Alkalmazások

This poster presents a straightforward ion chromatographic determination of HF, HNO3, short-chain organic acids and H2SiF6 in etching bath samples. Standard ions such as fluoride, nitrate, acetate and sulfate are determined via suppressed conductivity detection while dissolved silicate is spectrophotometrically detected in the same run after downstream post-column reaction (PCR) as molybdosilicic acid. Analytical results of several commercial HF-HNO3-H2SiF6 mixtures obtained by ion chromatography (IC) and titration showed good agreement, which confirms the applicability of the presented «dual» detection IC method for controlling the composition of acidic texturing baths.

A potentiometric method for the determination of nickel in gold and silver electroplating baths is described. The titration is carried out with KCN. Gold and silver are removed before titration by a reduction process. It is also possible to determine nickel in steel alloys, etc. (see the literature reference).Ni2+ + 4 KCN + 2NH4+ → (NH4)2[Ni(CN)4] + 4 K+

A routine method for the determination of copper is described. After dissolving the sample and adding a KI/KCNS solution, the released iodine is back-titrated with thiosulfate. The endpoint indication is potentiometric.

This Bulletin describes the simultaneous determination of gold and copper by potentiometric titration using an Fe(II) solution as titrant. Fe(II) reduces Au(III) directly to the free metal, whereas Cu(II) does not react. By the addition of fluoride ions the Fe(III) is complexed and a shift of the redox potential is effected. Afterwards, potassium iodide is added, thus reducing the Cu(II) to Cu(I), and the free iodine is again titrated with the Fe(II) solution using a Pt Titrode.Chemical reactions:Au(III) + 3 Fe(II) → Au + 3 Fe(III)2 Cu(II) + 2 I- → 2 Cu(I) + I2I2 + 2 Fe(II) → 2 I- + 2 Fe(III)

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.

The determination of cyanide is very important not only in electroplating baths and when decontaminating wastewater but, due to its high toxicity, also in water samples in general. Concentrations of 0.05 mg/L CN- can already be lethal for fish.This Bulletin describes the determination of cyanide in samples of different concentrations by potentiometric titration.Chemical reactions:2 CN- + Ag+ → [Ag(CN)2]-[Ag(CN)2]- + Ag+ → 2 AgCN

Silver is an important metal not only in jewelry and silverware but also in electrical conductors and contacts. The knowledge of the exact silver content in fine silver and silver alloys ensures that quality standards for jewelry and silverware are met. As for the plating industry, the knowledge of the amount of silver in silver plating baths helps to run the bath efficiently.While X-ray fluorescence (XRF) is a fast alternative to determine the silver content in fine silver and silver alloys, it can only determine the silver content of the outermost sections of the metal. In contrast, titration offers a more comprehensive solution considering the whole sample, thus preventing fraud by thick plating.This application bulletin describes the potentiometric determination of silver in fine silver and silver alloys accordingto EN ISO 11427, ISO 13756, GB/T 17823, and GB/T 18996 as well as in silver plating baths by a titration with potassium bromide or potassium chloride, respectively

Boric acid is used in many primary circuits of nuclear power plants, in nickel plating baths, and in the production of optical glasses. Furthermore, boron compounds are found in washing powders and fertilizers. This bulletin describes the potentiometric and thermometric determination of boric acid. The determination also covers further boron compounds, when acidic digestion is applied.

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.

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.

Potentiometric titration methods for the analysis of acid and alkaline tin plating baths are presented. The following methods are described: tin(II) / tin(IV) / total tin, free fluoroboric acid, or free sulfuric acid, chloride in acidic tin baths, free hydroxide, and carbonate in alkaline tin baths.

Methods are described for the potentiometric analysis of the following bath components:Brass plating bath: copper, zinc, free cyanide, ammonium, carbonate, and sulfite.Bronze plating bath: copper, tin, and free cyanide.

This Bulletin describes the potentiometric determination of lead, tin(II), and free fluoroboric acid.

This Bulletin describes titrimetric methods for the determination of cadmium, free sodium hydroxide, sodium carbonate, and total cyanide. The free cyanide can be calculated from the total cyanide and the Cd content.

This Bulletin describes the complexometric potentiometric titration of metal ions. An ion-selective copper electrode is used to indicate the endpoint of the titration. Since this electrode does not respond directly to complexing agents, the corresponding Cu complex is added to the solution. With the described electrode, it is possible to determine water hardness and to analyze metal concentrations in electroplating baths, metal salts, minerals, and ores. The following metal ions have been determined: Al3+, Ba2+, Bi3+, Ca2+, Co2+, Fe3+, Mg2+, Ni2+, Pb2+, Sr2+, and Zn2+.

This bulletin contains two parts. The first part gives a short theoretical overview while more details are offered in the Metrohm Monograph Conductometry. The second, practice-oriented part deals with the following subjects:Conductivity measurements in general; Determination of the cell constant; Determination of the temperature coefficient; Conductivity measurement in water samples; TDS – Total Dissolved Solids; Conductometric titrations;

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).

This Bulletin describes three potentiometric, one photometric, one thermometric and one conductometric titration method for sulfate determination. The question of which indication method is the most suitable depends primarily on the sample matrix.Method 1: Precipitation as barium sulfate and back titration of the Ba2+ surplus with EGTA. Use of the ion-selective calcium electrode as indicator electrode.Method 2: As with Method 1, although with the electrode combination tungsten/platinum.Method 3: Precipitation titration in semi-aqueous solution with lead nitrate in accordance with the European Pharmacopoeia using the ion-selective lead electrode as indicator electrode.Method 4: Photometric titration with lead nitrate, dithizone indicator and the Optrode 610 nm, particularly suitable for low concentrations (up to 5 mg SO42- in the sample solution).Method 5: Thermometric precipitation titration with Ba2+ in aqueous solution, particularly suitable for fertilizers.Method 6: Conductometric titration with barium acetate in accordance with DIN 53127

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.

This Bulletin describes the simultaneous potentiometric titration of free boric acid and free tetrafluoroboric acid in nickel plating baths. After addition of mannitol, the formed mannitol complexes are titrated with sodium hydroxide solution. The determination is carried out directly in the plating bath sample; nickel and other metal ions do not interfere.

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.

This bulletin deals with the automated determination of mixtures of HNO3, HF and H2SiF6 in the range of approximately 200-600 g/L HNO3, 50-160 g/L HF, and 0-185 g/L H2SiF6 using thermometric titration.Etch acid mixtures containing HNO3, HF and H2SiF6 from the etching of silicon substrates can be analyzed in a sequence of two determinations using the 859 Titrotherm. The first determination involves a direct titration with standard c(NaOH) = 2 mol/L, followed by a back titration with c(HCl) = 2 mol/L. This determination yields the H2SiF6 content plus a value for the combined (HNO3+HF) contents. The second determination consists of a titration with c(Al3+) = 0.5 mol/L to determine the HF content. For freshly made up mixtures of HNO3 and HF containing no H2SiF6, a linked two-titration sequence is employed. Results from the two determinations are used by tiamoTM to yield individual results for HNO3, HF and H2SiF6.

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.

Determination of zinc, sodium, calcium, and magnesium in an industrial bath containing cooling lubricants using cation chromatography with direct conductivity detection.

Corrosion refers to a process that involves deterioration or degradation of metal. The most common example of corrosion is the formation of rust on steel. Most corrosion phenomena are of electrochemical nature and consist of at least two reactions on the surface of the corroding metal.

Electrochemical methods provide an alternative to traditional methods used to determine the rate of corrosion. For example, corrosion rates, the rates at which a specimen corrodes, can be calculated from simple electrochemical measurements like a linear sweep voltammetry (LSV).

Polarization resistance (Rp) can quantify the corrosion resistance of metals as an alternative to Tafel analysis. Its methodology and practical use as described in ASTM G59 are discussed.

A corrosion inhibitor is a substance that reduces the corrosion rate of a metal. A corrosion inhibitor is usually added in a small concentration to the corrosive environment. This application note shows how Metrohm Autolab instruments can be used to check the quality of inhibitors.

This Application Note is based on the ASTM standard G150, developed to test the resistance of stainless steel, and otheralloys related to stainless steel, on pitting formation at elevated temperature. This is achieved by determining the potential-independent critical pitting temperature (CPT), defined as the lowest temperature at which pitting evolution occurs. The CPT experiment consists of applying a potential to the specimen while the cell temperature is raised and recording the current.

In this Application Note, EIS is applied on three coated aluminium samples, before and after the stepwise dissolution measurement (SDM). This technique has been reviewed in the Application Note AN-COR-08.

Corrosion of metals is a problem seriously affecting not only many industrial sectors, but also private life, resulting in enormous costs. In this application note, the results gained during electrochemical corrosion studies on different metals are compared to literature data.

The ASTM standard G100 is an electrochemical method to test localized corrosion of aluminum 3003-H14 and other alloys. A cyclic galvanostatic staircase polarization (galvanostaircase) is composed of an upward and a downward scan. The potential values at the end of each step are collected and linearly fitted, and the potential values at zero current are found.

This Application Note evaluates corrosion in Type 430 stainless steel according to ASTM G5 with VIONIC powered by INTELLO and an ASTM-compliant corrosion cell setup.

The rotating cylinder electrode (RCE) is a technique used in corrosion research to simulate in a laboratory environment the turbulent flow which usually occurs when liquids are transported through pipelines. The RCE is used to generate a turbulent flow at the surface of a sample, simulating the pipe flow conditions. Experiments that involve an RCE are regulated by the ASTM G185 standard. In this application note, The RCE with a 1018 carbon steel cylinder sample was used with the linear polarization (LP) measurement technique.

The rotating cylinder electrode (RCE) is successfully used in a laboratory environment to generate a turbulent flow at the surface of a sample, simulating realistic pipe flow conditions. In this application note, the corrosion rate is measured and compared between quiescent and turbulent flow conditions, while keeping all the other experimental conditions unchanged. The linear polarization (LP) technique was used together with the RCE (with and without rotation).

This Application Note details ASTM G61-compliant corrosion measurements performed with VIONIC powered by INTELLO using Metrohm’s ASTM-compliant corrosion cells.

The ASTM B825 is used to determine the corrosion and tarnish film on metal surfaces. This is achieved by using the so-called cathodic reduction method. With the help of a Metrohm Autolab PGSTAT302N and a Metrohm Autolab 1 L corrosion cell, a procedure to replicate the ASTM B825 is shown.

The International Standard ISO 17463 describes the determination of the anticorrosive properties of high impedance organic protective coatings on metals. This technique uses cycles composed of electrochemical impedance spectroscopy (EIS) measurements, cathodic polarizations and potential relaxation. This application note shows the compliance of the Metrohm Autolab PGSTAT M204 and flat cell with the standard ISO 17463.

Tafel analysis is an important electrochemical technique used to understand reaction kinetics. By studying the Tafel slope, it reveals the rate-determining steps in electrode reactions, aiding fields like corrosion and fuel cell research. This method helps industries optimize processes and improve device performance by tailoring materials and conditions for greater efficiency.

A reference electrode has a stable and well-defined electrochemical potential (at constant temperature), against which the applied or measured potentials in an electrochemical cell are referred. A good reference electrode is therefore stable and non-polarizable. In other words, the potential of such an electrode will remain stable in the used environment and also upon the passage of a small current. This application note lists the most used reference electrodes, together with their range of use.

This application explains ohmic iR drop in electrochemical cells, its causes, and strategies to minimize its impact for accurate and reliable potential measurements.

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.

The determination of heavy metal ions in a solution is one of the most successful application of electrochemistry. In this application note, anodic stripping voltammetry is used to measure the presence of two analytes, in a sample of tap water.

In this Application Note, hydrogen permeation experiments are conducted following the procedure described in the ASTM standard G148.

The Devanathan-Stachurski cell (or «H cell») is successfully used to evaluate the permeation of hydrogen through sheets or membranes. As small amounts of hydrogen pass through the sheet or membrane, a very sensitive potentiostat is required for its detection. A study of the hydrogen permeation properties of different iron sheets is discussed in this Application Note while taking the instrumental requirements into account.

Electrochemical impedance spectroscopy (EIS) is a widely used multidisciplinary technique for characterizing the behavior of complex electrochemical systems. EIS is employed in the study of a range of complex systems including batteries, catalysis, and corrosion processes. This Application Note focuses on the basic principles of EIS measurements.

A typical electrochemical impedance spectroscopy (EIS) experimental setup consists of an electrochemical cell, a potentiostat/galvanostat, and a frequency response analyzer (FRA). This Application Note introduces common EIS experimental setups as well as details of the main experimental parameters.

Here, the most common circuit elements for EIS are introduced which may be assembled in different configurations to obtain equivalent circuits used for data analysis.

Explore how to construct simple and complex equivalent circuit models for fitting EIS data in this Application Note. Nyquist plots are shown for each example.

In the application note AN-EIS-004 on equivalent circuit models, an overview of the different circuit elements that are used to build an equivalent circuit model was given. After identifying a suitable model for the system under investigation, the next step in the data analysis is estimation of the model parameters. This is done by the non-linear regression of the model to the data. Most impedance systems come with a data-fitting program. In this application note, the way NOVA is uses to fit the data is shown.

In this application note, the advantage of recording the raw time domain data for each individual frequency during an electrochemical impedance measurement is described.

Electrochemical impedance spectroscopy (EIS) is a powerful technique which provides information about the processes occurring at the electrode-electrolyte interface. The data collected with EIS are modeled with a suitable electrical equivalent circuit. The fitting procedure will change the values of the parameters until the mathematical function matches the experimental data within a certain margin of error. In this Application Note, some suggestions are given in order to get acceptable initial parameters and to perform an accurate fitting.

This Application Note explains how fluoride determination in acid etching baths can be performed with thermometric titration.

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

Determination of free acid in solutions containing metal ions, particularly Fe(III).

Determination of mixtures of phosphoric, nitric, and acetic acids used in etching aluminum in the manufacture of semiconductor devices.

Determination of free acid in copper refining solutions.

Determination of nickel in the absence of cobalt and other interferences.

Determination of phosphate content in an acid etching bath.

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 nickel in refinery and plating solutions. When other metals capable of being complexed by EDTA are present, these will interfere and enhance the result for nickel.

Determination of nickel in solution by titration with standard disodium dimethylglyoximate.

Determination of sodium hypophosphite in electroless plating solutions.

Thermometric titration of nickel in electroless plating solution with disodium dimethylglyoximate.

Determination of aluminum in acidic, basic, and neutral solutions; including aluminum chloride, aluminum chlorohydrate (also in anti-perspirant formulations), alum, etching solutions, and aluminate solutions.

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 hydrofluoric acid in mixed acid etchant solutions.

Automated thermometric titration of the nickel content of electroless nickel plating solutions. The determination is suitable for fully automated titration employing a 814 Sample Processor.

Determination of boric acid in electroless plating solutions.

Two separate titration sequences are required to analyze the mixture:- titration of the HF content with Al(NO3)3 (the «elpasolite» reaction)- titration of the H2SO4 with BaCl2 followed by titration with NaOH to determine the «total acids» contentThe HF, H2SO4, and «total acids» contents are converted to a HNO3 equivalent, with the HNO3 content found by subtracting the HF and H2SO4 from the «total acids» content.

A direct thermometric titration (TET) with 2 mol/L NaOH is used to determine the HF, NH4F, and maleic acid (C4H4O4) contents of acid cleaning solutions. Three endpoints (EPs) are obtained, which may be assigned as follows:EP1: C4H4O4 (pKa1 = 1.9), HF (pKa = 3.17)EP2: C4H4O4 (pKa2 = 6.07)EP2: NH4F (pKa = 8.2)The HF content is determined by subtracting the difference (EP2-EP1) from EP1.

The presence of the hydrated ion [Fe(H2O)6]3+ can interfere with the determination of «free acid» due to the low pKa value (~2.2) of this ion. Ions of metals such as Fe, Cu, and Al can be masked effectively with fluoride, and permit the determination of the acid content by thermometric alkalimetric titration with good accuracy and precision.

Silver and nitric acid are determined in silver electrolyte solutions by means of thermometric titration. The method provides accurate results in a short time and is ideally suited for routine process control.

Thermometric titration can be used for the ready determination of sulfuric acid and phosphoric acid in acid mixtures. An endpoint for each acid appears on the titration curve that can be used to quantify the respective acid.

Thermometric titration is used for the determination of hydrochloric acid and phosphoric acid in acid mixtures. Two endpoints appear on the titration curve that are used for the determination of the two acids.

Thermometric titration is used for the determination of hydrochloric acid and nitric acid in acid baths. The entire acid content is titrated with caustic soda in the initial titration; the hydrochloric acid content is then determined in a second titration using silver nitrate solution.

Thermometric titration is used to determine hydrochloric acid and hydrofluoric acid (hydrogen fluoride) in etching baths containing ethanol and acetonitrile. Two endpoints appear on the titration curve that are used individually for the quantification of the respective acid.

Thermometric titration is used to determine hydrofluoric acid and nitric acid in etching baths containing ethanol and acetonitrile. Two endpoints appear on the titration curve that are used individually for the quantification of the respective acid.

Nitric acid, phosphoric acid, and acetic acid are easily determined in etching baths using thermometric titration (TET). Compared to potentiometric titration, TET is faster and more convenient. Analysis is complete in less than two minutes.

Tartaric Sulfuric Anodizing (TSA) is an established technique for corrosion protection in the aerospace industry. It is an alternative to the environmentally harmful chromic anodizing process. As such, a method to monitor the levels of sulfuric acid and tartaric acid in TSA plating baths is required. Potentiometric titration methods have been developed, and are widely used across the industry. Their disadvantage is that two titrations with different electrodes and solvents are required.In this Application Note, an alternative method is presented, where the concentration of both acids is determined in sequence using a thermometric sensor. Compared to potentiometric titration, thermometric titration is faster and more convenient (no sensor maintenance required). On a fully automated system, the determination of both parameters takes about 7 minutes.

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

Determination of fluoride in a chromium plating bath by direct potentiometry using the F-ISE.

Determination of nitrate in a nickel plating bath using anion chromatography with UV/VIS detection (205 nm).

Determination of citrate and saccharin in a nickel plating bath using ion-exclusion chromatography with direct conductivity detection.

Determination of gluconate and salicylate in a zinc plating bath using ion-exclusion chromatography with direct conductivity detection.

Determination of lactate, formate, and acetate in a cataphoretic paint bath using ion-exclusion chromatography with direct conductivity detection.

Determination of citrate, fluoride, lactate, and acetate in a plating bath using ion-exclusion chromatography with direct conductivity detection.

Determination of citric acid and lactic acid in an electroplating bath using ion-exclusion chromatography with conductivity detection.

In an electroless plating bath, the consumed ingredients have to be regularly replenished to ensure an even layer of nickel-phosphorus alloy. This requires online monitoring of the active bath constituents. Parameters to be controlled are pH value (4.5–5.0) as well as nickel (NiSO4 < 10 g/L) and hypophosphite concentration (NaH2PO2: 1–12%). Other measurement options include sulfate, alkalinity, and organic additives (via CVS).

Anodizing metal surfaces improves resistance against corrosion and wear. Etching baths can be monitored precisely online with the 2060 TI Process Analyzer or 2026 HD Titrolyzer.

Pickling baths are used in the galvanic industry to clean steel surfaces and prevent corrosion through passivation. Maintaining specific Fe2+/Fe3+ and free acid/total acid ratios is vital to ensure the baths' optimal performance, which directly impacts the final product quality and reduces production costs by minimizing reagent consumption. This application presents a method to regularly monitor the acid and iron composition in pickling baths online by using a process analyzer from Metrohm Process Analytics.

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

This Application Note explains how the 2060 XRF Process Analyzer enables real-time chemical monitoring of copper, tin, and zinc concentrations in white bronze plating baths.

The 2060 XRF Process Analyzer continuously monitors elemental concentrations online within zinc-nickel electroplating baths to precisely guide chemical dosing.

Modern recreational use of DMT (N,N-Dimethyltryptamine) is growing and although it is legally protected in some countries, new legislation attempts to reduce its abuse and associated adverse health effects. MIRA XTR DS from Metrohm Raman provides rapid and sensitive detection of DMT in the field.

Determination of fluoride, chloride, and nitrate in a solution of NiSO4, ZnSO4 in sulfuric acid using anion chromatography with conductivity detection after chemical suppression.

Determination of fluoride, nitrate, phosphate, and sulfate in an etching reagent using anion chromatography with conductivity detection after chemical suppression.

Determination of chloride, sulfate, chromate, methanesulfonic acid (MSA), methanedisulfonic acid (MDSA), and ethanedisulfonic acid (EDSA) in a chromium plating bath using anion chromatography with conductivity detection after chemical suppression.

Determination of fluoride, chloride, nitrate, and sulfate in corrosion powder using anion chromatography with conductivity detection after chemical suppression.

Determination of nitrate, phosphate, sulfate, and chromate in a cataphoretic paint bath using anion chromatography with conductivity detection after chemical suppression.

Determination of nitrate and sulfate in sodium phosphinate (sodium hypophosphite) using anion chromatography with conductivity detection after chemical suppression.

Determination of chloride, nitrite, nitrate, phosphate, and sulfate in an electroplating bath after inline elimination of heavy metals by cation exchange on the 793 IC Sample Prep Module using anion chromatography with conductivity detection after chemical suppression.

Determination of borate and chloride with direct conductivity detection (exhausted MSM). After the introduction of the fresh MSM unit and after the eluent change, sulfate is analyzed with conductivity detection after chemical suppression.

Determination of hypophosphite, phosphite, tartrate, tungstate, phosphate, citrate, and pyrophosphate in an electroplating bath using anion chromatography with a high pressure gradient and conductivity detection after chemical suppression.

Determination of chloride, nitrite, nitrate, phosphate, and sulfate in a strongly alkaline solution using anion chromatography with conductivity detection after chemical suppression.

Determination of chloride, nitrite, and sulfate in a used zinc bath using anion chromatography with conductivity detection after chemical suppression.

Determination of fluoride, nitrate, phosphate, sulfite, and sulfate in an etching bath using anion chromatography with conductivity detection after chemical suppression.

Determination of sulfate, molybdate, and chromate in a plating bath using anion chromatography with conductivity detection after chemical suppression.

Determination of fluoride, MSA (methylsulfonic acid), EDSA (ethyldisulfonic acid), and MDSA (methyldisulfonic acid) using anion chromatography with conductivity detection after chemical suppression.

Determination of nitrate in a nickel plating bath using anion chromatography with UV/VIS detection (205 nm) after chemical suppression.

Determination of hypophosphite, phosphite, and phosphate in a nickel bath using anion chromatography with conductivity detection after chemical suppression and inline cation exchange.

Methanedisulfonic acid (MDSA) is used as a catalyst in chromium plating baths. The MDSA concentration in the bath must be known in order to monitor the chromating. The analysis of a bath sample requires dilution by a factor of 2,500. This Application Note shows the automatic Inline Dilution that takes place in two steps. While one sample is being analyzed, the time-optimized dilution of the next sample is already running. The MSM is regenerated using an 800 Dosino and the STREAM setup: The eluent is used for rinsing the regenerated MSM after exiting the detector.

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.

Chrome plating is an important electroplating technique that covers metal or plastic surfaces with a thin layer of chromium for both protection and decoration purposes. The sulfate and sulfuric acid concentrations in the baths are important parameters in the coating process and require continuous monitoring. The anions in the chrome baths are separated on the Metrosep A Supp 5 - 250/4.0 column and are determined using conductivity detection in accordance with sequential suppression.

Determination of anionic surfactants in a nickel plating bath by potentiometric titration with TEGO®trant A100 using the «Ionic Surfactant» electrode.

Simultaneous determination of cyanide and silver in a silver plating bath by potentiometric titration with silver nitrate using the Ag-Titrode.

Determination of Cr(VI) and Cr(III) in chromium baths by iodometric potentiometric titration with thiosulfate using the combined Pt electrode.

Determination of Sn(II) and sulfuric acid in an acidic tin plating bath by potentiometric titration.

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.

Determination of iron and nickel in binary mixtures by potentiometric titration with EDTA at different pH values using the Cu-ISE.

Determination of palladium(II) by potentiometric titration with hexadecylpyridinium chloride using the «Ionic Surfactant» electrode.

This Application Note treats the photometric titration of nickel using the Optrode (520 nm). Murexide was used as the indicator and EDTA as the titrant.

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.

This Application Note describes the fully automated complexometric determination of zinc(II) in aqueous solutions with a copper ion-selective electrode.

Zinc and magnesium ion mixtures are analyzed using back-titration at different pH values. The ion-selective copper electrode is used here as the indicator electrode. First, the zinc is determined in acidic solution and then the magnesium in alkali solution.

Copper can be determined using photometric titration with EDTA at a wavelength of 520 nm.

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.

This Application Note compares the OMNIS Titrator and 888 Titrando for determinations of nitric acid, phosphoric acid, and acetic acid in an aluminum etching bath, as well as the determination of tetramethylammonium hydroxide (TMAH). Identical analysis parameters were used, showing that OMNIS delivers results on par or even better than with other established titration systems.

Purity of rare earth elements (REEs) can be determined by absolute complexometric titration with xylenol orange (ISO 23597). This approach achieves around 100% recovery, eliminates the need for calibration, and offers higher accuracy and reproducibility than techniques such as AAS (atomic absorption spectroscopy). Photometric titration with the Optrode M2 offers adjustable wavelength detection, providing a fast, precise, and cost-effective alternative to other conventional methods.

Rare earth elements (REEs) are critical materials whose deposit viability and processing streams require accurate mass-fraction determination during ore dissolution and purification. This Application Note describes a rapid potentiometric back-titration using a copper ion-selective electrode (Cu-ISE) that enables selective quantification and partial separation of REEs in complex matrices with near-quantitative recovery. As an absolute, flexible, and cost-effective method with ICP-compatible sample preparation, back-titration is well suited both as a reference technique and for rapid on-site analysis.

Determination of saccharin, benzamide, and o-toluenesulfonamide in a nickel electroplating bath using RP chromatography with UV detection.

Determination of silicate and hexafluorosilicate (calculated) using anion chromatography with conductivity detection after chemical suppression (see AN S-277) and subsequent UV/VIS detection with post-column reaction. Hexafluorosilicate is hydrolyzed into fluoride and silicate. Both anion concentrations may be used for the calculation of the SiF62- concentration.

The determination of iodate and iodide in used electroplating baths is a demanding task due to the high concentration of other ions. Iodate is used as a stabilizer for the bath and needs to be checked for proper electroplating. The use of a sodium chloride eluent, the Metrosep A Supp 5 - 250/4.0 column and direct UV/VIS detection permits the analysis of these samples without matrix interferences.

Determination of Ni, Sb, Cd, Tl, and Cu in a neutral, highly concentrated zinc solution from the plating industry.

Determination of Ni, Fe, and Cu in a silver plating bath.

Determination of Cr and Se in a silver plating bath.

Determination of Sn and Pb in an organo plating bath.

Lead is commonly used as stabilizer in electroless nickel plating processes. The regular and precise determination of the electrochemically active Pb(II) concentration is essential to keep the plating process running optimally under stable conditions. Differential pulse anodic stripping voltammetry can be used to determine the active lead content after dilution. The voltammetric determination has been established as a straightforward, sensitive, selective, and interference-free method for this application.

Determination of Cu and Cr in an etching bath. Due to the high concentrations of Mn and Ni, Cu is determined as the EDTA complex and Mn as DTPA complex.

Determination of Fe and Zn in a nickel sulfate bath containing surfactants after UV digestion.

Determination of Cu in a nickel sulfate bath containing surfactants after UV digestion.

Determination of Zn, Cd, Pb, Ni, and Co in hydrochloric acid (37.8%).

Determination of Zn, Cd, Pb, Ni, and Co in Javelle water.

Cobalt can be determined in the presence of high concentrations of gold at the DME using 5-sulfosalicylic acid as supporting electrolyte and DMG as complexing agent.

Nickel can be determined in concentrated zinc solutions by adsorptive stripping voltammetry (AdSV) at the HMDE using ammonia buffer as supporting electrolyte and dimethylglyoxime (DMG) as complexing agent. The determination of cobalt does not work under these conditions as the very high Zn2+ concentration interferes with the Co signal. Therefore, an alternative complexing agent has to be used: α-benzil dioxime in ammonia buffer under addition of sodium nitrite.

The concentration of total Sb in zinc plant electrolytes is determined by anodic stripping voltammetry (ASV) in 5 mol/L HCl. If 0.6 mol/L HCl is used, only the concentration of antimony(III) is determined selectively. The interference of an excess of Cu is suppressed by the selective oxidation of Cu. Nevertheless, the concentration of Cu in the sample limits the amount of sample that can be used for the determination.

Germanium can be determined by adsorptive stripping voltammetry (AdSV) at the HMDE using acetate buffer as supporting electrolyte and catechol as complexing agent.

Thallium and cadmium can be determined by anodic stripping voltammetry (ASV) at the HMDE (Tl) and polarography at the DME (Cd), respectively using aqueous hydrochloric acid as supporting electrolyte. Since Cd is present in high excess and would therefore interfere with the determination of thallium, a post electrolysis procedure is applied to remove the co-deposited metal from the mercury drop.

Germanium is determined by adsorptive stripping voltammetry (AdSV) at the HMDE using aqueous sulfuric acid as supporting electrolyte and pyrocatechol violet as complexing agent. It is possible to determine 20 µg/L Ge in a sample containing 150 g/L Zn, 3 g/L Cd and 1 mg/L Pb.

Thiourea is determined by cathodic stripping voltammetry (CSV) at the HMDE in ammonia buffer at pH 8.9. Chloride in the sample does not interfere with this determination.

The concentration of Fe(total) is determined polarographically in a chromium electroplating bath. The method is suitable for iron in concentrations in the ppm range. Fe(II) and Fe(III) show signals with the same sensitivity.

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 «Ronastan TP Additive» in a tin/lead bath by dilution titration (DT) using cyclic voltammetric stripping (CVS).

Determination of suppressor «Solderon ST-200 Primary» in a tin bath by dilution titration (DT) using cyclic voltammetric 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).

The concentration of Ni in a Ni plating bath is determined by polarography in ammonia buffer pH 9.6.

The concentration of Co in a sulfamate Ni plating bath is determined by adsorptive stripping voltammetry (AdSV) inammonia buffer pH 9.6 with dimethylglyoxime (DMG) as complexing agent. All reagents have to be added in the order listed below. Special care has to be taken that the measuring solution is mixed well before the complexing agent is added. In case of precipitations of Ni-DMG further dilution of the sample is necessary.

The concentration of Cu in a Ni plating bath is determined by polarography in chloride-containing acetate buffer at pH 4.7.

The concentration of Sb(III) and Sb(total) in an electroless nickel bath is determined by anodic stripping voltammetry (ASV). In c(HCl) = 0.6 mol/L only Sb(III) shows a signal. In w(HCl) = 10% the Sb(total) content is determined.

The concentration of Tl in a cyanidic Au bath is determined by anodic stripping voltammety (ASV) without further addition of electrolyte.

NTA in a cyanidic gold bath is determined as Bi-NTA complex by polarography. For standard addition a Bi-NTA standard solution is used.

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 In in a Sn bath is determined in a HCl / Urotropin® containing electrolyte by anodic stripping voltammetry (ASV). The determination is linear up to approx. 0.5 mg/L with respect to the concentration of In in the measuring vessel. The standard addition solution is also prepared with HCl and Urotropin®.

The concentration of Bi in a Sn bath is determined in a HCl / Urotropin® containing electrolyte by anodic stripping voltammetry (ASV). A reaction time of at least 25 min is required before the determination is started. The standard addition solution is also prepared with HCl and Urotropin®.

The concentration of Pd in an activator bath is determined by polarography in ammonium chloride electrolyte.

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

The concentration of Fe(total) is determined by polarography in oxalate buffer pH 2. This method is suitable for iron concentrations in the mg/L range.

The concentration of Fe(total) is determined by polarography in an alkaline electrolyte containing triethanolamine (TEA) and KBrO3. All reagents typically contain iron impurities. Therefore a subtraction of the reagent blank is recommended.

The concentration of Ti in a Ti pickle bath is determined by polarography in an oxalic acid electrolyte.

The concentration of Zn in a zinc phosphatation bath is determined by polarography in ammonia buffer pH 9.3.

The concentration of Ni in a Zn phosphatation bath is determined by polarography in ammonia buffer pH 9.3.

The concentration of Cd in a Zn phosphatation bath is determined by polarography in HCl electrolyte.

The concentration of Pb in a Zn phosphatation bath is determined by anodic stripping voltammetry (ASV) in HCl electrolyte.

The concentration of Pb in Sn soldering contacts is determined by anodic stripping voltammetry (ASV) in an electrolyte containing citrate, oxalic acid, HCl, and cetyl trimethyl ammonium bromide.

The concentration of Se(IV) in zinc plant electrolyte is determined by cathodic stripping voltammetry (CSV) in ammonium sulfate electrolyte containing EDTA and Cu. The Cu concentration has to be adapted to the sample and the deposition time. With voltammetry only free selenium is determined, therefore it has to be taken into consideration that selenium forms sparingly soluble compounds with numerous cations (e.g. Fe2(SeO3 )3 with Ks = 2·10-31).

The concentration of Te(IV) in Zn plant electrolyte is determined by cathodic stripping voltammetry (CSV) in ammonium sulfate electrolyte containing EDTA and Cu. To get a proper complexation of the interfering Zn a high amount of EDTA is necessary at pH 3.4.

The concentration of Co in zinc plant electrolyte (neutral zinc sulfate solution) is determined by adsorptive stripping voltammetry (AdSV) in ammonia buffer with α-furildioxime as complexing agent.

The concentration of Pb in zinc sulfate solution is determined by anodic stripping voltammetry (ASV) in hydrochloric acid electrolyte.

The concentration of As(total) in zinc plant electrolyte is determined by anodic stripping voltammetry (ASV) on a lateral gold electrode in HCl electrolyte. Due to the high excess of zinc in the sample the deposition potential has to be adapted. A second potential approx. 100 mV more negative than the arsenic signal has to be applied to selectively oxidize interfering antimony. For sample preparation the sample was passed through a cation exchange column to reduce the concentration of zinc in the measuring solution.

The concentration of of Sb(III) in zinc plant electrolyte is determined by adsorptive stripping voltammetry (AdSV) with chloranilic acid as complexing agent. In this method high copper concentrations do not interfere. An approx. 10-fold excess of lead interferes, since it shows a signal close to the antimony. With the parameters given below the working range of this method is 1 - 30 µg/L antimony(III) with respect to the concentration in the measuring vessel.

The concentration of Fe(total) is determined by polarography in alkaline electrolyte containing triethanolamine (TEA) and KBrO3. All reagents typically contain Fe impurities. Therefore a subtraction of the reagent blank is recommended.

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).