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Hydroxyl is an important functional group and knowledge of its content is required in many intermediate and end-use products such as polyols, resins, lacquer raw materials and fats (petroleum industry). The test method to be described determines primary and secondary hydroxyl groups. The hydroxyl number is defined as the mg of KOH equivalent to the hydroxyl content of 1 g of sample.The most frequently described method for determining the hydroxyl number is the conversion with acetic anhydride in pyridine with subsequent titration of the acetic acid released: H3C-CO-O-CO-CH3 + R-OH -> R-O-CO-CH3 + CH3COOH. However, this method suffers from the following drawbacks: - The sample must be boiled under reflux for 1 h (long reaction time and laborious, expensive sample handling) - The method cannot be automated - Small hydroxyl numbers cannot be determined exactly - Pyridine has to be used, which is both toxic and foul-smellingBoth standards, ASTM E1899-08 and DIN 53240-2, offer alternative methods that do not require manual sample preparation and therefore can be fully automated: The method suggested in ASTM E1899-08 is based on the reaction of the hydroxyl groups attached to primary and secondary carbon atoms with excess toluene-4-sulfonyl-isocyanate (TSI) to form an acidic carbamate. The latter can then be titrated in a non-aqueous medium with the strong base tetrabutyl- ammonium hydroxide (TBAOH). The method suggested in DIN 53240-2 is based on the catalyzed acetylation of the hydroxyl group. After hydrolysis of the intermediate, the remaining acetic acid is titrated in a non-aqueous medium with alcoholic KOH solution. The present work demonstrates and discusses an easy way to determine the hydroxyl number according to ASTM E1899-08 or DIN 53240-2 with a fully automated titrimetric system for a great variety of industrial oil samples.

The poster describes the development of an automated Karl Fischer method for determining the water content in different edible oils.

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

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

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

The Rancimat method is an accelerated ageing test. Air is conducted through the sample in the reaction vessel at a constantly increased temperature. The fatty acids are oxidized during this process. Volatile secondary reaction products are formed at the end of the test that are conducted by air flow into a measuring vessel, where they are absorbed by a measuring solution (distilled water). The continually recorded electrical conductivity increases as a result of the absorption of the ionic reaction products. The time up to which the secondary reaction products arise is called the induction time. It characterizes the oxidation stability of oils and fats.This Application Bulletin provides a detailed description of the method, in particular also of the required sample preparation.

Only coulometric Karl Fischer titration can determine low water contents with sufficient accuracy.This Application Bulletin describes the direct determination according to ASTM D6304, ASTM E1064, ASTM D1533, ASTM D3401, ASTM D4928, EN IEC 60814, EN ISO 12937, ISO 10337, DIN 51777, and GB/T 11146. The oven technique is described according to ASTM D6304, EN IEC 60814, and DIN 51777.

The effectiveness of antioxidants can be expressed as antioxidant activity. It can be readily determined using the Rancimat method. This is accomplished by first determining the induction time of a mixture made up of hog fat and the antioxidant to be investigated and then by determining the corresponding time for hog fat alone. The quotient expresses the efficiency of the respective antioxidant and is referred to as the antioxidant activity index (AAI).This Application describes the determination of the antioxidant activity index of five common antioxidants.

In titration, the titrant reacts with the analyte either exothermically (gives off heat) or endothermically (absorbs heat). The Thermoprobe measures the temperature change during titration. When all of the analyte has reacted with the titrant, the temperature of the solution will change, and the endpoint of the titration is indicated by an inflection in the temperature curve. Catalytically enhanced titrations using paraformaldehyde as catalyst are based on the endothermic hydrolysis of the paraformaldehyde in the presence of excess hydroxide ions. Edible oils are dissolved in a mixture of toluene and 2-propanol (1:1) and titrated with standardized TBAH (0.01 mol/L) in 2-propanol to a catalytically enhanced endpoint.

The oxidation stability of fats and oils is an important parameter for quality controls in the food industry. Ideally, the determination is made with the Rancimat method, which is suitable for both liquid and solid samples. Its determination takes place directly in the sample or, in cases where this is not possible, in the extracted fat following cold extraction.

This Application Bulletin describes the determination of the total acid number in various oil samples by catalytic thermometric titration as per ASTM D8045.

Paraffin and lubricating oils are yielded from the wax fraction of raw oil distillation. The chloride content of both should be low. This Application Note describes chloride determination after inline combustion. Although it does not happen in this application, this method can also be used to quantify the sulfur content.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

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.

Determination of free fatty acids (FFA) in oils.

Determination of low content of HCl (around 10 ppm) in silicone oil.

Iodine value (IV) is a measure of the total number of double bonds present in fats and oils. It is expressed as the «number of grams of iodine that will react with the double bonds in 100 grams of fats or oils». The determination is conducted by dissolving a weighed sample in a non-polar solvent such as cyclohexane, then adding glacial acetic acid. The double bonds are reacted with an excess of a solution of iodine monochloride in glacial acetic acid («Wijs solution»). Mercuric ions are added to hasten the reaction. After completion of the reaction, the excess iodine monochloride is decomposed to iodine by the addition of aqueous potassium iodide solution, which is then titrated with standard sodium thiosulfate solution.

Automated determination of total acid number (TAN) in new and used lubricating oils and crude oils using the 814 USB Sample Processor. Dissolve oil sample in mixture of toluene and 2-propanol, add paraformaldehyde and titrate with 0.1 mol/L or 0.01 mol/L KOH in propan-2-ol. The endpoint is indicated by an endothermic response caused by the base-catalyzed depolymerization of paraformaldehyde.Reference: 1. M. J. D. Carneiro, M. A. Feres Júnior, and O. E. S. Godinho. Determination of the acidity of oils using paraformaldehyde as a thermometric end-point indicator. J. Braz. Chem. Soc. 13 (5) 692-694 (2002)

This Application Note describes the determination of the total concentration of sodium in precursor solutions used in the manufacturing of margarine. The solutions of the precursors are mixed with edible fats and oils to make margarine. Traces of sodium chloride and other sodium and potassium salts may be added to the margarine during this process, usually in the form of emulsifiers, stabilizers, antioxidants, vitamins, coloring agents or flavor enhancers. The analysis of the total sodium content in the precursor solutions is more efficient and cost-effective for the manufacturers than later total sodium content analyses in the final product.As a rule, argentometric titration of chloride is used for indirect determination of the sodium content of foodstuffs. The assumption behind this approach is that the chloride ions are present in a molar ratio of 1:1 with the sodium ions. This is however not the case when – as is usually the case with foodstuffs containing sodium – additional compounds containing sodium are also present in the margarine. The use of potassium chloride as a partial replacement for sodium chloride in some formulations is an additional source of error.The direct titration of sodium by means of thermometric endpoint titration (TET) eliminates these problems. TET is a direct determination method that not only takes into account the entire sodium content present in the solution but is also not hampered by the presence of potassium ions. In addition to this application note, you can find more information on thermometric sodium determination in foods in our application video available on YouTube:https://youtu.be/lnCp9jBxoEs

The water content of animal fat extract is determined according to Karl Fischer.

The water content of silicone oil is determined according to Karl Fischer by coulometric titration.

This Application Note shows the fast and parallel determination of water content and pH value in crude tall oil samples using near-infrared spectroscopy (NIRS). Crude tall oil is an important byproduct of pulp production in the power process. NIRS is an efficient alternative to conventional laboratory methods: It permits rapid raw material inspection, process monitoring and final product checking.

Determination of key quality parameters of palm oil, namely free fatty acids (FFA), iodine value (IV), moisture content, deterioration of bleachability index (DOBI), and carotene require the use of several different analytical methods, which are laborious and can lack in accuracy. This application note demonstrates that the XDS RapidLiquid Analyzer operating in the visible and near infrared spectral region (Vis-NIR) provides a cost-efficient and fast solution for the determination of these quality control parameters in palm oil. With no sample preparation or chemicals needed, Vis-NIR spectroscopy allows for the analysis of palm oil in less than a minute and can be used by anyone.

Cannabidiol (CBD) is a popular natural remedy from the cannabis plant used in many pharmaceutical, food, and cosmetic products. Unlike tetrahydrocannabinol (THC), CBD is not psychoactive, making it an appealing option for those who are looking for relief from pain and other symptoms without mind-altering effects. CBD oil is made by extracting the cannabinoid from the plant, then diluting it with a carrier oil (e.g., coconut or hemp seed oil). The standard HPLC method requires 45 minutes to perform by highly trained analysts. In contrast to the primary method, Vis-NIR spectroscopy is a cost-efficient and fast analytical solution for the determination of cannabinoid content in edible oils.

Near-infrared spectroscopy can quickly determine multiple edible oil quality parameters simultaneously without sample preparation as shown in this Application Note.

Near-infrared spectroscopy (NIRS) quickly assesses key quality parameters in palm oil such as iodine value and fatty acid profile without sample preparation.

Monitoring the iodine value in edible oil blends is crucial to produce vegetable oils with the desired properties. This Application Note displays the benefit of using the Metrohm NIRS DS2500 Liquid Analyzer for quality control in food laboratories.

Metrohm has partnered with industry leaders to develop an alternative standard for the measurement of acid number (AN) in crude oil and petroleum products to overcome shortcomings in the current method (ASTM D664). This new standard method (ASTM D8045) describes the use of thermometric catalytic titration for this analysis. Results agree closely with those from ASTM D664, but the thermometric catalytic titration method is far superior in terms of reproducibility and speed of analysis, with determinations being complete in one minute.Solvent usage is much less compared to older methods, saving on waste disposal cost. Comparison studies show very close data correlation between ASTM D8045 and traditional potentiometric AN titration methods making implementation into a refinery with historic data practical.

Wax has theoretically an unlimited shelf life, however many additives (flavor, softener, etc.) can affect it negatively. Since both synthetic and natural waxes are used in various products, such as cosmetics and foods, expiry dates have to be specified. The oxidation stability can give an approximate indication for the shelf life. A reproducible and accurate determination of the oxidation stability using the 892 Professional Rancimat can be realized.

Determining the oxidation stability of raw materials for the cosmetic and pharmaceutical industry.

The oxidative stability of sunflower oil using AOCS Cd 12b-92, EN ISO 6886, and a method based on EN ISO 6886 from Metrohm are compared. No significant differences are found.

This Application Note describes the determination of the oxidation stability of different sausages with the recommended method from Metrohm using an 892 Professional Rancimat.

This Application Note describes the determination of the oxidation stability of the fat in different sausages extracted with cold petroleum ether using an 892 Professional Rancimat.

Determination of the identity and purity of ingredients is essential for the product quality of functional foods (neutraceuticals) and cosmetics. It prevents the utilization of inferior substances in the production process and thus avoids expensive delays and out-of-spec products. This Application Note describes the identification and checking of fatty acids in functional foods and cosmetics using the Metrohm Instant Raman Analyzer MIRA P.

Determination of chloride, nitrite, nitrate, phosphate, and sulfate in cutting oil emulsion using anion chromatography with conductivity detection after chemical suppression and dialysis for sample preparation.

This application note shows how coconut oil ethoxylates can be determined via potentiometric titration.

This Application Note presents a modified time-saving method to determine iodine value (IV) in edible oils based on several standards (EN ISO 3961, ASTM D5554, etc.).

This Application Note details a method to determine the peroxide value of edible fats and oils based on EN ISO 27107, EN ISO 3960, AOAC 965.33, Ph.Eur. 2.5.5, and USP<401>.

The saponification value evaluates edible oil quality by indicating the average molecular weight of fatty acids. Its titrimetric determination in canola and olive oil is described here.

This Application Note describes the titration of acid value and free fatty acids in different edible oils, based on the standards EN ISO 660, USP<401>, and Ph.Eur. 2.5.1.

The hydroxyl number (HN) is an important sum parameter for quantifying the presence of hydroxyl groups in chemicals. As a key quality parameter, it is determined in various substances. For pharmaceutical samples, USP chapter <401> and Ph. Eur. Chapter 2.5.3 describe the determination. However these methods either use toxic pyridine and require refluxing or have long reaction times.In this Application Note, an alternative method according to ASTM E1899 is presented. This method is pyridine-free and does not require refluxing or long reaction times. The determination is performed at room temperature with only a small sample size. The analysis including all preparation steps is performed with a fully automatic OMNIS system. This allows parallel analysis of multiple samples, increasing productivity in the laboratory by 50%.

Direct titration is a simple and precise way to accurately measure the caffeine content in different nonaqueous products. The OMNIS Titrator equipped with a dSolvotrode reliably determines caffeine through flexible analyses combined with high-end software.

Determination of Cd, Pb, Cu, Ni, and Co in soybean oil after extraction by boiling with HCl under reflux.

Edible oils comprise a significant portion of any diet, and they also have important roles in the production of foods, cosmetics, and skincare products. For these reasons, a convenient and accurate method for materials identification of a variety of fats and oils is highly desirable. Historically, authentication of fats and oils was performed through intensive laboratory techniques involving chromatographic methods. Here, Raman spectroscopy combined with Principle Component Analysis (PCA) has been used for materials identification with 16 different edible oils, with excellent results. Raman is an ideal technique for evaluation of fats, as carboncarbon double- and single-bonds give strong Raman signals. PCA analysis in combination with Raman spectroscopy is a powerful tool for qualification and verification of different fats and oils, as there are few visual differences between spectra of edible oils.

The acid number (AN) is a measure for the quality of oils and their potential to enhance corrosion. When analyzing fresh, unused oils, the AN is used to ensure the specified quality from the manufacturer, whereas for used oils the AN is determined to observe its increase until a critical level is reached. Although it is generally assumed that the AN correlates to the corrosive potential of the oil, this is not exactly correct, as it is the change of the AN value which indicates this issue. Therefore it is necessary to determine the AN on a regular basis.Several standards already exist to determine AN via titration methods, however it is also possible to measure this parameter via spectroscopic (NIRS) methodology. No matter which technique you choose, Metrohm has you covered with high-performance instruments suitable for these published norms.

Rancidity of oils and fats is a factor which can immediately reduce the sale price of these products to customers in the food and cosmetics industries. Oils which remain stable over longer periods of time are more highly valued as they lead to a higher quality end product. Rancidity is a natural process which occurs as fats and oils age and oxidize, and can be delayed or even stopped by addition of antioxidants at the right time.Determination of rancidity is possible in several ways (e.g., measuring the acid number or peroxide value), though these tests only give information about the current state of the product, with no indication about the remaining shelf life. One analytical method that can measure this time span until spoilage is the Rancimat method, which artificially ages the samples to determine whether antioxidants may be needed to help manufacturers get the full value from their oils.