• Bulletin of the Korean Chemical Society
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• 제31권9호
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• pp.2593-2597
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• 2010

Second-order rate constants ($k_N$) have been measured spectrophotometrically for reactions of 2,4-dinitrophenyl X-substituted benzoates (X = 4-MeO, H and 4-$NO_2$) with a series of Z-substituted pyridines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plots exhibit downward curvature (e.g., $\beta_2$ = 0.89 ~ 0.96 when $pK_a$ < 9.5 while $\beta_1$ = 0.38 ~ 0.46 when $pK_a$ > 9.5), indicating that the reaction proceeds through a stepwise mechanism with a change in rate-determining step (RDS). The ${pK_a}^o$, defined as the $pK_a$ at the center of Br${\o}$nsted curvature, has been analyzed to be 9.5 regardless of the electronic nature of the substituent X in the benzoyl moiety. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio has revealed that $k_1$ is governed by the electronic nature of the substituent X but the $k_2/k_{-1}$ ratio is not. Theoretical calculations also support the argument that the electronic nature of the substituent X in the benzoyl moiety does not influence the $k_2/k_{-1}$ ratio.

• Macromolecular Research
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• 제14권4호
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• pp.466-472
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• 2006

The kinetic behavior of emulsion polymerizations of styrene in the presence of sulfonated N-hydroxy ethyl aniline (SHEA) was investigated with two initiators: 2,2'-azobisisobutyronitrile (AIBN) and potassium persulfate (KPS). SHEA was synthesized using a stepwise polyurethane reaction method from 3-hydroxy-1-propane sulfonic acid sodium salt, isophorone diisocyanate (IPDI), and N-(2-hydroxyethyl) aniline. Stable core-shell poly(styrene/sulfonated N-hydroxy ethyl aniline, St/SHEA) latex particles were successfully prepared by using an appropriate amount of AIBN, in which SHEA plays the role of 'surfmer', i.e., acting as both a surfactant in the emulsion polymerization and a monomer in the chemical oxidative polymerization. The kinetic behavior was dissimilar to that of typical emulsion polymerization systems. A long inhibition period and low rate of polymerization were observed due to radical loss by the oxidative polymerization of SHEA. It was concluded, due to the low water-solubility of AIBN and retardation reaction by SHEA, that the initial loci of polymerization were monomer droplets. However, growing polymer particles as polymerization loci became predominant as polymerization proceeded. It was suggested that AIBN was more effective than KPS in the preparation of the core-shell type poly(St/SHEA) latex particles. With KPS, no substantial polymerization was observed in any of the samples.

• KSBB Journal
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• 제22권3호
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• pp.157-161
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• 2007

본 연구는 수계에서의 생물학적 고찰이 거의 없었던 MEA 단독 물질을 전형적 활성슬러지와 Pseudomonas계 균주를 이용하여 분해특성을 분석한 것이다. 잠정적 결론으로서 첫째, MEA는 수계 유입 시 COD 및 $NH_4^+$ 농도의 상당한 증가를 유발하여 MEA는 $NH_4^+$로 78.1% 이상 전환되었다. 둘째, 공기 공급이 조절된 회분식 반응기에서 MEA 분해속도는 1000 mg/L에서 최대 19.23 mg/L/h, 고농도인 5000 mg/L에서 17.55 mg/L/h로서 미생물 순응이 담보되는 경우 큰 차이를 보이지 않았다. 셋째, 순차적 순응단계를 거쳐 MLVSS가 상대적으로 작은 조건 (최대 820 mg/L)에서도 약 3개월간 안정적 장기 운전이 가능하였고, 최대 분해율은 약 95%였다. 넷째, $COD_{cr}$를 기초로 한 반응속도론 분석에 의하면 MEA 생분해는 1차 반응에 부합하였다. 향후 MEA의 생물학적 공법을 확립하기 위해 활성슬러지 시스템의 미생물 효소분석을 통해 순응단계를 최적화하는 연구를 수행할 계획이다.

• Bulletin of the Korean Chemical Society
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• 제35권1호
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• pp.93-97
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl X-substituted-2-methylbenzoates (5a-e) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The Hammett plots for the aminolysis of 5a-e are nonlinear, e.g., substrates possessing an electron-donating group (EDG) in the benzoyl moiety deviate negatively from the linear line composed of substrates bearing no EDG. In contrast, the Yukawa-Tsuno plots for the same reactions exhibit excellent linear correlations with ${\rho}_X$ = 0.30-0.59 and r = 0.90-1.15, indicating that the nonlinear Hammett plots are caused by stabilization of the substrates possessing an EDG through resonance interactions but are not due to a change in the rate-determining step (RDS). The Br${\phi}$nsted-type plots are linear with ${\beta}_{nuc}$ = 0.66-0.82. Thus, the aminolysis of 5a-e has been suggested to proceed through a stepwise mechanism in which departure of the leaving group occurs at the RDS. The ${\rho}_X$ and ${\beta}_{nuc}$ values for the aminolysis of 5a-e increase as the reactivity of the substrates and amines increases, indicating that the reactivity-selectivity principle is not applicable to the current reactions.

• 대한환경공학회지
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• 제28권5호
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• pp.487-493
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• 2006

본 연구에서는 지하수에 존재하는 다양한 클로로페놀류 화합물을 제거하기 위하여 니켈로 코팅된 영가철을 이용하여 적용 타당성을 검토하였다. 다섯가지 종류의 클로로페놀 화합물을 대상으로 처리효과를 평가하였으며 중간 생성물을 분석하였다. 실험결과를 이용하여 개질된 영가철에 의한 반응경로 및 반응율을 평가하기 위하여 수치해석적 방법을 적용하였다. 개질된 영가철에 의한 오염물의 제거는 반응계수를 기준으로 2-CP>4-CP>2,4-DCP>2,4,6-TCP>2,6-DCP의 순서를 나타내었다. 수치해석 결과 각 클로로페놀 화합물의 탈염소화 반응은 연속적 단계와 평행적 단계를 거쳐 최종 생성물인 페놀화합물에 도달되는 결과를 보여주었다.

• Bulletin of the Korean Chemical Society
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• 제35권4호
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• pp.1128-1132
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• 2014

A kinetic study on aminolysis of 4-chloro-2-nitrophenyl X-substituted-benzoates (6a-i) in MeCN is reported. The Hammett plot for the reactions of 6a-i with piperidine consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X$ = 1.03 and r = 0.78. The nonlinear Hammett plot is not due to a change in rate-determining step (RDS) but is caused by the resonance stabilization of substrates possessing an electron-donating group in the benzoyl moiety. The Br${\phi}$nsted-type plot for the reactions of 4-chloro-2-nitrophenyl benzoate (6e) with a series of cyclic secondary amines is linear with ${\beta}_{nuc}$ = 0.69, an upper limit for reactions reported to proceed through a concerted mechanism. The aminolysis of 6e in aqueous medium has previously been reported to proceed through a stepwise mechanism with a change in RDS on the basis of a curved Br${\phi}$nsted-type plot. It has been concluded that instability of the zwitterionic tetrahedral intermediate ($T^{\pm}$) in MeCN forces the reaction to proceed through a concerted mechanism. This is further supported by the kinetic result that the amines used in this study are less reactive in MeCN than in $H_2O$, although they are more basic in MeCN over 7 $pK_a$ units.

• 대한화학회지
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• 제30권5호
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• pp.475-482
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• 1986

$Ni^{2+}$와 D-penicillamine사이의 착물형성반응에 대한 반응속도 및 평형에 관한 수용액중에서 실시하였다. 속도론적 실험은 압력-급변법을 사용하여 pH8~9범위에서 실시하였다. D-Penicillamine은 질소와 유황원자를 주게로 하여 pH＞9.2조건에서 $Ni^{2+}$이온에 배위하나 pH값 8.25∼9.07범위에서 총괄 안정도 상수값이 급격히 감소하며 비해리된 mercapto기가 결합에 참여하지 않는 것으로 밝혀졌다. 또한 이 착물 형성반응에 있어 율속단계는 $Ni^{2+}$이온의 내부 배위권으로 부터 물분자가 유리되는 과정임이 밝혀졌다.

• Advances in nano research
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• 제1권2호
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• pp.93-103
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• 2013

An ultrasonic-mediated assisted stepwise method has been developed for depositing transparent ZnO films from aqueous solution. Rinsing in low ethylene glycol temperature was easy to produce intermediate phase of $Zn(OH)_2$, rinsing in $120^{\circ}C$ ethylene glycol was observed the diffraction peak of intermediate $Zn(OH)_2$ in early report, the rinsing temperature plays an important role in the process of $Zn(OH)_2$ phase transformed to ZnO, high rinsing temperature actually improved the intermediate phase. However, the effect of rinsing on the intermediate phase is yet to be understood clearly. The effect of different rinsing procedures, involving either of or a combination of successive ionic layer adsorption and reaction (SILAR) and ultrasonic-assisted rinsing, prior to hydrolysis in ethylene glycol was found to improve the occurrence $Zn(OH)_2$ in ZnO thin films. In the zinc complex ($[Zn(NH_3)_4]^{2+}$) solution, excess ($[Zn(NH_3)_4]^{2+}$) absorbed in glass substrate transformed incompletely to ZnO and exist as $Zn(OH)_2$ phase in thin films. In films deposited at low temperature, rinsing procedure is applied to improve excess $Zn(OH)_2$ and obtain smoother transparent thin films.

• 대한간호학회지
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• 제38권5호
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• pp.667-675
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• 2008

Purpose: The aim of this study was to compare the relation between differently measured sports activities (metabolic equivalent [MET] and peak strain score) and distal radius bone mineral density in college-aged women. Methods: lifetime sports activity was scored in two different ways: 1) a sports activity score by multiplying the intensity (METs) and duration and 2) a sports activity score by adding up physical strain scores based on the ground reaction force of each sports activities. Bone mineral density was measured using dual energy x-ray densitometry (DTX-200) in the distal radius site. Results: In stepwise multiple regression analysis, body weight and sports activities during the college period were significant positive predictors for distal radius bone mineral density. The explained variance of sports activity measured with a peak strain score (8.8%) for distal radius bone mineral density was higher than one measured with the MET score (3.3%). Conclusion: It can be concluded that sports activity scores based on MET and peak strain scores during college are very important for determining the bone mineral density in the distal radius site in women under 30.

• Bulletin of the Korean Chemical Society
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• 제35권5호
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• pp.1460-1464
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• 2014

The substituent effects on the pyridinolysis (XC5H4N) of Y-aryl ethyl chlorophosphates are investigated in acetonitrile at $35.0^{\circ}C$. The two strong ${\pi}$-acceptor substituents, X = 4-Ac and 4-CN in the X-pyridines, exhibit large positive deviations from the Hammett plots but little positive deviations from the Br$\ddot{o}$nsted plots. The substituent Y effects on the rates are really significant and the Hammett plots for substituent Y variations in the substrates invariably change from biphasic concave downwards via isokinetic at X = H to biphasic concave upwards with a break point at Y = 3-Me as the pyridine becomes less basic. These are interpreted to indicate a mechanistic change at the break point from a stepwise mechanism with a rate-limiting bond formation (${\rho}_{XY}$ = -6.26) for Y = (4-MeO, 4-Me, 3-Me) to with a rate-limiting leaving group expulsion from the intermediate (${\rho}_{XY}$ = +5.47) for Y = (4-Me, H, 3-MeO). The exceptionally large magnitudes of ${\rho}_{XY}$ values imply frontside nucleophilic attack transition state.