• Bulletin of the Korean Chemical Society
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• 제2권3호
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• pp.86-89
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• 1981

The rate of the bromine-exchange reaction between gallium bromide and n-propyl bromide in 1,2,4-trichlorobenzene and in nitrobenzene was measured at 19, 25 and $40^{\circ}C$, using n-propyl bromide labelled with Br-82. The results indicated that the exchange reaction was second order with respect to gallium bromide and first order with respect to n-propyl bromide. The third-order rate constant determined at $19^{\circ}C$ is $2.9{\times} 10^{-2}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in 1,2,4-trichlorobenzene and $4.5{\times}10^{-3}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$. in nitrobenzene. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined. Reaction mechanism for the bromine exchange of n-propyl bromide seemed to be similar to those observed in earlier studies with other alkyl bromides.

• Bulletin of the Korean Chemical Society
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• 제19권6호
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• pp.676-680
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• 1998

The relaxation process of photogenerated carriers was investigated using conductivity measurement on ZnO under He, $H_2,\; CO_2\; and\; O_2$. The process was well explained with the rate constant of reaction or recombination of hole and electron, $k_h \;and\; k_e ( k_h > k_e)$, respectively. Generally, $k_h$ increased with the pressure of the gases. The slope of $k_h$ with respect to the pressure increased in the order of $H_2{\le}He, while $k_h$ of $O_2$ was sensitive to the history of the sample. The relaxation process on ZnO which was exposed to oxygen at 298 K and 573 K was observed during the illumination at 298 K and it was found that the rate constant of hole decreased with illumination time. From the result, it was suggested that the rate constant of photogenerated excess carriers was affected by the surface barrier of the semiconductor.

• 폴리머
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• 제26권4호
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• pp.422-430
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• 2002

Antimony trioxide 촉매를 사용하여 241 - $260^{\circ}C$ 범위에서 bishydroxyethyl naphthalate (BHEN)의 축중합 반응에 관한 속도론적 연구를 수행하였다. 반응은 회분식 반응기에서 진행되었고 반응물의 농도는 high performance liquid chromatography (HPLC)를 사용하여 측정하였다. 분자종 모델을 적용하여 구한 반응속도상수의 정반응 및 역반응 활성화 에너지 값은 각각 19.7과 31.4 kcal/mole 이었으며, 평형상수는 1.4-2.0으로 PET 축중합 반응의 경우보다 큰 값을 가지며 온도에 따라 어느 정도 변하였다. 말단기인 hydroxyethyl기의 반응속도는 분자의 크기에 관계없이 일정함을 Flory, 모델식으로부터 확인할 수 있었다. 관능기 모델을 적용한 결과 정반응과 역반응 활성화 에너지 길기 큰 차이가 없었으며, 평형상수는 1.4정도의 값을 가졌다. 관능기 모델로부터 구한 속도상수 값은 분자종 모델로부터 구한 값의 3-4배로서 두 모델이 모두 반응계를 잘 설명하였다. 제안된 분자종 모델이 10개의 분자종을 모두 예측해야 하는 어려움에도 불구하고 실험 결과와 잘 맞음을 알 수 있었다.

• 유기물자원화
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• 제23권1호
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• pp.23-28
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• 2015

본 연구는 회분식 실험을 통해 수거 형태에 따른 음식물류 폐기물의 혐기성 분해 특성을 평가하였다. 일반 종량제 봉투 내 음식물류 폐기물 (sample A)의 경우 최종 메탄 수율은 $285.6mL\;CH_4/g$ volatile solids (VS)로 가장 낮게 나타났으며 반응 속도는 $0.215d^{-1}$로 가장 높게 나타났다. RFID 기반의 폐기물 용기 내 음식물류 폐기물 (sample C)의 최종 메탄 수율 $493.4mL\;CH_4/g$ VS로 가장 높게 나타났으며 반응 속도는 $0.162d^{-1}$로 가장 낮게 나타났다. 모든 시료의 율속 단계 결정 계수는 양수로 나타나 메탄 생성 단계가 율속 단계인 것으로 나타났다.

• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1579-1582
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• 2009

The reaction rates of 4-X-2,6-dinitrochlorobenzenes (X = $NO_2,\;CN,\;CF_3$) with Y-substituted pyridines (Y = 3-$OCH_3,\;H,\;3-CH_3,\;4-CH_3$) in methanol-acetonitrile mixtures were measured by conductometry at 25 ${^{\circ}C}$. It was observed that the rate constant increased in the order of X = 4-$NO_2\;>\;4-CN\;>\;4-CF_3$ and the rate constant also increased in the order of Y = 4-$CH_3\;>\;3-CH_3\;>\;H\;>\;3-OCH_3$. When the solvent composition was varied, the rate constant increased in order of MeCN > 50% MeOH > MeOH. The electrophilic catalysis by methanol may be ascribed to the formation of hydrogen bonds between alcoholic hydrogen and nitrogen of pyridines in ground state. Based on the transition parameters, ${\rho}_S,\;{\rho}_N,\;{\beta}_Y,\;{\rho}_{XY}$ and solvent effects, the reaction seems to proceed via $S_N$Ar-Ad.E mechanism. We also estimated the isokinetic solvent mixtures (${\rho}_{XY}$ = 0) based on cross-interaction constants, where the substituent effects of the substrate and nucleophile are compensated.

• 공업화학
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• 제10권6호
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• pp.885-888
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• 1999

본 연구에서는 $Na_2B_4O_7{\cdot}10H_2O/Na_2B_4O_7{\cdot}5H_2O$ 반응계의 열분해 탈수반응에 의한 반응속도상수를 결정하고 반응계의 재현성 및 화학축열재의 반복사용에 따른 내구성을 검토하였다. 반응계의 열분해 탈수반응의 차수는 1차이었고, 열분해 탈수 반응속도는 수증기의 분압차에 정비례하였다. 반응계의 반응속도상수는 약 0.27이었고, 반응속도상수와 반응차수에 대한 반응의 재현성이 우수하였다. 또한 화학축열재의 내구성은 연속적으로 반복 사용하여도 활성변화는 ${\pm}5%$ 범위 내에 있었다.

• Bulletin of the Korean Chemical Society
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• 제31권10호
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• pp.2877-2883
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• 2010

The folding kinetics of $WT^*$ ubiquitin variant with valine to alanine mutation at sequence position 26 (HubWA) was studied by stopped-flow fluorescence spectroscopy. While unfolding kinetics showed a single exponential phase, refolding reaction showed three exponential phases. The semi-logarithmic plot of urea concentration vs. rate constant for the first phase showed v-shape pattern while the second phase showed v-shape with roll-over effect at low urea concentration. The rate constant and the amplitude of the third phase were constant throughout the urea concentrations, suggesting that this phase represents parallel process due to the configurational isomerization. Interestingly, the first and second phases appeared to be coupled since the amplitude of the second phase increased at the expense of the amplitude of the first phase in increasing urea concentrations. This observation together with the roll-over effect in the second folding phase indicates the presence of intermediate state during the folding reaction of HubWA. Quantitative analysis of Hub-WA folding kinetics indicated that this intermediate state is on the folding pathway. Folding kinetics measurement of a mutant HubWA with hydrophobic core residue mutation, Val to Ala at residue position 17, suggested that the intermediate state has significant amount of native interactions, supporting the interpretation that the intermediate is on the folding pathway. It is considered that HubWA is a useful model protein to study the contribution of residues to protein folding process using folding kinetics measurements in conjunction with protein engineering.

• 한국표면공학회지
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• 제18권1호
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• pp.5-11
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• 1985

Titanium was deposited onto AISI-430 stainless steel by chemical vapor deposition from $TiI_4\;and\;H_2$ gas mixture. Effects of temperature, flow rate of the gas, and $TiI_4$ partial pressure on the deposition rate were thoroughly investigated. The deposition rate of Ti was found to be constant at the given temperature and was increased with increasing temperature. The rate is controlled by surface reaction at the flow rate of gas higher than 500 ml/min, whereas at the flow rate lower than that by diffusional process. It is also interesting to note that the reaction mechanism changes at 1050$^{\circ}C$, at temperatures lower than 1050$^{\circ}C$ the activation energy is 56.9 Kcal/mol, whilst at temperatures higher than that is 8.3 Kcal/mol.

• 대한화학회지
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• 제10권2호
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• pp.76-90
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• 1966

Ammonium sulfate synthesized by the air oxidation methods without catalyst using the reaction vessel which was fitted with fritted glass at the bottom of it and introducing, through the bottom, ammonia and air with constant flow rates to sulfurous acid solution of constant concentrations at the given temperatures. The experiment showed that the oxidation process was accelerated in accord with the increase of the air flow rates when the ammonia flow rate was constantly kept at ca. 100ml/min. in high temperatures. When the pH of the solution reached 9.0, the oxidation was nearly completed. It is assumed that in the process of reaction, $[O_{2}{\to}HSO_{3}^-]^{\neq}$ would be produced as an activated complex and the reaction was thought to be first order. The experiment indicated that the 0.5M sulfurous solution could be oxidized up to 98.54% at the flow rates of ammonia and air, 100ml/min., and 4l/min., respectively at $50^{\circ}C$.

• 한국물환경학회지
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• 제20권5호
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• pp.488-493
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• 2004

The effects were examined from several conditions of $TiO_2$ photocatalysis reaction to phenols degradation by changing it's reacting conditions such as phenol concentration, pH, $TiO_2$ concentration, $H_2O_2$ concentration, flow rate, and intensity of ultraviolet rays. Phenol degradation was more efficient in low concentration of phenol, neutral pH. Phenol degradation appeared to increase as concentration of $TiO_2$ photocatalyst, that of $H_2O_2$ and intensity of ultraviolet rays increased. As $TiO_2$ dosage increased, initial rate constant k linearly increased. When $H_2O_2$ was injected more than optimum, phenol removal rate didn't increase in proportional to the change of $H_2O_2$ concentration as OH radicals was being consumed. When flow rate is less than $4.75m^3/m^2$ day, phenol removal efficiency appeared to decrease as ultraviolet rays transmission rate becomes low by $TiO_2$ suspension coated in photo reaction column. Meanwhile, initial rate constant according to light intensity change in less than $25mW/cm^2$ appeared to be in proportion to light intensity ($mW/cm^2$) Removal efficiency decreased about 12% after 180 minutes of reaction time while showed stable removal efficiency of 100% after 300 minutes when using regenerated $TiO_2$.