The Electromotive Force and Thermodynamic Properties of the Cell at High Pressure

지종기,정종재,황정의,Jee Jong-Gi,Jung Jong-Jae,Hwang Jung-Ui Korean Chemical Society 1974 대한화학회지 Vol.18 No.5

종래의 방법으로 고압하에서 전지의 표준기전력 $(E^{\circ})$를 산출하는 것은 불가능하다. 그러나 완전평형상수의 개념을 종래의 Nernst 방정식에 적용하므로서 고압하에서 표준기전력을 구할 수 있게 되었다(완전 Nernst방정식). 더욱이 다른 열역학적 성질 이를테면 수화수의 순변화(k), 용매의 압축을(${\beta}$), 전지반응에서 종래의 해리상수(K) 평형상태에서 표준자유에너지변화(${\Delta}G^{\circ}$) 표준엔탈피변화(${\Delta}H^{\circ}$) 및 표준엔트로피변화($S^{\circ}$) 등을 얻었다. 본 실험에서는 전지의 기전력(E)을 $20{\sim}35^{\circ}C$와 1∼2500 atms 범위에서 측정하였다. 일정한 온도에서 전지의 기전력은 압력이 증가함에 따라 증가하였으며, 일정한 압력에서 온도가 증가함에 따라 역시 증가하였다. 전지반응의 수화수의 순변화(k)는 $20^{\circ}C$에서 41.96으로서 압력에 따라 변하지 않고 일정한 값을 유지하였으나 한편 K와 ${\Delta}S^{\circ}C$는 압력에 따라 증가하였으나 ${\Delta}G^{\circ}$와 ${\Delta}H^{\circ}$는 감소하였다. 고압하에서도 완전 Nernst방정식으로부터 표준기전력을 계산할 수 있으므로 상압에서와 마찬가지로 화학평형론을 취급할 수 있게 되었다 It is unable to derive the standard emf ($E^{\circ}$) of the cell at high pressure from the conventional method. However, when the concept of the complete equilibrium constant($K{\circ})$) is available to the conventional Nernst equation, it is possible to get the standard emf of the cell at high pressure(complete Nernst equation). Moreover, the other thermodynamic properties, such as the net change of solvation number(k), the compressibility of solvent(${\beta}$), ionization constant(K), the standard free energy change(${\Delta}G^{\circ}$), the standard enthalpy change(${\Delta}H^{\circ}$) and the standard entropy change (${\Delta}S^{\circ}$) of the cell reaction at equilibrium state have been also obtained. In this experiment, the emf of the cell; 12.5 % Cd(Hg)│$CdSO_4(3.105{\times}10^{-3}M),\;Hg_2SO_4│Hg$ have bee measured at temperature from 20 to $35^{\circ}C$ and at pressures from 1 to 2500 atms. The emf of the cell increased with increasing pressure at constant temperature, and did with increasing temperature at constant pressure. The net change of solvation number(k) of the cell reaction was 41.96 at $25^{\circ}C$, and kept constant value with pressure, while, K and ${\Delta}S^{\circ}$ increased with pressure, but whereas ${\Delta}G^{\circ}$ and ${\Delta}H^{\circ}$ decreased. Since the standard emf of the cell at high pressure can be calculated from the complete Nernst equation, the theory of chemical equilibrium could be developed with at high pressure as well as at the atmosphere.

Dehydrogenation of Ethylalcohol Catalyzed by Alcoholdehydrogenase Under High Pressure

지종기,신진영,황정위,Jee Jong-Gi,Shin Jin-Young,Hwang Jung-Ui Korean Chemical Society 1989 Bulletin of the Korean Chemical Society Vol.10 No.1

A pressure effect of the dehydrogenation of ethylalcohol catalyzed by alcoholdehydrogenase was observed in Tris-HCl buffer, pH 8.8 from $25^{\circ}C$ to $35^{\circ}C$ under high pressure system by using our new theory. The theory makes it possible for us to obtain all rate and equilibrium constants for each step of all enzymatic reaction with a single intermediate. We had enthalpy and volume profiles of the dehydrogenation to suggest a detail and reasonable mechanism of the reaction. In these profiles, both enthalpy and entropy of the reaction are positive and their values decrease with enhancing pressure. It means that the first step is endothermic reaction, and its strength decrease with elevating pressure. At the same time, all activation entropies have large negative values, which prove that not only a ternary complex has a more ordered structure at transition state, but also water molecules make a iceberg close by the activated complex. In addition to this fact, the first and second step equilibrium states are controlled by enthalpy. The first step kinetic state is controlled by enthalpy but the second step kinetic state is controlled by entropy.

Transport of Some Solutes in Blood Plasma Through Poly(2-Hydroxyethyl Methacrylate) Hydrogel Membrane

지종기,전무식,이태규,Jee Jong Gi,Jhon Mu Shik,Ree Tai Kyue Korean Chemical Society 1978 대한화학회지 Vol.22 No.5

혈장내의 중요한 성분인 몇가지 염들이 poly(2-hydroxyethyl methacrylate) 격막을 통과하는 상대투과계수($U_{re}$), 분배계수($K_D$), 확산계수($D_m$)등을 측정하였다. 이 격막을 제조할 때 cross-linker로서 사용된 tetraethylene glycol dimethacrylate(TEGDMA)의 함량은 중량비로 2.8%였다. 이 염들의 확산계수는 그 분자량이 증가함에 따라서 지수함수적으로 감소하였으며, 그 분자의 원통반지름(a)에 대해서는 요소를 제외하고는 직선적으로 감소하였다. 이와 같은 사실을 sieve pore filow 모델로서 설명하였다. 여러 온도에서 요소의 $U_{re}$와 $D_m$은 글리신, ${\beta}$-알라닌, D-글루코오스, 사카로스 및 말레산과 같은 다른 염들의 값보다 더 컸다. 이와 같은 결과는 이 poly(HEMA) 격막이 혈투석 응용에 적합하다는 사실을 보여 주었다. The relative permeabilities, distribution coefficients and diffusion coefficient of some salts which are important components in blood plasma through a poly(HEMA) membrane were measured. The crosslinker which was used for preparing the membrane was tetraethylene glycol dimethacrylate(TEGDMA), the weight percentage of the latter was about 2.8. We found that the diffusion coefficients ($D_m$) of the solutes decrease exponentially with increasing molecular weight, and also that $D_m$'s decrease linearly (except urea) with cylindrical radius (a). These facts were explained by a sieve pore flow model. The relative permeability and diffusion coefficient of urea at various temperature were larger than those of other solutes such as glycine, ${\beta}$-alanine, D-glucose, saccharose and maleic acid. The result indicates that the poly(HEMA) membrane might be suitable for hemodialysis application.

진공증착법을 이용한 철프탈로시아닌 박막의 합성과 그 특성

지종기(Jong Gi Jee),이재구(Jae Gu Lee),황동욱(Dong Uk Hwang),임윤묵(Yoon Mook Lim),양현수(Hyun Soo Yang),류해일(Hai Il Ryu),박하선(Ha Sun Park) 한국공업화학회 1999 공업화학 Vol.10 No.5

N/A N/A

[화학] Tetra-n-Butyl Ammonium Chloride에 의한 알코올류의 상전이 반응에 대한 선택 특이성

지종기(Jong-Gi Jee),최원복(Won-Bok-Cboi),이광필(Kwang-pill Lee) 한국분석과학회 1995 분석과학 Vol.8 No.1

고압, 고온 유체의 물성연구. 메시틸렌과 요오드 사이의 전하이동착물에 대한 압력과 온도의 영향

권오천,지종기,김정림,Oh Cheun Kwun,Jong Gi Jee,Jeong Rim Kim 대한화학회 1980 대한화학회지 Vol.24 No.6

메시틸렌과 요오드 사이의 전하이동착물의 안정도에 미치는 압력과 온도의 영향을 n-헥산용액에서 자외선 분광광도법으로 연구하였다. 압력은 1에서 1600 bar, 온도는 25,40,$60^{\circ}C$ 사이에서 측정하였다. 착물의 평형상수는 압력 및 온도의 증가와 더불어 증가 및 감소하고 흡수계수는 대체로 증가함을 알았다. 이들 각 평형상수로부터 착물형성에 따른 부피, 엔탈피, 자유에너지 및 엔트로피 변화양을 구하였다. 또한 압력의 증가에 의한 red-shift, 온도의 증가에 의한 blue-shift 현상 및 압력변화에 의한 진동자 세기의 관계를 열역학적 함수와 관계지워 설명하였다. The effect of pressures and temperatures on the stabilities of the mesitylene-iodine charge transfer complex have been investigated through ultraviolet spectrophotometric measurements in n-hexane. The stabilities of complexes were measured at 25, 40 and $60^{\circ}C$ under 1∼1600 bars. The equilibrium constant of the complex was increased with pressure and decreased with temperature raising. The absorption coefficient was increased with both pressure and temperature. Changes of volume, enthalpy, free energy and entropy for the formation of complexes were obtained from the equilibrium constants. The red-shift observed a higher pressure, the blue-shift at a higher temperature and the relation between pressure and oscillator strength were discussed by means of thermodynamic functions.

The Pressure Effect of the Association of 2,4,6,N-Tetramethyl Pyridinium Iodide in Ethanol-Water Mixture

황정의,지종기,이영화,우의하,Jung-Ui Hwang,Jong-Gi Jee,Young-Hwa Lee,Uei-Ha Woo Korean Chemical Society 1984 대한화학회지 Vol.28 No.2

부피 퍼센트 95%의 에탄올-물 혼합용매내에서 2,4,6,N-테트라메틸 피리디늄요오드(TeMPI)의 이온회합 상수(K)를 수정한 자외선분광 및 전기 전도도 혼용법으로 온도범위 $25^{\circ}C{\sim} 50^{\circ}C$, 압력범위 1 ${\sim}$ 2,000 bars에서 결정하였다. K값은 압력이 증가함에 따라서 증가하였고 $40^{\circ}C$에서 최대값을 나타내었다. 부분몰부피변화(${\Delta}V$)는 비교적 작은 음의 값이었으며 ${\Delta}V$의 절대값은 $40^{\circ}C$에서 최소값을 보여주었다. TeMPI의 이온 크기 변수(a)는 $40^{\circ}C$에서 최대값을 가졌다. ${\Delta}H^{\circ}$값은 40, $25^{\circ}C$ 그리고 $50^{\circ}C$에서 각각 영, 음수 및 양수로 나타났으며 엔트로피(${\Delta}S^{\circ}$)와 자유에너지(${\Delta}G^{\circ}$)와 같은 다른 열역학변수 값도 계산하였다. 이와 같은 실험결과로부터 우리들은 TeMPI가 압력증가에 대하여 안정화되고, $40^{\circ}C$까지는 온도증가에 따라서도 안정화됨을 보여주었다. 그러나 $40^{circ}C$에서는 TeMPI 두 분자에 있는 8개 메틸기의 분자간 소수성 상호작용으로 인하여 약한 이량체를 형성하고 $50^{\circ}C$이상에서는 다시 열적으로 분해된다는 결론을 얻게 되었다. The ionic association constant(K) of 2,4,6, N-tetramethyl pyridinium iodide (TeMPI) in 95 volume percentage ethanol-water mixture were determined by a modified UV and conductance method at $25^{\circ}C$ to $50^{\circ}C$ under 1 to 2,000 bars. The K values increase with increasing pressure and have maximum value at $40^{\circ}C$. The partial molar volume hange (${\Delta}V$) has relatively small negative value and the absolute values of ${\Delta}$ are minimum at $40^{\circ}C$. The ion size parameter(a) of TeMPI have maximum value at $40^{\circ}C$. {\Delta}H^{\circ}$ values are zero, positive and negative at 40^{\circ}C$, $25^{\circ}C$ and $50^{\circ}C$ respectively. Other thermodynamic parameters such as the changes of standard entropy ({\Delta}S^{\circ}$) and free energy {\Delta}G^{\circ}$ were evaluated. From these experimental results, we came to conclusion that TeMPI is stabilized by the elevation of pressure and that of temperature below $40^{\circ}C$ but weakly dimerized at $40^{\circ}C$ because of the intermolecular hydrophobic interaction of eight methyl groups of two molecules. And it thermally decomposed above $50^{\circ}C$.

Kinetics for the Reaction of Benzyl Benzenesulfonate with Pyridine in Acetone Under High Pressure

황정의,여수동,지종기,Jung-Ui Hwang,Soo-Dong Yoh,Jong-Gi Jee Korean Chemical Society 1980 대한화학회지 Vol.24 No.2

Benzyl benzenesulfonate와 피리딘의 반응속도를 아세톤 용매중에서 20∼$40^{\circ}C$ 및 1∼2000 bars에서 전기전도도법으로 측정하였다. 반응속도는 온도 및 압력이 증가함에 따라 증가하였다. 이 반응의 활성화엔탈피$({\Delta}H^{\neq})$, 엔트로피$({\Delta}S^{\neq})$ 그리고 활성화부피$({\Delta}V^{\neq})$를 구하였다. 이 반응에서 압력변화에 대한 $({\Delta}H^{\neq})$와 $({\Delta}S^{\neq})$사이에 등속관계가 성립하였으며 등속온도는 $342^{\circ}K$였다. 이상의 결과로 본 반응은 전이상태에서 $C{\cdots}N$ 결합형성이 주로 반응속도를 결정하는 $S_N2$ 반응 메카니즘으로 진행된다는 것을 알았다. Kinetic studies of the reaction of benzyl benzenesulfonate with pyridine in acetone were carried out by the electric conductivity method under 1 to 2000 bars and at 20 to $40^{\circ}C$. The rate increases with increasing pressure and temperature. The activation enthalpy $({\Delta}H^{\neq}),\;entropy\;({\Delta}S^{\neq})$ and activation volume $({\Delta}V^{\neq})$ of the reaction are obtained by the above experiment. The isokinetic relationship between $({\Delta}H^{\neq})\;and\;({\Delta}S^{\neq})$ for pressure change in the reaction was shown, and its isokinetic temperature was $342^{\circ}K$. From all of the above results it was found that this reaction precedes on the $S_N2$ reaction mechanism in which the rate of the reaction was determined by $C{\cdots}N$ bond formation at transition state.

직교화된 Slater형 궤도함수를 이용한 Helium 원자의 Ab-initio Mo계산

池鍾基,李京姬,洪大一 慶北大學校 1988 論文集 Vol.45 No.-

Until now, the method of getting complete solution of Schro¨dinger wave equation without using mathematical approximation is only the case of hydrogen atom. Therefore, we got a solution of Schro¨dinger wave equation by introducing suitable approximate means in the case of all the atoms (or molecules) which have two-electron or more. Helium atom is the most important model of MO calculationn for two-electron system. In this study, Ab-initio MO calculation of the Helium atom of the first excited states is treated according to perturbation theory using orthogonalized Slater type orbitals. Eight wave equations of the first excited states of Helium atom were consisted of fourfolded degeneracy without perturbation theory. The perturbation calculation makes the degeneracy disappeared, to give an energy diagram of Helium atom at the first excited state.

고등학교 화학과 일반화학에서 반응속도에 대한 내용 및 실험의 비교 고찰

지종기,손영락 慶北大學校 師範大學 1990 敎育硏究誌 Vol.32 No.-

Chemical Kinetics is a field of chemistry connected with chemical rate and chemical reaction mechanism. Today the plants and chemical procession of many chemical factories are planned to produce things in large quantities fast and economically. Therefore the importance of this chemical kinetics, connected with chemical procession, goes on increasing. So this paper will be useful for the teaching methods of high school chemistry and general chemistry in university as comparing and analyzing the contents and experiments of chemical kinetics in newly revised high school chemistry textbooks, general chemistry in university, chem study, and American textbooks(chemistry ; the study of matter). The results are as follows. 1. Comparing the relative importance of chemical kinetics in newly revised high school chemistry textbooks, university general chemistry, chem study, and American chemistry textbook total pages of newly revised high school chemistry textbooks are simillar to the others but interesting pictures and problems are short and chemical equations are too much. So as far as economical cirumstances permit, colorful pictures and photos or examples of the newest high technology must be used to arose interest. 2. Comparing the contents of newly revised high school chemical textbooks, the quantity of contents and reaction mechanism are not the same. So the contents must be complemented and amendmented. 3. Taking into account of the importance of chemical industry and chemical kinetics in everyday life, the contents must be complemented with examples observed in real life and applied field in chemical industry to arose interest. 4. Reducing the difference of high school textbooks and general chemistry in university and putting the concepts for mathmatical thinking into high school textbooks, we must make consistent contents. 5. Experimental process must be complemented and amended to be a systemic experiment considering the connection with theory. 6. The experiments of chemical kinetics in a high school chemical process are much weaker than college chemistry. So the experiments of chemical kinetics must be richer and the experiment of determining reaction order must be complemented.