• Journal of the Korean Chemical Society
• /
• v.28 no.6
• /
• pp.403-411
• /
• 1984

Amberlite XAD-7 and XAD-4 resins impregnated with DXHQ (5,7-dihalo-8-hydroxyquinoline) were prepared for the adsorption, separation and recovery of heavy metal ions from aqueous solutions. The characteristics of the impregnated resins, DXHQ (X : Cl, Br, I)-XAD were studied to find out the proper pairs of resin and DXHQ for the adsorption of metal ions. The increasing order of the impregnated amount of DXHQ onto XAD-7 resin was as follows: DCHQ < DBHQ < DIHQ. It was observed from the plot of log $K_d$ vs. pH that the optimum pH range for the adsorption of DIHQ onto XAD-4 resin was from 3.0 to 7.0. The stabilities of the DXHQ-XAD resins were investigated by measuring the amount of DXHQ remained on the XAD resin after shaking the DXHQ-XAD resins in various solutions of pH ranging from 2 to 12 and hydrochloric acid solutions. The impregnated resins were considerably stable in both acidic and neutral solutions. The amount of DIHQ leached from DIHQ-XAD-4 resin by eluting with various HCl solutions (1 ∼ 5M) was negligible, but in the case of XAD-7 resin it increases as the concentration of HCl solution increases. The optimum pH ranges, absorption mole ratio (M : DXHQ) and adsorption capacities (mmol metal per gram of resin) for the adsorption of metal ions onto the DXHQ-XAD resins were determined respectively. The stability of metal ion absorbed by the DXHQ-XAD resins was observed as the following order: M-DCHQ-XAD-7 < M-DBHQ-XAD-7 < M-DIHQ-XAD-7. The adsorbed metal ions were quantitatively recovered by eluting with HCl (0.5 ∼ 5M) and DXHQ-XAD resins could be reused over 5 times without re-impregnation of DXHQ.

• Journal of the Korean Chemical Society
• /
• v.27 no.5
• /
• pp.353-360
• /
• 1983

The adsorption behavior of 8-hydroxyquinoline (8HQ) on Amberlite XAD-4 and-7 resins was investigated by measuring its distribution coefficients under various experimental conditions, such as shaking time, pH and concentration of methanol in the medium. The application of 8HQ-impregnated-XAD resins for the absorption and separation of metal ions was studied. The maximum adsorption of 8HQ on XAD resins was observed in the 30% methanol solution having pH range from 6.0 to 9.0. The impregnation capacities of XAD resins for 8HQ were 3.81${\times}$10-2mmol, 8HQ/g, XAD-4 resins and 2.60${\times}$10-2mmol, 8HQ/g, XAD-7 resin, respectively. The 8HQ-impregnated-XAD resins were stable in pH range from 6.0 to 10.0 and the amount of 8HQ leached from XAD-4 resin by eluting with hydrochloric acid(above 5M) was negligible. The optimum pH range for the adsorption of metal ions on 8HQ-impregnated XAD resin was also 6.0 to 10.0, and the adsorption mole ratio of metal ion to 8HQ were 1 : 2 for Cu(II), Cd(II) and Ni(II), and 1 : 3 for Fe(III) at the above pH range. It was found that the absorbed metal ions on 8HQ-impregnated-XAD resins were recovered quantitatively with 5M HCl and 8HQ-impregnated-XAD-4 resin could be reusable over 5 times without decrease in its impregnation capacity.

• Journal of the Korean Chemical Society
• /
• v.29 no.4
• /
• pp.397-405
• /
• 1985

The adsorption behaviors of some oxime compounds well known as metal chelating agents on the Amberlite XAD resins were compared by measuring their distribution coefficients (log Kd) in various media, respectively. Among the oxime compounds, salicylaldoxime (SAO) and $\alpha-benzoinoxime(${\alpha}$-BzO)$ which showed large log Kd values were chosen. The characteristics of XAD-4 resins impregnated with SAO and ${\alpha}$-BzO have been studied to apply them for the adsorption and recovery of minute quantities of metal ions in aqueous solution. The optimum conditions for adsorption of SAO and ${\alpha}$-BzO on the resin were 30% methanol media having pH range of 1~8(for SAO) and 1~9 (for ${\alpha}$-BzO), respectively. The distribution coefficients of two oxime compounds were decreased as temperature increased. From the adsorption enthalpy data of SAO and ${\alpha}$-BzO, ranging from 4.96 to 6.66 Kcal/mol, it is suggested that their adsorption mechanism on XAD-4 resin is likely due to molecular adsorption equivalent to dipole-dipole interaction. The impregnated resins were considerably stable in the aqueous solutions of pH 5.0~10.0 and in 0.1~5M hydrochloric acid solutions. The former is the medium for adsorption of metal ions, while the latter is for recovery of the adsorbed metal ions. The adsorption mole ratio of Mn(II), Co(II), Ni(II), Zn(II) ions on SAO-XAD-4 and ${\alpha}$-BzO-XAD-4 resins were about 1 : 2 at the optimum conditions, respectively. The adsorbed metal ions were recovered completely by eluting with 3M HCl-50% methanol solution

• Bulletin of the Korean Chemical Society
• /
• v.27 no.1
• /
• pp.77-81
• /
• 2006

The commercially available Amberlite XAD-2 and XAD-4 resins were modified with macrocyclic protoporphyrin IX (PPIX) or tetrakis(p-carboxyphenyl) porphyrin (TCPP) to enhance the adsorption capacity for phenol and chlorophenols. The chemically modified polymeric adsorbents (XAD-2+PPIX, XAD-2+TCPP, XAD-4+PPIX, and XAD-4+TCPP) were applied to the solid phase extraction as an adsorbent material for the preconcentration of phenol and chlorophenols in environmental waters. Generally, the synthesized adsorbents showed higher recoveries than underivatized adsorbents, XAD-2 and XAD-4, without matrix interferences. Especially, XAD-4+PPIX showed more than 90% recoveries for all compounds used in this study including hydrophilic phenol. The major factor for the increase of the adsorption capacity was the increase of $\pi$-$\pi$ interaction between adsorbents and samples due to the introduction of the porphyrin molecule. However, the breakthrough volumes and recovery values of the XADs+TCPP columns were slightly decreased for the bulky chlorophenols such as TCP and PCP. Using molecular mechanics methods, the structures of TCPP and PPIX were compared with that of porphine, the parent molecule of porphyrin. Four bulky p-carboxyphenyl groups of TCPP were torsional each other, thus the molecular plane of TCPP were not on the same level. In conclusion, the decrease of breakthrough volumes and recovery values of XADs+TCPP columns for bulky phenols can be explained by the steric hindrance of the $\pi$-$\pi$ interaction between porphyrin plane and the phenols.

• Analytical Science and Technology
• /
• v.8 no.3
• /
• pp.397-404
• /
• 1995

Three Arsenazo I-XAD Chelating resins, with different surface areas and pore sizes were synthesized and characterized. The total sorption capacities of these chelating resins for Cu(II) at pH 5.0 by batch method decreased as follows, Arsenazo I-XAD-16(0.59mmol/g)>Arsenazo I-XAD-4(0.56mmol/g)>Arsenazo I-XAD-2(0.38mmol/g). The sorption and desorption properties of Arsenazo I-XAD-16 chelating resins for U(VI), Th(IV), Hf(IV), Zr(IV), Ni(II), Mn(II), Cd(II). and Cu(II) were studied by both batch and elution method. The Arsenazo I-XAD-16 chelating resin was successfully applied to the separation and concentration of trace U(VI) and Th(IV) in sea and waste waters.

• Bulletin of the Korean Chemical Society
• /
• v.28 no.8
• /
• pp.1375-1382
• /
• 2007

A column preconcentration method with pulverized Amberlite XAD-4 loaded with bismuthiol I (BI) has been developed for the determination of trace Cd(II) and Cu(II) in various real samples by flame atomic absorption spectrophotometry. Various experimental conditions, such as the size of XAD-4, adsorption flow rate, amount of bismuthiol I, stirring time for adsorbing bismuthiol I on XAD-4, pH of sample solution, amount of XAD-4- BI, desorption solvent, and desorption flow rate, were optimized. Also, the adsorption capacity and the adsorption rate of Cd(II) and Cu(II) on XAD-4-BI were investigated. The interfering effects of various concomitant ions were investigated, Bi(III), Sn(II) and Fe(III) were found to affect the determination. But the interference by these ions was completely eliminated by adjusting the amount of XAD-4-BI resin to 0.70 g, although the adsorption flow rate was slower. For Cd(II) our proposed technique obtained a dynamic range of 0.5-40 ng mL-1, a correlation coefficient (R2) of 0.9913, and a detection limit of 0.3 ng mL-1. For Cu(II), the corresponding values were 2.0-120 ng mL-1, 0.9921 and 1.02 ng mL-1. To validate this proposed technique, the aqueous samples (stream water, reservoir water, tap water and wastewater), the diluted brass sample and the plastic sample, as real samples, were used. Recovery yields of 91-103% were obtained. These measured data were not different from ICP-MS data at 95% confidence level. Our proposed method was also validated using rice flour CRM (normal, fortified) samples. From the results of our experiment, we found that the technique we present here can be applied to the determination of Cd(II) and Cu(II) in various real samples.

• Analytical Science and Technology
• /
• v.13 no.3
• /
• pp.323-331
• /
• 2000

Two chelating resins, XAD-16-TAC and XAD-16-TAO were synthesized by Amberlite XAD-16 macroreticular resin with 2-(2-thiazolylazo)-p-cresol (TAC) and 4-(2-thiazolylazo)-orcinol (TAO) as functional groups. The sorption behaviour of Zr(IV), Th(IV) and U(VI) with two chelating resins were examined with respect to the effect of pH and masking agent by batch methods. It was obtained that the optimum pH was in the range of 5-6, and two chelating resins showed good separation efficiency of Zr(IV) or Th(IV) by using $NH_4F$ as a masking agent. Characteristics of desorption were investigated with 0.1-2 M $HNO_3$ as desorption agent. It was found that 2 M $HNO_3$ showed high desorption efficiency to most of metal ions except Zr(IV). XAD-16-TAC resin is applied to separation and preconcentration of trace Zr(IV) from mixed metal ions. Also, Th(IV) ion can be successfully separated from U(VI) and Zr(IV) ion by using XAD-16- TAO resin.

• Analytical Science and Technology
• /
• v.9 no.3
• /
• pp.279-291
• /
• 1996

The new chelating resins, XAD-2, 4, 16-TAC and XAD-2, 4, 16-TAO were synthesized by Amberlite XAD-2, XAD-4, and XAD-16 macroreticular resins with 2-(2-thiazolylazo)-p-cresol(TAC) and 4-(2-thiazolylazo)orcinol(TAO) as functional groups and were characterized by elemental analysis and FT-IR spectrometry. It was found that the content of functional group in chelating resin was 0.60mmol/g in XAD-16-TAC and 0.68mmol/g in XAD-16-TAO respectively. The chelating resins were stable in acidic and alkaline solution and can be reused over 10 times. The sorption behavior of some metalions to two chelating resins was investigated by batch method, which included batch equilibrium, effect of pH, coexisting ions and masking agent. For the optimum condition of sorption, the time required for equilibrium was about 1 hour and optimum pH was 5. In the presence of anions such as ${SO_4}^{2-}$ and $CH_3COO^-$, the sorption of U(VI) ion was slightly reduced but other anions such as $Cl^-$ and $NO{_3}^-$ revealed no interference effect. Also, sorption capacity of U(VI) ion was decreased by addition of $CO{_3}^{2-}$ ion because of complex formation of $[UO_2(CO_3)_3]^{4-}$, but alkali metals and alkali earth metals including Na(I), K(I), Mg(II), and Ca(II) were not affected for the sorption extent. Masking agent, NTA showed better separation efficiency of U(VI) ion from coexisting metal ions such as Th(IV), Zr(IV), Hf(IV), Cu(II), Cd(II), Pb(II), Ni(II), Zn(II) and Mn(II) than EDTA, CDTA.

• Journal of the Korean Chemical Society
• /
• v.31 no.4
• /
• pp.308-314
• /
• 1987

The adsorption behavior of some chelating agents on the Amberlite XAD-7 resin was studied to obtain the optimum conditions for the preparation of chelating agent-XAD-7 resins. The chosen chelating agents are cupferron (CP), diphenylcarbazone (DPC), salicylaldoxime (SAO), thiosalicylic acid (TSA), and dimethylglyoxime (DMG), which have been well known chelating agents to Cu(Ⅱ) and Ni (Ⅱ) ions. Among the chelating agent-XAD-7 resins, SAO-XAD-7 and DMG-XAD-7 resins were evaluated as appropriate impregnated resins by investigating their stabilities in the wide pH range and high abilities to adsorb Cu(Ⅱ) and Ni(Ⅱ) ions. The selective adsorption of Cu(Ⅱ) from Ni(Ⅱ) was possible by changing pH condition by SAO-XAD-7 resin. The adsorption capacities of SAO-XAD-7 and DMG-XAD-7 for Cu(Ⅱ) were $7{\times}10^{-3}mmol$ Cu(Ⅱ) per gram of resin and $2{\times}10^{-3}mmol$ Cu(Ⅱ) per gram of resin, respectively. The quantitative recovery of Cu(Ⅱ) adsorbed by the resin was demonstrated. The adsorption behavior of Cu(Ⅱ) and Ni(Ⅱ) by the single and mixed bed of chelating agent-XAD-7 resin was discussed.

• Journal of the Korean Chemical Society
• /
• v.32 no.5
• /
• pp.483-494
• /
• 1988

The adsorption behavior of aromatic acids on Amberlite XAD-4 resin was investigated by measuring the distribution coefficient by batch method. The adsorption of solutes on XAD-4 was affected by the several factors such as, analyte concentration, the pH of solution and concentration of pairing ion. The enhanced adsorption of solutes on XAD-4 in the presence of tetraalkylammonium salt as an ion pairing reagent, referred to as ion interaction, was suggested to follow a double layer model where the pairing ion occupies a primary layer at the adsorbent while the solute anion and other anions in the system comlpete for the secondary layer. Therefore, the ability of an ion pairing reagent to enhance solute adsorption depended significantly on the type and concentration of counter-ion and co-anion accompanying the ion pairing reagent or salt used for ionic strength control. In addition, a good linear relationship between the logarithm of capacity factors measured by batch and elution method as a function of the concentration of ion pairing reagent and methanol can be used to predict the retention in elution method on the basis of capacity factors measured by batch method.