Heat capacities of selected active pharmaceutical ingredients

• Condensed-phase heat capacities of selected APIs were measured. • Many literature data sets were found to be erroneous. • Availability of reliable API heat capacity data was significantly extended. Condensed-phase heat capacities of selected pharmaceutical active pharmaceutical ingredients (APIs), namely ( RS )-ibuprofen (CAS RN: 15687-27-1), ( S )-ibuprofen (CAS RN: 51146-56-6), ( S )-naproxen (CAS RN: 22204-53-1), indomethacin (CAS RN: 53-86-1), and carbamazepine (CAS RN: 298-46-4), were determined using Tian-Calvet calorimetry and power-compensated differential scanning calorimetry in the temperature range 216 to 471 K. In most cases, previously published heat capacities of the studied APIs are in significant disagreement both with each other and our measurements. By analyzing the literature values, many previously published data sets were shown to be erroneous. The heat capacities of supercooled liquid, an important parameter in the modeling of API solubility, were also measured in a wide temperature range when feasible. The phase behavior study of carbamazepine suggests that its thermal stability is lower than previously thought, which is in accordance with the most recent studies on carbamazepine decomposition. This work significantly extends the availability of reliable API heat capacity data for clearly defined polymorphic forms and liquid phase.