Aufklärung der Molekülstruktur von Rohölinhaltstoffen durch NMR-Spektroskopie. I. Struktur der Isoparaffine des Rohöls

Elucidation of the Molecular Structure of Petroleum Constituents by NMR Spectroscopy. I. Structure of Branched Paraffins in Petroleum Crude A correlation between the ¹³C resonance peaks and possible structural elements of branched paraffins of petroleum fractions is given. New information concerning the structure of branched paraffins of petroleum crude is provided.     

Aufklärung der Molekülstruktur von Rohölinhaltsstoffen durch NMR-Spektroskopie. IV. Strukturtypen- und Strukturgruppenanalyse von Erdölfraktionen durch 1H-NMR-Spektroskopie

Elucidation of the Molecular Structure of Petroleum Constituents by N.M.R. Spectroscopy. IV. Analysis of Petroleum Fractions with Respect to Types of Structure and Structural Groups by ¹H N.M.R. Spectroscopy An improved method is presented which permits a quantitative analysis of crude oil products with a final boiling point below 400°C by means of the data of the ¹H n.m.r. spectrum and the average boiling point of the petroleum fractions. The types of aromatic structures are distinguished with respect to mono-, bi-, and tricyclic aromatics, and additionally, further structural group information is obtained.     

Aufklärung der Molekülstruktur von Rohölinhaltstoffen durch NMR-Spektroskopie. III. Quantitative Analyse von Erdölfraktionen im Siedebereich über 220°C

Elucidation of the Molecular Structure of Petroleum Constituents by N.M.R. Spectroscopy. III. Quantitative Analysis of Crude Oil Fractions in the Boiling Range above 220°C A method is presented which permits a quantitative analysis of crude oil products boiling > 220°C by means of the data of the ¹H n.m.r. spectrum. Besides of the quantitative analysis (aromatics, paraffins/naphthenes), further structural informations for both of these groups are given, concerning the number of carbon atoms in aromatic rings, the degree of substitution of the aromatic rings, and the CH₃-share of paraffins/naphthenes.     

Bestimmung der festen und flüssigen Bestandteile des Palmöls in Abhängigkeit von den Kristallisationsbedingungen durch Messung der magnetischen Kernresonanz

Determination of Solid and Liquid Components of Palm Oil as Function of the Crystallization Conditions by Measurement of Nuclear Magnetic Resonance Digital measurement of viscosity and nuclear magnetic impulse spectroscopy have been found to be very useful for following the course of crystallization of palm oils of various origin, subjected to different pretreatments. Following a short introduction in the fundamentals of these methods, comparative measurements of solid/liquid ratio using these methods as well as the most important factors influencing the crystallization of palm oils are reported.     

Molekülstruktur und Retentionsverhalten. IV. Gaschromatographische Charakterisierung von Chlorierungsprodukten des Isobutens

Molecular Structure and Retention Behaviour. IV. Gaschromatographic Characterization of Chlorination Products of Isobutene The retention indices of 23 theoretically possible chlorination products of isobutene have been determined on liquid phases with different polarity (Squalane, phenyl methyl silicone, nitril silicone, polyethylene glycol 4000) in the temperature range from 90 to 130°C. The relationships between the retention behaviour and the position and the number of chlorine atoms are discussed by means of retention indices, homomorphic factors H^s and index differences ΔI, respectively. It is shown that polar and non-polar interaction forces are influenced in different manner by the position of chlorine atoms in the molecule. For example, chlorine atoms in vinyl position to the double bond have smaller ΔI-increments as in allyl position, whereas their H^s-values differ only to a very little extent. For primary chlorine atoms, significantly greater H^s-values are observed than for tertiary chlorine atoms. However, their ∂ΔI-values are almost the same.     

Über den Anbau von Pilinuß conorium ovatum und die Fettsäuren-und Triglycerid-Zusammensetzung des Öls

Cultivation of Pilinut conorium ovatum and the Composition of Fatty Acids and Triglycerides of the Oil It is reported on the cultivation of Pilinut conorium ovatum and the composition of the fatty acids and triglycerides of the pilinut oil. Characteristic for this oil is the high content in palmitic acid. Exceptional for nut oils is the content of the low fatty acids capryl-, caprin-, lauric- and myristic acid. Characteristic for the composition of the triglycerides of pilinut oil is the low content of triolein.     

Zur Kenntnis der Cashew-Öle II. Über einige Derivate der Hauptbestandteile des Schalenöls

Studies on Cashew Oils II: Some Derivatives of the Main Components of the Cashew Nut Shell Liquid Derivatives (esters and ethers) of the 3-pentadecyl-phenol, which were prepared by the hydrogenation of Cardanol and the addition of thiocyanogen to hydrogenated 2-carboxy-3-pentadecyl-phenol are described.     

Über das Lagerverhalten von Kartoffelchips bei Belichtung und im Dunkeln I Analyse der durch Licht ausgelösten Veränderungen des Röstöls

Storage Behavior of Potato Chips Exposed to Light and in the Dark I: Analysis of Alterations of the Frying Oil Caused by Light Two aspects should be considered in evaluating potato chips produced commercially: quality control within the production plant at the time of manufacture, and detection of alterations on storage during the period of circulation. Currently, these products are packaged without taking protective measures to eliminate light and atmospheric oxygen. The investigations in the first part of this study were therefore devoted towards the determination of the action of these two parameters on the oxidation of the frying oil. Since the fat content of such products is as high as 45%, one might assume that the state of oxidation of the fat determines the quality of the entire product. Based on the kinetics of peroxide formation and oxygen uptake it is shown that the light sensitivity of refined peanut oil increases with increasing thermal stress in the frying equipment. A common consideration of the oxygen uptake as measured physically, the peroxide formation, the absorption at 232 nm, and the carbonyle content gives a deep insight into the course of the reaction. Due to the tocopherols present in the oil conjugated hydroperoxides are predominantly formed in a wide region of the oxidative process. The parallel reaction of peroxide decomposition, which yields carbonyls having intense taste, occurs to such a small extent that methods suitable for routine analysis are unable to differentiate the samples. Addition of antioxidants was found to be of little use for the quality retention under the action of light. Exact knowledge of the storage behavior might enable to draw consequences for the practice. For example, one might use a packaging, which not only fulfils the technical requirements but also justifies economic considerations.     

Betriebserfahrungen mit den unverseifbaren Bestandteilen des Rohtallöls in einer Linder-Tallölaufbereitungsanlage

Practical Experiences with the Unsaponifiable Constituents of Crude Talloil in a Linder Tall Oil Processing Plant The presented work studies the behavior of the unsaponifiable matter from crude talloil during the fractionation in a “Linder-Talloil-Fractionation plant” by means of qualitative gaschromatography. The purpose of this examination was to understand the interrelation between crude talloil quality, plant adjustment, and yields and quality of the finished products. The application of the conclusions from this examination in practice enables an optimal run of the plant and a prediction of the behavior of different crude talloil qualities during fractionation in a “Linder-Plant”.     

Zum abbau von polymerlösungen durch kapillarscherung. Einfluß der kapillarlänge und strömungsform auf den abbau

The dependence of shear degradation of polymer solutions on capillary length at constant shear stress is investigated with solutions of poly(isobutylene) (M_vis=6,1 · 10⁶) in toluene. We examined concentrations of 0.1, 0.25, 1 and 4% and found the degradation to increase with capillary length. In 0,1% solution we found a decreased efficiency of degradation, due to a change in the structure of solution. Flow instabilities, which appear above a critical shear rate D in polymer solutions and pretend a loss in viscosity, are not caused by shear degradation. This result supports our interpretation of unstable flow of polymer solutions as slip flow (spurt).     

Desaktivierungsverhalten von Arenen und Heteroarenen. II. Fluoreszenzlöschung des Acridiziniumions durch äußeren Schweratomeffekt

Deactivation Behaviour of Arenes and Heteroaenes. II. Fluorescence Quenching of Acridizinium Ion by External Heavy Atom Effect The rate constants of fluorescence quenching of acridizinium ion by aliphatic and aromatic bromides and iodides are outlined by the donor properties of quencher (among the known influence of atomic number). The values of the rate constants determined by using the Stern-Volmer-equation correlate with the ionization potentials of donors and the TAFT -constants. If the ionization potentials of the quenchers are low, a participation of triplet states of quenchers or the formation of an exciplex (deactivating ratationless) is assumed.     

Über den Einfluß von Licht auf den oxydativen Verderb von Speiseölen IV: Abhängigkeit der Oxydationsgeschwindigkeit von der Wellenlänge des eingestrahlten Lichts

Influence of Light on Oxidative Deterioration of Edible Oils IV: Dependence of Rate of Oxidation on Wave-Length of Incident Light A distinct decrease in the rate of oxidation with increasing wave-length is observed for soybean, sunflower and peanut oils when these oils are irradiated with various coloured lights having the same quantum-density. While studying the causes of this behaviour, pure absorption curves for the aforesaid oils were determined. Light of short wave was completely absorbed, whereas long-wave light was barely absorbed to any measurable extent. A considerable increase in quantum yield during oxidation occurs with increasing wave-length. Inspite of this, the oxidation of oils is catalysed most strongly by short-wave light, because the influence of pure absorption exceeds the increase in quantum yield. Pure absorption is therefore considered as the decisive factor with regard to the dependence of photooxidation on wave-length. Finally, the rate of oxidation, as determined in darkness, was found to increase with decreasing wave-length of light used for pre-oxidation of the oil.     

Eigenschaften von gelösten und gequollenen Polymethylmethacrylaten in Abhängigkeit von der Struktur

The stereocomplex formation, which is observed after mixing of stereoregular samples of polymethylmethacrylate (PMMA) in various solvents was studied by dielectric and viscosimetric measurements. By means of X-ray wide angle diffraction measurements of mixtures of stereoregular polymers freed from solvent it was found that the stereocomplex consists of crystalline regions. From viscosity measurements of solutions of various tacticity in comparison with swelling properties of crosslinked PMMA it is concluded that the association of isotactic and syndiotactic sequences, which is considered to be the reason for stereocomplex formation, also exists in solutions and gels of atactic PMMA. From the temperature dependence of the reduced specific viscosity, the complex dielectric constant, and the swelling we deduce that the association in microcrystalline regions leads to formation of physical crosslinks, which melt in a certain temperature range. The properties of dilute solutions prepared from mixtures of isotactic and syndiotactic PMMA and toluene can be interpreted by intermolecular association mainly. The anomalies observed in very dilute solutions are explained by intramolecular association. The properties of solutions in which association occurs are dependent on their preliminary thermal treatment and their previous history.     

Der Einfluß des Fortfalls der Laugeentsäuerung auf den Hydrierungsprozeß von Sojaöl

Influence of Cessation of Lye-Neutralisation on the Hydrogenation Process of Soya Bean Oil A greater number of soya bean oils of standard quality have been hydrogenated with or without previous lye-neutralisation. The cessation of the lye-neutralisation has a negative influence on the hydrogenation velocity and the linoleic acid selectivity.