Benchmark Measurements for Energetic Salts: A Prerequisite toward Improved Estimation Methods for Lattice Enthalpy

Area of Science:

• Energetic materials science
• Physical chemistry
• Computational chemistry

Background:

• Accurate formation enthalpies of energetic salts are crucial for safety and performance.
• Current methods for determining lattice enthalpies are unreliable due to a lack of benchmark data.

Purpose of the Study:

• To synthesize and characterize new energetic salts.
• To establish benchmark lattice enthalpies for energetic salts.
• To develop a more accurate method for calculating lattice enthalpies.

Main Methods:

• Synthesis and characterization of twenty-one energetic salts (eight novel).
• Accurate measurement of formation enthalpies via calorimetry.
• Calculation of ab initio formation enthalpies for constituent ions.
• Determination of benchmark lattice enthalpies by subtracting ion enthalpies from salt enthalpies.

Main Results:

• Successfully synthesized and characterized twenty-one energetic salts.
• Obtained benchmark lattice enthalpies for the synthesized salts.
• Identified limitations of the volume-based thermodynamics (VBT) approach.
• Proposed a new, parameter-free, physically sound alternative for lattice enthalpy calculation.

Conclusions:

• The new method provides a more reliable approach to lattice enthalpy determination.
• The findings challenge the applicability of the VBT approach for energetic salts.
• Future work will expand the database and refine the proposed method.