Methanol nucleation in a supersonic nozzle

We determined the partial pressures p(Jmax), temperatures T(Jmax), monomer supersaturations S(Jmax), and characteristic times Δt(Jmax?) corresponding to the maximum nucleation rates of methanol in a supersonic nozzle. We found that T(Jmax) increased from 202.2 K to 223.7 K as p(Jmax) increased from 67.1 to 413.2 Pa, while the maximum nucleation rate J(max) changed by less than a factor of 4 over the measurement range. Our nucleation rates appear reasonably consistent with measurements in other devices and are within one order of magnitude of the nucleation rates predicted by classical nucleation theory.     

Homogeneous nucleation of n-propanol, n-butanol, and n-pentanol in a supersonic nozzle

We have measured the nucleation conditions of n-propanol, n-butanol, and n-pentanol in a supersonic Laval nozzle, and estimated that the maximum nucleation rate J is 5 x 10(16) cm(-3) s(-1) with an uncertainty factor of 2. Plotting the vapor pressures p(J(max) ) and temperatures T(J(max) ) corresponding to the maximum nucleation rate as ln(p) versus 1T, produces a series of well separated straight lines. When these values are scaled by their respective critical parameters, p(c) and T(c), the data lie close to a single straight line. Comparing the experimental data to the predictions of classical nucleation theory reveals much higher experimental rates, and the deviation increases with increasing alcohol chain length and decreasing temperature. A scaling analysis in terms of Hale's scaled nucleation model [Phys. Rev. A 33, 4156 (1986); Metall. Trans. A 23, 1863 (1992)], clearly shows that our data are consistent with experimental nucleation rates measured using other devices that have characteristic rates many orders of magnitude lower.     

Argon nucleation in a cryogenic nucleation pulse chamber

Homogeneous nucleation of argon droplets has been measured with a newly designed cryogenic nucleation pulse chamber presented already in a previous paper [Fladerer and Strey, J. Chem. Phys. 124, 16 (2006)]. Here we present the first systematic nucleation onset data for argon measured in a temperature range from 42 to 58 K and for vapor pressures from 0.3 to 10 kPa. For these data we provide an analytical fit function. From the geometry of the optical detection system and the time of nucleation the experimental nucleation-rate range can be estimated. This allows a comparison of the data with the predictions of classical nucleation theory. We found 16-26 orders of magnitude difference between theory and experiment, and a too strong theoretical dependence of the nucleation rate on temperature. A comparison with the self-consistent theory of Girshick and Chiu [J. Chem. Phys. 93, 1273 (1990)] showed improved temperature dependence but still discrepancies of 11-17 orders of magnitude compared to experimental data. The thermodynamically consistent theory of Kashchiev [J. Chem. Phys. 118, 1837 (2003)] was found to agree rather well with experiment in respect to the temperature dependence and to predict rates about 5-7 orders of magnitude below the experimental ones. With the help of the Gibbs-Thomson equation we were able to evaluate the size of the critical nucleus to be 40-80 argon atoms.     

Binary nucleation rates for ethanol/water mixtures in supersonic Laval nozzles

Although the conditions corresponding to the onset of condensation of aqueous-alcohol mixtures have been measured in supersonic nozzles [B. E. Wyslouzil et al., J. Chem. Phys. 113, 7317 (2000)], the true nucleation rates have not. Here, we propose a new analytical method to estimate the temperature, the concentrations of condensable species in both the vapor and the liquid phases, and the amount of the condensate using only the measured static pressure profiles in the nozzle. We applied the method to ethanol/water (CH(3)CH(2)OH/D(2)O or CH(3)CH(2)OD/D(2)O) mixtures and confirmed that the aerosol volume fractions derived from pressure measurements and small angle neutron scattering measurements are in very good agreement when this method is used. Combining the results from the pressure measurements with the number densities of the condensed droplets, measured either by small angle neutron or small angle x-ray scattering, we determined the first quantitative ethanol/water binary nucleation rates in the supersonic nozzle at a temperature of 229±1?K.     

Ionization of NO2 clusters in a supersonic nozzle beam: appearance of the odd-number cluster ions of NO2

Cluster ions (NO₂)⁺_n, n = 2−13, were detected mass spectrometrically in a supersonic nozzle beam by both photon- and electron-impact ionization. The odd-number cluster ions (NO₂)⁺_2m+1 appeared dominantly over the even-number cluster ions (NO₂)⁺_2m. The results are consistently explained by the dissociative ionization of the (sym-N₂O₄)_n clusters and ionization (involving intra-cluster charge transfer) of the (sym-N₂O₄)_nNO₂ clusters produced via supersonic expansion of NO₂: (sym-N₂O₄)₂ + hν → (sym-N₂O₄)_n–1NO⁺₂ + NO₂ + e⁻ and (sym-N₂O₄)_nNO₂ + hν → (sym-N₂O₄)_nNO⁺₂ + e⁻.     

Development of high-temperature pulsed slit nozzle and its application to supersonic jet absorption spectrometry

A high-temperature pulsed slit nozzle, consisting of a circular pulsed nozzle and an interface to convert a circular flow into a slit flow has been constructed. The absorption spectrum is measured by scanning the wavelength of the monochromator equipped with a xenon arc lamp and by detecting the transmitted light through a jet with a photomultiplier. A rotationally cooled spectrum is clearly observed for aniline only when a long slit nozzle is employed. The absorptivity increases proportionally to the slit length at least up to 6 cm. The time for recording a spectrum is 3.5 min, which is reduced to several seconds by transmitting a white light through a jet and by measuring the spectrum with an optical multichannel analyzer. The detection limit is estimated to a partial vapor pressure of 0.4 torr for aniline. The present system can be conveniently used in routine analysis, because of a wide spectral coverage of the lamp source.     

Simulation of homogeneous condensation of small polyatomic systems in high pressure supersonic nozzle flows using Bhatnagar-Gross-Krook model

In the present work, we have simulated the homogeneous condensation of carbon dioxide and ethanol using the Bhatnagar-Gross-Krook based approach. In an earlier work of Gallagher-Rogers et al. [J. Thermophys. Heat Transfer 22, 695 (2008)], it was found that it was not possible to simulate condensation experiments of Wegener et al. [Phys. Fluids 15, 1869 (1972)] using the direct simulation Monte Carlo method. Therefore, in this work, we have used the statistical Bhatnagar-Gross-Krook approach, which was found to be numerically more efficient than direct simulation Monte Carlo method in our previous studies [Kumar et al., AIAA J. 48, 1531 (2010)], to model homogeneous condensation of two small polyatomic systems, carbon dioxide and ethanol. A new weighting scheme is developed in the Bhatnagar-Gross-Krook framework to reduce the computational load associated with the study of homogeneous condensation flows. The solutions obtained by the use of the new scheme are compared with those obtained by the baseline Bhatnagar-Gross-Krook condensation model (without the species weighting scheme) for the condensing flow of carbon dioxide in the stagnation pressure range of 1-5 bars. Use of the new weighting scheme in the present work makes the simulation of homogeneous condensation of ethanol possible. We obtain good agreement between our simulated predictions for homogeneous condensation of ethanol and experiments in terms of the point of condensation onset and the distribution of mass fraction of ethanol condensed along the nozzle centerline.     

Benzene clusters in a supersonic beam

A supersonic beam is employed to produce benzene clusters (C₆H₆) _n up ton=40. Mass analysis is achieved after two-photon ionization in a reflectron mass spectrometer. Photon energy is chosen so that the internal energy of the cluster ions is less than 700 meV and a slow decay on the µs time scale is observed. By an energy analysis with the reflecting field it is found that the elimination of one neutral benzene monomer is the favoured dissociation process of the cluster ions. Information about the dissociation pathways of the cluster ions is essential if one is to obtain neutral cluster abundances from the ion mass spectrum. Furthermore an experimental method is presented to obtain pure intermediate state (S ₁←S₀) spectra of selected clusters without interferences from the other clusters present in the molecular beam. This method is based on the observation of the metastable decay of the corresponding cluster ion. When the metastable signal is recorded as a function of photon energy it reflects theS ₁←S ₀ intermediate state spectrum. Spectra are presented for the benzene dimer, trimer, tetramer and pentamer.     

Photodissociation of an I2 supersonic beam in the nozzle expansion region: Influence on cluster spectra

Iodine clusters are obtained by free expansion of iodine vapour. The I₂ molecule is then photodissociated by a cw laser in the nozzle expansion region. Hot dissociated 1 atoms partially prevent nucleation, allowing accurate probing of the nucleation region. Moreover, I atoms can act as germs for the formation of odd clusters I_2n-1, leading to an increase of the ratio (number of I_2n-1⁺/number of I_2n⁺).     

Electronic relaxation of biacetyl in a supersonic jet

Emission spectra have been recorded and decay times measured for biacetyl selectively excited in the 0⁰₀ band of the S₁S₀ (¹A_u¹A_g) transition. The spectrum of the “long emission” corresponds to a superposition of the fluorescence and of the “hot” phosphorescence. The results may be treated in terms of a uniform distribution of the singlet oscillator strength among the quasi-stationary levels, in the absence of vibrational redistribution on a microsecond scale.     

Photochemical dehydration of acetamide in a cryogenic matrix

Vacuum ultraviolet (VUV) irradiation of acetamide has been monitored by Fourier transform infrared spectroscopy in argon matrix at 10 K. Several primary photoproducts, including HNCO ratio CH(4) and CO ratio CH(3)NH(2) molecular complexes, and acetimidic acid, which is reported for the first time, were characterized. The acetimidic acid identification was based on comparison between the experimental and theoretical (B3LYP) infrared spectra. Acetimidic acid is found in argon matrix in the (s-Z)-(E) and (s-Z)-(Z) configurations. It is also an intermediate in the VUV decomposition process, its dehydration leads to the formation of CH(3)CN ratio H(2)O molecular complex. The assignment of the complex was achieved by co-depositing the pairs of respective species and by ab initio calculation.     

Tunable diode laser absorption spectroscopy study of CH(3)CH(2)ODD(2)O binary condensation in a supersonic Laval nozzle

We have developed a dual-beam tunable diode laser absorption spectroscopy system to follow the cocondensation of water and ethanol in a supersonic Laval nozzle. We determine the D(2)O monomer concentration in the vapor phase by fitting a Voigt profile to the measured line shape but had to develop a calibration scheme to evaluate the C(2)H(5)OD monomer concentration. To measure the temperature of the gas, we seed the flow with CH(4) and measure two absorption lines with different lower state energies. These data give a far more detailed picture of binary condensation than axially resolved pressure measurements. In particular, we observe that the C(2)H(5)OD monomer starts to be depleted from the gas phase well before D(2)O begins to condense.     

Electronic spectra of uracil in a supersonic jet

The fluorescence excitation and dispersed fluorescence spectra of uracil in a supersonic jet have been observed. The n,π¹ states of 2,4-diketo tautomer and enol-keto tautomer are found. The spectral analyses show an out-of-plane deformation of the molecules in the n,π¹ state. The coexistence of diketo and enol-keto tautomer in the vapor is discussed.     

FTIR spectrum of benzene in a supersonic expansion

The 700 and 3050 cm^?1 region of benzene seeded in argon is studied using Fourier-transform infrared absorption spectroscopy. Analysis of the sequence band structure in the 700 cm^?1 region gave new anharmonic constants and values of T_rot (79 ± 15 K) and T_vib (/2~160 K) which indicate a disequilibrium between the rotational and vibrational degrees of freedom. A band contour analysis of the 3050 cm^?1 Fermi triad is used to obtain new values of the Coriolis coupling constants and band origins.     

Homogeneous nucleation of metals in a plasma-quench reactor

We present a new and general application of the method of moments for modeling the nucleation of condensates in a steady-state supersonic nozzle flora generated in a plasma-quench reactor. A closed set of growth/evaporation rate equations has been employed to propagate the moments of the particle size distribution without invoking the usual coarse-graining or truncation approximations of conventional binning approaches. The method has been employed to calculate the nucleation rates, particle number density, and the particle-size distribution for 11 elemental metals (Ag, Al, Be, Ce, Cr, Fe, Gd, Ti, Th, U, and Zr) condensing in a model argon nozzle flow. We have identified the regions in the nozzle of maximum nucleation rate, and have shown how different particle-size distributions can develop in different regions.     

Kinetics of ion-induced nucleation in a vapor-gas mixture

A general solution for the steady-state ion-induced nucleation kinetics has been derived, considering the differences between ion-induced nucleation and homogeneous nucleation. This solution includes a new effect for nucleation kinetics, the interaction of charged clusters with vapor molecules. Analytical expressions for the ion-induced nucleation rate have been obtained for the limiting cases of high and low thermodynamic barriers. The physical explanation of the so-called sign effect is proposed based on multipole expansion of an electric field of the cluster ion. This theory gives good agreement with experiments and is used to elucidate experimentally observed phenomena.     

Computer simulation of nucleation in a gas-saturated liquid

Molecular dynamics methods have been used to investigate the kinetics of the liquid-gas phase transition in a two-component Lennard-Jones system at negative pressures and elastic stretches of the liquid to values close to spinodal ones. The molecular dynamics system consists of 2048 interacting particles with parameters of the Lennard-Jones potential for argon and neon. Density dependences of pressure and internal energy have been calculated for stable and metastable states of the mixture at a temperature T* approximately 0.7+/-0.01 and three values of the concentration. The location of mechanical and the diffusion spinodals has been determined. It has been established that a gas-saturated mixture retains its stability against finite variations of state variables up to stretches close to the values near the diffusion spinodal. The statistic laws of the process of destruction of the metastable state have been investigated. The lifetimes of the metastable phase have been determined. It is shown that owing to the small height of the potential barrier that separates the microheterogeneous from the homogeneous state a system of finite size has a possibility to make the reverse transition from the microheterogeneous into the homogeneous state. The lifetimes of the system in the microheterogeneous state, as well as the expectation times of the occurrence of a critical nucleus, are described by Poissonian distributions.     

Breakup of double emulsion droplets in a tapered nozzle

When double emulsion droplets flow through a tapered nozzle, the droplets may break up and cause the core to be released. We model the system on the basis of the capillary instability and show that a droplet will not break up when the tilt angle of the nozzle is larger than 9°. For smaller tilt angles, whether the droplet breaks up also depends on the diameter ratio of the core of the droplet to the orifice of the nozzle. We verified this mechanism by experiments. The ideas are useful for the design of nozzles not only to break droplets for controlled release but also to prevent the droplet from rupturing in applications requiring the reinjection of an emulsion.