Calibration method development

To estimate the calibration method developed in this chapter, calibrations were performed for the following four cases. 

A development project has been initiated with the aim of providing a radiotracer method that ultimately can be implemented as a routine calibration method for permanently installed multiphase flowmeters. The project is supported by a research grant from the Danish Ministry of Energy. 

The CHI can be obtained without preliminary method development direcdy from a single fast-gradient run with a cycle time less than 15 min with a 150-mm column [40] or 5 min with 50-mm column [42]. In this case, the obtained retention time, tr, is expressed within an organic phase concentration (< o) scale using a calibration set of compounds. CHI value can be obtained from ... 

The use of reference samples for method calibration and development/validation occurred hand-in-hand with the development of all modern instrumental methods of analysis. In fact, the two developments are intimately linked with one another. As already noted, G-i and W-i (Fairbaim et al. 1951 Stevens i960) illustrate first instance of reference samples specifically developed for calibration purposes. Following that, the use of BCR-i as a reference sample throughout the lunar program (Science 1970) is a prime illustration of the quality assurance and method validation applications in large-scale inter-laboratory measurement programs. 

Standards should be analyzed contemporaneously for both determinative and confirmatory procedures. The method developer needs to describe fully the preparation of all the standards and the calibration procedure to be used, such as calibration prior to sample analysis, interspersed standards, or bracketing standards (confirmatory only). 

For the extraction of rubber and rubber compounds a wide variety of solvents (ethyl acetate, acetone, toluene, chloroform, carbon tetrachloride, hexane) have been used [149]. Soxtec extraction has also been used for HDPE/(Tinuvin 770, Chimassorb 944) [114] and has been compared to ultrasonic extraction, room temperature diffusion, dissolution/precipitation and reflux extraction. The relatively poor performance of the Soxtec extraction (50% after 4h in DCM) as compared with the reflux extraction (95% after 2-4 h in toluene at 60 °C) was described to the large difference in temperature between the boiling solvents. Soxtec was also used to extract oil finish from synthetic polymer yam (calibration set range of 0.18-0.33 %, standard error 0.015 %) as reference data for NIRS method development [150]. 

The attached worksheet from MathCad ( 1986-2001 MathSoft Engineering Education, Inc., 101 Main Street Cambridge, MA 02142-1521) is used for computing the statistical parameters and graphics discussed in Chapters 58 through 61, in references [b-l-b-4]. It is recommended that the statistics incorporated into this series of Worksheets be used for evaluations of goodness of fit statistics such as the correlation coefficient, the coefficient of determination, the standard error of estimate and the useful range of calibration standards used in method development. If you would like this Worksheet sent to you, please request this by e-mail from the authors. 

QSPR models have been developed by six multivariate calibration methods as described in the previous sections. We focus on demonstration of the use of these methods but not on GC aspects. Since the number of variables is much larger than the number of observations, OLS and robust regression cannot be applied directly to the original data set. These methods could only be applied to selected variables or to linear combinations of the variables. 

Their increased application in light food and drink products has given a new impetus to develop fast and accurate method for their determination. Among computer-controlled instruments multivariate calibration methods and derivative techniques are playing very important role in the multicomponent analysis of mixtures by UV-VIS molecular absorption spectrophotometry [2]. Both approaches ate useful in the resolution of overlapping band in quantitative analysis [3, 4]. 

Cost. There is always a trade-off of cost versus data quality. Data quality can be improved by further method development, more extensive calibration, replicate analysis or better statistics. 

Method development procedure for calibration-curve-based analysis. (Reproduced with permission from D. 6. Mitchell and J. S. Garden, Talanta, 1982, 29, 921-929, copyright 1982,... 

Chemometrican Data management and data fusion Process data analysis Multivariate data analysis Analyzer calibration model development Method equivalence Process models development (e.g., MSPC) Experimental design (e.g., DOE)... 

NIR models are validated in order to ensure quality in the analytical results obtained in applying the method developed to samples independent of those used in the calibration process. Although constructing the model involves the use of validation techniques that allow some basic characteristics of the model to be established, a set of samples not employed in the calibration process is required for prediction in order to conhrm the goodness of the model. Such samples can be selected from the initial set, and should possess the same properties as those in the calibration set. The quality of the results is assessed in terms of parameters such as the relative standard error of prediction (RSEP) or the root mean square error of prediction (RMSEP). 

Step 5 Off-line method or analyzer development and validation This step is simply standard analytical chemistry method development. For an analyzer that is to be used off-line, the method development work is generally done in an R D or analytical lab and then the analyzer is moved to where it will be used (QA/ QC lab, at-line manufacturing lab, etc.). For an analyzer that is to be used on-line, it may be possible to calibrate the analyzer off-line in a lab, or in situ in a lab reactor or a semiworks unit, and then move the analyzer to its on-line process location. Often, however, the on-line analyzer will need to be calibrated (or recalibrated) once it is in place (see Step 7). Off-line method development and validation generally includes method development and optimization, identification of appropriate check samples, method validation, and written documentation. Again, the form of the documentation (often called the method or the procedure ) is company-specific, but it typically includes principles behind the method, equipment needed, safety precautions, procedure steps, and validation results (method accuracy, precision, etc.). It is also useful to document here which approaches did not work, for the benefit of future workers. 

Step 7 On-line analyzer calibration Calibrating an analyzer entirely on-line is a last resort, for reasons discussed in Section 15.2.6. It is preferable to do at least the initial work to calibrate the analyzer off-line, or to transfer to the on-line analyzer a method developed on an off-line analyzer or on another on-line analyzer. However, sometimes this is not possible. On-line analyzer calibration is similar to standard analytical chemistry method development, except that getting sufficient variation in sample composition to build a robust calibration model may be difficult or may take a long time. (Ways to address the challenges involved in on-line calibration are discussed in Section 15.2.6 and in Chapter 14.)... 

Ideally, an on-line analyzer will be calibrated before it is installed in the process. It may be possible to accomplish this by calibrating it off-line with process grab samples and/or synthetic samples. It may be possible to install the analyzer in a lab-scale reactor, or in a semi-works or pilot plant. It may be possible to transfer to the on-line analyzer a method developed on an off-line analyzer or on another on-line analyzer (e.g. at a different plant site). However, sometimes none of these are possible and the analyzer will need to be calibrated on-line. The challenges of on-line model development (calibration) and validation, as well as approaches to dealing with them, are discussed below. For information related to calibration transfer issues, please see Chapter 12 of this book. 

SEC calibration methods which employ a series of narrow MWD standards are based upon a peak position method and traditionally have been the most widely practiced calibration procedures. The peak position method simply correlates the peak elution volume of each standard to its nominal molecular weight or size value. A curve fitting procedure (usually a least squares regression) is used to obtain a working calibration curve. The serious limitation of polymer chemical types for which a series of narrow MWD standards covering a wide molecular weight range can be obtained led to the development of experimental approaches which could be applied to polymer chemical types other than that of the narrow MWD standards employed in calibration. 

A direct consequence of the development of hydrodynamic volume theory In SEC has been the universal calibration method as introduced by Benoit (17). Universal calibration methodology is based upon the fact that retention in SEC can be described as a function of the hydrodynamic volume of polymer molecules. 

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