Flow of fluidized solids and bubbles in standpipes and risers

Equations are presented for the densities of fluidized solid-bubble mixtures in downward and upward vertical flow. Data from a large commercial standpipe are in close agreement with calculations. Flow instability is predicted when downward solid flow is sufficient to hold a gas bubble stationary in a standpipe. Commercial experience of such instability is presented indicating the existence of slugs in a 45-in.-diam. standpipe.     

Preparation of lot samples of nut meats for mycotoxin assay

A procedure has been devised for preparing lot samples of mycotoxin-contaminated nut meats so that a representative analytical sample may be removed. The sample is rapidly reduced to coarse size. A relatively large portion (about 1/10 of total sample) of subsample is then split out and further comminuted to a fine particle size with the aid of a fat solvent (meat-solvent, w/v, 3:2). The analytical sample is removed from this mixture. The procedure was tested with shelled almonds and shelled walnuts using radioactive nuts to simulate the mycotoxin contamination and provide a simple, precise measure of the contaminated nut meat distribution. The pooled coefficient of variation was 18% for the subsamples and 4.4% for the analytical samples. Considering the dilution factors used (1.50 and 2.14 contaminated nuts/10⁴ nuts) and the low degree of reliability of the lot sample, the sample preparation methods tested appear to be practical and reliable.     

NMR chemical shift reagents in structural determination of lipid derivatives: IV. Methylcis- andtrans-9,10-epoxystearate and methylerythro- andthreo-9,10-dihydroxystearate

Chemical shift reagents were used to expand the amount of structural information obtainable from NMR studies of derivatives of methyl oleate and elaidate:methylcis-9,10-epoxystearate, methyltrans-9,10-epoxystearate, methyl erythro-9,10-dihydroxystearate, and methyl threo-9,10-dihydroxystearate. Chemical shift reagent studies of methyltrans-9,10-epoxystearate and methyl threo-9,10-dihydroxystearate afforded the most information. Chemical shift reagent studies of methylcis-9,10-epoxystearate and methyl erythro-9,10-dihydroxystearate were decidedly inferior. The series of complementary interpretive techniques previously developed during chemical shift reagent studies of monofunctional fatty esters and model polyfunctional fatty esters were found to be applicable in the current study. However, to avoid ambiguity in several proton assignments, supplementary spin decoupling experiments were necessary.     

Velocity and temperature profiles in compressible turbulent wall jets

The results of an experimental study on compressible turbulent wall jets resulting from a normally impinging round jet are presented. A finite difference technique was used for the calculation of velocity and temperature profiles. The eddy transfer coefficients used were functions of the distance from the plate throughout the flow field of the wall jet. The nozzle exit Mach number ranged up to 0.85. The nozzle exit temperature to the ambient temperature ratio ranged up to 2.92. The applicability of the calculational method has been thoroughly checked for a region of flow extending up to 12 nozzle diameters from the axis of symmetry. Using the empirical eddy transfer coefficients presented in this paper only starting profiles are needed to generate the solution for any point in the wall jet flow field which is described by a system of parabolic (boundary layer) equations.     

Superposition of the notched strength of composite laminates

An improved macroscopic model for predicting the strength of a composite laminate containing a circular notch is developed. Two constants are introduced which uniquely determine the notch sensitivity of a given material. A superposition method for the notched strength of composite laminates is developed which allows data for arbitrary materials and laminate configurations to be superimposed upon a single master curve. The influence of material orthotropy upon notched strength is discussed. A relative notch sensitivity parameter is introduced which allows quantification of the notch sensitivity of a given composite material system, stacking sequence, or laminate configuration.     

A vapor collection and thermal desorption method to measure semiochemical release rates from controlled release formulations

Chemicals (bp 270–490 °C/1 atm) evaporated from a controlled-release formulation dispenser were carried by an airflow to a collector packed with a polymeric adsorbent. After a set time, the chemicals were recovered by thermally desorbing them onto a gas-liquid chromatograpic column. They were then separated and quantified. The apparatus is described, and the requirements for its successful use are discussed. The soundness of the thermal desorption technique was confirmed by comparison with another technique: solvent elution from the collector. The advantages of the former technique are discussed.Mention of a commercial or proprietary product in this paper does not constitute an endorsement of that product by the USDA.     

Apparatus and procedure for measuring release rates from formulations of lepidopteran semiochemicals

An apparatus was developed wherein a vacuum source was used to pull air across a controlled-release-formulation dispenser or a planchet containing a known quantity of a semiochemical and into a collector filled with a polymeric adsorbent. After a set time, the semiochemical was eluted with solvent and was quantified by gas-liquid chromatography (GLC). High percentages of known quantities of the lepidopteran semiochemicals (Z)-7-dodecen-l -ol acetate (Z7DDA), boiling point (bp) 275 ° C/1 atm, (Z)-9-tetradecen-1-ol formate (Z9TDF), bp 289 °C/1 atm, and (Z,Z)-3,13-octadecadien-1-ol acetate (ZZODDA), bp 490 °C/1 atm, were recovered. The semiochemicals did not oxidize and were recovered quantitatively from the adsorbent. The release rates of Z9TDF from a controlled-release dispenser were found to be directly proportional to the airflow rates. Release rate measurements on the Z9TDF dispensers were made for the purpose of estimating the method's precision. The method was shown to give internally consistent results by measurements on another Z9TDF formulation. The accuracy of the method is discussed.Mention of a commercial or proprietary product in this paper does not constitute an endorsement by the USDA.     

Pyrolysis–molecular weight chromatography–vapor-phase infrared spectrophotometry: An on-line system for analysis of polymers. IV. Influence of cis/trans ratio on the thermal degradation of 1,4-polybutadienes

The influence of the cis/trans ratio of 1,4-polybutadienes on the volatile products formed during temperature-programmed thermal degradation to 15% weight loss has been investigated using a mass chromatograph (a gas chromatograph which directly provides mass numbers of resolved components of a mixture) and an “on the fly” vapor-phase infrared spectrophotometer. In order of amounts, major volatile products were 4-vinyl-1-cyclohexene (dimer), 1,3-butadiene (monomer), cyclopentene, and 1,3-cyclohexadiene. With increasing trans content, the relative quantities of 4-vinyl-1-cyclohexene decreased strongly, cyclopentene increased strongly, 1,3-butadiene decreased moderately, and 1,3-cyclohexadiene increased moderately. For a high-trans polybutadiene, increasing the heating rate produced relatively more monomer and dimer but less cyclopentene. Mass chromatograms from 1,4-polybutadienes which had been heated to 15% weight loss in their prehistory were similar to those obtained from 1,2-polybutadiene, indicating that 1,4-polybutadiene undergoes isomerization prior to degradation. Mechanisms for the formation of the main volatile products of decomposition are discussed.     

Solvation of ions—XX. The ferrocene—ferricinium couple and its role in the estimation of free energies of transfer of single ions

The ferrocene-ferricinium electrode (Pt/Foc, Fic⁺) was investigated in water, acetonitrile, ethanol, DMSO and DMF using single scan cyclic voltammetry and phase sensitive ac polarography. The oxidation-reduction is pseudo-reversible in all five solvents with an electrochemical rate constant of approximately 10⁻² cm/s. In all solvents a slow irreversible chemical step involving the ferricinium cation follows electron transfer, so that slow cyclic voltammetry or polarography rather than potentiometry is preferred if ferrocene is to be used as a reference electrode in non-aqueous solvents.

The Strehlow assumption, ΔG_tr(Foc) = ΔG_tr(Fic⁺ gives very different free energies of transfer of single ions from non-aqueous solvents to water when compared with the TATB assumption that ΔG_tr(Ph₄As⁺) = ΔG_tr(Ph₄B⁻). This discrepancy is likely to be because ferricinium is only a moderately large cation, so that ΔG_tr(Fic⁺) is less positive than ΔG_tr(Foc) for transfer to water. The discrepancy is not because of abnormal electrochemical behavior of the Pt/Foc, Fic⁺ electrode in water or other solvents. Values of E° vs nhe, H₂O in a variety of solvents based on the TATB assumption are presented.