Microheterogeneous solvation for aminolysis reactions in AOT-based water-in-oil microemulsions

Chemistry - A European Journal

Volumn 11, Issue 15, 2005, Pages 4361-4373

  García Río, Luis ^a   Mejuto, Juan Carlos ^b   Pérez Lorenzo, Moisés ^a  

^a UNIVERSITY OF SANTIAGO DE COMPOSTELA   (Spain)

^b UNIVERSITY OF VIGO   (Spain)

Author keywords

Aminolysis; Kinetics; Microemul sions; Reaction mechanism; Reactivity

Indexed keywords

HYDROGEN BONDS; OILS AND FATS; PHASE TRANSITIONS; RATE CONSTANTS; REACTION KINETICS; SOLVENTS; WATER;

AMINOLYSIS; DESOLVATION; REACTIVITY; REAGENTS;

MICROEMULSIONS;

EID: 22944447456     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200401067     Document Type: Article

References (53)

1. Handbook of microemulsions science and technology (Eds.: P. Kumar, K. L. Mittal), Marcel Dekker, New York, 1999.
2. R. Leung, M. H. Hou, C. Manohar, D. O. Shah, P. W. Chun, in Macro- and Microemulsions (Ed.: D. O. Shah), ACS, Washington, DC, 1985.
3. a) K. Holmberg, Adv. Colloid Interface Sci. 1994, 51, 137-174;
4. b) K. Holmberg, Curr. Opin. Colloid Interface Sci. 2003, 8, 187-196;
5. c) M. Häger, F. Currie, K. Holmberg, Top. Curr. Chem. 2003, 227, 53-74.
6. Nanoparticles and Nanostructured Films (Ed: J. H. Fendler), Wiley, Weinheim, 1998.
7. M. P. Pileni, J. Phys. Chem. 1993, 97, 6961-6973.
8. Reactivity in Reverse Micelles (Ed.: M. P. Pileni), Elsevier, 1989.
9. G. Onori, A. Santucci, J. Phys. Chem. 1993, 97, 5430-5434.
10. M. B. Temsamani, M. Maeck, I. El Hassani, H. D. Hurwitz, J. Phys. Chem. B 1998, 102, 3335-3340.
11. T. K. Jain, M. Varshney, A. Maitra, J. Phys. Chem. 1989, 93, 7409-7416.
12. D. S. Venables, K. Huang, C. A. Schmuttenmaer, J. Phys. Chem. B 2001, 105, 9132-9138.
13. D. M. Mittleman, M. C. Nuss, V. L. Colvin, Chem. Phys. Lett. 1997, 275, 332-338.
14. A. Maitra, J. Phys. Chem. 1984, 88, 5122-51 225.
15. H. Hauser, G. Haering, A. Pande, P. L. Luisi, J. Phys. Chem. 1989, 93, 7869-7876.
16. A. D'Aprano, A. Lizzio, V. T. Liveri, F. Aliotta, C. Vasi, P. Migliardo, J. Phys. Chem. 1988, 92, 4436-4439.
17. D. M. Willard, N. E. Levinger, J. Phys. Chem. B 2000, 104, 11 075-11 080.
18. R. E. Riter, J. R. Kimmel, E. P. Undiks, N. E. Levinger, J. Phys. Chem. B 1997, 101, 8292-8297.
19. R. E. Riter, D. M. Willard, N. E. Levinger, J. Phys. Chem. B 1998, 102, 2705-2714.
20. H. Shirota, K. Horie, J. Phys. Chem. B 1999, 103, 1437-1443.
21. J. Faeder, B. M. Ladanyi, J. Phys. Chem. B 2000, 104, 1033-1046.
22. L. Laaksonen, J. B. Rosenholm, Chem. Phys. Lett. 1993, 216, 429-434.
23. D. Brown, J. H. R. Clarke, J. Phys. Chem. 1988, 92, 2881-2888.
24. D. J. Tobias, M. L. Klein, J. Phys. Chem. 1996, 100, 6637-6648.
25. T. Simonson, Chem. Phys. Lett. 1996, 250, 450-454.
26. a) C. González-Blanco, L. J. Rodríguez, M. M. Velázquez, Langmuir 1997, 13, 1938-1945;
27. b) G.-W. Zhou, G.-Z. Li, W.-J. Chen, Langmuir 2002, 18, 4566-4571.
28. L. García-Río, J. R. Leis, E. Iglesias, J. Phys. Chem. 1995, 99, 12 318-12 326.
29. a) L. García-Río, J. R. Leis, Chem. Commun. 2000, 455-456;
30. b) L. García-Río, J. R. Leis, J. A. Moreira, J. Am. Chem. Soc. 2000, 122, 10 325-10 334;
31. c) L. García-Río, J. R. Leis, J. C. Mejuto, Langmuir 2003, 19, 3190-3197.
32. A. B. Maude, A. Williams, J. Chem. Soc. Perkin Trans. 2 1997, 179-183.
33. o correspond to the substrate concentrations in the aqueous microdroplet, the interface and the continuous medium respectively, referred in all cases to the total volume of the system.
34. L. García-Río, E. Iglesias, J. R. Leis, M. E. Peña, J. Phys. Chem. 1993, 97, 3437-3442.
35. L. García-Río, J. R. Leis, J. C. Mejuto, J. Phys. Chem. 1996, 100, 10 981-10 988.
36. There is a large body of studies showing the validity of the droplet model as a good description of the microheterogeneous structure of the microemulsions. The existence of this microstructure guarantees the compartmentalization of the reagents and hence the validity of the kinetic model. See for example the photon correlation spectroscopy studies showing the existence of a good correlation between the Stokes radii of AOT/Isooctane/Water ternary systems with W (M. Zulauf, H. F. Eicke, J. Phys. Chem. 1979, 83, 480-486).
37. SAXS and SANS studies also shown the existence of a linear dependence of the water pool radius with W (M. P. Pileni, J. Phys. Chem. 1993, 97, 6961-6973, and references therein).
38. Infrared spectroscopic studies of the water structure in the microemulsion show the existence of three types of water: trapped, bound and free water. These results also shown that the fraction of bound water is as much as the half of the water content for very small W values (M. B. Temsamani, M. Maeck, I. El Hassani, H. D. Hurwitz, J. Phys. Chem. B 1998, 102, 3335-3340, and references therein).
39. L. García-Río, J. C. Mejuto, M. Pérez-Lorenzo, New J. Chem. 2004, 28, 988-995.
40. There is evidence of the variation of rate constants with the W parameter of the microemulsion composition. In fact, studies on the solvolysis of microemulsions of AOT/Isooctane/water show that the rate constant of the solvolysis of the diphenylmethyl chloride in the interface of AOT-based microemulsions increases together with W as a consequence of the changes in the physical properties of the water (see ret. [25]). When solvolysis reactions are investigated in the interface of AOT-based microemulsions which occur by means of an associative mechanism it is possible to observe an increase in the rate constant as W decreases (see ref. [26b]).
41. A. C. Satterthwait, W. P. Jencks, J. Am. Chem. Soc. 1974, 96, 7018-7031.
42. A. Williams, Adv. Phys. Org. Chem. 1992, 27, 1-55.
43. Q. Li, S. Weng, J. Wu, N. Zhou, J. Phys. Chem. B 1998, 102, 3168-3174.
44. a) P. Haberfield, A. Nudelman, A. Bloom, R. Romm, H. Ginsberg, P. Steinber, J. Chem. Commun. 1968, 194-195;
45. b) P. Haberfield, L. Clayman, J. S. Cooper, J. Am. Chem. Soc. 1969, 91, 787-788;
46. c) P. Haberfield, A. Nudelman, A. Bloom, R. Romm, H. Ginsberg, J. Org. Chem. 1971, 56, 1792-1795.
47. A. J. Parker, Chem. Rev. 1969, 69, 1-32.
48. M. Balakrishnan, G. Venkoba Rao, N. Venkatasubramanian, J. Chem. Soc. Perkin Trans. 2 1974, 6-10.
49. W. P. Jencks, M. T. Haber, D. Herschlag, K. L. Nazaretian, J. Am. Chem. Soc. 1986, 108, 479-483.
50. a) J. P. Richard, J. Chem. Soc. Chem. Commun. 1987, 1768-1769;
51. b) R. A. McClelland, V. M. Kanagasabapathy, N. S. Banait, S. Steenken, J. Am. Chem. Soc. 1992, 114, 1816-1823.
52. C. F. Bernasconi, K. W. Kittredge, F. X. Flores, J. Am. Chem. Soc. 1999, 121, 6630-6639.
53. J. Andraos, A. Kresge, J. Am. Chem. Soc. 1992, 114, 5643-5646.