Laurate soaps

It is important to point out that our investigation of counterion effects in carboxylate soaps has so far been concerned almost exclusively with laurate soaps. Laurate soaps were chosen partly because they are generally convenient to handle in that many of them are readily soluble in water to give solutions of low viscosity, and partly because, as has been shown above, laurate soaps are very effective in enhancing the mechanical and chemical stability of natural rubber latex. It must therefore be borne in mind that the conclusions which have been drawn from this investigation concerning effects attributable to counterion variation in laurate soaps may not be generally valid for carboxylate soaps as a family. 

Table II Effects of added laurate soaps of various counterions upon mechanical stability of natural rubber latex (5)...

FIGURE 31.3 Swelling of porcine skin SC in sodium cocoyl isethionate (SCI, syndet) and Na laurate (soap) solutions (l%wt). Soap treated SC shows significantly higher swelling than that treated with syndet. 

Contrarily to fatty add salts (i.e., sodium laurate soap), the long-chain iV -acyl amino adds have excellent water solubility (due to the presence of additional CO-NH linkages), quick biodegradability and good lime resistance (i.e., caldum ion tolerance) [11]. The surfactant properties of pure sodium salts of iV -acyl amino acids (anionic surfactants) with different alkyl chains (saturated and unsaturated with 10-18 carbon atoms) and amino acid residues have been described and compared with those of sodium lauryl sulfate (SLS) and sodium laurate [11-14]. The authors showed that the critical micelle concentration (CMQ of the amino acid-based surfactants was lower than that of the SLS but higher than that of sodium laurate. The surface activity increased and the CMC decreased by raising the alkyl chain... 

Typically, soHd stabilizers utilize natural saturated fatty acid ligands with chain lengths of Cg—C g. Ziac stearate [557-05-1/, ziac neodecanoate [27253-29-8] calcium stearate [1592-23-0] barium stearate [6865-35-6] and cadmium laurate [2605-44-9] are some examples. To complete the package, the soHd products also contain other soHd additives such as polyols, antioxidants, and lubricants. Liquid stabilizers can make use of metal soaps of oleic acid, tall oil acids, 2-ethyl-hexanoic acid, octylphenol, and nonylphenol. Barium bis(nonylphenate) [41157-58-8] ziac 2-ethyIhexanoate [136-53-8], cadmium 2-ethyIhexanoate [2420-98-6], and overbased barium tallate [68855-79-8] are normally used ia the Hquid formulations along with solubilizers such as plasticizers, phosphites, and/or epoxidized oils. The majority of the Hquid barium—cadmium formulations rely on barium nonylphenate as the source of that metal. There are even some mixed metal stabilizers suppHed as pastes. The U.S. FDA approved calcium—zinc stabilizers are good examples because they contain a mixture of calcium stearate and ziac stearate suspended ia epoxidized soya oil. Table 4 shows examples of typical mixed metal stabilizers. 

Amphiphilic Molecules. In just about all cases of lyotropic Hquid crystals, the important component of the system is a molecule with two very different parts, one that is hydrophobic and one that is hydrophilic. These molecules are called amphiphilic because when possible they migrate to the iaterface between a polar and nonpolar Hquid. Soaps such as sodium laurate and phosphoHpids such as a-cephalin [5681-36-7] (phosphatidylethanolamine) (2) are important examples of amphiphilic molecules which form Hquid crystal phases (see Lecithin Soap). 

The sohd soaps are prepared from cadmium chloride solution by precipitation with sodium salts of the fatty acids. Cadmium laurate [2605-44-9] Cd(C22H2402)2, cadmium stearate [2223-93-0] cadmium palmitate [6427-86-7] and cadmium myristate [10196-67-5] ... 

Fig. 28.—Polymerization of isoprene in emulsion at 50°C using 0.3 g of K2S2O8 per 100 g. of monomer, and with the amounts of soap (potassium laurate) indicated in weight percent and in molality m. (Harkins. )...

The collector used in this experiment was sodium oleate at additions of 300 g/t. In addition to sodium oleate, other fatty acid collectors were examined. The results are given in Table 24.10. From these data, the saturated fatty acid soap was a poor collector for monazite, as well as sodium laurate. 

The composition data obtained for the series of mixed fatty acid-potassium soap systems, prepared by both the ethanol and petroleum ether routes, lend strong support to the formation of 1 to 1 acid-soap complexes. It is of interest to inquire into the phase relationships in these two-component systems. A phase diagram presented by McBain and Field (15) for the lauric acid-potassium laurate system shows that compound formation takes place between the two components at the 1 to 1 molar ratio, but the compound undergoes melting with decomposition at 91.3 °C. [A similar type of phase behavior has been reported by us for the sodium alkyl sulfate-alkyl alcohol (9) and sodium alkyl sulfonate-alkyl alcohol (12) systems, but in these cases the stoichiometry is 2 to 1]. 

Figure 1 shows the results obtained by Francois and Skoulios (27) on the conductivity of various liquid crystalline phases in the binary systems water-sodium lauryl sulfate and water-potassium laurate at 50 °C. As might be expected, the water-continuous normal hexagonal phase has the highest conductivity among the liquid crystals while the lamellar phase with its bimolecular leaflets of surfactant has the lowest conductivity. Francois (28) has presented data on the conductivity of the hexagonal phases of other soaps. She has also discussed the mechanism of ion transport in the hexagonal phase and its similarity to ion transport in aqueous solutions of rodlike polyelectrolytes. 

A spectrum of perdeuterated potassium laurate in oriented soap-water multilayers (5) is presented in Figure 2. The measured quadrupolar coupling constants are much smaller than those of a static C-D bond, which are about 167 kHz (6) the residual quadrupolar splittings... 

Discussion. We can now propose a coarse description of the paraffinic medium in a lamellar lyotropic mesophase (potassium laurate-water). Fast translational diffusion, with D 10"6 at 90 °C, occurs while the chain conformation changes. The characteristic times of the chain deformations are distributed up to 3.10"6 sec at 90 °C. Presence of the soap-water interface and of neighboring molecules limits the number of conformations accessible to the chains. These findings confirm the concept of the paraffinic medium as an anisotropic liquid. One must also compare the frequencies of the slowest deformation mode (106 Hz) and of the local diffusive jump (109 Hz). When one molecule wants to slip by the side of another, the way has to be free. If the swinging motions of the molecules, or their slowest deformation modes, were uncorrelated, the molecules would have to wait about 10"6 sec between two diffusive jumps. The rapid diffusion could then be understood if the slow motions were collective motions in the lamellae. In this respect, the slow motions could depend on the macroscopic structure (lamellar or cylindrical, for example)... 

Wherever possible, the soaps and surfactants were added to the natural rubber latex as dilute aqueous solutions. The cases where this was not possible were (a) ethylene oxide-fatty alcohol condensates of low ethylene oxide fatty alcohol mole ratio, and (b) sparingly-soluble fatty-acid soaps such as lithium laurate and calcium soaps. The former were added as pastes with water, the latter as dry powders. In all cases, the latex samples were allowed to mature for about three days at room temperature before their mechanical stabilities were determined. This allowed some opportunity for the attainment of adsorption equilibrium. 

The results for effects upon mechanical stability are summarised in Table II. That lithium laurate behaves similarly to, say, potassium laurate is perhaps surprising, in that it is known that a lithium salt is mor ffective in reducing the mechanical stability of natural rubber -ftian is the corresponding potassium salt (6.). The inference has been drawn that the counterion of the car-boxylate soap has a negligible effect upon the ability of the soap to enhance mechanical stability, relative to the effect of the anion, at least for those cations for which specific adsorption effects are absent. 

The first quantitative experiments on shifting the equilibrium in a foam have been conducted with soap solutions [108]. It was found that the foam which underwent decaying was acidic whereas the remaining solution was alkaline. Furthermore, the surface tension of this solution was twice as high as that of the liquid obtained from the foam. The hydrolysis was most pronounced in dilute solutions. When the concentration of sodium oleate was 0.0002%, the ratio between the proportions of the acid and the base in the foam was 2.7, and it was only slightly dependent on the nature of the base. Similar results have been obtained for the foam prepared from sodium laurate solution [3]. 

Lipase splits fatty acids from glycerol to produce free fatty acids, for example, butyric acid. If the original fat is butterfat then at low levels this produces a buttery or creamy flavour. As the free fatty acid content is increased, this strengthens the flavour to cheesy . Normally in toffees free butyric acid is not a problem at any practical level, possibly because of losses during cooking. Other free fatty acids have different flavours. Laurie acid, which is found in nuts, tastes of soap. This is not too surprising as soap often contains sodium laurate. Laurie fat sources, such as hardened palm kernel oil, are often used as a substitute for butter another potential source is nuts, which are sometimes combined with toffee. In any of these cases, lipolytic activity can shorten the shelf life of the product or render it totally unacceptable. 

Pesticidal soaps are potassium salts of fatty acids. The most effective soaps are potassium salts of capric (C10), lauric (C12), myristic (C14), palmitic (C16), and stearic (C,8) acids (Ware and Whitacre, 2004). The chemical structure of potassium laurate is as follows ... 

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