Design equation constant volume

Example 2.11 Suppose initially pure A dimerizes, 2A —> B, isothermally in the gas phase at a constant pressure of 1 atm. Find a solution to the batch design equation and compare the results with a hypothetical batch reactor in which the reaction is 2A B - - C so that there is no volume change upon reaction. 

Since the reaction takes place at constant volume, the pertinent design equation is equation 8.1.7. 

From the units on the reaction rate constant, the reaction is second order. There is a volume change on reaction and S = —1/2. Thermal expansion will also occur, so equations 3.1.44 and 3.1.46 must be combined to get the reactant concentrations. Since equimolar concentrations of reactants are used, the design equation becomes... 

One has to design the experiment to take a set of data designed to facilitate the task of parameter extraction. If a set of data is taken under constant volume conditions, and the pressure is plotted against the temperature, then there will be an intercept of —alV and a slope of R/ V — b). The van der Waals equation of state is the simplest of the equations of state beyond the perfect gas law, and the task of extracting parameter values from experimental data for the more complicated equations of state would require more ingenuity. The Redlich-Kwong equation has two parameters, A and B ... 

Clausius-Mossotti equation). In this expression, V designates the mole volume and Ae, Be, Cf,... are the first, second, third,... virial dielectric coefficients. A similar expansion exists for the refractive index, n, which is related to the (frequency dependent) dielectric constant as n2 = e (Lorentz-Lorenz equation, [87]). The second virial dielectric coefficient Be may be considered the sum of an orientational and a polarization term, Be = B0r + Bpo, arising from binary interactions, while the second virial refractive coefficient is given by just the polarization term, B = Bpo at high enough frequencies, the orientational component falls off to small values and the difference Be — B may be considered a measurement of the interaction-induced dipole moments [73],... 

REACTOR DESIGN-GENERAL PRINCIPLES Table 1.1. Rate Equations for Constant Volume Batch Reactors... 

If the rate equation is to be employed in its integrated form, the problem of determining kinetic constants from experimental data from batch or tubular reactors is in many ways equivalent to taking the design equations and working backwards. Thus, for a batch reactor with constant volume of reaction mixture at constant temperature, the equations listed in Table 1.1 apply. For example, if a reaction is suspected of being second order overall, the experimental results are plotted in the form ... 

In Chapter 3, the analytical method of solving kinetic schemes in a batch system was considered. Generally, industrial realistic schemes are complex and obtaining analytical solutions can be very difficult. Because this is often the case for such systems as isothermal, constant volume batch reactors and semibatch systems, the designer must review an alternative to the analytical technique, namely a numerical method, to obtain a solution. For systems such as the batch, semibatch, and plug flow reactors, sets of simultaneous, first order ordinary differential equations are often necessary to obtain the required solutions. Transient situations often arise in the case of continuous flow stirred tank reactors, and the use of numerical techniques is the most convenient and appropriate method. 

Equation (57) represents the basic design equation for use with batch reactors. In case the reactor volume (Vb) remains constant during the entire reaction, integration of the equation can be simplified by recognizing that Nio/Vb is merely the concentration of the reactant at the start of the reaction and removing the Vb term from under the integral sign. 

PI-4,4, Calculate the time to reduce the number of moles of A to 1 % of its initial value in a constant-volume batch reactor for the reaction and data in Example I -3. Pl-S 4 What assumptions were made in the derivation of the design equation for ... 

Rewrite the design equation in terms of the measured variabte. When there is a net increase or decrease in the totai number of moles in a gas phase reaction, the reaction order may be determined from experiments performed with a constant-volume batch reactor by monitoring the total pressure as a function of time. The total pressure data should not be converted to conversion and then analyzed as conversion-time data just because the design equations are written in terms of the variable conversions. Rather, transform the design equation to the measured variable, which in this case is pressure. Consequently, we need to express the concentration in terms of total pressure and then substitute for the concemtation of A in Equation (E5-I.1),... 

Equation (2 26) is a form of the design equation for constant volumetric flow rate Uq that may prove more useful in determining the space time or reactor volume for reaction rates that depend only on the concentration of one species. 

Because each globule acts as a batch reactor of constant volume, we use the batch reactor design equation to arrive at the equation giving conversion as a function of time ... 

Substituting this in the design equation for constant volume [Eq. (4-2)] yields... 

For constant-volume batch reactors with single reactions, and selecting the initial state as the reference state, the design equation, Eq. 6.2.1, reduces to... 

Equation 6.2.5 is the integral form of the design equation for an ideal, constant-volume batch reactor. Figure 6.3 shows the graphical presentation of this design equation. To solve the design equations, we have to express the reaction rate r in... 

The main difficulty in determining the reaction rate r is that the extent is not a measurable quantity. Therefore, we have to derive a relationship between the reaction rate and the appropriate measurable quantity. We do so by using the design equation and stoichiometric relations. Also, since the characteristic reaction time is not known a priori, we write the design equation in terms of operating time rather than dimensionless time. Assume that we measure the concentration of species j, Cj(t), as a function of time in an isothermal, constant-volume batch reactor. To derive a relation between the reaction rate, r, and Cj(t), we divide both sides of Eq. 6.2.4, by obtain... 

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