Capacity systems, transfer function

With most properties (enthalpies, volumes, heat capacities, etc.) the standard state is infinite dilution. It is sometimes possible to obtain directly the function near infinite dilution. For example, enthalpies of solution can be measured in solution where the final concentration is of the order of 10-3 molar. With properties such as volumes and heat capacities this is more difficult, and, to get standard values, it is usually necessary to measure apparent molal quantities 0y at various concentrations and extrapolate to infinite dilution (y° = Y°). Fortunately, it turns out that, at least with volumes and heat capacities, the transfer functions AYe (W — W + N) do not vary significantly with the electrolyte concentration as long as this concentration is relatively low (3). With most of the systems investigated, the transfer functions were calculated from apparent molal quantities at 0.1m and assumed to be equivalent to the standard values. 

Capacity Element Now consider the case where the valve in Fig. 8-7 is replaced with a pump. In this case, it is reasonable to assume that the exit flow from the tank is independent of the level in the tank. For such a case, Eq. (8-22) still holds, except that/i no longer depends on hi. For changes in fi, the transfer function relating changes in to changes in is shown in Fig. 8-10. This is an example of a pure capacity process, also called an integrating system. The cross sectional area of the tank is the chemical process equivalent of an electrical capacitor. If the inlet flow is step forced while the outlet is held... 

Medium-chain alcohols such as 2-butoxyethanol (BE) exist as microaggregates in water which in many respects resemble micellar systems. Mixed micelles can be formed between such alcohols and surfactants. The thermodynamics of the system BE-sodlum decanoate (Na-Dec)-water was studied through direct measurements of volumes (flow denslmetry), enthalpies and heat capacities (flow microcalorimetry). Data are reported as transfer functions. The observed trends are analyzed with a recently published chemical equilibrium model (J. Solution Chem. 13,1,1984). By adjusting the distribution constant and the thermodynamic property of the solute In the mixed micelle. It Is possible to fit nearly quantitatively the transfer of BE from water to aqueous NaDec. The model Is not as successful for the transfert of NaDec from water to aqueous BE at low BE concentrations Indicating self-association of NaDec Induced by BE. The model can be used to evaluate the thermodynamic properties of both components of the mixed micelle. 

The densities and volumetric heat capacities of the binary systems, which are required for the calculation of the transfer functions, were measured at the same time as those of the ternary systems. The derived apparent molar quantities of the binaries were In excellent agreement with those In the literature (11,16). 

Urea, as a cosolvent, is at the other extreme. All the concentration dependences of the binary and ternary systems are quite regular. The excess volume (Figure 6) is positive, which is rarely observed for nonelectrolytes in water. With the exception of the heat capacities of Bu4NBr, all the parameters Beu are positive for volumes and heat capacities, and the sign of the transfer functions is always opposite what we would expect for the structural hydration contribution to V° and Cp°. 

It is frequently required to examine the combined performance of two or more processes in series, e.g. two systems or capacities, each described by a transfer function in the form of equations 7.19 or 7.26. Such multicapacity processes do not necessarily have to consist of more than one physical unit. Examples of the latter are a protected thermocouple junction where the time constant for heat transfer across the sheath material surrounding the junction is significant, or a distillation column in which each tray can be assumed to act as a separate capacity with respect to liquid flow and thermal energy. 

Two tanks in series. Consider the two tanks shown in Fig. 7.16. In this system neither the rate of flow through tank 1 nor the level in tank 1 is affected by what occurs in tank 2. Thus the two processes (or capacity systems) are non-interacting and we can model their dynamic behaviours individually. To establish the relationship between the level in tank 2 and the volumetric flowrate entering tank 1 at any instant of time, we need only to determine the individual transfer functions between Q0 and Q, and between 2, and z2. 

In Section 11.3 we found that two capacities in series, interacting or noninteracting, give rise to a second-order system. If we extend the same procedure to N capacities (first-order systems) in series, we find that the overall response is of Nth order that is, the denominator of the overall transfer function is an iVth-order polynomial,... 

Bode diagram, 330-31, 334-37 frequency response, 323-24 interacting capacities, 197-200 noninteracting capacities, 194-96 pulse transfer function, 619 Multiple-input multiple-output system, 20 discrete-time model, 586 discrete transfer function, 612 input-output model, 83-85, 163-68 linearization, 121-26 transfer-function matrix, 164, 166 Multiple loop control systems, 394-409 Multiplexer, 560, 564 Multivariable control systems, 461-62 alternative configurations, 467-84 decoupling of loops, 503-8 design questions, 461-62 interaction of loops, 487-94 selection of loops, 494-503 Multivariable process (see Multiple-input multiple-output system)... 

In Chapter 11 we found that almost all second-order, open-loop processes are overdamped systems (( > 1) composed of two interacting capacities in series. Therefore, the transfer function can be written as... 

Other potentially useful transfer functions are the transfer heat capacity, SCI, transfer volume, and the transfer internal energy, SUl (Abraham, 1974). At present, measurements of these transfer functions are available for only a few systems, but they can in certain instances be predicted using scaled-particle theory (Desrosiers and Desnoyers, 1976). 

Perron, G., DeLisi, R., Davidson, L, Genereux, S., Desnoyers, J.E. On the use of thermodynamic transfer functions for the study of the effect of additives on micellization volumes and heat capacities of solutions of sodium octanoate systems. J. Colloid Interface Sci. 1981, 79(2), 432-442. 

When heat is liberated or absorbed in the calorimeter vessel, a thermal flux is established in the heat conductor and heat flows until the thermal equilibrium of the calorimetric system is restored. The heat capacity of the surrounding medium (heat sink) is supposed to be infinitely large and its temperature is not modified by the amount of heat flowing in or out. The quantity of heat flowing along the heat conductor is evaluated, as a function of time, from the intensity of a physical modification produced in the conductor by the heat flux. Usually, the temperature difference 0 between the ends of the conductor is measured. Since heat is transferred by conduction along the heat conductor, calorimeters of this type are often also named conduction calorimeters (20a). 

The Nusselt number with respect to the tube Nu(= hdt/k) is expressed as a function of four dimensionless groups the ratio of tube diameter to length, the ratio of tube to particle diameter, the ratio of the heat capacity per unit volume of the solid to that of the fluid, and the tube Reynolds number, Rec = (ucdtp/p,). However, equation 6.59 and other equations quoted in the literature should be used with extreme caution, as the value of the heat transfer coefficient will be highly dependent on the flow patterns of gas and solid and the precise geometry of the system. 

The types of equipment used, which range from stirred tanks and mixer-settlers to centrifugal contactors and various types of columns, affect both capital and operating costs [9]. In the decision to build a plant, the choice of the most suitable contactor for the specific situation is most important. In some systems, because of the chemistry and mass transfer rates involved, several alternative designs of contacting equipment are available. In the selection of a contactor, one must consider the capacity and stage requirements solvent type and residence time phase flow ratio physical properties direction of mass transfer phase dispersion and coalescence holdup kinetics equilibrium presence of solids overall performance and maintenance as a function of contactor complexity. This may appear very complicated, but with some experience, the choice is relatively simple. 

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