Comparative study of hydrocarbon, fluorocarbon, and aromatic bonded RP-HPLC stationary phases by linear solvation energy relationships.

The retention properties of eight alkyl, aromatic, and fluorinated reversed-phase high-performance liquid chromatography bonded phases were characterized through the use of linear solvation energy relationships (LSERs). The stationary phases were investigated in a series of methanol/water mobile phases. LSER results show that solute molecular size and hydrogen bond acceptor basicity under all conditions are the two dominant retention controlling factors and that these two factors are linearly correlated when either different stationary phases at a fixed mobile-phase composition or different mobile-phase compositions at a fixed stationary phase are considered. The large variation in the dependence of retention on solute molecular volume as only the stationary phase is changed indicates that the dispersive interactions between nonpolar solutes and the stationary phase are quite significant relative to the energy of the mobile-phase cavity formation process. PCA results indicate that one PCA factor is required to explain the data when stationary phases of the same chemical nature (alkyl, aromatic, and fluoroalkyl phases) are individually considered. However, three PCA factors are not quite sufficient to explain the whole data set for the three classes of stationary phases. Despite this, the average standard deviation obtained by the use of these principal component factors are significantly smaller than the average standard deviation obtained by the LSER approach. In addition, selectivities predicted through the LSER equation are not in complete agreement with experimental results. These results show that the LSER model does not properly account for all molecular interactions involved in RP-HPLC. The failure could reside in the V2 solute parameter used to account for both dispersive and cohesive interactions since "shape selectivity" predictions for a pair of structural isomers are very bad.     

Preparation of sulfoxide residue bonded silica stationary phase for separation of polychlorinated biphenyls from mineral oils

In this study, a sulfoxide residue bonded silica stationary phase was prepared for the separation of polychlorinated biphenyls (PCBs) from mineral oils, and its properties were investigated. Organic sulfide was attached to a silica surface by an amide bond, and the bonded sulfide residues were oxidized to sulfoxide with hydrogen peroxide to afford sulfoxide and sulfone residues bonded to the stationary phases (0.84 and 0.63 mmol of sulfur bonded per gram, respectively). The oxidation states of sulfur atoms bonded on the stationary phases could be determined using high-resolution X-ray fluorescence spectra. The modified stationary phases, especially sulfoxide-bonded one, separated PCBs from mineral oils (paraffin-based transformer oils) more efficiently than aminopropyl silica or other polar stationary phases that have been used for the cleanup of PCBs. The chromatographic parameters for an aliphatic hydrocarbon (eicosane) and some PCB congeners indicated strong retention of highly chlorinated biphenyls by the sulfoxide-bonded silica compared with the aminopropyl silica. A cleanup procedure was established for simple determination of PCBs in mineral oil samples using the sulfoxide-bonded silica packed column fractionation. The analytical method was validated using a certified reference material and a PCB-fortified transformer oil sample.     

Dependence of selectivity on eluent composition and temperature in the HPLC separation of taxanes using fluorinated and hydrocarbon phases

Optimized conditions of aqueous acetonitrile (ACN) eluent composition and temperature are established for the rapid separation of a standard mixture of 15 taxanes, on each of five different fluorinated phases and one C8 hydrocarbonaceous phase. On both types of stationary phase, the retention factors (k') of most of the taxanes decrease at the same rate with increasing ACN concentration. However, the taxanes containing a xylosyl group show a higher rate of decrease, which necessitates careful control of eluent composition to achieve separation of all the taxanes. Temperature can have a remarkable and counterintuitive effect on retention and selectivity. For the C8 phase with eluent compositions in the 40%-60% ACN range, the k' values of the xylosyl taxanes show an increase with increasing temperature over the range from 25 to 55 degrees C; the k' values for 10-deacetyl baccatin III and 10-deacetyl taxol go through a maximum over the same ranges. The other taxanes behave normally. The same pattern is observed on the propyl(perfluorophenyl) phase, although this and the other fluorinated phases are less retentive. This accounts for the common belief that fluorinated stationary phases offer resolution of taxanes superior to that on hydrocarbon phases. The higher retention on the latter requires eluent compositions near 50% ACN, where careful temperature optimization is required, which in practice is rarely performed. The lesser retention on the fluorinated phases allows use of lower ACN concentrations where the aberrant temperature effect is not found, so good separations without temperature optimization can be achieved. Further evidence of the lack of any fundamental difference in the selectivity of the two types of stationary phase is the similarity of the surface excess isotherms measured for ACN/H2O on both the fluorinated and hydrocarbon phases.     

Characterization of the polarity of reversed-phase liquid chromatographic stationary phases in the presence of 1-propanol using solvatochromism and multivariate curve resolution

This work characterizes solvation effects in reversed-phase liquid chromatography in the presence of 1-propanol. The solvatochromic method combined with a multivariate curve resolution-alternating least-squares analysis method has been used to characterize two modified silica surfaces--phenyl bonded and C18 bonded silica in mobile-phase mixtures of methanol--water and acetonitrile--water in the presence of 1-propanol. The presence of a small amount of 1-propanol has been shown to affect mainly the polarity properties of the stationary phases while the mobile-phase properties are largely unaffected. The chain collapse mechanism for the C18 stationary phase at higher concentrations of water seems to be inhibited in the presence of 1-propanol, and partitioning is the predominant solute retention mechanism. The phenyl-based phase shows considerably different behavior from that of the C18 phase, and propanol appears to disrupt the pi-stacking interactions between the solute and the phenyl rings anchored to the silica support.     

Structure-function relationships in high-density docosylsilane bonded stationary phases by Raman spectroscopy and comparison to octadecylsilane bonded stationary phases

Raman spectroscopy is used to investigate the effects of temperature, surface coverage, polymerization method (surface or solution polymerized), and nature of the alkylsilane precursor on alkyl chain conformational order in a series of high-density docosylsilane (C22) stationary phases at surface coverages ranging from 3.61 to 6.97 mumol/m(2). The results of this study contribute to an enhanced understanding of the shape-selective retention characteristics of these phases at a molecular level. Conformational order is evaluated using the intensity ratio of the antisymmetric and symmetric nu(CH2) modes as well as the frequency at which these modes are observed. Alkyl chain order is shown to be dependent on surface coverage, alkyl chain length, and polymerization method. In general, alkyl chain order increases with surface coverage. Temperature-induced changes are observed between 250 and 350 K for the three phases with surface coverages between 3.61 and 4.89 mumol/m(2). These changes occur over a broad range of temperatures characteristic of two-dimensional systems, but in general adhere to the behavior predicted for a simple first-order transition. This change is not believed to be an abrupt cooperative disassociation characteristic of a phase transition in a bulk phase, but instead is thought to involve significant changes in conformational order in segments of the surface-tethered molecules, mostly those segments at the outer edge of the alkylsilane. In contrast to the changes observed in coverages below 5 mumol/m(2), a first-order change is not observed for the stationary phase with coverage of 6.97 mumol/m(2). A molecular picture of the temperature-induced disorder is proposed with disorder originating at the distal carbon and propagating only a short distance toward the proximal carbon. A comparison is made between these C22 stationary phases and similar high-density octadecylsilane (C18) bonded phases.     

A prototype electrochemical chromatographic column for use with proteins

We developed electrochemical hardware and media targeted for protein chromatography. Two types of stationary phases were investigated. The first comprised gold-plated stainless 316L beads coated with a self-assembled monolayer of 6-mercaptohexan-1-ol and was expected to behave like an ion-exchange resin in the presence of an electric field. The secondary stationary phase comprised the first stationary phase with further functionalization with immobilized heme moieties and was expected to behave like immobilized metal affinity resin. We tested apparatus with both stationary phases using ribonuclease A as a model protein and applied potentials from -0.3 to +0.3 V versus the saturated calomel electrode. Despite low binding capacities, we demonstrated that protein retention on both stationary phases could be controlled with an applied potential. The greatest extent of electromodulation was achieved with the mercaptohexanol-based ion-exchange media.     

Highly cross-linked self-assembled monolayer stationary phases: an approach to greatly enhancing the low pH stability of silica-based stationary phases

A new type of silica-based stationary phase with dramatically improved acid stability compared to any currently available silica-based stationary phase has been developed. Superior low pH stability is achieved by first self-assembling a densely bonded monolayer of (chloromethyl)-phenylethyltrichlorosilane (CMPES). The self-assembly step is followed by a Friedel-Crafts cross-linking of the reactive moieties with their neighbors, by addition of secondary, cross-linkable aromatic reagents, or by both. This phase is not endcapped. Elemental analysis data shows that an aluminum chloride catalyst is very effective at bonding aromatic cross-linking reagents, such as styrene heptamer and triphenylmethane, to the reactive CMPES monolayer. The stability of the retention factor of decylbenzene on the cross-linked self-assembled CMPES phases is compared to a sterically protected C18 phase to illustrate its superior resistance to acid-catalyzed-phase loss. Inverse size exclusion chromatography and flow-curve comparisons of the cross-linked self-assembled CMPES and the sterically protected C18 stationary phases illustrate their similar chromatographic efficiency.     

A study of the enthalpy and entropy contributions of the stationary phase in reversed-phase liquid chromatography

The goal of this study was to elucidate the roles played by the stationary and mobile phases in retention in reversed-phase liquid chromatography (RPLC) in terms of their individual enthalpic and entropic contribution to the Gibbs free energy of retention. The experimental approach involved measuring standard enthalpies of transfer of alkylbenzenes from typical mobile phases used in RPLC (methanol/water and acetonitrile/water mixtures), as well as from n-hexadecane (a simple analogue of the stationary phase) to the gas phase, using high-precision headspace gas chromatography. By combining the measured enthalpies with independently measured free energies of transfer, the entropies of transfer were obtained. This allowed us to examine more fully the contribution that each phase makes to the overall retention. It was found that the standard enthalpy of retention in RPLC (i.e., solute transfer from the mobile phase to the stationary phase) is favorable, due to the large and favorable stationary-phase contribution, which actually overcomes an unfavorable mobile-phase contribution to the enthalpy of retention. Further, the net free energy of retention is favorable due to the favorable enthalpic contribution to retention, which arises from the net interactions in the stationary phase. Entropic contributions to retention are not controlling. Therefore, to a great extent, retention is due to enthalpically dominated lipophilic interaction of nonpolar solutes with the stationary phase and not from solvophobic processes in the mobile phase. Further, our enthalpy data support a "partition-like" mechanism of retention rather than an "adsorption-like" mechanism. These results indicate that the stationary phase plays a very significant role in the overall retention process. Our conclusions are in direct contrast to the solvophobic model that has been used extensively to interpret retention in RPLC.     

Molecular shape selectivity through multiple carbonyl-pi interactions with noncrystalline solid phase for RP-HPLC

A new approach for the synthesis of double-alkylated L-glutamide-derived stationary phases to use in RP-HPLC is described. TEM observation of lipid distearylglutamide (DSG) showed the formation of fibrous aggregates in methanol or in chloroform through intermolecular hydrogen bonding among the amide moieties while dibutylglutamide (DBG) cannot aggregate in aqueous or organic media due to its lower order of short alkyl chain. DSG and DBG were covalently bonded to silica via amino-propyl linkages. Lipid membrane analogues (e.g., DSG) attached to the silica surface have been found in noncrystalline and solid states and can form supramolecular assemblies with specific properties based on their highly ordered structures in aqueous and organic media. 13C CP/MAS NMR and suspension (in methanol)-state 1H NMR, elemental analysis, and DSC measurements were used to characterize Sil-DSG and were compared with the three other octadecyl phases, i.e., monomeric C18, polymeric C18, and silica grafted poly(octadecyl acrylate) Sil-ODA25. The chromatographic behavior of the new RP material was investigated using detailed retention studies of planar and nonplanar polyaromatic hydrocarbons (PAHs) and nonpolar aromatic positional isomers. Aspects of shape selectivity were also evaluated with Standard Reference Materials 869a, Column Selectivity Test Mixture for Liquid Chromatography. Detailed chromatographic study revealed that Sil-DSG showed extremely enhanced molecular shape selectivity compared with the other phases investigated. The higher molecular shape selectivity obtained by Sil-DSG can be explained by a carbonyl pi (present in lipid-grafted stationary phases)-benzene pi (present in guest PAHs) interaction mechanism, and these interactions are more effective for ordered carbonyl groups.     

Feasibility of supercritical fluid chromatography/mass spectrometry of polypeptides with up to 40-mers

Supercritical fluid chromatography (SFC) provides a number of advantages over traditional HPLC such as speed, practical use of longer columns, a normal-phase retention mechanism, and reduced use of organic solvents. Yet, it has been a technique traditionally limited to relatively nonpolar compounds. The nature of SFC mobile and stationary phases did not allow the elution of ionic compounds or of peptides, except, in the latter case, for the most hydrophobic peptides. The characterization of peptides is critically important for drug discovery and development in the pharmaceutical industry, as well as for a variety of other important applications. Here, for the first time to our knowledge, we show that relatively large peptides (at least 40 mers), containing a variety of acidic and basic residues, can be eluted in SFC. We used trifluoroacetic acid as additive in a CO2/methanol mobile phase to suppress deprotonation of peptide carboxylic acid groups and to protonate peptide amino groups. A 2-ethylpyridine bonded silica column, which was specifically developed for SFC, was used for the majority of this work. The relatively simple mobile phase was compatible with mass spectrometric detection.     

Effect of amine counterion type on the retention of basic compounds on octadecyl silane bonded silica-based and polybutadiene-coated zirconia phases

In a previous paper, we compared the mixed-mode retention characteristics of cationic solutes on octadecyl silane-bonded silica (ODS) and polybutadiene-coated zirconia (PBD-ZrO2) phases. It is well recognized that both reversed-phase and ion-exchange interactions contribute to the retention of cations on ODS phases. The reversed-phase interaction results from the bonded hydrocarbon chain; the ion-exchange interaction originates in the ionized residual silanol groups. These two types of interactions also exist on the PBD-ZrO2 phase. The polybutadiene contributes to the reversed-phase interaction and the ionized zirconol, but primarily, the adsorbed Lewis base anions, such as phosphate or fluoride, contribute to the ion-exchange interaction. We have shown that on ODS phases, reversed-phase interactions are much more important, whereas the opposite is true of PBD-ZrO2 phases. In this work, we investigate the effect of several amine mobile phase counterions on the retention of cationic solutes on ODS and PBD-ZrO2 phases. The effects of the chain length and the type of amine (1 degree, 2 degrees, 3 degrees) counterion on the retention of basic compounds were studied. In contrast to older studies of type A silica-based phases, the results show that the chain length and type of the amine blocker do not have a large effect on the retention of basic compounds with the newer type B silica-based materials. However, on the PBD-ZrO2 phase, very striking differences in retention were observed with different amine counterions. We show that the molecular geometry of the amine counterion has a significant effect on the retention of basic solutes on the PBD-ZrO2 phase.     

Retention and selectivity of teicoplanin stationary phases after copper complexation and isotopic exchange

Teicoplanin is a macrocyclic glycopeptide that is highly effective as a chiral selector for LC enantiomeric separations. Two possible interaction paths were investigated and related to solute retention and selectivity: (1) interactions with the only teicoplanin amine group and (2) role of hydrogen bonding interactions. Mobile phases containing 0.5 and 5 mM copper ions were used to try to block the amine group. In the presence of copper ions, it was found that the teicoplanin stationary phase has a decreased ability to separate most underivatized racemic amino acids. However, it maintained its ability to separate enantiomers that were not alpha-amino acids. It is established that there is little copper-teicoplanin complex formation. The effect of Cu2+ on the enantioseparation of some alpha-amino acids appears to be due to the fact that these solutes are good bidentate ligands and form complexes with copper ions in the mobile phase. Isotopic exchange with deuterium oxide was performed using acetonitrile-heavy water mobile phases. It was found that the retention times of all amino acids were lower with deuterated mobile phases. The retention times of polar or apolar molecules without amine groups were higher with deuterated mobiles phases. In all cases, the enantioselectivity factors were unaffected by the deuterium exchange. It is proposed that the electrostatic interactions are decreased in the deuterated mobile phases and the solute-accessible stationary-phase volume is somewhat swollen by deuterium oxide. The balance of these effects is a decrease in the amino acid retention times and an increase in the apolar solute retention time. The enantioselectivity factors of all of the molecules remain unchanged because all of the interactions are changed equally. We propose a new global quality criterion (the E factor) for comparing and evaluating enantiomeric separations.     

Synthesis and evaluation of an aromatic polymer-coated zirconia for reversed-phase liquid chromatography

We synthesized a novel aromatic polymer-coated zirconia-based RPLC stationary phase by chemical adsorption of a copolymer of chloromethylstyrene and diethoxymethylvinylsilane onto zirconia (CMS/VMS-ZrO2). Characterization of the pore structure of the support by nitrogen porosimetry and inverse size-exclusion chromatography indicates that CMS/VMS-ZrO2 maintains the well-defined pore structure of the base material. Flow studies show that CMS/VMS-ZrO2 has good mass transfer characteristics. The reversed-phase retention characteristics of the new support are comparable to those of conventional silica-bonded phases. We have also evaluated the mechanical, thermal, and pH stability of CMS/VMS-ZrO2. The results show that CMS/VMS-ZrO2 is stable over a very wide range of pH (pH = 1-13) and at temperatures as high as 160 degrees C. Chromatographic separations of some low molecular weight aromatic analytes on CMS/VMS-ZrO2 and octadecyl-bonded silica phases indicate that there are some subtle but significant differences in the chromatographic selectivity of these two types of phases.     

Ion-pair chromatographic separation of water-soluble gold monolayer-protected clusters

We demonstrate the efficacy of ion-pair chromatography for separations of samples of charged, polydisperse, water-soluble gold nanoparticles protected by monolayers of N-acetyl-l-cysteine and of tiopronin ligands. These nanoparticle mixtures have 1-2-nm-diameter Au core sizes as estimated from UV-visible spectra of the separated components. This size range encompasses the transition from bulk metal to molecular properties. The nanoparticle mixtures were resolved, the smallest nanoparticles eluting first, on an octadecylsilyl (C18) column using isocratic elution with a methanol/water mobile phase containing tetrabutylammonium fluoride (Bu4N+F-) and phosphate buffer. The column retention increases with Bu4N+F- concentration, lowered pH, and decreasing methanol volume fraction. The retention mechanism is dominated by ion-pairing in either the mobile phase or at the stationary/mobile-phase interface. Size exclusion effects, used in many previous nanoparticle separations, are insignificant.     

Shape-selective retention of polycyclic aromatic hydrocarbons on metalloprotoporphyrin-silica phases: effect of metal ion center and porphyrin coverage

Various metalloprotoporphyrins (MProP) covalently linked to silica are examined as stationary phases for reversed-phase HPLC separation of polycyclic aromatic hydrocarbons (PAHs). The MProP-silica stationary phases are shown to exhibit extraordinary shape selectivity for planar over nonplanar PAHs, with the selectivity factors for the triphenylene/o-terphenyl solute pair approaching 30 on Cu(II)ProP-silica phases using 100% acetonitrile as the mobile phase. Shape selectivity and solute retention are highly dependent on the metal ion (M) within the center of the immobilized protoporphyrin (ProP) structure in accordance with the following sequence: Cu(II) > Fe(III) > Ni(II) > H(2) > Zn(II) ≈ Cd(II). A face-to-face π-π interaction is believed to be the major retention mechanism of PAHs on ProP- and MProP-silica phases, with varying metal ion centers affecting the strength of this interaction. Beyond the influence of the central metal, varying surface coverages of metalloporphyrin also lead to significant changes in observed capacity factors and shape selectivities for PAH solutes. The extremely high shape selectivity for planar vs nonplanar PAHs suggests that MProP-silicas could be ideal materials for selectively preconcentrating the more toxic planar PAHs from environmental samples. Preliminary results relevant to this application are reported.     

Covalently bound ionene polyelectrolyte-silica gel stationary phases for HPLC

Micelle-mimetic ionene-based stationary phases for high-performance liquid chromatography (HPLC) are prepared by attaching [3,16]- and [3,22]-ionenes to aminopropyl silica through a carbon-nitrogen bond. These [x,y]-ionenes are polyelectrolytic molecules consisting of dimethylammonium charge centers interconnected by alternating alkyl chain segments containing x and y methylene groups, some of which can form aggregate species whose properties mimic those of conventional surfactant micelles. These ionene-bonded stationary phases were characterized using different recommended HPLC test mixtures. Test solute chromatographic behavior on the ionene phases was found to be similar to that of intermediate oligomeric or polymeric C-18 and/or phenyl phases, depending upon the specific test mixture employed. In addition, the phases exhibit significant solute shape recognition ability. The ionene stationary phases were successfully employed for the separation of the components of the recommended ASTM reversed-phase test mixture, as well as for ortho-, meta- and para-disubstituted benzenes and other positional or geometric isomeric compounds. The ionene materials allow for chromatographic separations under either reversed-phase or ion-exchange conditions. The retention mechanism on these multimodal phases can occur by hydrophobic partitioning or electrostatic interactions, depending upon the characteristics of the components of the analyte mixture (neutral or anionic). The effects of alteration of the percent organic modifier, flow rate and temperature of the mobile phase on chromatographic retention and efficiency on these phases were briefly examined.     

Application of cyclam-capped beta-cyclodextrin-bonded silica particles as a chiral stationary phase in capillary electrochromatography for enantiomeric separations

Two novel types of substituted cyclam-capped beta-cyclodextrin (beta-CD)-bonded silica particles have been prepared and used as chiral stationary phases in capillary electrochromatography (CEC). The two stationary phases have a chiral selector with three recognition sites: beta-CD, cyclam, and the latter's sidearm. They exhibit excellent enantioselectivities in CEC for a wide range of compounds as a result of the cooperative functioning of the anchored beta-CD and cyclam. After inclusion of the metal ion (Ni2+) from the running buffer into the substituted cyclams and their sidearm ligands, the bonded stationary phases become positively charged and can provide extra electrostatic interactions with ionizable solutes and enhance the dipolar interactions with some polar neutral solutes. This enhances the host-guest interaction with some solutes and improves chiral recognition and enantioselectivity. These new types of stationary phases exhibit great potential for fast chiral separations in CEC.     

High-stability ionic liquids. A new class of stationary phases for gas chromatography

Room-temperature ionic liquids are a class of non-molecular ionic solvents with low melting points. Their properties have the potential to be especially useful as stationary phases in gas-liquid chromatography (GLC). A series of common ionic liquids were evaluated as GLC stationary phases. It was found that many of these ionic liquids suffer from low thermal stability and possess unfavorable retention behavior for some classes of molecules. Two new ionic liquids were engineered and synthesized to overcome these drawbacks. The two new ionic liquids (1-benzyl-3-methylimidazolium trifluoromethanesulfonate and 1-(4-methoxyphenyl)-3-methylimidazolium trifluoromethanesulfonate) are based on "bulky" imidazolium cations with trifluoromethanesulfonate anions. Their solvation characteristics were evaluated using the Abraham solvation parameter model and correlations made between the structure of the cation and the degree to which the ionic liquids retain certain analytes. The new ionic liquids have good thermal stability up to 260 degrees C, provide symmetrical peak shapes, and because of their broad range of solvation-type interactions, exhibit dual-nature selectivity behavior. In addition, the ionic liquid stationary phases provided different retention behavior for many analytes compared to a commercial methylphenyl polysiloxane GLC stationary phase. This difference in selectivity is due to the unique solvation characteristics of the ionic liquids and makes them very useful as dualnature GLC stationary phases.     

Theory and use of the pseudophase model in gas-liquid chromatographic enantiomeric separations

The theory and use of the "three-phase" model in enantioselective gas-liquid chromatography utilizing a methylated cyclodextrin/polysiloxane stationary phase is presented for the first time. Equations are derived that account for all three partition equilibria in the system, including partitioning between the gas mobile phase and both stationary-phase components and the analyte equilibrium between the polysiloxane and cyclodextrin pseudophase. The separation of the retention contributions from the achiral and chiral parts of the stationary phase can be easily accomplished. Also, it allows the direct examination of the two contributions to enantioselctivity, i.e., that which occurs completely in the liquid stationary phase versus the direct transfer of the chiral analyte in the gas phase to the dissolved chiral selector. Six compounds were studied to verify the model: 1-phenylethanol, alpha-ionone, 3-methyl-1-indanone, o-(chloromethyl)phenyl sulfoxide, o-(bromomethyl)phenyl sulfoxide, and ethyl p-tolylsulfonate. Generally, the cyclodextrin component of the stationary phase contributes to retention more than the bulk liquid polysiloxane. This may be an important requirement for effective GC chiral stationary phases. In addition, the roles of enthalpy and entropy toward enantiorecognition by this stationary phase were examined. While enantiomeric differences in both enthalpy and entropy provide chiral discrimination, the contribution of entropy appears to be more significant in this regard. The three-phase model may be applied to any gas-liquid chromatography stationary phase involving a pseudophase.     

Oxygen transport phenomena at the liquid metal-vapour interface

A system made of an atmosphere, a liquid metal and an oxide phase at a given temperature and total pressure is zero-variant and allows only a particular set of partial pressures, compatible with thermodynamic equilibrium. For any different gas composition the system will show a tendency to evolution. Therefore, classical thermodynamics cannot give the answers to a number of problems of major interest, such as those concerning the conditions for interface saturation and oxide formation. Strictly speaking these are kinetic problems, but they can still be treated as pseudo-thermodynamic questions. The key to the problem is in considering the characteristic times of evolution, which suggest stationary state approximation for the condensed phases. In many instances, the evaluation of gas-atmosphere mass exchanges under stationary conditions makes it possible to determine the effective oxygen pressure at which the oxidation of the metal becomes evident. Surface tension measurements allow this condition to be detected with a good accuracy. According to experimental evidence, the effective oxygen pressure can be many orders of magnitude greater than the equilibrium value. The problem needs different theoretical approaches according to the molecular mechanisms involved. Moreover, from the experimental point of view, there are particularly delicate questions regarding the accuracy and the significance of the oxygen control and measurement.