表面活性剂化学和一般相行为

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1 : // / o A W mn W mn = o A - [1] 1

2 = o- o - (CMC) CMC CMC 2.3 CMC [2-5] [6-8] Gbbs [9] 2

3 α β τ α β 0 X α β 2.1 3

4 2.1 Gbbs Γ (a) Gbbs 0 (b) Gbbs X solvent C on ce ntr α β ( a ) X τ X C on ce ntr Solute α β ( b ) X Dstance to 4

5 Gbbs Gbbs X 0 Γ = n A (2.1.1) A α β XX' Γ XX' n α β U = U U U α β α = TS = TS + U α β β + U PV PV β α + + μ n μ n α β (2.1.2) U = TS + γa + μ n (2.1.3) T, S, A,µ, n, du = TdS + S dt + γda + Adγ + μ dn + n dμ (2.1.4) du = TdS PdV + μ dn (2.1.5) = TdS + γda + μ dn du (2.1.6) S dt + Adγ + n dμ = 0 (2.1.7) 5

6 2.1.9 Γ Gbbs dγ = Γ dμ (2.1.8) dγ = Γ dμ d (2.1.9) 1 1 Γ 2 μ 2 Gbbs Γ 1 = dγ = Γ 2 dμ 2 (2.1.10) Γ 2 μ = μ o + RT ln a so d μ = cste + RTd ln (2.1.11) a o μ 1 298K Gbbs dγ = Γ RTd ln (2.1.12) 2 a 2 1 dγ Γ 2 = (2.1.13) RT d ln a 2 R - M + CMC dγ = Γ dμ Γ dμ (2.1.14) R R Μ Γ R = Γ Μ M a = 1/ 2 2 (a Ra M) Gbbs 1 dγ Γ 2 = (2.1.15) 2RT d ln a M + M + Gbbs

7 Gbbs A B 25 o C 72.5mN CMC B C 7

8 2.2 Gbbs A Interfacal tenson, γ Amount adsorbed, Γ B near lnear part C γ = γ c ln concentraton Concentraton 8

9 Gbbs [14] -- Gbbs Langmur[15] Szyszkowsk[16] Frumkn[17] Guggenhem Adam [18] Gbbs mn m -1 Frumkn π γ Γ 1 γ = π = 2.303RT Γ m log (2.1.16) Γm mol cm -2 [19] mn m % pc 20 G pc 20 9

10 CH 3 (CH 2 )n M M n π= 20 mn m-1 G = n G (-CH 2 -) + G (M) + G (CH 3 -) (2.1.17) - G (-CH 2 -) log(c) 20 = pc 20 = n + constant 2.303RT (2.1.18) (G (M) 1 Γ m pc20 Traube Log C s = B n Log K T (2.1.19) Cs B n K T Traube K T 3 [21] n - G (-CH = K T = exp C + 2RT C 2 n 1 -) (2.1.20) 3.5 -CH 2 - pc 20 a b 10

11 20 mn m mn m -1 Ptt [22] γ CMC γ mn Γ m Γ m γ mn Γ m γ mn Krafft Gbbs Γ m Rosen Γ m C8 C20 [19]

12 2.2.1 Krafft Krafft Krafft T K CMC CMC. T K T K Krafft Krafft Krafft Krafft 12

13 2.3 Krafft T K T K T K 0.3 Solublty curve Mcelles Concentraton (mol dm -3 ) Hydrated crystals CMC curve Monomers n H 2 O T K Temperature / C 13

14 2.2.2 CMC Krafft POE OE OE POE CMC CMC 14

15 2.4 Magntude of property Osm otc pressure Turbdty Solublzaton Magnetc resonance Surface tenson Equvalent conductvty Self-dffus on CMC Concentraton of surfactant 15

16 G m = G(HC) + G(contact) + G(packng) + G(HG) (2.3.1) G(HC) G(contact) G(packng) G(HG) Gbbs-Helmholtz G m = H m - T S m H m S m G m H m 16

17 [27] Tanford [1] S m [28 29] 166 [30] S K K K S 2 3 n S + S S... S + S... (2.3.2) S n K n n = 2 ( G, H, S ) K n K n CMC K n ns S n (2.3.3) n S CMC ns ms + S (2.3.4) n m S n K m 17

18 [ mcelles] [ monomers] n [ Sn ] [] S n K m = = (2.3.5) n G ο = RT ln K = RT lns nrt lns (2.3.6) m m n + ο n G RT m = lns + RTlnS n n (2.3.7) CMC CMC S S n G ο RT ln(cmc) (2.3.8) M, m ns ( )C S x y α + n p n (2.3.9) C α α = p/n K m [ S ] n = (2.3.10) x n y ( n p) [ S ] [ C ] 18

19 p x y { [ n ] n S n p C } ο Gm = -RT ln S ln ( )ln (2.3.11) CMC [S - (+) ] = [C + (-) ] = CMC p G ο M, m RT 2 ln(cmc) n ( ) Gbbs S ( G ) d dln(cmc) S = = RT R ln(cmc) (2.3.13) dt dt Gbbs H o 2 dln(cmc) H = G + T S = -RT (2.3.14) dt 2 p dln( CMC) H = -RT 2 n dt (2.3.15) [33-35] 19

20 2.3.2 CMC CMC CMC CMC CMC CMC Klevens [36] log (CMC) = A B (2.3.16) 10 n c A B n c C n H 2n+1 A B log 10 2 (B ) [37] B 0.62 B CMC CMC [19] 3.5 CMC C12 CMC mol dm -3 CMC mol dm -3 CMC 20

21 CMC CMC L + > Na + > K + > Cs > N (CH 3 ) 4 > N(CH 2 CH 3) 4 > Ca 2+ Mg 2+ CMC F - > Cl - > Br - > I - CMC CMC CMC CMC log (CMC) a log + b (2.3.17) 10 = 10 C CMC 0 70 C CMC [38] 2.2 Krafft 21

22 2.3.3 [39 40] Hartley[41] 1936 ph Mtchell Nnham[42] Israelachvl[43] 2.5, a o ; (s), v;, c l. c l v R mc 3 [(4 / 3) π R ] v N = V / v = / (2.3.18) mc mc 22

23 A mc a o N 2 [ 4π Rmc ] o = A / a (2.3.19) mc ao = / v a R ) 1/ 3 (2.3.20) /( o mc = c l R mc v /( aolc ) 1/ 3 (2.3.21) P c P c = v/( aolc ) (2.3.22) v a o P c P c Table 2.1 P c, P c = v/a o c l < >1.0 23

24 Fgure 2.5 P c ( ) P c = v/a o c l (After Israelachvl [43] p. 247) Interfacal (hydrophobc) attracton Head group (hydrophlc) nteracton R mc l c Volume v Area a o 24

25 Fgure 2.6 (P c ) v/a o l c 1/3 Mcelles Cubc Ol-n-water 1/3 < v/a o l c <1/2 Hexagonal Cubc v/a o l c 1 Mrror plane Lamellar v/a o l c 1 Cubc Water-n-ol v/a o l c > 1 Reversed hexagonal Cubc Reversed mcelles 25

26 2.4 [ 44 45] %

27 H 1 H 2 H 2 H 1 L -. I 1 I 2 I [46 47]. V 1 V 2 V 1 V 2 H 1 L α L α H 2 > > 27

28 30-60% L a Neat H 1 Mddle H 2 I 1 Vscous sotropc I 2 V 1 V 2 L 1 Vscous sotropc L Fontell [46] 28

29 C16EO C16EO8- L 1 L (After Mtchell et al. J. Chem. Soc. Faraday Trans. I 1983, 79, 975). 90 Water + L 1 L α L 2 Temperature / C L 1 H 1 V 1 Surfactant 0 I Composton / Wt% C 16 EO 8 29

30 (After Laughln [44]) Lqud Lqud Temperature / C Lqud + Lα Lamellar (L α) Cubc Inverse hexagonal Composton / Wt% AOT 30

31 REFERENCES 1. Tanford, C. The Hydrophobc Effect: formaton of mcelles and bologcal membranes John Wley & Sons, 1978, USA. 2. Dukhn, S. S.; Kretzschmar, G.; Mller, R. Dynamcs of Adsorpton at Lqud Interfaces Elsever, Amsterdam, Rusanov, A. I.; Prokhorov, V. A. Interfacal Tensometry, Elsever, Amsterdam, Chang, C.-H.; Franses, E. I. Collod Surf. 1995, 100, Mller, R.; Joos, P.; Fanermann, V. Adv. Collod Interface Sc. 1994, 49, Ln, S. -Y.; McKegue, K.; Maldarell, C. Langmur 1991, 7, Hsu, C. -H.; Chang, C. -H.; Ln, S. -Y. Langmur 1999, 15, Eastoe, J.; Dalton, J. S. Adv. Collod Interface Sc. 2000, 85, Gbbs, J. W. The Collected Works o f J. W. Gbbs, Longmans, Green, New York, 1931, Vol. I, p Elworthy, P. H.; Mysels, K. J. J Collod Interface Sc. 1966, 21, Lu, J. R.; L, Z. X.; Su, T. J.; Thomas, R. K.; Penfold, J. Langmur 1993, 9, Bae, S.; Haage, K.; Wantke, K.; Motschmann, H. J. Phys. Chem. B 1999, 103, Downer, A.; Eastoe, J.; Ptt, A. R.; Penfold, J.; Heenan, R. K. Collods Surf. A 1999, 156, Eastoe, J.; Nave, S.; Downer, A.; Paul, A.; Rankn, A.; Trbe, K.; Penfold, J. Langmur 2000, 16, Langmur, I. J. Am. Chem. Soc. 1848, 39, Szyszkowsk, B. Z. Phys. Chem. 1908, 64, Frumkn, A. Z. Phys. Chem. 1925, 116, Guggenhem, E. A.; Adam, N. K. Proc. Roy. Soc. (London), 1933, A139, Rosen, M. J. Surfactants And Interfacal Phenomena, John Wley & Sons, 1989, USA. 20. Traube, I. Justus Lebgs Ann. Chem. 1891, 265, Tamak, K.; Yanagush, T.; Hor, R. Bull. Chem. Soc. Jpn. 1961, 34,

32 22. Ptt, A. R.; Morley, S. D; Burbdge, N. J.; Quckenden, E. L. Coll. Sur f. A 1996, 114, Hato, M.; Tahara, M.; Suda, Y. J. Coll. Interface Sc. 1979, 72, Staples, E. J.; Tddy, G. J. T. J. Chem. Soc., Faraday Trans , 74, Tddy, G. J. T. Phys. Rep. 1980, 57, Schott, H. J. Pharm. Sc. 1969, 58, Frank, H. S.; Evans, M.W. J. Chem. Phys. 1945, 13, Evans, D. F.; Wghtman, P. J. J. Collod Interface Sc. 1982, 86, Patterson, D.; Barbe, M. J. Phys. Chem. 1976, 80, Evans, D. F. Langmur 1988, 4, Hunter, R. J. Foundatons of Collod Scence Volume I, Oxford Unversty Press, 1987, New York. 32. Evans, D. F.; Nnham, B. W. J. Phys. Chem. 1986, 90, Corkhll, J. M.; Goodman, J. F.; Walker, T.; Wyer, J. Proc. Roy. Soc. (London),A 1969, 312, Mukerjee, P. J. Phys. Chem. 1972, 76, Anansson, E. A. G.; Wall, S. N. J. Phys. Chem. 1974, 78, Klevens, H. J. Am. Ol Chem. Soc. 1953, 30, 7, Wllams, E. F.; Woodberry, N. T.; Dxon, J. K. J. Collod Interface Sc. 1957, 12, Kresheck, G. C. In Water-a comprehensve treatse, pp Ed. F. Franks, Plenum Press, 1975, New York. 39. McBan, J. W. Trans. Faraday Soc. 1913, 9, Reychler, Kollod-Z., 1913, 12, Hartley, G. S. Aqueous solutons of paraffn chan salts, Hermann & Ce, Pars, Mtchell, D. J.; Nnham, B. W. J. Chem. Soc. Faraday Trans , 77, Israelachvl, J. N. Intermolecular and Surface Forces, Academc Press, London, 1985, p

33 44. Laughln, R. G. The Aqueous Phase Behavour of Surfactants, Academc Press, London, Chandrasekhar, S. Lqud Crystals Cambrdge Unversty Press, 1992, New York. 46. Fontell, K.; Kox, K. K.; Hansson, E. Mol. Cryst. Lqud Cryst. Letters 1985, 1, Fontell, K. Coll. Polymer Sc. 1990, 268,

34 1- Gbbs du Noüy - A.1.DU Noüy [A1-A4] A.1 - A.1 du Noüy Volume of lqud rased Rng γ eq = F 4π R (A.1) R F = ( ρ ρ ) 1 2 gv (A.2) 34

35 ρ 1 ρ 2 g (9.81 ms -2 ) V - ρ 1 ρ 2 Harkns Jordan[A1] (A1) γ eq F = γ eq f = 4π R f (A.3) f Harkns -Jordan γ eq mn m - 1 Harkns Jordan Zudema Waters A4 f = γ 1 2 U 4 eq ( ρ ρ ) Rr (A.4) R 10mm r 0.2mm U 120mm 20 C - (ρ 1 -ρ 2 ) = ( γ eq ) fk= (A.5) 35

36 A.2 -DVT DVT DVT Lauda TVT1 [A2,A3] DVT A.2 (mg) (2πr cap γ) V A.6 [A4] γ V ρg γ = f (A.6) 2πr cap ρ g r cap f [A5]. A.2 motor plunger syrnge soluton temperature controlled jacket capllary 2πr cap γ lght beam drop lght sensor mg sealed cuvette 36

37 A mol dm mol dm -3 1 Debye-Hückel [A6,A7] γ ± Debye-Hückel log 1 2 γ ± = A z + z I (A.7) z, I A I A 1 2 I = m z (A.8) 2 1/ 2 3 F ρ A = 3 4 N a ln10 2( o rrt) (A.9) π ε ε m z ρ. F, N a, R, ε 0 ε r 1:1 (A.7) 0.01 mol dm -3. Debye-Hückel 1 2 A z + z I log γ ± = (A.10) BaI a 3 9 Å [A8] B 37

38 1/ 2 2 2F ρ B = 0 rrt (A.11) ε ε (A.10) Debye-Hückel 1:1 0.1 mol dm -3 [A7]. 298 K, A = mol -1/2 kg 1/2 B = m -1 mol -1/2 kg 1/2 38

39 A1. Harkns, W.D.; Jordan, H.F., J. Am. Chem. Soc., 1930, 52, A2. Mller, R.; Joos, P.; Fanerman, V.B., Adv.Coll.Int.Sc., 1994, 49, 249. A3. Dukhn, S.S.; Kretzschmar, G.; Mller, R., Dynamcs of Adsorpton at Lqud Interfaces, 1995 (Amsterdam : Elsever). A4. Rusanov, A.I.; Prokhorov, V.A., 'Interfacal Tensometry', Eds. Möbus, D.; Mller, R., 1996 (Amsterdam : Elsever). A5. Mller, R.; Schano, K-H.; Hofmann, A., Collods Surf A, 1994, 92, 33. A6. Atkns, P.W.,'Physcal Chemstry' 6 th edton, 1998, (Oxford Unversty Press: Oxford). A7 Robbns, J.,'Ions n Soluton', 1972 (Oxford Unversty Press, Oxford). A8. Levne, I.N.'Physcal Chemstry', 4 th edton, 1995 (McGraw-Hll Book Co.; Sngapore). 39

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