A thermodynamically consistent kinetic framework for binary nucleation

The traditional theory for binary homogeneous nucleation follows the classical derivation of the nucleation rate in the supposition of a hypothetical constrained-equilibrium distribution in the calculation of the cluster evaporation rate. This model enables calculation of the nucleation rate, but requires evaluation of the cluster distribution and cluster properties for an unstable equilibrium with supersaturated vapor. An alternate derivation of the classical homomolecular nucleation rate eliminated the need for this nonphysical approximation by calculating the evaporative flux at full thermodynamic equilibrium. The present paper develops that approach for binary nucleation; the framework is readily extended to ternary nucleation. In this analysis, the evaporative flux is evaluated by applying mass balance at full thermodynamic equilibrium of the system under study. This approach eliminates both the need for evaluating cluster properties in an unstable constrained-equilibrium state and ambiguity in the normalization constant required in the nucleation-rate expression. Moreover, it naturally spans the entire composition range between the two pure monomers. The cluster fluxes derived using this new model are similar in form to those of classical derivations, so previously developed methods for evaluation of the net nucleation rate can be applied directly to the new formulation

Particulate emissions from energy systems

General models of aerosol dynamics, originally developed to simulate atmospheric aerosol behavior, have been extended for application to combustion and other high temperature processes. These models are now being used to study the fate of ash vapors in conventional pulverized-coal combustion. Field measurements have shown that the vapors condense preferentially on the surfaces of the smaller ash particles. Previous simplified calculations have suggested that large numbers of very small particles may also be formed by the condensation of these vapors. The new, exact calculations will be used to explore the relative importance of new particle formation and condensation on existing particles, the size distributions of the particles produced under various combustion conditions, and the distribution of chemical composition with respect to particle size

Excitation Mechanisms of the Nitrogen First‐Positive and First‐Negative Radiation at High Temperature

The kinetic mechanisms responsible for the excitation of the first-positive and first-negative emission of nitrogen have been investigated in a re-examination of previously reported shock-tube measurements of the nonequilibrium radiation for these systems. The rate coefficients of the collisional quenching reactions, N_2(A^(3)Σ^(+)_u)(^(k^(N)_(-2))⇒) N_2(X^(1)Σ^(+)_g) + N(^(4)S) and N^(+)_2(B^(2)Σ^(+)_u) + N_2(X^(1)Σ^(+)_g)(^(k^(N)_(q))⇒) N^(+)_2(X^(2)Σ^(+)_g) or N^(+)_2(A(^(2)II_u)+N_2(X^(1)Σ^(+)_g) were found to be given by the empirical expressions, k_(2^(N))=5.1x10^(-3)T^(-2.23) cm^3 sec^(-1) and k_(q^(N_2))=1.9x10^(-2)T^(-2.33)cm^3 sec^(-1), respectively, over the approximate temperature range 6000-14 000°K

Scale-up of electrospray atomization using linear arrays of Taylor cones

Linear arrays of Taylor cones were established on capillary electrode tubes opposite a slotted flat plate counterelectrode to investigate the feasibility of increasing the liquid throughput rate in electrospray atomizers. It was found that individual Taylor cones could be established on each capillary over a wide range of the capillary radius to spacing ratio R/S. The onset potential Vs required to establish the cones varied directly with R/S, but the liquid flow rate per cone and current per cone were nearly independent of R/S for a given overpotential ratio P=V/Vs. Only six working capillaries were used, but the results per cone are applicable to larger arrays of cones since end effects were minimized

A stochastic model of turbulent mixing with chemical reaction: Nitric oxide formulation in a plug-flow burner

A stochastic model of turbulent mixing was developed for a reactor in which mixing is represented by n-body fluid particle interactions. The model was used to justify the assumption (made in previous investigations of the role of turbulent mixing on burner generated thermal nitric oxide and carbon monoxide emissions) that for a simple plug flow reactor, composition nonuniformities can be described by a Gaussian distribution function in the local fuel:air equivalence ratio. Recent extensions of this stochastic model to include the combined effects of turbulent mixing and secondary air entrainment on thermal generation of nitric oxide in gas turbine combustors are discussed. Finally, rate limited upper and lower bounds of the nitric oxide produced by thermal fixation of molecular nitrogen and oxidation of organically bound fuel nitrogen are estimated on the basis of the stochastic model for a plug flow burner; these are compared with experimental measurements obtained using a laboratory burner operated over a wide range of test conditions; good agreement is obtained

Scholars Forum: A New Model For Scholarly Communication

Scholarly journals have flourished for over 300 years because they successfully address a broad range of authors' needs: to communicate findings to colleagues, to establish precedence of their work, to gain validation through peer review, to establish their reputation, to know the final version of their work is secure, and to know their work will be accessible by future scholars. Eventually, the development of comprehensive paper and then electronic indexes allowed past work to be readily identified and cited. Just as postal service made it possible to share scholarly work regularly and among a broad readership, the Internet now provides a distribution channel with the power to reduce publication time and to expand traditional print formats by supporting multi-media options and threaded discourse. Despite widespread acceptance of the web by the academic and research community, the incorporation of advanced network technology into a new paradigm for scholarly communication by the publishers of print journals has not materialized. Nor have journal publishers used the lower cost of distribution on the web to make online versions of journals available at lower prices than print versions. It is becoming increasingly clear to the scholarly community that we must envision and develop for ourselves a new, affordable model for disseminating and preserving results, that synthesizes digital technology and the ongoing needs of scholars. In March 1997, with support from the Engineering Information Foundation, Caltech sponsored a Conference on Scholarly Communication to open a dialogue around key issues and to consider the feasibility of alternative undertakings. A general consensus emerged recognizing that the certification of scholarly articles through peer review could be "decoupled" from the rest of the publishing process, and that the peer review process is already supported by the universities whose faculty serve as editors, members of editorial boards, and referees. In the meantime, pressure to enact regressive copyright legislation has added another important element. The ease with which electronic files may be copied and forwarded has encouraged publishers and other owners of copyrighted material to seek means for denying access to anything they own in digital form to all but active subscribers or licensees. Furthermore, should publishers retain the only version of a publication in a digital form, there is a significant risk that this material may eventually be lost through culling little-used or unprofitable back-files, through not investing in conversion expense as technology evolves, through changes in ownership, or through catastrophic physical events. Such a scenario presents an intolerable threat to the future of scholarship

Particle sizing in the electrodynamic balance

We report a new technique for sizing particles in the electrodynamic balance. In this technique, the trajectory of a falling particle is followed with a photomultiplier tube. Particle velocities are measured by placing a mask between the particle and the detector. The masked region in the particle trajectory is roughly 0.6 mm wide. Output from the PMT is sampled every millisecond by an A/D converter and stored in a computer. Flight times of several hundred milliseconds are measured and the size is then computed from the particle's terminal velocity. With a modification of the mask, the technique is used to verify the uniformity of the electric field through which the particle is falling. In the present work we use the technique to determine size of polystryrene latex microspheres having nominal diameters of 10 and 20 µ. The technique can be used on any size particle, independent of its charge-to-mass ratio, and provides the size information in a short time

Elemental analysis of chamber organic aerosol using an Aerodyne high-resolution aerosol mass spectrometer

The elemental composition of laboratory chamber secondary organic aerosol (SOA) from glyoxal uptake, α-pinene ozonolysis, isoprene photooxidation, single-ring aromatic photooxidation, and naphthalene photooxidation is evaluated using Aerodyne high-resolution time-of-flight mass spectrometer data. SOA O/C ratios range from 1.13 for glyoxal uptake experiments to 0.30–0.43 for α-pinene ozonolysis. The elemental composition of α-pinene and naphthalene SOA is also confirmed by offline mass spectrometry. The fraction of organic signal at m/z 44 is generally a good measure of SOA oxygenation for α-pinene/O3, isoprene/high-NO_x, and naphthalene SOA systems. The agreement between measured and estimated O/C ratios tends to get closer as the fraction of organic signal at m/z 44 increases. This is in contrast to the glyoxal uptake system, in which m/z 44 substantially underpredicts O/C. Although chamber SOA has generally been considered less oxygenated than ambient SOA, single-ring aromatic- and naphthalene-derived SOA can reach O/C ratios upward of 0.7, well within the range of ambient PMF component OOA, though still not as high as some ambient measurements. The spectra of aromatic and isoprene-high-NO_x SOA resemble that of OOA, but the spectrum of glyoxal uptake does not resemble that of any ambient organic aerosol PMF component

Silicon production in an aerosol reactor

An aerosol reactor system was developed in which large particles of silicon can be grown by silane pyrolysis. To grow particles to sizes larger than one micron, vapor deposition must be used to grow a relatively small number of seed particles. Suppression of nucleation is achieved by limiting the rate of gas phase chemical reactions such that the condensible products of the gas phase chemical reactions diffuse to the surface of the seed particles as rapidly as they are produced. This prevents high degrees of supersaturation and runaway nucleation during the growth process. Particles on the order of 10 microns were grown repeatedly with the present aersol reactor. The nucleation controlled aerosol reactor is, therefore, a suitable system for the production of powders that can readily be separated from the gas by aerodynamic means