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In this study, the vapor pressures of both Ils were obtained by Knudsen effusion mass-spectrometry (KEMS) with using original high temperature ion source with electron ionization (EI, Eion = 70 eV) of vapour components. Commercial MI1201 magnetic mass spectrometer (r = 200 mm, R = 500) was used. In addition, Matrix Assisted Laser Dissociation Ionization Mass Spectrometry (MALDI MS) was applied for qualitative analysis of the composition of the condensed phases – the initial ILs and their evaporation residues. During the complete isothermal evaporation/thermolysis of the samples, experimental dependences of the decomposition products pressures on time were obtained. Using the original procedure for processing of these functions, kinetic curves of chlorides [ЕMIm]Cl and [BuMIm]Cl decomposition according to established schemes, as well as the rate constants of the corresponding reactions, were obtained.