• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2448-2452
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• 2014

Second-order rate constants ($k_N$) have been measured spectrophotometrically for $S_NAr$ reactions of Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1g) with hydrazine and glycylglycine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Hydrazine is 14.6-23.4 times more reactive than glycylglycine. The magnitude of the ${\alpha}$-effect increases linearly as the substituent Y becomes a stronger electron-withdrawing group (EWG). The Br${\o}$nsted-type plots for the reactions with hydrazine and glycylglycine are linear with ${\beta}_{lg}=-0.21$ and -0.14, respectively, which is typical for reactions reported previously to proceed through a stepwise mechanism with expulsion of the leaving group occurring after rate-determining step (RDS). The Hammett plots correlated with ${\sigma}^{\circ}$ constants result in much better linear correlations than ${\sigma}^-$ constants, indicating that expulsion of the leaving group is not advanced in the transition state (TS). The reaction of 1a-1g with hydrazine has been proposed to proceed through a five-membered cyclic intermediate ($T_{III}$), which is structurally not possible for the reaction with glycylglycine. Stabilization of the intermediate $T_{III}$ through intramolecular H-bonding interaction has been suggested as an origin of the ${\alpha}$-effect exhibited by hydrazine.

• 대한화학회지
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• 제57권3호
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• pp.335-340
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• 2013

폴리에틸렌글리콜(PEGs)과 수산화칼륨(KOH)을 이용하여 서로 다른 온도와 시간의 반응조건에 따라 PBDEs의 화학반응을 수행하였다. PBDEs의 제거효율은 화학반응 전과 후의 농도의 차이로 측정하였다. PBDEs는 25와 $50^{\circ}C$의 낮은 온도에서는 제거되지 않았다. 하지만 온도를 증가시킴에 따라, 바이페닐기에 붙어있는 5-6개의 브롬이 치환되어 있는 PBDEs의 완전제거를 보이면서 ${\sigma}$-xylene에 있는 PBDEs의 제거효율은 점차적으로 증가하였다. 반응조건을 4시간과 $150^{\circ}C$까지 증가시켰을 때 PBDEs의 제거효율은 거의 100%에 도달하였다. 이와 같이 PEGs와 PBDEs의 화학반응 연구를 통해, PBDEs가 PEGs에 의해 브롬이 순차적으로 제거되는 진행에 의해서 탈브롬화 된다는 것을 확인할 수 있었다.

• Nuclear Engineering and Technology
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• 제47권6호
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• pp.700-711
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• 2015

Sodium-cooled fast breeder reactors use liquid sodium as a moderator and coolant to transfer heat from the reactor core. The main hazard associated with sodium is its rapid reaction with water. Sodium-water reaction (SWR) takes place when water or vapor leak into the sodium side through a crack on a heat-transfer tube in a steam generator. If the SWR continues for some time, the SWR will damage the surface of the defective area, causing it to enlarge. This self-enlargement of the crack is called "self-wastage phenomena." A stepwise numerical evaluation model of the self-wastage phenomena was devised using a computational code of multicomponent multiphase flow involving a sodium-water chemical reaction: sodiumwater reaction analysis physics of interdisciplinary multiphase flow (SERAPHIM). The temperature of gas mixture and the concentration of NaOH at the surface of the tube wall are obtained by a numerical calculation using SERAPHIM. Averaged thermophysical properties are used to assess the local wastage depth at the tube surface. By reflecting the wastage depth to the computational grid, the self-wastage phenomena are evaluated. A two-dimensional benchmark analysis of an SWAT (Sodium-Water reAction Test rig) experiment is carried out to evaluate the feasibility of the numerical model. Numerical results show that the geometry and scale of enlarged cracks show good agreement with the experimental result. Enlarged cracks appear to taper inward to a significantly smaller opening on the inside of the tube wall. The enlarged outer diameter of the crack is 4.72 mm, which shows good agreement with the experimental data (4.96 mm).

• 대한화학회지
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• 제67권3호
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• pp.191-198
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• 2023

본 연구에서는 2,4-dinitrophenyl-5-substituted-2-furoates (1a-d)와 R₂NH/R₂NH₂⁺-20 mol%DMSO(aq)의 아실 이동 반응을 반응속도론적으로 연구하였다. 이 반응은 이차반응이고, pK_a⁰ = 9.5, β₁= 0.23-0.35 및 β₂ = 0.88-0.99의 결과와 함께 아래 방향으로 굽은 Brönsted plots이 관측되었다. k₁값은 5-furyl 치환기의 전자끄는 능력이 증가하고 친핵체의 친핵성도가 커질수록 증가하였다. 반면, k₂/k_-1 값 비율은 5-furyl 치환기에 관계없이 거의 일정하였다. 실험결과로 부터 반응은 속도결정단계가 변하는 단계반응 메커니즘으로 진행됨을 제안하였다.

• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2271-2276
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• 2014

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reaction of 4-chloro-2-nitrophenyl X-substituted-benzoates (6a-6h) with a series of primary amines including hydrazine in 80 mol % $H_2O$/20 mol % DMSO at $25.0^{\circ}C$. The Br${\o}$nsted-type plot for the reaction of 4-chloro-2-nitrophenyl benzoate (6d) is linear with ${\beta}_{nuc}$ = 0.74 when hydrazine is excluded from the correlation. Such a linear Br${\o}$nsted-type plot is typical for reactions reported previously to proceed through a stepwise mechanism in which expulsion of the leaving group occurs in the rate-determining step (RDS). The Hammett plots for the reactions of 6a-6h with hydrazine and glycylglycine are nonlinear. In contrast, the Yukawa-Tsuno plots exhibit excellent linear correlations with ${\rho}_X$ = 1.29-1.45 and r = 0.53-0.56, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by resonance stabilization of the substrates possessing an electron-donating group (EDG). Hydrazine is ca. 47-93 times more reactive than similarly basic glycylglycine toward 6a-6h (e.g., the ${\alpha}$-effect). The ${\alpha}$-effect increases as the substituent X in the benzoyl moiety becomes a stronger electron-withdrawing group (EWG), indicating that destabilization of the ground state (GS) of hydrazine through the repulsion between the nonbonding electron pairs on the two N atoms is not solely responsible for the substituent-dependent ${\alpha}$-effect. Stabilization of transition state (TS) through five-membered cyclic TSs, which would increase the electrophilicity of the reaction center or the nucleofugality of the leaving group, contributes to the ${\alpha}$-effect observed in this study.

• Bulletin of the Korean Chemical Society
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• 제28권4호
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• pp.520-528
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• 2007

A practical and efficient disposal of PCBs (polychlorinated biphenyls) in waste transformer oil by a chemical dechlorination process has been reported. The transformer oil containing commercial PCB mixtures (Aroclor 1242, 1254 and 1260) was treated by the required amounts of PEG 600 (polyethylene glycol 600), potassium hydroxide (KOH) and aluminum (Al), along with different reaction temperatures and times. The reaction of PEG with PCBs under basic condition produces arylpolyglycols, the products of nucleophilic aromatic substitution. The relative efficiencies of PCB treatment process were assessed in terms of destruction and removal efficiency (DRE, %). Under the experimental conditions of PEG600/KOH/Al/100 oC/2hr, average DRE of PCBs was approximately 78%, showing completely removal of PCBs containing 7-9 chlorines on two rings of biphenyl which appear later than PCB no. 183 (2,2',3,4,4',5',6-heptaCB) in retention time of GC/ECD. However, when increasing the reaction temperature and time to 150 oC and 240 min, average DRE of PCBs including the most toxic PCBs (PCB no. 77, 105, 118, 123 and 169) in PCB family reached 99.99% or better, with the exception of PCB no. 5 and 8 (2,3-diCB and 2,4'-diCB). In studying the reaction of PEG with PCBs, it confirmed that the process led to less chlorinated PCBs through a stepwise process with the successive elimination of chlorines. The process also permits complete recovery of treated transformer oil through simple segregating procedures.

• Bulletin of the Korean Chemical Society
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• 제31권3호
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• pp.689-693
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• 2010

Second-order rate constants ($k_{CN^-}$) have been measured for nucleophilic substitution reactions of Y-substituted phenyl benzoates (1a-r) with $CN^-$ ion in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plot is linear with ${\beta}_{1g}$ = -0.49, a typical ${\beta}_{1g}$ value for reactions reported to proceed through a concerted mechanism. Hammett plots correlated with ${\sigma}^{\circ}$ and ${\sigma}^-$ constants exhibit many scattered points. In contrast, the Yukawa-Tsuno plot for the same reaction exhibits excellent linearity with ${\rho}_Y$ = 1.37 and r = 0.34, indicating that a negative charge develops partially on the oxygen atom of the leaving aryloxide in the rate-determining step (RDS). Although two different mechanisms are plausible (i.e., a concerted mechanism and a stepwise pathway in which expulsion of the leaving group occurs at the RDS), the reaction has been concluded to proceed through a concerted mechanism on the basis of the magnitude of ${\beta}_{1g}$ and ${\rho}_Y$ values.

• Bulletin of the Korean Chemical Society
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• 제34권6호
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• pp.1722-1726
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• 2013

A kinetic study on nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5j) with ethylamine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$ is reported. The plots of $k_{obsd}$ vs. [amine] are linear for the reactions of substrates possessing a strong electron-withdrawing group (EWG) but curve upward for those of substrates bearing a weak EWG, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. The reactions have been concluded to proceed through a stepwise mechanism with one or two intermediates (a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$) depending on the nature of the substituent Y. Analysis of Bronsted-type plots and dissection of $k_{obsd}$ into microscopic rate constants have revealed that the reactions of substrates possessing a strong EWG (e.g., 5a-5f) proceed through $T^{\pm}$ with its formation being the rate-determining step, while those of substrates bearing a weak EWG (e.g., 5g-5j) proceed through $T^{\pm}$ and $T^-$.

• Bulletin of the Korean Chemical Society
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• 제25권2호
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• pp.203-206
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• 2004

The kinetics of reactions between Z-aryl thiophene-2-carbodithioates and X-pyridines in acetonitrile at 60.0 $^{\circ}C$ have been investigated. The Bronsted plots obtained for the pyridinolysis of aryl thiophene-2-carbodithioates are curved, with the center of curvature at $pK_a$ ~ 5.2 ($pK_a^{\circ}$). The Bronsted plots for these nucleophilic reactions show a change in slope from a large ( ${\beta}_X{\cong}$0.78-0.87) to a small ( ${\beta}_X{\cong}$0.33-0.35) value, which can be attributed to a change in the rate-determining step from breakdown to formation of a zwitterionic tetrahedral intermediate in the reaction path as the basicity of the pyridine nucleophile increases. A clear-cut change in the crossinteraction constants, ${\rho}_{XZ}$, from +0.92 to -0.23 supports the proposed mechanistic change. The breakpoint at $pK_a$ = 5.2 for R = thiophene ring in the present work is in agreement with those for the pyridinolysis of R = Me and 2-furyl, and attests to the insignificant effects of acyl group, R, on the breakpoint.

• Bulletin of the Korean Chemical Society
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• 제25권7호
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• pp.1041-1045
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• 2004

Kinetic studies of the pyridinolysis $(XC_5H_4N)$ of aryl dithiomethylacetates $(CH_3CH_2C(=S)SC_6H_4Z,\;1)$ are carried out in acetonitrile at $60.0^{\circ}C$. A biphasic Bronsted plot is obtained with a change in slope from a large $({\beta}X\;{\cong}\;0.8)$ to a small $({\beta}X\;{\cong}\;0.2)$ value at $pK_a^{\circ}$ = 5.2, which is attributed to a change in the rate limiting step from breakdown to formation of a zwitterionic tetrahedral intermediate, $T^{\pm}$, in reaction path as the basicity of the pyridine nucleophile increases. This mechanism is supported by the change of the cross-interaction constant ${\rho}xz$ from a large positive ( ${\rho}xz$ = +1.36) for the weakly basic pyridines to a small negative ( ${\rho}_xz$ = -0.22) value for the strongly basic pyridines. The magnitudes of ${\rho}z$ and activation parameters are also consistent with the proposed mechanism.