• Bulletin of the Korean Chemical Society
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• 제23권8호
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• pp.1121-1126
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• 2002

Two anhydrous crystal structures of fully dehydrated Cd2+ - and Cs+ -exchanged zeolite X, Cd32Cs28Si100Al92O384 (Cd32Cs28-X: a = 24.828(11) $\AA)$ and fully dehydrated Cd,sup>2+ - and Rb+ -exchanged zeolite X, Cd28Rb36Si100Al92O384 (Cd28Rb36-X: a = 24.794(2) $\AA$), have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at $21(1)^{\circ}C.$ The structures were refined to the final error indices, R1 = 0.058 and R2 = 0.065 with 637 reflections for Cd32Cs28-X and R1 = 0.086 and R2 = 0.113 with 521 reflections for Cd28Rb36-X for which I > $3\sigma(I)$. In the structure of Cd,sub>32Cs28-X, 16 Cd2+ ions fill the octahedral sites I at the centers of the double six rings (Cd-O = $2.358(8)\AA$ and O-Cd-O = $90.8(3)^{\circ}$ ). The remaining 16 Cd2+ ions occupy site II (Cd-O = $2.194(8)\AA$ and O-Cd-O = $119.7(4)^{\circ})$ and six Cs+ ions occupy site II opposite to the single six-rings in the supercage; each is $2.322\AA$ from the plane of three oxygens (Cs-O = 3.193(13) and O-Cs-O = $73.0(2)^{\circ}).$ Aboutten Cs+ ions are found at site II', $1.974\AA$ into the sodalite cavity from their three oxygen plane (Cs-O = $2.947(8)\AA$ and O-Cs-O = $80.2(3)^{\circ}).$ The remaining 12 Cs+ ions are distributed over site III' (Cs-O = 3.143(9) and O-Cs-O= $59.1(2)^{\circ})$. In the structure of Cd28Rb36-X, 16 Cd2+ ions fill the octahedral sites I at the center of the double-sixrings (Cd-O = 2.349(15) and O-Cd-O = $91.3(5)^{\circ}$ ). Another 12 Cd2+ ions occupy two different II sites (Cd-O = $2.171(18)/2.269(17)\AA$ and O-Cd-O = $119.7(7)/113.2(7)^{\circ}).$ Fifteen Rb+ ions occupy site II (Rb-O = $2.707(17)\AA$ and O-Rb-O = $87.8(5)^{\circ}).$ The remaining 21 Rb+ ions are distributed over site III' (Rb-O = $3.001(16)\AA$ and O-Rb-O = $60.7(4)^{\circ})$. It appears that the smaller and more highly charged Cd2+ ions prefer sites I and Ⅱ in that order, and the larger Rb+ and Cs+ ions, which are less able to balance the anionic charge of the zeolite framework, occupy sites II and II' with the remainder going to the least suitable site in the structure, site III'.The maximum Cs+ and Rb+ ion exchanges were 30% and 39%, respectively. Because these cations are too largeto enter the small cavities and their charge distributions may be unfavorable, cation-sieve effects might appear.

• Bulletin of the Korean Chemical Society
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• 제28권1호
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• pp.41-48
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• 2007

Large colorless single crystals of sodium zeolite X, stoichiometry |Na80 |[Si112Al80O384]-FAU, with diameters up to 200 μm and Si/Al = 1.41 have been synthesized from gels with the composition of 2.40SiO2 : 2.00NaAlO2 : 7.52NaOH : 454H2O : 5.00TEA. One of these, a colorless octahedron about 200 μm in cross-section has been treated with aqueous 0.1 M KNO3 for the preparation of K+-exchanged zeolite X. The crystal structure of |K80|[Si112Al80O384]-FAU per unit cell, a = 24.838(4) A, dehydrated at 673 K and 1 × 10-6 Torr, has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd at 294 K. The structure was refined using all intensities to the final error indices (using only the 707 reflections for which Fo > 4σ (Fo)) R1 = 0.075 (based on F) and R2 = 0.236 (based on F2). About 80 K+ ions per unit cell are found at an unusually large number of crystallographically distinct positions, eight. Eleven K+ ions are at the centers of double 6-rings (D6Rs, site I; K-O = 2.492(6) A and O-K-O (octahedral) = 88.45(22)o and 91.55(22)o). Site-I' position (in the sodalite cavities opposite D6Rs) is occupied by five K+ ions per unit cell; these K+ ions are recessed 1.92 A into the sodalite cavities from their 3-oxygen planes (K-O = 2.820(19) A, and O-K-O = 78.6(6)o). Twety-three K+ ions are found at three nonequivalent site II (in the supercage) with occupancies of 5, 9, and 9 ions; these K+ ions are recessed 0.43 A, 0.75 A, and 1.55 A, respectively, into the supercage from the three oxygens to which it is bound (K-O = 2.36(13) A, 2.45(13) A, and 2.710(13) A, O-K-O = 116.5(20)o, 110.1(17)o, and 90.4(6)o, respectively). The remaining sixteen, thirteen, and twelve K+ ions occupy three sites III' near triple 4-rings in the supercage (K-O = 2.64(3) A, 2.94(3) A, 2.73(5) A, 2.96(6) A, 3.06(4) A, and 3.08(3) A).

• Bulletin of the Korean Chemical Society
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• 제30권3호
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• pp.543-550
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• 2009

The single-crystal structure of largely ammonium-exchanged zeolite Y dehydrated at room temperature (293 K) and 1 ${\times}\;10^{-6}$ Torr. has been determined using synchrotron X-radiation in the cubic space group $Fd\overline{3}m\;(a=24.9639(2)\AA)$ at 294 K. The structure was refined to the final error index $R_1$ = 0.0429 with 926 reflections where $F_o>4\sigma(F_o)$; the composition (best integers) was identified as |$(NH_4)_{60}Na_{11}$|[$Si_{121}Al_{71}O_{384}$]-FAU. The 11 $Na^{+}$ ions per unit cell were found at three different crystallographic sites and 60 ${NH_4}^{+}$ ions were distributed over three sites. The 3 $Na^{+}$ ions were located at site I, the center of the hexagonal prism ($Na-O\;=\;2.842(5)\;\AA\;and\;O-Na-O\;=\;85.98(12)^{\circ}$). The 4 $Na^{+}$ and 22 ${NH_4}^{+}$ ions were found at site I' in the sodalite cavity opposite the double 6-rings, respectively ($Na-O\;=\;2.53(13)\;\AA,\;O-Na-O\;=\;99.9(7)^{\circ},\;N-O\;=\;2.762(11)\;\AA,\;and\;O-N-O =\;89.1(5)^{\circ}$). About 4 $Na^{+}$ ions occupied site II ($(Na-O\;=\;2.40(4)\;\AA\;and\;O-Na-O\;=\;108.9(3)^{\circ}$) and 29 ${NH_4}^{+}$ ions occupy site II ($N-O\;=\;2.824(9)\;\AA\;and\;O-N-O\;=\;87.3(3)^{\circ}$) opposite to the single 6-rings in the supercage. The remaining 9 ${NH_4}^{+}$ ions were distributed over site III' ($N-O\;=\;2.55(3),\;2.725(13)\;\AA\;and\;O-N-O\;=\;94.1(13),\;62.16(15),\;155.7(14)^{\circ}$).

• Bulletin of the Korean Chemical Society
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• 제22권9호
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• pp.1023-1029
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• 2001

The positions of Kr atoms encapsulated in the molecular-dimensioned cavities of fully dehydrated zeolite A of unit-cell composition Cs3Na8HSi12Al12O48 (Cs3-A) have been determined. Cs3-A was exposed to 1025 atm of krypton gas at 400 $^{\circ}C$ for four days, followed by cooling at pressure to encapsulate Kr atoms. The resulting crystal structure of Cs3-A(6Kr) (a = $12.247(2)\AA$, R1 = 0.078, and R2 = 0.085) has been determined by single-crystal X-ray diffraction techniques in the cubic space group Pm3m at $21(1)^{\circ}C$ and 1 atm. In the crystal structure of Cs3-A(6Kr), six Kr atoms per unit cell are distributed over three crystallographically distinct positions: each unit cell contains one Kr atom at Kr(1) on a threefold axis in the sodalite unit, three at Kr(2) opposite four-rings in the large cavity, and two at Kr(3) on threefold axes in the large cavity. Relatively strong interactions of Kr atoms at Kr(1) and Kr(3) with Na+ ions of six-rings are observed: Na-Kr(1) = 3.6(1) $\AA$ and Na-Kr(3) = $3.08(5)\AA.$ In each sodalite unit, one Kr atom at Kr(1) was displaced $0.74\AA$ from the center of the sodalite unit toward a Na+ ion, where it can be polarized by the electrostatic field of the zeolite, avoiding the center of the sodalite unit which by symmetry has no electrostatic field. In each large cavity, five Kr atoms were found, forming a trigonal-bipyramid arrangement with three Kr(2) atoms at equatorial positions and two Kr(3) atoms at axial positions. With various reasonable distances and angles, the existence of Kr5 cluster was proposed (Kr(2)-Kr(3) = $4.78(6)\AA$ and Kr(2)-Kr(2) = $5.94(7)\AA$, Kr(2)-Kr(3)-Kr(2) = 76.9(3), Kr(3)-Kr(2)-Kr(3) = 88(1), and Kr(2)-Kr(2)-Kr(2) = $60^{\circ}).$ These arrangements of the encapsulated Kr atoms in the large cavity are stabilized by alternating dipoles induced on Kr(2) by four-ring oxygens and Kr(3) by six-ring Na+ ions, respectively.

• Bulletin of the Korean Chemical Society
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• 제14권5호
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• pp.603-610
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• 1993

The crystal structure of dehydrated $Ag_{5.6}K_{6.4}-A$, zeolite A ion-exchanged with $K^+\;and\;Ag^+$ as indicated and dehydrated at 360$^{\circ}$C, has been determined by single-crystal X-ray diffraction techniques. Also determined were the structures of the products of the reactions of this zeolite with 0.1 Torr of Cs vapor at 250$^{\circ}$C for 48 h and 72 h, and with 0.1 Torr of Rb vapor at 250$^{\circ}$C for 24 h. The structures were solved and refined in the cubic space group Pm3m at 21(l)$^{\circ}$C (a= 12.255(l) ${\AA}$ , 12.367(l) ${\AA}$, 12.350(l) ${\AA}$, and 12.263(l) ${\AA}$, respectively). Dehydrated $Ag_{5.6}K_{6.4}$-A was refined to the final error indices $R_1= 0.044\;and\;R_2=0.037$ with 202 reflections for which I>3${\sigma}$(I). The crystal structures of the reaction products were refined to $R_1=0.087\;and\;R_2= 0.089$ with 157 reflections, $R_1=0.080\;and\;R_2= 0.087$ with 161 reflections, and $R_1= 0.071\;and\;R_2=0.061$ with 88 reflections, respectively. In the structure of $Ag_{5.6}K_{6.4}-A,\;K^+$ ions block all 8-oxygen rings, and one reduced Ag atom is found per sodalite cavity. Also, ca. 4.6 $Ag^+ ions\;and\;3.4 K^+ ions$ are found at 6-ring sites in the large cavity. The crystal structures of the reaction products show that all $K^+$ and $Ag^+$ ions have been reduced, and that all K^+$ atoms have left the zeolite. Cs or Rb species are found at three different crystallographic sites: 3.0 $Cs^+\;or\;3.0Rb^+$ ions per unit cell occupy 8-ring centers, ca. 8.0 $Cs^+ ions\;or\;5.7 Rb^+$ ions, are found on threefold axes opposite 6-rings deep in the large cavity, and ca. 2.5 $Cs^+\;or\;2.3 Rb^+ ions are found on threefold axes in the sodalite unit. Also, 1 $Rb^+$ ion lies opposite a 4-ring. Silver atoms, corresponding to 75% or 40% occupancy of hexasilver clusters stabilized by coordination to $Cs^+\;or\;Rb^+$ ions, are found at the centers of the large cavities. In the crystal structures of dehydrated Ag_{5.6}K_{6.4}-A$ reacted with Cs vapor, excess Cs atoms are absorbed and these form (locally) cationic clusters such as $(Cs_4)3^+\;and\;(Cs_6)4^+$.

• Bulletin of the Korean Chemical Society
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• 제17권7호
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• pp.631-637
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• 1996

The structures of fully dehydrated Ca2+- and Rb+-exchanged zeolite X, Ca31Rb30Si100Al92O384(Ca31Rb30-X; a=25.009(1) Å) and Ca28Rb36Si100Al92O384(Ca28Rb36-X; a=24.977(1) Å), have been determined by single-crystal X-ray diffraction methods in the cubic space group Fd&bar{3} at 21(1) ℃. Their structures were refined to the final error indices R1=0.048 and R2=0.041 with 236 reflections for Ca31Rb30-X, and R1=0.052 and R2=0.043 with 313 reflections for Ca28Rb36-X; I>3σ(I). In both structures, Ca2+ and Rb+ ions are located at six different crystallographic sites. In dehydrated Ca31Rb30-X, sixteen Ca2+ ions fill site I, at the centers of the double 6-rings (Ca-O=2.43(1) Å and O-Ca-O=93.3(3)°). Another fifteen Ca2+ ions occupy site II (Ca-O=2.29(1) Å, O-Ca-O=119.5(5)°) and fifteen Rb+ ions occupy site II opposite single six-rings in the supercage; each is 1.60 Å from the plane of three oxygens (Rb-O=2.77(1) Å and O-Rb-O=91.1(4)°). About two Rb+ ions are found at site II', 1.99 Å into sodalite cavity from their three-oxygen plane (Rb-O=2.99(1) Å and O-Rb-O=82.8(4)°). The remaining thirteen Rb+ ions are statistically distributed over site III, a 48-fold equipoint in the supercages on twofold axes (Rb-O=3.05(1) Å and Rb-O=3.38(1) Å). In dehydrated Ca28Rb36-X, sixteen Ca2+ ions fill site I (Ca-O=2.41(1) Å and O-Ca-O=93.6(3)°) and twelve Ca2+ ions occupy site II (Ca-O=2.31(1) Å, O-Ca-O=119.7(4)°). Sixteen Rb+ ions occupy site II; each is 1.60 Å from the plane of three oxygens (Rb-O=2.81(1) Å and O-Rb-O=90.6(3)°) and four Rb+ ions occupy site II'; each is 1.88 Å into sodalite cavity from their three-oxygen plane (Rb-O=2.99(1) Å and O-Rb-O=83.8(2)°). The remaining sixteen Rb+ ions are found at III site in the supercage (Rb-O=2.97(1) Å and Rb-O=3.39(1) Å). It appears that Ca2+ ions prefer sites I and II in that order, and that Rb+ ions occupy the remaining sites. Rb+ ions are too large to be stable at site I, when they are competing with other smaller cations like Ca2+ ions.

• Bulletin of the Korean Chemical Society
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• 제10권3호
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• pp.243-247
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• 1989

Two crystal structures of dehydrated $Ag^+\;and\;Ca^{2+}$ exchanged zeolite A, $Ag_2Ca_$5-A, reacting with 0.01 Torr of Cs vapor at $200^{\circ}C$ for 2 hours and 0.1 Torr of Cs vapor at $250^{\circ}C$ for 48 hours, respectively, 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 stoichiometry of first crystal was $Ag_2Ca_5$-A (a = 12.294(1)${\AA}$), indicating that Cs vapor did not react with cations in zeolite A and that of second crystal was $Ag_2Cs_{10}$-A (a = 12.166(1)${\AA}$), indicating that all $Ca^{2+}$ ions were reduced by Cs vapor and replaced by $Cs^+$ ions. Full-matrix least-squares refinements of $Ag_2Ca_5-A\;and\;Ag_2Cs_{10}$-A has converged to the final error indices, $R_1\;=\;0.041\;and\;R_2$ = 0.048 with 227 reflections, and $R_1\;=\;0.117\;an\;n\;fdd\;R_2$ = 0.120 with 167 reflections, respectively, for which I > $3{\sigma}$(I). In the structure of $Ag_2Ca_5$-A, both $Ag^+$ ions and $Ca^{2+}$ ions lie on two crystal symmetrically independent threefold axis sites on the 6-rings; $2\;Ag^+$ ions are recessed 0.33 ${\;AA}$ from the (111) planes of three O(3) oxygens and 5 $Ca^{2+}$ ions lie on the nearly center of each 6-oxygen planes. In the structure of $Ag_2Cs_{10}-A,\;Cs^+$ ions lie on the 5 different crystallographic sites. 3 $Cs^+$ ions lie at the centers of the 8-rings at sites of D4h symmetry. 6 $Cs^+$ ions lie on the threefold axes of unit cell: $4\;Cs^+$ ions are found deep in the large cavity and 2 $Cs^+$ ions are found in the sodalite cavity. One $Cs^+$ ion is found in the large cavity near a 4-ring.

• Bulletin of the Korean Chemical Society
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• 제33권9호
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• pp.2917-2924
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• 2012

Four novel metal-organic complexes $[Cd_2(IP)_2(TBZ)_2(H_2O)_2]{\cdot}(H_2O)$ (1), $[Zn_4(IP)_4(TBZ)_4]{\cdot}2(H_2O)$ (2), $[Zn_2(BTC)(TBZ)_2(CO_2H)]$ (3), [Co(PDC)(TBZ)] (4) (where IP = isophthalate; TBZ = thiabendazole; BTC = 1,3,5-benzenetricarboxylate; PDC = pyridine-3,4-dicarboxylate) have been prepared and characterized by IR spectrum, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. X-ray structure analysis reveals that 1, 2, and 3 are one-dimensional chain polymers, while 4 is a two-dimensional network polymer. The TBZ acts as a typical chelating ligand coordinated to the metal center in all complexes. The 1D chain architecture of 1 is constructed from isophthalates and cadmium atoms. A simultaneous presence of chelating, monodentate and bidentate coordination modes of IP ligands is observed in complex 2. In complex 3, the 16-membered rings are alternately arranged forming an infinite 1D double-chain structure. The 2D skeleton of 4 is formed by cobalt ions as nodes and PDC dianions as spacers, through coordination bonds. The hydrogen bonds and ${\pi}-{\pi}$ stacking play important roles in affecting the final structure where complexes 1 and 3 have 2D supramolecular networks, while complexes 2 and 4 have 3D supramolecular architectures.

• 대한화학회지
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• 제16권5호
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• pp.271-283
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• 1972

DTA에 衣한 國産無煙炭의 燃燒反應過程을 速度論的으로 解析할 수 있는 아래의 關係式을 導出하였다. $K=\frac{C_3{\cdot}W_0}{{\Delta}H{\cdot}{\Delta}C{\cdot}M{\cdot}S_A}(\frac{dy}{dt}+A(y-y_3))$ 이 式을 利用하여 各炭種에 對한 活性化 energy값을 求한 結果 非黑鉛性炭種은 40Kcal/mole, 黑鉛性炭種은 45Kcal/mole로서 炭化度가 增加되면 活性化 energy값이 增加된다는 것을 알았다. 無煙炭을 空氣中에서 燃燒시킬때 溫度에 衣하여 d_{(002)}$ X-線回折强度가 점차적으로 커지는 現象으로부터 無煙産中의 一部가 層構造(黑鉛化)로 變化됨을 알았으며 이 變化된 層構造에 生成된 $CO_2$의 一部가 接觸分解되어 다시 CO로 환원됨을 알았다. 그리고 無煙炭의 反應性을 左右하는 活性基의 種類는 -OH, -SH, -NH, -$CH_2-CH_3,$ 및 -CO, -COC-, -COOH가 存在하며 IR 로서 炭化度를 測定할 수 있었다

• 폴리머
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• 제30권5호
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• pp.373-379
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• 2006

플로로글루시놀과 중합가능한 피리딘 유도체의 수소결합을 이용해 디아세틸렌과 아크릴로일 그룹을 함유 한 새로운 중합가능한 원반형 액정들을 제조하였고 제조된 액정들의 광중합 거동을 조사하였다. 합성된 원반형 액정 복합체들은 메소겐의 방향족 고리의 개수에 따라 원반형 컬럼상과 장방형 컬럼상을 형성하였다. 원반형 액정복합체들의 광중합은 액정상에서 자외선을 조사하여 수행하였다. 자외선 조사 후 디아세틸렌과 아크릴로일 그룹이 선택적으로 중합되었으며, 짧은 공액구조의 디아세틸렌 올리고머를 가지는 가교 고분자들이 1,4-반응에 의해 형성됨을 적외선 분광법과 자외선-가시광선 분광분석을 통해 확인하였다. X-선 회절 실험 결과, 페닐피리딘을 함유한 원반형 액정 복합체의 컬럼상 질서는 광중합 후에도 유지되었고, 바이페닐 단위를 지닌 액정 복합체의 장방형 컬럼상 질서는 라멜라 질서로 변화됨을 확인하였다.