Lithium carbonate (Li2CO3) and ammonium dihydrogen phosphate (NH4H2PO4) were used for synthesizing lithium diphosphate (Li4P2O7). The purity of the latter compound was checked up by X-ray diffraction. The heat of dissolution of (Li4P2O7) in phosphoric acid solution was measured in a C-80 SETARAM calorimeter. Many dilution and mixing processes in acid solutions of several concentrations (w/w) H3PO4, were also realized in the calorimeter in order to get the standard enthalpy of formation of this product. Two thermochemical cycles were investigated and the obtained values for the enthalpy of formation are: (-3383.4 and -3147) kJ . mol (1). The former one is in better agreement with literature data. (C) 2013 Elsevier Ltd. All rights reserved.