Rate-dependent lowering of surface tension during transformations of water-soluble surfactants from bolaform to monomeric structures

Langmuir

Volumn 14, Issue 9, 1998, Pages 2235-2237

  Jong, Lana I ^a   Abbott, Nicholas L ^a  

^a University of California   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; MONOMERS; REACTION KINETICS; REDOX REACTIONS; SOLUBILITY; SOLUTIONS; SURFACE TENSION; SYNTHESIS (CHEMICAL);

BOLAFORM;

SURFACE ACTIVE AGENTS;

EID: 0032051116     PISSN: 07437463     EISSN: None     Source Type: Journal    
DOI: 10.1021/la980235c     Document Type: Article

References (33)

1. Electrochemical oxidation and reduction of ferrocene-based surfactants in aqueous solution can lead to large and reversible changes in surface tension: (a) Gallardo, B. S.; Hwa, M. J.; Abbott, N. L. Langmuir 1995, 11, 4209-4212. (b) Bennett, D. E.; Gallardo, B. S.; Abbott, N. L. J. Am. Chem. Soc. 1996, 118, 6499-6505. (c) Gallardo, B. S.; Metcalfe, K. L.; Abbott, N. L. Langmuir 1996, 12, 4116-4124.
2. Electrochemical oxidation and reduction of ferrocene-based surfactants in aqueous solution can lead to large and reversible changes in surface tension: (a) Gallardo, B. S.; Hwa, M. J.; Abbott, N. L. Langmuir 1995, 11, 4209-4212. (b) Bennett, D. E.; Gallardo, B. S.; Abbott, N. L. J. Am. Chem. Soc. 1996, 118, 6499-6505. (c) Gallardo, B. S.; Metcalfe, K. L.; Abbott, N. L. Langmuir 1996, 12, 4116-4124.
3. Electrochemical oxidation and reduction of ferrocene-based surfactants in aqueous solution can lead to large and reversible changes in surface tension: (a) Gallardo, B. S.; Hwa, M. J.; Abbott, N. L. Langmuir 1995, 11, 4209-4212. (b) Bennett, D. E.; Gallardo, B. S.; Abbott, N. L. J. Am. Chem. Soc. 1996, 118, 6499-6505. (c) Gallardo, B. S.; Metcalfe, K. L.; Abbott, N. L. Langmuir 1996, 12, 4116-4124.
4. We use the term "equilibrium surface tension" to mean the surface tension of the system in the absence of an ongoing chemical reaction. See also ref 14 below.
5. Contact of a crude oil containing natural acids and an alkaline aqueous phase can give rise to transient minima in oil/water interfacial tensions. See, for example: Rubin, E.; Radke, C. J. Chem. Eng. Sci. 1980, 35, 1129-1138. Rudin, J.; Bernard, C.; Wasan, D. T. Ind. Eng. Chem. Res. 1994, 33, 1150-1158, and references therein.
6. Contact of a crude oil containing natural acids and an alkaline aqueous phase can give rise to transient minima in oil/water interfacial tensions. See, for example: Rubin, E.; Radke, C. J. Chem. Eng. Sci. 1980, 35, 1129-1138. Rudin, J.; Bernard, C.; Wasan, D. T. Ind. Eng. Chem. Res. 1994, 33, 1150-1158, and references therein.
7. Water-soluble, disulfide-containing, cationic surfactants have been reported in the past. Measurements of the surface tensions of aqueous solutions of these surfactants during their reduction to thiol fragments have not been described. Pinazo, A.; Diz, M.; Solans, C.; Pes, M. A.; Erra, P.; Infante, M. R. J. Am. Oil Chem. Soc. 1993, 70, 37-42.
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15. The surface tension of a solution of 2 prepared with deoxygenated buffer did not measurably change over a period of 8 h.
16. The upward curvature of the plot of surface tension of 1 shown in Figure 1 (for concentrations greater than ∼ 1 mM) may be caused by premicellar aggregation: Menger, F. M.; Littau, C. A. J. Am. Chem. Soc. 1993, 115, 10083-10090.
17. Surface tensions measured at bubble frequencies less than 0.1 Hz were similar to those measured at 0.1 Hz. The surface tensions of the reacting system reported in this paper correspond, therefore, to a local steady state at the surface of the solution. In the absence of reaction, these surface tensions are equilibrium ones.
18. The molecular areas were estimated by using the Gibbs adsorption equation in the presence of swamping concentrations of electrolyte and by assuming ideal solution behavior in the bulk of the solution. For a discussion of this calculation, see ref 1c.
19. Dimeric, trimeric, and polymeric surfactants that possess disulfide bonds can, we believe, provide the capability to effect large changes in surface tension over wide ranges of concentration. See, for example: Gallardo, B. S.; Abbott, N. L. Langmuir 1997, 13, 203-208.
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26. (b) Jocelyn, P. C. Methods Enzymol. 1987, 143, 246-256.
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28. The addition of 10 mM DTT and 1 mM oxidized DTT to water did not result in a change in surface tension.
29. The product of reduction was identified as 2 by using thin-layer chromatography (aluminum oxide plates, methanol as eluent).
30. Jong, L. I.; Abbott, N. L. Unpublished results.
31. Krisovitch, S. M.; Regen, S. L. J. Am. Chem. Soc. 1992, 114, 9828-9835.
32. Rosen, M. J. Surfactants and Interfacial Phenomena, 2nd ed.; Wiley: New York, 1989.
33. This observation is consistent with a past study that investigated oxidation of water-insoluble, 1-octadecanethiol to dioctadecyl disulfide at the surface of a solution. At constant surface pressure, oxidation was accompanied by a decrease in surface area: Ahmad, J. Langmuir 1996, 12, 963-965.