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The physicochemical properties of aqueous ternary ionic liquid (IL) and nanoparticle systems are affected by the various intermolecular interactions such as van der Waals, electrostatic and structural. Recently these systems have been considered both to increase the stability of nanofluids and to change the surface activity of the surface active ILs. A systematic experimental study was conducted on aqueous solutions containing a surface active ionic liquid, 1-octyl-3-methylimidazolium bromide ([C8mim][Br]), in pure water and in CuO-water nanofluids to a better understanding of the aggregation behavior occurring in these systems. The electrical conductivity (κ) data were obtained for [C8mim][Br] + water and [C8mim][Br] + CuO–water nanofluid (with 0.00066 wt%, 0.005 wt% and 0.01 wt% of CuO NPs) systems at 288.15, 293.15, 298.15 and 303.15 K. For these systems, surface tension (γ) measurements were taken at 298.15 K. The accurate analysis of the obtained data showed that the critical micelle concentration (cmc) for [C8mim][Br] in aqueous solution is increased with addition of CuO NPs to pure water, as well as with increasing concentration of CuO NPs in water-based fluid. The values of Gibbs energy, ΔG°mic, enthalpy, ΔH°mic, and entropy, ΔS°mic, of micellization were determined from the specific electrical conductivity data. The values of ΔG°mic were negative and magnitude of ΔG°mic (kJ⋅mol−1) followed the order: 288.15 K (− 21.95) 0) and with a temperature raise, this process becomes enthalpically driven process (ΔH°mic

The elastic modulus and hydrophilicity of cross-linked poly(dimethylsiloxane) (PDMS) are tunable via cross-linker concentration and the addition of a simple surfactant, C12E4, before curing. However, the surfactant concentration, [C12E4], reduces the elastic modulus (73% lower for 6.3% w/w) because it reduces the extent of curing. This is likely because the hygroscopic surfactant results in water poisoning of the catalyst. Three distinct time-dependent hydrophilicity profiles were identified using water contact angle analysis with [C12E4] determining which profile was observed. This indicates the concentration-dependent phase behavior of C12E4 within PDMS films. Changes in phase behavior were identified using small-angle neutron scattering (SANS) and a compatibility study. No surface excess or surface segregation of surfactant was observed at the PDMS–air interface. However, a surface excess revealed by neutron reflectivity against a D2O interface indicates that the increase in hydrophilicity results from the migration of C12E4 to the film interface when exposed to water.

The solution behaviors of the binary mixture of double chain cationic surfactant didodecyldimethylammonium bromide (DDAB) with nonionic surfactants of varied head groups, EO-9 and EO-40, in the presence and absence of electrolytes were studied and found nonideal behavior. The different physicochemical properties such as Gibb's surface excess (Γ), minimum area per molecule (Amin), and interaction parameters at bulk (βM) and interface (βσ) were calculated. In the presence of nonionic surfactants, lowering of CMC, CVC, and surface tension at these two concentrations of DDAB were observed. The βM and βσ values indicate strong interaction between DDAB and EO-40 mixed system. Further, addition of electrolytes to the mixed systems show increased interaction and change of physicochemical properties because of the combination of electrical and salting out effects.

The study of interactions between surfactant and salt in aqueous solutions has attracted significant interest in recent years because of their widespread applications and relatively complex behavior. This work reports the systematic study of surface phenomenon and self-aggregation behavior of cationic surfactant cetyltrimethyl ammonium bromide (CTAB) with ammonium nitrate (NH \begin{document}$ _4 $\end{document} NO \begin{document}$ _3 $\end{document} ) salt. Surface and thermodynamic properties of cationic surfactant CTAB with NH \begin{document}$ _4 $\end{document} NO \begin{document}$ _3 $\end{document} were investigated at different temperatures using different techniques such as conductometry and surface tensiometery. The surface tension measurement was carried out to find out the critical micelle concentration, free energy of adsorption, free energy of micellization, minimum area per molecule, and surface excess concentration. The study reveals that the process of micellization is spontaneous and exothermic in nature. Conductance measurement was carried out to determine critical micelle concentration, degree of ionization and degree of counter ion binding. Addition of NH \begin{document}$ _4 $\end{document} NO \begin{document}$ _3 $\end{document} to the surfactant solutions increase the values of degree of ionization and degree of counter ion binding, although it lowers the values of critical micelle concentration showing that the process of micellization is more favorable and spontaneous. The study is very helpful to develop better understanding about interaction between electrolyte and surfactant, which are used in many applications and in different processes (e.g., pharmaceutical, industrial foaming, drug solubilization, oil recovery, and medium for metal nanoparticle formation).

A series of nonionic ethoxylate surfactants containing different combinations of alkyl, phenyl, and adamantyl units in nine different arrangements, each combined with penta- and hexa-ethylene glycol groups, were synthesized and purified. The surface properties of all of the surfactants were investigated at the air-water (A-W) interface using surface tension (ST) to determine the limiting surface excess (Γlim), the limiting surface tension (σlim), and the critical micelle concentration (CMC). A smaller selection was investigated at the hydrophilic silica-water interface by neutron reflectometry to obtain the thickness of the adsorbed layer and the total adsorption at the CMC. An unusual and largely unrecognized feature of the ethoxylate group is that it is both hydrophilic and hydrophobic. It was found possible to account for the variation of σlim and Γlim of all of the adsorbed layers in terms of a balance of the estimated STs of the sublayers forming the overall adsorbed layer, including that of the underlying ethoxylate layer. The values of σlim were found to be highest for phenyl- and adamantyl-capped surfactants and lowest mainly when there was more than one methyl group at the surface. However, in terms of the concentration required to reach a given low ST, increasing the number of attached methyl groups was found to be less effective than using a smaller number of better-placed methyl groups. At the solid-liquid interface, adsorption at or above the CMC was in all cases in the form of a fragmented bilayer whose coverage varied approximately linearly with the packing parameter. However, results on the phenyl-capped surfactants showed that the high ST exhibited by these surfactants at the A-W interface becomes a high cohesion energy in the interior of the bilayer and they exhibited significantly higher adsorption than expected from simple packing arguments.

Hypothesis l -carnitine plays a crucial role in the cellular production of energy by transporting fatty acids into mitochondria. Acylated l -carnitines are amphiphilic and if appropriate physical properties were demonstrated, they could replace many currently used surfactants with improved biocompatibility and health benefits. Experiments This work evaluated the surface adsorption of lauroyl- l -carnitine (C12LC) and its aggregation behavior. The size and shape of the aggregates of C12LC surfactant were studied at different temperatures, concentrations, pH and ionic strength by dynamic light scattering (DLS) and small-angle neutron scattering (SANS). Surface tension measurements were carried out to determine the critical micellar concentration (CMC) of C12LC. Combining with the Gibbs equation, the surface excess at different concentrations could be determined. Neutron reflection (NR) was used to determine the structure of the adsorbed layer at the air/water interface with the help of isotopic contrast variations. Findings At pH 7, the limiting area per molecule (ACMC) of the zwitterionic C12LC adsorbed layer at the air/water interface was found to be 46 A2 from surface tension and neutron reflection, smaller than the values of C12PC, C12E5, DTAB, C12C4betaine and C12C8betaine but close to that of SDS. A pronounced surface tension minimum at pH 2 at the low ionic strength was linked to a minimum value of area per molecule of about 30 A2, indicating the competitive adsorption from traces of lauric acid produced by hydrolysis of C12LC. As the concentration increased, area per molecule reached a plateau of 37–39 A2, indicating the dissolution of the more surface-active lauric acid into the micelles of C12LC. DLS and SANS showed that the size and shape of micelles had little response to temperature, concentration, ionic strength or pH. The SANS profiles measured under 3 isotopic contrasts could be well fitted by the core–shell model, giving a spherical core radius of 15.7 A and a shell thickness of 10.5 A. The decrease of pH led to more protonated carboxyl groups and more positively charged micelles, but the micellar structures remained unchanged, in spite of their stronger interaction. These features make C12LC potentially attractive as a solubilizing agent.

A substantial amount of water used for fracking shale formations is trapped by capillary and interfacial forces. Such trapped water is detrimental to gas production because of its potential to obstruct gas’s desorption and, subsequently, its flow path. Surfactants are proposed to alleviate the problem; however, further insight is required to understand the underlying mechanism. In this study, a cationic surfactant, namely, cetyltrimethylammonium bromide (CTAB), and a clay-rich Marcellus shale are used to investigate and explain the mechanism. The study encompasses a series of systematic experiments and molecular simulations. First, laboratory measurements of CH₄–brine interfacial tension, CH₄ surface excess, and zeta potential at different CTAB concentrations were conducted. Then, we evaluated CH₄ adsorption in Marcellus shale before and after treatment with CTAB. Second, a molecular dynamics simulation by GROMACS software was used to explain the phenomenon at the molecular level. Experimental results indicated that CTAB reduced the CH₄–brine interfacial tension by up to 80%. The zeta potential data showed that shale’s dominant surface charge was altered from negative to positive after treatment with CTAB. Furthermore, the presence of CTAB has significantly influenced the distribution of CH₄ in the aqueous phase as indicated by the changes in the CH₄ surface excess concentration. Moreover, the adsorbed CH₄ amount decreased with increasing CTAB concentration when the CTAB concentration was kept below the critical micelle concentration (CMC). The reduction in adsorbed CH4 was explained by the molecular dynamics simulation results, which revealed a 62% shrinkage in vertical distances between CH₄ molecules and clays after introducing CTAB. Simulation findings also unfold that CTAB has reduced the density distribution of CH₄ molecules along with clay layers by 64%. One of the more significant result of this study is that surfactants injected at above CMC values can lessen fracking water trapping by reducing CH₄ brine interfacial tension, changing surface charges, and reducing molecular distances between CH₄ and hydrophilic clays.

Bile salts are bio-surfactant molecules, anionic in nature, and show an energetic character in cholesterol and lipid solubilization. These amphiphiles are also used as a drug carrier. Being anionic they can interact strongly with other cationic amphiphiles. Keeping in mind this fact, we have investigated the interfacial and spectroscopic performance of cationic phenothiazine drug with bile salt in the nonattendance and attendance 250 mM urea. Surface tension and absorbance (UV-visible spectroscopy) experiments have been performed to elucidate the nature of interactions. The composition and interaction parameters at the interface or surface were computed by using the Rosen theory of mixed monolayer. The other surface parameters were computed by adopting Gibbs adsorption isotherm. Benesi-Hildebrand (B–H) model was utilized to evaluate the binding constant.

2-Hydroxy-1, 4-napthoquinone (lawsone) natural red–orange dye was extracted from fresh henna (Lawsonia inermis) leaves in an alkaline media. The lawsone-surfactant solubilization constants (KLS) were calculated for the first time by using cationic cetyltrimethylammonium bromide (CTAB) and anionic sodium dodecyl sulphate (SDS). The standard free energy, concentration of solubilized lawsone and number of lawsone molecules solubilized into micelles were calculated and discussed. Surface excess, minimum surface area per molecule, surface pressure, free energy (adsorption and aggregation) and equilibrium constants of different states were determined from tensiometry. Different metal ions (Ag+, Co2+, Cu2+, Ni2+, Fe3+, Zn2+ and Al3+) were used to determine the complex forming ability with lawsone. Out of these, Ag+ ions have strong binding capacity with lawsone. The adsorption of lawsone on the surface of glass with silver ions in presence of CTAB was also observed at pH ≥ 9.0. The pseudo-first, second-order kinetic equation, intraparticles diffusion and Elovich models were used to determine the kinetics of lawsone adsorption onto the surface of glass and a probable mechanism has been discussed. Lawsone adsorption followed second-order kinetic equation (k2 = 0.019 g·mg−1·min−1).

Surfactants are centrally important in many scientific and engineering fields and are used for many purposes such as foaming agents and detergents. However, many challenges remain in providing a comprehensive understanding of their behavior. Here, we provide a brief historical overview of the study of surfactant adsorption at the air-water interface, followed by a discussion of some recent advances in this area from our group. The main focus is on incorporating an accurate description of the adsorption layer thickness of surfactant at the air-water interface. Surfactants have a wide distribution at the air-water interface, which can have a significant effect on important properties such as the surface excess, surface tension, and surface potential. We have developed a modified Poisson-Boltzmann (MPB) model to describe this effect, which we outline here. We also address the remaining challenges and future research directions in this area. We believe that experimental techniques, modeling, and simulation should be combined to form a holistic picture of surfactant adsorption at the air-water interface.

Titanium dioxide (TiO2) is a well-known photocatalyst that has been used in photocatalysis and has been studied as an alternative for artificial photosynthesis cells. Many works have tried doping this material with different elements to increase its photoactivity; however, a consequence of doping that has not received much attention is the segregation at the nanoparticle interfaces, such as the surface and the grain boundary (GB). In this study, Sb-doped TiO2 nanoparticles have been produced by the polymeric precursor method, with the compositional range varying from 0 to 2 mol% Sb. The surface excess was measured by the surface lixiviation method, and the GB excess was calculated considering the total amount of Sb and its solubility in the TiO2 bulk. The results showed that Sb interfacial segregation at both surface and GB increased the specific surface areas, reduced the crystallite sizes, increased the presence of the rutile phase, and changed the CO2 adsorption, evidenced by DRIFT spectroscopy. The photoactivity was tested by the degradation of acetaminophen (ACT) under UV irradiation, revealing an increase of ~53% of activity for 0.05 mol% Sb-doped TiO2 compared to undoped TiO2.

The cationic content of water represents a major quality control parameter that needs to be followed by a rapid, on-site, and low-cost method. Herein, we report a novel method for a facile monitoring of the mineral content of drinking water by making use of responsive complex emulsions. The morphology of biphasic oil-in-water droplets solely depends on the balance of interfacial tensions, and we demonstrate that changes in the surfactant effectiveness, caused by variations in the mineral content inside the continuous phase, can be visualized by monitoring internal droplet shapes. An addition of metal cations can significantly influence the surfactant critical micelle concentrations and the surface excess values and therefore induce changes in the effectiveness of ionic surfactants, such as sodium dodecyl sulfate. The morphological response of Janus emulsions droplets was tracked via a simple microscopic setup. We observed that the extent of the droplet response was dependent on the salt concentration and valency, with divalent cations (responsive for water hardness), resulting in a more pronounced response. In this way, Ca2+ and Mg2+ levels could be quantitatively measured, which we showcased by determination of the mineral content of commercial water samples. The herein demonstrated device concept may provide a new alternative rapid monitoring of water hardness levels in a simple and cost-effective setup.

The aim of this study was to investigate micellar and self-assembly properties of four sodium salts of naphthenic acid mixtures by determination and comparative analysis of their critical micelle concentration values at seven different temperatures ranging from 10 to 40 °C using spectrofluorophotometric measurements. It was concluded that fractions having the lowest percentage of aliphatic structures give the least flexible micelles due to sterically rigid structure of cyclic side chains, what makes them difficult to pack in the micellar core. Additionally, surface properties of aqueous solutions of investigated mixtures were studied by the determination of the maximum surface excess, Γ max and the minimum area per surfactant molecule (A min) values.

Preferential adsorption of nanorods onto smooth walls is investigated using dissipative particle dynamics in the absence of specific attraction and a depletant. Although the translational and rotational entropy of nanorods is significantly reduced after adsorption, the effective attraction between the nanorod and wall is clearly identified based on the distribution profile of rods. As the rod length increases, the attractive interaction grows stronger and clusters of aligned nanorods can emerge on the smooth wall. However, the presence of a depletion zone of nanorods adjacent to the adsorbed layer gives zero surface excess. These two regions correspond to the primary minimum and maximum mean force potentials observed. Since adsorbed nanorods lose their rotational and translational entropy, the strong adsorption of long nanorods has to be attributed to the entropy gain associated with the increase in free volume for the solvent in this athermal system. Nonetheless, as the surface roughness is present, entropy-driven attraction is lessened, similar to the depletion force between colloids.

The surface adsorption of bovine serum albumin in pure water and salted aqueous solutions was studied by neutron reflection. With the contrast match technique, the surface excess in null reflecting water as a function of the protein concentration was revealed. It is found that, in a concentration range from 1 ppm (parts per million, mg/L) to 1000 ppm, without salts, the surface excess shows a profound peak at around 20 ppm; with salts, the surface excess increases steadily with the protein concentration. When the surface excess at a specific protein concentration is viewed, the introduction of sodium chloride causes either a salting down effect (surface adsorption decline) or a salting up effect (surface adsorption increase), depending upon the protein concentration. The salting up effect is observed at the low (∼1 ppm) and high (∼1000 ppm) concentrations, and the salting down effect dominates the intermediate concentration range. The change in solution pH relative to the isoelectric point (PI) can act as a simple indicator for the salting up or salting down behavior. When the solution pH is shifted toward the PI by adding salts, surface adsorption enhances; when the solution pH is shifted away from the PI by adding salts, surface adsorption declines.

Several factors influence the IFT of oil and formation water. These factors are rooted in the complex composition of oil, presence of different salts in water, water salinity, temperature, and pressure of reservoir. In the first part of this paper, effect of salinity on IFT between brine and an Iranian live oil sample has been studied experimentally. It is observed that IFT increases almost linearly with brine concentration. Also, linear increasing behavior of IFT with respect to pressure is obviously seen. Then, using thermodynamic properties such as surface excess concentration, chemical potential, chemical activity, and activity coefficient, results were analyzed and observed effect of salinity and pressure were justified thermodynamically. In the second part, the effect of asphaltene on IFT reduction has been studied. In previous works, the investigators extracted resin and asphaltene and then examined their effects on IFT in the absence of other fractions of oil phase. We believe that all fractions play a role in this phenomenon so, in this paper, the effect of natural surfactants of oil phase on IFT has been investigated in presence of all fractions of oil. Hence, SARA test was performed on all samples. Then, IFT between oil samples and brine were measured using captive drop instrument at 25 °C and 3000 psia. Results showed that neither asphaltene content nor asphaltene/resin ratio is a good indicator for effect of asphaltene on IFT, whereas colloidal instability index could be a useful tool to predict asphaltene effect on IFT.

The imidazolinium chloride salts have improved as a potential new material for a wide variety of industrial operations, due to their exceptional structures and properties. Therefore, recognition of the surface proprieties and thermodynamic criteria of this product is extremely important for fundamental and industrial operations. In this investigation a mixture of fatty imidazolinium chlorides was synthesized dealing with a novel method using sunflower oil as a promoter of fatty acids. The reaction of ethane-1,2 diamine with a fatty acid yields a fatty imidazoline molecule. Hydrochloric acid was used to obtain fatty imidazolinium hydrochlorides with cationic surfactant properties. A FT-IR and NMR spectroscopic technique was using to establish the synthetic structure. The surface tension and conductivity as a function of the surfactant concentration in aqueous solution were measured at distinct temperatures, to figure out the micellization, adsorption and aggregation characteristics in aqueous solutions. Formerly the effect of temperature on the CMC was investigated. The HLB values were assumed for our surfactant and the results achieved indicate that it is O/W emulsifier. The Krafft point was identified at 288.45 K. All Surface adsorption parameters like, the maximum surface excess concentration (Γmax), minimum area per molecule (Amin), effectiveness (πCMC), and efficiency of surface tension reduction (pC20) were calculated using Gibb’s equation. Finally, an attentive study of the thermodynamic aspects of air-ionic surfactant aqueous system reveals that the process of both micellization and adsorbtion was spontaneous and that adsorption is more favored than micellization.

The surfactant properties of amphiphilic hyperbranched polyglycerols (HPGs) were investigated. The HPGs were prepared by ring-opening multibranching polymerization of glycidol using hydrophobic initiators of varying size and structure. The cloud points for all HPG surfactants were found to be >80 °C in deionized water with >1 wt % NaCl. The HPG surfactants with hydrophilic-lipophilic balance values between 16 and 18 were found to form stable octanol/water (o/w) emulsions within a 24 h period. Several surface properties, including critical micelle concentration (CMC), efficiency of surface tension reduction (pC20), effectiveness of surface tension reduction (γCMC), surface excess concentration at the CMC (Γmax), minimum area/molecule at the interface (Amin), and the CMC/C20 ratio of the HPG surfactants were measured in deionized water at 22.6 °C. In general, increasing HPG size was marked by an increase in minimum surface area per molecule (Amin) at the aqueous liquid/air interface. This increase in size also led to lower CMC and greater pC20 values of HPG surfactants prepared with Tergitol 15-S-7 initiator (HPG 5a-5d), a commercially available ethylene glycol oligomer with a branched hydrophobic tail.

The partition rate of 2 model compounds, 2-naphthol (NAP) and ritonavir (RTV), across the water-octanol (W/O) interface was determined from aqueous solutions with and without the presence of a variety of common pharmaceutical excipients. The NAP molecule was present as either a unionized species in the phosphate buffer solution or as an anion in 0.01 M NaOH solution while RTV was present as dications in 0.1 M HCl. Excipients examined include different type of polymers (e.g., PVP-VA, HPMC, HPMCAS, PVP, PEG 8000), small molecules (e.g., glucose, lactose, maltoheptaose), and surfactants (e.g., Tween 80 and SDS). A noticeable to significant reduction of the partition rate of both NAP and RTV across the W/O interface was observed with aqueous media containing 0.01–0.1 μg/mL polymers including PVP-VA, HPMC, and HPMCAS. Reduction of NAP and RTV partition rate associated with such extremely low concentration of polymers in the aqueous media affirms the presence of a surface excess of adsorbed excipients at the W/O interface. Pi values of NAP and RTV across the W/O interface are found to be sensitive to (1) the molecule surface area, molecular weight and the degree of the polymerization of these pharmaceutical excipients, and (2) the ionization state of the model compound.

Oppositely charged polyelectrolyte/surfactant and the coacervate polyanion/polycation mixtures are known to display complex properties at water/air interface which are not fully elucidated. The change in surface tension of the anionic polyelectrolyte sodium poly(styrene sulfonate) (NaPSS) with either benzyldimethylhexadecylammonium chloride (BAC) as the cationic surfactant or the cationic polyelectrolyte polyallylamine hydrochloride (PAACl) as a function of temperature and added salts was investigated. Neither of the pure polyelectrolytes showed significant surface activity; however, addition of oppositely charged surfactant or polyelectrolyte to varying concentrations of NaPSS solutions had changed the surface activity drastically. The surface tension of the NaPSS/BAC complex is lower than that of pure BAC surfactant. The surface tension of these complexes showed significant decrease with increasing temperatures and the surface excess entropy was deduced from these measurements. Addition of ionic salts enhanced the association of the polyelectrolyte/surfactant mixture but had little effect on the polyelectrolytes coacervate. The surface tension of low concentrations of NaPSS/PAACl coacervate displayed a peak which can be attributed to charge inversion.

By applying the Gibbs equation to the bulk binding isotherms and surface composition of the air–water (A–W) interface in polyelectrolyte–surfactant (PE–S) systems, we show that their surface behavior can be explained semiquantitatively in terms of four concentration regions, which we label as A, B, C, and D. In the lowest-concentration range A, there are no bound PE–S complexes in the bulk but there may be adsorption of PE–S complexes at the surface. When significant adsorption occurs in this region, the surface tension (ST) drops with increasing concentration like a simple surfactant solution. Region B extends from the onset of bulk PE–S binding to the end of cooperative binding, in which the slow variation of surfactant activity with cooperative binding means that the ST changes relatively little, although adsorption may be significant. This leads to an approximate plateau, which may be at high or low ST. Region C starts where the binding in the bulk complex loses its cooperativity leading to a rapid change of surfactant activity with the total concentration. This, combined with significant adsorption, often leads to a sharp drop in ST. Region D is where precipitation and redissolution of the bulk PE–S complex occur. ST peaks may arise in region D because of loss of the solution complex that matches the value of the preferred surface stoichiometry, which seems to have a well-defined value for each system. The analysis is applied to the experimental systems, sodium polystyrene sulfonate–alkyltrimethylammonium bromides and poly(diallyldimethyl chloride)–sodium alkyl sulfates, with and without the added electrolyte, and includes data from bulk binding isotherms, phase diagrams, aggregation behavior, and direct measurements of the surface excess and stoichiometry of the surface. The successful fits of the Gibbs equation to the data confirm that the surfaces in these systems are largely equilibrated.

Oil-soluble ionic liquids (ILs) have been proved as effective additives in lubricant oils through tribological experiments and post-test analytical analyses. In this study, surface structures of lubricant base oil, oil-soluble ILs, and their mixtures at the air/liquid and solid/liquid interfaces have been studied using sum frequency generation (SFG) vibrational spectroscopy. At the air/base oil and air/IL interfaces, the alkyl chains of the studied compounds were shown to be conformationally disordered and their terminal methyl groups point outward at the liquid surface. The base oil dominates the air/(base oil + IL) interface due to its higher surface excess propensity and larger bulk concentration. At the solid (silica) surface, ILs adopt a structure with their charged headgroups in contact with the silica surface, while their alkyl chains are more conformationally ordered or packed compared to the air/IL interface. At the interface between silica and (base oil + IL) mixtures, ILs also preferentially adsorb to the silica surface with their layer structures somewhat different from those of ILs alone. These results showed that ILs can adsorb onto the solid surface even before tribological contacts are made. The insights obtained from this SFG study provide a better understanding of the role of ionic liquids in lubrication.

One of the attempts to improve γ-alumina catalytic performance lies in the use of additives that prone to segregate on its interfaces. The catalytic activity depends on the acidity or basicity of the doping oxides. Li2O is one of these oxides that when is loaded on γ-alumina surface decreases the number of Lewis acid sites. However, little is known about the Li2O distribution in the γ-alumina structure and interfaces. Thus, a detailed study of the lithium oxide distribution in the nanostructure of γ-alumina is the aim of this study. Nanometric powders were synthesized by the polymeric precursor method. The nanopowders were doped with Li+ ions (0.1, 0.5, 1, 3, 5, and 10 mol%) followed by calcination at 650 °C and 750 °C for 15 h. The powders were characterized by XRD, XRF, FTIR-DRIFT, BET specific surface area (SSA) and helium pycnometry. The surface excess due to the lithium oxide segregation was determined by the selective lixiviation method which has proved to be effective in quantifying surface excess of segregated ions at oxide interfaces. The crystallite sizes of the nanopowders varied from 3.3 nm to 9.2 nm, while their SSA were between 82.0 m2/g to 119.9 m2/g. The chemical analyses suggest that the lithium segregates in the γ-alumina interfaces at 650 °C, but it volatilizes from the surface after calcination at 750 °C.

The interfacial properties of ultrahigh methoxylated pectin (UHMP) prepared via esterification of citrus pectin (CP) were investigated. The intrinsic viscosity ([η]) of pectin was significantly decreased from 1211.5 mL/g to 294.9 mL/g as the degree of methylation (DM) increased from 63.18 ± 0.08% to 91.52 ± 0.11%. Surface tension (γ) analysis indicated that UHMP had a critical micelle concentration (CMC) of 0.8 g/L, which was slightly smaller than that of sugar beet pectin (SBP) (1.0 g/L). The morphology of the UHMP aggregation presented a network structure and irregular clusters at 10 μg/mL and 1 μg/mL based on atomic force microscopy (AFM). Transmission electron microscopy (TEM) observations further confirmed the self-aggregation behaviours and rod-like micelles of UHMP. The surface excess (Γ) was 1.69 ± 0.17 μmol/m2 for UHMP, which was lower than the values of SBP (1.88 ± 0.21 μmol/m2) and CP (2.91 ± 0.57 μmol/m2). Correspondingly, UHMP possessed the highest molecular area (A) of 0.99 ± 0.10 nm2. Thus, UHMP was proposed to be more flexible and extendable at the interface. The interfacial shear rheology study suggested that UHMP was able to form an elastic-dominant interfacial film to stabilize the oil/water interface.

Six cocogem surfactants were synthesized from N,N,Nʹ,Nʹ-tetra-(propane-2-olyl)-1,6-hexanediamine and higher monocarboxylic acids: capric, lauric, myristic, palmitic, stearic and oleic. N,N,Nʹ,Nʹ-tetra-(propane-2-olyl)-1,6-hexanediamine was synthesized from hexamethylenediamine and propylene oxide at room temperature, without utilizing any catalyst or solvent. Surface tension, conductivity, foaming ability, foam stability, emulsion stability, viscosity and density measurements were performed on aqueous solutions of all cocogem surfactants. Their surface activity and colloidal-chemical parameters such as critical micelle concentration (CMC), surface pressure at CMC (πCMC), surface tension at CMC (γCMC), surface excess (Γmax), concentration required for 20 mN/m reduction of surface tension (C20), Gibbs energies of adsorption and micellization (ΔGad and ΔGmic) were recorded and variation of these parameters based on hydrophobic chain length and structure was investigated experimentally and computationally. Synthesized surfactants with myristic, palmitic, and stearic tail continued to decrease surface tension even above CMC. The possible reason of this unusual behavior was determined based on computational studies. Surface activity parameters of cocogem surfactant with oleic tail disobeyed the general tendency established by other cocogems with saturated tail group. Palmitic and stearic acid based cocogem surfactants had good foam stability and the reason of this high foam stability was rationalized with high viscosity of their solutions.

Method of hydrotopy was adopted for enhancing the solubility of poorly water soluble drug ibuprofen. Urea was the chosen hydrotopic agent. Solutions of IBP of different concentrations were prepared by 8 h of heating of the mixtures of IBP and the hydrotopic agent in aqueous medium. Concentrations of urea in solution were also varied. Setschenow constant values for IBP in aqueous urea solutions were calculated using the Setschenow relation. An extensive study of physico-chemical properties of the solutions were carried out. Relative viscosity ( η r ) , Jone-Dole’s coefficients ( B J ) and chemical potential (μ), molar conductance ( Λ m ) , limiting molar conductance ( Λ m 0 ), association constant ( K a ), activation energy ( E a ), Walden product ( Λ m 0 η 0 ), thermodynamic parameters ( Δ G 0 , Δ H 0 , Δ S 0 ) were determined and mean ionic activity a ± , surface excess ( Γ ) , were derived from experimentally obtained values of density (d), ultrasonic velocity (U) and surface tension ( γ ) of the solutions. Surface tension was also measured using drop number method. These experimemtal and derived data were used to understand the molecular interactions present in IBP solutions in presence of urea.

Surface adsorption of two commonly detected emerging contaminants, amlodipine (AMP) and carbamazepine (CBZ), onto model colloidal microplastics, natural organic matter (NOM), and fullerene nanomaterials have been investigated. It is found that AMP accumulation at these colloidal-aqueous interfaces is markedly higher than that of CBZ. Measurements of surface excess and particle zeta potential, along with pH-dependent adsorption studies, reveal a distinct influence of colloidal functional group on the adsorption properties of these pharmaceuticals. AMP shows a clear preference for a surface containing carboxylic group compared to an amine modified surface. CBZ, in contrast, exhibit a pH-dependent surface proclivity for both of these microparticles. The type of interactions and molecular differences with respect to structural rigidity and charge properties explain these observed behaviors. In this work, we also demonstrate a facile approach in fabricating uniform microspheres coated with NOM and C60 nanoclusters. Subsequent binding studies on these surfaces show considerable adsorption on the NOM surface but a minimal uptake of CBZ by C60. Adsorption induced colloidal aggregation was not observed. These findings map out the extent of contaminant removal by colloids of different surface properties available in the aquatic environment. The methodology developed for the adsorption study also opens up the possibility for further investigations into colloidal-contaminant interactions.

E/Z photo-isomerization of a new surfactant causes substantial changes in interfacial properties, which are a prerequisite for responsive and adaptive material control on a molecular level., Interfaces that can change their chemistry on demand have huge potential for applications and are prerequisites for responsive or adaptive materials. We report on the performance of a newly designed n-butyl-arylazopyrazole butyl sulfonate (butyl-AAP-C4S) surfactant that can change its structure at the air–water interface by E/Z photo-isomerization in an unprecedented way. Large and reversible changes in surface tension (Δγ = 27 mN m–1) and surface excess (ΔΓ > 2.9 μmol m–2) demonstrate superior performance of the butyl-AAP-C4S amphiphile to that of existing ionic surfactants. Neutron reflectometry and vibrational sum-frequency generation spectroscopy reveal that these large changes are caused by an unexpected monolayer-to-bilayer transition. This exceptional behavior is further shown to have dramatic consequences at larger length scales as highlighted by applications like the light-triggered collapse of aqueous foam which is tuned from high (>1 h) to low (

The microscopic picture of ions at the aqueous liquid-vapor interface continues to be an important and active area of research. Both experiments and simulations have shown that certain ions, such as Br- and I-, prefer to adsorb at the interface, but there is not yet a consensus as to the relative importance of various ion-specific properties that influence surface solvation. In a previous study, we systematically explored the effect of ion size on determining whether or not a monovalent ion would adsorb at the surface, and found that, for electrolyte mixtures represented by non-polarizable models, the larger/smaller anions are enriched/depleted at the interface. Here, we extend that study to include temperature effects enabling a van't Hoff analysis of the enthalpic and entropic contributions. We perform configurational-bias Monte Carlo simulations in the Gibbs ensemble to investigate the partitioning of mixtures of differently sized ions at the aqueous liquid-vapor interface from 284.09 K to 347.22 K at a pressure of 1 atm. Ions are represented using our own previously developed models that vary only in size (i.e., the Lennard-Jones σ parameter changes, while all other parameters are held constant across ion types). System properties studied include surface tension, interfacial width, ion surface excess, number density profiles, z-dependent transfer free energy, enthalpy, entropy, and anion-cation coordination numbers.

Tetradecylpyridinium (TP) based metallosurfactants, TP2[MCl4] (M = Mn, Co, Ni, Cu, Zn), were synthesized and characterized using elemental analysis, NMR (1H, 13C) and FT-IR spectroscopy. Thermal gravimetric analysis showed that TP2[MCl4] metallosurfactants are thermally more stable than the precursor tetradecylpyridinium chloride (TPC). Their aggregation and adsorption properties have been investigated in aqueous medium by measuring the surface tension and conductance, and using dynamic light scattering (DLS) and transmission electron microscopy (TEM) methods. The critical micelle concentration (cmc) values of the TP2[MCl4] metallosurfactants (cmc = 1.116–1.137 mmol kg−1) are about 71% lower than that of TPC (cmc = 3.983 mmol kg−1). The charge neutralization of the metallomicelles due to counterion binding is only about 30 to 35%. The surface excess and area per molecule of TP2[MCl4] metallosurfactants at the cmc are 0.64–0.68 μmol m−2 and 2.45–2.59 nm2, respectively. DLS, TEM and zeta potential (ζ) measurements revealed the presence of small (average hydrodynamic diameter = 4–7 nm), spherical and stable (ζ > +45 mV) micelles in aqueous solution. Binding of the metallosurfactants with bovine serum albumin (BSA) was studied using the steady-state fluorescence method. The metallosurfactants readily quench the intrinsic fluorescence intensity arising from the tryptophan residues incorporated in the BSA. The binding is of 1 : 1 type and the binding constant value depends on the metal ion. The influence of hydrocarbon chain length on the cmc, surface excess and binding with BSA has been discussed.

It is possible to obtain (excess) interfacial entropies from the temperature dependence of some characteristic surface parameter. Such excess entropies contain much valuable information. Their studies lead to deeper insight into the interfacial properties. In some cases, quite unexpected results are obtained. In the present paper, we shall consider three illustrations: (1) the surface excess entropy of the electrical double layer on silver iodide, (2) the surface excess entropy of the interface between air and electrolyte solutions and (3) the surface excess entropy of Langmuir polymeric monolayers. Their analysis starts with defining this characteristic parameter and measuring its temperature dependence, followed by a brief thermodynamic analysis to obtain the sought entropy. Given the generality of this methodology, its applicability is likely to be extended to a variety of other interfacial properties, in particular when competition between electric and non-electric forces plays a role as in self-assembly, hydrophobic bonding and polyelectrolytes.

In this work, the adsorptive behavior of Lycium barabrum polysaccharides (LBP) on 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine(POPC)/1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and POPC/DPPC/Cholesterol (Chol) monolayer films were investigated using the Langmuir films technique and atomic force microscopy (AFM). For the POPC/DPPC system, the π-A isotherms shifted to larger areas and the surface pressure variations (Δπ) in the adsorption curves (10 mN/m and 35 mN/m) increased with the increase in the LBP concentration. For the POPC/DPPC/Chol system, π-A isotherms moved to larger areas with the addition of LBP, and the Δπ values were also lower than those of the POPC/DPPC system. These were ascribed to hydrogen bond network formation between LBP and the lipids. The excess per molecular area (ΔAexc) and the excess Gibbs free energy of mixing ( $$\Delta {\text{G}}_{mix}^{Exc}$$ ) revealed that the repulsion force was the interaction between POPC and DPPC molecules. Meanwhile, the repulsion force increased with the addition of LBP. The addition of cholesterol decreased the force. The interactions among molecules were also evaluated by the values of K (the speed of adsorption of LBP), Ap (the number of each lipid molecule combining with the polysaccharide molecules in the mixed monolayer), Γ (the surface excess concentration) and A (the area per molecule). As shown in AFM images, the morphology of the monolayer films also indicated that LBP was easily adsorbed onto the POPC/DPPC monolayer film via hydrogen bond and the weak Van der Waals interaction. In summary, cholesterol could affect spontaneous insertion of LBP into the POPC/DPPC monolayer films from phosphate buffer solution.

The interfacial and micellization behavior of three dicarboxylic amino acid-based anionic surfactants, abbreviated as AAS (N-dodecyl derivative of -aminomalonate, -aspartate, and -glutamate) in combination with hexadecyltrimethylammonium bromide (HTAB) were investigated by surface tension, conductance, UV-vis absorption/emission spectroscopy, dynamic light scattering (DLS), and viscosity studies. Critical micelle concentration (CMC) values of the surfactant mixtures are significantly lower than the predicted values, indicating associative interaction between the components. Surface excess, limiting molecular area, surface pressure at the CMC, and Gibbs free energy indicate spontaneity of the micellization processes compared to the pure components. CMC values were also determined from the sigmoidal variation in the plot of micellar polarity and pyrene UV vis absorption/emission intensities with surfactant concentration. The aggregation number, determined by static fluorescence quenching method, increases with decreasing mole fraction of the AAS (alpha(AAS)), where the micelles are mainly dominated by the HTAB molecules. The size of the micelle increases with decreasing alpha(AAs), leading to the formation of larger and complex aggregates, as also supported by the viscosity studies. Micelles comprising 20-40 mol % AAS are highly viscous, in consonance with their sizes. Some of the mixed surfactant systems show unusual viscosity (shear thickening and increased viscosity with increasing temperature). Such mixed surfactant systems are considered to have potential in gel-based drug delivery and nanoparticle synthesis.

Hydraulic fracturing is an important technology for the development of unconventional resources, while the foam fracturing plays an essential role for the oil recovery in hydraulic fracturing. To further explore the anion effect of quaternary ammonium cationic surfactants on their relative performances, four fatty acid surfactants were prepared (cetyltrimethylammonium acetate (CTAAC), cetyltrimethylammonium butyrate (CTABU), cetyltrimethylammonium hexanoate (CTAHE), and cetyltrimethylammonium caprylate (CTACA)). The effect of anions on surface tension and foaming properties were discussed, and the emulsion stability was also investigated. The experimental results were presented that the CTAAC possesses the highest surface activities compared with other members in the prepared surfactants. The critical micelle concentration (CMC) and surface tension at the CMC (γCMC) increase as increasing methylene segments in the anions, the maximum surface excess concentration (Γmax), and minimum area per molecule (Amin) present an opposite trend with the increase of methylene segments. The CTAAC exhibits the best performances on foamability and foam stability than other synthesized surfactants at 70°C; the initial foam height (H0) and the foam height ratio (R3) at 0 min and 3 min are 34.9 cm and 52.9%, respectively; this is due to the lowest surface tension and shortest methylene segments. In addition, the emulsion stability was shown to follow the order of CTAAC>CTABU>CTAHE>CTACA.

The aim of the work was to exploit a methodology based on contact angle measurements for the purpose of membrane transport studies. Special attention has been paid to a model system of pharmacological relevance, consisting of the drug dithranol (from semisolid Vaseline suspension) in contact with an artificial skin barrier. The drug permeation has been monitored by the surface wettability evolution during the drug transport process. The surface wettability parameters, such as: surface free energy, 2D film pressure, contact angle hysteresis (CAH) and surface excess for long and short adsorption time intervals, have been derived from dynamic contact angle measurements of the probe liquid drops deposited on the outermost membrane layer. The analysis has allowed the apparent Arrhenius-type energy barrier for the drug surface adsorption (Ea/RgT = −8.04 ± 0.84 at 295 K), the characteristic lag-time of the transport process ( t lag = 20 ± 1.9 min) and the diffusion coefficient of the drug through the membrane (D = 1.25 ± 0.24·10−9 cm2 s−1) to be determined. The latter one remains in a good agreement with literature data for the same system investigated by means of spectroscopic methods.

Adipic acid was used to synthesize three nonionic Gemini surfactants containing different numbers of propylene oxide units in their structures. The produced surfactants have been characterized employing FTIR and 1H-NMR spectra. Some of the physical properties of them, namely, surface tension, maximum surface excess concentration, surface pressure, critical micelle concentration, and the minimal area of the surface taken by a single molecule, were computed. The inhibitory effect of the synthesized surfactants on the corrosion of C-steel (C45) in 1.0 M HCl solution was studied. Gravimetric and electrochemical methods were used for corrosion rate measurements. The outcomes acquired from the used methods showed that every one of the three surfactants works as a strong inhibitor for steel acidic corrosion. By raising surfactant concentration and exposure time, the inhibition proficiency improves. The inhibition efficiency exceeded 90% for the three compounds. The higher the propylene oxide units contained in the surfactant molecule the higher is its inhibition efficiency. Based on the findings, a mechanism for inhibitory action was proposed. Moreover, the density functional theory (DFT) and molecular electrostatic potential (MEP) were investigated for the three inhibitors. The calculated parameters were correlated with the inhibition efficiency.

Bottlebrush polymers are complex macromolecules with tunable physical properties dependent on the chemistry and architecture of both the side chains and the backbone. Prior work has demonstrated that bottlebrush polymer additives can be used to control the interfacial properties of blends with linear polymers but has not specifically addressed the effects of bottlebrush side chain microstructures. Here, using a combination of experiments and self-consistent field theory (SCFT) simulations, we investigated the effects of side chain microstructures by comparing the segregation of bottlebrush additives having random copolymer side chains with bottlebrush additives having a mixture of two different homopolymer side chain chemistries. Specifically, we synthesized bottlebrush polymers with either poly(styrene-ran-methyl methacrylate) side chains or with a mixture of polystyrene (PS) and poly(methyl methacrylate) (PMMA) side chains. The bottlebrush additives were matched in terms of PS and PMMA compositions, and they were blended with linear PS or PMMA chains that ranged in length from shorter to longer than the bottlebrush side chains. Experiments revealed similar behaviors of the two types of bottlebrushes, with a slight preference for mixed side-chain bottlebrushes at the film surface. SCFT simulations were qualitatively consistent with experimental observations, predicting only slight differences in the segregation of bottlebrush additives driven by side chain microstructures. Specifically, these slight differences were driven by the chemistries of the bottlebrush polymer joints and side chain end-groups, which were entropically repelled and attracted to interfaces, respectively. Using SCFT, we also demonstrated that the interfacial behaviors were dominated by entropic effects with high molecular weight linear polymers, leading to enrichment of bottlebrush near interfaces. Surprisingly, the SCFT simulations showed that the chemistry of the joints connecting the bottlebrush backbones and side chains played a more significant role compared with the side chain end groups in affecting differences in surface excess of bottlebrushes with random and mixed side chains. This work provides new insights into the effects of side chain microstructure on segregation of bottlebrush polymer additives.

This study develops a model to fit the surface tension of the water/ethanol mixture for the complete composition range from 0 to 1. The theoretical framework complements Van Der Waals’s theory on the density gradient. The modelling results overcome the limitation of Gibbs adsorption isotherm, which completely ignores the composition of the interfacial layer. Furthermore, the model presents a new method to correctly calculate the composition of the interfacial layer for binary liquid mixture and surfactant solutions.

The effects of wall composition and heat treatment on the formation and properties of core-in-wall emulsions (CIWEs) consisting of whey protein-coated milkfat (AMF) droplets and a dispersion of non-fat milk solids (MSNF) were investigated. Microcapsules were prepared by spray drying these CIWEs. The d3.2 of the CIWEs ranged from 0.36 to 0.54 μm. Surface excess of the CIWEs ranged from 1.39 to 6.57 mg/m2, and was influenced by concentration of whey proteins and heat treatment (30 min at 90 °C). Results indicated a preferential adsorption of β-lg at the O/W interface. Whey proteins accounted for up to 90% of the proteins adsorbed at the O/W interface. The core retention during spray drying ranged from 90.3% to 97.6% and microencapsulation efficiency ranged from 77.9% to 93.3%. The microcapsules exhibited an excellent long-term oxidative stability at 20 and 30 °C that was superior to that of microcapsules consisting of milkfat and MSNF, where the O/W interface was populated mainly by caseins. The superior oxidative stability could be attributed to the formation of dense whey-proteins-based films at the O/W interfaces of the CIWEs that isolated the core domains from the environment. The results open new opportunities in developing highly stable lipids-containing microcapsules and dairy powders.

We use molecular simulation to study the wetting behavior of antifouling polymer-tethered membranes. We obtain the interfacial properties (e.g., contact angle) of water at various temperatures for five polymer membranes, including a base polysulfone (PSF) membrane and four other PSF membranes grafted with antifouling polymers (two poly(ethylene glycol) (PEG) tethers and two zwitterionic tethers). We implement a coupled Monte Carlo (MC)/molecular dynamics (MD) approach to determine the interface potentials of water on the membrane surfaces in an efficient manner. Within this method, short MC and MD simulations are performed in cycles to collect the surface excess free energy of a thin water film on polymer membrane surfaces. Simulation results show that the grafting of zwitterionic tethers provides a more significant enhancement in the hydrophilicity of the PSF membrane than that of the PEG tethers. Water completely wets the surface of zwitterionic polymer membranes.

Understanding the structure of the electrical double layer (EDL) is of great importance for many different technological and scientific applications, but some information is not always accessible from experiments. In this sense, the aim of this study was to implement a simple one-dimensional computational model for the study of the EDL and solve by the finite element method. The details of the validation of the model are presented and frequency domain analysis is performed in order to obtain impedance information. From the impedance study, it was possible to obtain the total capacitance and confirm its dependence on applied potential. Moreover, calculations of the Gibbs excess surface concentration were carried out for different values of bulk concentration. Our results are in agreement with analytical predictions, showing that the model is suitable for the study of the EDL structure. DOI: http://dx.doi.org/10.17807/orbital.v13i2.1453

Alcoholic additives are used to enhance the heat and mass transfer of the absorber, which has been widely recognized as the bounding device of an absorption chiller. Small quantities of additives in the aqueous lithium bromide solution reduce its surface tension, leading to a better wetting of the tube bundle of the absorber and triggering the Marangoni convection. Nevertheless, the enhancement mechanism relies on many parameters which have not been yet studied in details. In this work, the adsorption mechanisms of surfactants at the interface of water drops are experimentally investigated. 2-ethylhexanol, 1-octanol, 3,5,5-trimethyl-1-hexanol and 3-phenyl-1-propanol are chosen as additives and are added to water in different concentrations. The static and dynamic surface tension is measured according to the pendant drop method and the surface excess concentration is hereafter calculated with the Gibbs isotherm. Drops are generated in a saturated atmosphere without inert gases at low pressure, which represents the real working condition of an absorber. The results show that 2-ethylhexanol, 1-octanol and 3,5,5-trimethyl-1-hexanol lead to high surface tension reduction at high concentrations, and they are characterized by a fast diffusion and adsorption. Contrary, 3-phenyl-1-propanol presents a slow adsorption kinetic and is not effective in reducing the surface tension of water.

Oil–brine interfaces play an important role in oil recovery and oil–brine separation, in which the effects of salinity on interfacial tension (IFT) have been much of debate in the past in experiments and modeling studies owing to complex oil compositions. In this work, we use molecular dynamics (MD) simulations to study the oil–brine interfacial properties by designing seven systems containing different oil compositions (decane with/without polar compounds) and the salinity in brine of up to ∼14 wt %. We carefully investigate the salinity and polar component effects by analyzing IFTs, density profiles, orientation parameters, hydrogen bond densities, and charge density profiles. The results indicate that O-bearing compounds (phenol and decanoic acid) can significantly reduce the oil–brine IFT and exhibit the highest Gibbs surface excess relative to water, while the others, including N-bearing compounds (pyridine and quinoline) and S-bearing compounds (thiophene and benzothiophene), only slightly decrease ...

PEO-PPO-PEO triblock copolymers (usually referred as EPE) have been employed in different fields, with a remarkable emphasis in biomedical-related applications. They are amphiphilic macromolecules,...

The interaction between mechanics and chemistry plays an essential and critical role in the behaviors and properties of materials, especially in nanoscale alloys. Based on the classical Gibbs and McLean adsorption isotherms, the present study takes the freestanding nanometer thick films of Pd-H solid solutions as a typic example to investigate surface segregation of hydrogen. The surface eigenstress model is further developed here to give analytic formulas, which have the capability to quantitatively predict the size-dependent surface segregation. Molecular dynamics (MD) simulations are conducted on free-standing Pd-H nanofilms. The MD simulations verify the theoretical analytic results and determine the values of parameters involved in the theoretical analysis. The integrated theoretical and numerical study exhibits that both surface excess H concentration and apparent biaxial Young’s modulus of Pd-H thin films depend on the nominal H concentration and the film thickness. The MD simulations determine the values of three parameters involved in the theoretical analysis. Especially, the parameter of the differentiation in reference chemical potential behaves like the molar free energy of segregation in the McLean adsorption isotherm.

This manuscript reports the volumetric, viscometric and aggregation properties of sodium valporate in aqueous solution. The interaction of drug with cationic surfactant (CTAB) was also studied. From volumetric study, partial molar volume, Hepler's constant, partial molar expansivity and isobaric thermal expansion coefficient were calculated while from viscometric study, the constants of Jones-Dole equation and thermodynamic parameters of viscous flow like free energy change, entropy change and enthalpy change were calculated. Critical micelle concentration of drug at four different temperatures was measured by surface tension and electrical conductivity measurements. The data was used to calculate surface excess concentration and thermodynamic parameters for the micellization process i.e. free energy of adsorption, free energy, entropy and enthalpy of micellization. Spectroscopic study of the drug/surfactant interaction was helpful to calculate partition coefficient, free energy of partition, binding constant and free energy of binding.

The Gibbsian surface excess (GSE) can unequivocally measure the extent of adsorption of a gas on a solid adsorbent. A differential iso-excess heat of adsorption based on the GSE thermodynamic framework provides a physically and thermodynamically consistent description of the adsorbent heterogeneity or homogeneity. The actual amount adsorbed (AAA) cannot be experimentally measured. It must be estimated from the experimental GSE by making extraordinary assumptions regarding the nature of the adsorbed phase. Thus, the AAA is a model dependent variable. A differential iso-steric heat of adsorption based on the AAA thermodynamic framework can be misleading and artificial. The NET amount adsorbed (NAA) is an experimental variable. It is also directly related to GSE. Thus, it provides no further insight into the adsorption system vis a vis the GSE. A differential iso-NET heat of adsorption based on the NAA thermodynamic framework can be misleading and fictitious.