• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.18-24
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• 1989

Two crystal structures of dehydrated $Ag^+$ and $Rb^+$ exchanged zeolite A, stoichiometries of $Ag_{9}Rb_{3}-A$ (a = 12.278(2)${\AA}$) and $Ag_{10}Rb_{2}-A$ (a = 12.286(2)${\AA}$) per unit cell, have been determined by single crystal x-ray diffraction techniques. Their structures were solved and refined in the cubic space group Pm3m at 21(1)$^{\circ}$C. The crystals of $Ag_{10}Rb_{2}-A$ and $Ag_{10}Rb_{2}-A$ were prepared by flow methods using exchanged solution in which mole ratios of AgNO$_3$ and RbNO$_3$ were 1:5 and 1:50, respectively, with the total concentration of 0.05 M. The structures of the dehydrated $Ag_{9}Rb_{3}-A$ and the $Ag_{10}Rb_{2}-A$ were refined to the final error indices, $R_1$ = 0.064 and $R_2$ = 0.060 with 291 reflections, and $R_1$ = 0.063 and $R_2$ = 0.080 with 416 reflections respectively, for which I >3${\sigma}$(I). In both structures, one reduced silver atom per unit cell was found inside the sodalite cavity. It may be present as a hexasilver cluster in 1/6 of the sodalite units or as an isolated Ag atom coordinated to 4 $Ag^+$ ions in each sodalite unit to give $(Ag_5)^{4+}$, symmetry 4 mm. In the structure of dehydrated $Ag_{9}Rb_{3}-A$, 8 $Ag^+$ ions lie on the threefold axis and each is nearly at the center of the 8-rings at the sites of $D_{4h}$ symmetry. In the structure of dehydrated $Ag_{10}Rb_{2}-A$, two crystallographically different eight 6-ring $Ag^+$ ions were found; $7Ag^+$ ions in the (111) planes of their O(3) framework oxygens and one $Ag^+$ ion inside of sodalite cavity. Two crystallographically different 8-ring cations were also found; two $Rb^+$ ions at the centers of the 8-oxygen rings and one $Ag^+$ ion into the large cavity. Both structures indicate that $Rb^+$ ions prefer to occupy the 8-ring sites, while $Ag^+$ ions prefer to occupy the 6-ring sites.

• Journal of the Korean Chemical Society
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• v.37 no.2
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• pp.191-198
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• 1993

The crystal structures of $Cd_{6-}A$ evacuated at $2{\times}10^{-6}$ torr and $750^{\circ}C$ (a = 12.204(1) $\AA$) and dehydrated $Cd_{6-}A$ reacted with 0.1 torr of Cs vapor at $250^{\circ}C$ for 12 hours (a = 12.279(1) $\AA$) have been determined by single crystal X-ray diffraction techniques in the cubic space group Pm3m at $21(1)^{\circ}C.$ Their structures were refined to final error indices, $R_1=$ 0.081 and $R_2=$ 0.091 with 151 reflections and $R_1=$ 0.095 and $R_2=$ 0.089 with 82 reflections, respectively, for which I > $3\sigma(I).$ In vacuum dehydrated $Cd_{6-}A$, six $Cd^{2+}$ ions occupy threefold-axis positions near 6-ring, recessed 0.460(3) $\AA$ into the sodalite cavity from the (111) plane at O(3) : Cd-O(3) = 2.18(2) $\AA$ and O(3)-Cd-O(3) = $115.7(4)^{\circ}.$ Upon treating it with 0.1 torr of Cs vapor at $250^{\circ}C$, all 6 $Cd^{2+}$ ions in dehydrated $Cd_{6-}A$ are reduced by Cs vapor and Cs species are found at 4 crystallographic sites : 3.0 $Cs^+$ ions lie at the centers of the 8-rings at sites of $D_{4h}$ symmetry; ca. 9.0 Cs+ ions lie on the threefold axes of unit cell, ca. 7 in the large cavity and ca. 2 in the sodalite cavity; ca. 0.5 $Cs^+$ ion is found near a 4-ring. In this structure, ca. 12.5 Cs species are found per unit cell, more than the twelve $Cs^+$ ions needed to balance the anionic charge of zeolite framework, indicating that sorption of Cs0 has occurred. The occupancies observed are simply explained by two unit cell arrangements, $Cs_{12}-A$ and $Cs_{13}-A$. About 50% of unit cells may have two $Cs^+$ ions in sodalite unit near opposite 6-rings, six in the large cavity near 6-ring and one in the large cavity near a 4-ring. The remaining 50% of unit cells may have two Cs species in the sodalite unit which are closely associated with two out of 8 $Cs^+$ ions in the large cavity to form linear $(Cs_4)^{3+}$ clusters. These clusters lie on threefold axes and extend through the centers of sodalite units. In all unit cells, three $Cs^+$ ions fill equipoints of symmetry $D_{4h}$ at the centers of 8-rings.

• Economic and Environmental Geology
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• v.26 no.3
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• pp.327-335
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• 1993

Phase relations in the system Pd-Sb-Te were investigated at $1000^{\circ}$, $800^{\circ}$, and $600^{\circ}C$, using the sealed-capsule technique; the quenched products were studied by reflected light microscopy, X-ray diffraction, and electron microprobe analysis. At $1000^{\circ}C$, the solid phases Pd, $Pd_{20}Sb_7$, $Pd_8Sb_3$, $Pd_{31}Sb_{12}$, and $Pd_5Sb_2$ are stable with a liquid phase that occupies most of the isothermal diagram. Additional solid phases at $800^{\circ}C$ are $Pd_5Sb_3$, PdSb, $Pd_8Te_3$, $Pd_7Te_3$, and a continuous $Pd_{20}Te_7-Pd_{20}Sb_7$ solid solution becomes stable. At $600^{\circ}$, $PdSb_2$, $Pd_{17}Te_4$, $Pd_9Te_4$, PdTe, $PdTe_2$, $Sb_2Te_3$, and Sb and continuous PdSb-PdTe and $PdTe-PdTe_2$ solid solutions are stable. All the solid phases exhibit solid solution, mainly by substitution between Sb and Te to an extent that varies with temperature of formation. The maximum substitution (at.%) of Te for Sb in the Pd-Sb phases is: 44.3 in $Pd_8Sb_3$, 52.0 in $Pd_{31}Sb_{12}$, 46.2 in $Pd_5Sb_2$ at $800^{\circ}C$; 15.3 in $Pd_5Sb_3$, 68.3 in $PdSb_2$ at $600^{\circ}C$. The maximum substitution (at.%) of Sb for Te in the Pd-Te phases is 34.5 in $Pd_5Sb_3$ at $800^{\circ}C$, and 41.6 in $Pd_7Te_3$, 5.2 in $Pd_{17}T_4$, 12.4 in $Pd_9Te_4$, and 19.1 in $PdTe_2$ at $600^{\circ}C$. Physical properties and X-ray data of the synthetic $Pd_9Te_4$, PdTe, $PdTe_2$, $Pd_8Sb_3$, PdSb, and $Sb_2Te_3$ correspond very well with those of telluropalladinite, kotulskite, merenskyite, mertieite II, sudburyite, and tellurantimony, respectively. Because X-ray powder diffraction data consistently reveal a 310 peak ($2.035{\AA}$), the $PdSb_2$ phase is most probably of cubic structure with space group $P2_13$. The X-ray powder pattern of a phase with PdSbTe composition, synthesized at $600^{\circ}C$, compares well with that of testibipalladite. Therefore, testibiopalladite may be a member of the $PdSb_2-Pd(Sb_{0.32}Te_{0.68})$ solid solution series which is cubic and $P2_13$ in symmetry. Thus the ideal fonnula for testibiopalladite, presently PdSbTe, must be revised to PdTe(Sb, Te). Borovskite($pd_3SbTe_4$) has not been found in the synthetic system in the temperature range $1000^{\circ}-600^{\circ}C$.