• Bulletin of the Korean Chemical Society
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• 제32권1호
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• pp.219-224
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• 2011

The new MPV type reagent, Al-trifluoromethanesulfonyldiisobutylalane ($DIBAO_3SCF_3$), has been prepared and its reducing characteristics in the reduction of selected organic compounds containing representative functional groups have been examined, and compared its reactivity with that of Al-methanesulfonyldiisobutylalane ($DIBAO_3SCH_3$) in order to understand the fluorine-substituent effect on its reactivity. In general, the reactivity of $DIBAO_3SCF_3$ appears to be much higher than that of $DIBAO_3SCH_3$, apparently due to the acidity increase by the electron-withdrawing fluorine-substituent. The reagent reduced aldehydes and ketones readily, but showed a perfect selectivity in the reduction of $\alpha,\beta$-unsaturated aldehydes and ketones to produce the corresponding allylic alcohols in an absolutely 100% purity. In addition, the reagent achieved the regioselective cleavage of phenyl- or/and alkyl-substituted epoxides to the less substituted alcohols in a perfect regioselectivity. Moreover, the reagent also showed an high stereoselectivity in the reduction of substituted cycloalkanones to produce the thermodynamically more stable alcohol epimers exclusively.

• Bulletin of the Korean Chemical Society
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• 제34권8호
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• pp.2335-2339
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• 2013

Relative reactivity of various Al-substituted dialkylalans ($AlR_2(X)$) in reduction of acetone has been studied with density functional theory and MP2 method. Formation of the alan dimers and the alan-acetone adduct, and the transition state for the Meerwein-Ponndorf-Verley (MPV) type reduction of the adduct were calculated to figure out the energy profile. Formation of dimeric alans is highly exothermic. Both the relative free energies for acetone-alan adduct formation and the TS barriers for the MPV type reduction with respect to alan dimers and acetone were calculated and they show the same trend. Based on these energetic data, relative reactivity of alans is expected to be; $AlR_2(Cl)$ > $AlR_2(OTf)$ > $AlR_2(O_2CCF_3)$ > $AlR_2(F)$ > $AlR_2(OMs)$ > $AlR_2(OAc)$ > $AlR_2(OMe)$ > $AlR_2(NMe_2)$. The energy profile is relatively well correlated with the experimental order of the reactivity of Al-substituted dialkylalans. It is noted that the substituents of alans have initial effects on the relative free energies for the carbonyl-adduct formation. Therefore, an $AlR_2(X)$ which forms a more stable carbonyl-adduct is more reactive in carbonyl reduction.

• Environmental Engineering Research
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• 제10권4호
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• pp.174-180
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• 2005

Nano-sized iron was synthesized using borohydride reduction of $Fe^{3+}$ in aqueous solution. A wide range of synthesis conditions including varying concentrations of reagents, reagent feeding rate, and solution pH was applied in an aqueous system under anaerobic condition. The reactivity of nano-sized iron from each synthesis was evaluated by reacting the iron with TCE in batch systems. Evidence obtained from this study suggest the reactivity of iron is strongly dependent on the synthesis solution pH. The iron reactivity increased as solution pH decreased. More rapid TCE reduction was observed for iron samples synthesized from higher initial $Fe^{3+}$ concentration, which resulted in lower solution pH during the synthesis reaction. Faster feeding of $BH_4^-$ solution to the $Fe^{3+}$ solution resulted in lower synthesis solution pH and the resultant iron samples gave higher TCE reduction rate. Lowering the pH of the solution after completion of the synthesis reaction significantly increased reactivity of iron. It is presumed that the increase in the reactivity of iron synthesized at lower pH is due to less precipitation of iron (hydr)oxides or less surface passivation of iron.

• Bulletin of the Korean Chemical Society
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• 제35권2호
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• pp.546-550
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• 2014

Relative reactivity of various carbonyl and acid derivatives in MPV-type (Meerwein-Ponndorf-Verley) reduction with an DIBAL(F) model has been studied via DFT and MP2 methods. Free energies of initial adduct formation (-Gadd) of DIBAL(F) model and carbonyls are in the order of amide < ester < aldehyde < ketone < acid chloride; in the alan-amide adduct, the developed positive charge at carbonyl carbon is expected to be stabilized by amide resonance, but in the acid chloride adduct it is destabilized by inductive effect of chloride. However the TS barrier energies (${\Delta}G_{TS}$) for the MPV-type hydride reduction of the carbonyl adducts are in the order of aldehyde < ketone < acid chloride << ester < amide; presumably decreasing order of electrophilicity of carbonyl carbon at adducts, which is well correlated with experimental data. It is noted that the relative reactivity of carbonyl derivatives in MPV-type reduction with DIBAL(X) is not governed by the alan-adduct formation energies, but follows the order of electrophilicity of carbonyl carbon of transition states.

• Nuclear Engineering and Technology
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• 제56권3호
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• pp.785-792
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• 2024

This article provides an overview of the design methodology used to develop a conceptual set of reactivity control mechanism of a micro reactor based on the U-Battery. The U-Battery is based on remote deployment and therefore it is favourable to provide a long fuel lifecycle. This is achieved by implementing a high fissile loading content, which proves challenging when considering reactivity control methods. This article follows the design methodology used to overcome these issues, with an emphasis on a new concept of a moveable moderator which utilises the size of the U-Battery as a small reduction in moderation provides a significant reduction in reactivity. The latest work on this project sees the moveable moderator investigated during a depressurised loss of forced coolant accident, where a reduction of moderator volume increases the maximum fuel temperature experienced. The overall conclusion is that the maximum fuel temperature is not significantly increased (4 K) due to the central reflector region relatively lower volumetric heat capacity compared to that of whole core. However, a small temperature increase is observed immediately after the transient due to the central reflector removal because it reaches energy equilibrium with the fuel region faster.

• 한국환경과학회지
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• 제29권12호
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• pp.1205-1211
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• 2020

In this study, the applicability of reduction-oxidation-linked treatment was evaluated for nitrobenzene and a by-product by analyzing the reaction kinetics. Nitrobenzene showed very low reactivity to persulfate that was activated using various methods. Nitrobenzene effectively reacted through the reduction process using Zero-Valent Iron (ZVI). However, aniline, a toxic substance, was produced as a by-product. Reduction-oxidation-linked treatment is a method that can allow the oxidative degradation of aniline after reducing nitrobenzene to aniline. The experimental results show improved reactivity and complete decomposition of the by-product. Improved reactivity and decomposition of the by-product were observed even under conditions in which the reduction-oxidation reaction was induced simultaneously. No activator was injected for persulfate activation in the process of reducing oxidant linkage, and the activation reaction was induced by ferrous iron eluted from the ZVI. This indicates that this method can be implemented relatively simply.

• 한국원자력학회:학술대회논문집
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• 한국원자력학회 1996년도 춘계학술발표회논문집(1)
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• pp.52-57
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• 1996

The coolant void reactivity is positive for CANDU reactor loaded with DUPIC fuel which has more fissile content compared to natural uranium. A parametric study was done to reduce the void reactivity of the fuel bundle and loss in discharge burnup was estimated. It is observed that the burnable absorbers like gadolinium, boron, europium are not able to keep the reduction in void reactivity uniform throughout fuel burnup. Dysprosium and erbium can keep the void reactivity reduction uniform throughout. fuel burnup but toss in discharge burnup for erbium case is more compared to that of dysprosium case.

• Bulletin of the Korean Chemical Society
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• 제25권10호
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• pp.1463-1464
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• 2004

• Environmental Engineering Research
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• 제10권4호
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• pp.165-173
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• 2005

Nano-sized iron particles were synthesized by reduction of $Fe^{3+}$ in aqueous solution under two reaction conditions, aerobic and anaerobic, and the reactivity of iron was tested by reaction with trichloroethene (TCE) using a batch system. Results showed that iron produced under anoxic condition for both synthesis and drying steps gave rise to iron with higher reduction reactivity, indicating the presence of oxygen is not favorable for production of nano-sized iron deemed to accomplish reactivity enhancement from particle sized reduction. Nano-sized iron sample obtained from the anoxic synthesis condition was further characterized using various instrumental measurements to identity particle morphology, composition, surface area, and particle size distribution. The scanning electron microscopic (SEM) image showed that synthesized particles were uniform, spherical particles (< 100 nm), and aggregated into various chain structures. The effects of other synthesis conditions such as solution pH, initial $Fe^{3+}$ concentration, and reductant injection rate on the reactivity of nano-sized iron, along with standardization of the synthesis protocol, are presented in the companion paper.

• 한국수소및신에너지학회논문집
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• 제27권5호
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• pp.589-596
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• 2016

Effects of pressure, temperature, gas velocity, and fuel flow rate on reduction of three oxygen carriers, SDN70, OC-1, OC-2, were measured and investigated in a pressurized bubbling fluidized bed reactor. Among three oxygen carriers OC-2 was selected as the best oxygen carrier in view of fuel conversion and $CO_2$ selectivity. However, all oxygen carriers showed good reactivity even at high pressure conditions. SDN70 particle showed maximum reactivity at $900^{\circ}C$ and low reactivity at $950^{\circ}C$. However, reactivity decay of OC-1 and OC-2 particles at high temperature condition was negligible. The fuel conversion and the $CO_2$ selectivity slightly decreased as the gas velocity increased, whereas they are slightly increased as the fuel concentration increased.