An inverse gas chromatography study of the adsorption of organics on nickel- and copper-hexacyanoferrates at zero surface coverage

The surface properties of Ni and Cu hexacyanoferrates were investigated by the inverse gas chromatography method. Retentions of 10 organic compounds were measured at zero surface coverage in the temperature range 80 to 95 degrees C. The gas/solid partition coefficients and the related thermodynamic data of adsorption (standard free energy change, standard state enthalpies, and entropy changes) also at zero surface coverage were determined. The dispersive component of free surface energy of both hexacyanoferrates, at investigated temperatures, was calculated. The surface acid/base properties were also evaluated using polar adsorbates and the results obtained indicate that nickel hexacyanoferrate is more acidic than copper hexacyanoferrate.     

The surface energy of hydrophilic and hydrophobic adsorbents

Water vapor adsorption and heats of water wetting are studied for hydrophilic quartz, hydrophobic-hydrophilic talc, and hydrophobized Silochrom samples. Water contact angles on the materials under examination are found. The surface thermodynamic parameters of the sorbents are calculated from the data obtained. It is shown that boundary water layers on hydrophilic quartz surface are ordered to a higher extent, while those on hydrophobic basal surfaces of talc particles and hydrophobic surfaces of modified Silochrom samples are ordered to a lower extent relative to liquid water. An empirical equation relating the surface pressure of water films adsorbed on hydrophilic high-energy surfaces with the surface free energy of the latter is proposed. The values of surface free energy are estimated from this equation for a number of important hydrophilic adsorbents.     

反气相色谱法研究煤直接液化残渣经分级提取前后的表面性质变化

采用反气相色谱法（IGC）分别对煤直接液化残渣（DCLR）脱灰处理后不溶物、正己烷不溶物、甲苯不溶物、四氢呋喃不溶物的表面性质进行表征。基于非极性探针净保留体积V_n分别采用Dorris-Gray方法和Schultz方法得到表面色散自由能,基于极性探针V_n得到吸附焓△H^sp,并通过△H^sp作图计算得到酸常数K_a和碱常数K_b。结果表明,经溶剂分级提取后表面色散自由能、K_a和K_b均发生明显变化。而DCLR呈现两性偏碱性这一特征并未随分级提取发生改变。IGC作为一种动力学吸附技术,可快速准确表征DCLR在经分级提取过程中表面性质的变化,相同温度下应用Dorris-Gray方法得到DCLR表面色散自由能略高于Schultz方法。     

Correlation between surface free energy of quartz and its wettability by aqueous solutions of nonionic, anionic and cationic surfactants

The measurements of the advancing contact angle for water, glycerol, diiodomethane and aqueous solutions of Triton X-100 (TX-100), Triton X-165 (TX-165), sodium dodecyl sulfate (SDDS), sodium hexadecyl sulfonate (SHDS), cetyltrimethylammonium bromide (CTAB) and cetylpyridinium bromide (CPyB) on quartz surface were carried out. On the basis of the contact angles values obtained for water, glycerol and diiodomethane the values of the Lifshitz–van der Waals component and electron-acceptor and electron-donor parameters of the acid–base component of the surface free energy of quartz were determined. The determined components and parameters of the quartz surface free energy were used for interpretation of the influence of nonionic, anionic and cationic surfactants on the wettability of the quartz. From obtained results it was appeared that the wettability of quartz by nonionic and anionic surfactants practically does not depend on the surfactants concentration in the range corresponding to their unsaturated monolayer at water–air interface and that there is linear dependence between adhesional and surface tension of aqueous solution of these surfactants. This dependence for TX-100, TX-165, SDDS and SHDS can be expressed by lines which slopes are positive. This slope and components of quartz surface free energy indicate that the interaction between the water molecules and quartz surface might be stronger than those between the quartz and surfactants molecules. So, the surface excess of surfactants concentration at the quartz–water interface is probably negative, and the possibility of surfactants to adsorb at the quartz/water film–water interface is higher than at the quartz–water interface. This conclusion is confirmed by the values of the adhesion work of “pure” surfactants, aqueous solutions of surfactants and water to quartz surface. In the case of the cationic surfactants the relationship between adhesional and surface tension is more complicated than that for nonionic and anionic surfactants and indicates that the relationship between the adsorption of the cationic surfactant at water–air and quartz–water interface depends on the concentration of the surfactants in the bulk phase.     

Solid surface mapping by inverse gas chromatography

Inverse gas chromatography (IGC) at infinite dilution, is a technique for characterising solid surfaces. Current practice is the injection of n-alkane homologous series to obtain the free energy of adsorption of the CH2 group, from which the London component of the solid surface free energy, gamma(d)s, is calculated. A value around 40 mJ/m2 is obtained for poly(ethylene), and 30 mJ/m2 for a clean glass fibre, while the potential surface interactivity of a glass fibre is far greater than that of poly(ethylene). A specific component of the surface, in mJ/m2, should be calculated in order to obtain significant parameters. As applied up to date, when calculating the specific component of the surface energy, the fact that W(sp)a energy values are in a totally different scale than AN or DN values is a major drawback. Consequently, Ka and Kb values obtained are in arbitrary energy units, different from those of the London component measured by injecting the n-alkane series. This paper proposes a method to obtain Ka and Kb values of the surface in the same energetic scale than the London component. The method enables us to correct the traditional London component of a solid, obtaining a new value, where the amount of WaCH2 accounting for Debye interactions with polar sites, is excluded. As a result, an approach to surface mapping is performed in several different substrate materials. We show results obtained on different solid surfaces: poly(ethylene), clean glass fibre, glass beads, chemically modified glass beads and carbon fibre.     

Investigation of acid–base and surface characteristics of a thermotropic semifluorinated salicylaldimine liquid crystal by inverse gas chromatography

The surface energy of a semifluorinated salicylaldimine liquid crystal has been characterised by inverse gas chromatography over the temperature range 303 to 323 K using n-alkanes, tetrahydrofurane, dichloromethane, chloroform, acetone and ethyl acetate molecular probes. The dispersive component of the surface free energy of the adsorbent surface studied was calculated according to the approaches of Fowkes and Dorris–Gray in the infinite dilution region. The specific free energy, enthalpy and entropy of adsorption of polar probes on the liquid crystal were determined. The values of the specific enthalpy of adsorption were correlated with both the donor and the acceptor numbers of the probes to quantify the acidic and the basic parameters of the liquid crystal surface. The surface of the semifluorinated salicylaldimine liquid crystal was found to show a basic nature, which determined the nature of its interaction with the polar probes.     

Surface characterization of poly(methyl methacrylate-co-n-butyl acrylate-co-cyclopentylstyryl-polyhedral oligomeric silsesquioxane) by inverse gas chromatography

The surface properties of poly(methyl methacrylate-co-n-butyl acrylate-co-cyclopentylstyryl polyhedral oligomeric silsesquioxane) (poly(MMA-co-BA-co-styryl-POSS)) were studied by means of inverse gas chromatography (IGC) using 10 non-polar and polar solvents as the probes. Thermodynamic parameters of adsorption, e.g., specific retention volume, the dispersive component of the surface free energy, the specific interaction contribution to the free energy of adsorption and the acid/base constants were obtained to investigate the interactions between the surfaces of the copolymers and different solvents. It was found that incorporation of styryl-POSS into polymer resulted in increasing interactions between polymers and solvents, dispersive component of surface free energy of polymer and acidity of the surfaces of the polymers. The more the styryl-POSS were embedded, the stronger the interaction between the polymer surface and solvent, the dispersive component of the surface free energy and the acidity of the polymer surface were.     

A study on the surface free energy of modified silica fillers and poly(ethylene terephthalate) fibers by inverse gas chromatography

The surface free energy of modified silica fillers and poly(ethylene terephthalate) (PET) fibers was analyzed by inverse gas chromatography in order to investigate the relationship between their surface characteristics and the performance of the composite formed from these materials. The adsorption isotherms of n-heptane and 1-propanol were determined by the elution-peak-maximum method. The dispersive and polar components of the surface free energy were determined by use of the Young–Dupré equation and the Fowkes equation on the basis of the saturated spreading pressure derived from the Gibbs adsorption equation. The acidity and the basicity of the surface were estimated by the specific retention volume of each probe molecule with different donor number and acceptor number. It was found that the dispersive component of the surface free energy for modified silica fillers was mostly lower than that for original silica filler. The polar component of the surface free energy for ethylene glycol modified silica filler became large, while that for n-butanol modified silica filler decreased remarkably. It was also found that original silica filler exhibited high acidity, while modified silica fillers exhibited low acidity. Although these methods have been applied to PET fibers, the surface free energy could not be determined quantitatively because of the surface change during the pretreatment of PET fibers. It was observed that the polar component of the surface free energy decreased when the pretreatment was made at a temperature higher than the glass-transition temperature of PET. It became clear that the interaction between modified silica fillers and PET fibers correlated well with the basicity of the fillers, but not with their acidity. Received: 18 October 1999 Accepted: 8 February 2000     

Determination of the acid/base properties of MgY and NH4Y molecular sieves by inverse gas chromatography

The surface characterization of MgY and NH(4)Y zeolites was performed using inverse gas chromatography (IGC). The adsorption thermodynamic parameters (the standard enthalpy (DeltaH degrees ), standard entropy change (DeltaS degrees ), and free energy change of adsorption (DeltaG degrees ), the dispersive component of the surface free energies (gamma(S)(d)), and the acid-base character of the surface of MgY and NH(4)Y zeolites were estimated using the retention time of different non-polar and polar probes at infinite dilution region. The specific free energy of adsorption (DeltaG(sp)), the specific enthalpy of adsorption (DeltaH(sp)), and the specific entropy of adsorption (DeltaS(sp)) of polar probes on MgY and NH(4)Y zeolites were determined. The values of the DeltaH(sp) were correlated with both the donor and acceptor numbers of the probes to quantify the acidic K(A) and the basic K(D) parameters of the zeolite surfaces. The values obtained for the K(A) and K(D) parameters indicated a basic character for the surface of MgY and NH(4)Y zeolites.     

反气相色谱法测定锌镁铝类水滑石的表面性能

采用水热合成法制备了锌镁铝类水滑石(ZnMgAl-HTLC),利用X射线衍射仪(XRD)对ZnMgAl-HTLC的晶体结构进行了表征,并以一系列非极性和极性分子为探针分子,采用反气相色谱法(IGC)研究了ZnMgAl-HTLC的表面性能.结果表明:XRD特征衍射峰窄、尖、高,水热合成法能够制得纯度较高的ZnMgAl-HTLC; ZnMgAl-HTLC表面吸附自由能小于零,表面色散自由能最大为6.02 mJ/m²,酸碱作用自由能最大为5.33 kJ/mol,吸附焓为43.6 kJ/mol,吸附熵为0.15 kJ/mol.本文的反气相色谱方法对研究锌镁铝类水滑石的表面性能具有重要的指导意义.     

十八烷基三氯硅烷表面改性钛酸钾晶须

利用十八烷基三氯硅烷(OTS)的自组装对钛酸钾晶须(PTW)进行表面改性. 通过测定苯、乙二醇、水在OTS改性的PTW压片上的接触角, 计算了OTS改性PTW后的表面能和极性分量, 并与传统方法(PMMA包裹和KH560表面改性)改性的PTW进行比较, 结果表明, OTS改性的PTW具有更低的表面能和极性分量, 以及更好的亲油疏水性能. IR分析和色散分量测定表明, 改性后OTS的烷基链倾斜在PTW表面.     

Effect of Cationic and Zwitterionic Surfactants on Contact Angle of Quartz–Water–Crude Oil System

The influences of four cationic surfactants hexadecyl glycidyl ether ammonium chloride and four zwitterionic surfactants hexadecyl glycidyl ether glycine Betaine solutions on contact angle of crude oil on a quartz surface were investigated using a captive drop method. The effects of surfactant type, structure, and concentration on contact angle were expounded. From obtained results it appears that the adsorbed surfactant at oil–water interface reduces the interfacial tension and the adsorption at quartz–water interface improves interfacial free energy, which results in reducing the stable value of contact angle and weakening dynamic behavior. At high concentration, the zwitterionic surfactant with branched-chain may form semi-micelle at quartz surface. As a result, the stable value of contact angle passes through a sharp minimum with the increasing concentration.     

Studies on the Surface Free Energy of Carbon-Carbon Composites: Effect of Filler Addition on the ILSS of Composites

The effect of an inorganic oxidation inhibitor, such as MoSi(2), on the surface energetics of carbon-carbon composites has been studied. According to contact angle measurements based on a linear fit method obtained from multiple testing liquids, such as water, diiodomethane, ethylene glycol, and glycerol, it is observed that increasing the MoSi(2) filler content of the composites leads to an increase of the surface free energy, mainly due to the increase of the London dispersive component of surface free energy, even if its specific or polar component is decreased. As an experimental result, the London dispersive component is strongly dependent on the results of the interlaminar shear strength of the composites. In this work, it has been possible to show that the results obtained from the linear fit method correlate with those determined from a two-liquid geometric mean when water and diiodomethane testing liquids are considered as a two-liquid pair. Copyright 2000 Academic Press.     

Surface free energies of silica fillers and their relation to the adsorption of poly(ethylene terephthalate)

The surface free energy of modified silica as well as of PET oligomers was evaluated through measurements of specific retention volumes of several probe molecules by use of the adsorption and adhesion principles in inverse gas chromatography. The nondispersive component of surface free energy of most silica fillers was larger than the dispersive component and the acidic component was much larger than the basic one, which indicated that the surfaces of most silica fillers were rather acidic. These methods were also applied to PET oligomer and it was found that the surface free energy of PET oligomer, regardless of preparation method, consisted of an almost dispersive component, suggesting that the surface of PET was neutral. The amount of PET oligomer adsorbed for the heat-treated silica fillers in acidic solvent increased linearly with increased acidic component of the surface free energy, which indicates that the acidic component of the surface free energy may be responsible for the adsorption. However, the adsorption amount on modified silica is much smaller than that for the heat-treated silica fillers because of steric hindrance caused by the attached organic chain, suggesting that the adsorption cannot be determined only by the surface free energy.     

Structure and Energetics of model amphiphilic molecules at the water liquid-vapor interface. A molecular dynamics study

A molecular dynamics study of adsorption of p-n-pentylphenol at infinite dilution at the water liquid-vapor interface is reported. The calculated free energy of adsorption is -8.8 +/- 0.7 kcal/mol, in good agreement with the experimental value of -7.3 kcal/mol. The transition between the interfacial region and the bulk solution is sharp and well-defined by energetic, conformational, and orientational criteria. At the water surface, the phenol head group is mostly immersed in aqueous solvent. The most frequent orientation of the hydrocarbon tail is parallel to the interface, due to dispersion interactions with the water surface. This arrangement of the phenol ring and the alkyl chain requires that the chain exhibits a kink. As the polar head group is being moved into the solvent, the chain length increases and the tail becomes increasingly aligned toward the surface normal, such that the nonpolar part of the molecule exposed to water is minimized. The same effect was achieved when phenol was replaced by a more polar head group, phenolate. This result underscores the difference between hydrophobic hydration at the surface and in the bulk solvent, when nonpolar molecular fragments adopt compact conformations.     

Free energy of adsorption of water and metal ions on the [1014] calcite surface

We calculated the free energy profiles of water and three metal ions (magnesium, calcium, and strontium) adsorbing on the [1014] calcite surface in aqueous solution. The approach uses molecular dynamics with parametrized equations to describe the interatomic forces. The potential model is able to reproduce the interactions between water and the metal ions regardless of whether they are at the mineral surface or in bulk water. The simulations predict that the free energy of adsorption of water is relatively small compared to the enthalpy of adsorption calculated in previous papers. This suggests a large change in entropy associated with the water adsorption on the surface. We also demonstrate that the free energy profile of a metal ion adsorbing on the surface correlates with the solvent density and that the rate of formation of an innersphere complex depends on overcoming a large free energy barrier, which is mainly electrostatic in nature. Furthermore, comparison among the rates of desorption of magnesium, calcium, and strontium from the calcite surface suggests that magnesium has a much lower rate of desorption due to its strong interactions with both water and the surface.     

Application of 1H NMR spectroscopy method for determination of characteristics of thin layers of water adsorbed on the surface of dispersed and porous adsorbents

The paper presents 1H NMR spectroscopy as a perspective method of the studies of the characteristics of water boundary layers in the hydrated powders and aqueous dispergated suspensions of the adsorbents. The method involves measurements of temperature dependence proton signals intensity in the adsorbed water at temperatures lower than 273 K. Free energy of water molecules at the adsorbent/water interface is diminished due to the adsorption interactions causing the water dosed to the adsorbent surface freezes at T < 273 K. Thickness of a non-freezing layer of water can be determined from the intensity of the water signal of 1H NMR during the freezing-thawing process. Due to a disturbing action of the adsorbent surface, water occurs in the quasi-liquid state. As a result, it is observed in the 1H NMR spectra as a relatively narrow signal. The signal of ice is not registered due to great differences in the transverse relaxation times of the adsorbed water and ice. The method of measuring the free surface energy of the adsorbents from the temperature dependence of the signal intensity of non-freezing water is based on the fact that the temperature of water freezing decreases by the quantity which depends on the surface energy and the distance of the adsorbed molecules from the solid surface. The water at the interface freezes when the free energies of the adsorbed water and ice are equal. To illustrate the applicability of the method under consideration the series of adsorption systems in which the absorbents used differed in the surface chemistry and porous structure. In particular, the behaviour of water on the surface of the following adsorbents is discussed: non-porous and porous silica (aerosils, silica gels); chemically and physically modified non-porous and porous silica (silanization, carbonization, biopolymer deposition); and pyrogeneous Al2O3 and aluminasilicas. The effect of preliminary treatment of the adsorbent (thermal, high pressure, wetting with polar and non-polar solvents) on the characteristics of the structurized water layers was discussed. The influence of the adsorbent porous structure on the free energy of the adsorbed water was also studied. The discussion of the obtained results was made.     

Ionic surfactant adsorption onto activated carbons

The adsorption of sodium dodecyl sulfate onto a set of activated carbons from aqueous solutions has been studied in the low concentration range. The adsorption isotherms are reasonably well fitted by a double Langmuir equation but the calorimetry of adsorption enthalpies shows a rather wide distribution of energies. This distribution is related to direct adsorbate-adsorbent interactions in pores of different size, without noticeable contributions from the chemical nature of the surface. The adsorbate-adsorbent interaction free energy through water is evaluated using the model proposed by van Oss and co-workers for the interfacial free energy. The obtained results indicate that the calculated free energy is in good agreement with that found from application of the double Langmuir equation to the adsorption isotherms.     

吸附与润湿II.Triton X-100和Triton x-305在炭黑/水和炭黑/环己烷界面上的吸附层结构

测定了15℃和30℃时炭黑自水和环己烷中吸附非离子型表面活性剂TritonX-100和Triton X-305的等温线;计算了吸附过程的标准热力学函数;测定了石墨/水/环己烷和石墨/水/空气的接触角与表面活性剂浓度的关系, 分析所得结果,可得结论:在炭黑/水或石墨/水界面上,Triton型表面活性分子形成单分子吸附层,分子以憎水的iso-C8H17C6H4基团附着在表面,而以亲水的聚氧乙烯链伸入水相的方式取向;在炭黑/环已烷或石墨/环己烷界面上,分子是通过聚氧乙烯链吸附到表面上的,当浓度增加时分子在表面可能通过聚氧乙烯链间的相互作用而发生聚集,即可能形成表面反式胶团。     

Tracking oxytetracyline mobility across environmental interfaces by second harmonic generation

This work examines the binding behavior of the antibiotic oxytetracycline (OTC) to mineral oxide/water interfaces in the presence and absence of organic functional groups using the interface-specific technique second harmonic generation (SHG). Studies show that OTC binding to fused quartz, methyl ester, carboxylic acid, and alkyl interfaces is fully reversible and highly dependent on solution pH, with appreciable adsorption occurring only at pH 8. Relative surface coverage at pH 8 is highest for the polar organic-functionalized surfaces, and surface saturation occurs for the methyl ester-functionalized fused quartz/water interface at 2 x 10(-5) M. Adsorption isotherm measurements indicate that the binding process is controlled by hydrogen bonding and hydrophobic interactions, with free energies of adsorption on the order of -40 kJ/mol for all interfaces studied. The results indicate that OTC transport in the environment will depend heavily on soil pH and composition and have implications for the development of bacterial antibiotic resistance.