Reaction kinetics homogeneous liquid

The concentrations of reactants are of little significance in the theoretical treatment of the kinetics of solid phase reactions, since this parameter does not usually vary in a manner which is readily related to changes in the quantity of undecomposed reactant remaining. The inhomogeneity inherent in solid state rate processes makes it necessary to consider always both numbers and local spatial distributions of the participants in a chemical change, rather than the total numbers present in the volume of reactant studied. This is in sharp contrast with methods used to analyse rate data for homogeneous reactions in the liquid or gas phases. 

Homogeneous liquid phase inorganic oscillatory reactions. D. O. Cooke, Prog. React. Kinet., 1978, 8,185-229(184). 

Table 5.4-3 summarizes the design equations and analytical relations between concentration, C/(, and batch time, t, or residence time, t, for a homogeneous reaction A —> products with simple reaction kinetics (Van Santen etal., 1999). Balance equations for multicomponent homogeneous systems for any reaction network and for gas-liquid and gas-liquid-solid systems are presented in Tables 5.4-7 and 5.4.8 at the end of Section 5.4.3. 

Romanainen, J.J and Salmi T (1992) The Effect of Reaction Kinetics, Mass Transfer and Flow Pattern on Noncatalytic and Homogeneously Catalyzed Gas-Liquid Reactions in Bubble Columns, Chem Eng Sci, 47 2493. 

A reaction occurring at an interface of two phases. Some heterogeneous processes also display homogeneous aspects for example, a particular reaction may occur in only one of the system s phases (e.g., the rapid dissolution of a gas into a liquid followed by a particular reaction). See Fractal Reaction Kinetics... 

A brief reading of the literature would indicate that the liquid-phase reaction is what is technically known as an absorption with fast reaction and that gaseous CO2 physically dissolves in the liquid phase and reacts in a region close to the gas—liquid interface with dissolved NH3, according to second order in ammonia, first order in CO2 homogeneous liquid-phase kinetics... 

Evidence in support of a carbonium ion type of mechanism for low temperature polymerization was also obtained in an investigation of the kinetics of the homogeneous liquid phase polymerization of propene in the presence of aluminum bromide and hydrogen bromide at about —78° (Fontana and Kidder, 89). The rate of reaction is approximately proportional to the concentration of the promoter, no polymerization occurring in its absence. During the main portion of the reaction, the rate is independent of the monomer concentration toward the end, it decreases, due apparently to the low-concentration of the monomer, addition of more olefin resulting in an increase in the rate. It was concluded that the reaction involves an active complex, which may be regarded as a carbonium ion coupled with an anion ... 

The kinetics of a homogeneous liquid reaction are studied in a flow reactor, and to approximate plug flow the 48-cm long reactor is packed with 5-mm nonporous pellets. If the conversion is 99% for a mean residence time of 1 sec, calculate the rate constant for the first-order reaction... 

As an alternative to investigating the kinetics of a gas-liquid reaction on a laboratory scale, the mass transfer resistance may be minimised or eliminated so that the measured rate corresponds to the rate of the homogeneous liquid-phase reaction. This method of approach will be considered after first describing those reactors giving rise to controlled surface exposure times. 

The rate-based models usually use the two-film theory and comprise the material and energy balances of a differential element of the two-phase volume in the packing (148). The classical two-film model shown in Figure 13 is extended here to consider the catalyst phase (Figure 33). A pseudo-homogeneous approach is chosen for the catalyzed reaction (see also Section 2.1), and the corresponding overall reaction kinetics is determined by fixed-bed experiments (34). This macroscopic kinetics includes the influence of the liquid distribution and mass transfer resistances at the liquid-solid interface as well as dififusional transport phenomena inside the porous catalyst. 

In rate-based multistage separation models, separate balance equations are written for each distinct phase, and mass and heat transfer resistances are considered according to the two-film theory with explicit calculation of interfacial fluxes and film discretization for non-homogeneous film layer. The film model equations are combined with relevant diffusion and reaction kinetics and account for the specific features of electrolyte solution chemistry, electrolyte thermodynamics, and electroneutrality in the liquid phase. 

Floyd, T.M., Schmidt, M.A., Jensen, K.F., A silicon microchip for infrared transmission kinetics studies of rapid homogeneous liquid reactions. Micro Total Analysis Systems, Proceedings 5th TTAS Symposium, Monterey, CA, Oct. 21-25,2001, 277-279. 

SECM is a powerful tool for studying structures and heterogeneous processes on the micrometer and nanometer scale [8], It can probe electron, ion, and molecule transfers, and other reactions at solid-liquid, liquid-liquid, and liquid-air interfaces [9]. This versatility allows for the investigation of a wide variety of processes, from metal corrosion to adsorption to membrane transport, as discussed below. Other physicochemical applications of this method include measurements of fast homogeneous kinetics in solution and electrocatalytic processes, and characterization of redox processes in biological cells. 

Section 7 of this Handbook presents the theory of reaction kinetics that deals with homogeneous reactions in batch and continuous equipment. Single-phase reactors typically contain a liquid or a gas with (or without) a homogeneous catalyst that is processed in a reactor at conditions required to complete the desired chemical transformation. 

In the above Da denotes the Damkohler number as the ratio of the characteristic process time H/V to the characteristic reaction time l/r0. The reaction rate r0 is a reference value at the system pressure and an arbitrary reference temperature, as the lowest or the highest boiling point. For catalytic reactions r0 includes a reference value of the catalyst amount. R is the dimensionless reaction rate R = r/r0. The kinetics of a homogeneous liquid-phase reaction is described in general as function of activities ... 

The holdups can play an important role in the reactor performance. For example, in a pilot-scale trickle-bed reactor, the liquid holdup can play an important role in changing the nature of the apparent kinetics of the reaction. When homogeneous and catalytic reactions occur simultaneously, the liquid holdup plays an important role in determining the relative rates of homogeneous and catalytic reactions. In a three-phase fluidized-bed reactor, the holdup of the solid phase plays an important role in the reaction rate, particularly when the solid phase is a reactant. The gas holdup, of course, always plays an important role in reactor performance when a gaseous reactant takes part in the reaction. 

In order to be able to represent the behaviour of fluidized bed reactors with confidence, one must have a thorough understanding of the bed hydrodynamics and of the reaction kinetics. Almost all of the reactions carried out in fluidized beds are either solid-catalysed gas phase reactions or gas-solid reactions. (We will not consider here homogeneous gas phase reactions, reactions in liquid fluidized beds or reactions in three phase fluidized beds.) While the chemical kinetics can often be highly complex. 

The microwave-detection method has been developed [141] for the study of ionic species and their reactions in nonpolar liquids on a nanosecond timescale, and relies on the fact that microwaves are attenuated in weakly conducting media. It is very useful, for example, for the study of geminate recombination of radical ions in liquid hydrocarbons. It is also more suitable than either optical or D.C. conductivity methods for the study of homogeneous ion recombination processes where problems in data analysis can arise from underlying absorptions and distortion of the kinetics due to separation of the ions, respectively. 

The rate of liquid-phase chemical reactions involving transfer of reactants from another phase depends on the homogeneous liquid-phase kinetics, physical mass transfer rates of reactants, and their thermodynamic equilibria at the phase boundaries. The interaction among these phenomena produces four distinct types of behavior depending on chemical reaction velocity. These will be examined in this paper. 

The analytical problems associated with differential reactors can be overcome by the use of the recirculation reactor. A simplified form, called a Schwab reactor, is described by Weisz and Prater . Boreskov.and other Russian workers have described a number of other modifications " . The recirculation reactor is equivalent kinetically to the well-stirred continuous reactor or backmix reactor , which is widely used for homogeneous liquid phase reactions. Fig. 28 illustrates the principle of this system. The reactor consists of a loop containing a volume of catalyst V and a circulating pump which can recycle gas at a much higher rate, G, than the constant feed and, withdrawal rates F. 

To simulate the effects of reaction kinetics, mass transfer, and flow pattern on homogeneously catalyzed gas-liquid reactions, a bubble column model is described [29, 30], Numerical solutions for the description of mass transfer accompanied by single or parallel reversible chemical reactions are known [31]. Engineering aspects of dispersion, mass transfer, and chemical reaction in multiphase contactors [32], and detailed analyses of the reaction kinetics of some new homogeneously catalyzed reactions have been recently presented, for instance, for polybutadiene functionalization by hydroformylation in the liquid phase [33], car-bonylation of 1,4-butanediol diacetate [34] and hydrogenation of cw-1,4-polybutadiene and acrylonitrile-butadiene copolymers, respectively [10], which can be used to develop design equations for different reactors. 

The kinetics of partial oxidation, ATR, and dry reforming of liquid hydrocarbons have also been reported recently.103,155 Pacheco et al.155 developed and validated a pseudo-homogeneous mathematical model for the ATR of isooctane and the subsequent WGS reaction, based on the reaction kinetics and intraparticle mass transfer resistance. They regressed the kinetic expressions from the literature for partial oxidation and steam reforming reactions to determine the kinetics parameters for the ATR of isooctane on Pt/ceria catalyst. The rate expressions used in the reformer modeling and the parameters of these rate expressions are given in Tables 2.19 and 2.20, respectively. 

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