• 공업화학
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• 제28권5호
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• pp.597-600
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• 2017

4,4'-비피리딘과 크롬(VI) 산화물을 반응시켜 $(C_{10}H_8N_2H)_2Cr_2O_7$을 합성하였다. 적외선분광광도법(FT-IR)과 원소분석으로 구조를 확인하였다. 여러 가지 용매 하에서 $(C_{10}H_8N_2H)_2Cr_2O_7$을 이용하여 벤질알코올의 산화반응을 측정한 결과, 용매의 유전상수 값이 증가함에 따라 반응수율이 증가했다. 그 순서는 DMF (N,N'-디메틸포름아미드) > 아세톤 > 클로로포름 > 시클로헥센이었다. $H_2SO_4$ 촉매를 이용한 DMF 용매 하에서, $(C_{10}-H_8N_2H)_2Cr_2O_7$은 벤질알코올(H)과 그의 유도체들($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$)을 효과적으로 산화시켰다. 전자받개 그룹들은 반응속도가 감소한 반면에 전자주개 치환체들은 반응속도를 증가시켰고, Hammett 반응상수(${\rho}$) 값은 -0.70 (308 K)이었다. 본 실험에서 알코올의 산화반응 과정은 속도결정단계에서 수소화 전이가 일어났다.

• 한국건설순환자원학회논문집
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• 제3권3호
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• pp.237-243
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• 2015

본 연구에서는 알칼리 활성화 슬래그 결합재의 반응성을 정량적으로 살펴보기 위해 미소수화열을 분석을 수행하였다. 알칼리 활성화 슬래그 결합재의 반응성 및 작업성 확보를 위해 다양한 알칼리 자극제의 종류 및 농도에 대해서 실험을 수행하였다. 알칼리 자극제 및 $SO_3$ 질량비를 변화하면서 미소수화열을 측정하였으며, 응결시간 제어를 위해 sodium tripolyphosphate ($Na_2P_3O_{10}$)와 hydrated sodium borate ($Na_2B_4O_710H_2O$)를 적용하였다. 그 결과, 알칼리 활성화 슬래그 결합재는 알칼리 활성에 의해 calcium silicate hydrate(C-S-H)를 촉진하는데 4~5% 농도의 알칼리가 필요한 것으로 나타났으며, $SO_3$ 함량이 높아질수록 누적 발열량이 작아지면서 전반적으로 발열이 지연되는 것으로 나타났다. 또한, 응결 지연제로서 hydrated sodium borate를 사용하였을 경우 발열을 억제하여 지연된 효과를 나타내며, 전체적인 누적 발열을 지연시키는 효과를 보이는 것을 확인할 수 있었다.

• 한국재료학회지
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• 제33권7호
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• pp.265-272
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• 2023

In this study, the synthesis of nitrobenzene was carried out using sulfated silica catalyst. The study delved into H₂SO₄/SiO₂ as a solid acid catalyst and the effect of its weight variation, as well as the use of a microwave batch reactor in the synthesis of nitrobenzene. SiO₂ was prepared using the sol-gel method from TEOS precursor. The formed gel was then refluxed with methanol and calcined at a temperature of 600 ℃. SiO₂ with a 200-mesh size was impregnated with 98 % H₂SO₄ by mixing for 1 h. The resulting 33 % (w/w) H₂SO₄/SiO₂ catalyst was separated by centrifugation, dried, and calcined at 600 ℃. The catalyst was then used as a solid acid catalyst in the synthesis of nitrobenzene. The weights of catalyst used were 0.5; 1; and 1.5 grams. The synthesis of nitrobenzene was carried out with a 1:3 ratio of benzene to nitric acid in a microwave batch reactor at 60 ℃ for 5 h. The resulting nitrobenzene liquid was analyzed using GC-MS to determine the selectivity of the catalyst. Likewise, the use of a microwave batch reactor was found to be appropriate and successful for the synthesis of nitrobenzene. The thermal energy produced by the microwave batch reactor was efficient enough to be used for the nitration reaction. Reactivity and selectivity tests demonstrated that 1 g of H₂SO₄/SiO₂ could generate an average benzene conversion of 40.33 %.

• 한국산학기술학회논문지
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• 제12권12호
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• pp.5990-5996
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• 2011

$H_2O$ 용매 하에서 6-methylquinoline 과 chromium trioxide의 반응을 통하여 6-methylquinolinium dichromate [$(C_{10}H_9NH)_2Cr_2O_7$]를 합성하여, 적외선분광광도법(IR), 유도결합 플라즈마(ICP) 등으로 구조를 확인하였다. 여러 가지 용매 하에서 6-methylquinolinium dichromate를 이용하여 벤질 알코올의 산화반응을 측정한 결과 유전상수(${\varepsilon}$) 값이 큰 용매 순서인 시클로헥센 < 클로로포름 < 아세톤 < N,N-디메틸포름아미드 용매 하에서 높은 산화반응성을 보였다. 산촉매($H_2SO_4$)를 이용한 DMF 용매 하에서 6-methylquinolinium dichromat는 벤질 알코올과 그의 유도체들(p-$OCH_3$, m-$CH_3$, H, m-$OCH_3$, m-Cl, m-$NO_2$)을 효과적으로 산화시켰다. 그리고 전자받개 그룹들은 반응속도가 감소한 반면에 전자주개 치환체들은 반응속도를 증가시켰다. 또한 Hammett 반응상수(${\rho}$) 값은 -0.67(303K) 이였다. 그러므로 본 실험에서 알코올의 산화반응 과정은 속도결정단계에서 수소화 전이가 일어나는 메카니즘임을 알 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제32권9호
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• pp.3281-3289
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• 2011

The materials composed of the 3d series transition metals are introduced into the hydrocarbon steam-reforming reaction in order to enhance the $H_2$ production and abruptly depress the catalytic deactivation resulting from the strong sintering between the Ni component and the ${\gamma}-Al_2O_3$ support. The conventional impregnation method is used to synthesize the Ni/3d series metal/${\gamma}-Al_2O_3$ materials through the sequentially loading Ni source and the 3d series metal (Ti, V, Cr, Mn, Fe, Co, Cu, and Zn) sources onto the ${\gamma}-Al_2O_3$ support. The Mnloaded material exhibits a significantly higher reforming reactivity than the conventional Ni/${\gamma}-Al_2O_3$ and the other Ni/3d series metal/${\gamma}-Al_2O_3$ materials. Particularly the addition of Mn selectively improves the $H_2$ product selectivity by eliminating the formation of $CH_4$ and CO. The $H_2$ production is maximized at a value of 95% over Ni(0.3)/Mn(0.3)/${\gamma}-Al_2O_4$(1.0) with a butane conversion of 100% above $750^{\circ}C$ for up to 55 h.

• Bulletin of the Korean Chemical Society
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• 제29권7호
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• pp.1359-1363
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• 2008

Second-order rate constants have been determined spectrophotometrically for reactions of 2,4-dinitrophenyl 2- thiophenecarboxylate (2) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The Brønsted-type plot exhibits a downward curvature, i.e., the slope decreases from 0.74 to 0.34 as the amine basicity increases. The $pK_a$ at the center of the Brønsted curvature, defined as $pK_a^o$, has been determined to be 9.1. Comparison of the Brønsted-type plot for the reactions of 2 with that for the corresponding reactions of 2,4-dinitrophenyl 2-furoate (1) suggests that reactions of 1 and 2 proceed through a common mechanism, although 2 is less reactive than 1. The curved Brønsted-type plot has been interpreted as a change in RDS of a stepwise mechanism. The replacement of the O atom in the furoyl ring by an S atom (1 $\rightarrow$ 2) does not alter the reaction mechanism but causes a decrease in reactivity. Dissection of the apparent second-order rate constants into the microscopic rate constants has revealed that the $k_2/k_{-1}$ ratio is not influenced upon changing the nonleaving group from furoyl to thiophenecarbonyl. However, $k_1$ has been calculated to be smaller for the reactions of 2 than for the corresponding reactions of 1, indicating that the C=O bond in the thiophenecarboxylate 2 is less electrophilic than that in the furoate 1. The smaller k1 for the reactions of 2 is fully responsible for the fact that 2 is less reactive than 1.

• 한국펄프종이공학회:학술대회논문집
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• 한국펄프종이공학회 1999년도 춘계학술발표논문집
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• pp.84-88
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• 1999

In chlorine dioxide delignigication or bleaching, chlorate is mainly formed by the reaction between chlorite and hypochlorous acid, thus scavengers of chlorine or hypochlorous acid can be used to reduce the formation of chlorate which is unfavorable to environment. In this study, additives such as sulfamic acid, DMSO, hydrogen peroxide, or sodium chlorite was added to chlorine solution or pure $ClO_2$ solution to check their reactivity with $Cl_2$ and $ClO_2$. These additives were also added directly into general $ClO_2$ solution which contained certain amount of chlorine, then the additive-treated $ClO_2$ solution were used in bleaching stages. The aim of this procedure was to remove the original amount of chlorine that was thought to be possibly the main reason for the formation of chlorate and AOX. The additives were found to be able to eliminate chlorine very fast and selectively, but $H_2$ $O_2$ should be used under pH4, otherwise it also reacts with $ClO_2$. After the additives reacted With $Cl_2$, DMSO turned into an inactive product $(CH_3)_2SO_2$, While Sulfamic acid turned into $HClSO_3H$ that still remained active in oxidation, and $NaClO_2$ produced $ClO_2$. The addition of $HNaClO_2$ showed significant improvement in delignification but the deeper delignification led to higher formation of chlorate. When the additive-treated chlorine dioxide solutions were used in bleaching, both sulfamic acid, DMSO, and hydrogen peroxide showed no significant changes of DE brightness and Kappa number. The formation of chlorate was reduced by addition of sulfamic acid, DMSO and hydrogen peroxide.

• Bulletin of the Korean Chemical Society
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• 제30권1호
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• pp.214-218
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• 2009

Second-order rate constants ($k_N$) have been measured for nucleophilic substitution reactions of S-4-nitrophenyl thiobenzoate with a series of alicyclic secondary amines in $H_2O$ containing 20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The Br$\phi$nsted-type plot exhibits a downward curvature, i.e., $\beta_{nuc}$ decreases from 0.94 to 0.34 as the amine basicity increases. The reactions in the aqueous DMSO have also been suggested to proceed through a zwitterionic tetrahedral intermediate (T${\pm}$) with change in the RDS on the basis of the curved Br$\phi$nsted-type plot. The reactions in the aqueous DMSO exhibit larger $k_N$ values than those in the aqueous EtOH. The macroscopic rate constants ($k_N$) for the reactions in the two solvent systems have been dissected into the microscopic rate constants ($k_1\;and\;k_2/k_{-1}$ ratio) to investigate effect of medium on reactivity in the microscopic level. It has been found that the $k_2/k_{-1}$ ratios are similar for the reactions in the two solvent systems, while $k_1$ values are larger for the reactions in 20 mol % DMSO than for those in 44 wt % EtOH, indicating that the larger $k_1$ is mainly responsible for the larger $k_N$. It has been suggested that the transition state is more stabilized in 20 mol % DMSO through mutual polarizability interaction than in 44 wt % EtOH through H-bonding interaction.

• Bulletin of the Korean Chemical Society
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• 제33권7호
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• pp.2269-2273
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• 2012

Pseudo-first-order rate constants $k_{amine}$ have been measured spectrophotometrically for the reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. The plots of $k_{amine}$ vs. [amine] curve upward, indicating that the reactions proceed through a stepwise mechanism with two intermediates, a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$. This contrasts to the report that the corresponding reactions of benzyl 2-pyridyl carbonate 5 proceed through a forced concerted pathway. The $k_{amine}$ values for the reactions of 6 have been dissected into the second-order rate constant $Kk_2$ and the thirdorder rate constant $Kk_3$. The Br${\o}$nsted-type plots are linear with ${\beta}_{nuc}=0.94$ and 1.18 for $Kk_2$ and $Kk_3$, respectively. The $Kk_2$ for the reaction of 6 is smaller than the second-order rate constant $k_N$ for the corresponding reaction of 5, although 4-pyridyloxide in 6 is less basic and a better nucleofuge than 2-pyridyloxide in 5.

• Bulletin of the Korean Chemical Society
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• 제20권12호
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• pp.1428-1432
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• 1999

[Fe$^{II}$(BLPA)DBCH]BPh₄ (1), a new functional model for the extradiol-cleaving catechol dioxygenases, has been synthesized, where BLPA is bis(6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine and DBCH is 3,5-di-tert-butylcatecholate monoanion. ¹H NMR and EPR studies confirm that 1 has a high-spin Fe(II) (S = 2) center. The electronic spectrum of 1 exhibits one absorption band at 386 nm, showing the yellow color of the typical [Fe$^{II}$(BLPA)] complex. Upon exposure to O₂, 1 is converted to an intense blue species within a minute. This blue species exhibits two intense bands at 586 and 960 nm and EPR signals at g = 5.5 and 8.0 corresponding to the high-spin Fe(III) complex (S = 5/2, E/D = 0.11). This blue complex further reacts with O₂ to be converted to (μ-oxo)Fe$^{III}_2$ complex within a few hours. Interestingly, 1 affords intradiol cleavage (65%) and extradiol cleavage (20%) products after the oxygenation. It can be suggested that 1 undergoes two different oxygenation pathways. The one takes the substrate activation mechanism proposed for the intradiol cleavage products after the oxidation of the $Fe^II\;to\;Fe^{III}$. The other involves the direct attack of O₂ to $Fe^{II}$ center, forming the $Fe^{III}$-superoxo intermediate which can give rise to the extradiol cleavage products. 1 is the first functional Fe(II) complex for extradiol-cleaving dioxygenases giving extradiol cleavage products.