• 제목/요약/키워드: $^1$ $O_2$ reaction rate constant

검색결과 142건 처리시간 0.023초

망간산화물(Birnessite)을 매개로한 산화-변환반응을 이용한 PAH-퀴논화합물의 제거 (Removals of PAH-quinones Using Birnessite-Mediated Oxidative-Transformation Processes)

  • 최찬규;한윤이;김성욱;신현상
    • 대한환경공학회지
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    • 제33권6호
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    • pp.396-404
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    • 2011
  • 본 연구에서는 PAHs 오염토양의 화학적 생물학적 처리과정에서 반응부산물로 흔히 발견되는 PAH-퀴논화합물을 대상으로 수용액 상에서의 망간산화물에 의한 산화-변환 제거 특성(제거율, 반응속도)을 조사하였다. 반응시간 경과에 따른 상등액의 HPLC 분석결과로부터 p-퀴논화합물인 Acenaphthenequinone (APQ)는 망간산화물 자체에 의한 산화-결합 반응을 통해 제거되며, o-퀴논화합물인 Anthraquinone (AQ)와 1,4-Naphthoquinone (1,4-NPQ)는 반응매개체(Catechol) 존재 하에서의 교차-결합반응을 통해 효과적으로 제거 가능함을 확인하였다. 망간산화물에 의한 PAH-퀴논화합물의 제거는 유사-일차 반응 속도식을 따랐으며, 본 실험조건(1,4-NPQ = 11.5 mg/L, CAT = 50 mg/L, $MnO_2$ = 1.0 g/L, pH 5, 반응시간 = 6~96 hr)에서의 1,4-NPQ의 교차-결합 반응속도상수(k, $hr^{-1}$)는 0.0426으로 APQ의 산화-결합 반응속도 상수(0.173)에 비교해 약 4배 정도의 차이를 보였다. 동일조건에서의 망간산화물 주입량별 속도상수를 망간산화물의 비표면적으로 표준화하여 얻은 1,4-NPQ의 교차-결합 반응에 대한 비표면적표준화속도상수($K_{surf}$)는 $8.5{\times}10^{-4}L/m^2{\cdot}hr$이었다. 망간산화물 주입량별 제거특성과 반응 속도상수의 비교 해석 결과로부터 1,4-NPQ의 교차-결합 반응은 반응시간 경과에 따라 서로 다른 반응기작을 거침을 확인하였으며, 이를 기존 문헌결과와 함께 해석하였다.

A Kinetic Study on Aminolysis of t-Butyl 4-Pyridyl Carbonate and Related Compounds: Effect of Leaving and Nonleaving Groups on Reaction Mechanism

  • Kang, Ji-Sun;Lee, Jae-In;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제33권9호
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    • pp.2971-2975
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    • 2012
  • Second-order rate constants $k_N$ have been measured spectrophotometrically for nucleophilic substitution reactions of t-butyl 4-pyridyl carbonate 8 with a series of alicyclic secondary amines in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. The Br${\emptyset}$nsted-type plot for the reactions of 8 is linear with ${\beta}_{nuc}$ = 0.84. The ${\beta}_{nuc}$ value obtained for the reactions of 8 is much larger than that reported for the corresponding reactions of t-butyl 2-pyridyl carbonate 6 (i.e., ${\beta}_{nuc}$ = 0.44), which was proposed to proceed through a forced concerted mechanism. Thus, the aminolysis of 8 has been concluded to proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate $T^{\pm}$, in which expulsion of the leaving-group from $T^{\pm}$ occurs at the rate-determining step (RDS). In contrast, aminolysis of benzyl 4-pyridyl carbonate 7 has been reported to proceed through two intermediates, $T^{\pm}$ and its deprotonated form $T^-$ on the basis of the fact that the plots of pseudo-first-order rate constant $k_{obsd}$ vs. amine concentration curve upward. The current study has demonstrated convincingly that the nature of the leaving and nonleaving groups governs the reaction mechanism. The contrasting reaction mechanisms have been rationalized in terms of an intramolecular H-bonding interaction, steric acceleration, and steric inhibition.

Characteristics of Alkali-activated Natural Hwangtoh Paste Utilizing Microwave Heating

  • Kim, Baek-Joong;Yi, Chong-Ku;Kang, Kyung-In
    • 한국건축시공학회지
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    • 제12권5호
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    • pp.503-509
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    • 2012
  • In this study, the potential use of indigenous natural loess(Hwangtoh) as a new construction material, via alkali activation in conjunction with microwave heating, was investigated. Hwangtoh pastes with three different mix proportions of varying alkali liquid concentrations at a constant liquid-to-Hwangtoh ratio of 0.55 were prepared. Through the investigation it was found that it is possible to prepare Hwangtoh paste with $19.02N/mm^2$ at the age of 4 hours with the alkali solution of 8M NaOH and 1:4.5 mass ratio of liquefied $Na_2SiO_3$ at the curing temperature of $60^{\circ}C$ by microwave heating. The strength development at early age of the alkali activated Hwangtoh paste specimens may be attributed to both a higher rate of reaction and moisture evaporation due to microwave heating.

N,N'-bis(3-pyrrol-1-yl-propyl)-4,4'-bipyridinium이온의 산화-환원 고분자 피막에 대한 전기화학 (Electrochemistry for Redox Polymer Film of N,N'-bis(3-pyrrol-1-yl-propyl)-4,4'-bipyridinium Ion)

  • 차성극
    • 폴리머
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    • 제25권1호
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    • pp.6-14
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    • 2001
  • 단량체인 N,N'-bis(3-pyrrol-1-yl-propyl)-4,4'-bipyridinium$(PF_6^-)_2$를 유리탄소전극 상에 전기화학적으로 중합하였다. 이 고분자 피막전극의 전기화학적 활성자리는 고분자 줄기에 분포된 bipyridinium이온이다. 이 전극은 인산염 완충용액(pH=5.7)에서 두 개의 산화-환원 쌍을 갖으며 그 형식전위는 각각 -0.41V와 -0.81V(vs. SSCE)였다. 이 고분자 피막 내에서 도판트 이온의 확산계수는 $V^{2+/+}$$V^{+/0}$ 단계에서 $1.57{\times}10^{-4}$$4.35{\times}10^{-5}cm^2s^{-1}$이였다. 환원과정보다 산화과정이 어려운 결과로 나타났다. 고분자 피막 내에서 전자전달 속도상수는 각 단계에서 각각 57.53과 $2.63 s^{-1}$으로 첫째 단계가 22배나 큰 값을 보이고 있다. 이 피막의 전자전달 저항은 적용된 전해질의 양이온에 크게 영향을 받는다. 즉, $LiClO_4,\; NaClO_4,\;KClO_4$ 및 인산염 완충용액에서 도판트이온으로 작용하는 $ClO_4^-$$PO_4^{3-}$ 이외에 이들의 대이온의 영향도 받아서 그 값이 각각 22.63, 16.81, 12.44 및 $11.36 k{\Omega}$로 크게 차이가 났다. EQCM에 의한 전기화학적 중합반응의 속도상수 값은 일차 반응으로 초기에 $1.31{\times}10^{-1}s^{-1}$였다. 이와 같이 $PO_4^{3-}$이 도판트인 G.C./p-BPB형의 전극이 CV과정에서 안정하고 20회 이상 사용이 가능하며 재현성이 뛰어나다.

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몰리브덴인산화물 촉매에 의한 메틸피라진의 가암모니아 산화반응 (Ammoxidation of Methylpyrazine over Molybdenum Phosphate Catalyst)

  • 신채호;장태선;조득희;이동구;이영길
    • 공업화학
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    • 제8권5호
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    • pp.749-755
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    • 1997
  • 몰리브덴산암모늄염과 인산의 반응으로 P/Mo=0.6의 비율을 가진 몰리브덴인산화물을 제조하고 이를 촉매로 사용하여 메틸피라진의 가암모니아 산화반응에 대한 메틸피라진, 산소, 암모니아의 각각의 분압과 반응온도 등의 반응변수의 영향을 살펴보았다. 표준실험조건하의 반응에서 300시간까지의 촉매활성은 안전상태를 유지하였다. 안정화 상태에서의 메틸피라진의 가암모니아 산화반응 속도식은 $-r=kP_{MP}P_{NH3}{^0}P_{O2}{^{\gamma}}({\gamma}=2.2;1.3{\leq}P_{O2}(kPa){\leq}4)$으로 메틸피라진에 대해서는 1차, 암모니아에 대해서는 0차, 산소에 대해서는 분압 4kPa이하에서 2.2차로 나타났다. 623K이하의 반응온도 하에서의 겉보기 활성화에너지는 29.6kcal/mol이었다. 메탈피리진의 주생성물은 시아노피라진으로서 선택도는 전환율에 관계없이 항상 90%이상을 유지하였다.

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비수용매에서 산소첨가된 네자리 Schiff Base Cobalt(II)(3MeOSED) 활성촉매에 의한 Hydrazobenzene의 산화반응과 전기화학적 성질 (제 1 보) (Electrochemical Propertics and Oxidation Reaction of Hydrazobenzene by Oxygen Adducted Tetradentate Schiff Base Cobalt(II)(3MeOSED) Activated Catalyst in Aprotic Solvents(I))

  • 조기형;최용국;김상복
    • 대한화학회지
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    • 제36권2호
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    • pp.261-272
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    • 1992
  • 네자리 Schiff base의 착물 Co(II)(3MeOSED)$(H_2O)_2$을 합성하였다. 이 착물의 균일 산화 활성촉매로서 산소첨가 착물은 DMF와 DMSO 용매에서는 ${\mu}$-peroxo형인 [Co(III)(3MeOSED)(DMF)]$_2O_2$와 [Co(III)(3MeOSED)(DMSO)]$_2O_2$이나 pyridine 용매에서는 superoxo형인 [Co(Ⅲ)(3MeOSED)(Py)]$O_2$로 주어진다. 이들의 CV법과 DPP법에 의한 전기화학적인 특성으로 ${\mu}$-peroxo형은 3단계 환원과정으로 일어나지만, superoxo형은 $O_2$의 prewave를 포함한 4단계 환원과정으로 일어난다. 산소가 포화된 메탄올 용액에서 [Co(III)(3MeOSED)(L)]$O_2(L: CH_3OH)$ 의 균일 산화 활성촉매에 의한 hydrazobenzene-$(H_2AB)$의 산화 주생성물은 trans-azobenzene(t-AB)이 선택적으로 다음과 같은 반응식으로 생성되고 이 때 속도상수는 k = (2.96 ${\pm}$ 0.2) ${\times}$ $10^{-1}$M/sec임을 알았다. $H_2AB$ + Co (Ⅱ)(3MeOSED)$(L_2)+O_2\;{\rightleftarrow^K}$ [Co(III)(3MeOSED)(L)]$O_2{\cdot}H_2AB{\longrightarrow^K}$ Co(II(3MeOSED)$(L)_2$+t-AB+$H_2O_2 $.

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Glass Dissolution Rates From MCC-1 and Flow-Through Tests

  • Jeong, Seung-Young
    • 한국방사성폐기물학회:학술대회논문집
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    • 한국방사성폐기물학회 2004년도 학술논문집
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    • pp.257-258
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    • 2004
  • The dose from radionuclides released from high-level radioactive waste (HLW) glasses as they corrode must be taken into account when assessing the performance of a disposal system. In the performance assessment (PA) calculations conducted for the proposed Yucca Mountain, Nevada, disposal system, the release of radionuclides is conservatively assumed to occur at the same rate the glass matrix dissolves. A simple model was developed to calculate the glass dissolution rate of HLW glasses in these PA calculations [1]. For the PA calculations that were conducted for Site Recommendation, it was necessary to identify ranges of parameter values that bounded the dissolution rates of the wide range of HLW glass compositions that will be disposed. The values and ranges of the model parameters for the pH and temperature dependencies were extracted from the results of SPFT, static leach tests, and Soxhlet tests available in the literature. Static leach tests were conducted with a range of glass compositions to measure values for the glass composition parameter. The glass dissolution rate depends on temperature, pH, and the compositions of the glass and solution, The dissolution rate is calculated using Eq. 1: $rate{\;}={\;}k_{o}10^{(ph){\eta})}{\cdot}e^{(-Ea/RT)}{\cdot}(1-Q/K){\;}+{\;}k_{long}$ where $k_{0},\;{\eta}$ and Eaare the parameters for glass composition, pH, $\eta$ and temperature dependence, respectively, and R is the gas constant. The term (1-Q/K) is the affinity term, where Q is the ion activity product of the solution and K is the pseudo-equilibrium constant for the glass. Values of the parameters $k_{0},\;{\eta}\;and\;E_{a}$ are the parameters for glass composition, pH, and temperature dependence, respectively, and R is the gas constant. The term (1-Q/C) is the affinity term, where Q is the ion activity product of the solution and K is the pseudo-equilibrium constant for the glass. Values of the parameters $k_0$, and Ea are determined under test conditions where the value of Q is maintained near zero, so that the value of the affinity term remains near 1. The dissolution rate under conditions in which the value of the affinity term is near 1 is referred to as the forward rate. This is the highest dissolution rate that can occur at a particular pH and temperature. The value of the parameter K is determined from experiments in which the value of the ion activity product approaches the value of K. This results in a decrease in the value of the affinity term and the dissolution rate. The highly dilute solutions required to measure the forward rate and extract values for $k_0$, $\eta$, and Ea can be maintained by conducting dynamic tests in which the test solution is removed from the reaction cell and replaced with fresh solution. In the single-pass flow-through (PFT) test method, this is done by continuously pumping the test solution through the reaction cell. Alternatively, static tests can be conducted with sufficient solution volume that the solution concentrations of dissolved glass components do not increase significantly during the test. Both the SPFT and static tests can ve conducted for a wide range of pH values and temperatures. Both static and SPFt tests have short-comings. the SPFT test requires analysis of several solutions (typically 6-10) at each of several flow rates to determine the glass dissolution rate at each pH and temperature. As will be shown, the rate measured in an SPFt test depends on the solution flow rate. The solutions in static tests will eventually become concentrated enough to affect the dissolution rate. In both the SPFt and static test methods. a compromise is required between the need to minimize the effects of dissolved components on the dissolution rate and the need to attain solution concentrations that are high enough to analyze. In the paper, we compare the results of static leach tests and SPFT tests conducted with simple 5-component glass to confirm the equivalence of SPFT tests and static tests conducted with pH buffer solutions. Tests were conducted over the range pH values that are most relevant for waste glass disssolution in a disposal system. The glass and temperature used in the tests were selected to allow direct comparison with SPFT tests conducted previously. The ability to measure parameter values with more than one test method and an understanding of how the rate measured in each test is affected by various test parameters provides added confidence to the measured values. The dissolution rate of a simple 5-component glass was measured at pH values of 6.2, 8.3, and 9.6 and $70^{\circ}C$ using static tests and single-pass flow-through (SPFT) tests. Similar rates were measured with the two methods. However, the measured rates are about 10X higher than the rates measured previously for a glass having the same composition using an SPFT test method. Differences are attributed to effects of the solution flow rate on the glass dissolution reate and how the specific surface area of crushed glass is estimated. This comparison indicates the need to standardize the SPFT test procedure.

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산화철 나노구조박막 이용한 도금폐수내의 시안제거 (Cyanide Degradation from Plating Wastewater Using Iron Oxide Nanocomposite Layer)

  • 장준원;김혜란;임형석;박재우
    • 한국물환경학회지
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    • 제30권3호
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    • pp.292-297
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    • 2014
  • We synthesized the self-organized nanoporous oxide with potentiostatic anodization of iron foil. The iron oxide nanocomposite (INCs) were fabricated in 1M $Na_2SO_4$ containing 0.5wt% NaF electrolyte holding the potential at 20, 40 and 60 V for 20min, respectively. Field Emmision Scanning Electron Microscopy (FESEM) and X-ray Diffractometer (XRD) were used to evaluate the micromorphology and crystalline structure of INC film. Also, this study was performed to evaluate the fenton reaction using INC film with hydroperoxide for degradation of cyanide dissolved in water. In case of INC-40V in the presence of $H_2O_2$ 3%, the first-order rate constant was found to be $1.7{\times}10^{-2}min^{-1}$, and indicated to be $1.2{\times}10^{-2}min^{-1}$ on commercial hematite powder. This result is shown to be good performance enough to replace the powder type for treatment of wastewater.

오존 처리 및 UV 조사를 이용한 Sulfamethoxazole 제거; 동역학적 고찰 및 pH 영향 (Removal of Sulfamethoxazole using Ozonation or UV Radiation; Kinetic Study and Effect of pH)

  • 정연정;김완기;장하영;최양훈;오병수;강준원
    • 한국물환경학회지
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    • 제24권1호
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    • pp.63-68
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    • 2008
  • This study was performed to assess the potential use of ozone or UV radiation for the treatment of water contaminated with sulfamethoxazole (SMX), which is frequently used antibiotic in human and veterinary medicines, especially focusing on the kinetic study and effect of pH. In a study using ozone alone, kinetic study was performed to determine second-order rate constant ($k_{O3,SMX}$) for the reactions of SMX with ozone, which was found to be $1.9{\times}10^6M^{-1}s^{-1}$ at pH 7. The removal efficiencies of SMX by ozone were decreased with increase of pH due to rapid decomposition of ozone under the condition of various pH (2.5, 5.3, 7, 8, 10). In a UV irradiation study at 254 nm, a kinetic model for direct photolysis of SMX was developed with determination of quantum yield ($0.08mol\;Einstein^{-1}$) and molar extinction coefficient ($15,872M^{-1}cm^{-1}$) values under the condition of quantum shielding due to the presence of reaction by-products formed during photolysis. For effect of pH on photolysis of SMX, SMX in the anionic state ($S^-$, pH > 5.6), most prevalent form at environmentally relevant pH values, degraded more slowly than in the neutral state (SH, 1.85 < pH < 5.6) by UV radiation at 254 nm.

수분함량, 가열온도 및 가열시간에 따른 전분 반죽의 호화특성 (Gelatinization Properties of Starch Dough with Moisture Content, Heating Temperature and Heating Time)

  • 이부용;이창호;이철호
    • 한국식품과학회지
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    • 제27권3호
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    • pp.428-438
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    • 1995
  • Corn starch와 waxy corn starch를 사용하여 중간수분계의 수분함량으로 반죽을 제조하고 수분함량과 가열온도, 가열시간에 따른 전분 반죽의 호화양상을 밝혀 보고자 하였다. Corn starch와 waxy corn starch의 amylograph 호화 특성은 1% CMC를 첨가하여 측정한 호화개시 온도가 모두 약 $64^{\circ}C$로 나타났다. DSC특성은 corn starch호화 개시 온도가 $68.15^{\circ}C$, 최대호화온도가 $74.01^{\circ}C$, 호화종결 온도가 $85.65^{\circ}C$, 호화엔탈피는 3.2 cal/gram이었으며, waxy corn starch의 호화개시온도는 $68.24^{\circ}C$, 최대호화온도 $75.43^{\circ}C$, 호화종결온도 $93^{\circ}C$, 호화엔탈피는 4.2 cal/gram으로 나타났다. 수분함량$(X_1)\;36{\sim}52%)$, 가열온도$(X_2)\;60{\sim}100^{\circ}C$, 가열시간$(X_3)$ $0{\sim}2.0$분으로 가열시 corn starch와 waxy corn starch 반죽의 호화도(Y) 변화를 실험계획법으로 조사한 반응표면 회귀 방정식은 corn starch 반죽의 경우 $Y=28.659+8.638\;X_1+15.675\;X_2+7.770\;X_3-1.620\;{X_1}^2+10.790\;X_1X_2-4.220\;{X_2}^2+0.510\;X_1X_3+1.980\;X_2X_3-6.850\;{X_3}^2$ $(R^2=0.9714)$ 이었고 waxy corn starch 반죽의 경우는 $Y=32.617+12.535\;X_1+20.470\;X_2+8.608\;X_3+4.093\;{X_1}^2+13.550\;X_1X_2-4.467\;{X_2}^2+1.560\;X_1X_3+2.160\;X_2X_3-9.527\;{X_3}^2$ $(R^2=0.9621)$이었다. 즉 수분함량과 가열온도, 가열시간이 증가할수록 반죽의 호화도는 모두 증가하는 경향을 나타내었고 같은 조건에서는 waxy corn starch가 corn starch 반죽보다 $10{\sim}20%$ 정도 더 호화되는 것을 알 수 있었다. Corn starch 와 waxy corn starch 반죽의 호화 속도를 보면 가열온도 $70^{\circ}C$$80^{\circ}C$에서는 가열시간 0.5분 이내에서 비교적 빠른 속도로 반죽이 호화되고 가열시간이 그 이상으로 증가할 때도 반죽의 호화가 약간은 진행되지만 $90^{\circ}C$ 이상의 가열온도에서는 가열시간 0.5분 이내에 반죽의 호화가 급속히 일어나고 가열 시간을 증가시켜도 더이상의 호화는 일어나지 않았다. 같은 조건에서는 waxy corn starch 반죽의 호화 속도가 corn starch보다 더 빠른 것으로 나타났다. 대표적으로 52% 수분함량에서 반응속도상수(k)와 가열온도(T)사이의 관계식은 corn starch의 경우 $logk=11.1140-4.1226{\times}10^3(1/T)$, waxy corn starch의 경우 $logk=10.1195-3.7090{\times}10^3(1/T)$이었다.

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