• Bulletin of the Korean Chemical Society
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• v.30 no.1
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• pp.214-218
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• 2009

Second-order rate constants ($k_N$) have been measured for nucleophilic substitution reactions of S-4-nitrophenyl thiobenzoate with a series of alicyclic secondary amines in $H_2O$ containing 20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The Br$\phi$nsted-type plot exhibits a downward curvature, i.e., $\beta_{nuc}$ decreases from 0.94 to 0.34 as the amine basicity increases. The reactions in the aqueous DMSO have also been suggested to proceed through a zwitterionic tetrahedral intermediate (T${\pm}$) with change in the RDS on the basis of the curved Br$\phi$nsted-type plot. The reactions in the aqueous DMSO exhibit larger $k_N$ values than those in the aqueous EtOH. The macroscopic rate constants ($k_N$) for the reactions in the two solvent systems have been dissected into the microscopic rate constants ($k_1\;and\;k_2/k_{-1}$ ratio) to investigate effect of medium on reactivity in the microscopic level. It has been found that the $k_2/k_{-1}$ ratios are similar for the reactions in the two solvent systems, while $k_1$ values are larger for the reactions in 20 mol % DMSO than for those in 44 wt % EtOH, indicating that the larger $k_1$ is mainly responsible for the larger $k_N$. It has been suggested that the transition state is more stabilized in 20 mol % DMSO through mutual polarizability interaction than in 44 wt % EtOH through H-bonding interaction.

• Journal of the Korea institute for structural maintenance and inspection
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• v.21 no.6
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• pp.74-82
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• 2017

This research presents the results of the strength and drying shrinkage properties to study the effect of ground granulated blast furnace slag(GGBFS), fly ash(FA) and calcium sulfoaluminate(CSA) for activated ternary blended slag cement. The activated ternary blended cement(ATBC) mortar were prepared having a constant water-cementitious materials ratios of 0.4. The GGBFS contents ratios of 100%, 80%, 70% and 60%, FA replacement ratios of 10%, 20%, 30% and 40%, CSA ratios of 0%, 10%, 20% and 30% were designed. The superplasticizer of polycarboxylate type were used. The activator was used of 10% sodium hydroxide(NaOH) + 10% sodium silicate($Na_2SiO_3$) by weight of binder. Test were conducted for mini slump, setting time, V-funnel, water absorption, compressive strength and drying shrinkage. According to the experimental results, the contents of superplasticizer, V-funnel and compressive strength increases with an increase in CSA contents for all mixtures. Moreover, the setting time, water absorption ratios and drying shrinkage ratio decrease with and increase in CSA. One of the major reason for the increase of strength and decrease of drying shrinkage is the accelerated reactivity of GGBFS with alkali activator and CSA. The CSA contents is the main parameter to explain the strength development and decreased drying shrinkage in the ATBC.

• Journal of the Korean Chemical Society
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• v.26 no.4
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• pp.235-246
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• 1982

The free radical polymerization and copolymerization of N-acetyl ${\alpha}$-aminoacrylic acid were investigated. From the result of kinetic investigation of N-acetyl ${\alpha}$-aminoacrylic acid in DMF at $60^{\circ}C$, a rate equation of $R_p$ = $k_p[M]^{0.97}[I]^{0.59}$ was obtained. The overall activation energy for the polymerization was found to be 25.2 kcal/mole. Copolymerization of N-acetyl ${\alpha}$-aminoacrylic acid with acrylic acid and styrene was carried out for the determination of monomer reactivity ratios. The monomer reactivity ratios for the monomer pairs determined at 70.0{\pm}0.1^{\circ}C$ using benzoyl peroxide as an initiator are; $r_1$(N-acetyl ${\alpha}$-aminoacrylic acid) = 0.49, $r_2$(acrylic acid) = 1.41, $r_1$(N-acetyl ${\alpha}$-aminoacrylic acid) = 0.44, $r_2$(styrene) = 0.91. The values of Alfrey-Price's Q and e parameters for N-acetyl ${\alpha}$-aminoacrylic acid were calculated to be 0.51 and 0.16 for the both systems. Differential thermal analysis and thermogravimetry showed that acrylic acid copolymers have poorer thermal stability as compared with the homopolymer of N-acetyl ${\alpha}$-aminoacrylic acid.

• Bulletin of the Korean Chemical Society
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• v.32 no.4
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• pp.1165-1169
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• 2011

Second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of 2,4-dinitrophenyl phenyl thionocarbonate 4 with a series of Z-substituted pyridines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plot for the reactions of 4 exhibits downward curvature (i.e., ${\beta}_1$ = 0.21 and ${\beta}_2$ = 1.04), indicating that the reactions proceed through a stepwise mechanism with a change in rate-determining step. It has been found that 4 is less reactive than its oxygen analogue, 2,4-dinitrophenyl phenyl carbonate 3, although the thionocarbonate is expected to be more electrophilic than its oxygen analogue. The $pK_a$ at the center of the Br${\o}$nsted curvature, defined as $pK_a^o$, has been analyzed to be 6.6 for the reactions of 4 and 8.5 for those of 3. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio has revealed that the reactions of 4 result in smaller $k_1$ values but larger $k_2/k_{-1}$ ratios than the corresponding reactions of 3. The larger $k_2/k_{-1}$ ratios have been concluded to be responsible for the smaller $pK_a^o$ found for the reactions of 4.

• Transactions of the Korean hydrogen and new energy society
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• v.23 no.5
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• pp.530-537
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• 2012

This work experimentally investigates that Diesel-DME blended fuel influences combustion characteristics and emissions (NOx, CO, HC, smoke) in a single-cylinder DI diesel engine. Diesel is used as a main fuel and DME is blended for the use of its quick evaporating characteristics. Diesel and DME are blended by the method of weight ratio. Weight ratios for Diesel and DME are 95:5 and 90:10 respectively and the both ratios have been used altogether in blended fuel. The experiments are conducted in this study single cylinder engine is equipped with common rail and injection pressure is 700 bar at 1200 rpm. The amount of injected fuels is adjusted to obtain the fixed input calorie value as 972.2 J/cycle in order to compare with the fuel conditions. DME is compressed to 15 bar by using nitrogen gas thus it can be maintained the liquid phase. In this study, different system compared others paper is common rail system, also there is combustion and emission about compared DME and diesel fuel. It is expected to be utilized about blended fuel.

• Journal of the Korean Applied Science and Technology
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• v.19 no.1
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• pp.33-42
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• 2002

Copolymerization of ${\alpha}$-Methylstyrene(AMS) with Acrylonitrile(AN) was carried out with benzoylperoxide(BPO) as an initiator in toluene at $80^{\circ}C$ in a continuous stirred tank reactor. Reaction volume and residence time were 0.6 liters and 3 hours, respectively. The monomer reactivity ratios, $r_{AMS}$ and $r_{AN}$ determined by both the Kele$T{\"{u}}d\"{o}s$ method and the Fineman-Ross method were $r_{AMS}$=0.16(0.14), $r_{AN}$=0.04(0.06). The cross-termination factor ${\Phi}$ of the copolymer over the entire AMS composition ranged from 0.75 to 0.92. The ${\Phi}$ factors of poly(AMS-co-AN) were increased with increasing AMS content. The simulated conversions and copolymerization rates were compared with the experimental results. It was observed that the average time to reach dynamic steady-state was three times the residence time.

• Macromolecular Research
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• v.15 no.4
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• pp.324-329
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• 2007

An octa-functional alkoxyamine initiator, with the 2,2,6,6-tetramethyl-l-piperidinyloxy (TEMPO) free radical, was synthesized based on resorcinarene, with its efficiency to initiate the nitroxide-mediated free radical copolymerization of styrene and methyl methacrylate (MMA) described. A difunctional analogue of this initiator was also synthesized, using resorcinol as the core molecule. The structures of the resulting initiators were confirmed by homolysis studies based on electron spin resonance spectroscopy and molecular modeling. The polymerization behavior and characteristics of the polymers obtained using these two initiators were also compared. Well-defined star-shaped and linear random copolymers, with low polydispersities and controlled molecular weights, were prepared. The efficiencies of these initiators towards copolymerization, as well as the parameters permitting the formation of well-defined polymers, were also investigated. The reactivity ratios were $r_a=0.42(a=styrene)\;and\;r_b=0.33(b=MMA)$ for the octa-functional initiator system and $r_a=0.45\;and\;r_b=0.39$ for the difunctional initiator system.

• Computers and Concrete
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• v.20 no.1
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• pp.77-84
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• 2017

Shirasu, a pyroclastic flow deposit, showed considerable performance as aluminosilicate source in geopolymer, based on past research. However, the polymerization reactivity was somewhat lower compared to the traditional fly ash based geopolymer even though the long-term strength was fairly good. The present study concentrates on the development of higher initial strength performance of Shirasu based geopolymer by utilizing ground granulated blast furnace slag as an admixture. Mortars with various mix proportions were adopted to study the effect of parametric changes on strength development along with the addition of slag in different percentages. A combination of sodium hydroxide and sodium silicate was used as alkaline activators considering parameters like molar ratios of alkali to geopolymer water and silica to alkali molar ratio. The mortars were cured at elevated temperatures under different curing conditions to analyze the effect on strength development. Compressive strength test, mercury intrusion porosimetry and X-ray powder diffraction were carried out to assess the strength performance and microstructure of slag-Shirasu based geopolymer. Based on the experimental study, it was observed that the initial and long-term strength development of Slag-Shirasu geopolymer were improved by the addition of slag.

• Applied Chemistry for Engineering
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• v.7 no.4
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• pp.661-669
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• 1996

Pt-Rh/NaY catalysts with various Pt/Rh ratios were prepared by an ion-exchange method and their characteristics were investigated by $^{129}Xe$-NMR and EXAFS. Both the $^{129}Xe$-NMR and EXAFS data indicate that the surface of PtRh bimetallic clusters was enriched with Rh atoms. The catalytic activities of these catalysts for conversion of CO, HC and $NO_x$ were measured by using simulated automobile engine exhausts under lean, rich and stoichiometric conditions. The Pt-Rh/NaY(Pt/Rh=1) catalyst exhibited the greatest reactive activity among the catalysts used in this study.

• Journal of the Korean Applied Science and Technology
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• v.33 no.4
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• pp.698-705
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• 2016

In this study, we have studied the polymerization of polyethylene wax using metallocene catalysts and its physical properties. Various polymerization conditions were tried for polymerization of polyethylene wax. We have evaluated hydrogen reactivity and studied on characteristics of polymerization effected by ligand structure of metallocene catalysts against Ziegler-Natta catalysts which are widely used for polymerization of polyethylene. We have also checked hydrogen used for chain transfer agent, molecular weight change and distribution by different ratios of ethylene gas. Finally, we suggest proper structure of metallocene catalysts for polymerization of polyethylene wax.