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.     

On the Theory of Micellization Kinetics

Summary: We consider certain general features of aggre‐ gation (micellization) processes in solutions of amphiphilic molecules, in particular, block‐copolymers. We demonstrate that non‐equilibrium effects can be very important for micellization. In particular, we show that micelle formation at the conventional (equilibrium) critical micelle concentration (CMC, ) can be inhibited by high activation energy barriers. This is likely to be the case when the micelles are large. In this case an aggregation actually occurs at higher concentrations, above an apparent CMC, . The concentration can be much higher than the equilibrium CMC. Hence significant hysteresis effects are inherent in amphiphilic systems since micelle formation and dissociation are activation processes. To further clarify this idea we consider relaxation of a micellar system after a temperature jump (or a jump of another essential parameter) and discuss qualitatively different relaxation times corresponding to the relaxations of the micellar sizes and of the total number of micelles. We also discuss different kinetic pathways of micelle formation and relaxation and show that in certain cases the ideal‐gas (combinatorial) contribution to the micelle free energy is significant for the kinetics.

Micelle association and dissociation times vs. reduced concentration.     

Effects of Aspartic Acid and Lysine on Thermodynamic Functions of SDS Micellization

Aspartic acid and lysine can promote SDS micellization. The critical micellar concentration of SDS decreases with amino acid concentration, but first does and then increases with temperature. In SDS micellization, the change of standard Gibbs free energy is negative in SDS/H₂O system with or without amino acid. With the increase of amino acid concentration, the changes of mole standard Gibbs free energy and enthalpy decrease, but the change of the system's entropy increases. The effect of lysine is more than that of aspartic acid on the thermodynamic functions.     

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 and Kinetic Polymerizability of Cyclic Esters

Recent advances in the controlled ring-opening polymerization (ROP) of cyclic aliphatic esters are reviewed with a particular attention to thermodynamics and kinetics of the polymerization of industrially important monomers, namely: lactide (LA), 1,4-dioxan-2-one (DX), and ϵ-caprolactone (CL). For comparison, polymerization of β-lactones is discussed. Progress in stereocontrolled polymerization of monomers bearing centers of chirality [LA and β-butyrolactone (BL)] is also briefly reviewed.     

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.     

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.     

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.     

Reduction of Methylene Green by EDTA:Kinetic and Thermodynamic Aspects

The reduction of methylene green (MG) into protonated leuco dye with ethylenediamine tetraacetic acid (EDTA) in aqueous alkaline medium was studied spectrophotometrically at λ_max 660 nm. EDTA behaved as an effective electron donor during the reduction of MG in an aerobic condition. Consumption of EDTA in the reduction of MG means that it is oxidized. This is an unexpected result since EDTA does not normally function as a reducing agent. The nitrogen-containing chelating agents with secondary or tertiary nitrogen behaved as an electron donor in photochemical reaction of dye. The rate of reduction depends upon pH in the same way as the base titration of EDTA. Effects of salt and temperature have been investigated for the reduction process. The salting agent KNO₃ has been found to uniquely enhance the rate of reduction of MG by EDTA in the aerobic condition. Detailed kinetic and thermodynamic aspects have been discussed to realize the interaction between MG and EDTA. Kinetic studies revealed that reaction was sensitive and regeneration of oxidized form of the dye was observed. Reversible first order reaction kinetics with respect to EDTA, MG and NaOH was found.     

非线性色谱的非平衡热力学分离理论 Ⅱ. 非线性-传质动力学过程的0-1模型

在制备色谱的优化设计和控制过程中,若试图把基于偏微分方程(PDE)-Eulerian描述的Wilson色谱理论框架和基于离散时间状态的优化控制方法(如Markov决策过程(MDP)和模型预测控制(MPC)等)衔接在一起时,就会出现明显的障碍。本文提出基于Lagrangian-Eulerian描述(L-ED)的非线性传质色谱(NTC)的0-1模型来克服这些障碍。该模型把一个溶质微元单元划分为在流动相中并以其线速度移动的流动相溶质微元(SCm)和在固定相中其移动速度为0的固定相溶质微元(SCs)。引入由溶质微元的序号集合、溶质微元的位置矢量、固定相溶质浓度矢量和流动相溶质浓度矢量组成的热力学状态矢量Sk，并用其来描述色谱过程的局域热力学路径(LTP)和宏观热力学路径(MTP)。在非线性-理想-传质色谱的理论分析和数值实验中,0-1模型的数值解表现出很好的一致性、稳定性、守恒性及精确性等。该模型能很好地与控制论中的Markov决策过程或其他基于离散时间状态的优化控制方法相衔接。     

Thermodynamic Analysis of the Adsorption and Micellization Activity of the Mixtures of Rhamnolipid and Surfactin with Triton X-165

The surface tension of aqueous solutions of Triton X-165 with rhamnolipid or surfactin mixtures was measured. The obtained results were applied for the determination of the concentration and composition of the Triton X-165 and biosurfactants mixture at the water–air interface as well as the contribution of the particular component of the mixtures to water surface tension reduction and the mutual influence of these components on the critical micelle concentration. The determination of these quantities was based on both the commonly used concepts and a new one proposed by us, which assumes that the composition of the mixed monolayer at the water–air interface depends directly on the pressure of the monolayer of the single mixture component and allows us to determine the surface concentration of each mixture component independently of surface tension isotherms shape. Taking into account the composition of the mixed monolayer at the water–air interface, the standard Gibbs adsorption free energy was considered. The obtained results allow us to state that the concentration of both mixture components corresponding to their saturated monolayer and the surface tension of their aqueous solution can be predicted using the surfactants’ single monolayer pressure and their mole fraction in the mixed monolayer determined in the proposed way.     

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.     

Manipulation of Organic Afterglow by Thermodynamic and Kinetic Control

The fabrication of room-temperature organic phosphorescence and afterglow materials, as well as the transformation of their photophysical properties, has emerged as an important topic in the research field of luminescent materials. Here, we report the establishment of energy landscapes in dopant-matrix organic afterglow systems where the aggregation states of luminescent dopants can be controlled by doping concentrations in the matrices and the methods of preparing the materials. Through manipulation by thermodynamic and kinetic control, dopant-matrix afterglow materials with different aggregation states and diverse afterglow properties can be obtained. The conversion from metastable aggregation state to thermodynamic stable aggregation state of the dopant-matrix afterglow materials to leads to the emergence of intriguing afterglow transformation behavior triggered by thermal and solvent annealing. The thermodynamically unfavorable reversible afterglow transformation process can also be achieved by coupling the dopant-matrix afterglow system to mechanical forces.     

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.     

尾链含对硝基苯醚基团的阳离子Gemini表面活性剂的胶束化热力学

利用等温滴定微量量热法和电导法研究了具有不同疏水链长并且疏水链尾部含有对硝基苯醚基团的Gemini表面活性剂胶束化过程的热力学, 分别利用相分离模型和质量作用模型对观察焓与浓度的关系曲线进行拟合, 获得了胶束化过程的热力学参数. 两种模型获得的胶束化焓一致, 均为较大负值, 而吉布斯自由能却相差较大. 用相分离模型得到的胶束化过程的热容变化均为负值, 并随链长增加绝对值增大, 胶束化过程总的热容变化主要来自非极性的烷基链去水合产生的热容变化, 证明处于疏水链末端的对硝基苯醚基团在表面活性剂形成胶束后依然与水相接触. 质量作用模型获得的胶束聚集数随疏水链长增加逐渐下降, 这是由具有长疏水链的表面活性剂形成预胶束所导致.     

Revising Complex Supramolecular Polymerization under Kinetic and Thermodynamic Control

Pathway complexity, hierarchical organization, out of equilibrium, and metastable or kinetically trapped species are common terms widely used in recent, high‐quality publications in the field of supramolecular polymers. Often, the terminologies used to describe the different self‐assembly pathways, the species involved, as well as their relationship and relative stability are not trivial. Different terms and classifications are commonly found in the literature, however, in many cases, without clear definitions or guidelines on how to use them and how to determine them experimentally. The aim of this Minireview is to classify, differentiate, and correlate the existing concepts with the help of recent literature reports to provide the reader with a general insight into thermodynamic and kinetic aspects of complex supramolecular polymerization processes. A good comprehension of these terms and concepts should contribute to the development of new complex, functional materials.     

次甲基硅SiH与HF反应的热力学及动力学性质研究

在量子化学对SiH与HF反应计算的基础上,运用统计热力学和Wigner校正的Eyring过渡态理论计算了该反应在200～2000K温度范围内的热力学函数、平衡常数、频率因子A和速率常数随温度的变化。计算结果表明该反应在低温下具有热力学优势,而在高温下具有动力学优势。该反应在研究的温度范围内是一放热、熵减少的反应,反应的速率常数随温度的升高而增大,且服从Arrhenius定律。     

Kinetic and Thermodynamic Control in Self-Assembly: Sequential Formation of Linear and Circular Helicates

NMR and MS analysis as a function of time has shown that the self-assembly of a linear ligand with Fe²⁺ or Ni²⁺, metal ions of octahedral coordination geometry, generates first a triple helicate and thereafter the circular helicate 1 as kinetic and thermodynamic products, respectively. The results provide insight into features of the energy hypersurface on which this self-assembly operates and point to the general role of kinetic and thermodynamic control in such processes.