• Title/Summary/Keyword: first-order kinetics

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Kinetics and Mechanisms of the Oxidation of Carbon Monoxide on Ni-Doped $\alpha-Fe_2O_3$

  • Kim, Keu-Hong;Jun, Jong-Ho;Choi, Jae-Shi
    • Bulletin of the Korean Chemical Society
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    • v.5 no.1
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    • pp.41-44
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    • 1984
  • The oxidation of carbon monoxide has been investigated on Ni-doped ${\alpha}-Fe_2O_3$ catalyst at 300 to $450^{\circ}$. The oxidation rates have been correlated with 1.5-order kinetics; first with respect to CO and 1/2 with respect to $O_2$. Carbon monoxide is adsorbed on lattice oxygen of Ni-doped ${\alpha}-Fe_2O_3$, while oxygen appears to be adsorbed on oxygen vacancy formed by Ni-doping. The conductivities show that adsorption of CO on O-lattice produces conduction electron and adsorption of $O_2$ on O-vacancy withdraws the conduction electron from vacancy. The adsorption process of CO on O-lattice is rate-determining step and dominant defect of Ni-doped ${\alpha}-Fe_2O_3$ is suggested from the agreement between kinetic and conductivity data.

Nucleiphilic Substitution Reactions of Thiophenyl Dimethylacetates and Trimethylacetates wkth Benzylamines in Acetonitfile

  • O, Hyeok Geun;Park, Chi Yeol;Lee, Jae Mun;Lee, Ik Chun
    • Bulletin of the Korean Chemical Society
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    • v.22 no.4
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    • pp.383-387
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    • 2001
  • The kinetics and mechanism of the reactions of thiophenyl dimethylacetates (TDA) and trimethylacetates (TTA) with benzylamines in acetonitrile are studied. The reactions are first order in both the amine and the substrate. Relatively large values of ${\beta}X(\betanuc$ = 1.1-1.5; TDA and 1.1-1.5; TTA) and ${\beta}Z({\beta}lg$ = -1.8~-2.0; DTA and -1.3~-1.6; TTA) for benzylamines, significantly large kH/kD values (=1.2-1.5; DTA and 1.2-1.5; TTA) involving deuterated benzylamines, and large ${\rho}XZ$ (=0.82; TDA and 1.05; TTA) values are interpreted to indicate stepwise acyl transfer mechanism, but with the hydrogen bonded four center type transition state for benzylamine. The relatively greater magnitudes of ${\rho}XZ$ and the secondary kinetic isotope effects involving deuterated nucleophiles are in line with the proposed mechanism.

Kinetics and Mechanism of $N_2H_4-KBrO_3$ Reaction in the Presence of Allyl Alcohol$^\dag$

  • Choi, Q.-Won;Chung, Keun-Ho
    • Bulletin of the Korean Chemical Society
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    • v.7 no.6
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    • pp.462-465
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    • 1986
  • Kinetics and Mechanism of $N_2H_4-KBrO_3$ reaction in the presence of allyl alcohol have been studied. The pseudo-first order rate constant for gas evolution was found to be $10^{-4}{\sim}10^{-2}\;sec^{-1}\;at\;25.0{\pm}0.1^{\circ}C$, increasing with concentration of hydrogen ion. When concentrations of sulfuric acid and allyl alcohol are both sufficiently high, the following overall reaction explains experimental results reasonably well: $N_2H_4\;+\;BrO_3^-\;+\;H^+\;{\to}\;N_2\;+\;HOBr\;+\;2H_2O,\;CH_2\;=\;CHCH_2OH\;+\;HOBr\;{\to}\;CH_2-OHCHBrCH_2OH$. More complicated reaction mechanisms at lower acidity conditions have been contemplated.

Kinetics of Metolachlor Degradation by Zerovalent Iron (Zerovalent Iron에 의한 Metolachlor의 분해 Kinetics)

  • Kim, Su-Jung;Oh, Sang-Eun;Yang, Jae-E.
    • Korean Journal of Environmental Agriculture
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    • v.26 no.1
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    • pp.55-61
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    • 2007
  • Metolachlor may pose a threat to surface and ground water qualities due to its high solubility in water, Zerovalent iron (ZVI) releases $e^-$ which can degrade the organochlorinated compounds. The objective of this research was to evaluate the kinetics of metolachlor degradation as affected by ZVI sources [Peerless unannealed (PU) and Peerless annealed (PA)] and ZVI levels (1 and 5%) under batch conditions at different metolachlor concentrations (200 and 1000 mg/l) and temperatures (15, 25, and $35^{\circ}C$). The effectiveness of ZVI on metolachlor degradation was assessed by characterizing the dechlorinated metolachlor byproduct molecules. Metolachlor degradation by ZVI followed the first-ordered kinetics with a higher rate constant at higher level of ZVI treatment. At 5% (w/v) of PU and PA treatment, the half-lives of metolachlor degradation were 9.93 and 6.51 h and all of the initial metolachlor were degraded in 72 and 48 h, respectively. Rate constants (k) of metolachlor degradation were higher at the lower initial metolachlor concentration. The metolachlor degradation by ZVI was temperature dependent showing that the rate constant (k) at 15, 25, and $35^{\circ}C$ were 0.0805, 0.1017, and 0.3116 /h, respectively. The ZVI-mediated metolachlor degradation yielded two byproduct molecules identified as dechlorinated metolachlor $(C_{13}H_{18}NO)$ and dechlorinated-dealkylated metolachlor $(C_{12}H_{17}NO)$. The PA ZVI was more effective than PU ZVI in metolachlor degradation.

Biochemical Methane Potential Analysis for Anaerobic Digestion of Marine Algae (해조류의 혐기소화를 위한 메탄생산퍼텐셜 분석)

  • Lee, Jun-Hyeong;Kim, Tae-Bong;Shin, Kook-Sik;Yoon, Young-Man
    • Journal of the Korea Organic Resources Recycling Association
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    • v.28 no.4
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    • pp.23-33
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    • 2020
  • Marine algae(Macro algae) are easily bio-degradable, and by-products are available as feed and fertilizer. The biomass of marine algae has higher CO2 absorption capacity than the wood system, and is highly valuable in use due to its fast growth speed and wide cultivation area without special cost for raw material production. In 2018, Marine algae production was 1,722,486ton, such as Saccharina japonica, Undaria pinnatifida and Porphyra tenera, the large amounts of by-products have been generated in the food processing facilities for commercialization. In this study, Saccharina japonica, Undaria pinnatifida were collected in the south coast region and Porphyra tenera was collected in the west coast region. The theoretical methane potential and biochemical methane potential(BMP) were analyzed, and Modified Gompertz model and Parallel first order kinetics model were adopted for the interpretation of the cumulative methane production curves. The theoretical methane potential of Saccharina japonica, Undaria pinnatifida and Porphyra tenera were 0.393, 0.373 and 0.435 N㎥/kg-VS, respectively. BMP obtained by the Modified gompertz model 0.226, 0.227, and 0.241 N㎥/kg-VS for Saccharina japonica, Undaria pinnatifida and Porphyra tenera, respectively. And BMP obtained by the Parallel first order kinetics model were 0.220, 0.243, and 0.240 N㎥/kg-VS for Saccharina japonica, Undaria pinnatifida and Porphyra tenera, respectively.

Removal Characteristics of Cu(II) ion in Aqueous Solution by Solid-Phase Extractant Immobilized D2EHPA and TBP in PVC (D2EHPA와 TBP를 PVC에 고정화한 고체상 추출제를 사용한 수용액 중의 Cu(II) 이온 제거특성)

  • Kam, Sang-Kyu;Lee, Song-Woo;Lee, Min-Gyu
    • Journal of Environmental Science International
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    • v.24 no.1
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    • pp.47-53
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    • 2015
  • Removal characteristics of Cu(II) ions by solid-phase extractant immobilized D2EHPA and TBP in PVC were investigated. Cu(II) ion concentrations in the solution and removal capacity of Cu(II) ion according to operation time were compared. The lower the initial concentration of Cu(II) ion in aqueous solution was, the removal capacity of Cu(II) ion by solid-phase extractant was increased relatively. The bigger the initial concentration of Cu(II) ion was, the removal capacity of Cu(II) ion was increased relatively. The pseudo-second-order kinetics according to operation time was showed more satisfying results than the pseudo-first-order kinetics for the removal velocity of Cu(II) ion. The removal capacity of Cu(II) ion was 0.025 mg/g in aqueous solution of pH 2, but the removal capacity of Cu(II) ion was increased to 0.33 mg/g mg/g in aqueous solution of pH 4 according to increasing pH.

Nucleophile Effects for the Reactions of Nucleophilic Substitution by Pressure and Temperature (친핵성치환반응에서 압력과 온도변화에 따른 친핵체 효과)

  • Kim, Se-Kyong;Choi, Sung-Yong;Ko, Young-Shin
    • Journal of the Korean Chemical Society
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    • v.48 no.5
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    • pp.461-466
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    • 2004
  • Kinetics for the nucleophiles have been studied under high vacuum and high pressures in various temperatures. Pseudo-first order rate constants, second order rate constants, thermodynamic parameters and Hammett ${\rho}$-values are determined. The values of ${\Delta}V^{\neq},\;{\Delta}{\beta}^{\neq}\;and\;{\Delta}S^{\neq}$are all negative. The Hammett r-values are negative for the nucleophile (${\rho}$x) over the pressure range studied. The results of kinetic studies for pressure and nucleophilet show that these reactions proceed in typical $S_N2$ reaction mechanism and change of mechanism.

과망간산을 이용한 지하수내 TCE 제거효과 평가

  • Yang Seung-Gwan;Go Seok-O
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2005.04a
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    • pp.53-56
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    • 2005
  • A Laboratory study was conducted to evaluate the kinetics of oxidation of trichloroethylene (TCE) in groundwater by potassium permanganate $(KMnO_4)$, Consumption of permanganate by TCE and aquifer materials was also evaluated to obtain an appropriate injection rate of $KMnO_4$. TCE degradation by $KMnO_4$ in the absence of aquifer material showed effective with pseudo-first order rate constant, $k_{obs}=1.8110^{-3}\;s^{-1}\;at\;KMnO_4=500mg/L$. TCE oxidation by $KMnO_4$ was found to be second order reaction and the rate constant, $k=0.65{\pm}0.08\;M^{-1}s^{-1}$, was independent of pH changes. $KMnO_4$ consumption rate by groundwater sampled from field site was not significant, indicating that groundwater containing negligible amount of dissolved organic matter does not have any influence on the $KMnO_4$ degradation. Meanwhile, aquifer materials from field site were actively reacted with permanganate, resulting in the significant consumption of $KMnO_4$. It might be attributed to the existence of metal oxides in aquifer materials, Based on the rate constants obtained from this study, appropriate injection rate of permanganate and TCE removal rate in groundwater could be estimated.

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Equilibrium and kinetic studies for the removal of cationic dye using banana pith

  • El-Maghraby, Azza;Taha, Nahla A.
    • Advances in environmental research
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    • v.3 no.3
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    • pp.217-230
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    • 2014
  • The large quantity of green cull bananas has the potential of being used industrially and, thereby, to improve banana economics and eliminate the large environmental problem presented by banana waste. Wastewaters from textile, cosmetics, printing, dying, food colouring, and paper-making industries are polluted by dyes. The adsorption of basic dye by waste banana pith was investigated by varying dye concentrations, adsorbent dose, particle size and agitation rate. The adsorption capacity was found to be maximum value of removal by using 0.1 g of sorbent with particle size 1mm at mixing speed 200 rpm for initial concentration 25 mg/l to reach value of approximate 89%. The Langmuir, Temkin and Freundlich adsorption models were used for mathematical description of the adsorption equilibrium and it was found that experimental data fitted very well to these models except Langmuir model. Adsorption of dye was applied on (pseudo-first and pseudo-second-order kinetics), and the experimental data was more fitted to pseudo second order. The results of this study showed that banana pith could be employed as effective and low-cost materials for the removal of dyes from aqueous solutions.

Synthesis of Pd/Cu-Fe polymetallic nanoparticles for in situ reductive degradation of p-nitrophenol

  • Wenbin, Zhang;Lanyu, Liu;Jin, Zhao;Fei, Gao;Jian, Wang;Liping, Fang
    • Membrane and Water Treatment
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    • v.13 no.2
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    • pp.97-104
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    • 2022
  • With a small particle size, specific surface area and chemical nature, Pd/Cu-Fe nanocomposites can efficiently remove the organic compounds. In order to understand the applicability for in situ remediation of contaminated groundwater, the degradation of p-nitrophenol by Pd/Cu-Fe nanoparticles was investigated. The degradation results demonstrated that these nanoparticles could effectively degrade p-nitrophenol and near 90% of degradation efficiency was achieved by Pd/Cu-Fe nanocomposites for 120 min treatment. The efficiency of degradation increased significantly when the Pd content increased from 0.05 wt.% and 0.10 wt.% to 0.20 wt.%. Meanwhile, the removal percentage of p-nitrophenol increased from 75.4% and 81.7% to 89.2% within 120 min. Studies on the kinetics of p-nitrophenol that reacts with Pd/Cu-Fe nanocomposites implied that their behaviors followed the pseudo-first-order kinetics. Furthermore, the batch experiment data suggested that some factors, including Pd/Cu-Fe availability, temperature, pH, different ions (SO42-, PO43-, NO3-) and humic acid content in water, also have significant impacts on p-nitrophenol degradation efficiency. The recyclability of the material was evaluated. The results showed that the Pd/Cu-Fe nanoparticles have good recycle performance, and after three cycles, the removal rate of p-nitrophenol is still more than 83%.