TY - JOUR
T1 - Energetics of Ternary Nitrides
T2 - Li-Ca-Zn-N and Ca-Ta-N Systems
AU - McHale, J. M.
AU - Navrotsky, A.
AU - Kowach, Glen R.
AU - Balbarin, Vincent E.
AU - Disalvo, F. J.
N1 - Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 1997/7
Y1 - 1997/7
N2 - High-temperature oxide melt drop solution calorimetry was used to study the energetics of ternary nitride formation. The standard enthalpies of formation of several binary and ternary nitrides were determined. These values in kJ mol-1 are ΔHfo(Li3N) = -166.1 ± 4.8, ΔHfo(Ca3N2) = -439.7 ± 6.6, ΔHfo(Zn3N2) = -43.5 ± 4.1, ΔHfo(Ta3N5) = -849.7 ± 11.7, ΔHfo(Ca2ZnN2) = -378.9 ± 8.6, ΔHfo(Sr2ZnN2) = -385.6 ± 14.3, ΔHfo(LiCaN) = -216.8 ± 10.8, ΔHfo(LiZnN) = -137.5 ± 6.8, and ΔHfo(CaTaN2) = -643.8 ± 9.6. These enthalpies of formation are small in magnitude compared to analogous values for oxides. However, the enthalpies of formation of the ternaries from binary nitrides can be quite substantial, confirming significant energetic stabilization of ternary nitrides. The energetics of ternary nitride formation appears to be dominated by the acid/base character of the cations. A linear relationship was found between the enthalpies of formation of the ternaries from binary nitrides and the ionic potential ratio of the two cations.
AB - High-temperature oxide melt drop solution calorimetry was used to study the energetics of ternary nitride formation. The standard enthalpies of formation of several binary and ternary nitrides were determined. These values in kJ mol-1 are ΔHfo(Li3N) = -166.1 ± 4.8, ΔHfo(Ca3N2) = -439.7 ± 6.6, ΔHfo(Zn3N2) = -43.5 ± 4.1, ΔHfo(Ta3N5) = -849.7 ± 11.7, ΔHfo(Ca2ZnN2) = -378.9 ± 8.6, ΔHfo(Sr2ZnN2) = -385.6 ± 14.3, ΔHfo(LiCaN) = -216.8 ± 10.8, ΔHfo(LiZnN) = -137.5 ± 6.8, and ΔHfo(CaTaN2) = -643.8 ± 9.6. These enthalpies of formation are small in magnitude compared to analogous values for oxides. However, the enthalpies of formation of the ternaries from binary nitrides can be quite substantial, confirming significant energetic stabilization of ternary nitrides. The energetics of ternary nitride formation appears to be dominated by the acid/base character of the cations. A linear relationship was found between the enthalpies of formation of the ternaries from binary nitrides and the ionic potential ratio of the two cations.
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U2 - 10.1021/cm970244r
DO - 10.1021/cm970244r
M3 - Article
AN - SCOPUS:0001753505
VL - 9
SP - 1538
EP - 1546
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 7
ER -