The kettle wax phase in the system sodium laurate,sodium chloride and water

Summary A study of the new phase, kettle wax, in the system sodium laurate, sodium chloride and water has been carried out using analytical and visual methods. The lower boundaries of kettle wax and its equilibria were established and when plotted occupy a highly dominant island region on the phase diagram. It occupies a portion between 60 and 70 wt. % soap and about 3 and 7 wt. % of salt. The effects of temperature on kettle wax in this system have also been studied. It was found that kettle wax existed above 75°C. and below 215°C. and has the same type of equilibria with lye throughout this temperature range. In the system sodium laurate, sodium chloride and water, curd is not formed, even by saturating the lye with salt at 90°C. Hence graining out results only in the formation of kettle wax and lye.     

Comparative value of fatty acids and resin acids of tall oil in soaps

Summary A study has been made of the detergency and foaming power of soaps made from a typical acid-refined American tall oil. Sodium soap of tall oil, straight tall oil fatty-acid soap, and straight tall oil resin-acid soap were evaluated. The effect of fatty acid-resin acid ratio was determined by using mixtures of those soaps. Sodium rosinate, sodium oleate, and mixtures of these soaps were used as comparison standards. Curves plotted show wash-test data and foaming values as functions of the ratio of fatty soap to resin soap. The data indicate in terms of detergency: a) tall oil soap has a higher value than sodium rosinate; b) sodium oleate is better than tall oil fatty-acid soap, but the latter is approximately equivalent to soaps from various unsaturated vegetable oils; c) both tall oil resin-acid soap and rosin soap have low detergency on cotton; d) the detergency of most mixtures of tall oil fatty-acid and resin-acid soaps at lower concentrations is greater than would be predicted from the individual soaps, indicating a synergistic effect. As a rough approximation, tall oil soap without unsaponifiables is equivalent to a corresponding mixture of sodium oleate and sodium rosinate. The presence of unsaponifiables lowers both detergency and foaming. Tall oil soap is somewhat less sensitive to hard water than sodium oleate. Significant differences between detergencies of soaps, and especially between soap mixtures, are obscured when launderometer tests are run at moderate soap concentrations. These differences are readily detected at lower concentrations. Presented at 113th meeting of the American Chemical Society, Chicago, Ill., April 14–23, 1948.     

Biological behavior of some soap-based detergents

The biodegradability of tallow soap, three soap-based detergent formulations and their component lime soap dispersing agents—sodium methyl α-sulfotallowate, sulfated N-(2-hydroxypropyl) tallowamide, and sodium N-methyl N-(2-sulfoethyl) tallowamide—was determined under aerobic and microaerophilic conditions. Both sewage and river water microorganisms were used as the sources of inoculum. The course of biodegradation was followed by loss of carbon and methylene blue active substance, and by increase in turbidity and surface tension. Carbon analysis for soap in solutions containing Ca⁺⁺ and Mg⁺⁺, which would precipitate soap, was performed by an improved technique using the disodium salt of ethylenediamine tetraacetic acid. Invariably a decrease in carbon content was accompanied by an increase in turbidity and surface tension. Also, loss in methylene blue active substance was concurrent with an increase in turbidity and surface tension of the degrading solutions of the detergent. Soap cannot be determined as methylene blue active substance because of the low pH of the test. Soap and the built soap formulations degraded under aerobic and microaerophilic conditions. Preliminary toxicity data upon mammals and fish indicated that the soap-based detergents are as safe as conventional commercial detergents. ARS, USDA.     

The solubility of sodium and potassium soaps and the phase diagrams of aqueous potassium soaps

Summary Solubility data are provided and collected for the pure sodium and potassium soaps. Hydrolysis obscures the temperatures of solution but is obviated by the presence of a small excess of alkali. Each sodium soap has a large range of temperature between fair and high solubility, whereas the potassium soaps go abruptly into solution, at almost the same temperature and concentration of each soap. The only soaps that are even moderately soluble at room temperature are potassium laurate, myristate, and oleate, the potassium salt of acids from coconut oil, and the sodium oleate. The other sodium and potassium soaps of the saturated fatty acids require elevated temperatures for solution. Phase diagrams for the five commonest potassium soaps are developed and recorded. This work was the basis of a thesis submitted in partial fulfillment of the requirements for the degree of Master of Science, Stanford University, 1947.     

Direct determination of sodium in soybean oil by flame photometry

The correlation of sodium content of alkalirefined soybean oil with the soap content of the oil has been widely accepted by oil processors. We have found that this sodium content can be determined by aspiration of an oil solvent solution directly into a flame emission spectrophotometer. The intensity of the sodium flame emission produced from the oil solution was compared with that from oil standards containing known amounts of sodium soaps. To prepare standards, sodium oleate was dissolved in ethylene glycol followed by the addition of a solvent and soybean oil containing low sodium of known amount; this solution aspirated at a rapid, constant rate. The method is capable of determining sodium at a lower limit of 0.1 ppm with accuracy comparable to that of neutron activation analysis. Presented at the AOCS Meeting in Minneapolis, October 5, 1969.     

Water-swelling behavior of an ethylene–vinyl alcohol copolymer in the presence of sorbed sodium chloride

The swelling behavior of water in a poly(ethylene–vinyl alcohol) copolymer (70 mol % vinyl alcohol) has been characterized at 25°C by vapor and liquid sorption experiments over a range of water activities. The activity of the vapor phase has been varied by incrementing the pressure of the water vapor in the sorption cell. Alternatively, for the liquid phase experiments, aqueous sodium chloride solutions of different concentrations have been used to vary systematically the activity of the water in the salt solution and to introduce various concentrations of salt into the copolymer films. Relaxation-controlled sorption and Fickian diffusion have been observed as limiting cases of the water sorption behavior at high and low water activities, respectively. The effects of sorbed sodium chloride on water vapor sorption kinetics and equilibria were determined independently. A second salt phase forms within the previously homogeneous and seemingly single phase polymeric system, upon contacting the salt-loaded film with a water vapor activity above a threshold value corresponding to the activity of water in the salt solution used to introduce the salt into the films. The water and salt solubilities in the ethylene–vinyl alcohol copolymer have been measured systematically to describe the complex sorption equilibria associated with this three-component, multiphase system.     

Behavior of subsilicates with soap

The behavior of sodium subsilicates as soap builders in commercial laundry operations is discussed, with particular reference to the technically anhydrous product containing 2 mols of sodium oxide per 1 mol of silicon dioxide. A system for evaluating soap builders is suggested, and subsilicates are evaluated according to this system. The data presented indicate that the technically anhydrous 2:1 ratio sodium subsilicate is eminently suitable as a soap builder in commercial laundering.     

Titrimetric determination of soap in refined vegetable oils

The low levels of soap encountered in well refined vegetable oils can be determined quickly and accurately in an isopropyl alcohol solution of the oil by a direct titration with .01 N hydrochloric acid in isopropyl alcohol using bromophenol blue as the indicator. Fifty parts per million soap calculated as sodium oleate can be determined with good accuracy and as little as 2 ppm can be detected in refined and bleached soybean oil. Soap in palm oil can be determined using the same solvent and titrant and titrating the sample to pH 5.0.     

Krafft Temperature,Critical Micelle Concentration,and Rheology of “Pseudo-Gemini” Surfactant Comprising Fatty Acid Soap and Bola-Type Quaternary Ammonium Salt

Bola-type quaternary ammonium salt can bridge with two fatty acid soaps through electrostatic attraction to form a pseudogemini surfactant, which enhances the solution viscosity. In this work, the effects of the building blocks (spacer and hydrophobic chain) of a pseudogemini surfactant on the Krafft temperature, critical micelle concentration, and rheological properties were investigated. The results revealed that the addition of bola-type salt obviously decreased the Krafft temperature of sodium stearate (C₁₈ONa), and a bola-type salt bearing a large benzene ring (Bola2be) was more effective than the one bearing an ethyl group (Bola2et) or a hydroxyethyl group (Bola2hy). When bola-type salt is mixed with fatty acid soap at a fixed molar ratio of 1:2, a pseudogemini surfactant forms in situ, and the viscosity of the solution is significantly enhanced by the formation of a worm-like micelle (WLM) network. The stronger the hydrophobicity of the bola-type salt or the tail of the fatty acid soap, the lower the critical overlapping and micelle concentrations, and the stronger is the ability to enhance viscosity. However, pseudogemini surfactants that use sodium stearate as a monomer show similar self-assembly abilities to those using sodium oleate as a monomer. In addition, the WLM formed by pseudogemini surfactants composed of Bola2be and sodium stearate or sodium oleate were liable to branch at high concentrations.     

Regeneration of Mixed Solvent by Ion Exchange Resin: Selective Removal of Chloride and Sulfate

Abstract

The selective extraction of sulfate and chloride ions from mixed solvent solutions was investigated. The mixed solvents consisted of water and 50 to 100%‐w (salt‐free solvent) ethylene glycol. The extraction was measured for mixed solvent solutions containing only sulfate and chloride, and mixed solvent solutions saturated with trona (sodium sesquicarbonate, Na₂CO₃ · NaHCO₃ · 2H₂O(s). Three anion exchange resins, Dowex 1X8‐50, Dowex 21K‐Cl, and Dowex MSA‐1, were investigated for their chemical and physical resistance to the mixed solvent carbonate/bicarbonate solutions, for their swelling behavior in the different mixed solvents, and for their extraction efficiency for chloride and sulfate.

The loading of the ion exchangers was fitted to a Langmuir‐type sorption model. While the extraction from trona‐free mixed solvents was well reproduced, the loading of the ion exchangers with chloride and sulfate from trona‐saturated mixed solvent solutions did not fit the sorption model. It appears, rather, that under these conditions chloride and sulfate are “salted out” of the bulk solution and driven into the ion exchangers.     

Salt Effects on the Recovery of Phenol by Liquid‐Liquid Extraction with Cyanex 923

Abstract

In this work, the effect of salt addition on the recovery of phenol from a 46 g/L aqueous solution simulating a phenolic resin plant effluent by liquid‐liquid extraction at 298 K has been studied by using an organic phase containing 0.6 M Cyanex 923 extractant in ShellSol T. Addition of sodium sulfate, potassium nitrate, and sodium chloride to the aqueous phase was tested and sodium chloride was selected. Based on the obtained results, a study of phenol recovery process was undergone by taking advantage of the salting‐out effect. Equilibrium curves are presented for liquid‐liquid extraction with and without salt addition to the aqueous phase. An integrated process involving salting‐out and liquid‐liquid extraction was proposed. The stripping concentrates can be reused for phenolic resin production.     

Soap-based detergent formulations: XI. Alternate synthesis and structural assignment of sodium methyl alkylbenzoylsulfopropionates

Sodium methyl alkylbenzoylsulfopropionates, derived from detergent alkylates, previously were reported to be good lime soap dispersing agents and beneficial additives in tallow soap based, sodium silicate built laundry detergents. Their synthesis from β-aroylacrylic acid intermediates has been facilitated by sulfonation with sodium bisulfite before esterification. This single phase process occurs rapidly at room temperature, whereas in the previously reported process, the sulfonation of the methyl ester requires a two-phase, high temperature, closed system procedure. Final esterification is mandatory for producing a useful lime soap dispersing agent, because the sulfonated disodium salt is a poor lime soap dispersing agent and not compatible with a soap-silicate mixture. Deoiling improves the detergency of the final products from either procedure; this is especially apparent when polyester-cotton permanent press fabric is laundered. Data from NMR spectra, base-induced decompositions, hydrolysis studies, and detergency screening tests suggest that the sulfopropionate product derived from the new procedure is structurally the same as that from the old one, and that these products have been sulfonated regiospecifically α to the carboxy group. Presented at AOCS Fall Meeting, Philadelphia, September 1974. ARS, USDA.     

The germicidal activity of rosin soap and fatty acid-rosin soap as indicated by hand-washing experiments

Summary and Conclusions Price’s procedure as slightly modified (4) was used for studying the germicidal action of cleaning agents on the hands and showed that rosin soap and a commercial soap containing rosin were more active germicidally on the bacteria normally found on human skin than the usual commercial fatty acid soaps free from rosin soap. The experiments indicate that the lather of a 10-percent coconut oil soap solution and of a 10-percent coconut oil-rosin soap solution are germicidally active against the organisms removed. However, three 2-minute washes with these soap solutions had little effect on the bacteria not removed from the hands. The use of a 10-percent rosin soap solution in the same manner had a marked germicidal effect against both the organisms removed and those remaining. The lather of a commercial soap containing rosin soap was shown to be germicidally active, but three 2-minute washes had only a slight effect on the resident flora. However, the regular use of this soap daily for one week led to substantial reduction of both the transient and resident flora of the hands. The evidence of germicidal activity of rosin soaps and soaps containing rosin, both with regard to these hand-washing experiments and the “in vitro” (7) experiments, indicates that wider consideration might well be given this type of soap where germicidal activity is of importance. L. S. Stuart was employed in the Industrial-Farm Products Research Division when this work was done.     

Surfactant promoting effects on clathrate hydrate formation: Are micelles really involved?

Critical micelle concentrations (CMCs) of several surfactants in water have been determined by conductivity measurements under hydrate-forming conditions (2 °C; 40 bar methane) and under the same conditions with nitrogen. Control experiments were also performed at room temperature and pressure. Surfactants investigated were the anionics sodium dodecylsulfate (SDS), sodium laurate (SL), sodium oleate (SO), 4-dodecylbenzenesulfonic acid (DBSA), and the cationics dodecylamine hydrochloride (DAHCl) and dodecyltrimethylammonium chloride (DTACl). For SO, DBSA and DTACl, CMC values were found to vary slightly under hydrate-forming conditions with respect to normal P-T, whereas SDS, SL and DAHCl solutions underwent precipitation before reaching the CMC under hydrate-forming conditions. Interestingly, no micellar formation was observed for any surfactants in the concentration range where strong hydrate promotion was previously reported.     

Hydrogenation of unsaturated fatty acids to unsaturated fatty alcohols: III. Comparison of different soap catalyst systems

Copper oleate and cadmium oleate catalysts have been replaced by other metal compounds. Silver was the only metal which could be substituted for copper in the ratio range studied. Using nickel oleate, the degree of saturation of the double bond decreased with increasing cadmium oleate concentration. No comparable substitute was found for Cd. The composition of the final components is influenced by the use of a paraffinic solvent, which also has an effect on the saturation of the double bond. An explanation is given for the behavior of the catalyst when the reaction is not selective and is carried out in a paraffinic solvent. The catalytic system Ag/Cd soaps was also studied kinetically and analytically. The results show that the mechanism of the reaction using silver soap is identical with the one using copper soap.     

盐效应对乙酸乙酯—甲醇—水体系液—液平衡的影响

盐效应对乙酸乙酯－甲醇－水体系液－液平衡的影响郑学明李坤英（河北科技大学化工系，石家庄市０５００１８）关键词乙酸乙酯甲醇盐效应液－液平衡１引言乙酸乙酯作为溶剂，在有机合成、化工萃取等领域广泛使用。其与甲醇、水混合体系的分离具有工业价值。例如从氨噻肟酸...     

Mechanism of acetic acid transfer from aqueous sodium chloride solutions to some orgranic solvents

Salting out of acetic acid from aqueous solutions containing various concentrations of sodium chloride into some organic solvents has been studied at various temperatures. The solvents include cyclohexane, carbon tetrachloride, 1,2-dichloroethane, isopropyl ether, 2-pentanone and 1-heptanol. The results are consistent with a transfer mechanism involving monomer partitioning, dimerization and dimer return to the aqueous phase. Factors favoring monomer partitioning such as rise in both temperature and salt level retard dimer return, a process which is found to be significant in dimerization-enhancing solvents. The sensitivity of various solvents towards salt effect increases in the order 1-heptanol < isopropylether < 1,2-dichloroethane < 2-pentanone < cyclohexane < carbon tetrachloride which generally parallels in the reverse order the extent of stabilization of the acid by various solvent interactions.     

A novel sample preparation for chloride analysis in bar soaps

A simple and rapid sample preparation technique is described for the potentiometric determination of chloride in bar soaps. Usual preparation of soap for potentiometric chloride analysis involves time-consuming dissolution of the sample in water or heating to affect dissolution, followed by a cooling step. Also, when performing potentiometric titrations for chloride under the usual acid conditions, aqueous solutions of soap bars (unlike combination soap/detergent bars) will form insoluble semisolid fatty acids that can occlude some chloride and make clean-up difficult. This paper describes a simple dissolution of bar soap sample in dilute H₂SO₄/methanol at ambient temperature that simultaneously acidifies the sample solution and produces noninterfering methyl esters from the soap fatty acids; water is then added, and the chloride is determined potentiometrically with standardized AgNO₃. This procedure has been shown to work well with automatic titrators.     

EXTRACTION OF NICKEL FROM AQUEOUS SULFATE SOLUTION INTO BIS(2,2,4-TRIMETHYLPENTYL)PHOSPHINIC ACID,CYANEX 272TM -EQUILIBRIUM AND KINETIC STUDIES

ABSTRACT

Equilibrium and kinetic studies have been carried out on the extraction of nickel from sulfate solutions using bis(2,2,4 trimethylpentyl) phosphinic acid HDTMPP, “Cyanex 272tm”- It was found that nickel extraction in HDTMPP was favored by the presence of sodium in the organic phase and that equilibrium nickel concentration could be written in terms of the pre-equilibrated extractant concentration

Kinetic studies were carried out using the rising drop method, reaction orders were determined with respect to the aqueous phase nickel concentration, Ni²⁺, the aqueous phase sodium concentration, Na ⁺ the pH, the organic phase dimer concentration ------ and the organic phase sodium salt concentration ---- In addition, it was found that the extraction kinetics could be explained in terms of an aqueous phase interfacial reaction accompanied by diffusion through the interface. Mass transfer coefficient values were determined indicating extraction rates for metal extraction into HDTMPP were the same order of magnitude as those found for HDEHP.     

Soap-based detergent formulations: XIII. Formulations with alpha-olefin sulfonates as lime soap dispersants

Heavy duty household type detergents were formulated from tallow soap-AOS(α-olefin sulfonate)-builder combinations. Various commercial AOS samples were evaluated. These were derived either from closely fractionated α-olefins such as C₁₄, C₁₆, and C₁₈ or from samples representing broader mol wt ranges such as C₁₄−C₁₆ and C₁₆−C₁₈. The builders incorporated into these combinations were a sodium silicate (Na₂O∶SiO₂=1∶1.6), sodium tripolyphosphate, sodium citrate, sodium carbonate, and trisodium nitrilotriacetate. Detergency evaluations of 0.2% solutions in 300 ppm hard water (as CaCO₃) were determined with three commercial soiled cloths and by a multiwash test in which clean cloth was repeatedly soiled and washed. The relative proportions of soap, AOS, and builder were varied to obtain maximum detergency, and comparisons were made to other soap-LSDA (lime soap dispersing agents)-builder combinations as well as to a commercial high phosphate detergent used as a control. Detergency performance of soap-AOS combinations ranked just below that of the commercial high phosphate detergent control and below that of soap formulations containing sodium methyl α-sulfotallowate. Presented at the AOCS meeting, Philadelphia, September 1974.