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Abstract  

Electrical conductivity of aqueous solutions of dodecylpyridinium chloride and bromide have been determined. From these data the critical micelle concentration (cmc) was determined. The thermal properties as standard Gibbs free energy, enthalpy and entropy of micellization was estimated from a uncharged-phase separation model and enables to obtain another properties like heat capacity of micellization and the relevant parameters in the minimum of temperature dependence of cmc. The enthalpy-entropy compensation was shown for the studied compounds.

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Abstract  

The molality dependence of specific conductivity of pentadecyl bromide, cetylpyridinium bromide and cetylpiridinium chloride in aqueous solutions has been studied in the temperature range of 30–45 °C. The critical micelle concentration (cmc) and ionization degree of the micelles, β, were determined directly from the experimental data. Thermal parameters, such as standard Gibbs free energy
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enthalpy
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and entropy
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of micellization were estimated by assuming that the system conforms to the pseudo-phase separation model. The change in heat capacity on micellization
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was estimated from the temperature dependence of
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An enthalpy–entropy compensation phenomenon for the studied system has been found.
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Abstract  

The critical micelle concentrations and the enthalpies of micellization of alkyltrimethylammonium bromides having dodecyl, tetradecyl and hexadecyl hydrocarbon chains have been studied using surface tension and calorimetry measurements as a function of temperature. As expected, the change of critical micelle concentrations is very small with an increase of temperature of 10 deg whereas we observe a drastic change of the enthalpies of micellization. As it has been found by applying the Van't Hoff law to thecmc values at different temperatures, the calorimetric measurements show that the enthalpy of micellization, exothermic above a minimal temperature, becomes endothermic below this temperature.

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Application of the calorimetry to studies of colloidal phenomena

Enthalpies of micellization and enthalpies of adsorption of zwitterionic surfactants onto silica gel

Journal of Thermal Analysis and Calorimetry
Authors: J. Zajac, M. Chorro, C. Chorro, and S. Partyka

Abstract  

The importance of calorimetric methods in studies of colloidal phenomena is illustrated by the analysis of the experimental enthalpies of dilution and adsorption for aqueous solutions of three zwitterionic surfactants: 1–12 betaine, 3–12 betaine, and 3–12 sulfobetaine. The batch microcalorimeter ‘Montcal 3’, used to obtain these data, is described. The molar enthalpies of micellization and the differential molar enthalpies of adsorption onto silica gel are shown to be functions of the headgroup hydrophilicity, fixed by the type of negatively charged center and the number of methylene groups separating the charged sites.

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Abstract  

Post-column derivatization detection system based on dithizone solubilized in cetyltrimethyl-ammonium hydrogenesulfate micellar media at pH 2.0 was devised and evaluated for selective detection of mercury(II), methylmercury and phenylmercury in reversed-phase HPLC system with photometric detection at 500 nm. This reagent solution is fully compatible with acidic organo-aqueous mobile phases generally used in RPHPLC. With the aid of the detection systematic study of the retention behaviour of three mercury species on octadecylsilica sorbent was carried out. Influence of pH, acetonitrile volume fraction, complex forming additives was investigated in detail. In mobile phase consisting of 5–30% of acetonitrile in water at pH 2.0 and 2·10–4 mol·I–1 DCTA linear calibration curves were measured in range 20–1000 ppb with correlation coefficient better than 0.99. Detection limits were 1–5 ng for this three mercury species. Interferences of copper(II) and silver(I) are negligible.

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of association is the isothermal titration microcalorimetry (ITC). It has been successfully applied in a growing number of studies of surfactant systems [ 7 – 19 ]. The major advantage of ITC for micellization studies is the ability to perform direct

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Abstract  

The micellization characteristics of sodium n-dodecyl sulfate (SDS) have been investigated by microcalorimetric technique at conditions close to the physiological ones. The thermodynamics of micellization were studied at 20, 25, 30, 35 and 40 °C in 50 mM HEPES buffer, pH 7.4 and 160 mM NaCl using isothermal titration calorimetric (ITC) technique. The calorimeter can operate in a stepwise addition mode, providing an excellent method of determination of critical micelle concentration (CMC) and enthalpy of demicellization (and hence micellization). It can as well distinguish between aggregating and non-aggregating amphiphiles (solutes) in solution. The dilution enthalpy (∆H dil) was calculated and graphed versus concentration in order to determine the micellization enthalpy (∆H mic) and CMC. In addition to the CMC and ∆H mic, the effective micellar charge fraction (α) of the ionic surfactant micellization process can also be determined from ITC curves. The Gibbs free energy of the micellization (∆G mic), entropy of the micellization (∆S mic), and specific heat capacity of the micellization (∆C P,mic) process have been evaluated by the direct calorimetric method (mass-action model) as well as by the indirect method of van’t Hoff by processing the CMC and α results of microcalorimetry at different temperatures. The differences of the results obtained by these two procedures have been discussed. The presence of NaCl (160 mM) in the solutions decreased the CMC of SDS. The enthalpy changes associated with micelle dissociation were temperature-dependent, indicating the importance of hydrophobic interactions. The ∆G mic was found to be negative, implying, as expected, that micellization occurs spontaneously once the CMC has been reached. The values of ∆G mic were found to become more negative with increasing temperature and the ∆S mic was found to decrease with increasing temperature in both models.

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Abstract  

Tetronic® comprises X-shaped copolymers formed by four poly(propylene oxide) (PPO) and poly(ethylene oxide) (PEO) block chains bonded to an ethylene diamine central group. Micellization behaviour of three representative Tetronics (T304, T904 and T1307) was characterized to gain an insight into the interactions between the copolymer unimers and the state of water in their solutions. The enthalpy of demicellization, recorded at 37°C in an isoperibol microcalorimeter, indicated that the process was in all cases exothermic and the enthalpy ranked in the order T1307≥T904>>T304. Micellization is entropy-driven owing to hydrophobic interactions between the PPO chains. DSC analysis showed that the crystallization and melting peaks of the free water remaining in T304 and T904 solutions were progressively shifted toward lower temperatures as the surfactant proportion increased, owing to a colligative effect. Bound water corresponded to 3 water molecules per EO repeating unit. In the case of T1307, which has longer PEO chains, a splitting of the melting peak was observed, one peak appearing around 0°C due to free water and another at –15°C due to interfacial water. As T1307 proportion raised, the enthalpy of the former decreased, whilst the enthalpy of the latter increased. In 40% T1307 solutions, interfacial water overcame the proportion of free water; there being 1 interfacial and 3 bound water molecules per EO repeating unit. Gaussian deconvolution of FTIR spectra also enabled to characterize the evolution of free water as a function of Tetronic proportion. The dependence of micellization and water interaction behaviour on Tetronics structure should be taken into account to use these copolymers as drug solubilizers and micellar carriers.

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Abstract  

A new batch titration microcalorimeter has been used for estimation of thermodynamic properties in various investigated colloidal systems. As examples, we present enthalpic and kinetic data obtained from this calorimetric device for four different processes widely encountered in colloid science: (i)  The dilution/micellization process of cationic gemini surfactants in aqueous solution. (ii)  The hydration process of non ionic surfactants in organic solution, i.e. the mechanism of micellar solubilization of water in the aggregates. (iii)  The complexation of calcium ions by polyacrylates sodium salts (PaNa). (iv)  The adsorption phenomenon of PaNa molecules on the calcium carbonate surface.

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