N‒N Bond Lengths and the Initiation Reactivity (Sensitivity) of Nitramines

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F20%3A39914302" target="_blank" >RIV/00216275:25310/20:39914302 - isvavai.cz</a>

Výsledek na webu

<a href="http://www.wydawnictwa.ipo.waw.pl/cejem/Vol-17-Number2-2020/CEJEM_01089.pdf" target="_blank" >http://www.wydawnictwa.ipo.waw.pl/cejem/Vol-17-Number2-2020/CEJEM_01089.pdf</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.22211/cejem/122723" target="_blank" >10.22211/cejem/122723</a>

Jazyk výsledku

angličtina

Název v původním jazyce

N‒N Bond Lengths and the Initiation Reactivity (Sensitivity) of Nitramines

Popis výsledku v původním jazyce

On 16 selected nitramines, it is shown that an increase in the energy content of their molecules (represented by enthalpies of formation) is connected with an increase in the lengths of the longest N‒N bonds in their molecules. These lengths are directly proportional to the activation energies of the low-temperature thermal decomposition of pure nitramines in all states of matter of this reaction. Raising the energy content leads also to a reduction in the rate constants of thermal decomposition. Both of these facts are in contrast with expectations and also with similar published findings about the thermal decomposition of nitramines in solution, which can be explained by the solvation effect and termination of the emerging aza-radicals in solutions. The calculated dissociation energies of the weakest N‒N bonds yielded a relatively good reciprocal conformity with the lengths of the longest N‒N bonds of the nitramines studied, especially when using the UB3LYP/6-31G* method. The relationship between the impact sensitivity of the nitramines studied and the length of the longest N‒N bonds in their molecules is not completely clear. Such lengths cannot be a measure of impact sensitivity, because the longest N‒N bond might be stabilized by a suitable intermolecular interaction with the adjacent molecule in the crystal lattice

Název v anglickém jazyce

N‒N Bond Lengths and the Initiation Reactivity (Sensitivity) of Nitramines

Popis výsledku anglicky

On 16 selected nitramines, it is shown that an increase in the energy content of their molecules (represented by enthalpies of formation) is connected with an increase in the lengths of the longest N‒N bonds in their molecules. These lengths are directly proportional to the activation energies of the low-temperature thermal decomposition of pure nitramines in all states of matter of this reaction. Raising the energy content leads also to a reduction in the rate constants of thermal decomposition. Both of these facts are in contrast with expectations and also with similar published findings about the thermal decomposition of nitramines in solution, which can be explained by the solvation effect and termination of the emerging aza-radicals in solutions. The calculated dissociation energies of the weakest N‒N bonds yielded a relatively good reciprocal conformity with the lengths of the longest N‒N bonds of the nitramines studied, especially when using the UB3LYP/6-31G* method. The relationship between the impact sensitivity of the nitramines studied and the length of the longest N‒N bonds in their molecules is not completely clear. Such lengths cannot be a measure of impact sensitivity, because the longest N‒N bond might be stabilized by a suitable intermolecular interaction with the adjacent molecule in the crystal lattice

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Central European Journal of Energetic Materials

ISSN

1733-7178

e-ISSN

—

Svazek periodika

17

Číslo periodika v rámci svazku

2

Stát vydavatele periodika

PL - Polská republika

Počet stran výsledku

32

Strana od-do

169-200

Kód UT WoS článku

000544036000001

EID výsledku v databázi Scopus

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