Standardization multiple-point

B.2 Single-Point versus Multiple-Point Standardizations ... 

A fifth spectrophotometric method for the quantitative determination of the concentration of Pb + in blood uses a multiple-point standard addition based on equation 5.6. The original blood sample has a volume of 1.00 mb, and the standard used for spiking the sample has a concentration of 1560 ppb Pb +. All samples were diluted to 5.00 mb before measuring the signal. A calibration curve of Sjpike versus Vj is described by... 

A multiple-point standardization presents a more difficult problem. Consider the data in Table 5.1 for a multiple-point external standardization. What is the best estimate of the relationship between Smeas and Cs It is tempting to treat this data as five separate single-point standardizations, determining k for each standard and reporting the mean value. Despite its simplicity, this is not an appropriate way to treat a multiple-point standardization. 

How do we find the best estimate for the relationship between the measured signal and the concentration of analyte in a multiple-point standardization Figure 5.8 shows the data in Table 5.1 plotted as a normal calibration curve. Although the data appear to fall along a straight line, the actual calibration curve is not intuitively obvious. The process of mathematically determining the best equation for the calibration curve is called regression. 

Standardizations using a single standard are common, but also are subject to greater uncertainty. Whenever possible, a multiple-point standardization is preferred. The results of a multiple-point standardization are graphed as a calibration curve. A linear regression analysis can provide an equation for the standardization. 

Data for Hypothetical Multiple-Point External Standardization... 

Creep, creep mpture, and stress relaxation tests are multiple-point tests requiring long periods of time (1000 h min) to generate useflil data these are standard tests for determining more fundamental polymer properties (202,203). Data for these tests are generated under several... 

BCR Analytical Approach for the Certification of PAHs in Natural Matrix CRMs Prior to the certification analyses for the CRM, each participating laboratory has to prepare standard solutions of the analytes to be determined from certified reference compounds (purity >99.0 %) to calibrate their instruments for response and response linearity (multiple point calibration), detection limit, and reproducibility. In the case of PAH measurements, reference compounds of certified purity are used as internal standards, which are not present at a detectable concentration in the matrix to be analyzed (e.g. indeno[i,2,3-cd]fluoranthene (CRM 267), 5-methylchrysene (CRM 081R), benzo[f ]chry-sene (CRM 046), picene (CRM 168), and/or phenanthrene-dio). 

The aids to chromatography include a) resolution calculations on chromatograms of standard mixtures to monitor column performance, b) calculation of Kovats retention index for help in identifying peaks, and (c) multiple point calibration curves for improved quantitation. The file searching routines access two sets of data. Information (such as molecular formula, molecular weight) is stored on 3100 compounds from the Arctander data( ). This allows a quick computer search through the data which is difficult... 

Case 3. Linearity demonstrated from 50% of the ICH reporting limit to 150% of the shelf life specification of a related substance, and a significant y-intercept is observed (Figure 3.8). Due to the significant -intercept, a single-point calibration (e.g., high-low or one-point external standard calibration) is not suitable. In this case, multiple-point external standard calibration is the most appropriate. See Section 3.3.3 for more discussion of the significant y-intercept. 

Prerequisites for the Calibration Types. It depends on the design of the analytical procedure as to which regression parameters are meaningful and which results are acceptable. In other words, the model to be used for quantitation must be justified. For a singlepoint calibration (external standardization), a linear function, zero intercept, and the homogeneity of variances are required. The prerequisites for a linear multiple-point calibration are a linear function and in case of an unweighted calibration also the homogeneity of variances. A non-linear calibration requires only a continuous function. With respect to the 100%... 

We use the method of standard additions when it is difficult or impossible to duplicate the sample matrix. In general, the sample is spiked with a known amount or amounts of a standard solution of the analyte. In the single-point standard addition method, two portions of the sample are taken. One portion is measured as usual, but a known amount of standard analyte solution is added to the second portion. The responses for the two portions are then used to calculate the unknown concentration, assuming a linear relationship between response and analyte concentration (see Example 8-8). In the multiple additions method, additions of known amounts of standard analyte solution are made to several portions of the sample, and a multiple additions cahbration eurve is obtained. The multiple additions method gives some... 

Single-point standard addition methods are inherently more risky than multiple-point methods. There is no check on linearity with single-point methods, and results depend strongly on the reliability of one measurement. 

The external standard method is the simplest one and should therefore only be used for simple analytical problems. The injection must be performed with good reproducibility thus it is recommended that the complete loop filling method be used (see Section 4.6). With multiple-point calibration it is not recommended to inject different volumes from a reference stock solution (e.g. 10, 20, 30, 40 and 50 (xl) because it is well possible that neither accuracy nor precision of these injections are high enough. It is better to prepare a number of calibration solutions with different concentrations and to inject equal volumes of them (with complete loop filling or with exactly the same procedure as is used also for the sample). 

Simple stab-ins or quills have been the standard addition points for many years, but a new generation of addition points is emerging. Metso s Retamix system delivers the product into the stock flow at multiple points, while the Wetend Technologies Limited Trumpjet systems allow additive dilution water to be replaced by clarified water or thin stock. 

A traceable standard carbon black supplied by Micromeritics Corporation (Sydney, Australia) with a recommended multiple-point BET-SSA of 113 5 m /g was used to calibrate and commission a newly designed, all stainless steel, high-pressure manometric adsorption apparatus. 

The cellular telephone industry points to a solution to the mobility problem. Move from the wire land to the wireless. Move from narrow-band powerful transmitters that block others from using the same part of the spectrum towards a broadband world where low power and new multiple access techniques increase available bandwidth. If the transmission distance is too short, create overlapping cells. Telephones cut the cord, why can t the computer Today s multiple cellular standards can be accommodated by inexpensive smart cellular phone units why can t LAN connections ... 

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