Capillary Drops Research Articles

Mechanism for drop formation on a coated vertical fibre

Rayleigh instability on an axisymmetric viscous film around a vertical fibre produces localized wave structures (pulses) on a flat substrate film that can grow by an order of magnitude to form large capillary drops. We show that this drop formation process is driven by a unique mechanism in the form of an ever-growing pulse which leaves behind a trailing film thinner than the one it advances into. In addition to accumulating liquid from the film, the growing pulse also captures smaller and slower pulses in coalescence cascades. We construct this supercritical growing pulse by matched asymptotics and show that it will eventually evolve into a capillary drop if the local film thickness h is larger than hc=1.68R3H−2 where R is the fibre radius and H the capillary length. We also show that subcritical pulses with h<hc will equilibrate into stationary pulses that do not grow or coalesce readily to form drops.

Fluctuations, temperature, and detailed balance in classical nucleation theory

The role of temperature in classical nucleation theory is examined. It is shown that while even small clusters are assigned a temperature in the classical theory, this must be a fluctuating quantity. Stochastic simulations of cluster evaporation and growth are presented to track the temperature fluctuations in time. The relation 〈‖δT‖2〉=kT20/Cν for the mean square temperature fluctuation is confirmed, where k is the Boltzmann constant, Cν is the cluster heat capacity, and T0 is the bath temperature. For small capillary drops (50–100 molecules), the resulting rms temperature fluctuations of 10°–20° might be expected to have a significant effect on the nucleation rate. However, the simulations reveal a cluster temperature distribution that is centered several degrees below T0. A theory is presented to explain this effect. To first order, which includes Gaussian fluctuations of the cluster temperature T, we find that the effective temperature for cluster evaporation is T−h/2Cν, where h is the latent heat. This temperature correction is precisely that required by detailed balance and results both in a centering of the cluster temperature distribution on T0 and a cancellation of any significant effect of temperature fluctuations on the nucleation rate.

Stability of the FID sensitivity during an analysis in capillary GC

AbstractThe sensitivity of an FID may change when the carrier gas flow rate changes during a chromatographic run. Sample parts which are eluted at reduced FID sensitivity produce a reduced peak area, hence are discriminated as compared to other components. Sensitivity changes were studied for hydrogen as carrier gas. For the detector tested, differences in the carrier gas flow rates of 1 ml/min shifted the FID sensitivity by 1 to 5% (depending on the fuel gas supply). Thus the stability of the sensitivity is no longer ensured as soon as the carrier gas flow rate is changed manually or by an automatic programmer during an analysis. Sensitivity drifts may also occur during temperature programmed runs with a pressure regulated carrier gas supply since the gas flow through the capillary drops with increasing temperature. Such shifts in the response became noticeable as soon as relatively high carrier gas flow rates combined with long range temperature programmes were used. The typical patterns of such discriminations are shown, closing with a discussion on the possibilities for minimizing such undesired effects.