• Title/Summary/Keyword: Substitution rate

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Durability in Concrete Containing Limestone Powder and Slag Powder (석회석 미분말과 슬래그 미분말을 혼합한 콘크리트의 내구성)

  • 구봉근;이재범;이현석;박주원
    • Proceedings of the Korea Concrete Institute Conference
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    • 2003.11a
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    • pp.82-85
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    • 2003
  • This study is to investigate durability in concrete containing slag powder and limestone power. The variables are the substitution ratio of slag powder and limestone powder. In order to study the effect of slag powder and limestone powder, all mixtures were prepared at a fixed water/cement ratio, slump, and entrained air quantity. When concrete containing slag powder is mixing rate 40%, durability appeared the highest in general. When concrete containing limestone powder is mixing rate 10% in all experiments, the most suitable result appeared.

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Kinetic Analysis by High Pressure and High Vacuum Apparatus for the Nucleophilic Substitution Reaction (고압 및 고진공장치를 이용한 친핵성치환반응에 대한 속도론적 분석)

  • Kim, Se-Kyong
    • Analytical Science and Technology
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    • v.17 no.5
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    • pp.375-380
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    • 2004
  • Kinetics have been studied by high vacuum and high pressure apparatus under various temperatures and pressures for the nucleophilic substitution reaction. Rate constants, activated parameters and Hammett ${\rho}$-values are determined. The values of ${\Delta}V^{\ddag}$, ${\Delta}{\beta}^{\ddag}$ and ${\Delta}S^{\ddag}$ are all negative. The Hammett ${\rho}$-values are negative for the nucleophile (${\rho}x$) over the pressure range studied. Consequently the rate constant increases as the pressure increases, and some decrease in vacuum. So these reactions proceed in typical $S_N2$ reaction mechanism.

The Rate Maxima and Hammett Correlation for the Nucleophilic Substitution (친핵성 치환반응에서 최대속도현상과 Hammett상관관계)

  • 성대동;임귀택
    • The Korean Journal of Food And Nutrition
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    • v.8 no.3
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    • pp.172-183
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    • 1995
  • The nucleophilic substitution reactions of p-substituted benzyl bromide with l-substituted N,N-dimethylanilines in methanol and acetonitrile binary solvent mixture which is known to an isodielectric solvent system kinetically and the results are as follows. The positive charge is developed on the reaction center of the substrate and it means that the bond cleavage is preceded more than bond formation in the transition state on the analogy of Hammett px values. The bond form3tlon is not progressed in the case of electron donating substituent of substrate. However, the bond formation is much developed in the case of electron withdrawing substituent of substrate on the analogy of Hammett py values. The nucleophilic attacking ability is shown a highest at 80% (V/V) methanol content and the bond formation is well progressed at the same methanol composition on the result of a cross interaction coefficient, pxy. The result of transition state structure that is applicated to the potential energy surface model is in accord with the result that Is applicated to the reaction susceptibilities. The reaction Is subject to the polarity-polarizability term more than the hydrogen bond donor acidity term by application to the solvatochromic parameter eouation.

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Rate and Mechanism for Substitution of Chloropentaamminecobalt(III) in Aqueous $Hg^{2+}$ Solution ($Hg^{2+}$이온 水溶液 內에서의 Chloropentaamminecobalt(III)의 置換反應速度와 메카니즘 (제 1 보))

  • Byung-Kak Park;Jae-Weon Lee;Joo-Sang Lim
    • Journal of the Korean Chemical Society
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    • v.30 no.3
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    • pp.282-288
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    • 1986
  • Kinetic studies were carried out for the substitution of $H-2$O for $Cl^-$ ligand of chloropentaamminecobalt(III) in the presence of $Hg^{2+}$ catalyst by UV spectrophotometer. It has been found that $Hg^{2+}$ ion appears first order dependence and the overall reaction is second order. The reaction system can be believed to occur via $S_N2$ reaction, because the calculated rate equation for our presumed $S_N2$ mechanism is in agreement with the observed one.

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An Experimental Study on the Mechanical Properties of Concrete with the Contents of Recycled coarse Aggregate (재생 굵은 골재를 사용한 재생 콘크리트의 역학적 특성에 관한 실험적 연구)

  • 김호수;백철우;반성수;최성우;류득현
    • Proceedings of the Korea Concrete Institute Conference
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    • 2003.05a
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    • pp.25-30
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    • 2003
  • Owing to the deterioration of reconstruction and the construction, much of the construction waste is discharged in our construction field. By supplementing aggregate resources that are insufficient by recycling waste concrete, it is considered that the resource-preserving effect according to the saving and reuse of resource as well as eco-friendly effect that is regarded as important in recent industrial society may be expected. In this study conducted an experiment by setting up 15 levels according to the variations in the rate of substitution of recycled coarse aggregate by the water cement ratio(40, 50, 60%). As the result of it, the slump and air contents was increased by ratio of coarse aggregate, and the elapsed characteristics by the ratio of recycled coarse aggregate showed that there is no clear difference in slump and the air contents. Further, in the characteristics of strength development, the lower the water cement ratio, the higher the compressive strength at early ages, compared with crushed stone, while the compression declined according to the increase of substitution rate of recycled gravel as it was tending upward long-term ages.

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An Experimental Study on the Performance Characteristics of the Vortex Tube for Substitution of the Intercooler in a Common-rail Diesel Engine (커먼레일 디젤기관의 인터쿨러 대체용 볼텍스 튜브 장치의 성능특성에 관한 실험 연구)

  • Im, Seok-Yeon;Choi, Doo-Seuk;Ryu, Jeong-In
    • Transactions of the Korean Society of Automotive Engineers
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    • v.16 no.3
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    • pp.172-178
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    • 2008
  • An object of this study is to confirm performance characteristics of the vortex tube apparatus for substitution of the intercooler in a common-rail diesel engine. The turbo pressure, the intake air flow rate and the ${\Delta}T_c$ decrease ratio of the intercooler were measured in a experimental engine. The vortex tube apparatus was made after confirmation of the geometric phenomena in fundamental experiments. To investigate energy separation characteristics of the vortex tube, the measured turbo pressure was applied to the vortex tube inlet and the ${\Delta}T_c$ decrease ratio was compared with one of the intercooler in the cold air mass flow ratio similar to the intake air flow rate of the experimental engine. From the results, we found that the energy separation ratio is increased according to of the inlet pressure and the ${\Delta}T_c$ decrease ratio of the vortex tube apparatus is higher than one of the intercooler at low engine speed and engine load of medium and low.

Kinetics and Mechanism for Alkaline Hydrolysis of Dinitrothiophene Disperse Dye(C. I. Disperse Green 9) (디니트로티오펜계 분산염료인 C. I. Disperse Green 9의 알칼리 가수분해 반응속도 및 반응메카니즘)

  • Park, Geon-Yong;Kim, Jae-Hyoun
    • Textile Coloration and Finishing
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    • v.19 no.4
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    • pp.18-25
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    • 2007
  • Kinetics and mechanism for alkaline hydrolysis of C. I. Disperse Green 9(G-9) of dinitrothiophene disperse dye were investigated. As soon as G-9 contacted with alkali, instant and continuous decreases of color strength of G-9 followed with increasing time. The hydrolysis rate of G-9 increased with increasing alkali, and it was found that alkali appeared first order dependence. The observed rate constants obtained from hydrolysis of various amount of dye were similar values, and calculation of initial rates showed that G-9 hydrolyzed by first order reaction for dye. Therefore it was confirmed that the overall reaction was second order, $SN_2$ of nucleophilic substitution reaction. Increasing temperature enhanced the hydrolysis of G-9. From the results of hydrolysis performed at various temperatures, it was obtained that activation energy(Ea) was 12.6 kcal/mole, enthalpy of reaction(${\triangle}H$) was 12.0 kcal/mole, and entropy of reaction(${\triangle}S$) was $29.8J/mol{\cdot}K$.

Effect of sodium on transmembrane calcium movement in the cat ileal longitudinal muscle

  • Rho, Young-Jae;Yun, Il;Kang, Jung-Sook
    • Archives of Pharmacal Research
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    • v.10 no.2
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    • pp.80-87
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    • 1987
  • To get a better insight into the exxistence and the role of a Na-Ca exchange mechanism in smooth muscle, the effect of Na substitution with sucrose on tension development, cellular Ca uptake and $^{45}Ca$ efflux was investigated using isolated cat ileal longitudinal muscle strips. Experimental results were summarized as follows;1) Exposure of the cat ileal longitudinal muscle to Na-free solution induced a contraction, and the magnitude of the contraction increased after incubation of the muscle strips with ouabain ($2{\times10^{-}5}$M) for 1hr. 2) Cellular Ca uptake in Na-free solution increased with an increase in Na content of the Na-loading media, and a linear relationship existed between tissue Na content and cellular Ca uptake for 10 min 3) After tissues were equilibrated in PSS containing $^{45}Ca$ for 2hr, cellular Ca uptake decreased with rising the external Na concentration. 4)Removal of medium Na or inhibition of the Na-K pump decreased the rate of $^{45}Ca$ efflux. These results strongly suggested that Na substitution increases cellular Ca uptake and decreases the rate of $^{45}Ca$ efflux via a Na-Ca exchange mechanism.

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A Mechanistic Study on Nucleophilic Substitution Reactions of Aryl Substituted Benzenesulfonates with Anionic Nucleophiles

  • Um Ik-Hwan;Lee Seok-Joo;Kim Jung-Joo;Kwon Dong-Sook
    • Bulletin of the Korean Chemical Society
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    • v.15 no.6
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    • pp.473-477
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    • 1994
  • Second-order rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates $(1,\;X-C_6H_4SO_2-OC_6H_4-Y)$ with aryloxides $(Z-C_6H_4O^{-})$ and ethoxide $(EtO^-)$ in absolute ethanol at $25^{circ}C$. The nucleophilicity of aryloxides increases with increasing electron donating ability of the substituent (Z) on aryloxides, and results in a good Hammett correlation with $\sigma^{-}$ constant. The reactivity of 1 toward aryloxides and ethoxide shows also significant dependence on the electronic nature of the substituent X and Y. Large positive ${\sigma}_{acyl}$ values have been obtained for the reaction of 1 with phenoxide and ethoxide, indicating that the leaving group departure is little advanced at the transition-state of the rate-determining step. This has been further supported from the fact that ${\sigma}^-$ constant gives extremely poor Hammett correlation, while ${\sigma}^0$ does reasonably good correlation for the reaction of 1 with ethoxide. Thus, the present sulfonyl-transfer reaction is proposed to proceed via a ratedetermining attack of nucleophile to the sulfur atom of 1 followed by a fast leaving group departure.

The Effect of Alkali Metal Ions on Nucleophilic Substitution Reactions of Aryl Substituted Benzenesulfonates

  • Ik-Hwan Um;Seok-Joo Lee;Hee-Sun Park;Dong-Sook Kwon
    • Bulletin of the Korean Chemical Society
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    • v.15 no.2
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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^+$.