Interference precipitation titration

Precipitation titrations are typified by the titration of chloride with silver or vice versa. In this case, interferences with the precipitation reaction may occur because of components in the soil, and the soil itself may interfere with detection of the end point. Thus, complexation reactions are rarely applied directly to soil however, they can be applied to soil extracts. Common environmental titration methods described in the United States Environmental Protection Agency (USEPA) methods are summarized in Table 10.1 [1,2],... 

Applications of precipitation titrations are listed in Table 7-1. Whereas the Volhard method is an argentometric titration, the Fajans method has wider applications. Because the Volhard titration is carried out in acidic solution (typically 0.2 M HN03), it avoids certain interferences that affect other titrations. Silver salts of CO -, C20 -, and AsO " are soluble in acidic solution, so these anions do not interfere. 

Industrial grade NaCl has a content of 92-98%. The precipitation titration can be conducted using 0.1 N AgNO, as the titrant and 5% K,Ci<) as the indicator (the Mohr method). The sample chloride solution should be buffered with calcium carbonate to a pH between 6.3 and 7.2 in order to avoid any interference from other... 

Amperometric titrations have a number of advantages over other titri-metric methods determinations can usually be carried out in very dilute solutions (about 10 N or even, in certain cases, 10 N) and they are rapid since only a few measurements of current, before and after the end-point, at a constant applied voltage, need be made. It is often possible to carry out titrations in cases where potentiometric or visual-indicator methods are unsuitable such as in acid-base titrations in which the reaction product is hydrolysed or in precipitation titrations in which the precipitate has a significant solubility. There is, too, no interference from foreign electrolytes. 

A further complication of precipitation titrations is the occlusion or adsorption of excess ions present early in the titration (such as the argentometric halide determinations). With complexometric titrations the presence of other ions which also form complexes can interfere. Any or all of these influences may be the reason behind why the theoretically possible accuracy of better than 0.1% is not always attained. In such cases the reader is referred to the appropriate literature in the field of analytical chemistry. 

Inorganic Analysis Complexation titrimetry continues to be listed as a standard method for the determination of hardness, Ca +, CN , and Ch in water and waste-water analysis. The evaluation of hardness was described earlier in Method 9.2. The determination of Ca + is complicated by the presence of Mg +, which also reacts with EDTA. To prevent an interference from Mg +, the pH is adjusted to 12-13, precipitating any Mg + as Mg(OH)2. Titrating with EDTA using murexide or Eri-ochrome Blue Black R as a visual indicator gives the concentration of Ca +. 

The precipitated acetyHde must be decomposed with hydrochloric acid after the titration as a safety measure. Concentrated solutions of silver nitrate or silver perchlorate form soluble complexes of silver acetyHde (89). Ammonia and hydrogen sulfide interfere with the silver nitrate method which is less... 

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-... 

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. 

Discussion. The theory of the titration of cyanides with silver nitrate solution has been given in Section 10.44. All silver salts except the sulphide are readily soluble in excess of a solution of an alkali cyanide, hence chloride, bromide, and iodide do not interfere. The only difficulty in obtaining a sharp end point lies in the fact that silver cyanide is often precipitated in a curdy form which does not readily re-dissolve, and, moreover, the end point is not easy to detect with accuracy. 

The effect of different ions upon the titration is similar to that given under iron(III) (Section 17.57). Iron(III) interferes (small amounts may be precipitated with sodium fluoride solution) tin(IV) should be masked with 20 per cent aqueous tartaric acid solution. The procedure may be employed for the determination of copper in brass, bronze, and bell metal without any previous separations except the removal of insoluble lead sulphate when present. 

In the indirect amperometric method [560], saturated uranyl zinc acetate solution is added to the sample containing 0.1-10 mg sodium. The solution is heated for 30 minutes at 100 °C to complete precipitation. The solution is filtered and the precipitate washed several times with 2 ml of the reagent and then five times with 99% ethanol saturated with sodium uranyl zinc acetate. The precipitate is dissolved and diluted to a known volume. To an aliquot containing up to 1.7 mg zinc, 1M tartaric acid (2-3 ml) and 3 M ammonium acetate (8-10 ml) are added and the pH adjusted to 7.5-8.0 with 2 M aqueous ammonia. The solution is diluted to 25 ml and an equal volume of ethanol added. It is titrated amperometrically with 0.01 M K4Fe(CN)6 using a platinum electrode. Uranium does not interfere with the determination of sodium. 

An acidic solution of tellurium (IV) or tellurium (VI) is treated with sulfur dioxide and hydrazine hydrochloride. Tellurium precipitated from solution can be estimated by gravimetry. Selenium interferes with this test. A volumetric test involves converting tellurium to tellurous acid and oxidizing the acid with excess ceric sulfate in hot sulfuric acid in the presence of Cr3+ ion as catalyst. The excess ceric sulfate is measured by titration with a standard solution of ferrous ammonium sulfate. 

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. 

To measure hardness, the sample is treated with ascorbic acid (or hydroxylamine) to reduce Fe3+ to Fe2+ and with cyanide to mask Fe2+, Cu+, and several other minor metal ions. Titration with EDTA at pH 10 in NH3 buffer then gives the total concentrations of Ca2+ and Mg2+. Ca2+ can be determined separately if the titration is carried out at pH 13 without ammonia. At this pH, Mg(OH)2 precipitates and is inaccessible to EDTA. Interference by many metal ions can be reduced by the right choice of indicators.21... 

The excess yellow Bil4 is then titrated with EDTA. The end point occurs when the yellow color disappears. (Sodium thiosulfate is used in the reaction to prevent the liberated I from being oxidized to yellow aqueous I2 by 02 from the air.) The precipitation is fairly selective for Cs+. The ions Li+. Na+, K+. and low concentrations of Rb+ do not interfere, although Tl+ does. Suppose that 25.00 mL of unknown containing Cs were treated with 25.00 mL of0.086 40 M NaBiI4 and the unreacted Bil4 required 14.24 mL of 0.043 7 M EDTA for complete titration. Find the concentration of Cs+ in the unknown. 

In a definitive series of experimental investigations H. N. Wilson showed that the quinolinium salt, (C isNJ fPCV I2M0O3]3- was anhydrous, contained exactly 12 moles of molybdenum trioxide per mole of phosphate, that the precipitate had a negligible solubility and could be dried to constant weight in two hours at 105 °C. This precipitate also lent itself to a precise alkalimetric titration. In the presence of citric acid interference by silica was inhibited so that the method was admirably suitable for the analysis of basic slags or fertilizers.34... 

Presence of oxidizable substances in the sample would interfere in the test, thus giving high results. These include S2. S 0,2. and certain metal ions such as Fe2+ in lower oxidation state. Sulfide should be removed by adding 0.5 g zinc acetate, allowing the zinc sulfide precipitate to settle and drawing out the supernatant liquid for analysis. If thiosulfate is present, determine its concentration in an aliquot of sample by iodometric titration using iodine standard. Subract the concentration of thiosulfate from the iodometric sulfite results to calculate the true value of SO,2. ... 

The first of these, utilized by Yoder, McCalip and Seibert,34 and by Balch, Broeg and Ambler,37 provides for the extraction of the aconitic acid from the sample being investigated, usually with diethyl ether, and the subsequent isolation of the acid from the solvent. In dealing with solid samples, e.g. alkaline earth aconitates, evaporator scale, etc., the prescribed procedure is to dissolve the material in aqueous mineral acid and to extract the acid solution exhaustively with ether. The ether extract is then evaporated under reduced pressure, the dried residue titrated with standard alkali and the titratable acid calculated as aconitic acid. In dealing with such solid samples it is often necessary to make an additional determination for oxalic acid which otherwise would be assumed to be aconitic acid.37 The aconitic acid in liquid samples is usually precipitated as the insoluble lead salt which is separated and treated as any other solid sample. In some cases this procedure is unnecessary and the liquid samples are merely acidified with a mineral acid and then extracted with ether.37 This method for the determination of aconitic acid, however, requires a considerable amount of time and is further complicated by the interference of ether-soluble waxes and non-volatile acids. 

As this is an indirect method of determining the equivalence point it has some advantages. Dilute solutions can be titrated, allowing titration of sparingly soluble precipitates with no interference from supporting electrolyte. Non-electroactive compounds can be titrated so long as the titrant is electroactive, or vice versa. Titrations are fast, only three points before and three points after the equivalent point being necessary. 

A 366 mg sample of a compound A, a corrosive volatile red liquid, is dissolved in water. The solution is distinctly acidic but cannot be titrated with NaOH because the orange color interferes with detection of the endpoint. However, the solution is titrated with standard Ba(OH) 2 solution, requiring 6 millimoles of the latter to reach the phenolphthalein endpoint. At the end of the titration, a precipitate, B. remains. 

Verma and Bhuchar determined copper by reducing its tartrate complex with glucose to form insoluble CujO, which was treated with an excess of standard iodine and back-titrated with standard As(III). Oxalate was added as a complexing agent to aid in the oxidation of the CU2O, and precautions were taken to avoid air oxidation. The method has the advantage of avoiding interference from V(V). For the determination of copper in alloys, Rooney and Pratt separated copper by precipitation as its diethyldithiocarbamate from EDTA solution. 

Puschel and Stefanac ° use alkaline hydrogen peroxide in the oxygen flask method to oxidize arsenic to arsenate. The arsenate is titrated directly with standard lead nitrate solution with 4-(2-pyridylazo) resorcinol or 8-hydroxy-7-(4-sulpho-l-naphthylazo) quino-line-5-sulphonic acid as indicator. Phosphorus interferes in this method. The precision at the 99% confidence limit is within 0.67% for a 3-mg sample. In another variation, Stefanac used sodium acetate as the absorbing liquid, and arsenite and arsenate are precipitated with silver nitrate. The precipitate is dissolved in potassium nickel cyanide (K2Ni(CN)4) solution and the displaced nickel is titrated with EDTA solution, with murexide as indicator. The average error is within + 0.19% for a 3-mg sample. Halogens and phosphate interfere in the procedure. 

---