Phase transitions of the system silver mercury iodide (Ag2HgI4)-copper mercury iodide (Cu2HgI4) at normal and high pressure studied by differential scanning calorimetry

Abstract

Differential scanning calorimetry has been applied for studying the system Ag{sub 2}HgI{sub 4}-Cu{sub 2}HgI{sub 4} at both normal and high pressure. It is confirmed that there is a miscibility gap in the ordered phase and that the order-disorder phase transition has a eutectoid point at 307 K and 42.7 mol % Cu{sub 2}HgI{sub 4} at normal pressure, which is about 30 K higher than expected from a calculation for ideal eutectic behavior. The order-disorder transition is of first-order character over the whole composition range, confirming the interpretation by Suchow and ruling out the suggestion by Jaffray that it should be of second-order character in the middle part of the range. The transition enthalpy is equal to 7.3 {plus minus} 0.2 kJ/mol for the eutectoid composition. The phase diagram of the eutectoid composition was determined for pressures up to 0.72 GPa, and the temperature of the order-disorder transition increased from 307 to about 325 K, The correlation was not linear over the whole pressure range, but an average dT/dP slope of 25 K/GPa is in good agreement with the 24 K/GPa calculated by means of van Laar,s formula. The transition enthalpy (kJ/mol) decreased linearly with increasing pressure with d{Delta}H/dp = -4.0more » kJ/(mol GPa). A calculation from simple additive rule gives instead d{Delta}H/dp = -1.5 kJ/(mol GPa).« less