The Schulman Method of Cosurfactant Titration of the Oil/Water Interface (Dilution Method): A Review on a Well-Known Powerful Technique in Interfacial Science for Characterization of Water-in-Oil Microemulsions

Journal of Surfactants and Detergents

Volumn 18, Issue 4, 2015, Pages 547-567

  Bardhan, Soumik ^a   Kundu, Kaushik ^b,c   Chakraborty, Gulmi ^a   Saha, Swapan K ^a   Paul, Bidyut K ^b  

^a UNIVERSITY OF NORTH BENGAL   (India)

^b INDIAN STATISTICAL INSTITUTE   (India)

^c INDIAN INSTITUTE OF TECHNOLOGY MADRAS   (India)

Author keywords

Ionic liquid; Mixed surfactant; Nanomaterial; Schulman titration; Temperature insensitive microemulsion; The dilution method; Thermodynamics

Indexed keywords

BLENDING; DILUTION; DISPERSIONS; ENZYME ACTIVITY; IONIC LIQUIDS; LIQUIDS; NANOSTRUCTURED MATERIALS; OIL WELLS; PHASE INTERFACES; SURFACE ACTIVE AGENTS; THERMODYNAMICS; TITRATION;

DILUTION METHOD; MIXED SURFACTANT; NANOMATERIAL; SCHULMAN; TEMPERATURE-INSENSITIVE;

MICROEMULSIONS;

EID: 84931009541     PISSN: 10973958     EISSN: 15589293     Source Type: Journal    
DOI: 10.1007/s11743-015-1694-6     Document Type: Review

References (108)

1. Fanun M (ed) (2009) Microemulsions: properties and applications. CRC Press, USA
2. Eastoe J, Hollamby MJ, Hudson L (2006) Recent advances in nanoparticle synthesis with reversed micelles. Adv Colloid Interface Sci 5:128-130
3. Zhang W, Qiao X, Chen J (2007) Synthesis of nanosilver colloidal particles in water/oil microemulsion. Colloids Surf A 299:22-28
4. 2- electron-transfer reaction in different microheterogeneous systems. J Am Chem Soc 124:5154-5164
5. Rodríguez A, Moyá ML, López P, Mugoz E (1990) The formation of the complex pentacyano(3-pyrazincarboxylate)ferrate(II) in various water-cosolvent mixtures. Int J Chem Kinet 22:1017-1026
6. Hoar TP, Schulman JH (1943) Transparent water-in-oil dispersions: the oleopathic hydro-micelle. Nature 152:102-103
7. Kokatnur VR (1935) US Patent 2 111 000
8. Bowden D, Holmstine J (1936) US Patent 2 045 455
9. Schulman JH, Stoeckenius W, Prince LM (1959) Mechanism of formation and structure of micro emulsions by electron microscopy. J Phys Chem 63:1677-1680
10. Danielsson I, Lindman B (1981) The definition of microemulsion. Colloids Surf 3:391-392
11. Winsor PA (1954) Solvent properties of amphiphilic compounds. Butterworths, London
12. Moulik SP, Paul BK (1998) Structure, dynamics and transport properties of microemulsions. Adv Colloid Interface Sci 78:99-195
13. Paul BK, Moulik SP (1997) Microemulsions: an overview. J Disp Sci Technol 18:301-367
14. Moulik SP, Rakshit AK (2006) Physicochemistry and applications of microemulsions. J Surf Sci Technol 22:159-186
15. Ress GD, Robinson BH (1993) Microemulsions and organogels: properties and novel applications. Adv Mater 5:608-619
16. Pileni MP (1993) Reverse micelles as microreactors. J Phys Chem 97:6961-6973
17. Pes MA, Aramaki K, Nakamura N, Kunieda H (1996) Temperature-insensitive microemulsions in a sucrose monoalkanoate system. J Colloid Interface Sci 178:666-672
18. Kunieda H, Ushio N, Nakano A, Miura M (1993) Three-phase behavior in a mixed sucrose alkanoate and polyethyleneglycol alkyl ether system. J Colloid Interface Sci 159:37-44
19. Zhou M, Rhue RD (2000) Effect of interfacial alcohol concentrations on oil solubilization by sodium dodecyl sulfate micelles. J Colloid Interface Sci 228:18-23
20. Sjöblom J, Lindberg R, Friberg SE (1996) Microemulsions-phase equilibria characterization, structures, applications and chemical reactions. Adv Colloid Interface Sci 65:125-287
21. Friberg SE, Bothorel P (eds) (1987) Microemulsions: structure and dynamics. CRC Press, Boca Raton
22. Chen SH, Rajagopalan R (eds) (1990) Micellar solutions and microemulsions: structure, dynamics and statistical thermodynamics. Springer, New York
23. Giustini M, Palazzo G, Ceglie A, Eastoe J, Bumajdad A, Heenan RK (2000) Studies of cationic and nonionic surfactant mixed microemulsions by small-angle neutron scattering and pulsed field gradient NMR. Prog Colloid Polym Sci 30:25-30
24. Shrestha LK, Shrestha RG, Aramaki K, Hillb JP, Ariga K (2012) Nonionic reverse micelle formulation and their microstructure transformations in an aromatic solvent ethylbenzene. Colloid Surf A 414:140-150
25. Bumajdad A, Eastoe J, Dave S, Steytler DC, Heenan RK, Grillo I (2003) Compositions of mixed surfactant layers in microemulsions determined by small-angle neutron scattering. Langmuir 19:2560-2567
26. Palazzo G, Carbone L, Colafemmina G, Angelico R, Ceglie A, Giustini M (2004) The role of the cosurfactant in the CTAB/water/n-pentanol/n-hexane system: effect on the phase equilibria and mesophase structure. Phys Chem Chem Phys 6:1423-1429
27. Romsted LS (2001) Interfacial composition of surfactant assemblies by chemical trapping with arenediazonium ions: method and application. In: Texter J (ed) Reactions and synthesis in surfactant systems. Marcel Dekker, New York, pp 265-298 (and references therein)
28. Kunieda H, Nakano A, Pes MA (1995) Effect of oil on the solubilization in microemulsion systems including nonionic surfactant mixtures. Langmuir 11:3302-3306
29. Kunieda H, Saito YY (1992) Recent progress on HLB system. In: Lindman B, Friberg SE (eds) Organized solutions. Marcel Dekker, New York, pp 67-88
30. Moulik SP, Digout L, Aylward W, Palepu R (2000) Studies on the interfacial composition and thermodynamic properties of w/o microemulsions. Langmuir 16:3101-3106
31. Giustini M, Murgia S, Palazzo G (2004) Does the Schulman's titration of microemulsions really provide meaningful parameters? Langmuir 20:7381-7384
32. Bisal SR, Bhattacharya PK, Moulik SP (1990) Conductivity study of microemulsions: dependence of structural behavior of water/oil systems on surfactant, cosurfactant, oil, and temperature. J Phys Chem 94:350-355
33. Bardhan S, Kundu K, Saha SK, Paul BK (2013) Physicochemical investigation of mixed surfactant microemulsions: water solubilization, thermodynamic properties, microstructure, and dynamics. J Colloid Interface Sci 411:152-161
34. Bardhan S, Kundu K, Paul BK, Saha SK (2013) Interfacial composition and characterization of a quaternary water-in-oil mixed surfactant (cationic of different alkyl chain lengths + polyoxyethylene type nonionic) microemulsions in absence and presence of inorganic salts. Colloids Surf A 433:219-229
35. Bardhan S, Kundu K, Saha SK, Paul BK (2014) Effects of water content and oil on physicochemical and microenvironmental properties of mixed surfactant microemulsions. Colloids Surf A 450:130-140
36. Bardhan S, Kundu K, Das S, Poddar M, Saha SK, Paul BK (2014) Formation, thermodynamic properties, microstructures and antimicrobial activity of mixed cationic/non-ionic surfactant microemulsions with isopropyl myristate as oil. J Colloid Interface Sci 430:129-139
37. Bowcott JE, Schulman JH (1955) Emulsions. Z Electrochem 59:283-290
38. Bumajdad A, Eastoe J, Griffiths P, Steytler DC, Heenan RK, Lu JR, Timmins P (1999) Interfacial compositions and phase structures in mixed surfactant microemulsions. Langmuir 15:5271-5278
39. 12·2Br/n-hexanol/n-heptane microemulsions studied by the dilution method. Langmuir 22:3528-3532
40. Jaitely V, Karatas A, Florence AT (2008) Water-immiscible room temperature ionic liquids (RTIL) as drug reservoirs for controlled release. Int J Pharm 354:168-173
41. Moniruzzaman M, Tahara Y, Tamura M, Kamiya N, Goto M (2010) Ionic liquid-assisted transdermal delivery of sparingly soluble drugs. Chem Commun 47:1452-1454
42. Zech O, Harrar A, Kunz W (2011) Nonaqueous microemulsions containing ionic liquids-properties and applications. In: Kokorin A (ed) Ionic liquids: theory, properties, new approaches. InTech, Rijeka, pp 245-270
43. Moulik SP, Hait SK (2002) Interfacial composition and thermodynamics of formation of water/isopropyl myristate water-in-oil microemulsions stabilized by butan-1-ol and surfactants like cetyl pyridinium chloride, cetyl trimethyl ammonium bromide, and sodium dodecyl sulfate. Langmuir 18:6736-6744
44. Bayrak Y (2004) Interfacial composition and formation of w/o microemulsion with different amphiphiles and oils. Colloid Surf A 247:99-103
45. Mitra RK, Paul BK, Moulik SP (2006) Phase behavior, interfacial composition and thermodynamic properties of mixed surfactant (CTAB and Brij-58) derived w/o microemulsions with 1-butanol and 1 pentanol as cosurfactants and n-heptane and n-decane as oils. J Colloid Interface Sci 300:755-764
46. Digout L, Bren K, Palepu R, Moulik SP (2001) Interfacial composition, structural parameters and thermodynamic properties of water-in-oil microemulsions. Colloid Polym Sci 279:655-663
47. Hirata H, Hattori N, Ishida M, Okabayashi H, Frusaka M, Zana R (1995) Small-angle neutron-scattering study of bis(quaternary ammonium bromide) surfactant micelles in water. Effect of the spacer chain length on micellar structure. J Phys Chem 99:17778-17784
48. Liu Y, Chen SH, Huang JS (1998) Small-angle neutron scattering analysis of the structure and interaction of triblock copolymer micelles in aqueous solution. Macromolecules 31:2236-2244
49. Kundu K, Guin G, Paul BK (2012) Interfacial composition, thermodynamic properties, and structural parameters of water-in-oil microemulsions stabilized by 1-pentanol and mixed surfactants. J Colloid Interface Sci 385:96-110
50. Kundu K, Paul BK (2013) Interfacial composition, thermodynamic properties and structural parameters of water-in-oil microemulsions stabilized by 1-pentanol and mixed anionic + polyoxyethylene type nonionic surfactants. Colloid Polym Sci 291:613-632
51. Israelachvili J (1992) Intermolecular and surface forces. Academic Press, San Diego
52. Israelachvili JN, Mitchell DJ, Ninham BW (1976) Theory of self-assembly of hydrocarbon amphiphiles into micelles and bilayers. J Chem Soc Faraday Trans 2(72):1525-1568
53. Tanford C (1972) Micelle shape and size. J Phys Chem 76:3020-3024
54. Mitchell DJ, Ninham BW (1981) Micelles, vesicles and microemulsions. J Chem Soc Faraday Trans 2:601-629
55. Warr GG, Sen R, Evans DF, Trend JE (1988) Microemulsion formation and phase behavior of diallyldimethylammonium bromide surfactants. J Phys Chem 92:774-783
56. 2-philic surfactants 1. Synthesis and properties of aqueous solutions. Langmuir 20:9953-9959
57. Evans DF, Ninham BW (1986) Molecular forces in the self-organization of amphiphiles. J Phys Chem 90:226-234
58. 12·2Br/n-hexanol/n-heptane microemulsions: effect of the oxyethylene groups in the spacer. J Colloid Interface Sci 310:331-336
59. Evans DF, Mitchell DJ, Ninham BW (1986) Oil, water, and surfactant: properties and conjectured structure of simple microemulsions. J Phys Chem 90:2817-2825
60. Shome A, Roy S, Das P (2007) Nonionic surfactants: a key to enhance the enzyme activity at cationic reverse micellar interface. Langmuir 23:4130-4136
61. Chen DH, Liao MH (2002) Effects of mixed reverse micellar structure on stability and activity of yeast alcohol dehydrogenase. J Mol Cat B Enzym 18:155-162
62. Lan J, Zhang Y, Huang X, Hu M, Liu W, Li Y, Qu Y, Gao P (2008) Improvement of the catalytic performance of lignin peroxidase in reversed micelles. J Chem Tech Biotechnol 83:64-70
63. Poulsen AK, Arleth L, Almdal K, Scharff-Poulsen AM (2007) Unusually large acrylamide induced effect on the droplet size in AOT/Brij30 water-in-oil microemulsions. J Colloid Interface Sci 306:143-153
64. 2. Chem Eur J 8:3879-3883
65. Singh PK, Satpati AK, Kumbhakar M, Pal H, Nath S (2008) A nanoreactor for tuning the chemical reactivity of a solute. J Phys Chem B 112:11447-11450
66. Furusaki S, Ichikawa S, Goto M (2000) Recent advances in reversed micellar techniques for bioseparation. Prog Biotechnol 16:133-136
67. Huibers PDT, Shah DO (1997) Evidence for synergism in nonionic surfactant mixtures: enhancement of solubilization in water-in-oil microemulsions. Langmuir 13:5762-5765
68. Pes MA, Kunieda H (1995) Surfactant distribution in mixed surfactant microemulsions. Trends Phys Chem 5:75-89
69. Melo EP, Aires-Barros MR, Cabral JMS (2001) Reverse micelles and protein biotechnology. Biotechnol Ann Rev 7:87-129
70. Kundu K, Paul BK (2013) Physicochemical investigation of mixed surfactant reverse micelles: water solubilization and conductometric studies. Colloids Surf A 433:154-165
71. Das A, Mitra RK (2014) Does the optimum hydrophilic lipophilic balance condition affect the physical properties of mixed reverse micelles? A spectroscopic investigation. J Phys Chem B 118:5488-5498
72. Das A, Patra A, Mitra RK (2013) Do the physical properties of water in mixed reverse micelles follow a synergistic effect: a spectroscopic investigation. J Phys Chem B 117:3593-3602
73. Bardhan S, Kundu K, Saha SK, Paul BK (2013) Physicochemical studies of mixed surfactant microemulsions with isopropyl myristate as oil. J Colloid Interface Sci 402:180-189
74. Chatterjee S, Nandi S, Bhattacharya SC (2006) Interface of AOT/Igepal CO720/cyclohexane/water mixed reverse micelle by spectroscopic approach. Colloids Surf A 279:58-63
75. 2O/AOT/NaDEHP/n-heptane systems. J Phys Chem B 104:9011-9016
76. Chai JL, Li Y, Xue XN, Lu JJ, Zhang JM (2010) Synergic effect of the mixed cationic-anionic surfactants on the interfacial composition and thermodynamics of w/o microemulsions. J Disp Sci Technol 31:1050-1054
77. Goloub TP, Pugh RJ (2005) The role of the surfactant head group in the emulsification process: binary (nonionic-ionic) surfactant mixtures. J Colloid Interface Sci 291:256-262
78. Nagarajan R, Ruckenstein E (2000) Molecular theory of microemulsions. Langmuir 16:6400-6415
79. Levinger NE, Swafford LA (2009) Ultrafast dynamics in reverse micelles. Ann Rev Phys Chem 60:385-406
80. Kaur G, Chiappisi L, Prevost S, Schweins R, Gradzielski M, Mehta SK (2012) Probing the microstructure of nonionic microemulsions with ethyl oleate by viscosity, ROESY, DLS, SANS, and cyclic voltammetry. Langmuir 28:10640-10652
81. Fanun M (ed) (2011) Colloids in biotechnology. CRC Press, Boca Raton
82. Gao HC, Zhao S, Mao SZ, Yuan HZ, Yu JY, Shen LF, Du YR (2002) Mixed micelles of polyethylene glycol (23) lauryl ether with ionic surfactants studied by proton 1D and 2D NMR. J Colloid Interface Sci 249:200-208
83. Li Y, Chai JL, Xue XN, Zhang ZM (2009) Studies on the interfacial composition, thermodynamic properties and structural parameters of w/o microemulsions containing surfactant-like ionic liquid. Pol J Chem 83:1809-1820
84. nmimBr/1-pentanol/n-octane microemulsions. Tenside Surf Deterg 48:459-465
85. Chai JL, Xu L, Liu W, Zhu M (2012) Comparison of the phase behavior and thermodynamic properties between ionic liquid-oil and water-oil microemulsion systems. Chem Eng Data 57:2394-2400
86. 4] + Brij-35 + 1-butanol + toluene microemulsion. J Chem Eng Data 56:3328-3335
87. 4] + cetyltrimethylammonium bromide + alkanol + toluene microemulsions. J Disp Sci Technol 33:141-146
88. Paul S, Panda AK (2013) Physico-chemical studies on ionic liquid microemulsion: phase manifestation, formation dynamics, size, viscosity, percolation of electrical conductance and spectroscopic investigations on 1-butyl-3-methyl imidazolium methanesulfonate + water/Tween 20 + n-pentanol/n-heptane pseudoternary system. Colloid Surf A 419:113-124
89. Mukherjee I, Mukherjee S, Naskar B, Ghosh S, Moulik SP (2013) Amphiphilic behavior of two phosphonium based ionic liquids. J Colloid Interface Sci 395:135-144
90. Kar B, Bardhan S, Kundu K, Saha SK, Paul BK, Das S (2014) Physicochemical studies of water-in-oil nonionic microemulsion in presence of benzimidazole-based ionic liquid and probing of microenvironment using model C-C cross coupling (Heck) reaction. RSC Adv 4:21000-21009
91. Chen QD, Shen XH, Gao HC (2007) Formation of solid and hollow cuprous oxide nanocubes in water-in-oil microemulsions controlled by the yield of hydrated electrons. J Colloid Interface Sci 312:272-278
92. 2 in reverse microemulsions. Chem Mater 19:3376-3380
93. Sui XM, Liu YC, Shao CL, Liu YX, Xu CS (2006) Structural and photoluminescent properties of ZnO hexagonal nanoprisms synthesized by microemulsion with polyvinyl pyrrolidone served as surfactant and passivant. Chem Phys Lett 424:340-344
94. Wu JM, Yan H, Zhang XH, Wei LQ, Liu XG, Xu BS (2008) Magnesium hydroxide nanoparticles synthesized in water-in-oil microemulsions. J Colloid Interface Sci 324:167-171
95. 3 nanoparticles from water-in-oil microemulsions. Powder Technol 113:9-13
96. Kishida M, Hanaoka T, Kim WY, Nagata H, Wakabayashi K (1997) Size control of rhodium particles of silica-supported catalysts using water-in-oil microemulsion. Appl Surf Sci 121-122:347-350
97. He Y, Yang B, Cheng G, Pan H (2004) Influence of the thermodynamic stability of microemulsion on the size of the nanoparticles prepared by a coupling route of microemulsion with homogeneous precipitation. Mater Lett 58:2019-2022
98. Zhu W, Xu L, Ma J, Yang R, Chen Y (2009) Effect of the thermodynamic properties of w/o microemulsions on samarium oxide nanoparticle size. J Colloid Interface Sci 340:119-125
99. Mitra DM, Chakraborty I, Bhattacharya SC, Moulik SP, Roy S, Das D, Das PK (2006) Physicochemical studies on cetylammonium bromide and its modified (mono-, di-, and trihydroxyethylated) head group analogues. Their micellization characteristics in water and thermodynamic and structural aspects of water-in-oil microemulsions formed with them along with n-hexanol and isooctane. J Phys Chem B 110:11314-11326
100. Wu X-F, Anbarasan P, Neumann H, Beller M (2010) From noble metal to Nobel prize: palladium-catalyzed coupling reactions as key methods in organic synthesis. Angew Chem Int Ed 49:9047-9050
101. Das K, Maiti S, Ghosh M, Mandal D, Das PK (2013) Graphene oxide in cetyltrimethylammonium bromide (CTAB) reverse micelle: a befitting soft nanocomposite for improving efficiency of surface-active enzymes. J Colloid Interface Sci 395:111-118
102. Singh S, Guleria A, Singh AK, Rath MC, Adhikari S, Sarkar SK (2013) Radiolytic synthesis and spectroscopic investigations of cadmium selenide quantum dots grown in cationic surfactant based quaternary water-in-oil microemulsions. J Colloid Interface Sci 398:112-119
103. Bauduin P, Touraud D, Kunz W (2005) Design of low-toxic and temperature-sensitive anionic microemulsions using short propyleneglycol alkyl ethers as cosurfactants. Langmuir 21:8138-8145
104. Curri ML, Agostiano A, Manna L, Monica MD, Catalano M, Chiavarone L, Spagnolo V, Lugara M (2000) Synthesis and characterization of CdS nanoclusters in a quaternary microemulsion: the role of the cosurfactant. J Phys Chem B 104:8391-8397
105. Lopez F, Cinelli G, Ambrosone L, Colafemmina G, Ceglie A, Palazzo G (2004) Role of the cosurfactant in water-in-oil microemulsion: interfacial properties tune the enzymatic activity of lipase. Colloids Surf A 237:49-59
106. Meziani A, Touraud D, Zradba A, Pulvin S, Pezron I, Clausse M, Kunz W (1997) Comparison of enzymatic activity and nanostructures in water/ethanol/Brij 35 and water/1-pentanol/Brij 35 systems. J Phys Chem B 101:3620-3625
107. Lopez-Quintela M, Tojo C, Blanco MC, Rio LG, Leis JR (2004) Microemulsion dynamics and reactions in microemulsions. Curr Opin Colloid Interface Sci 9:264-278
108. Leo G, Curri ML, Cola A, Catalano M, Manna L, Quaranta F, Agostiano A, Farinola GH, Babudri F, Naso F, Della Monica M, Vasanelli L (2000) Preparation and characterisation of organic-inorganic heterojunction based on BDA-PPV/CdS nanocrystals. Mater Sci Eng B 74:175-179