First-order reactions number

For weU-defined reaction zones and irreversible, first-order reactions, the relative reaction and transport rates are expressed as the Hatta number, Ha (16). Ha equals (k- / l ) where k- = reaction rate constant, = molecular diffusivity of reactant, and k- = mass-transfer coefficient. Reaction... 

First-order and pseudo-first-order reactions are represented by the upper curve in Fig. 14-14. We note that for first-order reactions when the Hatta number is larger than about 3, the rate coefficient k can be computed by the formula... 

The second type of coalescence arises from the rupture of films between adjacent bubbles [Vrij and Overbeek, y. Am. Chem. Soc., 90, 3074 (1968)]. Its rate appears to follow first-order reaction kinetics with respect to the number of bubbles [New, Proc. 4th Int. Congr. Suif. Active Substances, Brussels, 1964, 2, 1167 (1967)] and to decrease with film thickness [Steiner, Hunkeler, and Hartland, Trans. In.st. Chem. Fng., 55, 153 (1977)]. Many factors are involved [Biker-man, Foams, Springer-Verlag, New York, 1973 and Akers (ed.). Foams, Academic, New York, 1976]. 

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. 

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,... 

Generalization of Scheme X to any number of consecutive irreversible first-order reactions is obviously possible, although the equations quickly become very cumbersome. However, Eqs. (3-42) and (3-44) reveal patterns in their form, and West-man and DeLury have developed a systematic symbolism that allows the equations to be written down without integration. 

Any combination of first-order reactions can be simulated by extension of this procedure. Reversible reactions add only the feature that reacted species can be regenerated from their products. Second-order reactions introduce a new factor, for now two molecules must each be independently selected in order that reaction occur in the real situation the two molecules are in independent motion, and their collision must take place to cause reaction. We load the appropriate numbers of molecules into each of two grids. Now randomly select from the first grid, and then, separately, randomly select from the second grid. If in both selections a molecule exists at the respective selected sites, then reaction occurs and both are crossed out if only one of the two selections results in selection of a molecule, no reaction occurs. (Of course, if pseudo-first-order conditions apply, a second-order reaction can be handled just as is a first-order reaction.)... 

From this expression, it is obvious that the rate is proportional to the concentration of A, and k is the proportionality constant, or rate constant, k has the units of (time) usually sec is a function of [A] to the first power, or, in the terminology of kinetics, v is first-order with respect to A. For an elementary reaction, the order for any reactant is given by its exponent in the rate equation. The number of molecules that must simultaneously interact is defined as the molecularity of the reaction. Thus, the simple elementary reaction of A P is a first-order reaction. Figure 14.4 portrays the course of a first-order reaction as a function of time. The rate of decay of a radioactive isotope, like or is a first-order reaction, as is an intramolecular rearrangement, such as A P. Both are unimolecular reactions (the molecularity equals 1). 

Strategy Nuclear decays are first-order reactions. Use the first-order rate calculation to find k. Part (b) differs from part (c) in that (b) relates concentration and time, while (c) relates concentration and rate. For nuclear decay, concentration can be expressed in moles, grams, or number of atoms. 

The number calculated in (b) for the concentration of H+ in blood, 4.0 X 10-8 Af, is very small. You may wonder what difference it makes whether [H+] is 4.0 X 10-8M,4.0 X 10-7Af, or some other such tiny quantity. In practice, it makes a great deal of difference because a large number of biological processes involve H+ as a reactant, so the rates of these processes depend on its concentration. If [H+] increases from 4.0 X 10-8M to 4.0 X 10-7M, the rate of a first-order reaction involving H+ increases by a factor of 10. Indeed, if [H+] in blood increases by a much smaller amount, from 4.0 X 10-8 Af to 5.0 X 10-8 M (pH 7.40----- 7.30),... 

An interesting method, which also makes use of the concentration data of reaction components measured in the course of a complex reaction and which yields the values of relative rate constants, was worked out by Wei and Prater (28). It is an elegant procedure for solving the kinetics of systems with an arbitrary number of reversible first-order reactions the cases with some irreversible steps can be solved as well (28-30). Despite its sophisticated mathematical procedure, it does not require excessive experimental measurements. The use of this method in heterogeneous catalysis is restricted to the cases which can be transformed to a system of first-order reactions, e.g. when from the rate equations it is possible to factor out a function which is common to all the equations, so that first-order kinetics results. 

Any sequence of first-order reactions can be solved analytically, although the algebra can become tedious if the number of reactions is large. The ODEs that correspond to Equation (2.20) are... 

This is a more general version of Equation (1.24). For a first-order reaction, the number of molecules of the reactive component decreases exponentially with time. This is true whether or not the density is constant. If the density happens to be constant, the concentration of the reactive component also decreases exponentially as in Equation (1.24). 

The Merrill and Hamrin criterion was derived for a first-order reaction. It should apply reasonably well to other simple reactions, but reactions exist that are quite sensitive to diffusion. Examples include the decomposition of free-radical initiators where a few initial events can cause a large number of propagation reactions, and coupling or cross-linking reactions where a few events can have a large effect on product properties. 

In the previous chapter we examined cellular automata simulations of first-order reactions. Because these reactions involved just transformations of individual ingredients, the simulations were relatively simple and straightforward to set up. Second-order cellular automata simulations require more instructions than do the first-order models described earlier. First of all, since movement is involved and ingredients can only move into vacant spaces on the grid, one must allow a suitable number of vacant cells on the grid for movement to take place in a sensible manner. For a gas-phase reaction one might wish to allow at least 5-10 vacant cells for each ingredient, so that on a 100 x 100 = 10,000... 

RT) and ks - 3.11.10 exp(-13639/RT) m. kmof. s. The value of ki, obtained in this research are almost the same as that obtained by Venugopal. Venugopal neglected the side reactions. The value of E and Hatta Number -/m were greater than 3, so that the reaction system can be considered as pseudo-first order reaction with respect to oxygen and the process was controlled by mass transfer aspect. 

The apparent reaction rate constant for the first order reaction, k, was calculated from the conversion of CO2. Since the gas-volume reduction rate increased with k, a poor fluidization was induced by high reaction rate. We investigated the effect of the rate of the gas-volume change on the fluidization quality. The rate of the gas-volume change can be defined as rc=EA(dxA/dt), where Sa is the increase in the number of moles when the reactants completely react per the initial number of moles. This parameter is given by 7-1. When the parameter, Ea, is negative, the gas volume decreases as the reaction proceeds. 

In order to derive specific numbers for the temperature rise, a first-order reaction was considered and Eqs. (10) and (11) were solved numerically for a constant-density fluid. In Figure 1.17 the results are presented in dimensionless form as a function of k/tjjg. The y-axis represents the temperature rise normalized by the adiabatic temperature rise, which is the increase in temperature that would have been observed without any heat transfer to the channel walls. The curves are differentiated by the activation temperature, defined as = EJR. As expected, the temperature rise approaches the adiabatic one for very small reaction time-scales. In the opposite case, the temperature rise approaches zero. For a non-zero activation temperature, the actual reaction time-scale is shorter than the one defined in Eq. (13), due to the temperature dependence of the exponential factor in Eq. (12). For this reason, a larger temperature rise is foimd when the activation temperature increases. 

Hatta number = (k DAlkuA) for first order reaction in the gaseous reactant and zero order in the liquid reactant... 

Da Second Damkohler number K l2 ID K = first-order reaction rate constant l = characteristic length D = diffusion coefficient... 

In Illustrations 8.3 and 8.6 we considered the reactor size requirements for the Diels-Alder reaction between 1,4-butadiene and methyl acrylate. For the conditions cited the reaction may be considered as a pseudo first-order reaction with 8a = 0. At a fraction conversion of 0.40 the required PFR volume was 33.5 m1 2 3, while the required CSTR volume was 43.7 m3. The ratio of these volumes is 1.30. From Figure 8.8 the ratio is seen to be identical with this value. Thus this figure or equation 8.3.14 can be used in solving a number of problems involving the... 

We use expression (26.12), substituting the disintegration rate for the number of atoms, since we recognize that in this first-order reaction the rate is directly proportional to the amount of reactant, that is, the number of atoms. (All radioactive decay processes follow... 

A large number of analytical solutions of these equations appear in the literature. Mostly, however, they deal only with first order reactions. All others require solution by numerical or other approximate means. In this book, solutions of two examples are carried along analytically part way in P7.02.06 and P7.02.07. Section 7.4 considers flow through an external film, while Section 7.5 deals with diffusion and reaction in catalyst pores under steady state conditions. 

For first order reaction in a porous slab this problem is solved in P7.03.16. Three dimensionless groups are involved in the representation of behavior when both external and internal diffusion are present, namely, the Thiele number, a Damkohler nunmber and a Biot number. Problem P7.03.16 also relates r)t to the common effectiveness based on the surface concentration,... 

A reagent in solution can enhance a mass transfer coefficient in comparison with that of purely physical absorption. The data of Tables 8.1 and 8.2 have been cited. One of the simpler cases that can be analyzed mathematically is that of a pseudo-first order reaction that goes to completion in a liquid film, problem P8.02.01. It appears that the enhancement depends on the specific rate of reaction, the diffusivity, the concentration of the reagent and physical mass transfer coefficient (MTC). These quantities occur in a group called the Hatta number,... 

The numerical solution of these equations is shown on the plot which is due to van Krevelen Hoftijzer (Trans Instn Chem Engrs 32 S360, 1954). The plot is of the enhancement factor E against the Hatta number (3 which is defined in P8.02.01. The parameters along the curves are of a ratio, a = CbLDb/CaLD0. The uppermost curve is for a first order reaction. 

The parameter [3 is related to the contrast. If (3A> > 1, equation 1 reduces to that of a simple first order reaction (such as CEL materials are usually assumed to follow (6)). If 3A< < 1, the reaction becomes second order in A In a similar manner, the sensitized reaction varies between zero order and first order. For the anthracene loadings required by the PIE process (13,15), A is close to 1M, so (3 > > 1 is required for first order unsensitized kinetics. Although in solution, 3 for DMA is -500, and -25 for DPA (20), we have found [3 =3 for DMA/PEMA, and (3=1 for DPA/PBMA. Thus although the chemical trends are in the same direction in the polymer as in solution, the numbers are quite different, indicating a substantial... 

A radioactive isotope may be unstable, but it is impossible to predict when a certain atom will decay. However, if we have a statistically large enough sample, some trends become obvious. The radioactive decay follows first-order kinetics (see Chapter 13 for a more in-depth discussion of first-order reactions). If we monitor the number of radioactive atoms in a sample, we observe that it takes a certain amount of time for half the sample to decay it takes the same amount of time for half the remaining sample to decay, and so on. The amount of time it takes for half the sample to decay is the half-life of the isotope and has the symbol t1/2. The table below shows the percentage of the radioactive isotope remaining versus half-life. 

We develop the idea using a kinetic example. Any reaction scheme that consists exclusively of first order reactions, results in concentration profiles that are linear combinations of exponentials. There is no limit to the number of reacting components nc. 

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