Phenols titration

We found no enhanced basicity attributable to the amine group on amino-propylsilane-treated glass, as reported by every other investigator cited above except Fowkes et al. [7], Using calorimetric phenol titration, they found that an equivalent basicity was imparted to glass fiber by aminopropylsilane and two other silanes all three were more basic than bare glass. 

No single method for protein study gives much information by itself and spectrophotometric titrations also have been best exploited in conjunction with auxiliary studies. For example, Tanford has routinely coupled his studies with results obtained from electrometric H+-titration studies, to show with certainty that only part of the anomalous phenolic titration of proteins can be explained by a general electrostatic argument. The review by Tanford in this volume discusses these problems in detail. 

Fig. 157. Plot of the reversible portions of the phenolic titration curves of ribonuclease according to Eq. (VII-8) (Tanford et al., 1955a).

The method is based on the conversion of urea to amnionium carbonate and the estimation of the latter by titration with standard acid. For this purpose, two equal quantities of urea (or urine) are measured out into two flasks A and B. A is treated with 10 ml. of a strong urease preparation and some phenol-phthalein, warm water is added and the mixture is adjusted by the addition of V/io HCl from a burette A until the red colour is just discharged. This brings the mixture to about pH 8 (the optimum for urease) and also prevents loss of ammonia. 

These are crystalline compounds with sharp melting points, and possess the further advantage that their equivalent weights may be determined by dissolving in dilute alcohol and titrating with standard alkali. Nitro-phenols, however, give unsatisfactory derivatives. 

The imides, primaiy and secondary nitro compounds, oximes and sulphon amides of Solubility Group III are weakly acidic nitrogen compounds they cannot be titrated satisfactorily with a standard alkaU nor do they exhibit the reactions characteristic of phenols. The neutral nitrogen compounds of Solubility Group VII include tertiary nitro compounds amides (simple and substituted) derivatives of aldehydes and ketones (hydrazones, semlcarb-azones, ete.) nitriles nitroso, azo, hydrazo and other Intermediate reduction products of aromatic nitro compounds. All the above nitrogen compounds, and also the sulphonamides of Solubility Group VII, respond, with few exceptions, to the same classification reactions (reduction and hydrolysis) and hence will be considered together. 

Ethyl bis-(2,4-dinitrophenyl) acetate (indicator) the stock solution is prepared by saturating a solution containing equal volumes of alcohol and acetone with the indicator pH range colorless 7.4-9.1 deep blue. This compound is available commercially. The preparation of this compound is described by Fehnel and Amstutz, Ind. Eng. Chem., Anal. Ed. 16 53 (1944), and by von Richter, Ber. 21 2470 (1888), who recommended it for the titration of orange- and red-colored solutions or dark oils in which the endpoint of phenol-phthalein is not easily visible. The indicator is an orange solid which after crystallization from benzene gives pale yellow crystals melting at 150-153.5°C, uncorrected. 

Bromine is used as an analytical reagent to determine the amount of unsaturation in organic compounds because carbon—carbon double bonds add bromine quantitatively, and for phenols which add bromine in the ortho and para positions. Standard bromine is added in excess and the amount unreacted is deterrnined by an indirect iodine titration. Bromine is also used to oxidize several elements, such as T1(I) to T1(III). Excess bromine is removed by adding phenol. Bromine plus an acid, such as nitric and/or hydrochloric, provides an oxidizing acid mixture usefiil in dissolving metal or mineral samples prior to analysis for sulfur. 

To the same solution add a few drops of phenol phthalein, and titrate it against N/10 NaOH until a pink colour appears, which will indicate the total acidity of the bath. This is approximately 35 to 37 for a concentration of 5% for a hot process and 60 to 64 for a concentration of 10% for a cold process. Obtain the standard total acidity of the hot or cold process chemicals from the manufacturer. 

One 1-ml aliquot is added to 1.0 ml of freshly-distilled 1,2-dibromo-ethane (bp 132°C) in an oven-dried flask which contains a static atmosphere of nitrogen or argon. After the resulting solution has been allowed to stand at 25°C for 5 min, it Is diluted with 10 rat of water and titrated for base content (residual base) to a phenolphthalein endpoint with standard 0.100 M hydrochloric acid. The second 1-mL aliquot is added cautiously to 10 ml of water and then titrated for base content (total base) to a phenol phthalein endpoint with standard aqueous 0.100 M hydrochloric acid. The methyllithium concentration is the difference between the total base and residual base concentrations.2 Alternatively, the methynithiura concentration may be determined by titration with a standard solution of sec-butyl alcohol employing 2,2 -bipyridyl as an indicator. 

With 0.01M solutions, the ideal pH range is still further limited to 5.5-8.5 such indicators as methyl red, bromothymol blue, or phenol red will be suitable. The titration error for methyl orange will be 1-2 per cent. 

Acetonitrile (methyl cyanide, cyanomethane) is frequently used with other solvents such as chloroform and phenol, and particularly with acetic acid. It enables very sharp end points to be obtained in the titration of metal acetates6 when titrated with perchloric acid. 

Solochrome dark blue or calcon ( C.1.15705). This is sometimes referred to as eriochrome blue black RC it is in fact sodium l-(2-hydroxy-l-naphthylazo)-2-naphthol-4-sulphonate. The dyestuff has two ionisable phenolic hydrogen atoms the protons ionise stepwise with pK values of 7.4 and 13.5 respectively. An important application of the indicator is in the complexometric titration of calcium in the presence of magnesium this must be carried out at a pH of about 12.3 (obtained, for example, with a diethylamine buffer 5 mL for every 100 mL of solution) in order to avoid the interference of magnesium. Under these conditions magnesium is precipitated quantitatively as the hydroxide. The colour change is from pink to pure blue. 

Pipette 25 mL of an aluminium ion solution (approximately 0.01 M) into a conical flask and from a burette add a slight excess of 0.01 M EDTA solution adjust the pH to between 7 and 8 by the addition of ammonia solution (test drops on phenol red paper or use a pH meter). Boil the solution for a few minutes to ensure complete complexation of the aluminium cool to room temperature and adjust the pH to 7-8. Add 50 mg of solochrome black/potassium nitrate mixture [see Section 10.50(C)] and titrate rapidly with standard 0.01 M zinc sulphate solution until the colour changes from blue to wine red. 

Calculate the amount of excess bromate from the amount of thiosulphate needed for the back-titration of the free iodine, and hence the quantity of bromate which reacted with the phenol. 

It may be noted that very weak acids, such as boric acid and phenol, which cannot be titrated potentiometrically in aqueous solution, can be titrated conductimetrically with relative ease. Mixtures of certain acids can be titrated more accurately by conductimetric than by potentiometric (pH) methods. Thus mixtures of hydrochloric acid (or any other strong acid) and acetic (ethanoic) acid (or any other weak acid of comparable strength) can be titrated with a weak base (e.g. aqueous ammonia) or with a strong base (e.g. sodium hydroxide) reasonably satisfactory end points are obtained. 

Discussion. The formation of coloured compounds by coupling phenols with diazotised primary aromatic amines has long been recognised as a method of determining phenols, and procedures have been evolved whereby the phenol solution is titrated with a diazonium solution which has been calibrated against known concentrations of the phenol. The resultant reaction products are coloured, but many are only sparingly soluble in water and organic solvents and do not therefore lend themselves to colorimetric determination. 

Determination of organic compounds. The application of photometric titrimetry to organic compounds may be exemplified by the titration of phenols. This can be carried out by working at the /max value (in the ultraviolet) for the phenol being determined (see Section 17.50). It has been shown that by titrating with tetra-n-butylammonium hydroxide and using propan-2-ol as solvent, it is possible to differentiate between substituted phenols.24... 

Szmant and Suld88 measured pK values for various substituted benzoic acids and phenols in 48% aqueous ethanol by potentiometric titration. Substituent constants... 

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]. 

Marsh grapefhiit (MGF) pulp was homogenized in 5 volumes of extraction buffer at 4 C and maintained at pH 8.0 (28). The homogenate was stirred for one hour, centrifuged and the supernatant used as the PE extract. Activity was measured by titration with a Brinkman (Westbury, NY) pH stat titrator at pH 7.5 and 30°C in 25 mL of 1 % high methoxyl pectin (Citrus Colloids Limited, Hereford, UK) with O.IM NaCl. PE units are expressed as the microequivalents of ester hydrolysed per minute. Uronic acid analyses were conducted based on the m-phenyl phenol (4) as modified for microplate reading (30). 

Potentiometric titration procedures with sodium methoxide have been reported for non-sulfur-containing organotin compounds in solvent extracts of polymers, and for phenolic antioxidants with sodium isopropox-ide in pyridine medium [21]. Organotin compounds in solvent extracts of PVC can be determined by potentiometric and manual titration procedures [487,488]. 

Microcoulometric titration is used as the detection mode in some commercial sulfur-specific analysers. Sulfur in PP and waxes (range from 0.6 to 6 ppm S) were determined by means of an oxidative coulometric procedure [537]. The coulometric electrochemical array detector was used for determining a variety of synthetic phenolic antioxidants (PG, THBP, TBHQ, NDGA, BHA, OG, Ionox 100, BHT, DG) in food and oils [538],... 

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