Surface tension with a surfactant
How far does this much surfactant lower the water's surface tension, and is it past the point of doing any more?
- γ
- Surface tension, N/m
- γ0
- Clean surface tension, N/m
- a
- Thermal-adsorption scale, RTΓ, N/m
- K
- Adsorption constant, L/mol
- c
- Concentration, mol/L
- Γ
- Surface excess at saturation, mol/m²
LaTeX
γ = γ0 - a \cdot \ln\left(1 + K \cdot c\right), \qquad a = R \cdot T \cdot Γ
Method
- Convert the temperature to kelvin and the surface excess to moles per square metre. Multiply the gas constant R (8.314 J/mol·K) by both: this is the scale a, in newtons per metre, that sets how much surface tension one "e-fold" of surfactant removes. For SDS at 20 °C it is about 8 mN/m.
- Convert the concentration to moles per litre and multiply by the adsorption constant K; add one and take the natural log. This is the Langmuir isotherm's coverage term — how full the surface is at this concentration.
- Multiply the scale by that log and subtract from the clean surface tension. That is Szyszkowski's equation, and it holds up to the critical micelle concentration.
- Past the CMC, use the CMC's concentration instead: the surface is as full as it gets, further surfactant goes into micelles in the bulk, and the surface tension stays flat.
Assumptions
- A single, pure surfactant in a clean carrier, adsorbing by a Langmuir isotherm. Mixed or impure surfactants, and any oil or salt in the water, change both Γ and K.
- The defaults are SDS's, and K in particular is a fit, not a measurement: it is chosen so the curve passes through water's 72.8 mN/m and the roughly 38 mN/m every reference gives for SDS at its 8.2 mM CMC. Other surfactants need their own Γ, K and CMC — the shape of the curve is general, the numbers are not.
- The sharp corner at the CMC is an idealisation. Real curves round off over a factor of two or so in concentration either side of it.
- This is the surface tension against air. What keeps a particulate dispersed is the surfactant at the particle–liquid interface, a related but different adsorption; the air–water curve is the measurable proxy for how much surfactant is active, not the dispersing force itself.
- Nothing here is Meyer's — the estate material does not name a surfactant or, so far as the archive holds, mention one. The calculation exists because a slurry of metal in water needs one to stay a slurry.