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

This Bulletin describes the potentiometric determination of hydrogen sulfide, carbonyl sulfide, and mercaptans in gaseous and liquid products of the oil industry (natural gas, liquefied petroleum gas, used absorption solutions, distillate fuels, aviation gasoline, gasoline, kerosene, etc.). The samples are titrated with alcoholic silver nitrate solution using the Ag Titrode.

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.

Determination of chloride and sulfate (non-quantified) in a high-viscosity oil sample using combustion digestion and subsequent anion chromatography with conductivity detection following sequential suppression.Keyword: pyrohydrolysis

Determination of fluoride, chloride, bromide and sulfate in residual solvent using combustion digestion as sample preparation and subsequent anion chromatography with conductivity detection following sequential suppression. The analysis is significant for use in dividing waste products into non-halogenated and halogenated solvents.Keyword: pyrohydrolysis

The determination of halogens and sulfur in waste products is important. The inline combination of the Mitsubishi Combustion Module with the Metrohm IC is a suitable method for this type of samples. The recovery rates are analyzed with a certified reference material, e.g., a low-density polyethylene (LDPE).Keyword: pyrohydrolysis

Latex gloves are used in clean room environments in order to prevent contaminations. The use of gloves that release corrosive halogenides or sulfate is forbidden in nuclear power plants. The total content of halogen and sulfur is determined by means of Combustion Ion Chromatography. An eluate test is carried out to check the elutable percentage of halogens and sulfate from gloves. Sample preparation is comprised of preconcentration and matrix elimination (MiPCT-ME), as described in AN-S-304.Keyword: pyrohydrolysis

Combustion Ion Chromatography combines pro-hydrolytic sample combustion and the absorption of emerging combustion gases in an oxidizing, aqueous solution that is then channeled to an ion chromatograph for the analysis of halogenides and sulfur (as sulfate). The combustion and analysis of the certified reference materials (ZRM) makes clear the reliability of Metrohm Combustion Ion Chromatography.Keyword: pyrohydrolysis

This application describes the determination of fluoride, chloride, bromide and sulfur (as sulfate) in an ethanol standard solution with halo organic (4-halogen benzoic acids; F, Cl and Br) and sulfur organic compounds (3-(Cyclohexylamino)-1-propanesulfonic acid) by means of Metrohm Combustion Ion Chromatography with flame sensor and Inline Matrix Elimination.Keyword: pyrohydrolysis

Cyclohexane is an important organic solvent. Recycled cyclohexane must be tested for trace substances, e.g., chloride and sulfate. Metrohm Combustion Ion Chromatography with flame sensor and Inline Matrix Elimination is the method of choice.Keyword: pyrohydrolysis

The manufacture of ultrapure water for the pharmaceuticals industry or the semiconductor industry requires high-quality ion exchangers. Metrohm Combustion Ion Chromatography is an indispensable tool in this connection for testing the purity of anion exchange material. The output sample was wet and had to be dried at 105 °C in a special oven with waste air evacuation.Keyword: pyrohydrolysis

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

This Application Note looks at the determination of fluorine and sulfur in certified liquefied gas using Metrohm Combustion IC. Sequential determinations proceed in parallel to a certain extent: While the absorption solution of a sample that has already been combusted is being analyzed with IC, the combustion of the next sample is already underway.Keyword: pyrohydrolysis

This Note addresses the determination of the fluorine and chlorine content of a liquefied gas sample (LPG, Liquid Petroleum Gas), i.e. halogens in a mixture of propane and butane. Fluorine originates from perfluorobutane and chlorine from methyl chloride. LPG/GSS modules are used to introduce 50 µL of sample into the combustion system. The halogens released during combustion are determined using ion chromatography with intelligent partial loop injection technique following Inline Matrix Elimination.Keyword: pyrohydrolysis

Palm oil is a vegetable oil that is used not only in the food industry but also for the manufacture of soaps and body care products. It is furthermore an important raw material for the generation of biodiesel. Depending on the degree of refinement, palm oil can be red, reddish or even colorless in appearance. The carotenes responsible for the color are removed during refinement and the oil becomes increasingly clear. In this Note, the chlorine and sulfur content of various palm oils are determined using Combustion IC.Keyword: pyrohydrolysis

Coal contains a certain amount of fluorine, chlorine, and sulfur compounds. During combustion of the coal, these components release corrosive acids (e.g., fluorine compounds form hydrofluoric acid). Thermal power plants therefore request low-fluorine coal to avoid massive hydrofluoric acid production. In this application note, fluorine content in coal is determined by ion chromatography after pyrohydrolysis.

The content of organic chloride in crude oil is determined according to ASTM D8150 in the naphtha fraction after distillation. The naphtha fraction is whashed with caustic and water, respectively, to remove hydrogen sulfide and inorganic halides. Here, the determination of organic chloride after inline combustion is presented. Although the sulfur content was of no interest in this application, the same setup allows sulfur quantification.

Polymer materials that are used for building and decoration purposes need to be flame resistant. To reach the required level of resistance flame-retardants are added to the plain polymer. Flame-retardants are often haloorganic compounds. The use of such components and the respective concentration of introduced halogens can be determined by Combustion IC. The recovery over the full system is tested with acertified reference material (CRM).

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.

In textiles, the water-repelling effect may be introduced by different treatments, such as the application of fluorochemicals. These compounds, especially perfluoroorganic substances, are extremely persistent in the environment and are therefore listed as emergent contaminants. Combustion IC with pyrohydrolysis and subsequent ion chromatographic determination is applied to analyze the fluorine content in fabrics.

Sulfur species are critical contaminants in ammonia gas. They can cause high-temperature sulfidation of metals, form aggressive complexes with other elements, or react subsequently in processes where the ammonia gas is used. The concentration of such impurities tends to be very low, but they may not exceed critical levels of 0.5 mg/L. Although this level is very close to the system blank of the Combustion IC system, the setup can be used to prove that such critical limits are not exceeded.

Cellulose ester foils are produced using chlorinated solvents. The residual amount of the solvent used in production evaporates within a few days in ambient conditions. The residual solvent is determined by combustion IC, through the conversion of organically bound chlorine to chloride by pyrohydrolysis. The final product needs to be free of all chlorinated solvents. Therefore, critical contents of such compounds can be detected in quality control analysis. Application of MiPT in this study has enabled an automated and precise calibration out of a single standard.

Organic halides must be monitored in the environment. Combustion ion chromatography (CIC) is used for accurate halogen analysis in solids following EN 17813:2023.

This Application Note presents a walkthrough of an experiment on 4-nitrothiophenol using hyphenated EC-Raman, a combination of Raman spectroscopy and electrochemistry.

Determination of acetate and methansulfonate in an organic salt using anion chromatography with direct conductivity detection.

Determination of sodium dodecylsulfate (SDS, sodium laurylsulfate) using anion chromatography with direct conductivity detection.

Sulfathiazoles are sulfonamides with antibiotic effect that occur in various polymorphous forms and that are often used in veterinary medicine. This Application Note shows the differentiation between commercial and sulfathiazole form I using near-infrared spectroscopy (NIRS) with the help of the overtone frequencies of N-H stretching vibration. Form I is the least stable polymorphous form. Crystallization and polymorphism must be monitored as part of quality controls. In this, NIRS is considerably more rapid and more reliable than conventional laboratory methods.

Rapid quality control for toothpaste is achieved by Metrohm`s Vis-NIR analyzers. Vis-NIR technology offers significant advantages compared to standard reference analysis. It is a cost effective and safe method because no hazardous chemicals are used.

Raw oil contains several percent by weight of sulfur compounds. They not only have an unpleasant smell, they are also environmentally harmful and corrosive which is why they must be largely removed during refining. The 2045TI Ex proof Analyzer with a flexible sample pretreatment system is to be found in a very wide variety of refinery applications. On the one hand, it monitors mercaptan and H2S content in accordance with ASTM D3227 and UOP163; on the other hand it can be used for the determination of ammonia, halogen and phenol content as well as for the bromide index, saponification and acid number. The analyzer fulfills EU Directive 94/9/EC (ATEX95) and is certified for Zones 1 and 2.

This Application Note describes the rapid and non-destructive identification of conventional organic solvents using hand-held Raman spectrometers. Measurements with the handheld Raman spectrometer Mira M-1 require no sample preparation and provide immediate and unambiguous results.

Determination of fluoride, chloride, nitrite, nitrate, benzoate, and sulfate in PVC film using anion chromatography with conductivity detection after chemical suppression.

Determination of bromoacetate, methanesulfonate, chloride, phosphate, and sulfate in an acidic cleaning solution using anion chromatography with conductivity detection and chemical suppression.

Determination of octylsulfonate, octylsulfate, dodecylsulfate, and oleate in a shower cream using reversed phase chromatography with conductivity detection after chemical suppression applying gradient elution.

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.

Simultaneous determination of hydrogen sulfide and mercaptans in petroleum products by potentiometric titration with silver nitrate using the Ag-Titrode.

Potentiometric titration with silver nitrate can be used for the determination of mercaptans in refinery products. This Application Note describes their automatic determination in a middle distillate sample (gas oil).

The purity of sulfanilamide was determined by means of automatic potentiometric titration using sodium nitrite as the titrant. The solution was spiked with potassium bromide, because bromide ions catalyze diazotization titration.

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

Determination of thiamine hydrochloride according to USP 28-NF 23 (second supplement) using RP chromatography with UV detection.

In industrial cooling water systems, copper and its alloys are widely used because of their superior heat transfer properties. These materials are, however, susceptible to corrosion. Azoles are commonly used to protect copper and its alloys from corrosion. These corrosion inhibitors are quantified by ion chromatography with UV/VIS detection.

Determination of clothiapine in a pharmaceutical standard.

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.

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

Ion chromatography is used as a high-performance analysis method in numerous applications. For complex analysis tasks, alternative detectors such as the amperometric detector or the UV/VIS detector are often also used in addition to the conductivity detector. This article describes the areas of utilization of the amperometric detector. Catchword: Antibiotics