The enthalpies of formation of synthetic MgSO(4)·4H(2)O (starkeyite) and MgSO(4)·3H(2)O were obtained by solution calorimetry at T=298.15 K. The resulting enthalpies of formation from the elements are [Formula: see text] (starkeyite)=-2498.7±1.1 kJ·mol(-1) and [Formula: see text] (MgSO(4)·3H(2)O)=-2210.3±1.3 kJ·mol(-1). The standard entropy of starkeyite was derived from low-temperature heat capacity measurements acquired with a physical property measurement system (PPMS) in the temperature range 5 K<T<300 K: [Formula: see text] (starkeyite)=254.48±2.0 J·K(-1)·mol(-1). Additionally, differential scanning calorimetry (DSC) measurements with a Perkin Elmer Diamond DSC in the temperature range 270 K<T<300 K were performed to check the reproducibility of the PPMS measurements around ambient temperature. The experimental C(p) data of starkeyite between 229 and 303 K were fitted with a Maier-Kelley polynomial, yielding C(p)(T)=107.925+0.5532·T-1048894·T(-2). The hydration state of all Mg sulfate hydrates changes in response to local temperature and humidity conditions. Based on recently reported equilibrium relative humidities and the new standard properties described above, the internally consistent thermodynamic database for the MgSO(4)·nH(2)O system was refined by a mathematical programming (MAP) analysis. As can be seen from the resulting phase diagrams, starkeyite is metastable in the entire T-%RH range. Due to kinetic limitations of kieserite formation, metastable occurrence of starkeyite might be possible under martian conditions.