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黃正儀,朴斗元,吳相午,鄭倧在,朴裕哲,郭永佑 慶北大學校 1977 論文集 Vol.23 No.-
金屬실리콘과 鹽化메틸을 鹽化第一구리를 觸媒로 하여 메틸실란을 合成하고 메틸실란을 加水分解하여 실록산의 被膜을 만드는 方法을 調査하였다. 이들 被膜이 文化財 保護被膜이 될 수 있는가를 檢討하기 爲해서 材料를 文化財의 材質인 몇 가지 物質에 適用하여 膜의 性能을 調査하였다. 特히 撥水效果, 汲水量 耐久性等을 調査하였으며 外觀上 아무런 變化가 없는 좋은 被膜이 될수 있다는 結果를 얻었다. The organohalogensilicone was synthesized metal silicone and methylchloride applying the direct synthetic method using copperous chloride as catalyzer. The synthesized organosilane was hydrolyzed to siloxane by various method and coated on various materials which are composed of the cultural assets. The coating film was examined to decide whether it is profitable one to protect the assets from efflorescence or air pollution. Referring to the water repellency, permiability of water and the weather test of the film it was qualified that this film was good enough to apply to the cultural assets as protecting film.
니켈-카드뮴 蓄電池중의 니켈極의 特性에 미치는 電解質의 影響
黃正儀,鄭倧在,金昌鎬 慶北大學校 自然科學大學 1986 自然科學論文集 Vol.4 No.-
Properties of the Ni(OH) electrode in Nickel-Cadmium battery are studied by the cyclo-voltammetric method in base solutions (LiOH, NaOH, KOH)at 20℃. The nickel electrode was prepared chemical precipitation of Ni(OH)_2 on the conducting substrate. The redox current ratio(ipa/ipc) which is closely related to the charge ratio of the Ni(OH)_2 electrode is greater than unity. We can conclude that OH^-ions have been inserted into the Ni(OH)_2 intersheets or adsorbed on the Ni(OH)_2 layers. The electrooxidation of inserted or adsorbed OH^- ions can be explained through a catalytic process involving the participation of Ni(Ⅱ)→Ni(Ⅲ) electrochemical reaction. The reaction products such as (OH) or OH^- also were retained in the defects of Ni(OH)_2 crystalline layers. The redox current ratio is increased by the existence of molecular oxygen in the electrolyte, because the number of OH^- ion in IHP may be increased by reduction of molecular oxygen. Voltammograms run in LiOH solutions are comparable to those recorded in NaOH or KOH solutions. In the same perturbation conditions, redox current ratio related to the Ni(Ⅱ)/Ni(Ⅲ) redox couple values in LiOH are greater than those obtained in NaOH or KOH. The effect of LiOH solution may be ascribed to the presence of highly solvated cations Li^+. In order that OH- ions can be closely adsorbed on the electrode surface, chemical work must be done to take off some water molecules from its primary hydrated sheath. It is guessed that solvated cations take up these chemical works. The sequence of redox current ratio is Li^+>Na^+>K^+.
水溶液에서 K(Crtrdta)와 K(Cotrdta)의 電極還元·反應
黃正儀,鄭倧在,金鍾元 慶北大學校 1981 論文集 Vol.32 No.-
The electrode reduction reactions of chromium(Ⅲ) and cobalt(Ⅲ) complexes with trimethylenediaminetetraacetic acid (TRDTA) as ligand were studied in aqueous solution by using cyclic voltammetry and polarography. The experimental results were compared with the diagnostic criteria derived by Nicholson and Shain. The result of polarography indicated that the reduction of K[Crtrdta] took place by one step involving one electron. Also, it was found from the cyclic voltammetric study that the reduction of [Crtrdta]^- was the reversible charge transfer reaction coupled with a preceding homogeneous chemical reaction, the CE mechanism, and the reduction of [Crtrdta]^- was the ECE mechanism, that was, the reversible charge transfer reaction followed by a reversible chemical reaction and a reversible charge transfer reaction.
黃正儀,鄭倧在,車星極 慶北大學校 文理科大學 1978 文理學叢 Vol.5 No.-
The stick antimony electrode has advantage of simplicity in measuring pH. Its field of application has been very wide in industrial and medical part. But its accuracy, sensitivity and reproducibility are somewhat poorer than those of glass electrode. In this study this electrode was applied in determining pH of the solution at various temperatures (15∼30℃) under high pressures (1∼2,500 bars). The emf(E) of the cell, Sb(Sb_2O_3/ HCl(aq.) /AgCl/ Ag, was messured and plotted against pH. In this plot standard emf(E°) of the cell was obtained by extrapolation. The relationship of emf(E) and pH at 25℃ under 1 bar was as follows, E=0.034+0.05918 pH. The slopes were decreased with increasing pressure, and emf(E) was increased. These phenomena may be caused to the activities of water, Cl^-, Sb_2, Sb_2O_3, Ag, and AgCl. In plot of pressure and pH the decrease of pH values was due to the increase of dissociation constant of hydrochoric acid. Even though the stick antimony electrode could be useful to 500 bars at 30℃, it could be useful to 1000 bars below 30℃.
황정의,오상오 慶北大學校 自然科學大學 1987 自然科學論文集 Vol.5 No.-
The equivalent conductance of magnesium chloride and magnesium sulfate soulutions have been measured at different pressures and temperatures varying the solvent composition of components. The conductances of most solutions were increased with increasing pressure but the values of MgCl_2 were decreased in the high alcohol content. The phenomenon indicate that the solvent separated ion effect is predominant in magnesium sulfate solution than in magnesium chloride or sodium chloride which shows the lower conductivities at the higher pressure. The activation energies for the eletrical conductance were remained in constant value of 2∼3 Kcal/mole. The ionization constants of salts were calculated from the conductivity data and physical properties by using the Shedlovsky's equation. The K_d values for magnesium sulfate varied in the range of 1.0×10^-3∼9.0×10^-3 at 20℃. These values are comparable with the values of 1∼10 for sodium chloride at 100℃. These abnormally large values are explained as the results of higher charge and lower temperature effect of magnesium salt than sodium salt. From the concept of the complete ionization constant the hydration number change is also calculated to be 8. 5. This value is slightly different from the sodium chloride.
黃正儀,鄭倧在,朴龍泰,池鍾基,박은숙 慶北大學校 物理化學硏究所 1984 硏究論文集 Vol.5 No.-
Anilinium ion, o-toluidinium ion, phenol 및 o-chorophenol의 해리상수를 10∼40℃ 온도범위와 1∼2000 bar의 압력범위에서 분광광도법으로 측정하였다. phenols에서는 일반적인 약산에서처럼 온도와 압력이 증가할수록 해리상수가 증가하였으나 anilinium ions의 해리상수는 온도가 증가할수록 증가하였고, 압력이 증가할수록 감소하였다. 해리상수의 압력의 효과는 해리반응시의 하전의 증감으로 설명된다. 즉 phenols와 같이 하전이 증가하는 산은 압력이 증가할수록 해리상수가 증가하나 anilinium ions와 같이 하전의 증감이 없으면 해리상수는 감소한다. 이들 해리상수값에서 열역학적 파라미터, ΔH˚, ΔG˚, ΔS˚, ΔV˚ 및 β를 계산하고 해리반응의 성질을 고찰하였다. The dissociation constants of anilinium ion, o-toluidinium ion, phenol and o-chlorophenol were measured spectroscopically in aqueous solution over the temperature range of 10∼40℃ and at the pressures up to 2,000 bars. The effects of temperature and pressure on the dissociation of the phenols are the same as those of the ordinary weak acids. Meanwhile the dissociation constants of anilinium ions are increased with temperature raising and decreased with pressure elevation. The effects of pressure on the constants can be explained by taking account of change of charge during dissociation reaction; there are increase in charge in the dissociation of phenols but anilinium ions are not. Several thermodynamic properties, ΔH˚, ΔG˚, ΔS˚, ΔV˚ and β are calculated from those constants, and the dissociation reactions are discussed by item.
황정의,정종재,박용태,지종기,박의환 慶北大學校 1982 論文集 Vol.33 No.-
The temperature and pressure dependences of the dissociation constants of mono-, di- and tri-chloroacetic acids were studied by the conductimetry in the range of 20-35℃ and 1-2500 bars. The thermodynamic parameters ΔH, ΔS, and ΔV were evaluated from the dissociation constants. The dissociation constants were increased as the temperature and pressure was increased respectively. The pressure effects can be explained by the fact that the increase of the charges of reaction species enhances the solvation of ions and reduces the reaction volume. As the more chlorines were substituted to acetic acid, the effect of pressure on the dissociation constants was decreased because of the enhanced solvation effect. From the thermodynamic data it can be estimated that there are two types of dissociation reactions. They are an enthalpy-dominated reaction and an entropy-dominated one.
백금전극에서 진한 염소산이온의 음극환원기구에 관한 연구
黃正儀,黃金小 慶北大學校 文理科大學 1974 文理學叢 Vol.2 No.-
The mechamisms of the anodic oxidation and the cathodic reduction of chlorate ion were investigated, using Pt-electrode, by means of a technique of galvanostatic double pulses. The electrode potential exhibited sharp increase in the potential-tine curve-by applying first on anodic pulse at the current density, 15 and 60ma/㎠. Th seems due to the oxidation of ClO^-_3 to CIO^-_4 After applying anodic pulse which allowed constant potential, the two transition times, τ_1 and τ_2, could be detected by applying cathodic pulse. Furthermore, the obtained transition times allowed to calculated the ratios of the number of the electron related to a cathodic reduction and to propose the possible mechanisms as well. It was found that the electrode reduction processes of chlorate ion and perchlorate ion were different from those reported by others lately.
산·염기 및 착화합물의 해리 및 치환반응에 미치는 압력의 영향
황정의 慶北大學校 物理化學硏究所 1981 硏究論文集 Vol.1-2 No.-
고압하에서 몇가지 약산의 해리상수를 전도도법, 분광광도법 및 기전력법을 이용하여 측정했다. 식초산 유도체인 1, 2 및 3염화 식초산은 전도도법으로 o-toluidinium과 anilinium이온 및 페놀, o-염화페놀은 분광광도법으로 측정하고 페놀과 o-염화페놀은 다시 기전력법으로 측정하고 비교하였다. 해리상수는 온도가 증가하면 커지며 압력이 증가하면 anilinium ion이나 o-toluidinium 이온과 같이 전하의 증가가 일어나는 산은 커졌다. 이들 해리반응의 열역학적 성질들을 계산하고 반응의 성질을 고찰하였다. The dissociation constants of some weak acids were measured under high pressure by the methods of conductance, spectrophotometric and electvomotiveforce. The chloroacetic acids were measured by the conductance method, anilinium and o-toluidinium ions and phenols by spectrophotometric method and phenols, also, by electromotive force method. The dissociation constants were depended on the temperatures and pressure, i.e. as the temperature increased the constants of the all were increased or decreased whether the charge of the reaction species increase or unchanged. The reactions were, also, analyzed from the thermodynamic properties calculated from the dissociation constants.
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℃.