Standardization thiocyanate

APHA. 1992. Cyanide (45 00-CN)/thiocyanate. Standard methods for the examination of water and wastewater, 18th edition. American Public Health Association. Washington, D.C. 

Thiocyanate standard solns. 1.673 g potassium thiocyanate, KSCN in distilled water, diluted to 1 L. This stock soln. = 1000 mg SCN7L or 1 mL = 1 mg SCN". Prepare a secondary standard from the stock solution by diluting 1 mL stock solution to 100 mL with distilled water. Secondary std = 10 mg SCN-/L or 1 mL = 0.01 mg SCN". Prepare a series of calibration standards by diluting the secondary standard with distilled water as follows ... 

Reagents are added after pretreatment of the sample. The spot test is performed in a porcelain spot plate with 6 to 12 cavities. The test is performed using a few drops of sample, standards, and reagents. The color developed is compared with thiocyanate standards. The test is semiquantitative and is suitable for screening SCN in water. 

If the pH of the solution is above 10, add about 0.2 g Na2C03 and mix. Add a drop of phenophthalein indicator which will turn the solution red (or pink) in alkaline medium. Add 1 N HC1 dropwise till the color disappears. Place 3 drops of the above pretreated sample, 3 drops of distilled water, and 3 drops each of thiocyanate standards (0.05, 0.1, and 0.2 mg SCNYL) in the cavities of porcelain spot plate. Add 1 drop of chloramine-T solution to each cavity and mix with a clean glass rod. This is followed by the addition of 1 drop of pyridine-barbituric acid to each cavity. Again, mix the contents and allow it to stand for a minute. If thiocyanate is present, the sample spot will turn pink to red, depending on the concentration of SCN- in the sample. If deep red coloration is produced, dilute the sample and repeat the test. 

The above test would give SCN- concentration in an estimated range. For greater accuracy, place more standards in the cavities of spot plate for color comparison. Alternatively, once the SCN concentration range in the sample is known from the above screening test, prepare several thiocyanate standards within that range and repeat the spot test for color comparison. 

Thiocyanate standard solution the stock standard is made from KSCN. The secondary and working standards are prepared from this. See the preceding section under Colorimetric Method. 

A major advance was devised by Pehr Edman (University of Lund Sweden) that has become the standard method for N terminal residue analysis The Edman degrada tion IS based on the chemistry shown m Figure 27 12 A peptide reacts with phenyl iso thiocyanate to give a phenylthwcarbamoyl (PTC) denvative as shown m the first step This PTC derivative is then treated with an acid m an anhydrous medium (Edman used mtromethane saturated with hydrogen chloride) to cleave the amide bond between the N terminal ammo acid and the remainder of the peptide No other peptide bonds are cleaved m this step as amide bond hydrolysis requires water When the PTC derivative IS treated with acid m an anhydrous medium the sulfur atom of the C=S unit acts as... 

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). 

IQ. To determine the concentration of chloride ion, - a 5-mL aliquot of the methyl lithium solution is cautiously added to 25 ml of water and the resulting solution is acidified with concentrated sulfuric acid and then treated with 2-3 ml of ferric ammonium sulfate [Fe(NH4)( 04)2 12 H2O] indicator solution and 2-3 ml of benzyl alcohol. The resulting mixture is treated with 10.0 mL of standard aqueous 0.100 M silver nitrate solution and then titrated with standard aqueous 0.100 H potassium thiocyanate solution to a brownish-red endpoint. 

To limit the total porosity of the coating, checking by the Iron Solution Value (ISV) test in which samples are immersed under standard conditions in a solution of sulphuric acid, hydrogen peroxide and ammonium thiocyanate, and the amount of iron dissolved is measured... 

The following sections are concerned with the use of standard solutions of reagents such as silver nitrate, sodium chloride, potassium (or ammonium) thiocyanate, and potassium cyanide. Some of the determinations which will be considered strictly involve complex formation rather than precipitation reactions, but it is convenient to group them here as reactions involving the use of standard silver nitrate solutions. Before commencing the experimental work, the theoretical Sections 10.74 and 10.75 should be studied. 

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. 

Both ammonium and potassium thiocyanates are usually available as deliquescent solids the analytical-grade products are, however, free from chlorides and other interfering substances. An approximately 0.1M solution is, therefore, first prepared, and this is standardised by titration against standard 0.1 JVf silver nitrate. 

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. ... 

A commercial silver alloy in the form of wire or foil is suitable for this determination. Clean the alloy with emery cloth and weigh it accurately. Place it in a 250 mL conical flask, add 5 mL water and 10 mL concentrated nitric acid place a funnel in the mouth of the flask to avoid mechanical loss. Warm the flask gently until the alloy has dissolved. Add a little water and boil for 5 minutes in order to expel oxides of nitrogen. Transfer the cold solution quantitatively to a 100 mL graduated flask and make up to the mark with distilled water. Titrate 25 mL portions of the solution with standard 0.1 M thiocyanate. 

Discussion. The chloride solution is treated with excess of standard silver nitrate solution, and the residual silver nitrate determined by titration with standard thiocyanate solution. Now silver chloride is more soluble than silver thiocyanate, and would react with the thiocyanate thus ... 

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. 

From the volume of silver nitrate solution added, subtract the volume of silver nitrate solution that is equivalent to the volume of standard thiocyanate required. Then calculate the percentage of HCI in the sample. 

Bromides can also be determined by the Volhard method, but as silver bromide is less soluble than silver thiocyanate it is not necessary to filter off the silver bromide (compare chloride). The bromide solution is acidified with dilute nitric acid, an excess of standard 0.1M silver nitrate added, the mixture thoroughly shaken, and the residual silver nitrate determined with standard 0.1 M ammonium or potassium thiocyanate, using ammonium iron(III) sulphate as indicator. 

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. 

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. 

Procedure. Dissolve a weighed portion of the substance in which the amount of iron is to be determined in a suitable acid, and evaporate nearly to dryness to expel excess of acid. Dilute slightly with water, oxidise the iron to the iron(III) state with dilute potassium permanganate solution or with a little bromine water, and make up the liquid to 500 mL or other suitable volume. Take 40 mL of this solution and place in a 50 mL graduated flask, add 5 mL of the thiocyanate solution and 3 mL of AM nitric acid. Add de-ionised water to dilute to the mark. Prepare a blank using the same quantities of reagents. Measure the absorbance of the sample solution in a spectrophotometer at 480 nm (blue-green filter). Determine the concentration of this solution by comparison with values on a reference curve obtained in the same way from different concentrations of the standard iron solution. 

To use KBr discs for quantitative measurements it is best to employ an internal standard procedure in which a substance possessing a prominent isolated infrared absorption band is mixed with the potassium bromide. The substance most commonly used is potassium thiocyanate, KSCN, which is intimately mixed and ground to give a uniform concentration, usually 0.1-0.2 per cent, in the potassium bromide. A KBr/KSCN disc will give a characteristic absorption band at 2125 cm 1. Before quantitative measurements can be carried out it is necessary to prepare a calibration curve from a series of standards made using different amounts of the pure organic compound with the KBr/KSCN. A practical application of this is given in Section 19.9. 

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... 

A number of methods have been proposed for the detection of rancidity. The determination of active oxygen consists of dissolving the fat in a suitable medium such as chloroform and acetic acid, adding potassium iodide, and titrating the liberated iodine with a standard thiosulfate solution (16, 20). This is perhaps the most widely used method at the present time. Another procedure which has been proposed for the detection of peroxides employs ferrous ammonium sulfate and ammonium thiocyanate in acetone. The resulting red color of ferric thiocyanate is measured spectrophotometrically, and is said by the authors to yield more reproducible results than do the usual titration methods (21). 

These and similar results can be explained if the simultaneous reduction of hydrogen peroxide is due to an induced reaction. To show the characteristic features of this reaction some results are presented in Table 19 and Table 20. The procedure for these measurements was as follows. The solution of peroxy compounds given in columns 1 and 2 was made up to 20 ml and the pH was adjusted to the given value. Then potassium thiocyanate solution was added and, after the reaction time noted, the process was quenched by adding potassium iodide solution (0.3 g KI). After 5 sec the solution was acidified with 1 ml 2 iV sulphuric acid then using, molybdate catalyst solution, the iodine liberated was titrated with standard thiosulphate. 

To establish the well drainage boundaries and fluid flow patterns within the TFSA-waterflood pilot, an interwell chemical tracer study was conducted. Sodium thiocyanate was selected as the tracer on the basis of its low adsorption characteristics on reservoir rocks (36-38), its low and constant background concentration (0.9 mg/kg) in produced fluids and its ease and accuracy of analysis(39). On July 8, 1986, 500 lb (227 kg) of sodium thiocyanate dissolved in 500 gal (1.89 m3> of injection brine (76700 mg/kg of thiocyanate ion) were injected into Well TU-120. For the next five months, samples of produced fluids were obtained three times per week from each production well. The thiocyanate concentration in the produced brine samples were analyzed in duplicate by the standard ferric nitrate method(39) and in all cases, the precision of the thiocyanate determinations were within 0.3 mg/kg. The concentration of the ion in the produced brine returned to background levels when the sampling and analysis was concluded. 

Chlorine at the percentage level at which it occurs in sea water is usually determined by classical procedures using standard silver nitrate as the titrant and potassium chromate indicator, or alternatively by the mercuric thiocyanate procedure using dithizone as indicator. As large dilutions of the original sample are involved in these analyses, it is essential to use grade A glassware and take all other suitable precautions, such as temperature control. 

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