Spectrophotometry absorption

The one-electron reduction of thiazole in aqueous solution has been studied by the technique of pulse radiolysis and kinetic absorption spectrophotometry (514). The acetone ketyl radical (CH ljCOH and the solvated electron e were used as one-electron reducing agents. The reaction rate constant of with thiazole determined at pH 8.0 is fe = 2.1 X 10 mole sec in agreement with 2.5 x 10 mole sec" , the value given by the National Bureau of Standards (513). It is considerably higher than that for thiophene (6.5 x 10" mole" sec" ) (513) and pyrrole (6.0 X10 mole sec ) (513). The reaction rate constant of acetone ketyl radical with thiazolium ion determined at pH 0.8 is lc = 6.2=10 mole sec" . Relatively strong transient absorption spectra are observed from these one-electron reactions they show (nm) and e... 

The measurement of pK for bases as weak as thiazoles can be undertaken in two ways by potentiometric titration and by absorption spectrophotometry. In the cases of thiazoles, the second method has been used (140, 148-150). A certain number of anomalies in the results obtained by potentiometry in aqueous medium using Henderson s classical equation directly have led to the development of an indirect method of treatment of the experimental results, while keeping the Henderson equation (144). 

Relative uncertainties for absorption spectrophotometry as a function of absorbance for the three categories of indeterminate instrumental errors (see Table 10.8 for equations). 

Selectivity Selectivity is rarely a problem in molecular absorption spectrophotometry. In many cases it is possible to find a wavelength at which only the analyte absorbs or to use chemical reactions in a manner such that the analyte is the only species that absorbs at the chosen wavelength. When two or more species contribute to the measured absorbance, a multicomponent analysis is still possible, as shown in Example 10.6. 

Selectivity The selectivity of molecular fluorescence and phosphorescence is superior to that of absorption spectrophotometry for two reasons first, not every compound that absorbs radiation is fluorescent or phosphorescent, and, second, selectivity between an analyte and an interferant is possible if there is a difference in either their excitation or emission spectra. In molecular luminescence the total emission intensity is a linear sum of that from each fluorescent or phosphorescent species. The analysis of a sample containing n components, therefore, can be accomplished by measuring the total emission intensity at n wavelengths. 

Quigley, M. N. Determination of Calcium in Analgesic Tablets Using Atomic Absorption Spectrophotometry, ... 

Schematic diagrams of flow cell detectors for HPLC using (a) UVA/is absorption spectrophotometry and (b) amperometry.

Koscielniak and Parczewski investigated the influence of A1 on the determination of Ca by atomic absorption spectrophotometry using the 2 factorial design shown in the following table. ... 

Provide an SOP for the determination of cadmium in lake sediments by atomic absorption spectrophotometry using a normal calibration curve. 

Determination of gold concentrations to ca 1 ppm in solution via atomic absorption spectrophotometry (62) has become an increasingly popular technique because it is available in most modem analytical laboratories and because it obviates extensive sample preparation. A more sensitive method for gold analysis is neutron activation, which permits accurate determination to levels < 1 ppb (63). The sensitivity arises from the high neutron-capture cross section (9.9 x 10 = 99 barns) of the only natural isotope, Au. The resulting isotope, Au, decays by P and y emission with a half-life of 2.7 d. 

Concurrent with requirements for low levels of mercurials in discharge water is the problem of their deterrnination. The older methods of wet chemistry are inadequate, and total rehance is placed on instmmental methods. The most popular is atomic absorption spectrophotometry, which rehes on the absorption of light by mercury vapor (4). Solutions of mercury compounds not stabilized with an excess of acid tend to hydrolyze to form yeUow-to-orange basic hydrates. These frequendy absorb onto the walls of containers and may interfere with analytical results when low levels (ppm) of mercury are determined. 

Analytical deterrnination of nickel in solution is usually made by atomic absorption spectrophotometry and, often, by x-ray fluorescence spectroscopy. 

Potassium is analyzed in chemicals that are used in the fertilizer industry and in finished fertilizers by flame photometric methods (44) or volumetric sodium tertraphenylboron methods (45) as approved by the AO AC. Gravimetric deterrnination of potassium as K2PtClg, known as the Lindo-Gladding method (46), and the wet-digestion deterrnination of potassium (47) have been declared surplus methods by the AO AC. Other methods used for control purposes and special analyses include atomic absorption spectrophotometry, inductively coupled plasma (icp) emission spectrophotometry, and a radiometric method based on measuring the radioactivity of the minute amount of the isotope present in all potassium compounds (48). 

Spectrophotometric deterrnination at 550 nm is relatively insensitive and is useful for the deterrnination of vitamin B 2 in high potency products such as premixes. Thin-layer chromatography and open-column chromatography have been appHed to both the direct assay of cobalamins and to the fractionation and removal of interfering substances from sample extracts prior to microbiological or radioassay. Atomic absorption spectrophotometry of cobalt has been proposed for the deterrnination of vitamin B 2 in dry feeds. Chemical methods based on the estimation of cyanide or the presence of 5,6-dimethylben2irnida2ole in the vitamin B 2 molecule have not been widely used. 

Alkaline-earth metals are often deterruined volumetricaHy by complexometric titration at pH 10, using Eriochrome Black T as indicator. The most suitable complexing titrant for barium ion is a solution of diethylenetriaminepentaacetic acid (DTPA). Other alkaline earths, if present, are simultaneously titrated, and in the favored analytical procedure calcium and strontium are deterruined separately by atomic absorption spectrophotometry, and their values subtracted from the total to obtain the barium value. 

BeryUium aUoys ate usuaUy analyzed by optical emission or atomic absorption spectrophotometry. Low voltage spark emission spectrometry is used for the analysis of most copper-beryUium aUoys. Spectral interferences, other inter-element effects, metaUurgical effects, and sample inhomogeneity can degrade accuracy and precision and must be considered when constmcting a method (17). 

Metal Extraction. As with other carboxyhc acids, neodecanoic acid can be used in the solvent extraction of metal ions from aqueous solutions. Recent appHcations include the extraction of zinc from river water for deterrnination by atomic absorption spectrophotometry (105), the coextraction of metals such as nickel, cobalt, and copper with iron (106), and the recovery of copper from ammoniacal leaching solutions (107). 

Mean values from duplicate analyses of each of three samples by atomic absorption spectrophotometry. 

In vitro absorption-spectrophotometry techniques are available to assess a sunscreen s efficacy, but the preferred methods are in vivo procedures in which a small body site is irradiated with the desired wavelengths for different periods in the presence or absence of a uv protectant. Procedures vary from country to country to determine the incremental timing of the exposure that ultimately allows quantification via sun protective factor (SPE). In the United States, sunscreen preparations are considered OTC dmg products, and the SPE must be specified (54). Even in countries that do not identify these products as dmgs, SPE labeling has become customary. 

Metal Content. Two common analytical methods for determining metal content are by titration and by atomic absorption spectrophotometry (aas). The titration method is a complexiometric procedure utilizing the disodium salts of ethylenediaminetetraacetic acid (EDTA). The solvent, indicator. 

Testing and Control. Analysis and testing are required whenever a new plating solution is made up, and thereafter at periodic intervals. The analyses are relatively simple and require Httie equipment (78—80). Trace metal contaminants can be analy2ed using spot tests, colorimetricaHy, and with atomic absorption spectrophotometry (see Trace and residue analysis). Additives, chemical balance, impurity effects, and many other variables are tested with small plating cells, such as the Hull cell developed in 1937 (81,82). 

The end group of the polymers, photoinitiated with aromatic amine with or without the presence of carbonyl compound BP, has been detected with absorption spectrophotometry and fluororescence spectrophotometry [90]. The spectra showed the presence of tertiary amino end group in the polymers initiated with secondary amine such as NMA and the presence of secondary amino end group in the polymers initiated with primary amine such as aniline. These results show that the amino radicals, formed through the deprotonation of the aminium radical in the active state of the exciplex from the primary or secondary aromatic amine molecule, are responsible for the initiation of the polymerization. 

Further techniques which may be applied directly to the solvent extract are flame spectrophotometry and atomic absorption spectrophotometry (AAS).13 The direct use of the solvent extract in AAS may be advantageous since the presence of the organic solvent generally enhances the sensitivity of the method. However, the two main reasons for including a chemical separation in the preparation of a sample for AAS are ... 

Theory. Conventional anion and cation exchange resins appear to be of limited use for concentrating trace metals from saline solutions such as sea water. The introduction of chelating resins, particularly those based on iminodiacetic acid, makes it possible to concentrate trace metals from brine solutions and separate them from the major components of the solution. Thus the elements cadmium, copper, cobalt, nickel and zinc are selectively retained by the resin Chelex-100 and can be recovered subsequently for determination by atomic absorption spectrophotometry.45 To enhance the sensitivity of the AAS procedure the eluate is evaporated to dryness and the residue dissolved in 90 per cent aqueous acetone. The use of the chelating resin offers the advantage over concentration by solvent extraction that, in principle, there is no limit to the volume of sample which can be used. 

In the illustrative experiment described here, copper(II) ions in a brine solution are concentrated from 0.1 to about 3.3 ppm prior to determination by atomic absorption spectrophotometry. 

A. E. Lindh, Rontgenspektroskopie, Handbuch der Experimentalphysik (Wien u. Harms), Vol. XXIV 2, Akademische Yerlagsgesellschaft, Leipzig, 1930, page 291. B. Lindstrom, Roentgen Absorption Spectrophotometry in Quantitative Cytochemistry, Acta Radiol. SuppL, 125, 34 (1955). 

B. Lindstrom, "Roentgen Absorption Spectrophotometry in Quantitative Cytochemistry, Acta Radiol. Suppl., 125 (1955). 

Recent work in this laboratory has sought to provide some of this information. Unfortunately, absorption spectrophotometry is not suitable for monitoring the formation of Pu(IV) polymer... 

The complexation of Pu(IV) with carbonate ions is investigated by solubility measurements of 238Pu02 in neutral to alkaline solutions containing sodium carbonate and bicarbonate. The total concentration of carbonate ions and pH are varied at the constant ionic strength (I = 1.0), in which the initial pH values are adjusted by altering the ratio of carbonate to bicarbonate ions. The oxidation state of dissolved species in equilibrium solutions are determined by absorption spectrophotometry and differential pulse polarography. The most stable oxidation state of Pu in carbonate solutions is found to be Pu(IV), which is present as hydroxocarbonate or carbonate species. The formation constants of these complexes are calculated on the basis of solubility data which are determined to be a function of two variable parameters the carbonate concentration and pH. The hydrolysis reactions of Pu(IV) in the present experimental system assessed by using the literature data are taken into account for calculation of the carbonate complexation. 

Cell constants, cesium and hafnium. .53, 55/ Cell coupled with absorption spectrophotometry, electrochemical... 

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