Abstract
Complex formation in Ln chloride solutions is studied by spectrophotometric method. Electronic absorption spectra of Nd3+, Sm3+, and Ho3+ ions are measured in the range of supersensitive transitions in solution with Cl− ion concentration from 0 to 5 mol/l in 100–250°C temperature interval under saturated vapor pressure. The Nd and Sm spectra represent integrated curves that mainly consist of Ln3+ and LnCl2+ absorption bands (with stability constant β1), while the Ho spectra consist of Ho3+ and HoCl2+ absorption bands (with β2). The stability constants β1 and β2 calculated for each wave number by linear regression method acquire steady values and have the meaning of the best unbiased linear estimates. Thermodynamic values of logβ1 for Nd, Sm, and Ho monochlorides lie in a narrow interval at constant temperature. In the case of Nd and Sm, the temperature curves of logβ1 and logβ2 have smaller slopes as compared to that of Ho, which is explained by the effect of a covalent component in their spectra that adds to the ionic nature of the bonds in monochloride complexes. The β2 values increase in the order Nd<Sm<Ho in accordance with electrostatic model of a bond.
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