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A cationic surfactant with a sixteen-carbon hydrocarbon tail and a positively charged trimethylammonium head group, accompanied by a ${\mathrm{Br}}^{-}$ counterion. It is an amphiphile that can form aqueous micelles. Its head-group charge has the opposite sign to that of sodium dodecyl sulfate.

The critical micelle concentration is the approximate surfactant concentration above which additional dissolved amphiphile predominantly enters micelles rather than remaining as isolated molecules. It is a concentration crossover governed by equality of the molecular chemical potential in the two environments, not a claim that absolutely no aggregates exist below a sharp threshold. Temperature, ionic conditions and molecular structure affect its value.

A localized amount $M=\int Cdx$ of insoluble surfactant spreads over a planar film of depth scale $h_0$. Neglect gravity, capillarity and diffusion. Then $C\sim M/\ell$ and Marangoni stress drives $u_s\sim AM{h}_0/(\mu {\ell }^2)$, giving $\ell \sim (AM{h}_{0}t/\mu {)}^{1/3}$. The thin-film equations with insoluble surfactant admit a similarity solution in which the film height and concentration depend on $x/\ell$, conserving total surfactant and fluid volume relative to the undisturbed layer.

A gravity-capillary wave has restoring contributions from both gravity and surface tension. Consider an initially resting, horizontally unbounded liquid layer of constant depth $h$, with uniform mass density $\rho$, incompressible flow, inviscid flow and irrotational flow. The upper gas exerts constant pressure and has negligible inertia. Assume a clean interface with constant surface tension $\gamma$: no surfactant stresses, imposed current or wind. The wave amplitude $a$ must satisfy $ka\ll 1$ and $a\ll h$, so linearized boundary conditions apply. Deep water means $kh\gg 1$, rather than a particular depth in metres. ^[ref]

Let $z=0$ be the undisturbed free surface, with liquid below it. Potential flow gives a velocity potential $\varphi$ with $\mathbf{u}=\nabla \varphi$, and incompressible flow gives the Laplace equation. The linearized kinematic boundary condition for a free-surface graph and the Unsteady Bernoulli equation, including gravity and the Young–Laplace equation, giveHere $\eta (x,t)$ is the interface displacement; the signed small-slope pressure jump is $p_{\mathrm{liquid}}-p_{\mathrm{gas}}=-\gamma {\eta }_{xx}$. A wave crest has ${\eta }_{xx}<0$, so its capillary pressure is positive. Choose a right-travelling Fourier mode of positive wavenumber $k$ and angular frequency $\omega$:The factor $e^{kz}$ decays into the deep liquid, satisfies the Laplace equation, and makes ${\varphi }_z={\eta }_t$ at $z=0$. Substituting in the dynamic boundary condition leavesThis derivation displays the two restoring contributions with the same sign. Dimensional analysis also checks the result: $\gamma /\rho$ has units ${\mathrm{m}}^3{\mathrm{s}}^{-2}$, so both $gk$ and $(\gamma /\rho )k^3$ have units ${\mathrm{s}}^{-2}$. ^[ref]

At finite depth, a flat impermeable bottom at $z=-h$ requires ${\varphi }_z=0$. Replacing $e^{kz}$ by the normalized vertical factor $\cosh (k(z+h))/\cosh (kh)$ makes the surface ratio ${\varphi }_z/\varphi =k\tanh (kh)$. Eliminating the mode amplitudes then givesThus the same model supplies its own depth check: use the deep-water formula only when $\tanh (kh)$ is sufficiently close to one for the required accuracy. For example, $kh=3$ reduces $\omega$ by about $0.248\%$ relative to deep water, while $kh=1$ reduces it by about $12.7\%$. These percentages are calculations from this factor. ^[ref]

In deep water the phase velocity magnitude follows a wave crest, while the group velocity magnitude follows the wave envelope of a narrow wave packet. Differentiating the positive-frequency dispersion relation givesFor $k{\ell }_c\ll 1$, the surface gravity wave limit has $c_g\simeq c_p/2$. For $k{\ell }_c\gg 1$, the deep-water capillary-wave dispersion relation has $c_g\simeq 3c_p/2$: a wave crest slips backward relative to the faster wave envelope, even while both advance. Neither speed is the oscillating fluid element's own velocity. ^[ref]

There is a particularly neat coincidence at the crossover. Differentiate $c_p^2=g/k+\gamma k/\rho$: its unique minimum is at $k_c=\sqrt{\rho g/\gamma }=1/{\ell }_c$, exactly where the restoring terms are equal. ThereforeFor the stipulated parameters in capillary length, the minimum is $0.231\mathrm{m}{\mathrm{s}}^{-1}$. At $\lambda =3\mathrm{mm}$, direct substitution gives $f=\omega /(2\pi )\simeq 131\mathrm{Hz}$, $c_p\simeq 0.394\mathrm{m}{\mathrm{s}}^{-1}$ and $c_g\simeq 0.580\mathrm{m}{\mathrm{s}}^{-1}$. This short wavelength is capillary dominated, but its group velocity is still slightly below the pure-capillary ratio $3c_p/2$ because gravity has not vanished.

After gravity smoothing of a Marangoni front reaches the whole spreading pool, the film approaches uniform depth while surface transport continues. A small height gradient creates a hydrostatic pressure return flow that almost cancels the net Marangoni stress flux. Setting $q\simeq 0$ in the thin-film equations with insoluble surfactant gives $h_x\simeq -3A{C}_x/(2\rho g{h}_0)$ and fractional depth variation $O(AM/(\rho g{h}_0^2{x}_N))\ll 1$. The depressed region under the surfactant therefore becomes progressively shallower.

Zhu, Miao, Xu and Cao's 2007 experiment drove a triangular metal frame electromagnetically with a sinusoidal generator. In a roughly $3\mathrm{cm}$-deep, temperature-regulated pool, it produced nearly plane capillary waves. A $632.8\mathrm{nm}$ laser illuminated the surface obliquely; the moving ripples acted as a reflection diffraction grating. One split beam monitored laser stability, while a CCD recorded diffraction orders on a screen $6.76\mathrm{m}$ away. An air-supported optical table reduced ambient vibration. ^[ref]

The frequency sweep was $100$–$290\mathrm{Hz}$ in $10\mathrm{Hz}$ steps, using distilled water and kerosene at $20{}^{\circ }\mathrm{C}$. For each setting they averaged at least three measurements of first-order spot separation. Known optical geometry and the grating equation yielded $k=2\pi /\lambda$; generator readings yielded $\omega =2\pi f$. Agreement with the predicted log–log slope $3/2$ tests the capillary law, and its intercept gives surface tension if mass density is known. The authors identify surface contamination as a major error source; noncontact optical detection reduces additional disturbance. ^[ref]

The optical measurement can be understood from the grating equation. Let ${\lambda }_L$ be the laser wavelength, $\alpha$ the incident grazing angle above the mean surface, and ${\beta }_m$ the outgoing grazing angle of diffraction order $m$, with the sign of $m$ chosen so thatThus calibrated spot positions determine outgoing angles, which determine the ripple wavelength $\lambda$, independently of the mechanical dispersion relation. This optical geometry treats the surface as a reflection diffraction grating at the laser wavelength. ^[ref]

The inferred surface tension in the full deep-water model isThis formula makes useful experimental controls explicit. Measure mass density at the sample's temperature; check depth with $kh$; keep the driven wave amplitude small enough that $ka\ll 1$; and distinguish $f$ from angular frequency $\omega$. For the stipulated parameters, the $100$–$290\mathrm{Hz}$ window corresponds to calculated wavelengths about $3.62$–$1.76\mathrm{mm}$ and $kh\simeq 52$–$107$ at $h=30\mathrm{mm}$. Depth corrections are negligible here, but the gravity contribution is about $4.5\%$–$1.1\%$ of the capillary contribution. These are ideal predictions, not digitized results from the experiment.

Omitting gravity would infer ${\gamma }_{\mathrm{cap}}=\rho {\omega }^2/k^3=\gamma +\rho g/k^2$, biasing surface tension upward. In the capillary limit, the differential estimate $d\gamma /\gamma \simeq d\rho /\rho +2d\omega /\omega -3dk/k$ also shows why careful spot-spacing calibration matters. A clean surface and weak viscosity are modeling assumptions: appreciable damping, surfactant stresses or large wave amplitudes call for additional physics. The experiment tests the short-wave regime; its drive window does not establish the crossover or the long-wave surface gravity wave limit.

The material derivative follows surfactant carried by the moving interface. Tangential surface divergence changes the local surface area and hence dilutes or concentrates insoluble material. Normal motion changes area through the curvature: an expanding sphere has positive $u_n{\nabla }_s\cdot \mathbf{n}$ and its concentration decreases. The last term is surface diffusion, which smooths concentration gradients. There is no exchange with the bulk; this is conservation of insoluble surfactant on a moving interface.

The interfacial speed is of order $a|\mathbf{F}|$. Diffusion dominates redistribution when the surface Péclet number satisfiesThen $C^{\prime }/C_0=O({\mathrm{Pe}}_s)$, and advection of $C^{\prime }$ is a second-order effect. Write $S=\mathbf{n}\cdot \mathbf{Fn}$. Since ${\mathbf{u}}_s=\mathbf{Fx}-S\mathbf{x}$, the projected divergence of the first term is $\mathrm{tr}\mathbf{F}-S=-S$, whereas the second has divergence $2S$; its gradient contracted with $\mathbf{x}$ is zero. Hence ${\nabla }_s\cdot {\mathbf{u}}_s=-3S$.

The leading steady transport equation is $D_s{\Delta }_s{C}^{\prime }=C_0{\nabla }_s\cdot {\mathbf{u}}_s=-3C_{0}S$. Trace-freeness and the supplied surface Laplacian identity give ${\Delta }_{s}S=-6S/a^2$. Fixing the conserved total surfactant removes the uniform null mode and yieldsThis is quadrupolar surfactant distribution on a spherical interface; its spherical mean is zero because $⟨n_i{n}_j⟩={\delta }_{ij}/3$.

With $+$ outside, $-$ inside, and the normal directed out of the bubble, the interfacial stress balance with variable surface tension isNow ${\nabla }_{s}S=2I_s\mathbf{Fn}/a$, so $-{\nabla }_s\gamma =2A{\gamma }_1{I}_s\mathbf{Fn}/a$. Multiplying the curvature by the tension and retaining linear terms givesThe undeformed isotropic pressure jump is kept with its normal; the perturbation terms are evaluated on the reference sphere. Products of deformation and concentration perturbations are beyond the approximation.

The imposed tensor is symmetric and traceless, so $\mathbf{x}\cdot \mathbf{Ex}$ is a harmonic scalar of degree two. Its decaying partner is $\mathbf{E}:\nabla \nabla (1/r)$; the corresponding harmonic vector uses $\mathbf{E}\nabla (1/r)$. Linearity and rotational symmetry give precisely these tensorial modes, with the growing scalar chosen to reproduce the imposed strain. Thus in the unscaled convention one can takeThe coefficients multiply distinct decaying modes. No other angular harmonic is forced at this order.

No penetration in the steady state gives $P=3Q-1$. The given tangential surface velocity implies $\alpha =1+2Q$. The tangential stress balance, with $M=A{\gamma }_1/(\mu a)$, gives $1+P-8Q=M\alpha$, or $-5Q=M(1+2Q)$. ThereforeThe nonuniform normal stress is unaffected by the uniform inviscid interior pressure. Its balance isSubstitution and rearrangement giveAs $M\to \infty$, $\alpha \to 0$: the concentration-induced Marangoni stress suppresses tangential surface motion, making the exterior boundary behave like an immobile surface despite the inviscid interior. The deformation coefficient tends to $5\mu a/(2{\gamma }_0)$; the clean limit is $2\mu a/{\gamma }_0$. Both small surface Péclet number and small deformation, of order $\mu a|\mathbf{E}|/{\gamma }_0$, are required. This is Marangoni immobilization of a bubble in straining flow.

Let $\mathbf{n}$ point from fluid $-$ to fluid $+$, $P_s=I-\mathbf{nn}$, ${\nabla }_s=P_s\nabla$, and $\mathcal{K}={\nabla }_s\cdot \mathbf{n}$. A clean material interface without phase change has continuous velocity, with normal interface speed $V_n={\mathbf{u}}_{\pm }\cdot \mathbf{n}$. Its surface stress is $\gamma P_s$. The surface divergence of that tensor is ${\nabla }_s\gamma -\gamma \mathcal{K}\mathbf{n}$. Balancing forces on a small interfacial patch therefore gives the interfacial stress balance with variable surface tensionThe normal condition is $\mathbf{n}\cdot ({\mathbf{\sigma }}_{+}-{\mathbf{\sigma }}_{-})\mathbf{n}=\gamma \mathcal{K}$; the tangential condition is $P_s({\mathbf{\sigma }}_{+}-{\mathbf{\sigma }}_{-})\mathbf{n}=-{\nabla }_s\gamma$. On a stationary sphere with outward normal these reduce to $p_{-}-p_{+}=2\gamma /a$ when viscous normal stresses vanish. This fixes the sign convention for the Marangoni stress rather than leaving the direction ambiguous.

For the bubble take negligible internal dynamic viscosity, no contaminants, and initially the standard effectively insulating gas-bubble approximation. With heat advection neglected, the exterior temperature satisfies Laplace's equation, approaches $T_0+\mathbf{H}\cdot \mathbf{r}$ remotely, and has zero normal heat flux at $r=a$. The temperature dipole around an insulating sphere givesThe zero-flux condition follows by differentiating the radial factor. Let ${\gamma }_T=(d\gamma /dT{)}_{T_0}$. To first order in the weak gradient,

In the laboratory frame the force-free bubble can be described by the harmonic Papkovich–Neuber representation potentialsThey give constant exterior pressure and the decaying source dipole fieldAt the surface $\mathbf{u}\cdot \mathbf{n}=\mathbf{U}\cdot \mathbf{n}$, so the normal kinematic boundary condition holds for translation. In coordinates aligned with $\mathbf{U}$, $u_r=a^{3}U\cos \theta /r^3$ and $u_{\theta }=a^{3}U\sin \theta /(2r^3)$. Direct differentiation givesEquivalently, the surface tangential traction is $(3\mu /a)P_s\mathbf{U}$. The tangential stress condition therefore requiresFor the usual negative ${\gamma }_T$, the bubble moves toward hotter liquid. The normal condition is consistent as well: its viscous dipole is $-6\mu \mathbf{U}\cdot \mathbf{n}/a=3{\gamma }_T\mathbf{H}\cdot \mathbf{n}$, exactly the dipolar part of $2{\gamma }_s/a$. The constant part fixes $p_{\mathrm{gas}}-p_{\infty }=2{\gamma }_0/a$. There is no Stokeslet term, hence no net applied force or drag imbalance.

The thermal assumption matters. The problem gives the exterior thermal diffusivity but no gas thermal conductivity. For an inviscid bubble with conductivity ratio $K=k_{\mathrm{gas}}/k_{\mathrm{liquid}}$, temperature and normal heat-flux continuity instead giveso the same stress calculation givesThe insulating-bubble result uses $K\ll 1$. If instead an undisturbed surface temperature gradient is imposed, corresponding to $K=1$, the coefficient is $1/3$ rather than $1/2$. Exterior thermal diffusivity alone does not select between those thermal boundary conditions. This dependence is explicit rather than silently treating a missing gas property as a prescribed value.

The small parameters can now be stated precisely. With $U_{\ast }=a|{\gamma }_T||\mathbf{H}|/(2\mu )$ and $\nu =\mu /\rho$, requireSmall Reynolds number justifies Stokes flow; small Péclet number allows quasi-static heat conduction without advective distortion; small capillary number and fractional surface-tension variation support a nearly spherical interface and a weak perturbation of its base surface tension. These last two conditions are proportional for this velocity scale but describe different approximations. Linearizing $\gamma (T)$ also needs $a|\mathbf{H}||{\gamma }_{TT}/{\gamma }_T|\ll 1$ if its derivative varies appreciably. Negligible internal viscosity and the insulating specialization require the corresponding gas-to-liquid viscosity and conductivity ratios to be small. Gravity has been excluded; if restored, its buoyancy-induced migration must be small compared with $U_{\ast }$, not merely small enough to avoid deformation.

Finally, surfactants change both the constitutive surface tension and the surface stress dynamics. The surface flow driven by the thermal Marangoni effect carries insoluble surfactant toward the high-tension side, lowering its tension and producing an opposing concentration-driven gradient. When surface diffusion or exchange is slow, this tends to immobilize the interface, suppressing the clean-bubble thermocapillary migration of an insulating bubble, sometimes nearly stopping it. If the surfactant stays uniformly equilibrated, it can instead change ${\gamma }_T$ without a large opposing gradient. Its concentration, surface diffusivity and adsorption kinetics must be supplied to compute a replacement speed; no universal numerical reduction factor follows merely from its presence.

The quarter-rate limit is the strong-elasticity limit $\lambda /\alpha \ll 1$, not the weak-elasticity limit. The original PDF repeats $\alpha /\lambda \ll 1$ here; that is inconsistent with the preceding small-$\alpha$ result. In fact at $\alpha =0$ the maximum is $\lambda /4$, directly contradicting a quarter of that value in the same limit. The converted TeX repairs this particular ratio.

For $\alpha \gg \lambda$ and wavenumbers near the maximum, $S=\alpha s\gg L$. In the quadratic equation, the growing root is $O(\lambda )$, so its square and the $-L\beta$ term are small compared with $S\beta$. The leading balance is $S\beta -LS/4=0$. ConsequentlyThe second root is a rapidly damped surfactant-relaxation mode. Thus the stated quarter-rate result is correct after reversing the printed small-parameter ratio.

Without surfactant, capillary pressure drives a surface flow towards a growing bulge. Advection compresses the insoluble surfactant in converging parts of that motion, increasing concentration and lowering surface tension. The resulting gradient supplies a tangential Marangoni stress that opposes the surface motion. This additional resistance slows capillary-driven redistribution of liquid even after the base-tension decrease has already been accounted for.

In the strong-elasticity limit, concentration gradients suppress tangential interface motion. The surface behaves as effectively immobile at leading order. Setting $u_s\approx 0$ in the velocity formula gives ${\sigma }_x\approx h{p}_x/2$, henceone-quarter of the clean shear-free mobility $h^3/(3\mu )$. This mobility reduction explains the quarter-rate limit; it slows the unstable capillary mode without removing the long-wave unstable band.

The material derivative follows surfactant carried by the moving interface. The term $-C{\nabla }_s\cdot u_s$ is dilution or concentration by tangential area expansion or contraction. The term $-C(u\cdot n){\nabla }_s\cdot n$ is the additional area change produced by normal motion of a curved interface. The term $D_s{\nabla }_s^{2}C$ represents surface diffusion, while $-k(C-C_0)$ relaxes the concentration towards a reservoir value through exchange. All these terms refer to concentration per surface area, as in surfactant transport with exchange relaxation.

In the steady bubble frame, the spherical interface has $u\cdot n=0$. Write $C=C_0+C^{\prime }$ with uniform $C_0$ and regard both $u$ and $C^{\prime }$ as first order in the rising speed. Advection of $C^{\prime }$ and its product with surface dilation are second order. Hence the linear steady equation isSpherical symmetry and linearity leave only the tangential projection of the imposed translation vector: $u_s=A{I}_{s}U$. An azimuthal term $n\times U$ would change sign under reflection and is excluded for this non-chiral rising bubble. The degree-one forcing does not excite other spherical-harmonic degrees in the linear problem.

On $r=a$, differentiating $n=x/r$ givesEach component of $n$ is a degree-one spherical harmonic, soOne may also obtain the coefficient from $n\cdot n=1$: its surface Laplacian gives $n\cdot {\nabla }_s^{2}n=-|{\nabla }_{s}n{|}^2=-2/a^2$, while rotational symmetry makes the vector Laplacian parallel to $n$. Expanding $I_{s}U=U-n(U\cdot n)$ then yieldsThe candidate $C^{\prime }=BU\cdot n$ therefore solves the linear transport equation ifIts spherical mean is zero. This is the dipolar surfactant distribution. Assuming $k{a}^2+2D_s>0$, its consistency condition isDiffusion or exchange must restore uniform concentration faster than the interfacial flow redistributes it: this holds with a small surface Péclet number, fast exchange, or sufficiently immobilized surface velocity. These same conditions justify neglecting the perturbation's advection. Small capillary number and sufficiently small buoyancy-induced shape distortion are separate requirements for a spherical interface.

Take $+$ to mean the outer liquid, $-$ the bubble interior and $n$ outward from the bubble. The general interfacial stress balance with variable surface tension isFor $\gamma ={\gamma }_0-{\gamma }_1{C}^{\prime }$, its tangential part is $-{\nabla }_s\gamma ={\gamma }_{1}B{I}_{s}U/a$. Thus the requested form isThis positive parameter measures the strength of the restoring Marangoni stress relative to viscous stress, including the relaxation of concentration by diffusion and exchange.

The far velocity $-U$ is produced by the constant harmonic vector potential $\Phi =U$. The two independent decaying degree-one modes are the force-carrying vector potential $\alpha aU/r$ and the scalar dipole $\chi =\beta a^{3}U\cdot \nabla (1/r)$. They are harmonic outside the bubble and have precisely the symmetry of uniform translation. The Unscaled Papkovich–Neuber representation gives, at arbitrary radius,The velocity at $r=a$ agrees with the printed expression. However, the original PDF's traction formula has a factor-of-two error. Direct differentiation with $\sigma =-pI+\mu (\nabla u+\nabla u^T)$ givesnot the printed prefactor $12\mu /a$. This is traction of translating-sphere Papkovich–Neuber potentials. The $\alpha$ term follows immediately from the Stokeslet stress, and the scalar-potential part gives $6\mu \beta [U-3(U\cdot n)n]/a$; neither contribution contains the extra factor two.

With this consistent traction, no penetration requires $\beta -\alpha =1/2$, tangential velocity requires $A=-(1+\alpha +\beta )$, and tangential stress balance requires $\beta =A\lambda$. Solving,For comparison, taking the printed $12\mu /a$ literally would instead giveThose solve the supplied algebraic pair but not the Newtonian stress calculated from the supplied potentials. The factor-six result is the physically consistent translating surfactant-coated bubble solution.

As $\lambda \to 0$, $A\to -1/2$ and $\beta \to 0$: the clean bubble has a mobile interface and zero tangential traction. As $\lambda \to \infty$, $A\to 0$, $\alpha \to -3/4$ and $\beta \to -1/4$: the interface becomes immobilized and the exterior flow approaches that past a no-slip rigid sphere. The limiting tangential traction is $-3\mu I_{s}U/(2a)$, a useful check on the correct normalization.

The normal dynamic traction isapart from an arbitrary constant pressure. In the normal stress balance on a translating bubble, its degree-one part is balanced by the buoyant hydrostatic pressure difference and by the variation $-2{\gamma }_1{C}^{\prime }/a$ of normal capillary stress. A uniform internal gas pressure balances the constant Laplace-pressure term but cannot by itself balance this angular variation. If $U$ is upwards and $\Delta \rho$ is liquid minus bubble mass density, the degree-one balance can be writtenIt fixes $U=\Delta \rho g{a}^2(1+2\lambda )/[3\mu (1+3\lambda )]$, tending to the clean-bubble and rigid-sphere rise speeds. A degree-one radial displacement translates a sphere rather than changing its curvature, so a supposed dipolar shape distortion cannot replace this force balance.

An insoluble surfactant is advected with the surface fluid and has no exchange with the bulk. With negligible surface diffusion, its amount on a material surface strip is conserved. Under the small-slope lubrication approximation, surface arclength equals projected horizontal length to leading order, givingThis is the leading planar form of conservation of insoluble surfactant on a moving interface.

Let $y$ measure height above the substrate. The normal-stress and vertical momentum conditions give $p=p_{\mathrm{atm}}-\gamma h_{xx}+\rho g(h-y)$, so $p_x=\rho g{h}_x-(\gamma h_{xx}{)}_x$. Horizontal Stokes flow obeys $\mu u_{yy}=p_x$, with no slip at $y=0$ and Marangoni stress $\mu u_y(h)={\gamma }_x$. ThusUse $h_t+q_x=0$ and ${\gamma }_x=-A{C}_x$ to obtain the thin-film equations with insoluble surfactant:The differing flux coefficients are essential: the surfactant travels at the surface velocity, not at the depth-averaged liquid velocity.

Neglect the two pressure-gradient terms for the spreading outer region. If its half-length is $\ell$, fixed surfactant mass gives $C\sim M/\ell$, $C_x\sim M/{\ell }^2$. The surface velocity is then $u_s\sim AM{h}_0/(\mu {\ell }^2)$. Equating this to $\ell /t$ gives $\ell \propto t^{1/3}$. For the precise finite-mass Marangoni spreading on a liquid film solution choosewith symmetry about zero and support $0\le \eta \le {\eta }_N$ on the positive half-line. The reduced differential equations areTheir boundary conditions are zero flux at the centre and zero concentration at the moving front. The two integral constraints express conserved surfactant mass and zero net change of liquid volume relative to the original uniform layer:The second follows by integrating $h_t+q_x=0$ across the whole layer: the localized release adds surfactant but no liquid, and the flux vanishes at infinity. Outside the spreading region the leading depth remains $h_0$.

Integrating the concentration equation from the centre gives $H\Gamma {\Gamma }^{\prime }=-\eta \Gamma /3$. Where $\Gamma >0$, this is $H{\Gamma }^{\prime }=-\eta /3$. Substituting into the height equation givesTherefore $H=c\eta$, and ${\Gamma }^{\prime }=-1/(3c)$. With $\Gamma ({\eta }_N)=0$, the linear similarity profiles for surfactant spreading are $\Gamma =({\eta }_N-\eta )/(3c)$. The liquid-volume constraint gives $c{\eta }_N=2$, while the surfactant constraint gives ${\eta }_N^2/(3c)=1$. Thus ${\eta }_N^3=6$, andIn physical variables, the leading profiles on the whole line areOutside this interval $h=h_0$ and $C=0$. The formal outer solution reaches zero depth at the central point, and height $2h_0$ immediately inside the front. It is not a microscopic description of the central dry region or of the front transition. As a conservation check, the front velocity equals both the incoming surface velocity and the liquid Rankine–Hugoniot speed $q/(2h_0-h_0)=2AM{h}_0/(\mu x_N^2)={\dot{x}}_N$.

The jump from $2h_0$ to $h_0$ cannot persist as a smooth solution with both hydrostatic and capillary gradients absent. In an edge region of width $\Delta$, a depth change of order $h_0$ produces $h_x\sim h_0/\Delta$ and $h_{xxx}\sim h_0/{\Delta }^3$. Keep the stipulated concentration-gradient scale $M/x_N^2$. The three liquid-flux scales areFor $g=0$, balancing $q_M$ and $q_{\gamma }$ gives the capillary smoothing of a Marangoni front width

Gravity dominates capillarity when $q_g/q_{\gamma }\sim \rho g{\Delta }^2/{\gamma }_0\gg 1$. In physical units the condition is ${\Delta }^2\gg {\gamma }_0/(\rho g)$: the printed ${\gamma }_0/g$ omits density and is dimensionally incomplete unless surface tension has already been divided by density. Balancing the gravity flux with $q_M$ yields the gravity smoothing of a Marangoni front:This layer grows faster than the spreading half-length. It reaches the whole pool whenOnly scaling constants can be fixed by this balance, so an exact numerical coefficient in $t_{\ast }$ is not implied. The gravity-dominant assumption must hold at this crossover as well.

For $t\gg t_{\ast }$, the sharp-front linear-depth outer profile is replaced by a gravity-levelled surfactant film: the height approaches $h_0$, with a small depression under the surfactant and redistributed liquid outside. The rapid hydrostatic return flow almost cancels the net Marangoni liquid flux. Setting $q\simeq 0$ and $h\simeq h_0$ gives $h_x\simeq -3A{C}_x/(2\rho g{h}_0)$ and fractional depth variation $O(AM/(\rho g{h}_0^2{x}_N))\ll 1$. The surface still moves outward, with $u_s\simeq -A{h}_0{C}_x/(4\mu )$, so leveling the bulk liquid does not stop surfactant spreading.

Take pressure positive in compression, outward normal on the upper interface, and curvature $\kappa \simeq -h_{xx}$. The external-minus-internal traction convention gives the base pressure $p_0=V/h_0^3$. For the symmetric Fourier perturbation, the linearized upper-surface conditions areIsotropic base stress cancels all terms due merely to rotating the normal. Velocity $u$ is even and $v$ odd in $y$.

Use the same Papkovich–Neuber representation as in Q1, with $\mathbf{\Phi }=(0,\varphi )$ and symmetric harmonic potentialsSuppress the common exponential. They giveThe zero tangential stress is $A{h}_0\cosh K+B\sinh K=0$, where $K=k{h}_0>0$. Hence $B=-A{h}_0\coth K$, $v(h_0)=A\sinh K/2$ and the normal stress becomes $\mu kA(\cosh K+K/\sinh K)$. Eliminating $A$ using the kinematic condition gives the Van der Waals rupture instability of a viscous sheet rateAttraction destabilizes thickness variations; curvature pressure opposes them.

For the clean-sheet long-wave rupture plateau, writing $s_0=3V/(\mu h_0^3)$, the rate is $s/s_0\to 1/4$. Without capillarity, the curve decreases toward $1/(2K)$ at large $K$; with $\Gamma =1$ it changes sign at $K=1$ and behaves as $-K/2$. Thus short waves are weakly unstable without surface tension, but stabilized by it. The largest clean-sheet rate is approached at long wavelength. The strictly uniform $k=0$ thickness change is not an admissible fixed-volume Fourier mode; this is the limit of nonzero waves. Stress-free surfaces permit extensional, nearly plug-like motion whose mobility compensates the weak long-wave pressure gradient. Unsteady inertia eventually matters in that limit; finite sheet extent, drainage, gravity, surface elasticity/viscosity, surfactant transport and molecular-scale corrections can also modify wavelength selection.

For the comparison with surfactant, keep the same equilibrium tension ${\gamma }_0$. Flow away from a thinning neck stretches the surface, diluting its surfactant and raising tension there. Convergence into thicker regions concentrates surfactant and lowers tension. The resulting Marangoni stress points back toward the neck, opposing the draining surface motion. It therefore reduces mobility and the rupture rate relative to the clean constant-${\gamma }_0$ sheet. This mechanism needs surface transport to sustain concentration gradients; instantaneous concentration equilibration would remove it.

For the supplied strong-surfactant rate, unstable waves satisfy $K<{\Gamma }^{-1/2}$. When $\Gamma \gg 1$, all of them have $K\ll 1$. Expanding its mobility factor givesMaximizing in $K^2$ yields the strong-surfactant long-wave rupture maximumHere $\gamma$ is the equilibrium tension ${\gamma }_0$ in the soap-film comparison. Surface immobilization removes the clean long-wave plateau and selects a finite long wavelength. The growth timescale is lengthened by a factor about $3\Gamma$ compared with the clean maximum. A linear rupture-time estimate is $s_{\max }^{-1}\log (h_0/|{\eta }_{\mathrm{initial}}|)$, not a universal bubble lifetime: drainage and changing thickness, initial defects and nonlinear rupture also matter.

At leading order in the lubrication approximation, surface arclength is horizontal distance. An insoluble surfactant is transported by the surface velocity, without bulk exchange or diffusion. Conservation of insoluble surfactant on a moving interface therefore becomesThe local hydrostatic pressure and capillary normal stress giveSolve $\mu u_{zz}=p_x$ with no-slip boundary condition at $z=0$ and Marangoni stress $\mu u_z(h)={\gamma }_x=-A{C}_x$. The velocity, surface velocity and volume flux per unit width areMass conservation, $h_t+q_x=0$, yields the thin-film equations with insoluble surfactant:and the corresponding surfactant equation isThe hydrostatic and capillary terms thus affect both the film flux and the surface transport, with different coefficients.