• Title/Summary/Keyword: thermodynamic effect

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Smile Rearrangement of Herbicidal Flazasulfuron (제초성 Flazasulfuron의 Smile 자리옮김 반응)

  • Lee, Gwnag-Jae;Kim, Yong-Jip;Kim, Dae-Whang;Sung, Nack-Do
    • Applied Biological Chemistry
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    • v.39 no.1
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    • pp.70-76
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    • 1996
  • A series of the herbicidal pyridylsulfonyl areas, none substitutent, 1-(4,6-dimethoxypyrimidine-2-yl)-3-(2-pyridylsulfonyl) urea, 3 and 3-trifluoromethyl substitutent, 1-(4,6-dimethoxypyrimidine-2-yl)-3-(3-trifluoromethyl-2-pyridylsulfonyl) urea, 5(Flazasulfuron) were synthesizied and the rate of hydrolysis of their has been studied in 25%(v/v) aqueous dioxane at $45^{\circ}C$. From the results of solvent effect($m{\ll}1,\;n{\ll}3\;&\;{\mid}m{\mid}{\ll}{\mid}{\ell}{\mid}$), thermodynamic parameter (${\Delta}S^{\neq}=0.54{\sim}\;-2.19\;e.u.\;&\;{\Delta}H^{\neq}=0.025\;Kcal.mol.^{-1}$), hydrolysis product analysis, $pK_a$ constant(3: 4.9 & 5: lit.4.6) and the rate equation, a marked difference in the kinetics of the reaction of 3 and 5(Flazasulfuron) was observed. It may be concluded that the hydrolysis of 5 proceeds through the $A-S_N2Ar$ reaction via conjugate acid$(5H^+)$ below pH 7.0, whereas, above pH 9.0, the hydrolysis proceeds through irreversibly $(E_1)_{anion}$ and reversibly $(E_1CB)_R$ mechanism via conjugate base(CB), respectively. But in case of 5, $A-S_N2Ar,\;(E_1)anion\;and\;(E_1CB)_R$ mechanism involved Smile rearrangement. The mate of rearrangement of 5 to a 3-trifluoromethyl-2-pyridylpyrimidinyl urea(PPU) in acid and 3-trifluoromethyl-2-pyridyl-4.6-dimethoxypyridinyl amine (PPA) in base was increased about 3.5 times by the introduction of trifluoromethyl group in the 3-position on the 2-pyridyl ring. From the basis of these findings, a possible mechanism for the hydrolysis of 5 was proposed and discussed.

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The Influence of Thermal Condition on the Variation of Reaction Product Composition depending on the Constituent of Dolomite in the Absorption Process of SO2 by Dolomite (Dolomite에 의한 SO2 흡수공정에서 Dolomite 조성에 따른 생성물질 구성 변화에 대한 열적 조건 영향)

  • You, Dong-Ju;Kim, Dong-Su
    • Resources Recycling
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    • v.23 no.2
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    • pp.17-25
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    • 2014
  • The thermal effect on the compositional change of the $SO_2$ absorption process product was investigated compared with the composition of raw material when dolomite is employed in place of lime in the scrubbing process based on thermodynamic estimation. It was considered that the equilibrium reactions which directly related with the formation of $CaSO_4$ and $MgSO_4$, the absorption process products, are those between $Ca^{2+}$ and $Ca(OH)_2$, $Mg^{2+}$ and $Mg(OH)_2$, and the secondary dissociation reaction of $H_2SO_4$. It was thought to be necessary to examine the enthalpy change for the formation reactions of $CaSO_4$ and $MgSO_4$ along with the thermal feature of the relative reactions to figure out the influence of temperature on the compositional change of absorption process products. The stable regions for $Ca(OH)_2$ and $Mg(OH)_2$ in Pourbaix diagram were found to be increased as temperature rises and the equilibrium reaction between $Ca^{2+}$ and $Ca(OH)_2$ was investigated to be more strongly influence by temperature change compared with the equilibrium reaction between $Mg^{2+}$ and $Mg(OH)_2$. The amounts of $CaSO_4$ and $MgSO_4$ were anticipated to be decreased with temperature considering the thermal characteristics for the equilibrium reactions regarding calcium, magnesium, and $H_2SO_4$. It was understood that the formation ratio between $CaSO_4$ and $MgSO_4$ is greater than the composition ratio between calcium and magnesium contained in dolomite at specific temperature and the decrease of the formation ratio of $CaSO_4$ and $MgSO_4$ with temperature was estimated to be diminished as the content of calcium in dolomite is increased. In addition, the extent of the change in the compositional ratio between absorption process products was examined to be reduced compared with the composition of raw material as the calcium content in dolomite is raised.

Mobility of Transition Metals by Change of Redox Condition in Dump Tailings from the Dukum Mine, Korea (덕음광산 광미의 산화${\cdot}$환원 조건에 따른 전이원소의 이동성)

  • 문용희;문희수;박영석;문지원;송윤구;이종천
    • Economic and Environmental Geology
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    • v.36 no.4
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    • pp.285-293
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    • 2003
  • Tailings of Dukum mine in the vadose and saturated zone were investigated to reveal the mobility of metal elements and the condition of mineralogical solubility according to redox environments throughout the geochemical analysis, thermodynamic modelling, and mineralogical study for solid-samples and water samples(vadose zone; distilled water: tailings=5 : 1 reacted, saturated zone; pore-water extracted). In the vadose zone, sulfide oxidation has generated low-pH(2.72∼6.91) condition and high concentration levels of S $O_4$$^{2-}$(561∼1430mg/L) and other metals(Zn : 0.12∼l57 mg/L, Pb : 0.06∼0.83 mg/L, Cd : 0.06∼l.35 mg/L). Jarosite$(KFe_3(SO_4)_2(OH)_6)$ and gypsum$(CaSO_4{\cdot}2H_2O$) were identified on XRD patterns and thermodynamics modelling. In the saturated zone, concentration of metal ions decreased because pH values were neutral(7.25∼8.10). But Fe and Mn susceptible to redox potential increased by low-pe values(7.40∼3.40) as the depth increased. Rhodochrosite$(MnCO_3)$ identified by XRD and thermodynamics modelling suggested that $Mn^{4+}$ or $Mn^{3+}$ was reduced to $Mn^{2+}$. Along pH conditions, concentrations of dissolved metal ions has been most abundant in vadose zone throughout borehole samples. It was observed that pH had more effect on metal solubilities than redox potential. How-ever, the release of co-precipitated heavy metals following the dissolution of Fe-Mn oxyhydroxides could be the mechanism by which reduced condition affected heavy metal solubility considering the decrease of pe as depth increased in tile saturated zone.

Experimental Study on the Thermodynamic Characteristics of Commercial Small-size Moxa Combustion (상용 소형 쑥뜸의 열역학적 특성에 대한 실험적 연구)

  • Lee Geon-Mok;Hwang Yoo-Jin;Lee Gun-Hyee
    • Journal of Acupuncture Research
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    • v.18 no.6
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    • pp.171-187
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    • 2001
  • Objective : Moxibustion has been proved efficacious for many diseases, but isn't widespread in the clinics due to a danger of skin burning, the smoke produced while burning a moxa combustion and so on. Therefore, another type of moxa that can be resolved these troubles is required. To improve the effect of moxibustion and develop the new thermal stimulating treatment, the performance of commercial moxibustion widely used are studied systematically and found out quantitatively. Methods : We have selected two types (small-size moxa A(sMA), small-size moxa B (sMB)) among small-size moxaes used widely in the clinic. We examined combustion time, various temperatures, temperature gradient in each period during a combustion of moxa. Results : 1. The combustion time in the preheating period appeared somewhat longer in sMA than in sMB. 2, The combustion time in the heating period appeared longer in sMA by 26% than in sMB. 3. The average temperature in the heating period was $37.6{\sim}37.8^{\circ}C\;in\;sMA\;and\;36.2{\sim}36.8^{\circ}C$ in sMB and the maximum temperature measured at a center of contact surface in sMA was $48.6^{\circ}C$, higher by over $2.8^{\circ}C$ than that of sMB moxibustion. 4. The average ascending temperature gradient in the heating period was $0.08{\sim}0.1^{\circ}C/sec$ in both moxaes, and the average ascending temperature gradient of heating period in sMB appeared larger. The maximum ascending temperature gradient appeared higher in sMB, and the time reaching maximum ascending temperature gradient appeared much earlier in sMA than in sMB. 5. The combustion time in the retaining period was around 100 sec in sMA and around 275 sec in sMB. 6. The average temperature in the retaining period was $42.2{\sim}46.0^{\circ}C\;in\;sMA\;and\;39.3{\sim}41.4^{\circ}C/sec$ in sMB. The minimum temperature in the retaining period was over $38.80^{\circ}C$ in sMA but just $34.7^{\circ}C$ in sMB. 7. The average descending temperature gradient in sMA was $-0.050{\sim}0.067^{\circ}C/sec$ and in sMB was $-0.030{\sim}0.037^{\circ}C/sec$ 8. The combustion time in the cooling period appeared longer over two times in sMA than in sMB, and the time which the cooling period (minimum temperature) finished at appeared later in sMB by 55 sec. 9. We classified the combustion process that the measured temperature rose over body heat($37^{\circ}C$) into the effective combustion period. The effective combustion time was 233.3 sec in sMA and 300.4 sec in sMB respectively, and was longer by about 29% in sMB. The average temperature and maximum temperature in the effective combustion time appeared higher in sMA. The time taken until the maximum temperature was reached was 225.1 sec in sMA and 244.5 sec in sMB, faster by about 20 sec in sMA. The maximum ascending temperature gradient during the effective combustion period appeared larger about 1.4 times in sMB, but the time when the maximum ascending temperature gradient happened was faster in sMA. Conclusion : It appears that sMB, compared with sMA, is proper if necessary to apply the long time and weak stimulus, because of the gentle stimulus during the relatively longer time. In contrast, sMA that the symmetrical combustion happened is proper if necessary to apply the short time and strong stimulus.

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Recent Progress in Air Conditioning and Refrigeration Research - A Review of Papers Published in the Korean Journal of Air-Conditioning and Refrigeration Engineering in 2002 and 2003 - (공기조화, 냉동 분야의 최근 연구 동향 -2002년 및 2003년 학회지 논문에 대한 종합적 고찰 -)

  • Chung Kwang-Seop;Kim Min Soo;Kim Yongchan;Park Kyoung Kuhn;Park Byung-Yoon;Cho Keumnam
    • Korean Journal of Air-Conditioning and Refrigeration Engineering
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    • v.16 no.12
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    • pp.1234-1268
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    • 2004
  • A review on the papers published in the Korean Journal of Air-Conditioning and Refrigerating Engineering in 2002 and 2003 has been carried out. Focus has been put on current status of research in the aspect of heating, cooling, air-conditioning, ventilation, sanitation and building environment/design. The conclusions are as follows. (1) Most of fundamental studies on fluid flow were related with heat transportation in diverse facilities. Drop formation and rivulet flow on solid surfaces were interesting topics related with condensation augmentation. Research on micro environment considering flow, heat transfer, humidity was also interesting to promote comfortable living environment. It can be extended considering biological aspects. Development of fans and blowers of high performance and low noise were continuing research topics. Well developed CFD technologies were widely applied for analysis and design of various facilities and their systems. (2) Heat transfer characteristics of enhanced finned tube heat exchangers and heat sinks were extensively investigated. Experimental studies on the boiling heat transfer, vortex generators, fluidized bed heat exchangers, and frosting and defrosting characteristics were also conducted. In addition, the numerical simulations on various heat exchangers were performed and reported to show heat transfer characteristics and performance of the heat exchanger. (3) A review of the recent studies shows that the performance analysis of heat pump have been made by various simulations and experiments. Progresses have been made specifically on the multi-type heat pump systems and other heat pump systems in which exhaust energy is utilized. The performance characteristics of heat pipe have been studied numerically and experimentally, which proves the validity of the developed simulation programs. The effect of various factors on the heat pipe performance has also been examined. Studies of the ice storage system have been focused on the operational characteristics of the system and on the basics of thermal storage materials. Researches into the phase change have been carried out steadily. Several papers deal with the cycle analysis of a few thermodynamic systems which are very useful in the field of air-conditioning and refrigeration. (4) Recent studies on refrigeration and air-conditioning systems have focused on the system performance and efficiency enhancement when new alternative refrigerants are applied. Heat transfer characteristics during evaporation and condensation are investigated for several tube shapes and new alternative refrigerants including natural refrigerants. Efficiency of various compressors and performance of new expansion devices are also dealt with for better design of refrigeration/air conditioning system. In addition to the studies related with thermophysical properties of refrigerant mixtures, studies on new refrigerants are also carried out. It should be noted that the researches on two-phase flow are constantly carried out. (5) A review of the recent studies on absorption refrigeration system indicates that heat and mass transfer enhancement is the key factor in improving the system performance. Various experiments have been carried out and diverse simulation models have been presented. Study on the small scale absorption refrigeration system draws a new attention. Cooling tower was also the research object in the respect of enhancement its efficiency, and performance analysis and optimization was carried out. (6) Based on a review of recent studies on indoor thermal environment and building service systems, it is noticed that research issues have mainly focused on several innovative systems such as personal environmental modules, air-barrier type perimeterless system with UFAC, radiant floor cooling system, etc. New approaches are highlighted for improving indoor environmental conditions and minimizing energy consumption, various activities of building energy management and cost-benefit analysis for economic evaluation.