• Title/Summary/Keyword: Chemical Equilibrium

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Photo- and Sonic Degradation of Endosulfans(α, β, and sulfate) in Aqueous Solution (엔도설판류의 광 및 초음파분해)

  • Kwon, Sung Hyun;Kim, Jong Hyang;Cho, Daechul
    • Korean Chemical Engineering Research
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    • v.45 no.5
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    • pp.460-465
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    • 2007
  • Endosulfan-${\alpha}$ endosulfan-${\beta}$ and endosulfan-sulfate, which are classified as pesticides, were degraded by use of UV energy and ultrasonic irradiation. The degradation residuals were analysed by gas chromatography with an electron capture detector and TOC (total oragnic carbon) analysis. The reactions were conducted in a quartz annular reactor equipped with a low pressure mercury multilamp (8Wx2) and a sonic generator. All the aqueous solutions were concentrated as 10 mg/L initially. Endosulfans were degraded each to result in 48.2% (${\alpha}$), 50.0% (${\beta}$) and 76.5% (sulfate) of removal efficiency by UV energy, and 66.9% (${\alpha}$), 55.8% (${\beta}$) and 72.7% (sulfate) by ultrasonic irradiation, respectively. In contrast to the results of the single-component solutions, degradation of the endosulfan-sulfate was greatly suppressed to result in the lowest degradation rate and removal efficiency in the three-component solutions. This finding suggests that there should be a reversible reaction with a substantially low equilibrium constant between endosulfan-${\alpha}$ or -${\beta}$ and -sulfate in the coexistence of the three endosulfans. TOC data showed the endosulfans were decomposed by 20%~40% toward complete mineralization, producing a quantity of intermediates induced by the radical reactions. We found that all the decay reactions considered in this study nicely fell into pseudo first-order rate.

Stability Characteristics of Sn Species Behavior on Surface of a Sn-modified Pt Electrode for Electrolytic Reduction of Nitrate Ion (질산염 이온의 전해 환원을 위한 Sn-modified Pt 전극 표면에서의 Sn 안정성 거동 특성)

  • Kim, Kwang-Wook;Kim, Seong-Min;Kim, Yeon-Hwa;Lee, Eil-Hee;Jee, Kwang-Yong
    • Korean Chemical Engineering Research
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    • v.45 no.5
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    • pp.433-441
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    • 2007
  • This work investigated the stability of a Sn-modified Pt electrode, which was used for reduction of nitrate, fabricated by an adsorption or electro-deposition of Sn on Pt. In order to find the causes for instability of the electrode, the effects of the solutions in which the electrode was used and the potential applied to the electrode on the electrochemical and metallurgical behaviors of Sn on Pt were studied. The Sn of freshly- prepared modified-Sn Pt electrode existed as Sn hydroxide form, which brought about an easy loss of the electro-activity of the electrode even staying in water, especially in acid solution. When the Sn-modified Pt electrode was used for the reduction of nitrate, the electro-activity of the electrode was affected depending on the potential applied to the electrode. When a more negative potential than the redox equilibrium potential between $Sn(OH)_2$ and Sn was applied to the electrode, the Sn hydroxide was converted to Sn that could diffused into Pt, which leaded to the loss of electro-activity of the electrode as well. The solid diffusion of Sn increased linearly with the applied potential. The Sn-electrodeposited Pt electrode which had more Sn on the electrode was more favorable to maintaining the integrity of the electrode during the reduction of nitrate than the Sn-adsorbed Pt electrode prepared in the under-potential deposition way.

The Study on Complex of Gallium Bromide with Ethyl Bromide in Aniline and in o-Chloroaniline under High Vacuum (고진공 상태에서 아닐린과 o-클로로 아닐린 용액중 브롬화갈륨과 브롬화에탄과의 착물형성에 관한 연구)

  • Young Cheul Kim;Se Kyung Kim;Deog Ja Koo;Jong Wan Lim
    • Journal of the Korean Chemical Society
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    • v.35 no.5
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    • pp.480-486
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    • 1991
  • The solubilities of ethyl bromide in aniline and o-chloroaniline have been measured at 5, 15$^{\circ}$ and 25$^{\circ}$C in the presence and the absence of gallium bromide. When gallium bromide does not exist in the system, the solubility of ethyl bromide in o-chloroaniline is greater than in aniline, indicating a stronger interaction of ethyl bromide with o-chloroaniline than that with aniline. It could be thought that ethyl bromide forms unstable complex with gallium bromide in the presence of gallium bromide in the system. This complex has been assumed in various ways and evaluated, that instability constant (K value) is relatively constancy under the assumption of 1 : 1 complex, $C_2H_5Br{\cdot}GaBr_3$. Therefore, the complex forms the following equilibrium in the solution: $C_2H_5Br{\cdot}GaBr_3\;{\rightleftharpoons}\;C_2H_5Br +1/2Ga_2Br_6$ The instability of the complex of ethyl bromide with gallium bromide is compared with similar complexes of gallium bromide with methyl bromide. The changes of enthalpy, free energy and entropy fcor the dissociation of the complex are also calculated.

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Interactions between Hydrodenitrogenation of Pyridine and Hydrodeoxygenation of m-Cresol over sulfided CoMo/γ-Al2O3 Catalyst (황화 CoMo/γ-Al2O3 촉매상에서 수첨탈질반응과 수첨탈산소 반응의 상호작용)

  • Kim, Hak-Soo;Park, Hea-Kyung;Kim, Kyung-Lim
    • Applied Chemistry for Engineering
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    • v.2 no.2
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    • pp.108-118
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    • 1991
  • Interactions between pyridine hydrodenitrogenation (HDN) and m-cresol hydrodeoxygenation(HDO), and the kinetic analysis were studied over sulfided $CoMo/{\gamma}-Al_2O_3$ catalyst at the range of temperatures between 473 K and 723 K, the total pressures between $10{\times}10^5Pa$ and $50{\times}10^5Pa$, and the contact times between 0.0125 g-cat. hr/ml-feed and 0.03g-cat. hr/ml-feed. HDN of pyridine and HDO of m-cresol were inhibited by each other and the inhibition effect of HDO by pyridine is higher than that of HDN by m-cresol. But reactivity of m-cresol is higher than that of pyridine. The rate equations of pyridine and m-cresol were given to be ${\gamma}_{HDN}=k_{HDN}{\cdot}K_pC_p/(1+K_cC_c+K_pC_p)$ and ${\gamma}_{HDO}=k_{HDO}{\cdot}K_cC_c/(1+K_cC_c+K_pC_p)$ in terms of Langmuir-Hinshellwood-Hougen-Watson model. At each temperature, reaction rate constants and adsorption equilibrium constants were determined and activation energies of pyridine HDN and m-cresol HDO are 13.83kcal/mol, respectively and the heat of adsorption are -6.458 and -5.045kcal/mol, respectively.

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Geochemical Characteristics of Geothermal Water and Groundwater in the Dongrae Hot-Spring Area (동래온천지역의 지열수와 지하수의 지화학적 특성)

  • Suck Jong Han;Se-Yeong Hamm;Ig Hwan Sung;Byeong Dae Lee;Byong Wook Cho;Myong Hee Cho
    • The Journal of Engineering Geology
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    • v.9 no.3
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    • pp.207-225
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    • 1999
  • Twenty water samples (eleven groundwater and nine geothermal water samples) were collected to elucidate hydrogeochemical characteristics of the groundwater and geothermal water in the Dongrae hot-spring area and its vicinity. Major and minor elements were analyzed for ground and geothermal water samples. Physicochemical properties of the groundwater and the geothermal water were examined and chemical composition of the two waters were compared. Factor and correlation analyses were carried out to simplify the physicochemical data into grouping some factors and to find interaction between them. The groundwaters belong to $Ca-HCO_3$ type, while the geothermal waters belong to Na-Cl type. The Na and Cl concentrations in the Dongrae hot-spring area are higher than those of other granite areas in South Korea. The Na/Cl weight ratio ranges from 0.7 to 1.3 for the geothermal waters. On the phase stability diagram groundwaters fall effectively in the field of stability of kaolinite, while geothermal waters fall in the stability field of microcline or kolinite depending on the chemical composition system. Based on the Na-K, Na-K-Ca and Na-K-Ca-Mg geothermometers, the geothermal reservoir is estimated to have equilibrium temperature between 115 and $145^{\circ}C$.

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Treatment of Nickel Ions in Water Phase Using Biochar Prepared from Liriodendron tulipifera L. (백합나무 유래 biochar를 이용한 수중에서 니켈 이온의 처리)

  • Choi, Suk Soon;Choi, Jung Hoon;Kim, Seung-Soo
    • Applied Chemistry for Engineering
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    • v.28 no.5
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    • pp.529-533
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    • 2017
  • In this work, a new type of biosorbent was prepared from the biochar of Liriodendron tulipifera L. by adding an activation process using water vapor. By using the biosorbent, the removal characteristics of nikel ions in the water phase were investigated. When the equilibrium experiments to remove both 5 and 10 mg/L of nikel ions were performed, the adsorption amount of nickel ions was 4.2 and 5.4 mg/g, respectively. Also, the optimal initial pH was 6 to increase the removal efficiency with respect to two different nickel concentrations of 5 and 10 mg/L. To enhance the removal efficiency of 10 mg/L of nikel ions, a chemical treatment using critic acid was applied for the biosorbent. In addition, 100% removal efficiency was observed for 10 mg/L of nikel ions when the experiment was conducted for 2 h using the modified biosorbent treated by 4 M of critic acid. The results of desorption experiment to recover nikel ions indicated that 0.1 M of nitrilotriacetic acid (NTA) was selected as the optimal desorption agent. Consequently, these experimental results could be employed as an economical and environmentally friendly technology for the development of nickel removal processes.

Study on Adsorption Kinetic Characteristics of Propineb Pesticide on Activated Carbon (활성탄에 대한 프로피네브 농약의 흡착동력학적 특성 연구)

  • Lee, Jong-Jib;Cho, Jung-Ho;Kim, Heung-Tae
    • Clean Technology
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    • v.17 no.4
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    • pp.346-352
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    • 2011
  • The adsorption characteristics of propineb pesticide onto activated carbon has been investigated for the adsorption in aqueous solution with respect to initial concentration, contact time and temperature in batch experiment. The Langmuir and Freundlich adsorption models were applied to described the equilibrium isotherms and isotherm constants were also determined. The Freundlich model agrees with experimental data well. slope of isotherm line indicate that activated carbon could be employed as effective treatment for removal of propineb. The pseudo first order, pseudo second order kinetic models were use to describe the kinetic data and rate constants were evaluated. The adsorption process followed a pseudo second order model, and the adsorption rate constant($k_2$) decreased with increasing initial concentration of propineb. The activation energy, change of free energy, enthalpy, and entropy were also calculated to predict the nature adsorption. The estimated values for change of free energy were -7.28, -8.27 and -11.66 kJ/mol over activated carbon at 298, 308 and 318 K, respectively. The results indicated toward a spontaneous process. The positive value for change of enthalpy, 54.46 kJ/mol, found that the adsorption of propineb on activated carbon is an endothermic process.

The Thermodynamics of the Formation of Polymethylbenzene-Halogens Charge Transfer Complexes (III) (폴리메틸벤젠과 할로겐 사이의 전하이동착물 생성에 관한 열역학적 연구 (제3보))

  • Oh Cheun Kwun;Jin Burm Kyong;Jung Sung Kim
    • Journal of the Korean Chemical Society
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    • v.25 no.6
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    • pp.351-360
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    • 1981
  • Ultraviolet spectrophotometric investigations have been carried out on the system of durene with iodine, bromine, iodine monochloride and iodine monobromide in carbon tetrachloride. The results reveal the formation of the charge transfer complexes of the type, $C_6H_2(CH_3)_4{\cdot}X_2$ or $C_6H_2(CH_3)_4{\cdot}IX$(X denotes halogen atoms). The equilibrium constant were obtained in consideration of that absorption maxima due to the formation of the charge transfer complexes shift to blue with the increasing temperatures. The thermodynamic parameters, ${\Delta}H,\;{\Delta}G\;and\;{\Delta}S$ for the formation of the charge transfer complexes were calculated from these values. These results indicate that the relative stabilities of the durene complexes at each temperature decrease in the order, $ICl>IBr>I_2>Br_2$. This order may be a measure of their relative acidities toward durene, which is explained in terms of the relative polarizabilities of halogen molecules and the relative electronegativities of halogen atoms. These results combined with previous study of this series indicated that the relative stabilities of the polymethylbenzene complexes with iodine increase in the order; Benzene

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The Effects of Charge Transfer Complex on the Reaction of N,N-dimethylaniline and Iodine (N,N-Dimethylaniline과 Iodine간의 반응에 있어서 Charge Transfer Complex의 영향)

  • Oh-Yun Kwon;U-Hyon Paek;Eung-Ryul Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.191-196
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    • 1992
  • Reaction of N,N-dimethylaniline(N,N-DMA) and iodine in $CHCl_3,\;CH_2Cl_2 : CHCl_3$(1:1), $CH_2Cl_2$(1:1), and CH2Cl2 has been studied kinetically by using conductivity method. Pseudo first-order rate constants ($k_{obs}$) and second-order rate constants ($k_{obs}$/[N,N-DMA]) are dependent on the N,N-DMA concentration. Second-order rate constants obtained were decreased with increasing N,N-DMA concentration. We analysed these results on the basis of formation of charge transfer complex as a reaction intermediate. From the construction of reaction scheme and activation parameters for the formation and transformation of charge transfer complex. The equilibrium constants decreased when the dielectric constant of solvent was increased, and the value is 1.9${\sim}$4.2$M^{-1}$. The rate of transformation are markedly affected by the solvent polarity.${\Delta}H^{\neq}$ is 6.3-12.6kJ/mol, and ${\Delta}S^{\neq}$ is large negative value of -234J/mol K.

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Static Supercritical Fluid Extraction of PCBs from Soil Matrix (정적 초임계유체 방식에 의한 토양 중의 PCBs 추출)

  • Ryoo, Keon-Sang;Lee, Won-Kyoung;Hong, Yong-Pyo;Oh, In-Gyung;Kim, Yong-Gyun
    • Journal of the Korean Chemical Society
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    • v.47 no.6
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    • pp.578-584
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    • 2003
  • Polychlorinated biphenyls (PCBs) known as environmental contaminants in soil were analyzed by the soil pollution standard process test and the static supercritical $CO_2$ extraction mode. It was shown that the percent average recoveries of PCBs by the soil pollution standard process test were ranged in 25-35% and the corresponding standard deviations were above 10%. In contrast, the percent average recoveries of PCBs by the static supercritical $CO_2$ extraction mode were 2-2.5 times higher and standard deviations were within 7%. These results indicate that static supercritical $CO_2$ extraction mode may be a useful alternative to sample pretreatment certified by the soil pollution standard process test. The increasing supercritical $CO_2$ pressure from 1130 psi to 1996 psi at $40^{\circ}C$ enhanced the recovery of all PCB congeners from soil. However, at same Tc and Pc, the equilibrium time (5 versus 60 minutes) had no effect on the recovery of each PCB congener. Finally, similar PCB recoveries were obtained under the same extraction condition, regardless of the molecular weight and structure (coplanar versus non-coplanar) of PCB congeners.