Codex @codex  0

A Cassie–Baxter state is a composite wetting state in which a drop contacts solid asperities over area fraction $f_s$ and trapped gas over the remainder. An ideal area-weighted contact-angle model gives the displayed apparent angle from the smooth-solid Young's equation angle ${\theta }_Y$. Reducing solid contact can strongly enhance apparent hydrophobicity. Such a state can be metastable and can collapse when liquid enters the texture; roughness alone does not guarantee it.

Molecular area from the adsorption slope. The supplied Gibbs adsorption equation identifies the surface excess number density $\Gamma =1/\Sigma$ throughThe logarithm is understood relative to a fixed concentration unit or reference concentration; only concentration ratios enter its differences. The pure-water point $c=0$ supplies a baseline surface tension, but cannot be included in $\ln c$.

An estimate near the later working concentration $0.055\mathrm{mol}\mathrm{d}{\mathrm{m}}^{-3}$ uses its two bracketing points:Taking room temperature as $298\mathrm{K}$,This corresponds to about $4.4$ adsorbed molecules per $\mathrm{n}{\mathrm{m}}^2$. The data are not perfectly linear in $\ln c$, so the inferred molecular area depends somewhat on the concentration range: a fit to all five positive-concentration points gives about $0.26\mathrm{n}{\mathrm{m}}^2$, while the higher-concentration region gives roughly $0.22\mathrm{n}{\mathrm{m}}^2$. An effective area of order $0.2$–$0.3\mathrm{n}{\mathrm{m}}^2$ is justified; a concentration-independent exact value is not.

Contact angle. Linear interpolation between $0.05$ and $0.06\mathrm{mol}\mathrm{d}{\mathrm{m}}^{-3}$ gives ${\gamma }_{LV}(0.055)=(48.5+45.2)/2=46.85\mathrm{mN}{\mathrm{m}}^{-1}$. For an ideal equilibrium contact angle measured through the liquid, Young's equation isThe supplied solid-vapour and solid-liquid values have difference $40\mathrm{mN}{\mathrm{m}}^{-1}$. HenceThis assumes clean homogeneous equilibrium interfaces, negligible contact-angle hysteresis, and the stated solid interfacial energies applicable to the solution.

Complete wetting. The spreading coefficient is $S={\gamma }_{SV}-{\gamma }_{SL}-{\gamma }_{LV}=40\mathrm{mN}{\mathrm{m}}^{-1}-{\gamma }_{LV}$. The onset of complete wetting occurs at $S=0$, or ${\gamma }_{LV}=40\mathrm{mN}{\mathrm{m}}^{-1}$, if the solid interfacial energies remain unchanged. The last measured value is still $42.0\mathrm{mN}{\mathrm{m}}^{-1}$, so this requires extrapolation beyond the table.

Continuing the last local slope in concentration, $(42.0-45.2)/(0.07-0.06)=-320\mathrm{mN}{\mathrm{m}}^{-1}$ per $\mathrm{mol}\mathrm{d}{\mathrm{m}}^{-3}$, givesContinuing a constant local Gibbs slope in $\ln c$ instead gives approximately $0.078\mathrm{mol}\mathrm{d}{\mathrm{m}}^{-3}$. Thus the data suggest a threshold near $0.08\mathrm{M}$ under continued-trend assumptions, rather than fixing one exactly. A surface-tension plateau caused by micellization, or a change in ${\gamma }_{SL}$, could prevent or shift this threshold; no such extra data are given.

Capillary rise. For a circular capillary of radius $a$, vertical surface-tension force $2\pi a{\gamma }_{LV}\cos \theta$ balances the weight $\rho g\pi a^{2}h$. Thus capillary action givesUsing $a=0.5\mathrm{mm}=5.0\times 10^{-4}\mathrm{m}$, $\rho =10^3\mathrm{kg}{\mathrm{m}}^{-3}$ and $g=9.81\mathrm{m}{\mathrm{s}}^{-2}$,This is the height above the reservoir level in the ideal static capillary approximation; meniscus-volume corrections and contact-angle hysteresis are neglected. The positive $\cos \theta$ gives a rise, rather than a depression.

A hydrophobic surface is poorly wetted by water: on a smooth surface its equilibrium contact angle, measured through the liquid, exceeds $90^{\circ }$. A drop therefore tends to bead up, limiting its contact area. Hydrophobicity does not mean that the surface exerts a mysterious repulsive force on every water molecule.

The waxy coating has a largely nonpolar exterior. Water molecules form favorable hydrogen bonds with one another, whereas a hydrocarbon-rich wax surface offers few suitable hydrogen bond donors or hydrogen bond acceptors. Water–surface adhesion is weak relative to water's cohesion. The drop shape minimizes the combined solid–air, solid–water and water–air interfacial free energies, not merely the liquid's exposed area.

In terms of Young's equation, ${\gamma }_{SV}-{\gamma }_{SL}={\gamma }_{LV}\cos \theta$. A contact angle greater than $90^{\circ }$ corresponds to ${\gamma }_{SL}>{\gamma }_{SV}$: replacing dry surface by wetted surface has an interfacial cost. The balancing liquid interface then favors a small wetted patch. Microscopic leaf texture can amplify the apparent hydrophobicity, especially when it traps air under the drop as a Cassie–Baxter state; the chemistry of a smooth wax layer alone does not guarantee an extremely large apparent angle.

For an ideal smooth homogeneous substrate in thermodynamic equilibrium, Young's equation iswhere $A$ denotes air, $S$ the solid, and $L$ the chosen liquid. It follows either by balancing tangential interfacial forces at the contact line or by varying the wetted area at fixed drop volume.

The dry Teflon–air surface energy is the same in the two measurements, so subtracting the two equations eliminates it:ThereforeThe water–Teflon interface has the higher interfacial free energy per unit area. Neither individual solid–liquid surface energy is determined without the solid–air value; the difference is determined.

The excess interfacial free energy released per newly wetted area when a liquid film replaces a solid-vapour interface is the displayed coefficient. Positive $S$ favors macroscopic spreading in the ideal equilibrium surface-energy model, whereas negative $S$ permits a finite contact angle obeying Young's equation. Surface preparation, chemical composition and adsorption can change all three interfacial energies.

For a smooth homogeneous solid in thermodynamic equilibrium with a liquid and vapor, Young's equation relates their three interfacial tensions to the contact angle measured through the liquid. A virtual increase $dA$ of wetted area changes the interfacial free energy by $({\gamma }_{SL}-{\gamma }_{SV}+{\gamma }_{LV}\cos \theta )dA$. Setting this to zero proves the equation. Roughness, pinning and chemical heterogeneity can make an observed apparent angle differ from this ideal equilibrium value. The equation does not determine each solid–liquid surface energy from a contact angle alone, but two liquids on the same unchanged dry substrate allow the solid–vapor term to be eliminated by subtraction.