• Title/Summary/Keyword: Thermodynamic parameters

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Prediction of Thermal Behavior of Automotive LNG Fuel Tank (LNG 자동차 연료 탱크의 열적 거동에 대한 예측)

  • NamKoong, Kyu-Won;Chu, Seok-Jae
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.34 no.9
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    • pp.875-883
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    • 2010
  • The thermal performance of LNG fuel tanks of vehicles is determined by the time for non-venting storage of fuel and the amount of fuel supplied to the engine. In this study, we selected a double-walled vacuum-insulated fuel tank with a volume of 450 liter, and the properties of the fuel contained in it were assumed to be the same as those of the methane($CH_4$). For the increasing the non-venting fuel storage time, we propose the use of shielded penetration pipes in the tank. We compared the storage times of the tank used in our study with those of the conventional fuel tank. Further, the additional heat input required to maintain the fuel pressure necessary for an appropriate fuel supply rate was predicted. For these parameters, we derived a thermodynamic relationship that can be used to estimate the rate of increase in pressure for a known heat input, and we obtained equations for estimating the rate of heat leaked by using the established heat transfer model. From the results of numerical computation, we found the non-venting storage time of the tank with shielded pipes to be 25-30% higher than that of the tank with unshielded pipes. Further, we determined the appropriate operation conditions by taking into consideration the transfer rate of additional heat provided to the fuel tank.

Adsorption Thermodynamics of Polyamidoamide Epichlorohydrin Polymer in an Aqueous Fibrous Suspension (섬유 현탁액내 PAE 고분자 흡착의 열역학적 고찰)

  • Sung-Hoon Yoon;Kwang-Suk Joo;Tae-Won Lee;Kun-Han Kim;Byung-Bin Park
    • Journal of the Korean Chemical Society
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    • v.47 no.3
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    • pp.220-228
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    • 2003
  • This study was to examine the thermodynamic features of polyelecrolytic adsorption of polyamidoamine-epichlorohydrin(PAE) in a papermaking wet-end. The PAE adsorption experiments were conducted in a stirred jar containing an aqueous fibrous suspension and evaluated in terms of Langmuir and Freundlich parameters. The electrokinetic property of a stock was examined by measuring the zeta potential of each colloidal suspension. The polyelectrolytic PCD titration was employed to determine the adsorbed amounts of PAE polymer. The zeta potential of a stock, being varied significantly depending upon the addition of PAE polymer, showed initially a sharp increase and later an exponential decay as a function of time . The PAE adsorption exhibited a pseudo-Langmuir adsorption behavior at$20^{\circ}C$ , whereas its Freundlich power(v) increased in a proportional way at an elevated temperature. The train numbers calculated on the basis of adsorption thermodynamics were 7 to 8. The length of the extended loop of PAE was calculated as 215 nm at $20^{\circ}C$ and increased at a rate of 9% at every $10^{\circ}C$ rise in temperature. The PAE adsorption was proven to be an exothermic physisorption with the estimated adsorption enthalpy of -27 to -29 kJ/mol.

Mixed Micellizations of TTAB with Other Surfactants (DTAB, CTAB, Tween-20, Tween-40, and Tween-80) (TTAB와 다른 계면활성제(DTAB, CTAB, Tween-20, Tween-40 및 Tween-80)와의 혼합미셀화에 대한 연구)

  • Lee, Nam-Min;Lee, Byung-Hwan
    • Journal of the Korean Chemical Society
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    • v.56 no.5
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    • pp.556-562
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    • 2012
  • The critical micelle concentration (CMC) and the counter-ion binding constant (B) for the mixed micellizations of TTAB (tetradecyltrimethylammonium bromide) with other surfactants (DTAB, CTAB, Tween-20, Tween-40, and Tween-80) in aqueous solution of 4-chlorobenzoic acid (0.5 mM) at $25^{\circ}C$ were determined as a function of ${\alpha}_1$ (the overall mole fraction of TTAB) by using the spectrophotometric method and the conductivity method. Various thermodynamic parameters ($X_i$, ${\gamma}_i$, $C_i$, $a_i^M$, ${\beta}$, and ${\Delta}H_{mix}$) were calculated for each mixed surfactant system and compared with the other mixed surfactant systems by means of the equations derived from the nonideal mixed micellar model. The results show that TTAB/DTAB mixed system has a great positive deviation from the ideal mixed micellar model and the other mixed systems have great negative deviations from the ideal mixed model.

Hydrogeochemical study of a watershed in Pocheon area: controls of water chemistry

  • Kim, Kyoung-Ho;Yun, Seong-Taek;Chae, Soo-Ho;Jean, Jong-Wook;Lee, Jeong-Ho;Kweon, Hae-Woo
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2004.09a
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    • pp.121-121
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    • 2004
  • The groundwater in the Pocheon area occurs from both a fractured bedrock aquifer in igneous and metamorphic rocks and an alluvial aquifer with a thickness of <50 m, and forms a major source of domestic and agricultural water supply. In this study, we performed a hydrogeochemical study in order to identify the control of geochemical processes on groundwater quality. For this study, groundwater level and physicochemical parameters (EC, Eh, pH, alkalinity) were monitored once a month from a total of 150 groundwater wells between June 2003 to August 2004. A total of 153 water samples (13 surface water, 66 alluvial groundwater, 74 bedrock groundwater) were also collected and analyzed in February 2004. Groundwater chemistry in the study area is very complex, depending on a number of major factors such as geology, degree of chemical weathering, and quality of recharge water. Hydrochemical reactions such as the leaching of surficial and near-solace soil salts, dissolution of calcite, cation exchange, and weathering of silicate minerals are proposed to explain the chemistry of natural groundwater. Alluvial groundwaters locally have very high TDS concentrations, which are characterized by their chloride(nitrate)-sulfate-bicabonate facies and low Na/Cl ratio. Their grondwater levels are highly fluctuated according to rainfall event. We suggest that high nitrate content and salinity in such alluvial groundwaters originates from the local recharge of sewage effluents and/or fertilizers. Likewise, high concentrations of nitrate were also locally observed in some bedrock groundwaters, suggesting their effect of anthropogenic contamination. This is possibly due to the bypass flow taking place through macropores. Tile degree of the weathering of silicate minerals seems to be a major control of the distribution of major cations (sodium, calcium, magnesium, potassium) in bedrock groundwaters, which show a general increase with increasing depth of wells. Thermodynamic interpretation of groundwater chemistry shows that the groundwater in the study area is in chemical equilibrium with kaolinite and Na-montmorillonite, which indicates that weathering of plagioclase to those minerals is a major control of hydrochemistry of bedrock groundwater. The interpretation of the molar ratios among major ions, as well as the mass balance calculation, also indicates the role of both dissolution/precipitation of calcite and Ca-Na cationic exchange as bedrock groundwaters evolves progressively.

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Study on the Solubilization of 4-Chlorobenzoic Acid by Aqueous Solutions of Various Cationic, Nonionic, and Mixed Surfactant Systems (양이온성, 비이온성 및 혼합성 계면활성제에 의한 4-클로로벤조산의 가용화에 대한 연구)

  • Lee, Nam-Min;Lee, Byung-Hwan
    • Journal of the Korean Applied Science and Technology
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    • v.31 no.2
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    • pp.244-254
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    • 2014
  • The interactions of 4-chlorobenzoic acid with the micellar system of various cationic, nonionic, and mixed surfactant systems were studied by the UV/Vis spectrophotometric method. The solubilization constants ($K_s$) of 4-chlorobenzoic acid into those micellar systems have been measured at various temperatures and various thermodynamic parameters for the solubilization of 4-chlorobenzoic acid have been calculated and analyzed from those changes. The results show that the values of ${\Delta}G^o_s$ are all negative within the measured temperature range and that the values of ${\Delta}H^o_s$ and ${\Delta}S^o_s$ are all positive. The effects of alkyl-group's length of surfactant molecules on the solubilization of 4-chlorobenzoic acid have been also measured. The values of $K_s$ were dependent simultaneously on the alkyl-group's length and the kind of head-group in surfactant molecules. From these changes we can postulate the solubilization site and the degree of interaction of 4-chlorobenzoic acid with the micellar systems.

Studies on the Complexes of Lanthanide ion with Multidentate Ligand (I). Determination of Thermodynamic Parameters with Solution Calorimetric Method in Nonaqueous Solvents (란탄족 원소의 여러자리 리간드 착물에 관한 연구 (제 1 보) 물아닌 용액에서 용액열량계에 의한 열역학적 함수결정)

  • Sam-Woo Kang;Won-Hae Koo;Soo-Min Lee;Chang Choo-Hwan;Moo-Yol Seo
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.588-595
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    • 1989
  • Log K, ${\Delta}$H and ${\Delta}$S for the complexation of $La^{3+},\;Ce^{3+}$ and $Eu^{3+}$with various multidentate ligand containing crown ether, diaza crown ether and diamine ether have been determined in methanol and acetonitril solutions at $25^{\circ}C$ by solution calorimetric titration method. The greater stability constant of $La^{3+}$-15C5 than those of 18C6 diaza [2.2] in methanol are discussed in terms of the size of metal ion and the ligand cavity and of metal ion solvation. The stabilities of $Ce^{3+}$ and $La^{3+}$ ion complexes with a various multidentate ligand in acetonitril are in the order of (diamine ether)<18C6<15C5$Ce^{3+}$, $La^{3+}$ and $Eu^{3+}$-diaza [2.2] complexes in acetonitril are increased with the following order: $Eu^{3+}$ < $La^{3+}$ < $Ce^{3+}$, that is increasing order of the optimum size and of the charge density of metal ion.

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The Thermodynamics of the Formation of Polymethylbenzene-Halogens Charge Transfer Complexes (III) (폴리메틸벤젠과 할로겐 사이의 전하이동착물 생성에 관한 열역학적 연구 (제3보))

  • Oh Cheun Kwun;Jin Burm Kyong;Jung Sung Kim
    • Journal of the Korean Chemical Society
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    • v.25 no.6
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    • pp.351-360
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    • 1981
  • Ultraviolet spectrophotometric investigations have been carried out on the system of durene with iodine, bromine, iodine monochloride and iodine monobromide in carbon tetrachloride. The results reveal the formation of the charge transfer complexes of the type, $C_6H_2(CH_3)_4{\cdot}X_2$ or $C_6H_2(CH_3)_4{\cdot}IX$(X denotes halogen atoms). The equilibrium constant were obtained in consideration of that absorption maxima due to the formation of the charge transfer complexes shift to blue with the increasing temperatures. The thermodynamic parameters, ${\Delta}H,\;{\Delta}G\;and\;{\Delta}S$ for the formation of the charge transfer complexes were calculated from these values. These results indicate that the relative stabilities of the durene complexes at each temperature decrease in the order, $ICl>IBr>I_2>Br_2$. This order may be a measure of their relative acidities toward durene, which is explained in terms of the relative polarizabilities of halogen molecules and the relative electronegativities of halogen atoms. These results combined with previous study of this series indicated that the relative stabilities of the polymethylbenzene complexes with iodine increase in the order; Benzene

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Studies on the Coordination of Acetamide to Rare Earth Metal Ion (Ln(II) (희토류 금속이온 (Ln(III))과 Acetamide 사이의 상호작용에 대한 연구)

  • Sang-Won Lee;Jeonga Yu;Chang-Ju Yoon;Yoo-Hyek Jun;Young-Sang Choi
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.205-211
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    • 1992
  • The $2{\nu}_{C=0}$ + amide III combination band spectrum of acetamide (AA) was obtained in very dilute solutions of AA+lanthanide shift reagents (LSR) in carbon tetrachloride over the range of $15^{\circ}$ to $45^{\circ}C$. It was found that only 1 : 1 AA-LSR complex is formed by the interaction between carbonyl oxygen of AA and central metal ion(Ln(Ⅲ)) in LSR. The thermodynamic parameters for Ln(III)${\cdot}$O=C bond were determined by computer analysis of concentration and temperature dependent spectra. ${\Delta}H^{\circ}$ for the coordination of AA to Eu$(dpm)_3$, Yb$(dpm)_3$, and Pr$(dpm)_3$ have been found to be -39.1, -28.4, and -25.5 kJ/mol, respectively. It has shown that this type of ion-dipole interaction is more than twice stronger compared to the dipole-dipole interaction in the amide linkage, and largely depending on the steric hindrence effect by the bulky dpm groups around central metal ion (Ln(III)) rather than the ionic potential effect of central metal ion itself.

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Interactions between Water-Soluble Polyparacyclophanes and Drugs (III) -Complex Formation of Water-Soluble Polyparacyclophanes with Fluorescent Hydrophobic Naphthalene Derivatives in Aqueous Solution- (수용성 폴리파라시클로판류와 약물과의 상호작용(제 3보)-수용액 중 수용성 폴리파라시클로판류와 형광 소수 나프탈렌 유도체류와의 복합체 형성-)

  • Chun, In-Koo;Lee, Min-Hwa
    • Journal of Pharmaceutical Investigation
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    • v.19 no.2
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    • pp.71-79
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    • 1989
  • Complex formation of water-soluble polyparacyclophanes bearing two diphenylmethane or two diphenyl ether skeletons with l-anilinonaphthalene-8-sulfonate (ANS) and 2-p-toluidinylnaphthalene-6-sulfonate (TNS) was investigated quantitatively to develop useful host compounds comparing with ${\alpha}\;-\;and\;{\beta}-cyc1odextrins$$({\alpha}-\;and\;{\beta}-CyDs$) in aqueous solution. Benesi-Hildebrand type analysis of the fluorescent intensity showed that the dissociation constants (Kd) of paracyclophane-ANS complexes were $1.55\;{\times}\;10^{-4}M$ for 1,6,20,25-tetraaza[6.1.6.1]paracyclophane(CPM 44) and $1.23\;{\times}\;10^{-4}M$ for 1,7,21,27-tetraaza[7.1.7.1]paracyclophane (CPM 55), and those of paracyclophane-TNS complexes were $6.99\;{\times}\;10^{-6}M$ for CPM 44 and $6.23\;{\times}\;10^{-5}M$ for CPM 55, in 1:1 molar ratio. On the other hand, the Kd values of 1,7,21,27-tetraaza-14,34-dioxa[7.1.7.1]paracyclophane (CPE 55)-ANS, 1,8,22,29-tetraaza-15,36-dioxa[8.1.8.1]paracyclophane (CPE 66)-ANS, CPE 55-TNS, CPE 66-TNS complexes were $1.75\;{\times}\;10^{-3}M$, $3.07\;{\times}\;10^{-3}M$, $3.75\;{\times}\;10^{-3}M$ and $2.15\;{\times}\;10^{-3}M$, respectively. On the contrary, the Kd values of ${\alpha}-CyD-ANS$, ${\beta}-CyD-ANS$, ${\alpha}-CyD-TNS$ and ${\beta}-CyD-TNS$ complexes were found to be $3.98\;{\times}\;10^{-2}M$, $1.05\;{\times}\;10^{-2}M$, $1.38\;{\times}\;10^{-2}M$ and $3.52\;{\times}\;10^{-4}M$, respectively. These results mean that the complexation of CPMs with ANS or TNS is by 5.6-1,975 fold stronger than that for ${\alpha}-or\;{\beta}-CyDs$, and the complex formation of CPEs with ANS or TNS is nearly same as or somewhat stronger than that for ${\alpha}-or\;{\beta}-CyDs$. From the Kd values determined at different temperatures, thermodynamic parameters were calculated and the complexation was found to be a spontaneous exothermic reaction. The effects of pH on Kd values of CPM 44-ANS, and CPM 55-ANS complexes were negligible in the range of pH 1.2-1.8. However, the Kd values of these complexes increased significantly with increasing ionic strength.

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Kinetics and Hydrolysis Mechanism of Herbicidal N-(2,6-dimethoxypyrimidin-2-yl)aminocarbonyl-2-(1-hyd roxy-2-fluoroethyl)benzenesulfonamide Derivatives (제초성, N-(2,6-dimethoxypyrimidin-2-yl)aminocarbonyl-2-치환(Z)-6-(1-hyd roxy-2-fluoroethyl)benzenesulfonamide 유도체의 가수분해 반응 메카니즘)

  • Lee, Chan-Bog;Ryu, Jae-Wook;Kim, Dae-Whang;Sung, Nack-Do
    • Applied Biological Chemistry
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    • v.38 no.5
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    • pp.455-462
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    • 1995
  • The new six herbicidal N-[(pyrimidin-2-yl)aminocarbonyl]-2-substituted-6-(1-hydroxy-2-fluoroethyl)benzenesulfonamide derivatives(S) were synthesized and rate constants for the hydrolysis of thier in the range of pH $1.0{\sim}10.0$ have been studied in 15%(v/v) aqueous acetonitrile solution at $45^{\circ}C$. From the basis of the results, pH-effect, solvent effect, ortho-substituent effect, thermodynamic parameters(${\Delta}H^{\neq}$ & ${\Delta}S^{\neq}$), pKa constant(4.80), rate equation, analysis of hydrolysis products(2-(1-hydroxy-2-fluoroethyl)benzenesulfonamide & 4,6-dimethoxyaminopyrimidine), it may be concluded that the general acid catalyzed hydrolysis through $A-S_E2$ mechanism and specific acid catalyzed hydrolysis through A-2 type(or $A_{AC}2$) mechanism proceeds via conjugate acid($SH^+$) and tetrahedral intermediate(I) below pH 8.0, whereas, above pH 9.0, the general base catalyzed hydrolysis by water molecules(B) through $(E_1)_{anion}$ mechanism proceeds via conjugate base(CB). In the range between $pH\;7.0{\sim}pH\;9.0$, these two reactions occur competitively.

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