Two pure calcium borates of 2CaO·5B2O3·5H2O (I) and β-4CaO·5B2O3·7H2O (II) have been synthesized under
hydrothermal condition and characterized by X-ray diffraction, infrared spectra, and thermogravimetric analysis
as well as by chemical analysis. All the enthalpies of solution were measured at 298.15 K by using a heat conduction
microcalorimeter. The molar enthalpies of solution of (I) and (II) in 2.00 cm3 of 1 mol·dm-3 HCl(aq) were
measured to be −(60.30 ± 0.78) kJ·mol-1 and −(158.63 ± 0.72) kJ·mol-1, respectively. The molar enthalpies
of solution of H3BO3(s) in 2.00 cm3 of 1 mol·dm-3 HCl(aq) and of CaO(s) in 2.00 cm3 of (HCl + H3BO3)
aqueous solution were measured to be (21.84 ± 0.05) kJ·mol-1 and −(188.59 ± 0.42) kJ·mol-1, respectively.
The enthalpies change of borates (I) and (II) formation from the reaction of reagents in the solid phase,
−(98.3 ± 1.3) kJ·mol-1 and −(377.2 ± 1.9) kJ·mol-1 were calculated respectively on the basis of the appropriate
thermochemical cycles. From these data and the standard molar enthalpies of formation of CaO(s), H3BO3(s),
and H2O(l), the standard molar enthalpies of formation were calculated as −(9457.9 ± 8.3) kJ·mol-1 for (I) and
−(11578.7 ± 8.9) kJ·mol-1 for (II), respectively.
Thermochemistry E 3000Thermodynamic Properties of (NH 4 ) 2 Ca[B 4 O 5 (OH) 4 ] 2 ·8H 2 O. -The title compound is synthesized from an aqueous solution of H3BO3, CaCl2, and NH3·H2O (20 d) and characterized by chemical analysis, elemental analysis, XRD, IR spectroscopy, and TGA. The standard molar enthalpy of formation of the title compound is -10062.3 kJ·mol -1 . Further thermodynamic data such as the standard molar free energy of formation, the standard molar entropy of formation, and the standard entropy are given.
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