• Asian Journal of Atmospheric Environment
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• 제8권4호
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• pp.212-224
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• 2014

There are several studies on the effects of emissions of highly reactive volatile organic compounds (HRVOC) from the industrial sources in the Houston-Galveston-Brazoria (HGB) area on the high ozone events during the Texas Air Quality Study (TexAQS) in summer of 2000. They showed that the modeled atmosphere lacked reactivity to produce the observed high ozone event and suggested "imputation" of HRVOC emissions from the base inventory. Byun et al. (2007b) showed the imputed inventory leads to too high ethylene concentrations compared to the measurements at the chemical super sites but still too little aloft compared to the NOAA aircraft. The paper suggested that the lack of reactivity in the modeled Houston atmosphere must be corrected by targeted, and sometimes of episodic, increase of HRVOC emissions from the large sources such as flares in the Houston Ship Channel (HSC) distributed into the deeper level of the boundary layer. We performed retrospective meteorological and air quality modeling to achieve better air quality prediction of ozone by comparison with various chemical and meteorological measurements during the Texas Air Quality Study periods in August-September 2006 (TexA QS-II). After identifying several shortcomings of the forecast meteorological simulations and emissions inputs, we prepared new retrospective meteorological simulations and updated emissions inputs. We utilized assimilated MM5 inputs to achieve better meteorological simulations (detailed description of MM5 assimilation can be found in F. Ngan et al., 2012) and used them in this study for air quality simulations. Using the better predicted meteorological results, we focused on the emissions uncertainty in order to capture high peak ozone which occasionally happens in the HGB area. We described how the ozone predictions are affected by emissions uncertainty in the air quality simulations utilizing different emission inventories and adjustments.

• 한국재료학회지
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• 제23권12호
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• pp.695-701
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• 2013

To understand how reactivity between reinforcing nanoparticles and aqueous solution affects electrodeposited Cu thin films, two types of commercialized cerium oxide (ceria, $CeO_2$) nanoparticles were used with copper sulfate electrolyte to form in-situ nanocomposite films. During this process, we observed variation in colors and pH of the electrolyte depending on the manufacturer. Ceria aqueous solution and nickel sulfate ($NiSO_4$) aqueous solutions were also used for comparison. We checked several parameters which could be key factors contributing to the changes, such as the oxidation number of Cu, chemical impurities of ceria nanoparticles, and so on. Oxidation number was checked by salt formation by chemical reaction between $CuSO_4$ solution and sodium hydroxide (NaOH) solution. We observed that the color changed when $H_2SO_4$ was added to the $CuSO_4$ solution. The same effect was obtained when $H_2SO_4$ was mixed with ceria solution; the color of ceria solution changed from white to yellow. However, the color of $NiSO_4$ solution did not show any significant changes. We did observe slight changes in the pH of the solutions in this study. We did not obtain firm evidence to explain the changes observed in this study, but changes in the color of the electrolyte might be caused by interaction of Cu ion and the by-product of ceria. The mechanical properties of the films were examined by nanoindentation, and reaction between ceria and electrolyte presumably affect the mechanical properties of electrodeposited copper films. We also examined their crystal structures and optical properties by X-ray diffraction (XRD) and UV-Vis spectroscopy.

• Bulletin of the Korean Chemical Society
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• 제28권8호
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• pp.1353-1357
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• 2007

Second-order rate constants (kN) have been determined spectrophotometrically for reactions of Y-substituted phenyl 2-furoates (1a-h) with piperidine and morpholine in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 oC. The Brønsted-type plot exhibits a downward curvature for the reactions with strongly basic piperidine but is linear for the reactions with weakly basic morpholine. The slope of the curved Brønsted-type plot changes from -1.25 to ?0.28 as the pKa of the conjugate acid of the leaving aryloxides decreases. The pKa at the center of the Brønsted curvature, defined as pKa°, was determined to be 6.4. The aminolysis of 1a-h has been concluded to proceed through a stepwise mechanism on the basis of the curved Brønsted-type plot. The reactions of Ysubstituted phenyl cinnamates (2a-g) with piperidine resulted in a curved Brønsted-type plot with a pKa° values of 6.4. However, the curved Brønsted-type plot has been suggested to be not due to a change in the RDS but due to a normal Hammond effect of a concerted mechanism, since the Brønsted-type plot for the corresponding reactions with morpholine results in also a curved Brønsted-type plot with a pKa° values of 6.1. The furoates with a basic leaving group (i.e., 1b-g) are less reactive than the corresponding cinnamates (i.e., 2b-g). The k2/ k-1 ratios for the reactions of 1b-h are much smaller than unity, which has been suggested to be responsible for their low reactivity.

• 대한화학회지
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• 제36권2호
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• pp.197-204
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• 1992

Cyclic acetal류 산촉매하의 중합반응에 대해서 반경험적인 MINDO/3, MNDO, $AM_1$방법 등을 사용하여 이론적으로 고찰하였다. Oxacyclic acetal의 친핵성 및 염기성은 고리 아세탈의 산소와 음전하 크기로 설명할 수 있다. 공중합하의 성장단계에서 아세탈의 반응성은 반응 중심 탄소($C_2$)의 양전하 크기와 친전자체의 낮은 LUMO에너지에 좌우됨을 예측할 수 있다. 2-butyl-1,3-dioxepane의 성장단계의 화학종인 oxonuim 이온과 carbenium 이온 사이의 계산된 안정화 에너지는 5${\sim}$7kcal/mole로 carbenium 이온이 더 유리함을 예측할 수 있다. 공중합체의 성장단계에서 두 양이온형이 빠른 속도로 평형에 도달하며, 계산 결과에 의한 반응 좌표는 $S_N1$ 메카니즘이 $S_N2$ 메카니즘보다 빠르게 진행할 것으로 예측된다.

• Bulletin of the Korean Chemical Society
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• 제35권2호
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• pp.471-476
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• 2014

A kinetic study on aminolysis of 2-chloro-4-nitrophenyl X-substituted-benzoates (2a-k) in 80 mol % $H_2O/_20mol%$ DMSO at $25.0^{\circ}C$ is reported. The Br${\emptyset}$nsted-type plot for the reactions of 2-chloro-4-nitrophenyl benzoate (2g) with a series of cyclic secondary amines curves downward (e.g., ${\beta}_1=0.25$, ${\beta}_2=0.85$ and $pK_a^o=10.3$), which is typical of reactions reported to proceed through a stepwise mechanism with a change in ratedetermining step (RDS). The Hammett plot for the reactions of 2a-k with piperidine consists of two intersecting straight lines, while the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X=1.15$ and r = 0.59. Thus, it has been concluded that the nonlinear Hammett plot is not due to a change in RDS but is caused by stabilization of substrates through resonance interactions between the electron-donating substituent and the C=O bond. Substrates possessing a substituent at the 2-position of the leaving aryloxide deviate negatively from the curved Br${\emptyset}$nsted-type plot for the reactions of Y-substituted-phenyl benzoates (3a-i), implying that the steric hindrance exerted by the substituent at the 2-position is an important factor which governs the reactivity of Y-substituted-phenyl benzoates.

• Bulletin of the Korean Chemical Society
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• 제29권7호
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• pp.1359-1363
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• 2008

Second-order rate constants have been determined spectrophotometrically for reactions of 2,4-dinitrophenyl 2- thiophenecarboxylate (2) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The Brønsted-type plot exhibits a downward curvature, i.e., the slope decreases from 0.74 to 0.34 as the amine basicity increases. The $pK_a$ at the center of the Brønsted curvature, defined as $pK_a^o$, has been determined to be 9.1. Comparison of the Brønsted-type plot for the reactions of 2 with that for the corresponding reactions of 2,4-dinitrophenyl 2-furoate (1) suggests that reactions of 1 and 2 proceed through a common mechanism, although 2 is less reactive than 1. The curved Brønsted-type plot has been interpreted as a change in RDS of a stepwise mechanism. The replacement of the O atom in the furoyl ring by an S atom (1 $\rightarrow$ 2) does not alter the reaction mechanism but causes a decrease in reactivity. Dissection of the apparent second-order rate constants into the microscopic rate constants has revealed that the $k_2/k_{-1}$ ratio is not influenced upon changing the nonleaving group from furoyl to thiophenecarbonyl. However, $k_1$ has been calculated to be smaller for the reactions of 2 than for the corresponding reactions of 1, indicating that the C=O bond in the thiophenecarboxylate 2 is less electrophilic than that in the furoate 1. The smaller k1 for the reactions of 2 is fully responsible for the fact that 2 is less reactive than 1.

• 대한화학회지
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• 제30권6호
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• pp.516-520
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• 1986

본 연구는 ${\pi}$-알릴리간드를 갖는 산소가교 팔라듐착화합물의 반응성에 관한 것이다. 이 경우에 합성한 산소가교화합물은 산소원으로서 초과산화이온$(O_2^-$)을 사용했다. 합성한 산소가교 팔라듐착화합물의 형태를 검토하기 위하여 벤젠 용매중에서 물, 메탄올 및 아세트산과의 반응을 행하였다. 그 결과 산소가교 팔라듐착화합물은 이들과 반응하여 각각 과산화수소$(H_2O_2)$를 발생하면서 히드록시, 메톡시 및 아세톡시가교 팔라듐착화합물로 변환되었다. 또한 산소가교 팔라듐착화합물은 치환페놀류인 살리실알데히드, 8-히드록시퀴놀린 및 활성메틸렌화합물인 아세틸아세톤, 디메틸말론산과도 반응하여 과산화수소와 단핵팔라듐착화합물을 생성했다. 이것은 착화합물중의 배위산소가 과산화이온$(O_2^{2-})$이며, 강한 염기로서 작용하고 있음을 시사한다.

• Bulletin of the Korean Chemical Society
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• 제24권9호
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• pp.1293-1302
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• 2003

Rate constants at various temperatures and activation parameters are reported for solvolyses of acyl chlorides (RCOCl), with R = Me, Et, i-Pr, t-Bu, cyclopentylmethyl, benzyl, thiophenylmethyl, 2-phenylethyl, diphenylmethyl, and phenylthiomethyl in 100% ethanol, 100% 2,2,2-trifluoroethanol (TFE), 80% v/v ethanol/ water and 97% w/w TFE/water. Additional rate constants for solvolyses with R = Me, t-Bu, and $PhCH_2$ are reported for TFE/water and TFE/ethanol mixtures, and for solvolyses with R = t-Bu, and PhCH2 are reported for 1,1,1,3,3,3-hexafluoropropan-2-ol/water mixtures, as well as selected kinetic solvent isotope effects (MeOH/MeOD and TFE). Taft plots show that electron withdrawing groups (EWG) decrease reactivity significantly in TFE, but increase reactivity slightly in ethanol. Correlation of solvent effects using the extended Grunwald-Winstein (GW) equation shows an increasing sensitivity to solvent nucleophilicity for EWG. The effect of solvent stoichiometry in assumed third order reactions is evaluated for TFE/ethanol mixtures, which do not fit well in GW plots for R = Me, and t-Bu, and it is proposed that one molecule of TFE may have a specific role as electrophile; in contrast, reactions of substrates containing an EWG can be explained by third order reactions in which one molecule of solvent (ethanol or TFE) acts as a nucleophile, and a molecule of ethanol acts as a general base catalyst. Isokinetic relationships are also investigated.

• Bulletin of the Korean Chemical Society
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• 제32권1호
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• pp.179-182
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• 2011

Second-order rate constants ($k_{OH^-}$) have been measured spectrophotometrically for reactions of Y-substituted phenyl phenyl thionocarbonates (4a-i) with $OH^-$ in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The $k_{OH^-}$ values for the reactions of 4a-i have been compared with those reported previously for the corresponding reactions of Y-substituted phenyl phenyl carbonates (3a-i) to investigate the effect of changing the electrophilic center from C=O to C=S on reactivity and mechanism. Thionocarbonates 4a-i are less reactive than the corresponding carbonates 3a-i although 4a-i are expected to be more reactive than 3a-i. The Bronsted-type plot for reactions of 4a-i is linear with $\beta_{lg}$ = -0.33, a typical $\beta_{lg}$ value for reactions reported to proceed through a stepwise mechanism with formation of an intermediate being the rate-determining step (RDS). Furthermore, the Hammett plot correlated with $\sigma^o$ constants results in much better linearity than that correlated with $\sigma^-$ constants, indicating that expulsion of the leaving group is not advanced in the RDS. Thus, alkaline hydrolysis of 4a-i has been concluded to proceed through a stepwise mechanism with formation of an intermediate being RDS, which is in contrast to the forced concerted mechanism reported for the corresponding reactions of 3a-i. Enhanced stability of the intermediate upon modification of the electrophilic center from C=O to C=S has been concluded to be responsible for the contrasting mechanisms.

• 대한화학회지
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• 제36권3호
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• pp.366-375
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• 1992

카르밤산 화합물의 가아민 분해반응을 이론적으로 고찰하였다. AM1 이론적 계산 결과로서의 반응성은 결합의 형성-파괴효과 및 입체효과에 의하여 결정되는데, 결합의 형성에서 유리한 $B_{AC}2$ 반응메카니즘으로 진행되는데 결과를 줌으로써 실험과 잘 일치하였다. 특히 이론적으로 열적 forbidden인 2 + 2 반응의 구조적 특성을 가지더라도 반응에 관여하는 총 전자수가 6개인 5전자 4중심 반응의 경우 1단계 연속반응으로 진행됨을 밝혔다. 또한 각 반응경로의 활성화 장벽에 대한 차이를 정량적으로 고찰해 보면 전이상태에서 $\sigma$-결합이 깨어지는 것과 $\pi$-결합이 깨어지는 차이는 17kcal/mol이며, 6-각 고리형 구조가 갖는 입체 효과의 차이는 5kcal/mol임을 알았다.