Variables intensive

The second set of equations is obtained from the first set by the Gibbs integration at constant intensive variables, as was done in obtaining Eq. III-77. It is convenient, in dealing with a surface species, to introduce some special definitions, two of which are... 

This is Gibbs s phase rule. It specifies the number of independent intensive variables that can and must be fixed in order to estabbsh the intensive equibbrium state of a system and to render an equibbrium problem solvable. 

Solubility. Sohd—Hquid equihbrium, or the solubiHty of a chemical compound in a solvent, refers to the amount of solute that can be dissolved at constant temperature, pressure, and system composition in other words, the maximum concentration of the solute in the solvent at static conditions. In a system consisting of a solute and a solvent, specifying system temperature and pressure fixes ah. other intensive variables. In particular, the composition of each of the two phases is fixed, and solubiHty diagrams of the type shown for a hypothetical mixture of R and S in Figure 2 can be constmcted. Such a system is said to form an eutectic, ie, there is a condition at which both R and S crystallize into a soHd phase at a fixed ratio that is identical to their ratio in solution. Consequently, there is no change in the composition of residual Hquor as a result of crystallization. 

Labor intensive variability in observer perception suitable targets for visual range not generally available... 

The rate is defined as an intensive variable, and the definition is independent of any partieular reaetant or produet speeies. Beeause the reaetion rate ehanges with time, we ean use the time derivative to express the instantaneous rate of reaetion sinee it is influeneed by the eomposition and temperature (i.e., the energy of the material). Thus,... 

The intensive variable for volume (V) can be either the specific volume ( V, volume/mass) or the specific molal volume ( V volume/mole). 

Intensity variable with time during excitation No Yes... 

The fundamental idea of this procedure is as follows For a system of two fluid phases containing N components, we are concerned with N — 1 independent mole fractions in each phase, as well as with two other intensive variables, temperature T and total pressure P. Let us suppose that the two phases (vapor and liquid) are at equilibrium, and that we are given the total pressure P and the mole fractions of the liquid phase x, x2,. .., xN. We wish to find the equilibrium temperature T and the mole fractions of the vapor phase yu y2,. .., yN-i- The total number of unknowns is N + 2 there are N — 1 unknown mole fractions, one unknown temperature, and two unknown densities corresponding to the two limits of integration in Eq. (6), one for the liquid phase and the other for the vapor phase. To solve for these N +2 unknowns, we require N + 2 equations of equilibrium. For each component i we have an equation of the form... 

Before describing these thermodynamic variables, we must talk about their properties. The variables are classified as intensive or extensive. Extensive variables depend upon the amount while intensive variables do not. Density is an example of an intensive variable. The density of an ice crystal in an iceberg is the same as the density of the entire iceberg. Volume, on the other hand, is an extensive variable. The volume of the ocean is very different from the volume of a drop of sea water. When we talk about an extensive thermodynamic variable Z we must be careful to specify the amount. This is usually done in terms of the molar property Zm, defined as... 

Like pressure, temperature is an intensive variable. In a qualitative sense it may be thought of as the potential that drives the flow of heat. This can be seen by referring to Figure l.l. If two systems are in thermal contact, one at temperature 7) and the other at temperature 73, then heat will be exchanged between the two systems so that q flows from system 1 to system 2 and q2 flows from system 2 to system 1. If 73 > 7), then the rate of flow of heat from system 2 to system 1 will be greater than the rate of flow of heat from system 1 to system 2. The net effect will be that system 1 will increase in temperature and system 2 will decrease in temperature. With time, the difference between the two heat flow rates decreases until it becomes zero. When this occurs, 73 = 73 and the two systems are said to be in thermal equilibrium the flow of heat from system 1 to 2 balances the flow of heat from system 2 to 1. 

The substitutions can be made because the extensive thermodynamic variables in the equations are homogeneous of degree one.d Thus, dividing the equation by n converts the extensive variable to the corresponding molar intensive variable. For example, to prove that equation (3.48) follows from equation... 

Euler s theorem 612 exact differentials 604-5 extensive variables 598 graphical integrations 613-15 Simpson s rule 614-15 trapezoidal rule 613-14 inexact differentials 604-5 intensive variables 598 line integrals 605-8... 

Electrical conductivity is an easily measured transport property, and percolation in electrical conductivity appears a sensitive probe for characterizing microstructural transformations. A variety of field (intensive) variables have been found to drive percolation in reverse microemulsions. Disperse phase volume fraction has been often reported as a driver of percolation in electrical conductivity in such microemulsions [17-20]. 

Assuming that the coarse velocity can be regarded as an intensive variable, this shows that the second entropy is extensive in the time interval. The time extensivity of the second entropy was originally obtained by certain Markov and integration arguments that are essentially equivalent to those used here [2]. The symmetric matrix a 2 controls the strength of the fluctuations of the coarse velocity about its most likely value. That the symmetric part of the transport matrix controls the fluctuations has been noted previously (see Section 2.6 of Ref. 35, and also Ref. 82). 

The irreversible processes described must not occur even on open circuit. In a reversible cell, a definite equilibrium must be established and this may be defined in terms of the intensive variables in a similar way to the description of phase and chemical equilibria of electroneutral components. 

The rate is defined as an intensive variable. Note that the reciprocal of system volume is outside the derivative term. This consideration is important in treating variable volume systems. 

To this point, the acceptance rules have been defined for a simulation, in which the total number of molecules in the system, temperature and volume are constant. For pure component systems, the phase rule requires that only one intensive variable (in this case the system temperature) can be independently specified when two phases... 

The specific heat is the amount of heat required to change one mole of a substance by one degree in temperature. Therefore, unlike the extensive variable heat capacity, which depends on the quantity of material, specific heat is an intensive variable and has units of energy per number of moles (n) per degree. 

Perkins, E. H., 1992, Integration of intensive variable diagrams and fluid phase equilibrium with SOLMINEQ.88 pc/shell. In Y. K. Kharaka and A. S. Maest (eds.), Water-Rock Interaction, Balkema, Rotterdam, p. 1079-1081. 

The functions a and P are intensive because N, U and d In Q are extensive. If the size of the system is increased m-fold, while keeping the intensive variables fixed, integration gives... 

In both the entropy and energy representations the extensive parameters are the independent variables, whereas the intensive parameters are derived concepts. This is in contrast to reality in the laboratory where the intensive parameters, like the temperature, are the more easily measurable while a variable such as entropy cannot be measured or controlled directly. It becomes an attractive possibility to replace extensive by intensive variables as... 

The potential function of intensive variables only, U(T, P, pj) corresponds to the full Legendre transformation... 

In thermodynamics the state of a system is specified in terms of macroscopic state variables such as volume, V, temperature, T, pressure,/ , and the number of moles of the chemical constituents i, tij. The laws of thermodynamics are founded on the concepts of internal energy (U), and entropy (S), which are functions of the state variables. Thermodynamic variables are categorized as intensive or extensive. Variables that are proportional to the size of the system (e.g. volume and internal energy) are called extensive variables, whereas variables that specify a property that is independent of the size of the system (e.g. temperature and pressure) are called intensive variables. 

Type of work Intensive variable Extensive variable Differential work in dU... 

In general, dw is written in the form (intensive variable)-d(extensive variable) or as a product of a force times a displacement of some kind. Several types of work terms may be involved in a single thermodynamic system, and electrical, mechanical, magnetic and gravitational fields are of special importance in certain applications of materials. A number of types of work that may be involved in a thermodynamic system are summed up in Table 1.1. The last column gives the form of work in the equation for the internal energy. 

In order to focus on the driving force for phase transitions induced by a magnetic field it is advantageous to use the magnetic flux density as an intensive variable. This can be achieved through what is called a Legendre transform [12], A transformed Helmholtz energy is defined as... 

For three-component (C = 3) or ternary systems the Gibbs phase rule reads Ph + F = C + 2 = 5. In the simplest case the components of the system are three elements, but a ternary system may for example also have three oxides or fluorides as components. As a rule of thumb the number of independent components in a system can be determined by the number of elements in the system. If the oxidation state of all elements are equal in all phases, the number of components is reduced by 1. The Gibbs phase rule implies that five phases will coexist in invariant phase equilibria, four in univariant and three in divariant phase equilibria. With only a single phase present F = 4, and the equilibrium state of a ternary system can only be represented graphically by reducing the number of intensive variables. 

For obvious reasons, we need to introduce surface contributions in the thermodynamic framework. Typically, in interface thermodynamics, the area in the system, e.g. the area of an air-water interface, is a state variable that can be adjusted by the observer while keeping the intensive variables (such as the temperature, pressure and chemical potentials) fixed. The unique feature in selfassembling systems is that the observer cannot adjust the area of a membrane in the same way, unless the membrane is put in a frame. Systems that have self-assembly characteristics are conveniently handled in a setting of thermodynamics of small systems, developed by Hill [12], and applied to surfactant self-assembly by Hall and Pethica [13]. In this approach, it is not necessary to make assumptions about the structure of the aggregates in order to define exactly the equilibrium conditions. However, for the present purpose, it is convenient to take the bilayer as an example. 

The analogue to one-component thermodynamics applies to the nature of the variables. So Ay S, U and V are all extensive variables, i.e. they depend on the size of the system. The intensive variables are n and T -these are local properties independent of the mass of the material. The relationship between the osmotic pressure and the rate of change of Helmholtz free energy with volume is an important one. The volume of the system, while a useful quantity, is not the usual manner in which colloidal systems are handled. The concentration or volume fraction is usually used ... 

In the study of thermodynamics we can distinguish between variables that are independent of the quantity of matter in a system, the intensive variables, and variables that depend on the quantity of matter. Of the latter group, those variables whose values are directly proportional to the quantity of matter are of particular interest and are simple to deal with mathematically. They are called extensive variables. Volume and heat capacity are typical examples of extensive variables, whereas temperature, pressure, viscosity, concentration, and molar heat capacity are examples of intensive variables. 

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