Methods for the determination of cyclopropenoid fatty acids. VII. The dilution-HBr-titration technique as a general method

The stepwise HBr titration method for the cyclopropenoid analysis of cottonseed oils is subject to serious inaccuracies when applied to samples containing higher cyclopropenoid concentrations, particularly if they contain appreciable amounts of alumina-adsorbable materials. A modification of the method is described which eliminates these sources of error. Its validity has been established by the analysis of a wide range of synthetic compositions including compositions containing massive amounts of interfering HBr-reactive substances and other alumina-adsorbable materials. The method with further modification can be used to analyze glycerides with the same high degree of accuracy. Presented at the AOCS Meeting in Houston, April 1965. So. Utiliz. Res. Dev. Div., ARS, USDA.     

COMPUTER SIMULATION OF HYDRODEMETALLATION IN FIXED-BED REACTORS

An isothermal model for hydrodemetallation (HDM) of crude oils in catalytic fixed-bed reactors is proposed. This model involves a consecutive reaction mechanism, which is capable of accounting for particle deposit profiles with interior maxima. Consistent with the fact that HDM catalysts are conglomerates formed by precipitation, the porous catalyst itself is modeled as randomly overlapping spheres of equal size. The metal is deposited as growing metal sulfide crystallites on the inner surface of the catalyst. These crystallites originate from a certain number of randomly scattered nuclei and increase in size as the deposition proceeds. The random sphere model for the catalyst and the deposit provides the changes in the catalyst pore structure—local porosity and surface area.

The mass transport within the domain of the particle is due to restricted liquid diffusion, since the diameter of the metal bearing compound (porphyrin) and the intermediate are comparable to the pore size. The diffusion restrictions taken into account are the enhanced drag imposed on a molecule by adjacent pore walls and steric partitioning.

Since the deposition process is much slower than diffusion and reaction, the pseudo-steady-state assumption can be justified. The equations of conservation for mass are solved by orthogonal collocation on finite elements. Based on this solution technique a computer simulation program of HDM is designed that allows two modes of operation: constant temperature and constant conversion. The simulation program “SIMULA” is highly flexible with regard to reaction kinetics, catalyst structure, reactor design, and operating conditions. In comparison to a base case with uniform activity, the effect of intraparticle (radial) and bed (axial) activity profiles on the conversion rate is discussed. For the case investigated, a radial distribution of activity higher at the center of the particle than at the edge can increase catalyst life by 25%, but axial distribution was less successful.     

Microstructure and Microchemistry of Polymer-Derived Crystalline SiC Fibers

Stoichiometric and near-stoichiometric silicon carbide fibers, derived from the polymer polycarbosilane, have been characterized by scanning Auger and transmission electron microscope techniques. Excess carbon usually appeared in the fibers, but it could be eliminated by controlling processing conditions. The fibers consisted mainly of submicrometer-sized SiC microcrystals, with a considerably twinned and stacking-faulted β-SiC structure. Free carbon, which appeared in the form of graphite, was the only detectable intergranular phase in the nonstoichioinetric SiC fibers, while the stoichiometric SiC fibers contained no detectable second phase whatsoever.     

Chlorination of polystyrene

Chlorination of a low molecular weight polystyrene in the α position was studied by following changes in the infrared spectrum, glass transition temperature, and molecular weights of the polymer. The logarithm of the absorbance ratio at 2920 and 1500 cm^?1 as a function of mole per cent chlorination was linear. The glass transition temperatures, determined by use of a differential scanning calorimeter (DSC), were found to obey an equation developed by Dyvik for copolymers. The molecular weight of the chlorinated polystyrene decreased as a function of chlorination.     

An improved method for numerical solution of distillation processes

A new method for the numerical solution of a stagewise process is presented. The method consists of total linearization of all the equations in the distillation process, using the method of quasi-linearization. The resulting equations form a block-band matrix which can be readily solved by a method developed by the author. The method used for obtaining convergence is presented. The method has been tested for both binary and multi-component systems. The method has been compared with the Amundson-Pontinen method for a five component mixture. The method gives more rapid convergence. Numerical experiments indicate that the vapor and liquid flow rates are more stringent requirements than the bubble point.     

Studies on liver phosphatidyl cholines: I. Effects of fatty liver induction on phosphatidyl cholines from liver mitochondria and microsomes

Protein, total phospholipid, phosphatidyl cholines and phosphatidyl choline fractions from liver mitochondria and microsomes of female rats were analyzed after treatment with CCl₄ (0.3 ml of CCl₄ suspended in corn oil) or ethionine (50 mg in 0.9% saline) or after feeding a choline deficient, low protein diet for seven days. Phosphatidyl cholines were separated into four fractions differing in the degree of fatty acid unsaturation. Over 50% of total phosphatidyl choline phosphorus was present in fraction 3 of liver mitochondria and microsomes. The major fatty acid in fraction 1 was docosahexaenoic acid. Fraction 4 contains oleic and linoleic acids. Arachidonic acid occurs in fraction 2 and 3. Ethionine decreased the amount of microsomal protein and phosphatidyl choline fraction 1 of mitochondria. Microsomal protein was decreased by CCl₄. The choline deficient, low protein diet caused a decrease in mitochondrial and microsomal phospholipids. The amount of the mitochondrial phosphatidyl choline decreased. Corn oil increased the level of phosphatidyl choline fraction 3. Choline deficiency decreased the amount of phosphatidyl choline fraction 3, increased fraction 4 of mitochondria and microsomes and increased fraction 1 of microsomes.     

Cation Transport at 25°C from Binary Cd2+–Mn+ Mixtures in a H2O-CHCl3–H2O Liquid Membrane System Containing a Series of Macrocyclic Carriers[1]

Macrocycle-mediated fluxes of Cd(NO₃)₂ and of several binary mixtures of Cd(NO₃)₂ with the nitrate salt of either Na⁺, K⁺, Rb⁺ Cs⁺, Ag⁺, Ca²⁺, Sr²⁺, Pb²⁺, Zn²⁺, or Cu²⁺ have been determined in a H₂O-CHCl₃–H₂O liquid membrane system. Of the macrocycles studied, 2.2 and 2.2DD most successfully transported Cd²⁺ In the Cd²⁺–Mⁿ⁺ mixtures, Cd²⁺ was transported selectively with 2.2 when Mⁿ⁺ was either an alkali or an alkaline earth cation. However, when Mⁿ⁺ was either Ag⁺, Pb²⁺, or Cu²⁺ the Cd²⁺ flux was reduced sharply. Generally, cation flux was greater for 2.2DD than for 2.2 with selectivity for Cd²⁺ being altered also in several cases. Relative fluxes from binary cation mixtures depend on metal cation radius, macrocycle cavity diameter, ligand ring substituent and log K for metal ion-macrocycle interaction.     

A New Indole Synthesis Promoted by Metal Triflates

A new synthesis of 4- and 7-carbon-substituted indoles is described. The overall sequence involves the addition of a nitrile oxide to 1 carboethoxy-2-(or 3-) allylpyrrole, hydrogenation of the intermediate isoxazoline to β-hydroxy ketone and cyclization of the ketol using magnesium or zinc triflate to the substituted indole. This new indole-forming strategy can also accommodate the introduction of oxygen functionality into the indole 6-position. Possible mechanistic aspects of the reaction are detailed.     

Viscosity and Thermal Expansion of Mixed-Alkali Borate Glasses

Transformation-range viscosity and thermal expansion measurements were made for five series (Li-Na, Li-K, Li-Cs, Na-Cs, and K-Rb) of mixed-alkali borate glasses containing 30 mol% total alkali oxide. In each case, negative deviations from additivity were observed in the isokom and glass transformation temperatures. Positive deviations from additivity were observed in the thermal expansion coefficients for the Li-Na, Li-K, and K-Rb glasses, while the Li-Cs and Na-Cs glasses exhibited negative deviations. Maximization of the deviation from additivity in the viscosity and glass transformation temperatures occurred when the radius ratio of the two alkali ions was approximately 1.7 to 1.8. Combination of the results of this study with those of earlier studies indicates that the deviations from additivity observed for these properties are independent of the identity of the glass former.     

Foam fractionation of spent sulphite liquor: Part I: Separation of surfactants

The surface activity of spent sulphite liquor (SSL) and the separation of surface active components by foam fractionation were studied. The maximum activity (lowest surface tension) of SSL was observed at a high pH. The surface tension was found to be 42 mN/m and 38 mN/m at acidic and basic pH values, respectively, and also a maximum foaminess (Σ) of 7 min was observed at pH 10. Foam fractionation reduced the surfactant concentration by 90% at an optimum pH of 10. The surfactants were concentrated in the collapsed foam as shown by the fact that the critical micelle concentrations of the unfractionated SSL and foam were 70% (v/v) and 10% (v/v), respectively. The removed surfactants were concentrated in 20% of the original liquid volume.