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The equilibrium solubility of the quaternary system LuCl 3 -CdCl 2 -HCl-H 2 O was determined at 298.15 K, and the corresponding equilibrium diagram was constructed in this paper. The quaternary system is complicated with four equilibrium solid phases, CdCl 2 • H 2 O, Cd 3 LuCl 9 • 14H 2 O (3:1 type), CdLuCl 5 • 9H 2 O (1:1 type), and LuCl 3 • 6H 2 O, of which the new compounds Cd 3 LuCl 9 • 14H 2 O and CdLuCl 5 • 9H 2 O were found to be congruently soluble in the system. The two new compounds obtained were identified and characterized by the methods of X-ray diffraction, thermogravimetry, and differential thermogravimetry. The standard molar enthalpies of solution of Cd 3 LuCl 9 • 14H 2 O and CdLuCl 5 • 9H 2 O in deionized water were measured to be 28.79 ( 0.22 kJ • mol -1 and -15.48 ( 0.30 kJ • mol -1 , respectively, by heat conduction microcalorimetry. Their standard molar enthalpies of formation were calculated to be -6427.5 ( 1.3 kJ • mol -1 and -4133.7 ( 0.7 kJ • mol -1 , respectively.

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