The decomposition of La-valerate (La(C4H9CO2)(3)center dot xH(2)O (x approximate to 0.45)) and La-caproate (La(C5H11CO2)(3)center dot xH(2)O (x approximate to 0.30)) was studied upon heating at 5 degrees C/mm in a flow of argon. Using a variety of techniques including simultaneous TG-DTA, FTIR, X-ray diffraction with both laboratory Cu Ka and synchrotron sources as well as hot-stage microscopy, it was found that both compounds melt prior to decomposition and that the main decomposition stage from the molten, anhydrous state leads to the formation of La-dioxycarbonate (La2O2CO3) via an unstable intermediate product and release of symmetrical ketones. Final decomposition to La2O3 takes place with release of CO2. (C) 2015 Elsevier B.V. All rights reserved.