Photometric analysers

These include such instruments as opacity monitors, turbidimeters, colorimeters, refractometers and spectrophotometers. A selection of these is described—particularly where the instrument has a more general application as an on-line process analyser and/or to illustrate a general principle of operation. It is likely that development of fibre-optic techniques (Section 6.12.4) will extend the use of this type of sensor in the future(56). 

These instruments constitute a class of spectroradiometric analysers generally encountered in the chemical process industries and employed to monitor wavelengths between the middle infra-red (MIR) and ultra-violet (UV) regions of the electromagnetic spectrum (Table 6.8). 

The radiation may be due to emissions from a hot source, or to the luminescence, fluorescence or phosphorescence of the sample. An emission spectrum consists of a number of generally very narrow peaks (called spectral lines) occurring at certain wavelengths which are characteristic of the materials contained within the source. The amplitudes of the peaks are related to the abundance or concentration of the materials present. Alternatively, radiation from a source is passed through a sample. In this case the quantity absorbed by the sample at a particular wavelength is again characteristic of the materials present in the sample. This is termed absorption spectrometry and produces spectral transmission lines in the form of equally narrow valleys—or peaks (Fig. 6.42) where the information is expressed in terms of absorbance (si) rather than transmittance (20 57 , and  

Absorbance spectra of wet and dry polyalkylene glycol ether (brake fluid) in the near infra-red region of the electromagnetic spectrum 5  

Schematic diagram of a dual-beam NDIR analyser 

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Zimm plot analychem A graphical determination of the root-square-mean end-to-end distances of coillike polymer molecules during scattered-light photometric analyses. zim,plat ... 

Flame photometric analyses are much simpler. For example, when sodium is inserted in a flame at 200CTC, the sodium atoms are the only ones emitting radiation. Light measurement can be conducted using a simple coloured filter that isolates the relatively large spectral band corresponding to the yellow colouration in the flame. 

Analytical Methods. Iron (II) and Iron (III). Methanolic solutions of varying concentrations of iron (II) and iron (III) were made. Spectro-photometric analyses were performed and calibrated according to the reported procedure (20, 37). They both obey Beer s Law. In a kinetic... 

It must be evident to the reader that more work is needed to determine the amino acids other than tyrosine in proteins which react with iodine. Since iodine has a powerful effect on some absorbing groups, spectro-photometric analyses coupled with variations of pH and other factors might prove very useful. In the case of tyrosine, the ionization constants, or pKs of phenolic groups of the iodo derivatives have been determined spectrophotoroetrically (75, 307). For tyrosine (75, 308), mono iodo-tyrosine (308), and diiodotyrosine (75, 308) the pKs are 10.1, 8.2 and 6.4 respectively. 

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). 

Each sample was fortified with chlorpyrifos, as a reference standard, to determine the recovery during each extraction. Three portions of solvent were used, and the combined extract for each sample was dried with sodium sulfate. Analyses employed gas chromatography/flame photometric detection. Limits of detection for vegetation and animal tissues were 0.2 and 0.007 pg respectively. Recoveries from fortified samples were 82%. Diazoxon occurrence was infrequenf and at trace concentrations. 

Quantitation is performed by the calibration technique. Construct a new calibration curve with methomyl oxime standard solutions (0.2, 0.4, 0.6, 0.8 and 1.0 xgmL in acetone) for each set of analyses. Plot the peak area against the injected amount of methomyl oxime on logarithmic paper. As the amount of alanycarb is measured in terms of its oxime derivative, a conversion factor of 3.8 (the molecular weight ratio of alanycarb to methomyl oxime) should be applied to obtain the net amount. The injection volume should be kept constant as the peak area varies with the injection volume in flame photometric detection. Before each set of measurements, check the GC system by injecting more than one standard solution containing ca 2-10 ng of methomyl oxime. 

Phenolic antioxidants in rubber extracts were determined indirectly photometrically after reaction with Fe(III) salts which form a red Fe(II)-dipyridyl compound. The method was applicable to Vulkanox BKF and Vulkanox KB [52]. Similarly, aromatic amines (Vulkanox PBN, 4020, DDA, 4010 NA) were determined photometrically after coupling with Echtrotsalz GG (4-nitrobenzdiazonium fluoroborate). For qualitative analysis of vulcanisation accelerators in extracts of rubbers and elastomers colour reactions with dithio-carbamates (for Vulkacit P, ZP, L, LDA, LDB, WL), thiuram derivatives (for Vulkacit I), zinc 2-mercaptobenzthiazol (for Vulkacit ZM, DM, F, AZ, CZ, MOZ, DZ) and hexamethylene tetramine (for Vulkacit H30), were mentioned as well as PC and TLC analyses (according to DIN 53622) followed by IR identification [52]. 8-Hydroquinoline extraction of interference ions and alizarin-La3+ complexation were utilised for the spectrophotometric determination of fluorine in silica used as an antistatic agent in PE [74], Also Polygard (trisnonylphenylphosphite) in styrene-butadienes has been determined by colorimetric methods [75,76], Most procedures are fairly dated for more detailed descriptions see references [25,42,44],... 

In this development of a flow injection method for the determination of nitrate andnitrite, Anderson [168] chose the Shinn [155] method to reduce nitrate and nitrite because of its high sensitivity and relative freedom from interferences. Anderson [168] used flow injection in the photometric determination of nitrite and nitrate with sulfanilamide and N-( 1-naphthyl) ethylenediamine as reagents, as discussed next. The detection limit is 0.05 xm for nitrite and 0.1 xm for nitrate at a total sample volume of 200 iL. Up to 30 samples can be analysed per hour with relative precision of about 1%. 

Various approaches to the analysis of dissolved silicon have been tried. Most of them are based on the formation of /J-molybdosilic acid [ 199-203 ]. Dissolved silicon exists in seawater almost entirely as undissociated orthosilicic acid. This form and its dimer, termed reactive silicate , combine with molybdosilicic acid to form a- and /I-molybdosilicic acid [180]. The molybdosilicic acid can be reduced to molybdenum blue, which is determined photometrically [206]. The photometric determination of silicate as molybdenum blue is sufficiently sensitive for most seawater samples. It is amenable to automated analysis by segmented continuous flow analysers [206-208]. Most recent analyses of silicate in seawater have, therefore, used this chemistry. Furthermore, reactive silicate is probably the only silicon species in seawater that can be used by siliceous organisms [204]. 

Muller [76] has described a gas chromatographic method for the determination of tributyltin compounds in sediments. The tributyltin compounds are first converted to tributylmethyltin by reaction with ethyl magnesium bromide, and then analysed using capillary gas chromatography with flame photometric detection and gas chromatography-mass spectrometry. Tributyltin was found in samples of sediment and these results demonstrated that the technique has detection limits of less than 0.5pg L 1. 

Non-specific sum parameter analysis [12,13], which is still used today, failed [14,15] in the analyses of some of these compounds. Chromatographic methods in combination with non-substance specific detectors, e.g. colorimetric and photometric [5] or with substance specific detectors such as IR (infrared spectroscopy), NMR (nuclear magnetic resonance spectroscopy) or MS (mass spectrometry), are applied increasingly nowadays. 

Instruments in which each test is performed in its own container or slide are known as discrete analysers, in contrast to flow analysers in which the samples follow each other through the same system of tubing. All discrete analysers have a common basic design incorporating a pipetting system, a photometric detector and a microprocessor. A development of the single test instrument is the parallel fast analyser, which analyses several samples simultaneously but for only one constituent. However, the change-over from one analytical procedure to another is quick and simple. 

All primary samples were analysed on site using photometric tests... 

The results obtained with ISEs have been compared several times with those of other methods. When the determination of calcium using the Orion SS-20 analyser was tested, it was found that the results in heparinized whole blood and serum were sufficiently precise and subject to negligible interference from K and Mg ([82]), but that it is necessary to correct for the sodium error, as the ionic strength is adjusted with a sodium salt [82], and that a systematic error appears in the presence of colloids and cells due to complexa-tion and variations in the liquid-junction potential [76]. Determination of sodium and potassium with ISEs is comparable with flame photometric estimation [39, 113, 116] or is even more precise [165], but the values obtained with ISEs in serum are somewhat higher than those from flame photometry and most others methods [3, 25, 27, 113, 116]. This phenomenon is called pseudohyponatremia. It is caused by the fact that the samples are not diluted in ISE measurement, whereas in other methods dilution occurs before and during the measurement. On dilution, part of the water in serum is replaced by lipids and partially soluble serum proteins in samples with abnormally increased level of lipids and/or proteins. 

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