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A surfactant-stabilized dispersion can remain macroscopically uniform while its two liquids remain distinct phases. Lower interfacial tension reduces the work of making droplets, and repulsive interfacial films can slow droplet coalescence. Kinetic emulsion stability does not by itself establish equilibrium molecular miscibility or a thermodynamically stable microemulsion.

For identical spherical drops, total oil volume and interfacial area satisfyTaking $10\mathrm{vol}\%$ to mean the oil fraction of the final emulsion, $V_o/(V_o+V_w)=0.10$ gives $V_o=V_w/9=1.111\times 10^{-4}{\mathrm{m}}^3$. Thus $A=333.3{\mathrm{m}}^2$ and $E_s=16.7\mathrm{J}$. This corresponds to about $2.65\times 10^{13}$ drops.

There is a wording convention worth making explicit: if the oil addition instead means $0.10$ times the initial water volume, then $V_o=100\mathrm{mL}$, $A=300{\mathrm{m}}^2$ and $E_s=15.0\mathrm{J}$. These differ only in the stated volume-fraction convention. The calculation uses the oil–water interface and neglects the container and air interfaces.

In a regular solution, ideal combinatorial entropy competes with a nonzero unlike-contact energy. For equal molecular volumes and mole fraction $\varphi$ of species A, write mixing free energy per site aswhereHere $z$ is the coordination number and ${ϵ}_{ij}$ a pair-contact energy counted consistently in the lattice model. A positive $\chi$ penalizes unlike contacts; a negative value favors them. The logarithmic terms lower free energy on mixing. The sign of the enthalpy of mixing alone therefore does not determine miscibility.

At fixed temperature and composition, a homogeneous phase is globally stable only if no division into two compositions lowers its free energy. The common-tangent construction selects coexisting compositions ${\varphi }_a,{\varphi }_b$, equivalent to equality of both species' chemical potentials. Local stability to infinitesimal fluctuations instead requiresZero curvature gives the spinodal, while the coexistence boundary is the binodal. Between them a homogeneous state can be metastable and require nucleation; inside the spinodal its small composition fluctuations grow. The symmetric regular solution hasBelow this contact penalty, the free energy is convex at every composition. Above it a miscibility gap is possible around the central composition. If $\chi =A/T$ with $A>0$, heating promotes mixing, but specific interactions or temperature-dependent noncombinatorial terms can produce other trends.

For two polymers, let $N_A,N_B$ count equal-volume segments per chain, and now let $\varphi$ be the segment volume fraction of A. Connecting segments into chains reduces their independent translational entropy. The binary Flory-Huggins polymer blend hasThe energetic contact term remains extensive in the number of segments, while the favorable entropy per segment is reduced by $1/N_A$ and $1/N_B$. This is the key long-chain limit of polymer-blend miscibility: a small positive incompatibility can overcome the mixing entropy. The lattice treatment is a controlled model for this argument, rather than a claim that every real blend has composition-independent $\chi$.^[ref]

The local stability condition and critical interaction parameter becomeFor equal chain lengths, ${\chi }_c=2/N$. Similar segment chemistry and matched cohesive interactions can reduce the unlike-contact penalty; favorable specific interactions, such as complementary hydrogen bonding, can make mixing favorable even for long chains. Lower molar mass increases mixing entropy. temperature can help when it lowers the effective $\chi$, but heating is not universally sufficient. A suitable common solvent can facilitate processing or ternary mixing, and a block-copolymer compatibilizer can stabilize fine domains; neither guarantees that the final solvent-free binary material is one equilibrium molecular phase.

An oil–water emulsion illustrates emulsion stability versus molecular miscibility. A surfactant adsorbs with its water-affine head toward water and its oil-affine tail toward oil, lowering interfacial tension and the work $\gamma dA$ needed to make additional interface. Breaking a fixed oil volume $V_o$ into spherical droplets of radius $R$ gives total area $3V_o/R$, so creating small droplets still requires substantial area and usually mechanical work.

Adsorbed surfactants can oppose droplet coalescence through charged double-layer repulsion, hydrated-head interactions or steric repulsion from sufficiently extended groups. Adequate coverage, adsorption time, ionic conditions and film drainage affect the lifetime. A lower interfacial tension does not itself remove the bulk miscibility gap, and a protected emulsion is commonly kinetically stabilized. A thermodynamically stable microemulsion is a distinct situation requiring an appropriate composition and free-energy balance. The two liquids must not be called molecularly miscible simply because droplets disperse visibly.

For the capillary, balance upward contact-line force against hydrostatic column weight, neglecting meniscus volume and gas density. For inner radius $r$,The contact angle is measured through the liquid. complete wetting means ${\theta }_2=0$, so the contact-angle change of capillary rise givesThis follows from the stipulated wetting change, holding radius, bulk liquid surface tension and density fixed. One should not replace that premise with a general claim that grease always improves glass wetting; if contamination also changes the liquid surface tension, the original height and new angle alone would not determine the new height.

For two wide vertical plates separated by gap $d$, use unit width. There are two upward contact-line contributions and liquid cross-sectional area $d$, giving the capillary rise between parallel plates:Only one principal meniscus curvature contributes between wide plates, whereas a circular tube has two. For the same fluid and angle,If the plate gap equals the tube diameter, $d=2r$, the rise is half as large: the initial and completely wetting heights would be $2.50$ cm and $3.05$ cm. If instead $d=r$, the heights are equal. In either geometry, changing only the angle from $35^{\circ }$ to zero multiplies the height by $1/\cos 35^{\circ }$. Since the question specifies no plate spacing, the general gap-dependent relation is the unambiguous result; the half-height answer requires the equal-gap-to-diameter convention.

A colloid has dispersed constituents whose relevant dimensions are mesoscopic: roughly $1\mathrm{nm}$ to $1\mu \mathrm{m}$ in at least one direction. Interfaces and Brownian motion are consequently important. The size range is a useful convention, not a sharp boundary separating all physical behaviour. A sol of fine silicon dioxide particles in water illustrates solid in liquid; an oil-in-water emulsion illustrates liquid in another immiscible liquid; and a foam illustrates gas dispersed in a liquid, with thin intervening films supplying the small structural dimension. A colloid need not be a thermodynamic equilibrium state.^[ref]

Unprotected particles attract through Van der Waals forces. For two equal spheres of radius $a$ with a small surface gap $H$, the near-contact van der Waals attraction of spheres iswhere the Hamaker constant $A_H$ is positive for the attractive case. The large number of interacting constituent molecules can give a well much deeper than $k_{B}T$, even though individual molecular attractions are weak. Brownian motion brings particles together, and a sufficiently deep attractive well makes separation unlikely. This gives particle aggregation; solid particles can remain distinct within a cluster rather than merging into one continuous solid. Emulsion droplets can additionally coalesce if the separating film ruptures.

Charge stabilization of colloids supplies a repulsive barrier. Like-charged surfaces carry compensating counterions and electric double layers; bringing the layers together costs free energy. DLVO theory combines this repulsion with Van der Waals forces. A barrier large compared with $k_{B}T$ can make aggregation slow, even when sticking would lower the final free energy. Adding salt generally shortens the Debye–Hückel screening length and can lower the barrier; surface charge regulation and specific ion interactions also matter. A negatively charged particle and a positively charged particle need not repel.

Steric stabilization instead coats each particle with adsorbed or grafted polymer chains. In a good solvent, overlap and compression of these layers raise the osmotic pressure and reduce chain entropy, opposing close contact. Electrosteric stabilization combines the two mechanisms. Dense, securely bound layers matter: incomplete adsorption can allow polymer bridging, while nonadsorbing dissolved polymers can create an attractive depletion force. Poor solvent quality can collapse a protective layer. Reducing the density mismatch slows sedimentation but does not remove the interparticle attraction, so uniform suspension and resistance to aggregation are different requirements.

The left panel is an original qualitative potential with arbitrary coefficients: it illustrates a barrier and its reduction by shorter-ranged repulsion, without fitting an experimental DLVO theory curve or extrapolating the continuum attraction to molecular contact. The right panel plots the derived quasi-steady concentration profile in dimensionless variables.

In diffusion-controlled growth, attachment is rapid and delivery through the surrounding medium is the bottleneck. The growing surface depletes the neighboring solute, so a substantial concentration gradient develops. In reaction-controlled growth, arrival is fast compared with incorporation; many arrivals fail to attach, and the surface concentration stays near the reservoir value. The analogous distinction for particle aggregation is between near-unit sticking probability in diffusion-limited cluster aggregation and barrier-suppressed sticking in reaction-limited cluster aggregation. Here the subsequent calculation concerns accretion onto one growing particle, rather than a collision kernel for two mobile clusters.

The printed time-dependent equation is the diffusion equation, not the usual Poisson equation. For constant diffusion coefficient $D$, no bulk sources and negligible advection, Fick's laws give the number flux $\mathbf{j}=-D\nabla c$. Local conservation of mass, expressed here as conservation of the accreting constituent, then givesAn arbitrary time-independent exterior profile does not solve the full moving-boundary problem exactly. The required elementary result uses a quasi-steady approximation: diffusion establishes the exterior profile much faster than the particle radius changes. At each instantaneous radius $a$, set $\partial c/\partial t\simeq 0$. Thus the exterior field solves the homogeneous Laplace equation,Two integrations give $c=A+B/r$. The two boundary conditions fixFor growth, $c_{\infty }>c_s$, so the profile increases outwards. Its radial flux is negative, and the positive inward arrival rate isA material density is needed to turn an arrival rate into a radial velocity. Introduce the constant constituent number density $c_p$ inside the particle, using the same units as $c_s,c_{\infty }$. The sharp-interface balance, neglecting exterior advection, isThe difference $c_p-c_s$ accounts for material already present in the volume swept by the growing interface. In the usual dilute-feed approximation $c_s\ll c_p$, it can be replaced by $c_p$. With constant reservoir and surface concentrations, integration from radius $a_0$ gives the constant-reservoir diffusion-controlled particle growth lawConsequently $a\propto t^{1/2}$ when the growth contribution dominates $a_0^2$. For a finite seed at the literal limit $t\to 0$, the increment $a-a_0$ is instead initially proportional to $t$. Here “early time” means before appreciable reservoir depletion or interactions with other particles, while already beyond the rapid initial establishment of the diffusion field. Indeed, the ratio of diffusion-adjustment time $a^2/D$ to radial-growth time $a/\dot{a}$ is $(c_{\infty }-c_s)/(c_p-c_s)$; small supersaturation relative to the particle density makes the quasi-steady approximation self-consistent. No initial concentration field was specified, so an exact transient solution is not uniquely determined.

For comparison, let a finite surface-attachment coefficient be $k_s$ and the equilibrium surface concentration be $c_{\mathrm{eq}}$. In the dilute-feed approximation, the Robin boundary condition $D{c}^{\prime }(a)=k_s[c(a)-c_{\mathrm{eq}}]$ givesFor $k_{s}a/D\gg 1$ this recovers transport control; for $k_{s}a/D\ll 1$, the surface-reaction-controlled particle growth has approximately constant $\dot{a}=k_s(c_{\infty }-c_{\mathrm{eq}})/c_p$. Thus reaction control gives $a-a_0\propto t$, in contrast to the diffusion-controlled square-radius law. No numerical $c_p$ or $k_s$ is supplied or needed for these scaling results.

An emulsion stabilized by particles adsorbed at the liquid–liquid interface. A partially wetting sphere has a detachment-energy scale $\pi r^2\gamma (1-|\cos \theta |{)}^2$, which can greatly exceed $k_{B}T$ for nanoparticles; complete wetting and insufficient coverage prevent a universal stability guarantee.