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In mixed solutions of anionic and cationic surfactants, called catanionics, ion pairs are formed which behave like non-ionic surfactants with a much higher surface activity than the single components. In equimolar mixtures of NaCnSO4 and CmTAB, all surface-active ions are paired. For mixtures with n + m = const, the interfacial properties are rather similar. Catanionics containing one long-chain surfactant and one surfactant with medium chain length exhibit a strong increase in surface activity as compared with the single compounds. In contrast, catanionics of one medium- and one short chain surfactant have a surface activity similar to that of the medium-chain surfactant alone. Both the Frumkin model and the reorientation model describe the experimental equilibrium data equally well, while the adsorption kinetics of the mixed medium- and short-chain surfactants can be well described only with the reorientation model.

The dynamic and equilibrium properties of adsorption layers of poly (oxyethylene) alkyl ether (CnEOm) can be well described by the reorientation model. In its classical version, it assumes two adsorption states, however, there are obviously surfactants that can adsorb in more than two possible conformations. The experimental data for C14EO4 and C14EO8 (dynamic and equilibrium surface tensions and surface dilational visco-elasticity as measured by bubble profile analysis tensiometry) are used to verify if a reorientation model with more than two possible adsorption states can better describe the complete set data of CnEOm adsorption layers at the water/air interface. The proposed refined theoretical model allows s different states of the adsorbing molecules at the interface. The comparison between the model and experiment demonstrates that, for C14EO4, the assumption of s = 5 adsorption states provides a much better agreement than for s = 2, while for C14EO8, a number of s = 10 adsorption states allows an optimum data description.

The adsorption behaviour of linear poly(oxyethylene) alkyl ether (CnEOm) is best described by a reorientation model. Based on a complete set of experimental data, including the adsorption kinetics, the equilibrium surface tension isotherm and the surface dilational visco-elasticity, the thermodynamic and kinetic adsorption parameters for some CnEOm at the water/air interface were determined. For the study, six CnEOm surfactants were selected (n = 10, 12 and 14 and m = 4, 5 and 8) and were studied by bubble profile analysis and maximum bubble pressure tensiometry. A refined theoretical model based on a reorientation-adsorption model combined with a diffusion-controlled adsorption kinetics and exchange of matter allowed us to calculate the surface layer composition by adsorbing molecules in different orientations. It turns out that at larger surface coverage, the adsorption rate decreases, i.e., the apparent diffusion coefficients are smaller. This deceleration can be explained by the transition of molecules adsorbed in a state of larger molar surface area into a state with smaller molar surface area.

The theoretical description of the adsorption of proteins at liquid/fluid interfaces suffers from the inapplicability of classical formalisms, which soundly calls for the development of more complicated adsorption models. A Frumkin-type thermodynamic 2-d solution model that accounts for nonidealities of interface enthalpy and entropy was proposed about two decades ago and has been continuously developed in the course of comparisons with experimental data. In a previous paper we investigated the adsorption of the globular protein β-lactoglobulin at the water/air interface and used such a model to analyze the experimental isotherms of the surface pressure, Π(c), and the frequency-, f-, dependent surface dilational viscoelasticity modulus, E(c)f, in a wide range of protein concentrations, c, and at pH 7. However, the best fit between theory and experiment proposed in that paper appeared incompatible with new data on the surface excess, Γ, obtained from direct measurements with neutron reflectometry. Therefore, in this work, the same model is simultaneously applied to a larger set of experimental dependences, e.g., Π(c), Γ(c), E(Π)f, etc., with E-values measured strictly in the linear viscoelasticity regime. Despite this ambitious complication, a best global fit was elaborated using a single set of parameter values, which well describes all experimental dependencies, thus corroborating the validity of the chosen thermodynamic model. Furthermore, we applied the model in the same manner to experimental results obtained at pH 3 and pH 5 in order to explain the well-pronounced effect of pH on the interfacial behavior of β-lactoglobulin. The results revealed that the propensity of β-lactoglobulin globules to unfold upon adsorption and stretch at the interface decreases in the order pH 3 &gt, pH 7 &gt, pH 5, i.e., with decreasing protein net charge. Finally, we discuss advantages and limitations in the current state of the model.

The theoretical description of the adsorption of surfactants at interfaces between aqueous solutions and oil was based over a very long time on models derived for the solution/air interface. Thus, most of the experimentally observed peculiarities could not be specifically considered but were merely interpreted in terms of a penetration of oil molecules into the alkyl chain layer of the adsorbed surfactant molecules. These penetrating oil molecules enhance the surfactant adsorption as compared to the water/air interface. Later on, for the special situations at water/oil interfaces a competitive adsorption of surfactant and oil molecules was postulated, allowing a much better description of experimental data. This picture, however, was unable to explain why the interfacial tension of the water/oil interface decreases very quickly when extremely small amounts of surfactants are added to the water. This effect cannot be of competitive nature, but a cooperativity of surfactant and oil molecules forming a mixed adsorption layer is required instead. This cooperative effect means that already few surfactant molecules adsorbed at the interface can induce a significant ordering of oil molecules in the interfacial layer. This new interfacial structure, in turn, attracts further surfactant molecules to adsorb. Improving the theoretical description of experimental data was finally achieved by applying suitable adsorption models for the two adsorbing compounds, i.e. a Frumkin adsorption model for the oil molecules and a Langmuir, Frumkin, or reorientation model for the adsorbing surfactant molecules. Here, the progress in modelling surfactant adsorption at water/oil interfaces is discussed mainly for the homologous series of the cationic surfactants C(n)TAB, of the anionic surfactant SDS, and members of the homologous series of the non-ionic surfactants CnDMPO at water/alkane interfaces. (C) 2020 Elsevier B.V. All rights reserved.

The surface tension of C13DMPO aqueous solution drops in hexane vapor is studied using the drop profile method. The hexane was injected into the measuring cell at three different conditions: before the formation of the solution drop, at a certain moment during the adsorption process, and after reaching the equilibrium of surfactant adsorption. The surface tension values for all experiments at the same concentration and different injection situations ultimately coincide with each other after attaining the final equilibration stage. The equilibrium surface tension isotherms of C13DMPO solutions, and the adsorption of both components&mdash, surfactant and hexane&mdash, were calculated. It was shown that the presence of surfactant leads to an increased hexane adsorption.

Harmonic surface oscillations of drops are used to study the dilational surface rheology of solutions of the oxyethylated alcohols C10ЕO8, C12ЕO5 and C14ЕO8 at the fixed oscillation frequency of 0.1 Hz for adsorption times between 200 and 5000 s. It was found that at shorter adsorption times the visco-elasticity modulus is lower than its value at longer adsorption times or in the equilibrium state of the adsorption layer at the same surface pressure. This mechanism is explained by the fact that an actual surfactant, characterized by a certain number of EO groups, is in fact a mixture of compounds with a quite wide range of these groups. As molecules with a smaller number of EO groups exhibit a higher visco-elasticity modulus, the changes in the composition of the adsorbed layer during the adsorption lead to the given situation. These considerations are supported by theoretical calculations of the adsorption for mixed surfactants solution.

The surface tension isotherms and dilational visco-elasticity for three nonionic surfactants (C10EO8, C12EO5 and C14EO8) were comparatively studied using the bubble and drop profile analysis tensiometry. The experiments based on drop profiles were analysed assuming the depletion of surfactant molecules from the bulk of the drop due to adsorption. To process the experimental results, two theoretical adsorption layer models (Frumkin and reorientation) were applied, while the reorientation model provides a better description of the experimental results. In addition, the visco-elasticity moduli obtained from drop and bubble profile experiments were compared. It was shown that at higher surfactant concentrations the drop profile method provides visco-elasticities systematically larger than those obtained from bubble profile experiments, even though the adsorption-related depletion has been correctly considered. The proposed correction protocol provides the option for direct comparison between data obtained by the drop profile analysis method with those from other methods.

The influence of temperature on the dynamic surface tension of water in heptane vapour is studied using drop profile analysis tensiometry. The water drops are formed in air saturated by heptane and water vapours. For long life times a new phenomenon is found: a sharp decrease of surface tension from about 60 mN/m down to 30 mN/m. The time until this sharp surface tension sets in decreases with increasing temperature. This phenomenon is attributed to the formation of heptane adsorption layers with a significant thickness. To ensure that the sharp surface tension decrease is not an artefact, the experimental error (deviation of drop profiles from the Young-Gauss-Laplace equation) was determined using harmonic oscillations imposed to the surface of pure heptane drops. It was shown that fitting errors below 10 μm in the determination of the drop radius do not affect the calculated surface tension value. The sharp surface tension decrease was observed with fitting errors below 5 μm, so that this phenomenon was explained to be caused by the formation of multilayers. The surface tensions and adsorbed amounts are described by a model developed earlier. The experimental results depend essentially on the experimental method used. In another experiment the atmosphere in the measuring cell was pre-saturated only by water vapour, and heptane (pentane) was added onto the cell bottom just immediately before the water drop was formed. The increase of temperature results in a slower adsorption process which is opposite to the case where the composition of the mixed atmosphere inside the cell was established prior to the experiments.

Surface tension and dilational viscoelasticity of solutions of various surfactants measured with bubble and drop profile analysis tensiometry are discussed. The study also includes experiments on the co-adsorption of surfactant molecules from a solution drop and alkane molecules from saturated alkane vapor phase. Using experimental data for 12 surfactants with different surface activities, it is shown that depletion due to adsorption of surfactant from the drop bulk can be significant. An algorithm is proposed quantitatively to take into consideration the depletion effect which is required for a correct description of the co-adsorption of alkanes on the solution drop surface and the correct analysis of experimental dynamic surface tension data to determine the adsorption mechanism. Bubble and drop profile analysis tensiometry is also the method of choice for measuring the dilational viscoelasticity of the adsorbed interfacial layer. The same elasticity moduli are obtained with the bubble and drop method only when the equilibrium surface pressures are sufficiently small (Π

The adsorption of proteins (β-lactoglobulin, β-casein) and the oxyethylated non-ionic surfactants C10EO8 and C14EO8 at the aqueous solution/air interface is strongly enhanced and accelerated by the presence of hexane vapour in the air phase caused by the co-adsorption of hexane molecules. Due to this hexane co-adsorption, the dependence of dilational visco-elasticity modulus on surface pressure is shifted towards larger surface pressure values. The adsorption kinetics of the studied non-ionic surfactants shows the same picture as that observed for the two proteins. In contrast, the desorption process of the hexane molecules from a pre-adsorbed mixed adsorption layer is very slow. This decelerated desorption is explained by a rather large desorption energy required by the hexane molecules. The experimental data are compared with several theoretical models developed earlier. The results allow estimating the activation energy for the hexane desorption from adsorption layers of the two studied non-ionic surfactants.

Drop profile analysis tensiometry is applied to measure the dilational visco-elasticity of BLG at the buffered aqueous solution/tetradecane (W/TD) interface using oscillating drops of TD immersed in W at frequencies between 0.01–0.2 Hz. The buffered solutions were investigated at pH 3, pH 5 (isoelectric point) and pH 7 at different buffer concentrations (1 mM, 10 mM and 100 mM). The real part of the complex visco-elasticity shows a maximum when plotted as a function of the interfacial pressure Π. In contrast to the water/air surface (W/A) where we observe maximum elasticity values between 15 and 20 mN/m, at the W/TD interface these maximum values are up to 65–70 mM/m, which is in parallel with the much higher interfacial pressure values at the W/TD interface when compared to the W/A surface. Refereed/Peer-reviewed

The adsorption kinetics of beta-lactoglobulin (BLG) at the water/tetradecane (W/TD) interface as studied by drop profile analysis tensiometry is significantly controlled by the diffusional transport in the aqueous solution bulk. However, due to the contact with the hydrophobic oil phase the protein molecules change their conformation in order to adapt to the interfacial environment. This conformational change can be expressed via the adsorption activity constant. The analysis of the dynamic interfacial tensions leads to much lower activities at short adsorption times and low surface coverages. This allows to conclude that in the early stage of the adsorption layer formation the structure of the BLG adsorption layer at the W/TD interface is similar to that at the water/air (W/A) interface. Refereed/Peer-reviewed

The adsorption–desorption of water vapours on swelling layer silicate is considered in the framework of the Brunauer-Emmett-Teller (BET) and Frenkel-Halsey-Hill (FHH) formalisms. The theoretical dependencies calculated with reasonable and consistent values of model parameters are shown to agree quite satisfactorily with the experimental data. Based on these equations, the description of the adsorption hysteresis related to Type III adsorption isotherms is proposed, which also yields a good reproduction of the experimentally observed values.

The dynamic and equilibrium surface tension for drops of aqueous C14EO8 solutions at the interface to pure air or pentane, hexane, heptane and toluene saturated air, and the dynamic surface tension of pure water at these interfaces are presented. Two theoretical models were employed: both assuming a diffusion controlled adsorption of the surfactant, and either a diffusion or kinetic barrier governed adsorption of the alkanes. The experimental results are best described by the model which implies a diffusion control for the C14EO8 molecules and the existence of a kinetic barrier for the alkane molecules. The desorption of alkanes from the surface layer after equilibration and their subsequent removal from the measuring cell was studied as well. The desorption process was shown to be slow for heptane and hexane. However, for the pentane vapor the desorption is quite rapid, and after the desorption commences the surface tension becomes equal to that at the interface with pure air.

The surface tension and dilational surface visco-elasticity of the individual solutions of the biopolymer DNA and the azobenzene-containing cationic surfactant AzoTAB, as well as their mixtures were measured using the drop profile analysis tensiometry. The negatively charged DNA molecules form complexes with the cationic surfactant AzoTAB. Mixed DNA + AzoTAB solutions exhibit high surface activity and surface layer elasticity. Extremes in the dependence of these characteristics on the AzoTAB concentration exist within the concentration range of 3 × 10−6–5 × 10−5 M. The surface tension of the mixture shows a minimum with a subsequent maximum. In the same concentration range the elasticity shows first a maximum and then a subsequent minimum. A recently developed thermodynamic model was modified to account for the dependence of the adsorption equilibrium constant of the adsorbed complex on the cationic surfactant concentration. This modified theory shows good agreement with the experimental data both for the surface tension and the elasticity values over the entire range of studied AzoTAB concentrations.

The dilational viscoelasticity of adsorption layer was measured at different frequencies of drop and bubble surface area oscillations for aqueous C12EO5 solutions. The modulus values obtained by the two experimental protocols are the same for Π < 15 mN/m, while for higher surface pressures the values from drop experiments exceed those from bubble profile analysis. The nature of this phenomenon was studied using stress deformation experiments. At high surfactant concentrations the magnitude of surface tension variations is essentially higher for drops as compared with bubbles, leading to an increased viscoelasticity modulus for oscillating drops. The observed effects are analyzed quantitatively using a diffusion controlled exchange of matter model. The viscoelasticity moduli for a number of surfactants (different CnEOm and Tritons, C13DMPO, and SDS) are reported, and it is shown that the discrepancies between the data obtained by the two methods for many surfactants agree well with the predictions made here.

The state of sodium humate in aqueous solution and on a solid surface is studied using various methods. It is shown that in aqueous solution at neutral pH and low ionic strength this substance exists in an associated state. The values of molecular mass of the molecules in the preparation studied (Aldrich) are determined to be 1, 3–6 and 15 kDa. A new adsorption-based approach for initial estimation of the molecular mass and size of humic acid molecules is proposed, which can be used instead of any specific sophisticated equipment. The size of the molecules of the studied preparation estimated in this way (in the range of 2.3 to 9.0 nm), agree well with data obtained by chromatographic and electron microscopic measurements, which confirm the reliability of the proposed method.

Bubble profile analysis tensiometry was used to study the surface tension and dilational visco-elasticity of individual and mixed solutions of β-casein (BCS) and β-lactoglobulin (BLG) at various mixing ratios of the components. The results for the individual protein solutions were analysed based on a new theory, which is applicable in the pre-critical and post-critical concentration range of the surface tension isotherm. It is shown that these proteins are capable of displacing each other from the adsorption layer, which affects the surface tension and visco-elasticity modulus of the adsorbed layers. The model developed for protein mixtures agrees well with the experimental data and the calculated dependencies of the surface properties on the solution composition confirm the mutual influence of added proteins.

A thermodynamic model is used to analyse the adsorbed layers of CnDMPO (n = 12, 13), CnTAB (n = 10, 12, 14, 16) and SDS at the aqueous solution/hexane and aqueous solution/dodecane interfaces. The combined model assumes that the adsorption of alkane from the oil phase is governed by the Frumkin model, and the adsorption of the surfactant molecules from the solution obeys the reorientation model. We are able to show that at low surfactant concentrations a remarkable decrease of interfacial tension occurs due to a cooperative formation of a mixed adsorption layers by surfactant and alkane molecules. By a quantum chemical semi-empiric (PM3) simulation we analyse the orientation of oil and surfactant molecules in the interfacial layer, and calculate the relative amounts of adsorbed surfactant and alkane. The values obtained from the thermodynamic models agree well with those results calculated via the PM3 simulation. The results show, that at the interface the short-chain hexane molecules can form bi-layers with the long-chain surfactants, while the dodecane and surfactant molecules having commensurable chain lengths are mainly forming mixed monolayer.

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 C13DMPO (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 C13DMPO 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.

Drop profile analysis tensiometry used in the oscillating drop mode provides the dilational viscoelasticity of adsorption layers at liquid interfaces. Applied during the progress of adsorption the dynamic surface rheology can be monitored. For β-casein solutions at the same surface pressure values, the larger the dynamic dilational viscoelasticity the longer the adsorption time, i.e., the smaller the studied protein concentration is. For β-lactoglobulin and human serum albumin, the differences in the viscoelasticity values are less or not dependent on the adsorption time at identical surface pressures. The observed effects are caused by the flexibility of BCS, while the globular proteins BLG and HSA do not change their conformation significantly within the adsorption layer.

The measured dynamic surface tension of a water drop in air saturated by heptane vapor shows a sharp decrease from about 60 mN m−1 to 40 mN m−1, and less after a certain adsorption time. The observed adsorption kinetics is analyzed by a theoretical model based on multilayer adsorption of alkanes from the vapor phase at the water surface. The model assumes a dependence of the kinetic coefficients of adsorption and desorption on the surface coverage and in equilibrium it reduces to the classical Brunauer–Emmett–Teller adsorption isotherm. The calculated time dependencies of adsorption and surface tension agree well with experimental data and predict a five-layer adsorption of heptane.

For qualitative and quantitative description of adsorption equilibrium and hysteresis in open slit-like micropores, theoretically rigorous equations are proposed based on the theory of volume filling of micropores which imply the physical and formal analogy between the volume filling of micropores and capillary condensation. The applicability of the proposed equations for description of the hysteresis in such systems is demonstrated for water adsorption/desorption isotherm on the fibrous carbon material AUVM-Dnepr which possesses micro- and mesoporous structure.

The adsorption of surfactants from aqueous solution at the water/air interface is changed when the air phase contains hexane vapor. This co-adsorption of surfactant and hexane depends on the hexane vapor pressure. A thermodynamic model developed for the adsorption of surfactant mixtures can be adapted to the present situation. The surfactants studied were SDS, C12TAB and C12DMPO, and the dependence of their adsorption characteristics on the partial hexane vapor pressure was determined. The co-adsorption of hexane from the vapor phase increases the surface activity of the adsorbing surfactants.

In the framework of macroscopic thermodynamics of deformation, expressions are proposed for the calculation of deformation isotherms along the adsorption and desorption branches of the hysteresis loop within the linear and elastic deformation domains. With the assumption of spatially homogeneous (in the statistical sense) medium and scale-invariant behaviour of the relaxation rate, the generalized equation is proposed for the calculation of the hysteresis loop throughout the entire range of the adsorbate pressure in the bulk phase. In this equation, the irreversibility parameter is the governing one. The proposed equations are verified for the benzene adsorption–desorption isotherm on the organosubstituted synthetic fluorhectorite.

The influence of the addition of the nonionic surfactants C12DMPO, C14DMPO, C10OH, and C10EO5 at concentrations between 10(-5) and 10(-1) mmol/L to solutions of β-casein (BCS) and β-lactoglobulin (BLG) at a fixed concentration of 10(-5) mmol/L on the dilational surface rheology is studied. A maximum in the viscoelasticity modulus |E| occurs at very low surfactant concentrations (10(-4) to 10(-3) mmol/L) for mixtures of BCS with C12DMPO and C14DMPO and for mixtures of BLG with C10EO5, while for mixture of BCS with C10EO5 the value of |E| only slightly increased. The |E| values calculated with a recently developed model, which assumes changes in the interfacial molar area of the protein molecules due to the interaction with the surfactants, are in satisfactory agreement with experimental data. A linear dependence exists between the ratio of the maximum modulus for the mixture to the modulus of the single protein solution and the coefficient reflecting the influence of the surfactants on the adsorption activity of the protein.

In drop profile analysis tensiometry, the ratio of drop surfaces area S to volume V is large, i.e., S/V >> 1. In such a case, the concentration of a surfactant within the drop bulk decreases due to adsorption at the drop surface. In contrast, in bubble profile analysis tensiometry, we have S/V << 1 so that depletion due to adsorption is negligible. A protocol is presented to determine the correct adsorption parameters of surfactants from surface tension data measured by bubble and drop profile analysis tensiometry. The procedure is applied to experimental data measured for selected surfactants of different adsorption activities: C10OH, CTAB, Tween 20, and the equimolar mixture SDS + DoTAB. The results show that for surfactants with higher surface activity, the differences between the surface tensions measured with the drops and bubbles profile analysis tensiometry, respectively, are larger, while for less surface-active surfactants, such as SDS, the results obtained from drop and bubble profile experiments are very close. The correction procedure is based on the same set of adsorption parameters used to fit both the experimental data obtained from drop-based measurements (which involve the depletion effects) and those data measured in a way that depletion effects are negligible.

Using drop profile analysis tensiometry the adsorption dynamics and the equilibrium equation of state of beta-lactoglobulin (BLG) at the water/tetradecane (W/TD) interface are studied at pH 3, 5 and 7. The data are well described by a thermodynamic adsorption model using almost identical model parameters for all three pH values except for the surface activity coefficient. The surface pressure isotherms at the water/air (W/A) surface exhibit much steeper run than interfacial pressure at the W/TD interface for any of the studied cases at pH 3, 5 and 7, and the calculated adsorption isotherm data point at smaller adsorbed amounts for these pH. This seems to be in contrast to the much larger interfacial pressure changes reached at high BLG concentrations at the W/TD interface, which are almost three times higher than those at the W/A surface. The observations can be explained by a strong interaction between BLG and the oil molecules at the interface. The dynamic interfacial tensions can be adequately described by a mixed adsorption model, assuming a diffusional transport of the protein molecules in the aqueous bulk phase and an adsorption mechanism which assumes a change of the adsorption activity parameter in dependence of the interfacial coverage. Refereed/Peer-reviewed

The adsorption from mixed aqueous solutions of polyallyl amine hydrochloride (PAH)/sodium dodecyl sulphate (SDS), both in absence and presence of the inorganic electrolyte NaCl, at the solution/tetradecane interface is studied experimentally by drop profile analysis tensiometry. The results are discussed in terms of a competitive adsorption of PAH + SDS complexes and unbound SDS molecules. A thermodynamic model, developed originally for the adsorption of protein/surfactant mixtures, is modified such that it takes into account the formation of PAH + SDS complexes and the influence of the SDS concentration on their surface activity. It is shown that at low SDS concentrations the properties of the adsorbed monolayer are determined mostly by the adsorption of complexes, while at high SDS concentrations the properties are determined mostly by the SDS adsorption and the effect of the PAH + SDS complexes is negligibly small. The proposed modified model demonstrates good agreement with the experimental data.

The hydrophobicity of the talc basal surface is considered in the framework of the concept which relates the properties of layered silicates and their dispersions to the differences between the characteristics of the basal and side surfaces of their particles. The ab initio calculations of the energetics and geometry of the microclusters formed by water molecules adsorbed on the active sites (oxygen ions) located at the perfect basal surface of talc are performed. It is shown that the typical property of the hydrophobic surface is the adsorption of single molecules of water on extremely scarce or weak active sites of the surface, which act as secondary adsorption sites, and subsequent adsorption of water molecules on these secondary sites which results in the formation of ring-like structures. The heat of adsorption on this surface is shown to be essentially lower than the water condensation heat, which is also indicative of the hydrophobicity of the basal surface of talc.

The dynamic interfacial tension and dilational rheology of alkyltrimethylammonium bromides (C n TAB) solutions are studied for n = 10, 12, 14 and 16 using drop profile analysis and capillary pressure tensiometry. The experimental data are analyzed on the basis of two theoretical models, the Frumkin Ionic Compressibility and the Langmuir Compressibility models [1] . We show that even the simplified Langmuir Compressibility model is able to adequately describe the dynamic properties of the investigated ionic surfactants. Dynamic experiments point out the difficulties related to short chain surfactants due to their very fast adsorption kinetics which cannot be studied with conventional tensiometer setups.

The equilibrium and dynamic interfacial properties of β-casein (βCS) adsorbed at the water/hexane interface have been studied systematically over a wide range of pH. The results are analyzed in the context of a recently developed thermodynamic model, which is not only applied to characterize the adsorption behavior of βCS layers, but at the same time the visco-elastic properties of the surface layer. The equilibrium model can be adequately used for the adsorption layer when they are in a quasi-equilibrium state, however, it turned out that reliable information is provided only in the vicinity of equilibrium. Thus, the interfacial structure attained by the protein at the water/hexane interface resulting from the cohesive interaction between oil phase and the hydrophobic parts of the protein molecules is satisfactorily accounted in view of the results presented. The dilational viscosity of the adsorbed βCS layers is found to be very small and therefore, the interfacial layers behave essentially elastic. The analysis of the interfacial elasticity provides information on the conformational transitions within the interfacial layer. The selection of the model parameters is based on the slow structural change of βCS adsorption layers with increasing pH of the solution. The maxima encountered in the dynamic elasticity values even at pH 5, where βCS is in its most compact conformation, clearly suggest that the interfacial layer undergoes structural changes depending on the age of the adsorption layer.

In the present work, the properties of dodecyl dimethyl phosphine oxide (C12DMPO) at the water/decane interface are studied and compared with those obtained earlier at the interface to hexane. To simulate the interfacial behavior, a two-component thermodynamic model is proposed, which combines the equation of state and Frumkin isotherm for decane with the reorientation model involving the intrinsic compressibility for the surfactant. In this approach, the surface activity of decane is governed by its interaction with C12DMPO. The theory predicts the influence of decane on the decrease of the surface tension at a very low surfactant concentration for realistic values of the ratio of the adsorbed amounts of decane and surfactant. The surfactant&rsquo, s distribution coefficient between the aqueous and decane phases is determined. Two types of adsorption systems were used: a decane drop immersed into the C12DMPO aqueous solution, and a water drop immersed into the C12DMPO solution in decane. To determine the distribution coefficient, a method based on the analysis of the transfer of C12DMPO between water and decane is also employed.

We measured the interfacial tensions of aqueous solutions against different oil phases using drop profile analysis tensiometry (PAT-1, Sinterface Technologies, Germany) for decyl- and dodecyltrimethylammonium bromide (C10TAB and C12TAB) in phosphate buffer (10 mM, pH7). The following alkanes were used as oil phases: hexane, heptane, octane, nonane, decane, dodecane and tetradecane. The obtained equilibrium interfacial tension isotherms were fitted by the Frumkin Ionic Compressibility model (FIC). The surfactants adsorb at the water/oil interface in competition with the oil molecules. At high surfactant surface coverage this competitive adsorption is manifested in two ways. First, for short chain surfactants, the oil molecules are embedded into the adsorption layer. Second, for long chain surfactants, the short alkane chains of the oil molecules are squeezed out from the adsorption layer due to strong mutual interaction between surfactants' chains.

Mixed protein–surfactant adsorption layers at liquid interfaces are described including the thermodynamic basis, the adsorption kinetics and the shear and dilational interfacial rheology. It is shown that due to the protrusion of hydrophobic protein parts into the oil phase the adsorption layers at the water–hexane interface are stronger anchored as compared to the water-air surface. Based on the different adsorption protocols, a sequential and a simultaneous scheme, the peculiarities of complexes between proteins and added surfactants are shown when formed in the solution bulk or at a liquid interface. The picture drawn from adsorption studies is supported by the findings of interfacial rheology.

The adsorption behaviour of β-Lactoglobulin (BLG) at the air/water surface and the visco-elastic properties of the BLG adsorption layers are discussed in terms of quasi-equilibrium adsorption isotherms and equation of state gained by comparing a model with a set of experimental data obtained by bubble profile analysis tensiometry. The presented simultaneous characterization of the adsorption isotherm and the dilational visco-elasticity under dynamic and equilibrium conditions is based on measurements of the dynamic surface pressure and its response to sinusoidal bubble area variations. The thermodynamic model was applied to the set of experimental data under the assumptions of monolayer compressibility, surface dimerization and development of a secondary layer. The effect of the bubble surface age on the adsorption isotherm and equation of state, and also on the visco-elastic characteristics is discussed and it allows concluding that the existence of a bilayer structure, which is formed beyond a certain protein adsorption, is responsible for the observed relaxation processes.

The dynamics of surfactant interfacial layers was first discussed more than a century ago. In 1946 the most important work by Ward and Tordai was published which is still the theoretical basis of all new models to describe the time dependence of interfacial properties. In addition to the diffusion controlled adsorption mechanism, many other models have been postulated in literature, however, well performed experiments with well defined surfactant systems have shown that the diffusional transport is the main process governing the entire formation of surfactant adsorption layers. The main prerequisite, in addition to the diffusional transport, is the consideration of the right boundary condition at the interface, given by a respective equation of state. In addition to the classical models of Langmuir and Frumkin, also the so-called reorientation or interfacial aggregation models are to be assumed to reach a quantitative description of respective experimental data. Moreover, the adsorption of surfactants at the interface between water and a gas phase different from air can be strongly influenced by the type of molecules within the gas phase, such as alkane vapours. These oil molecules co-adsorb from the gas phase and change the adsorption kinetics strongly. Besides the discussion of how to apply theoretical adsorption kinetics models correctly, a large number of experimental data are presented and the way of a quantitative analysis of the adsorption mechanism and the main characteristic parameters is presented. This includes micellar solutions as well as mixtures of surfactants of ionic and non-ionic nature.

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 (CaCl(2) and MgCl(2) 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 0.01 M 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 0.005 Hz and 0.2 Hz. The visco-elasticity modulus in the presence of hardness salts is higher as compared with its values in the presence of 0.01 M NaCl additions. The ageing of SDS solutions leads to an essential increase of the visco-elastic modulus.

The surface tension and dilatational visco-elasticity isotherms for β-casein determined at pH 7 and 9 are essentially the same, but differ remarkably from those measured at the isoelectric point (i.e.p.) of the protein at pH 5. A recently developed thermodynamic model is applied to the experimental data, which were not only obtained at equilibrium, but also under quasi-equilibrium conditions. It turned out that such a model can be adequately applied to data obtained not too far from the equilibrium state of a protein adsorption layer. The change in the model parameters allows to understand slow changes in the structure of the adsorption layer. Even at pH 5, where β-casein is most hydrophobic and in its most compact conformation, the data point to the fact that conformational changes may happen at the interface upon adsorption.

Equilibrium and dynamic surface tension of non-ionic triblock copolymers, Pluronics, varying in the number of poly(ethylene oxide) and poly(propylene oxide) groups have been measured by means of drop profile tensiometry at the water–hexane interface. The experimental data have been explained on the basis of a theory previously developed for protein solutions [1] . This model assumes the coexistence of different adsorbed states at the interface, depending on the surface coverage. It has been shown that the best fit is achieved when a polylayer adsorption is considered. Reasonable values of the adsorption layer thickness and realistic values of the diffusion coefficient are obtained which validate the model proposed.

Each experimental method has a certain range of application, and so do the instruments for measuring dynamic interfacial tension and dilational rheology. While the capillary pressure tensiometry provides data for the shortest adsorption times starting from milliseconds at liquid/gas and tens of milliseconds at liquid/liquid interfaces, the drop profile tensiometry allows measurements in a time window from seconds to many hours. Although both methods together cover a time range of about eight orders of magnitude (10(-3) s to 10(5) s), not all surfactants can be investigated with these techniques in the required concentration range. The same is true for studies of the dilational rheology. While drop profile tensiometry allows oscillations between 10(-3) Hz and 0.2 Hz, which can be complemented by measurements with capillary pressure oscillating drops and the capillary wave damping method (up to 10(3) Hz) these six orders of magnitude in frequency are often insufficient for a complete characterization of interfacial dilational relaxations of surfactant adsorption layers. The presented analysis provides a guide to select the most suitable experimental method for a given surfactant to be studied. The analysis is based on a diffusion controlled adsorption kinetics and a Langmuir adsorption model.

A qualitative and quantitative description is given for the H3 hysteresis loop at low pressures using the generalized Dubinin–Astakhov equation. Irreversibility of the adsorption system was taken into account by introducing an additional governing parameter. A relationship was found between this parameter and the potential barrier for desorption from adsorption traps. The proposed equation satisfactorily describes the hysteresis loop at low pressures for a series of systems.

The adsorption of the anionic surfactant SDS in mixtures with non-ionic surfactants of the Triton type (X-45, X-100, X-165, X-405) is studied by bubble profile analysis tensiometry at the solution/air interface. The surface tension isotherms are described by a thermodynamic model for mixed surfactants which allows consideration of different adsorption models for the two compounds: a reorientation model for the Tritons and a Frumkin model for SDS. The experimental data are very well described by the model while for the mixtures the characteristic parameters of the single compounds have been used.

The Frenkel-Halsey-Hill equation is used to describe the adsorption branch of a hysteresis loop upon polylayer adsorption with an H3 loop according to IUPAC nomenclature. The equation for the desorption branch of a hysteresis loop is derived from a combined solution to the equation for the Gibbs potential change, given the adsorbent swelling and pore connectivity function, and the Laplace equation taken for the conditions of infinitely elongated meniscus. This equation is shown to connect the adsorbate relative pressure in a bulk phase for the desorption branch of a hysteresis loop with the key parameters of the adsorption system. The equation obtained was verified by a water adsorption isotherm on natural mineral schungite.

Harmonic drop surface area oscillations are performed at a fixed frequency (0.1 Hz) to measure the dilational visco-elasticity for three proteins: &beta, casein (BCS), &beta, lactoglobulin (BLG), and human serum albumin (HSA). The surface area oscillations were performed with different amplitudes in order to find the origin of non-linearity effects. The analysis of data shows that the non-linearity in the equation of state&mdash, i.e., the relation between surface pressure and surface concentration of adsorbed protein molecules&mdash, is the main source of the amplitude effects on the apparent visco-elasticity, while perturbations due to non-uniform expansions and compressions of the surface layer, inertia effects leading to deviations of the drop profile from the Laplacian shape, or convective transport in the drop bulk are of less importance. While for the globular proteins, HSA and BLG the amplitude effects on the apparent visco-elasticity are rather large, for the non-globular protein BCS this effect is negligible in the studied range of up to 10% area deformation.

Surface and interfacial tension measurements have been performed at the water/air and water/hexane interface by drop profile analysis tensiometry for a series of alkyl trimethylammonium bromides with different chain lengths (C10, C12, C14 and C16). The effect of neutral phosphate buffer (10 mM, pH 7) has been investigated and the results have been compared with literature data obtained for the same surfactants in the absence of salt. The use of a modified Frumkin isotherm (Ionic Compressibility) taking into account the mean activity of all ions in solution leads to a real improvement of the data interpretation, while the classical Frumkin Compressibility model yields similar results but overestimates the adsorption parameters. At the water/hexane interface, the hexane molecules are incorporated in the surfactant layer and it results a kind of competitive adsorption for the shortest chain surfactant (10 carbons). For the longest chains, the attractive interactions between the hydrophobic chains of the adsorbed surfactants are strong enough to replace the solvent molecules from the interface.

For the characterisation of interfaces between two immiscible liquids, capillary pressure tensiometry is the most versatile method. To measure short time interfacial tensions it has to be applied under very dynamic conditions for which the following protocols have been developed: 1—continuously growing drop (CGD); 2—pre-aged growing drop (PGD); 3—stopped growing drop (SGD). The CGD is a procedure analogous to the well-known maximum bubble pressure tensiometry for liquid–gas interfaces, however, the processes of drop detachment and formation of the subsequent drop require a rather complex data analysis. For the PGD protocol based on a growing drop with an initially pre-established equilibrium adsorption layer, the complexities are less, but for higher surfactant concentrations it is not optimum. The SGD protocol provides a drop with a fresh surface and the dynamic interfacial tension can be monitored in the absence of hydrodynamic effects. All three protocols complement each other and provide a good set of data for dynamic interfacial tensions at short adsorption times.

The adsorption kinetics of mixed non-ionic surfactants can be described by a diffusion controlled adsorption when the correct model is used, i.e. when for each adsorbing species the corresponding thermodynamic model for the adsorption equilibrium is applied. For non-ionic surfactants, such as oxyethylated alcohols C 12 EO 5 and C 14 EO 8 and Tritons X- n , the reorientation model is the appropriate model. The dynamic surface tensions measured by bubble profile tensiometry are described very well by an efficient diffusion coefficient decreasing with the total surfactant bulk concentration. The physical reason for the change in D eff is the effect of convection in the system becoming more pronounced with the increasing in adsorption time. Equimolar mixtures of Triton X-45 and X-165 mimic the adsorption behaviour of Triton X-100.