• Bulletin of the Korean Chemical Society
• /
• v.12 no.5
• /
• pp.510-514
• /
• 1991

Second-order rate constants have been determined spectrophotometrically for reactions of S-p-nitrophenyl substituted thiobenzoates with various phenoxide ions and S-aryl substituted thiobenzoates with $HO^-$ ion. Thiol esters have been found to be more reactive than the corresponding oxygen esters toward phenoxide ions. The high reactivity of thiol esters relative to oxygen esters becomes insignificant as the basicity of the nucleophile increases. Furthermore, the highly basic $HO^-$ ion is less reactive toward thiol esters than oxygen esters. The significant dependence of the reactivity of thiol esters on the basicity of nucleophiles has been attributed to the nature of the HSAB principle. The present kinetic study has also revealed that the reactivity of thiol esters compared to oxygen esters is not so pronounced as expected based on the enhanced nucleofugicity of thiol esters. However, the effects of substituents in the nucleophile and in the acyl moiety of the substrate on rate appear to be significant. These kinetic results have led to a conclusion that the present reactions proceed via a rate-determining formation of a tetrahedral intermediate followed by a fast breakdown of it. The magnitude of the ${\beta}$ values shows no tendency either to increase or to decrease with the intrinsic reactivity of the reagents. The constancy of ${\beta}$ values in the present system is suggestive that the RSP should have limited applicability.

• The Korean Journal of Applied Statistics
• /
• v.34 no.5
• /
• pp.671-683
• /
• 2021

Power allocation is a technique that evenly allocates samples for each stratum, although the overall efficiency of the allocation is less than that of optimal allocation, and it is often used as a square root proportional allocation in real survey. Also, considering the non-response that occurs in real survey, a larger sample size is used than that in the theoretical formula. In this study, in determining the sample size for each stratum, we study the new methods of allocating by adding information on the response rate per each stratum to power allocation method. The proposed allocation methods are compare with proportional, optimal, and square root proportional allocation in simulation. In addition, the comparison with the proportional and optimal allocation to which the response rate was added is examined through simulation. As a result, we examine the advantages and disadvantages of the allocation methods.

• Journal of the Semiconductor & Display Technology
• /
• v.23 no.2
• /
• pp.65-70
• /
• 2024

Using a computational fluid dynamics(CFD) simulation tool, we have provided a coating guideline for slot-die coating with a double layer slot die head. We have analyzed the fluid dynamics in terms of the coating speed, flow rate ratio, and viscosity ratio, which are critical for the stability of coating meniscus. We have identified the common coating defects such as break-up, air entrainment, and leakage by varying the coating speeds. The flow rate ratio is the critical parameter determining the wet film thickness of the top and bottom layers. It is shown that when the flow rate ratio exceeds or equals 1.8, air entrainment occurs due to insufficient hydraulic pressure in the bottom layer, even though the total flow rate remains constant. Furthermore, we have found that the flow of the bottom layer is significantly affected by the viscosity of top layer. The viscosity ratio of 4 or higher obstructs the flow of the bottom layer due to the increased hydraulic resistance, resulting in leakage. Finally, we have demonstrated that as the viscosity ratio increases from 0.1 to 10, the maximum coating speed rises from 0.4 mm/s to 1.6 mm/s, and the minimum wet film thickness decreases from 800 ㎛ to 200 ㎛.

• Korea Trade Review
• /
• v.44 no.2
• /
• pp.95-107
• /
• 2019

The ICSID arbitral tribunal shall determine the suitability of investors in accordance with the Article 25 of the ICSID convention and the investment or investor's provisions under the BIT. The eligibility of investors has an important role in establishing jurisdiction under international investment disputes. Therefore, this study draws implications on issues related to investor qualification, focusing on ICSID arbitration. The investor's nationality shall be taken into consideration in determining whether the investor is eligible. The criteria for determining the nationality of a corporate investor include the place of incorporation, main business location, and substantial ownership or control. The criterion of the place of incorporation that is used in a number of BIT have the problem of protecting investors from third countries not involved in the BIT. So, in recent years it is stipulated that the actual economic activity or the main business location as well as the place of incorporation criteria. And this problem is complemented by the denial of benefit clause. When determining whether a local corporation is controlled by foreigner in the host state it considers the shareholding rate, voting rights, and the exercise of managerial rights. There is a tendency to recognize shareholder's right to petition. Thus the same damage should not cause problems such as duplicate repayment or double reimbursement between the shareholders and the company. Unexpected problems can arise if the scope of investments and investors is broadly specified in the BIT. Therefore, it is necessary to clarify the scope of investment to be protected.

• Journal of Korean Society on Water Environment
• /
• v.20 no.1
• /
• pp.78-85
• /
• 2004

As an ozone contactor, we newly adopted HJLR (High-performance Jet Loop Reactor) for the decolorization of Reactive black 5 and the mineralization of oxalic acid, which has been applied exclusively in biological wastewater treatments and well-known for high oxygen transfer characteristics. The ozonation efficiency for organic removals and ozone utilization depending on the mass transfer rate were compared to those of Stirred bubble column reactor, which was controlled by varing energy input in the HJLR and Stirred bubble column reactor. The results were as follows; first, the decolorization rate of Reactive black 5 in the HJLR reactor was nearly proportional to the increasing $k_La$. When the $k_La$ was increased by 25 % from $13.0hr^{-1}$ to $16.4hr^{-1}$, 30 % of the k' (apparent reaction rate constant) was increased from 0.1966 to $0.2665min^{-1}$ (Stirred bubble column; from 0.1790 to $0.2564min^{-1}$). Ozone transfer was found to be a rate-determining step in decolorizing Reactive black 5, which was supported by that no residual ozone was detected in all of the experiments. Second, the mineralization of oxalic acid was not always proportional to the increasing $k_La$ in the RJLR reactor. The rate-determining step for this reaction was OH(OH radical) production with ozone transfer, because residual ozone was always detected during the ozonation of oxalic acid in contrast with Reactive black 5. This result indicates that the increase of $k_La$ in the HJLR reactor is beneficial only when there are in ozone transfer limited regions. In addition, regardless of $k_La$, the mineralization of oxalic acid was nearly accomplished within 60 minutes. It was interpreted as that the longer staying of residual ozone by whirling liquid in the HJLR reactor contributed to an high ozone utilization(83-94%), producing more OR radicals.

• Korean Chemical Engineering Research
• /
• v.50 no.2
• /
• pp.358-364
• /
• 2012

The kinetics of the Fischer-Tropsch synthesis and water gas shift reactions over a precipitated iron catalyst were studied in a 5 channel fixed-bed reactor. Experimental conditions were changed as follows: synthesis gas $H_2$/CO feed ratios of 0.5~2, reactants flow rate of 60~80 ml/min, and reaction temperature of $255{\sim}275^{\circ}C$ at a constant pressure of 1.5 MPa. The reaction rate of Fischer-Tropsch synthesis was calculated from Eley-Rideal mechanism in which the rate-determining step was the formation of the monomer species (methylene) by hydrogenation of associatively adsorbed CO. Whereas water gas shift reaction rate was determined by the formation of a formate intermediate species as the rate-determining step. As a result, the reaction rates of Fischer-Tropsch synthesis for the hydrocarbon formation and water gas shift for the $CO_2$ production were in good agreement with the experimental values, respectively. Therefore, the reaction rates ($r_{FT}$, $r_{WGS}$, $-r_{CO}$) derived from the reaction mechanisms showed good agreement both with experimental values and with some kinetic models from literature.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.6
• /
• pp.1907-1911
• /
• 2011

A kinetic study is reported for nucleophilic substitution reactions of 4-pyridyl X-substituted benzoates 7a-e with a series of alicyclic secondary amines in H2O. The Br${\o}$nsted-type plot for the reactions of 4-pyridyl benzoate 7c is linear with ${\beta}_{nuc}$ = 0.71. The corresponding reactions of 2-pyridyl benzoate 6, which is less reactive than 7c, resulted in also a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.77. The fact that the more reactive 7c results in a smaller ${\beta}_{nuc}$ value appears to be in accord with the reactivity-selectivity principle. The aminolysis of 7c has been suggested to proceed through a stepwise mechanism in which breakdown of the intermediate is the rate-determining step (RDS). The Hammett plot for the reactions of 7a-e with piperidine consists of two intersecting straight lines, i.e., ${\rho}_X$ = 1.47 for substrates possessing an electron-donating group (EDG) and ${\rho}_X$ = 0.91 for those possessing an electron-withdrawing group (EWG). In contrast, the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with ${\rho}_X$ = 0.79 and r = 0.56. Thus, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of the substrates possessing an EDG through resonance interaction between the EDG and the C=O bond of the substrates.

• Applied Chemistry for Engineering
• /
• v.16 no.1
• /
• pp.153-157
• /
• 2005

4-(Dimethylamino)pyridinium dichromate was synthesized by the reaction of 4-(dimethylamino)pyridine with chromium(VI)trioxide in $H_2O$, and characterized by IR, EA and ICP. The oxidation of benzyl alcohol using 4-(dimethylamino)pyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: cyclohexen < chloroform < acetone < N,N-dimethylformamide. In the presence of hydrochloric acid(HCl), 4-(dimethylamino)pyridinium dichromate oxidized benzyl alcohol and its derivatives ($p-CH_3$, H, m-Br, $m-NO_2$) smoothly in N,N-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron-withdrawing groups retarded the reaction. The Hammett reaction constant($\rho$) was -0.70 at 303K. The observed experimental data have been rationalized as follows: the proton transfer occurs after the prior formation of a chromate ester in the rate-determining step.

• 한국신재생에너지학회:학술대회논문집
• /
• 2007.11a
• /
• pp.306-308
• /
• 2007

Poly(ethylene glycol) dimethyl ether (PEGDME)/fumed silica/ 1-methyl -3-propylimidazolium iodide (MPII)/$I_2$ mixtures were used as polymer electrolytes in solid state dye-sensitized solar cells (DSSCs). The contents of MPII were changed and the concentration of $I_2$ was fixed at 0.1 mole% with respect to the MPII. The maximum ionic conductivity was obtained at [EG]:[MPII]:[$I_2$]=10:1.5:0.15. It was supposed that the maximum of ionic conductivities would match with that of cell efficiencies, if the ionic conductivity is a rate determining step in the sol id state DSSCs. However, the maximum composition did not show the maximum solar cell performance, indicating the mismatch between ionic conductivity and cell performance. This suggests that the ionic conductivity may not be the rate controlling step in determining the cell efficiency in these experimental conditions, whereas other parameters such as the electron recombination might play an important role. Thus, we tried to modify the surface of the $TiO_2$ particles by coating a thin metal oxide such as $Al_2O_3$ or $Nb_2O_5$ layer to prevent electron recombination. As a result, the maximum of the cell efficiency was shifted to that of the ionic conductivity. The peak shifts were also attempted to be explained by the diffusion coefficient and the lifetime of electrons in the $TiO_2$ layer.

• Journal of the Korea Academia-Industrial cooperation Society
• /
• v.13 no.1
• /
• pp.462-469
• /
• 2012

Cr(VI)-4,4'-bipyridine complex(4,4'-bipyridinium dichromate) was synthesized by the reaction of 4,4'-bipyridine with chromium trioxide in H2O, and characterized by IR, ICP. The oxidation of benzyl alcohol using 4,4'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene$CH_3$, H, m-Br, m-$NO_2$) smoothly in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.63(303K). The observed experimental data have been rationalized as follows; the proton transfer occurs after the prior formation of a chromate ester in the rate determining step.