Aplicații

A convenient adsorptive cathodic stripping voltammetric (AdCSV) method has been developed for trace determination of uranium(VI) in drinking water samples using chloranilic acid (CAA). The presence of various matrix components (KNO3, Cl-, Cu2+, organics) can impair the determination of the uranium-CAA complex. The interferences can be mitigated, however, by appropriate selection of the voltammetric parameters. While problematic water samples still allow uranium determination in the lower µg/L range, in slightly polluted tap water samples uranium can be determined down to the ng/L range, comparable to the determination by current ICP-MS methods.

The presence of copper in fuel ethanol blends has gained considerable attention, since Cu2+ catalyzes oxidative reactions in gasoline leading to a deterioration of olefins and the formation of gum. Anodic stripping voltammetry (ASV), one of the most sensitive and accurate techniques for trace-metal analysis, has been demonstrated for the determination of Cu(II) in ethanol/gasoline blends without any sample pretreatment. Copper ions are first electrodeposited onto the surface of a hanging mercury drop electrode (HMDE) before the amalgamated copper is quantitatively stripped (anodically dissolved), a current-voltage curve being recorded.Experimental conditions such as deposition time and potential as well as the suitable electrolyte and reference electrode were determined in preliminary experiments. For synthetic samples spiked with Cu2+ (5…100 µg/L), recovery rates between 96 and 112% were obtained. The copper-spiked E85 sample provided a recovery of 100%. The relative standard deviations for Cu2+ concentrations of 5 µg/L and above were 8.0 and 5.5% respectively. Using a preconcentration time of 60 s at -0.7 V versus Ag/AgCl, a linear range of 0…500 µg/L with a detection limit of 2 µg/L was obtained.

The Restriction of Hazardous Substances (RoHS) Directive 2002/95/EC stipulates maximum limits for the hazardous metals cadmium, lead and mercury as well as the hexavalent chromium and the brominated flame retardants in electrical and electronic products. To ensure compliance, reliable analysis methods are required.This poster deals with the wet-chemical determination of trace concentrations of the six RoHS-restricted substances in a wide variety of materials including metals, electrotechnical components, plastics and wires. After sample preparation according to IEC 62321, the metals lead, cadmium and mercury are best determined by anodic stripping voltammetry (ASV) and the flame retardants PBB and PBDE are quantified by direct-injection ion chromatography (IC) using spectrophotometric detection. Chromium(VI) can be determined either by adsorptive stripping voltammetry (AdSV) or IC. Both methods are very sensitive and meet prescribed RoHS limits.

This poster presents an approach that couples a Particle-Into-Liquid-Sampler (PILS) to a dual-channel ion chromatograph (IC) for measurement of aerosol anions and cations and a voltammetric measuring stand (VA) to determine the heavy metals. Feasibility of the PILS-IC-VA online system was demonstrated by collecting aerosol samples in Herisau Switzerland, at defined time intervals; air pollution events were simulated by burning lead- and cadmium-coated sparklers.

Because of its toxicity, the World Health Organization recommends a maximum arsenic content in drinking water of 10 μg/L. Anodic stripping voltammetry with the scTRACE Gold offers a straightforward, highly affordable alternative to spectroscopic determination.

In the following tables, the half-wave potentials or peak potentials of 90 metal ions are listed. The half-wave potentials (listed in volts) are measured at the dropping mercury electrode (DME) at 25 °C unless indicated otherwise.

Two methods are described for the determination of chromium: a biamperometric titration and a polarographic analysis.

The determination of the lead content in engine fuels has gained considerable importance since the introduction of the catalytic converter technique. Even small contents of lead interfere with the effectiveness of the catalysts or may destroy them. On the other hand, there are still many vehicles on the roads which run on leaded fuel (addition of tetraalkyl lead). Here also the knowledge of the lead content is of interest.With reference to DIN 51769 and ASTM 0-1269 a simplified procedure for the determination of lead in petrochemical products is described. The products are digested with HCl and the lead compounds are converted to lead(II) chloride. After extraction with water, the inverse voltammetric Pb determination is carried out.

The quantitative determination of the alkaloid nicotine, which is an essential constituent of the tobacco plant, can be carried out by polarography. The quantification limit is less than 0.1 mg/L in the polarographic vessel.

Fructose (fruit sugar) is the only ketose that occurs naturally. It is found free in a mixture with dextrose (honey, sweet fruits, tomatoes) or bound as a component of cane sugar and various starch-like carbohydrates. As fructose tastes sweeter than dextrose, it finds great use as a sweetening agent.In 1932, the polarographic reducibility of sugar was described for the first time by Heyrovsky and Smoler. The following method can be used to determine the fructose content of fruit, fruit juice and honey quantitatively.

The photometric determination of nitrate is limited by the fact that the respective methods (salicylic acid, brucine, 2,6-dimethyl phenol, Nesslers reagent after reduction of nitrate to ammonium) are subject to interferences. The direct potentiometric determination using an ion-selective nitrate electrode causes problems in the presence of fairly large amounts of chloride or organic compounds with carboxyl groups. The polarographic method, on the other hand, is not only more rapid, but also practically insensitive to chemical interference, thus ensuring more accurate results. The limit of quantification depends on the matrix of the sample and is approximately 1 mg/L.

This Bulletin is a supplement to Application Bulletin no. 36 (Half-wave potentials of inorganic substances) in the sense that the half-wave potentials of 100 different organic substances are listed. At the same time the supporting electrolytes used and the limits of determination are given.The various substances are listed in alphabetical order. The most important polarographically active functional groups are taken into consideration. This means that substances for related structures can also be determined polarographically in the same or similar supporting electrolytes, although they may not appear in the list.Unless otherwise stated, the half-wave potentials refer to a temperature of 20 °C, and the potentials are given in volts, measured with a sat. KCI-Ag/AgCl electrode assembly.The determination limits give the smallest concentrations which can be measured without risking serious errors in the results. In all cases, the limit of detection lies below the limit of determination.

This Application Bulletin describes the voltammetric determination of the elements antimony, bismuth, and copper. The limit of detection for the three elements is 0.5 ... 1 µg/L.

According to the described method, NTA and EDTA can be determined in mass concentrations of 0.05 mg/L up to 25 mg/L in polluted water and wastewater.At first NTA and EDTA are converted to the corresponding Bi complexes by addition of Bi3+ ions at a pH value of 2.0. As these Bi complexes have significantly different peak potentials, they can be determined simultaneously by DP polarography. The interfering anions nitrite, sulfite, and sulfide are removed from the sample by acidification and purging. Interfering cations are removed by cation exchange; any NTA or EDTA heavy metal complexes present in the sample are disintegrated during this procedure. To remove surfactants and other organic components interfering with the analysis, the sample solution is run through a column filled with non-polar adsorber resin.

This Application Bulletin describes the determination of mercury by anodic stripping voltammetry (ASV) at the rotating gold electrode. With a deposition time of 90 s, the calibration curve is linear from 0.4 to 15 μg/L; the limit of quantification is 0.4 μg/L.The method has primarily been drawn up for investigating water samples. After appropriate digestion, the determination of mercury is possible even in samples with a high load of organic substances (wastewater, food and semi-luxuries, biological fluids, pharmaceuticals).

Edible oils and fats contain natural tocopherols and, in some cases, also synthetic tocopherols added as antioxidants. The method described below allows the simple and rapid determination of the tocopherol content by voltammetry. The tocopherols are oxidized electrochemically at the glassy carbon electrode (GCE). The limit of quantitation is approximately 5 ppm (mg/kg) tocopherol.

In addition to its natural occurrence in fruit and vegetables, ascorbic acid (Vitamin C) is used as an antioxidant in foods and drinks. Ascorbic acid is furthermore also to be found in numerous drugs.Ascorbic acid and its salts and esters can be determined with titration or by using polarography, for which ascorbic acid is oxidized to form dehydroascorbic acid.Bi-voltammetric or photometric equivalence point indication can be used for titrimetric determination. It must be taken into account here that only bi-voltammetric indication is independent of the inherent color of the sample. Polarography is the most selective of the methods described, as other reducing or oxidizing substances are not recorded.

This Application Bulletin describes a polarographic method for the determination of cyanide that allows to determine free cyanide fast and accurately. The determination also succeeds in solutions containing sulfides, where other methods fail. Cyanide concentrations in the range b(CN–) = 0.01...10 mg/L cause no problems. Interference caused by anions and complexed cyanides has been investigated.

Wine sometimes contains heavy metals which can be precipitated out by the addition of potassium ferrocyanide. Generally, these are quantities of iron ranging between 1 and 5 mg, and exceptionally up to 9 mg Fe/L. Zinc, copper, and lead – in descending order of content – may also be present. To estimate the quantity of potassium ferrocyanide necessary for the «décassage of the wine», only very complicated and relatively inaccurate methods have been described until now.This Bulletin permits accurate results to be obtained easily with a simple instrumentation. The results are available in a short time.

Cadmium, lead, and copper can be determined simultaneously in oxalate buffer by anodic stripping voltammetry (ASV) after digestion with sulfuric acid and hydrogen peroxide. Tin present in the sample does not interfere with the determination of lead.For the voltammetric determination of tin please refer to Application Bulletin no. 176.

Cu2+, Co2+, Ni2+, Zn2+, and Fe2+/Fe3+ are determined simultaneously. Interference due to the presence of other metals is mentioned, and methods given to eliminate it. The threshold of determination is ρ = 20 µg/L for Co and Ni, and ρ = 50 µg/L each for Cu, Zn, and Fe.

This Application Bulletin describes methods for the polarographic and voltammetric determination of small quantities of chromium in water, effluent water and biological samples. Methods for the sample preparation for various matrices are given.

In the past, selenium determinations have always been either unreliable or have required complicated methods. However, as selenium is on the one hand an essential trace element (vegetable and animal tissues contain about 10 μg/kg), while on the other hand it is very toxic (threshold value 0.1 mg/m3), it is very important to cover determinations in the micro range. Cathodic stripping voltammetry (CSV) enables selenium to be determined in mass concentrations down to ρ(Se(IV)) = 0.3 μg/L.

"A sensitive methods to determine manganese is described. It is primarily suitable for the investigation of ground, drinking and surface waters, in which the concentration of manganese is important. The method can naturally also be used for trace analysis in other matrices.Manganese is determined in an alkaline borate buffer by the anodic stripping voltammetry (ASV). Interference by intermetallic compounds is prevented by the addition of zinc ions in the sample. The limit of determination lies at b(Mn) = 2 µg/L."

This Bulletin describes a simple polarographic method for the determination of quinine in drinks and tablets. Whereas in drinks quinine can be determined directly, in the case of tablets it must first be extracted. The limit of quantification is 0.2 mg/L or 4 μg/tablet.

Nitrite can be determined polarographically after its conversion to diphenylnitrosamine (C6H5)2NNO. Potassium thiocyanate is used as a catalyst in order for the conversion to proceed rapidly and quantitatively. The reaction takes place in acid solution at a pH value of approx. 1.5. The limit of quantification is 5 μg/L NO2-.

This Application Bulletin describes a voltammetric method for the determination of aluminum in water samples, dialysis solutions, sodium chloride solutions and digestion solutions (e.g. of lyophilisates). The method utilizes the complexation of the Al3+ ion by Calcon (Eriochrome blue black R). The formed complex can easily be reduced electrochemically at 60 °C. The limit of quantitation depends on the purity of the reagents used and is approx. 5 µg/L.

A method is described in this Bulletin that allows molybdenum to be determined in steel and other materials containing a high iron concentration. Mo(VI) is determined at the dropping mercury electrode by catalytic polarography. The determination limit is approx. 10 μg/L Mo(VI).

This Application Bulletin describes a simple polarographic method to determine monomeric styrene in polymers. The limit of determination lies at 5 mg/L. Before the determination, styrene is converted to the electrochemically active pseudonitrosite using sodium nitrite.

As the determination of the exact content of individual glycerides in fats and oils is difficult and time-consuming, several fat sum parameters or fat indices are used for the characterization and quality control of fats and oils. Fats and oils are not only essential for cooking, they are also an important ingredient in pharmaceuticals and personal care products, such as ointments and creams. Consequently, several norms and standards describe the determination of the most important quality control parameters. This Application Bulletin describes eight important analytical methods for the following fat parameters in edible oils and fats:Determination of water content in accordance with the Karl Fischer method; Oxidation stability in accordance with the Rancimat method; Iodine value; Peroxide value; Saponification value; Acid value, free fatty acids (FFA); Hydroxyl number; Traces of nickel using polarography; Special care is taken to avoid chlorinated solvents in these methods. Also, as many of the mentioned methods as possible are automated.

"Molybdenum is an essential trace element for plant growth. Since it occurs in natural waters only in trace amount, a very sensitive method of determination is needed. Using the following polarographic method, it is possible to determine 5·10-10 mol/L resp. 50 ng/L.The principle of the method is based on the reaction between the molybdate ion MoO42- and the complexing agent 8-hydroxy-7-iodo-quinoline-5-sulfonic acid (H2L) to form a MoO2L22- complex, which is adsorbed on the mercury electrode. The adsorbed Mo(VI) is reduced electrochemically to the Mo(V) complex. The hydrogen ions present in the solution oxidize Mo(V) again spontaneously to form the Mo(VI) complex, which is thus newly available for electrochemical reduction. This catalytic reaction is the reason for the high sensitivity of the method.Tungsten W(VI) exhibits practically the same electrochemical behavior as molybdenum, but is not described in detail in this Application Bulletin."

The metals Cd, Co, Cu, Fe, Ni, Pb, and Zn are determined in the sub-ppb range (limit of detection 0.05 µg/L) by means of stripping voltammetry. The DP-ASV method is used for Cd, Cu, Pb, and Zn whereas Co, Ni, and Fe are determined by means of the DP-CSV method (dimethylglyoxime or catechol complexes).Use of the VA Processor and the sample changer allows automatic determination of the above metal ions in one solution. The method has been specially developed for trace analysis in the manufacture of semiconductor chips based on silicon. It can naturally also be employed successfully in environmental analysis.

In most electrolytes the peak potentials of lead and tin are so close together, that a voltammetric determination is impossible. Difficulties occur especially if one of the metals is present in excess.Method 1 describes the determination of Pb and Sn. Anodic stripping voltammetry (ASV) is used under addition of cetyltrimethylammonium bromide. This method is used when:• one is mainly interested in Pb• Pb is in excess• Sn/Pb ratio is not higher than 200:1According to method 1, Sn and Pb can be determined simultaneously if the difference in the concentrations is not too high and Cd is absent.Method 2 is applied when traces of Sn and Pb are found or interfering TI and/or Cd ions are present. This method also uses DPASV in an oxalate buffer with methylene blue addition.

Maleic and fumaric acid can be reduced electrochemically to succinic acid. In acidic solutions a differentiation of the two acids is not possible since both are reduced at the same potential. On the other hand, separation at pH 7.8...8.0 is easily possible since fumaric acid is now more difficult to reduce at the lower proton concentration (as a result of cis-trans isomerism) than maleic acid.

This Bulletin describes the voltammetric determination of aluminum in water samples down to a concentration of 1 μg/L. An aluminum complex is formed with alizarin red S (DASA) and enriched at the HMDE. The following determination employs differential pulse adsorptive stripping voltammetry (DP-AdSV). Disturbing Zn ions are eliminated by addition of CaEDTA.

4-Carboxybenzaldehyde, in the following referred to as 4-CBA, can be reduced directly at the dropping mercury electrode (DME) in an ammoniacal solution. After a very simple sample preparation it is now possible to determine the concentration of 4-CBA in terephthalic acid quickly and precisely by polarography down to the lower ppm range.

After the degradation of biological samples (e.g. milk, wool, etc.), it is often important to know the cystine/cysteine ratio. This Application Bulletin describes the simultaneous, polarographic determination of the two amino acids. The determination is performed in perchloric acid solution at the DME. Samples with a high protein content require that the determination is performed in an alkaline solution.

Thiourea forms highly insoluble compounds with mercury. The resulting anodic waves are used for the polarographic determination of thiourea. For the analysis of very small quantities (µg/L), cathodic stripping voltammetry (CSV) is used. Differential Pulse measuring mode is used in both cases.

Formaldehyde can be determined reductively at the DME. Depending on the sample composition it may be possible to determine the formaldehyde directly in the sample. If interferences occur then sample preparation may be necessary, e.g. absorption, extraction, or distillation.Two methods are described. In the first method formaldehyde is reduced directly in alkaline solution. Higher concentrations of alkaline or alkaline earth metals interfere. In such cases the second method can be applied. Formaldehyde is derivatized with hydrazine forming the hydrazone, which can be measured polarographically in acidic solution.

Sulfide and sulfite can be determined polarographically without any problems. For sulfide, polarography is performed in an alkaline solution, for sulfite in a slightly acidic primary solution. The method is suitable for the analysis of pharmaceuticals (infusion solutions), wastewater/flue gas water, photographic solutions, etc.

This Application Bulletin describes the stripping analysis of Ag at the rotating disk electrode (RDE) with glassy carbon tip (GC) or Ultra Trace graphite tip. In routine operation, the determination limit lies at approx. 10 μg/L Ag, with careful work 5 μg/L Ag can be obtained. After appropriate digestion, silver determination is also possible with samples containing a relatively high proportion of organic substances (e.g. wine, foodstuffs etc.). The method has been developed primarily for water samples (well, ground and wastewater, desilvering solutions of the photographic industry).

This Application Bulletins describes the determination of nicotinamide (vitamin PP), a vitamin of the B series. Instructions for the determination in solutions (e.g. fruit juice), vitamin capsules and multivitamin tablets are given. The linearity range of the determination is also specified. The limit of detection is approximately 50 μg/L nicotinamide.

This Application Bulletin describes the polarographic determination of folic acid, a vitamin of the B series, also known as vitamin B9 or vitamin BC. Instructions for the determination in solutions (e.g. fruit juice), vitamin capsules and multivitamin tablets are given. The linear range of the determination is also specified. The limit of detection is approx. 75 µg/L folic acid.

This Application Bulletins describes the polarographic determination of thiamine (vitamin B1). The procedure allows an analysis in monovitamin preparations. The linear range of the determination is also given. The limit of detection is approx. 50 µg/L thiamine.

This Application Bulletin describes the polarographic determination of riboflavin (vitamin B2). The procedure allows an analysis in monovitamin preparations. The limit of determination is approx. 100 μg/L.

This Application Bulletin describes …

This Bulletin gives a survey of standard methods from the field of water analysis. You will also find the analytical instruments required for the respective determinations and references to the corresponding Metrohm Application Bulletins and Application Notes. The following parameters are dealt with: electrical conductivity, pH value, fluoride, ammonium and Kjeldahl nitrogen, anions and cations by means of ion chromatography, heavy metals by means of voltammetry, chemical oxygen demand (COD), water hardness, free chlorine as well as a few other water constituents.

This Application Bulletins describes the polarographic determination of pyridoxine (vitamin B6). The method given allows determination in monovitamin and in some multivitamin preparations. The linear range of the analysis is also specified. The limit of detection is approx. 100 µg/L pyridoxine · HCI.

This Bulletin describes the determination of arsenic by anodic stripping voltammetry (ASV) at the rotating gold electrode. A determination limit of 0.5 μg/L can be achieved with 10 mL sample solution. A differentiation between the As(III) concentration and the total arsenic concentration can be made by appropriate selection of the deposition potential. The analyses are performed with a special gold electrode whose active surface is located laterally; c(HCl) = 5 mol/L is used as supporting electrolyte. For the determination of the total arsenic content, As(III) and As(V) are reduced at -1200 mV by nascent hydrogen to As0, which is preconcentrated on the electrode surface. If the deposition is carried out at -200 mV then only As(III) is reduced; this allows the differentiation between total arsenic and As(III). During the subsequent voltammetric determination the preconcentrated As0 is again oxidized to As(III).

The standard method postulated by DIN 38406 Part 16 describes the determination of Zn, Cd, Pb, Cu, Tl, Ni, and Co in drinking, ground, surface and precipitation (e.g. rain) water. Because the presence of organic substances in the water samples can strongly interfere with the voltammetric determination, a pretreatment with UV digestion using hydrogen peroxide is necessary. This digestion ensures the elimination of all organic substances without introduction of blank values. These methods can, of course, also be applied for trace analysis in other materials, e.g. trace analysis in the production of semiconductor chips based on silicon. Zn, Cd, Pb, Cu, and Tl are determined on the HMDE by means of anodic stripping voltammetry (ASV), Ni and Co by means of adsorptive stripping voltammetry (AdSV).