• Textile Coloration and Finishing
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• v.13 no.5
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• pp.24-24
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• 2001

Kinetics and mechanism for alkaline hydrolysis of C. I. Disperse Blue 79(B-79) which is 4-N, N-diacetoxyethyl-2-acylamino-5-ethoxy -2′-bromo-4′,6′-dinitroazobenzene were investigated. The color strength of B-79 in acetone/water solutions of various NaOH concentrations decreased continuously. The hydrolysis rate of B-79 increased with increasing alkali concentration and appeared following first order reaction. The observed rate constants for various concentrations of B-79 showed similar values, and B-79 was hydrolyzed by first order reaction for dye concentration. Therefore, it was confirmed that the overall reaction follow second order kinetics and proceed via S/sub n/2 reaction. From the study on kinetics and spectrometric analysis, it was proposed that the rate determining step of the hydrolysis reaction of B-79 is the nucleophilic substitution reaction - that is the reaction of the rapid attack of $OH^{-}$ on the carbon atom, which is in acceptor ring, adjacent to azo group to break the C-N bond. And it was also found that the final hydrolysis products of B-79 include both the acceptor ring in the form of sodium salt and the donor ring possessing 4-N,N-dihydroxyethyl group converted from 4-N,N-diacetoxyethyl group.

• Textile Coloration and Finishing
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• v.13 no.5
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• pp.312-319
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• 2001

Kinetics and mechanism for alkaline hydrolysis of C. I. Disperse Blue 79(B-79) which is 4-N, N- diacetoxyethyl -2- acylamino-5-ethos y -2'-bromo-4',6'-dinitroazobenzene were investigated. The color strength of B-79 in acetone/water solutions of various NaOH concentrations decreased continuously. The hydrolysis rate of B-79 increased with increasing alkali concentration and appeared following first order reaction. The observed rate constants for various concentrations of B-79 showed similar values, and B-79 was hydrolyzed by first order reaction for dye concentration. Therefore, it was confirmed that the overall reaction follow second order kinetics and proceed via $S_N2$ reaction. From the study on kinetics and spectrometric analysis, it was proposed that the rate determining step of the hydrolysis reaction of B-79 is the nucleophilic substitution reaction - that is the reaction of the rapid attack of OH- on the carbon atom, which is in acceptor ring, adjacent to auto group to break the C-N bond. And it was also found that the final hydrolysis products of B-79 include both the acceptor ring in the form of sodium salt and the donor ring possessing 4-N,N-dihydroxyethyl group converted from 4-N, N-diacetoxyethyl group.

• Computers and Concrete
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• v.20 no.3
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• pp.263-273
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• 2017

An experimental investigation is carried out on the failure mechanism of foam concrete with cold formed steel double C-Channels embedment. The foam concrete is made of cement and fly ash with a compressive strength between 9 and 24 MPa with different densities. Forty-eight tests have been carried out in four groups of specimens with various embedment depths of the steel in the concrete. Four modes of failure are observed, which include the independent failure of the C-Channels with and without a concrete block inside the channel as well as the combined failure of the two channels, and the failure of the extrusion block. A theoretical model has been developed to understand the failure process. The peak compressive force applied onto the C-Channels that causes failure is calculated. It is concluded that the failure involves independent slippage between two C-Channels, and the steel and the foam concrete blocks inside the C-Channels. A method to calculate the peak force is also developed based on the test results. The calculations also show that the shear strength of the foam concrete is about 8% of the compressive strength with ${\alpha}$ coefficient of 0.4 between the steel and concrete.

• Journal of the Earthquake Engineering Society of Korea
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• v.6 no.5
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• pp.45-51
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• 2002

The characteristics of nonlinear seismic behavior and failure mechanism of RC space frame in railroad viaducts have been studied by the numerical analysis in time domain. The structure concerned is modeled in 3 dimensional extent and the RC frame elements consisting of fibers are employed for the columns. The fibers are characterized as RC zone and PC one to distinguish the different energy release after cracking resulted from the bond characteristic between concrete and re-bar. Due to the deviation of the mass center and the stiffness center of the entire structure the complex behavior is shown under seismic actions. The excessive shear force is concentrated on the column beside flexible one relatively, which leads to the failure of bridge concerned.

• International Journal of Concrete Structures and Materials
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• v.3 no.2
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• pp.119-126
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• 2009

This paper provides a brief summary of the performance of an innovative slip hardening twisted steel fiber in comparison with other fibers including straight steel smooth fiber, high strength steel hooked fiber, SPECTRA (high molecular weight polyethylene) fiber and PVA fiber. First the pull-out of a single fiber is compared under static loading conditions, and slip rate-sensitivity is evaluated. The unique large slip capacity of T-fiber during pullout is based on its untwisting fiber pullout mechanism, which leads to high equivalent bond strength and composites with high ductility. Due to this large slip capacity a smaller amount of T-fibers is needed to obtain strain hardening tensile behavior of fiber reinforced cementitious composites. Second, the performance of different composites using T-fibers and other fibers subjected to tensile and flexural loadings is described and compared. Third, strain rate effect on the behavior of composites reinforced with different types and amounts of fibers is presented to clarify the potential application of HPFRCC for seismic, impact and blast loadings.

• Journal of Photoscience
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• v.3 no.2
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• pp.91-93
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• 1996

In connection with our interest on the photochemical properties of heteroaryl halides, which are currently the subject of heterocyclic ring formation and haloarene degradation, we have studied the photochemistry of the haloarene linked to N-heteroarene compounds. Imidazo[5,1-a]isoindole was synthesized from N-(ochlorobenzyl)imidazole or N-(o-bromobenzyl) imidazole in acidic aqueous solution or acetonitrile via the intramolgcular photocyclization (Table 1). This type of reaction provides the synthetic methods for 5- and 6-membered polyheteroatomic heterocyclic ring compounds. However, the reaction mechanism for the intramolecular photocyclization of haloarene tethered heteroarenes has not yet been established. Grimshaw et al. suggested a mechanism for homolyric carbonhalogen bond fission assisted by radical complexation to explain their results in the photocyclization of 5-(2-chlorophenyl)-1,3-diphenylpyrazole. They also reported the detection of acyclohexadienyl intermediate involved in the above reaction. Park et al. reported several transient 'intermediates involved in the laser flash photolysis of N-(o-halobenzyl) pyridinium and N-benzyl-2-halopyridinium salts. Thus we performed the laser flash photolysis study on the photocyclization reaction of N-(o-chlorobenzyl) imidazole to identify the intermediate species involved in the reaction. Here, we report on the preliminary results in the photocyclization reaction of N-(o-halobenzyl)imidazole through the detection of reaction intermediates.

• Bulletin of the Korean Chemical Society
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• v.31 no.11
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• pp.3279-3282
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• 2010

The reaction rates of 4-X-2,6-dinitrochlorobenzenes (X = $NO_2$, CN, $CF_3$) with Y-substituted benzylamines (Y = p-$OCH_3$, p-$CH_3$, H, p-Cl) in MeOH-MeCN mixtures were measured by conductometry at $25^{\circ}C$. It was observed that the rate constant increased in the order of X = $NO_2$ > CN > $CF_3$ and in the order of Y = p-$OCH_3$ > p-$CH_3$ > H > p-Cl. When the solvent composition was varied, the rate constant increased in the order of 100% MeOH < 50% (v/v) MeOH-MeCN < 100% MeCN. These results may be ascribed to the formation of hydrogen bonds between the alcoholic hydrogen and nitrogen of benzylamines in groud state (GS). We conclude that the reaction takes place via $S_NAr$ base on the transition state parameters ${\rho}x$, ${\rho}Y$, $\beta_{nuc}$, and solvent effects.

• Journal of the Korean Applied Science and Technology
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• v.10 no.2
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• pp.73-80
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• 1993

The hydrolysis reaction kinetics of 2-thienyl chalcone derivatives $[II]{\sim}[V]$ was investigated by ultraviolet spectrophotometery in 20% dioxane-$H_2O$ at $25^{\circ}C$ and the structure of these compounds were ascertained by means of ultraviolet, infrared and NMR spectra. The rate equations which were applied over a wide pH range(pH $1.0{\sim}13.0$) were obtained. The substituent effects on 2-thienyl chalcone derivatives$[II]{\sim}[V]$ were studied, and the hydrolysis were facilitated by electron attracting groups. On the basis of the rate equation, substitutent effect and final product, the plausible hydrolysis reaction mechanism was proposed : At pH $1.0{\sim}9.0$, not relevant to the hydrogen ion concentration, neutral $H_2O$ molecule competitvely attacked on the double bond. By contraries, above pH 9.0, it was proportional to concentration of hydroxide ion.

• Journal of the Korean Applied Science and Technology
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• v.12 no.1
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• pp.35-41
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• 1995

The Hydrolysis kinetics of Benzoyl Styrene Derivatives[I]${\sim}$[IV] was investigated by ultraviolet spectrophotometery in 5% dioxane-$H_2O$ at $40^{\circ}C$. The structure of these compounds were ascertained by means of ultraviolet, melting point, IR and NMR spectra. The rate equations which were applied over a wide pH range (pH $1.0{\sim}13.0$) were obtained. The substituent effects on Benzoyl styrene derivatives[I]${\sim}$[IV] were studied, and the hydrolysis were facilitated by electron attracting groups. On the basis of the rate equation and substitutent effect and final product, the plausible hydrolysis reaction mechanism was proposed: At pH 1.0${\sim}$pH 9.0, not relevant to the hydrogenl ion concentration, neutral $H_2O$ molecule competitively attacked on the double bond. By contrary. Above pH 9.0, It was proportional to concentration of hydroxidel ion.

• Bulletin of the Korean Chemical Society
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• v.26 no.6
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• pp.935-938
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• 2005

Nucleophilic addition reactions of benzylamines (BA; $XC_6H_4CH_2NH_2$) to $\alpha-cyano-\beta$-phenylacrylamides (CPA; $YC_6H_4CH=C(CN)CONH_2$) have been investigated in acetonitrile at 25.0 ${^{\circ}C}$. The rate is first order with respect to BA and CPA and no base catalysis is observed. The addition of BA to CPA occurs in a single step in which the addition of BA to $C_{\beta}$ of CPA and proton transfer from BA to $C_{\alpha}$ of CPA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($\rho_X$) and Bronsted ($\beta_X$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the crossinteraction constant, $\rho_XY$ (= −D0.26), is comparable to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($k_H/k_D\;{\gt}$ 1.0) and relatively low ${\Delta}H^{\neq}$ and large negative ${\Delta}S^{\neq}$ values are also consistent with the mechanism proposed.