Relative standard deviation calibration

Determinarion of MW and MWD by SEC using commercial narrow molecular weight distribution polystyrene as calibration standards is an ASTM-D5296 standard method for polystyrene (11). However, no data on precision are included in the 1997 edition of the ASTM method. In the ASTM-D3536 method for gel-permeation chromatography from seven replicates, the M of a polystyrene is 263,000 30,000 (11.4%) for a single determination within the 95% confidence level (12). A relative standard deviation of 3.9% was reported for a cooperative determination of of polystyrene by SEC (7). In another cooperative study, a 11.3% relative standard deviation in M, of polystyrene by GPC was reported (13). 

Option (Valid) presents a graph of relative standard deviation (c.o.v.) versus concentration, with the relative residuals superimposed. This gives a clear overview of the performance to be expected from a linear calibration Signal = A + B Concentration, both in terms of (relative) precision and of accuracy, because only a well-behaved analytical method will show most of the residuals to be inside a narrow trumpet -like curve this trumpet is wide at low concentrations and should narrow down to c.o.v. = 5% and rel. CL = 10%, or thereabouts, at medium to high concentrations. Residuals that are not randomly distributed about the horizontal axis point either to the presence of outliers, nonlinearity, or errors in the preparation of standards. 

Optimizing the GC instrument is crucial for the quantitation of sulfentrazone and its metabolites. Before actual analysis, the temperatures, gas flow rates, and the glass insert liner should be optimized. The injection standards must have a low relative standard deviation (<15%) and the calibration standards must have a correlation coefficient of at least 0.99. Before injection of the analysis set, the column should be conditioned with a sample matrix. This can be done by injecting a matrix sample extract several times before the standard, repeating this conditioning until the injection standard gives a reproducible response and provides adequate sensitivity. 

Garcia et al. [45] determined penicillamine in pharmaceutical preparations by FIA. Powdered tablets were dissolved in water, and the solution was filtered. Portions (70 pL) of the filtrate were injected into a carrier stream of water that merged with a stream of 1 mM PdCl2 in 1 M HC1 for determination of penicillamine. The mixture was passed though a reaction coil (180 cm long) and the absorbance was measured at 400 nm. Flow rates were 1.2 and 2.2 mL/min for the determination of penicillamine, the calibration graphs were linear for 0.01-0.7 mM, and the relative standard deviation (n = 10) for 0.17 mM analyte was 0.8%. The method was sufficiently selective, and there were no significant differences between the labeled contents and the obtained results. 

Wakabayashi et al. [51] determined penicillamine in serum by HPLC. Serum (0.1 mL) was vortex-mixed for 30 s with 50 pL of 0.1% EDTA and 0.2 mL of 10% TCA. The solution was centrifuged at 1500 x g and filtered. A 5 pL portion was analyzed on a Shodex C18 column (15 cm x 4.6 mm i.d.), using a mobile phase of 19 1 methanolic 0.05 M phosphate buffer (pH 2.8) containing 1 mM sodium octylsulfate and 10 pM EDTA. Liver or kidney samples were similarly extracted, and the extracts were cleaned up on a Bond-Elut cartridge prior to HPLC analysis. Detection was effected with an Eicom WE-3G graphite electrode maintained at +0.9 V versus Ag/AgCl. The calibration graph was linear up to 500 ng, and the detection limits were 20 pg. For 1 pg of penicillamine added to serum, liver, or kidney, the respective relative standard deviations (n = 5) were 3.6, 5.1, and 4.4%. 

Cheng et al. reported the use of a synchronous fluorimetric method for the determination of primaquine in two-component antimalarial tablets [31]. Ground tablets were dissolved in water and the mixture was filtered. The fluorescence intensities of chloroquine phosphate and primaquine phosphate, in the filtrate, were measured at 380 nm (excitation at 355 nm) and 505 nm (excitation at 480 nm), respectively. The calibration graphs were linear from 1 to 8 pg/mL of chloroquine phosphate and 10 to 110 pg/mL of primaquine phosphate. The mean recoveries were 98.2-101.49% and the relative standard deviations were 2.23%. 

Sole use of the correlation coefficient (r) alone is not recommended as a means to demonstrate linearity. The correlation coefficient describes the relation between two random parameters, and shows no relevance for the analytical calibration [31]. The correlation coefficient does not indicate the linearity or lack thereof, unless r exceeds 0.999 [8, 32, 33]. If the value of r is less than 0.999, other parameters such as Vxo, Xp value, ANOVA linear testing, etc., should be calculated. Ebel [34] described using the transformation of r (i.e., Vu ) for expressing the degree of linearity, where the acceptance value of (1 — r ) should be less than 0.05. Camag (Muttents) described the sdv parameter (i.e., the relative standard deviation of the calibration curve) for expressing the linearity of a calibration curve for TLC/HPTLC in its CATS software, and can be calculated as follows ... 

In this method, inorganic lead in seawater samples are converted to tetra-ethylead using sodium tetraethylboron (NaB(C2H5)4) which is then trapped in a graphite furnace at 400 °C. Quantitation is achieved by using a simple calibration graph prepared from aqueous standards. An absolute detection limit of (3relative standard deviation. 

Based on these results, a simple and unique determination of 14 L-amino acids and glucose as substrates was developed. Thus, the calibration graph for a representative amino acid, L-phenylalanine was linear in the concentration range 1.0 x 10 6-2 x 10 8 M with a relative standard deviation of 5.78% and a correlation coefficient of 0.9974. The detection limit obtained was 1.05 X 10 8 M. In the case of glucose the calibration graph was linear in the concentration range 2.7 X 10 6-2.7 X 10 8 M with a relative standard deviation of 4.27% and a correlation coefficient of 0.9980. The detection limit was 2.7 X 10 8 M. The method was successfully applied to the determination of glucose in human blood serum. 

The beauty of this completely random approach to the analyte detection limit is the direct applicability of the statistical hypothesis testing formalism. Also, long-term trends in calibration slope or backgrounds have little influence. One important assumption is made that the form of the calibration curve [Equation 2c] is fixed. Also, a subtle change has occurred, the operation is no longer linear, with A in the denominator. Thus, the distribution of x is only asymptotically normal, as the relative standard deviation of becomes smaller. 

The cyanide sensor developed by the authors group is based on the formation of an addition product between cyanide ion and pyridoxal-5-phosphate, and its subsequent retention in the sensor (a fluorimetric flow-cell packed with QAE-Sephadex resin). The eluent is not injected, but merged with a stream of 0.05 M HCl after the reactor that is used both to acidify the complex and elute it after measurement. The calibration graph for the target analyte was linear from 50 ng/mL to 3.0 pg/mL, and the relative standard deviation and sample throughput were 1.4% (for 2 pg CN7mL) and... 

Since all the method development was performed with NaDCC, the established procedure was applied to TCCA. The calibration curve was determined from 19 TCCA standards ranging from 0.116 to 2.09 mg, indicating a pooled relative standard deviation of 3.9%. 

Pump The pump should be capable of a flow rate between 0.50 and 5.00mL/min. The pump should be a quaternary gradient pump and have a compositional accuracy of +1.5% of the theoretical values for the four channels. The pump should have relative standard deviation (RSD) of <2.0% for six successive readings from a calibrated flowmeter. 

Acceptance criteria for tailing factor, percent injection reproducibility, relative standard deviation of calibration and/or control standard... 

Lopez Garcia et al. [2] have described a rapid and sensitive spectrophotometric method for the determination of boron complex anions in plant extracts and waters which is based on the formation of a blue complex at pH 1 - 2 between the anionic complex of boric acid with 2,6-dihydroxybenzoic acid and crystal violet. The colour is stabilised with polyvinyl alcohol. At 600 nm the calibration graph is linear in the range 0.3-4.5 xg boron per 25 ml of final solution, with a relative standard deviation of 2.6% for xg/l of boron. In this procedure to determine borate in plant tissues, the dried tissue is treated with calcium hydroxide, then ashed at 400 °C. The ash is digested with 1N sulfuric acid and heated to 80 °C, neutralized with cadmium hydroxide and then treated with acidic 2,6-dihydroxybenzoic acid and crystal violet, and the colour evaluated spectrophotometrically at 600 nm. Most of the ions present in natural waters or plant extracts do not interfere in the determination of boron complex anions by this procedure. Recoveries of boron from water samples and plant extracts were in the range of 97 -102%. 

Calibrations were carried out for the GC/PID or the GC/MS daily. Calibration standards were prepared based on standard reference materials obtained from Supelco Chromatography products. A check standard was analyzed every ten samples to assure calibration and accuracy. A reagent blank was included in each analytic batch of samples. Blanks were made from reagent or make-up water and matrix similar to the sample. A spiked sample was analyzed every twenty samples. This was done by splitting an appropriate sample into two subsamples and adding a known quantity of TCE to one of the split samples. The purpose of a spiked sample is to determine the extent of matrix bias or interference on TCE recovery and sample to sample precision. Accuracy was assessed by analysis of external reference standards (separate from calibration standards) and by percent recoveries of spiked samples. Precision was assessed by means of replicate sample analysis. It is expressed as relative percent difference (RPD) in the case of duplicates or relative standard deviation (RSD) for triplicate (or more) analyses. Recovery was 96% or more for all spiked samples, and RPD/RSD are less than 7% for all samples. 

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