GC/MS 분석에 의한 4-Octylphenol의 Carboxen 흡착에 대한 열역학적 연구

이준배; 박우용; 손성건; 정지은; 정용애; 공보경; 김유나; 권오성; 팽기정; Joon-Bae Lee; Woo-Yong Park; Shungkun Shon; Ji Eun Jung; Yong Ae Jeong; Bokyoung Gong; Yu-Na Kim; O-Seong Kwon; Ki Jung Paeng

Applied Chemistry for Engineering, Vol.29, No.3, 356-361, June, 2018

DOI10.14478/ace.2018.1046 Export Citation

GC/MS 분석에 의한 4-Octylphenol의 Carboxen 흡착에 대한 열역학적 연구

Thermodynamic Studies on the Adsorption of 4-Octylphenol on Carboxen by GC/MS Analysis

이준배^†, 박우용, 손성건¹, 정지은, 정용애, 공보경², 김유나², 권오성, 팽기정³

국립과학수사연구원 대전과학수사연구소
¹대전보건대학교 과학수사과
²국립과학수사연구원 법화학과
³연세대학교 화학과

Joon-Bae Lee^†, Woo-Yong Park, Shungkun Shon¹, Ji Eun Jung, Yong Ae Jeong, Bokyoung Gong², Yu-Na Kim², O-Seong Kwon, and Ki Jung Paeng³

Daejeon Institute, National Forensic Service, Daejeon 34054, Korea
¹Dept. of Forensic Sci., Daejeon Health Institute of Technology, Daejeon 34504, Korea
²Forensic Chemistry Division, National Forensic Service, Wonju 26460, Korea
³Department of Chemistry, Yonsei University, Wonju 26493, Korea

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초록

혈액과 같이 다성분으로 이루어진 복잡한 matrix로 구성된 시료에서 휘발성 유기화합물(VOC)이나 반휘발성 유기화합물(SVOC)의 분석은 분리공정을 거쳐 분석되는 것이 일반적이다. 흡착은 어떤 성분이 다른 상의 표면에 축적되는 물리적 현상이다. 전처리 과정에서 번거로움을 극복하기 위해 흡착이 적용되며 이를 위해 다공성 탄소인 carboxen (CAR)이 도포된 solid phase microextraction (SPME) 장치가 흔히 사용된다. 본 연구에서는 플라스틱 제조시 가소제 등으로 사용되는 4-octylphenol의 carboxen에 대한 흡착특성을 살펴보았다. 이를 위해 dichloromethane (CH2Cl2, DCM), ethylacetate (CH3COOC2H5, EA) 및 diethylether (C2H5OC2H5, Et2O)에 대한 추출효율과 bistrimethylsilyltrifluoroacetamide (BSTFA), methylchloroformate (MCF) 및 pentafluorobenzylbromide (PFBBr)에 대한 유도체화 반응의 특성을 조사하였다. 열역학적 특성 파악을 위한 추출용제로는 DCM이 양호한 효과를 보였으며 BSTFA를 이용한 silylation의 분석특성이 우수하여 이를 적용하였다. 열역학적 및 동력학적 흡착실험 결과 흡착과정은 흡열특성을 보였고 Langmuir식보다는 Freundlich등온식에 더 근접하였으며 동력학적으로는 pseudo-2nd order kinetic model에 따르는 것을 보였다.

It is common to analyze volatile organic compound (VOC) or semi-VOC (SVOC) in a sample composed of a complex matrix consisting of multiple components such as bloods through a separation process. Adsorption is a physical phenomenon in which certain components accumulate on the surface of other phases. In order to overcome difficulties in the pretreatment process, an adsorption is frequently used. Solid phase microextraction (SPME) equipment with porous carbon carboxen (CAR) is an example of adsorption application. In this study, the adsorption of 4-octylphenol to carboxen was examined. To do so, the extraction efficiency for such solvents as dichloromethane (CH2Cl2, DCM), ethylacetate (CH3COOC2H5, EA) and diethylether (C2H5OC2H5, Et2O) was studied and also the derivatization reaction for 4-octylphenol with reagents of bistrimethylsilyltrifluoroacetamide (BSTFA), methylchloroformate (MCF) and pentafluorobenzylbromide (PFBBr) was compared. The combination of DCM and BSTFA showed good performance thus they were adopted for this study. Thermodynamic adsorption experiments showed that the adsorption process was endothermic and Freundlich isotherm equation was more suitable than Langmuir isotherm. It was also found that the adsorption followed a pseudo-2nd order kinetic model.

Keywords:carboxen;adsorption;derivatization;gas chromatograph/mass spectrometry

[References]

Pawliszyn J, Lord HL, Handbook of Sample Preparation, pp. 1-24, Wiley-Blackwell, NJ, USA (2010).
McCabe W, Smith J, Harriott P, Unit Operations of Chemical Engineering (7th ed.), pp. 836-844, McGraw-Hill, NY, USA (2005).
Wercinski SAS, Solid Phase Microextraction: A Practical Guide, pp. 114-116, Marcel Dekker, NY, USA (1999).
Pawliszyn J, Solid Phase Microextraction: Theory and Practice, pp. 21-23, Wiley-VCH, NY, USA (1997).
Mullett WM, Martin P, Pawliszyn J, Anal. Chem., 73, 2383 (2001)
Ho TD, Yu H, Cole WT, Anderson JL, Anal. Chem., 84, 9520 (2012)
Ying S, Lasekan O, Naidu KR, Lasekan S, Molecules, 17, 13795 (2012)
Ying GG, Kookana RS, Dillon P, Water Res., 37, 3785 (2003)
Fernandez AR, Costley CT, Rose M, Food Addit. Contam., 20, 846 (2003)
Tao LV, Zhao XE, Zhu S, Qu F, Song C, You J, Suo Y, J. Sep. Sci., 37, 2757 (2014)
Knapp DR, Handbook of Derivatization Reactions, pp. 30-38, John Wiley & Sons, NJ, USA (1979).
Chatterjee S, Woo SH, J. Hazard. Mater., 164(2-3), 1012 (2009)
Tan IAW, Ahmad AL, Hameed BH, J. Hazard. Mater., 154(1-3), 337 (2008)
Lee JJ, Um MH, Appl. Chem. Eng., 23(5), 450 (2012)

[1] Pawliszyn J, Lord HL, Handbook of Sample Preparation, pp. 1-24, Wiley-Blackwell, NJ, USA (2010).

[2] McCabe W, Smith J, Harriott P, Unit Operations of Chemical Engineering (7th ed.), pp. 836-844, McGraw-Hill, NY, USA (2005).

[3] Wercinski SAS, Solid Phase Microextraction: A Practical Guide, pp. 114-116, Marcel Dekker, NY, USA (1999).

[4] Pawliszyn J, Solid Phase Microextraction: Theory and Practice, pp. 21-23, Wiley-VCH, NY, USA (1997).

[5] Mullett WM, Martin P, Pawliszyn J, Anal. Chem., 73, 2383 (2001)

[6] Ho TD, Yu H, Cole WT, Anderson JL, Anal. Chem., 84, 9520 (2012)

[7] Ying S, Lasekan O, Naidu KR, Lasekan S, Molecules, 17, 13795 (2012)

[8] Ying GG, Kookana RS, Dillon P, Water Res., 37, 3785 (2003)

[9] Fernandez AR, Costley CT, Rose M, Food Addit. Contam., 20, 846 (2003)

[10] Tao LV, Zhao XE, Zhu S, Qu F, Song C, You J, Suo Y, J. Sep. Sci., 37, 2757 (2014)

[11] Knapp DR, Handbook of Derivatization Reactions, pp. 30-38, John Wiley & Sons, NJ, USA (1979).

[12] Chatterjee S, Woo SH, J. Hazard. Mater., 164(2-3), 1012 (2009)

[13] Tan IAW, Ahmad AL, Hameed BH, J. Hazard. Mater., 154(1-3), 337 (2008)

[14] Lee JJ, Um MH, Appl. Chem. Eng., 23(5), 450 (2012)