College of Science

Determination of Chloride Ion Concentration by Titration (Mohrs Method)

Safety
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.

Solutions Needed
Silver nitrate solution: (0.1 mol L1) If possible, dry 5 g of AgNO3 for 2 hours at 100C 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.
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Introduction

Determination of Chloride Ionchromate indicator solution: (approximately Potassium 0.25 Concentration by Titration molL ) DissolveMethod)20 mL distilled (Mohrs 1 g of K CrO in water.
2 4

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

The end point of the titration + occurs when all the Ag (aq) + Cl(aq) AgCl(s) chloride ions are precipitated. Then additional silver ions react withThe end point of the titration occurs when all the the chromate ions of the indicator, chloride ions are precipitated. Then additional chloride potassium chromate, to form a red-brown of the indicator, ions react with the chromate ions precipitate of silver chromate. potassium chromate, to form a red-brown precipitate of
2 Ag (aq) + CrO4 (aq) Ag2CrO4(s) This method can be used can determine the chloride ion ion to be used to determine the chloride This method concentration of water samples from many sources concentration of water samples from many sources such as seawater, stream water, river water and estuary such as seawater, stream water, river water and estuary water. Seawater is example here. water. Seawater is used as theused as the example here.
The pH of the sample solutions should be between The pH of the sample solutions should be between 6.5 and 10. (Refer to the additional notes (3) for the 6.5 and 10. (Refer to the additional notes (3) for the gravimetric explanation). If the solutions are acidic, the explanation). Ifmethod or Volhards method shouldgravimetric the solutions are acidic, the be used. method or Volhards method should be used.

of a solution by titration with silver nitrate. As the silver nitrate solution is slowly AgCl a precipitate of silver Ag+(aq) + Cl added,(s) chloride forms. (aq)

Burette containing silver nitrate solution

2 Ag+(aq) + CrO42(aq) Ag2CrO4(s) + 2

silver chromate.

Equipmentburette and stand Needed

Equipment Needed
Conical flask

10 and burette and stand 20 mL pipettes 100 mL volumetric flask 10 and 20 mL pipettes 250 mL conical 100 mL volumetric flask flasks 250 mL conical10 mL and 100 mL measuring cylinders flasks 10 mL and 100 mL measuring cylinders

Seawater and chromate indicator

Solutions Needed

Silver nitrate solution:(0.1 mol L1) If possible, dry 5 g of AgNO3 for 2 hours at 100C and allow to cool. Accurately

as sand orPreparationmust be filtered before use. Sample seaweed, it Otherwise they will end up being weighed along with If silver chloride precipitate. thethe seawater contains traces of solid matter such as sand or seaweed, it must be filtered before use. Otherwise Titration Method they will end up being weighed along with the silver chloride precipitate. 1. Dilute seawater by pipetting a 20 mL sample into Sample Preparationflask and making it up to the mark aTitration 100 mL volumetric If thedistilled water. with seawater contains traces of solid matter such as 1. Dilute seawater by be filtered before use. sand or seaweed, it mustpipetting a 20 mL sample into 2. 100 mL volumetricaliquot of diluted seawater into a a Pipette a 10 mL flask and making it up to the mark Titration and add about 50 mL distilled water and 1 conical flask water. with distilled mL of chromate indicator. 1.2. Pipette a 10 mL aliquot of diluted seawaterinto a Dilute seawater by pipetting a 20 mL sample into a 3. 100 mL volumetric flask and makingsilver nitrate mark Titrate the sample with 50 mol L1 it up to the conical flask and add about 0.1 mL distilled water and 1 with distilled water. solution. Although the silver chloride that forms is a mL of chromate indicator. white precipitate, aliquot of diluted seawater into a 2.3.Pipette a 10 mL the chromate indicator initially gives Titrate the sample with 0.1 mol L1 silver nitrate the cloudyflask and add about 50 mL distilled water and solution conical Although a faint lemon-yellow colour (figure solution. the silver chloride that forms is a 1). 1 mLendpoint of the titration is identified as the first The of chromate indicator. white precipitate, the chromate indicator initially gives appearance of a red-brown colour of silver chromate 3.the cloudy solution a faint lemon-yellow colour (figure Titrate the sample with 0.1 mol L1 silver nitrate (figure 2). 1). The endpoint of the titrationchloride that forms is solution. Although the silver is identified as the first 4. a white precipitate, the chromate indicator of diluted Repeat of red-brown colour of aliquots initially appearancetheatitration with further silver chromate seawater until concordant results (titres agreeing within (figure 2). cloudy solution a faint lemon-yellow colour gives the 0.1(figure 1).obtained. 4. mL) are the titration with further aliquots of diluted Repeat

Result Calculationsred-brown colouration. identify the first appearance of

incompletely titrated reference flask for comparison is a helpful way to

1. Determine the average volume of silver nitrate used from your concordant titres. Result Calculations 4. Repeat the titration with further aliquots of diluted 2. Calculate the moles of silver nitrate reacting. 1. seawater until concordant resultsof silveragreeing Determine the average volume (titres nitrate usedUse the mL) are obtained. equation to determine from your concordant titres. 3. within 0.1 following reaction the moles of chloride ionsof silver nitrate reacting. 2. Calculate the moles reacting.
the moles of reacting. 4. Determinechloride ions volume of silver nitrate used the concentration of chloride ions in the 1. Calculatethe average diluted seawater. + + Cl AgCl Ag (aq) from your concordant titres. (aq) (s) 5. Calculate the moles of silver nitrate reacting. in the Calculate the concentration of chloride ions 2. Calculate the concentration of chloride 4. originalthe following reaction equation to determine the diluted seawater. 3. Use undiluted seawater. 3. Use the following reaction equation Ag+(aq) + Cl Result Calculations(aq) AgCl(s) to determine

6. moles of chloride ions reacting. sodium chloridethe 5. Calculate the concentration of chloride ions in in Calculate the concentration of the seawater in molL1, gL1 and g/100 mL (%). original undiluted seawater.
6. Calculate the concentration of sodium chloride in 4. Calculate the concentration of chloride ions in the Additionalin molL1, gL1 and g/100 mL (%). the seawater Notes diluted seawater. 1. Calculate the concentrationstain clothes andin the 5. Silver nitrate solution will of chloride ions skin. Any spills should be rinsed with water immediately. Additional Notes original undiluted seawater.

Ag+(aq) + Cl(aq) AgCl(s)

2. Calculate the concentration stainare usually saved the 1. Silver nitrate solution will of sodium chloride in 6. Residues containing silver ions clothes and skin. later recovery be rinsed with Check this with Any spills shouldof 1, gL and g/100 mL (%). your seawater until concordant results (titres agreeing within forseawater in molLsilver1metal. water immediately. teacher. 0.1 mL) are obtained. 2. Residues containing silver ions are usually saved
for The Mohr Notes 3. later recovery of silver metal. Check this with your Additional titration should be carried out under teacher. conditions of pH 6.5 9. At higher pH silver ions may be removed by precipitation with hydroxide ions,under 3. The Mohr titration should be carried out and at low pH chromate 6.5 may be ions pH silveran acid-base 1. Residuesof pH ions 9.silver removed by ions may for conditions containing At higher are usually saved be reactionrecovery hydrogenwith hydroxide ions, and at later to form of silver chromate ions or dichromate removed by precipitation metal. Check this with your ions,pH chromatelaboratorybe the end point. acid-base teacher or the accuracy supervisor. low affecting theions may of removed by an

2. It is a good idea should be carriedrough titration reaction to form hydrogen chromate a out dichromate 4. The Mohr titrationto first carry outions or under conditions the 6.5 9. of the end point. ions, affectingof pHfamiliar At higher pH silver ions may in order to become accuracywith the colour change at removed thebe It is a good idea to first carry outhydroxide ions, 4. end point. by precipitation with a rough titration Figure 1 Before the addition of any silver nitrate the chromate indicator low The endpoint of a lemon-yellow is identified as the first 5. and atMohrpH chromate ions may be removed by an gives the clear solutionthe titration colour. in order to become familiar with the colour change at The titration is sensitive to the presence acid-base reaction to form hydrogen chromate ions appearance of a red-brown colour of silver chromate of both chloride and bromide ions in solution and the end point. or dichromate ions, affecting the accuracy of the (figure 2). will not be too accurate when there toa significant 5. end point. titration is sensitive is the presence The Mohr concentration of and bromide ionsas well as the of both chloride bromide present in solution and 3. It is a good to first cases, suchrough titration a chloride.be tooideain most carry out is aas seawater, will not However, accurate when there significant in order to become familiar with the colour change at the bromide concentrationpresent negligible.the this will be as well as For concentration of bromide the the method reason,end point. in most cases, such as seawater, chloride. However, can also be used to determine either the total concentration ofbe negligible. bromide 4. The Mohr titration is sensitivechloride and For this the bromide concentration will to the presence of both in solution, and bromide also be used to determinethebe chloride method can ions in of bromide when reason, the or the concentrationsolution and will not Figure 2 Left flask: before the titration endpoint, addition of Ag+ ions chloride concentration is knownsignificant concentration too the total when there is of chloride and bromide either accurate concentration a to be negligible. leads to formation of silver chloride precipitate, making the solution in of bromide present as well as thebromide when the solution, or the concentration of chloride. However, cloudy. The chromate indicator gives a faint lemon-yellow colour. Figure flask: atflask:endpoint,thethe Cl ions have precipitated. The Ag+ Figure 2 Left the before all titration endpoint, addition+ ions Centre 2 Left flask:before the titration endpoint, addition of Ag of in most cases, such as known to be negligible. chloride concentration is seawater, the bromide ions leads to formation ofchloridechloride precipitate, making a leads to formation of silver silver precipitate, making the solution slightest excess of Ag+ precipitates with the chromate indicator giving concentration will be negligible. For this reason, the cloudy. The cloudy. indicator gives indicator gives a colour. the solutionchromateThe chromate a faint lemon-yellowis continued slight red-brown colouration. Right flask: If addition of Ag+faint lemon method can also be used to determine either the total Centre endpoint, further silver the endpoint, all the Cl ions yellow colour. Centre flask: atchromate precipitate is formed The past the flask: at the endpoint, allthe Cl ions have precipitated. + slightest excess of The slightest with the chromate indicator with concentration of chloride and bromide in solution, have precipitated. Ag precipitatesexcess of Ag+ precipitates giving a slight red-brown colouration. Rightslight If addition ofcolouration. flask: red-brown Ag+ is continued or the concentration of bromide when the chloride a 2 the chromate indicator givingchromate precipitate is formed past the endpoint, further silver + Right flask: If addition of Ag is continued past the endpoint, concentration is known to be negligible.
Figure Before the addition of silver nitrate the chromate indicator Figure11Before the addition of any any silver nitrate the chromate gives the gives the clear solution a colour. indicatorclear solution a lemon-yellow lemon-yellow colour.

further silver chromate precipitate is formed and a stronger 2 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.