Formation and Dehydration Enthalpy of Potassium Hexaniobate

The formation energetics of hydrous and dehydrated potassium hexaniobates are investigated using high‐temperature oxide melt solution calorimetry. The enthalpies of formation of K 4 Nb 6 O 17 and K 4 Nb 6 O 17 ·3H 2 O from oxides are (−864.42 ± 10.63) and (−899.32 ± 11.48) kJ/mol, respectively. The formation enthalpy of K 4 Nb 6 O 17 from elements is (−7289.64 ± 12.50) kJ/mol, and of K 4 Nb 6 O 17 ·3H 2 O is (−8181.94 ± 13.24) kJ/mol. The enthalpy of dehydration (Δ H dehy ) for the reaction K 4 Nb 6 O 17 ·3H 2 O (xl, 25°C) = K 4 Nb 6 O 17 (xl, 25°C) + 3H 2 O (l, 25°C) is endothermic and is 34.60 ± 7.56 kJ/mol. The Δ H dehy per mole of water, 11.53 ± 2.52 kJ/mol, indicates the water molecules in K 4 Nb 6 O 17 ·3H 2 O are not just physically adsorbed, but loosely bonded in the K 4 Nb 6 O 17 phase, presumably in specific interlayer sites. The loss of this water near 100°C on heating is consistent with the weak bonding of water.