• Bulletin of the Korean Chemical Society
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• 제16권3호
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• pp.252-256
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• 1995

Semiempirical MO calculations using the PM3 method are performed on the reactions of acetate esters with substituted phenolate anions. The mechanistic change from rate-limiting formation to breakdown of the anionic intermediate is shown to occur in the gas-phase, especially for meta-nitrophenyl acetate. However the mechanistic change-over takes place at a lower basicity ($pK_0$) of the anion nucleophile than found for the corresponding formate. This lowering of $pK_0$ has been ascribed to the electron donating effect of the methyl group in the acetate. For the reactions involving rate-limiting breakdown of the intermediate, the large Bronsted coefficients, ${\beta}_X({\beta}_{nuc})$, are expected in general, but the magnitude increases to a larger value and the pK0 is lowered accordingly, when an electron-donating nonleaving group, like $CH_3$, is present. This type of nonleaving group effect provides a necessary condition for the carbonyl addition-elimination mechanism with rate-limiting breakdown of the intermediate.

• Bulletin of the Korean Chemical Society
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• 제31권1호
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• pp.234-237
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• 2010

• Bulletin of the Korean Chemical Society
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• 제30권11호
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• pp.2785-2788
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• 2009

• 한국광과학회:학술대회논문집
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• 한국광과학회 1999년도 학술대회지
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• pp.83-83
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• 1999

• 한국세라믹학회:학술대회논문집
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• 한국세라믹학회 2003년도 추계총회 및 연구발표회 초록집
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• pp.145.2-145
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• 2003

• Bulletin of the Korean Chemical Society
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• 제21권1호
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• pp.118-120
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• 2000

• 한국자기학회지
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• 제7권1호
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• pp.25-30
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• 1997

치환형 Ba-ferrite의 수소환원 거동은 순수한 Ba-ferrite와는 다르게 나타났다. 환원온도 250 .deg. C에서 520 .deg. C의 범위에서 치환형 Ba-ferrite의 보자력은 증가하다가 다시 감소하는 반면에 순수한 Ba-ferrite는 계속 감소 하였다. 치환형 Ba-ferrite의 환원과정은 환원되는 정도에 따라 3단계로 나뉘어진다. 1과 2단계에서 Ba-ferrite의 구조는 그대로 유지를 하지만 자기적 성질은 다르게 나타났다. 1단계에서 보자력은 증가하고 산화처리시 가역적이지만, 2단계에서는 보자력이 더욱 증가하고 산화처리시 비가역적이었다. 그러나 3단계에서는 Ba-ferrite 구조 자체가 붕괴되어 .alpha. -Fe와 소량의 BaFe $O_{3-x}$의 생성으로 $H_{c}$는 크게 감소하고 포화자화값은 130 emu/g으로 크게 증가하였다. 이 때 보자력 분포도는 크게 넓어지며 입자크기도 감소하였다. 또한 치환이온들은 환원과정에서 Ba-ferrite 구조의 붕괴를 억제하였으며, 2a + 4 $f_{IV}$ , 2b 및 12k 자리의 치환이온들이 4 $f_{VI}$ 와 12k'의 자리로 이동함을 확인하였다. 따라서 1과 2단계에서의 보자력 증가원인은 치환이온의 자리이동에 따른 고보자력 상의 생성 때문이었다.

• Bulletin of the Korean Chemical Society
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• 제15권2호
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• pp.161-167
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• 1994

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates (3) with alkali metal ethoxides ($EtO^-M^+$) and butane-2,3-dione monoximates ($Ox^-M^+$) in ethanol at $25^{\circ}C$. The reactivity of the alkali metal ethoxides decreases in the order $EtO^-K^+> EtO^- > EtO^-Li^+$, indicating that $K^+$ ion behaves as a catalyst and $Li^+$ ion acts as an inhibitor for all the substrates studied. For the corresponding reactions of 3 with Ox^-M^+$, $Li^+$ ion also exhibits inhibitory effect for all the substrates, while, $K^+$ ion shows catalytic or inhibitory effects depending on the nature of substituents on the acyl and phenyl moieties. A study of substituent effect on rate has revealed that both EtO^- $and Ox^-$ systems have the same reaction mechanism. The different behavior shown by $K^+$ ion for the reaction of 3 with $EtO^-$ and $Ox^-$ would be attributed to a difference in charge polarization of S=O bond in the transition state between the two systems and/or a change in conformation of Ox^-K^+$.

• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.2015-2018
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• 2010

Second-order rate constants $(k_{OH^-})$ have been measured spectrophotometrically for alkaline hydrolysis of Y-substituted phenyl phenyl carbonates (2a-j) and compared with the $k_{OH^-}$ values reported previously for the corresponding reactions of Y-substituted phenyl benzoates (1a-j). Carbonates 2a-j are 8~16 times more reactive than benzoates 1a-j. The Hammett plots correlated with $\sigma^-$ and $\sigma^o$ constants exhibit many scattered points, while the Yukawa-Tsuno plot results in excellent linear correlation with $\rho$ = 1.21 and $\gamma$ = 0.33. Thus, the reaction has been concluded to proceed through a concerted mechanism in which expulsion of the leaving group is advanced only a little. However, one cannot exclude a possibility that the current reaction proceeds through a forced concerted mechanism with a highly unstable intermediate.

• 한국해양공학회지
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• 제24권5호
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• pp.55-59
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• 2010

The effect of aging on the precipitation of the $\sigma$ phase and corrosion resistance in W-substituted, super-duplex stainless steel was investigated. The volume fraction of the $\sigma$ phase and the current density increased as the aging temperature increased up to $750^{\circ}C$, and, then, they decreased. As aging time increased, the volume fraction of the $\sigma$ phase and the current density also increased. The $\sigma$ phase considerably influenced to corrosion resistance. When Mo was substituted for W in super-duplex stainless steel, the volume fraction of the $\sigma$ phase and the current density both decreased markedly.