Past exam of the MPhil in micro- and nanotechnology enterprise course of the University of Cambridge / 2017 / Paper 1 / Section B / 10 / iv

Use the normal boiling point as the reference, $T_B=373.15\mathrm{K}$ and $P_B=101325\mathrm{Pa}$. At $T=313.15\mathrm{K}$,This is approximately 0.0795 atmosphere. It uses the supplied constant enthalpy of vaporization approximation across a 60 K interval; it should not be presented as an exact tabulated vapor pressure. Absolute temperature, rather than Celsius values, belongs in the exponential.

The Young–Laplace equation is $p_l-p_v=\gamma (1/R_1+1/R_2)$ with signed principal curvatures positive for a convex liquid droplet. A wetting bridge between plates has a strongly concave meridional curvature. If the contact angle through the liquid is $\theta$, the plate separation is $d$, and the bridge radius is approximately $a\gg d$, thenFor complete wetting, the leading suction is $p_v-p_l\simeq 2\gamma /d$. The neglected azimuthal curvature is of order $1/a$. A numerical pressure cannot be specified without the separation, surface tension and wetting condition. The full signed-curvature expression remains valid when the narrow-gap approximation is unsuitable.

Let $P_{\mathrm{sat}}$ denote the flat-interface saturation pressure at the same temperature, $P_V$ the surrounding equilibrium vapor pressure, and ${\overline{V}}_l$ the incompressible liquid molar volume. Equating liquid and ideal-vapor chemical potentials to their common reference at $P_{\mathrm{sat}}$ givesThus the pressure contribution to the attractive normal force on a wetted circular area isFor capillary pressures large compared with the vapor-pressure difference, and a bridge wetting essentially the plate area,Here $F$ is the magnitude of the external separating force balancing attraction, and $P_V<P_{\mathrm{sat}}$. A finite contact angle adds a contact-line force $2\pi a\gamma \sin \theta$ at each plate's rim, counted once in the force on that plate, while the exact pressure also retains both curvatures. The rim term is normally smaller than the narrow-gap pressure term by order $d/a$ for appreciable wetting; it cannot be neglected uniformly near $\theta =90^{\circ }$. For complete wetting the leading equivalent expression is $F\simeq 2\pi a^2\gamma /d$. The corresponding equilibrium humidity is $P_V/P_{\mathrm{sat}}\simeq \exp [-2\gamma {\overline{V}}_l/(RTd)]$.

These are quasistatic, equilibrium expressions for an existing bridge, neglecting viscous suction, contact-angle hysteresis, disjoining forces and deformation of the plates. The wetted radius must replace $a$ if the liquid does not reach the plate edge. During actual separation a bridge can shrink, depin or break, so this local force balance is not a promise of a constant force for arbitrary travel.