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.

메탄올-물 혼합용매내에서 3, 5, N-트리메틸피리디늄 요오드의 이온화합에 대한 압력 효과

지종기,이영화,이경희 慶北大學校 物理化學硏究所 1983 硏究論文集 Vol.4 No.-

95% 에탄올-물 혼합용매 내에서의 3. 4. N-트리메틸 피리디늄 요오드의 이온회합 상수(K)를 20˚, 30˚, 40˚, 50℃의 온도와, 1∼2000 bar의 압력범위에서 자외선 분광 및 전기전도도 혼용법에 의하여 구하였다. 이온회합 상수는 압력이 증가하고 온도가 감소함에 따라서 그 값이 커졌다. K값으로부터 총부피변화(ΔV)와 몇가지 열역학적인 변수들을 계산하였다. 아울러 전기적 수축부피변화(ΔV_el)와 내부부피변화(ΔV_in)값도 구하였다. ΔV, ΔV_el, ΔV_in은 각각, 음, 음, 양의 값을 가지고 이들의 절대치는 압력과 온도가 증가함에 따라 감소하였다. 이온크기(a)는 3 ∼ 6Å의 범위에서 압력과 온도에 따라 그 값이 변하며, 결합 신장 길이(Δl)는 약 1∼2Å의 값을 가졌다. 용매화 수( n )는 25℃에서는 약 2개 이었고 온도가 증가함에 따라 줄어 들어서 50℃에서는 약 0.5개 이었다. The association constants(K) of 3, 5, N-trimethyl pyridinium iodide in 95 volume percent ethanol-water mixed solvent were determined by a modified UV and conductance method at 25˚, 30℃, 40˚ and 50℃ over the pressure range 1 to 2000 bars. The association process is enhanced with increasing pressure and decreasing temperature. From K values, we obtained the total partial molar volume change (ΔV) and some thermodynamic parameters. The electrostriction volume (ΔV_el) and intrinsic volume (ΔV_in) were also evaluated. The values of ΔV, ΔV_el, ΔV_in are negative, negative and positive, respectively, and the absolute values of all these three decrease with increasing pressure and temperature. The ion-pair size(a) were varied 3 to 6Å with pressure and temperature and bond elongation distance(Δl) were about 1 to 2Å. The solvation number(n) decreased from 2 to 0.5 with increasing temperature.

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.

高壓下에서 電池 Pb(Hg)|PbX_2(m), AgX(s)|Ag(X=Cl, Br, I) 및 Hg|Hg_2Cl_2(s)KCl(m), AgCl(s)|Ag의 起電力과 그의 熱力學的 性質

黃正儀,池鍾基 慶北大學校 産業開發硏究所 1975 硏究報告 Vol.3 No.-

Appling the complete quilibrium constant to the electro-cell reaction, it was derived that the standard electromtive force of the cell at high pressure(1―2, 500 bars). This theory was briefly discussed and applied to some cells such as, Pb|PbX_2(m), AgX(s)|Ag(X=Cl, Br and I)and Hg|Hg_2Cl_2(s), KCl(m), AgCl(s)|Ag. The results were conterminous as the previous results which applied to some other cells i.e. the electromotive force of the cells were increased as the pressure and temperaure increase except the PbCl_2 cell. The net change of the hydration number of the cell reaction were 26.1 for PbCl_2, 23.5 for PbBr_2 and 26.9 for PbI_2 cell, respectively. From the k-values the standard electromotive force and some other related thermodynamic values were calculated.

에탄올-물 혼합용매내에서 2,4,6,N-Tetramethyl Pyridinium Iodide의 회합에 대한 압력효과

黃正儀,池鍾基,李永華,禹義夏 慶北大學校 物理化學硏究所 1984 硏究論文集 Vol.5 No.-

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∼50℃, 압력범위 1∼2,000bars에서 결정하였다. K값은 압력이 증가함에 따라서 증가하였고 40℃에서 최대값을 나타내었다. 부분몰부피변화(ΔV)는 비교적 작은 음의 값이 었으며 ΔV의 절대값은 40℃에서 최소값을 보여주었다. TeMPI의 이온 크기 변수(a)는 40℃에서 최대값을 가졌다. ΔH˚값은 40, 25℃ 그리고 50℃에서 각각 영, 음수 및 양수로 나타났으며 엔트로피(ΔS˚)와 자유에너지(ΔG˚)와 같은 다른 열역학변수 값도 계산하였다. 이와 같은 실험결과로부터 우리들은 TeMPI가 압력증가에 대하여 안정화되고, 40℃까지는 온도증가에 따라서도 안정화됨을 보여주었다. 그러나 40℃에서는 TeMPI 두 분자에 있는 8개 메틸기의 분자간 소수성 상호작용으로 인하여 약한 이량체를 형성하고 50℃ 이상에서는 다시 열적으로 분해된다는 결론을 얻게 되었다. The ionic association constants(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℃ to 50℃ under 1 to 2,000 bars. The K values increase with increasing pressure and have maximum value at 40℃. The partial molar volume change (ΔV) has relatively small negative value and the absolute values of Δ are minimum at 40℃. The ion size parameter(a) of TeMPI have maximum value at 40℃. ΔH˚ values are zero, positive and negative at 40℃, 25℃ and 50℃ respectively. Other thermodynamic parameters such as the changes of standard entropy (ΔS˚) and free energy(ΔG˚) 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℃ but weakly dimerized at 40℃ because of the intermolecular hydrophobic interaction of eight methyl groups of two molecules. And it thermally decomposed above 50℃.

PFAPA (Periodic Fever, Aphthous Stomatitis, Pharyngitis, and Cervical Adentis) 증후군 1예

강혜련,김신우,배기범,박지현,강영모,이종명,김능수 대한감염학회 2001 감염 Vol.33 No.3

PFAPA (Periodic Fever, Aphthous stomatitis, Pharyngitis, and cervical Adenitis) syndrome has characteristic features of an early onset, periodicity (interval <4 weeks), and a brisk rising high fever (>39℃) of 3 to 6 days' duration without signs of infection. An 18-year-old male was admitted for high fever, sore throat, headache, and abdominal pain. He had suffered from periodic fevers associated with pharyngitis and cervical adenitis for 14 years without any evidence of infection. The fever recurred approximately every 4 weeks lasting 4 to 7 days with intervening asymptomatic periods. Physical examination was unremarkable except for slightly injected tonsils. Most laboratory tests including CBC were normal except for elevation of Creactive protein level (3.47 mg/dL). Bacteriologic and radiologic studies were negative. The fever was spontaneously subsided in 6 days. To our knowledge, this is the first case report of PFAPA syndrome in Korea. (Korean J Infect Dis 33:219∼222, 2001)

The Solvolysis of Benzoyl Chloride in Water-Acetone Mixtures Under High Pressure

Jee, Jong-Gi,Ree, Taik-Yue Korean Chemical Society 1987 Bulletin of the Korean Chemical Society Vol.8 No.1

By using a complete rate constant($k_e$) which treats a solvent (water) as a reactant, and a conventional rate constant($k_c$), which ignores the solvent in describing the rate, the parameters ${\Delta}V^{\neq}_s,\;{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ were introduced. These quantities represent the volume change, the enthalpy change, and the entropy change accompanying the electrostriction which occurs when solvent molecules condense on the activated complex. The authors measured the rates of the solvolysis of benzoyl chloride in water-acetone mixtures at $15^{\circ}$ to $30^{\circ}C$ and 1 bar to 2500 bars. Applying the authors' theory to the experimental results, the parameters, ${\Delta}V^{\neq}_s,\;{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ were evaluated, and it was found that they are all negative, indicating that water dipoles condense on the activated complex. They also proposed the following equations: ${\Delta}H^{\neq}_c\;=\;{\Delta}H^{\neq}_e\;+\;{\Delta}H^{\neq}_s\;and\; {\Delta}S^{\neq}_c\;=\;{\Delta}S^{\neq}_e\;+{\Delta}S^{\neq}_s\;,\;where\;{\Delta}H^{\neq}_c\;and\;{\Delta}H^{\neq}_c\;and\;{\Delta}S^{\neq}_s $are the activation enthalpy change and the activation entropy change for the conventional reaction rate, respectively, and ${\Delta}H^{\neq}_e$ and ${\Delta}S^{\neq}_e$ are the corresponding quantities for the complete reaction rate. The authors proposed that for the $SN_1$ type, all the quantities, ${\Delta}V^{\neq}_s,\;{\Delta}S^{\neq}_s\;,{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ are comparatively large, and for the $SN_2$ type, these quantities are smaller than for the $SN_1$ type, and occasionally the case ${\Delta}S^{\neq}_e$ < 0 occurs. Using these criteria, the authors concluded that at high temperature, high pressure and for a high water content solvent, the SN_1$ type mechanism predominates whereas in the reversed case the $SN_2$M type predominates.

A Study of the Ionic Association of the Substituted N-Methyl Pyridinium Iodides (I). N-Methyl Pyridinium Iodide in Ethanol-Water Mixture

Jee, Jong-Gi,Kwun, Oh-Cheun Korean Chemical Society 1984 Bulletin of the Korean Chemical Society Vol.5 No.1

The ionic association constant (K) of N-methyl pyridinium iodide (NMPI) ion in several ethanol-water mixtures were determined by the combination of UV spectroscopy and conductance measurements using the Shedlovsky function as a correction factor. The measurement of electrical conductance and UV absorption were performed in 95, 90, 80 and 60 volume percentages of ethanol in the solvent mixture at 15, 25, 35 and 45 $({\pm}0.1)^{\circ}C$. The ion size parameter $(r_A+_D-)$ and the dipole moment $({\mu}_A+_D-)$ of NMPI ion were obtained from he linear plots of ln K vs. (1/D) and (D-1)/(2D+1), respectively. These ${\mu}_A+_D-$ values were in good agreement with the values of transition moment calculated from the equation, ${\mu}_{nm}=6.5168{\times}10^{-2}{\times}({\varepsilon}_{max}{\frac{\bar{\nu}_{\frac{1}{2}}}{\bar{\nu}_{max}})^{\frac{1}{2}}$ (Debye) which we have derived. The thermodynamic parameters indicate (1) that the water dipoles have an ordered rearrangement around the dipolar NMPI ions rather than the configuration existing in bulk free waters; and (2) that the equilibrium state between NMPI ion and its component ions are controlled by entropy.

Thermodynamics of 2, N-Dimethyl Pyridinium Iodide in Ethanol-Water Mixture under High Pressure

Jee, Jong-Gi,Lee, Young-Hwa,Woo, Eui-Ha,Lee, Kyung-Hee 慶北大學校 物理化學硏究所 1984 硏究論文集 Vol.5 No.-

The ionic association constants (K) of 2, N-dimethyl pyridinium iodide(2NDMPI) in 95 volume percentage ethanol-water mixture were determined by a modified UV and conductance method at 20℃-50℃ under 1 to 2000 bars. The K values increase with increasing pressure and decrease with temperature. The total partial molar volume change (ΔV) has relatively small negative value and the absolute ΔV value decrease with increasing pressure and temperature. The ion size (a) and solvation number (n) of 2NDMPI were about 5Å and changed from 1 to 3 with decreasing temperature. Other thermodynamic parameters such as enthalpy (ΔH˚) and entropy (ΔS˚) for the equilibrium of the 2NDMPI were evaluated. From all the parameters mentioned above, we came to conclusion that the electrostruction effect of 2NDMPI in the ethanol-water mixture is enhanced with increasing pressure and decreasing temperature.

Dehydrogenation of ethylalcohol catalyzed by alcoholdehydrogenase under high pressure

Jee, Jong Gi 慶北大學校 基礎科學硏究所 1989 慶北大學敎 基礎科學硏究所 硏究論文集 Vol.10 No.-