Blue surfactants

The spectophotometric methylene blue method for anionic surfactants has been applied to seawater. In one version, the surfactants are collected in ethyl acetate. The solvent is then evaporated, the surfactants put back in solution in water, and the standard spectrophotometric methylene blue method is applied to this solution. In this manner, the salt error introduced by seawater is eliminated [195]. A similar method, with the methylene blue-surfactant complex extracted into chloroform, and measured directly was proposed by Hagihara [192]. 

Add 10 mL of chloroform followed by methylene blue reagent. The separatory funnel is shaken vigorously for 30 s. Methylene blue-surfactant ion pair separates into the bottom chloroform layer. The aqueous layer should be colorless. The above chloroform extraction is performed two more times. The extracts are combined and then washed repeatedly in another separatory funnel with the acid wash solution. 

An example of the time effects in irreversible adsorption of a surfactant system is shown in Fig. XI-8 for barium dinonylnapthalene sulfonate (an oil additive) adsorbing on Ti02 (anatase). Adsorption was ineversible for aged systems, but much less so for those equilibrating for a short time. The adsorption of aqueous methylene blue (note Section XI-4) on TiOi (anatase) was also irreversible [128]. In these situations it seems necessary to postulate at least a two-stage sequence, such as... 

In hair coloring a light ash blond shade may require as Httie as 0.5—1% of intermediates, whereas a tme black may require up to about 5%. In principle, the formulator blends precursors that yield red, blue, and yellow dyes. The base in which the components are dissolved or suspended is similar to that used in simple bleaches and may include alkanolamides, various types of surfactants, thickening agents, and solvents. Removal of undesirable dyes is achieved by treating the discolored hair with a powerful reductant of the sulfite family. 

In this work hybrid method is suggested to determine anionic surfactants in waters. It is based on preconcentration of anionic surfactants as their ion associates with cationic dyes on the membrane filter and measurement of colour intensity by solid-phase spectrophotometry method. Effect of different basic dyes, nature and hydrophobicity of anionic surfactants, size of membrane filter pores, filtration rate on sensitivity of their determination was studied. Various cationic dyes, such as Methylene Blue, Crystal Violet, Malachite Green, Rhodamine 6G, Safranin T, Acridine Yellow were used as counter ions. The difference in reflection between the blank and the sample was significant when Crystal Violet or Rhodamine 6G or Acridine Yellow were used. 

SOLID-PHASE SPECTROPHOTOMETRIC AND TEST DETERMINATION OF CATIONIC SURFACTANTS ON PAPER FILTERS AS ION ASSOCIATE WITH BROMPHENOL BLUE... 

Poloxamers are used primarily in aqueous solution and may be quantified in the aqueous phase by the use of compleximetric methods. However, a major limitation is that these techniques are essentially only capable of quantifying alkylene oxide groups and are by no means selective for poloxamers. The basis of these methods is the formation of a complex between a metal ion and the oxygen atoms that form the ether linkages. Reaction of this complex with an anion leads to the formation of a salt that, after precipitation or extraction, may be used for quantitation. A method reported to be rapid, simple, and consistently reproducible [18] involves a two-phase titration, which eliminates interferences from anionic surfactants. The poloxamer is complexed with potassium ions in an alkaline aqueous solution and extracted into dichloromethane as an ion pair with the titrant, tet-rakis (4-fluorophenyl) borate. The end point is defined by a color change resulting from the complexation of the indicator, Victoria Blue B, with excess titrant. The Wickbold [19] method, widely used to determine nonionic surfactants, has been applied to poloxamer type surfactants 120]. Essentially the method involves the formation in the presence of barium ions of a complex be-... 

In this case the sulphonic acid group is present in a sulphon-phthalein dye namely the indicator bromophenol blue. As in the previous example, the species (R3NH + )(R S03 ) can be extracted into chloroform whilst the indicator itself is not extracted, and the colour of the extract is proportional to the quantity of surfactant in the material under test. 

The chemical properties of the alkylarylsulfonates are used in its analytical determination. As anions, LAS and other anionic surfactants react with large cations to salts, which are soluble in organic solvents (e.g., CHC13). By analysis it can be seen that cations such as Hyamine 1622 (25) and methylene blue, which rearrange with LAS to complex (26), are widely spread. These reactions are the basis for the so-called two-phase titration, an extensively used method... 

The two-phase titration is based on the reaction of anionic surfactants with cations—normally large cationic surfactants—to form an ion pair. The preferred cationic is benzethonium chloride (Hyamine 1622, 1) because of the purity of the commercially available product. On neutralization of the ionic charges, the ion pair has nonpolar character and can be extracted continuously into the organic phase, e.g., chloroform, as it is formed. The reaction is monitored by addition of a water-soluble cationic dye, dimidium bromide (2), and a water-soluble anionic dye, disulfine blue (3). The cationic dye forms an extractable... 

The method developed by Epton [212,213] became the universally accepted method for the analysis of active matter of anionic and cationic surfactants. Epton s method, also known as the two-phase titration, is based on the titration of the anionic surfactant with cetylpyridinium bromide, a cationic surfactant, in the presence of methylene blue as indicator. A solution of the anionic surfactant is mixed with the indicator dissolved in dilute sulfuric acid, followed by further addition of chloroform, and then it is titrated with the cationic surfactant. Methylene blue forms a complex with the anionic salt that is soluble in chloroform, giving the layer a blue color. As the titration proceeds there is a slow transference of color to the water layer until the equivalence point. At the equivalence point colors of the chloroform and water layers are visually the same. On successive additions of titrant the chloroform layer lightens in shade and finally becomes colorless. 

Other detection methods are based on optical transmittance [228-231], Alcohol sulfates have been determined by spectrophotometric titration with barium chloride in aqueous acetone at pH 3 and an indicator [232] or by titration with Septonex (carbethoxypentadecyltrimethylammonium bromide) and neutral red as indicator at pH 8.2-8.4 and 540 nm [233]. In a modified two-phase back-titration method, the anionic surfactant solution is treated with hyamine solution, methylene blue, and chloroform and then titrated with standard sodium dodecyl sulfate. The chloroform passing through a porous PTFE membrane is circulated through a spectrometer and the surfactant is analyzed by determining the absorbance at 655 nm [234]. The use of a stirred titration vessel combined with spectrophotometric measurement has also been suggested [235]. Alternative endpoint detections are based on physical methods, such as stalag-mometry [236] and nonfaradaic potentiometry [237]. 

Alcohol and alcohol ether sulfates are commonly considered as extremely rapid in primary biodegradation. The ester linkage in the molecule of these substances, prone to chemical hydrolysis in acid media, was considered the main reason for the rapid degradation. The hydrolysis of linear primary alcohol sulfates by bacterial enzymes is very easy and has been demonstrated in vitro. Since the direct consequence of this hydrolysis is the loss of surfactant properties, the primary biodegradation, determined by the methylene blue active substance analysis (MBAS), appears to be very rapid. However, the biodegradation of alcohol sulfates cannot be explained by this theory alone as it was proven by Hammerton in 1955 that other alcohol sulfates were highly resistant [386,387]. 

ISO 7875-1 1984, Water quality. Determination of surfactants—Part 1 Determination of anionic surfactants by the methylene blue spectrometric method. 

Active matter (anionic surfactant) in AOS consists of alkene- and hydroxy-alkanemonosulfonates, as well as small amounts of disulfonates. Active matter (AM) content is usually expressed as milliequivalents per 100 grams, or as weight percent. Three methods are available for the determination of AM in AOS calculation by difference, the two-phase titration such as methylene blue-active substances (MBAS) and by potentiometric titration with cationic. The calculation method has a number of inherent error factors. The two-phase titration methods may not be completely quantitative and can yield values differing by several percent from those obtained from the total sulfur content. These methods employ trichloromethane, the effects from which the analyst must be protected. The best method for routine use is probably the potentiometric titration method but this requires the availability of more expensive equipment. 

Gravimetric and volumetric methods are practicable for the quantitative determination of the a-sulfo fatty acid esters. Using gravimetric methods the surfactant is precipitated with p-toluidine or barium chloride [105]. The volumetric determination method is two-phase titration. In this technique different titrants and indicators are used. For the analysis of a-sulfo fatty acid esters the quaternary ammonium surfactant hyamine 1622 (p,f-octylphenoxyethyldimethyl-ammonium chloride) is used as the titrant [106]. The indicator depends on the pH value of the titration solution. Titration with a phenol red indicator is carried out at a pH of 9, methylene blue is used in acid medium [106], and a mixed indicator of a cationic (dimidium bromide) and an anionic (disulfine blue VN150) dye can be used in an acid and basic medium [105]. 

The amount of the ester sulfonates, besides the mono- and disalt of the a-sulfo fatty acid, can be calculated by two titrations, one in the acid and one in the basic range. In the basic range both sulfonates and carbocylate functionalities are negatively charged and titrated with the cationic surfactant hyamine. In acid medium the RCOOH group is protonated and no longer available for the titration. Since hyamine-methylene blue (acid conditions) titrates only sulfonate and hyamine-phenol red (basic conditions) determines both sulfonates and carbo-cylates, substraction of the titration value with phenol red from the double value of the titration with methylene blue yields only the a-sulfo fatty acid ester. This is the only species of the three which has merely the sulfonate function [106]. 

Another titration method makes use of benzalkonium chloride. A solution of an anionic surfactant ( — 0.1 meq) is put into a beaker, and 20 ml of a methylene blue solution (—0.25% in water) and chloroform is added. Titration is performed against a 0.004 M solution of benzalkonium chloride under vigorous stirring. When both water and chloroform phase show the same (blue) color, the endpoint of the titration is reached. 

BASIS OF MANUAL PHOTOMETRIC TITRATION. The determination of anionic surfactants by a photometric titration employs a cationic indicator to form a coloured complex with the surfactant which is insoluble in water but readily soluble in chlorinated solvents (1 ). The end point of the titration occurs when there is a loss of colour from the organic phase. A considerable improvement in this technique is achieved by the use of a mixture of anionic and cationic dyes (4 ), for example disulphine blue and dimidium bromide (Herring s indicator (3)). The sequence of colour changes which occurs during the two phase titration of an anionic surfactant (AS) with a cationic titrant (CT) using a mixed indicator consisting of an anionic indicator (AD) and cationic indicator (CD) is summarised in Scheme 1 ... 

CHOICE OF FILTER FOR AUTOMATED PHOTOMETRIC TITRATION. At the end of a photometric titration using the above two indicators the colour of the chloroform phase changes from pink to blue. To choose a filter to detect this end point the visible spectra of the separated chloroform layers of surfactant titrations were recorded before, at and beyond the end point, see Figure 2. At 580 nm there was a greater change in absorbance than at 440 nm, thus the 580 nm filter was preferred. 

FIGURE 13.5 AFM images of Prussian blue-modified monocrystalline graphite (a) conventional Prussian blue deposited without surfactants, (b) Prussian blue electrochemically deposited through liquid crystalline phase of non-ionic surfactant Brij-56. 

Ferric hydroxide coprecipitation techniques are lengthy, two days being needed for a complete precipitation. To speed up this analysis, Tzeng and Zeitlin [595] studied the applicability of an intrinsically rapid technique, namely adsorption colloid flotation. This separation procedure uses a surfactant-collector-inert gas system, in which a charged surface-inactive species is adsorbed on a hydrophobic colloid collector of opposite charge. The colloid with the adsorbed species is floated to the surface with a suitable surfactant and inert gas, and the foam layer is removed manually for analysis by a methylene blue spectrometric procedure. The advantages of the method include a rapid separation, simple equipment, and excellent recoveries. Tzeng and Zeitlin [595] used the floation unit that was devised by Kim and Zeitlin [517]. 

The methylene blue reaction can also be used in a fractionation procedure for surfactants. The complexes with methylene blue can be collected in an organic solvent, concentrated, dissolved in methanol, and separated by high-performance liquid chromatography [205]. A variation of this method, permitting the collection of surfactant from large volumes of sample, should be workable in seawater. 

---