• Title/Summary/Keyword: $S_N2-S_N2'$ Reaction

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Serial Degradation of Perchloroethylene by Delftia sp. N6 after Dechlorination Using Fenton's Reagent

  • Lee, Wan-Seok;Kim, Jang-Eok;Kim, Hee-Sik;Ahn, Chi-Yong;Oh, Hee-Mock
    • Journal of Microbiology and Biotechnology
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    • v.16 no.11
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    • pp.1734-1739
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    • 2006
  • The degradation of perchloroethylene (PCE) was investigated with the serial treatment of biological reaction after dechlorination using Fenton's reagent. The dechlorination of PCE was expressed using $D_m$ (dechlorination value), calculated from ${\Delta}Cl^-mol/{\Delta}PCE$ mol, and was 2.58 with 5 mM of $H_2O_2$ and $Fe^{3+}$. The $150{\mu}M$ of PCE was transformed to $37{\mu}M$ of dichloroacetic acid (DCAA). Biological treatment with Delftia sp. N6 was applied after degradation of PCE by the Fenton reaction. The optical densities indicating cell growth were 0.53/0.10 with/without the Fenton reaction after one day, respectively. The N6 strain degraded 95% of the DCAA produced from PCE by the Fenton reaction within one day. Consequently, it seemed that the serial treatment of a Fenton reaction and biological reaction was effective in the removal of not only PCE, but also DCAA, one of the major metabolites of PCE.

Assessment of the Nitrate Radical Chemistry and Chemical Composition on Jeju Island during the Asian Pollution Period in the Spring of 2001

  • Shon, Zang-Ho;Kim, Ki-Hyun;Keith N. Bower;Lee, Gangwoong;Kim, Jiyoung
    • Journal of Korean Society for Atmospheric Environment
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    • v.19 no.E3
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    • pp.137-148
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    • 2003
  • In this study, we examined the influence of long-range transport of dust particles and air pollutants on the photochemistry of NO$_3$on Jeju Island, Korea (33.17 N, 126.10$^{\circ}$E) during the Asian Dust-Storm (ADS) period of April 2001. Three ADS events were observed during the periods of 10∼12, 13∼14, and 25∼26 April. Average concentration level of nighttime NO$_3$on Jeju Island during the ADS period was estimated to be about 2 x 10$^{8}$ molecules cm$^{-3}$ ( - 9 pptv). Decreases in NO$_3$levels during the ADS period was likely to be determined mainly by the enhancement of the $N_2$O$_{5}$ heterogeneous reaction on dust aerosol surfaces. The reaction of N20s on aerosol surfaces was a more important sink for nighttime N03 during the ADS due to the significant loading of dust particles. The reaction of $N_2$O$_{5}$ with NMHCs and the gas-phase reaction of N20s with water vapor were both significant loss mechanisms during the study period, especially during the NADS. However, dry deposition of these oxidized nitrogen species and a heterogeneous reaction of NO$_3$were of no importance. Short-term observations of $O_3$, NO$_2$, DMS, and SO$_2$in the MBL indicated that concentrations of most of these chemical species were different between the ADS and non - Asian - Dust-Storm (NADS) periods, implying that their levels were affected sensitively by the differences in air mass trajectories.

Theoretical Studies on the Acid-Catalyzed Hydrolysis of Sulfinamide

  • 김찬경;이익준
    • Bulletin of the Korean Chemical Society
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    • v.18 no.8
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    • pp.880-886
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    • 1997
  • Ab initio calculations were carried out on the gas phase acid-catalyzed hydrolysis reactions of sulfinamide using the 3-21G* basis sets. Single point calculations were also performed at the MP2/6-31G* level. The first step in the acid-catalyzed hydrolysis of N-methylmethanesulfinamide, Ⅰ, involves protonation. The most favorable form is the O-protonated one, Ⅱ, which is then transformed into a sulfurane intermediate, Ⅲ, by addition of a water molecule. The reaction proceeds further by an intramolecular proton transfer from O to N (TS2), which is followed by N-S bond cleavage (TS3) leading to the final products. The rate determining step is the N-S bond cleavage (TS3) at the RHF/3-21G* level, whereas it becomes indeterminable at the MP2/6-31G*//3-21G* level of theory. However, the substituent effect studies with N-protonated N-arylmethanesulfinamide, ⅩⅢ, at the MP2/6-31G*//3-21G* level support the N-S bond breaking step as rate limiting.

Fabrication and Characteristics of $n-CdS_{0.69}Se_{0.31}/p-Cu_{2-x}S_{0.69}Se_{0.31}$ Heterojunction Solar Cell ($n-CdS_{0.69}Se_{0.31}/p-Cu_{2-x}S_{0.69}Se_{0.31}$ Heterojunction 태양전지의 제작과 특성)

  • Baek, Seung-Nam;Hong, Kwang-Joon
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2004.04b
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    • pp.51-55
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    • 2004
  • $CdS_{0.69}Se_{0.31}$ single crystal grown by sublimation method. Hall effect measurement were carried out by the Van der Pauw method. The measurement values under the temperature were found to be carrier density $n=1.95{\times}10^{23}m^{-3}$, Hall coeffcient $RH=3.21{\times}10^{-5}m^3/c$, conductivity ${\sigma}=362.41{\Omega}^{-1}m^{-1}$, and Hall mobility ${\mu}=1.16{\times}10^{-2}m^2/v.s.$ Heterojunction solar cells of $n-CdS_{0.69}Se_{0.31}/p-Cu_{2-x}S_{0.69}Se_{0.31}$ were fabricated by the substitution reaction. The open-circuit voltage, short-circuit currint density, fill factor and power conversion efficiency of $n-CdS_{0.69}Se_{0.31}/p-Cu_{2-x}S_{0.69}Se_{0.31}$ heterojunction solar cell under $80mW/cm^2$ illumination were found to be 0.41V, $19.5mA/cm^2$, 0.75 and 9.99%, respectivity.

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Kinetics and Mechanism for Redox Reaction of cis-$[Co(en)_2(N_3)_2]^+$ with Fe(II) in Acidic Solution (산 촉매하에서 cis-$[Co(en)_2(N_3)_2]^+$ 와 Fe(II) 와의 산화-환원반응에 대한 반응속도와 메카니즘)

  • Byung-Kak Park;Kwang-Jin Kim;Joo-Sang Lim
    • Journal of the Korean Chemical Society
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    • v.33 no.3
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    • pp.309-314
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    • 1989
  • A kinetic study was carried out for the redox reaction of cis-$[Co(en)_2(N_3)_2]^+$ with Fe(II) in acidic solution by spectrophotometric methods. This redox reaction system have been found to show a third order for overall reaction as the respective first order with respect to reactant cis-$[Co(en)_2(N_3)_2]^+$, Fe(II), and $H^+$ catalyst. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were obtained as 14.2Kcal/mol and -16.7 e.u., respectively. On the basis of the kinetic data, we suggest that the redox reaction system proceeds via inner sphere mechanism. The rate equation derived from the proposed mechanism is in agreement with the observed rate equation.

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The Mechanism of the Decomposition of a Bronchodilator, S-Nitroso-N-acetyl-D,L-penicillamine (SNAP), by a Bronchoconstrictor, Aqueous Sulfite: Detection of the N-Nitrosohydroxylamine-N-sulfonate ion

  • Holder, Alvin A.;Marshall, Sophia C.;Wang, Peng George;Kwak, Chee-Hun
    • Bulletin of the Korean Chemical Society
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    • v.24 no.3
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    • pp.350-356
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    • 2003
  • The mechanism of the decomposition of a bronchodilator, S-nitroso-N-acetyl-D,L-penicillamine (SNAP) by a bronchoconstrictor, aqueous sulfite, has been investigated in detail. The decomposition was studied using a conventional spectrophotometer at 336 nm over the ranges: 0.010 ≤ $[S^{IV}]_T$ ≤ 0.045 mol $dm^{-3}$, 3.96 ≤ pH ≤ 6.80 and 15.0 ≤ θ≤ 30.0 ℃, 0.60 ≤ I ≤ 1.00 mol $dm^{-3}$, and at ionic strength 1.00 mol $dm^{-3}$ (NaCl). The rate of reaction is dependent on the total sulfite concentration and pH in a complex manner, i.e., $k_{obs}\;=\;k_1K_2[S^{IV}]_T/ ([H^+]\;+\;K_2)$. At 25.0 ℃, the second order rate constant, $k_1$, was determined as $12.5\;{\pm}\;0.15\;mol^{-1}\;dm^3\;s^{-1}$. ${\Delta}H^{neq}\;=\;+32\;{\pm}\;3 kJ\;mol^{-1}\;and\;{\Delta}S^{\neq}\;=\;-138\;{\pm}\;13\;J\;mol^{-1}K^{-1}$. The N-nitrosohydroxylamine-N-sulfonate ion was detected as an intermediate before the formation of any of the by-products, namely, N-acetyl-D,L-penicillamine. The effect of concentration of aqueous copper(Ⅱ) ions on this reaction was also examined at pH 4.75, but there was no dependence on $[Cu^{2+}]$. In addition, the $pK_a$ of SNAP was determined as 3.51 ± 0.06 at 25.4 ℃ [I = 1.0 mol $dm^{-3}$ (NaCl)].

Application of the Extended Grunwald-Winstein Equation to the Solvolyses of 4-(Chlorosulfonyl)biphenyl

  • Kang, Suk Jin;Koh, Han Joong
    • Journal of the Korean Chemical Society
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    • v.61 no.1
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    • pp.25-28
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    • 2017
  • Solvolyses with the reaction center being the sulfur of 4-(chlorosulfonyl)biphenyl ($C_6H_5C_6H_4SO_2Cl$, 1) was studied under solvolytic conditions and the extended Grunwald-Winstein equation was applied. The thirty five kinds of solvents gave a reasonable extended Grunwald-Winstein plot with a correlation coefficient (R) of 0.940. The sensitivity values (l = 0.60 and m = 0.47) of 1 were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, 2; l = 1.10 and m = 0.61) proposed to undergo dissociative $S_N2$ mechanism. These l and m values for the solvolyses of 1 can be considered to support a $S_N2$ pathway with some ionization reaction. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction. The kinetic solvent isotope effect (KSIE) of 1.26 is also in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

Synthesis of Photoconductive N-unsaturated Alkylcarbazole Derivatives (광전도성 N-불포화알킬카르바졸 유도체의 합성)

  • Jung, Eun-Sil;Cho, Eul-Hoon;Chung, Pyung-Jin
    • Applied Chemistry for Engineering
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    • v.9 no.4
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    • pp.548-553
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    • 1998
  • The N-unsaturated alkylcarbazole derivatives were synthesized by the nucleophilic unimolucular substitution reaction ($S_N1$) of carbazole with unsaturated alkyl chloride. These reactions between carbazole and unsaturated alkyl chloride were conducted in dimethyl sulfoxide (DMSO) containing alkali (NaOH or KOH) at room temperature for 4 hrs under nitrogen atmosphere. The mole ratios of carbazole, alkali and unsaturated alkyl chloride were 1:6:1, respectively. All of the compounds of starting materials and reaction products were characterized by CHN analysis, $^1H$-NMR and FR-IR spectroscopy.

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A Novel Method for Preparing of Oxoruthenates Complexes: trans-[RuO3(OH)2]2-, [RuO4]-, (n-Pr4N)+[RuO4]- and [RuO4 and Their Use as Catalytic Oxidants

  • Shoair, Abdel-Ghany F.
    • Bulletin of the Korean Chemical Society
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    • v.26 no.10
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    • pp.1525-1528
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    • 2005
  • The synthesis and characterization of ${K_3[Ru(C_2O_4)3]{\cdot}4H_2O\;(C_2O_4}^{2-}$ = oxalato anoin) complex are described, and its redox properties (in buffer solution of pH = 12) have been investigated. This complex is used for in situ generation of oxoruthenates complexes which have been characterized by electronic spectroscopy. Reaction of ${K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${S_2O_8}^{2-}$ in molar KOH generates trans-${[RuO_3(OH)_2]^{2-}/S_2O_8}^{2-}$ reagent while with excess ${BrO_3}^-$ in molar $Na_2CO_3$ generates ${[RuO_4]^-/BrO_3}^-$ reagent. Avoiding the direct use of [$RuO_4$] the organic-soluble $(n-Pr_4N)^+[RuO_4]^-$, (TPAP) has been isolated by reaction of $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${BrO_3}^-$ in molar carbonate and n-$Pr_4$NOH. In a mixture of $H_2O/CCl_4$ ruthenium tetraoxide can be generated by reaction of $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${IO_4}^-$. The catalytic activities of oxoruthenates that have been made from $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ towards the oxidation of benzyl alcohol, piperonyl alcohol, benzaldehyde and benzyl amine at room temperature have been studied.