Streaming birefringence. VII. Influence of the intermolecular hydrodynamic interaction on the viscosity and streaming birefringence of polymer solutions

The cavity model used in the theory of dielectrics was applied to hydrodynamics to calculate the force exerted by a system of soft dumbbells on a reference dumbbell in a hydrodynamic field. The influence of this force on the viscosity and flow birefringence and its dependence on both the concentration and velocity gradient were calculated. The system of equations has a real solution only for values of β = M[η]η₀γ/RT which are smaller than a critical value rapidly decreasing with increasing concentration. At zero concentration the results obtained agree with the theory of a single isolated dumbbell model. The calculated Huggins constant is k′ = 0.4. The extinction angle is connected with the relative viscosity very nearly as derived from experiments. However, the theory fails at higher concentrations and gradients yielding an increase in viscosity with the gradient and infinite zero-shear viscosity for the concentration c = 2.5/[η].     

Automated classification of candidate structures for computer-assisted structure elucidation

In computer-assisted structure elucidation, a large number of candidate structures for the unknown compound can be generated. A computer program designed to aid in the recognition of significant differences between these structures is described. The goal of the program is to group the candidates into meaningful classes with a minimum of input from the user; each class is distinguished by a substructure its members have in common. A computational approach is developed based on the combinatorial problem of set covering. The program evaluates its results using an information-theoretical criterion. An application of the program to a real-word structure problem is presented.     

Intermolecular contact interactions and their temperature dependence

A model, based on inverse gas chromatography experiments, has been developed for intermolecular interaction and its temperature dependence. The model ascribes to each substance a four-component solubility parameter; the four components reflect the van der Waals, polar, electron donor, and electron acceptor interactive properties. Their values depend on temperature in the same manner as does the cohesive energy. The latter was found to depend only on the critical temperature, the acentric factor, and the reduced temperature. The model was used for evaluation of the solubility parameters from polymer-solvent interaction coefficients and their temperature dependence with high accuracy. For binary solventsolvent mixtures, the free energy of mixing and its temperature dependence, as well as enthalpy of mixing can be derived from this model with a good accuracy.     

An in situ FTIR study of the electrochemical oxidation of methanol at small platinum particles

It is shown for the first time that it is possible to employ electrochemical in situ Fourier transform infrared (FTIR) spectroscopy to study the electro-oxidation of methanol at small platinum particles. A number of differences with respect to the behaviour at a bulk metal electrode are observed; these observations demonstrate beyond doubt the very significant difference between bulk and particle electrode mechanisms for the oxidation of methanol, and reveal the dangers of extrapolating from the former to the latter.     

The one- and multi-sample problem for functional data with application to projective shape analysis

In this paper tests are derived for testing neighborhood hypotheses for the one- and multi-sample problem for functional data. Our methodology is used to generalize testing in projective shape analysis, which has traditionally involving data consisting of finite number of points, to the functional case. The one-sample test is applied to the problem of scene identification, in the context of the projective shape of a planar curve.     

Aspect-ratio dependent oscillatory thermocapillary convection in the floating half zone

The dependency of the critical Marangoni number on the geometrical aspect ratio of the floating half zone is essential to predict the onset of oscillatory thermocapillary convection.The experimental studies in the microgravity conditions on floating half zones of several centimeters in diameter have predicted that the critical Marangoni number increases with the increasing aspect ratio,and the terrestrial experimental studies have predicted the contradictory conclusion for floating half zones of several mil...     

Non-Gravitational Effects with Density-Matching in Evaluating the Influence of Sedimentation on Colloidal Coagulation

The method of density matching between the solid and liquid phases is often adopted to effectively eliminate the effect of sedimentation of suspensions in studies on dynamic behaviour of a colloidal system. However, the associated changes in the solvent composition may bring side effects to the properties investigated and therefore might lead to a faulty conclusion if the relevant correction is not made. To illustrate the importance of this side effect, we present an example of the sedimentation influence on the coagulation rate of suspensions of 2μm （diameter） polystyrene. The liquid mixtures, in the proper proportions of water （H2O）, deuterium oxide （D2O） and methanol （MeOH） as the liquid phase, density-matched and unmatched experiments are performed. Besides the influence of viscosity, the presence of methanol in solvent media, used to enhance the sedimentation effect, causes significant changes （reduction） in rapid coagulation rates compared to that in pure water. Without the relevant corrections for those non-gravitational factors it seems that gravitational sedimentation would retard the coagulation. The magnitude of the contribution from the non-gravitational factor is quantitatively determined, making the relevant correction possible. After necessary the influence of the sedimentation on coagulation rates at corrections for all factors, our experiments show that the initial stage of the coagulation is not observable.