Intensive variables, defined

TEST 1- Define and give examples of extensive and intensive variables. Define degrees of free-... 

Later on we shall consider other extensive variables Y which will correspond to intensive variables defined by... 

Quantities such as the volume V, the mass m, the number of moles <, the thermodynamic potentials. .. are called extensive variables since their values depend on the extent of the S5retem. On the other hand, variables such as the temperature, the pressure, the mole fraction Xi (= m/n) are intensive variables since they have definite values at each point in the system and do not depend on the total extent of the system. The ratio of two extensive variables is an intensive variable. To each extensive variable Y there correspond intensive variables defined by the partial derivative at constant pressure and temperature... 

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,... 

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... 

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... 

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 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. 

If the heat capacity functions of the various terms in the reaction are known and their molar enthalpy, molar entropy, and molar volume at the 2) and i). of reference (and their isobaric thermal expansion and isothermal compressibility) are also all known, it is possible to calculate AG%x at the various T and P conditions of interest, applying to each term in the reaction the procedures outlined in section 2.10, and thus defining the equilibrium constant (and hence the activity product of terms in reactions cf eq. 5.272 and 5.273) or the locus of the P-T points of univariant equilibrium (eq. 5.274). If the thermodynamic data are fragmentary or incomplete—as, for instance, when thermal expansion and compressibility data are missing (which is often the case)—we may assume, as a first approximation, that the molar volume of the reaction is independent of the P and T intensive variables. Adopting as standard state for all terms the state of pure component at the P and T of interest and applying... 

In Rietveld refinement [22, 27, 28], the variables that define the powder XRD profile (i.e. the variables (l)-(4) in Sect. 2.5) and the variables defining the stmctural model (which are used to determine the relative peak intensities in the calculated... 

The advantage of the chemical potential over the other thermodynamic quantities, U, H, and G, is that it is an intensive quantity—that is, is independent of the number of moles or quantity of species present. Internal energy, enthalpy, free energy, and entropy are all extensive variables. Their values depend on the extent of the system—that is, how much there is. We will see in the next section that intensive variables such as p., T, and P are useful in defining equilibrium. 

As we proceed, it will become more convenient to work in the intensive variable, mass density p, rather than in numbers of molecules. We will soon discuss intensive and extensive variables, but for now we simply define density as the mass per unit volume, p = M/ V... 

For a system, namely a uniquely identified mass of fluid, it is often appropriate to think of variables or properties that characterize the system as a whole. For example, what is the total mass, momentum, or energy of the system These are called extensive variables or properties. It is reasonable to expect that within a system there may be local spatial variations in variables or properties. The total system property is determined by integrating local distributions over the mass of the system. To accomplish the integration, it is useful to define an intensive variable, which is the extensive variable per unit mass. That is, if the extensive variable is called N, then the associated intensive variable r) is defined as... 

A curious feature of the space Ms of thermodynamic variables in an equilibrium state S is that its dimensionality varies with the number of phases, p, even though the values of the intensive variables (which might be used to parametrize the state S) do not. The intensive-type ket vectors R/ of (10.8) can actually be defined for all c + 2 intensities (T, —P, fjL, pi2, , pic) arising from the fundamental equation of a c-component system, U(S, V, n, ri2,. .., nc), even if only /of these remain linearly independent when p phases are present. 

Consider a material or system that is not at equilibrium. Its extensive state variables (total entropy number of moles of chemical component, i total magnetization volume etc.) will change consistent with the second law of thermodynamics (i.e., with an increase of entropy of all affected systems). At equilibrium, the values of the intensive variables are specified for instance, if a chemical component is free to move from one part of the material to another and there are no barriers to diffusion, the chemical potential, q., for each chemical component, i, must be uniform throughout the entire material.2 So one way that a material can be out of equilibrium is if there are spatial variations in the chemical potential fii(x,y,z). However, a chemical potential of a component is the amount of reversible work needed to add an infinitesimal amount of that component to a system at equilibrium. Can a chemical potential be defined when the system is not at equilibrium This cannot be done rigorously, but based on decades of development of kinetic models for processes, it is useful to extend the concept of the chemical potential to systems close to, but not at, equilibrium. 

An intensive variable [such as the temperature (T), pressure (P), or individual mole fractions of a single phase (xSi, Xu or y of the hydrate, liquid, or vapor phases, respectively)] is defined as a measured value that is independent of the phase amount. For example, T, P, xSi, xu y or density are intensive variables, while phase masses, volumes, or amounts are extensive variables, and thus not addressed by Gibbs Phase Rule. 

The inequalities of the previous paragraph are extremely important, but they are of little direct use to experimenters because there is no convenient way to hold U and S constant except in isolated systems and adiabatic processes. In both of these inequalities, the independent variables (the properties that are held constant) are all extensive variables. There is just one way to define thermodynamic properties that provide criteria of spontaneous change and equilibrium when intensive variables are held constant, and that is by the use of Legendre transforms. That can be illustrated here with equation 2.2-1, but a more complete discussion of Legendre transforms is given in Section 2.5. Since laboratory experiments are usually carried out at constant pressure, rather than constant volume, a new thermodynamic potential, the enthalpy H, can be defined by... 

The Gibbs phase rule allows /, the number of degrees of freedom of a system, to be determined. / is the number of intensive variables that can and must be specified to define the intensive state of a system at equilibrium. By intensive state is meant the properties of all phases in the system, but not the amounts of these phases. Phase equilibria are determined by chemical potentials, and chemical potentials are intensive properties, which are independent of the amount of the phase that is present. The overall concentration of a system consisting of several phases, however, is not a degree of freedom, because it depends on the amounts of the phases, as well as their concentration. In addition to the intensive variables, we are, in general, allowed to specify one extensive variable for each phase in the system, corresponding to the amount of that phase present. 

With the help of (12.89), it is now possible to establish some simple theorems concerning the possibility of stationary points (e.g., maxima, minima, or horizontal inflections) in thermodynamic phase diagrams. In each case, we suppose that R, Rj are chosen from any set of /+1 intensive variables (spanning at least / — 1 dimensions), and that rj, pj are defined as in (12.82) for a system of p coexisting phases. 

Among intensive variables important in thermodynamics are partial molar quantities, defined by the equation... 

We now examine the properties of the intensive variable fxj. Equation IV.8 (G = YLjPj ni) suggests a very useful way of defining fij. In particular, if we keep fLj and nt constant, we obtain the following expression ... 

The calculations in Chapters 3 to 5 have been based on the use of Legendre transforms to introduce pH and pMg as independent intensive variables. But now we need to discuss the reverse process - that is the transformation of Af G ° values calculated from measured apparent equilibrium constants in the literature to Af G° values of species and the transformation of Af° values calculated from calorimetric measurements in the literature to AfH° of species. This is accomplished by use of the inverse Legendre transform defined by (7) ... 

This implies that the intensive variables of the small system, which may not even be defined during the process, approach those of the large system... 

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