Reaction rate constant time dependence

A. P. J. Jansen. Monte Carlo simulation of chemical reactions on a surface with time-dependent reaction-rate constants. Comp Phys Commun 56 1-12, 1995. 

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... 

Every reaction has its own characteristic rate constant that depends on the intrinsic speed of that particular reaction. For example, the value of k in the rate law for NO2 decomposition is different from the value of k for the reaction of O3 with NO. Rate constants are independent of concentration and time, but as we discuss in Section 15-1. rate constants are sensitive to temperature. 

Specific interface in gas/liquid systems Mass-transfer coefficient Time-dependent dispersion coefficient Knudscn number Reaction rate constant... 

In general, the potential dependence of the current is determined by both the potential dependence of the concentrations of the reacting particles near the electrode surface and the potential dependence of the reaction rate constant itself (i.e., the probability of the elementary reaction act per unit time, W). 

The extraction system which was measured by the HSS method for the first time was the extraction kinetics of Ni(II) and Zn(II) with -alkyl substituted dithizone (HL) [14]. The observed extraction rate constants linearly depended on both concentrations of the metal ion [M j and the dissociated form of the ligand [L j. This seemed to suggest that the rate determining reaction was the aqueous phase complexation which formed a 1 1 complex. However, the observed extraction rate constant k was not decreased with the distribution constant Kj of the ligands as expected from the aqueous phase mechanism. 

Obviously the curve depicting the time-dependent behavior of the concentration of species C can take on even more forms than that for species B. The shape of the curve is dependent on the initial concentrations of the various species and the three reaction rate constants. Figure 5.3 depicts the time-dependent behavior for the specific case where only species A is present initially. 

For non-linear chemical reactions that are fast compared with the local micromixing time, the species concentrations in fluid elements located in the same zone cannot be assumed to be identical (Toor 1962 Toor 1969 Toor and Singh 1973 Amerja etal. 1976). The canonical example is a non-premixed acid-base reaction for which the reaction rate constant is essentially infinite. As a result of the infinitely fast reaction, a fluid element can contain either acid or base, but not both. Due to the chemical reaction, the local fluid-element concentrations will therefore be different depending on their stoichiometric excess of acid or base. Micromixing will then determine the rate at which acid and base are transferred between fluid elements, and thus will determine the mean rate of the chemical reaction. 

Chemical Reaction Rate Controlled Process If the diffusion is very rapid compared to the rate of chemical reaction, then the concentration of water and EG can be considered to be nearly zero throughout the pellet and the rate of the reverse reaction can be neglected [21], This represents the maximum possible reaction rate. It is characterized by a linear molecular weight increase with respect to time and is also dependent on the starting molecular weight and the reaction rate constants ki and k2. 

In summary, because the forward reaction rate constant is similar to the back reaction rate constant, the concentration evolution of a second-order isotopic exchange reaction often reduces to that of a first-order reaction (exponential evolution) but the rate "constants" and mean reaction time for the reduced reaction depend on total concentrations. 

The above models describe a simplified situation of stationary fixed chain ends. On the other hand, the characteristic rearrangement times of the chain carrying functional groups are smaller than the duration of the chemical reaction. Actually, in the rubbery state the network sites are characterized by a low but finite molecular mobility, i.e. R in Eq. (20) and, hence, the effective bimolecular rate constant is a function of the relaxation time of the network sites. On the other hand, the movement of the free chain end is limited and depends on the crosslinking density 82 84). An approach to the solution of this problem has been outlined elsewhere by use of computer-assisted modelling 851 Analytical estimation of the diffusion factor contribution to the reaction rate constant of the functional groups indicates that K 1/x, where t is the characteristic diffusion time of the terminal functional groups 86. ... 

In open, or flow, reactors chemical equilibrium need never be approached. The reaction is kept away from that state by the continuous inflow of fresh reactants and a matching outflow of product/reactant mixture. The reaction achieves a stationary state , where the rates at which all the participating species are being produced are exactly matched by their net inflow or outflow. This stationary-state composition will depend on the reaction rate constants, the inflow concentrations of all the species, and the average time a molecule spends in the reactor—the mean residence time or its inverse, the flow rate. Any oscillatory behaviour may now, under appropriate operating conditions, be sustained indefinitely, becoming a stable response even in the strictest mathematical sense. 

The traces in Fig. 3.9 were computed for a system with an uncatalysed reaction rate constant such that jcu > g, and hence there are no oscillatory responses in the corresponding pool chemical equations. For ku < we may also ask about the (time-dependent) local stability of the pseudo-stationary state. The concentration histories may become unstable to small perturbations for a limited time period. For sufficiently small e this should occur whilst the group p0e cr lies within the range... 

As an interesting fact, we can learn from Eq. 12-21 that the time to steady-state (or time to equilibrium) depends on the sum of the forward and reverse reaction rate constants. Thus, even if one rate constant is very small, time to equilibrium can be small, provided that the other rate constant is large. By using Eq. 4 in Box 12.1 (95% of equilibrium reached) we obtain ... 

The production of species i (number of moles per unit volume and time) is the velocity of reaction,. In the same sense, one understands the molar flux, jh of particles / per unit cross section and unit time. In a linear theory, the rate and the deviation from equilibrium are proportional to each other. The factors of proportionality are called reaction rate constants and transport coefficients respectively. They are state properties and thus depend only on the (local) thermodynamic state variables and not on their derivatives. They can be rationalized by crystal dynamics and atomic kinetics with the help of statistical theories. Irreversible thermodynamics is the theory of the rates of chemical processes in both spatially homogeneous systems (homogeneous reactions) and inhomogeneous systems (transport processes). If transport processes occur in multiphase systems, one is dealing with heterogeneous reactions. Heterogeneous systems stop reacting once one or more of the reactants are consumed and the systems became nonvariant. 

Spin-spin relaxation dynamics were also used in the study of the kinetics of the vulcanization of polysulphide rubbers. The T2 values decrease with the course of the reaction and the time dependence of log (T2/T ), where corresponds to the time equal to zero, exhibits an inflection. The inflection point is attributed to gel formation, and the reaction rate constants for the two separate processes are determined from the T2 data. It was also observed that the addition of carbon black reduces T2 by a factor of 2 or 3, because vulcanization occurs both through the thiol groups and by the chemical reaction between the polymer and carbon black 37>. 

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