Measurement, Correlation and Thermodynamics of Solubility of 2,6‐Diamino‐3,5‐Dinitropyrazine‐1‐Oxide (LLM‐105) in Eight Solvents

Abstract

The solubility of insensitive explosive 2,6‐diamino‐3,5‐dinitropyrazine‐1‐oxide (LLM‐105) in dimethyl sulphoxide (DMSO), N,N‐dimethylformamide (DMF), N‐methyl‐2‐pyrrolidone (NMP), N,N‐diethylformamide (DEF), 1,4‐dioxane, 1,4‐butyrolactone, ethyl acetate and 1‐butyl‐3‐methylimidazolium trifluoromethanesulfonate ([Bmim]CF3SO3), were measured by a polythermal method in the temperature range of 293.15 K to 375.15 K at the atmospheric pressure. The solubility of LLM‐105 decreased in the order of DMSO, NMP, DMF, DEF, 1,4‐butyrolactone, [Bmim]CF3SO3, 1,4‐dioxane, ethyl acetate. With higher temperature, the solubility of LLM‐105 increased in all solvents. The solubility data was correlated against temperature with the modified Apelblat equation and Ideal solution model. In addition, the dissolution enthalpy, entropy, and mole Gibbs free energy of LLM‐105 in each solvent were also calculated from the experimental solubility data by using van′t Hoff equation with the temperature dependence. The results show that the dissolution process of LLM‐105 in these solvents is endothermic and the mechanism is the entropy‐driving. DMSO is suggested as the appropriate solvent for the cooling crystallization or drowning‐out crystallization of LLM‐105.

Tuning the Crystal Habits of Organic Explosives by Antisolvent Crystallization: The Case Study of 2,6-dimaino-3,5-dinitropyrazine-1-oxid (LLM-105)

“…The antisolvent crystallization experiments of LLM-105 were performed in a stirred glass crystallizer, the speed of the magnetic stirrer was 300 rpm. On the basis of the solubility data of LLM-105 [36], LLM-105 raw materials were dissolved into DMSO to obtain a saturated solution with a concentration of 0.03 g/mL. The saturated solution of LLM-105 was heated to 10 • C above the saturation temperature for 30 min to ensure that no crystal nuclei remained in the solution.…”

Solubilities of 2,6‐Diamino‐3,5‐dinitropyrazine‐1‐oxide in the Binary Mixtures of DMSO+H2O, DMF+H2O and NMP+H2O in the Temperature Range from 293.15 to 323.15 K under the Atmospheric Pressure

“…To ensure the reliability and accuracy of the gravimetric method, the solubilities of LLM‐105 in pure DMSO, DMF and NMP were measured and the results were compared with those measured by Bu under similar conditions . As shown in Figure , the solubilities of LLM‐105 in all solvents increase with the increase of temperature.…”

“…To the best of our knowledge, there is some paper published for the solubility of LLM‐105 in pure solvents , and few in mixed solvents. It has been found that DMSO, DMF and NMP are three best good solvents for LLM‐105 . Water is usually used as the anti‐solvent for the recrystallization .…”

Phase Equilibrium and Thermodynamics Studies on Dissolving Processes of Energetic Compounds: A Brief Review

“…The nucleation order of LLM-105 was also studied via a turbidity method by using a CrystalSCAN muti-channel crystallization instrument, 102 and this process was achieved by adjusting the MSZW, controlled by initial concentration, stirring speed, and cooling rate. This method has also been used to measure the solubility of LLM-105 in eight solvents 103 including DMSO, DMF, NMP, DEF, 1,4-dioxane, GBL, EA, and 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([Bmim]CF 3 SO 3 ), and the results are shown in Figure 7a,b, in which a positive dependence of the LLM-105 solubility on temperature is observed. DMSO is a suitable solvent to dissolve LLM-105 with the highest solubility, while EA is not suggested.…”