Standard deviation chromatography

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). 

WLR.dat Section 2.2.10 A set of peak area vs. concentration results of a gas chromatography calibration. Use with LINREG to test the effect of a weighting scheme. The originally estimated dependence of the standard deviation of determination vs. concentration is described by the equation SD = 100 + 5 X. 

ECD = electron capture detector GC = gas chromatography HPLC = high-performance liquid chromatography MC = microcoulometric detector MS = mass spectrometry NICI = negative ion chemical ionization RSD = relative standard deviation SPE = solid phase extraction... 

Successful use of modern liquid chromatography in the clinical laboratory requires an appreciation of the method s analytical characteristics. The quantitative reproducibility with respect to peak height or peak area is quite good. With a sample loop injector relative standard deviations better than 1% are to be expected. The variability of syringe injection (3-4% relative standard deviation) requires the use of an internal standard to reach the 1% level (2,27). 

Percentage of total gas chromatography (GC) peak area (standard deviation). 

Prior to use, the linearity of the gas chromatography system should be verified by analyzing at least four standards of different concentrations. The linearity standards should range in concentration from 0.1 to 2.0 igmL A response factor for each standard is calculated by dividing the response of each standard by its concentration. The relative standard deviation (RSD) of these response factors should be <10%. 

The small peak volumes typical of samples eluted from small bore columns and short small diameter particle columns used in high-speed liquid chromatography place severe demands on the dispersion characteristics of all components of the liquid chromatograph. The standard deviation of a peak eluting from a column is given by... 

Chromatographic system (See Chromatography <621 >.) The liquid chromatograph is equipped with a 230 nm detector and a 4.6 mm x 30 cm column that contains packing L7. The flow rate is about 2 mL/min. Chromatograph the Resolution solution and the Standard preparation, and record the peak responses as directed under Procedure the resolution, R, between the dibutyl phthalate and miconazole peaks is not less than 5, the tailing factor for the miconazole peak is not more than 1.3, and the relative standard deviation for replicate injections of the Standard preparation is not more than 2%. The relative retention times are about 0.7 for dibutyl phthalate and 1 for miconazole. 

Sternson et al. [58] used a high performance liquid chromatographic method for the analysis of miconazole in plasma. Miconazole was extracted from alkalinized plasma with n-heptane-isamyl alcohol (98.5 1.5) and separated by high performance performance liquid chromatography on p-Bondapak Ci8 with ultraviolet detection at 254 nm. The mobile phase was methanol-tetrahydrofuran-acetate buffer (pH 5) (62.5 5 32.5) containing 5 mmol octanesulfonate per liter. The flow rate was 2 mL/min. Recovery was 100%. The relative standard deviation for injection-to-injection reproducibility was 0.4% and that for sample-to-sample variation was 5% at high miconazole concentrations (30 pg/mL) and 1% at low (1 pg/mL) concentrations. The limit of detection was 250 ng/mL. 

As a consequence of the previous considerations Kieber et al. [75] have developed an enzymic method to quantify formic acid in non-saline water samples at sub-micromolar concentrations. The method is based on the oxidation of formate by formate dehydrogenase with corresponding reduction of /3-nicotinamide adenine dinucleotide (j6-NAD+) to reduced -NAD+(/3-NADH) jS-NADH is quantified by reversed-phase high performance liquid chromatography with fluorimetric detection. An important feature of this method is that the enzymic reaction occurs directly in aqueous media, even seawater, and does not require sample pre-treatment other than simple filtration. The reaction proceeds at room temperature at a slightly alkaline pH (7.5-8.5), and is specific for formate with a detection limit of 0.5 im (SIN = 4) for a 200 xl injection. The precision of the method was 4.6% relative standard deviation (n = 6) for a 0.6 xM standard addition of formate to Sargasso seawater. Average re-... 

Fernandez et al. [9] used supercritical fluid extraction combined with ion pair liquid chromatography to determine quaternary ammonium in digested sludges and marine sediments. Carbon dioxide modified with 30% methanol was used as the extractant at an operating pressure of 380atm. Between 0.2 and 3.7g kg-1 surfactant was found in Swiss works effluent sludges, determined with a relative standard deviation of 7%. 

Xie [39] determined trace amounts of chlorophenols and chloroguaiacols in marine sediments collected off the Swedish coast. The compounds were desorbed from sediment surfaces by a mixture of acetic anhydride and hexane, after buffering with O.lmol L 1 sodium carbonate. The optimal pH was achieved by a 1 4 ratio of buffer to acetic anhydride. The acetylated extracts were analysed by glass capillary gas chromatography with electron capture detection. The recoveries, at the pg kg-1 level, ranged from 85-100% with standard deviations of 4-11%. 

Alford Stevens et al. [49] have reported on an inter-laboratory study of the determination of polychlorinated biphenyls in environmental sediments. Electron capture gas chromatography and mass spectrometry were used to identify and determine polychlorinated biphenyls. For electron capture, an overall standard deviation of 30% was achieved while mass spectrometry gave 38%. 

Bertoni et al. [70] used electron capture gas chromatography to determine 2,3,7,8-tetrachlorodibenzo-p-dioxin in Sevesco soil at the pbb level with a 15% standard deviation. 

Stable labelled isotopes are spiked into samples before extraction and the ratio of unlabelled compound and stable labelled isotope was used to quantitate the unlabelled compound. Analysis is by high-resolution gas chromatography-mass spectrometry. Fifteen standard water samples and ten standard soil samples containing 2,4-D at known concentrations were analysed. Compound concentrations ranged from 100 to lOOOOug per kg for soil samples. Average recoveries were over 84% and method precision, given as relative standard deviation, was better than 19%. 

The separation efficiency in chromatography and the sample throughput in CFA and FIA are better the narrower the test substances zones. The experimental conditions must therefore be selected so that the zone broadening in the detection system is as low as possible. The zone width is conveniently expressed in terms of the time standard deviation, o, or the volume standard deviation, oy, which are related by the expression,... 

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