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

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

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

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

Inward electrostatic precipitation of interplanetary particles

An inward precipitator collects particles initially dispersed in a gas throughout either a cylindrical or spherical chamber onto a small central planchet. The instrument is effective for particle diameters greater than about 1 µm. One use is the collection of interplanetary dust particles which are stopped in a noble gas (xenon) by drag and ablation after perforating the wall of a thin-walled spacecraft-mounted chamber. First, the particles are positively charged for several seconds by the corona production of positive xenon ions from inward facing needles placed on the chamber wall. Then an electric field causes the particles to migrate toward the center of the instrument and onto the planchet. The collection time (of the order of hours for a 1 m radius spherical chamber) is greatly reduced by the use of optimally located screens which reapportion the electric field. Some of the electric field lines terminate on the wires of the screens so a fraction of the total number of particles in the chamber is lost. The operation of the instrument is demonstrated by experiments which show the migration of carbon soot particles with radius of approximately 1 µm in a 5-cm-diam cylindrical chamber with a single field enhancing screen toward a 3.2 mm central collection rod

Single-particle levitation system for automated study of homogeneous solute nucleation

We present an instrument that addresses two critical requirements for quantitative measurements of the homogeneous crystal nucleation rate in supersaturated aqueous solution. First, the need to perform repeated measurements of nucleation incubation times is met by automating experiments to enable programmable cycling of thermodynamic conditions. Second, the need for precise and robust control of the chemical potential in supersaturated aqueous solution is met by implementing a novel technique for regulating relative humidity. The apparatus levitates and weighs micron-sized samples in an electric field, providing access to highly supersaturated states. We report repeated observations of the crystal nucleation incubation time in a supersaturated aqueous sodium chloride droplet, from which we infer the nucleation rate

Thermodynamic properties and homogeneous nucleation rates for surface-melted physical clusters

We predict the free energy of van der Waals clusters (Fn) in the surface-melted temperature regime. These free energies are used to predict the bulk chemical potential, surface tension, Tolman length, and vapor pressure of noble gas crystals. Together, these estimates allow us to make definitive tests of the capillarity approximation in classical homogeneous nucleation theory. We find that the capillarity approximation underestimates the nucleation rate by thirty orders of magnitude for argon. The best available experiments are consistent with our calculation of nucleation rate as a function of temperature and pressure. We suggest experimental conditions appropriate for determining quantitative nucleation rates which would be invaluable in guiding further development of the theory. To make the predictions of Fn, we develop the Shellwise Lattice Search (SLS) algorithm to identify isomer fragments and the Linear Group Contribution (LGC) method to estimate the energy of isomers composed of those fragments. Together, SLS/LGC approximates the distribution of isomers which contribute to the configurational partition function (for up to 147-atom clusters). Estimates of the remaining free energy contributions come from a previous paper in this series

Binary nucleation in acid–water systems. I. Methanesulfonic acid–water

Experimental measurements of binary nucleation between methanesulfonic acid and water vapor were carried out for relative acidities (Ra), 0.05<Ra<0.65, and relative humidities (Rh), 0.06<Rh<0.65, using a continuous flow mixing-type device. The number concentration of particles leaving the nucleation and growth tube was measured as a function of the initial relative humidity and the relative acidity in the temperature range from 20 to 30 °C. Particle size distributions were also measured and found to vary with the amount of water and acid present. The system was simulated to predict the total number of particles and the total mass of acid in the aerosol phase using a simple integral model and classical binary nucleation theory allowing for the formation of acid–water hydrates in the gas phase. At low particle concentrations, condensation rates did not significantly change the saturation levels and the nucleation rates were estimated from the total number concentration data as functions of Ra, Rh, and temperature. The values of experimental and theoretical nucleation rates differed significantly, with Jexpt/Jtheor changing as a function of temperature from 10^–8 to 10^–4 as temperature varied from 20 to 30 °C. This work represents the first systematic experimental study of the temperature dependence of binary nucleation