Synthesis and stability of some members of the pharmacosiderite group, AFe4(OH)4(AsO4)3·nH2O (A = K, Na, 0.5Ba, 0.5Sr)

Samples of the pharmacosiderite group were synthesized either directly, from aqueous solutions at 160 °C, or by ion exchange over extended periods of time at 100 °C. In more than 200 experiments, no pure pharmacosiderite sample was obtained, and a protocol was developed to remove scorodite and arsenical iron oxides from the samples. In this way, K-, Na-, Ba-, and Sr-dominant pharmacosiderite samples were prepared. The chemical compositions of the two samples used for further experiments were Ba0.702Fe4[(AsO4)0.953(SO4)0.047]3(OH)3.455O0.545·5.647H2O and K1.086Fe4[(AsO4)0.953(SO4)0.047]3 (OH)3.772O0.228·4.432H2O. The Ba-dominant pharmacosiderite is tetragonal at room temperature, and the K-dominant pharmacosiderite is cubic. Upon heating, both samples lose zeolitic H2O (shown by thermogravimetry), and this loss is accompanied by unit-cell contraction. In Ba-dominant pharmacosiderite, this loss also seems to be responsible for a symmetry change from tetragonal to cubic. The slight unit-cell contraction in Ba-dominant pharmacosiderite at <100 °C might be attributed to either negative thermal expansion or minor H2O loss; our data cannot differentiate between these two possibilities. Both samples persisted in a crystalline state up to 320 °C (the highest temperature of the powder XRD experiment), showing that pharmacosiderite is able to tolerate almost complete removal of the zeolitic H2O molecules. Low-temperature heat capacity measurements show a diffuse magnetic anomaly for K-dominant pharmacosiderite at ≈5 K and a sharp lambda transition for Ba-dominant pharmacosiderite at 15.2 K. The calculated standard entropy at T = 298.15 is 816.9 ± 5.7 J/molK for K-dominant pharmacosiderite (molecular mass 824.2076 g/mol, see formula above) and 814.1 ± 5.5 J/molK for Ba-dominant pharmacosiderite (899.7194 g/mol).

Analysis of the Factors Affecting the Realization of Lambda Transition Temperature of 4He

Analysis of the Factors Affecting the Realization of Lambda Transition Temperature of 4He Owing to the dramatic change in the thermal conductivity of 4He when its temperature crosses the transition of superfluid (HeI) and normalfluid (HeII), a sealed-cell with a capillary is used to realize the lambda transition temperature, Tλ. A small heat flow is controlled through the capillary of the sealed-cell so as to realize the coexistence of HeI and HeII and maintain the stay of HeI/HeII interface in the capillary. A stable and flat lambda transition temperature "plateau" is obtained. Because there is a depression effect of Tλ caused by the heat flow through the capillary, a series of heat flows and several temperature plateaus are made and an extrapolation is applied to determine Tλ with zero heat flow. A rhodium-iron resistance thermometer with series number A34 (RIRT A34) has been used in 24 Tλ -realization experiments to derive Tλ with a standard deviation of 0.022mK, which proves the stability and reproducibility of Tλ.