• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2023-2028
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• 2013

A kinetic study is reported for the nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5k) with piperidine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [piperidine] for the reactions of substrates possessing a strong electron-withdrawing group (EWG) in the leaving group (i.e., 5a-5i) are linear and pass through the origin. In contrast, the plots for the reactions of substrates bearing a weak EWG or no substituent (i.e., 5j or 5k) curve upward, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. Thus, it has been suggested that the reactions of 5a-5i proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate (i.e., $T^{\pm}$) while those of 5j and 5k proceed through a stepwise mechanism with two intermediates (i.e., $T^{\pm}$ and its deprotonated form $T^-$). The slope of the Br${\o}$nsted-type plot for the second-order rate constants (i.e., $k_N$ or $Kk_2$) changes from -0.41 to -1.89 as the leaving-group basicity increases, indicating that a change in the rate-determining step (RDS) occurs. The reactions of 5a-5k with piperidine result in larger $k_1$ values than the corresponding reactions with ethylamine.

• Journal of the Korean Association of Oral and Maxillofacial Surgeons
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• v.36 no.6
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• pp.548-552
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• 2010

The submandibular gland is the second largest major salivary gland, which secretes 40% of the total daily saliva. Owing to its anatomic characteristics as well as the high viscosity and basicity of the saliva, sialolithiasis is found most commonly in the submandibular gland. Sialolithiasis that cannot be treated by conservative treatment is conventionally removed by an excision of the submandibular gland. Generally, an excision of the submandibular gland is performed via an extra-oral approach but the disadvantages of this treatment include a risk of injuring the facial nerve and scar formation. Case reports have revealed an even less invasive intraoral surgical technique for the removal of sialolith that does not affect the submandibular gland function. The functional recovery of the gland, complications and recurrence rates after surgery with this conservative intraoral procedure were all successful. We report 5 patients from the department of Oral and Maxillofacial Surgery at Dental Hospital, Yonsei University, who had undergone a resection of the sialolith though the intraoral approach with successful results.

• Journal of the Korean Chemical Society
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• v.30 no.3
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• pp.265-272
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• 1986

Kinetic studies for the methanolysis of tert-butyl halides (t-BuCl, t-BuBr, t-BuI) were carried out in MeOH-1,1,2,2-tetrachloroethane mixtures. The solvatochromic comparison method was used with six indicators to analyze solvent effects on the ionizations of tert-butyl halides. It was shown that the cooperative effect of solvent polarity-polarizability was the most important factor influenced on the methanolysis rates of tert-butyl halides, but the electrophilic assistance for halide leaving group and the nucleophilic assistance for tert-butylium ion were considerably influential, too. And it was found that the electrophilic assistance caused by hydrogen bonding and the nucleophilic assistance for carbon center were stronger for more basic leaving group ($I^-) and more polarizable leaving group(t-BuCl

• Journal of the Korean Geosynthetics Society
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• v.14 no.1
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• pp.23-32
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• 2015

This paper describes a flow experiment and characteristics of heavy metals based on microfluidics, in order to improve the prefabricated vertical drain system that is possible pollutants removal and soil improvement in soft ground polluted with various pollutants, simultaneously. The result showed that the surface with hydrophobic condition affected large effect on flow velocity pollutants, and pH condition was also influence factor for change of flow velocity. Especially, the flow velocity of lead has risen slightly, when pH was close to basicity in complex heavy metal. This means that lead pollutant can reduce a hydrophobic characteristic in comparison with a copper pollutant.

• Journal of the Korean Chemical Society
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• v.35 no.6
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• pp.636-644
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• 1991

The cationic polymerization of substituted oxethanes which have pendant energetic groups such as methoxy, azido, and nitrato are investigated theoretically using the semiempirical MINDO/3, MNDO, and AM1 methods. The nucleophilicity and basicity of substituted oxethanes can be explained by the negative charge on oxygen atom of oxetanes. The reactivity of propagation in the polymerization of oxetanes can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxetanes. The reaction of the energetic cyclic oxonium ion forms to the open chain carbenium ion forms is expected by computational stability energy of the oxonium and carbenium ion (about 10~20 kcal/mole) favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium and open carbenium ions is found to be a major determinant of mechanism, owing to the rapid equilibrium of these cation forms and the expectation based on clauclation that the prepolymer propagation step SN1 mechanism will be at least as fast as that for SN2 mechanism.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.2135-2138
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• 2014

A kinetic study is reported for the SNAr reaction of 1-Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1h) with OH- in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The second-order rate constant ($k_{OH^-}$) increases as the substituent Y in the leaving group changes from an electron-donating group (EDG) to an electronwithdrawing group (EWG). The Br${\o}$nsted-type plot for the reactions of 1a-1h is linear with ${\beta}_{lg}$ = -0.16, indicating that the reactivity of substrates 1a-1h is little affected by the leaving-group basicity. A linear Br${\o}$nsted-type plot with ${\beta}_{lg}=-0.3{\pm}0.1$ is typical for reactions reported previously to proceed through a stepwise mechanism in which formation of a Meisenheimer complex is the rate-determining step (RDS). The Hammett plot correlated with ${\sigma}_Y{^{\circ}}$ constants results in a much better correlation than that correlated with ${\sigma}_Y{^-}$constants, implyng that no negative charge is developing on the O atom of the leaving group (or expulsion of the leaving group is not advanced at all in the TS). This excludes a possibility that the $S_NAr$ reaction of 1a-1h with $OH^-$ proceeds through a concerted mechanism or via a stepwise pathway with expulsion of the leaving group being the RDS. Thus, the current reactions have been concluded to proceed through a stepwise mechanism in which expulsion of the leaving group occurs rapidly after the RDS.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2410-2414
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of Y-substituted-phenyl picolinates (7a-7h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Comparison of the kinetic results with those reported previously for the corresponding reactions of Y-substituted-phenyl benzoates (1a-1f) reveals that 7a-7h are significantly more reactive than 1a-1f. The Br${\o}$nsted-type plot for the aminolysis of 4-nitrophenyl picolinate (7a) is linear with ${\beta}_{nuc}=0.78$, which is typical for reactions proceeding through a stepwise mechanism with expulsion of the leaving group being the rate-determining step. The Br${\o}$nsted-type plots for the piperidinolysis of 7a-7h and 1a-1f are also linear with ${\beta}_{lg}=-1.04$ and -1.39, respectively, indicating that the more reactive 7a-7h are less selective than the less reactive 1a-1f to the leaving-group basicity. One might suggest that the enhanced reactivity of 7a-7h is due to the inductive effect exerted by the electronegative N atom in the picolinyl moiety, while the decreased selectivity of the more reactive substrates is in accord with the reactivity-selectivity principle. However, the nature of intermediate (e.g., a stabilized cyclic intermediate through the intramolecular H-bonding interaction for the reactions of 7a-7h, which is structurally not possible for the reactions of 1a-1f) is also responsible for the enhanced reactivity with a decreased selectivity.

• Applied Chemistry for Engineering
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• v.5 no.1
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• pp.90-98
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• 1994

For elucidation of various parameters' effects on the reactive extraction of citric acids, citric-acetic-lactic acid system with various carriers, diluents, and modifiers were investigated. Carries used were secondary amines, tertiary amines, and solvation extract. Dileunts were n-butylacetate, methoisobutylketon(MIBK), kerosine, and xylene. Modifiers were TBP and isodecanol. The effects of temperature and pH in aquous phase were studied, and equilibrium constants for the reactive extraction were obtained. The re-extraction was performed by alkali solutions such as NaOH, $Na_2CO_3$, and $K_2HPO_4$. Based on the experiment Di-isotridecylamine(secondary amine ) gave higher degree of extraction and more selective than other extractants tested for the extraction of citric acid. N-butylacetate and TBP showed heigher performance for a diluent and modifier, repetitively. The degree of extraction was getting better with decreasing the pH in the aquous phase and the temperature of extraction system. The degree of re-extraction was getting higher with decreasing basicity in the stripping phase and the system temperature, and with increasing the concentration of alkali solution.

• Advances in concrete construction
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• v.9 no.4
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• pp.387-395
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• 2020

This study has been carried out in two-phases to develop Fiber Reinforced Self-Compacting Concrete (FRSCC) performance. In the first phase, the composition of the quaternary composite binder compromised CEM I 42.5N (58-70%), Rice Husk Ash (25-37%), quartz sand (2.5-7.5%) and limestone crushing waste (2.5-7.5%) were optimized. And in the second phase, the effect of two fiber types (steel brass-plated and basalt) was investigated on the SCC optimized with the optimum CB as disperse reinforcement at 6 different ratios of 1, 1.2, 1.4, 1.6, 1.8, and 2.0% by weight of mix for each type. In this study, the theoretical principles of the synthesis of self-compacting dispersion-reinforced concrete have been developed which consists of optimizing structure-formation processes through the use of a mineral modifier, together with ground crushed cement in a vario-planetary mill to a specific surface area of 550 m2 / kg. The amorphous silica in the modifier composition intensifies the binding of calcium hydroxide formed during the hydration of C3S, helps reduce the basicity of the cement-composite, while reducing the growth of portlandite crystals. Limestone particles contribute to the formation of calcium hydrocarbonate and, together with fine ground quartz sand; act as microfiller, clogging the pores of the cement. Furthermore, the results revealed that the effect of fiber addition improves the mechanical properties of FRSCC. It was found that the steel fiber performed better than basalt fiber on tensile strength and modulus of elasticity; however, both fibers have the same performance on the first crack strength and sample destruction of FRSCC. It also illustrates that there will be an optimum percentage of fiber addition.

• Journal of the Korean Applied Science and Technology
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• v.30 no.1
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• pp.88-95
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• 2013

This study attempts to capture the low level carbon dioxide from indoor spaces using a granular activated carbon (WSC-470) which was modified with primary monoethanolamine. Adsorption capacity of the prepared adsorbents was evaluated for pure $CO_2$ flow and 3000 ppm as a function of MEA concentration and solvents such as distilled water, ethanol and methanol. The AC based adsorbents then were characterized in terms of pore structure by BET and chemical functionalities by XPS. While high concentration of MEA reduced specific surface area, porosity and micro pores, nitrogen content which can enhance the surface basicity was increased. The maximum adsorption capacity decreased comparing to the initial AC pellets, whilst the potential of selective adsorption amount at low level $CO_2$ was increased at 45% (0.73 mmol/g).