Search results for "THERMODYNAMICS"
showing 10 items of 2774 documents
Basic Notions of the Theory of Heat
2016
This chapter summarizes some basic notions of thermodynamics and defines the empirical variables which are needed for the description of thermodynamic systems in equilibrium. Empirical temperature and several scales used to measure temperature are defined. The so-called “zeroth law of thermodynamics” is formulated which says that systems which are in mutual equilibrium have the same temperature. Thermodynamic ensembles corresponding to different macroscopic boundary conditions are introduced and are illustrated by simple models such as the ideal gas. Also, entropy appears on the scene for a first time, both in its statistical and its thermodynamical interpretation. Gibb’s fundamental form i…
Rate Theory for Electrocatalytic Systems: Fixed Potential Formulation for General, Electron Transfer, and Proton-Coupled Electron Transfer Reactions
2019
Atomistic modeling of electrocatalytic reactions is most naturally conducted within the grand canonical ensemble (GCE) which enables fixed chemical potential calculations. While GCE has been widely adopted for modeling electrochemical and electrocatalytic thermodynamics, the electrochemical reaction rate theory within GCE is lacking. Molecular and condensed phase rate theories are formulated within microcanonical and canonical ensembles, respectively, but electrocatalytic systems described within the GCE require extension of the conventionally used rate theories for computation reaction rates at fixed electrode potentials. In this work, rate theories from (micro) canonical ensemble are gene…
Unified Rate Theory of Electrochemistry and Electrocatalysis: Fixed Potential Formulation for General, Electron Transfer, and Proton-Coupled Electron…
2019
Atomistic modeling of electrocatalytic reactions is most naturally conducted within the grand canonical ensemble (GCE) which enables fixed chemical potential calculations. While GCE has been widely adopted for modeling electrochemical and electrocatalytic thermodynamics, the electrochemical reaction rate theory within GCE is lacking. Molecular and condensed phase rate theories are formulated within microcanonical and canonical ensembles, respectively, but electrocatalytic systems described within the GCE require extension of the conventionally used rate theories for computation reaction rates at fixed electrode potentials. In this work, rate theories from (micro)canonical ensemble are gener…
Influence of Component Temperature Derivation from Dual Angle Thermal Infrared Observations on TSEB Flux Estimates Over an Irrigated Vineyard
2015
A two-source model for deriving surface energy fluxes and their soil and canopy components was evaluated using multi-angle airborne observations. In the original formulation (TSEB1), a single temperature observation, Priestley–Taylor parameterization and the vegetation fraction are used to derive the component fluxes. When temperature observations are made from different angles, soil and canopy temperatures can be extracted directly. Two dual angle model versions are compared versus TSEB1: one incorporating the Priestley–Taylor parameterization (TSEB2I) and one using the component temperatures directly (TSEB2D), for which data from airborne campaigns over an agricultural area in Spain are u…
Effects of temperature and pressure on microcantilever resonance response.
2003
Abstract The variation in resonance response of microcantilevers was investigated as a function of pressure (10 −2 –10 6 Pa) and temperature (290–390 K) in atmospheres of helium (He) and dry nitrogen (N 2 ). Our results for a silicon cantilever under vacuum show that the frequency varies in direct proportion to the temperature. The linear response is explained by the decrease in Young's modulus with increasing the temperature. However, when the cantilever is bimaterial, the response is nonlinear due to differential thermal expansion. Resonance response as a function of pressure shows three different regions, which correspond to molecular flow regime, transition regime, and viscous regime. …
Dynamic thermal expansivity near the glass transition
2000
Dielectric techniques were used to investigate the thermal expansivity of polystyrene films. Capacitive scanning dilatometry (CSD) employs temperature ramping in order to monitor the non-linear structural relaxation in the glass transformation range and to quantify liquid fragility. In the linear response regime, the complex thermal expansivity is obtained as a function of the temperature cycling frequency and is observed to reflect the structural relaxation.
Pore Size Analysis of MCM-41 Type Adsorbents by Means of Nitrogen and Argon Adsorption
1998
Methods of nonlocal density functional theory (NLDFT), proposed recently for predictions of adsorption equilibrium and calculations of pore size distributions in micro- and mesoporous materials, were tested on reference MCM-41 materials. Five newly synthesized MCM-41 adsorbents with presumably uniform pore channels varying from 32 to 45 Å were characterized by X-ray diffraction (XRD), nitrogen adsorption at 77 K, and argon adsorption at 77 and 87 K. New sets of intermolecular interaction parameters of the NLDFT model for N2 and Ar adsorption on MCM-41 were determined. The parameters were specified to reproduce the bulk liquid-gas equilibrium densities and pressures, liquid-gas interfacial t…
Dimensional analysis and upscaling of two-phase flow in porous media with piecewise constant heterogeneities
2004
Dimensional analysis of the traditional equations of motion for two-phase flow in porous media allows to quantify the influence of heterogeneities. The heterogeneities are represented by position dependent capillary entry pressures and position dependent permeabilities. Dimensionless groups quantifying the influence of random heterogeneities are identified. For the case of heterogeneities with piecewise constant constitutive parameters (e.g., permeabilities, capillary pressures) we find that the upscaling ratio defined as the ratio of system size and the scale at which the constitutive parameters are known has to be smaller than the fluctuation strength of the heterogeneities defined, e.g.,…
Phase diagram of polymer blends in confined geometry
2001
Within self-consistent field theory we study the phase behavior of a symmetrical binary AB polymer blend confined into a thin film. The film surfaces interact with the monomers via short range potentials. One surface attracts the A component and the corresponding smei-infinite system exhibits a first order wetting transition. The surface interaction of the opposite surface is varied as to study the crossover from capillary condensation for symmetric surfaces fields to the interface localization/delocalization transition for antisymmetric surface fields. In the former case the phase diagram has a single critical point close to the bulk critical point. In the latter case the phase diagram exh…
PHASE EQUILIBRIA IN THIN POLYMER FILMS
2001
Within self-consistent field theory and Monte Carlo simulations the phase behavior of a symmetrical binary AB polymer blend confined into a thin film is studied. The film surfaces interact with the monomers via short ranged potentials. One surface attracts the A component and the corresponding semi-infinite system exhibits a first order wetting transition. The surface interaction of the opposite surface is varied as to study the crossover from capillary condensation for symmetric surface fields to interface localization/delocalization transition for antisymmetric surface fields. In the former case the phase diagram has a single critical point close to the bulk critical point. In the latter…