Search results for "physical chemistry"
showing 10 items of 1199 documents
Wetting and phase separation at surfaces
2005
We study the problem ofsurfacedirected spinodal decomposition, viz., the dynamical interplay of wetting and phase separation at surfaces. In particular, we focus on the kinetics of wetting-layer growth in a semi-infinite geometry for arbitrary surface potentials and mixture compositions. We also present representative results for phase separation in confined geometries, e.g., cylindrical pores, thin films, etc.
Relation of Interdiffusion and Self-Diffusion in Polymer Mixtures
1986
From different assumptions one obtains linear relationships either between the interdiffusion coefficient and the self-diffusion coefficients or between the inverse interdiffusion coefficient and the inverse self-diffusion coefficients. The nature of these assumptions and possible experiments for discriminating between them are discussed.
Magnetic properties of six-coordinated high-spin cobalt(II) complexes: Theoretical background and its application
2008
Abstract In this contribution we study and analyse the influence of the different parameters involved in the magnetic susceptibility of six-coordinated high-spin Co(II) complexes. We propose an empirical expression to fit the magnetic susceptibility of polycrystalline samples of mononuclear Co(II) complexes with an axial distortion, the variable parameters being Δ (axial distortion), α (orbital reduction factor) and λ (spin–orbit coupling). This expression avoids solving the 12 × 12 matrix associated to the distortion of the 4 T 1g term. In order to take into account the magnetic coupling ( J ) in the polynuclear Co(II) complexes, a perturbational approach is proposed to describe their magn…
Pressure Effect on Spin Crossover in [Fe(phen)2(NCS)2] and [CrI2(depe)2]
2004
In the present article, we discuss the results of investigations of the influence of hydrostatic pressure (up to 1.2 GPa) on the spin transition behavior in [Fe(phen)2(NCS)2] polymorph II and [CrI2(depe)2]. It is demonstrated that pressure effect studies are very helpful in elucidating the mechanism of cooperative dynamic electronic structure phenomena accompanied by significant volume changes. Application of hydrostatic pressure serves as a tool for modifying the ligand field strength in a controlled manner.
Self-assembly in surfactant-based liquid mixtures: Octanoic acid/Bis(2-ethylhexyl)amine systems
2012
Abstract The physico-chemical properties of Bis(2-ethylhexyl)amine (BEEA) plus octanoic acid (OA) mixtures have been investigated by IR, SAXS, WAXS, viscosimetry, and AC complex impedance spectroscopy in the whole composition range. Mainly driven by proton transfer from the acidic OA to the basic BEEA, the formation of stoichiometrically well-defined adducts takes place in the mixtures. This causes the slowing down of molecular dynamics and the increase in charge carrier number density. Interestingly, while the pure components possess no significant conductivity (about 10−12 S cm−1 at 25 °C), their mixtures show a composition-dependent enhanced conductivity (up to about 10−5 S cm−1), i.e., …
Memory effects in functionalized conducting polymer films: titanocene derivatized polypyrrole in contact with THF solutions
2003
Abstract Films with a polypyrrole matrix and pendant titanocene dichloride centers, p(Tc3Py), have been obtained by potentiostatic electropolymerization of the titanocene-pyrrolyl derivative, Tc3Py=Tc(CH 2 ) 3 NC 4 H 4 (Tc=Cl 2 TiCpCp′, Cp=C 5 H 5 , Cp′=C 5 H 4 ), in acetonitrile (AN) solutions on a Pt surface. The redox activity has been studied after the transfer of the film-coated electrode into the monomer-free solution of the same electrolyte, TBAPF 6 , in THF. Contrary to the case of AN or dichloromethane solutions, one can achieve a stable redox activity of the immobilized Tc centers in THF solutions during a series of cycles. A parallel between the redox properties of the Tc complex…
Structural control of mixed ionic and electronic transport in conducting polymers
2016
Poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate), PEDOT:PSS, has been utilized for over two decades as a stable, solution-processable hole conductor. While its hole transport properties have been the subject of intense investigation, recent work has turned to PEDOT:PSS as a mixed ionic/electronic conductor in applications including bioelectronics, energy storage and management, and soft robotics. Conducting polymers can efficiently transport both holes and ions when sufficiently hydrated, however, little is known about the role of morphology on mixed conduction. Here, we show that bulk ionic and electronic mobilities are simultaneously affected by processing-induced change…
The odd association of a C3h trisamidinium cation and tosylate anion with a series of linear oxalate-bridged trinuclear heterometallic complexes
2013
A series of six isostructural heterometallic trinuclear oxalate-bridged complexes of the formula (TDbenz)(2)(TsO)(2)[M(II)(H(2)O)(2){(μ-ox)M(III)(ox)(2)}(2)]·6H(2)O·2CH(3)OH (TDbenz = 1,3,5-tris[2-(1,3-diazolinium)]benzene; TsO = 4-methylbenzenesulfonate; ox = oxalate; M(III) = Fe, M(II) = Mn (1), Fe (2), Co (3); M(III) = Cr, M(II) = Mn (4), Fe (5), Co (6)) have been synthesized from (NH(4))(3)[M(III)(ox)(3)]·3H(2)O, the chloride salts of the divalent metal ions and the tosylate salt of 1,3,5-tris[2-(1,3-diazolinium)]benzene (trisamidinium). Whereas the crystal structures of compounds 2, 3, 4 and 5 have been investigated by single-crystal X-ray diffraction, the structures of 1 and 6 have be…
A Two-State Computational Investigation of Methane C-H and Ethane C-C Oxidative Addition to [CpM(PH3)]n+ (M=Co, Rh, Ir;n=0, 1)
2006
Reductive elimination of methane from methyl hydride half-sandwich phosphane complexes of the Group 9 metals has been investigated by DFT calculations on the model system [CpM(PH(3))(CH(3))(H)] (M = Co, Rh, Ir). For each metal, the unsaturated product has a triplet ground state; thus, spin crossover occurs during the reaction. All relevant stationary points on the two potential energy surfaces (PES) and the minimum energy crossing point (MECP) were optimized. Spin crossover occurs very near the sigma-CH(4) complex local minimum for the Co system, whereas the heavier Rh and Ir systems remain in the singlet state until the CH(4) molecule is almost completely expelled from the metal coordinati…
Influence of the preparative route on the properties of WOx–ZrO2 catalysts: A detailed structural, spectroscopic, and catalytic study
2007
Abstract Two series of tungstated zirconia (WZ) solid acids covering a wide range of tungsten surface densities ( δ, W at/nm2 ) were prepared by nonconventional impregnation and coprecipitation routes, leading to samples with enhanced surface area ( ∼ 70 – 120 m 2 / g ) on annealing at 973–1073 K. The materials were thoroughly characterized by N2 physisorption , XRD, Raman, XPS, H 2-TPR, and DR UV–vis spectroscopy. The catalytic behavior of the Pt-promoted WZ catalysts (1 wt% Pt) was evaluated for the hydroconversion of n-hexadecane used as model feed representative of Fischer–Tropsch waxes. Both series of catalysts displayed a pronounced maximum in the reaction rate and a minimum in the se…