Volume macroscopic

To define the thennodynamic state of a system one must specify fhe values of a minimum number of variables, enough to reproduce the system with all its macroscopic properties. If special forces (surface effecls, external fields—electric, magnetic, gravitational, etc) are absent, or if the bulk properties are insensitive to these forces, e.g. the weak terrestrial magnetic field, it ordinarily suffices—for a one-component system—to specify fliree variables, e.g. fhe femperature T, the pressure p and the number of moles n, or an equivalent set. For example, if the volume of a surface layer is negligible in comparison with the total volume, surface effects usually contribute negligibly to bulk thennodynamic properties. 

The total change d.S can be detennined, as has been seen, by driving the subsystem a back to its initial state, but the separation into dj.S and dj S is sometimes ambiguous. Any statistical mechanical interpretation of the second law requires that, at least for any volume element of macroscopic size, dj.S > 0. However, the total... 

In equilibrium statistical mechanics, one is concerned with the thennodynamic and other macroscopic properties of matter. The aim is to derive these properties from the laws of molecular dynamics and thus create a link between microscopic molecular motion and thennodynamic behaviour. A typical macroscopic system is composed of a large number A of molecules occupying a volume V which is large compared to that occupied by a molecule ... 

Then F( ) = S(/ -t d )- 2( ), and the density of states D E) = dS/d/ . A system containing a large number of particles N, or an indefinite number of particles but with a macroscopic size volume V, normally has the number of states S, which approaches asymptotically to... 

Relationships from thennodynamics provide other views of pressure as a macroscopic state variable. Pressure, temperature, volume and/or composition often are the controllable independent variables used to constrain equilibrium states of chemical or physical systems. For fluids that do not support shears, the pressure, P, at any point in the system is the same in all directions and, when gravity or other accelerations can be neglected, is constant tliroughout the system. That is, the equilibrium state of the system is subject to a hydrostatic pressure. The fiindamental differential equations of thennodynamics ... 

G. Ramachandran and T. Schlick. Beyond optimization Simulating the dynamics of supercoiled DNA by a macroscopic model. In P. M. Pardalos, D. Shal-loway, and G. Xue, editors. Global Minimization of Nonconvex Energy Functions Molecular Conformation and Protein Folding, volume 23 of DIM ACS Series in Discrete Mathematics and Theoretical Computer Science, pages 215-231, Providence, Rhode Island, 1996. American Mathematical Society. 

The correct treatment of boundaries and boundary effects is crucial to simulation methods because it enables macroscopic properties to be calculated from simulations using relatively small numbers of particles. The importance of boundary effects can be illustrated by considering the following simple example. Suppose we have a cube of volume 1 litre which is filled with water at room temperature. The cube contains approximately 3.3 X 10 molecules. Interactions with the walls can extend up to 10 molecular diameters into the fluid. The diameter of the water molecule is approximately 2.8 A and so the number of water molecules that are interacting with the boundary is about 2 x 10. So only about one in 1.5 million water molecules is influenced by interactions with the walls of the container. The number of particles in a Monte Carlo or molecular dynamics simulation is far fewer than 10 -10 and is frequently less than 1000. In a system of 1000 water molecules most, if not all of them, would be within the influence of the walls of the boundary. Clecirly, a simulation of 1000 water molecules in a vessel would not be an appropriate way to derive bulk properties. The alternative is to dispense with the container altogether. Now, approximately three-quarters of the molecules would be at the surface of the sample rather than being in the bulk. Such a situation would be relevcUit to studies of liquid drops, but not to studies of bulk phenomena. 

A macroscopic system maintains constant pressure by changing its volume. A simulation i the isothermal-isobaric ensemble also maintains constant pressure by changing the volurr... 

Molecules are in continuous random motion, and as a result of this, small volume elements within the liquid continuously experience compression or rarefaction such that the local density deviates from the macroscopic average value. If we represent by 6p the difference in density between one such domain and the average, then it is apparent that, averaged over all such fluctuations, 6p = 0 Equal contributions of positive and negative 6 s occur. However, if we consider the average value of 6p, this quantity has a nonzero value. Of these domains of density fluctuation, the following statements can be made ... 

The concentration [MB] constantly experiences tiny fluctuations, the duration of which can determine linewidths. It is also possible to adopt a traditional kinetic viewpoint and measure the time course of such spontaneous fluctuations directly by monitoring the time-varying concentration in an extremely small sample (6). Spontaneous fluctuations obey exactly the same kinetics of return to equiUbrium that describe relaxation of a macroscopic perturbation. Normally, fluctuations are so small they are ignored. The relative ampHtude of a fluctuation is inversely proportional to the square root of the number of AB entities being observed. Consequently, fluctuations are important when concentrations are small or, more usehiUy, when volumes are tiny. 

The analysis of steady-state and transient reactor behavior requires the calculation of reaction rates of neutrons with various materials. If the number density of neutrons at a point is n and their characteristic speed is v, a flux effective area of a nucleus as a cross section O, and a target atom number density N, a macroscopic cross section E = Na can be defined, and the reaction rate per unit volume is R = 0S. This relation may be appHed to the processes of neutron scattering, absorption, and fission in balance equations lea ding to predictions of or to the determination of flux distribution. The consumption of nuclear fuels is governed by time-dependent differential equations analogous to those of Bateman for radioactive decay chains. The rate of change in number of atoms N owing to absorption is as follows ... 

The systems of interest in chemical technology are usually comprised of fluids not appreciably influenced by surface, gravitational, electrical, or magnetic effects. For such homogeneous fluids, molar or specific volume, V, is observed to be a function of temperature, T, pressure, P, and composition. This observation leads to the basic postulate that macroscopic properties of homogeneous PPIT systems at internal equiUbrium can be expressed as functions of temperature, pressure, and composition only. Thus the internal energy and the entropy are functions of temperature, pressure, and composition. These molar or unit mass properties, represented by the symbols U, and S, are independent of system size and are intensive. Total system properties, J and S do depend on system size and are extensive. Thus, if the system contains n moles of fluid, = nAf, where Af is a molar property. Temperature... 

A colloid is a material that exists ia a finely dispersed state. It is usually a solid particle, but it may be a Hquid droplet or a gas bubble. Typically, coUoids have high surface-area-to-volume ratios, characteristic of matter ia the submicrometer-size range. Matter of this size, from approximately 100 nm to 5 nm, just above atomic dimensions, exhibits physicochemical properties that differ from those of both the constituent atoms or molecules and the macroscopic material. The differences ia composition, stmcture, and iateractions between the surface atoms or molecules and those on the iaterior of the colloidal particle lead to the unique character of finely divided material, specifics of which can be quite diverse (see Flocculating agents). 

Macroscopic and Microscopic Balances Three postulates, regarded as laws of physics, are fundamental in fluid mechanics. These are conservation of mass, conservation of momentum, and con-servation of energy. In addition, two other postulates, conservation of moment of momentum (angular momentum) and the entropy inequality (second law of thermodynamics) have occasional use. The conservation principles may be applied either to material systems or to control volumes in space. Most often, control volumes are used. The control volumes may be either of finite or differential size, resulting in either algebraic or differential consei vation equations, respectively. These are often called macroscopic and microscopic balance equations. 

Macroscopic Equations An arbitraiy control volume of finite size is bounded by a surface of area with an outwardly directed unit normal vector n. The control volume is not necessarily fixed in space. Its boundary moves with velocity w. The fluid velocity is v. Figure 6-3 shows the arbitraiy control volume. 

Heterogeneity, nonuniformity and anisotropy are defined as follows. On a macroscopic basis, they imply averaging over elemental volumes of radius e about a point in the media, where e is sufficiently large that Darcy s law can be applied for appropriate Reynolds numbers. In other words, volumes are large relative to that of a single pore. Further, e is the minimum radius that satisfies such a condition. If e is too large, certain nonidealities may be obscured by burying their effects far within the elemental volume. 

Heterogeneity, nonuniformity and anisotropy are based on the probability density distribution of permeability of random macroscopic elemental volumes selected from the medium, where the permeability is expressed by the one-dimensional form of Darcy s law. 

Use the bounding techniques of elasticity to determine upper and lower bounds on the shear modulus, G, of a dispersion-stiffened composite materietl. Express the results In terms of the shear moduli of the constituents (G for the matrix and G for the dispersed particles) and their respective volume fractions (V and V,j). The representative volume element of the composite material should be subjected to a macroscopically uniform shear stress t which results in a macroscopically uniform shear strain y. 

As the metallic particles are assumed to be sufficiently large for macroscopic dielectric theory to be applicable, we can substitute for a the expression for the polarisability of metallic particle immersed in an insulator. The dipole moment is given by the integration of the polarisation over the volume V. Thus, if the polarisation is uniform ... 

Continuum models of solvation treat the solute microscopically, and the surrounding solvent macroscopically, according to the above principles. The simplest treatment is the Onsager (1936) model, where aspirin in solution would be modelled according to Figure 15.4. The solute is embedded in a spherical cavity, whose radius can be estimated by calculating the molecular volume. A dipole in the solute molecule induces polarization in the solvent continuum, which in turn interacts with the solute dipole, leading to stabilization. 

Molecules do not consist of rigid arrays of point charges, and on application of an external electrostatic field the electrons and protons will rearrange themselves until the interaction energy is a minimum. In classical electrostatics, where we deal with macroscopic samples, the phenomenon is referred to as the induced polarization. I dealt with this in Chapter 15, when we discussed the Onsager model of solvation. The nuclei and the electrons will tend to move in opposite directions when a field is applied, and so the electric dipole moment will change. Again, in classical electrostatics we study the induced dipole moment per unit volume. 

Macroscopic observables, such as pressme P or heat capacity at constant volume C v, may be calculated as derivatives of thermodynamic functions. 

The description of mass transfer requires a separation of the contributions of convection and mutual diffusion. While convection means macroscopic motion of complete volume elements, mutual diffusion denotes the macroscopically perceptible relative motion of the individual particles due to concentration gradients. Hence, when measuring mutual diffusion coefficients, one has to avoid convection in the system or, at least has to take it into consideration. 

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