Aqueous Solution-air Interface Research Articles

Gold Nanoparticles at a Liquid Interface: Towards a Soft Nonlinear Metasurface

Optical second-harmonic generation (SHG) is achieved using adsorbed gold nanoparticles (AuNPs) with an average diameter of 16 nm at the aqueous solution–air interface in reflection. A detailed analysis of the depth profile of the SHG intensity detected shows that two contributions appear in the overall signal, one arising from the aqueous solution–air interface that is sensitive to the AuNP surface excess and one arising from the bulk aqueous phase. The latter is an incoherent signal also known as hyper-Rayleigh scattering (HRS). The results agree with those of an analysis involving Gaussian beam propagation optics and a Langmuir-like isotherm. Discrepancies are revealed for the largest AuNP concentrations used and indicate a new route for the design of soft metasurfaces.

Dimethylpiperazine on Air-Water Interface: Vibrational Sum frequency Generation study of a cyclic tertiary amine

Dimethyl piperazine (DMP) is a weakly basic, cyclic, tertiary diamine. Being a saturated 6-membered ring, it may attain a number of energetically close conformational orientations in the ground state. In a particular environment, its conformational distribution depends on the stabilising factors present in the surroundings. Though soluble in water, it is expected to have substantial surface propensity due to presence of multiple –CH2 and –CH3 bonds. Detection of Bohlmann bands in the C–H stretch region of the Vibrational Sum Frequency Generation (VSFG) spectrum revealed that comparatively higher energy chair conformer with one axial and one equatorial –CH3 bond is present on the pure liquid DMP-air interface. At the air-aqueous solution interface, those bands were found to disappear as the lone electron pair on N-atom is engaged in hydrogen bonding with water molecule. Due to this hydrogen bonding, the peak of “dangling free OH” bonds disappeared from VSFG spectrum of water molecules at air–water interface. Alongwith this hydrogen bonding, the hydrophobic nature of the –CH3 bonds of DMP molecules cause disorganisation of native hydrogen bonded network of water molecules in the air–water interface. Structure and orientation of DMP is expected to be pH-responsive since the chemical conditions of the surrounding medium directly affect the extent of protonation of the amine group. Upon addition of HCl to the bulk, protonated DMP ions, too, could be detected on the air-solution interface by their VSFG spectrum which were considerably different from unprotonated DMP. As the bulk pH of solution changed towards more acidic, spectral features of VSFG spectra of DMP on the surface showed significant change, implying variation in the surface pH, as structure and orientation changes at different degrees of protonation. Since the VSFG spectral features of DMP was found to be pH-responsive, it can be utilised to ascertain the pH of any surface that has DMP absorbed on it. pH-sensitivity of the DMP molecules on air–water interface also suggest that orientation of headgroups will have some effect on the surface orientation of cationic surfactants with amine based headgroups.

Interfacial Effects during Phase Change in Multiple Levitated Tetrahydrofuran Hydrate Droplets

Recent strategies developed to examine the nucleation of crystal structures like tetrahydrofuran (THF) hydrates without the effects of a solid interface have included acoustic levitation, where only a liquid-gas interface initially exists. However, the ability now exists to levitate and freeze multiple droplets simultaneously, which could reveal interdroplet effects and provide further insight into interfacial nucleation phenomena. In this study, using direct digital and infrared imaging techniques, the freezing of up to three simultaneous THF hydrate droplets was investigated for the first time. Nucleation was initiated at the aqueous solution-air interface. Two pseudo-heterogeneous mechanisms created additional nucleation interfaces: one from cavitation effects entraining microbubbles and another from subvisible ice particles, also called hydrate-nucleating particles (HNPs), impacting the droplet surface. For systems containing droplets in both the second and third positions, nucleation was statistically simultaneous between all droplets. This effect may have been caused by the high liquid-solid interfacial pressures that developed at nucleation, causing some cracking in the initial hydrate shell around the droplet and releasing additional HNPs (now of hydrate) into the air. During crystallization, the THF hydrate droplets developed a completely white opacity, termed optical clarity loss (OCL). It was suggested that high hydrate growth rates within the droplet resulted in the capture of tiny air bubbles within the solid phase. In turn, light refraction through many smaller bubbles resulted in the OCL. These bubbles created structural inhomogeneities, which may explain how the volumetric expansion of the droplets upon complete solidification was 23.6% compared with 7.4% in pure, stationary THF hydrate systems. Finally, the thermal gradient that developed between the top and bottom of the droplet during melting resulted in a surface tension gradient along the air-liquid interface. In turn, convective cells developed within the droplet, causing it to spin rapidly about the horizontal axis.

Synthesis of reactive copolymers with peroxide functionality for cross‐linking water‐soluble polymers

AbstractA series of reactive copolymers with peroxide functionality (RCPFs) were synthesized via radical copolymerization of monomer mixtures in an organic solvent comprised of a peroxide monomer 5‐(tert‐butyl peroxy)‐5‐methylhex‐1‐en‐3‐yne, acrylamide, maleic anhydride, and butyl methacrylate. Peroxide functionality allows the RCPFs to initiate a variety of radical processes, including cross‐linking of organic polymers. Hydrophilic monomer subunits (acrylamide and maleic anhydride) within the RCPF macromolecules promote cross‐linking of water‐soluble polymers. We aimed to investigate RCPF comonomer ratio and its effects on copolymerization kinetics and composition, as well as physico‐chemical and colloidal properties. We also evaluated and characterized the kinetic parameters of the thermal decomposition of peroxide moieties in the synthesized RCPF. Findings revealed that RCPF possessed surface‐active properties and reduced surface tension at its aqueous solution–air interface. The data indicated that the decomposition process complied with the first‐order kinetics, and complex thermal analysis confirmed the presence of peroxide moieties. RCPFs' ability to cross‐link water‐soluble polymers was demonstrated on poly(acrylamide) and poly(vinyl alcohol).

The opposing effect of butanol and butyric acid on the abundance of bromide and iodide at the aqueous solution–air interface

The efficient oxidation of iodide and bromide at the aqueous solution-air interface of the ocean or of sea spray aerosol particles had been suggested to be related to their surface propensity. The ubiquitous presence of organic material at the ocean surface calls for an assessment of the impact of often surface-active organic compounds on the interfacial density of halide ions. We used in situ X-ray photoelectron spectroscopy with a liquid micro-jet to obtain chemical composition information at aqueous solution-vapor interfaces from mixed aqueous solutions containing bromide or iodide and 1-butanol or butyric acid as organic surfactants. Core level spectra of Br 3d, Na 2s, C 1s and O 1s at ca. 160 eV kinetic energy and core level spectra of I 4d and O 1s at ca. 400 eV kinetic energy are compared for solutions with 1-butanol and butyric acid as a function of organic concentration. A simple model was developed to account for the attenuation of photoelectrons by the aliphatic carbon layer of the surfactants and for changing local density of bromide and iodide in response to the presence of the surfactants. We observed that 1-butanol increases the interfacial density of bromide by 25%, while butyric acid reduces it by 40%, both in comparison to the pure aqueous halide solution. Qualitatively similar behavior was observed for the case of iodide. Classical molecular dynamics simulations failed to reproduce the details of the response of the halide ions to the presence of the two organics. This is attributed to the lack of correct monovalent ion parameters at low concentration possibly leading to an overestimation of the halide ion concentration at the interface in absence of organics. The results clearly demonstrate that organic surfactants change the electrostatic interactions near the interface with headgroup specific effects. This has implications for halogen activation processes specifically when oxidants interact with halide ions at the aqueous solution-air interfaces of the ocean surface or sea spray aerosol particles.

The impact of electrolyte on the adsorption of the anionic surfactant methyl ester sulfonate at the air-solution interface: Surface multilayer formation

The methyl ester sulfonates represent a promising group of anionic surfactants which have the potential for improved performance and biocompatibility in a range of applications. Their solution properties, in particular their tolerance to hard water, suggests that surface ordering may occur in the presence of multi-valent counterion. Understanding their adsorption properties in a range of different circumstances is key to the exploitation of their potential.Neutron reflectivity and surface tension have been used to characterise the adsorption at the air-aqueous solution interface of the anionic surfactant sodium tetradecanoic 2-sulfo 1-methyl ester, C14MES, in the absence of electrolyte and in the presence of mono, di, and tri-valent counterions, Na+, Ca2+, and Al3+. In particular the emphasis has been on exploring the tendency to form layered structures at the interface.In the absence of electrolyte and in the presence of NaCl and CaCl2 and AlCl3 at low concentrations monolayer adsorption is observed, and the addition of electrolyte results in enhanced adsorption. In the presence of NaCl and CaCl2 only monolayer adsorption is observed. However at higher AlCl3 concentrations surface multilayer formation is observed, in which the number of bilayers at the surface depends upon the surfactant and AlCl3 concentrations.

Simulated photoelectron intensities at the aqueous solution-air interface for flat and cylindrical (microjet) geometries.

Ion spatial distributions at the aqueous-air/vacuum interface are accessible by energy-dependent X-ray photoelectron spectroscopy (XPS). Here we quantify the difference between a flat surface and a cylindrical microjet in terms of the energy-dependent information depth of the XPS experiment and in terms of the simulated photoelectron intensities using solutions of pure water and of 1 mol L-1 NaI as examples.

Octadecyl-viologen Photooxidation in Surface Films: Macroscopic Contraction of Langmuir Monolayer by UV Irradiation.

The effects of UV radiation on a viologen derivative, octadecylviologen (OV), in Langmuir monolayers at the air-aqueous solution interface and in Langmuir-Blodgett (LB) films have been investigated. Langmuir monolayers suffer a sharp contraction after UV irradiation, clearly visible by the drop in surface pressure or the loss of surface area observed in the surface pressure-area isotherms. The UV-vis reflection measurements reveal a deep change in the OV monolayer caused by a photochemical reaction, which suggests the pyridones formation as photoreaction products. LB films (Z type), before and after being irradiated with UV light, have been studied by using UV-vis absorption and infrared and X-ray photoelectron spectroscopy. The results confirm that after the photodegradation of the viologen films, the presence of oxygen results in the appearance of pyridones as reaction products. This article demonstrates that, in the absence of catalysts, the photooxidation of viologen surface films occurs only under a particular molecular organization imposed by the air-water interface.

Synthesis and surface-active properties of the fatty acid N-methylethylolamides and their phosphate derivatives

ABSTRACTN-Methylethylolamides have been synthesized on the basis of vegetable oils (corn, coconut, canola, olive, cotton-seed, and palm) and modified with orthophosphoric acid. The structure of the synthesized N-methylethylolamides and their phosphate derivatives has been identified by IR and NMR spectroscopies. Surface activity of the N-methylethylolamides and their derivatives at the water–air border has been determined and their colloidal-chemical parameters (maximum surface excess concentration and minimum area per molecule at the aqueous solution–air interface, surface pressure at the critical micellization concentration (CMC), standard thermodynamic parameters of adsorption and micellization) have been calculated. The character of influence of the surfactants structure on their colloidal-chemical parameter has been clarified. The petroleum-collecting and petroleum-dispersing capacities of the synthesized surfactants have been studied on the surface of the water of various mineralization degrees.

Competition between organics and bromide at the aqueous solution-air interface as seen from ozone uptake kinetics and X-ray photoelectron spectroscopy.

A more detailed understanding of the heterogeneous chemistry of halogenated species in the marine boundary layer is required. Here, we studied the reaction of ozone (O3) with NaBr solutions in the presence and absence of citric acid (C6H8O7) under ambient conditions. Citric acid is used as a proxy for oxidized organic material present at the ocean surface or in sea spray aerosol. On neat NaBr solutions, the observed kinetics is consistent with bulk reaction-limited uptake, and a second-order rate constant for the reaction of O3 + Br(-) is 57 ± 10 M(-1) s(-1). On mixed NaBr-citric acid aqueous solutions, the uptake kinetics was faster than that predicted by bulk reaction-limited uptake and also faster than expected based on an acid-catalyzed mechanism. X-ray photoelectron spectroscopy (XPS) on a liquid microjet of the same solutions at 1.0 × 10(-3)-1.0 × 10(-4) mbar was used to obtain quantitative insight into the interfacial composition relative to that of the bulk solutions. It revealed that the bromide anion becomes depleted by 30 ± 10% while the sodium cation gets enhanced by 40 ± 20% at the aqueous solution-air interface of a 0.12 M NaBr solution mixed with 2.5 M citric acid in the bulk, attributed to the role of citric acid as a weak surfactant. Therefore, the enhanced reactivity of bromide solutions observed in the presence of citric acid is not necessarily attributable to a surface reaction but could also result from an increased solubility of ozone at higher citric acid concentrations. Whether the acid-catalyzed chemistry may have a larger effect on the surface than in the bulk to offset the effect of bromide depletion also remains open.

Surface Active and Thermodynamic Properties in Relation to the Demulsification Efficiency for Some Ethoxylated Derivatives of Alkyldiamines and Polyalkylenepolyamines

In this work, nine monostearic esters of ethoxylated dialkyle-amine (group I) and ethoxylated polyalkylenepolyamine (group II) nonionic surfactants were prepared and characterized by FTIR spectroscopy and nitrogen content. The 1,4-diaminobutane (DAB), 1,6 diamino hexane (DAH), 1,8-diamino-octane (DAO), diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) were ethoxylated at 50, 100, 150 ethylene oxide units individually. The ethoxylated products of (group I) reacted with stearic acid to give the monostearate products. The surface tension of the prepared compounds were measured at 25°C and 60°C. The thermodynamic parameters of micellization and adsorption were also calculated. The surface active properties, such as critical micelle concentration (CMC), maximum surface excess concentration (Γmax), effectiveness of surface tension reduction (πcmc), and minimum area per molecule at the aqueous solution-air interface (Amin), have been calculated. The surface active and thermodynamic properties of the prepared compounds were correlated to their chemical structure. It was found that CMC decreases when increasing the molecular weight of polyethylene oxide units. Furthermore, the data show that the synthesized surfactants favor adsorption than micellization, so that they can be used as demulsifiers for waxy crude oil emulsion (BSW 18%). In this respect, the demulsification test was carried out and the results of demulsification efficiency were correlated to the chemical composition of the investigated compounds. Some factors that affect the demulsification efficiency were also considered such HLB, concentration and time. The maximum demulsification efficiency (100%) was obtained by DAOE150-M and TEPAE150 at 60 and 45 minutes (300 ppm), respectively.

Oxidized Aromatic–Aliphatic Mixed Films at the Air–Aqueous Solution Interface

Mixed organic films composed of molecules with differing hydrophobic groups are relevant to environmental interfaces such as the surface of atmospheric aerosols due to the complex composition of atmospheric emissions. In this work, mixed films composed of oxidized aromatics (benzaldehyde, benzoic acid) and stearic acid are studied using Langmuir trough methods, infrared reflection–absorption spectroscopy (IRRAS), and MD simulations, showing modifications to the surface due to both the hydrophobic and hydrophilic identity of the aromatic molecules. Aromatics are a known component of crude oil, and once released into the atmosphere through an event such as an oil spill, they can be weathered to produce varying degrees of oxidized products like benzaldehyde or benzoic acid. Molecules released through such anthropogenic processes are shown here to have complex interactions with organics released through biogenic emissions (like stearic acid) at the aqueous interface, resulting in diverse surface morphologies that may have an effect on the aerosol particle’s overall effect on atmospheric chemistry and climate. The result of these mixed films is discussed in the context of the modern atmosphere.

Interpolymer complexses of vinyl ether copolymer with polyacrylic and polymethacrylic acids

The interactions between macromolecules of copolymers based on vinyl ethers (vinyl ether of monoethanolamine and vinyl buthyl ether) and 2-acryloilamido-2-methylpropanesulphonic acid with polyacrylic and polymethacrylic acid and, as well as study the effect of interpolymer interactions in the adsorption of polymers at the aqueous solution-air interface were investigated. The observed synergistic increase in surface activity of macromolecules into polyelectrolyte mixtures explained by the formation of interpolymer complexes polyacid - copolymer.

Crown ethers at the aqueous solution–air interface. Part 2. Electrolyte effects, ethylene oxide hydration and temperature behaviour

Vibrational Sum Frequency Spectroscopy (VSFS) was employed to study adsorbing films of 4-Nitro Benzo-15-Crown-5 (NB15C5) and Benzo-15-Crown-5 (B15C5) at the aqueous solution-air interface. The surface of the solution is strongly influenced by the presence of crown ether species. Changes in the orientation of NB15C5 were monitored as a function of solution concentration, by targeting the ratio of peak intensities of the CN and NO(2) vibrational modes. The water of hydration has also been probed as a function of crown concentration, salt concentration, and temperature. The latter study strongly suggests that the surface can be treated as a charged interface, and that the associated ordered water decreases with increasing ionic strength of the bulk solution.

Crown ethers at the aqueous solution–air interface: 1. Assignments and surface spectroscopy

The surface of aqueous solutions of 4-Nitro Benzo-15-Crown-5 (NB15C5) and Benzo-15-Crown-5 (B15C5) has been studied using the surface sensitive technique vibrational sum frequency spectroscopy (VSFS). The NO, CN, COC and CH vibrational modes of these compounds at the air-water interface as well as OH vibrational modes of the surface water hydrating this compound have been targeted in order to obtain molecular information about arrangement and conformation of the adsorbed crown ether molecules at the air-water interface. The CH(2) vibrational modes of crown ethers have been identified and found to be split due to interaction with ether oxygen. The spectra provide evidence for the existence of a protonated crown complex moiety at the surface leading to the appearance of strongly ordered water species. The interfacial water species are influenced by the resulting charged interface and by the strong Zundel polarizability due to tunneling of the proton species between equivalent sites within the crown ring.

Development of a Method for the Extraction of Oil from Clay by Friendly Phase Transfer Catalyst

The separation of waste oil from clay was studied using benzyl triethanol ammonium chloride as phase transfer catalyst. The study showed that the surface tension has an effect on oil recovery. An induced air flotation process was used and polymeric decyl phenol formaldehyde ethoxylate was used as the collector. The effects of various parameters including concentration of catalyst, collector, time of flotation, contact angle, and zeta potential on oil extraction were studied. The results show that oil recovery increases with time of flotation up to a maximum and then levels off. Oil recovery is marginal if the flotation time is extended beyond 12 min. For example, oil recovery increases by only 4% for 25 g oil and 20 g surfactant in the feed when flotation time increases from 12 to 15 min. Oil recovery also increases with surfactant dosage. Furthermore, oil recovery was enhanced by controlling the interfacial tension at the oil–water and water–air interfaces. The mechanism of oil separation was discussed according to micelle composition and the calculated oil recovery obtained was 87%. Furthermore, the kinetic study proved that the process is first order and depends on catalyst concentration. Oil recovery follows a Gibbs adsorption equation. The molecular interaction parameter at the aqueous solution–air interface was also calculated. The results proved that the extraction of oil from solid phase can be conducted by adding phase transfer catalyst. Moreover, the article suggests a model of oil separation from soil according to specifications of adsorbed oil, including isoparaffin and n-paraffin that were analyzed by gas chromatography technique.

Adsorption of cetyltrimethylammonium bromide and propanol mixtures with regard to wettability of polytetrafluoroethylene. I. Adsorption at aqueous solution–air interface

Measurements of surface tension of aqueous solutions of cetyltrimethylammonium bromide (CTAB) and propanol mixtures ( γ L ) for 1 × 10 −5 , 1 × 10 −4 , 6 × 10 −4 , and 1 × 10 −3 M concentrations of CTAB as a function of propanol concentration in the range from 0 to 6.67 M at 293 K were carried out. The obtained results indicate that there is first-order exponential relationship between the surface tension and propanol concentration in the solution at constant CTAB concentration. These results were compared with those calculated from the equations derived by von Szyszkowski, Joos, Miller et al. From the comparison it resulted that the values of γ L determined by the Szyszkowski equation are correlated with those measured only in a limited propanol concentration range because of changes of the constant related to the specific capillary activity in this equation as a function of propanol concentration, particularly in the range of its high concentration. In the case of the modified Joos equation there is a correlation between the calculated and measured values of γ L only at a very low concentration of propanol. The values of the surface tension of aqueous solutions of CTAB and propanol mixtures determined by the relationships of Miller et al. at CTAB concentration, corresponding to unsaturated surface layer in the absence of propanol, are close to those measured, but there are bigger differences between the calculated and measured values of the surface tension for solutions at a constant value of CTAB concentration close to CMC. However, the values of the surface tension of aqueous solution of CTAB and propanol mixtures calculated from the modified Miller et al. equation, in which the aggregation process of alcohol molecules at water–air interface was taken into account, are in excellent agreement with those measured. The measured values of the surface tension and the Gibbs equations were used for determination of the surface excess of CTAB and propanol concentration at solution–air interface. The obtained results indicate that at the constant concentration of CTAB equal to 1 × 10 −5 and 1 × 10 −4 M there is a maximum of excess concentration of propanol in the surface region at its bulk concentration close to 1 M. Using the calculated values of the surface excess concentration of propanol and CTAB at solution–air interface and assuming the proper thickness of the interface region, the total values of their concentration in this region were evaluated. Next, the standard surface free energy of CTAB and propanol mixtures adsorption was calculated. The calculated values of this energy indicate that the tendency to adsorb molecules of CTAB and propanol decreases with increasing propanol concentration probably because of entropy of adsorption decrease resulting from water structure destruction by propanol molecules.

Specific Ion Adsorption and Short-Range Interactions at the Air Aqueous Solution Interface

We have investigated the surface composition of alkali-halide aqueous solutions using grazing incidence x-ray fluorescence. Using mixtures of salts as a means to enhance the short-range effects, small differences in concentration over a few angstrom could be resolved, with, for example I- or Br- > Cl-. In order to explain our data, we need to include an effective potential accounting for the short-range (A) solvent mediated couplings, responsible for specific effects together with dispersion forces. This attractive potential (few k{B}T for halides) leads to concentration profiles which are in good agreement with recent numerical simulations.

Self-aggregation of ionic liquids: micelle formation in aqueous solution

Interfacial tension (using a drop-shape analysis technique), fluorescence (of a widely used spectroscopic molecular probe, pyrene), and 1H NMR measurements were used to monitor the adsorption at the aqueous solution–air interface and self-aggregation behaviour (critical micelle concentration, CMC) of room-temperature ionic liquids (ionic liquids) of the 1-alkyl-3-methylimidazolium family of cations, [Cnmim]+, with different linear alkyl chain lengths, CnH2n+1 (½n = 1–7), and different counter-ions, namely [Cnmim]Cl (n = 2–14), [Cnmim][PF6] (n = 4 or 10), and [C10mim][NTf2]. Only [Cnmim]Cl with n > 8 unambiguously form aggregates in solution and the nature of this self-aggregation is discussed in terms of the electrostatic vs. hydrophobic contributions of the isolated cation. In contrast, the shortest chains behave, as anticipated, as simple salts. In turn, the transitional ionic liquid, [C6mim]Cl is able to develop a monolayer at the aqueous solution–air interface but shows no noticeable self-aggregation in the bulk fluid. Moreover, the micellar characteristics of the well-studied sodium dodecyl sulfate (SDS) aqueous solutions as a function of the total concentration of [Cnmim]Cl (½n = 1–7) showed a clear change in the behaviour of the mixtures [Cnmim]Cl + SDS for n ≈ 6–8, with a characteristic mixed-micelle formation for the longer and a pure salt effect for the shorter chain lengths of [Cnmim]Cl.

Resonance raman spectra and tautomeric structures of a surface-active azo dye, CI Acid Red 138, adsorbed at the aqueous solution–air interface

Raman spectra of Gibbs monolayers adsorbed from the aqueous solution to the solution–air interface were measured for the first time using resonance Raman technique against a surface-active azo dye, CI Acid Red 138 (AR138). The tautomeric structure change of AR138 from the azo form to the protonated hydrazone form occurred upon adsorption from a basic solution. This structural change was principally the same as those observed previously for the adsorption at the aqueous solution-CCl 4 interface and for micellization.