• Journal of the Korean Chemical Society
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• v.18 no.4
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• pp.259-266
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• 1974

Isotopic experiments using $H_2O^{18}$ on the oxidation of V(III) in acid perchlorate by molecular oxygen were performed in the range pH 1.0 to 3.0. At pH < 2, where a rate equation of the form TEX>$ -\frac{d[V(III)]}{dt}=k_1\frac{[O_2][V(III)]}{[H^+]}$ is adequate, the tracer study clearly indicated that all the product vanadyl ion's ($VO^{2+}$) oxygen originated from the molecular oxygen. At pH > ~2, where a different rate expression of the form $-\frac{d[V(III)]}{dt}=K_2\frac{[O_2][V(III)]^2}{[Ht]^2}$is required, the isotopic experiment showed that half the vanadyl oxygen originated from the molecular oxygen. Considering the results of the isotopic study, a mechanism for the V(Ⅲ)-O2 reaction at pH < ~2, may be suggested as follows: The tracer results at pH > ~2 imply that the rate determining step may be $$ V_2(OH)_2^{4+} + O_2 \rightarrow 2VO^{2+} + H_2O_2$$ followed by $$V_2(OH)_2^{4+} + H_2O_2 \rightarrow 2VO^{2+} + 2H_2O$$ after establishing the equilibria V^{3+} + H_2O \leftrightarrow VOH^{2+} + H^+, and 2VOH^{2+}\leftrightarrow V_2(OH)_2^{4+}$$

• Applied Biological Chemistry
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• v.3
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• pp.1-7
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• 1962

In order to study the rate control step in the protein metabolic course of the chlorophyll formation, the transaminase activities which are obtained freely in the extracts of cotyledons of germinating peas at the light and the dark places, are measured in Beckman mopel D.U, spectrophoto meter at 490 mu. In this case, of two enzymatic reaction products; oxalacetic acid and pyruvic acid, the former is converted to pyruvic acid by aniline citrate and after each pyruvate phenyl hydrazones are extracted by toluenes: when this is treated with strong alcoholic alkali, a colored hydrazone is formed and it is measured by above apparatus. The estimated G.O.T. and G.P.T. in the germinated cotyledons at dark and light places considerably differ in their activities; G.O.T. and G.P.T. activities which are formed at the light are more increased than at the dark and also they differ in their rates through germination, though G.O.T. activity increment is smoothly but that of G.P.T. is more sharply, and they are considered to be directly affected to the chlorophyll formation and indirectly to the growth. G.O.T. and G.P.T. in each fractions of cell in the cotyledons should be formed by dissociation of zymogens in the microsomal fractions and it seems to promoted by light. In the formation of the chlorophyll, the protein metabolism occurred mainly in the microsomal fractions and the rate determining step is found at the point where the zymogene that is able to produce G.P.T. is activated, and this activation is promoted by light as noted above.

• Applied Chemistry for Engineering
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• v.4 no.1
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• pp.82-93
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• 1993

To extract the tungsten component from the scheelite by the chlorination process, effects of major variables such as the reducing agent, reaction temperature, reaction time, flow rate of the $Cl_2$ gas, and the particle size of the sample, were examined in the batch-boat system. The optimum conditions for this chlorination process were as follows ; reaction temperature above $700^{\circ}C$, carbon weight ratio to the scheelite 0.08, reaction time 20 min, flow rate of the $Cl_2$ gas $0.6{\ell}/min$, particle size of scheelite ore -200 mesh. Under the above conditions, 99% of tungsten component was extracted from scheelite ore. The diffusion step and chemical reaction step were the rate-determining steps at high and low temperature, respectively. Activation energy was 7.98kcal/mol at high temperature region and 31.2kcal/mol at low temperature one.

• Bulletin of the Korean Chemical Society
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• v.34 no.10
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• pp.2983-2988
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• 2013

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of 4-chloro-2-nitrophenyl X-substituted-benzoates (1a-1h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 1a-1h with piperidine consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X $ = 1.25 and r = 0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step (RDS) but is caused by ground-state stabilization through resonance interactions for substrates possessing an electron-withdrawing group in the benzoyl moiety. The Br${\o}$nsted-type plot for the reactions of 4-chloro-2-nitrophenyl benzoate (1d) with a series of cyclic secondary amines curves downward with ${\beta}_2$ = 0.85, ${\beta}_1$ = 0.24, and $pK_a{^o}$ = 10.5, implying that a change in RDS occurs from the $k_2$ step to the $k_1$ process as the $pK_a$ of the conjugate acid of the amine exceeds 10.5. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio associated with the reaction of 1d reveals that $k_2$ is dependent on the amine basicity, which is contrary to generally held views.

• Bulletin of the Korean Chemical Society
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• v.29 no.8
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• pp.1459-1463
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• 2008

Second-order rate constants (kN) have been measured spectrophotometrically for reactions of 3,4-dinitrophenyl 2-thiophenecarboxylate (2) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % dimethyl sulfoxide at 25.0 ${^{\circ}C}$. The Brønsted-type plot exhibits a downward curvature for the aminolysis of 2. The curved Brønsted-type plot is similar to that reported for the corresponding reactions of 2,4-dinitrophenyl 2- thiophenecarboxylate (1). The reactions of 1 and 2 have been suggested to proceed through the same mechanism, i.e., through a zwitterionic tetrahedral intermediate ($T^{\pm}$) with a change in the rate-determining step. Substrate 2 is less reactive than 1 toward weakly basic amines (e.g., $pK_a$ < 10.4) but becomes more reactive as the basicity of amines increases further. Dissection of kN into the microscopic rate constants has revealed that the reaction of 2 results in a smaller $k_2/k_{-1}$ ratio but larger $k_1$ than the corresponding reaction of 1. Steric hindrance exerted by the ortho-nitro group has been suggested to be responsible for the smaller $k_1$ value found for the reactions of 1.

• The Journal of Sustainable Design and Educational Environment Research
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• v.16 no.2
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• pp.1-9
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• 2017

Defect dispute in apartment building has become a debating social issue. The system of defect lawsuit and the conciliation process are applicable to solve defect problems in South Korea. Among various defects, painting work defect is a critical issue because it requires large area works and entails a lot of cost. Accordingly, disputes on work procedure and cost calculation are argued oftenly between residents and housing providers. This study reviewed detailed main issues of painting work and propose relevant systems and standards. In this analysis, the main issues are categorized into pre-works, main work, and others. The most recent cases are compared and analyzed for each issue. After the analysis, following conclusions are obtained, (1) In defect lawsuit system, even though surface treatment work in pre-work step is part of main work, it has been separated and regarded as a separate work. (2) Although the main painting work are not significantly different from two systems, it is still necessary to achieve a consensus to close the gap in the methodology of painting area calculation and determining whole painting or partial painting. (3) In addition, unlike the profit rate of general construction works, that of painting work remained the maximum rate and additional charge rate for works carried out in higher place are different among cases. Therefore, it is determined that establishing consistent standards is urgent.

• 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.

• Microbiology and Biotechnology Letters
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• v.24 no.4
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• pp.493-499
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• 1996

Lactan gum produced by Rahnella aquatilis is a high viscous, anionic polysaccharide and has shear thinning behaviour. Lactan gum yield and cencentration was greater on disaccharide such as lactose and sucrose than on monosaccharides such as glucose and galactose. When initial carbon source concentration was 45g/l of sucrose of lactose, the microorgnisms produced 28 g/l and 27 g/l of lactan, respectively with a yield more than 60%. $\beta$-Galactosidase, hydrolyzing lactose into galactose and glucose, was induced by lactose or galactose. When initial corbon source was 45 g/l of mixed carbon I (glucose:galactose=1:1), lactan gum concentaration was higher than that from 45 g/l of monosaccharide (glucose pf galactose) but was similar to the result from 45 g/l of lactose. Therefore, lactose hydrolysis reaction by $\beta$-galactosidase does not seem to be a rate determining step in lactan gum biosynthesis. When initial carbon source was 45 g/l of mixed carbon II (glucose:fructose=1:1). total carbon source consumption rate was slower than that from sucrose, but glucose consumption rate was faster than that from fructose.

• Bulletin of the Korean Chemical Society
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• v.24 no.9
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• pp.1251-1255
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• 2003

Second-order rate constants have been determined spectrophotometrically for the reaction of phenyl 4-nitrophenyl carbonate with a series of primary amines in $H_2O$ containing 20 mol % DMSO at 25.0 ${\circ}$C. The Bronsted-type plot is linear with a ${\beta}_{nuc}\;0.69 {\pm} 0.04$, which is slightly smaller than the ${\beta}_{nuc}$ values for the reactions of 4-nitrophenyl acetate ( $\beta_{nuc}= 0.82 {\pm} 0.03$) and benzoate ( $\beta_{nuc} = 0.76 {\pm} 0.01$), indicating that the reaction proceeds through a tetrahedral zwitterionic intermediate $T^{\pm}$. The carbonate is more reactive than the corresponding acetate and benzoate. The changing Me (or Ph) to PhO has resulted in a decrease in the ${\beta}_{nuc}$ value without changing the reaction mechanism but an increase in the reactivity. The electronic effect of the substituent in the nonleaving group appears to be responsible for the enhanced reactivity of the carbonate compared with the corresponding acetate and benzoate.