Quantitative analysis external standard method

The determination of the relationship between detector response and the sample concentration is termed the calibration of the method. There are two types of methods in use for the quantitative analysis of a sample, i.e., the external standard and the internal standard method. An external standard method is a direct comparison of the detector response of a pure compound (standard) to a sample.2 The calibration of the method is performed by preparing standards of varying concentration and analyzing them by a developed method. Method 1 (below) was developed for toluene, and standards of varying concentration were prepared and analyzed. The results obtained are summarized in Table 2 see Figure 3. 

A 25-g soil sample was extracted with methylene chloride and the extract was concentrated to a final volume of 2 mL. A 10-component alkane mixture at a concentration of each component as 50 pg/mL was used in quantitation performed by external standard method. 1 pL of the extract and the standard were injected onto the column for analysis. Determine the concentration of diesel range organics in the sample from the following data ... 

Quantitation. The organic species identified by the GC-MS analyses were quantitated by GC analysis using internal and external standardization methods. Pure compounds representative of the various compound classes identified by GC-MS were selected as standards and methylated. A specific amount of each standard was co-injected with each sample to confirm the GC-MS identifications. For quantitation purposes, each standard was injected onto the gas chromatograph prior to and following sample analyses. The response factor of each standard was calculated under analytical conditions identical to those of the sample analyses. 

An external standard method is used when the standard is analyzed on a separate chromatogram from the sample. Quantitation is based on a comparison of the peak area/height (HPLC or GC) of the sample to that of the reference standard for the analyte of interest. The external standard method is more appropriate for samples with a single target analyte and narrow concentration range, where there is a simple sampling procedure, and for the analysis of hydrocarbon fractions. The calculation requires an accurate extract final volume and constant injection size. The peak area of an analyte is compared with that from a standard or standard curve and corrected for volume ... 

The standard addition method is commonly used in quantitative analysis with ion-sensitive electrodes and in atomic absorption spectroscopy. In TLC this method was used by Klaus 92). Linear calibration with R(m=o)=o must also apply for this method. However, there is no advantage compared with the external standard method even worse there is a loss in precision by error propagation. The attainable precision is not satisfactory and only in the order of 3-5 %, compared to 0.3-0.5 % using the internal standard method 93). 

The quantitative analysis of the hydroformylation reaction products was carried out by an external standard method using a Varian 3600 gas chromatograph on a 10% OV-17, packed column, 8 feet length. Synthetic standards were used for calibration purposes. 

Four techniques are commonly used in quantitative analysis the normalization method, the external standard method, the internal standard method, and the standard addition method. Whatever method is used, the accuracy often depends on the sample preparation and on the injection technique. Nowadays these are two main sources of error in quantitative analysis. The quantitative results produced by PCGC and CGC are comparable. 

Quantitative analysis using the external standards method is achieved by preparing a range of standards, containing known quantities of analyte, in the same matrix as the sample. The major disadvantage of this method is that the volume introduced... 

Quantification of the relative abundance of crystalline phases in a multiphase mixture is an everyday problem in a wide range of applications. Common examples are evaluation of the yield in inorganic synthesis and catalytic processes, characterization of raw mineral materials for industrial processes, quality check of fired ceramic products, and many more. While in most cases the required accuracy level of the analysis is a few percent at best, in particular cases such as in the quantification of phase contaminants in technologically important materials, or of hazardous and toxic phases in environmentally dispersed aerosols, the required level of accuracy must be substantially lower than 1 wt% relative abundance. Accuracy levels of 2-3 wt% are commonly reached if standard procedures of quantitative phase analysis by diffraction data are properly performed. Generally employed analytical methods include the internal or external standard method, the matrix flushing method, and the reference intensity ratio method. Very recently, the availability of analysis techniques of powder diffraction data based on full-profile (Rietveld method), originally developed... 

When quantification is required (Tier II), an external standards method (ESTD) is used. The quantitation technique typically requires a comparison of five peaks (minimum of three) between the chromatograms of an unknown sample and that of standard Aroclor obtained under identical conditions. Quantitation of either Aroclors 1016 or 1260 is performed using a five-point calibration of a mixed Aroclor standard containing Aroclors 1016 and 1260. All remaining Aroclors are quantitated from single point calibrations. Calibration is verified daily by comparison of results obtained for analysis of... 

Standardization—External standards, standard additions, and internal standards are a common feature of many quantitative analyses. Suggested experiments using these standardization methods are found in later chapters. A good project experiment for introducing external standardization, standard additions, and the importance of the sample s matrix is to explore the effect of pH on the quantitative analysis of an acid-base indicator. Using bromothymol blue as an example, external standards can be prepared in a pH 9 buffer and used to analyze samples buffered to different pHs in the range of 6-10. Results can be compared with those obtained using a standard addition. 

When possible, a quantitative analysis is best conducted using external standards. Unfortunately, matrix interferences are a frequent problem, particularly when using electrothermal atomization. Eor this reason the method of standard additions is often used. One limitation to this method of standardization, however, is the requirement that there be a linear relationship between absorbance and concentration. 

Table 5.17 Quantitative results obtained for the determination of four diarrhetic shellfish poisons (DSPs) using external standards and the method of standard additions. Reprinted from J. Chromatogr., A, 943, Matrix effect and correction by standard addition in quantitative liquid chromatographic-mass spectrometric analysis of diarrhetic shellfish poisoning toxins , Ito, S. and Tsukada, K., 39-46, Copyright (2002), with permission from Elsevier Science...

Quantitative analysis using FAB is not straightforward, as with all ionisation techniques that use a direct insertion probe. While the goal of the exercise is to determine the bulk concentration of the analyte in the FAB matrix, FAB is instead measuring the concentration of the analyte in the surface of the matrix. The analyte surface concentration is not only a function of bulk analyte concentration, but is also affected by such factors as temperature, pressure, ionic strength, pH, FAB matrix, and sample matrix. With FAB and FTB/LSIMS the sample signal often dies away when the matrix, rather than the sample, is consumed therefore, one cannot be sure that the ion signal obtained represents the entire sample. External standard FAB quantitation methods are of questionable accuracy, and even simple internal standard methods can be trusted only where the analyte is found in a well-controlled sample matrix or is separated from its sample matrix prior to FAB analysis. Therefore, labelled internal standards and isotope dilution methods have become the norm for FAB quantitation. 

Quantitative analysis of AP/APEO by HPLC-FL can be performed with external standard solutions of mixtures of AP or APEO. Initially quantification of oligomeric mixtures was based on the elaborate procedure of normal-phase analysis with subsequent quantification of all oligomeric peaks [27]. Kiewiet et al. [28] have described the general principle of quantification of ethoxymers in reversed-phase LC with spectroscopic detection in detail using the example of derivatised alcohol ethoxylates. Based on this method the quantitative analysis of... 

For quantitative analysis by either the external or internal standard methods, HPLC requires the use of calibration solutions that are injected under identical conditions. Thus to fully identify quantitative effects, calibration solutions plus standard solutions need to be analysed for each experiment in a ruggedness test. As duplicate determinations are required for the estimation of standard errors a single experiment can consist of up to six chromatographic experiments as shown below. 

An external standardisation method is employed to perform quantitative analysis. In the cited study, calibration curves for each compound are obtained by injecting amounts ranging from 0.08 to 10 nmol. The amount of injected standards is logarithmically proportional to the peak area. 

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