Unsaturation, analytical determination

Acetylene Derived from Hydrocarbons The analysis of purified hydrocarbon-derived acetylene is primarily concerned with the determination of other unsaturated hydrocarbons and iaert gases. Besides chemical analysis, physical analytical methods are employed such as gas chromatography, ir, uv, and mass spectroscopy. In iadustrial practice, gas chromatography is the most widely used tool for the analysis of acetylene. Satisfactory separation of acetylene from its impurities can be achieved usiag 50—80 mesh Porapak N programmed from 50—100°C at 4°C per minute. 

Extraction Solvent. Dimethyl sulfoxide is immiscible with alkanes but is a good solvent for most unsaturated and polar compounds. Thus, it can be used to separate olefins from paraffins (93). It is used in the Institute Fransais du Pntrole (IFF) process for extracting aromatic hydrocarbons from refinery streams (94). It is also used in the analytical procedure for determining polynuclear hydrocarbons in food additives (qv) of petroleum origin (95). 

Bromine is used as an analytical reagent to determine the amount of unsaturation in organic compounds because carbon—carbon double bonds add bromine quantitatively, and for phenols which add bromine in the ortho and para positions. Standard bromine is added in excess and the amount unreacted is deterrnined by an indirect iodine titration. Bromine is also used to oxidize several elements, such as T1(I) to T1(III). Excess bromine is removed by adding phenol. Bromine plus an acid, such as nitric and/or hydrochloric, provides an oxidizing acid mixture usefiil in dissolving metal or mineral samples prior to analysis for sulfur. 

Matrix Components The term matrix component refers to the constituents in the material aside from those being determined, which are denoted as analyte. Clearly, what is a matrix component to one analyst may be an analyte to another. Thus, in one hand for the case of analyses for elemental content, components such as dietary fibre, ash, protein, fat, and carbohydrate are classified as matrix components and are used to define the nature of the material. On the other hand, reference values are required to monitor the quality of determinations of these nutritionally significant matrix components. Hence, there is a challenging immediate need for certified values for dietary fibre, ash, protein, fat, and carbohydrate. Concomitantly, these values must be accompanied by scientifically sound definitions (e.g. total soluble dietary fibre, total sulpha-ted ash, total unsaturated fat, polyunsaturated fat, individual lipids, simple sugars, and complex carbohydrates). 

After prolonged degassing of a large batch of PPG, analyses showed that its hydroxyl, unsaturation, and water contents were 0.97 meq/g, 0.033 meq/g, and 0.0035%, respectively. The hydroxyl content was determined by an acetylation method, carried out with acetic anhydride (10). The amounts of unsaturation and water were determined by the mecuric acetate and Karl Fischer methods (10), respectively. The obtained analytical results indicate that the number-average molecular weight of the dihydroxy material is 2062, provided its molecular weight is arbitrarily assumed to be twice that of the monohydroxy material, and that the mole fraction of the monohydroxy poly (propylene oxide) is 0.066. This value corresponds to a number-average functionality of 1.93 for the PPG. 

Complexes 17-19 can be written in one valence structure as a, /3-unsaturated carbonyl compounds in which the carbonyl oxygen atom is coordinated to a BF2(OR) Lewis acid. The C=C double bonds of such organic systems are activated toward certain reactions, like Diels-Alder additions, and complexes 17-19 show similar chemistry. Complexes 17 and 18 undergo Diels-Alder additions with isoprene, 2,3-dimethyl-1,3-butadiene, tram-2-methyl-l,3-pentadiene, and cyclopentadiene to give Diels-Alder products 20-23 as shown in Scheme 1 for complex 17 (32). Compounds 20-23 are prepared in crude product yields of 75-98% and are isolated as analytically pure solids in yields of 16-66%. The X-ray structure of the isoprene product 20 has been determined and the ORTEP diagram (shown in Fig. 3) reveals the regiochemistry of the Diels-Alder addition. The C-14=C-15 double bond distance is 1.327(4) A, and the... 

Previously (Cataldo and Braun, 2007), it has been noted the interesting correlation between C60 fullerene solubility and the unsaturation level of the fatty acids present in the vegetable oils and measured by the iodine number , an analytical test, which determines the number of double bonds present in the oil by the addition of iodine (Martinenghi, 1963). This correlation is confirmed for C also with the new measurements and is extendable also to C, . The correla-tion is shown in Fig. 13.1 and suggests that the solubility S expressed in milligrams per litre (mg/1) is linked to the iodine number of the oil (NI) according to the following equations ... 

Not only fatty acids but every unsaturated lipid molecule can undergo oxidation. So sterol oxidation products have also been studied in this case, HPLC is used both as a preparative step and for analytical purposes [33,34], HPLC as a preparative step was proposed by several researchers to improve the speed of analysis in the case of sterols, stigmastadienes, and waxes [35,36], Stigmastadiene, which is used as a marker in the refining process applied to vegetable oils, is determined by capillary GC however, the International Organization for Standardization (ISO) method (ISO 15788-2 2003) [37] uses HPLC as a rapid screening technique. 

The addition of thiocyanogen107 to unsaturated compounds108 forms the basis of a classical analytical method for determination of the unsaturation in fats and oils.108 The addition has been found to afford... 

The analytes separated on GC column are determined by a halogen-specific detector, such as an electrolytic conductivity detector (ELCD) or a microcoulo-metric detector. An ECD, FID, quadrupole mass selective detector, or ion trap detector (ITD) may also be used. A photoionization detector (PID) may also be used to determine unsaturated halogenated hydrocarbons such as chlorobenzene or trichloroethylene. Among the detectors, ELCD, PID, and ECD give a lower level of detection than FID or MS. The detector operating conditions for ELCD are listed below ... 

In a series of review papers Gergely et al. [21-23] reported the use of CD detection to solve various quantitative analytical problems. CD curves can, in some cases, be usefully applied to determine a, 0-unsaturated ketosteroid impurities in basic drug materials [21]. For instance ethynodiol is manufactured from norethisterone, so norethisterone acetate might always remain as an impurity in... 

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