• Title/Summary/Keyword: halogens

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Thermodynamics of the Formation of Polymethylbenzene-Halogens Charge Transfer Complexes (IV) (폴리메틸벤젠과 할로겐 사이의 전하이동 착물생성에 관한 열역학적 연구 (제4보))

  • Oh Chun Kwun;Jeong Rim Kim;Je Ha Yang
    • Journal of the Korean Chemical Society
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    • v.26 no.5
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    • pp.274-281
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    • 1982
  • Ultraviolet spectrophotometric investigation have been carried out on the systems of pentamethylbenzene and hexamethylbenzene with iodine and iodine monochloride in carbon tetrachloride. The results reveal the formation of the one to one molecular complexes. The equilibrium constants were obtained in consideration of that absorption maxima due to the formation of the charge transfer complexes shift to blue with the increasing temperature. Thermodynamic parameters for the formation of the charge transfer complexes were calculated from these values. These results indicate that the complex formed between polymethylbenzene and iodine monochloride is more stable than that in the case of iodine. This may be a measure of their relative acidities toward polymethylbenzene, which is explained in terms of the relative electronegativities of halogen atoms. These results combined with previous studies of this series indicated that ${\lambda}_{max}$ shift to red with the increasing number of methyl groups on benezene ring and that the relative stabilities of these complexes increase in the order, Benzene < Toluene < Xylene < Durene < Mesitylene < Pentamethylbenzene < Hexamethylbenzene. The reason for the order found is thus additionally discussed.

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The Thermodynamics of the Formation of Polymethylbenzene-Halogens Charge Transfer Complexes (Ⅰ) (폴리메틸벤젠과 할로겐사이의 전하이동착물생성에 관한 열역학적 연구 (제1보))

  • Oh Cheun Kwun;Jin Burm Kyong
    • Journal of the Korean Chemical Society
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    • v.25 no.1
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    • pp.1-6
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    • 1981
  • Ultraviolet spectrophotometric investigations were carried out on the systems of o-, m-and p-xylene with iodine in carbon tetrachloride. The results reveal the formation of one to one molecular complexes of the type, $C_6H_4(CH_3)_2{\cdot}I_2. $The equilibrium constants of complexes were obtained in consideration of that absorption maxima has the blue shift with the increasing temperatures according to the formation of the charge transfer complexes. 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 combined with previous study of this series indicated that the relative stabilities of the polymethylbenzene complexes with iodine increase in the order, Benzene < Toluene < o-Xylene < p-Xylene These results are supposed to be the influence resulted from increase of electron density by the positive inductive effect and the steric hindrance effect.

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The Complexes of Benzene with Halogens and Interhalogens in Carbon Tetrachloride (벤젠과 할로겐 또는 할로겐間化合物 사이의 錯物에 관한 연구)

  • Choi, Sang-Up;Chang, Suck-Joo;Kwon, Shoon-Ja
    • Journal of the Korean Chemical Society
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    • v.9 no.4
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    • pp.153-160
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    • 1965
  • Ultraviolet spectrophotometric investigations have been carried out on the systems of benzene with iodine, bromine, chlorine and iodine monobromide in carbon tetrachloride. The results reveal the formation of one to one molecular complexes of the type, $C_6H_6{\cdot}X_2\;or\;C_6H_6{\cdot}IX$ (X denotes halogen atoms). The equilibrium constants obtained at $25^{\circ}$for the complex formation are 0.173, 0.137, 0.0643 and 0.341 $lmole^{-1}$ for $C_6H_6{\cdot}I_2,\;C_6H_6{\cdot}Br_2,\;C_6H_6{\cdot}Cl_2\;and\;C_6H_6{\cdot}IBr$, respectively. These results combined with those obtained by other workers indicate that the relative stabilities of the benzene complexes decrease in the order, $ICl > IBr > I_2 > Br_2 > Cl_2.$ This order may be measure of their relative acidities toward benzene, which is explained in terms of the relative polarizabilities of halogen molecules and the relative electronegativities of halogen atoms.

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A Study of Failure Mechanism through abnormal AlXOY Layer after pressure Cooker Test for DRAM device (DRAM 소자의 PCT 신뢰성 측정 후 비정상 AlXOY 층 형성에 의해 발생된 불량 연구)

  • Choi, Deuk-Sung;Jeong, Seung-Hyun;Choi, Chae-Hyoung
    • Journal of the Microelectronics and Packaging Society
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    • v.25 no.3
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    • pp.31-36
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    • 2018
  • This research scrutinizes the reason of failure after pressure cooker test (PCT) for DRAM device. We use the physical inspecting tools, such as microscope, SEM and TEM, and finally find the discolor phenomenon, corrosion of Al and delamination of inter-metal dielectric (IMD) in the failed devices after PCT. Furthermore, we discover the abnormal $Al_XO_Y$ layer on Al through the careful additional measurements. To find the reason, we evaluate the effect of package ball size and pinhole in passivation layer. Unfortunately, those aren't related to the problems. We also estimate halide effect of Al. The halogens such like Cl are contained within EMC material. Those result in the slight improving of PCT characteristics but do not perfectly solve the problems. We make a hypothesis of Galvanic corrosion. We can find the residue of Ti at the edge of pad open area. We can see the improving the PCT characteristics by the time split of repair etch. The possible mechanism of the PCT failure can be deduced as such following sequence of reactions. The remained Ti reacts on the pad Al by Galvanic corrosion. The ionized Al is easily react with the $H_2O$ supplied under PCT environment, and finally transfers to the abnormal $Al_XO_Y$ layer.

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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The Thermodynamics of the Formation of Polymethylbenzene-Halogens Charge Transfer Complexes (Ⅱ) (폴리메틸벤젠과 할로겐 사이의 전하이동착물 생성에 관한 열역학적 연구 (제2보))

  • Oh Cheun Kwun;Jeong Rim Kim
    • Journal of the Korean Chemical Society
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    • v.25 no.2
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    • pp.75-84
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    • 1981
  • Ultraviolet spectrophotometric investigations have been carried out on the systems of mesitylene with iodine, bromine, iodine monochloride and iodine monobromide in carbon tetrachloride. The results reveal the formation of the charge transfer complexes of the type, $C_6H_3(CH_3)_3{\cdot}X_2$ or $C_6H_3(CH_3)_3{\cdot}IX$ (X denotes halogen atoms). The equilibrium constants were obtained in consideration of that absorption maxima due to the formation of the charge transfer complexes shift to blue with the increasing temperatures. 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 mesitylene 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 mesitylene, which is explaned 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 < Toluene < Xylene < Mesitylene Thus, analysis of these findings is discussed.

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A Correlation Study between the Environmental, Personal Exposures and Biomarkers for Volatile Organic Compounds (대기 중 휘발성유기오염물질의 환경, 개인 및 인체 노출의 상관성 연구)

  • Jo, Seong-Joon;Shin, Dong-Chun;Chung, Yong;Breysse, Patrick N.
    • Environmental Analysis Health and Toxicology
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    • v.17 no.3
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    • pp.197-205
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    • 2002
  • Volatile organic compounds (VOCs) are an important public health problem throughout the world. Many important questions remain to be addressed in assessing exposure to these compounds. Because they are ubiquitous and highly volatile, special techniques must be applied in the analytical determination of VOCs. Personal exposure measurements are needed to evaluate the relationship between microenvironmental concentrations and actual exposures. It is also important to investigate exposure frequency, duration, and intensity, as well as personal exposure characteristics. In addition to air monitoring, biological monitoring may contribute significantly to risk assessment by allowing estimation of absorbed doses, rather than just the external exposure concentrations, which are evaluated by environmental and personal monitoring. This study was conducted to establish the analytic procedure of VOCs in air, blood, urine and exhaled breath and to evaluate the relationships among these environmental media. The subjects of this study were selected because they are occupationally exposed to high levels of VOCs. Environmental, personal, blood, urine and exhalation samples were collected. Purge & trap, thermal desorber, gas chromatography and mass selective detector were used to analyze the collected samples. Analytical procedures were validated with the“break through test”, 'quot;recovery test for storage and transportation”,“method detection limit test”and“inter-laboratory QA/QC study”. Assessment of halogenated compounds indicted that they were significantly correlated to each other (p value < 0.01). In a similar manner, aromatic compounds were also correlated, except in urine sample. Linear regression was used to evaluate the relationships between personal exposures and environmental concentrations. These relationships for aromatic and halogenated are as follows: Halogen $s_{personal}$ = 3.875+0.068Halogen $s_{environmet}$, ($R^2$= .930) Aromatic $s_{personal}$ = 34217.757-31.266Aromatic $s_{environmet}$, ($R^2$= .821) Multiple regression was used to evaluate the relationship between exposures and various exposure deter-minants including, gender, duration of employment, and smoking history. The results of the regression model-ins for halogens in blood and aromatics in urine are as follows: Halogen $s_{blood}$ = 8.181+0.246Halogen $s_{personal}$+3.975Gender ($R^2$= .925), Aromatic $s_{urine}$ = 249.565+0.135Aromatic $s_{personal}$ -5.651 D.S ($R^2$ = .735), In conclusion, we have established analytic procedures for VOC measurement in biological and environmental samples and have presented data demonstrating relationships between VOCs levels in biological media and environmental samples. Abbreviation GC/MS, Gas Chromatography/Mass Spectrometer; VOCs, Volatile Organic Compounds; OVM, Organic Vapor Monitor; TO, Toxic Organicsapor Monitor; TO, Toxic Organics.

Herbicidal Activity and Persistency in Aqueous Solution of Ortho Disubstituted Benzenesulfonyl Urea Derivatives (새로운 Ortho 이치환 Benzenesulfonyl Urea 유도체의 제초활성과 수용액중의 잔류성)

  • Kim, Yong-Jip;Chang, Hae-Sung;Kim, Dae-Whang;Sung, Nack-Do
    • Applied Biological Chemistry
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    • v.38 no.6
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    • pp.570-576
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    • 1995
  • The new sixteen herbicidal N-2-(1-hydroxy-2-fluoroethyl)-6-substituted(X)-benzenesulfonyl-N'-4,6-dimethoxypyrimidinyl-2-yl urea derivatives(S) were synthesized and thier herbicidal activities$(pI_{50})$ in vivo against rice(Orysa Sativa L.), Barnyard grass(Echninochloa orizicola) and Bulrush(Scirpus juncoides) were measured by the pot test under paddy conditions. The structure activity relationship(SAR) were studied using the physicochemical parameters of ortho-substituents(X) and hydrolysis rate constant(logk) and herbicidal activities by the multiple regression technique. The SAR suggested that the herbicidal activities were more dependant on the hydrolysis rate constant(logk>0) than the steric constants $(Es, small width($B_4$) and length($L_1$). Among them, halogens(2 & 5), methyl(15) and non(H) substituent(1) showed higher herbicidal activity for weeds which was not tolerent to rise and weeds. The herbicidal activity was increased and the persistency in aqueous solution was decreased by electron donating(${\sigma}0<0$) groups as ortho-substituent(X). From the relationship equation between herbicidal activity and hydrolysis rate constant, it was assumed that the both reactions would be proceeds with similar process. And the conditions on the ortho substituents to show higher herbicidal activity and the persistency in aqueous solution were also discussed.

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A Review of Pilot Plant Studies on Elemental Mercury Oxidation Using Catalytic DeNOxing Systems in MW-Scale Coal Combustion Flue Gases (MW급 석탄연소 배가스에서 탈질촉매시스템을 이용한 원소수은 산화 실증사례)

  • Kim, Moon Hyeon;Nguyen, Thi Phuong Thao
    • Clean Technology
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    • v.27 no.3
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    • pp.207-216
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    • 2021
  • Major anthropogenic emissions of elemental mercury (Hg0) occur from coal-fired power plants, and the emissions can be controlled successfully using NH3-SCR (selective catalytic reduction) systems with catalysts. Although the catalysts can easily convert the gaseous mercury into Hg2+ species, the reactions are greatly dependent on the flue gas constituents and SCR conditions. Numerous deNOxing catalysts have been proposed for considerable reduction in power plant mercury emissions; however, there are few studies to date of elemental mercury oxidation using SCR processes with MW- and full-scale coal-fired boilers. In these flue gas streams, the chemistry of the mercury oxidation is very complicated. Coal types, deNOxing catalytic systems, and operating conditions are critical in determining the extent of the oxidation. Of these parameters, halogen element levels in coals may become a key vehicle for obtaining better Hg0 oxidation efficiency. Such halogens are Cl, Br, and F and the former one is predominant in coals. The chlorine exists in the form of salts and is transformed to gaseous HCl with a trace amount of Cl2 during the course of coal combustion. The HCl acts as a very powerful promoter for high catalytic Hg0 oxidation; however, this can be strongly dependent on the type of coal because of a wide variation in the chlorine contents of coal.

Effects of Halogen and Light-Shielding Curtains on Acquisition of Hyperspectral Images in Greenhouses (온실 내 초분광 영상 취득 시 할로겐과 차광 커튼이 미치는 영향)

  • Kim, Tae-Yang;Ryu, Chan-Seok;Kang, Ye-seong;Jang, Si-Hyeong;Park, Jun-Woo;Kang, Kyung-Suk;Baek, Hyeon-Chan;Park, Min-Jun;Park, Jin-Ki
    • Korean Journal of Agricultural and Forest Meteorology
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    • v.23 no.4
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    • pp.306-315
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    • 2021
  • This study analyzed the effects of light-shielding curtains and halogens on spectrum when acquiring hyperspectral images in a greenhouse. The image data of tarp (1.4*1.4 m, 12%) with 30 degrees of angles was achieved three times with four conditions depending on 14 heights using the automatic image acquisition system installed in the greenhouse at the department of Southern Area of National Institute of Crop Science. When the image was acquired without both a light-shielding curtain and halogen lamp, there was a difference in spectral tendencies between direct light and shadow parts on the base of 550 nm. The average coefficient of variation (CV) for direct light and shadow parts was 1.8% and 4.2%, respective. The average CV value was increased to 12.5% regardless of shadows. When the image was acquired only used a halogen lamp, the average CV of the direct light and shadow parts were 2 .6% and 10.6%, and the width of change on the spectrum was increased because the amount of halogen light was changed depending on the height. In the case of shading curtains only used, the average CV was 1.6%, and the distinction between direct light and shadows disappeared. When the image was acquired using a shading curtain and halogen lamp, the average CV was increased to 10.2% because the amount of halogen light differed depending on the height. When the average CV depending on the height was calculated using halogen and light-shielding curtains, it was 1.4% at 0.1m and 1.9% at 0.2 m, 2 .6% at 0.3m, and 3.3% at 0.4m of height, respectively. When hyperspectral imagery is acquired, it is necessary to use a shading curtain to minimize the effect of shadows. Moreover, in case of supplementary lighting by using a halogen lamp, it is judged to be effective when the size of the object is less than 0.2 m and the distance between the object and the housing is kept constant.