Phase titration

Air passing through the NO pathway enters the reaction chamber, where the NO present reacts with the ozone. The light produced is measured by the photomultiplier tube and converted to an NO concentration. The NO2 in the air stream in this pathway is unchanged. In the NO pathway, the NO- and N02-laden air enters the converter, where the NO2 is reduced to form NO all of the NO exits the converter as NO and enters the reaction chamber. The NO reacts with O3 and the output signal is the total NO concentration. The NO2 concentration in the original air stream is the difference between NO and NO. Calibration techniques use gas-phase titration of an NO standard with O3 or an NOj permeation device. 

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-... 

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... 

A number of proven methods is available for the analysis of commercial alkanesulfonates. The total sulfonate content and the monosulfonate content can be determined quite accurately by extractive methods and different forms of two-phase titration. 

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... 

Recently, several modifications of the two-phase titration and their precisions have been compared. The two-phase titration with the above-mentioned mixed indicator system, dimidium bromide/disulfine blue, is standardized in DGF (Deutsche Gesellschaft fur Fettforschung) and DIN methods, and is less time consuming and simpler than the standard gravimetric and extraction methods [18]. 

When performing the two-phase titration with benzethonium chloride in alkaline medium and in the presence of phenolphthalein as indicator, not only the monosulfonates but also the di- and polysulfonates are determined [19]. The content of di- and polysulfonates is the difference between two titration results giving the amounts of total sulfonates and monosulfonates. Identifying the endpoint requires some experience. 

A ring test proved that surfactant-selective electrodes are suitable for quantitative determination of anionic surfactants including alkanesulfonates [21]. The precision of this method, however, does not yet correspond to the state-of-the-art of the two-phase titration. Therefore, further development is needed to enhance the reproducibility and competitiveness of surfactant-sensitive titration. 

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. 

One-phase titration methods have also been developed. These methods are not truly one-phase titrations but the term is used to indicate the absence of a second organic phase. One of these methods, applied to the analysis of sodium and triethanolamine lauryl sulfates and lauryl ether sulfates, use a quaternary amine as a titrant and cobalt(II) thiocyanate as indicator. Centrimide was found to avoid the use of chloroform which was not possible with other titrants examined, such as domiphen bromide and oxyphenonium bromide. The pink color of the indicator changes to violet as an excess of titrant forms a complex with the indicator [238]. 

Turbidimetric titration has also been applied to one-phase titration of alcohol sulfates and other anionic surfactants. The titration is carried out with hyamine 1622 in aqueous solution without the organic phase and indicator and the endpoint is taken as the point of maximum turbidity. The presence of nonionics and inorganic salts at high concentration interfere with the endpoint determination [243]. 

Electrochemical analytical techniques are a class of titration methods which in turn can be subdivided into potentiometric titrations using ion-selective electrodes and polarographic methods. Polarographic methods are based on the suppression of the overpotential associated with oxygen or other species in the polarographic cell caused by surfactants or on the effect of surfactants on the capacitance of the electrode. One example of this latter case is the method based on the interference of anionic surfactants with cationic surfactants, or vice versa, on the capacitance of a mercury drop electrode. This interference can be used in the one-phase titration of sulfates without indicator to determine the endpoint... 

The two-phase titration method is still the most commonly used method, but due to the current concern regarding the health risks of chloroform, nowadays efforts are being devoted to develop an alternative standard method. This subject is on the agenda of the CESIO (Comite Europeen des Agents de Surface et leurs Intermediaries Organiques) Analysis Working Group. 

A manual titrimetric method using methyl orange as indicator and sodium tetraphenylboron as titrant has been described [273]. Dodecyl sulfate at concentrations of approximately 10"5 M have been analyzed by a visual two-phase titration in the presence of dichloroethane and tetrabromophenolphthalein ethyl ester [274]. 

ISO 2271 1989, Surface active agents Determination of anionic-active matter by manual or mechanical direct two-phase titration procedure. 

Two-phase titration is an old but very good method requiring no special apparatus [50]. 

Highly concentrated ether carboxylic acids with a low degree of ethoxylation even at room temperature can give an esterification reaction with the non-converted nonionic, especially with the fatty alcohol, to several percentage points. The result may be that a too low value is found for the ether carboxylate content. This mistake in analysis can be avoided by saponification of the formed ester [238]. Two hundred to 300 mg matter and ca 100 mg NaOH were weighed in a 50-ml Erlenmeyer glass, heated with 20 ml ethanol under reflux, and after cooling supplied with water to 100 ml. Afterward a two-phase titration was carried out. 

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. 

The technique is especially useful for analysis of low molecular weight AOS (C8, C10), which has greater water solubility, and can be more accurate than the two-phase titration procedures. High molecular weight AOS with poor water solubility can still be analyzed if the ion exchange is performed at elevated temperature. 

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]. 

Analytical methods for qualitative and quantitative determination of all kinds of surfactants have long been established. There can be found either wet chemical methods—like titration—or methods of instrumental analytics. A classical method for anionic surfactants is the so-called two-phase-titration [63]. Using this method nearly every molecule bearing an anionic group is detected. The correct determination of sulfosuccinates is limited to the interferences of the other ingredients and byproducts present. With few exceptions all sulfosuccinates react with special indicators, e.g., hyamin 1622 (Rohm and Haas), to form an anionic-cationic complex and hence are to be analyzed by active content titration. 

Active content ( pure sulfosuccinate, as analyzed by a two-phase titration assuming a defined molecular weight) 32-35%... 

Although Eq. (25) has no physical meaning and although its simplification is not valid thermodynamically, since the condition of electroneutrality in both phases is not fulfilled if the proton cannot partition, it agrees very well with experimental data, which justifies its use. In fact, computerized fitting procedures correct for this error in commercial two-phase titrators, so that the experimental value of p K can directly be introduced in Eq. (25). 

Gur ev, I. A. Kiseleva, L. V., Dual-phase titration of aliphatic acids in the presence of neutral salts, J. Anal. Chem. USSR 33, 427 430 (Engl.) (1978). 

We will summarize the results of a systematical study of these systems by phase titration, turbidimetry and viscosimetry, The concentration ranges were 0[Pg.134]

Figure 4 Phase titration of system AD27 (5 g/1) - Al ( 5 ppm ) (see test)...

Phase titrations have well confirmed that the precipitated phase contains polymer, then the turbidity cannot be due to a flocculation of Al(0H)3 particles without polymer adsorption. pH 7 with added NaCl... 

The measurement of absorbance of light by a dyestuff-anionic surfactant complex, which has been extracted into an organic solvent is a key feature of many methods, and Sodergren has successfully used segmented flow colorimetry for an automated version of this procedure (2 ). An alternative is the two phase titration technique, pioneered by Herring (3) which uses dimidium... 

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 ... 

The sulfonate content was determined either by the well-known technique of two-phase titration with hyamine or by liquid chromatography (HPCL). Nonionic surfactants were analyzed by HPLC (16) in the reverse or normal phase mode depending on whether the aim was to determine their content in effluents or to compare their ethylene oxide distribution. 

Massaccesi reported the development of a two-phase titration method for the analysis of miconazole and other imidazole derivatives in pure form and in pharmaceutical formulation [14], To the sample (10 mg) are added 10 mL of water, 10 mL of 1 M-sulfuric acid, 25 mL of dichloromethane and 1 mL of 0.05% indophenol blue (C.I. No. 49700) in dichloromethane solution and the solution is titrated with 10 mM sodium dodecyl sulfate until the color of the organic phase changes from blue to pale yellow. Results obtained for the drug in pure form, tablets, suppositories, cream and lotion agreed with the expected values and the coefficient of variation (n = 6) were 0.3-0.35%. Imidazole and the other constituents of the pharmaceutical preparations did not interfere. 

Many methods have been developed to detect the Lewis acidity/basicity and Bronsted acid-ity/basicity. Liquid- or gas-phase titration, UV spectroscopy, and calorimetry are some of the non-spectroscopic methods of detecting acidity and basicity of an oxide material.26 However, we shall confine our discussion to the spectroscopic methods of detecting the acidity and basicity of an oxide material. IR, Raman, and NMR are the common spectroscopic techniques used to quantify the acidity or basicity of an oxide material. 

Formation of dihydrotropylium ions is a key feature of the C H9+ hypersurface. Currently, efforts in our laboratory276 have concentrated on the presence of different C H9+ isomers by probing their bimolecular reactivity. Thus, gas-phase titration in the FT-ICR mass spectrometer has revealed that mixtures of C7H9+ ions are formed by protonation of 1,3,5-cycloheptatriene, 6-methylfulvene and norbomadiene as the neutral precursors but that, in contrast to the results obtained by CS mass spectrometry, fragmentation of the radical cations of limonene yields almost exclusively toluenium ions275. 

The first two determinations by radiation absorption require accurate measurements of the extinction coefficients of ozone (a measurement of the absorption efficiency of the incoming radiation at a maximal absorption wavelength) in the ultraviolet and the infrared. Three different principles have been used over the last 20 years to measure the extinction coefficient of ozone in the ultraviolet at 254 nm manometric, decomposition stoichiometry, and gas-phase titration. The manometric method, which is based on pressure measurements of gaseous ozone, requires (in at least one case ) a substantial and somewhat uncertain correction for decomposition and the method of decomposition stoichiometry depends on the pressure change that accompanies the decomposition of ozone to oxygen, 20, 30,. Clyne and Coxon determined ozone... 

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