Kinetics errors

Samples from patients with multiple myeloma whose total protein is > 120 g/1 will yield enhanced AST values. Hence, these samples must be diluted with physiological saline solution or with 7% albumin solution 1 + 1. AST kinetic errors on the Ek-tachm was often found with patient having myeloma (EN135). 

EN134 Sullivan, M., Tang, M., Hayes, T. and Jessen, R. (1992). Dog and cat reference ranges on the Kodak Ektachem 700. Clin. Chem. 3S, 1073, Abstr. 591. EN135 Tang, M., Sullivan, M., Gibson, D., Truskolawski, C. and Jessen, R. (1992). Kinetic error on the Kodak Ektachem - A clue to unsuspected myeloma. Clin. Chem. 38, 1027, Abstr. 395. 

No kinetic errors Impurities must not cause significant detector signals... 

Figure 2 shows an idealized set of data for a radical clock study in which the clock reaction is reversible. The positive intercept is the indication of reversibility in the clock reaction. In this case, the rate constant for the forward reaction ( r) is twice as great as that for the reverse reaction (k R). The slope of the line from multiple experiments, shown as a solid line, will give an accurate ratio of rate constants (kTi/ka) = 5 M in this example. If a single experiment had been conducted at 0.2 M concentration of trapping agent, however, a line with an assumed intercept of zero would result in a considerable kinetic error. The result, shown as a dashed line in Fig. 2, gives an apparent value of (kn/kR) = 7.5 M . ... 

A kinetics text with a strong theoreticai bent that overviews transient kinetic methods and discusses data anaiysis issues such as error propagation and sensitivity anaiysis. 

Nitration at a rate independent of the concentration of the compound being nitrated had previously been observed in reactions in organic solvents ( 3.2.1). Such kinetics would be observed if the bulk reactivity of the aromatic towards the nitrating species exceeded that of water, and the measured rate would then be the rate of production of the nitrating species. The identification of the slow reaction with the formation of the nitronium ion followed from the fact that the initial rate under zeroth-order conditions was the same, to within experimental error, as the rate of 0-exchange in a similar solution. It was inferred that the exchange of oxygen occurred via heterolysis to the nitronium ion, and that it was the rate of this heterolysis which limited the rates of nitration of reactive aromatic compounds. 

Despite the variety of methods that had been developed, by 1960 kinetic methods were no longer in common use. The principal limitation to a broader acceptance of chemical kinetic methods was their greater susceptibility to errors from uncontrolled or poorly controlled variables, such as temperature and pH, and the presence of interferents that activate or inhibit catalytic reactions. Many of these limitations, however, were overcome during the 1960s, 1970s, and 1980s with the development of improved instrumentation and data analysis methods compensating for these errors. ... 

Miscellaneous Methods At the beginning of this section we noted that kinetic methods are susceptible to significant errors when experimental variables affecting the reaction s rate are difficult to control. Many variables, such as temperature, can be controlled with proper instrumentation. Other variables, such as interferents in the sample matrix, are more difficult to control and may lead to significant errors. Although not discussed in this text, direct-computation and curve-fitting methods have been developed that compensate for these sources of error. ... 

Until now we have been discussing the kinetics of catalyzed reactions. Losses due to volatility and side reactions also raise questions as to the validity of assuming a constant concentration of catalyst. Of course, one way of avoiding this issue is to omit an outside catalyst reactions involving carboxylic acids can be catalyzed by these compounds themselves. Experiments conducted under these conditions are informative in their own right and not merely as means of eliminating errors in the catalyzed case. As noted in connection with the discussion of reaction (5.G), the intermediate is stabilized by coordination with a proton from the catalyst. In the case of autoprotolysis by the carboxylic acid reactant, the rate-determining step is probably the slow reaction of intermediate [1] ... 

Nonetheless, these methods only estimate organ-averaged radiation dose. Any process which results in high concentrations of radioactivity in organs outside the MIRD tables or in very small volumes within an organ can result in significant error. In addition, the kinetic behavior of materials in the body can have a dramatic effect on radiation dose and models of material transport are constandy refined. Thus radiation dosimetry remains an area of significant research activity. 

The Cannon-Fenske viscometer (Fig. 24b) is excellent for general use. A long capillary and small upper reservoir result in a small kinetic energy correction the large diameter of the lower reservoir minimises head errors. Because the upper and lower bulbs He on the same vertical axis, variations in the head are minimal even if the viscometer is used in positions that are not perfecdy vertical. A reverse-flow Cannon-Fen ske viscometer is used for opaque hquids. In this type of viscometer the Hquid flows upward past the timing marks, rather than downward as in the normal direct-flow instmment. Thus the position of the meniscus is not obscured by the film of Hquid on the glass wall. 

Mechanism. The thermal cracking of hydrocarbons proceeds via a free-radical mechanism (20). Siace that discovery, many reaction schemes have been proposed for various hydrocarbon feeds (21—24). Siace radicals are neutral species with a short life, their concentrations under reaction conditions are extremely small. Therefore, the iategration of continuity equations involving radical and molecular species requires special iategration algorithms (25). An approximate method known as pseudo steady-state approximation has been used ia chemical kinetics for many years (26,27). The errors associated with various approximations ia predicting the product distribution have been given (28). 

Cropley, J.B., Systematic Errors in Recycle Reactor Kinetic Studies, Chemical Engineeiing Piogiess, February 1987, 46-51. (Model building, experimental design)... 

Phillips, A.G. and D.P. Harrison, Gross Error Detection and Data Reconciliation in Experimental Kinetics, Indushial and Engineeiing Chemistiy Reseaieh, 32, 1993,2530-2536. (Measurement test)... 

The second classification is the physical model. Examples are the rigorous modiiles found in chemical-process simulators. In sequential modular simulators, distillation and kinetic reactors are two important examples. Compared to relational models, physical models purport to represent the ac tual material, energy, equilibrium, and rate processes present in the unit. They rarely, however, include any equipment constraints as part of the model. Despite their complexity, adjustable parameters oearing some relation to theoiy (e.g., tray efficiency) are required such that the output is properly related to the input and specifications. These modds provide more accurate predictions of output based on input and specifications. However, the interactions between the model parameters and database parameters compromise the relationships between input and output. The nonlinearities of equipment performance are not included and, consequently, significant extrapolations result in large errors. Despite their greater complexity, they should be considered to be approximate as well. 

Verneuil et al. (Verneuil, V.S., P. Yan, and F. Madron, Banish Bad Plant Data, Chemical Engineering Progress, October 1992, 45-51) emphasize the importance of proper model development. Systematic errors result not only from the measurements but also from the model used to analyze the measurements. Advanced methods of measurement processing will not substitute for accurate measurements. If highly nonlinear models (e.g., Cropley s kinetic model or typical distillation models) are used to analyze unit measurements and estimate parameters, the Hkelihood for arriving at erroneous models increases. Consequently, resultant models should be treated as approximations. 

The velocity propagation is subject to relatively large errors, on the order O(At-). Recall that an accurate estimate of the velocity is required for the kinetic energy evaluations. An added inconvenience is that v can be computed only if r +i is already known. 

If the UCKRON expression is simplified to the form recommended for reactions controlled by adsorption of reactant, and if the original true coefficients are used, it results in about a 40% error. If the coefficients are selected by a least squares approach the approximation improves significantly, and the numerical values lose their theoretical significance. In conclusion, formalities of classical kinetics are useful to retain the basic character of kinetics, but the best fitting coefficients have no theoretical significance. 

For a sequenee of reaetion steps two more eoneepts will be used in kinetics, besides the previous rules for single reaetions. One is the steady-state approximation and the seeond is the rate limiting step eoneept. These two are in strict sense incompatible, yet assumption of both causes little error. Both were explained on Figure 6.1.1 Boudart (1968) credits Kenzi Tamaru with the graphical representation of reaction sequences. Here this will be used quantitatively on a logarithmic scale. 

Five percent random error was added to the error-free dataset to make the simulation more realistic. Data for kinetic analysis are presented in Table 6.4.3 (Berty 1989), and were given to the participants to develop a kinetic model for design purposes. For a more practical comparison, participants were asked to simulate the performance of a well defined shell and tube reactor of industrial size at well defined process conditions. Participants came from 8 countries and a total of 19 working groups. Some submitted more than one model. The explicit models are listed in loc.cit. and here only those results that can be graphically presented are given. 

Figure 6.4.2 Table of error-free kinetic data from CSTR simulation.

Figure 6.4.3 Data for kinetic analysis. Simulated CSTR results with random error added to UCKRON-I.

To facilitate the use of methanol synthesis in examples, the UCKRON and VEKRON test problems (Berty et al 1989, Arva and Szeifert 1989) will be applied. In the development of the test problem, methanol synthesis served as an example. The physical properties, thermodynamic conditions, technology and average rate of reaction were taken from the literature of methanol synthesis. For the kinetics, however, an artificial mechanism was created that had a known and rigorous mathematical solution. It was fundamentally important to create a fixed basis of comparison with various approximate mathematical models for kinetics. These were derived by simulated experiments from the test problems with added random error. See Appendix A and B, Berty et al, 1989. 

In addition to possible errors due to the steps in the kinetic mechanisms, there may be errors in the rate constants due to the smog chamber data... 

Casado et al. have analyzed the error of estimating the initial rate from a tangent to the concentration-time curve at t = 0 and conclude that the error is unimportant if the extent of reaction is less than 5%. Chandler et al. ° fit the kinetic data to a polynomial in time to obtain initial rate estimates. 

The relative fluctuations in Monte Carlo simulations are of the order of magnitude where N is the total number of molecules in the simulation. The observed error in kinetic simulations is about 1-2% when lO molecules are used. In the computer calculations described by Schaad, the grids of the technique shown here are replaced by computer memory, so the capacity of the memory is one limit on the maximum number of molecules. Other programs for stochastic simulation make use of different routes of calculation, and the number of molecules is not a limitation. Enzyme kinetics and very complex oscillatory reactions have been modeled. These simulations are valuable for establishing whether a postulated kinetic scheme is reasonable, for examining the appearance of extrema or induction periods, applicability of the steady-state approximation, and so on. Even the manual method is useful for such purposes. 

A more serious problem is that we lose all kinetic information about the system until the data collection begins, and ultimately this limits the rates that can be studied. For first-order reactions we may be able to sacrifice the data contained in the first one, two, or three half-lives, provided the system amplitude is adequate that is, the remaining extent of reaction must be quantitatively detectable. However, this practice of basing kinetic analyses on the last few percentage of reaction is subject to error from unknown side reactions or analytical difficulties. 

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