TY - JOUR
T1 - A DFT study on the enthalpies of thermite reactions and enthalpies of formation of metal composite oxide
AU - Zhang, Yu ying
AU - Wang, Meng jie
AU - Chang, Chun ran
AU - Xu, Kang zhen
AU - Ma, Hai xia
AU - Zhao, Feng qi
N1 - Publisher Copyright:
© 2018 Elsevier B.V.
PY - 2018/5/11
Y1 - 2018/5/11
N2 - The standard thermite reaction enthalpies (ΔrHm θ) for seven metal oxides were theoretically analyzed using density functional theory (DFT) under five different functional levels, and the results were compared with experimental values. Through the comparison of the linear fitting constants, mean error and root mean square error, the Perdew-Wang functional within the framework of local density approximation (LDA-PWC) and Perdew-Burke-Ernzerhof exchange-correlation functional within the framework of generalized gradient approximation (GGA-PBE) were selected to further calculate the thermite reaction enthalpies for metal composite oxides (MCOs). According to the Kirchhoff formula, the standard molar reaction enthalpies for these MCOs were obtained and their standard molar enthalpies of formation (ΔfHm θ) were finally calculated. The results indicated that GGA-PBE is the most suitable one out of the total five methods to calculate these oxides. Tungstate crystals present the maximum deviation of the enthalpies of thermite reactions for MCOs and these of their physical metal oxide mixtures, but ferrite crystals are the minimum. The correlation coefficients are all above 0.95, meaning linear fitting results are very precise. And the molar enthalpies of formation for NiMoO4, CuMoO4, PbZrO3 (Pm/3m), PbZrO3 (PBA2), PbZrO3 (PBam), MgZrO3, CdZrO3, MnZrO3, CuWO4 and Fe2WO6 were first obtained as −1078.75, −1058.45, −1343.87, −1266.54, −1342.29, −1333.03, −1210.43, −1388.05, −1131.07 and − 1860.11 kJ·mol−1, respectively.
AB - The standard thermite reaction enthalpies (ΔrHm θ) for seven metal oxides were theoretically analyzed using density functional theory (DFT) under five different functional levels, and the results were compared with experimental values. Through the comparison of the linear fitting constants, mean error and root mean square error, the Perdew-Wang functional within the framework of local density approximation (LDA-PWC) and Perdew-Burke-Ernzerhof exchange-correlation functional within the framework of generalized gradient approximation (GGA-PBE) were selected to further calculate the thermite reaction enthalpies for metal composite oxides (MCOs). According to the Kirchhoff formula, the standard molar reaction enthalpies for these MCOs were obtained and their standard molar enthalpies of formation (ΔfHm θ) were finally calculated. The results indicated that GGA-PBE is the most suitable one out of the total five methods to calculate these oxides. Tungstate crystals present the maximum deviation of the enthalpies of thermite reactions for MCOs and these of their physical metal oxide mixtures, but ferrite crystals are the minimum. The correlation coefficients are all above 0.95, meaning linear fitting results are very precise. And the molar enthalpies of formation for NiMoO4, CuMoO4, PbZrO3 (Pm/3m), PbZrO3 (PBA2), PbZrO3 (PBam), MgZrO3, CdZrO3, MnZrO3, CuWO4 and Fe2WO6 were first obtained as −1078.75, −1058.45, −1343.87, −1266.54, −1342.29, −1333.03, −1210.43, −1388.05, −1131.07 and − 1860.11 kJ·mol−1, respectively.
KW - Density functional theory
KW - Metal composite oxides
KW - Standard molar enthalpy of formation
KW - Thermite reaction
UR - https://www.scopus.com/pages/publications/85045581907
U2 - 10.1016/j.chemphys.2018.04.004
DO - 10.1016/j.chemphys.2018.04.004
M3 - 文章
AN - SCOPUS:85045581907
SN - 0301-0104
VL - 507
SP - 19
EP - 27
JO - Chemical Physics
JF - Chemical Physics
ER -