The effective surface energy of heterogeneous solids measured by inverse gas chromatography at infinite dilution

Inverse gas chromatography (IGC) at infinite dilution has been widely used to access the nonspecific surface free energy of solid materials. Since most practical surfaces are heterogeneous, the effective surface energy given by IGC at infinite dilution is somehow averaged over the whole sample surface, but the rule of averaging has thus far not been established. To address this problem, infinite dilution IGC analysis was carried out on mixtures of known heterogeneity. These materials are obtained by mixing two types of solid particles with significantly different surface energies as characterized individually with IGC, and results are obtained for binary combinations in varying proportions. It is found that when all surface components have the same accessibility by probe molecules, the effective surface energy of such a heterogeneous surface is related to the surface energy distribution by a square root linear relationship, square root sigma(eff)(LW)= summation operator (i)phi(i) square root sigma(i)(LW), where sigma(i)(LW) refers to the nonspecific (Lifshitz-van der Waals) surface energy of patches i, and phi(i) to their area fraction.     

A study of the oxidation of vegetable oils by inverse gas chromatography

Summary Inverse gas chromatography is shown to be suitable for the study of the oxidation of vegetable oils. With air as carrier gas characteristic plots of retention index versus time are obtained for hydroxylic test solutes that are consistent with the oxidation behaviour of vegetable oils. Shifts of retention are found to be accompanied by changes of column efficiency due to the oxidative crosslinking of polyunsaturated vegetable oils. The technique also leads to useful information concerning the oxidation of antioxidant inhibited systems. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Comparison of Dorris-Gray and Schultz methods for the calculation of surface dispersive free energy by inverse gas chromatography

Inverse gas chromatography (IGC) is an important technique for the characterization of surface properties of solid materials. A standard method of surface characterization is that the surface dispersive free energy of the solid stationary phase is firstly determined by using a series of linear alkane liquids as molecular probes, and then the acid-base parameters are calculated from the dispersive parameters. However, for the calculation of surface dispersive free energy, generally, two different methods are used, which are Dorris-Gray method and Schultz method. In this paper, the results calculated from Dorris-Gray method and Schultz method are compared through calculating their ratio with their basic equations and parameters. It can be concluded that the dispersive parameters calculated with Dorris-Gray method will always be larger than the data calculated with Schultz method. When the measuring temperature increases, the ratio increases large. Compared with the parameters in solvents handbook, it seems that the traditional surface free energy parameters of n-alkanes listed in the papers using Schultz method are not enough accurate, which can be proved with a published IGC experimental result.     

Estimation of the lateral to basal surface ratio of talc by inverse gas chromatography

Inverse Gas Chromatography at Infinite Dilution, i.e. IGC‐ID, allows following the evolution of surface properties of talc impregnated with increasing concentrations of polyethyleneglycol of molecular weight 20,000. Coupling Inverse chromatography in infinite dilution conditions measurements with controlled surface modification, we have developed a new method to estimate the lateral to basal surface ratio of talc crystals.     

Characterization of surface thermodynamic properties of p-toluene sulfonate-doped polypyrrole by inverse gas chromatography

Summary p-Toluene sulfonate-doped polypyrrole (PPyTos) powder has been characterized by inverse gas chromatography at various temperatures. We have used apolar n-alkanes and polar probes of differing acidity and basicity to interrogate the London dispersive and Lewis acid-base properties of PPyTos, respectively. We have found that the London component of the surface energy (γs^d) is about 90 mJ · m⁻² at 25°C and the acid-base contribution to the free energy of adsorption (ΔG_a ^AB) for Lewis bases is higher than 8 kJ · mol⁻¹. These results show that PPyTos is a high energy material and is capable of very strong specific acid-base interactions. Lewis acidity is, however, dominant and is shown to increase with temperature. The determination of the heats of adsorption for tetrahydrofuran and ethyl acetate enabled us to determine Drago’s E_A, C_A, E_B and C_B parameters. Whilst E_A and C_A are similar to those published for chloride-doped polypyrrole and rank PPyTos as a hard acidic species, the E_B and C_B values suggest that PPyTos is a very soft Lewis base.     

Surface energy of solid catalysts measured by inverse gas chromatography

The time separation of experimental surface energy on Pt-Rh bimetallic catalysts, together with the time-independent rate constants for adsorption and desorption of O(2), CO, and CO(2) on them, is described, applying the reversed-flow version of inverse gas chromatography. The standard free energy of adsorption DeltaG(z.plims;) and its probability density function over time, together with the geometrical mean of the London parts of the total surface free energy (gamma(L)(1)gamma(L)(2))(1/2) of the adsorbed probe and the solid surface, accompanied by the relevant probability density functions over time are also calculated. The time-resolved phenomena lead to quite varying values of DeltaG(z.plims;), (gamma(L)(1)gamma(L)(2))(1/2), and the distribution functions as time passes, their maximum values being given by the catalyst containing a Pt:Rh = 3:1 weight ratio of the active phase for all adsorbed gases. The conclusion is reached that the surface energy measured as described can be used as a good measure for catalyst characterization.     

Characterization of the surface properties of heavy residues of oil distillation by inverse gas chromatography

Summary Heavy residues from the distillation of oils (SAFANYA) have been analyzed by inverse gas chromatography (IGC). The dispersive components of the surface energies of the residues could readily be determined. Acid/base characteristics could be appreciated using an original method developed in this Laboratory.     

Application of inverse gas chromatography in the characterization of raw material used in manufacturing of abrasive materials

The raw material—aloxite used during the manufacturing of grinding tools was characterized by means of inverse gas chromatography (IGC). The surface properties of the different types of aloxite were determined including: (i) the specific surface area; (ii) the dispersive component of surface free energy as well as the sensitivity of this parameter on the environment humidity; and (iii) acidity and basicity of the examined surfaces. The results of our experiments proved the usefulness of IGC in the characterization of this kind of materials.     

The study of reversed phases by inverse gas chromatography

Summary The surface properties of three silica-based reversed phases have been studied by inverse gas chromatography. Theoretical deduction indicates that there is a linear relationship between the molar deformation polarisation of the test solute (P_D) and the dispersive interaction energy between the solute and the C18 and non-bonded silica surfaces. The specific interaction energy between the solute molecule and the silica surface (-G^SP) can be measured as the vertical distance between the solute experimental retention data point (RTl_nV_N) and the n-alkane RTl_nV_N vs P_D calibration line. From multiple regression analysis of-G^SP data with proton acceptor solubility parameter {ie290-1} and orientation solubility parameter {ie290-2} as variants, two coefficients can be obtained related to the influence of the residual silanol groups and the trace metal impurities.     

Surface characterization of poly(2,2,3,3,3-pentafluoropropyl methacrylate) by inverse gas chromatography and contact angle measurements

A fluorinated methacrylic homopolymer, poly(2,2,3,3,3-pentafluoropropyl methacrylate) (PPFPMA) was synthesized by a free radical polymerization reaction. The dispersive component of the surface energy () of PPFPMA was determined by contact angle measurements and inverse gas chromatography (IGC). An extensive surface characterization was conducted by means of IGC. Surface characterization demonstrated that PPFPMA has low value, even at 35 °C and is a Lewis amphoteric polymer with predominantly basic character, as confirmed by the Lewis acidity and basicity constants K_A and K_B, respectively. The values of obtained by IGC are slightly higher than those obtained by the contact angle method. This trend can be attributed to the fact that IGC evaluates, primarily, high energy sites of a surface.     

Characterization by inverse gas chromatography of the surface properties of silicas modified by poly(ethylene glycols) and their models (oligomers,diols)

Summary Silicas are modified by esterification of the surface silanol groups either with poly(ethylene glycol), its oligomers or diols of the same chain length. A whole series of samples carrying grafts differing in chemical nature, molecular weight and number are prepared. These samples are examined by inverse gas chromatography. The London component of the surface energy, the acid/base interaction parameter and the enthalpy of adsorption of alkanes and polar probes are measured. It is apparent for PEG-grafted silicas that the most important variable is the surface coverage, i.e., the number of monomer units of the grafted PEG per unit surface area, and not its molecular weight. The fixation of PEG changes drastically the surface properties of the silicas. According to the surface coverage, silica may acquire base-like properties. The strong PEG-silica interactions cause the polymer to adopt a flat configuration by spreading on the solid surface. Grafted diols behave entirely differently: the conformation of the longer grafts is best described by a sandwich structure in which the outer surface layer is formed by associated alcohol groups, whereas the middle part is formed by the highly organized aliphatic parts of the chains. IR spectroscopy supports these conclusions.     

Application of inverse gas chromatography in the surface characterization of diethanol amine modified polystyrene based polymer

In the present work, diethanol amine modified polystyrene based polymer (PVBC-Diethanol amine) was synthesized and characterized, then surface properties of the polymer were examined by inverse gas chromatography method at infinite dilution. The retention diagrams obtained based on the interaction of polar and nonpolar probes with the polymer were drawn over a temperature range from 30 to 55 °C. Through the diagrams, the dispersive component of the surface free energy, g _S ^D of the polymer surface, and the specific enthalpy of adsorption, DH _A ^S , of probes on the polymer were also calculated. Lewis acid, K _A , and Lewis base, K _D , parameters of PVBC-Diethanol amine surface were determined. The values of K _A and K _D indicated that PVBC-Diethanol amine surface exhibited a basic behavior.     

Acid/base characterization of sepiolite by inverse gas chromatography

Summary The surface properties of sepiolite were investigated by inverse gas chromatography. It is shown that the value of the dispersive component change uniformly with temperature, while the values obtained for the parameters K_A and K_D indicate an acidic character for the sepiolite surface.     

Time separation of adsorption sites on heterogeneous surfaces by inverse gas chromatography

Summary The measurement of local (homogeneous) adsorption energiesε _i , local monolayer capacities,c _max ^* , local adsorption isotherms,θ _i (p, T, ε), and probability density functions for adsorption, f(ε) and ϕ(ε,t), can be used to study the mechanism of adsorption of five gaseous hydrocarbons on the heterogeneous surface of magnesium oxide. The method does not use analytical or numerical solutions of a classical integral equation comprisingf(ε) as unknown, but it depends on a time function of gas chromatographic peaks obtained by short flow-reversals of the carrier gas. The results for adsorption of ethane, ethylene, acetylene, propene, and l-butene on MgO, in the absence and presence of O₃ are given and discussed on the basis of a mechanism proposed earlier for argon on titatium dioxide.     

Inverse gas chromatography applications: A review

Inverse gas chromatography (IGC) is a versatile, powerful, sensitive and relatively fast technique for characterizing the physicochemical properties of materials. Due to its applicability in determining surface properties of solids in any form such as films, fibres and powders of both crystalline and amorphous structures, IGC became a popular technique for surface characterization, used extensively soon after its development. One of the most appealing features of IGC that led to its popularity among analytical scientists in early years was its similarity in principle to analytical gas chromatography (GC). The main aspect which distinguishes IGC experiments from conventional GC is the role of mobile and stationary phases. Contrary to conventional GC, the material under investigation is placed in the chromatographic column and a known probe vapour is used to provide information on the surface.     

反相气相色谱法表征聚丁二烯橡胶的表面性质

采用反相气相色谱技术测定了聚丁二烯橡胶的表面性质。以正己烷、正庚烷、正辛烷、正壬烷作为非极性探针测定其表面色散自由能,以二氯甲烷、三氯甲烷、丙酮、乙酸乙酯、乙醚和四氢呋喃作为极性探针测定其路易斯酸碱常数。经计算得出聚丁二烯橡胶在303、313、323、333和343 K的表面色散自由能分别为47.07、46.46、45.85、45.60和45.09 mJ/m2。结果表明,聚丁二烯橡胶表面色散自由能随着温度的升高呈线性降低,路易斯酸常数Ka为0.34,碱常数Kb为1.77,总酸碱作用能力2.11,该聚合物为弱碱性Lewis两性聚合物材料。此外还计算出聚丁二烯橡胶的酸碱作用吸附自由能（~ΔGsa）和吸附焓（~ΔHsa）。     

Effect of acid treatment on surface properties evolution of attapulgite clay: An application of inverse gas chromatography

In this paper, the evolution of structural, textural and surface properties of attapulgite after treatment with increasing concentrations of hydrochloric acid (0.5, 1, 3 and 5 M) is reported. The solids obtained were characterized by SEM, XRD, FTIR and BET analysis. The surface properties were also evaluated using inverse gas chromatography at infinite dilution (IGC-ID) and finite concentration (IGC-FC). The IGC analysis permitted us to reach several parameters such as: specific surface area, BET constant with organic probes and the distribution functions of the adsorption energy sites on the solid surface. At dilute concentrations of acid, carbonates are eliminated and the specific surface area increases. However, the morphology and crystal structure of attapulgite are preserved. At higher concentrations of acid, dissolution of octahedral sheets and at the same time formation of an amorphous silica from the tetrahedral sheets occur. However, the fibrous morphology is still preserved. The calculation of distribution functions reveals a clear evolution in the heterogeneity of the surface during the acid treatment, the appearance of shoulders is attributed to the development of strong specific interactions between the injected polar probe and silanol groups on the surface of amorphous silica formed during the acid treatment.     

Investigation of thermodynamic properties of hyperbranched aliphatic polyesters by inverse gas chromatography

Thermodynamic properties of a series of commercial hyperbranched aliphatic polyesters (Boltorn^® H20, H30 and H40) were examined for the first time by inverse gas chromatography (IGC) using 13 different solvents at infinite dilution as probes. Retention data of probes were utilized for an extensive characterization of polymers, which includes the determination of the Flory–Huggins interaction parameter, the weight fraction activity coefficient as well as the total and partial solubility parameters. Analysis of the results indicated that the total and partial solubility parameters decrease with increase of temperature. Furthermore, upon increase of the molecular weight, while the hydrogen bonding component decreases, no influence on the total solubility parameter is noticed within the experimental error margins. Results from the present study while providing new insight to the thermodynamic characteristics of the examined systems, they are also expected to reflect more general aspects of the behavior of hyperbranched polymers bearing similar end-groups.     

The determination of surface polarity of bismuth-molybdenum oxidation catalysts by gas chromatography

Summary The adsorption of aromatic and aliphatic hydrocarbons was investigated using gas chromatography on Bi₂O₃, MoO₃ and mixed Bi–Mo oxidation catalysts. As a measure of polarity of a catalyst, the difference between the chemical potential of aromatic and aliphatic hydrocarbons at the same surface concentration was used. The chemical potentials were estimated from elution chromatographic data. The data for C₆–C₉ methylbenzenes and C₆–C₁₂ n-alkanes were obtained in the temperature range 60–300°C in nitrogen as a carrier gas. Using air as carrier gas, introduction of water pulses on a catalyst does not change the elution characteristics. The elution of alkenes, alkynes, dienes and carbonyl compounds was disturbed by reaction of these compounds on the surface. The polarity of catalysts decreased in the order mixed Bi–Mo catalysts, MoO₃, Bi₂O₃. The polarities observed are compared with polarities of some other solids and liquids and the role of polarity of the surface in catalytic oxidation reactions is briefly discussed.