• Journal of the Korean Chemical Society
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• v.16 no.2
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• pp.64-69
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• 1972

Nucleophilic reactivities of 1-and 2-phenethyl chlorides have been investigated MO-theoretically using the EHT method. It has been shown that results of population analysis are consistent with the experimental order of relative nucleophilic reactivities and furthermore the reversal of the reactivity order for the less reactive nucleophile, $I^-$, could also be explained satisfactorily.

• Journal of the Korean Chemical Society
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• v.15 no.2
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• pp.95-105
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• 1971

The apparent molal volumes ${\phi}_v$ of a series of homologous tetraalkylammonium chlorides, $Me_4NCl, Et_4NCl, Pr_4NCl,\;and\;Bu_4NCl$, in a series of isopropanol-water mixtures have been determined at $30^{\circ}C$ from precision density measurements using pycnometers. The values of ${\phi}_v$ extrapolated to infinite dilution give partial molal volumes $\={V}^{\circ}$s which are almost additive for successive homologues and enable one to determine the absolute individual ionic partial molal volumes. The experimental results are discussed in terrns of the varying size and surface charge of the ions and the structure of the binary solvent mixtures. The results indicate that at 0.1 mole fraction isopropanol the maximum structuredness of water causes a minimum in the tetraalkylammonium-cation partial molal volumes, while at 0.2 mole fraction the solvent structure is such that the free volumes is a minimum and the electrostrictive effect of chloride ion is a maximum.

• Bulletin of the Korean Chemical Society
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• v.34 no.10
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• pp.2989-2994
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• 2013

The solvolysis rate constants of 3,4- (1) and 3,5-dimethoxybenzoyl (2) chlorides were measured in various pure and binary solvents at $25.0^{\circ}C$, and studied by application of the extended Grunwald-Winstein (G-W) equation, kinetic solvent isotope effect in methanolysis and activation parameters. The solvolysis of 1 was interpreted as the unimolecular pathway due to a predominant resonance effect from para-methoxy substituent like 4-methoxybenzoyl chloride (3), while that of 2 was evaluated as the dual mechanism, with unimolecular or bimolecular reaction pathway according to the character of solvent systems (high electrophilic/nucleophilic) chosen, caused by the inductive effect by two meta-methoxy substituents, no resonance one. In the solvolyses of 1 and 2 with two $-OCH_3$ groups, the resonance effect of para-methoxy substituent is more important to decide the mechanism than the inductive effect with other corresponding evidences.

• Journal of the Korean institute of surface engineering
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• v.30 no.3
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• pp.159-166
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• 1997

The metalliding technique was adopted to obtain the diffusion coating of zirconium on AISI 304 Stainless Steel in molten mixed chlorides (32.9wt.%LICl-34.8wt.%NaCl-32.3wt.%). Experiments were carried out in argon gas atmosphere. The electrolytic cell was consisted of a AISI 304 Stainless steel cathode and a consumable zirconium anode. The quality of deposit was analysed by SEM, Optical Microscope, EDS, and also examined by the Micro-Vickers hardness and corrosion tests. Interface of deposit layer was identified as zirconium-iron alloy layer caused by diffusion process at elevated temperatures. The optimum condition for the metalliding was found to be the bath temperature of $550^{\circ}C$, the concentration of $K_2ZrF_6$ ,5wt.%, cathodic current derrent density of 7.0 to 10.0mA/$\textrm{cm}^2$ , and anodic current density of 2.0mA/$\textrm{cm}^2$.

• Proceedings of the Korea Concrete Institute Conference
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• 1997.04a
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• pp.149-154
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• 1997

In order to predict the onset of the corrosion of steel bars in the concrete, a mathematical model including the diffusion of chloride ion in aqueous phase of pores, the adsorption and desorption of chloride ions to and from the surface of solid phase of concrete, and the chemical reaction of chloride ions with solid phase was established. Finite element method was employed to carry out numerical analysis. The chlorides penetrating through the wall of concrete structure from the external environment and the chlorides contained in the concrete admixture were confirmed to be two important factors to determine the onset of corrosion of steel bars.

• Computers and Concrete
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• v.19 no.2
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• pp.161-169
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• 2017

Chloride induced reinforcement corrosion is widely accepted to be the most frequent mechanism causing premature degradation of reinforced concrete structures. The electrochemical impedance of reinforcing steel in diatomite- and zeolite-containing concrete exposed to sodium chloride was assessed. Chemical, physical and mineralogical properties of three concrete samples (20% diatomite, 20% zeolite, and a reference containing neither) were correlated with corrosion investigations. The steel-reinforced samples were exposed to 3.5% NaCl solution for 500 days, and measured every 15 days via EIS method. Results indicated that porosity and capillary spaces increase the diffusion rate of water and electrolytes throughout the concrete, making it more susceptible to cracking. Reinforcement in the reference concrete was the most corroded compare to the zeolite and the diatomite samples.

• Journal of the Korean Chemical Society
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• v.18 no.4
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• pp.251-258
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• 1974

The rate constants for the nucleophilic substitution reactions of substituted benzoyl chlorides with p-nitroaniline in such solvents as acetone, acetonitrile, methanol, ethanol, etc. were conductometrically determined, and the activation thermodynamic parameters were also evaluated. In result, the reaction rates were faster in protic solvents than in aprotic solvent; in the solvents of similar property, the reaction rate in the solvent of the large dielectric constant was faster than that in the solvent of the small dielectric constant. Hammett plots in individual solvents showed the straight lines with positive slope; and we concluded that the reaction occurred via the addition-elimination mechanism.

• Journal of the Korean Chemical Society
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• v.17 no.4
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• pp.235-239
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• 1973

Kinetic studies of benzoyl chlorides solvolysis have been carried out in acetone-water mixtures. Results show that bimolecular process predominates in the low water content region but SN1 process becomes increasingly important in the high water content solvent composition.

• Journal of the Korean Chemical Society
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• v.18 no.1
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• pp.8-11
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• 1974

The solvolysis of p-substituted benzenesulfonyl chlorides $(substituents:p-H, p-Br, p-NO_2, p-OCH_3)$ in acetonitrile-water mixtures below 50 % of water content has been studied kinetically. Results show that Hammett plots give concaved curves but the mechanism is predominantly $S_N2$ and water acts both as nucleophile and general-base.

• Journal of the Korean Chemical Society
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• v.41 no.10
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• pp.535-540
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• 1997

Potassium carbonate reacts with silicon tetrachloride to form trichlorosilyloxy carbonylchloride which reacts subsequently with another molecule of silicon tetrachloride leading to phosgene eventually in chlorinated solvents. This in situ generated trichlorosilyloxy carbonylchloride or phosgene were found to be very effective for the chlorination of a wide variety of alcohols to the corresponding chlorides. Primary, secondary and benzylic alcohols were converted into corresponding chlorides when treated with silicon tetrachloride in the presence of potassium carbonate at room temperature.