양쪽성 계면활성제의 유도체합성 및 계면성에 관한 연구(제6보)-양쪽성 계면활성제의 미셀 형성에 대한 열역학적 고찰-

노윤찬; 이선주; 남기대

Journal of the Korean Industrial and Engineering Chemistry, Vol.6, No.4, 548-555, August, 1995

Syntheses and Surface Active Properties of Amphoteric Surfaetant Derivatives(6) -Thermodynamics of Micellization of Amphoteric Surfactant Derivatives-

노윤찬, 이선주, 남기대

초록

합성한 카르복시화 아미드류 3종, 술폰화 또는 황산화 이미다졸린류 3종 그리고 술폰화 아미드류 3종 등 총 9종의 양쪽성 계면활성제에 대하여 15∼45℃의 온도 범위에서 임계미셀농도(cmc)를 결정하였다. 미셀 형성에 있어 자유 에너지 변화는 엔탈피 및 엔트로피의 변화로 전환될 수 있다. 즉 미셀화에 따른 표준자유에너지 변화 ΔG⁰m는 열역학적으로 취급해서 cmc로 부터 산출하고 ΔG⁰m를 ΔH⁰m과 ΔS⁰m으로 분리할 수 있다. 그리고 이들의 결과들은 이미 알려진 다른 문헌상의 값들과 비교하였다. 미셀 형성 과정은 전적으로 계면효과에 기인하는 결과를 얻었고 15∼45℃ 범위에서 온도와 관계없이 발열과정이며 ΔH⁰m 값은 -1.2∼-2.3Kca1/mol이었다. 이들 양쪽성 계면활성제의 친수성이 증가하면 계면 효과는 감소한다 15∼45℃ 범위에서 자발적으로 미셀 형성 과정이 진행되고, 엔트로피 조절 과정에 의하여 미셀 형성이 이루어지며 엔트로피는 증가한다.

The critical micelle concentrations(cmc) was studied on nine kinds of amphoteric surfactants; three kinds of carboxylated amides, three kinds of sulfated or sulfonated imidazoline and three kinds of sulfonated amides at 15 to 45℃ range. The change of free energy about micelle formation can be converted into the change of enthalpy and entropy. The standard free energy change ΔG⁰m of micellization was estimated from the cmc, by treating she formation of micelles as thermodynamics; she determination of the variation of cmc the enables ΔG⁰m to be split into the corresponding. ΔH⁰m and ΔS⁰m. These results were examined by making a comparison between this results and the previously known values. The process of micelle formation obtained the result that perfactly was attributed to interface effect and the exothermic reaction which ΔH⁰m values were -1.2∼ -2.3Kcal/mol was not related with temperature at 15 to 45℃ range. The interface effect was decresed with the hydrophilic increase of the amphoteric surfactants. The process of micelle formation was proceeded spontaneously at 15 to 45℃ range and entrophy increased with consisting of micelle formation to control entrophy process.

[References]

Tanford C, "The Hydrophobic Effect: Formation of Micelles and Biological Membranes," 2nd Ed., 52, John Wiley, New York (1980)
Stecker MM, Benedek GB, J. Phys. Chem., 88, 6519 (1984)
Hall DG, Pethica BA, "Nonionic Surfactants," M.J. Schick Ed., 516, Marcel Dekker, New York (1967)
Ruckenstein E, Chi JC, J. Chem. Soc.-Faraday Trans., 71, 1690 (1975)
Nagarajan R, Ruckenstein E, Sep. Sci. Technol., 16, 1429 (1981)
Miller CA, Neogi P, AIChE J., 26, 212 (1980)
Mallikarjun R, Dadyburjor DB, J. Colloid Interface Sci., 84, 73 (1981)
Schick MJ, Hall DG, "Thermodynamics of Micelle Formation," 517, Marcel Dekker, New York (1966)
Hall DG, Kolloid Z. Z. Polym., 250, 895 (1972)
Hill TL, "Thermodynamics of Small Systems," 1, 2, Benjamin, New York (1963)
노윤찬, 김홍수, 남기대, 한국유화학회지, 11, 107 (1994)
노윤찬, 강윤석, 남기대, 한국유화학회지, 11, 115 (1994)
노윤찬, 김태영, 남기대, 한국공업화학회지, 게재중 (1995)
KS-M0001 (1991)
Gurney, Ionic Processes in Solution ,McGraw-Hill, New York (1953)
Kauzmann, Adv. Protein Chem., 14, 1 (1959)
Goddard ED, Hoeve CA, J. Phys. Chem., 61, 593 (1957)
Swarbrick J, Daruwala J, J. Phys. Chem., 73, 2627 (1969)
Tori K, Nakagawa T, Kolloid Z. Z. Polym., 189, 50 (1963)
Flockhart BD, J. Colloid Sci., 16, 484 (1961)
Corkill JM, Goodman JF, Trans. Faraday Soc., 60, 996 (1964)
Crook EH, Trebbi GF, J. Phys. Chem., 68, 3592 (1964)
Mukerjee P, Adv. Colloid Interface Sci., 1, 241 (1967)
Schick MJ, J. Phys. Chem., 67, 1796 (1963)
Molyneux P, Rhodes CT, Trans. Faraday Soc., 61, 1043 (1965)
Benjamin L, J. Phys. Chem., 68, 3375 (1964)

[Referenced By]

[1] Tanford C, "The Hydrophobic Effect: Formation of Micelles and Biological Membranes," 2nd Ed., 52, John Wiley, New York (1980)

[2] Stecker MM, Benedek GB, J. Phys. Chem., 88, 6519 (1984)

[3] Hall DG, Pethica BA, "Nonionic Surfactants," M.J. Schick Ed., 516, Marcel Dekker, New York (1967)

[4] Ruckenstein E, Chi JC, J. Chem. Soc.-Faraday Trans., 71, 1690 (1975)

[5] Nagarajan R, Ruckenstein E, Sep. Sci. Technol., 16, 1429 (1981)

[6] Miller CA, Neogi P, AIChE J., 26, 212 (1980)

[7] Mallikarjun R, Dadyburjor DB, J. Colloid Interface Sci., 84, 73 (1981)

[8] Schick MJ, Hall DG, "Thermodynamics of Micelle Formation," 517, Marcel Dekker, New York (1966)

[9] Hall DG, Kolloid Z. Z. Polym., 250, 895 (1972)

[10] Hill TL, "Thermodynamics of Small Systems," 1, 2, Benjamin, New York (1963)

[11] 노윤찬, 김홍수, 남기대, 한국유화학회지, 11, 107 (1994)

[12] 노윤찬, 강윤석, 남기대, 한국유화학회지, 11, 115 (1994)

[13] 노윤찬, 김태영, 남기대, 한국공업화학회지, 게재중 (1995)

[14] KS-M0001 (1991)

[15] Gurney, Ionic Processes in Solution ,McGraw-Hill, New York (1953)

[16] Kauzmann, Adv. Protein Chem., 14, 1 (1959)

[17] Goddard ED, Hoeve CA, J. Phys. Chem., 61, 593 (1957)

[18] Swarbrick J, Daruwala J, J. Phys. Chem., 73, 2627 (1969)

[19] Tori K, Nakagawa T, Kolloid Z. Z. Polym., 189, 50 (1963)

[20] Flockhart BD, J. Colloid Sci., 16, 484 (1961)

[21] Corkill JM, Goodman JF, Trans. Faraday Soc., 60, 996 (1964)

[22] Crook EH, Trebbi GF, J. Phys. Chem., 68, 3592 (1964)

[23] Mukerjee P, Adv. Colloid Interface Sci., 1, 241 (1967)

[24] Schick MJ, J. Phys. Chem., 67, 1796 (1963)

[25] Molyneux P, Rhodes CT, Trans. Faraday Soc., 61, 1043 (1965)

[26] Benjamin L, J. Phys. Chem., 68, 3375 (1964)