The thermochemical behavior of 1-ethyl-3-methylimidazolium [EMIm] halides (Cl, Br and I) has been investigated for their crystalline and liquid states in the temperature range from -90 degrees C to 600 degrees C using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The temperatures and enthalpies of phase transitions have been determined: T-fus =86(1) degrees C, Delta H-fus = 14.2(0.7) kJ mol(-1) ([EMIm]Cl); T-fus= 67(1) degrees C, Delta H-fus= 19.3(0.7) kJ mol(-1) ([EMIm]Br); and T-fus = 74(1) degrees C, Delta H-fus = 16.9(0.6) kJ mol(-1) ([EMIm]l). The decomposition temperatures, determined by onset of DTG at 1 K min(-1) are 233 (5) degrees C ([EMIm]Cl), 246(5) degrees C ([EMIm]Br), and 249(5) degrees C ([EMIm]I). The maximum operation temperature (MOT) has been estimated based on dynamic TGA for an operation time of 24 h: 132 degrees C ([EMIm]Cl), 149 degrees C ([EMIm]Br), 139 degrees C ([EMIm]I) and 8000h: 76 degrees C ([EMIm]Cl), 90 degrees C ([EMIm]Br), 77 degrees C ([EMIm]l). The decomposition products of the investigated ionic liquids (ILs) after heating experiments were identified by means of TGA complemented with mass spectrometry (MS), for establishment of the mechanism of thermal decomposition of the ILs. Complete degradation of [EMIm]X ionic liquids occurs under formation of characteristic molecule fragments CH3+, NH+, and X+, CH3X+, C2H5X+ (X= Cl, Br, I). (C) 2015 Elsevier B.V. All rights reserved.