In colloidal and surface chemistry, the critical micelle concentration (CMC) is defined as the concentration of surfactants above which micelles form and all additional surfactants added to the system will form micelles. [1]
The CMC is an important characteristic of a surfactant. Before reaching the CMC, the surface tension changes strongly with the concentration of the surfactant. After reaching the CMC, the surface tension remains relatively constant or changes with a lower slope. The value of the CMC for a given dispersant in a given medium depends on temperature, pressure, and (sometimes strongly) on the presence and concentration of other surface active substances and electrolytes. Micelles only form above critical micelle temperature.
For example, the value of CMC for sodium dodecyl sulfate in water (without other additives or salts) at 25 °C, atmospheric pressure, is 8x10−3 mol/L. [2]
Surfactant | CMC (molarity) | Category |
---|---|---|
Sodium octyl sulfate | 0.13 | anionic surfactant |
Sodium dodecyl sulfate | 0.0083 | anionic surfactant |
Sodium tetradecyl sulfate | 0.0021 | anionic surfactant |
Decyltrimethylammonium bromide | 0.065 | cationic surfactant |
Dodecyltrimethylammonium bromide | 0.016 | cationic surfactant |
Hexadecyltrimethylammonium bromide | 0.00092 | cationic surfactant |
Penta(ethyleneglycol)monooctyl ether | 0.0009 | neutral surfactant |
Penta(ethyleneglycol)monodecyl ether | 0.0009 | neutral surfactant |
Penta(ethyleneglycol)monododecyl ether | 0.000065 | neutral surfactant |
Upon introducing surfactants (or any surface active materials) into a system, they will initially partition into the interface, reducing the system free energy by:
Subsequently, when the surface coverage by the surfactants increases, the surface free energy (surface tension) decreases and the surfactants start aggregating into micelles, thus again decreasing the system's free energy by decreasing the contact area of hydrophobic parts of the surfactant with water. [4] Upon reaching CMC, any further addition of surfactants will just increase the number of micelles (in the ideal case).
According to one well-known definition, CMC is the total concentration of surfactants under the conditions: [5]
The CMC generally depends on the method of measuring the samples, since A and B depend on the properties of the solution such as conductance, photochemical characteristics or surface tension. When the degree of aggregation is monodisperse, then the CMC is not related to the method of measurement. On the other hand, when the degree of aggregation is polydisperse, then CMC is related to both the method of measurement and the dispersion.
The common procedure to determine the CMC from experimental data is to look for the intersection (inflection point) of two straight lines traced through plots of the measured property versus the surfactant concentration. This visual data analysis method is highly subjective and can lead to very different CMC values depending on the type of representation, the quality of the data and the chosen interval around the CMC. [6] A preferred method is the fit of the experimental data with a model of the measured property. Fit functions for properties such as electrical conductivity, surface tension, NMR chemical shifts, absorption, self-diffusion coefficients, fluorescence intensity and mean translational diffusion coefficient of fluorescent dyes in surfactant solutions have been presented. [7] [8] [9] These fit functions are based on a model for the concentrations of monomeric and micellised surfactants in solution, which establishes a well-defined analytical definition of the CMC, independent from the technique.
The CMC is the concentration of surfactants in the bulk at which micelles start forming. The word bulk is important because surfactants partition between the bulk and interface and CMC is independent of interface and is therefore a characteristic of the surfactant molecule. In most situations, such as surface tension measurements or conductivity measurements, the amount of surfactant at the interface is negligible compared to that in the bulk and CMC can be approximated by the total concentration. In practice, CMC data is usually collected using laboratory instruments which allow the process to be partially automated, for instance by using specialised tensiometers.
When the interfacial areas are large, the amount of surfactant at the interface cannot be neglected. If, for example, air bubbles are introduced into a solution of a surfactant above CMC, these bubbles, as they rise to the surface, remove surfactants from the bulk to the top of the solution creating a foam column and thus reducing the concentration in bulk to below CMC. This is one of the easiest methods to remove surfactants from effluents (see foam flotation). Thus in foams with sufficient interfacial area are devoid of micelles. Similar reasoning holds for emulsions.
The other situation arises in detergents. One initially starts off with concentrations greater than CMC in water and on adding fabric with large interfacial area, the surfactant concentration drops below CMC and no micelles remain at equilibrium. Therefore, the solubilization plays a minor role in detergents. Removal of oily soil occurs by modification of the contact angles and release of oil in the form of emulsion.
In petroleum industry, CMC is considered prior to injecting surfactant in reservoir regarding enhanced oil recovery (EOR) application. Below the CMC point, interfacial tension between oil and water phase is no longer effectively reduced. [10] If the concentration of the surfactant is kept a little above the CMC, the additional amount covers the dissolution with existing brine in the reservoir. It is desired that the surfactant will work at the lowest interfacial tension (IFT).
A detergent is a surfactant or a mixture of surfactants with cleansing properties when in dilute solutions. There are a large variety of detergents, a common family being the alkylbenzene sulfonates, which are soap-like compounds that are more soluble in hard water, because the polar sulfonate is less likely than the polar carboxylate to bind to calcium and other ions found in hard water.
Surfactants are chemical compounds that decrease the surface tension or interfacial tension between two liquids, a liquid and a gas, or a liquid and a solid. Surfactants may function as emulsifiers, wetting agents, detergents, foaming agents, or dispersants. The word "surfactant" is a blend of surface-active agent, coined c. 1950.
A micelle or micella is an aggregate of surfactant amphipathic lipid molecules dispersed in a liquid, forming a colloidal suspension. A typical micelle in water forms an aggregate with the hydrophilic "head" regions in contact with surrounding solvent, sequestering the hydrophobic single-tail regions in the micelle centre.
Ammonium lauryl sulfate (ALS) is the common name for ammonium dodecyl sulfate (CH3(CH2)10CH2OSO3NH4). The anion consists of a nonpolar hydrocarbon chain and a polar sulfate end group. The combination of nonpolar and polar groups confers surfactant properties to the anion: it facilitates dissolution of both polar and non-polar materials. This salt is classified as a sulfate ester. It is made from coconut or palm kernel oil for use primarily in shampoos and body-wash as a foaming agent. Lauryl sulfates are very high-foam surfactants that disrupt the surface tension of water in part by forming micelles at the surface-air interface.
Micellar electrokinetic chromatography (MEKC) is a chromatography technique used in analytical chemistry. It is a modification of capillary electrophoresis (CE), extending its functionality to neutral analytes, where the samples are separated by differential partitioning between micelles and a surrounding aqueous buffer solution.
Surfactin is a cyclic lipopeptide, commonly used as an antibiotic for its capacity as a surfactant. It is an amphiphile capable of withstanding hydrophilic and hydrophobic environments. The Gram-positive bacterial species Bacillus subtilis produces surfactin for its antibiotic effects against competitors. Surfactin showcases antibacterial, antiviral, antifungal, and hemolytic effects.
A hydrotrope is a compound that solubilizes hydrophobic compounds in aqueous solutions by means other than micellar solubilization. Typically, hydrotropes consist of a hydrophilic part and a hydrophobic part, but the hydrophobic part is generally too small to cause spontaneous self-aggregation. Hydrotropes do not have a critical concentration above which self-aggregation spontaneously starts to occur. Instead, some hydrotropes aggregate in a step-wise self-aggregation process, gradually increasing aggregation size. However, many hydrotropes do not seem to self-aggregate at all, unless a solubilizate has been added. Examples of hydrotropes include urea, tosylate, cumenesulfonate and xylenesulfonate.
Micellar liquid chromatography (MLC) is a form of reversed phase liquid chromatography that uses an aqueous micellar solutions as the mobile phase.
Lyotropic liquid crystals result when fat-loving and water-loving chemical compounds known as amphiphiles dissolve into a solution that behaves both like a liquid and a solid crystal. This liquid crystalline mesophase includes everyday mixtures like soap and water.
Surface conductivity is an additional conductivity of an electrolyte in the vicinity of the charged interfaces. Surface and volume conductivity of liquids correspond to the electrically driven motion of ions in an electric field. A layer of counter ions of the opposite polarity to the surface charge exists close to the interface. It is formed due to attraction of counter-ions by the surface charges. This layer of higher ionic concentration is a part of the interfacial double layer. The concentration of the ions in this layer is higher as compared to the ionic strength of the liquid bulk. This leads to the higher electric conductivity of this layer.
Octyl glucoside is a nonionic surfactant frequently used to solubilise integral membrane proteins for studies in biochemistry. Structurally, it is a glycoside derived from glucose and octanol. Like Genapol X-100 and Triton X-100, it is a nonphysiological amphiphile that makes lipid bilayers less "stiff".
Lauryldimethylamine oxide (LDAO), also known as dodecyldimethylamine oxide (DDAO), is an amine oxide–based nonionic surfactant, with a C12 (dodecyl) alkyl tail. It is one of the most frequently-used surfactants of this type. Like other amine oxide–based surfactants it is antimicrobial, being effective against common bacteria such as S. aureus and E. coli, however, it is also non-denaturing and may be used to solubilize proteins.
Micellar solubilization (solubilization) is the process of incorporating the solubilizate into or onto micelles. Solubilization may occur in a system consisting of a solvent, an association colloid, and at least one other solubilizate.
Macroemulsions are dispersed liquid-liquid, thermodynamically unstable systems with particle sizes ranging from 1 to 100 μm, which, most often, do not form spontaneously. Macroemulsions scatter light effectively and therefore appear milky, because their droplets are greater than a wavelength of light. They are part of a larger family of emulsions along with miniemulsions. As with all emulsions, one phase serves as the dispersing agent. It is often called the continuous or outer phase. The remaining phase(s) are disperse or inner phase(s), because the liquid droplets are finely distributed amongst the larger continuous phase droplets. This type of emulsion is thermodynamically unstable, but can be stabilized for a period of time with applications of kinetic energy. Surfactants are used to reduce the interfacial tension between the two phases, and induce macroemulsion stability for a useful amount of time. Emulsions can be stabilized otherwise with polymers, solid particles or proteins.
Continuous foam separation is a chemical process closely related to foam fractionation in which foam is used to separate components of a solution when they differ in surface activity. In any solution, surface active components tend to adsorb to gas-liquid interfaces while surface inactive components stay within the bulk solution. When a solution is foamed, the most surface active components collect in the foam and the foam can be easily extracted. This process is commonly used in large-scale projects such as water waste treatment due to a continuous gas flow in the solution.
In colloidal chemistry, the critical micelle concentration (CMC) of a surfactant is one of the parameters in the Gibbs free energy of micellization. The concentration at which the monomeric surfactants self-assemble into thermodynamically stable aggregates is the CMC. The Krafft temperature of a surfactant is the lowest temperature required for micellization to take place. There are many parameters that affect the CMC. The interaction between the hydrophilic heads and the hydrophobic tails play a part, as well as the concentration of salt within the solution and surfactants.
Dominique Langevin is a French researcher in physical chemistry. She is research director at the Centre national de la recherche scientifique and leads the liquid interface group in the Laboratory of Solid State Physics at the University of Paris-Sud. She was the Life and Physical Sciences Panel chair for the European Space Sciences Committee of the European Science Foundation from 2013-2021.
Interfacial rheology is a branch of rheology that studies the flow of matter at the interface between a gas and a liquid or at the interface between two immiscible liquids. The measurement is done while having surfactants, nanoparticles or other surface active compounds present at the interface. Unlike in bulk rheology, the deformation of the bulk phase is not of interest in interfacial rheology and its effect is aimed to be minimized. Instead, the flow of the surface active compounds is of interest..
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Emmie Helena Lucassen-Reynders was a Dutch scientist specialising in colloid chemistry and theoretical physics. She worked in both academia and in industry.