• 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 Electrochemical Society
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• v.7 no.3
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• pp.138-142
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• 2004

The polyaniline films of emeraldine base (EB) and leucoemeraldine base (LEB) form doped with cam-phorsulfonic acid (CSA) were prepared by casting the mixed solution of chloroform and m-cresol on ITO (indium tin oxide) electrode. By analyzing UV-vis spectra of the mixed solutions, the effects of the secondary doping by m-cresol were obtained. And the conductivity of polyaniline film was increased with increasing m-cresol content. As the results of analyzing cyclic voltammograms, it was known that the redox peak currents of polyaniline electrode prepared from LEB were larger and more reversible than those of polyaniline eleclrodes prepared from EB. The charge transfer resistances $(R_{ct})$ of polyaniline electrodes were reduced with increasing m-cresol content, showing smaller Rct for LEB/CSA than EB/CSA.

• Korean Chemical Engineering Research
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• v.56 no.4
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• pp.474-478
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• 2018

For process safety, fire and explosion characteristics of combustible materials handled at industrial fields must be available. The combustion properties for the prevention of the accidents in the work place are flash point, fire point, explosion limit, and autoignition temperature (AIT) etc.. However, the combustion properties suggested in the Material Safety Data Sheet (MSDS) are presented differently according to the literatures. The accurate combustion properties are necessary to safely treatment, transportation and handling of flammable substances. In the chemical industries, n-ethylaniline which is widely used as a raw material of intermediate products and rubber chemicals was selected. For safe handling of n-ethyl aniline, the flash point, the fire point and the AIT were measured. The lower explosion limit (LEL)of n-ethylaniline was calculated using the lower flash point obtained in the experiment. The flash points of n- ethylaniline by using the Setaflash and Pensky-Martens closed-cup testers measured $77^{\circ}C$ and $82^{\circ}C$, respectively. The flash points of n-ethylaniline using the Tag and Cleveland open cup testers are measured $85^{\circ}C$ and $92^{\circ}C$, respectively. The AIT of the measured n-ethyl aniline by the ASTM E659 apparatus was measured at $396^{\circ}C$. The LEL of n-ethylaniline measured by Setaflash closed-cup tester at $77^{\circ}C$ was calculated to be 1.02 vol%. In this study, it was possible to predict the LEL by using the lower flash point of n-ethylaniline measured by closed-cup tester. The relationship between the ignition temperature and the ignition delay time of the n-ethylaniline proposed in this study makes it possible to predict the ignition delay time at different ignition temperatures.

• Microbiology and Biotechnology Letters
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• v.31 no.1
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• pp.25-31
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• 2003

Delftia acidovorans 51-A isolated from river water degrades aniline. In order to clone genes involved in aniline degradation, transposon Tn5-B20 was inserted into the strain 51-A to generate a mutant strain 10-4-2 that cannot utilize aniline as a carbon source. The mutant strain was not an auxotroph but could not degrade aniline. Southern hybridization analysis indicated that the transposon was inserted into the mutant bacterial DNA as a single copy. Flanking DNA fragment of Tn5-B2O insertion was cloned and sequenced. DNA sequence analysis revealed three ORFs encoding TdnQ, TdnT, and TdnA 1 that arc responsible for catechol formation from aniline through oxidative deamination. The analysis also confirmed that Tn5-B2O was inserted at the immediate downstream of tdnA1. The result suggests that the transposon insertion behind tdirA1 disrupted the pathway of the catechol formation from aniline, resulting in the mutant phenotype, which cannot degrade aniline. A large plasmid over 100-kb in size was detected from D. acidovorans 51-A and Southern hybridization analysis with Tn5-B2O probe showed that the transposon was inserted on the plasmid named pTDN51. Our results indicated that the tdn genes on pTDN51 of D. acidovorans 51-A are involved in aniline degradation.

• Korean Chemical Engineering Research
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• v.40 no.6
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• pp.729-734
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• 2002

In this study, the polyaniline films of emeraldine base(EB) and lucoemeraldine base(LEB) form chemically doping with poly(sodium-4 styrenesulfonate, PSS) were prepared by casting the mixed solution of chloroform and m-cresol on ITO(indium tin oxide) electrode. By analyzing UV-vis spectra of the mixed solutions, the effects of the secondary doping by m-cresol were obtained. And the conductivity of polyaniline film was increased with increasing m-cresol content. The results suggest that the improvement of conductivity obtained by secondary doping results primarily from interaction of polyaniline and m-cresol. As the results of analyzing cyclic voltammograms, it was known that the redox peak currents of polyaniline electrode prepared from LEB were larger and more reversible than those of polyaniline electrodes prepared from EB. The charge transfer resistances($R_{ct}$) of polyaniline electrodes were reduced with increasing m-cresol content, and LEB/PSS electrodes were smaller than EB/PSS electrodes. This result agrees to the analysis of the redox peak current of cyclic voltammograms. The solution resistance and the capacity of electrical double layer almost unchanged in all prepared polyaniline electrodes. It was confirmed that solution resistance was independent of frequency factor in AC impedance spectra. Also the polyaniline film doping with PSS was revealed pseudo n-type characteristics of conducting polymer.

• Applied Chemistry for Engineering
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• v.20 no.1
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• pp.75-79
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• 2009

The ratio of aniline dimer (p-aminodiphenylamine), which is a nucleation site of chain growth in a chemical polymerization of aniline monomer, to aniline monomer was controlled to synthesize polyaniline with the molecular weight ($M_w$) between 10000 and 20000 g/mol. The result of OCP measurement showed that the reaction rate of polymerization was increased as the mole ratio of dimer was increased. The increase in the molar ratio of dimer resulted in the shift of absorption wavelength of polyaniline to the short wavelength region on measurement of UV/Vis and the decrease of molecular weight on the measurement of GPC.

• Journal of the Korean Chemical Society
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• v.19 no.6
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• pp.449-453
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• 1975

Substituent effect of the leaving groups of the reaction of benzyl arenesulfonate with dimethylanilines in acetone at $35^{\circ}C$ was obtained with the following results. 1. Substituent effect of the leaving groups was not variable when changed from pyridine to N,N-dimethylaniline in nucleophile 2.In acetone, the Hammett ${\sigma}$ constant of p-MeO of the leaving group was -0.35. 3. The weaker the nucleophilicity in dimethylaniline, the stronger the movement of electron from N to C, and the cleavage of the C${\ldots}$0 bond in transition state proceeds.

• Journal of the Korean Chemical Society
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• v.19 no.3
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• pp.156-162
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• 1975

Rates of reactions of methanesulfonyl chloride with various substituted anilines have been measured in methanol. Substituent effects in aniline are found to be linearly correlated with pKa(Bronsted relation with ${\beta}$ = 0.84) and ${\rho}$(Hammett equation with ${\rho}$ = -2.46) respectively. The results are interpreted in terms of degree of bond-formation at the transition state, which was found to have progressed relatively further. The rates for o-methylaniline deviated from the Bronsted plot established by meta and para substituted anilines because of a steric effect of ortho position in aniline. Activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ have also been determined. The enthalpy of activation showed a regular variation in that electron donating substituents in the p-substituted aniline decrease ${\Delta}H^{\neq}$ and increase the negative value of ${\Delta}S^{\neq}$.

• Journal of the Korean Chemical Society
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• v.35 no.5
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• pp.480-486
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• 1991

The solubilities of ethyl bromide in aniline and o-chloroaniline have been measured at 5, 15$^{\circ}$ and 25$^{\circ}$C in the presence and the absence of gallium bromide. When gallium bromide does not exist in the system, the solubility of ethyl bromide in o-chloroaniline is greater than in aniline, indicating a stronger interaction of ethyl bromide with o-chloroaniline than that with aniline. It could be thought that ethyl bromide forms unstable complex with gallium bromide in the presence of gallium bromide in the system. This complex has been assumed in various ways and evaluated, that instability constant (K value) is relatively constancy under the assumption of 1 : 1 complex, $C_2H_5Br{\cdot}GaBr_3$. Therefore, the complex forms the following equilibrium in the solution: $C_2H_5Br{\cdot}GaBr_3\;{\rightleftharpoons}\;C_2H_5Br +1/2Ga_2Br_6$ The instability of the complex of ethyl bromide with gallium bromide is compared with similar complexes of gallium bromide with methyl bromide. The changes of enthalpy, free energy and entropy fcor the dissociation of the complex are also calculated.

• Applied Chemistry for Engineering
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• v.31 no.5
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• pp.539-544
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• 2020

A three-dimensional (3D) porous polyaniline (PANI) film was fabricated by a combined photo-and soft-lithography technique based on a large-area nanopillar array, followed by a controlled chemical dilute polymerization. The as-obtained 3D PANI film consisted of hierarchically interconnected PANI nanofibers, resulting in a 3D hierarchical nanoweb film with a large surface and open porous structure. Using electrochemical measurements, the resulting 3D PANI film was demonstrated as a flexible pH sensor electrode, exhibiting a high sensitivity of 60.3 mV/pH, which is close to the ideal Nernstian behavior. In addition, the 3D PANI electrode showed a fast response time of 10 s, good repeatability, and good selectivity. When the 3D PANI electrode was measured under a mechanically bent state, the electrode exhibited a high sensitivity of 60.4 mV/pH, demonstrating flexible pH sensor performance.