A Monte Carlo simulation of the heterogeneous adsorption of hydrogen ions on metal oxides: Effect of inert electrolyte

Charging of the surface of an oxide caused by the adsorption of hydrogen ions and ions of inert 1:1 electrolyte was investigated by using grand canonical Monte Carlo simulation technique. In particular, adsorption isotherms of protons as well as of ions of the electrolyte together with the resulting charge density of the surface were obtained for different system parameters. Also, the effect of the surface energetic heterogeneity and the concentration of the background electrolyte on the isotherms and the charge density curves was examined. Furthermore, lateral interactions in the mixed adsorbed phase were taken into account in the modeling of the system behavior. The obtained results, in general, suggest that the three factors mentioned above may have substantial influence on the charging mechanism at the liquid/oxide interface.     

Sticking probability for oxygen adsorption and readsorption on thin iron films

Sticking probability for oxygen adsorption on thin iron films and readsorption on surface sites liberated due to incorporation of the adsorbate adatoms below the surface during thermal treatment has been studied by means of the Wagener flow method. Sticking probability for oxygen adsorption on oxidized thin iron films has also been measured for comparison.

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Evaluation of a purge-and-trap injection system for capillary gas chromatography-microwave induced plasma-atomic emission spectrometry for the determination of volatile selenium compounds in water

A method is presented for the selective determination of the volatile selenium species dimethylselenide and dimethyldiselenide, using a commercially available purge-and-trap injection system coupled to capillary gas chromatography-microwave induced plasma-atomic emission spectrometry. The efficiency of the purging step was evaluated and the parameters affecting the purge and trap processes were optimized. The method was applied to the determination of volatile selenium compounds in lake water. Relative detection limits of 2ng/l for dimethylselenide and dimethyldiselenide, corresponding to an absolute detection limit of 10 pg, were achieved.     

Evidences for temperature-dependent mechanism of host-guest complexation

Summary High-performance liquid chromatography and ultraviolet spectroscopy methods were applied to the studies on the influence of temperature on the complexation of β-cyclodextrin with naphthalene and its derivatives. The strong nonlinearity of Van't Hoff plots suggests, that the retention mechanism of hydrocarbons investigated might be different in high and low temperature region. The total lack of correlation (r=−0.230) between chromatographic data (capacity factors ratio:k _PAH/k _PAH×CD) and spectrophotometric data (ΔA) at high temperature (60°) as well as a significant correlation (r=0.922) at subambient temperature (15°C) suggest, that the inclusion mechanism starts to be important at low temperature region and the predominant mechanism for chromatographic retention is the formation of an inclusion complexes in the mobile phase.     

Role of the surface heterogeneity in adsorption of hydrogen ions on metal oxides: theory and simulations

In this article we study the effect of energetic heterogeneity of a crystalline surface on the adsorption of hydrogen ions (protons) from the liquid phase. In particular, we examine the influence of the shape of the adsorption energy distribution on the equilibrium isotherms of hydrogen ions. To that purpose, a few popular distribution functions, including rectangular, exponential, and asymmetric Gaussian are considered. Additionally, multimodal distribution functions, which may correspond to the adsorption on different crystal planes of the oxide, are also used. Lateral interactions between adsorbed charges are modeled using the potential function proposed by Borkovec et al., which accounts also for polarization of the liquid medium. The results presented here are obtained using both Monte Carlo (MC) simulations and theoretical calculations involving Mean Field Approximation (MFA). They indicate that increased energetic heterogeneity of the adsorbing surface may, in general, considerably change the behavior of the adsorption isotherms, regardless of the assumed distribution function. It is also shown that the predictions of the proposed theory are consistent with the data obtained from the MC simulations.     

Formal Mathematical Analysis of the Existence of the Common Intersection Point in Relation to Determining the Parameters Describing Ion Adsorption at the Oxide/Electrolyte Interface: Comparison of the Triple and Four-Layer Models

For most oxide/electrolyte systems potentiometric titration curves measured for different ionic strengths have a Common Intersection Point (CIP) which corresponds to the Point of Zero Charge (PZC). However, there are systems where a CIP exists but the surface charge at this point does not equal zero (PZC CIP). In this paper theoretical analysis of the systems in which the PZC and CIP do not coincide is presented. It is based on the well-known 2-pK surface charging approach and Triple Layer Model (TLM) as well as the Four Layer Model (FLM) of the electric double layer. The appropriate mathematical criterion for CIP existence was applied with detailed derivations, both for TLM and FLM. Having determined in this manner the parameter values, one can draw proper conclusions about the features of oxide/electrolyte adsorption systems, in which PZC and CIP do not coincide. The values of adsorption parameters are found by fitting simultaneously the obtained theoretical expressions to both of the experimental titration isotherms, and to the individual isotherms of electrolyte cation adsorption measured using radiometric methods.     

Synthesis,thermal stability and structural characterisation of iron(II) phthalocyanine complex with 4-cyanopyridine

A new complex of bis-axially coordinated iron(II) phthalocyanine by 4-cyanopyridine (4-CNpy) has been obtained in crystalline form as an adduct with two 4-CNpy molecules. The [FePc(4-CNpy)₂] · 2(4-CNpy) crystallises in the monoclinic system, space group P2₁/c with two molecules in the unit cell. The iron(II) coordinates four isoindole nitrogen atoms of the almost planar phthalocyaninato(2−) macroring and axially two nitrogen atoms of 4-CNpy molecules. The coordination polyhedron around the Fe(II) atom approximates to a tetragonal by-pyramid. Four equatorial Fe–N bonds are shorter (1.936(2) Å) than two axial Fe–N bonds (2.027(2) Å). The centrosymmetric FePc(4-CNpy)₂ molecules form alternating sheets parallel to the bc crystallographic plane and solvated 4-CNpy molecules that are anti-parallel oriented by their polar cyano groups are located between the sheets of FePc(4-CNpy)₂ molecules. Ligation of the intermediate-spin iron(II) phthalocyanine by 4-CNpy molecules leads to the low spin Fe(II) complex. The importance of the d(π) → π^∗(Pc) back donation is manifested in the difference between the values of C–N isoindole and C–N azamethine bond lengths of the Pc macrocycle. The thermal analysis of the crystals of [FePc(4-CN)₂] · 2(4-CNpy) shows two steps responsible for a loss of solvated (∼170 °C) and coordinated (∼235 °C) 4-CNpy molecules.