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Abstract: The complementary drop and bubble profile analysis and maximum bubble pressure tensiometry are used to measure the dynamic surface tension of aqueous SDS solutions in the presence of hardness salts (CaCl2 and MgCl2 in the ratio of 2:1 at concentrations of 6 and 40FH). The presence of hardness salts results in an essential increase of the SDS adsorption activity, which indicates the formation of Ca(DS)2 and Mg(DS)2 in the SDS solutions. The surface tension isotherms of SDS in presence of Ca(DS)2 and Mg(DS)2 are described using the generalised Frumkin model. The presence of hardness salts accelerates the ageing of SDS solutions as compared with the addition of 0.01M NaCl due to a faster hydrolysis and hence formation of dodecanol. These results are used to estimate the possible concentration of dodecanol in the studied SDS solutions. The buoyant bubble profile method with harmonic surface oscillations is used to measure the dilational rheology of SDS solutions in presence of hardness salts in the frequency range between 0.005Hz and 0.2Hz. The visco-elasticity modulus in the presence of hardness salts is higher as compared with its values in the presence of 0.01M NaCl additions. The ageing of SDS solutions leads to an essential increase of the visco-elastic modulus. [Copyright &y& Elsevier]

Abstract: With modified measuring procedure and measuring cell design in the drop profile tensiometer PAT, it became possible to study the rate of water evaporation through adsorbed or spread surface layers. This method was employed to measure the rate of water evaporation from drops covered by adsorbed layers of some proteins and surfactants, in particular n-dodecanol. It was shown that the formation of dense (double or condensed) adsorbed layers of protein and the formation of 2D-condensed n-dodecanol layer decrease the water evaporation rate by 20–25% as compared with pure water. At the same time, the adsorbed layers of ordinary surfactants (sodium dodecyl sulfate and nonionic ethoxylated surfactant C14EO8) do not affect the water evaporation rate remarkably. [Copyright &y& Elsevier]

Abstract: Exact knowledge of the dead time as part of the bubble lifetime in the maximum bubble pressure method is an important prerequisite for accurate dynamic surface tension measurements. The duration of the dead time depends essentially on the capillary geometry and affects significantly the measured surface tensions of concentrated surfactant solutions. Increase of the dead time leads to a significant surface tension decrease of a freshly formed bubble surface due to the significantly higher residual adsorption of the surfactant molecules. It is shown that correct dynamic surface tensions are obtained with the experimental procedure of Sugden''s method only when in addition to the fixed frequency of bubble formation, also the dead time values for the two capillaries are kept constant. [Copyright &y& Elsevier]

Abstract: The analysis of the available bubble life times and dead times for the bubble pressure tensiometer BPA-1S shows that dynamic surface tensions can be measured also for surfactant solutions at concentrations many times higher than the corresponding CMC. For the three nonionic surfactants Triton X-100, Triton X-45, and C14EO8 experiments are performed for solutions with a concentration of up to 200 times the CMC (C14EO8). Comparison of the experimental data with micelle kinetics models yields rate constants for the fast micelle dissolution process, which are in a good agreement with values obtained by other experimental methodologies. [Copyright &y& Elsevier]

At low surfactant concentration the loss of molecules in the bulk phase due to adsorption can be significant if the surface-area-to-bulk-volume ratio is large. This loss of molecules, however, can be used to determine the adsorption of a surfactant if the experiments are performed under well-controlled conditions. Experiments are performed with the model surfactant tridecyldimethylphosphine oxide (C13DMPO) using drop profile analysis and ring tensiometry. Taking into account the different area/volume ratios and the measured equilibrium surface tensions as a measure of the final surfactant bulk concentration, the adsorption of C13DMPO is determined. [Copyright &y& Elsevier]

A thermodynamic model is derived which is suitable to describe adsorption from a mixed protein/surfactant solution. The comparison with experimental data for HSA mixed with the nonionic surfactant decyl dimethyl phosphine oxide shows good agreement. Some model calculations are discussed in terms of the competitive character of the process of adsorption from mixed protein/surfactant solutions. The behavior of globular (HSA) and flexible (β-casein) proteins appears to be quite different due to the possibility of changing the molar area of adsorbed protein molecules. [Copyright &y& Elsevier]

The thermodynamic model for describing the adsorption of surfactant molecules in different adsorption states, the reorientation model, is reconsidered on a more rigorous level. The resulting model equations are used to describe experimental surface pressure data published in the literature. The new model proposed contains three physical parameters and describes the experimental dependencies Π(c) for oxethylated alcohols very accurately. [Copyright &y& Elsevier]

The present analysis shows that the introduction of intrinsic two-dimensional compressibility of a surfactant adsorption layer allows a much better interpretation of experimental data on the limiting (high-frequency) elasticity and characteristic frequency of diffusional relaxation than models using Frumkin''s or other adsorption isotherms. The proposed model describes experimental data on surface dilational elasticity, as well as on surface pressure, sufficiently well at low and high surfactant concentrations, assuming the Lucassen and van den Tempel model of surface dilational elasticity is realized. [Copyright &y& Elsevier]

Graphical abstract Abstract The dilational visco-elasticity of surfactant adsorption layers was measured at low frequencies by the drop profile analysis tensiometry using oscillating drops. As the studied non-ionic surfactant C 13 DMPO (tridecyl dimethyl phosphine oxide) is soluble in water and in hexane, the partitioning of the surfactant between the two solvents had to be taken into consideration. The diffusion controlled exchange of matter theory was generalized in order to take into consideration the curvature of the interface, the diffusional transport in both adjacent bulk phases as well as the transfer across the liquid interface. Using two configurations, i.e. water drop in hexane and hexane drop in water, it is shown that the frequency dependence of the visco-elasticity modulus and the phase angle can be well described when the correct partition coefficient is applied. The surface activity of the selected surfactant C 13 DMPO is optimum to demonstrate the impact of matter transfer across the interface on the dilational visco-elasticity of interfacial adsorption layers of non-ionic surfactants. [ABSTRACT FROM AUTHOR]

Highlights: [•] C n TAB molecules adsorb from the water phase at the water/oil interface. [•] The presence of hexane phase enhances the C n TAB adsorption. [•] Lengths of the oil and surfactant molecules define the adsorption layer structure. [•] Good theoretical fitting is obtained with the Frumkin Ionic Compressibility model. [ABSTRACT FROM AUTHOR]

Abstract: The superposition-additive approach developed previously was shown to be applicable for the calculations of the thermodynamic parameters of formation and atomization of conjugate systems, their dipole polarizability, molecular diamagnetic susceptibility, π-electronic ring currents, etc. In the present work, the applicability of this approach for the calculation of the thermodynamic parameters of formation and clusterization at the water/air interface of alkanes, fatty alcohols, thioalcohols, amines, nitriles, fatty acids (C n H2 n +1X, X is the functional group) and cis-unsaturated carboxylic acids (C n H2 n −1COOH) is studied. Using the proposed approach the thermodynamic quantities determined agree well with the available data, either calculated using the semiempirical (PM3) quantum chemical method, or obtained in experiments. In particular, for enthalpy and Gibbs’ energy of the formation of substituted alkane monomers from the elementary substances, and their absolute entropy, the standard deviations of the values calculated according to the superposition-additive scheme with the mutual superimposition domain C n −2H2 n −4 (n is the number of carbon atoms in the alkyl chain) from the results of PM3 calculations for alkanes, alcohols, thioalcohols, amines, fatty acids, nitriles and cis-unsaturated carboxylic acids are respectively: 0.05, 0.004, 2.87, 0.02, 0.01, 0.77, and 0.01kJ/mol for enthalpy; 2.32, 5.26, 4.49, 0.53, 1.22, 1.02, 5.30J/(molK) for absolute entropy; 0.69, 1.56, 3.82, 0.15, 0.37, 0.69, 1.58kJ/mol for Gibbs’ energy, whereas the deviations from the experimental data are: 0.52, 5.75, 1.40, 1.00, 4.86kJ/mol; 0.52, 0.63, 1.40, 6.11, 2.21J/(molK); 2.52, 5.76, 1.58, 1.78, 4.86kJ/mol, respectively (for nitriles and cis-unsaturated carboxylic acids experimental data are not available). The proposed approach provides also quite accurate estimates of enthalpy, entropy and Gibbs’ energy of boiling and melting, critical temperatures and standard heat capacities for several classes of substituted alkanes. For the calculation of thermodynamic functions of clusterization of dimers, trimers and tetramers of fatty alcohols, thioalcohols, amines, carboxylic acids and cis-unsaturated carboxylic acids two superposition-additive schemes are proposed which ensure the correct superimposition of the molecular graphs, including intermolecular hydrogen–hydrogen interactions in the clusters. The calculations involve the thermodynamic parameters of clusterization obtained earlier by the PM3 method. It is shown that the proposed approach reproduces quite accurately the values calculated earlier and is applicable for the prediction of the thermodynamic parameters of the formation of surfactant monolayers. [Copyright &y& Elsevier]

Abstract: Even though sodium dodecyl sulphate (SDS) is the most frequently studied surfactant, its properties at liquid interfaces are not easily accessible. This is mainly caused by the fact that in aqueous solution SDS is subject to hydrolysis, by which the homologous dodecanol (C12OH) is formed. Due to its enormously high surface activity it competes with SDS at the interface. We demonstrate here that this “natural” impurity C12OH does not remarkably affect the adsorption dynamics of SDS at the water/hexane interface, due to its high solubility in hexane. Therefore, the dynamic adsorption properties can be determined independent of disturbing dodecanol effects. The surfactant adsorbs diffusion controlled and the interfacial tension isotherm at the water/hexane interface is well described by a Frumkin model. However complementary experiments via direct admixture of dodecanol in hexane indicate a significant decrease in interfacial tension of the water–hexane interface at concentrations higher than 10−3 mol/l in hexane. This condition may happen when the oil phase is distributed as small droplets in a high concentrated solution of SDS. The distribution coefficient of C12OH between water and hexane is estimated from adsorption experiments to be Kp = co /cw =6.7×103. [ABSTRACT FROM AUTHOR]

The experimental data on the surface rheological characteristics of dodecyl dimethyl phosphine oxide solutions obtained in a fully automatic oscillating bubble device under microgravity conditions in the frequency range 0.01–100 Hz are presented. The complex surface elasticity modulus is obtained form the amplitude- and phase-frequency characteristics of established pressure oscillations in a closed cell without calibration experiments by direct calculation of the necessary coefficients. The characteristics of the adsorption layers obtained from the elasticity modulus are in good agreement with adsorption isotherms and equations of state accounting for the intrinsic (2D) monolayer compressibility. [Copyright &y& Elsevier]

The adsorption kinetics of micellar solutions of anionic/cationic SDS/DATB mixtures with mixing ratios of 10/1 and 10/2, respectively, are studied experimentally by means of the maximum bubble pressure method. For long adsorption times the adsorption of the highly surface-active anionic/cationic complex leads to a decrease of dynamic surface tension in comparison to the single SDS system. However, the situation is the reverse for short adsorption times where the dynamic surface tension is increased by addition of the cationic surfactant, although the overall concentration is increased. This unexpected behavior is explained by partial solubilization of free SDS molecules into micelles formed by SDS/DTAB complexes. With increasing overall concentration, when eventually the CMC of SDS is reached, the anionic/cationic complex itself is solubilized by SDS micelles. Finally, no complex micelles, which for their part can solubilize an excess of SDS molecules, are present. Hence, the dynamic properties of the solution are no longer influenced by the depletion of SDS molecules and the mixture tends to behave like a pure SDS solution. [Copyright &y& Elsevier]