Volume 7 Issue 4

  1. Chi Sun Hahn 225
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    The nature of the two isomers of 4-nitroazoxybenzenes in strongly acidic solution have been analyzed by U.V. spectrophotometry. Oxygen atom in the azoxy-group of $\alpha$-and $\beta$-4-nitroazoxybenzene in strong acid solution migrates neither to para position nor ortho position of the unsubstituted benzene ring of the compound in contrast with the cases of methyl-and bromo-substituted azoxybenzene, and shown no Wallach rearrangement. Since the $^1A{\rightarrow}^1H$ bands of the spectra shown hyperchromic effect whereas the ${\pi}{\rightarrow}{\pi}^*$ bands of them exhibit extream hypochromic effect, it appears most likely that trans ${\rightarrow}$cis isomerization take place in the media. A mechanism of a triangular transition state by which the transformation might be proceeded, is proposed.
  2. Chi Sun Hahn 230
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    2-Methyl-5,5'-gem-disubstituted-$\Delta^2$-thiazoline系 化合物의 合成을 1,1'-gem-dusubstituted thiiranes의 三員環을 ammonis로 開環하여 骸當하는 N-또는 S-acetyl-amino mercaptan을 얻고 그것을 다시 閉環하는 方法과 또 하나는 같은 三員環인 gem-disubstitutes imines을 thiolacetic acid 로 開環하고 그것을 直接 다시 閉環하여 얻은 두가지 方法에 의하여 硏究하엿다. 前者는 thiirane ring은 gem-disubtitution의 compression 效果에 의하여 極히 安定化되어 여러가지 强力한 反應條件下에서의 sodium amide를 利用한 ammonia nuclephile에 頑强한 抵抗을 나타냈으며 反對로 後者의 三員環 imine은 같은 gem-disubstitution 效果를 받음에도 不拘하고 容易하게 開環하였다. 이 gem-disubstitution 效果에 의한 環狀化合物의 開環阻止性과 閉環促進性을 立體化學的인 見地에서 考察하였으며 本硏究로서 環狀化合物의 安定性에 미치는 gem-disubstitution의 compression 效果는 所謂 Thorpe-Ingold bond angle deformation에 緣由하는 것이 아니고 오히려 gem-dusubstituents와 異節環狀化物內의 hetero atom(s)이 미치는 bond interaction에 起因하다는 結論을 얻었다.
  3. Ikchoon Lee;Yong Ja Park 238
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    前報에서 誘導한 새로운 直線關係式,${\Delta}{\Delta}H^{\neq}=a{\sigma}+b{\Delta}{\Delta}S^\neq$ 및 ${\Delta}{\Delta}F^{\neq}=a{\sigma]+(b-T){\Delta}{\Delta}S^{\neq}$, 의 適用性을 57個反應으로 檢討하였다. 57個反應에 대한 ${\Delta}{\Delta}H^{\neq}-a{\sigma}$, 對 ${\Delta}{\Delta}S^{\neq}$의 直線關係 相關係數의 平均은 0.983이었고 直線으로부터의 標準備差의 平均値는 0.11이었다. 57個反應中 15個反應에 對해서는 Hammett方程式이 成立되지 않었고, 또 大部分의 反應에 對해서 Leffier의 式이 成立하지 않었다. 이와같이 從來의 關係式 이 成立하지 않는 反應도 새로운 關係式으로 設明되며, 그 理由를 檢討해 봄으로써 上記 2式이 더 一般的으로 適用되는 關係式임을 確認하였다.
  4. C. T. Rhee 245
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    TBPO와 TOPO와의 混合溶媒(稀釋制 : toluene)에 依한 三假狀態의 4f 稀土類元素의 抽出에 있어 相乘效果(synerigistic effect)가 나타남을 알았으며 이것은 各 單獨溶媒系에 있어서 生成抽出되는 $M(NO_3)_3\;(TBPO)_3$ 및 $M(NO_3)_3\;(TOPO)_3$型 外에 $M(NO_3)_3\;(TBPO)_2\;(TOPO)$型이 새로히 追加生成됨을 起因된 것으로 認定된다.
  5. W. K. Min 251
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    Six corrosion inhibitors for cooling water use were evaluated by means of a corrosometer in a laboratory bench scale test. A steel probe (Alloy 1020) was exposed and checked for the extent of corrosion in a recirculating water system, changing inhibitors and their concentrations at $40^{\circ}C$. A 95% inhibition was provided at the following concentrations of inhibitors. 50 ppm sodium hexametaphosphate 50 ppm commercial inhibitor A 50 ppm commercial inhibitor B 100 ppm disodium phosphate 200 ppm sodium chromate Sodium silicate was found to be use-less in this test. It was also observed that some inhibitors worked less effectively on the acid-cleaned steel probe.
  6. Jae-young Hwang 254
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    $KF-BaTiO_3$系와 $TiO_2-BaTiO_3$系에서 각각 成長시킨 $BaTiO_3$의 單結晶中의 중요 不純物을 分光化學分析法으로 定量하여 比較 檢討하였다. 이 分析法은 $SrTiO_3$의 單結晶의 分光化學分析에도 適用된다.
  7. Chung Hoe Koo;Hoon Sup Kim 257
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    The crystal structure of nicotinic acid hydrochloride has been determined by two-dimensional x-ray method. The unit cell is monoclinic with a = 7.21 ${\AA}$, b = 6.69 ${\AA}$, c = 7.54 ${\AA}$, ${\beta}=100^{\circ}$, space group $C{\frac{2}{2}}-P2_1$, and contains two formula units. Weissenberg diagrams have been taken along the a, b and c axes with Cu K${\alpha}$ radiation and the positions of the atoms have been fixed by means of two dimensional Patterson syntheses, a Fourier projection along the b-axis and trial and error method. The bond lengths are: pyridine ring C-C = 1.38, 1.39 ${\AA}$, C-N = 1.34, 1.36 ${\AA}$, carboxyl group $C_4-C_6$ = 1.46 ${\AA}$, $C_6-O_1$ = l.33 ${\AA}$, $C_6-O_2$ = 1.19 ${\AA}$. The ring nitrogen atom may be regarded as forming bifurcated hydrogen bond with an oxygen atom $O_2$ of one neighbouring molecule and with a neighbouring chlorine atom, being linked by forming a hydrogen bond with an other oxygen atom $O_1$ of above mentioned neighbouring molecule, in such a way that chains parallel to the c-axis are formed.
  8. Ikchoon Lee 264
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    前報에서 誘導한 置換基效果 一般關係式은 溶媒組成에 따르는 常數, Y를 potential energy 項에 代置함으로서 solvolysis 反應에 適用할 수가 있다. 新方程式, $\Delta{\Delta}H^\neq=a'Y+b\Delta{\Delta}S^\neq$, 의 適用性은 文獻에 報告된 35個反應에 對한 直線關係를 調査해 봄으로서 檢討하였다. 結果로 平均 相關係數 0.977을 얻었고, 따라서 이 方程式이 solvolysis反應에 一般的으로 適用됨을 밝혔고, 또 Grunwald-Winstein의 式이 지니는 몇몇 難點을 解決할 수가 있음을 알 수 있었다. enthalypy-entopy 直線效果는 外部 enthalpy와 外部 entropy에 限한 것이며, 嚴格히 말해서 外部 enthalpy entropy 直線效果임을 强調하였다.
  9. C. T. Rhee 271
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    TBPO-toluene 및 TOPO-toluene 系에 대한 4f 稀土類元素의 硝酸鹽의 溶媒濃度, 硝酸基濃度 및 原子番號(Z)의 變化에 따르는 分配率의 變化를 放射化學的으로 測定하였다. log Kd 對 Z의 關係는 Z=63∼64에서 交叉되는 二個의 直線으로 表示되면 溶媒濃度 依存度는 稀土類元素 全般에 걸쳐 一定하나 硝酸基濃度 依存度는 經稀土類元素와 重稀土類元素가 다르게 나타난다.
  10. Man Un Han;Chong Man Lee 277
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    The surface tension of solutions of synthesized ammonium caprylate and ammonium caprate was measured by the ring method. The changes with of surface tension of solution of ammonium caprylate showed evidently that the salt had the critical micelle concentration(c.m.c.) at $30^{\circ}C$. The c.m.c. values of above two salts were determined from the change of surface tension of solution with concentration at various temperatures. The temperature dependence of the c.m.c. and the influence of addition of excess ammonia on the c.m.c. were also investigated.
  11. Si-Joong Kim;Doo-Soon Shin 280
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    Spectrophotometry에 의한 몰比法, 運續變化法 및 傾科比法으로 chloroform phase에 存在하는 Fe(III)-cupferrate의 組成을 決定하였는데, 그 황化合物은 325m$\mu$에서와 385m$\mu$에서 모두 $FeCupf_3^인 化學式을 갖는 것이었다.
  12. Si-Joong Kim;Doo-Soon Shin 283
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    $H_2O$-chloroform系에서의 hydrogen cupferrate의 分配係數와 水溶液相의 pH, 이온强度 및 cupferron의 濃度와의 關係를 살폈는데, 分配係數는 pH(1.50∼3.00사이)와 이온强度(0.1∼2.0사이)에는 無關하지만 cupferron의 濃度가 커질수록 分配係數는 增加했으며, 熱力學的인 分配係數의 完全한 값으로 120.0이란 새로운 값을 얻었다. 한편 cupferron의 濃度가 커짐에 따라 分配係數가 增加하는 까닭은 chloroform相에 monomer로서의 HCup. 의 活動度의 감소로 간주하고, chloroform相에서의 HCup. 의 濃度와 chloroform相에서의 HCup. 의 活動度係數와의 關係를 表示하는 實驗式 $-logf_{CHCl3}=0.1285C_{CHCl3}+{7.775C^2}_{CHCl3}$를 얻었으며, 이 式은 HCup. 의 chloroform 溶液 0.1mole/l order 以下의 濃度에서 大端히 잘 맞는다.
  13. Tae Hee Hahn 288
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    The rates of reaction of various Korean anthracites with carbon dioxide were measured at temperatures ranging from $850^{\circ}C$ to $1100^{\circ}C$ with coal -6, +8 sieve size and the residence time of reactant gas in the fixed coal bed 14.0 to 15.0 seconds. The primary variables studied were the coal sources and temperature. The reactivity was considerably varies with the coal sources and the general trends show that the reactivity sharply increases with increasing reaction temperature except the Yongwol coal where the increase is not so sharp, which is considered to be due to high reactivity and high-pore structure of the coal. It was also found that a straight line was produced when a logarithm of the rate constant is plotted against the reciprocal of the absolute temperature up to 1000^${\circ}C$, but above that temperature it deviates from linearity. The information obtained will be of value in the design of the coal gasifier using Korean anthracites.
  14. Chung Hoe Koo;Moon Il Kim;Chung Soo Yoo 293
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    The crystal structure of ethylenediamine dihydrochloride has been determined by the two-dimensional Patterson methods and refined by two-dimensional Fourier syntheses. The unit cell dimensions are a = 4.44${\pm}$0.02, b = 6.88${\pm}$0.02, c = 9.97${\pm}$0.02 ${\AA}$, ${\beta}$ = 92${\pm}$$1^{\circ}$. The space group is $P2_1_{/c}$. The carbon and nitrogen atoms in the ethylenediamine itself lie on one plane and its structure has a trans-form with a centre of symmetry in it, and C-C distance of 1.54 ${\AA}$, C-N distance of 1.48${\AA}$ and C-C-N bond angle of $109.07^{\circ}$. The molecules are linked by N-H${\cdots}$Cl hydrogen bonds with distance of 3.14, 3.16 and 3.22 ${\AA}$ forming three dimensional network. The values of reliability factor for F(okl), F(hol) and F(hko) are 0.11, 0.10 and 0.09 respectively.
  15. Doo Won Park;Chong Nam Lee 299
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    A method of the colorimetric determination of titanium has been developed, based on the fact (IV) forms a stable blue complex with methylthymolblue(MTB) which is suitable for spectrophotometric determination of titanium in the concentration range of 0.2 to 22 $\mu$g per ml as $TiO_2$. The determination was carried out in the solution of pH range of 2.6 to 3.6, and the absorbancy of complex was at 600m$\mu$ with Coleman spectrophotometer. Titanium forms a 1:1 complex with MTB, which has a molar absorptivity, $1.1{\times}10^4$ at 600m\mu$. The effects of hydrogen ion concentration, reagent concentration, stability of complex, and hydrolysis were studied. Most of cations do not interfere seriously; however, many of anions such as oxalate, citrate, phosphate, chloride interfere in this determination.