First-order reactions solutions

It is readily apparent that equation 8.3.21 reduces to the basic design equation (equation 8.3.7) when steady-state conditions prevail. Under the presumptions that CA in undergoes a step change at time zero and that the system is isothermal, equation 8.3.21 has been solved for various reaction rate expressions. In the case of first-order reactions, solutions are available for both multiple identical CSTR s in series and individual CSTR s (12). In the case of a first-order irreversible reaction in a single CSTR, equation 8.3.21 becomes... 

The effect of nitrous acid on the nitration of mesitylene in acetic acid was also investigated. In solutions containing 5-7 mol 1 of nitric acid and < c. 0-014 mol of nitrous acid, the rate was independent of the concentration of the aromatic. As the concentration of nitrous acid was increased, the catalysed reaction intervened, and superimposed a first-order reaction on the zeroth-order one. The catalysed reaction could not be made sufficiently dominant to impose a truly first-order rate. Because the kinetic order was intermediate the importance of the catalysed reaction was gauged by following initial rates, and it was shown that in a solution containing 5-7 mol 1 of nitric acid and 0-5 mol 1 of nitrous acid, the catalysed reaction was initially twice as important as the general nitronium ion mechanism. 

The numerical solution of these equations is shown in Fig. 23-28. This is a plot of the enhancement fac tor E against the Hatta number, with several other parameters. The factor E represents an enhancement of the rate of transfer of A caused by the reaction compared with physical absorption with zero concentration of A in the liquid. The uppermost line on the upper right represents the pseudo-first-order reaction, for which E = P coth p. 

For a first-order reaction, m = I, the catalyst effectiveness T] is independent of A so that after elimination of A and A, the exphcit solution for the rate is... 

Scheme 10. Mechanislic possibililies for PF condensalion. Mechanism a involves an SN2-like attack of a phenolic ring on a methylol. This attack would be face-on. Such a mechanism is necessarily second-order. Mechanism b involves formation of a quinone methide intermediate and should be Hrst-order. The quinone methide should react with any nucleophile and should show ethers through both the phenolic and hydroxymethyl oxygens. Reaction c would not be likely in an alkaline solution and is probably illustrative of the mechanism for novolac condensation. The slow step should be formation of the benzyl carbocation. Therefore, this should be a first-order reaction also. Though carbocation formation responds to proton concentration, the effects of acidity will not usually be seen in the reaction kinetics in a given experiment because proton concentration will not vary.

For a first order reaction (-r ) = kC, and Equation 8-147 is then linear, has constant coefficients, and is homogeneous. The solution of Equation 8-147 subject to the boundary conditions of Danckwerts and Wehner and Wilhelm [23] for species A gives... 

Equations 8-148 and 8-149 give the fraction unreacted C /C o for a first order reaction in a closed axial dispersion system. The solution contains the two dimensionless parameters, Np and kf. The Peclet number controls the level of mixing in the system. If Np —> 0 (either small u or large [), diffusion becomes so important that the system acts as a perfect mixer. Therefore,... 

A third method, or phenomenon, capable of generating a pseudo reaction order is exemplified by a first-order solution reaction of a substance in the presence of its solid phase. Then if the dissolution rate of the solid is greater than the reaction rate of the dissolved solute, the solute concentration is maintained constant by the solubility equilibrium and the first-order reaction becomes a pseudo-zero-order reaction. 

Consecutive reactions involving one first-order reaction and one second-order reaction, or two second-order reactions, are very difficult problems. Chien has obtained closed-form integral solutions for many of the possible kinetic schemes, but the results are too complex for straightforward application of the equations. Chien recommends that the kineticist follow the concentration of the initial reactant A, and from this information rate constant k, can be estimated. Then families of curves plotted for the various kinetic schemes, making use of an abscissa scale that is a function of c kit, are compared with concentration-time data for an intermediate or product, seeking a match that will identify the kinetic scheme and possibly lead to additional rate constant estimates. 

Linear differential equations with constant coefficients can be solved by a mathematical technique called the Laplace transformation . Systems of zero-order or first-order reactions give rise to differential rate equations of this type, and the Laplaee transformation often provides a simple solution. 

Systems of reversible first-order reactions lead to sets of simultaneous linear differential equations with constant coefficients. A solution may be obtained by means of a matrix formulation that is widely used in quantum mechanics and vibrational... 

In solution arylpentazoles decompose spontaneously by a first-order reaction (see Section III), yielding arylazide and nitrogen quantitatively [Eq. (1)]. The stability of phenylpentazole in solution increases... 

Sucrose (Ci2H22On) hydrolyzes into glucose and fructose. The hydrolysis is a first-order reaction. The half-life for die hydrolysis of sucrose is 64.2 min at 25°C. How many grams of sucrose in 1.25 L of a 0.389 Af solution are hydrolyzed in 1.73 hours ... 

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... 

Westerterp et al. reported the first-order reaction rate constant with respect to oxygen concentration in a solution at 30°C containing 100 g of sodium sulfite per liter. The catalyst concentration was 0.001 g-mole/liter. They found that k is 37,000 sec 1 for the CoS04 catalyst and 9800 sec"1 for CuS04 catalyst. For the same sodium sulfite concentration but with copper sulfate concentration greater than 0.005 g-mole/liter, the reaction rate constant as a function of temperature is approximated by ... 

Danckwerts et al. (D6, R4, R5) recently used the absorption of COz in carbonate-bicarbonate buffer solutions containing arsenate as a catalyst in the study of absorption in packed column. The C02 undergoes a pseudo first-order reaction and the reaction rate constant is well defined. Consequently this reaction could prove to be a useful method for determining mass-transfer rates and evaluating the reliability of analytical approaches proposed for the prediction of mass transfer with simultaneous chemical reaction in gas-liquid dispersions. 

Emmert and Pigford (E2) have studied the reaction between carbon dioxide and aqueous solutions of monoethanolamine (MEA) and report that the reaction rate constant is 5400 liter/mole sec at 25°C. If it is assumed that MEA is present in excess, the reaction may be treated as pseudo first-order. This pseudo first-order reaction has been recently used by Johnson et al. (J4) to study the rate of absorption from single carbon dioxide bubbles under forced convection conditions, and the results were compared with their theoretical model. 

This peculiar form applies when a dimeric molecule dissociates to a reactive monomer that then undergoes a first-order or pseudo-first-order reaction. This scheme is considered in Section 4.3. Unless one can work at either of the limits, the form is such that a numerical solution or the method of initial rates will be needed, since the integrated equation has no solution for [A]r. 

Reversible reactions. Consider an experiment on the reversible first-order reaction A =i P in which two identical solutions were prepared at different times. The age separation between the two is denoted as t. The older solution is placed in the reference beam of a... 

This solution cannot be used for a first-order reaction where n = 1 because it is then indeterminate. 

A pure gas is absorbed into a liquid with which it reacts. The concentration in the liquid is sufficiently low for the mass transfer to be governed by Pick s law and the reaction is first order with respect to the solute gas. It may be assumed that the film theory may be applied to the liquid and that the concentration of solute gas falls from the saturation value to zero across the film. Obtain an expression for the mass transfer rate across the gas-liquid interface in terms of the molecular diffusivity, 1), the first order reaction rate constant k. the film thickness L and the concentration Cas of solute in a saturated solution. The reaction is initially carried our at 293 K. By what factor will the mass transfer rate across the interface change, if the temperature is raised to 313 K7... 

Pyruvic acid is an intermediate in the fermentation of grains. During fermentation the enzyme pyruvate carboxylase causes the pyruvate ion to release carbon dioxide. In one experiment a 200.-mL aqueous solution of the pyruvate in a sealed, rigid 500.-mL flask at 293 K had an initial concentration of 3.23 mmol-L -l. Because the concentration of the enzyme was kept constant, the reaction was pseudo-first order in pyruvate ion. The elimination of CU2 by the reaction was monitored by measuring the partial pressure of the C02 gas. The pressure of the gas was found to rise from zero to 100. Pa in 522 s. What is the rate constant of the pseudo-first order reaction ... 

Solution For the first-order reaction, a = —kdout = —A (0.1a ). Equation (1.54) gives... 

Equations (2.22) and (2.23) become indeterminate if ks = k. Special forms are needed for the analytical solution of a set of consecutive, first-order reactions whenever a rate constant is repeated. The derivation of the solution can be repeated for the special case or L Hospital s rule can be applied to the general solution. As a practical matter, identical rate constants are rare, except for multifunctional molecules where reactions at physically different but chemically similar sites can have the same rate constant. Polymerizations are an important example. Numerical solutions to the governing set of simultaneous ODEs have no difficulty with repeated rate constants, but such solutions can become computationally challenging when the rate constants differ greatly in magnitude. Table 2.1 provides a dramatic example of reactions that lead to stiff equations. A method for finding analytical approximations to stiff equations is described in the next section. 

Solution The first-order rate constant is 0.693/2.1=0.33 so that the fractional conversion for a first-order reaction will be 1 — exp(—0.227) where f is in seconds. The inlet and outlet pressures are known so Equation (3.27) can be used to And t given that [L/Mom ] = 57/9.96 = 5.72s. The result is f = 5.91 s, which is 3.4% higher than what would be expected if the entire reaction was at Pout- The conversion of the organic compound is 86 percent. 

Numerical calculations are the easiest way to determine the performance of CSTRs in series. Simply analyze them one at a time, beginning at the inlet. However, there is a neat analytical solution for the special case of first-order reactions. The outlet concentration from the nth reactor in the series of CSTRs is... 

Solution The component balance for component A (styrene) for a first-order reaction in a constant-volume, constant-density CSTR is... 

A solution to Equation (8.12) together with its boundary conditions gives a r, z) at every point in the reactor. An analytical solution is possible for the special case of a first-order reaction, but the resulting infinite series is cumbersome to evaluate. In practice, numerical methods are necessary. 

Solution For a first-order reaction, we can arbitrarily set = 1 so that the results can be interpreted as the fraction unreacted. The choices for 7 and J ... 

Repeat Example 8.1 and obtain an analytical solution for the case of first-order reaction and pressure-driven flow between flat plates. Feel free to use software for the S5anbolic manipulations, but do substantiate your results. 

Only numerical solutions are possible when Equation (9.24) is solved simultaneously with Equation (9.14). This is true even for first-order reactions because of the intractable nonlinearity of the Arrhenius temperature dependence. 

Example 9.4 Use forward shooting to solve Equation (9.15) for a first-order reaction with Pe = 16 and kt = 2. Compare the result with the analytical solution, Equation (9.20). 

In this study, the absorption rates of carbon dioxide into the solution of GMA and Aliquat 336 in such organic solvents as toluene, N-methyl-2-pirrolidinone(NMP), and dimethyl sulfoxide(DMSO) was measured to determine the pseudo-first-order reaction constant, which was used to obtain the elementary reaction rate constants. 

P with the pseudo-first-order reaction is expressed fix)m the analytic solution of Eq. (14) as follows ... 

The overall reaction between CO2 and GMA was assumed to consist of two elementary reactions such as a reversible reaction of GMA and catalyst to form an intermediate and an irreversible reaction of this intermediate and carbon dioxide to form five-membered cyclic carbonate. Absorption data for CO2 in the solution at 101.3 N/m were interpreted to obtain pseudo-first-order reaction rate constant, which was used to obtain the elementary reaction rate constants. The effects of the solubility parameter of solvent on lc2/k and IC3 were explained using the solvent polarity. 

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