TOWN : 6484. International Standard © 6703/1 ‘Reta ona onan ah OA STanOATD A SneNE RAY ADANAN TAR AOC ANRAP FOAISONGNTEATION NTE RNATIONAI DU NORUNTATIN Water quality — Determination of cyanide — Part 1: Determination of total cyanide Théng tin TCDLCL Quolté de Yeou ~ Dosage des cyanures — Partie 1: Dosage des cyanures totes First edition — 1984-09-01 upc Descriptors: water, qualty, tests, determination, cyanides, wate polltion 267 Ref. No. 10 6703/1-1984 (E) Price baad on 11 pagesForeword {80 (the International Organization for Standardization) @ worldwide federation of rational standards bodies {150 member bodies). The work of preparing international Standards is normally carted out through 1SO technical committees. Every member body interested in a gubject for which 2 technical committee has been established has the Nght to be represented on that committes. Intemational organizations, govern ‘mental and non-governmental, in liaison with !SO, also take pat in the work Dratt International Standards adopted by the technical committees ae circulated 10 the member bodies for anproval before their acceptance as International Standards by the 150 Counei, They are approved in accordance with ISO procedures requring at least 75% approval by the member bodies voting. International Standacd {SO 6702/1 was prepared by Technical Committee 'S0/TC 147, Water auafy © International Organization for Star Printed in SwitzerContents © Introduction 41. Scope and fild of appication 2 Definition Section one: Liberation and absorption of hydrogen cyanide 3 Principle 4 Reagents 5 Aopen ‘ , Sampling andreas Proce. Section two: Dataminaon of cyanide ne ~ Protas matad win pvidne/ooure 250 8 Aoplcabiy 9 Pence. 10. Roogons 11 Apparatus 2 Proce 12. Exoessoncfresits 14 recon 18 Testeport Saction tras: Determination of cyanide fons — Ttette meth using the Tye 18 Aopntity 17 Pine and reactions 18 Reagents 19 Avner 20 Proce... 2 eens ofreuits 22 Prison 2a TesreprtINTERNATIONAL STANDARD 180 6703/1-1984 (E) Water quality — Determination of cyanide — Part 1: Determination of total cyanide Thong tin TCDLCL ‘Attention is drawn to the toxicity of cyanide and to the need to take extreme care when handling cyanides and their sol Carry out all oper jane in 2 fume cupboard. Avoid contact with the skin and eyes. When pipetting, always use 9 safety pipette (pipette by bulb. Detoxify samples and solutions containing cyanides or heavy metals in accordance with local offical sgulations. Othor chemicals specified in this part of ISO 6703 are also hazardous, for example pyridine. 0 Introduction Cyanides may be present in water as hydrocyarie aca {prussic ‘20d, as cyanide ions and 2s complex cyanides. They may be determined as total cyanide or as easty liberatable cyanide. If ‘anide compounds ae chlorinated, cyanogen chiovide (CICN} 'S produced, and this compound has to be determined separately “This Intornational Standard comprises four parts a follows Part 1: Determination of total cyanide Part 2: Determination of easly Moeratabe cyanise Part 3: Determination of evenogen chive Part 4: Determination of cyanide by difusion at pH 6” ‘The methods desesibed in part 1, 2 and 3 are suitable for con troling the quality of water and for the examination of ‘municipal sewage and industrial effiwents, They are aporopriate to the technology avalable for the destruction of eyanides in treatment plants, and are based on the separation of liberated hydrogen evanide (or in the case of ISO 6703/3, of cyanogen Chloride) by stripping with a carrier gas. ‘The method specified in part 4 i eutable forthe determination ‘of smaller amounts of cyanide, depending on the concentra: tions of copper and nickel This part of ISO 6703 comprises four sections, Section one als wth the liberation and absorption of hydrogen cyanide. “The other three sections deal with alternative methods for the ‘quantitative determination of cyanide fons, a follows: ‘photometric mathod with pyridine barbituric acd (se. tion two ‘roset atthe stage a eat — tivimetic method using the Tyndall effect (section — titrimetric methad using an indicator (soetion four) The specification of three alternative methods is necessary because each of the methods has its advantages and disadvan- tages. None can be quoted as eoplcable inal) cases, ‘The applicability of each method is described in clauses 8, 16 and 24, NOTE — ue to the diferent chomical behaviour of cyanide: contaning or cyanideproducng substances, i tt not posse to spect only one method forthe quentetve detention of eynige 1. Scope and field of application This part of ISO 6703 specifies three methods for the deter ‘mination of total cyanide (see clause 2) n water. The methods aro applicable to water containing less than 100 mg of cyanide perlite, but higher concentrations may be determined by suitable dilution of the sample. ‘The methods and corresponding ranges of eyenide contents for which they are sutable re as follows: = Photometric method with pytidine/barbiture acid 0,002 te 0,025 mg: ~ Titvimettic method using the Tyndall effect > 0,006 mg; = Tivimettc method using an indicator: > 0,08 mg.ISO 6703/1-1984 (E) A large number of ions and compounds interfere with the ‘determination. These ae listedin the table 1, together withthe concentrations below which they do not interfere (the lt not ‘xhaustive). 1 present singly or in combination, up to the limiting concentrations, thay do not interfere with the separa tion of hydrogen cyanie. The presence of aldehydes, € 9. f%- rmaldehyde, causes low cyaride values because of the forma: tion of eyanohydrin. any of the inting concentrations ofthe interferences skaly tebe exceeded. the sample shall be uted with dstiled water botore stabilization {gee clause 6) Other interference may arise from the presence of fatty acid, which wil dist and form soaps during tration of alkaline solu- tion, and from the presence of elementary sulfur. 2. Definition For the purpose of this Intemational Standard, the folowing definition apps. total cyanide: Simple and complex bound cyanides including forgarie compounds containing cyanogen groups forming hnydrogen cyarige undor the conditions of this method. CCyenonycrins are detected in part. CN-groups of compounds defined as such may party ot completely form cyanide ions oF hhydrocyanic acd respectively in water. Mononitles (R-CNY, ‘eyanate and thiocyanate ions and cyanogen chloride are notin cluded 1 — Interferences ing Inteterence concentration. molt Suite ions 000 Poly tn 00 Sulfide and polyetige fone +00 Swfde lone 00 “Thonstete ons 100 Thioeyarats ions 1000 Carbonate ions 100 000 sm 00 ‘Ammonium ions 20 Tromt ana went) one 5.000 Siver ons ry Mercury ions 0 Chorate fons =» Propions acd 100 Phenol 100 antivacene 100 Napthlene 100 ‘Aelia 0 Prerona! 10 Pyrat 100 Prine 10 Chore (ements) 20 Hydrogen pode 0 Perborte tons 0Section one: Liberat 3 Principle Heating the sample with hydrochloric acid in the presence of copper ions. Eniziament of the liberated hydrogen cyanide ina currant of air into an absorption vessel containing sacium hhycrexide solution ores 1 Comalox cobalt cyanides wil not be determined quanta, ‘cause, according te the concentions, they are cacorpoted ‘he etont of batwoen & and 15 56 ony, thie sso apple to some ‘orgerocranie compounds 2. The llect ofthe spect digestion procede on cyarahydtine 4 Reagents All reagents shal be of recogaized analytical grade and the ‘water used shal be cistiled of deionized water, 4.1 Hydrochloric acid, solution, 0 1,12 g/m. 4.2. Hydrochloric acid, solution, CHC = 1 moti Sodium hydroxide, solution, (NaOH! = 1 mol. 5 mois! 4.4 Sodium hydroxide, solution, ciNaOH! 4.5. Tinll) chloride, solution." Dissolve $0 of tol chloride dihydrate (SnCly 24,0) in 40 ml ofthe hydrochloric acid solution (8.2) and elute with water 100 mi. Propare a fresh solution each wook 4.8 Phenolphthalein, sclution, containing chloroform. Dissolve 0.08 g of pherolphthalein in $0 ml of ethonol and edd 10 mi of chloroform, 4.7 Zine- and cadmium sulfate, solution.” Dissolve 100g of zine sulfate heptahydrate (2aS0,.7H,0) and 100 gof cadmium sulfate octahydrat (3Cd SO, BH;0) in water and diute with water to 1 00 mi 4.8 Copperilt sulfate, solution Dissolve 20 g of copper! sulfate pentahydrate {€u80, 54,0) in water and dilute with water to 1 O00 mi. 180 6703/1-1984 {E) In and absorption of hydrogen cyanide 49 Cedmium acetate, solution." Dissolve 300 g of cadmium acetate dinyarate [Ca{CHyC00),.24,01 in water and elute with water to 1000 mi. 4.10. Buffer solution, of pH 5,4 Dissolve 6 9 of sodium hydroxide (NaOH) in approximately 50 mi water, add 11,8 g of suecinic acid (C,Mg0,) and dite with water to. 100 ml 5 Apparatus Usual laboratory equipment, and 5.1. Apparatus for the separation of hydrogen cyanide by tipping “The apparatus shown in figute 1, oF its equivalent, i recom: ‘mended end comprises the folawing components. 5.1.1. Three-neoked distilation flask. of capacity 500 mi, with standard conical joints {cents neck 29/22, side necks 145/231, . 5.1.2 Reflux condenser (Liebig condenser. 5.1.3 Absorption vessels, protected against rturn of liquid. 544 Funnel. 5.18 Flowmeter. of capacity 250 a, for purification of the 5.2_pH motor, with a glass electrode which wil fit nto the ‘side necks of the distilation flask 5.3 One-mark volumettic flasks, of capacities 25, 50, 50 and 1 000 ra 6 Sampling and samples Ifthe sample contains undissolved cyanige, iti necessary to fensure homogeneous distribution of the ‘undissolved sub- stances in the sample and ite dilutions. Immodkately after sampling, 30d § ml of the sodium hydroxide solution (4.4), 10m of ‘the phenoiphthalein solution (4.6) and 5 mi of the ‘itt chloride solution (4.5) to each litre of sample or ditod {)Sntig is ace as a acucing agen: rin sats ase to provi stable nc hexacyaroterates,chdmium stare ae as elie acceptor ane eens O tha bocteiial effet180 6703/1-1984 (E) Dimensions in ritimates 4 ro-nommea ard pump 4 09. 2/2 4 openings ate? 7 Fr condenser \ ot pee 0.2182 wash pote e452 MY Disiation fas Figure 1 — Apparatus for separation of hydrogen cyanide by strippingsample Adjust the pH to about 8 by adding the hydrochioric ‘acid solution (4.21, oF the sodium hydroxide solution (4.3, drop by drop, unt the water tums sightly red. Adjust the pH values of highly coloured samples inthe same way after checking with the pl-meter (5.2) or with an indicator paper. Finaly, add 10'mi of the zine- and cadmium sulfate solution (4.7) to each tre of sample. [Analyse the sample as soon 2s possible. I itis necessary to sore it, Keep it cool and in the dar. After addition of the zine- and cadmium sulfate solution, a precipitate which may contain hxacyanotercate, ig formed, ‘Accordingly, the sample should be rendered homogenous im: ‘mediately prior to taking aliquot portions, If replicate deter- ‘mination are to be cariod out, the aliquot portions shall be taken as quickly a¢ possible in order to minimize any loeses of ‘gaseous hydrogen cyanide due to disturbance of the fequibrium between the gaseous hydrogen cyanide and the hhyrocyanic acid in the quid phase ofthe pretreated sample. I the required volume of sample is already known before samp! ing, itis advisable to take only this volume and to carry out the {determination on the whole sample. 7 Procedure Liberation and absorption of hydrogen cyanide Pour 10 ml of the sodium hydroxide solution (4.3) into the a sorption vessel (5.131, connect the vessel to the condenser, 180 6703/1-1984 (E) connect the suction tube and adfust the ai low rate to 20 1/6, Pour into the distilation flask, in the follwing order, 30 ml of water, 10 rv ef the copper sulfate solution (48), 2 ml of the tin) chloride solution (4.8), 100 rv of the sample [eee clause 6) and 10 ml of the hydroctioricaeld solution (1). Connect the wash bottie containing epproximately 100ml ofthe sodium hydroxide solution (431, to the funnel and heat the flask unt the contents bot. Readjust the at flow rate 1020 1/h, Allow to reflux ata rate of 1 to 2 drops per second. | low eyanide concentrations (less than 0,1 mg/l} ate ex- ected, he volume of the sample may be increased to 200 mi In this case, increase the volumes of the copper) sulfate solu tion (4.8) 1020 ml, of the tn) chlaride solution (4.5) to 4 mt {and of the hydrochloric acid gohtion (4.1) to 20 Attar Th, discontinue boing.” 7.2. Blank test Carry out & blank test in parallel withthe determination, pro: ‘seeding 8s specified in 7.1 and section two, three or four a8 3p- ropriata, but replacing the somolo by cyanide free water tneated inthe sare way as the sample (208 clause 6. 7.3 Quantitative determination of cyanide ions Proceed as specified in section two (photometric mothod with pyridine berbture aie), section te (uitimettic method with {end-point determination using the Tyndall effect) or section four Ititimetic method using an indicator). ibe content ofthe absorption vessl suri or interarenceisexpected fr example te simple contains mare than 1 000mg of sue or taty ees, ropaat the boing ena svpping procode. ‘Trantor the contonts of tho absorption vassal through the funn into seond eailation flak containing 10 ito the cadmium act (43) and Om of the buffer Soiton (4.10) Aine he sbsorption vessel with approximately 60 lof water and ad th washings othe contr of the setlation Fast. Repeat he procedure by ‘eg the absorstion vessel, heating ad stripping as described in 7-1 without dng Further reagents,180 6703/1-1984 (E) Section two: Determination of cyanide ions — Photometric method with pyridine/barbituric acid 8 Applicability ‘hie method may be apoled to absorption solutions which con: tain 0,002 to 0,025 mg of cyanide. Absorption solutions with higher cyanide contents may be diluted with the sodium hydroxide solution (10.1) ‘Tho mothod is net applicable if oxides of nitrogen oF sufut oxide reach the absorption vessel during separation of the cyanides. Other imerferances include substances that infuence the action of the chloramine-T solution. Jnadition, coloured or turbid absoxptin solutione and absorp sion solutions containing compounds Toring dyes cannot be analysed by this method In viow of these possible interferences, it ia recommended that the results are checked by tivation with siver nitrate solution (see sections tree and fourl 9. Principle Reaction of the cyanide ions with the active chlorine of Chloramine-T, leading to the formation of cyanogen chloride which reacte with pyridine to form a glutacondialdohyde, whieh, in tur, condenses with two moles of barbituric acd 10 form a red-volet dye 10 Reagents {All eagents shall be of recognized analytical grade and the ‘water Used shal be distited or deionized water 10.1. Sodium hydroxide, solution, cINGOHI = 0,4 mol 10.2 Potossium cyanide (KEN) 10.3 Chloramine-T, solution Dissolve 0.5 9 of chioramine-T wihydrate {CyHCINNaO,S.34,0) in water in 2 50 rl one mark volumetric flask and cute to the mark Prepare @ fresh solution each week 10.4 Pyridine/barbituric acid, solution Place 3 g of barbituric acd (CqH4NOs) in 2 50 ml one-mark voketrc flask, wash down the walls of the flask with just enough watar to moisten the barbitric acid add 15 mi of Pyridine (CeHN} and swid to mix. Add 3 mi of the hydrochloric ‘cid solution (@.1) and tute tothe mark with water. ‘Store overnight in a refigerator and, i necessary. fiter 10 eliminate any undissolved barbituric ac ‘The solution is stable for 1 doy if stored in the dark and for 1 Wook if stored in ¢ refrigerator 105 Potassium cyanide, standard solution conespanding to 10 mg of CN perlite Dissolve 25 mg of potassium cyanide (KCN in the sodium hhycroxide solution (10.1) and dilute with the same sodium hydroxide Solution 10 1000 ml in a one-mark volumetie fash, ‘Standardize this solution by titration with the sver nitrate solu: tion (18.1), immediately before use or once each day if numerous determinations are catied out 11 Apparatus Usual laboratory equipment, and 11.4. Photometer, with cals of optical path length 10 mm, 12 Procedure 12.1. Transfer the contents of the absorption vessel to & 25 ml one:mark volumetric flask. Rinse the absorption vessel tee times with approximately 3m portions of water, transfor the rnsings to the flask, lute tothe mark with water and mix Transfer, by means of a pipette, 10 mi of this solution into a second 25 mi one-mark volumetic flatk, end add whist mix: ing, 2 mi of the butfer salution (4.20), 4 ml of the hydrachlerie acid solution (4.2) and 1 mot the enloramine-T solution (10.2. Stopper the flask and leave for 5 1 min, ‘Add 3 mt ofthe pyedine/barbiture acid solution 110.41, cute wrth water to the mark arc mix, Messure the absorbance at S78 am in a cell of optical path length 10 mm against a reference liquid"), Cony out the measurement 20 5 min after addition of the pyridine /bar Diturle acid solution, ‘Measure the absorbance of the blank test solution (7.2) simi lay. 1) Prepare tis retorence qui sing 10 lo the Sedum hyde solution (10,1 insted ofthe absorption solton12.2. Preparation of calibration graph 122.1. Preparation of standard solutions ‘Transfer, by means of a pipette 2, 5, 20 and 25 mi respectively ofthe standard potassium cyanide solution (10.5) into a series ‘of four 250 mi one-mark volumetric flasks. Dilute to the mark with the sosium hydroxide solution 10.1) and mix Proceed as specified in 12.1, sacond and thied paragraphs. 122.2 Photometric measurements Proceed ae specified in 12.1, fourth paragraph. 1223 Plotting the graph Plot a graph of absorbance against the cyanide contents, in ritigrams, of the solutions. The relationship between absor- bance and concentration le linear. Check the graph from time 10 tie, especialy it new packages of chomicals ave used. ‘Check the absolute value ofthe standard solutions by tration wth siver nitrate solution, 13. Expression of results ‘The total eyanide concentration, expressed in miligrams per lie, is given by the formula (omy = my) 1.000 thy where ‘my_ the cyanide content, in miligrams, ofthe test solu- tian rea from the calibration graph 180 6703/1-1984 (E) ‘my_ is the cyanide content, in miligrams, of the blank tect solution; Va. isthe volume, in mililtes, of the sample; Jy = 0,4, a8 only 40 % of the contents of the absorption vessel are used for the determination: Jz, = 0,97, 8 the volume of the sample is increased by the ‘kition of preservatives immediately after sampling. This factor is lowered by 0,01 for each 10mi, if, during ‘neutralzeton, more than 10 mi of reagent wore used for ‘each live of sample. Report results in milligrams per five, taking into account the precision shown in table 2. 14 Precision ‘The precision data shown in table 2 were obtained in inter laboratory tials: the samples were taken from the ground Wwoter ofa lnefil ares, 15 Test report ‘The test report shal include the following information 2). tha reference of the method used li. 1$0 6703/1, pho- tomettic method): the results and the method of expression used: )-any unusual features noticed during the determination; )detais of any operating procedures not specified in see tions one and two of this part of (SO 6703, or regarded as ‘optional, together with any incidents kay to have affect the results Table 2 — Procision data (photometric method) . coe Seose | Sama cat | Se Fa aT oR * See eat eee (ere Seecasaaons1S0 6703/1-1984 (E) Section three: Deter: Titrimetric method using the Tyndalll effect 16 Applicability “This method may be applied to absorption solutions which con tain more than 0,005 mg of eyande ‘The method Is not applicable i the absorption solution is turbid, though slightly turbid solutions may sil be rated. ln many eases, highly turbid solutions can be “cleaned up" by shaking wath 1 10 2 mi of earbon tetrachloride. Phase separa: von may be accelerated by using a centrifuge. V7 Pr le and reactions Formation of complex silver cyanide ions in accordance with the equation: ZEN” + Ags ~[Agicn,]~ whieh, in the presence of an excess of silver ions causes procritation of sliver cyanide: [Asien] ~ Ags =2AcN “The addition of potassium iodide improves the detection of the end-point (as the solubilty pcoduct of silver iodide is lower than that of siver cyanide: V+ Agr Aa! ‘The fermation of colloidal siver iodide is indicated by the Tyndat effect 18 Reagents {Al reagents shall be of recognized analytical grade and the ‘wate: used shal be dietiled or deionized water 18.1. Silver nitrate, solution, c(AgNO,) = 0,01 moll 1B.2_ Silver nitrate, saltion, e(AgNOa) = 0,001 mol/l ‘Store this solution, and the burett in which its used, in the dark. Check the tive of the solition at frequent intervals oF ‘prepare fresh solutions prior to each use from the siver niwate solution (18.0, 18.3 Potassium iodide, solstion. Dissolve 20. of potassium iodide in water and diute with ‘water to 100 mi 19 Apparatus isee figure 2) Usual laboratory equipment, anc 19.1. Automatic [dark glass) burette, of capacity 10 mi, capable of measuring volumes to an accuracy of 0,005 mor if fan automate burette i not available, a microburetts, 19.2. Magnetic st string bar. with a lack platform and black 19.3 High intensity light source, tor example a microscope lamp with an adjustable focussing lans and a eiaphragm, or a side projector with a diaphragm or a double-beam lamp with Hibre-opties system. The ciameter of the aperture shall be 4t0 mm 19.4 Titration vessels, made of glass, unmarked, of internal ciometer about 25 mm and capacity 20 ml 20 Procedure ‘Teansfer the contents ofthe absorption vessel into a25 mi one- mark volumetic ask, Ringe the vessal three times with approx- imately 3 mi portions of water, wansfor the insinge to the las, lute 16 the mark with water and mix. ‘The tivation should preferably be performed in @ darkened Pace the volumetric flask in the ight beam (see figure 2) f the solution is turbid, see oluse 16, a Tyndall effect is not clearly visible, transfer, by means of a pipette, two 10 ml aliquot por tions of the solution 10 two tration vessels (19.4) and add 1 drop ofthe potassium iodide solution (18.3) to each, Place one titration vessel on the magnetic sirer and add the string bar. Place the other vessel erwean tho frst one nd the light source (see fgure 2}. Ifa double-beam lamp is used, place the vessels side by si. Immerse the tip ofthe burette contain- ing the siver nitrate solution (18.2) in the solution, switch on the magnetic ster and start the titration. Taete slowly ‘because the formation of sive lodke i sow, ‘The endpoint ie reached when the turbidity coused by the “Tyndall effects clearly visible. This can be easy recognized by ‘comparison with the reference sample to which the siver ritrate soliton has not been added. Record the volume of the siver nitrate solution used. If this volume is more than § mi, ‘wansfer, by means of a pipette, two smaller aliquot portions (for example Tm) of the solution in the volumatric flask t0 titration vassels and add the sodium hyéroxie solution (10.1) 10 bring the total volume up to 10 ml. Repeat the titration, Exchange the tiation vessels and tanster the staring Bar. irate the second solution to the same degree of turbidity 35, the first one and record the volume of siver nitrate solution sed. Proceed similarly using the blank test solution. The total volume of silver nitrate solution used in the two trations in this blank test is usually 0,02 rl, but it shal not exceed! 0,04 mt in cach caseFigure 2 ~ Apparatus for determination of cyanide ions using Tyndall 21 Expression of results “The total cyanide concentration, expressed in miligrams per lite, i given by the formula (H+ Va Vo yx 1000 LhY where Yo isthe total volume, in eiilires, of silver nitrate solu- tion (18.2) required for the two titrations inthe blank tst; is the volume, in mites, of siver nitrate solution (18.2) oquted for the Fist tivation Vis the volume, in mililives, of silver nitrate solution (18.2) requited for the second titration; Vis the volume, in militras, ofthe sample Ji = 0,082, i. the mass, in miligrams, of CN" equivalent 40-1 mf 0,001 mol! siver nitrate solution; Ja = 08, 2s only BO % of the contents of the absorption ‘Vessel ae taken for tration ‘fy = 0,87, a8 the volume of the samp is increased by the ‘addition of preservatives immediately after samping. This, Diaphean 10 6703/1-1984 (E) factor is lowered by 0,01 for each 10m), if, during neutralization, more than 10 ml of reagent were used for ach ire of sample Report results in mitigrams per lire, taking Into secount the precision shown in table 3 . 2 Precision “The precision data shown in table 3 were obtained in inter laboratory tals; the samples were taken from the ground water of a landfil area, 23 Test report ‘The test roport shal include the following information 1a} the rforence of the method used Ie. 10 6703/1, tivimetic method using the Tyndall effect: 7 the results and the method of expression used, ©) any unusual features noticed during the determination 4d} details of any operating procedures not specified in se- tions one and three ofthis part of ISO 6708, or regarded as ‘optional, together with any incidents Hkely to have affected the results, “Table 3 ~ Precision date (tivimetic method) Comparnve ‘sample umber ot | Cyanide | opnecen’ mornin contort rat te Patan PoacyanoTer Sn z a 7 subtieg ero ” asa a Stblaed some wih aon St pas heracyanoteetll) Lo» 10 2#80 6703/1-1984 (E) Section four: Determination of cyanide ions — Titrimetric method using an indicator 24 Applicability ‘This method may be applied to absorption solutions containing ‘more than 0,05 mg of cyanide. ‘The “nethod isnot applicable ifthe absorption sok ‘oured or highly turbid. B Principle Titration of the contents of the absorption vessel with siver nitrate solution, the siver ions, when in excess, forming 8 red silver complex with §-4-dimethylaminobenzyidene) thodanine, 26 Reagents All reagents shall be of recognized analytical grade and the ‘water used shall be dlstiled oF deionized water. ‘The reagents spacifiad in clause 18, together with 28.1 Indicator solution. Dissolve 0,02 g of 6-(4dimethyiaminobenzyidene) shodanine in acetone and diute with acetone t0 100 mi. “This solution is stable fr about 1 woek if kopt in the dark 27 Apparatus sua laberatory equipment, and 211 Magoatic steer, with ba. 12. Buratte, of capacity 10. 27.3 Titration vessel, mado of glass, of capacity $0 28 Procedure ‘Transfer the contents of the absorption vessel into a 60 mi beaker. Rinse the vessel three times with approximately 5 ml portions of water and add tho rinsings to the beaker. Add 0,1 mit of the incicator solution (26.11, immerse the tip of the ‘buretta containing the silver nitrate solution (18.2) inthe solu tion, switch on the magnetic ster and titrate unt the colour changes from yellow to red. ‘The colour is stable ony fora short time. 1 more than 10 ml of the siver nitrate solution (18.2) are necessary, carry out the titration using the sive nitrate solution cia, Proceed simianly using the blank solution ? ‘The volume of the silver ritrate solution (18.2) used in thie blank test is usualy 0,08 mi, but it shall not excsed 0,2 mi 29 Expression of results ‘The total cyanide concentration, expressed in miligrams per litre, is given by the formula (Uy = Vol fy 1.000 ay where Voie the volume, in militres, of sive nitrate solution (18.2) cequired forthe blank test; is the volume, in miles, of sivernitvate sokstion (18.2) requited forthe titration; , isthe volume, in militres, of the sample; Jy = 0.082, 0. the mass, in miligrame, of CN™ equivalent 10 1 mi of 0,001 moll siver nitrate solution; J, = 0,87, 28 the volume of the sample is increased by the ‘dition of preservatives immediately after samping. This factor is lowered by 0,01 for each TOM, if, during ‘neutralization, more than 10 mil of reagent were used for ‘each live of sample. Report the result 10 the nearest 0,1 mg/l NOTE — Ifthe 0.01 mol/l sver nate solon wat uted, an ap: ropristecerecion should be mae. 1) “The method may be cat out potaniometicaly in whic case it can be usd for coloured or highly turbid souion. 2). Prepare tis blank test solution using 10 mo the sum hydroxide sohition (4.3) and 20 ml water 1030 Test report The test report shall include the folowing information: 1} the reference of the method used (ie. ISO 6703/1, tiimetic method using an indicator; 1) the results and the method of expression used; Bibliography 180 6703/1-1984 (E) any unuoval features noticed during the determination; 4d}_detals of any operating procedures not specified in sec- tions one and four ofthis part of ISO 6703, or regarded as ‘optional, together with any incidents ikely to have atfected the results Menrens. H.. 24 Wasser und Abwasser Forschung, 9, 1978), pp. 189-196. ‘Mearens, H., Vom Wasser, 62, (19791, pp. 61-76 n