• Bulletin of the Korean Chemical Society
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• v.12 no.3
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• pp.301-303
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• 1991

The rate constants for the nucleophilic addition of thiophenol to $\alpha$, N-diphenylnitrone and it's derivatives (p-$OCH_3$, p-Cl, p-$NO_2$) were determined from pH 3.0 to 13.0 by UV spectrophotometry and rate equations which can be applied over a wide pH range were obtained. On the basis of rate equation, general base and substituent effect a plausible addition mechanism of thiophenol to ${\alpha}$, N-diphenylnitrone was proposed: At high pH, the addition of sulfide ion to carbon-nitrogen double bond was rate controlling, however, in acidic solution, reaction was proceeded by the addition of thiophenol molecule to carbon-nitrogen double bond after protonation at oxygen of ${\alpha}$, N-diphenylnitrone.

• Journal of the Korean Chemical Society
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• v.54 no.5
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• pp.556-566
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• 2010

A new kinetic spectrophotometric method is developed for the measurement of Mn(II) in natural water samples. The method is based on the catalytic effect of Mn(II) with the oxidation of Gallocyanin by $KIO_4$ using nitrilotriacetic acid (NTA) as an activation reagent at 620 nm. The optimum conditions obtained are $4.00{\times}1^{-5}\;M$ Gallocyanin, $KIO_4$, $1.00{\times}10^{-4}\;M$ NTA, 0.1 M HAc/NaAc buffer of pH = 3.50, the reaction time of 5 min and the temperature of $30^{\circ}C$. Under the optimum conditions, the proposed method allows the measurement of Mn(II) in a range of $0.1\;-\;4.0\;ng\;mL^{-1}$ and with a detection limit of down to $0.025\;ng\;mL^{-1}$. The recovery efficiency in measuring the standard Mn(II) solution is in a range of 98.5 - 102%, and the RSD is in a range of 0.76 - 1.25%. The newly developed kinetic method has been successfully applied to the measurement of Mn(II) in both some environmental water samples and certified standard reference river water sample, JAC-0031 with satisfying results. Moreover, few cations and anions interfere with the measurement of Mn(II). Compared with the other catalytic-kinetic methods and instrumental methods, the proposed kinetic method shows fairly good selectivity and sensitivity, low cost, cheapness, low detection limit and rapidity. It can easily and successfully be applied to the real water samples with relatively low salt content and complex matrices such as bottled drinking water, cold and hot spring waters, lake water, river water samples.

• Journal of the Korean Chemical Society
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• v.38 no.12
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• pp.885-890
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• 1994

Kinetics of electrochemical polymerization of aniline on a tungsten electrode in acidic aqueous solution was studied by means of cyclic voltammetry and kinetic measurements of anodic oxidation. Aniline molecule appeared to be intially oxidized via two-electron transfer to produce oxidized deprotonated aniline ion, which subsequently undergoes nucleophilic attack to the parent aniline and results in head to tail coupling to yield a dimerized species. But, being contrary to the case of Pt electrode, the propagation of polymerization occured through attack of the monomer by the oxidized aniline monomer to polymer. The growth rate of polyaniline was slow in comparison with the growth on Pt electrode. The degradation products were confirmed to be not p-benzoquinone(BQ) but p-phenylenediamine(p-PDA) by spectrophotometry, which agrees with the fact that oxidation of p-PDA was not observed below 1.0 V.

• Journal of the Korean Applied Science and Technology
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• v.8 no.1
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• pp.1-7
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• 1991

The kinetic of hydrolysis for cinnamylidene aniline derivatives has been investigated by ultraviolet spectrophotometry in 20% (v/v) dioxane - $H_2O$ at $25^{\circ}C$. A rate equation which can be applied over wide pH range was obtained. The substituent effects on cinnamylidene aniline derivatives were studied and the hydrolysis was facilitated by electron attracting group. Final products of the hydrolysis were cinnamaldehyde and aniline. From the rate equation, substituent effect and final products, the hydrolysis of cinnamylidene aniline derivatives was initiated by the neutral molecule of $H_2O$ which does not dissociate at below pH 9.0${\sim}$12.0, but proceeded by the hydrogen ion at above pH 5.0${\sim}$9.0.

• Journal of the Korean Chemical Society
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• v.26 no.6
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• pp.407-413
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• 1982

The rate constants of the nucleophilic addition of cysteine to 3,4-methylenedioxyphenylmethylene malononitrile were determined by UV Spectrophotometry and a rate equation which can be applied over wide pH range was obtained. On the basis of rate equation, it may be concluded that the rate constants were dependent upon only the concentration of hydroxide ion above pH 9.0, however, below pH 6.0, the reaction were initiated by the addition of neutral cysteine molecule to carbon-carbon double bond and at pH 7.0~9.0, the addition of a neutral cysteine molecule and it's anion occurred competitively.

• Journal of the Korean Applied Science and Technology
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• v.10 no.2
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• pp.65-72
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• 1993

The kinetics of the addition of thiourea to cinnamenylisophorone derivatives(X : H, p-Br, $p-CH_3$ $m-CH_3$, $p-OCH_3$) was investigated using ultraviolet spectrophotometry in 20%(v/v) dioxane-$H_2O$ at $25^{\circ}C$. A rate equation which can be applied over wide pH range(pH $1.0{\sim}13.0$) was obtained. In order to investigate the substituent effects of cinnamenylisophorone derivatives. Hammett constant was plotted. As the result, the rate of uncleophilic addition of thiourea to cinnamenylisophorone derivatives was facilitated by electron donating group. It was found that addition of neutral thiourea which was not dissociated at the pH $1.0{\sim}9.0$ was proceeded, the reaction was proceeded by addition of dissociated anion of thiourea above the pH 10.0. On the basis of this kinetic study, the reaction mechanism of nucleophilic addition of thiourea was investigated.

• Applied Chemistry for Engineering
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• v.4 no.4
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• pp.672-682
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• 1993

2, 4-Heptadione(abbreviated to 24HTD) was synthesized from methylpropyl ketone and ethyl acetate with sodium amide, and the equilibrium and the kinetic characteristics of copper extraction by 24HTD-chloroform were investigated. Equilibrium constants such as the dissociation constant and the distribution coefficient of 24HTD and the stability constant of the 24HTD-Cu chelate were evaluated from the spectrophotometry, and the overall equilibrium constant of the extraction was also determined. The extracted species of the 24HTD-Cu chelate was found to be $CuR_2$ and the initial rate of the extraction of coupper by 24HTD in chloroform was expressed by $R_0=k[\bar{HR}]([Cu^{2+}]/[H^+])^{0.5}$.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.127-134
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• 1989

The rate constants of the nucleophilic addition reaction of 3-mercaptopropionic acid to the ${\beta},\;{\beta}$-diethoxycarbonylstryene derivatives (H, p-OCH$_3$, 3,4,5-(OCH$_3)_3$, 3,4-methylenedioxy) were determined by ultraviolet spectrophotometry, and rate equation which could be applied over a wide pH range was obtained. On the basis of pH-rate profile and the presence of general base catalysis, a plausible mechanism of this addition reaction was propound:Below pH 6.0 the reaction was initiated by the addition of neutral 3-mercaptopropionic acid molecule, and in the range of pH 6.0∼8.0, a neutral 3-mercaptopropionic acid molecule and a sulfide anion competitively attacked to the double bond. Above pH 8.0, the reaction proceeded through the addition of a sulfide anion.

• Journal of the Korean Applied Science and Technology
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• v.8 no.2
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• pp.161-167
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• 1991

The kinetics of hydrolysis of cinnamenylisophorone derivatives (${rho}-H,\;{rho}-Br,\;P-Cl,\;{rho}-OCH_3$) was investigated using ultraviolet spectrophotometry in 20%(v/v) dicxane-$H_2O$ at 25$^{\circ}C$. A rate equation which can be applied over wide pH range (pH $1.0{\sim}13.0$) was obtained. In order to investigate the substituent effects on cinnarnenylisophorone derivatives, Hammett constant was plotted. As the result, the rate of hydrolysis of cinnamenylisophorone derivatives was facilitated by electron donating group. Final products of the hydrolysis were benzaldehyde and isophorone, From the measurement of reaction rate constant according to pH changes, substituent effect, and final products, it was found that the hydrolysis of cinnarnenylisophorone derivatives was initiated by the neutral $H_2O$ molecule which does not dissociated at below pH 9.0, and in the range of pH $9.0{\sim}11.0$ this reaction occurs by $H_2O$ or hydroxide ion competitively, but proceeded by the hydroxide ion above pH 11.0. On the basis of this kinetic study, the reaction mechanism of the hydrolysis of cinnamenylisophorone derivatives was proposed.

• Bulletin of the Korean Chemical Society
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• v.19 no.6
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• pp.671-676
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• 1998

The formation and dissociation rates of $Ce^{3+}$ Complexes of the 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-NN', N",N"'-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-N,N',N",N"'-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-N,N',N",N"'-tetrapropionic acid (3) have been measured by the use of stopped-flow spectrophotometry. Observations were made at 25.0±0.1 ℃ and at an ionic strength of 0.10 M $NaClO_4$. The complexation of $Ce^{3+}$ ion with 1 and 2 proceeds through the formation of an intermediate complex $(CeH_3L^{2+})^*$ in which the $Ce^{3+}$ ion is incompletely coordinated. This may then lead to be a final product in the rate-determining step. Between pH 4.76 and 5.76, the diprotonated $(H_2L^{2-})$ from is revealed to be a kinetically active species despite of its low concentration. The stability constants $(logK(CeH_3L^{2+}))$ and specific water-assisted rate constants $(k_{OH})$ of intermediate complexes have been determined from the kinetic data. The dissociation reactions of $Ce^{3+}$ complexes of 1, 2, and 3 were investigated with $Cu^{2+}$, ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed contributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on the dissociation rate of $Ce^{3+}$ complexes is discussed in terms of the side-pendant arms and the chelate ring sizes of the ligands.