A derivation of the particle size weighting factor in the measurement of rate coefficients

An analysis of the weighted concentration curve shows that the proper weighting for disperse populations of particle sizes varies according to the method of analysis used in data regression. A general form for the weighting factor is derived for the integral method. Several forms of the weighting factor for diffusion with a surface resistance are shown and the effect of particle size variations is demonstrated for a sample of Sepharose 6B (Pharmacia).     

Cathodic deposition of refractory intermetallic compounds from FLINAK melts Part II: Preparative cathodic deposition of TiB2 and ZrB2 and coatings thereof

At 700°C the production of TiB₂ was performed by cathodic deposition of this refractory intermetallic compound on carbon cathodes from FLINAK melts containing Ti(IV) and B(III) in concentration ratios ranging from 1:3 to 1:2 and total concentrations from 2 to 10 mol% at current densities from 0.2 to 3 A cm^–2. Current efficiencies were always lower than 100% but the purity of the deposited TiB₂ was in almost all cases better than 98%. Generating augmented mass transfer by the anode effect, which develops at high current densities, improved cathodic current efficiencies and enhanced the purity of the coarse deposit. Current efficiencies decreased with decreasing temperature. Smooth and dense coatings on carbon substrate were only obtained if the thickness of the coating was kept below a critical value of 0.5 mm. It was impossible to produce dense, well adhering coatings on copper rod electrodes since, due to the mismatch of the thermal expansion coefficients of copper and TiB₂ the coatings detached from the substrate on cooling. To produce pure ZrB₂ material or ZrB₂-coatings necessitates low current densities (i<0.04 A cm^–2). From the impure cathodically deposited mixtures of dendritic ZrB₂, which were obtained at higher current densities, solidified electrolyte and lower valent zirconium compounds could not be separated.     

Customizing the comonomer incorporation distribution in Ziegler–Natta-based LLDPE: Harnessing the influences of the titanation temperature during catalyst synthesis and of polymerization process parameters

The microstructure of linear low-density polyethylene (LLDPE) is strongly influenced by short-chain branches (SCBs) incorporated into the polymer backbone. Varying the number, distribution, and length of SCBs allows the properties of the resulting polymer to be tailored to meet specific requirements. Using Ziegler–Natta (ZN) catalysts for synthesis has disadvantages in terms of the comonomer incorporation distribution (CID) compared to, for instance, metallocene and post–metallocene catalysts. Nevertheless, ZN catalysts continue to be widely used, as many of the new generations of catalysts are more difficult to handle and cannot match the cheap cost of ZN catalysts. To improve this aspect of ZN catalysts, we investigated the influence of catalyst titanation temperature and polymerization process parameters on the CID. Our results show that it is possible to manipulate the process parameters of the present ZN catalyst system to yield a desired comonomer amount and CID in the polymer. Varying the titanation temperature clearly influenced the titanium content of the catalyst. Molecular-weight distribution analysis and deconvolution results indicate that changes in the amounts of comonomer incorporated and in the CID are directly related to the catalyst's active site that produces the lowest-molecular-weight fraction.     

Interlaboratory study on lipid oxidation during accelerated storage trials with rapeseed and sunflower oil analyzed by conjugated dienes as primary oxidation products

Accelerated storage tests are frequently used to assess the oxidative stability of foods and related systems due to its reproducibility. Various methods and experimental conditions are used to measure lipid oxidation. Differences between laboratories make it necessary to determine the repeatability and reproducibility of oxidation tests performed under the same conditions. The objective of the present interlaboratory study was to evaluate the outcome of a storage test for two different bulk oils, sunflower oil (SFO) and rapeseed oil (RSO), during a period of 9 weeks at 20°C, 30°C, 40°C, and 60°C. Sixteen laboratories were provided with bottled oils and conducted the storage tests according to a detailed protocol. Lipid oxidation was monitored by the formation of conjugated dienes (CD) and the activation energy (E_a) was determined for comparative purposes and statistically evaluated. An increase in CD formation was observed for both oils when the storage temperature was increased in all laboratories. The E_a,1 ranged from 47.9 to 73.3 kJ mol⁻¹ in RSO and from 27.8 to 62.6 kJ mol⁻¹ in SFO, with average values of 58.2 and 46.8 kJ mol⁻¹, respectively. The reproducibility coefficients were 10.9% and 18.2% for RSO and SFO, respectively. Practical applications: In order to compare results on oxidative stability of foods derived from different studies, the reproducibility of storage tests and methods employed to evaluate the oxidation level should be considered. This study provides fundamental data on the reproducibility of lipid oxidation under accelerated storage conditions and defines important parameters to be considered for the conduction of experiments.     

Evaluation of a Method to Measure Black Carbon Particles Suspended in Rainwater and Snow Samples

We conducted a detailed evaluation of a method for measuring the mass concentrations and size distributions of black carbon (BC) particles in rainwater and snow. The method uses an ultrasonic nebulizer (USN) and a single particle soot photometer (SP2). The USN disperses sample water into micron-size droplets at a constant rate and then dries them to release BC particles into the air. The masses of individual BC particles are measured by the SP2, using the laser-induced incandescence technique. The loss of BC particles during the extraction from liquid water to air depends on their sizes. We determined the size-dependent extraction efficiency using polystyrene latex (PSL) spheres with 12 different diameters between 107 and 1025 nm. The PSL concentrations in water were measured by the light extinction at 532 nm. The extraction efficiency of the USN showed a broad maximum of about 10% in the diameter range 200–500 nm and decreased substantially at larger sizes. The accuracy and reproducibility of the measured mass concentration of BC in sample water after long-term storage were about ±25% and ±35%, respectively. We tested the method by analyzing rainwater and surface snow samples collected in Okinawa and Sapporo, respectively. The measured number size distributions of BC in these samples showed negligible contributions of BC particles larger than 300 nm to the total number of BC particles. A dominant fraction of BC mass in these samples was observed in the diameter range 100–500 nm.

Copyright 2013 American Association for Aerosol Research     

Extrapolation of single particle soot photometer incandescent signal data

The Single Particle Soot Photometer (SP2) is an instrument for quantifying the refractory black carbon (rBC) mass of individual aerosol particles. It heats the particle’s rBC component to vaporization and quantifies the resulting visible thermal radiation to infer rBC mass. For purely technical reasons, SP2s are unable to quantify rBC mass beyond an easily adjustable limit due to eventual saturation of the electronics that record the visible light signals. Here, we evaluate an extrapolation algorithm to estimate rBC masses exceeding this upper limit in an SP2. The algorithm is based on identifying the crossing points of linear fits to unsaturated data, and using the duration of the saturated data to constrain potential errors. We find that extrapolation performance is quite insensitive to instrument parameters including laser intensity, rate of data acquisition, and particle speed through the laser. However, this approach increases uncertainty on the detection limit of the instrument, and is hence only useful in unknown aerosols for very limited extrapolation to approximately a factor of 1.5 increase in the upper mass range, corresponding to a 15% increase in the upper diameter limit. This increased range small enough that early identification of meaningful saturation during measurement campaigns remains the only tenable approach to robustly characterizing rBC mass size distributions and, in some cases, rBC mass concentrations.     

COSMO-RS:An ionic liquid prescreening tool for gas hydrate mitigation

Recently ionic liquids(ILs) are introduced as novel dual function gas hydrate inhibitors. However, no desired gas hydrate inhibition has been reported due to poor IL selection and/or tuning method. Trial error as well as selection based on existing literature are the methods currently employed for selecting and/or tuning ILs. These methods are probabilistic, time consuming, expensive and may not result in selecting high performance ILs for gas hydrate mitigation. In this work, COSMO-RS is considered as a prescreening tool of ILs for gas hydrate mitigation by predicting the hydrogen bonding energies(E_(HB)) of studied IL inhibitors and comparing the predicted E_(HB) to the depression temperature(?) and induction time. Results show that, predicted EHBand chain length of ILs strongly relate and significantly affect the gas hydrate inhibition depression temperature but correlate moderately(R = 0.70) with average induction time in literature. It is deduced from the results that, ? increases with increasing IL EHBand/or decreases with increasing chain length. However, the cation–anion pairing of ILs also affects IL gas hydrate inhibition performance. Furthermore, a visual and better understanding of IL/water behavior for gas hydrate inhibition in terms of hydrogen bond donor and acceptor interaction analysis is also presented by determining the sigma profile and sigma potential of studied IL cations and anions used for gas hydrate mitigation for easy IL selection.     

Separation of alkanes and alcohols with supercritical fluids. Part I: Phase equilibria and viability study

The chemical conversion of detergent range alkanes (12-14 carbon atoms) to alcohols is often incomplete and results in a large amount of residual alkane. This paper shows that these alkanes and alcohols can be separated by supercritical fluids. Ethane, propane and carbon dioxide were selected as possible supercritical solvents while n-tetradecane and 1-dodecanol were selected to represent the alkane-alcohol mixture, as these would be the two most difficult compounds to separate in a C12 to C14 alkane-alcohol mixture. A phase behaviour study and relative solubility analysis revealed that both ethane and carbon dioxide show promise in separating n-tetradecane and 1-dodecanol. Propane was eliminated as possible solvent because the phase behaviour of n-tetradecane and 1-dodecanol in supercritical propane is too similar. A pilot plant study showed that both supercritical ethane and carbon dioxide can be used to separate n-tetradecane and 1-dodecanol, with indications that supercritical ethane may affect a superior separation. An economic analysis, considering the energy requirements, revealed that the most important parameter with regard to energy consumption is the solvent-to-feed ratio. The process utilising ethane is more energy intensive, yet the energy requirements for both processes compare well with other petrochemical separation processes using supercritical fluids. Further investigations with both ethane and carbon dioxide should be conducted to determine which of these two solvents are superior and to optimise the operating parameters.     

Numerical simulation and validation of gas-particle rectangular jets in crossflow

This paper presents a numerical study of a gas-particle flow in three inclined rectangular jets in crossflow. The predicted gas phase velocities and particle phase velocities are validated against previously reported experimental data. Two turbulence models, the standard k-? model and Shear Stress Transfer (SST) model, are used to model the gas phase turbulence. This work shows that both models provide acceptable predictions of the gas flow and mixing generated by the three jets. Neither model could accurately reproduce the jet core and the flow near bottom wall. The particle phase in this flow comprises a large number of small particles. Thus particles follow the gas phase flow closely and any errors in the turbulence model and gas flow predictions are passed on to the particle phase simulation. This paper also includes a literature review on rectangular jets in crossflow and gas-particle laden jets in crossflow.     

The Role of Oxygen Storage in NO Conversion in Automotive Catalysts

An asymmetry in NO conversion efficiency is apparent during trans-stoichiometric air–fuel ratio steps over a three-way catalyst. After a lean-to-rich step, NO conversion becomes high very rapidly and asymptotes to a higher value, followed by a reduction to a high, but reduced level. Following a rich-to-lean step, conversion remains high for a period before gradually decreasing to the low level seen at steady lean operation. This dynamic response in NO conversion can be modelled by a three-way catalyst model which includes ceria reoxidation by way of NO dissociative adsorption. Five, periodic, different aspect triangular waveforms were tested to try to exploit the asymmetry by waveform shaping. No strong trends in average NO conversion efficiency resulted; however, some shapes seemed to give a better overall conversion.