表面活性剂复配体系的分析

介绍了一种使用经典的分析技术定量测定液体皂、皂胶、洗衣皂及香皂中存在的皂类、脂肪酸、非离子表面活性剂及除肥皂以外的阴离子表面活性剂和两性表面活性剂混合物的分析方法。这种方法克服了分析混合表面活性剂系统时常常会碰到的问题。     

Detergent action of rosin soaps and fatty acid — Rosin soaps

Summary A method for evaluating the detergent action of soaps has been described and applied to a series of soap solutions. The detergent action of rosin soaps, the effect of compounds present in soap or used with soap on the detergent action of a rosin soap, and the effect of rosin soap on the detergent action of tallow soap have been tested. The effect of temperature on the detergent action of some of the detergent solutions has also been determined. The results of these detergent tests on rosin, fatty acid and fatty acid-rosin soaps indicated the following: (1) Rosin soaps made from different gum rosins, produced from longleaf and slash pine gums, have equal detergent action; (2) The presence of soaps of oxidized rosin acids has no effect on detergent action of the rosin soap; (3) The detergent action of soaps made from pyroabietic acid, abietic acid and hydrogenated rosin parallels their ability to lower the surface tension of water and the amount of hydrogen present in the rosin acids; (4) The addition of builders that increase the alkalinity of the rosin soap solution improves the detergent action of the solution; (5) The blending of rosin soap with tallow soap improves the detergent action of the tallow soap in solutions having a soap concentration of 0.25 percent or more; (6) Temperature affects the detergent action of rosin and coconut oil soaps more than tallow soap.     

Determination of titanium dioxide in soaps by furnace atomic absorption spectrometry

A procedure for the determination of titanium dioxide in soaps by furnace atomic absorption spectrometry is described. The method has the advantage of being rapid and simple. After the soap is dispersed in water, the titanium dioxide content is determined directly without any preliminary treatment with acids and bases to solubilize the titanium dioxide.     

A rapid volumetric test for anhydrous soap

Summary The preceding describes a method for obtaining anhydrous soap in an elapsed time of less than a half-hour with a maximum error of less than five parts per thousand. The method agrees well with simultaneous analyses made by the official ether extraction method and with total analyses. The equipment is inexpensive and the technic is simple. The volumetric method is particularly well-suited to process control. Though its use in tallow and coconut oil soaps only has been attempted, the author feels that its scope may be extended to other soap bases.     

无毒金属皂间协同热稳定效果的研究

通过静态刚果红法、热烘法来研究锌皂与各种不同金属皂间的协同热稳定效果。研究结果表明：初期型锌皂与其它长期型金属皂复合能显著改善初期热烘变色,表现良好协同稳定作用;新型锌的热稳定时间是硬脂酸锌的两倍,采用新型锌的复合皂的热稳定性能均比采用硬脂酯锌的复合皂明显提高,其中新型锌与硬脂酸钙的复合皂热稳定性能最好。     

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.     

Determination of hexachlorophene content of soaps using ferric chloride reagent

Summary Hexachlorophene is determined in soap by measuring the color produced by reaction with ferric chloride in alcohol solution with controlled conditions of time and temperature. The precision is within ±5% of the hexachlorophene content at the 1/2% level or above. As a criterion, any soap that will give a finely dispersed barium soap and that does not form a precipitate with ferric chloride under the conditions of the method give good results. This includes all milled bar soaps. The effect of phenolic perfume ingredients on the result is negligible. Five per cent abietic acid in the fatty acid composition has no effect on the result. The method is slightly modified for use with liquid potassium soaps.     

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.     

Unsaponified and unsaponifiable determinations as applied to incompletely saponified soaps

Unsaponified and unsaponifiable determinations were made on toilet bar soap, potash vegetable oil paste soap, yellow laundry soap and hardwater cocoa bar soap according to the method of (1) the American Oil Chemists’ Society, and (2) the Society of Public Analysts (British). The results obtained by the two methods were comparable for toilet bar soap, potash vegetable oil paste soap and yellow laundry soap. The unsaponifiable matter in hardwater cocoa bar soap, however, appeared considerably lower when determined by the A. O. C. S. method than when determined by the S. P. A. method. Extraction of unsaponified matter in the former method is by petroleum ether; in the latter method by ethyl ether. In order to determine whether the difference in results could be traced to the difference in solvents, extraction with petroleum ether in the A. O. C. S. method was followed by extraction with ethyl ether. The weight of unsaponified matter (50 gram sample) was increased thereby from 0.791 g. to 1.423 g. The saponification value of the ethyl ether extract under the A. O. C. S. method tended to show that practically all of the additional material extracted with ethyl ether was made up of mono and diglycerides with the mono predominating.     

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.     

Studies on viscosity of calcium soaps in aqueous methanol

Viscosity measurements of calcium soaps show that two kinds of micelles are formed in aqueous methanol mixtures. The change in the nature of micelles from hydrophilic oleomicelles to lipophilic hydromicelles occurs in solvents containing 40–50% (v/v) of methanol. The equations of Vand and Moulik are applicable only above the critical micelle concentration of the soaps. The parameters of the equations have been evaluated. These may be used to calculate the viscosity of soap solutions in the concentration range in which the equations hold good.     

Column Chromatographic Determination of Unsaponifiable Matter in Fats and Oils

A column chromatographic method for determination of unsaponifiable matter (UM) in fats and oils has been developed. The procedure involves saponification of the oil and elution or UM through a mixed bed consisting of an upper layer of calcium oxide and a lower layer of basic aluminium oxide, using diethyl ether as the eluting solvent and finally quantitation of UM by weight. The method eliminates tedious and time-consuming extraction steps and the consequent problems due to possible emulsion by hydrolysis, UM contents of fats and oils can be determined with very good to excellent accuracy. The relative standard deviation for 6.0 per cent to 0.5 per cent of UM in oils is in the range of 0.5–2.0. The method is simple, readily adaptable, fairly rapid and is equally applicable to soap samples.     

Schnellmethode zur Isolierung der Sterine aus Fetten und Ölen

Rapid Method for Isolation of Sterols from Fats and Oils Isolation of sterols from fats and oils mostly takes place by the very time-consuming solvent extraction of the unsaponifiable from the soap solution. The time required can be reduced to about 1 hour by a new developed procedure which makes possible to separate soaps and polar components of the fats from the saponified sample by aluminium oxide columns. The use of 250 mg of fat is sufficient for a following sterol examination by gas chromatography.     

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.     

Determination of Fatty Matter,Silicate and Chloride in Soap from a Single Aliquot

A simple, rapid method for analysis of soap samples has been developed. The special features of the method are 1) it enables determination of fatty matter, silicate and chloride in a soap from a single aliquot, 2) it eliminates the requirement of alcohol for determination of silicate (alcohol-insolubles), 3) it makes use of an indicator, bromocresol green that permits better detection of equivalance point, 4) it significantly cuts down the time of analysis to less than one and a half hour. Fatty matter, silicate and chloride can all be determined with reasonable accuracy. The relative standard deviation data for silicates at 10 to 20 per cent levels in soaps are in the range of 0.13 to 0.55 while those for fatty matter at 30 to 70 percent levels lie in the range of 0.14 to 0.47. The method is simple, unsophisticated, utilizes only inexpensive and readily available chemicals and are easily adoptable to any laboratory. The method is particularly useful for process control laboratories where speed is a prerequisite to analysis.     

锌皂与其它金属皂的协同效应

通过刚果红法、热烘法及耐侯性实验研究了几种无毒硬脂酸皂与特种脂肪酸皂的耐热性、耐侯性以及锌皂与其它金属皂间的协同效应。研究结果表明,特种脂肪酸皂的热稳定性能优于相对应的硬脂酸皂;硬脂酸锌与其它硬脂酸皂复合,能改善初期着色,但长期稳定性差,耐侯性也不好;特种脂肪酸锌与其它特种脂肪酸皂复合,能改善初期着色,长期稳定性好,同时制品的耐候性也得到显著的改善,表现较好的协同稳定效果。     

Acoustic behaviour of chromium soap solutions in benzene–dimethyl formamide mixture

The critical micelle concentration and various acoustic parameters of chromium soaps (myristate, palmitate, and stearate) in a mixture of benzene and dimethyl formamide (4 : 1 v/v) have been determined by ultrasonic velocity measurements. The results showed that the ultrasonic velocity, specific acoustic impedance, molar sound velocity, and molar sound compressibility increase, while intermolecular freelength, adiabatic compressibility, and available volume decrease with increasing concentration and chain length of the soap. The results show that there is a significant interaction between soap and solvent molecules in dilute solutions and the soap molecules do not aggregate appreciably in dilute solutions. © 1993 John Wiley & Sons, Inc.     

Hydrogen bromide titration for soaps in fat products

Since none of the existing methods for determining soaps in fat products have been found to be entirely satisfactory, a method has been devised for the determination of alkali metal soaps by direct titration with Durbetaki reagent (hydrogen bromide dissolved in glacial acetic acid). When the titration was conducted at room temperature in acetic acid-benzene solution with crystal violet as indicator, soaps of potassium, sodium and lithium could be determined accurately in anhydrous oils, monoglycerides, and sucrose esters. The presence of alcohols, glycerol and sucrose did not interfere in the direct titration. However, oxidized oils, epoxides, and cyclopropenoid acids, which are known to consume hydrogen bromide, did interfere. Products containing the interfering substances could be analyzed by a modified procedure in which the alkali metal cations were extracted from a mixture of amyl acetate andn-butanol (1:3) into an aqueous solution of acetic acid, and titrated as the acetates.     

Potassium silicates in soaps

Summary Properties of potassium silicates of interest in regard to their use as a detergent with soaps have been studied. A 40% potassium coconut oil soap can be mixed in all proportions with the comercial 3.3 ratio potassium silicate containing 39.6% solids. The pH's of the silicate solutions vary from 9.6 to 11 at concentrations of most practical interest. The 3.3 ratio silicate increases the pH of a potassium coconut oil soap solution. More suds form when the soap is dissolved in a 0.031% K₂O·3.3SiO₂ solution than in the same molality of a potassium carbonate solution or in pure water. Quantitative measurements of their suspending action on ilmenite shows that at their optimum concentrations both silicates are more effective than potassium carbonate and almost as good as soap. The maximum effect of soap occurs at a higher concentration than that for the silicates. A mixture of soap and K₂O·3.3SiO₂ prevents the deposition of ferric oxide pigment on cotton cloth about equally as well as soap alone; this mixture is more effective than soap alone for preventing the deposition of raw umber. Both silicates prevented the deposition of raw umber more effectively than soap alone or soap-alkali mixtures below 0.1% and are not much less effective above this concentration. Soil removal experiments with a cottonseed oil-Oil-dag soil showed that a mixture of K₂O·3.3SiO₂ and potassium coconut oil soap was about equally as efficient in distilled water and more efficient in 300 p.p.m. hard water than soap alone.     

The effect of some inorganic salts in dilute solution on the formation of calcium and magnesium soaps

1. The reactions in mixtures of dilute solutions of builders, pure soaps and hard water have been examined under conditions for optimum foam stability for the soap solution.
2. An attempt has been made to interpret these reactions on the basis of solubility products.
3. For dilute solutions of soaps of pure fatty acids a minimum mole ratio of builder to calcium or magnesium salts is required to prevent the formation of alkaline earth soaps. These mole ratios are different for each soap studied and vary with the particular calcium or magnesium salt and builder combinations.
4. The procedure used by previous investigators of this subject is discussed.

The authors wish to express their appreciation to C. W. Jakob for performing many of the determinations upon which this paper is based.