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Identifiability estimation problem, compared

Consecutive reactions involving one first-order reaction and one second-order reaction, or two second-order reactions, are very difficult problems. Chien has obtained closed-form integral solutions for many of the possible kinetic schemes, but the results are too complex for straightforward application of the equations. Chien recommends that the kineticist follow the concentration of the initial reactant A, and from this information rate constant k, can be estimated. Then families of curves plotted for the various kinetic schemes, making use of an abscissa scale that is a function of c kit, are compared with concentration-time data for an intermediate or product, seeking a match that will identify the kinetic scheme and possibly lead to additional rate constant estimates. [Pg.75]

For multiplex measurements, when compared to fluorescence, SERRS also offers significant advantages. In multiplex measurements fluorescence has the disadvantage that the electronic spectra produced are broad (typically 50 to lOOnm full width at half maximum) and therefore overlap so that the technique is limited to the simultaneous measurement of around four dye labels [69, 77]. In contrast, SERRS uses the vibrational Raman spectrum of the label as a spectroscopic molecular fingerprint As a result the information content of the spectra is much higher and, because the vibrational bands are much narrower (about 1 nm full width at half maximum), spectral overlap is much less of a problem. Thus using SERRS it is possible to readily identify the components of a mixture without extensive separation procedures [78] and it has been estimated in the literature that simultaneous measurement with up to 30 SE(R)RS labels should be possible [79]. [Pg.278]

TLD uses multiple standards instead of one as in RAFA. The algorithm is similar to RAFA in that an eigenvalue problem is determined and solved through the use of singular-value decomposition. One important result of using second-order approaches such as RAFA and TLD is that the results of singular-value decomposition give estimates of the pure component response patterns which can be compared to the true response patterns. This ability allows users to check the performance of the procedure and identify components in the sample. [Pg.314]

There are three types of statistical problems in the light bulb example. One is identifying the shape of the failure distributions. Are they really the normal distribution as conjectured Another is to estimate such parameters as the average and the deviation from the average for the populations. Still another is to compare the old manufacturing process with the new. Is there a real difference and is the difference significant ... [Pg.2258]

If such direction cannot be identified (or if the direction does not exist at all), LS still provides correct estimates but at higher numerical costs (comparable to MCS). This is the case for structural reliability problems involving strong non linearities (Pradlwarter et al. 2007). [Pg.19]

The techniques are based on probabilities which many people find difficult to understand. In essence, the fact that an accident happens does not mean that the risk assessment was incorrect. For example, if it is correctly calculated that there is a very low likelihood of a multiple fatality, the fact that the multiple fatality occurs does not necessarily mean that the estimate of likelihood was incorrect. Rather, it is the third of the factors listed above, i.e. the operation of chance. Whaf is required in the longer term are numerical techniques for risk assessment which identify the xmderlying level of risk and fhe exfenf to which risk control measures will reduce the risk. It will then be possible to predict the number of accidents and incidents that will occur by chance and this can be compared with the numbers of accidenfs and incidents that do occur. It may then also be possible, by examining the accident and incident data in more detail, to determine whether any problems are due to an xmderestimate of fhe underl5ung level of risk or a failure to select or implement appropriate risk control measures. These are discussed by Boyle. ... [Pg.296]


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See also in sourсe #XX -- [ Pg.40 , Pg.311 ]




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