• Korean Chemical Engineering Research
• /
• v.59 no.4
• /
• pp.565-573
• /
• 2021

Isotherms, kinetics and thermodynamic properties for adsorption of Brilliant Green(BG), Quinoline Yellow(QY) dyes by activated carbon were carried out using variables such as dose of adsorbent, pH, initial concentration, contact time, temperature and competitive. BG showed the highest adsorption rate of 92.4% at pH 11, and QY was adsorbed at 90.9% at pH 3. BG was in good agreement with the Freundlich isothermal model, and QY was well matched with Langmuir model. The separation coefficients of isotherm model indicated that these dyes could be effectively treated by activated carbon. Estimated adsorption energy by Temkin isotherm model indicated that the adsorption of BG and QY by activated carbon is a physical adsorption. The kinetic experimental results showed that the pseudo second order model had a better fit than the pseudo first order model with a smaller in the equilibrium adsorption amount. It was confirmed that surface diffusion was a rate controlling step by the intraparticle diffusion model. The activation energy and enthalpy change of the adsorption process indicated that the adsorption process was a relatively easy endothermic reaction. The entropy change indicated that the disorder of the adsorption system increased as the adsorption of BG and QY dyes to activated carbon proceeded. Gibbs free energy was found that the adsorption reaction became more spontaneous with increasing temperature. As a result of competitive adsorption of the mixed solution, it was found that QY was disturbed by BG and the adsorption reduced.

• Journal of the Korean Chemical Society
• /
• v.37 no.5
• /
• pp.503-512
• /
• 1993

The purpose of this study was to investigate the retention behavior of phenols and to predict their retention in RPLC. The retention data of twenty-five phenols were measured on a $\mu-{Bondapak}\;C_{18}$ and a polymeric $C_{18}$ columns with methanol-water and acetonitrile-water as a mobile phase. From the observation of enthalpy-entropy compensation phenomenon, the following conclusions are drawn with regard to the retention mechanism: 1) the retention mechanism of nitrophenols in different from that of metheyl-and chlorophenols in both mobile phase; 2) in methanol-water mobile phase, the retention mechanism of methyl-and chlorophenols is consistent in the range of methanol-water composition; 3) on the other hand, in the case of acetonitrile-water mobile phase, the retention mechanism depends on the volume fraction of acetonitrile. It means that the retention mechanism can not be explained only by a simple interaction. Based on retention data as compared with two columns, it may be said that the hydrophobic interaction of phenols with polymeric $C_{18}$ column was greater than that with monomeric $C_{18}$ column. The equations for predicting the retention of phenols were derived by using hydrophobic substituent constant $(\pi)$ and the sum of Hammett's constant $(\sigma)$ and Taft's steric constant $(E_s)$.

• Applied Chemistry for Engineering
• /
• v.5 no.3
• /
• pp.406-412
• /
• 1994

The ion-exchange properties of $Ca^{2+}$ and $Mg^{2+}$ ions have been studied in ${\delta}-Na_2Si_2O_5$ synthesized from water glass. Results show that optimum temperature for synthesis of ${\delta}-Na_2Si_2O_5$ was $725^{\circ}C$. Ion-exchange isotherms for $Ca^{2+}$ and $Mg^{2+}$ exchange for $Na^+$ in the synthetic ${\delta}-Na_2Si_2O_5$ show that the ion-exchange capacity of magnesium is better than that of calcium, and the ion-exchange of magnesium is less sensitive for temperature than that of calcium. When initial pH of solution is increased between 2 and 6, the ion-exchange capacities of magnesium and calcium decrease a little. However, they are almost constant above pH 6 because of alkali buffer effect of ${\delta}-Na_2Si_2O_5$. In the thermodynamic studies, it was found that Gibbs free energies of reaction of calcium ion-exchange are larger than those of magnesium ion-exchange with inverse order of selectivity. The standard enthalpy and entropy of reaction of calcium ion-exchange are larger than those of magnesium ion-exchange.

• Microbiology and Biotechnology Letters
• /
• v.20 no.4
• /
• pp.422-429
• /
• 1992

The effect of various water-activity depressors, such as pol yo Is, sugars, and polymers, on the conversion yields of the enzymatic synthesis of maltosyl-$\beta$-cyclodextrin from $\beta$-cyc1odextrin and maltose through reverse reaction of pullulanase was investigated. PEG 6000 of concentration of 10% (w/w) was found to be the most acceptable water-activity depressor resulting for increment of conversion yield from 43.0% to 55.9%, corresponding maltosyl-$\beta$-cyc1odextrin concentration of 3.02 g/100 ml H20. Water activity was changed from initial 0.966 to 0.914 upon addition of 20% (w/w) of PEG 6000. The conversion yields were inversely proportional to the water activities, and the increased conversion yield was caused by water activity depression which inhibited the hydrolysis reaction of maltosyl-$\beta$-CD to maltose and $\beta$-cyc1odextrin. The changes of enthalpy ($\Delta$H), entropy ($\Delta$S), and Gibbs free energy ($\Delta$G) were calculated to be 36.788 kJ/mole, 0.067 kJ/mole K. and 14.433 kJ/mole, respectively. The synthesis of maltosyl-$\beta$-CD could be increased substantially by the intermittent feeding of $\beta$-cyclodextrin. PEG 6000 could be separated effectively from reaction mixture using ultrafiltration membrane for reutilization.

• Journal of the Korean Chemical Society
• /
• v.35 no.4
• /
• pp.343-349
• /
• 1991

Formation of charge transfer complex between iodine and substituted aniline [aniline, N,N-dimethylaniline(N,N-DMA), 2,6-dimethylaniline(2,6-DMA), 2,4,6-trimethylaniline(2,4,6-TMA)] in CHCl$_3$, CH$_2$Cl$_2$ : CHCl$_3$ (1 : 1), and CH$_2$Cl$_2$ have been studied kinetically by using conductivity method. In the transformation of initially formed outer charge transfer complex to inner complex, the effects of substituted aniline as electron donor and polar medium on the reaction were investigated. The rate of transformation depend on the dielectric contribution of medium and pK$_a$ value of substituted aniline. The order of rate increasing is 2,4,6-TMA, 2,6-DMA, aniline, and N,N-DMA. The activation enthalpy ${\Delta}H^{\neq}$ for 2.5 M-substituted aniline in CHCl$_3$ at 25$^{\circ}C$ is respectively N,N-DMA, 3.47 kcal/mol; aniline, 4.25 kcal/mol; 2,6-DMA, 7.79 kcal/mol and 2,4,6-TMA, 7.96 kcal/mol; and activation entropy ${\Delta}S^{\neq}$ is large and negative value of -41 ~ -55 cal/mol${\cdot}$K.

• Clean Technology
• /
• v.27 no.3
• /
• pp.261-268
• /
• 2021

Equilibrium, kinetics, and thermodynamics of adsorption of acid black 1 (AB1) by coal-based granular activated carbon (CGAC) were investigated with the adsorption variables of initial concentration of dye, contact time, temperature, and pH. The adsorption reaction of AB1 by activated carbon was caused by electrostatic attraction between the surface (H⁺) of activated carbon and the sulfite ions (SO₃^-) and nitrite ions (NO₂^-) possessed by AB1, and the degree of reaction was highest at pH 3 (97.7%). The isothermal data of AB1 were best fitted with Freundlich isotherm model. From the calculated separation factor (1/n) of Freundlich, it was confirmed that adsorption of AB1 by activated carbon could be very effective. The heat of adsorption in the Temkin model suggested a physical adsorption process (< 20 J mol^-1). The kinetic experiment favored the pseudo second order model, and the equilibrium adsorption amount estimated from the model agreed to that given by the experiments (error < 9.73% ). Intraparticle diffusion was a rate controlling step in this adsorption process. From the activation energy and enthalpy change, it was confirmed that the adsorption reaction is an endothermic reaction proceeding with physical adsorption. The entropy change was positive because of an active reaction at the solid-liquid interface during adsorption of AB1 on the activated carbon surface. The free energy change indicated that the spontaneity of the adsorption reaction increased as the temperature increased.

• Clean Technology
• /
• v.27 no.2
• /
• pp.182-189
• /
• 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 (R_L). 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.

• Journal of the Korean Chemical Society
• /
• v.18 no.3
• /
• pp.157-170
• /
• 1974

The effects of ionic strength on the polynucleation reaction of tungstate ions and the protonized reaction of polytungstate ions have been investigated in the range of ionic strength from 1 M to 4 M KCl.The hexatungstate ions and the protonized forms of hexatungstate ions are formed in the tungstate solutions whose ionic strengths are 1 M to 4 M KCl. The equilibrium constants for the formation of hexatungstate ions and the protonized forms of hexatungstate ions are calculated in the range of ionic strength from 1 M to 4M KCl. The enthalpy changes for the formation of hexatungstate ions and the protonized forms of hexatungstate ions are as follows; $7H^++{6WO_4}^{2-}={HW_6O_{21}}^{5-}+3H_2O\;\;{\Delta}H^{\circ}=-62.4{\pm}0.6$$H^++{HW_6O_{21}}^{5-}={H_2W_6O_{21}}^{4-}\;\;{\Delta}H+_1^{\circ}=-4.12{\pm}0.10$$H^++{H_2W_6O_{21}}^{4-}={ H_3W_6O_{21}}^{3-}\;\;{\Delta}H_2^{\circ}=-4.36{\pm}0.30$ The free energy and entropy changes for the above reactions have been also calculated. A linear relation is formed between $log k_{6,7}$ and ionic strength, and $log k_1\;or\;log k_2\;vs{\cdot}{\mu}.$ $log k_{6,7}\;=\;D{\mu}+I,\;\;where\;D\;=\;1.66{\pm}0.02$$log k_1\;=\;D_1{\mu}+I_1,\;\;where\;D_1\;=\;-8.065{\pm}0.001$$log k_2\;=\;D_2{\mu}+I_2,\;\;where\;D_2\;=\;-0.376{\pm}0.006$

• Analytical Science and Technology
• /
• v.6 no.1
• /
• pp.107-119
• /
• 1993

The purpose of this study is to investigated the elution behavior of platinoid metal acetylacetonates, which is the key to elucidate their retention mechanism and optimize their RPLC separation conditions. The retention data of four platinoid metal acetylacetonates have been measured on four different columns in methanol-water and acetonitrile-water systems. The retention of uncharged platinoid metal acetylacetonates is interpreted by solvophobic effect. The retention of platinoid metal acetylacetonates is also greatly influenced by the geometric structure of the complexes. The square planar chelates, $Pd(acac)_2$, $Pt(acac)_2$, are retained longer than the octahedral chelates, $Rh(acac)_3$, $Ir(acac)_3$. It is likely due to that square planar chelates show greater interaction with nonpolar stationary phase than octahedral chelates. The results of van't Hoff plots have shown that platinoid metal acetylacetonates is operated on the same retention mechanism in the temperature range of $25{\sim}45^{\circ}C$. The study of the retention mechanism by the enthalpy-entropy compensation phenomenon has indicated that the retention mechanism of octahedral chelates and square planar chelates do not vary with the composition change of methanol-water mobile phase, respectively. In acetonitrile-water mobile phase, however, the retention mechanism is observed to be more complicated. Optimum condition for the separation of four platinoid metal acetylacetonates is found to be 40% methanol, polymeric C18 column, and $45^{\circ}C$.

• Journal of the Korean Chemical Society
• /
• v.36 no.5
• /
• pp.669-673
• /
• 1992

The stability constants, K for the complexation of alkali metal cations(Li^+, Na^+, K^+, Rb^+, and Cs^+) with both 4,5: 13,14-dibenzo-6,9,12-triaza-bicyclo [15,3,1] heneicosa-1 (21),7,19-trioxa-2,16-dione (DBPDA) and 6,9,12-trioxa-3,15,21-triaza bicyclo [15,3,1] heneicosa-1 (21),17,19-triene-2,16-dione (PDA) in N,N-Dimethylformamide (DMF) were determined conductomatically at various temperatures. At all the experiment temperatures, the K value sequences of the alkali metal ions with DBPDA and PDA are Cs^+ > K^+ > Rb^+ > Li^+ > Na^+ and Cs^+ > K^+ > Rb^+ > Li^+ > Na+, respectively. The K values for DBPDA are larger those of PDA for alkali metal ions. The widely recounted "hole-size-selectivity" principle is not applicable to these complexation systems. From the K values obtained at different temperatures, {\delta}H and T{\delta}S for these complexation reactions were determined. The enthalpy change plays principal important role in the complex formation by DBPDA. However, in the case of PDA, the entropy change also contributes to its complex formation.