역상 액체크로마토그래피에서 벤젠 일치환체들의 머무름 메카니즘에 관한 연구 (Ⅰ). 벤젠 일치환체들의 용리거동

이대운,최용욱,김현주,정용순,Dai Woon Lee,Yong Wook Choi,Hyun Joo Kim,Yong Soon Chung 대한화학회 1987 대한화학회지 Vol.31 No.1

The systematic investigation of the retention behaviors of 18 monosubstituted benzenes in reversed-phase liquid chromatography(RPLC) was studied in order to predict the separation possibility of their mixtures and study the contribution of substituent group to the retentions of solutes. The columns and mobile phases employed in this study were $\mu$ -Bondapak $C_{18}$, $\mu$-Bondapak phenyl columns and methanol/water, acetonitrile/water, and THF/water, respectively. The polar substituents such as phenol, aniline, acetophenone and benzonitrile have smaller capacity factor(k') values than benzene, while nonpolar ones such as alkylbenzenes and halobenzenes show larger k' value. The capacity factors of all solutes increased on both C18 bonded and phenyl bonded phases as the organic solvent content of three organic solvent-water mixtures decreased. The absolute differences in capacity factor(${\Delta}k$') between substituent and benzene were graphically shown for the prediction of the separation of the mixture and interpretation of the elution behavior of substituent. In addition, the selectivity of solvent system for the separation of the mixture was investigated in both two columns and three mobile phases. 본 연구는 결합 정지상 컬럼을 이용한 역상 액체 크로마토그래피에서 치환기에 따른 시료의 용리거동을 알아 보기 위한 일련의 연구로서 비교적 극성인 치환체에서 비극성인 치환체까지 18종의 벤젠 일치환체를 대상으로 $\mu$-Bondapak $C_{18} 컬럼 및 $\mu$-Bondapak phenyl컬럼상에서 메탄올-물, 아세토니트릴-물, 및 THF-물의 혼합용액을 이동상으로 하여 시료의 용리거동을 알아 보았다. 극성인 치환기를 갖는 치환체들의 용량인자(k')는 벤젠에 k'값보다 적었으며, 반대로 비극성인 치환체들의 k'값은 벤젠보다 컸다. 이동상중의 유기용매의 농도가 감소함에 따라 모든 벤젠 일치환체들의 용량 인자값은 증가하였다. 혼합물의 분리의 가능성을 예측하고 치환체들의 용리거동을 설명하기 위하여 컬럼의 종류 및 이동상의 종류에 따라 달라지는 각 치환체들의 머무름의 변화를 벤젠을 기준으로 하여 용량인자의 절대치의 차(${\Delta}k$')로 도식화하였다. 두 컬럼과 세가지 용매시스템에서 치환체들의 용량인자를 상호 비교하므로써 선택성이 큰 용매시스템을 조사하였다.

엔진기술 동향

이대운 한국자동차공학회 2001 한국자동차공학회 Workshop Vol.2001 No.-

화학문헌 및 정보에 관한 소고

이대운 연세대학교 교육대학원 1981 연세교육과학 Vol.19 No.-

Amberlite XAD 수지들에 대한 8-Hydroxyquinoline과 그 유도체들의 흡착성에 관한 연구

이대운,정용순,유의경 연세대학교 대학원 1983 延世論叢 Vol.20 No.1

The adsorption behaviors of 8-hydroxyquinoline (8HQ) and its some derivatives on the synthetic rosins such as Amberlite XAD-2, XAD-4, XAD-7, XAD-8 have been investigated by measuring their distribution coefficients (Kd) in various media by batch technique. The derivatives of 8HQ are 5,7-dichloro-8-hydroxyquinoline (DCHQ), 5,7-dibromo-8-hydroxyquinoline (DBHQ), 5,7-diiodo-8-hydroxyquinoline (DIHQ) and 2-methyl-8-hydroxy-quinoline (MHQ). The adsorption behaviors of 8HQ and its derivatives on the resin can be interpreted by investigating the effect of pH of the medium on the distribution coefficients at a given condition. It has been observed that the distribution coefficients of 8HQ and its derivatives increase up to a certain pH values, which are corresponding isoelectric values, and then decrease as increasing pH. Since 8HQ and its derivatives hale phenol and pyridine structures in their molecules, the adsorption behaviors on the resins would be expected to be similar to the behavior of those of combined phenol and pyridine. The Amberlite XAD-7 resin impregnated with DBHQ has been studied for adsorption behaviors of Cu(II), Cd(II), and Pb(II) ions in the aqueous solution as an example of the application of the impregnated resin. The adsorption of the metal ions by DBHQ-XAD-7 resin is due to the chelation in 1 to 2 mole ratio. The adsorption capacity of DBHQ-XAD-7 resin for the metal ions is 7.5×10-3m mot per gram of the resin at the optimum condition which can be considered as the maximum adsorption capacity of the resin. The metal ions adsorbed on the retrain are recovered completely by eluting with acid and the resin can be reused serveral times.

음이온 교환수지에 대한 페놀류의 흡착에 관한 연구

李大云,鄭龍淳,兪義卿 연세대학교 자연과학연구소 1979 學術論文集 Vol.3 No.-

폐놀 및 그 유도체인 니트로, 히드록시, 아미노, 클로르 및 메톡시 폐놀들의 음이온교환수지에 대한 흡착성을 메탄올, 메탄올-KCl메디움에서 측정하여 정성적인 흡착메카니즘을 규명했다. 각 메디움에서 측정한 시료의 분배계수(Kd)값을 오르토, 메타 및 파라유도체별과 이성질체별로 시료의 pK_a, 및 용해도와 관련시켜 상관성을 조사하여 보았다. 여기서 pK_a값은 주로 이온화도보다는 시료의 극성의 정도를 의미하는 것으로 흡착성과 관련를 갖는다. The distribution coefficients (log K_d) of phenol and its derivatives on anion exchange resin were measured in methanol-water and methanol-water-KCl media. The derivatives were nitro, chloro, amino, hydroxy and methoxy phenols. The correlationship between tog K_d of phenols and their pK_a values and solubility was investigated to elucidate the qualiative absorption mechanism of phenols on the resin.

역상 액체 크로마토그래피에서 페놀 유도체들의 용리거동에 관한 연구

이대운,허덕순,유의경 연세대학교 교육대학원 1985 연세교육과학 Vol.28 No.-

The retention behaviors of phenol and its derivatives on μ-Bondapak C18 column was studied in methanol-water and acetonitrile-water solvent systems. The applicability of group constants for various substituents obtained from monosubstituted benzenes to the prediction of capacity factors of phenol derivatives was investigated by comparing capacity factors observed at the same chromatographic systems, 50% methanol and 50% accetonitrile solvents. It was found that the prediction of the capacity factors for the phenol derivatives having nonpolar substituent such as methyl and methoxy group was possible. On the other hand it was not for having polar substituents such as amino, cyano and nitro groups et al. It is likely due to the interaction between polar substituent and solvent. The Effect of substituents on the retention behaviour of benzen and phenol derivatives were studied with the Taft equation. It was observed that the effect of substituents in the phenol derivatives was more pronounced that in the monosubstituted benzens.

살리실산 착물들의 흡착성에 관한 연구 : 합성수지에 의한 철 A Study on Adsorption of Fe(Ⅲ)

이대운,문영자,이길상 연세대학교 자연과학연구소 1978 學術論文集 Vol.2 No.-

수용성이며, 색깔을 띠는 착물을 합성수지를 이용하여 수용액으로부터 흡착시켜, 이를 제거 또는 농축시키는 방법을 시도하였다. 선택한 착물은 살리실산 및 그 유도체와 Fe(Ⅲ)이온과의 착물이며, 흡착제로서는 무극성 수지인 Amberlite XAD-2와 XAD-7을 선택하여 착물들의 흡착정도를 뱃치법과 용리법으로 검토 하였으며, 흡착현상을 배위자인 살리실산 유도체들의 화학구조와 관련하여 검토하였다. 살리실산의 유도체들은 3-methyl, 4-methyl, 5-methyl, 3-nitro, 4-nitro, 5-nitro, 3,5-dinitro, 4-hydroxy, 5-chloro, 5-bromo, 5-sulfo 및 salicylic acid이며, salicylaldehyde, tiron도 아울러 시도하여 보았다. 사용한 수지들에 대한 Fe(Ⅲ)-salicylate 착물들의 기본 흡착메카니즘은 반델바알스인력에 의한 분자흡착이며, 배위자의 화학구조와 관계가 있었다. XAD-2와 XAD-7수지에 대한 Fe(Ⅲ)-salicylate 착물들의 흡착력은 일반적으로 배위자에-NO_2, -CH_3, -Cl, -Br 같은 소수성작용기가 있을수록 강하며, 배위자에 -OH나 -SO_3H같은 친수성 작용기가 있으면 흡착이 거의 무시되었다. 배위자인 살리실산들의 치환기 종류에 따른 흡착력의 감소 순위는 다음과 같다. -NO_2 ?? -Br ?? -Cl ?? -CH_3 > -H > -OH ?? -SO_3H 3,5-dinitrosalicylic acid의 Fe(Ⅲ)이온과의 착물은 흡착력이 강하여 매우 희박한 Fe(Ⅲ)수용액을 착물형성으로 수지에 농축시킬 수가 있었다. 이같은 흡착현상은 희박한 금속이온 정량에 필요한 단계인 농축실험에 이용할 수 있으며, 반대로 배위자의 선택적인 분리에도 응용이 가능하다. The water-soluble and colored complexes of Fe(Ⅲ) ion with salicylic acid and its derivatives have been extracted from aqueous solution using the nonpolar adsorbents, Amberlite XAD-2 and XAD-7 resins. The ligands studied are 3-nitro, 4-nitro, 5-nitro, 3.5-dinitro, 3-methyl, 4-methyl, 5-methyl, 4-hydroxy, 5-chloro, 5-bromo, 5-sulfo, salicylic acid, salicylaldehyde and tiron. The adsorption of the complexes on XAD copolymers as chromatographic adsorbents is likely due to primarily the van der Waal’s force. It has been investigated that in the adsorption process, the hydrophobic portion of the complex which has little affinity to water is preferentially oriented to the hydrophobic surface of the resin, while the hydrophilic portion of the complex will remain in the aqueous phase.. The adsorption of Fe(Ⅲ)-salicylate complexes is correlated with the nature of the substituted group of ligand molecule. The increase of the hydrophobic character of the substituted group results in an increase in retention (log D or V_R), i.e., the introduction of the hydrophilic substituted group shows lower log D or V_R values. For the Fe(Ⅲ)-salicylates, the decreasing order of log D or V_R values is as follows: -NO_2 ?? -Br ?? -Cl ?? -CH_3 > -H > -OH 〈 -SO_3H It is generally observed that the retention on XAD-7 is less than that XAD-2.

합성수지에 대한 유기성 공해물질의 흡착에 관한 연구

이대운,김용남,유의경,강삼우 연세대학교 자연과학연구소 1980 學術論文集 Vol.6 No.-

유기성 공해물질중 대표적인 유기화합물인 폐놀 및 폐놀유도체들의 합성수지에 대한 흡착성을 연구하므로서 일반적인 유기성 공해 물질의 흡착성을 조사하였으며, 이 연구는 유기성 공해물질로 오염된 오염수 처리를 위한 기초 연구가 될 것을 고려하여 시도하였다. 합성수지로는 생활주변에서 흔히 쓰이며 쉽게 구할 수 있는 수지인 폴리우레탄 수지를 선택하였는데 폐놀류의 흡착은 분자흡착으로 시료는 분자량이 크고, 소수성기를 갖고 물에 대한 용해도가 적을수록 증가되며, 액성이 알칼리성으로 되어 이온화가 될수록 급격히 흡착이 감소되었다. 폐놀외 다른 유기성 공해물질의 흡착도 비슷할 것으로 생각되며 우레탄 수지의 유기물의 흡착능은 오염수 처리를 위해 활용이 가능할 것으로 생각된다. 모든 흡착성 실험은 뱃취법으로 각 시료의 분포계수를 측정하여 조사하였다. A open-pore polyurethane foam was investigated as an adsorbent for phenol and its derivatives which are typical organic pollutants. Among the synthetic resins, polyurethane foam was chosen as an adsorbent because of its chemical structure and physical properties for the adsorption of organic compounds. Adsorption of phenols was presented as distribution coefficient (Kd) measured by batch method. The distribution coefficients of phenols as a function of pH was described. It was found that the adsorption behavior of phenols was closely related with their chemical structures. All the informations of this paper would be applicable to other organic pollutants.

이온쌍 형성에 의한 벤조산 이온들의 Amberlite XAD-4 수지에 대한 흡착성에 관한 연구

이대운,김진모,이인호,이택혁 연세대학교 교육대학원 1986 연세교육과학 Vol.29 No.-

This study investigated the adsorption trends of benzoic acid derivatives on Amberlite XAD-4 resin by measuring distribution coefficients to apply them for ion-pair chromatography. The adsorption of benzoic acids was decreased by increasing the dissociation of the acids. Thus, the adsorption of the acids was affected by the pH of the solution. Under the condition of minimum adsorption which caused by dissociation of the acids, the adsorption of the acids was increased by adding tetrabutylammonium chloride (TBACl) and tetrabutylammonium iodide (TBAI) as ion pairing reagents. It was found that the adsorption of the acids was also affected by the co-anions in solution. When the solute ions form ion-pair with pairing ion and adsorb on XAD-4 resin, the effects of co-anions on the adsorption were studied. The order of decreasing adsorption is as follows. I->Br->Cl- Under the concentration of TBACl having maximum adsorption of the acids, the effects of co·anions on the increase of relative adsorptivity, which is the ratio of the distribution coefficients of o-nitrobenzoic acid to that of m-nitrobenzoic acid are as follows : I->Br->Cl- But, with TBAI, the increase of relative adsorptivity by co·anions was not found. These effects of co-anions on the adsorption of the acids, agree with the ion selectivity in anion exchange resin. In this study, the adsorption mechanism of benzoate anions by ion-pair formation was inferred as ion-interaction. To increase the separation efficiency of solutes by increasing selective adsorption, it was found to be more favorable to use ion pairing reagents, whose counter ion has small ion selectivity, and to add co-anions having larger ion selectivity than its counter ion.

이온교환 수지에 대한 벤젠폴리칼 복시산들의 흡착성에 관한 연구

이대운,김영환,유의경 연세대학교 대학원 1980 延世論叢 Vol.16 No.2

Absorption behavior of benzene polycarbofylic acids such as benzoic, phthalic, trimesic, hemimellitic, trimellitic, pyromellitic, and mellitic acid, on Amberlite CG-400 and on XAD-2 was studied. In order to investigate sorption mechanism of these acids, effect of pH, concentration of MeOH, and other inorganic ion on long D value were studied. Several acids were separated by Amberlite CG-400, Cl- resin With ZnCl2-, NiCl2- and CdCl2- MeOH solutions