Thermal reactive hazards of 1,1-bis(tert-butylperoxy)cyclohexane with nitric acid contaminants by DSC

Hsueh, Kuang-Hua; Chen, Wei‐Ting; Chu, Yung-Chuan; Tsai, Lung-Chang; Shu, Chi‐Min

doi:10.1007/s10973-012-2338-y

Cited by 14 publications

(7 citation statements)

References 20 publications

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“…Under the right conditions, both peroxides can be safely destroyed by acid‐catalyzed hydrolysis back to starting materials; however, treatment of TATP with concentrated acids can lead to detonation . It had also been noted that it was dangerous to treat bisperoxide 71 with nitric acid (Figure b) . Although the controlled acid‐mediated decomposition of TATP showed no indications for a radical mechanism, it is at present unclear whether the explosive decomposition by acid involves alkenyl peroxides.…”

Section: Solution Chemistrymentioning

confidence: 99%

“…[58] It had also been noted that it was dangeroust ot reat bisperoxide 71 with nitric acid (Figure 4b). [59] Although the controlled acid-mediated decompositiono fT ATPs howed no indications for ar adicalm echanism, [58a] it is at presentu nclear whether the explosive decomposition by acidi nvolves alkenyl peroxides.…”

Section: Formation Of Alkenylperoxides From Carbonylcompounds By Acidmentioning

confidence: 99%

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Alkenyl and Aryl Peroxides

Klußmann

2017

Chemistry A European J

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Alkenyl and aryl peroxides are a special class of organic peroxides. Under ambient conditions, they are usually short-lived, rapidly decomposing into radicals by homolytic O-O bond cleavage. They play an important role in the chemistry of the lower atmosphere, where they are formed through ozonolysis of alkenes. In the dark, this pathway is considered the major source of hydroxyl radicals, the "detergent of the atmosphere". In solution, alkenyl and aryl peroxides can be formed by various methods and their decomposition can be harnessed synthetically. For example, reactions involving alkenyl peroxides can be used to introduce ketones through radical additions, and nucleophilic aromatic substitution reactions generating aryl peroxides have been used to synthesize phenols. The radicals can also initiate radical polymerization reactions or chain reactions and mediate oxidative coupling by C-H bond functionalization. Knowledge of their chemistry could be helpful for projects generating or utilizing peroxides.

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Section: Solution Chemistrymentioning

confidence: 99%

Section: Formation Of Alkenylperoxides From Carbonylcompounds By Acidmentioning

confidence: 99%

Alkenyl and Aryl Peroxides

Klußmann

2017

Chemistry A European J

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“…1)), taking into account the quality of the fit (characterized by the correlation coefficient), it could be seen from Table 1 that the mechanism was similar to that of a Prout-Tompkins type autocatalytic reaction. The oxidation of organic substances by nitric acid proceeds autocatalytically [19,20]. Thus, it is reasonable to approximate the rapid weight loss at approximately 200 C by the kinetic model of a Prout-Tompkins type autocatalytic reaction.…”

Section: Examination Of the Kinetics Parameters And Reaction Pathsmentioning

confidence: 99%

Kinetic Analysis and Prediction of Thermal Decomposition Behavior of Tertiary Pyridine Resin in the Nitrate Form

et al. 2015

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The thermal decomposition behavior of the tertiary pyridine resin, which was used during the nuclide-separation process in the Advanced Optimization by Recycling Instructive Elements (Advanced ORIENT) cycle, was investigated in its nitrate form (TPR-NO 3 ), in order to determine ways of preventing its runaway reaction. A thermal analysis of TPR-NO 3 and an analysis of the gases produced during decomposition were employed for the purpose. In addition, the kinetics parameters were evaluated via a kinetic analysis of the empirical thermal data. Finally, the validity of the reaction model was assessed by comparing the thermal behavior predicted by the estimated reaction model with that determined by the results of a gram-scale heating test performed in our previous study. We found that, when TPR-NO 3 was heated, first, nitric acid was removed. Subsequently, TPR-NO 3 was oxidized by the removed nitric acid. Under the assumption that it took place an autocatalytic oxidation and n th order thermal decomposition in parallel, the thermogravimetric analysis data could be fitted very well using a nonlinear regression model. The thermal behavior of TPR-NO 3 could be predicted by the reaction model determined in this study under conditions where the cooling effect owing to evaporation was ignored. In addition, the maximum temperature and time to maximum rate of a runaway reaction predicted using the determined reaction model gave the result on the side of prudence.

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“…BTBPC is an asymmetrical difunctional peroxide (two sets of symmetrical O-O bonds) with low volatility and yellowish liquid formation [2]. It is usually applied as an initiator during the styrene polymerization process to generate a lower residual styrene content and a higher degree of polymerization, mainly used for polystyrene in Taiwan's chemical plants.…”

Section: Introductionmentioning

confidence: 99%

A Method to Derive the Characteristic and Kinetic Parameters of 1,1-Bis(tert-butylperoxy)cyclohexane from DSC Measurements

et al. 2022

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A differential scanning calorimetry (DSC) experiment was carried out to determine the thermal characteristics of harmful substances. Most experimenters only use the results of measurement and rarely conduct in-depth research on the variety of information behind the measurement. This study used Wolfram’s Mathematica as a DSC measurement research tool to plot the peak curve and derive the characteristic parameters graphically for 1,1-Bis(tert-butylperoxy)cyclohexane. The research steps included raw data cleansing, peak curve normalization, characteristic parameter derivation, and total reaction heat calculation. The kinetic parameters of individual data were derived through the Borchardt and Daniels method, and the autocatalytic model was also verified. We applied the derived characteristic parameters to simulate the peak curve through the Gaussian curve model, which can be used for estimating the peak curve of other heating rates. The derived kinetic parameters were used to observe the effects on the peak curve. The simulation can be used to plan the test results at other rates in a similar temperature range and can also be used to explore the influence of different kinetic parameters on the configuration of the shape of the peak curve and a preliminary model test of materials for materials DSC research.

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Thermal reactive hazards of 1,1-bis(tert-butylperoxy)cyclohexane with nitric acid contaminants by DSC

Cited by 14 publications

References 20 publications

Alkenyl and Aryl Peroxides

Alkenyl and Aryl Peroxides

Kinetic Analysis and Prediction of Thermal Decomposition Behavior of Tertiary Pyridine Resin in the Nitrate Form

A Method to Derive the Characteristic and Kinetic Parameters of 1,1-Bis(tert-butylperoxy)cyclohexane from DSC Measurements

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