College of Science Determination of Chloride Ion Concentration by Titration (Mohr’s Method) Safety Solutions Needed Lab coats, safety glasses and enclosed footwear must be worn at all times in the laboratory. The chromate solution needs to be prepared and used with care as chromate is a known carcinogen. Silver nitrate solution causes staining of skin and fabric (chemical burns). Any spills should be rinsed with water immediately. Silver nitrate solution: (0.1 mol L−1) If possible, dry 5 g of AgNO3 for 2 hours at 100°C and allow to cool. Accurately weigh about 4.25 g of solid AgNO3 and dissolve it in 250 mL of distilled water in a conical flask. Store the solution in a brown bottle. Determination of Chloride Ionchromate indicator solution: (approximately Potassium 0.25 molL ) Dissolve 1 g of K CrO in 20 mL distilled Concentration by Titration (Mohr’s Method) water. -1 2 4 Introduction This method determines the chloride ion concentration of a solution by titration with silver nitrate. As the silver Introduction nitrate solution is slowly added, a precipitate of silver chloride forms.This method determines the chloride ion concentration of a solution by titration with silver nitrate. As the silver nitrate added, a precipitate of silver Ag+(aq)solution + Cl–is slowly → AgCl (s) chloride forms. (aq) Burette containing silver nitrate solution The end point of the titration +occurs–when all the Ag (aq) + Cl (aq) → AgCl(s) chloride ions are precipitated. Then additional silver point of the titration occurs when all the ions react withThe theend chromate ions of the indicator, chloride ions are precipitated. Then additional chloride potassium chromate, form red-brown precipitate of ions reactto with the achromate ions of the indicator, silver chromate. potassium chromate, to form a red-brown precipitate of silver chromate. 2 Ag+(aq) + CrO42–+ (aq) → Ag CrO4(s) 2– 2 2 Ag (aq) + CrO4 (aq) → Ag2CrO4(s) This method can be used to determine the chloride ion This method can be used to determine the chloride ion concentration of water samples many concentration of waterfrom samples fromsources many sources such as seawater, water, riverwater, water and estuary suchstream as seawater, stream river water and estuary Seawater is used as the example water. Seawaterwater. is used as the example here. here. The pH ofsolutions the sampleshould solutionsbe should be between The pH of the sample between 6.5 and 10. (Refer to the additional notes (3) for the 6.5 and 10. (Refer to the additional notes for the thegravimetric explanation). If the solutions are(3) acidic, explanation). Ifmethod the solutions are acidic, the gravimetric or Volhard’s method should be used. method or Volhard’s method should be used. Equipment Needed Equipmentburette Needed and stand 10 and 20 mL pipettes burette and stand 100 mL volumetric flask 10 and 20 mL pipettes 250 mL conical flasks 100 mL volumetric flask mL and 100 mL measuring cylinders 250 mL conical10flasks 10 mL and 100 mL measuring cylinders Solutions Needed Silver nitrate solution:(0.1 mol L−1) If possible, dry 5 g of AgNO3 for 2 hours at 100°C and allow to cool. Accurately Conical flask Seawater and chromate indicator asSample sand orPreparation seaweed, it must be filtered before use. Otherwise they will end up being weighed along with If the seawater contains traces of solid matter such the silver chloride precipitate. as sand or seaweed, it must be filtered before use. Otherwise they will end up being weighed along with Titration Method the silver chloride precipitate. 1. Dilute seawater by pipetting a 20 mL sample into Sample Preparation aTitration 100 mL volumetric flask and making it up to the mark Ifwith thedistilled seawaterwater. contains traces of solid matter such as 1. orDilute seawater by pipetting mL sample sand seaweed, it must be filtereda 20 before use. into 2.a 100Pipette a 10 mL aliquot of diluted seawater into a mL volumetric flask and making it up to the mark Titration conical flask and add about 50 mL distilled water and 1 with distilled water. mL of chromate indicator. 1.2.Dilute seawater by aliquot pipetting a 20 mLseawater sample into Pipette a 10 mL of diluted into aa −1 100Titrate mLflask volumetric and it upwater to theand mark nitrate 3.conical the sample with 0.1 moldistilled L silver and addflask about 50making mL 1 with distilled water. solution. Although the silver chloride that forms is a mL of chromate indicator. white precipitate, the chromate indicator initially 2.3.Pipette a 10the mLsample aliquot of diluted intogives a Titrate with 0.1 molseawater L−1 silver nitrate theconical cloudyflask solution a faint lemon-yellow colour (figure and add about 50 mL distilled water solution. Although the silver chloride that forms is aand 1). 1The of the titration is identified as the first mLendpoint of chromate indicator. white precipitate, the chromate indicator initially gives appearance of a red-brown colour of−1 silver chromate cloudy faint0.1 lemon-yellow 3.the Titrate thesolution sampleawith mol L silvercolour nitrate(figure (figure 2). 1).solution. The endpoint of thethe titration is identified the first Although silver chloride thatasforms is 4.appearance Repeat the further aliquots of diluted of atitration red-brown colour ofindicator silver chromate a white precipitate, thewith chromate initially seawater until concordant agreeing within (figure gives 2). the cloudy solutionresults a faint(titres lemon-yellow colour 0.1 mL) are obtained. (figure 1). 4. Repeat the titration with further aliquots of diluted incompletely titrated reference flask for comparison is a helpful way to Result identify theCalculations first appearance of red-brown colouration. 1. Determine the average volume of silver nitrate used fromCalculations your concordant titres. Result 4. Repeat the titration with further aliquots of diluted 2.1. Calculate the moles of silver nitratesilver reacting. Determine average volume nitrate seawater untilthe concordant resultsof (titres agreeing used from your concordant titres. 3. within Use the following reaction equation to determine 0.1 mL) are obtained. the of chloride ionsof reacting. 2. moles Calculate the moles silver nitrate reacting. 3. Use Calculations the following Ag+(aq) +reaction Cl–(aq) →equation AgCl(s) to determine Result the moles of chloride ions reacting. 4. Calculatethe theaverage concentration ions inused the 1. Determine volumeofofchloride silver nitrate + – diluted seawater. Ag (aq) + Cltitres. → AgCl(s) from your concordant (aq) 5.2. Calculate the concentration of ions in the the moles of silver nitrate reacting. 4. Calculate Calculate the concentration of chloride chloride original undiluted seawater. diluted seawater. 3. Use the following reaction equation to determine the of chloride ions reacting. 6.5. moles Calculate the of in Calculate theconcentration concentration of sodium chloridechloride ions in the −1 −1 , gL and g/100 mL (%). the seawater in molL original undiluted seawater. Ag+(aq) + Cl–(aq) → AgCl(s) 6. Calculate the concentration of sodium chloride in 4. Calculate the concentration of chloride ions in the Additional the seawater inNotes molL−1, gL−1 and g/100 mL (%). diluted seawater. 1.5. Calculate Silver nitrate solution will stain clothesions andin skin. the concentration of chloride the Any spills should be rinsed with water immediately. Additional Notes original undiluted seawater. 2. Residues containing ions are usually 1. Calculate Silver nitrate solutionsilver will stain clothes andsaved skin. 6. the concentration of sodium chloride in the later recovery of silver Check this with your Any spills should be with water immediately. −1rinsed −1metal. seawater until concordant results (titres agreeing within for seawater in molL , gL and g/100 mL (%). teacher. 0.1 mL) are obtained. 2. Residues containing silver ions are usually saved for later of silver metal.beCheck this with your 3.Additional The recovery Mohr titration should carried out under Notes teacher. conditions of pH 6.5 – 9. At higher pH silver ions may be removed precipitation with hydroxide and at 3. Theby Mohr titration should be carriedions, out under low pH chromate ions– may removed by an acid-base 1.conditions Residues ions aresilver usually saved ofcontaining pH 6.5 9.silver At be higher pH ions may for be reaction to form hydrogen chromate ions or dichromate later recovery of silver metal. Check this with your removed by precipitation with hydroxide ions, and at ions, affecting thelaboratory accuracy ofsupervisor. the end point. or the lowteacher pH chromate ions may be removed by an acid-base 2. The titration be carried out reaction form hydrogen or under dichromate 4. It Mohr is atogood idea toshould firstchromate carry outions a “rough” titration conditions ofthe pHaccuracy 6.5 – 9. with At pH silver ionsatmay affecting of higher the end point. inions, order to become familiar the colour change be removed by precipitation with hydroxide the end point. 4. It is a good idea to first carry out a “rough” ions, titration Figure 1 Before the addition of any silver nitrate the chromate indicator at low pH chromate ions be removed Thethe endpoint of the titration colour. is identified as the first 5.in and gives clear solution a lemon-yellow order become familiar with may thetocolour changeby atan Theto Mohr titration is sensitive the presence acid-base reaction to form hydrogen chromate ions appearance of a red-brown colour of silver chromate of the endchloride point. and bromide ions in solution and both or dichromate ions, affecting the accuracy of the (figure 2). will not be too accurate there to is athe significant 5. endThe Mohr titrationwhen is sensitive presence point. concentration of bromide present as well as the of both chloride and bromide ions in solution and 3. It is a good ideain tomost first carry out a “rough” titration chloride. However, cases, such as seawater, will not be too accurate when there is a significant in order to become familiar with the colour the bromide concentration will be negligible. Forchange this at concentration of bromide present as well as the the end point. reason, the methodincan alsocases, be used toas determine chloride. However, most such seawater, either the total concentration of chloride and 4. The Mohr titration is sensitive to the presence of both the bromide concentration will be negligible. bromide For this in solution, or the concentration of bromide when thebe chloride bromide ionsbe in used solution and will not reason, theand method can also to determine Figure 2 Left flask: before the titration endpoint, addition of Ag+ ions chloride concentration is known to be negligible. too accurate when there is aofsignificant concentration either the total concentration chloride and bromide leads to formation of silver chloride precipitate, making the solution of bromide present as well as the chloride. However, in solution, or the concentration of bromide when the cloudy. The chromate indicator gives a faint lemon-yellow colour. +of Ag+ Figure 22 Left beforethe the titration endpoint, addition Figureflask: Leftatflask: flask: before endpoint, addition of Ag ions have precipitated. The Centre the endpoint, alltitration the Cl− ions in most cases, such as seawater, the bromide chloride concentration is known to be negligible. ions leads to formation ofchloride silverwith chloride precipitate, leads toexcess formation silver precipitate, making themaking solution the chromate indicator giving a slightest of Agof+ precipitates concentration will be negligible. For this reason, the cloudy. The chromate indicator gives aindicator faint lemon-yellow the solution cloudy. The chromate gives a +faint lemoniscolour. continued slight red-brown colouration. Right flask: If addition of Ag − method can also be used to determine either the total − ions haveallprecipitated. The Centre flask: atCentre thefurther endpoint, allchromate the Cl yellow flask: at the endpoint, the Cl ions past thecolour. endpoint, silver precipitate is formed + with theofchromate indicator giving slightest excess of Ag concentration of chloride and bromide in solution, have precipitated. Theprecipitates slightest excess Ag+ precipitates with a + is continued slight red-brown colouration. Right flask: If addition of Ag or the concentration of bromide when the chloride indicator giving a slight red-brown colouration. 2 thepastchromate the endpoint, further silver + chromate precipitate is formed Right flask: If addition of Ag is continued past the endpoint, concentration is known to be negligible. Figure 11Before addition of any silversilver nitrate the chromate indicator Figure Beforethe the addition of any nitrate the chromate gives the clear a lemon-yellow colour. indicator givessolution the clear solution a lemon-yellow colour. silver chromate precipitate is formed and a stronger 2further red-brown colour results. NB: The titration should be stopped when the first trace of red-brown colour is observed. Using an incompletely titrated reference flask for comparison is a helpful way to identify the first appearance of red-brown colouration.