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Heat capacity and thermodynamic functions of b-/sup 242/Pu/sub 2/O/sub 3/ from 8 to 350 K. Contributions to the excess entropy

Journal Article · · J. Chem. Phys.; (United States)
OSTI ID:6401394
The heat capacity of b-/sup 242/Pu/sub 2/O/sub 3/ was determined by a quasiadiabatic method from 8 to 350 K. The preparation of a single-phase hexagonal plutonium sesquioxide by hydrogen reduction of /sup 242/PuO/sub 2/ at 2250 K is described. A l-type heat capacity anomaly with its peak at 17.65 K was found and this anomaly is associated with an antiferromagnetic transition which is reported by McCart et al. in the preceding paper. An excess entropy of b-/sup 242/Pu/sub 2/O/sub 3/ at 298.15 K is evaluated and shown to approach S/sub excess/ = 2R ln6 = 29.79 J K/sup -1/ mol/sup -1/. In the same manner the previously published experimental entropy of /sup 242/PuF/sub 3/ at 298.15 K was shown to contain an excess entropy contribution approaching S/sub excess/ = R ln6 at 298.15 K. For each compound it was concluded that the excess entropy associated with antiferromagnetic ordering is R ln2 per mol of Pu/sup +3/ ions. For b-/sup 242/Pu/sub 2/O/sub 3/ at 298.15 K the heat capacity C/sup degree//sub p/, entropy S/sup 0/, enthalpy increment H/sup 0/(T)-H/sup 0/(0), and the Gibbs energy divided by temperature (G/sup 0/(T)-H/sup 0/(0))/T are, respectively, (116.98 +- 0.47) J K/sup -1/ mol/sup -1/, (163.02 +- 0.65) J K/sup -1/ mol/sup -1/, (22 572 +- 90) J mol/sup -1/, and (-87.31 +- 0.35) J K/sup -1/ mol/sup -1/. The standard Gibbs free energy of formation of Pu/sub 2/O/sub 3/ at 298.15 K is calculated from available experimental data.
Research Organization:
Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439
DOE Contract Number:
W-31109-ENG-38
OSTI ID:
6401394
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 74:9; ISSN JCPSA
Country of Publication:
United States
Language:
English