• Nuclear Engineering and Technology
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• 제26권3호
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• pp.425-432
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• 1994

질산 용액중의 우라늄(VI) 환원에 대한 하이드라이진형태 및 티타늄 전극상태 영향을 알기위하여, 질산 및 하이드라이진($N_2$H$_4$) /하이드라이진 양이온($N_2$H$_{5}$$^{＋}$) 용액중의 전기화학적 미-처리 /처리 티타늄 전극에서 우라늄환원에 대한 voltammogram 해석을 수행하였다. 질산 및 하이드라이진 양이온 계를 사용한 전기화학적 미처리 티타늄 전극에서의 우라늄 환원은 그 전극에 존재하는 산화막에 의해 높은 활성화 과전압을 보이며, 하이드라이진에 기인한 질산용액중 수소이온의 소모에 의해 용액전도도의 감소 및 iR 저항의 증가 때문에 하이드라이진의 절대 농도보다는 하이드라이진/질산 농도 비에 의해 영향을 더 받았다. 질산 및 하이드라이진 양이온 계를 사용한 전기화학적 처리 티타늄 전극에서의 우라늄환원 전류는 같은 전위에서 전기화학적 미처리 티타늄전극에 비해 속도론을 해석하기에 충분히 분명하며, 높은 피크를 보였으며 질산에 의해 크게영향을 받았다. 용액중에 하이드라이진 양이온의 존재는 생성된 우라늄(IV)의 재산화 방지를 위해 중요하지만 그 농도는 우라늄 이온의 환원에는 영향을 미치지 않았다.다.

• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2371-2374
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• 2014

A kinetic study is reported on SNAr reaction of 1-fluoro-2,4-dinitrobenzene with a series of primary amines including hydrazine in $H_2O$ at $25.0^{\circ}C$. The plots of $k_{obsd}$ vs. [amine] are linear and pass through the origin, indicating that general-base catalysis by a second amine molecule is absent. The Br${\o}$nsted-type plot exhibits an excellent linear correlation with ${\beta}_{nuc}$ = 0.46 when hydrazine is excluded from the correlation. The reaction has been suggested to proceed through a stepwise mechanism, in which expulsion of the leaving group occurs after the rate-determining step (RDS). Hydrazine is ca. 10 times more reactive than similarly basic glycylglycine (i.e., the ${\alpha}$-effect). A five-membered cyclic intermediate has been suggested for the reaction with hydrazine, in which intramolecular H-bonding interactions would facilitate expulsion of the leaving group. However, the enhanced leaving-group ability is not responsible for the ${\alpha}$-effect shown by hydrazine because expulsion of the leaving group occurs after RDS. Destabilization of the ground-state of hydrazine through the electronic repulsion between the nonbonding electron pairs is responsible for the ${\alpha}$-effect found in the current $S_NAr$ reaction.

• 대한화학회지
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• 제19권5호
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• pp.339-342
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• 1975

요오드와 히드라진 사이의 반응을 요오드의 소비속도와 기체발생 속도를 비교하는 방법으로 검토하였다. 낮은 pH에서는 요오드의 소비속도가 율속단계이나 중성 및 약한 산성에서는 기체발생 속도가 율속과정이다. 요오드 소비속도가 기체 발생속도의 1000배쯤 된다. 이들 사실을 실명하기 위하여 중간몰(아마 $N_2H_2I_2$)이 생성되어 그 분해속도 상수가 중성에서 약 1.5${\times}10^{-3}sec^{-1}$쯤 된다는 가정을 제시하였다.

• 대한화학회지
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• 제45권5호
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• pp.454-460
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• 2001

3-Methoxycarbonylmethylene-2-oxo-1,2,3,4-tetrahydroquinoxaline(7)을 hydrazine hydrate와 반응시켜 3-hydrazinocarbonylmethylene-2-oxo-1,2,3,4-tetrahydroquinoxaline(8)을 합성하였다. 화합물 8을 alkyl (ethoxymethylene)cyanoacetate류와 반응시켜 [(quinoxalin-2-ylidene)ethanoyl]-1H-pyrazole류(9)를 합성하였고, 화합물 9b를 N-alkylaniline류와 반응시켜 N-alkyl-(quinoxalin-2-ylidene)-N-phenylethanamide류(10)를 합성하였다. 얻어진 화합물 9, 10은 용액에서 enamine 형과 methylene imine 형 사이에 토토머화 현상을 나타내었는데, 이들의 토토머비를 $^1H$ NMR 로서 측정하였다.

• 한국전산유체공학회:학술대회논문집
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• 한국전산유체공학회 2006년도 추계 학술대회논문집
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• pp.101-105
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• 2006

The computational fluid dynamic analysis has been conducted for the thermo-chemical flow field in an arcjet thruster with mono-propellant Hydrazine (N2H4) as a working fluid. The Reynolds Averaged Navier-Stokes (RANS) equations are modified to analyze compressible flows with the thermal radiation and electric field. The Maxwell equation, which is loosely coupled with the fluid dynamic equations through the Ohm heating and Lorentz forces, is adopted to analyze the electric field induced by the electric arc. The chemical reactions of Hydrazine were assumed to be infinitely fast due to the high temperature field inside the arcjet thruster. The chemical and the thermal radiation models for the nitrogen-hydrogen mixture and optically thick media respectively, were incorporated with the fluid dynamic equations. The results show that performance indices of the arcjet thruster with 1kW arc heating are improved by amount of 180% in thrust and 200% in specific impulse more than frozen flow. In addition to thermo-physical process inside the arcjet thruster is understood from the flow field results.

• 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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• 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.

• 센서학회지
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• 제16권1호
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• pp.11-16
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• 2007

CuO is an important transition metal oxide with many practical applications such as catalysts, p-type semiconductor, solar cells, magnetic storage media and cathode materials. In this contribution, nanocrystalline CuO powders were prepared by solution reduction method using copper chloride ($CuCl_{2}{\cdot}2H_{2}O$), hydrazine ($N_{2}H_{4}$) and NaOH and subsequent heat treatment. The gas sensor using nanocrystalline CuO powders showed high sensitivities to acetone and ethanol.

• Advances in Energy Research
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• 제1권1호
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• pp.1-12
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• 2013

In this work, we present the catalytic dehydrogenation of hydrazine borane $N_2H_4BH_3$ (HB) using supported nickel catalysts at $50^{\circ}C$. In the presence of monometallic nickel catalysts, the dehydrogenation of HB is a one-step reaction consisting of the hydrolysis of the $BH_3$ group only. The challenge is to activate nickel to make it reactive towards the $N_2H_4$ moiety of HB. A set of 52 catalysts were prepared by using 2 supports ($Al_2O_3$ and $TiO_2$), 5 nickel precursors and 3 preparation methods. For the first time, we show that the supported nickel catalysts are able to dehydrogenate the $NH_3$ moiety of HB. In our experimental conditions, the best results were obtained with 20 wt% Ni-$Al_2O_3$ and 20 wt% Ni-$TiO_2$, with ca. 190 mL $H_2+N_2$ generated over a total theoretical volume of 283 mL, suggesting $H_2$ selectivity of 37 and 32%, respectively. Both catalysts were then characterized by EDX, XPS, and XRD. Our achievement is the first step forward and opens new perspectives for developing catalysts for the total dehydrogenation of HB.

• Nuclear Engineering and Technology
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• 제54권6호
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• pp.2329-2333
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• 2022

Base metal corrosion forms a significant issue during the chemical decontamination of the primary coolant loop in nuclear power plants as it is directly related to the economic and safety viability of decommissioning. In this technical note, potentiodynamic evaluations of several base metals (304 stainless steel, SA106 Grade B carbon steel, and alloy 600) were performed to determine their corrosion behavior during the hydrazine (N₂H₄)-based reductive ion decontamination (HyBRID) process. The results suggested that N₂H₄ protected the surface of the base metals in the HyBRID solution, which is primarily composed of H₂SO₄. The corrosion resistance of the carbon steel was further improved through the addition of CuSO₄ to the solution. The corrosion rate of carbon steel in the H₂SO₄-N₂H₄-CuSO₄ solution was lower than that exhibited in an oxalic acid solution, a commonly used reaction medium during commercial decontamination processes. These results indicate the superiority of the HyBRID process with respect to the base metal stability.