Determination of acidic sites and binding toxic metal ions on cumin surface using nonideal competitive adsorption model

A fundamental study of the application of cumin biomass in the recovery of Cu and Zn metal ion uptake from food and drinks is carried out at different pH's and at fixed ionic strength. The chemical characteristics of protein in cumin seeds were investigated. Results showed that cumin contains 18.25% crude protein, which includes 18 amino acids. The main reactive groups on protein cumin are amino and carboxylic groups of dicarboxylic amino acids, leading to a pH-dependent charge. Therefore, the cumin surface is considered as a heterogeneous system. To describe protonation behavior in a heterogeneous cumin biomass (cumin/0.1 M NaNO(3)) system, acid-base titrations have been performed with conductometric and potentiometric titration. Measurement of the reactivity of cumin surface in the adsorption of Cu and Zn metal ions and determination of metal binding at different pH's were also carried out. To solve broad and ill-defined titration curves, a simplified version of nonideal competitive analysis (NICA) by Plette et al.) was applied. The results show that the sorption of the bivalent metal ions onto the whole surface of cumin could be attributed to a monodentate binding to one site mainly carboxylic-type site.     

On the Interaction of Two Finite-Dimensional Quantum Systems

Interaction of quantum system S ^a described by the generalised × eigenvalue equation A| _s =E _s S ^a | _s (s=1,...,) with quantum system S ^b described by the generalised n×n eigenvalue equation B| _i = _i S ^b | _i (i=1,...,n) is considered. With the system S ^a is associated -dimensional space X ^a and with the system S ^b is associated an n-dimensional space X _n ^b that is orthogonal to X ^a . Combined system S is described by the generalised (+n)×(+n) eigenvalue equation [A+B+V]| _k = _k [S ^a +S ^b +P]| _k (k=1,...,n+) where operators V and P represent interaction between those two systems. All operators are Hermitian, while operators S ^a ,S ^b and S=S ^a +S ^b +P are, in addition, positive definite. It is shown that each eigenvalue _{k i} of the combined system is the eigenvalue of the × eigenvalue equation . Operator in this equation is expressed in terms of the eigenvalues _i of the system S ^b and in terms of matrix elements _s |V| _i and _s |P| _i where vectors | _s form a base in X ^a . Eigenstate | _k ^a of this equation is the projection of the eigenstate | _k of the combined system on the space X ^a . Projection | _k ^b of | _k on the space X _n ^b is given by | _k ^b =( _k S ^b –B)^–1(V– _k P})| _k ^a where ( _k S ^b –B)^–1 is inverse of ( _k S ^b –B) in X _n ^b . Hence, if the solution to the system S ^b is known, one can obtain all eigenvalues _{k i} } and all the corresponding eigenstates | _k of the combined system as a solution of the above × eigenvalue equation that refers to the system S ^a alone. Slightly more complicated expressions are obtained for the eigenvalues _{k i} } and the corresponding eigenstates, provided such eigenvalues and eigenstates exist.     

Qualitative evaluation of aromatic herbs by direct headspace GC analysis. Applications of the method and comparison with the traditional analysis of essential oils

GC headspace analyses of various aromatizing herbs have been compared with those relating to the essential oils, obtained by steam distillation, of the same plants. In this way it was possible to establish the most significant differences between the composition of a herb flavor and that of its essential oil. In particular, we observed some very volatile compounds in the headspace samples which were absent from the essential oil; these components may make an important contribution to the herb flavor. The identification of these substances is still in progress.     

A Sensitive Spectrophotometric Determination of Nitrite in Water and Soil

A highly sensitive spectrophotometric method for the determination of nitrite in water and soil has been developed. The reaction of nitrite with acidified potassium iodide to liberate iodine which oxidizes leuco‐crystal violet (LCV) to form crystal violet having absorption maxima at 590 nm forms the bases of this method. In aqueous medium the system obeys Beer's law in the range of 0.1 to 1.0 μg per 25 mL (0.004–0.04 ppm), while in an extractive system the range is 0.025–0.25 μg in 100 mL (0.00025–0.0025 ppm). The molar absorptivity and Sandell's sensitivity were found to be 1.54 × 10⁶ 1 mol^?1 cm^?1 and 44 pg cm^?2, respectively.     

Variation of physicochemical properties in the aggregates of structual isomers

The regions of variation of density, enthalpy of formation, and detonation velocity of all of the formally possible structual isomers were determined for several molecular formulas of C,H,N,O-containing explosives. The histograms of the distribution of the structual isomers over these parameters were constructed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 859–862, May, 1995.The authors are grateful to Mrs. I. D. Solodukhina for the design of the graphical material.The work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 94-03-09323).     

Significance of Non-isothermal Kinetic Data. A statistical study

Arrhenius parameters values, in non-isothermal kinetic vaporisation processes for a series of compounds with related structures, have been calculated. This was made using a method of calculation that allows to find the most probable vaporisation mechanisms. According to this method DTG curves were compared with some theoretical ones reported in literature, whose shape results to be only a function of the mechanisms. In this way the choice of the mathematical functions which can be inserted in the kinetic equations, was influenced by the shape of the DTG plots and other thermal analysis signals thus allowing to choose the most probable mechanisms. The kinetic parameters derived from these mechanisms were compared, using statistical analysis, with those obtained from another method of calculation based on ‘a priori’ vaporisation mechanism chosen for the investigated liquid–gas transition. The standard deviations of the slope and of the intercept, together with the standard deviation and the square correlation coefficient (r ²) of the linear regression equations related to the mechanisms of the two methods were calculated. Student t-test, Fisher F-test, confidence intervals (c.i.) and residuals valueswere also given. Statistical analysis shows that the mechanisms obtained with the former method (diffusive and geometrical models) and the related Arrhenius parameters result to be more significant (in terms of probability) than the corresponding quantities of the latter for which a first-order model was chosen. This revised version was published online in August 2006 with corrections to the Cover Date.     

Ab initio studies on several species of the formula X3YO and X3YOH

Ab initio molecular orbital calculations using both minimal and extended basis sets have been applied to two isoelectronic sets of molecules. One set corresponds to the 18 electron species H₃NO, H₃CO^– and H₃COH while the second set contains the 42 electron fluorinated molecules F₃NO, F₃CO^– and F₃COH. The geometries of these molecules have been optimized, using both the minimal STO-3G and the extended 4-31G basis sets. These comparative calculations reveal that the 4-31G basis produced structural parameters in much better agreement with experiment. The effect of includingd-orbitals in the basis set was also investigated. For the fluorinated oxides it has been found that the optimized 4-31G structures were only slightly altered by the addition ofd-orbitals. For H₃NO, on the other hand, the inclusion ofd-orbitals considerably shortens the N-O bond distance. Both H₃NO and CF₃OH, which are unknown experimentally, are theoretically predicted to be capable of existence. The electronic structures of these molecules have also been examined using electronic partitioning according to the Mulliken scheme.     

Ab initio studies of the protonation of CO,N2 and NO+: Calculation of the minimum energy reaction paths

Ab initio molecular orbital calculations employing a 4-31G basis set have been used to study the minimum energy paths for the formation of HCO⁺, COH⁺, and HCOH²⁺ from CO by protonation. The protonation of N₂ to give NNH⁺ and HNNH²⁺ and of NO⁺ to form HNO²⁺ and NOH²⁺ have also been investigated. All species formed have linear equilibrium geometries and the minimum energy path for approach of the proton is along the line-of-centers of the heavy atoms. Energy barriers to the formation of the various species are given, where appropriate, and changes in geometry, ordering of molecular orbitals and orbital occupancy are discussed.     

Anomalies of the partition coefficient and properties of crystals in the region of low concentrations of an isomorphous admixture. 1. Unusual decomposition of solid solutions of the NaCl—CdCl2 system

Solid solutions NaCl—CdCl₂ were studied in an interval of CdCl₂ concentrations of 0.05—3 mol.% by Raman spectroscopy. The molecular form Na₂CdCl₄ decomposes: Na₂CdCl₄ 2Na⁺ + Cd²⁺ + 2Cl₂ ^– + 2e^–; 2Na + 2e^– 2Na⁰. Free sodium atoms form color centers of crystal (F centers) in the region of jumpwise changing the partition coefficient of CdCl₂ in NaCl (K jump).