TY - JOUR
T1 - Comparative theoretical studies on energetic substituted 1,2,4-triazole molecules and their corresponding ionic salts containing 1,2,4-triazole-based cations or anions
AU - Shao, Yuling
AU - Pan, Yong
AU - Wu, Qiong
AU - Zhu, Weihua
AU - Li, Jinshan
AU - Cheng, Bibo
AU - Xiao, Heming
PY - 2013/10
Y1 - 2013/10
N2 - We have studied the densities, heats of formation, energetic properties, and thermodynamics of formation for a series of substituted 1,2,4-triazole molecules and their corresponding ionic salts containing 1,2,4-triazolium cations or 1,2,4-triazolide anions using density functional theory and volume-based thermodynamics method. The results show that when the 1,2,4-triazole molecules lose a proton to form corresponding 1,2,4-triazole-based anions, their salts have smaller densities than corresponding molecules. When the molecules get a proton to form the 1,2,4-triazole-based cations, their salts have higher densities than corresponding molecules. The transformation of the 1,2,4-triazole derivatives from nonionic molecules to corresponding cations or anions are very helpful for increasing their heats of formation. Changing the 1,2,4-triazole derivatives into corresponding cations or anions produce different effects on their heats of detonation. Overall, as the compound numbering varies, the evolution trend of heat of detonation is very similar to heat of formation. The salts containing the 1,2,4-triazolide anions have smaller detonation velocities and pressures than corresponding 1,2,4-triazole molecules, whereas the salts containing the 1,2,4-triazolium cations have higher detonation velocities and pressures than corresponding molecules. Finally, the lattice enthalpies and entropies were used to construct a thermodynamic cycle for salt formation to predict the possibility to synthesize the salts.
AB - We have studied the densities, heats of formation, energetic properties, and thermodynamics of formation for a series of substituted 1,2,4-triazole molecules and their corresponding ionic salts containing 1,2,4-triazolium cations or 1,2,4-triazolide anions using density functional theory and volume-based thermodynamics method. The results show that when the 1,2,4-triazole molecules lose a proton to form corresponding 1,2,4-triazole-based anions, their salts have smaller densities than corresponding molecules. When the molecules get a proton to form the 1,2,4-triazole-based cations, their salts have higher densities than corresponding molecules. The transformation of the 1,2,4-triazole derivatives from nonionic molecules to corresponding cations or anions are very helpful for increasing their heats of formation. Changing the 1,2,4-triazole derivatives into corresponding cations or anions produce different effects on their heats of detonation. Overall, as the compound numbering varies, the evolution trend of heat of detonation is very similar to heat of formation. The salts containing the 1,2,4-triazolide anions have smaller detonation velocities and pressures than corresponding 1,2,4-triazole molecules, whereas the salts containing the 1,2,4-triazolium cations have higher detonation velocities and pressures than corresponding molecules. Finally, the lattice enthalpies and entropies were used to construct a thermodynamic cycle for salt formation to predict the possibility to synthesize the salts.
KW - Density functional theory
KW - Energetic properties
KW - Heats of formation
KW - Thermodynamics of salt formation
UR - http://www.scopus.com/inward/record.url?scp=84885181367&partnerID=8YFLogxK
U2 - 10.1007/s11224-012-0175-z
DO - 10.1007/s11224-012-0175-z
M3 - 文章
AN - SCOPUS:84885181367
SN - 1040-0400
VL - 24
SP - 1429
EP - 1442
JO - Structural Chemistry
JF - Structural Chemistry
IS - 5
ER -