A food manufacturer must consider a variety of factors when selecting a surfactant for a particular product, including its legal status as a food ingredient; its cost; the reliability of the supplier; the consistency of its quality from batch to batch; its ease of handling and dispersion; its shelf life; its compatibility with other ingredients; the processing, storage, and handling conditions it will experience; and the expected shelf life and physicochemical properties of the final product. How does a food manufacturer decide which surfactant is most suitable for a product? There have been various attempts to develop systems to classify surfactants according to their physicochemical properties. Classification schemes have been developed which are based on a surfactant's solubility in oil and/or water (Bancroft's rule), its ratio of hydrophilic to lipophilic groups (HLB number), and its molecular geometry (Davis 1994b, Dickinson and McClements 1995, Bergenstahl 1997). Ultimately, all of these properties depend on the chemical structure of the surfactant, and so the different classification schemes are closely related.
188.8.131.52. Bancroft's Rule
One of the first empirical rules developed to describe the type of emulsion that could be stabilized by a given surfactant was proposed by Bancroft (Davis 1996). Bancroft's rule states that the phase in which the surfactant is most soluble will form the continuous phase of an emulsion. Hence a water-soluble surfactant should stabilize oil-in-water emulsions, whereas an oil-soluble surfactant should stabilize water-in-oil emulsions. This rule is applicable to a wide range of surfactants, although there are many important exceptions. For example, many amphiphilic molecules are highly soluble in either one phase or the other, but do not form stable emulsions because they are not particularly surface active or do not protect droplets against aggregation. Bancroft's rule is a useful empirical method for classifying surfactants; however, it provides little insight into the relationship between the molecular structure of a surfactant and its ability to form or stabilize emulsions.
The hydrophile-lipophile balance (HLB) concept is a semiempirical method which is widely used for classifying surfactants. The HLB is described by a number which gives an indication of the relative affinity of a surfactant molecule for the oil and aqueous phases (Davis 1994b). Each surfactant is assigned an HLB number according to its chemical structure. A molecule with a high HLB number has a high ratio of hydrophilic groups to lipophilic groups and vice versa. The HLB number of a surfactant can be calculated from a knowledge of the number and type of hydrophilic and lipophilic groups it contains, or it can be estimated from experimental measurements of its cloud point (Shinoda and Friberg 1986). The HLB numbers of many surfactants have been tabulated in the literature (Shinoda and Kunieda 1983; Becher 1985, 1996). A widely used semiempirical method for calculating the HLB number of a surfactant is as follows (Davis 1994b):
HLB = 7 + £ (hydrophilic group numbers) ± £ (lipophilic group numbers) (4.8)
Group numbers have been assigned to many different types of hydrophilic and lipophilic groups (Table 4.6). The sums of the group numbers of all the lipophilic groups and of all the hydrophilic groups are substituted into Equation 4.8 and the HLB number is calculated. Despite originally being developed as a semiempirical equation, Equation 4.8 has been shown to have a thermodynamic basis, with the sums corresponding to the free energy changes in the hydrophilic and lipophilic parts of the molecule when micelles are formed (Becher 1985).
The HLB number of a surfactant gives a useful indication of its solubility in either the oil and/or water phase and can be used to predict the type of emulsion that will be formed (Davis 1994b). A surfactant with a low HLB number (3 to 6) is predominantly hydrophobic, dissolves preferentially in oil, stabilizes water-in-oil emulsions, and forms reverse micelles in oil. A surfactant with a high HLB number (8 to 18) is predominantly hydrophilic, dissolves preferentially in water, stabilizes oil-in-water emulsions, and forms micelles in water. A surfactant with an intermediate HLB number (6 to 8) has no particular preference for either oil or water. Molecules with HLB numbers below 3 and above 18 are not particularly surface active and tend to accumulate preferentially in bulk oil or aqueous phases, rather than at an oil-water interface. Emulsion droplets are particularly prone to coalescence when they are stabilized by surfactants that have extreme or intermediate HLB numbers. At very high or low HLB numbers, a surfactant has such a low surface activity that it does not accumulate appreciably at the droplet surface and therefore does not provide protection against coalescence. At intermediate HLB numbers (6 to 8), emulsions are unstable to coalescence because the interfacial tension is so low that very little energy is required to disrupt the membrane. Maximum stability of emulsions is obtained for oil-in-water emulsions using surfactants with an HLB number around 10 to 12 and for water-in-oil emulsions around 3 to 5. This is because the surfactants are surface active but do not lower the interfacial tension so much that the droplets are easily disrupted. It is possible to adjust the effective HLB number by using a combination of two or more surfactants with different HLB numbers (Becher 1957).
One of the major drawbacks of the HLB concept is that it does not take into account the fact that the functional properties of a surfactant molecule are altered significantly by changes in temperature or solution conditions (Davis 1994b). Thus a surfactant may be capable of stabilizing oil-in-water emulsions at one temperature but water-in-oil emulsions at another temperature, even though it has exactly the same chemical structure. The HLB concept could be extended to include temperature effects by determining the group numbers as a function of temperature, although this would be a rather tedious and time-consuming task.
184.108.40.206. Molecular Geometry and the Phase Inversion Temperature
The molecular geometry of a surfactant molecule can be described by a packing parameter, (p) (Israelachvili 1992, 1994; Kabalnov and Wennerstrom 1996):
where v and l are the volume and length of the hydrophobic tail and a0 is the cross-sectional area of the hydrophilic head group (Figure 4.14). When surfactant molecules associate with each other, they tend to form monolayers that have a curvature which allows the most efficient packing of the molecules. At this optimum curvature, the monolayer has its lowest free energy, and any deviation from this curvature requires the expenditure of energy. The optimum curvature (H0) of a monolayer depends on the packing parameter of the surfactant: for p = 1, monolayers with zero curvature (H0 = 0) are preferred; for p < 1, the optimum curvature is convex (H0 < 0); and for p > 1, the optimum curvature is concave (H0 > 0) (Figure 4.14). Simple geometrical considerations indicate that spherical micelles are formed when p is less than one-third, nonspherical micelles when p is between one-third and one-half, and bilayers when p is between one-half and one (Israelachvili 1992, 1994). Above a certain concentration, bilayers join up to form vesicles because energetically unfavorable end effects can be eliminated. At values of p greater than 1, reverse micelles are formed, in which the hydrophilic head groups are located in the interior (away from the oil) and the hydrophobic tail groups are located at the exterior (in contact with the oil) (Figure 4.14). The packing parameter therefore gives a useful indication of the type of association colloid that a surfactant molecule forms in solution.
The packing parameter is also useful because it accounts for the temperature dependence of the physicochemical properties of surfactant solutions and of emulsions (Kabalnov and Wennerstrom 1996). The temperature at which a surfactant solution converts from a micellar to a reverse-micellar system or an oil-in-water emulsion changes to a water-in-oil emulsion
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