Ideal behavior

In vapor-liquid equilibria, it is relatively easy to start the iteration because assumption of ideal behavior (Raoult s law) provides a reasonable zeroth approximation. By contrast, there is no obvious corresponding method to start the iteration calculation for liquid-liquid equilibria. Further, when two liquid phases are present, we must calculate for each component activity coefficients in two phases since these are often strongly nonlinear functions of compositions, liquid-liquid equilibrium calculations are highly sensitive to small changes in composition. In vapor-liquid equilibria at modest pressures, this sensitivity is lower because vapor-phase fugacity coefficients are usually close to unity and only weak functions of composition. For liquid-liquid equilibria, it is therefore more difficult to construct a numerical iteration procedure that converges both rapidly and consistently. 

Figure 3-7. Fugacity coefficients for a saturated mixture of propionic acid (1) and raethylisobutylketone (2). Calculations based on chemical method show large variations from ideal behavior.

A component in a vapor mixture exhibits nonideal behavior as a result of molecular interactions only when these interactions are very wea)c or very infrequent is ideal behavior approached. The fugacity coefficient (fi is a measure of nonideality and a departure of < ) from unity is a measure of the extent to which a molecule i interacts with its neighbors. The fugacity coefficient depends on pressure, temperature, and vapor composition this dependence, in the moderate pressure region covered by the truncated virial equation, is usually as follows ... 

So little systematic information is available about transport in liquids, or strongly non-ideal gaseous mixtures, that attention will be limited throughout to the behavior of ideal gas mixtures. It is not intende thereby, to minimize the importance of non-ideal behavior in practice. 

The tme driving force for any diffusive transport process is the gradient of chemical potential rather than the gradient of concentration. This distinction is not important in dilute systems where thermodynamically ideal behavior is approached. However, it becomes important at higher concentration levels and in micropore and surface diffusion. To a first approximation the expression for the diffusive flux may be written... 

Gaseous helium is commonly used as the working fluid ia closed-cycle cryogenic refrigerators because of chemical iaertness, nearly ideal behavior at all but the lowest temperatures, high heat capacity per unit mass, low viscosity, and high thermal conductivity. 

Departures from the ideal behavior expressed by equation 7 usually are found in alkaline solutions containing alkaH metal ions in appreciable concentration, and often in solutions of strong acids. The supposition that the alkaline error is associated with the development of an imperfect response to alkaH metal ions is substantiated by the successhil design of cation-sensitive electrodes that are used to determine sodium, silver, and other monovalent cations (3). 

From this equation, the temperature dependence of is known, and vice versa (21). The ideal-gas state at a pressure of 101.3 kPa (1 atm) is often regarded as a standard state, for which the heat capacities are denoted by CP and Real gases rarely depart significantly from ideaHty at near-ambient pressures (3) therefore, and usually represent good estimates of the heat capacities of real gases at low to moderate, eg, up to several hundred kPa, pressures. Otherwise thermodynamic excess functions are used to correct for deviations from ideal behavior when such situations occur (3). 

In principle, ideal decouphng eliminates control loop interactions and allows the closed-loop system to behave as a set of independent control loops. But in practice, this ideal behavior is not attained for a variety of reasons, including imperfect process models and the presence of saturation constraints on controller outputs and manipulated variables. Furthermore, the ideal decoupler design equations in (8-52) and (8-53) may not be physically realizable andthus would have to be approximated. 

A key limitation of sizing Eq. (8-109) is the limitation to incompressible flmds. For gases and vapors, density is dependent on pressure. For convenience, compressible fluids are often assumed to follow the ideal-gas-law model. Deviations from ideal behavior are corrected for, to first order, with nommity values of compressibihty factor Z. (See Sec. 2, Thvsical and Chemical Data, for definitions and data for common fluids.) For compressible fluids... 

Real reactors deviate more or less from these ideal behaviors. Deviations may be detected with re.sidence time distributions (RTD) obtained with the aid of tracer tests. In other cases a mechanism may be postulated and its parameters checked against test data. The commonest models are combinations of CSTRs and PFRs in series and/or parallel. Thus, a stirred tank may be assumed completely mixed in the vicinity of the impeller and in plug flow near the outlet. 

The distribution of residence times of reactants or tracers in a flow vessel, the RTD, is a key datum for determining reactor performance, either the expected conversion or the range in which the conversion must fall. In this section it is shown how tracer tests may be used to estabhsh how nearly a particular vessel approaches some standard ideal behavior, or what its efficiency is. The most useful comparisons are with complete mixing and with plug flow. A glossary of special terms is given in Table 23-3, and major relations of tracer response functions are shown in Table 23-4. 

Deviations from the ideal behavior that could be accounted for by the use of activity coefficients are neglected here.)... 

Wave profiles in the elastic-plastic region are often idealized as two distinct shock fronts separated by a region of constant elastic strain. Such an idealized behavior is seldom, if ever, observed. Near the leading elastic wave, relaxations are typical and the profile in front of the inelastic wave typically shows significant changes in stress with time. 

It is instructive to describe elastic-plastic responses in terms of idealized behaviors. Generally, elastic-deformation models describe the solid as either linearly or nonlinearly elastic. The plastic deformation material models describe rate-independent behaviors in terms of either ideal plasticity, strainhardening plasticity, strain-softening plasticity, or as stress-history dependent, e.g. the Bauschinger effect [64J01, 91S01]. Rate-dependent descriptions are more physically realistic and are the basis for viscoplastic models. The degree of flexibility afforded elastic-plastic model development has typically led to descriptions of materials response that contain more adjustable parameters than can be independently verified. 

Fig. 2.10. Certain high strength solids with low thermal conductivity show a loss or reduction of shear strength when loaded above the Hugoniot elastic limit. The idealized behavior of such solids upon loading is shown here. The complex, heterogeneous nature of such yield phenomena probably results in processes that are far from thermodynamic equilibrium.

The so-called potentiometric selectivity coefficient K " reflects the non-ideal behavior of ion-selective membranes and determines the specificity of this electro-... 

Fig. 59. Possible deviations from the ideal behavior of a binary system A-B...

There is a reasonable explanation for this type of deviation. The kinetic theory, which explains the pressure-volume behavior, is based upon the assumption that the particles exert no force on each other. But real molecules do exert force on each other The condensation of every gas on cooling shows that there are always attractive forces. These forces are not very important when the molecules are far apart (that is, at low pressures) but they become noticeable at higher pressures. With this explanation, we see that the kinetic theory is based on an idealized gas—one for which the molecules exert no force on each other whatsoever. Every gas approaches such ideal behavior if the pressure is low enough. Then ihe molecules are, on the average, so far apart that then-attractive forces are negligible. A gas that behaves as though the molecules exert no force on each other is called an ideal gas or a perfect gas. 

A dependence of w upon composition must also be adduced in the case of the Fe-Ni solid solutions. Over the range from 0 to 56 at. per cent Ni, these solid solutions exhibit essentially ideal behavior,39 so that w 0. Since the FeNi3 superlattice appears at lower temperatures, either w is markedly different at compositions about 75 at. per cent Ni than at lower Ni contents, or w 0 for the solid solutions about the superlattice. Either possibility represents a deviation from the requirements of the quasi-chemical theories. 

Let s compare these plots of the REV s to the plot in Figure 52. Notice that these REV s do not exhibit ideal behavior. Ideally, as rank increases, the REV s would drop to some minimum value and then remain at that level. These REV s begin to tail back up. This sort of non-ideal behavior is not uncommon when working with actual data. Unfortunately, it can complicate matters when we use the 2-way F-test to see which REV s represent basis vectors and which ones represent noise vectors. 

Kaye and Chou39 also studied the effect of base stacking on the conformation of PA using osmometry, intrinsic viscosity, and light-scattering. The ideal behavior (under the 0 conditions) of PA existed at neutral pH (= 7.4) and at 26 and 40 °C from the osmotic measurements. 

In eq. 8, the rate of polymerization is shown as being half order in initiator (T). This is only true for initiators that decompose to two radicals both of which begin chains. The form of this term depends on the particular initiator and the initiation mechanism. The equation takes a slightly different form in the case of thermal initiation (S), redox initiation, diradical initiation, etc. Side reactions also cause a departure from ideal behavior. 

The rate constants for chain transfer and propagation may well have a different dependence on temperature (i.e. the two reactions may have different activation parameters) and, as a consequence, transfer constants are temperature dependent. The temperature dependence of Clr has not been determined for most transfer agents. Care must therefore he taken when using literature values of Clr if the reaction conditions are different from those employed for the measurement of Ctr. For cases where the transfer constant is close to 1.0, it is sometimes possible to choose a reaction temperature such that the transfer constant is 1.0 and thus obtain ideal behavior. 3... 

When we consider equilibrium between two phases at high pressure, neither phase being dilute with respect to one of the components, we can no longer make the simplifying assumptions made in some of the earlier sections. We must now realistically describe deviations from ideal behavior in both phases for each phase, the effect of both pressure and composition must be seriously taken into account if we wish to describe vapor-liquid equilibria at high pressures for a wide range of conditions, including the critical. 

Gas thermometers that employ equation (1.10) can be constructed to measure either pressure while holding the volume constant (the most common procedure) or volume while holding the pressure constant. The (pV) product can be extrapolated to zero p. but this is an involved procedure. More often, an equation of state or experimental gas imperfection data are used to correct to ideal behavior. Helium is the usual choice of gas for a gas thermometer, since gas imperfection is small, although other gases such as hydrogen have also been used. In any event, measurement of absolute temperature with a gas thermometer is a difficult procedure. Instead, temperatures are usually referred to a secondary scale known as the International Temperature Scale or ITS-90. 

We will show later that /o x. = 0 for an ideal gas. Thus the change in temperature resulting from a Joule-Thomson expansion is associated with the non-ideal behavior of the gas. 

Thus, nj T = 0 for the ideal gas, and the change in temperature during the Joule-Thomson expansion depends upon non-ideal behavior of the gas. 

Figure 4.5 The correction to ideal behavior AS rr = Sm., — 5m r is given by ASjx>rr + AS. 2 + ASm.3 since S is a state function, (p is a very low pressure.)...

We need an equation of state for a real gas to calculate ASm. i. The modified Berthelot equation is often used for pressures near ambient and was used in the original reference to calculate the correction to ideal behavior for N gas.h This equation is as follows... 

---