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Title: A SPECTROPHOTOMETRIC STUDY OF THE HYDROLYSIS OF PLUTONIUM(IV)

Abstract

The hydrolysis of Pu(IV) in H/sub 2/O and D/sub 2/O was studied by means of spectrophotometric measurements at 3300 A and various acidities. The data were solved with the least squares method on an IBM computer (704) for the hydrolysis constant K = STAPuOH/sup 3+/!STAH/sup +/!/STAPu/sup 4+/!. Measurements were made at 15.4 and 25.0 deg C, and they give 8.5 plus or minus 0.9 and 19.4 plus or minus 1.3 kcal/mole for the heat of hydrolysis in H/sub 2/O and D/sub 2/O, respectively. For an ionic strength of 2 M and 25.0 deg C, the weighted K ia 0.0185 plus or minus 0.0004 in H/sub 2/O and 0.0115 plus or minus 0.0008 in D/sub 2/O. This is given a K/sub H//K/sub D/ of 1.6. which is in disagreement with that found from kinetic studies of the Pu(III)Pu(VI) reaction, but in qualitative agreement with the K/sub H//K/sub D/ ratios observed for Np(IV) and U(IV). The K/sub H/ is compared with the values derived from earlier spectrophotometric data for Pu(IV) and potentiometric data for the Pu(III)-Pu(IV) couple. (D.L.C.)

Authors:
;
Publication Date:
Research Org.:
Los Alamos Scientific Lab., N. Mex.
Sponsoring Org.:
USDOE
OSTI Identifier:
4169037
NSA Number:
NSA-14-014783
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry (U.S.)
Additional Journal Information:
Journal Volume: Vol: 64; Other Information: Orig. Receipt Date: 31-DEC-60
Country of Publication:
Country unknown/Code not available
Language:
English
Subject:
CHEMISTRY; ACIDITY; COMPUTERS; ELECTRIC POTENTIAL; HEAVY WATER; HYDROLYSIS; MEASURED VALUES; NEPTUNIUM; PHOTOMETRY; PLUTONIUM; SPECTRA; URANIUM; USES; WATER

Citation Formats

Rabideau, S W, and Kline, R J. A SPECTROPHOTOMETRIC STUDY OF THE HYDROLYSIS OF PLUTONIUM(IV). Country unknown/Code not available: N. p., 1960. Web. doi:10.1021/j100834a506.
Rabideau, S W, & Kline, R J. A SPECTROPHOTOMETRIC STUDY OF THE HYDROLYSIS OF PLUTONIUM(IV). Country unknown/Code not available. doi:10.1021/j100834a506.
Rabideau, S W, and Kline, R J. Sun . "A SPECTROPHOTOMETRIC STUDY OF THE HYDROLYSIS OF PLUTONIUM(IV)". Country unknown/Code not available. doi:10.1021/j100834a506.
@article{osti_4169037,
title = {A SPECTROPHOTOMETRIC STUDY OF THE HYDROLYSIS OF PLUTONIUM(IV)},
author = {Rabideau, S W and Kline, R J},
abstractNote = {The hydrolysis of Pu(IV) in H/sub 2/O and D/sub 2/O was studied by means of spectrophotometric measurements at 3300 A and various acidities. The data were solved with the least squares method on an IBM computer (704) for the hydrolysis constant K = STAPuOH/sup 3+/!STAH/sup +/!/STAPu/sup 4+/!. Measurements were made at 15.4 and 25.0 deg C, and they give 8.5 plus or minus 0.9 and 19.4 plus or minus 1.3 kcal/mole for the heat of hydrolysis in H/sub 2/O and D/sub 2/O, respectively. For an ionic strength of 2 M and 25.0 deg C, the weighted K ia 0.0185 plus or minus 0.0004 in H/sub 2/O and 0.0115 plus or minus 0.0008 in D/sub 2/O. This is given a K/sub H//K/sub D/ of 1.6. which is in disagreement with that found from kinetic studies of the Pu(III)Pu(VI) reaction, but in qualitative agreement with the K/sub H//K/sub D/ ratios observed for Np(IV) and U(IV). The K/sub H/ is compared with the values derived from earlier spectrophotometric data for Pu(IV) and potentiometric data for the Pu(III)-Pu(IV) couple. (D.L.C.)},
doi = {10.1021/j100834a506},
journal = {Journal of Physical Chemistry (U.S.)},
number = ,
volume = Vol: 64,
place = {Country unknown/Code not available},
year = {1960},
month = {5}
}