• Title/Summary/Keyword: pseudo second order

Search Result 431, Processing Time 0.024 seconds

Alkali Metal Ion Catalysis and Inhibition in Nucleophilic Substitution Reactions of 3,4-Dinitrophenyl Diphenylphosphinothioate with Alkali Metal Ethoxides in Anhydrous Ethanol: Effect of Changing Electrophilic Center from P=O to P=S

  • An, Jun-Sung;NamKoong, Gil;Kang, Ji-Sun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
    • /
    • v.32 no.7
    • /
    • pp.2423-2427
    • /
    • 2011
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 3,4-dinitrophenyl diphenylphosphinothioate 9 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] is linear for the reaction of 9 with EtOK. However, the plot curves downwardly for those with EtOLi and EtONa while it curves upwardly for the one with EtOK in the presence of 18-crown-6-ether (18C6). Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the reactivity increases in the order $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-}$ ${\approx}$ $k_{EtOK}$ < $k_{EtOK/18C6}$, indicating that the reaction is inhibited by $Li^+$ and $Na^+$ ions but is catalyzed by 18C6-crowned $K^+$ ion. The reactivity order found for the reactions of 9 contrasts to that reported previously for the corresponding reactions of 1, i.e., $k_{EtOLi}$ > $k_{EtONa}$ > $E_{EtOK}$ > $k_{EtO^-}$ ${\approx}$ $k_{EtOK/18C6}$, indicating that the effect of changing the electrophilic center from P=O to P=S on the role of $M^+$ ions is significant. A four-membered cyclic transition-state has been proposed to account for the $M^+$ ion effects found in this study, e.g., the polarizable sulfur atom of the P=S bond in 9 interacts strongly with the soft 18C6-crowned $K^+$ ion while it interacts weakly with the hard $Li^+$ and $Na^+$ ions.

Estimation of the Removal Capacity for Cadmium and Calculation of Minimum Reaction Time of BOF Slag (제강슬래그의 카드뮴 제거능 평가 및 필요반응시간 결정)

  • Lee, Gwang-Hun;Kim, Eun-Hyup;Park, Jun-Boum;Oh, Myoung-Hak
    • Journal of the Korean Geotechnical Society
    • /
    • v.27 no.10
    • /
    • pp.5-12
    • /
    • 2011
  • This study was focused on the reactivity of furnace slag against cadmium to design the vertical drain method with reactive column for improving contaminated sea shore sediment. The kinetic sorption test was performed by changing the initial concentration and pH. Using pseudo-second-order model, the reactivity of furnace slag was quantitatively analyzed. Equilibrium removal amount ($q_e$) of furnace slag increased and rate constant ($k_2$) decreased with the increase of initial cadmium concentration. With the increase of pH, the equilibrium removal amount ($q_e$) and rate constant ($k_2$) increased in the same initial concentration. Required retention time was related to the inverse of the product of the equilibrium removal amount ($q_e$) multiplied by rate constant ($k_2$). The required retention time could be used to design the length of reactive column.

Experimental investigation of Scalability of DDR DRAM packages

  • Crisp, R.
    • Journal of the Microelectronics and Packaging Society
    • /
    • v.17 no.4
    • /
    • pp.73-76
    • /
    • 2010
  • A two-facet approach was used to investigate the parametric performance of functional high-speed DDR3 (Double Data Rate) DRAM (Dynamic Random Access Memory) die placed in different types of BGA (Ball Grid Array) packages: wire-bonded BGA (FBGA, Fine Ball Grid Array), flip-chip (FCBGA) and lead-bonded $microBGA^{(R)}$. In the first section, packaged live DDR3 die were tested using automatic test equipment using high-resolution shmoo plots. It was found that the best timing and voltage margin was obtained using the lead-bonded microBGA, followed by the wire-bonded FBGA with the FCBGA exhibiting the worst performance of the three types tested. In particular the flip-chip packaged devices exhibited reduced operating voltage margin. In the second part of this work a test system was designed and constructed to mimic the electrical environment of the data bus in a PC's CPU-Memory subsystem that used a single DIMM (Dual In Line Memory Module) socket in point-to-point and point-to-two-point configurations. The emulation system was used to examine signal integrity for system-level operation at speeds in excess of 6 Gb/pin/sec in order to assess the frequency extensibility of the signal-carrying path of the microBGA considered for future high-speed DRAM packaging. The analyzed signal path was driven from either end of the data bus by a GaAs laser driver capable of operation beyond 10 GHz. Eye diagrams were measured using a high speed sampling oscilloscope with a pulse generator providing a pseudo-random bit sequence stimulus for the laser drivers. The memory controller was emulated using a circuit implemented on a BGA interposer employing the laser driver while the active DRAM was modeled using the same type of laser driver mounted to the DIMM module. A custom silicon loading die was designed and fabricated and placed into the microBGA packages that were attached to an instrumented DIMM module. It was found that 6.6 Gb/sec/pin operation appears feasible in both point to point and point to two point configurations when the input capacitance is limited to 2pF.

Physicochemical properties and methane adsorption performance of activated carbon nanofibers with different types of metal oxides

  • Othman, Faten Ermala Che;Yusof, Norhaniza;Hasbullah, Hasrinah;Jaafar, Juhana;Ismail, Ahmad Fauzi;Nasri, Noor Shawal
    • Carbon letters
    • /
    • v.24
    • /
    • pp.82-89
    • /
    • 2017
  • In this study, composite PAN-based ACNFs embedded with MgO and $MnO_2$ were prepared by the electrospinning method. The resultant pristine ACNFs, ACNF/MgO and $ACNF/MnO_2$ were characterized in terms of their morphological changes, SSA, crystallinity and functional group with FESEM-EDX, the BET method, XRD and FTIR analysis, respectively. Results from this study showed that the SSA of the ACNF/MgO composite ($1893m^2g^{-1}$) is significantly higher than that of the pristine ACNFs and $ACNF/MnO_2$ which is 478 and $430m^2g^{-1}$, respectively. FTIR analysis showed peaks of 476 and $547cm^{-1}$, indicating the presence of MgO and $MnO_2$, respectively. The FESEM micrographs analysis showed a smooth but coarser structure in all the ACNFs. Meanwhile, the ACNF/MgO has the smallest fiber diameter ($314.38{\pm}62.42nm$) compared to other ACNFs. The presence of MgO and $MnO_2$ inside the ACNFs was also confirmed with EDX analysis as well as XRD. The adsorption capacities of each ACNF toward $CH_4$ were tested with the volumetric adsorption method in which the ACNF/MgO exhibited the highest $CH_4$ adsorption up to $2.39mmol\;g^{-1}$. Meanwhile, all the ACNF samples followed the pseudo-second order kinetic model with a $R^2$ up to 0.9996.

Adsorption Characteristics of Cr6+ and As3+ Using Seaweed Biochar (해초 Biochar를 이용한 Cr6+과 As3+ 흡착 특성)

  • Kim, Bo-Ra;Shin, Woo-Seok;Kim, Young-Kee
    • Applied Chemistry for Engineering
    • /
    • v.26 no.4
    • /
    • pp.483-488
    • /
    • 2015
  • This study examined the adsorption characteristics of $Cr^{6+}$ and $As^{3+}$ in the aqueous solution by Hizikia susiformis biochar which was collected from Jeju Island. The optimal pH for $Cr^{6+}$ and $As^{3+}$ adsorption were 2 and pH 6, respectively. Kinetic data showed that the adsorption occurred during the first 100 min, and the most of heavy metals were bound to biochars within 300 min. Moreover, the kinetic data presented that the course of adsorption follows the Pseudo first and second order models. The equilibrium data were well fitted by the Langmuir model and the $Cr^{6+}$ adsorption capacity (25.91 mg/g) was higher than that of $As^{3+}$ (16.54 mg/g). From these results, the seaweed biochar was shown to be a efficient adsorbent for $Cr^{6+}$ and $As^{3+}$ metals in a contaminated environment.

Aqueous U(VI) removal by green rust and vivianite at phosphate-rich environment

  • Sihn, Youngho;Yoon, In-Ho
    • Membrane and Water Treatment
    • /
    • v.11 no.3
    • /
    • pp.207-215
    • /
    • 2020
  • Vivianite (Fe32+(PO4)2·8H2O) and green rust ([Fe42+Fe23+(OH)-12][SO42-·2H2O]2-), ferrous containing minerals, could remove aqueous U(VI) in 5 min. and the efficiencies of green rust were roughly 2 times higher than that of vivianite. The zeta potential measurement results implies that the better performance of green rust might be attributed to the favorable surface charge toward uranyl phosphate species. The removal behaviors of the minerals were well fitted by pseudo-second order kinetic model (R2 > 0.990) indicating the dominant removal process was chemical adsorption. Effects of Ca2+ and CO32- at pH 7 were examined in terms of removal kinetic and capacity. The kinetic constants of aqueous U(VI) were 8 and 13 times lower (0.492 × 10-3 g/(mg·min); 0.305 × 10-3 g/(mg·min)) compared to the value in the absence of the ions. The thermodynamic equilibrium calculation showed that the stable uranyl species (uranyl tri-carbonate) were newly formed at the condition. Surface investigation on the reacted mineral with uranyl phosphates species were carried out by XPS. Ferrous iron and U(VI) on the green rust surface were completely oxidized and reduced into Fe(III) and U(IV) after 7 d. It suggests that the ferrous minerals can retard U(VI) migration in phosphate-rich groundwater through the adsorption and subsequent reduction processes.

Studies on the Influence of Mercaptoacetic Acid (MAA) Modification of Cassava (Manihot sculenta Cranz) Waste Biomass on the Adsorption of Cu2+ and Cd2+ from Aqueous Solution

  • Horsfall, M. Jnr.;Spiff, A.I.;Abia, A.A.
    • Bulletin of the Korean Chemical Society
    • /
    • v.25 no.7
    • /
    • pp.969-976
    • /
    • 2004
  • Cassava peelings waste, which is both a waste and pollutant, was chemically modified using mercaptoacetic acid (MAA) and used to adsorb $Cu^{2+}\;and\;Cd^{2+}$ from aqueous solution over a wide range of reaction conditions at $30^{\circ}C$. Acid modification produced a larger surface area, which significantly enhanced the metal ion binding capacity of the biomass. An adsorption model based on the $Cu^{2+}/Cd^{2+}$ adsorption differences was developed to predict the competition of the two metal ions towards binding sites for a mixed metal ion system. The phytosorption process was examined in terms of Langmuir, Freundlich and Dubinin-Radushkevich models. The models indicate that the cassava waste biomass had a greater phytosorption capacity, higher affinity and greater sorption intensity for $Cu^{2+}\;than\;Cd^{2+}$. According to the evaluation using Langmuir equation, the monolayer binding capacity obtained was 127.3 mg/g $Cu^{2+}$ and 119.6 mg/g $Cd^{2+}$. The kinetic studies showed that the phytosorption rates could be described better by a pseudo-second order process and the rate coefficients was determined to be $2.04{\times}10^{-3}\;min^{-1}\;and\;1.98{\times}10^{-3}\;min^{-1}\;for\;Cu^{2+}\;and\;Cd^{2+}$ respectively. The results from these studies indicated that acid treated cassava waste biomass could be an efficient sorbent for the removal of toxic and valuable metals from industrial effluents.

Preparation of Hybrid Beads Containing Polysulfone Modified with Carbon Nanotubes, Tributyl Phosphate and Di-(2-ethylhexyl)-phosphoric Acid and Removal Characteristics of Sr(II) (Polysulfone에 Carbon Nanotubes, Tributyl Phosphate와 Di-(2-ethylhexyl)-phosphoric Acid를 고정화한 하이브리드 비드의 제조와 Sr(II)의 제거 특성)

  • Kam, Sang-Kyu;Suh, Jung-Ho;Yun, Jong-Won;Lee, Min-Gyu
    • Applied Chemistry for Engineering
    • /
    • v.29 no.3
    • /
    • pp.264-269
    • /
    • 2018
  • PSf/D2EHPA/TBP/CNTs beads were prepared by immobilizing carbon nanotubes (CNTs) and two extractants, di-(2-ethylhexyl)-phosphoric acid (D2EHPA) and tributyl phosphate (TBP) on polysulfone (PSf). The prepared PSf/D2EHPA/TBP/CNTs beads were characterized by SEM, TGA, and FTIR. The removal rate of Sr(II) by PSf/D2EHPA/TBP/CNTs beads was well described by the pseudo-second-order kinetic model. The maximum removal capacity of Sr(II) obtained from Langmuir isotherm was found to be 5.52 mg/g. The results showed that the removal efficiency of Sr(II) by PSf/D2EHPA/CNTs beads prepared in this study was significantly improved compared to that of using PSf/D2EHPA/CNTs beads without TBP.

Heavy Metal Removal of Acrylic Acid-grafted Bacterial Cellulose in Aqueous Solution (아크릴산으로 그라프트된 미생물셀룰로오스의 수용액 내 중금속 흡착거동)

  • Ahn, Yeong-Hee;Choi, Yong-Jin
    • Journal of Environmental Science International
    • /
    • v.23 no.8
    • /
    • pp.1419-1428
    • /
    • 2014
  • Electron beam-induced grafting polymerization was employed to prepare Acrylic acid-grafted bacterial cellulose (BC-g-AAc). BC-g-AAc as an adsorbent was applied to remove heavy metals (e.g., As, Pb, and Cd). This study examined followings; morphological change of surface, adsorptive behavior of BC-g-AAc, and interpretation of adsorptive kinetics. Specific surface areas of BC and BC-g-AAc were $0.9527m^2g^{-1}$ for BC and $0.2272m^2g^{-1}$ for BC-g-AAc, respectively as measured by BET nitrogen adsorption, revealing the morphological change of the surface of BC-g-AAc. Batch adsorption test was performed to investigate adsorptive behavior of BC-g-AAc in aqueous solution. The amounts of Pb and Cd adsorbed on BC-g-AAc were $69mg\;g^{-1}$ and $56mg\;g^{-1}$, respectively. However, As was not adsorbed on BC-g-AAc due to its neutral nature. Both the Benaissa model and the Kurniawan model were applied in the study to interpret adsorptive kinetics. From the value of correction coefficient ($R^2$), adsorptive kinetics of Pb and Cd were subjected to Kurniawan model referred to pseudo-second-order. Taken together, the results of this study show that BC-g-AAc has potential as a heavy metal (eg., Pb, Cd)-adsorbent made of an environmentally friendly material.

Studies on the Application of the Spent Alkaline Manganese Batteries Powder as an Adsorbent for Nickel Ion (폐(廢)알칼리망간전지(電池) 분말(粉末)의 니켈 이온 흡착제(吸着劑)로서의 활용(活用)에 관한 연구(硏究))

  • Baek, Mi-Hwa;Kim, Dong-Su;Sohn, Jeong-Soo
    • Resources Recycling
    • /
    • v.17 no.2
    • /
    • pp.63-69
    • /
    • 2008
  • The adsorption features of $Ni^{2+}$ onto spent alkaline manganese batteries powder have been investigated with the adsorbent dose, initial concentration of adsorbate and temperature as the experimental variables. The adsorption reaction of $Ni^{2+}$ ion followed the pseudo-second order rate model, and the adsorption rate constants($k_2$) decreased with increasing initial concentration of nickel ion. The equilibrium adsorption data were fitted to the Langmuir and Freundlich models. The Freundlich model represents the equilibrium data better than the Langmuir model in this initial adsorbate concentration range. As the temperature increased, the adsorbed amount of nickel ion at equilibrium was also increased, which indicated that the adsorption reaction was endothermic. Based on the experimental results obtained along with temperatures, thermodynamic parameters such as ${\Delta}H^{\circ},\;{\Delta}G^{\circ},\;and\;{\Delta}S^{\circ}$ were calculated.