• Journal of the Korean Chemical Society
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• v.39 no.7
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• pp.501-507
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• 1995

The electronic structure of cis-$[Cr(cyclam)Cl_2]Cl$ has been investigated by the emission and excitation spectroscopy at 77K, and infrared and visible spectroscopy at room temperature. The ten electronic transitions due to spin-allowed and spin-forbidden are assigned. The zero-phonon line in the excitation spectrum splits into two components by $139\;cm^{-1}$, and it can be reproduced by modern ligand field theory. According to the results of ligand field analysis, we can confirm that nitrogen atoms of the cyclam ligand have a strong ${\sigma}$-donor character, but chloride ligand has weak ${\sigma}-$ and ${\pi}-$donor properties toward chromium(III) ion.

• Journal of the Korean Ceramic Society
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• v.37 no.10
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• pp.944-948
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• 2000

TiCl$_4$, 물 및 propanol의 혼합용액으로부터 가수분해하여 미립의 TiO$_2$분말을 제조할 때 HPC 첨가와 HPC 존재하에서 TiCl$_4$mole 농도 및 유기용매 처리를 했을 때 입자크기, 응집성 및 형태 등을 관찰하였다. HPC는 TiO$_2$합성시 steric dispersant로 작용하여 응집을 적게 하는 경향을 나타내었고 HPC를 첨가한 상태에서 TiCl$_4$의 mole 농도 변화는 입자크기에 크게 영향을 주었는데 TiCl$_4$mole 농도가 증가함에 따라 입자크기는 증가하였다. 또한 유기용제 처리는 분산 효과가 있었다.

• Economic and Environmental Geology
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• v.27 no.3
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• pp.231-236
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• 1994

Fluid inclusions have been studied in phenocryst quartz from the Cretaceous porphyritic granite. Three main types of fluid inclusion were found: liquid-rich inclusion (I type), gas-rich inclusion (II type) and solid-bearing inclusions (III-A, III-B). The solid-bearing inclusions (III-A, B) represent the earliest trapped fluids. They have salinities between 63 and 67.5 wt.% equivalent NaCl. These are high saline inclusions containing NaCl and KCl daughter crystals. Homogenization temperature inferred from the fluid inclusion study ranges from 620 to $700^{\circ}C$. Type I and II inclusions were observed within the same fracture. This cause for these differences in degree of filling is evidence of boiling. Salinities of type I and II inclusions range from 10.24 wt.% to 13.44 wt.%, from 8.4 wt.% to 11.48 wt.% NaCl equivalent, respectively.

• Economic and Environmental Geology
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• v.46 no.1
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• pp.11-19
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• 2013

The Daehwa Mo-W deposit is located within the Gyeonggi massif. Quartz and calcite vein mineralization occurred in the Precambrian gneiss and Jurassic granites. Three main types (Type I: liquid-rich $H_2O$ type, Type II: vapor-rich $H_2O$ type, Type III: $CO_2-H_2O$ type) of fluid inclusions were observed and are classified herein based on their phase relations at room temperature. Within ore shoots, type III fluid inclusions have been classified into four subtypes (type IIIa, IIIb, IIIc and IIId) based on their volume percent of aqueous and carbonaceous ($CO_2$) phase at room temperatures combined with their total homogenization behavior and homogenization behavior of $CO_2$ phase. Homogenization temperatures of primary type I fluid inclusions in the quartz range from $374^{\circ}C$ to $161^{\circ}C$ with salinities between 13.6 and 0.5 equiv. wt.% NaCl. Homogenization temperatures of primary type III fluid inclusions in quartz of main generation, are in the range of $303^{\circ}C$ to $251^{\circ}C$. Clathrate melting temperatures of the type III fluid inclusions were 7.3 to $9.5^{\circ}C$, corresponding to salinities of 5.2 to 1.0 equiv. wt. % NaCl. Melting and homogenization temperatures of $CO_2$ phase of type III fluid inclusions were -57.4 to $-56.6^{\circ}C$ and 29.0 to $30.8^{\circ}C$, respectively. Fluid inclusion data indicate a complex geochemical evolution of hydrothermal fluids. The Daehwa early hydrothermal system is characterized by $H_2O-CO_2$-NaCl fluid at about $400^{\circ}C$. The main mineralization occurred by $CO_2$ immiscibility at temperatures of about 300 to $250^{\circ}C$. At the late base-metal mineralization aqueous fluid formed by mixing with cooler and less saline meteoric groundwater.

• Resources Recycling
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• v.17 no.6
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• pp.17-23
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• 2008

In order to simulate the leaching solution of copper sulfide ore in $FeCl_3$ solutions, synthetic solutions with composition of $FeCl_3$-$FeCl_2$-$CuCl_2$-CuCl-NaCl-HCl-$H_2O$ were prepared. The concentration of iron and copper chloride was varied from 0.1 to 1 m in synthetic solutions. The effect of composition on the mixed solution pH and potential at $25^{\circ}C$ was measured. When HCl concentration was constant, the increase of CuCl concentration increased solution pH. The increase of other solutes excluding HCl and CuCl decreased solution pH owing to the increase of the activity coefficient of hydrogen ion. A high CuCl concentration favored the redox equilibrium in the direction of Cu(I), while $FeCl_3$ had the opposite effect.

• Journal of the Mineralogical Society of Korea
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• v.20 no.1 s.51
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• pp.7-19
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• 2007

Four types of fluid inclusions are trapped within tourmaline from Daeyou pegmatite, Jangsu-Gun, Jeonllabukdo. They range $5{\sim}100\;{\mu}m$ in size and are grouped into I, II, III, and IV based on the phase behavior at the room temperature: (1) Type I inclusions are liquid-rich and NaCl equivalent salinity ranged $0{\sim}12\;wt%$, and the homogenization temperatures (Th) ranged $181{\sim}230^{\circ}C$ with eutectic temperatures (Te) $-54{\sim}-22^{\circ}C$. (2) Type II inclusions are vapor-rich and salinity ranged $3{\sim}8\;wt%$ NaCl, and Th ranged $177{\sim}304^{\circ}C$ also showing Te $-54{\sim}-29^{\circ}C$. (3) Type III inclusions contain a halite daughter mineral with $31{\sim}40\;wt%$ NaCl, Th $230{\sim}328^{\circ}C$. More than 90% of Type III homogenize by halite dissolution and are spatially associated with silicate melt inclusions. (4) Type IV inclusions are $CO_{2}$-bearing containing various daughter minerals such as sylvite and/or halite. The density of $CO_{2}$ system within the Type IV is $0.80{\sim}0.75\;g/cm^{3}$, Th $190{\sim}317^{\circ}C$, and salinity $2{\sim}35\;wt%$ NaCl. Type III fluid inclusions, considered as the earliest fluid, formed from the fluid exsolved from the crystallizing pegmatite. It is suggested that Type II fluid in the central part of tourmaline were exsolved earlier than Type I fluids in the margin indicating salinity fluctuation during the growth of tourmaline. It implies the fluctuation of the pressure since the salinity of fluid exsolved from the crystallizing melt is governed by the pressure. The last fluid was Type IV, which may be derived from the nearby limestone and metasedimentary rocks. It is suggested that Daeyou pegmatite containing muscovite without miarolitic cavities was formed by the partial melting resulted from the regional metamorphism. Subsequently, the exsolving fluids from the crystallizing melt were trapped in tourmaline at high pressure condition. The exsolved fluids contain various components such as $CaCl_{2}\;and\;MgCl_{2}$ as well as NaCl and KCl. The exsolution began at least at $2.7{\sim}5.3\;kbar\;and\;230{\sim}328^{\circ}C$ with the pressure fluctuation.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.923-928
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• 2000

[FeIII(BBA)DBC]ClO4 as a new functional model for catechol dioxygenases has been synthesized, where BBA is a bis(benzimidazolyl-2-methyl)amine and DBC is a 3,5-di-tert-butylcatecholate dianion.The BBA complex has a structuralfeature that iron cent er has a five-coordinate geometry similar to that of catechol dioxygenase-substrate complex.The BBA complex exhibits strong absorptionbands at 560 and 820 nm in CH3CN which are assigned to catecholate to Fe(III) charge transfer transitions. It also exhibits EPR signals at g = 9.3 and 4.3 which are typical values for the high-spin FeIII (S = 5/2) complex with rhombicsymmetry. Interestingly, the BBA complex reacts with O2 within an hour to afford intradiol cleavage (35%) and extradiol cleavage (60%) products. Surprisingly, a green color intermediate is observed during the oxygenation process of the BBA com-plex in CH3CN. This green intermediate shows a broad isotropic EPR signal at g = 2.0. Based on the variable temperature EPR study, this isotropic signalmight be originated from the [Fe(III)-peroxo-catecholate] species havinglow-spin FeIII center, not from the simple organic radical. Consequently,it allows O2 to bind to iron cen-ter forming the Fe(III)-superoxide species that converts to the Fe(III)-peroxide intermediate. These present data can lead us tosuggest that the oxygen activation mechanism take place for the oxidative cleavingcatechols of the five-coordinate model systems for catechol dioxygenases.

• Journal of the Korean Chemical Society
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• v.47 no.2
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• pp.109-114
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• 2003

The electronic absorption spectra of trans-$[CrX_2([15]aneN_4)]ClO_4\;([15]aneN_4$=1,4,8,12-tetraazacyclopentadecane; X=F, Cl) complexes have been interpreted using the ligand field theory. An AOMX program is used to optimize the differences between the calculated and the observed positions for the spin-allowed transition bands. The crystal field theory(CFT) parameter is directly related to the angular overlap model(AOM), normalized spherical harmonic hamiltonians(NSH), and semiempirical parameters. The various ligand field parameters are discussed in terms of their chemical significances. According to the ligand field analysis, we can confirm that the fluoride ligand is a very strong ${\sigma}-$ and ${\pi}-$donor while the chloride has weak ${\sigma}-$ and ${\pi}-$donor properties toward chromium(III) ion.

• Bulletin of the Korean Chemical Society
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• v.29 no.9
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• pp.1774-1780
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• 2008

New PVC based polymeric membrane electrodes (PME) and coated glassy carbon electrodes (CGCE) based on synthesized Schiff base complexes of Co(III); [Co(Salen)$(PBu_3)_2$]$ClO_4$, [Co($Me_2$Salen)$(PBu_3)_2$]$ClO_4$, [Co(Salen)$(PBu_3)H_2O$]$ClO_4$; as anion carriers for potentiometric determination of $ClO_4\;^-$were studied. The PME and also CGCE electrodes prepared with [Co(Me2Salen)$(PBu_3)_2$]$ClO_4$ showed excellent response characteristics to perchlorate ions. The electrodes exhibited Nernstian responses to $ClO_4\;^-$ ions over a wide concentration range with low detection limits ($1.0 {\times} 10^{-6}\;mol\;L^{-1}$ for PME and $9.0 {\times} 10^{-7}\;mol\;L^{-1}$ for CGCE). The electrodes possess fast response time, satisfactory reproducibility, appropriate lifetime and, most importantly, good selectivity toward $ClO_4\;^-$ relative to a variety of other common inorganic anions. The potentiometric response of the electrodes is independent of the pH in the pH range 2.5-8.5. The proposed sensors were used in potentiometric determination of perchlorate ions in mineral water and urine samples. The interaction of the ionophore with perchlorate ions was shown by UV/Vis spectroscopy.

• Journal of Photoscience
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• v.11 no.1
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• pp.19-23
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• 2004

The sharp-line absorption spectrum of microcrystalline samples of cis-[Cr(cycb)$Cl_2$]Cl (cycb=rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) has been measured between 13000 and $16000 cm^{-1}$ at temperatures down to 5K. The 77K emission and excitation spectra, and 298 K infrared and visible absorption spectra have also been measured. The nine electronic bands due to spin-allowed and spin-forbidden transitions were assigned. Using the observed transitions, a ligand field analysis has been performed to probe the ligand field properties of coordinated atoms in the title chromium(III) complex. The zero-phonon line in the sharp-line absorption spectrum splits into two components by $240 cm^{-1}$ , and the $large ^2$$_E{g}$ splitting can be reproduced by the modem ligand field theory. It is confirmed that nitrogen atoms of the macrocyclic cycb ligand have a strong $\sigma$-donor character, but chloride ligand has weak $\sigma$- nd $\pi$-donor properties toward chromium(III) ion.n.