• 대한화학회지
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• 제39권1호
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• pp.66-70
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• 1995

토양에서 얻어진 흄산(HA)을 한외 여과법을 이용 분자량에 따라 4개의 소부분(F1 : 100,000 dalton 이상; F2 : 100,000 dalton 이하;10,000 dalton 이하; F4 : 2,000 dalton 이하)으로 분리한 뒤 적외선 분광법과 핵자기 공명 분광법을 통하여 각 소부분들의 분광학적 특성을 규명하고 상호간에 비교 분석하였다. 4개 소부분들의 $1^H$과 $13^C$ NMR 스펙트럼은 전체적인 특성에서 모두 흄산 모액 스펙트럼과 유사하게 나타났다. 이 결과는 분자량이 변하더라도 흄산의 전체적 특성이 그대로 유지됨을 제시한다. 차이점으로는 IR 스펙트럼 결과 분자량이 적어지면서 다당류 성분 함량이 다소 감소된 반면 카르복실기 성분 함량은 조금 증가된 것으로 나타났다.

• Smart Structures and Systems
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• 제25권2호
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• pp.135-153
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• 2020

There has been a sustained interest towards the non-contact structural displacement measurement by means of videogrammetric technique. On the way forward, one of the major concerns is the spurious image drift induced by temperature variation. This study therefore carries out an investigation into the temperature effect of videogrammetric technique, focusing on the exploration of the mechanism behind the temperature effect and the elimination of the temperature-caused measurement error. 2D videogrammetric measurement tests under monotonic or cyclic temperature variation are first performed. Features of measurement error and the casual relationship between temperature variation and measurement error are then studied. The variation of the temperature of digital camera is identified as the main cause of measurement error. An excellent linear relationship between them is revealed. After that, camera parameters are extracted from the mapping between world coordinates and pixels coordinates of the calibration targets. The coordinates of principle point and focal lengths show variations well correlated with temperature variation. The measurement error is thought to be an outcome mainly attributed to the variation of the coordinates of principle point. An approach for eliminating temperature-caused measurement error is finally proposed. Correlation models between camera parameters and temperature are formulated. Thereby, camera parameters under different temperature conditions can be predicted and the camera projective matrix can be updated accordingly. By reconstructing the world coordinates with the updated camera projective matrix, the temperature-caused measurement error is eliminated. A satisfactory performance has been achieved by the proposed approach in eliminating the temperature-caused measurement error.

• Advances in concrete construction
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• 제2권2호
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• pp.109-123
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• 2014

This paper presents chloride induced corrosion durability of reinforcing steel in geopolymer concretes containing different contents of sodium silicate ($Na_2SiO_3$) and molarities of NaOH solutions. Seven series of mixes are considered in this study. The first series is ordinary Portland cement (OPC) concrete and is considered as the control mix. The rest six series are geopolymer concretes containing 14 and 16 molar NaOH and $Na_2SiO_3$ to NaOH ratios of 2.5, 3.0 and 3.5. In each series three lollypop specimens of 100 mm in diameter and 200 mm in length, each having one 12 mm diameter steel bar are considered for chloride induced corrosion study. The specimens are subjected to cyclic wetting and drying regime for two months. In wet cycle the specimens are immersed in water containing 3.5% (by wt.) NaCl salt for 4 days, while in dry cycle the specimens are placed in open air for three days. The corrosion activity is monitored by measuring the copper/copper sulphate ($Cu/CuSO_4$) half-cell potential according to ASTM C-876. The chloride penetration depth and sorptivity of all seven concretes are also measured. Results show that the geopolymer concretes exhibited better corrosion resistance than OPC concrete. The higher the amount of $Na_2SiO_3$ and higher the concentration of NaOH solutions the better the corrosion resistance of geopolymer concrete is. Similar behaviour is also observed in sorptivity and chloride penetration depth measurements. Generally, the geopolymer concretes exhibited lower sorptivity and chloride penetration depth than that of OPC concrete. Correlation between the sorptivity and the chloride penetration of geopolymer concretes is established. Correlations are also established between 28 days compressive strength and sorptivity and between 28 days compressive strength and chloride penetration of geopolymer concretes.

• Bulletin of the Korean Chemical Society
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• 제35권6호
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• pp.1749-1753
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• 2014

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reaction of Y-substituted-phenyl picolinates (7a-f) with potassium ethoxide (EtOK) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOK] curves upward while the plot of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ is linear with a positive intercept in all cases. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOK}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ ion and ion-paired EtOK, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. The ${\sigma}^{\circ}$ constants result in a much better Hammett correlation than ${\sigma}^-$ constants, indicating that the reaction proceeds through a stepwise mechanism in which departure of the leaving group occurs after the rate-determining step (RDS). $K^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through formation of a cyclic transition state (TS). The catalytic effect decreases as the substituent Y becomes a stronger electron-withdrawing group (EWG). Development of a positive charge on the N atom of the picolinyl moiety through resonance interactions is responsible for the decreasing $K^+$ ion catalysis.

• 대한화학회지
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• 제40권10호
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• pp.649-655
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• 1996

유기 리간드 tetramethylenesulfoxide(TMSO)을 Pd(II)와 Pt(II)의 착물들에 대한 거동을 UV-vis 분광학적, 자기적, 그리고 전기화학적 방법에 의해 조사하였다. 이들 착물들의 스펙트라에서 두 개의 에너지 흡수 띠가 관찰되었다. 결정장 갈라짐 에너지와 스핀 짝지움 에너지 그리고 결합 세기는 착물들의 스펙트라로부터 얻었다. 착물들의 전자적 성질은 비편재화이고, 낮은 스핀 상태임을 알았다. 리간드와 금속들은 강한 결합세기 였다. 이들 착물들은 반자기성 이었다. 착물들의 산화${\cdot}$환원 반응과정은 비수용매 속에서 순환${\cdot}$전압 전류법에 의해 조사하였다. 착물들의 산화${\cdot}$환원 과정은 일전자 일단계 반응이었으며, 확산과 반응 지배적 이었다.

• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4185-4190
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• 2011

The nucleophilic substitution reactions of ethylene phosphorochloridate (1c) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 1c involving a cyclic five-membered ring is four thousand times faster than its acyclic counterpart (1a: diethyl chlorophosphate) because of great positive value of the entropy of activation of 1c (${\Delta}S^{\neq}=+30\;cal\;mol^{-1}K^{-1}$ compared to negative value of 1a (${\Delta}S^{\neq}=-45\;cal\;mol^{-1}K^{-1}$) over considerably unfavorable enthalpy of activation of 1c (${\Delta}H^{\neq}=27.7\;kcal\;mol^{-1}$) compared to 1a (${\Delta}H^{\neq}=8.3\;kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. The free energy correlations exhibit biphasic concave upwards for substituent X variations in the X-anilines with a break point at X = 3-Me. The deuterium kinetic isotope effects are secondary inverse ($k_H/k_D$ < 1) with the strongly basic anilines and primary normal ($k_H/k_D$ > 1) with the weakly basic anilines and rationalized by the TS variation from a dominant backside attack to a dominant frontside attack, respectively. A concerted $S_N2$ mechanism is proposed and the primary normal deuterium kinetic isotope effects are substantiated by a hydrogen bonded, four-center-type TS.

• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2271-2276
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• 2014

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reaction of 4-chloro-2-nitrophenyl X-substituted-benzoates (6a-6h) with a series of primary amines including hydrazine in 80 mol % $H_2O$/20 mol % DMSO at $25.0^{\circ}C$. The Br${\o}$nsted-type plot for the reaction of 4-chloro-2-nitrophenyl benzoate (6d) is linear with ${\beta}_{nuc}$ = 0.74 when hydrazine is excluded from the correlation. Such a linear Br${\o}$nsted-type plot is typical for reactions reported previously to proceed through a stepwise mechanism in which expulsion of the leaving group occurs in the rate-determining step (RDS). The Hammett plots for the reactions of 6a-6h with hydrazine and glycylglycine are nonlinear. In contrast, the Yukawa-Tsuno plots exhibit excellent linear correlations with ${\rho}_X$ = 1.29-1.45 and r = 0.53-0.56, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by resonance stabilization of the substrates possessing an electron-donating group (EDG). Hydrazine is ca. 47-93 times more reactive than similarly basic glycylglycine toward 6a-6h (e.g., the ${\alpha}$-effect). The ${\alpha}$-effect increases as the substituent X in the benzoyl moiety becomes a stronger electron-withdrawing group (EWG), indicating that destabilization of the ground state (GS) of hydrazine through the repulsion between the nonbonding electron pairs on the two N atoms is not solely responsible for the substituent-dependent ${\alpha}$-effect. Stabilization of transition state (TS) through five-membered cyclic TSs, which would increase the electrophilicity of the reaction center or the nucleofugality of the leaving group, contributes to the ${\alpha}$-effect observed in this study.

• 한국지반환경공학회 논문집
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• 제14권2호
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• pp.51-55
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• 2013

연약지반을 개량하기 위한 심층혼합처리공법과 같은 다양한 공법은 지반보강을 위하여 그라우트를 광범위하게 사용하고 있다. 반복하중 및 동하중을 받는 지반-구조물계의 설계에 사용되는 중요한 동적변수는 사질토 및 화강풍화토, 암시편에 관하여 많이 연구 발표되었다. 하지만 그라우트로 보강된 지반에 대한 내진설계 연구는 미비한 실정이다. 이에 본 연구에서는 공진주시험기를 이용하여 점성토와 보통 포틀랜드 시멘트의 함수비와 그라우트 주입률의 변화에 따른 전단변형률과 전단탄성계수의 상관관계를 Ramberg-Osgood Model로 정규화하여 비교 분석하였다. 그 결과 동적계수는 함수비와 그라우트 주입율에 의해 영향을 받는 것으로 나타났다.

• 한국대기환경학회지
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• 제33권2호
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• pp.174-183
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• 2017

The background level and timely variation characteristics of atmospheric $^{222}Rn$ concentrations have been evaluated by the real time monitoring at Gosan site of Jeju Island, Korea, during 2008~2015. The average concentration of atmospheric radon was $2,480mBq\;m^{-3}$ for the study period. The cyclic seasonality of radon was characterized such as winter maximum and summer minimum, consistent with the reduction in terrestrial fetch going to summer. On monthly variations of radon, the mean concentration in October was the highest as $3,041mBq\;m^{-3}$, almost twice as that in July ($1,481mBq\;m^{-3}$). The diurnal radon concentrations increased throughout the nighttime approaching to the maximum ($2,819mBq\;m^{-3}$) at around 7 a.m., and then gradually decreased throughout the daytime by the minimum ($2,069mBq\;m^{-3}$) at around 3 p.m. The diurnal radon cycle in winter showed comparatively small amplitude due to little variability in atmospheric mixing depth, conversely, large amplitude was observed in summer due to relatively a big change in atmospheric mixing depth. The cluster back-trajectories of air masses showed that the high radon events occurred by the predominant continental fetch over through Asia continent, and the radon concentrations from China continent were about 1.9 times higher on the whole than those from the North Pacific Ocean. The concentrations of $PM_{10}$ also increased in proportion to the high radon concentrations, showing a good linear correlation between $PM_{10}$ and radon concentrations.

• 대한화학회지
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• 제36권1호
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• pp.44-50
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• 1992

착물들의 자기성과 스펙트라의 성질은 d 궤도 함수의 퇴화에 대한 분열과 자외선 가시 분광학적 방법으로 비수용액 속에서 조사하였다. 10Dq의 에너지 크기는 착물들의 스펙트라와 결합에너지 그리고 스핀상태로부터 얻어졌다. 전기화학적 거동은 순환전압 전류법에 의해 측정하였다. 이들의 환원 피크는 Ag/AgCl 전극으로 20mV/s에서 $[(C_6H_5)3_P]_2Pd(II)(CH_3COO)_2$는 $E_{pc1} = -1.32 V,\;E_{pc2} = -1.56 V$이고, 그리고 $[(C_6H_5)_3Pd]_2Pd(II)Cl_2$에서는 $E_{pc1} = -1.74 V,\;E_{pc2} = -1.88 V$로 일전자 비가역적인 과정이었다. 그러나 $Ni^{2+}$ 착물에서는 환원성으로 되지 않았다.