• Title/Summary/Keyword: Equilibrium Shift

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The Phase-Shift Method for the Langmuir Adsorption Isotherms of Electroadsorbed Hydrogens for the Cathodic H2 Evolution Reactions at the Poly-Pt Electrode Interfaces (다결정 Pt 전극계면에서 음극 H2 발생반응을 위한 전착된 수소의 Langmuir 흡착등온식에 관한 위상이동 방법)

  • Chun, Jang H.;Jeon, Sang K.;Lee, Jae H.
    • Journal of the Korean Electrochemical Society
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    • v.5 no.3
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    • pp.131-142
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    • 2002
  • The Langmuir adsorption isotherms of the under-potentially deposited hydrogen (UPD H) and the over-potentially deposited hydrogen (OPD H) at the poly-Pt/0.5M $H_2SO_4$ and 0.5 M LiOH aqueous electrolyte interfaces have been studied using cyclic voltammetric and ac impedance techniques. The behavior of the phase shift $(0^{\circ}{\leq}{-\phi}{\leq}90^{\circ})$ for the optimum intermediate frequency corresponds well to that of the fractional surface coverage $(1{\geq}{\theta}{\geq}0)$ at the interfaces. The phase-shift method, i.e., the phase-shift profile $({-\phi}\;vs.\;E)$ for the optimum intermediate frequency, can be used as a new electrochemical method to determine the Langmuir adsorption isotherms $({\theta}\;vs.\;E)$ of the UPD H and the OPD H for the cathodic $H_2$ evolution reactions at the interfaces. At the poly-Pt/0.5M $H_2SO_4$ aqueous electrolyte interface, the equilibrium constant (K) and the standard free energy $({\Delta}G_{ads})$ of the OPD H are $2.1\times10^{-4}$ and 21.0kJ/mol, respectively. At the poly-Pt/0.5M LiOH aqueous electrolyte interface, K transits from 2.7(UPD H) to $6.2\times10^{-6}$ (OPD H) depending on the cathode potential (E) and vice versa. Similarly, ${\Delta}G_{ads}$ transits from -2.5kJ/mol (UPD H) to 29.7kJ/mol (OPD H) depending on I and vice versa. The transition of K and ${\Delta}G_{ads}$ is attributed to the two distinct adsorption sites of the UPD H and the OPD H on the poly-Pt surface. The UPD H and the OPD H on the poly-Pt surface are the independent processes depending on the H adsorption sites themselves rather than the sequential processes for the cathodic $H_2$ evolution reactions. The criterion of the UPD H and the OPD H is the H adsorption sites and processes rather than the $H_2$ evolution reactions and potentials. The poly-Pt wire electrode is more efficient and useful than the Pt(100) disc electrode for the cathodic $H_2$ evolution reactions in the aqueous electrolytes. The phase-shift method is well complementary to the thermodynamic method rather than conflicting.

Determination of Adsorption Isotherms of Hydrogen at an Ir Electrode Interface Using the Phase-Shift Method and Correlation Constants (Ir 전극 계면에서 위상이동 방법 및 상관계수를 이용한 수소의 흡착동온식 결정)

  • Jeon, Sang-K.
    • Journal of the Korean Electrochemical Society
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    • v.10 no.2
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    • pp.132-140
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    • 2007
  • The phase-shift method and correlation constants for studying a linear relationship between the behavior ($-{\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and that (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}\theta{\geq}0$) have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) at noble metal/aqueous electrolyte interfaces. At an Ir/0.1 M KOH aqueous electrolyte interface, the Langmuir and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=3.3{\times}10^{-4}\;mol^{-1}$ for the Langmuir and $K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}$ for the Temkin adsorption isotherm), interaction parameter (g = 4.6 for the Temkin adsorption isotherm), and standard free energies (${\Delta}G_{ads}^0=19.9kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-4}\;mol^{-1}$ and $16.5<{\Delta}G_{\theta}^0<23.3\;kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}\;and\;0.2<\theta<0.8$) of H for the cathodic $H_2$ evolution reaction are determined using the phase-shift method and correlation constants. The inhomogeneous and lateral interaction effects on the adsorption of H are negligible. At the intermediate values of ${\theta},\;i.e,\;0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms (${\theta}\;vs.\;E$) and related electrode kinetic and thermodynamic parameters(K, g, ${\Delta}G_{ads}^0, {\Delta}G_{\theta}^0$).

The role of $Na^+-Ca^{2+}$ exchange on calcium activated chloride current in single isolated cardiac myocyte in pulmonary vein of rabbit.

  • Kim, Won-Tae;Lee, Yoon-Jin;Ha, Jeong-Mi;Han Choe;Jang, Yeon-Jin;Park, Chun-Sik;Lee, Chae-Hun m
    • Proceedings of the Korean Biophysical Society Conference
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    • 2003.06a
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    • pp.37-37
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    • 2003
  • We have shown the $Ca^{2+}$-activated chloride current is present in cardiac myocyte in rabbit pulmonary vein (Kim et al., 2002). This current amplitude was increased as [N $a^{+}$]$_{i}$ was increased and we suggested this chloride current may be involve in the spontaneous action potential frequency change. Since this current is activated by the increase of intracellular $Ca^{2+}$, we would like to test what is the inducer of the increase of [C $a^{2+}$]$_{i}$ between a L-type $Ca^{2+}$-current or a reverse mode of N $a^{+}$-C $a^{2+}$ exchange current. White rabbit (1.5 kg) was used and anesthetized with Ketamin (100 mg/kg). Pulmonary vein (PV) was isolated and sleeve area between left atrium and PV was dissected. Using collagenase (Worthington 0.7 mg/cc), single cardiac myocytes were isolated. In the presence of 15 mM of N $a^{+}$, three steps of voltage pulses were applied (holding potential : -40 ㎷, -80 ㎷ for 50 msec, 30 ㎷ for 5 msec, 10 ㎷ steps from -70 ㎷ to 60 ㎷). The inward and outward tail current was activated after brief 5 msec prepulse. The outward tail current was blocked by the removal of extracellular chloride substituted by glucuronic acid or by a chloride channel blocker, 5 mM 9-AC. But the inward tail current was still remained even though the amplitude was decreased. The reversal potentials were changed to the direction of the change of chloride equilibrium potential ( $E_{Cl}$ ) but the shift of equilibrium potential was not enough to match to the theoretical equilibrium potential shift. In the presence of L-type $Ca^{2+}$ channel blocker, nifedipine 1 uM, inward tail currents were greatly reduced but the outward current tail currents were still remained. In the presence of N $a^{+}$-C $a^{2+}$ exchange current blocker, 10 uM KB-R7943, the inward and outward tail currents were blocked almost completely. We tried to test the $Ca^{2+}$sensitivity of the chloride current with various [C $a^{2+}$]$_{i}$ in pipette solution from 100 nM to 1 uM but we failed to activate $Ca^{2+}$-activated chloride currents even though the cell became contracted in the presence of 1 uM $Ca^{2+}$. From these results, we could conclude that the increase of [C $a^{2+}$]$_{i}$ to activate the outward $Ca^{2+}$-activated chloride current was mainly induced by the activation of the reverse mode of N $a^{+}$-C $a^{2+}$ exchanger, But for the increase of [C $a^{2+}$]$_{i}$ to activate the inward tail current, L-type $Ca^{2+}$ current may be the major provoking current. Since the cytosolic increase of [C $a^{2+}$]$_{i}$ through pipette solution have failed to activate $Ca^{2+}$-activated chloride current, this chloride current may have very low $Ca^{2+}$ sensitivity or a comparmental increase $Ca^{2+}$ such as in subsarcolemmal space may activate the chloride current. Since there are several reports and models that the increase of $Ca^{2+}$ in subsarcolemmal space would be over several to tens of uM, both possibility may be valid together.uM, both possibility may be valid together.

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Analyzing Residential Land Use Change and Population Density Considering Climate Change Using Land Use Equilibrium Model in Jeju (토지이용균형모델을 이용한 기후변화에 따른 제주도 지역의 주거용 토지이용변화와 인구 밀도 예측)

  • YOO, So-Min;LEE, Woo-Kyun;Yamagata, Yoshiki;Lim, Chul-Hee;SONG, Chol-Ho;CHOI, Hyun-Ah
    • Journal of the Korean Association of Geographic Information Studies
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    • v.18 no.4
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    • pp.43-58
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    • 2015
  • The greenhouse gas emission caused by rapid economic growth and population is increasing in Korea. Also, climate change from greenhouse gases emission is accelerated. IPCC(Intergovernmental Panel on Climate Change) report projects an increase of greenhouse gas emissions by 90% from the year 2000 to 2030(SRES, 2000). Within this context, establishing countermeasures on climate adaptation and mitigation is becoming increasingly important to reduce the negative effect of climate change at a global level. Along with global efforts to tackle climate change, Korean government has incorporated 'Low Carbon Green Growth'strategies into its national policy agenda. Local governments have also conducted a number of studies to devise plans for environmentally friendly and sustainable city development. In this paper, the land-use equilibrium model, which reflects economic and geographical characteristics, is used to analyze the change in residential land use and population density. The target area for study is Jeju island in Korea. With an application of land use equilibrium model, it derived three types of scenarios of the land use change: (1) dispersion scenario-reflecting present-day conditions (2) adaptation scenario-applying adaptation measures to climate change and (3) combined scenario-integrating both adaptation and mitigation measures in model to climate change. By applying dispersion to combined scenario, the general trend shows a downward shift in population density. Subsequently, energy consumption and expected cost associated with casualties were calculated on the basis of the findings of respective scenario. The results show a descending trend in energy consumption and expected casualtie. Therefore, understanding for residential land use and population density of each scenario that analyzed land use equilibrium model in the study is expected to devise a environmental city plan for climate change stabilization and climate adaptation and mitigation.

The Thermodynamics of the Formation of Pyridine-Halogen and Interhalogens Charge Transfer Complexes (피리딘과 할로겐 또는 할로겐간 화합물 사이의 전하이동 착물생성에 관한 열역학적 연구)

  • Oh Cheun Kwun;Jin Burm Kyong;Kee Joon Choi
    • Journal of the Korean Chemical Society
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    • v.26 no.6
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    • pp.363-368
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    • 1982
  • Ultraviolet spectrophotometric investigations were carried out on the systems of pyridine with iodine, iodine monobromide and iodine monochloride in carbon tetrachloride. The results reveal the formation of the one to one molecular complexes of the type, $C_5H_5N{\cdot}I_2$, $ C_5H_5$N{\cdot}IBr and $ C_5H_5N{\cdot}ICl$. Considering ${\lambda}_max$ according to the formation of charge transfer complexes has the blue shift with the increasing temperatures$25, 40, 60^{\circ}C$ the equilibrium constants K and molar absorptivities $\varepsilon$ of complexes were obtained. From these values, the thermodynamic parameters ${\Delta}H$, ${\Delta}G$ and ${\Delta}S$ for the formation of the above charge transfer complexes were obtained. These results indicate that the relative stabilities of iodine, iodine monobromide and iodine monochloride complexes with pyridine increase in the order, $ C_5H_5N{\cdot}I_2$ < $ C_5H_5N{\cdot}IBr$ <$ C_5H_5N{\cdot}ICl$. This may be a measure of relative acidity of halogen and interhalogen toward pyridine and can be explained by the polarizabilities of electron acceptors and the difference of electronegativities of halogen atoms.

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Development Process of Agriculture And Technology -A Case Study of Korea

  • Gajendra-Singh;Ahn, Duck-Hyun
    • Proceedings of the Korean Society for Agricultural Machinery Conference
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    • 1993.10a
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    • pp.109-118
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    • 1993
  • Development process of agricultural technology has been studied with a case study of Korean agriculture. Technological is considered as a transformer of inputs into outputs and hence technological appropriateness, an important aspect of agricultural development strategies, is considered as a dynamic concepts. Considering the concept of agricultural system as a delivery system for providing essential materials and services to producers and consumers, it has been divided into two major groups of dimensions vis. external challenge dimensions and internal response dimensions. Market, investment and agro-ecosystem constitute the external challenge dimensions : whereas trade , technology as well as production and resources allocation constitute internal response dimensions. The system manager is responsible for maintaining equilibrium in the mentioned six sub-systems. Two kinds of alternatives paths of technological development viz. land saving technology and labour saving technolog have been studied. Technology is considered as a combination of four basic components viz. facilities, abilities, facts and frameworks. Adoption of innovation in agriculture depends on profitability, awareness, risk aversion, financial capacity, institutional infrastructure, availability of physical inputs and adaptability to the local conditions. For a cast study of Korea, changes in the agricultural system through external challenge dimensions are investigated. The impacts of industrialization on agro-ecosystem reported are shift of labour from the agricultural sector to non-agricultural sectors and continuously increasing demand of farm the agricultural sector to non-agricultural sectors accompanied by increase in land prices. The impacts on the commodity market discussed are shift in demand from rice, barley and other cereals to meat , dairy products and vegetables : and increasing in supply capacity of agricultural inputs. The process of agricultural development from 1962 to 19 1 9 (i.e. from start of the first to the end of the sixth five year plan) are also discussed in details with several policy measures taken. The trend of agricultural income and productivity are also analyzed. The main cause of increase in the agricultural income is considered as increase in labour productivity. The study revealed that during the span of 1965-88, holding size has not changed significantly, but both the land and labour productivity increased and so did the agricultural income. R&D activities in Korea have changed over time in three stages vix. import of improved technology, localization by adaptive research and technological mastery. For the new technology to be made affordable to farmers, policy measures like fertilizer and food grain exchange system, dual price system in rice and barely and loan for machinery were strengthened.

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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 Thermodynamics of the Formation of Polymethylbenzene-Halogens Charge Transfer Complexes (Ⅱ) (폴리메틸벤젠과 할로겐 사이의 전하이동착물 생성에 관한 열역학적 연구 (제2보))

  • Oh Cheun Kwun;Jeong Rim Kim
    • Journal of the Korean Chemical Society
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    • v.25 no.2
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    • pp.75-84
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    • 1981
  • Ultraviolet spectrophotometric investigations have been carried out on the systems of mesitylene with iodine, bromine, iodine monochloride and iodine monobromide in carbon tetrachloride. The results reveal the formation of the charge transfer complexes of the type, $C_6H_3(CH_3)_3{\cdot}X_2$ or $C_6H_3(CH_3)_3{\cdot}IX$ (X denotes halogen atoms). The equilibrium constants were obtained in consideration of that absorption maxima due to the formation of the charge transfer complexes shift to blue with the increasing temperatures. 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 mesitylene 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 mesitylene, which is explaned 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 < Toluene < Xylene < Mesitylene Thus, analysis of these findings is discussed.

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Effects of pH and Temperature on the Adsorption of Cationic Dyes from Aqueous Suspension by Maghnia Montmorillonite (수용액으로부터 양이온 염료 흡수에 대한 pH 및 온도 효과)

  • Elaziouti, A.;Laouedj, N.
    • Journal of the Korean Chemical Society
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    • v.55 no.2
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    • pp.208-217
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    • 2011
  • The effects of pH and temperature on the removal of two dyes (neutral red; NR and malachite green oxalates; MG) from aqueous effluents using Maghnia montmorillonite clay in a batch adsorption process were investigated. The results showed the stability of the optical properties of MG in aqueous solution and adsorbed onto clay under wide range of pH 3-9. However, the interaction of NR dye with clay is accompanied by a red shift of the main absorption bands of monomer cations under pH range of 3-5, whereas, those of neutral form remains nearly constant over the pH range of 8-12. The optimal pH for favorable adsorption of the dyes, i.e. ${\geq}$90% has been achieved in aqueous solutions at 6 and 7 for NR and VM respectively. The most suitable adsorption temperatures were 298 and 318 K with maximum adsorption capacities of 465.13mg/g for NR and 459.89 mg/g for MG. The adsorption equilibrium results for both dyes follow Langmuir, Freundlich isotherms. The numerical values of the mean free energy $E_a$ of 4.472-5.559 kj/mol and 2.000-2.886 kj/mol for NR and MG respectively indicated physical adsorption. Various thermodynamic parameters, such as ${\Delta}H^{\circ}$, ${\Delta}S^{\circ}$, ${\Delta}G^{\circ}$ and Ea have been calculated. The data showed that the adsorption process is spontaneous and endothermic. The sticking probability model was further used to assess the potential feasibility of the clay mineral as an alternative adsorbent for organic ion pollutants in aqueous solution.

FTIR and M ssbauer Spectroscopic Studies on the Hydrothermal Epidote from the Bobae Clay Deposit, Pusan, Korea (보배광산에서 산출하는 열수변질 기원 녹염석의 분광학적 특성: 적외선 및 뫼스바우어 연구)

  • 추창오;김수진
    • Journal of the Mineralogical Society of Korea
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    • v.9 no.2
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    • pp.55-63
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    • 1996
  • Epidote occurs as veinlets in the propylitic alteration zone of the Bobae clay deposit, Pusan, Korea. Its cell parameters apparently decrease with the contents of Al, Fe, and Ca. Fourier transform infrared (FTIR) spectra show one hydrosyl environment related to AlM2 at 3357-3358 cm-1. In the mid-infrared region, the peaks at 950 and 1030 cm-1 sharper with increasing Al shifting to higher energy region. The peak at 885 cm-1 shifts slightly to a lower energy region with a decreasing intensity as the Fe content increases. In the far-IR region, epidote exhibits absorption bands at 120 and 140 cm-1, which are related to the Ca-O bonds in A-sites.M ssbauer spectra of epidote show that the isomer shifts of Fe3+ range from 0.36-0.37 at the M3 site and from 0.35-0.44 at M1 site. Fe2+ shows the isomer shift ranging from 1.11 to 1.13. Quadrupole splitting is 2.04 for Fe3+M3, 0.52-0.70 for Fe3+M1, and 2.61-2.70 for Fe2+M3. Calculation shows Fe3+M386-90.7%, Fe3+M12.5-3.6%, and Fe2+M35.8-11.4% of total iron, showing preferential distribution of Fe3+ in the M3 site. The Fe3+M3 content is between 0.486 and 0.513 per formula unit. in the Fe-rich epidote, less Fe3+ and more Fe2+ are accommodated in the M1 and M3 sites. Hence, the overall disorder increases as total Fe content increase. The ordering parameter of the Bobae epidote is 0.93-0.95, suggesting a disequilibrium state below 200$^{\circ}C$. The constant temperature over a long period may be essential for the transition from disordered state to equilibrium state, despite the possible variation in flux and composition of the hydrothermal fluid.

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