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Journal of Thermal Analysis and Calorimetry
Authors: Y. Y. Di, Z. C. Tan, L. W. Li, S. L. Gao, and L. X. Sun


Low-temperature heat capacities of a solid complex Zn(Val)SO4·H2O(s) were measured by a precision automated adiabatic calorimeter over the temperature range between 78 and 373 K. The initial dehydration temperature of the coordination compound was determined to be, TD=327.05 K, by analysis of the heat-capacity curve. The experimental values of molar heat capacities were fitted to a polynomial equation of heat capacities (Cp,m) with the reduced temperatures (x), [x=f (T)], by least square method. The polynomial fitted values of the molar heat capacities and fundamental thermodynamic functions of the complex relative to the standard reference temperature 298.15 K were given with the interval of 5 K.

Enthalpies of dissolution of the [ZnSO4·7H2O(s)+Val(s)] (ΔsolHm,l0) and the Zn(Val)SO4·H2O(s) (ΔsolHm,20) in 100.00 mL of 2 mol dm−3 HCl(aq) at T=298.15 K were determined to be, ΔsolHm,l0=(94.588±0.025) kJ mol−1 and ΔsolHm,20=–(46.118±0.055) kJ mol−1, by means of a homemade isoperibol solution–reaction calorimeter. The standard molar enthalpy of formation of the compound was determined as: ΔfHm0 (Zn(Val)SO4·H2O(s), 298.15 K)=–(1850.97±1.92) kJ mol−1, from the enthalpies of dissolution and other auxiliary thermodynamic data through a Hess thermochemical cycle. Furthermore, the reliability of the Hess thermochemical cycle was verified by comparing UV/Vis spectra and the refractive indexes of solution A (from dissolution of the [ZnSO4·7H2O(s)+Val(s)] mixture in 2 mol dm−3 hydrochloric acid) and solution A’ (from dissolution of the complex Zn(Val)SO4·H2O(s) in 2 mol dm−3 hydrochloric acid).

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