• Korean Journal of Crystallography
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• v.8 no.1
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• pp.6-14
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• 1997

The crystal structures of $Sr_{31}K_{30}-X\;(Sr_{31}K_{30}Si_{100}A1_{92}O_{384};\;a=25.169(5) {\AA}$) and $Sr_{8.5}Tl_{75}-X (Sr_{8.5}Tl_{75}Si_{100}A1_{92}O_{384};\;a=25.041(5) {\AA}$) have been determined by single-crystal X-ray diffraction techniques in the cubic space group $\=F{d3}\;at\;21(1)^{\circ}C$. Each crystal was prepared by ion exchange in a flowing stream of aqueous $Sr(ClO_4)_2\;and\;(K\;or\;T1)NO_3$ whose mole ratio was 1 : 5 for five days. Vacuum dehydration was done at $360^{\circ}C$ for 2d. Their structures were refined to the final error indices $R_1=0.072\;and\;R_w=0.057$ with 293 reflections, and $R_1= 0.058\;and\;R_w=0.044$ with 351 reflections, for which $I>2{\sigma}(I)$, respectively. In dehydrated $Sr_{31}K_{30}-X,\;all\;Sr^{2+}$ ions and $K^+$ ions are located at five different crystallographic sites. Six-teen $Sr^{2+}$ ions per unit cell are at the centers of the double six-rings (site I), filling that position. The remaining 15 $Sr^{2+}$ ions and 17 $K^+$ ions fill site II in the supercage. These $Sr^{2+}$ and $K^+$ ions are recessed ca $0.45{\AA}\;and\;1.06{\AA}$ into the supercage, respectively, from the plane of three oxygens to which each is bound. ($Sr-O=2.45(1){\AA}\;and\;K-O=2.64(1){\AA}$) Eight $K^+$ ons occupy site III'($K-O=3.09(7){\AA}\;and\;3.11(10){\AA}$) and the remaining five $K^+$ ions occupy another site III'($K-O=2.88(7){\AA}\;and\;2.76(7){\AA}$). In $Sr_{8.5}Tl_{75}-X,\;Sr^{2+}\;and\;Tl^+$ ions also occupy five different crystallographic sites. About 8.5 $Sr^{2+}$ ions are at site I. Fifteen $Tl^+$ ions are at site I' in the sodalite cavities on threefold axes opposite double six-rings: each is $1.68{\AA}$ from the plane of its three oxygens ($T1-O=2.70(2){\AA}$). Together these fill the double six-rings. Another 32 $Tl^+$ ions fill site II opposite single six-rings in the supercage, each being $1.48{\AA}$ from the plane of three oxygens ($T1-O=2.70(1){\AA}$). About 18 $Tl^+$ ions occupy site III in the supercage ($T1-O=2.86(2){\AA}$), and the remaining 10 are found at site III' in the supercage ($T1-O=2.96(4){\AA}$).

• Economic and Environmental Geology
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• v.34 no.1
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• pp.13-23
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• 2001

Bentonite layers are intercalated within the basal conglomerates in the Tertiary sedimentary basins of Kampo, Janggi and Pohang, southeastern Korea. Eighteen samples of the bentonites went through X-ray diffraction, scanning electron microscopy, heavy mineral analyses, chemical analyses and oxygen, hydrogen stable isotope analyses to define the mineralogical characters of the bentonites. Heavy minerals such as zircons, apatites, amphiboles and biotites separated from bentonites show clean and euhedral surfaces, which are the characteristic features of volcanic origin. But biotites from the Chunbook Conglomerate are found as altered and heavily broken flakes which implies longer transportation of these bentonites. $TiO_{2}/Al_{2}O_{3} ratios of <2 $\mu$m particle fractions (the Chunbook Conglomerate 0.031; Janggi 0.029; Kampo 0.025) suggest that those are originated from volcanic tuffs. That is, the higher the value is, the more mafic in chemical compositions of the original tuffs. Authigenic montmorillonite and zeolite minerals were observed by SEM, which indicates diagenesis origin of bentonites. But the samples from the Chunbook Conglomerate showed only chaotically packed clay flakes in the matrix of sands or conglomerates, which implies detrital influence, not authigenic origin. The structural formulae of montmorillonite from these basins reflects their environment of formation. Fe (Ⅵ) can show the redox condition of its past environment and much lower $Fe^{2+}(Ⅵ)/Fe^{3+}(Ⅵ)$ ratios in montmorillonite of the Chunbook Conglomerate imply the greater oxidizing influence. Calculated burial depths from oxygen stable isotope data of the samples from the Chunbook Conglomerate generally fall to the range of 929~963 m whereas the real burial depth of this area is only 530~580 m. This could be explained as the bentonites of the Chunbook conglomerate had not been formed in situ. Discriminant analyses with the data from chemical analyses and structural formulae of montmorillonites show that bentonites from three different basins could definitely be distinguished with each other. This result arises from the different chemical compositions of original volcanic ashes and the difference of sedimentary environments.

• 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.