First order reaction, pseudo

First-Order or Pseudo-First-Order Reaction in a Liquid Film. 23-42 

FIRST-ORDER OR PSEUDO-FIRST-ORDER REACTION IN A LIQUID FILM 

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 

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

FIGURE 11.7 A pseudo-first-order reaction in one phase with reactant supplied from the other phase. See Example 11.10. 

One of the typical features of a (pseudo)-first order reaction is that a plot of the logarithm of the advancement of the reaction versus time (Fig. 2B) should give straight lines. However we observed deviation from linearity before the first half-life, in spite of the fact that another characteristic features of (pseudo)-first order reactions, namely that plots of the extent of reaction versus time were independant of the initial concentration (Fig. 3), was verified. We therefore investigated whether variation occured in the reaction conditions as a function of time. 

The mass balance of species A with a pseudo-first-order reaction is 

We know from equation 13.6 that for a pseudo-first-order reaction, the concentration of picrate at time t is 

Consider a reaction scheme consisting of a sequence of two first-order (or pseudo-first-order) reactions in which intermediate I builds up and later falls. 

Within the strictly chemical realm, sequences of pseudo-first-order reactions are quite common. The usually cited examples are hydrations carried out in water and slow oxidations carried out in air, where one of the reactants 

The reaction/mass-transfer technique is based on Danckwerts theory of mass transfer accompanied by a fast pseudo first-order reaction (10)  

Use of the isolation or pseudo-order technique. This approach is discussed in Chapter 2, where it was shown how a second-order reaction could be converted to a pseudo-first-order reaction by maintaining one of the reactant concentrations at an essentially eonstant level. The same method may be usefully applied to eomplex reactions. In this way, for example. Scheme XI can be studied under conditions such that it functions as Scheme IX. A corollary that must be kept in mind is that a reaction system that is observed to behave in accordance with (as an example) Scheme IX may actually be more complex than it appears to be, if an unsuspected reactant is present under pseudo-order conditions. 

Fig. 2 shows the plot of ln[(CEcVCEc] vs. time during first 2 h. Quite good straight lines were obtained, and the pseudo first-order reaction rate constants for 120,130 and 140 °C were 0.002421, 0.002481 and 0.002545 h, respectively. From the Arrhenius plot of the first order reaction rate constants, one can estimate the activation energy as 41.5 kJ/mol. 

Example 11.12 Solve Equations (11.31) and (11.32) for the simple case of constant parameters and a pseudo-first-order reaction occurring in the liquid phase of a component supplied from the gas phase. The gas-phase film resistance is negligible. The inlet concentration of the reactive component is 

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. 

P can not be obtained because the reaction rate constants such as ki, kj, and kj are unknown. Therefore, these constants are obtained using the pseudo-first-order reaction methods as following procedures. 

Equation 13.14 shows how [A]o is determined for a two-point fixed-time integral method in which the concentration of A for the pseudo-first-order reaction 

GL 16] [R 12] [P 15] As excess of cyclohexene was used, the kinetics were zero order for this species concentration and first order with respect to hydrogen [11]. For this pseudo-first-order reaction, a volumetric rate constant of 16 s was determined, considering the catalyst surface area of 0.57 m g and the catalyst loading density of1g cm.  

Example 5.5 Ingredients are quickly charged to a jacketed batch reactor at an initial temperature of 25°C. The jacket temperature is 80°C. A pseudo-first-order reaction occurs. Determine the reaction temperature and the fraction unreacted as a function of time. The following data are available  

Example 11.10 Determine phase concentrations for a liquid-liquid reaction in a packed-bed reactor. The reactive component is dilute in both phases. It enters the reactor in one phase but undergoes a pseudo-first-order reaction in the other phase. All parameters are constant. 

Example 5.7 A CSTR is commonly used for the bulk pol5anerization of styrene. Assume a mean residence time of 2 h, cold monomer feed (300 K), adiabatic operation UAgxt = ), and a pseudo-first-order reaction with rate constant 

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. 

In the case of 0-pipettes, the collection efficiency also decreases markedly with increasing separation. The situation becomes more complicated when the transferred ion participates in a homogeneous chemical reaction. For the pseudo-first-order reaction a semiquantita-tive description is given by the family of dimensionless working curves calculated for two disks (Fig. 6) [23]. Clearly, at any separation distance the collection efficiency approaches zero when the dimensionless rate constant (a = 2kr /D, where k is the first-order rate constant of the homogeneous ionic reaction) becomes 1. 

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. 

The demetalation kinetics of ZnTTP by an acidic aqueous phase have also been reported [61]. In this study, ZnTTP was considered to adsorb at the interface producing Zn and free base porphyrin by proton attack. The demetalation kinetics of ZnTTP were analyzed as a pseudo-first-order reaction, because the proton concentration in the aqueous phase was in large excess. The rate law was found to be described by 

A parameter such as a rate constant is usually obtained as a consequence of various arithmetic manipulations, and in order to estimate the uncertainly (error) in the parameter we must know how this error is related to the uncertainties in the quantities that contribute to the parameter. For example, Eq. (2-33) for a pseudo-first-order reaction defines k, which can be determined by a semilogarithmic plot according to Eq. (2-6). By a method to be described later in this section the uncertainty in itobs (expressed as its variance associated with cb. Thus, we need to know how the errors in fcobs and cb are propagated into the rate constant k. 

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. 

In a curve-fitting method the concentration of a reactant or product is monitored continuously as a function of time, and a regression analysis is used to fit an appropriate differential or integral rate equation to the data. Eor example, the initial concentration of analyte for a pseudo-first-order reaction, in which the concentration of a product is followed as a function of time, can be determined by fitting a rearranged form of equation 13.12 

Fixed-time integral methods are advantageous for systems in which the signal is a linear function of concentration. In this case it is not necessary to determine the concentration of the analyte or product at times ti or f2, because the relevant concentration terms can be replaced by the appropriate signal. For example, when a pseudo-first-order reaction is followed spectrophotometrically, when Beer s law 

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. 

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  

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