Mass spectrometric and theoretical study of the mixed complex NaCeCl4(g) Original Research Article

The vaporization of the NaCl–CeCl3 system was investigated at 919–1046 K by means of Knudsen effusion mass spectrometry. The vapor species NaCl, Na2Cl2, CeCl3, and NaCeCl4 were found in the equilibrium vapor and their partial pressures were evaluated. Theoretical calculations of the NaCeCl4(g) structure were performed and the thermodynamic functions of this molecule were evaluated. The enthalpy change of the dissociation reaction NaCeCl4(g)=NaCl(g)+CeCl3(g) was determined by the third-law method as 238.0±6.5 kJ mol−1. The volatility enhancement of CeCl3 by the formation of the vapor complex NaCeCl4 was estimated from obtained thermodynamic data of gaseous and condensed phases.