Stationary Mosaic Patterns and Segmented Waves in a Belousov-Zabotinsky/Sodium Dodecyl Sulfate System.

Effects of non-ionic micelles on transient chaos in an unstirred Belousov-Zhabotinsky reaction.

The behaviour of the Ce(IV)-catalyzed Belousov-Zhabotinsky (BZ) system has been monitored at 20.0 degrees C in unstirred batch conditions in the absence and presence of different amounts of the non-ionic micelle-forming surfactants hexaethylene glycol monodecyl ether (C10E6) and hexaethylene glycol monotetradecyl ether (C14E6). The influence of the non-ionic surfactants on both the kinetics of the oxidation of malonic acid (MA) by Ce(IV) species and the behaviour of the BZ reaction in stirred batch conditions has also been studied over a wide surfactant concentration range. The experimental results have shown that, in unstirred batch conditions, at surfactant concentrations below the critic…

Kinetic studies of the interaction between DNA and polycations based on polyasparthylhydrazide

Abstract In the present paper, a systematic kinetic study on the interaction between interpolyelectrolytes such as positive-charged polymers and DNA was carried out. In particular, a qualitative–quantitative kinetic investigation on the interaction between copolymers of the α,β-poly(aspartylhydrazide) and DNA calf thymus filaments was performed. This study gives a new model starting from a well known “pseudo-phase model”, and permits to give a qualitative explanation about the trends of experimentally observed kinetic constants by varying the concentration of one of the two poly-electrolytes. Moreover, this study permits to verify the dependence of the binding constants KPAHy–CPTA and KDNA …

Thermodynamic Behavior of Non-Ionic Tri-block Copolymers in Water at Three Temperatures

Apparent molar volumes (V Φ) of aqueous solutions of some copolymers, based on ethylene oxide (EO) and propylene oxide (PO) units, were determined as functions of concentration at three temperatures. Viscosity measurements were also carried out on some of these systems. The effects studied include how the molecular architecture and the molecular weight affect the aggregation of the copolymer, keeping constant the EO/PO ratio. Modeling of the volumetric data yielded the partial molar volume of the copolymer in the standard (V°) and the aggregated (V M) states, as well as the equilibrium constant for micellization and the aggregation number. Analysis of the viscosity data supported the insigh…

Calorimetric study of the solubilization of ethylenediamine, N,N-dimethylaminoethylamine and N,N,N?,N?-tetramethylethylenediamine by reversed AOT micelles

Distribution constants and standard enthalpies of transfer of ethylenediamine (en), N,N-dimethylaminoethylamine (dmen) and N,N,N′,N′-tetramethylethylenediamine (tmen) partitioned between n-heptane and water containing reversed sodium bis(2-ethylhexyl) sulfosuccinate (AOT) micelles as a function of the molar concentration ratio R (R=[water]/[AOT]) were evaluated by a calorimetric method. The results show that en, dmen and tmen molecules, solubilized in the reversed micelles, are distributed between the micellar aqueous core and the micellar palisade layer. An analysis of the thermodynamic parameters of the partition process demonstrates the peculiar solvent properties of the water containing…

Origin and extinction of chaotic oscillations in the Belousov-Zhabotinsky reaction

Interactions of tetradecyldimethylaminoxide with polyacrylic and polymethacrylic acids in aqueous solution

Abstract The interactions between the zwitterionic surfactant tetradecyldimethylaminoxide (C14DMAO) and the polyelectrolytes polyacrylic (PAA-205 and PAA-250) or polymethacrylic (PMA-100) acids have been investigated in aqueous solution. The physico-chemical properties of these systems have been monitored by measuring the solution pH, electric birefringence, zero-shear viscosity and density for increasing surfactant concentrations. The experimental results have shown that significant change in the physico-chemical properties of the polyacid/surfactant system occurs only in a narrow pH range and when the amphiphile forms rod-like micelles. Moreover, they clearly reveal the important role pla…

Dielectric properties of solutions of antimony (III) halides in methanol

The complex permittivities obtained by time domain reflectometry (TDR) measurements in the frequency range 0.1–15 GHz are reported for solutions of SbF3, SbCl3 and SbBr3 in methanol at 25°C. By increasing the concentration of the solutes, a marked increase of the main relaxation time and of the static permittivity of methanol is observed. These effects have been attributed to the ability of antimony (III) halides to strengthen the hydrogen bonding in methanol and to promote the shift of the dynamic equilibria among the various populations of hydrogen bonded methanol aggregates toward those characterized by a parallel orientation of neighboring dipoles. A second relaxation, occurring at low …

Photocatalytic degradation of toluene in aqueous suspensions of polycrystalline TiO2 in the presence of the surfactant tetradecyldimethylamino-oxide

The heterogeneous photocatalytic method has been used for carrying out the toluene oxidation in synthetic aqueous solutions containing also a zwitterionic surfactant, i.e. tetradecyldimethylamino-oxide (C 14 DMAO). A batch photoreactor with immersed lamp and two kinds of polycrystalline TiO 2 catalysts were used. The results indicate a substantial increase of the toluene degradation rate in the presence of the surfactant; the complete photo- oxidation of toluene was achieved in a few hours of irradiation at the used experimental conditions; at higher irradiation times also C 14 DMAO was completely degraded. The main intermediates of toluene degradation were p-cresol (4-methyiphenol) and ben…

Adsorption of triblock copolymers and their homopolymers at laponite clay/solution interface. Role played by the copolymer nature

The adsorption thermodynamics of copolymers, based on ethylene oxide (EO) and propylene oxide ( PO) units, at the laponite (RD) clay/liquid interface was determined at 298 K. The copolymer nature was tuned at molecular level by changing the hydrophilicity, the architecture and the molecular weight (Mw) keeping constant the EO/PO ratio. Polyethylene (PEGs) and polypropylene (PPGs) glycols with varying Mw and their mixture were also investigated to discriminate the role of the EO and the PO segments in the adsorption process. Enthalpies of transfer of RD, at fixed concentration, from water to the aqueous macromolecule solutions as functions of the macromolecule molality were determined. They …

Calorimetric and viscosimetric investigation of the interaction between α,β-polyasparthydrazide and sodium dodecyl sulfate micelles

Abstract The interaction between α,β-polyasparthydrazide (PAHy) and sodium dodecyl sulfate (SDS) micelles in aqueous solution was investigated by calorimetry and viscosimetry. The dependence of the enthalpic effect due to this interaction upon the surfactant concentration was rationalized in terms of a progressive binding of SDS micelles to the polymeric backbone. The analysis of the calorimetric data allow evaluation of the binding ability of SDS micelles to the polymeric chain. The viscosimetric behavior of SDS plus PAHy aqueous solutions, discussed in terms of the parameter F [F = ηrel(PAHy) + ηrel(PAHy) − ηrel(SDS+PAHy)], confirms the occurence of the interaction between SDS micelles an…

Perturbation of the oscillatory Belousov-Zhabotinsky reaction with polyethylene glycol

The effects of the water soluble non-ionic polymers poly(ethylene glycol) (PEG-400, PEG-900 and PEG-2000) and poly(ethylene glycol dimethylether) (MPEG-2000) on the dynamics of the cerium ion catalyzed oscillatory Belousov-Zhabotinsky (BZ) reaction were investigated in a stirred batch reactor by measuring CO2 evolution rate and Ce(IV) absorbance changes. Addition of increasing amounts of additives strongly influences all the oscillatory parameters (induction period, time period and amplitude) to an extent that depends on the type of the additive used. The polymer perturbation effects are compared with those previously obtained with methanol and ethylene glycol (1). All these experimental ob…