Crossover dynamics at large metastability in gas-liquid nucleation

We have developed an alternate description of dynamics of nucleation in terms of an extended set of order parameters. The order parameters consist of an ordered set of kth largest clusters, ordered such that k = 1 is the largest cluster in the system, k = 2 is the second largest cluster, and so on. We have derived an analytic expression for the free energy for the kth largest cluster, which is in excellent agreement with the simulated results. At large supersaturation, the free energy barrier for the growth of the kth largest cluster disappears and the nucleation becomes barrierless. The major success of this extended theoretical formalism is that it can clearly explain the observed change in mechanism at large metastability P. Bhimalapuram et al., Phys. Rev. Lett. 98, 206104 (2007)] and the associated dynamical crossover. The classical nucleation theory cannot explain this crossover. The crossover from activated to barrierless nucleation is found to occur at a supersaturation where multiple clusters cross the critical size. We attribute the crossover as the onset of the kinetic spinodal. We have derived an expression for the rate of nucleation in the barrierless regime by modeling growth as diffusion on the free energy surface of the largest cluster. The model reproduces the slower increase in the rate of growth as a function of supersaturation, as observed in experiments.

Reaction of normal and pseudo 2-formylbenzenesulfonyl chlorides with amines:experimental and theoretical studies on the structure of 2-formyl benzenesulfonamides in solid, solution and gas phases

The reaction of 2-formylbenzenesulfonyl chloride 1 and its pseudo isomer 2 with primary amines give either the corresponding sulfonamido Schiff bases or the corresponding 2-formylbenzenesulfonamide depending on the concentration of the amine used. The derivatives exist as an equilibrium mixture of the corresponding sulfonamide and 2-alkyl-3-hydroxy(or 3-aminoalkyl)-benzisothiazole-1,1-dioxide. Spectroscopic studies suggest that 2-formylbenzenesulfonamides exist as benzisothiazole-1,1-dioxides in the solid state, as a mixture of 2-formylbenzenesulfonamide and the corresponding benzisothiazole-1,1-dioxide in solution and as 2-formyl-benzenesulfonamides in the gas phase.

Thermal degradation products of poly(styrenesulfides) investigated by direct pyrolysis�mass spectrometry and flash pyrolysis�gas chromatography/mass spectrometry

The thermal degradation products of two sulfur polymers, poly(styrenedisulfide) (PSD) and poly(styrenetetrasulfide) (PST), were investigated in parallel by direct pyrolysis-mass spectrometry (DPMS) and by flash pyrolysis-GC/MS (Py-GC/MS). The time-scale of the two pyrolysis techniques is quite different, and therefore they were able to detect significantly different products in the pyrolysis of PSD and PST because of the thermal lability of sulfur-containing compounds. However, the results obtained are not contradictory, and satisfactory mechanisms for the thermal degradation of PSD and PST have been derived from the overall evidence available. Pyrolysis compounds containing sulfur, styrene, and a number of cyclic styrene sulfides and diphenyldithianes have been observed by DPMS. However, in flash pyrolysis-GC/MS, styrene, sulfur, only one cyclic styrene sulfide, and two isomers of diphenylthiophene have been detected. These thiophene derivatives were indeed absent among the compounds obtained by DPMS because they were the terminal (most thermally stable) species arising from further decomposition of the cyclic styrene sulfides formed in the primary thermal degradation processes of PSD and PST.

A thermodynamic criterion for selection of gas compositions for diamond deposition

Isoactivity lines for carbon with respect to diamond as the standard state have been calculated in the ternary system C-H-O at 1223 K to identify the diamond deposition domain. The gas composition is calculated by suppressing the formation of all condensed forms of carbon using the SOLGASMIX free-energy minimization program. Thirty six gas species were included in the calculation. From the gas composition, isoactivity lines are computed using recent data on the Gibbs energy of diamond. Except for activities less than 0.1, the isoactivity lines are almost linear on the C-H-O ternary diagram. Gas compositions which generate activity of diamond ranging from 1 to 100 at 1223 K fall inside a narrow wedge originating from the point representing CO. This wedge is very similar to the revised lens-shaped diamond growth domain identified by Bachman et al., using inputs from experiment. The small difference between the calculated and observed domains may be attributed to variation in the supersaturation required for diamond deposition with gas composition. The diamond solubility in the gas phase along the isoactivity line for a(di)=100 and P=6.7 kPa exhibits a minimum at 1280 K, which is close to the optimum temperature found experimentally. At higher supersaturations, non-diamond forms of carbon, including amorphous varieties, are expected. The results suggest that thermodynamic calculations can be useful for locating diamond growth domains in more complex CVD systems containing halogens, for which very little experimental data is available.

Gas-liquid nucleation at large metastability: unusual features and a new formalism

Nucleation at large metastability is still largely an unsolved problem, even though it is a problem of tremendous current interest, with wide-ranging practical value, from atmospheric research to materials science. It is now well accepted that the classical nucleation theory (CNT) fails to provide a qualitative picture and gives incorrect quantitative values for such quantities as activation-free energy barrier and supersaturation dependence of nucleation rate, especially at large metastability. In this paper, we present an alternative formalism to treat nucleation at large supersaturation by introducing an extended set of order parameters in terms of the kth largest liquid-like clusters, where k = 1 is the largest cluster in the system, k = 2 is the second largest cluster and so on. At low supersaturation, the size of the largest liquid-like cluster acts as a suitable order parameter. At large supersaturation, the free energy barrier for the largest liquid-like cluster disappears. We identify this supersaturation as the one at the onset of kinetic spinodal. The kinetic spinodal is system-size-dependent. Beyond kinetic spinodal many clusters grow simultaneously and competitively and hence the nucleation and growth become collective. In order to describe collective growth, we need to consider the full set of order parameters. We derive an analytic expression for the free energy of formation of the kth largest cluster. The expression predicts that, at large metastability (beyond kinetic spinodal), the barrier of growth for several largest liquid-like clusters disappears, and all these clusters grow simultaneously. The approach to the critical size occurs by barrierless diffusion in the cluster size space. The expression for the rate of barrier crossing predicts weaker supersaturation dependence than what is predicted by CNT at large metastability. Such a crossover behavior has indeed been observed in recent experiments (but eluded an explanation till now). In order to understand the large numerical discrepancy between simulation predictions and experimental results, we carried out a study of the dependence on the range of intermolecular interactions of both the surface tension of an equilibrium planar gas-liquid interface and the free energy barrier of nucleation. Both are found to depend significantly on the range of interaction for the Lennard-Jones potential, both in two and three dimensions. The value of surface tension and also the free energy difference between the gas and the liquid phase increase significantly and converge only when the range of interaction is extended beyond 6-7 molecular diameters. We find, with the full range of interaction potential, that the surface tension shows only a weak dependence on supersaturation, so the reason for the breakdown of CNT (with simulated values of surface tension and free energy gap) cannot be attributed to the supersaturation dependence of surface tension. This remains an unsettled issue at present because of the use of the value of surface tension obtained at coexistence.

Nitrogen Derivatives Of C-60 And C-70 - Interaction Of Fullerenes With Nitrogen In Gas-Phase

Mass spectrometric studies show that contact-arc vaporization of graphite in a partial atmosphere of N2 or NH3 yields nitrogenous products tentatively assigned to species such as C70N2, C59N6, C59N4 and C59N2 involving addition of or substitution by nitrogen along with the species due to C2 and C4 losses. Mass spectrometry and other techniques have been employed to identify products of the nucleophilic addition of aliphatic amines to C60 and C70 in solution phase.

Multi frequency interrogation of polypyrrole based gas sensors for organic vapors

Polypyrrole exhibits reversible changes in their direct current resistance on exposure to organic volatiles. However, one needs to employ an array of such sensors to discriminate organic volatiles present in a mixture. Hence, polypyrrole based gas sensor is designed for the detection and discrimination of different organic volatiles. Multi frequency impedance measurement technique is used to detect the organic vapors, such as acetone, ethanol and Isopropyl alcohol, in the gas phase, over a frequency range 10 Hz to 2 MHz. The sensor response is monitored by measuring the changes in its capacitance, resistance and the dissipation factor upon exposure to organic volatiles. It is observed that the capacitive property of the sensor is more sensitive to these volatiles than its resistive property. Each volatile responds to the sensor in terms of dissipation factor at specific frequency and found that the peak magnitude has a linear relationship with their concentrations.

Design of solid electrolytes for use with dissimilar gas electrodes

The design of a solid electrolyte that permits the use of dissimilar gas electrodes in an electrochemical cell is presented. It consists of a functionally gradient material with spatial variation in composition. The activity of the conducting ion is fixed at each electrode using different gas species. The system chosen for demonstrating the concept consists of a solid solution between K2CO3 and K2SO4. The composition of the solid solution varies from pure K2CO3 in contact with a CO2 + O2 gas mixture at one electrode to pure K2SO4 exposed to a mixture of SO3 + SO2 + O2 at the other. Two types of composition profiles are studied, one with monotonic variation in composition and the other with extrema. The e.m.f. of the cells is studied as a function of temperature and composition of the gas mixture at each electrode. The results indicate that the e.m.f. is determined primarily by the difference in the chemical potential of potassium at the two electrodes. The diffusion potential caused by ionic concentration gradients in the electrolyte appears to be negligible when the corresponding ionic transport numbers are insignificant. Studies on the response characteristics of the cell based on the gradient electrolyte indicate that the nature of the variation in composition of the electrolyte has only a minor effect on the time evolution of e.m.f. The gradient solid electrolytes have potential application in multielement galvanic sensors at high temperatures.

Swing amplification of nonaxisymmetric perturbations in stars and gas in a sheared galactic disk

We present a study of the growth of local, nonaxisymmetric perturbations in gravitationally coupled stars and gas in a differentially rotating galactic disk. The stars and gas are treated as two isothermal fluids of different velocity dispersions, with the stellar velocity dispersion being greater than that for the gas. We examine the physical effects of inclusion of a low-velocity dispersion component (gas) on the growth of non-axisymmetric perturbations in both stars and gas, as done for the axisymmetric case by Jog & Solomon. The amplified perturbations in stars and gas constitute trailing, material, spiral features which may be identified with the local spiral features seen in all spiral galaxies. The formulation of the two-fluid equations closely follows the one-fluid treatment by Goldreich & Lynden-Bell. The local, linearized perturbation equations in the sheared frame are solved to obtain the results for a temporary growth via swing amplification. The problem is formulated in terms of five dimensionless parameters-namely, the Q-factors for stars and gas, respectively; the gas mass fraction; the shearing rate in the galactic disk; and the length scale of perturbation. By using the observed values of these parameters, we obtain the amplifications and the pitch angles for features in stars and gas for dynamically distinct cases, as applicable for different regions of spiral galaxies. A real galaxy consisting of stars and gas may display growth of nonaxisymmetric perturbations even when it is stable against axisymmetric perturbations and/or when either fluid by itself is stable against non-axisymmetric perturbations. Due to its lower velocity dispersion, the gas exhibits a higher amplification than do the stars, and the amplified gas features are slightly more tightly wound than the stellar features. When the gas contribution is high, the stellar amplification and the range of pitch angles over which it can occur are both increased, due to the gravitational coupling between the two fluids. Thus, the two-fluid scheme can explain the origin of the broad spiral arms in the underlying old stellar populations of galaxies, as observed by Schweizer and Elmegreen & Elmegreen. The arms are predicted to be broader in gas-rich galaxies, as is indeed seen for example in M33. In the linear regime studied here, the arm contrast is shown to increase with radius in the inner Galaxy, in agreement with observations of external galaxies by Schweizer. These results follow directly due to the inclusion of gas in the problem.

Three- and Seven-Point Optimally Weighted Recursive Median Filters for Gas Turbine Diagnostics

Measured health signals incorporate significant details about any malfunction in a gas turbine. The attenuation of noise and removal of outliers from these health signals while preserving important features is an important problem in gas turbine diagnostics. The measured health signals are a time series of sensor measurements such as the low rotor speed, high rotor speed, fuel flow, and exhaust gas temperature in a gas turbine. In this article, a comparative study is done by varying the window length of acausal and unsymmetrical weighted recursive median filters and numerical results for error minimization are obtained. It is found that optimal filters exist, which can be used for engines where data are available slowly (three-point filter) and rapidly (seven-point filter). These smoothing filters are proposed as preprocessors of measurement delta signals before subjecting them to fault detection and isolation algorithms.

Gas-phase controlled mass transfer in a foam-bed reactor

Gas-phase controlled absorption of ammonia in foams made of solutions of sulphuric acid has been studied experimentally. Effects of gas-phase concentration of ammonia and type of surfactant on the performance of the foam-bed reactor are investigated. Gas-phase controlled absorption from a spherical bubble is anaylzed using the asymptotic value of Sherwood number (Sh = 6.58), for both negligible as well as significant changes in the volume of the bubble. The experimental data are shown to be in good agreement with the single-stage model of the foam-bed reactor using these asymptotic sub-models, as well as the diffusion-in-sphere analysis available in literature. Influence of effective diffusivity on the time dependence of fractional gas absorption has been found to be unimportant for foam columns with large times of contact. The asymptotic sub-models have been compared and use of the rigid-sphere asymptotic sub-model is recommended for foam columns of practical relevence.

Nonaxisymmetric convection in stationary Gas Tungsten Arc Weld Pools

Observations of surface flow patterns of steel and aluminum GTAW pools have been made using a pulsed laser visualization system. The weld pool convection is found to be three-dimensional with the azimuthal circulation depending on the location of the clamp with respect to the torch. Oscillation of steel pools and undulating motion in aluminum weld pools are also observed even with steady process parameters. Current axisymmetric numerical models are unable to explain such phenomena. A three-dimensional computational study is carried out in this study to explain the rotational flow in aluminum weld pools.

The 2D Coulomb gas on a 1D lattice

The statistical mechanics of a two-dimensional Coulomb gas confined to one dimension is studied, wherein hard core particles move on a ring. Exact self-duality is shown for a version of the sine-Gordon model arising in this context, thereby locating the transition temperature exactly. We present asymptotically exact results for the correlations in the model and characterize the low- and high-temperature phases. Numerical simulations provide support to these renormalization group calculations. Connections with other interesting problems, such as the quantum Brownian motion of a panicle in a periodic potential and impurity problems, are pointed out.

Tidally compressed gas in centers of early-type and ultraluminous galaxies

In this paper we propose that the compressive tidal held in the centers of flat-core early-type galaxies and ultraluminous galaxies compresses molecular clouds producing dense gas observed in the centers of these galaxies. The effect of galactic tidal fields is usually considered disruptive in the literature. However, for some galaxies, the mass profile flattens toward the center and the resulting galactic tidal field is not disruptive, but instead it is compressive within the flat-core region. We have used the virial theorem to determine the minimum density of a molecular cloud to be stable and gravitationally bound within the tidally compressive region of a galaxy. We have applied the mechanism to determine the mean molecular cloud densities in the centers of a sample of flat-core, early-type galaxies and ultraluminous galaxies. For early-type galaxies with a core-type luminosity profile, the tidal held of the galaxy is compressive within half the core radius. We have calculated the mean gas densities for molecular gas in a sample of early-type galaxies which have already been detected in CO emission, and we obtain mean densities of [n] similar to 10(3)-10(6) cm(-3) within the central 100 pc radius. We also use our model to calculate the molecular cloud densities in the inner few hundred parsecs of a sample of ultraluminous galaxies. From the observed rotation curves of these galaxies we show that they have a compressive core within their nuclear region. Our model predicts minimum molecular gas densities in the range 10(2)-10(4) cm(-3) in the nuclear gas disks; the smaller values are applicable typically for galaxies with larger core radii. The resulting density values agree well with the observed range. Also, for large core radii, even fairly low-density gas (similar to 10(2) cm(-3)) can remain bound and stable close to the galactic center.