On the Use of Differential Scanning Calorimetry for Thermal Hazard Assessment of New Chemistry: Avoiding Explosive Mistakes

Green, Sebastian P; Wheelhouse, Katherine M. P.; Payne, Andrew D.; Hallett, Jason P.; Miller, Philip W.; Bull, James A.

doi:10.1002/ange.202007028

Cited by 6 publications

(2 citation statements)

References 29 publications

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“…The thermograms of the control samples at 0.1 MPa show an endothermic peak at around 300 °C, immediately before the exotherm. This endotherm is consistent with the endothermic effect of a sudden loss of gaseous species from the crucible [28]. This observation, and a comparison of the emissions and decomposition enthalpies from the control samples, lead to the conclusion that measured energy releases from the control samples are more significantly affected by the loss of sensible heat with the gaseous products at 0.1 MPa than at higher pressures.…”

Section: Resultssupporting

confidence: 80%

Analysis of the thermal decomposition of munitions wastewater

Adhikari,

Parziale,

et al. 2023

Propellants Explo Pyrotec

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The thermal decomposition of ammonium nitrate (AN) laden munitions wastewater and comparable control samples were studied under air and nitrogen environments at pressures from 0.1 MPa to 10 MPa. The decomposition enthalpies, measured using a Differential Scanning Calorimeter (DSC), and gaseous emissions, measured using a Fourier‐Transform Infrared Spectrometer (FTIR), were used to evaluate the quality of decomposition. Experiments demonstrated that higher pressures improved the energy yield and reduced the quantities of harmful from the decomposition of all samples. At 10 MPa, experimentally measured decomposition enthalpy from the munitions wastewater was 1.8 MJ/kg, approximately 45 % of its standard enthalpy of decomposition, and NO and accounted for only 0.7 % and 0.08 % of the nitrogen in the sample, respectively. The emissions stream from the wastewater was found to primarily consist of , , and . An analysis of the heat releases and the emissions showed that higher pressures improved the extent and enthalpy of decomposition by preventing premature loss of gaseous intermediates and sensible heat through the pin‐hole crucibles used in the experiments. Moreover, high pressures precluded the evaporation of water and promoted the decomposition of AN via a radical mechanism.

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Section: Resultssupporting

confidence: 80%

Analysis of the thermal decomposition of munitions wastewater

Adhikari,

Parziale,

et al. 2023

Propellants Explo Pyrotec

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“…The bond dissociation energy (BDE) of the I−N bond in azidobenziodoxoles is lower than BDE of cyclic hypervalent iodine compounds with any other ligands [12,16–18] . Based on the results of differential scanning calorimetry (DSC), the azido reagents derived from benziodazoles and tert ‐butyl substituted benziodoxoles are expected to be safer for handling than the unsubstituted azidobenziodoxoles [19–20] . These reagents can be synthesized by adding TMSN 3 to the corresponding acetoxybenziodoxoles or benziodazoles [15,21–23] …”

Section: Azidobenziodoxoles and Azidobenziodazolesmentioning

confidence: 99%

Recent Progress in Synthetic Applications of Cyclic Hypervalent Iodine(III) Reagents

2023

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Hypervalent iodine compounds have found broad application in modern organic chemistry as reagents and catalysts. Cyclic hypervalent iodine reagents based on the benziodoxole heterocyclic system have higher stability compared to their acyclic analogues, which makes possible the preparation and safe handling of the reagents with special ligands such as azido, cyano, and trifluoromethyl groups. Numerous iodine‐substituted benziodoxole derivatives have been prepared and utilized as reagents for transfer of the substituent on hypervalent iodine to organic substrate. Reactions of these reagents with organic substrates can be performed under metal‐free conditions, in the presence of transition metal catalysts, or using photocatalysts under photoirradiation conditions. In this review, we focus on the most recent synthetic applications of cyclic hypervalent iodine(III) reagents with the following ligands: N3, NHR, CN, CF3, SCF3, OR, OAc, ONO2, and C(=N2)CO2R. The review covers literature published mainly in the last 5 years.magnified image

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Simple and Versatile Nitrooxylation: Noncyclic Hypervalent Iodine Nitrooxylating Reagent

et al. 2023

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Organic nitrates are broadly applied as pharmaceuticals (acting as efficient nitric oxide donor), energetic materials, building blocks in organic synthesis, etc. However, practical and direct methods to access organic nitrates efficiently are still rare, mainly due to the lack of powerful nitrooxylating reagents. Herein, we report bench-stable and highly reactive noncyclic hypervalent iodine nitrooxylating reagents, oxybis(aryl-λ 3iodanediyl) dinitrates (OAIDNs, 2), which are prepared just by using aryliodine diacetate and HNO 3 . The reagents are used to achieve a mild and operationally simple protocol to access diverse organic nitrates. By employing of 2, zinc-catalyzed regioselective nitrooxylation of cyclopropyl silyl ethers is realized efficiently to access the corresponding β-nitrooxy ketones with high functional-group tolerance. Moreover, a series of direct and catalyst-free nitrooxylations of enolizable CÀ H bonds are carried out smoothly to afford the desired organic nitrates within minutes by just mixing the substrates with 2 in dichloromethane.

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On the Use of Differential Scanning Calorimetry for Thermal Hazard Assessment of New Chemistry: Avoiding Explosive Mistakes

Cited by 6 publications

References 29 publications

Analysis of the thermal decomposition of munitions wastewater

Analysis of the thermal decomposition of munitions wastewater

Recent Progress in Synthetic Applications of Cyclic Hypervalent Iodine(III) Reagents

Simple and Versatile Nitrooxylation: Noncyclic Hypervalent Iodine Nitrooxylating Reagent

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