Antimony detection

Removal by Oxidation. The oxidizing process used to remove antimony, arsenic, and tin has been termed softening because lowering these impurities results in a readily detectable softening of the lead. 

Analysis of zinc solutions at the purification stage before electrolysis is critical and several metals present in low concentrations are monitored carefully. Methods vary from plant to plant but are highly specific and usually capable of detecting 0.1 ppm or less. Colorimetric process-control methods are used for cobalt, antimony, and germanium, turbidimetric methods for cadmium and copper. Alternatively, cadmium, cobalt, and copper are determined polarographicaHy, arsenic and antimony by a modified Gutzeit test, and nickel with a dimethylglyoxime spot test. 

Discussion. Iodine (or tri-iodide ion Ij" = I2 +1-) is readily generated with 100 per cent efficiency by the oxidation of iodide ion at a platinum anode, and can be used for the coulometric titration of antimony (III). The optimum pH is between 7.5 and 8.5, and a complexing agent (e.g. tartrate ion) must be present to prevent hydrolysis and precipitation of the antimony. In solutions more alkaline than pH of about 8.5, disproportionation of iodine to iodide and iodate(I) (hypoiodite) occurs. The reversible character of the iodine-iodide complex renders equivalence point detection easy by both potentiometric and amperometric techniques for macro titrations, the usual visual detection of the end point with starch is possible. 

Electrochemical detection has been achieved in a number of ways. The change in pH has been sensed with a traditional glass pH electrode antimony electrode or amperometrically via the pH sensitive oxidation of hydrazine... 

It is known [16] that at room temperature antimony evaporates as molecules. The molecules of antimony according to [17] do not affect conductivity of the sensor made of zinc oxide. Similar conclusion can be obtained from experiments with freshly reduced antimony films. It occurs that without initial adsorption of hydrogen atoms one fails to detect any signals from the sensor in contrast to experimental data (see Fig. 6.2). The resistivity of the sensor remains constant for any distance from the surface of the antimony film. Consequently, the signals of the sensor detected in experiment are not linked with effects of the antimony particles on the sensor. 

Figure 6.4 shows the change in the sensor conductivity as a function of temperature. Curve / shows the dependence of sensor resistivity with temperature when the sensor is positioned in evacuated installation. The introduction of antimony hydride was made at temperature - 75°C bringing about no change in resistivity. When the temperature of the sensor was increased up to - 20 C there were no effects detected on its resistivity caused by antimony hydride. Only at higher temperatures one can observe deviation of dependence RiT) from curve 1 which is caused by decomposition of SbHa on ZnO. These results led to experiments on emission of H-atoms in a special vial when Sb-film treated by H-atoms was kept at a room temperature and sensors were kept at the temperature of - 80 C. Under these conditions, as is shown by above reasoning. 

Simultaneous and continuous measurements of extracellular pH, potassium K+, and lactate in an ischemic heart were carried out to study lactic acid production, intracellular acidification, and cellular K+ loss and their quantitative relationships [6, 7], The pH sensor was fabricated on a flexible kapton substrate and the pH sensitive iridium oxide layer was electrodeposited on a planar platinum electrode. Antimony-based pH electrodes have also been used for the measurement of myocardial pH in addition to their application in esophageal acid reflux detection. 

Sturgeon et al. [59] have described a hydride generation atomic absorption spectrometry method for the determination of antimony in seawater. The method uses formation of stibene using sodium borohydride. Stibine gas was trapped on the surface of a pyrolytic graphite coated tube at 250 °C and antimony determined by atomic absorption spectrometry. An absolute detection limit of 0.2 ng was obtained and a concentration detection limit of 0.04 pg/1 obtained for 5 ml sample volumes. 

Tao et al. [658] have described a procedure in which antimony and arsenic were generated as hydrides and irradiated with ultraviolet light. The broad continuous emission bands were observed in the ranges about 240-750 nm and 220 - 720 nm, and the detection limits were 0.6 ng and 9.0 ng for antimony and arsenic, respectively. Some characteristics of the photoluminescence phenomenon were made clear from spectroscopic observations. The method was successfully applied to the determination of antimony in river water and seawater. The apparatus used in this technique is illustrated in Fig. 5.16. 

De Oliviera et al. [739] have described a technique for determining these elements based on the hydride generation technique. Detection limits are 1 xg/l for arsenic and antimony, and 0.5 pg/1 for selenium. 

Foreback CC (1973) Some studies on the detection and determination of mercury, arsenic, and antimony in gas discharges. Thesis. University of South Florida... 

Braman et al. [34] used sodium borohydride to reduce arsenic and antimony in their trivalent and pentavalent states to the corresponding hydrides. Total arsenic and antimony are then measured by their spectral emissions, respectively, at 228.8 nm and 242.5 nm. Limits of detection are 0.5 ng for antimony and 1 ng for arsenic, copper, and silver. Oxidants interfere in this procedure. 

It has been reported that the differential determination of arsenic [36-41] and also antimony [42,43] is possible by hydride generation-atomic absorption spectrophotometry. The HGA-AS is a simple and sensitive method for the determination of elements which form gaseous hydrides [35,44-47] and mg/1 levels of these elements can be determined with high precision by this method. This technique has also been applied to analyses of various samples, utilising automated methods [48-50] and combining various kinds of detection methods, such as gas chromatography [51], atomic fluorescence spectrometry [52,53], and inductively coupled plasma emission spectrometry [47]. 

Yamamoto et al. [33] applied this technique to the determination of arsenic (III), arsenic (V), antimony (III), and antimony (V) in Hiroshima Bay Water. These workers used a HGA-A spectrometric method with hydrogen-nitrogen flame using sodium borohydride solution as a reductant. For the determination of arsenic (III) and antimony (III) most of the elements, other than silver (I), copper (II), tin (II), selenium (IV), and tellurium (IV), do not interfere in at least 30 000-fold excess with respect to arsenic (III) or antimony (III). This method was applied to the determination of these species in sea water and it was found that a sample size of only 100 ml is enough to determine them with a precision of 1.5-2.5%. Analytical results for surface sea water of Hiroshima Bay were 0.72 xg/l, 0.27 xg/l, and 0.22 xg/l, for arsenic (total), arsenic (III), and antimony (total), respectively, but antimony (III) was not detected. The effect of acidification on storage was also examined. 

Tin, antimony, and selenium hydrides, produced by the borohydride reduction technique, were found to chemiluminesce with ozone in an analytical detection scheme. Limits of detection were 35, 10, and 110 ng of Sn, Sb, and Se,... 

The most commonly used and widely marketed GC detector based on chemiluminescence is the FPD [82], This detector differs from other gas-phase chemiluminescence techniques described below in that it detects chemiluminescence occurring in a flame, rather than cold chemiluminescence. The high temperatures of the flame promote chemical reactions that form key reaction intermediates and may provide additional thermal excitation of the emitting species. Flame emissions may be used to selectively detect compounds containing sulfur, nitrogen, phosphorus, boron, antimony, and arsenic, and even halogens under special reaction conditions [83, 84], but commercial detectors normally are configured only for sulfur and phosphorus detection [85-87], In the FPD, the GC column extends... 

The following species can be separately determined AsIII, AsV, Sblll, SbV. Detection limits are lOp mol L 1 (arsenic) and 3.3pmol L 1 (antimony). 

If necessary a preconcentration was carried out on this solution to lower the detection limits of the method. Preconcentration was achieved by a method involving co-precipitation of the antimony with hydrous zirconium oxide in which the digest is stirred with 150mg zirconyl chloride and the pH adjusted to 5 with ammonia to coprecipitate antimony and hydrous zirconium oxide. The isolated precipitate is dissolved is 7M hydrochloric acid and 30% sulphuric acid. Antimony is then converted to the pentavalent state by successive treatment with titanium III chloride and sodium nitrite and excess nitrite destroyed by urea. 

The selective hydride generation-gas chromatographic method [121] using photoionization detection discussed in section 12.10.2.1 for the determination of arsenic III and arsenic V has been applied to the determination of down to 3.3pmol L 1 of antimony (Sb III, SbV) in sediments. 

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