Solid + liquid equilibria and molecular structure studies of binary mixtures for nitrate ester's stabilizers: Measurement and modeling

Solid-liquid equilibria (SLE) data for two binary organic mixtures of N-(2-methoxyethyl)-p-nitroaniline+Nethyl- 4-nitroaniline (S1) and N-(2-ethanol)-p-nitroaniline+N-ethyl-4-nitroaniline (S2) have been measured using differential scanning calorimeter to build the corresponding solid-liquid phase diagrams. The quality of the SLE data has been checked by consistency tests, presenting good quality factors for both systems. Simple eutectic behavior has been observed for these systems with the presence of a solid-solid transition for S2. The SLE data have been correlated by means of Wilson, NRTL, and UNIQUAC equations. The used models calculate the equilibrium temperatures very satisfactorily. The best modeling results were obtained using the Wilson equation with a root mean square deviation between experimental and calculated values for S1 and S2 of 1.15 and 1.99, respectively. The Wilson, NRTL, and UNIQUAC equations have also been used to compute excess thermodynamic functions viz. excess Gibbs energy, enthalpy, and entropy. The obtained results demonstrated a moderate positive deviation to ideality for S1, and a strong positive deviation for S2, unveiling the nature of the interactions between the compounds forming each mixture. In addition, microstructural studies have been carried out by FTIR, XRD and optical microscopy. Weak molecular interactions have been shown for the eutectic compositions. Jackson’s roughness parameter was calculated and found to be greater than 2, suggesting the faceted morphology with irregular structures. The authors are grateful for the financial support of this research from Ecole Militaire Polytechnique (Doctoral Training Program) and from Associate Laboratory LSRE-LCM, Instituto Politécnico de Bragança (projectPOCI-01-0145-FEDER-006984) funded by European Regional Development Fund (ERDF) through COMPETE2020 –Programa Operacional Competitividade e Internacionalização (POCI) – and by national funds through FCT - Fundaçãopara a Ciência e a Tecnologia. C.M.S.S. Neves thanks FCT for the postdoctoral grant SFRH/BPD/ 109057/2015. info:eu-repo/semantics/publishedVersion