Use of Nonlinear Frequency Response for Discriminating Adsorption Kinetics Mechanisms Resulting with Bimodal Characteristic Functions

One of the characteristic examples of the inability of the classical linear frequency response (FR) method to identify the correct kinetic mechanism is adsorption of some substances (p-xylene, 2-butane, propane or n-hexane) on silicalite-1. The linear FR resulted with bimodal FR characteristic functions, which fitted equally well to three different kinetic models: nonisothermal micropore diffusion, two independent isothermal diffusion processes, and an isothermal diffusion-rearrangement process. We show that the second order frequency response functions (FRFs), obtained from the nonlinear FR, can be used for discrimination among these three mechanisms. Starting from the nonlinear models, we derive the theoretical expressions for the first and second order FRFs corresponding to these three mechanisms and show that different shapes of the second order FRFs are obtained for each mechanism. This would enable identification of the real mechanism from nonlinear FR data.     

CH3F absorption of the CO2-laser emission measured by the photoacoustic technique

Spectra of coincidence of CH₃F IR absorption with CO₂-laser emission at pressures of 2, 10 and 60 Torr were recorded by the use of a photoacoustic detection method in the whole range of CO₂-laser emission. The spectra show that CH₃F absorbs many CO₂-laser lines in the range 1084–1071 cm⁻¹ with the strongest absorption at 1046.80cm⁻¹, laser line P(20). Absorption is predominantly due to the fundamental of v₃, which is well spread over the whole laser emission range. The intensities of all absorptions rise with increasing pressure, but some absorptions change their relative intensity with respect to one another. In addition, the fine structure of the line spectrum, characteristic of lower pressure samples, disappears as pressure is increased.     

Self-organization in aqueous solutions of thermosensitive statistical copolymers based on N-(dimethylamino)ethyl methacrylate

Thermo- and pH-responsive statistical copolymers of N-(dimethylamino)ethyl methacrylate and lauryl methacrylate were synthesized by free radical copolymerization. Obtained samples differed in content of hydrophobic components (3 and 6?mol. %). Their molar masses were close to 30,000?g/mol. Self-organization in buffer solutions of copolymers were studied using light scattering and turbidimetry. It was found that copolymers as well as of poly(N-(dimethylamino)ethyl methacrylate) were thermosensitive at pH?>?7. Phase separation temperatures of investigated solutions decreased with dilution and pH increasing. Growth of lauryl methacrylate content in copolymers caused the decrease in phase separation temperatures.     

Radioactivity of building materials in Serbia and assessment of radiological hazard of gamma radiation and radon exhalation

Journal of Radioanalytical and Nuclear Chemistry - This paper presents a gamma spectrometric analysis of 47 samples of building materials produced and used in Serbia. Based on the measured activity...     

Investigation of gas transport through porous membranes based on nonlinear frequency response analysis

Theoretical development of a new experimental method for investigation of mass transport in porous membranes, based on the principle of the modified Wicke-Kallenbach diffusion cell and the nonlinear frequency response analysis is presented. The method is developed to analyze the transport of a binary gas mixture in a porous membrane. The mixture is assumed to consist of one adsorbable and one inert component. Complex mass transfer mechanism in the membrane, where bulk or transition diffusion in the pore volume and surface diffusion take place in parallel, is assumed. Starting from the basic mathematical model equations and following a rather standardized procedure, the frequency response functions (FRFs) up to the second order are derived. Based on the derived FRFs, correlations between some characteristic features of these functions on one side, and the whole set of equilibrium and transport parameters of the system, on the other, are established. As the FRFs can be estimated directly from different harmonics of the measured outputs, these correlations give a complete theoretical basis for the proposed experimental method. The method is illustrated by quantifying the transport of helium (inert gas) and C₃H₈ and CO₂ (adsorbable gases) through a porous Vycor glass membrane.     

The inhibiting effect of cobalt(III)–<Emphasis Type="Italic">cyclam</Emphasis> complexes with substituted β-diketones on iron corrosion in perchlorate solution

The inhibiting effect of cobalt(III) complexes with macrocyclic ligand cyclam (1,4,8,11-tetraazacyclotetradecane) and β-diketonato ligands have been investigated on iron corrosion in 0.1 M HClO₄ by potentiodynamic, linear polarization resistance (LPR), and electrochemical impedance spectroscopy (EIS) measurements. Analysis of the polarization curves and impedance spectra, by adding complex compounds to the acid solution and comparing with inhibitor-free solution, show corrosion current decrease and charge transfer resistance increase, respectively. Impedance data are fitted with equivalent circuit models. The stability of the adsorbed film was followed by LPR. Scanning electron microscopy (SEM) was used to screen physical changes of the reacted surfaces both treated and untreated. The differences in inhibitor efficiencies depend on the substituent group of the coordinated β-diketone ligand. Structural and electronic properties of this group of compounds in relation to inhibitor efficiency were analyzed by using the molecular modeling structures and correlated with previously reported spectroscopy data.