Composition of mixed octadecadienoates via ozonolysis,chromatography and computer solution of linear equations

An approach to the analysis of 55 possible nonconjugated positional isomers of octadecadienoic acid is described and tested with mixtures of individual synthetic methyl esters. In the first example, by ozonolysis a sevencomponent mixture consisting ofcis,cis 5,12-, 6,10-, 6,11-, 6,12-, 7,12-, 8,12-, and 9,12-octadecadienoates was converted to aldehydes, aldehyde-esters and dialdehydes. These fragments were separated on a 50 m×0.2 mm free fatty acid phase (FFAP) vitreous silica capillary column. Equations for an arbitrarily restricted 12×15 matrix of linear simultaneous equations and a computer solution of the matrix provided the composition of the initial methyl octadecadienoate mixture. The power and significance of this method became apparent with the observation that only two of the seven isomers in the known mixture were resolved as single peaks by state-of-the-art capillary gas chromatography, but all seven were identified and estimated with acceptable error by the ozonolysis-capillary gas chromatography-computer procedure. In a generalized approach to the analysis of the 55 possible nonconjugated isomers, a computer program selects the appropriate matrix of linear simultaneous equations based on the aldehyde data supplied by the analyst. Twenty of 21 combinations of seven isomeric esters taken five at a time have been analyzed to assess the efficiency of the method. To illustrate applicability at this stage of development, the method has been used to analyze the diene products of the hydrazine reduction of γ-linolenic acid and the diene products from the biological desaturation of isomeric monoenes. The possibility of distinguishing geometric and positional isomers of 18∶2 has been opened by the observed separation ofcis-andtrans-unsaturated aldehydes and aldehyde-esters. Presented in part at the 16th World Congress of the International Society for Fat Research, October 4–7, 1983, in Budapest, Hungary, and at the American Oil Chemists' Society Meeting, May 15, 1986, in Honolulu, Hawaii.     

连续冶炼冶金焦工艺初探──（Ⅰ）现状分析和连续混热式焦炉的结构

本文论述了炼焦工艺的现状和发展方向，分析了存在的问题，提出了一种全新的连续型混热式冶金焦炉结构及其工艺流程，为焦化工业的发展探讨了一条新的途径。     

The influence of F doping on the activity of PbO2 film electrodes in oxygen evolution reaction

The PbO₂ and F⁻-doped PbO₂ (F-PbO₂) film electrodes have been prepared by an electrodeposition process onto platinum substrate. The changes of their electrochemical activity for oxygen evolution (OE) reaction with accelerated electrolysis time have been studied. The results show that the activity of the electrodes decreases with increasing electrolysis time. This can be attributed to the conductivity variations, which are caused by the decrease of the oxygen vacancy concentration in PbO₂ films during OE. The mechanism of the decrease of the oxygen vacancies has been investigated. For F-PbO₂ film electrodes, though its electrochemical activity is somewhat lower than that of undoped one, its activity stability is much higher in comparison with that of PbO₂. The influence of F⁻ doping on the activity of PbO₂ film electrodes has been also discussed.     

硫磺延伸产品的现状及展望

介绍了硫脲、甲硫醇、蛋氨酸、硫肥、含硫建筑材料、不溶性硫磺、Na-S电池等硫磺延伸产品情况.指出硫酸企业要以硫磺、CS2、SO2、SO3和硫酸为原料,构建多层次、多元化的精细硫化工产业链,使硫酸企业走上特色化工和精细化工之路.     

Cold water detergency studies using radiolabeled soils

The effects of single and multiple washing and of resoiling-rewashing of cotton and synthetic fabrics have been studied in Tergotometer tests at various levels of temperature, detergent concentration and water hardness. The soiling mixture consisted of a seven component sebum tagged with tritium and carbon-14; in some tests gammaray emitting Kaolinite clay was also used. Linear primary alcohol ethoxylate (LAEO) and linear alkylbenzene sulfonate (LAS) were used for surfactant type comparisons. In single wash tests in both hot and cold water, LAEO was generally more effective than LAS in removing sebum. This was particularly noticeable at low product concentration where insufficient sodium tripolyphosphate was present to sequester the water hardness. A 1/1 blend of the two surfactants approached LAEO in performance. The nonpolar sebum fraction was more readily removed from Dacron or nylon in cold water; otherwise, detergency was generally better at high temperatures. In rewash tests, using labeled lube oil, cholesterol and clay, a progressive increase in soil removal was found during five wash cycles. The nonpolar lube oil component was the most difficult to remove from permanent press Dacron-cotton (PP), but was more readily removed from cotton. The more polar cholesterol and especially the clay were more easily removed from PP. LAEO gave better detergency both hot and cold than LAS, especially in hard water. On cotton swatches resoiled with sebum after each wash the residual sebum content was still increasing after five cycles. With PP in soft water, a steady state was reached after three to five cycles. Soil buildup was greater as hardness increased and as wash temperature and active matter concentration decreased, and was generally greater on cotton than on PP. LAEO allowed appreciably less soil buildup than did LAS especially at low concentration in hard water, indicating a reduced requirement for sodium tripolyphosphate. Presented before the AOCS Meeting, New Orleans, April 1970.     

高硫石油焦燃烧固硫基础性研究及工业技术的进展

本文概述了高硫石油焦固硫的基础性研究及工业上的最新进展。     

Structure of polyurethane elastomers. X-ray diffraction and conformational analysis of MDI-propandiol and MDI-ethylene glycol hard segments

X-ray diffraction and conformational analysis have been used to investigate the structure of polyurethane hard segments prepared from diphenylmethane 4,4′-diisocyanate (MDI) with propandiol (PDO) and ethylene glycol (EDO) as chain extenders. The results are compared with those obtained previously for MDI-butandiol (BDO) hard segments. In the latter system, the poly(MDI-BDO) chains are fully extended with an all-trans conformation for the O(CH₂)₄O unit, and a monomer repeat of 18.95 Å. The unit cell is triclinic with a tilted base plane such that adjacent chains are staggered along the fibre axis. In contrast both poly(MDI-PDO) and poly(MDI-EDO) adopt unstaggered structures, i.e. the chains are in register and the unit cell base planes are perpendicular to the chain axis. The monomer repeats of 16.2 Å for poly(MDI-PDO) and 15.0 Å for poly(MDI-EDO) are shorter than the predicted repeats for fully-extended chains, indicating that these polymers have contracted conformations containing some gauche CH₂ groups. Conformational analysis shows that the 16.2 Å repeat for poly(MDI-PDO) can be achieved with the O(CH₂)₃O unit in the trans-gauche⁺-gauche⁺-trans or gauche⁺-trans-trans-gauche⁺ conformations. Similarly the 15.0 Å repeat for poly(MDI-EDO) is predicted for the gauche⁺-trans-gauche^? conformation for the O(CH₂)₂O unit. These conformations are of higher energy than the all-trans fully-extended chains. This may explain the higher crystalline perfection of the poly(MDI-BDO) hard segments, for which crystallization in the all-trans form will probably provide a greater driving force for phase separation.     

The hydrogen-electrode reaction in the isotopically mixed system—II. Evaluation of the electrolytic separation factor of deuterium from the rest potential of the hydrogen electrode in the deuterium-containing system

The rest potential, E_r, of the hydrogen electrode in deuterium-containing hydrogen and a solution of light water as referred to the reversible hydrogen electrode in the light hydrogen and the same solution is formulated as a function of deuterium content of the gaseous hydrogen and the deuterium separation factor, S_b, in the hydrogen ionization reaction. It is shown that the relation is not significantly affected by the operative mechanism of the hydrogen-electrode reaction. Consequently, the relation provides a convenient method of evaluating S_b from the observation of E_r.

Experiments were carried out on Pt, Ni, Au and Ag in the system composed of deuterium-containing hydrogen and light water. The value of S_b as evaluated from E_r was practically independent of the deuterium content in the gaseous hydrogen. The values obtained were 1·1 for Pt in acidic and alkaline solutions, 1·6 for Ni in alkaline solution, 1·2 for Au and 1·5 for Ag, both in acidic solution. These values multiplied by the partition coefficient of deuterium between hydrogen and water (4·0 at room temperature) give approximate values of the deuterium separation factor in the hydrogen evolution reaction.     

Measurement of the melting points of oligomers obtained in the manufacture of poly(ethylene terephthalate)

The melting points (T_m) were measured for oligomers obtained by a direct continuous esterification process between terephthalic acid and ethylene glycol. Multiple regression analyses of data were carried out, and an equation was obtained for predicting melting points with correlation coefficient of ～0.99.     

Effects of hydrogen on the transition layers between diamond films and Zr, Hf substrates

Highly purified polycrystalline wafers of Zr and Hf were chosen as substrates for diamond deposition by means of the d.c. arc discharge plasma CVD method. Polycrystalline diamond films were formed on both substrates. Scanning electron microscopy and high resolution X-ray diffraction were used to investigate the surface morphology of the diamond films and the composition of the interface layers between the diamond films and substrates. The experiments showed that the transition layer between the diamond films and Zr substrates was ZrC, ZrH and ZrC_0.32H_1.2. For Hf substrates, in addition to HfC, it is supposed that there were also some hydrides or carbohydrides in the transition layer, because several X-ray reflections appeared which could not be assigned to Hf, HfC or diamond.