Calculation of IR- and Raman-active vibrations of hexacyano complexes of Fe, Co, Mn, Cr V

A complete vibrational analysis of the hexacyano complexes of Fe^II, Co^III, Mn^II, Cr^III V^II is presented on the basis of the valence force field method. The calculated frequencies of the complexes are in good agreement with the experimental values. The direct and inverse vibrational problems are solved for all the complexes and the correct force fields obtained. In the case of [Fe(CN)₆]⁴⁻ the direct and inverse electrooptical problem is also solved. The calculated electrooptical parameters satisfactorily describe the experimental intensities of the bands in the mid-IR region.     

Application of Continuous Kinetics to Polymer Degradation

Abstract

Degradation of polydisperse polymers is studied in the framework of continuous kinetics which is directly based on continuous distribution functions which depend on the molecular weight and the time. A firstorder formalism is presumed. A Schulz-Flory distribution (with time-dependent parameters) is assumed to be valid during the entire time of degradation. Thus, an essential simplification of the solution procedure of the continuous rate equation is achieved. As a proof of accuracy, the approximation solution and the exact solution are compared for the case of “random scission.” Furthermore, the developed method is shown to be suitable for describing the experimental data of dextran degradation caused by acid hydrolysis, by ultrasonic irradiation, and by enzymatic attack. The model parameters fitted to the experimental data allow the evaluation of the scission probability as a function of the molecular weight and of the location of the bond to be broken within the molecule.     

Computer aided exploitation of mathematical models of processes. A general description of the approach

An approach is described which helps the experimenter in: (a) selecting the most appropriate method of determination of physicochemical or technical parameters, (b) optimization of analytical procedures or of determination of physicochemical parameters, (c) indication of the possible improvements of the experimental technique applied, (d) diagnosis of the model and the data handling scheme applied in the determination of parameters, and other. The examples presented are based on simulated experiments. They concern selection of the best method for determination of an equilibrium constant and for determination of two analytes from a single instrumental (photometric, potentiometric) titration curve.     

Experimental Study of the Polydispersity of Aqueous Colloid of Palygorskite and Suspensions of Escherichia Coli and Pseudomonas Fluorescens by an Electrooptical Method

The results of experimental study on the polydispersity of an aqueous colloid of palygorskite and aqueous suspensions of Escherichia coli (E. coli) and Pseudomonas fluorescens(Ps. fluorescens) are reported. The study is based on the use of a new method; i.e., on the investigation of an electrooptical effect appearing when a weak sinusoidal electric field with sinusoidal amplitude modulation is applied on the system. This method was developed for studying systems in which only slight particle orientation is possible under action of an external electric field. Disperse systems with a high conductivity, including cell suspensions and other biocolloids, colloids containing small particles, as well as solutions of macromolecules and polyelectrolytes, are among such systems. The experimental setup developed in this work is described. The results obtained are compared with data of microscopic measurements and the results of the study of polydispersity in strong fields based on the investigation of the relaxation of electrooptical effect.     

Infrared intensities of methane and ethane. A starting set of electrooptical parameters for n-hydrocarbons

Sets of electrooptical parameters (eop's), suitable for longer n-paraffins and less constrained than those already used to fit the IR intensities of CH₄ and C₂H₆ and their deuterated derivatives, are presented and discussed. The technique adopted in the least-squares refinement of eop's from experimental data is discussed in detail.     

Electrooptical properties of polarization holographic gratings formed in liquid-crystal composites

The results of experimental study of the electrooptical properties of polarization holographic gratings formed in a liquid-crystal composite by polarization holography are presented. The influence of the formation conditions, the parameters of the controlling ac electric field, and the composite geometry on the diffraction efficiency of such gratings is considered.     

Low-temperature heat capacities and thermodynamic properties of crystalline isoproturon

An incremental integral isoconversional method for the determination of activation energy as a function of the extent of conversion is presented. The method is based on the treatment of experimental data without their transformation so that the resulting values of activation parameters should not be biased. The method was tested for recovering the activation energies from simulated data and employed for the treatment of experimental data of the NiS recrystallisation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Der einfluβ der molmassenverteilung und der kettenabstandsverteilung auf die streufunktion von polymeren in lösung

Universal expressions of the scattering function for coils with uniform and non-uniform expansion, gaussian and non-gaussian chain segment distribution functions and various types of molar mass distributions are given. Facilities to determine the parameters of the functions are discussed. Comparison of the calculated scattering functions with experimental data, for vinyl-polymers in good and poor solvents and for cellulose derivatives in solution, lead to the following statements: (1) Up to now light scattering measurements do not have the precision necessary to predict the form of the chain segment distribution function. Nevertheless measurements on vinyl-polymers in good solvents indicate non-gaussian chain segment distribution functions. (2) The experimental determined scattering function for vinyl-polymers in poor solvents and cellulose derivatives in solution correspond to the calculated scattering function for coils with uniform expansion and gaussian chain segment distribution function within experimental error.     

Polymer–polymer interaction parameters of polystyrene and polybutadiene from studies in solutions of toluene or tetrahydrofuran

Equations used for the determination of polymer–polymer interaction parameters for narrow molecular weight distribution polymers which have undergone phase separation in solutions are discussed. Binodals with tie lines and plait points are presented for ternary systems polystyrene-polybutadiene-toluene and polystyrene-polybutadiene-tetrahydrofuran. Typical interaction parameters determined from the experimental data for the polystyrene-polybutadiene systems are presented.     

Complex electrooptic research of nano-particle parameters in colloids

A research of some colloids has been carried out by means of dynamic light scattering, electrooptical and magnetooptical techniques. Intensity autocorrelation functions of scattered light have been compared to the relaxation curves of electrooptical effect for colloid particles of different shapes. The results of complex research confirm that the complicated character of light scattering by particles allows us to use the methods of birefringence and dichroism only formally when studying most colloid systems. Very thin nano-disperse structures are an exception to this rule. The investigation of polydispersity of some colloids was carried out by magnetooptical and two electrooptical techniques. Size distribution functions resulted from the different techniques agree. This justifies the suppositions about particle light scattering that are required for the use of the methods.     

Particle size analysis of polymer latexes by light scattering. V. The significance of an assumed distribution in the analysis of angular scattering data

In the analysis of light scattering data from polymer latex systems or other systems of spherical particles, it is necessary to assume a particle size distribution function. Theoretical angular scattering functions based on the assumed distribution and representing a wide range of size distribution parameters are compared to experimental data in order to obtain a best fit. In previous work, it has been shown that as the polydispersity increases beyond certain limits the uncertainty in the assignment of the size distribution parameters (i.e., the best fit) increases. This report is concerned with the analysis of angular scattering from unimodal systems and simulated cases where theoretical scattering functions for wide, negatively skewed distributions are used as “experimental data,” are analyzed by utilizing four different distribution functions. These functions represent different degrees of skewness and include negatively, positively, and normally skewed distributions. The results from the use of the various distribution functions are discussed with respect to the uncertainly in the assignment of distribution parameters resulting from the loss of structure in the angular scattering pattern due to increased polydispersity. Scattering data from the bimodal distribution are analyzed by assuming a unimodel distribution, and the consequences of this assumption are assessed.     

A long-pitch orthoconic antiferroelectric mixture modified by isomeric and racemic homostructural dopants

Orthoconic Antiferroelectric Liquid Crystals (OAFLC) are recognised as a promising medium for display and photonic applications due to their unique electrooptical properties. The application of OAFLC is still hampered by a number of parasitic effects deteriorating the electrooptical performance of contemporary available materials. An attempt elaborating of a working OAFLC mixture with the helical pitch longer than the typical cell gap is reported. Using this mixture, near-perfect optical uniformity and excellent dark state at the zero electric field applied were obtained. Basic OAFLC mixture was doped with two homostructural analogues to study the influence of the molecular polarity and chirality on the electrooptical performance and chosen physical parameters. The physical and structural properties of admixtures and their electrooptical performance are presented and discussed.     

Role of vibrational intensities in the determination of molecular structure and charge distribution

Vibrational intensities can be parametrized in terms of EOPs (electrooptical parameters). EOPs may be used for interpretation and prediction of vibrational intensities, for determination from the spectra of the structure of ordered and disordered materials, for check of the force fields. Recently it has been shown that EOPs have a physical meaning independently on intensity parametrization and that they can be used to describe the charge distribution in the molecules and to understand some electrostatic interactions between the molecules.     

Electrooptical and Conformational Properties of Poly(1-Trimethylsilyl-1-Propynes) with Different Chain Microstructures

The methods of the Kerr effect and solution hydrodynamics were applied to study the electrooptical and hydrodynamic properties of samples of disubstituted polyacetylenes, poly(1-trimethylsilyl-1-propynes), prepared by polymerization of 1-trimethylsilyl-1-propyne with NbCl₅ and TaCl₅/BuLi as catalysts. The experimental electrooptical characteristics of polymers were compared with those calculated by PM3 semiempirical quantum-chemical method.     

An electrooptical method for studying the mean length of stereoblocks in poly(1-trimethylsilyl-1-propynes) and poly(1-trimethylgermyl-1-propynes)

It was shown that equilibrium electrooptical properties (the Kerr effect) in solutions of disubstituted polyacetylenes poly(1-trimethylsilyl-1-propyne) and poly(1-trimethylgermyl-1-propyne) are related to the dipole structure of these polymers that is associated with the partial spiralization of their chains. A method of estimating the length of monomer unit sequences occurring in the same spatial configuration (stereoblocks) was developed. This method is based on the experimental measurement of the specific Kerr constant of disubstituted polyacetylenes. The sizes of stereoblocks in polymer chains that were synthesized with the use of various catalysts and that differ in the mean ratio of trans: cis C=C bonds, as estimated by the electrooptical method, were compared with the X-ray diffraction data on the same film polymers. There was good agreement between the results obtained by both methods.     

Average cluster size determination in supersonic beams from angular distribution measurements after scattering by a buffer gas

A method for the determination of average cluster size in supersonic beams is presented. Based on angular distribution broadening of the beams caused by passing through a buffer gas, this method is well suited for in situ determination of the mean cluster size when the apparatus contains a movable detector with sufficient spatial resolution. The shape and width of the beam profile after scattering by a buffer gas are evaluated theoretically as functions of buffer gas pressure and atom-cluster collision cross-section. Experimental results are presented for an argon beam, yielding average cluster sizes between 300 and 7000 atoms depending on the stagnation pressure. Simple criteria to assess the applicability of the method to a given experimental situation are discussed. The average cluster sizes determined in this work agree quite satisfactorily with previously published values for similar beam generation conditions.     

Flow Injection Analysis of Histidine with Enhanced Electrogenerated Chemiluminescence of Luminol

Histidine is one of the necessary basic amino acids in biological bases, which often controls the catalytic activity of enzymes and acts in holding the higher structure of proteins. Furthermore, it is also an important ingredient in pharmaceutical preparations used for treatment of hetpatosis and nephropathy. Therefore, the determination of histidine in biological fluids and pharmaceutical preparations is of great importance. Various methods have been proposed for the detection of histidine …     

Determination of spherulite size distribution by small-angle light scattering

The theoretical backgrounds of the method of spherulite size distribution determination, on the basis of the small-angle light scattering technique, are presented. Special corrections of experimental data are introduced to achieve great accuracy of the determination of scattered light intensity distribution. Experiments have been done on low-density polyethylene samples obtained in various crystallization conditions. For these samples, the stepwise distributions of spherulite size have been determined.     

A method to estimate the Leslie coefficients of liquid crystals based on MBBA data

A new effective approach for estimating the Leslie coefficients of liquid crystals based on MBBA data is presented. Literature values of the temperature-dependent Leslie viscosity coefficients of MBBA are used to fit with the analytical functions of Leslie coefficients based on the Imura and Okano theory, and a set of constants in these functions are determined. The same functions are then applied to two high birefringence liquid crystal mixtures, E7 and UCF-2, to extract their Leslie coefficients based on their order parameters. Using the extracted Leslie coefficients, the simulation results agree very well with the experimental data.     

Electronic factor in electron self-exchange reaction of hydrated redox ion pairs from thermodynamic data

An accurate scheme for determining the electronic factor of the electron self-exchange reaction in solution is presented in this paper. The used various activation parameters and slopes of potential energy surfaces are obtained in terms of an improved activation model and the accurate potential function determined from the vibrational spectroscopic and thermodynamic data. The coupling matrix elements are determined using numerical integral method over the perturbed double-zeta Slater-type state functions. Theoretical results of electronic factor in this work are found in close agreement with those extracted from experimental rate constant data and to be less than unity. Results indicate that outer-sphere electron transfer reactions in solution involving hydrated transition metal ions are nonadiabatic in nature.