• Title/Summary/Keyword: Reactivity Effect

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The Effect of Polarizability on Reactivity of 4-Nitrophenyl Benzoate and Its Sulfur Containing Analogues with Anionic Nucleophiles in Ethanol

  • Kwon, Dong-Sook;Park, Jee-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.15 no.10
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    • pp.860-864
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    • 1994
  • 2nd-order rate constants have been measured spectrophotometrically for the reactions of 4-nitrophenyl benzoate (1), S-4-nitrophenyl thiobenzoate (2) and 4-nitrophenyl thionbenzoate (3) with alkoxides, aryloxides and thioaryloxides in absolute ethanol at 25.0 ${\pm}0.1$${\circ}C$. The substitution of O by polarizable S in the leaving group has little affected the reactivity of 2 toward the charge localized species (eg. $EtO^-$ and $CF_3CH_2O^-$), while the effect of the similar replacement in the carbonyl group has led to a decrease in reactivity by a factor of 10. However, the reactivity of these esters toward charge delocalized aryloxides has been found to be in the order $1<3{\le}2$. The effect of replaced sulfur atom on reactivity becomes more significant for the reaction with polarizable thioaryloxides, i.e. the reactivity increases in the order $1<2{\ll}3$. The difference in reactivity for the present system is attributed to a polarizability effect.

The Effect of the Changing of C-O-C to C-S-C and C=O to C=S on Reactivity of 4-Nitrophenyl Benzoate with Alkali Metal Ethoxides in Ethanol

  • Kwon, Dong-Sook;Park, Hee-Sun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.12 no.1
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    • pp.93-97
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    • 1991
  • Rate constants have been measured spectrophotometrically for the reactions of alkali metal ethoxides with 4-nitrophenyl benzoate, S-4-nitrophenyl thiobenzoate and 4-nitrophenyl thionbenzoate in ethanol at 25$^{\circ}$C. Substitution of S for O in the leaving group has not affected reactivity significantly, while the effect of the similar replacement in the acyl group has led to rate decrease by a factor of 10, although pronounced rate enhancements have been expected for both systems. The replacement of O by a polarizable S has also influenced the reactivity of the esters toward alkali metal ethoxides, i.e. the reactivity decreases as the size of the metal ion decreases. The alkali metal ions have showed inhibition effect instead of catalytic effect which would have been expected for the present system. The effect of replaced sulfur atom on the reactivity for the present system is attributed to the nature of hard and soft acids and bases.

Physics Study of Canada Deuterium Uranium Lattice with Coolant Void Reactivity Analysis

  • Park, Jinsu;Lee, Hyunsuk;Tak, Taewoo;Shin, Ho Cheol;Lee, Deokjung
    • Nuclear Engineering and Technology
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    • v.49 no.1
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    • pp.6-16
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    • 2017
  • This study presents a coolant void reactivity analysis of Canada Deuterium Uranium (CANDU)-6 and Advanced Canada Deuterium Uranium Reactor-700 (ACR-700) fuel lattices using a Monte Carlo code. The reactivity changes when the coolant was voided were assessed in terms of the contributions of four factors and spectrum shifts. In the case of single bundle coolant voiding, the contribution of each of the four factors in the ACR-700 lattice is large in magnitude with opposite signs, and their summation becomes a negative reactivity effect in contrast to that of the CANDU-6 lattice. Unlike the coolant voiding in a single fuel bundle, the $2{\times}2$ checkerboard coolant voiding in the ACR-700 lattice shows a positive reactivity effect. The neutron current between the no-void and voided bundles, and the four factors of each bundle were analyzed to figure out the mechanism of the positive coolant void reactivity of the checkerboard voiding case. Through a sensitivity study of fuel enrichment, type of burnable absorber, and moderator to fuel volume ratio, a design strategy for the CANDU reactor was suggested in order to achieve a negative coolant void reactivity even for the checkerboard voiding case.

Evaluation of coolant density history effect in RBMK type fuel modelling

  • Tonkunas, Aurimas;Pabarcius, Raimоndas;Slavickas, Andrius
    • Nuclear Engineering and Technology
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    • v.52 no.11
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    • pp.2415-2421
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    • 2020
  • The axial heterogeneous void distribution in a fuel channel is a relevant and important issue during nuclear reactor analysis for LWR, especially for boiling water channel-type reactors. Variation of the coolant density in fuel channel has an effect on the neutron spectrum that will in turn have an impact on the values of absolute reactivity, the void reactivity coefficient, and the fuel isotopic compositions during irradiation. This effect is referring to as the history effect in light water reactor calculations. As the void reactivity effect is positive in RBMK type reactors, the underestimation of water density heterogeneity in 3D reactor core numerical calculations could cause an uncertainty during assessment of safe operation of nuclear reactor. Thus, this issue is analysed with different cross-section libraries which were generated with WIMS8 code at different reference water densities. The libraries were applied in single fuel model of the nodal code of QUABOX-CUBBOX/HYCA. The thermohydraulic part of HYCA allowed to simulate axial water distribution along fuel assembly model and to estimate water density history effect for RBMK type fuel.

Determination of Reactivity by MO Theory (Part 32). MO Studies of Substituent Effects on the Gas-Phase Decarboxylation of But-3-enoic Acid (분자궤도론에 의한 반응성 결정 (제32보). 3-부테노산의 기체상 탈탄산반응에 미치는 치환기 효과의 분자궤도론적 연구)

  • Jeoung Ki Cho;Ikchoon Lee;Hyuck Keun Oh;In Ho Cho
    • Journal of the Korean Chemical Society
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    • v.28 no.5
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    • pp.279-283
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    • 1984
  • ${\beta}$-Substituent effect on the reactivity of retro-ene decarboxylation of but-3-enoic acid was investigated theoretically. It was found that charge effect is important not only through ${\pi}$-electron transfer as has been claimed to rationalize experimental results but also through polarization as found for the $CH_3$ substituent. The reactivity was not determined by the charge effect alone but the HOMO-LUMO energy gap was also found to affect the reactivity. In general it was confirmed that the greater the ${\pi}$-electron donating power of the substituent, the greater is the reactivity.

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Effect of Kinetic Parameters on Simultaneous Ramp Reactivity Insertion Plus Beam Tube Flooding Accident in a Typical Low Enriched U3Si2-Al Fuel-Based Material Testing Reactor-Type Research Reactor

  • Nasir, Rubina;Mirza, Sikander M.;Mirza, Nasir M.
    • Nuclear Engineering and Technology
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    • v.49 no.4
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    • pp.700-709
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    • 2017
  • This work looks at the effect of changes in kinetic parameters on simultaneous reactivity insertions and beam tube flooding in a typical material testing reactor-type research reactor with low enriched high density ($U_3Si_2-Al$) fuel. Using a modified PARET code, various ramp reactivity insertions (from $0.1/0.5 s to $1.3/0.5 s) plus beam tube flooding ($0.5/0.25 s) accidents under uncontrolled conditions were analyzed to find their effects on peak power, net reactivity, and temperature. Then, the effects of changes in kinetic parameters including the Doppler coefficient, prompt neutron lifetime, and delayed neutron fractions on simultaneous reactivity insertion and beam tube flooding accidents were analyzed. Results show that the power peak values are significantly sensitive to the Doppler coefficient of the system in coupled accidents. The material testing reactor-type system under such a coupled accident is not very sensitive to changes in the prompt neutron life time; the core under such a coupled transient is not very sensitive to changes in the effective delayed neutron fraction.

A critical study on best methodology to perform UQ for RIA transients and application to SPERT-III experiments

  • Dokhane, A.;Vasiliev, A.;Hursin, M.;Rochman, D.;Ferroukhi, H.
    • Nuclear Engineering and Technology
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    • v.54 no.5
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    • pp.1804-1812
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    • 2022
  • The aim of this paper is to assess the reliability and accuracy of the PSI standard method, used in many previous works, for the quantification of ND uncertainties in the SPERT-III RIA transient, by quantifying the discrepancy between the actual inserted reactivity and the original static reactivity worth and their associated uncertainties. The assessment has shown that the inherent S3K neutron source renormalization scheme, introduced before starting the transient, alters the original static reactivity worth of the transient CR and reduces the associated uncertainty due to the ND perturbation. In order to overcome these limitations, two additional methods have been developed based on CR adjustment. The comparative study performed between the three methods has showed clearly the high sensitivity of the obtained results to the selected approach and pointed out the importance of using the right procedure in order to simulate correctly the effect of ND uncertainties on the overall parameters in a RIA transient. This study has proven that the approach that allows matching the original static reactivity worth and starting the transient from criticality is the most reliable method since it conservatively preserves the effect of the ND uncertainties on the inserted reactivity during a RIA transient.

Effect of fineness of high lime fly ash on pozzolanic reactivity and ASR mitigation

  • Afshinnia, Kaveh;Rangaraju, Prasada R.
    • Computers and Concrete
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    • v.20 no.2
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    • pp.197-204
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    • 2017
  • Typically, high lime fly ash (Class C) has been characterized as a fly ash, which at lower replacement levels is not as effective as the low lime (Class F) fly ash, in mitigating alkali-silica reaction (ASR) in portland cement concrete. The influence of fineness of Class C, obtained by grinding virgin fly ash into finer particles, on its pozzolanic reactivity and ASR mitigation performance was investigated in this study. In order to assess the pozzolanic reactivity of mortar mixtures containing virgin or ground fly ashes, the strength activity index (SAI) test and thermo-gravimetric analysis (TGA) were conducted on the mortar cubes and paste samples, respectively, containing virgin fly ash or two ground fly ashes. In addition, to evaluate any improvement in the ASR mitigation of ground fly ashes compared to that of the virgin fly ash, the accelerated mortar bar test (AMBT) was conducted on the mortar mixtures containing different dosages of either virgin or ground fly ashes. In all tests crushed glass aggregate was used as a highly reactive aggregate. Results from this study showed that the finest fly ash (i.e., with an average particle size of 3.1 microns) could increase the flow ability along with the pozzolanic reactivity of the mortar mixture. However, results from this study suggested that the fineness of high lime fly ash does not seem to have any significant effect on ASR mitigation.

The Effect of the Structural State of Silica on the Pozzolanic Reactivity (Silica의 형태가 Pozzolan 반응성에 미치는 영향)

  • 한기성
    • Journal of the Korean Ceramic Society
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    • v.11 no.1
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    • pp.10-18
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    • 1974
  • The hydration at $23^{\circ}C$ between $Ca(OH)_2$ and siliceous materials with various compositions of silica gel and quartz were studied in paste state, and also diatomite was empolyed as another form of silica. The effect of the structural state of silica on the pozzolanic reactivity was investigated by X-ray, DTA, electron microscopy, and chemical analysis. The results obtained were as follows. (1) The molar ratio of $Ca(OH)_2$ to silica gel(C/Sg) being changed in 0.49, 0.81 and 1.22, the free $Ca(OH)_2$ was disappeared within six hours, three days and two weeks respectively and ill-crystallized CSH(I) was formed. However, in the case fo molar ratio of C/Sg=2.45, almost lime was remained uncombinedly after twenty four weeks yet. (2) Though the molar ratio C/Sg of diatomite was 0.71, the hydration was stabilized at three weeks and the result exhibited very peculiar characteristics from silica gel. (3) Pozzolanic reactivity of quartz was negligible, but $\alpha$-cristobalite in diatomite showed appreciable reactivity. (4) The thermal curves showed the exothermic peaks in the range 830 to $930^{\circ}C$ and lower broad peaks at high temperature in the initial steps of hydration, transfered to lower temperature with sharp peaks by proceeding of hydration. (5) The samples containing more silica gel exhibited higher pozzolanic reactivity and martar strength, but the diatomite gave remarkable result for them and they were matched to the strength development rate.

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Free-Radical Copolymerization of Glycidyl Methacrylate with Phthalimidoethyl Acrylate : Synthesis and Determination of Monomer Reactivity Ratios (GMA와 프탈이미드아크릴레이트의 공중합체 합성과 반응성비)

  • Oh, Seung-Min;Oh, Dae-Hee
    • Journal of the Korean Applied Science and Technology
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    • v.30 no.2
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    • pp.297-304
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    • 2013
  • Free-radical copolymerization of glycidyl methacrylate(GMA) and N-phthalimidoethyl acrylate(NPEA) were carried out at $60^{\circ}C$ in dimethylformamide(DMF) solution in the presence of benzoylperoxide(BPO) at low conversion. The polymers were characterized by IR and $^1H$-NMR. The compositions of the copolymer was analyzed by ultra violet(UV/Vis) spectrophotometry. The reactivity ratios of the monomer was determined by the application of Fineman-Ross(FR) and Kelen-T$\ddot{u}$d$\ddot{o}$s(KT) methods. The monomer reactivity ratios of the system and Alfrey-Price's resonance effect(Q) and polar effect(e) value for NIEA were determined as follow. The reactivity ratios of the monomer obtained from FR and KT are found to be $r_1$=0.87, $r_2$=0.98 and $r_1$=0.88, $r_2$=0.99 respectively. The Q and e values of poly(GMA-co-NPEM) calculated from $r_1$ and $r_2$ was Q= 1.31, e=0.75 respectively.