Thermodynamics of molecular interactions in binary mixtures of non-electrolytes. Molar excess volumes

Molar excess volumes, V^E, for pyridine (A) + α-picoline (B), + β-picoline (B) and + γ-picoline (B) and benzene (A) + toluene (B), + o-xylene (B) and + p-xylene (B) and carbon tetrachloride (A) + n-heptane (B) have been measured dilatometrically as a function of temperature and composition and have been utilized to study B—B and B—B—B interactions in the presence of A via the Mayer—McMillan approach. A model has also been presented to account for these B—B and B—B—B interactions. The V^E data at 308.15 K have also been analysed in terms of the “graph theoretical” approach which describes the V^E data well for all these mixtures at 308.15 K. The “graph theoretical” approach has further been extended to successfully evaluate V^E data for a mixture at any temperature, T₂, when the V^E data at T₁ are known.     

Colorimetric method for the determination of captafol (difolatan) in commercial formulations and residues on grains and apples.

A simple and rapid colorimetric method for the microdetermination of captafol (difolatan), based on its reaction with a dithiocarbamate, has been developed. The bright yellow colour which develops instantaneously on mixing the fungicide with the reagent is stable for at least 12 h. The method has been successfully adapted to the determination of captafol in its formulated products and residues on grains and apples.     

Synthesis,structural and biochemical aspects of titanocene and zirconocene chelates of acetylferrocenyl thiosemicarbazones

The reactions of bis(cyclopentadienyl)titanium(IV)/zirconium(IV) dichloride with a new class of organometallic thiosemicarbazones (LH), derived by condensing acetylferrocene with substituted thiosemicarbazides, have been studied and two types of bimetallic products, viz. [Cp₂M(L)Cl] (M = Ti or Zr) and [CpZr(L)₃], have been isolated. On the basis of various physicochemical and spectral studies, five- and seven-coordinate structures have been assigned to these derivatives, respectively. Attempts have been made to establish a correlation between biological activity and the structures of the products.     

Chemical effects of neutron induced nuclear reactions in KIO4 at different pH of dissolution

Dissolution effect on recoil¹²⁸I retention in the form of IO ₄ ^– ion following /n,/ process in potassium periodate target has been studied. A remarkable variation in retention is found both in solid and solution phase with the pH of dissolution. A suitable mechanism is suggested to explain the observed results.     

Determination of lead concentration and lead isotope ratios in calcium supplements by inductively coupled plasma mass spectrometry after high pressure, high temperature digestion

The presence of lead as a contaminant in calcium supplements has aroused considerable public health interest in recent years. In this investigation lead and lead isotope ratios were determined by ICP-MS in ten brands of calcium supplements after high pressure/temperature digestion. Calcium supplements (200 to 250 mg) were digested in 2 mL of nitric acid at 230?°C and at a pressure of 1770 psi (1.2 × 10⁴ kPa). Lead concentrations were determined by matrix-matched lead standards prepared in a high-purity calcium carbonate matrix. Good recoveries of lead and calcium were obtained for certified animal bone reference material. High levels of Pb (8 to 28 μg Pb per g of calcium) were found in calcium supplements that contain dolomite or bone meal. Chelated and refined calcium supplements had lower Pb levels (0.8 to 0.9 μg Pb/g Ca). Application of lead isotope ratios to distinguish the origin of calcium sources was also explored.     

Addition Compounds of Organotin halides. III. Adducts of n-propyl tin Trichloride with Amines

n-Propyl tin trichloride and its complexes with bases as pyridine, α, β-and γ-picolines, isoquinoline, piperidine, morpholine, aniline and benzylamine have been prepared. The complexes have been characterised by their I.R. and molar conductance measurements. Assignments for some I.R. frequencies have been reported and discussed. Molar conductance values of some of the complexes in nitrobenzene categories them to be uni-univalent electrolytes.     

Kinetics of ion-exchange of transition metals on tin(IV) arseno-silicate cation exchanger

Exchange kinetics of some transition metal ions on tin(IV) arsenosilicate has been studied at various temperatures under particle diffusion controlled conditions. Various useful kinetic parameters such as self-diffusion coefficient (D_o), energy of activation (E_a) and entropy of activation (S^*) have been calculated and compared with other similar materials.

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(IV) . , (D_O), (E_a) (S^*), .

     

Embedding discrete flows on R in a continuous flow

The problem of determining when a given discrete flow on a topological space is embeddable in some continuous flow was mentioned by G. R. Sell (“Topological Dynamics and Ordinary Differential Equations,” Van Nostrand, New York, 1971) in his book on topological dynamics. In this book, the theory of generalized dynamical systems is exploited in the qualitative study of differential equations. Even more complicated is the problem of simultaneously embedding two or more discrete flows in a single continuous flow. We examine both of these problems when the underlying topological space is the space R of the real numbers.     

Adhesion and debonding of soft elastic films: crack patterns, metastable pathways, and forces

We study the phenomenon of debonding in a thin soft elastic film sandwiched between two rigid plates as one of the plates is brought into intimate contact and then pulled away from contact proximity by application of a normal force. Nonlinear simulations based on minimization of total energy (composed of stabilizing elastic strain energy and destabilizing adhesive interaction energy) are employed to address the problems of contact hysteresis, cavitation, crack morphology, variation of contact area, snap-off distance, pull-off force, work done, and energy loss. Below a critical distance (d(c)) upon approach, simulations show the formation of columnar structures and nonrandom, regularly arranged nanocavities at the soft interface at a length scale of approximately 3h (h being the thickness of the film). The persistence of such instability upon withdrawal (distance >d(c)) indicates a contact hysteresis, which is caused by an energy barrier that separates the metastable states of the patterned configuration and the global minimum state of the flat film. The energy and the pull-off force are found to be nonequilibrium and nonunique properties depending on the initial contact, defects, noise, etc. Three broad pathways of debonding leading to adhesive failure of the interface, depending on the stiffness of the film, step size of withdrawal, and the imposed noise, are identified: a catastrophic column collapse mode, a peeling mode involving a continuous decrease in the contact area, and a column splitting mode. The first two modes are caused by a very high stress concentration near the cavity edges. These metastable patterned configurations engender pull-off forces that are orders of magnitude smaller than that required to separate two flat surfaces from contact.