Molecular Mechanism and Chemical Kinetic Description of Nitrobenzene Liquid Membrane Oscillator Containing Benzyldimethyltetradecylammonium Chloride Surfactant

Szpakowska, Maria; Płocharska-Jankowska, Elżbieta; Ob, Nagy

doi:10.1021/jp9066873

Cited by 14 publications

(25 citation statements)

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“…A more detailed analysis of these kind of phenomena is described in a recent, extensive review by Kovalchuk and Vollhardt [39]. Also, in a very recent paper, Szpakowska et al [40] have described a latest kinetic model of the nitrobenzene-based liquid membrane oscillator (in the U-shaped cell) and have discussed the contribution of different factors to the measured oscillatory variations of the electric potential differences. It was also suggested again that hydrodynamic (Marangoni-type) instabilities cannot solely explain, but can only amplify oscillations appearing due to the decisive kinetic properties of the system.…”

Section: Recent Developments In Liquid Membrane Oscillatorsmentioning

confidence: 99%

Liquid Membrane and Other Membrane Oscillators

Orlik

2012

Self-Organization in Electrochemical Systems II

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In complement to the hydrodynamic instabilities driven by surface tension gradients, enclosed in Sects. 5.4-5.7, we describe here the dynamics of the liquid-liquid interface, formed by two fluids of very limited miscibility, e.g., by water and 2-nitropropane. First reports on this type of dynamical systems have been published by Dupeyrat and Nakache [1,2], and later analogous studies were continued also by .A representative example of that type of the systems is the water-2-nitropropane system [3]. The key point is that each phase should contain the dissolved species that is significantly better soluble in the other phase. In this way the initial state of such system is far from equilibrium and the natural trend to decrease the free Gibbs energy is the flow of each dissolved species to the other phase. In the example described here, the aqueous phase contains initially the hexadecyltrimethylammonium bromide (or cetyltrimethylammonium bromide, CTAB) the large organic CTA + cation of which exhibits, due to its hydrophobicity, higher affinity to the organic phase. In turn, the phase of 2-nitropropane contains initially dissolved picric acid (HA), better soluble and also partly dissociating in water (pK a % 0.2).When these two phases are brought into contact, with the organic layer placed over the aqueous layer, the oppositely directed flows of CTAB and HPi begin. This transport is associated with subtle oscillations of various characteristics: pH of aqueous solution, interfacial potential drop (Fig. 6.1), and interfacial tension. The latter phenomena are easily detectable as visible oscillations of the meniscus at the interface of both liquids. It is interesting that under such non-equilibrium conditions the presence of surfactant (CTAB) does not depress the surface tension gradients, but on the contrary, it is responsible for their periodic temporal variations.Yoshikawa and Matsubara [3] have proposed the mechanism of these oscillatory phenomena. First, one should note that CTA + cations in both phases form micelles above certain critical CTA + concentrations. Those micelles exhibit inverted M. Orlik, Self-Organization in Electrochemical Systems II, Monographs in Electrochemistry,

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Section: Recent Developments In Liquid Membrane Oscillatorsmentioning

confidence: 99%

Liquid Membrane and Other Membrane Oscillators

Orlik

2012

Self-Organization in Electrochemical Systems II

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“…In order to contribute to elucidation of the molecular mechanism responsible for the observed oscillations, the physico-chemical properties of bulk liquid membrane oscillators with anionic (Szpakowska et al, 2008) and cationic (Szpakowska et al, 2002(Szpakowska et al, , 2003(Szpakowska et al, , 2006a(Szpakowska et al, , 2009) mass transfer surfactants and dif-*Corresponding author, e-mail: mszpak@pg.gda.pl Brought to you by | New York University Bobst Library Technical Services Authenticated Download Date | 5/27/15 10:51 AM ferent membrane materials (Szpakowska et al, 2006a(Szpakowska et al, , 2006b(Szpakowska et al, , 2008(Szpakowska et al, , 2009 were investigated in detail. The influence of taste substances (Szpakowska et al, , 2006a was also examined and analysed in depth by the Gabor transformation (P locharska-Jankowska et al, , 2006.…”

Section: Introductionmentioning

confidence: 99%

“…The working kinetic equations are not always in accord with the laws of chemical kinetics or they are based on unrealistic assumptions (Szpakowska et al, 2006b;Yoshikawa et al, 1988;Yoshikawa & Matsubara, 1983;Toko et al, 1985;Pimienta et al, 2001). This situation led to the proposal of a new sufficiently general and physicochemically acceptable mechanism for analysis by the chemical kinetics method of the bulk liquid membrane oscillations observed (Szpakowska et al, 2009).…”

Section: Introductionmentioning

confidence: 99%

“…In a previous publication (Szpakowska et al, 2009), the physico-chemical properties of a nitrobenzene bulk liquid membrane oscillator containing BDMTACl surfactant in an aqueous donor phase were presented and a molecular mechanism was proposed using the chemical kinetic approach. It was shown that the actual oscillations of the electric potential difference between the two aqueous phases appeared at the liquid membrane-aqueous acceptor phase interface (m/a).…”

Section: Introductionmentioning

confidence: 99%

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New bulk liquid membrane oscillator composed of two coupled oscillators with diffusion-mediated physical coupling

2015

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A new type of bulk liquid membrane system, which represents the first example of a bulk liquid membrane oscillator characterised by the presence of two coupled oscillators, is described. When the benzyldimethyltetradecylammonium chloride surfactant undergoes an oscillatory mass transfer through a nitromethane liquid membrane, a new liquid layer (phase X) appears between the membrane and the acceptor phase. Kinetic analysis provides evidence that the whole system is composed of two coupled oscillators with diffusion-mediated physical coupling. The first component oscillator (based on nitromethane) of lower frequency delivers the driving material to the second one (phase X-based oscillator) leading to additional higher frequency oscillations. A new molecular mechanism is proposed for interpreting the experimental observations. The results might enhance understanding of intercellular communication in biology, where periodic signalling is more efficient than any other type of signalling mode.

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“…For applying this phenomenon in engineering, information regarding the kind of material that can be used is very important. To date, surfactants, including cationic [11][12][13], anionic [3,14], and nonionic forms [15][16][17], have been examined. Moreover, some spontaneous interfacial motion has also been observed in systems not incorporating a surfactant [18].…”

Section: Introductionmentioning

confidence: 99%