• Title/Summary/Keyword: pseudo second-order kinetics

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Characterization of the Behavior of Naturally Occurring Radioactive Elements in the Groundwater within the Chiaksan Gneiss Complex : Focusing on the Mineralogical Interpretation of Artificial Weathering Experiments (치악산 편마암 지질의 지하수 내 자연 방사성 원소의 거동 특성 연구: 인공풍화 실험을 통한 광물학적 해석)

  • Woo-Chun Lee;Sang-Woo Lee;Hyeong-Gyu Kim;Do-Hwan Jeong;Moon-Su Kim;Hyun-Koo Kim;Soon-Oh Kim
    • Korean Journal of Mineralogy and Petrology
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    • v.36 no.4
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    • pp.289-302
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    • 2023
  • The study area was Gangnim-myeon, Hoengseong-gun, Gangwon-do, composed of the Chiaksan gneiss complex, and it was revealed that the concentrations of uranium (U) and thorium (Th) within the groundwater of the study area exceeded their water quality standards. Hence, artificial weathering experiments were conducted to elucidate mineralogically the mechanisms of their leaching using drilling cores obtained from the corresponding groundwater aquifers. First of all, the mineralogical compositions of core samples were observed, and the results indicated that the content of clinochlore, a member of the chlorite group of minerals that can form through low- and intermediate-temperature metamorphisms, was relatively higher. In addition, the Th concentration was measured ten times higher than that of U. The results of artificial weathering experiments suggested that the Th concentrations gradually increased through the dissolution of radioactive-element-bearing minerals up to the first day, and then they tended to decrease. It could be attributed to the fact that Th was leached with the dissolution of thorite, which might be a secondary mineral, and then dissolved Th was re-precipitated as the various forms of salt, such as sulfate. Even though the U content was lower than that of Th in the core samples, the U concentration was one hundred times higher than that of Th after the weathering experiments. It is likely caused by the gradual dissolution and desorption of U included in intensively weathered thorite or adsorbed as a form of UO22+ on the mineral surface. In addition, the leaching tendency of U and Th was positively correlated with the bicarbonate concentration. However, the concentrations between U and Th in groundwater exhibited a relatively lower correlation, which might result from the fact that they occurred from different sources, as aforementioned. Among various kinetic models, the parabolic diffusion and pseudo-second-order kinetic models were confirmed to best fit the dissolution kinetics of both elements. The period that would be taken for the U concentration to exceed its drinking-water standard was inferred using the regressed parameters of the best-fitted models, and the duration of 29.4 years was predicted in the neutral-pH aquifers with relatively higher concentrations of HCO3, indicating that U could be relatively quickly leached out into groundwater.

Adsorption Characteristics and Parameters of Acid Black and Quinoline Yellow by Activated Carbon (활성탄에 의한 Acid Black과 Quinoline Yellow의 흡착특성 및 파라미터)

  • Yi, Kyung Ho;Hwang, Eun Jin;Baek, Woo Seung;Lee, Jong-Jib;Dong, Jong-In
    • Clean Technology
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    • v.26 no.3
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    • pp.186-195
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    • 2020
  • The isothermal adsorption, dynamic, and thermodynamic parameters of Acid black (AB) and Quinoline yellow (QY) adsorption by activated carbon were investigated using the initial concentration, contact time, temperature, and pH of the dyes as adsorption parameters. The adsorption equilibrium data fits the Freundlich isothermal adsorption model, and the calculated Freundlich separation factor values found that activated carbon can effectively remove AB and QY. Comparing the kinetic data showed that the pseudo second order model was within 10% error in the adsorption process. The intraparticle diffusion equation results were divided into two straight lines. Since the slope of the intraparticle diffusion line was smaller than the slope of the boundary layer diffusion line, it was confirmed that intraparticle diffusion was the rate-controlling step. The thermodynamic experiments indicated that the activation energies of AB and QY were 19.87 kJ mol-1 and 14.17 kJ mol-1, which corresponded with the physical adsorption process (5 ~ 40 kJ mol-1). The adsorption reaction was spontaneous because the free energy change in the adsorption of AB and QY by activated carbon was negative from 298 to 318 K. As the temperature increased, the free energy value decreased resulting in higher spontaneity. Adsorption of AB and QY by activated carbon showed the highest adsorption removal rate at pH 3 due to the effect of anions generated by dissociation. The adsorption mechanism was electrostatic attraction.

Adsorption Characteristics Analysis of 2,4-Dichlorophenol in Aqueous Solution with Activated Carbon Prepared from Waste Citrus Peel using Response Surface Modeling Approach (반응표면분석법을 이용한 폐감귤박 활성탄에 의한 수중의 2,4-Dichlorophenol 흡착특성 해석)

  • Lee, Chang-Han;Kam, Sang-Kyu;Lee, Min-Gyu
    • Korean Chemical Engineering Research
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    • v.55 no.5
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    • pp.723-730
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    • 2017
  • The batch experiments by response surface methodology (RSM) have been applied to investigate the influences of operating parameters such as temperature, initial concentration, contact time and adsorbent dosage on 2,4-dichlorophenol (2,4-DCP) adsorption with an activated carbon prepared from waste citrus peel (WCAC). Regression equation formulated for the 2,4-DCP adsorption was represented as a function of response variables. Adequacy of the model was tested by the correlation between experimental and predicted values of the response. A fairly high value of $R^2$ (0.9921) indicated that most of the data variation was explained by the regression model. The significance of independent variables and their interactions were tested by the analysis of variance (ANOVA) and t-test statistics. These results showed that the model used to fit response variables was significant and adequate to represent the relationship between the response and the independent variables. The kinetics and isotherm experiment data can be well described with the pseudo-second order model and the Langmuir isotherm model, respectively. The maximum adsorption capacity of 2,4-DCP on WCAC calculated from the Langmuir isotherm model was 345.49 mg/g. The rate controlling mechanism study revealed that film diffusion and intraparticle diffusion were simultaneously occurring during the adsorption process. The thermodynamic parameters indicated that the adsorption reaction of 2,4-DCP on WCAC was an endothermic and spontaneous process.

Fluoride Sorption Property of Lanthanum Hydroxide (란탄수산화물의 불소 흡착 특성)

  • Kim, Jung-Hwan;Park, Hyun-Ju;Jung, Kyung-Hun
    • Journal of Korean Society of Environmental Engineers
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    • v.32 no.7
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    • pp.714-721
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    • 2010
  • This research was undertaken to evaluate the feasibility of lanthanum hydroxide for fluoride removal from aqueous solutions. A batch sorption experiments were conducted to study the influence of various factors such as pH, contact time, initial fluoride concentration and temperature on the sorption of fluoride on lanthanum hydroxide. The optimum fluoride removal was observed in the $pH_{eq}{\leq}8.8$. Sorption equilibrium of fluoride on lanthanum hydroxide was better described by the Freundlish isotherm model than by the Langmuir isotherm model. The adsorption energy obtained from D-R model was 9.21 kJ/mol indicating an ion-exchange process as primary adsorption mechanism. The pseudo-second-order kinetic model described well the experimental kinetic data. Thermodynamic parameters such as ${\Delta}Go^{\circ}$, ${\Delta}H^{\circ}$ and ${\Delta}S^{\circ}$ indicated that the nature of fluoride sorption is spontaneous and endothermic. The used lanthanum hydroxide could be regenerated by washing with NaOH solution. Also, the results applied to real ground water indicate that fluoride selectivity and removal capacity of lanthanum hydroxide were superior to those of PA anion-exchange resin.

Study of Equilibrium, Kinetic and Thermodynamic Parameters about Fluorescein Dye Adsorbed onto Activated Carbon (활성탄을 이용한 플루오레세인 염료 흡착에 대한 평형, 동력학 및 열역학 파라미터의 연구)

  • Lee, Jong-Jib;Um, Myeong Heon
    • Applied Chemistry for Engineering
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    • v.23 no.5
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    • pp.450-455
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    • 2012
  • The paper includes the utlization of an activated carbon as a potential adsorbent to remove a hazardous fluorescein dye from an aqueous solution. Batch adsorption experiments were carried out for the removal of fluorescein dyes using a granular activated carbon as an adsorbent. The effects of various parameters such as pH, amount of adsorbent, contact time, initial concentration and temperature of the adsoprtion system were investigated. The experimental results revealed that activated carbon exhibit high efficiencies to remove fluorescein dyes from the aqueous solution. The equilibrium process can be well described by Freundlich isotherm in the temperature range from 298 K to 318 K. From adsorption kinetic experiments, the adsorption process followed a pseudo second order kinetic model, and the adsorption rate constant ($k_2$) decreased with increasing the initial concentration of fluorescein. The free energy of adsorption ${\Delta}G^0$), enthalpy ${\Delta}H^0$), and entropy (${\Delta}S^0$) change were calculated to predict the nature adsorption. The estimated values for ${\Delta}G^0$ were -17.11~-20.50 kJ/mol over an activated carbon at 250 mg/L, indicated toward a spontaneous process. The positve value for ${\Delta}H^0$, 33.2 kJ/mol, indicates that the adsorption of fluorescein dyes on an activated carbon is an endothermic process.

Equilibrium, Kinetic and Thermodynamic Parameter Studies on Adsorption of Allura Red from Aqueous Solution by Granular Activated Carbon (입상활성탄에 의한 수용액으로부터 오로라 레드의 흡착에 대한 평형, 동력학 및 열역학 파라미터에 관한 연구)

  • Lee, Jong-Jib
    • Applied Chemistry for Engineering
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    • v.25 no.4
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    • pp.430-436
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    • 2014
  • Allura Red (AR) is a water-soluble harmful tar-based food colorant (FD & C Red 40). Batch adsorption studies were performed for the removal of AR using bituminous coal based granular activated carbon as adsorbent by varying the operation parameters such as adsorbent dosage, initial concentration, contact time and temperature. Experimental equilibrium adsorption data were analyzed by Langmuir, Freundlich and Temkin isotherms. The equilibrium process was described well by Freundlich isotherm. From determined separation factor ($R_L$), adsorption of AR by granular activated carbon could be employed as effective treatment method. Temkin parameter, B was determined to 1.62~3.288 J/mol indicating a physical adsorption process. By estimation of adsorption rate experimental data, the value of intraparticle diffusion rate constant ($k_m$) increased with the increasing adsorption temperature. The adsorption process were found to confirm to the pseudo second order model with good correlation. Thermodynamic parameters like change of free energy, enthalpy, and entropy were also calculated to predict the nature adsorption in the temperature range of 298~318 K. The negative Gibbs free energy change (${\Delta}G$ = -2.16~-6.55 kJ/mol) and the positive enthalpy change (${\Delta}H$ = + 23.29 kJ/mol) indicated the spontaneous and endothermic nature of the adsorption process, respectively.

Adsorption Characteristics of Dimetridazole Antibiotics on Activated Carbon Prepared from Agricultural Waste Citrus Peel (폐감귤박 활성탄을 이용한 항생제 Dimetridazole의 흡착특성)

  • Lee, Chang-Han;Kam, Sang-Kyu;Lee, Min-Gyu
    • Korean Chemical Engineering Research
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    • v.55 no.6
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    • pp.798-806
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    • 2017
  • A activated carbon (WCAC, waste citrus activated carbon) prepared from an agricultural waste citrus peel material generated in Jeju was utilized for the removal of dimetridazole (DMZ) antibiotics in aqueous solution. The adsorption of DMZ on WCAC was investigated with the change of various parameters such as contact time, dosage of WCAC, particle size of WCAC, temperature, pH, and DMZ concentration. The DMZ adsorption capacity increased with increasing temperature and decreasing particle size. Also it was decreased at less than pH 4 but sustained almost constantly at pH 4 or greater. Isotherm parameters were determined from the Langmuir, Freundlich, Redlich-Peterson and Duinin-Radushkevich (D-R) isotherm models. The isotherm data were best described by the Redlich-Peterson isotherm model. And the adsorption kinetics can be successfully fitted to the pseudo-second-order kinetic model. The results of the intra-particle diffusion model suggested that film diffusion and intra-particle diffusion were occurred simultaneously during the adsorption process. Meanwhile, the thermodynamic parameters indicated that the adsorption reaction of DMZ on WCAC was an endothermic and spontaneous process. The experimental results showed that WCAC is a promising and cheap adsorbent for the removal of DMZ antibiotics.

Study on Equillibrium, Kinetic, Thermodynamic Parameters for Adsorption of Brilliant Green by Zeolite (제올라이트에 의한 Brilliant Green의 흡착에 대한 평형, 동역학 및 열역학 파라미터에 관한 연구)

  • Lee, Jong Jib
    • Korean Chemical Engineering Research
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    • v.56 no.1
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    • pp.112-118
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    • 2018
  • Adsorption equilibrium, kinetic and thermodynamic parameters of a brilliant green from aqueous solutions at various initial dye concentration (10~30 mg/L), contact time (1~24 h) and temperature (298~318 K) on zeolite were studied in a batch mode operation. The equilibrium adsorption values were analyzed by Langmuir, Freundlich and Dubinin-Radushkevich model. The results indicate that Langmuir and Freundlich model provides the best correlation of the experimental data. Base on the estimated values of Langmuir dimensionless separation factor ($R_L=0.041{\sim}0.057$) and Freundlich constant (1/n=0.30~0.47), this process could be employed as effective treatment method. calculated values of adsorption energy by Dubinin-Radushkevich model were 1.564~1.857 kJ/mol corresponding to physical adsorption. The adsorption kinetics of brilliant green were best described by the pseudo second-order rate model and followed by intraparticle diffusion model. Thermodynamic parameters such as activation energy, free energy, enthalpy and entropy were calculated to estimate nature of adsorption. negative Gibbs free energy (-10.3~-11.4 kJ/mol), positive enthalpy change (49.48 kJ/mol) and Arrehenius activation energy (27.05 kJ/mol) indicates that the adsorption is spontaneous, endothermic and physical adsorption process, respectively.

Characteristics of Equilibrium, Kinetics and Thermodynamics for Adsorption of Disperse Yellow 3 Dye by Activated Carbon (활성탄에 의한 Disperse Yellow 3 염료의 흡착에 있어서 평형, 동력학 및 열역학적 특성)

  • Lee, Jong-Jib
    • Clean Technology
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    • v.27 no.2
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    • pp.182-189
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    • 2021
  • The adsorption of disperse yellow 3 (DY 3) on granular activated carbon (GAC) was investigated for isothermal adsorption and kinetic and thermodynamic parameters by experimenting with initial concentration, contact time, temperature, and pH of the dye as adsorption parameters. In the pH change experiment, the adsorption percent of DY 3 on activated carbon was highest in the acidic region, pH 3 due to electrostatic attraction between the surface of the activated carbon with positive charge and the anion (OH-) of DY 3. The adsorption equilibrium data of DY 3 fit the Langmuir isothermal adsorption equation best, and it was found that activated carbon can effectively remove DY 3 from the calculated separation factor (RL). The heat of adsorption-related constant (B) from the Temkin equation did not exceed 20 J mol-1, indicating that it is a physical adsorption process. The pseudo second order kinetic model fits well within 10.72% of the error percent in the kinetic experiments. The plots for Weber and Morris intraparticle diffusion model were divided into two straight lines. The intraparticle diffusion rate was slow because the slope of the stage 2 (intraparticle diffusion) was smaller than that of stage 1 (boundary layer diffusion). Therefore, it was confirmed that the intraparticle diffusion was rate controlling step. The free energy change of the DY 3 adsorption by activated carbon showed negative values at 298 ~ 318 K. As the temperature increased, the spontaneity increased. The enthalpy change of the adsorption reaction of DY 3 by activated carbon was 0.65 kJ mol-1, which was an endothermic reaction, and the entropy change was 2.14 J mol-1 K-1.

Characteristics and Parameters for Adsorption of Carbol Fuchsin Dye by Coal-based Activated Carbon: Kinetic and Thermodynamic (석탄계 활성탄에 의한 Carbol Fuchsin의 흡착 특성과 파라미터: 동력학 및 열역학)

  • Lee, Jong Jib
    • Applied Chemistry for Engineering
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    • v.32 no.3
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    • pp.283-289
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    • 2021
  • Adsorption characteristics of carbol fuchsin (CF) dye by coal-based activated carbon (CAC) were investigated using pH, initial concentration, temperature and contact time as adsorption variables. CF dissociates in water to have a cation, NH2+, which is bonded to the negatively charged surface of the activated carbon in the basic region by electrostatic attraction. Under the optimum condition of pH 11, 96.6% of the initial concentration was adsorbed. Isothermal adsorption behavior was analyzed using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models. Langmuir's equation was the best fit for the experimental results. Therefore, the adsorption mechanism was expected to be adsorbed as a monolayer on the surface of activated carbon with a uniform energy distribution. From the evaluated Langmuir's dimensionless separation coefficients (RL = 0.503~0.672), it was found that CF can be effectively treated by activated carbon. The adsorption energies determined by Temkin and Dubinin-Radushkevich models were E = 15.31~7.12 J/mol and B = 0.223~0.365 kJ/mol, respectively. Therefore, the adsorption process was physical (E < 20 J/mol, B < 8 kJ/mol). The experimental result of adsorption kinetics fit better the pseudo second order model. In the adsorption reaction of CF dye to CAC, the negative free energy change increased as the temperature increased. It was found that the spontaneity also increased with increasing temperature. The positive enthalpy change (40.09 kJ/mol) indicated an endothermic reaction.