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Kinetic Studies of Chlorine Exchange between Benzyl Chloride and Radioactive Chloride Ion
박용자,이익춘,Park, Yong-Ja,Lee, Ik-Choon Korean Chemical Society 1965 대한화학회지 Vol.9 No.1
90% ethanol solution에서 benzyl chloride와 radioactive chloride($^{36}Cl^-$)와의 exchange를 反應速度論的으로 硏究하였으며 그 結果로 交換反應은 typical bimolecular reaction임을 알았고 그 activation parameter들은 각기 다음과 같았다. ${\Delta}H^{\neq}$= 18.50 Kcal ${\Delta}S^{\neq}$= -22.09 e.u. 특히 本實驗 缺課와 다른 實驗結果를 綜合討論함으로써 反應速度는 attacking anion의 nuclephilic ability에 크게 관계 됨을 입증할 수 있었으며 또한 exchange reaction에 있어서 halide들의 reactivity의 순서는 bond dissociation energy의 差로써 보다는 오히려 Swain의 nucleophilic parameter(n)로써 설명함이 더욱 타당함을 알았다. Halogen exchanges between benzyl chloride and chloride ion have been studied in 90% ethanol-water mixture, and activation parameters in the exchange reaction have been determined; ${\Delta}H^{\neq}$ = 18. 50 Kcal and ${\Delta}S^{\neq}$ = -22. 09 e. u. Results indicated that the reaction proceeded via a typical bimolecular mechanism. The importance of nucleophilic ability of attacking anion in $S_N2$ process has been stressed giving some experimental evidence. The order of reactivity of halides in the exchange reaction is better explained with the Swain's nucleophilic parameter than with the bond dissociation energies.
有機 Halides 와 Amines 間의 光反應에 關한 硏究
김유선,박용자,Kim, You-Sun,Park, Yong-Ja 대한화학회 1962 대한화학회지 Vol.6 No.2
The reactions between organic halides$(CCl_4,\;C_6H_5Br,\;C_6H_5Cl,\;C_6H_5I)$ and amines $(C_6H_5NH_2,\;R_2NH,\;R_3N,\;(CH_2)_5NH,\;pyridine)$ were studied under mixed u.v. irradiation. The modes of reactions were examined by means of gas chromatography and product-reactant ratio determination. The reaction of $CCl_4$ with amines give chloroform and hexachloroethanes, and the reaction of aromatic halides with amines gave biphenyl and benzene. In each series of reaction there obtained mainly corresponding amine hydrohalides, but no amination products. The reactivity was in the order of the basicity of amines and of the reactivity of organic hahides, except in the case of cyclic tertiary amine. The result was interpreted as a non-chain photodecomposition process. A competitive proton abstraction reaction path via the formation of a change transfer complex was proposed as the reaction mechanism.
Linear Relationships between Thermodynamic Parameters (Part II) Applicabiliy of New Equations
이익춘,박용자,Ikchoon Lee,Yong Ja Park Korean Chemical Society 1963 대한화학회지 Vol.7 No.4
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. Linear relationships between thermodynamic parameters, ,${\Delta}{\Delta}H^{\neq}=a{\sigma}+b{\Delta}{\Delta}S^{\neq}$, and $\Delta{\Delta}F^\neq=a\sigma+(b-T)\Delta{\Delta}S^\neq$, which were derived in the previous report have been tested with 57 reactions from literature. Linearities of plots $\Delta{\Delta}H^\neq-a\sigma$ vs. $\Delta{\Delta}S^\neq$ were generally good and the average correlation coefficient was 0.983 and the average of standard deviations from regression lines was 0.11. For 15 out of 57 reactions, Hammett plots were unsatisfactory and most of the reaction did not satisfy the Leffler equation. The general applicability of the new equations has been confirmed by the analysis of each reaction for which existing equations failed to correlate.
열역학함수간의 직선관계 (제6보) 염화벤질의 염소교환에 미치는 용매효과
이익춘,박용자,Lee, Ik-Choon,Park, Yong-Ja 대한화학회 1968 대한화학회지 Vol.12 No.4
Rate constants and activation parameters have been petermined for the chloride exchanges of benzyl chloride in 60, 70, 80 and 90 vol.% ethanol-water solutions. Results showed a good linearity when appiled to our general equation. The significance of this linear fit has been discussed in conjunction with the Dewar's relation which was derived from the PMO method.
熱力學函數間의 直線關係 第四報 Dimethylaniline 直換體의 鑒基度에 關한 硏究
이익춘,박용자,Lee, Ik-Choon,Park, Yong-Ja 대한화학회 1964 대한화학회지 Vol.8 No.1
Basicities of nine dimethylanilines have been determined in 50, 70, and 90 volume % ethanol, at $25^{\circ},\;30^{\circ},\;35^{\circ},\;and\;40^{\circ}C$. Temperature coefficients were found to be independent of solvent composition, while they showed a linear correlation with basicities of the compounds. Thermodynamic parameters obtained have been used in the discussion of substituent and solvent effects in conjunction with the general equation derived in the preceding papers.