Learning Objectives After completing this section, you should be able to write an equation to represent the formation of a soap. identify the structure of the fat required to produce a given soap. identify the structure of a soap, given the structure of the fat from which it is produced. describe the mechanism by which soaps exert their cleansing action. give a chemical explanation of the problems encountered when carboxylate soaps are used in hard‑water areas, and explain how they may be overcome by the use of sulphonate detergents. Key Terms Make certain that you can define, and use in context, the key terms below. hydrophilic lipophilic (hydrophobic) amphiphilic micelles Soap making has remained unchanged over the centuries. The ancient Roman tradition called for mixing rain water, potash and animal tallow (rendered form of beef or mutton fat). Making soap was a long and arduous process. First, the fat had to be rendered (melted and filtered). Then, potash solution was added. Since water and oil do not mix, this mixture had to be continuously stirred and heated sufficiently to keep the fat melted. Slowly, a chemical reaction called saponification would take place between the fat and the hydroxide which resulted in a liquid soap. When the fat and water no longer separated, the mixture was allowed to cool. At this point salt, such as sodium chloride, was added to separate the soap from the excess water. The soap came to the top, was skimmed off, and placed in wooden molds to cure. It was aged many months to allow the reaction to run to completion. All soap is made from fats and oils, mixed with alkaline (basic) solutions. There are many kinds of fats and oils, both animal and vegetable. As previously discussed, fats are usually solid at room temperature, but many oils are liquid at room temperature. Liquid cooking oils originate from corn, peanuts, olives, soybeans, and many other plants. For making soap, all different types of fats and oils can be used – anything from lard to exotic tropical plant oils. Carboxylic acids and salts having alkyl chains longer than eight carbons exhibit unusual behavior in water due to the presence of both hydrophilic (CO 2 ) and hydrophobic (alkyl) regions in the same molecule. Such molecules are termed amphiphilic (Gk. amphi = both) or amphipathic . Fatty acids made up of ten or more carbon atoms are nearly insoluble in water, and because of their lower density, float on the surface when mixed with water. Unlike paraffin or other alkanes, which tend to puddle on the waters surface, these fatty acids spread evenly over an extended water surface, eventually forming a monomolecular layer in which the polar carboxyl groups are hydrogen bonded at the water interface, and the hydrocarbon chains are aligned together away from the water. This behavior is illustrated in the diagram on the right. Substances that accumulate at water surfaces and change the surface properties are called surfactants . Alkali metal salts of fatty acids are more soluble in water than the acids themselves, and the amphiphilic character of these substances also make them strong surfactants. The most common examples of such compounds are soaps and detergents, four of which are shown below. Note that each of these molecules has a nonpolar hydrocarbon chain, the "tail", and a polar (often ionic) "head group". The use of such compounds as cleaning agents is facilitated by their surfactant character, which lowers the surface tension of water, allowing it to penetrate and wet a variety of materials. When minute amounts of soaps are put into water, instead of forming simple solutions, the molecules become concentrated at the surface of the water, with the saltlike ends sticking down into the water and the hydrocarbon chains forming a layer on the surface. This arrangement greatly reduces the surface tension of the water and contributes to the startling properties of soap films and bubbles. At higher concentrations, the solutions become turbid as the result of micelle formation. Micelles are spherical aggregates of soap molecules, wherein the hydrocarbon chains form a region of low polarity that is stabilized by having the polar salt ends of the molecules in contact with the water. By gathering the hydrophobic chains together in the center of the micelle, disruption of the hydrogen bonded structure of liquid water is minimized, and the polar head groups extend into the surrounding water where they participate in hydrogen bonding. The importance of soap to human civilization is documented by history, but some problems associated with its use have been recognized. One of these is caused by the weak acidity (pKa ca. 4.9) of the fatty acids. Solutions of alkali metal soaps are slightly alkaline (pH 8 to 9) due to hydrolysis. If the pH of a soap solution is lowered by acidic contaminants, insoluble fatty acids precipitate and form a scum. A second problem soaps are less effective in hard water, which is water that contains a significant concentration of magnesium, calcium and iron ions. These ions form precipitates with soap molecules, and this precipitate is often seen as a gray line on a bathtub or sink and is often called “soap scum”. Since soap forms a precipitate with these ions, it means that many of the soap molecules are no longer present in the solution. Therefore, soap will form fewer suds in hard water. “Soft water” is water that contains very few or no ions that precipitate with soap. Soap will therefore be much more effective in soft water than in hard water. These problems have been alleviated by the development of synthetic soaps called detergents. Detergents are similar to soaps in that they have a charged head group and a long nonpolar tail group, but they are not prepared from natural fats or oils. Detergents are useful because they do not form precipitates with magnesium, iron or calcium ions, which means that they work in both soft and hard water. By using a much stronger acid for the polar head group, water solutions of detergents are less sensitive to pH changes. Also the sulfonate functions used for virtually all anionic detergents confer greater solubility on micelles incorporating the alkaline earth cations found in hard water. Variations on the detergent theme have led to the development of other classes, such as the cationic and nonionic detergents shown above. Cationic detergents often exhibit germicidal properties, and their ability to change surface pH has made them useful as fabric softeners and hair conditioners. These versatile chemical "tools" have dramatically transformed the household and personal care cleaning product markets over the past fifty years Sodium Lauryl Sulfate (a non-biodegradable detergent) After detergents started being widely used, it was discovered that they were not broken down in sewage treatment plants. Many streams and lakes became contaminated with detergents and large amounts of foam appeared in natural waters. Biodegradable detergents were then developed. Shown below is an example of a biodegradable detergent, sodium laurylbenzenesulfonate. Sodium Laurylbenzenesulfonate (a biodegradable detergent) Exercise \(\PageIndex{1}\) Explain how soaps or surfactants decrease the surface tension of a liquid. How does the meniscus of an aqueous solution in a capillary change if a surfactant is added? Illustrate your answer with a diagram. Answer Adding a soap or a surfactant to water disrupts the attractive intermolecular interactions between water molecules, thereby decreasing the surface tension. Because water is a polar molecule, one would expect that a soap or a surfactant would also disrupt the attractive interactions responsible for adhesion of water to the surface of a glass capillary. As shown in the sketch, this would decrease the height of the water column inside the capillary, as well as making the meniscus less concave. Exercise \(\PageIndex{2}\) Draw the structure of calcium stearate, a component of soap scum. Answer (C 17 H 35 COO) 2 Ca 2 +