• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2413-2418
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• 2009

Rates of solvolyses of 4-nitrophenyl phenyl thiophosphorochloridate (4-N$O_2$PhOP(S)(Cl)OPh, $\underline{1}$) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, and 2,2,2-trifluroethanol (TFE) are reported. Thermodynamic parameters were determined at several temperatures in three representative solvents. The extended Grunwald-Winstein equation was applied to 29 solvents and the correlation coefficient (R) showed 0.959. The sensitivities (l = 1.37 and m = 0.62) are similar to those obtained for diphenyl thiophosphorochloridate (($PhO)_2$PSCl, $\underline{2}$), diphenyl phosphorochloridate (($PhO)_2$POCl, $\underline{3}$), diphenyl phosphinic chloride ($Ph_2$POCl, $\underline{4}$), and diphenyl thiophosphinic chloride ($Ph_2$PSCl, $\underline{5}$). The solvolytic reaction mechanism of 4-nitrophenyl phenyl thiophosphorochloridate ($\underline{1}$) is suggested to be proceeded a $S_N$2 process as previously reported result. The activation enthalpies are shown as slightly low as ${\Delta}H^{\neq}\;=\;9.62\;to\;11.9\;kcal{\cdot}mol^{-1}$ and the activation entropies are shown as slightly high negative value as ${\Delta}S^{\neq}\;=\;-34.1\;to\;-44.9\;cal{\cdot}mol^{-1}{\cdot}K^{-1}$ compared to the expected $S_N$2 reaction mechanism. Kinetic solvent isotope effects are accord with a typical $S_N$2 mechanism as shown in the range of 2.41 in MeOH/ MeOD and 2.57 in $H_2O/D_2O$ solvent mixtures.

• Journal of the Korean Chemical Society
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• v.37 no.8
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• pp.695-701
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• 1993

Rate constants of solvolysis of 2-thiophenesulfonyl chloride were determined in aqueous binary mixtures with methanol, ethanol, acetone in water and in methanol. These data are interpreted using the equation of Grunwald-Winstein and Kivinen relationship. Also, kinetic solvent isotope effects in water and in methanol and product selectivities in alcohol-water mixtures were determined. Kinetic solvent isotope effect for hydrolysis of 2-thiopenesulfonyl chloride was 2.24 and 1.47 for methanol and water, respectively. Selectivity values for formation of ester relative to acid in ethanol-water mixtures show maximum S value. From kinetic solvent isotope effect in methanol and water, selectivity data in aqueous alcoholic solvents and solvent effects, it is proposed that the reaction channel favoured in low polarity solvents is general-base catalysis and/or is possibly addition elimination (S$_A$N) reaction pathway and in high polarity solvents iS S$_N$2 reaction mechanism.

• Journal of The Korean Association For Science Education
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• v.20 no.4
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• pp.505-509
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• 2000

The kinetic structure of the content of instructions at the unit of 'heart and circulation' in "the common science", which was respectively given by two teachers majored in biology and two teachers majored in earth science was investigated. Concerning of the mean of the fundamental coefficient (B1), the mean of weighted coefficients (B2) and the progression of instruction (P), T4 (B1, 0.14; B2, 0.82; P; 0.86) teacher showed relatively lower kinetic structure and faster progression than those of the others. The other teachers showed a different level of the kinetic structure and progression: T1(B1, 0.21; B2, 0.86; P; 0.79), T2 (B1, 0.02; B2, 0.85; P; 0.80), and T3 (B1, 0.22; B2, 0.83; P; 0.78). T1 teacher who showed the largest total frequency of verbal elements, the great number of sorts of verbal elements and secondary span, had a higher level of the kinetic structure, but T4 teacher showed the lowest level of total frequency of verbal elements, the great number of sorts of verbal elements and secondary span. The main reason why T4 teacher's instruction achieved a lower level of kinetic structure was estimated that he neglected to reorganize teaching materials and he showed a small number of discourse units. In addition, the unit of 'heart and circulation' was less related to T4 teacher's major and T4 teacher had a shorter teaching experience than those of the others. T4 teacher also took charge of only one class, and this did not allow to instruct repeatedly.

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1729-1733
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• 2012

The solvolysis rate constants of 2,2,2-trichloroethyl chloroformate ($Cl_3CCH_2OCOCl$, $\mathbf{3}$) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and the $Y_{Cl}$ solvent ionizing scale, with sensitivity values of $1.28{\pm}0.06$ and $0.46{\pm}0.03$ for $l$ and $m$, respectively. The activation enthalpies (${\Delta}H^{\neq}$) are 10.1 to 12.8 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) are -27.8 to -36.8 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The kinetic solvent isotope effect ($k_{MeOH}/k_{MeOD}$) of 2.39 is also in accord with $S_N2$ mechanism probably assisted by general-base catalysis.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1897-1901
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• 2011

This report shows the rates of solvolyses for phenyl methanesulfonyl chloride ($C_6H_5CH_2SO_2Cl$, I) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Three representative solvents, studies were made at several temperatures and activation parameters were determined. The thirty kinds of solvents gave a reasonably precise extended Grunwald-Winstein plot, coefficient (R) of 0.954. The sensitivity values (l = 0.61 and m = 0.34, l/m = 1.8) of phenyl methanesulfonyl chloride (I) were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, II; l = 1.01 and m = 0.61) and 2-propanesulfonyl chloride ($(CH_3)_2CHSO_2Cl$, III; l = 1.28 and m = 0.64). As with the two previously studied solvolyses, an $S_N2$ pathway with somewhat ionization reaction is proposed for the solvolyses of I. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.34 in $CH_3OH/CH_3OD$ is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

• Journal of The Korean Association For Science Education
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• v.7 no.1
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• pp.69-79
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• 1987

학교 교실에서의 수업 활동 중 가장 주된 활동은 언어적 의사소통이며 대부분의 지식 전달이 교사의 언어 활동을 통해 이루어 지고 있다. 그리고 교사의 언어적 의사소통의 순서와 구조는 효과적이고 효율적인 학습에 중요한 의미를 가지므로 이를 조직적으로 분석 평가할 필요가 있다. 따라서, 이 연구는 교실에서의 교사 언어 행동의 구조를 분석 연구할 수 있는 방법론적 기초를 마련하고자 Anderson 의 역동적 구조 이론 (Theory of Kinetic Structure) 을 소개하고, 그의 정량적 분석 방법을 한국어에 적용 할 수 있도록 수정하였으며, 교사의 실제 강의 내용을 분석하였다. 분석에 사용한 자료는 50분 동안 진행된 고등학교 1학년 생물 강의를 녹음한 것으로 소화에 관한 내용이었다. 강의 내용에서 역동적 구조의 정량적 분석 결과는 다음과 같다. 강의는 316개의 담화단위 (discourse units) 로 구성되었으며. 261개의 어소 (verbal elements)가 동정되었다. 전체 강의에서 37개의 secondary span 이 동정되었고 이는 6개의 primary span으로 구분되었다. 전체 강의에 대한 평균 기본계수(mean fundamental coefficient, $\bar{B}_1$)는 0.26으로 낮은 수준의 연관도 (commonality )를 보였으며, 평균 가중 기본계수(mean weighted coefficient, $\bar{B}_2$)의 값은 0.88이었다. 전체적으로 이 강의는 중 내지 하 구조 (moderate to low structure)를 갖고 있으며, 높은 진행도 (high progression, $\bar{D}_s$=1.07)를 보였다.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2285-2289
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• 2014

The solvolysis rate constants of 5-dimethylamino-naphthalene-1-sulfonyl chloride ($(CH_3)_2NC_{10}H_6SO_2Cl$, 1) in 31 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale with sensitivity values of $0.96{\pm}0.09$ and $0.53{\pm}0.03$ for l and m, respectively; the correlation coefficient value was 0.955. These l and m values can be considered to support an $S_N2$ reaction pathway having a transition state (TS) structure similar to that of the benzenesulfonyl chloride reaction. This interpretation is further supported by the activation parameters, i.e., relatively small positive ${\Delta}H^{\neq}$ (12.0 to $15.9kcal{\cdot}mol^{-1}$) and large negative ${\Delta}S^{\neq}$ (-23.1 to $-36.3cal{\cdot}mol^{-1}{\cdot}K^{-1}$) values, and the solvent kinetic isotope effects (SKIEs, 1.34 to 1.88). Also, the selectivity values (S = 1.2 to 2.9) obtained in binary solvents are consistent with the proposed mechanism.

• Journal of the Korean Chemical Society
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• v.61 no.1
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• pp.25-28
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• 2017

Solvolyses with the reaction center being the sulfur of 4-(chlorosulfonyl)biphenyl ($C_6H_5C_6H_4SO_2Cl$, 1) was studied under solvolytic conditions and the extended Grunwald-Winstein equation was applied. The thirty five kinds of solvents gave a reasonable extended Grunwald-Winstein plot with a correlation coefficient (R) of 0.940. The sensitivity values (l = 0.60 and m = 0.47) of 1 were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, 2; l = 1.10 and m = 0.61) proposed to undergo dissociative $S_N2$ mechanism. These l and m values for the solvolyses of 1 can be considered to support a $S_N2$ pathway with some ionization reaction. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction. The kinetic solvent isotope effect (KSIE) of 1.26 is also in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

• Journal of the Korean Chemical Society
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• v.29 no.6
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• pp.623-628
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• 1985

Rate constants for complexing with thiocyanate after ring opening of molybdenum-oxalate in acid media were obtained spectrophotometrically at 460nm. The acid-assisted dissociation of molybdenum-oxalate and the reaction of thiocyanate with oxalatooxomolybdenum (V) complex in acid media were investigated with thiocyanate and hydrogen ion concentration. The kinetic data indicate that molybdenum-oxalate is protonated to a limited extent in acid media and the protonated complex is responsible for an increase in rate for the reaction of thiocyanate with oxalatooxomolybdenum (V) complex. Replacement of an oxalate ligand in acid media has been interpreted in terms of dissociative mechanism involving bond-breaking of the oxygen trans to the yl oxygen.

• Bulletin of the Korean Chemical Society
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• v.30 no.2
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• pp.383-388
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• 2009

Rates of solvolyses of diphenyl thiophosphorochloridate ($(PhO)_2$PSCl, 1) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone and 2,2,2-trifluoroethanol (TFE) are reported. For four representative solvents, studies were made at several temperatures and activation parameters were determined. The 30 solvents gave a reasonably precise extended Grunwald-Winstein plot, correlation coefficient (R) of 0.989. The sensitivity values (l = 1.29 and m = 0.64) of diphenyl thiophosphorochloridate ($(PhO)_2$PSCl, 1) were similar to those obtained for diphenyl phosphorochloridate ($(PhO)_2$POCl, 2), diphenylphosphinyl chloride ($Ph_2$POCl, 3) and diphenylthiophosphinyl chloride ($Ph_2$PSCl, 4). As with the previously studied of 3~4 solvolyses, an $S_N$ pathway is proposed for the solvolyses of diphenyl thiophosphorochloridate (1). The activation parameters, ${\Delta}H^{\neq}\;(=11.6{\sim}13.9\;kcal{\cdot}mol^{-1})\;and\;{\Delta}S^{\neq}\; (=\;-32.1\;{\sim}\;-42.7\;cal{\cdot}mol^{-1}{\cdot}K^{-1})$, were determined, and they were in line with values expected for an $S_N$2 reaction. The large kinetic solvent isotope effects (KSIE, 2.44 in MeOH/MeOD and 3.46 in $H_2O/D_2$O) are also well explained by the proposed $S_N$2 mechanism.