• 제목/요약/키워드: Irreversible adsorption

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The Application of Octa-Substituted Metallophthalocyanine Langmuir-Blodgett films for $NO_2$ Measurement (수정진동자를 이용한 프탈로시아닌 LB박막의 $NO_2$ 감지 특성)

  • Kwon, H.J.;Lee, Y.J.;Chang, Y.K.;Kim, J.D.
    • Journal of Sensor Science and Technology
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    • v.7 no.4
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    • pp.254-262
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    • 1998
  • Multilayer Langmuir-Blodgett (LB) films coated on quartz crystal microbalance (QCM) of octa-substituted metallophhtalocyanines ($MPc(OEH)_8$, M = Cu, Co, and Sn) and dihydrogen phthalocyanines ($H_2Pc(OEH)_8$) were used to quantify $NO_2$ concentrations. They were exposed to various concentrations of $NO_2$ in dry $N_2$. Among the four phthalocyanines we tested, the metal-free $H_2Pc(OEH)_8$ was observed to be most sensitive to $NO_2$. However, its LB film showed a partially irreversible behavior, that is part of the frequency change due to $NO_2$ adsorption could not be recovered even after purging with pure $N_2$ gas for an extended period. Examining the spectra of NMR and FTIR revealed fact that the irreversible portion of frequency change was due to ether groups in the linkage between side chains and the Pc unit. In order to remove the effect of such initial deactivation, on $NO_2$ quantification experiment, a freshly fabricated LB film was treated at a high concentration of $NO_2$ so that the ether sites were saturated. A pretreated LB film showed a reproducible performance for repeated uses. The $CuPc(OEH)_8$ LB film showed a satisfactory sensing performance down to as low as 4 ppm. For the $H_2Pc(OEH)_8$ LB film, the lower detection limit was found to be 35ppb of $NO_2$. In order to make the experimental condition more realistic, the carrier gas, dry nitrogen, was replaced by air. It was observed that the presence of oxygen, a weak electron acceptor, reduced the sensitivity and thus increased the sensing limit to hundreds of ppb. Results of experiments with moisture added showed that the interference of moisture was quite severe.

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Highly Dispersed Supported Gold Catalysts -I. Effect of Gold Addition and Active Site Formation- (고분산 담지 금촉매 - I. 금의 첨가 효과 및 활성점 생성 -)

  • Ahn, Ho-Geun;Niiyama, Hiroo
    • Applied Chemistry for Engineering
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    • v.5 no.2
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    • pp.285-294
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    • 1994
  • Some supported gold catalysts were prepared by impregnation and coprecipitation methods. Effect of gold addition and active sloe formation were studied by investigating particle sizes of gold, amounts of oxygen adsorbed, adsorption properties of CO and NO, and reduction and oxidation properties, etc.. The gold particles of the catalyst by impregnation were irregular and very large as 30~100 nm, but those by coprecipitation were uniform and ultra-fine as about 4 nm. On $Au/Al_2O_3$ catalyst, the addition of gold to inactive $Al_2O_3$ caused the decomposition of $N_2O$, and CO was not irreversibly adsorbed while $O_2$ was atomically and irreversibly adsorbed. The adsorption sites of oxygen were attributed to the active sites which were restricted to the circumference of hemispherical gold particle-support interface rather than all atoms on the surface of gold particle. Also, CO was reversibly and irreversibly adsorbed on $Al_2O_3$ at low temperature, and the addition of gold weakened both reversible and irreversible adsorptions. The affinity for CO on $Au/Co_3O_4$ catalyst decreased conspicuously compared to $Co_3O_4$. The effect of gold addition did not appear in reduction step but did remarkably in reoxidation step; the added gold promoted the reoxidation of the reduced cobalt atoms.

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Effect of GAC Packing Mass in Hybrid Water Treatment Process of PVdF Nanofibers Spiral Wound Microfiltration and Granular Activated Carbon (PVdF 나노섬유 나권형 정밀여과와 입상 활성탄의 혼성 수처리에서 활성탄 충진량의 영향)

  • Kyung, Kyu Myung;Park, Jin Yong
    • Membrane Journal
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    • v.27 no.1
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    • pp.68-76
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    • 2017
  • Flat membrane with $0.4{\mu}m$ pore size was prepared with PVdF (polyvinylidene fluoride) nanofiber, which has the advantages such as excellent strength, chemical resistance, non-toxicity, and incombustibility. The spiral wound module was manufactured with the flat membrane and a woven paper. Hybrid water treatment process was composed of the PVdF nanofibers spiral wound microfiltration and granular activated carbon (GAC) adsorption column. Effect of GAC packing mass was investigated by comparing the case of recycling or discharging the treated water using the synthetic solution of kaolin and humic acid. After each filtration experiment, water back-washing was performed, and recovery rate and filtration resistances were calculated. Also, effect of GAC adsorption was compared by measuring turbidity and $UV_{254}$ absorbance. As a result, there was no effect of GAC packing mass on turbidity treatment rate; however, the treatment rate of $UV_{254}$ absorbance was 0.7~3.6% for recycling the treated water, and increased to 3.2-5.7% for discharging the treated water. In the case of recycling the treated water, reversible filtration resistance ($R_r$) and irreversible filtration resistance ($R_{ir}$) trended to decrease as increasing GAC packing mass; however, total fitration resistance ($R_t$) was almost constant, and recovery rate of water back-washing trended to increase a little.

Study on Retardation Effect of a Heavy Metal in Sandy Soils

  • Kim, Dong-Ju;Sung, Baek-Doo
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 1998.06a
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    • pp.43-49
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    • 1998
  • Retardation effect of heavy metals in soils caused by adsorption onto the surfaces of solids particles is well known phenomena. The adsorption of metal ions has been recognized more strong in clay mineral and organic matter contents rather than sands and gravels. In this study, we investigated the retardation effect in two sandy soils by conducting batch and column tests. The column tests were conducted to obtain the relationship between concentration and time known as breakthrough curve (BTC). We applied pulse type injection of ZnCl$_2$solution on the inlet boundary and monitored the effluent concentration at the exit boundary under steady state condition using EC-meter and ICP-AES. Batch test consisted of an equilibrium procedure for fine fractions collected from two sandy soils for various initial ZnCl$_2$concentrations, and analysis of Zn ions in equilibrated solution using ICP-AES. The results of column test showed that i) the peak concentration of Zn analyzed by ICP was far less than that detected by EC-meter for both soils and ii) travel times for peak concentration were more less identical for two different monitoring techniques. The first result can be explained by ion exchange between Zn and other cations initially present in the soil particles since ICP analysis showed a significant amount of Ca, Mg ions in the effluent. From the second result, we found that retardation effect was not present in these soils due to strong cation exchange capacity of Zn ion over other cations since we did not apply a solution containing more adsorptive cations such as Al. The result of batch test also showed high distribution coefficients (K$_{d}$) for two soils supporting the dominant ion exchange phenomena. Based on the retardation factor obtained from the Kd, we predicted the BTC using CDE model and compared with the BTC of Zn concentration obtained from ICP The predicted BTC, however, disagreed with the monitored in terms of travel time and magnitude of the peak concentrations. The only way to describe the prominent decrease of Zn ion was to introduce decay or sink coefficient in the CDE model to account for irreversible decrease of Zn ions in liquid phase.e.

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Effect of coagaulation on ceramic microfiltration membrane fouling (응집공정이 세라믹 정밀여과막 파울링에 미치는 영향)

  • Hwang, Young Jin;Lim, Jae Lim;Choi, Young Jong;Wang, Chang Gun
    • Journal of Korean Society of Water and Wastewater
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    • v.23 no.4
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    • pp.459-469
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    • 2009
  • It is well known that coagulation pretreatment can reduce foulants prior to membrane filtration. The purpose of this research was to investigate the effects of coagulation on fouling of ceramic microfiltration membrane($0.1 {\mu}m$) using pilot plant of $150m^3/day/train$ capacity. Train A membrane system has pretreatment process of ozonation and coagulation while train B has only coagulation. Two types of coagulation operation were investigated: back mixer(rapid mixing with or without slow mixing) which is a conventional mechanically stirred mixer and an inline static mixer. Ozone dose rate for train A was 1 mg/L and ozone contact time was 12 min. The coagulation dose(PACl 10% as $Al_2O_3$) rate was changed 20~40 mg/L according to experimental schedule. In this experimental conditions, the coagulation of back mixer type with rapid mixing(GT=72,000) and slow mixing(GT=45,000) was the best effective in reduction of ceramic membrane fouling regardless preozonation. Especially, the effect of inline static mixer was sensitive to change in water quality. Ozonation mainly affected irreversible fouling rather than reversible fouling in accordance with less adsorption of NOM on the membrane surface. Thus, the increase rate of the nomalized TMP(trans membrane pressure) at $25^{\circ}C$ for train A was relatively lower than that of train B under same coagulation process with same coagulant dosage. The best performance of ceramic membrane appeared in case of combined process with ozonation, therefore this integrated process is able to archive less coagulant dosing and secure a stability of ceramic membrane system.

Electrochemical Reduction Behavior of Bilirubin (Bilirubin의 전기화학적 환원거동)

  • Bae Zun Ung;Lee Heung Lark;Jung Mi Sik;Park Tae Myung
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.374-378
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    • 1991
  • The electrochemical reduction behavior of Bilirubin (BR) in phosphate buffer (pH 7.8) solution was studied by DC polarography, differential pulse polarography, cyclic voltammetry and controlled potential coulometry. In DC polarogram, two reduction waves of BR were found. The half wave potentials of two reduction waves were -1.32 and -1.51 volts vs. Ag/AaCl respectively. The current type of 1st reduction wave was diffusion-controlled and the 2$^{nd}$ reduction wave was diffusion current containing a little kinetic current. The electrochemical reduction process of BR at each reduction step was all irreversible. The prewave appeared at lower concentration than 3.4 ${\times}$ 10$^{-4}$M, this prewave was identified as adsorption prewave. And the number of electron transfered in reduction steps, n$_{app}$ was two for the 1st reduction step and one for the 2$^{nd}$ reduction step.

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Sorption Studies of $Cd^{2+}$ on Calcite: Kinetics and Reversibility (방해석의 $Cd^{2+}$ 흡착현상에 대한 연구)

  • Yoon, Hyeon;Reeder, Richard J.
    • Journal of the Mineralogical Society of Korea
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    • v.15 no.2
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    • pp.104-113
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    • 2002
  • The sorption of Cd$^{2+}$ on calcite was studied in aqueous solutions of several electrolytes. The Cd$^{2+}$ concentration, 10$^{-8}$ M, was kept well below saturation with respect to CdCO$_3$(s). Sorption behavior of Cd$^{2+}$ in different ionic strengths of NaClO$_4$solutions shows that sorption is independent of ionic strength. This result suggests that Cd$^{2+}$ sorption on calcite surface is of a specific nature, and adsorption is controlled by an inner-sphere type of surface complex. Two stages in the sorption behavior could be identified: an initial rapid uptake, followed by slower uptake reaching a maximum steady state by 145 hrs. No evidence was observed for surface precipitation, although it can not be entirely ruled out. Desorption of Cd$^{2+}$ from the calcite surface after resuspension into Cd-free solution is initially very rapid, but depends partly on the previous sorption history. Desorption behavior of Cd$^{2+}$ show that an initial rapid desorption followed either by slow uptake reaching a maximum, as in the adsorption experiments, or slowing desorption to reach a steady state minimum. This irreversible behavior of Cd$^{2+}$ sorption and desorption may act as one of the controls for regulating the mobility of dissolved Cd$^{2+}$ natural aqueous systems. Calculated adsorption partition coefficients suggest that overall sorption and desorption process in the concentration range are controlled by d single mechanism.ingle mechanism.

Removal of Red Tide Organisms -1. flocculation of Red Tide Organisms by Using IOSP- (적조생물의 구제 -1. IOSP에 의한 적조생물의 응집제거-)

  • KIM Sung-Jae;CHO Kyu-Dae
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.33 no.5
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    • pp.448-454
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    • 2000
  • This study was to examine the physicochemical characteristics of coagulation reaction between ignited oyster shell powder (IOSP) and red tide organisms (RTO), and its feasibility, in developing a technology for the removal of RTO bloom in coastal sea,IOSP was made from oyster shell and its physicochemical characteristics were examined for particle size distribution, surface characteristic by scanning electron microscope, zeta potential, and alkalinity and pH variations in sea water. Two kinds of RTO that were used in this study, Cylindrotheca closterium and Skeletonema costatum, were sampled in Masan bay and were cultured in laboratory. Coagulation experiments were conducted using various c(Incentrations of IOSP, RTO, and a jar tester. The supernatant and RTO culture solution were analyzed for pH, alkalinity, RTO cell number, IOSP showed positive zeta potentials of $11.1{\~}50.1\;mV\;at\;pH\;6.2{\~}12.7$, A positive zeta potential of IOSP slowly decreased with decreasing pNa 4,0 to 2,0. When pNa reached zero, the zeta potential approached zero, When a pMg value was decreased, the positive zeta potential of IOSP increased until pMg 3.0 and decreased below pMg 3.0. IOSP showed 4.8 mV of positive zeta potential while RTO showed -9.2 mV of negative zeta potential in sea water. A positive-negative EDL (electrical double-layer) interaction occurred between $Mg(OH)_2$ adsorption layer of IOSP and RTO in sea water so that EDL attractive force always worked between them. Hence, their coagulation reaction occurred at primary minimum on which an extreme attractive force acted because of charge neutralization by $Mg(OH)_2$ adsorption layer of IOSP. As a result, the coagulation reaction was rapidly processed and was irreversible according to DLVO (Deriaguin-Landau-Verwey-Overbeek) theory. Removal rates of RTO were exponentially increased with increasing both IOSP concentration and G-value. The removal rates were steeply increased until 50 mg/l of IOSP and reached $100{\%}\;at\;400\;mg/l$ of IOSP. Removal rates of RTO were $70.5,\;70.5,\;81.7,\;85.3{\%}$ for G-values of $1,\;6,\;29,\;139\;sec^(-1)$at IOSP 100 mg/l, respectively. This indicated that mixing (i.e., collision among particles) was very important for a coagulation reaction.

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Electrochemical Reduction for trans-Complexes of Cobalt (III) with Bis(ethylenediamine) and Monodendate Ligands (한자리 리간드를 포함하는 트란스비스 (에틸렌디아민) 코발트 (III) 이온의 전극 환원반응)

  • Jung-Ui Hwang;Jong-Jae Chung;Jae-Duck Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.2
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    • pp.215-224
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    • 1989
  • Electrochemical reductions of $trans-[Co(en)_2X_2](ClO_4)_n$ (where X is cyanide, nitrite, ammonia, and isothiocyanate) were investigated by cyclic voltammetry and polarography at mercury and glassy carbon electrode. $trans-[Co(en)_2(CN)_2]ClO_4$ was reduced to Co(II) complex followed by adsorption to the mercury electrode. Cyanide ion was not released from the reduced Co(II) complex but the cyanide and (en) were released after the reduction to metallic cobalt. The other complexes except $trans-[Co(en)_2(CN)_2]ClO_4$ were reduced to cobalt(II) complexes followed by release of monodendate ligand, and (en) was released at the reduction step to metallic cobalt. $trans-[Co(en)_2(NO_2)_2]ClO_4$ was reduced to cobalt(Ⅱ) complex, and $NO_2^-$ ion was released followed by electroreduction through ECE mechanism at pH 2. On glassy carbon electrode, all complexes of Co(III) were reduced to Co(II) complexes with irreversible one-electron diffusion controlled reaction in which (en) was not released at this step. Increasing absorption wave number of complexes caused to negative shift of peak potential.

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Retardation Effect and Mobility of a Heavy Metal in a Sandy Soil (사질토양에서의 중금속의 지연효과와 이동성)

  • Kim, Dong-Ju;Baek, Doo-Sung
    • Journal of the Korean Society of Groundwater Environment
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    • v.5 no.3
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    • pp.155-161
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    • 1998
  • Retardation effect of heavy metals in soils caused by adsorption onto the surfaces of solids particles is well known phenomenon. In this study, we investigated the retardation effect on the mobility of a Zn in a sandy soil by conducting batch and column tests. The column test consisted of monitoring the concentrations of effluent versus time known as a breakthrough curve (BTC). We used NaCl and ZnCl$_2$ solutions with the concentration of 10 g/L as a tracer, and injected them respectively into the inlet boundary of the soil sample as a square pulse type, and monitored the effluent concentrations at the exit boundary under a steady state condition using an EC-meter and ICP-AES. The batch test was conducted based on the standard procedure of equilibrating fine fractions collected from the soil with various initial ZnCl$_2$ concentrations, and analysis of Zn ions in the equilibrated solutions using ICP-AES. The results of column test showed that i) the peak concentration of ZnCl$_2$analyzed by ICP was far less than that of either NaCl or bulk electrical conductivity and ⅱ) travel times of peak concentrations for two tracers were more less identical. The relatively low concentration of Zn can be explained by ion exchange between Zn and other cations, and possible precipitation of Zn in the form of Zn(OH)$_2$due to high pH range (7.0∼7.9) of the effluent. The identical result of travel times of peak concentrations indicates that the retardation effect is not present in the soil. The only way to describe the prominent decrease of Zn ion was to introduce decay or sink coefficient in the CDE model to account for irreversible decrease of Zn ions in the aqueous phase.

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