an exponential manner as temperature increases. The true activation energy was computed by incorporating the threshold stress in the power-law relation between the stress and the strain. The magnitude of the true activation energy, Qt dropped to 234 and 102 kJ/mol at the low and high-temperature range, respectively. These values are close to that of diffusion of Zinc in Aluminum and diffusion of Magnesium in Aluminum, respectively. The Zener–Hollomon parameter for the alloy was developed as a function of effective stress. The data in each region (low and high-temperature region) coalescence in a segment line in each region.

scholarly journals Effect of CaO on catalytic combustion of semi-coke

2021 ◽  
Vol 10 (1) ◽  
pp. 011-020
Author(s):  
Luyao Kou ◽  
Junjing Tang ◽  
Tu Hu ◽  
Baocheng Zhou ◽  
Li Yang
Keyword(s):  
Activation Energy ◽  
Apparent Activation Energy ◽  
Combustion Rate ◽  
Activation Energies ◽  
Combustion Reaction ◽  
Tg Analysis ◽  
Conversion Rates ◽  
Apparent Activation Energies ◽  
Ozawa Integral Method ◽  
Addition Amount

Abstract Generally, adding a certain amount of an additive to pulverized coal can promote its combustion performance. In this paper, the effect of CaO on the combustion characteristics and kinetic behavior of semi-coke was studied by thermogravimetric (TG) analysis. The results show that adding proper amount of CaO can reduce the ignition temperature of semi-coke and increase the combustion rate of semi-coke; with the increase in CaO content, the combustion rate of semi-coke increases first and then decreases, and the results of TG analysis showed that optimal addition amount of CaO is 2 wt%. The apparent activation energy of CaO with different addition amounts of CaO was calculated by Coats–Redfern integration method. The apparent activation energy of semi-coke in the combustion reaction increases first and then decreases with the increase in CaO addition. The apparent activation energies of different samples at different conversion rates were calculated by Flynn–Wall–Ozawa integral method. It was found that the apparent activation energies of semi-coke during combustion reaction decreased with the increase in conversion.

scholarly journals The Effect of α-Al(MnCr)Si Dispersoids on Activation Energy and Workability of Al-Mg-Si-Cu Alloys during Hot Deformation

2020 ◽  
Vol 2020 ◽  
pp. 1-12
Author(s):  
Xiaoguo Wang ◽  
Jian Qin ◽  
Hiromi Nagaumi ◽  
Ruirui Wu ◽  
Qiushu Li
Keyword(s):  
Activation Energy ◽  
Aluminum Alloys ◽  
Constitutive Equation ◽  
Hot Deformation ◽  
Flow Instability ◽  
Void Formation ◽  
Activation Energies ◽  
Compression Tests ◽  
Softening Mechanism ◽  
Dynamic Softening

The hot deformation behaviors of homogenized direct-chill (DC) casting 6061 aluminum alloys and Mn/Cr-containing aluminum alloys denoted as WQ1 were studied systematically by uniaxial compression tests at various deformation temperatures and strain rates. Hot deformation behavior of WQ1 alloy was remarkably changed compared to that of 6061 alloy with the presence of α-Al(MnCr)Si dispersoids. The hyperbolic-sine constitutive equation was employed to determine the materials constants and activation energies of both studied alloys. The evolution of the activation energies of two alloys was investigated on a revised Sellars’ constitutive equation. The processing maps and activation energy maps of both alloys were also constructed to reveal deformation stable domains and optimize deformation parameters, respectively. Under the influence of α dispersoids, WQ1 alloy presented a higher activation energy, around 40 kJ/mol greater than 6061 alloy’s at the same deformation conditions. Dynamic recrystallization (DRX) is main dynamic softening mechanism in safe processing domain of 6061 alloy, while dynamic recovery (DRV) was main dynamic softening mechanism in WQ1 alloy due to pinning effect of α-Al(MnCr)Si dispersoids. α dispersoids can not only resist DRX but also increase power required for deformation of WQ1 alloy. The microstructure analysis revealed that the flow instability was attributed to the void formation and intermetallic cracking during hot deformation of both alloys.

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