First-order reactions volume

The material balance for a continuous-flow, stirred-tank reactor with constant volume and first-order reaction is... 

A general mathematical formulation that is applicable to most models described in the earlier sections begins with the volume reaction model described by Equations (11.69) through (11.72). Then, for a reaction first order in the gaseous component, we recast these equations as... 

Applying Equation 2.5 in more explicit form to reaction R16, and assuming constant volume and first-order dependence of the rate on each concentration, we obtain... 

Herein [5.2]i is the total number of moles of 5.2 present in the reaction mixture, divided by the total reaction volume V is the observed pseudo-first-order rate constant Vmrji,s is an estimate of the molar volume of micellised surfactant S 1 and k , are the second-order rate constants in the aqueous phase and in the micellar pseudophase, respectively (see Figure 5.2) V is the volume of the aqueous phase and Psj is the partition coefficient of 5.2 over the micellar pseudophase and water, expressed as a ratio of concentrations. From the dependence of [5.2]j/lq,fe on the concentration of surfactant, Pj... 

Reactants must diffuse through the network of pores of a catalyst particle to reach the internal area, and the products must diffuse back. The optimum porosity of a catalyst particle is deterrnined by tradeoffs making the pores smaller increases the surface area and thereby increases the activity of the catalyst, but this gain is offset by the increased resistance to transport in the smaller pores increasing the pore volume to create larger pores for faster transport is compensated by a loss of physical strength. A simple quantitative development (46—48) follows for a first-order, isothermal, irreversible catalytic reaction in a spherical, porous catalyst particle. 

Different Sizes Ordinarily, it is most economical to make all stages of a CSTR battery the same size. For a first-order reaction the resulting total volume is a minimum for a specified performance, but not so for other orders. Take a two-stage battery ... 

The minimum total volume of a CSTR battery for first-order reaction, and near-minimum for second-order, is obtained when all vessels are the same size. 

FIG. 23-15 Chemical conversion by the dispersion model, (a) First-order reaction, volume relative to plug flow against residual concentration ratio, (h) Second-order reaction, residual concentration ratio against kC t. 

Assuming that the reactions are first order in a constant volume batch reactor, the rate equations for components A, B, C, and D, respectively, are ... 

For a cascade of N CFSTRs of equal volume, Vr, in which the first order forward reaction A—occurs with a throughput u, show that the system fractional conversion is... 

Volume of CFSTR and plug flow reactors with respect to conversion level for a first order reaction... 

Consider a first order, exothermic reaction (aA —> products) in a CFSTR having a constant supply of new reagents, and maintained at a steady state temperature T that is uniform throughout the system volume. Assuming perfect mixing and no density change, the material balance equation based on reactants is expressed as uC g = +... 

Consider the reversible first order reaction A R. It is possible to determine the minimum reactor volume at the optimum temperature Tgp( that is required to obtain a fractional conversion X, if the feed is pure A with a volumetric flowrate of u. A material balance for a CESTR is... 

A certain reaction is first-order in A and second-order in B. In the box shown below, which is assumed to have a volume of one liter, a mole of A is represented by a mole... 

This equation is that of a first-order reaction process, and thus the fraction of material electrolysed at any instant is independent of the initial concentration. It follows that if the limit of accuracy of the determination is set at C, = 0.001 C0, the time t required to achieve this result will be independent of the initial concentration. The constant k in the above equation can be shown to be equal to Am/ V, where A is the area of the pertinent electrode, V the volume of the solution and m the mass transfer coefficient of the electrolyte.20 It follows that to make t small A and m must be large, and V small, and this leads to the... 

In Fig. 28, the abscissa kt is the product of the reaction rate constant and the reactor residence time, which is proportional to the reciprocal of the space velocity. The parameter k co is the product of the CO inhibition parameter and inlet concentration. Since k is approximately 5 at 600°F these three curves represent c = 1, 2, and 4%. The conversion for a first-order kinetics is independent of the inlet concentration, but the conversion for the kinetics of Eq. (48) is highly dependent on inlet concentration. As the space velocity increases, kt decreases in a reciprocal manner and the conversion for a first-order reaction gradually declines. For the kinetics of Eq. (48), the conversion is 100% at low space velocities, and does not vary as the space velocity is increased until a threshold is reached with precipitous conversion decline. The conversion for the same kinetics in a stirred tank reactor is shown in Fig. 29. For the kinetics of Eq. (48), multiple solutions may be encountered when the inlet concentration is sufficiently high. Given two reactors of the same volume, and given the same kinetics and inlet concentrations, the conversions are compared in Fig. 30. The piston flow reactor has an advantage over the stirred tank... 

Non-isothermal measurements of the temperatures of dehydrations and decompositions of some 25 oxalates in oxygen or in nitrogen atmospheres have been reported by Dollimore and Griffiths [39]. Shkarin et al. [606] conclude, from the similarities they found in the kinetics of dehydration of Ni, Mn, Co, Fe, Mg, Ca and Th hydrated oxalates (first-order reactions and all values of E 100 kJ mole-1), that the mechanisms of reactions of the seven salts are probably identical. We believe, however, that this conclusion is premature when considered with reference to more recent observations for NiC204 2 H20 (see below [129]) where kinetic characteristics are shown to be sensitive to prevailing conditions. The dehydration of MnC204 2 H20 [607] has been found to obey the contracting volume... 

The kinetic effect of increased pressure is also in agreement with the proposed mechanism. A pressure of 2000 atm increased the first-order rates of nitration of toluene in acetic acid at 20 °C and in nitromethane at 0 °C by a factor of about 2, and increased the rates of the zeroth-order nitrations of p-dichlorobenzene in nitromethane at 0 °C and of chlorobenzene and benzene in acetic acid at 0 °C by a factor of about 559. The products of the equilibrium (21a) have a smaller volume than the reactants and hence an increase in pressure speeds up the rate by increasing the formation of H2NO. Likewise, the heterolysis of the nitric acidium ion in equilibrium (22) and the reaction of the nitronium ion with the aromatic are processes both of which have a volume decrease, consequently the first-order reactions are also speeded up and to a greater extent than the zeroth-order reactions. 

This form assumes that the effect of pressure on the molar volume of the solvent, which accelerates reactions of order > 1 by increasing the concentrations when they are expressed on the molar scale, has been allowed for. This effect is usually small, ignored but in the most precise work. Equation (7-41) shows that In k will vary linearly with pressure. We shall refer to this graph as the pressure profile. The value of A V is easily calculated from its slope. The values of A V may be nearly zero, positive, or negative. In the first case, the reaction rate shows little if any pressure dependence in the second and third, the applied hydrostatic pressure will cause k to decrease or increase, respectively. A positive value of the volume of activation means that the molar volume of the transition state is larger than the combined molar volume of the reactant(s), and vice versa. 

Since the value of the first-order rate constant is not given, X and cannot be calculated directly. The reaction rate per unit volume of catalyst 9tt. = rikC i (equation 10.217),... 

Since S/t has units of moles per volume per time and a has units of moles per volume, the rate constant for a first-order reaction has units of reciprocal time e.g., s. The best example of a truly first-order reaction is radioactive decay for example,... 

FIGURE 1.8 Comparison of reactor volume required for a given conversion for a first-order reaction in a PFR and a CSTR. 

Consider the gas-phase decomposition A B -b C in an isothermal tubular reactor. The tube i.d. is 1 in. There is no packing. The pressure drop is 1 psi with the outlet at atmospheric pressure. The gas flow rate is O.OSSCF/s. The molecular weights of B and C are 48 and 52, respectively. The entering gas contains 50% A and 50% inerts by volume. The operating temperature is 700°C. The cracking reaction is first order with a rate constant of 0.93 s . How long is the tube and what... 

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