• Bulletin of the Korean Chemical Society
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• v.25 no.9
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• pp.1379-1384
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• 2004

Rearrangements of 1,3-oxathiolane sulfoxides 8 and 9 in the presence of base are described from a mechanistic viewpoint of sigmatropic and elimination reactions. In the presence of triethylamine the (Z)-sulfoxide 8 gave the corresponding thiolsulfinate 10 by way of dimerization of the sulfenic acid intermediate 2 at room temperature while the (E)-sulfoxide 9 was recovered even after refluxing in ethyl acetate by the reversal of the [2,3]-sigmatropic rearrangement of the sulfenic acid 4. Triethylamine promoted the developing charge separation in the transition state of the sigmatropic rearrangement of the (Z)-sulfoxide 8 to facilitate the ring opening to the sulfenic acid 2. The reason for more facile ring opening of the (Z)-sulfoxide 8 in comparison with the corresponding (E)-sulfoxide 9 is attributable to the differences in the reactivity of the hydrogen adjacent to the carbonyl group. Triethylamine was not strong base to deprotonate the carbonyl-activated methylene hydrogen of the (E)-sulfoxide 9 but enough to catalyze the sigmatropic process of the sulfoxides. The sulfenic acid 2 dimerized to the thiolsulfinate 10 while the sulfenic acid 4 proceeded the sigmatropic ring closure. In the presence of strong base such as potassium hydroxide, the elimination reaction was predominant over the sigmatropic rearrangement. In this reaction condition, both sulfoxides 8a and 9a gave a mixture of the disulfide 12, the isomeric disulfide 14, and the sulfinic acid 13. Under the strong alkaline condition an elimination of activated hydrogen from the carbon adjacent to the carbonyl group to furnish the sulfenic acid 2a and the isomeric sulfenic acid 18. The formation of the transient intermediate in the reaction was proven by isolation of the isomeric disulfide 14. The reactive entity was regarded as the sulfenic acid rather than sulfenate anion under these reaction conditions.

• Journal of the Korean Chemical Society
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• v.37 no.6
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• pp.555-561
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• 1993

Ultraviolet spectrophotometric investigation has been carried out on the system of iododestannylation iodine and tetramethyltin in methanol. The transient CT absorption spectrum can be observed and the subsequent disappearance of CT absorption spectrum was accompained by the cleavage of tetramethyltin with iodine. From there, the rate constants for the iododestannylation were determined at 10, 25 and 35$^{\circ}C$ up to 1600 bar and the reaction rates were increased with increasing temperature and pressure. From these rate constants, the values of the activation parameters (${\Delta}V^\neq,\;{\Delta}{\beta}^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}\;and\;{\Delta}G^{\neq}$) were obtained. The activation volumes and activation compressibility coefficients were both negativity. The activation enthalpies were positive and activation entropies had large negative values. From these values discussed in terms of solvent structure variation of transition state and mechanism. From these results, it was found that the reaction is followed with $S_E2$ mechaenism and weakened $S_E2$ mechanism nature by increasing pressure.

• Journal of the Korean Society of Propulsion Engineers
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• v.12 no.4
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• pp.33-41
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• 2008

The prelaunch thermal transients in the cryogenic oxidizer tank of liquid propulsion rocket subjected to uniform heat flux from outside are numerically analyzed through thermodynamic equations and heat and mass transfer relations. The prelaunch stage is assumed to be composed of five idealized sub-stages including pressurization process by helium gas injection. The Peng-Robinson equation of state is utilized in the lumped analysis of ullage gas. The liquid region is divided into a number of horizontal layers of uniform properties to account for the thermal stratification. The computational result for the typical case shows that the temperature rise of liquid oxidizer is less than 1K and the adsorbed helium into the liquid is approximately 10g.

• Nuclear Engineering and Technology
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• v.36 no.6
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• pp.528-539
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• 2004

It is essential in commercial reactors that the safety limits imposed on the fuel pellets and fuel clad barriers, such as the linear power density (LPD) and the departure from nucleate boiling ratio (DNBR), are not violated during reactor operations. In order to accurately monitor the safety limits of current reactor states, a detailed three-dimensional (3D) core power distribution should be estimated from the in-core detector signals. In this paper, we propose a calculation methodology for detailed 3D core power distribution, using in-core detector signals and core monitoring constants such as the 3D Coupling Coefficients (3DCC), node power fraction, and pin-to-node factors. Also, the calculation method for several core safety parameters is introduced. The core monitoring constants for the real core state are promptly provided by the core design code and on-line MASTER (Multi-purpose Analyzer for Static and Transient Effects of Reactors), coupled with the core monitoring program. through the plant computer, core state variables, which include reactor thermal power, control rod bank position, boron concentration, inlet moderator temperature, and flow rate, are supplied as input data for MASTER. MASTER performs the core calculation based on the neutron balance equation and generates several core monitoring constants corresponding to the real core state in addition to the expected core power distribution. The accuracy of the developed method is verified through a comparison with the current CECOR method. Because in all the verification calculation cases the proposed method shows a more conservative value than the best estimated value and a less conservative one than the current CECOR and COLSS methods, it is also confirmed that this method secures a greater operating margin through the simulation of the YGN-3 Cycle-1 core from the viewpoint of the power peaking factor for the LPD and the pseudo hot pin axial power distribution for the DNBR calculation.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2006.06a
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• pp.521-522
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• 2006

In this paper, hybrid air-water discharges were used to develop an optimal condition for providing a high level of water decomposition for hydrogen yield. Electrical and optical phenomena accompanying the discharges were investigated along with feeding gases, flow rates, and point-to-plane electrode gap distance. The primary focus of this experiment was put on the optical emission of the near UV range, with the energy threshold sufficient for water dissociation and excitation. The $OH(A^{2+},'=0\;X^2,"=0$) band's optical emission intensity indicated the presence of plasma chemical reactions involving hydrogen formation. In the gaseous atmosphere saturated with water vapor the OH(A-X) band intensity was relatively high compared to the liquid and transient phases although the optical emission strongly depended on the flow rate and type of feeding gas. In the gaseous phase discharge phenomenon for Ar carrier gas transformed into a gliding arc via the flow rate growth. OH(A-X) band's intensity increased according to the flow rate or residence time of He feeding gas. Reciprocal tendency was acquired for $N_2$ and Ar carrier gases. The peak value of OH(A-X) intensity was observed in the proximity of the water surface, however in the cases of Ar and $N_2$ with 0.5 SLM flow rate peaks shifted to the region below the water surface. Rotational temperature ($T_{rot}$) was estimated to be in the range of 900-3600 K, according to the carrier gas and flow rate, which corresponds to the arc-like-streamer discharge.

• Korean Journal of Materials Research
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• v.4 no.7
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• pp.798-807
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• 1994

The increase in the resistance of $BaTio_{3}$ with addition of Ca is attributed to the formation ofthe acceptor impurity by $CaCa^{2+}$" which substitutes Ti4+. However, some authors suggested that $Ca^{2+}$ can not substitute $Ti^{4+}$ because of its larger ionic radius. In this work, the existence of acceptor by Ca hasbeen studied through the high temperature equilibrium electrical conductivity of $BaTiO_{3}$ codoped with Caand Nb, where Ba/(Ti+Ca+Nb) was kept equal to unity. It was measured at $1000^{\circ}C$, and the oxygenpartial pressure was controlled between $10^{-15}$ ~ 1 atm. Changing the amount of added Ca and Nbresulted in the compensation effect between donor and acceptor, i.e., Nb was compensated by the acceptor.And through the defect chemical interpretation of the measured data, it was concluded that Ti canbe substitued with Ca. The existence of such acceptor was reaffirmated by ICTS(Isotherma1 CapacitanceTransient Spectroscopy) measurements.oscopy) measurements.

• Journal of Energy Engineering
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• v.8 no.4
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• pp.540-545
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• 1999

The classical Fourier heat conduction equation is invalid at temperatures near absolute zero or at very early times in highly transient heat transfer processes. In such situations, a hyperbolic equation model for heat conduction based on the modified Fourier law is introduced because the wave nature of heat propagation becomes dominant. The Fourier model and the hyperbolic model for heat conduction are analyzed by using the Green's function technique together with the integral transform. Analytical expressions for the heat flux and temperature distributions in a finite slab subjected to a periodic surface heating at one of its surfaces are presented and the results obtained from each model are compared with each other. The thermal wave implied b the hyperbolic model is shown to travel through a medium and to reflect back toward the origin at the other insulated surface. On the other hand, the heat by the Fourier model propagates at an infinite speed instantaneously after a thermal disturbance is felt throughout the medium.

• Bulletin of the Society of Naval Architects of Korea
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• v.11 no.1
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• pp.35-44
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• 1974

열박음(shrink fitting)으로 인(因)한 동심형(同心形) 구멍을 가진 복합(複合)실린더의 과도적(過渡的) 온도분포(溫度分布), 열응력(熱應力) 및 열변형도(熱變形度)를 이론해석(理論解析)하였다. 온도분포해석(溫度分布解析)에서 외부(外部) 실린더는 균일온도(均一溫度)로 가열(加熱)되어, 실온(室溫)의 내부(內部) 실린더와 접촉면(接觸面)에서 일어나는 열전도(熱傳導)에 의(依)하여 냉각(冷却)되고, 외부(外部) 표면(表面)은 대기중(大氣中)에 노출(露出)된 상태(狀態)로 취급(取扱)하였다. 열응력(熱應力)은 평면변형도조건(平面變形度條件)을 만족(滿足)하는 것으로 생각하였으며, 물성(物性)은 온도(溫度)에 무관(無關)한 상수(常數)로 취급(取扱)하였다. 온도분포(溫度分布)는 열전도문제(熱傳導問題)만을 고려(考慮)함으로서도 유효(有效)한 해(解)를 얻을 수 있으며 열응력(熱應力)은 접촉면(接觸面)에서부터 형성(形成)되며, 반경방향응력(半徑方向應力)은 시간(時間)이 경과(經過)함에 따라 압축응력(壓縮應力)이 증가(增加)하여 접촉면(接觸面)에서 최대치(最大値)를 갖고, 원주방향응력(圓周方向應力)은 접촉면(接觸面)에서 초기(初期)부터 거의 최종상태(最終狀態)와 같은 크기를 갖음을 알 수 있다. 균일온도분포(均一溫度分布)가 이루어지면 열응력(熱應力)의 형성(形成)은 완료(完了)되게 되며, 이때의 열응력(熱應力)의 크기와 분포경향(分布傾向)은 평면응력조건(平面應力條件)을 사용(使用)하였다는 사실(事實)을 고려(考慮)하면 $Lam\acute{e}$의 이론해(理論解)와 일치(一致)함을 알 수 있었다.

• Nuclear Engineering and Technology
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• v.22 no.1
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• pp.66-74
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• 1990

The thermal-hydraulic characteristics of the 17$\times$17 OFA (Optimized Fuel Assembly) used in the KNU 7&8 are analyzed and compared with that of the 17$\times$17 SFA (Standard Fuel Assembly) loaded in the KNU 5&6. The thermal-hydraulic characteristics analyzed are minimum DNBR, fuel centerline temperature and exit void fraction at normal operation and design over power transient. Additionally, local linear rod power, which will cause fuel centerline melting, is calculated. The DNBR sensitivity calculations are performed with respect to the reactor operating parameters. COBRA-IV-I code is used for these calculations. The modified W-3 correltion and the drift-flux model are applied for the critical heat flux calculation and the void fraction calculation, respectively. From the calculated results, it has been found that the possibility of DNB occurrence is higher in the OFA than in the SFA. The other hand, the local linear power resulting in fuel centerline moiling of the OFA is nearly equal to that of the SFA.

• Nuclear Engineering and Technology
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• v.18 no.2
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• pp.107-116
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• 1986

The steady and unsteady state models were established for the performance analysis and design of heavy water distillation columns packed with corrugated wire mesh. After the steady state model was derived with pressure drops, separated D$_2$O concentration and temperature profiles and pressure gradients in the column were obtained by solving MESH equations with equation tearing method. For the analysis of unsteady state behavior, the equilibrium stage transient model deduced from modifying the Cohen's ideal cascade equation was used to predict the concentration change of heavy water with time. These models were in good agreement with the experimental results of heavy water distillation at total reflux. And the newly developed packing material turned out to be very efficient separation device for very small HETP, pressure drop and holdup.