Thiocyanate precipitation titration

Procedure B. Pipette 25 mL of the diluted solution into a 250 mL conical flask containing 5mL 6 M nitric acid. Add a slight excess of standard 0.1M silver nitrate (about 30 mL in all) from a burette. Then add 2-3 mL pure nitrobenzene and 1 mL of the iron(III) indicator, and shake vigorously to coagulate the precipitate. Titrate the residual silver nitrate with standard 0.1M thiocyanate until a permanent faint reddish-brown coloration appears. 

Pipette 25.0 mL of the potassium ion solution (about 10 mg K + ) into a 50 mL graduated flask, add 0.5 mL 1M nitric acid and mix. Introduce 20.0 mL of the sodium tetraphenylborate solution, dilute to the mark, mix, then pour the mixture into a 150mL flask provided with a ground stopper. Shake the stoppered flask for 5 minutes on a mechanical shaker to coagulate the precipitate, then filter most of the solution through a dry Whatman No. 40 filter paper into a dry beaker. Transfer 25.0 mL of the filtrate into a 250 mL conical flask and add 75 mL of water, 1.0 mL of iron(III) nitrate solution, and 1.0 mL of sodium thiocyanate solution. Titrate with the mercury(II) nitrate solution as described above. 

The end points of precipitation titrations can be variously detected. An indicator exhibiting a pronounced colour change with the first excess of the titrant may be used. The Mohr method, involving the formation of red silver chromate with the appearance of an excess of silver ions, is an important example of this procedure, whilst the Volhard method, which uses the ferric thiocyanate colour as an indication of the presence of excess thiocyanate ions, is another. A series of indicators known as adsorption indicators have also been utilized. These consist of organic dyes such as fluorescein which are used in silver nitrate titrations. When the equivalence point is passed the excess silver ions are adsorbed on the precipitate to give a positively charged surface which attracts and adsorbs fluoresceinate ions. This adsorption is accompanied by the appearance of a red colour on the precipitate surface. Finally, the electroanalytical methods described in Chapter 6 may be used to scan the solution for metal ions. Table 5.12 includes some examples of substances determined by silver titrations and Table 5.13 some miscellaneous precipitation methods. Other examples have already been mentioned under complexometric titrations. 

Ganescu et al. used thiocyanato Cr(III)-complexes in the titrimetric and spectrophotometric determination of dipyridamole [16]. For titrimetric analysis of the drug (1.36-27.2 mg), sample solutions (25-50 mL) were acidified with hydrochloric acid and treated with excess of a 3% solution of ammonium dianilinetetrakis (thiocyanato) chromium (III) in aqueous 25% ethanol. The red-violet precipitate was collected and washed, decomposed with NaOH, and the mixture again acidified. The liberated thiocyanate was titrated with potassium permanganate, potassium bromate, or potassium iodate. 

Table 13-3 lists some typical applications of precipitation titrations in which silver nitrate is the standard solution. In most of these methods, the analyte is precipitated with a measured excess of silver nitrate, and the excess is determined by a Volhard titration with standard potassium thiocyanate. 

Gravimetric method such as AgCl or fire assay is used. Gay-Lussac method involves the titration of Ag with NaCl and/or KBr in acid solution. The endpoint is taken as the point at which no further precipitation of silver halide is observed upon the addition of more precipitant. Fajans method is based on the precipitation of Ag with chloride or bromide ions, using an adsorption indicator to detect the endpoint. Rhodamine 6G or dichlorofluorescein is used as the adsorption indicators. Volhard method is based on the titration of Ag with potassium or sodium thiocyanate to form insoluble silver thiocyanate. This titration is... 

Mohr s method is essentially used for the titration of chloride and bromide ions. It is not satisfactory for iodide and thiocyanate ions because they exhibit a strong tendency to be adsorbed on the silver iodide and silver thiocyanate precipitates. Finally, some ions that give poorly soluble compounds with silver (see Sect. 37.1.2) may disturb the titration. 

To about 0-5 g add 25 ml of O IN silver nitrate. After the addition of 10 ml of dilute nitric acid and heating on a water-bath for thirty minutes the salt is completely decomposed and the silver iodide precipitated. Titrate the excess of silver nitrate with 0 1 N potassium thiocyanate solution, using ferric alum as indicator. 1 ml O IN = 0 01269 g I. 

Indicators for silver-halide precipitation titrations are of two types. The first react specifically when an excess of titrant becomes present immediately after the end point - for example, if a small amount of potassium chromate is added, it will react with excess silver ions to produce deep red silver chromate in neutral solutions (Mohi s method). In acid solutions, the silver is titrated with potassium thiocyanate (KCNS) solution (Volhard s method). Iron (III) ammonium sulfate solution is added and reacts with an excesss of thiocyanate to produce a deep red iron thiocyanate species. 

The major applications of precipitation titrations involve the determination of halides with silver, or the reverse, or the determination of silver in acid solutions with thiocyanate. 

Quantitative. Classically, silver concentration ia solution has been determined by titration with a standard solution of thiocyanate. Ferric ion is the iadicator. The deep red ferric thiocyanate color appears only when the silver is completely titrated. GravimetricaHy, silver is determined by precipitation with chloride, sulfide, or 1,2,3-benzotriazole. Silver can be precipitated as the metal by electro deposition or chemical reduciag agents. A colored silver diethjldithiocarbamate complex, extractable by organic solvents, is used for the spectrophotometric determination of silver complexes. 

Analysis. The abiUty of silver ion to form sparingly soluble precipitates with many anions has been appHed to their quantitative deterrnination. Bromide, chloride, iodide, thiocyanate, and borate are determined by the titration of solutions containing these anions using standardized silver nitrate solutions in the presence of a suitable indicator. These titrations use fluorescein, tartrazine, rhodamine 6-G, and phenosafranine as indicators (50). 

Ana.lytica.1 Methods. Thiocyanate is quantitatively precipitated as silver thiocyanate, and thus can be conveniendy titrated with silver nitrate. In the presence of a ferric salt, a red-brown color, produced by the ferric thiocyanate compex, indicates the end point. 

Cyanamide is precipitated by excess ammoniacal silver nitrate as disilver cyanamide [3384-87-0] which is dissolved in acid and titrated with thiocyanate solution (27). 

These reactions take place with sparingly soluble silver salts, and hence provide a method for the determination of the halide ions Cl", Br, I-, and the thiocyanate ion SCN ". The anion is first precipitated as the silver salt, the latter dissolved in a solution of [Ni(CN)4]2", and the equivalent amount of nickel thereby set free is determined by rapid titration with EDTA using an appropriate indicator (murexide, bromopyrogallol red). 

The method may be applied to those anions (e.g. chloride, bromide, and iodide) which are completely precipitated by silver and are sparingly soluble in dilute nitric acid. Excess of standard silver nitrate solution is added to the solution containing free nitric acid, and the residual silver nitrate solution is titrated with standard thiocyanate solution. This is sometimes termed the residual process. Anions whose silver salts are slightly soluble in water, but which are soluble in nitric acid, such as phosphate, arsenate, chromate, sulphide, and oxalate, may be precipitated in neutral solution with an excess of standard silver nitrate solution. The precipitate is filtered off, thoroughly washed, dissolved in dilute nitric acid, and the silver titrated with thiocyanate solution. Alternatively, the residual silver nitrate in the filtrate from the precipitation may be determined with thiocyanate solution after acidification with dilute nitric acid. 

Pipette 25 mL of the standard 0.1 M silver nitrate into a 250 mL conical flask, add 5mL of 6M nitric acid and 1 mL of the iron(III) indicator solution. Run in the potassium or ammonium thiocyanate solution from a burette. At first a white precipitate is produced, rendering the liquid of a milky appearance, and as each drop of thiocyanate falls in, it produces a reddish-brown cloud, which quickly disappears on shaking. As the end point approaches, the precipitate becomes flocculent and settles easily finally one drop of the thiocyanate solution produces a faint brown colour, which no longer disappears upon shaking. This is the end point. The indicator blank amounts to 0.01 mL ofO.lM silver nitrate. It is essential to shake vigorously during the titration in order to obtain correct results. ... 

Use of tartrazine as indicator. Satisfactory results may be obtained by the use of tartrazine as indicator. Proceed as above, but add 4 drops of tartrazine (0.5 per cent aqueous solution) in lieu of the iron(III) indicator. The precipitate will appear pale yellow during the titration, but the supernatant liquid (best viewed by placing the eye at the level of the liquid and looking through it) is colourless. At the end point, the supernatant liquid assumes a bright lemon-yellow colour. The titration is sharp to one drop of 0.1 M thiocyanate solution. 

Iodides can also be determined by this method, and in this case too there is no need to filter off the silver halide, since silver iodide is very much less soluble than silver thiocyanate. In this determination the iodide solution must be very dilute in order to reduce adsorption effects. The dilute iodide solution (ca 300 mL), acidified with dilute nitric acid, is treated very slowly and with vigorous stirring or shaking with standard 0.1 M silver nitrate until the yellow precipitate coagulates and the supernatant liquid appears colourless. Silver nitrate is then present in excess. One millilitre of iron(III) indicator solution is added, and the residual silver nitrate is titrated with standard 0.1M ammonium or potassium thiocyanate. 

Discussion. Arsenates in solution are precipitated as silver arsenate, Ag3 As04, by the addition of neutral silver nitrate solution the solution must be neutral, or if slightly acid, an excess of sodium acetate must be present to reduce the acidity if strongly acid, most of the acid should be neutralised by aqueous sodium hydroxide. The silver arsenate is dissolved in dilute nitric acid, and the silver titrated with standard thiocyanate solution. The silver arsenate has nearly six times the weight of the arsenic, hence quite small amounts of arsenic may be determined by this procedure. 

Discussion. Potassium may be precipitated with excess of sodium tetraphenyl-borate solution as potassium tetraphenylborate. The excess of reagent is determined by titration with mercury(II) nitrate solution. The indicator consists of a mixture of iron(III) nitrate and dilute sodium thiocyanate solution. The end-point is revealed by the decolorisation of the iron(III)-thiocyanate complex due to the formation of the colourless mercury(II) thiocyanate. The reaction between mercury( II) nitrate and sodium tetraphenylborate under the experimental conditions used is not quite stoichiometric hence it is necessary to determine the volume in mL of Hg(N03)2 solution equivalent to 1 mL of a NaB(C6H5)4 solution. Halides must be absent. 

After the addition of the potassium iodide solution, run in standard 0.1M sodium thiosulphate until the brown colour of the iodine fades, then add 2 mL of starch solution, and continue the addition of the thiosulphate solution until the blue colour commences to fade. Then add about 1 g of potassium thiocyanate or ammonium thiocyanate, preferably as a 10 per cent aqueous solution the blue colour will instantly become more intense. Complete the titration as quickly as possible. The precipitate possesses a pale pink colour, and a distinct permanent end point is readily obtained. 

Copper(II) compounds. Many other metallic ions which are capable of undergoing oxidation by potassium iodate can also be determined. Thus, for example, copper(II) compounds can be analysed by precipitation of copper)I) thiocyanate which is titrated with potassium iodate ... 

Mercury(II) chloranilate 700 Mercury(II) nitrate standard soln. of, 359 Mercury/mercury( II )-EDTA electrode (mercury electrode) 586 potentiometric titration of metallic ions with EDTA and, 588 prepn. of, 587 Mercury thiocyanate 700 Metaphosphoric acid in homogeneous precipitation, 426 Metal apparatus 93 Metal ion buffer 53... 

Soliman and Belal investigated argentimetric (67,68) and mercurimetric (69) methods. Hydralazine precipitates silver from ammoniacal silver nitrate solution. The silver is dissolved with hot nitric acid and titrated with ammonium thiocyanate solution. Alternatively, mercury is precipitated from alkaline potassium mercuric iodide solution. The precipitated mercury is dissolved by adding excess standard iodine solution. The excess iodine is back-titrated with sodium thiosulfate solution after acidifying with acetic acid. 

In actual practice, however, such titrations are more or less restricted to those involving precipitation of Ag+ with anions, for instance halogens (Cl , Br, I-) and thiocyanate (SCN-). Generally, it is quite difficult and tedious to locate the exact point at which further addition of reagent affords no more precipitation. Therefore, the choice and wisdom of a chemical reaction is preferably sought so as to result in either a coloured solution or a coloured precipitate at the end point. A typical instance may be cited by application of potassium chromate (K2Cr04) solution in the above case whereby any extra drop of silver nitrate, after all the chloride has been precipitated, immediately causes precipitation of red chromate showing that the end point has been duly achieved. 

Chlorides, bromides, and iodides can be quantitatively determined by treatment with silver nitrate, and, with suitable precautions, the precipitated halide is washed, dried, and weighed. Chlorides in neutral soln. can be determined by F. Mohr s volumetric process 27 by titration with a standard soln. of silver nitrate with a little potassium chromate or sodium phosphate as indicator. When all the chloride has reacted with the silver nitrate, any further addition of this salt gives a yellow coloration with the phosphate, and a red coloration with the chromate. In J. Volhard s volumetric process, the chloride is treated with an excess of an acidified soln. of silver nitrate of known concentration. The excess of silver nitrate is filtered from the precipitated chloride, and titrated with a standard soln. of ammonium thiocyanate, NH4CN8—a little ferric alum is used as indicator. When the silver nitrate is all converted into thiocyanate AgN03-fNH4CNS=AgCNS +NH4NOS, the blood-red coloration of ferric thiocyanate appears. 

To insure that all the chloride ions will be precipitated, excess AgN03 is added to the solution. The excess Ag+ ion will be measured by back-titration with SCN , thiocyanate ion. The net ionic equation describing this reaction is... 

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