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Detection of peroxide gives the initial evidence of rancidity in unsaturated fats and oils. Other methods are available, but peroxide value is the most widely used. It gives a measure of the extent to which an oil sample has undergone primary oxidation; extent of secondary oxidation may be determined from p-anisidine test. [1]
The double bonds found in fats and oils play a role in autoxidation. Oils with a high degree of unsaturation are most susceptible to autoxidation. The best test for autoxidation (oxidative rancidity) is determination of the peroxide value. Peroxides are intermediates in the autoxidation reaction.
Autoxidation is a free radical reaction involving oxygen that leads to deterioration of fats and oils which form off-flavours and off-odours. Peroxide value, concentration of peroxide in an oil or fat, is useful for assessing the extent to which spoilage has advanced.
The peroxide value is defined as the amount of peroxide oxygen per 1 kilogram of fat or oil. Traditionally this was expressed in units of milliequivalents, although in SI units the appropriate option would be in millimoles per kilogram (N.B. 1 milliequivalents = 0.5 millimole; because 1 mEq of O2 =1 mmol/2 of O2 =0.5 mmol of O2, where 2 is valence). The unit of milliequivalent has been commonly abbreviated as mequiv or even as meq.
The peroxide value is determined by measuring the amount of iodine which is formed by the reaction of peroxides (formed in fat or oil) with iodide ion.
The base produced in this reaction is taken up by the excess of acetic acid present. To measure the iodine, a redox titration is performed using sodium thiosulfate.
The acidic conditions (excess acetic acid) prevents formation of hypoiodite (analogous to hypochlorite), which would interfere with the reaction.
A starch indicator solution is used, for which amylose forms a blue to black solution with iodine and is colourless when the iodine is converted to iodide titrated.
Peroxide values of fresh oils are less than 10 milliequivalents/kg; when the peroxide value is between 30* and 40 milliequivalents/kg, a rancid taste is noticeable.
Iodine is a chemical element; it has symbol I and atomic number 53. The heaviest of the stable halogens, it exists at standard conditions as a semi-lustrous, non-metallic solid that melts to form a deep violet liquid at 114 °C (237 °F), and boils to a violet gas at 184 °C (363 °F). The element was discovered by the French chemist Bernard Courtois in 1811 and was named two years later by Joseph Louis Gay-Lussac, after the Ancient Greek Ιώδης, meaning 'violet'.
The Winkler test is used to determine the concentration of dissolved oxygen in water samples. Dissolved oxygen (D.O.) is widely used in water quality studies and routine operation of water reclamation facilities to analyze its level of oxygen saturation.
Rancidification is the process of complete or incomplete autoxidation or hydrolysis of fats and oils when exposed to air, light, moisture, or bacterial action, producing short-chain aldehydes, ketones and free fatty acids.
A drying oil is an oil that hardens to a tough, solid film after a period of exposure to air, at room temperature. The oil hardens through a chemical reaction in which the components crosslink by the action of oxygen. Drying oils are a key component of oil paint and some varnishes. Some commonly used drying oils include linseed oil, tung oil, poppy seed oil, perilla oil, castor oil and walnut oil. The use of natural drying oils has declined over the past several decades, as they have been replaced by alkyd resins and other binders.
Saponification value or saponification number represents the number of milligrams of potassium hydroxide (KOH) or sodium hydroxide (NaOH) required to saponify one gram of fat under the conditions specified. It is a measure of the average molecular weight of all the fatty acids present in the sample in form of triglycerides. The higher the saponification value, the lower the fatty acids average length, the lighter the mean molecular weight of triglycerides and vice versa. Practically, fats or oils with high saponification value are more suitable for soap making.
Lipid peroxidation, or lipid oxidation, is a complex chemical process that leads to oxidative degradation of lipids, resulting in the formation of peroxide and hydroperoxide derivatives. It occurs when free radicals, specifically reactive oxygen species (ROS), interact with lipids within cell membranes, typically polyunsaturated fatty acids (PUFAs) as they have carbon–carbon double bonds. This reaction leads to the formation of lipid radicals, collectively referred to as lipid peroxides or lipid oxidation products (LOPs), which in turn react with other oxidizing agents, leading to a chain reaction that results in oxidative stress and cell damage.
Diethyl ether hydroperoxide is the organic compound with the formula C2H5OCH(OOH)CH3. It is a colorless liquid. Diethyl ether hydroperoxide and its condensation products are responsible for the explosive organic peroxides that slowly form upon exposure of diethyl ether to ambient air and temperature conditions.
In chemistry, the iodine value is the mass of iodine in grams that is consumed by 100 grams of a chemical substance. Iodine numbers are often used to determine the degree of unsaturation in fats, oils and waxes. In fatty acids, unsaturation occurs mainly as double bonds which are very reactive towards halogens, the iodine in this case. Thus, the higher the iodine value, the more unsaturations are present in the fat. It can be seen from the table that coconut oil is very saturated, which means it is good for making soap. On the other hand, linseed oil is highly unsaturated, which makes it a drying oil, well suited for making oil paints.
In chemistry, acid value is a number used to quantify the acidity of a given chemical substance. It is the quantity of base, expressed as milligrams of KOH required to neutralize the acidic constituents in 1 gram of a sample. The acid value measures the acidity of water-insoluble substances like oils, fats, waxes and resins, which do not have a pH value.
Iodic acid is a white water-soluble solid with the chemical formula HIO3. Its robustness contrasts with the instability of chloric acid and bromic acid. Iodic acid features iodine in the oxidation state +5 and is one of the most stable oxo-acids of the halogens. When heated, samples dehydrate to give iodine pentoxide. On further heating, the iodine pentoxide further decomposes, giving a mix of iodine, oxygen and lower oxides of iodine.
Iodometry, known as iodometric titration, is a method of volumetric chemical analysis, a redox titration where the appearance or disappearance of elementary iodine indicates the end point.
The iodine clock reaction is a classical chemical clock demonstration experiment to display chemical kinetics in action; it was discovered by Hans Heinrich Landolt in 1886. The iodine clock reaction exists in several variations, which each involve iodine species and redox reagents in the presence of starch. Two colourless solutions are mixed and at first there is no visible reaction. After a short time delay, the liquid suddenly turns to a shade of dark blue due to the formation of a triiodide–starch complex. In some variations, the solution will repeatedly cycle from colorless to blue and back to colorless, until the reagents are depleted.
Autoxidation refers to oxidations brought about by reactions with oxygen at normal temperatures, without the intervention of flame or electric spark. The term is usually used to describe the gradual degradation of organic compounds in air at ambient temperatures. Many common phenomena can be attributed to autoxidation, such as food going rancid, the 'drying' of varnishes and paints, and the perishing of rubber. It is also an important concept in both industrial chemistry and biology. Autoxidation is therefore a fairly broad term and can encompass examples of photooxygenation and catalytic oxidation.
Hydroperoxides or peroxols are compounds of the form ROOH, where R stands for any group, typically organic, which contain the hydroperoxy functional group. Hydroperoxide also refers to the hydroperoxide anion and its salts, and the neutral hydroperoxyl radical (•OOH) consist of an unbond hydroperoxy group. When R is organic, the compounds are called organic hydroperoxides. Such compounds are a subset of organic peroxides, which have the formula ROOR. Organic hydroperoxides can either intentionally or unintentionally initiate explosive polymerisation in materials with unsaturated chemical bonds.
The Briggs–Rauscher oscillating reaction is one of a small number of known oscillating chemical reactions. It is especially well suited for demonstration purposes because of its visually striking colour changes: the freshly prepared colourless solution slowly turns an amber colour, then suddenly changes to a very dark blue. This slowly fades to colourless and the process repeats, about ten times in the most popular formulation, before ending as a dark blue liquid smelling strongly of iodine.
Iodine monochloride is an interhalogen compound with the formula ICl. It is a red-brown chemical compound that melts near room temperature. Because of the difference in the electronegativity of iodine and chlorine, this molecule is highly polar and behaves as a source of I+. Discovered in 1814 by Gay-Lussac, iodine monochloride is the first interhalogen compound discovered.
Iodine compounds are compounds containing the element iodine. Iodine can form compounds using multiple oxidation states. Iodine is quite reactive, but it is much less reactive than the other halogens. For example, while chlorine gas will halogenate carbon monoxide, nitric oxide, and sulfur dioxide, iodine will not do so. Furthermore, iodination of metals tends to result in lower oxidation states than chlorination or bromination; for example, rhenium metal reacts with chlorine to form rhenium hexachloride, but with bromine it forms only rhenium pentabromide and iodine can achieve only rhenium tetraiodide. By the same token, however, since iodine has the lowest ionisation energy among the halogens and is the most easily oxidised of them, it has a more significant cationic chemistry and its higher oxidation states are rather more stable than those of bromine and chlorine, for example in iodine heptafluoride.
The Bray–Liebhafsky reaction is a chemical clock first described by William C. Bray in 1921 and the first oscillating reaction in a stirred homogeneous solution. He investigated the role of the iodate, the anion of iodic acid, in the catalytic conversion of hydrogen peroxide to oxygen and water by the iodate. He observed that the concentration of iodine molecules oscillated periodically and that hydrogen peroxide was consumed during the reaction.
Organoiodine chemistry is the study of the synthesis and properties of organoiodine compounds, or organoiodides, organic compounds that contain one or more carbon–iodine bonds. They occur widely in organic chemistry, but are relatively rare in nature. The thyroxine hormones are organoiodine compounds that are required for health and the reason for government-mandated iodization of salt.