Sodium n-Octanoate(SOC) n-Octylammonium Chloride(OAC)

전체 글

(1)Journal of the Korean Chemical Society 2002, Vol. 46, No. 6 Printed in the Republic of Korea. n-Octylammonium Chloride(OAC)

(2) . Sodium n-Octanoate(SOC). .

(3) (2002. 8. 13 ) Mixed Micellar Properties of Sodium n-Octanoate(SOC) with n-Octylammonium Chloride(OAC) in Aqueous Solution Byung-Hwan Lee Department of Applied Chemical Engineering, Korea University of Technology, Chonan 333-860, Korea Received August 13, 2002). . Sodium n-octanoate(SOC) n-Octylammonium chloride(OAC) (CMC) !" #$(B) %& SOC '( )*+(α )& , -./0 1234. SOC/ OAC -56 7 89 :;< =%(X , γ , C , a > ∆H )& ?$< @ A BC *D34. E # 7 /FGH I $< JKLMNO P Q RS T& U VW4. EXC SOC, OAC > EY Z(α =0.5) :;< =%(∆G , ∆H > ∆S )& B " [\ CMC > B % , ] 1234. 7 , MNO B :;< = %& $^ ?=LM_ ` > /FGH *D34. : /FGH, , , !" #$ 1. i. i. i. M. i. mix. o. 1. m. o. m. o. m. ABSTRACT. The critical micelle concentration(CMC) and the counterion binding constant(B) for the mixed micellization of sodium n-octanoate(SOC) with n-octylammonium chloride(OAC) were determined as a function of the overall mole fraction of SOC(α1). Various thermodynamic parameters(Xi, γi, Ci, a iM , and ∆Hmix) for the mixed micellization of the SOC/OAC systems have been calculated and analyzed by means of the equations derived from the nonideal mixed micellar model. The results show that there are great deviations from the ideal behavior for the mixed micellization of these systems. And other thermodynamic parameters(∆Gmo ‚ ∆Hmo and ∆Smo ) associated with the micellization of SOC, OAC, and their mixture(α1=0.5) have been also estimated from the temperature dependence of CMC and B values, and the significance of these parameters and their relation to the theory of the micelle formation have been considered and analyzed by comparing each other. Key words: Mixed Surfactant System, Micellization, Critical Micelle Concentration, Counterion Binding Constant. a bc /FGH ZI de G* /F GH8 fgh iI j kX< l$Y& fgh V4. 9mn9 7 /FGH 1,2. op 8 qrsWLt, ju "G ?"G /FGH Z8 fgvI j l$Y op 8 qrsW4. EXC w G xwyz {8 0M 4|Jf }p ~XN* 8 0M 4\ Ke & I "G /F 3-5. 6,7. 495.

(4) . 496. GHY Z F 8 qrsW4. Clint p /FGH $< > ? $< l$& C 4 Y& H3Lt, Kamrath Frances p E Y & H /FGH < *D34. 0 7 bc /FGH 3Lt, ju /FGH I 7 89 > 8H F ] qr V4. 9mn9 G ~XN* 0M 4\ a bc /FGH ZI J N* 0 & 128 SLt op 8 qrs9 4. E7f wG xwyz {8 p " /FGH Q" /FGH ZI 12 * G& 89t 7 89 j l $Y& fg¡4. [¢0 0I " /F GH Q" /FGHM ££ n-octylammonium chloride(OAC) sodium n-octanoate(SOC)] ¤23 Lt, Y /FGH 34. Y /FGHI xwyz {8 ¥0 ` k0 CMC B %& 12 *. G& fgvW4. Q" /FGH¦ SOC ' ( )*+(α ) [\ CMC B % , ] 12 3Lt, 7 %Y , ?$< @A& < 7 89 :; =%& BC *D34. :;< C& ` SOC OAC > Y Z(α =0.5) 7 89 :; =%Y& BC *D34. Holland. 1,8. 9,10. 11-13. 14,15. 1. 16-18. 1. " /FGH¦ OACI n-octylamine& HClM. § -¨Lt Q" /FGH¦ SOCI n] NaOHM § -©0 H34. / FGH] H ª«k¬Yp ` 8 98% $¦ Aldrich y H& ® $ 2H9 C M y 34. (CMC) !" # $(B) %p ¯ °0 ± ²LM 1 234. ³¤ a bc /FGH] e2 ? +M ´µ & HC, ¶& kM ·< LM ¸¹0 Z /FGH 8 CMC] ºM I & 10» $ H £ % & 1234. /FGH [\ %& -/ ¼8 0M 4\ a » ¤ ½S9t, a ¤ ¾¿LMNO CMC %& EXC a ¤ ¼ ?MNO B %& #234. a bc /FGH '( )*+G& fgvI α & 0(` OAC)0 1(` SOC)n9 ¿¾<LM , ./0 CMC B %& 123Lt, :;< =%& B " ] 15 C0 35 Cn9 5 C ÀÁLM , -./0 1234. octanoic acid. 11,12,15. 19-21. 1. o. o. o.

(5) 0 SOC/OAC /FGH8 fgvI l$ CMC B %& α , [ ¢ 25 C0 123Lt, E # ] Table 1 fg vW4. 0 U VÂ ` SOC OAC % ? Y Z CMC B %p Ã³ Äp %& fg¡4. 2< ¦Å a bc / FGH ~XN* 0M #=LM_ Z<LM w G Æ8Ç sS0 CMC % ÈÇ Éw3Lt, $0 ! & I a G* ~XN * 0M #=LM_ /FGH*Ê !" 0M #& 9 ËÇ Ì4. $0 SOC 1. o. Table 1. Thermodynamic parameters for the micellization of SOC/OAC mixtures in water at 25 oC, derived by the nonideal mixed micellar model 1. CMC(mM). B. β. a1M. a2M. C1(mM). C2(mM). 0 0.15 0.34 0.50 0.66 0.83 1. 161 4.36 3.43 3.33 4.25 4.52 60.7. 0.53 0.08 0.07 0.07 0.07 0.07 0.28. − −13.8 −13.7 −13.0 −12.6 −13.1 −. 0 0.01 0.02 0.03 0.05 0.06 1. 1 0.02 0.01 0.01 0.01 0.01 0. 0 0.58 1.24 1.94 2.70 3.91 60.7. 161 3.38 2.37 1.50 1.43 0.67 0. ∆Hmix(kcal/mol) ∆Gmo (kcal/mol) − −2.04 −2.02 −1.92 −1.84 −1.88 −. −5.28 −6.04 −6.14 −6.16 −6.02 −5.94 −5.17. Journal of the Korean Chemical Society.

(6) OAC

(7) . 497. SOC. $0 a G*Y y $^Ä × ] fgvI β %p Î (2) BÏ VL t, B # ] Table 1 fgvW4. 0 U VÂ α , [¢ β %p P , 8 iLt 1 2 β % ØÙ%p −13.3& fg¡4. %p Ã³ P Q β %LM0 a bc /FGH*ÊY y Ã³ Ú ¦Å Ä =& 4. ¯ 0 "G/?"G /FGH Û³I β % Ò −2.2] EXC Ke "G/"G /FGH Û³I β % −1.4 Ã³ Äp Q %& fgvW4. a bc /FGH*ÊY y ¦Å ÈÇ Ä ÏÜ β % P Q %& fgÝ& U VW4. [¢0 SOC/OAC /F GH Û³I 0M 4\ ~XN*Y y 2 < ¦Å xwyz ÞXN*Y y wG ¦Å =ß Ä =LM_ β % Ã³ P Q %& fgvÇ Ì ¶4. ¯ Table 2 VI a G* y $^Ä ×] fgvI β %& / $0 a G* LM ¦ Z àáâ , ã¦ ∆H ] Î (3) BÏ V4. B # ] Table 1 fgvW4. Β %äå £ α 0 1 2 ∆H %p P ¾] (9 Lt, 12 ∆H % ØÙ%p Ò −1.94 kcal/molM0 P Q % & fg¡4. $0 a G*Y y Ú $ ^¦Å 0M #C æLM_ I ® ç 2 st, E # ∆H %p P Q %& èÇ Ì4. 1. 11-15. Fig. 1. Plot of X1 vs. α1 for the micellization of SOC/OAC mixtures in water at 25 oC.. )*+G(X )p ?$< @A Í Î (1) BÏ V4. 0 CMC CMC I ££ SOC OAC ] E XC X α I OAC $0 )*+G ' ( )*+G& ££ fg¡4. £ α 0 12 /FGH CMC %& Î (1) Ð=LM_ X & B3Lt, α [\ X , ] Fig. 1 fg vW4. Fig. 1 / 12 α Ñ v0 X %p Ò 0.40 0.6 Ñ v0 wÇ Æ83 4. 7 l$p $0 £ G* )*+G /FGH '( )*+G ÈÇ ÓÔ & Õ9 C e2=& fgvt, a G* J ±p ?+M 0M $& Ö& fg¡4. 1. 1,11-15. 1. 2. 2. 2. 1. 1. 1. 1. 1. 1. 2. X2 α2 - ln ------------------------ln CMC = ------------------2 2 X CMC ( 2 2) ( X 1 – X 2) 2. X1 α1 - ln ------------------------– ------------------2 2 ( X 1 – X 2 ) ( X1 CMC 1 ). (1). mix. 1. mix. mix. mix. α1 CMC 1 β = -------------------2 ln --------------------X 1 CMC 1 ( 1 – X1 ). (2). ∆H mix = X1 ( 1 – X 1 )β RT. (3). a G* 0M 4\ wG 2< $^Ä # M $ Ã$0 £ G* )*+G p 0M 4|Ç fgé4. Fig. 1 X êO] / Î (4) £ G* FK (γ )] 1. i. Table 2. Derived least square parameters of equation (8) and equation (12) for the micellization of SOC(α1=1), OAC(α1=0), and their mixture(α1=0.5) in water α1 0 (OAC) 0.5 (mix.) 1 (SOC). Eq. (8) 4. −2. −1. a(×10 K ). b(K ). c. 4.09 5.23 8.30. −0.24 −0.32 −0.49. 33.8 41.5 70.4. 2002, Vol. 46, No. 6. Eq. (12). T*(K) CMC*(mM) 295.4 297.4 297.0. 161 3.72 60.5. RMSD(%). A(K). B(kcal/mol). RMSD(%). 0.20 0.50 0.86. 323.5 305.3 306.6. −5.65 −6.29 −5.31. 1.03 1.94 2.93.

(8) . 498. %& / Î (7) BÏ V4. £ α 0 12 B CMC %& Ð=L M_ ∆ G %& B3Lt, E # ] Table 1 fgvW4. 0 U VÂ ∆ G %p α Æ 8 [¢ wÇ Éw48 Æ8I ÛÔ& (3 Lt, α % 0.5e ðw%& (34. ! & I a G* $0 0M æLM_ I ®ç 2 st, ju a G* '( )*+ G ±& a G* 0M ±p ?+M #& Ö LM_ I 8µ 2Ç Ì4. e!<LM lnCMC I " ¾=M0 Î (8) ± fgh VL ñM ∆ G p Î (9) ± fgh V4. 24. 1. o. m. o. m. 1. 1. 25. o. m. o. ∆G m = ( 1 + B )RT ln CMC 2. . Fig. 2. Plots of γ1( ) and γ2( ) vs. α1 for the micellization of SOC/OAC mixtures in water at 25 oC.. Ï VLt £ G* FK (a )I Î (5) BÏ V4. ± B γ ] α Fig. 2 -3Lt £ α 0 B a %& Table 1 fgvW4. Fig. 2 Table 1 0 (Â γ γ I £¤($< @ A)LMNO P Q RST& (3Lt, a α ? Ã³ Äp %& fgvÇ Ì4. 7 l$Yp a G* ~XN*Y y Ú 2< ¦ÅLM ¦ a G*Y 0M ÈÇ ÓÔ& LM_ eS fI l$Y4. EXC Ã$0 dãZM ëì I £ G* ) (C )I Fig. 1 Fig. 2 VI X γ êO] Î (6) Ð BÏ VLt, £ α 0 B # ] Table 1 fgvW4. 0 CMC I ` i G* ] fgvt, Table 10 U VÂ C I γ Û³äå α Æ 8 [¢ wÇ Æ848 α 8 1 íÏ î Áu Æ8=& (¦4. M. i. 22,23. i. 1. 1. i. M. 1. 2. M. i. i. i. ln CMC = aT + bT + c o. 3. (7) (8). 2. ∆G m = ( 1 + B )R( aT + bT + cT ). (9). ` SOC OAC > Y Z(α =0.5) :;< C& £ -56 " [\ CMC > B % , ] 123Lt, E # ] ££ Fig. 3 4 fgvW4. Fig. 3 40 (Â lnCMCI Î (8) ± " ¾=M f géLt BI " e¾=M wÇ Æ8I Û Ô& (34. [¢0 /FGH*Ê 1. i. 9. i. 1. i. i. i. i. i. 2. γi = exp [ β ( 1 – X 1 ) ] M. (4). a i = γ i Xi. (5). C i = γiXiCMCi. (6). /FGH Ê ï9 , ã(∆ G )p !" #$ SOC/OAC. o. m. Fig. 3. Plots of CMC vs. temperature for the micellization of SOC( ), OAC(), and their mixture( ) at α1=0.5 in water. Journal of the Korean Chemical Society.

(9) OAC

(10) . 499. SOC. Table 3. Variation of thermodynamic parameters with temperature for the micellization of SOC(α1=1), OAC(α1=0), and their mixture(α1=0.5) in water; the units of ∆Gmo and ∆Hmo are kcal/mol and that of ∆Smo is cal/mol K α1 Temp.(K). ∆Hm. ∆Sm. ∆Gm. ∆Hm. ∆Sm. ∆Gm. ∆Hm. ∆Smo. ∆Gmo. 288 293 298 303 308. −1.07 − 0.08 −1.01 −2.22 −3.54. 20.8 17.7 14.3 10.6 6.54. −4.92 −5.09 −5.28 −5.43 −5.55. −2.28 −1.40 −0.44 −0.59 −1.70. 28.1 25.2 22.0 18.6 15.1. −5.82 −5.98 −6.11 −6.23 −6.34. −2.48 −0.79 −1.06 −3.06 −5.21. 25.5 19.8 13.8 7.29 0.39. −4.86 −5.03 −5.17 −5.26 −5.33. 0(OAC) o. o. 0.5 (mixture) o. o. 1 (SOC). o. o. o. o. o 2 d ( ∆G m ⁄ T ) 3 2 ∆H m = –T ------------------------ = –( 1 + B )R ( 2aT + bT ) dT p (10) o. o. ∆H m – ∆G m o 2 ∆S m = -------------------------- = –( 1 + B )R (3aT + 2bT + c ) (11) T Table 3 êO / 12 @ó " 0 ` SOC OAC(4 a G* Z(α =0.5) ∆ G % ôõ P Q %& fgvWLt, /FGH ∆ S % ` G* %(4 ôõ P %& fgvW4. 0M 4\ a G*& / 2< ¦Å wG ¦Å a G* 0M #=LM_ ö k *Ê !" ÷Sø fùÇ st, E # /FGH ∆ S p P %& E XC ∆ G p P Q %& fg¡4. ¯ Table 3 / " Æ8 [\ :; =% , I ` G*f /FGH Û³ @a ÉwI Û Ô& (34. £ -56 B ∆ H %& ∆ S % Fig. 5 -3L t, E # @a ¤& W4. [¢0 ∆ H ∆ S yI Î (12) ± e¾=8 GúñM ∆ G (=∆ H -T∆ S )p Î (13) fgh V4. 0 ¼ AI " (isostructural temperature)M 0 ûÒ 12 " (T)8 A ±L/ Î (13) üý þp Ó Ì4. ÿ, ∆ G ∆ S 8 Ó sI " 8 " t ¯ BI E ∆ G %& fg¡4. ðwÊò²LM Fig. 5 £ 56 Î (12) ¼(A) ¯(B)& 3Lt RMSD % =ß Table 2 fgvW4. 0 U VÂ OAC " I 323.5 KM0 ` SOC /FGH(α =0.5) %(4 Ò 17 C 2 P %& fgvW4. Î (13) / A % 1. o. m. o. m. o. Fig. 4. Plots of β(counterion binding constant) vs. temperature for the micellization of SOC( ), OAC( ), and their mixture( ) at α1=0.5 in water.. ∆ G I Î (9) 0 EXC ∆ H ∆ S p £ £ Î (10) (11) BÏ V4. ³¤ Fig. 3 VI £ -56 CMC % Î (8)& <. ðwÊò²LM $ a, b > c] 3Lt, E # ] Table 2 fgvW4. EXC Table 2I £ -56 ðw% (CMC*) E " (T*) > RMSD(root mean square deviation) %& B =ß fgvW 4. 0 U VÂ ` OAC T* % ` SOC /FGH (α =0.5) T* %(4 Ò 2 C 2 ÄÇ fgé4 . Table 2 VI a, b > c %& £ -56 :; =%¦ ∆ G , ∆ H > ∆ S & ££ Î (9), (10) > (11) B3Lt, E # ] Table 3 f gvW4. o. o. m. o. m. m. 26. 1. o. o. m. 2002, Vol. 46, No. 6. o. m. o. m. m. o. m. o. o. m. m. o. m. o. m. o. m. o. m. o. m. o. o. m. m. o. m. 25,26. o. 1.

(11) . 500. 8I ÛÔ& (34. ju α 0.5e ∆ G p 8 µ Äp %& fgvWLt, ¶p $0 a G* #LM ¦ /FGH ∆ S % ®ç Æ83 4. " Æ 8 [¢ ∆ H , ∆ S > ∆ G %p @a ÉwI Û Ô& (3Lt, ∆ H & ∆ S - ½p " I ` OAC Û³8 ` SOC > /FGH(α =0.5) Û³(4 Ã³ P %& f gvW4. 1. o. m. o. m. o. m. o. o. m. o. m. m. o. m. 1. Fig. 5. Plots of ∆ Hmo vs. ∆ Smo for the micellization of SOC( ), OAC( ), and their mixture( ) at α1=0.5 in water.. Ä&Ü ∆ S % @a %ñM ∆ G % p ®ç P Q %& èÇÌ4. [¢0 OCA Û³ (4 SOC /FGH 0 ∆ S 8 ®ç ÈÇ Ä Ç Ì4. o. o. m. m. o. m. ∆H m = A ∆S m + B o. o. (12). ∆G m = B + ( A – T ) ∆S m o. o. (13). /FGH 0 ~XN* 0M 4LM ¦ a G* 2< ¦Å wG ¦Å 0M #& Ç st, E # $0I J ±p ?+M a G* 0M Ì4. $0 £ G* FK FK %p a G*Y y Ú ¦ÅLM ¦ Ã³ Äp %& fgvWLt $< l$0 ÈÇ Q RST& (34. a G*Y y Ú ¦ÅLM ¦ β ØÙ%p −13.2] E XC ∆ H ØÙ%p −1.94 kcal/molM0 Ã³ P Q %& fgvWLt, 7 %p 4\ bc /FGH %(4 ôõ Äp %& fgvW4 . ∆ G %p −5.2−6.2 kcal/molLM0 Q %& f gvWLt, α Æ8ÏÜ ∆ G %p Éw48 Æ SOC/OAC. mix. o. m. 1. o. m. 1. Holland, P. M. In Mixed Surfactant Systems; Holland, P. M.; Rubingh, D. D., Ed.; ACS Symposium Series; Washington DC., U. S. A., 1992; p. 31. 2. Park, J. W.; Chung, M. A.; Choi, K. M. Bull. Korean Chem. Soc. 1989, 10, 437. 3. Bergstrom, M.; Eriksson, J. C. Langmuir 2000, 16, 7173. 4. Matsubara, H.; Muroi, S.; Kameda, M.; Ikeda, N.; Ohta, A.; Aratono, M. Langmuir 2001, 17, 7752. 5. Bai, G.; Wang, J.; Yan, H.; Li, Z.; Thomas, R. K. J. Phys. Chem. B 2001, 105, 9576. 6. Kresheck, G. C. J. Phys. Chem. B 2001, 105, 4380. 7. Matsubara, H.; Ohta, A.; Kameda, M.; Ikeda, N.; Aratono, M. Langmuir 2000, 16, 7589. 8. Clint, J. H. In Surfactant Aggregation; Chapman and Hall; New York, 1992; p. 130. 9. Kamrath, D. F.; Franses, E. I. In Surfactants in Solution; Mittal K. L. Ed.; Plenum Press; New York, U. S. A., 1984; p. 129. 10. Kamrath, D. F.; Franses, E. I. J. Phys. Chem. 1984, 88, 1642. 11. Lee, B. H. J. Kor. Chem. Soc. 1999, 43, 614. 12. Lee, B. H. J. Kor. Chem. Soc. 1998, 42, 519. 13. Chung, J. J.; Kim, Y. C.; Lee, B. H. J. Kor. Chem. Soc. 1997, 41, 284. 14. Chung, J. J.; Lee, S. H.; Kim, Y. C.; Lee, B. H. J. Korean Ind. & Eng. Chemistry 1998, 9, 968. 15. Lee, B. H. J. Kor. Chem. Soc. 1997, 41, 12. 16. De Lesi, R.; Inglese, A.; Milioto, S.; Pellerito, A. J. Colloid & Interface Sci. 1996, 180, 174. 17. Semchyschyn, D. J.; Carbone, M. A.; MacDonald, P. M. Langmuir 1996, 12, 253. 18. Kamenka, N.; Burgaud, I.; Zana, R.; Lindman, B. J. Phys. Chem. 1994, 98, 6785. 19. Zana, R.; Levy, H. Langmuir 1997, 13, 402. 20. Chatterjee, A.; Moulik, S. P.; Sanyal, S. K.; Mishra, B. Journal of the Korean Chemical Society.

(12) OAC

(13) . SOC. K.; Puri, P. M. J. Phys. Chem. B 2001, 105, 12823. 21. Shanks, P. C.; Franses, E. I. J. Phys. Chem. 1992, 96, 1794. 22. Holland, P. M.; Rubingh, D. N. J. Phys. Chem. 1983, 87, 1984.. 2002, Vol. 46, No. 6. 501. 23. Rathman, J. F.; Christian, S. D. Langmuir 1990, 6, 391. 24. Zana, R.; Levy, H.; Papoutsi, D.; Beinert, G. Langmuir 1995, 11, 3694. 25. Lee, B. H. J. Kor. Chem. Soc. 2000, 44, 177. 26. Lee, B. H. J. Kor. Chem. Soc. 2001, 45, 7..

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Sodium n-Octanoate(SOC) n-Octylammonium Chloride(OAC) 

Sodium n-Octanoate(SOC) n-Octylammonium Chloride(OAC)