• 자원환경지질
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• 제26권1호
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• pp.11-20
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• 1993

본 연구에서는 세개의 대표적인 열수점토광상인 성산, 옥매, 해남광상으로 부터 채취한 석영, 견운모, 명반석과 카올린광물 및 광상들의 주변암에 대해 산소 및 수소동위원소 연구를 실시하였다. 생산광상의 석영, 견운모, 명반석과 카올린광물에 대한 산소동위원소값은 각기 +8.4에서 +11.1‰, +4.8에서 +5.8‰, + 3.0에서 +6.6‰, +3.6에서 +5.4‰의 값을 나타낸다 옥매산광상의 석영, 견운모1 명반석과 카올린광물에 대한 산소동위원소값은 각기 +8.0에서 + 13.6‰, + 4.8에서 +8.4‰, +0.9에서 +2.4‰, +2.8에서 +6.7‰의 값을 나타낸다. 해남광상의 석영과 견운모에 대한 산소동위원소값은 각기 +7.9에서 + 10.1‰ 과 +4.5에서 +6.5‰ 의 값을 나타낸다. 화강암류와 화산암류에 대한 산소동위원소값은 각기 +3.0에서 +7.8‰ 과 +3.2에서 +10.7‰의 값을 나타낸다. 성산광상의 견운모, 영반석과 카올린팡울에 대한 수소동위원소값은 각기 -71에서 -90‰, -43에서 -77‰, -78에서 86‰ 의 값을 나타낸다 옥매산광상의 견운모, 영반석과 카올린광물에 대한 수소동위원소값은 각기 -74에서 -88‰, -57에서 98‰, -73에서 80‰ 의 값을 나타낸다. 해남광상의 견운모에 대한 수소동위원소값은 -76에서 -85‰의 값을 나타낸다. 화강암류와 화산암류에 대한 수소동위원소값은 각기 77에서 105‰과 -76에서 100‰의 값을 나타낸다. 산소 및 수소동위원소비 분석결과로부터 점토광상에서 열수의 기원에 대해 다음과 같은 해석을 할 수 있다. 산소동위원소 분석결과로부터 공존하는 광물 즉, 석영-카올린광물과 석영-견운모광물로부터 정토광상의 형성온도를 구하였다. 성산광상은 $165{\sim}280^{\circ}C$, 옥매산광상은 $175{\sim}250^{\circ}C$, 해남광상은 $250{\sim}350^{\circ}C$로 나타났다. 이틀 세개의 광상은 magmatic water와 meteoric water의 혼합으로 형성되었다. 이러한 동위원소비 분석결과로부터 카올린과 명반석광물은 hypogene 기원으로 나타났고, steam-heated 환경에서 황화수소의 산화로서 형성되었다. 황화수소의 산화작용은 지하수면 아래에서 deep-seated water의 boiling에 기인된 수증기상에서 기인된 것으로 해석된다.

• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.1963-1967
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• 2010

The rates of solvolysis of 4-morpholinecarbonyl chloride (MPC) have measured at $35.0^{\circ}C$ in water, $D_2O$, $CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol, and 2,2,2-trifluoroethanol. An extended (two-term) Grunwald-Winstein equation correlation gave sensitivities towards changes in solvent nucleophilicity and solvent ionizing power as expected for a dissociative $S_N2$ and/or $S_N1$(ionization) pathway. For nine solvents specific rates were determined at two additional temperatures and higher enthalpies and smaller negative entropies of activation were observed, consistent with the typical dissociative $S_N2$ or $S_N1$(ionization) pathway. The solvent deuterium isotope effect values for the hydrolysis of MPC of $k_{H_2O}/k_{D_2O}$ = 1.27 and for the methanolysis of MPC of $k_{MeOH}/k_{MeOD}$ = 1.22 are typical magnitudes of the $S_N1$ or ionization mechanism.

• Bulletin of the Korean Chemical Society
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• 제28권11호
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• pp.2009-2014
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• 2007

The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

• Bulletin of the Korean Chemical Society
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• 제33권11호
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• pp.3544-3550
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• 2012

Cetrizine dihydrochloride (CTZH) is widely used as an anti-allergic drug. Sodium N-bromo-p-toluenesulfonamide or bromamine-T (BAT) is the bromine analogue of chloramine-T (CAT) and is found to be a better oxidizing agent than CAT. In the present research, the kinetics of oxidation of CTZH with BAT in acid and alkaline media was studied at 313 K. The experimental rate laws obtained are: -d[BAT]/dt=$k[BAT][CTZH]^{0.80}[H^+]^{-0.48}$ in acid medium and -d[BAT]/dt=$k[BAT][CTZH]^{0.48}[OH^-]^{0.52}[PTS]^{-0.40}$ in alkaline medium where PTS is p-toluenesulfonamide. Activation parameters and reaction constants were evaluated. The solvent isotope effect was studied using $D_2O$. The dielectric effect is positive. The stoichiometry of the reaction was found to be 1:1 and the oxidation products were identified as 4-chlorobenzophenone and (2-piperazin-1-yl-ethoxy)-acetic acid in both media. The rate of oxidation of CTZH is faster in acid medium. Suitable mechanisms and related rate laws have been worked out.

• 한국원자력학회:학술대회논문집
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• 한국원자력학회 1996년도 추계학술발표회논문집(2)
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• pp.571-576
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• 1996

The 3-stage cascade composed of the multisection-type bithermal $H_2$/$H_2O$-exchange columns was suggested for heavy water separation. In order to study the separation characteristics for the cascade, a matrix equation with 18 simultaneous equations was composed and the concentrations and flow rates were calculated for the all parts of the cascade. Product D-concentration decreases and extraction yield increases with increasing cut in each stage, which is one of the principal parameters of the separation characteristics. The optimization of the 3-stage cascade can be made by case study using the matrix equation.

• Bulletin of the Korean Chemical Society
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• 제34권6호
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• pp.1698-1702
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• 2013

Glucose is a common medical analyte measuring in human serum or blood samples. The development of a primary method is necessary for the establishment of traceability in measurements. We have developed an isotope dilution liquid chromatography tandem mass spectrometry as a primary method for the measurement of glucose in human serum. Glucose and glucose-$^{13}C_6$ in sample were ionized in ESI negative mode and monitored at mass transfers of m/z 179/89 and 185/92 in MRM, respectively. Glucose was separated on $NH_2P$-50 2D column, and the mobile phase was 20 mM $NH_4OAc$ in 30% acetonitrile/70% water. Verification of this method was performed by the comparison with NIST SRMs. Our results agreed well with the SRM values. We have developed two levels of glucose serum certified reference material using this method and distributed them to the clinical laboratories in Korea as samples for proficiency testings. The expended uncertainty was about 1.2% on 95% confidence level. In proficiency testings, the results obtained from the clinical laboratories showed about 3.6% and 3.9% RSD to the certified values. Primary method can provide the traceability to the field laboratories through proficiency testings or certified reference materials.

• 자원환경지질
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• 제36권6호
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• pp.441-455
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• 2003

광주지역의 지하수는 주로 Ca-$HCO_3$, Ca-Na-$HCO_3$, Ca-Na-$HCO_3$-Cl 유형의 다양한 수질을 보여준다 그러나 광주천인근 지하수는 50mg/L 이상의 비교적 높은 $Cl^-$농도를 보이고, EC는 400${\mu}s$/cm 이상의 값을 나타내며, Ca-Cl 유형의 수질 특성을 보이고 있다. 일부 지역에서는 하천과 인근 지하수 관정 사이의 거리에 따라서 $Cl^-$, $HCO_3^-$/의 농도, EC와 ${\gamma}^{18}O$ 값이 체계적으로 변화하여 하천수의 지하유입이 확인되고 있다. 안정동위원소 연구결과, 광주지역 전체 지하수의 ${\gamma}^{18}O$ 값의 범위는 -9.2∼-5.5${\textperthansand}$ 이나 광주 동남부 고지대에서는 비교적 가벼운 값(>-8${\textperthansand}$)을 나타내나, 저지대 층적층이 분포된 하천 인근 지하수에서는 -6${\textperthansand}$ 보다 무거운 ${\gamma}^{18}O$ 값이 분포 경향을 보인다. 하천 인근에서 채취된 14개 지하수 시료 사이에는 ${\gamma}$D 및 ${\gamma}^{18}D$ 값이 ${\gamma}D{=}7.1{\times}{\gamma}^{18}O$-1의 관계를 보여 증발작용에 의한 동위원소 비평형을 나타내나, 하천수와 인근 지하수의 ${\gamma}^{18}O$값은 일부 지역에서 하천수 유입에 의한 체계적인 분별효과를 나타내기도 한다. 하천 인근 지하수의 DIC(용존무기탄산염)에 대한 ${\gamma}^{13}C$ 값은 -17.6∼15.2${\textperthansand}$로써 매우 가벼운 값을 나타내며, 토양 유기물 기원의 $CO_2$실 영향이 우세한 것으로 확인되었다. $NO_3^-$에 대한 ${\gamma}^{15}N$ 및 ${\gamma}^{18}O$ 값은 각 0∼17.0${\textperthansand}$ 및 6.6∼17.4${\textperthansand}$로써 토양의 질산염, 생활하수 및 분뇨 기원의 질소가 혼합된 것으로 나타나고 있으며 대부분 시료는 탈질 화작용이 약 40∼60%까지 진행되면서 ${\gamma}^{15}N$ 및 ${\gamma}^{18}O$ 값의 체계적인 분별효과가 야기되었다.

• Rapid Communication in Photoscience
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• 제3권4호
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• pp.64-66
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• 2014

Synthesis of a deuterium-labeled derivative of nitrospirobenzopyran (NSP), one of representative photochromic compounds, has been described. Four deuteriums were successfully introduced on 1-methyl and ${\alpha}$-methyne relative to spiro-carbon in the title compound with more than 95atom%D purity. Main photodegraded products of NSP were two oxindoles in acetonitrile, and additional products were formed in poly(isobutyl-methacrylate) films possibly due to restricted molecular motion in polymer matrix. Quantitative HPLC analysis revealed that partial introduction of deuterium to NSP brought a noticeable isotope effect, recognizable enhancement in photo-resistivity of NSP, i.e.,8.3% in solutions and 29% in polymeric films.

• Bulletin of the Korean Chemical Society
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• 제17권8호
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• pp.712-715
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• 1996

Kinetic studies are carried out on the reactions of N-methyl-N-phenylcarbamoyl chlorides with benzylamines in acetonitrile. The selectivity parameters, ρX (=-0.6~-0.8), ρY (=1.0-1.1), and ρXY (=-0.14), suggest that the reaction proceeds by an SN2 mechanism. Kinetic isotope effects, kH/kD, involving deuterated nucleophiles (XC6H4CH2ND2) are all inverse type (<1.0), and the trends of changes in the magnitude are consistent with those expected for the observed negative sign of ρXY(=∂ρX/∂σY = ∂ρY/∂σX < 0). The relatively low activation enthalpies also support the proposed mechanism.

• Bulletin of the Korean Chemical Society
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• 제21권10호
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• pp.955-956
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• 2000

Solvolyses of methanesulfonyl chloride in water, $D^2O$, $CH^3OD$, and in aqueous binary mixtures of acetone, eth-anol and methanol are investigated at 25, 35 and $45^{\circ}C.$ The Grunwald-Winstein plot of first-order rate con-stants for the solvolytic react ion of methanesulfonyl chloride with YCl (based on 2-adamantyl chloride) shows marked dispersions into three separate lines for three aqueous mixtures with a small m value (m < 0.30), and shows a rate maximum for aqueous alcoholic solvents. Stoichiometric third-order rate constants, kww and kaa were calculated from the observed first-order rate constants and (kaw + kwa) was calculated from the kww and kaa values. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed and/or SAN/SN2 reaction mechanism for methanesulfonyl chloride solvolyses based on mass law and stoichiometric solvation effect studies.