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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.

This Bulletin describes potentiometric titration methods for checking sulfuric acid and chromic acid anodizing baths. In addition to the main components aluminum, sulfuric acid, and chromic acid, chloride, oxalic acid, and sulfate are determined.

It has been known for years that consuming too much nitrates from foodstuffs can result in cyanosis, particularly for small children and susceptible adults. According to the WHO standard, the hazard level lies at a mass concentration c(NO3-) ≥ 50 mg/L. However, more recent studies have shown that when nitrate concentrations in the human body are too high, they can (via nitrite) result in the formation of carcinogenic and even more hazardous nitrosamines.Known photometric methods for the determination of the nitrate anion are time-consuming and prone to a wide range of interferences. With nitrate analysis continually increasing in importance, the demand for a selective, rapid, and relatively accurate method has also increased. Such a method is described in this Application Bulletin. The Appendix contains a cselection of application examples where nitrate concentrations have been determined in water samples, soil extracts, fertilizers, vegetables, and beverages.

Potentiometric titration is an accurate method for determining chloride content. For detailed instructions and troubleshooting tips, download our Application Bulletin.

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).

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.

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.

The Application Bulletin describes the determination of suppressor in acid copper baths by smartDT. The determination of suppressor with dilution titration (DT) involves numerous additions with standard solution or sample to reach the evaluation ratio. Usually fixed, equidistant addition volumes are used. With smartDT, variable addition volumes are used that are dynamically calculated by the software. At the beginning, the volumes are bigger. Towards the evaluation ratio, the addition volume becomes smaller to guarantee a good accuracy of the result. The operator defines the first and the smallest addition volume to be used. All volumes in between are calculated by the software considering the progress of the determination. The time saving with smartDT compared to a classic DT with fixed addition volumes can be up to 40%. smartDT is suitable for nonlinear regression and quadratic regression as well as linear interpolation. It can be used for determination of suppressor in acid copper baths as well as in tin and tin-lead baths and works with 1, 2, and 3 mm Pt working electrodes. A 800 Dosino is required for the automatic addition of suppressor standard or sample. The method can also be used in fully automated systems.

Copper is arguably one of the most technologically relevant metals, especially for the semiconductor industry. The deposition process used in this industry is known as the dual-damascene process and it involves the electrodeposition of copper from an acidic cupric compound, in the presence of additives.This Application Note illustrates the use of the Autolab rotating ring disc electrode (RRDE) for the study of electrodeposition of copper and the detection of the Cu+ intermediate.

Determination of cuprous ions in the presence of ferrous ions in electrochemical copper leaching solutions.

Determination of free acid in copper refining solutions.

Determination of copper, principally in copper mining and refining solutions. The method may also be used fordetermination of purity of copper metal. Optimal results are obtained when aliquots containing copper in the rangeapproximately 3 - 6 mmol Cu are titrated.

Determination of Fe3+ and Cu2+ in copper refining solutions by thermometric titration. It was found that the conventional approach of masking Fe3+ to permit the iodometric determination of Cu2+ is not possible in some copper refining solutions.

Determination of nitrate in a copper plating bath after conversion of nitrate to ammonium. Direct potentiometric measurement using the NH3-ISE.

Monitoring organic additives in copper plating baths is crucial. The 2060 CVS Process Analyzer optimizes copper electroplating by providing precise bath control.

Special brighteners are used in electroplating baths in order to provide the refined surfaces with greater brightness. The concentration of brighteners must be kept constant at all times in order to ensure uniform end product quality. This Application Note describes how brighteners are determined in parallel with IC and CVS. The corresponding CVS application can be found under AN-V-183.

Determination of cyanide in alkaline plating baths by potentiometric titration with silver nitrate using the Ag-Titrode.

Determination of hydroxide and carbonate in alkaline plating baths by potentiometric titration with HCl using the combined glass electrode.

Determination of cadmium, copper, lead, and zinc in alkaline plating baths by potentiometric titration with EDTA using the Cu-ISE.

Acid copper baths are mainly used for the copper deposition on semiconductor wafers. Small amounts of chloride increase the speed of deposition and reduce anode polarization. However, higher concentrations are undesired, as this will decrease the quality of the copper deposition. Therefore, it is quite important to monitor the amount of chloride to have an effective, yet high-quality copper deposition process.In this Application Note, a fully automated solution based on titration is presented. In comparison to ion chromatography, titration offers the benefit that no dilution of the sample is necessary, and the hardware is comparatively low-priced. Furthermore, the fully automated solution allows users to minimize handling errors, to reduce workloads, and to guarantee outstanding reproducibility.

Electroplating processes are used in several different industry sectors to protect the surface quality of various products against corrosion or abrasion and significantly improve their working life. It is essential to check the bath composition on a regular basis to ensure that the process is operating correctly. Typical examples of electroplating baths include alkaline degreasing baths or acidic or alkaline baths containing metals e.g. copper, nickel, or chromium, or components like chloride and cyanide. It is crucial that the chosen analysis technique fulfills high safety standards for these kinds of analyses and produces reliable results. The OMNIS Sample Robot system automatically pipettes and analyzes aggressive electroplating bath samples on different workstations, increasing the safety in the lab. This provides more reliable results in comparison to manual titration and is more time efficient as different parameters can be analyzed in parallel.

Determination of suppressor «Copper GleamTM 2001 Carrier» in acid copper baths by dilution titration (DT) using cyclic voltammetric stripping (CVS).

Determination of brightener «Copper GleamTM 2001 Additive» in acid copper baths by modified linear approximation technique (MLAT) using cyclic voltammetric stripping (CVS).

Determination of suppressor «Cupracid BL-CT» in acid copper baths by dilution titration (DT) using cyclic voltammetric stripping (CVS).

Determination of brightener «Cupracid BL» in acid copper baths by linear approximation technique (LAT) using cyclicvoltammetric stripping (CVS).

Determination of suppressor «Cupraspeed» in acid copper baths by dilution titration (DT) using cyclic voltammetric stripping (CVS).

Determination of brightener «Cupraspeed» in acid copper baths by modified linear approximation technique (MLAT)using cyclic voltammetric stripping (CVS).

The concentration of Sb(total) in an acid Cu bath is determined by anodic stripping voltammetry using hydrochloric acid as electrolyte. Due to the excess of Cu the deposition potential has to be chosen only 50 mV more negative than the Sb signal

Determination of suppressor «MACuSpecTM PPR 100 Wetter» in acid copper baths by dilution titration (DT) using cyclic voltammetric stripping (CVS).

Determination of brightener «MACuSpecTM PPR 100 Brightener» in acid copper baths by modified linear approximation technique (MLAT) using cyclic voltammetric stripping (CVS).

Determination of suppressor «MultiBondTM 100 Part A20» in an acid copper bath by dilution titration (DT) using cyclicvoltammetric stripping (CVS).

Determination of suppressor «InPulse H6» in acid copper baths by dilution titration (DT) using cyclic voltammetric stripping (CVS).

Determination of brightener «InPulse H6» in acid copper baths by modified linear approximation technique (MLAT) using cyclic pulse voltammetric stripping (CPVS).

Determination of suppressor «Thru-Cup EVF-B» in acid copper baths by dilution titration (DT) using cyclic voltammetric stripping (CVS).

Determination of brightener «Thru-Cup EVF-1A» in acid copper baths by modified linear approximation technique (MLAT) using cyclic voltammetric stripping (CVS).

Determination of leveler «Thru-Cup EVF-R» in acid copper baths by response curve technique (RC) using cyclic voltammetric stripping (CVS).

The concentration of Cu in a cyanidic Cu bath is determined by polarography.

Determination of suppressor «Top Lucina α-M» in acid copper baths by dilution titration (DT) using cyclic voltammetric stripping (CVS).

Determination of brightener «Top Lucina α-2» in acid copper baths by modified linear approximation technique (MLAT) using cyclic voltammetric stripping (CVS).

Determination of leveler «Top Lucina α-3» in acid copper baths by response curve technique (RC) using cyclic voltammetric stripping (CVS).

Thiourea measurement during copper electrorefining can be complicated by high chloride levels. Voltammetric analysis overcomes this issue, improving copper quality.

The determination of suppressor with dilution titration (DT) involves numerous additions with standard solution or sample to reach the evaluation ratio. Usually fixed, equidistant addition volumes are used. With smartDT, variable addition volumes are used that are automatically calculated by the software. At the beginning, the volumes are bigger. Towards the evaluation ratio, the addition volume becomes smaller to guarantee a good accuracy of the result. The operator defines the first and the smallest addition volume to be used. All volumes in between are calculated by the software considering the progress of the determination. Using smartDT with intelligent addition volumes, the determination of suppressor can be significantly accelerated with the same or even better accuracy than with the classic DT. The time saving per determination is between 20 and 40%.

This Application Note describes the polarograhic determination of copper in electroplating baths used in the production of thin-film copper indium gallium diselenide solar cells (CIGS cells). The CIGS absorber layer is electrodeposited on a molybdenum-coated substrate.Copper analysis is carried out after dilution of the sample with sulfuric acid as supporting electrolyte.

This Application Note describes the polarographic determination of indium in electroplating baths used in the production of copper indium gallium diselenide thin-film solar cells (CIGS cells). The CIGS absorber layer is electrodeposited on the molybdenum-coated substrate. Indium analysis is carried out after dilution of the bath sample with sulfuric acid as supporting electrolyte.

This Application Note describes the determination of gallium in electroplating baths used in the production of copper indium gallium diselenide thin-film solar cells (CIGS cells). The CIGS absorber layer is electrodeposited on a molybdenum-coated substrate. Gallium analysis using anodic stripping voltammetry (ASV) is carried out after dilution of the sample with sulfuric acid as supporting electrolyte.

This Application Note describes the polarographic determination of selenite in electroplating baths used in the production of copper indium gallium diselenide thin-film solar cells (CIGS cells). The CIGS absorber layer is electrodeposited on a molybdenum-coated substrate. Selenite analysis is carried out after dilution of the sample with sulfuric acid as supporting electrolyte.

For the past three decades, Cyclic Voltammetric Stripping (CVS) has been the standard practice for analyzing organic additives in electroplating copper baths in the circuit board and wafer plating industries. The variations in the compositions of such baths have created a need for more optimized method development routines. New advancements in the hardware and software protocols for CVS have simplified the overall process of method optimization to a great extent. In this study, the process of method optimization is discussed in conjunction with these protocols.

Ion measurement can be conducted in several different ways, e.g., ion chromatography (IC), inductively coupled plasma optical emission spectrometry (ICP-OES), or atom absorption spectroscopy (AAS). Each of these are well-established, widely used methods in analytical laboratories. However, the initial costs are relatively high. In contrast, ion measurement by the use of an ion-selective electrode (ISE) is a promising alternative to these costly techniques. This White Paper explains the challenges which may be encountered when applying standard addition or direct measurement, and how to overcome them in order for analysts to gain more confidence with this type of analysis.