• Title/Summary/Keyword: thermodynamic effect

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Studies on the Complexes of Lanthanide ion with Multidentate Ligand (I). Determination of Thermodynamic Parameters with Solution Calorimetric Method in Nonaqueous Solvents (란탄족 원소의 여러자리 리간드 착물에 관한 연구 (제 1 보) 물아닌 용액에서 용액열량계에 의한 열역학적 함수결정)

  • Sam-Woo Kang;Won-Hae Koo;Soo-Min Lee;Chang Choo-Hwan;Moo-Yol Seo
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.588-595
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    • 1989
  • Log K, ${\Delta}$H and ${\Delta}$S for the complexation of $La^{3+},\;Ce^{3+}$ and $Eu^{3+}$with various multidentate ligand containing crown ether, diaza crown ether and diamine ether have been determined in methanol and acetonitril solutions at $25^{\circ}C$ by solution calorimetric titration method. The greater stability constant of $La^{3+}$-15C5 than those of 18C6 diaza [2.2] in methanol are discussed in terms of the size of metal ion and the ligand cavity and of metal ion solvation. The stabilities of $Ce^{3+}$ and $La^{3+}$ ion complexes with a various multidentate ligand in acetonitril are in the order of (diamine ether)<18C6<15C5$Ce^{3+}$, $La^{3+}$ and $Eu^{3+}$-diaza [2.2] complexes in acetonitril are increased with the following order: $Eu^{3+}$ < $La^{3+}$ < $Ce^{3+}$, that is increasing order of the optimum size and of the charge density of metal ion.

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A Study on Natural Ventilation by the Caloric Values of HLW in the Deep Geological Repository (지하처분장내 고준위 방사성 폐기물 발열량에 따른 자연환기력 연구)

  • Roh, Jang-Hoon;Choi, Heui-Joo;Yu, Yeong-Seok;Yoon, Chan-Hoon;Kim, Jin
    • Tunnel and Underground Space
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    • v.21 no.6
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    • pp.518-525
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    • 2011
  • In this study, the natural ventilation pressure resulting from the large altitude difference which is a characteristic of high radioactive waste repository and the caloric value of the heat emitted by wastes was calculated and based on the results, natural ventilation quantities were calculated. A high radioactive waste repository can be considered as being operated through closed cycle thermodynamic processes similar to those of thermal engines. The heat produced by the heating of high radioactive wastes in the underground repository is added to the surrounding air, and the air goes up through the upcast vertical shaft due to the added heat while working on its surroundings. Part of the heat added by the work done by the air can be temporarily changed into mechanical energy to promote the air flow. Therefore, if a sustained and powerful heat source exists in the repository, the heat source will naturally enable continued cyclic flows of air. Based on this assumption, the quantity of natural ventilation made during the disposal of high radioactive wastes in a deep geological layer was mathematically calculated and based on the results, natural ventilation pressure of $74{\sim}183$Pa made by the stack effect was identified along with the resultant natural ventilation quantity of $92.5{\sim}147.7m^3/s$. The result of an analysis by CFD was $82{\sim}143m^3/s$ which was very similar to the results obtained by the mathematical method.

Effects of Temperature and n-Alcohols (Propanol, Butanol, Pentanol and Hexanol) on the Micellization of Cetyltrimethylammonium Bromide (Cetyltrimethylammonium Bromide의 미셀화 현상에 미치는 온도 효과 및 n-알코올(프로판올, 부탄올, 펜탄올 및 헥산올) 효과)

  • Lee, Byeong Hwan
    • Journal of the Korean Chemical Society
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    • v.38 no.8
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    • pp.539-546
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    • 1994
  • The critical micelle concentration(CMC) and the counterion binding $constant(\beta)$ at the CMC of cetyltrimethylammonium bromide(CTAB) in a series of aqueous solutions containing medium chain-length n-alcohols(Propanol, Butanol, Pentanol and Hexanol) have been determined from the concentration dependence of electrical conductance at serveral temperature from $17^{\circ}C\;to\;41^{\circ}C.$ Thermodynamic parameters $({\Delta}G^o_m,\;{\Delta}H^o_m,\;{\Delta}S^o_m,\;and\;{\Delta}C_p)$ associated with micelle formation of CTAB have been also estimated from the temperature dependence of CMC and $\beta$ values, and the significance of these parameters and their relation to the theory of micelle formation have been considered. The results show that an enthalpy-entropy compensation effect is usually observed for the micellization of CTAB. The effects of n-alcohols on the micellar properties (CMC and $\beta$) of CTAB solutions have been also investigated. The addition of n-alcohol to the CTAB solution in a small quantity decreases the CMC value and the counterion binding constant $(\beta)$ at the CMC, but the addition of n-alcohol in an excessive quantity increases the CMC values on the conterary. These results have been explained in terms of the effect of the micelle-solubilized alcohol on the micellar surface charge density.

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Studies on the Coordination of Acetamide to Rare Earth Metal Ion (Ln(II) (희토류 금속이온 (Ln(III))과 Acetamide 사이의 상호작용에 대한 연구)

  • Sang-Won Lee;Jeonga Yu;Chang-Ju Yoon;Yoo-Hyek Jun;Young-Sang Choi
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.205-211
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    • 1992
  • The $2{\nu}_{C=0}$ + amide III combination band spectrum of acetamide (AA) was obtained in very dilute solutions of AA+lanthanide shift reagents (LSR) in carbon tetrachloride over the range of $15^{\circ}$ to $45^{\circ}C$. It was found that only 1 : 1 AA-LSR complex is formed by the interaction between carbonyl oxygen of AA and central metal ion(Ln(Ⅲ)) in LSR. The thermodynamic parameters for Ln(III)${\cdot}$O=C bond were determined by computer analysis of concentration and temperature dependent spectra. ${\Delta}H^{\circ}$ for the coordination of AA to Eu$(dpm)_3$, Yb$(dpm)_3$, and Pr$(dpm)_3$ have been found to be -39.1, -28.4, and -25.5 kJ/mol, respectively. It has shown that this type of ion-dipole interaction is more than twice stronger compared to the dipole-dipole interaction in the amide linkage, and largely depending on the steric hindrence effect by the bulky dpm groups around central metal ion (Ln(III)) rather than the ionic potential effect of central metal ion itself.

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Effect of Critical Cooling Rate on the Formation of Intermetallic Phase During Rapid Solidification of FeNbHfBPC Alloy

  • Kim, Song-Yi;Oh, Hye-Ryeong;Lee, A-Young;Jang, Haneul;Lee, Seok-Jae;Kim, Hwi-Jun;Lee, Min-Ha
    • Journal of Korea Foundry Society
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    • v.41 no.3
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    • pp.235-240
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    • 2021
  • We present the effect of the critical cooling rate during rapid solidification on the nucleation of precipitates in an Fe75B13P5Nb2Hf1C4 (at.%) alloy. The thermophysical properties of the rapidly solidified Fe75B13P5Nb2Hf1C4 liquids, which were obtained at various cooling rates with various sizes of gas-atomized powder during a high-pressure inert gas-atomization process, were evaluated. The cooling rate of the small-particle powder (≤20 ㎛) was 8.4×105 K/s, which was 13.5 times faster than that of the large-particle powder (20 to 45 mm; 6.2×104 K/s) under an atomized temperature. A thermodynamic calculation model used to predict the nucleation of the precipitates was confirmed by the microstructural observation of MC-type carbide in the Fe75B13P5Nb2Hf1C4 alloy. The primary carbide phase was only formed in the large-particle gas-atomized powder obtained during solidification at a slow cooling rate compared to that of the small-particle powder.

Experimental Study on the Characteristics of Combustion in the Indirect Moxibustion with Ginger (격강구(隔薑灸)의 연소(燃燒) 특성(特性)에 관한 실험적(實驗的) 연구(硏究))

  • Lee, Geon-mok;Lee, Geon-hui;Moon, Sung-jae;Hwang, Byung-chun;Guk, Uo-suk;Jang, Ji-yeon;Kim, Yang-jung;Jang, Jae-ho;Yun, Ju-young
    • Journal of Acupuncture Research
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    • v.21 no.3
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    • pp.193-214
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    • 2004
  • Objective : The purpose of this study is to investigate the mechanism and effect of moxibustion with ginger objectively, to be used as the quantitative data through the measurement of temperature, and to grasp the thermodynamic characteristics of moxibustion with ginger. Methods : We have selected the indirect moxibustion with ginger among many indirect moxibustions. We produced a slice of ginger to a thickness of 3, 4, 5mm and the moxa cone having a diameter of 8mm, a height of 10mm for making a comparative study of characteristics of moxa cone according to change the density. We have made a comparative study of the thermodynamic characteristics of moxibustion with ginger with or without holes. We measured combustion times and calculated temperatures, temperature gradients in each period during a combustion of moxa. Results : 1. We found out it was not significantly influenced by the existence of the punched holes in a slice of ginger because the punched holes grow smaller immediately. 2. The duration of the preheating period became longer according to thickness of a slice of ginger and was not directly proportional to the density of moxa cone. The duration of the preheating period was extremely short when it burned a 100mg moxa cone. That was influenced by the density of moxa cone. 3. The duration of the heating period became longer according to thickness of a slice of ginger likewise the preheating period bacause the density of moxa cone had effected on the combustion characteristics. The duration of the heating period was extremely long when it burned a 100mg moxa cone. On the other hand the maximum temperature in the heating period was appeared that the combustion with a thin slice of ginger was highest and measured that the large density of moxa cone was higher. But the maximum temperature in the heating period was about $37.8^{\circ}C{\sim}44.2^{\circ}C$respectively lower in others. 4. The duration of the retaining period was some doubling shorter than that of the heating period that is concerned the shape of moxa cone. The temperature measured the close of a retaining period was $36.6^{\circ}C{\sim}41.8^{\circ}C$, that was considerably lower temperature. 5. The mean ascending temperature velocity and the mean descending temperature velocity were $0.042{\sim}0.073^{\circ}C/sec$, $-0.027{\sim}-0.064^{\circ}C/sec$ respectively. Then, the ascending temperature velocity was some faster than the ascending temperature velocity. Conclusions : The quantitative standard for obtaining the effective heating stimulation is that if the slice of ginger made a hole in it, we had to use the needle above 1.5mm diameter. The recommended size of a slice ginger is the 14mm diameter and the 2~3mm thickness. The moxa cone is formed the conical shape that the base diameter was 8mm, the height was 10mm, the density was $600mg/cm^2$.

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Effect of Nitrogen Impurity on Process Design of $CO_2$ Marine Geological Storage: Evaluation of Equation of State and Optimization of Binary Parameter (질소 불순물이 이산화탄소 해양 지중저장 공정설계에 미치는 영향 평가: 상태방정식의 비교 분석 및 이성분 매개변수 최적화)

  • Huh, Cheol;Kang, Seong-Gil
    • Journal of the Korean Society for Marine Environment & Energy
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    • v.12 no.3
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    • pp.217-226
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    • 2009
  • Marine geological storage of $CO_2$ is regarded as one of the most promising options to response climate change. Marine geological storage of $CO_2$ is to capture $CO_2$ from major point sources, to transport to the storage sites and to store $CO_2$ into the marine geological structure such as deep sea saline aquifer. Up to now, process design for this $CO_2$ marine geological storage has been carried out mainly on pure $CO_2$. Unfortunately the captured $CO_2$ mixture contains many impurities such as $N_2$, $O_2$, Ar, $H_2O$, $SO_x$, $H_2S$. A small amount of impurities can change the thermodynamic properties and then significantly affect the compression, purification and transport processes. In order to design a reliable $CO_2$ marine geological storage system, it is necessary to perform numerical process simulation using thermodynamic equation of state. The purpose of the present paper is to compare and analyse the relevant equations of state including PR, PRBM, RKS and SRK equation of state for $CO_2-N_2$ mixture. To evaluate the predictive accuracy of the equation of the state, we compared numerical calculation results with reference experimental data. In addition, optimum binary parameter to consider the interaction of $CO_2$ and $N_2$ molecules was suggested based on the mean absolute percent error. In conclusion, we suggest the most reliable equation of state and relevant binary parameter in designing the $CO_2-N_2$ mixture marine geological storage process.

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Thermodynamic Properties for the Chemical Reactions of [Cu(dl-trans-[14]-diene)]$^{2+}$ with S$_2O_3^{2-},\;SCN^-,\;I^-\;and\;NO_2^-$ ([Cu(dl-trans-[14]-diene)]$^{2+}$ 착이온과 음이온 (S$_2O_3^{2-},\;SCN^-,\;I^-$ 및 NO$_2^-$)간의 화학반응에 대한 열역학적 성질 (${\Delta}G;\;{\Delta}H;\;{\Delta}V$))

  • Yu Chul Park;Jong Chul Byun
    • Journal of the Korean Chemical Society
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    • v.29 no.3
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    • pp.239-246
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    • 1985
  • The equilibria of chemical reaction between [Cu(dl-trans-[14]-diene)]$^{2+}$ and L$^{n-}$(S$_2$O$_3^{2-}$, SCN$^-$, I$^-$, NO$_2^-$) ions were studied by the spectrophotometric method in the range of 15 to 35$^{\circ}C$ and 1 to 1500bar. The equilibrium constants(K) for L$^{n-}$ = S$_2$O$_3^{2-}$, SCN$^-$, I$^-$ and NO$_2^-$ ions at 25$^{\circ}C$ and 1500bar were 3.0, 1.9, 0.6 and 0.5, respectively. The values of K decreased with increasing pressure and temperature. From the temperature effect on equlibrium constant, the thermodynamic parameters(${\Delta}G^{\circ}$, ${\Delta}H^{\circ}$, ${\Delta}S^{\circ}$) of reaction were evaluated and the reactions of [Cu(dl-trans-[14]-diene)]2+ ion with S$_2$O$_3^{2-}$, SCN$^-$ and I$^-$ except NO$_2^-$ ion were exothermic. The volume changes of reaction(${\Delta}$V) had positive values for all the used anions. The values of ${\Delta}$V in cm$^3$/mole for S$_2$O$_3^{2-}$ ion at 1,500, 1,000 and 1,500bar were 26, 22, 19 and 16, and those for S$_2$O$_3^{2-}$, SCN$^-$, I$^-$ and NO$_2^-$ ions at atmospheric pressure 26, 30, 64 and 45, respectively. Bonding character between Cu(Ⅱ)-complex ion and L$^{n-}$ was discussed by comparing both the equlibrium constants experimentally determined and those calculated according to Fuoss's ion-pair equation in case of S$_2$O$_3^{2-}$ ion.

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A Study of Fluoride Adsorption in Aqueous Solution Using Iron Sludge based Adsorbent at Mine Drainage Treatment Facility (광산배수 정화시설 철 슬러지 기반 흡착제를 활용한 수용액상 불소 흡착에 관한 연구)

  • Lee, Joon Hak;Kim, Sun Joon
    • Economic and Environmental Geology
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    • v.54 no.6
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    • pp.709-716
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    • 2021
  • In this study, an adsorbent prepared by natural drying of iron hydroxide-based sludge collected from settling basin at a mine drainage treatment facility located in Gangneung, Gangwon-do was used to remove fluoride in an artificial fluoride solution and mine drainage, and the adsorption characteristics of the adsorbent were investigated. As a result of analyzing the chemical composition, mineralogical properties, and specific surface area of the adsorbent used in the experiment, iron oxide (Fe2O3) occupies 79.2 wt.% as the main constituent, and a peak related to calcite (CaCO3) in the crystal structure analysis was analyzed. It was also identified that an irregular surface and a specific surface area of 216.78 m2·g-1. In the indoor batch-type experiment, the effect of changes in reaction time, pH, initial fluoride concentration and temperature on the change in adsorption amount was analyzed. The adsorption of fluoride showed an adsorption amount of 3.85 mg·g-1 16 hours after the start of the reaction, and the increase rate of the adsorption amount gradually decreased. Also, as the pH increased, the amount of fluoride adsorption decreased, and in particular, the amount of fluoride adsorption decreased rapidly around pH 5.5, the point of zero charge at which the surface charge of the adsorbent changes. Meanwhile, the results of the isotherm adsorption experiment were applied to the Langmuir and Freundlich isotherm adsorption models to infer the fluoride adsorption mechanism of the used adsorbent. To understand the thermodynamic properties of the adsorbent using the Van't Hoff equation, thermodynamic constants 𝚫H° and 𝚫G° were calculated using the adsorption amount information obtained by increasing the temperature from 25℃ to 65℃ to determine the adsorption characteristics of the adsorbent. Finally, the adsorbent was applied to the mine drainage having a fluoride concentration of about 12.8 mg·L-1, and the fluoride removal rate was about 50%.

Effect of Reaction Gases on PFCs Treatment Using Arc Plasma Process (아크 플라즈마를 이용한 과불화합물 처리공정에서 반응가스에 의한 효과)

  • Park, Hyun-Woo;Choi, Sooseok;Park, Dong-Wha
    • Clean Technology
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    • v.19 no.2
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    • pp.113-120
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    • 2013
  • The treatment of chemically stable perflourocompounds (PFCs) requires a large amount of energy. An energy efficient arc plasma system has been developed to overcome such disadvantage. $CF_4$, $SF_6$ and $NF_3$ were injected into the plasma torch directly, and net plasma power was estimated from the measurement of thermal efficiency of the system. Effects of net plasma power, waste gas flow rate and additive gases on the destruction and removal efficiency (DRE) of PFCs were examined. The calculation of thermodynamic equilibrium composition was also conducted to compare with experimental results. The average thermal efficiency was ranged from 60 to 66% with increasing waste gas flow rate, while DRE of PFCs was decreased with increasing gas flow rate. On the other hand, DRE of each PFCs was increased with the increasing input power. Maximum DREs of $CF_4$, $SF_6$ and $NF_3$ were 4%, 15% and 90%, respectively, without reaction gas at the fixed input power and waste gas flow rate of 3 kW and 70 L/min. A rapid increase of DRE was found using hydrogen or oxygen additional gases. Hydrogen was more effective than oxygen to decompose PFCs and to control by-products. The major by-product in the arc plasma process with hydrogen was hydrofluoric acid that is easy to be removed by a wet scrubber. DREs of $CF_4$, $SF_6$ and $NF_3$ were 25%, 39% and 99%, respectively, using hydrogen additional gas at the waste gas flow rate of 100 L/min and the input power of 3 kW.