Thermodynamic and Kinetic Foundations of the Micellization Theory: 4. Kinetics of Establishment of Equilibrium in a Micellar Solution

A system of the kinetic equations of the material balance for the concentrations of surfactant monomers and micelles in a micellar nonionic surfactant solution was formulated. The equilibrium state of a materially isolated micellar solution was analyzed. The system of the kinetic equations of the material balance of a micellar solution was solved. The total time of the establishment of equilibrium in a micellar solution was determined. It was shown that this time increases or (typically) decreases with an increase in micelle concentration, depending on the degree of micellization.     

Thermodynamic Characteristics of Micellization in the Droplet Model of Surfactant Spherical Molecular Aggregate

The dependence of the work of the molecular aggregate formation on the aggregation number and surfactant monomer concentration in solution that has the key role for the theory of micellization was studied on the basis of a simple realistic droplet model of spherical aggregate composed of surfactant molecules (the o/w micelle type). Analytical formulas were derived for the coordinates of maximum and minimum of aggregate formation work on the aggregation number axis arising with an increase in the concentration of micellar solution. Model calculations of the thermodynamic characteristics of the kinetics of micellization were performed for premicellar and micellar regions of aggregate sizes within a wide range of solution concentration including the critical micellization concentration.     

Anisotropically Polarizable Dispersions. Basic Thermodynamic Equations and Kinetic Coefficients

Dispersion media formed by anisotropically polarizable particles suspended in nonconducting viscous fluid are considered. The particle anisotropy is set by a freezing-in unit vector; the particle shape is assumed to be close to spherical. A complete hydrodynamic model of such a medium is constructed. The expression for the free energy of a system is derived, and the laws governing the polarization of a dispersion medium and the relaxation of its anisotropy are revealed. The dependence of the effective viscosity of dispersion medium on the strength of an electric field during the flow in plane capillaries is determined.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 3, 2005, pp. 293–298.Original Russian Text Copyright © 2005 by Vasil’eva, Cherney.     

Thermodynamic Investigation of the Micellization and the Adsorption of Short Perfluoroalkylated Diols via Fluorescence Spectroscopy and Tensiometry

The micellization and adsorption of two short chain perfluorodiols 3,3,4,4,5,5,6,6,6-nonafluorohexane-1,2-diol (nFHD) and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1,2-diol (tFOD) are examined from a thermodynamic point of view as a function of temperature and methanol content. The microenvironment of the fluorinated aggregates is evaluated by the fluorescence probe method using pyrene and a molecular rotor 1,1-dicyano-4-p-dimethylaminophenyl)-1,3-butadiene (DMAPhC). The formation of micellar aggregates being evidenced, the results are discussed in terms of the polarity and of the cohesion behavior of the micellar aggregates by taking into account the methanol (MeOH) effect. The critical micellization concentrations thus determined are compared with those given by surface tension measurements. Micellar and adsorption thermodynamic parameters such as Gibbs free energies, enthalpies, and entropies are determined together with the surface areas. The results are compared with literature data and discussed. A model for describing the adsorption process of the fluorinated compounds upon the influence of methanol is finally proposed. Copyright 2001 Academic Press.     

Effect of Temperature on Micellization and Thermodynamic Behavior of Gadolinium Alkanoates in Nonaqueous Media

The conductometric measurements were employed to determine the critical micellar concentration (CMC), degree of dissociation and dissociation constant of dilute solutions of Gadolinium decanoate and dodecanoate in benzene and methanol mixture (7:3 v/v). The results show that the Gadolinium alkanoates behave as moderate electrolyte below the CMC. The various thermodynamic parameters were also evaluated for both dissociation and association process.     

ChemInform Abstract: Hydrodesulfurization of FeS+: Predominance of Kinetic over Thermodynamic Control.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Thermodynamic and Kinetic Origins of Au250 Nanocluster Electrochemiluminescence

Au clusters with protecting organothiolate ligands and core diameters less than 2 nm are molecule‐like structures, suitable for catalysis, optoelectronics and biology applications. The spectroscopy and electrochemistry of Au₂₅⁰ (Au₂₅[(SCH₂CH₂Ph)₁₈], SCH₂CH₂Ph=2‐phenylethanethiol) allowed us to construct a Latimer‐type diagram for the first time, which revealed a rich photoelectrochemistry of the cluster and the unique relationship to its various oxidation states and corresponding excited states. The occurrence of cluster electrochemiluminescence (ECL) was examined in the presence of tri‐n‐propylamine (TPrA) as a co‐reactant and was discovered to be in the near‐infrared (NIR) region with peak wavelengths of 860, 865, and 960 nm, emitted by Au₂₅^+*, Au₂₅^0*, and Au₂₅^?*, respectively. The light emissions, with an efficiency up to 103 % relative to that of the efficient Ru(bpy)₃²⁺/TPrA system, depended on the kinetics of the reactions between the electrogenerated TPrA radical and Au₂₅^z (z=2+, 1+, 1?, and 2?) in the vicinity of the electrode or the bulk Au₂₅⁰. These thermodynamic and kinetic origins were further explored by means of spooling ECL and photoluminescence spectroscopy during a sweep of the potential or at a constant potential applied to the working electrode. NIR‐ECL emissions of the cluster can be tuned in wavelength and intensity by adjusting the applied potential and TPrA concentration based on the above discoveries.     

Scientific Foundations of the Theory of Catalytic Processes and Reactors

The problems of the theory of heterogeneous catalysis are discussed based on mathematical modeling of catalytic reactions, processes, and reactors. The combination of actual and computational experiments are used to develop mathematical models. The role of mathematics and especially qualitative methods for the analysis of nonlinear mathematical models is discussed.     

Thermodynamic Theory of Equilibrium Copolymerization

General equations are derived for the thermodynamics of equilibrium copolymerization based on the diad model of copolymer. Physical interactions between components in solution are taken into consideration. Several special cases are treated in detail. When these physical interactions are absent, the relations obtained from the theory agree completely with those derived from the kinetics. Equilibrium monomer concentrations are illustrated as functions of excess free energy due to formation of heterodiad, equilibrium constants of homopolymerization, and initial monomer concentrations. It is shown that when the physical interactions are present, their effects cannot be ignored even in dilute solution. In bulk copolymerization, the physical interactions have a considerable effect on equilibrium, especially when the equilibrium monomer volume fractions are relatively small.     

The Thermodynamic Driving Force in the Kinetic Evaluation of Thermoanalytical Curves

This paper outlines the different ways of taking the distance from thermodynamic equilibrium into account in kinetic studies based on thermoanalytical experiments. The three main approaches are: (i) avoiding or neglecting the effect of the reverse reaction, (ii) describing the influence of distance from equilibrium on apparent kinetic parameters, and (iii) incorporating a driving force factor in the rate equation. Finally, the contradiction of the microscopic nature of the processes and the macroscopic character of the usual rate equation are briefly discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Enantioselective Supramolecular Carriers for Nucleoside Drugs. A Thermodynamic and Kinetic Gas Phase Investigation

The enantioselective interactions between chiral tetra-amidic receptors and nucleosides have been investigated by the ESI-IT-MS and ESI-FT-ICR-MS methodologies. Configurational effects on the CID fragmentation of diastereomeric [M ^H ₂ ?H?A]?⁺ aggregates (A?=?2'-deoxycytidine dC, citarabine (ara-C) were found to be mostly offset by isotope effect in [S ^X ₂ ?H?A]?⁺ (X?=?H, D) differently from the results obtained on the analogues (A?=?cytidine C and gemcitabine G). This result points the involvement of two different nucleoside/tetraamide isoforms. The structural differences of the [M ^H ₂ ?H?A]?⁺ (A?=?C and G) complexes vs. the [M ^H ₂ ?H?A]?⁺ (dC and ara-C) ones is fully confirmed by the kinetics of their uptake of the 2-aminobutane enantiomers, measured by FT-ICR mass spectrometry. Indeed, uptake of the 2-aminobutane enantiomers by [M ^H _n ?H?A]?⁺ (n?=?1,2; A?=?dC and ara-C) complexes is reversible, while that by [M ^H _n ?H?A]?⁺ (n?=?1,2; A?=?C and G) is not. The most encouraging result concerning the measured fragmentation and kinetic differences between C and ara-C, that are just epimers, indicates the possibility to subtly modulate the non-covalent drug/receptor interactions, through the electronic properties of the 2'-substituent on the nucleoside furanose ring, and furthermore on its three-dimensional position.     

Kinetic and Thermodynamic Characterization of Lysine Production Process in Brevibacterium lactofermentum

Detailed kinetic and thermodynamic parameters for lysine production from Brevibacterium lactofermentum are investigated for the first time in this study. Production of the essential amino acid, l-lysine, by B. lactofermentum was assessed in a flask and a continuously stirred tank fermentor (22 L). Maximum lysine production was achieved after 40 h of growth and at 35 °C. The effect of different nitrogen sources such as NH₄NO₃, (NH₄)₂SO₄, (NH₄)₂HPO₄, corn steep liquor, NaNO₃, and urea showed that corn steep liquor gave a better lysine yield. Lysine production was increased when dissolved oxygen was maintained at 50 % saturation. The use of dissolved oxygen was critical for high productivity. This indicates that dissolved oxygen greatly affects l-lysine productivity. Kinetic and thermodynamic parameters during lysine production from molasses and glucose mixture showed that B. lactofermentum efficiently converted the substrate mixture into cell mass and lysine. Kinetic and thermodynamic parameters were significantly higher compared with other microorganisms which may be due to the high metabolic activity of B. lactofermentum. This study will have a significant impact on future strategies for lysine production at industrial scale.     

Micellization and Thermodynamic Parameters of Butanediyl-1,4-bis(tetradecyldimethylammonium Bromide) Gemini Surfactant at Different Temperatures: Effect of the Addition of 2-Methoxyethanol

The effect of the addition of 2-methoxyethanol on the critical micelle concentration (cmc) and on the degree of counterion dissociation (??) of butanediyl-1,4-bis(tetradecyldimethylammonium bromide) gemini surfactant, [C₁₄H₂₉N⁺(CH₃)₂?C(CH₂)₄?CN⁺(CH₃)₂C₁₄H₂₉,2Br^?] (referred as 14?C4?C14,2Br^?), has been studied by varying the compositions of the 2-methoxyethanol + water mixed solvent media (0 to 50?%). To determine various thermodynamic parameters of micellization, on the basis of the mass?Caction model for micelle formation, the experiments were performed at selected compositions of the mixed solvent at four temperatures ranging between 25?°C and 50?°C. Furthermore, the air/bulk surface tensions of the pure and mixed media were determined, and a successful attempt was made to correlate the cohesive energy density described through the Gordon parameter with the values of Gibbs energy of micellization.     

Molecular,Thermodynamic, and Kinetic Parameters of Chloromethanes and Chloromethyl Radicals: Ab Initio Calculations

Wave functions and enthalpies of formation of the ground states of chloromethanes CH_{4 - x} Cl _x and chloromethyl radicals CH_{3 - x} Cl _x (x = 1, 2, and 3) were calculated ab initio with inclusion of electron correlations. The geometry of these molecules, frequencies of normal modes, and other parameters were found and used for calculation of thermodynamic functions in the range 0-1500 K. The CH_{4 - x} Cl _x CH_{4 - x} Cl> _{- 1 x} + Cl and CH_{4 - x} Cl _x CH_{3 - x} Cl _x + H equilibrium constants were calculated from the thermodynamic functions and then used to obtain the corresponding dissociation rate constants within the limits of high concentrations.     

Structure and Reactivity of Uracil Derivatives. Thermodynamic Stability of 5-Diazouracil

The equilibrium position in the electrocyclization of certain model diazo compounds has been calculated using ab initio calculations based on RHF/6-31G with full optimization of the geometry. It was shown that on reducing the NN bond length the position of equilibrium is displaced towards the acyclic isomer. This effect is expressed to the greatest extent in -diazocarbonyl systems to which 5-diazouracil derivatives belong. An unusual polarized electron distribution was apparent for 5-diazouracil itself, which does not correspond with the classical Lewis structure.     

Bingel–Hirsch Addition on Endohedral Metallofullerenes: Kinetic Versus Thermodynamic Control

An extensive theoretical study of the Bingel–Hirsch addition of bromomalonate on scandium nitride endohedral fullerenes has been carried out. The prototypical and highly symmetrical Sc₃N@I_h‐C₈₀, with a structure that satisfies the isolated pentagon rule (IPR), and the non‐IPR Sc₃N@D₃(6140)‐C₆₈ fullerene show analogous reaction paths despite the distinct topology of the carbon networks and different rotation freedom of the internal nitride cluster. For the two metallofullerenes, our results predict that the reaction takes place under kinetic control yielding open‐cage fulleroids on [6,6] bonds, which is in good agreement with experimental data. The theoretical studies also show that predicting the reactivity of endohedral metallofullerenes is not straightforward and often an accurate analysis of the potential energy surface is required.