Applications

The coupling of highly efficient ion chromatography (IC) to multi-dimensional detectors such as a mass spectrometer (MS) or an inductively coupled plasma mass spectrometer (ICP/MS) significantly increases sensitivity while simultaneously reducing possible matrix interference to the absolute minimum. By means of IC/MS several oxyhalides such as bromate and perchlorate can be detected in the sub-ppb range. Additionally, organic acids can be precisely quantified through mass-based determination even in the presence of high salt matrices. By means of IC-ICP/MS different valence states of the potentially hazardous chromium, arsenic and selenium in the form of inorganic and organic species can be sensitively and unambiguously identified in one single run.

Metal precipitation and cyanide recovery in the SART process (sulfidization, acidification, recycling, thickening) depend to a great extent on the sulfide concentration. Among the flow injection analysis methods coupled to wet-chemical analyzers, the combination of a gas diffusion cell with an ion chromatograph (IC) plus subsequent direct spectrophotometric detection has proven to be one of the most convenient methods of sulfide analysis.This paper deals with the determination of sulfide anions via the coupling of a gas diffusion cell to an IC with subsequent spectrophotometric detection.

This poster presents a highly reproducible procedure for the determination of the sodium contribution of acid-extractable organic species in Bayer process liquor. The precision of the method is estimated to be 0.2% RSD.

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.

Thermometric titration can solve application problems that potentiometry cannot solve at all, or at least not satisfactorily.

An automatic titration method is described using biamperometric endpoint indication for the determination of antimony in antimony-alloyed cable lead (approx. 1% Sb). A 0.01 mol/L KBrO3 solution is used as the titrant.

Zinc, such as that occurring as a constituent of light alloys, can be determined by precipitation titration with potentiometric endpoint indication. The determination of zinc in the presence of cadmium is also possible.2 K4[Fe(CN)6] + 3 ZnCl2 → K2Zn3[Fe(CN)6]2 + 6 KCl

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.

A method for the potentiometric determination of CaCO3 in cement raw meal is described, in which the accurately weighed-out sample is treated with HCl, heated to boiling and the excess HCl is then back-titrated with NaOH.

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)

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

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

As much as the many types of cement may differ from one another, the characteristic that all of them have in common is the presence of the elements calcium, magnesium, iron, aluminum and silicon.Calcium, magnesium, iron and aluminum can be determined using various indicators following digestion of the cement sample using photometric titration with the Optrode at 610 nm. The determination of silicon, on the other hand, is gravimetric.

This Bulletin describes fluoride determination in various matrices with the help of the ion-selective fluoride electrode (F-ISE). The F-ISE is comprised of a lanthanum fluoride crystal and exhibits a response in accordance with the Nernst equation across a wide range of fluoride concentrations.The first part of this Bulletin contains notes regarding the handling and care of the electrode and the actual fluoride determination itself. The second part demonstrates the direct determination of fluoride with the standard addition technique in table salt, toothpaste and mouthwash.

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.

The potassium (or ammonium) ion is precipitated with sodium tetraphenyl borate, and the excess of this reagent back-titrated against the thallous(I) ion, using biamperometric endpoint detection. Ammonium can either be titrated together in an acid solution, or driven off by previous boiling in an alkaline solution. Methods are given for determining potassium in the presence of large excesses of sodium, ammonium, calcium, and magnesium.

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+.

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.

Mixtures of aluminum and magnesium ions can be analyzed automatically using potentiometric titration. The excess DCTA is back-titrated with copper(II) sulfate solution after the addition of 1,2-diaminocyclohexanetetraacetic acid (DCTA) and complex formation. The ion-selective copper electrode is used here as the indicator electrode. First, the aluminum is determined in acidic solution and then the magnesium in alkali 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.

This Bulletin describes the fully automated determination of uranium according to the method of Davies and Gray: Uranium(VI) is reduced in concentrated phosphoric acid solution with iron(II) to form Uranium(IV). With molybdenum as a catalyst, the excess iron(II) is oxidized with nitric acid. The nitrous acid that is formed is destroyed with sulfamic acid before uranium(IV) is titrated with a potassium dichromate solution in the presence of a vanadium catalyst.

The determination of the total causticizer, sodium carbonate and aluminum oxide contents in (Bayer) process liquors can be accomplished with high precision and speed by using the 859 Titrotherm in a thermometric acid-base titration. A complete titration takes approximately 5 minutes.The procedure is an automated adaptation of the traditional Watts-Utley method, and is similar to the VanDalen-Ward thermometric titration method, but with the added advantage that the analysis can also be performed for the carbonate content of the liquor.

Determination of calcium and magnesium in rock extracts using cation chromatography with direct conductivity detection.

Determination of traces of gadolinium, samarium, neodymium, cerium, and lanthanum using cation chromatography with direct conductivity detection after Metrohm Inline Filtration.

In order to extract aluminum from bauxite, the aluminum ore is exposed with a caustic soda solution under pressure in the temperature range of 150 to 200 °C. Dilution and pH value setting are implemented by the addition of 170 mmol/L citric acid prior to calcium determination with ion chromatography in the Bayer caustic soda. Doing so establishes a pH value of 4.5 and prevents precipitation of aluminum hydroxide. The IC separation takes place on the Metrosep C 4 - 150/4.0 column with a citric acid eluent.

The exploration and processing of lithium ores is gaining importance with the growing demand for lithium hydroxide. Lithium hydroxide is a key component in the manufacturing of rechargeable batteries for use in various applications including electric vehicles, home storage systems, power tools and consumer electronics. To ensure the efficiency for advanced processing of high purity lithium hydroxide, a fast and reliable quantitative detection technique is required. This application has been developed to monitor the lithium, sodium, and calcium content in the lithium processing samples and mineral concentrates.

Clay is used for the manufacture of roofing tiles. Quality controls during this process require the determination of halogen and sulfur content. This is ideally accomplished using Metrohm Combustion IC. With this method, the sulfur is determined as sulfate and the halogens as halogenides. Because clay often contains high contents of alkali and earth alkali metal ions that attack the pyrolysis tube, tungsten oxide is added prior to combustion.Keyword: pyrohydrolysis

Copper concentrate is an important raw material for copper mills. The concentrate is often contaminated with corrosive fluorine, which is why the fluorine concentration must be checked at regular intervals. A convenient and reliable determination method is Combustion IC in combination with sacrificing vial technology. The sample is placed inside the quartz combustion pipe in a horizontally positioned quartz vial, both ends of which are sealed with glass wool. During combustion, the quartz-destroying components (e.g., fluoride, alkali and earth alkali metals) that are released are captured by the quartz vial and the quartz wool, ensuring that they are thus unable to reach the quartz combustion pipe at all.Keyword: pyrohydrolysis

Iron ore is an important resource for steel production. Its natural content of halogens is a quality characteristic due to the corrosiveness of the respective halogenides. Combustion IC applying the sacrificial vial technology is used for the analysis of fluorine and chlorine in ore. WO3 usually is added to improve the release of SO2 and therefore sulfur recovery. In this application, it also significantly improves the recovery of fluoride.

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.

Electrochemical impedance spectroscopy or EIS has been used effectively to measure the polarization resistance for corrosion systems and for the determination of corrosion mechanisms.

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, stepwise dissolution measurement (SDM) is applied to aluminum samples coated with different materials, in order to gain insights in corrosion protection. The combination of the Autolab PGSTAT204 with the 1 L Autolab corrosion cell and the NOVA software provides the suitable setup to perform SDM and other corrosion experiments.

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.

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.

With the advent of electric automobiles, the demand for lithium batteries and with it the demand for lithium material will increase sharply. Brine lakes and hard silicate minerals are numbered among the most important sources of lithium. This Application Note addresses cation determination in seepage water from lithium minerals. Alkali and earth alkali metals are separated in the lithium digestions on the Metrosep C Supp 1 - 250/4.0 column, with subsequent conductivity detection after sequential suppression.

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.

This Application Note explains manual and automated iR drop correction with electrochemical impedance spectroscopy and cautions against using less accurate methods.

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.

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 water in moist particulate solids such as cobalt oxyhydroxide.

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

Determination of free acid in copper refining solutions.

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

This Application Note describes a method for the determination of causticizer, carbonate and aluminum oxide in used Bayer process liquors. The method is based on processes that were developed by Watts-Utley and VanDalen-Ward.

Determination of total basicity of extractable organic compounds of acidic character in Bayer process refinery liquors.

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 solution by titration with standard 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 chloride in Bayer process liquor.

Determination of Fe3+ by iodometric titration. Useful if Fe3+ is accompanied by Al3+, Mg2+, Ca2+ and Fe2+.

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 the total sodium content of sodium aluminate liquors, such as Bayer Process liquor. This method is suitable for the analysis of all sodium aluminate solutions down to at least 1 g/L as Na2CO3. The determination may be automated by adding an 814 USB sample processor to an 859 Titrotherm.

This Application Note outlines the determination of total acidic active surface sites in zeolites with thermometric titration.

This Application Note shows that the parameter of surface basicity of zeolites can be measured by thermometric titration.

Determination of mixtures of sulfuric, phosphoric, and nitric acids. The procedure is suitable for automated analysis using an 814 Sample Processor.

Determination of hydrofluoric acid in mixed acid etchant solutions.

Automated determination of the zirconium content of zirconium acetate, as well as other zirconium compounds which can be rendered soluble as zirconium acetate.

Determination of boron in ores of the element such as borax and ulexite.

A measured amount of acidic hydrometallurgical leach liquor is treated with potassium oxalate solution to mask potential interference from Fe(III) and other metal ions, and then titrated with standard 1 mol/L NaOH solution.

A measured amount of acidic hydrometallurgical leach liquor is first treated with hydrogen peroxide to oxidize Fe(II) to Fe(III), then with potassium pyrophosphate solution to mask interference from Fe(III) and other metal ions. Ammonium acetate solution is then added as a pH modifier, before being titrated with standardized disodium dimethylglyoximate to an exothermic endpoint.

A measured amount of acidic hydrometallurgical leach liquor is treated first with a complexing agent (sodium gluconate). It is then basified to ~pH 10.5 with a NH3 /NH4Cl buffer, prior to the addition of KCN solution to mask Fe(III). Caution! Do not add KCN to solutions of pH below 9! The Fe(III) is then reduced to Fe(II) by additon of ascorbic acid, prior to titrating the Mg content with standard Na4EDTA solution.

A measured amount of acidic hydrometallurgical leach liquor is further acidified with sulfuric acid, prior to being titrated with standard potassium dichromate solution to an exothermic endpoint. Thus, 1 mol K2Cr207 ≡ 6 mol Fe2+.

A measured amount of acidic hydrometallurgical leach liquor is pH modified with a small amount of glacial acetic acid, and the Fe(III) content reduced to Fe(II) with iodide ion. The liberated iodine is titrated with standard thiosulfate solution to an exothermic endpoint. Thus, 1 mol Fe3+= 1 mol S2O32-.

Results from three separate single endpoint titrations are used to calculate the results. The mixture of H2SO4, HF, and NH4F/HF contains H+ from H2SO4, HF, and NH4F/HF, SO42- from H2SO4, and F- from HF and NH4F/HF. Analysis of total H+ («total acids») by NaOH titration, F- by titrating with Al(NO3)3 («total fluoride») and SO42- by titrating with BaCl2 provides the information required to determine the composition of the mixture.

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.

This Application Note describes the determination of the free and total hydroxide and aluminum oxide content in Bayer process and other aluminate liquors. The method is not subject to interference by carbonate ions. An aliquot of sodium aluminate liquor is titrated with potassium hydrogen carbonate solution to yield the free hydroxide ion content of the liquor.

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.

This Application Note deals with the determination of ferric ion in acidic and copper-free solutions using thermometric titration. The ferric ion is reduced by iodide. The released iodine reacts exothermically when titrated with thiosulfate solution. The endpoint is determined through temperature plotting by the temperature sensor Thermoprobe.

This Application Note describes the determination of aluminum ion down to approximately 0.5 g/L in acidic solutions containing ferric, ferrous, and other ions whose hydroxides do not dissolve in strongly basic solutions.

This Application Note looks at the determination of ferrous ion in acidic solutions from approximately 0.25 g/L by thermometric titration with ceric titrant. The exothermic oxidation reaction shows a sharp endpoint that is detected using the Thermoprobe as a sensitive temperature sensor.

This Application Note describes the determination of aluminum in samples containing silicon dioxide using thermometric titration and EDTA as the titrant. Excess EDTA is titrated with a Cu2+ solution of known concentration. The initial, uncomplexed Cu2+ ions react immediately with the H2O2 present in the solution, leading to a recognizable sudden increase in temperature.

This Application Note looks at the determination of ferrous ion in acidic solutions through redox titration with potassium permanganate as titrant and thermometric titration.

Potash is commonly mined from ore, deposited after ancient inland oceans evaporated. The potassium salt is then purified in evaporation ponds. At the end of this process, the potash is typically obtained as potassium chloride. Potash is mainly used as fertilizer, providing potassium—an essential nutrient—to plants. Additionally, it is used in the chemical industry and to produce medicine. Potassium content in potash is typically determined by flame photometry (F-AES) or ICP-OES. However, these techniques have high investment and running costs. By applying the historically used gravimetric precipitation reaction as a thermometric titration, it becomes possible to rapidly and inexpensively determine the potassium content in potash within minutes.

Determination of fluoride in cement or clinker by direct potentiometry with the F-ISE.

The water content of lime is determined according to Karl Fischer using the oven method (150 °C).

Determination of nitrate, sulfate, and thiocyanate in additives for building materials using anion chromatography with direct conductometric detection.

Determination of fluoride and chloride in gypsum using anion chromatography and subsequent direct conductometric detection.

Determination of sulfate in hydrochloric acid digest of gypsum using anion chromatography with direct conductometric detection.

Pure sodium chloride contains much less iodide than e.g., table salt which usually is fortified with it. Trace determination of iodide is easily performed applying ion chromatography with amperometric detection. This detection mode is particularly selective and sensitive. The actual separation is achieved using a Metrosep A Supp 5 - 250/4.0 column. The detection happens at a silver working electrode. LOQ is at approximately 1.0 μg/L (in solution) and 50 μg/kg in the sample. The use of a shorter column might further improve the LOQ.

Conventional methods used to analyze moisture, ash, fixed carbon, and volatile content in coal samples, are time consuming and costly. Near-infrared (NIR) spectroscopy is excellently suited to determine all parameters simultaneously in less than one minute without any sample preparation.

Gold leaching by cyanidation requires precise monitoring of cyanide and gold. Online process analyzers perform such measurements, improving safety and compliance.

This Process Application Note is dedicated to the online analysis of zinc, iron and sulfuric acid in several stages of the zinc production process. Additionally, traces of germanium, antimony, as well as several transition metals (e.g., Ni, Co, Cu, Cd) can be precisely determined (<50 µg/L) in the purification filtrates and reactor trains.

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.

The Bayer Process is the method used to refine alumina from bauxite ore, as smelting aluminum directly from alumina is much more cost- and energy-effective. In this process, "aluminate liquors" are created by digesting the crushed bauxite with CaO and NaOH at high temperatures. Additionally, the CaO causticizes carbonate which forms in the alkaline solution from organic degradation and CO2 absorption from the atmosphere. Contaminations are removed at various steps in the process, and the liquor is filtered from the alumina crystals before it is recycled back to the digestion step. Before the spent liquor can be reused, a determination of the concentrations of the total hydroxyl (“caustic”), carbonate, and alumina values is required. These parameters can be determined quickly via thermometric titration with the 2035 Process Analyzer.

Lithium is a soft alkali metal that is typically obtained from salt lake brines. Lithium is used for many applications, but especially for production of lithium-ion batteries in electric cars, mobile phones, and more. This Process Application Note presents a method to monitor lithium as well as other cations in brines by online process ion chromatography (IC), a multiparameter analytical technique that can measure ionic analytes in a wide range of concentrations.

This Application Note documents the suitability of hand-held Raman spectrometers, e.g., the Mira M-1, for the identification and differentiation of salts such as carbonates, phosphates, and sulfates. The focus of the work was the rating of the influence of the cationic part and of the crystal water on the Raman spectroscopy identification of the salts.

Metrohm’s MIRA XTR handheld Raman spectrometer enables fast, reagent-free identification of phosphate species, enabling continuous monitoring of dynamic systems.

Raman spectroscopy with PLS modeling enables rapid, accurate, nondestructive quantification of the total phosphate content in solution with minimal sample preparation.

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

Determination of fluoride, chloride, bromide, sulfate, and iodide in mineral extracts using anion chromatography with conductivity detection after chemical suppression.

Determination of chromate in cement using anion chromatography with conductivity detection after chemical suppression.

Determination of fluoride, acetate, formate, chloride, sulfate, malonate, succinate, and oxalate in Bayer liquor using anion chromatography with conductivity detection after sequential suppression.

FDG gypsum originates from flue gas desulfurization systems in power plants. VGB-M 701 E (2008) describes aqueous extraction methods for determining chloride in FDG gypsum using ion chromatography. The sample preparation described in the VGB permits the determination of other anions besides chloride.

Determination of trace chloride in cement and clinker by potentiometric titration with silver nitrate using the Ag-Titrode.

Determination of sulfate in cement by indirect potentiometric titration with EDTA using platinum and tungsten electrodes.

Determination of hydrofluoric and nitric acid in etching baths by potentiometric titration.a) Determination of the total acid content using the combined Sb electrode and NaOH as titrant.b) Determination of hydrofluoric acid using the F-ISE and the titrant La(NO3)3.The concentration of nitric acid is then determined by calculation.

Determination of the iron content of iron powder by potentiometric titration with potassium dichromate using the Pt-Titrode.

Determination of calcium in aqueous solutions by photometric titration with EDTA using the 610 nm Spectrode.

Determination of the sum of calcium and magnesium in cement by photometric titration with EDTA using the 610 nm Spectrode.

Determination of aluminum in cement by photometric back-titration of the EDTA excess with zinc sulfate using the 610 nm Spectrode.

Simultaneous determination of titanium and iron by potentiometric titration with potassium dichromate using a platinum electrode. Before determination, Ti4+ and Fe3+ are reduced with Cr2+.

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

This Application Note describes the photometric determination of aluminum in cement using the Optrode (574 nm). Following breakdown of the cement sample, the dissolved aluminum is titrated with EDTA. The excess EDTA is titrated back with zinc sulfate solution.

This Application Note covers the photometric determination of calcium in cement using the Optrode (610 nm). After digestion of the cement sample, calcium is titrated with EDTA to the murexide endpoint.

This Application Note describes the digestion of a cement sample and the photometric determination of iron in accordance with DIN EN 196-2 by means of Optrode at 610 nm. Sulfosalicylic acid is used as the indicator and EDTA as the titrant for the determination.

This Application Note is devoted to the photometric determination of magnesium in cement using the Optrode (610 nm). After digestion of a sample aliquot, the magnesium content is determined using EDTA titration.

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.

In many countries, the aluminum concentration in water is limited to 0.2 mg/L. This application note shows how the analysis of aluminum in water can be done fully automatically by complexometric titration with EDTA.

This Application Note describes the fully automated complexometric determination of total iron in cement with a copper ion-selective electrode.

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

Manganese in aqueous solution can be determined using back titration in alkali solution. The ion-selective copper electrode is used here as the indicator electrode.

This application note shows the use of an ion-selective copper electrode to measure the indium concentration in an aqueous solution.

Thallium in aqueous solution can be determined using back titration in a weak acidic solution. The ion-selective copper electrode is used here as the indicator electrode.

Zirconium can be analyzed quickly and easily in slightly acidic solutions with back titration. The ion-selective copper electrode is used in this Application Note to determine zirconium in aqueous solution.

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

OMNIS is the ideal system for quick and accurate determination of aluminum in aluminum chloride using complexometric back titration with an ion-selective copper electrode (Cu-ISE). Copper sulfate is used as the titrant.

Lithium is a soft metal which is used for many applications, such as production of high-temperature lubricants or heat-resistant glass. Furthermore, lithium is used in large quantities in for battery production. It is obtained from brines and high-grade lithium ores. Depending on the lithium concentration, extraction may or may not be economically viable.This Application Note demonstrates a method to determine the lithium concentration in brines by potentiometric titration. Lithium and fluoride precipitate in ethanol as insoluble lithium fluoride. Using ammonium fluoride as the titrant and a fluoride ion-selective electrode (ISE), determination via potentiometric titration is possible. This method is more reliable, faster, and less expensive than the determination of lithium in brine by other more sophisticated techniques such as atomic absorption spectroscopy (AAS).

The total iron content in iron ore plays a central economic role for mining companies. The higher the iron content in the ore, the more profitable the mining operation. Therefore, a fast and accurate analysis is important to determine the most profitable areas to work.The iron ore is dissolved in hydrochloric acid at 80 °C. Afterwards, the iron is quickly and accurately determined by potentiometric titration using the Pt-ring electrode and potassium dichromate as titrant.

The knowledge of the exact silver content of silver allows used for jewelry is very important to ensure the quality of jewelry. Therefore, the determination procedure is regulated internationally and nationally. A common approach is the titration with potassium bromide after an acidic digestion of the silver using a silver electrode for indication.

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 sulfide in mining wastewater using anion chromatography with UV detection.

The determination of chromium in metal plate samples using anion exchange chromatography with UV/VIS detection after post-column reaction with diphenylcarbazide as per IEC 62321 method for RoHS testing. This method provides procedures for the determination of the presence of chromium(VI) in colorless and colored chromate coatings on metallic samples.

In gold mining, there is a tendency to switch from cyanide leaching to the much less toxic thiosulfate leaching process. Thiosulfate leaching is a sensitive process that requires more optimization of the components of the leach reaction to maximize gold recovery and reagent loss. Sulfite, thiosulfate, thiocyanate, and tetrathionate are separated on a Metrosep A Supp 5 - 250/4.0 column. Perchlorate is choosen as an eluent as most of the metal perchlorates are soluble in water. This avoids metal precipitation in the IC System.

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.

Copper, iron, and vanadium can be determined in salt samples in the µg/kg concentration range by adsorptive stripping voltammetry (AdSV) at the HMDE. No sample preparation is necessary.

Cadmium, lead, and copper are determined by anodic stripping voltammetry (ASV) at the HMDE using aqueous nitric acid as supporting electrolyte.

Ni and Co are determined in triphosphate by adsorptive stripping voltammetry (AdSV) in ammonia buffer at pH 9.5 with addition of dimethylglyoxime (DMG).

Anodic stripping voltammetry (ASV) at the HMDE is used to determine manganese in triphosphate. The sample is first digested and then measured in an alkaline solution.

Cr(VI) is determined at the HMDE in an electrolyte containing ethylenediamine and acetate. Because Cr(III) is electrochemically inactive, all Cr has to be oxidised prior to analysis.

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.

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 Cr(VI) in cement is determined in tartrate electrolyte after acid extraction of the sample.

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

Free white paper describes the effective use of electrochemical techniques to measure corrosion and the effectiveness of inhibitors.

This white paper summarizes the advantages and benefits of automated titration in comparison to manual titration. The increase in accuracy and precision of measurements as well as significant time and cost savings are discussed.

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.

White paper on monitoring corrosion and the benefits of online or inline chemical analysis over manual sampling and offline laboratory methods for corrosion monitoring. Online and inline process application solutions for corrosion prevention with related application notes for further information are presented.

This White Paper presents four different «green» sensors: the scTRACE Gold, screen-printed electrodes, the glassy carbon electrode, and the Bi drop electrode from Metrohm that can be used to determine low concentrations of heavy metals in different sample matrices, such as boiler feed water, drinking water, and sea water.

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