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An ionic compound is stable because of the electrostatic attraction between its positive and negative ions. The lattice energy of a compound is a measure of the strength of this attraction. The lattice energy (ΔHlattice) of an ionic compound is defined as the energy required to separate one mole of the solid into its component gaseous ions. For the ionic solid sodium chloride, the lattice energy is the enthalpy change of the process:

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Determination of Thermodynamic Properties of Alkaline Earth-liquid Metal Alloys Using the Electromotive Force Technique

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

Loïc Habert¹, Didier Mathieu¹, Stéphane Quéré¹

¹CEA, DAM, Le Ripault, Monts F-37260 France.

|November 10, 2025

Summary

This study synthesizes twenty-one energetic salts, providing benchmark lattice enthalpies. A new, physically sound method is proposed to overcome limitations in current energetic materials research.

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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.