# Surfactant phases

## Colloidal electrolytes - Evidence of a new phase

 Equivalent conductivity at 25 C of undecyl, dodecyl, and tetradecyl sulfonic acid over a wide concentration range. McBain, 1950, Fig. 17.1, p. 243. Deviation of specific conductivity from that for a fully dissociated electrolyte. McBain, 1950, Fig. 17.2, p. 243.
J.W, McBain, 1950ish

## Osmotic coefficient - More evidence of a new phase

 The variation of the osmotic coefficient with concentration for potassium chloride and for potassium laurate. The straight line is the Debye-Huckel-Onsager slope. McBain, 1950, p. 248

## Thermodynamic evidence of a new phase

Solution surface tension versus sodium dodecyl sulfate (SDS) concentration. (Note the logarithmic scale.)

Evans, Fig. 1.1, p. 6

\begin{align}  & d\sigma =-\Gamma _{2}d\mu _{2} \\ & \Gamma _{2}=-\frac{d\sigma }{d\mu _{2}}\simeq -\frac{1}{kT}\left( \frac{d\sigma }{d\ln c_{2}} \right)_{T} \\  \end{align}

The two linear regions represent concentration ranges where the surface excess is constant, but different.

WARNING! - This data may be more interesting than you think.

## Colligative evidence of micelle formation

Morrison, Fig. 13.7

## Micellization - a dynamic equilibrium

• If micellization is an equilibrium reaction:
• $KB\leftrightarrow B_{K}$
• The law of mass action gives:
• $\frac{\left[ B \right]^{K}}{\left[ B_{K} \right]}=\text{constant}$
• The value of K can be quite large; for SDS it is about 64. An equilibrium can look like a phase change (The argument of phase change vs kinetics is an old one largely settle in favor of kinetics.)
• Adsorption at the air/liquid interface and absorption into a micelle are competing processes. However, once the surface is saturated, any addition of surfactant produces more (not usually larger) micelles.

## Inverse micelles

• The lipophilic groups are on the outside, the hydrophilic groups are on the inside.
• Since the hydrophilic groups are typically the salts of strong acids or bases, the core of the inverse micelle is highly polar, somewhat like a room temperature molten salt.
• The micelles are typically large, 10's of nm.

## The Krafft temperature

Evans, Fig. 1.3

Krafft temperature is the temperature at which surfactant solubility equals the critical micelle concentration. Above the Krafft temperature surfactants form micellar dispersions; below the Krafft temperature the surfactant crystallizes out of solution as hydrated crystals. (Evans, Fig. 1.3, p. 9)

## Solubilization

• Simple solvent mixtures do not abruptly change the solubility of another component (see lower curve on the RHS).
• However, surfactants abruptly change the solubility of a component, even a nonsoluble one, above their critical micelle concentration.

 Solubility of 2-nitrodiphenylamine in aqueous solutions of potassium laurate. Solubilization of dye in solutions of Triton X-100 versus solvent action by acetone. Morrison, Fig. 13.14 McBain, 1950, Fig. 17.24, p. 264

## Biosurfactants

Surfactin is a very interesting biosurfactant: it has very impressive surfactant power and is important biologically as an antibiotic.

As an example of its surface active properties, it can lower the water's surface tension from 72 mN/m to 27 mN/m at a concentration as low as 20 µM (from this paper, also cited in Arima K et al., Biochem Biophys Res Commun 1968, 31, 488). This can be compared to SDS, a very common surfactant, that typically reduced water's surface tension from 72 mN/m to 40 mN/m.

This is an interesting piece from the Biophysical Journal on the how it interacts with synthesized membranes (which explains more physically how the antimicrobial properties come about and how it enters all types of cells indiscriminately cells): Interactions of surfactin with membrane models

And this one shows a way to study the interfacial tension of a biological surfactant: Molecular Dynamics Simulation of Surfactin Molecules at the Water-Hexane Interface

--BPappas 16:47, 30 October 2008 (UTC)

Biologically interesting functions can be immobilized by attaching the (hydrophilic) moiety to a hydrocarbon chain and making it surface active. For example:

 DNA surfactant immobilized via its hydrophobic tails. Its DNA head strand is capable of binding to its complementary strand tagged with a rhodamine fluorescence label). Lu et al. Current Contents in Colloid & Interface Sci, 12, 60, 2008.

## Particles as surfactants

Binks, Current Contents in Colloid & Interface Sci., 21, 68, 2002.

An analysis of the interfacial energy required to remove a partially partially wetted particle into either the oil or water phases (contact angle measured through the water phase) give the following two equations:

\begin{align}  & \Delta F_{1}=\pi r^{2}\sigma _{12}\left( 1-\cos \theta \right)^{2} \\ & \Delta F_{2}=\pi r^{2}\sigma _{12}\left( 1+\cos \theta \right)^{2} \\  \end{align}

 Calculated for a 10 nm radius particle at the O/W interface with an interfacial tension of 36 mN/m. Contact angle measured through the oil phase. Morrison, Fig. 22.4

## "Typical" soap phase diagram

 Phase diagram for sodium stearate-water. McBain, 1950, Fig. 17.23, p. 263. “Soaps are remarkable in that their aqueous solutions, depending upon the temperature and concentration, exist as different phases, some being ordinary isotropic, clear, transparent, fluid solutions, colloidal except in extreme dilution; and other being liquid crystalline, anisotropic, plastic, and translucent. Among the latter are middle soap, soap boiler’s neat soap, superneat, superwaxy, subneat, and neat soap phases..”

## Surfactant self assembly

When concentrations of surfactants reach critical levels, several unusual properties are observed that indicated that changes have occurred in the liquid's structure. Above a critical concentration, which varies depending on the surfactant, the osmotic pressure and surface tension remain constant while self-diffusion decreases and light-scattering increases. These observations are consistent with a transition from single surfactants to organized structure of the surfactants.

This self-assembly in surfactant micelles leads to a variety of different structures. These are nicely described in a picture in the lecture. Initially, surfactants gather in micelles with the non-polar portion directed towards the center (assuming we are discussing an aqueous solution). Many of these structures are studied in water because it is the most effective solvent to use for observing their formation.

Have these structures ever been directly observed? Is there any experimental evidence for bicontinous structure? From a quick literature search, it seems that they are only found in simulations.

source: Holmberg et al.

 (a) Spherical micelles with an interior composed of the hydrocarbon chains and a surface of the polar head groups (pictured as spheres) facing water. (b) Cylindrical micelles with an interior composed of the hydrocarbon chain and a surface of the polar head groups facing water. The cross-section of the hydrocarbon core is similar to that of micelles. The micellar length is highly variable so these micelles are polydisperse. (c) Surfactant bilayers which build up lamellar liquid crystals have for surfactant-water systems a hydrocarbon core with a thickness of ca. 80% of the length of two extended alkyl chains. (d) Reverse or inverted micelles have a water core surrounded by the surfactant polar head groups. (e) A bicontinuous structure with the surfactant molecules aggregated into connected films characterized by two curvatures of opposite sign. (f) Vesicles are build from bilayers similar to those of the lamellar phase and are characterized by two distinct water compartments.(Description from Holmberg et al. Fig. 2.1, p. 40; Diagrams from Evans et al., Fig. 1.6, pp 14-15).

## Kinetics in surfactant systems

• Transitions can be between all phases.
• Molecule entering micelles - microseconds
• Micelles to molecules - order of a minute.
• Micelles to vesicles – order of hours
Gradzielski, Current Contents in Colloid & Interface Sci, 8, 337, 2003.

## 3 Component Surfactant phase diagrams

 Morrison, Fig. 13.21, p. 272. Phase diagram of the E100P70E100–butanol–water system at 25oC. The tie-lines are represented by full straight lines. L1 denotes the water-rich (micellar) solutions region, I1 the normal (“oil”-in-water) micellar cubic liquid crystalline region, H1 the normal hexagonal liquid crystalline region, Lalpha the lamellar liquid crystalline region, and L2 the alkanol-rich solution region.

## Liquid crystal phases

 Chiral – having a mirror image. Sometimes causes neighboring molecules to align at a slight angle, leading to a helix in space with a well-defined pitch much longer that the size of a molecule. And can form chiral nematic phases. Smetic A – director is parallel to the layer normal Smetic C – director makes an angle to the layer normal (that is, layers of tilted molecules) Columnar (or discotic) – Molecules form disk-like phases.

Phase Positional order Orientational order
Liquid None None
Nematic None Yes
Smectic One-dimensional Yes
Columnar Two-dimensional Yes
Crystalline Three-dimensional Yes

## Critical packing shapes

 $\frac{v}{a_{0}l_{c}}$ where $\nu$ is the volume of the micelle, $a_{0}$ is the optimum area for the head groups and $l_{c}$ is the critical chain length. $M=\frac{4\pi l_{c}^{3}}{3v}$ $l_{c}$ is a length approximately the extension of the hydrocarbon before it loses a liquid-like state, and M is the mean aggregation number.
Israelachvili, 1991, p. 381

Holmberg p. 278

## Surfactant - Protein interactions

Missing reference!!!!

• The effect of gelatin on the surface tension of solutions of SDS (circles) and Triton-X100 (triangles). Without gelatin (filled) and with gelatin (open).
• For Triton X-100: no protein/surfactant interaction.
• For SDS: a plateau corresponding to a protein/surfactant association.

## Biogenic monolayers - Lung surfactant

Surface tension is greatly reduced by compression on exhaled breath, regulating capillary pressure, promoting involuntary inhaling. Premature babies lack lung surfactant. The layers are strong – maximum spreading pressures of 68-72 mN/m compared to stearic acid of about 40 mN/m. The collapsed films relax slowly on expansion.

 Fluorescence microscopy a monolayer of phospholipids containing Rh-DPPC at different surface pressures (in units of nMm-1) during continuous compression at 0.03 nm2 per molecule-min. The non-fluorescent area correspond liquid condensed domains, fluorescent areas correspond to liquid expanded domains. Highly fluorescent spots are collapsed structures.* Engelskirchen. Current Contents in Colloid & Interface Sci, 12, 68, 2008.