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151.
152.
半胱氨酸在碳钢与硫酸界面的缓蚀行为 总被引:2,自引:1,他引:1
OZCAN Muzaffer KARADAGG Faruk DEHRII Ilyas 《物理化学学报》2008,24(8):1387-1392
Interfacial behavior of cysteine (Cys) between mild steel and sulfuric acid solution as a corrosion inhibitor has been studied with electrochemical AC (alternating current) and DC (direct current) techniques at (25.0±0.1) ℃. The AC impedance results were evaluated using equivalent circuits in which a constant phase element (CPE) has been replaced with double layer capacitance (Cdl) to represent the frequency distribution of experimental data. Changes in impedance parameters (charge transfer resistance and double layer capacitance) indicated that cysteine molecules acted by accumulating at the metal/solution interface. The fractional coverage of the metal surface (θ) was determined using AC impedance results and it was found that the adsorption of cysteine on the mild steel surface followed a Langmuir isothermmodel with a standard free energy of adsorption (⊿G0ads) of -35.1 kJ·mol-1. To clarify the type of interaction between mild steel surface and cysteine molecules with a molecular orbital approach, electronic properties, such as, the highest occupied molecular orbital (HOMO) energy, the lowest unoccupied molecular orbital (LUMO) energy, and the frontier molecular orbital coefficients have been calculated. Energy gaps for the interaction of mild steel surface and cysteine molecules (ELUMOFe-EHOMOCys and ELUMOCys-EHOMOFe) were used to determine whether cysteine molecules acted as electron donors or electron acceptors when they interacted with the mild steel surface. The local reactivity was evaluated through the condensed Fukui indices. Theoretical calculations were carried out using the density functional theory (DFT) at B3LYP level with the 6-311++G(d,p) basis set for all atoms by Gaussian 03W program. 相似文献
153.
154.
Nascimento V Alberto EE Tondo DW Dambrowski D Detty MR Nome F Braga AL 《Journal of the American Chemical Society》2012,134(1):138-141
The reaction mechanism of the GPx-like oxidation of PhSH with H(2)O(2) catalyzed by selenoxides proceeds via formation of the hydroxy perhydroxy selenane, which is a stronger oxidizing agent than selenoxide. A hydroxy perhydroxy selenane intermediate was observed by electrospray ionization mass spectrometry and (77)Se NMR spectroscopy in reactions of selenoxide 8 with H(2)O(2).The initial velocity of oxidation of PhSH by H(2)O(2) with selenoxide 8 is 4 orders of magnitude higher than that of 8 without peroxide. Selenoxide 8 is not reduced to selenide 6 by PhSH in the presence of H(2)O(2). While electronic substituent effects have minimal impact on the catalytic performance of selenoxides, chelating groups increase the rate of catalysis. 相似文献
155.
Theoretical study of the importance of the spectator groups on the hydrolysis of phosphate triesters
The spontaneous hydrolysis of a series of five triaryl and two dialkyl aryl phosphate triesters, previously studied experimentally, is examined theoretically using two different hybrid density functional methods, B3LYP and M06; two basic sets, 6-31+G(d) and 6-311++G(d,p); and the Gaussian 09 program. The B3LYP/6-31+G(d) methodology combined excellent accuracy with minor computational cost. The calculations show excellent quantitative agreement with experiment, which is best in the presence of three discrete water molecules. The results support a two-step mechanism involving a pentacovalent addition intermediate, with a lifetime of tenths of a millisecond. The rate-determining formation of this intermediate involves general base catalysis, defined by concerted proton transfers in a six-membered cyclic activated complex (TS1), which involves two hydrogen-bonded water molecules supporting a well-developed H(2)O···P bond (mean % evolution 77.83 ± 0.97). The third water molecule is hydrogen-bonded to P═O and subsequently involved in product formation via TS2. The effects on reactivity of all the groups attached to phosphorus in TS1 are examined in detail: the two non-leaving groups in particular are found to play an important role, accounting for the substantial difference in reactivity between triaryl and dialkyl aryl phosphate triesters. 相似文献
156.
Fritzen MB Souza AJ Silva TA Souza L Nome RA Fiedler HD Nome F 《Journal of colloid and interface science》2006,296(2):465-471
The adsorption isotherms of Cr(VI) on kaolinite, montmorillonite, and alumina were adequately treated with Langmuir model showing behavior characteristic of single-layer adsorption. The efficiency of the adsorbents in removing Cr(VI) from water follows the order alumina > kaolinite > montmorillonite > silica. Speciation studies indicate that hydrogen chromate ions were the major adsorbed species and simultaneous adsorption of dichromate ion occurred at concentrations greater than approximately 10(-3) mol L(-1). It is most probable that the mechanism of adsorption of the hydrogen chromate ion at the surface of alumina is predominantly electrostatic adsorption, with outer sphere complex formation. 相似文献
157.
Shaval Mamedov Vilayet Alekperov Nursel Can Faruk Aras Gunes Yilmaz 《Macromolecular Symposia》2004,212(1):293-298
Degradation under the simultaneous effects of mechanical stress and temperature in polyolefins (PE, PP), composites on their basis (PE+PP fibre, PP+PP fibre, PP+glass fibre) and radiation low-density polyethylene (X-LDPE) used in high-voltage cables obeys the thermofluctuation theory of Zhourkov (in certain σ and τ0 intervals) based on the theory of Arrhenius is presented in the following form: τσ = τ0 exp[(U0 − γσ)/ RT] (1) where τ is durability. τ0 is a constant (10−12-10−13s) equal to period of vibrations of atoms around equilibrium position, U0 is the activation energy of the mechanical destruction process (at σ = 0), γ is a structure-sensitive parameter, T is absolute temperature and R is universal gas constant. Electric degradation under the effects of electric field and temperature in the materials mentioned above obeys the equation: τE = τ0 exp[(W0 − χE)/ RT] (2) Here, τE, W0 and χ are analogous to τσ, U0 and γ, respectively. It is assumed that the following equation is valid under the simultaneous effects of E, σ and T: τσ,E = τ0 exp[(U0 − (γσ + χE))/ RT]. (3) electric degradation 相似文献
158.
Assuming , we show that generalized eventually narrow sequences on a strongly inaccessible cardinal κ are preserved under a one step iteration of the Hechler forcing for adding a dominating κ-real. Moreover, we show that if κ is strongly unfoldable, and λ is a regular cardinal such that , then there is a set generic extension in which . 相似文献