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Abstract  

The numerical value of the first hydrolysis constant of tetravalent plutonium is uncertain by a factor of about ten. This article illustrates the estimation of that constant by a least squares method applied to simultaneous equations involving all of the Pu oxidation states.

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Abstract  

A new method for estimating the numerical value of the first hydrolysis constant of tetravalent plutonium is illustrated by examples. It uses the pH and the equilibrium fractions of two of the Pu oxidation states. They are substituted into one or more of a choice of formulas that render explicit estimates of the hydrolysis constant.

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Abstract  

Six discrete formulas are used to estimate the equilibrium constant of the first hydrolysis reaction of tetravalent plutonium. They apply the pH, the oxidation number, one equilibrium constant, and fractions of two of the plutonium oxidation states. The new formulas are not restricted to the equilibrium condition.

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Abstract  

Equilibrium-constant expressions for Pu disproportionation reactions traditionally contain three or four terms representing the concentrations or fractions of the oxidation states. The expressions can be rewritten so that one of the oxidation states is replaced by a term containing the oxidation number of the plutonium. Experimental estimations of the numerical values of the constants can then be checked in several ways.

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Abstract  

The first hydrolysis constant of tetravalent plutonium can be estimated by two methods that also estimate other solution parameters. The estimates of the hydrolysis constant compare favorably to the traditional values when the ancillary estimates compare favorably to the measurements.

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Abstract  

The first empirical method for preparing a plutonium predominance-region diagram used horizontal lines to locate the boundaries of the regions of forbidden, unique, and ambiguous oxidation-state distributions. A second approach changes the procedure by using vertical lines to illustrate these regions. In both cases, the boundary lines are determined by the Pu oxidation number and the equilibrium fraction of one oxidation state.

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Abstract  

An empirical method for preparing a plutonium predominance-region diagram is illustrated by an example. The method estimates the boundaries of the forbidden, unique, and ambiguous regions as defined by the equilibrium fraction of hexavalent plutonium and the plutonium oxidation number.

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Abstract  

The equilibrium constant for the first hydrolysis reaction of tetravalent plutonium is surrounded by uncertainty. A new method illustrates criteria by which the reliabilities of the numerical estimates can be judged. The new formulas are simple, the method is easy to apply, and the results are easy to compare.

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Abstract  

The percents of all oxidation states produced by Pu disproportionation, including unreacted starting material, can be obtained by new equations that are easy to apply. The equations are useful for quantifying the extent and the stoichiometry of disproportionation, the consequences of complexation, and the effects of temperature changes on the composition of the oxidation-state mixture.

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Abstract  

Disproportionation equations are illustrated for two oxidation numbers (N) and for the general case of any N. The new method illustrates the effect of N on the coefficients in disproportionation equations. An estimate of the equilibrium constant for the first hydrolysis reaction of tetravalent plutonium is obtained by a new approach. The estimated value agrees with many previous results.

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