• Nuclear Engineering and Technology
• /
• v.26 no.3
• /
• pp.425-432
• /
• 1994

Voltammogram analysis of U(VI) reduction at electrochemically non-pretreated/pretreated Ti electrodes in nitric acid and hydrazine($N_2$H$_4$)/protonated hydrazine($N_2$H$_{5}$$^{＋}$) media was done in order to determine the effect of hydrazine form and Ti electrode condition on the reduction of U(VI) in nitric acid. In the case of non-pretreated Ti electrode, the reduction in nitric acid and hydrazine mono-hydrate solution needed a high activation overpotential and was affected by the ratio of hydrazine to nitric acid rather than by only absolute amount of hydrazine because of the decrease of solution conductivity and increase of iR drop, which were caused by proton consumption in the solution by the hydrazine. In the case of pretreated Ti electrode in nitric acid and protonated hydrazine solution, the reduction current peaks of U(VI) were clearer and higher enough to perform a kinetic analysis, compared with the case with the non-pretreated Ti electrode at the same potential, and the behavior was strongly affected by nitric acid. The presence of hydrazine was important in the reduction of U(VI) at the pretreated Ti electrode for preventing the reoxidation of U(IV), but the concentration of protonated hydrazine was not.t.

• Bulletin of the Korean Chemical Society
• /
• v.35 no.8
• /
• pp.2371-2374
• /
• 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.

• Journal of the Korean Chemical Society
• /
• v.19 no.5
• /
• pp.339-342
• /
• 1975

The rates of consumption of iodine and gas evolution in hydrazine-iodine reaction in the presence of large excess of hydrazine have been studied in the pH range 0.5${\sim}$7. They are the same at very low pH and both increase to respective asymptotic values as pH is increased. The rate of iodine consumption is three orders of magnitude faster than the rate of gas evolution at higher pH. The results are explained by postulating that $N_2H_4$ but not protonated form reacts with iodine and an intermediate, probably $N_2H_2I_2$, is formed which decomposed by first order reaction of rate constant about 1.5${\times}10^{-3}sec^{-1}$ in neutral and weakly acidic solutions.

• Journal of the Korean Chemical Society
• /
• v.45 no.5
• /
• pp.454-460
• /
• 2001

The reaction of 3-methoxycarbonylmethylene-2-oxo-1,2,3,4-tetrahydroquinoxaline(7) with hydrazine hydrate gave 3-hydrazinocarbonylmethylene-2-oxo-1,2,3,4-tetrahydroquinoxaline(8). The reaction of compound 8 with alkyl (ethoxymethylene)cyanoacetates gave the [(quinoxalin-2-ylidene)ethanoyl]-1H-pyra-zoles(9). The reaction of compound 9b with N-alkylanilines provided the N-alkyl-(quinoxalin-2-ylidene)-N-phenylethanamides(10). Compounds 9 and 10 showed the tautomerism between the enamine and methylene imine forms in solution. The tautomer ratios were determined by the $^1H$ NMR.

• 한국전산유체공학회:학술대회논문집
• /
• 2006.10a
• /
• pp.101-105
• /
• 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
• /
• v.35 no.8
• /
• pp.2271-2276
• /
• 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
• /
• v.35 no.8
• /
• pp.2448-2452
• /
• 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.

• Journal of Sensor Science and Technology
• /
• v.16 no.1
• /
• pp.11-16
• /
• 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
• /
• v.1 no.1
• /
• pp.1-12
• /
• 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
• /
• v.54 no.6
• /
• pp.2329-2333
• /
• 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.