Actinoid pnictides--I : Heat capacities from 5 to 950 K and magnetic transitions of U3As4 and U3Sb4. Ferromagnetic transitions

Abstract

The heat capacities of triuranium tetraarsenide (U3As4) and triuranium tetraantimonide (U3Sb4), measured by adiabatic calorimetry over the temperature range 5-950 K, show sharp [lambda]-shaped transitions at 196.1 and 147.5 K, respectively. The maxima are related to the appearance of permanent magnetic moments below 198 and 148 K. Excess cooperative entropies associated with ferromagnetic ordering are tentatively estimated as 6.7 for U3As4 and 6.8 cal K-1 mole-1 for U3Sb4. These are larger than the two literature values reported for U3P4 (1.5 and 3.1 cal K-1 mole-1). The fact that these entropy of transition values are much smaller than would be expected from [Delta]St = R In (2J + 1) for the 3H4 ground term (J = 4) and that the observed heat capacities at high temperatures are much larger than would be expected from lattice plus dilational contributions are evidence of crystal field effects. The total electronic entropies to 950 K are estimated as 11.05 and 12.95 cal K-1 mole-1 for U3As4 and U3Sb4, respectively. Thermal functions for both U3As4 and U3Sb4 are integrated from the experimental data up to 950 K. At 298.15 K, the values of Cpo [So(T)-So(0)] and -{[Go(T)-Ho(0)]/T} in cal K-1 mole-1, are 44.82, 73.87 and 38.97, U3As4 and 44.98, 83.60 and 46.89, for U3Sb4.