• 제목/요약/키워드: chemical equilibrium

검색결과 1,136건 처리시간 0.023초

Determination of Adsorption Isotherms of Hydrogen on Zirconium in Sulfuric Acid Solution Using the Phase-Shift Method and Correlation Constants

  • Chun, Jang-H.;Chun, Jin-Y.
    • 전기화학회지
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    • 제12권1호
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    • pp.26-33
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    • 2009
  • The phase-shift method and correlation constants, i.e., the unique electrochemical impedance spectroscopy (EIS) techniques for studying the linear relationship between the behavior ($-{\varphi}$ vs. E) of the phase shift ($90^{\circ}{\geq}-{\varphi}{\geq}0^{\circ}$) for the optimum intermediate frequency and that ($\theta$ vs. E) of the fractional surface coverage ($0{\leq}{\theta}{\leq}1$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at noble metal (alloy)/aqueous solution interfaces. At a Zr/0.2 M ${H_2}{SO_4}$ aqueous solution interface, the Frumkin and Temkin adsorption isotherms ($\theta$ vs. E), equilibrium constants (K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ for the Frumkin and K = $1.401{\times}10^{-16}\exp(8.1{\theta})mol^{-1}$ for the Temkin adsorption isotherm), interaction parameters (g = 3.5 for the Frumkin and g = 8.1 for the Temkin adsorption isotherm), rates of change of the standard free energy (r = $8.7\;kJ\;mol^{-1}$ for g = 3.5 and r = $20\;kJ\;mol^{-1}$ for g = 8.1) of H with $\theta$, and standard free energies ($96.13{\leq}{\Delta}G^0_{\theta}{\leq}104.8\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ and $0{\leq}{\theta}{\leq}1$ and ($94.44<{\Delta}G^0_{\theta}<106.5\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-16}\exp(-8.1{\theta})mol^{-1}$ and $0.2<{\theta}<0.8$) of H are determined using the phase-shift method and correlation constants. At 0.2 < $\theta$ < 0.8, the Temkin adsorption isotherm correlating with the Frumkin adsorption isotherm, and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are probably the most accurate, useful, and effective ways to determine the adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at highly corrosion-resistant metal/aqueous solution interfaces.

방사선을 이용한 전기 활성 PAAc/PVA/PEG 하이드로겔 소프트 액추에이터의 제조 및 구동 특성 분석 (Synthesis of Electroactive PAAc/PVA/PEG Hydrogel Soft Actuator by Radiation Processing and Their Dynamic Characteristics)

  • 신예린;김소연
    • 공업화학
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    • 제30권6호
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    • pp.698-706
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    • 2019
  • 지난 수십 년 동안, 외부 자극에 대한 응답성이 우수하면서도 인체에 적용할 수 있는 소프트 액추에이터 개발을 위한 많은 노력이 이어졌다. 본 연구에서는 동역학적 정밀 제어가 가능한 의료용 소프트 액추에이터를 개발하기 위해, 유해한 화학적 첨가제나 개시제 없이 방사선을 이용하여 전기 자극 반응성과 물리적 특성이 우수한 3차원 가교 구조의 poly(acrylic acid) (PAAc)/poly(vinyl alcohol) (PVA)/poly(ethylene glycol) (PEG) 하이드로겔을 합성하였다. 방사선 조사 후, 모든 하이드로겔은 75% 이상의 겔 분율을 나타내었고, 표면 반사 적외선 분광법을 통해 PAAc/PVA/PEG 하이드로겔이 성공적으로 합성되었음을 확인하였다. 또한 PAAc/PVA/PEG 하이드로겔의 겔 분율, 평형 수분 함량, 압축 강도를 측정하여 감마선의 총 조사 선량과 구성 성분의 함량비 조절에 따른 하이드로겔의 물리적 특성 변화를 확인하였다. 조사된 감마선의 선량이 증가하거나 poly(ethylene glycol) diacrylate (PEGDA)의 함량이 많을수록 PAAc/PVA/PEG 하이드로겔은 높은 가교 밀도와 우수한 기계적 강도를 나타내었다. 또한 PAAc/PVA/PEG 하이드로겔은 3 V의 저전압에서도 전기적인 자극에 반응하였고, 전기장 하에서 이동성 이온의 움직임에 따른 하이드로겔의 밴딩 거동은 하이드로겔의 가교 밀도, 이온기의 함량, 인가 전압 및 전해질 용액의 이온 농도 등을 조절함으로써 제어할 수 있음을 확인하였다.

Ammonia Volatilization from Rice Paddy Soils Fertilized with 15N-Urea Under Elevated CO2 and Temperature

  • Lim, Sang-Sun;Kwak, Jin-Hyeob;Lee, Dong-Suk;Lee, Sun-Il;Park, Hyun-Jung;Kim, Han-Yong;Nam, Hong-Shik;Cho, Kyeong-Min;Choi, Woo-Jung
    • 한국환경농학회지
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    • 제28권3호
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    • pp.233-237
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    • 2009
  • It has widely been observed that the effect of elevating atmospheric $CO_2$ concentrations on rice productivity depends largely on soil N availabilities. However, the responses of ammonia volatilization from flooded paddy soil that is an important pathway of N loss and thus affecting fertilizer N availability to concomitant increases in atmospheric $CO_2$ and temperature has rarely been studied. In this paper, we first report the interactive effect of elevated $CO_2$ and temperature on ammonia volatilization from rice paddy soils applied with urea. Urea labeled with $^{15}N$ was used to quantitatively estimate the contribution of applied urea-N to total ammonia volatilization. This study was conducted using Temperature Gradient Chambers (TGCs) with two $CO_2$ levels [ambient $CO_2$ (AC), 383 ppmv and elevated $CO_2$ (EC), 645 ppmv] as whole-plot treatment (main treatment) and two temperature levels [ambient temperature (AT), $25.7^{\circ}C$ and elevated temperature (ET), $27.8^{\circ}C$] as split-plot treatments (sub-treatment) with triplicates. Elevated temperature increased ammonia volatilization probably due to a shift of chemical equilibrium toward $NH_3$ production via enhanced hydrolysis of urea to $NH_3$ of which rate is dependent on temperature. Meanwhile, elevated $CO_2$ decreased ammonia volatilization and that could be attributed to increased rhizosphere biomass that assimilates $NH_4^+$ otherwise being lost via volatilization. Such opposite effects of elevated temperature and $CO_2$ resulted in the accumulated amount of ammonia volatilization in the order of ACET>ACAT>ECET>ECAT. The pattern of ammonia volatilization from applied urea-$^{15}N$ as affected by treatments was very similar to that of total ammonia volatilization. Our results suggest that elevated $CO_2$ has the potential to decrease ammonia volatilization from paddy soils applied with urea, but the effect could partially be offset when air temperature rises concomitantly.

모사된 석탄가스화 합성가스를 이용한 La0.9Sr0.1Cr0.7B0.3O3±δ (B=Mn, Ni, Fe, Ru)의 수성가스전이반응 활성 및 특성에 관한 연구 (The Study on the Catalytic Performance and Characterization of La0.9Sr0.1Cr0.7B0.3O3±δ (B=Mn, Ni, Fe, Ru) for High Temperature Water-gas Shift Reaction with Simuated Coal-derived Syngas)

  • 이슬기;곽재훈;손정민
    • 한국수소및신에너지학회논문집
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    • 제24권6호
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    • pp.543-549
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    • 2013
  • In this study, $La_{0.9}Sr_{0.1}Cr_{0.7}M_{0.3}O_{3{\pm}{\delta}}$ (M=Mn, Ru, Fe, Ni) were prepared by sol-gel method and water gas shift reaction with simulated coal-derived syngas between $400{\sim}650^{\circ}C$ was conducted to evaluate the catalytic activity of prepared catalysts. Physico-chemical properties were characterized by XRD, BET, SEM-EDS and TPR. The formation of perovskite crystallite, $LaCrO_3$ was confirmed and the highest surface area was measured with $La_{0.9}Sr_{0.1}Cr_{0.7}Mn_{0.3}O_{3{\pm}{\delta}}$. Equilibrium conversion of CO above $550^{\circ}C$ was achieved except $La_{0.9}Sr_{0.1}Cr_{0.7}Fe_{0.3}O_{3{\pm}{\delta}}$. and methanation reaction was carried out as side reaction of water gas shift reaction with $La_{0.9}Sr_{0.1}Cr_{0.7}Ni_{0.3}O_{3{\pm}{\delta}}$ and $La_{0.9}Sr_{0.1}Cr_{0.7}Ru_{0.3}O_{3{\pm}{\delta}}$. Conclusively, $La_{0.9}Sr_{0.1}Cr_{0.7}M_n{0.3}O_{3{\pm}{\delta}}$ was the most suitable catalyst of water gas shift reaction above $500^{\circ}C$ for CO conversion and hydrogen production.

황산용액(黃酸溶液)으로부터 DOWEX G-26에 의한 구리의 회수(回收) (Ion Exchange of Copper from Sulphate Effluent using DOWEX G-26)

  • ;이재천;;김민석;정진기;황택성
    • 자원리싸이클링
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    • 제17권4호
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    • pp.37-46
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    • 2008
  • 본 연구는 전자산업으로부터 발생하는 CMP 폐수와 유사한 $0.3{\sim}0.5mg/ml$ 구리를 함유한 조제 황산 용액으로부터 DOWEX G-26 양이온 교환 수지를 사용한 구리 회수 공정 개발에 관한 것이다. 함구리 황산 용액으로부터 구리를 회수하기 위해 용액의 pH, 수지의 사용량, 용액의 산 농도, 용액과 수지의 접촉시간 등을 변수로 다양한 조건에서의 회수 실험을 실시하였다. 평형 pH 2.5, 용액/수지의 비 100mL/g 조건에서 14분의 접촉으로 99.99%의 구리가 흡착되었다. 구리의 흡착은 Langmuir isotherm을 따랐으며, 반응치수는 2차였다. 흡착된 구리는 묽은 황산에 의해 수지로부터 효과적으로 용리되었으며, 이로부터 농축용액을 만들 수 있었다.

티타늄 산화물과 유화물의 전지 전압을 결정하는 요소에 대한 제일원리계산 (First Principles Study on Factors Determining Battery Voltages of TiS2 and TiO2)

  • 김희진;문원진;김영민;배경서;윤재식;이영미;국진선;김양수
    • 한국표면공학회지
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    • 제42권1호
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    • pp.8-12
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    • 2009
  • Electronic structures and chemical bonding of Li-intercalated $LiTiS_2$ and $LiTiO_2$ were investigated by using discrete variational $X{\alpha}$ method as a first-principles molecular-orbital method. ${\alpha}-NaFeO_2$ structure is the equilibrium structure for $LiCoO_2$, which is widely used as a commercial cathode material for lithium secondary battery. The study especially focused on the charge state of Li ions and the magnitude of covalency around Li ions. The average voltage of lithium intercalation was calculated using pseudopotential method and the average intercalation voltage of $LiTiO_2$ was higher than that of $LiTiS_2$. It can be explained by the differences in Mulliken charge of lithium and the bond overlap population between the intercalated Li ions and anions in $LiTiO_2$ as well as $LiTiS_2$. The Mulliken charge, which means the ionicity of Li atom, was approximately 0.12 in $LiTiS_2$ and the bond overlap population (BOP) indicating the covalency between Ti and S was about 0.339. One the other hands, the Mulliken charge of lithium was about 0.79, which means that Li is fully ionized. The BOP, the covalency between Ti and O, was 0.181 in $LiTiO_2$. Because of high ionicity of Li and the weak covalency between Ti and the nearest anion, $LiTiO_2$ has a higher intercalation voltage than that of $LiTiS_2$.

세 개의 히드록실기를 가진 양이온 계면활성제 합성 및 계면 특성에 관한 연구 (Synthesis and Characterization of Interfacial Properties of a Cationic Surfactant Having Three Hydroxyl Groups)

  • 이병민;김지현;김승수;임종주
    • 공업화학
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    • 제23권5호
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    • pp.433-439
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    • 2012
  • 본 연구에서는 도데실 글리시딜 에테르와 아미노에탄올을 반응시킨 후 디메틸 설페이트로 4급화시켜 분자 내에 2개의 라우릴기, 3개의 히드록실기를 가진 양이온 계면활성제 BHMAS (N,N-bis-(3'-n-dodecyloxy-2'-hydroxypropyl)-N-methyl-2-hydroxyethylammonium methyl sulfate)를 합성하였고, 생성물의 분자구조는 $^{1}H-NMR$, FT-IR 등의 기기분석을 통하여 확인하였다. 합성한 계면활성제의 CMC (critical micelle concentration)는 $9.12\;{\times}\;10^{-4}$ mol/L이며, CMC에서의 표면장력은 28.71 mN/m이었다. Maximum bubble pressure tensiometer를 사용하여 동적 표면장력을 측정한 결과, 공기와 수용액의 계면이 계면활성제 단분자에 의하여 포화되는 데 비교적 오랜 시간이 소요되었다. 1 wt% 계면활성제 수용액과 n-decane 사이의 계면장력은 0.045 mN/m이며, 평형에 도달하는 데 약 5 min의 시간이 소요되었다. 합성된 계면활성제의 흡착 특성이 매우 우수하였으며, 합성한 양이온 계면활성제가 섬유표면에 효과적으로 흡착되어 유연효과를 나타낼 수 있음을 확인하였다.

Silver nanowires and nanodendrites synthesized by plasma discharge in solution for the catalytic oxygen reduction in alkaline media

  • 김회근;송면규;김동우;이상율
    • 한국표면공학회:학술대회논문집
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    • 한국표면공학회 2018년도 춘계학술대회 논문집
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    • pp.62-62
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    • 2018
  • Pt is still considered as one of the most active electrocatalysts for ORR in alkaline fuel cells. However, the high cost and scarcity of Pt hamper the widespread commercialization of fuel cells. As a strong candidate for the replacement of Pt catalyst, silver (Ag) has been extensively studied due to its high activity, abundance, and low cost. Ag is more stable than Pt in the pH range of 8~14 as the equilibrium potential of Ag/Ag+ being ${\approx}200mV$ higher than that of Pt/PtO. However, Ag is the overall catalytic activity of Ag for oxygen reduction reaction(ORR) is still not comparable to Pt catalyst since the surface Ag atoms are approximately 10 times less active than Pt atoms. Therefore, further enhancement in the ORR activity of Ag catalysts is necessary to be competitive with current cutting-edge Pt-based catalysts. We demonstrate the architectural design of Ag catalysts, synthesized using plasma discharge in liquid phase, for enhanced ORR kinetics in alkaline media. An attractive feature of this work is that the plasma status controlled via electric-field could form the Ag nanowires or dendrites without any chemical agents. The plasma reactor was made of a Teflon vessel with an inner diameter of 80 mm and a height of 80 mm, where a pair of tungsten(W) electrodes with a diameter of 2 mm was placed horizontally. The stock solutions were made by dissolving the 5-mM AgNO3 in DI water. For the synthesis of Agnanowires, the electricfield of 3.6kVcm-1 in a 200-ml AgNO3 aqueous solution was applied across the electrodes using a bipolar pulsed power supply(Kurita, Seisakusyo Co. Ltd). The repetition rate and pulse width were fixed at 30kHz and 2.0 us, respectively. The plasma discharge was carried out for a fixed reaction time of 60 min. In case of Ag nanodendrites, the electric field of 32kVcm-1 in a 200-ml AgNO3 aqueous solution was applied and other conditions were identical to the plasma discharge in water in terms of electrode configuration, repetition rate and discharge time. Using SEM and STEM, morphology of Ag nanowires and dendrites were investigated. With 3.6 kV/cm, Ag nanowire was obtained, while Ag dendrite was constructed with 32 kV/cm. The average diameter and legth of Ag nanowireses were 50 nm and 3.5 um, and thoes values of Ag dendrites were 40 nm and 3.0 um. As a results of XPS analysis, the surface defects in the Ag nanowires facilitated O2 incorporation into the surface region via the interaction between the oxygen and the electron cloud of the adjacent Ag atoms. The catalytic activity of Ag for oxygen reduction reaction(ORR) showed that the catalytic ORR activity of Ag nanowires are much better than Ag nanodendrites, and electron transfer number of Ag nanowires is similar to that of Pt (${\approx}4$).

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경북 옥산지역 열수동광상의 성인연구 (Genetic Environments of Hydrothermal Copper Deposits in Ogsan Mineralized Area, Gyeongsangbukdo Province)

  • 최선규;최상훈;윤성택;이재호;소칠섭
    • 자원환경지질
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    • 제25권3호
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    • pp.233-243
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    • 1992
  • 옥산지역에 위치하는 황학동광상은 초기백악기 퇴적암류내에 발달한 열극을 충진한 열수맥상 광상으로, 구조운동에 수반되어 3회에 걸쳐 생성된 석영 및 방해석맥으로 구성된다. 주된 금속광물로는 황철석, 자류철석, 황동석, 섬아연석, 방연석, 적철석 및 Ag-, Pb-, Bi-sulfosalts로, 이들의 침전은 주로 광화 제 1 기의 0.5~7.6 wt.% NaCl 상당염농도를 갖는 광화유체로부터 $370^{\circ}C$ 에서 약 $200^{\circ}C$ 에 걸쳐 진행되었으며, 광화 작용시의 압력은 <180 bar, 섬도는 700~2,400 m 였다. 광상내에서 보여주는 광물공생관계에 의한 열역학적 고찰과 유체포유물 및 안정동위원소 연구결과 등으로 미루어 본 광상광화유체내 Cu는 주로 chloride complex 상으로 이동되었으며, 주로 광화유체의 냉각작용과 이에 의한 지화학적 환경요인들($fs_2$, $fo_2$, pH)의 변화에 기인하여 침전되었음을 알수 있다. 유황안정동위원소 연구결과, 주광화시기인 광화1기중 광화유체의 ${\delta}^{34}S_{H_2S}$ 값이 초기 8.2‰ 에서 후기 4.7‰ 로 점차 감소함은 광화유체의 비등에 수반되어 수소이온농도와 함께 산소분압이 점진적으로 증가한 결과로 해석되며, 광화유체의 수소 및 산소동위원소 값으로부터 열수계에서 천수가 지배적인 역할을 하였음을 알수 있다.

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유연포장재료(柔軟包裝材料)를 이용(利用)한 고추 포장(包裝)에 관(關)한 연구(硏究) (Studies on Packaging of Chillies (Capsicum annum) in Flexible Films, and Their Laminates)

  • 장규섭;김재욱
    • Applied Biological Chemistry
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    • 제19권3호
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    • pp.145-154
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    • 1976
  • 현재(現在) 식품공업(食品工業)에 널리 이용(利用)되고 있는 포장재료(包裝材料)를 가지고 건조(乾燥)통고추와 고추분말(紛末)을 포장(包裝)하여 여러 조건(條件)에 저장(貯藏)하면서 포장재료(包裝材料)와 시료(試料)의 물리적(物理的) 및 화학적(化學的) 변화(變化)에 관(關)하여 연구검토(硏究檢討) 한바 다음과 같은 결과(結果)를 얻었다. 고추의 저장조건중(貯藏條件中), 상대습도(相對濕度) 55% 이상(以上)에서는 수분흡수(水分吸收)가 현저(顯著)하게 상승(上昇)하였으며, 10%에서는 곰장이가 발생(發生)하였는데 이때의 평형수분(平衡水分) 함량(含量)은 15%로써 고추의 저장수분(貯藏水分) 함량(含量)의 임계점(臨界點)에 도달(到達)하였다. 시료(試料)의 수분함량(水分含量)을 달리하여 저장(貯藏)하였을 때 색소(色素) Capsanthin함량(含量)은 저장온도(貯藏溫度)가 높을수록, 수분함량(水分含量)이 많아질수록 감소(減少)하였으며, 천일하(天日下)에 방치(放置)할때도 Capsanthin함량(含量)은 크게 변화(變化)하였다. 여러 포장재료중(包裝材料中) Aluminium foil packet이 장기저장시(長期貯藏時) 고추 성분(成分)의 변화(變化)를 줄이는데 가장 효과적(效果的)이였으며 단기저장시(短期貯藏時)에는 착색(着色) Polyethylene, L.D.P.E., Saran/cello, /Saran/P.E., 순서(順序)였다.

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