Lead/ions/salts determination

Following the lead in the study of anionic polymerisations, several workers used common-ion salts to shift equilibrium (11) in attempts to determine kp and by means of... 

Sulphur can be determined in sulphur-containing compounds with a lead ion-selective electrode by potentiometric titration after oxygen-flask combustion to sulphate [407], but any phosphate which forms a very insoluble lead salt must first be removed. The recently developed barium ion-selective electrode is also convenient for this purpose [408]. 

Polarography, because of its sensitivity, is well suited for the evaluation of the concentration in the final stages of analysis of certain elements. Thus the application of polarography was suggested long ago for the determination of sulphur after combustion. < > The concentration of sulphates was determined from the decrease of the wave-height for barium or lead ions or by retitration. ( ) Another method uses the peroxide bomb decomposition and retitration of an excess of a barium salt added, by amperometric control of potassium chromate. 

Lead salts have formed a favourite object of investigation because the adsorption of the potential-determining lead ions can easily be followed by the method of radioactive indicators (ThB). The first investigations in this direction were, from Paneth and VoRWERK Later the method was applied by Imre and by Kolthoff The latter also applied several other methods of adsorption measurement on PbSO. ... 

However, the peroxomonophosphate ion decomposes relatively rapidly ia aqueous solution. A mixture of peroxodiphosphoric and peroxomonophoshoric acids can be produced by treatiag a cold phosphoric acid solution with elemental fluorine (qv) (49). Peroxodiphosphoric acid is not produced commercially. Ammonium, lithium, sodium, potassium, mbidium, cesium, barium, 2iac, lead, and silver salts have all been reported. The crystal stmctures of the ammonium, lithium, sodium, and potassium compounds, which crysta11i2e with varyiag numbers of water molecules, have been determined (50). 

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-... 

Determination of silver as chloride Discussion. The theory of the process is given under Chloride (Section 11.57). Lead, copper(I), palladium)II), mercury)I), and thallium)I) ions interfere, as do cyanides and thiosulphates. If a mercury(I) [or copper(I) or thallium(I)] salt is present, it must be oxidised with concentrated nitric acid before the precipitation of silver this process also destroys cyanides and thiosulphates. If lead is present, the solution must be diluted so that it contains not more than 0.25 g of the substance in 200 mL, and the hydrochloric acid must be added very slowly. Compounds of bismuth and antimony that hydrolyse in the dilute acid medium used for the complete precipitation of silver must be absent. For possible errors in the weight of silver chloride due to the action of light, see Section 11.57. 

We illustrate this approach using the equilibrium shown in Figure 16-10. When solid LiF is added to water, a small amount of the salt dissolves, leading to equilibrium between the solid and a solution. Chemical analysis reveals that the equilibrium concentration of F ions in the solution is 6.16 X 10 M. We want to determine the equilibrium constant for this process. 

Salts such as silver chloride or lead sulfate which are ordinarily called insoluble do have a definite value of solubility in water. This value can be determined from conductance measurements of their saturated solutions. Since a very small amount of solute is present it must be completely dissociated into ions even in a saturated solution so that the equivalent conductivity, KV, is equal to the equivalent conductivity at infinite dilution which according to Kohlrausch s law is the sum of ionic conductances or ionic mobilities (ionic conductances are often referred to as ionic mobilities on account of the dependence of ionic conductances on the velocities at which ions migrate under the influence of an applied emf) ... 

The ethylene bromonium and 1-bromoethyl cations and their neutral and anionic counterparts have been the subject of a tandem mass spectrometric study of dissociation and gas-phase redox reactions. IR and Raman studies of the bioactive bromonium cation (19), as its hydrogensulfate salt, agree with the results of an X-ray structure determination, and theoretical calculations are also in agreement, except for the details of the NO2 groups. The azaallenium ion (22) is an intermediate in the photolysis of (20) (21) and (22) could both be seen. Flash photolysis of (23) leads to (24), (25), and (26), all of which could be trapped by nucleophiles (27) was not an intermediate. NMR lineshape analysis of the spectmm of (28) leads to reaction rate constants of formation for both the intimate ion pair (29) and the solvent-separated ion pair (30). ... 

The extremely low solubility of lead phosphate in water (about 6 x 10 15m) again suggests potentiometric analysis. Selig57,59 determined micro amounts of phosphate by precipitation with lead perchlorate in aqueous medium. The sample was buffered at pH 8.25-8.75 and a lead-selective electrode was used to establish the end-point. The detection limit is about 10 pg of phosphorus. Anions which form insoluble lead salts, such as molybdate, tungstate or chromate, interfere with the procedure. Similar direct potentiometric titrations of phosphate by precipitation as insoluble salts of lanthanum(III), copper(II) or cadmium(II) are suggested, the corresponding ion-selective electrodes being used to detect the end-point. 

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