During the past thirty years, public interest in handcrafted-soap has led to a resurgence of the small-scale manufacturer: the possibility of creating truly unique bars of soap with various shapes, molds, fragrances, and appearances that attract both entrepreneurs and hobbyist alike <xref linkend="R1"/>. The growing interest in organic alternatives to petroleum based inductrial detergents has also contributed to the handcrafted soap craze. As a result, these soap makers tend to be average people working in small home-kitchen laboratories with tools and ingredients found in a typical American supermarket. Their procedures tend to be adaptations of recipes found in unscientific cookbooks, and their ingredients are typically natural vegetable oils and fragrances. Despite relatively crude tools and procedures however, handcrafted soaps tend to be of extremely high quality and often sell for four or five times that of ready-made soaps and detergents found in one's local grocery store <xref linkend="R1"/>.
<bibliomixed id="R1">Dunn, Kevin M., <citetitle>Scientific Soapmaking. Unpublished Manuscript</citetitle>, July 2006.</bibliomixed>
Discounting or superfatting creates soaps that consist of excess oil. Discounting involves reducing the stoichiometric amount of lye solution added to the saponification mixture, while superfatting involves increasing the stoichiometric amount of oil added to the saponification mixture. The main reason for discounting/superfatting is to have excess oil in the resulting soap which increases the moisturizing or emollient features the soap. One problem which may arise from discounting/superfatting is that it is thought to cause dreaded orange spots (DOS)<xref linkend="R2"/>. Studies investigating this hypothesis have been carried out by Hampden Sydney Students under the supervision of faculty member Dr. Kevin Dunn. The cause of the DOS was attributed to oxidation of the soap from oxygen in the air. This conclusion was reached by conducting several experiments in which various mixtures of the antioxidants Sodium Ascorbate (Vitamin C), TocoPherol, Ethylenediaminetetraacetic acid (EDTA), Butylated Hydroxtoluene (BHT), and Rosemary Extract (ROE) were added to soap samples prior to saponification <xref linkend="R3"/>. The resulting samples were then saponified using the Cold Process method and placed in either pure oxygen or pure nitrogen environments <xref linkend="R3"/>. Subsequent photographic scans were canmducted everyday on each sample and compared using the GNU Manipulation Program (GIMP) <xref linkend="R3"/>. The results concluded that EDTA and ROE were the most effective at preventing DOS <xref linkend="R3"/>.
<bibliomixed id="R2">Dunn, Kevin M., <citetitle>The Journal of the Hand Crafted Soapmakers Guild</citetitle>, Winter 2005/2006.</bibliomixed>
<bibliomixed id="R3">Dieglemann, Stephen R.; Dunn, Kevin M., <citetitle>An Investigation into the Cause and Prevention of Rancidity and Soda Ash in Cold Process Soap. Hampden Sydney College</citetitle>, Spring 2005.</bibliomixed>
The composition of soap also interests soap makers. The process of soap making has remained relatively unchanged since the mid-eighteen hundreds; for the most part, soap consists of a mixture of fatty acids, usually a vegetable oil, and caustic alkali suck as Sodium Hydroxide (Lye) or Potassium Hudroxide: Sodium Hydroxide produces hard or solid soaps while Potassium Hydroxie produces soft or liquid soaps <xref linkend="R4"/>. The saponification process or the process by which these chemicals react to form soap is a delicate process as it requires precise ratiosof the two reactants: excess fatty-acid reduces the soap's ability to produce lather <xref linkend="R4"/>. Nevertheless, soap makers often emply a method known as superfatting or discounting in order to ensure the excess of a particular oil.
<bibliomixed id="R4">Wagner, Rudolph.<citetitle>Soap. Wagner Chemical Technology. Appleton & Company. </citetitle>, 1872, 239-249.</bibliomixed>
Superfatting or discountiong is commonly practiced by soapmakers in an effort to ensure that a particular oil has been reacted completely by using less than the stoichiometric amount of lye that is necessary. However, there is little scientific evidence confirming the effectiveness of this process. Therefore, an analysis of the structure of fatty-acid soap crystals may serve to illustrate how a soap crystal is formed as well as if a particular fatty-acid reacts more readily over another <xref linkend="R5"/>. What is worth noting is that while soap (the salt of the fatty acid) may keep for a long time, oil does not; some chemical change occurs that yields the unsightly orange spots.
<bibliomixed id="R5">Lynch, Matthew L; Wireko, Fred; Tarek, Mournir; Klein, Michael.<citetitle>Intermolecular Interactions and the Structure of Fatty Acid-Soap Crystals. Journal of Physical Chemistry B. </citetitle>, 2000, 552-561.</bibliomixed>