Search results for "physical chemistry"
showing 10 items of 1199 documents
Sorption Kinetics of Xenon on MFI-Type Zeolite Molecular Sieves
1990
Kinetic uptake data for xenon adsorbed onto large and uniform silicalite-I crystals are presented over a temperature range of 121 K to 296 K. — Adsorption isotherms and corrected diffusion coefficients derived from the uptake curves are given. The heat of adsorption and activation energy of diffusion were estimated from the plots of reciprocal temperature against the logarithm of equilibrium pressure and corrected diffusion coefficients, respectively. — While the corrected diffusion coefficient is independent of coverage for the higher temperatures, it decreases significantly at the lower temperatures investigated (<170 K) when the limiting adsorption capacity has been reached. — Comparing …
Thermodynamic properties of alcohols in a micellar phase. Binding constants and partial molar volumes of pentanol in sodium dodecylsulfate micelles a…
1984
Densities of the ternary system water-sodium dodecylsulfate (NaDS)-pentanol and of the binary systems butanol-octane and pentanol-octane were measured at 15, 25, and 35 °C. The apparent molar volume of pentanol in the ternary system was analyzed using a mass-action model for the alcohol distribution in micellar solutions. The partial molar volume of alcohol bound to the micelles and the ratio between the binding constant and the aggregation number of the surfactant are calculated. The partial molar volume binding constant, is discussed in terms of solubilization sites of the alcohol in the micelles whereas the binding constant is compared with that derived from the Nernstian partition const…
Dual emission of a bis(pyrene)-functionalized, perbenzylated beta-cyclodextrin
2008
A bis(pyrene)-functionalized β-cyclodextrin (1) has been prepared in two steps from perbenzylated β-cyclodextrin. This compound shows dual emission properties, which arise from the pyrenyl chromophores. Upon excitation of 1 at 355 nm, monomer blue fluorescence (386, 407 and 428 nm) is observed in DMSO solution, whereas excimer green fluorescence (477 nm) is seen upon addition of ≥20 vol% water in DMSO. This suggests that modified β-cyclodextrin 1 changes its shape in response to the environment. The sensing properties of 1 towards carboxylic acids and alcohols were investigated in H2O–DMSO (80 : 20 v/v). Monomer fluorescence is restored selectively by medium length normal carboxylic acids, …
Isomerization of C5–C7 n-alkanes on unidirectional large pore zeolites: activity, selectivity and adsorption features
2001
Abstract The hydroisomerization–hydrocracking of nC5–nC7 is studied with a 12MR unidirectional zeolite (ITQ-4). Selectivity and kinetic parameters indicate that differences in pore topology are more important than acidity for determining isomerization selectivity. The adsorption of the paraffins is determined by van der Waals interactions.
Electronic excitations of 1,4-disilyl-substituted 1,4-disilabicycloalkanes: a MS-CASPT2 study of the influence of cage size.
2007
We present a multistate complete active space second-order perturbation theory computational study aimed to predict the low-lying electronic excitations of four compounds that can be viewed as two disilane units connected through alkane bridges in a bicyclic cage. The analysis has focused on 1,4-disilyl-1,4-disilabicyclo[2.2.1]heptane (1a), 1,4-bis(trimethylsilyl)-1,4-disilabicyclo[2.2.1]heptane (1b), 1,4-disilyl-1,4-disilabicyclo[2.1.1]hexane (2a), and 1,4-bis(trimethylsilyl)-1,4-disilabicyclo[2.1.1]hexane (2b). The aim has been to find out the nature of the lowest excitations with significant oscillator strengths and to investigate how the cage size affects the excitation energies and the…
Theoretical characterization of iron and manganese porphyrins for catalyzed saturated alkane hydroxylations
1997
Abstract The theoretical characterization of porphin (H2Por), iron and manganese porphyrins MIII(Por) and their chlorine derivatives MIII(Por)Cl has been carried out. This work represents a first step for modelling catalyzed saturated alkane hydroxylations. The chlorine atom is responsible for the existence of a dipole moment of 1.2–2.0 D in the MIII(Por)Cl molecules and for a negative value of the mean quadrupole moment (−16–(−14)DA). The charge of the metal atom (1.8–2.2 e) is rather varied (to 2.1–2.6 e) and the effective polarizability (2.8–2.9 A3) is increased (to 3.5–3.6 A3) by the addition of the chlorine atom. Starting from the porphin molecule, the presence of the metal atom decrea…
Static and Dynamic Properties of a n-C100H202 Melt from Molecular Dynamics Simulations
1997
We present in this work results from atomistic molecular dynamics simulations of a n-C100H202 melt. This work represents a first effort to simulate a fully equilibrated ensemble of chains of suffic...
From C–S–H to C–A–S–H: Experimental study and thermodynamic modelling
2015
Abstract It has long been known that the stoichiometry of C–S–H varies with the calcium hydroxide concentration in solution. However, this issue is still far from understood. We revisit it in both experimental and modelling aspects. A careful analysis of the solubility confirms the existence of three different C–S–H phases, defined as Ca 4 H 4 Si 5 O 16 , Ca 2 H 2 Si 2 O 7 and Ca 6 (HSi 2 O 7 ) 2 (OH) 2 , respectively. The variation of the Ca/Si ratio of the three phases has been described by surface reactions: the increase of the Si content is accounted for by silicate bridging, the increase of calcium content and the surface charge are accounted for by reactions involving silanol groups v…
ENANTIOSELECTIVE REDUCTION OF PROCHIRAL KETONES PROMOTED BY AMINO AMIDE RUTHENIUM COMPLEXES: A DFT STUDY
2021
International audience; The origin of enantioselectivity in the reaction of chiral Ru amino amide complexes in the asymmetric transfer hydrogenation of acetophenone was investigated using DFT calculations. For the most stable active catalysts, the full free energy profiles for the reaction were calculated according to the concerted hydrogen transfer mechanism. We succeeded in reproducing the experimentally observed enantioselectivity for the studied Ru amino amide complexes. Our results indicate that the high enantioselectivity can be explained by a stabilizing CH-π interaction existing between the phenyl group of acetophenone and the aromatic substituent of the catalyst, which plays a sign…