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Use of thermal lensing spectrophotometry (TLS) for the study of mononuclear hydrolysis of uranium(IV)

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00300a016· OSTI ID:5852054
The possibility of using thermal lensing spectrophotometry (TLS) for the quantitative determination of chemical equilibria in very dilute (/approx/ 10/sup /minus/5/ M) aqueous solution has been explored. The hyrolysis of uranium(IV) has been used as a test case. TLS turned out to be a convenient, precise, and rapid method to obtain information about the mononuclear hydrolysis, information that is difficult to obtain with more traditional solution chemical methods. The TLS data were obtained at 25/degree/C in the concentration range of 0 /le/ /minus/log (H/sup +/) /le/ 2.8 by using a 3 M (Na,H)ClO/sub 4/ ionic medium. The data were described with the following chemical model: U/sup 4+/ + H/sub 2/O /r equilibrium/ UOH/sup 3+/ + H/sup +/, log */beta//sub 1/ = -1.65 /plus minus/ 0.05; U/sup 4+/ + 2H/sub 2/O /r equilibrium/ U(OH)/sub 2//sup 2+/ + 2H/sup +/, log */beta//sub 2/ < -4.5. Apart from its higher sensitivity, the TLS method has the same characteristics as ordinary spectrophotometric methods. The experimental results of this study and previous literature information were interpreted by using the specific ion interaction theory to give log */beta//degree//sub 1/ = -0.51 /plus minus/ 0.03 (log */beta//degree//sub 1/ is the equilibrium constant at zero ionic strength) and /Delta//epsilon/ is the ion interaction term /Delta//epsilon/ = /epsilon/(UOH/sup 3+/, ClO/sub 4//sup /minus//) + /epsilon/(H/sup +/, ClO/sub 4//sup /minus//) /minus/ /epsilon/(U/sup 4+/, ClO/sub 4//sup /minus//). 16 refs., 5 figs..
Research Organization:
Joint Research Centre, Ispra (Italy)
OSTI ID:
5852054
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 28:1; ISSN INOCA
Country of Publication:
United States
Language:
English