• Title/Summary/Keyword: reactivity

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A comparative study on the impact of Gd2O3 burnable neutron absorber in UO2 and (U, Th)O2 fuels

  • Uguru, Edwin Humphrey;Sani, S.F.Abdul;Khandaker, Mayeen Uddin;Rabir, Mohamad Hairie;Karim, Julia Abdul
    • Nuclear Engineering and Technology
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    • v.52 no.6
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    • pp.1099-1109
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    • 2020
  • The performance of gadolinium burnable absorber (GdBA) for reactivity control in UO2 and (U, Th)O2 fuels and its impact on spent fuel characteristics was performed. Five fuel assemblies: one without GdBA fuel rod and four each containing 16, 24, 34 and 44 GdBA fuel rods in both fuels were investigated. Reactivity swing in all the FAs with GdBA rods in UO2 fuel was higher than their counterparts with similar GdBA fuel rods in (U, Th)O2 fuel. The excess reactivity in all FAs with (U, Th)O2 fuel was higher than UO2 fuel. At the end of single discharge burn-up (~ 49.64 GWd/tHM), the excess reactivity of (U, Th) O2 fuel remained positive (16,000 pcm) while UO2 fuel shows a negative value (-6,000 pcm), which suggest a longer discharge burn-up in (U, Th)O2 fuel. The concentration of plutonium isotopes and minor actinides were significantly higher in UO2 fuel than in (U, Th)O2 fuel except for 236Np. However, the concentration of non-actinides (gadolinium and iodine isotopes) except for 135Xe were respectively smaller in (U, Th)O2 fuel than in UO2 fuel but may be two times higher in (U, Th)O2 fuel due to its potential longer discharge burn-up.

Kinetic Study on Aminolysis of Y-Substituted-Phenyl Picolinates: Effect of H-Bonding Interaction on Reactivity and Transition-State Structure

  • Kim, Min-Young;Kang, Tae-Ah;Yoon, Jung Hwan;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2410-2414
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    • 2014
  • A kinetic study is reported on nucleophilic substitution reactions of Y-substituted-phenyl picolinates (7a-7h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Comparison of the kinetic results with those reported previously for the corresponding reactions of Y-substituted-phenyl benzoates (1a-1f) reveals that 7a-7h are significantly more reactive than 1a-1f. The Br${\o}$nsted-type plot for the aminolysis of 4-nitrophenyl picolinate (7a) is linear with ${\beta}_{nuc}=0.78$, which is typical for reactions proceeding through a stepwise mechanism with expulsion of the leaving group being the rate-determining step. The Br${\o}$nsted-type plots for the piperidinolysis of 7a-7h and 1a-1f are also linear with ${\beta}_{lg}=-1.04$ and -1.39, respectively, indicating that the more reactive 7a-7h are less selective than the less reactive 1a-1f to the leaving-group basicity. One might suggest that the enhanced reactivity of 7a-7h is due to the inductive effect exerted by the electronegative N atom in the picolinyl moiety, while the decreased selectivity of the more reactive substrates is in accord with the reactivity-selectivity principle. However, the nature of intermediate (e.g., a stabilized cyclic intermediate through the intramolecular H-bonding interaction for the reactions of 7a-7h, which is structurally not possible for the reactions of 1a-1f) is also responsible for the enhanced reactivity with a decreased selectivity.

INHERENT SAFETY ANALYSIS OF THE KALIMER UNDER A LOFA WITH A REDUCED PRIMARY PUMP HALVING TIME

  • Chang, W.P.;Kwon, Y.M.;Jeong, H.Y.;Suk, S.D.;Lee, Y.B.
    • Nuclear Engineering and Technology
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    • v.43 no.1
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    • pp.63-74
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    • 2011
  • The 600 MWe, pool-type, sodium-cooled, metallic fuel loaded KALIMER-600 (Korea Advanced LiquId MEtal Reactor, 600 MWe) has been conceptually designed with an emphasis on safety by self-regulating (inherent/intrinsic) negative reactivity feedback in the core. Its inherent safety under the ATWS (Anticipated Transient Without Scram) events was demonstrated in an earlier study. Initiating events of an HCDA (Hypothetical Core Disruptive Accident), however, also need to be analyzed for assessment of the margins in the current design. In this study, a hypothetical triple-fault accident, ULOF (Unprotected Loss Of Flow) with a reduced pump halving time, is investigated as an initiator of a core disruptive accident. A ULOF with insufficient primary pump inertia may cause core sodium boiling due to a power-to-flow mismatch. If the positive sodium reactivity resulting from this boiling is not compensated for by other intrinsic negative reactivity feedbacks, the resulting core power burst would challenge the fuel integrity. The present study focuses on determination of the limit of the pump inertia for assuring inherent reactivity feedback and behavior of the core after sodium boiling as well. Transient analyses are performed with the safety analysis code SSC-K, which now incorporates a new sodium boiling model. The results show that a halving time of more than 6.0 s does not allow sodium boiling even with very conservative assumptions. Boiling takes place for a halving time of 1.8 s, and its behavior can be predicted reasonably by the SSC-K.

Aminolysis of Benzyl 2-Pyridyl Thionocarbonate and t-Butyl 2-Pyridyl Thionocarbonate: Effects of Nonleaving Groups on Reactivity and Reaction Mechanism

  • Kim, Min-Young;Lee, Jae-In;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.4
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    • pp.1115-1119
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    • 2013
  • A kinetic study is reported for nucleophilic substitution reactions of benzyl 2-pyridyl thionocarbonate (5b) and t-butyl 2-pyridyl thionocarbonate (6b) with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. General-base catalysis, which has often been reported to occur for aminolysis of esters possessing a C=S electrophilic center, is absent for the reactions of 5b and 6b. The Br${\o}$nsted-type plots for the reactions of 5b and 6b are linear with ${\beta}_{nuc}$ = 0.29 and 0.43, respectively, indicating that the reactions of 5b proceed through a stepwise mechanism with formation of a zwitterionic tetrahedral intermediate ($T^{\pm}$) being the rate-determining step while those of 6b proceed through a concerted mechanism. The reactivity of 5b and 6b is similar to that of their oxygen analogues (i.e., benzyl 2-pyridyl carbonate 5a and t-butyl 2-pyridyl carbonate 6a, respectively), indicating that the effect of modification of the electrophilic center from C=O to C=S (i.e., from 5a to 5b and from 6a to 6b) on reactivity is insignificant. In contrast, 6b is much less reactive than 5b, indicating that the replacement of the $PhCH_2$ in 5b by the t-Bu in 6b results in a significant decrease in reactivity as well as a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway). It has been concluded that the contrasting reactivity and reaction mechanism for the reactions of 5b and 6b are not due to the electronic effects of $PhCH_2$ and t-Bu but are caused by the large steric hindrance exerted by the bulky t-Bu in 6b.

A comparative study of immediate wound healing complications following cleft lip repair using either absorbable or non-absorbable skin sutures

  • Alawode, Akeem O.;Adeyemi, Michael O.;James, Olutayo;Ogunlewe, Mobolanle O.;Butali, Azeez;Adeyemo, Wasiu L.
    • Journal of the Korean Association of Oral and Maxillofacial Surgeons
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    • v.44 no.4
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    • pp.159-166
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    • 2018
  • Objectives: The aim of the study was to compare wound healing complications following the use of either absorbable or non-absorbable sutures for skin closure in cleft lip repair. Materials and Methods: This was a randomized controlled trial conducted at the Department of Oral and Maxillofacial Surgery, Lagos University Teaching Hospital, Idi Araba, Lagos State, Nigeria. Sixty subjects who required either primary or secondary cleft lip repair and satisfied all the inclusion criteria were recruited and randomized into two groups (Vicryl group or Nylon group). The surgical wounds in all subjects were examined on 3rd, 7th, and 14th postoperative days (POD) for presence or absence of tissue reactivity, wound dehiscence, and local wound infection. Results: Hemorrhage, tissue reactivity, wound dehiscence, and local wound infection were identified as wound healing complications following cleft lip repair. The incidence of postoperative wound healing complications on POD3 was 33.3%. Tissue reactivity was more common throughout the evaluation period with the use of an absorbable (Vicryl) suture compared to a non-absorbable (Nylon) suture, although the difference was statistically significant only on POD7 (P=0.002). There were no significant differences in the incidences of wound dehiscence and infection between the two groups throughout the observation period. Conclusion: There were no statistically significant differences in the incidences of wound dehiscence and surgical site wound infection following the use of either Vicryl or Nylon for skin closure during cleft lip repair. However, more cases of tissue reactivity were recorded in the Vicryl group than in the Nylon group on POD7. Particular attention must be paid to detect the occurrence of wound healing complications, most especially tissue reactivity, whenever a Vicryl suture is used for skin closure in cleft lip repair.

A Kinetic Study on Aminolysis of Benzyl 2-Pyridyl Thionocarbonate and t-Butyl 2-Pyridyl Thionocarbonate: Effects of Polarizability and Steric Hindrance on Reactivity and Reaction Mechanism

  • Kim, Min-Young;Bae, Ae Ri;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.8
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    • pp.2325-2329
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    • 2013
  • Second-order rate constants $k_N$ have been measured for reactions of benzyl 2-pyridyl thionocarbonate (4b) and t-butyl 2-pyridyl thionocarbonate (5b) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 4b and 5b have been compared with those reported previously for the corresponding reactions of benzyl 2-pyridyl carbonate (4a) and t-butyl 2-pyridyl carbonate (5a) to investigate the effect of changing the electrophilic center from C=O to C=S on reactivity and reaction mechanism. The thiono compound 4b is more reactive than its oxygen analogue 4a. The Br${\o}$nsted-type plots for the reactions of 4a and 4b are linear with ${\beta}_{nuc}=0.57$ and 0.37, respectively. The reactions of 4a were previously reported to proceed through a concerted mechanism, while those of 4b in this study have been concluded to proceed through a stepwise mechanism with formation of an intermediate being the rate-determining step on the basis of the ${\beta}_{nuc}$ value of 0.37. Enhanced polarizability upon changing the C=O in 4a by C=S has been suggested to be responsible for the reactivity order and the contrasting reaction mechanisms. In contrast, the reactivity of 5a and 5b is similar, but they are much less reactive than 4a and 4b. Furthermore, the reactions of 5a and 5b have been concluded to proceed through the same mechanism (i.e., a concerted mechanism) on the basis of linear Bronsted-type plots with ${\beta}_{nuc}=0.45$ or 0.47. It has been concluded that the strong steric hindrance exerted by the t-Bu in 5a and 5b causes a decrease in their reactivity and forces the reactions to proceed through a concerted mechanism.

An approach to minimize reactivity penalty of Gd2O3 burnable absorber at the early stage of fuel burnup in Pressurized Water Reactor

  • Nabila, Umme Mahbuba;Sahadath, Md. Hossain;Hossain, Md. Towhid;Reza, Farshid
    • Nuclear Engineering and Technology
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    • v.54 no.9
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    • pp.3516-3525
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    • 2022
  • The high capture cross-section (𝜎c) of Gadolinium (Gd-155 and Gd-157) causes reactivity penalty and swing at the initial stage of fuel burnup in Pressurized Water Reactor (PWR). The present study is concerned with the feasibility of the combination of mixed burnable poison with both low and high 𝜎c as an approach to minimize these effects. Two considered reference designs are fuel assemblies with 24 IBA rods of Gd2O3 and Er2O3 respectively. Models comprise nuclear fuel with a homogeneous mixture of Er2O3, AmO2, SmO2, and HfO2 with Gd2O3 as well as the coating of PaO2 and ZrB2 on the Gd2O3 pellet's outer surface. The infinite multiplication factor was determined and reactivity was calculated considering 3% neutron leakage rate. All models except Er2O3 and SmO2 showed expected results namely higher values of these parameters than the reference design of Gd2O3 at the early burnup period. The highest value was found for the model of PaO2 and Gd2O3 followed by ZrB2 and HfO2. The cycle burnup, discharge burnup, and cycle length for three batch refueling were calculated using Linear Reactivity Model (LRM). The pin power distribution, energy-dependent neutron flux and Fuel Temperature Coefficient (FTC) were also studied. An optimization of model 1 was carried out to investigate effects of different isotopic compositions of Gd2O3 and absorber coating thickness.

Molecular holographic QSPR analysis on the reactivity between glycine and ninhydrin analogues as latent fingerprints detector (잠재지문 검출제로서 Ninhydrin 유도체들과 Glycine과의 반응성에 관한 분자 홀로그래픽적인 QSPR 분석)

  • Kim, Se-Gon;Jang, Seok-Chan;Cho, Yun-Gi;Hwang, Tae-Yeon;Park, Sung-Woo;Sung, Nack-Do
    • Analytical Science and Technology
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    • v.20 no.4
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    • pp.339-346
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    • 2007
  • To search the ninhydrin derivatives that have high chromogenic and fluorogenic properties, molecular holographic quantitative structure property relationship (HQSPR) models on the reactivity between glycine and ninhydrin analogues as latent fingerprint detector were derived and investigated quantitatively. The ${\varepsilon}LUMO$ (e.v.) energy of ninhydrin molecule was an important factor to reactivity of ninhydrin. And, it is suggested that the nucleophilic reaction by orbital-controlled reaction from the frontier molecular orbital (FMO) interaction between glycine and ninhydrin derivatives was more superior than that of electrophilic reaction by charged controlled reaction. The analytical results in atomic contribution maps also shows that the reactivity of ninhydrin was increased by meta-substituents as strong electron withdrawing groups on the benzo ring. Therefore, it is sugested by HQSPR and QSPR model that the 5,6-dinitroninhydrin molecule would increase the reactivity as much as three times as compared to none substituted ninhydrin molecule.

MNSR transient analysis using the RELAP5/Mod3.2 code

  • Dawahra, S.;Khattab, K.;Alhabit, F.
    • Nuclear Engineering and Technology
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    • v.52 no.9
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    • pp.1990-1997
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    • 2020
  • To support the safe operation of the Miniature Neutron Source Reactor (MNSR), a thermo-hydraulic transient model using the RELAP5/Mod3.2 code was simulated. The model was verified by comparing the results with the measured and the previously calculated data. The comparisons consisted of comparing the MNSR parameters under normal constant power operation and reactivity insertion transients. Reactivity Insertion Accident (RIA) for three different initial reactivity values of 3.6, 6.0, and 6.53 mk have been simulated. The calculated peaks of the reactor power, fuel, clad and coolant temperatures in hot channel were calculated in this model. The reactor power peaks were: 103 kW at 240 s, 174 kW at 160 s and 195 kW at 140 s, respectively. The fuel temperature reached its maximum value of 116 ℃ at 240 s, 124 ℃ at 160 s and 126 ℃ at 140 s respectively. These calculation results ensured the high inherently safety features of the MNSR under all phases of the RIAs.

Characteristics of Co-Combustion of Korean Anthracite with Bituminous Coal in a Circulating Fluidized Bed (순환유동층에서 유.무연탄 혼소 특성)

  • Lee, J.M.;Kim, J.S.;Lee, E.M.
    • Journal of the Korean Society of Combustion
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    • v.10 no.3
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    • pp.1-9
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    • 2005
  • The characteristics of co-combustion of Korean anthracite and bituminous coal was determined in a TGA and a lab-scale CFB reactor. The combustion reactivity of Korean anthracite (E = 51.2 kcal/mol) was much lower than that of bituminous coal (E = 14.5 kcal/mol). As the addition amount of the bituminous coal into the anthracite was increased, the reactivity of the anthracite was found to be improved. The effluent rate of the emission gases from the CFB reactor was not changed appreciably when each coal burned. As the bituminous coal was added, however, the effluent rate of the emissions was increased. The unburned carbon in fly ash from the CFB reactor was decreased with increasing the ratio of bituminous coal in co-combustion. But as the ratio of the bituminous coal was larger than 40 %, the combustion reactivity was not increased any more.

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