Standard

Pressure DSC for energetic materials. Part 2. Switching between evaporation and thermal decomposition of 3,5-dinitropyrazole. / Gorn, Margarita V.; Monogarov, Konstantin A.; Dalinger, Igor L. и др.

в: Thermochimica Acta, Том 690, 178697, 01.08.2020.

Результаты исследований: Научные публикации в периодических изданияхстатьяРецензирование

Harvard

APA

Vancouver

Gorn MV, Monogarov KA, Dalinger IL, Melnikov IN, Kiselev VG, Muravyev NV. Pressure DSC for energetic materials. Part 2. Switching between evaporation and thermal decomposition of 3,5-dinitropyrazole. Thermochimica Acta. 2020 авг. 1;690:178697. doi: 10.1016/j.tca.2020.178697

Author

Gorn, Margarita V. ; Monogarov, Konstantin A. ; Dalinger, Igor L. и др. / Pressure DSC for energetic materials. Part 2. Switching between evaporation and thermal decomposition of 3,5-dinitropyrazole. в: Thermochimica Acta. 2020 ; Том 690.

BibTeX

@article{5016d7efb74d4a0791e5aad48a3cd7ec,
title = "Pressure DSC for energetic materials. Part 2. Switching between evaporation and thermal decomposition of 3,5-dinitropyrazole",
abstract = "Differential scanning calorimetry at an elevated external pressure (Pressure DSC) allows for shifting the vaporization of a sample to higher temperatures, thus often facilitating the direct observation of its thermal decomposition. In the present work, the thermolysis of a promising energetic material 3,5-dinitropyrazole was studied under pressures up to 10 MPa. The thermokinetic analysis of the datasets acquired at 2 and 5 MPa exhibited a pronounced kinetic compensation, thus allowing to build the joint formal kinetic model. The final kinetic scheme is comprised of the two parallel reactions, viz., the first-order process (Ea = 198 kJ mol−1) along with a first-order autocatalysis (Ea = 127 kJ mol−1). The experiment was complemented with the highly accurate CCSD(T)-F12 quantum chemical calculations. Theory revealed an unusual primary decomposition channel, viz., a sigmatropic [1,5]H-shift followed by the pyrazole ring opening yielding a molecular nitrogen and a nitro radical as simple primary products. Apart from this, the comparative thermogravimetry at a normal pressure yielded the vapor pressure of 3,5-dinitropyrazole along with the internally consistent set of phase change enthalpies. In general, the pressure DSC is a facile technique to study the true decomposition kinetics of the compounds that vaporize/sublime in conventional DSC experiments.",
keywords = "3,5-Dinitropyrazole, Energetic materials, Phase change data, Predictive electronic structure theory, Pressure DSC, Thermokinetic analysis, Thermolysis mechanism, Vapor pressure, STABILITY, FOX-7, STATE, MECHANISMS, PYRAZOLE, VAPOR-PRESSURE, TUNNELING CONTROL, KINETICS",
author = "Gorn, {Margarita V.} and Monogarov, {Konstantin A.} and Dalinger, {Igor L.} and Melnikov, {Igor N.} and Kiselev, {Vitaly G.} and Muravyev, {Nikita V.}",
year = "2020",
month = aug,
day = "1",
doi = "10.1016/j.tca.2020.178697",
language = "English",
volume = "690",
journal = "Thermochimica Acta",
issn = "0040-6031",
publisher = "Elsevier",

}

RIS

TY - JOUR

T1 - Pressure DSC for energetic materials. Part 2. Switching between evaporation and thermal decomposition of 3,5-dinitropyrazole

AU - Gorn, Margarita V.

AU - Monogarov, Konstantin A.

AU - Dalinger, Igor L.

AU - Melnikov, Igor N.

AU - Kiselev, Vitaly G.

AU - Muravyev, Nikita V.

PY - 2020/8/1

Y1 - 2020/8/1

N2 - Differential scanning calorimetry at an elevated external pressure (Pressure DSC) allows for shifting the vaporization of a sample to higher temperatures, thus often facilitating the direct observation of its thermal decomposition. In the present work, the thermolysis of a promising energetic material 3,5-dinitropyrazole was studied under pressures up to 10 MPa. The thermokinetic analysis of the datasets acquired at 2 and 5 MPa exhibited a pronounced kinetic compensation, thus allowing to build the joint formal kinetic model. The final kinetic scheme is comprised of the two parallel reactions, viz., the first-order process (Ea = 198 kJ mol−1) along with a first-order autocatalysis (Ea = 127 kJ mol−1). The experiment was complemented with the highly accurate CCSD(T)-F12 quantum chemical calculations. Theory revealed an unusual primary decomposition channel, viz., a sigmatropic [1,5]H-shift followed by the pyrazole ring opening yielding a molecular nitrogen and a nitro radical as simple primary products. Apart from this, the comparative thermogravimetry at a normal pressure yielded the vapor pressure of 3,5-dinitropyrazole along with the internally consistent set of phase change enthalpies. In general, the pressure DSC is a facile technique to study the true decomposition kinetics of the compounds that vaporize/sublime in conventional DSC experiments.

AB - Differential scanning calorimetry at an elevated external pressure (Pressure DSC) allows for shifting the vaporization of a sample to higher temperatures, thus often facilitating the direct observation of its thermal decomposition. In the present work, the thermolysis of a promising energetic material 3,5-dinitropyrazole was studied under pressures up to 10 MPa. The thermokinetic analysis of the datasets acquired at 2 and 5 MPa exhibited a pronounced kinetic compensation, thus allowing to build the joint formal kinetic model. The final kinetic scheme is comprised of the two parallel reactions, viz., the first-order process (Ea = 198 kJ mol−1) along with a first-order autocatalysis (Ea = 127 kJ mol−1). The experiment was complemented with the highly accurate CCSD(T)-F12 quantum chemical calculations. Theory revealed an unusual primary decomposition channel, viz., a sigmatropic [1,5]H-shift followed by the pyrazole ring opening yielding a molecular nitrogen and a nitro radical as simple primary products. Apart from this, the comparative thermogravimetry at a normal pressure yielded the vapor pressure of 3,5-dinitropyrazole along with the internally consistent set of phase change enthalpies. In general, the pressure DSC is a facile technique to study the true decomposition kinetics of the compounds that vaporize/sublime in conventional DSC experiments.

KW - 3,5-Dinitropyrazole

KW - Energetic materials

KW - Phase change data

KW - Predictive electronic structure theory

KW - Pressure DSC

KW - Thermokinetic analysis

KW - Thermolysis mechanism

KW - Vapor pressure

KW - STABILITY

KW - FOX-7

KW - STATE

KW - MECHANISMS

KW - PYRAZOLE

KW - VAPOR-PRESSURE

KW - TUNNELING CONTROL

KW - KINETICS

UR - http://www.scopus.com/inward/record.url?scp=85087336233&partnerID=8YFLogxK

U2 - 10.1016/j.tca.2020.178697

DO - 10.1016/j.tca.2020.178697

M3 - Article

AN - SCOPUS:85087336233

VL - 690

JO - Thermochimica Acta

JF - Thermochimica Acta

SN - 0040-6031

M1 - 178697

ER -

ID: 24721705