Spectrophotometric solvent acidity

Analytical Techniques. Sorbic acid and potassium sorbate are assayed titrimetricaHy (51). The quantitative analysis of sorbic acid in food or beverages, which may require solvent extraction or steam distillation (52,53), employs various techniques. The two classical methods are both spectrophotometric (54—56). In the ultraviolet method, the prepared sample is acidified and the sorbic acid is measured at 250 260 nm. In the colorimetric method, the sorbic acid in the prepared sample is oxidized and then reacts with thiobarbituric acid the complex is measured at - 530 nm. Chromatographic techniques are also used for the analysis of sorbic acid. High pressure Hquid chromatography with ultraviolet detection is used to separate and quantify sorbic acid from other ultraviolet-absorbing species (57—59). Sorbic acid in food extracts is deterrnined by gas chromatography with flame ionization detection (60—62). 

All stated pK values in this book are for data in dilute aqueous solutions unless otherwise stated, although the dielectric constants, ionic strengths of the solutions and the method of measurement, e.g. potentiometric, spectrophotometric etc, are not given. Estimated values are also for dilute aqueous solutions whether or not the material is soluble enough in water. Generally the more dilute the solution the closer is the pK to the real thermodynamic value. The pK in mixed aqueous solvents can vary considerably with the relative concentrations and with the nature of the solvents. For example the pK values for V-benzylpenicillin are 2.76 and 4.84 in H2O and H20/EtOH (20 80) respectively the pK values for (-)-ephedrine are 9.58 and 8.84 in H2O and H20/Me0CH2CH20H (20 80) respectively and for cyclopentylamine the pK values are 10.65 and 4.05 in H2O and H20/EtOH (50 50) respectively. pK values in acetic acid or aqueous acetic acid are generally lower than in H2O. 

Spectrophotometric methods may often be applied directly to the solvent extract utilising the absorption of the extracted species in the ultraviolet or visible region. A typical example is the extraction and determination of nickel as dimethylglyoximate in chloroform by measuring the absorption of the complex at 366 nm. Direct measurement of absorbance may also be made with appropriate ion association complexes, e.g. the ferroin anionic detergent system, but improved results can sometimes be obtained by developing a chelate complex after extraction. An example is the extraction of uranyl nitrate from nitric acid into tributyl phosphate and the subsequent addition of dibenzoylmethane to the solvent to form a soluble coloured chelate. 

Discussion. Sodium diethyldithiocarbamate (B) reacts with a weakly acidic or ammoniacal solution of copper(II) in low concentration to produce a brown colloidal suspension of the copper(II) diethyldithiocarbamate. The suspension may be extracted with an organic solvent (chloroform, carbon tetrachloride or butyl acetate) and the coloured extract analysed spectrophotometrically at 560 nm (butyl acetate) or 435 nm (chloroform or carbon tetrachloride). 

In cases where it proves impossible to find a suitable indicator (and this will occur when dealing with strongly coloured solutions) then titration may be possible by an electrometric method such as conductimetric, potentiometric or amperometric titration see Chapters 13-16. In some instances, spectrophotometric titration (Chapter 17) may be feasible. It should also be noted that ifit is possible to work in a non-aqueous solution rather than in water, then acidic and basic properties may be altered according to the solvent chosen, and titrations which are difficult in aqueous solution may then become easy to perform. This procedure is widely used for the analysis of organic materials but is of very limited application with inorganic substances and is discussed in Sections 10.19-10.21. 

Ifydroxamic acids reagents for the solvent extraction and spectrophotometric determination of metals. Y. K. Agrawal and S. A. Patel, Rev. Anal. Chem., 1980, 4, 237-278 (167). 

Klooster, N. Th. M., van der Trouw, F. Mandel, M. (1984). Solvent effects in polyelectrolyte solutions. 3. Spectrophotometric results with (partially) neutralised poly(acrylic acid) in methanol and general conclusions regarding these systems. Macromolecules, 17, 2087-93. 

Here we shall confine ourselves to the solvents benzene and 1,2-dichloroethane (class 8). Considering benzene, many investigators have demonstrated since the 1930s the feasibility of titrations in this solvent using both potentiometric and spectrophotometric methods, paying much attention to acid-base indicator reactions under the influence of primary, secondary and tertiary amines. Association of carboxylic acids in benzene was studied at a later stage, mainly on the basis of colligative properties, IR spectroscopy and solvent extraction. ... 

The light-absorbing impurities of oxytetracycline hydrochloride and oxytetracycline dihydrate [2,4,6] are detected using a UV-spectrophotometric method. In all the compendia, the absorbance of a solution of 2.0 mg/mL in a mixture of 1 volume of hydrochloric acid solution (0.1 mol/L) and 99 volumes of methanol at 430 nm not greater than 0.50 is required the absorbance of a solution of 10 mg/mL in the same solvent at 490 nm is not greater than 0.20. The measurements are carried out within 1 h of the preparation of the solutions. 

Brzelinski and Nelson [214] have described a solvent extraction procedure for the spectrophotometric determination of nanomolar concentrations of silicic acid in seawater. 

In the Nile blue spectrophotometric method, 10 ml 2% aqueous hydrofluoric acid is added to a 10 ml sample contained in a polyethylene bottle. The mixture is shaken for about 2h. Aqueous ferrous sulfate 10% 10 ml and 1ml 0.1% aqueous Nile blue A are added, then extracted with o-dichlorobenzene (10 ml and 3x5 ml). The combined organic extracts are diluted to 50 ml with the solvent and the extinction measured at 647 nm. Interference from chloride ions up to 100 mg/1 can be eliminated by precipitation as silver chloride. 

The pKa of the protonation of the nitrogen in position 8 has been reported as 6.02 and the pKa for the carboxylate anion formulation has been reported as -0.94. These were determined by Staroscik and Sulkowska by a spectrophotometric method.(14) Further study by the same workers on the partition equilibria of nalidixic acid between water and various organic solvents led to calculations of the pKa values of 5.99 + 0.03 for N-protonation and -0.86 4- 0.07 for carboxylate anion formation.(12) Takasugi and co-workers reported the apparent pKa of nalidixic acid to be 5.9 at 28° by a spectrophotometric method.(13)... 

The plateau region corresponds to effectively complete N-protonation. The pK value measured spectrophotometrically (1.90) agreed with that derived from the kinetic measurements. Similar good agreement was obtained for the N-Et and 4-Me reactants and also for the unsubstituted phenylhydroxylamine in D2O. The measured solvent KIE was also in agreement with the mechanism in Scheme 7. Acid catalysis at high acidity is believed... 

Drinking water, waste water, natural water Direct distillation or distillation of solvent-cleaned sample (if necessary) at acidic pH, react with 4-amino-antipyrine and potassium Spectrophotometric 1 pg/L for 500-mL sample NG... 

In the spectrophotometric determination of enthalpies of adduct formation, one usually measures the equilibrium concentration of [AB] or [A]. Following a treatment of competing equilibria reported by Tamres 25) consider the effect of base-solvent interaction on this experiment when one investigates the properties corresponding to the free and complexed acid. Now, [AB] can be determined even if the base interacts with the solvent, say CCI4. Again, describing the system by equation ... 

Extraction can be nsed for separation or isolation of the analyte from the sample matrix or vice versa as well as a preconcentration method. Extraction of metal ions is based on the reaction of weak organic acids with metal ions that give nncharged complexes that are highly solnble in organic solvents as ethers, hydrocarbons, ketones and polychlorinated species (generally chloroform and carbon tetrachloride). The efficacy of the extraction is mainly dependent on the extent to which solntes distribnte themselves between two immiscible solvents. The amonnts of analyte can be determined spectrophotometrically as well as with other available analytical methods. 

Procedure 1 We select several HA-type acids, for which pKa values of <7.5 are expected, and determine their pKa and K HAJ) accurately by method(s) other than potentiometry. If the selected acid is a nitro-substituted phenol that has no tendency to homoconjugate (p. 71), we dissolve various amounts of it in the solvent and measure the UV/vis spectrophotometric absorption for the phenolate anion formed by dissociation. For the conductimetric determination of pKa and K HA])), see Section 7.3.2. 

A comparison of ELISA, HPLC, and HPLC-ELISA methods was published for the determination of SAL in chicken liver tissue. Samples were homogenized with MeOH and extracted with methylenechloride. Some samples were analyzed by HPLC using the isocratic solvent system and postcolumn derivatization (vanillin in MeOH containing sulphuric acid), with the eluent monitoring at 520 nm. The HPLC-ELISA system was used to characterize nonspecific effects analyzing column fractions by ELISA, since this detection is over 1000 times more sensitive than the spectrophotometric one. This alleviated the need to derivatize the drug prior to the detection (104). 

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